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.

Mind the Microgap in Iridescent Cellulose Nanocrystal Films.

PubMed

Fernandes, Susete N; Almeida, Pedro L; Monge, Nuno; Aguirre, Luis E; Reis, Dennys; de Oliveira, Cristiano L P; Neto, António M F; Pieranski, Pawel; Godinho, Maria H

2017-01-01

A new photonic structure is produced from cellulose nanocrystal iridescent films reflecting both right and left circularly polarized light. Micrometer-scale planar gaps perpendicular to the films' cross-section between two different left-handed films' cholesteric domains are impregnated with a nematic liquid crystal. This photonic feature is reversibly tuned by the application of an electric field or a temperature variation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2017-04-25

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

Processing and Characterization of Cellulose Nanocrystals/Polylactic Acid Nanocomposite Films

Treesearch

Erin Sullivan; Robert Moon; Kyriaki Kalaitzidou

2015-01-01

The focus of this study is to examine the effect of cellulose nanocrystals (CNC) on the properties of polylactic acid (PLA) films. The films are fabricated via melt compounding and melt fiber spinning followed by compression molding. Film fracture morphology, thermal properties, crystallization behavior, thermo-mechanical behavior, and mechanical behavior were...

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.

Copper indium gallium selenide (CIGS) photovoltaic devices made using multistep selenization of nanocrystal films.

PubMed

Harvey, Taylor B; Mori, Isao; Stolle, C Jackson; Bogart, Timothy D; Ostrowski, David P; Glaz, Micah S; Du, Jiang; Pernik, Douglas R; Akhavan, Vahid A; Kesrouani, Hady; Vanden Bout, David A; Korgel, Brian A

2013-09-25

The power conversion efficiency of photovoltaic devices made with ink-deposited Cu(InxGa1-x)Se2 (CIGS) nanocrystal layers can be enhanced by sintering the nanocrystals with a high temperature selenization process. This process, however, can be challenging to control. Here, we report that ink deposition followed by annealing under inert gas and then selenization can provide better control over CIGS nanocrystal sintering and yield generally improved device efficiency. Annealing under argon at 525 °C removes organic ligands and diffuses sodium from the underlying soda lime glass into the Mo back contact to improve the rate and quality of nanocrystal sintering during selenization at 500 °C. Shorter selenization time alleviates excessive MoSe2 formation at the Mo back contact that leads to film delamination, which in turn enables multiple cycles of nanocrystal deposition and selenization to create thicker, more uniform absorber films. Devices with power conversion efficiency greater than 7% are fabricated using the multiple step nanocrystal deposition and sintering process.

Thermal Expansion of Self-Organized and Shear-Oriented Cellulose Nanocrystal Films

Treesearch

Jairo A. Diaz; Xiawa Wu; Ashlie Martini; Jeffrey P. Youngblood; Robert J. Moon

2013-01-01

The coefficient of thermal expansion (CTE) of cellulose nanocrystal (CNC) films was characterized using novel experimental techniques complemented by molecular simulations. The characteristic birefringence exhibited by CNC films was utilized to calculate the in-plane CTE of selforganized and shear-oriented self-standing CNC films from room temperature to 100 °...

Effect of particle Alignment on mechanical properties of neat cellulose nanocrystal films

Treesearch

Alexander B. Reising; Robert J. Moon; Jeffrey P. Youngblood

2012-01-01

Shear-based film casting methods were used to cast neat films from wood-based cellulose nanocrystal (CNC) suspensions. The degree of CNC alignment in dried films was characterized using the Hermans order parameter (S), and the film elastic modulus (E), ultimate tensile strength (σf ), elongation at failure (εf...

Thermal Conductivity in Nanostructured Films: From Single Cellulose Nanocrystals to Bulk Films

Treesearch

Jairo A. Diaz; Zhijiang Ye; Xiawa Wu; Arden L. Moore; Robert J. Moon; Ashlie Martini; Dylan J. Boday; Jeffrey P. Youngblood

2014-01-01

We achieved a multiscale description of the thermal conductivity of cellulose nanocrystals (CNCs) from single CNCs (~­0.72−5.7 W m−1 K−1) to their organized nanostructured films (~­0.22−0.53 W m−1 K−1) using...

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

PubMed

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

2018-05-07

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

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.

Sulvanite (Cu 3VS 4) nanocrystals for printable thin film photovoltaics

DOE PAGES

Chen, Ching -Chin; Stone, Kevin H.; Lai, Cheng -Yu; ...

2017-09-21

Copper Vanadium Sulfide (Cu 3VS 4), also known as sulvanite, has recently emerged as a suitable absorber material for thin film photovoltaics. The synthesis of Cu 3VS 4 nanocrystals via a rapid solvothermal route is reported for the first time. The phase purity of the Cu 3VS 4 nanocrystals has been confirmed by X-ray powder diffraction (XRD) and Raman spectroscopy, while the nanoparticle size, of about 10 nm, was evaluated by transmission electron microscopy (TEM). Successful ligand exchange with sulfide, an inorganic ligand, demonstrated that the nanoparticles are amenable to surface modifications, key element in solution processing. Further annealing ofmore » as-synthesized nanocrystals under a sulfur/argon atmosphere at 600 °C, rendered highly crystalline Cu 3VS 4 powders exhibiting an impurity that could be potentially mitigated by annealing temperature optimization. Furthermore, Cu 3VS 4, formed solely from Earth-abundant elements, could provide an inexpensive, reliable approach to fabricating solution processed thin film photovoltaic absorbers.« less

Sulvanite (Cu 3VS 4) nanocrystals for printable thin film photovoltaics

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

Chen, Ching -Chin; Stone, Kevin H.; Lai, Cheng -Yu

Copper Vanadium Sulfide (Cu 3VS 4), also known as sulvanite, has recently emerged as a suitable absorber material for thin film photovoltaics. The synthesis of Cu 3VS 4 nanocrystals via a rapid solvothermal route is reported for the first time. The phase purity of the Cu 3VS 4 nanocrystals has been confirmed by X-ray powder diffraction (XRD) and Raman spectroscopy, while the nanoparticle size, of about 10 nm, was evaluated by transmission electron microscopy (TEM). Successful ligand exchange with sulfide, an inorganic ligand, demonstrated that the nanoparticles are amenable to surface modifications, key element in solution processing. Further annealing ofmore » as-synthesized nanocrystals under a sulfur/argon atmosphere at 600 °C, rendered highly crystalline Cu 3VS 4 powders exhibiting an impurity that could be potentially mitigated by annealing temperature optimization. Furthermore, Cu 3VS 4, formed solely from Earth-abundant elements, could provide an inexpensive, reliable approach to fabricating solution processed thin film photovoltaic absorbers.« less

Structure and performance of dielectric films based on self-assembled nanocrystals with a high dielectric constant.

PubMed

Huang, Limin; Liu, Shuangyi; Van Tassell, Barry J; Liu, Xiaohua; Byro, Andrew; Zhang, Henan; Leland, Eli S; Akins, Daniel L; Steingart, Daniel A; Li, Jackie; O'Brien, Stephen

2013-10-18

Self-assembled films built from nanoparticles with a high dielectric constant are attractive as a foundation for new dielectric media with increased efficiency and range of operation, due to the ability to exploit nanofabrication techniques and emergent electrical properties originating from the nanoscale. However, because the building block is a discrete one-dimensional unit, it becomes a challenge to capture potential enhancements in dielectric performance in two or three dimensions, frequently due to surface effects or the presence of discontinuities. This is a recurring theme in nanoparticle film technology when applied to the realm of thin film semiconductor and device electronics. We present the use of chemically synthesized (Ba,Sr)TiO3 nanocrystals, and a novel deposition-polymerization technique, as a means to fabricate the dielectric layer. The effective dielectric constant of the film is tunable according to nanoparticle size, and effective film dielectric constants of up to 34 are enabled. Wide area and multilayer dielectrics of up to 8 cm(2) and 190 nF are reported, for which the building block is an 8 nm nanocrystal. We describe models for assessing dielectric performance, and distinct methods for improving the dielectric constant of a nanocrystal thin film. The approach relies on evaporatively driven assembly of perovskite nanocrystals with uniform size distributions in a tunable 7-30 nm size range, coupled with the use of low molecular weight monomer/polymer precursor chemistry that can infiltrate the porous nanocrystal thin film network post assembly. The intercrystal void space (low k dielectric volume fraction) is minimized, while simultaneously promoting intercrystal connectivity and maximizing volume fraction of the high k dielectric component. Furfuryl alcohol, which has good affinity to the surface of (Ba,Sr)TiO3 nanocrystals and miscibility with a range of solvents, is demonstrated to be ideal for the production of nanocomposites. The

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

NASA Astrophysics Data System (ADS)

Sato, Kazuhisa; Abe, Seishi

2016-10-01

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

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

PubMed

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

2015-05-15

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

Tunable d-Limonene Permeability in Starch-Based Nanocomposite Films Reinforced by Cellulose Nanocrystals.

PubMed

Liu, Siyuan; Li, Xiaoxi; Chen, Ling; Li, Lin; Li, Bing; Zhu, Jie

2018-01-31

In order to control d-limonene permeability, cellulose nanocrystals (CNC) were used to regulate starch-based film multiscale structures. The effect of sphere-like cellulose nanocrystal (CS) and rod-like cellulose nanocrystal (CR) on starch molecular interaction, short-range molecular conformation, crystalline structure, and micro-ordered aggregated region structure were systematically discussed. CNC aspect ratio and content were proved to be independent variables to control d-limonene permeability via film-structure regulation. New hydrogen bonding formation and increased hydroxypropyl starch (HPS) relative crystallinity could be the reason for the lower d-limonene permeability compared with tortuous path model approximation. More hydrogen bonding formation, higher HPS relative crystallinity and larger size of micro-ordered aggregated region in CS0.5 and CR2 could explain the lower d-limonene permeability than CS2 and CR0.5, respectively. This study provided new insight for the control of the flavor release from starch-based films, which favored its application in biodegradable food packaging and flavor encapsulation.

The Antifungal Activity of Functionalized Chitin Nanocrystals in Poly (Lactid Acid) Films

PubMed Central

Salaberria, Asier M.; H. Diaz, Rene; Andrés, María A.; Fernandes, Susana C.M.; Labidi, Jalel

2017-01-01

As, in the market, poly (lactic acid) (PLA) is the most used polymer as an alternative to conventional plastics, and as functionalized chitin nanocrystals (CHNC) can provide structural and bioactive properties, their combination sounds promising in the preparation of functional nanocomposite films for sustainable packaging. Chitin nanocrystals were successfully modified via acylation using anhydride acetic and dodecanoyl chloride acid to improve their compatibility with the matrix, PLA. The nanocomposite films were prepared by extrusion/compression approach using different concentrations of both sets of functionalized CHNC. This investigation brings forward that both sets of modified CHNC act as functional agents, i.e., they slightly improved the hydrophobic character of the PLA nanocomposite films, and, very importantly, they also enhanced their antifungal activity. Nonetheless, the nanocomposite films prepared with the CHNC modified with dodecanoyl chloride acid presented the best properties. PMID:28772902

Fabrication of nanocrystal ink based superstrate-type CuInS₂ thin film solar cells.

PubMed

Cho, Jin Woo; Park, Se Jin; Kim, Woong; Min, Byoung Koun

2012-07-05

A CuInS₂ (CIS) nanocrystal ink was applied to thin film solar cell devices with superstrate-type configuration. Monodispersed CIS nanocrystals were synthesized by a colloidal synthetic route and re-dispersed in toluene to form an ink. A spray method was used to coat CIS films onto conducting glass substrates. Prior to CIS film deposition, TiO₂ and CdS thin films were also prepared as a blocking layer and a buffer layer, respectively. We found that both a TiO₂ blocking layer and a CdS buffer layer are necessary to generate photoresponses in superstrate-type devices. The best power conversion efficiency (∼1.45%) was achieved by the CIS superstrate-type thin film solar cell device with 200 and 100 nm thick TiO₂ and CdS films, respectively.

Influence of high loading of cellulose nanocrystals in polyacrylonitrile composite films

Treesearch

Jeffrey Luo; Huibin Chang; Amir A. Bakhtiary Davijani; H. Clive Liu; Po-Hsiang Wang; Robert J. Moon; Satish Kumar

2017-01-01

Polyacrylonitrile-co-methacrylic acid (PAN-co-MAA) and cellulose nanocrystal (CNC) composite films were produced with up to 40 wt% CNC loading through the solution casting method. The rheological properties of the solution/suspensions and the structural, optical, thermal, and mechanical properties of the resulting films were investigated. The viscosity of the composite...

Predicting kinetic nanocrystal shapes through multi-scale theory and simulation: Polyvinylpyrrolidone-mediated growth of Ag nanocrystals

NASA Astrophysics Data System (ADS)

Balankura, Tonnam; Qi, Xin; Zhou, Ya; Fichthorn, Kristen A.

2016-10-01

In the shape-controlled synthesis of colloidal Ag nanocrystals, structure-directing agents, particularly polyvinylpyrrolidone (PVP), are known to be a key additive in making nanostructures with well-defined shapes. Although many Ag nanocrystals have been successfully synthesized using PVP, the mechanism by which PVP actuates shape control remains elusive. Here, we present a multi-scale theoretical framework for kinetic Wulff shape predictions that accounts for the chemical environment, which we used to probe the kinetic influence of the adsorbed PVP film. Within this framework, we use umbrella-sampling molecular dynamics simulations to calculate the potential of mean force and diffusion coefficient profiles of Ag atom deposition onto Ag(100) and Ag(111) in ethylene glycol solution with surface-adsorbed PVP. We use these profiles to calculate the mean-first passage times and implement extensive Brownian dynamics simulations, which allows the kinetic effects to be quantitatively evaluated. Our results show that PVP films can regulate the flux of Ag atoms to be greater towards Ag(111) than Ag(100). PVP's preferential binding towards Ag(100) over Ag(111) gives PVP its flux-regulating capabilities through the lower free-energy barrier of Ag atoms to cross the lower-density PVP film on Ag(111) and enhanced Ag trapping by the extended PVP film on Ag(111). Under kinetic control, {100}-faceted nanocrystals will be formed when the Ag flux is greater towards Ag(111). The predicted kinetic Wulff shapes are in agreement with the analogous experimental system.

Concentration dependent carriers dynamics in CsPbBr3 perovskite nanocrystals film with transient grating

NASA Astrophysics Data System (ADS)

Wang, Yinghui; Wang, Yanting; Dev Verma, Sachin; Tan, Mingrui; Liu, Qinghui; Yuan, Qilin; Sui, Ning; Kang, Zhihui; Zhou, Qiang; Zhang, Han-Zhuang

2017-05-01

The concentration dependence of the carrier dynamics is a key parameter to describe the photo-physical properties of semiconductor films. Here, we investigate the carrier dynamics in the CsPbBr3 perovskite nanocrystal film by employing the transient grating (TG) technique with continuous bias light. The concentration of initial carriers is determined by the average number of photons per nanocrystals induced by pump light (⟨N⟩). The multi-body interaction would appear and accelerate the TG dynamics with ⟨N⟩. When ⟨N⟩ is more than 3.0, the TG dynamics slightly changes, which implies that the Auger recombination would be the highest order multi-body interaction in carrier recombination dynamics. The concentration of non-equilibrium carriers in the film is controlled by the average number of photons per nanocrystals excited by continuous bias light (⟨nne⟩). Increasing ⟨nne⟩ would improve the trapping-detrapping process by filling the trapping state, which would accelerate the carrier diffusion and add the complexity of the mono-molecular recombination mechanism. The results should be useful to further understand the mechanism of carrier dynamics in the CsPbBr3 perovskite nanocrystal film and of great importance for the operation of the corresponding optoelectronic devices.

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

PubMed

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

2015-05-20

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

Processing and Characterization of Cellulose Nanocrystals/Polylactic Acid Nanocomposite Films

PubMed Central

Sullivan, Erin M.; Moon, Robert J.; Kalaitzidou, Kyriaki

2015-01-01

The focus of this study is to examine the effect of cellulose nanocrystals (CNC) on the properties of polylactic acid (PLA) films. The films are fabricated via melt compounding and melt fiber spinning followed by compression molding. Film fracture morphology, thermal properties, crystallization behavior, thermo-mechanical behavior, and mechanical behavior were determined as a function of CNC content using scanning electron microscopy, differential scanning calorimetry, X-ray diffraction, dynamic mechanical analysis, and tensile testing. Film crystallinity increases with increasing CNC content indicating CNC act as nucleating agents, promoting crystallization. Furthermore, the addition of CNC increased the film storage modulus and slightly broadened the glass transition region. PMID:28793701

Oral fast-dissolving films containing lutein nanocrystals for improved bioavailability: formulation development, in vitro and in vivo evaluation.

PubMed

Liu, Chen; Chang, Daoxiao; Zhang, Xinhui; Sui, Hong; Kong, Yindi; Zhu, Rongyue; Wang, Wenping

2017-11-01

Lutein is widely used as diet supplement for prevention of age-related macular degeneration. However, the application and efficacy of lutein in food and nutritional products has been hampered due to its poor solubility and low oral bioavailability. This study aimed to develop and evaluate the formulation of oral fast-dissolving film (OFDF) containing lutein nanocrystals for enhanced bioavailability and compliance. Lutein nanocrystals were prepared by anti-solvent precipitation method and then encapsulated into the films by solvent casting method. The formulation of OFDF was optimized by Box-Behnken Design (BBD) as follows: HPMC 2.05% (w/v), PEG 400 1.03% (w/v), Cremophor EL 0.43% (w/v). The obtained films exhibited uniform thickness of 35.64 ± 1.64 μm and drug content of 0.230 ± 0.003 mg/cm 2 and disintegrated rapidly in 29 ± 8 s. The nanocrystal-loaded films with reconstituted particle size of 377.9 nm showed better folding endurance and faster release rate in vitro than the conventional OFDFs with raw lutein. The microscope images, thermograms, and diffractograms indicated that lutein nanocrystals were highly dispersed into the films. After administrated to SD rats, t max was decreased from 3 h for oral solution formulation to less than 0.8 h for OFDF formulations, and C max increased from 150 ng/mL for solution to 350 ng/mL for conventional OFDF or 830 ng/mL for nanocrystal OFDF. The AUC 0-24h of conventional or nanocrystal OFDF was 1.37 or 2.08-fold higher than that of the oral solution, respectively. These results suggested that drug nanocrystal-loaded OFDF can be applied as a promising approach for enhanced bioavailability of poor soluble drugs like lutein.

Low temperature thin films formed from nanocrystal precursors

DOEpatents

Alivisatos, A. Paul; Goldstein, Avery N.

1993-01-01

Nanocrystals of semiconductor compounds are produced. When they are applied as a contiguous layer onto a substrate and heated they fuse into a continuous layer at temperatures as much as 250, 500, 750 or even 1000.degree. K below their bulk melting point. This allows continuous semiconductor films in the 0.25 to 25 nm thickness range to be formed with minimal thermal exposure.

Low temperature thin films formed from nanocrystal precursors

DOEpatents

Alivisatos, A.P.; Goldstein, A.N.

1993-11-16

Nanocrystals of semiconductor compounds are produced. When they are applied as a contiguous layer onto a substrate and heated they fuse into a continuous layer at temperatures as much as 250, 500, 750 or even 1000 K below their bulk melting point. This allows continuous semiconductor films in the 0.25 to 25 nm thickness range to be formed with minimal thermal exposure. 9 figures.

Fabrication of all-inorganic nanocrystal solids through matrix encapsulation of nanocrystal arrays.

PubMed

Kinder, Erich; Moroz, Pavel; Diederich, Geoffrey; Johnson, Alexa; Kirsanova, Maria; Nemchinov, Alexander; O'Connor, Timothy; Roth, Dan; Zamkov, Mikhail

2011-12-21

A general strategy for low-temperature processing of colloidal nanocrystals into all-inorganic films is reported. The present methodology goes beyond the traditional ligand-interlinking scheme and relies on encapsulation of morphologically defined nanocrystal arrays into a matrix of a wide-band gap semiconductor, which preserves optoelectronic properties of individual nanoparticles while rendering the nanocrystal film photoconductive. Fabricated solids exhibit excellent thermal stability, which is attributed to the heteroepitaxial structure of nanocrystal-matrix interfaces, and show compelling light-harvesting performance in prototype solar cells. © 2011 American Chemical Society

Processing of Copper Zinc Tin Sulfide Nanocrystal Dispersions for Thin Film Solar Cells

NASA Astrophysics Data System (ADS)

Williams, Bryce Arthur

A scalable and inexpensive renewable energy source is needed to meet the expected increase in electricity demand throughout the developed and developing world in the next 15 years without contributing further to global warming through CO2 emissions. Photovoltaics may meet this need but current technologies are less than ideal requiring complex manufacturing processes and/or use of toxic, rare-earth materials. Copper zinc tin sulfide (Cu 2ZnSnS4, CZTS) solar cells offer a true "green" alternative based upon non-toxic and abundant elements. Solution-based processes utilizing CZTS nanocrystal dispersions followed by high temperature annealing have received significant research attention due to their compatibility with traditional roll-to-roll coating processes. In this work, CZTS nanocrystal (5-35 nm diameters) dispersions were utilized as a production pathway to form solar absorber layers. Aerosol-based coating methods (aerosol jet printing and ultrasonic spray coating) were optimized for formation of dense, crack-free CZTS nanocrystal coatings. The primary variables underlying determination of coating morphology within the aerosol-coating parameter space were investigated. It was found that the liquid content of the aerosol droplets at the time of substrate impingement play a critical role. Evaporation of the liquid from the aerosol droplets during coating was altered through changes to coating parameters as well as to the CZTS nanocrystal dispersions. In addition, factors influencing conversion of CZTS nanocrystal coatings into dense, large-grained polycrystalline films suitable for solar cell development during thermal annealing were studied. The roles nanocrystal size, carbon content, sodium uptake, and sulfur pressure were found to have pivotal roles in film microstructure evolution. The effects of these parameters on film morphology, grain growth rates, and chemical makeup were analyzed from electron microscopy images as well as compositional analysis

Mapping the exciton diffusion in semiconductor nanocrystal solids.

PubMed

Kholmicheva, Natalia; Moroz, Pavel; Bastola, Ebin; Razgoniaeva, Natalia; Bocanegra, Jesus; Shaughnessy, Martin; Porach, Zack; Khon, Dmitriy; Zamkov, Mikhail

2015-03-24

Colloidal nanocrystal solids represent an emerging class of functional materials that hold strong promise for device applications. The macroscopic properties of these disordered assemblies are determined by complex trajectories of exciton diffusion processes, which are still poorly understood. Owing to the lack of theoretical insight, experimental strategies for probing the exciton dynamics in quantum dot solids are in great demand. Here, we develop an experimental technique for mapping the motion of excitons in semiconductor nanocrystal films with a subdiffraction spatial sensitivity and a picosecond temporal resolution. This was accomplished by doping PbS nanocrystal solids with metal nanoparticles that force the exciton dissociation at known distances from their birth. The optical signature of the exciton motion was then inferred from the changes in the emission lifetime, which was mapped to the location of exciton quenching sites. By correlating the metal-metal interparticle distance in the film with corresponding changes in the emission lifetime, we could obtain important transport characteristics, including the exciton diffusion length, the number of predissociation hops, the rate of interparticle energy transfer, and the exciton diffusivity. The benefits of this approach to device applications were demonstrated through the use of two representative film morphologies featuring weak and strong interparticle coupling.

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

NASA Astrophysics Data System (ADS)

Chernomordik, Boris David

Significant reduction in greenhouse gas emission and pollution associated with the global power demand can be accomplished by supplying tens-of-terawatts of power with solar cell technologies. No one solar cell material currently on the market is poised to meet this challenge due to issues such as manufacturing cost, material shortage, or material toxicity. For this reason, there is increasing interest in efficient light-absorbing materials that are comprised of abundant and non-toxic elements for thin film solar cell. Among these materials are copper zinc tin sulfide (Cu2ZnSnS4, or CZTS), copper zinc tin selenide (Cu2ZnSnSe4, or CZTSe), and copper zinc tin sulfoselenide alloys [Cu2ZnSn(SxSe1-x )4, or CZTSSe]. Laboratory power conversion efficiencies of CZTSSe-based solar cells have risen to almost 13% in less than three decades of research. Meeting the terawatt challenge will also require low cost fabrication. CZTSSe thin films from annealed colloidal nanocrystal coatings is an example of solution-based methods that can reduce manufacturing costs through advantages such as high throughput, high material utilization, and low capital expenses. The film microstructure and grain size affects the solar cell performance. To realize low cost commercial production and high efficiencies of CZTSSe-based solar cells, it is necessary to understand the fundamental factors that affect crystal growth and microstructure evolution during CZTSSe annealing. Cu2ZnSnS4 (CZTS) nanocrystals were synthesized via thermolysis of single-source cation and sulfur precursors copper, zinc and tin diethyldithiocarbamates. The average nanocrystal size could be tuned between 2 nm and 40 nm, by varying the synthesis temperature between 150 °C and 340 °C. The synthesis is rapid and is completed in less than 10 minutes. Characterization by X-ray diffraction, Raman spectroscopy, transmission electron microscopy and energy dispersive X-ray spectroscopy confirm that the nanocrystals are nominally

Self-bonded composite films based on cellulose nanofibers and chitin nanocrystals as antifungal materials.

PubMed

Robles, Eduardo; Salaberria, Asier M; Herrera, Rene; Fernandes, Susana C M; Labidi, Jalel

2016-06-25

Cellulose nanofibers and chitin nanocrystals, two main components of agricultural and aquacultural by-products, were obtained from blue agave and yellow squat lobster industrial residues. Cellulose nanofibers were obtained using high pressure homogenization, while chitin nanocrystals were obtained by hydrolysis in acid medium. Cellulose nanofibers and chitin nanocrystals were characterized by X-ray diffraction, Atomic Force Microscopy and Infrared spectroscopy. Self-bonded composite films with different composition were fabricated by hot pressing and their properties were evaluated. Antifungal activity of chitin nanocrystals was studied using a Cellometer(®) cell count device, mechanical properties at tension were measured with a universal testing machine, water vapor permeability was evaluated with a thermohygrometer and surface tension with sessile drop contact angle method. The addition of chitin nanocrystals reduced slightly the mechanical properties of the composite. Presence of chitin nanocrystals influenced the growth of Aspergillus sp fungus in the surface of the composites as expected. Copyright © 2016 Elsevier Ltd. All rights reserved.

Superconductivity in films of Pb/PbSe core/shell nanocrystals.

PubMed

Zolotavin, Pavlo; Guyot-Sionnest, Philippe

2012-09-25

Superconductivity in films of electronically coupled colloidal lead nanocrystals is reported. The coupling between particles is in situ controlled through the conversion of the oxides present on the surface of the nanoparticles to chalcogenides. This transformation allows for a 10(9)-fold increase in the conductivity. The temperature of the onset of the superconductivity was found to depend upon the degree of coupling of the nanoparticles in the vicinity of the insulator-superconductor transition. The critical current density of the best sample of Pb/PbSe nanocrystals at zero magnetic field was determined to be 4 × 10(3) A/cm(2). In turn, the critical field of the sample shows 50-fold enhancement compared to bulk Pb.

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.

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

Robust and Bright Photoluminescence from Colloidal Nanocrystal/Al2O3 Composite Films Fabricated by Atomic Layer Deposition.

PubMed

Palei, Milan; Caligiuri, Vincenzo; Kudera, Stefan; Krahne, Roman

2018-06-22

Colloidal nanocrystals are a promising fluorescent class of materials whose spontaneous emission features can be tuned over a broad spectral range via their composition, geometry, and size. However, toward embedding nanocrystal films in elaborated device geometries, one significant drawback is the sensitivity of their emission properties on further fabrication processes like lithography, metal or oxide deposition, etc. In this work, we demonstrate how bright-emitting and robust thin films can be obtained by combining nanocrystal deposition from solutions via spin coating with subsequent atomic layer deposition of alumina. For the resulting composite films, the layer thickness can be controlled on the nanoscale and their refractive index can be finely tuned by the amount of deposited alumina. Ellipsometry is used to measure the real and imaginary part of the dielectric permittivity, which gives direct access to the wavelength dependent refractive index and absorbance of the film. Detailed analysis of the photophysics of thin films of core-shell nanocrystals with different shapes and different shell thicknesses allows to correlate the behavior of the photoluminescence and of the decay lifetime to the changes in the nonradiative rate that are induced by the alumina deposition. We show that the photoemission properties of such composite films are stable in wavelength and intensity over several months and that the photoluminescence completely recovers from heating processes up to 240 °C. The latter is particularly interesting since it demonstrates robustness to the typical heat treatment that is needed in several process steps like resist-based lithography and deposition by thermal or electron beam evaporation of metals or oxides.

Preparation of Nanocomposite Plasmonic Films Made from Cellulose Nanocrystals or Mesoporous Silica Decorated with Unidirectionally Aligned Gold Nanorods.

PubMed

Campbell, Michael G; Liu, Qingkun; Sanders, Aric; Evans, Julian S; Smalyukh, Ivan I

2014-04-11

Using liquid crystalline self-assembly of cellulose nanocrystals, we achieve long-range alignment of anisotropic metal nanoparticles in colloidal nanocrystal dispersions that are then used to deposit thin structured films with ordering features highly dependent on the deposition method. These hybrid films are comprised of gold nanorods unidirectionally aligned in a matrix that can be made of ordered cellulose nanocrystals or silica nanostructures obtained by using cellulose-based nanostructures as a replica. The ensuing long-range alignment of gold nanorods in both cellulose-based and nanoporous silica films results in a polarization-sensitive surface plasmon resonance. The demonstrated device-scale bulk nanoparticle alignment may enable engineering of new material properties arising from combining the orientational ordering of host nanostructures and properties of the anisotropic plasmonic metal nanoparticles. Our approach may also allow for scalable fabrication of plasmonic polarizers and nanoporous silica structures with orientationally ordered anisotropic plasmonic nanoinclusions.

Ready fabrication of thin-film electrodes from building nanocrystals for micro-supercapacitors.

PubMed

Chen, Zheng; Weng, Ding; Wang, Xiaolei; Cheng, Yanhua; Wang, Ge; Lu, Yunfeng

2012-04-18

Thin-film pseudocapacitor electrodes with ultrafast lithium storage kinetics, high capacitance and excellent cycling stability were fabricated from monodispersed TiO(2) building nanocrystals, providing a novel approach towards next-generation micro-supercapacitor applications. This journal is © The Royal Society of Chemistry 2012

Hyperspectral Probing of Exciton dynamics and Multiplication in PbSe Nanocrystals

NASA Astrophysics Data System (ADS)

Gdor, I.; Sachs, H.; Roitblat, A.; Strasfeld, D.; Bawendi, M. G.; Ruhman, S.

2013-03-01

Height time hyperspectral near IR probing providing broad-band coverage is employed on PbSe nanocrystals, uncovering spectral evolution following high energy photo-excitation due to hot exciton relaxation and recombination. Separation of single, double and triple exciton state contributions to these spectra is demonstrated, and the mechanisms underlying the course of spectral evolution are investigated. In addition no sign of MEG was detected in this sample up to a photon energy 3.7 times that of the band gap.

Chiral Nematic Structure of Cellulose Nanocrystal Suspensions and Films; Polarized Light and Atomic Force Microscopy

PubMed Central

Gray, Derek G.; Mu, Xiaoyue

2015-01-01

Cellulosic liquid crystalline solutions and suspensions form chiral nematic phases that show a rich variety of optical textures in the liquid crystalline state. These ordered structures may be preserved in solid films prepared by evaporation of solvent or suspending medium. Film formation from aqueous suspensions of cellulose nanocrystals (CNC) was investigated by polarized light microscopy, optical profilometry and atomic force microscopy (AFM). An attempt is made to interpret qualitatively the observed textures in terms of the orientation of the cellulose nanocrystals in the suspensions and films, and the changes in orientation caused by the evaporative process. Mass transfer within the evaporating droplet resulted in the formation of raised rings whose magnitude depended on the degree of pinning of the receding contact line. AFM of dry films at short length scales showed a radial orientation of the CNC at the free surface of the film, along with a radial height variation with a period of approximately P/2, ascribed to the anisotropic shrinkage of the chiral nematic structure. PMID:28793684

Nanocrystals for electronics.

PubMed

Panthani, Matthew G; Korgel, Brian A

2012-01-01

Semiconductor nanocrystals are promising materials for low-cost large-area electronic device fabrication. They can be synthesized with a wide variety of chemical compositions and size-tunable optical and electronic properties as well as dispersed in solvents for room-temperature deposition using various types of printing processes. This review addresses research progress in large-area electronic device applications using nanocrystal-based electrically active thin films, including thin-film transistors, light-emitting diodes, photovoltaics, and thermoelectrics.

Electrochemically Induced Insulator-Metal-Insulator Transformations of Vanadium Dioxide Nanocrystal Films

NASA Astrophysics Data System (ADS)

Milliron, Delia; Dahlman, Clayton; Leblanc, Gabriel; Bergerud, Amy

Vanadium dioxide (VO2) undergoes significant optical, electronic, and structural changes as it transforms between the low-temperature monoclinic and high-temperature rutile phases. The low-temperature state is insulating and transparent, while the high-temperature state is metallic and IR blocking. Alternative stimuli have been utilized to trigger insulator-to-metal transformations in VO2, including electrochemical gating. Here, VO2 nanocrystal films have been prepared by solution deposition of V2O3 nanocrystals followed by oxidative annealing. Nanocrystalline VO2 films are electrochemically reduced, inducing changes in their electronic and optical properties. We observe a reversible transition between infrared transparent insulating phases and a darkened metallic phase by in situ visible-near-infrared spectroelectrochemistry and correlate these observations with structural and electronic changes monitored by X-ray absorption spectroscopy, X-ray diffraction, Raman spectroscopy, and conductivity measurements. Reduction causes an initial transformation to a metallic, IR-colored distorted monoclinic phase. However, an unexpected reversible transition from conductive, reduced monoclinic VO2 to an infrared-transparent insulating phase is observed upon further reduction.

Nanocrystal synthesis and thin film formation for earth abundant photovoltaics

NASA Astrophysics Data System (ADS)

Carter, Nathaniel J.

Providing access to on-demand energy at the global scale is a grand challenge of our time. The fabrication of solar cells from nanocrystal inks comprising earth abundant elements represents a scalable and sustainable photovoltaic technology with the potential to meet the global demand for electricity. Solar cells with Cu2ZnSn(S,Se)4 (CZTSSe) absorber layers are of particular interest due to the high absorption coefficient of CZTSSe, its band gap in the ideal range for efficient photovoltaic power conversion, and the relative abundance of its constituent elements in the earth's crust. Despite the promise of this material system, CZTSSe solar cell efficiencies reported throughout literature have failed to exceed 12.6%, principally due to the low open-circuit voltage (VOC) achieved in these devices compared to the absorber band gap. The work presented herein primarily aims to address the low VOC problem. First, the fundamental cause for such low VOC's is investigated. Interparticle compositional inhomogeneities identified in the synthesized CZTS nanocrystals and their effect on the absorber layer formation and device performance are characterized. Real-time energy-dispersive x-ray diffraction (EDXRD) elucidates the role of these inhomogeneities in the mechanism by which a film of CZTS nanocrystals converts into a dense absorber layer comprising micron-sized CZTSSe grains upon annealing in a selenium atmosphere (selenization). Additionally, a direct correlation between the nanocrystal inhomogeneities and the VOC in completed devices is observed. Detailed characterization of CZTSSe solar cells identifies electrical potential fluctuations in the CZTSSe absorber - due to spatial composition variations not unlike those observed in the nanocrystals - as a primary V OC inhibitor. Additional causes for low VOC's in CZTSSe solar cells proposed in the literature involve recombination at the interface between the CZTSSe absorber and: (1) the n-type, CdS buffer layer, or (2) the

Properties of cast films made of chayote (Sechium edule Sw.) tuber starch reinforced with cellulose nanocrystals

USDA-ARS?s Scientific Manuscript database

In this study, cellulose (C) and cellulose nanocrystals (CN) were blended with chayote tuber (Sechium edule Sw.) starch (CS) in formulations cast into films. The films were conditioned at different storage temperatures and relative humidity (RH), and analyzed by mechanical tests, X-ray diffraction, ...

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.

Semiconductor nanocrystal-aptamer bioconjugate probes for specific prostate carcinoma cell targeting

NASA Astrophysics Data System (ADS)

Shieh, Felice; Lavery, Laura; Chu, Chitai T.; Richards-Kortum, Rebecca; Ellington, Andrew D.; Korgel, Brian A.

2005-04-01

Cancer of the prostate affects approximately 1 in 11 men. Current early screening for prostate cancer utilizes digital rectal examinations to detect anomalies in the prostate gland and blood test screenings for upregulated levels of prostate specific antigen (PSA). Many of these tests are invasive and can often be inconclusive as PSA levels may be heightened due to benign factors. Prostate specific membrane antigen (PSMA), a well-characterized integral membrane protein, is expressed in virtually all prostate cancers and often correlates with cancer aggressiveness. Therefore, it may be used as an indicator of cancer growth and metastases. PSMA-specific antibodies have been identified and conjugated to fluorescent markers for cancer cell targeting; however, both the antibodies and markers possess significant limitations in their pharmaceutical and diagnostic value. Here we report the use of semiconductor nanocrystals bioconjugated to PSMA-specific aptamer recognition molecules for prostate carcinoma cell targeting. The nanocrystal/aptamer bioconjugates are small biocompatible probes with the potential for color-tunability for multicolor imaging. Ongoing in vitro and in vivo research seeks to introduce these nanoparticle bioconjugates into medical diagnostics.

Influence of composition on the performance of sintered Cu(In,Ga)Se2 nanocrystal thin-film photovoltaic devices.

PubMed

Akhavan, Vahid A; Harvey, Taylor B; Stolle, C Jackson; Ostrowski, David P; Glaz, Micah S; Goodfellow, Brian W; Panthani, Matthew G; Reid, Dariya K; Vanden Bout, David A; Korgel, Brian A

2013-03-01

Thin-film photovoltaic devices (PVs) were prepared by selenization using oleylamine-capped Cu(In,Ga)Se2 (CIGS) nanocrystals sintered at a high temperature (>500 °C) under Se vapor. The device performance varied significantly with [Ga]/[In+Ga] content in the nanocrystals. The highest power conversion efficiency (PCE) observed in the devices studied was 5.1 % under air mass 1.5 global (AM 1.5 G) illumination, obtained with [Ga]/[In+Ga]=0.32. The variation in PCE with composition is partly a result of bandgap tuning and optimization, but the main influence of nanocrystal composition appeared to be on the quality of the sintered films. The [Cu]/[In+Ga] content was found to be strongly influenced by the [Ga]/[In+Ga] concentration, which appears to be correlated with the morphology of the sintered film. For this reason, only small changes in the [Ga]/[In+Ga] content resulted in significant variations in device efficiency. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and Doping of Silicon Nanocrystals for Versatile Nanocrystal Inks

NASA Astrophysics Data System (ADS)

Kramer, Nicolaas Johannes

atmospheric pressures necessitates high plasma densities to reach temperatures required for crystallization of nanoparticles. Using experimentally determined plasma properties from the literature, the model estimates the nanoparticle temperature that is achieved during synthesis at atmospheric pressures. It was found that temperatures well above those required for crystallization can be achieved. Now that the synthesis of nanocrystals is understood, the second half of this thesis will focus on doping of the nanocrystals. The doping of semiconductor nanocrystals, which is vital for the optimization of nanocrystal-based devices, remains a challenge. Gas phase plasma approaches have been very successful in incorporating dopant atoms into nanocrystals by simply adding a dopant precursor during synthesis. However, little is known about the electronic activation of these dopants. This was investigated with field-effect transistor measurements using doped silicon nanocrystal films. It was found that, analogous to bulk silicon, boron and phosphorous electronically dope silicon nanocrystals. However, the dopant activation efficiency remains low as a result of self-purification of the dopants to the nanocrystal surface. Next the plasmonic properties of heavily doped silicon nanocrystals was explored. While the synthesis method was identical, the plasmonic behavior of phosphorus-doped and boron-doped nanocrystals was found the be significantly different. Phosphorus-doped nanocrystals exhibit a plasmon resonance immediately after synthesis, while boron-doped nanocrystals require a post-synthesis annealing or oxidation treatment. This is a result of the difference in dopant location. Phosphorus is more likely to be incorporated into the core of the nanocrystal, while the majority of boron is placed on the surface of the nanocrystal. The oxidized boron-doped particles exhibit stable plasmonic properties, and therefore this allows for the production of air-stable silicon-based plasmonic

Composite Films Formed by Cellulose nanocrystals and Latex Nanoparticles: Optical, Structural, and Mechanical Properties

NASA Astrophysics Data System (ADS)

Vollick, Brandon McRae

This thesis describes the preparation of iridescent, birefringent, composite films composed of cellulose nanocrystals (CNCs), latex nanoparticles (NPs) and a NP crosslinker; hexanediamine (HDA). First, aqueous suspensions were prepared with varying quantities of CNCs, NPs and HDA before equilibrating for one week. The cholesteric (Ch) phase was then cast and dried into a film. The optical, structural and mechanical properties of the film was analyzed. Second, films with identical compositions of CNCs, NPs, and HDA were fabricated in three different ways to yield films of different morphology, (i) fast drying of an isotropic suspension, yielding an isotropic film, (ii) slow drying of an isotropic suspension, yielding a partially Ch films, (iii) slow drying of an equilibrated suspension, yielding a highly Ch film. The optical and mechanical properties of the films was analyzed.

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

Interfacial Properties of Lignin-Based Electrospun Nanofibers and Films Reinforced with Cellulose Nanocrystals

Treesearch

Mariko Ago; Joseph E. Jakes; Leena-Sisko Johansson; Sunkyu Park; Orlando J. Rojas

2012-01-01

Sub-100 nm resolution local thermal analysis, X-ray photoelectron spectroscopy (XPS), and water contact angle (WCA) measurements were used to relate surface polymer distribution with the composition of electrospun fiber mats and spin coated films obtained from aqueous dispersions of lignin, polyvinyl alcohol (PVA), and cellulose nanocrystal (CNC). Defect-free lignin/...

Structure and transformation of tactoids in cellulose nanocrystal suspensions

NASA Astrophysics Data System (ADS)

Wang, Pei-Xi; Hamad, Wadood Y.; MacLachlan, Mark J.

2016-05-01

Cellulose nanocrystals obtained from natural sources are of great interest for many applications. In water, cellulose nanocrystals form a liquid crystalline phase whose hierarchical structure is retained in solid films after drying. Although tactoids, one of the most primitive components of liquid crystals, are thought to have a significant role in the evolution of this phase, they have evaded structural study of their internal organization. Here we report the capture of cellulose nanocrystal tactoids in a polymer matrix. This method allows us to visualize, for the first time, the arrangement of cellulose nanocrystals within individual tactoids by electron microscopy. Furthermore, we can follow the structural evolution of the liquid crystalline phase from tactoids to iridescent-layered films. Our insights into the early nucleation events of cellulose nanocrystals give important information about the growth of cholesteric liquid crystalline phases, especially for cellulose nanocrystals, and are crucial for preparing photonics-quality films.

Photophysical properties of wavelength-tunable methylammonium lead halide perovskite nanocrystals

DOE PAGES

Freppon, Daniel J.; Men, Long; Burkhow, Sadie J.; ...

2016-11-25

Here we present the time-correlated luminescence of isolated nanocrystals of five methylammonium lead mixed-halide perovskite compositions (CH 3NH 3PbBr 3$-$xI x) that were synthesized with varying iodide and bromide anion loading. All analyzed nanocrystals had a spherical morphology with diameters in the range of 2 to 32 nm. The luminescence maxima of CH 3NH 3PbBr 3$-$xI x nanocrystals were tuned to wavelengths ranging between 498 and 740 nm by varying the halide loading. Both CH 3NH 3PbI 3 and CH 3NH 3PbBr 3 nanocrystals exhibited no luminescence intermittency for more than 90% of the 250 s analysis time, as definedmore » by a luminescence intensity three standard deviations above the background. The mixed halide CH 3NH 3PbBr 0.75I 0.25, CH 3NH 3PbBr 0.50I 0.50, and CH 3NH 3PbBr 0.25I 0.75 nanocrystals exhibited luminescence intermittency in 18%, 4% and 26% of the nanocrystals, respectively. Irrespective of luminescence intermittency, luminescence intensities were classified for each nanocrystal as: (a) constant, (b) multimodal, (c) photobrightening, and (d) photobleaching. Finally, based on their photophysics, the CH 3NH 3PbBr 3$-$xI x nanocrystals can be expected to be useful in a wide-range of applications where low and non-intermittent luminescence is desirable, for example as imaging probes and in films for energy conversion devices.« less

Photophysical properties of wavelength-tunable methylammonium lead halide perovskite nanocrystals

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

Freppon, Daniel J.; Men, Long; Burkhow, Sadie J.

