Inorganic colloidal nanocrystals: Synthesis and bioapplications

NASA Astrophysics Data System (ADS)

Wu, Huimeng

Nanocrystals (NCs) are very small particles, which contain from a few hundred to thousands of atoms depending on the size of NCs. Because of their special properties compared with the bulk materials, NCs have found many promising applications in areas, such as biomedical diagnosis, catalysis, plasmonics, high-density data storage and solar energy conversion. This dissertation presents studies on the syntheses of metal oxide NCs and hybrid NCs, the surface functionalization of NCs by dual-interaction ligands, and gold-NC-based assay for the detection of beta-galactosidase. Monodisperse colloidal uranium dioxide NCs (UO2 NCs) were synthesized by decomposition of uranyl acetylacetonate. By changing the amount of added surfactant, the sizes of the NCs could vary from 2 ˜ 8 nm. Mechanistic studies of the formation of UO2 NCs showed that the condensation product (amide) of oleic acid and oleylamine plays an important role in controlling the particle size. Normally, high-quality NCs are synthesized in organic phase, but most of NC-based bio-applications require water-soluble NCs. To convert these hydrophobic NCs to hydrophilic particles, surface modification is employed. Here dual interaction ligands based on the Tween-derivatives (TDs) were synthesized. Stability tests on TD-capped NCs showed that these dual interaction ligands can significantly increase the stability of NCs compared to single interaction ligands. Further, These TD-capped QDs were further tested as fluorescent labels to detect virusprotein expression in cells. To exploit bio-applications of nanocrystals, gold nanocrystal-based assay to detect enzyme activity was designed. The optical properties of Au-NCs are not only dependent on the particle sizes and shapes, but also the distances between the particles. Here, Lipoic acid-tyramine-beta-galactopyranosyl (LTbeta-gal) was synthesized, as ligands, to cap Au-NCs; and the resultant LTbeta-gal-capped Au-NCs could disperse in water. After the hydrolysis of the

Heterostructures Prepared by Surface Modification of Nanocrystals

ERIC Educational Resources Information Center

Lee, Bo Hyun

2009-01-01

Inorganic nanocrystals (NCs) have drawn the attention from many researchers due to their promising potentials for next generation technologies, from photovoltaics to biological applications. Various types of NCs have become available by synthetic protocols developed in the last two decades. In addition, multicomponent hybrid NCs which can be…

Red-luminescence band: A tool for the quality assessment of germanium and silicon nanocrystals

NASA Astrophysics Data System (ADS)

Fraj, I.; Favre, L.; David, T.; Abbarchi, M.; Liu, K.; Claude, J. B.; Ronda, A.; Naffouti, M.; Saidi, F.; Hassen, F.; Maaref, H.; Aqua, J. N.; Berbezier, I.

2017-10-01

We present the photoluminescence (PL) emission of Silicon and Germanium nanocrystals (NCs) of different sizes embedded in two different matrices. Formation of the NCs is achieved via solid-state dewetting during annealing in a molecular beam epitaxy ultra-high vacuum system of ultrathin amorphous Si and Ge layers deposited at room temperature on SiO2. During the dewetting process, the bi-dimensional amorphous layers transform into small pseudo-spherical islands whose mean size can be tuned directly with the deposited thickness. The nanocrystals are capped either ex situ by silicon dioxide or in situ by amorphous Silicon. The surface-state dependent emission (typically in the range 1.74 eV-1.79 eV) exhibited higher relative PL quantum yields compared to the emission originating from the band gap transition. This red-PL emission comes from the radiative transitions between a Si band and an interface level. It is mainly ascribed to the NCs and environment features deduced from morphological and structural analyses. Power dependent analysis of the photoluminescence intensity under continuous excitation reveals a conventional power law with an exponent close to 1, in agreement with the type II nature of the emission. We show that Ge-NCs exhibit much lower quantum efficiency than Si-NCs due to non-radiative interface states. Low quantum efficiency is also obtained when NCs have been exposed to air before capping, even if the exposure time is very short. Our results indicate that a reduction of the non-radiative surface states is a key strategy step in producing small NCs with increased PL emission for a variety of applications. The red-PL band is then an effective tool for the quality assessment of NCs based structures.

Si-nanocrystal-based nanofluids for nanothermometry

NASA Astrophysics Data System (ADS)

Cardona-Castro, M. A.; Morales-Sánchez, A.; Licea-Jiménez, L.; Alvarez-Quintana, J.

2016-06-01

The measurement of local temperature in nanoscale volumes is becoming a technological frontier. Photoluminescent nanoparticles and nanocolloids are the natural choice for nanoscale temperature probes. However, the influence of a surrounding liquid on the cryogenic behavior of oxidized Si-nanocrystals (Si-NCs) has never been investigated. In this work, the photoluminescence (PL) of oxidized Si-NCs/alcohol based nanocolloids is measured as a function of the temperature and the molecule length of monohydric alcohols above their melting-freezing point. The results unveil a progressive blue shift on the emission peak which is dependent on the temperature as well as the dielectric properties of the surrounding liquid. Such an effect is analyzed in terms of thermal changes of the Si-NCs bandgap, quantum confinement and the polarization effects of the embedding medium; revealing an important role of the dielectric constant of the surrounding liquid. These results are relevant because they offer a general insight to the fundamental behavior of photoluminescent nanocolloids under a cooling process and moreover, enabling PL tuning based on the dielectric properties of the surrounding liquid. Hence, the variables required to engineer PL of nanofluids are properly identified for use as temperature sensors at the nanoscale.

Methods for preparing colloidal nanocrystal-based thin films

DOEpatents

Kagan, Cherie R.; Fafarman, Aaron T.; Choi, Ji-Hyuk; Koh, Weon-kyu; Kim, David K.; Oh, Soong Ju; Lai, Yuming; Hong, Sung-Hoon; Saudari, Sangameshwar Rao; Murray, Christopher B.

2016-05-10

Methods of exchanging ligands to form colloidal nanocrystals (NCs) with chalcogenocyanate (xCN)-based ligands and apparatuses using the same are disclosed. The ligands may be exchanged by assembling NCs into a thin film and immersing the thin film in a solution containing xCN-based ligands. The ligands may also be exchanged by mixing a xCN-based solution with a dispersion of NCs, flocculating the mixture, centrifuging the mixture, discarding the supernatant, adding a solvent to the pellet, and dispersing the solvent and pellet to form dispersed NCs with exchanged xCN-ligands. The NCs with xCN-based ligands may be used to form thin film devices and/or other electronic, optoelectronic, and photonic devices. Devices comprising nanocrystal-based thin films and methods for forming such devices are also disclosed. These devices may be constructed by depositing NCs on to a substrate to form an NC thin film and then doping the thin film by evaporation and thermal diffusion.

High-Bandgap Silicon Nanocrystal Solar Cells: Device Fabrication, Characterization, and Modeling

NASA Astrophysics Data System (ADS)

Löper, Philipp; Canino, Mariaconcetta; Schnabel, Manuel; Summonte, Caterina; Janz, Stefan; Zacharias, Margit

Silicon nanocrystals (Si NCs) embedded in Si-based dielectrics provide a Si-based high-bandgap material (1.7 eV) and enable the construction of crystalline Si tandem solar cells. This chapter focusses on Si NC embedded in silicon carbide, because silicon carbide offers electrical conduction through the matrix material. The material development is reviewed, and optical modeling is introduced as a powerful method to monitor the four material components, amorphous and crystalline silicon as well as amorphous and crystalline silicon carbide. In the second part of this chapter, recent device developments for the photovoltaic characterization of Si NCs are examined. The controlled growth of Si NCs involves high-temperature annealing which deteriorates the properties of any previously established selective contacts. A membrane-based device is presented to overcome these limitations. In this approach, the formation of both selective contacts is carried out after high-temperature annealing and is therefore not affected by the latter. We examine p-i-n solar cells with an intrinsic region made of Si NCs embedded in silicon carbide. Device failure due to damaged insulation layers is analyzed by light beam-induced current measurements. An optical model of the device is presented for improving the cell current. A characterization scheme for Si NC p-i-n solar cells is presented which aims at determining the fundamental transport and recombination properties, i.e., the effective mobility lifetime product, of the nanocrystal layer at device level. For this means, an illumination-dependent analysis of Si NC p-i-n solar cells is carried out within the framework of the constant field approximation. The analysis builds on an optical device model, which is used to assess the photogenerated current in each of the device layers. Illumination-dependent current-voltage curves are modelled with a voltage-dependent current collection function with only two free parameters, and excellent

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 Ti

Broadband enhancement of photoluminance from colloidal metal halide perovskite nanocrystals on plasmonic nanostructured surfaces.

PubMed

Zhang, Si; Liang, Yuzhang; Jing, Qiang; Lu, Zhenda; Lu, Yanqing; Xu, Ting

2017-11-07

Metal halide perovskite nanocrystals (NCs) as a new kind of promising optoelectronic material have attracted wide attention due to their high photoluminescence (PL) quantum yield, narrow emission linewidth and wideband color tunability. Since the PL intensity always has a direct influence on the performance of optoelectronic devices, it is of vital importance to improve the perovskite NCs' fluorescence emission efficiency. Here, we synthesize three inorganic perovskite NCs and experimentally demonstrate a broadband fluorescence enhancement of perovskite NCs by exploiting plasmonic nanostructured surface consisting of nanogrooves array. The strong near-field optical localization associated with surface plasmon polariton-coupled emission effect generated by the nanogrooves array can significantly boost the absorption of perovskite NCs and tailor the fluorescence emissions. As a result, the PL intensities of perovskite NCs are broadband enhanced with a maximum factor higher than 8-fold achieved in experimental demonstration. Moreover, the high efficiency PL of perovskite NCs embedded in the polymer matrix layer on the top of plasmonic nanostructured surface can be maintained for more than three weeks. These results imply that plasmonic nanostructured surface is a good candidate to stably broadband enhance the PL intensity of perovskite NCs and further promote their potentials in the application of visible-light-emitting devices.

Synthesis and characterization of some metal oxide nanocrystals by microwave irradiation

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

Rashad, M.; Gaber, A.; Abdelrahim, M. A.

2013-12-16

Copper oxide and cobalt oxide (CuO, Co3O4) nanocrystals (NCs) have been successfully prepared in a short time using microwave irradiation. The resulted powders of nanocrystals (NCs) were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Thermogravimetric analysis (TGA) measurements are also studied. Fourier-transform infrared (FT-IR) and UV–visible absorption spectroscopy of both kind of nanoparticels are illustrated. Optical absorption analysis indicated the direct band gap for both kinds of nanocrystals.

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.

Photoluminescence of CuInS2 nanocrystals: effect of surface modification

NASA Astrophysics Data System (ADS)

Kim, Young-Kuk; Cho, Young-Sang; Chung, Kookchae; Choi, Chul-Jin

2011-09-01

We have synthesized highly luminescent Cu-In-S(CIS) nanocrystals (NCs) by heating the mixture of metal carboxylates and alkylthiol under inert atmosphere. We modified the surface of CIS NCs with zinc carboxylate and subsequent injection of alkylthiol. As a result of the surface modification, highly luminescent CIS@ZnS core/shell nanocrystals were synthesized. The luminescence quantum yield (QY) of best CIS@ZnS NCs was above 50%, which is 10 times higher than the initial QY of CIS NCs before surface modification (QY=3%). Detailed study on the luminescence mechanism implies that etching of the surface of NCs by dissociated carboxylate group (CH3COO-) and formation of epitaxial shell by Zn with sulfur from alkylthiol efficiently removed the surface defects which are known to be major non-radiative recombination sites in semiconductor nanocrystals. In this study, we developed a novel surface modification route for monodispersed highly luminescent Cu-In-S NCs with less toxic and highly stable precursors. Investigation with the timeand the temperature-dependent photoluminescence showed that the trap related emission was minimized by surface modification and the donor-acceptor pair recombination was enhanced by controlling copper stoichiometry.xb

Optical properties and ensemble characteristics of size purified Silicon nanocrystals

NASA Astrophysics Data System (ADS)

Miller, Joseph Bradley

Nanotechnology is at the forefront of current scientific research and nanocrystals are being hailed as the 'artificial' atoms of the 21st century. Semiconducting silicon nanocrystals (SiNCs) are prime candidates for potential commercial applications because of silicon's already ubiquitous presence in the semiconductor industry, nontoxicity and abundance in nature. For realization of these potential applications, the properties and behavior of SiNCs need to be understood and enhanced. In this report, some of the main SiNC synthesis schemes are discussed, including those we are currently experimenting with to create our own SiNCs and the one utilized to create the SiNCs used in this study. The underlying physics that governs the unique behavior of SiNCs is then presented. The properties of the as-produced SiNCs are determined to depend strongly on surface passivation and environment. Size purification, an important aspect of nanomaterial utilization, was successfully performed on our SiNCs though density gradient ultracentrifugation. We demonstrate that the size-purified fractions exhibit an enhanced ability for colloidal self-assembly, with better aligned nanocrystal energy levels which promotes greater photostability in close-packed films and produces a slight increase in photoluminescence (PL) quantum yield. The qualities displayed by the fractions are exploited to form SiNC clusters that exhibit photostable PL. An analysis of SiNC cluster (from individual nanocrystals to collections of more than one thousand) blinking and PL shows an improvement in their PL emitting 'on' times. Pure SiNC films and SiNC-polymer nanocomposites are created and the dependence of their PL on temperature is measured. For such nanocomposites, the coupling between the 'coffee-ring' effect and liquid-liquid phase separation is also examined for ternary mixtures of solvent, polymer and semiconducting nanocrystal. We discover that with the right SiNC-polymer concentration and polymer

Electrical and Plasmonic Properties of Ligand-Free Sn(4+) -Doped In2 O3 (ITO) Nanocrystals.

PubMed

Jagadeeswararao, Metikoti; Pal, Somnath; Nag, Angshuman; Sarma, D D

2016-03-03

Sn(4+) -doped In2 O3 (ITO) is a benchmark transparent conducting oxide material. We prepared ligand-free but colloidal ITO (8 nm, 10 % Sn(4+) ) nanocrystals (NCs) by using a post-synthesis surface-modification reaction. (CH3 )3 OBF4 removes the native oleylamine ligand from NC surfaces to give ligand-free, positively charged NCs that form a colloidal dispersion in polar solvents. Both oleylamine-capped and ligand-free ITO NCs exhibit intense absorption peaks, due to localized surface plasmon resonance (LSPR) at around λ=1950 nm. Compared with oleylamine-capped NCs, the electrical resistivity of ligand-free ITO NCs is lower by an order of magnitude (≈35 mΩ cm(-1) ). Resistivity over a wide range of temperatures can be consistently described as a composite of metallic ITO grains embedded in an insulating matrix by using a simple equivalent circuit, which provides an insight into the conduction mechanism in these systems. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Red-ultraviolet photoluminescence tuning by Ni nanocrystals in epitaxial SrTiO3 matrix

NASA Astrophysics Data System (ADS)

Xiong, Z. W.; Cao, L. H.

2018-07-01

In this work, the self-organized Ni nanocrystals (NCs) were embedded in the epitaxial SrTiO3 matrix using pulsed laser deposition method. With the in-situ monitoring of reflection high-energy electron diffraction, both matrix and NCs could be precisely engineered with desired qualities by regulating the growth conditions according to the full release of stress energy at the interfaces of Ni NCs and SrTiO3. We achieved a controllable strained system according to the transformation of growth modes from three dimensional (3D) islands of Ni NCs to 2D layer-by-layer of SrTiO3, corresponding to the (1 1 1) and (0 0 l) orientation for Ni and SrTiO3, respectively. With the increase of Ni NCs concentration, the absorption intensity is increasing in the regions of 190-300 nm, and the band gap is gradually decreased. Besides, photoluminescence (PL) spectra reveal that the energy levels of Ni 3d bands contribute to the different PL colors, further inducing the enhancement of PL intensity and red-shift of emission peaks. Compared with the pure SrTiO3 published in the literature, much wider ranges of PL emission from red to ultraviolet can be tuned by the Ni NCs.

Location and Electronic Nature of Phosphorus in the Si Nanocrystal − SiO2 System

PubMed Central

König, Dirk; Gutsch, Sebastian; Gnaser, Hubert; Wahl, Michael; Kopnarski, Michael; Göttlicher, Jörg; Steininger, Ralph; Zacharias, Margit; Hiller, Daniel

2015-01-01

Up to now, no consensus exists about the electronic nature of phosphorus (P) as donor for SiO2-embedded silicon nanocrystals (SiNCs). Here, we report on hybrid density functional theory (h-DFT) calculations of P in the SiNC/SiO2 system matching our experimental findings. Relevant P configurations within SiNCs, at SiNC surfaces, within the sub-oxide interface shell and in the SiO2 matrix were evaluated. Atom probe tomography (APT) and its statistical evaluation provide detailed spatial P distributions. For the first time, we obtain ionisation states of P atoms in the SiNC/SiO2 system at room temperature using X-ray absorption near edge structure (XANES) spectroscopy, eliminating structural artefacts due to sputtering as occurring in XPS. K energies of P in SiO2 and SiNC/SiO2 superlattices (SLs) were calibrated with non-degenerate P-doped Si wafers. results confirm measured core level energies, connecting and explaining XANES spectra with h-DFT electronic structures. While P can diffuse into SiNCs and predominantly resides on interstitial sites, its ionization probability is extremely low, rendering P unsuitable for introducing electrons into SiNCs embedded in SiO2. Increased sample conductivity and photoluminescence (PL) quenching previously assigned to ionized P donors originate from deep defect levels due to P. PMID:25997696

One-pot size-controlled growth of graphene-encapsulated germanium nanocrystals

NASA Astrophysics Data System (ADS)

Lee, Jae-Hyun; Lee, Eun-Kyung; Kang, Seog-Gyun; Jung, Su-Ho; Son, Seok-Kyun; Nam, Woo Hyun; Kim, Tae-Hoon; Choi, Byong Lyong; Whang, Dongmok

2018-05-01

To realize graphene-encapsulated semiconductor nanocrystals (NCs), an additional graphene coating process, which causes shape destruction and chemical contamination, has so far been inevitable. We report herein one-pot growth of uniform graphene-germanium core-shell nanocrystals (Ge@G NCs) in gram scale by the addition of methane as a carbon source during the thermal pyrolysis of germane. The methane plays a critical role in the growth of the graphene shell, as well as in the determination of the nucleation density and diameter of the NCs, similar to a surfactant in the liquid-phase growth of monodisperse NCs. By adjusting the gas ratio of precursors, a mixture of germane and methane, we can control the size of the Ge@G NCs in the range of ∼5-180 nm. The Ge@G NCs were characterized by various microscopic and spectroscopic tools, which indicated that the Ge core is single crystalline, and is completely covered by the graphene shell. We further investigated the merits of the graphene shell, which can enhance the electrical conductivity of nanocrystalline materials.

Photo-sensitive Ge nanocrystal based films controlled by substrate deposition temperature

NASA Astrophysics Data System (ADS)

Stavarache, Ionel; Maraloiu, Valentin Adrian; Negrila, Catalin; Prepelita, Petronela; Gruia, Ion; Iordache, Gheorghe

2017-10-01

Lowering the temperature of crystallization by deposition of thin films on a heated substrate represents the easiest way to find new means to develop and improve new working devices based on nanocrystals embedded in thin films. The improvements are strongly related with the increasing of operation speed, substantially decreasing the energy consumption and reducing unit fabrication costs of the respective semiconductor devices. This approach avoids major problems, such as those related to diffusion or difficulties in controlling nanocrystallites size, which appear during thermal treatments at high temperatures after deposition. This article reports on a significant progress given by structuring Ge nanocrystals (Ge-NCs) embedded in silicon dioxide (SiO2) thin films by heating the substrate at 400 °C during co-deposition of Ge and SiO2 by magnetron sputtering. As a proof-of-concept, a Si/Ge-NCs:SiO2 photo-sensitive structure was fabricated thereof and characterized. The structure shows superior performance on broad operation bandwidth from visible to near-infrared, as strong rectification properties in dark, significant current rise in the inversion mode when illuminated, high responsivity, high photo-detectivity of 1014 Jones, quick response and significant conversion efficiency with peak value reaching 850% at -1 V and about 1000 nm. This simple preparation approach brings an important contribution to the effort of structuring Ge nanocrystallites in SiO2 thin films at a lower temperature for the purpose of using these materials for devices in optoelectronics, solar cells and electronics on flexible substrates.

Fabrication of multilayered Ge nanocrystals embedded in SiO xGeN y films

NASA Astrophysics Data System (ADS)

Gao, Fei; Green, Martin A.; Conibeer, Gavin; Cho, Eun-Chel; Huang, Yidan; Perez-Wurfl, Ivan; Flynn, Chris

2008-09-01

Multilayered Ge nanocrystals embedded in SiO xGeN y films have been fabricated on Si substrate by a (Ge + SiO 2)/SiO xGeN y superlattice approach, using a rf magnetron sputtering technique with a Ge + SiO 2 composite target and subsequent thermal annealing in N 2 ambient at 750 °C for 30 min. X-ray diffraction (XRD) measurement indicated the formation of Ge nanocrystals with an average size estimated to be 5.4 nm. Raman scattering spectra showed a peak of the Ge-Ge vibrational mode downward shifted to 299.4 cm -1, which was caused by quantum confinement of phonons in the Ge nanocrystals. Transmission electron microscopy (TEM) revealed that Ge nanocrystals were confined in (Ge + SiO 2) layers. This superlattice approach significantly improved both the size uniformity of Ge nanocrystals and their uniformity of spacing on the 'Z' growth direction.

Low capping group surface density on zinc oxide nanocrystals.

PubMed

Valdez, Carolyn N; Schimpf, Alina M; Gamelin, Daniel R; Mayer, James M

2014-09-23

The ligand shell of colloidal nanocrystals can dramatically affect their stability and reaction chemistry. We present a methodology to quantify the dodecylamine (DDA) capping shell of colloidal zinc oxide nanocrystals in a nonpolar solvent. Using NMR spectroscopy, three different binding regimes are observed: strongly bound, weakly associated, and free in solution. The surface density of bound DDA is constant over a range of nanocrystal sizes, and is low compared to both predictions of the number of surface cations and maximum coverages of self-assembled monolayers. The density of strongly bound DDA ligands on the as-prepared ZnO NCs is 25% of the most conservative estimate of the maximum surface DDA density. Thus, these NCs do not resemble the common picture of a densely capped surface ligand layer. Annealing the ZnO NCs in molten DDA for 12 h at 160 °C, which is thought to remove surface hydroxide groups, resulted in a decrease of the weakly associated DDA and an increase in the density of strongly bound DDA, to ca. 80% of the estimated density of a self-assembled monolayer on a flat ZnO surface. These findings suggest that as-prepared nanocrystal surfaces contain hydroxide groups (protons on the ZnO surfaces) that inhibit strong binding of DDA.

Annealing temperature and environment effects on ZnO nanocrystals embedded in SiO2: a photoluminescence and TEM study

PubMed Central

2013-01-01

We report on efficient ZnO nanocrystal (ZnO-NC) emission in the near-UV region. We show that luminescence from ZnO nanocrystals embedded in a SiO2 matrix can vary significantly as a function of the annealing temperature from 450°C to 700°C. We manage to correlate the emission of the ZnO nanocrystals embedded in SiO2 thin films with transmission electron microscopy images in order to optimize the fabrication process. Emission can be explained using two main contributions, near-band-edge emission (UV range) and defect-related emissions (visible). Both contributions over 500°C are found to be size dependent in intensity due to a decrease of the absorption cross section. For the smallest-size nanocrystals, UV emission can only be accounted for using a blueshifted UV contribution as compared to the ZnO band gap. In order to further optimize the emission properties, we have studied different annealing atmospheres under oxygen and under argon gas. We conclude that a softer annealing temperature at 450°C but with longer annealing time under oxygen is the most preferable scenario in order to improve near-UV emission of the ZnO nanocrystals embedded in an SiO2 matrix. PMID:24314071

Annealing temperature and environment effects on ZnO nanocrystals embedded in SiO2: a photoluminescence and TEM study.

PubMed

Pita, Kantisara; Baudin, Pierre; Vu, Quang Vinh; Aad, Roy; Couteau, Christophe; Lérondel, Gilles

2013-12-06

We report on efficient ZnO nanocrystal (ZnO-NC) emission in the near-UV region. We show that luminescence from ZnO nanocrystals embedded in a SiO2 matrix can vary significantly as a function of the annealing temperature from 450°C to 700°C. We manage to correlate the emission of the ZnO nanocrystals embedded in SiO2 thin films with transmission electron microscopy images in order to optimize the fabrication process. Emission can be explained using two main contributions, near-band-edge emission (UV range) and defect-related emissions (visible). Both contributions over 500°C are found to be size dependent in intensity due to a decrease of the absorption cross section. For the smallest-size nanocrystals, UV emission can only be accounted for using a blueshifted UV contribution as compared to the ZnO band gap. In order to further optimize the emission properties, we have studied different annealing atmospheres under oxygen and under argon gas. We conclude that a softer annealing temperature at 450°C but with longer annealing time under oxygen is the most preferable scenario in order to improve near-UV emission of the ZnO nanocrystals embedded in an SiO2 matrix.

Direct exchange between silicon nanocrystals and tunnel oxide traps under illumination on single electron photodetector

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

Chatbouri, S., E-mail: Samir.chatbouri@yahoo.com; Troudi, M.; Sghaier, N.

2016-09-15

In this paper we present the trapping of photogenerated charge carriers for 300 s resulted by their direct exchange under illumination between a few silicon nanocrystals (ncs-Si) embedded in an oxide tunnel layer (SiO{sub x} = 1.5) and the tunnel oxide traps levels for a single electron photodetector (photo-SET or nanopixel). At first place, the presence of a photocurrent limited in the inversion zone under illumination in the I–V curves confirms the creation of a pair electron/hole (e–h) at high energy. This photogenerated charge carriers can be trapped in the oxide. Using the capacitance-voltage under illumination (the photo-CV measurements) wemore » show a hysteresis chargement limited in the inversion area, indicating that the photo-generated charge carriers are stored at traps levels at the interface and within ncs-Si. The direct exchange of the photogenerated charge carriers between the interface traps levels and the ncs-Si contributed on the photomemory effect for 300 s for our nanopixel at room temperature.« less

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

A Silicon Nanocrystal Schottky Junction Solar Cell produced from Colloidal Silicon Nanocrystals

PubMed Central

2010-01-01

Solution-processed semiconductors are seen as a promising route to reducing the cost of the photovoltaic device manufacture. We are reporting a single-layer Schottky photovoltaic device that was fabricated by spin-coating intrinsic silicon nanocrystals (Si NCs) from colloidal suspension. The thin-film formation process was based on Si NCs without any ligand attachment, exchange, or removal reactions. The Schottky junction device showed a photovoltaic response with a power conversion efficiency of 0.02%, a fill factor of 0.26, short circuit-current density of 0.148 mA/cm2, and open-circuit voltage of 0.51 V. PMID:20676200

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.

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

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

High-Brightness Blue and White LEDs based on Inorganic Perovskite Nanocrystals and their Composites

DOE PAGES

Yao, En -Ping; Yang, Zhanlue; Meng, Lei; ...

2017-04-10

Inorganic metal halide perovskite nanocrystals (NCs) have been employed universally in light-emitting applications during the past two years. Here, blue-emission (≈ 470 nm) Cs-based perovskite NCs are derived by directly mixing synthesized bromide and chloride nanocrystals with a weight ratio of 2:1. High-brightness blue perovskite light-emitting diodes (PeLEDs) are obtained by controlling the grain size of the perovskite films. Moreover, a white PeLED is demonstrated for the first time by blending orange polymer materials with the blue perovskite nanocrystals as the active layer. Exciton transfer from the blue nanocrystals to the orange polymers via Forster or Dexter energy transfer ismore » analyzed through time resolved photoluminescence. In conclusion, by tuning the ratio between the perovskite nanocrystals and polymers, pure white light is achieved with the a CIE coordinate at (0.33,0.34).« less

High-Brightness Blue and White LEDs based on Inorganic Perovskite Nanocrystals and their Composites

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

Yao, En -Ping; Yang, Zhanlue; Meng, Lei

Inorganic metal halide perovskite nanocrystals (NCs) have been employed universally in light-emitting applications during the past two years. Here, blue-emission (≈ 470 nm) Cs-based perovskite NCs are derived by directly mixing synthesized bromide and chloride nanocrystals with a weight ratio of 2:1. High-brightness blue perovskite light-emitting diodes (PeLEDs) are obtained by controlling the grain size of the perovskite films. Moreover, a white PeLED is demonstrated for the first time by blending orange polymer materials with the blue perovskite nanocrystals as the active layer. Exciton transfer from the blue nanocrystals to the orange polymers via Forster or Dexter energy transfer ismore » analyzed through time resolved photoluminescence. In conclusion, by tuning the ratio between the perovskite nanocrystals and polymers, pure white light is achieved with the a CIE coordinate at (0.33,0.34).« less

Using Plasmonic Copper Sulfide Nanocrystals as Smart Light-Driven Sterilants.

PubMed

Liu, Zhen; Liu, Xianjun; Du, Yingda; Ren, Jinsong; Qu, Xiaogang

2015-10-27

As an efficient route to control pet overpopulation and develop neutered experimental animals, male sterilization via surgical techniques, chemical injections, and antifertility vaccines has brought particular attention recently. However, these traditional ways usually induce long-term adverse reactions, immune suppression, and serious infection and pain. To overcome the above limitations, we developed a platform in the present study by using plasmonic copper sulfide nanocrystals (Cu2-xS NCs) as intelligent light-driven sterilants with ideal outcomes. Upon NIR laser irradiation, these well-prepared Cu2-xS NCs can possess NIR-induced hyperthermia and generate high levels of reactive oxygen species (ROS). Due to the cooperation of photothermal and photodynamic effects, these nanocrystals exhibited NIR-mediated toxicity toward Sertoli cells both in vitro and in vivo in a mild manner. We attribute the potential mechanism of cellular injury to the apoptosis-related death and denaturation of protein in the testicles. Furthermore, the possible metabolism route and long-term toxicity of these nanocrystals after testicular injection indicate their high biocompatibility. Taking together, our study on the NIR-induced toxicity of Cu2-xS NCs provides keen insights for the usage of plasmonic nanomaterials in biomedicine.

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.

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.

Nanocrystals embedded in hafnium dioxide-based dielectrics as charge storage nodes of nano-floating gate memory

NASA Astrophysics Data System (ADS)

Lee, Pui Fai

2007-12-01

Nanocrystals (NC) embedded in dielectrics have attracted a great deal of attention recently because they can potentially be applied in nonvolatile, high-speed, high-density and low-power memory devices. This device benefits from a relatively low operating voltage, high endurance, fast write-erase speeds and better immunity to soft errors. The nanocrystal materials suitable for such an application can be either metals or semiconductors. Recent studies have shown that high-k dielectrics, instead of SiO2 , for the tunneling layer in nanocrystal floating gate memory can improve the trade-off between data retention and program efficiency due to the unique band alignment of high-k dielectrics in the programming and retention modes. In this project, HfAlO has been selected as the high- k dielectric for the nanocrystal floating gate memory structure. The trilayer structure (HfAlO/Ge-NC/HfAlO) on Si was fabricated by PLD. Results revealed that relatively low substrate temperature and growth rate are favourable for the formation of smaller-size Ge nanocrystals. Effects of size/density of the Ge nanocrystal, the tunneling and control oxide layer thicknesses and the oxygen partial pressure during their growth on the charge storage and charge retention characteristics have also been studied. The island structure of the Ge nanocrystal suggests that the growth is based on the Volmer-Webber mode. The self-organized Ge nanocrystals so formed were uniform in size (5--20 nm diameter) and distribution with a density approaching 1012--1013cm-2. Flat-band voltage shift (DeltaVFB) of about 3.6 V and good retention property have been achieved. By varying aggregation distance, sputtering gas pressure and ionization power of the nanocluster source, nanoclusters of Ge with different sizes can be formed. The memory effect of the trilayer structure so formed with 10 nm Ge nanoclusters are manifested by the counter-clockwise hysteresis loop in the C-V curves and a maximum flat-band voltage

Synthesis and characterization of rare-earth-doped calcium tungstate nanocrystals

NASA Astrophysics Data System (ADS)

Suneeta, P.; Rajesh, Ch.; Ramana, M. V.

2018-02-01

In this paper, we report synthesis and characterization of rare-earth-ion-doped calcium tungstate (CaWO4) nanocrystals (NCs). Rare-earth ions, such as gadolinium (Gd), neodymium (Nd), praseodymium (Pr), samarium (Sm) and holmium (Ho), were successfully doped in the CaWO4 NCs by changing the synthesis conditions. The adopted synthesis route was found to be fast and eco-friendly. Structural characterizations, such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and compositional analysis, were performed using energy dispersive analysis of X-rays (EDAX) on as-synthesized NCs. The results indicate the size of the NCs ranging between 47 to 68nm and incorporation of rare-earth ions in CaWO4 NCs.

Influences of CdSe NCs on the photovoltaic parameters of BHJ organic solar cells

NASA Astrophysics Data System (ADS)

Ongul, Fatih; Yuksel, Sureyya Aydin; Allahverdi, Cagdas; Bozar, Sinem; Kazici, Mehmet; Gunes, Serap

2018-04-01

In this study, the high quality CdSe nanocrystals (NCs) capped with stearic acid were synthesized in a solvent and then purified four times by using the precipitation and redissolution process. The average size of the synthesized CdSe NCs was determined 3.0 nm via transmission electron microscopy (TEM) measurement and their corresponding optical band edge energy was also calculated as 2.1 eV using ultraviolet-visible (UV-Vis) absorption spectroscopy. The bulk heterojunction (BHJ) hybrid solar cells based on a ternary system including P3HT, PCBM and CdSe NCs at different weight concentrations (0 wt%, 0.1 wt%, 0.5 wt%, 1 wt% and 2 wt%) were fabricated by spin-casting process. The effect of the concentration of CdSe NCs on the photovoltaic parameters of these BHJ organic solar cells was investigated. The surface morphology of the photoactive layer modified by the incorporation of CdSe NCs into P3HT:PCBM matrix was observed with scanning electron microscopy (SEM). It was shown that when the concentration of CdSe NCs increases above 0.1 wt% in this ternary system, the photovoltaic performance of the devices significantly decreases. The power conversion efficiency of the organic photovoltaic (OPV) device was enhanced 20% by incorporating CdSe NCs with 0.1 wt% with respect to those without CdSe NCs.

Chemical composition of matrix-embedded ternary II-VI nanocrystals derived from first- and second-order Raman spectra

NASA Astrophysics Data System (ADS)

Azhniuk, Yu. M.; Hutych, Yu. I.; Lopushansky, V. V.; Prymak, M. V.; Gomonnai, A. V.; Zahn, D. R. T.

2016-12-01

A one- and multiphonon Raman scattering study is performed for an extensive set of CdS1-xSex, Cd1-yZnyS, Cd1-yZnySe, and CdSe1-xTex nanocrystals to investigate the applicability of first- and second-order Raman spectra for the determination of the matrix-embedded ternary nanocrystal composition. For one-mode ternary systems both the LO and 2LO phonon frequencies in the Raman spectra are shown to be a good measure of the nanocrystal composition. For two-mode systems, the approaches based on the difference of the LO phonon frequencies (first-order Raman spectra) or double LO overtone and combination tone frequencies (second-order Raman spectra) as well as on the LO phonon band intensity ratios are analysed. The weak electron-phonon coupling in the II-VI nanocrystals and the polaron constant values for the nanocrystal sublattices are discussed.

3D assembly of upconverting NaYF4 nanocrystals by AFM nanoxerography: creation of anti-counterfeiting microtags

NASA Astrophysics Data System (ADS)

Sangeetha, Neralagatta M.; Moutet, Pierre; Lagarde, Delphine; Sallen, Gregory; Urbaszek, Bernhard; Marie, Xavier; Viau, Guillaume; Ressier, Laurence

2013-09-01

Formation of 3D close-packed assemblies of upconverting NaYF4 colloidal nanocrystals (NCs) on surfaces, by Atomic Force Microscopy (AFM) nanoxerography is presented. The surface potential of the charge patterns, the NC concentration, the polarizability of the NCs and the polarity of the dispersing solvent are identified as the key parameters controlling the assembly of NaYF4 NCs into micropatterns of the desired 3D architecture. This insight allowed us to fabricate micrometer sized Quick Response (QR) codes encoded in terms of upconversion luminescence intensity or color. Topographically hidden messages could also be readily incorporated within these microtags. This work demonstrates that AFM nanoxerography has enormous potential for generating high-security anti-counterfeiting microtags.Formation of 3D close-packed assemblies of upconverting NaYF4 colloidal nanocrystals (NCs) on surfaces, by Atomic Force Microscopy (AFM) nanoxerography is presented. The surface potential of the charge patterns, the NC concentration, the polarizability of the NCs and the polarity of the dispersing solvent are identified as the key parameters controlling the assembly of NaYF4 NCs into micropatterns of the desired 3D architecture. This insight allowed us to fabricate micrometer sized Quick Response (QR) codes encoded in terms of upconversion luminescence intensity or color. Topographically hidden messages could also be readily incorporated within these microtags. This work demonstrates that AFM nanoxerography has enormous potential for generating high-security anti-counterfeiting microtags. Electronic supplementary information (ESI) available: Detailed experimental procedures for the synthesis of upconverting NaYF4 nanocrystals and their transmission electron microscopy images. KFM and AFM images corresponding to the assembly of positively charged β-NaYF4:Er3+,Yb3+ nanocrystals from water suspensions by AFM nanoxerography. Photoluminescence spectra of β-NaYF4:Er3+,Yb3+ nanocrystals

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.

Influences of CdSe NCs on the photovoltaic parameters of BHJ organic solar cells.

PubMed

Ongul, Fatih; Yuksel, Sureyya Aydin; Allahverdi, Cagdas; Bozar, Sinem; Kazici, Mehmet; Gunes, Serap

2018-04-05

In this study, the high quality CdSe nanocrystals (NCs) capped with stearic acid were synthesized in a solvent and then purified four times by using the precipitation and redissolution process. The average size of the synthesized CdSe NCs was determined ~3.0nm via transmission electron microscopy (TEM) measurement and their corresponding optical band edge energy was also calculated as ~2.1eV using ultraviolet-visible (UV-Vis) absorption spectroscopy. The bulk heterojunction (BHJ) hybrid solar cells based on a ternary system including P3HT, PCBM and CdSe NCs at different weight concentrations (0wt%, 0.1wt%, 0.5wt%, 1wt% and 2wt%) were fabricated by spin-casting process. The effect of the concentration of CdSe NCs on the photovoltaic parameters of these BHJ organic solar cells was investigated. The surface morphology of the photoactive layer modified by the incorporation of CdSe NCs into P3HT:PCBM matrix was observed with scanning electron microscopy (SEM). It was shown that when the concentration of CdSe NCs increases above 0.1wt% in this ternary system, the photovoltaic performance of the devices significantly decreases. The power conversion efficiency of the organic photovoltaic (OPV) device was enhanced ~20% by incorporating CdSe NCs with 0.1wt% with respect to those without CdSe NCs. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of X-ray irradiation on the optical absorption of СdSe1-xTex nanocrystals embedded in borosilicate glass

NASA Astrophysics Data System (ADS)

Prymak, M. V.; Azhniuk, Yu. M.; Solomon, A. M.; Krasilinets, V. M.; Lopushansky, V. V.; Bodnar, I. V.; Gomonnai, A. V.; Zahn, D. R. T.

2012-07-01

The effect of X-ray irradiation on the optical absorption spectra of CdSe1-xTex nanocrystals embedded in a borosilicate matrix is studied. The observed blue shift of the absorption edge and bleaching of the confinement-related features in the spectra are related to X-ray induced negative ionization of the nanocrystals with charge transfer across the nanocrystal/matrix interface. The radiation-induced changes are observed to recover after longer post-irradiation storage at room temperature.

Spectroscopic characterization of ligands on the surface of water dispersible NaGdF4:Ln3+ nanocrystals

NASA Astrophysics Data System (ADS)

Cichos, J.; Karbowiak, M.

2012-05-01

For electronic or biomedical applications it is desirable to have ligand-free water-dispersible nanocrystals (NCs). The commonly used FTIR spectroscopy often provides a direct evidence for molecules on the surface. In some cases, however, the strong bands of solvent molecules may obscure the peaks of surface bounded ligands. We show that in this regard the emission spectroscopy may be used as a more reliable probing tool. The relevant information can be obtained from emission and excitation spectra, emission decay times as well as from analysis of relative efficiency of excitation energy transfer from Gd3+ to Eu3+ ions. Using these methods we tested samples obtained by various synthetic routes and indicated that only nitrosonium tetrafluoroborate (NOBF4) removes successfully the organic ligands from the nanocrystals surface, yielding organic ligand-free NCs dispersible in aqueous solutions. The conclusions drawn from emission spectroscopy are useful for interpretation of results of FTIR, Raman and NMR studies. The detailed assignment of FTIR peaks for oleate-capped and oleate-free NCs is also provided. Finally, we point to the risk of drawing erroneous conclusions about colloidal stability of nanocrystals if refractive indexes of NCs and medium are similar.

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

Size and shape effects in β-NaGdF4: Yb3+, Er3+ nanocrystals

NASA Astrophysics Data System (ADS)

Noculak, Agnieszka; Podhorodecki, Artur

2017-04-01

Three sets of β-NaGdF4:Yb3+, Er3+ nanocrystals (NCs) with different shapes (spherical and more complex flower shapes), different sizes (6-17 nm) and Yb3+ concentrations (2%-15%) were synthesized by a co-precipitation method using oleic acid as a stabilizing agent. The uncommon, single-crystalline flower-shaped NCs were obtained by simply adjusting the fluorine-to-lanthanides molar ratio. Additionally, some of the NCs with different sizes have been covered by the un-doped shell. The crystal phase, shapes and sizes of all NCs were examined using transmission electron microscopy and x-ray diffraction methods. Simultaneously, upconversion luminescence and lifetimes, under 980 nm excitation, were measured and the changes in green to red (G/R) emission ratios as well as emission decay times were correlated with the evolution of nanocrystal sizes and surface to volume ratios. Three different mechanisms responsible for the changes in G/R ratios were presented and discussed.

Material parameters from frequency dispersion simulation of floating gate memory with Ge nanocrystals in HfO2

NASA Astrophysics Data System (ADS)

Palade, C.; Lepadatu, A. M.; Slav, A.; Lazanu, S.; Teodorescu, V. S.; Stoica, T.; Ciurea, M. L.

2018-01-01

Trilayer memory capacitors with Ge nanocrystals (NCs) floating gate in HfO2 were obtained by magnetron sputtering deposition on p-type Si substrate followed by rapid thermal annealing at relatively low temperature of 600 °C. The frequency dispersion of capacitance and resistance was measured in accumulation regime of Al/HfO2 gate oxide/Ge NCs in HfO2 floating gate/HfO2 tunnel oxide/SiOx/p-Si/Al memory capacitors. For simulation of the frequency dispersion a complex circuit model was used considering an equivalent parallel RC circuit for each layer of the trilayer structure. A series resistance due to metallic contacts and Si substrate was necessary to be included in the model. A very good fit to the experimental data was obtained and the parameters of each layer in the memory capacitor, i.e. capacitances and resistances were determined and in turn the intrinsic material parameters, i.e. dielectric constants and resistivities of layers were evaluated. The results are very important for the study and optimization of the hysteresis behaviour of floating gate memories based on NCs embedded in oxide.

Effect of metal ions on photoluminescence, charge transport, magnetic and catalytic properties of all-inorganic colloidal nanocrystals and nanocrystal solids.

PubMed

Nag, Angshuman; Chung, Dae Sung; Dolzhnikov, Dmitriy S; Dimitrijevic, Nada M; Chattopadhyay, Soma; Shibata, Tomohiro; Talapin, Dmitri V

2012-08-22

Colloidal semiconductor nanocrystals (NCs) provide convenient "building blocks" for solution-processed solar cells, light-emitting devices, photocatalytic systems, etc. The use of inorganic ligands for colloidal NCs dramatically improved inter-NC charge transport, enabling fast progress in NC-based devices. Typical inorganic ligands (e.g., Sn(2)S(6)(4-), S(2-)) are represented by negatively charged ions that bind covalently to electrophilic metal surface sites. The binding of inorganic charged species to the NC surface provides electrostatic stabilization of NC colloids in polar solvents without introducing insulating barriers between NCs. In this work we show that cationic species needed for electrostatic balance of NC surface charges can also be employed for engineering almost every property of all-inorganic NCs and NC solids, including photoluminescence efficiency, electron mobility, doping, magnetic susceptibility, and electrocatalytic performance. We used a suite of experimental techniques to elucidate the impact of various metal ions on the characteristics of all-inorganic NCs and developed strategies for engineering and optimizing NC-based materials.

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).

A low thermal impact annealing process for SiO2-embedded Si nanocrystals with optimized interface quality

NASA Astrophysics Data System (ADS)

Hiller, Daniel; Gutsch, Sebastian; Hartel, Andreas M.; Löper, Philipp; Gebel, Thoralf; Zacharias, Margit

2014-04-01

Silicon nanocrystals (Si NCs) for 3rd generation photovoltaics or optoelectronic applications can be produced by several industrially compatible physical or chemical vapor deposition technologies. A major obstacle for the integration into a fabrication process is the typical annealing to form and crystallize these Si quantum dots (QDs) which involves temperatures ≥1100 °C for 1 h. This standard annealing procedure allows for interface qualities that correspond to more than 95% dangling bond defect free Si NCs. We study the possibilities to use rapid thermal annealing (RTA) and flash lamp annealing to crystallize the Si QDs within seconds or milliseconds at high temperatures. The Si NC interface of such samples exhibits huge dangling bond defect densities which makes them inapplicable for photovoltaics or optoelectronics. However, if the RTA high temperature annealing is combined with a medium temperature inert gas post-annealing and a H2 passivation, luminescent Si NC fractions of up to 90% can be achieved with a significantly reduced thermal load. A new figure or merit, the relative dopant diffusion length, is introduced as a measure for the impact of a Si NC annealing procedure on doping profiles of device structures.

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.

Water-soluble CdTe nanocrystals under high pressure

NASA Astrophysics Data System (ADS)

Lin, Yan-Cheng

2015-02-01

The application of static high pressure provides a method for precisely controlling and investigating many fundamental and unique properties of semiconductor nanocrystals (NCs). This study systematically investigates the high-pressure photoluminescence (PL) and time-resolved carrier dynamics of thiol-capped CdTe NCs of different sizes, at different concentrations, and in various stress environments. The zincblende-to-rocksalt phase transition in thiol-capped CdTe NCs is observed at a pressure far in excess of the bulk phase transition pressure. Additionally, the process of transformation depends strongly on NC size, and the phase transition pressure increases with NC size. These peculiar phenomena are attributed to the distinctive bonding of thiols to the NC surface. In a nonhydrostatic environment, considerable flattening of the PL energy of CdTe NCs powder is observed above 3.0 GPa. Furthermore, asymmetric and double-peak PL emissions are obtained from a concentrated solution of CdTe NCs under hydrostatic pressure, implying the feasibility of pressure-induced interparticle coupling.

The influence of conjugated alkynyl(aryl) surface groups on the optical properties of silicon nanocrystals: photoluminescence through in-gap states.

PubMed

Angı, Arzu; Sinelnikov, Regina; Heenen, Hendrik H; Meldrum, Al; Veinot, Jonathan G C; Scheurer, Christoph; Reuter, Karsten; Ashkenazy, Or; Azulay, Doron; Balberg, Isaac; Millo, Oded; Rieger, Bernhard

2018-08-31

Developing new methods, other than size and shape, for controlling the optoelectronic properties of semiconductor nanocrystals is a highly desired target. Here we demonstrate that the photoluminescence (PL) of silicon nanocrystals (SiNCs) can be tuned in the range 685-800 nm solely via surface functionalization with alkynyl(aryl) (phenylacetylene, 2-ethynylnaphthalene, 2-ethynyl-5-hexylthiophene) surface groups. Scanning tunneling microscopy/spectroscopy on single nanocrystals revealed the formation of new in-gap states adjacent to the conduction band edge of the functionalized SiNCs. PL red-shifts were attributed to emission through these in-gap states, which reduce the effective band gap for the electron-hole recombination process. The observed in-gap states can be associated with new interface states formed via (-Si-C≡C-) bonds in combination with conjugated molecules as indicated by ab initio calculations. In contrast to alkynyl(aryl)s, the formation of in-gap states and shifts in PL maximum of the SiNCs were not observed with aryl (phenyl, naphthalene, 2-hexylthiophene) and alkynyl (1-dodecyne) surface groups. These outcomes show that surface functionalization with alkynyl(aryl) molecules is a valuable tool to control the electronic structure and optical properties of SiNCs via tuneable interface states, which may enhance the performance of SiNCs in semiconductor devices.

Dendrimer ligands-capped CH3NH3PbBr3 perovskite nanocrystals with delayed halide exchange and record stability against both moisture and water.

PubMed

Xu, Yiren; Xu, Shuhong; Shao, Haibao; Jiang, Han; Cui, Yiping; Wang, Chunlei

2018-06-08

CH 3 NH 3 PbBr 3 perovskite nanocrystals (NCs) suffer from poor stability because of their high sensitivity to environmental moisture and water. To solve this problem, previous works mainly focus on embedding perovskite NCs into water-resistant matrix to form large composites (size of microns or larger). As an alternative solution without serious changing of NC size, enhancing the stability of perovskite NCs themselves by ligand engineering is rarely reported. In this work, we used hyperbranched polyamidoamine (PAMAM) dendrimers with two different generations (G0 and G4) to synthesize CH 3 NH 3 PbBr 3 perovskite NCs with high photoluminescence (PL) quantum yields (QY) above 70% and a new record stability. A novel dendrimers generation-dependent stability of perovskite NCs was observed. The water-resistance time is 18 h (27 h) for perovskite NCs capped by G0 (G4) generation of PAMAM, which is 7 times (11 times) longer than that of traditional oleic acid-capped NCs. Similar PAMAM generation-related stability is also observed in moisture-resistance tests. The stability time against moisture is 500 h (800 h) for G0 (G4) generation of PAMAM-capped perovskite NCs, which is a new record stability time against moisture for CH 3 NH 3 PbBr 3 perovskite NCs. In addition, our results also indicate that PAMAM ligands outside perovskite NCs can dramatically slow down the speed of halide exchange. Even for the mixture of perovskite NCs with two different halide composition, the original luminescence properties of PAMAM-capped perovskite NCs can retain after mixing. In view of slow halide exchange speed, excellent water and moisture stability, PAMAM dendrimers-capped perovskite NCs and their mixture are available as color conversion single layer in fabrication of light-emitting diodes (LED).

Dendrimer ligands-capped CH3NH3PbBr3 perovskite nanocrystals with delayed halide exchange and record stability against both moisture and water

NASA Astrophysics Data System (ADS)

Xu, Yiren; Xu, Shuhong; Shao, Haibao; Jiang, Han; Cui, Yiping; Wang, Chunlei

2018-06-01

CH3NH3PbBr3 perovskite nanocrystals (NCs) suffer from poor stability because of their high sensitivity to environmental moisture and water. To solve this problem, previous works mainly focus on embedding perovskite NCs into water-resistant matrix to form large composites (size of microns or larger). As an alternative solution without serious changing of NC size, enhancing the stability of perovskite NCs themselves by ligand engineering is rarely reported. In this work, we used hyperbranched polyamidoamine (PAMAM) dendrimers with two different generations (G0 and G4) to synthesize CH3NH3PbBr3 perovskite NCs with high photoluminescence (PL) quantum yields (QY) above 70% and a new record stability. A novel dendrimers generation-dependent stability of perovskite NCs was observed. The water-resistance time is 18 h (27 h) for perovskite NCs capped by G0 (G4) generation of PAMAM, which is 7 times (11 times) longer than that of traditional oleic acid-capped NCs. Similar PAMAM generation-related stability is also observed in moisture-resistance tests. The stability time against moisture is 500 h (800 h) for G0 (G4) generation of PAMAM-capped perovskite NCs, which is a new record stability time against moisture for CH3NH3PbBr3 perovskite NCs. In addition, our results also indicate that PAMAM ligands outside perovskite NCs can dramatically slow down the speed of halide exchange. Even for the mixture of perovskite NCs with two different halide composition, the original luminescence properties of PAMAM-capped perovskite NCs can retain after mixing. In view of slow halide exchange speed, excellent water and moisture stability, PAMAM dendrimers-capped perovskite NCs and their mixture are available as color conversion single layer in fabrication of light-emitting diodes (LED).

Hybrid solar cells from MDMO-PPV and silicon nanocrystals.

PubMed

Liu, Chin-Yi; Kortshagen, Uwe R

2012-07-07

Solution-processed bulk heterojunction solar cells from silicon nanocrystals (Si NCs) and poly(3-hexylthiophene) (P3HT) have shown promising power conversion efficiencies. Here we report on an attempt to enhance the performance of Si NC-polymer hybrid solar cells by using poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) as a hole conductor, which is expected to yield a higher open circuit voltage than P3HT due to its lower highest occupied molecular orbital (HOMO). Bulk heterojunction solar cells consisting of 3-5 nm silicon nanocrystals (Si NCs) and poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) have been fabricated. The properties of the hybrid Si NC/MDMO-PPV devices were studied as a function of the Si NC/MDMO-PPV weight ratio. Cells of 58 wt% 3-5 nm Si NCs showed the best overall performance under simulated one-sun AM 1.5 global illumination (100 mW cm(-2)). Compared to composite films of Si NCs and poly(3-hexylthiophene), we indeed observed an improved open circuit voltage but a lower power conversion efficiency from the Si NC/MDMO-PPV devices. The lower efficiency of Si NC/MDMO-PPV is correlated to the lower hole mobility and narrower absorption spectrum of MDMO-PPV compared to P3HT.

Eu-doped ZnO-HfO2 hybrid nanocrystal-embedded low-loss glass-ceramic waveguides

NASA Astrophysics Data System (ADS)

Ghosh, Subhabrata; N, Shivakiran Bhaktha B.

2016-03-01

We report on the sol-gel fabrication, using a dip-coating technique, of low-loss Eu-doped 70SiO2 -(30-x) HfO2-xZnO (x = 2, 5, 7 and 10 mol%) ternary glass-ceramic planar waveguides. Transmission electron microscopy and grazing incident x-ray diffraction experiments confirm the controlled growth of hybrid nanocrystals with an average size of 3 nm-25 nm, composed of ZnO encapsulated by a thin layer of nanocrystalline HfO2, with an increase of ZnO concentration from x = 2 mol% to 10 mol% in the SiO2-HfO2 composite matrix. The effect of crystallization on the local environment of Eu ions, doped in the ZnO-HfO2 hybrid nanocrystal-embedded glass-ceramic matrix, is studied using photoluminescence spectra, wherein an intense mixed-valence state (divalent as well as trivalent) emission of Eu ions is observed. The existence of Eu2+ and Eu3+ in the SiO2-HfO2-ZnO ternary matrix is confirmed by x-ray photoelectron spectroscopy. Importantly, the Eu{}2+,3+-doped ternary waveguides exhibit low propagation losses (0.3 ± 0.2 dB cm-1 at 632.8 nm) and optical transparency in the visible region of the electromagnetic spectrum, which makes ZnO-HfO2 nanocrystal-embedded SiO2-HfO2-ZnO waveguides a viable candidate for the development of on-chip, active, integrated optical devices.

Shrinking of silicon nanocrystals embedded in an amorphous silicon oxide matrix during rapid thermal annealing in a forming gas atmosphere

NASA Astrophysics Data System (ADS)

van Sebille, M.; Fusi, A.; Xie, L.; Ali, H.; van Swaaij, R. A. C. M. M.; Leifer, K.; Zeman, M.

2016-09-01

We report the effect of hydrogen on the crystallization process of silicon nanocrystals embedded in a silicon oxide matrix. We show that hydrogen gas during annealing leads to a lower sub-band gap absorption, indicating passivation of defects created during annealing. Samples annealed in pure nitrogen show expected trends according to crystallization theory. Samples annealed in forming gas, however, deviate from this trend. Their crystallinity decreases for increased annealing time. Furthermore, we observe a decrease in the mean nanocrystal size and the size distribution broadens, indicating that hydrogen causes a size reduction of the silicon nanocrystals.

Energy and charge transfer dynamics between Alq3 and CdSeS nanocrystals.

PubMed

Zhang, Shuping; Liu, Yuqiang; Yang, Yanqiang

2010-03-01

The photoluminescence properties of the blend films consisting of organic small molecules and nanocrystals (NCs)--Alq3 and CdSeS NCs--were studied by steady-state and time-resolved photoluminescence (PL) spectroscopy with different excited wavelengths. Both the fluorescence intensity and lifetime are intensively dependent on the NC concentration. The detailed analysis of experiment data proves that Forster energy transfer from the Alq3 to the NCs exists simultaneously with the charge transfer and both compete with each other in the blend films.

Quantum-dot light-emitting diodes utilizing CdSe /ZnS nanocrystals embedded in TiO2 thin film

NASA Astrophysics Data System (ADS)

Kang, Seung-Hee; Kumar, Ch. Kiran; Lee, Zonghoon; Kim, Kyung-Hyun; Huh, Chul; Kim, Eui-Tae

2008-11-01

Quantum-dot (QD) light-emitting diodes (LEDs) are demonstrated on Si wafers by embedding core-shell CdSe /ZnS nanocrystals in TiO2 thin films via plasma-enhanced metallorganic chemical vapor deposition. The n-TiO2/QDs /p-Si LED devices show typical p-n diode current-voltage and efficient electroluminescence characteristics, which are critically affected by the removal of QD surface ligands. The TiO2/QDs /Si system we presented can offer promising Si-based optoelectronic and electronic device applications utilizing numerous nanocrystals synthesized by colloidal solution chemistry.

Anomalous Suppression of Valley Splittings in Lead Salt Nanocrystals

NASA Astrophysics Data System (ADS)

Poddubny, Alexander; Nestoklon, Mikhail; Goupalov, Serguei

2012-02-01

Atomistic sp^3d^5s^* tight-binding theory of PbSe and PbS nanocrystals is developed. It is demonstrated, that the valley splittings of confined electrons and holes strongly and peculiarly depend on the geometry of a nanocrystal. When the nanocrystal lacks a microscopic center of inversion and has Td symmetry, the splittings are strongly suppressed as compared to the more symmetric nanocrystals with Oh symmetry, having an inversion center. This effect is quite unusual because typically a higher symmetry of a physical system implies a higher degeneracy of its energy levels, while in our case the suppression of the splittings occurs in NCs having lower symmetry. Nevertheless, we were able to explain this puzzling behavior using mathematical apparatus of the group theory.

A generalized ligand-exchange strategy enabling sequential surface functionalization of colloidal nanocrystals.

PubMed

Dong, Angang; Ye, Xingchen; Chen, Jun; Kang, Yijin; Gordon, Thomas; Kikkawa, James M; Murray, Christopher B

2011-02-02

The ability to engineer surface properties of nanocrystals (NCs) is important for various applications, as many of the physical and chemical properties of nanoscale materials are strongly affected by the surface chemistry. Here, we report a facile ligand-exchange approach, which enables sequential surface functionalization and phase transfer of colloidal NCs while preserving the NC size and shape. Nitrosonium tetrafluoroborate (NOBF4) is used to replace the original organic ligands attached to the NC surface, stabilizing the NCs in various polar, hydrophilic media such as N,N-dimethylformamide for years, with no observed aggregation or precipitation. This approach is applicable to various NCs (metal oxides, metals, semiconductors, and dielectrics) of different sizes and shapes. The hydrophilic NCs obtained can subsequently be further functionalized using a variety of capping molecules, imparting different surface functionalization to NCs depending on the molecules employed. Our work provides a versatile ligand-exchange strategy for NC surface functionalization and represents an important step toward controllably engineering the surface properties of NCs.

Enhanced red photoluminescence of quartz by silicon nanocrystals thin film deposition

NASA Astrophysics Data System (ADS)

Momeni, A.; Pourgolestani, M.; Taheri, M.; Mansour, N.

2018-03-01

The room-temperature photoluminescence properties of silicon nanocrystals (SiNCs) thin film on a quartz substrate were investigated, which presents the red emission enhancement of quartz. We show that the photoluminescence intensity of quartz, in the wavelength range of 640-700 nm, can be enhanced as much as 15-fold in the presence of the SiNCs thin film. Our results reveal that the defect states at the SiNCs/SiO2 interface can be excited more efficiently by indirect excitation via the SiNCs, leading to the prominent red photoluminescence enhancement under the photo-excitation in the range of 440-470 nm. This work suggests a simple pathway to improve silicon-based light emitting devices for photonic applications.

Colloidal nanocrystals for photoelectrochemical and photocatalytic water splitting

NASA Astrophysics Data System (ADS)

Gadiyar, Chethana; Loiudice, Anna; Buonsanti, Raffaella

2017-02-01

Colloidal nanocrystals (NCs) are among the most modular and versatile nanomaterial platforms for studying emerging phenomena in different fields thanks to their superb compositional and morphological tunability. A promising, yet challenging, application involves the use of colloidal NCs as light absorbers and electrocatalysts for water splitting. In this review we discuss how the tunability of these materials is ideal to understand the complex phenomena behind storing energy in chemical bonds and to optimize performance through structural and compositional modification. First, we describe the colloidal synthesis method as a means to achieve a high degree of control over single material NCs and NC heterostructures, including examples of the role of the ligands in modulating size and shape. Next, we focus on the use of NCs as light absorbers and catalysts to drive both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER), together with some of the challenges related to the use of colloidal NCs as model systems and/or technological solution in water splitting. We conclude with a broader prospective on the use of colloidal chemistry for new material discovery.

Transparent luminescent bulk nanocomposites of polysiloxane embedded with CdS nanocrystallines by a direct dispersion process.

PubMed

Shen, Zhu-Rui; Li, Ya-Li; Liu, Jian-Bin; Chen, Ming-Xia; Hou, Feng; Wang, Li-Qun

2012-03-07

Transparent luminescent bulk nanocomposites of polysiloxane (PSO) embedded with semiconductor nanocrystals (NCs) have been fabricated by the direct dispersion of CdS NCs in alkyl-(poly)siloxane (APS) followed by co-polymerization. The non-polar characteristics of the APS precursor are compatible with the CdS NC surface (oleylamine), which allows the direct dispersion of the CdS NCs without the need of any surfactant exchange. Chemical crosslinking of the NC-APS dispersion via hydrosilylation between Si-H and the vinyl group in APS immobilizes the CdS NCs in the polysiloxane network. Net-shaped three-dimensional bulk transparent polysiloxane/CdS NC composites were obtained by liquid casting of the NC-precursor dispersion and chemical crosslinking. The PSO/CdS NC composites show visible luminescence under ultraviolet excitation and the luminescent color is tunable from blue to red by controlling the NC concentration in the composite. Photoluminescence spectral analyses reveal the origin of the luminescence as being from the defect emission of the CdS NCs (550-900 nm) and an emission from the PSO matrix (380-550 nm). The luminescent spectra covered a wide range from the ultraviolet to the near-infrared region. The luminescence of the PSO/CdS NC nanocomposites was stable without any apparent degradation after exposure to air for a long time. This simple direct dispersion process is feasible for the fabrication of luminescent nanocomposites with useful optical properties for potential applications in optics and photoelectron devices.

