Science.gov

Sample records for metal nanocrystals simple

  1. A simple and generic approach for synthesizing colloidal metal and metal oxide nanocrystals

    NASA Astrophysics Data System (ADS)

    Cloud, Jacqueline E.; Yoder, Tara S.; Harvey, Nathan K.; Snow, Kyle; Yang, Yongan

    2013-07-01

    A simple and generic approach--alternating voltage induced electrochemical synthesis (AVIES)--has been reported for synthesizing highly dispersed colloidal metal (Au, Pt, Sn, and Pt-Pd) and metal oxide (ZnO and TiO2) nanocrystals. The respective nanocrystals are produced when a zero-offset alternating voltage at 60 Hz is applied to a pair of identical metal wires, which are inserted in an electrolyte solution containing capping ligands. In the case of Au, the obtained nanocrystals are highly crystalline nano-icosahedra of 14 +/- 2 nm in diameter, the smallest Au icosahedra synthesized in aqueous solutions via green chemistry. Their catalytic activity has been demonstrated through facilitating the reduction of 4-nitrophenol to 4-aminophenol by sodium borohydride. This AVIES approach is an environmentally benign process and can be adopted by any research lab.

  2. A simple approach for producing colloidal noble metal nanocrystals: Alternating voltage induced electrochemical synthesis

    NASA Astrophysics Data System (ADS)

    McCann, Kevin

    Intense research has been focused on developing bottom-up nanocrystal synthesis techniques to obtain nanocrystals with sophisticated compositions and enhanced perfomances. Three popular methods are: 1) the reduction of metal complex ions or molecules with selected reducing agents, 2) the decomposition of metal compounds at elevated temperatures, and 3) the electrochemical reduction of metal ions using specialized potentiostats. The first two require expensive metal salt precursors while the last requires specialized potentiostats and either employ a single sacrificial electrode or metal salt precursors. To resolve these issues, we have focused on a facile and generic approach to generate nanocrystals by an alternating voltage induced electrochemical synthesis (AVIES) method. Nanocrystals are produced when an alternating voltage is applied by a common laboratory transformer to two sacrificial electrodes that are inserted in an electrolyte solution containing capping ligands. This work focuses on the ability of the AVIES approach to synthesize Au, Pd, and Pt noble metal nanocrystals. The nanocrystals synthesized were found to be dependent on the electrolyte identity, capping ligand, applied voltage, reaction temperature. The ability of AVIES to produce alloyed nanocrystals starting with alloyed electrodes will be discussed. The AVIES approach requires neither expensive metal compounds nor specialized instruments, is environmentally benign, and can be easily adoptable to any research lab.

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

    PubMed Central

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

    2009-01-01

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

  4. A simple dissolved metals mixing method to produce high-purity MgTiO{sub 3} nanocrystals

    SciTech Connect

    Pratapa, Suminar E-mail: suminar-pratapa@physics.its.ac.id; Baqiya, Malik A. E-mail: suminar-pratapa@physics.its.ac.id; Istianah, E-mail: suminar-pratapa@physics.its.ac.id; Lestari, Rina E-mail: suminar-pratapa@physics.its.ac.id; Angela, Riyan E-mail: suminar-pratapa@physics.its.ac.id

    2014-02-24

    A simple dissolved metals mixing method has been effectively used to produce high-purity MgTiO{sub 3} (MT) nanocrystals. The method involves the mixing of independently dissolved magnesium and titanium metal powders in hydrochloric acid followed by calcination. The phase purity and nanocrystallinity were determined by making use of laboratory x-ray diffraction data, to which Rietveld-based analyses were performed. Results showed that the method yielded only one type magnesium titanate powders, i.e. MgTiO{sub 3}, with no Mg{sub 2}TiO{sub 4} or MgTi{sub 2}O{sub 5} phases. The presence of residual rutile or periclase was controlled by adding excessive Mg up to 5% (mol) in the stoichiometric mixing. The method also resulted in MT nanocrystals with estimated average crystallite size of 76±2 nm after calcination at 600°C and 150±4 nm (at 800°C). A transmission electron micrograph confirmed the formation of the nanocrystallites.

  5. Simple Preparation and Stabilization of Nickel Nanocrystals on Cellulose Nanocrystal

    SciTech Connect

    Shin, Yongsoon; Bae, In-Tae; Arey, Bruce W.; Exarhos, Gregory J.

    2007-06-01

    Nickel nanocrystals were simply prepared on the carbon through a thermal reduction process at 400-500oC under N2 after Ni(II) ions were deposited and stabilized on cellulose nanocrystal (CNXL) surface. Hydroxyl groups on the CNXL anchor and stabilize Ni(II) ions. Well-dispersed Ni nanocrystals on the carbonized CNXL were about 5-12 nm in size. XRD, FESEM, and TEM were employed to characterize the products.

