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 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.

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.

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

Modified spontaneous emission of silicon nanocrystals embedded in artificial opals

NASA Astrophysics Data System (ADS)

Janda, Petr; Valenta, Jan; Rehspringer, Jean-Luc; Mafouana, Rodrigue R.; Linnros, Jan; Elliman, Robert G.

2007-10-01

Si nanocrystals (NCs) were embedded in synthetic silica opals by means of Si-ion implantation or opal impregnation with porous-Si suspensions. In both types of sample photoluminescence (PL) is strongly Bragg-reflection attenuated (up to 75%) at the frequency of the opal stop-band in a direction perpendicular to the (1 1 1) face of the perfect hcp opal structure. Time-resolved PL shows a rich distribution of decay rates, which contains both shorter and longer decay components compared with the ordinary stretched exponential decay of Si NCs. This effect reflects changes in the spontaneous emission rate of Si NCs due to variations in the local density of states of real opal containing defects.

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

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.

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.

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.

Doping effect in Si nanocrystals

NASA Astrophysics Data System (ADS)

Li, Dongke; Xu, Jun; Zhang, Pei; Jiang, Yicheng; Chen, Kunji

2018-06-01

Intentional doping in semiconductors is a fundamental issue since it can control the conduction type and ability as well as modify the optical and electronic properties. To realize effective doping is the basis for developing semiconductor devices. However, by reducing the size of a semiconductor, like Si, to the nanometer scale, the doping effects become complicated due to the coupling between the quantum confinement effect and the surfaces and/or interfaces effect. In particular, by introducing phosphorus or boron impurities as dopants into material containing Si nanocrystals with a dot size of less than 10 nm, it exhibits different behaviors and influences on the physical properties from its bulk counterpart. Understanding the doping effects in Si nanocrystals is currently a challenge in order to further improve the performance of the next generation of nano-electronic and photonic devices. In this review, we present an overview of the latest theoretical studies and experimental results on dopant distributions and their effects on the electronic and optical properties of Si nanocrystals. In particular, the advanced characterization techniques on dopant distribution, the carrier transport process as well as the linear and nonlinear optical properties of doped Si nanocrystals, are systematically summarized.

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.

Strong visible electroluminescence from silicon nanocrystals embedded in a silicon carbide film

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

Huh, Chul, E-mail: chuh@etri.re.kr; Kim, Tae-Youb; Ahn, Chang-Geun

2015-05-25

We report the strong visible light emission from silicon (Si) nanocrystals (NCs) embedded in a Si carbide (SiC) film. Compared to Si NC light-emitting diode (LED) by employing the Si nitride (SiN{sub x}) film as a surrounding matrix, the turn-on voltage of the Si NC LED with the SiC film was significantly decreased by 4 V. This was attributed to a smaller barrier height for injecting the electrons into the Si NCs due to a smaller band gap of SiC film than a SiN{sub x} film. The electroluminescence spectra increases with increasing forward voltage, indicating that the electrons are efficiently injectedmore » into the Si NCs in the SiC film. The light output power shows a linear increase with increasing forward voltage. The light emission originated from the Si NCs in a SiC film was quite uniform. The power efficiency of the Si NC LED with the SiC film was 1.56 times larger than that of the Si NC LED with the SiN{sub x} film. The Si NCs in a SiC film show unique advantages and are a promising candidate for application in optical devices.« less

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

Emission efficiency limit of Si nanocrystals

PubMed Central

Limpens, Rens; Luxembourg, Stefan L.; Weeber, Arthur W.; Gregorkiewicz, Tom

2016-01-01

One of the important obstacles on the way to application of Si nanocrystals for development of practical devices is their typically low emissivity. In this study we explore the limits of external quantum yield of photoluminescence of solid-state dispersions of Si nanocrystals in SiO2. By making use of a low-temperature hydrogen passivation treatment we demonstrate a maximum emission quantum efficiency of approximately 35%. This is the highest value ever reported for this type of material. By cross-correlating PL lifetime with EQE values, we obtain a comprehensive understanding of the efficiency limiting processes induced by Pb-defects. We establish that the observed record efficiency corresponds to an interface density of Pb-centers of 1.3 × 1012 cm12, which is 2 orders of magnitude higher than for the best Si/SiO2 interface. This result implies that Si nanocrystals with up to 100% emission efficiency are feasible. PMID:26786062

Si nanocrystals-based multilayers for luminescent and photovoltaic device applications

NASA Astrophysics Data System (ADS)

Lu, Peng; Li, Dongke; Cao, Yunqing; Xu, Jun; Chen, Kunji

2018-06-01

Low dimensional Si materials have attracted much attention because they can be developed in many kinds of new-generation nano-electronic and optoelectronic devices, among which Si nanocrystals-based multilayered material is one of the most promising candidates and has been extensively studied. By using multilayered structures, the size and distribution of nanocrystals as well as the barrier thickness between two adjacent Si nanocrystal layers can be well controlled, which is beneficial to the device applications. This paper presents an overview of the fabrication and device applications of Si nanocrystals, especially in luminescent and photovoltaic devices. We first introduce the fabrication methods of Si nanocrystals-based multilayers. Then, we systematically review the utilization of Si nanocrystals in luminescent and photovoltaic devices. Finally, some expectations for further development of the Si nanocrystals-based photonic and photovoltaic devices are proposed. Project supported by the National Natural Science Foundation of China (Nos. 11774155, 11274155).

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.

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.

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

Stress evolution of Ge nanocrystals in dielectric matrices.

PubMed

Bahariqushchi, Rahim; Raciti, Rosario; Kasapoğlu, Ahmet Emre; Gür, Emre; Sezen, Meltem; Kalay, Eren; Mirabella, Salvatore; Aydinli, A

2018-05-04

Germanium nanocrystals (Ge NCs) embedded in single and multilayer silicon oxide and silicon nitride matrices have been synthesized using plasma enhanced chemical vapor deposition followed by conventional furnace annealing or rapid thermal processing in N 2 ambient. Compositions of the films were determined by Rutherford backscattering spectrometry and x-ray photoelectron spectroscopy. The formation of NCs under suitable process conditions was observed with high resolution transmission electron microscope micrographs and Raman spectroscopy. Stress measurements were done using Raman shifts of the Ge optical phonon line at 300.7 cm -1 . The effect of the embedding matrix and annealing methods on Ge NC formation were investigated. In addition to Ge NCs in single layer samples, the stress on Ge NCs in multilayer samples was also analyzed. Multilayers of Ge NCs in a silicon nitride matrix separated by dielectric buffer layers to control the size and density of NCs were fabricated. Multilayers consisted of SiN y :Ge ultrathin films sandwiched between either SiO 2 or Si 3 N 4 by the proper choice of buffer material. We demonstrated that it is possible to tune the stress state of Ge NCs from compressive to tensile, a desirable property for optoelectronic applications. We also observed that there is a correlation between the stress and the crystallization threshold in which the compressive stress enhances the crystallization, while the tensile stress suppresses the process.

Stress evolution of Ge nanocrystals in dielectric matrices

NASA Astrophysics Data System (ADS)

Bahariqushchi, Rahim; Raciti, Rosario; Emre Kasapoğlu, Ahmet; Gür, Emre; Sezen, Meltem; Kalay, Eren; Mirabella, Salvatore; Aydinli, A.

2018-05-01

Germanium nanocrystals (Ge NCs) embedded in single and multilayer silicon oxide and silicon nitride matrices have been synthesized using plasma enhanced chemical vapor deposition followed by conventional furnace annealing or rapid thermal processing in N2 ambient. Compositions of the films were determined by Rutherford backscattering spectrometry and x-ray photoelectron spectroscopy. The formation of NCs under suitable process conditions was observed with high resolution transmission electron microscope micrographs and Raman spectroscopy. Stress measurements were done using Raman shifts of the Ge optical phonon line at 300.7 cm-1. The effect of the embedding matrix and annealing methods on Ge NC formation were investigated. In addition to Ge NCs in single layer samples, the stress on Ge NCs in multilayer samples was also analyzed. Multilayers of Ge NCs in a silicon nitride matrix separated by dielectric buffer layers to control the size and density of NCs were fabricated. Multilayers consisted of SiN y :Ge ultrathin films sandwiched between either SiO2 or Si3N4 by the proper choice of buffer material. We demonstrated that it is possible to tune the stress state of Ge NCs from compressive to tensile, a desirable property for optoelectronic applications. We also observed that there is a correlation between the stress and the crystallization threshold in which the compressive stress enhances the crystallization, while the tensile stress suppresses the process.

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.

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.

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.

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.

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.

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.

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.

Effects of PEGylated paclitaxel nanocrystals on breast cancer and its lung metastasis

NASA Astrophysics Data System (ADS)

Zhang, Hua; Hu, Hongxiang; Zhang, Haoran; Dai, Wenbing; Wang, Xinglin; Wang, Xueqing; Zhang, Qiang

2015-06-01

As an attractive strategy developed rapidly in recent years, nanocrystals are used to deliver insoluble drugs. PEGylation may further prolong the circulation time of nanoparticles and improve the therapeutic outcome of drugs. In this study, paclitaxel (PTX) nanocrystals (PTX-NCs) and PEGylated PTX nanocrystals (PEG-PTX-NCs) were prepared using antisolvent precipitation augmented by probe sonication. The characteristics and antitumor efficacy of nanocrystals were investigated. The results indicated that the nanocrystals showed rod-like morphology, and the average particle size was 240 nm and 330 nm for PTX-NCs and PEG-PTX-NCs, respectively. The PEG molecules covered the surface of nanocrystals with an 11.54 nm fixed aqueous layer thickness (FALT), much higher than that of PTX-NCs (0.2 nm). PEG-PTX-NCs showed higher stability than PTX-NCs under both storage and physiological conditions. In breast cancer xenografted mice, PEG-PTX-NCs showed significantly better tumor inhibition compared to saline (p < 0.001) and PTX-NC groups (p < 0.05) after intravenous administration. In a model of lung tumor metastasis quantified by the luciferase activity, the PEG-PTX-NCs group showed higher anticancer efficacy not only than saline and PTX-NCs groups, but also than Taxol®, achieving an 82% reduction at the end of the experiment. These studies suggested the potential advantages of PEGylated PTX nanocrystals as alternative drug delivery systems for anticancer therapy.

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

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.

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.

Structural and electrical characterization of annealed Si1-xCx/SiC thin film prepared by magnetron sputtering

NASA Astrophysics Data System (ADS)

Huang, Shi-Hua; Liu, Jian

2014-05-01

Si-rich Si1—xCx /SiC multilayer thin films are prepared using magnetron sputtering, subsequently followed by thermal annealing in the range of 800-1200 °C. The influences of annealing temperature (Ta) on the formation of Si and/or SiC nanocrystals (NCs) and on the electrical characteristics of the multilayer film are investigated by using a variety of analytical techniques, including X-ray diffraction (XRD), Raman spectroscopy and Fourier transform infrared spectrometry (FT-IR), current—voltage (I—V) technique, and capacitance-voltage (C—V) technique. XRD and Raman analyses indicate that Si NCs begin to form in samples for Ta >= 800 °C. At annealing temperatures of 1000 °C or higher, the formation of Si NCs is accompanied by the formation of SiC NCs. With the increase in the annealing temperature, the shift of FT-IR Si—C bond absorption spectra toward a higher wave number along with the change of band shape can be explained by a Si—C transitional phase between the loss of substitutional carbon and the formation of SiC precipitates and a precursor for the growth of SiC crystalline. The C—V and I—V results indicate that the interface quality of Si1—xCx/SiC multilayer film is improved significantly and the leakage current is reduced rapidly for Ta >= 1000 °C, which can be ascribed to the formation of Si and SiC NCs.

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

Nanocrystal floating gate memory with solution-processed indium-zinc-tin-oxide channel and colloidal silver nanocrystals

NASA Astrophysics Data System (ADS)

Hu, Quanli; Ha, Sang-Hyub; Lee, Hyun Ho; Yoon, Tae-Sik

2011-12-01

A nanocrystal (NC) floating gate memory with solution-processed indium-zinc-tin-oxide (IZTO) channel and silver (Ag) NCs embedded in thin gate dielectric layer (SiO2(30 nm)/Al2O3(3 nm)) was fabricated. Both the IZTO channel and colloidal Ag NC layers were prepared by spin-coating and subsequent annealing, and dip-coating process, respectively. A threshold voltage shift up to ~0.9 V, corresponding to the electron density of 6.5 × 1011 cm-2, at gate pulsing <=10 V was achieved by the charging of high density NCs. These results present the successful non-volatile memory characteristics of an oxide-semiconductor transistor fabricated through solution processes.

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.

