Simple eco-friendly synthesis of the surfactant free SnS nanocrystal toward the photoelectrochemical cell application.

PubMed

Huang, Xiaoguang; Woo, Heechul; Wu, Peinian; Hong, Hyo Jin; Jung, Wan Gil; Kim, Bong-Joong; Vanel, Jean-Charles; Choi, Jin Woo

2017-11-28

A simple, low cost, non-toxic and eco-friendly pathway for synthesizing efficient sunlight-driven tin sulfide photocatalyst was studied. SnS nanocrystals were prepared by using mechanical method. The bulk SnS was obtained by evaporation of SnS nanocrystal solution. The synthesized samples were characterized by using XRD, SEM, TEM, UV-vis, and Raman analyses. Well crystallized SnS nanocrystals were verified and the electrochemical characterization was also performed under visible light irradiation. The SnS nanocrystals have shown remarkable photocurrent density of 7.6 mA cm -2 under 100 mW cm -2 which is about 10 times larger than that of the bulk SnS under notably stable operation conditions. Furthermore, the SnS nanocrystals presented higher stability than the bulk form. The IPCE(Incident photon to current conversion efficiency) of 9.3% at 420 nm was obtained for SnS nanocrystal photoanode which is strikingly higher than that of bulk SnS, 0.78%. This work suggests that the enhancement of reacting area by using SnS nanocrystal absorbers could give rise to the improvement of photoelectrochemical cell efficiency.

Hydroxyapatite nanocrystals: simple preparation, characterization and formation mechanism.

PubMed

Mohandes, Fatemeh; Salavati-Niasari, Masoud; Fathi, Mohammadhossein; Fereshteh, Zeinab

2014-12-01

Crystalline hydroxyapatite (HAP) nanoparticles and nanorods have been successfully synthesized via a simple precipitation method. To control the shape and particle size of HAP nanocrystals, coordination ligands derived from 2-hydroxy-1-naphthaldehyde were first prepared, characterized by Fourier transform infrared (FT-IR) and proton nuclear magnetic resonance ((1)H-NMR) spectroscopies, and finally applied in the synthesis process of HAP. On the other hand, the HAP nanocrystals were also characterized by several techniques including powder X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). According to the FE-SEM and TEM micrographs, it was found that the morphology and crystallinity of the HAP powders depended on the coordination mode of the ligands. Copyright © 2014 Elsevier B.V. All rights reserved.

Colloidal Nanocrystals with Near-infrared Optical Properties: Synthesis, Characterization, and Applications

NASA Astrophysics Data System (ADS)

Panthani, Matthew George

2011-07-01

Colloidal nanocrystals with optical properties in the near-infrared (NIR) are of interest for many applications such as photovoltaic (PV) energy conversion, bioimaging, and therapeutics. For PVs and other electronic devices, challenges in using colloidal nanomaterials often deal with the surfaces. Because of the high surface-to-volume ratio of small nanocrystals, surfaces and interfaces play an enhanced role in the properties of nanocrystal films and devices. Organic ligand-capped CuInSe2 (CIS) and Cu(InXGa 1-X)Se2 (CIGS) nanocrystals were synthesized and used as the absorber layer in prototype solar cells. By fabricating devices from spray-coated CuInSe nanocrystals under ambient conditions, solar-to-electric power conversion efficiencies as high as 3.1% were achieved. Many treatments of the nanocrystal films were explored. Although some treatments increased the conductivity of the nanocrystal films, the best devices were from untreated CIS films. By modifying the reaction chemistry, quantum-confined CuInSe XS2-X (CISS) nanocrystals were produced. The potential of the CISS nanocrystals for targeted bioimaging was demonstrated via oral delivery to mice and imaging of nanocrystal fluorescence. The size-dependent photoluminescence of Si nanocrystals was measured. Si nanocrystals supported on graphene were characterized by conventional transmission electron microscopy and spherical aberration (Cs)-corrected scanning transmission electron microscopy (STEM). Enhanced imaging contrast and resolution was achieved by using Cs-corrected STEM with a graphene support. In addition, clear imaging of defects and the organic-inorganic interface was enabled by utilizing this technique.

Synthesis of germanium nanocrystals in high temperature supercritical CO2

NASA Astrophysics Data System (ADS)

Lu, Xianmao; Korgel, Brian A.; Johnston, Keith P.

2005-07-01

Germanium nanocrystals were synthesized in supercritical (sc) CO2 by thermolysis of diphenylgermane (DPG) or tetraethylgermane (TEG) with octanol as a capping ligand at 500 °C and 27.6 MPa. The Ge nanocrystals were characterized with high resolution transmission electron microscopy (HRTEM), energy-dispersive x-ray spectroscopy (EDS), and x-ray diffraction (XRD). On the basis of TEM, the mean diameters of the nanocrystals made from DPG and TEG were 10.1 and 5.6 nm, respectively. The synthesis in sc-CO2 produced much less organic contamination compared with similar reactions in organic supercritical fluids. When the same reaction of DPG with octanol was performed in the gas phase without CO2 present, bulk Ge crystals were formed instead of nanocrystals. Thus, the solvation of the hydrocarbon ligands by CO2 was sufficient to provide steric stabilization. The presence of steric stabilization in CO2 at a reduced temperature of 2.5, with a reduced solvent density of only 0.4, may be attributed to a reduction in the differences between ligand-ligand interactions and ligand-CO2 interactions relative to thermal energy.

Polar-solvent-free colloidal synthesis of highly luminescent alkylammonium lead halide perovskite nanocrystals

NASA Astrophysics Data System (ADS)

Vybornyi, Oleh; Yakunin, Sergii; Kovalenko, Maksym V.

2016-03-01

A novel synthesis of hybrid organic-inorganic lead halide perovskite nanocrystals (CH3NH3PbX3, X = Br or I) that does not involve the use of dimethylformamide or other polar solvents is presented. The reaction between methylamine and PbX2 salts is conducted in a high-boiling nonpolar solvent (1-octadecene) in the presence of oleylamine and oleic acid as coordinating ligands. The resulting nanocrystals are characterized by high photoluminescence quantum efficiencies of 15-50%, outstanding phase purity and tunable shapes (nanocubes, nanowires, and nanoplatelets). Nanoplatelets spontaneously assemble into micrometer-length wires by face-to-face stacking. In addition, we demonstrate amplified spontaneous emission from thin films of green-emitting CH3NH3PbBr3 nanowires with low pumping thresholds of 3 μJ cm-2.A novel synthesis of hybrid organic-inorganic lead halide perovskite nanocrystals (CH3NH3PbX3, X = Br or I) that does not involve the use of dimethylformamide or other polar solvents is presented. The reaction between methylamine and PbX2 salts is conducted in a high-boiling nonpolar solvent (1-octadecene) in the presence of oleylamine and oleic acid as coordinating ligands. The resulting nanocrystals are characterized by high photoluminescence quantum efficiencies of 15-50%, outstanding phase purity and tunable shapes (nanocubes, nanowires, and nanoplatelets). Nanoplatelets spontaneously assemble into micrometer-length wires by face-to-face stacking. In addition, we demonstrate amplified spontaneous emission from thin films of green-emitting CH3NH3PbBr3 nanowires with low pumping thresholds of 3 μJ cm-2. Electronic supplementary information (ESI) available: Materials and methods, additional figures. See DOI: 10.1039/c5nr06890h

Synthesis and structure characterization of chromium oxide prepared by solid thermal decomposition reaction.

PubMed

Li, Li; Yan, Zi F; Lu, Gao Q; Zhu, Zhong H

2006-01-12

Mesoporous chromium oxide (Cr2O3) nanocrystals were first synthesized by the thermal decomposition reaction of Cr(NO3)3.9H2O using citric acid monohydrate (CA) as the mesoporous template agent. The texture and chemistry of chromium oxide nanocrystals were characterized by N2 adsorption-desorption isotherms, FTIR, X-ray diffraction (XRD), UV-vis, and thermoanalytical methods. It was shown that the hydrate water and CA are the crucial factors in influencing the formation of mesoporous Cr2O3 nanocrystals in the mixture system. The decomposition of CA results in the formation of a mesoporous structure with wormlike pores. The hydrate water of the mixture provides surface hydroxyls that act as binders, making the nanocrystals aggregate. The pore structures and phases of chromium oxide are affected by the ratio of precursor-to-CA, thermal temperature, and time.

Hierarchial Junction Solar Cells Based on Hyper-Branched Semiconductor Nanocrystals

DTIC Science & Technology

2009-06-30

Hyper-Branched Semiconductor Nanocrystals 4 2. Cu2S- CdS all-inorganic nanocrystal solar cells. We demonstrated the rational synthesis of... Hydrothermal Synthesis of Single Phase Pyrite FeS2 Nanocrystals. We demonstrated a single-source molecular precursor that can be used for the synthesis ... CdS Semiconductor Nanostructures,” Advanced Materials, (2008), 20(22), 4306. Y. Wu, C. Wadia, W. Ma, B. Sadtler, A. P. Alivisatos, “ Synthesis of

Synthesis and characterization of monodispersed polymer/polydiacetylene nanocrystal composite particles.

PubMed

Wei, Zhong; Ujiiye-Ishii, Kento; Masuhara, Akito; Kasai, Hitoshi; Okada, Shuji; Matsune, Hideki; Asahi, Tsuyoshi; Masuhara, Hiroshi; Nakanishi, Hachiro

2005-06-01

Monodispersed polymer/polydiacetylenecomposite particles were synthesized by soap-free seeded emulsion polymerization of styrene andmethyl methacrylate; the products were characterized by XRD, SEM, TEM, UV-visible spectroscopy, and single particle scattering spectroscopy. In the synthesis process, polydiacetylene nanocrystals were found to act as inhibitor, and consequently a relatively low concentration was necessary. Different monomers lead to the differences in reaction condition and particle morphology; the PMMA composite particles were simpler in preparation than polystyrene particles, but the latter havebetter spherical morphology. The composite particles were composed of polymer shells and polydiacetylene cores, which kept their crystal structure and optical properties. A high percentage of cored particles could be achieved with optimized reaction conditions where the amount of seed was sufficient and the oily oligomer by-product was suppressed.

Inorganic Chemistry Solutions to Semiconductor Nanocrystal Problems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alvarado, Samuel R.; Guo, Yijun; Ruberu, T. Purnima A.

2014-03-15

The optoelectronic and chemical properties of semiconductor nanocrystals heavily depend on their composition, size, shape and internal structure, surface functionality, etc. Available strategies to alter these properties through traditional colloidal syntheses and ligand exchange methods place a premium on specific reaction conditions and surfactant combinations. In this invited review, we apply a molecular-level understanding of chemical precursor reactivity to reliably control the morphology, composition and intimate architecture (core/shell vs. alloyed) of semiconductor nanocrystals. We also describe our work aimed at achieving highly selective, low-temperature photochemical methods for the synthesis of semiconductor–metal and semiconductor–metal oxide photocatalytic nanocomposites. In addition, we describemore » our work on surface modification of semiconductor nanocrystal quantum dots using new approaches and methods that bypass ligand exchange, retaining the nanocrystal's native ligands and original optical properties, as well as on spectroscopic methods of characterization useful in determining surface ligand organization and chemistry. Using recent examples from our group and collaborators, we demonstrate how these efforts have lead to faster, wider and more systematic application of semiconductor nanocrystal-based materials to biological imaging and tracking, and to photocatalysis of unconventional substrates. We believe techniques and methods borrowed from inorganic chemistry (including coordination, organometallic and solid state chemistry) have much to offer in reaching a better understanding of the synthesis, functionalization and real-life application of such exciting materials as semiconductor nanocrystals (quantum dots, rods, tetrapods, etc.).« less

The dual role of sulfur-containing amino acids in the synthesis of IV-VI semiconductor nanocrystals: a mechanochemical approach.

PubMed

Baláž, Peter; Baláž, Matej; Caplovičová, Mária; Zorkovská, Anna; Caplovič, Lubomír; Psotka, Miroslav

2014-01-01

PbS@cystine nanocrystals were synthesized mechanochemically, with lead acetate and L-cystine being used as the lead and sulfur precursors, respectively. The resulting nanocrystals are 22-34 nm in size, well-faceted and octahedral in shape. Characterization by XRD, FT-IR, NMR, FE-SEM, EDS, TEM (HRTEM) and surface area measurement methods showed that the particles are single, defect-free crystals with a high crystallinity. Furthermore, the crystals were prepared using a solvent-free procedure that was performed under ambient temperature and atmospheric pressure.

Correlation between CdSe QD Synthesis, Post-Synthetic Treatment, and BHJ Hybrid Solar Cell Performance

PubMed Central

Eck, Michael; Krueger, Michael

2016-01-01

In this publication we show that the procedure to synthesize nanocrystals and the post-synthetic nanocrystal ligand sphere treatment have a great influence not only on the immediate performance of hybrid bulk heterojunction solar cells, but also on their thermal, long-term, and air stability. We herein demonstrate this for the particular case of spherical CdSe nanocrystals, post-synthetically treated with a hexanoic acid based treatment. We observe an influence from the duration of this post-synthetic treatment on the nanocrystal ligand sphere size, and also on the solar cell performance. By tuning the post-synthetic treatment to a certain degree, optimal device performance can be achieved. Moreover, we show how to effectively adapt the post-synthetic nanocrystal treatment protocol to different nanocrystal synthesis batches, hence increasing the reproducibility of hybrid nanocrystal:polymer bulk-heterojunction solar cells, which usually suffers due to the fluctuations in nanocrystal quality of different synthesis batches and synthesis procedures. PMID:28335243

Colloidal chemical synthesis and formation kinetics of uniformly sized nanocrystals of metals, oxides, and chalcogenides.

PubMed

Kwon, Soon Gu; Hyeon, Taeghwan

2008-12-01

Nanocrystals exhibit interesting electrical, optical, magnetic, and chemical properties not achieved by their bulk counterparts. Consequently, to fully exploit the potential of nanocrystals, the synthesis of nanocrystals must focus on producing materials with uniform size and shape. Top-down physical processes can produce large quantities of nanocrystals, but controlling the size is difficult with these methods. On the other hand, colloidal chemical synthetic methods can produce uniform nanocrystals with a controlled particle size. In this Account, we present our synthesis of uniform nanocrystals of various shapes and materials, and we discuss the kinetics of nanocrystal formation. We employed four different synthetic approaches including thermal decomposition, nonhydrolytic sol-gel reactions, thermal reduction, and use of reactive chalcogen reagents. We synthesized uniform oxide nanocrystals via heat-up methods. This method involved slowly heat-up reaction mixtures composed of metal precursors, surfactants, and solvents from room temperature to high temperature. We then held reaction mixtures at an aging temperature for a few minutes to a few hours. Kinetics studies revealed a three-step mechanism for the synthesis of nanocrystals through the heat-up method with size distribution control. First, as metal precursors thermally decompose, monomers accumulate. At the aging temperature, burst nucleation occurs rapidly; at the end of this second phase, nucleation stops, but continued diffusion-controlled growth leads to size focusing to produce uniform nanocrystals. We used nonhydrolytic sol-gel reactions to synthesize various transition metal oxide nanocrystals. We employed ester elimination reactions for the synthesis of ZnO and TiO(2) nanocrystals. Uniform Pd nanoparticles were synthesized via a thermal reduction reaction induced by heating up a mixture of Pd(acac)(2), tri-n-octylphosphine, and oleylamine to the aging temperature. Similarly, we synthesized nanoparticles of copper and nickel using metal(II) acetylacetonates. Ni/Pd core/shell nanoparticles were synthesized by simply heating the reaction mixture composed of acetylacetonates of nickel and palladium. Using alternative chalcogen reagents, we synthesized uniform nanocrystals of various metal chalcogenides. Uniform nanocrystals of PbS, ZnS, CdS, and MnS were obtained by heating reaction mixtures composed of metal chlorides and sulfur dissolved in oleylamine. In the future, a detailed understanding of nanocrystal formation kinetics and synthetic chemistry will lead to the synthesis of uniform nanocrystals with controlled size, shape, and composition. In particular, the synthesis of uniform nanocrystals of doped materials, core/shell materials, and multicomponent materials is still a challenge. We expect that these uniformly sized nanocrystals will find important applications in areas including information technology, biomedicine, and energy/environmental technology.

Framework for automatic information extraction from research papers on nanocrystal devices

PubMed Central

Yoshioka, Masaharu; Hara, Shinjiro; Newton, Marcus C

2015-01-01

Summary To support nanocrystal device development, we have been working on a computational framework to utilize information in research papers on nanocrystal devices. We developed an annotated corpus called “ NaDev” (Nanocrystal Device Development) for this purpose. We also proposed an automatic information extraction system called “NaDevEx” (Nanocrystal Device Automatic Information Extraction Framework). NaDevEx aims at extracting information from research papers on nanocrystal devices using the NaDev corpus and machine-learning techniques. However, the characteristics of NaDevEx were not examined in detail. In this paper, we conduct system evaluation experiments for NaDevEx using the NaDev corpus. We discuss three main issues: system performance, compared with human annotators; the effect of paper type (synthesis or characterization) on system performance; and the effects of domain knowledge features (e.g., a chemical named entity recognition system and list of names of physical quantities) on system performance. We found that overall system performance was 89% in precision and 69% in recall. If we consider identification of terms that intersect with correct terms for the same information category as the correct identification, i.e., loose agreement (in many cases, we can find that appropriate head nouns such as temperature or pressure loosely match between two terms), the overall performance is 95% in precision and 74% in recall. The system performance is almost comparable with results of human annotators for information categories with rich domain knowledge information (source material). However, for other information categories, given the relatively large number of terms that exist only in one paper, recall of individual information categories is not high (39–73%); however, precision is better (75–97%). The average performance for synthesis papers is better than that for characterization papers because of the lack of training examples for characterization papers. Based on these results, we discuss future research plans for improving the performance of the system. PMID:26665057

Framework for automatic information extraction from research papers on nanocrystal devices.

PubMed

Dieb, Thaer M; Yoshioka, Masaharu; Hara, Shinjiro; Newton, Marcus C

2015-01-01

To support nanocrystal device development, we have been working on a computational framework to utilize information in research papers on nanocrystal devices. We developed an annotated corpus called " NaDev" (Nanocrystal Device Development) for this purpose. We also proposed an automatic information extraction system called "NaDevEx" (Nanocrystal Device Automatic Information Extraction Framework). NaDevEx aims at extracting information from research papers on nanocrystal devices using the NaDev corpus and machine-learning techniques. However, the characteristics of NaDevEx were not examined in detail. In this paper, we conduct system evaluation experiments for NaDevEx using the NaDev corpus. We discuss three main issues: system performance, compared with human annotators; the effect of paper type (synthesis or characterization) on system performance; and the effects of domain knowledge features (e.g., a chemical named entity recognition system and list of names of physical quantities) on system performance. We found that overall system performance was 89% in precision and 69% in recall. If we consider identification of terms that intersect with correct terms for the same information category as the correct identification, i.e., loose agreement (in many cases, we can find that appropriate head nouns such as temperature or pressure loosely match between two terms), the overall performance is 95% in precision and 74% in recall. The system performance is almost comparable with results of human annotators for information categories with rich domain knowledge information (source material). However, for other information categories, given the relatively large number of terms that exist only in one paper, recall of individual information categories is not high (39-73%); however, precision is better (75-97%). The average performance for synthesis papers is better than that for characterization papers because of the lack of training examples for characterization papers. Based on these results, we discuss future research plans for improving the performance of the system.

Colloidal synthesis of monodispersed ZnS and CdS nanocrystals from novel zinc and cadmium complexes

NASA Astrophysics Data System (ADS)

Onwudiwe, Damian C.; Mohammed, Aliyu D.; Strydom, Christien A.; Young, Desmond A.; Jordaan, Anine

2014-06-01

Monodispersed spherical and hexagonal shaped ZnS and CdS nanocrystals respectively, have been synthesized using novel heteroleptic complexes of xanthate (S2CObu) and dithiocarbamate (S2CNMePh). The nanocrystals were prepared via colloidal route and stabilized in hexadecylamine (HDA). The morphology of the as-prepared nanocrystals was characterized using transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), and powdered X-ray diffraction (p-XRD) analysis. An average diameter of 7.2 nm and 8.6 nm were obtained for the ZnS and CdS respectively. The optical properties of the nanoparticles studied by UV-vis and photoluminescence (PL) spectroscopy showed a blue shift in the absorption spectra, and band edge emission respectively.

A novel one-pot room-temperature synthesis route to produce very small photoluminescent silicon nanocrystals

NASA Astrophysics Data System (ADS)

Douglas-Gallardo, Oscar A.; Burgos-Paci, Maxi A.; Mendoza-Cruz, Rubén; Putnam, Karl G.; Josefina Arellano-Jiménez, M.; José-Yacamán, Miguel; Mariscal, Marcelo M.; Macagno, Vicente A.; Sánchez, Cristián G.; Pérez, Manuel A.

2018-03-01

A novel strategy to synthesize photoluminescent silicon nanocrystals (SiNCs) from a reaction between tetraethylorthosilicate (TEOS) and trimethyl-hexadecyl-ammonium borohydride (CTABH4) in organic solvent is presented. The formation reaction occurs spontaneously at room temperature in homogeneous phase. The produced silicon nanocrystals are characterized by using their photoluminescent properties and via HRTEM. In addition, theoretical calculations of the optical absorption spectrum of silicon quantum dots in vacuum with different sizes and surface moieties were performed in order to compare with the experimental findings. The new chemical reaction is simple and can be implemented to produce silicon nanocrystal with regular laboratory materials by performing easy and safe procedures. [Figure not available: see fulltext.

Colloidal inorganic nanocrystals: Nucleation, growth and biological applications

NASA Astrophysics Data System (ADS)

Lynch, Jared James

Colloidal inorganic nanocrystals are a class of material whose size ranges from a few nanometers to a hundred nanometers in dimension. These nanocrystals have size dependent properties that differ significantly from the bulk material counterparts. Due to their unique physical properties colloidal inorganic nanocrystals have several promising applications in a diverse range of areas, such as biomedical diagnosis, catalysis, plasmonics, high-density data storage and solar energy conversion. This dissertation presents the study of the formation of iron oxide nanocrystals under the influence of solvent and Ar gas bubbles, the phase transfer of metal oxide nanocrystals into water using inorganic ions, and the doping of semiconductor CdS/ZnS core/shell nanocrystals with copper and silver ions. First, the formation of iron oxide nanocrystals is investigated in the presence of boiling solvent or Ar bubbles. Using a non-injection based synthesis method, the thermal decomposition of iron oleate was studied under various reaction conditions, and the role of the bubbles on the nucleation and growth of iron oxide nanocrystals was determined. Kinetics studies were used to elucidate how latent heat transfer from the bubbles allows for "active monomers" to form preferentially from exothermic reactions taking place during nucleation. General insights into colloidal inorganic nanocrystal formation are discussed. Second, a non-injection based synthesis for CdS/ZnS core/shell nanocrystals is used to make high quality semiconductor particles which are intentionally doped with Cu or Ag ions. The Ag ions effect on the optical properties of the CdS/ZnS nanocrystals is investigated. The absorption and fluorescence of the samples is measured as a function of time and temperature. Proposed mechanisms for the observations are given and thoroughly discussed. Comparisons between previous results for Cu doped CdS/ZnS nanocrystals are also made to further understand how doping of semiconductor nanocrystals can be realized. Finally, a novel phase transfer process is demonstrated using inorganic salts, such as sodium arsenite, to make water soluble metal oxide nanocrystals. The water soluble iron oxide nanocrystals are fully characterized by several complementary techniques and then used in cellular studies. The arsenite-coated iron oxide composite nanocrystals (AICN) are shown to be effective cancer therapy agents.

Room temperature synthesis of Cu₂O nanospheres: optical properties and thermal behavior.

PubMed

Nunes, Daniela; Santos, Lídia; Duarte, Paulo; Pimentel, Ana; Pinto, Joana V; Barquinha, Pedro; Carvalho, Patrícia A; Fortunato, Elvira; Martins, Rodrigo

2015-02-01

The present work reports a simple and easy wet chemistry synthesis of cuprous oxide (Cu2O) nanospheres at room temperature without surfactants and using different precursors. Structural characterization was carried out by X-ray diffraction, transmission electron microscopy, and scanning electron microscopy coupled with focused ion beam and energy-dispersive X-ray spectroscopy. The optical band gaps were determined from diffuse reflectance spectroscopy. The photoluminescence behavior of the as-synthesized nanospheres showed significant differences depending on the precursors used. The Cu2O nanospheres were constituted by aggregates of nanocrystals, in which an on/off emission behavior of each individual nanocrystal was identified during transmission electron microscopy observations. The thermal behavior of the Cu2O nanospheres was investigated with in situ X-ray diffraction and differential scanning calorimetry experiments. Remarkable structural differences were observed for the nanospheres annealed in air, which turned into hollow spherical structures surrounded by outsized nanocrystals.

Synthesis of colloidal metal nanocrystals in droplet reactors: the pros and cons of interfacial adsorption.

PubMed

Zhang, Lei; Wang, Yi; Tong, Limin; Xia, Younan

2014-07-09

Droplet reactors have received considerable attention in recent years as an alternative route to the synthesis and potentially high-volume production of colloidal metal nanocrystals. Interfacial adsorption will immediately become an important issue to address when one seeks to translate a nanocrystal synthesis from batch reactors to droplet reactors due to the involvement of higher surface-to-volume ratios for the droplets and the fact that nanocrystals tend to be concentrated at the water-oil interface. Here we report a systematic study to compare the pros and cons of interfacial adsorption of metal nanocrystals during their synthesis in droplet reactors. On the one hand, interfacial adsorption can be used to generate nanocrystals with asymmetric shapes or structures, including one-sixth-truncated Ag octahedra and Au-Ag nanocups. On the other hand, interfacial adsorption has to be mitigated to obtain nanocrystals with uniform sizes and controlled shapes. We confirmed that Triton X-100, a nonionic surfactant, could effectively alleviate interfacial adsorption while imposing no impact on the capping agent typically needed for a shape-controlled synthesis. With the introduction of a proper surfactant, droplet reactors offer an attractive platform for the continuous production of colloidal metal nanocrystals.

Semiconductor nanowhiskers: Synthesis, properties, and applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dubrovskii, V. G., E-mail: dubrovskii@mail.ioffe.ru; Cirlin, G. E., E-mail: Cirlin@beam.ioffe.ru; Ustinov, V. M., E-mail: Vmust@beam.ioffe.ru

2009-12-15

Recent results of studying the semiconductor's whisker nanocrystals are reviewed. Physical grounds of growing whisker nanocrystals using the mechanism vapor-liquid-crystal are given and the main epitaxial technologies of synthesis of whisker nanocrystals are described. Thermodynamic and kinetic factors controlling the morphological properties, composition, and crystal structure of whisker nanocrystals are considered in detail. The main theoretical models of the growth and structure of whisker nanocrystals are described. The data on physical properties of whisker nanocrystals and possibilities of their use in nanophotonics, nanoelectronics, and nanobiotechnology are presented.

Infrared emitting and photoconducting colloidal silver chalcogenide nanocrystal quantum dots from a silylamide-promoted synthesis.

PubMed

Yarema, Maksym; Pichler, Stefan; Sytnyk, Mykhailo; Seyrkammer, Robert; Lechner, Rainer T; Fritz-Popovski, Gerhard; Jarzab, Dorota; Szendrei, Krisztina; Resel, Roland; Korovyanko, Oleksandra; Loi, Maria Antonietta; Paris, Oskar; Hesser, Günter; Heiss, Wolfgang

2011-05-24

Here, we present a hot injection synthesis of colloidal Ag chalcogenide nanocrystals (Ag(2)Se, Ag(2)Te, and Ag(2)S) that resulted in exceptionally small nanocrystal sizes in the range between 2 and 4 nm. Ag chalcogenide nanocrystals exhibit band gap energies within the near-infrared spectral region, making these materials promising as environmentally benign alternatives to established infrared active nanocrystals containing toxic metals such as Hg, Cd, and Pb. We present Ag(2)Se nanocrystals in detail, giving size-tunable luminescence with quantum yields above 1.7%. The luminescence, with a decay time on the order of 130 ns, was shown to improve due to the growth of a monolayer thick ZnSe shell. Photoconductivity with a quantum efficiency of 27% was achieved by blending the Ag(2)Se nanocrystals with a soluble fullerene derivative. The co-injection of lithium silylamide was found to be crucial to the synthesis of Ag chalcogenide nanocrystals, which drastically increased their nucleation rate even at relatively low growth temperatures. Because the same observation was made for the nucleation of Cd chalcogenide nanocrystals, we conclude that the addition of lithium silylamide might generally promote wet-chemical synthesis of metal chalcogenide nanocrystals, including in as-yet unexplored materials.

Cellulose nanocrystals as templates for cetyltrimethylammonium bromide mediated synthesis of Ag nanoparticles and their novel use in PLA films.

PubMed

Yalcinkaya, E E; Puglia, D; Fortunati, E; Bertoglio, F; Bruni, G; Visai, L; Kenny, J M

2017-02-10

In the present paper, we reported how cellulose nanocrystals (CNC) from microcrystalline cellulose have the capacity to assist in the synthesis of metallic nanoparticles chains. A cationic surfactant, cetyltrimethylammonium bromide (CTAB), was used as modifier for CNC surface. Silver nanoparticles were synthesized on CNC, and nanoparticle density and size were optimized by varying concentrations of nitrate and reducing agents, and the reduction time. The experimental conditions were optimized for the synthesis and the resulting Ag grafted CNC (Ag-g-CNC) were characterized by means of TGA, SEM, FTIR and XRD, and then introduced in PLA matrix. PLA nanocomposite containing silver grafted cellulose nanocrystals (PLA/0.5Ag-g-1CNC) was characterized by optical and thermal analyses and the obtained data were compared with results from PLA nanocomposites containing 1% wt. of CNC (PLA/1CNC), 0.5% wt. of silver nanoparticles (PLA/0.5Ag) and hybrid system containing CNC and silver in the same amount (PLA/1CNC/0.5Ag). The results demonstrated that grafting of silver nanoparticles on CNC positively affected the thermal degradation process and cold crystallization processes of PLA matrix. Finally, the antibacterial activity of the different systems was studied at various incubation times and temperatures, showing the best performance for PLA/1CNC/0.5Ag based nanocomposite. Copyright © 2016 Elsevier Ltd. All rights reserved.

Multicolour synthesis in lanthanide-doped nanocrystals through cation exchange in water

NASA Astrophysics Data System (ADS)

Han, Sanyang; Qin, Xian; An, Zhongfu; Zhu, Yihan; Liang, Liangliang; Han, Yu; Huang, Wei; Liu, Xiaogang

2016-10-01

Meeting the high demand for lanthanide-doped luminescent nanocrystals across a broad range of fields hinges upon the development of a robust synthetic protocol that provides rapid, just-in-time nanocrystal preparation. However, to date, almost all lanthanide-doped luminescent nanomaterials have relied on direct synthesis requiring stringent controls over crystal nucleation and growth at elevated temperatures. Here we demonstrate the use of a cation exchange strategy for expeditiously accessing large classes of such nanocrystals. By combining the process of cation exchange with energy migration, the luminescence properties of the nanocrystals can be easily tuned while preserving the size, morphology and crystal phase of the initial nanocrystal template. This post-synthesis strategy enables us to achieve upconversion luminescence in Ce3+ and Mn2+-activated hexagonal-phased nanocrystals, opening a gateway towards applications ranging from chemical sensing to anti-counterfeiting.

Influence of experimental parameters on iron oxide nanoparticle properties synthesized by thermal decomposition: size and nuclear magnetic resonance studies

NASA Astrophysics Data System (ADS)

Belaïd, Sarah; Stanicki, Dimitri; Vander Elst, Luce; Muller, Robert N.; Laurent, Sophie

2018-04-01

A study of the experimental conditions to synthesize monodisperse iron oxide nanocrystals prepared from the thermal decomposition of iron(III) acetylacetonate was carried out in the presence of surfactants and a reducing agent. The influence of temperature, synthesis time and surfactant amounts on nanoparticle properties is reported. This investigation combines relaxometric characterization and size properties. The relaxometric behavior of the nanomaterials depends on the selected experimental parameters. The synthesis of iron oxide nanoparticles with a high relaxivity and a high saturation magnetization can be obtained with a short reaction time at high temperature. Moreover, the influence of surfactant concentrations determines the optimal value in order to produce iron oxide nanoparticles with a narrow size distribution. The optimized synthesis is rapid, robust and reproductive, and produces nearly monodisperse magnetic nanocrystals.

Quantitative phase analysis and microstructure characterization of magnetite nanocrystals obtained by microwave assisted non-hydrolytic sol–gel synthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sciancalepore, Corrado, E-mail: corrado.sciancalepore@unimore.it; Bondioli, Federica; INSTM Consortium, Via G. Giusti 9, 51121 Firenze

2015-02-15

An innovative preparation procedure, based on microwave assisted non-hydrolytic sol–gel synthesis, to obtain spherical magnetite nanoparticles was reported together with a detailed quantitative phase analysis and microstructure characterization of the synthetic products. The nanoparticle growth was analyzed as a function of the synthesis time and was described in terms of crystallization degree employing the Rietveld method on the magnetic nanostructured system for the determination of the amorphous content using hematite as internal standard. Product crystallinity increases as the microwave thermal treatment is increased and reaches very high percentages for synthesis times longer than 1 h. Microstructural evolution of nanocrystals wasmore » followed by the integral breadth methods to obtain information on the crystallite size-strain distribution. The results of diffraction line profile analysis were compared with nanoparticle grain distribution estimated by dimensional analysis of the transmission electron microscopy (TEM) images. A variation both in the average grain size and in the distribution of the coherently diffraction domains is evidenced, allowing to suppose a relationship between the two quantities. The traditional integral breadth methods have proven to be valid for a rapid assessment of the diffraction line broadening effects in the above-mentioned nanostructured systems and the basic assumption for the correct use of these methods are discussed as well. - Highlights: • Fe{sub 3}O{sub 4} nanocrystals were obtained by MW-assisted non-hydrolytic sol–gel synthesis. • Quantitative phase analysis revealed that crystallinity up to 95% was reached. • The strategy of Rietveld refinements was discussed in details. • Dimensional analysis showed nanoparticles ranging from 4 to 8 nm. • Results of integral breadth methods were compared with microscopic analysis.« less

Shape-Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics?

PubMed Central

Xia, Younan; Xiong, Yujie; Lim, Byungkwon; Skrabalak, Sara E.

2009-01-01

Nanocrystals are fundamental to modern science and technology. Mastery over the shape of a nanocrystal enables control of its properties and enhancement of its usefulness for a given application. The aim of this article is to present a comprehensive review of current research activities that center on the shape-controlled synthesis of metal nanocrystals. We begin with a brief introduction to nucleation and growth within the context of metal nanocrystal synthesis, followed by a discussion of the possible shapes that a metal nanocrystal might take under different conditions. We then focus on a variety of experimental parameters that have been explored to manipulate the nucleation and growth of metal nanocrystals in solution-phase syntheses in an effort to generate specific shapes. We then elaborate on these approaches by selecting examples in which there is already reasonable understanding for the observed shape control or at least the protocols have proven to be reproducible and controllable. Toward the end of this article, we highlight a number of applications that have been enabled and/or enhanced by the shape-controlled synthesis of metal nanocrystals. We conclude this article with personal perspectives on the directions toward which future research in this field might take. PMID:19053095

Shape-controlled synthesis of metal nanocrystals: simple chemistry meets complex physics?

PubMed

Xia, Younan; Xiong, Yujie; Lim, Byungkwon; Skrabalak, Sara E

2009-01-01

Nanocrystals are fundamental to modern science and technology. Mastery over the shape of a nanocrystal enables control of its properties and enhancement of its usefulness for a given application. Our aim is to present a comprehensive review of current research activities that center on the shape-controlled synthesis of metal nanocrystals. We begin with a brief introduction to nucleation and growth within the context of metal nanocrystal synthesis, followed by a discussion of the possible shapes that a metal nanocrystal might take under different conditions. We then focus on a variety of experimental parameters that have been explored to manipulate the nucleation and growth of metal nanocrystals in solution-phase syntheses in an effort to generate specific shapes. We then elaborate on these approaches by selecting examples in which there is already reasonable understanding for the observed shape control or at least the protocols have proven to be reproducible and controllable. Finally, we highlight a number of applications that have been enabled and/or enhanced by the shape-controlled synthesis of metal nanocrystals. We conclude this article with personal perspectives on the directions toward which future research in this field might take.

Bio-inspired routes for synthesizing efficient nanoscale platinum electrocatalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cha, Jennifer N.; Wang, Joseph

2014-08-31

The overall objective of the proposed research is to use fundamental advances in bionanotechnology to design powerful platinum nanocrystal electrocatalysts for fuel cell applications. The new economically-viable, environmentally-friendly, bottom-up biochemical synthetic strategy will produce platinum nanocrystals with tailored size, shape and crystal orientation, hence leading to a maximum electrochemical reactivity. There are five specific aims to the proposed bio-inspired strategy for synthesizing efficient electrocatalytic platinum nanocrystals: (1) isolate peptides that both selectively bind particular crystal faces of platinum and promote the nucleation and growth of particular nanocrystal morphologies, (2) pattern nanoscale 2-dimensional arrays of platinum nucleating peptides from DNA scaffolds,more » (3) investigate the combined use of substrate patterned peptides and soluble peptides on nanocrystal morphology and growth (4) synthesize platinum crystals on planar and large-area carbon electrode supports, and (5) perform detailed characterization of the electrocatalytic behavior as a function of catalyst size, shape and morphology. Project Description and Impact: This bio-inspired collaborative research effort will address key challenges in designing powerful electrocatalysts for fuel cell applications by employing nucleic acid scaffolds in combination with peptides to perform specific, environmentally-friendly, simultaneous bottom-up biochemical synthesis and patterned assembly of highly uniform and efficient platinum nanocrystal catalysts. Bulk synthesis of nanoparticles usually produces a range of sizes, accessible catalytic sites, crystal morphologies, and orientations, all of which lead to inconsistent catalytic activities. In contrast, biological systems routinely demonstrate exquisite control over inorganic syntheses at neutral pH and ambient temperature and pressures. Because the orientation and arrangement of the templating biomolecules can be precisely controlled, the nanocrystals boast a defined shape, morphology, orientation and size and are synthesized at benign reaction conditions. Adapting the methods of biomineralization towards the synthesis of platinum nanocrystals will allow effective control at a molecular level of the synthesis of highly active metal electrocatalysts, with readily tailored properties, through tuning of the biochemical inputs. The proposed research will incorporate many facets of biomineralization by: (1) isolating peptides that selectively bind particular crystal faces of platinum (2) isolating peptides that promote the nucleation and growth of particular nanocrystal morphologies (3) using two-dimensional DNA scaffolds to control the spatial orientation and density of the platinum nucleating peptides, and (4) combining bio-templating and soluble peptides to control crystal nucleation, orientation, and morphology. The resulting platinum nanocrystals will be evaluated for their electrocatalytic behavior (on common carbon supports) to determine their optimal size, morphology and crystal structure. We expect that such rational biochemical design will lead to highly uniform and efficient platinum nanocrystal catalysts for fuel cell applications.« less

Barium titanate nanocrystals and nanocrystal thin films: Synthesis, ferroelectricity, and dielectric properties

NASA Astrophysics Data System (ADS)

Huang, Limin; Chen, Zhuoying; Wilson, James D.; Banerjee, Sarbajit; Robinson, Richard D.; Herman, Irving P.; Laibowitz, Robert; O'Brien, Stephen

2006-08-01

Advanced applications for high k dielectric and ferroelectric materials in the electronics industry continues to demand an understanding of the underlying physics in decreasing dimensions into the nanoscale. We report the synthesis, processing, and electrical characterization of thin (<100nm thick) nanostructured thin films of barium titanate (BaTiO3) built from uniform nanoparticles (<20nm in diameter). We introduce a form of processing as a step toward the ability to prepare textured films based on assembly of nanoparticles. Essential to this approach is an understanding of the nanoparticle as a building block, combined with an ability to integrate them into thin films that have uniform and characteristic electrical properties. Our method offers a versatile means of preparing BaTiO3 nanocrystals, which can be used as a basis for micropatterned or continuous BaTiO3 nanocrystal thin films. We observe the BaTiO3 nanocrystals crystallize with evidence of tetragonality. We investigated the preparation of well-isolated BaTiO3 nanocrystals smaller than 10nm with control over aggregation and crystal densities on various substrates such as Si, Si /SiO2, Si3N4/Si, and Pt-coated Si substrates. BaTiO3 nanocrystal thin films were then prepared, resulting in films with a uniform nanocrystalline grain texture. Electric field dependent polarization measurements show spontaneous polarization and hysteresis, indicating ferroelectric behavior for the BaTiO3 nanocrystalline films with grain sizes in the range of 10-30nm. Dielectric measurements of the films show dielectic constants in the range of 85-90 over the 1KHz -100KHz, with low loss. We present nanocrystals as initial building blocks for the preparation of thin films which exhibit highly uniform nanostructured texture and grain sizes.

Formic acid-assisted synthesis of palladium nanocrystals and their electrocatalytic properties.

PubMed

Wang, Qinchao; Wang, Yiqian; Guo, Peizhi; Li, Qun; Ding, Ruixue; Wang, Baoyan; Li, Hongliang; Liu, Jingquan; Zhao, X S

2014-01-14

Palladium (Pd) nanocrystals have been synthesized by using formic acid as the reducing agent at room temperature. When the concentration of formic acid was increased continuously, the size of Pd nanocrystals first decreased to a minimum and then increased slightly again. The products have been investigated by a series of techniques, including X-ray diffraction, high-resolution transmission electron microscopy (HRTEM), UV-vis absorption, and electrochemical measurements. The formation of Pd nanocrystals is proposed to be closely related to the dynamical imbalance of the growth and dissolution rate of Pd nanocrystals associated with the adsorption of formate ions onto the surface of the intermediates. It is found that small Pd nanocrystals showed blue-shifted adsorption peaks compared with large ones. Pd nanocrystals with the smallest size display the highest electrocatalytic activity for the electrooxidation of formic acid and ethanol on the basis of cyclic voltammetry and chronoamperometric data. It is suggested that both the electrochemical active surface area and the small size effect are the key roles in determining the electrocatalytic performances of Pd nanocrystals. A "dissolution-deposition-aggregation" process is proposed to explain the variation of the electrocatalytic activity during the electrocatalysis according to the HRTEM characterization.

Direct ultrasonic-assisted synthesis of sphere-like nanocrystals of spinel Co3O4 and Mn3O4.

PubMed

Askarinejad, Azadeh; Morsali, Ali

2009-01-01

A simple sonochemical method was developed to synthesize uniform sphere-like or cubic Co(3)O(4) and Mn(3)O(4) nanocrystals by using acetate salts and sodium hydroxide or tetramethylammonium hydroxide (TMAH) as precursors. Influence of some parameters such as time of reaction, alkali salts, and power of the ultrasound and the molar ratio of the starting materials on the size, morphology and degree of crystallinity of the products was studied. Powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), FTIR spectroscopy, Thermal gravimetry analysis and differential thermal analysis (TGA/DTA) were used to characterize the nanocrystals.

Synthesis of ligand-stabilized metal oxide nanocrystals and epitaxial core/shell nanocrystals via a lower-temperature esterification process.

PubMed

Ito, Daisuke; Yokoyama, Shun; Zaikova, Tatiana; Masuko, Keiichiro; Hutchison, James E

2014-01-28

The properties of metal oxide nanocrystals can be tuned by incorporating mixtures of matrix metal elements, adding metal ion dopants, or constructing core/shell structures. However, high-temperature conditions required to synthesize these nanocrystals make it difficult to achieve the desired compositions, doping levels, and structural control. We present a lower temperature synthesis of ligand-stabilized metal oxide nanocrystals that produces crystalline, monodisperse nanocrystals at temperatures well below the thermal decomposition point of the precursors. Slow injection (0.2 mL/min) of an oleic acid solution of the metal oleate complex into an oleyl alcohol solvent at 230 °C results in a rapid esterification reaction and the production of metal oxide nanocrystals. The approach produces high yields of crystalline, monodisperse metal oxide nanoparticles containing manganese, iron, cobalt, zinc, and indium within 20 min. Synthesis of tin-doped indium oxide (ITO) can be accomplished with good control of the tin doping levels. Finally, the method makes it possible to perform epitaxial growth of shells onto nanocrystal cores to produce core/shell nanocrystals.

Mg-MOF-74@SBA-15 hybrids: Synthesis, characterization, and adsorption properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chakraborty, Anindita; Maji, Tapas Kumar, E-mail: tmaji@jncasr.ac.in

2014-12-01

Nanocrystals of Mg-MOF-74 have been immobilized into the mesopores of SBA-15 rods to fabricate Mg-MOF-74@SBA-15 hybrid materials. To furnish such composites, a relatively simple synthetic strategy has been adopted by direct dispersion of the metal-organic framework (MOF) precursors in SBA-15 matrix to prepare the hybrid materials in situ. The hybrid materials have been characterized using powder X-ray diffraction and several spectroscopic and microscopic techniques, which suggest growth of the MOF nanocrystals inside the SBA-15 mesopores and the composites exhibit characteristics of both the components. N{sub 2} adsorption isotherms at 77 K reveal that the composites contain additional mesopores, compared tomore » only micropores of pristine MOF nanocrystals. In addition to such combination of both micro and mesoporosity, the composites also demonstrate significant CO{sub 2} adsorption at room temperature.« less

Synthesis and characterization of InN nanocrystals on glass substrate by plasma assisted reactive evaporation

NASA Astrophysics Data System (ADS)

Ganesh, V.; Alizadeh, M.; Shuhaimi, A.; Sundaram, S.; Hakim, K. M.; Goh, B. T.; Rahman, S. A.

2017-07-01

InN nanocrystals were grown on glass substrate by plasma assisted reactive evaporation technique and the quality was compared with InN on Si (111) substrate. Single phase InN was confirmed by X-ray diffraction and micro Raman analysis on both the substrates. Agglomerated and Hexagonal faceting nanocrystals observed by field emission scanning electron microscopy. Energy dispersive X-ray analysis shows InN nanocrystals are nearly stochiometric. Photoluminescence reveals a broad emission near bandedge at 2 .04 eV and defect band at 1.07 eV. The Hall measurement on both the substrates reveals high electron carrier concentration. These encouraging results obtained suggested that high quality single crystalline InN can be obtained on glass substrate further optimizing the growth parameters. This novel growth of InN nanocrystals on glass substrate is an important step towards the development of monolithic, high efficiency low-cost InGaN-based renewable energy sources.

Facile synthesis of high-temperature (1000 °C) phase-stable rice-like anatase TiO2 nanocrystals

NASA Astrophysics Data System (ADS)

Lv, Lizhen; Chen, Qirong; Liu, Xiuyun; Wang, Miaomiao; Meng, Xiangfu

2015-05-01

High-temperature phase-stable rice-like anatase TiO2 nanocrystals were synthesized by one-pot solvothermal method using soluble titania xerogel and isopropyl alcohol (IPA) as the precursor and the solvent, respectively. Sample characterization was carried out by powder X-ray diffraction, high-resolution transmission electron microscopy, field emission scanning electron microscope, X-ray photoelectron spectroscopy, and N2 adsorption-desorption isotherms. The results showed that TiO2 nanocrystals had rice-like shapes with an average size of 5 nm in width and 35 nm in length. The BET surface area was 153 m2/g. Unexpectedly, the rice-like TiO2 nanocrystals exhibited high-temperature phase stability, which could remain as pure anatase phase after calcinations at 1000 °C. Growth mechanism investigation revealed that the IPA solvent played a key role in nucleation and growth of rice-like anatase TiO2 nanocrystals. The photodegradation of rhodamine B demonstrated that rice-like anatase TiO2 nanocrystals exhibited enhanced photocatalytic activity under visible light irradiation.

Mesoporous Colloidal Superparticles of Platinum-Group Nanocrystals with Surfactant-Free Surfaces and Enhanced Heterogeneous Catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Yongxing; Liu, Yuzi; Sun, Yugang

2015-01-23

Synthesis of colloidal superparticles (CSPs) of nanocrystals, a class of assembled nanocrystals in the form of colloidal particles, has been emerging as a new frontier in the field of nanotechnology because of their potential novel properties originated from coupling of individual nanocrystals in CSPs. Here, a facile approach is reported for the controlled synthesis of mesoporous CSPs made of various platinum-group nanocrystals that exhibit high colloidal stability and ligand-free surfaces to significantly benefit their applications in solution-phase heterogeneous catalysis. The synthesis relies on self-limiting growth of composite particles through coprecipitation of both Pt-group nanocrystals (or their precursor compounds) and silvermore » halides on sacrificial substrates of colloidal silver particles. The intermediate silver halides in the composite particles play the critical role in limiting the continuous growth (and/or coalescence) of individual Pt-group nanocrystals and they can be selectively dissolved to create nanoscale pores in the resulting CSPs.« less

Selective epitaxial growth of zinc blende-derivative on wurtzite-derivative: the case of polytypic Cu2CdSn(S1-xSex)4 nanocrystals

NASA Astrophysics Data System (ADS)

Wu, Liang; Fan, Feng-Jia; Gong, Ming; Ge, Jin; Yu, Shu-Hong

2014-02-01

Polytypic nanocrystals with zinc blende (ZB) cores and wurtzite (WZ) arms, such as tetrapod and octopod nanocrystals, have been widely reported. However, polytypic nanocrystals with WZ cores and ZB arms or ends have been rarely reported. Here, we report a facile, solution-based approach to the synthesis of polytypic Cu2CdSn(S1-xSex)4 (CCTSSe) nanocrystals with ZB-derivative selectively engineered on (000+/-2)WZ facets of WZ-derived cores. Accordingly, two typical morphologies, i.e., bullet-like nanocrystals with a WZ-derivative core and one ZB-derivative end, and rugby ball-like nanocrystals with a WZ-derivative core and two ZB-derivative ends, can be selectively prepared. The epitaxial growth mechanism is confirmed by the time-dependent experiments. The ratio of rugby ball-like and bullet-like polytypic CCTSSe nanocrystals can be tuned through changing the amount of Cd precursor to adjust the reactivity difference between (0002)WZ and (000-2)WZ facets. These unique polytypic CCTSSe nanocrystals may find applications in energetic semiconducting materials for energy conversion in the future.Polytypic nanocrystals with zinc blende (ZB) cores and wurtzite (WZ) arms, such as tetrapod and octopod nanocrystals, have been widely reported. However, polytypic nanocrystals with WZ cores and ZB arms or ends have been rarely reported. Here, we report a facile, solution-based approach to the synthesis of polytypic Cu2CdSn(S1-xSex)4 (CCTSSe) nanocrystals with ZB-derivative selectively engineered on (000+/-2)WZ facets of WZ-derived cores. Accordingly, two typical morphologies, i.e., bullet-like nanocrystals with a WZ-derivative core and one ZB-derivative end, and rugby ball-like nanocrystals with a WZ-derivative core and two ZB-derivative ends, can be selectively prepared. The epitaxial growth mechanism is confirmed by the time-dependent experiments. The ratio of rugby ball-like and bullet-like polytypic CCTSSe nanocrystals can be tuned through changing the amount of Cd precursor to adjust the reactivity difference between (0002)WZ and (000-2)WZ facets. These unique polytypic CCTSSe nanocrystals may find applications in energetic semiconducting materials for energy conversion in the future. Electronic supplementary information (ESI) available: Detailed information about the polytypic CCTSSe nanocrystals syntheses, measurement and characterization, additional TEM and HRTEM images, PXRD analysis, EDS spectra and UV-vis-NIR spectra. See DOI: 10.1039/c3nr04948e.

Polycatenar Ligand Control of the Synthesis and Self-Assembly of Colloidal Nanocrystals.

PubMed

Diroll, Benjamin T; Jishkariani, Davit; Cargnello, Matteo; Murray, Christopher B; Donnio, Bertrand

2016-08-24

Hydrophobic colloidal nanocrystals are typically synthesized and manipulated with commercially available ligands, and surface functionalization is therefore typically limited to a small number of molecules. Here, we report the use of polycatenar ligands derived from polyalkylbenzoates for the direct synthesis of metallic, chalcogenide, pnictide, and oxide nanocrystals. Polycatenar molecules, branched structures bearing diverging chains in which the terminal substitution pattern, functionality, and binding group can be independently modified, offer a modular platform for the development of ligands with targeted properties. Not only are these ligands used for the direct synthesis of monodisperse nanocrystals, but nanocrystals coated with polycatenar ligands self-assemble into softer bcc superlattices that deviate from conventional harder close-packed structures (fcc or hcp) formed by the same nanocrystals coated with commercial ligands. Self-assembly experiments demonstrate that the molecular structure of polycatenar ligands encodes interparticle spacings and attractions, engineering self-assembly, which is tunable from hard sphere to soft sphere behavior.

Nanocrystal synthesis in microfluidic reactors: where next?

PubMed

Phillips, Thomas W; Lignos, Ioannis G; Maceiczyk, Richard M; deMello, Andrew J; deMello, John C

2014-09-07

The past decade has seen a steady rise in the use of microfluidic reactors for nanocrystal synthesis, with numerous studies reporting improved reaction control relative to conventional batch chemistry. However, flow synthesis procedures continue to lag behind batch methods in terms of chemical sophistication and the range of accessible materials, with most reports having involved simple one- or two-step chemical procedures directly adapted from proven batch protocols. Here we examine the current status of microscale methods for nanocrystal synthesis, and consider what role microreactors might ultimately play in laboratory-scale research and industrial production.

Effect of surface hydrophobicity on the function of the immobilized biomineralization protein Mms6

DOE PAGES

Liu, Xunpei; Zhang, Honghu; Nayak, Srikanth; ...

2015-08-13

Magnetotactic bacteria produce magnetic nanocrystals with uniform shapes and sizes in nature, which has inspired in vitro synthesis of uniformly sized magnetite nanocrystals under mild conditions. Mms6, a biomineralization protein from magnetotactic bacteria with a hydrophobic N-terminal domain and a hydrophilic C-terminal domain, can promote formation of magnetite nanocrystals in vitro with well-defined shape and size in gels under mild conditions. Here we investigate the role of surface hydrophobicity on the ability of Mms6 to template magnetite nanoparticle formation on surfaces. Our results confirmed that Mms6 can form a protein network structure on a monolayer of hydrophobic octadecanethiol (ODT)-coated goldmore » surfaces and facilitate magnetite nanocrystal formation with uniform sizes close to those seen in nature, in contrast to its behavior on more hydrophilic surfaces. We propose that this hydrophobicity effect might be due to the amphiphilic nature of the Mms6 protein and its tendency to incorporate the hydrophobic N-terminal domain into the hydrophobic lipid bilayer environment of the magnetosome membrane, exposing the hydrophilic C-terminal domain that promotes biomineralization. Supporting this hypothesis, the larger and well-formed magnetite nanoparticles were found to be preferentially located on ODT surfaces covered with Mms6 as compared to control samples, as characterized by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and atomic force microscopy studies. A C-terminal domain mutant of this protein did not form the same network structure as wild-type Mms6, suggesting that the network structure is important for the magnetite nanocrystal formation. This article provides valuable insights into the role of surface hydrophilicity on the action of the biomineralization protein Mms6 to synthesize magnetic nanocrystals and provides a facile route to controlling bioinspired nanocrystal synthesis in vitro.« less

Photobactericidal porphyrin-cellulose nanocrystals: synthesis, characterization, and antimicrobial properties.

PubMed

Feese, Elke; Sadeghifar, Hasan; Gracz, Hanna S; Argyropoulos, Dimitris S; Ghiladi, Reza A

2011-10-10

Adherence and survival of pathogenic bacteria on surfaces leading to concomitant transmission to new hosts significantly contributes to the proliferation of pathogens, which in turn considerably increases the threat to human health, particularly by antibiotic-resistant bacteria. Consequently, more research into effective surface disinfection and alternative materials (fabrics, plastics, or coatings) with antimicrobial and other bioactive characteristics is desirable. This report describes the synthesis and characterization of cellulose nanocrystals that were surface-modified with a cationic porphyrin. The porphyrin was appended onto the cellulose surface via the Cu(I)-catalyzed Huisgen-Meldal-Sharpless 1,3-dipolar cycloaddition having occurred between azide groups on the cellulosic surface and porphyrinic alkynes. The resulting, generally insoluble, crystalline material, CNC-Por (5), was characterized by infrared and diffusion (1)H NMR spectroscopies, gel permeation chromatography, and thermogravimetric analysis. Although only suspended, and not dissolved, in an aqueous system, CNC-Por (5) showed excellent efficacy toward the photodynamic inactivation of Mycobacterium smegmatis and Staphylococcus aureus , albeit only slight activity against Escherichia coli . The synthesis, properties, and activity of CNC-Por (5) described herein serve as a benchmark toward our overall objectives of developing novel, potent, bioactive, photobactericidal materials that are effective against a range of bacteria, with potential utilization in the health care and food preparation industries.

A Safer, Easier, Faster Synthesis for CdSe Quantum Dot Nanocrystals

ERIC Educational Resources Information Center

Boatman, Elizabeth M.; Lisensky, George C.; Nordell, Karen J.

2005-01-01

The synthesis for CdSe quantum dot nanocrystals that vary in color and are a visually engaging way to demonstrate quantum effects in chemistry is presented. CdSe nanocrystals are synthesized from CdO and elemental Se using a kinetic growth method where particle size depends on reaction time.

Labeling of HeLa cells using ZrO2:Yb3+-Er3+ nanoparticles with upconversion emission

NASA Astrophysics Data System (ADS)

Ceja-Fdez, Andrea; López-Luke, Tzarara; Oliva, Jorge; Vivero-Escoto, Juan; Gonzalez-Yebra, Ana Lilia; Rojas, Ruben A. Rodriguez; Martínez-Pérez, Andrea; de la Rosa, Elder

2015-04-01

This work reports the synthesis, structural characterization, and optical properties of ZrO2:Yb3+-Er3+ (2-1 mol%) nanocrystals. The nanoparticles were coated with 3-aminopropyl triethoxysilane (APTES) and further modified with biomolecules, such as Biotin-Anti-rabbit (mouse IgG) and rabbit antibody-AntiKi-67, through a conjugation method. The conjugation was successfully confirmed by Fourier transform infrared, zeta potential, and dynamic light scattering. The internalization of the conjugated nanoparticles in human cervical cancer (HeLa) cells was followed by two-photon confocal microscopy. The ZrO2:Yb3+-Er3+ nanocrystals exhibited strong red emission under 970-nm excitation. Moreover, the luminescence change due to the addition of APTES molecules and biomolecules on the nanocrystals was also studied. These results demonstrate that ZrO2:Yb3+-Er3+ nanocrystals can be successfully functionalized with biomolecules to develop platforms for biolabeling and bioimaging.

Elastase kinetics and structural features of colorimetric and fluorescent peptides on cellulose nanocrystals

USDA-ARS?s Scientific Manuscript database

Human neutrophil elastase (HNE) and porcine pancreatic elastase (PPE) are serine proteases with destructive proteolytic activity. Because of this activity, there is considerable interest in elastase sensors. Herein we report the synthesis, characterization, and kinetic profiles of tri- and tetrapept...

Influence of the solvent in the synthesis of zeolitic imidazolate framework-8 (ZIF-8) nanocrystals at room temperature.

PubMed

Bustamante, Eugenia L; Fernández, José L; Zamaro, Juan M

2014-06-15

The effect of the solvent on the synthesis process and on the nanocrystal characteristics of the zeolitic imidazolate framework-8 (ZIF-8) was investigated. A synthesis protocol at room temperature employing a series of aliphatic alcohols, water, dimethylformamide and acetone was employed. The results show that the solvent modifies the evolution of the reaction, altering the crystallization rates and nanocrystal sizes. Its hydrogen bond donation ability is the main factor that governs this effect. More precisely, the solvent modulates the formation of ZIF-8 nanocrystals with sizes in the range between 15 and 42 nm. When synthesized in alcohol and acetone, these nanocrystals form globular aggregates with sizes between 130 and 420 nm. In contrast, under the same synthesis conditions, when using water or dimethylformamide the ZIF phase is not developed. In alcohols other than methanol, the crystals develop pill-shaped morphologies with poorly defined facets. Moreover, a markedly fast growing kinetics is verified in these alcohols, leading to an ultra-fast crystallization of ZIF-8 in about 60s. These findings provide new information about the role of the solvent in the synthesis process of nanoZIF-8, which can be useful for controlling the crystallization rates and nanocrystal sizes of this material. Copyright © 2014 Elsevier Inc. All rights reserved.

A Novel Thermal Electrochemical Synthesis Method for Production of Stable Colloids of "Naked" Metal (Ag) Nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Michael Z.; Easterly, Clay E

Solution synthesis of nanocrystal silver is reviewed. This paper reports a novel thermal electrochemical synthesis (TECS) for producing metal Ag nanocrystals as small as a few nanometers. The TECS method requires mild conditions (25-100oC), low voltage (1-50 V DC) on Ag electrodes, and simple water or aqueous solutions as reaction medium. Furthermore, a tubular dialysis membrane surround electrodes proves favorable to produce nanosized (<10 nm) Ag nanocrystals. Different from those nanocrystals reported in literature, our nanocrystals have several unique features: (1) small nanometer size, (2) nakedness , i.e., surfaces of metal nanocrystals are free of organic ligands or capping moleculesmore » and no need of dispersant in synthesis solutions, and (3) colloidally stable in water solutions. It was discovered that Ag nanoparticles with initially large size distribution can be homogenized into near-monodispersed system by a low power (< 15 mW) He-Ne laser exposure treatment. The combination of the TECS technique and the laser treatment could lead to a new technology that produces metal nanoparticles that are naked, stable, and uniform sized. In the presence of stabilizing agent (also as supporting electrolyte) such as polyvinyl alcohol (PVA), large yield of silver nanoparticles (<100nm) in the form of thick milky sols are produced.« less

Tailoring indium oxide nanocrystal synthesis conditions for air-stable high-performance solution-processed thin-film transistors.

PubMed

Swisher, Sarah L; Volkman, Steven K; Subramanian, Vivek

2015-05-20

Semiconducting metal oxides (ZnO, SnO2, In2O3, and combinations thereof) are a uniquely interesting family of materials because of their high carrier mobilities in the amorphous and generally disordered states, and solution-processed routes to these materials are of particular interest to the printed electronics community. Colloidal nanocrystal routes to these materials are particularly interesting, because nanocrystals may be formulated with tunable surface properties into stable inks, and printed to form devices in an additive manner. We report our investigation of an In2O3 nanocrystal synthesis for high-performance solution-deposited semiconductor layers for thin-film transistors (TFTs). We studied the effects of various synthesis parameters on the nanocrystals themselves, and how those changes ultimately impacted the performance of TFTs. Using a sintered film of solution-deposited In2O3 nanocrystals as the TFT channel material, we fabricated devices that exhibit field effect mobility of 10 cm(2)/(V s) and an on/off current ratio greater than 1 × 10(6). These results outperform previous air-stable nanocrystal TFTs, and demonstrate the suitability of colloidal nanocrystal inks for high-performance printed electronics.

Synthesis of icosahedral gold nanocrystals: a thermal process strategy.

PubMed

Zhou, Min; Chen, Shenhao; Zhao, Shiyong

2006-03-16

We demonstrate a one-step thermal process route to the synthesis of icosahedral gold nanocrystals. By regulating the concentrations of poly(vinyl pyrrolidone) (PVP) and HAuCl4 or changing the temperature, we can readily access the shapes of icosahedral nanocrystals with good uniformity. These gold nanostructures, with unique geometrical shapes, might find use in areas that include photonics, optoelectronics, and optical sensing. We also observed that these gold nanocrystals have a strong tendency to be immobilized spontaneously on the glass substrate.

Engineering Plasmonic Nanocrystal Coupling through Template-Assisted Self-Assembly

NASA Astrophysics Data System (ADS)

Greybush, Nicholas J.

The construction of materials from nanocrystal building blocks represents a powerful new paradigm for materials design. Just as nature's materials orchestrate intricate combinations of atoms from the library of the periodic table, nanocrystal "metamaterials" integrate individual nanocrystals into larger architectures with emergent collective properties. The individual nanocrystal "meta-atoms" that make up these materials are themselves each a nanoscale atomic system with tailorable size, shape, and elemental composition, enabling the creation of hierarchical materials with predesigned structure at multiple length scales. However, an improved fundamental understanding of the interactions among individual nanocrystals is needed in order to translate this structural control into enhanced functionality. The ability to form precise arrangements of nanocrystals and measure their collective properties is therefore essential for the continued development of nanocrystal metamaterials. In this dissertation, we utilize template-assisted self-assembly and spatially-resolved spectroscopy to form and characterize individual nanocrystal oligomers. At the intersection of "top-down" and "bottom-up" nanoscale patterning schemes, template-assisted self-assembly combines the design freedom of lithography with the chemical control of colloidal synthesis to achieve unique nanocrystal configurations. Here, we employ shape-selective templates to assemble new plasmonic structures, including heterodimers of Au nanorods and upconversion phosphors, a series of hexagonally-packed Au nanocrystal oligomers, and triangular formations of Au nanorods. Through experimental analysis and numerical simulation, we elucidate the means through which inter-nanocrystal coupling imparts collective optical properties to the plasmonic assemblies. Our self-assembly and measurement strategy offers a versatile platform for exploring optical interactions in a wide range of material systems and application areas.

Novel green synthetic strategy to prepare ZnO nanocrystals using rambutan (Nephelium lappaceum L.) peel extract and its antibacterial applications.

PubMed

Yuvakkumar, R; Suresh, J; Nathanael, A Joseph; Sundrarajan, M; Hong, S I

2014-08-01

In the present investigation, we report a sustainable novel green synthetic strategy to synthesis zinc oxide nanocrystals. This is the first report on sustainable biosynthesis of zinc oxide nanocrystals employing Nephelium lappaceum L., peel extract as a natural ligation agent. Green synthesis of zinc oxide nanocrystals was carried out via zinc-ellagate complex formation using rambutan peel wastes. The successful formation of zinc oxide nanocrystals was confirmed employing standard characterisation studies. A possible mechanism for the formation of ZnO nanocrystals with rambutan peel extract was also proposed. The prepared ZnO nanocrystals were coated on the cotton fabric and their antibacterial activity were analyzed. ZnO nanocrystals coated cotton showed good antibacterial activity towards Escherichia coli (E. coli), gram negative bacteria and Staphylococcus aureus (S. aureus), gram positive bacteria. Copyright © 2014 Elsevier B.V. All rights reserved.

One-Step Synthesis of Monodisperse In-Doped ZnO Nanocrystals

NASA Astrophysics Data System (ADS)

Wang, Qing Ling; Yang, Ye Feng; He, Hai Ping; Chen, Dong Dong; Ye, Zhi Zhen; Jin, Yi Zheng

2010-05-01

A method for the synthesis of high quality indium-doped zinc oxide (In-doped ZnO) nanocrystals was developed using a one-step ester elimination reaction based on alcoholysis of metal carboxylate salts. The resulting nearly monodisperse nanocrystals are well-crystallized with typically crystal structure identical to that of wurtzite type of ZnO. Structural, optical, and elemental analyses on the products indicate the incorporation of indium into the host ZnO lattices. The individual nanocrystals with cubic structures were observed in the 5% In-ZnO reaction, due to the relatively high reactivity of indium precursors. Our study would provide further insights for the growth of doped oxide nanocrystals, and deepen the understanding of doping process in colloidal nanocrystal syntheses.

Synthesis of gold nanochains via photoactivation technique and their catalytic applications.

PubMed

Sinha, Arun Kumar; Basu, Mrinmoyee; Sarkar, Sougata; Pradhan, Mukul; Pal, Tarasankar

2013-05-15

The article reports a simple photoactivation technique for the synthesis of chain like assembly of spherical Au nanocrystals using a nontoxic biochemical, β-cyclodextrin under ~365 nm UV-light irradiation. Under UV irradiation, β-cyclodextrin acts as a reducing as well as capping agent and eventually becomes a stabilizing linker for Au nanoparticles. The UV-visible spectroscopy, transmission electron microscopy (TEM), selected area electron diffraction (SAED), X-ray diffraction (XRD), and X-ray photoelectron spectroscopic techniques are employed to systematically characterize the Au nanochains. Additionally, it is shown that the Au nanocrystals act as an effective catalyst for the reduction in nitrobenzene to aniline and methylene blue to leuco methylene blue in presence of suitable reducing agent. The catalytic reduction reactions and kinetic parameters are evaluated from UV-visible spectroscopy. Copyright © 2013 Elsevier Inc. All rights reserved.

A general and robust strategy for the synthesis of nearly monodisperse colloidal nanocrystals

NASA Astrophysics Data System (ADS)

Pang, Xinchang; Zhao, Lei; Han, Wei; Xin, Xukai; Lin, Zhiqun

2013-06-01

Colloidal nanocrystals exhibit a wide range of size- and shape-dependent properties and have found application in myriad fields, incuding optics, electronics, mechanics, drug delivery and catalysis, to name but a few. Synthetic protocols that enable the simple and convenient production of colloidal nanocrystals with controlled size, shape and composition are therefore of key general importance. Current strategies include organic solution-phase synthesis, thermolysis of organometallic precursors, sol-gel processes, hydrothermal reactions and biomimetic and dendrimer templating. Often, however, these procedures require stringent experimental conditions, are difficult to generalize, or necessitate tedious multistep reactions and purification. Recently, linear amphiphilic block co-polymer micelles have been used as templates to synthesize functional nanocrystals, but the thermodynamic instability of these micelles limits the scope of this approach. Here, we report a general strategy for crafting a large variety of functional nanocrystals with precisely controlled dimensions, compositions and architectures by using star-like block co-polymers as nanoreactors. This new class of co-polymers forms unimolecular micelles that are structurally stable, therefore overcoming the intrinsic instability of linear block co-polymer micelles. Our approach enables the facile synthesis of organic solvent- and water-soluble nearly monodisperse nanocrystals with desired composition and architecture, including core-shell and hollow nanostructures. We demonstrate the generality of our approach by describing, as examples, the synthesis of various sizes and architectures of metallic, ferroelectric, magnetic, semiconductor and luminescent colloidal nanocrystals.

Biomimetic synthesis of noble metal nanocrystals

NASA Astrophysics Data System (ADS)

Chiu, Chin-Yi

At the nanometer scale, the physical and chemical properties of materials heavily depend on their sizes and shapes. This fact has triggered considerable efforts in developing controllable nanomaterial synthesis. The controlled growth of colloidal nanocrystal is a kinetic process, in which high-energy facets grow faster and then vanish, leading to a nanocrystal enclosed by low-energy facets. Identifying a surfactant that can selectively bind to a particular crystal facet and thus lower its surface energy, is critical and challenging in shape controlled synthesis of nanocrystals. Biomolecules exhibiting exquisite molecular recognition properties can be exploited to precisely engineer nanostructured materials. In the first part of my thesis, we employed the phage display technique to select a specific multifunctional peptide sequence which can bind on Pd surface and mediate Pd crystal nucleation and growth, achieving size controlled synthesis of Pd nanocrystals in aqueous solution. We further demonstrated a rational biomimetic approach to the predictable synthesis of nanocrystals enclosed by a particular facet in the case of Pt. Specifically, Pt {100} and Pt {111} facet-specific peptides were identified and used to synthesize Pt nanocubes and Pt nano-tetrahedrons, respectively. The mechanistic studies of Pt {111} facet-specific peptide had led us to study the facet-selective adsorption of aromatic molecules on noble metal surfaces. The discoveries had achieved the development of design strategies to select facet-selective molecules which can synthesize nanocrystals with expected shapes in both Pt and Pd system. At last, we exploited Pt facet-specific peptides and controlled the molecular interaction to produce one- and three- dimensional nanostructures composed of anisotropic nanoparticles in synthetic conditions without supramolecular pre-organization, demonstrating the full potential of biomolecules in mediating material formation process. My research on biomimetic synthesis of nanocrystals with shape control and nanostructures with control over the anisotropy are unprecedented, representing a step forward in achieving the goal of producing complex nanostructures with required properties. The fundamental studies on the biomolecule-inorganic interfaces have contributed to advancing the synthesis tool of colloidal nanomaterials and enriching understating of organic-inorganic interface, impacting many applications.

Cobalt ferrite nanocrystals: out-performing magnetotactic bacteria.

PubMed

Prozorov, Tanya; Palo, Pierre; Wang, Lijun; Nilsen-Hamilton, Marit; Jones, DeAnna; Orr, Daniel; Mallapragada, Surya K; Narasimhan, Balaji; Canfield, Paul C; Prozorov, Ruslan

2007-10-01

Magnetotactic bacteria produce exquisitely ordered chains of uniform magnetite (Fe(3)O(4)) nanocrystals, and the use of the bacterial mms6 protein allows for the shape-selective synthesis of Fe(3)O(4) nanocrystals. Cobalt ferrite (CoFe(2)O(4)) nanoparticles, on the other hand, are not known to occur in living organisms. Here we report on the use of the recombinant mms6 protein in a templated synthesis of CoFe(2)O(4) nanocrystals in vitro. We have covalently attached the full-length mms6 protein and a synthetic C-terminal domain of mms6 protein to self-assembling polymers in order to template hierarchical CoFe(2)O(4) nanostructures. This new synthesis pathway enables facile room-temperature shape-specific synthesis of complex magnetic crystalline nanomaterials with particle sizes in the range of 40-100 nm that are difficult to produce using conventional techniques.

The in situ synthesis of PbS nanocrystals from lead(II) n-octylxanthate within a 1,3-diisopropenylbenzene–bisphenol A dimethacrylate sulfur copolymer

PubMed Central

Bear, J. C.; Mayes, A. G.; Parkin, I. P.; O'Brien, P.

2017-01-01

The synthesis of lead sulfide nanocrystals within a solution processable sulfur ‘inverse vulcanization’ polymer thin film matrix was achieved from the in situ thermal decomposition of lead(II) n-octylxanthate, [Pb(S2COOct)2]. The growth of nanocrystals within polymer thin films from single-source precursors offers a faster route to networks of nanocrystals within polymers when compared with ex situ routes. The ‘inverse vulcanization’ sulfur polymer described herein contains a hybrid linker system which demonstrates high solubility in organic solvents, allowing solution processing of the sulfur-based polymer, ideal for the formation of thin films. The process of nanocrystal synthesis within sulfur films was optimized by observing nanocrystal formation by X-ray photoelectron spectroscopy and X-ray diffraction. Examination of the film morphology by scanning electron microscopy showed that beyond a certain precursor concentration the nanocrystals formed were not only within the film but also on the surface suggesting a loading limit within the polymer. We envisage this material could be used as the basis of a new generation of materials where solution processed sulfur polymers act as an alternative to traditional polymers. PMID:28878986

A feasible strategy to balance the crystallinity and specific surface area of metal oxide nanocrystals

NASA Astrophysics Data System (ADS)

Zhang, Q. P.; Xu, X. N.; Liu, Y. T.; Xu, M.; Deng, S. H.; Chen, Y.; Yuan, H.; Yu, F.; Huang, Y.; Zhao, K.; Xu, S.; Xiong, G.

2017-04-01

Practical, efficient synthesis of metal oxide nanocrystals with good crystallinity and high specific surface area by a modified polymer-network gel method is demonstrated, taking ZnO nanocrystals as an example. A novel stepwise heat treatment yields significant improvement in crystal quality. Such nanophase materials can effectively degrade common organic dyes under solar radiation and can perform very well in photo-assisted detection of NO2 gas. Other typical metal oxide nanocrystals with good crystallinity and high specific surface area were also synthesized successfully under similar conditions. This work provides a general strategy for the synthesis of metal oxide nanocrystals, balancing the crystallinity and specific surface area.

Structural phase transitions in niobium oxide nanocrystals

NASA Astrophysics Data System (ADS)

Yuvakkumar, R.; Hong, Sun Ig

2015-09-01

Niobium oxide nanocrystals were successfully synthesized employing the green synthesis method. Phase formation, microstructure and compositional properties of 1, 4 and 7 days incubation treated samples after calcinations at 450 °C were examined using X-ray diffraction, Raman, photoluminescence (PL), infrared, X-ray photoelectron spectra and transmission electron microscopic characterizations. It was observed that phase formation of Nb2O5 nanocrystals was dependent upon the incubation period required to form stable metal oxides. The characteristic results clearly revealed that with increasing incubation and aging, the transformation of cubic, orthorhombic and monoclinic phases were observed. The uniform heating at room temperature (32 °C) and the ligation of niobium atoms due to higher phenolic constituents of utilized rambutan during aging processing plays a vital role in structural phase transitions in niobium oxide nanocrystals. The defects over a period of incubation and the intensities of the PL spectra changing over a period of aging were related to the amount of the defects induced by the phase transition.

Formation of noble metal nanocrystals in the presence of biomolecules

NASA Astrophysics Data System (ADS)

Burt, Justin Lockheart

One of the most promising, yet least studied routes for producing biocompatible nanostructures involves synthesis in the presence of biomolecules. I hypothesized that globular proteins could provide a suitable framework to regulate the formation of noble metal nanocrystals. As proof of concept, I designed two novel synthesis protocols utilizing bovine serum albumin (BSA) protein to regulate the formation of gold nanocrystals. In the first case, the standard protocol for polyol reduction was modified by replacing ethylene glycol with glycerin, replacing synthetic polymers with BSA as protecting agent, and decreasing the reaction temperature. In the second case, the Brust-Schiffrin two-phase reduction was modified by replacing alkylthiols with BSA as protecting agent, which facilitated a strictly aqueous phase synthesis. Due to superior product yield and rapid reduction at room temperature, the aqueous protocol became the foundation for subsequent studies. I extended this approach to produce well-dispersed ˜2nm silver, gold, and platinum nanocrystals. Having demonstrated the feasibility of BSA-functionalized nanocrystals, some potential uses were explored. BSA-functionalized silver nanocrystals were employed in a broader study on the interaction of silver nanocrystals with HIV. BSA-functionalized gold nanocrystals were utilized for in vivo dosage of a contrast enhancing agent to bacteria. BSA-functionalized platinum nanocrystals were studied as hydrogenation catalysts. Since many intriguing uses for protein-functionalized nanocrystals involve incorporation into biosystems, I sought to enhance biocompatibility by using ascorbic acid as reducing agent. Initial experiments revealed elongated and branched nanocrystals. Such structures were not observed in previous synthesis protocols with BSA, so I hypothesized ascorbic acid was driving their formation. To test my assertion, I reduced ionic gold in an aqueous solution of ascorbic acid, thereby discovering a new method for producing multiply-branched gold nanocrystals. Two conditions were necessary to achieve multiply-branched structures: rapid kinetics, and strongly acidic pH. By exploiting ascorbic acid complexation with BSA to moderate reaction kinetics, and using sodium hydroxide to provide basic pH, the two conditions for branching were negated, and well-dispersed ˜2.5nm gold nanocrystals were obtained. This protocol represents a novel, environmentally benign approach to producing biocompatible nanocrystals, relying on proteins, ascorbic acid, sodium hydroxide, and water, all at ambient temperature.

A ceramic microreactor for the synthesis of water soluble CdS and CdS/ZnS nanocrystals with on-line optical characterization

NASA Astrophysics Data System (ADS)

Pedro, Sara Gómez-De; Puyol, Mar; Izquierdo, David; Salinas, Iñigo; de La Fuente, J. M.; Alonso-Chamarro, Julián

2012-02-01

In this paper, a computer controlled microreactor to synthesize water soluble CdS and CdS/ZnS nanocrystals with in situ monitoring of the reaction progress is developed. It is based on ceramic tapes and the Low-Temperature Co-fired Ceramics technology (LTCC). As well the microsystem set-up, the microreactor fluidic design has also been thoroughly optimized. The final device is based on a hydrodynamic focusing of the reagents followed by a three-dimensional micromixer. This generates monodispersed and stable CdS and core-shell CdS/ZnS nanocrystals of 4.5 and 4.2 nm, respectively, with reproducible optical properties in terms of fluorescence emission wavelengths, bandwidth, and quantum yields, which is a key requirement for their future analytical applications. The synthetic process is also controlled in real time with the integration of an optical detection system for absorbance and fluorescence measurements based on commercial miniaturized optical components. This makes possible the efficient managing of the hydrodynamic variables to obtain the desired colloidal suspension. As a result, a simple, economic, robust and portable microsystem for the well controlled synthesis of CdS and CdS/ZnS nanocrystals is presented. Moreover, the reaction takes place in aqueous medium, thus allowing the direct modular integration of this microreactor in specific analytical microsystems, which require the use of such quantum dots as labels.

High-yield sol-gel synthesis of well-dispersed, colorless ZrO(2) nanocrystals.

PubMed

Mizuno, Mikihisa; Sasaki, Yuichi; Lee, Sungkil; Katakura, Hitoshi

2006-08-15

A 93% high-yield synthesis of well-dispersed, colorless zirconium dioxide (ZrO(2)) nanocrystals is reported. In this synthesis, hydrolysis and condensation reactions of zirconium(IV) tert-butoxide in the presence of oleic acid (100 degrees C) formed ZrO(2) precursors. The ZrO(2) precursors were made of -Zr-O-Zr- networks surrounded by oleic acid molecules. Annealing (280 degrees C) the precursors dispersed in dioctyl ether caused crystallization of the -Zr-O-Zr- networks, thereby generating 4 nm ZrO(2) nanocrystals stabilized with oleic acid. The particles were highly crystalline and tetragonal phase. A dense ZrO(2) nanocrystal dispersion in toluene (280 mg/mL) showed a transmittance of about 90% (3 mm optical path length) in the whole visible region.