Here we present the time-correlated luminescence of isolated nanocrystals of five methylammonium lead mixed-halide perovskite compositions (CH 3NH 3PbBr 3$-$xI x) that were synthesized with varying iodide and bromide anion loading. All analyzed nanocrystals had a spherical morphology with diameters in the range of 2 to 32 nm. The luminescence maxima of CH 3NH 3PbBr 3$-$xI x nanocrystals were tuned to wavelengths ranging between 498 and 740 nm by varying the halide loading. Both CH 3NH 3PbI 3 and CH 3NH 3PbBr 3 nanocrystals exhibited no luminescence intermittency for more than 90% of the 250 s analysis time, as definedmore » by a luminescence intensity three standard deviations above the background. The mixed halide CH 3NH 3PbBr 0.75I 0.25, CH 3NH 3PbBr 0.50I 0.50, and CH 3NH 3PbBr 0.25I 0.75 nanocrystals exhibited luminescence intermittency in 18%, 4% and 26% of the nanocrystals, respectively. Irrespective of luminescence intermittency, luminescence intensities were classified for each nanocrystal as: (a) constant, (b) multimodal, (c) photobrightening, and (d) photobleaching. Finally, based on their photophysics, the CH 3NH 3PbBr 3$-$xI x nanocrystals can be expected to be useful in a wide-range of applications where low and non-intermittent luminescence is desirable, for example as imaging probes and in films for energy conversion devices.« less

Sub-micron Polymer–Zeolitic Imidazolate Framework Layered Hybrids via Controlled Chemical Transformation of Naked ZnO Nanocrystal Films

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

Meckler, Stephen M.; Li, Changyi; Queen, Wendy L.

2015-11-02

Here we show that sub-micron coatings of zeolitic imidazolate frameworks (ZIFs) and even ZIF–ZIF bilayers can be grown directly on polymers of intrinsic microporosity from zinc oxide (ZnO) nanocrystal precursor films, yielding a new class of all-microporous layered hybrids. The ZnO-to-ZIF chemical transformation proceeded in less than 30 min under microwave conditions using a solution of the imidazole ligand in N,N-dimethylformamide (DMF), water, or mixtures thereof. By varying the ratio of DMF to water, it was possible to control the morphology of the ZIF-on-polymer from isolated crystallites to continuous films. Grazing incidence X-ray diffraction was used to confirm the presencemore » of crystalline ZIF in the thin films, and X-ray absorption spectroscopy was used to quantify film purity, revealing films with little to no residual ZnO. The role solvent plays in the transformation mechanism is discussed in light of these findings, which suggest the ZnO nanocrystals may be necessary to localize heterogeneous nucleation of the ZIF to the polymer surface.« less

Sub-micron Polymer–Zeolitic Imidazolate Framework Layered Hybrids via Controlled Chemical Transformation of Naked ZnO Nanocrystal Films

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

Meckler, Stephen M.; Li, Changyi; Queen, Wendy L.

Here we show that sub-micron coatings of zeolitic imidazolate frameworks (ZIFs) and even ZIF–ZIF bilayers can be grown directly on polymers of intrinsic microporosity from zinc oxide (ZnO) nanocrystal precursor films, yielding a new class of all-microporous layered hybrids. The ZnO-to-ZIF chemical transformation proceeded in less than 30 min under microwave conditions using a solution of the imidazole ligand in N,N-dimethylformamide (DMF), water, or mixtures thereof. By varying the ratio of DMF to water, it was possible to control the morphology of the ZIF-on-polymer from isolated crystallites to continuous films. Grazing incidence X-ray diffraction was used to confirm the presencemore » of crystalline ZIF in the thin films, and X-ray absorption spectroscopy was used to quantify film purity, revealing films with little to no residual ZnO. The role solvent plays in the transformation mechanism is discussed in light of these findings, which suggest the ZnO nanocrystals may be necessary to localize heterogeneous nucleation of the ZIF to the polymer surface.« less

Thin Cu film resistivity using four probe techniques: Effect of film thickness and geometrical shapes

NASA Astrophysics Data System (ADS)

Choudhary, Sumita; Narula, Rahul; Gangopadhyay, Subhashis

2018-05-01

Precise measurement of electrical sheet resistance and resistivity of metallic thin Cu films may play a significant role in temperature sensing by means of resistivity changes which can further act as a safety measure of various electronic devices during their operation. Four point probes resistivity measurement is a useful approach as it successfully excludes the contact resistance between the probes and film surface of the sample. Although, the resistivity of bulk samples at a particular temperature mostly depends on its materialistic property, however, it may significantly differ in the case of thin films, where the shape and thickness of the sample can significantly influence on it. Depending on the ratio of the film thickness to probe spacing, samples are usually classified in two segments such as (i) thick films or (ii) thin films. Accordingly, the geometric correction factors G can be related to the sample resistivity r, which has been calculated here for thin Cu films of thickness up to few 100 nm. In this study, various rectangular shapes of thin Cu films have been used to determine the shape induced geometric correction factors G. An expressions for G have been obtained as a function of film thickness t versus the probe spacing s. Using these expressions, the correction factors have been plotted separately for each cases as a function of (a) film thickness for fixed linear probe spacing and (b) probe distance from the edge of the film surface for particular thickness. Finally, we compare the experimental results of thin Cu films of various rectangular geometries with the theoretical reported results.

Structure and properties of composite films formed by cellulose nanocrystals and charged latex nanoparticles

NASA Astrophysics Data System (ADS)

Thérien-Aubin, Héloïse; Lukach, Ariella; Pitch, Natalie; Kumacheva, Eugenia

2015-04-01

We report the structural and optical properties of composite films formed from mixed suspensions of cellulose nanocrystals (CNCs) and fluorescent latex nanoparticles (NPs). We explored the effect of NP concentration, size, surface charge, glass transition temperature and film processing conditions on film structure and properties. The chiral nematic order, typical of CNC films, was preserved in films with up to 50 wt% of negatively-charged latex NPs. Composite films were characterized by macroscopically close-to-uniform fluorescence, birefringence, and circular dichroism properties. In contrast, addition of positively charged latex NPs led to gelation of CNC-latex suspensions and disruption of the chiral nematic order in the composite films. Large latex NPs disrupted the chiral nematic order to a larger extend than small NPs. Furthermore, the glass transition of latex NPs had a dramatic effect on the structure of CNC-latex films. Latex particles in the rubbery state were easily incorporated in the ordered CNC matrix and improved the structural integrity of its chiral nematic phase.We report the structural and optical properties of composite films formed from mixed suspensions of cellulose nanocrystals (CNCs) and fluorescent latex nanoparticles (NPs). We explored the effect of NP concentration, size, surface charge, glass transition temperature and film processing conditions on film structure and properties. The chiral nematic order, typical of CNC films, was preserved in films with up to 50 wt% of negatively-charged latex NPs. Composite films were characterized by macroscopically close-to-uniform fluorescence, birefringence, and circular dichroism properties. In contrast, addition of positively charged latex NPs led to gelation of CNC-latex suspensions and disruption of the chiral nematic order in the composite films. Large latex NPs disrupted the chiral nematic order to a larger extend than small NPs. Furthermore, the glass transition of latex NPs had a dramatic

Measuring the Valence of Nanocrystal Surfaces

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

Owen, Jonathan Scharle

2016-11-30

The goal of this project is to understand and control the interplay between nanocrystal stoichiometry, surface ligand binding and exchange, and the optoelectronic properties of semiconductor nanocrystals in solution and in thin solid films. We pursued three research directions with this goal in mind: 1) We characterized nanocrystal stoichiometry and its influence on the binding of L-type and X-type ligands, including the thermodynamics of binding and the kinetics of ligand exchange. 2) We developed a quantitative understanding of the relationship between surface ligand passivation and photoluminescence quantum yield. 3) We developed methods to replace the organic ligands on the nanocrystalmore » with halide ligands and controllably deposit these nanocrystals into thin films, where electrical measurements were used to investigate the electrical transport and internanocrystal electronic coupling.« less

Hypervalent surface interactions for colloidal stability and doping of silicon nanocrystals

PubMed Central

Wheeler, Lance M.; Neale, Nathan R.; Chen, Ting; Kortshagen, Uwe R.

2013-01-01

Colloidal semiconductor nanocrystals have attracted attention for cost-effective, solution-based deposition of quantum-confined thin films for optoelectronics. However, two significant challenges must be addressed before practical nanocrystal-based devices can be realized. The first is coping with the ligands that terminate the nanocrystal surfaces. Though ligands provide the colloidal stability needed to cast thin films from solution, these ligands dramatically hinder charge carrier transport in the resulting film. Second, after a conductive film is achieved, doping has proven difficult for further control of the optoelectronic properties of the film. Here we report the ability to confront both of these challenges by exploiting the ability of silicon to engage in hypervalent interactions with hard donor molecules. For the first time, we demonstrate the significant potential of applying the interaction to the nanocrystal surface. In this study, hypervalent interactions are shown to provide colloidal stability as well as doping of silicon nanocrystals. PMID:23893292

Magnetoelectricity in CoFe2O4 nanocrystal-P(VDF-HFP) thin films

PubMed Central

2013-01-01

Transition metal ferrites such as CoFe2O4, possessing a large magnetostriction coefficient and high Curie temperature (Tc > 600 K), are excellent candidates for creating magnetic order at the nanoscale and provide a pathway to the fabrication of uniform particle-matrix films with optimized potential for magnetoelectric coupling. Here, a series of 0–3 type nanocomposite thin films composed of ferrimagnetic cobalt ferrite nanocrystals (8 to 18 nm) and a ferroelectric/piezoelectric polymer poly(vinylidene fluoride-co-hexafluoropropene), P(VDF-HFP), were prepared by multiple spin coating and cast coating over a thickness range of 200 nm to 1.6 μm. We describe the synthesis and structural characterization of the nanocrystals and composite films by XRD, TEM, HRTEM, STEM, and SEM, as well as dielectric and magnetic properties, in order to identify evidence of cooperative interactions between the two phases. The CoFe2O4 polymer nanocomposite thin films exhibit composition-dependent effective permittivity, loss tangent, and specific saturation magnetization (Ms). An enhancement of the effective permittivity and saturation magnetization of the CoFe2O4-P(VDF-HFP) films was observed and directly compared with CoFe2O4-polyvinylpyrrolidone, a non-ferroelectric polymer-based nanocomposite prepared by the same method. The comparison provided evidence for the observation of a magnetoelectric effect in the case of CoFe2O4-P(VDF-HFP), attributed to a magnetostrictive/piezoelectric interaction. An enhancement of Ms up to +20.7% was observed at room temperature in the case of the 10 wt.% CoFe2O4-P(VDF-HFP) sample. PMID:24004499

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.

Recent Advances in Chiral Nematic Structure and Iridescent Color of Cellulose Nanocrystal Films

PubMed Central

Gray, Derek G.

2016-01-01

One unique property of cellulose nanocrystals (CNC) is their property of forming suspensions with chiral nematic order. This order can be preserved in films cast from the suspensions, raising the possibility of applications as photonic materials and templates. However, it has proved difficult to generate uniform, well-ordered chiral nematic materials from CNC. Recently, the importance of kinetic arrest due to gel formation in the later stages of evaporation has been recognized as a key step in film formation. In this brief review, recent developments regarding the structure of chiral nematic suspensions and films as monitored by polarized light microscopy are outlined, and attention is drawn to the importance of shear forces on the self-organization process. PMID:28335340

Cassava starch-based films plasticized with sucrose and inverted sugar and reinforced with cellulose nanocrystals.

PubMed

da Silva, Jania B A; Pereira, Fabiano V; Druzian, Janice I

2012-06-01

Bionanocomposites films of cassava starch plasticized with sucrose and inverted sugar and reinforced by cellulose nanocrystals (CNCs) were prepared by solution casting method incorporating 0.1 to 5 wt% of eucalyptus CNCs. The nanocrystals were characterized using transmission electron microscopy, whereas the bionanocomposites properties were studied using Fourier transform infrared spectroscopy, tensile measurements, water solubility, swelling behavior, and water activity (a(w)). The water resistance properties (solubility and swelling behavior) of the nanocomposites were enhanced with the addition of cellulose nanofillers. These results were explained in terms of the high crystallinity of the nanocrystals and the formation of a rigid network with the nanofillers, which provide physical barriers to the permeation of water within the hydrophilic cassava matrix. The addition of CNCs in the bionanocomposites decreases a(w) linearly, reaching values below 0.5 (for CNCs concentration higher than 4 wt%), a reference value for no microbial proliferation for food product design. The presence of small concentrations of CNCs (0.1-0.3 wt%) also effectively increased the maximum tensile strength (more than 90%) and elastic modulus (more than 400%), indicating the formation of a suitable percolation network in this concentration range. Because the cellulose nanofillers enhanced the mechanical and water stability properties of the nanocomposites, the obtained results in this work may be applied to the development of biodegradable packaging or coatings to enhance shelf life of food products. The main drawbacks of using starch-based polymers as packaging or coating in the food industry are their low mechanical properties and inherent water sensitivity. This study demonstrates that cellulose nanocrystals can be used to: (i) obtain better mechanical properties (increasing the tensile strength and modulus more than 90% and 400%, respectively; (ii) enhance the water stability and (iii

Use of CdS quantum dot-functionalized cellulose nanocrystal films for anti-counterfeiting applications

NASA Astrophysics Data System (ADS)

Chen, L.; Lai, C.; Marchewka, R.; Berry, R. M.; Tam, K. C.

2016-07-01

Structural colors and photoluminescence have been widely used for anti-counterfeiting and security applications. We report for the first time the use of CdS quantum dot (QD)-functionalized cellulose nanocrystals (CNCs) as building blocks to fabricate nanothin films via layer-by-layer (LBL) self-assembly for anti-counterfeiting applications. Both negatively- and positively-charged CNC/QD nanohybrids with a high colloidal stability and a narrow particle size distribution were prepared. The controllable LBL coating process was characterized by scanning electron microscopy and ellipsometry. The rigid structure of CNCs leads to nanoporous structured films on poly(ethylene terephthalate) (PET) substrates with high transmittance (above 70%) over the entire range of visible light and also resulted in increased hydrophilicity (contact angles of ~40 degrees). Nanothin films on PET substrates showed good flexibility and enhanced stability in both water and ethanol. The modified PET films with structural colors from thin-film interference and photoluminescence from QDs can be used in anti-counterfeiting applications.Structural colors and photoluminescence have been widely used for anti-counterfeiting and security applications. We report for the first time the use of CdS quantum dot (QD)-functionalized cellulose nanocrystals (CNCs) as building blocks to fabricate nanothin films via layer-by-layer (LBL) self-assembly for anti-counterfeiting applications. Both negatively- and positively-charged CNC/QD nanohybrids with a high colloidal stability and a narrow particle size distribution were prepared. The controllable LBL coating process was characterized by scanning electron microscopy and ellipsometry. The rigid structure of CNCs leads to nanoporous structured films on poly(ethylene terephthalate) (PET) substrates with high transmittance (above 70%) over the entire range of visible light and also resulted in increased hydrophilicity (contact angles of ~40 degrees). Nanothin films

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.

PZT Thin-Film Micro Probe Device with Dual Top Electrodes

NASA Astrophysics Data System (ADS)

Luo, Chuan

Lead zirconate titanate (PZT) thin-film actuators have been studied intensively for years because of their potential applications in many fields. In this dissertation, a PZT thin-film micro probe device is designed, fabricated, studied, and proven to be acceptable as an intracochlear acoustic actuator. The micro probe device takes the form of a cantilever with a PZT thin-film diaphragm at the tip of the probe. The tip portion of the probe will be implanted in cochlea later in animal tests to prove its feasibility in hearing rehabilitation. The contribution of the dissertation is three-fold. First, a dual top electrodes design, consisting of a center electrode and an outer electrode, is developed to improve actuation displacement of the PZT thin-film diaphragm. The improvement by the dual top electrodes design is studied via a finite element model. When the dimensions of the dual electrodes are optimized, the displacement of the PZT thin-film diaphragm increases about 30%. A PZT thin-film diaphragm with dual top electrodes is fabricated to prove the concept, and experimental results confirm the predictions from the finite element analyses. Moreover, the dual electrode design can accommodate presence of significant residual stresses in the PZT thin-film diaphragm by changing the phase difference between the two electrodes. Second, a PZT thin-film micro probe device is fabricated and tested. The fabrication process consists of PZT thin-film deposition and deep reactive ion etching (DRIE). The uniqueness of the fabrication process is an automatic dicing mechanism that allows a large number of probes to be released easily from the wafer. Moreover, the fabrication is very efficient, because the DRIE process will form the PZT thin-film diaphragm and the special dicing mechanism simultaneously. After the probes are fabricated, they are tested with various possible implantation depths (i.e., boundary conditions). Experimental results show that future implantation depths

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

Exciton-Delocalizing Ligands Can Speed Up Energy Migration in Nanocrystal Solids.

PubMed

Azzaro, Michael S; Dodin, Amro; Zhang, Diana Y; Willard, Adam P; Roberts, Sean T

2018-05-09

Researchers have long sought to use surface ligands to enhance energy migration in nanocrystal solids by decreasing the physical separation between nanocrystals and strengthening their electronic coupling. Exciton-delocalizing ligands, which possess frontier molecular orbitals that strongly mix with nanocrystal band-edge states, are well-suited for this role because they can facilitate carrier-wave function extension beyond the nanocrystal core, reducing barriers for energy transfer. This report details the use of the exciton-delocalizing ligand phenyldithiocarbamate (PDTC) to tune the transport rate and diffusion length of excitons in CdSe nanocrystal solids. A film composed of oleate-terminated CdSe nanocrystals is subjected to a solid-state ligand exchange to replace oleate with PDTC. Exciton migration in the films is subsequently investigated by femtosecond transient absorption. Our experiments indicate that the treatment of nanocrystal films with PDTC leads to rapid (∼400 fs) downhill energy migration (∼80 meV), while no such migration occurs in oleate-capped films. Kinetic Monte Carlo simulations allow us to extract both rates and length scales for exciton diffusion in PDTC-treated films. These simulations reproduce dynamics observed in transient absorption measurements over a range of temperatures and confirm excitons hop via a Miller-Abrahams mechanism. Importantly, our experiments and simulations show PDTC treatment increases the exciton hopping rate to 200 fs, an improvement of 5 orders of magnitude relative to oleate-capped films. This exciton hopping rate stands as one of the fastest determined for CdSe solids. The facile, room-temperature processing and improved transport properties offered by the solid-state exchange of exciton-delocalizing ligands show they offer promise for the construction of strongly coupled nanocrystal arrays.

Relationship between tribology and optics in thin films of mechanically oriented nanocrystals.

PubMed

Wong, Liana; Hu, Chunhua; Paradise, Ruthanne; Zhu, Zina; Shtukenberg, Alexander; Kahr, Bart

2012-07-25

Many crystalline dyes, when rubbed unidirectionally with cotton on glass slides, can be organized as thin films of highly aligned nanocrystals. Commonly, the linear birefringence and linear dichroism of these films resemble the optical properties of single crystals, indicating precisely oriented particles. Of 186 colored compounds, 122 showed sharp extinction and 50 were distinctly linearly dichroic. Of the latter 50 compounds, 88% were more optically dense when linearly polarized light was aligned with the rubbing axis. The mechanical properties of crystals that underlie the nonstatistical correlation between tribological processes and the direction of electron oscillations in absorption bands are discussed. The features that give rise to the orientation of dye crystallites naturally extend to colorless molecular crystals.

Preparation and physical properties of tara gum film reinforced with cellulose nanocrystals.

PubMed

Ma, Qianyun; Hu, Dongying; Wang, Lijuan

2016-05-01

Cellulose nanocrystals (CNC) prepared from microcrystalline cellulose were blended in tara gum solution to prepare nanocomposite films. The morphology, crystallinity, and thermal properties of the CNC and films were evaluated by using transmission electron microscopy, X-ray diffractometry, and thermogravimetric analysis, respectively. The resultant CNC was rod-shaped with diameters of around 8.6 nm. The effect of CNC content on physical and thermal properties of films was studied. The composite film tensile strength increased from 27.86 to 65.73 MPa, elastic modulus increased from 160.98 MPa to 882.49 MPa and the contact angle increased from 55.8° to 98.7° with increasing CNC content from 0 to 6 wt%. However, CNC addition increased the thermal stability slightly and CNC content above 6 wt% decreased the tensile strength by CNC aggregation in the matrix. The nanocomposite film containing 6 wt% CNC possessed the highest light transmittance, mechanical properties, and lowest oxygen permeability. CNC addition is a suitable method to modify tara gum matrix polymer properties. Copyright © 2016 Elsevier B.V. All rights reserved.

Optoelectronic properties and depth profile of charge transport in nanocrystal films

NASA Astrophysics Data System (ADS)

Aigner, Willi; Bienek, Oliver; Desta, Derese; Wiggers, Hartmut; Stutzmann, Martin; Pereira, Rui N.

2017-07-01

We investigate the charge transport in nanocrystal (NC) films using field effect transistors (FETs) of silicon NCs. By studying films with various thicknesses in the dark and under illumination with photons with different penetration depths (UV and red light), we are able to predictably change the spatial distribution of charge carriers across the films' profile. The experimental data are compared with photoinduced charge carrier generation rates computed using finite-difference time-domain (FDTD) simulations complemented with optical measurements. This enables us to understand the optoelectronic properties of NC films and the depth profile dependence of the charge transport properties. From electrical measurements, we extract the total (bulk) photoinduced charge carrier densities (nphoto) and the photoinduced charge carrier densities in the FETs channel (nphoto*). We observe that the values of nphoto and their dependence on film thickness are similar for UV and red light illumination, whereas a significant difference is observed for the values of nphoto*. The dependencies of nphoto and nphoto* on film thickness and illumination wavelength are compared with data from FDTD simulations. Combining experimental data and simulation results, we find that charge carriers in the top rough surface of the films cannot contribute to the macroscopic charge transport. Moreover, we conclude that below the top rough surface of NC films, the efficiency of charge transport, including the charge carrier mobility, is homogeneous across the film thickness. Our work shows that the use of NC films as photoactive layers in applications requiring harvesting of strongly absorbed photons such as photodetectors and photovoltaics demands a very rigorous control over the films' roughness.

Utilization of flax (Linum usitatissimum) cellulose nanocrystals as reinforcing material for chitosan films.

PubMed

Mujtaba, Muhammad; Salaberria, Asier M; Andres, María A; Kaya, Murat; Gunyakti, Ayse; Labidi, Jalel

2017-11-01

Use of plastic based packaging tools is causing both health and economic problems. To overcome this situation, researchers are focusing on the use of different biomaterials such as chitosan and cellulose. The current study was conducted to check the effect of flax (Linum usitatissimum) cellulose nanocrystals (CNC) on mechanical and barrier properties of chitosan-based films. CNC was incorporated in different concentrations (5, 10, 20 and 30%). CNC was isolated from flax fiber using acid hydrolysis method. Tensile strength (TS) and young modulus (YM) values increased with the increase of CNC concentration. Chitosan film with 20% CNC revealed the highest YM value as 52.35MPa. No significant improvement was recorded in water vapor permeability due to overall lower film crystallinity. All the films were observed to be transparent up to an acceptable level. SEM and AFM analysis confirmed the homogeneity of films. A gradual enhancement was recorded in the antimicrobial activity of chitosan/CNC composite films. No significant improvement revealed in the thermal stability of composites. Copyright © 2017 Elsevier B.V. All rights reserved.

Water barrier properties of starch films reinforced with cellulose nanocrystals obtained from sugarcane bagasse.

PubMed

Slavutsky, Aníbal M; Bertuzzi, María A

2014-09-22

Water transport in edible films based on hydrophilic materials such as starch, is a complex phenomenon due to the strong interaction of sorbed water molecules with the polymeric structure. Cellulose nanocrystals (CNC) were obtained from sugarcane bagasse. Starch and starch/CNC films were formulated and their water barrier properties were studied. The measured film solubility, contact angle, and water sorption isotherm indicated that reinforced starch/CNC films have a lower affinity to water molecules than starch films. The effects that the driving force and the water activity (aw) values at each side of the film have on permeability were analyzed. Permeability, diffusivity, and solubility coefficients indicated that the permeation process depends mostly on the tortuous pathway formed by the incorporation of CNC and therefore were mainly controlled by water diffusion. The interaction between CNC and starch chain is favoured by the chemical similarities of both molecules. Copyright © 2014 Elsevier Ltd. All rights reserved.

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.

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

Tin-dioxide nanocrystals as Er3+ luminescence sensitizers: Formation of glass-ceramic thin films and their characterization

NASA Astrophysics Data System (ADS)

Zur, Lidia; Tran, Lam Thi Ngoc; Meneghetti, Marcello; Tran, Van Thi Thanh; Lukowiak, Anna; Chiasera, Alessandro; Zonta, Daniele; Ferrari, Maurizio; Righini, Giancarlo C.

2017-01-01

Silica-tin dioxide thin films doped with Er3+ ions were fabricated and investigated. Different parameters such as heat-treatment temperatures, molar concentrations of SnO2 as well as Er3+ ions concentration were changed in order to obtain the best properties of presented thin films. Using several techniques, thin films were characterized and proved to be crack-free, water-free and smooth after a heat-treatment at 1200 °C. Aiming to application in optics, the transparency of thin films was also evidenced by transmission spectra. Based on the photoluminescence measurements, the mechanism of energy transfer from SnO2 nanocrystals to Er3+ ions was examined and discussed.

Use of CdS quantum dot-functionalized cellulose nanocrystal films for anti-counterfeiting applications.

PubMed

Chen, L; Lai, C; Marchewka, R; Berry, R M; Tam, K C

2016-07-21

Structural colors and photoluminescence have been widely used for anti-counterfeiting and security applications. We report for the first time the use of CdS quantum dot (QD)-functionalized cellulose nanocrystals (CNCs) as building blocks to fabricate nanothin films via layer-by-layer (LBL) self-assembly for anti-counterfeiting applications. Both negatively- and positively-charged CNC/QD nanohybrids with a high colloidal stability and a narrow particle size distribution were prepared. The controllable LBL coating process was characterized by scanning electron microscopy and ellipsometry. The rigid structure of CNCs leads to nanoporous structured films on poly(ethylene terephthalate) (PET) substrates with high transmittance (above 70%) over the entire range of visible light and also resulted in increased hydrophilicity (contact angles of ∼40 degrees). Nanothin films on PET substrates showed good flexibility and enhanced stability in both water and ethanol. The modified PET films with structural colors from thin-film interference and photoluminescence from QDs can be used in anti-counterfeiting applications.

Structural, optical, and electrical properties of PbSe nanocrystal solids treated thermally or with simple amines.

PubMed

Law, Matt; Luther, Joseph M; Song, Qing; Hughes, Barbara K; Perkins, Craig L; Nozik, Arthur J

2008-05-07

We describe the structural, optical, and electrical properties of films of spin-cast, oleate-capped PbSe nanocrystals that are treated thermally or chemically in solutions of hydrazine, methylamine, or pyridine to produce electronically coupled nanocrystal solids. Postdeposition heat treatments trigger nanocrystal sintering at approximately 200 degrees C, before a substantial fraction of the oleate capping group evaporates or pyrolyzes. The sintered nanocrystal films have a large hole density and are highly conductive. Most of the amine treatments preserve the size of the nanocrystals and remove much of the oleate, decreasing the separation between nanocrystals and yielding conductive films. X-ray scattering, X-ray photoelectron and optical spectroscopy, electron microscopy, and field-effect transistor electrical measurements are used to compare the impact of these chemical treatments. We find that the concentration of amines adsorbed to the NC films is very low in all cases. Treatments in hydrazine in acetonitrile remove only 2-7% of the oleate yet result in high-mobility n-type transistors. In contrast, ethanol-based hydrazine treatments remove 85-90% of the original oleate load. Treatments in pure ethanol strip 20% of the oleate and create conductive p-type transistors. Methylamine- and pyridine-treated films are also p-type. These chemically treated films oxidize rapidly in air to yield, after short air exposures, highly conductive p-type nanocrystal solids. Our results aid in the rational development of solar cells based on colloidal nanocrystal films.

Self-assembly of water-soluble nanocrystals

DOEpatents

Fan, Hongyou [Albuquerque, NM; Brinker, C Jeffrey [Albuquerque, NM; Lopez, Gabriel P [Albuquerque, NM

2012-01-10

A method for forming an ordered array of nanocrystals where a hydrophobic precursor solution with a hydrophobic core material in an organic solvent is added to a solution of a surfactant in water, followed by removal of a least a portion of the organic solvent to form a micellar solution of nanocrystals. A precursor co-assembling material, generally water-soluble, that can co-assemble with individual micelles formed in the micellar solution of nanocrystals can be added to this micellar solution under specified reaction conditions (for example, pH conditions) to form an ordered-array mesophase material. For example, basic conditions are used to precipitate an ordered nanocrystal/silica array material in bulk form and acidic conditions are used to form an ordered nanocrystal/silica array material as a thin film.

Modifying Mechanical, Optical Properties and Thermal Processability of Iridescent Cellulose Nanocrystal Films Using Ionic Liquid.

PubMed

Liu, Ping; Guo, Xin; Nan, Fuchun; Duan, Yongxin; Zhang, Jianming

2017-01-25

Iridescent films formed from the self-assembly of cellulose nanocrystals (CNCs) are brittle and difficult to handle or integrate within an industrial process. Here we present a simple approach to prepare iridescent CNC films with tunable pliability and coloration through the addition of ionic liquids (ILs) of 1-allyl-3-methylimidazolium chloride (AmimCl) as plasticizers. By using the undried CNC film as a filter membrane and ILs solution as a leaching liquid, it was found that the filtration process made ILs uniformly interpenetrate into CNC film due to the strong ionic interaction between CNC and AmimCl. Unexpectedly, the filtration process also gave rise to partial desulfurization of CNC film, which is conducive to the improvement of thermal stability. Benefiting from the improved thermal stability and the dissolving capacity of AmimCl for cellulose at high temperature, the incorporated ILs enable the cholesteric CNC film to be further toughened via a hot-pressing treatment. This study demonstrates that ionic liquids have great potential to modify the mechanical, optical properties as well as the thermal stability of iridescent CNC films.

Hygroscopic Swelling Determination of Cellulose Nanocrystal (CNC) Films by Polarized Light Microscopy Digital Image Correlation.

PubMed

Shrestha, Shikha; Diaz, Jairo A; Ghanbari, Siavash; Youngblood, Jeffrey P

2017-05-08

The coefficient of hygroscopic swelling (CHS) of self-organized and shear-oriented cellulose nanocrystal (CNC) films was determined by capturing hygroscopic strains produced as result of isothermal water vapor intake in equilibrium. Contrast enhanced microscopy digital image correlation enabled the characterization of dimensional changes induced by the hygroscopic swelling of the films. The distinct microstructure and birefringence of CNC films served in exploring the in-plane hygroscopic swelling at relative humidity values ranging from 0% to 97%. Water vapor intake in CNC films was measured using dynamic vapor sorption (DVS) at constant temperature. The obtained experimental moisture sorption and kinetic profiles were analyzed by fitting with Guggenheim, Anderson, and deBoer (GAB) and Parallel Exponential Kinetics (PEK) models, respectively. Self-organized CNC films showed isotropic swelling, CHS ∼0.040 %strain/%C. By contrast, shear-oriented CNC films exhibited an anisotropic swelling, resulting in CHS ∼0.02 and ∼0.30 %strain/%C, parallel and perpendicular to CNC alignment, respectively. Finite element analysis (FEA) further predicted moisture diffusion as the predominant mechanism for swelling of CNC films.

Interaction model between a liquid film and a spherical probe

NASA Astrophysics Data System (ADS)

Ledesma Alonso, Rene; Legendre, Dominique; Tordjeman, Philippe

2012-11-01

To find a liquid surface profile, when performing AFM measurements, probe interaction effects should be identified. Herein, the behavior of a liquid film free surface (thickness E, surface tension γ and density difference Δρ), disposed over a flat surface and in the presence of a spherical probe (radius R) is forecast. A bump-like surface shape is observed, due to the probe/film interaction (characterized by the Hamaker constant Hpl). In addition, the attraction between the film and the substrate (depicted by Hsl) opposes the axial and radial deformation ranges. Several parameters portray the equilibrium shape: Bond Bo = (ΔρgR2) / γ and modified Hamaker Ha = 4Hpl / (3 πγR2) numbers, Hamaker ratio A =Hls /Hpl , separation distance D / R and film thickness E / R . We focus on the effect of geometry, nevertheless special attention is given to the role of physical parameters. Employing an augmented Young-Laplace equation, the equilibrium profile is described by a strongly non-linear ODE. A critical distance, below which the irreversible wetting process of the spherical probe occurs, is predicted. Our results provide simple relationships between parameters, which determine the optimal scanning conditions over liquid films.

Picoampere Resistive Switching Characteristics Realized with Vertically Contacted Carbon Nanotube Atomic Force Microscope Probe

NASA Astrophysics Data System (ADS)

Nakano, Haruhisa; Takahashi, Makoto; Sato, Motonobu; Kotsugi, Masato; Ohkochi, Takuo; Muro, Takayuki; Nihei, Mizuhisa; Yokoyama, Naoki

2013-11-01

The resistive switching characteristics of a TiO2/Ti structure have been investigated using a conductive atomic force microscopy (AFM) system with 5-nm-diameter carbon nanotube (CNT) probes. The resistive switching showed bipolar resistive random access memory (ReRAM) behaviors with extremely low switching currents in the order of Picoamperes when voltages were applied. From transmission electron microscopy (TEM) observation, we confirmed that filament-like nanocrystals, having a diameter of about 10 nm, existed in TiO2 films at resistive switching areas after not only set operation but also reset operation. Moreover, photoemission electron microscopy (PEEM) analysis showed that the anatase-type TiO2 structure did not change after set and reset operations. From these results, we suggested that the Picoampere resistive switching occurred at the interface between the TiO2 dielectric and conductive nanocrystal without any structural changes in the TiO2 film and nanocrystal. The resistive switching mechanism we suggested is highly promising to realize extremely low-power-consumption ReRAMs with vertically contacted CNT electrodes.

Controlled Chemical Doping of Semiconductor Nanocrystals Using Redox Buffers

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

Engel, Jesse H.; Surendranath, Yogesh; Alivisatos, Paul

Semiconductor nanocrystal solids are attractive materials for active layers in next-generation optoelectronic devices; however, their efficient implementation has been impeded by the lack of precise control over dopant concentrations. Herein we demonstrate a chemical strategy for the controlled doping of nanocrystal solids under equilibrium conditions. Exposing lead selenide nanocrystal thin films to solutions containing varying proportions of decamethylferrocene and decamethylferrocenium incrementally and reversibly increased the carrier concentration in the solid by 2 orders of magnitude from their native values. This application of redox buffers for controlled doping provides a new method for the precise control of the majority carrier concentrationmore » in porous semiconductor thin films.« less

Surface oxidation of tin chalcogenide nanocrystals revealed by 119Sn-Mössbauer spectroscopy.

PubMed

de Kergommeaux, Antoine; Faure-Vincent, Jérôme; Pron, Adam; de Bettignies, Rémi; Malaman, Bernard; Reiss, Peter

2012-07-18

Narrow band gap tin(II) chalcogenide (SnS, SnSe, SnTe) nanocrystals are of high interest for optoelectronic applications such as thin film solar cells or photodetectors. However, charge transfer and charge transport processes strongly depend on nanocrystals' surface quality. Using (119)Sn-Mössbauer spectroscopy, which is the most sensitive tool for probing the Sn oxidation state, we show that SnS nanocrystals exhibit a Sn((IV))/Sn((II)) ratio of around 20:80 before and 40:60 after five minutes exposure to air. Regardless of the tin or sulfur precursors used, similar results are obtained using six different synthesis protocols. The Sn((IV)) content before air exposure arises from surface related SnS(2) and Sn(2)S(3) species as well as from surface Sn atoms bound to oleic acid ligands. The increase of the Sn((IV)) content upon air exposure results from surface oxidation. Full oxidation of the SnS nanocrystals without size change is achieved by annealing at 500 °C in air. With the goal to prevent surface oxidation, SnS nanocrystals are capped with a cadmium-phosphonate complex. A broad photoluminescence signal centered at 600 nm indicates successful capping, which however does not reduce the air sensitivity. Finally we demonstrate that SnSe nanocrystals exhibit a very similar behavior with a Sn((IV))/Sn((II)) ratio of 43:57 after air exposure. In the case of SnTe nanocrystals, the ratio of 55:45 is evidence of a more pronounced tendency for oxidation. These results demonstrate that prior to their use in optoelectronics further surface engineering of tin chalcogenide nanocrystals is required, which otherwise have to be stored and processed under inert atmosphere.

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.

Colloidal infrared reflective and transparent conductive aluminum-doped zinc oxide nanocrystals

DOEpatents

Buonsanti, Raffaella; Milliron, Delia J

2015-02-24

The present invention provides a method of preparing aluminum-doped zinc oxide (AZO) nanocrystals. In an exemplary embodiment, the method includes (1) injecting a precursor mixture of a zinc precursor, an aluminum precursor, an amine, and a fatty acid in a solution of a vicinal diol in a non-coordinating solvent, thereby resulting in a reaction mixture, (2) precipitating the nanocrystals from the reaction mixture, thereby resulting in a final precipitate, and (3) dissolving the final precipitate in an apolar solvent. The present invention also provides a dispersion. In an exemplary embodiment, the dispersion includes (1) nanocrystals that are well separated from each other, where the nanocrystals are coated with surfactants and (2) an apolar solvent where the nanocrystals are suspended in the apolar solvent. The present invention also provides a film. In an exemplary embodiment, the film includes (1) a substrate and (2) nanocrystals that are evenly distributed on the substrate.

Charge Transport in Semiconductor Nanocrystal Solids

NASA Astrophysics Data System (ADS)

Talapin, Dmitri; Shevchenko, Elena; Lee, Jong Soo; Urban, Jeffrey; Mitzi, David; Murray, Christopher

2007-03-01

Self-assembly of chemically-synthesized nanocrystals can yield complex long-range ordered structures which can be used as model systems for studying transport phenomena in low-dimensional materials [1]. Treatment of close-packed PbSe nanocrystal arrays with hydrazine enhanced exchange coupling between the nanocrystals and improved conductance by more than ten orders of magnitude compared to native nanocrystal films [2]. The conductivity of PbSe nanocrystal solids can be switched between n- and p-type transports by controlling the saturation of electronic states at nanocrystal surfaces. Nanocrystal arrays form the n- and p-channels of field-effect transistors with electron and hole mobilities of 2.5 cm^2V-1s-1 and 0.3 cm^2V-1s-1, respectively, and current modulation Ion/Ioff˜10^3-10^4. The field-effect mobility in PbSe nanocrystal arrays is higher than the mobility of organic transistors while the easy switch between n- and p-transport allows realization of complimentary circuits and p-n junctions for nanocrystal-based solar cells and thermoelectric devices. [1] E. V. Shevchenko, D. V. Talapin, N. A. Kotov, S. O'Brien, C. B. Murray. Nature 439, 55 (2006). [2] D. V. Talapin, C. B. Murray. Science 310, 86 (2005).

Flexible and low-voltage integrated circuits constructed from high-performance nanocrystal transistors.

PubMed

Kim, David K; Lai, Yuming; Diroll, Benjamin T; Murray, Christopher B; Kagan, Cherie R

2012-01-01

Colloidal semiconductor nanocrystals are emerging as a new class of solution-processable materials for low-cost, flexible, thin-film electronics. Although these colloidal inks have been shown to form single, thin-film field-effect transistors with impressive characteristics, the use of multiple high-performance nanocrystal field-effect transistors in large-area integrated circuits has not been shown. This is needed to understand and demonstrate the applicability of these discrete nanocrystal field-effect transistors for advanced electronic technologies. Here we report solution-deposited nanocrystal integrated circuits, showing nanocrystal integrated circuit inverters, amplifiers and ring oscillators, constructed from high-performance, low-voltage, low-hysteresis CdSe nanocrystal field-effect transistors with electron mobilities of up to 22 cm(2) V(-1) s(-1), current modulation >10(6) and subthreshold swing of 0.28 V dec(-1). We fabricated the nanocrystal field-effect transistors and nanocrystal integrated circuits from colloidal inks on flexible plastic substrates and scaled the devices to operate at low voltages. We demonstrate that colloidal nanocrystal field-effect transistors can be used as building blocks to construct complex integrated circuits, promising a viable material for low-cost, flexible, large-area electronics.

Silicon nanocrystals as handy biomarkers

NASA Astrophysics Data System (ADS)

Fujioka, Kouki; Hoshino, Akiyoshi; Manabe, Noriyoshi; Futamura, Yasuhiro; Tilley, Richard; Yamamoto, Kenji

2007-02-01

Quantum dots (QDs) have brighter and longer fluorescence than organic dyes. Therefore, QDs can be applied to biotechnology, and have capability to be applied to medical technology. Currently, among the several types of QDs, CdSe with a ZnS shell is one of the most popular QDs to be used in biological experiments. However, when the CdSe QDs were applied to clinical technology, potential toxicological problems due to CdSe core should be considered. To eliminate the problem, silicon nanocrystals, which have the potential of biocompatibility, could be a candidate of alternate probes. Silicon nanocrystals have been synthesized using several techniques such as aerosol, electrochemical etching, laser pyrolysis, plasma deposition, and colloids. Recently, the silicon nanocrystals were reported to be synthesized in inverse micelles and also stabilized with 1-heptene or allylamine capping. Blue fluorescence of the nanocrystals was observed when excited with a UV light. The nanocrystals covered with 1-heptene are hydrophobic, whereas the ones covered with allylamine are hydrophilic. To test the stability in cytosol, the water-soluble nanocrystals covered with allylamine were examined with a Hela cell incorporation experiment. Bright blue fluorescence of the nanocrystals was detected in the cytosol when excited with a UV light, implying that the nanocrystals were able to be applied to biological imaging. In order to expand the application range, we synthesized and compared a series of silicon nanocrystals, which have variable surface modification, such as alkyl group, alcohol group, and odorant molecules. This study will provide a wider range of optoelectronic applications and bioimaging technology.

Increased functional properties and thermal stability of flexible cellulose nanocrystal/ZnO films.

PubMed

Lizundia, E; Urruchi, A; Vilas, J L; León, L M

2016-01-20

In this work we attempt to improve the functional properties and thermal stability of cellulose nanocrystal (CNC) films by means of eco-friendly materials and processes. Mechanically flexible films of closely packed CNCs with concentrations up to 5 wt.% of zinc oxide (ZnO) nanoparticles have been prepared by a simple, standard and environmentally friendly method using solely water. Results reveal that ultraviolet light is blocked by 98.5% at 1 wt.% ZnO while good transparency is maintained. A sharp hydrophobicity increase is observed with the addition of ZnO which would enhance the durability of films by decreasing the water diffusion through the material. The thermal degradation activation energy (E) presents an increase of 141%, denoting a high thermal stability of films, which would result beneficial for their potential application in the field of flexible electronics. Mechanical results demonstrate a high structural integrity of CNC/ZnO as a result of the occurring strong cellulosic inter- and intramolecular interactions within the closely packed CNC network. In overall, this work highlights the potential for environmentally friendly processing of sustainable nanostructured functional materials based on cellulose. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

Metal Nanoparticles Embedded in Cellulose Nanocrystal Based Films: Material Properties and Post-use Analysis.

PubMed

Lizundia, Erlantz; Goikuria, Uribarri; Vilas, José Luis; Cristofaro, Francesco; Bruni, Giovanna; Fortunati, Elena; Armentano, Ilaria; Visai, Livia; Torre, Luigi

2018-04-25

The dispersion of nanoparticles having different size-, shape-, and composition-dependent properties is an exciting approach to design and synthesize multifunctional materials and devices. This work shows a detailed investigation of the preparation and properties of free-standing nanocomposite films based on cellulose nanocrystals (CNC) loaded with three different types of metal nanoparticles. CNC-based nanocomposites having zinc oxide (ZnO), titanium dioxide (TiO 2 ), and silver oxide (Ag 2 O) have been obtained through evaporation-induced self-assembly (EISA) in acqueous solution. Morphological and optical characteristics, chemical properties, wettability, and antimicrobial assays of the produced films were conducted. Furthermore, disintegrability in composting condition of CNC based nanocomposites was here investigated for the first time. The morphological observations revealed the formation of a chiral nematic structure with uniformly distributed nanoparticles. The bionanocomposite films based on the metal nanoparticles had effective antimicrobial activity, killing both Escherichia coli RB ( E. coli RB) and Staphylococcus aureus 8325-4 ( S. aureus 8325-4). The simplicity method of film preparation, the large quantity of cellulose in the world, and the free-standing nature of the nanocomposite films offer highly advantageous characteristics that can for the new development of multifunctional materials.

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

NASA Astrophysics Data System (ADS)

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

2017-05-01

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

Fundamental Study on One-Dimensional-Array Medical Ultrasound Probe with Piezoelectric Polycrystalline Film by Hydrothermal Method: Experimental Fabrication of One-Dimensional-Array Ultrasound Probe

NASA Astrophysics Data System (ADS)

Endo, Akito; Kawashima, Norimichi; Takeuchi, Shinichi; Ishikawa, Mutsuo; Kurosawa, Minoru Kuribayashi

2007-07-01

We deposited a lead zirconate titanete (PZT) polycrystalline film on a titanium substrate by the hydrothermal method and fabricated a transducer using the PZT film for use as an ultrasound probe. A 10 MHz miniature one-dimensional-array medical ultrasound probe containing the PZT film was developed. After sputtering titanium on the surface of a hydroxyapatite substrate, the titanium film on the substrate was etched by the photolithography to form a one-dimensional titanium film electrode array. We could thus fabricate a miniature one-dimensional-array ultrasound probe by the hydrothermal method. Transmitted ultrasound pulses from a 10 MHz commercial ultrasound probe were received by the newly fabricated one-dimensional-array ultrasound probe. The fabrication process of the probe and the results of experiments on receiving waveforms were reported in this paper.