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

High performance SONOS flash memory with in-situ silicon nanocrystals embedded in silicon nitride charge trapping layer

NASA Astrophysics Data System (ADS)

Lim, Jae-Gab; Yang, Seung-Dong; Yun, Ho-Jin; Jung, Jun-Kyo; Park, Jung-Hyun; Lim, Chan; Cho, Gyu-seok; Park, Seong-gye; Huh, Chul; Lee, Hi-Deok; Lee, Ga-Won

2018-02-01

In this paper, SONOS-type flash memory device with highly improved charge-trapping efficiency is suggested by using silicon nanocrystals (Si-NCs) embedded in silicon nitride (SiNX) charge trapping layer. The Si-NCs were in-situ grown by PECVD without additional post annealing process. The fabricated device shows high program/erase speed and retention property which is suitable for multi-level cell (MLC) application. Excellent performance and reliability for MLC are demonstrated with large memory window of ∼8.5 V and superior retention characteristics of 7% charge loss for 10 years. High resolution transmission electron microscopy image confirms the Si-NC formation and the size is around 1-2 nm which can be verified again in X-ray photoelectron spectroscopy (XPS) where pure Si bonds increase. Besides, XPS analysis implies that more nitrogen atoms make stable bonds at the regular lattice point. Photoluminescence spectra results also illustrate that Si-NCs formation in SiNx is an effective method to form deep trap states.

The effect of oxide shell thickness on the structural, electronic, and optical properties of Si-SiO{sub 2} core-shell nano-crystals: A (time dependent)density functional theory study

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

Nazemi, Sanaz, E-mail: s.nazemi@ut.ac.ir, E-mail: pourfath@ut.ac.ir; Soleimani, Ebrahim Asl; Pourfath, Mahdi, E-mail: s.nazemi@ut.ac.ir, E-mail: pourfath@ut.ac.ir

2016-04-14

Due to their tunable properties, silicon nano-crystals (NC) are currently being investigated. Quantum confinement can generally be employed for size-dependent band-gap tuning at dimensions smaller than the Bohr radius (∼5 nm for silicon). At the nano-meter scale, however, increased surface-to-volume ratio makes the surface effects dominant. Specifically, in Si-SiO{sub 2} core-shell semiconductor NCs the interfacial transition layer causes peculiar electronic and optical properties, because of the co-existence of intermediate oxidation states of silicon (Si{sup n+}, n = 0–4). Due to the presence of the many factors involved, a comprehensive understanding of the optical properties of these NCs has not yet been achieved. Inmore » this work, Si-SiO{sub 2} NCs with a diameter of 1.1 nm and covered by amorphous oxide shells with thicknesses between 2.5 and 4.75 Å are comprehensively studied, employing density functional theory calculations. It is shown that with increased oxide shell thickness, the low-energy part of the optical transition spectrum of the NC is red shifted and attenuated. Moreover, the absorption coefficient is increased in the high-energy part of the spectrum which corresponds to SiO{sub 2} transitions. Structural examinations indicate a larger compressive stress on the central silicon cluster with a thicker oxide shell. Examination of the local density of states reveals the migration of frontier molecular orbitals from the oxide shell into the silicon core with the increase of silica shell thickness. The optical and electrical properties are explained through the analysis of the density of states and the spatial distribution of silicon sub-oxide species.« less

White light emission and optical gains from a Si nanocrystal thin film

NASA Astrophysics Data System (ADS)

Wang, Dong-Chen; Hao, Hong-Chen; Chen, Jia-Rong; Zhang, Chi; Zhou, Jing; Sun, Jian; Lu, Ming

2015-11-01

We report a Si nanocrystal thin film consisting of free-standing Si nanocrystals, which can emit white light and show positive optical gains for its red, green and blue (RGB) components under ultraviolet excitation. Si nanocrystals with ϕ = 2.31 ± 0.35 nm were prepared by chemical etching of Si powder, followed by filtering. After being mixed with SiO2 sol-gel and thermally annealed, a broadband photoluminescence (PL) from the thin film was observed. The RGB ratio of the PL can be tuned by changing the annealing temperature or atmosphere, which is 1.00/3.26/4.59 for the pure white light emission. The origins of the PL components could be due to differences in oxygen-passivation degree for Si nanocrystals. The results may find applications in white-light Si lasing and Si lighting.

Surface modified SiO2 nanoparticles by thiamine and ultrasonication synthesis of PCL/SiO2-VB1 NCs: Morphology, thermal, mechanical and bioactivity investigations.

PubMed

Mallakpour, Shadpour; Khani, Zahra

2018-03-01

The influence of silica (SiO 2 ) nanoparticles (NPs) on the properties of polycaprolactone (PCL) was investigated. Due to the intense tendency of SiO 2 NPs to aggregation and their high surface energy, the surface of SiO 2 NPs was treatment via Vitamin B 1 (VB 1 ) as a biosafe coupling agent. Novel PCL/SiO 2 -VB 1 nanocomposites (NC) films by variety of percentage of SiO 2 -VB 1 NPs were prepared under ultrasonic irradiation as an eco-friendly and fast procedure following by casting method. Fourier transform infrared spectroscopy and energy dispersive X-ray analysis exposed the presence of SiO 2 NPs into the polymer matrix. A good distribution of the silica into the polymer matrix was detected by microscopic observations and EDX testing. According to the UV-Vis spectra, the absorption of prepared NCs was improved via increasing the amount of SiO 2 NPs. PCL/SiO 2 -VB 1 NCs showed more thermal stability compared to the pure polymer. The tensile test was investigated and good arrangement among the experimental data and the predicted flexibility of NCs was obtained. Moreover, PCL/SiO 2 -VB 1 6wt% had noticeable increase values for tensile strength. Finally, in vitro bioactivity investigation designated that by rising SiO 2 contents in the NCs, the amount of the hydroxyapatite formed was increased and NC films are bioactive and have a potential to be utilized in bone tissue engineering. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

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

Expansion and melting of Xe nanocrystals in Si

NASA Astrophysics Data System (ADS)

Faraci, Giuseppe; Pennisi, Agata R.; Zontone, Federico; Li, Boquan; Petrov, Ivan

2006-12-01

Xe agglomerates confined in a Si matrix by ion implantation were synthesized with different size depending on the implantation process and/or the thermal treatment. At low temperature Xe nanocrystals are formed, whose expansion and melting were studied in the range 15- 300K . Previous high resolution x-ray diffraction spectra were corroborated with complementary techniques such as two-dimensional imaging plate patterns and transmission electron microscopy. We detected fcc Xe nanocrystals whose properties were size dependent. The experiments showed that in annealed samples epitaxial condensation of small Xe clusters, on the cavities of the Si matrix, gave in fact expanded and oriented Xe, suggesting a possible preferential growth of Xe(311) planes oriented orthogonally to the Si[02-2] direction. On the contrary, small Xe clusters in an amorphous Si matrix have a fcc lattice contracted as a consequence of surface tension. Furthermore, a solid-to-liquid phase transition size dependent was found. Expansion of fcc Xe lattice was accurately determined as a function of the temperature. Overpressurized nanocrystals and/or binary size distributions were disproved.

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.

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

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

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.

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

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.

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

Titanium-tungsten nanocrystals embedded in a SiO(2)/Al(2)O(3) gate dielectric stack for low-voltage operation in non-volatile memory.

PubMed

Yang, Shiqian; Wang, Qin; Zhang, Manhong; Long, Shibing; Liu, Jing; Liu, Ming

2010-06-18

Titanium-tungsten nanocrystals (NCs) were fabricated by a self-assembly rapid thermal annealing (RTA) process. Well isolated Ti(0.46)W(0.54) NCs were embedded in the gate dielectric stack of SiO(2)/Al(2)O(3). A metal-oxide-semiconductor (MOS) capacitor was fabricated to investigate its application in a non-volatile memory (NVM) device. It demonstrated a large memory window of 6.2 V in terms of flat-band voltage (V(FB)) shift under a dual-directional sweeping gate voltage of - 10 to 10 V. A 1.1 V V(FB) shift under a low dual-directional sweeping gate voltage of - 4 to 4 V was also observed. The retention characteristic of this MOS capacitor was demonstrated by a 0.5 V memory window after 10(4) s of elapsed time at room temperature. The endurance characteristic was demonstrated by a program/erase cycling test.

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…

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.

Charge storage and tunneling mechanism of Ni nanocrystals embedded HfOx film

NASA Astrophysics Data System (ADS)

Zhu, H. X.; Zhang, T.; Wang, R. X.; Zhang, Y. Y.; Li, L. T.; Qiu, X. Y.

2016-05-01

A nano-floating gate memory structure based on Ni nanocrystals (NCs) embedded HfOx 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 HfOx matrix. Pt/Ni-NCs embedded HfOx/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 × 1012 electrons/cm2, is achieved. These capacitor memory cells exhibit good endurance characteristic up to 4 × 104 cycles and excellent retention performance of 105 s, fulfilling the requirements of next generation non-volatile memory devices. Schottky tunneling is proven to be responsible for electrons tunneling in these capacitors.

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.

The Preparation and Microstructure of Nanocrystal 3C-SiC/ZrO2 Bilayer Films

PubMed Central

Ye, Chao; Ran, Guang; Zhou, Wei; Qu, Yazhou; Yan, Xin; Cheng, Qijin; Li, Ning

2017-01-01

The nanocrystal 3C-SiC/ZrO2 bilayer films that could be used as the protective coatings of zirconium alloy fuel cladding were prepared on a single-crystal Si substrate. The corresponding nanocrystal 3C-SiC film and nanocrystal ZrO2 film were also dividedly synthesized. The microstructure of nanocrystal films was analyzed by grazing incidence X-ray diffraction (GIXRD) and cross-sectional transmission electron microscopy (TEM). The 3C-SiC film with less than 30 nm crystal size was synthesized by Plasma Enhanced Chemical Vapor Deposition (PECVD) and annealing. The corresponding formation mechanism of some impurities in SiC film was analyzed and discussed. An amorphous Zr layer about 600 nm in width was first deposited by magnetron sputtering and then oxidized to form a nanocrystal ZrO2 layer during the annealing process. The interface characteristics of 3C-SiC/ZrO2 bilayer films prepared by two different processes were obviously different. SiZr and SiO2 compounds were formed at the interface of 3C-SiC/ZrO2 bilayer films. A corrosion test of 3C-SiC/ZrO2 bilayer films was conducted to qualitatively analyze the surface corrosion resistance and the binding force of the interface. PMID:29168782

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.

Atomic Layer Deposited Oxide-Based Nanocomposite Structures with Embedded CoPtx Nanocrystals for Resistive Random Access Memory Applications.

PubMed

Wang, Lai-Guo; Cao, Zheng-Yi; Qian, Xu; Zhu, Lin; Cui, Da-Peng; Li, Ai-Dong; Wu, Di

2017-02-22

Al 2 O 3 - or HfO 2 -based nanocomposite structures with embedded CoPt x nanocrystals (NCs) on TiN-coated Si substrates have been prepared by combination of thermal atomic layer deposition (ALD) and plasma-enhanced ALD for resistive random access memory (RRAM) applications. The impact of CoPt x NCs and their average size/density on the resistive switching properties has been explored. Compared to the control sample without CoPt x NCs, ALD-derived Pt/oxide/100 cycle-CoPt x NCs/TiN/SiO 2 /Si exhibits a typical bipolar, reliable, and reproducible resistive switching behavior, such as sharp distribution of RRAM parameters, smaller set/reset voltages, stable resistance ratio (≥10 2 ) of OFF/ON states, better switching endurance up to 10 4 cycles, and longer data retention over 10 5 s. The possible resistive switching mechanism based on nanocomposite structures of oxide/CoPt x NCs has been proposed. The dominant conduction mechanisms in low- and high-resistance states of oxide-based device units with embedded CoPt x NCs are Ohmic behavior and space-charge-limited current, respectively. The insertion of CoPt x NCs can effectively improve the formation of conducting filaments due to the CoPt x NC-enhanced electric field intensity. Besides excellent resistive switching performances, the nanocomposite structures also simultaneously present ferromagnetic property. This work provides a flexible pathway by combining PEALD and TALD compatible with state-of-the-art Si-based technology for multifunctional electronic devices applications containing RRAM.

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

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.

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.

Electronic and optical properties of Si and Ge nanocrystals: An ab initio study

NASA Astrophysics Data System (ADS)

Pulci, Olivia; Degoli, Elena; Iori, Federico; Marsili, Margherita; Palummo, Maurizia; Del Sole, Rodolfo; Ossicini, Stefano

2010-01-01

First-principles calculations within density functional theory and many-body perturbation theory have been carried out in order to investigate the structural, electronic and optical properties of undoped and doped silicon nanostructures. We consider Si nanoclusters co-doped with B and P. We find that the electronic band gap is reduced with respect to that of the undoped crystals, suggesting the possibility of impurity based engineering of electronic and optical properties of Si nanocrystals. Finally, motivated by recent suggestions concerning the chance of exploiting Ge dots for photovoltaic nanodevices, we present calculations of the electronic and optical properties of a Ge 35H 36 nanocrystal, and compare the results with those for the corresponding Si 35H 36 nanocrystals and the co-doped Si 33BPH 36.