Cellulose nanocrystals with tunable surface charge for nanomedicine

NASA Astrophysics Data System (ADS)

Hosseinidoust, Zeinab; Alam, Md Nur; Sim, Goeun; Tufenkji, Nathalie; van de Ven, Theo G. M.

2015-10-01

Crystalline nanoparticles of cellulose exhibit attractive properties as nanoscale carriers for bioactive molecules in nanobiotechnology and nanomedicine. For applications in imaging and drug delivery, surface charge is one of the most important factors affecting the performance of nanocarriers. However, current methods of preparation offer little flexibility for controlling the surface charge of cellulose nanocrystals, leading to compromised colloidal stability under physiological conditions. We report a synthesis method that results in nanocrystals with remarkably high carboxyl content (6.6 mmol g-1) and offers continuous control over surface charge without any adjustment to the reaction conditions. Six fractions of nanocrystals with various surface carboxyl contents were synthesized from a single sample of softwood pulp with carboxyl contents varying from 6.6 to 1.7 mmol g-1 and were fully characterized. The proposed method resulted in highly stable colloidal nanocrystals that did not aggregate when exposed to high salt concentrations or serum-containing media. Interactions of these fractions with four different tissue cell lines were investigated over a wide range of concentrations (50-300 μg mL-1). Darkfield hyperspectral imaging and confocal microscopy confirmed the uptake of nanocrystals by selected cell lines without any evidence of membrane damage or change in cell density; however a charge-dependent decrease in mitochondrial activity was observed for charge contents higher than 3.9 mmol g-1. A high surface carboxyl content allowed for facile conjugation of fluorophores to the nanocrystals without compromising colloidal stability. The cellular uptake of fluoresceinamine-conjugated nanocrystals exhibited a time-dose dependent relationship and increased significantly with doubling of the surface charge.Crystalline nanoparticles of cellulose exhibit attractive properties as nanoscale carriers for bioactive molecules in nanobiotechnology and nanomedicine. For applications in imaging and drug delivery, surface charge is one of the most important factors affecting the performance of nanocarriers. However, current methods of preparation offer little flexibility for controlling the surface charge of cellulose nanocrystals, leading to compromised colloidal stability under physiological conditions. We report a synthesis method that results in nanocrystals with remarkably high carboxyl content (6.6 mmol g-1) and offers continuous control over surface charge without any adjustment to the reaction conditions. Six fractions of nanocrystals with various surface carboxyl contents were synthesized from a single sample of softwood pulp with carboxyl contents varying from 6.6 to 1.7 mmol g-1 and were fully characterized. The proposed method resulted in highly stable colloidal nanocrystals that did not aggregate when exposed to high salt concentrations or serum-containing media. Interactions of these fractions with four different tissue cell lines were investigated over a wide range of concentrations (50-300 μg mL-1). Darkfield hyperspectral imaging and confocal microscopy confirmed the uptake of nanocrystals by selected cell lines without any evidence of membrane damage or change in cell density; however a charge-dependent decrease in mitochondrial activity was observed for charge contents higher than 3.9 mmol g-1. A high surface carboxyl content allowed for facile conjugation of fluorophores to the nanocrystals without compromising colloidal stability. The cellular uptake of fluoresceinamine-conjugated nanocrystals exhibited a time-dose dependent relationship and increased significantly with doubling of the surface charge. Electronic supplementary information (ESI) available: Additional results are presented in the ESI in Fig. S1 through S4. See DOI: 10.1039/c5nr02506k

Synthesis of a conjugated pyrrolopyridazinedione-benzodithiophene (PPD-BDT) copolymer and its application in organic and hybrid solar cells.

PubMed

Knall, Astrid-Caroline; Jones, Andrew O F; Kunert, Birgit; Resel, Roland; Reishofer, David; Zach, Peter W; Kirkus, Mindaugas; McCulloch, Iain; Rath, Thomas

2017-01-01

Herein, we describe the synthesis and characterization of a conjugated donor-acceptor copolymer consisting of a pyrrolopyridazinedione (PPD) acceptor unit, and a benzodithiophene (BDT) donor unit. The polymerization was done via a Stille cross-coupling polycondensation. The resulting PPD-BDT copolymer revealed an optical bandgap of 1.8 eV and good processability from chlorobenzene solutions. In an organic solar cell in combination with PC 70 BM, the polymer led to a power conversion efficiency of 4.5%. Moreover, the performance of the copolymer was evaluated in polymer/nanocrystal hybrid solar cells using non-toxic CuInS 2 nanocrystals as inorganic phase, which were prepared from precursors directly in the polymer matrix without using additional capping ligands. The PPD-BDT/CuInS 2 hybrid solar cells showed comparably high photovoltages and a power conversion efficiency of 2.2%.

Low-temperature synthesis of homogeneous solid solutions of scheelite-structured Ca 1-xSr xWO 4 and Sr 1-xBa xWO 4 nanocrystals

DOE PAGES

Culver, Sean P.; Greaney, Matthew J.; Tinoco, Antonio; ...

2015-07-24

Here, a series of compositionally complex scheelite-structured nanocrystals of the formula A 1-xA’ xWO 4 (A = Ca, Sr, Ba) have been prepared under benign synthesis conditions using the vapor diffusion sol–gel method. Discrete nanocrystals with sub-20 nm mean diameters were obtained after kinetically controlled hydro- lysis and polycondensation at room temperature, followed by composition-dependent thermal aging at or below 60 °C. Rietveld analysis of X-ray diffraction data and Raman spectroscopy verified the synthesis of continuous and phase-pure nanocrystal solid solutions across the entire composition space for A 1-xA’ xWO 4, where 0 ≤ x ≤ 1. Elemental analysis bymore » X-ray photoelectron and inductively coupled plasma- atomic emission spectroscopies demonstrated excellent agreement between the nominal and experi- mentally determined elemental stoichiometries, while energy dispersive X-ray spectroscopy illustrated good spatial elemental homogeneity within these nanocrystals synthesized under benign conditions.« less

Microwave-Assisted Size Control of Colloidal Nickel Nanocrystals for Colloidal Nanocrystals-Based Non-volatile Memory Devices

NASA Astrophysics Data System (ADS)

Yadav, Manoj; Velampati, Ravi Shankar R.; Mandal, D.; Sharma, Rohit

2018-03-01

Colloidal synthesis and size control of nickel (Ni) nanocrystals (NCs) below 10 nm are reported using a microwave synthesis method. The synthesised colloidal NCs have been characterized using x-ray diffraction, transmission electron microscopy (TEM) and dynamic light scattering (DLS). XRD analysis highlights the face centred cubic crystal structure of synthesised NCs. The size of NCs observed using TEM and DLS have a distribution between 2.6 nm and 10 nm. Furthermore, atomic force microscopy analysis of spin-coated NCs over a silicon dioxide surface has been carried out to identify an optimum spin condition that can be used for the fabrication of a metal oxide semiconductor (MOS) non-volatile memory (NVM) capacitor. Subsequently, the fabrication of a MOS NVM capacitor is reported to demonstrate the potential application of colloidal synthesized Ni NCs in NVM devices. We also report the capacitance-voltage (C-V) and capacitance-time (C-t) response of the fabricated MOS NVM capacitor. The C-V and C-t characteristics depict a large flat band voltage shift (V FB) and high retention time, respectively, which indicate that colloidal Ni NCs are excellent candidates for applications in next-generation NVM devices.

Germanium–Tin/Cadmium Sulfide Core/Shell Nanocrystals with Enhanced Near-Infrared Photoluminescence

DOE PAGES

Boote, Brett W.; Men, Long; Andaraarachchi, Himashi P.; ...

2017-06-27

Ge 1–xSn x alloy nanocrystals and Ge 1–xSn x/CdS core/shell nanocrystals were prepared via solution phase synthesis, and their size, composition, and optical properties were characterized. We found that the diameter of the nanocrystal samples ranged from 6 to 13 nm. Furthermore, the crystal structure of the Ge 1–xSn x materials was consistent with a cubic diamond phase, while the CdS shell was consistent with the zinc blende polytype. Inclusion of Sn alone does not result in enhanced photoluminescence intensity; however, adding an epitaxial CdS shell onto the Ge 1–xSn x nanocrystals does enhance the photoluminescence up to 15-fold versusmore » that of Ge/CdS nanocrystals with a pure Ge core. There is more effective passivation of surface defects, and a consequent decrease in the level of surface oxidation, by the CdS shell as a result of improved epitaxy (smaller lattice mismatch) is the most likely explanation for the increased photoluminescence observed for the Ge 1–xSn x/CdS materials. With enhanced photoluminescence in the near-infrared region, Ge 1–xSn x core/shell nanocrystals might be useful alternatives to other materials for energy capture and conversion applications and as imaging probes.« less

Charge transport in metal oxide nanocrystal-based materials

NASA Astrophysics Data System (ADS)

Runnerstrom, Evan Lars

There is probably no class of materials more varied, more widely used, or more ubiquitous than metal oxides. Depending on their composition, metal oxides can exhibit almost any number of properties. Of particular interest are the ways in which charge is transported in metal oxides: devices such as displays, touch screens, and smart windows rely on the ability of certain metal oxides to conduct electricity while maintaining visible transparency. Smart windows, fuel cells, and other electrochemical devices additionally rely on efficient transport of ionic charge in and around metal oxides. Colloidal synthesis has enabled metal oxide nanocrystals to emerge as a relatively new but highly tunable class of materials. Certain metal oxide nanocrystals, particularly highly doped metal oxides, have been enjoying rapid development in the last decade. As in myriad other materials systems, structure dictates the properties of metal oxide nanocrystals, but a full understanding of how nanocrystal synthesis, the processing of nanocrystal-based materials, and the structure of nanocrystals relate to the resulting properties of nanocrystal-based materials is still nascent. Gaining a fundamental understanding of and control over these structure-property relationships is crucial to developing a holistic understanding of metal oxide nanocrystals. The unique ability to tune metal oxide nanocrystals by changing composition through the introduction of dopants or by changing size and shape affords a way to study the interplay between structure, processing, and properties. This overall goal of this work is to chemically synthesize colloidal metal oxide nanocrystals, process them into useful materials, characterize charge transport in materials based on colloidal metal oxide nanocrystals, and develop ways to manipulate charge transport. In particular, this dissertation characterizes how the charge transport properties of metal oxide nanocrystal-based materials depend on their processing and structure. Charge transport can obviously be taken to mean the conduction of electrons, but it also refers to the motion of ions, such as lithium ions and protons. In many cases, the transport of ions is married to the motion of electrons as well, either through an external electrical circuit, or within the same material in the case of mixed ionic electronic conductors. The collective motion of electrons over short length scales, that is, within single nanocrystals, is also a subject of study as it pertains to plasmonic nanocrystals. Finally, charge transport can also be coupled to or result from the formation of defects in metal oxides. All of these modes of charge transport in metal oxides gain further complexity when considered in nanocrystalline systems, where the introduction of numerous surfaces can change the character of charge transport relative to bulk systems, providing opportunities to exploit new physical phenomena. Part I of this dissertation explores the combination of electronic and ionic transport in electrochromic devices based on nanocrystals. Colloidal chemistry and solution processing are used to fabricate nanocomposites based on electrochromic tin-doped indium oxide (ITO) nanocrystals. The nanocomposites, which are completely synthesized using solution processing, consist of ITO nanocrystals and lithium bis(trifluoromethylsulfonyl)amide (LiTFSI) salt dispersed in a lithium ion-conducting polymer matrix of either poly(ethylene oxide) (PEO) or poly(methyl methacrylate) (PMMA). ITO nanocrystals are prepared by colloidal synthetic methods and the nanocrystal surface chemistry is modified to achieve favorable nanocrystal-polymer interactions. Homogeneous solutions containing polymer, ITO nanocrystals, and lithium salt are thus prepared and deposited by spin casting. Characterization by DC electronic measurements, microscopy, and x-ray scattering techniques show that the ITO nanocrystals form a complete, connected electrode within a polymer electrolyte matrix, and that the morphology and properties of the nanocomposites can be manipulated by changing the chemical composition of the deposition solution. Careful application of AC impedance spectroscopy techniques and DC measurements are used to show that the nanocomposites exhibit mixed ionic and electronic conductivity, where electronic charge is transported through the ITO nanocrystal phase, and ionic charge is transported through the polymer matrix phase. The synthetic methods developed here and understanding of charge transport ultimately lead to the fabrication of a solid state nanocomposite electrochromic device based on nanocrystals of ITO and cerium oxide. Part II of this dissertation considers electron transport within individual metal oxide nanocrystals themselves. It primarily examines relationships between synthetic chemistry, doping mechanisms in metal oxides, and the accompanying physics of free carrier scattering within the interior of highly doped metal oxide nanocrystals, with particular mind paid to ITO nanocrystals. Additionally, synthetic methods as well as metal oxide defect chemistry influences the balance between activation and compensation of dopants, which limits the nanocrystals' free carrier concentration. Furthermore, because of ionized impurity scattering of the oscillating electrons by dopant ions, scattering must be treated in a fundamentally different way in semiconductor metal oxide materials when compared with conventional metals. (Abstract shortened by ProQuest.).

Colloidal synthesis of biocompatible iron disulphide nanocrystals.

PubMed

Santos-Cruz, J; Nuñez-Anita, R E; Mayén-Hernández, S A; Martínez-Alvarez, O; Acosta-Torres, L S; de la Fuente-Hernández, J; Campos-González, E; Vega-González, M; Arenas-Arrocena, M C

2018-08-01

The aim of this research was to synthesis biocompatible iron disulphide nanocrystals at different reaction temperatures using the colloidal synthesis methodology. Synthesis was conducted at the 220-240 °C range of reaction temperatures at intervals of 5 °C in an inert argon atmosphere. The toxicity of iron disulphide nanocrystals was evaluated in vitro using mouse fibroblast cell line. Two complementary assays were conducted: the first to evaluate cell viability of the fibroblast via an MTT assay and the second to determine the preservation of fibroblast nuclei integrity through DAPI staining, which labels nuclear DNA in fluorescence microscopes. Through TEM and HRTEM, we observed a cubic morphology of pyrite iron disulphide nanocrystals ranging in sizes 25-50 nm (225 °C), 50-70 nm (230 °C) and >70 nm (235 °C). Through X-ray diffraction, we observed a mixture of pyrite and pyrrohotite in the samples synthesized at 225 °C and 240 °C, showing the best photocatalytic activity at 80% and 65%, respectively, for the degradation of methylene blue after 120 minutes. In all experimental groups, iron disulphide nanocrystals were biocompatible, i.e. no statistically significant differences were observed between experimental groups as shown in a one-way ANOVA and Tukey's test. Based on all of these results, we recommend non-cytotoxic semiconductor iron sulphide nanocrystals for biomedical applications.

In situ bioinspired synthesis of silver chloride nanocrystals on silk fibroin fibers

NASA Astrophysics Data System (ADS)

Su, Huilan; Han, Jie; Dong, Qun; Xu, Jia; Chen, Ying; Gu, Yu; Song, Weiqiang; Zhang, Di

2011-02-01

Silver chloride (AgCl) nanocrystals were formed and grown on silk fibroin fibers (SFFs) by a room-temperature process. Practically, the degummed SFFs were immersed into silver nitrate solution and sodium chloride solution in turn. The amino acids on the SFF surface were negatively charged in alkaline impregnant, providing locations to immobilize silver ions and form silver chloride seeds. AgCl nanocrystals can further grow into cubic AgCl nanocrystals with an edge of about 100 nm. The morphologies of the AgCl nanocrystals were mostly influenced by the concentration of sodium chloride solution and the special configurations of the SFFs. The target AgCl/SFF nanocomposites constructed by AgCl nanocrystals and substrate SFFs could be used as photocatalysts in water splitting and antibacterial agents. This work provides an important example in the introduction of natural biofibers to the synthesis of functional hybrid nanocomposites by a green and mild technique.

Linearly arranged polytypic CZTSSe nanocrystals

PubMed Central

Fan, Feng-Jia; Wu, Liang; Gong, Ming; Chen, Shi You; Liu, Guang Yao; Yao, Hong-Bin; Liang, Hai-Wei; Wang, Yi-Xiu; Yu, Shu-Hong

2012-01-01

Even colloidal polytypic nanostructures show promising future in band-gap tuning and alignment, researches on them have been much less reported than the standard nano-heterostructures because of the difficulties involved in synthesis. Up to now, controlled synthesis of colloidal polytypic nanocrsytals has been only realized in II-VI tetrapod and octopod nanocrystals with branched configurations. Herein, we report a colloidal approach for synthesizing non-branched but linearly arranged polytypic I2-II-IV-VI4 nanocrystals, with a focus on polytypic non-stoichiometric Cu2ZnSnSxSe4−x nanocrystals. Each synthesized polytypic non-stoichiometric Cu2ZnSnSxSe4−x nanocrystal is consisted of two zinc blende-derived ends and one wurtzite-derived center part. The formation mechanism has been studied and the phase composition can be tuned through adjusting the reaction temperature, which brings a new band-gap tuning approach to Cu2ZnSnSxSe4-x nanocrystals. PMID:23233871

Synthesis and Characterization of Chalcopyrite (CuInS2 and CuhInSe2) Colloidal Nanoparticles for Optoelectronic Applications via Low-Temperature Pyrolysis of Single-Source Precursors

NASA Technical Reports Server (NTRS)

Castro, S. L.; Bailey, S. G.; Raffaelle, R. P.; Banger, K. K.; Fahey, Stephen; Hepp, A. F.

2003-01-01

Nanocrystalline (or quantum dot) materials hold potential as components of next-generation photovoltaic (PV) devices. The inclusion of quantum dots in PV devices has been proposed as a means to improve the efficiency of photon conversion (quantum dot solar cell), enable low-cost deposition of thin-films, provide sites for exciton dissociation, and pathways for electron transport. Quantum dots are also expected to be more resistant to degradation from electron, proton, and alpha particle radiation than the corresponding bulk material, a requirement for use in space solar sells. Chalcopyrite nanocrystals can be produced by low-temperature thermal decomposition of single-source precursors such as (PR3)2CuIn(ER')4 (R = Ph, R' = Et, E = S; R = R' = Ph, E = Se). Single-source precursors are molecules which contain all the necessary elements for synthesis of a desired material. Thermal decomposition of the precursor results in the formation of material with the correct stoichiometry as a nanocrystalline powder or a thin film, often at significantly lower temperatures than those typically employed for thin-film deposition by multi-source evaporation techniques, typically less than 500 C. We show that CuInSz and CuInSe2 nanocrystals can be synthesized from the precursors at temperatures as low as 250 C. The nanocrystals are characterized by optical spectroscopy, X-ray diffraction, and electron microscopy.

Supramolecular Assembly of Single-Source Metal-Chalcogenide Nanocrystal Precursors.

PubMed

Smith, Stephanie C; Bryks, Whitney; Tao, Andrea R

2018-05-28

In this Feature Article, we discuss our recent work in the synthesis of novel supramolecular precursors for semiconductor nanocrystals. Metal chalcogenolates that adopt liquid crystalline phases are employed as single-source precursors that template the growth of shaped solid-state nanocrystals. Supramolecular assembly is programmed by both precursor chemical composition and molecular parameters such alkyl chain length, steric bulk, and the intercalation of halide ions. Here, we explore the various design principles that enable the rational synthesis of these single-source precursors, their liquid crystalline phases, and the various semiconductor nanocrystal products that can be generated by thermolysis, ranging from highly anisotropic two-dimensional nanosheets and nanodisks to spheres.

Synthesis of optimized indium phosphide/zinc sulfide core/shell nanocrystals and titanium dioxide nanotubes for quantum dot sensitized solar cells

NASA Astrophysics Data System (ADS)

Lee, Seungyong

Synthesis of InP/ZnS core/shell nanocrystals and TiO 2 nanotubes and the optimization study to couple them together were explored for quantum dot sensitized solar cells. Its intrinsic nontoxicity makes the direct band gap InP/ZnS core/shell be one of the most promising semiconductor nanocrystals for optoelectric applications, with the advantage of tuning the optical absorption range in the desired solar spectrum region. Highly luminescent and monodisperse InP/ZnS nanocrystals were synthesized in a non-coordinating solvent. By varying the synthesis scheme, different size InP/ZnS nanocrystals with emission peaks ranging from 520 nm to 620 nm were grown. For the purpose of ensuring air stability, a ZnS shell was grown. The ZnS shell improves the chemical stability in terms of oxidation prevention. Transmission electron microscopy (TEM) image shows that the nanocrystals are highly crystalline and monodisperse. Free-standing TiO2 nanotubes were produced by an anodization method using ammonium fluoride. The free-standing nanotubes were formed under the condition that the chemical dissolution speed associated with fluoride concentration was faster than the speed of Ti oxidation. Highly ordered free-standing anatase form TiO2 nanotubes, which are transformed by annealing at the optimized temperature, are expected to be ideal for coupling with the prepared InP/ZnS nanocrystals. Electrophoretic deposition was carried out to couple the InP/ZnS nanocrystals with the TiO2 nanotubes. Under the adjusted applied voltage condition, the current during the electrophoretic deposition decreased continuously with time. The amount of the deposited nanocrystals was estimated by calculation and the evenly deposited nanocrystals on the TiO2 nanotubes were observed by TEM.

Biomolecular Assembly of Gold Nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Micheel, Christine Marya

2005-05-20

Over the past ten years, methods have been developed to construct discrete nanostructures using nanocrystals and biomolecules. While these frequently consist of gold nanocrystals and DNA, semiconductor nanocrystals as well as antibodies and enzymes have also been used. One example of discrete nanostructures is dimers of gold nanocrystals linked together with complementary DNA. This type of nanostructure is also known as a nanocrystal molecule. Discrete nanostructures of this kind have a number of potential applications, from highly parallel self-assembly of electronics components and rapid read-out of DNA computations to biological imaging and a variety of bioassays. My research focused inmore » three main areas. The first area, the refinement of electrophoresis as a purification and characterization method, included application of agarose gel electrophoresis to the purification of discrete gold nanocrystal/DNA conjugates and nanocrystal molecules, as well as development of a more detailed understanding of the hydrodynamic behavior of these materials in gels. The second area, the development of methods for quantitative analysis of transmission electron microscope data, used computer programs written to find pair correlations as well as higher order correlations. With these programs, it is possible to reliably locate and measure nanocrystal molecules in TEM images. The final area of research explored the use of DNA ligase in the formation of nanocrystal molecules. Synthesis of dimers of gold particles linked with a single strand of DNA possible through the use of DNA ligase opens the possibility for amplification of nanostructures in a manner similar to polymerase chain reaction. These three areas are discussed in the context of the work in the Alivisatos group, as well as the field as a whole.« less

Template-free synthesis and structural evolution of discrete hydroxycancrinite zeolite nanorods from high-concentration hydrogels.

PubMed

Chen, Shaojiang; Sorge, Lukas P; Seo, Dong-Kyun

2017-12-07

We report the synthesis and characterization of hydroxycancrinite zeolite nanorods by a simple hydrothermal treatment of aluminosilicate hydrogels at high concentrations of precursors without the use of structure-directing agents. Transmission electron microscopy (TEM) analysis reveals that cancrinite nanorods, with lengths of 200-800 nm and diameters of 30-50 nm, exhibit a hexagonal morphology and are elongated along the crystallographic c direction. The powder X-ray diffraction (PXRD), Fourier transform infrared (FT-IR) and TEM studies revealed sequential events of hydrogel formation, the formation of aggregated sodalite nuclei, the conversion of sodalite to cancrinite and finally the growth of cancrinite nanorods into discrete particles. The aqueous dispersion of the discrete nanorods displays a good stability between pH 6-12 with the zeta potential no greater than -30 mV. The synthesis is unique in that the initial aggregated nanocrystals do not grow into microsized particles (aggregative growth) but into discrete nanorods. Our findings demonstrate an unconventional possibility that discrete zeolite nanocrystals could be produced from a concentrated hydrogel.

Synthesis and Manipulation of Semiconductor Nanocrystals inMicrofluidic Reactors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chan, Emory Ming-Yue

2006-01-01

Microfluidic reactors are investigated as a mechanism tocontrol the growth of semiconductor nanocrystals and characterize thestructural evolution of colloidal quantum dots. Due to their shortdiffusion lengths, low thermal masses, and predictable fluid dynamics,microfluidic devices can be used to quickly and reproducibly alterreaction conditions such as concentration, temperature, and reactiontime, while allowing for rapid reagent mixing and productcharacterization. These features are particularly useful for colloidalnanocrystal reactions, which scale poorly and are difficult to controland characterize in bulk fluids. To demonstrate the capabilities ofnanoparticle microreactors, a size series of spherical CdSe nanocrystalswas synthesized at high temperature in a continuous-flow, microfabricatedglass reactor. Nanocrystalmore » diameters are reproducibly controlled bysystematically altering reaction parameters such as the temperature,concentration, and reaction time. Microreactors with finer control overtemperature and reagent mixing were designed to synthesize nanoparticlesof different shapes, such as rods, tetrapods, and hollow shells. The twomajor challenges observed with continuous flow reactors are thedeposition of particles on channel walls and the broad distribution ofresidence times that result from laminar flow. To alleviate theseproblems, I designed and fabricated liquid-liquid segmented flowmicroreactors in which the reaction precursors are encapsulated inflowing droplets suspended in an immiscible carrier fluid. The synthesisof CdSe nanocrystals in such microreactors exhibited reduced depositionand residence time distributions while enabling the rapid screening aseries of samples isolated in nL droplets. Microfluidic reactors werealso designed to modify the composition of existing nanocrystals andcharacterize the kinetics of such reactions. The millisecond kinetics ofthe CdSe-to-Ag 2Se nanocrystal cation exchange reaction are measured insitu with micro-X-ray Absorption Spectroscopy in silicon microreactorsspecifically designed for rapid mixing and time-resolved X-rayspectroscopy. These results demonstrate that microreactors are valuablefor controlling and characterizing a wide range of reactions in nLvolumes even when nanoscale particles, high temperatures, causticreagents, and rapid time scales are involved. These experiments providethe foundation for future microfluidic investigations into the mechanismsof nanocrystal growth, crystal phase evolution, and heterostructureassembly.« less

An in-situ phosphorus source for the synthesis of Cu 3P and the subsequent conversion to Cu 3PS 4 nanoparticle clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sheets, Erik J.; Stach, Eric A.; Yang, Wei -Chang

2015-09-20

The search for alternative earth abundant semiconducting nanocrystals for sustainable energy applications has brought forth the need for nanoscale syntheses beyond bulk synthesis routes. Of particular interest are metal phosphides and derivative I-V-VI chalcogenides including copper phosphide (Cu 3P) and copper thiophosphate (Cu 3PS 4). Herein, we report a one-pot, solution-based synthesis of Cu 3P nanocrystals utilizing an in-situ phosphorus source: phosphorus pentasulfide (P 2S 5) in trioctylphosphine (TOP). By injecting this phosphorus source into a copper solution in oleylamine (OLA), uniform and size controlled Cu 3P nanocrystals with a phosphorous-rich surface are synthesized. The subsequent reaction of the Cumore » 3P nanocrystals with decomposing thiourea forms nanoscale Cu 3PS 4 particles having p-type conductivity and an effective optical band gap of 2.36 eV.« less

Enhanced photocatalytic activity of ternary CuInS2 nanocrystals synthesized from the combination of a binary Cu(I)S precursor and InCl3

NASA Astrophysics Data System (ADS)

Mondal, Gopinath; Santra, Ananyakumari; Jana, Sumanta; Pramanik, Nimai Chand; Mondal, Anup; Bera, Pulakesh

2018-04-01

Ternary copper indium sulfide (CIS) nanocrystals (NCs) have been synthesized by mixing of binary precursor [CuI(bdpa)2][CuICl2] ( 1) and/or [CuI(mdpa)2][CuICl2] ( 2) (where, mdpa and bdpa represent methyl and benzyl ester of 3,5-dimethyl pyrazole-1-dithioic acid, respectively) with InCl3 in a low-temperature solvothermal process. The +1 oxidation state of copper and the atomic ratio Cu to S (1:2) is atomically maintained in the pyrazole-based Cu(I)-S precursor to synthesize phase pure CuInS2. Coordinating solvents like ethylene diamine (EN) and ethylene glycol (EG) have been used in the synthesis without any surfactants. No use of external surfactants in the synthesis of CIS nanoparticles reveals that precursor acts as stabilizing agent. The synthesized nanocrystals were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and energy dispersive X-ray spectroscopy (EDX) studies. The optical property of the nanocrystals shows a pronounced quantum confinement effect in the particles with band gap energy ca. 1.5 eV. The formation mechanism of ternary CIS has been proposed. The pore size distributions of the particles show the average pore diameters 13.1 nm from 1 and 5.3 nm from 2. The calculated values of the specific surface area are 8.123 and 9.577 m2/g for 1 and 2, respectively. The excellent photocatalytic degradation of rose bengal (RB) and rhodamine B (RhB) was demonstrated by the porous CIS nanocrystals. [Figure not available: see fulltext.

Ultrafast synthesis of flower-like ordered Pd3Pb nanocrystals with superior electrocatalytic activities towards oxidation of formic acid and ethanol

NASA Astrophysics Data System (ADS)

Jana, Rajkumar; Subbarao, Udumula; Peter, Sebastian C.

2016-01-01

Ordered intermetallic nanocrystals with high surface area are highly promising as efficient catalysts for fuel cell applications because of their unique electrocatalytic properties. The present work discusses about the controlled synthesis of ordered intermetallic Pd3Pb nanocrystals in different morphologies at relatively low temperature for the first time by polyol and hydrothermal methods both in presence and absence of surfactant. Here for the first time we report surfactant free synthesis of ordered flower-like intermetallic Pd3Pb nanocrystals in 10 s. The structural characteristics of the nanocrystals are confirmed by powder X-ray diffraction, transmission electron microscopy, field emission scanning electron microscopy, X-ray photoelectron spectroscopy and energy-dispersive X-ray spectroscopy. The as synthesized ordered Pd3Pb nanocrystals exhibit far superior electrocatalytic activity and durability towards formic acid and ethanol oxidation over commercially available Pd black (Pd/C). The morphological variation of nanocrystals plays a crucial role in the electrocatalytic oxidation of formic acid and ethanol. Among the catalysts, the flower-like Pd3Pb shows enhanced activity and stability in electrocatalytic formic acid and ethanol oxidation. The current density and mass activity of flower-like Pd3Pb catalyst are higher by 2.5 and 2.4 times than that of Pd/C for the formic acid oxidation and 1.5 times each for ethanol oxidation.

A ceramic microreactor for the synthesis of water soluble CdS and CdS/ZnS nanocrystals with on-line optical characterization.

PubMed

Gómez-de Pedro, Sara; Puyol, Mar; Izquierdo, David; Salinas, Iñigo; de la Fuente, J M; Alonso-Chamarro, Julián

2012-02-21

In this paper, a computer controlled microreactor to synthesize water soluble CdS and CdS/ZnS nanocrystals with in situ monitoring of the reaction progress is developed. It is based on ceramic tapes and the Low-Temperature Co-fired Ceramics technology (LTCC). As well the microsystem set-up, the microreactor fluidic design has also been thoroughly optimized. The final device is based on a hydrodynamic focusing of the reagents followed by a three-dimensional micromixer. This generates monodispersed and stable CdS and core-shell CdS/ZnS nanocrystals of 4.5 and 4.2 nm, respectively, with reproducible optical properties in terms of fluorescence emission wavelengths, bandwidth, and quantum yields, which is a key requirement for their future analytical applications. The synthetic process is also controlled in real time with the integration of an optical detection system for absorbance and fluorescence measurements based on commercial miniaturized optical components. This makes possible the efficient managing of the hydrodynamic variables to obtain the desired colloidal suspension. As a result, a simple, economic, robust and portable microsystem for the well controlled synthesis of CdS and CdS/ZnS nanocrystals is presented. Moreover, the reaction takes place in aqueous medium, thus allowing the direct modular integration of this microreactor in specific analytical microsystems, which require the use of such quantum dots as labels. This journal is © The Royal Society of Chemistry 2012

Hybrid Drug Delivery Patches Based on Spherical Cellulose Nanocrystals and Colloid Titania—Synthesis and Antibacterial Properties

PubMed Central

Svensson, Fredric G.; Agafonov, Alexander V.; Håkansson, Sebastian; Seisenbaeva, Gulaim A.

2018-01-01

Spherical cellulose nanocrystal-based hybrids grafted with titania nanoparticles were successfully produced for topical drug delivery. The conventional analytical filter paper was used as a precursor material for cellulose nanocrystals (CNC) production. Cellulose nanocrystals were extracted via a simple and quick two-step process based on first the complexation with Cu(II) solution in aqueous ammonia followed by acid hydrolysis with diluted H2SO4. Triclosan was selected as a model drug for complexation with titania and further introduction into the nanocellulose based composite. Obtained materials were characterized by a broad variety of microscopic, spectroscopic, and thermal analysis methods. The drug release studies showed long-term release profiles of triclosan from the titania based nanocomposite that agreed with Higuchi model. The bacterial susceptibility tests demonstrated that released triclosan retained its antibacterial activity against Escherichia coli and Staphylococcus aureus. It was found that a small amount of titania significantly improved the antibacterial activity of obtained nanocomposites, even without immobilization of model drug. Thus, the developed hybrid patches are highly promising candidates for potential application as antibacterial agents. PMID:29642486

Hybrid Drug Delivery Patches Based on Spherical Cellulose Nanocrystals and Colloid Titania-Synthesis and Antibacterial Properties.

PubMed

Evdokimova, Olga L; Svensson, Fredric G; Agafonov, Alexander V; Håkansson, Sebastian; Seisenbaeva, Gulaim A; Kessler, Vadim G

2018-04-08

Spherical cellulose nanocrystal-based hybrids grafted with titania nanoparticles were successfully produced for topical drug delivery. The conventional analytical filter paper was used as a precursor material for cellulose nanocrystals (CNC) production. Cellulose nanocrystals were extracted via a simple and quick two-step process based on first the complexation with Cu(II) solution in aqueous ammonia followed by acid hydrolysis with diluted H₂SO₄. Triclosan was selected as a model drug for complexation with titania and further introduction into the nanocellulose based composite. Obtained materials were characterized by a broad variety of microscopic, spectroscopic, and thermal analysis methods. The drug release studies showed long-term release profiles of triclosan from the titania based nanocomposite that agreed with Higuchi model. The bacterial susceptibility tests demonstrated that released triclosan retained its antibacterial activity against Escherichia coli and Staphylococcus aureus . It was found that a small amount of titania significantly improved the antibacterial activity of obtained nanocomposites, even without immobilization of model drug. Thus, the developed hybrid patches are highly promising candidates for potential application as antibacterial agents.

Synthesis of Cesium Lead Halide Perovskite Nanocrystals in a Droplet-Based Microfluidic Platform: Fast Parametric Space Mapping.

PubMed

Lignos, Ioannis; Stavrakis, Stavros; Nedelcu, Georgian; Protesescu, Loredana; deMello, Andrew J; Kovalenko, Maksym V

2016-03-09

Prior to this work, fully inorganic nanocrystals of cesium lead halide perovskite (CsPbX3, X = Br, I, Cl and Cl/Br and Br/I mixed halide systems), exhibiting bright and tunable photoluminescence, have been synthesized using conventional batch (flask-based) reactions. Unfortunately, our understanding of the parameters governing the formation of these nanocrystals is still very limited due to extremely fast reaction kinetics and multiple variables involved in ion-metathesis-based synthesis of such multinary halide systems. Herein, we report the use of a droplet-based microfluidic platform for the synthesis of CsPbX3 nanocrystals. The combination of online photoluminescence and absorption measurements and the fast mixing of reagents within such a platform allows the rigorous and rapid mapping of the reaction parameters, including molar ratios of Cs, Pb, and halide precursors, reaction temperatures, and reaction times. This translates into enormous savings in reagent usage and screening times when compared to analogous batch synthetic approaches. The early-stage insight into the mechanism of nucleation of metal halide nanocrystals suggests similarities with multinary metal chalcogenide systems, albeit with much faster reaction kinetics in the case of halides. Furthermore, we show that microfluidics-optimized synthesis parameters are also directly transferrable to the conventional flask-based reaction.

Control of oleylamine to perovskite ratio in synthesis of MAPbBr3 nanoparticles

NASA Astrophysics Data System (ADS)

Huang, Jing; Wu, Yi-Hua; Zhu, Zhi-Gang; Shih, Wan Y.; Shih, Wei-Heng

2018-06-01

Methylammonium lead bromide (CH3NH3PbBr3) nanocrystals have great potentials for lighting and display applications. Previously we synthesized CH3NH3PbBr3 nanocrystals using oleylamine as capping molecule and found that by increasing the oleylamine to CH3NH3PbBr3 perovskite ratio (OPR), the photoluminescence wavelengths and morphology of CH3NH3PbBr3 nanocrystals could be varied from 530 nm (green) platelets to 460 nm (blue) particles. Here we modified the synthesis to direct injection of precursors into toluene and found that increasing OPR not only changes the wavelength and morphology of nanocrystals but also the size of the unit cells.

Low-cost fabrication of ternary CuInSe{sub 2} nanocrystals by colloidal route using a novel combination of volatile and non-volatile capping agents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chawla, Parul; Narain Sharma, Shailesh, E-mail: shailesh@nplindia.org; Singh, Son

2014-11-15

Wet-route synthesis of CuInSe{sub 2} (CISe) nanocrystals has been envisaged with the utilization of the unique combination of coordinating ligand and non coordinating solvent. Our work demonstrates the formation of a single-phase, nearly stoichiometric and monodispersive, stable and well-passivated colloidal ternary CISe nanocrystals (band gap (E{sub g})∼1.16 eV) using a novel combination of ligands; viz. volatile arylamine aniline and non-volatile solvent 1-octadecene. The synthesis and growth conditions have been manoeuvred using the colligative properties of the mixture and thus higher growth temperature (∼250 °C) could be attained that promoted larger grain growth. The beneficial influence of the capping agents (anilinemore » and 1-octadecene) on the properties of chalcopyrite nanocrystals has enabled us to pictorally model the structural, morphological and optoelectronic aspects of CISe nanoparticles. - Graphical abstract: Without resorting to any post-selenization process and using the colligative properties of the mixture comprising of volatile aniline and non-volatile 1-octadecene to manoeuvre the growth conditions to promote Ostwald ripening, a single phase, monodispersive and nearly stoichiometric ternary CISe nanocrystals are formed by wet-synthesis route. - Highlights: • Wet-route synthesis of CISe nanocrystals reported without post-selenization process. • Single-phase, stable and well-passivated colloidal ternary CISe nanocrystals formed. • Novel combination of capping agents: volatile aniline and non-volatile 1-octadecene. • Higher growth temperature attained using the colligative properties of the mixture. • Metallic salts presence explains exp. and theoretical boiling point difference.« less

Part I: Structural Characterization of Doped Nanostructured Magnesium: Understanding Disorder for Enhanced Hydrogen Absorption Kinetics Part II: Synthesis, Film Deposition, and Characterization of Quaternary Metal Chalcogenide Nanocrystals for Photovoltaic Applications

NASA Astrophysics Data System (ADS)

Braun, Max B.

The production, storage, and subsequent consumption of energy are at the foundation of all human activity and livelihood. The theme of this dissertation is the pursuit of fundamental understanding of the chemistry of materials that are used for energy production and storage. A strong emphasis is placed on a synthetic foundation that allows for systematic investigation into the fundamental chemistry that controls the applicable properties of the materials of interest. This dissertation is written in the "journals format" style--which is accepted by the Graduate School at Colorado State University--and is based on one peer-reviewed publication that has appeared in Chemistry of Materials as well as two manuscripts to be submitted, one to The Journal of Physical Chemistry C, and one to ACS Applied Materials and Interfaces. In order to create a context for these publications, Chapters 1 and 3 provide an overview of the motivations for the projects, and then continue to detail the initial synthetic investigations and considerations for the two projects. In addition to recounting Mg nanocrystals synthetic refinement that was necessary for reproducible hydride kinetic analysis, Chapter 1 also briefly introduces some of the conventional models used for fitting of the hydriding kinetics data. Furthermore, initial investigations into the use of these models for our system are presented. Chapter 2 is a paper to be submitted to The Journal of Physical Chemistry C that describes the local and extended structure characterization of Mg nanocrystals (NCs) with a small amount of nickel added during synthesis. Ni has a dramatic effect on the de/hydriding kinetics of Mg NCs, and this chapter describes the use of a combination of multiple state-of-the-art characterization techniques to gain insight into the structural perturbations due to Ni inclusion in the Mg NCs. This insight is then used to establish the characteristics of Ni inclusion that results in the enhanced hydrogen absorption processes. Chapter 3 introduces the many considerations needed to be taken into account during the development of a novel synthesis for copper zinc tin chalcogenide colloidal nanocrystals. In addition to introducing synthetic approaches to achieve this goal, Chapter 3 also describes essential characteristics that need to be considered for further investigation into the properties of films made from the nanocrystals. Chapter 4 is a publication that appeared in Chemistry of Materials, that describes an approach to tuning the surface and ligand chemistry of Cu2ZnSnS4 nanocrystals for use as an absorber layer in next generation photovoltaic devices. The publication describes ligand exchange chemistry achieved via layer-by-layer dip-casting of nanocrystal thin films, and the effects that this exchange chemistry has on the resulting films. It also details the fabrication of full photovoltaic (PV) devices to characterize the benefits of controlling the surface chemistry can have on PV performance. Chapter 5 is a paper--to be submitted to ACS Applied Materials and Interfaces--that describes the investigations into how varying the chalcogen ratio (i.e., S:Se) leads to changes in the physical and electrical properties of thin films made from Cu2ZnSn(S1-xSex)4 (where 0 < x < 1) NCs. It highlights the novel synthetic procedure (detailed in chapter 3) that was required for a systematic, deconvoluted evaluation of S:Se composition on the materials optical and electronic properties. Moreover, the characteristics of full PV devices based on thin films of each stoichiometry (x=0 to x=1) are assessed to establish a relationship between composition and the materials performance.

L-serine capped ZnS:Mn nanocrystals for plant cell biological studies and as a growth enhancing agent for micropropagation of Bacopa monnieri Linn. (Brahmi:Scrophulariaceae)

NASA Astrophysics Data System (ADS)

Augustine, M. Sajimol; Mathew, Lizzy; Alex, Roselin; Deepa, G. D.; Jayalekshmi, S.

2014-01-01

In the present work, the prospects of ZnS:Mn nanocrystals capped with L- serine, a bio-compatible amino acid, synthesized by wet chemical route, as efficient fluorescent probes for plant cell biological studies have been investigated. The present synthesis route using bio-compatible material is a low cost and easy to control method. The colloidal stability of the capped nano crystals is very good as they remain stable without settling down for long time. It is observed that L- serine significantly modifies the structural and optical characteristics of the ZnS:Mn nanocrystals and hence is suitable as a bio-compatible capping agent. The structural properties of L- serine capped nanocrystals were investigated by XRD technique. The size of the L- serine capped ZnS:Mn nanocrystals is found to be around 2 nm . The optical characterization of the nanocrystals was carried out on the basis of photoluminescence (PL) spectroscopic studies. The intense photoluminescence emission observed around 597nm for L-serine capped ZnS:Mn offers high prospects of applications in bio-imaging fields. The unique optical properties of nanoparticles make them appealing as in vivo and in vitro fluorophores in a variety of biological investigations. In the present study, L-serine capped ZnS:Mn nanocrystals were used as a staining dye in fluorescent microscope for observing cell division, cell structure etc. These nanocrystals were also incorporated into the culture media along with the normal auxin- cytokinin hormone combinations in Murashige and Skoog (MS) medium for micropropagation of Bacopa monnieri Linn. (Brahmi:Scrophulariaceae), an Ayurvedic medicine. The results suggest that L-serine capped ZnS:Mn nanocrystals can act as efficient enhancers towards quick callusing and shoot proliferation.

Synthesis and characterization of colloidal ZnTe nanocrystals and ZnTe/ZnSe quantum dots

NASA Astrophysics Data System (ADS)

Gonzales, Gavin P.; Alas, Gema; Senthil, Arjun; Withers, Nathan J.; Minetos, Christina; Sandoval, Alejandro; Ivanov, Sergei A.; Smolyakov, Gennady A.; Huber, Dale L.; Osiński, Marek

2018-02-01

Quantum dots (QDs) emitting in the visible are of interest for many biomedical applications, including bioimaging, biosensing, drug targeting, and photodynamic therapy. However, a significant limitation is that QDs typically contain cadmium, which makes prospects for their FDA approval very unlikely. Previous work has focused on InP and ZnO as alternative semiconductor materials for QDs. However, these nanoparticles have also been shown to be cytotoxic. High-efficiency luminescent ZnTe-based QDs could be a reasonable alternative to Cd-containing QDs. In this paper, we present preliminary results of our recent studies of ZnTe-based QDs, including their synthesis, structural characterization, and optical properties.

Viral assembly of oriented quantum dot nanowires

NASA Astrophysics Data System (ADS)

Mao, Chuanbin; Flynn, Christine E.; Hayhurst, Andrew; Sweeney, Rozamond; Qi, Jifa; Georgiou, George; Iverson, Brent; Belcher, Angela M.

2003-06-01

The highly organized structure of M13 bacteriophage was used as an evolved biological template for the nucleation and orientation of semiconductor nanowires. To create this organized template, peptides were selected by using a pIII phage display library for their ability to nucleate ZnS or CdS nanocrystals. The successful peptides were expressed as pVIII fusion proteins into the crystalline capsid of the virus. The engineered viruses were exposed to semiconductor precursor solutions, and the resultant nanocrystals that were templated along the viruses to form nanowires were extensively characterized by using high-resolution analytical electron microscopy and photoluminescence. ZnS nanocrystals were well crystallized on the viral capsid in a hexagonal wurtzite or a cubic zinc blende structure, depending on the peptide expressed on the viral capsid. Electron diffraction patterns showed single-crystal type behavior from a polynanocrystalline area of the nanowire formed, suggesting that the nanocrystals on the virus were preferentially oriented with their [001] perpendicular to the viral surface. Peptides that specifically directed CdS nanocrystal growth were also engineered into the viral capsid to create wurtzite CdS virus-based nanowires. Lastly, heterostructured nucleation was achieved with a dual-peptide virus engineered to express two distinct peptides within the same viral capsid. This work represents a genetically controlled biological synthesis route to a semiconductor nanoscale heterostructure.

Viral assembly of oriented quantum dot nanowires.

PubMed

Mao, Chuanbin; Flynn, Christine E; Hayhurst, Andrew; Sweeney, Rozamond; Qi, Jifa; Georgiou, George; Iverson, Brent; Belcher, Angela M

2003-06-10

The highly organized structure of M13 bacteriophage was used as an evolved biological template for the nucleation and orientation of semiconductor nanowires. To create this organized template, peptides were selected by using a pIII phage display library for their ability to nucleate ZnS or CdS nanocrystals. The successful peptides were expressed as pVIII fusion proteins into the crystalline capsid of the virus. The engineered viruses were exposed to semiconductor precursor solutions, and the resultant nanocrystals that were templated along the viruses to form nanowires were extensively characterized by using high-resolution analytical electron microscopy and photoluminescence. ZnS nanocrystals were well crystallized on the viral capsid in a hexagonal wurtzite or a cubic zinc blende structure, depending on the peptide expressed on the viral capsid. Electron diffraction patterns showed single-crystal type behavior from a polynanocrystalline area of the nanowire formed, suggesting that the nanocrystals on the virus were preferentially oriented with their [001] perpendicular to the viral surface. Peptides that specifically directed CdS nanocrystal growth were also engineered into the viral capsid to create wurtzite CdS virus-based nanowires. Lastly, heterostructured nucleation was achieved with a dual-peptide virus engineered to express two distinct peptides within the same viral capsid. This work represents a genetically controlled biological synthesis route to a semiconductor nanoscale heterostructure.

Automated microfluidic platform for systematic studies of colloidal perovskite nanocrystals: towards continuous nano-manufacturing.

PubMed

Epps, Robert W; Felton, Kobi C; Coley, Connor W; Abolhasani, Milad

2017-11-21

Colloidal organic/inorganic metal-halide perovskite nanocrystals have recently emerged as a potential low-cost replacement for the semiconductor materials in commercial photovoltaics and light emitting diodes. However, unlike III-V and IV-VI semiconductor nanocrystals, studies of colloidal perovskite nanocrystals have yet to develop a fundamental and comprehensive understanding of nucleation and growth kinetics. Here, we introduce a modular and automated microfluidic platform for the systematic studies of room-temperature synthesized cesium-lead halide perovskite nanocrystals. With abundant data collection across the entirety of four orders of magnitude reaction time span, we comprehensively characterize nanocrystal growth within a modular microfluidic reactor. The developed high-throughput screening platform features a custom-designed three-port flow cell with translational capability for in situ spectral characterization of the in-flow synthesized perovskite nanocrystals along a tubular microreactor with an adjustable length, ranging from 3 cm to 196 cm. The translational flow cell allows for sampling of twenty unique residence times at a single equilibrated flow rate. The developed technique requires an average total liquid consumption of 20 μL per spectra and as little as 2 μL at the time of sampling. It may continuously sample up to 30 000 unique spectra per day in both single and multi-phase flow formats. Using the developed plug-and-play microfluidic platform, we study the growth of cesium lead trihalide perovskite nanocrystals through in situ monitoring of their absorption and emission band-gaps at residence times ranging from 100 ms to 17 min. The automated microfluidic platform enables a systematic study of the effect of mixing enhancement on the quality of the synthesized nanocrystals through a direct comparison between single- and multi-phase flow systems at similar reaction time scales. The improved mixing characteristics of the multi-phase flow format results in high-quality perovskite nanocrystals with kinetically tunable emission wavelength, ranging as much as 25 nm at equivalent residence times. Further application of this unique platform would allow rapid parameter optimization in the colloidal synthesis of a wide range of nanomaterials (e.g., metal or semiconductor), that is directly transferable to continuous manufacturing in a numbered-up platform with a similar characteristic length scale.

Controllable synthesis of protein-conjugated lead sulfide nanocubes by using bovine hemoglobin as a capping agent

NASA Astrophysics Data System (ADS)

Yang, Guangrui; Qin, Dezhi; Zhang, Li

2014-06-01

A simple, convenient, and controllable strategy was reported in this contribution for protein-assisted synthesis BHb-conjugated PbS nanocubes. Powder X-ray diffraction, energy disperse X-ray spectroscopy, transmission electron microscopy, high-resolution transmission electron microscopy, and selected-area electron diffraction characterizations were used to determine the structure and morphology of BHb-conjugated PbS nanocubes. The prepared PbS nanocrystals with cubic rock salt structure were uniform and monodispersed with homogeneous size around 12 nm. The results of Fourier transform infrared and circular dichroism assay proved that Pb2+/PbS had coordination interaction with functional groups of BHb besides physical-binding effect, and the secondary structure of protein significantly changed with this interaction. Thermogravimetric analysis results confirmed the existence of BHb in PbS nanocrystals and indicated that the conjugate bonds existed between PbS and BHb. A clear perspective was shown here that special nanostructure could be created by using proteins as a mediating template at the inorganic-organic interface.

Self-assembly and alignment of semiconductor nanoparticles on cellulose nanocrystals

Treesearch

Sonal Padalkar; Jeff R. Capadona; Stuart J. Rowan; Christoph Weder; Robert J. Moon; Lia A. Stanciu

2011-01-01

The synthesis of cadmium sulfide (CdS), zinc sulfide (ZnS), and lead sulfide (PbS) nanoparticle chains on cellulose nanocrystal (CNC) templates can be accomplished by the reaction of the precursor salts. The use of a cationic surfactant, cetyltrimethylammonium bromide (CTAB), was critical for the synthesis of well-defined semiconductor nanoparticle chains on the...

A top-down strategy to synthesize wurtzite Cu2ZnSnS4 nanocrystals by green chemistry.

PubMed

Sun, Yiwen; Hu, Zhengqiao; Zhang, Junjun; Wang, Li; Wu, Chunyan; Xu, Jun

2016-07-28

Green synthesis of metastable wurtzite Cu2ZnSnS4 nanocrystals through a top-down synthetic strategy is presented. Formation mechanisms associated with Kirkendall and etching effects are illustrated in detail. The nanocrystals exhibit remarkable photoluminescence properties at room temperature.

Ultra-low-energy ion-beam synthesis of nanometer-separated Si nanoparticles and Ag nanocrystals 2D layers

NASA Astrophysics Data System (ADS)

Carrada, M.; Haj Salem, A.; Pecassou, B.; Paillard, V.; Ben Assayag, G.

2018-03-01

2D networks of Si and Ag nanocrystals have been fabricated in the same SiO2 matrix by Ultra-Low-Energy Ion-Beam-Synthesis. Our synthesis scheme differs from a simple sequential ion implantation and its key point is the control of the matrix integrity through an appropriate intermediate thermal annealing. Si nanocrystal layer is synthesised first due to high thermal budget required for nucleation, while the second Ag nanocrystal plane is formed during a subsequent implantation due to the high diffusivity of Ag in silica. The aim of this work is to show how it is possible to overcome the limitation related to ion mixing and implantation damage to obtain double layers of Si-NCs and Ag-NCs with controlled characteristics. For this, we take advantage of annealing under slight oxidizing ambient to control the oxidation of Si-NCs and the Si excess in the matrix. The nanocrystal characteristics and in particular their position and size can be adjusted thanks to a compromise between the implantation energy, the implanted dose for both Si and Ag ions and the intermediate annealing conditions (atmosphere, temperature and duration).

Coordination ability determined transition metal ions substitution of Tb in Tb-Asp fluorescent nanocrystals and a facile ions-detection approach.

PubMed

Duan, Jiazhi; Ma, Baojin; Liu, Feng; Zhang, Shan; Wang, Shicai; Kong, Ying; Du, Min; Han, Lin; Wang, Jianjun; Sang, Yuanhua; Liu, Hong

2018-04-26

Although the synthesis and fluorescent properties of lanthanide-amino acid complex nanostructures have been investigated extensively, limited studies have been reported on metal ions' substitution ability for the lanthanide ions in the complex and their effect on the fluorescent property. In this study, taking biocompatible Tb-aspartic acid (Tb-Asp) complex nanocrystals as a model, the substitution mechanism of metal ions, particularly transition metals, for Tb ions in Tb-Asp nanocrystals and the change in the fluorescent property of the Tb-Asp nanocrystals after substitution were systematically investigated. The experimental results illustrated that metal ions with higher electronegativity, higher valence, and smaller radius possess stronger ability for Tb ions' substitution in Tb-Asp nanocrystals. Based on the effect of substituting ions' concentration on the fluorescent property of Tb-Asp, a facile method for copper ions detection with high sensitivity was proposed by measuring the fluorescent intensity of Tb-Asp nanocrystals' suspensions containing different concentrations of copper ions. The good biocompatibility, great convenience of synthesis and sensitive detection ability make Tb-Asp nanocrystals a very low cost and effective material for metal ions detection, which also opens a new door for practical applications of metal-Asp coordinated nanocrystals.

Cloning nanocrystal morphology with soft templates

NASA Astrophysics Data System (ADS)

Thapa, Dev Kumar; Pandey, Anshu

2016-08-01

In most template directed preparative methods, while the template decides the nanostructure morphology, the structure of the template itself is a non-general outcome of its peculiar chemistry. Here we demonstrate a template mediated synthesis that overcomes this deficiency. This synthesis involves overgrowth of silica template onto a sacrificial nanocrystal. Such templates are used to copy the morphologies of gold nanorods. After template overgrowth, gold is removed and silver is regrown in the template cavity to produce a single crystal silver nanorod. This technique allows for duplicating existing nanocrystals, while also providing a quantifiable breakdown of the structure - shape interdependence.

Catalytic performance of Mn 3O 4 and Co 3O 4 nanocrystals prepared by sonochemical method in epoxidation of styrene and cyclooctene

NASA Astrophysics Data System (ADS)

Askarinejad, Azadeh; Bagherzadeh, Mojtaba; Morsali, Ali

2010-09-01

A simple sonochemical method was developed to synthesis uniform sphere-like Co 3O 4 and Mn 3O 4 nanocrystals. Epoxidation of styrene and cyclooctene by anhydrous tert-butyl hydroperoxide over the prepared Co 3O 4 and Mn 3O 4 nanocatalysts was investigated. The results of conversion activity were compared with bulk Co 3O 4 and Mn 3O 4. Under optimized reaction conditions, the nanocatalysts showed a superior catalytic performance as compared to the bulk catalysts. Powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and BET surface area, were used to characterize and investigate the nanocatalysts.

Electroluminescence in CdSe/PVA nanocomposites

NASA Astrophysics Data System (ADS)

Kumari, Sarita; Ramrakhiani, M.; Khare, P. K.

2018-05-01

The synthesis of II-VI nanocrystal into the polymer matrix to form nanocomposites with adjustable nanocrystal is of great interest size is a big challenge to the scientific community. In present work semiconducting CdSe/PVA thin film were synthesized by single step solution method with different concentration of CdSe. The as-prepared products were characterized by UV-Visible absorption spectra and FESEM. Absorption spectra of CdSe/PVA nanocomposites indicated that the position of absorption edge shifts to smaller wavelength by increasing the concentration of CdSe. For Electroluminescence a turn on voltage is required for light emission and brightness increases with voltage. Turn on voltage is found to decrease as CdSe concentration is increased. The voltage-current curve represents ohmic nature for all EL cells.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jia, Li-Ping; Zhang, Qiang; State Key Laboratory of Pollution Control and Resource Reuse

Graphical abstract: Lanthanide ions doped bare earth rare earth fluoride nanocrystals are synthesized by hydrothermal technology and characterized. The down/up-conversion luminescence of them are discussed. - Highlights: • Mixed hydrothermal system H{sub 2}O–OA (EDA)–O-A(LO-A) is used for synthesis. • Barium rare earth fluoride nanocrystals are synthesized comprehensively. • Luminescence for down-conversion and up-conversion are obtained for these systems. - Abstract: Mixed hydrothermal system H{sub 2}O–OA (EDA)–O-A(LO-A) is developed to synthesize barium rare earth fluorides nanocrystals (OA = oleylamine, EDA = ethylenediamine, O-A = oleic acid and LO-A = linoleic acid). They are presented as BaREF{sub 5} (RE = Ce, Pr,more » Nd, Eu, Gd, Tb, Dy, Y, Tm, Lu) and Ba{sub 2}REF{sub 7} (RE = La, Sm, Ho, Er, Yb). The influence of reaction parameters (rare earth species, hydrothermal system and temperature) is checked on the phase and shape evolution of the fluoride nanocrystals. It is found that reaction time and temperature of these nanocrystals using EDA (180 °C, 6 h) is lower than those of them using OA (220 °C, 10 h). The photoluminescence properties of these fluorides activated by some rare earth ions (Nd{sup 3+}, Eu{sup 3+}, Tb{sup 3+}) are studied, and especially up-conversion luminescence of the four fluoride nanocrystal systems (Ba{sub 2}LaF{sub 7}:Yb, Tm(Er), Ba{sub 2}REF{sub 7}:Yb, Tm(Er) (RE = Gd, Y, Lu)) is observed.« less

Sub-10 nm lanthanide doped BaLuF{sub 5} nanocrystals: Shape controllable synthesis, tunable multicolor emission and enhanced near-infrared upconversion luminescence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rao, Ling; Lu, Wei; Wang, Haibo

2015-04-15

Highlights: • Sub-10 nm cubic phase BaLuF{sub 5} nanocrystals were synthesized by a hydrothermal method for the first time. • Tunable multicolor from yellow to yellow-green was achieved by controlling Gd{sup 3+} content in BaLuF{sub 5}:Yb/Er system. • Intense near-infrared upconversion luminescence in BaLuF{sub 5}:Gd/Yb/Tm nanocrystal. • The enhancement near-infrared luminescence can be realized by adjusting the content of Gd{sup 3+} in BaLuF{sub 5}:Gd/Yb/Tm system. - Abstract: In this study, sub-10 nm BaLuF{sub 5} nanocrystals with cubic phase structure were synthesized by a solvothermal method using oleic acid as the stabilizing agent. The as-prepared BaLuF{sub 5} nanocrystals were characterized bymore » transmission electron microscopy (TEM), X-ray diffraction (XRD), and analyzed by the upconversion (UC) spectra. The TEM results reveal that these samples present high uniformity. Compared with Gd-free samples, the size of BaLuF{sub 5}:Yb/Er doped with 10% Gd{sup 3+} decreased to 5.6 nm. In addition, BaLuF{sub 5}:Yb/Tm/Gd upconversion nanoparticles (UCNPs) presented efficient near-infrared (NIR)-NIR UC luminescence. Therefore, it is expected that these ultra-small BaLuF{sub 5} nanocrystals with well-controlled shape, size, and UC emission have potential applications in biomedical imaging fields.« less

Colloidal synthesis of Cu-ZnO and Cu@CuNi-ZnO hybrid nanocrystals with controlled morphologies and multifunctional properties

NASA Astrophysics Data System (ADS)

Zeng, Deqian; Gong, Pingyun; Chen, Yuanzhi; Zhang, Qinfu; Xie, Qingshui; Peng, Dong-Liang

2016-06-01

Metal-semiconductor hybrid nanocrystals have received extensive attention owing to their multiple functionalities which can find wide technological applications. The utilization of low-cost non-noble metals to construct novel metal-semiconductor hybrid nanocrystals is important and meaningful for their large-scale applications. In this study, a facile solution approach is developed for the synthesis of Cu-ZnO hybrid nanocrystals with well-controlled morphologies, including nanomultipods, core-shell nanoparticles, nanopyramids and core-shell nanowires. In the synthetic strategy, Cu nanocrystals formed in situ serve as seeds for the heterogeneous nucleation and growth of ZnO, and it eventually forms various Cu-ZnO hetero-nanostructures under different reaction conditions. These hybrid nanocrystals possess well-defined and stable heterostructure junctions. The ultraviolet-visible-near infrared spectra reveal morphology-dependent surface plasmon resonance absorption of Cu and the band gap absorption of ZnO. Furthermore, we construct a novel Cu@CuNi-ZnO ternary hetero-nanostructure by incorporating the magnetic metal Ni into the pre-synthesized colloidal Cu nanocrystals. Such hybrid nanocrystals possess a magnetic Cu-Ni intermediate layer between the ZnO shell and the Cu core, and exhibit ferromagnetic/superparamagnetic properties which expand their functionalities. Finally, enhanced photocatalytic activities are observed in the as-prepared non-noble metal-ZnO hybrid nanocrystals. This study not only provides an economical way to prepare high-quality morphology-controlled Cu-ZnO hybrid nanocrystals for potential applications in the fields of photocatalysis and photovoltaic devices, but also opens up new opportunities in designing ternary non-noble metal-semiconductor hybrid nanocrystals with multifunctionalities.Metal-semiconductor hybrid nanocrystals have received extensive attention owing to their multiple functionalities which can find wide technological applications. The utilization of low-cost non-noble metals to construct novel metal-semiconductor hybrid nanocrystals is important and meaningful for their large-scale applications. In this study, a facile solution approach is developed for the synthesis of Cu-ZnO hybrid nanocrystals with well-controlled morphologies, including nanomultipods, core-shell nanoparticles, nanopyramids and core-shell nanowires. In the synthetic strategy, Cu nanocrystals formed in situ serve as seeds for the heterogeneous nucleation and growth of ZnO, and it eventually forms various Cu-ZnO hetero-nanostructures under different reaction conditions. These hybrid nanocrystals possess well-defined and stable heterostructure junctions. The ultraviolet-visible-near infrared spectra reveal morphology-dependent surface plasmon resonance absorption of Cu and the band gap absorption of ZnO. Furthermore, we construct a novel Cu@CuNi-ZnO ternary hetero-nanostructure by incorporating the magnetic metal Ni into the pre-synthesized colloidal Cu nanocrystals. Such hybrid nanocrystals possess a magnetic Cu-Ni intermediate layer between the ZnO shell and the Cu core, and exhibit ferromagnetic/superparamagnetic properties which expand their functionalities. Finally, enhanced photocatalytic activities are observed in the as-prepared non-noble metal-ZnO hybrid nanocrystals. This study not only provides an economical way to prepare high-quality morphology-controlled Cu-ZnO hybrid nanocrystals for potential applications in the fields of photocatalysis and photovoltaic devices, but also opens up new opportunities in designing ternary non-noble metal-semiconductor hybrid nanocrystals with multifunctionalities. Electronic supplementary information (ESI) available: Synthesis and TEM images of pure ZnO nanocrystals. Photocatalytic testing procedures and degradation curves. SEM and TEM images, SAED pattern and EDS spectra and maps of parts of Cu-ZnO hybrid samples. A schematic image of coincident lattice matching between Cu and ZnO. STEM-EDS elemental maps and XRD pattern of the Cu@CuNi-ZnO sample. Comparative synthetic parameters. See DOI: 10.1039/c6nr02055k

Hydrothermal synthesis and tunable luminescence of CaSiO{sub 3}:RE{sup 3+}(RE{sup 3+} = Eu{sup 3+}, Sm{sup 3+}, Tb{sup 3+}, Dy{sup 3+}) nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, Linlin; Yang, Xingxing; Fu, Zuoling, E-mail: zlfu@jlu.edu.cn

2015-05-15

Highlights: • Near-spherical CaSiO{sub 3} nanocrystals were synthesized via a hydrothermal method. • The effect of calcination temperature on crystalline phase formation was discussed. • Optical properties of trivalent ions doped CaSiO{sub 3} nanocrystals were investigated. • Tunable luminescence of CaSiO{sub 3}:Tb{sup 3+}, Eu{sup 3+} can be achieved by a simple method. - Abstract: CaSiO{sub 3}:RE{sup 3+} (RE{sup 3+} = Eu{sup 3+}, Sm{sup 3+}, Tb{sup 3+}, Dy{sup 3+}) nanocrystals were prepared by facile hydrothermal method with further calcinations. The crystal structure and the effects of annealing temperature on phase transition have been characterized by X-ray diffraction (XRD). The photoluminescence (PL)more » and PL excitation (PLE) spectra were used to characterize the optical properties of all samples. The effect of Eu{sup 3+} and Sm{sup 3+} doping concentrations on the luminescent intensity were also investigated in details, respectively. Moreover, the luminescence colors of the Tb{sup 3+} and Eu{sup 3+} co-doped CaSiO{sub 3} samples can be tuned by simply adjusting the relative doping concentrations of the rare earth ions under a single wavelength excitation, which might find potential applications in the fields of light display systems and optoelectronic devices.« less

Near-infrared emitting AgInTe2 and Zn-Ag-In-Te colloidal nanocrystals

NASA Astrophysics Data System (ADS)

Langevin, Marc-Antoine; Pons, Thomas; Ritcey, Anna M.; Nì. Allen, Claudine

2015-06-01

The synthesis of AgInTe2 nanocrystals emitting between 1095 nm and 1160 nm is presented. Evolution of the Ag:In:Te ratio shows progressive incorporation of In3+ in Ag2Te, leading to the formation of orthorhombic AgInTe2. When zinc is added to the synthesis, the photoluminescence quantum yield reaches 3.4 %.

Green and microwave synthesis of SrAl2O4 nanoparticles by application of pomegranate juice: study and characterization

NASA Astrophysics Data System (ADS)

Riahi-Madvaar, Ramin; Taher, Mohammad Ali; Fazelirad, Hamid

2017-11-01

In the present paper, a green method was applied for the synthesis of SrAl2O4 nanostructures with the aid of microwave irradiation and pomegranate juice. SrAl2O4 nanocrystals were obtained when the raw materials were irradiated with 720-900 W for 6-10 min and then calcinated at 550 °C for 5 h. Using pomegranate juice as a dispersion and stabilizing agent, SrAl2O4 nanoparticles have been made with better properties in view of morphology and particle size. Also, the effect of some parameters affecting synthesis process such as microwave power and reaction time on the morphology and particle size of product was studied and optimized. X-ray diffraction and field emission-scanning electron microscopy were used to study and characterize the manufactured SrAl2O4 nanoparticles.

Hybrid nanocomposites based on electroactive hydrogels and cellulose nanocrystals for high-sensitivity electro-mechanical underwater actuation

NASA Astrophysics Data System (ADS)

Santaniello, Tommaso; Migliorini, Lorenzo; Locatelli, Erica; Monaco, Ilaria; Yan, Yunsong; Lenardi, Cristina; Comes Franchini, Mauro; Milani, Paolo

2017-08-01

We report the synthesis, fabrication and characterization of a hybrid hydrogel/cellulose nanocomposite, which exhibits high-performance electro-mechanical underwater actuation and high sensitivity in response to electrical stimuli below the standard potential of water electrolysis. The macromolecular structure of the material is constituted by an electroactive hydrogel, obtained through a photo-polymerization reaction with the use of three vinylic co-monomers: Na-4-vinylbenzenesulfonate, 2-hydroxyethylmethacrylate, and acrylonitrile. Different amounts (from 0.1% to 1.4% w/w) of biodegradable cellulose nanocrystals (CNCs) with sulfonate surface groups, obtained through the acidic hydrolysis of sulphite pulp lapsheets, are physically incorporated into the gel matrix during the synthesis step. Freestanding thin films of the nanocomposites are molded, and their swelling, mechanical and responsive properties are fully characterized. We observed that the embedding of the CNCs enhanced both the material Young’s modulus and its sensitivity to the applied electric field in the sub-volt regime (down to 5 mV cm-1). A demonstrator integrating multiple actuators that cooperatively bend together, mimicking the motion of an electro-valve, is also prototyped and tested. The presented nanocomposite is suitable for the development of soft smart components for bio-robotic applications and cells-based and bio-hybrid fluidic devices fabrication.

Template-directed assembly of metal-chalcogenide nanocrystals into ordered mesoporous networks.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vamvasakis, Ioannis; Subrahmanyam, Kota S.; Kanatzidis, Mercouri G.

Although great progress in the synthesis of porous networks of metal and metal oxide nanoparticles with highly accessible pore surface and ordered mesoscale pores has been achieved, synthesis of assembled 3D mesostructures of metal-chalcogenide nanocrystals is still challenging. In this work we demonstrate that ordered mesoporous networks, which comprise well-defined interconnected metal sulfide nanocrystals, can be prepared through a polymer-templated oxidative polymerization process. The resulting self-assembled mesostructures that were obtained after solvent extraction of the polymer template impart the unique combination of light-emitting metal chalcogenide nanocrystals, three-dimensional open-pore structure, high surface area, and uniform pores. We show that the poremore » surface of these materials is active and accessible to incoming molecules, exhibiting high photocatalytic activity and stability, for instance, in oxidation of 1-phenylethanol into acetophenone. We demonstrate through appropriate selection of the synthetic components that this method is general to prepare ordered mesoporous materials from metal chalcogenide nanocrystals with various sizes and compositions.« less

A developed Ullmann reaction to III-V semiconductor nanocrystals in sealed vacuum tubes.

PubMed

Wang, Junli; Yang, Qing

2008-11-21

Group III-V (13-15, III = Ga, In, and V = P, As) semiconductor nanocrystals were effectively obtained via a developed Ullmann reaction route through the reactions of preformed nanoscale metallic indium or commercial gallium with triphenylphosphine (PPh(3)) and triphenylarsine (AsPh(3)) in sealed vacuum quartz tubes under moderate conditions at 320-400 degrees C for 8-24 h. The developed synthetic strategy in sealed vacuum tubes extends the synthesis of III-V semiconductor materials, and the air-stable PPh(3) and AsPh(3) with low toxicity provide good alternative pnicogen precursors for the synthesis of III-V nanocrystals. The analysis of XRD, ED and HRTEM established the production of one-dimensional (1D) metastable wurtzite (W) InP, InAs and GaP nanostructures in the zinc blende (ZB) products. Further investigations showed that 1D W nanostructures resulted from kinetic effects under the moderate synthetic conditions employed and the steric effect of PPh(3) and AsPh(3), and that the tendency for the synthesis of III-V nanocrystals was in the orders of IIIP > IIIAs and GaV > InV on the basis of experiments and thermodynamic calculations. Meanwhile, the microstructures and growth mechanism of the III-V nanocrystals were investigated.

Solvothermal synthesis of platinum alloy nanoparticles for oxygen reduction electrocatalysis.

PubMed

Carpenter, Michael K; Moylan, Thomas E; Kukreja, Ratandeep Singh; Atwan, Mohammed H; Tessema, Misle M

2012-05-23

Platinum alloy nanoparticles show great promise as electrocatalysts for the oxygen reduction reaction (ORR) in fuel cell cathodes. We report here on the use of N,N-dimethylformamide (DMF) as both solvent and reductant in the solvothermal synthesis of Pt alloy nanoparticles (NPs), with a particular focus on Pt-Ni alloys. Well-faceted alloy nanocrystals were generated with this method, including predominantly cubic and cuboctahedral nanocrystals of Pt(3)Ni, and octahedral and truncated octahedral nanocrystals of PtNi. X-ray diffraction (XRD) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), coupled with energy dispersive spectroscopy (EDS), were used to characterize crystallite morphology and composition. ORR activities of the alloy nanoparticles were measured with a rotating disk electrode (RDE) technique. While some Pt(3)Ni alloy nanoparticle catalysts showed specific activities greater than 1000 μA/cm(2)(Pt), alloy catalysts prepared with a nominal composition of PtNi displayed activities close to 3000 μA/cm(2)(Pt), or almost 15 times that of a state-of-the-art Pt/carbon catalyst. XRD and EDS confirmed the presence of two NP compositions in this catalyst. HAADF-STEM examination of the PtNi nanoparticle catalyst after RDE testing revealed the development of hollows in a number of the nanoparticles due to nickel dissolution. Continued voltage cycling caused further nickel dissolution and void formation, but significant activity remained even after 20,000 cycles.

Gold nanocrystals with DNA-directed morphologies.

PubMed

Ma, Xingyi; Huh, June; Park, Wounjhang; Lee, Luke P; Kwon, Young Jik; Sim, Sang Jun

2016-09-16

Precise control over the structure of metal nanomaterials is important for developing advanced nanobiotechnology. Assembly methods of nanoparticles into structured blocks have been widely demonstrated recently. However, synthesis of nanocrystals with controlled, three-dimensional structures remains challenging. Here we show a directed crystallization of gold by a single DNA molecular regulator in a sequence-independent manner and its applications in three-dimensional topological controls of crystalline nanostructures. We anchor DNA onto gold nanoseed with various alignments to form gold nanocrystals with defined topologies. Some topologies are asymmetric including pushpin-, star- and biconcave disk-like structures, as well as more complex jellyfish- and flower-like structures. The approach of employing DNA enables the solution-based synthesis of nanocrystals with controlled, three-dimensional structures in a desired direction, and expands the current tools available for designing and synthesizing feature-rich nanomaterials for future translational biotechnology.

Adsorption of vitamin E on mesoporous titania nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shih, C.J., E-mail: cjshih@kmu.edu.tw; Lin, C.T.; Wu, S.M.

2010-07-15

Tri-block nonionic surfactant and titanium chloride were used as starting materials for the synthesis of mesoporous titania nanocrystallite powders. The main objective of the present study was to examine the synthesis of mesoporous titania nanocrystals and the adsorption of vitamin E on those nanocrystals using X-ray diffraction (XRD), transmission electron microscopy, and nitrogen adsorption and desorption isotherms. When the calcination temperature was increased to 300 {sup o}C, the reflection peaks in the XRD pattern indicated the presence of an anatase phase. The crystallinity of the nanocrystallites increased from 80% to 98.6% with increasing calcination temperature from 465 {sup o}C tomore » 500 {sup o}C. The N{sub 2} adsorption data and XRD data taken after vitamin E adsorption revealed that the vitamin E molecules were adsorbed in the mesopores of the titania nanocrystals.« less

Gold nanocrystals with DNA-directed morphologies

NASA Astrophysics Data System (ADS)

Ma, Xingyi; Huh, June; Park, Wounjhang; Lee, Luke P.; Kwon, Young Jik; Sim, Sang Jun

2016-09-01

Precise control over the structure of metal nanomaterials is important for developing advanced nanobiotechnology. Assembly methods of nanoparticles into structured blocks have been widely demonstrated recently. However, synthesis of nanocrystals with controlled, three-dimensional structures remains challenging. Here we show a directed crystallization of gold by a single DNA molecular regulator in a sequence-independent manner and its applications in three-dimensional topological controls of crystalline nanostructures. We anchor DNA onto gold nanoseed with various alignments to form gold nanocrystals with defined topologies. Some topologies are asymmetric including pushpin-, star- and biconcave disk-like structures, as well as more complex jellyfish- and flower-like structures. The approach of employing DNA enables the solution-based synthesis of nanocrystals with controlled, three-dimensional structures in a desired direction, and expands the current tools available for designing and synthesizing feature-rich nanomaterials for future translational biotechnology.

Colloidal synthesis of Cu-ZnO and Cu@CuNi-ZnO hybrid nanocrystals with controlled morphologies and multifunctional properties.

PubMed

Zeng, Deqian; Gong, Pingyun; Chen, Yuanzhi; Zhang, Qinfu; Xie, Qingshui; Peng, Dong-Liang

2016-06-02

Metal-semiconductor hybrid nanocrystals have received extensive attention owing to their multiple functionalities which can find wide technological applications. The utilization of low-cost non-noble metals to construct novel metal-semiconductor hybrid nanocrystals is important and meaningful for their large-scale applications. In this study, a facile solution approach is developed for the synthesis of Cu-ZnO hybrid nanocrystals with well-controlled morphologies, including nanomultipods, core-shell nanoparticles, nanopyramids and core-shell nanowires. In the synthetic strategy, Cu nanocrystals formed in situ serve as seeds for the heterogeneous nucleation and growth of ZnO, and it eventually forms various Cu-ZnO hetero-nanostructures under different reaction conditions. These hybrid nanocrystals possess well-defined and stable heterostructure junctions. The ultraviolet-visible-near infrared spectra reveal morphology-dependent surface plasmon resonance absorption of Cu and the band gap absorption of ZnO. Furthermore, we construct a novel Cu@CuNi-ZnO ternary hetero-nanostructure by incorporating the magnetic metal Ni into the pre-synthesized colloidal Cu nanocrystals. Such hybrid nanocrystals possess a magnetic Cu-Ni intermediate layer between the ZnO shell and the Cu core, and exhibit ferromagnetic/superparamagnetic properties which expand their functionalities. Finally, enhanced photocatalytic activities are observed in the as-prepared non-noble metal-ZnO hybrid nanocrystals. This study not only provides an economical way to prepare high-quality morphology-controlled Cu-ZnO hybrid nanocrystals for potential applications in the fields of photocatalysis and photovoltaic devices, but also opens up new opportunities in designing ternary non-noble metal-semiconductor hybrid nanocrystals with multifunctionalities.

Shape-programmed nanofabrication: understanding the reactivity of dichalcogenide precursors.

PubMed

Guo, Yijun; Alvarado, Samuel R; Barclay, Joshua D; Vela, Javier

2013-04-23

Dialkyl and diaryl dichalcogenides are highly versatile and modular precursors for the synthesis of colloidal chalcogenide nanocrystals. We have used a series of commercially available dichalcogenide precursors to unveil the molecular basis for the outcome of nanocrystal preparations, more specifically, how precursor molecular structure and reactivity affect the final shape and size of II-VI semiconductor nanocrystals. Dichalcogenide precursors used were diallyl, dibenzyl, di-tert-butyl, diisopropyl, diethyl, dimethyl, and diphenyl disulfides and diethyl, dimethyl, and diphenyl diselenides. We find that the presence of two distinctively reactive C-E and E-E bonds makes the chemistry of these precursors much richer and interesting than that of other conventional precursors such as the more common phosphine chalcogenides. Computational studies (DFT) reveal that the dissociation energy of carbon-chalcogen (C-E) bonds in dichalcogenide precursors (R-E-E-R, E=S or Se) increases in the order (R): diallyl

Shape-Controlled Synthesis of Isotopic Yttrium-90-Labeled Rare Earth Fluoride Nanocrystals for Multimodal Imaging.

PubMed

Paik, Taejong; Chacko, Ann-Marie; Mikitsh, John L; Friedberg, Joseph S; Pryma, Daniel A; Murray, Christopher B

2015-09-22

Isotopically labeled nanomaterials have recently attracted much attention in biomedical research, environmental health studies, and clinical medicine because radioactive probes allow the elucidation of in vitro and in vivo cellular transport mechanisms, as well as the unambiguous distribution and localization of nanomaterials in vivo. In addition, nanocrystal-based inorganic materials have a unique capability of customizing size, shape, and composition; with the potential to be designed as multimodal imaging probes. Size and shape of nanocrystals can directly influence interactions with biological systems, hence it is important to develop synthetic methods to design radiolabeled nanocrystals with precise control of size and shape. Here, we report size- and shape-controlled synthesis of rare earth fluoride nanocrystals doped with the β-emitting radioisotope yttrium-90 ((90)Y). Size and shape of nanocrystals are tailored via tight control of reaction parameters and the type of rare earth hosts (e.g., Gd or Y) employed. Radiolabeled nanocrystals are synthesized in high radiochemical yield and purity as well as excellent radiolabel stability in the face of surface modification with different polymeric ligands. We demonstrate the Cerenkov radioluminescence imaging and magnetic resonance imaging capabilities of (90)Y-doped GdF3 nanoplates, which offer unique opportunities as a promising platform for multimodal imaging and targeted therapy.