  6. 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

  7. Shaping metal nanocrystals through epitaxial seeded growth

    SciTech Connect

    Habas, Susan E.; Lee, Hyunjoo; Radmilovic, Velimir; Somorjai,Gabor A.; Yang, Peidong

    2008-02-17

    Morphological control of nanocrystals has becomeincreasingly important, as many of their physical and chemical propertiesare highly shape-dependent. Nanocrystal shape control for both single andmultiple material systems, however, remains fairly empirical andchallenging. New methods need to be explored for the rational syntheticdesign of heterostructures with controlled morphology. Overgrowth of adifferent material on well-faceted seeds, for example, allows for the useof the defined seed morphology to control nucleation and growth of thesecondary structure. Here, we have used highly faceted cubic Pt seeds todirect the epitaxial overgrowth of a secondary metal. We demonstrate thisconcept with lattice matched Pd to produce conformal shape-controlledcore-shell particles, and then extend it to lattice mismatched Au to giveanisotropic growth. Seeding with faceted nanocrystals may havesignificant potential towards the development of shape-controlledheterostructures with defined interfaces.

  8. Defect Engineering in Plasmonic Metal Oxide Nanocrystals.

    PubMed

    Runnerstrom, Evan L; Bergerud, Amy; Agrawal, Ankit; Johns, Robert W; Dahlman, Clayton J; Singh, Ajay; Selbach, Sverre M; Milliron, Delia J

    2016-05-11

    Defects may tend to make crystals interesting but they do not always improve performance. In doped metal oxide nanocrystals with localized surface plasmon resonance (LSPR), aliovalent dopants and oxygen vacancies act as centers for ionized impurity scattering of electrons. Such electronic damping leads to lossy, broadband LSPR with low quality factors, limiting applications that require near-field concentration of light. However, the appropriate dopant can mitigate ionized impurity scattering. Herein, we report the synthesis and characterization of a novel doped metal oxide nanocrystal material, cerium-doped indium oxide (Ce:In2O3). Ce:In2O3 nanocrystals display tunable mid-infrared LSPR with exceptionally narrow line widths and the highest quality factors observed for nanocrystals in this spectral region. Drude model fits to the spectra indicate that a drastic reduction in ionized impurity scattering is responsible for the enhanced quality factors, and high electronic mobilities reaching 33 cm(2)V(-1) s(-1) are measured optically, well above the optical mobility for tin-doped indium oxide (ITO) nanocrystals. We investigate the microscopic mechanisms underlying this enhanced mobility with density functional theory calculations, which suggest that scattering is reduced because cerium orbitals do not hybridize with the In orbitals that dominate the bottom of the conduction band. Ce doping may also reduce the equilibrium oxygen vacancy concentration, further enhancing mobility. From the absorption spectra of single Ce:In2O3 nanocrystals, we determine the dielectric function and by simulation predict strong near-field enhancement of mid-IR light, especially around the vertices of our synthesized nanocubes. PMID:27111427

  9. Metal halide solid-state surface treatment for nanocrystal materials

    DOEpatents

    Luther, Joseph M.; Crisp, Ryan; Beard, Matthew C.

    2016-04-26

    Methods of treating nanocrystal and/or quantum dot devices are described. The methods include contacting the nanocrystals and/or quantum dots with a solution including metal ions and halogen ions, such that the solution displaces native ligands present on the surface of the nanocrystals and/or quantum dots via ligand exchange.

  10. Silicon nanocrystal-noble metal hybrid nanoparticles.

    PubMed

    Sugimoto, H; Fujii, M; Imakita, K

    2016-06-01

    We report a novel and facile self-limiting synthesis route of silicon nanocrystal (Si NC)-based colloidally stable semiconductor-metal (gold, silver and platinum) hybrid nanoparticles (NPs). For the formation of hybrid NPs, we employ ligand-free colloidal Si NCs with heavily boron (B) and phosphorus (P) doped shells. By simply mixing B and P codoped colloidal Si NCs with metal salts, hybrid NPs consisting of metal cores and Si NC shells are spontaneously formed. We demonstrate the synthesis of highly uniform and size controllable hybrid NPs. It is shown that codoped Si NCs act as a reducing agent for metal salts and also as a protecting layer to stop metal NP growth. The process is thus self-limiting. The development of a variety of Si NC-based hybrid NPs is a promising first step for the design of biocompatible multifunctional NPs with broad material choices for biosensing, bioimaging and solar energy conversion. PMID:27121127

  11. Hydroxyapatite nanocrystals: simple preparation, characterization and formation mechanism.

    PubMed

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

    2014-12-01

    Crystalline hydroxyapatite (HAP) nanoparticles and nanorods have been successfully synthesized via a simple precipitation method. To control the shape and particle size of HAP nanocrystals, coordination ligands derived from 2-hydroxy-1-naphthaldehyde were first prepared, characterized by Fourier transform infrared (FT-IR) and proton nuclear magnetic resonance ((1)H-NMR) spectroscopies, and finally applied in the synthesis process of HAP. On the other hand, the HAP nanocrystals were also characterized by several techniques including powder X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). According to the FE-SEM and TEM micrographs, it was found that the morphology and crystallinity of the HAP powders depended on the coordination mode of the ligands. PMID:25491798