A novel approach for the fabrication of all-inorganic nanocrystal solids: Semiconductor matrix encapsulated nanocrystal arrays

NASA Astrophysics Data System (ADS)

Moroz, Pavel

Growing fossil fuels consumption compels researchers to find new alternative pathways to produce energy. Along with new materials for the conversion of different types of energy into electricity innovative methods for efficient processing of energy sources are also introduced. The main criteria for the success of such materials and methods are the low cost and compelling performance. Among different types of materials semiconductor nanocrystals are considered as promising candidates for the role of the efficient and cheap absorbers for solar energy applications. In addition to the anticipated cost reduction, the integration of nanocrystals (NC) into device architectures is inspired by the possibility of tuning the energy of electrical charges in NCs via nanoparticle size. However, the stability of nanocrystals in photovoltaic devices is limited by the stability of organic ligands which passivate the surface of semiconductors to preserve quantum confinement. The present work introduces a new strategy for low-temperature processing of colloidal nanocrystals into all-inorganic films: semiconductor matrix encapsulated nanocrystal arrays (SMENA). This methodology goes beyond the traditional ligand-interlinking scheme and relies on the encapsulation of morphologically-defined nanocrystal arrays into a matrix of a wide-band gap semiconductor, which preserves optoelectronic properties of individual nanoparticles. Fabricated solids exhibit excellent thermal stability, which is attributed to the heteroepitaxial structure of nanocrystal-matrix interfaces. The main characteristics and properties of these solids were investigated and compared with ones of traditionally fabricated nanocrystal films using standard spectroscopic, optoelectronic and electronic techniques. As a proof of concept, we. We also characterized electron transport phenomena in different types of nanocrystal films using all-optical approach. By measuring excited carrier lifetimes in either ligand-linked or

Silk fibroin/gold nanocrystals: a new example of biopolymer-based nanocomposites

NASA Astrophysics Data System (ADS)

Noinville, S.; Garnier, A.; Courty, A.

2017-05-01

The dispersion of nanoparticles in ordered polymer nanostructures can provide control over particle location and orientation, and pave the way for tailored nanomaterials that have enhanced mechanical, electrical, or optical properties. Here we used silk fibroin, a natural biopolymer, to embed gold nanocrystals (NCs), so as to obtain well-ordered structures such as nanowires and self-assembled triangular nanocomposites. Monodisperse gold NCs synthesized in organic media are mixed to silk fibroin and the obtained nanocomposites are characterized by UV-visible spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (FE-SEM), atomic force microscopy (AFM) and Infrared spectroscopy. The optical properties study of gold NCs and silk-gold nanocomposites shows that the Surface Plasmon band is blue shifted compared to gold NCs. The size and shape of NCs gold superlattices can be well controlled by the presence of silk fibroin giving nanowires and also self-assembled triangular nanocomposites as characterized by TEM, FE-SEM and AFM. The strong interaction between gold NCs and silk fibroin is also revealed by the conformation change of silk protein in presence of gold NCs, as shown by FTIR analysis. The formation of such ordered nanocomposites (gold NCs/silk fibroin) will provide new nanoplasmonic devices.

Effect of protons on the redox chemistry of colloidal zinc oxide nanocrystals.

PubMed

Valdez, Carolyn N; Braten, Miles; Soria, Ashley; Gamelin, Daniel R; Mayer, James M

2013-06-12

Electron transfer (ET) reactions of colloidal 3-5 nm diameter ZnO nanocrystals (NCs) with molecular reagents are explored in aprotic solvents. Addition of an excess of the one-electron reductant Cp*2Co (Cp* = pentamethylcyclopentadienyl) gives NCs that are reduced by up to 1-3 electrons per NC. Protons can be added stoichiometrically to the NCs by either a photoreduction/oxidation sequence or by addition of acid. The added protons facilitate the reduction of the ZnO NCs. In the presence of acid, NC reduction by Cp*2Co can be increased to over 15 electrons per NC. The weaker reductant Cp*2Cr transfers electrons only to ZnO NCs in the presence of protons. Cp*2M(+) counterions are much less effective than protons at stabilizing reduced NCs. With excess Cp*2Co or Cp*2Cr, the extent of reduction increases roughly linearly with the number of protons added. Some of the challenges in understanding these results are discussed.

Enhanced biostability and cellular uptake of zinc oxide nanocrystals shielded with a phospholipid bilayer.

PubMed

Dumontel, B; Canta, M; Engelke, H; Chiodoni, A; Racca, L; Ancona, A; Limongi, T; Canavese, G; Cauda, V

2017-11-28

The widespread use of ZnO nanomaterials for biomedical applications, including therapeutic drug delivery or stimuli-responsive activation, as well as imaging, imposes a careful control over the colloidal stability and long-term behaviour of ZnO in biological media. Moreover, the effect of ZnO nanostructures on living cells, in particular cancer cells, is still under debate. This paper discusses the role of surface chemistry and charge of zinc oxide nanocrystals, of around 15 nm in size, which influence their behaviour in biological fluids and effect on cancer cells. In particular, we address this problem by modifying the surface of pristine ZnO nanocrystals (NCs), rich of hydroxyl groups, with positively charged amino-propyl chains or, more innovatively, by self-assembling a double-lipidic membrane, shielding the ZnO NCs. Our findings show that the prolonged immersion in simulated human plasma and in the cell culture medium leads to highly colloidally dispersed ZnO NCs only when coated by the lipidic bilayer. In contrast, the pristine and amine-functionalized NCs form huge aggregates after already one hour of immersion. Partial dissolution of these two samples into potentially cytotoxic Zn 2+ cations takes place, together with the precipitation of phosphate and carbonate salts on the NCs' surface. When exposed to living HeLa cancer cells, higher amounts of lipid-shielded ZnO NCs are internalized with respect to the other samples, thus showing a reduced cytotoxicity, based on the same amount of internalized NCs. These results pave the way for the development of novel theranostic platforms based on ZnO NCs. The new formulation of ZnO shielded with a lipid-bilayer will prevent strong aggregation and premature degradation into toxic by-products, and promote a highly efficient cell uptake for further therapeutic or diagnostic functions.

Preparation of nanocrystals and nanocomposites of nanocrystal-conjugated polymer, and their photophysical properties in confined geometries

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

Xu, Jun

2007-01-01

Semiconductors nanocrystals (NCs), also called quantum dots (QDs), have attracted tremendous interest over the past decade in the fields of physics, chemistry, and engineering. Due to the quantum-confined nature of QDs, the variation of particle size provides continuous and predictable changes in fluorescence emission. On the other hand, conjugated polymers (CPs) have been extensively studied for two decades due to their semiconductor-like optical and electronic properties. The electron and energy transfer between NCs and CPs occur in solar cells and light emitting diodes (LEDs), respectively. Placing CPs in direct contact with a NC (i.e., preparing NC-CP nanocomposites) carries advantage overmore » cases where NC aggregation dominates. Such NC-CP nanocomposites possess a well-defined interface that significantly promotes the charge or energy transfer between these two components. However, very few studies have centered on such direct integration. We prepared NCs and NC-CP nanocomposites based on heck coupling and investigated the energy and charge transfer between semiconductor NCs (i.e., CdSe QDs), CPs (i.e., poly(3-hexyl thiophene) (P3HT)) in the nanocomposites in confined geometries. Two novel strategies were used to confine NC and/or NC-CP nanocomposites: (a) directly immobilizing nanohybrids, QDs and nanorods in nanoscopic porous alumina membrane (PAM) , and (b) confining the QDs and CPs in sphere-on-flat geometry to induce self-assembly. While investigating the confinement effect, gradient concentric ring patterns of high regularity form spontaneously simply by allowing a droplet of solution containing either conjugated polymer or semiconductor nanocrystal in a consecutive stick-slip mothion in a confined geometry. Such constrained evaporation can be utilized as a simple, cheap, and robust strategy for self-assembling various materials with easily tailored optical and electronic properties into spatially ordered, two-dimensional patterns. These self

Size Dependence of Doping by a Vacancy Formation Reaction in Copper Sulfide Nanocrystals

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

Elimelech, Orian; Liu, Jing; Plonka, Anna M.

Doping of nanocrystals (NCs) is a key, yet underexplored, approach for tuning of the electronic properties of semiconductors. An important route for doping of NCs is by vacancy formation. The size and concentration dependence of doping was studied in copper(I) sulfide (Cu2S) NCs through a redox reaction with iodine molecules (I2), which formed vacancies accompanied by a localized surface plasmon response. X-ray spectroscopy and diffraction reveal transformation from Cu2S to Cu-depleted phases, along with CuI formation. Greater reaction efficiency was observed for larger NCs. This behavior is attributed to interplay of the vacancy formation energy, which decreases for smaller sizedmore » NCs, and the growth of CuI on the NC surface, which is favored on well-defined facets of larger NCs. This doping process allows tuning of the plasmonic properties of a semiconductor across a wide range of plasmonic frequencies by varying the size of NCs and the concentration of iodine. Controlled vacancy doping of NCs may be used to tune and tailor semiconductors for use in optoelectronic applications.« less

Diazonium salts as grafting agents and efficient radical-hydrosilylation initiators for freestanding photoluminescent silicon nanocrystals.

PubMed

Höhlein, Ignaz M D; Kehrle, Julian; Helbich, Tobias; Yang, Zhenyu; Veinot, Jonathan G C; Rieger, Bernhard

2014-04-07

The reactivity of diazonium salts towards freestanding, photoluminescent silicon nanocrystals (SiNCs) is reported. It was found that SiNCs can be functionalized with aryl groups by direct reductive grafting of the diazonium salts. Furthermore, diazonium salts are efficient radical initiators for SiNC hydrosilylation. For this purpose, novel electron-deficient diazonium salts, highly soluble in nonpolar solvents were synthesized. The SiNCs were functionalized with a variety of alkenes and alkynes at room temperature with short reaction times. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Role of the inversion layer on the charge injection in silicon nanocrystal multilayered light emitting devices

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

Tondini, S.; Dipartimento di Fisica, Informatica e Matematica, Università di Modena e Reggio Emilia, Via Campi 213/a, 41125 Modena; Pucker, G.

2016-09-07

The role of the inversion layer on injection and recombination phenomena in light emitting diodes (LEDs) is here studied on a multilayer (ML) structure of silicon nanocrystals (Si-NCs) embedded in SiO{sub 2}. Two Si-NC LEDs, which are similar for the active material but different in the fabrication process, elucidate the role of the non-radiative recombination rates at the ML/substrate interface. By studying current- and capacitance-voltage characteristics as well as electroluminescence spectra and time-resolved electroluminescence under pulsed and alternating bias pumping scheme in both the devices, we are able to ascribe the different experimental results to an efficient or inefficient minoritymore » carrier (electron) supply by the p-type substrate in the metal oxide semiconductor LEDs.« less

Synthesis and characterization of colloidal CdTe nanocrystals

NASA Astrophysics Data System (ADS)

Semendy, Fred; Jaganathan, Gomatam; Dhar, Nibir; Trivedi, Sudhir; Bhat, Ishwara; Chen, Yuanping

2008-08-01

We synthesized CdTe nano crystals (NCs) in uniform sizes and in good quality as characterized by photoluminescence (PL), AFM, and X-ray diffraction. In this growth procedure, CdTe nano-crystal band gap is strongly dependent on the growth time and not on the injection temperature or organic ligand concentration. This is very attractive because of nano-crystal size can be easily controlled by the growth time only and is very attractive for large scale synthesis. The color of the solution changes from greenish yellow to light orange then to deep orange and finally grayish black to black over a period of one hour. This is a clear indication of the gradual growth of different size (and different band gap) of CdTe nano-crystals as a function of the growth time. In other words, the size of the nano-crystal and its band gap can be controlled by adjusting the growth time after injection of the tellurium. The prepared CdTe NCs were characterized by absorption spectra, photoluminescence (PL), AFM and X-ray diffraction. Measured absorption maxima are at 521, 560, 600 and 603 nm corresponding to band gaps of 2.38, 2.21,2,07 and 2.04 eV respectively for growth times of 15, 30, 45 and 60 minutes. From the absorption data nano-crystal growth size saturates out after 45 minutes. AFM scanning of these materials indicate that the size of these particles is between 4 - 10 nm in diameter for growth time of 45 minutes. XD-ray diffraction indicates that these nano crystals are of cubic zinc blende phase. This paper will present growth and characterization data on CdTe nano crystals for various growth times.

Ligand induced shape transformation of thorium dioxide nanocrystals.

PubMed

Wang, Gaoxue; Batista, Enrique R; Yang, Ping

2018-04-27

Nanocrystals (NCs) with size and shape dependent properties are a thriving research field. Remarkable progress has been made in the controlled synthesis of NCs of stable elements in the past two decades; however, the knowledge of the NCs of actinide compounds has been considerably limited due the difficulties in handling them both experimentally and theoretically. Actinide compounds, especially actinide oxides, play a critical role in many stages of the nuclear fuel cycle. Recently, a non-aqueous surfactant assisted approach has been developed for the synthesis of actinide oxide NCs with different morphologies, but an understanding of its control factors is still missing to date. Herein we present a comprehensive study on the low index surfaces of thorium dioxide (ThO2) and their interactions with relevant surfactant ligands using density functional calculations. A systematic picture on the thermodynamic stability of ThO2 NCs of different sizes and shapes is obtained employing empirical models based on the calculated surface energies. It is found that bare ThO2 NCs prefer the octahedral shape terminated by (111) surfaces. Oleic acid displays selective adsorption on the (110) surface, leading to the shape transformation from octahedrons to nanorods. Other ligands such as acetylacetone, oleylamine, and trioctylphosphine oxide do not modify the equilibrium shape of ThO2 NCs. This work provides atomic level insights into the anisotropic growth of ThO2 NCs that was recently observed in experiments, and thus may contribute to the controlled synthesis of actinide oxide NCs with well-defined size and shape for future applications.

Pt Single Atoms Embedded in the Surface of Ni Nanocrystals as Highly Active Catalysts for Selective Hydrogenation of Nitro Compounds.

PubMed

Peng, Yuhan; Geng, Zhigang; Zhao, Songtao; Wang, Liangbing; Li, Hongliang; Wang, Xu; Zheng, Xusheng; Zhu, Junfa; Li, Zhenyu; Si, Rui; Zeng, Jie

2018-06-13

Single-atom catalysts exhibit high selectivity in hydrogenation due to their isolated active sites, which ensure uniform adsorption configurations of substrate molecules. Compared with the achievement in catalytic selectivity, there is still a long way to go in exploiting the catalytic activity of single-atom catalysts. Herein, we developed highly active and selective catalysts in selective hydrogenation by embedding Pt single atoms in the surface of Ni nanocrystals (denoted as Pt 1 /Ni nanocrystals). During the hydrogenation of 3-nitrostyrene, the TOF numbers based on surface Pt atoms of Pt 1 /Ni nanocrystals reached ∼1800 h -1 under 3 atm of H 2 at 40 °C, much higher than that of Pt single atoms supported on active carbon, TiO 2 , SiO 2 , and ZSM-5. Mechanistic studies reveal that the remarkable activity of Pt 1 /Ni nanocrystals derived from sufficient hydrogen supply because of spontaneous dissociation of H 2 on both Pt and Ni atoms as well as facile diffusion of H atoms on Pt 1 /Ni nanocrystals. Moreover, the ensemble composed of the Pt single atom and nearby Ni atoms in Pt 1 /Ni nanocrystals leads to the adsorption configuration of 3-nitrostyrene favorable for the activation of nitro groups, accounting for the high selectivity for 3-vinylaniline.

Direct printing of microstructures by femtosecond laser excitation of nanocrystals in solution

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

Shou, Wan; Pan, Heng, E-mail: hp5c7@mst.edu

2016-05-23

We report direct printing of micro/sub-micron structures by femtosecond laser excitation of semiconductor nanocrystals (NCs) in solution. Laser excitation with moderate intensity (10{sup 11}–10{sup 12} W/cm{sup 2}) induces 2D and 3D deposition of CdTe nanocrystals in aqueous solution, which can be applied for direct printing of microstructures. It is believed that laser irradiation induces charge formation on nanocrystals leading to deposition. Furthermore, it is demonstrated that the charged nanocrystals can respond to external electrical bias, enabling a printing approach based on selective laser induced electrophoretic deposition. Finally, energy dispersive X-ray analysis of deposited structures shows oxidation occurs and deposited structure mainlymore » consists of Cd{sub x}O.« less

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.

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.

Doped silicon nanocrystals from organic dopant precursor by a SiCl4-based high frequency nonthermal plasma

NASA Astrophysics Data System (ADS)

Zhou, Shu; Ding, Yi; Pi, Xiaodong; Nozaki, Tomohiro

2014-11-01

Doped silicon nanocrystals (Si NCs) are of great interest in demanding low-cost nanodevices because of the abundance and nontoxicity of Si. Here, we demonstrate a cost-effective gas phase approach to synthesize phosphorous (P)-doped Si NCs in which the precursors used, i.e., SiCl4, trimethyl phosphite (TMP), are both safe and economical. It is found that the TMP-enabled P-doping does not change the crystalline structure of Si NCs. The surface of P-doped Si NCs is terminated by both Cl and H. The Si-H bond density at the surface of P-doped Si NCs is found to be much higher than that of undoped Si NCs. The X-ray photoelectron spectroscopy and electron spin resonance results indicate that P atoms are doped into the substitutional sites of the Si-NC core and electrically active in Si NCs. Unintentional impurities, such as carbon contained in TMP, are not introduced into Si NCs.

Understanding and Curing Structural Defects in Colloidal GaAs Nanocrystals

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

Srivastava, Vishwas; Liu, Wenyong; Janke, Eric M.

2017-02-22

Nearly three decades since the first report on the synthesis of colloidal GaAs nanocrystals (NCs), the preparation and properties of this material remain highly controversial. Traditional synthetic routes either fail to produce the GaAs phase or result in materials that do not show expected optical properties such as excitonic transitions. In this work, we demonstrate a variety of synthetic routes toward crystalline GaAs NCs. By using a combination of Raman, EXAFS and transient absorption spectroscopies, we conclude that unusual optical properties of 2 colloidal GaAs NCs can be related to the presence of vacancies and lattice disorder. We introduce novelmore » molten salt based annealing approach to alleviate these structural defects and show the emergence of size-dependent excitonic transitions in colloidal GaAs quantum dots.« less

Nanocrystal doped matrixes

DOEpatents

Parce, J. Wallace; Bernatis, Paul; Dubrow, Robert; Freeman, William P.; Gamoras, Joel; Kan, Shihai; Meisel, Andreas; Qian, Baixin; Whiteford, Jeffery A.; Ziebarth, Jonathan

2010-01-12

Matrixes doped with semiconductor nanocrystals are provided. In certain embodiments, the semiconductor nanocrystals have a size and composition such that they absorb or emit light at particular wavelengths. The nanocrystals can comprise ligands that allow for mixing with various matrix materials, including polymers, such that a minimal portion of light is scattered by the matrixes. The matrixes of the present invention can also be utilized in refractive index matching applications. In other embodiments, semiconductor nanocrystals are embedded within matrixes to form a nanocrystal density gradient, thereby creating an effective refractive index gradient. The matrixes of the present invention can also be used as filters and antireflective coatings on optical devices and as down-converting layers. Processes for producing matrixes comprising semiconductor nanocrystals are also provided. Nanostructures having high quantum efficiency, small size, and/or a narrow size distribution are also described, as are methods of producing indium phosphide nanostructures and core-shell nanostructures with Group II-VI shells.

Crystal that remembers: several ways to utilize nanocrystals in resistive switching memory

NASA Astrophysics Data System (ADS)

Banerjee, Writam; Liu, Qi; Long, Shibing; Lv, Hangbing; Liu, Ming

2017-08-01

The attractive usability of quantum phenomena in futuristic devices is possible by using zero-dimensional systems like nanocrystals (NCs). The performance of nonvolatile flash memory devices has greatly benefited from the use of NCs over recent decades. The quantum abilities of NCs have been used to improve the reliability of flash devices. Its appeal is extended to the design of emerging devices such as resistive random-access memory (RRAM), a technology where the use of silicon is optional. Here, we are going to review the recent progress in the design, characterization, and utilization of NCs in RRAM devices. We will first introduce the physical design of the RRAM devices using NCs and the improvement of electrical performance in NC-RRAM over conventional ones. In particular, special care has been taken to review the ways of development provided by the NCs in the RRAM devices. In a broad sense, the NCs can play a charge trapping role in the NC-RRAM structure or it can be responsible for the localization and improvement of the stability of the conductive filament or it can play a part in the formation of the conductive filament chain by the NC migration under applied bias. Finally, the scope of NCs in the RRAM devices has also been discussed.

Charge Trapping Properties of Ge Nanocrystals Grown via Solid-State Dewetting

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

Johnston, Steven; Jadli, I.; Aouassa, M.

2018-05-04

In the present work, we report on the charge trapping properties of Germanium Nanocrystals (Ge NCs) self assembled on SiO2 thin layer for promising applications in next-generation non volatile memory by the means of Deep Level Transient Spectroscopy (DLTS) and high frequency C-V method. The Ge NCs were grown via dewetting phenomenon at solid state by Ultra-High Vacuum (UHV) annealing and passivated with silicon before SiO2 capping. The role of the surface passivation is to reduce the electrical defect density at the Ge NCs-SiO2 interface. The presence of the Ge NCs in the oxide of the MOS capacitors strongly affectsmore » the C-V characteristics and increases the accumulation capacitance, causes a negative flat band voltage (VFB) shift. The DLTS has been used to study the individual Ge NCs as a single point deep level defect in the oxide. DLTS reveals two main features: the first electron traps around 255 K could correspond to dangling bonds at the Si/SiO2 interface and the second, at high-temperature (>300 K) response, could be originated from minority carrier generation in Ge NCs.« less

Graphene enhanced field emission from InP nanocrystals.

PubMed

Iemmo, L; Di Bartolomeo, A; Giubileo, F; Luongo, G; Passacantando, M; Niu, G; Hatami, F; Skibitzki, O; Schroeder, T

2017-12-08

We report the observation of field emission (FE) from InP nanocrystals (NCs) epitaxially grown on an array of p-Si nanotips. We prove that FE can be enhanced by covering the InP NCs with graphene. The measurements are performed inside a scanning electron microscope chamber with a nano-controlled W-thread used as an anode. We analyze the FE by Fowler-Nordheim theory and find that the field enhancement factor increases monotonically with the spacing between the anode and the cathode. We also show that InP/p-Si junction has a rectifying behavior, while graphene on InP creates an ohmic contact. Understanding the fundamentals of such nanojunctions is key for applications in nanoelectronics.

Graphene enhanced field emission from InP nanocrystals

NASA Astrophysics Data System (ADS)

Iemmo, L.; Di Bartolomeo, A.; Giubileo, F.; Luongo, G.; Passacantando, M.; Niu, G.; Hatami, F.; Skibitzki, O.; Schroeder, T.

2017-12-01

We report the observation of field emission (FE) from InP nanocrystals (NCs) epitaxially grown on an array of p-Si nanotips. We prove that FE can be enhanced by covering the InP NCs with graphene. The measurements are performed inside a scanning electron microscope chamber with a nano-controlled W-thread used as an anode. We analyze the FE by Fowler-Nordheim theory and find that the field enhancement factor increases monotonically with the spacing between the anode and the cathode. We also show that InP/p-Si junction has a rectifying behavior, while graphene on InP creates an ohmic contact. Understanding the fundamentals of such nanojunctions is key for applications in nanoelectronics.

Crystalline phase transformation of colloidal cadmium sulfide nanocrystals

NASA Astrophysics Data System (ADS)

Ghali, M.; Eissa, A. M.; Mosaad, M. M.

2017-03-01

In this paper, we give a microscopic view concerning influence of the growth conditions on the physical properties of nanocrystals (NCs) thin films made of CdS, prepared using chemical bath deposition CBD technique. We show a crystalline phase transformation of CdS NCs from hexagonal wurtzite (W) structure to cubic zincblende (ZB) when the growth conditions change, particularly the solution pH values. This effect was confirmed using X-ray diffraction (XRD), transmission electron microscopy (TEM), optical absorption and photoluminescence (PL) measurements. The optical absorption spectra allow calculation of the bandgap value, Eg, where significant increase ˜200 meV in the CdS bandgap when transforming from Hexagonal to Cubic phase was found.

Au–CsPbBr 3 Hybrid Architecture: Anchoring Gold Nanoparticles on Cubic Perovskite Nanocrystals

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

Balakrishnan, Subila K.; Kamat, Prashant V.

A selective growth of gold (Au) nanoparticles on the corners of CsPbBr 3 nanocrystals (NCs) is made possible with the treatment of Au(III) salts such as Au(III) bromide and Au(III) chloride in solution. The surface bound oleylamine ligands not only stabilize NCs but also facilitate reduction of the Au(III) salts followed by nucleation of the Au nanoparticles on the corners of the perovskite NCs. The luminescence quantum yield of NCs is decreased when Au nanoparticles are formed on the corners of CsPbBr 3 NCs, suggesting interaction between the two systems. Formation of Au nanoparticles as well as an anion exchangemore » is seen when Au(III) bromide was replaced with Au(III) chloride as a precursor. This simple strategy of designing perovskite-gold hybrid nanostructures with good colloidal stability offers new opportunities to explore their photocatalytic properties.« less

Au–CsPbBr 3 Hybrid Architecture: Anchoring Gold Nanoparticles on Cubic Perovskite Nanocrystals

DOE PAGES

Balakrishnan, Subila K.; Kamat, Prashant V.

2016-11-29

A selective growth of gold (Au) nanoparticles on the corners of CsPbBr 3 nanocrystals (NCs) is made possible with the treatment of Au(III) salts such as Au(III) bromide and Au(III) chloride in solution. The surface bound oleylamine ligands not only stabilize NCs but also facilitate reduction of the Au(III) salts followed by nucleation of the Au nanoparticles on the corners of the perovskite NCs. The luminescence quantum yield of NCs is decreased when Au nanoparticles are formed on the corners of CsPbBr 3 NCs, suggesting interaction between the two systems. Formation of Au nanoparticles as well as an anion exchangemore » is seen when Au(III) bromide was replaced with Au(III) chloride as a precursor. This simple strategy of designing perovskite-gold hybrid nanostructures with good colloidal stability offers new opportunities to explore their photocatalytic properties.« less

Morphology-dependent low-frequency Raman scattering in ultrathin spherical, cubic, and cuboid SnO2 nanocrystals

NASA Astrophysics Data System (ADS)

Liu, L. Z.; Wu, X. L.; Li, T. H.; Xiong, S. J.; Chen, H. T.; Chu, Paul K.

2011-12-01

Nanoscale spherical, cubic, and cuboid SnO2 nanocrystals (NCs) are used to investigate morphology-dependent low-frequency Raman scattering. A double-peak structure in which the linewidths and energy separation between two subpeaks decrease with increasing sizes of cuboid NCs is observed and attributed to the surface acoustic phonon modes confined in three dimensional directions and determined by the surface/interface compositions. The decrease in energy separation is due to weaker coupling between the acoustic modes in different vibration directions. Our experimental and theoretical studies clearly disclose the morphology-dependent surface vibrational behavior in self-assembled NCs.

Evaluation of in vitro cytotoxicity, biocompatibility, and changes in the expression of apoptosis regulatory proteins induced by cerium oxide nanocrystals

NASA Astrophysics Data System (ADS)

Khan, Shahanavaj; Ansari, Anees A.; Rolfo, Christian; Coelho, Andreia; Abdulla, Maha; Al-Khayal, Khayal; Ahmad, Rehan

2017-12-01

Cerium oxide nanocrystals (CeO2-NCs) exhibit superoxide dismutase and catalase mimetic activities. Based on these catalytic activities, CeO2-NCs have been suggested to have the potential to treat various diseases. The crystalline size of these materials is an important factor that influences the performance of CeO2-NCs. Previous reports have shown that several metal-based nanocrystals, including CeO2-NCs, can induce cytotoxicity in cancer cells. However, the underlying mechanisms have remained unclear. To characterize the anticancer activities of CeO2-NCs, several assays related to the mechanism of cytotoxicity and induction of apoptosis has been performed. Here, we have carried out a systematic study to characterize CeO2-NCs phase purity (X-ray diffraction), morphology (electron microscopy), and optical features (optical absorption, Raman scattering, and photoluminescence) to better establish their potential as anticancer drugs. Our study revealed anticancer effects of CeO2-NCs in HT29 and SW620 colorectal cancer cell lines with half-maximal inhibitory concentration (IC50) values of 2.26 and 121.18 μg ml-1, respectively. Reductions in cell viability indicated the cytotoxic potential of CeO2-NCs in HT29 cells based on inverted and florescence microscopy assessments. The mechanism of cytotoxicity confirmed by estimating possible changes in the expression levels of Bcl2, BclxL, Bax, PARP, cytochrome c, and β-actin (control) proteins in HT29 cells. Down-regulation of Bcl2 and BclxL and up-regulation of Bax, PARP, and cytochrome c proteins suggested the significant involvement of CeO2-NCs exposure in the induction of apoptosis. Furthermore, biocompatibility assay showed minimum effect of CeO2-NCs on human red blood cells.

Host-guest chemistry for tuning colloidal solubility, self-organization and photoconductivity of inorganic-capped nanocrystals

NASA Astrophysics Data System (ADS)

Bodnarchuk, Maryna I.; Yakunin, Sergii; Piveteau, Laura; Kovalenko, Maksym V.

2015-12-01

Colloidal inorganic nanocrystals (NCs), functionalized with inorganic capping ligands, such as metal chalcogenide complexes (MCCs), have recently emerged as versatile optoelectronic materials. As-prepared, highly charged MCC-capped NCs are dispersible only in highly polar solvents, and lack the ability to form long-range ordered NC superlattices. Here we report a simple and general methodology, based on host-guest coordination of MCC-capped NCs with macrocyclic ethers (crown ethers and cryptands), enabling the solubilization of inorganic-capped NCs in solvents of any polarity and improving the ability to form NC superlattices. The corona of organic molecules can also serve as a convenient knob for the fine adjustment of charge transport and photoconductivity in films of NCs. In particular, high-infrared-photon detectivities of up to 3.3 × 1011 Jones with a fast response (3 dB cut-off at 3 kHz) at the wavelength of 1,200 nm were obtained with films of PbS/K3AsS4/decyl-18-crown-6 NCs.

Colloidal Inorganic Nanocrystal Based Nanocomposites: Functional Materials for Micro and Nanofabrication

PubMed Central

Ingrosso, Chiara; Panniello, AnnaMaria; Comparelli, Roberto; Curri, Maria Lucia; Striccoli, Marinella

2010-01-01

The unique size- and shape-dependent electronic properties of nanocrystals (NCs) make them extremely attractive as novel structural building blocks for constructing a new generation of innovative materials and solid-state devices. Recent advances in material chemistry has allowed the synthesis of colloidal NCs with a wide range of compositions, with a precise control on size, shape and uniformity as well as specific surface chemistry. By incorporating such nanostructures in polymers, mesoscopic materials can be achieved and their properties engineered by choosing NCs differing in size and/or composition, properly tuning the interaction between NCs and surrounding environment. In this contribution, different approaches will be presented as effective opportunities for conveying colloidal NC properties to nanocomposite materials for micro and nanofabrication. Patterning of such nanocomposites either by conventional lithographic techniques and emerging patterning tools, such as ink jet printing and nanoimprint lithography, will be illustrated, pointing out their technological impact on developing new optoelectronic and sensing devices.

Doping Lanthanide into Perovskite Nanocrystals: Highly Improved and Expanded Optical Properties.

PubMed

Pan, Gencai; Bai, Xue; Yang, Dongwen; Chen, Xu; Jing, Pengtao; Qu, Songnan; Zhang, Lijun; Zhou, Donglei; Zhu, Jinyang; Xu, Wen; Dong, Biao; Song, Hongwei

2017-12-13

Cesium lead halide (CsPbX 3 ) perovskite nanocrystals (NCs) have demonstrated extremely excellent optical properties and great application potentials in various optoelectronic devices. However, because of the anion exchange, it is difficult to achieve white-light and multicolor emission for practical applications. Herein, we present the successful doping of various lanthanide ions (Ce 3+ , Sm 3+ , Eu 3+ , Tb 3+ , Dy 3+ , Er 3+ , and Yb 3+ ) into the lattices of CsPbCl 3 perovskite NCs through a modified hot-injection method. For the lanthanide ions doped perovskite NCs, high photoluminescence quantum yield (QY) and stable and widely tunable multicolor emissions spanning from visible to near-infrared (NIR) regions are successfully obtained. This work indicates that the doped perovskite NCs will inherit most of the unique optical properties of lanthanide ions and deliver them to the perovskite NC host, thus endowing the family of perovskite materials with excellent optical, electric, or magnetic properties.

Solution-processed phase-change VO(2) metamaterials from colloidal vanadium oxide (VO(x)) nanocrystals.

PubMed

Paik, Taejong; Hong, Sung-Hoon; Gaulding, E Ashley; Caglayan, Humeyra; Gordon, Thomas R; Engheta, Nader; Kagan, Cherie R; Murray, Christopher B

2014-01-28

We demonstrate thermally switchable VO2 metamaterials fabricated using solution-processable colloidal nanocrystals (NCs). Vanadium oxide (VOx) NCs are synthesized through a nonhydrolytic reaction and deposited from stable colloidal dispersions to form NC thin films. Rapid thermal annealing transforms the VOx NC thin films into monoclinic, nanocrystalline VO2 thin films that show a sharp, reversible metal-insulator phase transition. Introduction of precise concentrations of tungsten dopings into the colloidal VOx NCs enables the still sharp phase transition of the VO2 thin films to be tuned to lower temperatures as the doping level increases. We fabricate "smart", differentially doped, multilayered VO2 films to program the phase and therefore the metal-insulator behavior of constituent vertically structured layers with temperature. With increasing temperature, we tailored the optical response of multilayered films in the near-IR and IR regions from that of a strong light absorber, in a metal-insulator structure, to that of a Drude-like reflector, characteristic of a pure metallic structure. We demonstrate that nanocrystal-based nanoimprinting can be employed to pattern multilayered subwavelength nanostructures, such as three-dimensional VO2 nanopillar arrays, that exhibit plasmonic dipolar responses tunable with a temperature change.

Colloidal CuInSe2 nanocrystals thin films of low surface roughness

NASA Astrophysics Data System (ADS)

de Kergommeaux, Antoine; Fiore, Angela; Faure-Vincent, Jérôme; Pron, Adam; Reiss, Peter

2013-03-01

Thin-film processing of colloidal semiconductor nanocrystals (NCs) is a prerequisite for their use in (opto-)electronic devices. The commonly used spin-coating is highly materials consuming as the overwhelming amount of deposited matter is ejected from the substrate during the spinning process. Also, the well-known dip-coating and drop-casting procedures present disadvantages in terms of the surface roughness and control of the film thickness. We show that the doctor blade technique is an efficient method for preparing nanocrystal films of controlled thickness and low surface roughness. In particular, by optimizing the deposition conditions, smooth and pinhole-free films of 11 nm CuInSe2 NCs have been obtained exhibiting a surface roughness of 13 nm root mean square (rms) for a 350 nm thick film, and less than 4 nm rms for a 75 nm thick film. Invited talk at the 6th International Workshop on Advanced Materials Science and Nanotechnology, 30 October-2 November 2012, Ha Long, Vietnam.

Probing surface states in PbS nanocrystal films using pentacene field effect transistors: controlling carrier concentration and charge transport in pentacene.

PubMed

Park, Byoungnam; Whitham, Kevin; Bian, Kaifu; Lim, Yee-Fun; Hanrath, Tobias

2014-12-21

We used a bilayer field effect transistor (FET) consisting of a thin PbS nanocrystals (NCs) film interfaced with vacuum-deposited pentacene to probe trap states in NCs. We interpret the observed threshold voltage shift in context of charge carrier trapping by PbS NCs and relate the magnitude of the threshold voltage shift to the number of trapped carriers. We explored a series of NC surface ligands to modify the interface between PbS NCs and pentacene and demonstrate the impact of interface chemistry on charge carrier density and the FET mobility in a pentacene FET.

Mn-doped Zinc Sulphide nanocrystals for immunofluorescent labeling of epidermal growth factor receptors on cells and clinical tumor tissues

NASA Astrophysics Data System (ADS)

J, Aswathy; V, Seethalekshmy N.; R, Hiran K.; R, Bindhu M.; K, Manzoor; Nair, Shantikumar V.; Menon, Deepthy

2014-11-01

The field of molecular detection and targeted imaging has evolved considerably with the introduction of fluorescent semiconductor nanocrystals. Manganese-doped zinc sulphide nanocrystals (ZnS:Mn NCs), which are widely used in electroluminescent displays, have been explored for the first time for direct immunofluorescent (IF) labeling of clinical tumor tissues. ZnS:Mn NCs developed through a facile wet chemistry route were capped using amino acid cysteine, conjugated to streptavidin and thereafter coupled to biotinylated epidermal growth factor receptor (EGFR) antibody utilizing the streptavidin-biotin linkage. The overall conjugation yielded stable EGFR antibody conjugated ZnS:Mn NCs (EGFR ZnS:Mn NCs) with a hydrodynamic diameter of 65 ± 15 nm, and having an intense orange-red fluorescence emission at 598 nm. Specific labeling of EGF receptors on EGFR+ve A431 cells in a co-culture with EGFR-ve NIH3T3 cells was demonstrated using these nanoprobes. The primary antibody conjugated fluorescent NCs could also clearly delineate EGFR over-expressing cells on clinical tumor tissues processed by formalin fixation as well as cryopreservation with a specificity of 86% and accuracy of 88%, in comparison to immunohistochemistry. Tumor tissues labeled with EGFR ZnS:Mn NCs showed good fluorescence emission when imaged after storage even at 15 months. Thus, ZnS nanobioconjugates with dopant-dependent and stable fluorescence emission show promise as an efficient, target-specific fluorophore that would enable long term IF labeling of any antigen of interest on clinical tissues.

Er3+ -doped anatase TiO2 nanocrystals: crystal-field levels, excited-state dynamics, upconversion, and defect luminescence.

PubMed

Luo, Wenqin; Fu, Chengyu; Li, Renfu; Liu, Yongsheng; Zhu, Haomiao; Chen, Xueyuan

2011-11-04

A comprehensive survey of electronic structure and optical properties of rare-earth ions embedded in semiconductor nanocrystals (NCs) is of vital importance for their potential applications in areas as diverse as luminescent bioprobes, lighting, and displays. Er3+ -doped anatase TiO2 NCs, synthesized via a facile sol-gel solvothermal method, exhibit intense and well-resolved intra-4f emissions of Er3+ . Crystal-field (CF) spectra of Er3+ in TiO2 NCs are systematically studied by means of high-resolution emission and excitation spectra at 10-300 K. The CF analysis of Er3+ assuming a site symmetry of C(2v) yields a small root-mean-square deviation of 25.1 cm(-1) and reveals the relatively large CF strength (549 cm(-1) ) of Er3+, thus verifying the rationality of the C(2v) symmetry assignment of Er3+ in anatase TiO2 NCs. Based on a simplified thermalization model for the temperature-dependent photoluminescence (PL) dynamics from (4) S(3/2) , the intrinsic radiative luminescence lifetimes of (4) S(3/2) and (2) H(11/2) are experimentally determined to be 3.70 and 1.73 μs, respectively. Green and red upconversion (UC) luminescence of Er3+ can be achieved upon laser excitation at 974.5 nm. The UC intensity of Er3+ in Yb/Er-codoped NCs is found to be about five times higher than that of Er-singly-doped counterparts as a result of efficient Yb3+ sensitization and energy transfer upconversion (ETU) evidenced by its distinct UC luminescence dynamics. Furthermore, the origin of defect luminescence is revealed based on the temperature-dependent PL spectra upon excitation above the TiO2 bandgap at 325 nm. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bidentate Ligand-Passivated CsPbI3 Perovskite Nanocrystals for Stable Near-Unity Photoluminescence Quantum Yield and Efficient Red Light-Emitting Diodes.

PubMed

Pan, Jun; Shang, Yuequn; Yin, Jun; De Bastiani, Michele; Peng, Wei; Dursun, Ibrahim; Sinatra, Lutfan; El-Zohry, Ahmed M; Hedhili, Mohamed N; Emwas, Abdul-Hamid; Mohammed, Omar F; Ning, Zhijun; Bakr, Osman M

2018-01-17

Although halide perovskite nanocrystals (NCs) are promising materials for optoelectronic devices, they suffer severely from chemical and phase instabilities. Moreover, the common capping ligands like oleic acid and oleylamine that encapsulate the NCs will form an insulating layer, precluding their utility in optoelectronic devices. To overcome these limitations, we develop a postsynthesis passivation process for CsPbI 3 NCs by using a bidentate ligand, namely 2,2'-iminodibenzoic acid. Our passivated NCs exhibit narrow red photoluminescence with exceptional quantum yield (close to unity) and substantially improved stability. The passivated NCs enabled us to realize red light-emitting diodes (LEDs) with 5.02% external quantum efficiency and 748 cd/m 2 luminance, surpassing by far LEDs made from the nonpassivated NCs.

Characterizing the biocompatibility and tumor-imaging capability of Cu2S nanocrystals in vivo

NASA Astrophysics Data System (ADS)

Poulose, Aby Cheruvathoor; Veeranarayanan, Srivani; Mohamed, M. Sheikh; Sakamoto, Yasushi; Hirosawa, Narumi; Suzuki, Yuko; Zhang, Minfang; Yudasaka, Masako; Radhakrishnan, Neelima; Maekawa, Toru; Mohanan, P. V.; Sakthi Kumar, D.

2015-07-01

Multifunctional nanomaterial-based probes have had key impacts on high-resolution and high-sensitivity bioimaging and therapeutics. Typically, NIR-absorbing metal sulfide-based nanocrystals (NCs) are highly assuring due to their unique optical properties. Yet, their in vivo behavior remains undetermined, which in turn undermines their potential bioapplications. Herein, we have examined the application of PEGylated Cu2S NCs as tumor contrast optical nanoprobes as well as investigated the short- and long-term in vivo compatibility focusing on anti-oxidant defense mechanism, genetic material, immune system, and vital organs. The studies revealed an overall safe profile of the NCs with no apparent toxicity even at longer exposure periods. The acquired observations culminate into a set of primary safety data of this nanomaterial and the use of PEGylated Cu2S NCs as promising optical nanoprobes with immense futuristic bioapplications.

Harmonic Quantum Coherence of Multiple Excitons in PbS/CdS Core-Shell Nanocrystals

NASA Astrophysics Data System (ADS)

Tahara, Hirokazu; Sakamoto, Masanori; Teranishi, Toshiharu; Kanemitsu, Yoshihiko

2017-12-01

The generation and recombination dynamics of multiple excitons in nanocrystals (NCs) have attracted much attention from the viewpoints of fundamental physics and device applications. However, the quantum coherence of multiple exciton states in NCs still remains unclear due to a lack of experimental support. Here, we report the first observation of harmonic dipole oscillations in PbS/CdS core-shell NCs using a phase-locked interference detection method for transient absorption. From the ultrafast coherent dynamics and excitation-photon-fluence dependence of the oscillations, we found that multiple excitons cause the harmonic dipole oscillations with ω , 2 ω , and 3 ω oscillations, even though the excitation pulse energy is set to the exciton resonance frequency, ω . This observation is closely related to the quantum coherence of multiple exciton states in NCs, providing important insights into multiple exciton generation mechanisms.

Fabrication of Eu-TiO2 NCs functionalized cotton textile as a multifunctional photocatalyst for dye pollutants degradation

NASA Astrophysics Data System (ADS)

Caschera, Daniela; Federici, Fulvio; de Caro, Tilde; Cortese, Barbara; Calandra, Pietro; Mezzi, Alessio; Lo Nigro, Raffaella; Toro, Roberta G.

2018-01-01

A modified one step and cost-effective chemical green route has been used to synthesize oleate-capped TiO2 anatase nanocrystals (NCs) doped with different amounts of europium, with high yields and without high-temperature post-calcination processes. Europium doping endowed TiO2 NCs with an intense red luminescence associated with the 5D0 → 7F2 transition of the electronic structure of Eu3+ and was responsible for both the morphological change of the NCs structure (from nanorods to spherical nanoparticles) and the blue shift in the absorption edge respect to the undoped TiO2 NCs. Furthermore, photocatalytic experiments revealed that a low-content (0.5 mol%) Eu3+ doped TiO2 NCs showed the best ability as photocatalyst for the degradation of methylene blue (MB) under both UV and visible light irradiation, even if all the Eu3+ doped oleate-capped TiO2 NCs were more effective under visible light. Moreover, taking advantage of their photocatalytic activity, the 0.5% Eu3+ doped oleate-capped TiO2 photocatalysts has been employed on cotton fabrics. Our results highlighted that functionalization of cotton textile with Eu3+ doped oleate-capped TiO2 NCs imparted new functionalities, such as a high photocatalytic activity toward MB degradation under visible light. In addition, it determined also the change in the wetting behaviour of cotton that switches to a superhydrophobic nature. The obtained fabric also showed stable and robust superhydrophobicity against strong acid and alkaline environments. Multifunctional materials having simultaneously luminescence, superhydrophobicity and visible light photocatalysis are expected to be very useful in many technological applications.

Efficient Steplike Carrier Multiplication in Percolative Networks of Epitaxially Connected PbSe Nanocrystals.

PubMed

Kulkarni, Aditya; Evers, Wiel H; Tomić, Stanko; Beard, Matthew C; Vanmaekelbergh, Daniel; Siebbeles, Laurens D A

2018-01-23

Carrier multiplication (CM) is a process in which a single photon excites two or more electrons. CM is of interest to enhance the efficiency of a solar cell. Until now, CM in thin films and solar cells of semiconductor nanocrystals (NCs) has been found at photon energies well above the minimum required energy of twice the band gap. The high threshold of CM strongly limits the benefits for solar cell applications. We show that CM is more efficient in a percolative network of directly connected PbSe NCs. The CM threshold is at twice the band gap and increases in a steplike fashion with photon energy. A lower CM efficiency is found for a solid of weaker coupled NCs. This demonstrates that the coupling between NCs strongly affects the CM efficiency. According to device simulations, the measured CM efficiency would significantly enhance the power conversion efficiency of a solar cell.

Full-color tuning in binary polymer:perovskite nanocrystals organic-inorganic hybrid blends

NASA Astrophysics Data System (ADS)

Perulli, A.; Balena, A.; Fernandez, M.; Nedelcu, G.; Cretí, A.; Kovalenko, M. V.; Lomascolo, M.; Anni, M.

2018-04-01

The excellent optical and electronic properties of metal halide perovskites recently proposed these materials as interesting active materials for optoelectronic applications. In particular, the high color purity of perovskite colloidal nanocrystals (NCs) had recently motivated their exploration as active materials for light emitting diodes with tunable emission across the visible range. In this work, we investigated the emission properties of binary blends of conjugated polymers and perovskite NCs. We demonstrate that the emission color of the blends is determined by the superposition of the component photoluminescence spectra, allowing color tuning by acting on the blend relative composition. The use of two different polymers, two different perovskite NCs, and different blend compositions is exploited to tune the blend color in the blue-green, yellow-red, and blue-red ranges, including white light generation.

Rapid dissolution of ZnO nanocrystals in acidic cancer microenvironment leading to preferential apoptosis

NASA Astrophysics Data System (ADS)

Sasidharan, Abhilash; Chandran, Parwathy; Menon, Deepthy; Raman, Sreerekha; Nair, Shantikumar; Koyakutty, Manzoor

2011-09-01

The microenvironment of cancer plays a very critical role in the survival, proliferation and drug resistance of solid tumors. Here, we report an interesting, acidic cancer microenvironment-mediated dissolution-induced preferential toxicity of ZnO nanocrystals (NCs) against cancer cells while leaving primary cells unaffected. Irrespective of the size-scale (5 and 200 nm) and surface chemistry differences (silica, starch or polyethylene glycol coating), ZnO NCs exhibited multiple stress mechanisms against cancer cell lines (IC50 ~150 μM) while normal human primary cells (human dermal fibroblast, lymphocytes, human umbilical vein endothelial cells) remain less affected. Flow cytometry and confocal microscopy studies revealed that ZnO NCs undergo rapid preferential dissolution in acidic (pH ~5-6) cancer microenvironment causing elevated ROS stress, mitochondrial superoxide formation, depolarization of mitochondrial membrane, and cell cycle arrest at S/G2 phase leading to apoptosis. In effect, by elucidating the unique toxicity mechanism of ZnO NCs, we show that ZnO NCs can destabilize cancer cells by utilizing its own hostile acidic microenvironment, which is otherwise critical for its survival.The microenvironment of cancer plays a very critical role in the survival, proliferation and drug resistance of solid tumors. Here, we report an interesting, acidic cancer microenvironment-mediated dissolution-induced preferential toxicity of ZnO nanocrystals (NCs) against cancer cells while leaving primary cells unaffected. Irrespective of the size-scale (5 and 200 nm) and surface chemistry differences (silica, starch or polyethylene glycol coating), ZnO NCs exhibited multiple stress mechanisms against cancer cell lines (IC50 ~150 μM) while normal human primary cells (human dermal fibroblast, lymphocytes, human umbilical vein endothelial cells) remain less affected. Flow cytometry and confocal microscopy studies revealed that ZnO NCs undergo rapid preferential dissolution in

The affects of doping Eu 3+ on structures and morphology of ZrO 2 nanocrystals

NASA Astrophysics Data System (ADS)

Yu, Lixin; Liu, Hai; Nogami, Masayuki

2010-07-01

The ZrO 2 and ZrO 2:Eu 3+ nanocrystals (NCs) were prepared by a hydrothermal method. The samples were sintered at different temperatures (500, 800 and 1100 °C). The results indicate that the Eu 3+ ions affect not only the structures of hosts (ZrO 2), but also the morphology of hosts. The shape of ZrO 2:Eu 3+ NCs heated at 1100 °C is the one-dimensional nanorod, while is the zero-dimensional nanoparticle for pure ZrO 2 samples sintered at the same temperature. The excitation and emission spectra of ZrO 2:Eu 3+ NCs were studied. In excitation spectra, the charge transfer band of Eu 3+ in ZrO 2 NCs heated at 1100 °C evidently blue-shifts in comparison with the NCs calcined at 500 and 800 °C. The relative intensity of 5D-7F transitions of Eu 3+ ions and color chromaticity for nanorods are increased in comparison with the nanoparticles.

Effect of Zinc Incorporation on the Performance of Red Light Emitting InP Core Nanocrystals.

PubMed

Xi, Lifei; Cho, Deok-Yong; Besmehn, Astrid; Duchamp, Martial; Grützmacher, Detlev; Lam, Yeng Ming; Kardynał, Beata E

2016-09-06

This report presents a systematic study on the effect of zinc (Zn) carboxylate precursor on the structural and optical properties of red light emitting InP nanocrystals (NCs). NC cores were assessed using X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), energy-dispersive X-ray spectroscopy (EDX), and high-resolution transmission electron microscopy (HRTEM). When moderate Zn:In ratios in the reaction pot were used, the incorporation of Zn in InP was insufficient to change the crystal structure or band gap of the NCs, but photoluminescence quantum yield (PLQY) increased dramatically compared with pure InP NCs. Zn was found to incorporate mostly in the phosphate layer on the NCs. PL, PLQY, and time-resolved PL (TRPL) show that Zn carboxylates added to the precursors during NC cores facilitate the synthesis of high-quality InP NCs by suppressing nonradiative and sub-band-gap recombination, and the effect is visible also after a ZnS shell is grown on the cores.

Host-guest chemistry for tuning colloidal solubility, self-organization and photoconductivity of inorganic-capped nanocrystals.

PubMed

Bodnarchuk, Maryna I; Yakunin, Sergii; Piveteau, Laura; Kovalenko, Maksym V

2015-12-09

Colloidal inorganic nanocrystals (NCs), functionalized with inorganic capping ligands, such as metal chalcogenide complexes (MCCs), have recently emerged as versatile optoelectronic materials. As-prepared, highly charged MCC-capped NCs are dispersible only in highly polar solvents, and lack the ability to form long-range ordered NC superlattices. Here we report a simple and general methodology, based on host-guest coordination of MCC-capped NCs with macrocyclic ethers (crown ethers and cryptands), enabling the solubilization of inorganic-capped NCs in solvents of any polarity and improving the ability to form NC superlattices. The corona of organic molecules can also serve as a convenient knob for the fine adjustment of charge transport and photoconductivity in films of NCs. In particular, high-infrared-photon detectivities of up to 3.3 × 10(11) Jones with a fast response (3 dB cut-off at 3 kHz) at the wavelength of 1,200 nm were obtained with films of PbS/K3AsS4/decyl-18-crown-6 NCs.

Host–guest chemistry for tuning colloidal solubility, self-organization and photoconductivity of inorganic-capped nanocrystals

PubMed Central

Bodnarchuk, Maryna I.; Yakunin, Sergii; Piveteau, Laura; Kovalenko, Maksym V.

2015-01-01

Colloidal inorganic nanocrystals (NCs), functionalized with inorganic capping ligands, such as metal chalcogenide complexes (MCCs), have recently emerged as versatile optoelectronic materials. As-prepared, highly charged MCC-capped NCs are dispersible only in highly polar solvents, and lack the ability to form long-range ordered NC superlattices. Here we report a simple and general methodology, based on host–guest coordination of MCC-capped NCs with macrocyclic ethers (crown ethers and cryptands), enabling the solubilization of inorganic-capped NCs in solvents of any polarity and improving the ability to form NC superlattices. The corona of organic molecules can also serve as a convenient knob for the fine adjustment of charge transport and photoconductivity in films of NCs. In particular, high-infrared-photon detectivities of up to 3.3 × 1011 Jones with a fast response (3 dB cut-off at 3 kHz) at the wavelength of 1,200 nm were obtained with films of PbS/K3AsS4/decyl-18-crown-6 NCs. PMID:26647828

Femtosecond Measurements Of Size-Dependent Spin Crossover In FeII(pyz)Pt(CN)4 Nanocrystals

DOE PAGES

Sagar, D. M.; Baddour, Frederick G.; Konold, Patrick; ...

2016-01-07

We report a femtosecond time-resolved spectroscopic study of size-dependent dynamics in nanocrystals (NCs) of Fe(pyz)Pt(CN) 4. We observe that smaller NCs (123 or 78 nm cross section and < 25 nm thickness) exhibit signatures of spin crossover (SCO) with time constants of ~ 5-10 ps whereas larger NCs with 375 nm cross section and 43 nm thickness exhibit a weaker SCO signature accompanied by strong spectral shifting on a ~20 ps time scale. For the small NCs, the fast dynamics appear to result from thermal promotion of residual low-spin states to high-spin states following nonradiative decay, and the size dependencemore » is postulated to arise from differing high-spin vs low-spin fractions in domains residing in strained surface regions. The SCO is less efficient in larger NCs owing to their larger size and hence lower residual LS/HS fractions. Our results suggest that size-dependent dynamics can be controlled by tuning surface energy in NCs with dimensions below ~25 nm for use in energy harvesting, spin switching, and other applications.« less

Origin of blue photoluminescence from colloidal silicon nanocrystals fabricated by femtosecond laser ablation in solution.

PubMed

Hao, H L; Wu, W S; Zhang, Y; Wu, L K; Shen, W Z

2016-08-12

We present a detailed investigation into the origin of blue emission from colloidal silicon (Si) nanocrystals (NCs) fabricated by femtosecond laser ablation of Si powder in 1-hexene. High resolution transmission electron microscopy and Raman spectroscopy observations confirm that Si NCs with average size 2.7 nm are produced and well dispersed in 1-hexene. Fourier transform infrared spectrum and x-ray photoelectron spectra have been employed to reveal the passivation of Si NCs surfaces with organic molecules. On the basis of the structural characterization, UV-visible absorption, temperature-dependent photoluminescence (PL), time-resolved PL, and PL excitation spectra investigations, we deduce that room-temperature blue luminescence from colloidal Si NCs originates from the following two processes: (i) under illumination, excitons first form within colloidal Si NCs by direct transition at the X or Γ (Γ25 → Γ'2) point; (ii) and then some trapped excitons migrate to the surfaces of colloidal Si NCs and further recombine via the surface states associated with the Si-C or Si-C-H2 bonds.

Surface Chemistry and Nano-/Microstructure Engineering on Photocatalytic In2S3 Nanocrystals.

PubMed

Berestok, Taisiia; Guardia, Pablo; Portals, Javier Blanco; Estradé, Sònia; Llorca, Jordi; Peiró, Francesca; Cabot, Andreu; Brock, Stephanie L

2018-06-05

Colloidal nanocrystals (NCs) compete with molecular catalysts in the field of homogenous catalysis, offering easier recyclability and a number of potentially advantageous functionalities, such as tunable band gaps, plasmonic properties, or a magnetic moment. Using high-throughput printing technologies, colloidal NCs can also be supported onto substrates to produce cost-effective electronic, optoelectronic, electrocatalytic, and sensing devices. For both catalytic and technological application, NC surface chemistry and supracrystal organization are key parameters determining final performance. Here, we study the influence of the surface ligands and the NC organization on the catalytic properties of In 2 S 3 , both as a colloid and as a supported layer. As a colloid, NCs stabilized by inorganic ligands show the highest photocatalytic activities, which we associate with their large and more accessible surfaces. On the other hand, when NCs are supported on a substrate, their organization becomes an essential parameter determining performance. For instance, NC-based films produced through a gelation process provided five-fold higher photocurrent densities than those obtained from dense films produced by the direct printing of NCs.

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.

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.

Ensemble averaged structure–function relationship for nanocrystals: effective superparamagnetic Fe clusters with catalytically active Pt skin [Ensemble averaged structure-function relationship for composite nanocrystals: magnetic bcc Fe clusters with catalytically active fcc Pt skin

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

Petkov, Valeri; Prasai, Binay; Shastri, Sarvjit

Practical applications require the production and usage of metallic nanocrystals (NCs) in large ensembles. Besides, due to their cluster-bulk solid duality, metallic NCs exhibit a large degree of structural diversity. This poses the question as to what atomic-scale basis is to be used when the structure–function relationship for metallic NCs is to be quantified precisely. In this paper, we address the question by studying bi-functional Fe core-Pt skin type NCs optimized for practical applications. In particular, the cluster-like Fe core and skin-like Pt surface of the NCs exhibit superparamagnetic properties and a superb catalytic activity for the oxygen reduction reaction,more » respectively. We determine the atomic-scale structure of the NCs by non-traditional resonant high-energy X-ray diffraction coupled to atomic pair distribution function analysis. Using the experimental structure data we explain the observed magnetic and catalytic behavior of the NCs in a quantitative manner. Lastly, we demonstrate that NC ensemble-averaged 3D positions of atoms obtained by advanced X-ray scattering techniques are a very proper basis for not only establishing but also quantifying the structure–function relationship for the increasingly complex metallic NCs explored for practical applications.« less

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.

Efficient Steplike Carrier Multiplication in Percolative Networks of Epitaxially Connected PbSe Nanocrystals

DOE PAGES

Kulkarni, Aditya; Evers, Wiel H.; Tomic, Stanko; ...

2017-12-14

Here, carrier multiplication (CM) is a process in which a single photon excites two or more electrons. CM is of interest to enhance the efficiency of a solar cell. Until now, CM in thin films and solar cells of semiconductor nanocrystals (NCs) has been found at photon energies well above the minimum required energy of twice the band gap. The high threshold of CM strongly limits the benefits for solar cell applications. We show that CM is more efficient in a percolative network of directly connected PbSe NCs. The CM threshold is at twice the band gap and increases inmore » a steplike fashion with photon energy. A lower CM efficiency is found for a solid of weaker coupled NCs. This demonstrates that the coupling between NCs strongly affects the CM efficiency. According to device simulations, the measured CM efficiency would significantly enhance the power conversion efficiency of a solar cell.« less

Colloidal thallium halide nanocrystals with reasonable luminescence, carrier mobility and diffusion length.

PubMed

Mir, Wasim J; Warankar, Avinash; Acharya, Ashutosh; Das, Shyamashis; Mandal, Pankaj; Nag, Angshuman

2017-06-01

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 Pb 2+ and Tl + exhibit a 6s 2 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 × 10 13 photons per cm 2 on NC films shows that the TlBr NCs possess high effective carrier mobility (∼220 to 329 cm 2 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.

Architectural design of heterogeneous metallic nanocrystals--principles and processes.

PubMed

Yu, Yue; Zhang, Qingbo; Yao, Qiaofeng; Xie, Jianping; Lee, Jim Yang

2014-12-16

CONSPECTUS: Heterogeneous metal nanocrystals (HMNCs) are a natural extension of simple metal nanocrystals (NCs), but as a research topic, they have been much less explored until recently. HMNCs are formed by integrating metal NCs of different compositions into a common entity, similar to the way atoms are bonded to form molecules. HMNCs can be built to exhibit an unprecedented architectural diversity and complexity by programming the arrangement of the NC building blocks ("unit NCs"). The architectural engineering of HMNCs involves the design and fabrication of the architecture-determining elements (ADEs), i.e., unit NCs with precise control of shape and size, and their relative positions in the design. Similar to molecular engineering, where structural diversity is used to create more property variations for application explorations, the architectural engineering of HMNCs can similarly increase the utility of metal NCs by offering a suite of properties to support multifunctionality in applications. The architectural engineering of HMNCs calls for processes and operations that can execute the design. Some enabling technologies already exist in the form of classical micro- and macroscale fabrication techniques, such as masking and etching. These processes, when used singly or in combination, are fully capable of fabricating nanoscopic objects. What is needed is a detailed understanding of the engineering control of ADEs and the translation of these principles into actual processes. For simplicity of execution, these processes should be integrated into a common reaction system and yet retain independence of control. The key to architectural diversity is therefore the independent controllability of each ADE in the design blueprint. The right chemical tools must be applied under the right circumstances in order to achieve the desired outcome. In this Account, after a short illustration of the infinite possibility of combining different ADEs to create HMNC design

High efficiency carrier multiplication in PbSe nanocrystals: implications for solar energy conversion.

PubMed

Schaller, R D; Klimov, V I

2004-05-07

We demonstrate for the first time that impact ionization (II) (the inverse of Auger recombination) occurs with very high efficiency in semiconductor nanocrystals (NCs). Interband optical excitation of PbSe NCs at low pump intensities, for which less than one exciton is initially generated per NC on average, results in the formation of two or more excitons (carrier multiplication) when pump photon energies are more than 3 times the NC band gap energy. The generation of multiexcitons from a single photon absorption event is observed to take place on an ultrafast (picosecond) time scale and occurs with up to 100% efficiency depending upon the excess energy of the absorbed photon. Efficient II in NCs can be used to considerably increase the power conversion efficiency of NC-based solar cells.

Ensemble brightening and enhanced quantum yield in size-purified silicon nanocrystals

DOE PAGES

Miller, Joseph B.; Van Sickle, Austin R.; Anthony, Rebecca J.; ...

2012-07-18

Here, we report on the quantum yield, photoluminescence (PL) lifetime and ensemble photoluminescent stability of highly monodisperse plasma-synthesized silicon nanocrystals (SiNCs) prepared though density-gradient ultracentrifugation in mixed organic solvents. Improved size uniformity leads to a reduction in PL line width and the emergence of entropic order in dry nanocrystal films. We find excellent agreement with the anticipated trends of quantum confinement in nanocrystalline silicon, with a solution quantum yield that is independent of nanocrystal size for the larger fractions but decreases dramatically with size for the smaller fractions. We also find a significant PL enhancement in films assembled from themore » fractions, and we use a combination of measurement, simulation and modeling to link this ‘brightening’ to a temporally enhanced quantum yield arising from SiNC interactions in ordered ensembles of monodisperse nanocrystals. Using an appropriate excitation scheme, we exploit this enhancement to achieve photostable emission.« less

Shape-Controlled Synthesis of High-Quality Cu7 S4 Nanocrystals for Efficient Light-Induced Water Evaporation.

PubMed

Zhang, Changbo; Yan, Cong; Xue, Zhenjie; Yu, Wei; Xie, Yinde; Wang, Tie

2016-10-01

Copper sulfides (Cu 2-x S), are a novel kind of photothermal material exhibiting significant photothermal conversion efficiency, making them very attractive in various energy conversion related devices. Preparing high quality uniform Cu 2-x S nanocrystals (NCs) is a top priority for further energy-and sustainability relevant nanodevices. Here, a shape-controlled high quality Cu 7 S 4 NCs synthesis strategy is reported using sulfur in 1-octadecene as precursor by varying the heating temperature, as well as its forming mechanism. The performance of the Cu 7 S 4 NCs is further explored for light-driven water evaporation without the need of heating the bulk liquid to the boiling point, and the results suggest that as-synthesized highly monodisperse NCs perform higher evaporation rate than polydisperse NCs under the identical morphology. Furthermore, disk-like NCs exhibit higher water evaporation rate than spherical NCs. The water evaporation rate can be further enhanced by assembling the organic phase Cu 7 S 4 NCs into a dense film on the aqueous solution surface. The maximum photothermal conversion efficiency is as high as 77.1%. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Combined plasma gas-phase synthesis and colloidal processing of InP/ZnS core/shell nanocrystals.