L-serine capped ZnS:Mn nanocrystals for plant cell biological studies and as a growth enhancing agent for micropropagation of Bacopa monnieri Linn. (Brahmi:Scrophulariaceae)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Augustine, M. Sajimol, E-mail: sajimollazar@gmail.com; Mathew, Lizzy; Alex, Roselin

2014-01-28

In the present work, the prospects of ZnS:Mn nanocrystals capped with L- serine, a bio-compatible amino acid, synthesized by wet chemical route, as efficient fluorescent probes for plant cell biological studies have been investigated. The present synthesis route using bio-compatible material is a low cost and easy to control method. The colloidal stability of the capped nano crystals is very good as they remain stable without settling down for long time. It is observed that L- serine significantly modifies the structural and optical characteristics of the ZnS:Mn nanocrystals and hence is suitable as a bio-compatible capping agent. The structural propertiesmore » of L- serine capped nanocrystals were investigated by XRD technique. The size of the L- serine capped ZnS:Mn nanocrystals is found to be around 2 nm . The optical characterization of the nanocrystals was carried out on the basis of photoluminescence (PL) spectroscopic studies. The intense photoluminescence emission observed around 597nm for L-serine capped ZnS:Mn offers high prospects of applications in bio-imaging fields. The unique optical properties of nanoparticles make them appealing as in vivo and in vitro fluorophores in a variety of biological investigations. In the present study, L-serine capped ZnS:Mn nanocrystals were used as a staining dye in fluorescent microscope for observing cell division, cell structure etc. These nanocrystals were also incorporated into the culture media along with the normal auxin- cytokinin hormone combinations in Murashige and Skoog (MS) medium for micropropagation of Bacopa monnieri Linn. (Brahmi:Scrophulariaceae), an Ayurvedic medicine. The results suggest that L-serine capped ZnS:Mn nanocrystals can act as efficient enhancers towards quick callusing and shoot proliferation.« less

Living Nanocrystals: Synthesis of Precisely Defined Metal Oxide Nanocrystals Through a Continuous Growth Process

NASA Astrophysics Data System (ADS)

Jansons, Adam Wayne

Colloidal nanocrystals offer new and improved performance in applications as well as less environmental impact when compared to traditional device fabrication methods. The important properties that enable improved applications are a direct result of nanocrystal structure. While there have been many great advances in the production of colloidal nanocrystals over the past three decades, precise, atomic-level control of the size, composition, and structure of the inorganic core remains challenging. Rather than dictate these material aspects through traditional synthetic routes, this dissertation details the development and exploitation of a colloidal nanocrystal synthetic method inspired by polymerization reactions. Living polymerization reactions offer precise control of polymer size and structure and have tremendously advanced polymer science, allowing the intuitive production of polymers and block co-polymers of well-defined molecular weights. Similarly, living nanocrystal synthetic methods allow an enhanced level of structural control, granting the synthesis of binary, doped, and core/shell nanocrystals of well-defined size, composition, and structure. This improved control in turn grants enhanced nanocrystal property performance and deepens our understanding of structure/property relationships. This dissertation defines living nanocrystal growth and demonstrates the potential of the living methods in the colloidal production of oxide nanocrystals. After a brief introduction, living growth is defined and discussed in the context of synthetic prerequisites, attributes, and outcomes. Living growth is also compared to more traditional colloidal nanocrystal synthetic methods. The following chapters then demonstrate the precise control living approaches offer in three separate studies; the first highlights sub-nanometer control of nanocrystal size from 2-22+ nm in diameter. Next the improvement in nanocrystal composition is illustrated using several transition metal dopants into an oxide nanocrystal matrix at near thermodynamically allowed compositions. Additionally, precise radial dopant placement is demonstrated, which has striking implications for material properties. The radial position of tin in tin-doped indium oxide nanocrystals and the resulting differences on the localized surface plasmon resonance are discussed. Finally, future opportunities are reviewed. This dissertation includes previously published co-authored material.

Goat red blood cells as precursor for iron oxide nanocrystal synthesis to develop nuclear targeted lung cancer therapy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sreevani, Vellingiri; Shanthi, Krishnamurthy; Kannan, Soundarapandian, E-mail: sk_protein@buc.edu.in

Graphical abstract: - Highlights: • Molecular approach of synthesis of Fe{sub 2}O{sub 3}-NC using goat blood as a bio-precursor. • The method is simple, efficient and environment friendly. • Synthesized nanocrystals were characterized by UV–vis spectroscopy, XRD, SEM, TEM, DLS and EDS. • Nanocrystals exhibited potent cytotoxicity against A549 cancer cell. • Nuclear targeting with expression of caspase-3, caspase-7 and Bcl-2 in A549 cancer cells. - Abstract: In this study, we synthesised iron oxide nanocrystals (Fe{sub 2}O{sub 3}-NC) from goat blood (bio-precursor) using red blood cells (RBC) lysis method (a molecular level approach) for the first time. The formation ofmore » Fe{sub 2}O{sub 3}-NC was achieved through a single-phase chemical reduction method. The size distribution of Fe{sub 2}O{sub 3}-NC falls between 20–30 nm for pellet and 100–200 nm for lysate and were found to be crystalline. Fe{sub 2}O{sub 3}-NC demonstrated significant cytotoxicity on A549. We report the direct visualization of interactions between Fe{sub 2}O{sub 3}-NC and the cancer cell nucleus. The active transport of Fe{sub 2}O{sub 3}-NC to the nucleus induces major changes to nuclear phenotype via nuclear envelope invaginations. We further examined the root cause for the involvement of Fe{sub 2}O{sub 3}-NC on the expression of caspase-3, caspase-7 and Bcl-2 in A549 cancer cells. This functional proteomic analysis clearly implies that the lung cancer cell proliferation is perfectly targeted by the biosynthesised Fe{sub 2}O{sub 3}-NC which could provide new insight for nuclear-targeted cancer therapy.« less

Controlled synthesis of bright and compatible lanthanide-doped upconverting nanocrystals

DOEpatents

Cohen, Bruce E.; Ostrowski, Alexis D.; Chan, Emory M.; Gargas, Daniel J.; Katz, Elan M.; Schuck, P. James; Milliron, Delia J.

2017-01-31

Certain nanocrystals possess exceptional optical properties that may make them valuable probes for biological imaging, but rendering these nanoparticles biocompatible requires that they be small enough not to perturb cellular systems. This invention describes a phosphorescent upconverting sub-10 nm nanoparticle comprising a lanthanide-doped hexagonal .beta.-phase NaYF.sub.4 nanocrystal and methods for making the same.

Nanocrystal synthesis

DOEpatents

Tisdale, William; Prins, Ferry; Weidman, Mark; Beck, Megan

2016-11-01

A method of preparing monodisperse MX semiconductor nanocrystals can include contacting an M-containing precursor with an X donor to form a mixture, where the molar ratio between the M containing precursor and the X donor is large. Alternatively, if additional X donor is added during the reaction, a smaller ratio between the M containing precursor and the X donor can be used to prepare monodisperse MX semiconductor nanocrystals.

Highly efficient one-step synthesis of carbon encapsulated nanocrystals by the oxidation of metal π-complexes

NASA Astrophysics Data System (ADS)

Liu, Boyang; Shao, Yingfeng; Xiang, Xin; Zhang, Fuhua; Yan, Shengchang; Li, Wenge

2017-08-01

Various carbon encapsulated nanocrystals, including MnS and MnO, Cr2O3, MoO2, Fe7S8 and Fe3O4, and ZrO2, are prepared in one step and in situ by a simple and highly efficient synthesis approach. The nanocrystals have an equiaxed morphology and a median size smaller than 30 nm. Tens and hundreds of these nanocrystals are entirely encapsulated by a wormlike amorphous carbon shell. The formation of a core-shell structure depends on the strongly exothermic reaction of metal π-complexes with ammonium persulfate in an autoclave at below 200 °C. During the oxidation process, the generated significant amounts of heat will destroy the molecular structure of the metal π-complex and cleave the ligands into small carbon fragments, which further transform into an amorphous carbon shell. The central metal atoms are oxidized to metal oxide/sulfide nanocrystals. The formation of a core-shell structure is independent of the numbers of ligands and carbon atoms as well as the metal types, implying that any metal π-complex can serve as a precursor and that various carbon encapsulated nanocrystals can be synthesized by this method.

Controlling the size of hot injection made nanocrystals by manipulating the diffusion coefficient of the solute.

PubMed

De Nolf, Kim; Capek, Richard K; Abe, Sofie; Sluydts, Michael; Jang, Youngjin; Martins, José C; Cottenier, Stefaan; Lifshitz, Efrat; Hens, Zeger

2015-02-25

We investigate the relation between the chain length of ligands used and the size of the nanocrystals formed in the hot injection synthesis. With two different CdSe nanocrystal syntheses, we consistently find that longer chain carboxylic acids result in smaller nanocrystals with improved size dispersions. By combining a more in-depth experimental investigation with kinetic reaction simulations, we come to the conclusion that this size tuning is due to a change in the diffusion coefficient and the solubility of the solute. The relation between size tuning by the ligand chain length and the coordination of the solute by the ligands is further explored by expanding the study to amines and phosphine oxides. In line with the weak coordination of CdSe nanocrystals by amines, no influence of the chain length on the nanocrystals is found, whereas the size tuning brought about by phosphine oxides can be attributed to a solubility change. We conclude that the ligand chain length provides a practical handle to optimize the outcome of a hot injection synthesis in terms of size and size dispersion and can be used to probe the interaction between ligands and the actual solute.

Synthesis and characterization of a BaGdF5:Tb glass ceramic as a nanocomposite scintillator for x-ray imaging.

PubMed

Lee, Gyuhyon; Struebing, Christian; Wagner, Brent; Summers, Christopher; Ding, Yong; Bryant, Alex; Thadhani, Naresh; Shedlock, Daniel; Star-Lack, Josh; Kang, Zhitao

2016-05-20

Transparent glass ceramics with embedded light-emitting nanocrystals show great potential as low-cost nanocomposite scintillators in comparison to single crystal and transparent ceramic scintillators. In this study, cubic structure BaGdF5:Tb nanocrystals embedded in an aluminosilicate glass matrix are reported for potential high performance MeV imaging applications. Scintillator samples with systematically varied compositions were prepared by a simple conventional melt-quenching method followed by annealing. Optical, structural and scintillation properties were characterized to guide the design and optimization of selected material systems, aiming at the development of a system with higher crystal volume and larger crystal size for improved luminosity. It is observed that enhanced scintillation performance was achieved by tuning the glass matrix composition and using GdF3 in the raw materials, which served as a nucleation agent. A 26% improvement in light output was observed from a BaGdF5:Tb glass ceramic with addition of GdF3.

Synthesis of Copper-Antimony-Sulfide Nanocrystals for Solution-Processed Solar Cells.

PubMed

Suehiro, Satoshi; Horita, Keisuke; Yuasa, Masayoshi; Tanaka, Tooru; Fujita, Katsuhiko; Ishiwata, Yoichi; Shimanoe, Kengo; Kida, Tetsuya

2015-08-17

The p-type nanocrystals (NCs) of copper-based chalcogenides, such as CuInSe2 and Cu2ZnSnS4, have attracted increasing attention in photovoltaic applications due to their potential to produce cheap solution-processed solar cells. Herein, we report the synthesis of copper-antimony-sulfide (CAS) NCs with different crystal phases including CuSbS2, Cu3SbS4, and Cu12Sb4S13. In addition, their morphology, crystal phase, and optical properties were characterized using transmission electron microscopy, X-ray diffractometry, UV-vis-near-IR spectroscopy, and photoemission yield spectroscopy. The morphology, crystal phase, and electronic structure were significantly dependent on the chemical composition in the CAS system. Devices were fabricated using particulate films consisting of CAS NCs prepared by spin coating without a high-temperature treatment. The CAS NC-based devices exhibited a diode-like current-voltage characteristic when coupled with an n-type CdS layer. In particular, the CuSbS2 NC devices exhibited photovoltaic responses under simulated sunlight, demonstrating its applicability for use in solution-processed solar cells.

Grafting polycaprolactone diol onto cellulose nanocrystals via click chemistry: Enhancing thermal stability and hydrophobic property.

PubMed

Zhou, Ling; He, Hui; Li, Mei-Chun; Huang, Siwei; Mei, Changtong; Wu, Qinglin

2018-06-01

Hydrophobic and thermally-stable cellulose nanocrystals (CNCs) were synthesized by polycarpolactone diol (PCL diol) grafting via click chemistry strategy. The synthesis was designed as a three-step procedure containing azide-modification of CNCs, alkyne-modification of PCL diol and sequent copper(I)-catalyzed azide-alkyne cycloaddition reaction. The structure of azide-modified CNCs and alkyne-modified PCL diol, the structure, hydrophobic ability and thermal stability of click products CNC-PCL were characterized. FTIR, XPS and H 1 NMR results indicated a successful grafting of the N 3 groups onto the CNCs, synthesis of PCL diol-CCH, and formation of the CNC-PCL material. CNC-PCL had enhanced dispersion in the non-polar solvent chloroform owing to the well-maintained microscale size and PCL-induced hydrophobic surface. The thermal stability of CNC-PCL was largely increased due to the grafting of thermally-stable PCL. This work demonstrates that click chemistry is an attractive modification strategy to graft CNCs with polyester chains for further potential application in polymer composites. Copyright © 2018 Elsevier Ltd. All rights reserved.

Volumetric flame synthesis of well-defined molybdenum oxide nanocrystals.

PubMed

Merchan-Merchan, Wilson; Saveliev, Alexei V; Desai, Milind

2009-11-25

Well-defined faceted inorganic Mo oxide nanocrystals are synthesized in the gas phase using a solid-fed-precursor flame synthesis method. The solid crystals have rectangular cross-section with characteristic size of 10-20 nm and with lengths ranging from 50 nm to a few hundred nanometres. A 1 mm diameter high purity Mo probe introduced in the oxygen-rich part of the flame serves as the material source. A combination of the strong temperature gradient and varying chemical species concentrations within the flame volume provides the ideal conditions for the rapid and direct formation of these unique nanocrystals. Oxidation and evaporation of MoO3 in the oxygen-rich zone are followed by reduction to MoO2 in the lower temperature, more fuel-rich zone. The MoO3 vapours formed are pushed in the direction of the gas flow and transformed into mature well-defined convex polyhedron nanocrystals bounded with six faces resembling rectangular parallelepipeds.

Low temperature oxidation synthesis of carbon encapsulated Cr2O3 nanocrystals and its lithium storage performance

NASA Astrophysics Data System (ADS)

Zhou, Yun; Liu, Boyang; Shao, Yingfeng; Fan, Chunhua; Fan, Runhua; Wen, Bosheng

A highly efficient and convenient strategy is developed for the one-step in-situ synthesis of carbon encapsulated Cr2O3 nanocrystals with core-shell structure (Cr2O3@C). The explosive reaction of chromocene with ammonium persulfate in an autoclave at 200∘C is crucial for the formation of this nanostructure. The Cr2O3 nanocrystals have a diameter of 5 to 20nm, which are entirely encapsulated by the amorphous carbon shell. The Cr2O3@C anode can retain a stable reversible capacity of 397mAhg-1 after 50 cycles at a current density of 119mA g-1.

Synthesis and surface chemistry of high quality wurtzite and kesterite Cu2ZnSnS4 nanocrystals using tin(II) 2-ethylhexanoate as a new tin source.

PubMed

Gabka, Grzegorz; Bujak, Piotr; Gryszel, Maciej; Ostrowski, Andrzej; Malinowska, Karolina; Zukowska, Grazyna Z; Agnese, Fabio; Pron, Adam; Reiss, Peter

2015-08-21

A novel synthesis method for the preparation of Cu2ZnSnS4 nanocrystals is presented using a liquid precursor of tin, namely tin(II) 2-ethylhexanoate, which yields small and nearly monodisperse NCs either in the kesterite or in the wurtzite phase depending on the sulfur source (elemental sulfur in oleylamine vs. dodecanethiol).

Promoted Iron Nanocrystals Obtained via Ligand Exchange as Active and Selective Catalysts for Synthesis Gas Conversion

PubMed Central

2017-01-01

Colloidal synthesis routes have been recently used to fabricate heterogeneous catalysts with more controllable and homogeneous properties. Herein a method was developed to modify the surface composition of colloidal nanocrystal catalysts and to purposely introduce specific atoms via ligands and change the catalyst reactivity. Organic ligands adsorbed on the surface of iron oxide catalysts were exchanged with inorganic species such as Na2S, not only to provide an active surface but also to introduce controlled amounts of Na and S acting as promoters for the catalytic process. The catalyst composition was optimized for the Fischer–Tropsch direct conversion of synthesis gas into lower olefins. At industrially relevant conditions, these nanocrystal-based catalysts with controlled composition were more active, selective, and stable than catalysts with similar composition but synthesized using conventional methods, possibly due to their homogeneity of properties and synergic interaction of iron and promoters. PMID:28824820

Precision synthesis of colloidal inorganic nanocrystals using metal and metalloid amides

NASA Astrophysics Data System (ADS)

Yarema, Maksym; Caputo, Riccarda; Kovalenko, Maksym V.

2013-08-01

Rational selection of molecular precursors is the key consideration in the synthesis of inorganic nanocrystals and nanoparticles. This review highlights the state-of-the-art and future potential of metal amides as precursors in the solution-phase synthesis of monodisperse colloidal nanocrystals of metals and metal alloys, as well as metal oxides and chalcogenides. We exclusively focus on homoleptic metal and metalloid alkylamides M(NR2)n and silylamides M[N(SiMe3)2]n as predominant choice of element-nitrogen bonded precursors, which are often advantageous to commonly used metal-oxygen and metal-carbon bonded counterparts. In particular, these amides are highly reactive in oxidation, reduction and metathesis reactions; they are oxygen-free, easy-to-make and/or commercially available. A comprehensive literature review is complemented by our theoretical studies on the thermal stability of metal silylamides using molecular dynamics simulations.

Large-scale and green synthesis of octahedral flower-like cupric oxide nanocrystals with enhanced photochemical properties

NASA Astrophysics Data System (ADS)

Li, Shi-Kuo; Pan, Yu-Yi; Wu, Mi; Huang, Fang-Zhi; Li, Chuan-Hao; Shen, Yu-Hua

2014-10-01

In this work, a large-scale and green method is reported for the facile synthesis of octahedral flower-like CuO nanocrystals via a coordination-deposition route by using Fehling regents. Not any harmful organic chemicals were used during the reaction period. The obtained hierarchical nanostructure can be rationally tailored by varying the concentration of tartrate ions and reaction time. The typical flower-like CuO nanocrystals in the range of 200-250 nm are consisted of numerous small crystalline whiskers, which present a porous surface with a specific surface area of 32.12 m2/g and a narrow band gap of 1.5 eV. Importantly, the flower-like CuO nanocrystals show an enhanced photocatalytic activity toward decomposing Rhodamine B (RhB) molecules. The degradation rate is about 87.9% in 40 min under visible light irradiation, which is about 2.5 times for the commercial CuO powers (35.2%). Moreover, the uniform flower-like monolayered CuO film exhibits an excellent photoelectrochemical (PEC) performance with a maximum photocurrent density of 58.8 μA/cm2, which is nearly five times higher than the commercial CuO film. This novel synthesis approach provides a large-scale and green protocol for synthesizing hierarchical metal oxide nanocrystals that are useful for photocatalysis, PEC water splitting and photovoltaic device.

Green and scalable production of colloidal perovskite nanocrystals and transparent sols by a controlled self-collection process

NASA Astrophysics Data System (ADS)

Liu, Shuangyi; Huang, Limin; Li, Wanlu; Liu, Xiaohua; Jing, Shui; Li, Jackie; O'Brien, Stephen

2015-07-01

Colloidal perovskite oxide nanocrystals have attracted a great deal of interest owing to the ability to tune physical properties by virtue of the nanoscale, and generate thin film structures under mild chemical conditions, relying on self-assembly or heterogeneous mixing. This is particularly true for ferroelectric/dielectric perovskite oxide materials, for which device applications cover piezoelectrics, MEMs, memory, gate dielectrics and energy storage. The synthesis of complex oxide nanocrystals, however, continues to present issues pertaining to quality, yield, % crystallinity, purity and may also suffer from tedious separation and purification processes, which are disadvantageous to scaling production. We report a simple, green and scalable ``self-collection'' growth method that produces uniform and aggregate-free colloidal perovskite oxide nanocrystals including BaTiO3 (BT), BaxSr1-xTiO3 (BST) and quaternary oxide BaSrTiHfO3 (BSTH) in high crystallinity and high purity. The synthesis approach is solution processed, based on the sol-gel transformation of metal alkoxides in alcohol solvents with controlled or stoichiometric amounts of water and in the stark absence of surfactants and stabilizers, providing pure colloidal nanocrystals in a remarkably low temperature range (15 °C-55 °C). Under a static condition, the nanoscale hydrolysis of the metal alkoxides accomplishes a complete transformation to fully crystallized single domain perovskite nanocrystals with a passivated surface layer of hydroxyl/alkyl groups, such that the as-synthesized nanocrystals can exist in the form of super-stable and transparent sol, or self-accumulate to form a highly crystalline solid gel monolith of nearly 100% yield for easy separation/purification. The process produces high purity ligand-free nanocrystals excellent dispersibility in polar solvents, with no impurity remaining in the mother solution other than trace alcohol byproducts (such as isopropanol). The afforded stable and transparent suspension/solution can be treated as inks, suitable for printing or spin/spray coating, demonstrating great capabilities of this process for fabrication of high performance dielectric thin films. The simple ``self-collection'' strategy can be described as green and scalable due to the simplified procedure from synthesis to separation/purification, minimum waste generation, and near room temperature crystallization of nanocrystal products with tunable sizes in extremely high yield and high purity.Colloidal perovskite oxide nanocrystals have attracted a great deal of interest owing to the ability to tune physical properties by virtue of the nanoscale, and generate thin film structures under mild chemical conditions, relying on self-assembly or heterogeneous mixing. This is particularly true for ferroelectric/dielectric perovskite oxide materials, for which device applications cover piezoelectrics, MEMs, memory, gate dielectrics and energy storage. The synthesis of complex oxide nanocrystals, however, continues to present issues pertaining to quality, yield, % crystallinity, purity and may also suffer from tedious separation and purification processes, which are disadvantageous to scaling production. We report a simple, green and scalable ``self-collection'' growth method that produces uniform and aggregate-free colloidal perovskite oxide nanocrystals including BaTiO3 (BT), BaxSr1-xTiO3 (BST) and quaternary oxide BaSrTiHfO3 (BSTH) in high crystallinity and high purity. The synthesis approach is solution processed, based on the sol-gel transformation of metal alkoxides in alcohol solvents with controlled or stoichiometric amounts of water and in the stark absence of surfactants and stabilizers, providing pure colloidal nanocrystals in a remarkably low temperature range (15 °C-55 °C). Under a static condition, the nanoscale hydrolysis of the metal alkoxides accomplishes a complete transformation to fully crystallized single domain perovskite nanocrystals with a passivated surface layer of hydroxyl/alkyl groups, such that the as-synthesized nanocrystals can exist in the form of super-stable and transparent sol, or self-accumulate to form a highly crystalline solid gel monolith of nearly 100% yield for easy separation/purification. The process produces high purity ligand-free nanocrystals excellent dispersibility in polar solvents, with no impurity remaining in the mother solution other than trace alcohol byproducts (such as isopropanol). The afforded stable and transparent suspension/solution can be treated as inks, suitable for printing or spin/spray coating, demonstrating great capabilities of this process for fabrication of high performance dielectric thin films. The simple ``self-collection'' strategy can be described as green and scalable due to the simplified procedure from synthesis to separation/purification, minimum waste generation, and near room temperature crystallization of nanocrystal products with tunable sizes in extremely high yield and high purity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02351c

Generalized syntheses of nanocrystal-graphene hybrids in high-boiling-point organic solvents.

PubMed

Pang, Danny Wei-Ping; Yuan, Fang-Wei; Chang, Yan-Cheng; Li, Guo-An; Tuan, Hsing-Yu

2012-08-07

Nanocrystal-graphene have been proposed as a new kind of promising hybrid for a wide range of application areas including catalysts, electronics, sensors, biomedicine, and energy storage, etc. Although a variety of methods have been developed for the preparation of hybrids, a facile and general synthetic approach is still highly required. In this study, nanocrystal-graphene hybrids were successfully synthesized in high-boiling-point organic solvents. Graphene oxide (GO) nanosheets were modified by oleylamine (OLA) to form a OLA-GO complex in order to be readily incorporated into hydrophobic synthesis. A rich library of highly crystalline nanocrystals, with types including noble metal, metal oxide, magnetic material and semiconductor were successfully grown on chemically converted graphene (CCG), which is simultaneously reduced from GO during the synthesis. High boiling-point solvents afford sufficient thermal energy to assure the high-quality crystalline nature of NCs, therefore the post-annealing process is obviated. Controlled experiments revealed that OLA-GO triggers heterogeneous nucleation and serves as excellent nuclei anchorage media. The protocol developed here brings one step closer to achieve "unity in diversity" on the preparation of nanocrystal-graphene hybrids.

Methylcellulose-Directed Synthesis of Nanocrystalline Zeolite NaA with High CO₂ Uptake.

PubMed

Shakarova, Dilshod; Ojuva, Arto; Bergström, Lennart; Akhtar, Farid

2014-07-28

Zeolite NaA nanocrystals with a narrow particle size distribution were prepared by template-free hydrothermal synthesis in thermo-reversible methylcellulose gels. The effects of the amount of methylcellulose, crystallization time and hydrothermal treatment temperature on the crystallinity and particle size distribution of the zeolite NaA nanocrystals were investigated. We found that the thermogelation of methylcellulose in the alkaline Na₂O-SiO₂-Al₂O₃-H₂O system played an important role in controlling the particle size. The synthesized zeolite nanocrystals are highly crystalline, as demonstrated by X-ray diffraction (XRD), and scanning electron microscopy (SEM) shows that the nanocrystals can also display a well-defined facetted morphology. Gas adsorption studies on the synthesized nanocrystalline zeolite NaA showed that nanocrystals with a size of 100 nm displayed a high CO₂ uptake capacity (4.9 mmol/g at 293 K at 100 kPa) and a relatively rapid uptake rate compared to commercially available, micron-sized particles. Low-cost nanosized zeolite adsorbents with a high and rapid uptake are important for large scale gas separation processes, e.g., carbon capture from flue gas.

Nanocrystal growth and morphology of PbTeSe-ZnSe composite thin films prepared by one-step synthesis method

NASA Astrophysics Data System (ADS)

Sato, Kazuhisa; Abe, Seishi

2016-10-01

The microstructure of polycrystalline PbTe1-xSex-ZnSe composite thin films has been studied by scanning transmission electron microscopy and electron diffraction. The films were prepared by the one-step synthesis method using simultaneous evaporation of PbTe and ZnSe. The nanocrystals of PbTe1-xSex are formed in a ZnSe matrix. Tellurium concentration can be tuned by controlling the PbTe evaporation source temperatures between 753 K and 793 K. Binary PbSe nanocrystals were formed at 753 K, while ternary PbTe1-xSex nanocrystals were formed at 793 K. The nanocrystals grow in a granular shape at the initial stage of film growth, and the morphology changes to nanowire-shape as the film grows, irrespective of the Te concentration. The ternary PbTe1-xSex nanocrystals were composed of two phases with different Te concentration; Te-rich (Se-poor) granular crystals were formed near the bottom half parts of the film and Te-poor (Se-rich) nanowires were formed at the upper half parts of the film. Columnar ZnSe crystals contain high-density {111} stacking faults due to the low stacking fault energy of ZnSe. A balance of deposition and re-evaporation on the substrate during the film growth will be responsible for the resultant nanocrystal morphology.

Plasmonic Properties of Silicon Nanocrystals Doped with Boron and Phosphorus.

PubMed

Kramer, Nicolaas J; Schramke, Katelyn S; Kortshagen, Uwe R

2015-08-12

Degenerately doped silicon nanocrystals are appealing plasmonic materials due to silicon's low cost and low toxicity. While surface plasmonic resonances of boron-doped and phosphorus-doped silicon nanocrystals were recently observed, there currently is poor understanding of the effect of surface conditions on their plasmonic behavior. Here, we demonstrate that phosphorus-doped silicon nanocrystals exhibit a plasmon resonance immediately after their synthesis but may lose their plasmonic response with oxidation. In contrast, boron-doped nanocrystals initially do not exhibit plasmonic response but become plasmonically active through postsynthesis oxidation or annealing. We interpret these results in terms of substitutional doping being the dominant doping mechanism for phosphorus-doped silicon nanocrystals, with oxidation-induced defects trapping free electrons. The behavior of boron-doped silicon nanocrystals is more consistent with a strong contribution of surface doping. Importantly, boron-doped silicon nanocrystals exhibit air-stable plasmonic behavior over periods of more than a year.

Synthesis of Core-shell Lanthanide-doped Upconversion Nanocrystals for Cellular Applications.

PubMed

Ai, Xiangzhao; Lyu, Linna; Mu, Jing; Hu, Ming; Wang, Zhimin; Xing, Bengang

2017-11-10

Lanthanide-doped upconversion nanocrystals (UCNs) have attracted much attention in recent years based on their promising and controllable optical properties, which allow for the absorption of near-infrared (NIR) light and can subsequently convert it into multiplexed emissions that span over a broad range of regions from the UV to the visible to the NIR. This article presents detailed experimental procedures for high-temperature co-precipitation synthesis of core-shell UCNs that incorporate different lanthanide ions into nanocrystals for efficiently converting deep-tissue penetrable NIR excitation (808 nm) into a strong blue emission at 480 nm. By controlling the surface modification with biocompatible polymer (polyacrylic acid, PAA), the as-prepared UCNs acquires great solubility in buffer solutions. The hydrophilic nanocrystals are further functionalized with specific ligands (dibenzyl cyclooctyne, DBCO) for localization on the cell membrane. Upon NIR light (808 nm) irradiation, the upconverted blue emission can effectively activate the light-gated channel protein on the cell membrane and specifically regulate the cation (e.g., Ca 2+ ) influx in the cytoplasm. This protocol provides a feasible methodology for the synthesis of core-shell lanthanide-doped UCNs and subsequent biocompatible surface modification for further cellular applications.

Facile synthesis of uniform large-sized InP nanocrystal quantum dots using tris(tert-butyldimethylsilyl)phosphine

PubMed Central

2012-01-01

Colloidal III-V semiconductor nanocrystal quantum dots [NQDs] have attracted interest because they have reduced toxicity compared with II-VI compounds. However, the study and application of III-V semiconductor nanocrystals are limited by difficulties in their synthesis. In particular, it is difficult to control nucleation because the molecular bonds in III-V semiconductors are highly covalent. A synthetic approach of InP NQDs was presented using newly synthesized organometallic phosphorus [P] precursors with different functional moieties while preserving the P-Si bond. Introducing bulky side chains in our study improved the stability while facilitating InP formation with strong confinement at a readily low temperature regime (210°C to 300°C). Further shell coating with ZnS resulted in highly luminescent core-shell materials. The design and synthesis of P precursors for high-quality InP NQDs were conducted for the first time, and we were able to control the nucleation by varying the reactivity of P precursors, therefore achieving uniform large-sized InP NQDs. This opens the way for the large-scale production of high-quality Cd-free nanocrystal quantum dots. PMID:22289352

Capping agents in nanoparticle synthesis: Surfactant and solvent system

NASA Astrophysics Data System (ADS)

Gulati, Shivani; Sachdeva, M.; Bhasin, K. K.

2018-05-01

The preparation of nanomaterials by organometallic precursors require a capping agent, which primarily acts as stabilizing agent and provide colloidal stability along with preventing agglomeration and stopping uncontrolled growth. Final morphology of nanocrystal largely depends on the type of capping agent which is adsorbed on the surface of nanocrystal. Thus capping agents are the keys to obtain the small-sized nanoparticles and are very frequently used in colloidal synthesis of nanoparticles to avoid its overgrowth.

Large Scale Synthesis of Colloidal Si Nanocrystals and their Helium Plasma Processing into Spin-On, Carbon-Free Nanocrystalline Si Films.

PubMed

Mohapatra, Pratyasha; Mendivelso-Perez, Deyny; Bobbitt, Jonathan M; Shaw, Santosh; Yuan, Bin; Tian, Xinchun; Smith, Emily A; Cademartiri, Ludovico

2018-05-30

This paper describes a simple approach to the large scale synthesis of colloidal Si nanocrystals and their processing by He plasma into spin-on carbon-free nanocrystalline Si films. We further show that the RIE etching rate in these films is 1.87 times faster than for single crystalline Si, consistent with a simple geometric argument that accounts for the nanoscale roughness caused by the nanoparticle shape.

Effect of alkali ions (Na+, K+, Cs+) on reaction mechanism of CZTS nano-particles synthesis

NASA Astrophysics Data System (ADS)

Kumar, Suresh; Altosaar, Mare; Grossberg, Maarja; Mikli, Valdek

2018-04-01

The control of morphology, elemental composition and phase composition of Cu2ZnSnS4 (CZTS) nano-crystals depends on the control of complex formation and surface stabilization of nano-particles in solution-based synthesis in oleylamine. At temperatures ≥280 °C, the control of nano-crystal's morphology and homogenous growth is difficult because of fast poly-nuclear growth occurring at higher temperatures. In the present work the effect of oleylamine complex formation with different alkali ions (Na+, K+ and Cs+) on nano-crystals growth at synthesis temperature of 280 °C was studied. It was found that nano-powders synthesized in the presence of Na+ and K+ ions showed the formation of crystals of different sizes - small nano-particles (18 nm-30 nm), large aggregated crystals (few nm to 1 μm) and large single crystals (1 μm - 4 μm). The presence of Cs+ ions in the nano-powder synthesis in oleylamine-metal precursor-CsOH solution promoted growth of nano-crystals of homogenous size. It is proposed that the formed oleylamine-Cs complexes a) enhance the formation and stabilization of oleylamine-metal (Cu, Zn and Sn) complexes before the injection of sulphur precursor into the oleylamine-metal precursor solution and b) after addition of sulphur stabilize the fast nucleated nano-particles and promote diffusion limited growth.

Controlled synthesis and novel photoluminescence properties of BaTiO{sub 3}:Eu{sup 3+}/Eu{sup 2+} nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Li; Li, Ying; Wang, Guofeng, E-mail: wanggf75@gmail.com

2015-01-15

Highlights: • Tetragonal phase BaTiO{sub 3}:Eu nanocrystals were successfully synthesized using a hydrothermal method. • Under 398 nm excitation, the emissions from Eu{sup 2+} and Eu{sup 3+} ions were observed. • The emission band of Eu{sup 2+} from BaTiO{sub 3}:Eu was observed to broaden with increasing Eu concentration. - Abstract: Tetragonal phase BaTiO{sub 3}:Eu nanocrystals were successfully synthesized using a hydrothermal method and a subsequent calcination treatment. The structures and morphologies of nanocrystals were characterized by X-ray diffraction, Raman spectroscopy, transmission electron microscopy, and scanning electron microscopy. The photoluminescence properties of BaTiO{sub 3}:Eu were investigated in detail. Under 398 nmmore » excitation, the emissions from Eu{sup 2+} and Eu{sup 3+} ions were observed, indicating that Eu{sup 2+} and Eu{sup 3+} ions coexisted in BaTiO{sub 3}:Eu nanocrystals. Especially, the emission band of Eu{sup 2+} from BaTiO{sub 3}:Eu was observed to broaden with increasing Eu concentration. When the Eu concentration was 0.5 mol%, the {sup 5}D{sub 0} → {sup 7}F{sub 0} and {sup 5}D{sub 1} → {sup 7}F{sub 0} emissions were observed. In addition, under 537 nm excitation, the emission intensity increased with increasing Eu concentration.« less

Inhibitors of the serotonin transporter protein (SERT): the design and synthesis of biotinylated derivatives of 3-(1,2,3,6-tetrahydro-pyridin-4-yl)-1H-indoles. High-affinity serotonergic ligands for conjugation with quantum dots.

PubMed

Tomlinson, Ian D; Mason, John N; Blakely, Randy D; Rosenthal, Sandra J

2005-12-01

There is a growing demand for compounds with specificity for the serotonin transporter protein (SERT) that can be conjugated to cadmium selenide/zinc sulfide core shell nanocrystals. This letter describes the design and synthesis of two different biotinylated SERT antagonists that can be attached to streptavidin-coated cadmium selenide/zinc sulfide core shell nanocrystals.

Hydrothermal Synthesis of PbTiO3 Nanocrystals with a pH-Adjusting Agent of Ammonia Solution

NASA Astrophysics Data System (ADS)

Li, Xinyi; Huang, Zhixiong; Zhang, Lianmeng; Guo, Dongyun

2018-05-01

The PbTiO3 nanocrystals were synthesized by a hydrothermal method, and ammonia solution was firstly used as a pH-adjusting agent. The effect of ammonia concentration on formation and morphologies of PbTiO3 nanocrystals was investigated. At low ammonia concentration (0-2.2 mol/L), no perovskite PbTiO3 phase was formed. When the ammonia concentration was 4.4 mol/L, the rod-like PbTiO3 nanocrystals with highly crystalline were successfully synthesized. As the ammonia concentration further increased to 13.2 mol/L, the flake-like PbTiO3 nanocrystals were formed.

A facile and green preparation of high-quality CdTe semiconductor nanocrystals at room temperature

NASA Astrophysics Data System (ADS)

Liu, Yan; Shen, Qihui; Yu, Dongdong; Shi, Weiguang; Li, Jixue; Zhou, Jianguang; Liu, Xiaoyang

2008-06-01

One chemical reagent, hydrazine hydrate, was discovered to accelerate the growth of semiconductor nanocrystals (cadmium telluride) instead of additional energy, which was applied to the synthesis of high-quality CdTe nanocrystals at room temperature and ambient conditions within several hours. Under this mild condition the mercapto stabilizers were not destroyed, and they guaranteed CdTe nanocrystal particle sizes with narrow and uniform distribution over the largest possible range. The CdTe nanocrystals (photoluminescence emission range of 530-660 nm) synthesized in this way had very good spectral properties; for instance, they showed high photoluminescence quantum yield of up to 60%. Furthermore, we have succeeded in detecting the living Borrelia burgdorferi of Lyme disease by its photoluminescence image using CdTe nanocrystals.

A general procedure to synthesize highly crystalline metal oxide and mixed oxidenanocrystals in aqueous medium and photocatalytic activity of metal/oxide nanohybrids

NASA Astrophysics Data System (ADS)

Nguyen, Thanh-Dinh; Dinh, Cao-Thang; Do, Trong-On

2011-04-01

A conventional and general route has been exploited to the high yield synthesis of many kinds of highly crystalline metal oxide and mixed oxidenanocrystals with different morphologies including belt, rod, truncated-octahedron, cubic, sphere, sheet via the hydrothermal reaction of inorganic precursors in aqueous solution in the presence of bifunctional 6-aminohexanoic acid (AHA) molecules as a capping agent. This method is a simple, reproducible and general route for the preparation of a variety of high-crystalline inorganic nanocrystals in scale-up. The shape of inorganic nanocrystals such as CoWO4, La2(MoO4)3 can be controlled by simply adjusting the synthesis conditions including pH solution and reaction temperature. Further, by tuning precursor monomer concentration, the mesocrystal hierarchical aggregated microspheres (e.g., MnWO4, La2(MoO4)3) can be achieved, due to the spontaneous assembly of individual AHA-capped nanoparticles. These obtained AHA-capped nanocrystals are excellent supports for the synthesis of a variety of hybrid metal/oxidenanocrystals in which noble metal particles are uniformly deposited on the surface of each individual nanosupport. The photocatalytic activity of Ag/TiO2 nanobelts as a typical hybrid photocatalyst sample for Methylene Blue degradation was also studied.A conventional and general route has been exploited to the high yield synthesis of many kinds of highly crystalline metal oxide and mixed oxidenanocrystals with different morphologies including belt, rod, truncated-octahedron, cubic, sphere, sheet via the hydrothermal reaction of inorganic precursors in aqueous solution in the presence of bifunctional 6-aminohexanoic acid (AHA) molecules as a capping agent. This method is a simple, reproducible and general route for the preparation of a variety of high-crystalline inorganic nanocrystals in scale-up. The shape of inorganic nanocrystals such as CoWO4, La2(MoO4)3 can be controlled by simply adjusting the synthesis conditions including pH solution and reaction temperature. Further, by tuning precursor monomer concentration, the mesocrystal hierarchical aggregated microspheres (e.g., MnWO4, La2(MoO4)3) can be achieved, due to the spontaneous assembly of individual AHA-capped nanoparticles. These obtained AHA-capped nanocrystals are excellent supports for the synthesis of a variety of hybrid metal/oxidenanocrystals in which noble metal particles are uniformly deposited on the surface of each individual nanosupport. The photocatalytic activity of Ag/TiO2 nanobelts as a typical hybrid photocatalyst sample for Methylene Blue degradation was also studied. Electronic supplementary information (ESI) available: Additional TEM, XRD, XPS, FTIR, UV-vis and photoluminescence results of the nanocrystals. See DOI: 10.1039/c1nr10109a

The use of castor oil and ricinoleic acid in lead chalcogenide nanocrystal synthesis

NASA Astrophysics Data System (ADS)

Kyobe, Joseph W. M.; Mubofu, Egid B.; Makame, Yahya M. M.; Mlowe, Sixberth; Revaprasadu, Neerish

2016-08-01

A green solution-based thermolysis method for the synthesis of lead chalcogenide (PbE, E = S, Se, Te) nanocrystals in castor oil (CSTO) and its isolate ricinoleic acid (RA) is described. The blue shift observed from the optical spectra of CSTO and RA-capped PbE nanocrystals (NCs) confirmed the evidence of quantum confinement. The dimensions of PbE NCs obtained from NIR absorption spectra, transmission electron microscopy (TEM), and X-ray diffraction (XRD) studies were in good agreement. The particle sizes estimated were in the range of 20, 25, and 130 nm for castor oil-capped PbS, PbSe, and PbTe, respectively. Well-defined close to cubic-shaped particles were observed in the scanning electron microscopy (SEM) images of PbSe and PbTe nanocrystals. The high-resolution TEM and selective area electron diffraction (SAED) micrographs of the as-synthesized crystalline PbE NCs showed distinct lattice fringes with d-spacing distances corroborating with the standard values reported in literature.

Synthesis, screening, and nanocrystals preparation of rhein amide derivatives.

PubMed

Chen, Lijiang; Zhang, Jinfeng; Rong, Jinghong; Liu, Yu; Zhao, Jinhua; Cui, Qingguo; Wang, Xin; Liang, Xiao; Pan, Hao; Liu, Hongsheng

2018-04-23

Rhein (RH) have many bioactivities, but the application was limited of its poor solubility. The present study aimed to establish an efficient method for the synthesis of rhein amide derivatives (RAD) to increase the solubility and anti-tumor activity. RAD exhibited stronger anti-tumor activity than RH in MTT assay. The solubility and oil/water partition coefficient results indicated that rhein-phenylalanine and rhein-isoleucine have better absorption effect, which was consolidated in pharmacokinetic study. Then, rhein-phenylalanine and rhein-isoleucine were prepared into nanocrystals via the precipitation-high pressure homogenization method. Additionally, the nanocrystals both displayed much higher dissolution profiles than the bulk drugs. Pharmacokinetics study indicated that the AUC 0-∞ and C max of nanocrystals increased markedly (p < 0.01). However, the concentration of RH-Phe-NC was far less than RH-Ile-NC in plasma. Consequently, RH-Ile-NC was validated to be an applicable way to improve the bioavailability of RH, which owns a promising future in clinical application.

Cellulose nanocrystals: synthesis, functional properties, and applications

PubMed Central

George, Johnsy; Sabapathi, SN

2015-01-01

Cellulose nanocrystals are unique nanomaterials derived from the most abundant and almost inexhaustible natural polymer, cellulose. These nanomaterials have received significant interest due to their mechanical, optical, chemical, and rheological properties. Cellulose nanocrystals primarily obtained from naturally occurring cellulose fibers are biodegradable and renewable in nature and hence they serve as a sustainable and environmentally friendly material for most applications. These nanocrystals are basically hydrophilic in nature; however, they can be surface functionalized to meet various challenging requirements, such as the development of high-performance nanocomposites, using hydrophobic polymer matrices. Considering the ever-increasing interdisciplinary research being carried out on cellulose nanocrystals, this review aims to collate the knowledge available about the sources, chemical structure, and physical and chemical isolation procedures, as well as describes the mechanical, optical, and rheological properties, of cellulose nanocrystals. Innovative applications in diverse fields such as biomedical engineering, material sciences, electronics, catalysis, etc, wherein these cellulose nanocrystals can be used, are highlighted. PMID:26604715

Synthesis of Colloidal Nanocrystal Heterostructures for High-Efficiency Light Emission

NASA Astrophysics Data System (ADS)

Lu, Yifei

Group II-VI semiconductor nanocrystals, particularly those based on ZnCdS(Se), can be synthesized using well established chemical colloidal processes, and have been a subject of extensive research over the past decade. Their optical properties can be easily tuned through size and composition variations, making them very attractive for many optoelectronic applications including light-emitting diodes (LEDs) and solar cells. Incorporation of diverse internal heterostructures provides an additional means for tuning the optical and electronic properties of conventional ZnCdS(Se) nanocrystals. Extensive bandgap and strain engineering may be applied to the resultant nanocrystal heterostructures to achieve desirable properties and enhanced performance. Despite the high scientific and practical interests of this unique class of nanomaterials, limited efforts have been made to explore their synthesis and potential device applications. This thesis focuses on the synthesis, engineering, characterization, and device demonstration of two types of CdSe-based nanocrystal heterostructures: core/multishell quantum dots (QDs) and QD quantum wells (QDQWs). Their optical properties have been tuned by bandgap and strain engineering to achieve efficient photoluminescence (PL) and electroluminescence (EL).Firstly, yellow light-emitting CdSe QDs with a strain-compensated ZnS/ZnCdS bilayer shell were synthesized using the successive ion layer adsorption and reaction technique and the effects of the shell on the luminescent properties were investigated. The core/shell/shell QDs enjoyed the benefits of excellent exciton confinement by the ZnS intermediate shell and strain compensation by the ZnCdS outer shell, and exhibited 40% stronger PL and a smaller peak redshift upon shell growth compared to conventional CdSe/ZnCdS/ZnS core/shell/shell QDs with an intermediate lattice adaptor. CdSe/ZnS/ZnCdS QD-LEDs had a luminance of 558 cd/m2 at 20 mA/cm 2, 28% higher than that of CdSe/ZnCdS/ZnS QD-LEDs. Secondly, CdS/CdSe/ZnS QDQWs were synthesized and their luminescence was tuned in an effort to realize efficient blue light emission from CdSe nanocrystals. CdSe QWs with a well width of 1.05 nm emitted at 467 nm with a spectral full-width-at-half-maximum of ~30 nm. With a 3-monolayer ZnS cladding layer which also acts as a passivating and strain-compensating layer, the QDQWs acquired a ~35% PL quantum yield (QY). Blue and green EL was obtained from QDQW-LEDs with 3-4.5 monolayers (MLs) QWs. It was found that as the well width and peak wavelength decreased, the overall EL was increasingly dominated by defect state emission, suggesting the device performance is mainly limited by poor charge injection into the QDQWs.

Terbium-Aspartic Acid Nanocrystals with Chirality-Dependent Tunable Fluorescent Properties.

PubMed

Ma, Baojin; Wu, Yu; Zhang, Shan; Wang, Shicai; Qiu, Jichuan; Zhao, Lili; Guo, Daidong; Duan, Jiazhi; Sang, Yuanhua; Li, Linlin; Jiang, Huaidong; Liu, Hong

2017-02-28

Terbium-aspartic acid (Tb-Asp) nanocrystals with chirality-dependent tunable fluorescent properties can be synthesized through a facile synthesis method through the coordination between Tb and Asp. Asp with different chirality (dextrorotation/d and levogyration/l) changes the stability of the coordination center following fluorescent absorption/emission ability differences. Compared with l-Asp, d-Asp can coordinate Tb to form a more stable center, following the higher quantum yield and longer fluorescence life. Fluorescence intensity of Tb-Asp linearly increases with increase ratio of d-Asp in the mixed chirality Tb-Asp system, and the fluorescent properties of Tb-Asp nanocrystals can be tuned by adjusting the chirality ratio. Tb-Asp nanocrystals possess many advantage, such as high biocompatibility, without any color in visible light irradiation, monodispersion with very small size, and long fluorescent life. Those characteristics will give them great potential in many application fields, such as low-cost antifake markers and advertisements using inkjet printers or for molds when dispersed in polydimethylsiloxane. In addition, europium can also be used to synthesize Eu-Asp nanoparticles. Importantly, the facile, low-cost, high-yield, mass-productive "green" process provides enormous advantages for synthesis and application of fluorescent nanocrystals, which will have great impact in nanomaterial technology.

Synthesis, Optical and Structural Properties of Copper Sulfide Nanocrystals from Single Molecule Precursors

PubMed Central

Ajibade, Peter A.; Botha, Nandipha L.

2017-01-01

We report the synthesis and structural studies of copper sulfide nanocrystals from copper (II) dithiocarbamate single molecule precursors. The precursors were thermolysed in hexadecylamine (HDA) to prepare HDA-capped CuS nanocrystals. The optical properties of the nanocrystals studied using UV–visible and photoluminescence spectroscopy showed absorption band edges at 287 nm that are blue shifted, and the photoluminescence spectra show emission curves that are red-shifted with respect to the absorption band edges. These shifts are as a result of the small crystallite sizes of the nanoparticles leading to quantum size effects. The structural studies were carried out using powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and atomic force microscopy. The XRD patterns indicates that the CuS nanocrystals are in hexagonal covellite crystalline phases with estimated particles sizes of 17.3–18.6 nm. The TEM images showed particles with almost spherical or rod shapes, with average crystallite sizes of 3–9.8 nm. SEM images showed morphology with ball-like microspheres on the surfaces, and EDS spectra confirmed the presence of CuS nanoparticles. PMID:28336865

Direct Single-Enzyme Biomineralization of Catalytically Active Ceria and Ceria–Zirconia Nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Curran, Christopher D.; Lu, Li; Jia, Yue

Biomineralization is an intriguing approach to the synthesis of functional inorganic materials for energy applications whereby biological systems are engineered to mineralize inorganic materials and control their structure over multiple length scales under mild reaction conditions. Herein we demonstrate a single-enzyme-mediated biomineralization route to synthesize crystalline, catalytically active, quantum-confined ceria (CeO2–x) and ceria–zirconia (Ce1–yZryO2–x) nanocrystals for application as environmental catalysts. In contrast to typical anthropogenic synthesis routes, the crystalline oxide nanoparticles are formed at room temperature from an otherwise inert aqueous solution without the addition of a precipitant or additional reactant. An engineered form of silicatein, rCeSi, as a singlemore » enzyme not only catalyzes the direct biomineralization of the nanocrystalline oxides but also serves as a templating agent to control their morphological structure. The biomineralized nanocrystals of less than 3 nm in diameter are catalytically active toward carbon monoxide oxidation following an oxidative annealing step to remove carbonaceous residue. The introduction of zirconia into the nanocrystals leads to an increase in Ce(III) concentration, associated catalytic activity, and the thermal stability of the nanocrystals.« less

Tuning surface grafting density of CeO2 nanocrystals with near- and supercritical solvent characteristics.

PubMed

Giroire, B; Slostowski, C; Marre, S; Aymonier, C; Aida, T; Hojo, D; Aoki, N; Takami, S; Adschiri, T

2016-01-21

In this work, the solvent effect on the synthesis of CeO2 nanocrystals synthesized in near- and supercritical alcohols is discussed. The materials prepared displayed a unique morphology of small nanocrystals (<10 nm) aggregated into larger nanospheres (∼100-200 nm). In such syntheses, alcohol molecules directly interact with the nanocrystal surface through alkoxide and carboxylate bondings. The grafting density was quantified from the weight loss measured using thermogravimetric analysis. A direct correlation between the grafting density and the alcohol chain length can be established. It was demonstrated that the shorter the alcohol chain length (i.e. methanol), the higher the surface coverage is. This trend is independent of the synthesis mode (batch or continuous). Additionally, an influence of the grafting density on the resulting nanocrystal size was established. It is suggested that the surface coverage has a high influence on the early stages of the nucleation and growth. Indeed, when high surface coverages are reached, all surface active sites are blocked, limiting the growth step and therefore leading to smaller particles. This effect was noticed with the materials prepared in the continuous mode where shorter reaction time was performed.

Synthesis and characterization of Na(Gd0.5Lu0.5)F4: Nd3+,a core-shell free multifunctional contrast agent.

PubMed

Mimun, L Christopher; Ajithkumar, G; Rightsell, Chris; Langloss, Brian W; Therien, Michael J; Sardar, Dhiraj K

2017-02-25

Compared to conventional core-shell structures, core-shell free nanoparticles with multiple functionalities offer several advantages such as minimal synthetic complexity and low production cost. In this paper, we present the synthesis and characterization of Nd 3+ doped Na(Gd 0.5 Lu 0.5 )F 4 as a core-shell free nanoparticle system with three functionalities. Nanocrystals with 20 nm diameter, high crystallinity and a narrow particle size distributions were synthesized by the solvothermal method and characterized by various analytical techniques to understand their phase and morphology. Fluorescence characteristics under near infrared (NIR) excitation at 808 nm as well as X-ray excitation were studied to explore their potential in NIR optical and X-ray imaging. At 1.0 mol% Nd concentration, we observed a quantum yield of 25% at 1064 nm emission with 13 W/cm 2 excitation power density which is sufficiently enough for imaging applications. Under 130 kVp (5 mA) power of X-ray excitation, Nd 3+ doped Na(Gd 0.5 Lu 0.5 )F 4 shows the characteristic emission bands of Gd 3+ and Nd 3+ with the strongest emission peak at 1064 nm due to Nd 3+ . Furthermore, magnetization measurements show that the nanocrystals are paramagnetic in nature with a calculated magnetic moment per particle of ~570 μB at 2T. These preliminary results support the suitability of the present nanophosphor as a multimodal contrast agent with three imaging features viz. optical, magnetic and X-ray.

Designing Selectivity in Metal-Semiconductor Nanocrystals: Synthesis, Characterization, and Self-Assembly

NASA Astrophysics Data System (ADS)

Pavlopoulos, Nicholas George

This dissertation contains six chapters detailing recent advances that have been made in the synthesis and characterization of metal-semiconductor hybrid nanocrystals (HNCs), and the applications of these materials. Primarily focused on the synthesis of well-defined II-VI semiconductor nanorod (NR) and tetrapod (TP) based constructs of interest for photocatalytic and solar energy applications, the research described herein discusses progress towards the realization of key design rules for the synthesis of functional semiconductor nanocrystals (NCs). As such, a blend of novel synthesis, advanced characterization, and direct application of heterostructured nanoparticles are presented. The first chapter is a review summarizing the design, synthesis, properties, and applications of multicomponent nanomaterials composed of disparate semiconductor and metal domains. By coupling two compositionally distinct materials onto a single nanocrystal, synergistic properties can arise that are not present in the isolated components, ranging from self-assembly to photocatalysis. For semiconductor nanomaterials, this was first realized in the ability to tune nanomaterial dimensions from 0-D quantum dot (QD) structures to cylindrical (NR) and branched (TP) structures by exploitation of advanced colloidal synthesis techniques and understandings of NC facet reactivities. The second chapter is focused on the synthesis and characterization of well-defined CdSe-seeded-CdS (CdSe CdS) NR systems synthesized by overcoating of wurtzite (W) CdSe quantum dots with W-CdS shells. 1-dimensional NRs have been interesting constructs for applications such as solar concentrators, optical gains, and photocatalysis. Through synthetic control over CdSe CdS NR systems, materials with small and large CdSe seeds were prepared, and for each seed size, multiple NR lengths were prepared. Through transient absorption studies, it was found that band alignment did not affect the efficiency of charge localization in the CdSe core, whereas NR length had a profound effect. This work indicated that longer NRs resulted in poor exciton localization efficiencies owing to ultrafast trapping of photoexcited excitons generated in the CdS NR. The third chapter describes the synthesis of Au-tipped CdSe NRs and studies of the effects of selective metal nanoparticle deposition on the band edge energetics of these model photocatalytic systems. Previous studies had demonstrated ultrafast localization of photoexcited electrons in Au nanoparticles (AuNP) (and PtNP) deposited at the termini of CdSe and CdSe CdS NR constructs. Also, for similar systems, the hydrogen evolution reaction (HER) had been studied, for which it was found that noble metal nanoparticle tips were necessary to extract photoexcited electrons from the NR constructs and drive catalytic reactions. However, in these studies, energetic trap states, generally ascribed to surface defects on the NC surface, are often cited as contributing to loss of catalytic efficiency. Through a combination of ultraviolet photoelectron spectroscopy and waveguide based spectroelectrochemistry on films of 40 nm long CdSe NRs before and after AuNP functionalization, we found that metal deposition resulted in the formation of mid-gap energy states, which were assigned as metal-semiconductor interface states. The fourth chapter transitions from NR constructs to highly absorbing CdSe CdS TP materials, for which a single zincblende (ZB) CdSe NC is used to seed the growth of four identical CdS arms. These arms act as highly efficient light absorbers, resulting in absorption cross sections an order of magnitude greater than for comparable NR systems. In the past, many studies have been published on the striking properties of TP nanocrystals, such as dual wavelength fluorescence, multiple exciton generation, and inherent self-assembly owing to their unique geometry. Nonetheless, these materials have not been exploited for photocatalysis, primarily owing to challenges in preparing TP from ultrasmall ZB-CdSe seed size, thus preventing access to quasi-type II structures necessary for efficient photocatalysis. In this study, we successfully break through the type I/quasi-type II barrier for TP NCs, reclaiming lost ground in this field and demonstrating for the first time quasi-type II behavior in CdSe CdS TPs through transient absorption measurements. The fifth chapter continues with the study of CdSe CdS TPs, and elaborates on a new method for the selective functionalization of the highly symmetrical TP construct. TP materials have been notoriously difficult to selectively functionalize, owing to their symmetric nature. Using a novel photoinduced electrochemical Ostwald ripening process, we found that initially randomly deposited AuNPs could be ripened to a single, large AuNP tip at the end of one arm of a type I CdSe CdS TP with 40 nm arms. The sixth chapter elaborates further on the preparation of colloidal polymers, further extending the analogy between molecular and colloidal levels of synthetic control. One challenge in the field of colloidal science is the realization of new modes of self-assemble for compositionally distinct nanoparticles. In this work, it was found that Au Co nanoparticle dipole strength could be systematically varied by tuning of AuNP size on CdSe CdS nanorods/tetrapods. (Abstract shortened by ProQuest.).

Direct synthesis of antimicrobial coatings based on tailored bi-elemental nanoparticles

NASA Astrophysics Data System (ADS)

Benetti, Giulio; Cavaliere, Emanuele; Canteri, Adalberto; Landini, Giulia; Rossolini, Gian Maria; Pallecchi, Lucia; Chiodi, Mirco; Van Bael, Margriet J.; Winckelmans, Naomi; Bals, Sara; Gavioli, Luca

2017-03-01

Ultrathin coatings based on bi-elemental nanoparticles (NPs) are very promising to limit the surface-related spread of bacterial pathogens, particularly in nosocomial environments. However, tailoring the synthesis, composition, adhesion to substrate, and antimicrobial spectrum of the coating is an open challenge. Herein, we report on a radically new nanostructured coating, obtained by a one-step gas-phase deposition technique, and composed of bi-elemental Janus type Ag/Ti NPs. The NPs are characterized by a cluster-in-cluster mixing phase with metallic Ag nano-crystals embedded in amorphous TiO2 and present a promising antimicrobial activity including also multidrug resistant strains. We demonstrate the flexibility of the method to tune the embedded Ag nano-crystals dimension, the total relative composition of the coating, and the substrate type, opening the possibility of tailoring the dimension, composition, antimicrobial spectrum, and other physical/chemical properties of such multi-elemental systems. This work is expected to significantly spread the range of applications of NPs coatings, not only as an effective tool in the prevention of healthcare-associated infections but also in other technologically relevant fields like sensors or nano-/micro joining.

Synthesis and characterization of surface-modified colloidal CdTe Quantum Dots

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rajh, T.; Micic, O.I.; Nozik, A.J.

1993-11-18

The controlled synthesis of quantized colloidal CdTe nanocrystals (in aqueous solutions) with narrow size distributions and stabilized against rapid oxidation was achieved by capping the quantum dot particles with 3-mercapto-1,2-propanediol. Nanocrystals (i.e., quantum dots) with mean diameters of 20, 25, 35, and 40 A were produced. Optical absorption spectra showed strong excitonic peaks at the smallest size; the absorption coefficient was shown to follow an inverse cube dependence on particle diameter, while the extinction coefficient per particle remained constant. The quantum yield for photoluminescence increased with decreasing particle size and reached 20% at 20 A. The valence band edges ofmore » the CdTe quantum dots were determined by pulse radiolysis experiments (hole injection from oxidizing radicals); the bandgaps were estimated from pulse radiolysis data (redox potentials of hole and electron injecting radicals) and from the optical spectra. The dependence of the CdTe bandgap on quantum dot size was found to be much weaker than predicted by the effective mass approximation; this result is consistent with recently published theoretical calculations by several groups. 36 refs., 5 figs., 1 tab.« less

Microwave hydrothermal synthesis and characterization of rare-earth stannate nanoparticles

NASA Astrophysics Data System (ADS)

Huang, Shuang; Xu, Hua-lan; Zhong, Sheng-liang; Wang, Lei

2017-07-01

Rare-earth stannate (Ln2Sn2O7 (Ln = Y, La-Lu)) nanocrystals with an average diameter of 50 nm were prepared through a facile microwave hydrothermal method at 200°C within 60 min. The products were well characterized. The effect of reaction parameters such as temperature, reaction time, pH value, and alkali source on the preparation was investigated. The results revealed that the pH value plays an important role in the formation process of gadolinium stannate (Gd2Sn2O7) nanoparticles. By contrast, the alkali source had no effect on the phase composition or morphology of the final product. Uniform and sphere-like nanoparticles with an average size of approximately 50 nm were obtained at the pH value of 11.5. A possible formation mechanism was briefly proposed. Gd2Sn2O7:Eu3+ nanoparticles displayed strong orange-red emission. Magnetic measurements revealed that Gd2Sn2O7 nanoparticles were paramagnetic. The other rare-earth stannate Ln2Sn2O7 (Ln = Y, La-Lu) nanocrystals were prepared by similar approaches.

Synthesis and structural characterization of CdS nanoparticles

NASA Astrophysics Data System (ADS)

Kotkata, M. F.; Masoud, A. E.; Mohamed, M. B.; Mahmoud, E. A.

2009-08-01

Amorphous CdS nanoparticles capped with cetyltrimethyl ammonium bromide (CTAB) were synthesised under various conditions using a coprecipitation method. A blue shift in the band gap was observed in the UV-visible absorption spectra indicating the formation of nanoparticles of an approximate size of 8 nm. The recorded transmission electron micrographs confirmed this result. The phase-nature, phase transformation as well as the structure of the synthesised CdS nanoparticles have been extensively characterized using X-ray diffraction (XRD), radial distribution function (RDF), differential scanning calorimetry (DSC), Fourier transform infrared (FT-IR), Raman scattering (RS) and/or heat stage X-ray diffraction (HSXRD). Analysis of the obtained results revealed that the synthesised amorphous CdS nanoparticles could be transformed into CdS nanocrystals having a zinc blende or a wurtzite structure, relying on the applied heat treatment scheme. The rate of nanocrystal growth depends on the aging period, prior filtering the reacted materials, and its relation to the quality of the capping process. Five days aging period tends to enhance the stability of the grown phase with a remarkable surface stability.

Size Dependence of Metal-Insulator Transition in Stoichiometric Fe₃O4₄Nanocrystals.

PubMed

Lee, Jisoo; Kwon, Soon Gu; Park, Je-Geun; Hyeon, Taeghwan

2015-07-08

Magnetite (Fe3O4) is one of the most actively studied materials with a famous metal-insulator transition (MIT), so-called the Verwey transition at around 123 K. Despite the recent progress in synthesis and characterization of Fe3O4 nanocrystals (NCs), it is still an open question how the Verwey transition changes on a nanometer scale. We herein report the systematic studies on size dependence of the Verwey transition of stoichiometric Fe3O4 NCs. We have successfully synthesized stoichiometric and uniform-sized Fe3O4 NCs with sizes ranging from 5 to 100 nm. These stoichiometric Fe3O4 NCs show the Verwey transition when they are characterized by conductance, magnetization, cryo-XRD, and heat capacity measurements. The Verwey transition is weakly size-dependent and becomes suppressed in NCs smaller than 20 nm before disappearing completely for less than 6 nm, which is a clear, yet highly interesting indication of a size effect of this well-known phenomena. Our current work will shed new light on this ages-old problem of Verwey transition.

Lanthanide-activated scheelite nanocrystal phosphors prepared by the low-temperature vapor diffusion sol-gel method

DOE PAGES

Culver, Sean P.; Brutchey, Richard L.

2016-10-25

A series of Eu 3+-, Tb 3+-, and Tm 3+-doped CaWO 4 phosphor nanocrystals have been synthesized under benign conditions using the vapor diffusion sol–gel method. Here the high degree of synthetic flexibility inherent to this approach has enabled the synthesis of a CaWO 4:(Eu,Tb) dual-sensitized white light emitting nanocrystal phosphor upon commercial UV excitation at 366 nm with a long lifetime exceeding 1 ms.

Synthesis and characterization of cellulose nanocrystals as reinforcing agent in solely palm based polyurethane foam

NASA Astrophysics Data System (ADS)

Septevani, Athanasia Amanda; Annamalai, Pratheep K.; Martin, Darren J.

2017-11-01

The increasing awareness of the environment and the economy of petroleum resources has driven the development of alternative processes and raw materials based on sustainable and renewable biomaterials with excellent properties. This study is aimed to use biologically renewable cellulose nanocrystals (CNC) as reinforcing agent to enhance the properties of polyurethane foams (PUF) based on solely palm-polyol. Rod-like shape cellulose nanocrystals (CNC) was successfully isolated from cotton based resources via strong acid hydrolysis with the average width, length and aspect ratio about 14.7 ± 4.9 nm, 167.7 ± 23.2 nm and 11.4, respectively. The crystallinity of CNC was confirmed by using X-ray diffraction (XRD) and differential scanning calorimetry (DSC) and was found at 82.8% and 83.8%, respectively. This obtained cellulose nanocrystals (CNC) at a loading of 0.4 wt. % was then incorporated via solvent-free sonication method in the model of palm based polyurethane foam. The preliminary results showed that the effect of CNC on the mechanical properties afforded a significant improvement on the compressive strength and modulus without affecting much their tensile strength. The results on thermal stability and thermal transitions were found unchanged whereas the storage modulus revealed substantial improvement with the presence of CNC with almost two fold from 0.7 MPa to 1.3 MPa (˜86 %).

Synthesis and spectroscopic properties of silica-dye-semiconductor nanocrystal hybrid particles.

PubMed

Ren, Ting; Erker, Wolfgang; Basché, Thomas; Schärtl, Wolfgang

2010-12-07

We prepared silica-dye-nanocrystal hybrid particles and studied the energy transfer from semiconductor nanocrystals (= donor) to organic dye molecules (= acceptor). Multishell CdSe/CdS/ZnS semiconductor nanocrystals were adsorbed onto monodisperse Stöber silica particles with an outer silica shell of thickness 2-23 nm containing organic dye molecules (Texas Red). The thickness of this dye layer has a strong effect on the energy transfer efficiency, which is explained by the increase in the number of dye molecules homogeneously distributed within the silica shell, in combination with an enhanced surface adsorption of nanocrystals with increasing dye amount. Our conclusions were underlined by comparison of the experimental results with numerically calculated FRET efficiencies and by control experiments confirming attractive interaction between the nanocrystals and Texas Red freely dissolved in solution.

Phage-directed synthesis of copper sulfide: structural and optical characterization

NASA Astrophysics Data System (ADS)

Shahriar Zaman, Mohammed; Moon, Chung Hee; Bozhilov, Krassimir N.; Haberer, Elaine D.

2013-08-01

The growth of crystalline copper sulfide using a viral template was investigated using sequential incubation in CuCl2 and Na2S precursors. Non-specific electrostatic attraction between a genetically-modified M13 bacteriophage and copper cations in the CuCl2 precursor caused phage agglomeration and bundle formation. Following the addition of Na2S, polydisperse nanocrystals 2-7 nm in size were found along the length of the viral scaffold. The structure of the copper sulfide material was identified as cubic anti-fluorite type Cu1.8S, space group F m\\bar {3}m. Strong interband absorption was observed within the ultraviolet to visible range with an onset near 800 nm. Furthermore, free carrier absorption, associated with the localized surface plasmon resonance of the copper sulfide nanocrystals, was seen in the near infrared with absorbance maxima at 1060 nm and 3000 nm, respectively.

Enhancement of room temperature ferromagnetism in tin oxide nanocrystal using organic solvents

NASA Astrophysics Data System (ADS)

Sakthiraj, K.; Hema, M.; Balachandra Kumar, K.

2017-10-01

The effect of organic solvents (ethanol & ethylene glycol) on the room temperature ferromagnetism in nanocrystalline tin oxide has been studied. The samples were synthesized using sol-gel method with the mixture of water & organic liquid as solvent. It is found that pristine SnO2 nanocrystal contain two different types of paramagnetic centres over their surface:(i) surface chemisorbed oxygen species and (ii) Sn interstitial & oxygen vacancy defect pair. The magnetic moment induced in the as-prepared samples is mainly contributed by the alignment of local spin moments resulting from these defects. These surface defect states are highly activated by the usage of ethylene glycol solvent rather than ethylene in tin oxide nanostructure synthesis. Powder X-ray diffraction, transmission electron microscope imaging, energy dispersive spectrometry, Fourier transformed infrared spectroscopy, UV-vis absorption spectroscopy, photoluminescence spectroscopy, vibrating sample magnetometer measurement and electron spin resonance spectroscopy were employed to characterize the nanostructured tin oxide materials.

Polymer-grafted cellulose nanocrystals as pH-responsive reversible flocculants.

PubMed

Kan, Kevin H M; Li, Jian; Wijesekera, Kushlani; Cranston, Emily D

2013-09-09

Cellulose nanocrystals (CNCs) are a sustainable nanomaterial with applications spanning composites, coatings, gels, and foams. Surface modification routes to optimize CNC interfacial compatibility and functionality are required to exploit the full potential of this material in the design of new products. In this work, CNCs have been rendered pH-responsive by surface-initiated graft polymerization of 4-vinylpyridine with the initiator ceric(IV) ammonium nitrate. The polymerization is a one-pot, water-based synthesis carried out under sonication, which ensures even dispersion of the cellulose nanocrystals during the reaction. The resultant suspensions of poly(4-vinylpyridine)-grafted cellulose nanocrystals (P4VP-g-CNCs) show reversible flocculation and sedimentation with changes in pH; the loss of colloidal stability is visible by eye even at concentrations as low as 0.004 wt %. The presence of grafted polymer and the ability to tune the hydrophilic/hydrophobic properties of P4VP-g-CNCs were characterized by Fourier transform infrared spectroscopy, elemental analysis, electrophoretic mobility, mass spectrometry, transmittance spectroscopy, contact-angle measurements, thermal analysis, and various microscopies. Atomic force microscopy showed no observable changes in the CNC dimensions or degree of aggregation after polymer grafting, and a liquid crystalline nematic phase of the modified CNCs was detected by polarized light microscopy. Controlled stability and wettability of P4VP-g-CNCs is advantageous both in composite design, where cellulose nanocrystals generally have limited dispersibility in nonpolar matrices, and as biodegradable flocculants. The responsive nature of these novel nanoparticles may offer new applications for CNCs in biomedical devices, as clarifying agents, and in industrial separation processes.

Nanorings of self-assembled fullerene C(70) as templating nanoreactors.

PubMed

Iyer, K Swaminathan; Saunders, Martin; Becker, Thomas; Evans, Cameron W; Raston, Colin L

2009-11-18

Micelles, polyelectrolytes, peptides, and plasmid DNA with well-defined growth cavities can function as templates for the synthesis of metal nanocrystals. In a similar way, carbon-based toroidal 'nanoreactors' composed of clustered fullerenes could be used to synthesize nanohybrids by forming metal nanocrystals within the confines of the ring.

A totally phosphine-free synthesis of metal telluride nanocrystals by employing alkylamides to replace alkylphosphines for preparing highly reactive tellurium precursors.

PubMed

Yao, Dong; Liu, Yi; Zhao, Wujun; Wei, Haotong; Luo, Xintao; Wu, Zhennan; Dong, Chunwei; Zhang, Hao; Yang, Bai

2013-10-21

Despite the developments in the wet chemical synthesis of high-quality semiconductor nanocrystals (NCs) with diverse elemental compositions, telluride NCs are still irreplaceable materials owing to their excellent photovoltaic and thermoelectric performances. Herein we demonstrate the dissolution of elemental tellurium (Te) in a series of alkylamides by sodium borohydride (NaBH4) reduction at relatively low temperature to produce highly reactive precursors for hot-injection synthesis of telluride NCs. The capability to tune the reactivity of Te precursors by selecting injection temperature permits control of NC size over a broad range. The current preparation of Te precursors is simple, economical, and totally phosphine-free, which will promote the commercial synthesis and applications of telluride NCs.

Molten Salt Synthesis and Structural Characterization of BaTiO3 Nanocrystal Ceramics

NASA Astrophysics Data System (ADS)

Ahda, S.; Misfadhila, S.; Parikin, P.; Putra, T. Y. S. P.

2017-02-01

A new synthesis route to obtain high-purity barium titanate powder, BaTiO3, using the molten salt method by reacting the raw materials (BaCO3 and TiO2) in an atmosphere of molten NaCl and KCl, has been developed. The synthesized BaTiO3 ceramic particles have been successfully carried out at the sintering temperature 950°C for 4 hours. The Rietveld refinement of the XRD diffraction patterns was employed to characterize the structural information of the nanocrystalline BaTiO3 ceramics. The lattice parameters (a=4.0043 Å, b=4.0308Å with space group P4mm) of tetragonal perovskite structure, as an indication of piezoelectric characteristics, have been successfully determined by the Rietveld refinement. While the crystallitte particle size and strains have been obtained for the values of 110.6 nm and 0.74 % respectively

Synthesis of renewable diesel through hydrodeoxygenation reaction from nyamplung oil (Calophyllum Inophyllum oil) using NiMo/Z and NiMo/C catalysts with rapid heating and cooling method

NASA Astrophysics Data System (ADS)

Susanto, B. H.; Prakasa, M. B.; Shahab, M. H.

2016-11-01

The synthesis of metal nanocrystal was conducted by modification preparation from simple heating method which heating and cooling process run rapidly. The result of NiMo/Z 575 °C characterizations are 33.73 m2/gram surface area and 31.80 nm crystal size. By used NiMo/C 700 °C catalyst for 30 minutes which had surface area of 263.21 m2/gram, had 31.77 nm crystal size, and good morphology, obtained catalyst with high activity, selectivity, and stability. After catalyst activated, synthesis of renewable diesel performed in hydrogenation reactor at 375 °C, 12 bar, and 800 rpm. The result of conversion was 81.99%, yield was 68.08%, and selectivity was 84.54%.

Synthesis, characterization, and cytocompatibility of potential cockle shell aragonite nanocrystals for osteoporosis therapy and hormonal delivery.

PubMed

Jaji, Alhaji Zubair; Bakar, Md Zuki Bin Abu; Mahmud, Rozi; Loqman, Mohamad Yusof; Hezmee, Mohamad Noor Mohamad; Isa, Tijani; Wenliang, Fu; Hammadi, Nahidah Ibrahim

2017-01-01

Calcium carbonate is a porous inorganic nanomaterial with huge potential in biomedical applications and controlled drug delivery. This study aimed at evaluating the physicochemical properties and in vitro efficacy and safety of cockle shell aragonite calcium carbonate nanocrystals (ANC) as a potential therapeutic and hormonal delivery vehicle for osteoporosis management. Free and human recombinant parathyroid hormone 1-34 (PTH 1-34)-loaded cockle shell aragonite calcium carbonate nanocrystals (PTH-ANC) were synthesized and evaluated using standard procedures. Transmission electron microscopy and field emission scanning electron microscopy results demonstrated highly homogenized spherical-shaped aragonite nanocrystals of 30±5 nm diameter. PTH-ANC had a zeta potential of -27.6±8.9 mV. The encapsulation efficiency of the formulation was found to be directly proportional to the concentrations of the drug fed. The X-ray diffraction patterns revealed strong crystallizations with no positional change of peaks before and after PTH-ANC synthesis. Fourier transform infrared spectroscopy demonstrated no detectable interactions between micron-sized aragonite and surfactant at molecular level. PTH-ANC formulation was stabilized at pH 7.5, enabling sustained slow release of PTH 1-34 for 168 h (1 week). A 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide cytocompatibility assay in Human Foetal Osteoblast Cell Line hFOB 1.19 showed that ANC can safely support osteoblast proliferation up to 48 h whereas PTH-ANC can safely support the proliferation at 72 h and beyond due to the sustained slow release of PTH 1-34. It was concluded that due to its biogenic nature, ANC is a cytocompatible antiosteoporotic agent. It doubles as a nanocarrier for the enhancement of efficacy and safety of the bone anabolic PTH 1-34. ANC is expected to reduce the cost, dosage, and dose frequency associated with the use of PTH 1-34 management of primary and secondary forms of osteoporosis.

Synthesis, characterization, and cytocompatibility of potential cockle shell aragonite nanocrystals for osteoporosis therapy and hormonal delivery

PubMed Central

Jaji, Alhaji Zubair; Bakar, Md Zuki Bin Abu; Mahmud, Rozi; Loqman, Mohamad Yusof; Hezmee, Mohamad Noor Mohamad; Isa, Tijani; Wenliang, Fu; Hammadi, Nahidah Ibrahim

2017-01-01

Calcium carbonate is a porous inorganic nanomaterial with huge potential in biomedical applications and controlled drug delivery. This study aimed at evaluating the physicochemical properties and in vitro efficacy and safety of cockle shell aragonite calcium carbonate nanocrystals (ANC) as a potential therapeutic and hormonal delivery vehicle for osteoporosis management. Free and human recombinant parathyroid hormone 1-34 (PTH 1-34)-loaded cockle shell aragonite calcium carbonate nanocrystals (PTH-ANC) were synthesized and evaluated using standard procedures. Transmission electron microscopy and field emission scanning electron microscopy results demonstrated highly homogenized spherical-shaped aragonite nanocrystals of 30±5 nm diameter. PTH-ANC had a zeta potential of −27.6±8.9 mV. The encapsulation efficiency of the formulation was found to be directly proportional to the concentrations of the drug fed. The X-ray diffraction patterns revealed strong crystallizations with no positional change of peaks before and after PTH-ANC synthesis. Fourier transform infrared spectroscopy demonstrated no detectable interactions between micron-sized aragonite and surfactant at molecular level. PTH-ANC formulation was stabilized at pH 7.5, enabling sustained slow release of PTH 1-34 for 168 h (1 week). A 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide cytocompatibility assay in Human Foetal Osteoblast Cell Line hFOB 1.19 showed that ANC can safely support osteoblast proliferation up to 48 h whereas PTH-ANC can safely support the proliferation at 72 h and beyond due to the sustained slow release of PTH 1-34. It was concluded that due to its biogenic nature, ANC is a cytocompatible antiosteoporotic agent. It doubles as a nanocarrier for the enhancement of efficacy and safety of the bone anabolic PTH 1-34. ANC is expected to reduce the cost, dosage, and dose frequency associated with the use of PTH 1-34 management of primary and secondary forms of osteoporosis. PMID:28176933

Solvothermal synthesis of TiO2 nanocrystals with {001} facets using titanic acid nanobelts for superior photocatalytic activity

NASA Astrophysics Data System (ADS)

Cao, Yuhui; Zong, Lanlan; Li, Qiuye; Li, Chen; Li, Junli; Yang, Jianjun

2017-01-01

Anatase TiO2 nanocrystals exposed with {001} facets were fabricated by solvothermal strategy in HF-C4H9OH mixed solution, using titanic acid nanobelts (TAN) as a precursor. The shape of TAN is a long flat plane with a high aspect ratio, and F- is easily adsorbed on the surface of the nanobelts, inducing a higher exposure of {001} facet of TiO2 nanoparticles during the structure reorganization. The exposed percentage of {001} facets could vary from 40 to 77% by adjusting the amount of HF. The as-prepared samples were characterized by transmission electron microscopy, N2 adsorption-desorption isotherms, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscope. The photocatalytic measurement showed that TiO2 nanocrystals with 77% {001} facets exhibited much superior photocatalytic activity for photodegradation of methyl orange, methylene blue, and rhodamine B. And what's more, the mineralization rate of methyl orange was as high as 96% within 60 min. The photocatalytic enhancement is due to a large amount of the high energetic {001} facets exposing, the special truncated octahedral morphology and a stronger ability for dyes adsorption.