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

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.

Lifetime of excitons localized in Si nanocrystals in amorphous silicon

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

Gusev, O. B.; Belolipetskiy, A. V., E-mail: alexey.belolipetskiy@mail.ioffe.ru; Yassievich, I. N.

2016-05-15

The introduction of nanocrystals plays an important role in improving the stability of the amorphous silicon films and increasing the carrier mobility. Here we report results of the study on the photoluminescence and its dynamics in the films of amorphous hydrogenated silicon containing less than 10% of silicon nanocrystals. The comparing of the obtained experimental results with the calculated probability of the resonant tunneling of the excitons localized in silicon nanocrystals is presented. Thus, it has been estimated that the short lifetime of excitons localized in Si nanocrystal is controlled by the resonant tunneling to the nearest tail state ofmore » the amorphous matrix.« less

Charge injection and discharging of Si nanocrystals and arrays by atomic force microscopy

NASA Technical Reports Server (NTRS)

Boer, E.; Ostraat, M.; Brongersma, M. L.; Flagan, R. C.; Atwater, H. A.

2000-01-01

Charge injection and storage in dense arrays of silicon nanocrystals in SiO(sub 2) is a critical aspect of the performance of potential nanocrystal flash memory structures. The ultimate goal for this class of devices is few-or single- electron storage in a small number of nanocrystal elements.

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

Scaling dependence of memory windows and different carrier charging behaviors in Si nanocrystal nonvolatile memory devices

NASA Astrophysics Data System (ADS)

Yu, Jie; Chen, Kun-ji; Ma, Zhong-yuan; Zhang, Xin-xin; Jiang, Xiao-fan; Wu, Yang-qing; Huang, Xin-fan; Oda, Shunri

2016-09-01

Based on the charge storage mode, it is important to investigate the scaling dependence of memory performance in silicon nanocrystal (Si-NC) nonvolatile memory (NVM) devices for its scaling down limit. In this work, we made eight kinds of test key cells with different gate widths and lengths by 0.13-μm node complementary metal oxide semiconductor (CMOS) technology. It is found that the memory windows of eight kinds of test key cells are almost the same of about 1.64 V @ ± 7 V/1 ms, which are independent of the gate area, but mainly determined by the average size (12 nm) and areal density (1.8 × 1011/cm2) of Si-NCs. The program/erase (P/E) speed characteristics are almost independent of gate widths and lengths. However, the erase speed is faster than the program speed of test key cells, which is due to the different charging behaviors between electrons and holes during the operation processes. Furthermore, the data retention characteristic is also independent of the gate area. Our findings are useful for further scaling down of Si-NC NVM devices to improve the performance and on-chip integration. Project supported by the State Key Development Program for Basic Research of China (Grant No. 2010CB934402) and the National Natural Science Foundation of China (Grant Nos. 11374153, 61571221, and 61071008).

A multilayered approach of Si/SiO to promote carrier transport in electroluminescence of Si nanocrystals

PubMed Central

2012-01-01

The electroluminescence (EL) and photoluminescence of Si nanocrystals (Si-nc) from multilayered samples of Si/SiO are investigated. Si-nc are formed within Si and SiO layers after furnace annealing. It is found that the presence of Si interlayers creates extra carrier paths for EL emission. A comparative study is further performed on a multilayered Si/SiO sample and a single-layered one with Si and SiO homogeneously mixed. Both samples have the same ratio of Si to O and the same contents of Si and O. The multilayered sample is found to have higher EL intensity, less turn-on voltage, lower resistance, and higher current efficiency than the single-layered one. The results indicate that Si interlayers in Si/SiO may act as carrier channels, which promote carrier transport and enhance the EL emission of Si-nc. PMID:22448989

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.

Nonvolatile memory with Co-SiO2 core-shell nanocrystals as charge storage nodes in floating gate

NASA Astrophysics Data System (ADS)

Liu, Hai; Ferrer, Domingo A.; Ferdousi, Fahmida; Banerjee, Sanjay K.

2009-11-01

In this letter, we reported nanocrystal floating gate memory with Co-SiO2 core-shell nanocrystal charge storage nodes. By using a water-in-oil microemulsion scheme, Co-SiO2 core-shell nanocrystals were synthesized and closely packed to achieve high density matrix in the floating gate without aggregation. The insulator shell also can help to increase the thermal stability of the nanocrystal metal core during the fabrication process to improve memory performance.

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.

In-situ high resolution transmission electron microscopy observation of silicon nanocrystal nucleation in a SiO{sub 2} bilayered matrix

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

Yang, T. C.-J., E-mail: terry.yang@unsw.edu.au; Wu, L.; Lin, Z.

2014-08-04

Solid-state nucleation of Si nanocrystals in a SiO{sub 2} bilayered matrix was observed at temperatures as low as 450 °C. This was achieved by aberration corrected high-resolution transmission electron microscopy (HRTEM) with real-time in-situ heating up to 600 °C. This technique is a valuable characterization tool especially with the recent interest in Si nanostructures for light emitting devices, non-volatile memories, and third-generation photovoltaics which all typically require a heating step in their fabrication. The control of size, shape, and distribution of the Si nanocrystals are critical for these applications. This experimental study involves in-situ observation of the nucleation of Si nanocrystals inmore » a SiO{sub 2} bilayered matrix fabricated through radio frequency co-sputtering. The results show that the shapes of Si nanocrystals in amorphous SiO{sub 2} bilayered matrices are irregular and not spherical, in contrast to many claims in the literature. Furthermore, the Si nanocrystals are well confined within their layers by the amorphous SiO{sub 2}. This study demonstrates the potential of in-situ HRTEM as a tool to observe the real time nucleation of Si nanocrystals in a SiO{sub 2} bilayered matrix. Furthermore, ideas for improvements on this in-situ heating HRTEM technique are discussed.« less

Enhanced optical properties of Si nanocrystals in planar microcavity

NASA Astrophysics Data System (ADS)

Toshikiyo, Kimiaki; Fujii, Minoru; Hayashi, Shinji

2003-04-01

The emission property of Si nanocrystals (nc-Si) in an optical microcavity was studied by photoluminescence (PL) and time resolved PL measurements. The PL from the microcavity was narrowed to the line width of 17 meV, enhanced by a factor of 20 compared to the same film without microcavity. The lifetime for nc-Si became shorter by putting the film in microcavity. This results could be well-explained by the redistribution of the optical modes in the cavity due to the presence of the optical resonator.

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.

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.

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.

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.

Ge nanocrystals formed by furnace annealing of Ge(x)[SiO2](1-x) films: structure and optical properties

NASA Astrophysics Data System (ADS)

Volodin, V. A.; Cherkov, A. G.; Antonenko, A. Kh; Stoffel, M.; Rinnert, H.; Vergnat, M.

2017-07-01

Ge(x)[SiO2](1-x) (0.1  ⩽  x  ⩽  0.4) films were deposited onto Si(0 0 1) or fused quartz substrates using co-evaporation of both Ge and SiO2 in high vacuum. Germanium nanocrystals were synthesized in the SiO2 matrix by furnace annealing of Ge x [SiO2](1-x) films with x  ⩾  0.2. According to electron microscopy and Raman spectroscopy data, the average size of the nanocrystals depends weakly on the annealing temperature (700, 800, or 900 °C) and on the Ge concentration in the films. Neither amorphous Ge clusters nor Ge nanocrystals were observed in as-deposited and annealed Ge0.1[SiO2]0.9 films. Infrared absorption spectroscopy measurements show that the studied films do not contain a noticeable amount of GeO x clusters. After annealing at 900 °C intermixing of germanium and silicon atoms was still negligible thus preventing the formation of GeSi nanocrystals. For annealed samples, we report the observation of infrared photoluminescence at low temperatures, which can be explained by exciton recombination in Ge nanocrystals. Moreover, we report strong photoluminescence in the visible range at room temperature, which is certainly due to Ge-related defect-induced radiative transitions.

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

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

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.

Optical properties of Si and Ge nanocrystals: Parameter-free calculations

NASA Astrophysics Data System (ADS)

Ramos, L. E.; Weissker, H.-Ch.; Furthmüller, J.; Bechstedt, F.

2005-12-01

The cover picture of the current issue refers to the Edi-tor's Choice article of Ramos et al. [1]. The paper gives an overview of the electronic and optical properties of silicon and germanium nanocrystals determined by state-of-the-art ab initio methods. Nanocrystals have promising applications in opto-electronic devices, since they can be used to confine electrons and holes and facilitate radiative recombination. Since meas-urements for single nanoparticles are difficult to make, ab initio theoretical investigations become important to understand the mechanisms of luminescence.The cover picture shows nanocrystals of four sizes with tetrahedral coordination whose dangling bonds at the surface are passivated with hydrogen. As often observed in experiments, the nanocrystals are not perfectly spherical, but contain facets. Apart from the size of the nanocrystals, which determines the quantum confinement, the way their dangling bonds are passivated is relevant for their electronic and optical properties. For instance, the passivation with hydroxyls reduces the quantum confine-ment. On the other hand, the oxidation of the silicon nanocrys-tals increases the quantum confinement and reduces the effect of single surface terminations on the gap. Due to the oscillator strengths of the lowest-energy optical transitions, Ge nanocrys-tals are in principle more suitable for opto-electronic applica-tions than Si nanocrystals.The first author, Luis E. Ramos, is a postdoc at the Institute of Solid-State Physics and Optics (IFTO), Friedrich-Schiller University Jena, Germany. He investigates electronic and optical properties of semiconductor nanocrystallites and is a member of the European Network of Excellence NANO-QUANTA and of the European Theoretical Spectroscopy Facility (ETSF).

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.

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

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.

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.

Size-dependent characterization of embedded Ge nanocrystals: Structural and thermal properties

NASA Astrophysics Data System (ADS)

Araujo, L. L.; Giulian, R.; Sprouster, D. J.; Schnohr, C. S.; Llewellyn, D. J.; Kluth, P.; Cookson, D. J.; Foran, G. J.; Ridgway, M. C.

2008-09-01

A combination of conventional and synchrotron-based techniques has been used to characterize the size-dependent structural and thermal properties of Ge nanocrystals (NCs) embedded in a silica (a-SiO2) matrix. Ge NC size distributions with four different diameters ranging from 4.0 to 9.0 nm were produced by ion implantation and thermal annealing as characterized with small-angle x-ray scattering and transmission electron microscopy. The NCs were well represented by the superposition of bulklike crystalline and amorphous environments, suggesting the formation of an amorphous layer separating the crystalline NC core and the a-SiO2 matrix. The amorphous fraction was quantified with x-ray-absorption near-edge spectroscopy and increased as the NC diameter decreased, consistent with the increase in surface-to-volume ratio. The structural parameters of the first three nearest-neighbor shells were determined with extended x-ray-absorption fine-structure (EXAFS) spectroscopy and evolved linearly with inverse NC diameter. Specifically, increases in total disorder, interatomic distance, and the asymmetry in the distribution of distances were observed as the NC size decreased, demonstrating that finite-size effects govern the structural properties of embedded Ge NCs. Temperature-dependent EXAFS measurements in the range of 15-300 K were employed to probe the mean vibrational frequency and the variation of the interatomic distance distribution (mean value, variance, and asymmetry) with temperature for all NC distributions. A clear trend of increased stiffness (higher vibrational frequency) and decreased thermal expansion with decreasing NC size was evident, confirming the close relationship between the variation of structural and thermal/vibrational properties with size for embedded Ge NCs. The increase in surface-to-volume ratio and the presence of an amorphous Ge layer separating the matrix and crystalline NC core are identified as the main factors responsible for the observed

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

Optical and Structural Properties of Si Nanocrystals in SiO2 Films.

PubMed

Nikitin, Timur; Khriachtchev, Leonid

2015-04-22

Optical and structural properties of Si nanocrystals (Si-nc) in silica films are described. For the SiOx (x < 2) films annealed above 1000 °C, the Raman signal of Si-nc and the absorption coefficient are proportional to the amount of elemental Si detected by X-ray photoelectron spectroscopy. A good agreement is found between the measured refractive index and the value estimated by using the effective-medium approximation. The extinction coefficient of elemental Si is found to be between the values of crystalline and amorphous Si. Thermal annealing increases the degree of Si crystallization; however, the crystallization and the Si-SiO2 phase separation are not complete after annealing at 1200 °C. The 1.5-eV PL quantum yield increases as the amount of elemental Si decreases; thus, this PL is probably not directly from Si-nc responsible for absorption and detected by Raman spectroscopy. Continuous-wave laser light can produce very high temperatures in the free-standing films, which changes their structural and optical properties. For relatively large laser spots, the center of the laser-annealed area is very transparent and consists of amorphous SiO2. Large Si-nc (up to ∼300 nm in diameter) are observed in the ring around the central region. These Si-nc lead to high absorption and they are typically under compressive stress, which is connected with their formation from the liquid phase. By using strongly focused laser beams, the structural changes in the free-standing films can be made in submicron areas.