  12. Continuous Growth of Metal Oxide Nanocrystals: Enhanced Control of Nanocrystal Size and Radial Dopant Distribution.

    PubMed

    Jansons, Adam W; Hutchison, James E

    2016-07-26

    The ability to precisely control the composition of nanocrystals, similar to the way organic chemists control the structure of small molecules, remains an important challenge in nanoscience. Rather than dictating nanocrystal size through the nucleation event, growth of nanocrystals through continuous precursor addition would allow fine structural control. Herein, we present a method of growth for indium oxide nanocrystals that relies on the slow addition of an indium carboxylate precursor into hot oleyl alcohol. Nanocrystal size and structure can be governed at a subnanometer scale, and it is possible to precisely control core size over a range of three to at least 22 nm with dispersities as low as 7%. Growth can be stopped and restarted repeatedly without aggregation or passivation. We show that the volume of the nanocrystal core (and thus molecular weight) increases linearly with added monomer and the number of nanocrystals remains constant throughout the growth process, yielding an extremely predictable approach to size control. It is also possible to place metal oxide shells (e.g., Sn-doped In2O3 (ITO)) at various radial positions within the nanocrystal, and we use this approach to synthesize ITO/In2O3 core/shell nanocrystals as well as In2O3/ITO/In2O3 core/shell/shell nanocrystals. PMID:27328328

  13. Silicon nanocrystal-noble metal hybrid nanoparticles

    NASA Astrophysics Data System (ADS)

    Sugimoto, H.; Fujii, M.; Imakita, K.

    2016-05-01

    We report a novel and facile self-limiting synthesis route of silicon nanocrystal (Si NC)-based colloidally stable semiconductor-metal (gold, silver and platinum) hybrid nanoparticles (NPs). For the formation of hybrid NPs, we employ ligand-free colloidal Si NCs with heavily boron (B) and phosphorus (P) doped shells. By simply mixing B and P codoped colloidal Si NCs with metal salts, hybrid NPs consisting of metal cores and Si NC shells are spontaneously formed. We demonstrate the synthesis of highly uniform and size controllable hybrid NPs. It is shown that codoped Si NCs act as a reducing agent for metal salts and also as a protecting layer to stop metal NP growth. The process is thus self-limiting. The development of a variety of Si NC-based hybrid NPs is a promising first step for the design of biocompatible multifunctional NPs with broad material choices for biosensing, bioimaging and solar energy conversion.We report a novel and facile self-limiting synthesis route of silicon nanocrystal (Si NC)-based colloidally stable semiconductor-metal (gold, silver and platinum) hybrid nanoparticles (NPs). For the formation of hybrid NPs, we employ ligand-free colloidal Si NCs with heavily boron (B) and phosphorus (P) doped shells. By simply mixing B and P codoped colloidal Si NCs with metal salts, hybrid NPs consisting of metal cores and Si NC shells are spontaneously formed. We demonstrate the synthesis of highly uniform and size controllable hybrid NPs. It is shown that codoped Si NCs act as a reducing agent for metal salts and also as a protecting layer to stop metal NP growth. The process is thus self-limiting. The development of a variety of Si NC-based hybrid NPs is a promising first step for the design of biocompatible multifunctional NPs with broad material choices for biosensing, bioimaging and solar energy conversion. Electronic supplementary information (ESI) available: Additional TEM images and extinction spectra of Si-metal hybrid NPs are shown in Fig. S1

  14. Simple low-cost miniaturization approach for pharmaceutical nanocrystals production.

    PubMed

    Romero, Gregori B; Keck, Cornelia M; Müller, Rainer H

    2016-03-30

    Systematic screening for optimal formulation composition and production parameters for nanosuspensions consumes a lot of time and also drug material when performed at lab scale. Therefore, a cost-effective miniaturized scale top down approach for nanocrystals production by wet bead milling was developed. The final set-up consisted of 3 magnetic stirring bars placed vertically one over the other in a 2 mL glass vial and agitated by a common magnetic stirring plate. All of the tested actives (cyclosporin A, resveratrol, hesperitin, ascorbyl palmitate, apigenin and hesperidin) could be converted to nanosuspensions. For 4 of them, the particles sizes achieved were smaller than previously reported on the literature (around 90 nm for cyclosporin A; 50 nm for hesperitin; 160 nm for ascorbyl palmitate and 80 nm for apigenin). The "transferability" of the data collect by the miniaturized method was evaluated comparing the production at larger scale using both wet bead milling and high pressure homogenization. Transferable information obtained from the miniaturized scale is minimum achievable size, improvements in size reduction by reduction of beads size, diminution kinetics and potentially occurring instabilities during processing. The small scale batches also allow identification of optimal stabilizer types and concentrations. The batch size is 0.5 mL, requiring approximately 50 mg or 5 mg of drug (5% and 1% suspension, respectively). Thus, a simple, accessible, low-cost miniaturized scale method for the production of pharmaceutical nanocrystals was established. PMID:26642945