Metal Sulfide Nanocrystals inside Ferritin with Photovoltaic Applications

NASA Astrophysics Data System (ADS)

Hansen, Kameron; Peterson, J. Ryan; Olsen, Cameron; Hogg, Heather; Colton, John; Watt, Richard; Colton Team

Ferritin is a spherical protein shell used universally by organisms to store iron. Due to a number of ferritin's properties (a conductive shell, ability to be arranged in ordered arrays, and high stability), recent theoretical work has proposed that non-native semiconductor nanocrystals inside ferritin can be used for high-efficiency solar energy conversion. We present research on the synthesis of a variety of these nanocrystals (PbS, CuS, Mo2S, ZnS, and PbSe) inside ferritin's hollow interior and band gap energies of the resulting ferritin-nanocrystal constructs. We also report preliminary solar cell results for dye sensitized solar cells with PbS-ferritin as the dye.

Colloidal Synthesis and Thermoelectric Properties of CuFeSe2 Nanocrystals

PubMed Central

Zhang, Bing-Qian; Zuo, Yong; Chen, Jing-Shuai; Niu, He-Lin; Mao, Chang-Jie

2017-01-01

Copper-based chalcogenides that contain abundant, low-cost and environmentally-friendly elements, are excellent materials for numerous energy conversion applications, such as photocatalysis, photovoltaics, photoelectricity and thermoelectrics (TE). Here, we present a high-yield and upscalable colloidal synthesis route for the production of monodisperse ternary I-III-VI2 chalcogenides nanocrystals (NCs), particularly stannite CuFeSe2, with uniform shape and narrow size distributions by using selenium powder as the anion precursor and CuCl2·2H2O and FeCl3 as the cationic precursors. The composition, the state of valence, size and morphology of the CuFeSe2 materials were examined by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), transmission electron microscope (TEM) and high resolution transmission electron microscope (HRTEM), respectively. Furthermore, the TE properties characterization of these dense nanomaterials compacted from monodisperse CuFeSe2 NCs by hot press at 623 K were preliminarily studied after ligand removal by means of hydrazine and hexane solution. The TE performances of the sintered CuFeSe2 pellets were characterized in the temperature range from room temperature to 653 K. Finally, the dimensionless TE figure of merit (ZT) of this Earth-abundant and intrinsic p-type CuFeSe2 NCs is significantly increased to 0.22 at 653 K in this work, which is demonstrated to show a promising TE materialand makes it a possible p-type candidate for medium-temperature TE applications. PMID:29278381

Morphology evolution of single-crystalline hematite nanocrystals: magnetically recoverable nanocatalysts for enhanced facet-driven photoredox activity

NASA Astrophysics Data System (ADS)

Patra, Astam K.; Kundu, Sudipta K.; Bhaumik, Asim; Kim, Dukjoon

2015-12-01

We have developed a new green chemical approach for the shape-controlled synthesis of single-crystalline hematite nanocrystals in aqueous medium. FESEM, HRTEM and SAED techniques were used to determine the morphology and crystallographic orientations of each nanocrystal and its exposed facets. PXRD and HRTEM techniques revealed that the nanocrystals are single crystalline in nature; twins and stacking faults were not detected in these nanocrystals. The structural, vibrational, and electronic spectra of these nanocrystals were highly dependent on their shape. Different shaped hematite nanocrystals with distinct crystallographic planes have been synthesized under similar reaction conditions, which can be desired as a model for the purpose of properties comparison with the nanocrystals prepared under different reaction conditions. Here we investigated the photocatalytic performance of these different shaped-nanocrystals for methyl orange degradation in the presence of white light (λ > 420 nm). In this study, we found that the density of surface Fe3+ ions in particular facets was the key factor for the photocatalytic activity and was higher on the bitruncated-dodecahedron shape nanocrystals by coexposed {104}, {100} and {001} facets, attributing to higher catalytic activity. The catalytic activity of different exposed facet nanocrystals were as follows: {104} + {100} + {001} (bitruncated-dodecahedron) > {101} + {001} (bitruncated-octahedron) > {001} + {110} (nanorods) > {012} (nanocuboid) which provided the direct evidence of exposed facet-driven photocatalytic activity. The nanocrystals were easily recoverable using an external magnet and reused at least six times without significant loss of its catalytic activity.We have developed a new green chemical approach for the shape-controlled synthesis of single-crystalline hematite nanocrystals in aqueous medium. FESEM, HRTEM and SAED techniques were used to determine the morphology and crystallographic orientations of each nanocrystal and its exposed facets. PXRD and HRTEM techniques revealed that the nanocrystals are single crystalline in nature; twins and stacking faults were not detected in these nanocrystals. The structural, vibrational, and electronic spectra of these nanocrystals were highly dependent on their shape. Different shaped hematite nanocrystals with distinct crystallographic planes have been synthesized under similar reaction conditions, which can be desired as a model for the purpose of properties comparison with the nanocrystals prepared under different reaction conditions. Here we investigated the photocatalytic performance of these different shaped-nanocrystals for methyl orange degradation in the presence of white light (λ > 420 nm). In this study, we found that the density of surface Fe3+ ions in particular facets was the key factor for the photocatalytic activity and was higher on the bitruncated-dodecahedron shape nanocrystals by coexposed {104}, {100} and {001} facets, attributing to higher catalytic activity. The catalytic activity of different exposed facet nanocrystals were as follows: {104} + {100} + {001} (bitruncated-dodecahedron) > {101} + {001} (bitruncated-octahedron) > {001} + {110} (nanorods) > {012} (nanocuboid) which provided the direct evidence of exposed facet-driven photocatalytic activity. The nanocrystals were easily recoverable using an external magnet and reused at least six times without significant loss of its catalytic activity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06509g

Size-tunable phosphorescence in colloidal metastable gamma-Ga2O3 nanocrystals.

PubMed

Wang, Ting; Farvid, Shokouh S; Abulikemu, Mutalifu; Radovanovic, Pavle V

2010-07-14

We report a colloidal synthesis of gallium oxide (Ga(2)O(3)) nanocrystals having metastable cubic crystal structure (gamma phase) and uniform size distribution. Using the synthesized nanocrystal size series we demonstrate for the first time a size-tunable photoluminescence in Ga(2)O(3) from ultraviolet to blue, with the emission shifting to lower energies with increasing nanocrystal size. The observed photoluminescence is dominated by defect-based donor-acceptor pair recombination and has a lifetime of several milliseconds. Importantly, the decay of this phosphorescence is also size dependent. The phosphorescence energy and the decay rate increase with decreasing nanocrystal size, owing to a reduced donor-acceptor separation. These results allow for a rational and predictable tuning of the optical properties of this technologically important material and demonstrate the possibility of manipulating the localized defect interactions via nanocrystal size. Furthermore, the same defect states, particularly donors, are also implicated in electrical conductivity rendering monodispersed Ga(2)O(3) nanocrystals a promising material for multifunctional optoelectronic structures and devices.

Turning the halide switch in the synthesis of Au–Pd alloy and core–shell nanoicosahedra with terraced shells: Performance in electrochemical and plasmon-enhanced catalysis

DOE PAGES

Hsu, Shih -Cheng; Chuang, Yu -Chun; Sneed, Brian T.; ...

2016-01-01

Au Pd nanocrystals are an intriguing system to study the integrated functions of localized surface plasmon resonance (LSPR) and heterogeneous catalysis. Gold is both durable and can harness incident light energy to enhance the catalytic activity of another metal, such as Pd, via the SPR effect in bimetallic nanocrystals. Despite the superior catalytic performance of icosahedral (IH) nanocrystals compared to alternate morphologies, the controlled synthesis of alloy and core shell IH is still greatly challenged by the disparate reduction rates of metal precursors and lack of continuous epigrowth on multiply twinned boundaries of such surfaces. Herein, we demonstrate a one-stepmore » strategy for the controlled growth of monodisperse Au Pd alloy and core shell IH with terraced shells by turning an ionic switch between [Br ]/[Cl –] in the coreduction process. The core shell IH nanocrystals contain AuPd alloy cores and ultrathin Pd shells (<2 nm). They not only display more than double the activity of the commercial Pd catalysts in ethanol electrooxidation attributed to monatomic step terraces but also show SPR-enhanced conversion of 4-nitrophenol. Furthermore, this strategy holds promise toward the development of alternate bimetallic IH nanocrystals for electrochemical and plasmon-enhanced catalysis.« less

A GREENER SYNTHESIS OF CORE (FE, CU)-SHELL (AU, PT, PD AND AG) NANOCRYSTALS USING AQUEOUS VITAMIN C

EPA Science Inventory

A greener method to fabricate the novel core (Fe and Cu)-shell (noble metals) metal nanocrystals using aqueous ascorbic acid (vitamin C) is described. Transition metal salts such as Cu and Fe were reduced using ascorbic acid, a benign naturally available antioxidant, and then add...

In situ functionalization and PEO coating of iron oxide nanocrystals using seeded emulsion polymerization.

PubMed

Kloust, Hauke; Schmidtke, Christian; Feld, Artur; Schotten, Theo; Eggers, Robin; Fittschen, Ursula E A; Schulz, Florian; Pöselt, Elmar; Ostermann, Johannes; Bastús, Neus G; Weller, Horst

2013-04-16

Herein we demonstrate that seeded emulsion polymerization is a powerful tool to produce multiply functionalized PEO coated iron oxide nanocrystals. Advantageously, by simple addition of functional surfactants, functional monomers, or functional polymerizable linkers-solely or in combinations thereof-during the seeded emulsion polymerization process, a broad range of in situ functionalized polymer-coated iron oxide nanocrystals were obtained. This was demonstrated by purposeful modulation of the zeta potential of encapsulated iron oxide nanocrystals and conjugation of a dyestuff. Successful functionalization was unequivocally proven by TXRF. Furthermore, the spatial position of the functional groups can be controlled by choosing the appropriate spacers. In conclusion, this methodology is highly amenable for combinatorial strategies and will spur rapid expedited synthesis and purposeful optimization of a broad scope of nanocrystals.

Aqueous based synthesis of N-acetyl-L-cysteine capped ZnSe nanocrystals with intense blue emission

NASA Astrophysics Data System (ADS)

Soheyli, Ehsan; Sahraei, Reza; Nabiyouni, Gholamreza

2016-10-01

In this work a very simple reflux route for preparation of ZnSe nanocrystals with minor modification and faster preparation over conventional ones is introduced. X-ray diffraction analysis indicated that the ZnSe nanocrystals have a cubic structure. The complete disappearance of the S-H band in FT-IR spectrum of N-acetyl-L-cysteine capped ZnSe nanocrystals was an indication over formation of Zn-thiol covalent bonds at the surface of the nanocrystals which results in passivation of small nanocrystals. The strong size-quantization regime was responsible of significant blue shift in absorption/emission spectra. Using the well-known calculations, band gap and Urbach energy of the ZnSe nanocrystals were measured and their average size was estimated optically to be around 4.6 nm along with the TEM image. A dark blue emission with higher relative intensity of excitonic to trap emissions (compared to conventional method), very narrow excitonic emission peak of about 16 nm and remarkable stability was obtained from the ZnSe nanocrystals.

Osteoblasts Growth Behaviour on Bio-Based Calcium Carbonate Aragonite Nanocrystal

PubMed Central

Zakaria, Zuki Abu Bakar

2014-01-01

Calcium carbonate (CaCO3) nanocrystals derived from cockle shells emerge to present a good concert in bone tissue engineering because of their potential to mimic the composition, structure, and properties of native bone. The aim of this study was to evaluate the biological response of CaCO3 nanocrystals on hFOB 1.19 and MC3T3 E-1 osteoblast cells in vitro. Cell viability and proliferation were assessed by MTT and BrdU assays, and LDH was measured to determine the effect of CaCO3 nanocrystals on cell membrane integrity. Cellular morphology was examined by SEM and fluorescence microscopy. The results showed that CaCO3 nanocrystals had no toxic effects to some extent. Cell proliferation, alkaline phosphatase activity, and protein synthesis were enhanced by the nanocrystals when compared to the control. Cellular interactions were improved, as indicated by SEM and fluorescent microscopy. The production of VEGF and TGF-1 was also affected by the CaCO3 nanocrystals. Therefore, bio-based CaCO3 nanocrystals were shown to stimulate osteoblast differentiation and improve the osteointegration process. PMID:24734228

Atomic level characterization of cadmium selenide nanocrystal systems using atomic number contrast scanning transmission electron microscopy and Rutherford backscattering spectroscopy

NASA Astrophysics Data System (ADS)

McBride, James R.

This project involved the characterization of CdSe nanocrystals. Through the use of Atomic Number Contrast Scanning Transmission Electron Microscopy (Z-STEM) and Rutherford Backscattering Spectroscopy (RBS), atomic level structure and chemical information was obtained. Specifically, CdSe nanocrystals produced using a mixture of hexadecylamine (HDA) and trioctylphosphine oxide (TOPO) were determined to be spherical compared to nanocrystals produced in TOPO only, which had elongated (101) facets. Additionally, the first Z-STEM images of CdSe/ZnS core/shell nanocrystals were obtained. From these images, the growth mechanism of the ZnS shell was determined and the existence of non-fluorescent ZnS particles was confirmed. Through collaboration with Quantum Dot Corp., core/shell nanocrystals with near unity quantum yield were developed. These core/shell nanocrystals included a US intermediate layer to improve shell coverage.

Continuous and rapid synthesis of nanoclusters and nanocrystals using scalable microstructured reactors

NASA Astrophysics Data System (ADS)

Jin, Hyung Dae

Recent advances in nanocrystalline materials production are expected to impact the development of next generation low-cost and/or high efficiency solar cells. For example, semiconductor nanocrystal inks are used to lower the fabrication cost of the absorber layers of the solar cells. In addition, some quantum confined nanocrystals display electron-hole pair generation phenomena with greater than 100% quantum yield, called multiple exciton generation (MEG). These quantum dots could potentially be used to fabricate solar cells that exceed the Schockley-Queisser limit. At present, continuous syntheses of nanoparticles using microreactors have been reported by several groups. Microreactors have several advantages over conventional batch synthesis. One advantage is their efficient heat transfer and mass transport. Another advantage is the drastic reduction in the reaction time, in many cases, down to minutes from hours. Shorter reaction time not only provides higher throughput but also provide better particle size control by avoiding aggregation and by reducing probability of oxidizing precursors. In this work, room temperature synthesis of Au11 nanoclusters and high temperature synthesis of chalcogenide nanocrystals were demonstrated using continuous flow microreactors with high throughputs. A high rate production of phosphine-stabilized Au11 nanoclusters was achieved using a layer-up strategy which involves the use of microlamination architectures; the patterning and bonding of thin layers of material (laminae) to create a multilayered micromixer in the range of 25-250 mum thick was used to step up the production of phosphine-stabilized Au11 nanoclusters. Continuous production of highly monodispersed phosphine-stabilized Au 11 nanoclusters at a rate of about 11.8 [mg/s] was achieved using a microreactor with a size of 1.687cm3. This result is about 30,000 times over conventional batch synthesis according to production rate/per reactor volume. We have elucidated the formation mechanism of CuInSe2 nanocrystals for the development of a continuous flow process for their synthesis. It was found that copper-rich CuInSe2 with a sphalerite structure was formed initially followed by the formation of more ordered CuInSe2 at longer reaction times, along with the formation of Cu2Se and In2Se3. It was found that Cu2Se was formed at a much faster rate than In2Se3 under the same reaction conditions. By adjusting the Cu/In precursor ratio, we were able to develop a very rapid and simple synthesis of CuInSe2 nanocrystals using a continuous flow microreactor with a high throughput per reactor volume. The microreactor has a simple design which uses readily available low cost components. It comprised an inner microtube to precisely control the injection of TOPSe into a larger diameter tube that preheated CuCl and InCl3 hot mixture was pumped through. Rapid injection plays an important role in dividing the nucleation and growth process which is crucial in getting narrow size distribution. The design of this microreactor also has the advantages of alleviating sticking of QDs on the growth channel wall since QDs were formed from the center of the reactor. Furthermore, size-controlled synthesis of CuInSe2 nanocrystals was achieved using this reactor simply by adjusting ratio between coordinating solvents. Semiconductors with a direct bandgap between 1 and 2eV including Cu(In,Ga)Se 2 (1.04--1.6eV) and CuIn(Se,S)2 (1.04--1.53eV) are ideal for single junction cells utilize the visible spectrum. However, half of the solar energy available to the Earth lies in the infrared region. Inorganic QD-based solar cells with a decent efficiency near 1.5 mum have been reported. Therefore, syntheses of narrow gap IV-VI (SnTe, PbS, PbSe, PbTe), II-IV (HgTe, CdXHg1-XTe), and III-V (InAs) QDs have attracted significant attention and these materials have potential uses for a variety of other optical, electronic, and optoelectronic applications. SnTe with an energy gap of 0.18eV at 300K can be used for IR photodetectors, laser diodes, and thermophotovoltaic energy converters. First continuous synthesis of shape-controlled SnTe nanocrystals were also accomplished in this work. SnCl2, and TOPTe were used as reactants successfully in coordinating OA and TOP solvents. Both rod shape and dot shape SnTe nanocrystals with uniform size distributions could be obtained. A blue shift was observed from these SnTe nanocrystals. Production rate at about 5mg/min (300mg/hr) was achieved using a microreactor at a size of 1.78cm3.

High-temperature crystallization of nanocrystals into three-dimensional superlattices.

PubMed

Wu, Liheng; Willis, Joshua J; McKay, Ian Salmon; Diroll, Benjamin T; Qin, Jian; Cargnello, Matteo; Tassone, Christopher J

2017-08-10

Crystallization of colloidal nanocrystals into superlattices represents a practical bottom-up process with which to create ordered metamaterials with emergent functionalities. With precise control over the size, shape and composition of individual nanocrystals, various single- and multi-component nanocrystal superlattices have been produced, the lattice structures and chemical compositions of which can be accurately engineered. Nanocrystal superlattices are typically prepared by carefully controlling the assembly process through solvent evaporation or destabilization or through DNA-guided crystallization. Slow solvent evaporation or cooling of nanocrystal solutions (over hours or days) is the key element for successful crystallization processes. Here we report the rapid growth (seconds) of micrometre-sized, face-centred-cubic, three-dimensional nanocrystal superlattices during colloidal synthesis at high temperatures (more than 230 degrees Celsius). Using in situ small-angle X-ray scattering, we observe continuous growth of individual nanocrystals within the lattices, which results in simultaneous lattice expansion and fine nanocrystal size control due to the superlattice templates. Thermodynamic models demonstrate that balanced attractive and repulsive interparticle interactions dictated by the ligand coverage on nanocrystal surfaces and nanocrystal core size are responsible for the crystallization process. The interparticle interactions can also be controlled to form different superlattice structures, such as hexagonal close-packed lattices. The rational assembly of various nanocrystal systems into novel materials is thus facilitated for both fundamental research and for practical applications in the fields of magnetics, electronics and catalysis.

High-temperature crystallization of nanocrystals into three-dimensional superlattices

NASA Astrophysics Data System (ADS)

Wu, Liheng; Willis, Joshua J.; McKay, Ian Salmon; Diroll, Benjamin T.; Qin, Jian; Cargnello, Matteo; Tassone, Christopher J.

2017-08-01

Crystallization of colloidal nanocrystals into superlattices represents a practical bottom-up process with which to create ordered metamaterials with emergent functionalities. With precise control over the size, shape and composition of individual nanocrystals, various single- and multi-component nanocrystal superlattices have been produced, the lattice structures and chemical compositions of which can be accurately engineered. Nanocrystal superlattices are typically prepared by carefully controlling the assembly process through solvent evaporation or destabilization or through DNA-guided crystallization. Slow solvent evaporation or cooling of nanocrystal solutions (over hours or days) is the key element for successful crystallization processes. Here we report the rapid growth (seconds) of micrometre-sized, face-centred-cubic, three-dimensional nanocrystal superlattices during colloidal synthesis at high temperatures (more than 230 degrees Celsius). Using in situ small-angle X-ray scattering, we observe continuous growth of individual nanocrystals within the lattices, which results in simultaneous lattice expansion and fine nanocrystal size control due to the superlattice templates. Thermodynamic models demonstrate that balanced attractive and repulsive interparticle interactions dictated by the ligand coverage on nanocrystal surfaces and nanocrystal core size are responsible for the crystallization process. The interparticle interactions can also be controlled to form different superlattice structures, such as hexagonal close-packed lattices. The rational assembly of various nanocrystal systems into novel materials is thus facilitated for both fundamental research and for practical applications in the fields of magnetics, electronics and catalysis.

Nanocrystals-Related Synthesis, Assembly, and Energy Applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zou, Bo; Yu, Williams; Seo, Jaetae

2012-01-01

During the past decades, nanocrystals have attracted broad attention due to their unique shape- and size-dependent physical and chemical properties that differ drastically from their bulk counterparts. Hitherto, much effort has been dedicated to achieving rational controlling over the morphology, assembly, and related energy applications of the nanomaterials. Therefore, the ability to manipulate the morphology, size, and size distribution of inorganic nanomaterials is still an important goal in modern materials physics and chemistry. Especially, the world s demand for energy supply is causing a dramatic escalation of social and political unrest. Likewise, the environmental impact of the global climate changemore » due to the combustion of fossil fuel is becoming increasingly alarming. These problems compel us to search for effective routes to build devices that can supply sustainable energy, with not only high efficiency but also environmental friendship. One of ways to relieve the energy crisis is to exploit devices based on renewable energy sources, such as solar energy and water power. Aiming at this exploration, the primary stage requires the design of appropriate strategies for the synthesis of high-quality nanocrystals with respect to size uniformity and superior electrochemical performances. As a consequence, we organize the current special issue for Journal of Nanomaterials to provide the authors with a platform and readers with the latest achievements of nanocrystals-related synthesis, assembly, and energy applications.« less

Non-Aqueous Sol-Gel Synthesis of FePt Nanoparticles in the Absence of In Situ Stabilizers

PubMed Central

Preller, Tobias; Knickmeier, Saskia; Porsiel, Julian Cedric; Temel, Bilal

2018-01-01

The synthesis of FePt nanocrystals is typically performed in an organic solvent at rather high temperatures, demanding the addition of the in situ stabilizers oleic acid and oleylamine to produce monomodal particles with well-defined morphologies. Replacing frequently-used solvents with organic media bearing functional moieties, the use of the stabilizers can be completely circumvented. In addition, various morphologies and sizes of the nanocrystals can be achieved by the choice of organic solvent. The kinetics of particle growth and the change in the magnetic behavior of the superparamagnetic FePt nanocrystals during the synthesis with a set of different solvents, as well as the resulting morphologies and stoichiometries of the nanoparticles were determined by powder X-ray diffraction (PXRD), small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), inductively coupled plasma optical emission spectroscopy (ICP-OES)/mass spectrometry (ICP-MS), and superconducting quantum interference device (SQUID) measurements. Furthermore, annealing of the as-prepared FePt nanoparticles led to the ordered L10 phase and, thus, to hard magnetic materials with varying saturation magnetizations and magnetic coercivities. PMID:29751508

Mono- and bi-functional arenethiols as surfactants for gold nanoparticles: synthesis and characterization

PubMed Central

2011-01-01

Stable gold nanoparticles stabilized by different mono and bi-functional arenethiols, namely, benzylthiol and 1,4-benzenedimethanethiol, have been prepared by using a modified Brust's two-phase synthesis. The size, shape, and crystalline structure of the gold nanoparticles have been determined by high-resolution electron microscopy and full-pattern X-ray powder diffraction analyses. Nanocrystals diameters have been tuned in the range 2 ÷ 9 nm by a proper variation of Au/S molar ratio. The chemical composition of gold nanoparticles and their interaction with thiols have been investigated by X-ray photoelectron spectroscopy. In particular, the formation of networks has been observed with interconnected gold nanoparticles containing 1,4-benzenedimethanethiol as ligand. PMID:21711615

Mesoporous CdS via Network of Self-Assembled Nanocrystals: Synthesis, Characterization and Enhanced Photoconducting Property.

PubMed

Patra, Astam K; Banerjee, Biplab; Bhaumik, Asim

2018-01-01

Semiconduction nanoparticles are intensively studied due to their huge potential in optoelctronic applications. Here we report an efficient chemical route for hydrothermal synthesis of aggregated mesoporous cadmium sulfide (CdS) nanoparticles using supramolecular-assembly of ionic and water soluble sodium salicylate as the capping agent. The nanostructure, mesophase, optical property and photoconductivity of these mesoporous CdS materials have been characterized by using small and wide angle powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), N2-sorption, Raman analysis, Fourier transformed infrared (FT-IR), UV-Visible DSR spectroscopy, and photoconductivity measurement. Wide angle XRD pattern and high resolution TEM image analysis suggested that the particle size of the materials is within 10 nm and the nanoparticles are in well-crystallized cubic phase. Mesoporous CdS nanoparticles showed drastically enhanced photoelectrochemical response under visible light irradiation on entrapping a photosensitizer (dye) molecule in the interparticle spaces. Efficient synthesis strategy and the enhanced photo response in the mesoporous CdS material could facilitate the designing of other porous semiconductor oxide/sulfide and their applications in photon-to-electron conversion processes.

One-step DNA-programmed growth of luminescent and biofunctionalized nanocrystals

NASA Astrophysics Data System (ADS)

Ma, Nan; Sargent, Edward H.; Kelley, Shana O.

2009-02-01

Colloidal semiconductor nanocrystals are widely used as lumiphores in biological imaging because their luminescence is both strong and stable, and because they can be biofunctionalized. During synthesis, nanocrystals are typically passivated with hydrophobic organic ligands, so it is then necessary either to replace these ligands or encapsulate the nanocrystals with hydrophilic moieties to make the lumiphores soluble in water. Finally, biological labels must be added to allow the detection of nucleic acids, proteins and specific cell types. This multistep process is time- and labour-intensive and thus out of reach of many researchers who want to use luminescent nanocrystals as customized lumiphores. Here, we show that a single designer ligand-a chimeric DNA molecule-can controllably program both the growth and the biofunctionalization of the nanocrystals. One part of the DNA sequence controls the nanocrystal passivation and serves as a ligand, while another part controls the biorecognition. The synthetic protocol reported here is straightforward and produces a homogeneous dispersion of nanocrystal lumiphores functionalized with a single biomolecular receptor. The nanocrystals exhibit strong optical emission in the visible region, minimal toxicity and have hydrodynamic diameters of ~6 nm, which makes them suitable for bioimaging. We show that the nanocrystals can specifically bind DNA, proteins or cells that have unique surface recognition markers.

Semiconductor nanocrystals covalently bound to solid inorganic surfaces using self-assembled monolayers

DOEpatents

Alivisatos, A. Paul; Colvin, Vicki L.

1998-01-01

Methods are described for attaching semiconductor nanocrystals to solid inorganic surfaces, using self-assembled bifunctional organic monolayers as bridge compounds. Two different techniques are presented. One relies on the formation of self-assembled monolayers on these surfaces. When exposed to solutions of nanocrystals, these bridge compounds bind the crystals and anchor them to the surface. The second technique attaches nanocrystals already coated with bridge compounds to the surfaces. Analyses indicate the presence of quantum confined clusters on the surfaces at the nanolayer level. These materials allow electron spectroscopies to be completed on condensed phase clusters, and represent a first step towards synthesis of an organized assembly of clusters. These new products are also disclosed.

Atmospheric-pressure glow plasma synthesis of plasmonic and photoluminescent zinc oxide nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bilik, N., E-mail: bilik006@umn.edu, E-mail: kortshagen@umn.edu; Greenberg, B. L.; Yang, J.

In this paper, we present a large-volume (non-micro) atmospheric pressure glow plasma capable of rapid, large-scale zinc oxide nanocrystal synthesis and deposition (up to 400 μg/min), whereas in the majority of the literature, nanoparticles are synthesized using micro-scale or filamentary plasmas. The reactor is an RF dielectric barrier discharge with a non-uniform gap spacing. This design encourages pre-ionization during the plasma breakdown, making the discharge uniform over a large volume. The produced zinc oxide nanocrystals typically have diameters ranging from 4 to 15 nm and exhibit photoluminescence at ≈550 nm and localized surface plasmon resonance at ≈1900 cm{sup −1} due to oxygen vacancies. Themore » particle size can be tuned to a degree by varying the gas temperature and the precursor mixing ratio.« less

Self-assembled ultra small ZnO nanocrystals for dye-sensitized solar cell application

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patra, Astam K.; Dutta, Arghya; Bhaumik, Asim, E-mail: msab@iacs.res.in

2014-07-01

We demonstrate a facile chemical approach to produce self-assembled ultra-small mesoporous zinc oxide nanocrystals using sodium salicylate (SS) as a template under hydrothermal conditions. These ZnO nanomaterials have been successfully fabricated as a photoanode for the dye-sensitized solar cell (DSSC) in the presence of N719 dye and iodine–triiodide electrolyte. The structural features, crystallinity, purity, mesophase and morphology of the nanostructure ZnO are investigated by several characterization tools. N{sub 2} sorption analysis revealed high surface areas (203 m{sup 2} g{sup −1}) and narrow pore size distributions (5.1–5.4 nm) for different samples. The mesoporous structure and strong photoluminescence facilitates the high dyemore » loading at the mesoscopic void spaces and light harvesting in DSSC. By utilizing this ultra-small ZnO photoelectrode with film thickness of about 7 μm in the DSSC with an open-circuit voltage (V{sub OC}) of 0.74 V, short-circuit current density (J{sub SC}) of 3.83 mA cm{sup −2} and an overall power conversion efficiency of 1.12% has been achieved. - Graphical abstract: Ultra-small ZnO nanocrystals have been synthesized with sodium salicylate as a template and using it as a photoanode in a dye-sensitized solar cell 1.12% power conversion efficiency has been observed. - Highlights: • Synthesis of self-assembled ultra-small mesoporous ZnO nanocrystals by using sodium salicylate as a template. • Mesoporous ZnO materials have high BET surface areas and void space. • ZnO nanoparticles serve as a photoanode for the dye-sensitized solar cell (DSSC). • Using ZnO nanocrystals as photoelectrode power conversion efficiency of 1.12% has been achieved.« less

Negative results of growing titania nanotubes on cellulose nanocrystals - Effect of hydrothermal reaction

NASA Astrophysics Data System (ADS)

Chamakh, Mariem Mohamed; Ponnamma, Deepalekshmi; Al-Maadeed, Mariam Al Ali

Titania nanotubes (TiO2 nanotubes or TNT) are grown hydrothermally on cellulose nanocrystals (CNC) synthesized from microcrystalline cellulose. It is observed that the CNC are lost during synthesis due to its low thermal stability. This negative result of metal growth on CNC and its influence on thermal degradation are reported here.

Low temperature synthesis and characterization of carbonated hydroxyapatite nanocrystals

NASA Astrophysics Data System (ADS)

Anwar, Aneela; Asghar, Muhammad Nadeem; Kanwal, Qudsia; Kazmi, Mohsin; Sadiqa, Ayesha

2016-08-01

Carbonate substituted hydroxyapatite (CHA) nanorods were synthesized via coprecipitation method from aqueous solution of calcium nitrate tetrahydrate and diammonium hydrogen phosphate (with urea as carbonate ion source) in the presence of ammonium hydroxide solution at 70 °C at the conditions of pH 11. The obtained powders were physically characterized using transmission electron microscopy (TEM), X-ray powder diffraction analysis (XRD), and FTIR and Raman spectroscopy. The particle size was evaluated by Dynamic light scattering (DLS). The chemical structural analysis of as prepared sample was performed using X-ray photoelectron spectroscopy (XPS). After ageing for 12 h, and heat treatment at 1000 °C for 1 h, the product was obtained as highly crystalline nanorods of CHA.

Designing lanthanide-doped nanocrystals with both up- and down-conversion luminescence for anti-counterfeiting

NASA Astrophysics Data System (ADS)

Liu, Yanlan; Ai, Kelong; Lu, Lehui

2011-11-01

The widespread forgery in all kinds of paper documents and certificates has become a real threat to society. Traditional fluorescent anti-counterfeiting materials generally exhibit unicolor display and suffer greatly from substitution, thus leading to a poor anti-counterfeiting effect. In this work, unseen but significant enhanced blue down-conversion emission from oleic acid-stabilized lanthanide-doped fluoride nanocrystals is first present and the mechanism is proposed and validated. This not only endows these nanocrystals with dual-mode fluorescence, but also offers a simplified synthesis approach for dual-mode fluorescent nanocrystals involving no further complicated assembly or coating procedures, unlike the traditional methods. Furthermore, by changing the host/dopant combination or the content of dopant, these nanocrystals can exhibit simultaneously multicolor up-conversion emission under excitation at near-infrared light and unalterable blue down-conversion emission under ultraviolet light. A preliminary investigation of their anti-counterfeiting performance has been made, and the results indicate that this color tuning capability and high concealment makes these nanocrystals behave in a similar way to chameleons and can provide a strengthened and more reliable anti-counterfeiting effect.The widespread forgery in all kinds of paper documents and certificates has become a real threat to society. Traditional fluorescent anti-counterfeiting materials generally exhibit unicolor display and suffer greatly from substitution, thus leading to a poor anti-counterfeiting effect. In this work, unseen but significant enhanced blue down-conversion emission from oleic acid-stabilized lanthanide-doped fluoride nanocrystals is first present and the mechanism is proposed and validated. This not only endows these nanocrystals with dual-mode fluorescence, but also offers a simplified synthesis approach for dual-mode fluorescent nanocrystals involving no further complicated assembly or coating procedures, unlike the traditional methods. Furthermore, by changing the host/dopant combination or the content of dopant, these nanocrystals can exhibit simultaneously multicolor up-conversion emission under excitation at near-infrared light and unalterable blue down-conversion emission under ultraviolet light. A preliminary investigation of their anti-counterfeiting performance has been made, and the results indicate that this color tuning capability and high concealment makes these nanocrystals behave in a similar way to chameleons and can provide a strengthened and more reliable anti-counterfeiting effect. Electronic supplementary information (ESI) available: Fig. S1-S6, Table S. See DOI: 10.1039/c1nr10752f

Green Synthesis of Nanocrystals and Nanocomposites

EPA Science Inventory

Metal nanomaterials have attracted considerable attention because of their unique magnetic, optical, electrical, and catalytic properties and their potential applications in nanoelectronics as well as in various wet chemical synthesis methods. There is also great interest in synt...

High-temperature crystallization of nanocrystals into three-dimensional superlattices

DOE PAGES

Wu, Liheng; Willis, Joshua J.; McKay, Ian Salmon; ...

2017-07-31

Crystallization of colloidal nanocrystals into superlattices represents a practical bottom-up process with which to create ordered metamaterials with emergent functionalities. With precise control over the size, shape and composition of individual nanocrystals, various single-and multi-component nanocrystal superlattices have been produced, the lattice structures and chemical compositions of which can be accurately engineered. Nanocrystal superlattices are typically prepared by carefully controlling the assembly process through solvent evaporation or destabilization or through DNA-guided crystallization. Slow solvent evaporation or cooling of nanocrystal solutions (over hours or days) is the key element for successful crystallization processes. Here we report the rapid growth (seconds) ofmore » micrometre-sized, face-centred-cubic, three-dimensional nanocrystal superlattices during colloidal synthesis at high temperatures (more than 230 degrees Celsius). Using in situ small-angle X-ray scattering, we observe continuous growth of individual nanocrystals within the lattices, which results in simultaneous lattice expansion and fine nanocrystal size control due to the superlattice templates. Thermodynamic models demonstrate that balanced attractive and repulsive interparticle interactions dictated by the ligand coverage on nanocrystal surfaces and nanocrystal core size are responsible for the crystallization process. The interparticle interactions can also be controlled to form different superlattice structures, such as hexagonal close-packed lattices. In conclusion, the rational assembly of various nanocrystal systems into novel materials is thus facilitated for both fundamental research and for practical applications in the fields of magnetics, electronics and catalysis.« less

Iron-doped nickel oxide nanocrystals as highly efficient electrocatalysts for alkaline water splitting.

PubMed

Fominykh, Ksenia; Chernev, Petko; Zaharieva, Ivelina; Sicklinger, Johannes; Stefanic, Goran; Döblinger, Markus; Müller, Alexander; Pokharel, Aneil; Böcklein, Sebastian; Scheu, Christina; Bein, Thomas; Fattakhova-Rohlfing, Dina

2015-05-26

Efficient electrochemical water splitting to hydrogen and oxygen is considered a promising technology to overcome our dependency on fossil fuels. Searching for novel catalytic materials for electrochemical oxygen generation is essential for improving the total efficiency of water splitting processes. We report the synthesis, structural characterization, and electrochemical performance in the oxygen evolution reaction of Fe-doped NiO nanocrystals. The facile solvothermal synthesis in tert-butanol leads to the formation of ultrasmall crystalline and highly dispersible FexNi1-xO nanoparticles with dopant concentrations of up to 20%. The increase in Fe content is accompanied by a decrease in particle size, resulting in nonagglomerated nanocrystals of 1.5-3.8 nm in size. The Fe content and composition of the nanoparticles are determined by X-ray photoelectron spectroscopy and energy-dispersive X-ray spectroscopy measurements, while Mössbauer and extended X-ray absorption fine structure analyses reveal a substitutional incorporation of Fe(III) into the NiO rock salt structure. The excellent dispersibility of the nanoparticles in ethanol allows for the preparation of homogeneous ca. 8 nm thin films with a smooth surface on various substrates. The turnover frequencies (TOF) of these films could be precisely calculated using a quartz crystal microbalance. Fe0.1Ni0.9O was found to have the highest electrocatalytic water oxidation activity in basic media with a TOF of 1.9 s(-1) at the overpotential of 300 mV. The current density of 10 mA cm(-2) is reached at an overpotential of 297 mV with a Tafel slope of 37 mV dec(-1). The extremely high catalytic activity, facile preparation, and low cost of the single crystalline FexNi1-xO nanoparticles make them very promising catalysts for the oxygen evolution reaction.

Tiny Grains Give Huge Gains: Nanocrystal–Based Signal Amplification for Biomolecule Detection

PubMed Central

Tong, Sheng; Ren, Binbin; Zheng, Zhilan; Shen, Han; Bao, Gang

2013-01-01

Nanocrystals, despite their tiny sizes, contain thousands to millions of atoms. Here we show that the large number of atoms packed in each metallic nanocrystal can provide a huge gain in signal amplification for biomolecule detection. We have devised a highly sensitive, linear amplification scheme by integrating the dissolution of bound nanocrystals and metal-induced stoichiometric chromogenesis, and demonstrated that signal amplification is fully defined by the size and atom density of nanocrystals, which can be optimized through well-controlled nanocrystal synthesis. Further, the rich library of chromogenic reactions allows implementation of this scheme in various assay formats, as demonstrated by the iron oxide nanoparticle linked immunosorbent assay (ILISA) and blotting assay developed in this study. Our results indicate that, owing to the inherent simplicity, high sensitivity and repeatability, the nanocrystal based amplification scheme can significantly improve biomolecule quantification in both laboratory research and clinical diagnostics. This novel method adds a new dimension to current nanoparticle-based bioassays. PMID:23659350

Controllable synthesis of nickel bicarbonate nanocrystals with high homogeneity for a high-performance supercapacitor

NASA Astrophysics Data System (ADS)

Gu, Jianmin; Liu, Xin; Wang, Zhuang; Bian, Zhenpan; Jin, Cuihong; Sun, Xiao; Yin, Baipeng; Wu, Tianhui; Wang, Lin; Tang, Shoufeng; Wang, Hongchao; Gao, Faming

2017-08-01

The electrochemical performance of supercapacitors might be associated with the homogeneous structure of the electrode materials. However, the relationship between the degree of uniformity for the electrode materials and the electrochemical performance of the supercapacitor is not clear. Herein, we synthesize two types of nickel bicarbonate nanocrystals with different degrees of uniformity to investigate this relationship. As the electroactive material, the nickel bicarbonate nanocrystals with a homogeneous structure could provide a larger space and offer more exposed atoms for the electrochemical reaction than the nanocrystals with a heterogeneous structure. The homogeneous nickel bicarbonate nanocrystals exhibit better electrochemical performance and show excellent specific capacitance (1596 F g-1 at 2 A g-1 and 1260 F g-1 at 30 A g-1), which is approximately twice that of the heterogeneous nickel bicarbonate nanocrystals. The cycling stability for the homogeneity (˜80%) is higher than the inhomogeneity (˜61%) at a high current density of 5 A g-1.

Shape-Controlled Synthesis of Colloidal Metal Nanocrystals: Thermodynamic versus Kinetic Products.

PubMed

Xia, Younan; Xia, Xiaohu; Peng, Hsin-Chieh

2015-07-01

This Perspective provides a contemporary understanding of the shape evolution of colloidal metal nanocrystals under thermodynamically and kinetically controlled conditions. It has been extremely challenging to investigate this subject in the setting of one-pot synthesis because both the type and number of seeds involved would be changed whenever the experimental conditions are altered, making it essentially impossible to draw conclusions when comparing the outcomes of two syntheses conducted under different conditions. Because of the uncertainty about seeds, most of the mechanistic insights reported in literature for one-pot syntheses of metal nanocrystals with different shapes are either incomplete or ambiguous, and some of them might be misleading or even wrong. Recently, with the use of well-defined seeds for such syntheses, it became possible to separate growth from nucleation and therefore investigate the explicit role(s) played by a specific thermodynamic or kinetic parameter in directing the evolution of colloidal metal nanocrystals into a specific shape. Starting from single-crystal seeds enclosed by a mix of {100}, {111}, and {110} facets, for example, one can obtain colloidal nanocrystals with diversified shapes by adjusting various thermodynamic or kinetic parameters. The mechanistic insights learnt from these studies can also be extended to account for the products of conventional one-pot syntheses that involve self-nucleation only. The knowledge can be further applied to many other types of seeds with twin defects or stacking faults, making it an exciting time to design and synthesize colloidal metal nanocrystals with the shapes sought for a variety of fundamental studies and technologically important applications.

One-pot synthesis of highly luminescent InP/ZnS nanocrystals without precursor injection.

PubMed

Li, Liang; Reiss, Peter

2008-09-03

InP/ZnS core/shell nanocrystals are prepared using a single-step heating-up method relying on the difference in reactivity of the applied InP and ZnS precursors. The obtained particles exhibit size-dependent emission in the range of 480-590 nm, a fluorescence quantum yield of 50-70%, and high photostability.

Semiconductor nanocrystals covalently bound to solid inorganic surfaces using self-assembled monolayers

DOEpatents

Alivisatos, A.P.; Colvin, V.L.

1998-05-12

Methods are described for attaching semiconductor nanocrystals to solid inorganic surfaces, using self-assembled bifunctional organic monolayers as bridge compounds. Two different techniques are presented. One relies on the formation of self-assembled monolayers on these surfaces. When exposed to solutions of nanocrystals, these bridge compounds bind the crystals and anchor them to the surface. The second technique attaches nanocrystals already coated with bridge compounds to the surfaces. Analyses indicate the presence of quantum confined clusters on the surfaces at the nanolayer level. These materials allow electron spectroscopies to be completed on condensed phase clusters, and represent a first step towards synthesis of an organized assembly of clusters. These new products are also disclosed. 10 figs.

Solvothermal synthesis and controlled self-assembly of monodisperse titanium-based perovskite colloidal nanocrystals

NASA Astrophysics Data System (ADS)

Caruntu, Daniela; Rostamzadeh, Taha; Costanzo, Tommaso; Salemizadeh Parizi, Saman; Caruntu, Gabriel

2015-07-01

The rational design of monodisperse ferroelectric nanocrystals with controlled size and shape and their organization into hierarchical structures has been a critical step for understanding the polar ordering in nanoscale ferroelectrics, as well as the design of nanocrystal-based functional materials which harness the properties of individual nanoparticles and the collective interactions between them. We report here on the synthesis and self-assembly of aggregate-free, single-crystalline titanium-based perovskite nanoparticles with controlled morphology and surface composition by using a simple, easily scalable and highly versatile colloidal route. Single-crystalline, non-aggregated BaTiO3 colloidal nanocrystals, used as a model system, have been prepared under solvothermal conditions at temperatures as low as 180 °C. The shape of the nanocrystals was tuned from spheroidal to cubic upon changing the polarity of the solvent, whereas their size was varied from 16 to 30 nm for spheres and 5 to 78 nm for cubes by changing the concentration of the precursors and the reaction time, respectively. The hydrophobic, oleic acid-passivated nanoparticles exhibit very good solubility in non-polar solvents and can be rendered dispersible in polar solvents by a simple process involving the oxidative cleavage of the double bond upon treating the nanopowders with the Lemieux-von Rudloff reagent. Lattice dynamic analysis indicated that regardless of their size, BaTiO3 nanocrystals present local disorder within the perovskite unit cell, associated with the existence of polar ordering. We also demonstrate for the first time that, in addition to being used for fabricating large area, crack-free, highly uniform films, BaTiO3 nanocubes can serve as building blocks for the design of 2D and 3D mesoscale structures, such as superlattices and superparticles. Interestingly, the type of superlattice structure (simple cubic or face centered cubic) appears to be determined by the type of solvent in which the nanocrystals were dispersed. This approach provides an excellent platform for the synthesis of other titanium-based perovskite colloidal nanocrystals with controlled chemical composition, surface structure and morphology and for their assembly into complex architectures, therefore opening the door for the design of novel mesoscale functional materials/nanocomposites with potential applications in energy conversion, data storage and the biomedical field.The rational design of monodisperse ferroelectric nanocrystals with controlled size and shape and their organization into hierarchical structures has been a critical step for understanding the polar ordering in nanoscale ferroelectrics, as well as the design of nanocrystal-based functional materials which harness the properties of individual nanoparticles and the collective interactions between them. We report here on the synthesis and self-assembly of aggregate-free, single-crystalline titanium-based perovskite nanoparticles with controlled morphology and surface composition by using a simple, easily scalable and highly versatile colloidal route. Single-crystalline, non-aggregated BaTiO3 colloidal nanocrystals, used as a model system, have been prepared under solvothermal conditions at temperatures as low as 180 °C. The shape of the nanocrystals was tuned from spheroidal to cubic upon changing the polarity of the solvent, whereas their size was varied from 16 to 30 nm for spheres and 5 to 78 nm for cubes by changing the concentration of the precursors and the reaction time, respectively. The hydrophobic, oleic acid-passivated nanoparticles exhibit very good solubility in non-polar solvents and can be rendered dispersible in polar solvents by a simple process involving the oxidative cleavage of the double bond upon treating the nanopowders with the Lemieux-von Rudloff reagent. Lattice dynamic analysis indicated that regardless of their size, BaTiO3 nanocrystals present local disorder within the perovskite unit cell, associated with the existence of polar ordering. We also demonstrate for the first time that, in addition to being used for fabricating large area, crack-free, highly uniform films, BaTiO3 nanocubes can serve as building blocks for the design of 2D and 3D mesoscale structures, such as superlattices and superparticles. Interestingly, the type of superlattice structure (simple cubic or face centered cubic) appears to be determined by the type of solvent in which the nanocrystals were dispersed. This approach provides an excellent platform for the synthesis of other titanium-based perovskite colloidal nanocrystals with controlled chemical composition, surface structure and morphology and for their assembly into complex architectures, therefore opening the door for the design of novel mesoscale functional materials/nanocomposites with potential applications in energy conversion, data storage and the biomedical field. Electronic supplementary information (ESI) available: FE-SEM image of 12 nm BaTiO3 nanocubes deposited onto a silicon wafer (Fig. SI1), the X-ray diffraction pattern of a superlattice structure formed by monodisperse 10 nm BaTiO3 cuboidal nanocrystals (Fig. SI2) and TEM images of a BaTiO3 superparticle (Fig. SI3). See DOI: 10.1039/c5nr00737b

Novel silica stabilization method for the analysis of fine nanocrystals using coherent X-ray diffraction imaging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Monteforte, Marianne; Estandarte, Ana K.; Chen, Bo

2016-06-23

High-energy X-ray Bragg coherent diffraction imaging (BCDI) is a well established synchrotron-based technique used to quantitatively reconstruct the three-dimensional morphology and strain distribution in nanocrystals. The BCDI technique has become a powerful analytical tool for quantitative investigations of nanocrystals, nanotubes, nanorods and more recently biological systems. BCDI has however typically failed for fine nanocrystals in sub-100?nm size regimes ? a size routinely achievable by chemical synthesis ? despite the spatial resolution of the BCDI technique being 20?30?nm. The limitations of this technique arise from the movement of nanocrystals under illumination by the highly coherent beam, which prevents full diffraction datamore » sets from being acquired. A solution is provided here to overcome this problem and extend the size limit of the BCDI technique, through the design of a novel stabilization method by embedding the fine nanocrystals into a silica matrix. Chemically synthesized FePt nanocrystals of maximum dimension 20?nm and AuPd nanocrystals in the size range 60?65?nm were investigated with BCDI measurement at beamline 34-ID-C of the APS, Argonne National Laboratory. Novel experimental methodologies to elucidate the presence of strain in fine nanocrystals are a necessary pre-requisite in order to better understand strain profiles in engineered nanocrystals for novel device development.« less

Novel silica stabilization method for the analysis of fine nanocrystals using coherent X-ray diffraction imaging.

PubMed

Monteforte, Marianne; Estandarte, Ana K; Chen, Bo; Harder, Ross; Huang, Michael H; Robinson, Ian K

2016-07-01

High-energy X-ray Bragg coherent diffraction imaging (BCDI) is a well established synchrotron-based technique used to quantitatively reconstruct the three-dimensional morphology and strain distribution in nanocrystals. The BCDI technique has become a powerful analytical tool for quantitative investigations of nanocrystals, nanotubes, nanorods and more recently biological systems. BCDI has however typically failed for fine nanocrystals in sub-100 nm size regimes - a size routinely achievable by chemical synthesis - despite the spatial resolution of the BCDI technique being 20-30 nm. The limitations of this technique arise from the movement of nanocrystals under illumination by the highly coherent beam, which prevents full diffraction data sets from being acquired. A solution is provided here to overcome this problem and extend the size limit of the BCDI technique, through the design of a novel stabilization method by embedding the fine nanocrystals into a silica matrix. Chemically synthesized FePt nanocrystals of maximum dimension 20 nm and AuPd nanocrystals in the size range 60-65 nm were investigated with BCDI measurement at beamline 34-ID-C of the APS, Argonne National Laboratory. Novel experimental methodologies to elucidate the presence of strain in fine nanocrystals are a necessary pre-requisite in order to better understand strain profiles in engineered nanocrystals for novel device development.

Single and couple doping ZnO nanocrystals characterized by positron techniques

NASA Astrophysics Data System (ADS)

Pasang, Tenzin; Namratha, Keerthiraj; Guagliardo, Paul; Byrappa, Kullaiah; Ranganathaiah, Chikkakuntappa; Samarin, S.; Williams, J. F.

2015-04-01

Zinc oxide (ZnO) nanocrystals have been synthesized using a mild hydrothermal process using low temperatures and pressures with the advantages of free growth catalyst, low cost and alternative technology. Positron annihilation lifetime spectroscopy and coincidence Doppler broadening (CDB) spectroscopic methods have been used to investigate the roles of single- and co-dopants and native defects of the ZnO nanocrystals controlled by the synthesis process. It is shown that single Ag1+ and Pd2+ dopants occupy interstitial sites of the ZnO lattice and single Ru3+ doping replaces Zn vacancies substitutionally with a significant effect on the CDB momentum ratio curves when compared using ZnO as the reference spectrum. The co-doping of the ZnO lattice with (Sn4+ + Co2+) shows similar CDB ratios as Ru3+ single-doping. Also co-doping with (Ag1+ + Pd2+) or (Ag1+ + W6+) shows significant decreases in the band gap energy up to about 12.6% compared to single doping. The momentum ratio curves, referenced to undoped ZnO, indicate dopants in interstitial and substitutional sites. The presence of transition metal ions interstitially will trap electrons which resist the recombination of electrons and in turn affect the conductivity of the material.

One-step rapid synthesis of ultrafine γ-Ga2O3 nanocrystals by microwave hydrothermal method in ammonium hydroxide medium

NASA Astrophysics Data System (ADS)

Cui, Lu; Wang, Hong; Xin, Baifu; Mao, Guijie

2017-10-01

Ultrafine nanocrystals of γ-gallium oxide (γ-Ga2O3) were rapidly synthesized via microwave hydrothermal method at 140 °C, in which Ga(NO3)3 was used as the gallium source and urea was the precipitant. The samples were characterized by X-ray diffraction (XRD), ultraviolet-visible absorption spectroscopy (UV-Vis), transmission electron microscopy (TEM), nitrogen physisorption and photoluminescence spectroscopy (PL). The crystallite size of ultrafine spinel γ-Ga2O3 was in the range from 4 to 5 nm and the optical bandgap was 4.61 eV. To improve the crystallinity, the ultrafine γ-Ga2O3 nanocrystals were calcined at 300-700 °C further. The ultrafine γ-Ga2O3 calcined at 500 °C (calcined-γ-Ga2O3) still remained the metastable γ-phase with relatively high crystallinity and the crystallite size around 5-7 nm. Photocatalytic performances of the synthesized samples were also evaluated by the degradation of rhodamine B (RhB). Results revealed that the ultrafine γ-Ga2O3 and the calcined-γ-Ga2O3 samples exhibited high photocatalytic efficiencies of 68.2 and 90.7%, respectively.

Nano-sized quaternary CuGa2In3S8 as an efficient photocatalyst for solar hydrogen production.

PubMed

Kandiel, Tarek A; Anjum, Dalaver H; Takanabe, Kazuhiro

2014-11-01

The synthesis of quaternary metal sulfide (QMS) nanocrystals is challenging because of the difficulty to control their stoichiometry and phase structure. Herein, quaternary CuGa2In3S8 photocatalysts with a primary particle size of ≈4 nm are synthesized using a facile hot-injection method by fine-tuning the sulfur source injection temperature and aging time. Characterization of the samples reveals that quaternary CuGa2In3S8 nanocrystals exhibit n-type semiconductor characteristics with a transition band gap of ≈1.8 eV. Their flatband potential is located at -0.56 V versus the standard hydrogen electrode at pH 6.0 and is shifted cathodically by 0.75 V in solutions with pH values greater than 12.0. Under optimized conditions, the 1.0 wt % Ru-loaded CuGa2In3S8 photocatalyst exhibits a photocatalytic H2 evolution response up to 700 nm and an apparent quantum efficiency of (6.9±0.5) % at 560 nm. These results indicate clearly that QMS nanocrystals have great potential as nano-photocatalysts for solar H2 production. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Single-phase and well-dispersed Cu1.75S nanocrystals by ambient pressure diethylene glycol solution synthesis

NASA Astrophysics Data System (ADS)

Zheng, Xuerong; Jin, Zhengguo; Liu, Hui; Wang, Yueqiu; Wang, Xin; Du, Haiyan

2013-02-01

Single-phase, well-dispersed Cu1.75S nanocrystals were synthesized by an ambient pressure, hydrazine hydrate and ethylenediamine co-assisted diethylene glycol based solution chemical process using copper chloride and thioacetamide as precursors at the temperature range from 180 to 210 °C. Influence of hydrazine hydrate and ethylenediamine adding amounts, synthetic temperature on crystal growth, size distribution and optical properties of the synthesized Cu1.75S nanocrystals were investigated by XRD, TEM, HRTEM, EDX and UV-vis measurements. The synthetic reaction at above 200 °C grew flaky-shaped nanocrystals with relatively narrow size distribution. The formation of single-phase Cu1.75S nanocrystals in the diethylene glycol based solution process might be involved in the presence of intermediate [Cu(en)n]1+ and [Cu(NH3)4]2+ complexes in reaction solution, providing a stable Cu(I) and Cu(II) valent-mixed precursor.

Transition-Metal Decorated Aluminum Nanocrystals.

PubMed

Swearer, Dayne F; Leary, Rowan K; Newell, Ryan; Yazdi, Sadegh; Robatjazi, Hossein; Zhang, Yue; Renard, David; Nordlander, Peter; Midgley, Paul A; Halas, Naomi J; Ringe, Emilie

2017-10-24

Recently, aluminum has been established as an earth-abundant alternative to gold and silver for plasmonic applications. Particularly, aluminum nanocrystals have shown to be promising plasmonic photocatalysts, especially when coupled with catalytic metals or oxides into "antenna-reactor" heterostructures. Here, a simple polyol synthesis is presented as a flexible route to produce aluminum nanocrystals decorated with eight varieties of size-tunable transition-metal nanoparticle islands, many of which have precedence as heterogeneous catalysts. High-resolution and three-dimensional structural analysis using scanning transmission electron microscopy and electron tomography shows that abundant nanoparticle island decoration in the catalytically relevant few-nanometer size range can be achieved, with many islands spaced closely to their neighbors. When coupled with the Al nanocrystal plasmonic antenna, these small decorating islands will experience increased light absorption and strong hot-spot generation. This combination makes transition-metal decorated aluminum nanocrystals a promising material platform to develop plasmonic photocatalysis, surface-enhanced spectroscopies, and quantum plasmonics.

Synthesis and near-infrared fluorescence of K5NdLi2F10 nanocrystals and their dispersion with high doping concentration and long lifetime.

PubMed

Duan, Weikuan; Zhang, Yanyan; Wang, Zhongyue; Jiang, Jingyi; Liang, Chen; Wei, Wei

2014-06-07

K5NdLi2F10 nanocrystals were synthesized by a novel synthetic route in the liquid phase, which could improve the morphology and reduce the size effectively, for the first time. The luminescence intensities of the K5NdLi2F10 nanocrystals and their dispersion in polyethylene glycol 400 (PEG-400) approximate to that of neodymium doped phosphate glass (3 mol%), while the lifetimes of the nanocrystals alone and when dispersed with Nd(3+) ions (1 × 10(20) cm(-3)) are 303.4 μs and 174.6 μs respectively. Based on the Judd-Ofelt analysis, the emission quantum yield of the dispersion reaches 39.57%. In all, the K5NdLi2F10 nanocrystals and their dispersion have promising applications as liquid laser materials and biological fluorescent markers.

Chalcogenide and pnictide nanocrystals from the silylative deoxygenation of metal oxides

DOE PAGES

Lin, Chia-Cheng; Tan, Shannon J.; Vela, Javier

2017-09-11

Transition metal chalcogenide and pnictide nanocrystals are of interest for optoelectronic and catalytic applications. In this paper, we present a generalized route to the synthesis of these materials from the silylative deoxygenation of metal oxides with trimethylsilyl reagents. Specific nanophases produced in this way include Ni 3S 2, Ni 5Se 5, Ni 2P, Co 9S 8, Co 3Se 4, CoP, Co 2P, and heterobimetallic (Ni/Co) 9S 8. The resulting chalcogenide nanocrystals are hollow, likely due to differential rates of ion diffusion during the interfacial phase transformation reaction (Kirkendall-type effect). In contrast, the phosphide nanocrystals are solid, likely because they formmore » at higher reaction temperatures. Finally, in all cases, simultaneous partial decomposition of the deoxygenating silyl reagent produces a coating of amorphous silica around the newly formed nanocrystals, which could impact their stability and recyclability.« less

Salt-assistant combustion synthesis of nanocrystalline Nd{sub 2}(Zr{sub 1-x}Sn{sub x}){sub 2}O{sub 7} (0 {<=} x {<=} 1) solid solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tong Yuping, E-mail: huabeitong@yahoo.cn; Wang Yanping

2009-11-15

Nanocrystalline Nd{sub 2}(Zr{sub 1-x}Sn{sub x}){sub 2}O{sub 7} series solid solutions were prepared by a convenient salt-assisted combustion process using glycine as fuel. The samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, transmission electron microscopy and high-resolution transmission electron microscopy. The results showed the Zr ion can be partially replaced by Sn ion. The partial substituted products were still single-phase solid solutions and the crystal form remained unchanged. TEM images reveal that the products are composed of well-dispersed square-shaped nanocrystals. The method provides a convenient and low-cost route for the synthesis of nanostructures of oxide materials.

One-step synthesis of highly dispersed gold nanocrystals on silica spheres.

PubMed

Phonthammachai, Nopphawan; White, Timothy J

2007-11-06

Highly dispersed gold nanocrystals decorating silica spheres were prepared from HAuCl4 and NaOH via a deposition-precipitation (DP) process, in which the isoelectric point (IEP) of the substrate was adjusted during sphere synthesis by interaction of the surface with ammonia molecules. Through the systematic variation of pH (4-8), reaction temperature (65-96 degrees C), and time (10-30 min), a superior product with small (2-5 nm), homogeneously distributed gold crystals was obtained at pH 7 and a reaction temperature of 96 degrees C. These materials will offer enhanced performance as catalysts and contrast enhancers in biomedical imaging.

Colloidal thallium halide nanocrystals with reasonable luminescence, carrier mobility and diffusion length† †Electronic supplementary information (ESI) available: Synthesis and additional characterization of nanocrystals, characterization of nanocrystal films, temperature-dependent phase transition, coefficient of volume expansion, PL decay dynamics, tabulated best fit parameters, and methodology analysis of ultrafast optical pump THz probe (OPTP) spectroscopy. See DOI: 10.1039/c7sc01219e Click here for additional data file.

PubMed Central

Mir, Wasim J.; Warankar, Avinash; Acharya, Ashutosh; Das, Shyamashis

2017-01-01

Colloidal lead halide based perovskite nanocrystals (NCs) have been recently established as an interesting class of defect-tolerant NCs with potential for superior optoelectronic applications. The electronic band structure of thallium halides (TlX, where X = Br and I) show a strong resemblance to lead halide perovskites, where both Pb2+ and Tl+ exhibit a 6s2 inert pair of electrons and strong spin–orbit coupling. Although the crystal structure of TlX is not perovskite, the similarities of its electronic structure with lead halide perovskites motivated us to prepare colloidal TlX NCs. These TlX NCs exhibit a wide bandgap (>2.5 eV or <500 nm) and the potential to exhibit a reduced density of deep defect states. Optical pump terahertz (THz) probe spectroscopy with excitation fluence in the range of 0.85–5.86 × 1013 photons per cm2 on NC films shows that the TlBr NCs possess high effective carrier mobility (∼220 to 329 cm2 V–1 s–1), long diffusion length (∼0.77 to 0.98 μm), and reasonably high photoluminescence efficiency (∼10%). This combination of properties is remarkable compared to other wide-bandgap (>2.5 eV) semiconductor NCs, which suggests a reduction in the deep-defect states in the TlX NCs. Furthermore, the ultrafast carrier dynamics and temperature-dependent reversible structural phase transition together with its influence on the optical properties of the TlX NCs are studied. PMID:28970882

Biomolecule-controlled hydrothermal synthesis of C-N-S-tridoped TiO2 nanocrystalline photocatalysts for NO removal under simulated solar light irradiation.

PubMed

Wang, Yawen; Huang, Yu; Ho, Wingkei; Zhang, Lizhi; Zou, Zhigang; Lee, Shuncheng

2009-09-30

In this study, C-N-S-tridoped titanium dioxide (TiO(2)) nanocrystals were synthesized by using a facile hydrothermal method in the presence of a biomolecule l-cysteine. This biomolecule could not only serve as the common source for the carbon, sulfur and nitrogen tridoping, but also could control the final crystal phases and morphology. The resulting materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption and UV-vis diffuse reflectance spectroscopy. XPS analysis revealed that S was incorporated into the lattice of TiO(2) through substituting oxygen atoms, N might coexist in the forms of N-Ti-O and Ti-O-N in tridoped TiO(2) and most C could form a mixed layer of carbonate species deposited on the surface of TiO(2) nanoparticles. The photocatalytic activities of the samples were tested on the removal of NO at typical indoor air level in a flow system under simulated solar light irradiation. The tridoped TiO(2) samples showed much higher removal efficiency than commercial P25 and the undoped counterpart photocatalyst. The enhanced visible light photocatalytic activity of C-N-S-tridoped TiO(2) nanocrystals was explained on the basis of characterizations. The possible formation process of the monodispersed C-N-S-tridoped anatase TiO(2) nanocrystals was also proposed. This study provides a new method to prepare visible light active TiO(2) photocatalyst.

Roles of aromatic side chains and template effects of the hydrophobic cavity of a self-assembled peptide nanoarchitecture for anisotropic growth of gold nanocrystals.

PubMed

Tomizaki, Kin-ya; Kishioka, Kohei; Kobayashi, Hiroki; Kobayashi, Akitsugu; Yamada, Naoki; Kataoka, Shunsuke; Imai, Takahito; Kasuno, Megumi

2015-11-15

Gold nanocrystals are promising as catalysts and for use in sensing/imaging systems, photonic/plasmonic devices, electronics, drug delivery systems, and for photothermal therapy due to their unique physical, chemical, and biocompatible properties. The use of various organic templates allows control of the size, shape, structure, surface modification and topology of gold nanocrystals; in particular, currently the synthesis of gold nanorods requires a cytotoxic surfactant to control morphology. To control the shape of gold nanocrystals, we previously demonstrated the de novo design and synthesis of a β-sheet-forming nonapeptide (RU006: Ac-AIAKAXKIA-NH2, X=L-2-naphthylalanine, Nal) and the fabrication of gold nanocrystals by mixing RU006 and HAuCl4 in water. The reaction afforded ultrathin gold nanoribbons 50-100 nm wide, several nanometers high, and microns long. To understand the mechanism underlying gold nanoribbon formation by the RU006 system, we here report (i) the effects of replacement of the Nal aromatic side chain in the RU006 sequence with other aromatic moieties, (ii) the electrochemical properties of aromatic side chains in the de novo designed template peptides to estimate the redox potential and number of electrons participating in the gold crystallization process, and (iii) the stoichiometry of the RU006 system for gold nanoribbon synthesis. Interestingly, RU006 bearing a naphthalene moiety (oxidation peak potential of 1.50 V vs Ag/Ag(+)) and an analog [Ant(6)]-RU006 bearing a bulky anthracene moiety (oxidation peak potential of 1.05 V vs Ag/Ag(+)) allowed the growth of anisotropic (ribbon-like) and isotropic (round) gold nanocrystals, respectively. This trend in morphology of gold nanocrystals was attributed to spatially-arranged hydrophobic cavities sufficiently large to accommodate the gold precursor and to allow directed crystal growth driven by cross-linking reactions among the naphthalene rings. Support for this mechanism was obtained by decreasing the mole fraction of [Ant(6)]-RU006 against the total concentration of [Ant(6)]-RU006 and [Phe(6)]-RU006: absorption spectra similar to that for RU006 were obtained. Differences in the redox properties of the anthracene and naphthalene moieties scarcely affected morphology. We propose that construction of an appropriate hydrophobic cavity is important for templating gold nanocrystal architectures by peptide self-assembly. This mechanism would be applicable for developing simple, low toxicity, mild synthetic methods for constructing metallic nanomaterials for therapeutic use. Copyright © 2015 Elsevier Ltd. All rights reserved.

Microfluidic Technology: Uncovering the Mechanisms of Nanocrystal Nucleation and Growth.

PubMed

Lignos, Ioannis; Maceiczyk, Richard; deMello, Andrew J

2017-05-16

The controlled and reproducible formation of colloidal semiconductor nanocrystals (or quantum dots) is of central importance in nanoscale science and technology. The tunable size- and shape-dependent properties of such materials make them ideal candidates for the development of efficient and low-cost displays, solar cells, light-emitting devices, and catalysts. The formidable difficulties associated with the macroscale preparation of semiconductor nanocrystals (possessing bespoke optical and chemical properties) result from the fact that underlying reaction mechanisms are complex and that the reactive environment is difficult to control. Automated microfluidic reactors coupled with monitoring systems and optimization algorithms aim to elucidate complex reaction mechanisms that govern both nucleation and growth of nanocrystals. Such platforms are ideally suited for the efficient optimization of reaction parameters, assuring the reproducible synthesis of nanocrystals with user-defined properties. This Account aims to inform the nanomaterials community about how microfluidic technologies can supplement flask experimentation for the ensemble investigation of formation mechanisms and design of semiconductor nanocrystals. We present selected studies outlining the preparation of quantum dots using microfluidic systems with integrated analytics. Such microfluidic reaction systems leverage the ability to extract real-time information regarding optical, structural, and compositional characteristics of quantum dots during nucleation and growth stages. The Account further highlights our recent research activities focused on the development and application of droplet-based microfluidics with integrated optical detection systems for the efficient and rapid screening of reaction conditions and a better understanding of the mechanisms of quantum dot synthesis. We describe the features and operation of fully automated microfluidic reactors and their subsequent application to high-throughput parametric screening of metal chalcogenides (CdSe, PbS, PbSe, CdSeTe), ternary and core/shell heavy metal-free quantum dots (CuInS 2 , CuInS 2 /ZnS), and all-inorganic perovskite nanocrystals (CsPbX 3 , X = Cl, Br, I) syntheses. Critically, concurrent absorption and photoluminescence measurements on millisecond to second time scales allow the extraction of basic parameters governing nanocrystal formation. Moreover, experimental data obtained from such microfluidic platforms can be directly supported by theoretical models of nucleation and growth. To this end, we also describe the use of metamodeling algorithms able to accurately predict optimized conditions of CdSe synthesis using a minimal number of sample parameters. Importantly, we discuss future challenges that must be addressed before microfluidic technologies are in a position to be widely adopted for the on-demand formation of nanocrystals. From a technology perspective, these challenges include the development of novel engineering platforms for the formation of complex architectures, the integration of monitoring systems able to harvest photophysical and structural information, the incorporation of continuous purification systems, and the application of optimization algorithms to multicomponent quantum dot systems.

Highly Luminescent Zn(x)Cd(1-x)Se/C Core/Shell Nanocrystals: Large Scale Synthesis, Structural and Cathodoluminescence Studies.

PubMed

Bhattacharyya, Sayan; Estrin, Yevgeni; Moshe, Ofer; Rich, Daniel H; Solovyov, Leonid A; Gedanken, A

2009-07-28

Zn(x)Cd(1-x)Se/C core/shell nanocrystals with 31-39 nm semiconducting core and 11-25 nm carbon shell were synthesized from solid state precursors in large scale amounts. A mixture of spherical and tripod nanostructures were obtained only in the one-step reaction (ZC3), where the Zn- and Cd-precursors were reacted simultaneously, rather than in the two step reactions (ZC1 and ZC2), where largely spherical nanostructures were observed. Rietveld analysis of the X-ray diffraction patterns of the samples prepared in three different ways, all under their autogenic pressure, reveal varying compositions of the Zn(x)Cd(1-x)Se nanocrystal core, where the cubic phases with higher Zn content were dominant compared to the hexagonal phases. Carbon encapsulation offers excellent protection to the nanocrystal core and is an added advantage for biological applications. Cathodoluminescence (CL) measurements with spatially integrated and highly localized excitations show distinct peaks and sharp lines at various wavelengths, representing emissions from single nanostructures possessing different compositions, phases, and sizes. Transmission electron microscopy (TEM) showed striations in the nanocrystals that are indicative of a composition modulation, and possibly reveal a phase separation and spinodal decomposition within the nanocrystals. Thermal quenching of the luminescence for both the near band-edge and defect related emissions were observed in the range 60-300 K. The measured activation energies of ∼50-70 meV were related to the presence of shallow donors or acceptors, deep level emissions, and thermal activation and quenching of the luminescence due to the thermal release of electrons from shallow donors to the conduction band or a thermal release of holes from shallow acceptors to the valence band. Spatially integrated CL spectra revealed the existence of broadening and additional components that are consistent with the presence of a composition modulation in the nanocrystals. Spatial localization of the emission in isolated single nanocrystals was studied using monochromatic CL imaging and local CL spectroscopy. CL spectra acquired by a highly localized excitation of individual nanocrystals showed energy shifts in the excitonic luminescence that are consistent with a phase separation into Zn- and Cd-rich regions. The simultaneous appearance of both structural and compositional phase separation for the synthesis of Zn(x)Cd(1-x)Se nanocrystals reveals the complexity and uniqueness of these results.

Characterization of memory and measurement history in photoconductivity of nanocrystal arrays

NASA Astrophysics Data System (ADS)

Fairfield, Jessamyn A.; Dadosh, Tali; Drndic, Marija

2010-10-01

Photoconductivity in nanocrystal films has been previously characterized, but memory effects have received little attention despite their importance for device applications. We show that the magnitude and temperature dependence of the photocurrent in CdSe/ZnS core-shell nanocrystal arrays depends on the illumination and electric field history. Changes in photoconductivity occur on a few-hour timescale, and subband gap illumination of nanocrystals prior to measurements modifies the photocurrent more than band gap illumination. The observed effects can be explained by charge traps within the band gap that are filled or emptied, which may alter nonradiative recombination processes and affect photocurrent.

Ultrafast and scalable laser liquid synthesis of tin oxide nanotubes and its application in lithium ion batteries

NASA Astrophysics Data System (ADS)

Liu, Zhikun; Cao, Zeyuan; Deng, Biwei; Wang, Yuefeng; Shao, Jiayi; Kumar, Prashant; Liu, C. Richard; Wei, Bingqing; Cheng, Gary J.

2014-05-01

Laser-induced photo-chemical synthesis of SnO2 nanotubes has been demonstrated by employing a nanoporous polycarbonate membrane as a template. The SnO2 nanotube diameter can be controlled by the nanoporous template while the nanotube length can be tuned by laser parameters and reaction duration. The microstructure characterization of the nanotubes indicates that they consist of mesoporous structures with sub 5 nm size nanocrystals connected by the twinning structure. The application of SnO2 nanotubes as an anode material in lithium ion batteries has also been explored, and they exhibited high capacity and excellent cyclic stability. The laser based emerging technique for scalable production of crystalline metal oxide nanotubes in a matter of seconds is remarkable. The compliance of the laser based technique with the existing technologies would lead to mass production of novel nanomaterials that would be suitable for several emerging applications.Laser-induced photo-chemical synthesis of SnO2 nanotubes has been demonstrated by employing a nanoporous polycarbonate membrane as a template. The SnO2 nanotube diameter can be controlled by the nanoporous template while the nanotube length can be tuned by laser parameters and reaction duration. The microstructure characterization of the nanotubes indicates that they consist of mesoporous structures with sub 5 nm size nanocrystals connected by the twinning structure. The application of SnO2 nanotubes as an anode material in lithium ion batteries has also been explored, and they exhibited high capacity and excellent cyclic stability. The laser based emerging technique for scalable production of crystalline metal oxide nanotubes in a matter of seconds is remarkable. The compliance of the laser based technique with the existing technologies would lead to mass production of novel nanomaterials that would be suitable for several emerging applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr06444a

Controlled synthesis of quantum confined CsPbBr3 perovskite nanocrystals under ambient conditions

NASA Astrophysics Data System (ADS)

He, Huimei; Tang, Bing; Ma, Ying

2018-02-01

Room temperature recrystallization is a simple and convenient method for synthesis of all-inorganic perovskite nanomaterials with excellent luminescent properties. However, the fast crystallization usually brings the colloidal stability and uncontrollable synthesis issues in the formation of all-inorganic perovskite. In the present study, we present a new strategy to prepare the quantum confined CsPbBr3 nanocrystals with controlled morphology under ambient condition. With the assist of fatty acid-capped precursor, the crystallization and the following growth rate can be retarded. Thanks to the retarded reaction, the morphology can be varied from nanowires to nanoplates and the thickness can be controlled from 5-7 monolayers by simply adjusting the amount of octylammonium cations and oleic acid. The nanoplates exhibit a higher photoluminescence quantum yield than the nanowires possibly due to fewer defects in the nanoplates.

A chemical reduction approach to the synthesis of copper nanoparticles

NASA Astrophysics Data System (ADS)

Khan, Ayesha; Rashid, Audil; Younas, Rafia; Chong, Ren

2016-11-01

Development of improved methods for the synthesis of copper nanoparticles is of high priority for the advancement of material science and technology. Herein, starch-protected zero-valent copper (Cu) nanoparticles have been successfully synthesized by a novel facile route. The method is based on the chemical reduction in aqueous copper salt using ascorbic acid as reducing agent at low temperature (80 °C). X-ray diffraction, scanning electron microscopy and energy-dispersive X-ray spectroscopy measurements were taken to investigate the size, structure and composition of synthesized Cu nanocrystals, respectively. Average crystallite size of Cu nanocrystals calculated from the major diffraction peaks using the Scherrer formula is about 28.73 nm. It is expected that the outcomes of the study take us a step closer toward designing rational strategies for the synthesis of nascent Cu nanoparticles without inert gas protection.

Synthesis, surface chemistry and pseudocapacitance mechanisms of VN nanocrystals derived by a simple two-step halide approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choi, Daiwon; Jampani, Prashanth H.; Jayakody, J. R. P.

Chloroamide precursors generated via a simple two-step ammonolysis reaction of transition metal chloride in the liquid phase at room temperature were heat treated in ammonia at moderate temperature to yield nano-sized VN crystallites. Grain growth inhibited by lowering the synthesis temperature (≈400°C) yielded agglomerated powders of spherical crystallites of cubic phase of VN with particle sizes as small as 6nm in diameter. X-ray diffraction, FTIR, mass spectroscopy (MS), and nuclear magnetic resonance (NMR) spectroscopy assessed the ammonolysis and nitridation reaction of the VCl 4-NH 3 system. X-ray Rietveld refinement, the BET technique and high-resolution transmission microscopy (HRTEM), energy dispersive x-raymore » (EDX) and thermogravimetric analysis (TGA) helped assess the crystallographic and microstructural nature of the VN nanocrystals. The surface chemistry and redox reaction leading to the gravimetric pseudo-capacitance value of (≈855 F/g) measured for the VN nanocrystals was determined and validated using FTIR, XPS and cyclic voltammetry analyses.« less

Synthesis and Luminescence Properties of Transparent Nanocrystalline GdF3:Tb Glass-Ceramic Scintillator.

PubMed

Lee, Gyuhyon; Savage, Nicholas; Wagner, Brent; Zhang, Yuelan; Jacobs, Benjamin; Menkara, Hisham; Summers, Christopher; Kang, Zhitao

2014-03-01

Transparent glass-ceramic containing rare-earth doped halide nanocrystals exhibits enhanced luminescence performance. In this study, a glass-ceramic with Tb doped gadolinium fluoride nanocrystals embedded in an aluminosilicate glass matrix is investigated for X-ray imaging applications. The nanocrystalline glass-ceramic scintillator was prepared by a melt-quench method followed by an anneal. The GdF 3 :Tb nanocrystals precipitated within the oxide glass matrix during the processing and their luminescence and scintillation properties were investigated. In this nanocomposite scintillator system, the incorporation of high atomic number Gd compound into the glass matrix increases the X-ray stopping power of the glass scintillator, and effective energy transfer between Gd 3+ and Tb 3+ ions in the nanocrystals enhances the scintillation efficiency.

Synthesis and Luminescence Properties of Transparent Nanocrystalline GdF3:Tb Glass-Ceramic Scintillator

PubMed Central

Lee, Gyuhyon; Savage, Nicholas; Wagner, Brent; Zhang, Yuelan; Jacobs, Benjamin; Menkara, Hisham; Summers, Christopher; Kang, Zhitao

2014-01-01

Transparent glass-ceramic containing rare-earth doped halide nanocrystals exhibits enhanced luminescence performance. In this study, a glass-ceramic with Tb doped gadolinium fluoride nanocrystals embedded in an aluminosilicate glass matrix is investigated for X-ray imaging applications. The nanocrystalline glass-ceramic scintillator was prepared by a melt-quench method followed by an anneal. The GdF3:Tb nanocrystals precipitated within the oxide glass matrix during the processing and their luminescence and scintillation properties were investigated. In this nanocomposite scintillator system, the incorporation of high atomic number Gd compound into the glass matrix increases the X-ray stopping power of the glass scintillator, and effective energy transfer between Gd3+ and Tb3+ ions in the nanocrystals enhances the scintillation efficiency. PMID:24610960

NaGd(MoO4)2 nanocrystals with diverse morphologies: controlled synthesis, growth mechanism, photoluminescence and thermometric properties.

PubMed

Li, Anming; Xu, Dekang; Lin, Hao; Yang, Shenghong; Shao, Yuanzhi; Zhang, Yueli

2016-08-10

Pure tetragonal phase, uniform and well-crystallized sodium gadolinium molybdate (NaGd(MoO4)2) nanocrystals with diverse morphologies, e.g. nanocylinders, nanocubes and square nanoplates have been selectively synthesized via oleic acid-mediated hydrothermal method. The phase, structure, morphology and composition of the as-synthesized products are studied. Contents of both sodium molybdate and oleic acid of the precursor solutions are found to affect the morphologies of the products significantly, and oleic acid plays a key role in the morphology-controlled synthesis of NaGd(MoO4)2 nanocrystals with diverse morphologies. Growth mechanism of NaGd(MoO4)2 nanocrystals is proposed based on time-dependent morphology evolution and X-ray diffraction analysis. Morphology-dependent down-shifting photoluminescence properties of NaGd(MoO4)2: Eu(3+) nanocrystals, and upconversion photoluminescence properties of NaGd(MoO4)2: Yb(3+)/Er(3+) and Yb(3+)/Tm(3+) nanoplates are investigated in detail. Charge transfer band in the down-shifting excitation spectra shows a slight blue-shift, and the luminescence intensities and lifetimes of Eu(3+) are decreased gradually with the morphology of the nanocrystals varying from nanocubes to thin square nanoplates. Upconversion energy transfer mechanisms of NaGd(MoO4)2: Yb(3+)/Er(3+), Yb(3+)/Tm(3+) nanoplates are proposed based on the energy level scheme and power dependence of upconversion emissions. Thermometric properties of NaGd(MoO4)2: Yb(3+)/Er(3+) nanoplates are investigated, and the maximum sensitivity is determined to be 0.01333 K(-1) at 285 K.