Development of polylactic acid nanocomposite films reinforced with cellulose nanocrystals derived from coffee silverskin.

PubMed

Sung, Soo Hyun; Chang, Yoonjee; Han, Jaejoon

2017-08-01

Bio-nanocomposite films based on polylactic acid (PLA) matrix reinforced with cellulose nanocrystals (CNCs) were developed using a twin-screw extruder. The CNCs were extracted from coffee silverskin (CS), which is a by-product of the coffee roasting process. They were extracted by alkali treatment followed by sulfuric acid hydrolysis. They were used as reinforcing agents to obtain PLA/CNC nanocomposites by addition at different concentrations (1%, 3%, and 5% CNCs). Morphological, tensile, and barrier properties of the bio-nanocomposites were analyzed. The tensile strength and Young's modulus increased with both 1% and 3% CNCs. The water vapor permeability decreased gradually with increasing addition of CNCs up to 3% and good oxygen barrier properties were found for all nanocomposites. These results suggest that CNCs from CS can improve the physical properties of PLA-based biopolymer film. The developed PLA/CNC bio-nanocomposite films can potentially be used for biopolymer materials with enhanced barrier and mechanical properties. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ultrasonication of Bismuth Telluride Nanocrystals Fabricated by Solvothermal Method

NASA Technical Reports Server (NTRS)

Chu, Sang-Hyon; Choi, Sang H.; Kim, Jae-Woo; King, Glen C.; Elliott, James R.

2006-01-01

The objective of this study is to evaluate the effect of ultrasonication on bismuth telluride nanocrystals prepared by solvothermal method. In this study, a low dimensional nanocrystal of bismuth telluride (Bi2Te3) was synthesized by a solvothermal process in an autoclave at 180 C and 200 psi. During the solvothermal reaction, organic surfactants effectively prevented unwanted aggregation of nanocrystals in a selected solvent while controlling the shape of the nanocrystal. The atomic ratio of bismuth and tellurium was determined by energy dispersive spectroscopy (EDS). The cavitational energy created by the ultrasonic probe was varied by the ultrasonication process time, while power amplitude remained constant. The nanocrystal size and its size distribution were measured by field emission scanning electron microscopy (FESEM) and a dynamic light scattering system. When the ultrasonication time increased, the average size of bismuth telluride nanocrystal gradually increased due to the direct collision of nanocrystals. The polydispersity of the nanocrystals showed a minimum when the ultrasonication was applied for 5 min. Keywords: bismuth telluride, nanocrystal, low-dimensional, ultrasonication, solvothermal

Thermomechanical Properties of Lignin-Based Electrospun Nanofibers and Films Reinforced with Cellulose Nanocrystals: A Dynamic Mechanical and Nanoindentation Study

Treesearch

Mariko Ago; Joseph E. Jakes; Orlando J. Rojas

2013-01-01

We produced defect-free electrospun fibers from aqueous dispersions of lignin, poly(vinyl alcohol) (PVA), and cellulose nanocrystals (CNCs), which were used as reinforcing nanoparticles. The thermomechanical performance of the lignin-based electrospun fibers and the spin-coated thin films was improved when they were embedded with CNCs. Isochronal dynamic mechanical...

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.

Characteristics of unique HBr-hydrolyzed cellulose nanocrystals from freshwater green algae (Cladophora rupestris) and its reinforcement in starch-based film.

PubMed

Sucaldito, Melvir R; Camacho, Drexel H

2017-08-01

Cellulose nanocrystals (CNCs) are promising materials that are readily extracted from plants and other cellulose-containing organisms. In this study, CNCs were isolated from freshwater green algae (Cladophora rupestris) thriving in a volcanic lake, using hydrobromic acid (HBr) hydrolysis. Morphological and structural studies revealed highly crystalline CNCs (94.0% crystallinity index) with preferred orientation to [100] lattice plane as shown by XRD measurements and have an average diameter of 20.0 (±4.4)nm as shown by TEM. Thermal studies showed increased temperature for thermal decomposition of CNCs (381.6°C), which is a result of HBr hydrolysis for CNCs isolation. The isolated CNCs were reinforced into starch based biocomposites via solution casting and evaporation method. Mechanical strength was improved as high as 78% upon addition of 1% cellulose nanocrystals in the films. The produced films are promising materials for their high mechanical strength, biodegradability and availability of raw materials. Copyright © 2017 Elsevier Ltd. All rights reserved.

Self-assembled pit arrays as templates for the integration of Au nanocrystals in oxide surfaces.

PubMed

Konstantinović, Z; Sandiumenge, F; Santiso, J; Balcells, Ll; Martínez, B

2013-02-07

We report on the fabrication of long-range ordered arrays of Au nanocrystals (sub-50 nm range) on top of manganite (La(2/3)Sr(1/3)MnO(3)) thin films achieving area densities around 2 × 10(10) gold nanocrystals per cm(2), well above the densities achievable by using conventional nanofabrication techniques. The gold-manganite interface exhibits excellent conduction properties. Long-range order is achieved by a guided self-assembling process of Au nanocrystals on self-organized pit-arrays acting as a template for the nucleation of gold nanocrystals. Self-organization of pits on the manganite film surface promoted by the underlying stepped SrTiO(3) substrate is achieved by a fine tuning of the growth kinetic pathway, taking advantage of the unusual misfit strain relaxation behaviour of manganite films.

Single-particle mapping of nonequilibrium nanocrystal transformations

DOE PAGES

Ye, Xingchen; Jones, Matthew R.; Frechette, Layne B.; ...

2016-11-18

Chemists have developed mechanistic insight into numerous chemical reactions by thoroughly characterizing nonequilibrium species. Although methods to probe these processes are well established for molecules, analogous techniques for understanding intermediate structures in nanomaterials have been lacking. For this study, we monitor the shape evolution of individual anisotropic gold nanostructures as they are oxidatively etched in a graphene liquid cell with a controlled redox environment. Short-lived, nonequilibrium nanocrystals are observed, structurally analyzed, and rationalized through Monte Carlo simulations. Understanding these reaction trajectories provides important fundamental insight connecting high-energy nanocrystal morphologies to the development of kinetically stabilized surface features and demonstrates themore » importance of developing tools capable of probing short-lived nanoscale species at the single-particle level.« less

Low-frequency (1/f) noise in nanocrystal field-effect transistors.

PubMed

Lai, Yuming; Li, Haipeng; Kim, David K; Diroll, Benjamin T; Murray, Christopher B; Kagan, Cherie R

2014-09-23

We investigate the origins and magnitude of low-frequency noise in high-mobility nanocrystal field-effect transistors and show the noise is of 1/f-type. Sub-band gap states, in particular, those introduced by nanocrystal surfaces, have a significant influence on the 1/f noise. By engineering the device geometry and passivating nanocrystal surfaces, we show that in the linear and saturation regimes the 1/f noise obeys Hooge's model of mobility fluctuations, consistent with transport of a high density of accumulated carriers in extended electronic states of the NC thin films. In the subthreshold regime, the Fermi energy moves deeper into the mobility gap and sub-band gap trap states give rise to a transition to noise dominated by carrier number fluctuations as described in McWhorter's model. CdSe nanocrystal field-effect transistors have a Hooge parameter of 3 × 10(-2), comparable to other solution-deposited, thin-film devices, promising high-performance, low-cost, low-noise integrated circuitry.

Solvent-Assisted Surface Engineering for High-Performance All-Inorganic Perovskite Nanocrystal Light-Emitting Diodes.

PubMed

Wang, Lin; Liu, Baiquan; Zhao, Xin; Demir, Hilmi Volkan; Gu, Haoshuang; Sun, Handong

2018-06-13

All-inorganic cesium halide perovskite nanocrystals have attracted much interest in optoelectronic applications for the sake of the readily adjustable band gaps, high photoluminescence quantum yield, pure color emission, and affordable cost. However, because of the ineluctable utilization of organic surfactants during the synthesis, the structural and optical properties of CsPbBr 3 nanocrystals degrade upon transforming from colloidal solutions to solid thin films, which plagues the device operation. Here, we develop a novel solvent-assisted surface engineering strategy, producing high-quality CsPbBr 3 thin films for device applications. A good solvent is first introduced as an assembly trigger to conduct assembly in a one-dimensional direction, which is then interrupted by adding a nonsolvent. The nonsolvent drives the adjacent nanoparticles connecting in a two-dimensional direction. Assembled CsPbBr 3 nanocrystal thin films are densely packed and very smooth with a surface roughness of ∼4.8 nm, which is highly desirable for carrier transport in a light-emitting diode (LED) device. Meanwhile, the film stability is apparently improved. Benefiting from this facile and reliable strategy, we have achieved remarkably improved performance of CsPbBr 3 nanocrystal-based LEDs. Our results not only enrich the methods of nanocrystal surface engineering but also shed light on developing high-performance LEDs.

Effect of Ionic Strength and Surface Charge Density on the Kinetics of Cellulose Nanocrystal Thin Film Swelling.

PubMed

Reid, Michael S; Kedzior, Stephanie A; Villalobos, Marco; Cranston, Emily D

2017-08-01

This work explores cellulose nanocrystal (CNC) thin films (<50 nm) and particle-particle interactions by investigating film swelling in aqueous solutions with varying ionic strength (1-100 mM). CNC film hydration was monitored in situ via surface plasmon resonance, and the kinetics of liquid uptake were quantified. The contribution of electrostatic double-layer forces to film swelling was elucidated by using CNCs with different surface charges (anionic sulfate half ester groups, high and low surface charge density, and cationic trimethylammonium groups). Total water uptake in the thin films was found to be independent of ionic strength and surface chemistry, suggesting that in the aggregated state van der Waals forces dominate over double-layer forces to hold the films together. However, the rate of swelling varied significantly. The water uptake followed Fickian behavior, and the measured diffusion constants decreased with the ionic strength gradient between the film and the solution. This work highlights that nanoparticle interactions and dispersion are highly dependent on the state of particle aggregation and that the rate of water uptake in aggregates and thin films can be tailored based on surface chemistry and solution ionic strength.

Probing Active Nematic Films with Magnetically Manipulated Colloids

NASA Astrophysics Data System (ADS)

Rivas, David; Chen, Kui; Henry, Robert; Reich, Daniel; Leheny, Robert

We study microtubule-based extensile active nematic films using rod-like and disk-shaped magnetic colloids to probe the mechanical and hydrodynamic properties of this quasi-two dimensional out-of-equilibrium system. The active nematics are driven by molecular motors that hydrolyze ATP and cause sliding motion between microtubular bundles. This motion produces a dynamic nematic director field, which continuously creates pairs of +1/2 and -1/2 defects. In the absence of externally applied forces or torques, we observe that the magnetic rods in contact with the films align with the local director, indicating the existence of mechanical coupling between the film and probe. By applying known magnetic torques to the rods and observing their rotation with respect to the director, we gain insight into this coupling. We also find that by rotating magnetic microdisks using magnetic fields, hydrodynamic flows are produced that compete with the films' intrinsic flow, leading to significant effects on the director field and the defect landscape. At certain rotation rates, the disks produce a vortex-like structure in the director field and cause the creation and shedding of defects from the disk boundary.

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.

In vivo investigation of hybrid Paclitaxel nanocrystals with dual fluorescent probes for cancer theranostics.

PubMed

Hollis, Christin P; Weiss, Heidi L; Evers, B Mark; Gemeinhart, Richard A; Li, Tonglei

2014-06-01

To develop novel hybrid paclitaxel (PTX) nanocrystals, in which bioactivatable (MMPSense® 750 FAST) and near infrared (Flamma Fluor® FPR-648) fluorophores are physically incorporated, and to evaluate their anticancer efficacy and diagnostic properties in breast cancer xenograft murine model. The pure and hybrid paclitaxel nanocrystals were prepared by an anti-solvent method, and their physical properties were characterized. The tumor volume change and body weight change were evaluated to assess the treatment efficacy and toxicity. Bioimaging of treated mice was obtained non-invasively in vivo. The released MMPSense molecules from the hybrid nanocrystals were activated by matrix metalloproteinases (MMPs) in vivo, similarly to the free MMPSense, demonstrating its ability to monitor cancer progression. Concurrently, the entrapped FPR-648 was imaged at a different wavelength. Furthermore, when administered at 20 mg/kg, the nanocrystal formulations exerted comparable efficacy as Taxol®, but with decreased toxicity. Hybrid nanocrystals that physically integrated two fluorophores were successfully prepared from solution. Hybrid nanocrystals were shown not only exerting antitumor activity, but also demonstrating the potential of multi-modular bioimaging for diagnostics.

Controlled synthesis of bright and compatible lanthanide-doped upconverting nanocrystals

DOEpatents

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

2017-01-31

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

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.

Room-temperature processed films of colloidal carved rod-shaped nanocrystals of reduced tungsten oxide as interlayers for perovskite solar cells.

PubMed

Masi, Sofia; Mastria, Rosanna; Scarfiello, Riccardo; Carallo, Sonia; Nobile, Concetta; Gambino, Salvatore; Sibillano, Teresa; Giannini, Cinzia; Colella, Silvia; Listorti, Andrea; Cozzoli, P Davide; Rizzo, Aurora

2018-04-25

Thanks to their high stability, good optoelectronic and extraordinary electrochromic properties, tungsten oxides are among the most valuable yet underexploited materials for energy conversion applications. Herein, colloidal one-dimensional carved nanocrystals of reduced tungsten trioxide (WO3-x) are successfully integrated, for the first time, as a hole-transporting layer (HTL) into CH3NH3PbI3 perovskite solar cells with a planar inverted device architecture. Importantly, the use of such preformed nanocrystals guarantees the facile solution-cast-only deposition of a homogeneous WO3-x thin film at room temperature, allowing achievement of the highest power conversion efficiency ever reported for perovskite solar cells incorporating raw and un-doped tungsten oxide based HTL.

Solvent-like ligand-coated ultrasmall cadmium selenide nanocrystals: strong electronic coupling in a self-organized assembly.

PubMed

Lawrence, Katie N; Johnson, Merrell A; Dolai, Sukanta; Kumbhar, Amar; Sardar, Rajesh

2015-07-21

Strong inter-nanocrystal electronic coupling is a prerequisite for delocalization of exciton wave functions and high conductivity. We report 170 meV electronic coupling energy of short chain poly(ethylene glycol) thiolate-coated ultrasmall (<2.5 nm in diameter) CdSe semiconductor nanocrystals (SNCs) in solution. Cryo-transmission electron microscopy analysis showed the formation of a pearl-necklace assembly of nanocrystals in solution with regular inter-nanocrystal spacing. The electronic coupling was studied as a function of CdSe nanocrystal size where the smallest nanocrystals exhibited the largest coupling energy. The electronic coupling in spin-cast thin-film (<200 nm in thickness) of poly(ethylene glycol) thiolate-coated CdSe SNCs was studied as a function of annealing temperature, where an unprecedentedly large, ∼400 meV coupling energy was observed for 1.6 nm diameter SNCs, which were coated with a thin layer of poly(ethylene glycol) thiolates. Small-angle X-ray scattering measurements showed that CdSe SNCs maintained an order array inside the films. The strong electronic coupling of SNCs in a self-organized film could facilitate the large-scale production of highly efficient electronic materials for advanced optoelectronic device application.

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

Probing the formation of silicon nano-crystals (Si-ncs) using variable energy positron annihilation spectroscopy

NASA Astrophysics Data System (ADS)

Knights, A. P.; Bradley, J. D. B.; Hulko, O.; Stevanovic, D. V.; Edwards, C. J.; Kallis, A.; Coleman, P. G.; Crowe, I. F.; Halsall, M. P.; Gwilliam, R. M.

2011-01-01

We describe preliminary results from studies of the formation of silicon nano-crystals (Si-ncs) embedded in stoichiometric, thermally grown SiO2 using Variable Energy Positron Annihilation Spectroscopy (VEPAS). We show that the VEPAS technique is able to monitor the introduction of structural damage. In SiO2 through the high dose Si+ ion implantation required to introduce excess silicon as a precursor to Si-nc formation. VEPAS is also able to characterize the rate of the removal of this damage with high temperature annealing, showing strong correlation with photoluminescence. Finally, VEPAS is shown to be able to selectively probe the interface between Si-ncs and the host oxide. Introduction of hydrogen at these interfaces suppresses the trapping of positrons at the interfaces.

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

PubMed Central

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

2017-01-01

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

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.

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.

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.

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

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.

Piezoelectric immunochip coated with thin films of bacterial cellulose nanocrystals for dengue detection.

PubMed

Pirich, Cleverton Luiz; de Freitas, Rilton Alves; Torresi, Roberto Manuel; Picheth, Guilherme Fadel; Sierakowski, Maria Rita

2017-06-15

Low-cost piezoelectric devices, such as simple frequency monitoring quartz crystal microbalance (QCM) devices, have good clinical utility as fast diagnostic tools for the detection of several diseases. However, unspecific antigen recognition, poor molecular probe adsorption and the need for sample dilution are still common drawbacks that hinder their use in routine diagnosis. In this work, piezoelectric sensors were previously coated with thin films of bacterial cellulose nanocrystals (CN) to provide a more sensitive and adapted interface for the attachment of monoclonal immunoglobulin G (IgGNS1) and to favor specific detection of non-structural protein 1 (NS1) of dengue fever. The assembly of the immunochip surface was analyzed by atomic force microscopy (AFM) and the NS1 detection was followed by quartz crystal microbalance with (QCM-D) and without energy dissipation monitoring (QCM). The CN surface was able to immobilize 2.30±0.5mgm -2 of IgGNS1, as confirmed by AFM topography and phase images along with QCM-D. The system was able to detect the NS1 protein in serum with only 10-fold dilution in the range of 0.01-10µgmL -1 by both QCM and QCM-D. The limits of detection of the two devices were 0.1μgmL -1 for QCM-D and 0.32μgmL -1 for QCM. As a result, QCM-D and QCM apparatuses can be used to follow NS1 recognition and have good potential for more sensitive, fast and/or less expensive diagnostic assays for dengue. Copyright © 2017 Elsevier B.V. All rights reserved.

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

Flexible probe for measuring local conductivity variations in Li-ion electrode films

NASA Astrophysics Data System (ADS)

Hardy, Emilee; Clement, Derek; Vogel, John; Wheeler, Dean; Mazzeo, Brian

2018-04-01

Li-ion battery performance is governed by electronic and ionic properties of the battery. A key metric that characterizes Li-ion battery cell performance is the electronic conductivity of the electrodes, which are metal foils with thin coatings of electrochemically active materials. To accurately measure the spatial variation of electronic conductivity of these electrodes, a micro-four-line probe (μ4LP) was designed and used to non-destructively measure the properties of commercial-quality Li-ion battery films. This previous research established that the electronic conductivity of film electrodes is not homogeneous throughout the entirety of the deposited film area. In this work, a micro-N-line probe (μNLP) and a flexible micro-flex-line probe (μFLP) were developed to improve the non-destructive micro-scale conductivity measurements that we can take. These devices were validated by comparing test results to that of the predecessor, the micro-four-line probe (μ4LP), on various commercial-quality Li-ion battery electrodes. Results show that there is significant variation in conductivity on a millimeter and even micrometer length scale through the electrode film. Compared to the μ4LP, the μNLP and μFLP also introduce additional measurement configuration possibilities, while providing a more robust design. Researchers and manufacturers can use these probes to identify heterogeneity in their electrodes during the fabrication process, which will lead to the development of better batteries.

Fabrication of Si heterojunction solar cells using P-doped Si nanocrystals embedded in SiNx films as emitters

PubMed Central

2013-01-01

Si heterojunction solar cells were fabricated on p-type single-crystal Si (sc-Si) substrates using phosphorus-doped Si nanocrystals (Si-NCs) embedded in SiNx (Si-NCs/SiNx) films as emitters. The Si-NCs were formed by post-annealing of silicon-rich silicon nitride films deposited by electron cyclotron resonance chemical vapor deposition. We investigate the influence of the N/Si ratio in the Si-NCs/SiNx films on their electrical and optical properties, as well as the photovoltaic properties of the fabricated heterojunction devices. Increasing the nitrogen content enhances the optical gap E04 while deteriorating the electrical conductivity of the Si-NCs/SiNx film, leading to an increased short-circuit current density and a decreased fill factor of the heterojunction device. These trends could be interpreted by a bi-phase model which describes the Si-NCs/SiNx film as a mixture of a high-transparency SiNx phase and a low-resistivity Si-NC phase. A preliminary efficiency of 8.6% is achieved for the Si-NCs/sc-Si heterojunction solar cell. PMID:24188725

Effect of argon implantation on solid-state dewetting: control of size and surface density of silicon nanocrystals.

PubMed

Almadori, Y; Borowik, Ł; Chevalier, N; Barbé, J-C

2017-01-27

Thermally induced solid-state dewetting of ultra-thin films on insulators is a process of prime interest, since it is capable of easily forming nanocrystals. If no particular treatment is performed to the film prior to the solid-state dewetting, it is already known that the size, the shape and the density of nanocrystals is governed by the initial film thickness. In this paper, we report a novel approach to control the size and the surface density of silicon nanocrystals based on an argon-implantation preliminary surface treatment. Using 7.5 nm thin layers of silicon, we show that increasing the implantation dose tends to form smaller silicon nanocrystals with diameter and height lower than 50 nm and 30 nm, respectively. Concomitantly, the surface density is increased by a factor greater than 20, going from 5 μm -2 to values over 100 μm -2 .

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.

Water Vapor Uptake of Ultrathin Films of Biologically Derived Nanocrystals: Quantitative Assessment with Quartz Crystal Microbalance and Spectroscopic Ellipsometry.

PubMed

Niinivaara, Elina; Faustini, Marco; Tammelin, Tekla; Kontturi, Eero

2015-11-10

Despite the relevance of water interactions, explicit analysis of vapor adsorption on biologically derived surfaces is often difficult. Here, a system was introduced to study the vapor uptake on a native polysaccharide surface; namely, cellulose nanocrystal (CNC) ultrathin films were examined with a quartz crystal microbalance with dissipation monitoring (QCM-D) and spectroscopic ellipsometry (SE). A significant mass uptake of water vapor by the CNC films was detected using the QCM-D upon increasing relative humidity. In addition, thickness changes proportional to changes in relative humidity were detected using SE. Quantitative analysis of the results attained indicated that in preference to being soaked by water at the point of hydration each individual CNC in the film became enveloped by a 1 nm thick layer of adsorbed water vapor, resulting in the detected thickness response.

Uncovering the intrinsic size dependence of hydriding phase transformations in nanocrystals.

PubMed

Bardhan, Rizia; Hedges, Lester O; Pint, Cary L; Javey, Ali; Whitelam, Stephen; Urban, Jeffrey J

2013-10-01

A quantitative understanding of nanocrystal phase transformations would enable more efficient energy conversion and catalysis, but has been hindered by difficulties in directly monitoring well-characterized nanoscale systems in reactive environments. We present a new in situ luminescence-based probe enabling direct quantification of nanocrystal phase transformations, applied here to the hydriding transformation of palladium nanocrystals. Our approach reveals the intrinsic kinetics and thermodynamics of nanocrystal phase transformations, eliminating complications of substrate strain, ligand effects and external signal transducers. Clear size-dependent trends emerge in nanocrystals long accepted to be bulk-like in behaviour. Statistical mechanical simulations show these trends to be a consequence of nanoconfinement of a thermally driven, first-order phase transition: near the phase boundary, critical nuclei of the new phase are comparable in size to the nanocrystal itself. Transformation rates are then unavoidably governed by nanocrystal dimensions. Our results provide a general framework for understanding how nanoconfinement fundamentally impacts broad classes of thermally driven solid-state phase transformations relevant to hydrogen storage, catalysis, batteries and fuel cells.

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.

Exciton Dynamics in Alternative Solar Cell Materials: Polymers, Nanocrystals, and Small Molecules

NASA Astrophysics Data System (ADS)

Pundsack, Thomas J.

To keep fossil fuel usage in 2040 even with 2010 usage, 50% of global energy will need to come from alternative sources such as solar cells. While the photovoltaic market is currently dominated by crystalline silicon, there are many low-cost solar cell materials such as conjugated polymers, semiconductor nanocrystals, and organic small molecules which could compete with fossil fuels. To create cost-competitive devices, understanding the excited state dynamics of these materials is necessary. The first section of this thesis looks at aggregation in poly(3-hexylthiophene) (P3HT) which is commonly used in organic photovoltaics. The amount of aggregation in P3HT thin films was controlled by using a mixture of regioregular and regiorandom P3HT. Even with few aggregates present, excited states were found to transfer from amorphous to aggregate domains in <50 fs which could indicate efficient long-range energy transfer. To further study P3HT aggregation, a triblock consisting of two P3HT chains with a coil polymer between them was investigated. By changing solvents, aggregation was induced in a stable and reversible manner allowing for spectroscopic studies of P3HT aggregates in solution. The polarity of the solvent was adjusted, and no change in excited state dynamics was observed implying the excited state has little charge-transfer character. Next, the conduction band density of states for copper zinc tin sulfide nanocrystals (CZTS NCs) was measured using pump-probe spectroscopy and found to be in agreement with theoretical results. The density of states shifted and dilated for smaller NCs indicative of quantum confinement. The excited state lifetime was found to be short (<20 ps) and independent of NC size which could limit the efficiency of CZTS photovoltaic devices. Finally, triplet-triplet annihilation (TTA) was studied in platinum octaethylporphyrin (PtOEP) thin films. By analyzing pump-probe spectra, the product of TTA in PtOEP thin films was assigned to a long

Fenofibrate Nanocrystals Embedded in Oral Strip-Films for Bioavailability Enhancement

PubMed Central

Barvaliya, Manish; Zhang, Lu; Anovadiya, Ashish; Brahmbhatt, Harshad; Paul, Parimal; Tripathi, Chandrabhanu

2018-01-01

The aim of the present study was to make a fenofibrate (FNB) nanocrystal (NC) by wet media milling, characterizations and formulates into oral strip-films (OSFs). Mechanical properties, redispersion study, and solid-state characterizations results suggested that reduction of drug crystal size at nanoscale and incorporation into OSFs does not affect the solid-state properties of the drug. In vitro dissolution kinetics showed enhanced dissolution rate was easily manipulated by changing the thickness of the OSF. In situ UV-imaging was used to monitor drug dissolution qualitatively and quantitatively in real time. Results confirm that the intrinsic dissolution rates and surface drug concentration measured with this device were in agreement with the USP-IV dissolution profiles. In vivo pharmacokinetics in rabbits showed a significant difference in the pharmacokinetics parameter (1.4 fold increase bioavailability) of FNB NC-loaded OSFs as compared to the marketed formulation “Tricor” and as-received (pristine) drug. This approach of drug nanocrystallization and incorporation into OSFs may have significant applications in cost-effective tools for bioavailability enhancement of FNB. PMID:29438297

Multifunctional PLA-PHB/cellulose nanocrystal films: processing, structural and thermal properties.

PubMed

Arrieta, M P; Fortunati, E; Dominici, F; Rayón, E; López, J; Kenny, J M

2014-07-17

Cellulose nanocrystals (CNCs) synthesized from microcrystalline cellulose by acid hydrolysis were added into poly(lactic acid)-poly(hydroxybutyrate) (PLA-PHB) blends to improve the final properties of the multifunctional systems. CNC were also modified with a surfactant (CNCs) to increase the interfacial adhesion in the systems maintaining the thermal stability. Firstly, masterbatch pellets were obtained for each formulation to improve the dispersion of the cellulose structures in the PLA-PHB and then nanocomposite films were processed. The thermal stability as well as the morphological and structural properties of nanocomposites was investigated. While PHB increased the PLA crystallinity due to its nucleation effect, well dispersed CNC and CNCs not only increased the crystallinity but also improved the processability, the thermal stability and the interaction between both polymers especially in the case of the modified CNCs based PLA-PHB formulation. Likewise, CNCs were better dispersed in PLA-CNCs and PLA-PHB-CNCs, than CNC. Copyright © 2014 Elsevier Ltd. All rights reserved.

Ti Ni shape memory alloy film-actuated microstructures for a MEMS probe card

NASA Astrophysics Data System (ADS)

Namazu, Takahiro; Tashiro, Youichi; Inoue, Shozo

2007-01-01

This paper describes the development of a novel silicon (Si) cantilever beam device actuated by titanium-nickel (Ti-Ni) shape memory alloy (SMA) films. A Ti-Ni SMA film can yield high work output per unit volume, so a Ti-Ni film-actuated Si cantilever beam device is a prospective tool for use as a microelectromechanical system (MEMS) probe card that provides a relatively large contact force between the probe and electrode pad in spite of its minute size. Before fabrication of the device, the thermomechanical deformation behavior of Ti-Ni SMA films with various compositions was investigated in order to determine a sufficient constituent film for a MEMS actuator. As a result, Ti-Ni films having a Ti content of 50.2 to 52.6 atomic% (at%) were found to be usable for operation as a room temperature actuator. We have developed a Ti-Ni film-actuated Si cantilever beam device, which can produce a contact force by the cantilever bending when in contact, and also by the shape memory effect (SME) of the Ti-Ni film arising from Joule heating. The SME of the Ti-Ni film can generate an additional average contact force of 200 µN with application of 500 mW to the film. In addition to physical contact, a dependable electric contact between the Au film-coated probe tip and the Al film electrode was achieved. However, the contact resistance exhibited an average value of 25 Ω, which would have to be reduced for practical use. Reliability tests confirmed the durability of the Ti-Ni film-actuated Si cantilever-beam, in that the contact resistance was constant throughout a large number of physical contacts (>104 times).

Extraordinary Interfacial Stitching between Single All-Inorganic Perovskite Nanocrystals

PubMed Central

2018-01-01

All-inorganic cesium lead halide perovskite nanocrystals are extensively studied because of their outstanding optoelectronic properties. Being of a cubic shape and typically featuring a narrow size distribution, CsPbX3 (X = Cl, Br, and I) nanocrystals are the ideal starting material for the development of homogeneous thin films as required for photovoltaic and optoelectronic applications. Recent experiments reveal spontaneous merging of drop-casted CsPbBr3 nanocrystals, which is promoted by humidity and mild-temperature treatments and arrested by electron beam irradiation. Here, we make use of atom-resolved annular dark-field imaging microscopy and valence electron energy loss spectroscopy in a state-of-the-art low-voltage monochromatic scanning transmission electron microscope to investigate the aggregation between individual nanocrystals at the atomic level. We show that the merging process preserves the elemental composition and electronic structure of CsPbBr3 and takes place between nanocrystals of different sizes and orientations. In particular, we reveal seamless stitching for aligned nanocrystals, similar to that reported in the past for graphene flakes. Because the crystallographic alignment occurs naturally in drop-casted layers of CsPbX3 nanocrystals, our findings constitute the essential first step toward the development of large-area nanosheets with band gap energies predesigned by the nanocrystal choice—the gateway to large-scale photovoltaic applications of inorganic perovskites. PMID:29355301

Extraordinary Interfacial Stitching between Single All-Inorganic Perovskite Nanocrystals.

PubMed

Gomez, Leyre; Lin, Junhao; de Weerd, Chris; Poirier, Lucas; Boehme, Simon C; von Hauff, Elizabeth; Fujiwara, Yasufumi; Suenaga, Kazutomo; Gregorkiewicz, Tom

2018-02-14

All-inorganic cesium lead halide perovskite nanocrystals are extensively studied because of their outstanding optoelectronic properties. Being of a cubic shape and typically featuring a narrow size distribution, CsPbX 3 (X = Cl, Br, and I) nanocrystals are the ideal starting material for the development of homogeneous thin films as required for photovoltaic and optoelectronic applications. Recent experiments reveal spontaneous merging of drop-casted CsPbBr 3 nanocrystals, which is promoted by humidity and mild-temperature treatments and arrested by electron beam irradiation. Here, we make use of atom-resolved annular dark-field imaging microscopy and valence electron energy loss spectroscopy in a state-of-the-art low-voltage monochromatic scanning transmission electron microscope to investigate the aggregation between individual nanocrystals at the atomic level. We show that the merging process preserves the elemental composition and electronic structure of CsPbBr 3 and takes place between nanocrystals of different sizes and orientations. In particular, we reveal seamless stitching for aligned nanocrystals, similar to that reported in the past for graphene flakes. Because the crystallographic alignment occurs naturally in drop-casted layers of CsPbX 3 nanocrystals, our findings constitute the essential first step toward the development of large-area nanosheets with band gap energies predesigned by the nanocrystal choice-the gateway to large-scale photovoltaic applications of inorganic perovskites.

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

PubMed

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

2015-09-22

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

Effect of cellulose nanocrystals from corn cob with dispersion agent polyvinyl pyrrolidone in natural rubber latex film after aging treatment

NASA Astrophysics Data System (ADS)

Harahap, H.; Ridha, M.; Halimatuddahliana; Taslim; Iriany

2018-02-01

This study about the resistance of natural rubber latex films using nanocrystals cellulose filler from corn cob waste by aging treatment. Corn cob used as organic filler composed of cellulose, hemicellulose, and lignin. Each component has a potential for reuse, such as cellulose. Cellulose from corn cob has potential application as a filler prepared by hydrolysis process using a strong acid. The producing of natural rubber latex films through coagulant dowsing process. This research started with the pre-vulcanization process of natural rubber latex at 70 °C and followed by process of vulcanization at 110 °C for 20 minutes. Natural rubber latex films that have been produced continued with the aging treatment at 70 °C for 168 hours. The mechanical properties of natural rubber latex films after aging treatment are the tensile strength, elongation at break, M100 and M300 have performed.

Design and Operation of a Fast, Thin-Film Thermocouple Probe on a Turbine Engine

NASA Technical Reports Server (NTRS)

Meredith, Roger D.; Wrbanek, John D.; Fralick, Gustave C.; Greer, Lawrence C., III; Hunter, Gary W.; Chen, Liang-Yu

2014-01-01

As a demonstration of technology maturation, a thin-film temperature sensor probe was fabricated and installed on a F117 turbofan engine via a borescope access port to monitor the temperature experienced in the bleed air passage of the compressor area during an engine checkout test run. To withstand the harsh conditions experienced in this environment, the sensor probe was built from high temperature materials. The thin-film thermocouple sensing elements were deposited by physical vapor deposition using pure metal elements, thus avoiding the inconsistencies of sputter-depositing particular percentages of materials to form standardized alloys commonly found in thermocouples. The sensor probe and assembly were subjected to a strict protocol of multi-axis vibrational testing as well as elevated temperature pressure testing to be qualified for this application. The thin-film thermocouple probe demonstrated a faster response than a traditional embedded thermocouple during the engine checkout run.

Identifying barriers to charge-carriers in the bulk and surface regions of Cu2ZnSnS4 nanocrystal films by x-ray absorption fine structures (XAFSs)

NASA Astrophysics Data System (ADS)

Turnbull, Matthew J.; Vaccarello, Daniel; Yiu, Yun Mui; Sham, Tsun-Kong; Ding, Zhifeng

2016-11-01

Solar cell performance is most affected by the quality of the light absorber layer. For thin-film devices, this becomes a two-fold problem of maintaining a low-cost design with well-ordered nanocrystal (NC) structure. The use of Cu2ZnSnS4 (CZTS) NCs as the light absorber films forms an ideal low-cost design, but the quaternary structure makes it difficult to maintain a well-ordered layer without the use of high-temperature treatments. There is little understanding of how CZTS NC structures affect the photoconversion efficiency, the charge-carriers, and therefore the performance of the device manufactured from it. To examine these relationships, the measured photoresponse from the photo-generation of charge-carrier electron-hole pairs was compared against the crystal structure, as short-range and long-range crystal orders for the films. The photoresponse simplifies the electronic properties into three basic steps that can be associated with changes in energy levels within the band structure. These changes result in the formation of barriers to charge-carrier flow. The extent of these barriers was determined using synchrotron-based X-ray absorbance fine structure to probe the individual metal centers in the film, and comparing these to molecular simulations of the ideal extended x-ray absorbance fine structure scattering. This allowed for the quantification of bond lengths, and thus an interpretation of the distortions in the crystal lattice. The various characteristics of the photoresponse were then correlated to the crystallographic order and used to gain physical insight into barriers to charge-carriers in the bulk and surface regions of CZTS films.

Characterization of memory and measurement history in photoconductivity of nanocrystal arrays

NASA Astrophysics Data System (ADS)

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

2010-10-01

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

In situ growth of CuInS2 nanocrystals on nanoporous TiO2 film for constructing inorganic/organic heterojunction solar cells

PubMed Central

2013-01-01

Inorganic/organic heterojunction solar cells (HSCs) have attracted increasing attention as a cost-effective alternative to conventional solar cells. This work presents an HSC by in situ growth of CuInS2(CIS) layer as the photoabsorption material on nanoporous TiO2 film with the use of poly(3-hexylthiophene) (P3HT) as hole-transport material. The in situ growth of CIS nanocrystals has been realized by solvothermally treating nanoporous TiO2 film in ethanol solution containing InCl3 · 4H2O, CuSO4 · 5H2O, and thioacetamide with a constant concentration ratio of 1:1:2. InCl3 concentration plays a significant role in controlling the surface morphology of CIS layer. When InCl3 concentration is 0.1 M, there is a layer of CIS flower-shaped superstructures on TiO2 film, and CIS superstructures are in fact composed of ultrathin nanoplates as ‘petals’ with plenty of nanopores. In addition, the nanopores of TiO2 film are filled by CIS nanocrystals, as confirmed using scanning electron microscopy image and by energy dispersive spectroscopy line scan analysis. Subsequently, HSC with a structure of FTO/TiO2/CIS/P3HT/PEDOT:PSS/Au has been fabricated, and it yields a power conversion efficiency of 1.4%. Further improvement of the efficiency can be expected by the optimization of the morphology and thickness of CIS layer and the device structure. PMID:23947562

A comparative study on cellulose nanocrystals extracted from bleached cotton and flax and used for casting films with glycerol and sorbitol plasticisers.

PubMed

Csiszár, Emilia; Nagy, Sebestyén

2017-10-15

Cellulose nanocrystals (CNCs) were released from bleached cotton and flax by a sulphuric acid hydrolysis with about 40 and 34% yield, respectively. The rod-like cotton-CNC particles were slightly longer and wider and had a less pronounced aggregation ability in aqueous suspension than the flax-CNC ones. Films were cast from the CNC suspensions with sorbitol and glycerol plasticisers. The concept behind this research was to explore how the plasticisers - with similar structure but different molecular weight - and their concentrations affect the perceptible and measured properties of CNC films. Results revealed that the type of plasticiser determined the morphology and the optical and tensile properties of films. The best quality CNC film with an averaged thickness of 50μm was obtained with 20% sorbitol from cotton-CNC. It was proved that behaviour of sorbitol and glycerol plasticisers in CNC films was very similar to that reported previously for starch films. Copyright © 2017 Elsevier Ltd. All rights reserved.

Capillary levelling as a probe of rheology in polymer thin films

NASA Astrophysics Data System (ADS)

McGraw, Joshua D.; Jago, Nick M.; Dalnoki-Veress, Kari

2011-03-01

While measuring the rheology of bulk polymer systems is routine, when the size of a system becomes comparable to the molecular size, flow properties are poorly understood and hard to measure. Here, we present the results of experiments that are easily performed and can probe the rheological properties of polymer films that are mere tens of nanometres in thickness. We prepare glassy bilayer polymer films with height profiles well approximated by a step function. Upon annealing above the glass transition, broadening of the height profiles due to gradients in the Laplace pressure is observed. By validating the technique as a probe of the rheology with a range of molecular weights, we will show that this robust technique can be used to investigate the effects of confinement and interfaces on the rheology of ultrathin polymer films. Financial support from NSERC of Canada is gratefully acknowledged.

Optical sensor platform based on cellulose nanocrystals (CNC) - 4'-(hexyloxy)-4-biphenylcarbonitrile (HOBC) bi-phase nematic liquid crystal composite films.

PubMed

Santos, Moliria V; Tercjak, Agnieszka; Gutierrez, Junkal; Barud, Hernane S; Napoli, Mariana; Nalin, Marcelo; Ribeiro, Sidney J L

2017-07-15

The preparation of composite materials has gained tremendous attention due to the potential synergy of the combined materials. Here we fabricate novel thermal/electrical responsive photonic composite films combining cellulose nanocrystals (CNC) with a low molecular weight nematic liquid crystal (NLC), 4'-(hexyloxy)-4-biphenylcarbonitrile (HOBC). The obtained composite material combines both intense structural coloration of photonic cellulose and thermal and conductive properties of NLC. Scanning electron microscopy (SEM) results confirmed that liquid crystals coated CNC films maintain chiral nematic structure characteristic of CNC film and simultaneously, transversal cross-section scanning electron microscopy images indicated penetration of liquid crystals through the CNC layers. Investigated composite film maintain NLC optical properties being switchable as a function of temperature during heating/cooling cycles. The relationship between the morphology and thermoresponsive in the micro/nanostructured materials was investigated by using transmission optical microscopy (TOM). Conductive response of the composite films was proved by Electrostatic force microscopy (EFM) measurement. Designed thermo- and electro-responsive materials open novel simple pathway of fabrication of CNC-based materials with tunable properties. Copyright © 2017. Published by Elsevier Ltd.

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.

Potentiometric Titrations for Measuring the Capacitance of Colloidal Photodoped ZnO Nanocrystals.

PubMed

Brozek, Carl K; Hartstein, Kimberly H; Gamelin, Daniel R

2016-08-24

Colloidal semiconductor nanocrystals offer a unique opportunity to bridge molecular and bulk semiconductor redox phenomena. Here, potentiometric titration is demonstrated as a method for quantifying the Fermi levels and charging potentials of free-standing colloidal n-type ZnO nanocrystals possessing between 0 and 20 conduction-band electrons per nanocrystal, corresponding to carrier densities between 0 and 1.2 × 10(20) cm(-3). Potentiometric titration of colloidal semiconductor nanocrystals has not been described previously, and little precedent exists for analogous potentiometric titration of any soluble reductants involving so many electrons. Linear changes in Fermi level vs charge-carrier density are observed for each ensemble of nanocrystals, with slopes that depend on the nanocrystal size. Analysis indicates that the ensemble nanocrystal capacitance is governed by classical surface electrical double layers, showing no evidence of quantum contributions. Systematic shifts in the Fermi level are also observed with specific changes in the identity of the charge-compensating countercation. As a simple and contactless alternative to more common thin-film-based voltammetric techniques, potentiometric titration offers a powerful new approach for quantifying the redox properties of colloidal semiconductor nanocrystals.

Cation Exchange Reactions for Improved Quality and Diversity of Semiconductor Nanocrystals

NASA Astrophysics Data System (ADS)

Beberwyck, Brandon James

Observing the size and shape dependent physical properties of semiconductor nanocrystals requires synthetic methods capable of not only composition and crystalline phase control but also molecular scale uniformity for a particle consisting of tens to hundreds of thousands of atoms. The desire for synthetic methods that produce uniform nanocrystals of complex morphologies continues to increase as nanocrystals find roles in commercial applications, such as biolabeling and display technologies, that are simultaneously restricting material compositions. With these constraints, new synthetic strategies that decouple the nanocrystal's chemical composition from its morphology are necessary. This dissertation explores the cation exchange reaction of colloidal semiconductor nanocrystals, a template-based chemical transformation that enables the interconversion of nanocrystals between a variety of compositions while maintaining their size dispersity and morphology. Chapter 1 provides an introduction to the versatility of this replacement reaction as a synthetic method for semiconductor nanocrystals. An overview of the fundamentals of the cation exchange reaction and the diversity of products that are achievable is presented. Chapter 2 examines the optical properties of nanocrystal heterostructures produced through cation exchange reactions. The deleterious impact of exchange on the photoluminescence is correlated to residual impurities and a simple annealing protocol is demonstrated to achieve photoluminescence yields comparable to samples produced by conventional methods. Chapter 3 investigates the extension of the cation exchange reaction beyond ionic nanocrystals. Covalent III-V nanocrystal of high crystallinity and low size dispersity are synthesized by the cation exchange of cadmium pnictide nanocrystals with group 13 ions. Lastly, Chapter 4 highlights future studies to probe cation exchange reactions in colloidal semiconductor nanocrystals and progress that needs to be

Influence of cellulose nanocrystals concentration and ionic strength on the elaboration of cellulose nanocrystals-xyloglucan multilayered thin films.