PubMed

Gresback, Ryan; Hue, Ryan; Gladfelter, Wayne L; Kortshagen, Uwe R

2011-01-12

Indium phosphide nanocrystals (InP NCs) with diameters ranging from 2 to 5 nm were synthesized with a scalable, flow-through, nonthermal plasma process at a rate ranging from 10 to 40 mg/h. The NC size is controlled through the plasma operating parameters, with the residence time of the gas in the plasma region strongly influencing the NC size. The NC size distribution is narrow with the standard deviation being less than 20% of the mean NC size. Zinc sulfide (ZnS) shells were grown around the plasma-synthesized InP NCs in a liquid phase reaction. Photoluminescence with quantum yields as high as 15% were observed for the InP/ZnS core-shell NCs.

Combined plasma gas-phase synthesis and colloidal processing of InP/ZnS core/shell nanocrystals

PubMed Central

2011-01-01

Indium phosphide nanocrystals (InP NCs) with diameters ranging from 2 to 5 nm were synthesized with a scalable, flow-through, nonthermal plasma process at a rate ranging from 10 to 40 mg/h. The NC size is controlled through the plasma operating parameters, with the residence time of the gas in the plasma region strongly influencing the NC size. The NC size distribution is narrow with the standard deviation being less than 20% of the mean NC size. Zinc sulfide (ZnS) shells were grown around the plasma-synthesized InP NCs in a liquid phase reaction. Photoluminescence with quantum yields as high as 15% were observed for the InP/ZnS core-shell NCs. PMID:21711589

Combined plasma gas-phase synthesis and colloidal processing of InP/ZnS core/shell nanocrystals

NASA Astrophysics Data System (ADS)

Gresback, Ryan; Hue, Ryan; Gladfelter, Wayne L.; Kortshagen, Uwe R.

2011-12-01

Indium phosphide nanocrystals (InP NCs) with diameters ranging from 2 to 5 nm were synthesized with a scalable, flow-through, nonthermal plasma process at a rate ranging from 10 to 40 mg/h. The NC size is controlled through the plasma operating parameters, with the residence time of the gas in the plasma region strongly influencing the NC size. The NC size distribution is narrow with the standard deviation being less than 20% of the mean NC size. Zinc sulfide (ZnS) shells were grown around the plasma-synthesized InP NCs in a liquid phase reaction. Photoluminescence with quantum yields as high as 15% were observed for the InP/ZnS core-shell NCs.

Slow cooling and highly efficient extraction of hot carriers in colloidal perovskite nanocrystals

PubMed Central

Li, Mingjie; Bhaumik, Saikat; Goh, Teck Wee; Kumar, Muduli Subas; Yantara, Natalia; Grätzel, Michael; Mhaisalkar, Subodh; Mathews, Nripan; Sum, Tze Chien

2017-01-01

Hot-carrier solar cells can overcome the Shockley-Queisser limit by harvesting excess energy from hot carriers. Inorganic semiconductor nanocrystals are considered prime candidates. However, hot-carrier harvesting is compromised by competitive relaxation pathways (for example, intraband Auger process and defects) that overwhelm their phonon bottlenecks. Here we show colloidal halide perovskite nanocrystals transcend these limitations and exhibit around two orders slower hot-carrier cooling times and around four times larger hot-carrier temperatures than their bulk-film counterparts. Under low pump excitation, hot-carrier cooling mediated by a phonon bottleneck is surprisingly slower in smaller nanocrystals (contrasting with conventional nanocrystals). At high pump fluence, Auger heating dominates hot-carrier cooling, which is slower in larger nanocrystals (hitherto unobserved in conventional nanocrystals). Importantly, we demonstrate efficient room temperature hot-electrons extraction (up to ∼83%) by an energy-selective electron acceptor layer within 1 ps from surface-treated perovskite NCs thin films. These insights enable fresh approaches for extremely thin absorber and concentrator-type hot-carrier solar cells. PMID:28176882

Slow cooling and highly efficient extraction of hot carriers in colloidal perovskite nanocrystals.

PubMed

Li, Mingjie; Bhaumik, Saikat; Goh, Teck Wee; Kumar, Muduli Subas; Yantara, Natalia; Grätzel, Michael; Mhaisalkar, Subodh; Mathews, Nripan; Sum, Tze Chien

2017-02-08

Hot-carrier solar cells can overcome the Schottky-Queisser limit by harvesting excess energy from hot carriers. Inorganic semiconductor nanocrystals are considered prime candidates. However, hot-carrier harvesting is compromised by competitive relaxation pathways (for example, intraband Auger process and defects) that overwhelm their phonon bottlenecks. Here we show colloidal halide perovskite nanocrystals transcend these limitations and exhibit around two orders slower hot-carrier cooling times and around four times larger hot-carrier temperatures than their bulk-film counterparts. Under low pump excitation, hot-carrier cooling mediated by a phonon bottleneck is surprisingly slower in smaller nanocrystals (contrasting with conventional nanocrystals). At high pump fluence, Auger heating dominates hot-carrier cooling, which is slower in larger nanocrystals (hitherto unobserved in conventional nanocrystals). Importantly, we demonstrate efficient room temperature hot-electrons extraction (up to ∼83%) by an energy-selective electron acceptor layer within 1 ps from surface-treated perovskite NCs thin films. These insights enable fresh approaches for extremely thin absorber and concentrator-type hot-carrier solar cells.

The Redox Potentials of n-type Colloidal Semiconductor Nanocrystals

NASA Astrophysics Data System (ADS)

Carroll, Gerard Michael

This thesis presents investigations for two related fields of semiconductor electrochemistry: redox potential determination of colloidal semiconductor nanocrystals, and mechanistic analysis of photoelectrochemical water oxidation with electrocatalyst modified mesostructured hematite photoanodes. Adapting electrochemical techniques to colloidal semiconductor nanocrystals (SC NC) is a long-standing challenge for this class of materials. Subject to a variety of complications, standard voltammetric techniques are not as straight forward for SC NCs as they are for small molecules. As a result, researchers have developed creative ways to side step these complications by coupling electrochemistry with NC spectroscopy. Chapter 1 discusses the fundamental electronic and spectroscopic properties of SC NCs at different redox states. We present a brief review of some of the notable studies employing SC NC spectroelectrochemistry that provide the theoretical and experimental context for the following chapters. Chapter 2 presents an investigation on NC redox potentials of photochemically reduced colloidal ZnO NCs using a solvated redox-indicator method. In the one electron limit, conduction band electrons show evidence of quantum confinement, but at higher electron concentrations, the NC Fermi-level becomes dependent on the electron density across all NC sizes. Chapter 3 outlines a poteniometric method for monitoring the NC redox potentials in situ. NC redox potentials for ZnO and CdSe are measured, and as predicted from these measurements, spontaneous electron transfer from CdSe to ZnO is demonstrated. Chapter 4 details the impact of the surface of CdSe NCs on the NC redox potentials. We find that the ratio of Cd2+:Se2- on the surface of CdSe NCs changes both the NC band edge potentials, as well as the maximum electron density achievable by photochemical reduction. These changes are proposed to arise from interfacial dipoles when CdSe has a Se2-rich surface. Chapters 5 and 6

Perspective on the prospects of a carrier multiplication nanocrystal solar cell.

PubMed

Nair, Gautham; Chang, Liang-Yi; Geyer, Scott M; Bawendi, Moungi G

2011-05-11

This article presents a perspective on the experimental and theoretical work to date on the efficiency of carrier multiplication (CM) in colloidal semiconductor nanocrystals (NCs). Early reports on CM in NCs suggested large CM efficiency enhancements. However, recent experiments have shown that CM in nanocrystalline samples is not significantly stronger, and often is weaker, than in the parent bulk when compared on an absolute photon energy basis. This finding is supported by theoretical consideration of the CM process and the competing intraband relaxation. We discuss the experimental artifacts that may have led to the apparently strong CM estimated in early reports. The finding of bulklike CM in NCs suggests that the main promise of quantum confinement is to boost the photovoltage at which carriers can be extracted. With this in mind, we discuss research directions that may result in effective use of CM in a solar cell.

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.

Photoelectrochemical processes in polymer-tethered CdSe nanocrystals.

PubMed

Shallcross, R Clayton; D'Ambruoso, Gemma D; Pyun, Jeffrey; Armstrong, Neal R

2010-03-03

We demonstrate the electrochemical capture of CdSe semiconductor nanocrystals (NCs), with thiophene-terminated carboxylic acid capping ligands, at the surfaces of electrodeposited poly(thiophene) films (i) poly((diethyl)propylenedixoythiophene), P(Et)(2)ProDOT; (ii) poly(propylenedioxythiophene), PProDOT; and (iii) poly(ethylenedioxythiophene), PEDOT, coupled with the exploration of their photoelectrochemical properties. Host polymer films were created using a kinetically controlled electrodeposition protocol on activated indium-tin oxide electrodes (ITO), producing conformal films that facilitate high rates of electron transfer. ProDOT-terminated, ligand-capped CdSe-NCs were captured at the outer surface of the host polymer films using a unique pulse-potential step electrodeposition protocol, providing for nearly close-packed monolayers of the NCs at the host polymer/solution interface. These polymer-confined CdSe NCs were used as sensitizers in the photoelectrochemical reduction of methyl viologen (MV(+2)). High internal quantum efficiencies (IQEs) are estimated for photoelectrochemical sensitized MV(+2) reduction using CdSe NCs ranging from 3.1 to 7.0 nm diameters. Cathodic photocurrent at high MV(+2) concentrations are limited by the rate of hole-capture by the host polymer from photoexcited NCs. The rate of this hole-capture process is determined by (a) the onset potential for reductive dedoping of the host polymer film; (b) the concentration ratio of neutral to oxidized forms of the host polymer ([P(n)]/[P(ox)]); and (c) the NC diameter, which controls its valence band energy, E(VB). These relationships are consistent with control of photoinduced electron transfer by Marcus-like excess free energy relationships. Our electrochemical assembly methods provide an enabling route to the capture of functional NCs in conducting polymer hosts in both photoelectrochemical and photovoltaic energy conversion systems.

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.

Colloidal PbS nanocrystals integrated to Si-based photonics for applications at telecom wavelengths

NASA Astrophysics Data System (ADS)

Humer, M.; Guider, R.; Jantsch, W.; Fromherz, T.

2013-05-01

In the last decade, Si based photonics has made major advances in terms of design, fabrication, and device implementation. But due to Silicon's indirect bandgap, it still remains a challenge to create efficient Si-based light emitting devices. In order to overcome this problem, an approach is to develop hybrid systems integrating light-emitting materials into Si. A promising class of materials for this purpose is the class of semiconducting nanocrystal quantum dots (NCs) that are synthesized by colloidal chemistry. As their absorption and emission wavelength depends on the dot size, which can easily be controlled during synthesis, they are extremely attractive as building blocks for nanophotonic applications. For applications in telecom wavelength, Lead chalcogenide colloidal NCs are optimum materials due to their unique optical, electronic and nonlinear properties. In this work, we experimentally demonstrate the integration of PbS nanocrystals into Si-based photonic structures like slot waveguides and ring resonators as optically pumped emitters for room temperature applications. In order to create such hybrid structures, the NCs were dissolved into polymer resists and drop cast on top of the device. Upon optical pumping, intense photoluminescence emission from the resonating modes is recorded at the output of the waveguide with transmission quality factors up to 14000. The polymer host material was investigated with respect to its ability to stabilize the NC's photoluminescence emission against degradation under ambient conditions. The waveguide-ring coupling efficiency was also investigated as function of the NCs concentrations blended into the polymer matrix. The integration of colloidal quantum dots into Silicon photonic structures as demonstrated in this work is a very versatile technique and thus opens a large range of applications utilizing the linear and nonlinear optical properties of PbS NCs at telecom wavelengths.

Ensemble averaged structure–function relationship for nanocrystals: effective superparamagnetic Fe clusters with catalytically active Pt skin

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

Petkov, Valeri; Prasai, Binay; Shastri, Sarvjit

2017-09-12

Practical applications require the production and usage of metallic nanocrystals (NCs) in large ensembles. Besides, due to their cluster-bulk solid duality, metallic NCs exhibit a large degree of structural diversity. This poses the question as to what atomic-scale basis is to be used when the structure–function relationship for metallic NCs is to be quantified precisely. In this paper, we address the question by studying bi-functional Fe core-Pt skin type NCs optimized for practical applications. In particular, the cluster-like Fe core and skin-like Pt surface of the NCs exhibit superparamagnetic properties and a superb catalytic activity for the oxygen reduction reaction,more » respectively. We determine the atomic-scale structure of the NCs by non-traditional resonant high-energy X-ray diffraction coupled to atomic pair distribution function analysis. Using the experimental structure data we explain the observed magnetic and catalytic behavior of the NCs in a quantitative manner. Lastly, we demonstrate that NC ensemble-averaged 3D positions of atoms obtained by advanced X-ray scattering techniques are a very proper basis for not only establishing but also quantifying the structure–function relationship for the increasingly complex metallic NCs explored for practical applications.« less

Number series of atoms, interatomic bonds and interface bonds defining zinc-blende nanocrystals as function of size, shape and surface orientation: Analytic tools to interpret solid state spectroscopy data

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

König, Dirk, E-mail: dirk.koenig@unsw.edu.au

2016-08-15

Semiconductor nanocrystals (NCs) experience stress and charge transfer by embedding materials or ligands and impurity atoms. In return, the environment of NCs experiences a NC stress response which may lead to matrix deformation and propagated strain. Up to now, there is no universal gauge to evaluate the stress impact on NCs and their response as a function of NC size d{sub NC}. I deduce geometrical number series as analytical tools to obtain the number of NC atoms N{sub NC}(d{sub NC}[i]), bonds between NC atoms N{sub bnd}(d{sub NC}[i]) and interface bonds N{sub IF}(d{sub NC}[i]) for seven high symmetry zinc-blende (zb) NCsmore » with low-index faceting: {001} cubes, {111} octahedra, {110} dodecahedra, {001}-{111} pyramids, {111} tetrahedra, {111}-{001} quatrodecahedra and {001}-{111} quadrodecahedra. The fundamental insights into NC structures revealed here allow for major advancements in data interpretation and understanding of zb- and diamond-lattice based nanomaterials. The analytical number series can serve as a standard procedure for stress evaluation in solid state spectroscopy due to their deterministic nature, easy use and general applicability over a wide range of spectroscopy methods as well as NC sizes, forms and materials.« less

Cube-shaped theranostic paclitaxel prodrug nanocrystals with surface functionalization of SPC and MPEG-DSPE for imaging and chemotherapy.

PubMed

Guo, Fuqiang; Shang, Jiajia; Zhao, Hai; Lai, Kangrong; Li, Yang; Fan, Zhongxiong; Hou, Zhenqing; Su, Guanghao

2017-12-01

As one of nanomedicine delivery systems (NDSs), drug nanocrystals exhibited an excellent anticancer effect. Recently, differences of internalization mechanisms and subcellular localization of both drug nanocrystals and small molecular free drug have drawn much attention. In this paper, paclitaxel (PTX) as a model anticancer drug was directly labeled with 4-chloro-7-nitro-1, 2, 3-benzoxadiazole (NBD-Cl) (a drug-fluorophore conjugate Ma et al. (2016) and Wang et al. (2016) [1,2] (PTX-NBD)). PTX-NBD was synthesized by nucleophilic substitution reaction of PTX with NBD-Cl in high yield and characterized by fluorescence, XRD, ESI-MS, and FT-IR analysis. Subsequently, the cube-shaped PTX-NBD nanocrystals were prepared with an antisolvent method followed by surface functionalization of SPC and MPEG-DSPE. The obtained specific shaped PTX-NBD@PC-PEG NCs had a hydrodynamic particle size of ∼50nm, excellent colloidal stability, and a high drug-loading content of ∼64%. Moreover, in comparison with free PTX-NBD and the sphere-shaped PTX-NBD nanocrystals with surface functionalization of SPC and MPEG-DSPE (PTX-NBD@PC-PEG NSs), PTX-NBD@PC-PEG NCs remarkably reduced burst release and improved cellular uptake efficiency and in vitro cancer cell killing ability. In a word, the work highlights the potential of theranostic prodrug nanocrystals based on the drug-fluorophore conjugates for cell imaging and chemotherapy. Copyright © 2017 Elsevier B.V. All rights reserved.

Flexible and fragmentable tandem photosensitive nanocrystal skins

NASA Astrophysics Data System (ADS)

Akhavan, S.; Uran, C.; Bozok, B.; Gungor, K.; Kelestemur, Y.; Lesnyak, V.; Gaponik, N.; Eychmüller, A.; Demir, H. V.

2016-02-01

We proposed and demonstrated the first account of large-area, semi-transparent, tandem photosensitive nanocrystal skins (PNSs) constructed on flexible substrates operating on the principle of photogenerated potential buildup, which avoid the need for applying an external bias and circumvent the current-matching limitation between junctions. We successfully fabricated and operated the tandem PNSs composed of single monolayers of colloidal water-soluble CdTe and CdHgTe nanocrystals (NCs) in adjacent junctions on a Kapton polymer tape. Owing to the usage of a single NC layer in each junction, noise generation was significantly reduced while keeping the resulting PNS films considerably transparent. In each junction, photogenerated excitons are dissociated at the interface of the semi-transparent Al electrode and the NC layer, with holes migrating to the contact electrode and electrons trapped in the NCs. As a result, the tandem PNSs lead to an open-circuit photovoltage buildup equal to the sum of those of the two single junctions, exhibiting a total voltage buildup of 128.4 mV at an excitation intensity of 75.8 μW cm-2 at 350 nm. Furthermore, we showed that these flexible PNSs could be bent over 3.5 mm radius of curvature and cut out in arbitrary shapes without damaging the operation of individual parts and without introducing any significant loss in the total sensitivity. These findings indicate that the NC skins are promising as building blocks to make low-cost, flexible, large-area UV/visible sensing platforms with highly efficient full-spectrum conversion.We proposed and demonstrated the first account of large-area, semi-transparent, tandem photosensitive nanocrystal skins (PNSs) constructed on flexible substrates operating on the principle of photogenerated potential buildup, which avoid the need for applying an external bias and circumvent the current-matching limitation between junctions. We successfully fabricated and operated the tandem PNSs composed of

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.

Formation of highly luminescent Zn1-xCdxSe nanocrystals using CdSe and ZnSe seeds

NASA Astrophysics Data System (ADS)

Zhang, Ruili; Yang, Ping

2013-05-01

High-quality colloidal Zn1-xCdxSe nanocrystals (NCs) with tunable photoluminescence (PL) from blue to orange were synthesized using oleic acid as a capping agent. The Zn1-xCdxSe NCs were prepared through two approaches: using CdSe or ZnSe seeds. In the case of CdSe NCs as seeds, Zn1-xCdxSe NCs were fabricated by the reaction of Zn, Cd, and Se precursors in the coordinating solvent system at high temperature. The Zn1-xCdxSe NCs revealed orange emitting. A significant blue-shift of absorption and PL spectra were observed with time, indicating the formation of ternary NCs. In contrast, Zn1-xCdxSe NCs revealed blue to green PL for ZnSe NCs as seeds. This is ascribed to an embryonic nuclei-induced alloying process. With increasing time, the Zn1-xCdxSe NCs exhibited a red-shift both in their absorption and PL spectra. This is attributed to the engineering in band gap energy via the control of NC composition. The PL properties of as-prepared alloyed NCs are comparable or even better than those for the parent binary systems. The PL peak wavelength of the Zn1-xCdxSe NCs depended strongly on reaction time and the molar ratio of Cd/Zn. The Zn1-xCdxSe NCs revealed a spherical morphology and exhibited a wurtzite structure according to transmission electron microscopy observation and an X-ray diffraction analysis.

Design of free patterns of nanocrystals with ad hoc features via templated dewetting

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

Aouassa, M.; Berbezier, I.; Favre, L.

Design of monodisperse ultra-small nanocrystals (NCs) into large scale patterns with ad hoc features is demonstrated. The process makes use of solid state dewetting of a thin film templated through alloy liquid metal ion source focused ion beam (LMIS-FIB) nanopatterning. The solid state dewetting initiated at the edges of the patterns controllably creates the ordering of NCs with ad hoc placement and periodicity. The NC size is tuned by varying the nominal thickness of the film while their position results from the association of film retraction from the edges of the lay out and Rayleigh-like instability. The use of ultra-highmore » resolution LMIS-FIB enables to produce monocrystalline NCs with size, periodicity, and placement tunable as well. It provides routes for the free design of nanostructures for generic applications in nanoelectronics.« less

Tuning Confinement in Colloidal Silicon Nanocrystals with Saturated Surface Ligands.

PubMed

Carroll, Gerard M; Limpens, Rens; Neale, Nathan R

2018-05-09

The optical properties of silicon nanocrystals (Si NCs) are a subject of intense study and continued debate. In particular, Si NC photoluminescence (PL) properties are known to depend strongly on the surface chemistry, resulting in electron-hole recombination pathways derived from the Si NC band-edge, surface-state defects, or combined NC-conjugated ligand hybrid states. In this Letter, we perform a comparison of three different saturated surface functional groups-alkyls, amides, and alkoxides-on nonthermal plasma-synthesized Si NCs. We find a systematic and size-dependent high-energy (blue) shift in the PL spectrum of Si NCs with amide and alkoxy functionalization relative to alkyl. Time-resolved photoluminescence and transient absorption spectroscopies reveal no change in the excited-state dynamics between Si NCs functionalized with alkyl, amide, or alkoxide ligands, showing for the first time that saturated ligands-not only surface-derived charge-transfer states or hybridization between NC and low-lying ligand orbitals-are responsible for tuning the Si NC optical properties. To explain these PL shifts we propose that the atom bound to the Si NC surface strongly interacts with the Si NC electronic wave function and modulates the Si NC quantum confinement. These results reveal a potentially broadly applicable correlation between the optoelectronic properties of Si NCs and related quantum-confined structures based on the interaction between NC surfaces and the ligand binding group.

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.

Identification of nasopharyngeal carcinoma from photoluminescence spectra of 3C-SiC nanocrystals

NASA Astrophysics Data System (ADS)

Wang, Li-Fen; Guo, Jun-Hong; Huang, Zhi-Chun; Gu, Jian-Sen; Feng, Li-Ren; Liu, Li-Zhe

2017-09-01

The identification of intracellular pH (pHi) during carcinogenesis progression plays a crucial role in the studies of biochemistry, cytology, and clinical medicine. In this work, 3C-SiC nanocrystals (NCs), which can effectively monitor the pH environment by using the linear relation between photoluminescence intensity and surface OH- and H+ concentration, are adapted as fluorescent probes for monitoring carcinogenesis progression of nasopharyngeal carcinoma. Our results demonstrated that 3C-SiC NCs are compatible with living cells and have low cytotoxicity. The pHi measurements in different carcinogenesis environments indicate the validity and sensitivity of this technology in identifying nasopharyngeal carcinoma in application.

Negligible Electronic Interaction between Photoexcited Electron–Hole Pairs and Free Electrons in Phosphorus–Boron Co-Doped Silicon Nanocrystals

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

Limpens, Rens; Fujii, Minoru; Neale, Nathan R.

Phosphorus (P) and boron (B) co-doped Si nanocrystals (NCs) have raised interest in the optoelectronic industry due to their electronic tunability, optimal carrier multiplication properties, and straightforward dispersibility in polar solvents. Yet a basic understanding of the interaction of photoexcited electron-hole (e-h) pairs with new physical features that are introduced by the co-doping process (free carriers, defect states, and surface chemistry) is missing. Here, we present the first study of the ultrafast carrier dynamics in SiO2-embedded P-B co-doped Si NC ensembles using induced absorption spectroscopy through a two-step approach. First, the induced absorption data show that the large fraction ofmore » the dopants residing on the NC surface slows down carrier relaxation dynamics within the first 20 ps relative to intrinsic (undoped) Si NCs, which we interpret as enhanced surface passivation. On longer time-scales (picosecond to nanosecond regime), we observe a speeding up of the carrier relaxation dynamics and ascribe it to doping-induced trap states. This argument is deduced from the second part of the study, where we investigate multiexciton interactions. From a stochastic modeling approach we show that localized carriers, which are introduced by the P or B dopants, have minor electronic interactions with the photoexcited e-h pairs. This is understood in light of the strong localization of the introduced carriers on their original P- or B-dopant atoms, due to the strong quantum confinement regime in these relatively small NCs (<6 nm).« less

Negligible Electronic Interaction between Photoexcited Electron-Hole Pairs and Free Electrons in Phosphorus-Boron Co-Doped Silicon Nanocrystals

DOE PAGES

Limpens, Rens; Neale, Nathan R; Fujii, Minoru; ...

2018-03-05

Phosphorus (P) and boron (B) co-doped Si nanocrystals (NCs) have raised interest in the optoelectronic industry due to their electronic tunability, optimal carrier multiplication properties, and straightforward dispersibility in polar solvents. Yet a basic understanding of the interaction of photoexcited electron-hole (e-h) pairs with new physical features that are introduced by the co-doping process (free carriers, defect states, and surface chemistry) is missing. Here, we present the first study of the ultrafast carrier dynamics in SiO2-embedded P-B co-doped Si NC ensembles using induced absorption spectroscopy through a two-step approach. First, the induced absorption data show that the large fraction ofmore » the dopants residing on the NC surface slows down carrier relaxation dynamics within the first 20 ps relative to intrinsic (undoped) Si NCs, which we interpret as enhanced surface passivation. On longer time-scales (picosecond to nanosecond regime), we observe a speeding up of the carrier relaxation dynamics and ascribe it to doping-induced trap states. This argument is deduced from the second part of the study, where we investigate multiexciton interactions. From a stochastic modeling approach we show that localized carriers, which are introduced by the P or B dopants, have minor electronic interactions with the photoexcited e-h pairs. This is understood in light of the strong localization of the introduced carriers on their original P- or B-dopant atoms, due to the strong quantum confinement regime in these relatively small NCs (<6 nm).« less

Negligible Electronic Interaction between Photoexcited Electron–Hole Pairs and Free Electrons in Phosphorus–Boron Co-Doped Silicon Nanocrystals

DOE PAGES

Limpens, Rens; Fujii, Minoru; Neale, Nathan R.; ...

2018-02-28

Phosphorus (P) and boron (B) co-doped Si nanocrystals (NCs) have raised interest in the optoelectronic industry due to their electronic tunability, optimal carrier multiplication properties, and straightforward dispersibility in polar solvents. Yet a basic understanding of the interaction of photoexcited electron-hole (e-h) pairs with new physical features that are introduced by the co-doping process (free carriers, defect states, and surface chemistry) is missing. Here, we present the first study of the ultrafast carrier dynamics in SiO2-embedded P-B co-doped Si NC ensembles using induced absorption spectroscopy through a two-step approach. First, the induced absorption data show that the large fraction ofmore » the dopants residing on the NC surface slows down carrier relaxation dynamics within the first 20 ps relative to intrinsic (undoped) Si NCs, which we interpret as enhanced surface passivation. On longer time-scales (picosecond to nanosecond regime), we observe a speeding up of the carrier relaxation dynamics and ascribe it to doping-induced trap states. This argument is deduced from the second part of the study, where we investigate multiexciton interactions. From a stochastic modeling approach we show that localized carriers, which are introduced by the P or B dopants, have minor electronic interactions with the photoexcited e-h pairs. This is understood in light of the strong localization of the introduced carriers on their original P- or B-dopant atoms, due to the strong quantum confinement regime in these relatively small NCs (<6 nm).« less

Photoluminescence and time-resolved carrier dynamics in thiol-capped CdTe nanocrystals under high pressure

NASA Astrophysics Data System (ADS)

Lin, Yan-Cheng; Chou, Wu-Ching; Susha, Andrei S.; Kershaw, Stephen V.; Rogach, Andrey L.

2013-03-01

The application of static high pressure provides a method for precisely controlling and investigating many fundamental and unique properties of semiconductor nanocrystals (NCs). This study systematically investigates the high-pressure photoluminescence (PL) and time-resolved carrier dynamics of thiol-capped CdTe NCs of different sizes, at different concentrations, and in various stress environments. The zincblende-to-rocksalt phase transition in thiol-capped CdTe NCs is observed at a pressure far in excess of the bulk phase transition pressure. Additionally, the process of transformation depends strongly on NC size, and the phase transition pressure increases with NC size. These peculiar phenomena are attributed to the distinctive bonding of thiols to the NC surface. In a nonhydrostatic environment, considerable flattening of the PL energy of CdTe NC powder is observed above 3.0 GPa. Furthermore, asymmetric and double-peak PL emissions are obtained from a concentrated solution of CdTe NCs under hydrostatic pressure, implying the feasibility of pressure-induced interparticle coupling.

"Intact" Carrier Doping by Pump-Pump-Probe Spectroscopy in Combination with Interfacial Charge Transfer: A Case Study of CsPbBr3 Nanocrystals.

PubMed

Wang, Junhui; Ding, Tao; Leng, Jing; Jin, Shengye; Wu, Kaifeng

2018-06-21

Carrier doping is important for semiconductor nanocrystals (NCs) as it offers a new knob to tune NCs' functionalities, in addition to size and shape control. Also, extensive studies on NC devices have revealed that under operating conditions NCs are often unintentionally doped with electrons or holes. Thus, it is essential to be able to control the doping of NCs and study the carrier dynamics of doped NCs. The extension of previously reported redox-doping methods to chemically sensitive materials, such as recently introduced perovskite NCs, has remained challenging. We introduce an "intact" carrier-doping method by performing pump-pump-probe transient absorption spectroscopy on NC-acceptor complexes. The first pump pulse is used to trigger charge transfer from the NC to the acceptor, leading to NCs doped with a band edge carrier; the following pump-probe pulses measure the dynamics of carrier-doped NCs. We performed this measurement on CsPbBr 3 NCs and deduced positive and negative trion lifetimes of 220 ± 50 and 150 ± 40 ps, respectively, for 10 nm diameter NCs, both dominated by Auger recombination. It also allowed us to identify randomly photocharged excitons in CsPbBr 3 NCs as positive trions.

Colloidal InP/ZnS core shell nanocrystals studied by linearly and circularly polarized photoluminescence

NASA Astrophysics Data System (ADS)

Langof, L.; Fradkin, L.; Ehrenfreund, E.; Lifshitz, E.; Micic, O. I.; Nozik, A. J.

2004-02-01

The magneto-optical properties of InP/ZnS core-shell nanocrystals (NCs) were investigated by measuring the degree of linear and circular polarization of photoluminescence (PL) spectra, in the presence of an external magnetic field under resonant or non-resonant excitation. The linearly polarized PL data strongly indicate that InP/ZnS NCs have a prolongated shape. The resonant-excited circularly polarized PL decay curves indicate that the spin relaxation time of the studied samples is shorter than the radiative lifetime of their exciton. Furthermore, the magnetic field-induced circularly polarized PL process reveals an exciton g factor ( gex) of 0.55. Thus, such studies may serve as a tool to directly estimate the NC's shape anisotropy and to determine the g-factor of charge carriers and excitons in those NCs.

Phosphorus Doping in Si Nanocrystals/SiO2 msultilayers and Light Emission with Wavelength compatible for Optical Telecommunication

PubMed Central

Lu, Peng; Mu, Weiwei; Xu, Jun; Zhang, Xiaowei; Zhang, Wenping; Li, Wei; Xu, Ling; Chen, Kunji

2016-01-01

Doping in semiconductors is a fundamental issue for developing high performance devices. However, the doping behavior in Si nanocrystals (Si NCs) has not been fully understood so far. In the present work, P-doped Si NCs/SiO2 multilayers are fabricated. As revealed by XPS and ESR measurements, P dopants will preferentially passivate the surface states of Si NCs. Meanwhile, low temperature ESR spectra indicate that some P dopants are incorporated into Si NCs substitutionally and the incorporated P impurities increase with the P doping concentration or annealing temperature increasing. Furthermore, a kind of defect states will be generated with high doping concentration or annealing temperature due to the damage of Si crystalline lattice. More interestingly, the incorporated P dopants can generate deep levels in the ultra-small sized (~2 nm) Si NCs, which will cause a new subband light emission with the wavelength compatible with the requirement of the optical telecommunication. The studies of P-doped Si NCs/SiO2 multilayers suggest that P doping plays an important role in the electronic structures and optoelectronic characteristics of Si NCs. PMID:26956425

Combination of surface- and interference-enhanced Raman scattering by CuS nanocrystals on nanopatterned Au structures

PubMed Central

Yeryukov, Nikolay A; Sveshnikova, Larisa L; Duda, Tatyana A; Rodyakina, Ekaterina E; Gridchin, Victor A; Sheremet, Evgeniya S; Zahn, Dietrich R T

2015-01-01

Summary We present the results of a Raman study of optical phonons in CuS nanocrystals (NCs) with a low areal density fabricated through the Langmuir–Blodgett technology on nanopatterned Au nanocluster arrays using a combination of surface- and interference-enhanced Raman scattering (SERS and IERS, respectively). Micro-Raman spectra of one monolayer of CuS NCs deposited on a bare Si substrate reveal only features corresponding to crystalline Si. However, a new relatively strong peak occurs in the Raman spectrum of CuS NCs on Au nanocluster arrays at 474 cm−1. This feature is related to the optical phonon mode in CuS NCs and manifests the SERS effect. For CuS NCs deposited on a SiO2 layer this phonon mode is also observed due to the IERS effect. Its intensity changes periodically with increasing SiO2 layer thickness for different laser excitation lines and is enhanced by a factor of about 30. CuS NCs formed on Au nanocluster arrays fabricated on IERS substrates combine the advantages of SERS and IERS and demonstrate stronger SERS enhancement allowing for the observation of Raman signals from CuS NCs with an ultra-low areal density. PMID:25977845

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.

High-Performance Low-Cost Portable Radiological and Nuclear Detectors Based on Colloidal Nanocrystals (TOPIC 07-B)

DTIC Science & Technology

2016-07-01

concluded that more gamma interactions are occurring with the NCs, leading to more down- scattered photons. Conversely, that also means that there is a...15 6. Colloidal Synthesis of Lead -Based Scintillating Nanocrystals (Task 2)………..…………...15 6.A. Colloidal Synthesis of PbI2 Scintillating...LaF3 Nanocrystals Synthesized in Water………………………………………...……….………………………...27 8. Characterization of Lead -Based Scintillating

Sol-gel-derived double-layered nanocrystal memory

NASA Astrophysics Data System (ADS)

Ko, Fu-Hsiang; You, Hsin-Chiang; Lei, Tan-Fu

2006-12-01

The authors have used the sol-gel spin-coating method to fabricate a coexisting hafnium silicate and zirconium silicate double-layered nanocrystal (NC) memories. From transmission electron microscopic and x-ray photoelectron spectroscopic analyses, the authors determined that the hafnium silicate and zirconium silicate NCs formed after annealing at 900°C for 1min. When using channel hot electron injection for charging and band-to-band tunneling-induced hot hole injection for discharging, the NC memories exhibited superior Vth shifting because of the higher probability for trapping the charge carrier.

Tailoring characteristic thermal stability of Ni-Au binary nanocrystals via structure and composition engineering: theoretical insights into structural evolution and atomic inter-diffusion

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

Li, Bangquan; Wang, Hailong; Xing, Guozhong

We report on the structural evolution and atomic inter-diffusion characteristics of the bimetallic Ni-Au nanocrystals (NCs) by molecular dynamics simulations studies. Our results reveal that the thermal stability dynamics of Ni-Au NCs strongly depends on the atomic configurations. By engineering the structural construction with Ni:Au = 1:1 atomic composition, compared with core-shell Au@Ni and alloy NCs, the melting point of core-shell Ni@Au NCs is significantly enhanced up to 1215 K. Unexpectedly, with atomic ratio of Au:Ni= 1:9, the melting process initiates from the atoms in the shell of Ni@Au and alloy NCs, while starts from the core of Au@Ni NCs.more » The corresponding features and evolution process of structural motifs, mixing and segregation are illustrated via a series of dynamic simulations videos. Moreover, our results revealed that the face centered cubic phase Au{sub 0.75}Ni{sub 0.25} favorably stabilizes in NCs form but does not exist in the bulk counterpart, which elucidates the anomalies of previously reported experimental results on such bimetallic NCs.« less

Bi-continuous Multi-component Nanocrystal Superlattices for Solar Energy Conversion

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

Kagan, Cherie; Murray, Christopher; Kikkawa, James

2017-06-14

Our SISGR program studied an emerging class of nanomaterials wherein different combinations of semiconductor or semiconductor and plasmonic nanocrystals (NCs) are self-assembled into three-dimensional multi-component superlattices. The NC assemblies were designed to form bicontinuous semiconductor NC sublattices with type-II energy offsets to drive charge separation onto electron and hole transporting sublattices for collection and introduce plasmonic NCs to increase solar absorption and charge separation. Our group is expert in synthesizing and assembling an extraordinary variety of artificial systems by tailoring the NC building blocks and the superlattice unit cell geometry. Under this DOE BES Materials Chemistry program, we introduced chemicalmore » methods to control inter-particle distance and to dope NC assemblies, which enabled our demonstration of strong electronic communication between NCs and the use of NC thin films as electronic materials. We synthesized, assembled and structurally, spectroscopically, and electrically probed NC superlattices to understand and manipulate the flow of energy and charge toward discovering the design rules and optimizing these complex architectures to create materials that efficiently convert solar radiation into electricity.« less

Colloid-Interface-Assisted Laser Irradiation of Nanocrystals Superlattices to be Scalable Plasmonic Superstructures with Novel Activities.

PubMed

Huang, Liu; Wan, Xiaodong; Rong, Hongpan; Yao, Yuan; Xu, Meng; Liu, Jia; Ji, Muwei; Liu, Jiajia; Jiang, Lan; Zhang, Jiatao

2018-04-01

High-efficient charge and energy transfer between nanocrystals (NCs) in a bottom-up assembly are hard to achieve, resulting in an obstacle in application. Instead of the ligands exchange strategies, the advantage of a continuous laser is taken with optimal wavelength and power to irradiate the film-scale NCs superlattices at solid-liquid interfaces. Owing to the Au-based NCs' surface plasmon resonance (SPR) effect, the gentle laser irradiation leads the Au NCs or Au@CdS core/shell NCs to attach each other with controlled pattern at the interfaces between solid NCs phase and liquid ethanol/ethylene glycol. A continuous wave 532 nm laser (6.68-13.37 W cm -2 ), to control Au-based superlattices, is used to form the monolayer with uniformly reduced interparticle distance followed by welded superstructures. Considering the size effect to Au NCs' melting, when decreasing the Au NCs size to ≈5 nm, stronger welding nanostructures are obtained with diverse unprecedented shapes which cannot be achieved by normal colloidal synthesis. With the help of facile scale-up and formation at solid-liquid interfaces, and a good connection of crystalline between NCs, the obtained plasmonic superstructured films that could be facilely transferred onto different substrates exhibit broad SPR absorption in the visible and near-infrared regime, enhanced electric conductivities, and wide applications as surface enhanced Raman scattering (SERS)-active substrates. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-Pressure-Induced Comminution and Recrystallization of CH3 NH3 PbBr3 Nanocrystals as Large Thin Nanoplates.

PubMed

Yin, Tingting; Fang, Yanan; Chong, Wee Kiang; Ming, Koh Teck; Jiang, Shaojie; Li, Xianglin; Kuo, Jer-Lai; Fang, Jiye; Sum, Tze Chien; White, Timothy J; Yan, Jiaxu; Shen, Ze Xiang

2018-01-01

High pressure (HP) can drive the direct sintering of nanoparticle assemblies for Ag/Au, CdSe/PbS nanocrystals (NCs). Instead of direct sintering for the conventional nanocrystals, this study experimentally observes for the first time high-pressure-induced comminution and recrystallization of organic-inorganic hybrid perovskite nanocrystals into highly luminescent nanoplates with a shorter carrier lifetime. Such novel pressure response is attributed to the unique structural nature of hybrid perovskites under high pressure: during the drastic cubic-orthorhombic structural transformation at ≈2 GPa, (301) the crystal plane fully occupied by organic molecules possesses a higher surface energy, triggering the comminution of nanocrystals into nanoslices along such crystal plane. Beyond bulk perovskites, in which pressure-induced modifications on crystal structures and functional properties will disappear after pressure release, the pressure-formed variants, i.e., large (≈100 nm) and thin (<10 nm) perovskite nanoplates, are retained and these exhibit simultaneous photoluminescence emission enhancing (a 15-fold enhancement in the photoluminescence) and carrier lifetime shortening (from ≈18.3 ± 0.8 to ≈7.6 ± 0.5 ns) after releasing of pressure from 11 GPa. This pressure-induced comminution of hybrid perovskite NCs and a subsequent amorphization-recrystallization treatment offer the possibilities of engineering the advanced hybrid perovskites with specific properties. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Germanium Nanocrystal Solar Cells

NASA Astrophysics Data System (ADS)

Holman, Zachary Charles

Greenhouse gas concentrations in the atmosphere are approaching historically unprecedented levels from burning fossil fuels to meet the ever-increasing world energy demand. A rapid transition to clean energy sources is necessary to avoid the potentially catastrophic consequences of global warming. The sun provides more than enough energy to power the world, and solar cells that convert sunlight to electricity are commercially available. However, the high cost and low efficiency of current solar cells prevent their widespread implementation, and grid parity is not anticipated to be reached for at least 15 years without breakthrough technologies. Semiconductor nanocrystals (NCs) show promise for cheap multi-junction photovoltaic devices. To compete with photovoltaic materials that are currently commercially available, NCs need to be inexpensively cast into dense thin films with bulk-like electrical mobilities and absorption spectra that can be tuned by altering the NC size. The Group II-VI and IV-VI NC communities have had some success in achieving this goal by drying and then chemically treating colloidal particles, but the more abundant and less toxic Group IV NCs have proven more challenging. This thesis reports thin films of plasma-synthesized Ge NCs deposited using three different techniques, and preliminary solar cells based on these films. Germanium tetrachloride is dissociated in the presence of hydrogen in a nonthermal plasma to nucleate Ge NCs. Transmission electron microscopy and X-ray diffraction indicate that the particles are nearly monodisperse (standard deviations of 10-15% the mean particle diameter) and the mean diameter can be tuned from 4-15 nm by changing the residence time of the Ge NCs in the plasma. In the first deposition scheme, a Ge NC colloid is formed by reacting nanocrystalline powder with 1-dodecene and dispersing the functionalized NCs in a solvent. Films are then formed on substrates by drop-casting the colloid and allowing it to dry

Synthesis of bimetallic Pt-Pd core-shell nanocrystals and their high electrocatalytic activity modulated by Pd shell thickness

NASA Astrophysics Data System (ADS)

Li, Yujing; Wang, Zhi Wei; Chiu, Chin-Yi; Ruan, Lingyan; Yang, Wenbing; Yang, Yang; Palmer, Richard E.; Huang, Yu

2012-01-01

Bimetallic Pt-Pd core-shell nanocrystals (NCs) are synthesized through a two-step process with controlled Pd thickness from sub-monolayer to multiple atomic layers. The oxygen reduction reaction (ORR) catalytic activity and methanol oxidation reactivity of the core-shell NCs for fuel cell applications in alkaline solution are systematically studied and compared based on different Pd thickness. It is found that the Pd shell helps to reduce the over-potential of ORR by up to 50mV when compared to commercial Pd black, while generating up to 3-fold higher kinetic current density. The carbon monoxide poisoning test shows that the bimetallic NCs are more resistant to the CO poisoning than Pt NCs and Pt black. It is also demonstrated that the bimetallic Pt-Pd core-shell NCs can enhance the current density of the methanol oxidation reaction, lowering the over-potential by 35 mV with respect to the Pt core NCs. Further investigation reveals that the Pd/Pt ratio of 1/3, which corresponds to nearly monolayer Pd deposition on Pt core NCs, gives the highest oxidation current density and lowest over-potential. This study shows for the first time the systematic investigation of effects of Pd atomic shells on Pt-Pd bimetallic nanocatalysts, providing valuable guidelines for designing high-performance catalysts for fuel cell applications.Bimetallic Pt-Pd core-shell nanocrystals (NCs) are synthesized through a two-step process with controlled Pd thickness from sub-monolayer to multiple atomic layers. The oxygen reduction reaction (ORR) catalytic activity and methanol oxidation reactivity of the core-shell NCs for fuel cell applications in alkaline solution are systematically studied and compared based on different Pd thickness. It is found that the Pd shell helps to reduce the over-potential of ORR by up to 50mV when compared to commercial Pd black, while generating up to 3-fold higher kinetic current density. The carbon monoxide poisoning test shows that the bimetallic NCs are more

Chemical Insight Into The Origin of Red and Blue Photoluminescence Arising From Freestanding Silicon Nanocrystals

PubMed Central

Dasog, Mita; Yang, Zhenyu; Regli, Sarah; Atkins, Tonya M.; Faramus, Angelique; Singh, Mani P.; Muthuswamy, Elayaraja; Kauzlarich, Susan M.; Tilley, Richard D.; Veinot, Jonathan G. C.

2013-01-01

Silicon nanocrystals (Si NCs) are attractive functional materials. They are compatible with standard electronics and communications platforms as well being biocompatible. Numerous methods have been developed to realize size-controlled Si NC synthesis. While these procedures produce Si NCs that appear identical, their optical responses can differ dramatically. Si NCs prepared using high-temperature methods routinely exhibit photoluminescence agreeing with the effective mass approximation (EMA), while those prepared via solution methods exhibit blue emission that is somewhat independent of particle size. Despite many proposals, a definitive explanation for this difference has been elusive for no less than a decade. This apparent dichotomy brings into question our understanding of Si NC properties and potentially limits the scope of their application. The present contribution takes a substantial step forward toward identifying the origin of the blue emission that is not expected based upon EMA predictions. It describes a detailed comparison of Si NCs obtained from three of the most widely cited procedures as well as the conversion of red-emitting Si NCs to blue-emitters upon exposure to nitrogen containing reagents. Analysis of the evidence is consistent with the hypothesis that the presence of trace nitrogen and oxygen even at the ppm level in Si NCs gives rise to the blue emission. PMID:23394574

Chemical insight into the origin of red and blue photoluminescence arising from freestanding silicon nanocrystals.

PubMed

Dasog, Mita; Yang, Zhenyu; Regli, Sarah; Atkins, Tonya M; Faramus, Angelique; Singh, Mani P; Muthuswamy, Elayaraja; Kauzlarich, Susan M; Tilley, Richard D; Veinot, Jonathan G C

2013-03-26

Silicon nanocrystals (Si NCs) are attractive functional materials. They are compatible with standard electronics and communications platforms and are biocompatible. Numerous methods have been developed to realize size-controlled Si NC synthesis. While these procedures produce Si NCs that appear identical, their optical responses can differ dramatically. Si NCs prepared using high-temperature methods routinely exhibit photoluminescence agreeing with the effective mass approximation (EMA), while those prepared via solution methods exhibit blue emission that is somewhat independent of particle size. Despite many proposals, a definitive explanation for this difference has been elusive for no less than a decade. This apparent dichotomy brings into question our understanding of Si NC properties and potentially limits the scope of their application. The present contribution takes a substantial step forward toward identifying the origin of the blue emission that is not expected based upon EMA predictions. It describes a detailed comparison of Si NCs obtained from three of the most widely cited procedures as well as the conversion of red-emitting Si NCs to blue emitters upon exposure to nitrogen-containing reagents. Analysis of the evidence is consistent with the hypothesis that the presence of trace nitrogen and oxygen even at the parts per million level in Si NCs gives rise to the blue emission.

Bioimaging and toxicity assessments of near-infrared upconversion luminescent NaYF4:Yb,Tm nanocrystals.

PubMed

Zhou, Jia-Cai; Yang, Zheng-Lin; Dong, Wei; Tang, Ruo-Jin; Sun, Ling-Dong; Yan, Chun-Hua

2011-12-01

In vitro or in vivo bioimaging utilizing the upconversion (UC) luminescence of rare earth fluoride nanocrystals (NCs) has attracted much attention, especially for Yb(3+)/Tm(3+) doped NCs with a near-infrared (NIR) UC emission at 800 nm. Herein, water-soluble NaYF(4):Yb,Tm NCs with strong NIR UC emission were synthesized with a solvothermal method. In vitro and in vivo bioimaging and toxicity assessments were carried out with HeLa cell and Caenorhabditis elegans (C. elegans) cases, respectively. NaYF(4):Yb,Tm NCs afforded an efficient NIR image of the HeLa cells with an incubation concentration of 10 μg mL(-1), and CCK-8 assay revealed a low cytotoxicity. Fed with Escherichia coli (E. coli) and NCs together, the C. elegans showed a NIR image in the gut from the pharynx to the anus. Further, these NCs could be excreted out when those worms were then fed with only E. coli. Toxicity studies were further addressed with protein expression, life span, egg production, egg viability, and growth rate of the worms in comparison with those of the intact ones. The feeding of rare earth fluoride NCs with a dose of 100 μg does not arise obvious toxicity effect from the growth to procreation. The in vitro and in vivo studies confirm that NaYF(4):Yb,Tm NCs could be served as an excellent NIR emission bioprobe with low toxicity. Copyright © 2011 Elsevier Ltd. All rights reserved.

Impact of Silicon Nanocrystal Oxidation on the Nonmetallic Growth of Carbon Nanotubes.

PubMed

Rocks, Conor; Mitra, Somak; Macias-Montero, Manuel; Maguire, Paul; Svrcek, Vladimir; Levchenko, Igor; Ostrikov, Kostya; Mariotti, Davide

2016-07-27

Carbon nanotube (CNT) growth has been demonstrated recently using a number of nonmetallic semiconducting and metal oxide nanoparticles, opening up pathways for direct CNT synthesis from a number of more desirable templates without the need for metallic catalysts. However, CNT growth mechanisms using these nonconventional catalysts has been shown to largely differ and reamins a challenging synthesis route. In this contribution we show CNT growth from partially oxidized silicon nanocrystals (Si NCs) that exhibit quantum confinement effects using a microwave plasma enhanced chemical vapor deposition (PECVD) method. On the basis of solvent and a postsynthesis frgamentation process, we show that oxidation of our Si NCs can be easily controlled. We determine experimentally and explain with theoretical simulations that the Si NCs morphology together with a necessary shell oxide of ∼1 nm is vital to allow for the nonmetallic growth of CNTs. On the basis of chemical analysis post-CNT-growth, we give insight into possible mechanisms for CNT nucleation and growth from our partially oxidized Si NCs. This contribution is of significant importance to the improvement of nonmetallic catalysts for CNT growth and the development of Si NC/CNT interfaces.

Tuning Confinement in Colloidal Silicon Nanocrystals with Saturated Surface Ligands

DOE PAGES

Carroll, Gerard M.; Limpens, Rens; Neale, Nathan R.

2018-04-16

The optical properties of silicon nanocrystals (Si NCs) are a subject of intense study and continued debate. In particular, Si NC photoluminescence (PL) properties are known to depend strongly on the surface chemistry, resulting in electron-hole recombination pathways derived from the Si NC band-edge, surface-state defects, or combined NC-conjugated ligand hybrid states. In this Letter, we perform a comparison of three different saturated surface functional groups - alkyls, amides, and alkoxides - on nonthermal plasma-synthesized Si NCs. We find a systematic and size-dependent high-energy (blue) shift in the PL spectrum of Si NCs with amide and alkoxy functionalization relative tomore » alkyl. Time-resolved photoluminescence and transient absorption spectroscopies reveal no change in the excited-state dynamics between Si NCs functionalized with alkyl, amide, or alkoxide ligands, showing for the first time that saturated ligands - not only surface-derived charge-transfer states or hybridization between NC and low-lying ligand orbitals - are responsible for tuning the Si NC optical properties. To explain these PL shifts we propose that the atom bound to the Si NC surface strongly interacts with the Si NC electronic wave function and modulates the Si NC quantum confinement. Furthermore, these results reveal a potentially broadly applicable correlation between the optoelectronic properties of Si NCs and related quantum-confined structures based on the interaction between NC surfaces and the ligand binding group.« less

Plasmonic light-sensitive skins of nanocrystal monolayers

NASA Astrophysics Data System (ADS)

Akhavan, Shahab; Gungor, Kivanc; Mutlugun, Evren; Demir, Hilmi Volkan

2013-04-01

We report plasmonically coupled light-sensitive skins of nanocrystal monolayers that exhibit sensitivity enhancement and spectral range extension with plasmonic nanostructures embedded in their photosensitive nanocrystal platforms. The deposited plasmonic silver nanoparticles of the device increase the optical absorption of a CdTe nanocrystal monolayer incorporated in the device. Controlled separation of these metallic nanoparticles in the vicinity of semiconductor nanocrystals enables optimization of the photovoltage buildup in the proposed nanostructure platform. The enhancement factor was found to depend on the excitation wavelength. We observed broadband sensitivity improvement (across 400-650 nm), with a 2.6-fold enhancement factor around the localized plasmon resonance peak. The simulation results were found to agree well with the experimental data. Such plasmonically enhanced nanocrystal skins hold great promise for large-area UV/visible sensing applications.

Blocking germanium diffusion inside silicon dioxide using a co-implanted silicon barrier

NASA Astrophysics Data System (ADS)

Barba, D.; Wang, C.; Nélis, A.; Terwagne, G.; Rosei, F.

2018-04-01

We investigate the effect of co-implanting a silicon sublayer on the thermal diffusion of germanium ions implanted into SiO2 and the growth of Ge nanocrystals (Ge-ncs). High-resolution imaging obtained by transmission electron microscopy and energy dispersive spectroscopy measurements supported by Monte-Carlo calculations shows that the Si-enriched region acts as a diffusion barrier for Ge atoms. This barrier prevents Ge outgassing during thermal annealing at 1100 °C. Both the localization and the reduced size of Ge-ncs formed within the sample region co-implanted with Si are observed, as well as the nucleation of mixed Ge/Si nanocrystals containing structural point defects and stacking faults. Although it was found that the Si co-implantation affects the crystallinity of the formed Ge-ncs, this technique can be implemented to produce size-selective and depth-ordered nanostructured systems by controlling the spatial distribution of diffusing Ge. We illustrate this feature for Ge-ncs embedded within a single SiO2 monolayer, whose diameters were gradually increased from 1 nm to 5 nm over a depth of 100 nm.

Real-Space Mapping of Surface Trap States in CIGSe Nanocrystals Using 4D Electron Microscopy.

PubMed

Bose, Riya; Bera, Ashok; Parida, Manas R; Adhikari, Aniruddha; Shaheen, Basamat S; Alarousu, Erkki; Sun, Jingya; Wu, Tom; Bakr, Osman M; Mohammed, Omar F

2016-07-13

Surface trap states in copper indium gallium selenide semiconductor nanocrystals (NCs), which serve as undesirable channels for nonradiative carrier recombination, remain a great challenge impeding the development of solar and optoelectronics devices based on these NCs. In order to design efficient passivation techniques to minimize these trap states, a precise knowledge about the charge carrier dynamics on the NCs surface is essential. However, selective mapping of surface traps requires capabilities beyond the reach of conventional laser spectroscopy and static electron microscopy; it can only be accessed by using a one-of-a-kind, second-generation four-dimensional scanning ultrafast electron microscope (4D S-UEM) with subpicosecond temporal and nanometer spatial resolutions. Here, we precisely map the collective surface charge carrier dynamics of copper indium gallium selenide NCs as a function of the surface trap states before and after surface passivation in real space and time using S-UEM. The time-resolved snapshots clearly demonstrate that the density of the trap states is significantly reduced after zinc sulfide (ZnS) shelling. Furthermore, the removal of trap states and elongation of carrier lifetime are confirmed by the increased photocurrent of the self-biased photodetector fabricated using the shelled NCs.

Matrix photochemical study and conformational analysis of CH3C(O)NCS and CF3C(O)NCS.

PubMed

Ramos, Luis A; Ulic, Sonia E; Romano, Rosana M; Beckers, Helmut; Willner, Helge; Della Védova, Carlos O

2014-01-30

The vapor of acetyl isocyanide, CH3C(O)NCS, and trifluoroacetyl isocyanide, CF3C(O)NCS, were isolated in solid Ar at 15 K. The existence of rotational isomerism was confirmed when the matrixes were irradiated with broad-band UV-vis light (200 ≤ λ ≤ 800 nm) and also by temperature-dependent Ar-matrix IR spectroscopy. The initial spectra showed the vapor of CH3C(O)NCS and CF3C(O)NCS consist of two conformers syn-syn and syn-anti (with the C═O bond syn with respect to the C-H or C-F bond and syn or anti with respect to the N═C double bond). When CH3C(O)NCS is irradiated, simultaneously with the randomization process, H2CCO and HSCN are produced. In the case of the photolysis of CF3C(O)NCS, the main products are CF3NCS and CO. The assignment of the IR bands to the different photoproducts was made on the basis of the usual criteria, taking account reported antecedents in the literature.

Effects of surface functionalization of hydrophilic NaYF4 nanocrystals doped with Eu3+ on glutamate and GABA transport in brain synaptosomes

NASA Astrophysics Data System (ADS)

Sojka, Bartlomiej; Kociołek, Daria; Banski, Mateusz; Borisova, Tatiana; Pozdnyakova, Natalia; Pastukhov, Artem; Borysov, Arsenii; Dudarenko, Marina; Podhorodecki, Artur

2017-08-01

Specific rare earth doped nanocrystals (NCs), a recent class of nanoparticles with fluorescent features, have great bioanalytical potential. Neuroactive properties of NaYF4 nanocrystals doped with Eu3+ were assessed based on the analysis of their effects on glutamate- and γ-aminobutyric acid (GABA) transport process in nerve terminals isolated from rat brain (synaptosomes). Two types of hydrophilic NCs were examined in this work: (i) coated by polyethylene glycol (PEG) and (ii) with OH groups at the surface. It was found that NaYF4:Eu3+-PEG and NaYF4:Eu3+-OH within the concentration range of 0.5-3.5 and 0.5-1.5 mg/ml, respectively, did not influence Na+-dependent transporter-dependent l-[14C]glutamate and [3H]GABA uptake and the ambient level of the neurotransmitters in the synaptosomes. An increase in NaYF4:Eu3+-PEG and NaYF4:Eu3+-OH concentrations up to 7.5 and 3.5 mg/ml, respectively, led to the (1) attenuation of the initial velocity of uptake of l-[14C]glutamate and [3H]GABA and (2) elevation of ambient neurotransmitters in the suspension of nerve terminals. In the mentioned concentrations, nanocrystals did not influence acidification of synaptic vesicles that was shown with pH-sensitive fluorescent dye acridine orange, however, decreased the potential of the plasma membrane of synaptosomes. In comparison with other nanoparticles studied with similar methodological approach, NCs start to exhibit their effects on neurotransmitter transport at concentrations several times higher than those shown for carbon dots, detonation nanodiamonds and an iron storage protein ferritin, whose activity can be registered at 0.08, 0.5 and 0.08 mg/ml, respectively. Therefore, NCs can be considered lesser neurotoxic as compared to above nanoparticles.

Multiple exciton generation and recombination in carbon nanotubes and nanocrystals.

PubMed

Kanemitsu, Yoshihiko

2013-06-18

Semiconducting nanomaterials such as single-walled carbon nanotubes (SWCNTs) and nanocrystals (NCs) exhibit unique size-dependent quantum properties. They have therefore attracted considerable attention from the viewpoints of fundamental physics and functional device applications. SWCNTs and NCs also provide an excellent new stage for experimental studies of many-body effects of electrons and excitons on optical processes in nanomaterials. In this Account, we discuss multiple exciton generation and recombination in SWCNTs and NCs for next-generation photovoltaics. Strongly correlated ensembles of conduction-band electrons and valence-band holes in semiconductors are complex quantum systems that exhibit unique optical phenomena. In bulk crystals, the carrier recombination dynamics can be described by a simple model, which includes the nonradiative single-carrier trapping rate, the radiative two-carrier recombination rate, and the nonradiative three-carrier Auger recombination rate. The nonradiative Auger recombination rate determines the carrier recombination dynamics at high carrier density and depends on the spatial localization of carriers in two-dimensional quantum wells. The Auger recombination and multiple exciton generation rates can be advantageously manipulated by nanomaterials with designated energy structures. In addition, SWCNTs and NCs show quantized recombination dynamics of multiple excitons and carriers. In one-dimensional SWCNTs, excitons have large binding energies and are very stable at room temperature. The extremely rapid Auger recombination between excitons determines the photoluminescence (PL) intensity, the PL linewidth, and the PL lifetime. SWCNTs can undergo multiple exciton generation, while strong exciton-exciton interactions and complicated exciton structures affect the quantized Auger rate and the multiple exciton generation efficiency. Interestingly, in zero-dimensional NC quantum dots, quantized Auger recombination causes unique

Transient Melting and Recrystallization of Semiconductor Nanocrystals Under Multiple Electron–Hole Pair Excitation

DOE PAGES

Kirschner, Matthew S.; Hannah, Daniel C.; Diroll, Benjamin T.; ...

2017-07-28

Ultrafast optical pump, X-ray diffraction probe experiments were performed on CdSe nanocrystal (NC) colloidal dispersions as functions of particle size, polytype, and pump fluence. Bragg peak shifts relate heating and peak amplitude reduction confers lattice disordering. For smaller NCs, melting initiates upon absorption of as few as ~15 electron-hole pair excitations per NC on average (0.89 excitations/nm 3 for a 1.5-nm radius) with roughly the same excitation density inducing melting for all examined NCs. Diffraction intensity recovery kinetics, attributable to recrystallization, occur over hundreds of picoseconds with slower recoveries for larger particles. Zincblende and wurtzite NCs revert to initial structuresmore » following intense photoexcitation suggesting melting occurs primarily at the surface, as supported by simulations. Electronic structure calculations relate significant band gap narrowing with decreased crystallinity. Here, these findings reflect the need to consider the physical stability of nanomaterials and related electronic impacts in high intensity excitation applications such as lasing and solid-state lighting.« less

Transient Melting and Recrystallization of Semiconductor Nanocrystals Under Multiple Electron–Hole Pair Excitation

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

Kirschner, Matthew S.; Hannah, Daniel C.; Diroll, Benjamin T.

Ultrafast optical pump, X-ray diffraction probe experiments were performed on CdSe nanocrystal (NC) colloidal dispersions as functions of particle size, polytype, and pump fluence. Bragg peak shifts relate heating and peak amplitude reduction confers lattice disordering. For smaller NCs, melting initiates upon absorption of as few as ~15 electron-hole pair excitations per NC on average (0.89 excitations/nm 3 for a 1.5-nm radius) with roughly the same excitation density inducing melting for all examined NCs. Diffraction intensity recovery kinetics, attributable to recrystallization, occur over hundreds of picoseconds with slower recoveries for larger particles. Zincblende and wurtzite NCs revert to initial structuresmore » following intense photoexcitation suggesting melting occurs primarily at the surface, as supported by simulations. Electronic structure calculations relate significant band gap narrowing with decreased crystallinity. Here, these findings reflect the need to consider the physical stability of nanomaterials and related electronic impacts in high intensity excitation applications such as lasing and solid-state lighting.« less

Transient Melting and Recrystallization of Semiconductor Nanocrystals Under Multiple Electron-Hole Pair Excitation.

PubMed

Kirschner, Matthew S; Hannah, Daniel C; Diroll, Benjamin T; Zhang, Xiaoyi; Wagner, Michael J; Hayes, Dugan; Chang, Angela Y; Rowland, Clare E; Lethiec, Clotilde M; Schatz, George C; Chen, Lin X; Schaller, Richard D

2017-09-13

Ultrafast optical pump, X-ray diffraction probe experiments were performed on CdSe nanocrystal (NC) colloidal dispersions as functions of particle size, polytype, and pump fluence. Bragg peak shifts related to heating and peak amplitude reduction associated with lattice disordering are observed. For smaller NCs, melting initiates upon absorption of as few as ∼15 electron-hole pair excitations per NC on average (0.89 excitations/nm 3 for a 1.5 nm radius) with roughly the same excitation density inducing melting for all examined NCs. Diffraction intensity recovery kinetics, attributable to recrystallization, occur over hundreds of picoseconds with slower recoveries for larger particles. Zincblende and wurtzite NCs revert to initial structures following intense photoexcitation suggesting melting occurs primarily at the surface, as supported by simulations. Electronic structure calculations relate significant band gap narrowing with decreased crystallinity. These findings reflect the need to consider the physical stability of nanomaterials and related electronic impacts in high intensity excitation applications such as lasing and solid-state lighting.