NaGd(MoO4)2 nanocrystals with diverse morphologies: controlled synthesis, growth mechanism, photoluminescence and thermometric properties

PubMed Central

Li, Anming; Xu, Dekang; Lin, Hao; Yang, Shenghong; Shao, Yuanzhi; Zhang, Yueli

2016-01-01

Pure tetragonal phase, uniform and well-crystallized sodium gadolinium molybdate (NaGd(MoO4)2) nanocrystals with diverse morphologies, e.g. nanocylinders, nanocubes and square nanoplates have been selectively synthesized via oleic acid-mediated hydrothermal method. The phase, structure, morphology and composition of the as-synthesized products are studied. Contents of both sodium molybdate and oleic acid of the precursor solutions are found to affect the morphologies of the products significantly, and oleic acid plays a key role in the morphology-controlled synthesis of NaGd(MoO4)2 nanocrystals with diverse morphologies. Growth mechanism of NaGd(MoO4)2 nanocrystals is proposed based on time-dependent morphology evolution and X-ray diffraction analysis. Morphology-dependent down-shifting photoluminescence properties of NaGd(MoO4)2: Eu3+ nanocrystals, and upconversion photoluminescence properties of NaGd(MoO4)2: Yb3+/Er3+ and Yb3+/Tm3+ nanoplates are investigated in detail. Charge transfer band in the down-shifting excitation spectra shows a slight blue-shift, and the luminescence intensities and lifetimes of Eu3+ are decreased gradually with the morphology of the nanocrystals varying from nanocubes to thin square nanoplates. Upconversion energy transfer mechanisms of NaGd(MoO4)2: Yb3+/Er3+, Yb3+/Tm3+ nanoplates are proposed based on the energy level scheme and power dependence of upconversion emissions. Thermometric properties of NaGd(MoO4)2: Yb3+/Er3+ nanoplates are investigated, and the maximum sensitivity is determined to be 0.01333 K−1 at 285 K. PMID:27506629

Tolerance to structural disorder and tunable mechanical behavior in self-assembled superlattices of polymer-grafted nanocrystals

DOE PAGES

Gu, X. Wendy; Ye, Xingchen; Koshy, David M.; ...

2017-02-27

Large, freestanding membranes with remarkably high elastic modulus ( > 10 GPa) have been fabricated through the self-Assembly of ligand-stabilized inorganic nanocrystals, even though these nanocrystals are connected only by soft organic ligands (e.g., dodecanethiol or DNA) that are not cross-linked or entangled. Recent developments in the synthesis of polymer-grafted nanocrystals have greatly expanded the library of accessible superlattice architectures,which allows superlattice mechanical behavior to be linked to specific structural features. Here, colloidal self-Assembly is used to organize polystyrene-grafted Au nanocrystals at a fluid interface to form ordered solids with sub-10-nm periodic features. We used thin-film buckling and nanoindentation tomore » evaluate the mechanical behavior of polymer-grafted nanocrystal superlattices while exploring the role of polymer structural conformation, nanocrystal packing, and superlattice dimensions. Superlattices containing 3-20 vol % Au are found to have an elastic modulus of ~6-19 GPa, and hardness of ~120-170 MPa. We also found that rapidly self-Assembled superlattices have the highest elastic modulus, despite containing significant structural defects. Polymer extension, interdigitation, and grafting density are determined to be critical parameters that govern superlattice elastic and plastic deformation.« less

Tolerance to structural disorder and tunable mechanical behavior in self-assembled superlattices of polymer-grafted nanocrystals

NASA Astrophysics Data System (ADS)

Gu, X. Wendy; Ye, Xingchen; Koshy, David M.; Vachhani, Shraddha; Hosemann, Peter; Alivisatos, A. Paul

2017-03-01

Large, freestanding membranes with remarkably high elastic modulus (>10 GPa) have been fabricated through the self-assembly of ligand-stabilized inorganic nanocrystals, even though these nanocrystals are connected only by soft organic ligands (e.g., dodecanethiol or DNA) that are not cross-linked or entangled. Recent developments in the synthesis of polymer-grafted nanocrystals have greatly expanded the library of accessible superlattice architectures, which allows superlattice mechanical behavior to be linked to specific structural features. Here, colloidal self-assembly is used to organize polystyrene-grafted Au nanocrystals at a fluid interface to form ordered solids with sub-10-nm periodic features. Thin-film buckling and nanoindentation are used to evaluate the mechanical behavior of polymer-grafted nanocrystal superlattices while exploring the role of polymer structural conformation, nanocrystal packing, and superlattice dimensions. Superlattices containing 3-20 vol % Au are found to have an elastic modulus of ˜6-19 GPa, and hardness of ˜120-170 MPa. We find that rapidly self-assembled superlattices have the highest elastic modulus, despite containing significant structural defects. Polymer extension, interdigitation, and grafting density are determined to be critical parameters that govern superlattice elastic and plastic deformation.

The synthesis, characterization and application of iron oxide nanocrystals in magnetic separations for arsenic and uranium removal

NASA Astrophysics Data System (ADS)

Mayo, John Thomas

Arsenic and uranium in the environment are hazardous to human health and require better methods for detection and remediation. Nanocrystalline iron oxides offer a number of advantages as sorbents for water purification and environmental remediation. First, highly uniform and crystalline iron oxide nanocrystals (nMAG) were prepared using thermal decomposition of iron salts in organic solutions; for the applications of interest in this thesis, a central challenge was the adaptation of these conventional synthetic methods to the needs of low infrastructure and economically disadvantaged settings. We show here that it is possible to form highly uniform and magnetically responsive nanomaterials using starting reagents and equipment that are readily available and economical. The products of this approach, termed the 'Kitchen Synthesis', are of comparable quality and effectiveness to laboratory materials. The narrow size distributions of the iron oxides produced in the laboratory synthesis made it possible to study the size-dependence of the magnetic separation efficiency of nanocrystals; generally as the diameter of particles increased they could be removed under lower applied magnetic fields. In this work we take advantage of this size-dependence to use magnetic separation as a tool to separate broadly distributed populations of magnetic materials. Such work makes it possible to use these materials in multiplexed separation and sensing schemes. With the synthesis and magnetic separation studies of these materials completed, it was possible to optimize their applications in water purification and environmental remediation. These materials removed both uranium and arsenic from contaminated samples, and had remarkably high sorption capacities --- up to 12 wt% for arsenic and 30 wt% for uranium. The contaminated nMAG is removed from the drinking water by either retention in a sand column, filter, or by magnetic separation. The uranium adsorption process was also utilized for the enhanced detection of uranium in environmental matrices. By relying on alpha-particle detection in well-formed and dense nMAG films, it was possible to improve soil detection of uranium by more than ten-thousand-fold. Central for this work was a detailed understanding of the chemistry at the iron oxide interface, and the role of the organic coatings in mediating the sorption process.

PTFE-based microreactor system for the continuous synthesis of full-visible-spectrum emitting cesium lead halide perovskite nanocrystals.

PubMed

Zhang, Chengxi; Luan, Weiling; Yin, Yuhang; Yang, Fuqian

2017-01-01

Colloidal perovskite nanocrystals comprised of all inorganic cesium lead halide (CsPbX 3 , X = Cl, Br, I or a mixture thereof) have potential as optical gain materials due to their high luminescence efficiency. In this work, cesium lead halide nanocrystals are continuously synthesized via a microreactor system consisting of poly(tetrafluoroethylene) (PTFE) capillaries. The synthesized nanocrystals possess excellent optical properties, including a full width at half maximum of 19-35 nm, high fluorescence quantum yield of 47.8-90.55%, and photoluminescence emission in the range of 450-700 nm. For the same precursor concentrations, the photoluminescence emission peak generally increases with increasing reaction temperature, revealing a controllable temperature effect on the photoluminescence characteristics of the synthesized nanocrystals. For quantum dots synthesized with a Br/I ratio of 1:3, a slight blue shift was observed for reaction temperatures greater than 100 °C. This PTFE-based microreactor system provides the unique capability of continuously synthesizing high-quality perovskite nanocrystals that emit over the full visible spectrum with applications ranging from displays and optoelectronic devices.

PTFE-based microreactor system for the continuous synthesis of full-visible-spectrum emitting cesium lead halide perovskite nanocrystals

PubMed Central

Zhang, Chengxi; Yin, Yuhang

2017-01-01

Colloidal perovskite nanocrystals comprised of all inorganic cesium lead halide (CsPbX3, X = Cl, Br, I or a mixture thereof) have potential as optical gain materials due to their high luminescence efficiency. In this work, cesium lead halide nanocrystals are continuously synthesized via a microreactor system consisting of poly(tetrafluoroethylene) (PTFE) capillaries. The synthesized nanocrystals possess excellent optical properties, including a full width at half maximum of 19–35 nm, high fluorescence quantum yield of 47.8–90.55%, and photoluminescence emission in the range of 450–700 nm. For the same precursor concentrations, the photoluminescence emission peak generally increases with increasing reaction temperature, revealing a controllable temperature effect on the photoluminescence characteristics of the synthesized nanocrystals. For quantum dots synthesized with a Br/I ratio of 1:3, a slight blue shift was observed for reaction temperatures greater than 100 °C. This PTFE-based microreactor system provides the unique capability of continuously synthesizing high-quality perovskite nanocrystals that emit over the full visible spectrum with applications ranging from displays and optoelectronic devices. PMID:29259867

Low Temperature Vacuum Synthesis of Triangular CoO Nanocrystal/Graphene Nanosheets Composites with Enhanced Lithium Storage Capacity

PubMed Central

Guan, Qun; Cheng, Jianli; Li, Xiaodong; Wang, Bin; Huang, Ling; Nie, Fude; Ni, Wei

2015-01-01

CoO nanocrystal/graphene nanosheets (GNS) composites, consisting of a triangular CoO nanocrystal of 2~20 nm on the surface of GNS, are synthesized by a mild synthetic method. First, cobalt acetate tetrahydrate is recrystallized in the alcohol solution at a low temperature. Then, graphene oxide mixed with cobalt-precursor followed by high vacuum annealing to form the CoO nanocrystal/GNS composites. The CoO nanocrystal/GNS composites exhibit a high reversible capacity of 1481.9 m Ah g−1 after 30 cycles with a high Coulombic efficiency of over 96% when used as anode materials for lithium ion battery. The excellent electrochemical performances may be attributed to the special structure of the composites. The well-dispersed triangular CoO nanocrystal on the substrate of conductive graphene can not only have a shorter diffusion length for lithium ions, better stress accommodation capability during the charge-discharge processes and more accessible active sites for lithium-ion storage and electrolyte wetting, but also possess a good conductive network, which can significantly improve the whole electrochemical performance. PMID:25961670

Synthesis, Deposition, and Microstructure Development of Thin Films Formed by Sulfidation and Selenization of Copper Zinc Tin Sulfide Nanocrystals

NASA Astrophysics Data System (ADS)

Chernomordik, Boris David

Significant reduction in greenhouse gas emission and pollution associated with the global power demand can be accomplished by supplying tens-of-terawatts of power with solar cell technologies. No one solar cell material currently on the market is poised to meet this challenge due to issues such as manufacturing cost, material shortage, or material toxicity. For this reason, there is increasing interest in efficient light-absorbing materials that are comprised of abundant and non-toxic elements for thin film solar cell. Among these materials are copper zinc tin sulfide (Cu2ZnSnS4, or CZTS), copper zinc tin selenide (Cu2ZnSnSe4, or CZTSe), and copper zinc tin sulfoselenide alloys [Cu2ZnSn(SxSe1-x )4, or CZTSSe]. Laboratory power conversion efficiencies of CZTSSe-based solar cells have risen to almost 13% in less than three decades of research. Meeting the terawatt challenge will also require low cost fabrication. CZTSSe thin films from annealed colloidal nanocrystal coatings is an example of solution-based methods that can reduce manufacturing costs through advantages such as high throughput, high material utilization, and low capital expenses. The film microstructure and grain size affects the solar cell performance. To realize low cost commercial production and high efficiencies of CZTSSe-based solar cells, it is necessary to understand the fundamental factors that affect crystal growth and microstructure evolution during CZTSSe annealing. Cu2ZnSnS4 (CZTS) nanocrystals were synthesized via thermolysis of single-source cation and sulfur precursors copper, zinc and tin diethyldithiocarbamates. The average nanocrystal size could be tuned between 2 nm and 40 nm, by varying the synthesis temperature between 150 °C and 340 °C. The synthesis is rapid and is completed in less than 10 minutes. Characterization by X-ray diffraction, Raman spectroscopy, transmission electron microscopy and energy dispersive X-ray spectroscopy confirm that the nanocrystals are nominally stoichiometric kesterite CZTS. The ~2 nm nanocrystals synthesized at 150 °C exhibit quantum confinement, with a band gap of 1.67 eV. Larger nanocrystals have the expected bulk CZTS band gap of 1.5 eV. Several micron thick films deposited by drop casting colloidal dispersions of ~40 nm CZTS nanocrystals were crack-free, while those cast using 5 nm nanocrystals had micron-scale cracks. We showed the applicability of these nanocrystal coatings for thin film solar cells by demonstrating a CZTS thin film solar cell using coatings annealed in a sulfur atmosphere. We conducted a systematic study of the factors controlling crystal growth and microstructure development during sulfidation annealing of films cast from colloidal dispersions of CZTS nanocrystals. The film microstructure is controlled by concurrent normal and abnormal grain growth. At 600 °C to 800 °C and low sulfur pressures (50 Torr), abnormal CZTS grains up to 10 microm in size grow on the surface of the CZTS nanocrystal film via transport of material from the nanocrystals to the abnormal grains. Meanwhile, the nanocrystals coarsen, sinter, and undergo normal grain growth. The driving force for abnormal grain growth is the reduction in total energy associated with the high surface area nanocrystals. The eventual coarsening of the CZTS nanocrystals reduces the driving force for abnormal crystal growth. Increasing the sulfur pressure by an order of magnitude to 500 Torr accelerates both normal and abnormal crystal growth though sufficient acceleration of the former eventually reduces the latter by reducing the driving force for abnormal grain growth. For example, at high temperatures (700-800 oC) and sulfur pressures (500 Torr) normal grains quickly grow to ~500 nm which significantly reduces abnormal grain growth. The use of soda lime glass as the substrate, instead of quartz, accelerates normal grain growth. Normal grains grow to ~500 nm at lower temperatures and sulfur pressures (i.e., 600 °C and 50 Torr) than those required to grow the same size grains on quartz (700 °C and 500 Torr). Moreover, carbon is removed by volatilization from films where normal crystal growth is fast. There are significant differences in the chemistry and in the thermodynamics involved during selenization and sulfidation of CZTS colloidal nanocrystal coatings to form CZTSSe or CZTS thin films, respectively. To understand these differences, the roles of vapor pressure, annealing temperature, and heating rate in the formation of different microstructures of CZTSSe films were investigated. Selenization produced a bi-layer microstructure where a large CZTSSe-crystal layer grew on top of a nanocrystalline carbon-rich bottom layer. Differences in the chemistry of carbon and selenium and that of carbon and sulfur account for this segregation of carbon during selenization. For example, CSe 2 and CS2, both volatile species, may form as a result of chalcogen interactions with carbon during annealing. Unlike CS2, however, CSe2 may readily polymerize at room temperature and one atmosphere. Carbon segregation may be occurring only during selenization due to the formation of a Cu-Se polymer [i.e., (CSe 2-x)] within the nanocrystal film. The (CSe2-x) inhibits sintering of nanocrystals in the bottom layer. Additionally, a fast heating rate results in temperature variations that lead to transient condensation of selenium on the film. This is observed only during selenization because the equilibrium vapor pressure of selenium is lower than that of sulfur. The presence of liquid selenium during sintering accelerates coarsening and densification of the normal crystal layer (no abnormal crystal layer) by liquid phase sintering. Carbon segregation does not occur where liquid selenium was present.

Aqueous synthesis of III-V semiconductor GaP and InP exhibiting pronounced quantum confinement.

PubMed

Gao, Shanmin; Lu, Jun; Chen, Nan; Zhao, Yan; Xie, Yi

2002-12-21

A mild aqueous synthesis route was successfully established to synthesize well crystallized and monodisperse GaP and InP nanocrystals, which were proved to exhibit pronounced quantum confinement by room-temperature UV/Vis adsorption and photoluminescence (PL) spectra.

In-situ nano-crystal-to-crystal transformation synthesis of energetic materials based on three 5,5′-azotetrazolate Cr(III) salts

PubMed Central

Miao, Yu; Qiu, Yanxuan; Cai, Jiawei; Wang, Zizhou; Yu, Xinwei; Dong, Wen

2016-01-01

The in-situ nano-crystal-to-crystal transformation (SCCT) synthesis provides a powerful approach for tailoring controllable feature shapes and sizes of nano crystals. In this work, three nitrogen-rich energetic nano-crystals based on 5,5′-azotetrazolate(AZT2−) Cr(III) salts were synthesized by means of SCCT methodology. SEM and TEM analyses show that the energetic nano-crystals feature a composition- and structure-dependent together with size-dependent thermal stability. Moreover, nano-scale decomposition products can be obtained above 500 °C, providing a new method for preparing metallic oxide nano materials. PMID:27869221

Nanocrystal synthesis and thin film formation for earth abundant photovoltaics

NASA Astrophysics Data System (ADS)

Carter, Nathaniel J.

Providing access to on-demand energy at the global scale is a grand challenge of our time. The fabrication of solar cells from nanocrystal inks comprising earth abundant elements represents a scalable and sustainable photovoltaic technology with the potential to meet the global demand for electricity. Solar cells with Cu2ZnSn(S,Se)4 (CZTSSe) absorber layers are of particular interest due to the high absorption coefficient of CZTSSe, its band gap in the ideal range for efficient photovoltaic power conversion, and the relative abundance of its constituent elements in the earth's crust. Despite the promise of this material system, CZTSSe solar cell efficiencies reported throughout literature have failed to exceed 12.6%, principally due to the low open-circuit voltage (VOC) achieved in these devices compared to the absorber band gap. The work presented herein primarily aims to address the low VOC problem. First, the fundamental cause for such low VOC's is investigated. Interparticle compositional inhomogeneities identified in the synthesized CZTS nanocrystals and their effect on the absorber layer formation and device performance are characterized. Real-time energy-dispersive x-ray diffraction (EDXRD) elucidates the role of these inhomogeneities in the mechanism by which a film of CZTS nanocrystals converts into a dense absorber layer comprising micron-sized CZTSSe grains upon annealing in a selenium atmosphere (selenization). Additionally, a direct correlation between the nanocrystal inhomogeneities and the VOC in completed devices is observed. Detailed characterization of CZTSSe solar cells identifies electrical potential fluctuations in the CZTSSe absorber - due to spatial composition variations not unlike those observed in the nanocrystals - as a primary V OC inhibitor. Additional causes for low VOC's in CZTSSe solar cells proposed in the literature involve recombination at the interface between the CZTSSe absorber and: (1) the n-type, CdS buffer layer, or (2) the Mo back contact, and work is presented to address these issues. A chemical-mechanical polishing procedure is developed to afford modification of the CZTSSe absorber surface, and in turn the CZTSSe/CdS interface. However, such treatment results in a failure of the resultant solar cells to produce any photogenerated current without annealing/selenizing the absorber again prior to the deposition of CdS. For nanocrystal-based CZTSSe solar cells, the possibility of V OC limitations due to back surface recombination may be related to the formation of the C- and Se-rich layer of fine grains between the CZTSSe layer and the Mo contact, which is largely attributed to the long-chain organic solvent and ligand typically utilized in formulating the nanocrystal ink. CZTS nanocrystals are synthesized using a lighter but chemically similar organic solvent, and while films selenized from these particles appear to contain qualitatively less carbon, devices with these absorbers fail to produce noteworthy efficiencies. Finally, Cu2ZnSn(S,Se)4 (CMTSSe) is investigated as a proof-of-concept PV material due to its structural similarity to CZTSSe and the magnetic properties of Mn, which may prove advantageous in spintronic photovoltaic hybrid devices. While initial results demonstrate diode behavior and photoresponse from a CMTSSe/CdS junction, further processing optimization is necessary to realize meaningful device efficiencies.

Synthesis of ZnO Nanocrystal-Graphene Composite by Mechanical Milling and Sonication-Assisted Exfoliation

NASA Astrophysics Data System (ADS)

Arora, Sweety; Srivastava, Chandan

2017-02-01

A ZnO nanocrystal-graphene composite was synthesized by a two-step method involving mechanical milling and sonication-assisted exfoliation. Zn metal powder was first ball-milled with graphite powder for 30 h in water medium. This ball-milled mixture was then subjected to exfoliation by sonication in the presence of sodium lauryl sulfate surfactant to produce graphene decorated with spherical agglomerates of ultrafine nanocrystalline ZnO. The presence of a few layers of graphene was confirmed by Raman spectroscopy and atomic force microscopy measurements. The size, phase identity and composition of the ZnO nanocrystals was determined by transmission electron microscopy measurements.

Optically imprinted reconfigurable photonic elements in a VO{sub 2} nanocomposite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jostmeier, Thorben; Betz, Markus; Zimmer, Johannes

We investigate the optical and thermal hysteresis of single-domain vanadium dioxide nanocrystals fabricated by ion beam synthesis in a fused silica matrix. The nanocrystals exhibit a giant hysteresis, which permits to optically generate a long-time stable supercooled metallic phase persistent down to practically room temperature. Spatial patterns of supercooled and insulating nanocrystals feature a large dielectric contrast, in particular, for telecom wavelengths. We utilize this contrast to optically imprint reconfigurable photonic elements comprising diffraction gratings as well as on- and off-axis zone plates. The structures allow for highly repetitive (>10{sup 4}) cycling through the phase transition without structural damage.

Atomistic understanding of cation exchange in PbS nanocrystals using simulations with pseudoligands

PubMed Central

Fan, Zhaochuan; Lin, Li-Chiang; Buijs, Wim; Vlugt, Thijs J. H.; van Huis, Marijn A.

2016-01-01

Cation exchange is a powerful tool for the synthesis of nanostructures such as core–shell nanocrystals, however, the underlying mechanism is poorly understood. Interactions of cations with ligands and solvent molecules are systematically ignored in simulations. Here, we introduce the concept of pseudoligands to incorporate cation-ligand-solvent interactions in molecular dynamics. This leads to excellent agreement with experimental data on cation exchange of PbS nanocrystals, whereby Pb ions are partially replaced by Cd ions from solution. The temperature and the ligand-type control the exchange rate and equilibrium composition of cations in the nanocrystal. Our simulations reveal that Pb ions are kicked out by exchanged Cd interstitials and migrate through interstitial sites, aided by local relaxations at core–shell interfaces and point defects. We also predict that high-pressure conditions facilitate strongly enhanced cation exchange reactions at elevated temperatures. Our approach is easily extendable to other semiconductor compounds and to other families of nanocrystals. PMID:27160371

Transparent 'solution' of ultrathin magnesium hydroxide nanocrystals for flexible and transparent nanocomposite films.

PubMed

Wang, Jie-Xin; Sun, Qian; Chen, Bo; Wu, Xi; Zeng, Xiao-Fei; Zhang, Cong; Zou, Hai-Kui; Chen, Jian-Feng

2015-05-15

Transparent solutions of nanocrystals exhibit many unique properties, and are thus attractive materials for numerous applications. However, the synthesis of transparent nanocrystal solutions of magnesium hydroxide (MH) with wide applications is yet to be realized. Here, we report a facile two-step process, which includes a direct reactive precipitation in alcohol phase instead of aqueous phase combined with a successive surface modification, to prepare transparent alcohol solutions containing lamellar MH nanocrystals with an average size of 52 nm and an ultrathin thickness of 1-2 nm, which is the thinnest MH nanoplatelet reported in the literatures. Further, highly flexible and transparent nanocomposite films are fabricated with a solution mixing method by adding the transparent MH nanocrystal solutions into PVB solution. Considering the simplicity of the fabrication process, high transparency and good flexibility, this MH/polymer nanocomposite film is promising for flame-resistant applications in plastic electronics and optical devices with high transparency, such as flexible displays, optical filters, and flexible solar cells.

Microstructure and magnetic properties of MFe2O4 (M = Co, Ni, and Mn) ferrite nanocrystals prepared using colloid mill and hydrothermal method

NASA Astrophysics Data System (ADS)

Wang, Wei; Ding, Zui; Zhao, Xiruo; Wu, Sizhu; Li, Feng; Yue, Ming; Liu, J. Ping

2015-05-01

Three kinds of spinel ferrite nanocrystals, MFe2O4 (M = Co, Ni, and Mn), are synthesized using colloid mill and hydrothermal method. During the synthesis process, a rapid mixing and reduction of cations with sodium borohydride (NaBH4) take place in a colloid mill then through a hydrothermal reaction, a slow oxidation and structural transformation of the spinel ferrite nanocrystals occur. The phase purity and crystal lattice parameters are estimated by X-ray diffraction studies. Scanning electron microscopy and transmission electron microscopy images show the morphology and particle size of the as-synthesized ferrite nanocrystals. Raman spectrum reveals active phonon modes at room temperature, and a shifting of the modes implies cation redistribution in the tetrahedral and octahedral sites. Magnetic measurements show that all the obtained samples exhibit higher saturation magnetization (Ms). Meanwhile, experiments demonstrate that the hydrothermal reaction time has significant effects on microstructure, morphologies, and magnetic properties of the as-synthesized ferrite nanocrystals.

Growth mechanisms of MgO nanocrystals via a sol-gel synthesis using different complexing agents

PubMed Central

2014-01-01

In the preparation of nanostructured materials, it is important to optimize synthesis parameters in order to obtain the desired material. This work investigates the role of complexing agents, oxalic acid and tartaric acid, in the production of MgO nanocrystals. Results from simultaneous thermogravimetric analysis (STA) show that the two different synthesis routes yield precursors with different thermal profiles. It is found that the thermal profiles of the precursors can reveal the effects of crystal growth during thermal annealing. X-ray diffraction confirms that the final products are pure, single phase and of cubic shape. It is also found that complexing agents can affect the rate of crystal growth. The structures of the oxalic acid and tartaric acid as well as the complexation sites play very important roles in the formation of the nanocrystals. The complexing agents influence the rate of growth which affects the final crystallite size of the materials. Surprisingly, it is also found that oxalic acid and tartaric acid act as surfactants inhibiting crystal growth even at a high temperature of 950°C and a long annealing time of 36 h. The crystallite formation routes are proposed to be via linear and branched polymer networks due to the different structures of the complexing agents. PMID:24650322

Origin and chemical composition of the amorphous material from the intergrain pores of self-assembled cubic ZnS:Mn nanocrystals

NASA Astrophysics Data System (ADS)

Stefan, Mariana; Vlaicu, Ioana Dorina; Nistor, Leona Cristina; Ghica, Daniela; Nistor, Sergiu Vasile

2017-12-01

We have shown in previous investigations that the low temperature collective magnetism observed in mesoporous cubic ZnS:Mn nanocrystalline powders prepared by colloidal synthesis, with nominal doping concentrations above 0.2 at.%, is due to the formation of Mn2+ clusters with distributed antiferromagnetic coupling localized in an amorphous phase found between the cubic ZnS:Mn nanocrystals. Here we investigate the composition, origin and thermal annealing behavior of this amorphous phase in such a mesoporous ZnS:Mn sample doped with 5 at.% Mn nominal concentration. Correlated analytical transmission electron microscopy, multifrequency electron paramagnetic resonance and Fourier transform infrared spectroscopy data show that the amorphous nanomaterial consists of unreacted precursor hydrated zinc and manganese acetates trapped inside the pores and on the surface of the cubic ZnS nanocrystals. The decomposition of the acetates under isochronal annealing up to 270 °C, where the mesoporous structure is still preserved, lead to changes in the nature and strength of the magnetic interactions between the aggregated Mn2+ ions. These results strongly suggest the possibility to modulate the magnetic properties of such transition metal ions doped II-VI mesoporous structures by varying the synthesis conditions and/or by post-synthesis thermochemical treatments.

State of the art of nanocrystals technology for delivery of poorly soluble drugs

NASA Astrophysics Data System (ADS)

Zhou, Yuqi; Du, Juan; Wang, Lulu; Wang, Yancai

2016-09-01

Formulation of nanocrystals is a distinctive approach which can effectively improve the delivery of poorly water-soluble drugs, thus enticing the development of the nanocrystals technology. The characteristics of nanocrystals resulted in an exceptional drug delivery conductance, including saturation solubility, dissolution velocity, adhesiveness, and affinity. Nanocrystals were treated as versatile pharmaceuticals that could be delivered through almost all routes of administration. In the current review, oral, pulmonary, and intravenous routes of administration were presented. Also, the targeting of drug nanocrystals, as well as issues of efficacy and safety, were also discussed. Several methods were applied for nanocrystals production including top-down production strategy (media milling, high-pressure homogenization), bottom-up production strategy (antisolvent precipitation, supercritical fluid process, and precipitation by removal of solvent), and the combination approaches. Moreover, this review also described the evaluation and characterization of the drug nanocrystals and summarized the current commercial pharmaceutical products utilizing nanocrystals technology.

Nanocrystals Technology for Pharmaceutical Science.

PubMed

Cheng, Zhongyao; Lian, Yumei; Kamal, Zul; Ma, Xin; Chen, Jianjun; Zhou, Xinbo; Su, Jing; Qiu, Mingfeng

2018-05-17

Nanocrystals technology is a promising method for improving the dissolution rate and enhancing the bioavailability of poorly soluble drugs. In recent years, it has been developing rapidly and applied to drug research and engineering. Nanocrystal drugs can be formulated into various dosage forms. This review mainly focused on the nanocrystals technology and its application in pharmaceutical science. Firstly, different preparation methods of nanocrystal technology and the characterization of nanocrystal drugs are briefly described. Secondly, the application of nanocrystals technology in pharmaceutical science is mainly discussed followed by the introduction of sustained release formulations. Then, the scaling up process, marketed nanocrystal drug products and regulatory aspects about nanodrugs are summarized. Finally, the specific challenges and opportunities of nanocrystals technology for pharmaceutical science are summarized and discussed. This review will provide a comprehensive guide for scientists and engineers in the field of pharmaceutical science and biochemical engineering. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Characterization of Dust-Plasma Interactions In Non-Thermal Plasmas Under Low Pressure and the Atmospheric Pressure

NASA Astrophysics Data System (ADS)

Bilik, Narula

This dissertation research focuses on the experimental characterization of dust-plasma interactions at both low and atmospheric pressure. Its goal is to fill the knowledge gaps in (1) the fundamental research of low pressure dusty plasma electrons, which mainly relied on models with few experimental results; and (2) the nanoparticle synthesis process in atmospheric pressure uniform glow plasmas (APGDs), which is largely unexplored in spite of the economical advantage of APGDs in nanotechnology. The low pressure part of the dissertation research involves the development of a complete diagnostic process for an argon-siline capacitively-coupled RF plasma. The central part of the diagnostic process is the Langmuir probe measurement of the electron energy probability function (EEPF) in a dusty plasma, which has never been measured before. This is because the dust particles in the plasma cause severe probe surface contamination and consequently distort the measurement. This problem is solved by adding a solenoid-actuated shield structure to the Langmuir probe, which physically protects the Langmuir probe from the dust particle deposition to ensure reliable EEPF measurements. The dusty plasma EEPFs are characterized by lower electron density and higher electron temperature accompanied by a drop in the low energy electron population. The Langmuir probe measurement is complemented with other characterizations including the capacitive probe measurement, power measurement, and dust particle collection. The complete diagnostic process then gives a set of local plasma parameters as well as the details of the dust-electron interactions reflected in the EEPFs. This set of data serves as input for an analytical model of nanoparticle charging to yield the time evolution of nanoparticle size and charge in the dusty plasma. The atmospheric pressure part of the dissertation focuses on the design and development of an APGD for zinc oxide nanocrystal synthesis. One of the main difficulties in maintaining an APGD is ensuring its uniformity over large discharge volume. By examining past atmospheric pressure plasma reactor designs and looking into the details of the atmospheric pressure gas breakdown mechanism, three design features are proposed to ensure the APGD uniformity. These include the use of a dielectric barrier and the RF driving frequency, as well as a pre-ionization technique achieved by having a non-uniform gap spacing in a capacitively-coupled concentric cylinder reactor. The resulting APGD reactor operates stably in the abnormal glow regime using either helium or argon as the carrier gas. Diethylzinc (DEZ) and oxygen precursors are injected into the APGD to form zinc oxide nanocrystals. The physical and optical properties of these nanocrystals are characterized, and the system parameters that impact the nanoparticle size and deposition rate are identified.

Rare Earth Ion-Doped Upconversion Nanocrystals: Synthesis and Surface Modification

PubMed Central

Chang, Hongjin; Xie, Juan; Zhao, Baozhou; Liu, Botong; Xu, Shuilin; Ren, Na; Xie, Xiaoji; Huang, Ling; Huang, Wei

2014-01-01

The unique luminescent properties exhibited by rare earth ion-doped upconversion nanocrystals (UCNPs), such as long lifetime, narrow emission line, high color purity, and high resistance to photobleaching, have made them widely used in many areas, including but not limited to high-resolution displays, new-generation information technology, optical communication, bioimaging, and therapy. However, the inherent upconversion luminescent properties of UCNPs are influenced by various parameters, including the size, shape, crystal structure, and chemical composition of the UCNPs, and even the chosen synthesis process and the surfactant molecules used. This review will provide a complete summary on the synthesis methods and the surface modification strategies of UCNPs reported so far. Firstly, we summarize the synthesis methodologies developed in the past decades, such as thermal decomposition, thermal coprecipitation, hydro/solvothermal, sol-gel, combustion, and microwave synthesis. In the second part, five main streams of surface modification strategies for converting hydrophobic UCNPs into hydrophilic ones are elaborated. Finally, we consider the likely directions of the future development and challenges of the synthesis and surface modification, such as the large-scale production and actual applications, stability, and so on, of the UCNPs. PMID:28346995

Novel Magnetic Nanomaterials Inspired by Magnetotactic Baterial: Topical Review

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prozorov, Tanya; Bazylinki, Dennis A.; Mallapragada, Surya K.

2013-05-14

Magnetotactic bacteria, known to produce magnetic nanocrystals with uniform shapes and sizes at physiological conditions, serve as an inspiration and source of a number of biological macromolecules used for the biomimetic synthesis of a variety of magnetic nanomaterials. This review discusses the current state of understanding of magnetosome biomineralization in magnetotactic bacteria, as well as the ways in which iron biomineralization processes can be utilized for tailored in vivo formation of complex magnetic nanomaterials, not occurring in magnetotactic bacteria naturally. The review assesses the current efforts on in vitro synthesis of a variety of magnetic nanoparticles using bioinspired approaches bymore » utilizing mineralization proteins from magnetotactic bacteria, and surveys biomimetic strategies for the rational synthesis of various magnetic nanomaterials under ambient conditions. Finally, this review presents magnetic characterization of nanoparticles, highlighting differences in magnetic behavior between magnetic nanoparticles produced using bioinspired in vivo and in vitro strategies, compared to those produced using conventional methods. This in turn impacts their utility in a wide range of applications for magnetic nanoparticles, which are examined in detail, where bioinspired synthesis methods have potentially provided added advantages.« less

Synthesis of nanometer-sized sodalite without adding organic additives.

PubMed

Fan, Wei; Morozumi, Kazumasa; Kimura, Riichiro; Yokoi, Toshiyuki; Okubo, Tatsuya

2008-06-01

Aggregates (80 nm) of sodalite nanocrystals with crystallite sizes ranging from 20 to 40 nm have been synthesized from a sodium aluminosilicate solution at low temperature, without adding any organic additives, while paying attention to the key factors for the synthesis of nanosized zeolite crystals. The physical properties of nanosized sodalite crystals were characterized by X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, 29Si solid-state magic-angle spinning (MAS) NMR, and N2 adsorption. As expected, the external surface area of nanosized sodalite crystals is significantly increased compared with that of microsized sodalite crystals. The size of synthesized sodalite crystals can be controlled from 20 nm to 10 microm. It is found that the preparation of a homogeneous aluminosilicate solution followed by the formation of an aluminosilicate hard gel by adjusting the initial composition, for example, SiO2/Al2O3 and Na2O/H2O ratios, is critical for synthesis.

Seeded Growth Route to Noble Calcium Carbonate Nanocrystal.

PubMed

Islam, Aminul; Teo, Siow Hwa; Rahman, M Aminur; Taufiq-Yap, Yun Hin

2015-01-01

A solution-phase route has been considered as the most promising route to synthesize noble nanostructures. A majority of their synthesis approaches of calcium carbonate (CaCO3) are based on either using fungi or the CO2 bubbling methods. Here, we approached the preparation of nano-precipitated calcium carbonate single crystal from salmacis sphaeroides in the presence of zwitterionic or cationic biosurfactants without external source of CO2. The calcium carbonate crystals were rhombohedron structure and regularly shaped with side dimension ranging from 33-41 nm. The high degree of morphological control of CaCO3 nanocrystals suggested that surfactants are capable of strongly interacting with the CaCO3 surface and control the nucleation and growth direction of calcium carbonate nanocrystals. Finally, the mechanism of formation of nanocrystals in light of proposed routes was also discussed.

Seeded Growth Route to Noble Calcium Carbonate Nanocrystal

PubMed Central

Islam, Aminul; Teo, Siow Hwa; Rahman, M. Aminur; Taufiq-Yap, Yun Hin

2015-01-01

A solution-phase route has been considered as the most promising route to synthesize noble nanostructures. A majority of their synthesis approaches of calcium carbonate (CaCO3) are based on either using fungi or the CO2 bubbling methods. Here, we approached the preparation of nano-precipitated calcium carbonate single crystal from salmacis sphaeroides in the presence of zwitterionic or cationic biosurfactants without external source of CO2. The calcium carbonate crystals were rhombohedron structure and regularly shaped with side dimension ranging from 33–41 nm. The high degree of morphological control of CaCO3 nanocrystals suggested that surfactants are capable of strongly interacting with the CaCO3 surface and control the nucleation and growth direction of calcium carbonate nanocrystals. Finally, the mechanism of formation of nanocrystals in light of proposed routes was also discussed. PMID:26700479

Nanostructures by ion beams

NASA Astrophysics Data System (ADS)

Schmidt, B.

Ion beam techniques, including conventional broad beam ion implantation, ion beam synthesis and ion irradiation of thin layers, as well as local ion implantation with fine-focused ion beams have been applied in different fields of micro- and nanotechnology. The ion beam synthesis of nanoparticles in high-dose ion-implanted solids is explained as phase separation of nanostructures from a super-saturated solid state through precipitation and Ostwald ripening during subsequent thermal treatment of the ion-implanted samples. A special topic will be addressed to self-organization processes of nanoparticles during ion irradiation of flat and curved solid-state interfaces. As an example of silicon nanocrystal application, the fabrication of silicon nanocrystal non-volatile memories will be described. Finally, the fabrication possibilities of nanostructures, such as nanowires and chains of nanoparticles (e.g. CoSi2), by ion beam synthesis using a focused Co+ ion beam will be demonstrated and possible applications will be mentioned.

Synthesis, Characterization, and Fabrication of All Inorganic Quantum Dot LEDs

NASA Astrophysics Data System (ADS)

Salman, Haider Baqer

Quantum Dot LEDs with all inorganic materials are investigated in this thesis. The research was motivated by the potential disruptive technology of core shell quantum dots in lighting and display applications. These devices consisted of three main layers: hole transport layer (HTL), electron transport layer (ETL), and emissive layer where the emission of photons occurs. The latter part was formed of CdSe / ZnS core-shell quantum dots, which were synthesized following hot injection method. The ETL and the HTL were formed of zinc oxide nanocrystals and nickel oxide, respectively. Motivated by the low cost synthesis and deposition, NiO and ZnO were synthesized following sol-gel method and deposited using spin coating. The anode of the device was a commercial slide of indium tin oxide deposited on glass substrate while the cathode was a 100 nm aluminum layer that was deposited using an Auto 306T Edwards thermal evaporator. In this research, Raman spectroscopy, micro-photoluminescence spectroscopy, absorbance spectroscopy, X-ray diffraction (XRD) spectroscopy, and atomic force microscopy, were used to characterize the materials. Three sharp peaks were observed in the XRD measurements of the NiO thin film related to three planes and indicated a proper level of crystallinity. The AFM image of the same material indicated a roughness RMS value of 2 nm which was accepted for a device fabrication. The photoluminescence spectrum exhibited a peak at 515 nm for the quantum dots and a peak at 315 nm for the ZnO nanocrystals. The narrow shape of these spectra proved a limited amount of size variation. The transfer characteristics of the fabricated device indicated that the current density ramped up producing green light when the voltage was higher than 5 V to reach 160 mA cm -2 at 9 V.

Synthesis of new nanocrystal materials

NASA Astrophysics Data System (ADS)

Hassan, Yasser Hassan Abd El-Fattah

Colloidal semiconductor nanocrystals (NCs) have sparked great excitement in the scientific community in last two decades. NCs are useful for both fundamental research and technical applications in various fields owing to their size and shape-dependent properties and their potentially inexpensive and excellent chemical processability. These NCs are versatile fluorescence probes with unique optical properties, including tunable luminescence, high extinction coefficient, broad absorption with narrow photoluminescence, and photobleaching resistance. In the past few years, a lot of attention has been given to nanotechnology based on using these materials as building blocks to design light harvesting assemblies. For instant, the pioneering applications of NCs are light-emitting diodes, lasers, and photovoltaic devices. Synthesis of the colloidal stable semiconductor NCs using the wet method of the pyrolysis of organometallic and chalcogenide precursors, known as hot-injection approach, is the chart-topping preparation method in term of high quality and monodisperse sized NCs. The advancement in the synthesis of these artificial materials is the core step toward their applications in a broad range of technologies. This dissertation focuses on exploring various innovative and novel synthetic methods of different types of colloidal nanocrystals, both inorganic semiconductors NCs, also known as quantum dots (QDs), and organic-inorganic metal halide-perovskite materials, known as perovskites. The work presented in this thesis focuses on pursuing fundamental understanding of the synthesis, material properties, photophysics, and spectroscopy of these nanostructured semiconductor materials. This thesis contains 6 chapters and conclusions. Chapters 1?3 focus on introducing theories and background of the materials being synthesized in the thesis. Chapter 4 demonstrates our synthesis of colloidal linker--free TiO2/CdSe NRs heterostructures with CdSe QDs grown in the presence of TiO2 NRs using seeded--growth type colloidal injection approach. Chapter 5 explores a novel approach of directly synthesized CdSe NCs with electroactive ligands. The last Chapter focuses on a new class of perovskites. I describe my discovery of a (bottom-up) simple method to synthesize colloidally stable methyl ammonium lead halide perovskite nanocrystals seeded from high quality PbX2 NCs with a pre-targeted size. This chapter reports advances in preparation of both these materials (PbX2, and lead halide perovskite NCs).

Biomimetic Synthesis of Noble Metal Nanocrystals and the Mechanism Studies

NASA Astrophysics Data System (ADS)

Ruan, Lingyan

Nanostructured materials with dimensions reaching the nanoscale possess novel properties different from their bulk counterparts. Engineering nanomaterials to exploit their improved functions show important applications in catalysis, electrocatalysis, electronics, optoelectronics, and energy devices. One of the challenges to date is to develop methods for producing nanomaterials in a controllable and predictable fashion. We seek to develop novel biomimetic synthetic protocols for programmable nanomaterial synthesis, i.e., using biomolecules with specific material recognition properties to manipulate nanomaterial morphologies and structures. Starting with three Pt binding peptides with distinct recognition properties, i.e., a Pt material specific peptide BP7A and two Pt facet specific peptides T7 (Pt {100} facet specific) and S7 (Pt {111} facet specific), we demonstrate a rational creation of Pt bipyramids, a new type of shape for Pt nanocrystals. The BP7A peptide is found to be able to introduce twinning during Pt nanocrystal growth. We use it to generate single twinned seeds for Pt nanocrystals. Together with targeted facet stabilization using T7/S7 peptides, Pt {100} bipyramid and {111} bipyramid are successfully synthesized for the first time. We further utilize the twin introducing property of the BP7A peptide to generate ultrathin Pt nanowire with high twin densities. We show that the Pt nanowire possesses higher electrocatalytic activity and durability in oxygen reduction and methanol oxidation reactions due to its one-dimensional nanostructure and the presence of dense twin defects, demonstrating the concept of defect engineering in nanocrystals as a strategy in the design of novel electrocatalyst. The organic-inorganic interface is a key issue in many fields including colloidal syntheses and biomimetics, the understanding of which can enable the design of new material synthetic strategies. We aim to understand how the Pt binding peptides modulate the formations of specific Pt nanostructures. We start with mechanistic investigations on S7 peptide's Pt {111} recognition property, and proceed to studying BP7A peptide's twin introducing property. With combined experimental and computational efforts, we identify the molecular origins of the biorecognition properties of these two peptides. Moreover, we extend extracted biomimetic principles to the rational design/selection of small organic molecules that deliver anticipated traits for controlled colloidal synthesis for other noble metals (Pd and Rh). Overall, we demonstrate the power of biomimetic synthesis in rationally creating nanomaterial structures with novel properties. Our mechanism studies demonstrate the rich information one can derive from biomimetic synthesis, and the broad applicability of biomimetic principles to engineering material structures for many potential applications.

Synthesis, characterization and photovoltaic performance of Mn-doped ZnS quantum dots- P3HT hybrid bulk heterojunction solar cells

NASA Astrophysics Data System (ADS)

Jabeen, Uzma; Adhikari, Tham; Shah, Syed Mujtaba; Pathak, Dinesh; Nunzi, Jean-Michel

2017-11-01

Zinc sulphide (ZnS) and transition metal-doped ZnS nanocrystals were synthesized by co-precipitation method. Further the synthesized nanocrystals were characterized by Field Emission Scanning Electron Microscope (FESEM), High Resolution Transmission Electron Microscope (HRTEM), Fluorescence, UV-Visible, X-ray diffraction (XRD) and Fourier Transformed Infra-red (FTIR) Spectrometer (FTIR). Scanning electron microscope supplemented with EDAX was employed to attain grain size and chemical composition of the nanomaterials. A considerable blue shift of absorption band was noted by the manganese concentration (0.5 M) in the doped sample in comparison with ZnS quantum dots because of the decrease in the size of nanoparticles which may be due to quantum confinement. The photoluminescence emission observed at 596 nm is due to the emission of divalent manganese and can be ascribed to a 4T1→6A1 transition within the 3d shell. Though, the broad blue emission band was observed at 424 nm which may originates from the radiative recombination comprising defect states in the un-doped zinc sulphide quantum dots. XRD analysis exhibited that the synthesized nanomaterial endured in cubic structure. The synthesized nanomaterial combined with organic polymer P3HT, poly (3-hexyl thiophene) and worked in the construction of inverted solar cells. The photovoltaic devices with un-doped zinc sulphide quantum dots showed power conversion efficiency of 0.48% without annealing and 0.52% with annealing. By doping with manganese, the efficiency was enhanced by a factor of 0.52 without annealing and 0.59 with annealing. The morphology and packing behavior of blend of nanocrystals with organic polymer were explored using Atomic Force Microscopy.

Faradaurate-940: Synthesis, Mass Spectrometry, STEM, PDF, and SAXS Study of Au~940(SR)~160 Nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumara, Chanaka; Zuo, Xiaobing; Cullen, David A

2014-01-01

Obtaining monodisperse nanocrystals, and determining its composition to the atomic level and its atomic structure is highly desirable, but is generally lacking. Here, we report the discovery and comprehensive characterization of a 3-nm plasmonic nanocrystal with a composition of Au940 20(SCH2CH2Ph)160 4, which is, the largest mass spectrometrically characterized gold thiolate nanoparticle produced to date. The compositional assignment has been made using electrospray ionization (ESI) and matrix assisted laser desorption ionization (MALDI) mass spectrometry (MS). The MS results show an unprecedented size monodispersity, where the number of Au atoms vary by only 40 atoms (940 20). The mass spectrometrically-determined sizemore » and composition are supported by aberration-corrected scanning transmission electron microscopy (STEM) and synchrotron-based methods such as atomic pair distribution function (PDF) and small angle X-ray scattering (SAXS). Lower resolution STEM images show an ensemble of particles 1000 s per frame visually demonstrating monodispersity. Modelling of SAXS on statistically significant nanoparticle population approximately 1012 individual nanoparticles - shows that the diameter is 3.0 0.2nm, supporting mass spectrometry and electron microscopy results on monodispersity. Atomic PDF based on high energy X-ray diffraction experiments show decent match with either a Marks decahedral or truncated octrahedral structure. Atomic resolution STEM images of single particles and its FFT suggest face-centered cubic (fcc) arrangement. UV-visible spectroscopy data shows that the 940-atom size supports a surface plasmon resonance peak at 505 nm. These monodisperse plasmonic nanoparticles minimize averaging effects and has potential application in solar cells, nano-optical devices, catalysis and drug delivery.« less

Cellulose nanocrystals the next big nano-thing?

NASA Astrophysics Data System (ADS)

Postek, Michael T.; Vladar, Andras; Dagata, John; Farkas, Natalia; Ming, Bin; Sabo, Ronald; Wegner, Theodore H.; Beecher, James

2008-08-01

Biomass surrounds us from the smallest alga to the largest redwood tree. Even the largest trees owe their strength to a newly-appreciated class of nanomaterials known as cellulose nanocrystals (CNC). Cellulose, the world's most abundant natural, renewable, biodegradable polymer, occurs as whisker like microfibrils that are biosynthesized and deposited in plant material in a continuous fashion. Therefore, the basic raw materials for a future of new nanomaterials breakthroughs already abound in the environment and are available to be utilized in an array of future materials once the manufacturing processes and nanometrology are fully developed. This presentation will discuss some of the instrumentation, metrology and standards issues associated with nanomanufacturing of cellulose nanocrystals. The use of lignocellulosic fibers derived from sustainable, annually renewable resources as a reinforcing phase in polymeric matrix composites provides positive environmental benefits with respect to ultimate disposability and raw material use. Today we lack the essential metrology infrastructure that would enable the manufacture of nanotechnology-based products based on CNCs (or other new nanomaterial) to significantly impact the U.S. economy. The basic processes common to manufacturing - qualification of raw materials, continuous synthesis methods, process monitoring and control, in-line and off-line characterization of product for quality control purposes, validation by standard reference materials - are not generally in place for nanotechnology based products, and thus are barriers to innovation. One advantage presented by the study of CNCs is that, unlike other nanomaterials, at least, cellulose nanocrystal manufacturing is already a sustainable and viable bulk process. Literally tons of cellulose nanocrystals can be generated each day, producing other viable byproducts such as glucose (for alternative fuel) and gypsum (for buildings).There is an immediate need for the development of the basic manufacturing metrology infrastructure to implement fundamental best practices for manufacturing and in the determination of properties for these for nanoscale materials and the resultant products.

MICROWAVE-ASSISTED SHAPE-CONTROLLED BULK SYNTHESIS OF NOBLE NANOCRYSTALS AND THEIR CATALYTIC PROPERTIES

EPA Science Inventory

Bulk and shape-controlled synthesis of gold (Au) nanostructures with various shapes such as prisms, cubes and hexagons is described that occurs via microwave-assisted spontaneous reduction of noble metal salts using an aqueous solution of α-D-glucose, sucrose and maltose. The exp...

Williamson-Hall analysis and optical properties of small sized ZnO nanocrystals

NASA Astrophysics Data System (ADS)

Kalita, Amarjyoti; Kalita, Manos P. C.

2017-08-01

We apply Williamson-Hall (WH) method of X-ray diffraction (XRD) line profile analysis for lattice strain estimation of small sized ZnO nanocrystals (crystallite size≈4 nm). The ZnO nanocrystals are synthesized by room temperature chemical co-precipitation followed by heating at 40 °C. Zinc acetate, sodium hydroxide and 2-mercaptoethanol (ME) are used for the synthesis of the nanocrystals. {100}, {002}, {101} and {200}, {112}, {201} line profiles in the XRD pattern are significantly merged, therefore determination of the full width at half maximum values and peak positions of the line profiles required for WH analysis has been carried out by executing Rietveld refinement of the XRD pattern. Lattice strain of the 4 nm sized ZnO nanocrystals is found to be 5.8×10-3 which is significantly higher as compared to the literature reported values for larger ones (crystallite size≈17-47 nm). Role of ME as capping agent is confirmed by Fourier transform infrared spectroscopy. The band gap of the nanocrystals is determined from the UV-Visible absorption spectrum and is found to be 3.68 eV. The photoluminescence spectrum exhibits emissions in the visible (408 nm-violet, 467 nm-blue and 538 nm-green) regions showing presence of zinc interstitial and oxygen vacancy in the ZnO nanocrystals.

Facet‐Controlled Synthetic Strategy of Cu2O‐Based Crystals for Catalysis and Sensing

PubMed Central

Shang, Yang

2015-01-01

Shape‐dependent catalysis and sensing behaviours are primarily focused on nanocrystals enclosed by low‐index facets, especially the three basic facets ({100}, {111}, and {110}). Several novel strategies have recently exploded by tailoring the original nanocrystals to greatly improve the catalysis and sensing performances. In this Review, we firstly introduce the synthesis of a variety of Cu2O nanocrystals, including the three basic Cu2O nanocrystals (cubes, octahedra and rhombic dodecahedra, enclosed by the {100}, {111}, and {110} facets, respectively), and Cu2O nanocrystals enclosed by high‐index planes. We then discuss in detail the three main facet‐controlled synthetic strategies (deposition, etching and templating) to fabricate Cu2O‐based nanocrystals with heterogeneous, etched, or hollow structures, including a number of important concepts involved in those facet‐controlled routes, such as the selective adsorption of capping agents for protecting special facets, and the impacts of surface energy and active sites on reaction activity trends. Finally, we highlight the facet‐dependent properties of the Cu2O and Cu2O‐based nanocrystals for applications in photocatalysis, gas catalysis, organocatalysis and sensing, as well as the relationship between their structures and properties. We also summarize and comment upon future facet‐related directions. PMID:27980909

Facet-Controlled Synthetic Strategy of Cu2O-Based Crystals for Catalysis and Sensing.

PubMed

Shang, Yang; Guo, Lin

2015-10-01

Shape-dependent catalysis and sensing behaviours are primarily focused on nanocrystals enclosed by low-index facets, especially the three basic facets ({100}, {111}, and {110}). Several novel strategies have recently exploded by tailoring the original nanocrystals to greatly improve the catalysis and sensing performances. In this Review, we firstly introduce the synthesis of a variety of Cu 2 O nanocrystals, including the three basic Cu 2 O nanocrystals (cubes, octahedra and rhombic dodecahedra, enclosed by the {100}, {111}, and {110} facets, respectively), and Cu 2 O nanocrystals enclosed by high-index planes. We then discuss in detail the three main facet-controlled synthetic strategies (deposition, etching and templating) to fabricate Cu 2 O-based nanocrystals with heterogeneous, etched, or hollow structures, including a number of important concepts involved in those facet-controlled routes, such as the selective adsorption of capping agents for protecting special facets, and the impacts of surface energy and active sites on reaction activity trends. Finally, we highlight the facet-dependent properties of the Cu 2 O and Cu 2 O-based nanocrystals for applications in photocatalysis, gas catalysis, organocatalysis and sensing, as well as the relationship between their structures and properties. We also summarize and comment upon future facet-related directions.

Phase- and size-controllable synthesis of hexagonal upconversion rare-earth fluoride nanocrystals through an oleic acid/ionic liquid two-phase system.

PubMed

He, Meng; Huang, Peng; Zhang, Chunlei; Ma, Jiebing; He, Rong; Cui, Daxiang

2012-05-07

Herein, we introduce a facile, user- and environmentally friendly (n-octanol-induced) oleic acid (OA)/ionic liquid (IL) two-phase system for the phase- and size-controllable synthesis of water-soluble hexagonal rare earth (RE = La, Gd, and Y) fluoride nanocrystals with uniform morphologies (mainly spheres and elongated particles) and small sizes (<50 nm). The unique role of the IL 1-butyl-3-methylimidazolium hexafluorophosphate (BmimPF(6)) and n-octanol in modulating the phase structure and particle size are discussed in detail. More importantly, the mechanism of the (n-octanol-induced) OA/IL two-phase system, the formation of the RE fluoride nanocrystals, and the distinctive size- and morphology-controlling capacity of the system are presented. BmimPF(6) is versatile in term of crystal-phase manipulation, size and shape maintenance, and providing water solubility in a one-step reaction. The luminescent properties of Er(3+)-, Ho(3+)-, and Tm(3+)-doped LaF(3), NaGdF(4), and NaYF(4) nanocrystals were also studied. It is worth noting that the as-prepared products can be directly dispersed in water due to the hydrophilic property of Bmim(+) (cationic part of the IL) as a capping agent. This advantageous feature has made the IL-capped products favorable in facile surface modifications, such as the classic Stober method. Finally, the cytotoxicity evaluation of NaYF(4):Yb,Er nanocrystals before and after silica coating was conducted for further biological applications. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis And Characterization of Copper Zinc Tin Sulfide Nanoparticles And Thin Films

NASA Astrophysics Data System (ADS)

Khare, Ankur

Copper zinc tin sulfide (Cu2ZnSnS4, or CZTS) is emerging as an alternative material to the present thin film solar cell technologies such as Cu(In,Ga)Se2 and CdTe. All the elements in CZTS are abundant, environmentally benign, and inexpensive. In addition, CZTS has a band gap of ˜1.5 eV, the ideal value for converting the maximum amount of energy from the solar spectrum into electricity. CZTS has a high absorption coefficient (>104 cm-1 in the visible region of the electromagnetic spectrum) and only a few micron thick layer of CZTS can absorb all the photons with energies above its band gap. CZT(S,Se) solar cells have already reached power conversion efficiencies >10%. One of the ways to improve upon the CZTS power conversion efficiency is by using CZTS quantum dots as the photoactive material, which can potentially achieve efficiencies greater than the present thin film technologies at a fraction of the cost. However, two requirements for quantum-dot solar cells have yet to be demonstrated. First, no report has shown quantum confinement in CZTS nanocrystals. Second, the syntheses to date have not provided a range of nanocrystal sizes, which is necessary not only for fundamental studies but also for multijunction photovoltaic architectures. We resolved these two issues by demonstrating a simple synthesis of CZTS, Cu2SnS3, and alloyed (Cu2SnS3) x(ZnS)y nanocrystals with diameters ranging from 2 to 7 nm from diethyldithiocarbamate complexes. As-synthesized nanocrystals were characterized using high resolution transmission electron microscopy, X-ray diffraction, Raman spectroscopy, and energy dispersive spectroscopy to confirm their phase purity. Nanocrystals of diameter less than 5 nm were found to exhibit a shift in their optical absorption spectra towards higher energy consistent with quantum confinement and previous theoretical predictions. Thin films from CZTS nanocrystals deposited on Mo-coated quartz substrates using drop casting were found to be continuous but highly porous. Annealing CZTS nanocrystal films at temperatures as low as 400 °C led to an intense grain growth; however, thin films from CZTS nanocrystals cracked on annealing due to their high porosity. Although quantum confinement in CZTS is only accessible in nanocrystals of diameters less than 5 nm, the high volume of the ligands as compared to the volume of the nanocrystals makes it a challenge to deposit continuous compacted thin films from small nanocrystals. Films deposited from thermal decomposition of a stoichiometric mix of metal dithiocarbamate complexes were found to be predominantly CZTS. These films from complexes were found to be continuous but microporous. The diameter of the spheres making up the microporous structure could be changed by changing the anneal temperature. The structural composition of the final film could be altered by changing the heating rate of the complexes. CZTS exists in three different crystal structures: kesterite, stannite, and pre-mixed Cu-Au (PMCA) structures. Due to the similarity in the crystal structures, it is extremely difficult to distinguish them based on X-ray diffraction. We computed the phonon dispersion curves for the three structures using ab-initio calculations, and found characteristic discontinuities at the Gamma-point which can potentially be used to distinguish the three. In addition, the Gamma-point phonon frequencies, which correspond to the Raman peak positions, for the three structures were found to be shifted from each other by a few wavenumbers. By deconvoluting the experimental Raman spectra for both CZTS and Cu2ZnSnSe4 (CZTSe) using Gaussian peaks, we observed that the most intense Raman scattering peak in both CZTS and CZTSe is a sum of two different peaks which correspond to scattering from their respective kesterite and stannite phases. The electronic, structural, and vibrational properties of a series of CZTS-CZTSe alloys (CZTSSe) were studied using ab-initio calculations. The S-to-Se ratio and the spatial distribution of the anions in the unit cell were found to determine the energy splitting between the electronic states at the top of the valence band and the hole mobility in CZTSSe alloys and solar cells. X-ray diffraction patterns and phonon distribution curves were found to be sensitive to the local anion ordering. The predicted Raman scattering frequencies and their variation with x agree with experimentally determined values and trends.

Light-controlled synthesis of gold nanoparticles using a rigid, photoresponsive surfactant

NASA Astrophysics Data System (ADS)

Huang, Youju; Kim, Dong-Hwan

2012-09-01

We report a new strategy for shape control over the synthesis of gold nanoparticles (AuNPs) by using a photoresponsive surfactant based on a modified seed growth method. Owing to photoresponsive properties of the azo group, the designed surfactant, N1,N3,N5-tris[(4'-azobenzene-4-sulphonic acid)phenyl]benzene-1,3,5-tricarboxamide, exhibits a distinctive molecular configuration under light leading to different growth processes of AuNPs. As a result, the blackberry-like, spherical AuNPs and multilayered Au plates were successfully prepared in high yield under visible and UV light. The size and morphological control of Au nanocrystals are described and the synthesized Au nanocrystals are evaluated for SERS applications.We report a new strategy for shape control over the synthesis of gold nanoparticles (AuNPs) by using a photoresponsive surfactant based on a modified seed growth method. Owing to photoresponsive properties of the azo group, the designed surfactant, N1,N3,N5-tris[(4'-azobenzene-4-sulphonic acid)phenyl]benzene-1,3,5-tricarboxamide, exhibits a distinctive molecular configuration under light leading to different growth processes of AuNPs. As a result, the blackberry-like, spherical AuNPs and multilayered Au plates were successfully prepared in high yield under visible and UV light. The size and morphological control of Au nanocrystals are described and the synthesized Au nanocrystals are evaluated for SERS applications. Electronic supplementary information (ESI) available: The UV-vis spectra, representative field-emission scanning electron microscopy (FESEM) images and size distributions of Au seeds (18 nm) and spherical AuNPs (50 nm), photograph images of AuNPs solution and TEM images of blackberry-like AuNPs. See DOI: 10.1039/c2nr31717f

Solution synthesis of germanium nanocrystals

DOEpatents

Gerung, Henry [Albuquerque, NM; Boyle, Timothy J [Kensington, MD; Bunge, Scott D [Cuyahoga Falls, OH

2009-09-22

A method for providing a route for the synthesis of a Ge(0) nanometer-sized material from. A Ge(II) precursor is dissolved in a ligand heated to a temperature, generally between approximately 100.degree. C. and 400.degree. C., sufficient to thermally reduce the Ge(II) to Ge(0), where the ligand is a compound that can bond to the surface of the germanium nanomaterials to subsequently prevent agglomeration of the nanomaterials. The ligand encapsulates the surface of the Ge(0) material to prevent agglomeration. The resulting solution is cooled for handling, with the cooling characteristics useful in controlling the size and size distribution of the Ge(0) materials. The characteristics of the Ge(II) precursor determine whether the Ge(0) materials that result will be nanocrystals or nanowires.

Synthesis of Multicolor Core/Shell NaLuF4:Yb3+/Ln3+@CaF2 Upconversion Nanocrystals

PubMed Central

Li, Hui; Hao, Shuwei; Yang, Chunhui; Chen, Guanying

2017-01-01

The ability to synthesize high-quality hierarchical core/shell nanocrystals from an efficient host lattice is important to realize efficacious photon upconversion for applications ranging from bioimaging to solar cells. Here, we describe a strategy to fabricate multicolor core @ shell α-NaLuF4:Yb3+/Ln3+@CaF2 (Ln = Er, Ho, Tm) upconversion nanocrystals (UCNCs) based on the newly established host lattice of sodium lutetium fluoride (NaLuF4). We exploited the liquid-solid-solution method to synthesize the NaLuF4 core of pure cubic phase and the thermal decomposition approach to expitaxially grow the calcium fluoride (CaF2) shell onto the core UCNCs, yielding cubic core/shell nanocrystals with a size of 15.6 ± 1.2 nm (the core ~9 ± 0.9 nm, the shell ~3.3 ± 0.3 nm). We showed that those core/shell UCNCs could emit activator-defined multicolor emissions up to about 772 times more efficient than the core nanocrystals due to effective suppression of surface-related quenching effects. Our results provide a new paradigm on heterogeneous core/shell structure for enhanced multicolor upconversion photoluminescence from colloidal nanocrystals. PMID:28336867

Transition‐Metal‐Doped NIR‐Emitting Silicon Nanocrystals

PubMed Central

Chandra, Sourov; Masuda, Yoshitake

2017-01-01

Abstract Impurity‐doping in nanocrystals significantly affects their electronic properties and diversifies their applications. Herein, we report the synthesis of transition metal (Mn, Ni, Co, Cu)‐doped oleophilic silicon nanocrystals (SiNCs) through hydrolysis/polymerization of triethoxysilane with acidic aqueous metal salt solutions, followed by thermal disproportionation of the resulting gel into a doped‐Si/SiO2 composite that, upon HF etching and hydrosilylation with 1‐n‐octadecene, produces free‐standing octadecyl‐capped doped SiNCs (diameter≈3 to 8 nm; dopant <0.2 atom %). Metal‐doping triggers a red‐shift of the SiNC photoluminescence (PL) of up to 270 nm, while maintaining high PL quantum yield (26 % for Co doping). PMID:28374522

Atomic force microscopy characterization of cellulose nanocrystals

Treesearch

Roya R. Lahiji; Xin Xu; Ronald Reifenberger; Arvind Raman; Alan Rudie; Robert J. Moon

2010-01-01

Cellulose nanocrystals (CNCs) are gaining interest as a “green” nanomaterial with superior mechanical and chemical properties for high-performance nanocomposite materials; however, there is a lack of accurate material property characterization of individual CNCs. Here, a detailed study of the topography, elastic and adhesive properties of individual wood-derived CNCs...

In situ synthesis of TiO2/polyethylene terephthalate hybrid nanocomposites at low temperature

NASA Astrophysics Data System (ADS)

Peng, Xinyan; Ding, Enyong; Xue, Feng

2012-06-01

TiO2 nanoflowers were in situ grown on polyethylene terephthalate (PET) non-woven fabric by hydrolysis of TiCl4 in aqueous solution in the presence of nanocrystal cellulose grafted PET fabric (NCC-g-PET) at a low temperature of 70 °C. Nanocrystal cellulose (NCC) pre-grafted on PET fabric acted as hydrophilic substrate and morphology inducing agent to promote the nucleation and crystal growth of TiO2. Detailed information on the synthetic process was presented. The resulting samples were characterized using FE-SEM, EDS, ATR-IR, Raman microscopy, XRD and TG analysis. The photocatalytic activity of the samples was evaluated by the degradation of orange methyl under solar light. Characteristic results indicate that rutile TiO2 nanoflowers have grown abundantly on PET non-woven fabric, and the established hydrogen bonding strengthens the interfacial interaction between the inorganic particles and the polymeric substrates. The methyl orange decoloration test under natural solar light demonstrates that this TiO2/PET hybrid nanocomposites exhibit excellent self-cleaning performance which is expected to have a good potential for commercialization.

In situ development of self-reinforced cellulose nanocrystals based thermoplastic elastomers by atom transfer radical polymerization.

PubMed

Yu, Juan; Wang, Chunpeng; Wang, Jifu; Chu, Fuxiang

2016-05-05

Recently, the utilization of cellulose nanocrystals (CNCs) as a reinforcing material has received a great attention due to its high elastic modulus. In this article, a novel strategy for the synthesis of self-reinforced CNCs based thermoplastic elastomers (CTPEs) is presented. CNCs were first surface functionalized with an initiator for surface-initiated atom transfer radical polymerization (SI-ATRP). Subsequently, SI-ATRP of methyl methacrylate (MMA) and butyl acrylate (BA) was carried out in the presence of sacrificial initiator to form CTPEs in situ. The CTPEs together with the simple blends of CNCs and linear poly(MMA-co-BA) copolymer (P(MMA-co-BA)) were characterized for comparative study. The results indicated that P(MMA-co-BA) was successfully grafted onto the surface of CNCs and the compatibility between CNCs and the polymer matrix in CTPEs was greatly enhanced. Specially, the CTPEs containing 2.15wt% CNCs increased Tg by 19.2°C and tensile strength by 100% as compared to the linear P(MMA-co-BA). Copyright © 2016 Elsevier Ltd. All rights reserved.

Solvothermal synthesis of well-dispersed MF2 (M = Ca,Sr,Ba) nanocrystals and their optical properties

NASA Astrophysics Data System (ADS)

Zhang, Xiaoming; Quan, Zewei; Yang, Jun; Yang, Piaoping; Lian, Hongzhou; Lin, Jun

2008-02-01

MF2 (M = Ca,Sr,Ba) nanocrystals (NCs) were synthesized via a solvothermal process in the presence of oleic acid and characterized by x-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectra, UV/vis absorption spectra, photoluminescence (PL) excitation and emission spectra, and lifetimes, respectively. In the synthetic process, oleic acid as a surfactant played a crucial role in confining the growth and solubility of the MF2 NCs. The as-prepared CaF2, SrF2 and BaF2 NCs present morphologies of truncated octahedron, cube and sheet in a narrow distribution, respectively. Possible growth mechanisms were proposed to explain these results. The as-prepared NCs are highly crystalline and can be well dispersed in cyclohexane to form stable and clear colloidal solutions, which demonstrate strong emission bands centred at 400 nm in photoluminescence (PL) spectra compared with the cyclohexane solvent. The PL properties of the colloidal solutions of the as-prepared NCs can be ascribed to the trap states of surface defects.

Phytofabrication of bioinspired zinc oxide nanocrystals for biomedical application.

PubMed

Velmurugan, Palanivel; Park, Jung-Hee; Lee, Sang-Myeong; Jang, Jum-Suk; Yi, Young-Joo; Han, Sang-Sub; Lee, Sang-Hyun; Cho, Kwang-Min; Cho, Min; Oh, Byung-Taek

2016-09-01

In the present study, we investigated a novel green route for synthesis of zinc oxide nanoparticles (ZnO NPs) using the extract of young cones of Pinus densiflora as a reducing agent. Standard characterization studies were carried out to confirm the obtained product using UV-Vis spectra, SEM-EDS, FTIR, and XRD. TEM images showed that various shapes of ZnO NPs were synthesized, including hexagonal (wurtzite), triangular, spherical, and oval-shaped particles, with average sizes between 10 and 100 nm. The synthesized ZnO NPs blended with the young pine cone extract have very good activity against bacterial and fungal pathogens, similar to that of commercial ZnO NPs.

Synthesis of Mn doped ZnS nanocrystals: Crystallographic and morphological study

NASA Astrophysics Data System (ADS)

Shaikh, Azharuddin Z.; Shirsath, Narendra B.; Sonawane, Prabhakar S.

2018-05-01

The influence of doping concentration on the physical properties of ZnS nanocrystals synthesized using coprecipitation method at room temperature is reported in this paper. In particular, we have studied the structural properties of Zn1-xMnxS where (x=0.01, 0.03, 0.05) by X-ray diffraction. X-ray peak broadening analysis used to calculate the crystalline sizes, lattice parameters, number of unit cell per particle and volume of unit cell. Crystalline ZnS with a cubic structure is confirmed by XRD results. The grain size of pure and Mn doped samples were found in the range of 7nm to 9nm. All the physical parameters of cubic ZnS nanocrystals were calculated are similar with standard values. The scanning electron microscope (SEM) which revealed that the synthesized nanocrystals are well-crystalline and possessing cubic phase.

Tuning the Luminescence Properties of Colloidal I-III-VI Semiconductor Nanocrystals for Optoelectronics and Biotechnology Applications.

PubMed

Zhong, Haizheng; Bai, Zelong; Zou, Bingsuo

2012-11-01

In the past 5 years, colloidal I-III-VI nanocrystals such as CuInS2, CuInSe2, and AgInS2 have been intensively investigated for the potential to replace commonly available colloidal nanocrystals containing toxic elements in light-emitting and solar-harvesting applications. Many researchers from different disciplines are working on developing new synthetic protocols, performing spectroscopic studies to understand the luminescence mechanisms, and exploring various applications. To achieve enhanced performance, it is very desirable to obtain high-quality materials with tunable luminescence properties. In this Perspective, we highlight the current progress on tuning the luminescence properties of I-III-VI nanocrystals, especially focusing on the advances in the synthesis, spectroscopic properties, as well as the primary applications in light-emitting devices and bioimaging techniques. Finally, we outline the challenges concerning luminescent I-III-VI NCs and list a few important research tasks in this field.

Benzimidazole-functionalized Zr-UiO-66 nanocrystals for luminescent sensing of Fe3+ in water

NASA Astrophysics Data System (ADS)

Dong, Yingying; Zhang, Hanzhuo; Lei, Fan; Liang, Mei; Qian, Xuefeng; Shen, Peilian; Xu, Hui; Chen, Zhihui; Gao, Junkuo; Yao, Juming

2017-01-01

Zr-based MOF structure UiO-66 exhibits unprecedented high thermal and chemical stability, making it to be one of the most used MOFs in various applications. Yet, the poor photoluminescent (PL) properties of UiO-66 limit its applications in luminescent sensing. Herein, a new benzimidazole-functionalized UiO-66 nanocrystal (UiO-66-BI) was successfully fabricated via microwave synthesis. UiO-66-BI displayed octahedral nanocrystal morphology with a diameter smaller than 200 nm and could disperse well in water and common organic solvents. UiO-66-BI demonstrated extended optical absorption in the visible-light region and efficiently improved PL emission compared with UiO-66 pristine. The sensing properties of UiO-66-BI nanocrystals towards different ions were studied, and the results demonstrated that UiO-66-BI showed excellent selective luminescent sensing of Fe3+ ions in water.

Cellulose nanocrystals, nanofibers, and their composites as renewable smart materials

NASA Astrophysics Data System (ADS)

Kim, Jaehwan; Zhai, Lindong; Mun, Seongcheol; Ko, Hyun-U.; Yun, Young-Min

2015-04-01

Cellulose is one of abundant renewable biomaterials in the world. Over 1.5 trillion tons of cellulose is produced per year in nature by biosynthesis, forming microfibrils which in turn aggregate to form cellulose fibers. Using new effective methods these microfibrils can be disintegrated from the fibers to nanosized materials, so called cellulose nanocrystal (CNC) and cellulose nanofiber (CNF). The CNC and CNF have extremely good strength properties, dimensional stability, thermal stability and good optical properties on top of their renewable behavior, which can be a building block of new materials. This paper represents recent advancement of cellulose nanocrystals and cellulose nanofibers, followed by their possibility for smart materials. Natural behaviors, extraction, modification of cellulose nanocrystals and fibers are explained and their synthesis with nanomaterials is introduced, which is necessary to meet the technological requirements for smart materials. Also, its challenges are addressed.

PdCuPt Nanocrystals With Multi-branches for Enzyme-free Glucose Detection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, Shaofang; Zhu, Chengzhou; Song, Junhua

By carefully controlling the synthesis condition, branched PtCu bimetallic templates were synthesized in aqueous solution. After the galvanic replacement reaction between PtCu templates and the Pt precursors, PdCuPt trimetallic nanocrystals with branched structures were obtained. Owing to the open structure and the optimized composition, the electrochemical experimental results reveal that the PdCuPt trimetallic nanocrystals exhibit high electrocatalytic activity, selectivity and stability for the oxidation of glucose in alkaline solution. In details, a sensitivity of 378 μA/mM/cm2 and a detection limit of 1.29 μM can be achieved. The good electrocatalytic performance should be attributed to the unique branched nanostructure as wellmore » as the synergistic effect among metals. The superior catalytic properties suggest that these nanocrystals are promising for enzyme-free detection of glucose.« less

Benzimidazole-functionalized Zr-UiO-66 nanocrystals for luminescent sensing of Fe{sup 3+} in water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Yingying; Zhang, Hanzhuo; Lei, Fan

2017-01-15

Zr-based MOF structure UiO-66 exhibits unprecedented high thermal and chemical stability, making it to be one of the most used MOFs in various applications. Yet, the poor photoluminescent (PL) properties of UiO-66 limit its applications in luminescent sensing. Herein, a new benzimidazole-functionalized UiO-66 nanocrystal (UiO-66-BI) was successfully fabricated via microwave synthesis. UiO-66-BI displayed octahedral nanocrystal morphology with a diameter smaller than 200 nm and could disperse well in water and common organic solvents. UiO-66-BI demonstrated extended optical absorption in the visible-light region and efficiently improved PL emission compared with UiO-66 pristine. The sensing properties of UiO-66-BI nanocrystals towards different ionsmore » were studied, and the results demonstrated that UiO-66-BI showed excellent selective luminescent sensing of Fe{sup 3+} ions in water.« less

Internal structure of InP/ZnS nanocrystals unraveled by high-resolution soft X-ray photoelectron spectroscopy.

PubMed

Huang, Kai; Demadrille, Renaud; Silly, Mathieu G; Sirotti, Fausto; Reiss, Peter; Renault, Olivier

2010-08-24

High-energy resolution photoelectron spectroscopy (DeltaE < 200 meV) is used to investigate the internal structure of semiconductor quantum dots containing low Z-contrast elements. In InP/ZnS core/shell nanocrystals synthesized using a single-step procedure (core and shell precursors added at the same time), a homogeneously alloyed InPZnS core structure is evidenced by quantitative analysis of their In3d(5/2) spectra recorded at variable excitation energy. When using a two-step method (core InP nanocrystal synthesis followed by subsequent ZnS shell growth), XPS analysis reveals a graded core/shell interface. We demonstrate the existence of In-S and S(x)-In-P(1-x) bonding states in both types of InP/ZnS nanocrystals, which allows a refined view on the underlying reaction mechanisms.

Development of curcumin-cyclodextrin/cellulose nanocrystals complexes: New anticancer drug delivery systems.

PubMed

Ndong Ntoutoume, Gautier M A; Granet, Robert; Mbakidi, Jean Pierre; Brégier, Frédérique; Léger, David Y; Fidanzi-Dugas, Chloë; Lequart, Vincent; Joly, Nicolas; Liagre, Bertrand; Chaleix, Vincent; Sol, Vincent

2016-02-01

The synthesis of curcumin-cyclodextrin/cellulose nanocrystals (CNCx) nano complexes was performed. CNCx were functionalized by ionic association with cationic β-cyclodextrin (CD) and CD/CNCx complexes were used to encapsulate curcumin. Preliminary in vitro results showed that the resulting curcumin-CD/CNCx complexes exerted antiproliferative effect on colorectal and prostatic cancer cell lines, with IC50s lower than that of curcumin alone. Copyright © 2015 Elsevier Ltd. All rights reserved.

General method for the synthesis of hierarchical nanocrystal-based mesoporous materials.

PubMed

Rauda, Iris E; Buonsanti, Raffaella; Saldarriaga-Lopez, Laura C; Benjauthrit, Kanokraj; Schelhas, Laura T; Stefik, Morgan; Augustyn, Veronica; Ko, Jesse; Dunn, Bruce; Wiesner, Ulrich; Milliron, Delia J; Tolbert, Sarah H

2012-07-24

Block copolymer templating of inorganic materials is a robust method for the production of nanoporous materials. The method is limited, however, by the fact that the molecular inorganic precursors commonly used generally form amorphous porous materials that often cannot be crystallized with retention of porosity. To overcome this issue, here we present a general method for the production of templated mesoporous materials from preformed nanocrystal building blocks. The work takes advantage of recent synthetic advances that allow organic ligands to be stripped off of the surface of nanocrystals to produce soluble, charge-stabilized colloids. Nanocrystals then undergo evaporation-induced co-assembly with amphiphilic diblock copolymers to form a nanostructured inorganic/organic composite. Thermal degradation of the polymer template results in nanocrystal-based mesoporous materials. Here, we show that this method can be applied to nanocrystals with a broad range of compositions and sizes, and that assembly of nanocrystals can be carried out using a broad family of polymer templates. The resultant materials show disordered but homogeneous mesoporosity that can be tuned through the choice of template. The materials also show significant microporosity, formed by the agglomerated nanocrystals, and this porosity can be tuned by the nanocrystal size. We demonstrate through careful selection of the synthetic components that specifically designed nanostructured materials can be constructed. Because of the combination of open and interconnected porosity, high surface area, and compositional tunability, these materials are likely to find uses in a broad range of applications. For example, enhanced charge storage kinetics in nanoporous Mn(3)O(4) is demonstrated here.

Fabrication and characterization of morphology-tuned single-crystal monodisperse Fe3O4 nanocrystals

NASA Astrophysics Data System (ADS)

Yu, Xuegang; Shan, Yan; Chen, Kezheng

2018-05-01

Monodisperse Fe3O4 nanocrystals with different size and morphology have been successfully fabricated by a facile high temperature reflow method. The presented materials were characterized by X-ray diffraction (XRD), fourier transform infrared (FTIR) spectroscopy, transmission electron microscope (TEM), selection area electron diffraction (SAED) and magnetic property measurement system (MPMS). The results showed that the as-prepared materials have face-centered cubic structures. Oleic acid plays a key role in the dispersion of Fe3O4 nanocrystals. The cubic and octahedral nanocrystals are enclosed by {1 0 0} and {1 1 1} lattice planes. The MPMS measurements show that magnetic properties are closely related to the sizes of the materials, and there is a stronger dipolar interaction between Fe3O4 nanocrystals with larger sizes. The controllable magnetic property and good dispersion endow the as-synthesized materials with great potential applications in magnetic fluid fields including sealing, medical equipment, mineral processing and other aspects.