PubMed

Dammak, Abir; Moreau, Céline; Azzam, Firas; Jean, Bruno; Cousin, Fabrice; Cathala, Bernard

2015-12-15

The effect of the variation of CNC concentration on the growth pattern of CNC-XG films is investigated. We found that a transition in the growth slope occurs at a CNC concentration of roughly 3-4gL(-1). A close effect can be obtained by the increase of the ionic strength of the CNC suspensions, suggesting that electrostatic interactions are involved. Static light scattering investigation of CNC dispersions at increasing concentrations demonstrated that the particle-particle interactions change as the CNC concentration increases. Neutron Reflectivity (NR) was used to probe the internal structure of the films. The increase of the CNC concentration as well as the increase of the ionic strength in the CNC suspension were found to induce a densification of the adsorbed CNC layers, even though the mechanisms are not strictly identical in both cases. Small changes in these parameters provide a straightforward way of controlling the architecture of CNC-based multilayered thin films and, as a result, their functional properties. Copyright © 2015 Elsevier Inc. All rights reserved.

Nanocrystal Core Lipoprotein Biomimetics for Imaging of Lipoproteins and Associated Diseases.

PubMed

Fay, Francois; Sanchez-Gaytan, Brenda L; Cormode, David P; Skajaa, Torjus; Fisher, Edward A; Fayad, Zahi A; Mulder, Willem J M

2013-02-01

Lipoproteins are natural nanoparticles composed of phospholipids and apolipoproteins that transport lipids throughout the body. As key effectors of lipid homeostasis, the functions of lipoproteins have been demonstrated to be crucial during the development of cardiovascular diseases. Therefore various strategies have been used to study their biology and detect them in vivo. A recent approach has been the production of lipoprotein biomimetic particles loaded with diagnostically active nanocrystals in their core. These include, but are not limited to: quantum dots, iron oxide or gold nanocrystals. Inclusion of these nanocrystals enables the utilization of lipoproteins as probes for a variety of imaging modalities (computed tomography, magnetic resonance imaging, fluorescence) while preserving their biological activity. Furthermore as some lipoproteins naturally accumulate in atherosclerotic plaque or specific tumor tissues, nanocrystal core lipoprotein biomimetics have been developed as contrast agents for early diagnosis of these diseases.

Positioning growth of NPB crystalline nanowires on the PTCDA nanocrystal template.

PubMed

Wang, Hong; Lin, Haiping; Fan, Xing; Ostendorp, Stefan; Wang, Yandong; Huang, Lizhen; Jiang, Lin; Li, Youyong; Wilde, Gerhard; Fuchs, Harald; Wang, Wenchong; Chi, Lifeng

2018-05-31

Non-planar organic molecules often form amorphous films via vapor phase deposition on surfaces. In this study, we demonstrate for the first time that direct crystalline growth of non-planar NPB is possible when the orientation of initially deposited molecules on a PTCDA nanocrystal template is controlled to make it analogous to the structure of the molecular crystal. The crystalline NPB nanowires can be further positioned by controlling the site-selective growth of PTCDA nanocrystal templates at pre-determined locations. Short channel bottom contact OFET array with the NPB nanowires directly grown on electrodes were subsequently fabricated. The hole mobility of NPB nanowires is improved by 40-fold in comparison to that of the amorphous films.

Nanocomposite films

DOEpatents

Mitlin, David; , Ophus, Colin; Evoy, Stephane; Radmilovic, Velimir; Mohammadi, Reza; Westra, Ken; Nelson-Fitzpatrick, Nathaniel; Lee, Zonghoon

2010-07-20

A thin-film composition of nanocrystal molybdenum in an amorphous metallic matrix may be formed by co-sputtering Mo with aluminum or nickel. NEMS cantilevers may be formed from the film. The films exhibit high nanoindentation hardness and a reduction in roughness and intrinsic stress, while maintaining resistivity in the metallic range.

Surface interaction forces of cellulose nanocrystals grafted with thermoresponsive polymer brushes.

PubMed

Zoppe, Justin O; Osterberg, Monika; Venditti, Richard A; Laine, Janne; Rojas, Orlando J

2011-07-11

The colloidal stability and thermoresponsive behavior of poly(N-isopropylacrylamide) brushes grafted from cellulose nanocrystals (CNCs) of varying graft densities and molecular weights was investigated. Indication of the grafted polymer brushes was obtained after AFM imaging of CNCs adsorbed on silica. Also, aggregation of the nanoparticles carrying grafts of high degree of polymerization was observed. The responsiveness of grafted CNCs in aqueous dispersions and as an ultrathin film was evaluated by using light scattering, viscosimetry, and colloidal probe microscopy (CPM). Light transmittance measurements showed temperature-dependent aggregation originating from the different graft densities and molecular weights. The lower critical solution temperature (LCST) of grafted poly(NiPAAm) brushes was found to decrease with the ionic strength, as is the case for free poly(NiPAAm) in aqueous solution. Thermal responsive behavior of grafted CNCs in aqueous dispersions was observed by a sharp increase in dispersion viscosity as the temperature approached the LCST. CPM in liquid media for asymmetric systems consisting of ultrathin films of CNCs and a colloidal silica probe showed the distinctive effects of the grafted polymer brushes on interaction and adhesive forces. The origin of such forces was found to be mainly electrostatic and steric in the case of bare and grafted CNCs, respectively. A decrease in the onset of attractive and adhesion forces of grafted CNCs films were observed with the ionic strength of the aqueous solution. The decreased mobility of polymer brushes upon partial collapse and decreased availability of hydrogen bonding sites with higher electrolyte concentration were hypothesized as the main reasons for the less prominent polymer bridging between interacting surfaces.

Probing crystal structure and mesoscale assembly of cellulose microfibrils in plant cell walls, tunicate tests, and bacterial films using vibrational sum frequency generation (SFG) spectroscopy.

PubMed

Lee, Christopher M; Kafle, Kabindra; Park, Yong Bum; Kim, Seong H

2014-06-14

This study reports that the noncentrosymmetry and phase synchronization requirements of the sum frequency generation (SFG) process can be used to distinguish the three-dimensional organization of crystalline cellulose distributed in amorphous matrices. Crystalline cellulose is produced as microfibrils with a few nanometer diameters by plants, tunicates, and bacteria. Crystalline cellulose microfibrils are embedded in wall matrix polymers and assembled into hierarchical structures that are precisely designed for specific biological and mechanical functions. The cellulose microfibril assemblies inside cell walls are extremely difficult to probe. The comparison of vibrational SFG spectra of uniaxially-aligned and disordered films of cellulose Iβ nanocrystals revealed that the spectral features cannot be fully explained with the crystallographic unit structure of cellulose. The overall SFG intensity, the alkyl peak shape, and the alkyl/hydroxyl intensity ratio are sensitive to the lateral packing and net directionality of the cellulose microfibrils within the SFG coherence length scale. It was also found that the OH SFG stretch peaks could be deconvoluted to find the polymorphic crystal structures of cellulose (Iα and Iβ). These findings were used to investigate the cellulose crystal structure and mesoscale cellulose microfibril packing in intact plant cell walls, tunicate tests, and bacterial films.

Femtosecond transient absorption dynamics of close-packed gold nanocrystal monolayer arrays*1

NASA Astrophysics Data System (ADS)

Eah, Sang-Kee; Jaeger, Heinrich M.; Scherer, Norbert F.; Lin, Xiao-Min; Wiederrecht, Gary P.

2004-03-01

Femtosecond transient absorption spectroscopy is used to investigate hot electron dynamics of close-packed 6 nm gold nanocrystal monolayers. Morphology changes of the monolayer caused by the laser pump pulse are monitored by transmission electron microscopy. At low pump power, the monolayer maintains its structural integrity. Hot electrons induced by the pump pulse decay through electron-phonon (e-ph) coupling inside the nanocrystals with a decay constant that is similar to the value for bulk films. At high pump power, irreversible particle aggregation and sintering occur in the nanocrystal monolayer, which cause damping and peak shifting of the transient bleach signal.

Stoichiometric control of lead chalcogenide nanocrystal solids to enhance their electronic and optoelectronic device performance.

PubMed

Oh, Soong Ju; Berry, Nathaniel E; Choi, Ji-Hyuk; Gaulding, E Ashley; Paik, Taejong; Hong, Sung-Hoon; Murray, Christopher B; Kagan, Cherie R

2013-03-26

We investigate the effects of stoichiometric imbalance on the electronic properties of lead chalcogenide nanocrystal films by introducing excess lead (Pb) or selenium (Se) through thermal evaporation. Hall-effect and capacitance-voltage measurements show that the carrier type, concentration, and Fermi level in nanocrystal solids may be precisely controlled through their stoichiometry. By manipulating only the stoichiometry of the nanocrystal solids, we engineer the characteristics of electronic and optoelectronic devices. Lead chalcogenide nanocrystal field-effect transistors (FETs) are fabricated at room temperature to form ambipolar, unipolar n-type, and unipolar p-type semiconducting channels as-prepared and with excess Pb and Se, respectively. Introducing excess Pb forms nanocrystal FETs with electron mobilities of 10 cm(2)/(V s), which is an order of magnitude higher than previously reported in lead chalcogenide nanocrystal devices. Adding excess Se to semiconductor nanocrystal solids in PbSe Schottky solar cells enhances the power conversion efficiency.

Nanocrystal Core Lipoprotein Biomimetics for Imaging of Lipoproteins and Associated Diseases

PubMed Central

Fay, Francois; Sanchez-Gaytan, Brenda L.; Cormode, David P.; Skajaa, Torjus; Fisher, Edward A.; Fayad, Zahi A.

2013-01-01

Lipoproteins are natural nanoparticles composed of phospholipids and apolipoproteins that transport lipids throughout the body. As key effectors of lipid homeostasis, the functions of lipoproteins have been demonstrated to be crucial during the development of cardiovascular diseases. Therefore various strategies have been used to study their biology and detect them in vivo. A recent approach has been the production of lipoprotein biomimetic particles loaded with diagnostically active nanocrystals in their core. These include, but are not limited to: quantum dots, iron oxide or gold nanocrystals. Inclusion of these nanocrystals enables the utilization of lipoproteins as probes for a variety of imaging modalities (computed tomography, magnetic resonance imaging, fluorescence) while preserving their biological activity. Furthermore as some lipoproteins naturally accumulate in atherosclerotic plaque or specific tumor tissues, nanocrystal core lipoprotein biomimetics have been developed as contrast agents for early diagnosis of these diseases. PMID:23687557

The peculiarity of the formation of zinc films on a glass substrate

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

Tomaev, V. V., E-mail: tvaza@mail.ru; Saint Petersburg Mining University, Russia, 199106, St. Petersburg, V.O., 21-st line, 2; Polishchuk, V. A., E-mail: vpvova2010@yandex.ru

2016-06-17

Thin Nanocrystalline films of the zinc have been fabricated by thermal spraying on the glass substrate. Morphologies and structure of the films had been investigated by the methods X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). It is found that the surface of the films has a different types of the nanocrystals zinc. Were detected intergrowths of two or more the nanocrystals, hexagonal shape. Using the theory of homogeneous and heterogeneous nucleation of a new phase, had been evaluated the geometrical and thermodynamic parameters nanocrystals zinc.

Ferromagnetic cobalt nanocrystals achieved by soft annealing approach—From individual behavior to mesoscopic organized properties

NASA Astrophysics Data System (ADS)

Petit, C.; Wang, Z. L.; Pileni, M. P.

2007-05-01

By gentle annealing, 7 nm cobalt nanoparticles synthesized by soft chemistry, are transformed to hard magnetic hexagonal close packed (HCP) cobalt nanocrystals without changing the size, size distribution and passivating layer. This method permits to recover the nanocrystals isolated in solution after the annealing process and then to study the magnetic properties of the HCP cobalt nanocrystals at isolated status or in a self-organized film. Monolayer self-assembly of the HCP cobalt nanocrystals is obtained, and due to the dipolar interaction, ferromagnetic behavior close to room temperature has been observed. The magnetic properties differ significantly due to the influence of the substrate on the annealing process. This different approach of the annealing process of nanocrystals is compared to the classical approach of annealing in which the nanocrystals are first deposited on a substrate and then annealed.

Assembling tungsten oxide hydrate nanocrystal colloids formed by laser ablation in liquid into fast-response electrochromic films.

PubMed

Wang, Shalong; Dou, Kang; Zou, Yousheng; Dong, Yuhang; Li, Jubin; Ju, Dan; Zeng, Haibo

2017-03-01

High-performance electrochromic films based on tungsten oxide hydrate ([WO 2 (O 2 )H 2 O]·1.66H 2 O) colloidal nanocrystals with fast switching speed were fabricated by laser ablation in a mixture of water and hydrogen peroxide followed by electrophoretic methods. Through electrophoretic deposition, the nanoparticles in the colloids synthesized by laser ablation aggregated onto the FTO coated glass substrate forming a lager cell with a uniform size of around 200nm, which subsequently self-assembled into a porous tungsten oxide hydrate film. By optimizing the electrophoretic time (800s) and voltage (-0.5V), the mesh-like porous tungsten oxide hydrate film achieved a wide optical modulation of 32% at 632nm, fast coloration and bleaching response speed of 7.8 s and 1.7s respectively due to the synergetic effect of the unique atomic structure of [WO 2 (O 2 )H 2 O]·1.66H 2 O and porous structure with large surface area that facilitates the ion insertion/extraction. Thus the tungsten oxide hydrate can be a promising electrochromic material for practical applications. Copyright © 2016 Elsevier Inc. All rights reserved.

Temperature induced CuInSe2 nanocrystal formation in the Cu2Se-In3Se2 multilayer thin films

NASA Astrophysics Data System (ADS)

Mohan, A.; Rajesh, S.

2017-04-01

The paper deals with the impact of annealing on Cu2Se-In3Se2 multilayer structure and discusses the quantum confinements. Thermal evaporation technique was used to prepare multilayer films over the glass substrates. The films were annealed at different temperatures (150 °C-350 °C) under vacuum atmosphere. The XRD pattern reveals that the films exhibit (112) peaks with CuInSe2 Chalcopyrite structure and upon annealing crystallinity improved. The grain size comes around 13-19 nm. The optical band gap value was found to be 2.21 to 2.09 eV and band gap splitting was observed for higher annealing temperatures. The increase in the band gap is related to quantum confinement effect. SEM image shows nano crystals spread over the entire surface for higher annealing temperatures. Optical absorption and PL spectra shows the blue shift during annealing. The HR-TEM shows the particle size in the nano range and which confirms the CuInSe2 nanocrystal formation. AFM image shows the rough surface with homogenous grains for the as deposited films and smooth surface for annealed films.

Nanocrystal structures

DOEpatents

Eisler, Hans J [Stoneham, MA; Sundar, Vikram C [Stoneham, MA; Walsh, Michael E [Everett, MA; Klimov, Victor I [Los Alamos, NM; Bawendi, Moungi G [Cambridge, MA; Smith, Henry I [Sudbury, MA

2008-12-30

A structure including a grating and a semiconductor nanocrystal layer on the grating, can be a laser. The semiconductor nanocrystal layer can include a plurality of semiconductor nanocrystals including a Group II-VI compound, the nanocrystals being distributed in a metal oxide matrix. The grating can have a periodicity from 200 nm to 500 nm.

Nanocrystal structures

DOEpatents

Eisler, Hans J.; Sundar, Vikram C.; Walsh, Michael E.; Klimov, Victor I.; Bawendi, Moungi G.; Smith, Henry I.

2006-12-19

A structure including a grating and a semiconductor nanocrystal layer on the grating, can be a laser. The semiconductor nanocrystal layer can include a plurality of semiconductor nanocrystals including a Group II–VI compound, the nanocrystals being distributed in a metal oxide matrix. The grating can have a periodicity from 200 nm to 500 nm.

Electronic Disorder in Organic Semiconducting Films Observed with Kelvin Probe Force Microscopy

NASA Astrophysics Data System (ADS)

Hoffman, Benjamin Carl

This work is a study into electronic disorder within organic semiconducting (OSC) films from a scan-probe perspective. Organic electronics are an exciting technology poised for use in next generation devices with unique applications such as transparent displays and ultrathin flexible solar cells. Understanding and mapping electronic disorder in OSC has a high degree of relevance towards recognizing the properties of charge trapping that hinders transport and diminishes device performance. Evidence of surface potential inhomogeneity is identified by using Kelvin probe force microscopy (KPFM) to measure the contact potential difference (CPD) between probe and sample. OSC films are grown via organic molecular beam deposition (OMBD) to create well-ordered crystals with precise control of nominal thickness. Further research methods involve the study of diffraction peaks from grazing-incidence wide-angle x-ray scattering (GIWAXS) for crystallographic analysis as well as use of a probe station for transfer characteristics of fabricated thin film transistors. Initial research into this subject involved thin films of the novel organic molecule 2,8- diflouro-5,11-bis(triethylsilylethynyl)-anthradithiophene (diF-TES-ADT) that were grown on silicon substrates with a native oxide layer and analyzed with GIWAXS and KPFM. The crystallography of the films is that of a uniform (001) orientation. Variations in surface potential in diF-TES-ADT crystallites are observed to be unique from variations in the substrate. Nevertheless, surface potential variations in thick films are influenced by chemical passivation of the substrate and so the source of CPD variations are assigned to be intrinsic defects. Chemical treatment and processing methods control the growth kinetics which are linked to charge traps locally distorting the surface potential in OSC films. To continue the research into identifying charge trapping in ultra-thin films, 1.5 monolayer thick films of alpha-sexithiophene (6T

Recent progress in cellulose nanocrystals: sources and production.

PubMed

Trache, Djalal; Hussin, M Hazwan; Haafiz, M K Mohamad; Thakur, Vijay Kumar

2017-02-02

Cellulose nanocrystals, a class of fascinating bio-based nanoscale materials, have received a tremendous amount of interest both in industry and academia owing to its unique structural features and impressive physicochemical properties such as biocompatibility, biodegradability, renewability, low density, adaptable surface chemistry, optical transparency, and improved mechanical properties. This nanomaterial is a promising candidate for applications in fields such as biomedical, pharmaceuticals, electronics, barrier films, nanocomposites, membranes, supercapacitors, etc. New resources, new extraction procedures, and new treatments are currently under development to satisfy the increasing demand of manufacturing new types of cellulose nanocrystals-based materials on an industrial scale. Therefore, this review addresses the recent progress in the production methodologies of cellulose nanocrystals, covering principal cellulose resources and the main processes used for its isolation. A critical and analytical examination of the shortcomings of various approaches employed so far is made. Additionally, structural organization of cellulose and nomenclature of cellulose nanomaterials have also been discussed for beginners in this field.

Preparation and characterization of potato starch nanocrystal reinforced natural rubber nanocomposites.

PubMed

Rajisha, K R; Maria, H J; Pothan, L A; Ahmad, Zakiah; Thomas, S

2014-06-01

Potato starch nanocrystals were found to serve as an effective reinforcing agent for natural rubber (NR). Starch nanocrystals were obtained by the sulfuric acid hydrolysis of potato starch granules. After mixing the latex and the starch nanocrystals, the resulting aqueous suspension was cast into film by solvent evaporation method. The composite samples were successfully prepared by varying filler loadings, using a colloidal suspension of starch nanocrystals and NR latex. The morphology of the nanocomposite prepared was analyzed by field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). FESEM analysis revealed the size and shape of the crystal and their homogeneous dispersion in the composites. The crystallinity of the nanocomposites was studied using XRD analysis which indicated an overall increase in crystallinity with filler content. The mechanical properties of the nanocomposites such as stress-strain behavior, tensile strength, tensile modulus and elongation at break were measured according to ASTM standards. The tensile strength and modulus of the composites were found to improve tremendously with increasing nanocrystal content. This dramatic increase observed can be attributed to the formation of starch nanocrystal network. This network immobilizes the polymer chains leading to an increase in the modulus and other mechanical properties. Copyright © 2014 Elsevier B.V. All rights reserved.

Nanocrystal-based complementary inverters constructed on flexible plastic substrates.

PubMed

Jang, Jaewon; Cho, Kyoungah; Yun, Junggwon; Kim, Sangsig

2013-05-01

We demonstrate a nanocrystal (NC)-based complementary inverter constructed on a flexible plastic substrate. The NC-based complementary inverter consists of n-type HgSe NC- and p-type HgTe NC-based thin-film transistors (TFTs). Solid films on a plastic substrate obtained from HgSe and HgTe nanocrystals by thermal transformation are utilized as the n- and p-channel layers in these TFTs, respectively. The electrical properties of these component TFTs on unstrained and strained substrates are characterized and the performance of the inverter on the flexible substrate is investigated. The inverter on the unstrained substrate exhibits a logic gain of about 8, a logic swing of 90%, and a noise margin of 2.0 V. The characteristics of the inverter are changed under tensile and compressive strains, but not very significantly. Moreover, a comparison of the electrical characteristics of the n- and p-channel TFTs and the inverter is made in this paper.

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.

Conjugated polymers/semiconductor nanocrystals hybrid materials--preparation, electrical transport properties and applications.

PubMed

Reiss, Peter; Couderc, Elsa; De Girolamo, Julia; Pron, Adam

2011-02-01

This critical review discusses specific preparation and characterization methods applied to hybrid materials consisting of π-conjugated polymers (or oligomers) and semiconductor nanocrystals. These materials are of great importance in the quickly growing field of hybrid organic/inorganic electronics since they can serve as active components of photovoltaic cells, light emitting diodes, photodetectors and other devices. The electronic energy levels of the organic and inorganic components of the hybrid can be tuned individually and thin hybrid films can be processed using low cost solution based techniques. However, the interface between the hybrid components and the morphology of the hybrid directly influences the generation, separation and transport of charge carriers and those parameters are not easy to control. Therefore a large variety of different approaches for assembling the building blocks--conjugated polymers and semiconductor nanocrystals--has been developed. They range from their simple blending through various grafting procedures to methods exploiting specific non-covalent interactions between both components, induced by their tailor-made functionalization. In the first part of this review, we discuss the preparation of the building blocks (nanocrystals and polymers) and the strategies for their assembly into hybrid materials' thin films. In the second part, we focus on the charge carriers' generation and their transport within the hybrids. Finally, we summarize the performances of solar cells using conjugated polymer/semiconductor nanocrystals hybrids and give perspectives for future developments.

Volumetric flame synthesis of well-defined molybdenum oxide nanocrystals.

PubMed

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

2009-11-25

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

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

Aluminum-thin-film packaged fiber Bragg grating probes for monitoring the maximum tensile strain of composite materials.

PubMed

Im, Jooeun; Kim, Mihyun; Choi, Ki-Sun; Hwang, Tae-Kyung; Kwon, Il-Bum

2014-06-10

In this paper, new fiber Bragg grating (FBG) sensor probes are designed to intermittently detect the maximum tensile strain of composite materials, so as to evaluate the structural health status. This probe is fabricated by two thin Al films bonded to an FBG optical fiber and two supporting brackets, which are fixed on the surface of composite materials. The residual strain of the Al packaged FBG sensor probe is induced by the strain of composite materials. This residual strain can indicate the maximum strain of composite materials. Two types of sensor probes are prepared-one is an FBG with 18 μm thick Al films, and the other is an FBG with 36 μm thick Al films-to compare the thickness effect on the detection sensitivity. These sensor probes are bonded on the surfaces of carbon fiber reinforced plastics composite specimens. In order to determine the strain sensitivity between the residual strain of the FBG sensor probe and the maximum strain of the composite specimen, tensile tests are performed by universal testing machine, under the loading-unloading test condition. The strain sensitivities of the probes, which have the Al thicknesses of 18 and 36 μm, are determined as 0.13 and 0.23, respectively.

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.

Size and composition-controlled fabrication of thermochromic metal oxide nanocrystals

NASA Astrophysics Data System (ADS)

Clavero, César; Slack, Jonathan L.; Anders, André

2013-09-01

Finding new methods for the fabrication of metal oxide nanocrystals with high control on their composition, size and crystallinity is paramount for making large-area and low-cost optical coatings. Here, we demonstrate the fabrication of thermochromic VO2 nanocrystals using a physical vapour deposition-based route, with high control over their composition, size and crystallinity. This technique presents great potential to be scaled up and integrated with in-line coaters, commonly used for large-area deposition. Optimum crystallization of the VO2 nanoparticles is achieved after post-growth annealing at 350 °C, a temperature drastically lower than that required by chemical or implantation fabrication methods. The obtained nanoparticle thin films exhibit superior modulation of the transmittance in the visible and near IR portion of the spectrum as compared to conventional VO2 thin films due to plasmonic effects, opening up a new horizon in applications such as smarts windows.

Near-infrared luminescent cubic silicon carbide nanocrystals for in vivo biomarker applications: an ab initio study

NASA Astrophysics Data System (ADS)

Somogyi, Bálint; Zólyomi, Viktor; Gali, Adam

2012-11-01

Molecule-sized fluorescent emitters are much sought-after to probe biomolecules in living cells. We demonstrate here by time-dependent density functional calculations that the experimentally achievable 1-2 nm sized silicon carbide nanocrystals can emit light in the near-infrared region after introducing appropriate color centers in them. These near-infrared luminescent silicon carbide nanocrystals may act as ideal fluorophores for in vivo bioimaging.

Boosting the down-shifting luminescence of rare-earth nanocrystals for biological imaging beyond 1500 nm.

PubMed

Zhong, Yeteng; Ma, Zhuoran; Zhu, Shoujun; Yue, Jingying; Zhang, Mingxi; Antaris, Alexander L; Yuan, Jie; Cui, Ran; Wan, Hao; Zhou, Ying; Wang, Weizhi; Huang, Ngan F; Luo, Jian; Hu, Zhiyuan; Dai, Hongjie

2017-09-29

In vivo fluorescence imaging in the near-infrared region between 1500-1700 nm (NIR-IIb window) affords high spatial resolution, deep-tissue penetration, and diminished auto-fluorescence due to the suppressed scattering of long-wavelength photons and large fluorophore Stokes shifts. However, very few NIR-IIb fluorescent probes exist currently. Here, we report the synthesis of a down-conversion luminescent rare-earth nanocrystal with cerium doping (Er/Ce co-doped NaYbF 4 nanocrystal core with an inert NaYF 4 shell). Ce doping is found to suppress the up-conversion pathway while boosting down-conversion by ~9-fold to produce bright 1550 nm luminescence under 980 nm excitation. Optimization of the inert shell coating surrounding the core and hydrophilic surface functionalization minimize the luminescence quenching effect by water. The resulting biocompatible, bright 1550 nm emitting nanoparticles enable fast in vivo imaging of blood vasculature in the mouse brain and hindlimb in the NIR-IIb window with short exposure time of 20 ms for rare-earth based probes.Fluorescence imaging in the near-infrared window between 1500-1700 nm (NIR-IIb window) offers superior spatial resolution and tissue penetration depth, but few NIR-IIb probes exist. Here, the authors synthesize rare earth down-converting nanocrystals as promising fluorescent probes for in vivo imaging in this spectral region.

Processing and properties of eco-friendly bio-nanocomposite films filled with cellulose nanocrystals from sugarcane bagasse.

PubMed

El Achaby, Mounir; El Miri, Nassima; Aboulkas, Adil; Zahouily, Mohamed; Bilal, Essaid; Barakat, Abdellatif; Solhy, Abderrahim

2017-03-01

Novel synthesis strategy of eco-friendly bio-nanocomposite films have been exploited using cellulose nanocrystals (CNC) and polyvinyl alcohol/carboxymethyl cellulose (PVA/CMC) blend matrix as a potential in food packaging application. The CNC were extracted from sugarcane bagasse using sulfuric acid hydrolysis, and they were successfully characterized regarding their morphology, size, crystallinity and thermal stability. Thereafter, PVA/CMC-CNC bio-nanocomposite films, at various CNC contents (0.5-10wt%), were fabricated by the solvent casting method, and their properties were investigated. It was found that the addition of 5wt% CNC within a PVA/CMC increased the tensile modulus and strength by 141% and 83% respectively, and the water vapor permeability was reduced by 87%. Additionally, the bio-nanocomposites maintained the same transparency level of the PVA/CMC blend film (transmittance of ∼90% in the visible region), suggesting that the CNC were dispersed at the nanoscale. In these bio-nanocomposites, the adhesion properties and the large number of functional groups that are present in the CNC's surface and the macromolecular chains of the PVA/CMC blend are exploited to improve the interfacial interactions between the CNC and the blend. Consequently, these eco-friendly structured bio-nanocomposites with superior properties are expected to be useful in food packaging applications. Copyright © 2016. Published by Elsevier B.V.

Surface-potential decay of biased-probe contact-charged amorphous polymer films

NASA Astrophysics Data System (ADS)

Knorr, Nikolaus; Rosselli, Silvia; Nelles, Gabriele

2010-03-01

We have investigated the decay of scanning Kelvin probe force microscopy (KPFM) and electric force microscopy (EFM) signals from biased-probe contact-charged films of three different amorphous polymers representing wide-ranging water absorption capabilities. The surface-potential decay (SPD) has been measured by repeatedly scanning the charge pattern as a function of dissipation time t while varying the relative humidity (RH), the film thickness d, the temperature, the charging voltage, and the load on the scanning probe. Whereas increases in KPFM and EFM peak widths are appreciable only in the long run, the decay in the peak heights is rapid at the beginning and then strongly slowing down with time. Peak heights can be approximated for t <1 hour by power laws of negative exponents (-β), with 0<β<0.5 in dry conditions. β increases for thinner films and when scanning with higher probe loads. Raising the humidity or heating to temperatures well below the glass transition temperature of the polymer considerably increases β, with much stronger impacts for polymers with a higher water uptake capability. From the findings, we conclude that ionic charge carriers are trapped by the charge injection process in the volume of the polymers at low depths. A main contribution to SPD is by drift of the ions in their own space-charge field, mutually repelling each other and being attracted by their mirror charge in the grounded back electrode. Lateral drifts for small t are not resolved, increases in peak widths for t ≫1 h are predominantly due to increased probe—charge carrier distances. We interpret the power law approximation in terms of dispersive transport theory. We approximate trap-controlled apparent mobilities μ from isothermal KPFM peak height data, taken within a few minutes after charging, by a linear and a hyperbolic SPD model. Both models yield μ ≈10-14 cm2/(V s) for thin films (d ≈50 nm) in dry conditions. For mobilities derived similarly from isohumid

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.

Synthesis and applications of heterostructured semiconductor nanocrystals

NASA Astrophysics Data System (ADS)

Khon, Elena

light emmision tunability. We reported a general strategy for the assembly of all-inorganic light-emitting nanocrystal films with an emission quantum yield in the 30-52% range. Our methodology relies on solution-processing of CdSe nanocrystals into a crystalline matrix of a wide band gap semiconductor (CdS, ZnS). As a result, we replace original organic ligands on nanocrystal surfaces with an inorganic medium which efficiently preserves the quantum confinement of electrical charges in CdSe NCs. In addition to strong emission, fabricated films demonstrated excellent thermal and chemical stability, and a large refractive index, which avails their integration into emerging solid-state nanocrystal devices. The ability to control size and shape of NCs is essential as it automatically affects the optoelectronic properties of the crystals. Colloidal chemistry offers an assortment of synthetic tools for tuning the shape of NCs, but some nanoparticle morphologies require alternative processing strategies. We have shown that chemical etching of colloidal nanoparticles can facilitate the realization of desirable nanocrystal geometries. This methodology allows both CdSe and CdS composed semiconductor domains be exposed to the external environment, while maintaining a structural design that is highly desirable for catalytic applications. Hydrogen production tests confirmed the improved catalytic activity of CdSe/CdS dimers. We expect that the demonstrated application will become a common methodology in the synthesis of charge-separating nanocrystals, leading to advanced nanoparticle architectures for applications in the areas of photocatalysis, photovoltaics, and light detection.

Nanocrystal grain growth and device architectures for high-efficiency CdTe ink-based photovoltaics.

PubMed

Crisp, Ryan W; Panthani, Matthew G; Rance, William L; Duenow, Joel N; Parilla, Philip A; Callahan, Rebecca; Dabney, Matthew S; Berry, Joseph J; Talapin, Dmitri V; Luther, Joseph M

2014-09-23

We study the use of cadmium telluride (CdTe) nanocrystal colloids as a solution-processable "ink" for large-grain CdTe absorber layers in solar cells. The resulting grain structure and solar cell performance depend on the initial nanocrystal size, shape, and crystal structure. We find that inks of predominantly wurtzite tetrapod-shaped nanocrystals with arms ∼5.6 nm in diameter exhibit better device performance compared to inks composed of smaller tetrapods, irregular faceted nanocrystals, or spherical zincblende nanocrystals despite the fact that the final sintered film has a zincblende crystal structure. Five different working device architectures were investigated. The indium tin oxide (ITO)/CdTe/zinc oxide structure leads to our best performing device architecture (with efficiency >11%) compared to others including two structures with a cadmium sulfide (CdS) n-type layer typically used in high efficiency sublimation-grown CdTe solar cells. Moreover, devices without CdS have improved response at short wavelengths.

Improving polymer/nanocrystal hybrid solar cell performance via tuning ligand orientation at CdSe quantum dot surface.

PubMed

Fu, Weifei; Wang, Ling; Zhang, Yanfang; Ma, Ruisong; Zuo, Lijian; Mai, Jiangquan; Lau, Tsz-Ki; Du, Shixuan; Lu, Xinhui; Shi, Minmin; Li, Hanying; Chen, Hongzheng

2014-11-12

Achieving superior solar cell performance based on the colloidal nanocrystals remains challenging due to their complex surface composition. Much attention has been devoted to the development of effective surface modification strategies to enhance electronic coupling between the nanocrystals to promote charge carrier transport. Herein, we aim to attach benzenedithiol ligands onto the surface of CdSe nanocrystals in the "face-on" geometry to minimize the nanocrystal-nanocrystal or polymer-nanocrystal distance. Furthermore, the "electroactive" π-orbitals of the benzenedithiol are expected to further enhance the electronic coupling, which facilitates charge carrier dissociation and transport. The electron mobility of CdSe QD films was improved 20 times by tuning the ligand orientation, and high performance poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT):CdSe nanocrystal hybrid solar cells were also achieved, showing a highest power conversion efficiency of 4.18%. This research could open up a new pathway to improve further the performance of colloidal nanocrystal based solar cells.

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

NASA Astrophysics Data System (ADS)

Braun, Max B.

absorption processes. Chapter 3 introduces the many considerations needed to be taken into account during the development of a novel synthesis for copper zinc tin chalcogenide colloidal nanocrystals. In addition to introducing synthetic approaches to achieve this goal, Chapter 3 also describes essential characteristics that need to be considered for further investigation into the properties of films made from the nanocrystals. Chapter 4 is a publication that appeared in Chemistry of Materials, that describes an approach to tuning the surface and ligand chemistry of Cu2ZnSnS4 nanocrystals for use as an absorber layer in next generation photovoltaic devices. The publication describes ligand exchange chemistry achieved via layer-by-layer dip-casting of nanocrystal thin films, and the effects that this exchange chemistry has on the resulting films. It also details the fabrication of full photovoltaic (PV) devices to characterize the benefits of controlling the surface chemistry can have on PV performance. Chapter 5 is a paper--to be submitted to ACS Applied Materials and Interfaces--that describes the investigations into how varying the chalcogen ratio (i.e., S:Se) leads to changes in the physical and electrical properties of thin films made from Cu2ZnSn(S1-xSex)4 (where 0 < x < 1) NCs. It highlights the novel synthetic procedure (detailed in chapter 3) that was required for a systematic, deconvoluted evaluation of S:Se composition on the materials optical and electronic properties. Moreover, the characteristics of full PV devices based on thin films of each stoichiometry (x=0 to x=1) are assessed to establish a relationship between composition and the materials performance.

Microstructure, thermal properties and crystallinity of amadumbe starch nanocrystals.

PubMed

Mukurumbira, Agnes; Mariano, Marcos; Dufresne, Alain; Mellem, John J; Amonsou, Eric O

2017-09-01

Amadumbe (Colocasia esculenta), commonly known as taro is a tropical tuber that produces starch-rich underground corms. In this study, the physicochemical properties of starch nanocrystals (SNC) prepared by acid hydrolysis of amadumbe starches were investigated. Two varieties of amadumbe corms were used for starch extraction. Amadumbe starches produced substantially high yield (25%) of SNC's. These nanocrystals appeared as aggregated and individual particles and possessed square-like platelet morphology with size: 50-100nm. FTIR revealed high peak intensities corresponding to OH stretch, CH stretch and H 2 O bending vibrations for SNCs compared to their native starch counterparts. Both the native starch and SNC exhibited the A-type crystalline pattern. However, amadumbe SNCs showed higher degree of crystallinity and slightly reduced melting temperatures than their native starches. Amadumbe SNCs presented similar thermal decomposition property as their native starches. Amadumbe starch nanocrystals may have potential application in biocomposite films due to their square-like platelet morphology. Copyright © 2017 Elsevier B.V. All rights reserved.

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

Plasmon induced modification of silicon nanocrystals photoluminescence in presence of gold nanostripes

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

Dyakov, S. A.; Zhigunov, D. M.; Marinins, A.

Here, we report on the results of theoretical and experimental studies of photoluminescense of silicon nanocrystals in the proximity to plasmonic modes of different types. In the studied samples, the type of plasmonic mode is determined by the filling ratio of a one-dimensional array of gold stripes which covers the thin film with silicon nanocrystals on a quartz substrate. We analyze the extinction, photoluminesce spectra and decay kinetics of silicon nanocrystals and show that the incident and emitted light is coupled to the corresponding plasmonic mode. We demonstrate the modification of the extinction and photoluminesce spectra under the transition frommore » wide to narrow gold stripes. The experimental extinction and photoluminescense spectra are in good agreement with theoretical calculations performed by the rigorous coupled wave analysis. Finally, we study the contribution of individual silicon nanocrystals to the overall photoluminescense intensity, depending on their spacial position inside the structure.« less

Plasmon induced modification of silicon nanocrystals photoluminescence in presence of gold nanostripes

DOE PAGES

Dyakov, S. A.; Zhigunov, D. M.; Marinins, A.; ...

2018-03-20

Here, we report on the results of theoretical and experimental studies of photoluminescense of silicon nanocrystals in the proximity to plasmonic modes of different types. In the studied samples, the type of plasmonic mode is determined by the filling ratio of a one-dimensional array of gold stripes which covers the thin film with silicon nanocrystals on a quartz substrate. We analyze the extinction, photoluminesce spectra and decay kinetics of silicon nanocrystals and show that the incident and emitted light is coupled to the corresponding plasmonic mode. We demonstrate the modification of the extinction and photoluminesce spectra under the transition frommore » wide to narrow gold stripes. The experimental extinction and photoluminescense spectra are in good agreement with theoretical calculations performed by the rigorous coupled wave analysis. Finally, we study the contribution of individual silicon nanocrystals to the overall photoluminescense intensity, depending on their spacial position inside the structure.« less

Electrical Study of Trapped Charges in Copper-Doped Zinc Oxide Films by Scanning Probe Microscopy for Nonvolatile Memory Applications

PubMed Central

Su, Ting; Zhang, Haifeng

2017-01-01

Charge trapping properties of electrons and holes in copper-doped zinc oxide (ZnO:Cu) films have been studied by scanning probe microscopy. We investigated the surface potential dependence on the voltage and duration applied to the copper-doped ZnO films by Kelvin probe force microscopy. It is found that the Fermi Level of the 8 at.% Cu-doped ZnO films shifted by 0.53 eV comparing to undoped ZnO films. This shift indicates significant change in the electronic structure and energy balance in Cu-doped ZnO films. The Fermi Level (work function) of zinc oxide films can be tuned by Cu doping, which are important for developing this functional material. In addition, Kelvin probe force microscopy measurements demonstrate that the nature of contact at Pt-coated tip/ZnO:Cu interface is changed from Schottky contact to Ohmic contact by increasing sufficient amount of Cu ions. The charge trapping property of the ZnO films enhance greatly by Cu doping (~10 at.%). The improved stable bipolar charge trapping properties indicate that copper-doped ZnO films are promising for nonvolatile memory applications. PMID:28135335

Optical properties and ensemble characteristics of size purified Silicon nanocrystals

NASA Astrophysics Data System (ADS)

Miller, Joseph Bradley

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

Ultrafast exciton fine structure relaxation dynamics in lead chalcogenide nanocrystals.

PubMed

Johnson, Justin C; Gerth, Kathrine A; Song, Qing; Murphy, James E; Nozik, Arthur J; Scholes, Gregory D

2008-05-01

The rates of fine structure relaxation in PbS, PbSe, and PbTe nanocrystals were measured on a femtosecond time scale as a function of temperature with no applied magnetic field by cross-polarized transient grating spectroscopy (CPTG) and circularly polarized pump-probe spectroscopy. The relaxation rates among exciton fine structure states follow trends with nanocrystal composition and size that are consistent with the expected influence of material dependent spin-orbit coupling, confinement enhanced electron-hole exchange interaction, and splitting between L valleys that are degenerate in the bulk. The size dependence of the fine structure relaxation rate is considerably different from what is observed for small CdSe nanocrystals, which appears to result from the unique material properties of the highly confined lead chalcogenide quantum dots. Modeling and qualitative considerations lead to conclusions about the fine structure of the lowest exciton absorption band, which has a potentially significant bearing on photophysical processes that make these materials attractive for practical purposes.

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.

Soluble Supercapacitors: Large and Reversible Charge Storage in Colloidal Iron-Doped ZnO Nanocrystals.

PubMed

Brozek, Carl K; Zhou, Dongming; Liu, Hongbin; Li, Xiaosong; Kittilstved, Kevin R; Gamelin, Daniel R

2018-05-09

Colloidal ZnO semiconductor nanocrystals have previously been shown to accumulate multiple delocalized conduction-band electrons under chemical, electrochemical, or photochemical reducing conditions, leading to emergent semimetallic characteristics such as quantum plasmon resonances and raising prospects for application in multielectron redox transformations. Here, we demonstrate a dramatic enhancement in the capacitance of colloidal ZnO nanocrystals through aliovalent Fe 3+ -doping. Very high areal and volumetric capacitances (33 μF cm -2 , 233 F cm -3 ) are achieved in Zn 0.99 Fe 0.01 O nanocrystals that rival those of the best supercapacitors used in commercial energy-storage devices. The redox properties of these nanocrystals are probed by potentiometric titration and optical spectroscopy. These data indicate an equilibrium between electron localization by Fe 3+ dopants and electron delocalization within the ZnO conduction band, allowing facile reversible charge storage and removal. As "soluble supercapacitors", colloidal iron-doped ZnO nanocrystals constitute a promising class of solution-processable electronic materials with large charge-storage capacity attractive for future energy-storage applications.

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

DOE PAGES

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

2017-06-27

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

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.

Preparation of plasmonic vesicles from amphiphilic gold nanocrystals grafted with polymer brushes

PubMed Central

Song, Jibin; Huang, Peng; Chen, Xiaoyuan

2016-01-01

Gold nanovesicles contain multiple nanocrystals within a polymeric coating. The strong plasmonic coupling between adjacent nanoparticles in their vesicular shell makes ultrasensitive biosensing and bioimaging possible. In our laboratory, multifunctional plasmonic vesicles are assembled from amphiphilic gold nanocrystals (such as gold nanoparticles and gold nanorods) coated with mixed hydrophilic and hydrophobic polymer brushes or amphiphilic diblock co-polymer brushes. To fulfill the different requirements of biomedical applications, different polymers that are either pH=responsive, photoactive or biodegradable can be used to form the hydrophobic brush, while the hydrophilicity is maintained by polyethylene glycol (PEG). This protocol covers the preparation, surface functionalization and self-assembly of amphiphilic gold nanocrystals grafted covalently with polymer brushes. The protocol can be completed within 2 d. The preparation of amphiphilic gold nanocrystals, coated with amphiphilic diblock polymer brushes using a ‘grafting to’ method or mixed hydrophilic and hydrophobic polymer brushes using tandem ‘grafting to’ and ‘grafting from’ methods, is described. We also provide detailed procedures for the preparation and characterization of pH-responsive plasmonic gold nanovesicles from amphiphilic gold nanocrystals using a film-rehydration method that can be completed within ~3 d. PMID:27763624

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

Photosensitivity enhancement with TiO2 in semitransparent light-sensitive skins of nanocrystal monolayers.

PubMed

Akhavan, Shahab; Yeltik, Aydan; Demir, Hilmi Volkan

2014-06-25

We propose and demonstrate light-sensitive nanocrystal skins that exhibit broadband sensitivity enhancement based on electron transfer to a thin TiO2 film grown by atomic layer deposition. In these photosensors, which operate with no external bias, photogenerated electrons remain trapped inside the nanocrystals. These electrons generally recombine with the photogenerated holes that accumulate at the top interfacing contact, which leads to lower photovoltage buildup. Because favorable conduction band offset aids in transferring photoelectrons from CdTe nanocrystals to the TiO2 layer, which decreases the exciton recombination probability, TiO2 has been utilized as the electron-accepting material in these light-sensitive nanocrystal skins. A controlled interface thickness between the TiO2 layer and the monolayer of CdTe nanocrystals enables a photovoltage buildup enhancement in the proposed nanostructure platform. With TiO2 serving as the electron acceptor, we observed broadband sensitivity improvement across 350-475 nm, with an approximately 22% enhancement. Furthermore, time-resolved fluorescence measurements verified the electron transfer from the CdTe nanocrystals to the TiO2 layer in light-sensitive skins. These results could pave the way for engineering nanocrystal-based light-sensing platforms, such as smart transparent windows, light-sensitive walls, and large-area optical detection systems.