The determination of extinction coefficient of CuInS2, and ZnCuInS3 multinary nanocrystals.

PubMed

Qin, Lei; Li, Dongze; Zhang, Zhuolei; Wang, Kefei; Ding, Hong; Xie, Renguo; Yang, Wensheng

2012-10-21

A pioneering work for determining the extinction coefficient of colloidal semiconductor nanocrystals (NCs) has been cited over 1500 times (W. Yu, W. Guo, X. G. Peng, Chem. Mater., 2003, 15, 2854-2860), indicating the importance of calculating NC concentration for further research and applications. In this study, the size-dependent nature of the molar extinction coefficient of "greener" CuInS(2) and ZnCuInS(3) NCs with emission covering the whole visible to near infrared (NIR) is presented. With the increase of NC size, the resulting quantitative values of the extinction coefficients of ternary CuInS(2) and quaternary ZnCuInS(3) NCs are found to follow a power function with exponents of 2.1 and 2.5, respectively. Obviously, a larger value of extinction coefficient is observed in quaternary NCs for the same size of particles. The difference of the extinction coefficient from both samples is clearly demonstrated due to incorporating ZnS with a much larger extinction coefficient into CuInS(2) NCs.

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.

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.

Biocompatible fluorescent silicon nanocrystals for single-molecule tracking and fluorescence imaging

PubMed Central

Nishimura, Hirohito; Ritchie, Ken; Kasai, Rinshi S.; Goto, Miki; Morone, Nobuhiro; Sugimura, Hiroyuki; Tanaka, Koichiro; Sase, Ichiro; Yoshimura, Akihiko; Nakano, Yoshitaro; Fujiwara, Takahiro K.

2013-01-01

Fluorescence microscopy is used extensively in cell-biological and biomedical research, but it is often plagued by three major problems with the presently available fluorescent probes: photobleaching, blinking, and large size. We have addressed these problems, with special attention to single-molecule imaging, by developing biocompatible, red-emitting silicon nanocrystals (SiNCs) with a 4.1-nm hydrodynamic diameter. Methods for producing SiNCs by simple chemical etching, for hydrophilically coating them, and for conjugating them to biomolecules precisely at a 1:1 ratio have been developed. Single SiNCs neither blinked nor photobleached during a 300-min overall period observed at video rate. Single receptor molecules in the plasma membrane of living cells (using transferrin receptor) were imaged for ≥10 times longer than with other probes, making it possible for the first time to observe the internalization process of receptor molecules at the single-molecule level. Spatial variations of molecular diffusivity in the scale of 1–2 µm, i.e., a higher level of domain mosaicism in the plasma membrane, were revealed. PMID:24043702

Emission and Structure-Varying ZnO and Carbon Nanocrystal Composite in Mechanical Processing

NASA Astrophysics Data System (ADS)

Torchynska, T.; Perez Millan, B.; Polupan, G.; Kakazey, M.

2018-03-01

Morphology, photoluminescence (PL), and Raman scattering spectra have been investigated for mixtures of ZnO+0.1%C nanocrystals (NCs) at different stages of mechanical processing (MP). The transformation of graphite into graphene monolayers covering the ZnO NC surface is revealed for the first MP stage. The interaction with oxygen has been detected in the second MP stage which leads to the dissolution of oxygen interstitials in the ZnO NCs and to the formation of graphene (graphite) oxides. Increasing the concentration of the oxygen interstitials in ZnO NCs also enhances the intensity stimulation of the orange PL band (2.18eV). Simultaneously, the PL band peaking at 2.82-2.90 eV is detected in the PL spectra of the ZnO+0.1%C NC mixture after MP for 9-90 min. Then, the variation of the ZnO NC shape, agglomeration of ZnO NCs, modification of ZnO defects and decreasing PL intensity have been detected after prolonged MP for 390 min. It is expected that short stages of MP can be useful for ZnO NC surface covering by graphene layers or graphene (graphite) oxides.

Formation of SiGe nanocrystals embedded in Al2O3 for the application of write-once-read-many-times memory

NASA Astrophysics Data System (ADS)

Wu, Min-Lin; Wu, Yung-Hsien; Lin, Chia-Chun; Chen, Lun-Lun

2012-10-01

The structure of SiGe nanocrystals embedded in Al2O3 formed by sequential deposition of Al2O3/Si/Ge/Al2O3 and a subsequent annealing was confirmed by transmission electron microscopy and energy dispersive spectroscopy (EDS), and its application for write-once-read-many-times (WORM) memory devices was explored in this study. By applying a -10 V pulse for 1 s, a large amount of holes injected from Si substrate are stored in the nanocrystals and consequently, the current at +1.5 V increases by a factor of 104 as compared to that of the initial state. Even with a smaller -5 V pulse for 1 μs, a sufficiently large current ratio of 36 can still be obtained, verifying the low power operation. Since holes are stored in nanocrystals which are isolated from Si substrate by Al2O3 with good integrity and correspond to a large valence band offset with respect to Al2O3, desirable read endurance up to 105 cycles and excellent retention over 100 yr are achieved. Combining these promising characteristics, WORM memory devices are appropriate for high-performance archival storage applications.

Hybrid Silicon Nanocrystal/Poly(3-hexylthiophene-2,5-diyl) Solar Cells from a Chlorinated Silicon Precursor

NASA Astrophysics Data System (ADS)

Ding, Yi; Gresback, Ryan; Yamada, Riku; Okazaki, Ken; Nozaki, Tomohiro

2013-11-01

Freestanding silicon nanocrystals (Si NCs) synthesized by a nonthermal plasma from silicon tetrachloride (SiCl4) were successfully employed in hybrid Si NC/poly(3-hexylthiophene-2,5-diyl) (P3HT) bulk-hetrojunction (BHJ) solar cells. The weight fraction of Si NCs in P3HT greatly influences device performance. As the weight fraction increases up to 50 wt %, short-circuit current dramatically increases, while open-circuit voltage (Voc) and fill factor (FF) do not change significantly. The improvement in device performance is attributed to both increased probability of exciton dissociation in P3HT and an enhancement in the light conversion of wavelengths where P3HT is a poor absorber. These results demonstrate an alternative approach to synthesizing Si NCs from SiCl4 instead of silane (SiH4) for optoelectronic devices.

Structural Evolution of Sub-10 nm Octahedral Platinum$-$Nickel Bimetallic Nanocrystals

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

Chang, Qiaowan; Xu, Yuan; Duan, Zhiyuan

Octahedral Pt alloy nanocrystals (NCs) have shown excellent activities as electrocatalysts toward oxygen reduction reaction (ORR). As the activity and stability of NCs are highly dependent on their structure and the elemental distribution, it is of great importance to understand the formation mechanism of octahedral NCs and to rationally synthesize shape-controlled alloy catalysts with optimized ORR activity and stability. However, the factors controlling the structural and compositional evolution during the synthesis have not been well understood yet. Here in this paper, we systematically investigated the structure and composition evolution pathways of Pt–Ni octahedra synthesized with the assistance of W(CO) 6more » and revealed a unique core–shell structure consisting of a Pt core and a Pt–Ni alloy shell. Below 140 °C, sphere-like pure Pt NCs with the diameter of 3–4 nm first nucleated, followed by the isotropic growth of Pt–Ni alloy on the seeds at temperatures between 170 and 230 °C forming Pt@Pt–Ni core–shell octahedra with {111} facets. Owing to its unique structure, the Pt@Pt–Ni octahedra show an unparalleled stability during potential cycling, that is, no activity drop after 10 000 cycles between 0.6 and 1.0 V. This work proposes the Pt@Pt–Ni octahedra as a high profile electrocatalyst for ORR and reveals the structural and composition evolution pathways of Pt-based bimetallic NCs.« less

Structural Evolution of Sub-10 nm Octahedral Platinum$-$Nickel Bimetallic Nanocrystals

DOE PAGES

Chang, Qiaowan; Xu, Yuan; Duan, Zhiyuan; ...

2017-05-11

Octahedral Pt alloy nanocrystals (NCs) have shown excellent activities as electrocatalysts toward oxygen reduction reaction (ORR). As the activity and stability of NCs are highly dependent on their structure and the elemental distribution, it is of great importance to understand the formation mechanism of octahedral NCs and to rationally synthesize shape-controlled alloy catalysts with optimized ORR activity and stability. However, the factors controlling the structural and compositional evolution during the synthesis have not been well understood yet. Here in this paper, we systematically investigated the structure and composition evolution pathways of Pt–Ni octahedra synthesized with the assistance of W(CO) 6more » and revealed a unique core–shell structure consisting of a Pt core and a Pt–Ni alloy shell. Below 140 °C, sphere-like pure Pt NCs with the diameter of 3–4 nm first nucleated, followed by the isotropic growth of Pt–Ni alloy on the seeds at temperatures between 170 and 230 °C forming Pt@Pt–Ni core–shell octahedra with {111} facets. Owing to its unique structure, the Pt@Pt–Ni octahedra show an unparalleled stability during potential cycling, that is, no activity drop after 10 000 cycles between 0.6 and 1.0 V. This work proposes the Pt@Pt–Ni octahedra as a high profile electrocatalyst for ORR and reveals the structural and composition evolution pathways of Pt-based bimetallic NCs.« less

Long-Range Order in Nanocrystal Assemblies Determines Charge Transport of Films

DOE PAGES

Sainato, Michela; Shevitski, Brian; Sahu, Ayaskanta; ...

2017-07-18

Self-assembly of semiconductor nanocrystals (NCs) into two-dimensional patterns or three-dimensional (2- 3D) superstructures has emerged as a promising low-cost route to generate thin-film transistors and solar cells with superior charge transport because of enhanced electronic coupling between the NCs. Here, we show that lead sulfide (PbS) NCs solids featuring either short-range (disordered glassy solids, GSs) or long-range (superlattices, SLs) packing order are obtained solely by controlling deposition conditions of colloidal solution of NCs. In this study, we demonstrate the use of the evaporation-driven self-assembly method results in PbS NC SL structures that are observed over an area of 1 mmmore » × 100 μm, with long-range translational order of up to 100 nm. A number of ordered domains appear to have nucleated simultaneously and grown together over the whole area, imparting a polycrystalline texture to the 3D SL films. By contrast, a conventional, optimized spin-coating deposition method results in PbS NC glassy films with no translational symmetry and much shorter-range packing order in agreement with state-of-the-art reports. Further, we investigate the electronic properties of both SL and GS films, using a field-effect transistor configuration as a test platform. The long-range ordering of the PbS NCs into SLs leads to semiconducting NC-based solids, the mobility (μ) of which is 3 orders of magnitude higher than that of the disordered GSs. Furthemore, although spin-cast GSs of PbS NCs have weak ambipolar behavior with limited gate tunability, SLs of PbS NCs show a clear p-type behavior with significantly higher conductivities.« less

{331}-Faceted trisoctahedral gold nanocrystals: synthesis, superior electrocatalytic performance and highly efficient SERS activity

NASA Astrophysics Data System (ADS)

Song, Yahui; Miao, Tingting; Zhang, Peina; Bi, Cuixia; Xia, Haibing; Wang, Dayang; Tao, Xutang

2015-04-01

We investigate the effect of gold (Au) seeds prepared in cetyltrimethylammonium chloride solution (CTAC-Au seeds) on the index facets of trisoctahedral gold nanocrystals (TOH Au NCs). We demonstrate that monodisperse {331}-faceted TOH Au NCs with controllable sizes (from 60 to 255 nm) can be successfully prepared in high yield by using 3.0 nm CTAC-Au seeds or as-prepared 70 nm TOH Au NCs as seeds. We find that the electrocatalytic performance on methanol oxidation and surface enhancement Raman spectroscopy (SERS) activity of {331}-faceted TOH Au NCs is size-dependent. In comparison with well-known nanoporous gold (0.088 mA cm-2), {331}-faceted TOH Au NCs with sizes of 110 nm exhibit fairly high catalytic activity (0.178 mA cm-2) on methanol oxidation (1.0 M) in alkaline media due to the presence of increasing density of atomic steps, ledges, and kinks on the NC surfaces. Their current density is reduced by less than 7% after 500 cycling tests. {331}-Faceted TOH Au NCs with sizes of 175 nm exhibit the highest SERS activity for 4-aminothiophenol (4-ATP) molecules. The enhancement factors of a1 modes of 4-ATP molecules can reach the order of 109 when the 4-ATP concentration is 3 × 10-6 M. Moreover, Raman signals (ag modes) of 4,4'-dimercaptoazobenzene (DMAB) molecules on TOH Au NCs are stronger than those on spherical Au NCs of comparable size due to the enhanced laser-induced transformation of 4-ATP molecules by high-index {331}-facets during SERS measurement. Furthermore, the SERS intensities of 4-methylbenzenethiol (4-MTP) molecules on TOH Au NCs are also higher than those on spherical Au NCs of comparable size due to sharp extremities.We investigate the effect of gold (Au) seeds prepared in cetyltrimethylammonium chloride solution (CTAC-Au seeds) on the index facets of trisoctahedral gold nanocrystals (TOH Au NCs). We demonstrate that monodisperse {331}-faceted TOH Au NCs with controllable sizes (from 60 to 255 nm) can be successfully prepared in high yield by

Unravelling the surface chemistry of metal oxide nanocrystals, the role of acids and bases.

PubMed

De Roo, Jonathan; Van den Broeck, Freya; De Keukeleere, Katrien; Martins, José C; Van Driessche, Isabel; Hens, Zeger

2014-07-09

We synthesized HfO2 nanocrystals from HfCl4 using a surfactant-free solvothermal process in benzyl alcohol and found that the resulting nanocrystals could be transferred to nonpolar media using a mixture of carboxylic acids and amines. Using solution (1)H NMR, FTIR, and elemental analysis, we studied the details of the transfer reaction and the surface chemistry of the resulting sterically stabilized nanocrystals. As-synthesized nanocrystals are charge-stabilized by protons, with chloride acting as the counterion. Treatment with only carboxylic acids does not lead to any binding of ligands to the HfO2 surface. On the other hand, we find that the addition of amines provides the basic environment in which carboxylic acids can dissociate and replace chloride. This results in stable, aggregate-free dispersions of HfO2 nanocrystals, sterically stabilized by carboxylate ligands. Moreover, titrations with deuterated carboxylic acid show that the charge on the carboxylate ligands is balanced by coadsorbed protons. Hence, opposite from the X-type/nonstoichiometric nanocrystals picture prevailing in literature, one should look at HfO2/carboxylate nanocrystals as systems where carboxylic acids are dissociatively adsorbed to bind to the nanocrystals. Similar results were obtained with ZrO2 NCs. Since proton accommodation on the surface is most likely due to the high Brønsted basicity of oxygen, our model could be a more general picture for the surface chemistry of metal oxide nanocrystals with important consequences on the chemistry of ligand exchange reactions.

Effect of Phosphine-Free Selenium Precursor Reactivity on The Optical and Vibrational properties of Colloidal CdSe Nanocrystals

NASA Astrophysics Data System (ADS)

Thi, L. A.; Lieu, N. T. T.; Hoa, N. M.; Tran, N.; Binh, N. T.; Quang, V. X.; Nghia, N. X.

2018-03-01

Phosphine-free selenium precursor solutions have been prepared by heating at temperatures ranging from 160 °C to 240 °C and studied by means of infrared absorption spectroscopy. The colloidal CdSe nanocrystals (NCs) synthesized from all those solutions by the wet chemical method. The influence of heating temperature on the chemical reactivity of selenium precursor and its role on the optical and vibrational properties of CdSe NCs are discussed in details. Their morphology, particle size, structural, optical and vibrational properties were investigated using transmission electron microscopy, X-ray diffraction, UV-Vis, fluorescence and Raman spectroscopy, respectively.

Folate receptor targeted, rare-earth oxide nanocrystals for bi-modal fluorescence and magnetic imaging of cancer cells.

PubMed

Setua, Sonali; Menon, Deepthy; Asok, Adersh; Nair, Shantikumar; Koyakutty, Manzoor

2010-02-01

Targeted cancer imaging using rare-earth oxide nanocrystals, free from heavy metals (Cd, Se, Te, Hg and Pb), showing bright red-fluorescence and magnetic resonance imaging (MRI) is presented. Y(2)O(3) nanocrystals (YO NC) doped in situ with fluorescent (Eu(3+)) and paramagnetic (Gd(3+)) impurities and conjugated with a potential cancer targeting ligand, folic acid (FA), were prepared using an all-aqueous wet-chemical process. Structural, optical and magnetic properties of these multifunctional nanocrystals were investigated by X-ray diffraction, electron microscopy, photoluminescence and magnetization studies. Highly monodisperse nanocrystals of size approximately 20 nm with cubic bixbyite crystal structure showed bright red-fluorescence when doped with Eu(3+). Co-doping with Gd(3+) and mild air drying resulted significantly enhanced fluorescence quantum efficiency of approximately 60% together with paramagnetic functionality, enabling T(1)-weighted MR contrast with approximately 5 times higher spin-lattice relaxivity compared to the clinically used Gd(3+) contrast agent. Cytotoxicity and reactive oxygen stress studies show no toxicity by YO NC in both normal and cancer cells up to higher doses of 500 microm and longer incubation time, 48h. Cancer targeting capability of FA conjugated NCs was demonstrated on folate receptor positive (FR+) human nasopharyngeal carcinoma cells (KB) with FR depressed KB (FRd) and FR negative (FR-) lung cancer cells A549 as controls. Fluorescence microscopy and flow-cytometry data show highly specific binding and cellular uptake of large concentration of FA conjugated NCs on FR+ve cells compared to the controls. Thus, the present study reveals, unique bi-modal contrast imaging capability, non-toxicity and cancer targeting capability of multiple impurities doped rare-earth oxide nanocrystals that can find promising application in molecular imaging.

In situ growth of well-dispersed CdS nanocrystals in semiconducting polymers

PubMed Central

2013-01-01

A straight synthetic route to fabricate hybrid nanocomposite films of well-dispersed CdS nanocrystals (NCs) in poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) is reported. A soluble cadmium complex [Cd(SBz)2]2·MI, obtained by incorporating a Lewis base (1-methylimidazole, MI) on the cadmium bis(benzyl)thiol, is used as starting reagent in an in situ thermolytic process. CdS NCs with spherical shape nucleate and grow well below 200°C in a relatively short time (30 min). Photoluminescence spectroscopy measurements performed on CdS/MEH-PPV nanocomposites show that CdS photoluminescence peaks are totally quenched inside MEH-PPV, if compared to CdS/PMMA nanocomposites, as expected due to overlapping of the polymer absorption and CdS emission spectra. The CdS NCs are well-dispersed in size and homogeneously distributed within MEH-PPV matrix as proved by transmission electron microscopy. Nanocomposites with different precursor/polymer weight ratios were prepared in the range from 1:4 to 4:1. Highly dense materials, without NCs clustering, were obtained for a weight/weight ratio of 2:3 between precursor and polymer, making these nanocomposites particularly suitable for optoelectronic and solar energy conversion applications. PMID:24015753

White light emission from Mn2 + doped ZnS nanocrystals through the surface chelating of 8-hydroxyquinoline-5-sulfonic acid

NASA Astrophysics Data System (ADS)

Lü, Xiaodan; Yang, Jing; Fu, Yuqin; Liu, Qianqian; Qi, Bin; Lü, Changli; Su, Zhongmin

2010-03-01

White light emitting semiconductor nanocrystals (NCs) have been successfully synthesized from 8-hydroxyquinoline-5-sulfonic acid (HQS) decorated manganese doped ZnS NCs through fine tuning the surface-coordination emission and dopant emission of the NC host. The HQS functionalized manganese doped ZnS NCs (QS-ZnS:Mn), with a cubic crystal structure, have the same diameter of about 4.0 nm as ZnS:Mn NCs without HQS. The intensity of the surface-coordination emission peak increased with increasing HQS content or augmenting excited wavelength. The emission of white light was achieved by carefully controlling the dosage of HQS in NCs and appropriately tuning the excited wavelength. The color coordinates (0.35, 0.34) for the efficient white light emitting NCs were very close to the ideal Commission Internationale de l'Eclairage (CIE) chromaticity coordinates for pure white light (0.33, 0.33). The photoluminescence (PL) decay study revealed that the white light emitting NCs exhibited maximum lifetime values at different emission peaks for different NC samples. The study results also indicated that the HQS molecules were attached to the surface of ZnS:Mn NCs in a single coordination fashion due to the steric hindrance effect of the special spherical surface of NCs, which made the QS-ZnS:Mn NCs possess stable and high fluorescent properties in different organic solvents as compared with the conventional small molecule complexes.

Plasmonic doped semiconductor nanocrystals: Properties, fabrication, applications and perspectives

NASA Astrophysics Data System (ADS)

Kriegel, Ilka; Scotognella, Francesco; Manna, Liberato

2017-02-01

Degenerately doped semiconductor nanocrystals (NCs) are of recent interest to the NC community due to their tunable localized surface plasmon resonances (LSPRs) in the near infrared (NIR). The high level of doping in such materials with carrier densities in the range of 1021cm-3 leads to degeneracy of the doping levels and intense plasmonic absorption in the NIR. The lower carrier density in degenerately doped semiconductor NCs compared to noble metals enables LSPR tuning over a wide spectral range, since even a minor change of the carrier density strongly affects the spectral position of the LSPR. Two classes of degenerate semiconductors are most relevant in this respect: impurity doped semiconductors, such as metal oxides, and vacancy doped semiconductors, such as copper chalcogenides. In the latter it is the density of copper vacancies that controls the carrier concentration, while in the former the introduction of impurity atoms adds carriers to the system. LSPR tuning in vacancy doped semiconductor NCs such as copper chalcogenides occurs by chemically controlling the copper vacancy density. This goes in hand with complex structural modifications of the copper chalcogenide crystal lattice. In contrast the LSPR of degenerately doped metal oxide NCs is modified by varying the doping concentration or by the choice of host and dopant atoms, but also through the addition of capacitive charge carriers to the conduction band of the metal oxide upon post-synthetic treatments, such as by electrochemical- or photodoping. The NIR LSPRs and the option of their spectral fine-tuning make accessible important new features, such as the controlled coupling of the LSPR to other physical signatures or the enhancement of optical signals in the NIR, sensing application by LSPR tracking, energy production from the NIR plasmon resonance or bio-medical applications in the biological window. In this review we highlight the recent advances in the synthesis of various different plasmonic

Femtosecond laser-induced size reduction and emission quantum yield enhancement of colloidal silicon nanocrystals: Effect of laser ablation time.

PubMed

Zhang, Yingxiong; Wu, Wenshun; Hao, Huilian; Shen, Wenzhong

2018-06-19

Colloidal silicon (Si) nanocrystals (NCs) with different sizes were successfully prepared by femtosecond laser ablation under different laser ablation time (LAT). The mean size decreases from 4.23 to 1.42 nm with increasing LAT from 30 to 120 min. In combination with structural characterization, temperature-dependent photoluminescence (PL), time-resolved PL, and PL excitation spectra, we attribute room temperature blue emissions peaked at 405 and 430 nm to the radiative recombination of electron-hole pairs via the oxygen deficient centers related to Si-C-H2 and Si-O-Si bonds of colloidal Si NCs prepared in 1-octene, respectively. In particular, the measured PL quantum yield of colloidal Si NCs has been enhanced significantly from 23.6% to 55.8% with prolonging LAT from 30 to 120 min. © 2018 IOP Publishing Ltd.

Photoluminescence spectral study of single cadmium selenide/zinc sulfide colloidal nanocrystals in poly(methyl methacrylate) and quantum dots molecules

NASA Astrophysics Data System (ADS)

Shen, Yaoming

Quantum dots (QDs)and Nano-crystals (NCs) have been studies for decades. Because of the nanoscale quantum confinement, delta shape like energy density states and narrowband emitters properties, they hold great promise for numerous optoelectronics and photonics applications. They could be used for tunable lasers, white LED, Nano-OLED, non-volatile memory and solar cells. They are also the most promising candidates for the quantum computing. The benefits for NCs over QDs is that NCs can be incorporated into a variety of polymers as well as thin films of bulk semiconductors. These exceptional flexibility and structural control distinguish NCs from the more traditional QD structures fabricated using epitaxial growth techniques. In my research of work, I studied the photoluminescence (PL) and absorption character of ensemble NCs incorporated in Polymethyl methacrylate (PMMA). To understand the behavior of the NCs in PMMA, it is important to measure a singe NC to avoid the inhomogenous broading of many NCs. So I particularly studied the behavior of a single NC in PMMA matrix. A microphotoluminescence setup to optically isolate a single nanocrystal is used. Random spectral shift and blinking behavior (on and off) are found. Addition to that, two color spectral shifting, is a major phenomena found in the system. Other interesting results such as PL intensity changes (decreasing or increasing with time) and quenching effect are observed and explained too. From the correlation function, we can distinguish the phonon replicas. The energy of these phonons can be calculated very accurately from the experiment result. The Huang-Rhys factors can be estimated too. Self-assembled semiconductor quantum dots (QDs), from highly strained-layer heteroepitaxy in the Stranski-Krastanow (S-K) growth mode, have been intensively studied because of the delta-function-like density of states, which is significant for optoelectronic applications. Spontaneous formation of semiconductor quantum

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.

Ultra-small plutonium oxide nanocrystals: an innovative material in plutonium science.

PubMed

Hudry, Damien; Apostolidis, Christos; Walter, Olaf; Janssen, Arne; Manara, Dario; Griveau, Jean-Christophe; Colineau, Eric; Vitova, Tonya; Prüssmann, Tim; Wang, Di; Kübel, Christian; Meyer, Daniel

2014-08-11

Apart from its technological importance, plutonium (Pu) is also one of the most intriguing elements because of its non-conventional physical properties and fascinating chemistry. Those fundamental aspects are particularly interesting when dealing with the challenging study of plutonium-based nanomaterials. Here we show that ultra-small (3.2±0.9 nm) and highly crystalline plutonium oxide (PuO2 ) nanocrystals (NCs) can be synthesized by the thermal decomposition of plutonyl nitrate ([PuO2 (NO3 )2 ]⋅3 H2 O) in a highly coordinating organic medium. This is the first example reporting on the preparation of significant quantities (several tens of milligrams) of PuO2 NCs, in a controllable and reproducible manner. The structure and magnetic properties of PuO2 NCs have been characterized by a wide variety of techniques (powder X-ray diffraction (PXRD), X-ray absorption fine structure (XAFS), X-ray absorption near edge structure (XANES), TEM, IR, Raman, UV/Vis spectroscopies, and superconducting quantum interference device (SQUID) magnetometry). The current PuO2 NCs constitute an innovative material for the study of challenging problems as diverse as the transport behavior of plutonium in the environment or size and shape effects on the physics of transuranium elements. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Template-free fabrication of hollow N-doped carbon sphere (h-NCS) to synthesize h-NCS@PANI positive material for MoO3//h-NCS@PANI asymmetric supercapacitor

NASA Astrophysics Data System (ADS)

Li, Xiaoqin; Xiang, Xinxin; Liu, Yunhua; Xiao, Dan

2018-06-01

Asymmetric supercapacitors (ASCs) based on pseudocapacitor electrode materials are vital to improve the electrochemical properties of devices in aqueous electrolytes. This study fabricates hollow N-doped carbon sphere (h-NCS) to produce h-NCS@PANI nanocomposite as positive electrode and α-MoO3 as negative electrode to assemble ASC device. In particular, a facile template-free synthesis method, catalyzed by Cu2+, is used to prepare hollow PANI nanosphere precursor to build h-NCS. The mechanism of the precursor formation is illustrated in detail. After polymerization of PANI on the surface of h-NCS, the capacitance increases to 327 F g-1 at 1 A g-1. Furthermore, a hydrothermal reaction is carried out to produce α-MoO3 negative electrode material. The maximum specific capacitance of 720 F g-1 is achieved at 1 A g-1. The obtained h-NCS@PANI and α-MoO3 are utilized to construct an ASC device. The electrochemical properties of this device are investigated comprehensively. The maximum energy density of 34.1 W h kg-1 and power density of 9350.6 W kg-1 are observed, which provide an insight into the development of ASCs.

Water-Assisted Size and Shape Control of CsPbBr3 Perovskite Nanocrystals.

PubMed

Zhang, Xiaoyu; Bai, Xue; Wu, Hua; Zhang, Xiangtong; Sun, Chun; Zhang, Yu; Zhang, Wei; Zheng, Weitao; Yu, William W; Rogach, Andrey L

2018-03-19

Lead-halide perovskites are well known to decompose rapidly when exposed to polar solvents, such as water. Contrary to this common-place observation, we have found that through introducing a suitable minor amount of water into the reaction mixture, we can synthesize stable CsPbBr 3 nanocrystals. The size and the crystallinity, and as a result the band gap tunability of the strongly emitting CsPbBr 3 nanocrystals correlate with the water content. Suitable amounts of water change the crystallization environment, inducing the formation of differently shaped perovskites, namely spherical NCs, rectangular nanoplatelets, or nanowires. Bright CsPbBr 3 nanocrystals with the photoluminescence quantum yield reaching 90 % were employed for fabrication of inverted hybrid inorganic/organic light-emitting devices, with the peak luminance of 4428 cd m -2 and external quantum yield of 1.7 %. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Zhu, H. X.; Zhang, T.; Wang, R. X.

A nano-floating gate memory structure based on Ni nanocrystals (NCs) embedded HfO{sub x} film is deposited by means of radio-frequency magnetron sputtering. Microstructure investigations reveal that self-organized Ni-NCs with diameters of 4-8 nm are well dispersed in amorphous HfO{sub x} matrix. Pt/Ni-NCs embedded HfO{sub x}/Si/Ag capacitor structures exhibit voltage-dependent capacitance-voltage hysteresis, and a maximum flat-band voltage shift of 1.5 V, corresponding to a charge storage density of 6.0 × 10{sup 12} electrons/cm{sup 2}, is achieved. These capacitor memory cells exhibit good endurance characteristic up to 4 × 10{sup 4} cycles and excellent retention performance of 10{sup 5} s, fulfilling themore » requirements of next generation non-volatile memory devices. Schottky tunneling is proven to be responsible for electrons tunneling in these capacitors.« less

Nanocomposite Phosphor Consisting of CaI2:Eu2+ Single Nanocrystals Embedded in Crystalline SiO2.

PubMed

Daicho, Hisayoshi; Iwasaki, Takeshi; Shinomiya, Yu; Nakano, Akitoshi; Sawa, Hiroshi; Yamada, Wataru; Matsuishi, Satoru; Hosono, Hideo

2017-11-29

High luminescence efficiency is obtained in halide- and chalcogenide-based phosphors, but they are impractical because of their poor chemical durability. Here we report a halide-based nanocomposite phosphor with excellent luminescence efficiency and sufficient durability for practical use. Our approach was to disperse luminescent single nanocrystals of CaI 2 :Eu 2+ in a chemically stable, translucent crystalline SiO 2 matrix. Using this approach, we successfully prepared a nanocomposite phosphor by means of self-organization through a simple solid-state reaction. Single nanocrystals of 6H polytype (thr notation) CaI 2 :Eu 2+ with diameters of about 50 nm could be generated not only in a SiO 2 amorphous powder but also in a SiO 2 glass plate. The nanocomposite phosphor formed upon solidification of molten CaI 2 left behind in the crystalline SiO 2 that formed from the amorphous SiO 2 under the influence of a CaI 2 flux effect. The resulting nanocomposite phosphor emitted brilliant blue luminescence with an internal quantum efficiency up to 98% upon 407 nm violet excitation. We used cathodoluminescence microscopy, scanning transmission electron microscopy, and Rietveld refinement of the X-ray diffraction patterns to confirm that the blue luminescence was generated only by the CaI 2 :Eu 2+ single nanocrystals. The phosphor was chemically durable because the luminescence sites were embedded in the crystalline SiO 2 matrix. The phosphor is suitable for use in near-ultraviolet light-emitting diodes. The concept for this nanocomposite phosphor can be expected to be effective for improvements in the practicality of poorly durable materials such as halides and chalcogenides.

``Flash'' synthesis of ``giant'' Mn-doped CdS/ZnSe/ZnS nanocrystals with ZnSe layer as hole quantum-well

NASA Astrophysics Data System (ADS)

Xu, Ruilin; Zhang, Jiayu

Usually, exciton-Mn energy transfer in Mn-doped CdS/ZnS nanocrystals (NCs) can readily outcompete the exciton trapping by an order of magnitude. However, with the accumulation of non-radiative defects in the giant shell during the rapid growth of the thick shell (up to ~20 monolayers in no more than 10 minutes), the photoluminescence (PL) quantum yield of this kind of ``giant'' NCs is significantly reduced by the accumulation of non-radiative defects during the rapid growth of thick shell. That is because the exciton-Mn energy transfer in Mn-doped CdS/ZnS NCs is significantly inhibited by the hole trapping as the major competing process, resulting from the insufficient hole-confinement in CdS/ZnS NCs. Accordingly ``flash'' synthesis of giant Mn-doped CdS/ZnSe/ZnS NCs with ZnSe layer as hole quantum-well is developed to suppress the inhibition. Meanwhile Mn2+ PL peak changes profoundly from ~620 nm to ~540 nm after addition of ZnSe layer. Studies are under the way to explore the relevant mechanisms.

Tuning Nanocrystal Surface Depletion by Controlling Dopant Distribution as a Route Toward Enhanced Film Conductivity

NASA Astrophysics Data System (ADS)

Staller, Corey M.; Robinson, Zachary L.; Agrawal, Ankit; Gibbs, Stephen L.; Greenberg, Benjamin L.; Lounis, Sebastien D.; Kortshagen, Uwe R.; Milliron, Delia J.

2018-05-01

Electron conduction through bare metal oxide nanocrystal (NC) films is hindered by surface depletion regions resulting from the presence of surface states. We control the radial dopant distribution in tin-doped indium oxide (ITO) NCs as a means to manipulate the NC depletion width. We find in films of ITO NCs of equal overall dopant concentration that those with dopant-enriched surfaces show decreased depletion width and increased conductivity. Variable temperature conductivity data shows electron localization length increases and associated depletion width decreases monotonically with increased density of dopants near the NC surface. We calculate band profiles for NCs of differing radial dopant distributions and, in agreement with variable temperature conductivity fits, find NCs with dopant-enriched surfaces have narrower depletion widths and longer localization lengths than those with dopant-enriched cores. Following amelioration of NC surface depletion by atomic layer deposition of alumina, all films of equal overall dopant concentration have similar conductivity. Variable temperature conductivity measurements on alumina-capped films indicate all films behave as granular metals. Herein, we conclude that dopant-enriched surfaces decrease the near-surface depletion region, which directly increases the electron localization length and conductivity of NC films.

Tuning Nanocrystal Surface Depletion by Controlling Dopant Distribution as a Route Toward Enhanced Film Conductivity.

PubMed

Staller, Corey M; Robinson, Zachary L; Agrawal, Ankit; Gibbs, Stephen L; Greenberg, Benjamin L; Lounis, Sebastien D; Kortshagen, Uwe R; Milliron, Delia J

2018-05-09

Electron conduction through bare metal oxide nanocrystal (NC) films is hindered by surface depletion regions resulting from the presence of surface states. We control the radial dopant distribution in tin-doped indium oxide (ITO) NCs as a means to manipulate the NC depletion width. We find in films of ITO NCs of equal overall dopant concentration that those with dopant-enriched surfaces show decreased depletion width and increased conductivity. Variable temperature conductivity data show electron localization length increases and associated depletion width decreases monotonically with increased density of dopants near the NC surface. We calculate band profiles for NCs of differing radial dopant distributions and in agreement with variable temperature conductivity fits find NCs with dopant-enriched surfaces have narrower depletion widths and longer localization lengths than those with dopant-enriched cores. Following amelioration of NC surface depletion by atomic layer deposition of alumina, all films of equal overall dopant concentration have similar conductivity. Variable temperature conductivity measurements on alumina-capped films indicate all films behave as granular metals. Herein, we conclude that dopant-enriched surfaces decrease the near-surface depletion region, which directly increases the electron localization length and conductivity of NC films.

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.

Insight into the mechanism revealing the peroxidase mimetic catalytic activity of quaternary CuZnFeS nanocrystals: colorimetric biosensing of hydrogen peroxide and glucose

NASA Astrophysics Data System (ADS)

Dalui, Amit; Pradhan, Bapi; Thupakula, Umamahesh; Khan, Ali Hossain; Kumar, Gundam Sandeep; Ghosh, Tanmay; Satpati, Biswarup; Acharya, Somobrata

2015-05-01

Artificial enzyme mimetics have attracted immense interest recently because natural enzymes undergo easy denaturation under environmental conditions restricting practical usefulness. We report for the first time chalcopyrite CuZnFeS (CZIS) alloyed nanocrystals (NCs) as novel biomimetic catalysts with efficient intrinsic peroxidase-like activity. Novel peroxidase activities of CZIS NCs have been evaluated by catalytic oxidation of the peroxidase substrate 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of hydrogen peroxide (H2O2). CZIS NCs demonstrate the synergistic effect of elemental composition and photoactivity towards peroxidase-like activity. The quaternary CZIS NCs show enhanced intrinsic peroxidase-like activity compared to the binary NCs with the same constituent elements. Intrinsic peroxidase-like activity has been correlated with the energy band position of CZIS NCs extracted using scanning tunneling spectroscopy and ultraviolet photoelectron spectroscopy. Kinetic analyses indicate Michaelis-Menten enzyme kinetic model catalytic behavior describing the rate of the enzymatic reaction by correlating the reaction rate with substrate concentration. Typical color reactions arising from the catalytic oxidation of TMB over CZIS NCs with H2O2 have been utilized to establish a simple and sensitive colorimetric assay for detection of H2O2 and glucose. CZIS NCs are recyclable catalysts showing high efficiency in multiple uses. Our study may open up the possibility of designing new photoactive multi-component alloyed NCs as enzyme mimetics in biotechnology applications.Artificial enzyme mimetics have attracted immense interest recently because natural enzymes undergo easy denaturation under environmental conditions restricting practical usefulness. We report for the first time chalcopyrite CuZnFeS (CZIS) alloyed nanocrystals (NCs) as novel biomimetic catalysts with efficient intrinsic peroxidase-like activity. Novel peroxidase activities of CZIS NCs have been

47 CFR Appendix to Part 216 - NCS Directives

Code of Federal Regulations, 2011 CFR

2011-10-01

...—Telecommunications Operations—Shared Resources (SHARES) High Frequency (HF) Radio Program Note: NCS Directives and... Telecommunication OFFICE OF SCIENCE AND TECHNOLOGY POLICY AND NATIONAL SECURITY COUNCIL NATIONAL COMMUNICATIONS..., Membership and Administration—National Communications System (NCS) Issuance System NCS Directive 1-2...

47 CFR Appendix to Part 216 - NCS Directives

Code of Federal Regulations, 2013 CFR

2013-10-01

...—Telecommunications Operations—Shared Resources (SHARES) High Frequency (HF) Radio Program Note: NCS Directives and... Telecommunication OFFICE OF SCIENCE AND TECHNOLOGY POLICY AND NATIONAL SECURITY COUNCIL NATIONAL COMMUNICATIONS..., Membership and Administration—National Communications System (NCS) Issuance System NCS Directive 1-2...

47 CFR Appendix to Part 216 - NCS Directives

Code of Federal Regulations, 2010 CFR

2010-10-01

...—Telecommunications Operations—Shared Resources (SHARES) High Frequency (HF) Radio Program Note: NCS Directives and... Telecommunication OFFICE OF SCIENCE AND TECHNOLOGY POLICY AND NATIONAL SECURITY COUNCIL NATIONAL COMMUNICATIONS..., Membership and Administration—National Communications System (NCS) Issuance System NCS Directive 1-2...

47 CFR Appendix to Part 216 - NCS Directives

Code of Federal Regulations, 2012 CFR

2012-10-01

...—Telecommunications Operations—Shared Resources (SHARES) High Frequency (HF) Radio Program Note: NCS Directives and... Telecommunication OFFICE OF SCIENCE AND TECHNOLOGY POLICY AND NATIONAL SECURITY COUNCIL NATIONAL COMMUNICATIONS..., Membership and Administration—National Communications System (NCS) Issuance System NCS Directive 1-2...

47 CFR Appendix to Part 216 - NCS Directives

Code of Federal Regulations, 2014 CFR

2014-10-01

...—Telecommunications Operations—Shared Resources (SHARES) High Frequency (HF) Radio Program Note: NCS Directives and... Telecommunication OFFICE OF SCIENCE AND TECHNOLOGY POLICY AND NATIONAL SECURITY COUNCIL NATIONAL COMMUNICATIONS..., Membership and Administration—National Communications System (NCS) Issuance System NCS Directive 1-2...

Dense Ge nanocrystals embedded in TiO2 with exponentially increased photoconduction by field effect.

PubMed

Lepadatu, A-M; Slav, A; Palade, C; Dascalescu, I; Enculescu, M; Iftimie, S; Lazanu, S; Teodorescu, V S; Ciurea, M L; Stoica, T

2018-03-20

Si and Ge nanocrystals in oxides are of a large interest for photo-effect applications due to the fine-tuning of the optical bandgap by quantum confinement in nanocrystals. In this work, dense Ge nanocrystals suitable for enhanced photoconduction were fabricated from 60% Ge in TiO 2 amorphous layers by low temperature rapid thermal annealing at 550 °C. An exponential increase of the photocurrent with the applied voltage was observed in coplanar structure of Ge nanocrystals composite films deposited on oxidized Si wafers. The behaviour was explained by field effect control of the Fermi level at the Ge nanocrystals-TiO 2 layer/substrate interfaces. The blue-shift of the absorption gap from bulk Ge value to 1.14 eV was evidenced in both photocurrent spectra and optical reflection-transmission experiments, in good agreement with quantum confinement induced bandgap broadening in Ge nanocrystal with sizes of about 5 nm as found from HRTEM and XRD investigations. A nonmonotonic spectral dependence of the refractive index is associated to the Ge nanocrystals formation. The nanocrystal morphology is also in good agreement with the Coulomb gap hopping mechanism of T -1/2 -type explaining the temperature dependence of the dark conduction.

Interface traps contribution on transport mechanisms under illumination in metal-oxide-semiconductor structures based on silicon nanocrystals

NASA Astrophysics Data System (ADS)

Chatbouri, S.; Troudi, M.; Kalboussi, A.; Souifi, A.

2018-02-01

The transport phenomena in metal-oxide-semiconductor (MOS) structures having silicon nanocrystals (Si-NCs) inside the dielectric layer have been investigated, in dark condition and under visible illumination. At first, using deep-level transient spectroscopy (DLTS), we find the presence of series electron traps having very close energy levels (comprised between 0.28 and 0.45 eV) for ours devices (with/without Si-NCs). And a single peak appears at low temperature only for MOS with Si-NCs related to Si-NCs DLTS response. In dark condition, the conduction mechanism is dominated by the thermionic fast emission/capture of charge carriers from the highly doped polysilicon layer to Si-substrate through interface trap states for MOS without Si-NCs. The tunneling of charge carriers from highly poly-Si to Si substrate trough the trapping/detrapping mechanism in the Si-NCs, at low temperature, contributed to the conduction mechanism for MOS with Si-NCs. The light effect on transport mechanisms has been investigated using current-voltage ( I- V), and high frequency capacitance-voltage ( C- V) methods. We have been marked the photoactive trap effect in inversion zone at room temperature in I- V characteristics, which confirm the contribution of photo-generated charge on the transport mechanisms from highly poly-Si to Si substrate trough the photo-trapping/detrapping mechanism in the Si-NCs and interfaces traps levels. These results have been confirmed by an increasing about 10 pF in capacity's values for the C- V characteristics of MOS with Si-NCs, in the inversion region for inverse high voltage applied under photoexcitation at low temperature. These results are helpful to understand the principle of charge transport in dark condition and under illumination, of MOS structures having Si-NCs in the SiO x = 1.5 oxide matrix.

Enhancing optical gains in Si nanocrystals via hydrogenation and cerium ion doping

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

Wang, Dong-Chen; Li, Yan-Li; Song, Sheng-Chi

We report optical gain enhancements in Si nanocrystals (Si-NCs) via hydrogenation and Ce{sup 3+} ion doping. Variable stripe length technique was used to obtain gains. At 0.3 W/cm{sup 2} pumping power density of pulsed laser, net gains were observed together with gain enhancements after hydrogenation and/or Ce{sup 3+} ion doping; gains after loss corrections were between 89.52 and 341.95 cm{sup −1}; and the photoluminescence (PL) lifetime was found to decrease with the increasing gain enhancement. At 0.04 W/cm{sup 2} power density, however, no net gain was found and the PL lifetime increased with the increasing PL enhancement. The results were discussed according tomore » stimulated and spontaneous excitation and de-excitation mechanisms of Si-NCs.« less

Conversion of invisible metal-organic frameworks to luminescent perovskite nanocrystals for confidential information encryption and decryption.

PubMed

Zhang, Congyang; Wang, Bo; Li, Wanbin; Huang, Shouqiang; Kong, Long; Li, Zhichun; Li, Liang

2017-10-31

Traditional smart fluorescent materials, which have been attracting increasing interest for security protection, are usually visible under either ambient or UV light, making them adverse to the potential application of confidential information protection. Herein, we report an approach to realize confidential information protection and storage based on the conversion of lead-based metal-organic frameworks (MOFs) to luminescent perovskite nanocrystals (NCs). Owing to the invisible and controlled printable characteristics of lead-based MOFs, confidential information can be recorded and encrypted by MOF patterns, which cannot be read through common decryption methods. Through our conversion strategy, highly luminescent perovskite NCs can be formed quickly and simply by using a halide salt trigger that reacts with the MOF, thus promoting effective information decryption. Finally, through polar solvents impregnation and halide salt conversion, the luminescence of the perovskite NCs can be quenched and recovered, leading to reversible on/off switching of the luminescence signal for multiple information encryption and decryption processes.

Crystal phase-controlled synthesis of rod-shaped AgInTe2 nanocrystals for in vivo imaging in the near-infrared wavelength region

NASA Astrophysics Data System (ADS)

Kameyama, Tatsuya; Ishigami, Yujiro; Yukawa, Hiroshi; Shimada, Taisuke; Baba, Yoshinobu; Ishikawa, Tetsuya; Kuwabata, Susumu; Torimoto, Tsukasa

2016-03-01

Rod-shaped AgInTe2 nanocrystals (NCs) exhibiting intense near-band edge photoluminescence in the near-infrared (NIR) wavelength region, were successfully prepared by the thermal reaction of metal acetates and Te precursors in 1-dodecanethiol. Increasing the reaction temperature resulted in the formation of larger AgInTe2 NCs with crystal structures varying from hexagonal to tetragonal at reaction temperatures of 280 °C or higher. The energy gap was increased from 1.13 to 1.20 eV with a decrease in rod width from 8.3 to 5.6 nm, accompanied by a blue shift in the photoluminescence (PL) peak wavelength from 1097 to 1033 nm. The optimal PL quantum yield was approximately 18% for AgInTe2 NCs with rod widths of 5.6 nm. The applicability of AgInTe2 NCs as a NIR-emitting material for in vivo biological imaging was examined by injecting AgInTe2 NC-incorporated liposomes into the back of a C57BL/6 mouse, followed by in vivo photoluminescence imaging in the NIR region.Rod-shaped AgInTe2 nanocrystals (NCs) exhibiting intense near-band edge photoluminescence in the near-infrared (NIR) wavelength region, were successfully prepared by the thermal reaction of metal acetates and Te precursors in 1-dodecanethiol. Increasing the reaction temperature resulted in the formation of larger AgInTe2 NCs with crystal structures varying from hexagonal to tetragonal at reaction temperatures of 280 °C or higher. The energy gap was increased from 1.13 to 1.20 eV with a decrease in rod width from 8.3 to 5.6 nm, accompanied by a blue shift in the photoluminescence (PL) peak wavelength from 1097 to 1033 nm. The optimal PL quantum yield was approximately 18% for AgInTe2 NCs with rod widths of 5.6 nm. The applicability of AgInTe2 NCs as a NIR-emitting material for in vivo biological imaging was examined by injecting AgInTe2 NC-incorporated liposomes into the back of a C57BL/6 mouse, followed by in vivo photoluminescence imaging in the NIR region. Electronic supplementary information (ESI) available

CuGaS₂ and CuGaS₂-ZnS Porous Layers from Solution-Processed Nanocrystals.

PubMed

Berestok, Taisiia; Guardia, Pablo; Estradé, Sònia; Llorca, Jordi; Peiró, Francesca; Cabot, Andreu; Brock, Stephanie L

2018-04-05

The manufacturing of semiconducting films using solution-based approaches is considered a low cost alternative to vacuum-based thin film deposition strategies. An additional advantage of solution processing methods is the possibility to control the layer nano/microstructure. Here, we detail the production of mesoporous CuGaS₂ (CGS) and ZnS layers from spin-coating and subsequent cross-linking through chalcogen-chalcogen bonds of properly functionalized nanocrystals (NCs). We further produce NC-based porous CGS/ZnS bilayers and NC-based CGS-ZnS composite layers using the same strategy. Photoelectrochemical measurements are used to demonstrate the efficacy of porous layers, and particularly the CGS/ZnS bilayers, for improved current densities and photoresponses relative to denser films deposited from as-produced NCs.

Low-resistivity bulk silicon prepared by hot-pressing boron- and phosphorus-hyperdoped silicon nanocrystals

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

Luan, Qingbin; Ni, Zhenyi; Zhu, Tiejun

2014-12-15

Technologically important low-resistivity bulk Si has been usually produced by the traditional Czochralski growth method. We now explore a novel method to obtain low-resistivity bulk Si by hot-pressing B- and P-hyperdoped Si nanocrystals (NCs). In this work bulk Si with the resistivity as low as ∼ 0.8 (40) mΩ•cm has been produced by hot pressing P (B)-hyperdoped Si NCs. The dopant type is found to make a difference for the sintering of Si NCs during the hot pressing. Bulk Si hot-pressed from P-hyperdoped Si NCs is more compact than that hot-pressed from B-hyperdoped Si NCs when the hot-pressing temperature ismore » the same. This leads to the fact that P is more effectively activated to produce free carriers than B in the hot-pressed bulk Si. Compared with the dopant concentration, the hot-pressing temperature more significantly affects the structural and electrical properties of hot-pressed bulk Si. With the increase of the hot-pressing temperature the density of hot-pressed bulk Si increases. The highest carrier concentration (lowest resistivity) of bulk Si hot-pressed from B- or P-hyperdoped Si NCs is obtained at the highest hot-pressing temperature of 1050 °C. The mobility of carriers in the hot-pressed bulk Si is low (≤  ∼ 30 cm{sup -2}V{sup -1}s{sup -1}) mainly due to the scattering of carriers induced by structural defects such as pores.« less

Highly Efficient Light-Emitting Diodes of Colloidal Metal-Halide Perovskite Nanocrystals beyond Quantum Size.

PubMed

Kim, Young-Hoon; Wolf, Christoph; Kim, Young-Tae; Cho, Himchan; Kwon, Woosung; Do, Sungan; Sadhanala, Aditya; Park, Chan Gyung; Rhee, Shi-Woo; Im, Sang Hyuk; Friend, Richard H; Lee, Tae-Woo

2017-07-25

Colloidal metal-halide perovskite quantum dots (QDs) with a dimension less than the exciton Bohr diameter D B (quantum size regime) emerged as promising light emitters due to their spectrally narrow light, facile color tuning, and high photoluminescence quantum efficiency (PLQE). However, their size-sensitive emission wavelength and color purity and low electroluminescence efficiency are still challenging aspects. Here, we demonstrate highly efficient light-emitting diodes (LEDs) based on the colloidal perovskite nanocrystals (NCs) in a dimension > D B (regime beyond quantum size) by using a multifunctional buffer hole injection layer (Buf-HIL). The perovskite NCs with a dimension greater than D B show a size-irrespective high color purity and PLQE by managing the recombination of excitons occurring at surface traps and inside the NCs. The Buf-HIL composed of poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS) and perfluorinated ionomer induces uniform perovskite particle films with complete film coverage and prevents exciton quenching at the PEDOT:PSS/perovskite particle film interface. With these strategies, we achieved a very high PLQE (∼60.5%) in compact perovskite particle films without any complex post-treatments and multilayers and a high current efficiency of 15.5 cd/A in the LEDs of colloidal perovskite NCs, even in a simplified structure, which is the highest efficiency to date in green LEDs that use colloidal organic-inorganic metal-halide perovskite nanoparticles including perovskite QDs and NCs. These results can help to guide development of various light-emitting optoelectronic applications based on perovskite NCs.

Synthesis of blue-shifted luminescent colloidal GaN nanocrystals through femtosecond pulsed laser ablation in organic solution

NASA Astrophysics Data System (ADS)

Demirel, Abdülmelik; Öztaş, Tuğba; Kurşungöz, Canan; Yılmaz, İbrahim; Ortaç, Bülend

2016-05-01

We demonstrate the synthesis of GaN nanocrystals (NCs) with the sizes of less than the doubled exciton Bohr radius leading quantum confinement effects via a single-step technique. The generation of colloidal GaN nanoparticles (NPs) in organic solution through nanosecond (ns) and femtosecond (fs) pulsed laser ablation (PLA) of GaN powder was carried out. Ns PLA in ethanol and polymer matrix resulted in amorphous GaN-NPs with the size distribution of 12.4 ± 7.0 and 6.4 ± 2.3 nm, respectively, whereas fs PLA in ethanol produced colloidal GaN-NCs with spherical shape within 4.2 ± 1.9 nm particle size distribution. XRD and selected area electron diffraction analysis of the product via fs PLA revealed that GaN-NCs are in wurtzite structure. Moreover, X-ray photoelectron spectroscopy measurements also confirm the presence of GaN nanomaterials. The colloidal GaN-NCs solution exhibits strong blue shift in the absorption spectrum compared to that of the GaN-NPs via ns PLA in ethanol. Furthermore, the photoluminescence emission behavior of fs PLA-generated GaN-NCs in the 295-400 nm wavelength range is observed with a peak position located at 305 nm showing a strong blue shift with respect to the bulk GaN.

Optically Active CdSe-Dot/CdS-Rod Nanocrystals with Induced Chirality and Circularly Polarized Luminescence.

PubMed

Cheng, Jiaji; Hao, Junjie; Liu, Haochen; Li, Jiagen; Li, Junzi; Zhu, Xi; Lin, Xiaodong; Wang, Kai; He, Tingchao

2018-05-30

Ligand-induced chirality in semiconductor nanocrystals (NCs) has attracted attention because of the tunable optical properties of the NCs. Induced circular dichroism (CD) has been observed in CdX (X = S, Se, Te) NCs and their hybrids, but circularly polarized luminescence (CPL) in these fluorescent nanomaterials has been seldom reported. Herein, we describe the successful preparation of l- and d-cysteine-capped CdSe-dot/CdS-rods (DRs) with tunable CD and CPL behaviors and a maximum anisotropic factor ( g lum ) of 4.66 × 10 -4 . The observed CD and CPL activities are sensitive to the relative absorption ratio of the CdS shell to the CdSe core, suggesting that the anisotropic g-factors in both CD and CPL increase to some extent for a smaller shell-to-core absorption ratio. In addition, the molar ratio of chiral cysteine to the DRs is investigated. Instead of enhancing the chiral interactions between the chiral molecules and DRs, an excess of cysteine molecules in aqueous solution inhibits both the CD and CPL activities. Such chiral and emissive NCs provide an ideal platform for the rational design of semiconductor nanomaterials with chiroptical properties.

The role of ion exchange in the passivation of In(Zn)P nanocrystals with ZnS

PubMed Central

Cho, Deok-Yong; Xi, Lifei; Boothroyd, Chris; Kardynal, Beata; Lam, Yeng Ming

2016-01-01

We have investigated the chemical state of In(Zn)P/ZnS core/shell nanocrystals (NCs) for color conversion applications using hard X-ray absorption spectroscopy (XAS) and photoluminescence excitation (PLE). Analyses of the edge energies as well as the X-ray absorption fine structure (XAFS) reveal that the Zn2+ ions from ZnS remain in the shell while the S2− ions penetrate into the core at an early stage of the ZnS deposition. It is further demonstrated that for short growth times, the ZnS shell coverage on the core was incomplete, whereas the coverage improved gradually as the shell deposition time increased. Together with evidence from PLE spectra, where there is a strong indication of the presence of P vacancies, this suggests that the core-shell interface in the In(Zn)P/ZnS NCs are subject to substantial atomic exchanges and detailed models for the shell structure beyond simple layer coverage are needed. This substantial atomic exchange is very likely to be the reason for the improved photoluminescence behavior of the core-shell particles compare to In(Zn)P-only NCs as S can passivate the NCs surfaces. PMID:26972936

Effect of rapid thermal annealing temperature on the dispersion of Si nanocrystals in SiO2 matrix

NASA Astrophysics Data System (ADS)

Saxena, Nupur; Kumar, Pragati; Gupta, Vinay

2015-05-01

Effect of rapid thermal annealing temperature on the dispersion of silicon nanocrystals (Si-NC's) embedded in SiO2 matrix grown by atom beam sputtering (ABS) method is reported. The dispersion of Si NCs in SiO2 is an important issue to fabricate high efficiency devices based on Si-NC's. The transmission electron microscopy studies reveal that the precipitation of excess silicon is almost uniform and the particles grow in almost uniform size upto 850 °C. The size distribution of the particles broadens and becomes bimodal as the temperature is increased to 950 °C. This suggests that by controlling the annealing temperature, the dispersion of Si-NC's can be controlled. The results are supported by selected area diffraction (SAED) studies and micro photoluminescence (PL) spectroscopy. The discussion of effect of particle size distribution on PL spectrum is presented based on tight binding approximation (TBA) method using Gaussian and log-normal distribution of particles. The study suggests that the dispersion and consequently emission energy varies as a function of particle size distribution and that can be controlled by annealing parameters.

Rapid and High-Efficiency Laser-Alloying Formation of ZnMgO Nanocrystals

PubMed Central

Liu, Peisheng; Wang, Hao; Chen, Jun; Li, Xiaoming; Zeng, Haibo

2016-01-01

Applications of ZnMgO nanocrystals (NCs), especially in photoelectric detectors, have significant limitations because of the unresolved phase separation in the synthesis process. Here, we propose a rapid and highly efficient ZnMgO NC alloying method based on pulsed laser ablation in liquid. The limit value of homogeneous magnesium (Mg) is pushed from 37% to 62%, and the optical band gap is increased to 3.7 eV with high doping efficiency (>100%). Further investigations on the lattice geometry of ZnMgO NCs indicate that all ZnMgO NCs are hexagonal wurtzite structures, and the (002) and (100) peaks shift to higher diffraction angles with the increase in Mg doping content. The calculated results of the lattice constants a and c slightly decrease based on Bragg’s law and lattice geometry equations. Furthermore, the relationship between annealing temperature and the limit value of homogeneous Mg is examined, and the results reveal that the latter decreases with the former because of the phase separation of MgO. A probable mechanism of zinc magnesium alloy is introduced to expound on the details of the laser-alloying process. PMID:27324296

Postsynthesis Phase Transformation for CsPbBr3/Rb4PbBr6 Core/shell Nanocrystals with Exceptional Photostability.

PubMed

Wang, Bo; Zhang, Congyang; Huang, Shouqiang; Li, Zhichun; Kong, Long; Jin, Ling; Wang, Junhui; Wu, Kaifeng; Li, Liang

2018-06-15

Lead halide perovskite nanocrystals (NCs) as promising optoelectronic materials are intensively researched. However, the instability is one of the biggest challenges needed to overcome before fulfill their practical applications. To improve their stability, we present a postsynthetic controlled phase transformation of CsPbBr3 toward CsPbBr3/Rb4PbBr6 core/shell structure triggered by rubidium oleate treatment. The resulted core/shell NCs show exceptional photostability both in solution and on-chip. The solution of CsPbBr3/Rb4PbBr6 NCs can remain over 90% of the initial emission photoluminescence quantum yields (PLQY) after 42 h of intense light-emitting diodes illumination (450 nm, 175 mW/cm2), which is even better than the conventional CdSe/CdS quantum dots whose emission drop to 50% after 18 h under the same condition. We believe that the exceptional photostability should be resulted from the protection of the robust Rb4PbBr6 shell on CsPbBr3 NCs.

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.

Heavily doped n-type PbSe and PbS nanocrystals using ground-state charge transfer from cobaltocene

DOE PAGES

Koh, Weon-kyu; Koposov, Alexey Y.; Stewart, John T.; ...

2013-06-18

Colloidal nanocrystals (NCs) of lead chalcogenides are a promising class of tunable infrared materials for applications in devices such as photodetectors and solar cells. Such devices typically employ electronic materials in which charge carrier concentrations are manipulated through “doping;” however, persistent electronic doping of these NCs remains a challenge. In this paper, we demonstrate that heavily doped n-type PbSe and PbS NCs can be realized utilizing ground-state electron transfer from cobaltocene. This allows injecting up to eight electrons per NC into the band-edge state and maintaining the doping level for at least a month at room temperature. Doping is confirmedmore » by inter- and intra-band optical absorption, as well as by carrier dynamics. In conclusion, FET measurements of doped NC films and the demonstration of a p-n diode provide additional evidence that the developed doping procedure allows for persistent incorporation of electrons into the quantum-confined NC states.« less

Cu3-xP Nanocrystals as a Material Platform for Near-Infrared Plasmonics and Cation Exchange Reactions

PubMed Central

2015-01-01

Synthesis approaches to colloidal Cu3P nanocrystals (NCs) have been recently developed, and their optical absorption features in the near-infrared (NIR) have been interpreted as arising from a localized surface plasmon resonance (LSPR). Our pump–probe measurements on platelet-shaped Cu3-xP NCs corroborate the plasmonic character of this absorption. In accordance with studies on crystal structure analysis of Cu3P dating back to the 1970s, our density functional calculations indicate that this material is substoichiometric in copper, since the energy of formation of Cu vacancies in certain crystallographic sites is negative, that is, they are thermodynamically favored. Also, thermoelectric measurements point to a p-type behavior of the majority carriers from films of Cu3-xP NCs. It is likely that both the LSPR and the p-type character of our Cu3-xP NCs arise from the presence of a large number of Cu vacancies in such NCs. Motivated by the presence of Cu vacancies that facilitate the ion diffusion, we have additionally exploited Cu3-xP NCs as a starting material on which to probe cation exchange reactions. We demonstrate here that Cu3-xP NCs can be easily cation-exchanged to hexagonal wurtzite InP NCs, with preservation of the anion framework (the anion framework in Cu3-xP is very close to that of wurtzite InP). Intermediate steps in this reaction are represented by Cu3-xP/InP heterostructures, as a consequence of the fact that the exchange between Cu+ and In3+ ions starts from the peripheral corners of each NC and gradually evolves toward the center. The feasibility of this transformation makes Cu3-xP NCs an interesting material platform from which to access other metal phosphides by cation exchange. PMID:25960605

Bio-NCs--the marriage of ultrasmall metal nanoclusters with biomolecules.