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.

Optical and Structural Properties of Si Nanocrystals in SiO2 Films

PubMed Central

Nikitin, Timur; Khriachtchev, Leonid

2015-01-01

Optical and structural properties of Si nanocrystals (Si-nc) in silica films are described. For the SiOx (x < 2) films annealed above 1000 °C, the Raman signal of Si-nc and the absorption coefficient are proportional to the amount of elemental Si detected by X-ray photoelectron spectroscopy. A good agreement is found between the measured refractive index and the value estimated by using the effective-medium approximation. The extinction coefficient of elemental Si is found to be between the values of crystalline and amorphous Si. Thermal annealing increases the degree of Si crystallization; however, the crystallization and the Si–SiO2 phase separation are not complete after annealing at 1200 °C. The 1.5-eV PL quantum yield increases as the amount of elemental Si decreases; thus, this PL is probably not directly from Si-nc responsible for absorption and detected by Raman spectroscopy. Continuous-wave laser light can produce very high temperatures in the free-standing films, which changes their structural and optical properties. For relatively large laser spots, the center of the laser-annealed area is very transparent and consists of amorphous SiO2. Large Si-nc (up to ~300 nm in diameter) are observed in the ring around the central region. These Si-nc lead to high absorption and they are typically under compressive stress, which is connected with their formation from the liquid phase. By using strongly focused laser beams, the structural changes in the free-standing films can be made in submicron areas. PMID:28347028

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.

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

PubMed

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

2018-05-30

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

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

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.

Modification of SiO2 nanowires with metallic nanocrystals from supercritical CO2.

PubMed

Ye, Xiang-Rong; Zhang, Hai-Feng; Lin, Yuehe; Wang, Lai-Sheng; Wai, Chien M

2004-01-01

Through hydrogen reduction of metal precursors in supercritical CO2, Cu, and Pd, nanocrystals were deposited onto SiO2 nanowires to form different types of nanostructured materials, including nanocrystal-nanowire, spherical aggregation-nanowire, shell-nanowire composites, and "mesoporous" metals supported by the framework of nanowires. This supercritical fluid deposition technique is an attractive approach for modifying nanowires because of its generality and simplicity; the modified nanowires could be useful as catalysts and for further fabrication of multifunctional composites.

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

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.

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.

Evaluation of quantum confinement effect in nanocrystal Si dot layer by Raman spectroscopy.

PubMed

Mizukami, Y; Kosemura, D; Numasawa, Y; Ohshita, Y; Ogura, A

2012-11-01

Quantum confinement effect in the nanocrystal-Si (nc-Si) was evaluated by Raman spectroscopy. The nc-Si dot layers were fabricated by the H2 plasma treatment for the nucleation site formation followed by the SiH4 irradiation for the nc-Si growth. Post-oxidation annealing was also performed to improve the crystalline quality. After post-oxidation annealing for 5 or 10 min, the asymmetric broadening on the lower frequency sides in Raman spectra were obtained, which can be attributed to the phonon confinement effect in nc-Si. Furthermore we confirmed that hydrostatic stress of approximately 500 MPa was induced in nc-Si after post-oxidation annealing.

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.

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.

Generation of silicon nanocrystals by damage free continuous wave laser annealing of substrate-bound SiO{sub x} films

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

Fricke-Begemann, T., E-mail: fricke-begemann@llg-ev.de; Ihlemann, J.; Wang, N.

2015-09-28

Silicon nanocrystals have been generated by laser induced phase separation in SiO{sub x} films. A continuous wave laser emitting at 405 nm is focused to a 6 μm diameter spot on 530 nm thick SiO{sub x} films deposited on fused silica substrates. Irradiation of lines is accomplished by focus scanning. The samples are investigated by atomic force microscopy, TEM, Raman spectroscopy, and photoluminescence measurements. At a laser power of 35 mW corresponding to an irradiance of about 1.2 × 10{sup 5 }W/cm{sup 2}, the formation of Si-nanocrystals in the film without any deterioration of the surface is observed. At higher laser power, the centralmore » irradiated region is oxidized to SiO{sub 2} and exhibits some porous character, while the surface remains optically smooth, and nanocrystals are observed beside and beneath this oxidized region. Amorphous Si-nanoclusters are formed at lower laser power and around the lines written at high power.« less

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.

Quantitative Analysis of Charge Injection and Discharging of Si Nanocrystals and Arrays by Electrostatic Force Microscopy

NASA Technical Reports Server (NTRS)

Bell, L. D.; Boer, E.; Ostraat, M.; Brongersma, M. L.; Flagan, R. C.; Atwater, H. A.

2000-01-01

NASA requirements for computing and memory for microspacecraft emphasize high density, low power, small size, and radiation hardness. The distributed nature of storage elements in nanocrystal floating-gate memories leads to intrinsic fault tolerance and radiation hardness. Conventional floating-gate non-volatile memories are more susceptible to radiation damage. Nanocrystal-based memories also offer the possibility of faster, lower power operation. In the pursuit of filling these requirements, the following tasks have been accomplished: (1) Si nanocrystal charging has been accomplished with conducting-tip AFM; (2) Both individual nanocrystals on an oxide surface and nanocrystals formed by implantation have been charged; (3) Discharging is consistent with tunneling through a field-lowered oxide barrier; (4) Modeling of the response of the AFM to trapped charge has allowed estimation of the quantity of trapped charge; and (5) Initial attempts to fabricate competitive nanocrystal non-volatile memories have been extremely successful.

X-ray structural analysis of two-dimensional assembling lead sulfide nanocrystals of different sizes

NASA Astrophysics Data System (ADS)

Ushakova, Elena V.; Golubkov, Valery V.; Litvin, Aleksandr P.; Parfenov, Peter S.; Cherevkov, Sergei A.; Fedorov, Anatoly V.; Baranov, Alexander V.

2016-08-01

We report on the structural investigation of self-organized assemblies of PbS nanocrystals (NCs) of different sizes, which were deposited on a glass substrate or embedded in a porous matrix. Regardless of the NC size and the type of the substrate and matrix, the assemblies were ordered in two-dimensional superlattices with densely packed NCs.

Phase separation within NiSiN coatings during reactive HiPIMS discharges: A new pathway to grow NixSi nanocrystals composites at low temperature

NASA Astrophysics Data System (ADS)

Keraudy, J.; Boyd, R. D.; Shimizu, T.; Helmersson, U.; Jouan, P.-Y.

2018-10-01

The precise control of the growth nanostructured thin films at low temperature is critical for the continued development of microelectronic enabled devices. In this study, nanocomposite Ni-Si-N thin films were deposited at low temperature by reactive high-power impulse magnetron sputtering. A composite Ni-Si target (15 at.% Si) in combination with a Ar/N2 plasma were used to deposit films onto Si(0 0 1) substrates, without any additional substrate heating or any post-annealing. The films microstructure changes from a polycrystalline to nanocomposite structure when the nitrogen content exceeds 16 at.%. X-ray diffraction and (scanning) transmission electron microscopy analyses reveal that the microstructure consists of nanocrystals, NixSi (x > 1) 7-8 nm in size, embedded in an amorphous SiNx matrix. It is proposed that this nanostructure is formed at low temperatures due to the repeated-nucleation of NixSi nanocrystals, the growth of which is restricted by the formation of the SiNx phase. X-ray photoelectron spectroscopy revealed the trace presence of a ternary solid solution mainly induced by the diffusion of Ni into the SiNx matrix. Four-probe electrical measurements reveal all the deposited films are electrically conducting.

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.

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.

Growth and relaxation processes in Ge nanocrystals on free-standing Si(001) nanopillars.

PubMed

Kozlowski, G; Zaumseil, P; Schubert, M A; Yamamoto, Y; Bauer, J; Schülli, T U; Tillack, B; Schroeder, T

2012-03-23

We study the growth and relaxation processes of Ge crystals selectively grown by chemical vapour deposition on free-standing 90 nm wide Si(001) nanopillars. Epi-Ge with thickness ranging from 4 to 80 nm was characterized by synchrotron based x-ray diffraction and transmission electron microscopy. We found that the strain in Ge nanostructures is plastically released by nucleation of misfit dislocations, leading to degrees of relaxation ranging from 50 to 100%. The growth of Ge nanocrystals follows the equilibrium crystal shape terminated by low surface energy (001) and {113} facets. Although the volumes of Ge nanocrystals are homogeneous, their shape is not uniform and the crystal quality is limited by volume defects on {111} planes. This is not the case for the Ge/Si nanostructures subjected to thermal treatment. Here, improved structure quality together with high levels of uniformity of the size and shape is observed.

Preparation of Si nano-crystals with controlled oxidation state from SiO disproportionated by ZrO2 ball-milling

NASA Astrophysics Data System (ADS)

Okamoto, Yuji; Harada, Yoshitomo; Ohta, Narumi; Takada, Kazunori; Sumiya, Masatomo

2016-09-01

We demonstrate that a SiO disproportionation reaction can be achieved simply by high energy mechanochemical milling. The planetary ball-milling of ZrO2 for a few minutes generated Si nano-crystals. Milling conditions including rotation speed, ball number, milling time, and type of ball material were able to control the oxidation states of Si. The ball-milled SiO powder was tested as an anode of a lithium battery. ZrO2 contamination from the vial and balls was eliminated by dipping the ball-milled SiO powder in (NH4)HSO4 molten salt and heating for 5 min. The disproportionated SiO powder showed characteristics comparable to those of a powder prepared by a conventional heating process taking several hours.

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.

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.

Bright and multicolor luminescent colloidal Si nanocrystals prepared by pulsed laser irradiation in liquid

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

Nakamura, Toshihiro, E-mail: nakamura@el.gunma-u.ac.jp; Watanabe, Kanta; Adachi, Sadao

2016-01-11

We reported the preparation of bright and multicolor luminescent colloidal Si nanocrystal (Si-nc) by pulsed UV laser irradiation to porous Si (PSi) in an organic solvent. The different-luminescence-color (different-sized) colloidal Si-nc was produced by the pulsed laser-induced fragmentation of different-sized porous nanostructures. The colloidal Si-nc samples were found to have higher photoluminescence quantum efficiencies (20%–23%) than the PSi samples (1%–3%). The brighter emission of the colloidal Si-nc was attributed to an enhanced radiative band-to-band transition rate due to the presence of a surface organic layer formed by UV laser-induced hydrosilylation.

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.

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

NASA Astrophysics Data System (ADS)

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

2006-08-01

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

Correlation of TEM data with confined phonons to determine strain and size of Ge nanocrystals embedded in SixNy matrix

NASA Astrophysics Data System (ADS)

Bahariqushchi, Rahim; Gündoğdu, Sinan; Aydinli, Atilla

2017-11-01

Models that use phonon confinement fail to provide consistent results for nanocrystal sizes in differing dielectric matrices due to varying stress experienced by nanocrystals in different dielectric environments. In cases where direct measurement of stress is difficult, the possibility of stress saturation as a function of size opens up a window for the use of phonon confinement to determine size. We report on a test of this possibility in Ge: SixNy system. Ge nanocrystals (NCs) embedded in silicon nitride matrix have been fabricated using plasma enhanced chemical vapor deposition (PECVD) followed by post annealing in Ar ambient. Nanocrystal size dependence of Raman spectra was studied taking into account associated stress and an improved phonon confinement approach. Our analysis show same stress for NCs which have sizes below 7.0 nm allowing the use of phonon confinement to determine the nanocrystal size. The results are compared with TEM data and good agreement is observed.

Effects of nitrogen impurities on the microstructure and electronic properties of P-doped Si nanocrystals emebedded in silicon-rich SiNx films

NASA Astrophysics Data System (ADS)

Ma, Deng-Hao; Zhang, Wei-Jia; Luo, Rui-Ying; Jiang, Zhao-Yi; Ma, Qiang; Ma, Xiao-Bo; Fan, Zhi-Qiang; Song, Deng-Yuan; Zhang, Lei

2016-05-01

Phosphorus doped Si nanocrystals (SNCs) emebedded in silicon-rich SiNx:H films were prepared using plasma enhanced chemical vapor deposition technique, and the effects of nitrogen incorporation on the microstructure and electronic properties of the thin films have been systematically studied. Transmission electron microscope and Raman observation revealed that nitrogen incorporation prevents the growth of Si nanocrystals, and that their sizes can be adjusted by varying the flow rate of NH3. The reduction of photoluminescence (PL) intensity in the range of 2.1-2.6 eV of photon energy was observed with increasing nitrogen impurity, and a maximal PL intensity in the range 1.6-2.0 eV was obtained when the incorporation flow ratio NH3/(SiH4+H2+PH3) was 0.02. The conductivity of the films is improved by means of proper nitrogen impurity doping, and proper doping causes the interface charge density of the heterojunction (H-J) device to be lower than the nc-Si:H/c-Si H-J device. As a result, the proper incorporation of nitrogen could not only reduce the silicon banding bond density, but also fill some carrier capture centers, and suppress the nonradiative recombination of electrons.