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

    SciTech Connect

    Hu, Michael Z.; Easterly, Clay E

    2009-01-01

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

  16. Shape-Controlled Metal Nanocrystals for Heterogeneous Catalysis.

    PubMed

    Ruditskiy, Aleksey; Peng, Hsin-Chieh; Xia, Younan

    2016-06-01

    The ability to control the shape of metal nanocrystals allows us to not only maneuver their physicochemical properties but also optimize their activity in a variety of applications. Heterogeneous catalysis, in particular, would benefit tremendously from the availability of metal nanocrystals with controlled shapes and well-defined facets or surface structures. The immediate benefits may include significant enhancements in catalytic activity and/or selectivity along with reductions in the materials cost. We provide a brief account of recent progress in the development of metal nanocrystals with controlled shapes and thereby enhanced catalytic performance for several reactions, including formic acid oxidation, oxygen reduction, and hydrogenation. In addition to monometallic nanocrystals, we also cover a bimetallic system, in which the two metals are formulated as alloyed, core-shell, or core-frame structures. We hope this article will provide further impetus for the development of next-generation heterogeneous catalysts essential to a broad range of applications. PMID:27023659

  17. Metal-insulator transition in films of doped semiconductor nanocrystals.

    PubMed

    Chen, Ting; Reich, K V; Kramer, Nicolaas J; Fu, Han; Kortshagen, Uwe R; Shklovskii, B I

    2016-03-01

    To fully deploy the potential of semiconductor nanocrystal films as low-cost electronic materials, a better understanding of the amount of dopants required to make their conductivity metallic is needed. In bulk semiconductors, the critical concentration of electrons at the metal-insulator transition is described by the Mott criterion. Here, we theoretically derive the critical concentration nc for films of heavily doped nanocrystals devoid of ligands at their surface and in direct contact with each other. In the accompanying experiments, we investigate the conduction mechanism in films of phosphorus-doped, ligand-free silicon nanocrystals. At the largest electron concentration achieved in our samples, which is half the predicted nc, we find that the localization length of hopping electrons is close to three times the nanocrystals diameter, indicating that the film approaches the metal-insulator transition. PMID:26618885

  18. Metal-insulator transition in films of doped semiconductor nanocrystals

    NASA Astrophysics Data System (ADS)

    Chen, Ting; Reich, K. V.; Kramer, Nicolaas J.; Fu, Han; Kortshagen, Uwe R.; Shklovskii, B. I.

    2016-03-01

    To fully deploy the potential of semiconductor nanocrystal films as low-cost electronic materials, a better understanding of the amount of dopants required to make their conductivity metallic is needed. In bulk semiconductors, the critical concentration of electrons at the metal-insulator transition is described by the Mott criterion. Here, we theoretically derive the critical concentration nc for films of heavily doped nanocrystals devoid of ligands at their surface and in direct contact with each other. In the accompanying experiments, we investigate the conduction mechanism in films of phosphorus-doped, ligand-free silicon nanocrystals. At the largest electron concentration achieved in our samples, which is half the predicted nc, we find that the localization length of hopping electrons is close to three times the nanocrystals diameter, indicating that the film approaches the metal-insulator transition.

  19. Ion irradiation effects on metallic nanocrystals

    NASA Astrophysics Data System (ADS)

    Kluth, P.; Johannessen, B.; Giulian, R.; Schnohr, C. S.; Foran, G. J.; Cookson, D. J.; Byrne, A. P.; Ridgway, M. C.

    We have investigated structural and morphological properties of metallic nanocrystals (NCs) exposed to ion irradiation. NCs were characterized by transmission electron microscopy in combination with advanced synchrotron-based analytical techniques, in particular X-ray absorption spectroscopy and small-angle X-ray scattering. A number of different effects were observed depending on the irradiation conditions. At energies where nuclear stopping is predominant, structural disorder/amorphization followed by inverse Ostwald ripening/dissolution due to ion beam mixing was observed for Au and Cu NCs embedded in SiO2. The ion-irradiation-induced crystalline to amorphous transition in the NCs, which cannot be achieved in the corresponding bulk metals, was attributed to their initially higher structural energy as compared to bulk material and possibly preferential nucleation of the amorphous phase at the NC/SiO2 interface. At very high irradiation energies (swift heavy ion irradiation), where the energy loss is nearly entirely due to electronic stopping, a size-dependent shape transformation of the NCs from spheres to rod like shapes was apparent in Au NCs. Our preliminary results are in good agreement with considerations on melting of the NCs in the ion track as one mechanism involved in the shape transformation.