Effect of post-treatments and concentration of cotton linter cellulose nanocrystals on the properties of agar-based nanocomposite films.

PubMed

Oun, Ahmed A; Rhim, Jong-Whan

2015-12-10

Cellulose nanocrystals (CNCs) were prepared by acid hydrolysis of cotton linter pulp fibers and three different purification methods, i.e., without post purification (CNC1), dialyzed against distilled water (CNC2), and neutralized with NaOH (CNC3), and their effect on film properties was evaluated by preparation of agar/CNCs composite films. All the CNCs were rod in shape with diameter of 15-50 nm and length of 210-480 nm. FTIR result indicated that there was no distinctive differences in the chemical structure between CNCs and cotton linter cellulose fiber. No significant relationship was observed between the sulfate content and crystallinity index of CNCs. The CNC3 showed higher thermal stability than the other type of CNCs due to the less adverse effect on the thermal stability of sulfate groups induced by the neutralization with NaOH. The tensile strength (TS) of agar film increased by 15% with incorporation of 5 wt% of CNC3, on the contrary, it decreased by 10% and 15% with incorporation of CNC1 and CNC2, respectively. Other performance properties of agar/CNCs composite films such as optical and water vapor barrier properties showed that the CNC3 was more effective filler than the other CNCs. In the range of concentration of CNC3 tested (1-10 wt%), inclusion of 5 wt% of CNC3 was the maximum concentration for improving or maintaining film properties of the composite films. The neutralization of acid hydrolyzed cellulose using NaOH was simple and convenient for the preparation of CNC and bionanocomposite films. Copyright © 2015 Elsevier Ltd. All rights reserved.

Confining metal-halide perovskites in nanoporous thin films

PubMed Central

Demchyshyn, Stepan; Roemer, Janina Melanie; Groiß, Heiko; Heilbrunner, Herwig; Ulbricht, Christoph; Apaydin, Dogukan; Böhm, Anton; Rütt, Uta; Bertram, Florian; Hesser, Günter; Scharber, Markus Clark; Sariciftci, Niyazi Serdar; Nickel, Bert; Bauer, Siegfried; Głowacki, Eric Daniel; Kaltenbrunner, Martin

2017-01-01

Controlling the size and shape of semiconducting nanocrystals advances nanoelectronics and photonics. Quantum-confined, inexpensive, solution-derived metal halide perovskites offer narrowband, color-pure emitters as integral parts of next-generation displays and optoelectronic devices. We use nanoporous silicon and alumina thin films as templates for the growth of perovskite nanocrystallites directly within device-relevant architectures without the use of colloidal stabilization. We find significantly blue-shifted photoluminescence emission by reducing the pore size; normally infrared-emitting materials become visibly red, and green-emitting materials become cyan and blue. Confining perovskite nanocrystals within porous oxide thin films drastically increases photoluminescence stability because the templates auspiciously serve as encapsulation. We quantify the template-induced size of the perovskite crystals in nanoporous silicon with microfocus high-energy x-ray depth profiling in transmission geometry, verifying the growth of perovskite nanocrystals throughout the entire thickness of the nanoporous films. Low-voltage electroluminescent diodes with narrow, blue-shifted emission fabricated from nanocrystalline perovskites grown in embedded nanoporous alumina thin films substantiate our general concept for next-generation photonic devices. PMID:28798959

3D-calibration of three- and four-sensor hot-film probes based on collocated sonic using neural networks

NASA Astrophysics Data System (ADS)

Kit, Eliezer; Liberzon, Dan

2016-09-01

High resolution measurements of turbulence in the atmospheric boundary layer (ABL) are critical to the understanding of physical processes and parameterization of important quantities, such as the turbulent kinetic energy dissipation. Low spatio-temporal resolution of standard atmospheric instruments, sonic anemometers and LIDARs, limits their suitability for fine-scale measurements of ABL. The use of miniature hot-films is an alternative technique, although such probes require frequent calibration, which is logistically untenable in field setups. Accurate and truthful calibration is crucial for the multi-hot-films applications in atmospheric studies, because the ability to conduct calibration in situ ultimately determines the turbulence measurements quality. Kit et al (2010 J. Atmos. Ocean. Technol. 27 23-41) described a novel methodology for calibration of hot-film probes using a collocated sonic anemometer combined with a neural network (NN) approach. An important step in the algorithm is the generation of a calibration set for NN training by an appropriate low-pass filtering of the high resolution voltages, measured by the hot-film-sensors and low resolution velocities acquired by the sonic. In Kit et al (2010 J. Atmos. Ocean. Technol. 27 23-41), Kit and Grits (2011 J. Atmos. Ocean. Technol. 28 104-10) and Vitkin et al (2014 Meas. Sci. Technol. 25 75801), the authors reported on successful use of this approach for in situ calibration, but also on the method’s limitations and restricted range of applicability. In their earlier work, a jet facility and a probe, comprised of two orthogonal x-hot-films, were used for calibration and for full dataset generation. In the current work, a comprehensive laboratory study of 3D-calibration of two multi-hot-film probes (triple- and four-sensor) using a grid flow was conducted. The probes were embedded in a collocated sonic, and their relative pitch and yaw orientation to the mean flow was changed by means of motorized

Analysis of non-contact and contact probe-to-sample thermal exchange for quantitative measurements of thin film and nanostructure thermal conductivity by the scanning hot probe method

NASA Astrophysics Data System (ADS)

Wilson, Adam A.

The ability to measure thermal properties of thin films and nanostructured materials is an important aspect of many fields of academic study. A strategy especially well-suited for nanoscale investigations of these properties is the scanning hot probe technique, which is unique in its ability to non-destructively interrogate the thermal properties with high resolution, both laterally as well as through the thickness of the material. Strategies to quantitatively determine sample thermal conductivity depend on probe calibration. State of the art calibration strategies assume that the area of thermal exchange between probe and sample does not vary with sample thermal conductivity. However, little investigation has gone into determining whether or not that assumption is valid. This dissertation provides a rigorous study into the probe-to-sample heat transfer through the air gap at diffusive distances for a variety of values of sample thermal conductivity. It is demonstrated that the thermal exchange radius and gap/contact thermal resistance varies with sample thermal conductivity as well as tip-to-sample clearance in non-contact mode. In contact mode, it is demonstrated that higher thermal conductivity samples lead to a reduction in thermal exchange radius for Wollaston probe tips. Conversely, in non-contact mode and in contact mode for sharper probe tips where air contributes the most to probe-to-sample heat transfer, the opposite trend occurs. This may be attributed to the relatively strong solid-to-solid conduction occurring between probe and sample for the Wollaston probes. A three-dimensional finite element (3DFE) model was developed to investigate how the calibrated thermal exchange parameters vary with sample thermal conductivity when calibrating the probe via the intersection method in non-contact mode at diffusive distances. The 3DFE model was then used to explore the limits of sensitivity of the experiment for a range of simulated experimental conditions. It

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

Band gap and composition engineering on a nanocrystal (BCEN) in solution.

PubMed

Peng, Xiaogang

2010-11-16

Colloidal nanocrystals with "artificial" composition and electron band structure promise to expand the fields of nanomaterials and inorganic chemistry. Despite their promise as functional materials, the fundamental science associated with the synthesis, characterization, and properties of colloidal nanocrystals is still in its infancy and deserves systematic study. Furthermore, such studies are important for our basic understanding of crystallization, surface science, and solid state chemistry. "Band gap and composition engineering on a nanocrystal" (BCEN) refers to the synthesis of a colloidal nanocrystal with composition and/or electron energy band structure that are not found in natural bulk crystals. The BCEN nanostructure shown in the Figure includes a magnetic domain for the separation and recycling of the complex nanostructure, a photoactivated catalytic center, and an additional chemical catalytic center. A thin but porous film (such as a silicate) might be coated onto the nanocrystal, both to provide chemical stability and to isolate the reaction processes from the bulk solution. This example is a catalytic complex analogous to an enzyme that facilitates two sequential reactions in a microenvironment different from bulk solution. The synthesis of colloidal nanocrystals has advanced by a quantum leap in the past two decades. The field now seems ready to extend colloidal nanocrystal synthesis into the BCEN regime. Although BCEN is a very new branch of synthetic chemistry, this Account describes advances in related synthetic and characterization techniques that can serve as a useful starting point for this new area of investigation. To put these ideas into context, this Account compares this new field with organic synthesis, the most developed branch in synthetic chemistry. The structural and functional diversity of organic compounds results from extending design and synthesis beyond the construction of natural organic compounds. If this idea also holds true

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.

Stratified Turbulence Measurements in Complex Terrain Using Hot-film Probes and a Collocated Sonic Anemometer

NASA Astrophysics Data System (ADS)

Hocut, C.; Kit, E.; Liberzon, D.; Fernando, H. J. S.; Materhorn Team

2014-11-01

In the fall of 2012 and spring 2013, the Mountain Terrain Atmospheric Modeling and Observations Program (MATERHORN) conducted extensive field experiments at the Granite Mountain Atmospheric Science Testbed (GMAST), US Army Dugway Proving Grounds (DPG), Utah. This provided a unique opportunity to deploy tower mounted three-dimensional hot-film combo probes, consisting of sonic anemometers collocated with hot-film anemometers able to respond to the wind direction. The combo probes follow mean winds using a feedback control loop and use a Neural Network to calibrate the hot-films in-situ. Once calibrated, these probes can handle a vast range of background flow conditions and scales from mesoscale flow down to the Kolmogorov scale. Of particular interest are the observed variation in velocity spectra during the evenings. Sometimes the velocity spectra shows the turbulence is Kolmogorov and is isotropic at small scales while in other spectra there is evidence of turbulence production at finer scales. An explanation on different spectral shapes will be presented as well as the relevant length/time scales of the production events. Funded by ONR Grant N00014-11-1-0709.

1/f noise in semiconductor and metal nanocrystal solids

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

Liu, Heng, E-mail: leophy@gmail.com; Lhuillier, Emmanuel, E-mail: emmanuel.lhuillier@espci.fr; Guyot-Sionnest, Philippe

2014-04-21

Electrical 1/f noise is measured in thin films of CdSe, CdSe/CdS, ZnO, HgTe quantum dots and Au nanocrystals. The 1/f noise, normalized per nanoparticle, shows no systematic dependence on the nanoparticle material and the coupling material. However, over 10 orders of magnitude, it correlates well with the nearest neighbor conductance suggesting some universal magnitude of the 1/f noise in these granular conductors. In the hopping regime, the main mechanism of 1/f noise is determined to be mobility fluctuated. In the metallic regime obtained with gold nanoparticle films, the noise drops to a similar level as bulk gold films and withmore » a similar temperature dependence.« less

Quantifying charge carrier concentration in ZnO thin films by Scanning Kelvin Probe Microscopy

PubMed Central

Maragliano, C.; Lilliu, S.; Dahlem, M. S.; Chiesa, M.; Souier, T.; Stefancich, M.

2014-01-01

In the last years there has been a renewed interest for zinc oxide semiconductor, mainly triggered by its prospects in optoelectronic applications. In particular, zinc oxide thin films are being widely used for photovoltaic applications, in which the determination of the electrical conductivity is of great importance. Being an intrinsically doped material, the quantification of its doping concentration has always been challenging. Here we show how to probe the charge carrier density of zinc oxide thin films by Scanning Kelvin Probe Microscopy, a technique that allows measuring the contact potential difference between the tip and the sample surface with high spatial resolution. A simple electronic energy model is used for correlating the contact potential difference with the doping concentration in the material. Limitations of this technique are discussed in details and some experimental solutions are proposed. Two-dimensional doping concentration images acquired on radio frequency-sputtered intrinsic zinc oxide thin films with different thickness and deposited under different conditions are reported. We show that results inferred with this technique are in accordance with carrier concentration expected for zinc oxide thin films deposited under different conditions and obtained from resistivity and mobility measurements. PMID:24569599

Nanocrystal doped matrixes

DOEpatents

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

2010-01-12

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

Surface chemical modification of nanocrystals

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

Helms, Brett Anthony; Milliron, Delia Jane; Rosen, Evelyn Louise

Nanocrystals comprising organic ligands at surfaces of the plurality of nanocrystals are provided. The organic ligands are removed from the surfaces of the nanocrystals using a solution comprising a trialkyloxonium salt in a polar aprotic solvent. The removal of the organic ligands causes the nanocrystals to become naked nanocrystals with cationic surfaces.

Superconducting thin-film gyroscope readout for Gravity Probe-B

NASA Technical Reports Server (NTRS)

Lockhart, James M.; Cheung, W. Stephen; Gill, Dale K.

1987-01-01

The high-resolution gyroscope readout system for the Stanford Gravity Probe-B experiment, whose purpose is to measure two general relativistic precessions of gyroscopes in earth orbit, is described. In order to achieve the required resolution in angle (0.001 arcsec), the readout system combines high-precision mechanical fabrication and measurement techniques with superconducting thin-film technology, ultralow magnetic fields, and SQUID detectors. The system design, performance limits achievable with current technology, and the results of fabrication and laboratory testing to date are discussed.

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

Order of magnitude enhancement of monolayer MoS 2 photoluminescence due to near-field energy influx from nanocrystal films

DOE PAGES

Guo, Tianle; Sampat, Siddharth; Zhang, Kehao; ...

2017-02-03

Two-dimensional transition metal dichalcogenides (TMDCs) like MoS 2 are promising candidates for various optoelectronic applications. The typical photoluminescence (PL) of monolayer MoS 2 is however known to suffer very low quantum yields. We demonstrate a 10-fold increase of MoS 2 excitonic PL enabled by nonradiative energy transfer (NRET) from adjacent nanocrystal quantum dot (NQD) films. The understanding of this effect is facilitated by our application of transient absorption (TA) spectroscopy to monitor the energy influx into the monolayer MoS 2 in the process of ET from photoexcited CdSe/ZnS nanocrystals. In contrast to PL spectroscopy, TA can detect even non-emissive excitons,more » and we register an order of magnitude enhancement of the MoS 2 excitonic TA signatures in hybrids with NQDs. The appearance of ET-induced nanosecond-scale kinetics in TA features is consistent with PL dynamics of energy-accepting MoS 2 and PL quenching data of the energy-donating NQDs. The observed enhancement is attributed to the reduction of recombination losses for excitons gradually transferred into MoS 2 under quasi-resonant conditions as compared with their direct photoproduction. Furthermore, the TA and PL data clearly illustrate the efficacy of MoS 2 and likely other TMDC materials as energy acceptors and the possibility of their practical utilization in NRET-coupled hybrid nanostructures.« less

Bottom-up approach to fabricate nanostructured thin films from colloidal nanocrystal precursors

NASA Astrophysics Data System (ADS)

Shaw, Santosh

Control over microstructures at the nanoscale (<100nm) still seems challenging due to, among other things, the stochastic nature of nucleation in the bulk phase. The densification of assemblies of ligand-capped nanocrystals (colloidal nanocrystal assemblies, CNAs) could bypass this challenge that limits our control over the nanostructure and, therefore, the properties of materials. However, the removal of the ligands and the cracking that follows it are the two critical hurdles that have been stymieing this approach. We show that low-pressure plasma processing can effectively remove ligands from CNAs (down to 0.6 at.% of carbon which can be accounted for adventitious carbon) without harming the properties of the inorganic cores of the nanoparticles and the structure of CNAs. The cracking of CNAs is correlated with the structure of the CNAs, which can be controlled and easily predicted by Hansen solubility parameters of solvent in which the nanoparticles are dispersed. While a fully solvated ligand shell leads to the formation of close-packed ordered CNAs - which cracked after self-assembly or ligand removal - a partially solvated one results in interdigitation of the ligand shell yielding disordered CNAs, which remained crack-free after ligand removal and sintering up to a critical cracking thickness of 440nm. The process is demonstrated with particles of different compositions, ligands, sizes, shapes, as well as with binary systems. These findings allowed for the fabrication of cm2 crack-free, phase-pure polycrystalline films with tunable, near-monodisperse grain sizes using CNAs as precursors. We observed electrical conductivities of PbS films produced by this approach over 1 cm to be 1.370 S/cm which is comparable to those of bulk crystal. This conductivity value is remarkable considering the fact that the typical porosity in fully processed CNAs is around 40%. We simultaneously answered the fundamental question that how microstructure of CNAs evolves during

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

DOE PAGES

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

2017-02-27

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

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

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

Probing the bulk ionic conductivity by thin film hetero-epitaxial engineering

NASA Astrophysics Data System (ADS)

Pergolesi, Daniele; Roddatis, Vladimir; Fabbri, Emiliana; Schneider, Christof W.; Lippert, Thomas; Traversa, Enrico; Kilner, John A.

2015-02-01

Highly textured thin films with small grain boundary regions can be used as model systems to directly measure the bulk conductivity of oxygen ion conducting oxides. Ionic conducting thin films and epitaxial heterostructures are also widely used to probe the effect of strain on the oxygen ion migration in oxide materials. For the purpose of these investigations a good lattice matching between the film and the substrate is required to promote the ordered film growth. Moreover, the substrate should be a good electrical insulator at high temperature to allow a reliable electrical characterization of the deposited film. Here we report the fabrication of an epitaxial heterostructure made with a double buffer layer of BaZrO3 and SrTiO3 grown on MgO substrates that fulfills both requirements. Based on such template platform, highly ordered (001) epitaxially oriented thin films of 15% Sm-doped CeO2 and 8 mol% Y2O3 stabilized ZrO2 are grown. Bulk conductivities as well as activation energies are measured for both materials, confirming the success of the approach. The reported insulating template platform promises potential application also for the electrical characterization of other novel electrolyte materials that still need a thorough understanding of their ionic conductivity.

Donor ionization in size controlled silicon nanocrystals: The transition from defect passivation to free electron generation

NASA Astrophysics Data System (ADS)

Crowe, I. F.; Papachristodoulou, N.; Halsall, M. P.; Hylton, N. P.; Hulko, O.; Knights, A. P.; Yang, P.; Gwilliam, R. M.; Shah, M.; Kenyon, A. J.

2013-01-01

We studied the photoluminescence spectra of silicon and phosphorus co-implanted silica thin films on (100) silicon substrates as a function of isothermal annealing time. The rapid phase segregation, formation, and growth dynamics of intrinsic silicon nanocrystals are observed, in the first 600 s of rapid thermal processing, using dark field mode X-TEM. For short annealing times, when the nanocrystal size distribution exhibits a relatively small mean diameter, formation in the presence of phosphorus yields an increase in the luminescence intensity and a blue shift in the emission peak compared with intrinsic nanocrystals. As the mean size increases with annealing time, this enhancement rapidly diminishes and the peak energy shifts further to the red than the intrinsic nanocrystals. These results indicate the existence of competing pathways for the donor electron, which depends strongly on the nanocrystal size. In samples containing a large density of relatively small nanocrystals, the tendency of phosphorus to accumulate at the nanocrystal-oxide interface means that ionization results in a passivation of dangling bond (Pb-centre) type defects, through a charge compensation mechanism. As the size distribution evolves with isothermal annealing, the density of large nanocrystals increases at the expense of smaller nanocrystals, through an Ostwald ripening mechanism, and the majority of phosphorus atoms occupy substitutional lattice sites within the nanocrystals. As a consequence of the smaller band-gap, ionization of phosphorus donors at these sites increases the free carrier concentration and opens up an efficient, non-radiative de-excitation route for photo-generated electrons via Auger recombination. This effect is exacerbated by an enhanced diffusion in phosphorus doped glasses, which accelerates silicon nanocrystal growth.

Tunable infrared absorption and visible transparency of colloidal aluminum-doped zinc oxide nanocrystals.

PubMed

Buonsanti, Raffaella; Llordes, Anna; Aloni, Shaul; Helms, Brett A; Milliron, Delia J

2011-11-09

Plasmonic nanocrystals have been attracting a lot of attention both for fundamental studies and different applications, from sensing to imaging and optoelectronic devices. Transparent conductive oxides represent an interesting class of plasmonic materials in addition to metals and vacancy-doped semiconductor quantum dots. Herein, we report a rational synthetic strategy of high-quality colloidal aluminum-doped zinc oxide nanocrystals. The presence of substitutional aluminum in the zinc oxide lattice accompanied by the generation of free electrons is proved for the first time by tunable surface plasmon absorption in the infrared region both in solution and in thin films.

Microstructure and mechanical properties of Zr-Si-N films prepared by rf-reactive sputtering

NASA Astrophysics Data System (ADS)

Nose, M.; Chiou, W. A.; Zhou, M.; Mae, T.; Meshii, M.

2002-05-01

ZrN and ZrSiN films were prepared in an rf sputtering apparatus that has a pair of targets facing each other (referred to as the facing target-type rf sputtering). Films were deposited on silicon wafers without bias application or substrate heating in order to examine only the effect of silicon addition to the transition metal nitride films. The contents of zirconium, nitrogen, and silicon of the films were determined with an electron probe microanalyzer. The transmission electron microscopy studies were carried out in addition to x-ray diffraction. For the high resolution transmission electron microscopy observation, the field emission type transmission electron microscope was used, which provides a point-to-point resolution of 0.1 nm. The samples were observed both parallel and perpendicular to the film surface, which were plane and cross sectional views, respectively. In order to investigate the relationship between the mechanical properties and microstructure of films, the hardness was measured by a nanoindentation system at room temperature. The load was selected to keep the impression depth below 60 nm (not more than 5% of film thickness) so that the influence from the substrate can be neglected. The hardness of the films increases with small Si additions reaching the maximum value of 35 GPa at around 3 at. % Si. The tendency to grow columnar grains was strongest around this composition, while grains became equiaxial above 5 at. % of Si. The films containing 12.8% Si, which showed the lowest hardness of 18 GPa, consist of nanocrystal grains. The presence of ZrN nanocrystals embedded in Si3N4 was not observed in the present study. The hardening mechanism due to the addition of small amounts of Si in ZrN can not be determined at this time. The grain size and residual stress can make minor contributions to the hardening. A possibility of solid solution hardening due to atomistic strain, such as nitrogen atoms at interstitial sites or other point defects is

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

NASA Astrophysics Data System (ADS)

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

2014-10-01

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

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

NASA Astrophysics Data System (ADS)

Jansons, Adam Wayne

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

Nanoscale Investigation of Grain Growth in RF-Sputtered Indium Tin Oxide Thin Films by Scanning Probe Microscopy

NASA Astrophysics Data System (ADS)

Lamsal, B. S.; Dubey, M.; Swaminathan, V.; Huh, Y.; Galipeau, D.; Qiao, Q.; Fan, Q. H.

2014-11-01

This work studied the electronic characteristics of the grains and grain boundaries of indium tin oxide (ITO) thin films using electrostatic and Kelvin probe force microscopy. Two types of ITO films were compared, deposited using radiofrequency magnetron sputtering in pure argon or 99% argon + 1% oxygen, respectively. The average grain size and surface roughness increased with substrate temperature for the films deposited in pure argon. With the addition of 1% oxygen, the increase in the grain size was inhibited above 150°C, which was suggested to be due to passivation of the grains by the excess oxygen. Electrostatic force microscopy and Kelvin probe force microscopy (KPFM) images confirmed that the grain growth was defect mediated and occurred at defective interfaces at high temperatures. Films deposited at room temperature with 1% oxygen showed crystalline nature, while films deposited with pure argon at room temperature were amorphous as observed from KPFM images. The potential drop across the grain and grain boundary was determined by taking surface potential line profiles to evaluate the electronic properties.

[Fluorescence spectra and quantum yield of TiO2 nanocrystals synthesized by alcohothermal method].

PubMed

Song, Cui-Hong; Li, Yan-Ting; Li, Jing; Wei, Yong-Ju; Hu, Yu-Zhu; Wei, Yu

2008-01-01

Fluorescence spectra and fluorescence quantum yield of TiO2 nanocrystals were studied. Using tetra n-butyl titanate as a starting material, a facile alcohothermal technique was used to synthesize TiO2 nanocrystals. As can be seen from the transmittance electron microscopy (TEM) image, TiO2 nanocrystals with a relatively uniform particle size distribution of < 10 nm are present in the transparent sol. The transparent sol presents a strong stable fluorescence emission with a maximum at 450 nm, which is greatly dependent on the size quantization effects, defect energy level and the surface state of TiO2 nanocrystals. The quantum yield (gamma) of TiO2 was determined by the relative comparison procedure, using freshly prepared analytical purity quinine sulfate in 0.05 mol x L(-1) H2SO4 as a relative quantum yield standard. The emission quantum yield of TiO2 nanocrystals prepared in alcoholic media was calculated to be about 0.20 at wavelengths ranging from 330 to 370 nm, which was much higher than the values reported in previous works. So, it is supposed that nano-TiO2 will be applied as a potential quantum dots fluorescence probe in biological analysis.

Nanocrystal/sol-gel nanocomposites

DOEpatents

Klimov, Victor L.; Petruska, Melissa A.

2010-05-25

The present invention is directed to a process for preparing a solid composite having colloidal nanocrystals dispersed within a sol-gel matrix, the process including admixing colloidal nanocrystals with an amphiphilic polymer including hydrophilic groups selected from the group consisting of --COOH, --OH, --SO.sub.3H, --NH.sub.2, and --PO.sub.3H.sub.2 within a solvent to form an alcohol-soluble colloidal nanocrystal-polymer complex, admixing the alcohol-soluble colloidal nanocrystal-polymer complex and a sol-gel precursor material, and, forming the solid composite from the admixture. The present invention is also directed to the resultant solid composites and to the alcohol-soluble colloidal nanocrystal-polymer complexes.

Single laser based pump-probe technique to study plasma shielding during nanosecond laser ablation of copper thin films

NASA Astrophysics Data System (ADS)

Nammi, Srinagalakshmi; Vasa, Nilesh J.; Gurusamy, Balaganesan; Mathur, Anil C.

2017-09-01

A plasma shielding phenomenon and its influence on micromachining is studied experimentally and theoretically for laser wavelengths of 355 nm, 532 nm and 1064 nm. A time resolved pump-probe technique is proposed and demonstrated by splitting a single nanosecond Nd3+:YAG laser into an ablation laser (pump laser) and a probe laser to understand the influence of plasma shielding on laser ablation of copper (Cu) clad on polyimide thin films. The proposed nanosecond pump-probe technique allows simultaneous measurement of the absorption characteristics of plasma produced during Cu film ablation by the pump laser. Experimental measurements of the probe intensity distinctly show that the absorption by the ablated plume increases with increase in the pump intensity, as a result of plasma shielding. Theoretical estimation of the intensity of the transmitted pump beam based on the thermo-temporal modeling is in qualitative agreement with the pump-probe based experimental measurements. The theoretical estimate of the depth attained for a single pulse with high pump intensity value on a Cu thin film is limited by the plasma shielding of the incident laser beam, similar to that observed experimentally. Further, the depth of micro-channels produced shows a similar trend for all three wavelengths, however, the channel depth achieved is lesser at the wavelength of 1064 nm.

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

NASA Astrophysics Data System (ADS)

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

2015-07-01

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

Visualizing Current Flow at the Mesoscale in Disordered Assemblies of Touching Semiconductor Nanocrystals

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

Chen, Qinyi; Guest, Jeffrey R.; Thimsen, Elijah

2017-07-12

The transport of electrons through assemblies of nanocrystals is important to performance in optoelectronic applications for these materials. Previous work has primarily focused on single nanocrystals or transitions between pairs of nanocrystals. There is a gap in knowledge of how large numbers of nanocrystals in an assembly behave collectively, and how this collective behavior manifests at the mesoscale. In this work, the variable range hopping (VRH) transport of electrons in disordered assemblies of touching, heavily doped ZnO nanocrystals was visualized at the mesoscale as a function of temperature both theoretically, using the model of Skinner, Chen and Shklovskii (SCS), andmore » experimentally, with conductive atomic force microscopy on ultrathin films only a few particle layers thick. Agreement was obtained between the model and experiments, with a few notable exceptions. The SCS model predicts that a single network within the nanocrystal assembly, comprised of sites connected by small resistances, dominates conduction - namely the optimum band from variable range hopping theory. However, our experiments revealed that in addition to the optimum band, there are subnetworks that appear as additional peaks in the resistance histogram of conductive atomic force microscopy (CAFM) maps. Furthermore, the connections of these subnetworks to the optimum band change in time, such that some subnetworks become connected to the optimum band while others become disconnected and isolated from the optimum band; this observation appears to be an experimental manifestation of the ‘blinking’ phenomenon in our images of mesoscale transport.« less

Nanocrystals Technology for Pharmaceutical Science.

PubMed

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

2018-05-17

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

De-vitrification of nanoscale phase-separated amorphous thin films in the immiscible copper-niobium system

NASA Astrophysics Data System (ADS)

Puthucode, A.; Devaraj, A.; Nag, S.; Bose, S.; Ayyub, P.; Kaufman, M. J.; Banerjee, R.

2014-05-01

Copper and niobium are mutually immiscible in the solid state and exhibit a large positive enthalpy of mixing in the liquid state. Using vapour quenching via magnetron co-sputter deposition, far-from equilibrium amorphous Cu-Nb films have been deposited which exhibit a nanoscale phase separation. Annealing these amorphous films at low temperatures (~200 °C) initiates crystallization via the nucleation and growth of primary nanocrystals of a face-centred cubic Cu-rich phase separated by the amorphous matrix. Interestingly, subsequent annealing at a higher temperature (>300 °C) leads to the polymorphic nucleation and growth of large spherulitic grains of a body-centred cubic Nb-rich phase within the retained amorphous matrix of the partially crystallized film. This sequential two-stage crystallization process has been investigated in detail by combining transmission electron microscopy [TEM] (including high-resolution TEM) and atom probe tomography studies. These results provide new insights into the crystallization behaviour of such unusual far-from equilibrium phase-separated metallic glasses in immiscible systems.

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

PubMed

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

2015-02-25

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

Probing the shear viscosity of an active nematic film

NASA Astrophysics Data System (ADS)

Guillamat, Pau; Ignés-Mullol, Jordi; Shankar, Suraj; Marchetti, M. Cristina; Sagués, Francesc

2016-12-01

In vitro reconstituted active systems, such as the adenosine triphosphate (ATP)-driven microtubule bundle suspension developed by the Dogic group [T. Sanchez, D. T. Chen, S. J. DeCamp, M. Heymann, and Z. Dogic, Nature (London) 491, 431 (2012), 10.1038/nature11591], provide a fertile testing ground for elucidating the phenomenology of active liquid crystalline states. Controlling such novel phases of matter crucially depends on our knowledge of their material and physical properties. In this Rapid Communication, we show that the shear viscosity of an active nematic film can be probed by varying its hydrodynamic coupling to a bounding oil layer. Using the motion of disclinations as intrinsic tracers of the flow field and a hydrodynamic model, we obtain an estimate for the shear viscosity of the nematic film. Knowing this now provides us with an additional handle for robust and precision tunable control of the emergent dynamics of active fluids.

A versatile rotary-stage high frequency probe station for studying magnetic films and devices

NASA Astrophysics Data System (ADS)

He, Shikun; Meng, Zhaoliang; Huang, Lisen; Yap, Lee Koon; Zhou, Tiejun; Panagopoulos, Christos

2016-07-01

We present a rotary-stage microwave probe station suitable for magnetic films and spintronic devices. Two stages, one for field rotation from parallel to perpendicular to the sample plane (out-of-plane) and the other intended for field rotation within the sample plane (in-plane) have been designed. The sample probes and micro-positioners are rotated simultaneously with the stages, which allows the field orientation to cover θ from 0∘ to 90∘ and φ from 0∘ to 360∘. θ and φ being the angle between the direction of current flow and field in a out-of-plane and an in-plane rotation, respectively. The operation frequency is up to 40 GHz and the magnetic field up to 1 T. The sample holder vision system and probe assembly are compactly designed for the probes to land on a wafer with diameter up to 3 cm. Using homemade multi-pin probes and commercially available high frequency probes, several applications including 4-probe DC measurements, the determination of domain wall velocity, and spin transfer torque ferromagnetic resonance are demonstrated.

Water adsorption on surface-modified cellulose nanocrystals

NASA Astrophysics Data System (ADS)

Wei, Zonghui; Sinko, Robert; Keten, Sinan; Luijten, Erik

Cellulose nanocrystals (CNCs) have attracted much attention as a filler phase for polymer nanocomposites due to their impressive mechanical properties, low cost, and environmental sustainability. Despite their promise for this application, there are still numerous obstacles that prevent optimal performance of CNC-polymer nanocomposites, such as poor filler dispersion and high levels of water absorption. One way to mitigate these negative effects is to modify CNC surfaces. Computational approaches can be utilized to obtain direct insight into the properties of modified CNC surfaces and probe the interactions of CNCs with other materials to facilitate the experimental design of nanocomposites. We use atomistic grand-canonical Monte Carlo simulations to study how surface modification of ion-exchanged sulfated cellulose nanocrystals (Na-CNCs) impacts water adsorption. We find that methyl(triphenyl)phosphonium-exchanged CNCs adsorb less water than Na-CNCs at the same relative humidity, supporting recent experimental dynamic vapor sorption measurements. By characterizing the distribution and configuration of water molecules near the modified CNC surfaces we determine how surface modifications disrupt CNC-water interactions.

Exploring exciton relaxation and multiexciton generation in PbSe nanocrystals using hyperspectral near-IR probing.

PubMed

Gdor, Itay; Sachs, Hanan; Roitblat, Avishy; Strasfeld, David B; Bawendi, Moungi G; Ruhman, Sanford

2012-04-24

Hyperspectral femtosecond transient absorption spectroscopy is employed to record exciton relaxation and recombination in colloidal lead selenide (PbSe) nanocrystals in unprecedented detail. Results obtained with different pump wavelengths and fluences are scrutinized with regard to three issues: (1) early subpicosecond spectral features due to "hot" excitons are analyzed in terms of suggested underlying mechanisms; (2) global kinetic analysis facilitates separation of the transient difference spectra into single, double, and triple exciton state contributions, from which individual band assignments can be tested; and (3) the transient spectra are screened for signatures of multiexciton generation (MEG) by comparing experiments with excitation pulses both below and well above the theoretical threshold for multiplication. For the latter, a recently devised ultrafast pump-probe spectroscopic approach is employed. Scaling sample concentrations and pump pulse intensities inversely with the extinction coefficient at each excitation wavelength overcomes ambiguities due to direct multiphoton excitation, uncertainties of absolute absorption cross sections, and low signal levels. As observed in a recent application of this method to InAs core/shell/shell nanodots, no sign of MEG was detected in this sample up to photon energy 3.7 times the band gap. Accordingly, numerous reports of efficient MEG in other samples of PbSe suggest that the efficiency of this process varies from sample to sample and depends on factors yet to be determined.

Surface and interface effects on non-radiative exciton recombination and relaxation dynamics in CdSe/Cd,Zn,S nanocrystals

NASA Astrophysics Data System (ADS)

Walsh, Brenna R.; Saari, Jonathan I.; Krause, Michael M.; Nick, Robert; Coe-Sullivan, Seth; Kambhampati, Patanjali

2016-06-01

Excitonic state-resolved pump/probe spectroscopy and time correlate single photon counting were used to study exciton dynamics from the femtosecond to nanosecond time scales in CdSe/Cd,Zn,S nanocrystals. These measurements reveal the role of the core/shell interface as well as surface on non-radiative excitonic processes over three time regimes. Time resolved photoluminescence reports on how the interface controls slow non-radiative processes that dictate emission at the single excitonic level. Heterogeneity in decay is minimized by interfacial structure. Pump/probe measurements explore the non-radiative multiexcitonic recombination processes on the picosecond timescale. These Auger based non-radiative processes dictate lifetimes of multiexcitonic states. Finally state-resolved pump/probe measurements on the femtosecond timescale reveal the influence of the interface on electron and hole relaxation dynamics. We find that the interface has a profound influence on all three types of non-radiative processes which ultimately control light emission from nanocrystals.

Novel four-sided neural probe fabricated by a thermal lamination process of polymer films.

PubMed

Shin, Soowon; Kim, Jae-Hyun; Jeong, Joonsoo; Gwon, Tae Mok; Lee, Seung-Hee; Kim, Sung June

2017-02-15

Ideally, neural probes should have channels with a three-dimensional (3-D) configuration to record the activities of 3-D neural circuits. Many types of 3-D neural probes have been developed; however, most of them were designed as an array of multiple shanks with electrodes located along one side of the shanks. We developed a novel liquid crystal polymer (LCP)-based neural probe with four-sided electrodes. This probe has electrodes on four sides of the shank, i.e., the front, back and two sidewalls. To generate the proposed configuration of the electrodes, we used a thermal lamination process involving LCP films and laser micromachining. The proposed novel four-sided neural probe, was used to successfully perform in vivo multichannel neural recording in the mouse primary somatosensory cortex. The multichannel neural recording showed that the proposed four-sided neural probe can record spiking activities from a more diverse neuronal population than single-sided probes. This was confirmed by a pairwise Pearson correlation coefficient (Pearson's r) analysis and a cross-correlation analysis. The developed four-sided neural probe can be used to record various signals from a complex neural network. Copyright © 2016 Elsevier B.V. All rights reserved.

"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.

Bright long-lived luminescence of silicon nanocrystals sensitized by two-photon absorbing antenna

PubMed Central

Ravotto, Luca; Chen, Qi; Ma, Yuguo; Vinogradov, Sergei A.; Locritani, Mirko; Bergamini, Giacomo; Negri, Fabrizia; Yu, Yixuan; Korgel, Brian A.; Ceroni, Paola

2017-01-01

Summary Silicon nanocrystals of the average diameter of 5 nm, functionalized with 4,7-di(2-thienyl)-2,1,3-benzothiadiazole chromophores (TBT) and dodecyl chains, exhibit near-infrared emission upon one-photon (1P) excitation at 515 nm and two-photon (2P) excitation at 960 nm. By using TBT chromophores as an antenna we were able to enhance both 1P and 2P absorption cross-sections of the silicon nanocrystals to more efficiently excite their long-lived luminescence. These results chart a path to two-photon-excitable imaging probes with long-lived oxygen-independent luminescence - a rare combination of properties that should allow for a substantial increase in imaging contrast. PMID:28966989

Probing molecular orientations in thin films by x-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Li, Y.; Li, P.; Lu, Z.-H.

2018-03-01

A great number of functional organic molecules in active thin-film layers of optoelectronic devices have highly asymmetric structures, such as plate-like, rod-like, etc. This makes molecular orientation an important aspect in thin-films as it can significantly affect both the optical and electrical performance of optoelectronic devices. With a combination of in-situ ultra violet photoelectron spectroscopy (UPS) and x-ray photoelectron spectroscopy (XPS) investigations for organic molecules having a broad range of structural properties, we discovered a rigid connection of core levels and frontier highest occupied molecular orbital levels at organic interfaces. This finding opens up opportunities of using X-ray photoemission spectroscopy as an alternative tool to UPS for providing an easy and unambiguous data interpretation in probing molecular orientations.

Imaging ac losses in superconducting films via scanning Hall probe microscopy

NASA Astrophysics Data System (ADS)

Dinner, Rafael B.; Moler, Kathryn A.; Feldmann, D. Matthew; Beasley, M. R.

2007-04-01

Various local probes have been applied to understanding current flow through superconducting films, which are often surprisingly inhomogeneous. Here, we show that magnetic imaging allows quantitative reconstruction of both current density J and electric field E resolved in time and space in a film carrying subcritical ac current. Current reconstruction entails inversion of the Biot-Savart law, while electric fields are reconstructed using Faraday’s law. We describe the corresponding numerical procedures, largely adapting existing work to the case of a strip carrying ac current, but including other methods of obtaining the complete electric field from the inductive portion determined by Faraday’s law. We also delineate the physical requirements behind the mathematical transformations. We then apply the procedures to images of a strip of YBa2Cu3O7-δ carrying an ac current at 400Hz . Our scanning Hall probe microscope produces a time series of magnetic images of the strip with 1μm spatial resolution and 25μs time resolution. Combining the reconstructed J and E , we obtain a complete characterization including local critical current density, E-J curves, and power losses. This analysis has a range of applications from fundamental studies of vortex dynamics to practical coated conductor development.

Harvesting solar energy by means of charge-separating nanocrystals and their solids.

PubMed

Diederich, Geoffrey; O'Connor, Timothy; Moroz, Pavel; Kinder, Erich; Kohn, Elena; Perera, Dimuthu; Lorek, Ryan; Lambright, Scott; Imboden, Martene; Zamkov, Mikhail

2012-08-23

Conjoining different semiconductor materials in a single nano-composite provides synthetic means for the development of novel optoelectronic materials offering a superior control over the spatial distribution of charge carriers across material interfaces. As this study demonstrates, a combination of donor-acceptor nanocrystal (NC) domains in a single nanoparticle can lead to the realization of efficient photocatalytic materials, while a layered assembly of donor- and acceptor-like nanocrystals films gives rise to photovoltaic materials. Initially the paper focuses on the synthesis of composite inorganic nanocrystals, comprising linearly stacked ZnSe, CdS, and Pt domains, which jointly promote photoinduced charge separation. These structures are used in aqueous solutions for the photocatalysis of water under solar radiation, resulting in the production of H2 gas. To enhance the photoinduced separation of charges, a nanorod morphology with a linear gradient originating from an intrinsic electric field is used. The inter-domain energetics are then optimized to drive photogenerated electrons toward the Pt catalytic site while expelling the holes to the surface of ZnSe domains for sacrificial regeneration (via methanol). Here we show that the only efficient way to produce hydrogen is to use electron-donating ligands to passivate the surface states by tuning the energy level alignment at the semiconductor-ligand interface. Stable and efficient reduction of water is allowed by these ligands due to the fact that they fill vacancies in the valence band of the semiconductor domain, preventing energetic holes from degrading it. Specifically, we show that the energy of the hole is transferred to the ligand moiety, leaving the semiconductor domain functional. This enables us to return the entire nanocrystal-ligand system to a functional state, when the ligands are degraded, by simply adding fresh ligands to the system. To promote a photovoltaic charge separation, we use a

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

PubMed

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

2010-04-14

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

Effects of addition of supramolecular assembly on the anatase nanocrystalline precipitation of sol-gel derived SiO2-TiO2 coating films by hot-water treatment.

PubMed

Katagiri, Kiyofumi; Harada, Genki; Matsuda, Atsunori; Kogure, Toshihiro; Muto, Hiroyuki; Sakai, Mototsugu

2006-06-01

Effects of the addition of a supramolecular assembly of cetyltrimethylammonium bromide in SiO2-TiO2 gel films on the formation of anatase type TiO2 nanocrystals with hot-water treatment were investigated. Anatase nanocrystals were formed in the whole SiO2-TiO2 gel films with the addition of cetyltrimethylammonium bromide by the treatment, whereas the nanocrystals were formed only on the film surface in the case of gel films without cetyltrimethylammonium bromide. Cetyltrimethylammonium bromide molecules in the SiO2-TiO2 gel films were completely removed by the hot-water treatment and the following UV irradiation. In the usual procedure for preparation of porous materials, the removal of template molecular assemblies required high temperature treatment over 400 degrees C. In this system, all the processes were performed at temperatures less than 100 degrees C. Additionally, the porous structure produced by the removal of micellar assembly allowed anatase nanocrystals to be formed inside the films. Therefore, the method presented in this work provides us with the novel photocatalyst coatings of porous membrane with highly-dispersed TiO2 nanocrystals via low temperature process.

Hybrid nanocomposites of CdSe nanocrystals distributed in complexing thiophene-based copolymers.

PubMed

Aldakov, Dmitry; Jiu, Tonggang; Zagorska, Malgorzata; de Bettignies, Rémi; Jouneau, Pierre-Henri; Pron, Adam; Chandezon, Frédéric

2010-07-21

Two types of conjugated polymers were prepared with the goal to blend them with rod-like CdSe nanocrystals. The polymers of the first type were synthesized through copolymerization of 3-octylthiophene and 3-methylene-ethylcarboxylate-thiophene to give polythiophene with solubilizing alkyl groups and methylene ester functional groups (PE series). Post-polymerization hydrolysis of the ester type polymers yielded acid-type ones (PA series). Photoluminescence (PL) quenching in these polymers induced by their titration with nanocrystals solution was chosen as a measure of the polymer-nanocrystal interactions. PL of polyacids turned out to be more efficiently quenched as compared to the case of polymers with ester groups which was interpreted as an indication of better electronic communication between the hybrid components. Infrared (IR) spectroscopy confirmed efficient coordination of the carboxylic groups to CdSe. Voltammetric studies combined with UV-vis spectroelectrochemistry enabled the determination of energy levels alignment of the molecular composite components which turned out to be of staggered type-appropriate for photovoltaic applications. The obtained blends of polyacids with CdSe nanocrystals, when studied by transmission electron microscopy (TEM), revealed the presence of an interpenetrating network in which nanorods were homogeneously distributed within the polymer matrix without any indication of agglomerates formation both on the film surface and in the cross-section. Blends with polymers containing ester groups were less homogeneous which could be explained by weaker polymer-nanocrystals interactions. Photovoltaic cells based on these hybrid materials are also discussed.