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.

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

PubMed

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

2013-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2013-10-01

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

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

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.

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.

Biotin-decorated silica coated PbS nanocrystals emitting in the second biological near infrared window for bioimaging

NASA Astrophysics Data System (ADS)

Corricelli, M.; Depalo, N.; di Carlo, E.; Fanizza, E.; Laquintana, V.; Denora, N.; Agostiano, A.; Striccoli, M.; Curri, M. L.

2014-06-01

Nanoparticles (NPs) emitting in the second biological near infrared (NIR) window of the electromagnetic spectrum have been successfully synthesized by growing a silica shell on the hydrophobic surface of OLEA/TOP PbS nanocrystals (NCs), by means of a reverse microemulsion approach, and subsequently decorated with biotin molecules. The fabrication of very uniform and monodisperse NPs, formed of SiO2 shell coated single core PbS NCs, has been demonstrated by means of a set of complementary optical and structural techniques (Vis-NIR absorption and photoluminescence spectroscopy, transmission electron microscopy) that have highlighted how experimental parameters, such as PbS NC and silica precursor concentration, are crucial to direct the morphology and optical properties of silica coated PbS NPs. Subsequently, the silica surface of the core-shell NPs has been grafted with amino groups, in order to achieve covalent binding of biotin to NIR emitting silica coated NPs. Finally the successful reaction with a green-fluorescent labelled streptavidin has verified the molecular recognition response of the biotin molecules decorating the PbS@SiO2 NP surface. Dynamic light scattering (DLS) and ζ-potential techniques have been used to monitor the hydrodynamic diameter and colloidal stability of both PbS@SiO2 and biotin decorated NPs, showing their high colloidal stability in physiological media, as needed for biomedical applications. Remarkably the obtained biotinylated PbS@SiO2 NPs have been found to retain emission properties in the `second optical window' of the NIR region of the electromagnetic spectrum, thus representing attractive receptor-targeted NIR fluorescent probes for in vivo tumour imaging.Nanoparticles (NPs) emitting in the second biological near infrared (NIR) window of the electromagnetic spectrum have been successfully synthesized by growing a silica shell on the hydrophobic surface of OLEA/TOP PbS nanocrystals (NCs), by means of a reverse microemulsion

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.

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.

Reduced distribution of threshold voltage shift in double layer NiSi2 nanocrystals for nano-floating gate memory applications.

PubMed

Choi, Sungjin; Lee, Junhyuk; Kim, Donghyoun; Oh, Seulki; Song, Wangyu; Choi, Seonjun; Choi, Eunsuk; Lee, Seung-Beck

2011-12-01

We report on the fabrication and capacitance-voltage characteristics of double layer nickel-silicide nanocrystals with Si3N4 interlayer tunnel barrier for nano-floating gate memory applications. Compared with devices using SiO2 interlayer, the use of Si3N4 interlayer separation reduced the average size (4 nm) and distribution (+/- 2.5 nm) of NiSi2 nanocrystal (NC) charge traps by more than 50% and giving a two fold increase in NC density to 2.3 x 10(12) cm(-2). The increased density and reduced NC size distribution resulted in a significantly decrease in the distribution of the device C-V characteristics. For each program voltage, the distribution of the shift in the threshold voltage was reduced by more than 50% on average to less than 0.7 V demonstrating possible multi-level-cell operation.

Single-source-precursor synthesis of hafnium-containing ultrahigh-temperature ceramic nanocomposites (UHTC-NCs).

PubMed

Yuan, Jia; Hapis, Stefania; Breitzke, Hergen; Xu, Yeping; Fasel, Claudia; Kleebe, Hans-Joachim; Buntkowsky, Gerd; Riedel, Ralf; Ionescu, Emanuel

2014-10-06

Amorphous SiHfBCN ceramics were prepared from a commercial polysilazane (HTT 1800, AZ-EM), which was modified upon reactions with Hf(NEt2)4 and BH3·SMe2, and subsequently cross-linked and pyrolyzed. The prepared materials were investigated with respect to their chemical and phase composition, by means of spectroscopy techniques (Fourier transform infrared (FTIR), Raman, magic-angle spinning nuclear magnetic resonance (MAS NMR)), as well as X-ray diffraction (XRD) and transmission electron microscopy (TEM). Annealing experiments of the SiHfBCN samples in an inert gas atmosphere (Ar, N2) at temperatures in the range of 1300-1700 °C showed the conversion of the amorphous materials into nanostructured UHTC-NCs. Depending on the annealing atmosphere, HfC/HfB2/SiC (annealing in argon) and HfN/Si3N4/SiBCN (annealing in nitrogen) nanocomposites were obtained. The results emphasize that the conversion of the single-phase SiHfBCN into UHTC-NCs is thermodynamically controlled, thus allowing for a knowledge-based preparative path toward nanostructured ultrahigh-temperature stable materials with adjusted compositions.

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.

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

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

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

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.

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.

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.

Swift heavy ion irradiation of Pt nanocrystals: II. Structural changes and H desorption

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

Giulian, R.; Araujo, L.L.; Kluth, P.

2014-09-24

The structural properties and H desorption from embedded Pt nanocrystals (NCs) following irradiation with swift heavy ions were investigated as a function of energy and fluence. From x-ray absorption near-edge spectroscopy analysis, Pt-H bonding was identified in NCs annealed in a forming gas (95% N{sub 2} + 5% H{sub 2}) ambient. The H content decreased upon irradiation and the desorption process was NC-size dependent such that larger NCs required a higher fluence to achieve a H-free state. Pt-H bonding and NC dissolution both perturbed the NC structural parameters (coordination number, bond-length and mean-square relative displacement) as determined with extended x-raymore » absorption fine structure measurements.« less

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.

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

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.

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.

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.

SiGe layer thickness effect on the structural and optical properties of well-organized SiGe/SiO2 multilayers

NASA Astrophysics Data System (ADS)

Vieira, E. M. F.; Toudert, J.; Rolo, A. G.; Parisini, A.; Leitão, J. P.; Correia, M. R.; Franco, N.; Alves, E.; Chahboun, A.; Martín-Sánchez, J.; Serna, R.; Gomes, M. J. M.

2017-08-01

In this work, we report on the production of regular (SiGe/SiO2)20 multilayer structures by conventional RF-magnetron sputtering, at 350 °C. Transmission electron microscopy, scanning transmission electron microscopy, raman spectroscopy, and x-ray reflectometry measurements revealed that annealing at a temperature of 1000 °C leads to the formation of SiGe nanocrystals between SiO2 thin layers with good multilayer stability. Reducing the nominal SiGe layer thickness (t SiGe) from 3.5-2 nm results in a transition from continuous SiGe crystalline layer (t SiGe ˜ 3.5 nm) to layers consisting of isolated nanocrystals (t SiGe ˜ 2 nm). Namely, in the latter case, the presence of SiGe nanocrystals ˜3-8 nm in size, is observed. Spectroscopic ellipsometry was applied to determine the evolution of the onset in the effective optical absorption, as well as the dielectric function, in SiGe multilayers as a function of the SiGe thickness. A clear blue-shift in the optical absorption is observed for t SiGe ˜ 2 nm multilayer, as a consequence of the presence of isolated nanocrystals. Furthermore, the observed near infrared values of n = 2.8 and k = 1.5 are lower than those of bulk SiGe compounds, suggesting the presence of electronic confinement effects in the nanocrystals. The low temperature (70 K) photoluminescence measurements performed on annealed SiGe/SiO2 nanostructures show an emission band located between 0.7-0.9 eV associated with the development of interface states between the formed nanocrystals and surrounding amorphous matrix.

Effect of embedded metal nanocrystals on the resistive switching characteristics in NiN-based resistive random access memory cells

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

Yun, Min Ju; Kim, Hee-Dong; Man Hong, Seok

2014-03-07

The metal nanocrystals (NCs) embedded-NiN-based resistive random access memory cells are demonstrated using several metal NCs (i.e., Pt, Ni, and Ti) with different physical parameters in order to investigate the metal NC's dependence on resistive switching (RS) characteristics. First, depending on the electronegativity of metal, the size of metal NCs is determined and this affects the operating current of memory cells. If metal NCs with high electronegativity are incorporated, the size of the NCs is reduced; hence, the operating current is reduced owing to the reduced density of the electric field around the metal NCs. Second, the potential wells aremore » formed by the difference of work function between the metal NCs and active layer, and the barrier height of the potential wells affects the level of operating voltage as well as the conduction mechanism of metal NCs embedded memory cells. Therefore, by understanding these correlations between the active layer and embedded metal NCs, we can optimize the RS properties of metal NCs embedded memory cells as well as predict their conduction mechanisms.« 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.

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.

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.

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

Nanocrystal assembly for tandem catalysis

DOEpatents

Yang, Peidong; Somorjai, Gabor; Yamada, Yusuke; Tsung, Chia-Kuang; Huang, Wenyu

2014-10-14

The present invention provides a nanocrystal tandem catalyst comprising at least two metal-metal oxide interfaces for the catalysis of sequential reactions. One embodiment utilizes a nanocrystal bilayer structure formed by assembling sub-10 nm platinum and cerium oxide nanocube monolayers on a silica substrate. The two distinct metal-metal oxide interfaces, CeO.sub.2--Pt and Pt--SiO.sub.2, can be used to catalyze two distinct sequential reactions. The CeO.sub.2--Pt interface catalyzed methanol decomposition to produce CO and H.sub.2, which were then subsequently used for ethylene hydroformylation catalyzed by the nearby Pt--SiO.sub.2 interface. Consequently, propanal was selectively produced on this nanocrystal bilayer tandem catalyst.

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.

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.

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

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

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

Singlet Oxygen Generation Mediated By Silicon Nanocrystal Assemblies

DTIC Science & Technology

2011-01-01

Lattice fringes in Fig.3 d correspond to the (111) atomic planes of Si nanocrystals. Length scales are indicated. Downscaling of the stain etched PSi...intensity of 1W/cm2 in a time scale of a few hours a monolayer of oxygen is formed on the surface of Si nanocrystals. Fig. 8. Infrared absorption...solution. Fig. 10. PL intensity as a function of continuously prolonged etching of Si powder. Inset: PL suppression level (can be scaled as singlet

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

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.

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.

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.

Atomic force microscopy nanomanipulation of silicon nanocrystals for nanodevice fabrication

NASA Astrophysics Data System (ADS)

Decossas, Sébastien; Mazen, Frédéric; Baron, Thierry; Brémond, Georges; Souifi, Abdelkader

2003-12-01

An atomic force microscopy (AFM) tip has been used to manipulate silicon nanocrystals deposited by low-pressure chemical vapour deposition on thermally oxidized p-type Si wafer. Three nanomanipulation methods are presented. The first one catches a nanocrystal with the AFM tip and deposits it elsewhere: the tip is used as an electrostatic 'nano-crane'. The second one simultaneously manipulates a set of nanocrystals in order to draw well-defined unidimensional lines: the tip is used as a 'nano-broom'. The third one manipulates individual nanocrystals with a precision of about 10 nm using both oscillating and contact AFM modes. Switching from strong interaction forces (chemical) to weak ones (van der Waals, electrostatic or capillarity) is the basis of these manipulation methods. We have applied the second method to connect two electrodes drawn by e-beam and lift-off with a 70 nm long silicon nanocrystal chain. Current versus voltage characterization of the nanofabricated device shows that the increase in nanocrystal density gives rise to conduction between the connected electrodes. Resonant tunnelling effects resulting from Si nanocrystal (nc-Si) multiple tunnel junctions have been observed at 300 K. We also show that offset charges directly influence the position of the resonant tunnelling peaks. Finally, the possibility of manipulating nc-Si with a diameter of around 5 nm is shown to be a promising way to fabricate single electron devices operating at room temperature and fully compatible with silicon technology.

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.

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.

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.

Introduction of Si/SiO{sub 2} interface states by annealing Ge-implanted films

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

Marstein, E.S.; Gunnaes, A.E.; Olsen, A.