Synthesis and characterization of biopolymer protected zinc sulphide nanoparticles

NASA Astrophysics Data System (ADS)

Senapati, U. S.; Sarkar, D.

2015-09-01

Zinc sulphide (ZnS) nanoparticles are prepared by a simple, economic and green synthesis route. X-ray diffraction patterns confirm zinc blend structure. ZnS formation is confirmed through chemical analysis by energy dispersive analysis of X-rays. Transmission electron microscopy reveals formation of nanosize with dimension in the range of 8-2 nm. Band gap of the nanocrystals is found to lie in the range of 4.51-4.65 eV. Photoluminescence study indicate defect like vacancies. The growth mechanism of ZnS nanoparticles is discussed with the help of Fourier transform infrared spectroscopy and thermogravimetric analysis. The materials show high dielectric constant compared to its bulk counterpart. The dielectric loss of the samples shows anomalous behaviour. The frequency dependent A.C. conductivity of the samples is discussed both in high and low frequency regimes. Current-voltage (I-V) characteristic performed under dark and under illumination, shows excellent light response of the material.

Facile Synthesis of Monodisperse Gold Nanocrystals Using Virola oleifera

NASA Astrophysics Data System (ADS)

Milaneze, Bárbara A.; Oliveira, Jairo P.; Augusto, Ingrid; Keijok, Wanderson J.; Côrrea, Andressa S.; Ferreira, Débora M.; Nunes, Otalíbio C.; Gonçalves, Rita de Cássia R.; Kitagawa, Rodrigo R.; Celante, Vinícius G.; da Silva, André Romero; Pereira, Ana Claudia H.; Endringer, Denise C.; Schuenck, Ricardo P.; Guimarães, Marco C. C.

2016-10-01

The development of new routes and strategies for nanotechnology applications that only employ green synthesis has inspired investigators to devise natural systems. Among these systems, the synthesis of gold nanoparticles using plant extracts has been actively developed as an alternative, efficient, cost-effective, and environmentally safe method for producing nanoparticles, and this approach is also suitable for large-scale synthesis. This study reports reproducible and completely natural gold nanocrystals that were synthesized using Virola oleifera extract. V. oleifera resin is rich in epicatechin, ferulic acid, gallic acid, and flavonoids (i.e., quercetin and eriodictyol). These gold nanoparticles play three roles. First, these nanoparticles exhibit remarkable stability based on their zeta potential. Second, these nanoparticles are functionalized with flavonoids, and third, an efficient, economical, and environmentally friendly mechanism can be employed to produce green nanoparticles with organic compounds on the surface. Our model is capable of reducing the resin of V. oleifera, which creates stability and opens a new avenue for biological applications. This method does not require painstaking conditions or hazardous agents and is a rapid, efficient, and green approach for the fabrication of monodisperse gold nanoparticles.

Structural, spectroscopic and cytotoxicity studies of TbF3@CeF3 and TbF3@CeF3@SiO2 nanocrystals.

PubMed

Grzyb, Tomasz; Runowski, Marcin; Dąbrowska, Krystyna; Giersig, Michael; Lis, Stefan

2013-01-01

Terbium fluoride nanocrystals, covered by a shell, composed of cerium fluoride were synthesized by a co-precipitation method. Their complex structure was formed spontaneously during the synthesis. The surface of these core/shell nanocrystals was additionally modified by silica. The properties of TbF 3 @CeF 3 and TbF 3 @CeF 3 @SiO 2 nanocrystals, formed in this way, were investigated. Spectroscopic studies showed that the differences between these two groups of products resulted from the presence of the SiO 2 shell. X-ray diffraction patterns confirmed the trigonal crystal structure of TbF 3 @CeF 3 nanocrystals. High resolution transmission electron microscopy in connection with energy-dispersive X-ray spectroscopy showed a complex structure of the formed nanocrystals. Crystallized as small discs, 'the products', with an average diameter around 10 nm, showed an increase in the concentration of Tb 3+ ions from surface to the core of nanocrystals. In addition to photo-physical analyses, cytotoxicity studies were performed on HSkMEC (Human Skin Microvascular Endothelial Cells) and B16F0 mouse melanoma cancer cells. The cytotoxicity of the nanomaterials was neutral for the investigated cells with no toxic or antiproliferative effect in the cell cultures, either for normal or for cancer cells. This fact makes the obtained nanocrystals good candidates for biological applications and further modifications of the SiO 2 shell. .

Structural, spectroscopic and cytotoxicity studies of TbF3@CeF3 and TbF3@CeF3@SiO2 nanocrystals

NASA Astrophysics Data System (ADS)

Grzyb, Tomasz; Runowski, Marcin; Dąbrowska, Krystyna; Giersig, Michael; Lis, Stefan

2013-10-01

Terbium fluoride nanocrystals, covered by a shell, composed of cerium fluoride were synthesized by a co-precipitation method. Their complex structure was formed spontaneously during the synthesis. The surface of these core/shell nanocrystals was additionally modified by silica. The properties of TbF3@CeF3 and TbF3@CeF3@SiO2 nanocrystals, formed in this way, were investigated. Spectroscopic studies showed that the differences between these two groups of products resulted from the presence of the SiO2 shell. X-ray diffraction patterns confirmed the trigonal crystal structure of TbF3@CeF3 nanocrystals. High resolution transmission electron microscopy in connection with energy-dispersive X-ray spectroscopy showed a complex structure of the formed nanocrystals. Crystallized as small discs, `the products', with an average diameter around 10 nm, showed an increase in the concentration of Tb3+ ions from surface to the core of nanocrystals. In addition to photo-physical analyses, cytotoxicity studies were performed on HSkMEC (Human Skin Microvascular Endothelial Cells) and B16F0 mouse melanoma cancer cells. The cytotoxicity of the nanomaterials was neutral for the investigated cells with no toxic or antiproliferative effect in the cell cultures, either for normal or for cancer cells. This fact makes the obtained nanocrystals good candidates for biological applications and further modifications of the SiO2 shell.

In Situ Preparation of Metal Halide Perovskite Nanocrystal Thin Films for Improved Light-Emitting Devices.

PubMed

Zhao, Lianfeng; Yeh, Yao-Wen; Tran, Nhu L; Wu, Fan; Xiao, Zhengguo; Kerner, Ross A; Lin, YunHui L; Scholes, Gregory D; Yao, Nan; Rand, Barry P

2017-04-25

Hybrid organic-inorganic halide perovskite semiconductors are attractive candidates for optoelectronic applications, such as photovoltaics, light-emitting diodes, and lasers. Perovskite nanocrystals are of particular interest, where electrons and holes can be confined spatially, promoting radiative recombination. However, nanocrystalline films based on traditional colloidal nanocrystal synthesis strategies suffer from the use of long insulating ligands, low colloidal nanocrystal concentration, and significant aggregation during film formation. Here, we demonstrate a facile method for preparing perovskite nanocrystal films in situ and that the electroluminescence of light-emitting devices can be enhanced up to 40-fold through this nanocrystal film formation strategy. Briefly, the method involves the use of bulky organoammonium halides as additives to confine crystal growth of perovskites during film formation, achieving CH 3 NH 3 PbI 3 and CH 3 NH 3 PbBr 3 perovskite nanocrystals with an average crystal size of 5.4 ± 0.8 nm and 6.4 ± 1.3 nm, respectively, as confirmed through transmission electron microscopy measurements. Additive-confined perovskite nanocrystals show significantly improved photoluminescence quantum yield and decay lifetime. Finally, we demonstrate highly efficient CH 3 NH 3 PbI 3 red/near-infrared LEDs and CH 3 NH 3 PbBr 3 green LEDs based on this strategy, achieving an external quantum efficiency of 7.9% and 7.0%, respectively, which represent a 40-fold and 23-fold improvement over control devices fabricated without the additives.

Hydrogen-Bonded Organic Semiconductor Micro- And Nanocrystals: From Colloidal Syntheses to (Opto-)Electronic Devices

PubMed Central

2014-01-01

Organic pigments such as indigos, quinacridones, and phthalocyanines are widely produced industrially as colorants for everyday products as various as cosmetics and printing inks. Herein we introduce a general procedure to transform commercially available insoluble microcrystalline pigment powders into colloidal solutions of variously sized and shaped semiconductor micro- and nanocrystals. The synthesis is based on the transformation of the pigments into soluble dyes by introducing transient protecting groups on the secondary amine moieties, followed by controlled deprotection in solution. Three deprotection methods are demonstrated: thermal cleavage, acid-catalyzed deprotection, and amine-induced deprotection. During these processes, ligands are introduced to afford colloidal stability and to provide dedicated surface functionality and for size and shape control. The resulting micro- and nanocrystals exhibit a wide range of optical absorption and photoluminescence over spectral regions from the visible to the near-infrared. Due to excellent colloidal solubility offered by the ligands, the achieved organic nanocrystals are suitable for solution processing of (opto)electronic devices. As examples, phthalocyanine nanowire transistors as well as quinacridone nanocrystal photodetectors, with photoresponsivity values by far outperforming those of vacuum deposited reference samples, are demonstrated. The high responsivity is enabled by photoinduced charge transfer between the nanocrystals and the directly attached electron-accepting vitamin B2 ligands. The semiconducting nanocrystals described here offer a cheap, nontoxic, and environmentally friendly alternative to inorganic nanocrystals as well as a new paradigm for obtaining organic semiconductor materials from commercial colorants. PMID:25253644

Synthesis and applications of heterostructured semiconductor nanocrystals

NASA Astrophysics Data System (ADS)

Khon, Elena

Semiconductor nanocrystals (NCs) have been of great interest to researchers for several decades due to their unique optoelectronic properties. These nanoparticles are widely used for a variety of different applications. However, there are many unresolved issues that lower the efficiency and/or stability of devices which incorporate these NCs. Our research is dedicated to addressing these issues by identifying potential problems and resolving them, improving existing systems, generating new synthetic strategies, and/or building new devices. The general strategies for the synthesis of different nanocrystals were established in this work, one of which is the colloidal growth of gold domains onto CdS semiconductor nanocrystals. Control of shape and size was achieved simply by adjusting the temperature and the time of the reaction. Depending on the exact morphology of Au and CdS domains, fabricated nano-composites can undergo evaporation-induced self-assembly onto a substrate, which is very useful for building devices. CdS/Au heterostructures can assemble in two different ways: through end-to-end coupling of Au domains, resulting in the formation of one-dimensional chains; and via side-by-side packing of CdS nanorods, leading to the onset of two-dimensional superlattices. We investigated the nature of exciton-plasmon interactions in Au-tipped CdS nanorods using femtosecond transient absorption spectroscopy. The study demonstrated that the key optoelectronic properties of electrically coupled metal and semiconductor domains are significantly different from those observed in systems with weak inter-domain coupling. In particular, strongly-coupled nanocomposites promote mixing of electronic states at semiconductor-metal domain interfaces, which causes a significant suppression of both plasmon and exciton carrier excitations. Colloidal QDs are starting to replace organic molecules in many different applications, such as organic light emmiting diods (OLEDs), due to their light emmision tunability. We reported a general strategy for the assembly of all-inorganic light-emitting nanocrystal films with an emission quantum yield in the 30-52% range. Our methodology relies on solution-processing of CdSe nanocrystals into a crystalline matrix of a wide band gap semiconductor (CdS, ZnS). As a result, we replace original organic ligands on nanocrystal surfaces with an inorganic medium which efficiently preserves the quantum confinement of electrical charges in CdSe NCs. In addition to strong emission, fabricated films demonstrated excellent thermal and chemical stability, and a large refractive index, which avails their integration into emerging solid-state nanocrystal devices. The ability to control size and shape of NCs is essential as it automatically affects the optoelectronic properties of the crystals. Colloidal chemistry offers an assortment of synthetic tools for tuning the shape of NCs, but some nanoparticle morphologies require alternative processing strategies. We have shown that chemical etching of colloidal nanoparticles can facilitate the realization of desirable nanocrystal geometries. This methodology allows both CdSe and CdS composed semiconductor domains be exposed to the external environment, while maintaining a structural design that is highly desirable for catalytic applications. Hydrogen production tests confirmed the improved catalytic activity of CdSe/CdS dimers. We expect that the demonstrated application will become a common methodology in the synthesis of charge-separating nanocrystals, leading to advanced nanoparticle architectures for applications in the areas of photocatalysis, photovoltaics, and light detection.

Nanocomposites Based on Luminescent Colloidal Nanocrystals and Polymeric Ionic Liquids towards Optoelectronic Applications

PubMed Central

Panniello, Annamaria; Ingrosso, Chiara; Coupillaud, Paul; Tamborra, Michela; Binetti, Enrico; Curri, Maria Lucia; Agostiano, Angela; Taton, Daniel; Striccoli, Marinella

2014-01-01

Polymeric ionic liquids (PILs) are an interesting class of polyelectrolytes, merging peculiar physical-chemical features of ionic liquids with the flexibility, mechanical stability and processability typical of polymers. The combination of PILs with colloidal semiconducting nanocrystals leads to novel nanocomposite materials with high potential for batteries and solar cells. We report the synthesis and properties of a hybrid nanocomposite made of colloidal luminescent CdSe nanocrystals incorporated in a novel ex situ synthesized imidazolium-based PIL, namely, either a poly(N-vinyl-3-butylimidazolium hexafluorophosphate) or a homologous PIL functionalized with a thiol end-group exhibiting a chemical affinity with the nanocrystal surface. A capping exchange procedure has been implemented for replacing the pristine organic capping molecules of the colloidal CdSe nanocrystals with inorganic chalcogenide ions, aiming to disperse the nano-objects in the PILs, by using a common polar solvent. The as-prepared nanocomposites have been studied by TEM investigation, UV-Vis, steady-state and time resolved photoluminescence spectroscopy for elucidating the effects of the PIL functionalization on the morphological and optical properties of the nanocomposites. PMID:28788477

Microstructure and magnetic properties of MFe{sub 2}O{sub 4} (M = Co, Ni, and Mn) ferrite nanocrystals prepared using colloid mill and hydrothermal method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Wei, E-mail: wangwei@mail.buct.edu.cn; Ding, Zui; Zhao, Xiruo

2015-05-07

Three kinds of spinel ferrite nanocrystals, MFe{sub 2}O{sub 4} (M = Co, Ni, and Mn), are synthesized using colloid mill and hydrothermal method. During the synthesis process, a rapid mixing and reduction of cations with sodium borohydride (NaBH{sub 4}) take place in a colloid mill then through a hydrothermal reaction, a slow oxidation and structural transformation of the spinel ferrite nanocrystals occur. The phase purity and crystal lattice parameters are estimated by X-ray diffraction studies. Scanning electron microscopy and transmission electron microscopy images show the morphology and particle size of the as-synthesized ferrite nanocrystals. Raman spectrum reveals active phonon modesmore » at room temperature, and a shifting of the modes implies cation redistribution in the tetrahedral and octahedral sites. Magnetic measurements show that all the obtained samples exhibit higher saturation magnetization (M{sub s}). Meanwhile, experiments demonstrate that the hydrothermal reaction time has significant effects on microstructure, morphologies, and magnetic properties of the as-synthesized ferrite nanocrystals.« less

Chalcogenide Sensitized Carbon Based TiO2 Nanomaterial For Solar Driven Applications

NASA Astrophysics Data System (ADS)

Pathak, Pawan

The demand for renewable energy is growing because fossils fuels are depleting at a rapid pace. Solar energy an abundant green energy resource. Utilizing this resource in a smart manner can resolve energy-crisis related issues. Sun light can be efficiently harvested using semiconductor based materials by utilizing photo-generated charges for numerous beneficial applications. The main goal of this thesis is to synthesize different nanostructures of TiO2, develop a novel method of coupling and synthesizing chalcogenide nanocrystals with TiO2 and to study the charge transportation effects of the various carbon allotropes in the chalcogenide nanocrystal sensitized TiO2 nanostructure. We have fabricated different nanostructures of TiO2 as solar energy harvesting materials. Effects of the different phases of TiO2 have also been studied. The anatase phase of TiO2 is more photoactive than the rutile phase of TiO2, and the higher dimension of the TiO2 can increase the surface area of the material which can produce higher photocurrent. Since TiO2 only absorbs in the UV range; to increase the absorbance TiO2 should be coupled to visible light absorbing materials. This dissertation presents a simple approach to synthesize and couple chalcogenide nanocrystals with TiO2 nanostructure to form a heterostructured composite. An atmospheric pressure based, single precursor, one-pot approach has been developed and tested to assemble chalcogenide nanocrystal on the TiO2 surface. Surface characterization using microscopy, X-ray diffraction, and elemental analysis indicates the formation of nanocrystals along the nanotube walls and inter-tubular spacing. Optical measurements indicate that the chalcogenide nanocrystals absorb in the visible region and demonstrate an increase in photocurrent in comparison to bare TiO2 nanostructure. The CdS synthesized TiO2 nanostructure produced the highest photocurrent as measured in the three electrode system. We have also assembled the PbS nanocrystal sensitized photoanode using the one pot method. Finally, the charge transportation effect of carbon allotropes has been studied. For this we assembled TiO2 conductive carbon chalcogenide nanocomposite system. Surface and elemental characterization using electron microscopy, EDX (energy dispersive x-ray) and x-ray diffraction pattern, provide the insights into the assembly of the nanostructure. Optical absorbance, Photo chronometry, Linear sweep voltammetry, and electrochemical impedance analysis have been used to provide opto-electronic performance of the material. We have studied the loading effect of various carbon allotropes, [fullerene (C 60), reduced graphene oxide (RGO), carbon nanotubes (CNTs), and graphene quantum dots (GQDs)], loading effect of chalcogenide, and effect of nitrogen doping on the carbon allotropes to optimize the performance of the heterostructure. This dissertation is expected to impact the materials synthesis strategies and assemble the nanostructures used in composite electrode driven applications in the area of photo electrochemistry, PV, solar-fuels, and other associated topics of energy storage and sensing.

Synthesis and characterization of CaCO3 (calcite) nano particles from cockle shells (Anadara granosa Linn) by precipitation method

NASA Astrophysics Data System (ADS)

Widyastuti, Sri; Intan Ayu Kusuma, P.

2017-06-01

Calcium supplements can reduce the risk of osteoporosis, but they are not automatically absorbed in the gastrointestinal tract. Nanotechnology is presumed to have a capacity in resolving this problem. The preparation and characterization of calcium carbonate nano particle to improve the solubility was performed. Calcium carbonate nano particles were synthesized using precipitation method from cockle shells (Anadara granosa Linn). Samples of the cockle shells were dried in an oven at temperature of 50°C for 7 (seven) days and subsequently they were crushed and blended into fine powder that was sieved through 125-μm sieve. The synthesis of calcium carbonate nanocrystals was done by extracting using hydro chloride acid and various concentrations of sodium hydroxide were used to precipitate the calcium carbonate nano particles. The size of the nano particles was determined by SEM, XRD data, and Fourier transform infrared spectroscopy (FT-IR). The results of XRD indicated that the overall crystalline structure and phase purity of the typical calcite phase CaCO3 particles were approximately 300 nm in size. The method to find potential applications in industry to yield the large scale synthesis of aragonite nano particles by a low cost but abundant natural resource such as cockle shells is required.

Combining Pre- and Post-Nucleation Trajectories for the Synthesis of High FAU-Content Faujasite Nanocrystals from Organic-Free Sols

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khaleel, Maryam; Xu, Wenqian; Lesch, David A.

The effects of synthesis conditions on the FAU/EMT content and the size of nanocrystals, formed from inorganic aluminosilicate sols, were investigated. High resolution transmission electron microscopy imaging and comparison of experimental X-ray diffraction patterns with simulations demonstrated that all materials made starting from synthesis mixtures in the composition range (1.8-33) SiO2: 1 Al2O3: (2.7-33) Na2O: (41-1000) H2O contain FAU/EMT intergrowths. Compositions with low water content increase the FAU fraction up to 0.8 but the crystal size exceeds 100 nm. Extension of the higher FAU purity to nanocrystals was achieved only by first mixing the sol at high water content compositionsmore » that favor nanocrystal formation and then - after a certain time - lowering by freeze-drying the water to levels favoring the formation of FAU. Cryogenic transmission electron microscopy and small angle X-ray scattering from representative optically clear and colloidally stable precursor sols (aged and crystallized at ambient temperature) reveal the formation of amorphous aggregates before the detection of crystals, in agreement with earlier findings and an existing model for the aggregative growth of the zeolite MFI. The presence of these amorphous aggregates coincides with the aforementioned state of sol that preserves the original trajectory towards nano-crystals after the pronounced reduction of water content by freeze-drying. If water reduction by freeze-drying is applied earlier (before the detection of amorphous aggregates), the sol follows the low water content trajectory towards larger crystals. Despite this memory effect, the sol at this stage is still agnostic towards FAU or EMT formation, the relative content of which is dominantly determined by the final water content. These findings demonstrate that it is possible to combine the effects of pre-and post-nucleation sol composition to steer crystal size and crystal structure, respectively. They confirm precursor nanoparticle evolution, while they emphasize the importance of solution phase composition at both pre- and post-nucleation stages of aggregative crystal growth.« less

Confining the nucleation and overgrowth of Rh to the {111} facets of Pd nanocrystal seeds: the roles of capping agent and surface diffusion.

PubMed

Xie, Shuifen; Peng, Hsin-Chieh; Lu, Ning; Wang, Jinguo; Kim, Moon J; Xie, Zhaoxiong; Xia, Younan

2013-11-06

This article describes a systematic study of the spatially confined growth of Rh atoms on Pd nanocrystal seeds, with a focus on the blocking effect of a surface capping agent and the surface diffusion of adatoms. We initially used Pd cuboctahedrons as the seeds to illustrate the concept and to demonstrate the capabilities of our approach. Because the Pd{100} facets were selectively capped by a layer of chemisorbed Br(–) or I(–) ions, we were able to confine the nucleation and deposition of Rh atoms solely on the {111} facets of a Pd seed. When the synthesis was conducted at a relatively low temperature, the deposition of Rh atoms followed an island growth mode because of the high Rh–Rh interatomic binding energy. We also facilitated the surface diffusion of deposited Rh atoms by increasing the reaction temperature and decreasing the injection rate for the Rh precursor. Under these conditions, the deposition of Rh on the Pd{111} facets was switched to a layered growth mode. We further successfully extended this approach to a variety of other types of Pd polyhedral seeds that contained Pd{111} and Pd{100} facets in different proportions on the surface. As expected, a series of Pd–Rh bimetallic nanocrystals with distinctive elemental distributions were obtained. We could remove the Pd cores through selective chemical etching to generate Rh hollow nanoframes with different types and degrees of porosity. This study clearly demonstrates the importance of facet capping, surface diffusion, and reaction kinetics in controlling the morphologies of bimetallic nanocrystals during a seed-mediated process. It also provides a new direction for the rational design and synthesis of nanocrystals with spatially controlled distributions of elements for a variety of applications.

Synthesis of coesite nanocrystals from ethane bridged periodic mesoporous organosilica at low temperature and extreme pressure.

PubMed

Liang, Zhili; Mohanty, Paritosh; Fei, Yingwei; Landskron, Kai

2010-12-14

Coesite nanocrystals have been synthesized from periodic mesoporous organosilica (PMO) with (CH(2))(2) bridges heated at 300 °C for 150 min and 12 GPa. The crystals are not sintered, single crystalline, and have diameters of ca. 100-300 nm. Below 300 °C, an amorphous non-porous organosilica glass was obtained. Heating above 300 °C at 12 GPa results in the rapid crystal growth and micron size coesite crystals were formed.

Phage as a template to grow bone mineral nanocrystals.

PubMed

Cao, Binrui; Xu, Hong; Mao, Chuanbin

2014-01-01

Phage display is a biotechnique that fuses functional peptides on the outer surface of filamentous phage by inserting DNA encoding the peptides into the genes of its coat proteins. The resultant peptide-displayed phage particles have been widely used as biotemplates for the synthesis of functional hybrid nanomaterials. Here, we describe the bioengineering of M13 filamentous phage to surface-display bone mineral (hydroxyapatite (HAP))-nucleating peptides derived from dentin matrix protein-1 and using the engineered phage as a biotemplate to grow HAP nanocrystals.

Cellulose nanocrystal zero-valent iron nanocomposites for groundwater remediation†

PubMed Central

Bossa, Nathan; Carpenter, Alexis Wells; Kumar, Naresh; de Lannoy, Charles-François

2018-01-01

Zero-valent iron nanoparticles (nano-ZVIs) have been widely studied for in situ remediation of groundwater and other environmental matrices. Nano-ZVI particle mobility and reactivity are still the main impediments in achieving efficient in situ groundwater remediation. Compared to the nano-ZVI “coating” strategy, nano-ZVI stabilization on supporting material allows direct contact with the contaminant, reduces the electron path from the nano-ZVI to the target contaminant and increases nano-ZVI reactivity. Herein, we report the synthesis of nano-ZVI stabilized by cellulose nanocrystal (CNC) rigid nanomaterials (CNC-nano-ZVI; Fe/CNC = 1 w/w) with two different CNC functional surfaces (–OH and –COOH) using a classic sodium borohydride synthesis pathway. The final nanocomposites were thoroughly characterized and the reactivity of CNC-nano-ZVIs was assessed by their methyl orange (MO) dye degradation potential. The mobility of nanocomposites was determined in (sand/glass bead) porous media by utilizing a series of flowthrough transport column experiments. The synthesized CNC-nano-ZVI provided a stable colloidal suspension and demonstrated high mobility in porous media with an attachment efficiency (α) value of less than 0.23. In addition, reactivity toward MO increased up to 25% compared to bare ZVI. The use of CNC as a delivery vehicle shows promising potential to further improve the capability and applicability of nano-ZVI for in situ groundwater remediation and can spur advancements in CNC-based nanocomposites for their application in environmental remediation. PMID:29725541

Joey Luther | NREL

Science.gov Websites

Laboratory to study synthesis and chemical transformation of uniquely shaped colloidal nanocrystals for Advanced Solar Photophysics as well as in NREL's perovskite team. Education B.S. Electrical and Computer

A Feasible One-Step Synthesis of Hierarchical Zeolite Beta with Uniform Nanocrystals via CTAB

PubMed Central

Zhang, Weimin; Hu, Sufang; Qin, Bo; Li, Ruifeng

2018-01-01

A hierarchical zeolite Beta has been prepared by a feasible one-pot and one-step method, which is suitable for application in industrial production. The synthesis is a simple hydrothermal process with low-cost raw materials, without adding alcohol or adding seeds, and without aging, recrystallization, and other complex steps. The hierarchical zeolite Beta is a uniform nanocrystal (20–50 nm) aggregation with high external surface area (300 m2/g) and mesoporous volume (0.50 cm3/g), with the mesoporous structure composed of intercrystal and intracrystal pores. As an acid catalyst in benzylation of naphthalene with benzyl chloride, the hierarchical zeolite Beta has shown high activity in the bulky molecule reaction due to its introduction of mesostructure. PMID:29695044

Nimodipine nanocrystals for oral bioavailability improvement: preparation, characterization and pharmacokinetic studies.

PubMed

Fu, Qiang; Sun, Jin; Zhang, Dong; Li, Mo; Wang, Yongjun; Ling, Guixia; Liu, Xiaohong; Sun, Yinghua; Sui, Xiaofan; Luo, Cong; Sun, Le; Han, Xiaopeng; Lian, He; Zhu, Meng; Wang, Siling; He, Zhonggui

2013-09-01

This study intended to develop nimodipine (NMD) nanocrystals with different sizes for oral administration and to investigate the relationship between dissolution and pharmacokinetics for NMD nanocrystals and Nimotop(®). NMD nanocrystals were prepared by combination of microprecipitation and high pressure homogenization and were further lyophilized. The particle size, morphology and aqueous solubility of the NMD nanocrystals were determined. With Nimotop(®) as the control, the dissolution rate was evaluated and the pharmacokinetic study was undertaken in beagle dogs. NMD nanocrystals with mean diameters of about 159.0, 503.0 and 833.3 nm were prepared, respectively. The lyophilization didn't affect the particle sizes of the redispersed nanocrystals. The aqueous solubility was significantly improved and displayed a size-dependent manner. The nanocrystals exhibited lower dissolution patterns than Nimotop(®) under non-sink condition, but bioavailability of the two nanocrystals (159.0 and 833.3 nm) was equivalent, about 2.6-fold higher than Nimotop(®). In conclusion, oral nanocrystal drug delivery system was a promising strategy in improving the oral bioavailability of poorly soluble or insoluble drugs. But we could not establish a favorable in vitro in vivo correlation for NMD nanocrystals and Nimotop(®) and thus the oral absorption mechanism of the NMD nanocrystals required further study. Copyright © 2013 Elsevier B.V. All rights reserved.

Phase- and shape-controlled hydrothermal synthesis of CdS nanoparticles, and oriented attachment growth of its hierarchical architectures

NASA Astrophysics Data System (ADS)

Cao, Yali; Hu, Pengfei; Jia, Dianzeng

2013-01-01

Hydrothermal strategies were successfully used to control the phases and morphologies of CdS nanocrystals. In the absence of an external direction-controlling process, the hexagonal and cubic phase well-defined leaf- and flower-like CdS nanocrystals were controlled obtained via adjusting the reaction duration or the concentration of surfactant. Oriented attachment growth modes were suggested for the formation of CdS superstructures, which was clarified through the tracing of temporal evolution of CdS nanoparticles. The CdS superstructures were structured by primary building nanoparticles, and held excellent visible emission with a peak in the green regions. This strategy is very helpful for studying the phase and morphology controlled fabrication of sulfides nanocrystals.

Low Temperature Synthesis of CdSe Quantum Dots with Amine Derivative and Their Chemical Kinetics

NASA Astrophysics Data System (ADS)

Seongmi Hwang,; Youngmin Choi,; Sunho Jeong,; Hakyun Jung,; Chang Gyoun Kim,; Teak-Mo Chung,; Beyong-Hwan Ryu,

2010-05-01

The chemical kinetics of growing CdSe nanocrystals was studied in order to investigate the effects of amine capping agents on the size of resulting quantum dots (QDs). CdSe QDs were prepared in phenyl ether, and the amine ligand dependence of QD size was determined. The results show that the size of CdSe nanocrystals can be regulated by controlling reaction rate, with smaller QDs being formed in slower processes. The results of photoluminescence (PL) studies show that the emission wavelengths of the QDs well correlate with particle size. This simple process for forming different-sized QDs, which uses a cheap solvent and various capping agents, has the potential for preparing CdSe nanocrystals more economically.

One-step colloidal synthesis of biocompatible water-soluble ZnS quantum dot/chitosan nanoconjugates

NASA Astrophysics Data System (ADS)

Ramanery, Fábio P.; Mansur, Alexandra AP; Mansur, Herman S.

2013-12-01

Quantum dots (QDs) are luminescent semiconductor nanocrystals with great prospective for use in biomedical and environmental applications. Nonetheless, eliminating the potential cytotoxicity of the QDs made with heavy metals is still a challenge facing the research community. Thus, the aim of this work was to develop a novel facile route for synthesising biocompatible QDs employing carbohydrate ligands in aqueous colloidal chemistry with optical properties tuned by pH. The synthesis of ZnS QDs capped by chitosan was performed using a single-step aqueous colloidal process at room temperature. The nanobioconjugates were extensively characterised by several techniques, and the results demonstrated that the average size of ZnS nanocrystals and their fluorescent properties were influenced by the pH during the synthesis. Hence, novel 'cadmium-free' biofunctionalised systems based on ZnS QDs capped by chitosan were successfully developed exhibiting luminescent activity that may be used in a large number of possible applications, such as probes in biology, medicine and pharmacy.

Uncovering the intrinsic size dependence of hydriding phase transformations in nanocrystals.

PubMed

Bardhan, Rizia; Hedges, Lester O; Pint, Cary L; Javey, Ali; Whitelam, Stephen; Urban, Jeffrey J

2013-10-01

A quantitative understanding of nanocrystal phase transformations would enable more efficient energy conversion and catalysis, but has been hindered by difficulties in directly monitoring well-characterized nanoscale systems in reactive environments. We present a new in situ luminescence-based probe enabling direct quantification of nanocrystal phase transformations, applied here to the hydriding transformation of palladium nanocrystals. Our approach reveals the intrinsic kinetics and thermodynamics of nanocrystal phase transformations, eliminating complications of substrate strain, ligand effects and external signal transducers. Clear size-dependent trends emerge in nanocrystals long accepted to be bulk-like in behaviour. Statistical mechanical simulations show these trends to be a consequence of nanoconfinement of a thermally driven, first-order phase transition: near the phase boundary, critical nuclei of the new phase are comparable in size to the nanocrystal itself. Transformation rates are then unavoidably governed by nanocrystal dimensions. Our results provide a general framework for understanding how nanoconfinement fundamentally impacts broad classes of thermally driven solid-state phase transformations relevant to hydrogen storage, catalysis, batteries and fuel cells.

Optical determination of crystal phase in semiconductor nanocrystals

PubMed Central

Lim, Sung Jun; Schleife, André; Smith, Andrew M.

2017-01-01

Optical, electronic and structural properties of nanocrystals fundamentally derive from crystal phase. This is especially important for polymorphic II–VI, III–V and I-III-VI2 semiconductor materials such as cadmium selenide, which exist as two stable phases, cubic and hexagonal, each with distinct properties. However, standard crystallographic characterization through diffraction yields ambiguous phase signatures when nanocrystals are small or polytypic. Moreover, diffraction methods are low-throughput, incompatible with solution samples and require large sample quantities. Here we report the identification of unambiguous optical signatures of cubic and hexagonal phases in II–VI nanocrystals using absorption spectroscopy and first-principles electronic-structure theory. High-energy spectral features allow rapid identification of phase, even in small nanocrystals (∼2 nm), and may help predict polytypic nanocrystals from differential phase contributions. These theoretical and experimental insights provide simple and accurate optical crystallographic analysis for liquid-dispersed nanomaterials, to improve the precision of nanocrystal engineering and improve our understanding of nanocrystal reactions. PMID:28513577

Natural biopolymers : novel templates for the synthesis of nanostructures.

Treesearch

Sonal Padalkar; J.R. Capadona; S.J. Rowan; C. Weder; Yu-Ho Won; Lia A. Stanciu; Robert J. Moon

2010-01-01

Biological systems such as proteins, viruses, and DNA have been most often reported to be used as templates for the synthesis of functional nanomaterials, but the properties of widely available biopolymers, such as cellulose, have been much less exploited for this purpose. Here, we report for the first time that cellulose nanocrystals (CNC) have the capacity to assist...

Solvent-Assisted Surface Engineering for High-Performance All-Inorganic Perovskite Nanocrystal Light-Emitting Diodes.

PubMed

Wang, Lin; Liu, Baiquan; Zhao, Xin; Demir, Hilmi Volkan; Gu, Haoshuang; Sun, Handong

2018-06-13

All-inorganic cesium halide perovskite nanocrystals have attracted much interest in optoelectronic applications for the sake of the readily adjustable band gaps, high photoluminescence quantum yield, pure color emission, and affordable cost. However, because of the ineluctable utilization of organic surfactants during the synthesis, the structural and optical properties of CsPbBr 3 nanocrystals degrade upon transforming from colloidal solutions to solid thin films, which plagues the device operation. Here, we develop a novel solvent-assisted surface engineering strategy, producing high-quality CsPbBr 3 thin films for device applications. A good solvent is first introduced as an assembly trigger to conduct assembly in a one-dimensional direction, which is then interrupted by adding a nonsolvent. The nonsolvent drives the adjacent nanoparticles connecting in a two-dimensional direction. Assembled CsPbBr 3 nanocrystal thin films are densely packed and very smooth with a surface roughness of ∼4.8 nm, which is highly desirable for carrier transport in a light-emitting diode (LED) device. Meanwhile, the film stability is apparently improved. Benefiting from this facile and reliable strategy, we have achieved remarkably improved performance of CsPbBr 3 nanocrystal-based LEDs. Our results not only enrich the methods of nanocrystal surface engineering but also shed light on developing high-performance LEDs.

Exciton-to-Dopant Energy Transfer in Mn-Doped Cesium Lead Halide Perovskite Nanocrystals.

PubMed

Parobek, David; Roman, Benjamin J; Dong, Yitong; Jin, Ho; Lee, Elbert; Sheldon, Matthew; Son, Dong Hee

2016-12-14

We report the one-pot synthesis of colloidal Mn-doped cesium lead halide (CsPbX 3 ) perovskite nanocrystals and efficient intraparticle energy transfer between the exciton and dopant ions resulting in intense sensitized Mn luminescence. Mn-doped CsPbCl 3 and CsPb(Cl/Br) 3 nanocrystals maintained the same lattice structure and crystallinity as their undoped counterparts with nearly identical lattice parameters at ∼0.2% doping concentrations and no signature of phase separation. The strong sensitized luminescence from d-d transition of Mn 2+ ions upon band-edge excitation of the CsPbX 3 host is indicative of sufficiently strong exchange coupling between the charge carriers of the host and dopant d electrons mediating the energy transfer, essential for obtaining unique properties of magnetically doped quantum dots. Highly homogeneous spectral characteristics of Mn luminescence from an ensemble of Mn-doped CsPbX 3 nanocrystals and well-defined electron paramagnetic resonance spectra of Mn 2+ in host CsPbX 3 nanocrystal lattices suggest relatively uniform doping sites, likely from substitutional doping at Pb 2+ . These observations indicate that CsPbX 3 nanocrystals, possessing many superior optical and electronic characteristics, can be utilized as a new platform for magnetically doped quantum dots expanding the range of optical, electronic, and magnetic functionality.

Development and characterization of silk fibroin coated quantum dots

NASA Astrophysics Data System (ADS)

Nathwani, B. B.; Needham, C.; Mathur, A. B.; Meissner, K. E.

2008-02-01

Recent progress in the field of semiconductor nanocrystals or Quantum Dots (QDs) has seen them find wider acceptance as a tool in biomedical research labs. As produced, high quality QDs, synthesized by high temperature organometallic synthesis, are coated with a hydrophobic ligand. Therefore, they must be further processed to be soluble in water and to be made biocompatible. To accomplish this, the QDs are generally coated with a synthetic polymer (eg. block copolymers) or the hydrophobic surface ligands exchanged with hydrophilic material (eg. thiols). Advances in this area have enabled the QDs to experience a smooth transition from being simple inorganic fluorophores to being smart sensors, which can identify specific cell marker proteins and help in diagnosis of diseases such as cancer. In order to improve the biocompatibility and utility of the QDs, we report the development of a procedure to coat QDs with silk fibroin, a fibrous crystalline protein extracted from Bombyx Mori silkworm. Following the coating process, we characterize the size, quantum yield and two-photon absorption cross section of the silk coated QDs. Additionally, the results of biocompatibility studies carried out to compare the properties of these QD-silks with conventional QDs are presented. These natural polymer coatings on QDs could enhance the intracellular delivery and enable the use of these nanocrystals as an imaging tool for studying subcellular machinery at the molecular level.

Surface oxidation of tin chalcogenide nanocrystals revealed by 119Sn-Mössbauer spectroscopy.

PubMed

de Kergommeaux, Antoine; Faure-Vincent, Jérôme; Pron, Adam; de Bettignies, Rémi; Malaman, Bernard; Reiss, Peter

2012-07-18

Narrow band gap tin(II) chalcogenide (SnS, SnSe, SnTe) nanocrystals are of high interest for optoelectronic applications such as thin film solar cells or photodetectors. However, charge transfer and charge transport processes strongly depend on nanocrystals' surface quality. Using (119)Sn-Mössbauer spectroscopy, which is the most sensitive tool for probing the Sn oxidation state, we show that SnS nanocrystals exhibit a Sn((IV))/Sn((II)) ratio of around 20:80 before and 40:60 after five minutes exposure to air. Regardless of the tin or sulfur precursors used, similar results are obtained using six different synthesis protocols. The Sn((IV)) content before air exposure arises from surface related SnS(2) and Sn(2)S(3) species as well as from surface Sn atoms bound to oleic acid ligands. The increase of the Sn((IV)) content upon air exposure results from surface oxidation. Full oxidation of the SnS nanocrystals without size change is achieved by annealing at 500 °C in air. With the goal to prevent surface oxidation, SnS nanocrystals are capped with a cadmium-phosphonate complex. A broad photoluminescence signal centered at 600 nm indicates successful capping, which however does not reduce the air sensitivity. Finally we demonstrate that SnSe nanocrystals exhibit a very similar behavior with a Sn((IV))/Sn((II)) ratio of 43:57 after air exposure. In the case of SnTe nanocrystals, the ratio of 55:45 is evidence of a more pronounced tendency for oxidation. These results demonstrate that prior to their use in optoelectronics further surface engineering of tin chalcogenide nanocrystals is required, which otherwise have to be stored and processed under inert atmosphere.

Metal complexes of alkyl-aryl dithiocarbamates: Structural studies, anticancer potentials and applications as precursors for semiconductor nanocrystals

NASA Astrophysics Data System (ADS)

Andrew, Fartisincha P.; Ajibade, Peter A.

2018-03-01

Dithiocarbamates are versatile ligands able to stabilize wide range of metal ions in their various oxidation states with the partial double bond character of Csbnd N and Csbnd S of thioureide moiety. Variation of the substituents attached to the nitrogen atom of dithiocarbamate moiety generates various intermolecular interactions, which lead to different structural arrangement in the solid state. The presence of bulky substituents on the N atom obviates the supramolecular aggregation via secondary Msbnd S interactions whereas smaller substituents encourage such aggregation that results in their wide properties and applications. Over the past decades, the synthesis and structural studies of metal complexes of dithiocarbamates have received considerable attention as potential anticancer agents with various degree of DNA binding affinity and cytotoxicity and as single molecule precursors for the preparation of semiconductor nanocrystals. In this paper, we review the synthesis, structural studies, anticancer potency and the use of alkyl-phenyl dithiocarbamate complexes as precursors for the preparation of semiconductor nanocrystals. The properties of these compounds and activities are ascribed to be due to either the dithiocarbamate moieties, the nature or type of the substituents around the dithiocarbamate backbone and the central metal ions or combination of these factors.

The Use of Cellulose Nanocrystals for Potential Application in Topical Delivery of Hydroquinone.

PubMed

Taheri, Azade; Mohammadi, Mina

2015-07-01

Nanotechnology-based drug delivery systems can enhance drug permeation through the skin and improve the drug stability. The biodegradability and biocompatibility of cellulose nanocrystals have made these nanoparticles good candidates to use in biomedical applications. The hyperpigmentation is a common skin disorder that could be caused by number of reasons such as sun exposure and pregnancy. Hydroquinone could inhibit the production of melanin and eliminate the discolorations of skin. This study is aimed at introducing cellulose nanocrystals as suitable carriers for drug delivery to skin. Prepared cellulose nanocrystals were characterized by dynamic light scattering and atomic force microscopy. The size of cellulose nanocrystals determined using dynamic light scattering was 301 ± 10 nm. Hydroquinone-cellulose nanocrystal complex was prepared by incubating of hydroquinone solution in cellulose nanocrystals suspension. The size of hydroquinone-cellulose nanocrystal complex determined using dynamic light scattering was 310 ± 10 nm. The hydroquinone content of the hydroquinone-cellulose complex was determined using UV/vis spectroscopy. Hydroquinone was bound to cellulose nanocrystals representing 79.3 ± 2% maximum binding efficiency when 1.1 mg hydroquinone was added to 1 mL of cellulose nanocrystals suspension (2 mg cellulose nanocrystal). The hydroquinone-cellulose nanocrystal complex showed an approximately sustained release profile of hydroquinone. Approximately, 80% of bound hydroquinone released in 4 h. © 2014 John Wiley & Sons A/S.

The Synthesis and Photoluminescent Properties of CaMoO₄:Eu³⁺ Nanocrystals by a Soft Chemical Route.

PubMed

Li, Fuhai; Yu, Lixin; Sun, Jiaju; Li, Songchu; Wei, Shuilin

2017-04-01

In this paper, the CaMoO4:Eu3+ phosphors were prepared by a simple hydrothermal method assisted by the citric acid as the surfactant, and characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and fluorescent spectrophotometry. The results of XRD show that the as-prepared samples are single phase. The process of the Ostwald ripening is controlled by the content of the citric acid in the hydrothermal reaction. The pH value of the precursor affects the shift of the charge transition band (CTB) in the excitation spectra. The reaction condition can strongly affect the luminescent intensity of the samples.

Synthesis and Photoluminescence Characteristics of Eu(3+)-Doped Molybdates Nanocrystals.

PubMed

Li, Fuhai; Yu, Lixin; Wei, Shuilin; Sun, Jiaju; Chen, Weiqing; Sun, Wei

2015-12-01

In this paper, the Eu(3+)-doped molybdate (CaMoO4, ZnMoO4 and BaMoO4) phosphors have been prepared by a hydrothermal method through modulating the pH value of the precursor solution (pH = 8, 10, and 12, respectively). The crystalline phase, morphology, photoluminescent properties of the prepared samples were systematically characterized by means of X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and photoluminescence (PL) spectra. The results indicate that the photoluminescence and morphology can be affected by the precursor solution. And the growth of the ZnMoO4 crystals also can be affected by the pH value of the precursor solution.

In vitro cytotoxicity effect and antibacterial performance of human lung epithelial cells A549 activity of Zinc oxide doped TiO2 nanocrystals: Investigation of bio-medical application by chemical method.

PubMed

Kaviyarasu, K; Geetha, N; Kanimozhi, K; Maria Magdalane, C; Sivaranjani, S; Ayeshamariam, A; Kennedy, J; Maaza, M

2017-05-01

We report the synthesis of high quality ZnO doped TiO 2 nanocrystals by chemical method at room temperature (RT), it can cause serious oxidative stress and DNA damage to human lung epithelial cells (A549) lines. Our aim in this study, to reduce the cytotoxicity effect of ZnO doped TiO 2 nanocrystals are widely in biological fields. Several studies have been performed to understand the influence of ZnO doped titanium dioxide (TiO 2 -NPs) on cell function; however the effects of nanoparticle against to exposure on the cell membrane have been duly addressed fascinatingly so far. However, In this interaction, which may alter cell metabolism and integrity, it is one of the importance to understand the modifications of the cell membrane, mechanisms of pulmonary A549 cell lines nanoparticles were uptake and the molecular pathway during the initial cell responses are still unclear and much more investigative efforts are need to properly characterize the ZnO doped titanium dioxide nanoparticles were reported successfully. In particular of the epithelial cells, upon particles are exposed human pulmonary epithelial cells (A549) to various concentrations of composition, structure and morphology of the nanocrystals were analyzed by X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). XRD assessed the crystal structure of the nanocrystals which identified peaks associated with (002), (100) and (101) planes of hexagonal wurtzite-type ZnO with lattice constants of a=b=3.249Å and c=5.219Å. The IR results showed high purity of products and indicated that the nanocrystals are made up of TiO and ZnO bonds. The Photoluminescence (PL) spectra are dominated by a strong narrow band edge emission tunable in the blue region of the visible spectra indicating a narrow size distribution of ZnO/TiO 2 nanocrystals which exhibits antibacterial activity over a broad range of bacterial species and in particular against Stre. Mut where it out competes four other commonly used E.coli, Pse. Aug, Stre. Mut and Salm. sps, well as testing four different appropriate concentration from the results showed a significant gain in viable cell numbers of all four bacteria species, with 5mM and 10mM being the most effective and 2mM being the worst, where it provided an effective improvement from the growth mechanism has been also proposed to the current interest of these nanocrystals will discussed in detail. Copyright © 2016 Elsevier B.V. All rights reserved.

Sulvanite (Cu 3VS 4) nanocrystals for printable thin film photovoltaics

DOE PAGES

Chen, Ching -Chin; Stone, Kevin H.; Lai, Cheng -Yu; ...

2017-09-21

Copper Vanadium Sulfide (Cu 3VS 4), also known as sulvanite, has recently emerged as a suitable absorber material for thin film photovoltaics. The synthesis of Cu 3VS 4 nanocrystals via a rapid solvothermal route is reported for the first time. The phase purity of the Cu 3VS 4 nanocrystals has been confirmed by X-ray powder diffraction (XRD) and Raman spectroscopy, while the nanoparticle size, of about 10 nm, was evaluated by transmission electron microscopy (TEM). Successful ligand exchange with sulfide, an inorganic ligand, demonstrated that the nanoparticles are amenable to surface modifications, key element in solution processing. Further annealing ofmore » as-synthesized nanocrystals under a sulfur/argon atmosphere at 600 °C, rendered highly crystalline Cu 3VS 4 powders exhibiting an impurity that could be potentially mitigated by annealing temperature optimization. Furthermore, Cu 3VS 4, formed solely from Earth-abundant elements, could provide an inexpensive, reliable approach to fabricating solution processed thin film photovoltaic absorbers.« less

Ultrafine and well dispersed silver nanocrystals on 2D nanosheets: synthesis and application as a multifunctional material for electrochemical catalysis and biosensing.

PubMed

Gao, Tao; Yang, Dawei; Ning, Limin; Lei, Lin; Ye, Zonghuang; Li, Genxi

2014-12-21

The strong coupling of inorganic nanocrystals with 2D nanosheets to produce function-enhanced nano-materials with uniform size, dispersion, and high coverage density has long been of interest to scientists from various research fields. Here, a simple and effective method has been described to fabricate ultrafine and well dispersed silver nanocrystals (AgNCs) on graphene oxide (GO), based on a facial-induced co-reduction strategy. The synthesized nanohybrid has shown uniform and well dispersed AgNCs (2.9 ± 1.4 nm), individually separated GO sheets, as well as highly covered surface (5250 nanocrystals per square micrometer), indicating the formation of a high-quality GO-based nanohybrid. Moreover, this material shows excellent catalytic activity for oxygen reduction reactions (ORRs) and exhibits enhanced signal readout for molecular sensing, demonstrating the potential application of this newly synthesized inorganic hybrid with strong synergistic coupling effects on advanced functional systems.

Sulvanite (Cu 3VS 4) nanocrystals for printable thin film photovoltaics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Ching -Chin; Stone, Kevin H.; Lai, Cheng -Yu

Copper Vanadium Sulfide (Cu 3VS 4), also known as sulvanite, has recently emerged as a suitable absorber material for thin film photovoltaics. The synthesis of Cu 3VS 4 nanocrystals via a rapid solvothermal route is reported for the first time. The phase purity of the Cu 3VS 4 nanocrystals has been confirmed by X-ray powder diffraction (XRD) and Raman spectroscopy, while the nanoparticle size, of about 10 nm, was evaluated by transmission electron microscopy (TEM). Successful ligand exchange with sulfide, an inorganic ligand, demonstrated that the nanoparticles are amenable to surface modifications, key element in solution processing. Further annealing ofmore » as-synthesized nanocrystals under a sulfur/argon atmosphere at 600 °C, rendered highly crystalline Cu 3VS 4 powders exhibiting an impurity that could be potentially mitigated by annealing temperature optimization. Furthermore, Cu 3VS 4, formed solely from Earth-abundant elements, could provide an inexpensive, reliable approach to fabricating solution processed thin film photovoltaic absorbers.« less

Bioinspired greigite magnetic nanocrystals: chemical synthesis and biomedicine applications

PubMed Central

Feng, Mei; Lu, Yang; Yang, Yuan; Zhang, Meng; Xu, Yun-Jun; Gao, Huai-Ling; Dong, Liang; Xu, Wei-Ping; Yu, Shu-Hong

2013-01-01

Large scale greigite with uniform dimensions has stimulated significant demands for applications such as hyperthermia, photovoltaics, medicine and cell separation, etc. However, the inhomogeneity and hydrophobicity for most of the as prepared greigite crystals has limited their applications in biomedicine. Herein, we report a green chemical method utilizing β-cyclodextrin (β-CD) and polyethylene glycol (PEG) to synthesize bioinspired greigite (Fe3S4) magnetic nanocrystals (GMNCs) with similar structure and magnetic property of magnetosome in a large scale. β-CD and PEG is responsible to control the crystal phase and morphology, as well as to bound onto the surface of nanocrystals and form polymer layers. The GMNCs exhibit a transverse relaxivity of 94.8 mM−1s−1 which is as high as iron oxide nanocrystals, and an entrapment efficiency of 58.7% for magnetic guided delivery of chemotherapeutic drug doxorubicin. Moreover, enhanced chemotherapeutic treatment of mice tumor was obtained via intravenous injection of doxorubicin loaded GMNCs. PMID:24141204

The Nanocrystalline State of Narrow Gap Semiconducting Chalcogenides

DTIC Science & Technology

2010-08-23

using a 1 nm scanning probe and the EDS microanalysis . For Annealing studies nanocrystal powder samples were placed in ceramic crucibles and annealed...nanocrystals are homogenous single phase EDS spectral images were collected in scanning transmission electron microcopy using a 1 nm electron probe...explorations with alio-valent elements (e.g. Sb3+, Ag+ doping in PbTe). • Perform chemical and physical characterization to demonstrate that nanocrystals are

Synthesis of bulk-size transparent gadolinium oxide–polymer nanocomposites for gamma ray spectroscopy

PubMed Central

Cai, Wen; Chen, Qi; Cherepy, Nerine; Dooraghi, Alex; Kishpaugh, David; Chatziioannou, Arion; Payne, Stephen; Xiang, Weidong

2015-01-01

Heavy element loaded polymer composites have long been proposed to detect high energy X- and γ-rays upon scintillation. The previously reported bulk composite scintillators have achieved limited success because of the diminished light output resulting from fluorescence quenching and opacity. We demonstrate the synthesis of a transparent nanocomposite comprising gadolinium oxide nanocrystals uniformly dispersed in bulk-size samples at a high loading content. The strategy to avoid luminescence quenching and opacity in the nanocomposite was successfully deployed, which led to the radioluminescence light yield of up to 27 000/MeV, about twice as much as standard commercial plastic scintillators. Nanocomposites monoliths (14 mm diameter by 3 mm thickness) with 31 wt% loading of nanocrystals generated a photoelectric peak for Cs-137 gamma (662 keV) with 11.4% energy resolution. PMID:26478816

Morphology, Microstructure and Transport Properties of ZnO Decorated SiO2 Nanoparticles (Preprint)

DTIC Science & Technology

2010-04-15

ZnO decorated SiO2 nanoparticles . While the growth conditions we employ for synthesis of ZnO nanocrys- tals are similar to... oxide nanocrystal synthesis on semiconductor oxide nanoparticles is an area yet to be fully explored. One advantage of this approach is that it enables... nanoparticles were resuspended. This washing process was repeated three times. In the hydrolytic ZnO synthesis method, a 1 ml suspension of SiO2 nanoshells

Organization of 'nanocrystal molecules' using DNA

NASA Astrophysics Data System (ADS)

Alivisatos, A. Paul; Johnsson, Kai P.; Peng, Xiaogang; Wilson, Troy E.; Loweth, Colin J.; Bruchez, Marcel P.; Schultz, Peter G.

1996-08-01

PATTERNING matter on the nanometre scale is an important objective of current materials chemistry and physics. It is driven by both the need to further miniaturize electronic components and the fact that at the nanometre scale, materials properties are strongly size-dependent and thus can be tuned sensitively1. In nanoscale crystals, quantum size effects and the large number of surface atoms influence the, chemical, electronic, magnetic and optical behaviour2-4. 'Top-down' (for example, lithographic) methods for nanoscale manipulation reach only to the upper end of the nanometre regime5; but whereas 'bottom-up' wet chemical techniques allow for the preparation of mono-disperse, defect-free crystallites just 1-10 nm in size6-10, ways to control the structure of nanocrystal assemblies are scarce. Here we describe a strategy for the synthesis of'nanocrystal molecules', in which discrete numbers of gold nanocrystals are organized into spatially defined structures based on Watson-Crick base-pairing interactions. We attach single-stranded DNA oligonucleotides of defined length and sequence to individual nanocrystals, and these assemble into dimers and trimers on addition of a complementary single-stranded DNA template. We anticipate that this approach should allow the construction of more complex two-and three-dimensional assemblies.

Induced synthesis of toroid-like lead sulfide nanocomposites in ethanol solution through a protein templating route

NASA Astrophysics Data System (ADS)

Zhang, Li; Qin, Dezhi; Yang, Guangrui; Du, Xian; Zhang, Qiuxia; Li, Feng

2015-09-01

The toroid-like PbS nanocrystals have been prepared in zein ethanol solution based on self-assembly template of protein molecules. From transmission electron microscopy observation, the obtained samples were monodispersed with an average size of about 47 nm. The chemical composition and crystal structure of nanocomposites were determined by X-ray diffraction and energy-dispersive X-ray spectrum measurements. The interaction between PbS and zein was investigated through Fourier transform infrared, photoluminescence, circular dichroism (CD) spectra, and thermogravimetric analysis. The PbS nanocrystals could react with nitrogen and oxygen atoms of zein molecules through coordination and electrostatic force. The CD spectra results suggested that PbS nanocrystals induced the conformational transition of protein from α-helix to β-sheet and then self-assembled into ring or toroid nanostructure. The quenching of zein fluorescence induced by PbS nanocrystals also showed the change in the chemical microenvironments of the fluorescent amino acid residues in the protein structure. The key step of this facile, biomimetic route was the formation of self-assembly nanostructure of zein, which could regulate the nucleation and growth of toroid-like PbS nanocrystals.

Electron tomography and 3D molecular simulations of platinum nanocrystals

NASA Astrophysics Data System (ADS)

Florea, Ileana; Demortière, Arnaud; Petit, Christophe; Bulou, Hervé; Hirlimann, Charles; Ersen, Ovidiu

2012-07-01

This work reports on the morphology of individual platinum nanocrystals with sizes of about 5 nm. By using the electron tomography technique that gives 3D spatial selectivity, access to quantitative information in the real space was obtained. The morphology of individual nanoparticles was characterized using HAADF-STEM tomography and it was shown to be close to a truncated octahedron. Using molecular dynamics simulations, this geometrical shape was found to be the one minimizing the nanocrystal energy. Starting from the tomographic reconstruction, 3D crystallographic representations of the studied Pt nanocrystals were obtained at the nanometer scale, allowing the quantification of the relative amount of the crystallographic facets present on the particle surface.This work reports on the morphology of individual platinum nanocrystals with sizes of about 5 nm. By using the electron tomography technique that gives 3D spatial selectivity, access to quantitative information in the real space was obtained. The morphology of individual nanoparticles was characterized using HAADF-STEM tomography and it was shown to be close to a truncated octahedron. Using molecular dynamics simulations, this geometrical shape was found to be the one minimizing the nanocrystal energy. Starting from the tomographic reconstruction, 3D crystallographic representations of the studied Pt nanocrystals were obtained at the nanometer scale, allowing the quantification of the relative amount of the crystallographic facets present on the particle surface. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr30990d

Shape control of II-VI semiconductor nanomaterials.

PubMed

Kumar, Sandeep; Nann, Thomas

2006-03-01

Anisotropic II-VI semiconductor nanocrystals and nanoparticles have become important building blocks for (potential) nanotechnological applications. Even though a wide variety of differently shaped nanoparticles of this class can be prepared, the underlying mechanisms are mostly not fully understood. This Review article provides a brief overview of the currently studied shape-evolution mechanisms and the most prominent synthesis methods for such particles, with an aim to provide a fundamental understanding on how different morphologies evolve, and to function as a tool to aid in the preparation of specific nanocrystals.

Luminescence characteristics of impurities-activated ZnS nanocrystals prepared in microemulsion with hydrothermal treatment

NASA Astrophysics Data System (ADS)

Xu, S. J.; Chua, S. J.; Liu, B.; Gan, L. M.; Chew, C. H.; Xu, G. Q.

1998-07-01

Cu-, Eu-, or Mn-doped ZnS nanocrystalline phosphors were prepared at room temperature using a chemical synthesis method. Transmission electron microscopy observation shows that the size of the ZnS clusters is in the 3-18 nm range. New luminescence characteristics such as strong and stable visible-light emissions with different colors were observed from the doped ZnS nanocrystals at room temperature. These results strongly suggest that impurities, especially transition metals and rare-earth metals-activated ZnS nanoclusters form a new class of luminescent materials.

Self-bonded composite films based on cellulose nanofibers and chitin nanocrystals as antifungal materials.

PubMed

Robles, Eduardo; Salaberria, Asier M; Herrera, Rene; Fernandes, Susana C M; Labidi, Jalel

2016-06-25

Cellulose nanofibers and chitin nanocrystals, two main components of agricultural and aquacultural by-products, were obtained from blue agave and yellow squat lobster industrial residues. Cellulose nanofibers were obtained using high pressure homogenization, while chitin nanocrystals were obtained by hydrolysis in acid medium. Cellulose nanofibers and chitin nanocrystals were characterized by X-ray diffraction, Atomic Force Microscopy and Infrared spectroscopy. Self-bonded composite films with different composition were fabricated by hot pressing and their properties were evaluated. Antifungal activity of chitin nanocrystals was studied using a Cellometer(®) cell count device, mechanical properties at tension were measured with a universal testing machine, water vapor permeability was evaluated with a thermohygrometer and surface tension with sessile drop contact angle method. The addition of chitin nanocrystals reduced slightly the mechanical properties of the composite. Presence of chitin nanocrystals influenced the growth of Aspergillus sp fungus in the surface of the composites as expected. Copyright © 2016 Elsevier Ltd. All rights reserved.

Structural, spectroscopic, and magnetic properties of Eu3+-doped GdVO4 nanocrystals synthesized by a hydrothermal method.

PubMed

Szczeszak, Agata; Grzyb, Tomasz; Śniadecki, Zbigniew; Andrzejewska, Nina; Lis, Stefan; Matczak, Michał; Nowaczyk, Grzegorz; Jurga, Stefan; Idzikowski, Bogdan

2014-12-01

New interesting aspects of the spectroscopic properties, magnetism, and method of synthesis of gadolinium orthovanadates doped with Eu(3+) ions are discussed. Gd(1-x)Eu(x)VO4 (x = 0, 0.05, 0.2) bifunctional luminescent materials with complex magnetic properties were synthesized by a microwave-assisted hydrothermal method. Products were formed in situ without previous precipitation. The crystal structures and morphologies of the obtained nanomaterials were analyzed by X-ray diffraction and transmission and scanning electron microscopy. Crystallographic data were analyzed using Rietveld refinement. The products obtained were nanocrystalline with average grain sizes of 70-80 nm. The qualitative and quantitative elemental composition as well as mapping of the nanocrystals was proved using energy-dispersive X-ray spectroscopy. The spectroscopic properties of red-emitting nanophosphors were characterized by their excitation and emission spectra and luminescence decays. Magnetic measurements were performed by means of vibrating sample magnetometry. GdVO4 and Gd0.8Eu0.2VO4 exhibited paramagnetic behavior with a weak influence of antiferromagnetic couplings between rare-earth ions. In the substituted sample, an additional magnetic contribution connected with the population of low-lying excited states of europium was observed.

Prospects of nanoscience with nanocrystals

DOE PAGES

Kovalenko, Maksym V.; Manna, Liberato; Cabot, Andreu; ...

2015-01-22

Colloidal nanocrystals (NCs, i.e., crystalline nanoparticles) have become an important class of materials with great potential for applications ranging from medicine to electronic and optoelectronic devices. Today’s strong research focus on NCs has been prompted by the tremendous progress in their synthesis. Impressively narrow size distributions of just a few percent, rational shape-engineering, compositional modulation, electronic doping, and tailored surface chemistries are now feasible for a broad range of inorganic compounds. The performance of inorganic NC-based photovoltaic and light-emitting devices has become competitive to other state-of-the-art materials. Semiconductor NCs hold unique promise for near- and mid-infrared technologies, where very fewmore » semiconductor materials are available. On a purely fundamental side, new insights into NC growth, chemical transformations, and self-organization can be gained from rapidly progressing in situ characterization and direct imaging techniques. In addition, new phenomena are constantly being discovered in the photophysics of NCs and in the electronic properties of NC solids. In this Nano Focus, we review the state of the art in research on colloidal NCs focusing on the most recent works published in the last 2 years.« less

Prospects of nanoscience with nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kovalenko, Maksym V.; Manna, Liberato; Cabot, Andreu

Colloidal nanocrystals (NCs, i.e., crystalline nanoparticles) have become an important class of materials with great potential for applications ranging from medicine to electronic and optoelectronic devices. Today’s strong research focus on NCs has been prompted by the tremendous progress in their synthesis. Impressively narrow size distributions of just a few percent, rational shape-engineering, compositional modulation, electronic doping, and tailored surface chemistries are now feasible for a broad range of inorganic compounds. The performance of inorganic NC-based photovoltaic and light-emitting devices has become competitive to other state-of-the-art materials. Semiconductor NCs hold unique promise for near- and mid-infrared technologies, where very fewmore » semiconductor materials are available. On a purely fundamental side, new insights into NC growth, chemical transformations, and self-organization can be gained from rapidly progressing in situ characterization and direct imaging techniques. In addition, new phenomena are constantly being discovered in the photophysics of NCs and in the electronic properties of NC solids. In this Nano Focus, we review the state of the art in research on colloidal NCs focusing on the most recent works published in the last 2 years.« less

A wearable multiplexed silicon nonvolatile memory array using nanocrystal charge confinement

PubMed Central

Kim, Jaemin; Son, Donghee; Lee, Mincheol; Song, Changyeong; Song, Jun-Kyul; Koo, Ja Hoon; Lee, Dong Jun; Shim, Hyung Joon; Kim, Ji Hoon; Lee, Minbaek; Hyeon, Taeghwan; Kim, Dae-Hyeong

2016-01-01

Strategies for efficient charge confinement in nanocrystal floating gates to realize high-performance memory devices have been investigated intensively. However, few studies have reported nanoscale experimental validations of charge confinement in closely packed uniform nanocrystals and related device performance characterization. Furthermore, the system-level integration of the resulting devices with wearable silicon electronics has not yet been realized. We introduce a wearable, fully multiplexed silicon nonvolatile memory array with nanocrystal floating gates. The nanocrystal monolayer is assembled over a large area using the Langmuir-Blodgett method. Efficient particle-level charge confinement is verified with the modified atomic force microscopy technique. Uniform nanocrystal charge traps evidently improve the memory window margin and retention performance. Furthermore, the multiplexing of memory devices in conjunction with the amplification of sensor signals based on ultrathin silicon nanomembrane circuits in stretchable layouts enables wearable healthcare applications such as long-term data storage of monitored heart rates. PMID:26763827

A wearable multiplexed silicon nonvolatile memory array using nanocrystal charge confinement.

PubMed

Kim, Jaemin; Son, Donghee; Lee, Mincheol; Song, Changyeong; Song, Jun-Kyul; Koo, Ja Hoon; Lee, Dong Jun; Shim, Hyung Joon; Kim, Ji Hoon; Lee, Minbaek; Hyeon, Taeghwan; Kim, Dae-Hyeong

2016-01-01

Strategies for efficient charge confinement in nanocrystal floating gates to realize high-performance memory devices have been investigated intensively. However, few studies have reported nanoscale experimental validations of charge confinement in closely packed uniform nanocrystals and related device performance characterization. Furthermore, the system-level integration of the resulting devices with wearable silicon electronics has not yet been realized. We introduce a wearable, fully multiplexed silicon nonvolatile memory array with nanocrystal floating gates. The nanocrystal monolayer is assembled over a large area using the Langmuir-Blodgett method. Efficient particle-level charge confinement is verified with the modified atomic force microscopy technique. Uniform nanocrystal charge traps evidently improve the memory window margin and retention performance. Furthermore, the multiplexing of memory devices in conjunction with the amplification of sensor signals based on ultrathin silicon nanomembrane circuits in stretchable layouts enables wearable healthcare applications such as long-term data storage of monitored heart rates.

Structure and properties of composite films formed by cellulose nanocrystals and charged latex nanoparticles

NASA Astrophysics Data System (ADS)

Thérien-Aubin, Héloïse; Lukach, Ariella; Pitch, Natalie; Kumacheva, Eugenia

2015-04-01

We report the structural and optical properties of composite films formed from mixed suspensions of cellulose nanocrystals (CNCs) and fluorescent latex nanoparticles (NPs). We explored the effect of NP concentration, size, surface charge, glass transition temperature and film processing conditions on film structure and properties. The chiral nematic order, typical of CNC films, was preserved in films with up to 50 wt% of negatively-charged latex NPs. Composite films were characterized by macroscopically close-to-uniform fluorescence, birefringence, and circular dichroism properties. In contrast, addition of positively charged latex NPs led to gelation of CNC-latex suspensions and disruption of the chiral nematic order in the composite films. Large latex NPs disrupted the chiral nematic order to a larger extend than small NPs. Furthermore, the glass transition of latex NPs had a dramatic effect on the structure of CNC-latex films. Latex particles in the rubbery state were easily incorporated in the ordered CNC matrix and improved the structural integrity of its chiral nematic phase.We report the structural and optical properties of composite films formed from mixed suspensions of cellulose nanocrystals (CNCs) and fluorescent latex nanoparticles (NPs). We explored the effect of NP concentration, size, surface charge, glass transition temperature and film processing conditions on film structure and properties. The chiral nematic order, typical of CNC films, was preserved in films with up to 50 wt% of negatively-charged latex NPs. Composite films were characterized by macroscopically close-to-uniform fluorescence, birefringence, and circular dichroism properties. In contrast, addition of positively charged latex NPs led to gelation of CNC-latex suspensions and disruption of the chiral nematic order in the composite films. Large latex NPs disrupted the chiral nematic order to a larger extend than small NPs. Furthermore, the glass transition of latex NPs had a dramatic effect on the structure of CNC-latex films. Latex particles in the rubbery state were easily incorporated in the ordered CNC matrix and improved the structural integrity of its chiral nematic phase. Electronic supplementary information (ESI) available: Detailed latex synthesis. Additional characterization of the nanoparticles and films. See DOI: 10.1039/c5nr00660k

Seed-induced growth of flower-like Au-Ni-ZnO metal-semiconductor hybrid nanocrystals for photocatalytic applications.

PubMed

Chen, Yuanzhi; Zeng, Deqian; Cortie, Michael B; Dowd, Annette; Guo, Huizhang; Wang, Junbao; Peng, Dong-Liang

2015-03-25

The combination of metal and semiconductor components in nanoscale to form a hybrid nanocrystal provides an important approach for achieving advanced functional materials with special optical, magnetic and photocatalytic functionalities. Here, a facile solution method is reported for the synthesis of Au-Ni-ZnO metal-semiconductor hybrid nanocrystals with a flower-like morphology and multifunctional properties. This synthetic strategy uses noble and magnetic metal Au@Ni nanocrystal seeds formed in situ to induce the heteroepitaxial growth of semiconducting ZnO nanopyramids onto the surface of metal cores. Evidence of epitaxial growth of ZnO{0001} facets on Ni {111} facets is observed on the heterojunction, even though there is a large lattice mismatch between the semiconducting and magnetic components. Adjustment of the amount of Au and Ni precursors can control the size and composition of the metal core, and consequently modify the surface plasmon resonance (SPR) and magnetic properties. Room-temperature superparamagnetic properties can be achieved by tuning the size of Ni core. The as-prepared Au-Ni-ZnO nanocrystals are strongly photocatalytic and can be separated and re-cycled by virtue of their magnetic properties. The simultaneous combination of plasmonic, semiconducting and magnetic components within a single hybrid nanocrystal furnishes it multifunctionalities that may find wide potential applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of quaternary chalcogenide CZTS nanoparticles by a hydrothermal route

NASA Astrophysics Data System (ADS)

Das, S.; Sa, K.; Mahakul, P. C.; Raiguru, J.; Alam, I.; Subramanyam, BVRS; Mahanandia, P.

2018-03-01

Cu2ZnSnS4 (CZTS) has emerged as a potential absorber towards inorganic photovoltaic device application for its outstanding properties like non toxicity, earth abundancy nature, optimal band gap matched with solar spectrum (1.45- 1.65eV), high absorption coefficient (104cm‑1). Here, a low cost, environment friendly facile hydrothermal route to synthesize phase pure CZTS nanoparticles using Cu (II), Zn (II), Sn (II) inorganic metal salts and thiourea as Sulphur source in distilled water solution as precursor is reported. The as synthesized samples characterized by X-Ray diffraction (XRD) and RAMAN confirmed structure and phase of CZTS nanocrystals. The morphology of the prepared CZTS have been characterized by scanning electron microscopy (SEM). The particle size is found in the range 4-5 nm with crystalline nature have been characterized by transmission electron microscope (TEM). The optical band gap of the as prepared samples is calculated to be 1.65eV from UV-Visible analysis which proves it can be used towards photovoltaic applications.

Direct growth and patterning of multilayer graphene onto a targeted substrate without an external carbon source.

PubMed

Kang, Dongseok; Kim, Won-Jun; Lim, Jung Ah; Song, Yong-Won

2012-07-25

Using only a simple tube furnace, we demonstrate the synthesis of patterned graphene directly on a designed substrate without the need for an external carbon source. Carbon atoms are absorbed onto Ni evaporator sources as impurities, and incorporated into catalyst layers during the deposition. Heat treatment conditions were optimized so that the atoms diffused out along the grain boundaries to form nanocrystals at the catalyst-substrate interfaces. Graphene patterns were obtained under patterned catalysts, which restricted graphene formation to within patterned areas. The resultant multilayer graphene was characterized by Raman spectroscopy and transmission electron microscopy to verify the high crystallinity and two-dimensional nanomorphology. Finally, a metal-semiconductor diode with a catalyst-graphene contact structure were fabricated and characterized to assess the semiconducting properties of the graphene sheets with respect to the display of asymmetric current-voltage behavior.

Characterization and evaluation in vivo of baicalin-nanocrystals prepared by an ultrasonic-homogenization-fluid bed drying method.

PubMed

Shi-Ying, Jin; Jin, Han; Shi-Xiao, Jin; Qing-Yuan, Lv; Jin-Xia, Bai; Chen, Hong-Ge; Rui-Sheng, Li; Wei, Wu; Hai-Long, Yuan

2014-01-01

To improve the absorption and bioavailability of baicalin using a nanocrystal (or nanosuspension) drug delivery system. A tandem, ultrasonic-homogenization-fluid bed drying technology was applied to prepare baicalin-nanocrystal dried powders, and the physicochemical properties of baicalin-nanocrystals were characterized by scanning electron microscopy, photon correlation spectroscopy, powder X-ray diffraction, physical stability, and solubility experiments. Furthermore, in situ intestine single-pass perfusion experiments and pharmacokinetics in rats were performed to make a comparison between the microcrystals of baicalin and pure baicalin in their absorption properties and bioavailability in vivo. The mean particle size of baicalin-nanocrystals was 236 nm, with a polydispersity index of 0.173, and a zeta potential value of -34.8 mV, which provided a guarantee for the stability of the reconstituted nanosuspension. X-Ray diffraction results indicated that the crystallinity of baicalin was decreased through the ultrasonic-homogenization process. Physical stability experiments showed that the prepared baicalin-nanocrystals were sufficiently stable. It was shown that the solubility of baicalin in the form of nanocrystals, at 495 μg·mL(-1), was much higher than the baicalin-microcrystals and the physical mixture (135 and 86.4 μg·mL(-1), respectively). In situ intestine perfusion experiments demonstrated a clear advantage in the dissolution and absorption characteristics for baicalin-nanocrystals compared to the other formulations. In addition, after oral administration to rats, the particle size decrease from the micron to nanometer range exhibited much higher in vivo bioavailability (with the AUC(0-t) value of 206.96 ± 21.23 and 127.95 ± 14.41 mg·L(-1)·h(-1), respectively). The nanocrystal drug delivery system using an ultrasonic-homogenization-fluid bed drying process is able to improve the absorption and in vivo bioavailability of baicalin, compared with pure baicalin coarse powder and micronized baicalin. Copyright © 2014 China Pharmaceutical University. Published by Elsevier B.V. All rights reserved.

Photoluminescence properties of arsenic and boron doped Si3N4 nanocrystal embedded in SiN x O y matrix

NASA Astrophysics Data System (ADS)

Puglia, Denise; Sombrio, Guilherme; dos Reis, Roberto; Boudinov, Henri

2018-03-01

Photoluminescence emission of Si3N4 nanocrystals embedded in SiN x O y matrices was investigated. Nanocrystals were grown by annealing of silicon oxynitride films deposited by sputtering, passivated in forming gas atmosphere and implanted with boron and arsenic. Emission energy was tuned from green to ultraviolet by changing the composition of SiN x O y matrices. Structural characterization of the nanocrystals was performed by Transmission Electron Microscopy. Photoluminescence at room and low temperatures was analyzed and the results suggest that light emission originates in the interface between the nanocrystals and the matrix. The highest photoluminescence intensity at room temperature was achieved by arsenic doped silicon oxynitride films deposited with an excess of nitrogen.

Measuring the Valence of Nanocrystal Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Owen, Jonathan Scharle

2016-11-30

The goal of this project is to understand and control the interplay between nanocrystal stoichiometry, surface ligand binding and exchange, and the optoelectronic properties of semiconductor nanocrystals in solution and in thin solid films. We pursued three research directions with this goal in mind: 1) We characterized nanocrystal stoichiometry and its influence on the binding of L-type and X-type ligands, including the thermodynamics of binding and the kinetics of ligand exchange. 2) We developed a quantitative understanding of the relationship between surface ligand passivation and photoluminescence quantum yield. 3) We developed methods to replace the organic ligands on the nanocrystalmore » with halide ligands and controllably deposit these nanocrystals into thin films, where electrical measurements were used to investigate the electrical transport and internanocrystal electronic coupling.« less

Electroluminescent devices formed using semiconductor nanocrystals as an electron transport media and method of making such electroluminescent devices

DOEpatents

Alivisatos, A. Paul; Colvin, Vickie

1996-01-01

An electroluminescent device is described, as well as a method of making same, wherein the device is characterized by a semiconductor nanocrystal electron transport layer capable of emitting visible light in response to a voltage applied to the device. The wavelength of the light emitted by the device may be changed by changing either the size or the type of semiconductor nanocrystals used in forming the electron transport layer. In a preferred embodiment the device is further characterized by the capability of emitting visible light of varying wavelengths in response to changes in the voltage applied to the device. The device comprises a hole processing structure capable of injecting and transporting holes, and usually comprising a hole injecting layer and a hole transporting layer; an electron transport layer in contact with the hole processing structure and comprising one or more layers of semiconductor nanocrystals; and an electron injecting layer in contact with the electron transport layer for injecting electrons into the electron transport layer. The capability of emitting visible light of various wavelengths is principally based on the variations in voltage applied thereto, but the type of semiconductor nanocrystals used and the size of the semiconductor nanocrystals in the layers of semiconductor nanometer crystals may also play a role in color change, in combination with the change in voltage.

Photoluminescence studies on Cd(1-x)Zn(x)S:Mn2+ nanocrystals.

PubMed

Sethi, Ruchi; Kumar, Lokendra; Pandey, A C

2009-09-01

Highly monodispersed, undoped and doped with Mn2+, binary and ternary (CdS, ZnS, Cd(1-x)Zn(x)S) compound semiconductor nanocrystals have been synthesized by co-precipitation method using citric acid as a stabilizer. As prepared sample are characterized by X-ray diffraction, Small angle X-ray scattering, Transmission electron microscope, Optical absorption and Photoluminescence spectroscopy, for their optical and structural properties. X-ray diffraction, Small angle X-ray scattering and Transmission electron microscope results confirm the preparation of monodispersed nanocrystals. Photoluminescence studies show a significant blue shift in the wavelength with an increasing concentration of Zn in alloy nanocrystals.

Spectral and dynamical properties of single excitons, biexcitons, and trions in cesium-lead-halide perovskite quantum dots

DOE PAGES

Makarov, Nikolay Sergeevich; Guo, Shaojun; Isaienko, Oleksandr; ...