PubMed

Goswami, Nirmal; Zheng, Kaiyuan; Xie, Jianping

2014-11-21

Ultrasmall metal nanoclusters (NCs) have attracted increasing attention due to their fascinating physicochemical properties. Today, functional metal NCs are finding growing acceptance in biomedical applications. To achieve a better performance in biomedical applications, metal NCs can be interfaced with biomolecules, such as proteins, peptides, and DNA, to form a new class of biomolecule-NC composites (or bio-NCs in short), which typically show synergistic or novel physicochemical and physiological properties. This feature article focuses on the recent studies emerging at the interface of metal NCs and biomolecules, where the interactions could impart unique physicochemical properties to the metal NCs, as well as mutually regulate biological functions of the bio-NCs. In this article, we first provide a broad overview of key concepts and developments in the novel biomolecule-directed synthesis of metal NCs. A special focus is placed on the key roles of biomolecules in metal NC synthesis. In the second part, we describe how the encapsulated metal NCs affect the structure and function of biomolecules. Followed by that, we discuss several unique synergistic effects observed in the bio-NCs, and illustrate them with examples highlighting their potential biomedical applications. Continued interdisciplinary efforts are required to build up in-depth knowledge about the interfacial chemistry and biology of bio-NCs, which could further pave their ways toward biomedical applications.

Bio-NCs - the marriage of ultrasmall metal nanoclusters with biomolecules

NASA Astrophysics Data System (ADS)

Goswami, Nirmal; Zheng, Kaiyuan; Xie, Jianping

2014-10-01

Ultrasmall metal nanoclusters (NCs) have attracted increasing attention due to their fascinating physicochemical properties. Today, functional metal NCs are finding growing acceptance in biomedical applications. To achieve a better performance in biomedical applications, metal NCs can be interfaced with biomolecules, such as proteins, peptides, and DNA, to form a new class of biomolecule-NC composites (or bio-NCs in short), which typically show synergistic or novel physicochemical and physiological properties. This feature article focuses on the recent studies emerging at the interface of metal NCs and biomolecules, where the interactions could impart unique physicochemical properties to the metal NCs, as well as mutually regulate biological functions of the bio-NCs. In this article, we first provide a broad overview of key concepts and developments in the novel biomolecule-directed synthesis of metal NCs. A special focus is placed on the key roles of biomolecules in metal NC synthesis. In the second part, we describe how the encapsulated metal NCs affect the structure and function of biomolecules. Followed by that, we discuss several unique synergistic effects observed in the bio-NCs, and illustrate them with examples highlighting their potential biomedical applications. Continued interdisciplinary efforts are required to build up in-depth knowledge about the interfacial chemistry and biology of bio-NCs, which could further pave their ways toward biomedical applications.

Glycerol-bonded 3C-SiC nanocrystal solid films exhibiting broad and stable violet to blue-green emission.

PubMed

Wang, J; Xiong, S J; Wu, X L; Li, T H; Chu, Paul K

2010-04-14

We have produced glycerol-bonded 3C-SiC nanocrystal (NC) films, which when excited by photons of different wavelengths, produce strong and tunable violet to blue-green (360-540 nm) emission as a result of the quantum confinement effects rendered by the 3C-SiC NCs. The emission is so intense that the emission spots are visible to the naked eyes. The light emission is very stable and even after storing in air for more than six months, no intensity degradation can be observed. X-ray photoelectron spectroscopy and absorption fine structure measurements indicate that the Si-terminated NC surfaces are completely bonded to glycerol molecules. Calculations of geometry optimization and electron structures based on the density functional theory for 3C-SiC NCs with attached glycerol molecules show that these molecules are bonded on the NCs causing strong surface structural change, while the isolated levels in the conduction band of the bare 3C-SiC NCs are replaced with quasi-continuous bands that provide continuous tunability of the emitted light by changing the frequencies of exciting laser. As an application, we demonstrate the potential of using 3C-SiC NCs to fabricate full-color emitting solid films by incorporating porous silicon.

Quasi-self-trapped Frenkel-exciton near-UV luminescence with large Stokes shift in wide-bandgap Cs4PbCl6 nanocrystals

NASA Astrophysics Data System (ADS)

Zhang, Yumeng; Fan, Baolu; Liu, Yuzhen; Li, Hongxia; Deng, Kaiming; Fan, Jiyang

2018-04-01

Inorganic lead halide perovskite nanocrystals (NCs) have attracted great interest owing to their superior luminescence and optoelectronic properties. In comparison to cubic CsPbX3 (X = Cl, Br, or I) that has visible luminescence, trigonal Cs4PbX6 has a much larger bandgap and distinct optical properties. Little has been known about the luminescence properties of the Cs4PbX6 NCs. In this study, we synthesize the well-crystallized Cs4PbCl6 NCs with sizes of 2.2-11.8 nm, which exhibit stable and near-UV luminescence (with a lifetime of 19.7-24.2 ns) with a remarkable quantum confinement effect at room temperature. In comparison to the negligible Stokes shift in the CsPbCl3 NCs, the Stokes shift of the Cs4PbCl6 NCs is very large (0.91 eV). The experimental results in combination with the first-principles calculations reveal that the near-UV luminescence of the Cs4PbCl6 NCs stems from the Frenkel excitons self-trapped in the isolated PbCl64- octahedrons. This is different from the CsPbCl3 NCs whose luminescence originates from the free Wannier excitons. The theoretical model based on the lattice relaxation is proposed to account for the large Stokes shift and its abnormal decrease with the decreasing particle size.

Novel red-emission of ternary ZnCdSe semiconductor nanocrystals

NASA Astrophysics Data System (ADS)

Chung, Shu-Ru; Wang, Kuan-Wen; Chen, Hong-Shuo; Chen, Hong-Hong

2015-02-01

The effect of chain lengths of fatty acids on the physical properties of CdSe and ZnCdSe semiconductor nanocrystals (NCs) synthesized by the colloidal chemistry procedure is investigated. The fatty acids, lauric acid (LA), and stearic acid (SA), with different lengths of carbon chains, are used to prepare CdSe and ZnCdSe NCs when hexyldecylamine (HDA) is applied as the sole surfactant. For CdSe-SA and ZnCdSe-SA, they have the same emission wavelength at 592 nm and the same particle size of 3.3 nm; however, their quantum yield (QY) is 75 and 16 %, respectively. In contrast, the emission wavelength of CdSe-LA and ZnCdSe-LA NCs is 609 and 615 nm, the particle size is about 3.5 and 4 nm under the same reaction time, and the QY of them are 33 and 59 %, respectively. The X-ray diffraction pattern shows that ZnCdSe NCs all have the wurtzite structure, and their main peaks are located between those of pure CdSe and ZnSe materials. The main phase of ZnCdSe-SA and ZnCdSe-LA is ZnSe and CdSe, respectively, implying that alloyed ZnCdSe NC can be prepared and ZnSe and CdSe phase can be promoted by SA and LA, respectively. Moreover, the QY of red-emission ZnCdSe-LA is higher than 50 %. These results suggest that the growth rate of CdSe as well as ZnCdSe NC can be enhanced by using LA as complex reagent and HDA as sole surfactant. It is expected that the reported effective synthetic strategy can be developed as a very practical, easy and not time-consuming approach to prepare red emissive NCs with high QY and high reproducibility.

Benzoyl Halides as Alternative Precursors for the Colloidal Synthesis of Lead-Based Halide Perovskite Nanocrystals

PubMed Central

2018-01-01

We propose here a new colloidal approach for the synthesis of both all-inorganic and hybrid organic–inorganic lead halide perovskite nanocrystals (NCs). The main limitation of the protocols that are currently in use, such as the hot injection and the ligand-assisted reprecipitation routes, is that they employ PbX2 (X = Cl, Br, or I) salts as both lead and halide precursors. This imposes restrictions on being able to precisely tune the amount of reaction species and, consequently, on being able to regulate the composition of the final NCs. In order to overcome this issue, we show here that benzoyl halides can be efficiently used as halide sources to be injected in a solution of metal cations (mainly in the form of metal carboxylates) for the synthesis of APbX3 NCs (in which A = Cs+, CH3NH3+, or CH(NH2)2+). In this way, it is possible to independently tune the amount of both cations and halide precursors in the synthesis. The APbX3 NCs that were prepared with our protocol show excellent optical properties, such as high photoluminescence quantum yields, low amplified spontaneous emission thresholds, and enhanced stability in air. It is noteworthy that CsPbI3 NCs, which crystallize in the cubic α phase, are stable in air for weeks without any postsynthesis treatment. The improved properties of our CsPbX3 perovskite NCs can be ascribed to the formation of lead halide terminated surfaces, in which Cs cations are replaced by alkylammonium ions. PMID:29378131

Benzoyl Halides as Alternative Precursors for the Colloidal Synthesis of Lead-Based Halide Perovskite Nanocrystals.

PubMed

Imran, Muhammad; Caligiuri, Vincenzo; Wang, Mengjiao; Goldoni, Luca; Prato, Mirko; Krahne, Roman; De Trizio, Luca; Manna, Liberato

2018-02-21

We propose here a new colloidal approach for the synthesis of both all-inorganic and hybrid organic-inorganic lead halide perovskite nanocrystals (NCs). The main limitation of the protocols that are currently in use, such as the hot injection and the ligand-assisted reprecipitation routes, is that they employ PbX 2 (X = Cl, Br, or I) salts as both lead and halide precursors. This imposes restrictions on being able to precisely tune the amount of reaction species and, consequently, on being able to regulate the composition of the final NCs. In order to overcome this issue, we show here that benzoyl halides can be efficiently used as halide sources to be injected in a solution of metal cations (mainly in the form of metal carboxylates) for the synthesis of APbX 3 NCs (in which A = Cs + , CH 3 NH 3 + , or CH(NH 2 ) 2 + ). In this way, it is possible to independently tune the amount of both cations and halide precursors in the synthesis. The APbX 3 NCs that were prepared with our protocol show excellent optical properties, such as high photoluminescence quantum yields, low amplified spontaneous emission thresholds, and enhanced stability in air. It is noteworthy that CsPbI 3 NCs, which crystallize in the cubic α phase, are stable in air for weeks without any postsynthesis treatment. The improved properties of our CsPbX 3 perovskite NCs can be ascribed to the formation of lead halide terminated surfaces, in which Cs cations are replaced by alkylammonium ions.

Pick a Color MARIA: Adaptive Sampling Enables the Rapid Identification of Complex Perovskite Nanocrystal Compositions with Defined Emission Characteristics.

PubMed

Bezinge, Leonard; Maceiczyk, Richard M; Lignos, Ioannis; Kovalenko, Maksym V; deMello, Andrew J

2018-06-06

Recent advances in the development of hybrid organic-inorganic lead halide perovskite (LHP) nanocrystals (NCs) have demonstrated their versatility and potential application in photovoltaics and as light sources through compositional tuning of optical properties. That said, due to their compositional complexity, the targeted synthesis of mixed-cation and/or mixed-halide LHP NCs still represents an immense challenge for traditional batch-scale chemistry. To address this limitation, we herein report the integration of a high-throughput segmented-flow microfluidic reactor and a self-optimizing algorithm for the synthesis of NCs with defined emission properties. The algorithm, named Multiparametric Automated Regression Kriging Interpolation and Adaptive Sampling (MARIA), iteratively computes optimal sampling points at each stage of an experimental sequence to reach a target emission peak wavelength based on spectroscopic measurements. We demonstrate the efficacy of the method through the synthesis of multinary LHP NCs, (Cs/FA)Pb(I/Br) 3 (FA = formamidinium) and (Rb/Cs/FA)Pb(I/Br) 3 NCs, using MARIA to rapidly identify reagent concentrations that yield user-defined photoluminescence peak wavelengths in the green-red spectral region. The procedure returns a robust model around a target output in far fewer measurements than systematic screening of parametric space and additionally enables the prediction of other spectral properties, such as, full-width at half-maximum and intensity, for conditions yielding NCs with similar emission peak wavelength.

Versatile hydrogel-based nanocrystal microreactors towards uniform fluorescent photonic crystal supraballs

NASA Astrophysics Data System (ADS)

Zhang, Jing; Tian, Yu; Ling, Lu-Ting; Yin, Su-Na; Wang, Cai-Feng; Chen, Su

2014-12-01

Versatile hydrogel-based nanocrystal (NC) microreactors were designed in this work for the construction of uniform fluorescence colloidal photonic crystal (CPC) supraballs. The hydrogel-based microspheres with sizes ranging from 150 to 300 nm were prepared by seeded copolymerization of acrylic acid and 2-hydroxyethyl methacrylate with micrometer-sized PS seed particles. As an independent NC microreactor, the as-synthesized hydrogel microsphere can effectively capture the guest cadmium ions due to the abundant carboxyl groups inside. Followed by the introduction of chalcogenides, in situ generation of higher-uptake NCs with sizes less than 5 nm was finally realized. Additionally, with the aid of the microfluidic device, the as-obtained NC-latex hybrids can be further self-assembled to bi-functional CPC supraballs bearing brilliant structural colors and uniform fluorescence. This research offers an alternative way to finely bind CPCs with NCs, which will facilitate progress in fields of self-assembled functional colloids and photonic materials.

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

Formation of SiGe nanocrystals embedded in Al{sub 2}O{sub 3} for the application of write-once-read-many-times memory

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

Wu, Min-Lin; Wu, Yung-Hsien; Lin, Chia-Chun

2012-10-15

The structure of SiGe nanocrystals embedded in Al{sub 2}O{sub 3} formed by sequential deposition of Al{sub 2}O{sub 3}/Si/Ge/Al{sub 2}O{sub 3} and a subsequent annealing was confirmed by transmission electron microscopy and energy dispersive spectroscopy (EDS), and its application for write-once-read-many-times (WORM) memory devices was explored in this study. By applying a -10 V pulse for 1 s, a large amount of holes injected from Si substrate are stored in the nanocrystals and consequently, the current at +1.5 V increases by a factor of 10{sup 4} as compared to that of the initial state. Even with a smaller -5 V pulsemore » for 1 {mu}s, a sufficiently large current ratio of 36 can still be obtained, verifying the low power operation. Since holes are stored in nanocrystals which are isolated from Si substrate by Al{sub 2}O{sub 3} with good integrity and correspond to a large valence band offset with respect to Al{sub 2}O{sub 3}, desirable read endurance up to 10{sup 5} cycles and excellent retention over 100 yr are achieved. Combining these promising characteristics, WORM memory devices are appropriate for high-performance archival storage applications.« less

Effect of CdS nanocrystals on charge transport mechanism in poly(3-hexylthiophene)

NASA Astrophysics Data System (ADS)

Khan, Mohd Taukeer; Almohammedi, Abdullah

2017-08-01

The present manuscript demonstrates the optical and electrical characteristics of poly(3-hexylthiophene) (P3HT) and cadmium sulphide (CdS) hybrid nanocomposites. Optical results suggest that there is a formation of charge transfer complex (CTC) between host P3HT and guest CdS nanocrystals (NCs). Electrical properties of P3HT and P3HT-CdS thin films have been studied in hole only device configurations at different temperatures (290 K-150 K), and results were analysed by the space charge limited conduction mechanism. Density of traps and characteristic trap energy increase on incorporation of inorganic NCs in the polymer matrix, which might be due to the additional favourable energy states created by CdS NCs in the band gap of P3HT. These additional trap states assist charge carriers to move quicker which results in enhancement of hole mobility from 7 × 10-6 to 5.5 × 10-5 cm2/V s in nanocomposites. These results suggest that the P3HT-CdS hybrid system has desirable optical and electrical properties for its applications to photovoltaics devices.

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.

Application of hybrid SiO2-coated CdTe nanocrystals for sensitive sensing of Cu2+ and Ag+ ions.

PubMed

Cao, Yongqiang; Zhang, Aiyu; Ma, Qian; Liu, Ning; Yang, Ping

2013-01-01

A new ion sensor based on hybrid SiO2 -coated CdTe nanocrystals (NCs) was prepared and applied for sensitive sensing of Cu(2+) and Ag(+) for the selective quenching of photoluminescence (PL) of NCs in the presence of ions. As shown by ion detection experiments conducted in pure water rather than buffer solution, PL responses of NCs were linearly proportional to concentrations of Cu(2+) and Ag(+) ions < 3 and 7 uM, respectively. Much lower detection limits of 42.37 nM for Cu(2+) and 39.40 nM for Ag(+) were also observed. In addition, the NC quenching mechanism was discussed in terms of the characterization of static and transient optical spectra. The transfer and trapping of photoinduced charges in NCs by surface energy levels of CuS and Ag2 S clusters as well as surface defects generated by the exchange of Cu(2+) and Ag(+) ions with Cd(2+) ion in NCs, resulted in PL quenching and other optical spectra changes, including steady-state absorption and transient PL spectra. It is our hope that these results will be helpful in the future preparation of new ion sensors. Copyright © 2012 John Wiley & Sons, Ltd.

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.

Perovskite nanocrystals: across-dimensional attachment, film-scale assembly on a flexible substrate and their fluorescence properties

NASA Astrophysics Data System (ADS)

Huang, Wenyi; Liu, Jiajia; Bai, Bing; Huang, Liu; Xu, Meng; Liu, Jia; Rong, Hongpan; Zhang, Jiatao

2018-03-01

Perovskite nanocrystals (NCs), which are a good fluorescence candidate with excellent photoelectric properties, have opened new avenues in the fabrication of highly efficient solar cells, light-emitting diodes (LEDs), and other optoelectronic devices. Further advances will rely on the multitude of compositional, structural variants that enable the formation of lower-dimensionality layered and three-dimensional (3D) perovskites with architectural innovations. In this work, the perovskite film was fabricated on a flexible substrate using simple dip-coating technology and 3D assemblies of perovskite NCs were obtained through an attachment process. Original perovskite NCs had a rectangular or square morphology with high particle uniformity and the narrow and symmetric fluorescence emission peak was adjustable at 515-527 nm. The controllable self-assembly of the micron size cuboid-like 3D assembly had an apparent enhancement on peak (111) in the x-ray diffraction (XRD) pattern. Surface ligands not only play a role in the attachment process but also keep the independence of each NC in 3D assemblies. Such assembly of the perovskite film maintained the original perovskite NCs fluorescence emission peak and narrow full width at the half-maximum (FWHM), which is of great importance for the investigation of future devices.

The electrical conductivity and energy band gap of ‘bunga belimbing buluh’/tio2 nanocrystals as hybrid solar cell

NASA Astrophysics Data System (ADS)

Kamarulzaman, N. H.; Salleh, H.; Ghazali, M. S. M.; Ghazali, S. M.; Ahmad, Z.

2018-05-01

This research intends to explore the effect of thickness of inorganic titania nanocrystals (TiO2 NCs) materials and Averrhoe bilimbi’s flower towards the electrical conductivity. Averrhoe bilimbi’s flower or also known as ‘bunga belimbing buluh’ was used for the first time as a natural dye in hybrid solar cells. The performance of electrical conductivity can be improved in bilayer heterojunction hybrid solar cell (HCS). The TiO2 NCs was deposited on the ITO substrate using Electrochemistry method at room temperature. The dye extracted from Averrhoe bilimbi’s flower was deposited on the top of TiO2 NCs layered using the same method. The electrical conductivity can be recorded using Four Point Probe (FPP) under dark and light radiation (range of 0 Wm-2 to 200Wm-2). From the results, electrical conductivity was increased by the increment light intensity and suitable for further solar cell fabrications.

CuGaS2 and CuGaS2–ZnS Porous Layers from Solution-Processed Nanocrystals

PubMed Central

Guardia, Pablo; Estradé, Sònia; Peiró, Francesca; Cabot, Andreu

2018-01-01

The manufacturing of semiconducting films using solution-based approaches is considered a low cost alternative to vacuum-based thin film deposition strategies. An additional advantage of solution processing methods is the possibility to control the layer nano/microstructure. Here, we detail the production of mesoporous CuGaS2 (CGS) and ZnS layers from spin-coating and subsequent cross-linking through chalcogen-chalcogen bonds of properly functionalized nanocrystals (NCs). We further produce NC-based porous CGS/ZnS bilayers and NC-based CGS–ZnS composite layers using the same strategy. Photoelectrochemical measurements are used to demonstrate the efficacy of porous layers, and particularly the CGS/ZnS bilayers, for improved current densities and photoresponses relative to denser films deposited from as-produced NCs. PMID:29621198

Robust, functional nanocrystal solids by infilling with atomic layer deposition.

PubMed

Liu, Yao; Gibbs, Markelle; Perkins, Craig L; Tolentino, Jason; Zarghami, Mohammad H; Bustamante, Jorge; Law, Matt

2011-12-14

Thin films of colloidal semiconductor nanocrystals (NCs) are inherently metatstable materials prone to oxidative and photothermal degradation driven by their large surface-to-volume ratios and high surface energies. (1) The fabrication of practical electronic devices based on NC solids hinges on preventing oxidation, surface diffusion, ripening, sintering, and other unwanted physicochemical changes that can plague these materials. Here we use low-temperature atomic layer deposition (ALD) to infill conductive PbSe NC solids with metal oxides to produce inorganic nanocomposites in which the NCs are locked in place and protected against oxidative and photothermal damage. Infilling NC field-effect transistors and solar cells with amorphous alumina yields devices that operate with enhanced and stable performance for at least months in air. Furthermore, ALD infilling with ZnO lowers the height of the inter-NC tunnel barrier for electron transport, yielding PbSe NC films with electron mobilities of 1 cm2 V(-1) s(-1). Our ALD technique is a versatile means to fabricate robust NC solids for optoelectronic devices.

Robust, functional nanocrystal solids by infilling with atomic layer deposition

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

Liu, Yao; Gibbs, Markelle; Perkins, Craig L.

2011-12-14

Thin films of colloidal semiconductor nanocrystals (NCs) are inherently metatstable materials prone to oxidative and photothermal degradation driven by their large surface-to-volume ratios and high surface energies. The fabrication of practical electronic devices based on NC solids hinges on preventing oxidation, surface diffusion, ripening, sintering, and other unwanted physicochemical changes that can plague these materials. Here we use low-temperature atomic layer deposition (ALD) to infill conductive PbSe NC solids with metal oxides to produce inorganic nanocomposites in which the NCs are locked in place and protected against oxidative and photothermal damage. Infilling NC field-effect transistors and solar cells with amorphousmore » alumina yields devices that operate with enhanced and stable performance for at least months in air. Furthermore, ALD infilling with ZnO lowers the height of the inter-NC tunnel barrier for electron transport, yielding PbSe NC films with electron mobilities of 1 cm² V -1 s -1. Our ALD technique is a versatile means to fabricate robust NC solids for optoelectronic devices.« less

Organic-inorganic interface-induced multi-fluorescence of MgO nanocrystal clusters and their applications in cellular imaging.

PubMed

Xie, Shuifen; Bao, Shixiong; Ouyang, Junjie; Zhou, Xi; Kuang, Qin; Xie, Zhaoxiong; Zheng, Lansun

2014-04-25

Surface functionalization of inorganic nanomaterials through chemical binding of organic ligands on the surface unsaturated atoms, forming unique organic-inorganic interfaces, is a powerful approach for creating special functions for inorganic nanomaterials. Herein, we report the synthesis of hierarchical MgO nanocrystal clusters (NCs) with an organic-inorganic interface induced multi-fluorescence and their application as new alternative labels for cellular imaging. The synthetic method was established by a dissolution and regrowth process with the assistance of carboxylic acid, in which the as-prepared MgO NCs were modified with carboxylic groups at the coordinatively unsaturated atoms of the surface. By introducing acetic acid to partially replace oleic acid in the reaction, the optical absorption of the produced MgO NCs was progressively engineered from the UV to the visible region. Importantly, with wider and continuous absorption profile, those MgO NCs presented bright and tunable multicolor emissions from blue-violet to green and yellow, with the highest absolute quantum yield up to (33±1) %. The overlap for the energy levels of the inorganic-organic interface and low-coordinated states stimulated a unique fluorescence resonance energy transfer phenomenon. Considering the potential application in cellular imaging, such multi-fluorescent MgO NCs were further encapsulated with a silica shell to improve the water solubility and stability. As expected, the as-formed MgO@SiO2 NCs possessed great biocompatibility and high performance in cellular imaging. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Calcium Sensor, NCS-1, Promotes Tumor Aggressiveness and Predicts Patient Survival.

PubMed

Moore, Lauren M; England, Allison; Ehrlich, Barbara E; Rimm, David L

2017-07-01

Neuronal Calcium Sensor 1 (NCS-1) is a multi-functional Ca 2+ -binding protein that affects a range of cellular processes beyond those related to neurons. Functional characterization of NCS-1 in neuronal model systems suggests that NCS-1 may influence oncogenic processes. To this end, the biological role of NCS-1 was investigated by altering its endogenous expression in MCF-7 and MB-231 breast cancer cells. Overexpression of NCS-1 resulted in a more aggressive tumor phenotype demonstrated by a marked increase in invasion and motility, and a decrease in cell-matrix adhesion to collagen IV. Overexpression of NCS-1 was also shown to increase the efficacy of paclitaxel-induced cell death in a manner that was independent of cellular proliferation. To determine the association between NCS-1 and clinical outcome, NCS-1 expression was measured in two independent breast cancer cohorts by the Automated Quantitative Analysis method of quantitative immunofluorescence. Elevated levels of NCS-1 were significantly correlated with shorter survival rates. Furthermore, multivariate analysis demonstrated that NCS-1 status was prognostic, independent of estrogen receptor, progesterone receptor, HER2, and lymph node status. These findings indicate that NCS-1 plays a role in the aggressive behavior of a subset of breast cancers and has therapeutic or biomarker potential. Implications: NCS-1, a calcium-binding protein, is associated with clinicopathologic features of aggressiveness in breast cancer cells and worse outcome in two breast cancer patient cohorts. Mol Cancer Res; 15(7); 942-52. ©2017 AACR . ©2017 American Association for Cancer Research.

High Efficiency Dye-sensitized Solar Cells Constructed with Composites of TiO2 and the Hot-bubbling Synthesized Ultra-Small SnO2 Nanocrystals.

PubMed

Mao, Xiaoli; Zhou, Ru; Zhang, Shouwei; Ding, Liping; Wan, Lei; Qin, Shengxian; Chen, Zhesheng; Xu, Jinzhang; Miao, Shiding

2016-01-13

An efficient photo-anode for the dye-sensitized solar cells (DSSCs) should have features of high loading of dye molecules, favorable band alignments and good efficiency in electron transport. Herein, the 3.4 nm-sized SnO2 nanocrystals (NCs) of high crystallinity, synthesized via the hot-bubbling method, were incorporated with the commercial TiO2 (P25) particles to fabricate the photo-anodes. The optimal percentage of the doped SnO2 NCs was found at ~7.5% (SnO2/TiO2, w/w), and the fabricated DSSC delivers a power conversion efficiency up to 6.7%, which is 1.52 times of the P25 based DSSCs. The ultra-small SnO2 NCs offer three benefits, (1) the incorporation of SnO2 NCs enlarges surface areas of the photo-anode films, and higher dye-loading amounts were achieved; (2) the high charge mobility provided by SnO2 was confirmed to accelerate the electron transport, and the photo-electron recombination was suppressed by the highly-crystallized NCs; (3) the conduction band minimum (CBM) of the SnO2 NCs was uplifted due to the quantum size effects, and this was found to alleviate the decrement in the open-circuit voltage. This work highlights great contributions of the SnO2 NCs to the improvement of the photovoltaic performances in the DSSCs.

High Efficiency Dye-sensitized Solar Cells Constructed with Composites of TiO2 and the Hot-bubbling Synthesized Ultra-Small SnO2 Nanocrystals

PubMed Central

Mao, Xiaoli; Zhou, Ru; Zhang, Shouwei; Ding, Liping; Wan, Lei; Qin, Shengxian; Chen, Zhesheng; Xu, Jinzhang; Miao, Shiding

2016-01-01

An efficient photo-anode for the dye-sensitized solar cells (DSSCs) should have features of high loading of dye molecules, favorable band alignments and good efficiency in electron transport. Herein, the 3.4 nm-sized SnO2 nanocrystals (NCs) of high crystallinity, synthesized via the hot-bubbling method, were incorporated with the commercial TiO2 (P25) particles to fabricate the photo-anodes. The optimal percentage of the doped SnO2 NCs was found at ~7.5% (SnO2/TiO2, w/w), and the fabricated DSSC delivers a power conversion efficiency up to 6.7%, which is 1.52 times of the P25 based DSSCs. The ultra-small SnO2 NCs offer three benefits, (1) the incorporation of SnO2 NCs enlarges surface areas of the photo-anode films, and higher dye-loading amounts were achieved; (2) the high charge mobility provided by SnO2 was confirmed to accelerate the electron transport, and the photo-electron recombination was suppressed by the highly-crystallized NCs; (3) the conduction band minimum (CBM) of the SnO2 NCs was uplifted due to the quantum size effects, and this was found to alleviate the decrement in the open-circuit voltage. This work highlights great contributions of the SnO2 NCs to the improvement of the photovoltaic performances in the DSSCs. PMID:26758941

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.

Influence of spray drying and dispersing agent on surface and dissolution properties of griseofulvin micro and nanocrystals.

PubMed

Shah, Dhaval A; Patel, Manan; Murdande, Sharad B; Dave, Rutesh H

2016-11-01

The purpose for the current research is to compare and evaluate physiochemical properties of spray-dried (SD) microcrystals (MCs), nanocrystals (NCs), and nanocrystals with a dispersion agent (NCm) from a poorly soluble compound. The characterization was carried out by performing size and surface analysis, interfacial tension (at particle moisture interface), and in-vitro drug dissolution rate experiments. Nanosuspensions were prepared by media milling and were spray-dried. The SD powders that were obtained were characterized morphologically using scanning electron microscopy (SEM), polarized light microscopy (PLM), and Flowchem. Solid-state characterization was performed using X-ray powder diffraction (XRPD), Fourier transfer infrared spectroscopy (FT-IR), and differential scanning calorimetry (DSC) for the identification of the crystalline nature of all the SD powders. The powders were characterized for their redispersion tendency in the water and in pH 1.2. Significant differences in redispersion were noted for both the NCs in both dissolution media. The interfacial tension for particle moisture interface was determined by applying the BET (Braunauer-Emmett-Teller) equation to the vapor sorption data. No significant reduction in the interfacial tension was observed between MCs and NCs; however, a significant reduction in the interfacial tension was observed for NCm at both 25 °C and 35 °C temperatures. The difference in interfacial tension and redispersion behavior can be attributed to a difference in the wetting tendency for all the SD powders. The dissolution studies were carried out under sink and under non-sink conditions. The non-sink dissolution approach was found suitable for quantification of the dissolution rate enhancement, and also for providing the rank order to the SD formulations.

Ultrafast carrier dynamics and third-order nonlinear optical properties of AgInS2/ZnS nanocrystals.

PubMed

Yu, Kuai; Yang, Yang; Wang, Junzhong; Tang, Xiaosheng; Xu, Qing-Hua; Wang, Guo Ping

2018-06-22

Broad photoluminescence (PL) emission, a large Stokes shift and extremely long-lived radiative lifetimes are the characteristics of ternary I-III-VI semiconductor nanocrystals (NCs), such as CuInS 2 and AgInS 2 . However, the lack of understanding regarding the intriguing PL mechanisms and photo-carrier dynamics limits their further applications. Here, AgInS 2 and AgInS 2 /ZnS NCs were chemically synthesized and their carrier dynamics were studied by time-resolved PL spectroscopy. The results demonstrated that the surface defect state, which contributed dominantly to the non-radiative decay processes, was effectively passivated through ZnS alloying. Femtosecond transient absorption spectroscopy was also used to investigate the carrier dynamics, revealing the electron storage at the surface state and donor state. Furthermore, the two photon absorption properties of AgInS 2 and AgInS 2 /ZnS NCs were measured using an open-aperture Z-scan technique. The improved third-order nonlinear susceptibility [Formula: see text] of AgInS 2 through ZnS alloying demonstrates potential application in two photon PL biological imaging.

Ultrafast carrier dynamics and third-order nonlinear optical properties of AgInS2/ZnS nanocrystals

NASA Astrophysics Data System (ADS)

Yu, Kuai; Yang, Yang; Wang, Junzhong; Tang, Xiaosheng; Xu, Qing-Hua; Wang, Guo Ping

2018-06-01

Broad photoluminescence (PL) emission, a large Stokes shift and extremely long-lived radiative lifetimes are the characteristics of ternary I–III–VI semiconductor nanocrystals (NCs), such as CuInS2 and AgInS2. However, the lack of understanding regarding the intriguing PL mechanisms and photo-carrier dynamics limits their further applications. Here, AgInS2 and AgInS2/ZnS NCs were chemically synthesized and their carrier dynamics were studied by time-resolved PL spectroscopy. The results demonstrated that the surface defect state, which contributed dominantly to the non-radiative decay processes, was effectively passivated through ZnS alloying. Femtosecond transient absorption spectroscopy was also used to investigate the carrier dynamics, revealing the electron storage at the surface state and donor state. Furthermore, the two photon absorption properties of AgInS2 and AgInS2/ZnS NCs were measured using an open-aperture Z-scan technique. The improved third-order nonlinear susceptibility {χ }(3) of AgInS2 through ZnS alloying demonstrates potential application in two photon PL biological imaging.

Postsynthetic Doping of MnCl2 Molecules into Preformed CsPbBr3 Perovskite Nanocrystals via a Halide Exchange-Driven Cation Exchange.

PubMed

Huang, Guangguang; Wang, Chunlei; Xu, Shuhong; Zong, Shenfei; Lu, Ju; Wang, Zhuyuan; Lu, Changgui; Cui, Yiping

2017-08-01

Unlike widely used postsynthetic halide exchange for CsPbX 3 (X is halide) perovskite nanocrystals (NCs), cation exchange of Pb is of a great challenge due to the rigid nature of the Pb cationic sublattice. Actually, cation exchange has more potential for rendering NCs with peculiar properties. Herein, a novel halide exchange-driven cation exchange (HEDCE) strategy is developed to prepare dually emitting Mn-doped CsPb(Cl/Br) 3 NCs via postsynthetic replacement of partial Pb in preformed perovskite NCs. The basic idea for HEDCE is that the partial cation exchange of Pb by Mn has a large probability to occur as a concomitant result for opening the rigid halide octahedron structure around Pb during halide exchange. Compared to traditional ionic exchange, HEDCE is featured by proceeding of halide exchange and cation exchange at the same time and lattice site. The time and space requirements make only MnCl 2 molecules (rather than mixture of Mn and Cl ions) capable of doping into perovskite NCs. This special molecular doping nature results in a series of unusual phenomenon, including long reaction time, core-shell structured mid states with triple emission bands, and dopant molecules composition-dependent doping process. As-prepared dual-emitting Mn-doped CsPb(Cl/Br) 3 NCs are available for ratiometric temperature sensing. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hybrid photodetector based on CsPbBr3 perovskite nanocrystals and PC71BM fullerene derivative

NASA Astrophysics Data System (ADS)

Li, Tengteng; Liu, Meihong; Li, Qingyan; Chen, Run; Liu, Xin

2018-05-01

Here, a hybrid perovskite-organic photodetector was fabricated by integrating CsPbBr3 nanocrystals (NCs) with [6,6]-phenyl C71 butyric acid methyl ester (PC71BM), exhibiting remarkable optoelectronic properties in terms of photoresponsivity (1.72 A/W), detectivity (1.76 × 107 Jones), external quantum efficiency (EQE) (530%) under the illumination of 405 nm laser, and photoresponse time is shorter than 0.1 ms due to the assistance of heterojunction on the separation of photoexcitons.

Dismantling the "Red Wall" of Colloidal Perovskites: Highly Luminescent Formamidinium and Formamidinium-Cesium Lead Iodide Nanocrystals.

PubMed

Protesescu, Loredana; Yakunin, Sergii; Kumar, Sudhir; Bär, Janine; Bertolotti, Federica; Masciocchi, Norberto; Guagliardi, Antonietta; Grotevent, Matthias; Shorubalko, Ivan; Bodnarchuk, Maryna I; Shih, Chih-Jen; Kovalenko, Maksym V

2017-03-28

Colloidal nanocrystals (NCs) of APbX 3 -type lead halide perovskites [A = Cs + , CH 3 NH 3 + (methylammonium or MA + ) or CH(NH 2 ) 2 + (formamidinium or FA + ); X = Cl - , Br - , I - ] have recently emerged as highly versatile photonic sources for applications ranging from simple photoluminescence down-conversion (e.g., for display backlighting) to light-emitting diodes. From the perspective of spectral coverage, a formidable challenge facing the use of these materials is how to obtain stable emissions in the red and infrared spectral regions covered by the iodide-based compositions. So far, red-emissive CsPbI 3 NCs have been shown to suffer from a delayed phase transformation into a nonluminescent, wide-band-gap 1D polymorph, and MAPbI 3 exhibits very limited chemical durability. In this work, we report a facile colloidal synthesis method for obtaining FAPbI 3 and FA-doped CsPbI 3 NCs that are uniform in size (10-15 nm) and nearly cubic in shape and exhibit drastically higher robustness than their MA- or Cs-only cousins with similar sizes and morphologies. Detailed structural analysis indicated that the FAPbI 3 NCs had a cubic crystal structure, while the FA 0.1 Cs 0.9 PbI 3 NCs had a 3D orthorhombic structure that was isostructural to the structure of CsPbBr 3 NCs. Bright photoluminescence (PL) with high quantum yield (QY > 70%) spanning red (690 nm, FA 0.1 Cs 0.9 PbI 3 NCs) and near-infrared (near-IR, ca. 780 nm, FAPbI 3 NCs) regions was sustained for several months or more in both the colloidal state and in films. The peak PL wavelengths can be fine-tuned by using postsynthetic cation- and anion-exchange reactions. Amplified spontaneous emissions with low thresholds of 28 and 7.5 μJ cm -2 were obtained from the films deposited from FA 0.1 Cs 0.9 PbI 3 and FAPbI 3 NCs, respectively. Furthermore, light-emitting diodes with a high external quantum efficiency of 2.3% were obtained by using FAPbI 3 NCs.

Sustainable, Rapid Synthesis of Bright-Luminescent CuInS2-ZnS Alloyed Nanocrystals: Multistage Nano-xenotoxicity Assessment and Intravital Fluorescence Bioimaging in Zebrafish-Embryos

NASA Astrophysics Data System (ADS)

Chetty, S. Shashank; Praneetha, S.; Basu, Sandeep; Sachidanandan, Chetana; Murugan, A. Vadivel

2016-05-01

Near-infrared (NIR) luminescent CuInS2-ZnS alloyed nanocrystals (CIZS-NCs) for highly fluorescence bioimaging have received considerable interest in recent years. Owing, they became a desirable alternative to heavy-metal based-NCs and organic dyes with unique optical properties and low-toxicity for bioimaging and optoelectronic applications. In the present study, bright and robust CIZS-NCs have been synthesized within 5 min, as-high-as 230 °C without requiring any inert-gas atmosphere via microwave-solvothermal (MW-ST) method. Subsequently, the in vitro and in vivo nano-xenotoxicity and cellular uptake of the MUA-functionalized CIZS-NCs were investigated in L929, Vero, MCF7 cell lines and zebrafish-embryos. We observed minimal toxicity and acute teratogenic consequences upto 62.5 μg/ml of the CIZS-NCs in zebrafish-embryos. We also observed spontaneous uptake of the MUA-functionalized CIZS-NCs by 3 dpf older zebrafish-embryos that are evident through bright red fluorescence-emission at a low concentration of 7.8 μg/mL. Hence, we propose that the rapid, low-cost, large-scale “sustainable” MW-ST synthesis of CIZS-NCs, is an ideal bio-nanoprobe with good temporal and spatial resolution for rapid labeling, long-term in vivo tracking and intravital-fluorescence-bioimaging (IVBI).

Phase diagrams of ferroelectric nanocrystals strained by an elastic matrix

NASA Astrophysics Data System (ADS)

Nikitchenko, A. I.; Azovtsev, A. V.; Pertsev, N. A.

2018-01-01

Ferroelectric crystallites embedded into a dielectric matrix experience temperature-dependent elastic strains caused by differences in the thermal expansion of the crystallites and the matrix. Owing to the electrostriction, these lattice strains may affect polarization states of ferroelectric inclusions significantly, making them different from those of a stress-free bulk crystal. Here, using a nonlinear thermodynamic theory, we study the mechanical effect of elastic matrix on the phase states of embedded single-domain ferroelectric nanocrystals. Their equilibrium polarization states are determined by minimizing a special thermodynamic potential that describes the energetics of an ellipsoidal ferroelectric inclusion surrounded by a linear elastic medium. To demonstrate the stability ranges of such states for a given material combination, we construct a phase diagram, where the inclusion’s shape anisotropy and temperature are used as two parameters. The ‘shape-temperature’ phase diagrams are calculated numerically for PbTiO3 and BaTiO3 nanocrystals embedded into representative dielectric matrices generating tensile (silica glass) or compressive (potassium silicate glass) thermal stresses inside ferroelectric inclusions. The developed phase maps demonstrate that the joint effect of thermal stresses and matrix-induced elastic clamping of ferroelectric inclusions gives rise to several important features in the polarization behavior of PbTiO3 and BaTiO3 nanocrystals. In particular, the Curie temperature displays a nonmonotonic variation with the ellipsoid’s aspect ratio, being minimal for spherical inclusions. Furthermore, the diagrams show that the polarization orientation with respect to the ellipsoid’s symmetry axis is controlled by the shape anisotropy and the sign of thermal stresses. Under certain conditions, the mechanical inclusion-matrix interaction qualitatively alters the evolution of ferroelectric states on cooling, inducing a structural transition

Observation of Quantum Confinement in Monodisperse Methylammonium Lead Halide Perovskite Nanocrystals Embedded in Mesoporous Silica.

PubMed

Malgras, Victor; Tominaka, Satoshi; Ryan, James W; Henzie, Joel; Takei, Toshiaki; Ohara, Koji; Yamauchi, Yusuke

2016-10-13

Hybrid organic-inorganic metal halide perovskites have fascinating electronic properties and have already been implemented in various devices. Although the behavior of bulk metal halide perovskites has been widely studied, the properties of perovskite nanocrystals are less well-understood because synthesizing them is still very challenging, in part because of stability. Here we demonstrate a simple and versatile method to grow monodisperse CH 3 NH 3 PbBr x I x-3 perovskite nanocrystals inside mesoporous silica templates. The size of the nanocrystal is governed by the pore size of the templates (3.3, 3.7, 4.2, 6.2, and 7.1 nm). In-depth structural analysis shows that the nanocrystals maintain the perovskite crystal structure, but it is slightly distorted. Quantum confinement was observed by tuning the size of the particles via the template. This approach provides an additional route to tune the optical bandgap of the nanocrystal. The level of quantum confinement was modeled taking into account the dimensions of the rod-shaped nanocrystals and their close packing inside the channels of the template. Photoluminescence measurements on CH 3 NH 3 PbBr clearly show a shift from green to blue as the pore size is decreased. Synthesizing perovskite nanostructures in templates improves their stability and enables tunable electronic properties via quantum confinement. These structures may be useful as reference materials for comparison with other perovskites, or as functional materials in all solid-state light-emitting diodes.

Communication: Visualization and spectroscopy of defects induced by dehydrogenation in individual silicon nanocrystals

NASA Astrophysics Data System (ADS)

Kislitsyn, Dmitry A.; Mills, Jon M.; Kocevski, Vancho; Chiu, Sheng-Kuei; DeBenedetti, William J. I.; Gervasi, Christian F.; Taber, Benjamen N.; Rosenfield, Ariel E.; Eriksson, Olle; Rusz, Ján; Goforth, Andrea M.; Nazin, George V.

2016-06-01

We present results of a scanning tunneling spectroscopy (STS) study of the impact of dehydrogenation on the electronic structures of hydrogen-passivated silicon nanocrystals (SiNCs) supported on the Au(111) surface. Gradual dehydrogenation is achieved by injecting high-energy electrons into individual SiNCs, which results, initially, in reduction of the electronic bandgap, and eventually produces midgap electronic states. We use theoretical calculations to show that the STS spectra of midgap states are consistent with the presence of silicon dangling bonds, which are found in different charge states. Our calculations also suggest that the observed initial reduction of the electronic bandgap is attributable to the SiNC surface reconstruction induced by conversion of surface dihydrides to monohydrides due to hydrogen desorption. Our results thus provide the first visualization of the SiNC electronic structure evolution induced by dehydrogenation and provide direct evidence for the existence of diverse dangling bond states on the SiNC surfaces.

Laser-induced growth of nanocrystals embedded in porous materials

PubMed Central

2013-01-01

Space localization of the linear and nonlinear optical properties in a transparent medium at the submicron scale is still a challenge to yield the future generation of photonic devices. Laser irradiation techniques have always been thought to structure the matter at the nanometer scale, but combining them with doping methods made it possible to generate local growth of several types of nanocrystals in different kinds of silicate matrices. This paper summarizes the most recent works developed in our group, where the investigated nanoparticles are either made of metal (gold) or chalcogenide semiconductors (CdS, PbS), grown in precursor-impregnated porous xerogels under different laser irradiations. This review is associated to new results on silver nanocrystals in the same kind of matrices. It is shown that, depending on the employed laser, the particles can be formed near the sample surface or deep inside the silica matrix. Photothermal and/or photochemical mechanisms may be invoked to explain the nanoparticle growth, depending on the laser, precursor, and matrix. One striking result is that metal salt reduction, necessary to the production of the corresponding nanoparticles, can efficiently occur due to the thermal wrenching of electrons from the matrix itself or due to multiphoton absorption of the laser light by a reducer additive in femtosecond regime. Very localized semiconductor quantum dots could also be generated using ultrashort pulses, but while PbS nanoparticles grow faster than CdS particles due to one-photon absorption, this better efficiency is counterbalanced by a sensitivity to oxidation. In most cases where the reaction efficiency is high, particles larger than the pores have been obtained, showing that a fast diffusion of the species through the interconnected porosity can modify the matrix itself. Based on our experience in these techniques, we compare several examples of laser-induced nanocrystal growth in porous silica xerogels, which allows

Decorating fiber nanotip with single perovskite quantum dot and other luminescent nanocrystals synthesized in oil-phase

NASA Astrophysics Data System (ADS)

Qian, Yu; Xing, Xing; Xu, Ya; Lu, Zhenda; Zhang, Weihua

2017-11-01

We report a simple yet robust method for fabricating single perovskite quantum dot (QD) decorated fiber nanotips. In this method, a single QD is directly picked up and subsequently glued on the apex of a specially fabricated cantilever fiber tip with a high success rate (approx. 70%) without using expensive close-loop feedback systems. Thanks to the flexibility and robustness of the fiber tips, no damage of the tips was observed in the process. Moreover, nanocrystal (NC) dispersing technique was developed to avoid undesired aggregations of QDs, and it guarantees that only one QD is glued each time. Finally, we demonstrate that this technique can also be applied to other oil-phase synthesized NCs, including CdSe QDs and upconversion luminescent NCs. It leads to many important applications on probing the local environment using high performance luminescent nanoprobes.

Interaction of polymer-coated silicon nanocrystals with lipid bilayers and surfactant interfaces

NASA Astrophysics Data System (ADS)

Elbaradei, Ahmed; Brown, Samuel L.; Miller, Joseph B.; May, Sylvio; Hobbie, Erik K.

2016-10-01

We use photoluminescence (PL) microscopy to measure the interaction between polyethylene-glycol-coated (PEGylated) silicon nanocrystals (SiNCs) and two model surfaces: lipid bilayers and surfactant interfaces. By characterizing the photostability, transport, and size-dependent emission of the PEGylated nanocrystal clusters, we demonstrate the retention of red PL suitable for detection and tracking with minimal blueshift after a year in an aqueous environment. The predominant interaction measured for both interfaces is short-range repulsion, consistent with the ideal behavior anticipated for PEGylated phospholipid coatings. However, we also observe unanticipated attractive behavior in a small number of scenarios for both interfaces. We attribute this anomaly to defective PEG coverage on a subset of the clusters, suggesting a possible strategy for enhancing cellular uptake by controlling the homogeneity of the PEG corona. In both scenarios, the shape of the apparent potential is modeled through the free or bound diffusion of the clusters near the confining interface.

Alkyl Passivation and Amphiphilic Polymer Coating of Silicon Nanocrystals for Diagnostic Imaging

PubMed Central

Hessel, Colin M.; Rasch, Michael R.; Hueso, Jose L.; Goodfellow, Brian W.; Akhavan, Vahid A.; Puvanakrishnan, Priyaveena; Tunnell, James W.

2011-01-01

We show a method to produce biocompatible polymer-coated silicon (Si) nanocrystals for medical imaging. Silica-embedded Si nanocrystals are formed by HSQ thermolysis. The nanocrystals are then liberated from the oxide and terminated with Si-H bonds by HF etching, followed by alkyl monolayer passivation by thermal hydrosilylation. The Si nanocrystals have an average diameter of 2.1 ± 0.6 nm and photoluminesce (PL) with a peak emission wavelength of 650 nm, which lies within the transmission window of 650–900 nm that is useful for biological imaging. The hydrophobic Si nanocrystals are then coated with an amphiphilic polymer for dispersion in aqueous media with pH ranging between 7 and 10 and ionic strength between 30 mM and 2 M, while maintaining a bright and stable PL and a hydrodynamic radius of only 20 nm. Fluorescence imaging of polymer-coated Si nanocrystals in a biological tissue host is demonstrated, showing the potential for in vivo imaging. PMID:20818646

Towards environmentally benign approaches for the synthesis of CZTSSe nanocrystals by a hot injection method: a status review.

PubMed

Ghorpade, Uma; Suryawanshi, Mahesh; Shin, Seung Wook; Gurav, Kishor; Patil, Pramod; Pawar, Sambhaji; Hong, Chang Woo; Kim, Jin Hyeok; Kolekar, Sanjay

2014-10-07

With the earth's abundance of kesterite, recent progress in chalcogenide based Cu2ZnSn(Sx,Se1-x)4 (CZTSSe) thin films has drawn prime attention in thin film solar cells (TFSCs) research and development. This review is focused on the current developments in the synthesis of CZTS nanocrystals (NCs) using a hot injection (HI) technique and provides comprehensive discussions on the current status of CZTSSe TFSCs. This article begins with a description of the advantages of nanoparticulate based thin films, and then introduces the basics of this technique and the corresponding growth mechanism is also discussed. A brief overview further addresses a series of investigations on the developments in the HI based CZTSSe NCs using different solvents in terms of their high toxicity to environmentally benign materials. A variety of recipes and techniques for the NCs ink formulation and thereby the preparation of absorber layers using NC inks are outlined, respectively. The deposition of precursor thin films, post-deposition processes such as sulfurization or selenization treatments and the fabrication of CZTSSe NCs based solar cells and their performances are discussed. Finally, we discussed concluding remarks and the perspectives for further developments in the existing research on CZTSSe based nanoparticulate (NP) TFSCs towards future green technology.

Sn Cation Valency Dependence in Cation Exchange Reactions Involving Cu2-xSe Nanocrystals

PubMed Central

2014-01-01

We studied cation exchange reactions in colloidal Cu2-xSe nanocrystals (NCs) involving the replacement of Cu+ cations with either Sn2+ or Sn4+ cations. This is a model system in several aspects: first, the +2 and +4 oxidation states for tin are relatively stable; in addition, the phase of the Cu2-xSe NCs remains cubic regardless of the degree of copper deficiency (that is, “x”) in the NC lattice. Also, Sn4+ ions are comparable in size to the Cu+ ions, while Sn2+ ones are much larger. We show here that the valency of the entering Sn ions dictates the structure and composition not only of the final products but also of the intermediate steps of the exchange. When Sn4+ cations are used, alloyed Cu2–4ySnySe NCs (with y ≤ 0.33) are formed as intermediates, with almost no distortion of the anion framework, apart from a small contraction. In this exchange reaction the final stoichiometry of the NCs cannot go beyond Cu0.66Sn0.33Se (that is Cu2SnSe3), as any further replacement of Cu+ cations with Sn4+ cations would require a drastic reorganization of the anion framework, which is not possible at the reaction conditions of the experiments. When instead Sn2+ cations are employed, SnSe NCs are formed, mostly in the orthorhombic phase, with significant, albeit not drastic, distortion of the anion framework. Intermediate steps in this exchange reaction are represented by Janus-type Cu2-xSe/SnSe heterostructures, with no Cu–Sn–Se alloys. PMID:25340627

Modifying the size and uniformity of upconversion Yb/Er:NaGdF4 nanocrystals through alkaline-earth doping.

PubMed

Lei, Lei; Chen, Daqin; Huang, Ping; Xu, Ju; Zhang, Rui; Wang, Yuansheng

2013-11-21

NaGdF4 is regarded as an ideal upconversion (UC) host material for lanthanide (Ln(3+)) activators because of its unique crystal structure, high Ln(3+) solubility, low phonon energy and high photochemical stability, and Ln(3+)-doped NaGdF4 UC nanocrystals (NCs) have been widely investigated as bio-imaging and magnetic resonance imaging agents recently. To realize their practical applications, controlling the size and uniformity of the monodisperse Ln(3+)-doped NaGdF4 UC NCs is highly desired. Unlike the routine routes by finely adjusting the multiple experimental parameters, herein we provide a facile and straightforward strategy to modify the size and uniformity of NaGdF4 NCs via alkaline-earth doping for the first time. With the increase of alkaline-earth doping content, the size of NaGdF4 NCs increases gradually, while the size-uniformity is still retained. We attribute this "focusing" of size distribution to the diffusion controlled growth of NaGdF4 NCs induced by alkaline-earth doping. Importantly, adopting the Ca(2+)-doped Yb/Er:NaGdF4 NCs as cores, the complete Ca/Yb/Er:NaGdF4@NaYF4 core-shell particles with excellent size-uniformity can be easily achieved. However, when taking the Yb/Er:NaGdF4 NCs without Ca(2+) doping as cores, they could not be perfectly covered by NaYF4 shells, and the obtained products are non-uniform in size. As a result, the UC emission intensity of the complete core-shell NCs increases by about 30 times in comparison with that of the cores, owing to the effective surface passivation of the Ca(2+)-doped cores and therefore protection of Er(3+) in the cores from the non-radiative decay caused by surface defects, whereas the UC intensity of the incomplete core-shell NCs is enhanced by only 3 times.

Tunable bandgap energy of fluorinated nanocrystals for flash memory applications produced by low-damage plasma treatment.

PubMed

Huang, Chi-Hsien; Lin, Chih-Ting; Wang, Jer-Chyi; Chou, Chien; Ye, Yu-Ren; Cheng, Bing-Ming; Lai, Chao-Sung

2012-11-30

A plasma system with a complementary filter to shield samples from damage during tetrafluoromethane (CF(4)) plasma treatment was proposed in order to incorporate fluorine atoms into gadolinium oxide nanocrystals (Gd(2)O(3)-NCs) for flash memory applications. X-ray photoelectron spectroscopy confirmed that fluorine atoms were successfully introduced into the Gd(2)O(3)-NCs despite the use of a filter in the plasma-enhanced chemical vapour deposition system to shield against several potentially damaging species. The number of incorporated fluorine atoms can be controlled by varying the treatment time. The optimized memory window of the resulting flash memory devices was twice that of devices treated by a filterless system because more fluorine atoms were incorporated into the Gd(2)O(3)-NCs film with very little damage. This enlarged the bandgap energy from 5.48 to 6.83 eV, as observed by ultraviolet absorption measurements. This bandgap expansion can provide a large built-in electric field that allows more charges to be stored in the Gd(2)O(3)-NCs. The maximum improvement in the retention characteristic was >60%. Because plasma damage during treatment is minimal, maximum fluorination can be achieved. The concept of simply adding a filter to a plasma system to prevent plasma damage exhibits great promise for functionalization or modification of nanomaterials for advanced nanoelectronics while introducing minimal defects.

Cell-Penetrating CaCO3 Nanocrystals for Improved Transport of NVP-BEZ235 across Membrane Barrier in T-Cell Lymphoma

PubMed Central

Civallero, Monica; Citti, Cinzia; Cosenza, Maria; Baldassarre, Francesca; Cannazza, Giuseppe; Pozzi, Samantha; Sacchi, Stefano

2018-01-01

Owing to their nano-sized porous structure, CaCO3 nanocrystals (CaCO3NCs) hold the promise to be utilized as desired materials for encapsulating molecules which demonstrate wide promise in drug delivery. We evaluate the possibility to encapsulate and release NVP-BEZ235, a novel and potent dual PI3K/mTOR inhibitor that is currently in phase I/II clinical trials for advanced solid tumors, from the CaCO3NCs. Its chemical nature shows some intrinsic limitations which induce to administer high doses leading to toxicity; to overcome these problems, here we proposed a strategy to enhance its intracellular penetration and its biological activity. Pristine CaCO3 NCs biocompatibility, cell interactions and internalization in in vitro experiments on T-cell lymphoma line, were studied. Confocal microscopy was used to monitor NCs-cell interactions and cellular uptake. We have further investigated the interaction nature and release mechanism of drug loaded/released within/from the NCs using an alternative approach based on liquid chromatography coupled to mass spectrometry. Our approach provides a good loading efficiency, therefore this drug delivery system was validated for biological activity in T-cell lymphoma: the anti-proliferative test and western blot results are very interesting because the proposed nano-formulation has an efficiency higher than free drug at the same nominal concentration. PMID:29370086

Dismantling the “Red Wall” of Colloidal Perovskites: Highly Luminescent Formamidinium and Formamidinium–Cesium Lead Iodide Nanocrystals

PubMed Central

2017-01-01

Colloidal nanocrystals (NCs) of APbX3-type lead halide perovskites [A = Cs+, CH3NH3+ (methylammonium or MA+) or CH(NH2)2+ (formamidinium or FA+); X = Cl–, Br–, I–] have recently emerged as highly versatile photonic sources for applications ranging from simple photoluminescence down-conversion (e.g., for display backlighting) to light-emitting diodes. From the perspective of spectral coverage, a formidable challenge facing the use of these materials is how to obtain stable emissions in the red and infrared spectral regions covered by the iodide-based compositions. So far, red-emissive CsPbI3 NCs have been shown to suffer from a delayed phase transformation into a nonluminescent, wide-band-gap 1D polymorph, and MAPbI3 exhibits very limited chemical durability. In this work, we report a facile colloidal synthesis method for obtaining FAPbI3 and FA-doped CsPbI3 NCs that are uniform in size (10–15 nm) and nearly cubic in shape and exhibit drastically higher robustness than their MA- or Cs-only cousins with similar sizes and morphologies. Detailed structural analysis indicated that the FAPbI3 NCs had a cubic crystal structure, while the FA0.1Cs0.9PbI3 NCs had a 3D orthorhombic structure that was isostructural to the structure of CsPbBr3 NCs. Bright photoluminescence (PL) with high quantum yield (QY > 70%) spanning red (690 nm, FA0.1Cs0.9PbI3 NCs) and near-infrared (near-IR, ca. 780 nm, FAPbI3 NCs) regions was sustained for several months or more in both the colloidal state and in films. The peak PL wavelengths can be fine-tuned by using postsynthetic cation- and anion-exchange reactions. Amplified spontaneous emissions with low thresholds of 28 and 7.5 μJ cm–2 were obtained from the films deposited from FA0.1Cs0.9PbI3 and FAPbI3 NCs, respectively. Furthermore, light-emitting diodes with a high external quantum efficiency of 2.3% were obtained by using FAPbI3 NCs. PMID:28231432

Controllable synthesis of Co3O4 nanocrystals as efficient catalysts for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Li, Baoying; Zhang, Yihe; Du, Ruifeng; Liu, Lei; Yu, Xuelian

2018-03-01

The electrochemical oxygen reduction reaction (ORR) has received great attention due to its importance in fuel cells and metal-air batteries. Here, we present a simple approach to prepare non-noble metal catalyst-Co3O4 nanocrystals (NCs). The particle size and shape were simply controlled by different types and concentrations of metal precursor. Furthermore, different sizes and shapes of Co3O4 NCs are explored as electrocatalysts for ORR, and it has been observed that particles with a similar shape, and smaller particle size led to greater catalytic current densities because of the greater surface area. For particles with a comparable size, the shape or crystalline structure governed the activity of the electrocatalytic reactions. Most importantly, the 9 nm-Co3O4 were demonstrated to act as low-cost catalysts for the ORR with a similar performance to that of Pt catalysts.

Application of L-Aspartic Acid-Capped ZnS:Mn Colloidal Nanocrystals as a Photosensor for the Detection of Copper (II) Ions in Aqueous Solution

PubMed Central

Heo, Jungho; Hwang, Cheong-Soo

2016-01-01

Water-dispersible ZnS:Mn nanocrystals (NCs) were synthesized by capping the surface with polar L-aspartic acid (Asp) molecules. The obtained ZnS:Mn-Asp NC product was optically and physically characterized using the corresponding spectroscopic methods. The ultra violet-visible (UV-VIS) absorption spectrum and photoluminescence (PL) emission spectrum of the NCs showed broad peaks at 320 and 590 nm, respectively. The average particle size measured from the obtained high resolution-transmission electron microscopy (HR-TEM) image was 5.25 nm, which was also in accordance with the Debye-Scherrer calculations using the X-ray diffraction (XRD) data. Moreover, the surface charge and degree of aggregation of the ZnS:Mn-Asp NCs were determined by electrophoretic and hydrodynamic light scattering methods, respectively. These results indicated the formation of agglomerates in water with an average size of 19.8 nm, and a negative surface charge (−4.58 mV) in water at ambient temperature. The negatively-charged NCs were applied as a photosensor for the detection of specific cations in aqueous solution. Accordingly, the ZnS:Mn-Asp NCs showed an exclusive luminescence quenching upon addition of copper (II) cations. The kinetic mechanism study on the luminescence quenching of the NCs by the addition of the Cu2+ ions proposed an energy transfer through the ionic binding between the two oppositely-charged ZnS:Mn-Asp NCs and Cu2+ ions. PMID:28335210

Growth Patterns of the Neurocentral Synchondrosis (NCS) in Immature Cadaveric Vertebra.

PubMed

Blakemore, Laurel; Schwend, Richard; Akbarnia, Behrooz A; Dumas, Megan; Schmidt, John

2018-03-01

Gross anatomic study of osteological specimens. To evaluate the age of closure for the neurocentral synchondrosis (NCS) in all 3 regions of the spine in children aged 1 to 18 years old. The ossification of the human vertebra begins from a vertebral body ossification center and a pair of neural ossification centers located within the centrum called the NCS. These bipolar cartilaginous centers of growth contribute to the growth of the vertebral body, spinal canal, and posterior elements of the spine. The closure of the synchondroses is dependent upon location of the vertebra and previous studies range from 2 to 16 years of age. Although animal and cadaveric studies have been performed regarding NCS growth and early instrumentation's effect on its development, the effects of NCS growth disturbances are still not completely understood. The vertebrae of 32 children (1 to 18 y old) from the Hamann-Todd Osteological collection were analyzed (no 2 or 9 y old specimens available). Vertebrae studied ranged from C1 to L5. A total of 768 vertebral specimens were photographed on a background grid to allow for measurement calibration. Measurements of the right and left NCS, pedicle width at the NCS, and spinal canal area were taken using Scandium image-analysis software (Olympus Soft Imaging Solutions, Germany). The percentage of the growth plate still open was found by dividing the NCS by the pedicle width and multiplying by 100. Data were analyzed with JMP 11 software (SAS Institute Inc., Cary, NC). The NCS was 100% open in all 3 regions of the spine in the 1- to 3-year age group. The cervical NCS closed first with completion around 5 years of age. The lumbar NCS was nearly fully closed by age 11. Only the thoracic region remained open through age 17 years. The left and right NCS closed simultaneously as there was no statistical difference between them. In all regions of the spine, the NCS appeared to close sooner in males than in females. Spinal canal area increased with age

Directional Carrier Transfer in Strongly Coupled Binary Nanocrystal Superlattice Films Formed by Assembly and in Situ Ligand Exchange at a Liquid–Air Interface

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

Wu, Yaoting; Li, Siming; Gogotsi, Natalie

Two species of monodisperse nanocrystals (NCs) can self-assemble into a variety of complex 2D and 3D periodic structures, or binary NC superlattice (BNSL) films, based on the relative number and size of the NCs. BNSL films offer great promise for both fundamental scientific studies and optoelectronic applications; however, the utility of as-assembled structures has been limited by the insulating ligands that originate from the synthesis of NCs. Here we report the application of an in situ ligand exchange strategy at a liquid–air interface to replace the long synthesis ligands with short ligands while preserving the long-range order of BNSL films.more » This approach is demonstrated for BNSL structures consisting of PbSe NCs of different size combinations and ligands of interest for photovoltaic devices, infrared detectors, and light-emitting diodes. To confirm enhanced coupling introduced by ligand exchange, we show ultrafast (~1 ps) directional carrier transfer across the type-I heterojunction formed by NCs of different sizes within ligand-exchanged BNSL films. In conclusion, this approach shows the potential promise of functional BNSL films, where the local and long-range energy landscape and electronic coupling can be adjusted by tuning NC composition, size, and interparticle spacing.« less

Mid-Gap States and Normal vs Inverted Bonding in Luminescent Cu+- and Ag+-Doped CdSe Nanocrystals.