2004-10-15

Nanocrystals embedded in SiO{sub 2} films are the subject of a number of recent works, mainly because of their potential usefulness in the fabrication of optoelectronic devices and nanocrystal memory structures. One interesting method for the fabrication of such nanocrystals is the ion implantation of segregating species into SiO{sub 2} films followed by heat treatment in order to induce nanocrystal formation. This method is both relatively simple and also compatible with the current MOS (metal-oxide-semiconductor) device technology. An unintentional effect can occur during the fabrication of nanocrystals using this method, namely a significant diffusion of the implanted species during annealing,more » away from the regions with the highest concentration. The Si/SiO{sub 2} interface can be exposed to this diffusion flux. This can result in an altered interface and have a significant influence on electronic devices. Here, we report on ion implantation of Ge into SiO{sub 2} on Si followed by annealing under conditions, resulting in Ge accumulation at the Si/SiO{sub 2} interface as determined by secondary-ion mass spectroscopy analysis, transmission electron microscopy with energy dispersive analysis of x-rays, and Rutherford backscattering spectrometry. The accumulation of Ge at the Si/SiO{sub 2} interface has also been reported before. The resulting effect on the electronic structure of the interface is a priori unknown. We have fabricated MOS capacitors on the sample structures and their capacitance-voltage characteristics were measured and analyzed. We measure an interface state density around 1x10{sup 12} cm{sup -2}, which is high compared to standard Si MOS devices. We discuss the results in terms of the previous electrical measurements on Ge-oxide interfaces and SiGe interfaces, which also can yield a high interface state density. The specific conditions we report result in a sufficiently low Ge concentration that nanocrystals are not segregated in the Si

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.

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

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.

Charge trapping phenomena of tetraethylorthosilicate thin film containing Si nanocrystals synthesized by solid-state reaction.

PubMed

Lau, H W; Tan, O K; Liu, Y; Trigg, D A; Chen, T P

2006-08-28

In this work, we report on the fabrication of tetraethylorthosilicate (TEOS) thin dielectric film containing silicon nanocrystals (Si nc), synthesized by solid-state reaction, in a capacitor structure. A metal-insulator-semi-conductor (MIS) capacitor, with 28 nm thick Si nc in a TEOS thin film, has been fabricated. For this MIS, both electron and hole trapping in the Si nc are possible, depending on the polarity of the bias voltage. A V(FB) shift greater than 1 V can be experienced by a bias voltage of 16 V applied to the metal electrode for 1 s. Though there is no top control oxide, the discharge time for 10% of charges can be up to 4480 s when it is biased at 16 V for 1 s. It is further demonstrated that charging and discharging mechanisms are due to the Si nc rather than the TEOS oxide defects. This form of Si nc in a TEOS thin film capacitor provides the possibility of memory applications at low cost.

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.

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.

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.

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.

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.

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

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

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. 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

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.

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

Optimizing non-radiative energy transfer in hybrid colloidal-nanocrystal/silicon structures by controlled nanopillar architectures for future photovoltaic cells

NASA Astrophysics Data System (ADS)

Seitz, O.; Caillard, L.; Nguyen, H. M.; Chiles, C.; Chabal, Y. J.; Malko, A. V.

2012-01-01

To optimize colloidal nanocrystals/Si hybrid structures, nanopillars are prepared and organized via microparticle patterning and Si etching. A monolayer of CdSe nanocrystals is then grafted on the passivated oxide-free nanopillar surfaces, functionalized with carboxy-alkyl chain linkers. This process results to a negligible number of non-radiative surface state defects with a tightly controlled separation between the nanocrystals and Si. Steady-state and time-resolved photoluminescence measurements confirm the close-packing nanocrystal arrangement and the dominance of non-radiative energy transfer from nanocrystals to Si. We suggest that radially doped p-n junction devices based on energy transfer offer a viable approach for thin film photovoltaic devices.

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.

High-dose MeV electron irradiation of Si-SiO2 structures implanted with high doses Si+

NASA Astrophysics Data System (ADS)

Kaschieva, S.; Angelov, Ch; Dmitriev, S. N.

2018-03-01

The influence was studied of 22-MeV electron irradiation on Si-SiO2 structures implanted with high-fluence Si+ ions. Our earlier works demonstrated that Si redistribution is observed in Si+-ion-implanted Si-SiO2 structures (after MeV electron irradiation) only in the case when ion implantation is carried out with a higher fluence (1016 cm-2). We focused our attention on the interaction of high-dose MeV electron irradiation (6.0×1016 cm-2) with n-Si-SiO2 structures implanted with Si+ ions (fluence 5.4×1016 cm-2 of the same order magnitude). The redistribution of both oxygen and silicon atoms in the implanted Si-SiO2 samples after MeV electron irradiation was studied by Rutherford back-scattering (RBS) spectroscopy in combination with a channeling technique (RBS/C). Our results demonstrated that the redistribution of oxygen and silicon atoms in the implanted samples reaches saturation after these high doses of MeV electron irradiation. The transformation of amorphous SiO2 surface into crystalline Si nanostructures (after MeV electron irradiation) was evidenced by atomic force microscopy (AFM). Silicon nanocrystals are formed on the SiO2 surface after MeV electron irradiation. The shape and number of the Si nanocrystals on the SiO2 surface depend on the MeV electron irradiation, while their size increases with the dose. The mean Si nanocrystals height is 16-20 nm after irradiation with MeV electrons at the dose of 6.0×1016 cm-2.

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

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.

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

Enhanced photovoltaic performance of ultrathin Si solar cells via semiconductor nanocrystal sensitization: Energy transfer vs. optical coupling effects

DOE PAGES

Hoang, Son; Ashraf, Ahsan; Eisaman, Matthew D.; ...

2015-12-07

Excitonic energy transfer (ET) offers exciting opportunities for advances in optoelectronic devices such as solar cells. While recent experimental attempts have demonstrated its potential in both organic and inorganic photovoltaics (PVs), what remains to be addressed is quantitative understanding of how different ET modes contribute to PV performance and how ET contribution is differentiated from the classical optical coupling (OC) effects. In this study, we implement an ET scheme using a PV device platform, comprising CdSe/ZnS nanocrystal energy donor and 500 nm-thick ultrathin Si acceptor layers, and present the quantitative mechanistic description of how different ET modes, distinguished from themore » OC effects, increase the light absorption and PV efficiency. We find that nanocrystal sensitization enhances the short circuit current of ultrathin Si solar cells by up to 35%, of which the efficient ET, primarily driven by a long-range radiative mode, contributes to 38% of the total current enhancement. Lastly, these results not only confirm the positive impact of ET but also provide a guideline for rationally combining the ET and OC effects for improved light harvesting in PV and other optoelectronic devices.« less

Enhanced photovoltaic performance of ultrathin Si solar cells via semiconductor nanocrystal sensitization: energy transfer vs. optical coupling effects.

PubMed

Hoang, Son; Ashraf, Ahsan; Eisaman, Matthew D; Nykypanchuk, Dmytro; Nam, Chang-Yong

2016-03-21

Excitonic energy transfer (ET) offers exciting opportunities for advances in optoelectronic devices such as solar cells. While recent experimental attempts have demonstrated its potential in both organic and inorganic photovoltaics (PVs), what remains to be addressed is quantitative understanding of how different ET modes contribute to PV performance and how ET contribution is differentiated from the classical optical coupling (OC) effects. In this study, we implement an ET scheme using a PV device platform, comprising CdSe/ZnS nanocrystal energy donor and 500 nm-thick ultrathin Si acceptor layers, and present the quantitative mechanistic description of how different ET modes, distinguished from the OC effects, increase the light absorption and PV efficiency. We find that nanocrystal sensitization enhances the short circuit current of ultrathin Si solar cells by up to 35%, of which the efficient ET, primarily driven by a long-range radiative mode, contributes to 38% of the total current enhancement. These results not only confirm the positive impact of ET but also provide a guideline for rationally combining the ET and OC effects for improved light harvesting in PV and other optoelectronic devices.

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.

``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.

Size-Tunable Photothermal Germanium Nanocrystals.

PubMed

Sun, Wei; Zhong, Grace; Kübel, Christian; Jelle, Abdinoor A; Qian, Chenxi; Wang, Lu; Ebrahimi, Manuchehr; Reyes, Laura M; Helmy, Amr S; Ozin, Geoffrey A

2017-05-22

Germanium nanocrystals (ncGe) have not received as much attention as silicon nanocrystals (ncSi). However, Ge has demonstrated superiority over Si nanomaterials in some applications. Examples include, high charge-discharge rate lithium-ion batteries, small band-gap opto-electronic devices, and photo-therapeutics. When stabilized in an oxide matrix (ncGe/GeO x ), its high charge-retention has enabled non-volatile memories. It has also found utility as a high-capacity anode material for Li-ion batteries with impressive stability. Herein, we report an organic-free synthesis of size-controlled ncGe in a GeO x matrix as well as freestanding ncGe, via the thermal disproportionation of GeO prepared from thermally induced dehydration of Ge(OH) 2 . The photothermal effect of ncGe, quantified by Raman spectroscopy, is found to be size dependent and superior to ncSi. This advance suggests applications of ncGe in photothermal therapy, desalination, and catalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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...

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

NASA Astrophysics Data System (ADS)

Panthani, Matthew George

2011-07-01

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

Inorganic Nanocrystals Functionalized Mesoporous Silica Nanoparticles: Fabrication and Enhanced Bio-applications

NASA Astrophysics Data System (ADS)

Zhao, Tiancong; Nguyen, Nam-Trung; Xie, Yang; Sun, Xiaofei; Li, Qin; Li, Xiaomin

2017-12-01

Mesoporous SiO2 nanoparticles (MSNs) are one of the most promising materials for bio-related applications due to advantages such as good biocompatibility, tunable mesopores and large pore volume. However, unlike the inorganic nanocrystals with abundant physical properties, MSNs alone lack functional features. Thus, they are not sufficiently suitable for bio-applications that require special functions. Consequently, MSNs are often functionalized by incorporating inorganic nanocrystals, which provide a wide range of intriguing properties. This review focuses on inorganic nanocrystals functionalized MSNs, both their fabrication and bio-applications. Some of the most utilized methods for coating mesoporous silica (mSiO2) on nanoparticles were summarized. Magnetic, fluorescence and photothermal inorganic nanocrystals functionalized MSNs were taken as examples to demonstrate the bio-applications. Furthermore, asymmetry of MSNs and their effects on functions were also highlighted.

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.

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.

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

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

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

2015-05-15

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

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

Temperature effect on the structural stabilities and electronic properties of X22H28 (X=C, Si and Ge) nanocrystals: A first-principles study

NASA Astrophysics Data System (ADS)

Deng, Xiao-Lin; Zhao, Yu-Jun; Wang, Ya-Ting; Liao, Ji-Hai; Yang, Xiao-Bao

2016-12-01

Based on ab initio molecular dynamic simulations, we have theoretically investigated the structural stabilities and electronic properties of X22H28 (X=C, Si, and Ge) nanocrystals, as a function of temperature with consideration of vibrational entropy effects. To compare the relative stabilities of X22H28 isomers, the vibration free energies are obtained according to the calculated phonon spectrum, where the typical modes are shown to be dominant to the structural stabilities. In addition, there is a significant gap reduction as the temperature increases from 0 K to 300 K, where the decrements are 0.2 /0.5 /0.6eV for C/Si/Ge nanocrystals, respectively. The dependence of energy gap on the variance of bond length is also analyzed according to the corresponding atomic attributions to the HOMO and LUMO levels.

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.

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.

Study of the correlation properties of the surface structure of nc-Si/a-Si:H films with different fractions of the crystalline phase

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

Alpatov, A. V., E-mail: pgnv@mail.ru; Vikhrov, S. P.; Kazanskii, A. G.

The correlation properties of the structure of nc-Si/a-Si:H films with different volume fractions of the crystalline phase are studied using 2D detrended fluctuation analysis. Study of the surface relief of experimental samples showed that with increasing in volume fraction of the crystalline phase in the nc-Si/a-Si:H films, the size and number of nanoclusters on their surface grow. The size of Si nanocrystals in the a-Si:H matrix (6–8 nm) indicates the formation of coarse nanoclusters due to the self-organization of Si nanocrystals in groups under laser radiation. According to 2D detrended fluctuation analysis data, the number of correlation vectors (harmonic components)more » in the nc-Si/a-Si:H film structure increased with an increase in the nanocrystal fraction in the films.« less

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

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.

Glass-ceramic optical fiber containing Ba2TiSi2O8 nanocrystals for frequency conversion of lasers

NASA Astrophysics Data System (ADS)

Fang, Zaijin; Xiao, Xusheng; Wang, Xin; Ma, Zhijun; Lewis, Elfed; Farrell, Gerald; Wang, Pengfei; Ren, Jing; Guo, Haitao; Qiu, Jianrong

2017-03-01

A glass-ceramic optical fiber containing Ba2TiSi2O8 nanocrystals fabricated using a novel combination of the melt-in-tube method and successive heat treatment is reported for the first time. For the melt-in-tube method, fibers act as a precursor at the drawing temperature for which the cladding glass is softened while the core glass is melted. It is demonstrated experimentally that following heat treatment, Ba2TiSi2O8 nanocrystals with diameters below 10 nm are evenly distributed throughout the fiber core. Comparing to the conventional rod-in-tube method, the melt-in-tube method is superior in terms of controllability of crystallization to allow for the fabrication of low loss glass-ceramic fibers. When irradiated using a 1030 nm femtosecond laser, an enhanced green emission at a wavelength of 515 nm is observed in the glass-ceramic fiber, which demonstrates second harmonic generation of a laser action in the fabricated glass-ceramic fibers. Therefore, this new glass-ceramic fiber not only provides a highly promising development for frequency conversion of lasers in all optical fiber based networks, but the melt-in-tube fabrication method also offers excellent opportunities for fabricating a wide range of novel glass-ceramic optical fibers for multiple future applications including fiber telecommunications and lasers.