  20. Ion irradiation effects on metallic nanocrystals

    SciTech Connect

    Kluth, P.; Johannessen, B.; Giulian, R.; Schnohr, C.S.; Foran, G.J.; Cookson, D.J.; Byrne, A.P.; Ridgway, M.C.

    2008-04-02

    We have investigated structural and morphological properties of metallic nanocrystals (NCs) exposed to ion irradiation. NCs were characterized by transmission electron microscopy in combination with advanced synchrotron-based analytical techniques, in particular X-ray absorption spectroscopy and small-angle X-ray scattering. A number of different effects were observed depending on the irradiation conditions. At energies where nuclear stopping is predominant, structural disorder/amorphization followed by inverse Ostwald ripening/dissolution due to ion beam mixing was observed for Au and Cu NCs embedded in SiO{sub 2}. The ion-irradiation-induced crystalline to amorphous transition in the NCs, which cannot be achieved in the corresponding bulk metals, was attributed to their initially higher structural energy as compared to bulk material and possibly preferential nucleation of the amorphous phase at the NC/SiO{sub 2} interface. At very high irradiation energies (swift heavy ion irradiation), where the energy loss is nearly entirely due to electronic stopping, a size-dependent shape transformation of the NCs from spheres to rod like shapes was apparent in Au NCs. Our preliminary results are in good agreement with considerations on melting of the NCs in the ion track as one mechanism involved in the shape transformation.

  1. Defect Chemistry and Plasmon Physics of Colloidal Metal Oxide Nanocrystals

    SciTech Connect

    Lounis, SD; Runnerstrorm, EL; Llordes, A; Milliron, DJ

    2014-05-01

    Plasmonic nanocrystals of highly doped metal oxides have seen rapid development in the past decade and represent a class of materials with unique optoelectronic properties. In this Perspective, we discuss doping mechanisms in metal oxides and the accompanying physics of free carrier scattering, both of which have implications in determining the properties of localized surface plasmon resonances (LSPRs) in these nanocrystals. The balance between activation and compensation of dopants limits the free carrier concentration of the most common metal oxides, placing a ceiling on the LSPR frequency. Furthermore, because of ionized impurity scattering of the oscillating plasma by dopant ions, scattering must be treated in a fundamentally different way in semiconductor metal oxide materials when compared with conventional metals. Though these effects are well-understood in bulk metal oxides, further study is needed to understand their manifestation in nanocrystals and corresponding impact on plasmonic properties, and to develop materials that surpass current limitations in free carrier concentration.

  2. Formation of noble metal nanocrystals in the presence of biomolecules

    NASA Astrophysics Data System (ADS)

    Burt, Justin Lockheart

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

  3. Simple approach to reinforce hydrogels with cellulose nanocrystals

    NASA Astrophysics Data System (ADS)

    Yang, Jun; Han, Chun-Rui; Xu, Feng; Sun, Run-Cang

    2014-05-01

    The physical crosslinking of colloidal nanoparticles via dynamic and directional non-covalent interactions has led to significant advances in composite hydrogels. In this paper, we report a simple approach to fabricate tough, stretchable and hysteretic isotropic nanocomposite hydrogels, where rod-like cellulose nanocrystals (CNCs) are encapsulated by flexible polymer chains of poly(N,N-dimethylacrylamide) (PDMA). The CNC-PDMA colloidal clusters build a homogeneously cross-linked network and lead to significant reinforcing effect of the composites. Hierarchically structured CNC-PDMA clusters, from isolated particles to an interpenetrated network, are observed by transmission electron microscopy measurements. Dynamic shear oscillation measurements are applied to demystify the differences in network rheological behaviors, which were compared with network behaviors of chemically cross-linked PDMA counterparts. Tensile tests indicate that the hybrid hydrogels possess higher mechanical properties and a more efficient energy dissipation mechanism. In particular, with only 0.8 wt% of CNC loading, a 4.8-fold increase in Young's modulus, 9.2-fold increase in tensile strength, and 5.8-fold increase in fracture strain are achieved, which is ascribed to a combination of CNC reinforcement in the soft matrix and CNC-PDMA colloidal cluster conformational rearrangement under stretching. Physical interactions within networks serve as reversible sacrificial bonds that dissociate upon deformation, exhibiting large hysteresis as an energy dissipation mechanism via cluster mobility. This result contrasts with the case of chemically cross-linked PDMA counterparts where the stress relaxation is slow due to the permanent cross-links and low resistance against crack propagation within the covalent network.The physical crosslinking of colloidal nanoparticles via dynamic and directional non-covalent interactions has led to significant advances in composite hydrogels. In this paper, we report