PubMed

Nelson, Heidi D; Hinterding, Stijn O M; Fainblat, Rachel; Creutz, Sidney E; Li, Xiaosong; Gamelin, Daniel R

2017-05-10

Mid-gap luminescence in copper (Cu + )-doped semiconductor nanocrystals (NCs) involves recombination of delocalized conduction-band electrons with copper-localized holes. Silver (Ag + )-doped semiconductor NCs show similar mid-gap luminescence at slightly (∼0.3 eV) higher energy, suggesting a similar luminescence mechanism, but this suggestion appears inconsistent with the large difference between Ag + and Cu + ionization energies (∼1.5 eV), which should make hole trapping by Ag + highly unfavorable. Here, Ag + -doped CdSe NCs (Ag + :CdSe) are studied using time-resolved variable-temperature photoluminescence (PL) spectroscopy, magnetic circularly polarized luminescence (MCPL) spectroscopy, and time-dependent density functional theory (TD-DFT) to address this apparent paradox. In addition to confirming that Ag + :CdSe and Cu + :CdSe NCs display similar broad PL with large Stokes shifts, we demonstrate that both also show very similar temperature-dependent PL lifetimes and magneto-luminescence. Electronic-structure calculations further predict that both dopants generate similar localized mid-gap states. Despite these strong similarities, we conclude that these materials possess significantly different electronic structures. Specifically, whereas photogenerated holes in Cu + :CdSe NCs localize primarily in Cu(3d) orbitals, formally oxidizing Cu + to Cu 2+ , in Ag + :CdSe NCs they localize primarily in 4p orbitals of the four neighboring Se 2- ligands, and Ag + is not oxidized. This difference reflects a shift from "normal" to "inverted" bonding going from Cu + to Ag + . The spectroscopic similarities are explained by the fact that, in both materials, photogenerated holes are localized primarily within covalent [MSe 4 ] dopant clusters (M = Ag + , Cu + ). These findings reconcile the similar spectroscopies of Ag + - and Cu + -doped semiconductor NCs with the vastly different ionization potentials of their Ag + and Cu + dopants.

Syntheses, structures and properties of homo- and heterobimetallic complexes of the type [Zn(tren)NCS] 2[M(NCS) 4] [tren = tris(2-aminoethyl)amine; M = Zn, Cu

NASA Astrophysics Data System (ADS)

Chattopadhyay, Soumi; Bhar, Kishalay; Das, Sumitra; Chantrapromma, Suchada; Fun, Hoong-Kun; Ghosh, Barindra Kumar

2010-04-01

A 2:2:1:6 molar ratio of Zn(ClO 4) 2·6H 2O, tris(2-aminoethyl)amine (tren), Zn(ClO 4) 2·6H 2O/Cu(ClO 4) 2·6H 2O and NH 4NCS in methanol-water solution mixtures affords homo-/heterobimetallic compounds of the type [Zn(tren)NCS] 2[M(NCS) 4] (M = Zn, 1; M = Cu, 2) which have been characterized using microanalytical, spectroscopic, magnetic and other physicochemical results. The structures of the compounds are determined by X-ray diffraction measurements. Structural analyses reveal that 1 and 2 are isomorphous and consist of two discrete [Zn(tren)NCS] + cations and a [M(NCS) 4] 2- (M = Zn/Cu) anion. Zinc(II) centers in the [Zn(tren)NCS] + units adopt distorted trigonal bipyramidal geometry with ZnN 5 chromophores coordinated through four N atoms of tren and one N atom of terminal thiocyanate. Each metal(II) center in [M(NCS) 4] 2- has a distorted tetrahedral coordination environment with an MN 4 chromophore ligated by four N atoms of the terminal thiocyanates. In solid state, doubly N-H…S hydrogen bonded 1D chains of [Zn(tren)NCS] + cations are interconnected by tetrahedral [Zn(NCS) 4] 2-/[Cu(NCS) 4] 2- anions through cooperative N-H…S and N-H…N (in 1) and N-H…S and C-H…S (in 2) hydrogen bonds resulting in 3D network structures. Establishment of such networks seems to be aiding the crystallization.

Phonon Raman spectra of colloidal CdTe nanocrystals: effect of size, non-stoichiometry and ligand exchange

PubMed Central

2011-01-01

Resonant Raman study reveals the noticeable effect of the ligand exchange on the nanocrystal (NC) surface onto the phonon spectra of colloidal CdTe NC of different size and composition. The oleic acid ligand exchange for pyridine ones was found to change noticeably the position and width of the longitudinal optical (LO) phonon mode, as well as its intensity ratio to overtones. The broad shoulder above the LO peak frequency was enhanced and sharpened after pyridine treatment, as well as with decreasing NC size. The low-frequency mode around 100 cm-1 which is commonly related with the disorder-activated acoustical phonons appears in smaller NCs but is not enhanced after pyridine treatment. Surprisingly, the feature at low-frequency shoulder of the LO peak, commonly assigned to the surface optical phonon mode, was not sensitive to ligand exchange and concomitant close packing of the NCs. An increased structural disorder on the NC surface, strain and modified electron-phonon coupling is discussed as the possible reason of the observed changes in the phonon spectrum of ligand-exchanged CdTe NCs. PACS: 63.20.-e, 78.30.-j, 78.67.-n, 78.67.Bf PMID:21711581

Reaction Dynamics of Proton-Coupled Electron Transfer from Reduced ZnO Nanocrystals.

PubMed

Braten, Miles N; Gamelin, Daniel R; Mayer, James M

2015-10-27

The creation of systems that efficiently interconvert chemical and electrical energies will be aided by understanding proton-coupled electron transfers at solution-semiconductor interfaces. Steps in developing that understanding are described here through kinetic studies of reactions of photoreduced colloidal zinc oxide (ZnO) nanocrystals (NCs) with the nitroxyl radical TEMPO. These reactions proceed by proton-coupled electron transfer (PCET) to give the hydroxylamine TEMPOH. They occur on the submillisecond to seconds time scale, as monitored by stopped-flow optical spectroscopy. Under conditions of excess TEMPO, the reactions are multiexponential in character. One of the contributors to this multiexponential kinetics may be a distribution of reactive proton sites. A graphical overlay method shows the reaction to be first order in [TEMPO]. Different electron concentrations in otherwise identical NC samples were achieved by three different methods: differing photolysis times, premixing with an unphotolyzed sample, or prereaction with TEMPO. The reaction velocities were consistently higher for NCs with higher numbers of electrons. For instance, NCs with an average of 2.6 e(-)/NC reacted faster than otherwise identical samples containing ≤1 e(-)/NC. Surprisingly, NC samples with the same average number of electrons but prepared in different ways often had different reaction profiles. These results show that properties beyond electron content determine PCET reactivity of the particles.

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).

Characterization of Silicon Nanocrystal Surfaces by Multidimensional Solid-State NMR Spectroscopy

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

Hanrahan, Michael P.; Fought, Ellie L.; Windus, Theresa L.

The chemical and photophysical properties of silicon nanocrystals (Si NCs) are strongly dependent on the chemical composition and structure of their surfaces. Here we use fast magic angle spinning (MAS) and proton detection to enable the rapid acquisition of dipolar and scalar 2D 1H– 29Si heteronuclear correlation (HETCOR) solid-state NMR spectra and reveal a molecular picture of hydride-terminated and alkyl-functionalized surfaces of Si NCs produced in a nonthermal plasma. 2D 1H– 29Si HETCOR and dipolar 2D 1H– 1H multiple-quantum correlation spectra illustrate that resonances from surface mono-, di-, and trihydride groups cannot be resolved, contrary to previous literature assignments. Insteadmore » the 2D NMR spectra illustrate that there is large distribution of 1H and 29Si chemical shifts for the surface hydride species in both the as-synthesized and functionalized Si NCs. However, proton-detected 1H– 29Si refocused INEPT experiments can be used to unambiguously differentiate NMR signals from the different surface hydrides. Varying the 29Si evolution time in refocused INEPT experiments and fitting the oscillation of the NMR signals allows for the relative populations of the different surface hydrides to be estimated. This analysis confirms that monohydride species are the predominant surface species on the as-synthesized Si NCs. A reduction in the populations of the di- and trihydrides is observed upon functionalization with alkyl groups, consistent with our previous hypothesis that the trihydride, or silyl (*SiH 3), group is primarily responsible for initiating surface functionalization reactions. Density functional theory (DFT) calculations were used to obtain quantum chemical structural models of the Si NC surface and reproduce the observed 1H and 29Si chemical shifts. Furthermore, the approaches outlined here will be useful to obtain a more detailed picture of surface structures for Si NCs and other hydride-passivated nanomaterials.« less

Characterization of Silicon Nanocrystal Surfaces by Multidimensional Solid-State NMR Spectroscopy

DOE PAGES

Hanrahan, Michael P.; Fought, Ellie L.; Windus, Theresa L.; ...

2017-11-22

The chemical and photophysical properties of silicon nanocrystals (Si NCs) are strongly dependent on the chemical composition and structure of their surfaces. Here we use fast magic angle spinning (MAS) and proton detection to enable the rapid acquisition of dipolar and scalar 2D 1H– 29Si heteronuclear correlation (HETCOR) solid-state NMR spectra and reveal a molecular picture of hydride-terminated and alkyl-functionalized surfaces of Si NCs produced in a nonthermal plasma. 2D 1H– 29Si HETCOR and dipolar 2D 1H– 1H multiple-quantum correlation spectra illustrate that resonances from surface mono-, di-, and trihydride groups cannot be resolved, contrary to previous literature assignments. Insteadmore » the 2D NMR spectra illustrate that there is large distribution of 1H and 29Si chemical shifts for the surface hydride species in both the as-synthesized and functionalized Si NCs. However, proton-detected 1H– 29Si refocused INEPT experiments can be used to unambiguously differentiate NMR signals from the different surface hydrides. Varying the 29Si evolution time in refocused INEPT experiments and fitting the oscillation of the NMR signals allows for the relative populations of the different surface hydrides to be estimated. This analysis confirms that monohydride species are the predominant surface species on the as-synthesized Si NCs. A reduction in the populations of the di- and trihydrides is observed upon functionalization with alkyl groups, consistent with our previous hypothesis that the trihydride, or silyl (*SiH 3), group is primarily responsible for initiating surface functionalization reactions. Density functional theory (DFT) calculations were used to obtain quantum chemical structural models of the Si NC surface and reproduce the observed 1H and 29Si chemical shifts. Furthermore, the approaches outlined here will be useful to obtain a more detailed picture of surface structures for Si NCs and other hydride-passivated nanomaterials.« less

Colloidal Cobalt Phosphide Nanocrystals as Trifunctional Electrocatalysts for Overall Water Splitting Powered by a Zinc–Air Battery

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

Li, Hui; Li, Qi; Wen, Peng

Highly efficient and stable electrocatalysts, particularly those that are capable of multifunctionality in the same electrolyte, are in high demand for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). In this paper, highly monodisperse CoP and Co 2P nanocrystals (NCs) are synthesized using a robust solution-phase method. The highly exposed (211) crystal plane and abundant surface phosphide atoms make the CoP NCs efficient catalysts toward ORR and HER, while metal-rich Co 2P NCs show higher OER performance owing to easier formation of plentiful Co 2P@COOH heterojunctions. Density functional theory calculation results indicate that themore » desorption of OH* from cobalt sites is the rate-limiting step for both CoP and Co 2P in ORR and that the high content of phosphide can lower the reaction barrier. A water electrolyzer constructed with a CoP NC cathode and a Co 2P NC anode can achieve a current density of 10 mA cm -2 at 1.56 V, comparable even to the noble metal-based Pt/C and RuO 2/C pair. Finally and furthermore, the CoP NCs are employed as an air cathode in a primary zinc–air battery, exhibiting a high power density of 62 mW cm -2 and good stability.« less

Colloidal Cobalt Phosphide Nanocrystals as Trifunctional Electrocatalysts for Overall Water Splitting Powered by a Zinc–Air Battery

DOE PAGES

Li, Hui; Li, Qi; Wen, Peng; ...

2018-01-15

Highly efficient and stable electrocatalysts, particularly those that are capable of multifunctionality in the same electrolyte, are in high demand for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). In this paper, highly monodisperse CoP and Co 2P nanocrystals (NCs) are synthesized using a robust solution-phase method. The highly exposed (211) crystal plane and abundant surface phosphide atoms make the CoP NCs efficient catalysts toward ORR and HER, while metal-rich Co 2P NCs show higher OER performance owing to easier formation of plentiful Co 2P@COOH heterojunctions. Density functional theory calculation results indicate that themore » desorption of OH* from cobalt sites is the rate-limiting step for both CoP and Co 2P in ORR and that the high content of phosphide can lower the reaction barrier. A water electrolyzer constructed with a CoP NC cathode and a Co 2P NC anode can achieve a current density of 10 mA cm -2 at 1.56 V, comparable even to the noble metal-based Pt/C and RuO 2/C pair. Finally and furthermore, the CoP NCs are employed as an air cathode in a primary zinc–air battery, exhibiting a high power density of 62 mW cm -2 and good stability.« less

14N NQR lineshape in nanocrystals: An ab initio investigation of urea

PubMed Central

Gregorovič, Alan

2017-01-01

14N nuclear quadrupole resonance (NQR) lineshapes mostly contain information of low interest, although in nanocrystals they may display some unexpected behaviour. In this work, we present an ab initio computational study of the 14N NQR lineshapes in urea nanocrystals as a function of the nanocrystal size and geometry, focusing on the surface induced broadening of the lineshapes. The lineshapes were obtained through a calculation of the electric field gradient for each nitrogen site in the nanocrystal separately, taking into account the individual crystal field by embedding the molecule of interest in a suitable lattice of point multipoles representing other urea molecules in the nanocrystal. The small influence of distant molecules is found with a series expansion, using the in-crystal Sternheimer shieldings which we also calculated ab initio. We have considered nanocrystals with two geometries: a sphere and a cube, with characteristic sizes between 5 and 100 nm. Our calculations suggest that there is a dramatic difference between the linewidths for the two geometries. For spheres, we find a steep drop in linewidths at ∼10 nm; at 5 nm the linewidth is ∼11 kHz, whereas for sizes above 20 nm the linewidth is practically negligible (<100 Hz). For cubes, on the other hand, we find a steady 1/size decrease, from 12 kHz at 10 nm to 1.2 kHz at 100 nm. This analysis is important for 14N NQR spectroscopy of crystalline pharmaceuticals, where nanoparticles are increasingly more often embedded in some sort of matrix. Although this is only a theoretical analysis, we believe that this work can serve as a guidance for the forthcoming experimental analysis. PMID:28527464

pH-dependent optical properties of N-acetyl-L-cysteine-capped ZnSe(S) nanocrystals with intense/stable emissions

NASA Astrophysics Data System (ADS)

Soheyli, Ehsan; Sahraei, Reza; Nabiyouni, Gholamreza

2017-03-01

In the present study, a series of aqueous-based ZnSe(S) nanocrystals (NCs) was prepared at different solution pH ranging from 8 to 11.9, and using N-acetyl-L-cysteine (NAC) as capping agent. In addition to zinc blende structure, the X-ray diffraction studies demonstrated the quantum size regime of the ZnSe(S) NCs. To gain further insight toward the influence of the quantum confinement and pH values on optical properties of the as-prepared NCs, their UV-visible absorption and photoluminescence spectra were systematically analyzed. The absorption spectra experienced a red shift from 340 to 382 nm as the pH increased from 8.0 to 11.9, indicating the growth of the as-prepared ZnSe(S) NCs. The emission spectra also show the obvious red shift and the relative area of excitonic to trap emission, firstly increases from pH = 8.0 to 10.7, and then decreases by further increasing of the solution pH. The initial behavior might be due to the improved surface passivation of the trap dangling states by better deprotonation of thiol groups in NAC, whereas at pH >10.7, the faster growth rate of the ZnSe(s) NCs may lead to the formation of many defect sites. All of these phenomena were combined in the scheme which displays the effect of quantum confinement and solution pH on variation of the excitonic and trap-related emissions.

Nano-electron beam induced current and hole charge dynamics through uncapped Ge nanocrystals

NASA Astrophysics Data System (ADS)

Marchand, A.; El Hdiy, A.; Troyon, M.; Amiard, G.; Ronda, A.; Berbezier, I.

2012-04-01

Dynamics of hole storage in spherical Ge nanocrystals (NCs) formed by a two step dewetting/nucleation process on an oxide layer grown on an n-doped <001> silicon substrate is studied using a nano-electron beam induced current technique. Carrier generation is produced by an electron beam irradiation. The generated current is collected by an atomic force microscope—tip in contact mode at a fixed position away from the beam spot of about 0.5 µm. This distance represents the effective diffusion length of holes. The time constants of holes charging are determined and the effect of the NC size is underlined.

Sensitized luminescence from water-soluble LaF3:Eu nanocrystals via partially-capped 1,10-phenanthroline: time-gated emission and multiple lifetimes.

PubMed

Irfanullah, Mir; Bhardwaj, Navneet; Chowdhury, Arindam

2016-08-02

Water dispersible citrate-capped LaF3:Eu(5%) nanocrystals (NCs) have been partially surface-functionalized by 1,10-phenanthroline (phen) via a ligand exchange method to produce novel water dispersed citrate/phen-capped LaF3:Eu(5%) NCs in which citrate ligands preserve the water dispersibility of the NCs and phen ligands act as sensitizers of surface Eu(3+)-dopant sites. The partial ligand exchange and the formation of water dispersed NCs have been monitored by (1)H NMR spectroscopy, as well as luminescence measurements at different time intervals during the reaction. These NCs display a distinct phen-sensitized Eu(3+)-emission profile with enhanced intensity in water as compared to the emission profile and intensity obtained upon direct excitation. Time-resolved (or time-gated) emission spectroscopy (TRES) has been used to probe PL dynamics of Eu(3+)-sites of LaF3:Eu(5%) NCs by taking advantage of selectively sensitizing surface Eu(3+)-dopant sites by phen ligands as well as by exciting all the Eu(3+)-sites in the NCs upon direct excitation. TRES upon direct excitation of the citrate-capped LaF3:Eu(5%) NCs reveals that Eu(3+)-dopants occupy at least three different sites, each with a different emission profile and lifetime, and emission from purely interior Eu(3+)-sites has been resolved due to their long lifetime as compared to the lifetime of purely surface and near surface Eu(3+)-sites. In contrast, the phen-sensitized emission from citrate/phen-capped LaF3:Eu(5%) NCs displays similar emission profiles and lifetimes in TRES measurements, which reveal that phen truly sensitizes purely surface dopant sites of the NCs in water, all of which have nearly the same local environment. The phen-sensitized Eu(3+)-emission of the NCs in water remains stable even upon addition of various buffer solutions at physiological pH, as well as upon addition of water-miscible organic solvents. Furthermore, the two-photon excitation (λex. = 720 nm) of these water-soluble phen

Exploration of Near-Infrared-Emissive Colloidal Multinary Lead Halide Perovskite Nanocrystals Using an Automated Microfluidic Platform.

PubMed

Lignos, Ioannis; Morad, Viktoriia; Shynkarenko, Yevhen; Bernasconi, Caterina; Maceiczyk, Richard M; Protesescu, Loredana; Bertolotti, Federica; Kumar, Sudhir; Ochsenbein, Stefan T; Masciocchi, Norberto; Guagliardi, Antonietta; Shih, Chih-Jen; Bodnarchuk, Maryna I; deMello, Andrew J; Kovalenko, Maksym V

2018-05-22

Hybrid organic-inorganic and fully inorganic lead halide perovskite nanocrystals (NCs) have recently emerged as versatile solution-processable light-emitting and light-harvesting optoelectronic materials. A particularly difficult challenge lies in warranting the practical utility of such semiconductor NCs in the red and infrared spectral regions. In this context, all three archetypal A-site monocationic perovskites-CH 3 NH 3 PbI 3 , CH(NH 2 ) 2 PbI 3 , and CsPbI 3 -suffer from either chemical or thermodynamic instabilities in their bulk form. A promising approach toward the mitigation of these challenges lies in the formation of multinary compositions (mixed cation and mixed anion). In the case of multinary colloidal NCs, such as quinary Cs x FA 1- x Pb(Br 1- y I y ) 3 NCs, the outcome of the synthesis is defined by a complex interplay between the bulk thermodynamics of the solid solutions, crystal surface energies, energetics, dynamics of capping ligands, and the multiple effects of the reagents in solution. Accordingly, the rational synthesis of such NCs is a formidable challenge. Herein, we show that droplet-based microfluidics can successfully tackle this problem and synthesize Cs x FA 1- x PbI 3 and Cs x FA 1- x Pb(Br 1- y I y ) 3 NCs in both a time- and cost-efficient manner. Rapid in situ photoluminescence and absorption measurements allow for thorough parametric screening, thereby permitting precise optical engineering of these NCs. In this showcase study, we fine-tune the photoluminescence maxima of such multinary NCs between 700 and 800 nm, minimize their emission line widths (to below 40 nm), and maximize their photoluminescence quantum efficiencies (up to 89%) and phase/chemical stabilities. Detailed structural analysis revealed that the Cs x FA 1- x Pb(Br 1- y I y ) 3 NCs adopt a cubic perovskite structure of FAPbI 3 , with iodide anions partially substituted by bromide ions. Most importantly, we demonstrate the excellent transference of reaction

Structural and optical characterization of GaAs nano-crystals selectively grown on Si nano-tips by MOVPE.

PubMed

Skibitzki, Oliver; Prieto, Ivan; Kozak, Roksolana; Capellini, Giovanni; Zaumseil, Peter; Arroyo Rojas Dasilva, Yadira; Rossell, Marta D; Erni, Rolf; von Känel, Hans; Schroeder, Thomas

2017-03-01

We present the nanoheteroepitaxial growth of gallium arsenide (GaAs) on nano-patterned silicon (Si) (001) substrates fabricated using a CMOS technology compatible process. The selective growth of GaAs nano-crystals (NCs) was achieved at 570 °C by MOVPE. A detailed structure and defect characterization study of the grown nano-heterostructures was performed using scanning transmission electron microscopy, x-ray diffraction, micro-Raman, and micro-photoluminescence (μ-PL) spectroscopy. The results show single-crystalline, nearly relaxed GaAs NCs on top of slightly, by the SiO 2 -mask compressively strained Si nano-tips (NTs). Given the limited contact area, GaAs/Si nanostructures benefit from limited intermixing in contrast to planar GaAs films on Si. Even though a few growth defects (e.g. stacking faults, micro/nano-twins, etc) especially located at the GaAs/Si interface region were detected, the nanoheterostructures show intensive light emission, as investigated by μ-PL spectroscopy. Achieving well-ordered high quality GaAs NCs on Si NTs may provide opportunities for superior electronic, photonic, or photovoltaic device performances integrated on the silicon technology platform.

Origin of visible and near-infrared photoluminescence from chemically etched Si nanowires decorated with arbitrarily shaped Si nanocrystals.

PubMed

Ghosh, Ramesh; Giri, P K; Imakita, Kenji; Fujii, Minoru

2014-01-31

Arrays of vertically aligned single crystalline Si nanowires (NWs) decorated with arbitrarily shaped Si nanocrystals (NCs) have been fabricated by a silver assisted wet chemical etching method. Scanning electron microscopy and transmission electron microscopy are performed to measure the dimensions of the Si NWs as well as the Si NCs. A strong broad band and tunable visible (2.2 eV) to near-infrared (1.5 eV) photoluminescence (PL) is observed from these Si NWs at room temperature (RT). Our studies reveal that the Si NCs are primarily responsible for the 1.5-2.2 eV emission depending on the cross-sectional area of the Si NCs, while the large diameter Si/SiOx NWs yield distinct NIR PL consisting of peaks at 1.07, 1.10 and 1.12 eV. The latter NIR peaks are attributed to TO/LO phonon assisted radiative recombination of free carriers condensed in the electron-hole plasma in etched Si NWs observed at RT for the first time. Since the shape of the Si NCs is arbitrary, an analytical model is proposed to correlate the measured PL peak position with the cross-sectional area (A) of the Si NCs, and the bandgap (E(g)) of nanostructured Si varies as E(g) = E(g) (bulk) + 3.58 A(-0.52). Low temperature PL studies reveal the contribution of non-radiative defects in the evolution of PL spectra at different temperatures. The enhancement of PL intensity and red-shift of the PL peak at low temperatures are explained based on the interplay of radiative and non-radiative recombinations at the Si NCs and Si/SiO(x) interface. Time resolved PL studies reveal bi-exponential decay with size correlated lifetimes in the range of a few microseconds. Our results help to resolve a long standing debate on the origin of visible-NIR PL from Si NWs and allow quantitative analysis of PL from arbitrarily shaped Si NCs.

FINAL REPORT: NATIONAL CHILDREN'S STUDY (NCS) ESTIMATING SUBJECT BURDEN FOR POTENTIAL NCS MEASUREMENTS

EPA Science Inventory

Purpose The National Children's Study (NCS), a large longitudinal cohort study of environmental exposures among children, is currently in the planning stage. Prior to enrollment of 100,000 pregnant women across the United Sates for this study, a better understanding of the partic...

Hot injection synthesis of Cu(In, Ga)Se2 nanocrystals with tunable bandgap

NASA Astrophysics Data System (ADS)

Latha, M.; Aruna Devi, R.; Velumani, S.

2018-05-01

CuIn1-xGaxSe2 nanocrystals (CIGSe NCs) were synthesized with different gallium (Ga) content by the hot injection process at low reaction temperature for the first time. The Ga content [x = Ga(In + Ga)] was varied such as 0, 0.25, 0.50 and 0.75 to study their influences on the structural, morphological, compositional and optical properties of CIGSe NCs. X-ray diffraction (XRD) analysis showed the peak shift towards higher 2θ angle. The lattice parameters a and c were decreased linearly as x value increases which propitiated Vegard's law. Transmission electron microscopy (TEM) analysis revealed a decrease in the particle size from 55 to 22 nm. Ultraviolet-visible-near infrared (UV-vis-NIR) absorption spectra indicated a blue shift towards the lower wavelength and bandgap was tuned from 1.04 to 1.41eV. Apart from this, CIGSe thin films were prepared by doctor blade coating method followed by annealing under Se/Ar atmosphere. The mobility of CIGSe thin film increased whereas resistivity decreased. Moreover, the photoconductivity of CIGSe annealed thin film exhibited almost 2-fold increase under an illumination of light. We realize from these results that the synthesized CIGSe NCs with x = 0.25 is expected to have the important perspective to be efficiently exploited as an absorber layer in cost-effective thin film solar cells.

Facile preparation and characterization of ZnCdS nanocrystals for interfacial applications in photovoltaic devices.

PubMed

Duan, Chenghao; Luo, Weining; Jiu, Tonggang; Li, Jiangsheng; Wang, Yao; Lu, Fushen

2018-02-15

Recently, ZnCdS nanocrystals (NCs) have attracted intense attention because of their specific optical properties and electrical characteristics. In this paper, a green and facile solution method is reported for the preparation of ZnCdS nanocrystals using dimethylsulfoxide as small molecular ligands. The ZnCdS nanocrystals are used as an interface modification material in the photovoltaic devices. It is found that the modification of ZnCdS on TiO 2 surface not only suppresses the recombination loss of carriers but also reduces the series resistance of TiO 2 /active layer. Consequently, both of the short circuit current (J sc ) and the fill factor (FF) of the solar cells were significantly improved. Power conversion efficiency (PCE) of 7.75% based on TiO 2 /ZnCdS was achieved in contrast to 6.65% of the reference devices based on pure TiO 2 film in organic solar cells. Furthermore, the PCE of perovskite solar cells based on TiO 2 /ZnCdS was observed with 8.3% enhancement compared to that of pure TiO 2 -based ones. Copyright © 2017 Elsevier Inc. All rights reserved.

Electrochemiluminescent pH sensor measured by the emission potential of TiO2 nanocrystals and its biosensing application.

PubMed

Liu, Xuan; Wang, Nianyue; Zhao, Wei; Jiang, Hui

2015-02-01

This work reports for the first time a potential-based nano-electrochemiluminescent (ECL) pH sensor, using anatase TiO2 nanocrystals (NCs) as the ECL probe. The first ECL peak potential of the TiO2 NCs shifted negatively with increasing pH, showing a linear range from -0.47 V (vs Ag/AgCl) at pH 3 to -1.06 V at pH 10. This phenomenon was attributed to the absorption of 'potential-determining ions' of OH(-) on the surface of TiO2 NCs, leading to larger impedance of the electron injection. Other common 'potential-determining ions', such as phosphate, induced a slight potential shift of 0.03 V at a concentration of 0.1 M. Using urease as an enzyme model, a urea biosensor was developed by the simultaneous modification of urease and TiO2 NCs on indium-tin oxide (ITO) electrodes. The biosensor, measured on the basis of the pH increase caused by the enzyme catalysis reaction, had a linear range of 0.01-2.0 mM, with a potential shift of 0.175 V. The as-prepared pH sensor, which has simple construction procedures and acceptable sensitivity and selectivity, may provide new avenues for the construction of ECL bioanalytical methodologies. Copyright © 2014 John Wiley & Sons, Ltd.

Tuning Li-Ion Diffusion in α-LiMn 1–x Fe x PO 4 Nanocrystals by Antisite Defects and Embedded β-Phase for Advanced Li-Ion Batteries

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

Hu, Jiangtao; Xiao, Yinguo; Tang, Hanting

Olivine-structured LiMn1-xFexPO4 has become a promising candidate for cathode materials owing to its higher working voltage of 4.1 V and thus larger energy density than that of LiFePO4, which has been used for electric vehicles batteries with the advantage of high safety but disadvantage of low energy density due to its lower working voltage of 3.4 V. One drawback of LiMn1-xFexPO4 electrode is its relatively low electronic and Li-ionic conductivity with Li-ion one-dimensional diffusion. Herein, olivine-structured α-LiMn0.5Fe0.5PO4 nanocrystals were synthesized with optimized Li-ion diffusion channels in LiMn1-xFexPO4 nanocrystals by inducing high concentrations of Fe2+-Li+ antisite defects, which showed impressive capacitymore » improvements of approaching 162, 127, 73, and 55 mAh g-1 at 0.1, 10, 50, and 100 C, respectively, and a long-term cycling stability of maintaining about 74% capacity after 1000 cycles at 10 C. By using high-resolution transmission electron microscopy imaging and joint refinement of hard X-ray and neutron powder diffraction patterns, we revealed that the extraordinary high-rate performance could be achieved by suppressing the formation of electrochemically inactive phase (β-LiMn1-xFexPO4, which is first reported in this work) embedded in α-LiMn0.5Fe0.5PO4. Because of the coherent orientation relationship between β- and α- phases, the β-phase embedded would impede the Li+ diffusion along the [100] and/or [001] directions that was activated by the high density of Fe2+-Li+ antisite (4.24%) in α-phase. Thus, by optimizing concentrations of Fe2+-Li+ antisite defects and suppressing β-phase-embedded olivine structure, Li-ion diffusion properties in LiMn1-xFexPO4 nanocrystals can be tuned by generating new Li+ tunneling. These findings may provide insights into the design and generation of other advanced electrode materials with improved rate performance.« less

Tuning Li-Ion Diffusion in α-LiMn 1–xFe xPO 4 Nanocrystals by Antisite Defects and Embedded β-Phase for Advanced Li-Ion Batteries

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

Hu, Jiangtao; Xiao, Yinguo; Tang, Hanting

Olivine-structured LiMn 1–xFe xPO 4 has become a promising candidate for cathode materials owing to its higher working voltage of 4.1 V and thus larger energy density than that of LiFePO 4, which has been used for electric vehicles batteries with the advantage of high safety but disadvantage of low energy density due to its lower working voltage of 3.4 V. One drawback of LiMn 1–xFe xPO 4 electrode is its relatively low electronic and Li-ionic conductivity with Li-ion one-dimensional diffusion. In this paper, olivine-structured α-LiMn 0.5Fe 0.5PO 4 nanocrystals were synthesized with optimized Li-ion diffusion channels in LiMn 1–xFemore » xPO 4 nanocrystals by inducing high concentrations of Fe 2+–Li + antisite defects, which showed impressive capacity improvements of approaching 162, 127, 73, and 55 mAh g –1 at 0.1, 10, 50, and 100 C, respectively, and a long-term cycling stability of maintaining about 74% capacity after 1000 cycles at 10 C. By using high-resolution transmission electron microscopy imaging and joint refinement of hard X-ray and neutron powder diffraction patterns, we revealed that the extraordinary high-rate performance could be achieved by suppressing the formation of electrochemically inactive phase (β-LiMn 1–xFe xPO 4, which is first reported in this work) embedded in α-LiMn 0.5Fe 0.5PO 4. Because of the coherent orientation relationship between β- and α-phases, the β-phase embedded would impede the Li + diffusion along the [100] and/or [001] directions that was activated by the high density of Fe 2+–Li + antisite (4.24%) in α-phase. Thus, by optimizing concentrations of Fe 2+–Li + antisite defects and suppressing β-phase-embedded olivine structure, Li-ion diffusion properties in LiMn 1–xFe xPO 4 nanocrystals can be tuned by generating new Li + tunneling. Finally, these findings may provide insights into the design and generation of other advanced electrode materials with improved rate performance.« less

Tuning Li-Ion Diffusion in α-LiMn 1–xFe xPO 4 Nanocrystals by Antisite Defects and Embedded β-Phase for Advanced Li-Ion Batteries

DOE PAGES

Hu, Jiangtao; Xiao, Yinguo; Tang, Hanting; ...

2017-07-13

Olivine-structured LiMn 1–xFe xPO 4 has become a promising candidate for cathode materials owing to its higher working voltage of 4.1 V and thus larger energy density than that of LiFePO 4, which has been used for electric vehicles batteries with the advantage of high safety but disadvantage of low energy density due to its lower working voltage of 3.4 V. One drawback of LiMn 1–xFe xPO 4 electrode is its relatively low electronic and Li-ionic conductivity with Li-ion one-dimensional diffusion. In this paper, olivine-structured α-LiMn 0.5Fe 0.5PO 4 nanocrystals were synthesized with optimized Li-ion diffusion channels in LiMn 1–xFemore » xPO 4 nanocrystals by inducing high concentrations of Fe 2+–Li + antisite defects, which showed impressive capacity improvements of approaching 162, 127, 73, and 55 mAh g –1 at 0.1, 10, 50, and 100 C, respectively, and a long-term cycling stability of maintaining about 74% capacity after 1000 cycles at 10 C. By using high-resolution transmission electron microscopy imaging and joint refinement of hard X-ray and neutron powder diffraction patterns, we revealed that the extraordinary high-rate performance could be achieved by suppressing the formation of electrochemically inactive phase (β-LiMn 1–xFe xPO 4, which is first reported in this work) embedded in α-LiMn 0.5Fe 0.5PO 4. Because of the coherent orientation relationship between β- and α-phases, the β-phase embedded would impede the Li + diffusion along the [100] and/or [001] directions that was activated by the high density of Fe 2+–Li + antisite (4.24%) in α-phase. Thus, by optimizing concentrations of Fe 2+–Li + antisite defects and suppressing β-phase-embedded olivine structure, Li-ion diffusion properties in LiMn 1–xFe xPO 4 nanocrystals can be tuned by generating new Li + tunneling. Finally, these findings may provide insights into the design and generation of other advanced electrode materials with improved rate performance.« less

Light-induced changes in silicon nanocrystal based solar cells: Modification of silicon-hydrogen bonding on silicon nanocrystal surface under illumination

NASA Astrophysics Data System (ADS)

Kim, Ka-Hyun; Johnson, Erik V.; Cabarrocas, Pere Roca i.

2016-07-01

Hydrogenated polymorphous silicon (pm-Si:H) is a material consisting of a small volume fraction of nanocrystals embedded in an amorphous matrix. pm-Si:H solar cells demonstrate interesting initial degradation behaviors such as rapid initial change in photovoltaic parameters and self-healing after degradation during light-soaking. The precise dynamics of the light-induced degradation was studied in a series of light-soaking experiments under various illumination conditions such as AM1.5G and filtered 570 nm yellow light. Hydrogen effusion experiment before and after light-soaking further revealed that the initial degradation of pm-Si:H solar cells originate from the modification of silicon-hydrogen bonding on the surface of silicon nanocrystals in pm-Si:H.

Pyrite (FeS2) nanocrystals as inexpensive high-performance lithium-ion cathode and sodium-ion anode materials

NASA Astrophysics Data System (ADS)

Walter, Marc; Zünd, Tanja; Kovalenko, Maksym V.

2015-05-01

In light of the impeding depletion of fossil fuels and necessity to lower carbon dioxide emissions, economically viable high-performance batteries are urgently needed for numerous applications ranging from electric cars to stationary large-scale electricity storage. Due to its low raw material cost, non-toxicity and potentially high charge-storage capacity pyrite (FeS2) is a highly promising material for such next-generation batteries. In this work we present the electrochemical performance of FeS2 nanocrystals (NCs) as lithium-ion and sodium-ion storage materials. First, we show that nanoscopic FeS2 is a promising lithium-ion cathode material, delivering a capacity of 715 mA h g-1 and average energy density of 1237 Wh kg-1 for 100 cycles, twice higher than for commonly used LiCoO2 cathodes. Then we demonstrate, for the first time, that FeS2 NCs can serve as highly reversible sodium-ion anode material with long cycling life. As sodium-ion anode material, FeS2 NCs provide capacities above 500 mA h g-1 for 400 cycles at a current rate of 1000 mA g-1. In all our tests and control experiments, the performance of chemically synthesized nanoscale FeS2 clearly surpasses bulk FeS2 as well as large number of other nanostructured metal sulfides.In light of the impeding depletion of fossil fuels and necessity to lower carbon dioxide emissions, economically viable high-performance batteries are urgently needed for numerous applications ranging from electric cars to stationary large-scale electricity storage. Due to its low raw material cost, non-toxicity and potentially high charge-storage capacity pyrite (FeS2) is a highly promising material for such next-generation batteries. In this work we present the electrochemical performance of FeS2 nanocrystals (NCs) as lithium-ion and sodium-ion storage materials. First, we show that nanoscopic FeS2 is a promising lithium-ion cathode material, delivering a capacity of 715 mA h g-1 and average energy density of 1237 Wh kg-1 for 100

A pyrazolyl-based thiolato single-source precursor for the selective synthesis of isotropic copper-deficient copper(I) sulfide nanocrystals: synthesis, optical and photocatalytic activity

NASA Astrophysics Data System (ADS)

Mondal, Gopinath; Santra, Ananyakumari; Bera, Pradip; Acharjya, Moumita; Jana, Sumanta; Chattopadhyay, Dipankar; Mondal, Anup; Seok, Sang Il; Bera, Pulakesh

2016-10-01

Hexagonal copper-deficient copper(I) sulfide (Cu2- x S, x = 0.03, 0.2) nanocrystals (NCs) are synthesized from a newly prepared single-source precursor (SP), [Cu(bdpa)2][CuCl2], where bdpa is benzyl 3,5-dimethyl-pyrazole-1-carbodithioate. The SP is crystallized with space group Pī and possesses a distorted tetrahedron structure with a CuN2S2 chromophore where the central copper is in +1 oxidation state. Distortion in copper(I) structure and the low decomposition temperature of SP make it favorable for the low-temperature solvent-assisted selective growth of high-copper content sulfides. The nucleation and growth of Cu2- x S ( x = 0.03, 0.2) are effectively controlled by the SP and the solvent in the solvothermal decomposition process. During decomposition, fragment benzyl thiol (PhCH2SH) from SP effectively passivates the nucleus leading to spherical nanocrystals. Further, solvent plays an important role in the selective thermochemical transformation of CuI-complex to Cu2- x S ( x = 0.03, 0.2) NCs. The chelating binders (solvent) like ethylene diamine (EN) and ethylene glycol (EG) prefer to form spherical Cu1.97S nanoparticles (djurleite), whereas nonchelating hydrazine hydrate (HH) shows the tendency to furnish hexagonal platelets of copper-deficient Cu1.8S. The optical band gap values (2.25-2.50 eV) show quantum confinement effect in the structure. The synthesized NCs display excellent catalytic activity ( 87 %) toward photodegradation of organic dyes like Congo Red (CR) and Methylene Blue (MB).

Size-Dependent Photon Emission from Organometal Halide Perovskite Nanocrystals Embedded in an Organic Matrix

PubMed Central

2015-01-01

In recent years, organometal halide perovskite materials have attracted significant research interest in the field of optoelectronics. Here, we introduce a simple and low-temperature route for the formation of self-assembled perovskite nanocrystals in a solid organic matrix. We demonstrate that the size and photoluminescence peak of the perovskite nanocrystals can be tuned by varying the concentration of perovskite in the matrix material. The physical origin of the blue shift of the perovskite nanocrystals’ emission compared to its bulk phase is also discussed. PMID:25949773

A near-infrared BSA coated DNA-AgNCs for cellular imaging.

PubMed

Mu, Wei-Yu; Yang, Rui; Robertson, Akrofi; Chen, Qiu-Yun

2018-02-01

Near-infrared silver nanoclusters, have potential applications in the field of biosensing and biological imaging. However, less stability of most DNA-AgNCs limits their application. To obtain stable near-infrared fluorescence DNA-AgNCs for biological imaging, a new kind of near-infrared fluorescent DNA-Ag nanoclusters was constructed using the C3A rich aptamer as a synthesis template, GAG as the enhancer. In particular, a new DNA-AgNCs-Trp@BSA was obtained based on the self-assembly of bovine serum albumin (BSA) and tryptophan loaded DNA-AgNCs by hydrophobic interaction. This self-assembly method can be used to stabilize DNAn-Ag (n = 1-3) nanoclusters. Hence, the near-infrared fluorescence DNA-AgNCs-Trp@BSA was applied in cellular imaging of HepG-2 cells. Copyright © 2017 Elsevier B.V. All rights reserved.

Dynamic Evolution of 2D Layers Within Perovskite Nanocrystals via Salt Pair Extraction and Reinsertion

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

Wheeler, Lance M; Anderson, Nicholas C; Bliss, Taylor

Metal halide perovskite (MHP) semiconductors exhibit unprecedented optoelectronic properties coupled with low formation energies that enable scalable, cost-efficient solution processing. The low formation energies additionally facilitate dynamic transformation of the chemical composition and crystal structure of the MHP material. In this work, we show that CsBr salt is selectively extracted from CsPbBr3 nanocrystals (NCs) to yield PbBr2 NCs. The PbBr2 NCs are then exposed to different glacial acetic acid ABr salt solutions to generate a variety of emissive compounds with the generic structure A'2An-1PbnBr3n-1X'2, where A = cesium (Cs+), methylammonium (MA+), formamidinium (FA+); A' = A or H+; X' =more » Br- or acetate (CH3COO-); and n is the number of lead halide layers, where n = 1, 2, 3, ...8. We systematically vary the ratios of PbBr2/ABr/CH3COOH and show that certain ratios result in isolable single-phase APbBr3 NCs - an effective A-site cation exchange from the parent CsPbBr3 NCs. Importantly, time-resolved photoluminescence (PL) spectroscopy shows the dynamic evolution of many additional species as evidenced by blue-shifted emission peaks from 2.85-2.49 eV for MA+-based structures. We assign these species to n = 1, 2, 3, 4, and 5 quasi-two-dimensional network (2DN) sheets, in which CH3COO- anions and Br- anions compete for the c-axis X' sites separating haloplumbate(II) layers within the A'2An-1PbnBr3n-1X'2 NCs. Finally, we demonstrate the degree of CH3COO- incorporation, and thus the 2DN layer thickness and PL energy, is controlled in the early reaction times by kinetic factors. After a longer time (3 h), thermodynamic forces dictated by Le Chatelier's principle tune the structure in A'2An-1PbnBr3n-1X'2 NCs from exclusively n = 1 to n = 8 depending on the PbBr2/ABr/CH3COOH ratio.« less

High-efficiency hybrid solar cells based on polymer/PbSx Se1-x nanocrystals benefiting from vertical phase segregation.

PubMed

Liu, Zeke; Sun, Yaxiang; Yuan, Jianyu; Wei, Huaixin; Huang, Xiaodong; Han, Lu; Wang, Weiwei; Wang, Haiqiao; Ma, Wanli

2013-10-25

Solution-processed hybrid solar cells employing a low band-gap polymer and PbSx Se1-x alloy nanocrystals, achieving a record high PCE of 5.50% and an optimal FF of 67% are presented. The remarkable device efficiency can be attributed to the high-performance active materials, the optimal polymer/NCs ratio and, more importantly, the vertical donor/(donor:acceptor)/acceptor structure which benefits charge dissociation and transport. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electron energy-loss spectroscopy of single nanocrystals: mapping of tin allotropes.

PubMed

Roesgaard, Søren; Ramasse, Quentin; Chevallier, Jacques; Fyhn, Mogens; Julsgaard, Brian

2018-05-25

Using monochromated electron energy-loss spectroscopy (EELS), we are able to map different allotropes in Sn-nanocrystals embedded in Si. It is demonstrated that α-Sn and β-Sn, as well as an interface related plasmon, can be distinguished in embedded Sn-nanostructures. The EELS data is interpreted by standard non-negative matrix factorization followed by a manual Lorentzian decomposition. The decomposition allows for a more physical understanding of the EELS mapping without reducing the level of information. Extending the analysis from a reference system to smaller nanocrystals demonstrates that allotrope determination in nanoscale systems down below 5 nm is possible. Such local information proves the use of monochromated EELS mapping as a powerful technique to study nanoscale systems. This possibility enables investigation of small nanostructures that cannot be investigated through other means, allowing for a better understanding and thus leading to realizations that can result in nanomaterials with improved properties.

Electron energy-loss spectroscopy of single nanocrystals: mapping of tin allotropes

NASA Astrophysics Data System (ADS)

Roesgaard, Søren; Ramasse, Quentin; Chevallier, Jacques; Fyhn, Mogens; Julsgaard, Brian

2018-05-01

Using monochromated electron energy-loss spectroscopy (EELS), we are able to map different allotropes in Sn-nanocrystals embedded in Si. It is demonstrated that α-Sn and β-Sn, as well as an interface related plasmon, can be distinguished in embedded Sn-nanostructures. The EELS data is interpreted by standard non-negative matrix factorization followed by a manual Lorentzian decomposition. The decomposition allows for a more physical understanding of the EELS mapping without reducing the level of information. Extending the analysis from a reference system to smaller nanocrystals demonstrates that allotrope determination in nanoscale systems down below 5 nm is possible. Such local information proves the use of monochromated EELS mapping as a powerful technique to study nanoscale systems. This possibility enables investigation of small nanostructures that cannot be investigated through other means, allowing for a better understanding and thus leading to realizations that can result in nanomaterials with improved properties.

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

Interplay between Surface Chemistry, Precursor Reactivity, and Temperature Determines Outcome of ZnS Shelling Reactions on CuInS2 Nanocrystals

PubMed Central

2018-01-01

ZnS shelling of I–III–VI2 nanocrystals (NCs) invariably leads to blue-shifts in both the absorption and photoluminescence spectra. These observations imply that the outcome of ZnS shelling reactions on I–III–VI2 colloidal NCs results from a complex interplay between several processes taking place in solution, at the surface of, and within the seed NC. However, a fundamental understanding of the factors determining the balance between these different processes is still lacking. In this work, we address this need by investigating the impact of precursor reactivity, reaction temperature, and surface chemistry (due to the washing procedure) on the outcome of ZnS shelling reactions on CuInS2 NCs using a seeded growth approach. We demonstrate that low reaction temperatures (150 °C) favor etching, cation exchange, and alloying regardless of the precursors used. Heteroepitaxial shell overgrowth becomes the dominant process only if reactive S- and Zn-precursors (S-ODE/OLAM and ZnI2) and high reaction temperatures (210 °C) are used, although a certain degree of heterointerfacial alloying still occurs. Remarkably, the presence of residual acetate at the surface of CIS seed NCs washed with ethanol is shown to facilitate heteroepitaxial shell overgrowth, yielding for the first time CIS/ZnS core/shell NCs displaying red-shifted absorption spectra, in agreement with the spectral shifts expected for a type-I band alignment. The insights provided by this work pave the way toward the design of improved synthesis strategies to CIS/ZnS core/shell and alloy NCs with tailored elemental distribution profiles, allowing precise tuning of the optoelectronic properties of the resulting materials. PMID:29657360

Emerging Hierarchical Aerogels: Self-Assembly of Metal and Semiconductor Nanocrystals.

PubMed

Cai, Bin; Sayevich, Vladimir; Gaponik, Nikolai; Eychmüller, Alexander

2018-06-19

Aerogels assembled from colloidal metal or semiconductor nanocrystals (NCs) feature large surface area, ultralow density, and high porosity, thus rendering them attractive in various applications, such as catalysis, sensors, energy storage, and electronic devices. Morphological and structural modification of the aerogel backbones while maintaining the aerogel properties enables a second stage of the aerogel research, which is defined as hierarchical aerogels. Different from the conventional aerogels with nanowire-like backbones, those hierarchical aerogels are generally comprised of at least two levels of architectures, i.e., an interconnected porous structure on the macroscale and a specially designed configuration at local backbones at the nanoscale. This combination "locks in" the inherent properties of the NCs, so that the beneficial genes obtained by nanoengineering are retained in the resulting monolithic hierarchical aerogels. Herein, groundbreaking advances in the design, synthesis, and physicochemical properties of the hierarchical aerogels are reviewed and organized in three sections: i) pure metallic hierarchical aerogels, ii) semiconductor hierarchical aerogels, and iii) metal/semiconductor hybrid hierarchical aerogels. This report aims to define and demonstrate the concept, potential, and challenges of the hierarchical aerogels, thereby providing a perspective on the further development of these materials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Colloidal GdVO4:Eu3+@SiO2 nanocrystals for highly selective and sensitive detection of Cu2+ ions

NASA Astrophysics Data System (ADS)

Liang, Yanjie; Noh, Hyeon Mi; Park, Sung Heum; Choi, Byung Chun; Jeong, Jung Hyun

2018-03-01

Nowadays, in view of health and safety demands, the controlled design of selective and sensitive sensors for Cu2+ detection is of considerable importance. Therefore, we construct herein core-shell colloidal GdVO4:Eu3+@SiO2 nanocrystals (NCs) as optical sensor for the detection of Cu2+, which were synthesized by a facile hydrothermal reaction and encapsulated with a uniform layer of ultrathin silica through a sol-gel strategy. The NCs present strong red emission due to energy transfer from VO43- groups to Eu3+ when exciting with ultraviolet (UV) light. This intense red emission from Eu3+ could be selectively quenched in the presence of Cu2+ in comparison to other metal ions and the limit of detection is as low as 80 nM in aqueous solution. It is revealed that the spectral overlap between the emission band of NCs and the absorption of Cu2+ accounts for this intriguing luminescence behavior. The detection ability is highly reversible by the addition of ethylenediaminetetraacetic acid (EDTA) with the recovery of almost 100% of the original luminescence. The luminescence quenching and recovery processes can be performed repeatedly with good sensing ability. These remarkable performances allow the colloidal GdVO4:Eu3+@SiO2 NCs a promising fluorescence chemosensor for detecting Cu2+ ions in aqueous solution.

First-principles real-space study of electronic and optical excitations in rutile TiO 2 nanocrystals

DOE PAGES

Hung, Linda; Baishya, Kopinjol; Öğüt, Serdar

2014-10-17

We model rutile titanium dioxide nanocrystals (NCs) up to ~1.5 nm in size to study the effects of quantum confinement on their electronic and optical properties. Ionization potentials (IPs) and electron affinities (EAs) are obtained via the perturbative GW approximation (G 0W 0) and ΔSCF method for NCs up to 24 and 64 TiO 2 formula units, respectively. These demanding GW computations are made feasible by using a real-space framework that exploits quantum confinement to reduce the number of empty states needed in GW summations. Time-dependent density functional theory (TDDFT) is used to predict the optical properties of NCs upmore » to 64 TiO 2 units. For a NC containing only 2 TiO 2 units, the offsets of the IP and the EA from the corresponding bulk limits are of similar magnitude. However, as NC size increases, the EA is found to converge more slowly to the bulk limit than the IP. The EA values computed at the G 0W 0 and ΔSCF levels of theory are found to agree fairly well with each other, while the IPs computed with ΔSCF are consistently smaller than those computed with G 0W 0 by a roughly constant amount. TDDFT optical gaps exhibit weaker size dependence than GW quasiparticle gaps, and result in exciton binding energies on the order of eV. Finally, altering the dimensions of a fixed-size NC can change electronic and optical excitations up to several tenths of an eV. The largest NCs modeled are still quantum confined and do not yet have quasiparticle levels or optical gaps at bulk values. Nevertheless, we find that classical Mie-Gans theory can quite accurately reproduce the line shape of TDDFT absorption spectra, even for (anisotropic) TiO 2 NCs of subnanometer size.« less

First-principles real-space study of electronic and optical excitations in rutile TiO2 nanocrystals

NASA Astrophysics Data System (ADS)

Hung, Linda; Baishya, Kopinjol; Ã-ǧüt, Serdar

2014-10-01

We model rutile titanium dioxide nanocrystals (NCs) up to ˜1.5 nm in size to study the effects of quantum confinement on their electronic and optical properties. Ionization potentials (IPs) and electron affinities (EAs) are obtained via the perturbative GW approximation (G0W0) and ΔSCF method for NCs up to 24 and 64 TiO2 formula units, respectively. These demanding GW computations are made feasible by using a real-space framework that exploits quantum confinement to reduce the number of empty states needed in GW summations. Time-dependent density functional theory (TDDFT) is used to predict the optical properties of NCs up to 64 TiO2 units. For a NC containing only 2 TiO2 units, the offsets of the IP and the EA from the corresponding bulk limits are of similar magnitude. However, as NC size increases, the EA is found to converge more slowly to the bulk limit than the IP. The EA values computed at the G0W0 and ΔSCF levels of theory are found to agree fairly well with each other, while the IPs computed with ΔSCF are consistently smaller than those computed with G0W0 by a roughly constant amount. TDDFT optical gaps exhibit weaker size dependence than GW quasiparticle gaps, and result in exciton binding energies on the order of eV. Altering the dimensions of a fixed-size NC can change electronic and optical excitations up to several tenths of an eV. The largest NCs modeled are still quantum confined and do not yet have quasiparticle levels or optical gaps at bulk values. Nevertheless, we find that classical Mie-Gans theory can quite accurately reproduce the line shape of TDDFT absorption spectra, even for (anisotropic) TiO2 NCs of subnanometer size.

Relevance of LiPF6 as Etching Agent of LiMnPO4 Colloidal Nanocrystals for High Rate Performing Li-ion Battery Cathodes.

PubMed

Chen, Lin; Dilena, Enrico; Paolella, Andrea; Bertoni, Giovanni; Ansaldo, Alberto; Colombo, Massimo; Marras, Sergio; Scrosati, Bruno; Manna, Liberato; Monaco, Simone

2016-02-17

LiMnPO4 is an attractive cathode material for the next-generation high power Li-ion batteries, due to its high theoretical specific capacity (170 mA h g(-1)) and working voltage (4.1 V vs Li(+)/Li). However, two main drawbacks prevent the practical use of LiMnPO4: its low electronic conductivity and the limited lithium diffusion rate, which are responsible for the poor rate capability of the cathode. The electronic resistance is usually lowered by coating the particles with carbon, while the use of nanosize particles can alleviate the issues associated with poor ionic conductivity. It is therefore of primary importance to develop a synthetic route to LiMnPO4 nanocrystals (NCs) with controlled size and coated with a highly conductive carbon layer. We report here an effective surface etching process (using LiPF6) on colloidally synthesized LiMnPO4 NCs that makes the NCs dispersible in the aqueous glucose solution used as carbon source for the carbon coating step. Also, it is likely that the improved exposure of the NC surface to glucose facilitates the formation of a conductive carbon layer that is in intimate contact with the inorganic core, resulting in a high electronic conductivity of the electrode, as observed by us. The carbon coated etched LiMnPO4-based electrode exhibited a specific capacity of 118 mA h g(-1) at 1C, with a stable cycling performance and a capacity retention of 92% after 120 cycles at different C-rates. The delivered capacities were higher than those of electrodes based on not etched carbon coated NCs, which never exceeded 30 mA h g(-1). The rate capability here reported for the carbon coated etched LiMnPO4 nanocrystals represents an important result, taking into account that in the electrode formulation 80% wt is made of the active material and the adopted charge protocol is based on reasonable fast charge times.

Numerical simulation of capacitively coupled RF plasma flowing through a tube for the synthesis of silicon nanocrystals

NASA Astrophysics Data System (ADS)

Le Picard, Romain; Song, Sang-Heon; Porter, David; Kushner, Mark; Girshick, Steven

2014-10-01

Silicon nanocrystals (SiNCs) are of interest for applications in the photonics, electronics, and biomedical areas. Nonthermal plasmas offer several potential advantages for synthesizing SiNCs. In this work, we have developed a numerical model of a capacitively coupled RF plasma used for the synthesis of SiNCs. The plasma, consisting of silane diluted in argon at a total pressure of about 2 Torr, flows through a narrow quartz tube with two ring electrodes. The numerical model is 2D, assuming axisymmetry. An aerosol sectional model is added to the Hybrid Plasma Equipment Model developed by Kushner and coworkers. The aerosol module solves for aerosol size distributions and size-dependent charge distributions. A detailed chemical kinetic mechanism considering silicon hydride species containing up to 5 Si atoms is used to model particle nucleation and surface growth. The sectional model calculates coagulation, particle transport by electric force, neutral drag and ion drag, and particle charging using orbital motion limited theory. Simulation results are presented for selected operating conditions, and are compared to experimental results. This work was partially supported by the US Dept. of Energy Office of Fusion Energy Science (DE-SC0001939), the US National Science Foundation (CHE-124752), and the Minnesota Supercomputing Institute.

Aqueous-Processed Inorganic Thin-Film Solar Cells Based on CdSe(x)Te(1-x) Nanocrystals: The Impact of Composition on Photovoltaic Performance.

PubMed

Zeng, Qingsen; Chen, Zhaolai; Zhao, Yue; Du, Xiaohang; Liu, Fangyuan; Jin, Gan; Dong, Fengxia; Zhang, Hao; Yang, Bai

2015-10-21

Aqueous processed nanocrystal (NC) solar cells are attractive due to their environmental friendliness and cost effectiveness. Controlling the bandgap of absorbing layers is critical for achieving high efficiency for single and multijunction solar cells. Herein, we tune the bandgap of CdTe through the incorporation of Se via aqueous process. The photovoltaic performance of aqueous CdSexTe1-x NCs is systematically investigated, and the impacts of charge generation, transport, and injection on device performance for different compositions are deeply discussed. We discover that the performance degrades with the increasing Se content from CdTe to CdSe. This is mainly ascribed to the lower conduction band (CB) of CdSexTe1-x with higher Se content, which reduces the driving force for electron injection into TiO2. Finally, the performance is improved by mixing CdSexTe1-x NCs with conjugated polymer poly(p-phenylenevinylene) (PPV), and power conversion efficiency (PCE) of 3.35% is achieved based on ternary NCs. This work may provide some information to further optimize the aqueous-processed NC and hybrid solar cells.

Doped and codoped silicon nanocrystals: The role of surfaces and interfaces

NASA Astrophysics Data System (ADS)

Marri, Ivan; Degoli, Elena; Ossicini, Stefano

2017-12-01

Si nanocrystals have been extensively studied because of their novel properties and their potential applications in electronic, optoelectronic, photovoltaic, thermoelectric and biological devices. These new properties are achieved through the combination of the quantum confinement of carriers and the strong influence of surface chemistry. As in the case of bulk Si the tuning of the electronic, optical and transport properties is related to the possibility of doping, in a controlled way, the nanocrystals. This is a big challenge since several studies have revealed that doping in Si nanocrystals differs from the one of the bulk. Theory and experiments have underlined that doping and codoping are influenced by a large number of parameters such as size, shape, passivation and chemical environment of the silicon nanocrystals. However, the connection between these parameters and dopant localization as well as the occurrence of self-purification effects are still not clear. In this review we summarize the latest progress in this fascinating research field considering free-standing and matrix-embedded Si nanocrystals both from the theoretical and experimental point of view, with special attention given to the results obtained by ab-initio calculations and to size-, surface- and interface-induced effects.

Fundamental studies of chalcogenide nanocrystals, carbonaceous nanoparticles, and chromatographic materials

NASA Astrophysics Data System (ADS)

Baker, Jared Scott

2011-12-01

electrophoretic mobilities under a wide range of pH values. The mobility of these nanoparticles as a function of ionic strength was compared to classical electrokinetic theory, suggesting that the species are small, highly charged particles with appreciable zeta potentials, even at low pH. In an attempt to reduce the complexity of the CNP solution, two molecular-weight based fractionation techniques were employed and evaluated. Traditional dialysis and ultracentrifugation filtration techniques were modified to generate multiple CNPs fractions based on size. Analysis of the fractions by absorption and photoluminescence spectroscopy as well as CE revealed specific characteristics for a given sized-fraction. Namely, a strong correlation between the size of the CNPs and their luminescent emission was observed. CE was utilized to characterize each fraction and to ultimately judge the effectiveness of the fractionation techniques. The characterization of the persistence and degradation of magic-sized CdSe nanocrystals (NCs) after their removal from the original reaction mixture and dispersion into basic aqueous solutions was performed by absorption spectroscopy. NCs degraded after dilution into aqueous NaOH, resulting in red-shifted excitonic absorption bands and eventual flocculation. Dilution of NCs into basic aqueous solutions of cysteinate resulted in degradation via a different mechanism with an absence of flocculation; kinetics varied with concentration of cysteinate. The chemical fate of NCs after dilution into basic aqueous solutions containing both Cd2+ and cysteinate varied with the cysteinate-to-Cd 2+ molar ratio, which determined the relative solute mole fractions of various Cd2+-cysteinate complexes. CdSe NCs persisted on long timescales only when dispersed in solutions containing [Cd(cysteinate) 3]4-. Equilibria are presented to account for the observed spectral changes after dilution of CdSe into various basic media. Cadmium(II)-cysteinate complex-formation equilibria

Matrix-assisted relaxation in Fe(phen)2(NCS)2 spin-crossover microparticles, experimental and theoretical investigations

NASA Astrophysics Data System (ADS)

Enachescu, Cristian; Tanasa, Radu; Stancu, Alexandru; Tissot, Antoine; Laisney, Jérôme; Boillot, Marie-Laure

2016-07-01

In this study, we present the influence of the embedding matrix on the relaxation of Fe(phen)2(NCS)2 (phen = 1,10-phenanthroline) spin-transition microparticles as revealed by experiments and provide an explanation within the framework of an elastic model based on a Monte-Carlo method. Experiments show that the shape of the high-spin → low-spin relaxation curves is drastically changed when the particles are dispersed in glycerol. This effect was considered in the model by means of interactions between the microparticles and the matrix. A faster start of the relaxation for microparticles embedded in glycerol is due to an initial positive local pressure acting on the edge spin-crossover molecules from the matrix side. This local pressure diminishes and eventually becomes negative during relaxation, as an effect of the decrease of the volume of spin-crossover microparticles from high-spin to low-spin.

Static and Dynamical Structural Investigations of Metal-Oxide Nanocrystals by Powder X-ray Diffraction: Colloidal Tungsten Oxide as a Case Study

DOE PAGES

Caliandro, Rocco; Sibillano, Teresa; Belviso, B. Danilo; ...