Glass-ceramic optical fiber containing Ba2TiSi2O8 nanocrystals for frequency conversion of lasers

PubMed Central

Fang, Zaijin; Xiao, Xusheng; Wang, Xin; Ma, Zhijun; Lewis, Elfed; Farrell, Gerald; Wang, Pengfei; Ren, Jing; Guo, Haitao; Qiu, Jianrong

2017-01-01

A glass-ceramic optical fiber containing Ba2TiSi2O8 nanocrystals fabricated using a novel combination of the melt-in-tube method and successive heat treatment is reported for the first time. For the melt-in-tube method, fibers act as a precursor at the drawing temperature for which the cladding glass is softened while the core glass is melted. It is demonstrated experimentally that following heat treatment, Ba2TiSi2O8 nanocrystals with diameters below 10 nm are evenly distributed throughout the fiber core. Comparing to the conventional rod-in-tube method, the melt-in-tube method is superior in terms of controllability of crystallization to allow for the fabrication of low loss glass-ceramic fibers. When irradiated using a 1030 nm femtosecond laser, an enhanced green emission at a wavelength of 515 nm is observed in the glass-ceramic fiber, which demonstrates second harmonic generation of a laser action in the fabricated glass-ceramic fibers. Therefore, this new glass-ceramic fiber not only provides a highly promising development for frequency conversion of lasers in all optical fiber based networks, but the melt-in-tube fabrication method also offers excellent opportunities for fabricating a wide range of novel glass-ceramic optical fibers for multiple future applications including fiber telecommunications and lasers. PMID:28358045

Glass-ceramic optical fiber containing Ba2TiSi2O8 nanocrystals for frequency conversion of lasers.

PubMed

Fang, Zaijin; Xiao, Xusheng; Wang, Xin; Ma, Zhijun; Lewis, Elfed; Farrell, Gerald; Wang, Pengfei; Ren, Jing; Guo, Haitao; Qiu, Jianrong

2017-03-30

A glass-ceramic optical fiber containing Ba 2 TiSi 2 O 8 nanocrystals fabricated using a novel combination of the melt-in-tube method and successive heat treatment is reported for the first time. For the melt-in-tube method, fibers act as a precursor at the drawing temperature for which the cladding glass is softened while the core glass is melted. It is demonstrated experimentally that following heat treatment, Ba 2 TiSi 2 O 8 nanocrystals with diameters below 10 nm are evenly distributed throughout the fiber core. Comparing to the conventional rod-in-tube method, the melt-in-tube method is superior in terms of controllability of crystallization to allow for the fabrication of low loss glass-ceramic fibers. When irradiated using a 1030 nm femtosecond laser, an enhanced green emission at a wavelength of 515 nm is observed in the glass-ceramic fiber, which demonstrates second harmonic generation of a laser action in the fabricated glass-ceramic fibers. Therefore, this new glass-ceramic fiber not only provides a highly promising development for frequency conversion of lasers in all optical fiber based networks, but the melt-in-tube fabrication method also offers excellent opportunities for fabricating a wide range of novel glass-ceramic optical fibers for multiple future applications including fiber telecommunications and lasers.

Effect of annealing under tensile loading on the structure of nanocrystals in the Finemet alloy

NASA Astrophysics Data System (ADS)

Ershov, N. V.; Chernenkov, Yu. P.; Fedorov, V. I.; Lukshina, V. A.; Potapov, A. P.

2014-11-01

The effect of nanocrystallization annealing under tensile loading on the structure of nanocrystals in the soft magnetic alloy Fe-Si-Nb-B-Cu (Finemet) has been investigated. It has been shown that the body-centered cubic (bcc) lattice of α-FeSi nanocrystals is extended along the direction of the application of the load upon annealing and is compressed in the transverse direction. Nanocrystals in the Finemet alloy have a higher degree of anisotropy of mechanical properties as compared to bulk crystals of α-FeSi, so that agreement between the measured and calculated values of the elongation is achieved only with a significant increase in the elastic moduli. Substantial changes in mechanical properties of the crystals with a decrease in their size to the nanometer scale are caused by the influence of the rigid amorphous matrix of the Fe(Nb)-B phase surrounding the nanocrystals.

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.

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).

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

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.

Liquid phase epitaxy of binary III–V nanocrystals in thin Si layers triggered by ion implantation and flash lamp annealing

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

Wutzler, Rene, E-mail: r.wutzler@hzdr.de; Rebohle, Lars; Prucnal, Slawomir

2015-05-07

The integration of III–V compound semiconductors in Si is a crucial step towards faster and smaller devices in future technologies. In this work, we investigate the formation process of III–V compound semiconductor nanocrystals, namely, GaAs, GaSb, and InP, by ion implantation and sub-second flash lamp annealing in a SiO{sub 2}/Si/SiO{sub 2} layer stack on Si grown by plasma-enhanced chemical vapor deposition. Raman spectroscopy, Rutherford Backscattering spectrometry, and transmission electron microscopy were performed to identify the structural and optical properties of these structures. Raman spectra of the nanocomposites show typical phonon modes of the compound semiconductors. The formation process of themore » III–V compounds is found to be based on liquid phase epitaxy, and the model is extended to the case of an amorphous matrix without an epitaxial template from a Si substrate. It is shown that the particular segregation and diffusion coefficients of the implanted group-III and group-V ions in molten Si significantly determine the final appearance of the nanostructure and thus their suitability for potential applications.« less

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).

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.

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.

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

Some fundamental and applicative properties of [polymer/nano-SiC] hybrid nanocomposites

NASA Astrophysics Data System (ADS)

Kassiba, A.; Bouclé, J.; Makowska-Janusik, M.; Errien, N.

2007-08-01

Hybrid nanocomposites which combine polymer as host matrix and nanocrystals as active elements are promising functional materials for electronics, optics or photonics. In these systems, the physical response is governed by the nanocrystal features (size, surface and defect states), the polymer properties and the polymer-nanocrystal interface. This work reviews some selective nanostructured architectures based on active elements such as silicon carbide (SiC) nanocrystals and polymer host matrices. Beyond an overview of some key properties of the nanocrystals, a main part will be devoted to the electro-optical (EO) properties of SiC based hybrid systems where SiC nanocrystals are embedded in polymer matrices of different chemical nature such as poly-(methylmethacrylate) (PMMA), poly-vinylcarbazole (PVK) or polycarbonate. Using this approach, the organic-inorganic interface effects are emphasised with regard to the dielectric or hole transporting behaviour of PMMA and PVK respectively. These effects are illustrated through different EO responses associated with hybrid composites based on PMMA or PVK.

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

Highly sensitive and stable Ag@SiO2 nanocubes for label-free SERS-photoluminescence detection of biomolecules

NASA Astrophysics Data System (ADS)

Nguyen, Minh-Kha; Su, Wei-Nien; Chen, Ching-Hsiang; Rick, John; Hwang, Bing-Joe

2017-03-01

Surface-enhanced Raman scattering (SERS) and fluorescence microscopy are a widely used biological and chemical characterization techniques. However, the peak overlapping in multiplexed experiments and rapid photobleaching of fluorescent organic dyes is still the limitations. When compared to Ag nanocubes (NCs), higher SERS sensitivities can be obtained with thin shelled silica Ag@SiO2 NCs, in contrast metal-enhanced photoluminescence (MEPL) is only found with NCs that have thicker silica shells. A 'dual functionality' represented by the simultaneous strengthening of SERS and MEPL signals can be achieved by mixing Ag@SiO2 NCs, with a silica shell thickness of 1.5 nm and 4.4 nm. This approach allows both the Ag@SiO2 NCs SERS and MEPL sensitivities to be maintained at 90% after 12 weeks of storage. Based on the distinguished detection of creatinine and flavin adenine dinucleotide in the mixture, the integration of SERS and MEPL together on a stable single plasmonic nanoparticle platform offers an opportunity to enhance both biomarker detection sensitivity and specificity.

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).

Creating ligand-free silicon germanium alloy nanocrystal inks.

PubMed

Erogbogbo, Folarin; Liu, Tianhang; Ramadurai, Nithin; Tuccarione, Phillip; Lai, Larry; Swihart, Mark T; Prasad, Paras N

2011-10-25

Particle size is widely used to tune the electronic, optical, and catalytic properties of semiconductor nanocrystals. This contrasts with bulk semiconductors, where properties are tuned based on composition, either through doping or through band gap engineering of alloys. Ideally, one would like to control both size and composition of semiconductor nanocrystals. Here, we demonstrate production of silicon-germanium alloy nanoparticles by laser pyrolysis of silane and germane. We have used FTIR, TEM, XRD, EDX, SEM, and TOF-SIMS to conclusively determine their structure and composition. Moreover, we show that upon extended sonication in selected solvents, these bare nanocrystals can be stably dispersed without ligands, thereby providing the possibility of using them as an ink to make patterned films, free of organic surfactants, for device fabrication. The engineering of these SiGe alloy inks is an important step toward the low-cost fabrication of group IV nanocrystal optoelectronic, thermoelectric, and photovoltaic devices.

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

Neutral six-coordinate bis(dithiocarbamato)silicon(iv) complexes with an SiCl2S4 skeleton.

PubMed

Baus, Johannes A; Tacke, Reinhold

2017-07-11

Treatment of SiCl 4 with lithium dithiocarbamates of the formula type Li[R 2 NCS 2 ] (R = Ph, iPr) in a molar ratio of 1 : 2 afforded the respective six-coordinate silicon(iv) complexes [Ph 2 NCS 2 ] 2 SiCl 2 (3) and [iPr 2 NCS 2 ] 2 SiCl 2 (4), which were isolated as the solvates 3·MeCN and 4·MeCN. Compounds 3·MeCN and 4·MeCN were structurally characterised by single-crystal X-ray diffraction and multinuclear NMR spectroscopic studies in the solid state and in solution. In this study, dithiocarbamato ligands were implemented in silicon coordination chemistry for the first time. Compounds 3 and 4 represent the first six-coordinate silicon(iv) complexes with an SiCl 2 S 4 skeleton.

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.

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.

Tin induced a-Si crystallization in thin films of Si-Sn alloys

NASA Astrophysics Data System (ADS)

Neimash, V.; Poroshin, V.; Shepeliavyi, P.; Yukhymchuk, V.; Melnyk, V.; Kuzmich, A.; Makara, V.; Goushcha, A. O.

2013-12-01

Effects of tin doping on crystallization of amorphous silicon were studied using Raman scattering, Auger spectroscopy, scanning electron microscopy, and X-ray fluorescence techniques. Formation of silicon nanocrystals (2-4 nm in size) in the amorphous matrix of Si1-xSnx, obtained by physical vapor deposition of the components in vacuum, was observed at temperatures around 300 °C. The aggregate volume of nanocrystals in the deposited film of Si1-xSnx exceeded 60% of the total film volume and correlated well with the tin content. Formation of structures with ˜80% partial volume of the nanocrystalline phase was also demonstrated. Tin-induced crystallization of amorphous silicon occurred only around the clusters of metallic tin, which suggested the crystallization mechanism involving an interfacial molten Si:Sn layer.

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

Investigation of radiation hardened SOI wafer fabricated by ion-cut technique

NASA Astrophysics Data System (ADS)

Chang, Yongwei; Wei, Xing; Zhu, Lei; Su, Xin; Gao, Nan; Dong, Yemin

2018-07-01

Total ionizing dose (TID) effect on Silicon-on-Insulator (SOI) wafers due to inherent buried oxide (BOX) is a significant concern as it leads to the degradation of electrical properties of SOI-based devices and circuits, even failures of the systems associated with them. This paper reports the radiation hardening implementation of SOI wafer fabricated by ion-cut technique integrated with low-energy Si+ implantation. The electrical properties and radiation response of pseudo-MOS transistors are analyzed. The results demonstrate that the hardening process can significantly improve the TID tolerance of SOI wafers by generating Si nanocrystals (Si-NCs) within the BOX. The presence of Si-NCs created through Si+ implantation is evidenced by high-resolution transmission electron microscopy (HR-TEM). Under the pass gate (PG) irradiation bias, the anti-radiation properties of H-gate SOI nMOSFETs suggest that the radiation hardened SOI wafers with optimized Si implantation dose can perform effectively in a radiation environment. The radiation hardening process provides an excellent way to reinforce the TID tolerance of SOI wafers.