  4. Simple approach to reinforce hydrogels with cellulose nanocrystals.

    PubMed

    Yang, Jun; Han, Chun-rui; Xu, Feng; Sun, Run-cang

    2014-06-01

    The physical crosslinking of colloidal nanoparticles via dynamic and directional non-covalent interactions has led to significant advances in composite hydrogels. In this paper, we report a simple approach to fabricate tough, stretchable and hysteretic isotropic nanocomposite hydrogels, where rod-like cellulose nanocrystals (CNCs) are encapsulated by flexible polymer chains of poly(N,N-dimethylacrylamide) (PDMA). The CNC-PDMA colloidal clusters build a homogeneously cross-linked network and lead to significant reinforcing effect of the composites. Hierarchically structured CNC-PDMA clusters, from isolated particles to an interpenetrated network, are observed by transmission electron microscopy measurements. Dynamic shear oscillation measurements are applied to demystify the differences in network rheological behaviors, which were compared with network behaviors of chemically cross-linked PDMA counterparts. Tensile tests indicate that the hybrid hydrogels possess higher mechanical properties and a more efficient energy dissipation mechanism. In particular, with only 0.8 wt% of CNC loading, a 4.8-fold increase in Young's modulus, 9.2-fold increase in tensile strength, and 5.8-fold increase in fracture strain are achieved, which is ascribed to a combination of CNC reinforcement in the soft matrix and CNC-PDMA colloidal cluster conformational rearrangement under stretching. Physical interactions within networks serve as reversible sacrificial bonds that dissociate upon deformation, exhibiting large hysteresis as an energy dissipation mechanism via cluster mobility. This result contrasts with the case of chemically cross-linked PDMA counterparts where the stress relaxation is slow due to the permanent cross-links and low resistance against crack propagation within the covalent network. PMID:24763379

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

    PubMed

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

    2014-12-16

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

  6. How many electrons make a semiconductor nanocrystal film metallic

    NASA Astrophysics Data System (ADS)

    Reich, Konstantin; Chen, Ting; Kramer, Nicolaas; Fu, Han; Kortshagen, Uwe; Shklovskii, Boris

    For films of semiconductor nanocrystals to achieve their potential as novel, low-cost electronic materials, a better understanding of their doping to tune their conductivity is required. So far, it not known how many dopants will turn a nanocrystal film from semiconducting to metallic. In bulk semiconductors, the critical concentration nM of electrons at the metal-insulator transition is described by the famous Mott criterion: nMaB3 ~= 0 . 02 , where aB is the effective Bohr radius. We show theoretically that in a dense NC film, where NCs touch each other by small facets, the concentration of electrons nc >>nM at the metal-insulator transition satisfies the condition: ncρ3 ~= 0 . 3 , where ρ is a radius of contact facets. In the accompanying experiments, we investigate the conduction mechanism in films of phosphorus-doped, ligand-free silicon nanocrystals. At the largest electron concentration achieved in our samples, which is half the predicted nc, we find that the localization length of hopping electrons is close to three times the nanocrystals diameter, indicating that the film approaches the metal-insulator transition. This work was supported primarily by the National Science Foundation through the University of Minnesota MRSEC under Award No. DMR-1420013.

  7. Metal nanocrystals embedded in single nanocrystals of MOFs give unusual selectivity as heterogeneous catalysts.

    PubMed

    Na, Kyungsu; Choi, Kyung Min; Yaghi, Omar M; Somorjai, Gabor A

    2014-10-01

    The growth of nanocrystalline metal-organic frameworks (nMOFs) around metal nanocrystals (NCs) is useful in controlling the chemistry and metric of metal NCs. In this Letter, we show rare examples of nMOFs grown in monocrystalline form around metal NCs. Specifically, Pt NCs were subjected to reactions yielding Zr(IV) nMOFs [Zr6O4(OH)4(fumarate)6, MOF-801; Zr6O4(OH)4(BDC)6 (BDC = 1,4-benzenedicarboxylate), UiO-66; Zr6O4(OH)4(BPDC)6 (BPDC = 4,4'-biphenyldicarboxylate), UiO-67] as a single crystal within which the Pt NCs are embedded. These constructs (Pt⊂nMOF)nanocrystal are found to be active in gas-phase hydrogenative conversion of methylcyclopentane (MCP) and give unusual product selectivity. The Pt⊂nUiO-66 shows selectivity to C6-cyclic hydrocarbons such as cyclohexane and benzene that takes place with 100 °C lower temperature than the standard reaction (Pt-on-SiO2). We observe a pore size effect in the nMOF series where the small pore of Pt⊂nMOF-801 does not produce the same products, while the larger pore Pt⊂nUiO-67 catalyst provides the same products but with different selectivity. The (Pt⊂nMOF)nanocrystal spent catalyst is found to maintain the original crystallinity, and be recyclable without any byproduct residues. PMID:25198135

  8. Methyl oleate-capped upconverting nanocrystals: a simple and general ligand exchange strategy to render nanocrystals dispersible in aqueous and organic medium.