Syntheses and applications of manganese-doped II-VI semiconductor nanocrystals

NASA Astrophysics Data System (ADS)

Yang, Heesun

Syntheses, characterizations, and applications of two different Mn-doped semiconductor nanocrystals, ZnS:Mn and CdS:Mn/ZnS core/shell, were investigated. ZnS:Mn nanocrystals with sizes between 3 and 4 nm were synthesized via a competitive reaction chemistry. A direct current (dc) electroluminescent (EL) device having a hybrid organic/inorganic multilayer structure of an indium tin oxide (ITO) transparent conducting electrode, a (poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT-PSS) and a poly(N-vinylcarbazole) (PVK) bilayer hole transport film, a ZnS:Mn nanocrystal layer, and Al dot contacts was demonstrated to emit blue (˜445 and ˜495 nm) from PVK and yellow (˜600 nm) light from Mn activator in ZnS. The EL emission spectrum was dependent upon both the voltage and Mn concentration, showing a decreasing nanocrystal to PVK emission ratio from 10 at 20 V to 4 at 28 V, and an increasing ratio from 1.3 at 0.40 mol % to 4.3 at 2.14 mol %. Mn-doped CdS core nanocrystals were produced ranging from 1.5 to 2.3 nm in diameter with a ZnS shell via a reverse micelle process. In contrast to CdS:Mn nanocrystals passivated by n-dodecanethiol, ZnS-passivated CdS:Mn (CdS:Mn/ZnS core/shell) nanocrystals were efficient and photostable. CdS:Mn/ZnS core/shell nanocrystals exhibited a quantum yield of ˜18%, and the photoluminescence (PL) intensity increased by 40% after 400 nm UV irradiation in air. X-ray photoelectron spectroscopy (XPS) data showed that UV irradiation of CdS:Mn/ZnS nanocrystals induces the photooxidation of the ZnS shell surface to ZnSO4. This photooxidation product is presumably responsible for the increased PL emission by serving as a passivating surface layer. Luminescent lifetime data from the core/shell nanocrystals could be fit with two exponential functions, with a time constant of ˜170 nsec for the defect-related centers and of ˜1 msec for the Mn centers. The CdS:Mn/ZnS nanocrystals with a core crystal diameter of 2.3 nm and a 0.4 nm thick Zn

Photon Reabsorption in Mixed CsPbCl3:CsPbI3 Perovskite Nanocrystal Films for Light-Emitting Diodes

PubMed Central

2017-01-01

Cesium lead halide nanocrystals, CsPbX3 (X = Cl, Br, I), exhibit photoluminescence quantum efficiencies approaching 100% without the core–shell structures usually used in conventional semiconductor nanocrystals. These high photoluminescence efficiencies make these crystals ideal candidates for light-emitting diodes (LEDs). However, because of the large surface area to volume ratio, halogen exchange between perovskite nanocrystals of different compositions occurs rapidly, which is one of the limiting factors for white-light applications requiring a mixture of different crystal compositions to achieve a broad emission spectrum. Here, we use mixtures of chloride and iodide CsPbX3 (X = Cl, I) perovskite nanocrystals where anion exchange is significantly reduced. We investigate samples containing mixtures of perovskite nanocrystals with different compositions and study the resulting optical and electrical interactions. We report excitation transfer from CsPbCl3 to CsPbI3 in solution and within a poly(methyl methacrylate) matrix via photon reabsorption, which also occurs in electrically excited crystals in bulk heterojunction LEDs. PMID:28316756

Utilizing dynamic laser speckle to probe nanoscale morphology evolution in nanoporous gold thin films

DOE PAGES

Chapman, Christopher A. R.; Ly, Sonny; Wang, Ling; ...

2016-03-02

Here we show the use of dynamic laser speckle autocorrelation spectroscopy in conjunction with the photothermal treatment of nanoporous gold (np-Au) thin films to probe nanoscale morphology changes during the photothermal treatment. Utilizing this spectroscopy method, backscattered speckle from the incident laser is tracked during photothermal treatment and both the characteristic feature size and annealing time of the film are determined. These results demonstrate that this method can successfully be used to monitor laser-based surface modification processes without the use of ex-situ characterization.

Utilizing dynamic laser speckle to probe nanoscale morphology evolution in nanoporous gold thin films

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

Chapman, Christopher A. R.; Ly, Sonny; Wang, Ling

Here we show the use of dynamic laser speckle autocorrelation spectroscopy in conjunction with the photothermal treatment of nanoporous gold (np-Au) thin films to probe nanoscale morphology changes during the photothermal treatment. Utilizing this spectroscopy method, backscattered speckle from the incident laser is tracked during photothermal treatment and both the characteristic feature size and annealing time of the film are determined. These results demonstrate that this method can successfully be used to monitor laser-based surface modification processes without the use of ex-situ characterization.

Layer-by-layer deposition of nanostructured CsPbBr3 perovskite thin films

NASA Astrophysics Data System (ADS)

Reshetnikova, A. A.; Matyushkin, L. B.; Andronov, A. A.; Sokolov, V. S.; Aleksandrova, O. A.; Moshnikov, V. A.

2017-11-01

Layer-by-layer deposition of nanostructured perovskites cesium lead halide thin films is described. The method of deposition is based on alternate immersion of the substrate in the precursor solutions or colloidal solution of nanocrystals and methyl acetate/lead nitrate solution using the device for deposition of films by SILAR and dip-coating techniques. An example of obtaining a photosensitive structure based on nanostructures of ZnO nanowires and layers of CsBbBr3 nanocrystals is also shown.

A versatile rotary-stage high frequency probe station for studying magnetic films and devices

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

He, Shikun; Division of Physics and Applied Physics, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371; Meng, Zhaoliang

We present a rotary-stage microwave probe station suitable for magnetic films and spintronic devices. Two stages, one for field rotation from parallel to perpendicular to the sample plane (out-of-plane) and the other intended for field rotation within the sample plane (in-plane) have been designed. The sample probes and micro-positioners are rotated simultaneously with the stages, which allows the field orientation to cover θ from 0{sup ∘} to 90{sup ∘} and φ from 0{sup ∘} to 360{sup ∘}. θ and φ being the angle between the direction of current flow and field in a out-of-plane and an in-plane rotation, respectively. Themore » operation frequency is up to 40 GHz and the magnetic field up to 1 T. The sample holder vision system and probe assembly are compactly designed for the probes to land on a wafer with diameter up to 3 cm. Using homemade multi-pin probes and commercially available high frequency probes, several applications including 4-probe DC measurements, the determination of domain wall velocity, and spin transfer torque ferromagnetic resonance are demonstrated.« less

Free radical grafting of gallic acid (GA) on cellulose nanocrystals (CNCS) and evaluation of antioxidant reinforced gellan gum films

NASA Astrophysics Data System (ADS)

Criado, P.; Fraschini, C.; Salmieri, S.; Becher, D.; Safrany, A.; Lacroix, M.

2016-01-01

Antiradical properties were introduced on cellulose nanocrystals (CNCs) by redox pair (RP) initiator and γ-radiation treatments. Different procedures were tested on CNC, first a 2 h reaction of hydrogen peroxide (H2O2)/ascorbic acid (AA) was performed on CNC solution. γ-Radiation treatment at 20 kGy dose was then applied and immediately after GA was reacted during 24 h with the pretreated CNCs, giving CNC-H2O2-AA-γ-GA. The formation of new carboxylic acids and carbonyl groups were characterized by FT-IR at 1650 and 1730 cm-1 respectively. Carboxylic acid functionalities were also analyzed by conductometric titration where an increase from 49 to 134 mmol COOH kg-1 was found from native to irradiated CNCs. A similar increase in the carboxylic acid content (132 mmol kg-1) was observed for CNC-H2O2-AA-γ-GA, showing the highest radical scavenging properties (8 mM Trolox eq/mg CNC). Thermogravimetric analysis confirmed the structural changes onto CNC. Film packaging containing 20% of CNC-H2O2-AA-γ-GA was then added to a gellan-based film packaging. A significant improvement (p<0.05) of the tensile strength (TS), the tensile modulus (TM) and the elongation at break (EB) and water vapor permeability reduction was observed when CNC-H2O2-AA-γ-GA was added to the film packaging formulation.

Enhanced photovoltaic performance in nanoimprinted pentacene-PbS nanocrystal hybrid device

NASA Astrophysics Data System (ADS)

Dissanayake, D. M. N. M.; Adikaari, A. A. D. T.; Silva, S. R. P.

2008-03-01

Pentacene and PbS nanocrystal bilayer photovoltaic devices are fabricated after the pentacene layer is subjected to nanoimprinting using a laser textured silicon stamp. Increased short circuit current densities are observed for the imprinted devices, which are attributed to increased charge mobility in the pentacene film caused by the decrease in the intermolecular distances during nanoimprinting. This work is consistent with previous reports where hydrostatic pressure induced mobility increases have been observed in polyacenes under gigapascal pressure regimes. It is believed that the pentacene film undergoes localized high pressures during nanoimprinting, giving rise to the increased hole mobilities.

A composite generator film impregnated with cellulose nanocrystals for enhanced triboelectric performance

Treesearch

Jun Peng; Huilong Zhang; Qifeng Zheng; Craig M. Clemons; Ronald C. Sabo; Shaoqin Gong; Zhenqiang Ma; Lih-Sheng Turng

2017-01-01

A novel polydimethylsiloxane (PDMS)/cellulose nanocrystal flake (CNCF) composite triboelectric nanogenerator (CTG) using CNCFs as effective dielectrics a 10-times-enhanced triboelectric performance compared with its pure PDMS counterpart. Positive charges generated on the surface of the CNCFs during cyclic compression boosted electron transfer and induced extra charges...

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

NASA Astrophysics Data System (ADS)

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

2016-03-01

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

Optical Probe of the Density of Defect States in Organic Thin-Film Transistors

NASA Astrophysics Data System (ADS)

Breban, Mihaela; Romero, Danilo; Ballarotto, Vincent; Williams, Ellen

2006-03-01

We investigate the role of defect states associated with different gate dielectric materials on charge transport in organic thin film transistors. Using a modulation technique we measure the magnitude and the phase of the photocurrent^1 in pentacene thin film transistors as a function of the modulation frequency. The photocurrent generation process is modeled as exciton dissociation due to interaction with localized traps. A time domain analyses of this multi-step process allows us to extract the density of defect states. We use this technique to compare the physical mechanism underlying performances of pentacene devices fabricated with different dielectric materials. *Supported by the Laboratory for Physical Science ^1 M. Breban, et al. ``Photocurrent probe of field-dependent mobility in organic thin-film transistors'' Appl. Phys. Letts. 87, 203503 (2005)

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

NASA Astrophysics Data System (ADS)

Khare, Ankur

Copper zinc tin sulfide (Cu2ZnSnS4, or CZTS) is emerging as an alternative material to the present thin film solar cell technologies such as Cu(In,Ga)Se2 and CdTe. All the elements in CZTS are abundant, environmentally benign, and inexpensive. In addition, CZTS has a band gap of ˜1.5 eV, the ideal value for converting the maximum amount of energy from the solar spectrum into electricity. CZTS has a high absorption coefficient (>104 cm-1 in the visible region of the electromagnetic spectrum) and only a few micron thick layer of CZTS can absorb all the photons with energies above its band gap. CZT(S,Se) solar cells have already reached power conversion efficiencies >10%. One of the ways to improve upon the CZTS power conversion efficiency is by using CZTS quantum dots as the photoactive material, which can potentially achieve efficiencies greater than the present thin film technologies at a fraction of the cost. However, two requirements for quantum-dot solar cells have yet to be demonstrated. First, no report has shown quantum confinement in CZTS nanocrystals. Second, the syntheses to date have not provided a range of nanocrystal sizes, which is necessary not only for fundamental studies but also for multijunction photovoltaic architectures. We resolved these two issues by demonstrating a simple synthesis of CZTS, Cu2SnS3, and alloyed (Cu2SnS3) x(ZnS)y nanocrystals with diameters ranging from 2 to 7 nm from diethyldithiocarbamate complexes. As-synthesized nanocrystals were characterized using high resolution transmission electron microscopy, X-ray diffraction, Raman spectroscopy, and energy dispersive spectroscopy to confirm their phase purity. Nanocrystals of diameter less than 5 nm were found to exhibit a shift in their optical absorption spectra towards higher energy consistent with quantum confinement and previous theoretical predictions. Thin films from CZTS nanocrystals deposited on Mo-coated quartz substrates using drop casting were found to be continuous

PbSe Nanocrystal Solids for n- and p-Channel Thin Film Field-Effect Transistors

NASA Astrophysics Data System (ADS)

Talapin, Dmitri V.; Murray, Christopher B.

2005-10-01

Initially poorly conducting PbSe nanocrystal solids (quantum dot arrays or superlattices) can be chemically ``activated'' to fabricate n- and p-channel field effect transistors with electron and hole mobilities of 0.9 and 0.2 square centimeters per volt-second, respectively; with current modulations of about 103 to 104; and with current density approaching 3 × 104 amperes per square centimeter. Chemical treatments engineer the interparticle spacing, electronic coupling, and doping while passivating electronic traps. These nanocrystal field-effect transistors allow reversible switching between n- and p-transport, providing options for complementary metal oxide semiconductor circuits and enabling a range of low-cost, large-area electronic, optoelectronic, thermoelectric, and sensing applications.

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.

Hybrid systems of AlInP microdisks and colloidal CdSe nanocrystals showing whispering-gallery modes at room temperature

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

Strelow, Christian; Weising, Simon; Bonatz, Dennis

2014-09-01

We report on the realization of hybrid systems composed of passive optical microdisk resonators prepared from epitaxial layer systems and nanocrystal quantum emitters synthesized by colloidal chemistry. The AlInP disk material allows for the operation in the visible range, as probed by CdSe-based nanocrystals. Photoluminescence spectra at room temperature reveal sets of whispering-gallery modes consistent with finite-difference time-domain simulations. In the experiments, a special sample geometry renders it possible to detect resonant optical modes perpendicular to the disk plane.

Semiconductor nanocrystal-based phagokinetic tracking

DOEpatents

Alivisatos, A Paul; Larabell, Carolyn A; Parak, Wolfgang J; Le Gros, Mark; Boudreau, Rosanne

2014-11-18

Methods for determining metabolic properties of living cells through the uptake of semiconductor nanocrystals by cells. Generally the methods require a layer of neutral or hydrophilic semiconductor nanocrystals and a layer of cells seeded onto a culture surface and changes in the layer of semiconductor nanocrystals are detected. The observed changes made to the layer of semiconductor nanocrystals can be correlated to such metabolic properties as metastatic potential, cell motility or migration.

Reliability design and assessment of a micro-probe using the results of a tensile test of a beryllium-copper alloy thin film

NASA Astrophysics Data System (ADS)

Park, Jun-Hyub; Shin, Myung-Soo

2011-09-01

This paper describes the results of tensile tests for a beryllium-copper (BeCu) alloy thin film and the application of the results to the design of a probe. The copper alloy films were fabricated by electroplating. To obtain the tensile characteristics of the film, the dog-bone type specimen was fabricated by the etching method. The tensile tests were performed with the specimen using a test machine developed by the authors. The BeCu alloy has an elastic modulus of 119 GPa and the 0.2% offset yield and ultimate tensile strengths of 1078 MPa and 1108 MPa, respectively. The design and manufacture of a smaller probe require higher pad density and smaller pad-pitch chips. It should be effective in high-frequency testing. For the design of a new micro-probe, we investigated several design parameters that may cause problems, such as the contact force and life, using the tensile properties and the design of experiment method in conjunction with finite element analysis. The optimal dimensions of the probe were found using the response surface method. The probe with optimal dimensions was manufactured by a precision press process. It was verified that the manufactured probe satisfied the life, the contact force and the over drive through the compression tests and the life tests of the probes.

Thermally Stable Cellulose Nanocrystals toward High-Performance 2D and 3D Nanostructures.

PubMed

Jia, Chao; Bian, Huiyang; Gao, Tingting; Jiang, Feng; Kierzewski, Iain Michael; Wang, Yilin; Yao, Yonggang; Chen, Liheng; Shao, Ziqiang; Zhu, J Y; Hu, Liangbing

2017-08-30

Cellulose nanomaterials have attracted much attention in a broad range of fields such as flexible electronics, tissue engineering, and 3D printing for their excellent mechanical strength and intriguing optical properties. Economic, sustainable, and eco-friendly production of cellulose nanomaterials with high thermal stability, however, remains a tremendous challenge. Here versatile cellulose nanocrystals (DM-OA-CNCs) are prepared through fully recyclable oxalic acid (OA) hydrolysis along with disk-milling (DM) pretreatment of bleached kraft eucalyptus pulp. Compared with the commonly used cellulose nanocrystals from sulfuric acid hydrolysis, DM-OA-CNCs show several advantages including large aspect ratio, carboxylated surface, and excellent thermal stability along with high yield. We also successfully demonstrate the fabrication of high-performance films and 3D-printed patterns using DM-OA-CNCs. The high-performance films with high transparency, ultralow haze, and excellent thermal stability have the great potential for applications in flexible electronic devices. The 3D-printed patterns with porous structures can be potentially applied in the field of tissue engineering as scaffolds.

Magnetic Cellulose Nanocrystal Based Anisotropic Polylactic Acid Nanocomposite Films: Influence on Electrical, Magnetic, Thermal, and Mechanical Properties.

PubMed

Dhar, Prodyut; Kumar, Amit; Katiyar, Vimal

2016-07-20

This paper reports a single-step co-precipitation method for the fabrication of magnetic cellulose nanocrystals (MGCNCs) with high iron oxide nanoparticle content (∼51 wt % loading) adsorbed onto cellulose nanocrystals (CNCs). X-ray diffraction (XRD), Fourier transform infrared (FTIR), and Raman spectroscopic studies confirmed that the hydroxyl groups on the surface of CNCs (derived from the bamboo pulp) acted as anchor points for the adsorption of Fe3O4 nanoparticles. The fabricated MGCNCs have a high magnetic moment, which is utilized to orient the magnetoresponsive nanofillers in parallel or perpendicular orientations inside the polylactic acid (PLA) matrix. Magnetic-field-assisted directional alignment of MGCNCs led to the incorporation of anisotropic mechanical, thermal, and electrical properties in the fabricated PLA-MGCNC nanocomposites. Thermomechanical studies showed significant improvement in the elastic modulus and glass-transition temperature for the magnetically oriented samples. Differential scanning calorimetry (DSC) and XRD studies confirmed that the alignment of MGCNCs led to the improvement in the percentage crystallinity and, with the absence of the cold-crystallization phenomenon, finds a potential application in polymer processing in the presence of magnetic field. The tensile strength and percentage elongation for the parallel-oriented samples improved by ∼70 and 240%, respectively, and for perpendicular-oriented samples, by ∼58 and 172%, respectively, in comparison to the unoriented samples. Furthermore, its anisotropically induced electrical and magnetic properties are desirable for fabricating self-biased electronics products. We also demonstrate that the fabricated anisotropic PLA-MGCNC nanocomposites could be laminated into films with the incorporation of directionally tunable mechanical properties. Therefore, the current study provides a novel noninvasive approach of orienting nontoxic bioderived CNCs in the presence of low

Epoxy Monomers Cured by High Cellulosic Nanocrystal Loading.

PubMed

Khelifa, Farid; Habibi, Youssef; Bonnaud, Leila; Dubois, Philippe

2016-04-27

The present study focuses on the use of cellulose nanocrystals (CNC) as the main constituent of a nanocomposite material and takes advantage of hydroxyl groups, characteristic of the CNC chemical structure, to thermally cross-link an epoxy resin. An original and simple approach is proposed, based on the collective sticking of CNC building blocks with the help of a DGEBA/TGPAP-based epoxy resin. Scientific findings suggest that hydroxyl groups act as a toxic-free cross-linking agent of the resin. The enhanced protection against water degradation as compared to neat CNC film and the improvement of mechanical properties of the synthesized films are attributed to a good compatibility between the CNC and the resin. Moreover, the preservation of CNC optical properties at high concentrations opens the way to applying these materials in photonic devices.

Template-Free Mesoporous Electrochromic Films on Flexible Substrates from Tungsten Oxide Nanorods

DOE PAGES

Heo, Sungyeon; Kim, Jongwook; Ong, Gary K.; ...

2017-08-08

Low-temperature processed mesoporous nanocrystal thin films are platforms for fabricating functional composite thin films on flexible substrates. Using a random arrangement of anisotropic nanocrystals can be a facile solution to generate pores without templates. However, the tendency for anisotropic particles to spontaneously assemble into a compact structure must be overcome. Here in this paper, we present a method to achieve random networking of nanorods during solution phase deposition by switching their ligand-stabilized colloidal nature into a charge-stabilized nature by a ligand-stripping chemistry. Ligand-stripped tungsten suboxide (WO 2.72) nanorods result in uniform mesoporous thin films owing to repulsive electrostatic forces preventingmore » nanorods from densely packing. Porosity and pore size distribution of thin films are controlled by changing the aspect ratio of the nanorods. This template-free mesoporous structure, achieved without annealing, provides a framework for introducing guest components, therefore enabling our fabrication of inorganic nanocomposite electrochromic films on flexible substrates. Following infilling of niobium polyoxometalate clusters into pores and successive chemical condensation, a WO x–NbO x composite film is produced that selectively controls visible and near-infrared light transmittance without any annealing required. The composite shows rapid switching kinetics and can be stably cycled between optical states over 2000 times. This simple strategy of using anisotropic nanocrystals gives insight into mesoporous thin film fabrication with broader applications for flexible devices.« less

Template-Free Mesoporous Electrochromic Films on Flexible Substrates from Tungsten Oxide Nanorods

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

Heo, Sungyeon; Kim, Jongwook; Ong, Gary K.

Low-temperature processed mesoporous nanocrystal thin films are platforms for fabricating functional composite thin films on flexible substrates. Using a random arrangement of anisotropic nanocrystals can be a facile solution to generate pores without templates. However, the tendency for anisotropic particles to spontaneously assemble into a compact structure must be overcome. Here in this paper, we present a method to achieve random networking of nanorods during solution phase deposition by switching their ligand-stabilized colloidal nature into a charge-stabilized nature by a ligand-stripping chemistry. Ligand-stripped tungsten suboxide (WO 2.72) nanorods result in uniform mesoporous thin films owing to repulsive electrostatic forces preventingmore » nanorods from densely packing. Porosity and pore size distribution of thin films are controlled by changing the aspect ratio of the nanorods. This template-free mesoporous structure, achieved without annealing, provides a framework for introducing guest components, therefore enabling our fabrication of inorganic nanocomposite electrochromic films on flexible substrates. Following infilling of niobium polyoxometalate clusters into pores and successive chemical condensation, a WO x–NbO x composite film is produced that selectively controls visible and near-infrared light transmittance without any annealing required. The composite shows rapid switching kinetics and can be stably cycled between optical states over 2000 times. This simple strategy of using anisotropic nanocrystals gives insight into mesoporous thin film fabrication with broader applications for flexible devices.« less

Switchable Ni–Mn–Ga Heusler nanocrystals

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

Zayak, Alexey T.; Beckman, Scott P.; Tiago, Murilo L.

2008-10-02

Here, we examined bulk-like Heusler nanocrystals using real-space pseudopotentials constructed within density functional theory. The nanocrystals were made of various compositions of Ni-Mn-Ga in the size range from 15 up to 169 atoms. Among these compositions, the closest to the stoichiometric Ni 2MnGa were found to be the most stable. The Ni-based nanocrystals retained a tendency for tetragonal distortion, which is inherited from the bulk properties. Surface effects suppress the tetragonal structure in the smaller Ni-based nanocrystals, while bigger nanocrystals develop a bulk-like tetragonal distortion. We suggest the possibility of switchable Ni-Mn-Ga nanocrystals, which could be utilized for magnetic nano-shape-memorymore » applications.« less

Nanocrystal synthesis

DOEpatents

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

2016-11-01

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

Biomolecular Assembly of Gold Nanocrystals

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

Micheel, Christine Marya

2005-05-20

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

Electron transfer between colloidal ZnO nanocrystals.

PubMed

Hayoun, Rebecca; Whitaker, Kelly M; Gamelin, Daniel R; Mayer, James M

2011-03-30

Colloidal ZnO nanocrystals capped with dodecylamine and dissolved in toluene can be charged photochemically to give stable solutions in which electrons are present in the conduction bands of the nanocrystals. These conduction-band electrons are readily monitored by EPR spectroscopy, with g* values that correlate with the nanocrystal sizes. Mixing a solution of charged small nanocrystals (e(-)(CB):ZnO-S) with a solution of uncharged large nanocrystals (ZnO-L) caused changes in the EPR spectrum indicative of quantitative electron transfer from small to large nanocrystals. EPR spectra of the reverse reaction, e(-)(CB):ZnO-L + ZnO-S, showed that electrons do not transfer from large to small nanocrystals. Stopped-flow kinetics studies monitoring the change in the UV band-edge absorption showed that reactions of 50 μM nanocrystals were complete within the 5 ms mixing time of the instrument. Similar results were obtained for the reaction of charged nanocrystals with methyl viologen (MV(2+)). These and related results indicate that the electron-transfer reactions of these colloidal nanocrystals are quantitative and very rapid, despite the presence of ~1.5 nm long dodecylamine capping ligands. These soluble ZnO nanocrystals are thus well-defined redox reagents suitable for studies of electron transfer involving semiconductor nanostructures.

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.

DNA conformations in mismatch repair probed in solution by X-ray scattering from gold nanocrystals

PubMed Central

Hura, Greg L.; Tsai, Chi-Lin; Claridge, Shelley A.; Mendillo, Marc L.; Smith, Jessica M.; Williams, Gareth J.; Mastroianni, Alexander J.; Alivisatos, A. Paul; Putnam, Christopher D.; Kolodner, Richard D.; Tainer, John A.

2013-01-01

DNA metabolism and processing frequently require transient or metastable DNA conformations that are biologically important but challenging to characterize. We use gold nanocrystal labels combined with small angle X-ray scattering to develop, test, and apply a method to follow DNA conformations acting in the Escherichia coli mismatch repair (MMR) system in solution. We developed a neutral PEG linker that allowed gold-labeled DNAs to be flash-cooled and stored without degradation in sample quality. The 1,000-fold increased gold nanocrystal scattering vs. DNA enabled investigations at much lower concentrations than otherwise possible to avoid concentration-dependent tetramerization of the MMR initiation enzyme MutS. We analyzed the correlation scattering functions for the nanocrystals to provide higher resolution interparticle distributions not convoluted by the intraparticle distribution. We determined that mispair-containing DNAs were bent more by MutS than complementary sequence DNA (csDNA), did not promote tetramer formation, and allowed MutS conversion to a sliding clamp conformation that eliminated the DNA bends. Addition of second protein responder MutL did not stabilize the MutS-bent forms of DNA. Thus, DNA distortion is only involved at the earliest mispair recognition steps of MMR: MutL does not trap bent DNA conformations, suggesting migrating MutL or MutS/MutL complexes as a conserved feature of MMR. The results promote a mechanism of mismatch DNA bending followed by straightening in initial MutS and MutL responses in MMR. We demonstrate that small angle X-ray scattering with gold labels is an enabling method to examine protein-induced DNA distortions key to the DNA repair, replication, transcription, and packaging. PMID:24101514

Preparation of hybrid nano biocomposite κ-carrageenan/cellulose nanocrystal/nanoclay

NASA Astrophysics Data System (ADS)

Zakuwan, Siti Zarina; Ahmad, Ishak; Ramli, Nazaruddin

2013-11-01

Biodegradable composites film based on κ-carrageenan and nano particles as filler was prepared to study the mechanical strength of carrageenan composites. Solution casting technique was used to prepare_this biocomposite. Preparation of composite film and nano filler involve two stages, preparation of cellulose nanocrystals (CNC) from kenaf with alkali treatment, bleaching, and hydrolysis followed by the preparation of two types of nano composite. Tensile test was carried on the composite film based on κ-carrageenan with the variation percentage of CNC and nano clay to obtain the optimum CNC and nano clay loading. After that hybrid nano-biocomposite film based on κ-carrageenan with the variation percentage of CNC/nano clay (OMMT) according to optimum value of composite carrageenan/CNC and composite carrageenan/nano clay film was prepared. The effect of nano filler on the mechanical properties of carrageenan films was examined. κ-carrageenan biocomposite increased with the optimum at 4% CNC and nano clay composition. Additional improvement of tensile strength with hybridization of CNC and nanoclay indicated better mechanical properties.

Planar Heterojunction Perovskite Solar Cells Incorporating Metal-Organic Framework Nanocrystals.

PubMed

Chang, Ting-Hsiang; Kung, Chung-Wei; Chen, Hsin-Wei; Huang, Tzu-Yen; Kao, Sheng-Yuan; Lu, Hsin-Che; Lee, Min-Han; Boopathi, Karunakara Moorthy; Chu, Chih-Wei; Ho, Kuo-Chuan

2015-11-25

Zr-based porphyrin metal-organic framework (MOF-525) nanocrystals with a crystal size of about 140 nm are synthesized and incorporated into perovskite solar cells. The morphology and crystallinity of the perovskite thin film are enhanced since the micropores of MOF-525 allow the crystallization of perovskite to occur inside; this observation results in a higher cell efficiency of the obtained MOF/perovskite solar cell. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

PLLA-grafted cellulose nanocrystals: Role of the CNC content and grafting on the PLA bionanocomposite film properties.

PubMed

Lizundia, Erlantz; Fortunati, Elena; Dominici, Franco; Vilas, José Luis; León, Luis Manuel; Armentano, Ilaria; Torre, Luigi; Kenny, Josè M

2016-05-20

Cellulose nanocrystals (CNC), extracted from microcrystalline cellulose by acid hydrolysis, were grafted by ring opening polymerization of L-Lactide initiated from the hydroxyl groups available at their surface and two different CNC:L-lactide ratios (20:80 and 5:95) were obtained. The resulting CNC-g-PLLA nanohybrids were incorporated in poly(lactic acid) (PLA) matrix by an optimized extrusion process at two different content (1 wt.% and 3 wt.%) and obtained bionanocomposite films were characterized by thermal, mechanical, optical and morphological properties. Thermal analysis showed CNC grafted with the higher ratio of lactide play a significant role as a nucleating agent. Moreover, they contribute to a significant increase in the crystallization rate of PLA, and the best efficiency was revealed with 3 wt.% of CNC-g-PLLA. This effect was confirmed by the increased in Young's modulus, suggesting the CNC graft ratio and content contribute significantly to the good dispersion in the matrix, positively affecting the final bionanocomposite properties. Copyright © 2016 Elsevier Ltd. All rights reserved.

Adaptive laser conditioning of reflective thin film based on photo thermal lens probe

NASA Astrophysics Data System (ADS)

Liu, Zhichao; Zheng, Yi; Zhang, Qinghua; Pan, Feng; Wei, Yaowei; Wang, Jian; Xu, Qiao

2017-12-01

A novel laser conditioning (LC) concept that performs adaptive control of exposure fluence is proposed. As photo-thermal absorption effect can discover defects responsible for laser-induced damage of reflective thin film, in situ photo-thermal lens probe is introduced in conventional LC procedure to detect defects during raster-scanning. The absorptance signal is fed back to guide the adaptive control of exposure fluence. By this method, the damage risk accompanying with LC can be reduced to a rather low level. In order to test the performance of adaptive laser conditioning (ALC), an experimental setup has been built, and several film samples have been tested. The results show that ALC is effective at reducing laser damage risk.

Highly anisotropic mobility in solution processed TIPS-pentacene film studied by independently driven four GaIn probes

NASA Astrophysics Data System (ADS)

Yoshimoto, Shinya; Takahashi, Kohtaro; Suzuki, Mitsuharu; Yamada, Hiroko; Miyahara, Ryosuke; Mukai, Kozo; Yoshinobu, Jun

2017-08-01

We have studied in-plane anisotropy in the field-effect mobility of solution-processed organic semiconductor 6,13-bis(triisopropylsilylethynyl)pentacene by using independently driven four gallium indium (Ga-In) probes. Liquid-metal Ga-In probes are highly effective for reproducible conductivity measurements of organic thin films. We demonstrated that a high mobility anisotropy of 44 was obtained by using a square four-probe method and a feedback circuit to keep the channel potential constant. The present method minimized the influences of the contact resistance and the insensitivity of anisotropy in a linear arrangement in two-dimensional field-effect transistors.

Iridescent cellulose nanocrystal/polyethylene oxide composite films with low coefficient of thermal expansion

Treesearch

Jairo A. Diaz; Julia L. Braun; Robert J. Moon; Jeffrey P. Youngblood

2015-01-01

Simultaneous control over optical and thermal properties is particularly challenging and highly desired in fields like organic electronics. Here we incorporated cellulose nanocrystals (CNCs) into polyethylene oxide (PEO) in an attempt to preserve the iridescent CNC optical reflection given by their chiral nematic organisation, while reducing the composite thermal...

Electrocrystallization and scanning probe microscopy of ceramic thin films and superlattices

NASA Astrophysics Data System (ADS)

Hung, Chen-Jen

This dissertation presents an investigation of the electrocrystallization and scanning probe microscopy of ceramic thin films and superlattices. All of the films were deposited from aqueous solution at room temperature with no subsequent heat treatment needed to effect crystallization. Thallium(III) oxide defect chemistry superlattices were electrodeposited by pulsing the applied overpotential during deposition. The defect chemistry of the oxide is dependent on the applied overpotential. High overpotentials favor oxygen vacancies, while low overpotentials favor cation interstitials. Nanometer-scale holes were formed in thin thallium(III) oxide films using the scanning tunneling microscope in humid ambient conditions. Both cathodic and anodic etching reactions were performed on this metal oxide surface. The hole formation was attributed to localized electrochemical etching reactions beneath the STM tip. The scanning tunneling microscope (STM) was also used to both induce local surface modifications and image cleaved Pb-Tl-O superlattices. A trench of 100 nm in width, 32 nm in depth, and over 1 μm in length was formed after sweeping a bias voltage of ±2.5 V for 1 minute using a fixed STM tip. It has been suggested that STM results obtained under ambient conditions must be evaluated with great care because of the possibility of localized electrochemcial reactions. A novel synthesis method for the production of Cu(II) oxide from an alkaline solution containing Cu(II) tartrate was developed. Rietveld refinement of the cupric oxide films reveals pure Cu(II) oxide with no Cu(I) oxide present in the film.

Two-photon pumped amplified spontaneous emission based on all-inorganic perovskite nanocrystals embedded with gold nanorods

NASA Astrophysics Data System (ADS)

Liu, Shaoying; Fang, Xiaohui; Wang, Yimeng; Zhang, Xinping

2018-07-01

CsPbBr3 nanocrystals have attracted great interest owing to their high fluorescence quantum efficiency, adjustable photoluminescence wavelength, and good stability. We report a device that consists of disordered gold nanorods underneath a film of CsPbBr3 nanocrystals. Two-photon pumping using femtosecond laser pulses at 800 nm enables amplified spontaneous emission (ASE) at about 523 nm. In this work, a narrow peak with linewidth of 5 nm is observed when the pump fluence reaches a low threshold of 0.65 mJ/cm2. The results show that plasmonic resonance of gold nanorods improves the emission transition rate and enables low threshold ASE.

Solid-state infrared-to-visible upconversion sensitized by colloidal nanocrystals

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

Wu, Mengfei; Congreve, Daniel N.; Wilson, Mark W. B.

2015-11-23

Optical upconversion via sensitized triplet–triplet exciton annihilation converts incoherent low-energy photons to shorter wavelengths under modest excitation intensities1,2,3. Here, we report a solid-state thin film for infrared-to-visible upconversion that employs lead sulphide colloidal nanocrystals as a sensitizer. Upconversion is achieved from pump wavelengths beyond λ = 1 μm to emission at λ = 612 nm. When excited at λ = 808 nm, two excitons in the sensitizer are converted to one higher-energy state in the emitter at a yield of 1.2 ± 0.2%. Peak efficiency is attained at an absorbed intensity equivalent to less than one sun. We demonstrate thatmore » colloidal nanocrystals are an attractive alternative to existing molecular sensitizers, given their small exchange splitting, wide wavelength tunability, broadband infrared absorption, and our transient observations of efficient energy transfer. This solid-state architecture for upconversion may prove useful for enhancing the capabilities of solar cells and photodetectors.« less

Solid-state infrared-to-visible upconversion sensitized by colloidal nanocrystals

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

Wu, Mengfei; Congreve, Daniel N.; Wilson, Mark W. B.

2015-11-23

Optical upconversion via sensitized triplet–triplet exciton annihilation converts incoherent low-energy photons to shorter wavelengths under modest excitation intensities1, 2, 3. Here, we report a solid-state thin film for infrared-to-visible upconversion that employs lead sulphide colloidal nanocrystals as a sensitizer. Upconversion is achieved from pump wavelengths beyond λ = 1 μm to emission at λ = 612 nm. When excited at λ = 808 nm, two excitons in the sensitizer are converted to one higher-energy state in the emitter at a yield of 1.2 ± 0.2%. Peak efficiency is attained at an absorbed intensity equivalent to less than one sun. Wemore » demonstrate that colloidal nanocrystals are an attractive alternative to existing molecular sensitizers, given their small exchange splitting, wide wavelength tunability, broadband infrared absorption, and our transient observations of efficient energy transfer. This solid-state architecture for upconversion may prove useful for enhancing the capabilities of solar cells and photodetectors.« less

Solid-state infrared-to-visible upconversion sensitized by colloidal nanocrystals

NASA Astrophysics Data System (ADS)

Wu, Mengfei; Congreve, Daniel N.; Wilson, Mark W. B.; Jean, Joel; Geva, Nadav; Welborn, Matthew; van Voorhis, Troy; Bulović, Vladimir; Bawendi, Moungi G.; Baldo, Marc A.

2016-01-01

Optical upconversion via sensitized triplet-triplet exciton annihilation converts incoherent low-energy photons to shorter wavelengths under modest excitation intensities. Here, we report a solid-state thin film for infrared-to-visible upconversion that employs lead sulphide colloidal nanocrystals as a sensitizer. Upconversion is achieved from pump wavelengths beyond λ = 1 μm to emission at λ = 612 nm. When excited at λ = 808 nm, two excitons in the sensitizer are converted to one higher-energy state in the emitter at a yield of 1.2 ± 0.2%. Peak efficiency is attained at an absorbed intensity equivalent to less than one sun. We demonstrate that colloidal nanocrystals are an attractive alternative to existing molecular sensitizers, given their small exchange splitting, wide wavelength tunability, broadband infrared absorption, and our transient observations of efficient energy transfer. This solid-state architecture for upconversion may prove useful for enhancing the capabilities of solar cells and photodetectors.

CsPbBr3 nanocrystal saturable absorber for mode-locking ytterbium fiber laser

NASA Astrophysics Data System (ADS)

Zhou, Yan; Hu, Zhiping; Li, Yue; Xu, Jianqiu; Tang, Xiaosheng; Tang, Yulong

2016-06-01

Cesium lead halide perovskite nanocrystals (CsPbX3, X = Cl, Br, I) have been reported as efficient light-harvesting and light-emitting semiconductor materials, but their nonlinear optical properties have been seldom touched upon. In this paper, we prepare layered CsPbBr3 nanocrystal films and characterize their physical properties. Broadband linear absorption from ˜0.8 to over 2.2 μm and nonlinear optical absorption at the 1-μm wavelength region are measured. The CsPbBr3 saturable absorber (SA), manufactured by drop-casting of colloidal CsPbBr3 liquid solution on a gold mirror, shows modulation depth and saturation intensity of 13.1% and 10.7 MW/cm2, respectively. With this SA, mode-locking operation of a polarization-maintained ytterbium fiber laser produces single pulses with duration of ˜216 ps, maximum average output power of 10.5 mW, and the laser spectrum is centered at ˜1076 nm. This work shows that CsPbBr3 films can be efficient SA candidates for fiber lasers and also have great potential to become broadband linear and nonlinear optical materials for photonics and optoelectronics.

Preparation methodologies and nano/microstructural evaluation of metal/semiconductor thin films.

PubMed

Chen, Zhiwen; Jiao, Zheng; Wu, Minghong; Shek, Chan-Hung; Wu, C M Lawrence; Lai, Joseph K L

2012-01-01

Metal/semiconductor thin films are a class of unique materials that are widespread technological applications, particularly in the field of microelectronic devices. Assessment strategies of fractal and tures are of fundamental importance in the development of nano/microdevices. This review presents the preparation methodologies and nano/microstructural evaluation of metal/semiconductor thin films including Au/Ge bilayer films and Pd-Ge alloy thin films, which show in the form of fractals and nanocrystals. Firstly, the extended version of Au/Ge thin films for the fractal crystallization of amorphous Ge and the formation of nanocrystals developed with improved micro- and nanostructured features are described in Section 2. Secondly, the nano/microstructural characteristics of Pd/Ge alloy thin films during annealing have been investigated in detail and described in Section 3. Finally, we will draw the conclusions from the present work as shown in Section 4. It is expected that the preparation methodologies developed and the knowledge of nano/microstructural evolution gained in metal/semiconductor thin films, including Au/Ge bilayer films and Pd-Ge alloy thin films, will provide an important fundamental basis underpinning further interdisciplinary research in these fields such as physics, chemistry, materials science, and nanoscience and nanotechnology, leading to promising exciting opportunities for future technological applications involving these thin films.

In Situ Growth of Metal Sulfide Nanocrystals in Poly(3-hexylthiophene): [6,6]-Phenyl C61-Butyric Acid Methyl Ester Films for Inverted Hybrid Solar Cells with Enhanced Photocurrent.

PubMed

Yang, Chunyan; Sun, Yingying; Li, Xinjie; Li, Cheng; Tong, Junfeng; Li, Jianfeng; Zhang, Peng; Xia, Yangjun

2018-06-20

It has been reported that the performance of bulk heterojunction organic solar cells can be improved by incorporation of nano-heterostructures of metals, semiconductors, and dielectric materials in the active layer. In this manuscript, CdS or Sb 2 S 3 nanocrystals were in situ generated inside the poly(3-hexylthiophene): [6,6]-phenyl C61-butyric acid (P3HT:PC 61 BM) system by randomly mixing P3HT and PC 61 BM in the presence of cadmium or antimony xanthate precursor. Hybrid solar cells (HSCs) with the configurations of tin-doped indium oxide substrate (ITO)/CdS interface layer/P3HT:PC 61 BM: x wt.% CdS/MoO 3 /Ag and ITO/CdS interface layer /P3HT:PC 61 BM: x wt.% Sb 2 S 3 /MoO 3 /Ag were fabricated. Hybrid active layers (P3HT:PC 61 BM: x wt.% CdS or P3HT:PC 61 BM: x wt.% Sb 2 S 3 ) were formed completely by thermally annealing the film resulting in the decomposition of the cadmium or antimony xanthate precursor to CdS or Sb 2 S 3 nanocrystals, respectively. The effects of x wt.% CdS (or Sb 2 S 3 ) nanocrystals on the performance of the HSCs were studied. From UV-Vis absorption, hole mobilities, and surface morphological characterizations, it has been proved that incorporation of 3 wt.% CdS (or Sb 2 S 3 ) nanocrystals in the active layer of P3HT:PC 61 BM-based solar cells improved the optical absorption, the hole mobility, and surface roughness in comparison with P3HT:PC 61 BM-based solar cells, thus resulting in the improved power conversion efficiencies (PCEs) of the devices.

Engineering and Probing Topological Properties of Dirac Semimetal Films by Asymmetric Charge Transfer.

PubMed

Villanova, John W; Barnes, Edwin; Park, Kyungwha

2017-02-08

Dirac semimetals (DSMs) have topologically robust three-dimensional Dirac (doubled Weyl) nodes with Fermi-arc states. In heterostructures involving DSMs, charge transfer occurs at the interfaces, which can be used to probe and control their bulk and surface topological properties through surface-bulk connectivity. Here we demonstrate that despite a band gap in DSM films, asymmetric charge transfer at the surface enables one to accurately identify locations of the Dirac-node projections from gapless band crossings and to examine and engineer properties of the topological Fermi-arc surface states connecting the projections, by simulating adatom-adsorbed DSM films using a first-principles method with an effective model. The positions of the Dirac-node projections are insensitive to charge transfer amount or slab thickness except for extremely thin films. By varying the amount of charge transfer, unique spin textures near the projections and a separation between the Fermi-arc states change, which can be observed by gating without adatoms.

Phase transition studies in bismuth ferrite thin films synthesized via spray pyrolysis technique

NASA Astrophysics Data System (ADS)

Goyal, Ankit; Lakhotia, Harish

2013-06-01

Multiferroic are the materials, which combine two or more "ferroic" properties, ferromagnetism, ferroelectricity or ferroelasticity. BiFeO3 is the only single phase multiferroic material which possesses a high Curie temperature (TC ˜ 1103 K), and a high Neel temperature (TN ˜ 643 K) at room temperature. Normally sophisticated methods are being used to deposit thin films but here we have tried a different method Low cost Spray Pyrolysis Method to deposit BiFeO3 thin film of Glass Substrate with rhombohedral crystal structure and R3c space group. Bismuth Ferrite thin films are synthesized using Bismuth Nitrate and Iron Nitrate as precursor solutions. X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) were used to study structural analysis of prepared thin films. XRD pattern shows phase formation of BiFeO3 and SEM analysis shows formation of nanocrystals of 200 nm. High Temperature Resistivity measurements were done by using Keithley Electrometer (Two Probe system). Abrupt behavior in temperature range (313 K - 400K) has been observed in resistance studies which more likely suggests that in this transition the structure is tetragonal rather than rhombohedral. BiFeO3 is the potential active material in the next generation of ferroelectric memory devices.