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...

On the role of spatial position of bridged oxygen atoms as surface passivants on the ground-state gap and photo-absorption spectrum of silicon nano-crystals

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

Nazemi, Sanaz; Soleimani, Ebrahim Asl; Pourfath, Mahdi, E-mail: pourfath@ut.ac.ir, E-mail: pourfath@iue.tuwien.ac.at

2015-11-28

Silicon nano-crystals (NCs) are potential candidates for enhancing and tuning optical properties of silicon for optoelectronic and photo-voltaic applications. Due to the high surface-to-volume ratio, however, optical properties of NC result from the interplay of quantum confinement and surface effects. In this work, we show that both the spatial position of surface terminants and their relative positions have strong effects on NC properties as well. This is accomplished by investigating the ground-state HOMO-LUMO band-gap, the photo-absorption spectra, and the localization and overlap of HOMO and LUMO orbital densities for prototype ∼1.2 nm Si{sub 32–x}H{sub 42–2x}O{sub x} hydrogenated silicon NC with bridgedmore » oxygen atoms as surface terminations. It is demonstrated that the surface passivation geometry significantly alters the localization center and thus the overlap of frontier molecular orbitals, which correspondingly modifies the electronic and optical properties of NC.« less

Selective Epitaxy of InP on Si and Rectification in Graphene/InP/Si Hybrid Structure.

PubMed

Niu, Gang; Capellini, Giovanni; Hatami, Fariba; Di Bartolomeo, Antonio; Niermann, Tore; Hussein, Emad Hameed; Schubert, Markus Andreas; Krause, Hans-Michael; Zaumseil, Peter; Skibitzki, Oliver; Lupina, Grzegorz; Masselink, William Ted; Lehmann, Michael; Xie, Ya-Hong; Schroeder, Thomas

2016-10-12

The epitaxial integration of highly heterogeneous material systems with silicon (Si) is a central topic in (opto-)electronics owing to device applications. InP could open new avenues for the realization of novel devices such as high-mobility transistors in next-generation CMOS or efficient lasers in Si photonics circuitry. However, the InP/Si heteroepitaxy is highly challenging due to the lattice (∼8%), thermal expansion mismatch (∼84%), and the different lattice symmetries. Here, we demonstrate the growth of InP nanocrystals showing high structural quality and excellent optoelectronic properties on Si. Our CMOS-compatible innovative approach exploits the selective epitaxy of InP nanocrystals on Si nanometric seeds obtained by the opening of lattice-arranged Si nanotips embedded in a SiO 2 matrix. A graphene/InP/Si-tip heterostructure was realized on obtained materials, revealing rectifying behavior and promising photodetection. This work presents a significant advance toward the monolithic integration of graphene/III-V based hybrid devices onto the mainstream Si technology platform.

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.

Interfacial interactions between calcined hydroxyapatite nanocrystals and substrates.

PubMed

Okada, Masahiro; Furukawa, Keiko; Serizawa, Takeshi; Yanagisawa, Yoshihiko; Tanaka, Hidekazu; Kawai, Tomoji; Furuzono, Tsutomu

2009-06-02

Interfacial interactions between calcined hydroxyapatite (HAp) nanocrystals and surface-modified substrates were investigated by measuring adsorption behavior and adhesion strength with a quartz crystal microbalance (QCM) and a contact-mode atomic force microscope (AFM), respectively. The goal was to develop better control of HAp-nanocrystal coatings on biomedical materials. HAp nanocrystals with rodlike or spherical morphology were prepared by a wet chemical process followed by calcination at 800 degrees C with an antisintering agent to prevent the formation of sintered polycrystals. The substrate surface was modified by chemical reaction with a low-molecular-weight compound, or graft polymerization with a functional monomer. QCM measurement showed that the rodlike HAp nanocrystals adsorbed preferentially onto anionic COOH-modified substrates compared to cationic NH2- or hydrophobic CH3-modified substrates. On the other hand, the spherical nanocrystals adsorbed onto NH2- and COOH-modified substrates, which indicates that the surface properties of the HAp nanocrystals determined their adsorption behavior. The adhesion strength, which was estimated from the force required to move the nanocrystal in contact-mode AFM, on a COOH-grafted substrate prepared by graft polymerization was almost 9 times larger than that on a COOH-modified substrate prepared by chemical reaction with a low-molecular-weight compound, indicating that the long-chain polymer grafted on the substrate mitigated the surface roughness mismatch between the nanocrystal and the substrate. The adhesion strength of the nanocrystal bonded covalently by the coupling reaction to a Si(OCH3)-grafted substrate prepared by graft polymerization was approximately 1.5 times larger than that when adsorbed on the COOH-grafted substrate.

Fabrication and Gas-Sensing Properties of Ni-Silicide/Si Nanowires.

PubMed

Hsu, Hsun-Feng; Chen, Chun-An; Liu, Shang-Wu; Tang, Chun-Kai

2017-12-01

Ni-silicide/Si nanowires were fabricated by atomic force microscope nano-oxidation on silicon-on-insulator substrates, selective wet etching, and reactive deposition epitaxy. Ni-silicide nanocrystal-modified Si nanowire and Ni-silicide/Si heterostructure multi-stacked nanowire were formed by low- and high-coverage depositions of Ni, respectively. The Ni-silicide/Si Schottky junction and Ni-silicide region were attributed high- and low-resistance parts of nanowire, respectively, causing the resistance of the Ni-silicide nanocrystal-modified Si nanowire and the Ni-silicide/Si heterostructure multi-stacked nanowire to be a little higher and much lower than that of Si nanowire. An O 2 sensing device was formed from a nanowire that was mounted on Pt electrodes. When the nanowires exposed to O 2 , the increase in current in the Ni-silicide/Si heterostructure multi-stacked nanowire was much larger than that in the other nanowires. The Ni-silicide nanocrystal-modified Si nanowire device had the highest sensitivity. The phenomenon can be explained by the formation of a Schottky junction at the Ni-silicide/Si interface in these two types of Ni-Silicide/Si nanowire and the formation of a hole channel at the silicon nanowire/native oxide interface after exposing the nanowires to O 2 .

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).

Necessary conditions for superior thermoelectric power of Si/Au artificial superlattice thin-film

NASA Astrophysics Data System (ADS)

Okamoto, Yoichi; Watanabe, Shin; Miyazaki, Hisashi; Morimoto, Jun

2018-03-01

The Si-Ge-Au ternary artificial superlattice thin-films showed superior thermoelectric power with low reproducibility. Superior thermoelectric power was only generated, when nanocrystals existed. Therefore, the origin of superior thermoelectric power was considered to be the quantum size effect of nanocrystals. However, even with the presence of nanocrystals, superior thermoelectric power was often not generated. In order to investigate the generation conditions of superior thermoelectric power in more detail, the samples were simplified to Si-Au binary artificial superlattice samples. Furthermore, annealings were carried out under conditions where nanocrystals were likely to be formed. From the results of Raman scattering spectroscopy and X-ray diffraction (XRD) analysis, the diameter of nanocrystals and the spacing between nanocrystals were calculated with an isotropic three-dimensional mosaic model. It was found that superior thermoelectric power was generated only when the diameter of nanocrystals was 11 nm or less and the spacing between nanocrystals was 3 nm or less.

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

Influence of the deposition and annealing temperatures on the luminescence of germanium nanocrystals formed in GeO x films and multilayer Ge/SiO2 structures

NASA Astrophysics Data System (ADS)

Grachev, D. A.; Ershov, A. V.; Karabanova, I. A.; Pirogov, A. V.; Nezhdanov, A. V.; Mashin, A. I.; Pavlov, D. A.

2017-05-01

The GeO x films and multilayer nanoperiodic Ge/SiO2 structures containing germanium nanocrystals were prepared by physical vapor deposition in vacuum. The properties of the films and multilayer structures were controlled by varying the deposition temperature in the range of 35-590°C and the annealing temperature in the range of 400-1000°C. A comparative study of the optical and structural characteristics of the nanosystems was performed using the methods of Raman scattering spectroscopy, IR spectroscopy, photoluminescence, and electron microscopy, which demonstrated a qualitative similarity of the nanosystems. It was found that annealing at temperatures in the range of 600-800°C leads to the formation of germanium nanocrystals with a high density ( 1012 cm-2), whereas in the materials not subjected to annealing, their density did not exceed 1010 cm-2. The average size of the nanocrystals was found to be 5 ± 2 nm. For both nanosystems, three luminescence bands were observed at 1.2, 1.5-1.7, and 1.7-2.0 eV. It was assumed that the origin of these bands is associated with germanium nanocrystals, oxygen-deficient centers in GeOx, and defects at the Ge/dielectric interface, respectively.

Defect-Induced Luminescence Quenching vs. Charge Carrier Generation of Phosphorus Incorporated in Silicon Nanocrystals as Function of Size.

PubMed

Hiller, Daniel; López-Vidrier, Julian; Gutsch, Sebastian; Zacharias, Margit; Nomoto, Keita; König, Dirk

2017-04-13

Phosphorus doping of silicon nanostructures is a non-trivial task due to problems with confinement, self-purification and statistics of small numbers. Although P-atoms incorporated in Si nanostructures influence their optical and electrical properties, the existence of free majority carriers, as required to control electronic properties, is controversial. Here, we correlate structural, optical and electrical results of size-controlled, P-incorporating Si nanocrystals with simulation data to address the role of interstitial and substitutional P-atoms. Whereas atom probe tomography proves that P-incorporation scales with nanocrystal size, luminescence spectra indicate that even nanocrystals with several P-atoms still emit light. Current-voltage measurements demonstrate that majority carriers must be generated by field emission to overcome the P-ionization energies of 110-260 meV. In absence of electrical fields at room temperature, no significant free carrier densities are present, which disproves the concept of luminescence quenching via Auger recombination. Instead, we propose non-radiative recombination via interstitial-P induced states as quenching mechanism. Since only substitutional-P provides occupied states near the Si conduction band, we use the electrically measured carrier density to derive formation energies of ~400 meV for P-atoms on Si nanocrystal lattice sites. Based on these results we conclude that ultrasmall Si nanovolumes cannot be efficiently P-doped.

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.

Light-emitting Si nanostructures formed by swift heavy ions in a-Si:H/SiO2 multilayer heterostructures

NASA Astrophysics Data System (ADS)

Cherkova, S. G.; Volodin, V. A.; Cherkov, A. G.; Antonenko, A. Kh; Kamaev, G. N.; Skuratov, V. A.

2017-08-01

Light-emitting nanoclusters were formed in Si/SiO2 multilayer structures irradiated with 167 MeV Xe ions to the doses of 1011-3  ×  1014 cm-2 and annealed in the forming-gas at 500 °C and in nitrogen at 800-1100 °C, 30 min. The thicknesses were ~4 nm or ~7-8 for the Si, and ~10 nm for the SiO2 layers. The structures were studied using photoluminescence (PL), Raman spectroscopy, and the cross-sectional high resolution transmission electron microscopy (HRTEM). As-irradiated samples showed the PL, correlating with the growth of the ion doses. HRTEM found the layers to be partly disintegrated. The thickness of the amorphous Si layer was crucial. For 4 nm thick Si layers the PL was peaking at ~490 nm, and quenched by the annealing. It was ascribed to the structural imperfections. For the thicker Si layers the PL was peaking at ~600 nm and was attributed to the Si-rich nanoclusters in silicon oxide. The annealing increases the PL intensity and shifts the band to ~790 nm, typical of Si nanocrystals. Its intensity was proportional to the dose. Raman spectra confirmed the nanocrystals formation. All the results obtained evidence the material melting in the tracks for 10-11-10-10 s providing thereby fast diffusivities of the atoms. The thicker Si layers provide more excess Si to create the nanoclusters via a molten state diffusion.

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

Structural, optical and Carrier dynamics of self-assembled InGaN nanocolumns on Si(111)

NASA Astrophysics Data System (ADS)

Kumar, Praveen; Devi, Pooja; Soto Rodriguez, P. E. D.; Jain, Rishabh; Jaggi, Neena; Sinha, R. K.; Kumar, Mahesh

2018-05-01

We investigated the morphological, structural, optical, electrical and carrier relaxation dynamic changes on the self-assembled grown InGaN nanocolumns (NCs) directly on p-Si(111) substrate at two different substrate temperature, namely 580 °C (A) and 500 °C (B). The emission wavelength of comparably low temperature (LT) grown NCs was red-shifted from 3.2eV to 2.4eV. First observations on the charge carrier dynamics of these directly grown NCs show comparable broad excited state absorption (ESA) for LT gown NCs, which manifest bi-exponential decay due to the radiative defects generated during the coalescence of these NCs.

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.

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