    PubMed

    Meesaragandla, Brahmaiah; Adusumalli, Venkata N K B; Mahalingam, Venkataramanan

    2015-05-19

    We report a simple and general ligand exchange strategy to functionalize the nanocrystals with both hydrophobic and hydrophilic ligands. This is achieved by first capping the Er/Yb-doped NaYF4 nanocrystals with a weak ligand such as methyl oleate and subsequently ligand exchanged with various organic ligands which can strongly coordinate to the surface of the nanocrystals. The method involves only a simple stirring or sonication of the nanocrystals dispersion with the ligands of interest. Dicarboxylic acids such as sebacic acid, adipic acid, succinic acid, and malonic acid-functionalized nanocrystals which are difficult to achieve via thermal decomposition method were easily prepared by this ligand exchange strategy. In addition, low boiling point ligands like hexanoic acid can easily be coated over the surface of the Er/Yb-doped NaYF4 nanocrystals. Both size and shape of the nanocrystals were preserved after the ligand exchange process. The methyl oleate-capped Er/Yb-doped NaYF4 nanocrystals display strong upconversion emission after ligand exchanged with hydrophobic and hydrophilic molecules. The high stability of the nanocrystals after ligand exchange process is verified by performing time-dependent luminescent measurements at different pH, buffers, etc. PMID:25902373

  9. Solvothermal crystallization of nanocrystals of metal oxides

    NASA Astrophysics Data System (ADS)

    Furukawa, S.; Amino, H.; Iwamoto, S.; Inoue, M.

    2008-07-01

    Solvothermal crystallization of the hydroxide gels obtained by hydrolysis of alkoxides (Zr, Ta, Nb, ln, Sn, Ti and Al) was examined. Nanocrystals having high surface areas (SBET > 170 m2 g-1) were obtained except for the product derived from indium isopropoxide. The effect of water in organic solvent upon the crystallinity of the product was investigated. The increase in the activity of water by using high concentration of alkoxide or intentional addition of water to the solvothermal medium led to crystal growth of the products. In contrast, decrease in activity of water by adding ethylene glycol before solvothermal treatment caused a decrease in crystallinity of the product.

  10. Bridging the Gap: Electron Relay and Plasmonic Sensitization of Metal Nanocrystals for Metal Clusters.

    PubMed

    Xiao, Fang-Xing; Zeng, Zhiping; Liu, Bin

    2015-08-26

    In recent years, enormous attention has been paid to the construction of metal cluster-semiconductor nanocomposites because of the fascinating and unique properties of metal clusters; however, investigations on photoelectrochemical (PEC) and photocatalytic properties of metal cluster-semiconductor systems are still rare. Moreover, to date, intrinsic correlation between metal clusters and bulk metal nanocrystals has yet to be elucidated. In this work, a facile layer-by-layer (LbL) self-assembly strategy has been developed to judiciously and intimately integrate gold nanocrystals (Au) within the interface between gold clusters (Au(x)) and hierarchically ordered TiO2 nanotube arrays framework, by which imperative roles of Au nanocrystals as electron relay mediator and plasmonic sensitizer for Aux clusters were revealed. In addition, it was found that synergistic interaction between Au nanocrystals and Aux clusters contributed to promising visible-light-driven photocatalytical and PEC performances. It is anticipated that our work could provide a general way for rationally constructing metal and metal clusters codecorated semiconductor heterostructures and, more significantly, bridge the gap between metal clusters and metal nanocrystals for a diverse range of applications. PMID:26258281

  11. Template Synthesis of Nanostructured Metals using Cellulose Nanocrystal

    SciTech Connect

    Shin, Yongsoon; Exarhos, Gregory J.

    2009-11-01

    In this chapter, cellulose nanocrystal (CNXL) has been used as a template and reducing agent for synthesizing nanoscale inorganic solids such as metal oxide, metal carbide, and nanocrystalline metals. CNXL selectively nucleates metal or metal oxide phases in ordered arrangements commensurate with the attendant structure and chemistry of the fiber. The reaction has an analogy to the well-known Tollen’s reagent where addition of an aldehyde or glucose analyte to a glass vessel containing a soluble ammoniacal silver complex causes reduction of the silver to form a mirror on the vessel surface. For the synthesis of TiO2, CNXL produced mesoporous anatase with 5-10 nm particle sizes and 170-200 m2/g surface area after air-calcination. Silica-infiltrated CNXL produced very homogeneous SiC nanowires with 70 nm in diameter at 1400 oC in Ar. For the syntheses of metal nanoparticles, upon addition of aqueous metal ion containing solutions (Cu(II), Ni(II), Ag(I), Au(III), Pd(II), Pt(IV), or even selenite, Se(IV)) into the CNXL suspension, reduction to the metal occurs under hydrothermal conditions to form ordered metal nanostructures. Ni (II) and Cu(II) ions required high temperature (300-400 oC) to be reduced due to their low reduction potentials. However, metal ions including Ag(I), Au(III), Pt(IV), Pd(II), Se(IV) needed lower temperatures (160-200 oC) to be reduced. Enhanced catalytic activity on these templated surfaces has been demonstrated for a methylene-blue dye photo-induced decomposition (Se nanocrystals resident on crystalline cellulose).