2016-02-02

In this study, we have developed a general X-ray powder diffraction (XPD) methodology for the simultaneous structural and compositional characterization of inorganic nanomaterials. The approach is validated on colloidal tungsten oxide nanocrystals (WO 3-x NCs), as a model polymorphic nanoscale material system. Rod-shaped WO 3-x NCs with different crystal structure and stoichiometry are comparatively investigated under an inert atmosphere and after prolonged air exposure. An initial structural model for the as-synthesized NCs is preliminarily identified by means of Rietveld analysis against several reference crystal phases, followed by atomic pair distribution function (PDF) refinement of the best-matching candidates (static analysis). Subtlemore » stoichiometry deviations from the corresponding bulk standards are revealed. NCs exposed to air at room temperature are monitored by XPD measurements at scheduled time intervals. The static PDF analysis is complemented with an investigation into the evolution of the WO 3-x NC structure, performed by applying the modulation enhanced diffraction technique to the whole time series of XPD profiles (dynamical analysis). Prolonged contact with ambient air is found to cause an appreciable increase in the static disorder of the O atoms in the WO 3-x NC lattice, rather than a variation in stoichiometry. Finally, the time behavior of such structural change is identified on the basis of multivariate analysis.« less

Interference-enhanced infrared-to-visible upconversion in solid-state thin films sensitized by colloidal nanocrystals

NASA Astrophysics Data System (ADS)

Wu, Mengfei; Jean, Joel; Bulović, Vladimir; Baldo, Marc A.

2017-05-01

Infrared-to-visible photon upconversion has potential applications in photovoltaics, sensing, and bioimaging. We demonstrate a solid-state thin-film device that utilizes sensitized triplet-triplet exciton annihilation, converting infrared photons absorbed by colloidal lead sulfide nanocrystals (NCs) into visible photons emitted from a luminescent dopant in rubrene at low incident light intensities. A typical bilayer device consisting of a monolayer of NCs and a doped film of rubrene is limited by low infrared absorption in the thin NC film. Here, we augment the bilayer with an optical spacer layer and a silver-film back reflector, resulting in interference effects that enhance the optical field and thus the absorption in the NC film. The interference-enhanced device shows an order-of-magnitude increase in the upconverted emission at the wavelength of λ = 610 nm when excited at λ = 980 nm. At incident light intensities above 1.1 W/cm2, the device attains maximum efficiency, converting (1.6 ± 0.2)% of absorbed infrared photons into higher-energy singlet excitons in rubrene.

Highly Efficient Visible Colloidal Lead-Halide Perovskite Nanocrystal Light-Emitting Diodes

NASA Astrophysics Data System (ADS)

Yan, Fei; Xing, Jun; Xing, Guichuan; Quan, Lina; Tan, Swee Tiam; Zhao, Jiaxin; Su, Rui; Zhang, Lulu; Chen, Shi; Zhao, Yawen; Huan, Alfred; Sargent, Edward H.; Xiong, Qihua; Demir, Hilmi Volkan

2018-05-01

Lead-halide perovskites have been attracting attention for potential use in solid-state lighting. Following the footsteps of solar cells, the field of perovskite light-emitting diodes (PeLEDs) has been growing rapidly. Their application prospects in lighting, however, remain still uncertain due to a variety of shortcomings in device performance including their limited levels of luminous efficiency achievable thus far. Here we show high-efficiency PeLEDs based on colloidal perovskite nanocrystals (PeNCs) synthesized at room temperature possessing dominant first-order excitonic radiation (enabling a photoluminescence quantum yield of 71% in solid film), unlike in the case of bulk perovskites with slow electron-hole bimolecular radiative recombination (a second-order process). In these PeLEDs, by reaching charge balance in the recombination zone, we find that the Auger nonradiative recombination, with its significant role in emission quenching, is effectively suppressed in low driving current density range. In consequence, these devices reach a record high maximum external quantum efficiency of 12.9% reported to date and an unprecedentedly high power efficiency of 30.3 lm W-1 at luminance levels above 1000 cd m-2 as required for various applications. These findings suggest that, with feasible levels of device performance, the PeNCs hold great promise for their use in LED lighting and displays.

CdS/ZnS core-shell nanocrystal photosensitizers for visible to UV upconversion.

PubMed

Gray, Victor; Xia, Pan; Huang, Zhiyuan; Moses, Emily; Fast, Alexander; Fishman, Dmitry A; Vullev, Valentine I; Abrahamsson, Maria; Moth-Poulsen, Kasper; Lee Tang, Ming

2017-08-01

Herein we report the first example of nanocrystal (NC) sensitized triplet-triplet annihilation based photon upconversion from the visible to ultraviolet (vis-to-UV). Many photocatalyzed reactions, such as water splitting, require UV photons in order to function efficiently. Upconversion is one possible means of extending the usable range of photons into the visible. Vis-to-UV upconversion is achieved with CdS/ZnS core-shell NCs as the sensitizer and 2,5-diphenyloxazole (PPO) as annihilator and emitter. The ZnS shell was crucial in order to achieve any appreciable upconversion. From time resolved photoluminescence and transient absorption measurements we conclude that the ZnS shell affects the NC and triplet energy transfer (TET) from NC to PPO in two distinct ways. Upon ZnS growth the surface traps are passivated thus increasing the TET. The shell, however, also acts as a tunneling barrier for TET, reducing the efficiency. This leads to an optimal shell thickness where the upconversion quantum yield ( Φ ' UC ) is maximized. Here the maximum Φ ' UC was determined to be 5.2 ± 0.5% for 4 monolayers of ZnS shell on CdS NCs.

Enhancing Docetaxel Delivery to Multidrug-Resistant Cancer Cells with Albumin-Coated Nanocrystals.

PubMed

Gad, Sheryhan F; Park, Joonyoung; Park, Ji Eun; Fetih, Gihan N; Tous, Sozan S; Lee, Wooin; Yeo, Yoon

2018-01-29

Intravenous delivery of poorly water-soluble anticancer drugs such as docetaxel (DTX) is challenging due to the low bioavailability and the toxicity related to solubilizing excipients. Colloidal nanoparticles are used as alternative carriers, but low drug loading capacity and circulation instability limit their clinical translation. To address these challenges, DTX nanocrystals (NCs) were prepared using Pluronic F127 as an intermediate stabilizer and albumin as a functional surface modifier, which were previously found to be effective in producing small and stable NCs. We hypothesize that the albumin-coated DTX NCs (DTX-F-alb) will remain stable in serum-containing medium so as to effectively leverage the enhanced permeability and retention effect. In addition, the surface-bound albumin, in its native form, may contribute to cellular transport of NCs through interactions with albumin-binding proteins such as secreted protein acidic and rich in cysteine (SPARC). DTX-F-alb NCs showed sheet-like structure with an average length, width, and thickness of 284 ± 96, 173 ± 56, and 40 ± 8 nm and remained stable in 50% serum solution at a concentration greater than 10 μg/mL. Cytotoxicity and cellular uptake of DTX-F-alb and unformulated (free) DTX were compared on three cell lines with different levels of SPARC expression and DTX sensitivity. While the uptake of free DTX was highly dependent on DTX sensitivity, DTX-F-alb treatment resulted in relatively consistent cellular levels of DTX. Free DTX was more efficient in entering drug-sensitive B16F10 and SKOV-3 cells than DTX-F-alb, with consistent cytotoxic effects. In contrast, multidrug-resistant NCI/ADR-RES cells took up DTX-F-alb more than free DTX with time and responded better to the former. This difference was reduced by SPARC knockdown. The high SPARC expression level of NCI/ADR-RES cells, the known affinity of albumin for SPARC, and the opposing effect of SPARC knockdown support that DTX-F-alb have exploited the

Surface structure, optoelectronic properties and charge transport in ZnO nanocrystal/MDMO-PPV multilayer films.

PubMed

Lian, Qing; Chen, Mu; Mokhtar, Muhamad Z; Wu, Shanglin; Zhu, Mingning; Whittaker, Eric; O'Brien, Paul; Saunders, Brian R

2018-05-07

Blends of semiconducting nanocrystals and conjugated polymers continue to attract major research interest because of their potential applications in optoelectronic devices, such as solar cells, photodetectors and light-emitting diodes. In this study we investigate the surface structure, morphological and optoelectronic properties of multilayer films constructed from ZnO nanocrystals (NCs) and poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV). The effects of layer number and ZnO concentration (C ZnO ) used on the multilayer film properties are investigated. An optimised solvent blend enabled well-controlled layers to be sequentially spin coated and the construction of multilayer films containing six ZnO NC (Z) and MDMO-PPV (M) layers (denoted as (ZM) 6 ). Contact angle data showed a strong dependence on C ZnO and indicated distinct differences in the coverage of MDMO-PPV by the ZnO NCs. UV-visible spectroscopy showed that the MDMO-PPV absorption increased linearly with the number of layers in the films and demonstrates highly tuneable light absorption. Photoluminescence spectra showed reversible quenching as well as a surprising red-shift of the MDMO-PPV emission peak. Solar cells were constructed to probe vertical photo-generated charge transport. The measurements showed that (ZM) 6 devices prepared using C ZnO = 14.0 mg mL -1 had a remarkably high open circuit voltage of ∼800 mV. The device power conversion efficiency was similar to that of a control bilayer device prepared using a much thicker MDMO-PPV layer. The results of this study provide insight into the structure-optoelectronic property relationships of new semiconducting multilayer films which should also apply to other semiconducting NC/polymer combinations.

Albendazole nanocrystals in experimental alveolar echinococcosis: Enhanced chemoprophylactic and clinical efficacy in infected mice.

PubMed

Pensel, Patricia; Paredes, Alejandro; Albani, Clara M; Allemandi, Daniel; Sanchez Bruni, Sergio; Palma, Santiago D; Elissondo, María C

2018-02-15

Human alveolar echinococcosis is caused by the fox tapeworm Echinococcus multilocularis and is usually fatal if left untreated. Medical treatment with albendazole (ABZ) remains an effective option. However, due to its low aqueous solubility, ABZ is poorly and erratically absorbed following oral administration resulting in low drug levels in plasma and liver distribution. Thus, there arises the need to find a simple, efficient and scalable method to produce new ABZ formulations with increased bioavailability. Bearing this in mind, ABZ nanocrystals (ABZ-NCs) appears to be a useful tool to achieve this goal. The aim of the current study was to investigate the chemoprophylactic and clinical efficacy of an ABZ-NC formulation on mice infected with E. multilocularis. In the chemoprophylactic efficacy study, mean weight of the cysts recovered from the ABZ-NC group was 50% lower than that recorded from untreated mice, whereas the treatment with ABZ suspension did not show preventive effect. The viability of protoscoleces isolated from ABZ-NC treated mice was significantly lower than control groups. In the clinical efficacy studies, both ABZ formulations resulted in a reduction in the mean weight of the cysts obtained from mice, however only the treatment with the nanosuspension revealed significant differences (P < 0.05) compared to the control groups. Treatment with ABZ-NCs reduced the weight of the cysts by 77% and the viability of their protoscoleces to 34%. All these results coincided with the tissue damage determined at the ultrastructural level. The enhanced chemoprophylactic and clinical efficacy of ABZ-NCs observed in this study could be attributed to an increase in the oral bioavailability of the drug. In a next step, we will characterize the cyst concentration profile after the administration of ABZ-NCs in mice infected with E. multilocularis. Copyright © 2017 Elsevier B.V. All rights reserved.

Combining ligand-induced quantum-confined stark effect with type II heterojunction bilayer structure in CdTe and CdSe nanocrystal-based solar cells.

PubMed

Yaacobi-Gross, Nir; Garphunkin, Natalia; Solomeshch, Olga; Vaneski, Aleksandar; Susha, Andrei S; Rogach, Andrey L; Tessler, Nir

2012-04-24

We show that it is possible to combine several charge generation strategies in a single device structure, the performance of which benefits from all methods used. Exploiting the inherent type II heterojunction between layered structures of CdSe and CdTe colloidal quantum dots, we systematically study different ways of combining such nanocrystals of different size and surface chemistry and with different linking agents in a bilayer solar cell configuration. We demonstrate the beneficial use of two distinctly different sizes of NCs not only to improve the solar spectrum matching but also to reduce exciton binding energy, allowing their efficient dissociation at the interface. We further make use of the ligand-induced quantum-confined Stark effect in order to enhance charge generation and, hence, overall efficiency of nanocrystal-based solar cells.

Highly Efficient Flexible Quantum Dot Solar Cells with Improved Electron Extraction Using MgZnO Nanocrystals.

PubMed

Zhang, Xiaoliang; Santra, Pralay Kanti; Tian, Lei; Johansson, Malin B; Rensmo, Håkan; Johansson, Erik M J

2017-08-22

Colloidal quantum dot (CQD) solar cells have high potential for realizing an efficient and lightweight energy supply for flexible or wearable electronic devices. To achieve highly efficient and flexible CQD solar cells, the electron transport layer (ETL), extracting electrons from the CQD solid layer, needs to be processed at a low-temperature and should also suppress interfacial recombination. Herein, a highly stable MgZnO nanocrystal (MZO-NC) layer is reported for efficient flexible PbS CQD solar cells. Solar cells fabricated with MZO-NC ETL give a high power conversion efficiency (PCE) of 10.4% and 9.4%, on glass and flexible plastic substrates, respectively. The reported flexible CQD solar cell has the record efficiency to date of flexible CQD solar cells. Detailed theoretical simulations and extensive characterizations reveal that the MZO-NCs significantly enhance charge extraction from CQD solids and diminish the charge accumulation at the ETL/CQD interface, suppressing charge interfacial recombination. These important results suggest that the low-temperature processed MZO-NCs are very promising for use in efficient flexible solar cells or other flexible optoelectronic devices.

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

Nanocrystal structures

DOEpatents

Eisler, Hans J [Stoneham, MA; Sundar, Vikram C [Stoneham, MA; Walsh, Michael E [Everett, MA; Klimov, Victor I [Los Alamos, NM; Bawendi, Moungi G [Cambridge, MA; Smith, Henry I [Sudbury, MA

2008-12-30

A structure including a grating and a semiconductor nanocrystal layer on the grating, can be a laser. The semiconductor nanocrystal layer can include a plurality of semiconductor nanocrystals including a Group II-VI compound, the nanocrystals being distributed in a metal oxide matrix. The grating can have a periodicity from 200 nm to 500 nm.

Nanocrystal structures

DOEpatents

Eisler, Hans J.; Sundar, Vikram C.; Walsh, Michael E.; Klimov, Victor I.; Bawendi, Moungi G.; Smith, Henry I.

2006-12-19

A structure including a grating and a semiconductor nanocrystal layer on the grating, can be a laser. The semiconductor nanocrystal layer can include a plurality of semiconductor nanocrystals including a Group II–VI compound, the nanocrystals being distributed in a metal oxide matrix. The grating can have a periodicity from 200 nm to 500 nm.

Si Nanocrystal-Embedded SiO x nanofoils: Two-Dimensional Nanotechnology-Enabled High Performance Li Storage Materials.

PubMed

Yoo, Hyundong; Park, Eunjun; Bae, Juhye; Lee, Jaewoo; Chung, Dong Jae; Jo, Yong Nam; Park, Min-Sik; Kim, Jung Ho; Dou, Shi Xue; Kim, Young-Jun; Kim, Hansu

2018-05-02

Silicon (Si) based materials are highly desirable to replace currently used graphite anode for lithium ion batteries. Nevertheless, its usage is still a big challenge due to poor battery performance and scale-up issue. In addition, two-dimensional (2D) architectures, which remain unresolved so far, would give them more interesting and unexpected properties. Herein, we report a facile, cost-effective, and scalable approach to synthesize Si nanocrystals embedded 2D SiO x nanofoils for next-generation lithium ion batteries through a solution-evaporation-induced interfacial sol-gel reaction of hydrogen silsesquioxane (HSiO 1.5 , HSQ). The unique nature of the thus-prepared centimeter scale 2D nanofoil with a large surface area enables ultrafast Li + insertion and extraction, with a reversible capacity of more than 650 mAh g -1 , even at a high current density of 50 C (50 A g -1 ). Moreover, the 2D nanostructured Si/SiO x nanofoils show excellent cycling performance up to 200 cycles and maintain their initial dimensional stability. This superior performance stems from the peculiar nanoarchitecture of 2D Si/SiO x nanofoils, which provides short diffusion paths for lithium ions and abundant free space to effectively accommodate the huge volume changes of Si during cycling.

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.

47 CFR 216.1 - NCS Directives.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 47 Telecommunication 5 2013-10-01 2013-10-01 false NCS Directives. 216.1 Section 216.1 Telecommunication OFFICE OF SCIENCE AND TECHNOLOGY POLICY AND NATIONAL SECURITY COUNCIL NATIONAL COMMUNICATIONS... Directives, which establish and implement organizational responsibilities, authorities, policies and...

47 CFR 216.1 - NCS Directives.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 47 Telecommunication 5 2011-10-01 2011-10-01 false NCS Directives. 216.1 Section 216.1 Telecommunication OFFICE OF SCIENCE AND TECHNOLOGY POLICY AND NATIONAL SECURITY COUNCIL NATIONAL COMMUNICATIONS... Directives, which establish and implement organizational responsibilities, authorities, policies and...

47 CFR 216.1 - NCS Directives.

Code of Federal Regulations, 2012 CFR

2012-10-01

... 47 Telecommunication 5 2012-10-01 2012-10-01 false NCS Directives. 216.1 Section 216.1 Telecommunication OFFICE OF SCIENCE AND TECHNOLOGY POLICY AND NATIONAL SECURITY COUNCIL NATIONAL COMMUNICATIONS... Directives, which establish and implement organizational responsibilities, authorities, policies and...

47 CFR 216.1 - NCS Directives.

Code of Federal Regulations, 2014 CFR

2014-10-01

... 47 Telecommunication 5 2014-10-01 2014-10-01 false NCS Directives. 216.1 Section 216.1 Telecommunication OFFICE OF SCIENCE AND TECHNOLOGY POLICY AND NATIONAL SECURITY COUNCIL NATIONAL COMMUNICATIONS... Directives, which establish and implement organizational responsibilities, authorities, policies and...

47 CFR 216.1 - NCS Directives.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 47 Telecommunication 5 2010-10-01 2010-10-01 false NCS Directives. 216.1 Section 216.1 Telecommunication OFFICE OF SCIENCE AND TECHNOLOGY POLICY AND NATIONAL SECURITY COUNCIL NATIONAL COMMUNICATIONS... Directives, which establish and implement organizational responsibilities, authorities, policies and...

High Br- Content CsPb(Cl yBr1- y)3 Perovskite Nanocrystals with Strong Mn2+ Emission through Diverse Cation/Anion Exchange Engineering.

PubMed

Li, Fei; Xia, Zhiguo; Pan, Caofeng; Gong, Yue; Gu, Lin; Liu, Quanlin; Zhang, Jin Z

2018-04-11

The unification of tunable band edge (BE) emission and strong Mn 2+ doping luminescence in all-inorganic cesium lead halide perovskite nanocrystals (NCs) CsPbX 3 (X = Cl and Br) is of fundamental importance in fine tuning their optical properties. Herein, we demonstrate that benefiting from the differentiation of the cation/anion exchange rate, ZnBr 2 and preformed CsPb 1- x Cl 3 : xMn 2+ NCs can be used to obtain high Br - content Cs(Pb 1- x- z Zn z )(Cl y Br 1- y ) 3 : xMn 2+ perovskite NCs with strong Mn 2+ emission, and the Mn 2+ substitution ratio can reach about 22%. More specifically, the fast anion exchange could be realized by the soluble halide precursors, leading to anion exchange within a few seconds as observed from the strong BE emission evolution, whereas the cation exchange instead generally required at least a few hours; moreover, their exchange mechanism and dynamics process have been evaluated. The Mn 2+ emission intensity could be further varied by controlling the replacement of Mn 2+ by Zn 2+ with prolonged ion exchange reaction time. White light emission of the doped perovskite NCs via this cation/anion synergistic exchange strategy has been realized, which was also successfully demonstrated in a prototype white light-emitting diode (LED) device based on a commercially available 365 nm LED chip.

The National Comorbidity Survey Adolescent Supplement (NCS-A): I. Background and Measures

PubMed Central

Merikangas, Kathleen R.; Avenevoli, Shelli; Costello, E. Jane; Koretz, Doreen; Kessler, Ronald C.

2009-01-01

Objective This paper presents an overview of the background and measures used in the National Comorbidity Survey Replication Adolescent Supplement (NCS-A). Methods The NCS-A is a national psychiatric epidemiological survey of adolescents ages 13–17. Results The NCS-A was designed to provide the first nationally representative estimates of the prevalence, correlates and patterns of service use for DSM-V mental disorders among US adolescents and to lay the groundwork for follow-up studies of risk-protective factors, consequences, and early expressions of adult mental disorders. The core NCS-A diagnostic interview, the World Health Organization (WHO) Composite International Diagnostic Interview (CIDI), is a fully-structured research diagnostic interview designed for use by trained lay interviewers. A multi-construct, multi-method, multi-informant battery was also included to assess risk and protective factors and barriers to service use. Design limitations due to the NCS-A evolving as a supplement to an ongoing survey of mental disorders of US adults include restricted age range of youth, cross-sectional assessment, and lack of full parental/surrogate informant reports on youth mental disorders and correlates. Conclusions Despite these limitations, the NCS-A contains unparalleled information that can be used to generate national estimates of prevalence and correlates of adolescent mental disorders, risk and protective factors, patterns of service use, and barriers to receiving treatment for these disorders. The retrospective NCS-A data on the development of psychopathology can additionally complement data from longitudinal studies based on more geographically restricted samples and serve as a useful baseline for future prospective studies of the onset and progression of mental disorders in adulthood. PMID:19242382

Diffraction peak profiles of surface relaxed spherical nanocrystals

NASA Astrophysics Data System (ADS)

Perez-Demydenko, C.; Scardi, P.

2017-09-01

A model is proposed for surface relaxation of spherical nanocrystals. Besides reproducing the primary effect of changing the average unit cell parameter, the model accounts for the inhomogeneous atomic displacement caused by surface relaxation and its effect on the diffraction line profiles. Based on three parameters with clear physical meanings - extension of the sub-coordination effect, maximum radial displacement due to sub-coordination, and effective hydrostatic pressure - the model also considers elastic anisotropy and provides parametric expressions of the diffraction line profiles directly applicable in data analysis. The model was tested on spherical nanocrystals of several fcc metals, matching atomic positions with those provided by Molecular Dynamics (MD) simulations based on embedded atom potentials. Agreement was also verified between powder diffraction patterns generated by the Debye scattering equation, using atomic positions from MD and the proposed model.

Optical, colloidal and biological properties of up-converting nanoparticles embedded in polyester nanocarriers

NASA Astrophysics Data System (ADS)

Wawrzyńczyk, Dominika; Kulbacka, Julita; Bazylińska, Urszula

2017-08-01

We have investigated the change in optical properties and biocompatibility of up-converting NaYF4 nanoparticles (NPs) upon encapsulation inside the polyester nanocarriers (NCs) stabilized by Crempophor RH40 (CRH40), poly(D,L-lactide) (PLA), Pluronic P123 (P123). NaYF4:Er3+,Yb3+ NPs showed intense green and red emission, and upon encapsulation the increase of red band in respect to green one was observed, with no luminescence lifetime shortening. Obtained NCs showed prolonged colloidal stability and protective effect of the polymer shell simultaneously preserving the high emission efficiency of nanoparticles embedded within the silicon oil (SO) core. Based on emission spectra, kinetic measurements and cytotoxicity studies upon human malignant melanoma Me45 cell line we have shown the advantages of using polyester NCs as containers for the up-converting NPs. Due to the possibility of co-encapsulation of photosensitizers the obtained nanocarriers showed potential for application in theranostics.

High rectifying behavior in Al/Si nanocrystal-embedded SiOxNy/p-Si heterojunctions

NASA Astrophysics Data System (ADS)

Jacques, E.; Pichon, L.; Debieu, O.; Gourbilleau, F.; Coulon, N.

2011-05-01

We examine the electrical properties of MIS devices made of Al/Si nanocrystal-SiOxNy/p-Si. The J-V characteristics of the devices present a high rectifying behavior. Temperature measurements show that the forward current is thermally activated following the thermal diffusion model of carriers. At low reverse bias, the current is governed by thermal emission amplified by the Poole-Frenkel effect of carriers from defects located at the silicon nanocrystals/SiOxNy interfaces, whereas tunnel conduction in silicon oxynitride matrix dominates at high reverse bias. The devices exhibit a rectification ratio >104 for the current measured at V = ± 1 V. Study reveals that thermal annealing in forming gas (H2/N2) improves the electrical properties of the devices due to the passivation of defects.

Surface Properties and Photocatalytic Activities of the Colloidal ZnS:Mn Nanocrystals Prepared at Various pH Conditions

PubMed Central

Heo, Jungho; Hwang, Cheong-Soo

2015-01-01

Water-dispersible ZnS:Mn nanocrystals (NC) were synthesized by capping the surface with mercaptoacetic acid (MAA) molecules at three different pH conditions. The obtained ZnS:Mn-MAA NC products were physically and optically characterized by corresponding spectroscopic methods. The UV-Visible absorption spectra and PL emission spectra showed broad peaks at 310 and 590 nm, respectively. The average particle sizes measured from the HR-TEM images were 5 nm, which were also supported by the Debye-Scherrer calculations using the X-ray diffraction (XRD) data. Moreover, the surface charges and the degrees of aggregation of the ZnS:Mn-MAA NCs were determined by electrophoretic and hydrodynamic light scattering methods, indicating formation of agglomerates in water with various sizes (50–440 nm) and different surface charge values accordingly the preparation conditions of the NCs (−7.59 to −24.98 mV). Finally, the relative photocatalytic activities of the ZnS:Mn-MAA NCs were evaluated by measuring the degradation rate of methylene blue (MB) molecule in a pseudo first-order reaction condition under the UV-visible light irradiation. As a result, the ZnS:Mn-MAA NC prepared at the pH 7 showed the best photo-degradation efficiency of the MB molecule with the first-order rate constant (kobs) of 2.0 × 10−3·min−1. PMID:28347105

Using lead chalcogenide nanocrystals as spin mixers: a perspective on near-infrared-to-visible upconversion.

PubMed

Nienhaus, Lea; Wu, Mengfei; Bulović, Vladimir; Baldo, Marc A; Bawendi, Moungi G

2018-03-01

The process of upconversion leads to emission of photons higher in energy than the incident photons. Near-infrared-to-visible upconversion, in particular, shows promise in sub-bandgap sensitization of silicon and other optoelectronic materials, resulting in potential applications ranging from photovoltaics that exceed the Shockley-Queisser limit to infrared imaging. A feasible mechanism for near-infrared-to-visible upconversion is triplet-triplet annihilation (TTA) sensitized by colloidal nanocrystals (NCs). Here, the long lifetime of spin-triplet excitons in the organic materials that undergo TTA makes upconversion possible under incoherent excitation at relatively low photon fluxes. Since this process relies on optically inactive triplet states, semiconductor NCs are utilized as efficient spin mixers, absorbing the incident light and sensitizing the triplet states of the TTA material. The state-of-the-art system uses rubrene with a triplet energy of 1.14 eV as the TTA medium, and thus allows upconversion of light with photon energies above ∼1.1 eV. In this perspective, we review the field of lead sulfide (PbS) NC-sensitized near-infrared-to-visible upconversion, discuss solution-based upconversion, and highlight progress made on solid-state upconversion devices.

Synthesis and Doping of Silicon Nanocrystals for Versatile Nanocrystal Inks

NASA Astrophysics Data System (ADS)

Kramer, Nicolaas Johannes

The impact of nanotechnology on our society is getting larger every year. Electronics are becoming smaller and more powerful, the "Internet of Things" is all around us, and data generation is increasing exponentially. None of this would have been possible without the developments in nanotechnology. Crystalline semiconductor nanoparticles (nanocrystals) are one of the latest developments in the field of nanotechnology. This thesis addresses three important challenges for the transition of silicon nanocrystals from the lab bench to the marketplace: A better understanding of the nanocrystal synthesis was obtained, the electronic properties of the nanocrystals were characterized and tuned, and novel silicon nanocrystal inks were formed and applied using simple coating technologies. Plasma synthesis of nanocrystals has numerous advantages over traditional solution-based synthesis methods. While the formation of nanoparticles in low pressure nonthermal plasmas is well known, the heating mechanism leading to their crystallization is poorly understood. A combination of comprehensive plasma characterization with a nanoparticle heating model presented here reveals the underlying plasma physics leading to crystallization. The model predicts that the nanoparticles reach temperatures as high as 900 K in the plasma as a result of heating reactions on the nanoparticle surface. These temperatures are well above the gas temperature and sufficient for complete nanoparticle crystallization. Moving the field of plasma nanoparticle synthesis to atmospheric pressures is important for lowering its cost and making the process attractive for industrial applications. The heating and charging model for silicon nanoparticles was adapted in Chapter 3 to study plasmas maintained over a wide range of pressures (10 -- 105 Pa). The model considers three collisionality regimes and determines the dominant contribution of each regime under various plasma conditions. Strong nanoparticle cooling at

Highly Luminescent Hybrid SiO2-Coated CdTe Quantum Dots Retained Initial Photoluminescence Efficiency in Sol-Gel SiO2 Film.

PubMed

Sun, Hongsheng; Xing, Yugui; Wu, Qinan; Yang, Ping

2015-02-01

A highly luminescent silica film was fabricated using tetraethyl orthosilicate (TEOS) and 3-aminopropyltrimethoxysilane (APS) through a controlled sol-gel reaction. The pre-hydrolysis of TEOS and APS which resulted in the mixture of TEOS and APS in a molecular level is a key for the formation of homogenous films. The aminopropyl groups in APS play an important role for obtaining homogeneous film with high photoluminescence (PL). Red-emitting hybrid SiO2-coated CdTe nano-crystals (NCs) were fabricated by a two-step synthesis including a thin SiO2 coating via a sol-gel process and a subsequent refluxing using green-emitting CdTe NCs. The hybrid SiO2-coated CdTe NCs were embedded in a functional SiO2 film via a two-step process including adding the NCs in SiO2 sol with a high viscosity and almost without ethanol and a subsequent spinning coating. The hybrid SiO2-coated CdTe NCs retained their initial PL efficiency (54%) in the film. Being encapsulated with the hybrid NCs in the film, no change on the absorption and PL spectra of red-emitting CdTe NCs (632 nm) was observed. This indicates the hybrid NCs is stable enough during preparation. This phenomenon is ascribed to the controlled sol-gel process and a hybrid SiO2 shell on CdTe NCs. Because these films exhibited high PL efficiency and stability, they will be utilizable for potential applications in many fields.

Interfacial dynamic surface traps of lead sulfide (PbS) nanocrystals: test-platform for interfacial charge carrier traps at the organic/inorganic functional interface

NASA Astrophysics Data System (ADS)

Kim, Youngjun; Ko, Hyungduk; Park, Byoungnam

2018-04-01

Nanocrystal (NC) size and ligand dependent dynamic trap formation of lead sulfide (PbS) NCs in contact with an organic semiconductor were investigated using a pentacene/PbS field effect transistor (FET). We used a bilayer pentacene/PbS FET to extract information of the surface traps of PbS NCs at the pentacene/PbS interface through the field effect-induced charge carrier density measurement in the threshold and subthreshold regions. PbS size and ligand dependent trap properties were elucidated by the time domain and threshold voltage measurements in which threshold voltage shift occurs by carrier charging and discharging in the trap states of PbS NCs. The observed threshold voltage shift is interpreted in context of electron trapping through dynamic trap formation associated with PbS NCs. To the best of our knowledge, this is the first demonstration of the presence of interfacial dynamic trap density of PbS NC in contact with an organic semiconductor (pentacene). We found that the dynamic trap density of the PbS NC is size dependent and the carrier residence time in the specific trap sites is more sensitive to NC size variation than to NC ligand exchange. The probing method presented in the study offers a means to investigate the interfacial surface traps at the organic-inorganic hetero-junction, otherwise understanding of the buried surface traps at the functional interface would be elusive.

Simulation of ultraviolet- and soft X-ray-pulse generation as a result of cooperative recombination of excitons in diamond nanocrystals embedded in a polymer film

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

Kukushkin, V. A., E-mail: vakuk@appl.sci-nnov.ru

2013-11-15

Using numerical simulation, it is shown that the recombination of free excitons photoexcited in diamond nanocrystals embedded in a polymer film can occur in the cooperative mode. It is found that this mode can be implemented despite the fact that diamond is an 'indirect' semiconductor. It is shown that the power of the generated radiation at the pulse peak during the cooperative recombination of free excitons can exceed that of the incoherent spontaneous emission of the same initial number of free excitons by more than an order of magnitude. Finally, it is shown that the process under consideration can bemore » used to generate picosecond pulses of ultraviolet and soft X-ray electromagnetic field at a wavelength of 235 nm.« less

Self-directed exploration provides a Ncs1-dependent learning bonus

PubMed Central

Mun, Ho-Suk; Saab, Bechara J.; Ng, Enoch; McGirr, Alexander; Lipina, Tatiana V.; Gondo, Yoichi; Georgiou, John; Roder, John C.

2015-01-01

Understanding the mechanisms of memory formation is fundamental to establishing optimal educational practices and restoring cognitive function in brain disease. Here, we show for the first time in a non-primate species, that spatial learning receives a special bonus from self-directed exploration. In contrast, when exploration is escape-oriented, or when the full repertoire of exploratory behaviors is reduced, no learning bonus occurs. These findings permitted the first molecular and cellular examinations into the coupling of exploration to learning. We found elevated expression of neuronal calcium sensor 1 (Ncs1) and dopamine type-2 receptors upon self-directed exploration, in concert with increased neuronal activity in the hippocampal dentate gyrus and area CA3, as well as the nucleus accumbens. We probed further into the learning bonus by developing a point mutant mouse (Ncs1P144S/P144S) harboring a destabilized NCS-1 protein, and found this line lacked the equivalent self-directed exploration learning bonus. Acute knock-down of Ncs1 in the hippocampus also decoupled exploration from efficient learning. These results are potentially relevant for augmenting learning and memory in health and disease, and provide the basis for further molecular and circuit analyses in this direction. PMID:26639399

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

Li, Bo; Zhang, Xiaosong, E-mail: zhangxiaosong@tjut.edu.cn; Li, Lan

Trap-rich CdS nanocrystals were synthesized by employing CdSt{sub 2} and sulfur as precursors via thermal decomposition. Furthermore, X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), absorption and photoluminescence (PL) spectra were used to characterize structure, morphology and luminescence properties of CdS nanocrystals (NCs). CdS NCs have a broad emission across 500–700 nm under the excitation of blue light with 460 nm, consequently, white light can be produced by mixing broad emission from CdS NCs excited by blue light, with the remaining blue light. In addition, the broad emission generation is closely and inseparably related to surface defects. Moreover, LaMer modelmore » was used to explain the phenomenon that the intensity of the trap emission gradually decreases as the reaction time increases in contrast with that of the band-edge emission. - Graphical abstract: Trap-rich CdS nanocrystals were synthesized. Furthermore, white light is produced by mixing broad emission across 500–700 nm from CdS NCs excited by blue light, in combination with the remaining blue light. - Highlights: • Trap-rich CdS nanocrystals were synthesized. • CdS NCs have a broad emission across 500–700 nm under the excitation of blue light. • White light can be produced by mixing broad emission with the remaining blue light.« less

Matrix-assisted relaxation in Fe(phen){sub 2}(NCS){sub 2} spin-crossover microparticles, experimental and theoretical investigations

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

Enachescu, Cristian, E-mail: cristian.enachescu@uaic.ro; Stancu, Alexandru; Tanasa, Radu

2016-07-18

In this study, we present the influence of the embedding matrix on the relaxation of Fe(phen){sub 2}(NCS){sub 2} (phen = 1,10-phenanthroline) spin-transition microparticles as revealed by experiments and provide an explanation within the framework of an elastic model based on a Monte-Carlo method. Experiments show that the shape of the high-spin → low-spin relaxation curves is drastically changed when the particles are dispersed in glycerol. This effect was considered in the model by means of interactions between the microparticles and the matrix. A faster start of the relaxation for microparticles embedded in glycerol is due to an initial positive local pressure actingmore » on the edge spin-crossover molecules from the matrix side. This local pressure diminishes and eventually becomes negative during relaxation, as an effect of the decrease of the volume of spin-crossover microparticles from high-spin to low-spin.« less

Reactive Precipitation of Anhydrous Alkali Sulfide Nanocrystals with Concomitant Abatement of Hydrogen Sulfide and Cogeneration of Hydrogen.

PubMed

Li, Xuemin; Zhao, Yangzhi; Brennan, Alice; McCeig, Miranda; Wolden, Colin A; Yang, Yongan

2017-07-21

Anhydrous alkali sulfide (M 2 S, M=Li or Na) nanocrystals (NCs) are important materials central to the development of next generation cathodes and solid-state electrolytes for advanced batteries, but not commercially available at present. This work reports an innovative method to directly synthesize M 2 S NCs through alcohol-mediated reactions between alkali metals and hydrogen sulfide (H 2 S). In the first step, the alkali metal is complexed with alcohol in solution, forming metal alkoxide (ROM) and releasing hydrogen (H 2 ). Next, H 2 S is bubbled through the ROM solution, where both chemicals are completely consumed to produce phase-pure M 2 S NC precipitates and regenerate alcohol that can be recycled. The M 2 S NCs morphology may be tuned through the choice of the alcohol and solvent. Both synthetic steps are thermodynamically favorable (ΔG m o <-100 kJ mol -1 ), proceeding rapidly to completion at ambient temperature with almost 100 % atom efficiency. The net result, H 2 S+2 m→M 2 S+H 2 , makes good use of a hazardous chemical (H 2 S) and delivers two value-added products that naturally phase separate for easy recovery. This scalable approach provides an energy-efficient and environmentally benign solution to the production of nanostructured materials required in emerging battery technologies. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Double-Protected All-Inorganic Perovskite Nanocrystals by Crystalline Matrix and Silica for Triple-Modal Anti-Counterfeiting Codes.

PubMed

Xu, Leimeng; Chen, Jiawei; Song, Jizhong; Li, Jianhai; Xue, Jie; Dong, Yuhui; Cai, Bo; Shan, Qingsong; Han, Boning; Zeng, Haibo

2017-08-09

Novel fluorescence with highly covert and reliable features is quite desirable to combat the sophisticated counterfeiters. Herein, we report a simultaneously triple-modal fluorescent characteristic of CsPbBr 3 @Cs 4 PbBr 6 /SiO 2 by the excitation of thermal, ultraviolet (UV) and infrared (IR) light for the first time, which can be applied for the multiple modal anti-counterfeiting codes. The diphasic structure CsPbBr 3 @Cs 4 PbBr 6 nanocrystals (NCs) was synthesized via the typical reprecipitation method followed by uniformly encapsulation into silica microspheres. Cubic CsPbBr 3 is responsible for the functions of anti-counterfeiting, while Cs 4 PbBr 6 crystalline and SiO 2 are mainly to protect unstable CsPbBr 3 NCs from being destroyed by ambient conditions. The as-prepared CsPbBr 3 @Cs 4 PbBr 6 /SiO 2 NCs possess improved stability and are capable of forming printable ink with organic binders for patterns. Interestingly, the fluorescence of diphasic CsPbBr 3 @Cs 4 PbBr 6 /SiO 2 capsule patterns can be reversibly switched by the heating, UV, and IR light irradiation, which has been applied as triple-modal fluorescent anti-counterfeiting codes. The results demonstrate that the perovskite@silica capsules are highly promising for myriad applications in areas such as fluorescent anti-counterfeiting, optoelectronic devices, medical diagnosis, and biological imaging.

Harvesting solar energy by means of charge-separating nanocrystals and their solids.

PubMed

Diederich, Geoffrey; O'Connor, Timothy; Moroz, Pavel; Kinder, Erich; Kohn, Elena; Perera, Dimuthu; Lorek, Ryan; Lambright, Scott; Imboden, Martene; Zamkov, Mikhail

2012-08-23

composite two-layer solid of PbS and TiO2 films. In this configuration, photoinduced electrons are injected into TiO2 and are subsequently picked up by an FTO electrode, while holes are channeled to a Au electrode via PbS layer. To develop the latter we introduce a Semiconductor Matrix Encapsulated Nanocrystal Arrays (SMENA) strategy, which allows bonding PbS NCs into the surrounding matrix of CdS semiconductor. As a result, fabricated solids exhibit excellent thermal stability, attributed to the heteroepitaxial structure of nanocrystal-matrix interfaces, and show compelling light-harvesting performance in prototype solar cells.

Well-Coupled Nanohybrids Obtained by Component-Controlled Synthesis and in Situ Integration of Mn xPd y Nanocrystals on Vulcan Carbon for Electrocatalytic Oxygen Reduction.

PubMed

Lu, Yanan; Zhao, Shulin; Yang, Rui; Xu, Dongdong; Yang, Jing; Lin, Yue; Shi, Nai-En; Dai, Zhihui; Bao, Jianchun; Han, Min

2018-03-07

Development of cheap, highly active, and robust bimetallic nanocrystal (NC)-based nanohybrid (NH) electrocatalysts for oxygen reduction reaction (ORR) is helpful for advancing fuel cells or other renewable energy technologies. Here, four kinds of well-coupled Mn x Pd y (MnPd 3 , MnPd-Pd, Mn 2 Pd 3 , Mn 2 Pd 3 -Mn 11 Pd 21 )/C NHs have been synthesized by in situ integration of Mn x Pd y NCs with variable component ratios on pretreated Vulcan XC-72 C using the solvothermal method accompanied with annealing under Ar/H 2 atmosphere and used as electrocatalysts for ORR. Among them, the MnPd 3 /C NHs possess the unique "half-embedded and half-encapsulated" interfaces and exhibit the highest catalytic activity, which can compete with some currently reported non-Pt catalysts (e.g., Ag-Co nanoalloys, Pd 2 NiAg NCs, PdCo/N-doped porous C, G-Cu 3 Pd nanocomposites, etc.), and close to commercial Pt/C. Electrocatalytic dynamic measurements disclose that their ORR mechanism abides by the direct 4e - pathway. Moreover, their durability and methanol-tolerant capability are much higher than that of Pt/C. As revealed by spectroscopic and electrochemical analyses, the excellent catalytic performance of MnPd 3 /C NHs results from the proper component ratio of Mn and Pd and the strong interplay of their constituents, which not only facilitate to optimize the d-band center or the electronic structure of Pd but also induce the phase transformation of MnPd 3 active components and enhance their conductivity or interfacial electron transfer dynamics. This work demonstrates that MnPd 3 /C NHs are promising methanol-tolerant cathode electrocatalysts that may be employed in fuel cells or other renewable energy option.

Poly(allyl methacrylate) functionalized hydroxyapatite nanocrystals via the combination of surface-initiated RAFT polymerization and thiol-ene protocol: a potential anticancer drug nanocarrier.

PubMed

Bach, Long Giang; Islam, Md Rafiqul; Vo, Thanh-Sang; Kim, Se-Kwon; Lim, Kwon Taek

2013-03-15

Hydroxyapatite nanocrystals (HAP NCs) were encapsulated by poly(allyl methacrylate) (PolyAMA) employing controlled surface-initiated reversible addition-fragmentation chain transfer (SI-RAFT) polymerization of allyl methacrylate to afford HAP-PolyAMA nanohybrids. The subsequent thiol-ene coupling of nanohybrids with 2-mercaptosuccinic acid resulted HAP-Poly(AMA-COOH) possessing multicarboxyl group. The formation of the nanohybrids was confirmed by FT-IR and EDS analyses. The TGA and FE-SEM investigation were further suggested the grafting of PolyAMA onto HAP NCs. The utility of the HAP-PolyAMA nanohybrid as drug carrier was also explored. The pendant carboxyl groups on the external layers of nanohybrids were conjugated with anticancer drug cisplatin to afford HAP-Poly(AMA-COOH)/Pt complex. The formation of the complex was confirmed by FT-IR, XPS, and FE-SEM. In vitro evaluation of the synthesized complex as nanomedicine revealed its potential chemotherapeutic efficacy against cancer cell lines. Copyright © 2012 Elsevier Inc. All rights reserved.

A Study of Utah's New Century Scholarship (NCS) Program

ERIC Educational Resources Information Center

Kearl, Christine; Byrnes, Deborah; Maahs-Fladung, Cathy

2013-01-01

This was a study about the New Century Scholarship (NCS) program offered to Utah high school students at commencement for earning an Associate of Arts (AA) degree by the time they graduate from high school. An Associate of Arts degree is earning 60 college credits toward a specific AA program. The goal of the NCS program was to assist students to…

Annealing temperature and barrier thickness effect on the structural and optical properties of silicon nanocrystals/SiO₂ superlattices

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

López-Vidrier, J., E-mail: jlopezv@el.ub.edu; Hernández, S.; López-Conesa, L.

2014-10-07

The effect of the annealing temperature and the SiO₂ barrier thickness of silicon nanocrystal (NC)/SiO₂ superlattices (SLs) on their structural and optical properties is investigated. Energy-filtered transmission electron microscopy (TEM) revealed that the SL structure is maintained for annealing temperatures up to 1150 °C, with no variation on the nanostructure morphology for different SiO₂ barrier thicknesses. Nevertheless, annealing temperatures as high as 1250 °C promote diffusion of Si atoms into the SiO₂ barrier layers, which produces larger Si NCs and the loss of the NC size control expected from the SL approach. Complementary Raman scattering measurements corroborated these results formore » all the SiO₂ and Si-rich oxynitride layer thicknesses. In addition, we observed an increasing crystalline fraction up to 1250 °C, which is related to a decreasing contribution of the suboxide transition layer between Si NCs and the SiO₂ matrix due to the formation of larger NCs. Finally, photoluminescence measurements revealed that the emission of the superlattices exhibits a Gaussian-like lineshape with a maximum intensity after annealing at 1150 °C, indicating a high crystalline degree in good agreement with Raman results. Samples submitted to higher annealing temperatures display a progressive emission broadening, together with an increase in the central emission wavelength. Both effects are related to a progressive broadening of the size distribution with a larger mean size, in agreement with TEM observations. On the other hand, whereas the morphology of the Si NCs is unaffected by the SiO₂ barrier thickness, the emission properties are slightly modified. These observed modifications in the emission lineshape allow monitoring the precipitation process of Si NCs in a direct non-destructive way. All these experimental results evidence that an annealing temperature of 1150 °C and 1-nm SiO₂ barrier can be reached whilst preserving the SL structure

Direct and inverse auger processes in InAs nanocrystals: can the decay signature of a trion be mistaken for carrier multiplication?

PubMed

Califano, Marco

2009-09-22

A complete and detailed theoretical investigation of the main processes involved in the controversial detection and quantification of carrier multiplication (CM) is presented, providing a coherent and comprehensive picture of excited state relaxation in InAs nanocrystals (NCs). The observed rise and decay times of the 1S transient bleach are reproduced, in the framework of the Auger model, using an atomistic semiempirical pseudopotential method, achieving excellent agreement with experiment. The CM time constants for small core-only and core/shell nanocrystals are obtained as a function of the excitation energy, assuming an impact-ionization-like process. The resulting lifetimes at energies close to the observed CM onset are consistent with the upper limits deduced experimentally from PbSe and CdSe samples. Most interestingly, as the Auger recombination lifetimes calculated for charged excitons are found to be of a similar order of magnitude to those computed for biexcitons, both species are expected to exhibit the fast decay component in NC population dynamics so far attributed exclusively to the presence of biexcitons and therefore identified as the signature of CM occurrence in high-energy low-pump-fluence spectroscopic studies. However, the ratio between trions and biexcitons time constants is found to be larger than the typical experimental accuracy. It is therefore concluded that, in InAs NCs, it should be experimentally possible to discriminate between the two species and that the origin of the observed discrepancies in CM yields is unlikely to lay in the presence of charged excitons.

The solute specificity profiles of nucleobase cation symporter 1 (NCS1) from Zea mays and Setaria viridis illustrate functional flexibility.

PubMed

Rapp, Micah; Schein, Jessica; Hunt, Kevin A; Nalam, Vamsi; Mourad, George S; Schultes, Neil P

2016-03-01

The solute specificity profiles (transport and binding) for the nucleobase cation symporter 1 (NCS1) proteins, from the closely related C4 grasses Zea mays and Setaria viridis, differ from that of Arabidopsis thaliana and Chlamydomonas reinhardtii NCS1. Solute specificity profiles for NCS1 from Z. mays (ZmNCS1) and S. viridis (SvNCS1) were determined through heterologous complementation studies in NCS1-deficient Saccharomyces cerevisiae strains. The four Viridiplantae NCS1 proteins transport the purines adenine and guanine, but unlike the dicot and algal NCS1, grass NCS1 proteins fail to transport the pyrimidine uracil. Despite the high level of amino acid sequence similarity, ZmNCS1 and SvNCS1 display distinct solute transport and recognition profiles. SvNCS1 transports adenine, guanine, hypoxanthine, cytosine, and allantoin and competitively binds xanthine and uric acid. ZmNCS1 transports adenine, guanine, and cytosine and competitively binds, 5-fluorocytosine, hypoxanthine, xanthine, and uric acid. The differences in grass NCS1 profiles are due to a limited number of amino acid alterations. These amino acid residues do not correspond to amino acids essential for overall solute and cation binding or solute transport, as previously identified in bacterial and fungal NCS1, but rather may represent residues involved in subtle solute discrimination. The data presented here reveal that within Viridiplantae, NCS1 proteins transport a broad range of nucleobase compounds and that the solute specificity profile varies with species.

Two-photon pumped amplified spontaneous emission based on all-inorganic perovskite nanocrystals embedded with gold nanorods

NASA Astrophysics Data System (ADS)

Liu, Shaoying; Fang, Xiaohui; Wang, Yimeng; Zhang, Xinping

2018-07-01

CsPbBr3 nanocrystals have attracted great interest owing to their high fluorescence quantum efficiency, adjustable photoluminescence wavelength, and good stability. We report a device that consists of disordered gold nanorods underneath a film of CsPbBr3 nanocrystals. Two-photon pumping using femtosecond laser pulses at 800 nm enables amplified spontaneous emission (ASE) at about 523 nm. In this work, a narrow peak with linewidth of 5 nm is observed when the pump fluence reaches a low threshold of 0.65 mJ/cm2. The results show that plasmonic resonance of gold nanorods improves the emission transition rate and enables low threshold ASE.

Atomistic Description of Thiostannate-Capped CdSe Nanocrystals: Retention of Four-Coordinate SnS4 Motif and Preservation of Cd-Rich Stoichiometry

PubMed Central

2016-01-01

Colloidal semiconductor nanocrystals (NCs) are widely studied as building blocks for novel solid-state materials. Inorganic surface functionalization, used to displace native organic capping ligands from NC surfaces, has been a major enabler of electronic solid-state devices based on colloidal NCs. At the same time, very little is known about the atomistic details of the organic-to-inorganic ligand exchange and binding motifs at the NC surface, severely limiting further progress in designing all-inorganic NCs and NC solids. Taking thiostannates (K4SnS4, K4Sn2S6, K6Sn2S7) as typical examples of chalcogenidometallate ligands and oleate-capped CdSe NCs as a model NC system, in this study we address these questions through the combined application of solution 1H NMR spectroscopy, solution and solid-state 119Sn NMR spectroscopy, far-infrared and X-ray absorption spectroscopies, elemental analysis, and by DFT modeling. We show that through the X-type oleate-to-thiostannate ligand exchange, CdSe NCs retain their Cd-rich stoichiometry, with a stoichiometric CdSe core and surface Cd adatoms serving as binding sites for terminal S atoms of the thiostannates ligands, leading to all-inorganic (CdSe)core[Cdm(Sn2S7)yK(6y-2m)]shell (taking Sn2S76– ligand as an example). Thiostannates SnS44– and Sn2S76– retain (distorted) tetrahedral SnS4 geometry upon binding to NC surface. At the same time, experiments and simulations point to lower stability of Sn2S64– (and SnS32–) in most solvents and its lower adaptability to the NC surface caused by rigid Sn2S2 rings. PMID:25597625

Anti-infiltration for fabrication of a suspended nanoparticle layer on porous close-packed colloidal arrays.

PubMed

Teh, Lay K; Yan, Qingfeng; Wong, Chee C

2009-04-01

We develop a new method to fabricate suspended sheets of nanocrystals (NCs) on porous surfaces. The method relies on the resistance of an aqueous suspension droplet to infiltrate a porous network; hence, the method is named anti-infiltration. The process works by combining fluid dynamics of a liquid droplet during impact/absorption onto a porous surface with the convective self-assembly of NCs. The immobilization of the liquid droplet edge due to the self-assembly of NCs at the meniscus is harnessed to halt the lateral spreading of the droplet and, consequently, the capillary penetration of the liquid immediately after droplet impact. Further capillary penetration of the liquid is drastically reduced because of the competition between capillary forces and convective losses as well as the rapid occlusion of the pores as soon as a continuous NC film has formed upon evaporation of the suspension. This method holds promise for a wide variety of optoelectronic, sensing, and separation membrane applications. As an example, we demonstrate that these suspended NC layers are suitable candidates as planar defects embedded within a colloidal photonic crystal.

Integration, photostability and spontaneous emission rate enhancement of colloidal PbS nanocrystals for Si-based photonics at telecom wavelengths.

PubMed

Humer, Markus; Guider, Romain; Jantsch, Wolfgang; Fromherz, Thomas

2013-08-12

We experimentally investigate PbS nanocrystal (NC) photoluminescence (PL) coupled to all-integrated Si-based ring resonators and waveguides at telecom wavelengths. Dissolving the NCs into Novolak polymer significantly improves their stability in ambient atmosphere. Polymer-NC blends of various NC concentrations can be applied to and removed from the same device. For NC concentrations up to 4vol%, the spontaneous emission rate into ring-resonator modes is enhanced by a factor of ~13 with respect to that into a straight waveguide. The PL intensity shows a linear dependence on the excitation intensity up to 1.64kW/cm(2) and stable quality factors of ~2500.

Enhancing the luminescence efficiency of silicon-nanocrystals by interaction with H+ ions.

PubMed

Cannas, Marco; Camarda, Pietro; Vaccaro, Lavinia; Amato, Francesco; Messina, Fabrizio; Fiore, Tiziana; Li Vigni, Maria

2018-04-18

The emission of silicon nanocrystals (Si-NCs), synthesized by pulsed laser ablation in water, was investigated on varying the pH of the solution. These samples emit μs decaying orange photoluminescence (PL) associated with radiative recombination of quantum-confined excitons. Time-resolved spectra reveal that both the PL intensity and the lifetime increase by a factor of ∼20 when the pH decreases from 10 to 1 thus indicating that the emission quantum efficiency increases by inhibiting nonradiative decay rates. Infrared (IR) absorption and electron paramagnetic resonance (EPR) experiments allow addressing the origin of defects on which the excitons nonradiatively recombine. The linear correlation between the PL and the growth of SiH groups demonstrates that H+ ions passivate the nonradiative defects that are located in the interlayer between the Si-NC core and the amorphous SiO2 shell.

Weaving a two-dimensional fishing net from titanoniobate nanosheets embedded with Fe3O4 nanocrystals for highly efficient capture and isotope labeling of phosphopeptides

NASA Astrophysics Data System (ADS)

Chen, Xueqin; Li, Siyuan; Zhang, Xiaoxia; Min, Qianhao; Zhu, Jun-Jie

2015-03-01

Qualitative and quantitative characterization of phosphopeptides by means of mass spectrometry (MS) is the main goal of MS-based phosphoproteomics, but suffers from their low abundance in the large haystack of various biological molecules. Herein, we introduce two-dimensional (2D) metal oxides to tackle this biological separation issue. A nanocomposite composed of titanoniobate nanosheets embedded with Fe3O4 nanocrystals (Fe3O4-TiNbNS) is constructed via a facile cation-exchange approach, and adopted for the capture and isotope labeling of phosphopeptides. In this nanoarchitecture, the 2D titanoniobate nanosheets offer enlarged surface area and a spacious microenvironment for capturing phosphopeptides, while the Fe3O4 nanocrystals not only incorporate a magnetic response into the composite but, more importantly, also disrupt the restacking process between the titanoniobate nanosheets and thus preserve a greater specific surface for binding phosphopeptides. Owing to the extended active surface, abundant Lewis acid sites and excellent magnetic controllability, Fe3O4-TiNbNS demonstrates superior sensitivity, selectivity and capacity over homogeneous bulk metal oxides, layered oxides, and even restacked nanosheets in phosphopeptide enrichment, and further allows in situ isotope labeling to quantify aberrantly-regulated phosphopeptides from sera of leukemia patients. This composite nanosheet greatly contributes to the MS analysis of phosphopeptides and gives inspiration in the pursuit of 2D structured materials for separation of other biological molecules of interests.Qualitative and quantitative characterization of phosphopeptides by means of mass spectrometry (MS) is the main goal of MS-based phosphoproteomics, but suffers from their low abundance in the large haystack of various biological molecules. Herein, we introduce two-dimensional (2D) metal oxides to tackle this biological separation issue. A nanocomposite composed of titanoniobate nanosheets embedded with Fe3

Biosynthesis of micro- and nanocrystals of Pb (II), Hg (II) and Cd (II) sulfides in four Candida species: a comparative study of in vivo and in vitro approaches.

PubMed

Cuéllar-Cruz, Mayra; Lucio-Hernández, Daniela; Martínez-Ángeles, Isabel; Demitri, Nicola; Polentarutti, Maurizio; Rosales-Hoz, María J; Moreno, Abel

2017-03-01

Nature produces biominerals (biogenic minerals) that are synthesized as complex structures, in terms of their physicochemical properties. These biominerals are composed of minerals and biological macromolecules. They are produced by living organisms and are usually formed through a combination of chemical, biochemical and biophysical processes. Microorganisms like Candida in the presence of heavy metals can biomineralize those metals to form microcrystals (MCs) and nanocrystals (NCs). In this work, MCs and NCs of PbS, HgS or HgCl 2 as well as CdS are synthesized both in vitro (gels) and in vivo by four Candida species. Our in vivo results show that, in the presence of Pb 2+ , Candida cells are able to replicate and form extracellular PbS MCs, whereas in the presence of Hg 2+ and Cd 2+ , they did synthesize intercellular MCs from HgS or HgCl 2 and CdS NCs respectively. The MCs and NCs biologically obtained in Candida were compared with those PbS, HgS and CdS crystals synthetically obtained in vitro through the gel method (grown either in agarose or in sodium metasilicate hydrogels). This is, to our knowledge, the first time that the biosynthesis of the various MCs and NCs (presented in several species of Candida) has been reported. This biosynthesis is differentially regulated in each of these pathogens, which allows them to adapt and survive in different physiological and environmental habitats. © 2017 The Authors. Microbial Biotechnology published by John Wiley & Sons Ltd and Society for Applied Microbiology.

Phosphine-free synthesis of high-quality reverse type-I ZnSe/CdSe core with CdS/CdxZn1 - xS/ZnS multishell nanocrystals and their application for detection of human hepatitis B surface antigen

NASA Astrophysics Data System (ADS)

Shen, Huaibin; Yuan, Hang; Niu, Jin Zhong; Xu, Shasha; Zhou, Changhua; Ma, Lan; Li, Lin Song

2011-09-01

Highly photoluminescent (PL) reverse type-I ZnSe/CdSe nanocrystals (NCs) and ZnSe/CdSe/CdS/CdxZn1 - xS/ZnS core/multishell NCs were successfully synthesized by a phosphine-free method. By this low-cost, 'green' synthesis route, more than 10 g of high-quality ZnSe/CdSe/CdS/CdxZn1 - xS/ZnS NCs were synthesized in a large scale synthesis. After the overgrowth of a CdS/CdxZn1 - xS/ZnS multishell on ZnSe/CdSe cores, the PL quantum yields (QYs) increased from 28% to 75% along with the stability improvement. An amphiphilic oligomer was used as a surface coating agent to conduct a phase transfer experiment, core/multishell NCs were dissolved in water by such surface modification and the QYs were still kept above 70%. The as-prepared water dispersible ZnSe/CdSe/CdS/CdxZn1 - xS/ZnS core/multishell NCs not only have high fluorescence QYs but also are extremely stable in various physiological conditions. Furthermore, a biosensor system (lateral flow immunoassay system, LFIA) for the detection of human hepatitis B surface antigen (HBsAg) was developed by using this water-soluble core/multishell NCs as a fluorescent label and a nitrocellulose filter membrane for lateral flow. The result showed that such ZnSe/CdSe/CdS/CdxZn1 - xS/ZnS core/multishell NCs were excellent fluorescent labels to detect HBsAg. The sensitivity of HBsAg detection could reach as high as 0.05 ng ml - 1.

VizieR Online Data Catalog: SFiNCs: X-ray, IR and membership catalogs (Getman+, 2017)

NASA Astrophysics Data System (ADS)

Getman, K. V.; Broos, P. S.; Kuhn, M. A.; Feigelson, E. D.; Richert, A. J. W.; Ota, Y.; Bate, M. R.; Garmire, G. P.

2017-06-01

Sixty five X-ray observations for the 22 Star Formation in Nearby Clouds (SFiNCs) star-forming regions (SFRs) (see tables 1 and 2), made with the imaging array on the Advanced CCD Imaging Spectrometer (ACIS), were pulled from the Chandra archive (spanning 2000 Jan to 2015 Apr; see table 2). Our final Chandra-ACIS catalog for the 22 SFiNCs SFRs comprises 15364 X-ray sources (Tables 3 and 4 and section 3.2). To obtain MIR photometry for X-ray objects and to identify and measure MIR photometry for additional non-Chandra disky stars that were missed in previous studies of the SFiNCs regions (typically faint YSOs), we have reduced the archived Spitzer-IRAC data by homogeneously applying the MYStIX-based Spitzer-IRAC data reduction methods of Kuhn+ (2013, J/ApJS/209/29) to the 423 Astronomical Object Request (AORs) data sets for the 22 SFiNCs SFRs (Table 5). As in MYStIX, here the SFiNCs IRAC source catalog retains all point sources with the photometric signal-to-noise ratio >5 in both [3.6] and [4.5] channels. This catalog covers the 22 SFiNCs SFRs and their vicinities on the sky and comprises 1638654 IRAC sources with available photometric measurements for 100%, 100%, 29%, and 23% of these sources in the 3.6, 4.5, 5.8, and 8.0um bands, respectively (see table 6 and section 3.4). Source position cross correlations between the SFiNCs Chandra X-ray source catalog and an IR catalog, either the "cut-out" IRAC or 2MASS, were made using the steps described in section 3.5. Tables 7 and 8 provide the list of 8492 SFiNCs probable cluster members (SPCMs) and their main IR and X-ray properties (see section 4). (9 data files).

All-silicon tandem solar cells: Practical limits for energy conversion and possible routes for improvement

NASA Astrophysics Data System (ADS)

Jia, Xuguang; Puthen-Veettil, Binesh; Xia, Hongze; Yang, Terry Chien-Jen; Lin, Ziyun; Zhang, Tian; Wu, Lingfeng; Nomoto, Keita; Conibeer, Gavin; Perez-Wurfl, Ivan

2016-06-01

Silicon nanocrystals (Si NCs) embedded in a dielectric matrix is regarded as one of the most promising materials for the third generation photovoltaics, owing to their tunable bandgap that allows fabrication of optimized tandem devices. Previous work has demonstrated fabrication of Si NCs based tandem solar cells by sputter-annealing of thin multi-layers of silicon rich oxide and SiO2. However, these device efficiencies were much lower than expected given that their theoretical values are much higher. Thus, it is necessary to understand the practical conversion efficiency limits for these devices. In this article, practical efficiency limits of Si NC based double junction tandem cells determined by fundamental material properties such as minority carrier, mobility, and lifetime are investigated. The practical conversion efficiency limits for these devices are significantly different from the reported efficiency limits which use Shockley-Queisser assumptions. Results show that the practical efficiency limit of a double junction cell (1.6 eV Si NC top cell and a 25% efficient c-Si PERL cell as the bottom cell) is 32%. Based on these results suggestions for improvement to the performance of Si nanocrystal based tandem solar cells in terms of the different parameters that were simulated are presented.

Translation, cross-cultural adaptation and validation of the Italian version of the Nottingham Clavicle Score (NCS).