A Surface Plasmon Resonance-Based Optical Fiber Probe Fabricated with Electropolymerized Molecular Imprinting Film for Melamine Detection

PubMed Central

Zheng, Yongping; Zhang, Tingwei; Wu, Songjie; Zhang, Jue; Fang, Jing

2018-01-01

Molecularly imprinted polymer (MIP) films prepared by bulk polymerization suffer from numerous deficiencies, including poor mass transfer ability and difficulty in controlling reaction rate and film thickness, which usually result in poor repeatability. However, polymer film synthesized by electropolymerization methods benefit from high reproducibility, simplicity and rapidity of preparation. In the present study, an Au film served as the refractive index-sensitive metal film to couple with the light leaked out from optical fiber core and the electrode for electropolymerizing MIP film simultaneously. The manufactured probe exhibited satisfactory sensitivity and specificity. Furthermore, the surface morphology and functional groups of the synthesized MIP film were characterized by Atomic Force Microscopy (AFM) and Fourier transform infrared microspectroscopy (FTIR) for further insights into the adsorption and desorption processes. Given the low cost, label-free test, simple preparation process and fast response, this method has a potential application to monitor substances in complicated real samples for out-of-lab test in the future. PMID:29522472

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

Linearly arranged polytypic CZTSSe nanocrystals

PubMed Central

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

2012-01-01

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

Glass transition in thin supported polystyrene films probed by temperature-modulated ellipsometry in vacuum.

PubMed

Efremov, Mikhail Yu; Kiyanova, Anna V; Last, Julie; Soofi, Shauheen S; Thode, Christopher; Nealey, Paul F

2012-08-01

Glass transition in thin (1-200 nm thick) spin-cast polystyrene films on silicon surfaces is probed by ellipsometry in a controlled vacuum environment. A temperature-modulated modification of the method is used alongside a traditional linear temperature scan. A clear glass transition is detected in films with thicknesses as low as 1-2 nm. The glass transition temperature (T(g)) shows no substantial dependence on thickness for coatings greater than 20 nm. Thinner films demonstrate moderate T(g) depression achieving 18 K for thicknesses 4-7 nm. Less than 4 nm thick samples are excluded from the T(g) comparison due to significant thickness nonuniformity (surface roughness). The transition in 10-20 nm thick films demonstrates excessive broadening. For some samples, the broadened transition is clearly resolved into two separate transitions. The thickness dependence of the glass transition can be well described by a simple 2-layer model. It is also shown that T(g) depression in 5 nm thick films is not sensitive to a wide range of experimental factors including molecular weight characteristics of the polymer, specifications of solvent used for spin casting, substrate composition, and pretreatment of the substrate surface.

Redox Potentials of Colloidal n-Type ZnO Nanocrystals: Effects of Confinement, Electron Density, and Fermi-Level Pinning by Aldehyde Hydrogenation.

PubMed

Carroll, Gerard M; Schimpf, Alina M; Tsui, Emily Y; Gamelin, Daniel R

2015-09-02

Electronically doped colloidal semiconductor nanocrystals offer valuable opportunities to probe the new physical and chemical properties imparted by their excess charge carriers. Photodoping is a powerful approach to introducing and controlling free carrier densities within free-standing colloidal semiconductor nanocrystals. Photoreduced (n-type) colloidal ZnO nanocrystals possessing delocalized conduction-band (CB) electrons can be formed by photochemical oxidation of EtOH. Previous studies of this chemistry have demonstrated photochemical electron accumulation, in some cases reaching as many as >100 electrons per ZnO nanocrystal, but in every case examined to date this chemistry maximizes at a well-defined average electron density of ⟨Nmax⟩ ≈ (1.4 ± 0.4) × 10(20) cm(-3). The origins of this maximum have never been identified. Here, we use a solvated redox indicator for in situ determination of reduced ZnO nanocrystal redox potentials. The Fermi levels of various photodoped ZnO nanocrystals possessing on average just one excess CB electron show quantum-confinement effects, as expected, but are >600 meV lower than those of the same ZnO nanocrystals reduced chemically using Cp*2Co, reflecting important differences between their charge-compensating cations. Upon photochemical electron accumulation, the Fermi levels become independent of nanocrystal volume at ⟨N⟩ above ∼2 × 10(19) cm(-3), and maximize at ⟨Nmax⟩ ≈ (1.6 ± 0.3) × 10(20) cm(-3). This maximum is proposed to arise from Fermi-level pinning by the two-electron/two-proton hydrogenation of acetaldehyde, which reverses the EtOH photooxidation reaction.

Intracellular delivery of peptide nucleic acid and organic molecules using zeolite-L nanocrystals.

PubMed

Bertucci, Alessandro; Lülf, Henning; Septiadi, Dedy; Manicardi, Alex; Corradini, Roberto; De Cola, Luisa

2014-11-01

The design and synthesis of smart nanomaterials can provide interesting potential applications for biomedical purposes from bioimaging to drug delivery. Manufacturing multifunctional systems in a way to carry bioactive molecules, like peptide nucleic acids able to recognize specific targets in living cells, represents an achievement towards the development of highly selective tools for both diagnosis and therapeutics. This work describes a very first example of the use of zeolite nanocrystals as multifunctional nanocarriers to deliver simultaneously PNA and organic molecules into living cells. Zeolite-L nanocrystals are functionalized by covalently attaching the PNA probes onto the surface, while the channel system is filled with fluorescent guest molecules. The cellular uptake of the PNA/Zeolite-L hybrid material is then significantly increased by coating the whole system with a thin layer of biodegradable poly-L-lysine. The delivery of DAPI as a model drug molecule, inserted into the zeolite pores, is also demonstrated to occur in the cells, proving the multifunctional ability of the system. Using this zeolite nanosystem carrying PNA probes designed to target specific RNA sequences of interest in living cells could open new possibilities for theranostic and gene therapy applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Numerical model of a single nanocrystal devoted to the study of disordered nanocrystal floating gates of new flash memories

NASA Astrophysics Data System (ADS)

Leroy, Yann; Armeanu, Dumitru; Cordan, Anne-Sophie

2011-05-01

The improvement of our model concerning a single nanocrystal that belongs to a nanocrystal floating gate of a flash memory is presented. In order to extend the gate voltage range applicability of the model, the 3D continuum of states of either metallic or semiconducting electrodes is discretized into 2D subbands. Such an approach gives precise information about the mechanisms behind the charging or release processes of the nanocrystal. Then, the self-energy and screening effects of an electron within the nanocrystal are evaluated and introduced in the model. This enables a better determination of the operating point of the nanocrystal memory. The impact of those improvements on the charging or release time of the nanocrystal is discussed.

Solution-Processed Solar Cells via Nanocrystal Inks and Molecular Solutions

NASA Astrophysics Data System (ADS)

Miskin, Caleb K.

On February 15, 2008 the National Academy of Engineering unveiled their fourteen grand challenges of engineering for the 21st century. At the top of the list and voted by the public as the most important challenge was the thrust to make solar energy economical. My research has been dedicated to solving this millennial challenge by developing routes to high-efficiency, solution-processed photovoltaics (PV) for low-cost and low-energy manufacturing. My research has primarily advanced two methods for solution processed PV. In one method, semiconducting nanocrystals are synthesized and then suspended in an appropriate solvent to form an ink. The ink is then applied to a substrate by a variety of high-throughput methods such as spray coating or doctor blading and then annealed to form a polycrystalline absorber layer for solar energy. I have applied this method with great success to Cu2ZnSnS 4, a promising earth-abundant, non-toxic semiconductor. A challenge with this material is its propensity to form binary and ternary undesired phases. Using advanced nano-characterization techniques, my colleagues and I have been able to determine the spatially resolved composition of these nanoparticles and have found them to be highly non-uniform. In addition, I developed synthesis techniques aimed at controlling the nucleation and growth of this material to improve nanocrystal compositional homogeneity. Though particles produced in this work still exhibit some non-uniformities, they are greatly improved. When combined with optimized fabrication techniques, I have been able to advance the efficiency of nanocrystal ink based solar cells of CZTS from 7.2 to 9.0 percent in our lab. Another promising route to solution-processed PV is by directly coating molecular precursor solutions (rather than first forming nanocrystals) and annealing the coating to form the polycrystalline solar absorber layer. Unfortunately, a major challenge is that many metals, metal salts, and chalcogens that

Connecting the Particles in the Box - Controlled Fusion of Hexamer Nanocrystal Clusters within an AB6 Binary Nanocrystal Superlattice

PubMed Central

Treml, Benjamin E.; Lukose, Binit; Clancy, Paulette; Smilgies, Detlef-M; Hanrath, Tobias

2014-01-01

Binary nanocrystal superlattices present unique opportunities to create novel interconnected nanostructures by partial fusion of specific components of the superlattice. Here, we demonstrate the binary AB6 superlattice of PbSe and Fe2O3 nanocrystals as a model system to transform the central hexamer of PbSe nanocrystals into a single fused particle. We present detailed structural analysis of the superlattices by combining high-resolution X-ray scattering and electron microscopy. Molecular dynamics simulations show optimum separation of nanocrystals in agreement with the experiment and provide insights into the molecular configuration of surface ligands. We describe the concept of nanocrystal superlattices as a versatile ‘nanoreactor' to create and study novel materials based on precisely defined size, composition and structure of nanocrystals into a mesostructured cluster. We demonstrate ‘controlled fusion' of nanocrystals in the clusters in reactions initiated by thermal treatment and pulsed laser annealing. PMID:25339169

The Surface Chemistry of Metal Chalcogenide Nanocrystals

NASA Astrophysics Data System (ADS)

Anderson, Nicholas Charles

The surface chemistry of metal chalcogenide nanocrystals is explored through several interrelated analytical investigations. After a brief discussion of the nanocrystal history and applications, molecular orbital theory is used to describe the electronic properties of semiconductors, and how these materials behave on the nanoscale. Quantum confinement plays a major role in dictating the optical properties of metal chalcogenide nanocrystals, however surface states also have an equally significant contribution to the electronic properties of nanocrystals due to the high surface area to volume ratio of nanoscale semiconductors. Controlling surface chemistry is essential to functionalizing these materials for biological imaging and photovoltaic device applications. To better understand the surface chemistry of semiconducting nanocrystals, three competing surface chemistry models are presented: 1.) The TOPO model, 2.) the Non-stoichiometric model, and 3.) the Neutral Fragment model. Both the non-stoichiometric and neutral fragment models accurately describe the behavior of metal chalcogenide nanocrystals. These models rely on the covalent bond classification system, which divides ligands into three classes: 1.) X-type, 1-electron donating ligands that balance charge with excess metal at the nanocrystal surface, 2.) L-type, 2-electron donors that bind metal sites, and 3.) Z-type, 2-electron acceptors that bind chalcogenide sites. Each of these ligand classes is explored in detail to better understand the surface chemistry of metal chalcogenide nanocrystals. First, chloride-terminated, tri-n-butylphosphine (Bu 3P) bound CdSe nanocrystals were prepared by cleaving carboxylate ligands from CdSe nanocrystals with chlorotrimethylsilane in Bu3P solution. 1H and 31P{1H} nuclear magnetic resonance spectra of the isolated nanocrystals allowed assignment of distinct signals from several free and bound species, including surface-bound Bu3P and [Bu3P-H]+[Cl]- ligands as well as a Bu

Composite material including nanocrystals and methods of making

DOEpatents

Bawendi, Moungi G.; Sundar, Vikram C.

2010-04-06

Temperature-sensing compositions can include an inorganic material, such as a semiconductor nanocrystal. The nanocrystal can be a dependable and accurate indicator of temperature. The intensity of emission of the nanocrystal varies with temperature and can be highly sensitive to surface temperature. The nanocrystals can be processed with a binder to form a matrix, which can be varied by altering the chemical nature of the surface of the nanocrystal. A nanocrystal with a compatibilizing outer layer can be incorporated into a coating formulation and retain its temperature sensitive emissive properties.

Composite material including nanocrystals and methods of making

DOEpatents

Bawendi, Moungi G [Boston, MA; Sundar, Vikram C [New York, NY

2008-02-05

Temperature-sensing compositions can include an inorganic material, such as a semiconductor nanocrystal. The nanocrystal can be a dependable and accurate indicator of temperature. The intensity of emission of the nanocrystal varies with temperature and can be highly sensitive to surface temperature. The nanocrystals can be processed with a binder to form a matrix, which can be varied by altering the chemical nature of the surface of the nanocrystal. A nanocrystal with a compatibilizing outer layer can be incorporated into a coating formulation and retain its temperature sensitive emissive properties

Quantum confinement of nanocrystals within amorphous matrices

NASA Astrophysics Data System (ADS)

Lusk, Mark T.; Collins, Reuben T.; Nourbakhsh, Zahra; Akbarzadeh, Hadi

2014-02-01

Nanocrystals encapsulated within an amorphous matrix are computationally analyzed to quantify the degree to which the matrix modifies the nature of their quantum-confinement power—i.e., the relationship between nanocrystal size and the gap between valence- and conduction-band edges. A special geometry allows exactly the same amorphous matrix to be applied to nanocrystals of increasing size to precisely quantify changes in confinement without the noise typically associated with encapsulating structures that are different for each nanocrystal. The results both explain and quantify the degree to which amorphous matrices redshift the character of quantum confinement. The character of this confinement depends on both the type of encapsulating material and the separation distance between the nanocrystals within it. Surprisingly, the analysis also identifies a critical nanocrystal threshold below which quantum confinement is not possible—a feature unique to amorphous encapsulation. Although applied to silicon nanocrystals within an amorphous silicon matrix, the methodology can be used to accurately analyze the confinement softening of other amorphous systems as well.

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

PubMed

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

2014-01-28

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

Photoluminescence of ZnS-SiO2:Ce Thin Films Deposited by Magnetron Sputtering

NASA Astrophysics Data System (ADS)

Mizuno, Masao

2011-12-01

Photoluminescent emissions of zinc sulfide-silica-cerium thin films deposited by magnetron sputtering were observed. The films consisted of ZnS nanocrystals embedded in amorphous SiO2 matrices. ZnS-SiO2:Ce films exhibited photoluminescence even without postannealing. Their emission spectra showed broad patterns in the visible range; the emitted colors depended on film composition.

Nanocrystal/sol-gel nanocomposites

DOEpatents

Petruska, Melissa A [Los Alamos, NM; Klimov, Victor L [Los Alamos, NM

2007-06-05

The present invention is directed to solid composites including colloidal nanocrystals within a sol-gel host or matrix and to processes of forming such solid composites. The present invention is further directed to alcohol soluble colloidal nanocrystals useful in formation of sol-gel based solid composites.

Nanocrystal/sol-gel nanocomposites

DOEpatents

Petruska, Melissa A [Los Alamos, NM; Klimov, Victor L [Los Alamos, NM

2012-06-12

The present invention is directed to solid composites including colloidal nanocrystals within a sol-gel host or matrix and to processes of forming such solid composites. The present invention is further directed to alcohol soluble colloidal nanocrystals useful in formation of sol-gel based solid composites

Laser irradiation of carbon nanotube films: Effects and heat dissipation probed by Raman spectroscopy

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

Mialichi, J. R.; Brasil, M. J. S. P.; Iikawa, F.

We investigate the thermal properties of thin films formed by single- and multi-walled carbon nanotubes submitted to laser irradiation using Raman scattering as a probe of both the tube morphology and the local temperature. The nanotubes were submitted to heating/cooling cycles attaining high laser intensities ({approx}1.4 MW/cm{sup 2}) under vacuum and in the presence of an atmosphere, with and without oxygen. We investigate the heat diffusion of the irradiated nanotubes to their surroundings and the effect of laser annealing on their properties. The presence of oxygen during laser irradiation gives rise to an irreversible increase of the Raman efficiency ofmore » the carbon nanotubes and to a remarkable increase of the thermal conductivity of multi-walled films. The second effect can be applied to design thermal conductive channels in devices based on carbon nanotube films using laser beams.« less

Probing Dynamically Tunable Localized Surface Plasmon Resonances of Film-Coupled Nanoparticles by Evanescent Wave Excitation

PubMed Central

Mock, Jack J.; Hill, Ryan T.; Tsai, Yu-Ju; Chilkoti, Ashutosh; Smith, David R.

2012-01-01

The localized surface plasmon resonance (LSPR) spectrum associated with a gold nanoparticle (NP) coupled to a gold film exhibits extreme sensitivity to the nano-gap region where the fields are tightly localized. The LSPR of an ensemble of film-coupled NPs can be observed using an illumination scheme similar to that used to excite the surface plasmon resonance (SPR) of a thin metallic film; however, in the present system, the light is used to probe the highly sensitive distance-dependent LSPR of the gaps between NPs and film rather than the delocalized SPR of the film. We show that the SPR and LSPR spectral contributions can be readily distinguished, and we compare the sensitivities of both modes to displacements in the average gap between a collection of NPs and the gold film. The distance by which the NPs are suspended in solution above the gold film is fixed via a thin molecular spacer layer, and can be further modulated by subjecting the NPs to a quasistatic electric field. The observed LSPR spectral shifts triggered by the applied voltage can be correlated with Angstrom scale displacements of the NPs, suggesting the potential for chip-scale or flow-cell plasmonic nanoruler devices with extreme sensitivity. PMID:22429053

Colloidal inorganic nanocrystals: Nucleation, growth and biological applications

NASA Astrophysics Data System (ADS)

Lynch, Jared James

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

Calcination does not remove all carbon from colloidal nanocrystal assemblies

DOE PAGES

Mohapatra, Pratyasha; Shaw, Santosh; Mendivelso-Perez, Deyny; ...

2017-12-11

Removing organics from hybrid nanostructures is a crucial step in many bottom-up materials fabrication approaches. It is usually assumed that calcination is an effective solution to this problem, especially for thin films. This assumption has led to its application in thousands of papers. Here in this paper, we show that this general assumption is incorrect by using a relevant and highly controlled model system consisting of thin films of ligand-capped ZrO 2 nanocrystals. After calcination at 800 °C for 12 h, while Raman spectroscopy fails to detect the ligands after calcination, elastic backscattering spectrometry characterization demonstrates that ~18% of themore » original carbon atoms are still present in the film. By comparison plasma processing successfully removes the ligands. Our growth kinetic analysis shows that the calcined materials have significantly different interfacial properties than the plasma-processed counterparts. Calcination is not a reliable strategy for the production of single-phase all-inorganic materials from colloidal nanoparticles.« 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.

Synthesis and Characterizations of Novel Ca-Mg-Ti-Fe-Oxides Based Ceramic Nanocrystals and Flexible Film of Polydimethylsiloxane Composite with Improved Mechanical and Dielectric Properties for Sensors

PubMed Central

Tripathy, Ashis; Pramanik, Sumit; Manna, Ayan; Azrin Shah, Nabila Farhana; Shasmin, Hanie Nadia; Radzi, Zamri; Abu Osman, Noor Azuan

2016-01-01

Armalcolite, a rare ceramic mineral and normally found in the lunar earth, was synthesized by solid-state step-sintering. The in situ phase-changed novel ceramic nanocrystals of Ca-Mg-Ti-Fe based oxide (CMTFOx), their chemical reactions and bonding with polydimethylsiloxane (PDMS) were determined by X-ray diffraction, infrared spectroscopy, and microscopy. Water absorption of all the CMTFOx was high. The lower dielectric loss tangent value (0.155 at 1 MHz) was obtained for the ceramic sintered at 1050 °C (S1050) and it became lowest for the S1050/PDMS nanocomposite (0.002 at 1 MHz) film, which was made by spin coating at 3000 rpm. The excellent flexibility (static modulus ≈ 0.27 MPa and elongation > 90%), viscoelastic property (tanδ = E″/E′: 0.225) and glass transition temperature (Tg: −58.5 °C) were obtained for S1050/PDMS film. Parallel-plate capacitive and flexible resistive humidity sensors have been developed successfully. The best sensing performance of the present S1050 (3000%) and its flexible S1050/PDMS composite film (306%) based humidity sensors was found to be at 100 Hz, better than conventional materials. PMID:26927116

Synthesis and Characterizations of Novel Ca-Mg-Ti-Fe-Oxides Based Ceramic Nanocrystals and Flexible Film of Polydimethylsiloxane Composite with Improved Mechanical and Dielectric Properties for Sensors.

PubMed

Tripathy, Ashis; Pramanik, Sumit; Manna, Ayan; Shah, Nabila Farhana Azrin; Shasmin, Hanie Nadia; Radzi, Zamri; Abu Osman, Noor Azuan

2016-02-27

Armalcolite, a rare ceramic mineral and normally found in the lunar earth, was synthesized by solid-state step-sintering. The in situ phase-changed novel ceramic nanocrystals of Ca-Mg-Ti-Fe based oxide (CMTFOx), their chemical reactions and bonding with polydimethylsiloxane (PDMS) were determined by X-ray diffraction, infrared spectroscopy, and microscopy. Water absorption of all the CMTFOx was high. The lower dielectric loss tangent value (0.155 at 1 MHz) was obtained for the ceramic sintered at 1050 °C (S1050) and it became lowest for the S1050/PDMS nanocomposite (0.002 at 1 MHz) film, which was made by spin coating at 3000 rpm. The excellent flexibility (static modulus ≈ 0.27 MPa and elongation > 90%), viscoelastic property (tanδ = E″/E': 0.225) and glass transition temperature (Tg: -58.5 °C) were obtained for S1050/PDMS film. Parallel-plate capacitive and flexible resistive humidity sensors have been developed successfully. The best sensing performance of the present S1050 (3000%) and its flexible S1050/PDMS composite film (306%) based humidity sensors was found to be at 100 Hz, better than conventional materials.

Vacuum ellipsometry as a method for probing glass transition in thin polymer films.

PubMed

Efremov, Mikhail Yu; Soofi, Shauheen S; Kiyanova, Anna V; Munoz, Claudio J; Burgardt, Peter; Cerrina, Franco; Nealey, Paul F

2008-04-01

A vacuum ellipsometer has been designed for probing the glass transition in thin supported polymer films. The device is based on the optics of a commercial spectroscopic phase-modulated ellipsometer. A custom-made vacuum chamber evacuated by oil-free pumps, variable temperature optical table, and computer-based data acquisition system was described. The performance of the tool has been demonstrated using 20-200 nm thick poly(methyl methacrylate) and polystyrene films coated on silicon substrates at 10(-6)-10(-8) torr residual gas pressure. Both polymers show pronounced glass transitions. The difficulties in assigning in the glass transition temperature are discussed with respect to the experimental challenges of the measurements in thin polymer films. It is found that the experimental curves can be significantly affected by a residual gas. This effect manifests itself at lower temperatures as a decreased or even negative apparent thermal coefficient of expansion, and is related to the uptake and desorption of water by the samples during temperature scans. It is also found that an ionization gauge--the standard accessory of any high vacuum system--can cause a number of spurious phenomena including drift in the experimental data, roughening of the polymer surface, and film dewetting.

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

NASA Astrophysics Data System (ADS)

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

2015-07-01

The rational design of monodisperse ferroelectric nanocrystals with controlled size and shape and their organization into hierarchical structures has been a critical step for understanding the polar ordering in nanoscale ferroelectrics, as well as the design of nanocrystal-based functional materials which harness the properties of individual nanoparticles and the collective interactions between them. We report here on the synthesis and self-assembly of aggregate-free, single-crystalline titanium-based perovskite nanoparticles with controlled morphology and surface composition by using a simple, easily scalable and highly versatile colloidal route. Single-crystalline, non-aggregated BaTiO3 colloidal nanocrystals, used as a model system, have been prepared under solvothermal conditions at temperatures as low as 180 °C. The shape of the nanocrystals was tuned from spheroidal to cubic upon changing the polarity of the solvent, whereas their size was varied from 16 to 30 nm for spheres and 5 to 78 nm for cubes by changing the concentration of the precursors and the reaction time, respectively. The hydrophobic, oleic acid-passivated nanoparticles exhibit very good solubility in non-polar solvents and can be rendered dispersible in polar solvents by a simple process involving the oxidative cleavage of the double bond upon treating the nanopowders with the Lemieux-von Rudloff reagent. Lattice dynamic analysis indicated that regardless of their size, BaTiO3 nanocrystals present local disorder within the perovskite unit cell, associated with the existence of polar ordering. We also demonstrate for the first time that, in addition to being used for fabricating large area, crack-free, highly uniform films, BaTiO3 nanocubes can serve as building blocks for the design of 2D and 3D mesoscale structures, such as superlattices and superparticles. Interestingly, the type of superlattice structure (simple cubic or face centered cubic) appears to be determined by the type of solvent

Electronic displays using optically pumped luminescent semiconductor nanocrystals

DOEpatents

Weiss, Shimon; Schlamp, Michael C.; Alivisatos, A. Paul

2010-04-13

A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit light of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

Electronic displays using optically pumped luminescent semiconductor nanocrystals

DOEpatents

Weiss, Shimon; Schlamp, Michael C.; Alivisatos, A. Paul

2005-03-08

A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit light of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

Electronic displays using optically pumped luminescent semiconductor nanocrystals

DOEpatents

Weiss, Shimon; Schlamp, Michael C.; Alivisatos, A. Paul

2015-06-23

A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit light of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

Electronic displays using optically pumped luminescent semiconductor nanocrystals

DOEpatents

Weiss, Shimon; Schlamp, Michael C; Alivisatos, A. Paul

2014-02-11

A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit light of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

Electronic displays using optically pumped luminescent semiconductor nanocrystals

DOEpatents

Weiss, Shimon; Schlamp, Michael C.; Alivisatos, Paul A.

2015-11-10

A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit tight of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

Electronic displays using optically pumped luminescent semiconductor nanocrystals

DOEpatents

Weiss, Shimon [Pinole, CA; Schlamp, Michael C [Plainsboro, NJ; Alivisatos, A Paul [Oakland, CA

2011-09-27

A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit light of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

Electronic displays using optically pumped luminescent semiconductor nanocrystals

DOEpatents

Weiss, Shimon; Schlam, Michael C; Alivisatos, A. Paul

2014-03-25

A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit tight of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

Electronic displays using optically pumped luminescent semiconductor nanocrystals

DOEpatents

Weiss, Shimon; Schlamp, Michael C.; Alivisatos, A. Paul

2017-06-06

A multicolor electronic display is based on an array of luminescent semiconductor nanocrystals. Nanocrystals which emit tight of different colors are grouped into pixels. The nanocrystals are optically pumped to produce a multicolor display. Different sized nanocrystals are used to produce the different colors. A variety of pixel addressing systems can be used.

Charge transport in metal oxide nanocrystal-based materials

NASA Astrophysics Data System (ADS)

Runnerstrom, Evan Lars

There is probably no class of materials more varied, more widely used, or more ubiquitous than metal oxides. Depending on their composition, metal oxides can exhibit almost any number of properties. Of particular interest are the ways in which charge is transported in metal oxides: devices such as displays, touch screens, and smart windows rely on the ability of certain metal oxides to conduct electricity while maintaining visible transparency. Smart windows, fuel cells, and other electrochemical devices additionally rely on efficient transport of ionic charge in and around metal oxides. Colloidal synthesis has enabled metal oxide nanocrystals to emerge as a relatively new but highly tunable class of materials. Certain metal oxide nanocrystals, particularly highly doped metal oxides, have been enjoying rapid development in the last decade. As in myriad other materials systems, structure dictates the properties of metal oxide nanocrystals, but a full understanding of how nanocrystal synthesis, the processing of nanocrystal-based materials, and the structure of nanocrystals relate to the resulting properties of nanocrystal-based materials is still nascent. Gaining a fundamental understanding of and control over these structure-property relationships is crucial to developing a holistic understanding of metal oxide nanocrystals. The unique ability to tune metal oxide nanocrystals by changing composition through the introduction of dopants or by changing size and shape affords a way to study the interplay between structure, processing, and properties. This overall goal of this work is to chemically synthesize colloidal metal oxide nanocrystals, process them into useful materials, characterize charge transport in materials based on colloidal metal oxide nanocrystals, and develop ways to manipulate charge transport. In particular, this dissertation characterizes how the charge transport properties of metal oxide nanocrystal-based materials depend on their processing and

Copper Selenide Nanocrystals for Photothermal Therapy

PubMed Central

Hessel, Colin M.; Pattani, Varun; Rasch, Michael; Panthani, Matthew G.; Koo, Bonil; Tunnell, James W.; Korgel, Brian A.

2011-01-01

Ligand-stabilized copper selenide (Cu2−xSe) nanocrystals, approximately 16 nm in diameter, were synthesized by a colloidal hot injection method and coated with amphiphilic polymer. The nanocrystals readily disperse in water and exhibit strong near infrared (NIR) optical absorption with a high molar extinction coefficient of 7.7 × 107 cm−1 M−1 at 980 nm. When excited with 800 nm light, the Cu2−xSe nanocrystals produce significant photothermal heating with a photothermal transduction efficiency of 22%, comparable to nanorods and nanoshells of gold (Au). In vitro photothermal heating of Cu2−xSe nanocrystals in the presence of human colorectal cancer cell (HCT-116) led to cell destruction after 5 minutes of laser irradiation at 33 W/cm2, demonstrating the viabilitiy of Cu2−xSe nanocrystals for photothermal therapy applications. PMID:21553924

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

Development Considerations for Nanocrystal Drug Products.

PubMed

Chen, Mei-Ling; John, Mathew; Lee, Sau L; Tyner, Katherine M

2017-05-01

Nanocrystal technology has emerged as a valuable tool for facilitating the delivery of poorly water-soluble active pharmaceutical ingredients (APIs) and enhancing API bioavailability. To date, the US Food and Drug Administration (FDA) has received over 80 applications for drug products containing nanocrystals. These products can be delivered by different routes of administration and are used in a variety of therapeutic areas. To aid in identifying key developmental considerations for these products, a retrospective analysis was performed on the submissions received by the FDA to date. Over 60% of the submissions were for the oral route of administration. Based on the Biopharmaceutics Classification System (BCS), most nanocrystal drugs submitted to the FDA are class II compounds that possess low aqueous solubility and high intestinal permeability. Impact of food on drug bioavailability was reduced for most nanocrystal formulations as compared with their micronized counterparts. For all routes of administration, dose proportionality was observed for some, but not all, nanocrystal products. Particular emphasis in the development of nanocrystal products was placed on the in-process tests and controls at critical manufacturing steps (such as milling process), mitigation and control of process-related impurities, and the stability of APIs or polymorphic form (s) during manufacturing and upon storage. This emphasis resulted in identifying challenges to the development of these products including accurate determination of particle size (distribution) of drug substance and/or nanocrystal colloidal dispersion, identification of polymorphic form (s), and establishment of drug substance/product specifications.

Cellulose nanocrystals: synthesis, functional properties, and applications

PubMed Central

George, Johnsy; Sabapathi, SN

2015-01-01

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

Hydrothermal synthesis of tungsten doped tin dioxide nanocrystals

NASA Astrophysics Data System (ADS)

Zhou, Cailong; Li, Yufeng; Chen, Yiwen; Lin, Jing

2018-01-01

Tungsten doped tin dioxide (WTO) nanocrystals were synthesized through a one-step hydrothermal method. The structure, composition and morphology of WTO nanocrystals were characterized by x-ray diffraction, x-ray photoelectron spectroscopy, energy dispersive x-ray spectroscopy, UV-vis diffuse reflectance spectra, zeta potential analysis and high-resolution transmission electron microscopy. Results show that the as-prepared WTO nanocrystals were rutile-type structure with the size near 13 nm. Compared with the undoped tin dioxide nanocrystals, the WTO nanocrystals possessed better dispersity in ethanol phase and formed transparent sol.

Simulation of ultraviolet- and soft X-ray-pulse generation as a result of cooperative recombination of excitons in diamond nanocrystals embedded in a polymer film

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

Kukushkin, V. A., E-mail: vakuk@appl.sci-nnov.ru

2013-11-15

Using numerical simulation, it is shown that the recombination of free excitons photoexcited in diamond nanocrystals embedded in a polymer film can occur in the cooperative mode. It is found that this mode can be implemented despite the fact that diamond is an 'indirect' semiconductor. It is shown that the power of the generated radiation at the pulse peak during the cooperative recombination of free excitons can exceed that of the incoherent spontaneous emission of the same initial number of free excitons by more than an order of magnitude. Finally, it is shown that the process under consideration can bemore » used to generate picosecond pulses of ultraviolet and soft X-ray electromagnetic field at a wavelength of 235 nm.« less

Multifunctional Polypeptide EQCN Sensors: Probing the Cysteamine-Glutathione Film Permeability with Hg(II) Ions

PubMed Central

Hepel, Maria; Dallas, Julia

2008-01-01

Multifunctional films are the basis of biosensors and play an important role in the emerging field of nanobioelectronics. In this work, films of a tripeptide glutathione (GSH) immobilized on a self-assembled monolayer of cysteamine (CA-SAM) on a quartz crystal Au piezosensor have been synthesized and characterized using electrochemical quartz crystal nanogravimetry (EQCN) with a Hg(II) ion probe. It has been found that in contrast to previously studied Au/GSH films, the Au/CA-GSH films strongly hinder the formation of Hg0 with bulk properties while still allowing for relatively easy permeation by Hg(II) ions. This results in complete disappearance of the sharp Hg0 electrodissolution peak which is observed on bare Au and Au/GSH piezosensors. The multiple-peak anodic behavior of Au/CA and bare Au is replaced by a single high-field anodic peak of mercury reoxidation in the case of Au/CA-GSH sensors. The mass-to-charge plots indicate predominant ingress/egress of Hg(II) to/from the film. The strong hindrance of CA-SAM to bulk-Hg0 formation is attributed to film-stabilizing formation of surface (CA)2Hg2+ complexes with conformation evaluated by ab initio quantum mechanical calculations of electronic structure using Hartree-Fock methods. The associates CA-GSH provide an additional functionality of the side sulfhydryl group which is free for interactions, e.g. with heavy metals. It is proposed that in the film, the CA-GSH molecules can assume open (extended) conformation or bent hydrogen-bonded conformation with up to four possible internal hydrogen bonds. PMID:27873925

Measuring the reactivity of a silicon-terminated probe

NASA Astrophysics Data System (ADS)

Sweetman, Adam; Stirling, Julian; Jarvis, Samuel Paul; Rahe, Philipp; Moriarty, Philip

2016-09-01

It is generally accepted that the exposed surfaces of silicon crystals are highly reactive due to the dangling bonds which protrude into the vacuum. However, surface reconstruction not only modifies the reactivity of bulk silicon crystals, but also plays a key role in determining the properties of silicon nanocrystals. In this study we probe the reactivity of silicon clusters at the end of a scanning probe tip by examining their interaction with closed-shell fullerene molecules. Counter to intuitive expectations, many silicon clusters do not react strongly with the fullerene cage, and we find that only specific highly oriented clusters have sufficient reactivity to break open the existing carbon-carbon bonds.

Optical determination of crystal phase in semiconductor nanocrystals

PubMed Central

Lim, Sung Jun; Schleife, André; Smith, Andrew M.

2017-01-01

Optical, electronic and structural properties of nanocrystals fundamentally derive from crystal phase. This is especially important for polymorphic II–VI, III–V and I-III-VI2 semiconductor materials such as cadmium selenide, which exist as two stable phases, cubic and hexagonal, each with distinct properties. However, standard crystallographic characterization through diffraction yields ambiguous phase signatures when nanocrystals are small or polytypic. Moreover, diffraction methods are low-throughput, incompatible with solution samples and require large sample quantities. Here we report the identification of unambiguous optical signatures of cubic and hexagonal phases in II–VI nanocrystals using absorption spectroscopy and first-principles electronic-structure theory. High-energy spectral features allow rapid identification of phase, even in small nanocrystals (∼2 nm), and may help predict polytypic nanocrystals from differential phase contributions. These theoretical and experimental insights provide simple and accurate optical crystallographic analysis for liquid-dispersed nanomaterials, to improve the precision of nanocrystal engineering and improve our understanding of nanocrystal reactions. PMID:28513577

Method of synthesizing pyrite nanocrystals

DOEpatents

Wadia, Cyrus; Wu, Yue

2013-04-23

A method of synthesizing pyrite nanocrystals is disclosed which in one embodiment includes forming a solution of iron (III) diethyl dithiophosphate and tetra-alkyl-ammonium halide in water. The solution is heated under pressure. Pyrite nanocrystal particles are then recovered from the solution.

Characterizing the local optoelectronic performance of organic solar cells with scanning-probe microscopy

NASA Astrophysics Data System (ADS)

Coffey, David C.

2007-12-01

Conjugated polymers, small molecules, and colloidal semiconductor nanocrystals are promising materials for use in low-cost, thin-film solar cells. The photovoltaic performance of these materials, however, is highly dependent on film structure, and directly correlating local film structures with device performance remains challenging. This dissertation describes several techniques we have developed to probe and control the local optoelectronic properties of organic semiconducting films. First, with an aim of rapidly fabricating photovoltaic films with varying morphology, we demonstrate that Dip-Pen Nanolithography (DPN) can be used to control nanoscale phase separation with sub-150 nm lateral resolution in polymer films that are 20--80 nm thick. This control is based on writing monolayer chemical templates that nucleate phase separation, and we use this technique to study heterogeneous nucleation in thin films. Second, we use time-resolved electrostatic force microscopy (trEFM) to measure photoexcited charge in polymer films with a resolution of 100 nm and 100 mus. We show that such data can predict the external quantum efficiencies of polymer photodiodes, and can thus link device performance with local optoelectronic properties. When applied to the study of blended polyfluorene films, we show that domain centers can buildup charge faster then domain interfaces, which indicates that polymer/polymer blend devices should be modeled as having impure donor/acceptor domains. Third, we use photoconductive atomic force microscopy (pcAFM) to map local photocurrents with 20 nm-resolution in polymer/fullerene solar cells- achieving an order of magnitude better resolution than previous techniques. We present photocurrent maps under short-circuit conditions (zero applied bias), as well as under various applied voltages. We find significant variations in the short-circuit current between regions that appear identical in AFM topography. These variations occur from one domain to

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.

Solid-to-solid phase transformations of nanostructured selenium-tin thin films induced by thermal annealing in oxygen atmosphere

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

Serra, A.; Rossi, M.; Buccolieri, A.

2014-06-19

The structural and morphological evolution of nanostructured thin films obtained from thermal evaporation of polycrystalline Sn-Se starting charge as a function of the subsequent annealing temperature in an oxygen flow has been analysed. High-resolution transmission electron microscopy, small area electron diffraction, digital image processing, x-ray diffraction and Raman spectroscopy have been employed in order to investigate the structure and the morphology of the obtained films. The results evidenced, in the temperature range from RT to 500°C, the transition of the material from a homogeneous mixture of SnSe and SnSe{sub 2} nanocrystals, towards a homogeneous mixture of SnO{sub 2} and SeO{submore » 2} nanocrystals, with an intermediate stage in which only SnSe{sub 2} nanocrystals are present.« less

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

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

Imbedded Nanocrystals of CsPbBr3 in Cs4 PbBr6 : Kinetics, Enhanced Oscillator Strength, and Application in Light-Emitting Diodes.

PubMed

Xu, Junwei; Huang, Wenxiao; Li, Peiyun; Onken, Drew R; Dun, Chaochao; Guo, Yang; Ucer, Kamil B; Lu, Chang; Wang, Hongzhi; Geyer, Scott M; Williams, Richard T; Carroll, David L

2017-11-01

Solution-grown films of CsPbBr 3 nanocrystals imbedded in Cs 4 PbBr 6 are incorporated as the recombination layer in light-emitting diode (LED) structures. The kinetics at high carrier density of pure (extended) CsPbBr 3 and the nanoinclusion composite are measured and analyzed, indicating second-order kinetics in extended and mainly first-order kinetics in the confined CsPbBr 3 , respectively. Analysis of absorption strength of this all-perovskite, all-inorganic imbedded nanocrystal composite relative to pure CsPbBr 3 indicates enhanced oscillator strength consistent with earlier published attribution of the sub-nanosecond exciton radiative lifetime in nanoprecipitates of CsPbBr 3 in melt-grown CsBr host crystals and CsPbBr 3 evaporated films. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Plasmonic light-sensitive skins of nanocrystal monolayers

NASA Astrophysics Data System (ADS)

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

2013-04-01

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

Solution-processable pyrite FeS(2) nanocrystals for the fabrication of heterojunction photodiodes with visible to NIR photodetection.

PubMed

Wang, Di-Yan; Jiang, You-Ting; Lin, Chih-Cheng; Li, Shao-Sian; Wang, Yaw-Tyng; Chen, Chia-Chun; Chen, Chun-Wei

2012-07-03

A heterojunction photodiode with NIR photoresponse using solution processable pyrite FeS(2) nanocrystal ink is demonstrated which has the advantages of earth-abundance and non-toxicity. The device consists of a FeS(2) nanocrystal (NC) thin film sandwiched with semiconducting metal oxides with a structure of ITO/ZnO/FeS(2) NC/MoO(3) /Au, which exhibits an excellent photoresponse with a spectral response extended to NIR wavelengths of up to 1150 nm and a high photocurrent/dark current ratio of up to 8000 at -1 V under AM1.5 illumination (100 mW cm(-2) ). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optical properties of silicon nanocrystals synthesized in supercritical fluids

NASA Astrophysics Data System (ADS)

Pell, Lindsay; Korgel, Brian A.

2002-11-01

We developed a supercritical solution phase synthesis of silicon nanocrystals. High temperature and pressure (500°C, >140 bar) conditions allow a wet chemical approach to this challenging synthesis. Diphenylsilane was used as a silicon precursor and long chain thiols and alcohols were used to sterically stabilize the luminescent nanocrystals. Moderate size separation was achieved via size exclusion chromatography using crosslinked styrene divinylbenzene beads. Size separated fractions of silicon nanocrystals exhibit quantum efficiencies of 12% while polydisperse samples have quantum efficiencies of 5%. Nanocrystal size distributions have been determined with transmission electron microscopy and further characterized with atomic force microscopy (AFM). These silicon nanocrystals have size tunable photoluminescence as indicated by their ensemble spectroscopy and further verified through AFM and single nanocrystal photoluminescence spectroscopy. Fluorescence intermittency (characteristic of single CdSe nanocrystals) is present in our isolated silicon nanocrystals and is one of the criteria used to distinguish single crystals from clusters of particles.

High-temperature crystallization of nanocrystals into three-dimensional superlattices

DOE PAGES

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

2017-07-31

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

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

PubMed

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

2017-08-10

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

High-temperature crystallization of nanocrystals into three-dimensional superlattices

NASA Astrophysics Data System (ADS)

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

2017-08-01

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

CsPbBr{sub 3} nanocrystal saturable absorber for mode-locking ytterbium fiber laser

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

Zhou, Yan; Li, Yue; Xu, Jianqiu

Cesium lead halide perovskite nanocrystals (CsPbX{sub 3}, X = Cl, Br, I) have been reported as efficient light-harvesting and light-emitting semiconductor materials, but their nonlinear optical properties have been seldom touched upon. In this paper, we prepare layered CsPbBr{sub 3} nanocrystal films and characterize their physical properties. Broadband linear absorption from ∼0.8 to over 2.2 μm and nonlinear optical absorption at the 1-μm wavelength region are measured. The CsPbBr{sub 3} saturable absorber (SA), manufactured by drop-casting of colloidal CsPbBr{sub 3} liquid solution on a gold mirror, shows modulation depth and saturation intensity of 13.1% and 10.7 MW/cm{sup 2}, respectively. With this SA, mode-locking operationmore » of a polarization-maintained ytterbium fiber laser produces single pulses with duration of ∼216 ps, maximum average output power of 10.5 mW, and the laser spectrum is centered at ∼1076 nm. This work shows that CsPbBr{sub 3} films can be efficient SA candidates for fiber lasers and also have great potential to become broadband linear and nonlinear optical materials for photonics and optoelectronics.« less

Transition-Metal Decorated Aluminum Nanocrystals.

PubMed

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

2017-10-24

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

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.

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.

Electrical four-point probing of spherical metallic thin films coated onto micron sized polymer particles

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

Pettersen, Sigurd R., E-mail: sigurd.r.pettersen@ntnu.no, E-mail: jianying.he@ntnu.no; Stokkeland, August Emil; Zhang, Zhiliang

Micron-sized metal-coated polymer spheres are frequently used as filler particles in conductive composites for electronic interconnects. However, the intrinsic electrical resistivity of the spherical thin films has not been attainable due to deficiency in methods that eliminate the effect of contact resistance. In this work, a four-point probing method using vacuum compatible piezo-actuated micro robots was developed to directly investigate the electric properties of individual silver-coated spheres under real-time observation in a scanning electron microscope. Poly(methyl methacrylate) spheres with a diameter of 30 μm and four different film thicknesses (270 nm, 150 nm, 100 nm, and 60 nm) were investigated. By multiplying the experimental resultsmore » with geometrical correction factors obtained using finite element models, the resistivities of the thin films were estimated for the four thicknesses. These were higher than the resistivity of bulk silver.« less

Probing nanoscale ion dynamics in ultrathin films of polymerized ionic liquids by broadband dielectric spectroscopy

NASA Astrophysics Data System (ADS)

Sangoro, Joshua; Heres, Maximilian; Cosby, Tyler

Continuous progress in energy storage and conversion technologies necessitates novel experimental approaches that can provide fundamental insights regarding the impact of reduced dimensions on the functional properties of materials. In this talk, a nondestructive experimental approach to probe nanoscale ion dynamics in ultrathin films of polymerized ionic liquids over a broad frequency range spanning over six orders of magnitude by broadband dielectric spectroscopy will be presented. The approach involves using an electrode configuration with lithographically patterned silica nanostructures, which allow for an air gap between the confined ion conductor and one of the electrodes. It is observed that the characteristic ion dynamics rates significantly slow down with decreasing film thicknesses above the calorimetric glass transition of the bulk polymer. However, the mean rates remain bulk-like at lower temperatures. These results highlight the increasing influence of the polymer/substrate interactions with decreasing film thickness on ion dynamics. The authors gratefully acknowledge the National Science Foundation for financial support through the Polymers Program award DMR-1508394.