2016-02-16

Organic–inorganic lead-halide perovskites have been the subject of recent intense interest due to their unusually strong photovoltaic performance. A new addition to the perovskite family is all-inorganic Cs–Pb-halide perovskite nanocrystals, or quantum dots, fabricated via a moderate-temperature colloidal synthesis. While being only recently introduced to the research community, these nanomaterials have already shown promise for a range of applications from color-converting phosphors and light-emitting diodes to lasers, and even room-temperature single-photon sources. Knowledge of the optical properties of perovskite quantum dots still remains vastly incomplete. Here we apply various time-resolved spectroscopic techniques to conduct a comprehensive study of spectral andmore » dynamical characteristics of single- and multiexciton states in CsPbX3 nanocrystals with X being either Br, I, or their mixture. Specifically, we measure exciton radiative lifetimes, absorption cross-sections, and derive the degeneracies of the band-edge electron and hole states. We also characterize the rates of intraband cooling and nonradiative Auger recombination and evaluate the strength of exciton–exciton coupling. The overall conclusion of this work is that spectroscopic properties of Cs–Pb-halide quantum dots are largely similar to those of quantum dots of more traditional semiconductors such as CdSe and PbSe. At the same time, we observe some distinctions including, for example, an appreciable effect of the halide identity on radiative lifetimes, considerably shorter biexciton Auger lifetimes, and apparent deviation of their size dependence from the “universal volume scaling” previously observed for many traditional nanocrystal systems. The high efficiency of Auger decay in perovskite quantum dots is detrimental to their prospective applications in light-emitting devices and lasers. Furthermore, this points toward the need for the development of approaches for effective suppression of Auger recombination in these nanomaterials, using perhaps insights gained from previous studies of II–VI nanocrystals.« less

Hydrothermal synthesis of iron phosphate microspheres constructed by mesoporous polyhedral nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Haojie; Sun, Yali; Jia, Xiaohua, E-mail: Jiaxh@ujs.edu.cn

2015-09-15

Novel monodispersed Fe{sub 5}(PO{sub 4}){sub 4}(OH){sub 3}·2H{sub 2}O microspheres with the diameters of several micrometers were prepared by a facile one-step hydrothermal method without using any templates, only employing FeCl{sub 3}·6H{sub 2}O and NaNH{sub 4}HPO{sub 4} as the initial materials. The obtained samples were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HR-TEM), respectively. The characterizations revealed that the as-prepared microspheres are constructed by the polyhedral nanoparticles with an average diameter of 100 nm. The corresponding FePO{sub 4} microspheres assembled by mesoporous polyhedral nanocrystals can be easily obtained by calcining a sphere-like Fe{sub 5}(PO{submore » 4}){sub 4}(OH){sub 3}·2H{sub 2}O precursor. - Graphical abstract: Novel monodispersed Fe{sub 5}(PO{sub 4}){sub 4}(OH){sub 3}·H{sub 2}O microspheres with a diameter of several micrometers were successfully obtained by a simple, template-free hydrothermal route. FePO{sub 4} microspheres constructed by mesoporous polyhedral FePO{sub 4} nanocrystals could be easily prepared by calcining an Fe{sub 5}(PO{sub 4}){sub 4}(OH){sub 3}·2H{sub 2}O precursor. Display Omitted - Highlights: • Monodispersed Fe{sub 5}(PO{sub 4}){sub 4}(OH){sub 3}·2H{sub 2}O microspheres were prepared by a facile hydrothermal method without using any templates • Fe{sub 5}(PO{sub 4}){sub 4}(OH){sub 3}·2H{sub 2}O microspheres present a novel morphology, which was constructed by closely polyhedral nanoparticles. • The FePO{sub 4} microspheres assembled by mesoporous polyhedral nanocrystals obtained by calcining Fe{sub 5}(PO{sub 4}){sub 4}(OH){sub 3}·2H{sub 2}O precursor.« less

Tunable Room-Temperature Synthesis of Coinage Metal Chalcogenide Nanocrystals from N -Heterocyclic Carbene Synthons

DOE PAGES

Lu, Haipeng; Brutchey, Richard L.

2017-01-23

Here we present a new toolset of precursors for semiconductor nanocrystal synthesis, N-heterocyclic carbene (NHC)-metal halide complexes, which enables a tunable molecular platform for the preparation of coinage metal chalcogenide quantum dots (QDs). Phase-pure and highly monodisperse coinage metal chalcogenide (Ag 2E, Cu 2-xE; E = S, Se) QDs are readily synthesized from the direct reaction of an NHC-MBr synthon (where M = Ag, Cu) with alkylsilyl chalcogenide reagents at room temperature. We demonstrate that the size of the resulting QDs is well tailored by the electron-donating ability of the L-type NHC ligands, which are further confirmed to be themore » only organic capping ligands on the QD surface, imparting excellent colloidal stability. Local superstructures of the NHC-capped Ag 2S QDs are observed by TEM, further demonstrating their potential for synthesizing monodisperse ensembles and mediating self-assembly.« less

Tunable Room-Temperature Synthesis of Coinage Metal Chalcogenide Nanocrystals from N -Heterocyclic Carbene Synthons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Haipeng; Brutchey, Richard L.

Here we present a new toolset of precursors for semiconductor nanocrystal synthesis, N-heterocyclic carbene (NHC)-metal halide complexes, which enables a tunable molecular platform for the preparation of coinage metal chalcogenide quantum dots (QDs). Phase-pure and highly monodisperse coinage metal chalcogenide (Ag 2E, Cu 2-xE; E = S, Se) QDs are readily synthesized from the direct reaction of an NHC-MBr synthon (where M = Ag, Cu) with alkylsilyl chalcogenide reagents at room temperature. We demonstrate that the size of the resulting QDs is well tailored by the electron-donating ability of the L-type NHC ligands, which are further confirmed to be themore » only organic capping ligands on the QD surface, imparting excellent colloidal stability. Local superstructures of the NHC-capped Ag 2S QDs are observed by TEM, further demonstrating their potential for synthesizing monodisperse ensembles and mediating self-assembly.« less

Superhydrophobic Silicon Nanocrystal-Silica Aerogel Hybrid Materials: Synthesis, Properties, and Sensing Application.

PubMed

Kehrle, Julian; Purkait, Tapas K; Kaiser, Simon; Raftopoulos, Konstantinos N; Winnacker, Malte; Ludwig, Theresa; Aghajamali, Maryam; Hanzlik, Marianne; Rodewald, Katia; Helbich, Tobias; Papadakis, Christine M; Veinot, Jonathan G C; Rieger, Bernhard

2018-04-24

Silicon nanocrystals (SiNCs) are abundant and exhibit exquisitely tailorable optoelectronic properties. The incorporation of SiNCs into highly porous and lightweight substrates such as aerogels leads to hybrid materials possessing the attractive features of both materials. This study describes the covalent deposition of SiNCs on and intercalation into silica aerogels, explores the properties, and demonstrates a prototype sensing application of the composite material. SiNCs of different sizes were functionalized with triethoxyvinylsilane (TEVS) via a radical grafting approach and subsequently used for the synthesis of photoluminescent silica hybrids. The resulting SiNC-containing aerogels possess high porosities, SiNC-based size-dependent photoluminescence, transparency, and a superhydrophobic macroscopic surface. The materials were used to examine the photoluminescence response toward low concentrations of 3-nitrotoluene (270 μM), demonstrating their potential as a sensing platform for high-energy materials.

Near white light emission of silicon nanocrystals

NASA Astrophysics Data System (ADS)

Lee, Soojin; Han, Il-Ki; Cho, Woon-Jo

2003-11-01

Silicon nanoparticles in the range from 2 nm to 5 nm was prepared from Zintl salt, soldium silicide (NaSi) by sonochemical method. This synthesis permits the reaction completed as fast as in a few hours and the easy alkyl-modification of nanocrystals surface at room temperature and ambient pressure. The average size of nanoparticles measured by the dynamic light scattering analysis was 2.7 nm. The high-resolution transmission electron micrograph cofirmed the material identity of nanoparticles as crystalline silicon. FT-IR spectra are consistent with the surface states of nanocrystals that is chlorine- or butyl-capped. The emission peak center moved to longer wavelength (up to 430 nm) with the reaction time, under a 325 nm excitation. The luminescence of silicon colloids looks bright bluish-white under excitation using a commercial low-intensity UV lamp.

Synthesis and Characterization of Microencapsulated Phase Change Materials with Poly(urea-urethane) Shells Containing Cellulose Nanocrystals.

PubMed

Yoo, Youngman; Martinez, Carlos; Youngblood, Jeffrey P

2017-09-20

The main objective of this study is to develop microencapsulation technology for thermal energy storage incorporating a phase change material (PCM) in a composite wall shell, which can be used to create a stable environment and allow the PCM to undergo phase change without any outside influence. Surface modification of cellulose nanocrystals (CNCs) was conducted by grafting poly(lactic acid) oligomers and oleic acid to improve the dispersion of nanoparticles in a polymeric shell. A microencapsulated phase change material (methyl laurate) with poly(urea-urethane) (PU) composite shells containing the hydrophobized cellulose nanocrystals (hCNCs) was fabricated using an in situ emulsion interfacial polymerization process. The encapsulation process of the PCMs with subsequent interfacial hCNC-PU to form composite microcapsules as well as their morphology, composition, thermal properties, and release rates was examined in this study. Oil soluble Sudan II dye solution in methyl laurate was used as a model hydrophobic fill, representing other latent fills with low partition coefficients, and their encapsulation efficiency as well as dye release rates were measured spectroscopically in a water medium. The influence of polyol content in the PU polymer matrix of microcapsules was investigated. An increase in polyol contents leads to an increase in the mean size of microcapsules but a decrease in the gel content (degree of cross-linking density) and permeability of their shell structure. The encapsulated PCMs for thermal energy storage demonstrated here exhibited promising performance for possible use in building or paving materials in terms of released heat, desired phase transformation temperature, chemical and physical stability, and concrete durability during placement.

Mangifera Indica leaf-assisted biosynthesis of well-dispersed silver nanoparticles

NASA Astrophysics Data System (ADS)

Philip, Daizy

2011-01-01

The use of various parts of plants for the synthesis of nanoparticles is considered as a green technology as it does not involve any harmful chemicals. The present study reports a facile and rapid biosynthesis of well-dispersed silver nanoparticles. The method developed is environmentally friendly and allows the reduction to be accelerated by changing the temperature and pH of the reaction mixture consisting of aqueous AgNO 3 and Mangifera Indica leaf extract. At a pH of 8, the colloid consists of well-dispersed triangular, hexagonal and nearly spherical nanoparticles having size ˜20 nm. The UV-vis spectrum of silver nanoparticles gave surface plasmon resonance (SPR) at 439 nm. The synthesized nanocrystals were characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. Water soluble organics present in the leaf are responsible for the reduction of silver ions. This green method provides faster synthesis comparable to chemical methods and can be used in areas such as cosmetics, foods and medical applications.

Spindly cobalt ferrite nanocrystals: preparation, characterization and magnetic properties.

PubMed

Cao, Xuebo; Gu, Li

2005-02-01

In this paper we describe the preparation of homogeneously needle-shaped cobalt ferrite (CoFe(2)O(4)) nanocrystals on a large scale through the smooth decomposition of urea and the resulting co-precipitation of Co(2+) and Fe(3+) in oleic acid micelles. Furthermore, we found that other ferrite nanocrystals with a needle-like shape, such as zinc ferrite (ZnFe(2)O(4)) and nickel ferrite (NiFe(2)O(4)), can be prepared by the same process. Needle-shaped CoFe(2)O(4) nanocrystals dispersed in an aqueous solution containing oleic acid exhibit excellent stability and the formed colloid does not produce any precipitations after two months, which is of prime importance if these materials are applied in magnetic fluids. X-ray diffraction (XRD) measurements were used to characterize the phase and component of the co-precipitation products, and demonstrate that they are spinel ferrite with a cubic symmetry. Transmission electron microscopy (TEM) observation showed that all the nanocrystals present a needle-like shape with a 22 nm short axis and an aspect ratio of around 6. Varying the concentration of oleic acid did not bring about any obvious influence on the size distribution and shapes of CoFe(2)O(4). The magnetic properties of the needle-shaped CoFe(2)O(4) nanocrystals were evaluated by using a vibrating sample magnetometer (VSM), electron paramagnetic resonance (EPR), and a Mössbauer spectrometer, and the results all demonstrated that CoFe(2)O(4) nanocrystals were superparamagnetic at room temperature.

Far from the equilibrium crystallization of oxide quantum dots in dried inorganic gels

NASA Astrophysics Data System (ADS)

Costille, B.; Dumoulin, M.; Ntsame Abagha, A. M.; Thune, E.; Guinebretière, R.

2018-06-01

We synthesized, through the sol-gel process, far from the equilibrium amorphous materials in which heterogeneous crystallization allowed the formation of oxide quantum dots. The isothermal evolutions of the mean size of the nanocrystals and the crystallinity of the materials were determined through x-ray diffraction experiments. The heterogeneous crystallization is characterized by a kinetic behavior that is far from that expected, according to the classical nucleation theory. We demonstrate that the evolution of the crystallinity is characterized by an Avrami exponent largely smaller than 1. Finally, nanocrystals exhibiting a size significantly below their Bohr radius are obtained and the number of these nanocrystals increases during isothermal treatment, whereas their mean size remains quasi-constant.

Quantitative tunneling spectroscopy of nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

First, Phillip N; Whetten, Robert L; Schaaff, T Gregory

2007-05-25

The proposed goals of this collaborative work were to systematically characterize the electronic structure and dynamics of 3-dimensional metal and semiconducting nanocrystals using scanning tunneling microscopy/spectroscopy (STM/STS) and ballistic electron emission spectroscopy (BEES). This report describes progress in the spectroscopic work and in the development of methods for creating and characterizing gold nanocrystals. During the grant period, substantial effort also was devoted to the development of epitaxial graphene (EG), a very promising materials system with outstanding potential for nanometer-scale ballistic and coherent devices ("graphene" refers to one atomic layer of graphitic, sp2 -bonded carbon atoms [or more loosely, few layers]).more » Funding from this DOE grant was critical for the initial development of epitaxial graphene for nanoelectronics« less

Improved oral bioavailability for lutein by nanocrystal technology: formulation development, in vitro and in vivo evaluation.

PubMed

Chang, Daoxiao; Ma, Yanni; Cao, Guoyu; Wang, Jianhuan; Zhang, Xia; Feng, Jun; Wang, Wenping

2018-08-01

Lutein is a kind of natural carotenoids possessing many pharmacological effects. The application of lutein was limited mainly due to its low oral bioavailability caused by poor aqueous solubility. Nanocrystal formulation of lutein was developed to improve the oral bioavailability in this study. The nanosuspension was prepared by the anti-solvent precipitation-ultrasonication method and optimized by Box-Behnken design, followed by freeze-drying to obtain lutein nanocrystals. The nanocrystals were characterized on their physical properties, in vitro dissolution and in vivo absorption performance. Lutein nanocrystals showed as tiny spheres with an average particle size of 110.7 nm. The result of diffractograms indicated that the percent crystallinity of lutein was 89.4% in coarse powder and then declined in nanocrystal formulation. The saturated solubility of lutein in water increased from 7.3 μg/ml for coarse powder up to 215.7 μg/ml for lutein nanocrystals. The dissolution rate of lutein nanocrystals was significantly higher than that of coarse powder or the physical mixture. The C max and AUC 0-24 h of lutein nanocrystals after oral administration in rats was 3.24 and 2.28 times higher than those of lutein suspension, respectively. These results indicated that the nanocrystal formulation could significantly enhance the dissolution and absorption of lutein and might be a promising approach for improving its oral bioavailability.

Synthesis and near-infrared fluorescence of K5NdLi2F10 nanocrystals and their dispersion with high doping concentration and long lifetime

NASA Astrophysics Data System (ADS)

Duan, Weikuan; Zhang, Yanyan; Wang, Zhongyue; Jiang, Jingyi; Liang, Chen; Wei, Wei

2014-05-01

K5NdLi2F10 nanocrystals were synthesized by a novel synthetic route in the liquid phase, which could improve the morphology and reduce the size effectively, for the first time. The luminescence intensities of the K5NdLi2F10 nanocrystals and their dispersion in polyethylene glycol 400 (PEG-400) approximate to that of neodymium doped phosphate glass (3 mol%), while the lifetimes of the nanocrystals alone and when dispersed with Nd3+ ions (1 × 1020 cm-3) are 303.4 μs and 174.6 μs respectively. Based on the Judd-Ofelt analysis, the emission quantum yield of the dispersion reaches 39.57%. In all, the K5NdLi2F10 nanocrystals and their dispersion have promising applications as liquid laser materials and biological fluorescent markers.K5NdLi2F10 nanocrystals were synthesized by a novel synthetic route in the liquid phase, which could improve the morphology and reduce the size effectively, for the first time. The luminescence intensities of the K5NdLi2F10 nanocrystals and their dispersion in polyethylene glycol 400 (PEG-400) approximate to that of neodymium doped phosphate glass (3 mol%), while the lifetimes of the nanocrystals alone and when dispersed with Nd3+ ions (1 × 1020 cm-3) are 303.4 μs and 174.6 μs respectively. Based on the Judd-Ofelt analysis, the emission quantum yield of the dispersion reaches 39.57%. In all, the K5NdLi2F10 nanocrystals and their dispersion have promising applications as liquid laser materials and biological fluorescent markers. Electronic supplementary information (ESI) available: Fitting curve of refractive index and detailed contents of Judd-Ofelt analysis. See DOI: 10.1039/c3nr06825k

Ion beam synthesis of indium-oxide nanocrystals for improvement of oxide resistive random-access memories

NASA Astrophysics Data System (ADS)

Bonafos, C.; Benassayag, G.; Cours, R.; Pécassou, B.; Guenery, P. V.; Baboux, N.; Militaru, L.; Souifi, A.; Cossec, E.; Hamga, K.; Ecoffey, S.; Drouin, D.

2018-01-01

We report on the direct ion beam synthesis of a delta-layer of indium oxide nanocrystals (In2O3-NCs) in silica matrices by using ultra-low energy ion implantation. The formation of the indium oxide phase can be explained by (i) the affinity of indium with oxygen, (ii) the generation of a high excess of oxygen recoils generated by the implantation process in the region where the nanocrystals are formed and (iii) the proximity of the indium-based nanoparticles with the free surface and oxidation from the air. Taking advantage of the selective diffusivity of implanted indium in SiO2 with respect to Si3N4, In2O3-NCs have been inserted in the SiO2 switching oxide of micrometric planar oxide-based resistive random access memory (OxRAM) devices fabricated using the nanodamascene process. Preliminary electrical measurements show switch voltage from high to low resistance state. The devices with In2O3-NCs have been cycled 5 times with identical operating voltages and RESET current meanwhile no switch has been observed for non implanted devices. This first measurement of switching is very promising for the concept of In2O3-NCs based OxRAM memories.

Probing the interface between semiconducting nanocrystals and molecular metal chalcogenide surface ligands: insights from first principles

NASA Astrophysics Data System (ADS)

Scalise, Emilio; Wippermann, Stefan; Galli, Giulia; Talapin, Dmitri

Colloidal nanocrystals (NCs) are emerging as cost-effective materials offering exciting prospects for solar energy conversion, light emission and electronic applications. Recent experimental advances demonstrate the synthesis of fully inorganic nanocrystal solids from chemical solution processing. The properties of the NC-solids are heavily determined by the NCs surface and their interactions with the host matrix. However, information on the atomistic structure of such composites is hard to obtain, due to the complexity of the synthesis conditions and the unavailability of robust experimental techniques to probe nanointerfaces at the microscopic level. Here we present a systematic theoretical study of the interaction between InAs and InP NCs with Sn2S64- ligands. Employing a grand canonical ab initio thermodynamic approach we investigate the relative stability of a multitude of configurations possibly realized at the NC-ligand interface. Our study highlights the importance of different structural details and their strong impact on the resulting composite's properties. We show that to obtain a detailed understanding of experimental data it is necessary to take into account complex interfacial structures beyond simplified NC-ligand model interfaces. S. W. acknowledges BMBF NanoMatFutur Grant No. 13N12972. G.G. acknowledges DOE-BES for funding part of this work.

Tuning the Magnetic Properties of Metal Oxide Nanocrystal Heterostructures by Cation Exchange

PubMed Central

2013-01-01

For three types of colloidal magnetic nanocrystals, we demonstrate that postsynthetic cation exchange enables tuning of the nanocrystal’s magnetic properties and achieving characteristics not obtainable by conventional synthetic routes. While the cation exchange procedure, performed in solution phase approach, was restricted so far to chalcogenide based semiconductor nanocrystals, here ferrite-based nanocrystals were subjected to a Fe2+ to Co2+ cation exchange procedure. This allows tracing of the compositional modifications by systematic and detailed magnetic characterization. In homogeneous magnetite nanocrystals and in gold/magnetite core shell nanocrystals the cation exchange increases the coercivity field, the remanence magnetization, as well as the superparamagnetic blocking temperature. For core/shell nanoheterostructures a selective doping of either the shell or predominantly of the core with Co2+ is demonstrated. By applying the cation exchange to FeO/CoFe2O4 core/shell nanocrystals the Neél temperature of the core material is increased and exchange-bias effects are enhanced so that vertical shifts of the hysteresis loops are obtained which are superior to those in any other system. PMID:23362940

In vivo investigation of hybrid Paclitaxel nanocrystals with dual fluorescent probes for cancer theranostics.

PubMed

Hollis, Christin P; Weiss, Heidi L; Evers, B Mark; Gemeinhart, Richard A; Li, Tonglei

2014-06-01

To develop novel hybrid paclitaxel (PTX) nanocrystals, in which bioactivatable (MMPSense® 750 FAST) and near infrared (Flamma Fluor® FPR-648) fluorophores are physically incorporated, and to evaluate their anticancer efficacy and diagnostic properties in breast cancer xenograft murine model. The pure and hybrid paclitaxel nanocrystals were prepared by an anti-solvent method, and their physical properties were characterized. The tumor volume change and body weight change were evaluated to assess the treatment efficacy and toxicity. Bioimaging of treated mice was obtained non-invasively in vivo. The released MMPSense molecules from the hybrid nanocrystals were activated by matrix metalloproteinases (MMPs) in vivo, similarly to the free MMPSense, demonstrating its ability to monitor cancer progression. Concurrently, the entrapped FPR-648 was imaged at a different wavelength. Furthermore, when administered at 20 mg/kg, the nanocrystal formulations exerted comparable efficacy as Taxol®, but with decreased toxicity. Hybrid nanocrystals that physically integrated two fluorophores were successfully prepared from solution. Hybrid nanocrystals were shown not only exerting antitumor activity, but also demonstrating the potential of multi-modular bioimaging for diagnostics.

A VO-seeded Approach for the Growth of Star-shaped VO2 and V2O5 Nanocrystals: Facile Synthesis Structural Characterization and Elucidation of Electronic Structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

L Whittaker; J Velazquez; S Banerjee

2011-12-31

Obtaining shape and size control of strongly correlated materials is imperative to obtain a fundamental understanding of the influence of finite size and surface restructuring on electronic instabilities in the proximity of the Fermi level. We present here a novel synthetic approach that takes advantage of the intrinsic octahedral symmetry of rock-salt-structured VO to facilitate the growth of six-armed nanocrystallites of related, technologically important binary vanadium oxides VO2 and V2O5. The prepared nanostructures exhibit clear six-fold symmetry and most notably show remarkable retention of electronic structure. The latter has been evidenced through extensive X-ray absorption spectroscopy measurements.

Photoswitching in azobenzene self-assembled monolayers capped on zinc oxide: nanodots vs nanorods.

PubMed

Shah, Syed Mujtaba; Martini, Cyril; Ackermann, Jörg; Fages, Frédéric

2012-02-01

We report the synthesis and spectroscopic characterization of nanohybrid structures consisting of an azobenzene compound grafted on the surface of zinc oxide nanoparticles. Characteristic bathochromic shifts indicate that the azobenzene photochromic molecules self-assemble onto the surface of the nanocrystals. The extent of packing is dependent on the shape of the nanoparticle. ZnO nanorods, with flat facets, enable a tighter organization of the molecules in the self-assembled monolayer than in the case of nanodots that display a more curvated shape. Consistently, the efficiency of photochromic switching of the self-assembled monolayer on ZnO nanoparticles is also shown to be strongly affected by nanoparticle shape. Copyright © 2011 Elsevier Inc. All rights reserved.

Additive-mediated electrochemical synthesis of platelike copper crystals for methanol electrooxidation.

PubMed

Venkatasubramanian, Rajesh; He, Jibao; Johnson, Michael W; Stern, Ilan; Kim, Dae Ho; Pesika, Noshir S

2013-10-29

A room-temperature electrochemical approach to synthesizing anisotropic platelike copper microcrystals and nanocrystals in the presence of potassium bromide is presented. Morphological and elemental characterization was performed using SEM, TEM, and XRD to confirm the anisotropic morphology and crystal structure of the synthesized copper particles. A possible mechanism for explaining the anisotropic crystal growth is proposed on the basis of the preferential adsorption of bromide ions to selective crystal faces. The shape-dependent electrocatalytic property of copper particles is demonstrated by its enhanced catalytic activity for methanol oxidation. Further development of such anisotropic copper particles localized on an electrode surface will lead us to find a suitable alternative for noble metal-based electrocatalysts for the methanol oxidation reaction relevant to fuel cells.

Synthesis and characterization of Graphene oxide/Zinc oxide nanorods sandwich structure

NASA Astrophysics Data System (ADS)

Boukhoubza, I.; Khenfouch, M.; Achehboune, M.; Mouthudi, B.; Zorkani, I.; Jorio, A.

2018-03-01

Graphene-ZnO nanostructures composite materials have been used as very efficient candidates for various optoelectronic applications. Nowadays, the composite structure formation of ZnO nanostructures with graphene or graphene oxide is a novel, cost effective and efficient approach to control the morphology, surface defect states, band gap of ZnO nanocrystals. In this paper, we have prepared ZnO nanorods between two layers graphene oxide (GO/ZnO NRs/GO) via a simple hydrothermal method. Their morphology, structural and optical properties have been investigated. The obtained results of our composites GO/ZnO NRs/GO presented here showing an enhancement in the structural and optical properties. Thus may hold great promise to the development of the optoelectronic devices.

Tuning the relative concentration ratio of bulk defects to surface defects in TiO2 nanocrystals leads to high photocatalytic efficiency.

PubMed

Kong, Ming; Li, Yuanzhi; Chen, Xiong; Tian, Tingting; Fang, Pengfei; Zheng, Feng; Zhao, Xiujian

2011-10-19

TiO(2) nanocrystals with tunable bulk/surface defects were synthesized and characterized with TEM, XRD, BET, positron annihilation, and photocurrent measurements. The effect of defects on photocatalytic activity was studied. It was found for the first time that decreasing the relative concentration ratio of bulk defects to surface defects in TiO(2) nanocrystals could significantly improve the separation efficiency of photogenerated electrons and holes, thus significantly enhancing the photocatalytic efficiency.

Radiation damage and nanocrystal formation in uranium-niobium titanates

NASA Astrophysics Data System (ADS)

Lian, J.; Wang, S. X.; Wang, L. M.; Ewing, R. C.

2001-07-01

Two uranium-niobium titanates, U 2.25Nb 1.90Ti 0.32O 9.8 and Nb 2.75U 1.20Ti 0.36O 10, formed during the synthesis of brannnerite (UTi 2O 6), a minor phase in titanate-based ceramics investigated for plutonium immobilization. These uranium titanates were subjected to 800 keV Kr 2+ irradiation from 30 to 973 K. The critical amorphization dose of the U-rich and Nb-rich titanates at room temperature were 4.72×10 17 and 5×10 17 ions/ m2, respectively. At elevated temperature, the critical amorphization dose increases due to dynamic thermal annealing. The critical amorphization temperature for both Nb-rich and U-rich titanates is ˜933 K under a 800 keV Kr 2+ irradiation. Above the critical amorphization temperature, nanocrystals with an average size of ˜15 nm were observed. The formation of nanocrystals is due to epitaxial recrystallization. At higher temperatures, an ion irradiation-induced nucleation-growth mechanism also contributes to the formation of nanocrystals.

Controlled growth of gold nanocrystals on biogenic As-S nanotubes by galvanic displacement

NASA Astrophysics Data System (ADS)

Liu, Fang; Chen, Wilfred; Myung, Nosang V.

2018-02-01

Traditional methods for fabricating nanoscale arrays are usually based on lithographic techniques while alternative new approaches rely on the use of nanoscale templates made of synthetic or biological materials. Here, gold (Au) nanocrystals were grown on the surface of the microbiologically formed As-S nanotubes through the process of galvanic displacement. The size and organization of the synthesized Au nanocrystals were affected by the pH dependent speciation of HAuCl4 precursors as well as the initial ratio of As-S/HAuCl4. We found that as pH increased, the Au nanocrystals grown on As-S nanotubes had smaller sizes but were more likely to assemble in one-dimension along the nanotubes. At a proper initial ratio of As-S/HAuCl4, Au nanotubes were formed at pH 6.0. The mechanism of Au nanostructures formation and the synthesis process at different pHs were proposed. The resulting Au nanoparticle/As-S nanotube and Au nanotube/As-S nanotube hetero-structures may provide important properties to be used for novel nano-electronic devices.

Formation of nanostructures in Eu3+ doped glass-ceramics: an XAS study.

PubMed

Pellicer-Porres, J; Segura, A; Martínez-Criado, G; Rodríguez-Mendoza, U R; Lavín, V

2013-01-16

We describe the results of x-ray absorption experiments carried out to deduce structural and chemical information in Eu(3+) doped, transparent, oxyfluoride glass and nanostructured glass-ceramic samples. The spectra were measured at the Pb and Eu-L(III) edges. The Eu environment in the glass samples is observed to be similar to that of EuF(3). Complementary x-ray diffraction experiments show that thermal annealing creates β-PbF(2) type nanocrystals. X-ray absorption indicates that Eu ions act as seeds in the nanocrystal formation. There is evidence of interstitial fluorine atoms around Eu ions as well as Eu dimers. X-ray absorption at the Pb-L(III) edge shows that after the thermal treatment most lead atoms form a PbO amorphous phase and that only 10% of the lead atoms remain available to form β-PbF(2) type nanocrystals. Both x-ray diffraction and absorption point to a high Eu content in the nanocrystals. Our study suggests new approaches to the oxyfluoride glass-ceramic synthesis in order to further improve their properties.

Synthesis of indium phosphide nanocrystals by sonochemical method and survey of optical properties

NASA Astrophysics Data System (ADS)

Trung, Ho Minh; Duy Thien, Nguyen; Van Vu, Le; Long, Nguyen Ngoc; Hieu, Truong Kim

2013-10-01

Indium phosphide semiconductor materials (InP) have various applications in the field of semiconductor optoelectronics because of its advantages. But the making of this material is difficult due to the very weak chemical activity of In element. In this report we present a simple method to synthesize InP nanocrystals from inorganic precursors such as indium chloride (InCl3), yellow phosphorus (P4), reduction agent NaBH4 at low temperature with the aid of ultrasound. Structural, morphological and optical properties of the formed InP nanocrystals were examined by transmission electron microscopy (TEM), X-ray diffraction (XRD), energy dispersed X-ray analysis (EDS), Raman scattering, absorption and photoluminscence (PL) spectroscopy. After the surface treatment of InP nanocrystals with liquid hydrofluoric (HF) acid, the luminescence spectra have an enhanced intensity and consist of the peaks in the region from 500 nm to 700 nm. The intensity of these peaks strongly depends on the concentration and etching time of HF. International Workshop on Advanced Materials and Nanotechnology 2012 (IWAMN 2012).

Genesis, challenges and opportunities for colloidal lead halide perovskite nanocrystals

NASA Astrophysics Data System (ADS)

Akkerman, Quinten A.; Rainò, Gabriele; Kovalenko, Maksym V.; Manna, Liberato

2018-05-01

Lead halide perovskites (LHPs) in the form of nanometre-sized colloidal crystals, or nanocrystals (NCs), have attracted the attention of diverse materials scientists due to their unique optical versatility, high photoluminescence quantum yields and facile synthesis. LHP NCs have a `soft' and predominantly ionic lattice, and their optical and electronic properties are highly tolerant to structural defects and surface states. Therefore, they cannot be approached with the same experimental mindset and theoretical framework as conventional semiconductor NCs. In this Review, we discuss LHP NCs historical and current research pursuits, challenges in applications, and the related present and future mitigation strategies explored.

Mineral contents and their solubility on calcium carbonat calcite nanocrystals from cockle shell powder (Anadara granosa Linn)

NASA Astrophysics Data System (ADS)

Widyastuti, S.; Pramushinta, I. A.

2018-03-01

Prepared and characterized calcium carbonat calcite nanocrystals improves solubility. Calcium carbonat calcite nanocrystals were synthesized using precipitation method from the waste of blood clam cockle shells (Anadara granosa Linn). This study was conducted to analyze mineral composition of nanocrystals calcium carbonat calcite cockle (Anadara granosa) shell for calcium fortification of food applications and to evaluate the solubilities of Calsium and Phospor. The sample of nanocrystals from cockle shells was evaluated to determine the content of 11 macro-and micro-elements. These elements are Calcium (Ca), Magnesium (Mg), Sodium (Na), Phosphorus (P), Potassium (K), Ferrum (Fe), Copper (Cu), Nickel (Ni), Zink (Zn), Boron (B) and Silica (Si)). Cockleshell powders were found to contain toxic elements below detectable levels. The solubilities of Calcium and Phospor were p<0.05.

Solution-Processed Solar Cells via Nanocrystal Inks and Molecular Solutions

NASA Astrophysics Data System (ADS)

Miskin, Caleb K.

On February 15, 2008 the National Academy of Engineering unveiled their fourteen grand challenges of engineering for the 21st century. At the top of the list and voted by the public as the most important challenge was the thrust to make solar energy economical. My research has been dedicated to solving this millennial challenge by developing routes to high-efficiency, solution-processed photovoltaics (PV) for low-cost and low-energy manufacturing. My research has primarily advanced two methods for solution processed PV. In one method, semiconducting nanocrystals are synthesized and then suspended in an appropriate solvent to form an ink. The ink is then applied to a substrate by a variety of high-throughput methods such as spray coating or doctor blading and then annealed to form a polycrystalline absorber layer for solar energy. I have applied this method with great success to Cu2ZnSnS 4, a promising earth-abundant, non-toxic semiconductor. A challenge with this material is its propensity to form binary and ternary undesired phases. Using advanced nano-characterization techniques, my colleagues and I have been able to determine the spatially resolved composition of these nanoparticles and have found them to be highly non-uniform. In addition, I developed synthesis techniques aimed at controlling the nucleation and growth of this material to improve nanocrystal compositional homogeneity. Though particles produced in this work still exhibit some non-uniformities, they are greatly improved. When combined with optimized fabrication techniques, I have been able to advance the efficiency of nanocrystal ink based solar cells of CZTS from 7.2 to 9.0 percent in our lab. Another promising route to solution-processed PV is by directly coating molecular precursor solutions (rather than first forming nanocrystals) and annealing the coating to form the polycrystalline solar absorber layer. Unfortunately, a major challenge is that many metals, metal salts, and chalcogens that would be useful precursors to such films have poor solubility in organic solvents compatible with roll-to-roll manufacturing techniques. Interestingly, we have found that mixtures of commonly available thiols and amines are able to dissolve at room temperature and pressure a host of metals and salts that are otherwise insoluble in either solvent by itself. In this work, I have primarily focused on CdTe--which has been by far the most successful technology in terms of production cost ($/peak watt) and energy payback time for thin-film solar cells. In this research thrust I demonstrate for the first time the fabrication of CdTe thin-films via a solution-processed molecular precursor approach by dissolving CdCl2 and Te in ethylenediamine and 1-propanethiol. The films are formed by spin-coating thin layers of the solution and then annealing each layer until a 1.5 mum thick film is achieved. I have achieved 0.5% efficient devices by this method. As thiol-amine mixtures have the potential to leave residual sulfur in these films, other novel solvent systems are presented as future work. While amine-thiol mixtures are excellent solvents for many materials, they do not dissolve lead chalcogenides with ease. I leverage this to develop room-temperature synthesis routes to PbS, PbSe, PbTe, and PbSxSe 1-x nanoparticles. This is achieved by mixing a lead salt dissolved in thiol-amine with a chalcogen dissolved in thiol-amine at room temperature. We find that when particles produced in this manner are pressed into pellets, they show comparable thermoelectric performance to more complicated and energy intensive synthesis techniques. Ultimately, we wish to enable the use of these particles in room-temperature fabricated quantum dot solar cells. This requires the synthesis of highly monodisperse, stable colloids and is the subject of future work using thiol-amine mixtures and related aqueous analogues.

Autoclave mediated one-pot-one-minute synthesis of AgNPs and Au-Ag nanocomposite from Melia azedarach bark extract with antimicrobial activity against food pathogens.

PubMed

Pani, Alok; Lee, Joong Hee; Yun, Soon-Ii

2016-01-01

The increasing use of nanoparticles and nanocomposite in pharmaceutical and processed food industry have increased the demand for nontoxic and inert metallic nanostructures. Chemical and physical method of synthesis of nanostructures is most popular in industrial production, despite the fact that these methods are labor intensive and/or generate toxic effluents. There has been an increasing demand for rapid, ecofriendly and relatively cheaper synthesis of nanostructures. Here, we propose a strategy, for one-minute green synthesis of AgNPs and a one-pot one-minute green synthesis of Au-Ag nanocomposite, using Melia azedarach bark aqueous extract as reducing agent. The hydrothermal mechanism of the autoclave technology has been successfully used in this study to accelerate the nucleation and growth of nano-crystals. The study also presents high antimicrobial potential of the synthesized nano solutions against common food and water born pathogens. The multistep characterization and analysis of the synthesized nanomaterial samples, using UV-visible spectroscopy, ICP-MS, FT-IR, EDX, XRD, HR-TEM and FE-SEM, also reveal the reaction dynamics of AgNO3, AuCl3 and plant extract in synthesis of the nanoparticles and nanocomposite. The antimicrobial effectiveness of the synthesized Au-Ag nanocomposite, with high gold to silver ratio, reduces the dependency on the AgNPs, which is considered to be environmentally more toxic than the gold counterpart. We hope that this new strategy will change the present course of green synthesis. The rapidity of synthesis will also help in industrial scale green production of nanostructures using Melia azedarach.

Bottom-up meets top-down: tailored raspberry-like Fe 3 O 4 –Pt nanocrystal superlattices

DOE PAGES

Qiu, Fen; Vervuurt, René H. J.; Verheijen, Marcel A.; ...

2018-01-01

Bottom up colloidal synthesis is combined with top down atomic layer deposition to achieve raspberry-like Pt-decorated Fe 3 O 4 nanoparticle superlattices with good metal–oxide–metal contact for photoelectrocatalysis.

Bottom-up meets top-down: tailored raspberry-like Fe 3 O 4 –Pt nanocrystal superlattices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qiu, Fen; Vervuurt, René H. J.; Verheijen, Marcel A.

Bottom up colloidal synthesis is combined with top down atomic layer deposition to achieve raspberry-like Pt-decorated Fe 3 O 4 nanoparticle superlattices with good metal–oxide–metal contact for photoelectrocatalysis.

A Facile Methodology for Engineering the Morphology of CsPbX3 Perovskite Nanocrystals under Ambient Condition

NASA Astrophysics Data System (ADS)

Seth, Sudipta; Samanta, Anunay

2016-11-01

A facile and highly reproducible room temperature, open atmosphere synthesis of cesium lead halide perovskite nanocrystals of six different morphologies is reported just by varying the solvent, ligand and reaction time. Sequential evolution of the quantum dots, nanoplates and nanobars in one medium and nanocubes, nanorods and nanowires in another medium is demonstrated. These perovskite nanoparticles are shown to be of excellent crystalline quality with high fluorescence quantum yield. A mechanism of the formation of nanoparticles of different shapes and sizes is proposed. Considering the key role of morphology in nanotechnology, this simple method of fabrication of a wide range of high quality nanocrystals of different shapes and sizes of all-inorganic lead halide perovskites, whose potential is already demonstrated in light emitting and photovoltaic applications, is likely to help widening the scope and utility of these materials in optoelectronic devices.

Quantum confinement effects on superconducting properties of Lead nanocrystals

NASA Astrophysics Data System (ADS)

Aubin, Herve; Moreira, Helena; Mahler, Benoit; Dubertret, Benoit

2008-03-01

We developed a new chemical synthesis method for producing large quantities of monodispersed lead (Pb) nanocrystals. They are obtained from the alcohol reduction of a mixture of two lead carboxylates with alkyl chains of different lengths, dissolved in a high temperature solvent. The nanocrystals obtained are protected from oxydation and aggregation by long chain fatty acids and their diameter can be tuned to reach values as low as 10 nm. Our results suggest that monodispersed particules are obtained when nucleation and growth occur at distincts temperatures, possibly as a consequence of different reactivities of the two lead carboxylates used in the solution. Owing to the large quantities of monodispersed particles produced, thermodynamics studies as function of particles diameter become possible. In particular, we will present a study of the effect of quantum confinement on superconducting properties of these Pb particles through SQUID magnetometry measurements.

Superparamagnetic magnetite nanocrystals-graphene oxide nanocomposites: facile synthesis and their enhanced electric double-layer capacitor performance.

PubMed

Wang, Qihua; Wang, Dewei; Li, Yuqi; Wang, Tingmei

2012-06-01

Superparamagnetic magnetite nanocrystals-graphene oxide (FGO) nanocomposites were successfully synthesized through a simple yet versatile one-step solution-processed approach at ambient conditions. Magnetite (Fe3O4) nanocrystals (NCs) with a size of 10-50 nm were uniformly deposited on the surfaces of graphene oxide (GO) sheets, which were confirmed by transmission electron microscopy (TEM) and high-angle annular dark field scanning transmission election microscopy (HAADF-STEM) studies. FGO with different Fe3O4 loadings could be controlled by simply manipulating the initial weight ratio of the precursors. The M-H measurements suggested that the as-prepared FGO nanocomposites have a large saturation magnetizations that made them can move regularly under an external magnetic field. Significantly, FGO nanocomposites also exhibit enhanced electric double-layer capacitor (EDLC) activity compared with pure Fe3O4 NCs and GO in terms of specific capacitance and high-rate charge-discharge.

Strain relaxation in epitaxial GaAs/Si (0 0 1) nanostructures

NASA Astrophysics Data System (ADS)

Kozak, Roksolana; Prieto, Ivan; Arroyo Rojas Dasilva, Yadira; Erni, Rolf; Skibitzki, Oliver; Capellini, Giovanni; Schroeder, Thomas; von Känel, Hans; Rossell, Marta D.

2017-11-01

Crystal defects, present in 100 nm GaAs nanocrystals grown by metal organic vapour phase epitaxy on top of (0 0 1)-oriented Si nanotips (with a tip opening 50-90 nm), have been studied by means of high-resolution aberration-corrected high-angle annular dark-field scanning transmission electron microscopy. The role of 60° perfect, 30° and 90° Shockley partial misfit dislocations (MDs) in the plastic strain relaxation of GaAs on Si is discussed. Formation conditions of stair-rod dislocations and coherent twin boundaries in the GaAs nanocrystals are explained. Also, although stacking faults are commonly observed, we show here that synthesis of GaAs nanocrystals with a minimum number of these defects is possible. On the other hand, from the number of MDs, we have to conclude that the GaAs nanoparticles are fully relaxed plastically, such that for the present tip sizes no substrate compliance can be observed.

Engineering the architectural diversity of heterogeneous metallic nanocrystals.

PubMed

Yu, Yue; Zhang, Qingbo; Xie, Jianping; Lee, Jim Yang

2013-01-01

Similar to molecular engineering where structural diversity is used to create more property variations for application explorations, the architectural engineering of heterogeneous metallic nanocrystals (HMNCs) can likewise increase the versatility of metallic nanocrystals (NCs). Here we present a synthesis strategy capable of engineering the architectural diversity of HMNCs through rational and independent programming of every architecture-determining element, that is, the shape and size of the component NCs and their spatial arrangement. The strategy is based on the galvanic replacement reaction of a self-sustaining layer formed by underpotential deposition on a polyhedral NC. The selective deposition of satellite NCs on specific site of the central NC is realized by creating a geometry-dependent heterogeneous electron distribution. This site-selective deposition approach is applicable to central NCs in various polyhedral shapes and sizes. The satellite NCs can further develop their own shape and size through crystal growth kinetics control.

Photoluminescent silicon nanocrystals with chlorosilane surfaces - synthesis and reactivity

NASA Astrophysics Data System (ADS)

Höhlein, Ignaz M. D.; Kehrle, Julian; Purkait, Tapas K.; Veinot, Jonathan G. C.; Rieger, Bernhard

2014-12-01

We present a new efficient two-step method to covalently functionalize hydride terminated silicon nanocrystals with nucleophiles. First a reactive chlorosilane layer was formed via diazonium salt initiated hydrosilylation of chlorodimethyl(vinyl)silane which was then reacted with alcohols, silanols and organolithium reagents. With organolithium compounds a side reaction is observed in which a direct functionalization of the silicon surface takes place.We present a new efficient two-step method to covalently functionalize hydride terminated silicon nanocrystals with nucleophiles. First a reactive chlorosilane layer was formed via diazonium salt initiated hydrosilylation of chlorodimethyl(vinyl)silane which was then reacted with alcohols, silanols and organolithium reagents. With organolithium compounds a side reaction is observed in which a direct functionalization of the silicon surface takes place. Electronic supplementary information (ESI) available: Detailed experimental procedures and additional NMR, PL, EDX, DLS and TEM data. See DOI: 10.1039/C4NR05888G

Size-controlled synthesis of gold bipyramids using an aqueous mixture of CTAC and salicylate anions as the soft template.

PubMed

Yoo, Hyojong; Jang, Min Hoon

2013-08-07

One-dimensional (1D) gold (Au) bipyramids are successfully synthesized through a facile seed-mediated method using cetyltrimethylammonium chloride (CTAC), Au seed nanoparticles, Ag(+) ions, and ascorbic acid. The length and optical properties of the synthesized Au bipyramids are controlled with precision by varying the amount of salicylate anions (Sal(-)) added during the synthesis. The micelles formed from CTA(+)-Sal(-) mixtures in aqueous solutions act as effective templates for the size-controlled synthesis of 1D nanocrystals.

Near-Infrared Photoluminescence Enhancement in Ge/CdS and Ge/ZnS Core/Shell Nanocrystals: Utilizing IV/II-VI Semiconductor Epitaxy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Yijun; Rowland, Clare E; Schaller, Richard D

2014-08-26

Ge nanocrystals have a large Bohr radius and a small, size-tunable band gap that may engender direct character via strain or doping. Colloidal Ge nanocrystals are particularly interesting in the development of near-infrared materials for applications in bioimaging, telecommunications and energy conversion. Epitaxial growth of a passivating shell is a common strategy employed in the synthesis of highly luminescent II–VI, III–V and IV–VI semiconductor quantum dots. Here, we use relatively unexplored IV/II–VI epitaxy as a way to enhance the photoluminescence and improve the optical stability of colloidal Ge nanocrystals. Selected on the basis of their relatively small lattice mismatch comparedmore » with crystalline Ge, we explore the growth of epitaxial CdS and ZnS shells using the successive ion layer adsorption and reaction method. Powder X-ray diffraction and electron microscopy techniques, including energy dispersive X-ray spectroscopy and selected area electron diffraction, clearly show the controllable growth of as many as 20 epitaxial monolayers of CdS atop Ge cores. In contrast, Ge etching and/or replacement by ZnS result in relatively small Ge/ZnS nanocrystals. The presence of an epitaxial II–VI shell greatly enhances the near-infrared photoluminescence and improves the photoluminescence stability of Ge. Ge/II–VI nanocrystals are reproducibly 1–3 orders of magnitude brighter than the brightest Ge cores. Ge/4.9CdS core/shells show the highest photoluminescence quantum yield and longest radiative recombination lifetime. Thiol ligand exchange easily results in near-infrared active, water-soluble Ge/II–VI nanocrystals. We expect this synthetic IV/II–VI epitaxial approach will lead to further studies into the optoelectronic behavior and practical applications of Si and Ge-based nanomaterials.« less

LDH nanocages synthesized with MOF templates and their high performance as supercapacitors

NASA Astrophysics Data System (ADS)

Jiang, Zhen; Li, Zhengping; Qin, Zhenhua; Sun, Haiyan; Jiao, Xiuling; Chen, Dairong

2013-11-01

Layered double hydroxides (LDHs) are currently attracting intense research interest for their various applications. Three LDH hollow nano-polyhedra are synthesized with zeolitic imidazolate framework-67 (ZIF-67) nanocrystals as the templates. The nanocages well inherit the rhombic dodecahedral shape of the ZIF-67 templates, and the shell is composed of nanosheets assembled with an edge-to-face stacking. This is the first synthesis of the LDH non-spherical structures. And the mechanism of utilizing metal-organic framework (MOF) nanocrystals as templates is explored. Control of the simultaneous reactions, the precipitation of the shells and the template etching, is extremely crucial to the preparation of the perfect nanocages. And the Ni-Co LDH nanocages exhibit superior pseudocapacitance property due to their novel hierarchical and submicroscopic structures.Layered double hydroxides (LDHs) are currently attracting intense research interest for their various applications. Three LDH hollow nano-polyhedra are synthesized with zeolitic imidazolate framework-67 (ZIF-67) nanocrystals as the templates. The nanocages well inherit the rhombic dodecahedral shape of the ZIF-67 templates, and the shell is composed of nanosheets assembled with an edge-to-face stacking. This is the first synthesis of the LDH non-spherical structures. And the mechanism of utilizing metal-organic framework (MOF) nanocrystals as templates is explored. Control of the simultaneous reactions, the precipitation of the shells and the template etching, is extremely crucial to the preparation of the perfect nanocages. And the Ni-Co LDH nanocages exhibit superior pseudocapacitance property due to their novel hierarchical and submicroscopic structures. Electronic supplementary information (ESI) available: Experimental details, XRD, TEM, SEM, and XPS images. See DOI: 10.1039/c3nr03829g

Influences of urea–glycerol mixtures as mixed mesopore-controlling agents on tailoring physicochemical properties and photocatalytic H{sub 2} production activity of sol–gel-derived mesoporous-assembled TiO{sub 2} nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sreethawong, Thammanoon, E-mail: sreethawongt@imre.a-star.edu.sg; Ngamsinlapasathian, Supachai, E-mail: wonone@hotmail.com; Yoshikawa, Susumu

2013-01-15

Graphical abstract: Display Omitted Highlights: ► Mesoporous-assembled TiO{sub 2} nanocrystals were synthesized by modified sol–gel process. ► Urea–glycerol mixtures were applied as mixed mesopore-controlling agents. ► Urea and glycerol contents affected physicochemical properties of synthesized TiO{sub 2}. ► Photocatalytic H{sub 2} production activity also depended on urea and glycerol contents. ► 75 mol% urea and 25 mol% glycerol yielded the most photocatalytically active TiO{sub 2}. -- Abstract: In this work, the mesoporous-assembled TiO{sub 2} nanocrystal photocatalysts were successfully synthesized by a sol–gel process with the aid of urea–glycerol mixtures used as mixed mesopore-controlling agents. The photocatalytic activity of the synthesizedmore » mesoporous-assembled TiO{sub 2} nanocrystal photocatalysts was investigated for hydrogen production from the water splitting reaction using methanol as a hole scavenger under UV light irradiation. The synthesized TiO{sub 2} nanocrystal photocatalysts were systematically characterized by TG–DTA, N{sub 2} adsorption–desorption, SEM, high resolution TEM, and XRD analyses. The characterization results showed that the well-controlled contents of urea and glycerol in a urea–glycerol mixture at 75 mol% urea and 25 mol% glycerol resulted in not only the most highly porous network (i.e. the highest specific surface area and total pore volume, and the smallest mean mesopore diameter), but also the smallest crystallite size of the synthesized TiO{sub 2} nanocrystal photocatalyst. The photocatalytic reaction results, hence, revealed a much superior photocatalytic hydrogen production activity of the mesoporous-assembled TiO{sub 2} nanocrystal synthesized with 75 mol% urea and 25 mol% glycerol to the other synthesized TiO{sub 2} nanocrystals, also being much higher than those of the commercially available P-25 TiO{sub 2} and ST-01 TiO{sub 2} powders.« less

Capping Ligand Vortices as “Atomic Orbitals” in Nanocrystal Self-Assembly

DOE PAGES

Waltmann, Curt; Horst, Nathan; Travesset, Alex

2017-10-27

In this work, we present a detailed analysis of the interaction between two nanocrystals capped with ligands consisting of hydrocarbon chains by united atom molecular dynamics simulations. We show that the bonding of two nanocrystals is characterized by ligand textures in the form of vortices. These results are generalized to nanocrystals of different types (differing core and ligand sizes) where the structure of the vortices depends on the softness asymmetry. We provide rigorous calculations for the binding free energy, show that these energies are independent of the chemical composition of the cores, and derive analytical formulas for the equilibrium separation.more » We discuss the implications of our results for the self-assembly of single-component and binary nanoparticle superlattices. Overall, our results show that the structure of the ligands completely determines the bonding of nanocrystals, fully supporting the predictions of the recently proposed Orbifold topological model.« less

Effects of La0.2Ce0.6Eu0.2F3 nanocrystals capped with polyethylene glycol on human pancreatic cancer cells in vitro

NASA Astrophysics Data System (ADS)

Withers, Nathan J.; Glazener, Natasha N.; Rivera, Antonio C.; Akins, Brian A.; Armijo, Leisha M.; Plumley, John B.; Cook, Nathaniel C.; Sugar, Jacqueline M.; Chan, Rana; Brandt, Yekaterina I.; Smolyakov, Gennady A.; Heintz, Philip H.; Osiński, Marek

2013-02-01

Lanthanide fluoride colloidal nanocrystals offer a way to improve the diagnosis and treatment of cancer through the enhanced absorption of ionizing radiation, in addition to providing visible luminescence. In order to explore this possibility, tests with a kilovoltage therapy unit manufactured by the Universal X-Ray Company were performed to estimate the energy sensitivity of this technique. La0.2Ce0.6Eu0.2F3 nanocrystals capped with polyethylene glycol of molecular weight 6000 were synthesized, suspended in deionized water, and made tolerant to biological ionic pressures by incubation with fetal bovine serum. These nanocrystals were characterized by dynamic light scattering, muffle furnace ashing, and photoluminescence spectroscopy. Clonogenic assays were performed on the cells to assay the cytotoxicity and radiotoxicity of the nanocrystals on the human pancreatic cancer cell line PANC-1, purchased from ATCC.

Capping Ligand Vortices as "Atomic Orbitals" in Nanocrystal Self-Assembly.

PubMed

Waltmann, Curt; Horst, Nathan; Travesset, Alex

2017-11-28

We present a detailed analysis of the interaction between two nanocrystals capped with ligands consisting of hydrocarbon chains by united atom molecular dynamics simulations. We show that the bonding of two nanocrystals is characterized by ligand textures in the form of vortices. These results are generalized to nanocrystals of different types (differing core and ligand sizes) where the structure of the vortices depends on the softness asymmetry. We provide rigorous calculations for the binding free energy, show that these energies are independent of the chemical composition of the cores, and derive analytical formulas for the equilibrium separation. We discuss the implications of our results for the self-assembly of single-component and binary nanoparticle superlattices. Overall, our results show that the structure of the ligands completely determines the bonding of nanocrystals, fully supporting the predictions of the recently proposed Orbifold topological model.

Highly aqueous soluble CaF2:Ce/Tb nanocrystals: effect of surface functionalization on structural, optical band gap, and photoluminescence properties.

PubMed

Ansari, Anees A; Parchur, Abdul K; Kumar, Brijesh; Rai, S B

2016-12-01

The design of nanostructured materials with highly stable water-dispersion and luminescence efficiency is an important concern in nanotechnology and nanomedicine. In this paper, we described the synthesis and distinct surface modification on the morphological structure and optical (optical absorption, band gap energy, excitation, emission, decay time, etc.) properties of highly crystalline water-dispersible CaF 2 :Ce/Tb nanocrystals (core-nanocrystals). The epitaxial growth of inert CaF 2 and silica shell, respectively, on their surface forming as CaF 2 :Ce/Tb@CaF 2 (core/shell) and CaF 2 :Ce/Tb@CaF 2 @SiO 2 (core/shell/SiO 2 ) nanoarchitecture. X-ray diffraction and transmission electron microscope image shows that the nanocrystals were in irregular spherical phase, highly crystalline (~20 nm) with narrow size distribution. The core/shell nanocrystals confirm that the surface coating is responsible in the change of symmetrical nanostructure, which was determined from the band gap energy and luminescent properties. It was found that an inert inorganic shell formation effectively enhances the luminescence efficiency and silica shell makes the nanocrystals highly water-dispersible. In addition, Ce 3+ /Tb 3+ -co-doped CaF 2 nanocrystals show efficient energy transfer from Ce 3+ to Tb 3+ ion and strong green luminescence of Tb 3+ ion at 541 nm( 5 D 4 → 7 F 5 ). Luminescence decay curves of core and core/shell nanocrystals were fitted using mono and biexponential equations, and R 2 regression coefficient criteria were used to discriminate the goodness of the fitted model. The lifetime values for the core/shell nanocrystals are higher than core-nanocrystals. Considering the high stable water-dispersion and intensive luminescence emission in the visible region, these luminescent core/shell nanocrystals could be potential candidates for luminescent bio-imaging, optical bio-probe, displays, staining, and multianalyte optical sensing. A newly designed CaF 2 :Ce/Tb nanoparticles via metal complex decomposition rout shows high dispersibility in aqueous solvents with enhanced photoluminescence. The epitaxial growth of inert CaF 2 shell and further amorphous silica, respectively, enhanced their optical and luminescence properties, which is highly usable for luminescent biolabeling, and optical bioprobe etc.

Electrical and optical properties of NdAlO{sub 3} synthesized by an optimized combustion process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harilal, Midhun; Faculty of Industrial Sciences and Technology, Universiti Malaysia Pahang, 26300 Kuantan, Pahang; Nair, V. Manikantan

2014-04-01

Nanocrystals of neodymium aluminate (NdAlO{sub 3}) are synthesized using an optimized single step auto-ignition citrate complex combustion process. The combustion product was characterized by X-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy and Ultraviolet–visible reflection spectroscopy. The combustion product is single phase and composed of aggregates of nanocrystals of sizes in the range 20–40 nm. The NdAlO{sub 3} crystallized in rhombohedral perovskite structure with lattice parameters a = 5.3223 Å and c = 12.9292 Å. The absorption spectrum of the NdAlO{sub 3} nanocrystals shows characteristic absorption bands of the Nd atom. The polycrystalline fluffy combustion product ismore » sintered to high density (∼ 97%) at ∼ 1450 °C for 4 h and the microstructure was characterized by scanning electron microscopy. The electrical properties of the sintered product were studied using dielectric measurements. The sintered NdAlO{sub 3} has a dielectric constant (ε{sub r}) and a dielectric loss (tan δ) of 21.9 and ∼ 10{sup −3} at 5 MHz, respectively. - Highlights: • NdAlO{sub 3} nanocrystals were synthesized through a citrate combustion process. • The nanocrystals were sintered to ∼ 97% of theoretical density. • The materials were characterized using a number of analytical techniques. • Nanostructured NdAlO{sub 3} showed crystal field splitting of Nd ions. • Dielectric properties of the sintered NdAlO{sub 3} ceramics were studied.« less

Hydrophilic ionic liquid-passivated CdTe quantum dots for mercury ion detection.

PubMed

Chao, Mu-Rong; Chang, Yan-Zin; Chen, Jian-Lian

2013-04-15

A hydrophilic ionic liquid, 1-ethyl-3-methylimidazolium dicyanamide (EMIDCA), was used as a medium for the synthesis of highly luminescent CdTe nanocrystals (NCs) capped with thioglycolic acid (TGA). The synthesis was performed for 8 h at 130 °C, was similar to nanocrystal preparation in an aqueous medium, and used safe, low-cost inorganic salts as precursors. After the reaction, the photoluminescence quantum yield of the CdTe NCs (NC(IL-130)) prepared in EMIDCA was significantly higher than that of the nanocrystals prepared in water (NC(w)) at 100 °C (86% vs. 35%). Moreover, the emission wavelength and particle size of NC(IL-130) were smaller than NC(w) (450 nm vs. 540 nm and 4.0 nm vs. 5.2 nm, respectively). The activation of NC(IL-130) was successful due to the coordinated action of two ligands, EMIDCA and TGA, in the primary steps of the NC formation pathway. An increase or decrease in the synthesis temperature, to 160 °C or 100 °C, respectively, was detrimental to the luminescence quality. However, the quenching effect of Hg²⁺ on the fluorescence signals of the NC(IL-130) was distinctively unique, whereas certain interfering ions, such as Pb²⁺, Fe³⁺, Co²⁺, Ni²⁺, Ag⁺, and Cu²⁺, could also quench the emission of the NC(w). Based on the Perrin model, the quenching signals of NC(w) and NC(IL-130) were well correlated with the Hg²⁺ concentrations in the phosphate buffer (pH 7.5, 50 mM). In comparison with the NC(w), the NC(IL-130) had a high tolerance of the interfering ions coexisting with the Hg²⁺ analyte, high recovery of Hg²⁺ spiked in the BSA- or FBS-containing medium, and high stability of fluorescence quenching signals between trials and days. The NC(IL-130) nanocrystals can potentially be used to develop a probe system for the determination of Hg²⁺ in physiological samples. Copyright © 2012 Elsevier B.V. All rights reserved.

Design, synthesis, and activity of nanocellulosic protease sensors

USDA-ARS?s Scientific Manuscript database

Here we contrast the molecular assembly, and biochemical utility of nanocellulosic materials prepared from cotton and wood as protease sensors. The cotton-based nanocellulosic substrates were prepared in a variety of ways to produce nanocrystals, films and aerogels, which were derivatized with eithe...

Mechanical and thermal properties of waterborne epoxy composites containing cellulose nanocrystals

Treesearch

Shanhong Xu; Natalie Girouard; Gregory Schueneman; Meisha L. Shofner; J. Carson Meredith

2013-01-01

Cellulose nanocrystals (CNCs) are reinforcing fillers of emerging interest for polymers due to their high modulus and potential for sustainable production. In this study, CNC-based composites with a waterborne epoxy resin matrix were prepared and characterized to determine morphology, water content, and thermal and mechanical properties. While some CNC aggregation was...

Effect of particle Alignment on mechanical properties of neat cellulose nanocrystal films

Treesearch

Alexander B. Reising; Robert J. Moon; Jeffrey P. Youngblood

2012-01-01

Shear-based film casting methods were used to cast neat films from wood-based cellulose nanocrystal (CNC) suspensions. The degree of CNC alignment in dried films was characterized using the Hermans order parameter (S), and the film elastic modulus (E), ultimate tensile strength (σf ), elongation at failure (εf...

Thermal Expansion of Self-Organized and Shear-Oriented Cellulose Nanocrystal Films

Treesearch

Jairo A. Diaz; Xiawa Wu; Ashlie Martini; Jeffrey P. Youngblood; Robert J. Moon

2013-01-01

The coefficient of thermal expansion (CTE) of cellulose nanocrystal (CNC) films was characterized using novel experimental techniques complemented by molecular simulations. The characteristic birefringence exhibited by CNC films was utilized to calculate the in-plane CTE of selforganized and shear-oriented self-standing CNC films from room temperature to 100 °...

Processing and Characterization of Cellulose Nanocrystals/Polylactic Acid Nanocomposite Films

Treesearch

Erin Sullivan; Robert Moon; Kyriaki Kalaitzidou

2015-01-01

The focus of this study is to examine the effect of cellulose nanocrystals (CNC) on the properties of polylactic acid (PLA) films. The films are fabricated via melt compounding and melt fiber spinning followed by compression molding. Film fracture morphology, thermal properties, crystallization behavior, thermo-mechanical behavior, and mechanical behavior were...

Design and characterization of cellulose nanocrystal-enhanced epoxy hardeners

Treesearch

Shane X. Peng; Robert J. Moon; Jeffrey P. Youngblood

2014-01-01

Cellulose nanocrystals (CNCs) are renewable, sustainable, and abundant nanomaterial widely used as reinforcing fillers in the field of polymer nanocomposites. In this study, two-part epoxy systems with CNC-enhanced hardeners were fabricated. Three types of hardeners, Jeffamine D400 (JD400), diethylenetriamine (DETA), and (±)-trans-1,2- diaminocyclohexane (DACH), were...

Single step synthesis of high-purity CoO nanocrystals.

PubMed

Yang, Huaming; Ouyang, Jing; Tang, Aidong

2007-07-19

Both octahedral and slice-shaped cubic cobalt monoxide (CoO) nanocrystals with narrow size distributions have been successfully synthesized by a simple solvothermal route. It was found that conditions of the solvothermal treatment showed obvious effects on the formation and purity of the as-synthesized CoO nanocrystals, only when cobalt acetate was used as the cobalt source and when temperature reached 190 degrees C could CoO be produced; also, freeze-drying was necessary for obtaining pure CoO. Size of the CoO nanocrystals varied from 30 to 130 nm. Morphology of the products could be controlled by simply changing the type of surfactant in solvent, and the octahedral CoO nanocrystals showed rounded turns. Purity of the products was detected by intensive X-ray photoelectron spectroscopy (XPS) investigation and Fourier transform infrared spectroscopy (FTIR) combined with differential scanning calorimetry/thermal gravity (DSC/TG). The results indicated an absence of unexpected trivalence cobalt series on surface of the samples, thanks to the protection of the surface by trace amount of carbonate ions, adsorbed hydroxylation, and surfactant with a maximum thickness of 2 nm, which were proved by high-resolution transmission electron microscopy (HRTEM). The as-synthesized CoO nanoparticles were added into positive electrode of Ni/MH batteries, and discharge/charge cycling tests were performed under different rates from 0.1C to 5.0C. The results indicated that the specific capacities of batteries with addition of 5% octahedral or slice CoO nanocrystals at 0.1C were 393.3 and 318.1 mAh/g, respectively, which were higher than that without CoO (269.2mAh/g). Specific capacity of battery with addition of 5% octahedral CoO nanocrystals was 40% higher than that without CoO at 5.0C. Octahedral CoO nanocrystals show better electrochemical activity than slice CoO and indicate interesting potential in the field of electrochemical application.

Non-injection synthesis of monodisperse Cu-Fe-S nanocrystals and their size dependent properties.

PubMed

Gabka, Grzegorz; Bujak, Piotr; Żukrowski, Jan; Zabost, Damian; Kotwica, Kamil; Malinowska, Karolina; Ostrowski, Andrzej; Wielgus, Ireneusz; Lisowski, Wojciech; Sobczak, Janusz W; Przybylski, Marek; Pron, Adam

2016-06-01

It is demonstrated that ternary Cu-Fe-S nanocrystals differing in composition (from Cu-rich to Fe-rich), structure (chalcopyrite or high bornite) and size can be obtained from a mixture of CuCl, FeCl3, thiourea and oleic acid (OA) in oleylamine (OLA) using the heating up procedure. This new preparation method yields the smallest Cu-Fe-S nanocrystals ever reported to date (1.5 nm for the high bornite structure and 2.7 nm for the chalcopyrite structure). A comparative study of nanocrystals of the same composition (Cu1.6Fe1.0S2.0) but different in size (2.7 nm and 9.3 nm) revealed a pronounced quantum confinement effect, confirmed by three different techniques: UV-vis spectroscopy, cyclic voltammetry and Mössbauer spectroscopy. The optical band gap increased from 0.60 eV in the bulk material to 0.69 eV in the nanocrystals of 9.3 nm size and to 1.39 eV in nanocrystals of 2.7 nm size. The same trend was observed in the electrochemical band gaps, derived from cyclic voltammetry studies (band gaps of 0.74 eV and 1.54 eV). The quantum effect was also manifested in Mössbauer spectroscopy by an abrupt change in the spectrum from a quadrupole doublet to a Zeeman sextet below 10 K, which could be interpreted in terms of the well defined energy states in these nanoparticles, resulting from quantum confinement. The Mössbauer spectroscopic data confirmed, in addition to the results of XPS spectroscopy, the co-existence of Fe(iii) and Fe(ii) in the synthesized nanocrystals. The organic shell composition was investigated by NMR (after dissolution of the inorganic core) and IR spectroscopy. Both methods identified oleylamine (OLA) and 1-octadecene (ODE) as surfacial ligands, the latter being formed in situ via an elimination-hydrogenation reaction occurring between OLA and the nanocrystal surface.

Synthesis and Characterizations of Novel Ca-Mg-Ti-Fe-Oxides Based Ceramic Nanocrystals and Flexible Film of Polydimethylsiloxane Composite with Improved Mechanical and Dielectric Properties for Sensors

PubMed Central

Tripathy, Ashis; Pramanik, Sumit; Manna, Ayan; Azrin Shah, Nabila Farhana; Shasmin, Hanie Nadia; Radzi, Zamri; Abu Osman, Noor Azuan

2016-01-01

Armalcolite, a rare ceramic mineral and normally found in the lunar earth, was synthesized by solid-state step-sintering. The in situ phase-changed novel ceramic nanocrystals of Ca-Mg-Ti-Fe based oxide (CMTFOx), their chemical reactions and bonding with polydimethylsiloxane (PDMS) were determined by X-ray diffraction, infrared spectroscopy, and microscopy. Water absorption of all the CMTFOx was high. The lower dielectric loss tangent value (0.155 at 1 MHz) was obtained for the ceramic sintered at 1050 °C (S1050) and it became lowest for the S1050/PDMS nanocomposite (0.002 at 1 MHz) film, which was made by spin coating at 3000 rpm. The excellent flexibility (static modulus ≈ 0.27 MPa and elongation > 90%), viscoelastic property (tanδ = E″/E′: 0.225) and glass transition temperature (Tg: −58.5 °C) were obtained for S1050/PDMS film. Parallel-plate capacitive and flexible resistive humidity sensors have been developed successfully. The best sensing performance of the present S1050 (3000%) and its flexible S1050/PDMS composite film (306%) based humidity sensors was found to be at 100 Hz, better than conventional materials. PMID:26927116

Synthesis of Water Dispersible Fluorescent Carbon Nanocrystals from Syzygium cumini Fruits for the Detection of Fe3+ Ion in Water and Biological Samples and Imaging of Fusarium avenaceum Cells.

PubMed

Bhamore, Jigna R; Jha, Sanjay; Singhal, Rakesh Kumar; Kailasa, Suresh Kumar

2017-01-01

In this work, water dispersible fluorescent carbon nanocrystals (NCs) were synthesized by a simple, green and low cost hydrothermal method using Syzygium cumini (jamun) as a carbon source at 180 °C for 6 h. The average size of carbon NCs was found to be 2.1 ± 0.5 nm and shown bright blue fluorescence when excited at 365 nm under UV lamp. The carbon NCs were characterized by spectroscopic (UV-visible and fluorescence, Fourier transform infrared and dynamic light scattering) and high resolution transmission electron microscopic techniques. The quantum yield of carbon NCs was found to be ~5.9 % at 438 nm emission wavelength when excited at 360 nm. It was noticed that none of the metal ions quenched the fluorescence intensity of carbon NCs at 438 nm except for Fe 3+ , indicating the formation of Fe 3+ ion-carbon NCs complexes. The linear range was observed in the concentration range of 0.01-100 μM with the corresponding detection limits of 0.001 μM, respectively. Furthermore, the carbon NCs were used as probes for imaging of fungal (Fusarium avenaceum) cells.

Atomic Layer Deposition of Titanium Oxide on Single-Layer Graphene: An Atomic-Scale Study toward Understanding Nucleation and Growth

PubMed Central

2017-01-01

Controlled synthesis of a hybrid nanomaterial based on titanium oxide and single-layer graphene (SLG) using atomic layer deposition (ALD) is reported here. The morphology and crystallinity of the oxide layer on SLG can be tuned mainly with the deposition temperature, achieving either a uniform amorphous layer at 60 °C or ∼2 nm individual nanocrystals on the SLG at 200 °C after only 20 ALD cycles. A continuous and uniform amorphous layer formed on the SLG after 180 cycles at 60 °C can be converted to a polycrystalline layer containing domains of anatase TiO2 after a postdeposition annealing at 400 °C under vacuum. Using aberration-corrected transmission electron microscopy (AC-TEM), characterization of the structure and chemistry was performed on an atomic scale and provided insight into understanding the nucleation and growth. AC-TEM imaging and electron energy loss spectroscopy revealed that rocksalt TiO nanocrystals were occasionally formed at the early stage of nucleation after only 20 ALD cycles. Understanding and controlling nucleation and growth of the hybrid nanomaterial are crucial to achieving novel properties and enhanced performance for a wide range of applications that exploit the synergetic functionalities of the ensemble. PMID:28356613

Unveiling the Shape Evolution and Halide-Ion-Segregation in Blue-Emitting Formamidinium Lead Halide Perovskite Nanocrystals Using an Automated Microfluidic Platform.

PubMed

Lignos, Ioannis; Protesescu, Loredana; Emiroglu, Dilara Börte; Maceiczyk, Richard; Schneider, Simon; Kovalenko, Maksym V; deMello, Andrew J

2018-02-14

Hybrid organic-inorganic perovskites and in particular formamidinium lead halide (FAPbX 3 , X = Cl, Br, I) perovskite nanocrystals (NCs) have shown great promise for their implementation in optoelectronic devices. Specifically, the Br and I counterparts have shown unprecedented photoluminescence properties, including precise wavelength tuning (530-790 nm), narrow emission linewidths (<100 meV) and high photoluminescence quantum yields (70-90%). However, the controlled formation of blue emitting FAPb(Cl 1-x Br x ) 3 NCs lags behind their green and red counterparts and the mechanism of their formation remains unclear. Herein, we report the formation of FAPb(Cl 1-x Br x ) 3 NCs with stable emission between 440 and 520 nm in a fully automated droplet-based microfluidic reactor and subsequent reaction upscaling in conventional laboratory glassware. The thorough parametric screening allows for the elucidation of parametric zones (FA-to-Pb and Br-to-Cl molar ratios, temperature, and excess oleic acid) for the formation of nanoplatelets and/or NCs. In contrast to CsPb(Cl 1-x Br x ) 3 NCs, based on online parametric screening and offline structural characterization, we demonstrate that the controlled synthesis of Cl-rich perovskites (above 60 at% Cl) with stable emission remains a challenge due to fast segregation of halide ions.

Synthesis and Characterizations of Novel Ca-Mg-Ti-Fe-Oxides Based Ceramic Nanocrystals and Flexible Film of Polydimethylsiloxane Composite with Improved Mechanical and Dielectric Properties for Sensors.

PubMed

Tripathy, Ashis; Pramanik, Sumit; Manna, Ayan; Shah, Nabila Farhana Azrin; Shasmin, Hanie Nadia; Radzi, Zamri; Abu Osman, Noor Azuan

2016-02-27

Armalcolite, a rare ceramic mineral and normally found in the lunar earth, was synthesized by solid-state step-sintering. The in situ phase-changed novel ceramic nanocrystals of Ca-Mg-Ti-Fe based oxide (CMTFOx), their chemical reactions and bonding with polydimethylsiloxane (PDMS) were determined by X-ray diffraction, infrared spectroscopy, and microscopy. Water absorption of all the CMTFOx was high. The lower dielectric loss tangent value (0.155 at 1 MHz) was obtained for the ceramic sintered at 1050 °C (S1050) and it became lowest for the S1050/PDMS nanocomposite (0.002 at 1 MHz) film, which was made by spin coating at 3000 rpm. The excellent flexibility (static modulus ≈ 0.27 MPa and elongation > 90%), viscoelastic property (tanδ = E″/E': 0.225) and glass transition temperature (Tg: -58.5 °C) were obtained for S1050/PDMS film. Parallel-plate capacitive and flexible resistive humidity sensors have been developed successfully. The best sensing performance of the present S1050 (3000%) and its flexible S1050/PDMS composite film (306%) based humidity sensors was found to be at 100 Hz, better than conventional materials.

Synthesis of CuInSe2 nanocrystals using a continuous hot-injection microreactor

NASA Astrophysics Data System (ADS)

Jin, Hyung Dae; Chang, Chih-Hung

2012-10-01

A very rapid and simple synthesis of CuInSe2 nanocrystals (NCs) was successfully performed using a continuous hot-injection microreactor with a high throughput per reactor volume. It was found that copper-rich CuInSe2 with a sphalerite structure was formed initially followed by the formation of more ordered CuInSe2 at longer reaction times along with the formation of Cu2Se and In2Se3. Binary syntheses were performed and the results show a much faster formation rate of Cu2Se than In2Se3. The rate limiting step in the formation of CuInSe2 is forming the In2Se3 intermediate. Rapid synthesis of stoichiometric CuInSe2 NCs using a continuous-flow microreactor was accomplished by properly adjusting the Cu/In precursor ratio. Tuning the ratio of coordinating solvents can cause size differences from 2.6 to 4.1 nm, bandgaps from 1.1 to 1.3 eV, and different production yields of NCs. The highest production yield as determined by weight was achieved up to 660 mg/h using a microreactor with a small volume of 3.2 cm3.

Nonequilibrium-Plasma-Synthesized ZnO Nanocrystals with Plasmon Resonance Tunable via Al Doping and Quantum Confinement.

PubMed

Greenberg, Benjamin L; Ganguly, Shreyashi; Held, Jacob T; Kramer, Nicolaas J; Mkhoyan, K Andre; Aydil, Eray S; Kortshagen, Uwe R

2015-12-09

Metal oxide semiconductor nanocrystals (NCs) exhibit localized surface plasmon resonances (LSPRs) tunable within the infrared (IR) region of the electromagnetic spectrum by vacancy or impurity doping. Although a variety of these NCs have been produced using colloidal synthesis methods, incorporation and activation of dopants in the liquid phase has often been challenging. Herein, using Al-doped ZnO (AZO) NCs as an example, we demonstrate the potential of nonthermal plasma synthesis as an alternative strategy for the production of doped metal oxide NCs. Exploiting unique, thoroughly nonequilibrium synthesis conditions, we obtain NCs in which dopants are not segregated to the NC surfaces and local doping levels are high near the NC centers. Thus, we achieve overall doping levels as high as 2 × 10(20) cm(-3) in NCs with diameters ranging from 12.6 to 3.6 nm, and for the first time experimentally demonstrate a clear quantum confinement blue shift of the LSPR energy in vacancy- and impurity-doped semiconductor NCs. We propose that doping of central cores and heavy doping of small NCs are achievable via nonthermal plasma synthesis, because chemical potential differences between dopant and host atoms-which hinder dopant incorporation in colloidal synthesis-are irrelevant when NC nucleation and growth proceed via irreversible interactions among highly reactive gas-phase ions and radicals and ligand-free NC surfaces. We explore how the distinctive nucleation and growth kinetics occurring in the plasma influences dopant distribution and activation, defect structure, and impurity phase formation.

Magnetoelectricity in CoFe2O4 nanocrystal-P(VDF-HFP) thin films

PubMed Central

2013-01-01

Transition metal ferrites such as CoFe2O4, possessing a large magnetostriction coefficient and high Curie temperature (Tc > 600 K), are excellent candidates for creating magnetic order at the nanoscale and provide a pathway to the fabrication of uniform particle-matrix films with optimized potential for magnetoelectric coupling. Here, a series of 0–3 type nanocomposite thin films composed of ferrimagnetic cobalt ferrite nanocrystals (8 to 18 nm) and a ferroelectric/piezoelectric polymer poly(vinylidene fluoride-co-hexafluoropropene), P(VDF-HFP), were prepared by multiple spin coating and cast coating over a thickness range of 200 nm to 1.6 μm. We describe the synthesis and structural characterization of the nanocrystals and composite films by XRD, TEM, HRTEM, STEM, and SEM, as well as dielectric and magnetic properties, in order to identify evidence of cooperative interactions between the two phases. The CoFe2O4 polymer nanocomposite thin films exhibit composition-dependent effective permittivity, loss tangent, and specific saturation magnetization (Ms). An enhancement of the effective permittivity and saturation magnetization of the CoFe2O4-P(VDF-HFP) films was observed and directly compared with CoFe2O4-polyvinylpyrrolidone, a non-ferroelectric polymer-based nanocomposite prepared by the same method. The comparison provided evidence for the observation of a magnetoelectric effect in the case of CoFe2O4-P(VDF-HFP), attributed to a magnetostrictive/piezoelectric interaction. An enhancement of Ms up to +20.7% was observed at room temperature in the case of the 10 wt.% CoFe2O4-P(VDF-HFP) sample. PMID:24004499

Filling of single-walled carbon nanotubes by CuI nanocrystals via capillary technique

NASA Astrophysics Data System (ADS)

Chernysheva, M. V.; Eliseev, A. A.; Lukashin, A. V.; Tretyakov, Yu. D.; Savilov, S. V.; Kiselev, N. A.; Zhigalina, O. M.; Kumskov, A. S.; Krestinin, A. V.; Hutchison, J. L.

2007-03-01

The present study is focused on the synthesis and investigation of the nanocomposite CuI@SWNT obtained by the filling of metallic single-walled carbon nanotubes (SWNTs) (inner diameter 1-1.4 nm) by wide-gap semiconducting CuI nanocrystals using so-called capillary technique. The method is based on the impregnation of pre-opened SWNTs by molten CuI in vacuum with subsequent slow cooling to room temperature. SWNTs and CuI@SWNT nanocomposites were studied by nitrogen capillary adsorption method, EDX microanalysis, HRTEM microscopy and Raman spectroscopy. The changing of electronic properties of CuI@SWNT as compare to row nanotubes was observed.