PubMed

Vascellari, Alberto; Schiavetti, Stefano; Rebuzzi, Enrico; Coletti, Nicolò

2015-11-01

The Nottingham Clavicle Score (NCS) is a specific Patient Reported Outcome Measure of injuries to the clavicle, acromio-clavicular joint (ACJ) and sterno-clavicular joint. The purpose of this study was to translate the NCS into Italian and establish its cultural adaptiveness and validity. The original version of the NCS was translated into Italian in accordance with the cross-cultural adaptation guidelines described by Guillemin. Sixty-six patients [average age 45.7 years (SD 11.3)] who had received surgical treatment for injuries of the ACJ and the clavicle were included in the study. The study population completed the NCS twice within 5 days, the Oxford Shoulder Score (OSS), the Disability of the Arm, Shoulder and Hand (DASH) questionnaire and the short-form 36 (SF-36). Statistical tests assessed the construct validity, discriminant validity, internal consistency, reliability and feasibility of the NCS. The translation and adaptation of the NCS for an Italian context required no major cultural adaptation. Internal consistency was high (Cronbach's α, 0.86). Test-retest reproducibility was excellent (ρ = 0.981, p < 0.00001). Administration time was 45 s (range 1 min 32 s-8 min), and all items were answered. The Italian NCS showed strong correlation with the DASH (-0.87), the OSS (-0.84) and those subscales of the SF-36 (physical functioning, role physical and bodily pain) which aim to measure similar constructs. The Italian NCS scale is a reliable, valid, consistent shoulder assessment form that can be used to assess the functional limitations of patients with injuries of clavicle or ACJ. III.

Photocatalytic growth of Ag nanocrystals on hydrothermally synthesized multiphasic TiO2/reduced graphene oxide (rGO) nanocomposites and their SERS performance

NASA Astrophysics Data System (ADS)

Guo, Tian-Long; Li, Ji-Guang; Sun, Xudong; Sakka, Yoshio

2017-11-01

TiO2/reduced graphene oxide (rGO) nanocomposites were prepared via a facile one-step hydrothermal method using TiCl3 as the TiO2 precursor. Cetyltrimethyl ammonium bromide (CTAB) was introduced as a stabilizer for GO in solution. The effects of GO content, Ti3+ concentration and urea additive on phase constituent and morphology of the TiO2 crystallites in the nanocomposites were systematically investigated. UV-vis absorption ability of the as-made composites was further tested and discussed. Ag nanocrystals (NCs) were photocatalytically grown on the surfaces of biphasic (anatase + brookite) and triphasic (anatase + brookite + rutile) TiO2/rGO nanocomposites to evaluate their surface-enhanced Raman scattering (SERS) performances. Morphology evolution of the Ag NCs in response to different photocatalytic ability of the TiO2/rGO nanocomposite was also investigated in detail. The nanocomposite with triphasic TiO2 of proper phase constituents was confirmed to favor the growth of Ag particles of two distinctly different sizes and to produce SERS substrates of substantially better performance.

Exciton Dynamics in Alternative Solar Cell Materials: Polymers, Nanocrystals, and Small Molecules

NASA Astrophysics Data System (ADS)

Pundsack, Thomas J.

To keep fossil fuel usage in 2040 even with 2010 usage, 50% of global energy will need to come from alternative sources such as solar cells. While the photovoltaic market is currently dominated by crystalline silicon, there are many low-cost solar cell materials such as conjugated polymers, semiconductor nanocrystals, and organic small molecules which could compete with fossil fuels. To create cost-competitive devices, understanding the excited state dynamics of these materials is necessary. The first section of this thesis looks at aggregation in poly(3-hexylthiophene) (P3HT) which is commonly used in organic photovoltaics. The amount of aggregation in P3HT thin films was controlled by using a mixture of regioregular and regiorandom P3HT. Even with few aggregates present, excited states were found to transfer from amorphous to aggregate domains in <50 fs which could indicate efficient long-range energy transfer. To further study P3HT aggregation, a triblock consisting of two P3HT chains with a coil polymer between them was investigated. By changing solvents, aggregation was induced in a stable and reversible manner allowing for spectroscopic studies of P3HT aggregates in solution. The polarity of the solvent was adjusted, and no change in excited state dynamics was observed implying the excited state has little charge-transfer character. Next, the conduction band density of states for copper zinc tin sulfide nanocrystals (CZTS NCs) was measured using pump-probe spectroscopy and found to be in agreement with theoretical results. The density of states shifted and dilated for smaller NCs indicative of quantum confinement. The excited state lifetime was found to be short (<20 ps) and independent of NC size which could limit the efficiency of CZTS photovoltaic devices. Finally, triplet-triplet annihilation (TTA) was studied in platinum octaethylporphyrin (PtOEP) thin films. By analyzing pump-probe spectra, the product of TTA in PtOEP thin films was assigned to a long

Surface chemical modification of nanocrystals

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

Helms, Brett Anthony; Milliron, Delia Jane; Rosen, Evelyn Louise

Nanocrystals comprising organic ligands at surfaces of the plurality of nanocrystals are provided. The organic ligands are removed from the surfaces of the nanocrystals using a solution comprising a trialkyloxonium salt in a polar aprotic solvent. The removal of the organic ligands causes the nanocrystals to become naked nanocrystals with cationic surfaces.

White up-conversion emission in Ho3+/Tm3+/Yb3+ tri-doped glass ceramics embedding BaF2 nanocrystals

NASA Astrophysics Data System (ADS)

Li, Chenxia; Xu, Shiqing; Ye, Rengguang; Deng, Degang; Hua, Youjie; Zhao, Shilong; Zhuang, Songlin

2011-04-01

Ho3+/Tm3+/Yb3+ tri-doped glass ceramics with white light emitting have been developed and demonstrated. Pumped by 980 nm laser diode (LD), intensive red, green and blue up-conversions (UC) were obtained. The green emission is assigned to Ho3+ ion and the blue emission is assigned to Tm3+ ion, whereas the red emission is the combination contribution of the Ho3+ and Tm3+ ions. The RGB intensities could be adjusted by tuning the rare-earth ion concentration and pump power intensity. Thus, multicolor of the luminescence, including perfect white light with CIE-X=0.329 and CIE-Y=0.342 in the 1931 CIE chromaticity diagram can be obtained in 0.15 Ho3+/0.2Tm3+/3Yb3+ tri-doped glass ceramics embedding BaF2 nanocrystals pumped by a single infrared laser diode source of 980 nm at 500 mW. The up-conversion luminescence mechanism of Yb3+ sensitize Ho3+ and Tm3+ ions and the energy transfer from Ho3+ to Tm3+ in oxy-fluoride silicate glass ceramics were analyzed.

Temperature profiles for laser-induced heating of nanocrystals embedded in glass matrices

NASA Astrophysics Data System (ADS)

Bhatnagar, Promod K.; Nagpal, Swati

2001-05-01

Quantum confined nanostructures are very important because of their application towards optoelectronic devices. Commercial colored glass filters, which have large semiconductor particles, are being used to manufacture nanocrystals by suitable heat treatments. The progress in this area has been hampered by high size dispersion of these dots in the glass matrix which leads to reduction in higher order susceptibility thereby reducing non-linearity. In the present paper attempt has been made to theoretically model the temperature profiles of a laser irradiated CdS doped Borosilicate sample. Laser being used has a beam diameter of 1.5 mm and energy for 10 nsec pulse is 10 mJ. Two different particle radii of 5 nm and 10 nm have been considered. It is found that larger particles reach higher temperatures for the same pulse characteristics. This is because smaller particles have larger surface to volume ratio and hence dissipates out heat faster to the surrounding. Hence bigger particles will reach dissolution temperature faster than smaller particle and particle beyond a certain size should dissolve in the glass matrix when a sample is heat treated by laser. This could lead to a reduction in size dispersion of the nanocrystals. Also photodarkening effect found in semiconductor doped glasses is a big handicap for practical application of these materials in fast optical switching and non-linear optical devices. Photodarkening effect has been established to be a photochemical effect and it is important to study the temperature profiles around a particle since it will effect the impurity migration.

Synthesis and Study of Fe-Doped Bi₂S₃ Semimagnetic Nanocrystals Embedded in a Glass Matrix.

PubMed

Silva, Ricardo S; Mikhail, Hanna D; Guimarães, Eder V; Gonçalves, Elis R; Cano, Nilo F; Dantas, Noelio O

2017-07-11

Iron-doped bismuth sulphide (Bi 2- x Fe x S₃) nanocrystals have been successfully synthesized in a glass matrix using the fusion method. Transmission electron microscopy images and energy dispersive spectroscopy data clearly show that nanocrystals are formed with an average diameter of 7-9 nm, depending on the thermic treatment time, and contain Fe in their chemical composition. Magnetic force microscopy measurements show magnetic phase contrast patterns, providing further evidence of Fe incorporation in the nanocrystal structure. The electron paramagnetic resonance spectra displayed Fe 3+ typical characteristics, with spin of 5/2 in the 3d⁵ electronic state, thereby confirming the expected trivalent state of Fe ions in the Bi₂S₃ host structure. Results from the spin polarized density functional theory simulations, for the bulk Fe-doped Bi₂S₃ counterpart, corroborate the experimental fact that the volume of the unit cell decreases with Fe substitutionally doping at Bi1 and Bi2 sites. The Bader charge analysis indicated a pseudo valency charge of 1.322| e | on Fe Bi ₁ and 1.306| e | on Fe Bi ₂ ions, and a spin contribution for the magnetic moment of 5.0 µ B per unit cell containing one Fe atom. Electronic band structures showed that the (indirect) band gap changes from 1.17 eV for Bi₂S₃ bulk to 0.71 eV (0.74 eV) for Bi₂S₃:Fe Bi1 (Bi₂S₃:Fe Bi2 ). These results are compatible with the 3d⁵ high-spin state of Fe 3+ , and are in agreement with the experimental results, within the density functional theory accuracy.

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

Influence of dimensionality and interface type on optical and electronic properties of CdS/ZnS core-shell nanocrystals—A first-principles study

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

Kocevski, V., E-mail: vancho.vk@gmail.com, E-mail: vancho.kocevski@physics.uu.se; Eriksson, O.; Gerard, C.

2015-10-28

Semiconducting nanocrystals (NCs) have become one of the leading materials in a variety of applications, mainly due to their size tunable band gap and high intensity emission. Their photoluminescence (PL) properties can be notably improved by capping the nanocrystals with a shell of another semiconductor, making core-shell structures. We focus our study on the CdS/ZnS core-shell nanocrystals that are closely related to extensively studied CdSe/CdS NCs, albeit exhibiting rather different photoluminescence properties. We employ density functional theory to investigate the changes in the electronic and optical properties of these nanocrystals with size, core/shell ratio, and interface structure between the coremore » and the shell. We have found that both the lowest unoccupied eigenstate (LUES) and the highest occupied eigenstate (HOES) wavefunction (WF) are localized in the core of the NCs, with the distribution of the LUES WF being more sensitive to the size and the core/shell ratio. We show that the radiative lifetimes are increasing, and the Coulomb interaction energies decrease with increasing NC size. Furthermore, we investigated the electronic and optical properties of the NCs with different interfaces between the core and the shell and different core types. We find that the different interfaces and core types have rather small influence on the band gaps and the absorption indexes, as well as on the confinement of the HOES and LUES WFs. Also the radiative lifetimes are found to be only slightly influenced by the different structural models. In addition, we compare these results with the previous results for CdSe/CdS NCs, reflecting the different PL properties of these two types of NCs. We argue that the difference in their Coulomb interaction energies is one of the main reasons for their distinct PL properties.« less

Low-dimensional quantum magnetism in Cu (NCS) 2: A molecular framework material

NASA Astrophysics Data System (ADS)

Cliffe, Matthew J.; Lee, Jeongjae; Paddison, Joseph A. M.; Schott, Sam; Mukherjee, Paromita; Gaultois, Michael W.; Manuel, Pascal; Sirringhaus, Henning; Dutton, Siân E.; Grey, Clare P.

2018-04-01

Low-dimensional magnetic materials with spin-1/2 moments can host a range of exotic magnetic phenomena due to the intrinsic importance of quantum fluctuations to their behavior. Here, we report the structure, magnetic structure, and magnetic properties of copper ii thiocyanate, Cu(NCS ) 2, a one-dimensional coordination polymer which displays low-dimensional quantum magnetism. Magnetic susceptibility, electron paramagnetic resonance spectroscopy, 13C magic-angle spinning nuclear magnetic resonance spectroscopy, and density functional theory investigations indicate that Cu(NCS ) 2 behaves as a two-dimensional array of weakly coupled antiferromagnetic spin chains [J2=133 (1 ) K , α =J1/J2=0.08 ] . Powder neutron-diffraction measurements confirm that Cu(NCS ) 2 orders as a commensurate antiferromagnet below TN=12 K , with a strongly reduced ordered moment (0.3 μB ) due to quantum fluctuations.

Investigating the Effect of Nanoscale Changes on the Chemistry and Energetics of Nanocrystals with a Novel Photoemission Spectroscopy Methodology

NASA Astrophysics Data System (ADS)

Liao, Michael W.

This dissertation explores the effect of nanometer-scale changes in structure on the energetics of photocatalytic and photovoltaic materials. Of particular interest are semiconductor nanocrystals (NCs), which have interesting chemical properties that lead to novel structures and applications. Chief among these properties are quantum confinement and the high surface area-to-volume ratio, which allow for chemical tuning of the energetics and structure of NCs. This tunable energetic landscape has led to increasing application of NCs in various areas of research, including solar energy conversion, light-emitting diode technologies, and photocatalysis. However, spectroscopic methods to determine the energetics of NCs have not been well developed, due to chemical complexities of relevant NCs such as polydispersity, capping ligand effects, core-shell structures, and other chemical modifications. In this work, we demonstrate and expand the utility of photoelectron spectroscopy (PES) to probe the energetics of NCs by considering the physical processes that lead to background and secondary photoemission to enhance photoemission from the sample of interest. A new methodology for the interpretation of UP spectra was devised in order to emphasize the minute changes to the UP spectra line shape that arise from nanoscopic changes to the NCs. We applied various established subtractions that correct for photon source satellites, secondary photoelectrons, and substrate photoemission. We then investigated the effect of ligand surface coverage on the surface chemistry and density of states at the top of valence band (VB). We systematically removed ligands by increasing numbers of purification steps for two diameters of NCs and found that doing so increased photoemission density at the top of the VB, which is due to undercoordinated surface atoms. Deeper VB structure was also altered, possibly due to reorganization of the atoms in the NC. Using the new UPS interpretation methodology

Nanocrystal/sol-gel nanocomposites

DOEpatents

Klimov, Victor L.; Petruska, Melissa A.

2010-05-25

The present invention is directed to a process for preparing a solid composite having colloidal nanocrystals dispersed within a sol-gel matrix, the process including admixing colloidal nanocrystals with an amphiphilic polymer including hydrophilic groups selected from the group consisting of --COOH, --OH, --SO.sub.3H, --NH.sub.2, and --PO.sub.3H.sub.2 within a solvent to form an alcohol-soluble colloidal nanocrystal-polymer complex, admixing the alcohol-soluble colloidal nanocrystal-polymer complex and a sol-gel precursor material, and, forming the solid composite from the admixture. The present invention is also directed to the resultant solid composites and to the alcohol-soluble colloidal nanocrystal-polymer complexes.

Solution-Processed Transistors Using Colloidal Nanocrystals with Composition-Matched Molecular "Solders": Approaching Single Crystal Mobility.

PubMed

Jang, Jaeyoung; Dolzhnikov, Dmitriy S; Liu, Wenyong; Nam, Sooji; Shim, Moonsub; Talapin, Dmitri V

2015-10-14

Crystalline silicon-based complementary metal-oxide-semiconductor transistors have become a dominant platform for today's electronics. For such devices, expensive and complicated vacuum processes are used in the preparation of active layers. This increases cost and restricts the scope of applications. Here, we demonstrate high-performance solution-processed CdSe nanocrystal (NC) field-effect transistors (FETs) that exhibit very high carrier mobilities (over 400 cm(2)/(V s)). This is comparable to the carrier mobilities of crystalline silicon-based transistors. Furthermore, our NC FETs exhibit high operational stability and MHz switching speeds. These NC FETs are prepared by spin coating colloidal solutions of CdSe NCs capped with molecular solders [Cd2Se3](2-) onto various oxide gate dielectrics followed by thermal annealing. We show that the nature of gate dielectrics plays an important role in soldered CdSe NC FETs. The capacitance of dielectrics and the NC electronic structure near gate dielectric affect the distribution of localized traps and trap filling, determining carrier mobility and operational stability of the NC FETs. We expand the application of the NC soldering process to core-shell NCs consisting of a III-V InAs core and a CdSe shell with composition-matched [Cd2Se3](2-) molecular solders. Soldering CdSe shells forms nanoheterostructured material that combines high electron mobility and near-IR photoresponse.

PyNCS: a microkernel for high-level definition and configuration of neuromorphic electronic systems

PubMed Central

Stefanini, Fabio; Neftci, Emre O.; Sheik, Sadique; Indiveri, Giacomo

2014-01-01

Neuromorphic hardware offers an electronic substrate for the realization of asynchronous event-based sensory-motor systems and large-scale spiking neural network architectures. In order to characterize these systems, configure them, and carry out modeling experiments, it is often necessary to interface them to workstations. The software used for this purpose typically consists of a large monolithic block of code which is highly specific to the hardware setup used. While this approach can lead to highly integrated hardware/software systems, it hampers the development of modular and reconfigurable infrastructures thus preventing a rapid evolution of such systems. To alleviate this problem, we propose PyNCS, an open-source front-end for the definition of neural network models that is interfaced to the hardware through a set of Python Application Programming Interfaces (APIs). The design of PyNCS promotes modularity, portability and expandability and separates implementation from hardware description. The high-level front-end that comes with PyNCS includes tools to define neural network models as well as to create, monitor and analyze spiking data. Here we report the design philosophy behind the PyNCS framework and describe its implementation. We demonstrate its functionality with two representative case studies, one using an event-based neuromorphic vision sensor, and one using a set of multi-neuron devices for carrying out a cognitive decision-making task involving state-dependent computation. PyNCS, already applicable to a wide range of existing spike-based neuromorphic setups, will accelerate the development of hybrid software/hardware neuromorphic systems, thanks to its code flexibility. The code is open-source and available online at https://github.com/inincs/pyNCS. PMID:25232314

PyNCS: a microkernel for high-level definition and configuration of neuromorphic electronic systems.

PubMed

Stefanini, Fabio; Neftci, Emre O; Sheik, Sadique; Indiveri, Giacomo

2014-01-01

Neuromorphic hardware offers an electronic substrate for the realization of asynchronous event-based sensory-motor systems and large-scale spiking neural network architectures. In order to characterize these systems, configure them, and carry out modeling experiments, it is often necessary to interface them to workstations. The software used for this purpose typically consists of a large monolithic block of code which is highly specific to the hardware setup used. While this approach can lead to highly integrated hardware/software systems, it hampers the development of modular and reconfigurable infrastructures thus preventing a rapid evolution of such systems. To alleviate this problem, we propose PyNCS, an open-source front-end for the definition of neural network models that is interfaced to the hardware through a set of Python Application Programming Interfaces (APIs). The design of PyNCS promotes modularity, portability and expandability and separates implementation from hardware description. The high-level front-end that comes with PyNCS includes tools to define neural network models as well as to create, monitor and analyze spiking data. Here we report the design philosophy behind the PyNCS framework and describe its implementation. We demonstrate its functionality with two representative case studies, one using an event-based neuromorphic vision sensor, and one using a set of multi-neuron devices for carrying out a cognitive decision-making task involving state-dependent computation. PyNCS, already applicable to a wide range of existing spike-based neuromorphic setups, will accelerate the development of hybrid software/hardware neuromorphic systems, thanks to its code flexibility. The code is open-source and available online at https://github.com/inincs/pyNCS.

A room-temperature-operated Si LED with β-FeSi2 nanocrystals in the active layer: μW emission power at 1.5 μm

NASA Astrophysics Data System (ADS)

Shevlyagin, A. V.; Goroshko, D. L.; Chusovitin, E. A.; Balagan, S. A.; Dotsenko, S. A.; Galkin, K. N.; Galkin, N. G.; Shamirzaev, T. S.; Gutakovskii, A. K.; Latyshev, A. V.; Iinuma, M.; Terai, Y.

2017-03-01

This article describes the development of an Si-based light-emitting diode with β-FeSi2 nanocrystals embedded in the active layer. Favorable epitaxial conditions allow us to obtain a direct band gap type-I band alignment Si/β-FeSi2 nanocrystals/Si heterostructure with optical transition at a wavelength range of 1500-1550 nm at room temperature. Transmission electron microscopy data reveal strained, defect-free β-FeSi2 nanocrystals of diameter 6 and 25 nm embedded in the Si matrix. Intense electroluminescence was observed at a pumping current density as low as 0.7 A/cm2. The device reached an optical emission power of up to 25 μW at 9 A/cm2 with an external quantum efficiency of 0.009%. Watt-Ampere characteristic linearity suggests that the optical power margin of the light-emitting diode has not been exhausted. Band structure calculations explain the luminescence as being mainly due to radiative recombination in the large β-FeSi2 nanocrystals resulting from the realization of an indirect-to-direct band gap electronic configuration transformation arising from a favorable deformation of nanocrystals. The direct band gap structure and the measured short decay time of the luminescence of several tens of ns give rise to a fast operation speed for the device. Thus a method for developing a silicon-based photonic integrated circuit, combining complementary metal-oxide-semiconductor technology functionality and near-infrared light emission, is reported here.

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.

Fabrication of all-inorganic nanocrystal solids through matrix encapsulation of nanocrystal arrays.

PubMed

Kinder, Erich; Moroz, Pavel; Diederich, Geoffrey; Johnson, Alexa; Kirsanova, Maria; Nemchinov, Alexander; O'Connor, Timothy; Roth, Dan; Zamkov, Mikhail

2011-12-21

A general strategy for low-temperature processing of colloidal nanocrystals into all-inorganic films is reported. The present methodology goes beyond the traditional ligand-interlinking scheme and relies on encapsulation of morphologically defined nanocrystal arrays into a matrix of a wide-band gap semiconductor, which preserves optoelectronic properties of individual nanoparticles while rendering the nanocrystal film photoconductive. Fabricated solids exhibit excellent thermal stability, which is attributed to the heteroepitaxial structure of nanocrystal-matrix interfaces, and show compelling light-harvesting performance in prototype solar cells. © 2011 American Chemical Society

Energy Transfer Efficiency from ZnO-Nanocrystals to Eu3+ Ions Embedded in SiO₂ Film for Emission at 614 nm.

PubMed

Mangalam, Vivek; Pita, Kantisara

2017-08-10

In this work, we study the energy transfer mechanism from ZnO nanocrystals (ZnO-nc) to Eu 3+ ions by fabricating thin-film samples of ZnO-nc and Eu 3+ ions embedded in a SiO₂ matrix using the low-cost sol-gel technique. The time-resolved photoluminescence (TRPL) measurements from the samples were analyzed to understand the contribution of energy transfer from the various ZnO-nc emission centers to Eu 3+ ions. The decay time obtained from the TRPL measurements was used to calculate the energy transfer efficiencies from the ZnO-nc emission centers, and these results were compared with the energy transfer efficiencies calculated from steady-state photoluminescence emission results. The results in this work show that high transfer efficiencies from the excitonic and Zn defect emission centers is mostly due to the energy transfer from ZnO-nc to Eu 3+ ions which results in the radiative emission from the Eu 3+ ions at 614 nm, while the energy transfer from the oxygen defect emissions is most probably due to the energy transfer from ZnO-nc to the new defects created due to the incorporation of the Eu 3+ ions.

Magneto-optical Faraday rotation of semiconductor nanoparticles embedded in dielectric matrices.

PubMed

Savchuk, Andriy I; Stolyarchuk, Ihor D; Makoviy, Vitaliy V; Savchuk, Oleksandr A

2014-04-01

Faraday rotation has been studied for CdS, CdTe, and CdS:Mn semiconductor nanoparticles synthesized by colloidal chemistry methods. Additionally these materials were prepared in a form of semiconductor nanoparticles embedded in polyvinyl alcohol films. Transmission electron microscopy and atomic force microscopy analyses served as confirmation of nanocrystallinity and estimation of the average size of the nanoparticles. Spectral dependence of the Faraday rotation for the studied nanocrystals and nanocomposites is correlated with a blueshift of the absorption edge due to the confinement effect in zero-dimensional structures. Faraday rotation spectra and their temperature behavior in Mn-doped nanocrystals demonstrates peculiarities, which are associated with s, p-d exchange interaction between Mn²⁺ ions and band carriers in diluted magnetic semiconductor nanostructures.

Silicon-containing polymer-derived ceramic nanocomposites (PDC-NCs): preparative approaches and properties.

PubMed

Ionescu, Emanuel; Kleebe, Hans-Joachim; Riedel, Ralf

2012-08-07

Composites consist by definition of at least two materials (Gibbsian phases) with rather different properties. They exhibit a heterogeneous microstructure and possess improved properties with respect to their components. Furthermore, the design of their microstructure allows for tailoring their overall properties. In the last decades, intense work was performed on the synthesis of nanocomposites, which have the feature that at least one of their components is nanoscaled. However, the microstructure-property relationship of nanocomposite materials is still a challenging topic. This tutorial review paper deals with a special class of nanocomposites, i.e. polymer-derived ceramic nanocomposites (PDC-NCs), which have been shown to be promising materials for various structural and functional applications. Within this context, different preparative approaches for PDC-NCs as well as some of their properties will be presented and discussed. Furthermore, recent results concerning the relationship between the nano/microstructure of PDC-NCs and their properties will be highlighted.

Silicon nanocrystal inks, films, and methods

DOEpatents

Wheeler, Lance Michael; Kortshagen, Uwe Richard

2015-09-01

Silicon nanocrystal inks and films, and methods of making and using silicon nanocrystal inks and films, are disclosed herein. In certain embodiments the nanocrystal inks and films include halide-terminated (e.g., chloride-terminated) and/or halide and hydrogen-terminated nanocrystals of silicon or alloys thereof. Silicon nanocrystal inks and films can be used, for example, to prepare semiconductor devices.

Synthesis, crystal structure and DFT studies of a Zinc(II) complex of 1,3-diaminopropane (Dap), [Zn(Dap)(NCS)2][Zn(Dap)(NCS)2]n. The additional stabilizing role of S⋯π chalcogen bond

NASA Astrophysics Data System (ADS)

Alotaibi, Mshari A.; Alharthi, Abdulrahman I.; Zierkiewicz, Wiktor; Akhtar, Muhammad; Tahir, Muhammad Nawaz; Mazhar, Muhammad; Isab, Anvarhusein A.; Ahmad, Saeed

2017-04-01

A zinc(II) complex of 1,3-diaminopropane (Dap), [Zn(Dap)(NCS)2][Zn(Dap)(NCS)2]n (1) has been prepared and characterized by elemental analysis, IR, 1H &13C NMR spectroscopy, and its crystal structure was determined by X-ray crystallography. The crystal structure of 1 consists of two types of molecules, a discrete monomer and a polymeric one. In the monomeric unit, the zinc atom is bound to one terminal Dap molecule and to two N-bound thiocyanate ions, while in the polymeric unit, Dap acts as a bridging ligand forming a linear chain. The Zn(II) ions in both assume a slightly distorted tetrahedral geometry. The structures of two systems: the [Zn(Dap)(NCS)2][Zn(Dap)(NCS)2]3 complex as a model of 1 and [Zn(Dap)(NCS)2]4 as a simple polymeric structure were optimized with the B3LYP-D3 method. The DFT results support that the experimentally determined structure (1) is more stable in comparison to a simple polymeric structure, [Zn(Dap)(NCS)2]n (2). The interaction energies (ΔE) for NCS anions obtained by B3LYP-D3 method are about -145 kcal mol-1, while the calculated ΔE values for neutral organic ligands are about twice smaller. The X-ray structure of 1 shows that the complex is stabilized mainly by hydrogen bonds. We also found that weak chalcogen bonds play an additional role in stabilization of compound 1. Some of the intermolecular S⋯N distances are smaller than the sum of the van der Waals radii of the corresponding atoms. To the best of our knowledge, this is the first study that shows the structure where the trivalent sulfur is involved in formation of a S⋯π chalcogen bond. The NBO and NCI analyses confirm the existence of this kind of interactions.

Unified random access memory (URAM) by integration of a nanocrystal floating gate for nonvolatile memory and a partially depleted floating body for capacitorless 1T-DRAM

NASA Astrophysics Data System (ADS)

Ryu, Seong-Wan; Han, Jin-Woo; Kim, Chung-Jin; Kim, Sungho; Choi, Yang-Kyu

2009-03-01

This paper describes a unified memory (URAM) that utilizes a nanocrystal SOI MOSFET for multi-functional applications of both nonvolatile memory (NVM) and capacitorless 1T-DRAM. By using a discrete storage node (Ag nanocrystal) as the floating gate of the NVM, high defect immunity and 2-bit/cell operation were achieved. The embedded nanocrystal NVM also showed 1T-DRAM operation (program/erase time = 100 ns) characteristics, which were realized by storing holes in the floating body of the SOI MOSFET, without requiring an external capacitor. Three-bit/cell operation was accomplished for different applications - 2-bits for nonvolatility and 1-bit for fast operation.

The National Comorbidity Survey Adolescent Supplement (NCS-A): II. Overview and Design

PubMed Central

Kessler, Ronald C.; Avenevoli, Shelli; Costello, E. Jane; Green, Jennifer Greif; Gruber, Michael J.; Heeringa, Steven; Merikangas, Kathleen R.; Pennell, Beth-Ellen; Sampson, Nancy A.; Zaslavsky, Alan M.

2009-01-01

OBJECTIVE To present an overview of the design and field procedures of the National Comorbidity Survey Replication Adolescent Supplement (NCS-A) METHOD The NCS-A is a nationally representative face-to-face household survey of the prevalence and correlates of DSM-IV mental disorders among US adolescents (ages 13–17) that was carried out between February 2001 and January 2004 by the Survey Research Center of the Institute for Social Research at the University of Michigan. The sample was based on a dual-frame design that included 904 adolescent residents of the households that participated in the National Comorbidity Survey Replication (85.9% response rate) and 9244 adolescent students selected from a representative sample of 320 schools in the same nationally representative sample of counties as the NCS-R (74.7% response rate). RESULTS Comparisons of sample and population distributions on Census socio-demographic variables and, in the school sample, school characteristics documented only minor differences that were corrected with post-stratification weighting. Comparisons of DSM-IV disorder prevalence estimates among household vs. school sample respondents in counties that differed in the use of replacement schools for originally selected schools that refused to participate showed that the use of replacement schools did not introduce bias into prevalence estimates. CONCLUSIONS The NCS-A is a rich nationally representative dataset that will substantially increase understanding of the mental health and well-being of adolescents in the United States. PMID:19242381

A comparative study of CO adsorption on tetrahexahedral Pt nanocrystals and interrelated Pt single crystal electrodes by using cyclic voltammetry and in situ FTIR spectroscopy.

PubMed

Liu, Hai-Xia; Tian, Na; Ye, Jin-Yu; Lu, Bang-An; Ren, Jie; Huangfu, Zhi-Chao; Zhou, Zhi-You; Sun, Shi-Gang

2014-01-01

This study focuses on CO adsorption at tetrahexahedral Pt nanocrystals (THH Pt NCs) by using cyclic voltammetry and in situ FTIR spectroscopy. Since the electrochemically prepared THH Pt NCs in this study are enclosed by {730} facets which could be considered by a subfacet configuration of 2{210} + {310}, we have also studied CO adsorption on the interrelated Pt(310) and Pt(210) single crystal electrodes as a comparison. Cyclic voltammetry results demonstrated that CO adsorbs dominantly on the (100) sites of THH Pt NCs at low CO coverage (θ(CO)≤ 0.135), while on both (100) and (110) sites at higher CO coverage. On ordered Pt(310) and Pt(210), i.e. they were flame annealed and then cooled in H(2) + Ar, CO adsorption also illustrates relative priority on (100) sites at low CO coverage; while at high CO coverage or on oxygen-disordered Pt(310) and Pt(210) when they were cooled in air after flame annealing, the adsorption of CO presents a weak preference on (100) sites of Pt(310) and even no preference at all on (100) sites of Pt(210). In situ FTIR spectroscopic studies illustrated that CO adsorption on THH Pt NCs yields anomalous infrared effects (AIREs), which are depicted by the Fano-like IR feature on a dense distribution (60 μm(-2)) and the enhancement of abnormal IR absorption on a sparse distribution (22 μm(-2)) of THH Pt NCs on glassy carbon substrate. Systematic investigation of CO coverage dependence of IR features revealed that, on THH Pt NCs, the IR band center (ν(COL)) of linearly bonded CO (COL) is rapidly shifted to higher wavenumbers along with the increase of CO coverage to 0.184, yielding a fast linear increase rate with a high slope (dν(COL)/dθ(IR)(CO) = 219 cm(-1)); when θ > 0.184, the increase of ν(COL) with θCO slows down and deviates drastically from linearity. In contrast, the ν(COL) on the ordered Pt(310) electrode maintains a linear increase with θ(IR)(CO) for the whole range of θ(IR)(CO) variation, and gives a much smaller

Fenofibrate Nanocrystals Embedded in Oral Strip-Films for Bioavailability Enhancement

PubMed Central

Barvaliya, Manish; Zhang, Lu; Anovadiya, Ashish; Brahmbhatt, Harshad; Paul, Parimal; Tripathi, Chandrabhanu

2018-01-01

The aim of the present study was to make a fenofibrate (FNB) nanocrystal (NC) by wet media milling, characterizations and formulates into oral strip-films (OSFs). Mechanical properties, redispersion study, and solid-state characterizations results suggested that reduction of drug crystal size at nanoscale and incorporation into OSFs does not affect the solid-state properties of the drug. In vitro dissolution kinetics showed enhanced dissolution rate was easily manipulated by changing the thickness of the OSF. In situ UV-imaging was used to monitor drug dissolution qualitatively and quantitatively in real time. Results confirm that the intrinsic dissolution rates and surface drug concentration measured with this device were in agreement with the USP-IV dissolution profiles. In vivo pharmacokinetics in rabbits showed a significant difference in the pharmacokinetics parameter (1.4 fold increase bioavailability) of FNB NC-loaded OSFs as compared to the marketed formulation “Tricor” and as-received (pristine) drug. This approach of drug nanocrystallization and incorporation into OSFs may have significant applications in cost-effective tools for bioavailability enhancement of FNB. PMID:29438297

The Small RNA ncS35 Regulates Growth in Burkholderia cenocepacia J2315

PubMed Central

Kiekens, Sanne; Sass, Andrea; Van Nieuwerburgh, Filip; Deforce, Dieter

2018-01-01

ABSTRACT Burkholderia cenocepacia J2315 is a member of the B. cepacia complex. It has a large genome with three replicons and one plasmid; 7,261 genes code for annotated proteins, while 113 code for functional RNAs. Small regulatory RNAs of B. cenocepacia have not yet been functionally characterized. We investigated a small regulatory RNA, designated ncS35, that was discovered by differential RNA sequencing. Its expression under various conditions was quantified, and a deletion mutant, ΔncS35, was constructed. Compared to planktonic growth in a rich medium, the expression of ncS35 was elevated when B. cenocepacia J2315 was grown in biofilms and in minimal medium. Cells of the deletion mutant showed increased aggregation, higher metabolic activity, a higher growth rate, and an increased susceptibility to tobramycin. A transcriptomic analysis revealed upregulation of the phenylacetic acid and tryptophan degradation pathways in ΔncS35. Computational target prediction indicated that ncS35 likely interacts with the first gene of the tryptophan degradation pathway. Overall, we demonstrated that small RNA ncS35 is a noncoding RNA with an attenuating effect on the metabolic rate and growth. It is possible that slower growth protects B. cenocepacia J2315 against stressors acting on fast-dividing cells and enhances survival under unfavorable conditions. IMPORTANCE Small RNAs play an important role in the survival of bacteria in diverse environments. We explored the physiological role of ncS35, a small RNA expressed in B. cenocepacia J2315, an opportunistic pathogen in cystic fibrosis patients. In cystic fibrosis patients, infections can lead to “cepacia syndrome,” a rapidly progressing and often fatal pneumonia. Infections with Burkholderia spp. are difficult to threat with antibiotics because of their high intrinsic resistance and ability to form biofilms. We show that ncS35 attenuates the growth and reduces the metabolic rate of B. cenocepacia and influences

Thermomechanical Properties of Lignin-Based Electrospun Nanofibers and Films Reinforced with Cellulose Nanocrystals: A Dynamic Mechanical and Nanoindentation Study

Treesearch

Mariko Ago; Joseph E. Jakes; Orlando J. Rojas

2013-01-01

We produced defect-free electrospun fibers from aqueous dispersions of lignin, poly(vinyl alcohol) (PVA), and cellulose nanocrystals (CNCs), which were used as reinforcing nanoparticles. The thermomechanical performance of the lignin-based electrospun fibers and the spin-coated thin films was improved when they were embedded with CNCs. Isochronal dynamic mechanical...

Atomistic simulation of the thermal conductivity in amorphous SiO2 matrix/Ge nanocrystal composites

NASA Astrophysics Data System (ADS)

Kuryliuk, Vasyl V.; Korotchenkov, Oleg A.

2017-04-01

We use nonequilibrium molecular dynamics computer simulations with the Tersoff potential aiming to provide a comprehensive picture of the thermal conductivity of amorphous SiO2 (a-SiO2) matrix with embedded Ge nanocrystals (nc-Ge). The modelling predicts the a-SiO2 matrix thermal conductivity in a temperature range of 50 < T < 500 K yielding a fair agreement with experiment at around room temperature. It is worth noticing that the predicted room-temperature thermal conductivity in a-SiO2 is in very good agreement with the experimental result, which is in marked contrast with the thermal conductivity calculated employing the widely used van Beest-Kramer-van Santen (BKS) potential. We show that the thermal conductivity of composite nc-Ge/a-SiO2 systems decreases steadily with increasing the volume fraction of Ge inclusions, indicative of enhanced interface scattering of phonons imposed by embedded Ge nanocrystals. We also observe that increasing the volume fractions above a certain threshold value results in a progressively increased thermal conductivity of the nanocomposite, which can be explained by increasing volume fraction of a better thermally conducting Ge. Finally, non-equilibrium molecular dynamics simulations with the Tersoff potential are promising for computing the thermal conductivity of nanocomposites based on amorphous SiO2 and can be readily scaled to more complex composite structures with embedded nanoparticles, which thus help design nanocomposites with desired thermal properties.

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.

Semiconductor nanocrystal-based phagokinetic tracking

DOEpatents

Alivisatos, A Paul; Larabell, Carolyn A; Parak, Wolfgang J; Le Gros, Mark; Boudreau, Rosanne

2014-11-18

Methods for determining metabolic properties of living cells through the uptake of semiconductor nanocrystals by cells. Generally the methods require a layer of neutral or hydrophilic semiconductor nanocrystals and a layer of cells seeded onto a culture surface and changes in the layer of semiconductor nanocrystals are detected. The observed changes made to the layer of semiconductor nanocrystals can be correlated to such metabolic properties as metastatic potential, cell motility or migration.

Heterogeneous Nature of Relaxation Dynamics of Room-Temperature Ionic Liquids (EMIm) 2[Co(NCS) 4] and (BMIm) 2[Co(NCS) 4

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

Hensel-Bielowka, Stella; Wojnarowska, Zaneta; Dzida, Marzena

2015-08-11

Dynamic crossover above T g has been recognized as a characteristic feature of molecular dynamics of liquids approaching glass transition. Experimentally, it is manifested as a change in Vogel–Fulcher–Tammann dependence or a breakdown of the Stokes–Einstein and related relations. In this study, we report the exception from this rather general pattern of behavior. By means of dielectric, ultrasonic, rheological, and calorimetric methods, dynamics of two good ionic conductors (BMIm) 2[Co(NCS) 4] and (EMIm) 2[Co(NCS) 4] of less common stoichiometry (2:1) was studied in a very broad temperature range. However, none of the mentioned dynamic changes was observed in the entiremore » studied temperature range. On the contrary, the single VFT and the same fractional Walden coefficient were found for conductivity and viscosity changes over 12 decades. Finally and moreover, ultrasonic studies revealed that the data at temperatures which cover the normal liquid region cannot be fitted by a single exponential decay, and the Cole–Cole function should be used instead.« less

Heterogeneous nature of relaxation dynamics of room-temperature ionic liquids (EMIm) 2[Co(NCS) 4] and (BMIm) 2[Co(NCS) 4

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

Hensel-Bielowka, Stella; Wojnarowska, Zaneta E.; Dzida, Marzena

2015-08-11

Dynamic crossover above T g has been recognized as a characteristic feature of molecular dynamics of liquids approaching glass transition. Experimentally, it is manifested as a change in Vogel Fulcher Tammann dependence or a breakdown of the Stokes Einstein and related relations. In this paper, we report the exception from this rather general pattern of behavior. By means of dielectric, ultrasonic, rheological, and calorimetric methods, dynamics of two good ionic conductors (BMIm) 2[Co(NCS) 4] and (EMIm) 2[Co(NCS) 4] of less common stoichiometry (2:1) was studied in a very broad temperature range. However, none of the mentioned dynamic changes was observedmore » in the entire studied temperature range. On the contrary, the single VFT and the same fractional Walden coefficient were found for conductivity and viscosity changes over 12 decades. Furthermore, ultrasonic studies revealed that the data at temperatures which cover the normal liquid region cannot be fitted by a single exponential decay, and the Cole Cole function should be used instead.« less

Rationally Controlled Synthesis of CdSexTe1-x Alloy Nanocrystals and Their Application in Efficient Graded Bandgap Solar Cells.

PubMed

Wen, Shiya; Li, Miaozi; Yang, Junyu; Mei, Xianglin; Wu, Bin; Liu, Xiaolin; Heng, Jingxuan; Qin, Donghuan; Hou, Lintao; Xu, Wei; Wang, Dan

2017-11-08

CdSe x Te 1-x semiconductor nanocrystals (NCs), being rod-shaped/irregular dot-shaped in morphology, have been fabricated via a simple hot-injection method. The NCs composition is well controlled through varying molar ratios of Se to Te precursors. Through changing the composition of the CdSe x Te 1-x NCs, the spectral absorption of the NC thin film between 570-800 nm is proved to be tunable. It is shown that the bandgap of homogeneously alloyed CdSe x Te 1-x active thin film is nonlinearly correlated with the different compositions, which is perceived as optical bowing. The solar cell devices based on CdSe x Te 1-x NCs with the structure of ITO/ZnO/CdSe/CdSe x Te 1-x /MoO x /Au and the graded bandgap ITO/ZnO/CdSe( w / o )/CdSe x Te 1-x /CdTe/MoO x /Au are systematically evaluated. It was found that the performance of solar cells degrades almost linearly with the increase of alloy NC film thickness with respect to ITO/ZnO/CdSe/CdSe 0.2 Te 0.8 /MoO x /Au. From another perspective, in terms of the graded bandgap structure of ITO/ZnO/CdSe/CdSe x Te 1-x /CdTe/MoO x /Au, the performance is improved in contrast with its single-junction analogues. The graded bandgap structure is proved to be efficient when absorbing spectrum and the solar cells fabricated under the structure of ITO/ZnO/CdSe 0.8 Te 0.2 /CdSe 0.2 Te 0.8 /CdTe/MoO x /Au indicate power conversion efficiency (PCE) of 6.37%, a value among the highest for solution-processed inversely-structured CdSe x Te 1-x NC solar cells. As the NC solar cells are solution-processed under environmental conditions, they are promising for fabricating solar cells at low cost, roll by roll and in large area.

Origin of stretched-exponential photoluminescence relaxation in size-separated silicon nanocrystals

DOE PAGES

Brown, Samuel L.; Krishnan, Retheesh; Elbaradei, Ahmed; ...

2017-05-25

A detailed understanding of the photoluminescence (PL) from silicon nanocrystals (SiNCs) is convoluted by the complexity of the decay mechanism, including a stretched-exponential relaxation and the presence of both nanosecond and microsecond time scales. In this publication, we analyze the microsecond PL decay of size-resolved SiNC fractions in both full-spectrum (FS) and spectrally resolved (SR) configurations, where the stretching exponent and lifetime are used to deduce a probability distribution function (PDF) of decay rates. For the PL decay measured at peak emission, we find a systematic shift and narrowing of the PDF in comparison to the FS measurements. In amore » similar fashion, we resolve the PL lifetime of the ‘blue’, ‘peak’, and ‘red’ regions of the spectrum and map PL decays of different photon energy onto their corresponding location in the PDF. Furthermore, a general trend is observed where higher and lower photon energies are correlated with shorter and longer lifetimes, respectively, which we relate to the PL line width and electron-phonon coupling.« less

Oxygen plasma immersion ion implantation treatment to enhance data retention of tungsten nanocrystal nonvolatile memory

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

Wang, Jer-Chyi, E-mail: jcwang@mail.cgu.edu.tw; Chang, Wei-Cheng; Lai, Chao-Sung, E-mail: cslai@mail.cgu.edu.tw

Data retention characteristics of tungsten nanocrystal (W-NC) memory devices using an oxygen plasma immersion ion implantation (PIII) treatment are investigated. With an increase of oxygen PIII bias voltage and treatment time, the capacitance–voltage hysteresis memory window is increased but the data retention characteristics become degraded. High-resolution transmission electron microscopy images show that this poor data retention is a result of plasma damage on the tunneling oxide layer, which can be prevented by lowering the bias voltage to 7 kV. In addition, by using the elevated temperature retention measurement technique, the effective charge trapping level of the WO{sub 3} film surrounding themore » W-NCs can be extracted. This measurement reveals that a higher oxygen PIII bias voltage and treatment time induces more shallow traps within the WO{sub 3} film, degrading the retention behavior of the W-NC memory.« less

Silicon nanocrystals as handy biomarkers

NASA Astrophysics Data System (ADS)

Fujioka, Kouki; Hoshino, Akiyoshi; Manabe, Noriyoshi; Futamura, Yasuhiro; Tilley, Richard; Yamamoto, Kenji

2007-02-01

Quantum dots (QDs) have brighter and longer fluorescence than organic dyes. Therefore, QDs can be applied to biotechnology, and have capability to be applied to medical technology. Currently, among the several types of QDs, CdSe with a ZnS shell is one of the most popular QDs to be used in biological experiments. However, when the CdSe QDs were applied to clinical technology, potential toxicological problems due to CdSe core should be considered. To eliminate the problem, silicon nanocrystals, which have the potential of biocompatibility, could be a candidate of alternate probes. Silicon nanocrystals have been synthesized using several techniques such as aerosol, electrochemical etching, laser pyrolysis, plasma deposition, and colloids. Recently, the silicon nanocrystals were reported to be synthesized in inverse micelles and also stabilized with 1-heptene or allylamine capping. Blue fluorescence of the nanocrystals was observed when excited with a UV light. The nanocrystals covered with 1-heptene are hydrophobic, whereas the ones covered with allylamine are hydrophilic. To test the stability in cytosol, the water-soluble nanocrystals covered with allylamine were examined with a Hela cell incorporation experiment. Bright blue fluorescence of the nanocrystals was detected in the cytosol when excited with a UV light, implying that the nanocrystals were able to be applied to biological imaging. In order to expand the application range, we synthesized and compared a series of silicon nanocrystals, which have variable surface modification, such as alkyl group, alcohol group, and odorant molecules. This study will provide a wider range of optoelectronic applications and bioimaging technology.

Development and characterization of lecithin stabilized glibenclamide nanocrystals for enhanced solubility and drug delivery.

PubMed

Kumar, B Sajeev; Saraswathi, R; Kumar, K Venkates; Jha, S K; Venkates, D P; Dhanaraj, S A

2014-05-01

Novel LNCs (lipid nanocrystals) were developed with an aim to improve the solubility, stability and targeting efficiency of the model drug glibenclamide (GLB). PEG 20000, Tween 80 and soybean lecithin were used as polymer, surfactant and complexing agent, respectively. GLB nanocrystals (NCs) were prepared by precipitation process and complexed using hot and cold melt technique. The LNCs were evaluated by drug loading, saturation solubility (SL), optical clarity, in vitro dissolution, solid state characterization, in vivo and stability analysis. LNCs exhibited a threefold increase in SL and a higher dissolution rate than GLB. The percentage dissolution efficiency was found to decrease with increase in PEG 20000. The average particle size was in the range of 155-842 nm and zeta potential values tend to increase after complexation. X-ray powder diffractometry and differential scanning calorimetry results proved the crystallinity prevailed in the samples. Spherical shaped particles (<1000 nm) with a lipid coat on the surface were observed in scanning electron microscopy analysis. Fourier transform infrared results proved the absence of interaction between drug and polymer and stability study findings proved that LNCs were stable. In vivo study findings showed a decrease in drug concentration to pancreas in male Wistar rats. It can be concluded that LNCs are could offer enhanced solubility, dissolution rate and stability for poorly water soluble drugs. The targeting efficiency of LNCs was decreased and further membrane permeability studies ought to be carried out.

Switchable Ni–Mn–Ga Heusler nanocrystals

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

Zayak, Alexey T.; Beckman, Scott P.; Tiago, Murilo L.

2008-10-02

Here, we examined bulk-like Heusler nanocrystals using real-space pseudopotentials constructed within density functional theory. The nanocrystals were made of various compositions of Ni-Mn-Ga in the size range from 15 up to 169 atoms. Among these compositions, the closest to the stoichiometric Ni 2MnGa were found to be the most stable. The Ni-based nanocrystals retained a tendency for tetragonal distortion, which is inherited from the bulk properties. Surface effects suppress the tetragonal structure in the smaller Ni-based nanocrystals, while bigger nanocrystals develop a bulk-like tetragonal distortion. We suggest the possibility of switchable Ni-Mn-Ga nanocrystals, which could be utilized for magnetic nano-shape-memorymore » applications.« less

Charge Transport in Semiconductor Nanocrystal Solids

NASA Astrophysics Data System (ADS)

Talapin, Dmitri; Shevchenko, Elena; Lee, Jong Soo; Urban, Jeffrey; Mitzi, David; Murray, Christopher

2007-03-01

Self-assembly of chemically-synthesized nanocrystals can yield complex long-range ordered structures which can be used as model systems for studying transport phenomena in low-dimensional materials [1]. Treatment of close-packed PbSe nanocrystal arrays with hydrazine enhanced exchange coupling between the nanocrystals and improved conductance by more than ten orders of magnitude compared to native nanocrystal films [2]. The conductivity of PbSe nanocrystal solids can be switched between n- and p-type transports by controlling the saturation of electronic states at nanocrystal surfaces. Nanocrystal arrays form the n- and p-channels of field-effect transistors with electron and hole mobilities of 2.5 cm^2V-1s-1 and 0.3 cm^2V-1s-1, respectively, and current modulation Ion/Ioff˜10^3-10^4. The field-effect mobility in PbSe nanocrystal arrays is higher than the mobility of organic transistors while the easy switch between n- and p-transport allows realization of complimentary circuits and p-n junctions for nanocrystal-based solar cells and thermoelectric devices. [1] E. V. Shevchenko, D. V. Talapin, N. A. Kotov, S. O'Brien, C. B. Murray. Nature 439, 55 (2006). [2] D. V. Talapin, C. B. Murray. Science 310, 86 (2005).

Rationally Controlled Synthesis of CdSexTe1−x Alloy Nanocrystals and Their Application in Efficient Graded Bandgap Solar Cells

PubMed Central

Wen, Shiya; Li, Miaozi; Yang, Junyu; Mei, Xianglin; Wu, Bin; Liu, Xiaolin; Heng, Jingxuan; Hou, Lintao; Xu, Wei; Wang, Dan

2017-01-01

CdSexTe1−x semiconductor nanocrystals (NCs), being rod-shaped/irregular dot-shaped in morphology, have been fabricated via a simple hot-injection method. The NCs composition is well controlled through varying molar ratios of Se to Te precursors. Through changing the composition of the CdSexTe1−x NCs, the spectral absorption of the NC thin film between 570–800 nm is proved to be tunable. It is shown that the bandgap of homogeneously alloyed CdSexTe1−x active thin film is nonlinearly correlated with the different compositions, which is perceived as optical bowing. The solar cell devices based on CdSexTe1−x NCs with the structure of ITO/ZnO/CdSe/CdSexTe1−x/MoOx/Au and the graded bandgap ITO/ZnO/CdSe(w/o)/CdSexTe1−x/CdTe/MoOx/Au are systematically evaluated. It was found that the performance of solar cells degrades almost linearly with the increase of alloy NC film thickness with respect to ITO/ZnO/CdSe/CdSe0.2Te0.8/MoOx/Au. From another perspective, in terms of the graded bandgap structure of ITO/ZnO/CdSe/CdSexTe1−x/CdTe/MoOx/Au, the performance is improved in contrast with its single-junction analogues. The graded bandgap structure is proved to be efficient when absorbing spectrum and the solar cells fabricated under the structure of ITO/ZnO/CdSe0.8Te0.2/CdSe0.2Te0.8/CdTe/MoOx/Au indicate power conversion efficiency (PCE) of 6.37%, a value among the highest for solution-processed inversely-structured CdSexTe1−x NC solar cells. As the NC solar cells are solution-processed under environmental conditions, they are promising for fabricating solar cells at low cost, roll by roll and in large area. PMID:29117132

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.

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

All-in-One Cellulose Nanocrystals for 3D Printing of Nanocomposite Hydrogels.

PubMed

Wang, Jieping; Chiappone, Annalisa; Roppolo, Ignazio; Shao, Feng; Fantino, Erika; Lorusso, Massimo; Rentsch, Daniel; Dietliker, Kurt; Pirri, Candido Fabrizio; Grützmacher, Hansjörg

2018-02-23

Cellulose nanocrystals (CNCs) with >2000 photoactive groups on each can act as highly efficient initiators for radical polymerizations, cross-linkers, as well as covalently embedded nanofillers for nanocomposite hydrogels. This is achieved by a simple and reliable method for surface modification of CNCs with a photoactive bis(acyl)phosphane oxide derivative. Shape-persistent and free-standing 3D structured objects were printed with a mono-functional methacrylate, showing a superior swelling capacity and improved mechanical properties. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electron transfer between colloidal ZnO nanocrystals.

PubMed

Hayoun, Rebecca; Whitaker, Kelly M; Gamelin, Daniel R; Mayer, James M

2011-03-30

Colloidal ZnO nanocrystals capped with dodecylamine and dissolved in toluene can be charged photochemically to give stable solutions in which electrons are present in the conduction bands of the nanocrystals. These conduction-band electrons are readily monitored by EPR spectroscopy, with g* values that correlate with the nanocrystal sizes. Mixing a solution of charged small nanocrystals (e(-)(CB):ZnO-S) with a solution of uncharged large nanocrystals (ZnO-L) caused changes in the EPR spectrum indicative of quantitative electron transfer from small to large nanocrystals. EPR spectra of the reverse reaction, e(-)(CB):ZnO-L + ZnO-S, showed that electrons do not transfer from large to small nanocrystals. Stopped-flow kinetics studies monitoring the change in the UV band-edge absorption showed that reactions of 50 μM nanocrystals were complete within the 5 ms mixing time of the instrument. Similar results were obtained for the reaction of charged nanocrystals with methyl viologen (MV(2+)). These and related results indicate that the electron-transfer reactions of these colloidal nanocrystals are quantitative and very rapid, despite the presence of ~1.5 nm long dodecylamine capping ligands. These soluble ZnO nanocrystals are thus well-defined redox reagents suitable for studies of electron transfer involving semiconductor nanostructures.

Mechanochemical approach for the capping of mixed core CdS/ZnS nanocrystals: Elimination of cadmium toxicity.

PubMed

Bujňáková, Zdenka; Baláž, Matej; Dutková, Erika; Baláž, Peter; Kello, Martin; Mojžišová, Gabriela; Mojžiš, Ján; Vilková, Mária; Imrich, Ján; Psotka, Miroslav

2017-01-15

The wet mechanochemical procedure for the capping of the CdS and CdS/ZnS quantum dot nanocrystals is reported. l-cysteine and polyvinylpyrrolidone (PVP) were used as capping agents. When using l-cysteine, the dissolution of cadmium(II) was almost none for CdS/ZnS nanocrystals. Moreover, prepared CdS- and CdS/ZnS-cysteine nanosuspensions exhibited unimodal particle size distributions with very good stability, which was further supported by the zeta potential measurements. The Fourier-transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopy showed the successful embedment of cysteine into the structure of the nanocrystals. Additionally, the optical properties were examined, and the results showed that the cysteine nanosuspension has promising fluorescence properties. On the other hand, PVP was not determined to be a very suitable capping agent for the present system. In this case, the release of cadmium(II) was higher in comparison to the l-cysteine capped samples. The nanosuspensions were successfully used for in vitro studies on selected cancer cell lines. Using fluorescence microscopy, it was evidenced that the nanocrystals enter the cell and that they can serve as imaging agents in biomedical applications. Copyright © 2016. Published by Elsevier Inc.

Phase separation in SiGe nanocrystals embedded in SiO{sub 2} matrix during high temperature annealing

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

Mogaddam, N. A. P.; Turan, R.; Alagoz, A. S.

2008-12-15

SiGe nanocrystals have been formed in SiO{sub 2} matrix by cosputtering Si, Ge, and SiO{sub 2} independently on Si substrate. Effects of the annealing time and temperature on structural and compositional properties are studied by transmission electron microscopy, x-ray diffraction (XRD), and Raman spectroscopy measurements. It is observed that Ge-rich Si{sub (1-x)}Ge{sub x} nanocrystals do not hold their compositional uniformity when annealed at high temperatures for enough long time. A segregation process leading to separation of Ge and Si atoms from each other takes place. This process has been evidenced by a double peak formation in the XRD and Ramanmore » spectra. We attributed this phase separation to the differences in atomic size, surface energy, and surface diffusion disparity between Si and Ge atoms leading to the formation of nonhomogenous structure consist of a Si-rich SiGe core covered by a Ge-rich SiGe shell. This experimental observation is consistent with the result of reported theoretical and simulation methods.« less

Enhanced electrochemiluminescence quenching of CdS:Mn nanocrystals by CdTe QDs-doped silica nanoparticles for ultrasensitive detection of thrombin.

PubMed

Shan, Yun; Xu, Jing-Juan; Chen, Hong-Yuan

2011-07-01

This work reports an aptasensor for ultrasensitive detection of thrombin based on remarkably efficient energy-transfer induced electrochemiluminescence (ECL) quenching from CdS:Mn nanocrystals (NCs) film to CdTe QDs-doped silica nanoparticles (CdTe/SiO(2) NPs). CdTe/SiO(2) NPs were synthesized via the Stöber method and showed black bodies' strong absorption in a wide spectral range without excitonic emission, which made them excellent ECL quenchers. Within the effective distance of energy scavenging, the ECL quenching efficiency was dependent on the number of CdTe QDs doped into the silica NPs. Using ca. 200 CdTe QDs doped silica NPs on average of 40 nm in diameter as ECL quenching labels, attomolar detection of thrombin was successfully realized. The protein detection involves a competition binding event, based on thrombin replacing CdTe/SiO(2) NPs labeled probing DNA which is hybridized with capturing aptamer immobilized on a CdS:Mn NCs film modified glassy carbon electrode surface by specific aptamer-protein affinity interactions. It results in the displacement of ECL quenching labels from CdS:Mn NCs film and concomitant ECL signal recovery. Owing to the high-content CdTe QDs in silica NP, the increment of ECL intensity (ΔI(ECL)) and the concentration of thrombin showed a double logarithmic linear correlation in the range of 5.0 aM∼5.0 fM with a detection limit of 1aM. And, the aptasensor hardly responded to antibody, bovine serum albumin (BSA), haemoglobin (Hb) and lysozyme, showing good detection selectivity for thrombin. This long-distance energy scavenging could have a promising application perspective in the detection of biological recognition events on a molecular level.

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

Electron transport within transparent assemblies of tin-doped indium oxide colloidal nanocrystals

NASA Astrophysics Data System (ADS)

Grisolia, J.; Decorde, N.; Gauvin, M.; Sangeetha, N. M.; Viallet, B.; Ressier, L.

2015-08-01

Stripe-like compact assemblies of tin-doped indium oxide (ITO) colloidal nanocrystals (NCs) are fabricated by stop-and-go convective self-assembly (CSA). Systematic evaluation of the electron transport mechanisms in these systems is carried out by varying the length of carboxylate ligands protecting the NCs: butanoate (C4), octanoate (C8) and oleate (C18). The interparticle edge-to-edge distance L0, along with a number of carbon atoms in the alkyl chain of the coating ligand, are deduced from small-angle x-ray scattering (SAXS) measurements and exhibit a linear relationship with a slope of 0.11 nm per carbon pair unit. Temperature-dependent resistance characteristics are analyzed using several electron transport models: Efros-Shklovskii variable range hopping (ES-VRH), inelastic cotunneling (IC), regular island array and percolation. The analysis indicated that the first two models (ES-VRH and IC) fail to explain the observed behavior, and that only simple activated transport takes place in these systems under the experimental conditions studied (T = 300 K to 77 K). Related transport parameters were then extracted using the regular island array and percolation models. The effective tunneling decay constant βeff of the ligands and the Coulomb charging energy EC are found to be around 5.5 nm-1 and 25 meV, respectively, irrespective of ligand lengths. The theoretical tunneling decay constant β calculated using the percolation model is in the range 9 nm-1. Electromechanical tests on the ITO nanoparticle assemblies indicate that their sensitivities are as high as ˜30 and remain the same regardless of ligand lengths, which is in agreement with the constant effective βeff extracted from regular island array and percolation models.

First-principles calculations of the magnetic properties of (Cd,Mn)Te nanocrystals

NASA Astrophysics Data System (ADS)

Echeverría-Arrondo, C.; Pérez-Conde, J.; Ayuela, A.

2009-04-01

We investigate the electronic and magnetic properties of Mn-doped CdTe nanocrystals (NCs) with ˜2nm in diameter which can be experimentally synthesized with Mn atoms inside. Using the density-functional theory, we consider two doping cases: NCs containing one or two Mn impurities. Although the Mnd peaks carry five up electrons in the dot, the local magnetic moment on the Mn site is 4.65μB . It is smaller than 5μB because of the sp-d hybridization between the localized 3d electrons of the Mn atoms and the s - and p -type valence states of the host compound. The sp-d hybridization induces small magnetic moments on the Mn-nearest-neighbor Te sites, antiparallel to the Mn moment affecting the p -type valence states of the undoped dot, as usual for a kinetic-mediated exchange magnetic coupling. Furthermore, we calculate the parameters standing for the sp-d exchange interactions. Conduction N0α and valence N0β are close to the experimental bulk values when the Mn impurities occupy bulklike NCs’ central positions, and they tend to zero close to the surface. This behavior is further explained by an analysis of valence-band-edge states showing that symmetry breaking splits the states and in consequence reduces the exchange. For two Mn atoms in several positions, the valence edge states show a further departure from an interpretation based in a perturbative treatment. We also calculate the d-d exchange interactions |Jdd| between Mn spins. The largest |Jdd| value is also for Mn atoms on bulklike central sites; in comparison with the experimental d-d exchange constant in bulk Cd0.95Mn0.05Te , it is four times smaller.

Numerical model of a single nanocrystal devoted to the study of disordered nanocrystal floating gates of new flash memories

NASA Astrophysics Data System (ADS)

Leroy, Yann; Armeanu, Dumitru; Cordan, Anne-Sophie

2011-05-01

The improvement of our model concerning a single nanocrystal that belongs to a nanocrystal floating gate of a flash memory is presented. In order to extend the gate voltage range applicability of the model, the 3D continuum of states of either metallic or semiconducting electrodes is discretized into 2D subbands. Such an approach gives precise information about the mechanisms behind the charging or release processes of the nanocrystal. Then, the self-energy and screening effects of an electron within the nanocrystal are evaluated and introduced in the model. This enables a better determination of the operating point of the nanocrystal memory. The impact of those improvements on the charging or release time of the nanocrystal is discussed.