Nanocrystalline high-entropy alloy (CoCrFeNiAl 0.3 ) thin-film coating by magnetron sputtering

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

Liao, Weibing; Lan, Si; Gao, Libo

High-entropy CoCrFeNiAl0.3 alloy thin films were prepared by magnetron sputtering technique. The thin film surface was very smooth and homogeneous. The synchrotron X-ray experiment confirmed that (111) type of texture existed in the thin film, and the structure was face-centered cubic nanocrystals with a minor content of ordered NiAl-type body-centered cubic structures. Interestingly, the elastic modulus of the thin film was nearly the same to the bulk single-crystal counterpart, however, the nanohardness is about four times of the bulk single-crystal counterpart. It was found that the high hardness was due to the formation of nanocrystal structure inside the thin filmsmore » and the preferred growth orientation, which could be promising for applications in micro fabrication and advanced coating technologies.« less

Engineering Plasmonic Nanocrystal Coupling through Template-Assisted Self-Assembly

NASA Astrophysics Data System (ADS)

Greybush, Nicholas J.

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

Building Materials from Colloidal Nanocrystal Assemblies: Molecular Control of Solid/Solid Interfaces in Nanostructured Tetragonal ZrO 2

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

Shaw, Santosh; Silva, Tiago F.; Bobbitt, Jonathan M.

We describe in this paper a bottom-up approach to control the composition of solid/solid interfaces in nanostructured materials, and we test its effectiveness on tetragonal ZrO 2, an inorganic phase of great technological significance. Colloidal nanocrystals capped with trioctylphosphine oxide (TOPO) or oleic acid (OA) are deposited, and the organic fraction of the ligands is selectively etched with O 2 plasma. The interfaces in the resulting all-inorganic colloidal nanocrystal assemblies are either nearly bare (for OA-capped nanocrystals) or terminated with phosphate groups (for TOPO-capped nanocrystals) resulting from the reaction of phosphine oxide groups with plasma species. The chemical modification ofmore » the interfaces has extensive effects on the thermodynamics and kinetics of the material. Different growth kinetics indicate different rate limiting processes of growth (surface diffusion for the phosphate-terminated surfaces and dissolution for the “bare” surfaces). Phosphate termination led to a higher activation energy of growth, and a 3-fold reduction in interfacial energy, and facilitated significantly the conversion of the tetragonal phase into the monoclinic phase. Finally, films devoid of residual ligands persisted in the tetragonal phase at temperatures as high as 900 °C for 24 h.« less

Building Materials from Colloidal Nanocrystal Assemblies: Molecular Control of Solid/Solid Interfaces in Nanostructured Tetragonal ZrO 2

DOE PAGES

Shaw, Santosh; Silva, Tiago F.; Bobbitt, Jonathan M.; ...

2017-08-28

We describe in this paper a bottom-up approach to control the composition of solid/solid interfaces in nanostructured materials, and we test its effectiveness on tetragonal ZrO 2, an inorganic phase of great technological significance. Colloidal nanocrystals capped with trioctylphosphine oxide (TOPO) or oleic acid (OA) are deposited, and the organic fraction of the ligands is selectively etched with O 2 plasma. The interfaces in the resulting all-inorganic colloidal nanocrystal assemblies are either nearly bare (for OA-capped nanocrystals) or terminated with phosphate groups (for TOPO-capped nanocrystals) resulting from the reaction of phosphine oxide groups with plasma species. The chemical modification ofmore » the interfaces has extensive effects on the thermodynamics and kinetics of the material. Different growth kinetics indicate different rate limiting processes of growth (surface diffusion for the phosphate-terminated surfaces and dissolution for the “bare” surfaces). Phosphate termination led to a higher activation energy of growth, and a 3-fold reduction in interfacial energy, and facilitated significantly the conversion of the tetragonal phase into the monoclinic phase. Finally, films devoid of residual ligands persisted in the tetragonal phase at temperatures as high as 900 °C for 24 h.« less

Surface potential measurement of n-type organic semiconductor thin films by mist deposition via Kelvin probe microscopy

NASA Astrophysics Data System (ADS)

Odaka, Akihiro; Satoh, Nobuo; Katori, Shigetaka

2017-08-01

We partially deposited fullerene (C60) and phenyl-C61-butyric acid methyl ester thin films that are typical n-type semiconductor materials on indium-tin oxide by mist deposition at various substrate temperatures. The topographic and surface potential images were observed via dynamic force microscopy/Kelvin probe force microscopy with the frequency modulation detection method. We proved that the area where a thin film is deposited depends on the substrate temperature during deposition from the topographic images. It was also found that the surface potential depends on the substrate temperature from the surface potential images.

Nanocrystal Targeting In Vivo

DTIC Science & Technology

2002-08-01

Shearwater Polymers , Huntsville, AL) was thiolated with iminothiolane. Thiolated PEG was directly added to a solution of mercaptoacetic acid- coated qdots...Nanocrystal targeting in vivo Maria E. Åkerman*†‡, Warren C. W. Chan†‡, Pirjo Laakkonen*, Sangeeta N. Bhatia†, and Erkki Ruoslahti*§ *Cancer Research...set out to explore the feasibility of in vivo targeting by using semiconductor quantum dots (qdots). Qdots are small (᝺ nm) inorganic nanocrystals

Colloidal nanocrystals and method of making

DOEpatents

Kahen, Keith

2015-10-06

A tight confinement nanocrystal comprises a homogeneous center region having a first composition and a smoothly varying region having a second composition wherein a confining potential barrier monotonically increases and then monotonically decreases as the smoothly varying region extends from the surface of the homogeneous center region to an outer surface of the nanocrystal. A method of producing the nanocrystal comprises forming a first solution by combining a solvent and at most two nanocrystal precursors; heating the first solution to a nucleation temperature; adding to the first solution, a second solution having a solvent, at least one additional and different precursor to form the homogeneous center region and at most an initial portion of the smoothly varying region; and lowering the solution temperature to a growth temperature to complete growth of the smoothly varying region.

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

Green synthesis of water soluble semiconductor nanocrystals and their applications

NASA Astrophysics Data System (ADS)

Wang, Ying

II-VI semiconductor nanomaterials, e.g. CdSe and CdTe, have attracted great attention over the past decades due to their fascinating optical and electrical properties. The research presented here focuses on aqueous semiconductor nanomaterials. The work can be generally divided into three parts: synthesis, property study and application. The synthetic work is devoted to develop new methods to prepare shape- and structure-controlled II-VI semiconductor nanocrystals including nanoparticles and nanowires. CdSe and CdSe CdS semiconductor nanocrystals have been synthesized using sodium citrate as a stabilizer. Upon prolonged illumination with visible light, photoluminescence quantum yield of those quantum dots can be enhanced up to 5000%. The primary reason for luminescence enhancement is considered to be the removing of specific surface states (photocorrosion) and the smoothing of the CdSe core surface (photoannealing). CdTe nanowires are prepared through self-organization of stabilizer-depleted CdTe nanoparticles. The dipolar-dipolar attraction is believed to be the driving force of nanowire formation. The rich surface chemistry of CdTe nanowire is reflected by the formation of silica shell with different morphologies when nanowires with different capping ligands are used. Te and Se nanowires are prepared by chemical decomposition of CdTe and CdSe nanoparticles in presence of an external chemical stimulus, EDTA. These results not only provide a new example of NP→NW transformation, but also lead to a better understanding of the molecular process occurring in the stabilizer-depleted nanoparticles. The applications of those semiconductor materials are primarily based on the construction of nano-structured ultrathin films with desirable functions by using layer-by-layer technique (LBL). We demonstrate that light-induced micro-scale multicolor luminescent patterns can be obtained on photoactivable CdSe/CdS nanoparticles thin films by combining the advantages of LBL as

Volmer-Weber growth stages of polycrystalline metal films probed by in situ and real-time optical diagnostics

NASA Astrophysics Data System (ADS)

Abadias, G.; Simonot, L.; Colin, J. J.; Michel, A.; Camelio, S.; Babonneau, D.

2015-11-01

The Volmer-Weber growth of high-mobility metal films is associated with the development of a complex compressive-tensile-compressive stress behavior as the film deposition proceeds through nucleation of islands, coalescence, and formation of a continuous layer. The tensile force maximum has been attributed to the end of the islands coalescence stage, based on ex situ morphological observations. However, microstructural rearrangements are likely to occur in such films during post-deposition, somewhat biasing interpretations solely based on ex situ analysis. Here, by combining two simultaneous in situ and real-time optical sensing techniques, based on surface differential reflectance spectroscopy (SDRS) and change in wafer curvature probed by multibeam optical stress sensor (MOSS), we provide direct evidence that film continuity does coincide with tensile stress maximum during sputter deposition of a series of metal (Ag, Au, and Pd) films on amorphous SiOx. Stress relaxation after growth interruption was testified from MOSS, whose magnitude scaled with adatom mobility, while no change in SDRS signal could be revealed, ruling out possible changes of the surface roughness at the micron scale.

Optical Properties of CdSe/ZnS Nanocrystals

PubMed Central

Gaigalas, Adolfas K; DeRose, Paul; Wang, Lili; Zhang, Yu-Zhong

2014-01-01

Measurements are presented of the absorbance, fluorescence emission, fluorescence quantum yield, and fluorescence lifetime of CdSe/ZnS nanocrystals, also known as quantum dots (QDs). The study included three groups of nanocrystals whose surfaces were either passivated with organic molecules, modified further with carboxyl groups, or conjugated with CD14 mouse anti-human antibodies. The surface modifications had observable effects on the optical properties of the nanocrystals. The oscillator strength (OS) of the band edge transition was about 1.0 for the nanocrystals emitting at 565 nm, 605 nm, and 655 nm. The OS could not be determined for QDs with emission at 700 nm and 800 nm. The fluorescence lifetimes varied from 26 ns for nanocrystals emitting near 600 nm to 150 ns for nanocrystals emitting near 800 nm. The quantum yield ranged between 0.4 and 0.9 for the nanocrystals in this study. A brightness index (BI) was used to evaluate the suitability of the nanocrystal labels for flow cytometer measurements. Most QD labels are at least as bright as fluorescein for applications in flow cytometer assays with 488 nm excitation. For optimal brightness the QDs should be excited with 405 nm light. We observed a strong dependence of the QD absorbance at 250 nm on the surface modification of the QD. PMID:26601047

Quantitative measurement of adhesion of ink on plastic films with a Nano Indenter and a Scanning Probe Microscope

NASA Astrophysics Data System (ADS)

Shen, Weidian

2005-03-01

Plastic film packaging is widely used these days, especially in the convenience food industry due to its flexibility, boilability, and microwavability. Almost every package is printed with ink. The adhesion of ink on plastic films merits increasing attention to ensure quality packaging. However, inks and plastic films are polymeric materials with complicated molecular structures. The thickness of the jelly-like ink is only 500nm or less, and the thickness of the soft and flexible film is no more than 50μm, which make the quantitative measurement of their adhesion very challenging. Up to now, no scientific quantitative measurement method for the adhesion of ink on plastic films has been documented. We have tried a technique, in which a Nano-Indenter and a Scanning Probe Microscope were used to evaluate the adhesion strength of ink deposited on plastic films, quantitatively, as well as examine the configurations of adhesion failure. It was helpful in better understanding the adhesion mechanism, thus giving direction as to how to improve the adhesion.

Conductive scanning probe microscopy of the semicontinuous gold film and its SERS enhancement toward two-step photo-induced charge transfer and effect of the supportive layer

NASA Astrophysics Data System (ADS)

Sinthiptharakoon, K.; Sapcharoenkun, C.; Nuntawong, N.; Duong, B.; Wutikhun, T.; Treetong, A.; Meemuk, B.; Kasamechonchung, P.; Klamchuen, A.

2018-05-01

The semicontinuous gold film, enabling various electronic applications including development of surface-enhanced Raman scattering (SERS) substrate, is investigated using conductive atomic force microscopy (CAFM) and Kelvin probe force microscopy (KPFM) to reveal and investigate local electronic characteristics potentially associated with SERS generation of the film material. Although the gold film fully covers the underlying silicon surface, CAFM results reveal that local conductivity of the film is not continuous with insulating nanoislands appearing throughout the surface due to incomplete film percolation. Our analysis also suggests the two-step photo-induced charge transfer (CT) play the dominant role in the enhancement of SERS intensity with strong contribution from free electrons of the silicon support. Silicon-to-gold charge transport is illustrated by KPFM results showing that Fermi level of the gold film is slightly inhomogeneous and far below the silicon conduction band. We propose that inhomogeneity of the film workfunction affecting chemical charge transfer between gold and Raman probe molecule is associated with the SERS intensity varying across the surface. These findings provide deeper understanding of charge transfer mechanism for SERS which can help in design and development of the semicontinuous gold film-based SERS substrate and other electronic applications.

Scanning Probe Microscopy and Electrical Transport Studies of Ferroelectric Thin Films and 2D van der Waals Materials

NASA Astrophysics Data System (ADS)

Xiao, Zhiyong

In this dissertation, I present the scanning microscopy and electrical transport studies of ferroelectric thin films and ferroic/2D van der Waals heterostructures. Based on the conducting probe atomic force microscopy and piezo-response force microscopy (PFM) studies of the static and dynamic behavior of ferroelectric domain walls (DW), we found that the ferroelectric polymer poly(vinylidene-fluoride-trifluorethylene) P(VDF-TrFE) is composed of two-dimensional (2D) ferroelectric monolayers (MLs) that are weakly coupled to each other. We also observed polarization asymmetry in epitaxial thin films of ferroelectric Pb(Zr,Ti)O3, which is attributed to the screening properties of the underlying conducting oxide. PFM studies also reveal ferroelectric relaxor-type behavior in ultrathin Sr(Zr,Ti)O3 films epitaxially deposited on Ge. We exploited scanning-probe-controlled domain patterning in a P(VDF-TrFE) top layer to induce nonvolatile modulation of the conduction characteristic of ML molybdenum disulfide (MoS2) between a transistor and a junction state. In the presence of a DW, MoS2 exhibits rectified Ids-Vds (IV) characteristics that are well described by the thermionic emission model. This approach can be applied to a wide range of van der Waals materials to design various functional homojunctions and nanostructures. We also studied the interfacial charge transfer effect between graphene and magnetoelectric Cr2O3 via electrostatic force microscopy and Kelvin probe force microscopy, which reveal p-type doping with up to 150 meV shift of the Fermi level. The graphene/Cr2O3 heterostructure is promising for developing magnetoelectric graphene transistors for spintronic applications.

Nanocrystal dispersed amorphous alloys

NASA Technical Reports Server (NTRS)

Perepezko, John H. (Inventor); Allen, Donald R. (Inventor); Foley, James C. (Inventor)

2001-01-01

Compositions and methods for obtaining nanocrystal dispersed amorphous alloys are described. A composition includes an amorphous matrix forming element (e.g., Al or Fe); at least one transition metal element; and at least one crystallizing agent that is insoluble in the resulting amorphous matrix. During devitrification, the crystallizing agent causes the formation of a high density nanocrystal dispersion. The compositions and methods provide advantages in that materials with superior properties are provided.

Charge transport through exciton shelves in cadmium chalcogenide quantum dot-DNA nano-bioelectronic thin films

NASA Astrophysics Data System (ADS)

Goodman, Samuel M.; Noh, Hyunwoo; Singh, Vivek; Cha, Jennifer N.; Nagpal, Prashant

2015-02-01

Quantum dot (QD), or semiconductor nanocrystal, thin films are being explored for making solution-processable devices due to their size- and shape-tunable bandgap and discrete higher energy electronic states. While DNA has been extensively used for the self-assembly of nanocrystals, it has not been investigated for the simultaneous conduction of multiple energy charges or excitons via exciton shelves (ES) formed in QD-DNA nano-bioelectronic thin films. Here, we present studies on charge conduction through exciton shelves, which are formed via chemically coupled QDs and DNA, between electronic states of the QDs and the HOMO-LUMO levels in the complementary DNA nucleobases. While several challenges need to be addressed in optimizing the formation of devices using QD-DNA thin films, a higher charge collection efficiency for hot-carriers and our detailed investigations of charge transport mechanism in these thin films highlight their potential for applications in nano-bioelectronic devices and biological transducers.

Measurement of Electronic States of PbS Nanocrystal Quantum Dots Using Scanning Tunneling Spectroscopy: The Role of Parity Selection Rules in Optical Absorption

NASA Astrophysics Data System (ADS)

Diaconescu, Bogdan; Padilha, Lazaro A.; Nagpal, Prashant; Swartzentruber, Brian S.; Klimov, Victor I.

2013-03-01

We study the structure of electronic states in individual PbS nanocrystal quantum dots by scanning tunneling spectroscopy (STS) using one-to-two monolayer nanocrystal films treated with 1, 2-ethanedithiols (EDT). Up to six individual valence and conduction band states are resolved for a range of quantum dot sizes. The measured states’ energies are in good agreement with calculations using the k·p four-band envelope function formalism. A comparison of STS and optical absorption spectra indicates that some of the absorption features can only be explained by asymmetric transitions involving the states of different symmetries (e.g., S and P or P and D), which points towards the relaxation of the parity selection rules in these nanostructures. STS measurements also reveal a midgap feature, which is likely similar to one observed in previous charge transport studies of EDT-treated quantum dot films.

Highly aqueous soluble CaF2:Ce/Tb nanocrystals: effect of surface functionalization on structural, optical band gap, and photoluminescence properties.

PubMed

Ansari, Anees A; Parchur, Abdul K; Kumar, Brijesh; Rai, S B

2016-12-01

The design of nanostructured materials with highly stable water-dispersion and luminescence efficiency is an important concern in nanotechnology and nanomedicine. In this paper, we described the synthesis and distinct surface modification on the morphological structure and optical (optical absorption, band gap energy, excitation, emission, decay time, etc.) properties of highly crystalline water-dispersible CaF 2 :Ce/Tb nanocrystals (core-nanocrystals). The epitaxial growth of inert CaF 2 and silica shell, respectively, on their surface forming as CaF 2 :Ce/Tb@CaF 2 (core/shell) and CaF 2 :Ce/Tb@CaF 2 @SiO 2 (core/shell/SiO 2 ) nanoarchitecture. X-ray diffraction and transmission electron microscope image shows that the nanocrystals were in irregular spherical phase, highly crystalline (~20 nm) with narrow size distribution. The core/shell nanocrystals confirm that the surface coating is responsible in the change of symmetrical nanostructure, which was determined from the band gap energy and luminescent properties. It was found that an inert inorganic shell formation effectively enhances the luminescence efficiency and silica shell makes the nanocrystals highly water-dispersible. In addition, Ce 3+ /Tb 3+ -co-doped CaF 2 nanocrystals show efficient energy transfer from Ce 3+ to Tb 3+ ion and strong green luminescence of Tb 3+ ion at 541 nm( 5 D 4 → 7 F 5 ). Luminescence decay curves of core and core/shell nanocrystals were fitted using mono and biexponential equations, and R 2 regression coefficient criteria were used to discriminate the goodness of the fitted model. The lifetime values for the core/shell nanocrystals are higher than core-nanocrystals. Considering the high stable water-dispersion and intensive luminescence emission in the visible region, these luminescent core/shell nanocrystals could be potential candidates for luminescent bio-imaging, optical bio-probe, displays, staining, and multianalyte optical sensing. A newly designed CaF 2 :Ce

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.

Enhanced oral bioavailability of glycyrrhetinic acid via nanocrystal formulation.

PubMed

Lei, Yaya; Kong, Yindi; Sui, Hong; Feng, Jun; Zhu, Rongyue; Wang, Wenping

2016-10-01

The purpose of this study was to prepare solid nanocrystals of glycyrrhetinic acid (GA) for improved oral bioavailability. The anti-solvent precipitation-ultrasonication method followed by freeze-drying was adopted for the preparation of GA nanocrystals. The physicochemical properties, drug dissolution and pharmacokinetic of the obtained nanocrystals were investigated. GA nanocrystals showed a mean particle size of 220 nm and shaped like short rods. The analysis results from differential scanning calorimetry and X-ray powder diffraction indicated that GA remained in crystalline state despite a huge size reduction. The equilibrium solubility and dissolution rate of GA nanocrystal were significantly improved in comparison with those of the coarse GA or the physical mixture. The bioavailability of GA nanocrystals in rats was 4.3-fold higher than that of the coarse GA after oral administration. With its rapid dissolution and absorption performance, the solid nanocrystal might be a more preferable formulation for oral administration of poorly soluble GA.

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.

Isolating and moving single atoms using silicon nanocrystals

DOEpatents

Carroll, Malcolm S.

2010-09-07

A method is disclosed for isolating single atoms of an atomic species of interest by locating the atoms within silicon nanocrystals. This can be done by implanting, on the average, a single atom of the atomic species of interest into each nanocrystal, and then measuring an electrical charge distribution on the nanocrystals with scanning capacitance microscopy (SCM) or electrostatic force microscopy (EFM) to identify and select those nanocrystals having exactly one atom of the atomic species of interest therein. The nanocrystals with the single atom of the atomic species of interest therein can be sorted and moved using an atomic force microscope (AFM) tip. The method is useful for forming nanoscale electronic and optical devices including quantum computers and single-photon light sources.

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.

Iron Oxide Nanocrystals for Magnetic Hyperthermia Applications

PubMed Central

Armijo, Leisha M.; Brandt, Yekaterina I.; Mathew, Dimple; Yadav, Surabhi; Maestas, Salomon; Rivera, Antonio C.; Cook, Nathaniel C.; Withers, Nathan J.; Smolyakov, Gennady A.; Adolphi, Natalie; Monson, Todd C.; Huber, Dale L.; Smyth, Hugh D. C.; Osiński, Marek

2012-01-01

Magnetic nanocrystals have been investigated extensively in the past several years for several potential applications, such as information technology, MRI contrast agents, and for drug conjugation and delivery. A specific property of interest in biomedicine is magnetic hyperthermia—an increase in temperature resulting from the thermal energy released by magnetic nanocrystals in an external alternating magnetic field. Iron oxide nanocrystals of various sizes and morphologies were synthesized and tested for specific losses (heating power) using frequencies of 111.1 kHz and 629.2 kHz, and corresponding magnetic field strengths of 9 and 25 mT. Polymorphous nanocrystals as well as spherical nanocrystals and nanowires in paramagnetic to ferromagnetic size range exhibited good heating power. A remarkable 30 °C temperature increase was observed in a nanowire sample at 111 kHz and magnetic field of 25 mT (19.6 kA/m), which is very close to the typical values of 100 kHz and 20 mT used in medical treatments. PMID:28348300

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.

Complementary Characterization of Cu(In,Ga)Se₂ Thin-Film Photovoltaic Cells Using Secondary Ion Mass Spectrometry, Auger Electron Spectroscopy, and Atom Probe Tomography.

PubMed

Jang, Yun Jung; Lee, Jihye; Jeong, Jeung-Hyun; Lee, Kang-Bong; Kim, Donghwan; Lee, Yeonhee

2018-05-01

To enhance the conversion performance of solar cells, a quantitative and depth-resolved elemental analysis of photovoltaic thin films is required. In this study, we determined the average concentration of the major elements (Cu, In, Ga, and Se) in fabricated Cu(In,Ga)Se2 (CIGS) thin films, using inductively coupled plasma atomic emission spectroscopy, X-ray fluorescence, and wavelengthdispersive electron probe microanalysis. Depth profiling results for CIGS thin films with different cell efficiencies were obtained using secondary ion mass spectrometry and Auger electron spectroscopy to compare the atomic concentrations. Atom probe tomography, a characterization technique with sub-nanometer resolution, was used to obtain three-dimensional elemental mapping and the compositional distribution at the grain boundaries (GBs). GBs are identified by Na increment accompanied by Cu depletion and In enrichment. Segregation of Na atoms along the GB had a beneficial effect on cell performance. Comparative analyses of different CIGS absorber layers using various analytical techniques provide us with understanding of the compositional distributions and structures of high efficiency CIGS thin films in solar cells.

High-performance and flexible thermoelectric films by screen printing solution-processed nanoplate crystals.

PubMed

Varghese, Tony; Hollar, Courtney; Richardson, Joseph; Kempf, Nicholas; Han, Chao; Gamarachchi, Pasindu; Estrada, David; Mehta, Rutvik J; Zhang, Yanliang

2016-09-12

Screen printing allows for direct conversion of thermoelectric nanocrystals into flexible energy harvesters and coolers. However, obtaining flexible thermoelectric materials with high figure of merit ZT through printing is an exacting challenge due to the difficulties to synthesize high-performance thermoelectric inks and the poor density and electrical conductivity of the printed films. Here, we demonstrate high-performance flexible films and devices by screen printing bismuth telluride based nanocrystal inks synthesized using a microwave-stimulated wet-chemical method. Thermoelectric films of several tens of microns thickness were screen printed onto a flexible polyimide substrate followed by cold compaction and sintering. The n-type films demonstrate a peak ZT of 0.43 along with superior flexibility, which is among the highest reported ZT values in flexible thermoelectric materials. A flexible thermoelectric device fabricated using the printed films produces a high power density of 4.1 mW/cm(2) with 60 °C temperature difference between the hot side and cold side. The highly scalable and low cost process to fabricate flexible thermoelectric materials and devices demonstrated here opens up many opportunities to transform thermoelectric energy harvesting and cooling applications.

High-performance and flexible thermoelectric films by screen printing solution-processed nanoplate crystals

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

Varghese, Tony; Hollar, Courtney; Richardson, Joseph

Screen printing allows for direct conversion of thermoelectric nanocrystals into flexible energy harvesters and coolers. However, obtaining flexible thermoelectric materials with high figure of merit ZT through printing is an exacting challenge due to the difficulties to synthesize high-performance thermoelectric inks and the poor density and electrical conductivity of the printed films. Here, we demonstrate high-performance flexible films and devices by screen printing bismuth telluride based nanocrystal inks synthesized using a microwave-stimulated wet-chemical method. Thermoelectric films of several tens of microns thickness were screen printed onto a flexible polyimide substrate followed by cold compaction and sintering. The n-type films demonstratemore » a peak ZT of 0.43 along with superior flexibility, which is among the highest reported ZT values in flexible thermoelectric materials. A flexible thermoelectric device fabricated using the printed films produces a high power density of 4.1 mW/cm 2 with 60°C temperature difference between the hot side and cold side. In conclusion, the highly scalable and low cost process to fabricate flexible thermoelectric materials and devices demonstrated here opens up many opportunities to transform thermoelectric energy harvesting and cooling applications.« less

High-performance and flexible thermoelectric films by screen printing solution-processed nanoplate crystals

DOE PAGES

Varghese, Tony; Hollar, Courtney; Richardson, Joseph; ...

2016-09-12

Screen printing allows for direct conversion of thermoelectric nanocrystals into flexible energy harvesters and coolers. However, obtaining flexible thermoelectric materials with high figure of merit ZT through printing is an exacting challenge due to the difficulties to synthesize high-performance thermoelectric inks and the poor density and electrical conductivity of the printed films. Here, we demonstrate high-performance flexible films and devices by screen printing bismuth telluride based nanocrystal inks synthesized using a microwave-stimulated wet-chemical method. Thermoelectric films of several tens of microns thickness were screen printed onto a flexible polyimide substrate followed by cold compaction and sintering. The n-type films demonstratemore » a peak ZT of 0.43 along with superior flexibility, which is among the highest reported ZT values in flexible thermoelectric materials. A flexible thermoelectric device fabricated using the printed films produces a high power density of 4.1 mW/cm 2 with 60°C temperature difference between the hot side and cold side. In conclusion, the highly scalable and low cost process to fabricate flexible thermoelectric materials and devices demonstrated here opens up many opportunities to transform thermoelectric energy harvesting and cooling applications.« less

High-performance and flexible thermoelectric films by screen printing solution-processed nanoplate crystals

PubMed Central

Varghese, Tony; Hollar, Courtney; Richardson, Joseph; Kempf, Nicholas; Han, Chao; Gamarachchi, Pasindu; Estrada, David; Mehta, Rutvik J.; Zhang, Yanliang

2016-01-01

Screen printing allows for direct conversion of thermoelectric nanocrystals into flexible energy harvesters and coolers. However, obtaining flexible thermoelectric materials with high figure of merit ZT through printing is an exacting challenge due to the difficulties to synthesize high-performance thermoelectric inks and the poor density and electrical conductivity of the printed films. Here, we demonstrate high-performance flexible films and devices by screen printing bismuth telluride based nanocrystal inks synthesized using a microwave-stimulated wet-chemical method. Thermoelectric films of several tens of microns thickness were screen printed onto a flexible polyimide substrate followed by cold compaction and sintering. The n-type films demonstrate a peak ZT of 0.43 along with superior flexibility, which is among the highest reported ZT values in flexible thermoelectric materials. A flexible thermoelectric device fabricated using the printed films produces a high power density of 4.1 mW/cm2 with 60 °C temperature difference between the hot side and cold side. The highly scalable and low cost process to fabricate flexible thermoelectric materials and devices demonstrated here opens up many opportunities to transform thermoelectric energy harvesting and cooling applications. PMID:27615036

Application of precipitation methods for the production of water-insoluble drug nanocrystals: production techniques and stability of nanocrystals.

PubMed

Xia, Dengning; Gan, Yong; Cui, Fude

2014-01-01

This review focuses on using precipitation (bottom-up) method to produce water-insoluble drug nanocrystals, and the stability issues of nanocrystals. The precipitation techniques for production of ultra-fine particles have been widely researched for last few decades. In these techniques, precipitation of solute is achieved by addition of a non-solvent for solute called anti-solvent to decrease the solvent power for the solute dissolved in a solution. The anti-solvent can be water, organic solvents or supercritical fluids. In this paper, efforts have been made to review the precipitation techniques involving the anti-solvent precipitation by simple mixing, impinging jet mixing, multi-inlet vortex mixing, the using of high-gravity, ultrasonic waves and supercritical fluids. The key to the success of yielding stable nanocrystals in these techniques is to control the nucleation kinetics and particle growth through mixing during precipitation based on crystallization theories. The stability issues of the nanocrystals, such as sedimentation, Ostwald ripening, agglomeration and cementing of crystals, change of crystalline state, and the approaches to stabilizing nanocrystals are also discussed in detail.

Atomistic tight-binding computations of the structural and optical properties of CdTe/CdX (X=S and Se)/ZnS core/shell/shell nanocrystals

NASA Astrophysics Data System (ADS)

Sukkabot, Worasak

2018-05-01

A study of CdTe/CdX (X=S and Se)/ZnS core/shell/shell nanocrystals is carried out using atomistic tight-binding theory and the configuration interaction method to provide information for applications in bioimaging, biolabeling, display devices and near-infrared electronic instruments. The calculations yield the dependences of the internal and external passivated shells on the natural behaviours of CdTe/CdX (X=S and Se)/ZnS core/shell/shell nanocrystals. The reduction of the optical band gaps is observed with increasing numbers of monolayers in the external ZnS shell due to quantum confinement. Interestingly, the optical band gaps of CdTe/CdS/ZnS core/shell/shell nanocrystals are greater than those of CdTe/CdSe/ZnS core/shell/shell nanocrystals. In the presence of an external ZnS-coated shell, electron-hole wave function overlaps, oscillation strengths, ground-state exchange energies and Stokes shift are improved, whereas ground-state coulomb energies and fine-structure splitting are reduced. The oscillation strengths, Stokes shift and fine-structure splitting are reduced with the increase in external ZnS shell thickness. The oscillation strengths, Stokes shift and fine-structure splitting of CdTe/CdS/ZnS core/shell/shell nanocrystals are larger than those of CdTe/CdSe/ZnS core/shell/shell nanocrystals. Reduction of the atomistic electron-hole interactions is observed with increasing external ZnS shell size. The strong electron-hole interactions are more probed in CdTe/CdS/ZnS core/shell/shell nanocrystals than in CdTe/CdSe/ZnS core/shell/shell nanocrystals.

Enhanced luminescence of Cu-In-S nanocrystals by surface modification.

PubMed

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

2012-04-01

We have synthesized highly luminescent Cu-In-S nanocrystals by heating the mixture of metal carboxylates and alkylthiol under inert atmosphere. We modified the surface of CIS nanocrystals 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 nanocrystals was above 50%, which is more than 10 times higher than the initial QY of CIS nanocrystals before surface modification (QY = 3%). Detailed study on the luminescence mechanism implies that etching of the surface of nanocrystals by dissociated carboxylate group (CH3COO-) and formation of epitaxial shell by Zn with sulfur from alkylthiol efficiently removed the surface defects which are 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 nanocrystals with less toxic and highly stable precursors.

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.

Hollow nanocrystals and method of making

DOEpatents

Alivisatos, A Paul [Oakland, CA; Yin, Yadong [Moreno Valley, CA; Erdonmez, Can Kerem [Berkeley, CA

2011-07-05

Described herein are hollow nanocrystals having various shapes that can be produced by a simple chemical process. The hollow nanocrystals described herein may have a shell as thin as 0.5 nm and outside diameters that can be controlled by the process of making.

2-Hydroxypropyltrimethylammonium xylan adsorption onto rod-like cellulose nanocrystal.

PubMed

Sim, Jae Hyun; Dong, Shuping; Röemhild, Katrin; Kaya, Abdulaziz; Sohn, Daewon; Tanaka, Keiji; Roman, Maren; Heinze, Thomas; Esker, Alan R

2015-02-15

Chemical incompatibility and relatively weak interaction between lignocellulosic fibers and synthetic polymers have made studies of wood fiber-thermoplastic composite more challenging. In this study, adsorption of 2-hydroxypropyltrimethylammonium xylans onto rod-like cellulose nanocrystals are investigated by zeta-potential measurements, and polarized and depolarized dynamic light scattering as a factor for better understanding of lignocellulosic fibers and cellulose nanocrystals. Zeta-potential measurements show xylan derivative adsorption onto cellulose nanocrystals. Decay time distributions of the ternary system and binary system from dynamic light scattering show that aggregates exist in the binary system and they disappear in the ternary system. At low 2-hydroxypropyltrimethylammonium xylan concentrations relative to that of cellulose nanocrystal, xylan derivatives adsorbed onto some of the cellulose nanocrystal. Hence, more xylan derivatives adsorbed onto cellulose nanocrystal increased with increasing xylan derivative concentration. Also, the concentration dependence of the ratio of the rotational diffusion coefficient to the translational diffusion coefficient revealed a strong adsorptive interaction between xylan derivatives and the cellulose nanocrystals. Copyright © 2014 Elsevier Inc. All rights reserved.

Localized surface plasmons modulated nonlinear optical processes in metal film-coupled and upconversion nanocrystals-coated nanoparticles (Conference Presentation)

NASA Astrophysics Data System (ADS)

Lei, Dangyuan

2016-09-01

In the first part of this talk, I will show our experimental investigation on the linear and nonlinear optical properties of metal film-coupled nanosphere monomers and dimers both with nanometric gaps. We have developed a new methodology - polarization resolved spectral decomposition and color decoding to "visualizing" unambiguously the spectral and radiation properties of the complex plasmonic gap modes in these hybrid nanostructures. Single-particle spectroscopic measurements indicate that these hybrid nanostructures can simultaneously enhance several nonlinear optical processes, such as second harmonic generation, two-photon absorption induced luminescence, and hyper-Raman scattering. In the second part, I will show how the polarization state of the emissions from sub-10 nm upconversion nanocrystals (UCNCs) can be modulated when they form a hybrid complex with a gold nanorod (GNR). Our single-particle scattering experiments expose how an interplay between excitation polarization and GNR orientation gives rise to an extraordinary polarized nature of the upconversion emissions from an individual hybrid nanostructure. We support our results by numerical simulations and, using Förster resonance energy transfer theory, we uncover how an overlap between the UCNC emission and GNR extinction bands as well as the mutual orientation between emission and plasmonic dipoles jointly determine the polarization state of the UC emissions.

Controlling upconversion nanocrystals for emerging applications

NASA Astrophysics Data System (ADS)

Zhou, Bo; Shi, Bingyang; Jin, Dayong; Liu, Xiaogang

2015-11-01

Lanthanide-doped upconversion nanocrystals enable anti-Stokes emission with pump intensities several orders of magnitude lower than required by conventional nonlinear optical techniques. Their exceptional properties, namely large anti-Stokes shifts, sharp emission spectra and long excited-state lifetimes, have led to a diversity of applications. Here, we review upconversion nanocrystals from the perspective of fundamental concepts and examine the technical challenges in relation to emission colour tuning and luminescence enhancement. In particular, we highlight the advances in functionalization strategies that enable the broad utility of upconversion nanocrystals for multimodal imaging, cancer therapy, volumetric displays and photonics.

Core/Shell NaGdF4:Nd3+/NaGdF4 Nanocrystals with Efficient Near-Infrared to Near-Infrared Downconversion Photoluminescence for Bioimaging Applications

PubMed Central

Chen, Guanying; Ohulchanskyy, Tymish Y.; Liu, Sha; Law, Wing-Cheung; Wu, Fang; Swihart, Mark T.; Ågren, Hans; Prasad, Paras N.

2012-01-01

We have synthesized core/shell NaGdF4:Nd3+/NaGdF4 nanocrystals with an average size of 15 nm and exceptionally high photoluminescence (PL) quantum yield. When excited at 740 nm, the nanocrystals manifest spectrally distinguished, near infrared to near infrared (NIR-to-NIR) downconversion PL peaked at ~900, ~1050, and ~1300 nm. The absolute quantum yield of NIR-to-NIR PL reached 40% for core-shell nanoparticles dispersed in hexane. Time-resolved PL measurements revealed that this high quantum yield was achieved through suppression of nonradiative recombination originating from surface states and cross relaxations between dopants. NaGdF4:Nd3+/NaGdF4 nanocrystals, synthesized in organic media, were further converted to be water-dispersible by eliminating the capping ligand of oleic acid. NIR-to-NIR PL bioimaging was demonstrated both in vitro and in vivo through visualization of the NIR-to-NIR PL at ~900 nm under incoherent lamp light excitation. The fact that both excitation and the PL of these nanocrystals are in the biological window of optical transparency, combined with their high quantum efficiency, spectral sharpness and photostability, makes these nanocrystals extremely promising as optical biomaging probes. PMID:22401578

Scanning micro-Hall probe mapping of magnetic flux distributions and current densities in YBa2Cu3O7 thin films

NASA Technical Reports Server (NTRS)

Xing, W.; Heinrich, B.; Zhou, HU; Fife, A. A.; Cragg, A. R.; Grant, P. D.

1995-01-01

Mapping of the magnetic flux density B(sub z) (perpendicular to the film plane) for a YBa2Cu3O7 thin-film sample was carried out using a scanning micro-Hall probe. The sheet magnetization and sheet current densities were calculated from the B(sub z) distributions. From the known sheet magnetization, the tangential (B(sub x,y)) and normal components of the flux density B were calculated in the vicinity of the film. It was found that the sheet current density was mostly determined by 2B(sub x,y)/d, where d is the film thickness. The evolution of flux penetration as a function of applied field will be shown.

Zirconia nanocrystals as submicron level biological label

NASA Astrophysics Data System (ADS)

Smits, K.; Liepins, J.; Gavare, M.; Patmalnieks, A.; Gruduls, A.; Jankovica, D.

2012-08-01

Inorganic nanocrystals are of increasing interest for their usage in biology and pharmacology research. Our interest was to justify ZrO2 nanocrystal usage as submicron level biological label in baker's yeast Saccharomyces cerevisia culture. For the first time (to our knowledge) images with sub micro up-conversion luminescent particles in biologic media were made. A set of undoped as well as Er and Yb doped ZrO2 samples at different concentrations were prepared by sol-gel method. The up-conversion luminescence for free standing and for nanocrystals with baker's yeast cells was studied and the differences in up-conversion luminescence spectra were analyzed. In vivo toxic effects of ZrO2 nanocrystals were tested by co-cultivation with baker's yeast.

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.

Experimental and numerical investigation of the recovery ratio of a wedge-shaped hot-film probe

NASA Astrophysics Data System (ADS)

Krause, M.; Gaisbauer, U.; Kraemer, E.; Kosinov, A. D.

2017-03-01

The recovery ratio of a wedge-shaped hot-film probe was determined in an experimental as well as numerical study, since this information is still unpublished and essential for using the probe in hot-film anemometry. The experiments were conducted at the Khristianovich Institute of Theoretical and Applied Mechanics (ITAM) in Novosibirsk, Russia, and the simulations were performed with StarCCM+, a commercial 2nd order finite volume code. In the analysis, the Mach number was varied between M = 2 and M = 4, and the unit Reynolds number ranged from Re1 = 3.8•106 to Re1 = 26.1•106 m-1, depending on the Mach number. During the experiment, the stagnation temperature was kept constant for each Mach number at a separate value in the range of T 0 = 289 ± 7 K. Three different stagnation temperatures were used in the simulations: T 0 = 259 K, T 0 = 289 K, and T 0 = 319 K. The difference between the experimental and the numerical results is ≤ 0.5 %, and, therefore, both are in very good accordance. The influence of the Mach number, of the unit Reynolds number, and of the stagnation temperature was analysed, and three different fitting functions for the recovery ratio were established. In general, the recovery ratio shows small variations with all three tested parameters. These dependencies are of the same order of magnitude.

Quantification of deep traps in nanocrystal solids, their electronic properties, and their influence on device behavior.

PubMed

Bozyigit, Deniz; Volk, Sebastian; Yarema, Olesya; Wood, Vanessa

2013-11-13

We implement three complementary techniques to quantify the number, energy, and electronic properties of trap states in nanocrystal (NC)-based devices. We demonstrate that, for a given technique, the ability to observe traps depends on the Fermi level position, highlighting the importance of a multitechnique approach that probes trap coupling to both the conduction and the valence bands. We then apply our protocol for characterizing traps to quantitatively explain the measured performances of PbS NC-based solar cells.

Single-exciton optical gain in semiconductor nanocrystals.

PubMed

Klimov, Victor I; Ivanov, Sergei A; Nanda, Jagjit; Achermann, Marc; Bezel, Ilya; McGuire, John A; Piryatinski, Andrei

2007-05-24

Nanocrystal quantum dots have favourable light-emitting properties. They show photoluminescence with high quantum yields, and their emission colours depend on the nanocrystal size--owing to the quantum-confinement effect--and are therefore tunable. However, nanocrystals are difficult to use in optical amplification and lasing. Because of an almost exact balance between absorption and stimulated emission in nanoparticles excited with single electron-hole pairs (excitons), optical gain can only occur in nanocrystals that contain at least two excitons. A complication associated with this multiexcitonic nature of light amplification is fast optical-gain decay induced by non-radiative Auger recombination, a process in which one exciton recombines by transferring its energy to another. Here we demonstrate a practical approach for obtaining optical gain in the single-exciton regime that eliminates the problem of Auger decay. Specifically, we develop core/shell hetero-nanocrystals engineered in such a way as to spatially separate electrons and holes between the core and the shell (type-II heterostructures). The resulting imbalance between negative and positive charges produces a strong local electric field, which induces a giant ( approximately 100 meV or greater) transient Stark shift of the absorption spectrum with respect to the luminescence line of singly excited nanocrystals. This effect breaks the exact balance between absorption and stimulated emission, and allows us to demonstrate optical amplification due to single excitons.

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

NASA Astrophysics Data System (ADS)

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

2009-02-01

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

Plasmonic Properties of Silicon Nanocrystals Doped with Boron and Phosphorus.

PubMed

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

2015-08-12

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

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).

Some aspects of pulsed laser deposition of Si nanocrystalline films

NASA Astrophysics Data System (ADS)

Polyakov, B.; Petruhins, A.; Butikova, J.; Kuzmin, A.; Tale, I.

2009-11-01

Nanocrystalline silicon films were deposited by a picosecond laser ablation on different substrates in vacuum at room temperature. A nanocrystalline structure of the films was evidenced by atomic force microscopy (AFM), optical and Raman spectroscopies. A blue shift of the absorption edge was observed in optical absorption spectra, and a decrease of the optical phonon energy at the Brillouin zone centre was detected by Raman scattering. Early stages of nanocrystalline film formation on mica and HOPG substrates were studied by AFM. Mechanism of nanocrystal growth on substrate is discussed. in here

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

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

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

2014-07-01

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

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

PubMed

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

2013-09-01

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