Development of low-cost technology for the next generation of high efficiency solar cells composed of earth abundant elements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Agrawal, Rakesh

2014-09-28

The development of renewable, affordable, and environmentally conscious means of generating energy on a global scale represents a grand challenge of our time. Due to the “permanence” of radiation from the sun, solar energy promises to remain a viable and sustainable power source far into the future. Established single-junction photovoltaic technologies achieve high power conversion efficiencies (pce) near 20% but require complicated manufacturing processes that prohibit the marriage of large-scale throughput (e.g. on the GW scale), profitability, and quality control. Our approach to this problem begins with the synthesis of nanocrystals of semiconductor materials comprising earth abundant elements and characterizedmore » by material and optoelectronic properties ideal for photovoltaic applications, namely Cu2ZnSn(S,Se)4 (CZTSSe). Once synthesized, such nanocrystals are formulated into an ink, coated onto substrates, and processed into completed solar cells in such a way that enables scale-up to high throughput, roll-to-roll manufacturing processes. This project aimed to address the major limitation to CZTSSe solar cell pce’s – the low open-circuit voltage (Voc) reported throughout literature for devices comprised of this material. Throughout the project significant advancements have been made in fundamental understanding of the CZTSSe material and device limitations associated with this material system. Additionally, notable improvements have been made to our nanocrystal based processing technique to alleviate performance limitations due to the identified device limitations. Notably, (1) significant improvements have been made in reducing intra- and inter-nanoparticle heterogeneity, (2) improvements in device performance have been realized with novel cation substitution in Ge-alloyed CZTGeSSe absorbers, (3) systematic analysis of absorber sintering has been conducted to optimize the selenization process for large grain CZTSSe absorbers, (4) novel electrical characterization analysis techniques have been developed to identify significant limitations to traditional electrical characterization of CZTSSe devices, and (5) the developed electrical analysis techniques have been used to identify the role that band gap and electrostatic potential fluctuations have in limiting device performance for this material system. The device modeling and characterization of CZTSSe undertaken with this project have significant implications for the CZTSSe research community, as the identified limitations due to potential fluctuations are expected to be a performance limitation to high-efficiency CZTSSe devices fabricated from all current processing techniques. Additionally, improvements realized through enhanced absorber processing conditions to minimize nanoparticle and large-grain absorber heterogeneity are suggested to be beneficial processing improvements which should be applied to CZTSSe devices fabricated from all processing techniques. Ultimately, our research has indicated that improved performance for CZTSSe will be achieved through novel absorber processing which minimizes defect formation, elemental losses, secondary phase formation, and compositional uniformity in CZTSSe absorbers; we believe this novel absorber processing can be achieved through nanocrystal based processing of CZTSSe which is an active area of research at the conclusion of this award. While significant fundamental understanding of CZTSSe and the performance limitations associated with this material system, as well as notable improvements in the processing of nanocrystal based CZTSSe absorbers, have been achieved under this project, the limitation of two years of research funding towards our goals prevents further significant advancements directly identified through pce. improvements relative to those reported herein. As the characterization and modeling subtask of this project has been the main driving force for understanding device limitations, the conclusions of this analysis have just recently been applied to the processing of nanocrystal based CZTSSe absorbers -- with notable success. We expect the notable fundamental understanding of device limitations and absorber sintering achieved under this project will lead to significant improvements in device performance for CZTSSe devices in the near future for devices fabricated from a variety of processing techniques« less

Synthesis and morphology of Ba1-xRE2x/3Nb2O6 nanocrystals with tungsten bronze structure in RE2O3-BaO-Nb2O5-B2O3 glasses (RE: Sm, Eu, Gd, Dy, Er)

NASA Astrophysics Data System (ADS)

Ida, H.; Shinozaki, K.; Honma, T.; Oh-ishi, K.; Komatsu, T.

2012-12-01

Ba1-xRE2x/3Nb2O6 nanocrystals with a tetragonal tungsten bronze (TTB) structure are synthesized using a conventional glass crystallization technique in 2.3RE2O3-27.4BaO-34.3Nb2O5-36B2O3 (mol%) (RE=Sm, Eu, Gd, Dy, and Er) glasses. One sharp crystallization peak is observed at ∼670 °C in both powdered and bulk glasses, and the formation of Ba1-xRE2x/3Nb2O6 nanocrystals with unit cell parameters of a∼1.24 nm and c∼0.39 nm was confirmed. It is found from high resolution transmission electron microscope observations that the morphology of Ba1-xRE2x/3Nb2O6 nanocrystals is ellipsoidal. Their average particle size is in the range of 15-60 nm and decreases with decreasing ionic radius of RE3+ being present in the precursor glasses. The optical transparent crystallized glass (bulk) shows the total photoluminescence (PL) quantum yield of 53% in the visible region of Eu3+ ions, suggesting a high potential of Ba1-xRE2x/3Nb2O6 nanocrystals as PL materials.

Low-temperature processed Ga-doped ZnO coatings from colloidal inks.

PubMed

Della Gaspera, Enrico; Bersani, Marco; Cittadini, Michela; Guglielmi, Massimo; Pagani, Diego; Noriega, Rodrigo; Mehra, Saahil; Salleo, Alberto; Martucci, Alessandro

2013-03-06

We present a new colloidal synthesis of gallium-doped zinc oxide nanocrystals that are transparent in the visible and absorb in the near-infrared. Thermal decomposition of zinc stearate and gallium nitrate after hot injection of the precursors in a mixture of organic amines leads to nanocrystals with tunable properties according to gallium amount. Substitutional Ga(3+) ions trigger a plasmonic resonance in the infrared region resulting from an increase in the free electrons concentration. These nanocrystals can be deposited by spin coating, drop casting, and spray coating resulting in homogeneous and high-quality thin films. The optical transmission of the Ga-ZnO nanoparticle assemblies in the visible is greater than 90%, and at the same time, the near-infrared absorption of the nanocrystals is maintained in the films as well. Several strategies to improve the films electrical and optical properties have been presented, such as UV treatments to remove the organic compounds responsible for the observed interparticle resistance and reducing atmosphere treatments on both colloidal solutions and thin films to increase the free carriers concentration, enhancing electrical conductivity and infrared absorption. The electrical resistance of the nanoparticle assemblies is about 30 kΩ/sq for the as-deposited, UV-exposed films, and it drops down to 300 Ω/sq after annealing in forming gas at 450 °C, comparable with state of the art tin-doped indium oxide coatings deposited from nanocrystal inks.

Processing-Structure-Property Relationships in Laser-Annealed PbSe Nanocrystal Thin Films.

PubMed

Treml, Benjamin E; Robbins, Andrew B; Whitham, Kevin; Smilgies, Detlef-M; Thompson, Michael O; Hanrath, Tobias

2015-01-01

As nanocrystal (NC) synthesis techniques and device architectures advance, it becomes increasingly apparent that new ways of connecting NCs with each other and their external environment are required to realize their considerable potential. Enhancing inter-NC coupling by thermal annealing has been a long-standing challenge. Conventional thermal annealing approaches are limited by the challenge of annealing the NC at sufficiently high temperatures to remove surface-bound ligands while at the same time limiting the thermal budget to prevent large-scale aggregation. Here we investigate nonequilibrium laser annealing of NC thin films that enables separation of the kinetic and thermodynamic aspects of nanocrystal fusion. We show that laser annealing of NC assemblies on nano- to microsecond time scales can transform initially isolated NCs in a thin film into an interconnected structure in which proximate dots "just touch". We investigate both pulsed laser annealing and laser spike annealing and show that both annealing methods can produce "confined-but-connected" nanocrystal films. We develop a thermal transport model to rationalize the differences in resulting film morphologies. Finally we show that the insights gained from study of nanocrystal mono- and bilayers can be extended to three-dimensional NC films. The basic processing-structure-property relationships established in this work provide guidance to future advances in creating functional thin films in which constituent NCs can purposefully interact.

The upconversion luminescence and magnetism in Yb3+/Ho3+ co-doped LaF3 nanocrystals for potential bimodal imaging

NASA Astrophysics Data System (ADS)

Syamchand, Sasidharanpillai S.; George, Sony

2016-12-01

Biocompatible upconversion nanoparticles with multifunctional properties can serve as potential nanoprobes for multimodal imaging. Herein, we report an upconversion nanocrystal based on lanthanum fluoride which is developed to address the imaging modalities, upconversion luminescence imaging and magnetic resonance imaging (MRI). Lanthanide ions (Yb3+ and Ho3+) doped LaF3 nanocrystals (LaF3 Yb3+/Ho3+) are fabricated through a rapid microwave-assisted synthesis. The hexagonal phase LaF3 nanocrystals exhibit nearly spherical morphology with average diameter of 9.8 nm. The inductively coupled plasma mass spectrometry (ICP-MS) analysis estimated the doping concentration of Yb3+ and Ho3+ as 3.99 and 0.41%, respectively. The nanocrystals show upconversion luminescence when irradiated with near-infrared (NIR) photons of wavelength 980 nm. The emission spectrum consists of bands centred at 542, 645 and 658 nm. The stronger green emission at 542 nm and the weak red emissions at 645 and 658 nm are assigned to 5S2 → 5I8 and 5F5 → 5I8 transitions of Ho3+, respectively. The pump power dependence of luminescence intensity confirmed the two-photon upconversion process. The nanocrystals exhibit paramagnetism due to the presence of lanthanide ion dopant Ho3+ and the magnetization is 19.81 emu/g at room temperature. The nanocrystals exhibit a longitudinal relaxivity ( r 1) of 0.12 s-1 mM-1 and transverse relaxivity ( r 2) of 28.18 s-1 mM-1, which makes the system suitable for developing T2 MRI contrast agents based on holmium. The LaF3 Yb3+/Ho3+ nanocrystals are surface modified by PEGylation to improve biocompatibility and enhance further functionalisation. The PEGylated nanocrystals are found to be non-toxic up to 50 μg/mL for 48 h of incubation, which is confirmed by the MTT assay as well as morphological studies in HeLa cells. The upconversion luminescence and magnetism together with biocompatibility enables the adaptability of the present system as a nanoprobe for potential bimodal imaging.

Role of the nanocrystallinity on the chemical ordering of Co(x)Pt(100-x) nanocrystals synthesized by wet chemistry.

PubMed

Kameche, Farid; Ngo, Anh-Tu; Salzemann, Caroline; Cordeiro, Marco; Sutter, Eli; Petit, Christophe

2015-11-14

Co(x)Pt(100-x) nanoalloys have been synthesized by two different chemical processes either at high or at low temperature. Their physical properties and the order/disorder phase transition induced by annealing have been investigated depending on the route of synthesis. It is demonstrated that the chemical synthesis at high temperature allows stabilization of the fcc structure of the native nanoalloys while the soft chemical approach yields mainly poly or non crystalline structure. As a result the approach of the order/disorder phase transition is strongly modified as observed by high-resolution transmission electron microscopy (HR-TEM) studies performed during in situ annealing of the different nanoalloys. The control of the nanocrystallinity leads to significant decrease in the chemical ordering temperature as the ordered structure is observed at temperatures as low as 420 °C. This in turn preserves the individual nanocrystals and prevents their coalescence usually observed during the annealing necessary for the transition to an ordered phase.

A Mesopore-Dependent Catalytic Cracking of n-Hexane Over Mesoporous Nanostructured ZSM-5.

PubMed

Qamar, M; Ahmed, M I; Qamaruddin, M; Asif, M; Sanhoob, M; Muraza, O; Khan, M Y

2018-08-01

Herein, pore size, crystalinity, and Si/Al ratio of mesoporous ZSM-5 (MFI) nanocrystals was controlled by synthesis parameters, such as surfactant concentration ([3-(trimethoxysilyl)propyl] hexa-decyl dimethyl ammonium chloride), sodium hydroxide concentrations, synthesis temperature and time. The morphology, surface structure and composition of the MFI particles was systematically investigated. More notably, the mesopore-dependent catalytic activity of ZSM-5 was evaluated by studying the cracking of n-hexane. The findings suggest the porosity has pronounced impact on the catalytic activity, selectivity and stability of ZSM-5 nanocrystals. Critical surface attributes such as nature of acid sites (Brønsted and Lewis), concentration, and strength are obtained by the infrared study of adsorbed probe molecules (pyridine) and the temperature programmed desorption. In spite of being weaker in Si/Al ratio or acidic strength, mesoporous catalysts showed more stable and efficient cracking of n-hexane suggesting that acidity seems not the predominant factor operative in the activity, selectivity and stability.

Fabrication of Worm-Like Nanorods and Ultrafine Nanospheres of Silver Via Solid-State Photochemical Decomposition

PubMed Central

2009-01-01

Worm-like nanorods and nanospheres of silver have been synthesized by photochemical decomposition of silver oxalate in water by UV irradiation in the presence of CTAB and PVP, respectively. No external seeds have been employed for the synthesis of Ag nanorods. The synthesized Ag colloids have been characterized by UV-visible spectra, powder XRD, HRTEM, and selected area electron diffraction (SAED). Ag nanospheres of average size around 2 nm have been obtained in the presence of PVP. XRD and TEM analyses revealed that top and basal planes of nanorods are bound with {111} facets. Williamson–Hall plot has revealed the presence of defects in the Ag nanospheres and nanorods. Formation of defective Ag nanocrystals is attributed to the heating effect of UV-visible irradiation. PMID:20596513

Thermal Stability of Metal Nanocrystals: An Investigation of the Surface and Bulk Reconstructions of Pd Concave Icosahedra [On the Thermal Stability of Metal Nanocrystals: An Investigation of the Surface and Bulk Reconstructions of Pd Concave Icosahedra

DOE PAGES

Gilroy, Kyle D.; Elnabawy, Ahmed O.; Yang, Tung -Han; ...

2017-04-27

Despite the remarkable success in controlling the synthesis of metal nanocrystals, it still remains a grand challenge to stabilize and preserve the shapes or internal structures of metastable kinetic products. In this work, we address this issue by systematically investigating the surface and bulk reconstructions experienced by a Pd concave icosahedron when subjected to heating up to 600 °C in vacuum. We used in situ high-resolution transmission electron microscopy to identify the equilibration pathways of this far-from-equilibrium structure. We were able to capture key structural transformations occurring during the thermal annealing process, which were mechanistically rationalized by implementing self-consistent plane-wavemore » density functional theory (DFT) calculations. Specifically, the concave icosahedron was found to evolve into a regular icosahedron via surface reconstruction in the range of 200–400 °C, and then transform into a pseudospherical crystalline structure through bulk reconstruction when further heated to 600 °C. As a result, the mechanistic understanding may lead to the development of strategies for enhancing the thermal stability of metal nanocrystals.« less

Control over the branched structures of platinum nanocrystals for electrocatalytic applications.

PubMed

Ma, Liang; Wang, Chengming; Gong, Ming; Liao, Lingwen; Long, Ran; Wang, Jinguo; Wu, Di; Zhong, Wei; Kim, Moon J; Chen, Yanxia; Xie, Yi; Xiong, Yujie

2012-11-27

Structural control of branched nanocrystals allows tuning two parameters that are critical to their catalytic activity--the surface-to-volume ratio, and the number of atomic steps, ledges, and kinks on surface. In this work, we have developed a simple synthetic system that allows tailoring the numbers of branches in Pt nanocrystals by tuning the concentration of additional HCl. In the synthesis, HCl plays triple functions in tuning branched structures via oxidative etching: (i) the crystallinity of seeds and nanocrystals; (ii) the number of {111} or {100} faces provided for growth sites; (iii) the supply kinetics of freshly formed Pt atoms in solution. As a result, tunable Pt branched structures--tripods, tetrapods, hexapods, and octopods with identical chemical environment--can be rationally synthesized in a single system by simply altering the etching strength. The controllability in branched structures enables to reveal that their electrocatalytic performance can be optimized by constructing complex structures. Among various branched structures, Pt octopods exhibit particularly high activity in formic acid oxidation as compared with their counterparts and commercial Pt/C catalysts. It is anticipated that this work will open a door to design more complex nanostructures and to achieve specific functions for various applications.

Synthesis of three-dimensional reduced graphene oxide layer supported cobalt nanocrystals and their high catalytic activity in F-T CO2 hydrogenation.

PubMed

He, Fei; Niu, Na; Qu, Fengyu; Wei, Shuquan; Chen, Yujin; Gai, Shili; Gao, Peng; Wang, Yan; Yang, Piaoping

2013-09-21

The reduced graphene oxide (rGO) supported cobalt nanocrystals have been synthesized through an in situ crystal growth method using Co(acac)2 under solvothermal conditions by using DMF as the solvent. By carefully controlling the reaction temperature, the phase transition of the cobalt nanocrystals from the cubic phase to the hexagonal phase has been achieved. Moreover, the microscopic structure and morphology as well as the reduction process of the composite have been investigated in detail. It is found that oxygen-containing functional groups on the graphene oxide (GO) can greatly influence the formation process of the Co nanocrystals by binding the Co(2+) cations dissociated from the Co(acac)2 in the initial reaction solution at 220 °C, leading to the 3D reticular structure of the composite. Furthermore, this is the first attempt to use a Co/rGO composite as the catalyst in the F-T CO2 hydrogenation process. The catalysis testing results reveal that the as-synthesized 3D structured composite exhibits ideal catalytic activity and good stability, which may greatly extend the scope of applications for this kind of graphene-based metal hybrid material.

Gas-phase synthesis of semiconductor nanocrystals and its applications

NASA Astrophysics Data System (ADS)

Mandal, Rajib

Luminescent nanomaterials is a newly emerging field that provides challenges not only to fundamental research but also to innovative technology in several areas such as electronics, photonics, nanotechnology, display, lighting, biomedical engineering and environmental control. These nanomaterials come in various forms, shapes and comprises of semiconductors, metals, oxides, and inorganic and organic polymers. Most importantly, these luminescent nanomaterials can have different properties owing to their size as compared to their bulk counterparts. Here we describe the use of plasmas in synthesis, modification, and deposition of semiconductor nanomaterials for luminescence applications. Nanocrystalline silicon is widely known as an efficient and tunable optical emitter and is attracting great interest for applications in several areas. To date, however, luminescent silicon nanocrystals (NCs) have been used exclusively in traditional rigid devices. For the field to advance towards new and versatile applications for nanocrystal-based devices, there is a need to investigate whether these NCs can be used in flexible and stretchable devices. We show how the optical and structural/morphological properties of plasma-synthesized silicon nanocrystals (Si NCs) change when they are deposited on stretchable substrates made of polydimethylsiloxane (PDMS). Synthesis of these NCs was performed in a nonthermal, low-pressure gas phase plasma reactor. To our knowledge, this is the first demonstration of direct deposition of NCs onto stretchable substrates. Additionally, in order to prevent oxidation and enhance the luminescence properties, a silicon nitride shell was grown around Si NCs. We have demonstrated surface nitridation of Si NCs in a single step process using non?thermal plasma in several schemes including a novel dual-plasma synthesis/shell growth process. These coated NCs exhibit SiNx shells with composition depending on process parameters. While measurements including photoluminescence (PL), surface analysis, and defect identification indicate the shell is protective against oxidation compared to Si NCs without any shell growth. Gallium Nitride (GaN) is one of the most well-known semiconductor material and the industry standard for fabricating LEDs. The problem is that epitaxial growth of high-quality GaN requires costly substrates (e.g. sapphire), high temperatures, and long processing times. Synthesizing freestanding NCs of GaN, on the other hand, could enable these novel device morphologies, as the NCs could be incorporated into devices without the requirements imposed by epitaxial GaN growth. Synthesis of GaN NCs was performed using a fully gas-phase process. Different sizes of crystalline GaN nanoparticles were produced indicating versatility of this gas-phase process. Elemental analysis using X-ray photoelectron spectroscopy (XPS) indicated a possible nitrogen deficiency in the NCs; addition of secondary plasma for surface treatment indicates improving stoichiometric ratio and points towards a unique method for creating high-quality GaN NCs with ultimate alloying and doping for full-spectrum luminescence.

Spatially Resolved Characterization of Cellulose Nanocrystal-Polypropylene Composite by Confocal Raman Microscopy

Treesearch

Umesh P. Agarwal; Ronald Sabo; Richard S. Reiner; Craig M. Clemons; Alan W. Rudie

2012-01-01

Raman spectroscopy was used to analyze cellulose nanocrystal (CNC)–polypropylene (PP) composites and to investigate the spatial distribution of CNCs in extruded composite filaments. Three composites were made from two forms of nanocellulose (CNCs from wood pulp and the nanoscale fraction of microcrystalline cellulose) and two of the three composites investigated used...

Cellulose nanocrystals as a reinforcing material for electrospun poly(methyl methacrylate) fibers: formation, properties and nanomechanical characterization

Treesearch

Hong Dong; Kenneth E. Strawhecker; James A. Snyder; Joshua A. Orlicki; Richard S. Reiner; Alan W. Rudie

2012-01-01

Uniform fibers composed of poly(methyl methacrylate) (PMMA) reinforced with progressively increasing contents of cellulose nanocrystals (CNCs), up to 41 wt% CNCs, have been successfully produced by electrospinning. The morphological, thermal and nanomechanical properties of the composite sub-micron fibers were investigated. The CNCs derived from wood pulp by sulfuric...

Structural Characterization of Bimetallic Nanocrystal Electrocatalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cullen, David A

2016-01-01

Late transition metal nanocrystals find applications in heterogeneous catalysis such as plasmon-enhanced catalysis and as electrode materials for fuel cells, a zero-emission and sustainable energy technology. Their commercial viability for automotive transportation has steadily increased in recent years, almost exclusively due to the discovery of more efficient bimetallic nanocatalysts for the oxygen reduction reaction (ORR) at the cathode. Despite improvements to catalyst design, achieving high activity while maintaining durability is essential to further enhance their performance for this and other important applications in catalysis. Electronic effects arising from the generation of metal-metal interfaces, from plasmonic metals, and from lattice distortions,more » can vastly improve sorption properties at catalytic surfaces, while increasing durability.[1] Multimetallic lattice-strained nanoparticles are thus an interesting opportunity for fundamental research.[2,3] A colloidal synthesis approach is demonstrated to produce AuPd alloy and Pd@Au core-shell nanoicosahedra as catalysts for electro-oxidations. The nanoparticles are characterized using aberration-corrected scanning transmission electron microscopy (ac-STEM) and large solid angle energy dispersive X-ray spectroscopy (EDS) on an FEI Talos 4-detector STEM/EDS system. Figure 1 shows bright-field (BF) and high-angle annular dark-field (HAADF) ac-STEM images of the alloy and core-shell nanoicosahedra together with EDS line-scans and elemental maps. These structures are unique in that the presence of twin boundaries, alloying, and core-shell morphology could create highly strained surfaces and interfaces. The shell thickness of the core-shell structures observed in HAADF-STEM images is tuned by adjusting the ratio between metal precursors (Figure 2a-f) to produce shells ranging from a few to several monolayers. Specific activity was measured in ethanol electro-oxidation to examine the effect of shell thickness on catalytic activity. A volcano relationship was observed for the core-shell nanoicosahedra having different Pd-shell thicknesses as Pd content is increased (Figure 2g). Durability tests are ongoing for the AuPd system; however, promising ORR materials and morphologies have also been synthesized for a more cost-effective Cu-based system of Cu-CuM (M = Pd, Rh, Pt) core-alloy-shell nanocrystals. The synthesis, characterization, and catalytic behavior of different high-index faceted morphologies of Cu-based materials towards ORR and methanol oxidation catalysis will be discussed, where we show how they exceed the performance of commercial Pd- and Pt- based catalysts. The development of new materials and their characterization is critical to understanding the effects of structure and composition on catalysis. Future efforts are directed at resolving these structures and more industrially relevant fuel cell catalysts in 3D through electron tomography.[4] References: [1] X. Huang, et al., Science 348 (2015) p. 1230. [2] P. Strasser, et al., Nat. Chem. 2 (2010) p. 454. [3] C. Chen, et al., Science 343 (2014) p. 1339. [4] Microscopy performed as part of a user project through ORNL s Center for Nanophase Materials Sciences, which is a U.S. DOE Office of Science User Facility, and instrumentation provided by the U.S. DOE Office of Nuclear Energy, Fuel Cycle R&D Program, and the Nuclear Science User Facilities.« less

Green synthesis of gold nanoparticles using Trigonella foenum-graecum and its size-dependent catalytic activity

NASA Astrophysics Data System (ADS)

Aswathy Aromal, S.; Philip, Daizy

2012-11-01

The development of new synthesis methods for monodispersed nanocrystals using cheap and nontoxic chemicals, environmentally benign solvents and renewable materials remains a challenge to the scientific community. Most of the current methods involve known protocols which may be potentially harmful to either environment or human health. Recent research has been focused on green synthesis methods to produce new nanomaterials, ecofriendly and safer with sustainable commercial viability. The present work reports the green synthesis of gold nanoparticles using the aqueous extract of fenugreek (Trigonella foenum-graecum) as reducing and protecting agent. The pathway is based on the reduction of AuCl4- by the extract of fenugreek. This method is simple, efficient, economic and nontoxic. Gold nanoparticles having different sizes in the range from 15 to 25 nm could be obtained by controlling the synthesis parameters. The nanoparticles have been characterized by UV-Visible spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) and FTIR analysis. The high crystallinity of nanoparticles is evident from clear lattice fringes in the HRTEM images, bright circular spots in the SAED pattern and peaks in the XRD pattern. FTIR spectrum indicates the presence of different functional groups present in the biomolecule capping the nanoparticles. The synthesized gold nanoparticles show good catalytic activity for the reduction of 4-nitrophenol to 4-aminophenol by excess NaBH4. The catalytic activity is found to be size-dependent, the smaller nanoparticles showing faster activity.

Green synthesis of silver nanoparticles by Bacillus methylotrophicus, and their antimicrobial activity.

PubMed

Wang, Chao; Kim, Yeon Ju; Singh, Priyanka; Mathiyalagan, Ramya; Jin, Yan; Yang, Deok Chun

2016-06-01

The synthesis of silver nanoparticles (AgNPs) by microorganisms is an area attracting growing interest in nanobiotechnology, due to the applications of these nanoparticles in various products including cosmetics and biosensors, and in the biomedical, clinical, and bioimaging fields as well. Various microorganisms have been found to be able to synthesize AgNPs when silver salts are supplied in the reaction system. The main objectives of this study were to evaluate the efficiency of synthesis of AgNPs by the strain Bacillus methylotrophicus DC3, isolated from the soil of Korean ginseng, a traditionally known oriental medicinal plant in Korea. The AgNPs showed maximum absorbance at 416 nm, when assayed by ultraviolet-visible spectroscopy (UV-vis). The field emission transmission electron micrograph (FE-TEM) results showed that the particles were spherical and 10-30 nm in size. In addition, the product was also characterized by energy dispersive X-ray spectroscopy (EDX), which displayed a 3 keV peak corresponding to the silver nanocrystal. Elemental mapping results also confirmed the presence of silver elements in the electron micrograph region. Furthermore, the AgNPs demonstrated antimicrobial activity against various pathogenic microorganisms such as Candida albicans, Salmonella enterica, Escherichia coli, and Vibrio parahaemolyticus, with enhanced antimicrobial activity being exhibited against C. albicans. Therefore, the current study describes the simple, efficient, and green method of synthesis of AgNPs by B. methylotrophicus DC3.

Revisiting 30 years of biofunctionalization and surface chemistry of inorganic nanoparticles for nanomedicine

PubMed Central

Conde, João; Dias, Jorge T.; Grazú, Valeria; Moros, Maria; Baptista, Pedro V.; de la Fuente, Jesus M.

2014-01-01

In the last 30 years we have assisted to a massive advance of nanomaterials in material science. Nanomaterials and structures, in addition to their small size, have properties that differ from those of larger bulk materials, making them ideal for a host of novel applications. The spread of nanotechnology in the last years has been due to the improvement of synthesis and characterization methods on the nanoscale, a field rich in new physical phenomena and synthetic opportunities. In fact, the development of functional nanoparticles has progressed exponentially over the past two decades. This work aims to extensively review 30 years of different strategies of surface modification and functionalization of noble metal (gold) nanoparticles, magnetic nanocrystals and semiconductor nanoparticles, such as quantum dots. The aim of this review is not only to provide in-depth insights into the different biofunctionalization and characterization methods, but also to give an overview of possibilities and limitations of the available nanoparticles. PMID:25077142

Hydrothermal synthesis and shape-reactivity correlation study of automotive three-way nanocatalysts.

DOT National Transportation Integrated Search

2014-02-01

In this project, we have shown that the hydrothermal method can be used to tune : the shape/size of CeO2 nanocrystals. CeO2 nanorods and nanocubes have been successfully : prepared at low and high hydrothermal reaction temperature, respectively. The ...

Fullerene-like colloidal nanocrystal of nickel hydroxychloride.

PubMed

Hu, Shi; Wang, Xun

2010-07-21

In this work, we successfully fabricated near-monodisperse colloids of a new type of inorganic fullerene-like structure (IF) of nickel hydroxychloride as the first example of the application of colloidal synthetic routes to the synthesis of IFs. The formation mechanism and interesting magnetic properties are briefly discussed.

High-surface-area mesoporous TiO2 microspheres via one-step nanoparticle self-assembly for enhanced lithium-ion storage

NASA Astrophysics Data System (ADS)

Wang, Hsin-Yi; Chen, Jiazang; Hy, Sunny; Yu, Linghui; Xu, Zhichuan; Liu, Bin

2014-11-01

Mesoporous TiO2 microspheres assembled from TiO2 nanoparticles with specific surface areas as high as 150 m2 g-1 were synthesized via a facile one-step solvothermal reaction of titanium isopropoxide and anhydrous acetone. Aldol condensation of acetone gradually releases structural H2O, which hydrolyzes and condenses titanium isopropoxide, forming TiO2 nanocrystals. Simultaneous growth and aggregation of TiO2 nanocrystals leads to the formation of high-surface-area TiO2 microspheres under solvothermal conditions. After a low-temperature post-synthesis calcination, carbonate could be incorporated into TiO2 as a dopant with the carbon source coming from the organic byproducts during the synthesis. Carbonate doping modifies the electronic structure of TiO2 (e.g., Fermi level, Ef), and thus influences its electrochemical properties. Solid electrolyte interface (SEI) formation, which is not common for titania, could be initiated in carbonate-doped TiO2 due to elevated Ef. After removing carbonate dopants by high-temperature calcination, the mesoporous TiO2 microspheres showed much improved performance in lithium insertion and stability at various current rates, attributed to a synergistic effect of high surface area, large pore size and good anatase crystallinity.Mesoporous TiO2 microspheres assembled from TiO2 nanoparticles with specific surface areas as high as 150 m2 g-1 were synthesized via a facile one-step solvothermal reaction of titanium isopropoxide and anhydrous acetone. Aldol condensation of acetone gradually releases structural H2O, which hydrolyzes and condenses titanium isopropoxide, forming TiO2 nanocrystals. Simultaneous growth and aggregation of TiO2 nanocrystals leads to the formation of high-surface-area TiO2 microspheres under solvothermal conditions. After a low-temperature post-synthesis calcination, carbonate could be incorporated into TiO2 as a dopant with the carbon source coming from the organic byproducts during the synthesis. Carbonate doping modifies the electronic structure of TiO2 (e.g., Fermi level, Ef), and thus influences its electrochemical properties. Solid electrolyte interface (SEI) formation, which is not common for titania, could be initiated in carbonate-doped TiO2 due to elevated Ef. After removing carbonate dopants by high-temperature calcination, the mesoporous TiO2 microspheres showed much improved performance in lithium insertion and stability at various current rates, attributed to a synergistic effect of high surface area, large pore size and good anatase crystallinity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr04729j

Preparation and characterization of potato starch nanocrystal reinforced natural rubber nanocomposites.

PubMed

Rajisha, K R; Maria, H J; Pothan, L A; Ahmad, Zakiah; Thomas, S

2014-06-01

Potato starch nanocrystals were found to serve as an effective reinforcing agent for natural rubber (NR). Starch nanocrystals were obtained by the sulfuric acid hydrolysis of potato starch granules. After mixing the latex and the starch nanocrystals, the resulting aqueous suspension was cast into film by solvent evaporation method. The composite samples were successfully prepared by varying filler loadings, using a colloidal suspension of starch nanocrystals and NR latex. The morphology of the nanocomposite prepared was analyzed by field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). FESEM analysis revealed the size and shape of the crystal and their homogeneous dispersion in the composites. The crystallinity of the nanocomposites was studied using XRD analysis which indicated an overall increase in crystallinity with filler content. The mechanical properties of the nanocomposites such as stress-strain behavior, tensile strength, tensile modulus and elongation at break were measured according to ASTM standards. The tensile strength and modulus of the composites were found to improve tremendously with increasing nanocrystal content. This dramatic increase observed can be attributed to the formation of starch nanocrystal network. This network immobilizes the polymer chains leading to an increase in the modulus and other mechanical properties. Copyright © 2014 Elsevier B.V. All rights reserved.

Bi-Functional Biobased Packing of the Cassava Starch, Glycerol, Licuri Nanocellulose and Red Propolis

PubMed Central

Costa, Samantha Serra; Druzian, Janice Izabel; Machado, Bruna Aparecida Souza; de Souza, Carolina Oliveira; Guimarães, Alaíse Gil

2014-01-01

The aim of this study was to characterize and determine the bi-functional efficacy of active packaging films produced with starch (4%) and glycerol (1.0%), reinforced with cellulose nanocrystals (0–1%) and activated with alcoholic extracts of red propolis (0.4 to 1.0%). The cellulose nanocrystals used in this study were extracted from licuri leaves. The films were characterized using moisture, water-activity analyses and water vapor-permeability tests and were tested regarding their total phenolic compounds and mechanical properties. The antimicrobial and antioxidant efficacy of the films were evaluated by monitoring the use of the active films for packaging cheese curds and butter, respectively. The cellulose nanocrystals increased the mechanical strength of the films and reduced the water permeability and water activity. The active film had an antimicrobial effect on coagulase-positive staphylococci in cheese curds and reduced the oxidation of butter during storage. PMID:25383783

Bi-functional biobased packing of the cassava starch, glycerol, licuri nanocellulose and red propolis.

PubMed

Costa, Samantha Serra; Druzian, Janice Izabel; Machado, Bruna Aparecida Souza; de Souza, Carolina Oliveira; Guimarães, Alaíse Gil

2014-01-01

The aim of this study was to characterize and determine the bi-functional efficacy of active packaging films produced with starch (4%) and glycerol (1.0%), reinforced with cellulose nanocrystals (0-1%) and activated with alcoholic extracts of red propolis (0.4 to 1.0%). The cellulose nanocrystals used in this study were extracted from licuri leaves. The films were characterized using moisture, water-activity analyses and water vapor-permeability tests and were tested regarding their total phenolic compounds and mechanical properties. The antimicrobial and antioxidant efficacy of the films were evaluated by monitoring the use of the active films for packaging cheese curds and butter, respectively. The cellulose nanocrystals increased the mechanical strength of the films and reduced the water permeability and water activity. The active film had an antimicrobial effect on coagulase-positive staphylococci in cheese curds and reduced the oxidation of butter during storage.

Exciton Energy Transfer from Halide Terminated Nanocrystals to Graphene in Solar Photovoltaics

NASA Astrophysics Data System (ADS)

Ajayi, Obafunso; Abramson, Justin; Anderson, Nicholas; Owen, Jonathan; Zhao, Yue; Kim, Phillip; Gesuele, Felice; Wong, Chee Wei

2011-03-01

Graphene, a zero-gap semiconductor, has been identified as an ideal electrode for nanocrystal solar cell photovoltaic applications due to its high carrier mobility. Further advances in efficient current extraction are required towards this end. We investigate the resonant energy transfer dynamics between photoexcited nanocrystals and graphene, where the energy transfer rate is characterized by the fluorescent quenching of the quantum dots in the presence of graphene. Energy transfer has been shown to have a d -4 dependence on the nanocrystal distance from the graphene surface, with a correction due to blinking statistics. We investigate this relationship with single and few layer graphene. We study halide-terminated CdSe quantum dots; where the absence of the insulating outershell improves the electronic coupling of the donor-acceptor system leads to improved electron transfer. We observe quenching of the halide terminated nanocrystals on graphene, with the quenching factor ρ defined as IQ /IG (the relative intensities on quartz and graphene).

Polymorph (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}RE{sub 3}F{sub 10}·xH{sub 2}O (RE = Ho-Lu, Y) and REF{sub 3} nanocrystals: Hydrothermal synthesis, characterization and luminescence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jia, Li-Ping; Zhang, Qiang; Yan, Bing, E-mail: byan@tongji.edu.cn

Graphical abstract: A hydrothermal system is developed to prepare one new polymorph of (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}RE{sub 3}F{sub 10}·xH{sub 2}O and known rare earth fluorides involving REF{sub 3} nanocrystals under mild condition. Highlights: ► A new polymorph of (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}RE{sub 3}F{sub 10}·xH{sub 2}O has been synthesized. ► The RE{sup 3+} radius decides the shape evolution and phase control for REF{sub 3} NCs. ► The RE{sup 3+} radius has influence on the microstructure and morphology of REF{sub 3} NCs. -- Abstract: In this paper, a solvents-thermal system is developed to prepare one new polymorph of (C{sub 2}N{submore » 2}H{sub 10}){sub 0.5}Ho{sub 3}F{sub 10}·xH{sub 2}O and rare earth fluorides REF{sub 3} nanocrystals under mild condition. It is found that the ionic radius of RE{sup 3+} is the key factor responsible for the shape evolution and phase control for rare earth fluorides nanocrystals at selected temperatures, which has an influence on the microstructure and morphology of the products to some extent. With the increase of the atomic number, the shape of fluoride changes from hexagonal REF{sub 3} phase (RE = La, Sm) to orthorhombic REF{sub 3} phase (RE = Eu-Dy), and finally to diamond structure (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}Ho{sub 3}F{sub 10}·xH{sub 2}O (RE = Ho, Er, Tm, Yb, Lu, Y). In addition, the characteristic energy level transition {sup 5}D{sub 0}–{sup 7}F{sub 1} of Eu{sup 3+} splits into 585 and 591 nm emission peaks, and the dominant peak is the orange emission at 591 nm.« less

Preparation and characterization of cellulose nanocrystals from the bio-ethanol residuals

Treesearch

Lanxing Du; Jinwu Wang; Yang Zhang; Chusheng Qi; Michael Wolcott; Zhiming Yu

2017-01-01

This study was to explore the conversion of low-cost bio-residuals into high value-added cellulose nanocrystals. Two enzymatic hydrolyzed residuals (i.e., HRMMW and HRSPW) were collected from two different bio-ethanol producing processes—hydrolyzing medium-milled wood (MMW) and hydrolyzing acid sulfite pretreated wood (SPW), respectively. The results showed that both...

Hydrothermal synthesis of NiWO4 crystals for high performance non-enzymatic glucose biosensors

NASA Astrophysics Data System (ADS)

Mani, Sivakumar; Vediyappan, Veeramani; Chen, Shen-Ming; Madhu, Rajesh; Pitchaimani, Veerakumar; Chang, Jia-Yaw; Liu, Shang-Bin

2016-04-01

A facile hydrothermal route for the synthesis of ordered NiWO4 nanocrystals, which show promising applications as high performance non-enzymatic glucose sensor is reported. The NiWO4-modified electrodes showed excellent sensitivity (269.6 μA mM-1 cm-2) and low detection limit (0.18 μM) for detection of glucose with desirable selectivity, stability, and tolerance to interference, rendering their prospective applications as cost-effective, enzyme-free glucose sensors.

Hydrothermal synthesis of NiWO4 crystals for high performance non-enzymatic glucose biosensors.

PubMed

Mani, Sivakumar; Vediyappan, Veeramani; Chen, Shen-Ming; Madhu, Rajesh; Pitchaimani, Veerakumar; Chang, Jia-Yaw; Liu, Shang-Bin

2016-04-18

A facile hydrothermal route for the synthesis of ordered NiWO4 nanocrystals, which show promising applications as high performance non-enzymatic glucose sensor is reported. The NiWO4-modified electrodes showed excellent sensitivity (269.6 μA mM(-1 )cm(-2)) and low detection limit (0.18 μM) for detection of glucose with desirable selectivity, stability, and tolerance to interference, rendering their prospective applications as cost-effective, enzyme-free glucose sensors.

Semiconductor nanocrystal quantum dot synthesis approaches towards large-scale industrial production for energy applications

DOE PAGES

Hu, Michael Z.; Zhu, Ting

2015-12-04

This study reviews the experimental synthesis and engineering developments that focused on various green approaches and large-scale process production routes for quantum dots. Fundamental process engineering principles were illustrated. In relation to the small-scale hot injection method, our discussions focus on the non-injection route that could be scaled up with engineering stir-tank reactors. In addition, applications that demand to utilize quantum dots as "commodity" chemicals are discussed, including solar cells and solid-state lightings.

Evolution of biofunctional semiconductor nanocrystals: a calorimetric investigation.

PubMed

Ghosh, Debasmita; Mondal, Somrita; Roy, Chandra Nath; Saha, Abhijit

2013-12-14

Semiconductor nanomaterials have found numerous applications in optoelectronic device fabrication and in platforms for drug delivery and hyperthermia cancer treatment, and in various other biomedical fields because of their high photochemical stability and size-tunable photoluminescence (PL). However, little attention has been paid to exploring the energetics of formation of these semiconductor nanoparticles. We demonstrate that formation of nanocrystals with biofunctionalization supported by widely used groups, BSA and cysteine, is an exothermic spontaneous process driven by enthalpy. The whole energetics of the reaction shows that formation of smaller particles is favored with lower synthesis temperature. Further, it is shown that the thermodynamics of nanoparticle formation is strongly influenced by the conformation of the protein matrix. We also demonstrate that protein supported formation of nanocrystals is thermodynamically more favorable compared to that involving smaller organic thiol groups. The favorable enthalpy of formation compensates unfavorable entropy, resulting in favorable Gibbs free energy. Thus, this study can open up new avenues for establishing a thermodynamic basis for the design of nanosystems with new and tunable properties.

Low temperature biosynthesis of Li2O-MgO-P2O5-TiO2 nanocrystalline glass with mesoporous structure exhibiting fast lithium ion conduction.

PubMed

Du, Xiaoyong; He, Wen; Zhang, Xudong; Ma, Jinyun; Wang, Chonghai; Li, Chuanshan; Yue, Yuanzheng

2013-04-01

We demonstrate a biomimetic synthesis methodology that allows us to create Li2O-MgO-P2O5-TiO2 nanocrystalline glass with mesoporous structure at lower temperature. We design a 'nanocrystal-glass' configuration to build a nanoarchitecture by means of yeast cell templates self-assembly followed by the controlled in-situ biomineralization of materials on the cell wall. Electrochemically active nanocrystals are used as the lamellar building blocks of mesopores, and the semiconductive glass phase can act both as the 'glue' between nanocrystals and functionalized component. The Li2O-MgO-P2O5-TiO2 nanocrystalline glass exhibits outstanding thermal stability, high conductivity and wide potential window. This approach could be applied to many other multicomponent glass-ceramics to fabricate mesoporous conducting materials for solid-state lithium batteries. Copyright © 2012 Elsevier B.V. All rights reserved.

Transition from CZTSe to CZTS via multicomponent CZTSSe: Potential low cost photovoltaic absorbers

NASA Astrophysics Data System (ADS)

Chawla, Parul; Jain, Shefali; Vashishtha, Parth; Ahamed, Mansoor; Sharma, Shailesh Narain

2018-01-01

A quintessential perspective for elaborating the pivotal role of quinary chalogenides such as CZTSSe plunges the thrust for exploration of non-vacuum approach for development of multicomponent chalcogenides utilizing organic surfactants and solvents for the nanocrystals ideal for photovoltaic applications. The piece of study envisages employment of TOPO-TOP as capping agents-cum-solvents for the very first time and have not been reported for CZTSSe-based materials till date. The work has been forwarded with the variation of anionic ratios in pristine counterparts of CZTSSe; i.e. CZTSe and CZTS in order to envision the potential of quinary chalcogenides wherein properties of two different materials coalesce to impart improved characteristics in CZTSSe. Varying Se:S ratios gradually during nanocrystals' synthesis by high-temperature colloidal route ensued precise control over the phase formation and morphology. With the employment of these capping agents, as-synthesized nanocrystals' are inherently Se-rich and high crystallinity restrains the need for selenization and high temperature annnealing respectively.

Size-Tunable Photothermal Germanium Nanocrystals.

PubMed

Sun, Wei; Zhong, Grace; Kübel, Christian; Jelle, Abdinoor A; Qian, Chenxi; Wang, Lu; Ebrahimi, Manuchehr; Reyes, Laura M; Helmy, Amr S; Ozin, Geoffrey A

2017-05-22

Germanium nanocrystals (ncGe) have not received as much attention as silicon nanocrystals (ncSi). However, Ge has demonstrated superiority over Si nanomaterials in some applications. Examples include, high charge-discharge rate lithium-ion batteries, small band-gap opto-electronic devices, and photo-therapeutics. When stabilized in an oxide matrix (ncGe/GeO x ), its high charge-retention has enabled non-volatile memories. It has also found utility as a high-capacity anode material for Li-ion batteries with impressive stability. Herein, we report an organic-free synthesis of size-controlled ncGe in a GeO x matrix as well as freestanding ncGe, via the thermal disproportionation of GeO prepared from thermally induced dehydration of Ge(OH) 2 . The photothermal effect of ncGe, quantified by Raman spectroscopy, is found to be size dependent and superior to ncSi. This advance suggests applications of ncGe in photothermal therapy, desalination, and catalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The optical and structural properties of graphene nanosheets and tin oxide nanocrystals composite

NASA Astrophysics Data System (ADS)

Farheen, Parveen, Azra; Azam, Ameer

2018-05-01

A nanocomposite material consisting of metal oxide and reduced graphene oxide was prepared via simple, economic, and effective chemical reduction method. The synthesis strategy was based on the reduction of GO with Sn2+ ion that combines tin oxidation and GO reduction in one step, which provides a simple, low-cost and effective way to prepare graphene nanosheets/SnO2 nanocrystals composites because no additional chemicals were needed. SEM and TEM images shows the uniform distribution of the SnO2 nanocrystals on the Graphene nanosheets (GNs) surface and transmission electron microscope shows an average particle size of 2-4 nm. The mean crystallite size was calculated by Debye Scherrer formula and was found to be about 4.0 nm. Optical analysis was done by using UV-Visible spectroscopy technique and the band gap energy of the GNs/SnO2 nanocomposite was calculated by Tauc relation and came out to be 3.43eV.

An Anion-Induced Hydrothermal Oriented-Explosive Strategy for the Synthesis of Porous Upconversion Nanocrystals

PubMed Central

Qiu, Peiyu; Sun, Rongjin; Gao, Guo; Zhang, Chunlei; Chen, Bin; Yan, Naishun; Yin, Ting; Liu, Yanlei; Zhang, Jingjing; Yang, Yao; Cui, Daxiang

2015-01-01

Rare-earth (RE)-doped upconversion nanocrystals (UCNCs) are deemed as the promising candidates of luminescent nanoprobe for biological imaging and labeling. A number of methods have been used for the fabrication of UCNCs, but their assembly into porous architectures with desired size, shape and crystallographic phase remains a long-term challenging task. Here we report a facile, anion-induced hydrothermal oriented-explosive method to simultaneously control size, shape and phase of porous UCNCs. Our results confirmed the anion-induced hydrothermal oriented-explosion porous structure, size and phase transition for the cubic/hexagonal phase of NaLuF4 and NaGdF4 nanocrystals with various sizes and shapes. This general method is very important not only for successfully preparing lanthanide doped porous UCNCs, but also for clarifying the formation process of porous UCNCs in the hydrothermal system. The synthesized UCNCs were used for in vitro and in vivo CT imaging, and could be acted as the potential CT contrast agents. PMID:25767613

Size Control of Porous Silicon-Based Nanoparticles via Pore-Wall Thinning.

PubMed

Secret, Emilie; Leonard, Camille; Kelly, Stefan J; Uhl, Amanda; Cozzan, Clayton; Andrew, Jennifer S

2016-02-02

Photoluminescent silicon nanocrystals are very attractive for biomedical and electronic applications. Here a new process is presented to synthesize photoluminescent silicon nanocrystals with diameters smaller than 6 nm from a porous silicon template. These nanoparticles are formed using a pore-wall thinning approach, where the as-etched porous silicon layer is partially oxidized to silica, which is dissolved by a hydrofluoric acid solution, decreasing the pore-wall thickness. This decrease in pore-wall thickness leads to a corresponding decrease in the size of the nanocrystals that make up the pore walls, resulting in the formation of smaller nanoparticles during sonication of the porous silicon. Particle diameters were measured using dynamic light scattering, and these values were compared with the nanocrystallite size within the pore wall as determined from X-ray diffraction. Additionally, an increase in the quantum confinement effect is observed for these particles through an increase in the photoluminescence intensity of the nanoparticles compared with the as-etched nanoparticles, without the need for a further activation step by oxidation after synthesis.

Study of low-temperature active rare-earth oxide catalysts for automotive exhaust clean-up.

DOT National Transportation Integrated Search

2014-02-01

We report a facile onepot synthesis of CexZr1-xO2 (0x1) solid solution nanocrystals using hydrothermal reactions. A direct formation of oxide solid solutions in aqueous solution under pressure at low temperatures was clearly revealed by X-ra...

Classification of Magnetic Nanoparticle Systems—Synthesis, Standardization and Analysis Methods in the NanoMag Project

PubMed Central

Bogren, Sara; Fornara, Andrea; Ludwig, Frank; del Puerto Morales, Maria; Steinhoff, Uwe; Fougt Hansen, Mikkel; Kazakova, Olga; Johansson, Christer

2015-01-01

This study presents classification of different magnetic single- and multi-core particle systems using their measured dynamic magnetic properties together with their nanocrystal and particle sizes. The dynamic magnetic properties are measured with AC (dynamical) susceptometry and magnetorelaxometry and the size parameters are determined from electron microscopy and dynamic light scattering. Using these methods, we also show that the nanocrystal size and particle morphology determines the dynamic magnetic properties for both single- and multi-core particles. The presented results are obtained from the four year EU NMP FP7 project, NanoMag, which is focused on standardization of analysis methods for magnetic nanoparticles. PMID:26343639

Fabrication of a magnetic helical mesostructured silica rod

NASA Astrophysics Data System (ADS)

Zhang, Lei; Zhang Qiao, Shi; Cheng, Lina; Yan, Zifeng; Qing Lu, Gao Max

2008-10-01

We report a one-step synthesis of magnetic helical mesostructured silica (MHMS) by self-assembly of an achiral surfactant, magnetic nanocrystals with stearic acid ligands and silicate. This core-shell structured material consists of an Fe3O4 superparamagnetic nanocrystal core and a highly ordered periodic helical mesoporous silica shell. We propose that the formation of the helical structure is induced by the interaction between the surfactant and dissociated stearic acid ligands. The MHMS obtained possesses superparamagnetism, uniform mesostructure, narrow pore size distribution, high surface area, and large pore volume. Furthermore, the drug release process is demonstrated using aspirin as a drug model and MHMS as a drug carrier in a sodium phosphate buffer solution.

Photochemical versus Thermal Synthesis of Cobalt Oxyhydroxide Nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alvarado, Samuel R.; Guo, Yijun; Ruberu, T. Purnima A.

2012-04-18

Photochemical methods facilitate the generation, isolation, and study of metastable nanomaterials having unusual size, composition, and morphology. These harder-to-isolate and highly reactive phases, inaccessible using conventional high-temperature pyrolysis, are likely to possess enhanced and unprecedented chemical, electromagnetic, and catalytic properties. We report a fast, low-temperature and scalable photochemical route to synthesize very small (3 nm) monodisperse cobalt oxyhydroxide (Co(O)OH) nanocrystals. This method uses readily and commercially available pentaamminechlorocobalt(III) chloride, [Co(NH3)5Cl]Cl2, under acidic or neutral pH and proceeds under either near-UV (350 nm) or Vis (575 nm) illumination. Control experiments showed that the reaction proceeds at competent rates only in themore » presence of light, does not involve a free radical mechanism, is insensitive to O2, and proceeds in two steps: (1) Aquation of [Co(NH3)5Cl]2+ to yield [Co(NH3)5(H2O)]3+, followed by (2) slow photoinduced release of NH3 from the aqua complex. This reaction is slow enough for Co(O)OH to form but fast enough so that nanocrystals are small (ca. 3 nm). The alternative dark thermal reaction proceeds much more slowly and produces much larger (250 nm) polydisperse Co(O)OH aggregates. UV–Vis absorption measurements and ab initio calculations yield a Co(O)OH band gap of 1.7 eV. Fast thermal annealing of Co(O)OH nanocrystals leads to Co3O4 nanocrystals with overall retention of nanoparticle size and morphology. Thermogravimetric analysis shows that oxyhydroxide to mixed-oxide phase transition occurs at significantly lower temperatures (up to ΔT = 64 °C) for small nanocrystals compared with the bulk.« less

Synthesis of ZnO-Pt nanoflowers and their photocatalytic applications.

PubMed

Yuan, Jiaquan; Choo, Eugene Shi Guang; Tang, Xiaosheng; Sheng, Yang; Ding, Jun; Xue, Junmin

2010-05-07

The photocatalytic behaviors of ZnO nanoparticles have been intensively studied recently. However, the photocatalytic efficiency of pure ZnO nanoparticles always suffers from the quick recombination of photoexcited electrons and holes. In order to suppress the electron-hole recombination and then raise the photocatalytic efficiency of ZnO, metal nanoparticles have been combined with ZnO to form ZnO-metal heterostructures. In this work, the feasibility of synthesizing ZnO-Pt composite nanoflowers for optimized catalytic properties was studied. Three different Pt nanocrystals, i.e. cubic Pt nanocrystals enclosed by {100} facets, octahedral Pt nanocrystals enclosed by {111} facets, and truncated octahedral Pt nanocrystals enclosed by both {111} and {100} facets, were selected as seeds for epitaxial growth of ZnO. A ZnO-Pt flowerlike nanostructure was formed by selective growth of ZnO nanolobes at {111} facets of the truncated octahedral Pt nanocrystals. The resultant nanoflowers had well defined ZnO-Pt interfaces and exposed Pt {100} facets, as confirmed by transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) measurements. The photocatalytic behaviors of the resultant ZnO-Pt nanoflowers were demonstrated in the photodegradation of ethyl violet. In comparison with the commercial TiO(2) photocatalyst P25, the ZnO-Pt flowerlike nanostructures showed improved catalytic efficiency. Notable ferromagnetism of the obtained ZnO-Pt flowerlike nanostructures was also observed. It is believed that the ZnO-Pt interface played an important role in the enlarged magnetic coercivity of the ZnO-Pt nanoflowers.

Predicting kinetic nanocrystal shapes through multi-scale theory and simulation: Polyvinylpyrrolidone-mediated growth of Ag nanocrystals

NASA Astrophysics Data System (ADS)

Balankura, Tonnam; Qi, Xin; Zhou, Ya; Fichthorn, Kristen A.

2016-10-01

In the shape-controlled synthesis of colloidal Ag nanocrystals, structure-directing agents, particularly polyvinylpyrrolidone (PVP), are known to be a key additive in making nanostructures with well-defined shapes. Although many Ag nanocrystals have been successfully synthesized using PVP, the mechanism by which PVP actuates shape control remains elusive. Here, we present a multi-scale theoretical framework for kinetic Wulff shape predictions that accounts for the chemical environment, which we used to probe the kinetic influence of the adsorbed PVP film. Within this framework, we use umbrella-sampling molecular dynamics simulations to calculate the potential of mean force and diffusion coefficient profiles of Ag atom deposition onto Ag(100) and Ag(111) in ethylene glycol solution with surface-adsorbed PVP. We use these profiles to calculate the mean-first passage times and implement extensive Brownian dynamics simulations, which allows the kinetic effects to be quantitatively evaluated. Our results show that PVP films can regulate the flux of Ag atoms to be greater towards Ag(111) than Ag(100). PVP's preferential binding towards Ag(100) over Ag(111) gives PVP its flux-regulating capabilities through the lower free-energy barrier of Ag atoms to cross the lower-density PVP film on Ag(111) and enhanced Ag trapping by the extended PVP film on Ag(111). Under kinetic control, {100}-faceted nanocrystals will be formed when the Ag flux is greater towards Ag(111). The predicted kinetic Wulff shapes are in agreement with the analogous experimental system.

Preparation of plasmonic vesicles from amphiphilic gold nanocrystals grafted with polymer brushes

PubMed Central

Song, Jibin; Huang, Peng; Chen, Xiaoyuan

2016-01-01

Gold nanovesicles contain multiple nanocrystals within a polymeric coating. The strong plasmonic coupling between adjacent nanoparticles in their vesicular shell makes ultrasensitive biosensing and bioimaging possible. In our laboratory, multifunctional plasmonic vesicles are assembled from amphiphilic gold nanocrystals (such as gold nanoparticles and gold nanorods) coated with mixed hydrophilic and hydrophobic polymer brushes or amphiphilic diblock co-polymer brushes. To fulfill the different requirements of biomedical applications, different polymers that are either pH=responsive, photoactive or biodegradable can be used to form the hydrophobic brush, while the hydrophilicity is maintained by polyethylene glycol (PEG). This protocol covers the preparation, surface functionalization and self-assembly of amphiphilic gold nanocrystals grafted covalently with polymer brushes. The protocol can be completed within 2 d. The preparation of amphiphilic gold nanocrystals, coated with amphiphilic diblock polymer brushes using a ‘grafting to’ method or mixed hydrophilic and hydrophobic polymer brushes using tandem ‘grafting to’ and ‘grafting from’ methods, is described. We also provide detailed procedures for the preparation and characterization of pH-responsive plasmonic gold nanovesicles from amphiphilic gold nanocrystals using a film-rehydration method that can be completed within ~3 d. PMID:27763624

Atomic force microscopy nanomanipulation of silicon nanocrystals for nanodevice fabrication

NASA Astrophysics Data System (ADS)

Decossas, Sébastien; Mazen, Frédéric; Baron, Thierry; Brémond, Georges; Souifi, Abdelkader

2003-12-01

An atomic force microscopy (AFM) tip has been used to manipulate silicon nanocrystals deposited by low-pressure chemical vapour deposition on thermally oxidized p-type Si wafer. Three nanomanipulation methods are presented. The first one catches a nanocrystal with the AFM tip and deposits it elsewhere: the tip is used as an electrostatic 'nano-crane'. The second one simultaneously manipulates a set of nanocrystals in order to draw well-defined unidimensional lines: the tip is used as a 'nano-broom'. The third one manipulates individual nanocrystals with a precision of about 10 nm using both oscillating and contact AFM modes. Switching from strong interaction forces (chemical) to weak ones (van der Waals, electrostatic or capillarity) is the basis of these manipulation methods. We have applied the second method to connect two electrodes drawn by e-beam and lift-off with a 70 nm long silicon nanocrystal chain. Current versus voltage characterization of the nanofabricated device shows that the increase in nanocrystal density gives rise to conduction between the connected electrodes. Resonant tunnelling effects resulting from Si nanocrystal (nc-Si) multiple tunnel junctions have been observed at 300 K. We also show that offset charges directly influence the position of the resonant tunnelling peaks. Finally, the possibility of manipulating nc-Si with a diameter of around 5 nm is shown to be a promising way to fabricate single electron devices operating at room temperature and fully compatible with silicon technology.

Cubic to tetragonal phase transition of Tm{sup 3+} doped nanocrystals in oxyfluoride glass ceramics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Yiming; Fu, Yuting; Shi, Yahui

2016-02-15

Tm{sup 3+} ions doped β-PbF{sub 2} nanocrystals in oxyfluoride glass ceramics with different doping concentrations and thermal temperatures are prepared by a traditional melt-quenching and thermal treatment method to investigate the structure and the phase transition of Tm{sup 3+} doped nanocrystals. The structures are characterized by X-ray diffraction Rietveld analysis and confirmed with numerical simulation. The phase transitions are proved further by the emission spectra. Both of the doping concentration and thermal temperature can induce an O{sub h} to D{sub 4h} site symmetry distortion and a cubic to tetragonal phase transition. The luminescence of Tm{sup 3+} doped nanocrystals at 800more » nm was modulated by the phase transition of the surrounding crystal field.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Waltmann, Curt; Horst, Nathan; Travesset, Alex

In this work, we present a detailed analysis of the interaction between two nanocrystals capped with ligands consisting of hydrocarbon chains by united atom molecular dynamics simulations. We show that the bonding of two nanocrystals is characterized by ligand textures in the form of vortices. These results are generalized to nanocrystals of different types (differing core and ligand sizes) where the structure of the vortices depends on the softness asymmetry. We provide rigorous calculations for the binding free energy, show that these energies are independent of the chemical composition of the cores, and derive analytical formulas for the equilibrium separation.more » We discuss the implications of our results for the self-assembly of single-component and binary nanoparticle superlattices. Overall, our results show that the structure of the ligands completely determines the bonding of nanocrystals, fully supporting the predictions of the recently proposed Orbifold topological model.« less

Engineering of Organic Nanocrystals by Electrocrystallization

NASA Astrophysics Data System (ADS)

Kilani, Mohamed

This work discusses the experimental and theoretical methods used to control the morphology of nanocrystals. The hypothesis of the thermodynamic/kinetic control of the morphology was verified. We applied the electrocrystallization to make K(def)TCP nanocrystals and we tuned the electrochemical parameters to determine their influence on the nanocrystals morphologies. The characterization was mainly performed with AFM and FE-SEM. We presented in this work the possibility to control the morphology of K(def)TCP using the electrochemical parameters. The obtained shapes ranged from nanorods to rhombohedral shape, which is reported for the first time. The observed growth behavior was modeled and simulated with a method based on Monte-Carlo techniques. The simulation results show a qualitative match with the experimental findings. This work contributes to the understanding of the crystal growth behavior and the thermodynamic/kinetic morphology transition using electrocrystallization.

Annealing effect and photovoltaic properties of nano-ZnS/textured p-Si heterojunction.

PubMed

Ji, Liang-Wen; Hsiao, Yu-Jen; Tang, I-Tseng; Meen, Teen-Hang; Liu, Chien-Hung; Tsai, Jenn-Kai; Wu, Tien-Chuan; Wu, Yue-Sian

2013-11-09

The preparation and characterization of heterojunction solar cell with ZnS nanocrystals synthesized by chemical bath deposition method were studied in this work. The ZnS nanocrystals were characterized by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). Lower reflectance spectra were found as the annealing temperature of ZnS film increased on the textured p-Si substrate. It was found that the power conversion efficiency (PCE) of the AZO/ZnS/textured p-Si heterojunction solar cell with an annealing temperature of 250°C was η = 3.66%.

Annealing effect and photovoltaic properties of nano-ZnS/textured p-Si heterojunction

PubMed Central

2013-01-01

The preparation and characterization of heterojunction solar cell with ZnS nanocrystals synthesized by chemical bath deposition method were studied in this work. The ZnS nanocrystals were characterized by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). Lower reflectance spectra were found as the annealing temperature of ZnS film increased on the textured p-Si substrate. It was found that the power conversion efficiency (PCE) of the AZO/ZnS/textured p-Si heterojunction solar cell with an annealing temperature of 250°C was η = 3.66%. PMID:24206942

Annealing effect and photovoltaic properties of nano-ZnS/textured p-Si heterojunction

NASA Astrophysics Data System (ADS)

Ji, Liang-Wen; Hsiao, Yu-Jen; Tang, I.-Tseng; Meen, Teen-Hang; Liu, Chien-Hung; Tsai, Jenn-Kai; Wu, Tien-Chuan; Wu, Yue-Sian

2013-11-01

The preparation and characterization of heterojunction solar cell with ZnS nanocrystals synthesized by chemical bath deposition method were studied in this work. The ZnS nanocrystals were characterized by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). Lower reflectance spectra were found as the annealing temperature of ZnS film increased on the textured p-Si substrate. It was found that the power conversion efficiency (PCE) of the AZO/ZnS/textured p-Si heterojunction solar cell with an annealing temperature of 250°C was η = 3.66%.

Tuning the Emission and Quantum Yield of Gold and Silver Nanoclusters Through Ligand Design and Doping

NASA Astrophysics Data System (ADS)

Mishra, Dinesh

Nanoparticles have been extensively studied in the past few decades due to the possibilities they offer in applications ranging from medicine to energy generation. A new class of ultra-small noble metal nanoparticles consisting of tens to hundreds of atoms, commonly known as clusters or nanoclusters, have drawn interest of the research community recently due to their unique optical, electronic and structural properties. Over the past few years, advances have been made in the synthesis of atomically precise noble metal clusters (for example, silver and gold) with distinct optical properties. Their ultra-small size distinguishes them from conventional plasmonic nanoparticles and the properties are very sensitive to the slight variation in the compositon of the cluster, i.e. the number of the metal atoms and/or the nature of the ligands. These clusters are interesting because of their potential applications in field such as sensing, imaging, catalysis, clean energy, photonics, etc. as well as they provide fundamental insight into the evolution of the optical and electronic properties of these clusters. In this project, we explored the strategies to synthesize luminescent metallic clusters of gold and silver and to promote their solubility and stability in aqueous and biological medium. We focused particularly on the thiolate protected clusters due to the higher affinity of gold and silver to sulfur. Lipoic acid (Thioctic acid) is a bio-molecule with a cyclic disulfide ring, which also acts as a chelating ligand. Due to the higher binding affinity of the cyclic disulfide ring to nanocrystal surface, lipoic acid and chemically modified lipoic acid molecules have been widely reported for the synthesis and functionalization of inorganic nanocrystals. Here, we describe the use of bidentate lipoic acid ligands in the one phase growth of luminescent gold and silver nanoclusters. In addition, we have synthesized a new set of monothiol ligands containing PEG and zwitterion for the functionalization of fluorescent clusters. Chapter 1 introduces the fundamental properties of metallic clusters and the origin of these properties from electronic and structural point of view. The optical properties of ultra-small nanocrystals (<2 nm) in comparison to the plasmonic particles is described. In addition, the variation of optical and structural properties from one metal to another as well as one ligand to another is also compared. Chapter 2 describes the synthesis of ultra-small size gold clusters with different optical emission (ranging from blue to red) using photo-activated LA-PEG ligands. The influence of various factors on the growth of the clusters is also studied. Optical properties of the clusters were studied by UV-visible absorption, PL emission and excitation and time resolved fluorescence spectroscopy. XPS and DOSY NMR were used to characterize the oxidation states and sizes of these clusters. The photo-chemical transformation of LA-PEG ligands to thiols and the effect of various experimental parameters such as solvent, oxygen, ligand functional group and effect of acid are described in chapter 3. Thiol yield percentage was quantified using ellman assay. Chapter 4 describes the one phase aqueous synthesis of Ag29 clusters capped with bidentate dihydrolipoic acid (DHLA). We also describe the drastic enhancement of the PL intensity upon gold doping of the Ag29 clusters. Optical properties along with the size characterization by electrospray ionization mass spectrometry is also described. We further describe the growth of these clusters using DHLA-PEG molecules. Chapter 5 describes the synthesis of highly fluorescent Au25-xAgx clusters stabilized with two types of ligands (triphenylphosphine and thiols). We designed a set of monothiolate ligands appended with PEG and zwitterionic moieties. This approach allows to prepare water soluble and stable metallic clusters with enhanced photoluminescence and well defined optical properties. Chapter 6 is the overall summary of our findings and prospects and outlook.

Extraction and characterization of mixed phase KNO2-KNO3 nanocrystals derived from flat-leaf green spinach

NASA Astrophysics Data System (ADS)

Hazarika, S.; Mohanta, D.

2013-01-01

Naturally available green spinach, which is a rich source of potassium, was used as the key ingredient to extract mixed-phase ferroelectric crystals of nitrite and nitrate derivatives (KNO2 + KNO3). The KNO3 phase was found to be dominant for higher pH values, as revealed by the x-ray diffraction patterns. The characteristic optical absorption spectra exhibited intra-band π-π* electronic transitions, whereas Fourier transform infrared spectra exhibited characteristic N-O stretching vibrations. Differential scanning calorimetry revealed a broad endothermic peak at ˜121.8 °C, highlighting a transition from phase II to I via phase III of KNO3. Obtaining nanoscale ferroelectrics via the adoption of green synthesis is economically viable for large-scale production and possible application in ferroelectric elements/devices.

Ferroelectric devices using lead zirconate titanate (PZT) nanoparticles.

PubMed

Paik, Young Hun; Kojori, Hossein Shokri; Kim, Sung Jin

2016-02-19

We successfully demonstrate the synthesis of lead zirconate titanate nanoparticles (PZT NPs) and a ferroelectric device using the synthesized PZT NPs. The crystalline structure and the size of the nanocrystals are studied using x-ray diffraction and transmission electron microscopy, respectively. We observe <100 nm of PZT NPs and this result matches dynamic light scattering measurements. A solution-based low-temperature process is used to fabricate PZT NP-based devices on an indium tin oxide substrate. The fabricated ferroelectric devices are characterized using various optical and electrical measurements and we verify ferroelectric properties including ferroelectric hysteresis and the ferroelectric photovoltaic effect. Our approach enables low-temperature solution-based processes that could be used for various applications. To the best of our knowledge, this low-temperature solution processed ferroelectric device using PZT NPs is the first successful demonstration of its kind.

Ferroelectric devices using lead zirconate titanate (PZT) nanoparticles

NASA Astrophysics Data System (ADS)

Paik, Young Hun; Shokri Kojori, Hossein; Kim, Sung Jin

2016-02-01

We successfully demonstrate the synthesis of lead zirconate titanate nanoparticles (PZT NPs) and a ferroelectric device using the synthesized PZT NPs. The crystalline structure and the size of the nanocrystals are studied using x-ray diffraction and transmission electron microscopy, respectively. We observe <100 nm of PZT NPs and this result matches dynamic light scattering measurements. A solution-based low-temperature process is used to fabricate PZT NP-based devices on an indium tin oxide substrate. The fabricated ferroelectric devices are characterized using various optical and electrical measurements and we verify ferroelectric properties including ferroelectric hysteresis and the ferroelectric photovoltaic effect. Our approach enables low-temperature solution-based processes that could be used for various applications. To the best of our knowledge, this low-temperature solution processed ferroelectric device using PZT NPs is the first successful demonstration of its kind.

Synthesis, characterization, and ion-exchange properties of colloidal zeolite nanocrystals

NASA Astrophysics Data System (ADS)

Jawor, Anna; Jeong, Byeong-Heon; Hoek, Eric M. V.

2009-10-01

Here, we present physical-chemical properties of Linde type A (LTA) zeolite crystals synthesized via conventional hydrothermal and microwave heating methods. Both heating methods produced LTA crystals that were sub-micron in size, highly negatively charged, super-hydrophilic, and stable when dispersed in water. However, microwave heating produced relatively narrow crystal size distributions, required much shorter heating times, and did not significantly change composition, crystallinity, or surface chemistry. Moreover, microwave heating allowed systematic variation of crystal size by varying heating temperature and time during the crystallization reaction, thus producing a continuous gradient of crystal sizes ranging from about 90 to 300 nm. In ion-exchange studies, colloidal zeolites exhibited excellent sorption kinetics and capacity for divalent metal ions, suggesting their potential for use in water softening, scale inhibition, and scavenging of toxic metal ions from water.

Synthesis and characterization of hollow spherical copper phosphide (Cu 3P) nanopowders

NASA Astrophysics Data System (ADS)

Liu, Shuling; Qian, Yitai; Xu, Liqiang

2009-03-01

In this paper, hollow spherical Cu 3P nanopowders were synthesized by using copper sulfate pentahydrate (CuSO 4ṡ5H 2O) and yellow phosphorus in a mixed solvent of glycol, ethanol and water at 140-180 ∘C for 12 h. X-ray powder diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), electron diffraction pattern (ED) and transmission electronic microscopy (TEM) studies show that the as-synthesized nanocrystal is pure hexagonal phase Cu 3P with a hollow spherical morphology. Based on the TEM observations, a possible aggregation growth mechanism was proposed for the formation of Cu 3P hollow structures. Meanwhile, the effects of some key factors such as solvents, reaction temperature and reaction time on the final formation of the Cu 3P hollow structure were also discussed.

High-strength magnetically switchable plasmonic nanorods assembled from a binary nanocrystal mixture

DOE PAGES

Zhang, Mingliang; Magagnosc, Daniel J.; Liberal, Iñigo; ...

2016-11-07

Next-generation ‘smart’ nanoparticle systems should be precisely engineered in size, shape and composition to introduce multiple functionalities, unattainable from a single material. Bottom-up chemical methods are prized for the synthesis of crystalline nanoparticles, that is, nanocrystals, with size- and shape-dependent physical properties, but they are less successful in achieving multifunctionality. Top-down lithographic methods can produce multifunctional nanoparticles with precise size and shape control, yet this becomes increasingly difficult at sizes of ~10 nm. In this paper, we report the fabrication of multifunctional, smart nanoparticle systems by combining top-down fabrication and bottom-up self-assembly methods. Particularly, we template nanorods from a mixturemore » of superparamagnetic Zn 0.2Fe 2.8O 4 and plasmonic Au nanocrystals. The superparamagnetism of Zn 0.2Fe 2.8O 4 prevents these nanorods from spontaneous magnetic-dipole-induced aggregation, while their magnetic anisotropy makes them responsive to an external field. Ligand exchange drives Au nanocrystal fusion and forms a porous network, imparting the nanorods with high mechanical strength and polarization-dependent infrared surface plasmon resonances. Finally, the combined superparamagnetic and plasmonic functions enable switching of the infrared transmission of a hybrid nanorod suspension using an external magnetic field.« less

Inhibition of palm oil oxidation by zeolite nanocrystals.

PubMed

Tan, Kok-Hou; Awala, Hussein; Mukti, Rino R; Wong, Ka-Lun; Rigaud, Baptiste; Ling, Tau Chuan; Aleksandrov, Hristiyan A; Koleva, Iskra Z; Vayssilov, Georgi N; Mintova, Svetlana; Ng, Eng-Poh

2015-05-13

The efficiency of zeolite X nanocrystals (FAU-type framework structure) containing different extra-framework cations (Li(+), Na(+), K(+), and Ca(2+)) in slowing the thermal oxidation of palm oil is reported. The oxidation study of palm oil is conducted in the presence of zeolite nanocrystals (0.5 wt %) at 150 °C. Several characterization techniques such as visual analysis, colorimetry, rheometry, total acid number (TAN), FT-IR spectroscopy, (1)H NMR spectroscopy, and Karl Fischer analyses are applied to follow the oxidative evolution of the oil. It was found that zeolite nanocrystals decelerate the oxidation of palm oil through stabilization of hydroperoxides, which are the primary oxidation product, and concurrently via adsorption of the secondary oxidation products (alcohols, aldehydes, ketones, carboxylic acids, and esters). In addition to the experimental results, periodic density functional theory (DFT) calculations are performed to elucidate further the oxidation process of the palm oil in the presence of zeolite nanocrystals. The DFT calculations show that the metal complexes formed with peroxides are more stable than the complexes with alkenes with the same ions. The peroxides captured in the zeolite X nanocrystals consequently decelerate further oxidation toward formation of acids. Unlike the monovalent alkali metal cations in the zeolite X nanocrystals (K(+), Na(+), and Li(+)), Ca(2+) reduced the acidity of the oil by neutralizing the acidic carboxylate compounds to COO(-)(Ca(2+))1/2 species.

In-situ high resolution transmission electron microscopy observation of silicon nanocrystal nucleation in a SiO{sub 2} bilayered matrix

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, T. C.-J., E-mail: terry.yang@unsw.edu.au; Wu, L.; Lin, Z.

2014-08-04

Solid-state nucleation of Si nanocrystals in a SiO{sub 2} bilayered matrix was observed at temperatures as low as 450 °C. This was achieved by aberration corrected high-resolution transmission electron microscopy (HRTEM) with real-time in-situ heating up to 600 °C. This technique is a valuable characterization tool especially with the recent interest in Si nanostructures for light emitting devices, non-volatile memories, and third-generation photovoltaics which all typically require a heating step in their fabrication. The control of size, shape, and distribution of the Si nanocrystals are critical for these applications. This experimental study involves in-situ observation of the nucleation of Si nanocrystals inmore » a SiO{sub 2} bilayered matrix fabricated through radio frequency co-sputtering. The results show that the shapes of Si nanocrystals in amorphous SiO{sub 2} bilayered matrices are irregular and not spherical, in contrast to many claims in the literature. Furthermore, the Si nanocrystals are well confined within their layers by the amorphous SiO{sub 2}. This study demonstrates the potential of in-situ HRTEM as a tool to observe the real time nucleation of Si nanocrystals in a SiO{sub 2} bilayered matrix. Furthermore, ideas for improvements on this in-situ heating HRTEM technique are discussed.« less

Facile synthesis and luminescence characteristics of high-quality CdS: Eu/ZnS core/shell nanocrystals with biocompatibility.

PubMed

Zhang, Kexin; Zhang, Rui; Yu, Yaxin; Sun, Shuqing

2012-04-01

In this paper, we report a facile method to synthesize high quality CdS: Eu nanocrystals (NCs) and CdS: Eu/ZnS NCs with strong photoluminescence (PL). The influence of various experimental variables including the concentration of Eu3+ ions, the reaction time and the reaction temperature were investigated systematically. In addition, the PL properties of CdS: Eu NCs exhibited pH sensitive. Under the acid condition, pH value of the CdS: Eu NCs solution played an important role in determining PL emission intensity. However, under the alkaline condition, the obtained CdS: Eu NCs exhibited a tunable PL emission wavelength (from 490 nm to 610 nm) when pH value was adjusted from pH 7 to 10. After coating with ZnS shell, the CdS: Eu/ZnS NCs showed enhanced PL intensity compare with one of the CdS: Eu NCs. The CdS: Eu NCs and CdS: Eu/ZnS NCs were characterized by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). In addition, the biocompatibility of these NCs was measured by hemolytic test, which indicated that CdS: Eu/ZnS NCs were more biocompatible than CdS: Eu NCs at the same conditions. It can be expected that CdS: Eu/ZnS NCs are promising biolabeling materials.

Synthesis and the luminescent properties of the Nd3+ ions doped three kinds of fluoride nanocrystals in organic solvents

NASA Astrophysics Data System (ADS)

Chen, Zhuo; Tian, Changyong; Bo, Shuhui; Liu, Xinhou; Zhen, Zhen

2015-10-01

Oleic acid (OA)-modified LaF3:Nd, NaYF4:Nd and CaF2:Nd nanocrystals (NCs) with the different Nd3+ ion concentration (2% and 5%) have been prepared. The structure and morphology of NCs were identified by XRD, TEM, FT-IR and TGA. The size of OA-modified NC is a mean diameter of 5-10 nm and can be dispersed in common organic solvents to form a transparent solution. The optical loss of NCs in organic solvent is the first time to discuss in this work. The luminescence properties of NCs were also characterized and studied by fluorescence spectrometer. The nanoparticles in solid and in the solution all exhibited the strong emission at the 1060 nm when the materials were excited around 800 nm. Compared with the LaF3 and CaF2 matrix, NaYF4 as the host can protect the Nd3+ ions more efficiently away from the nonradiative transitions. The longest luminescent lifetime of the solid NaYF4:2%Nd NCs was up to 136 μs, and the little difference of the fluorescence lifetime existed between the NCs in solid state and in solution. The low optical loss in organic solvent indicated that the Nd3+ ions-doped fluoride NCs are promising materials for optical amplification fields.

Processing and properties of eco-friendly bio-nanocomposite films filled with cellulose nanocrystals from sugarcane bagasse.

PubMed

El Achaby, Mounir; El Miri, Nassima; Aboulkas, Adil; Zahouily, Mohamed; Bilal, Essaid; Barakat, Abdellatif; Solhy, Abderrahim

2017-03-01

Novel synthesis strategy of eco-friendly bio-nanocomposite films have been exploited using cellulose nanocrystals (CNC) and polyvinyl alcohol/carboxymethyl cellulose (PVA/CMC) blend matrix as a potential in food packaging application. The CNC were extracted from sugarcane bagasse using sulfuric acid hydrolysis, and they were successfully characterized regarding their morphology, size, crystallinity and thermal stability. Thereafter, PVA/CMC-CNC bio-nanocomposite films, at various CNC contents (0.5-10wt%), were fabricated by the solvent casting method, and their properties were investigated. It was found that the addition of 5wt% CNC within a PVA/CMC increased the tensile modulus and strength by 141% and 83% respectively, and the water vapor permeability was reduced by 87%. Additionally, the bio-nanocomposites maintained the same transparency level of the PVA/CMC blend film (transmittance of ∼90% in the visible region), suggesting that the CNC were dispersed at the nanoscale. In these bio-nanocomposites, the adhesion properties and the large number of functional groups that are present in the CNC's surface and the macromolecular chains of the PVA/CMC blend are exploited to improve the interfacial interactions between the CNC and the blend. Consequently, these eco-friendly structured bio-nanocomposites with superior properties are expected to be useful in food packaging applications. Copyright © 2016. Published by Elsevier B.V.

GREEN SYNTHESIS OF SILVER AND PALLADIUM NANOPARTICLES AT ROOM TEMPERATURE USING COFFEE AND TEA EXTRACT

EPA Science Inventory

An extremely simple green approach that generates bulk quantities of nanocrystals of noble metals such as silver (Ag) and palladium (Pd) using coffee and tea extract at room temperature is described. The single-pot method uses no surfactant, capping agent, and/or template. The ob...

Controlled synthesis and facets-dependent photocatalysis of TiO2 nanocrystals

NASA Astrophysics Data System (ADS)

Roy, Nitish; Park, Yohan; Sohn, Youngku; Pradhan, Debabrata

2015-04-01

Titanium dioxide (TiO2) is a wide band gap semiconductor that has been extensively used in several environmental applications including degradation of organic hazardous chemicals, water splitting to generate hydrogen, dye sensitized solar cells, self cleaning agents, and pigments. Herein we demonstrate the synthesis of TiO2 nanocrystals (NCs) with the shapes of ellipsoids, rods, cuboids, and sheets with different exposed facets using a noncorrosive and nontoxic chemical (i.e. diethanolamine) as the shape controlling agent, unlike hydrofluoric acid commonly used. The TiO2 NCs of diverse shapes with different exposed facets were tested for photocatalytic hydroxyl radical (OH•) formation, which determines their photocatalytic behavior and the results were compared with the standard P-25 Degussa. The formation rate of OH• per specific surface area was found to be >6 fold higher for rod-shaped TiO2 NCs than that of commercial Degussa P25 catalyst. The highest photocatalytic activity of rod-shaped TiO2 NCs is ascribed to the unique chemical environment of {010} exposed facets which facilitates the electron/hole separation in presence of {101} facets.