  12. Generalized chemical route to develop fatty acid capped highly dispersed semiconducting metal sulphide nanocrystals

    SciTech Connect

    Patel, Jayesh D.; Mighri, Frej; Ajji, Abdellah

    2012-08-15

    Highlights: ► Chemical route for the synthesis of OA-capped CdS, ZnS and PbS at low temperature. ► Synthesized nanocrystals via thermolysis of their metal–oleate complexes. ► Size quantized nanocrystals were highly dispersed and stable at room temperature. -- Abstract: This work deals with the synthesis of highly dispersed semiconducting nanocrystals (NCs) of cadmium sulphide (CdS), zinc sulphide (ZnS) and lead sulphide (PbS) through a simple and generalized process using oleic acid (OA) as surfactant. To synthesize these NCs, metal–oleate (M–O) complexes were obtained from the reaction at 140 °C between metal acetates and OA in hexanes media. Subsequently, M–O complexes were sulphurized using thioacetamide at the same temperature. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) characterizations show that the synthesized products are of nanoscale-size with highly crystalline cubic phase. The optical absorption of OA-capped metal sulphide NCs confirms that their size quantization induced a large shift towards visible region. Photoluminescence (PL) spectrum of CdS NCs shows a broad band-edge emission with shallow and deep-trap emissions, while PL spectrum of ZnS NCs reveals a broad emission due to defects states on the surface. The thermogravimetric analysis (TGA) and Fourier transform infrared (FTIR) spectroscopy indicate that fatty acid monolayers were bound strongly on the nanocrystal surface as a carboxylate and the two oxygen atoms of the carboxylate were coordinated symmetrically to the surface of the NCs. The strong binding between the fatty acid and the NCs surface enhances the stability of NCs colloids. In general, this generalized route has a great potential in developing nanoscale metal sulphides for opto-electronic devices.

  13. Metallic Carbon Nanotubes and Ag Nanocrystals

    SciTech Connect

    Brus, Louis E

    2014-03-04

    The goal of this DOE solar energy research was to understand how visible light interacts with matter, and how to make electric excitations evolve into separated electrons and holes in photovoltaic cells, especially in nanoparticles and nanowires. Our specific experiments focused on A) understanding plasmon enhanced spectroscopy and charge-transfer (metal-to-molecule) photochemistry on the surface of metallic particles and B) the spectroscopy and photochemistry of carbon nanotubes and graphene. I also worked closely with R. Friesner on theoretical studies of photo-excited electrons near surfaces of titanium dioxide nanoparticles; this process is relevant to the Gratzel photovoltaic cell.

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

    PubMed

    Kwon, Soon Gu; Hyeon, Taeghwan

    2008-12-01

    Nanocrystals exhibit interesting electrical, optical, magnetic, and chemical properties not achieved by their bulk counterparts. Consequently, to fully exploit the potential of nanocrystals, the synthesis of nanocrystals must focus on producing materials with uniform size and shape. Top-down physical processes can produce large quantities of nanocrystals, but controlling the size is difficult with these methods. On the other hand, colloidal chemical synthetic methods can produce uniform nanocrystals with a controlled particle size. In this Account, we present our synthesis of uniform nanocrystals of various shapes and materials, and we discuss the kinetics of nanocrystal formation. We employed four different synthetic approaches including thermal decomposition, nonhydrolytic sol-gel reactions, thermal reduction, and use of reactive chalcogen reagents. We synthesized uniform oxide nanocrystals via heat-up methods. This method involved slowly heat-up reaction mixtures composed of metal precursors, surfactants, and solvents from room temperature to high temperature. We then held reaction mixtures at an aging temperature for a few minutes to a few hours. Kinetics studies revealed a three-step mechanism for the synthesis of nanocrystals through the heat-up method with size distribution control. First, as metal precursors thermally decompose, monomers accumulate. At the aging temperature, burst nucleation occurs rapidly; at the end of this second phase, nucleation stops, but continued diffusion-controlled growth leads to size focusing to produce uniform nanocrystals. We used nonhydrolytic sol-gel reactions to synthesize various transition metal oxide nanocrystals. We employed ester elimination reactions for the synthesis of ZnO and TiO(2) nanocrystals. Uniform Pd nanoparticles were synthesized via a thermal reduction reaction induced by heating up a mixture of Pd(acac)(2), tri-n-octylphosphine, and oleylamine to the aging temperature. Similarly, we synthesized

  15. Nonthermal plasma synthesis of metal sulfide nanocrystals from metalorganic vapor and elemental sulfur

    NASA Astrophysics Data System (ADS)

    Thimsen, Elijah; Kortshagen, Uwe R.; Aydil, Eray S.

    2015-08-01

    Nanocrystal synthesis in nonthermal plasmas has been focused on elemental group IV semiconductors such as Si and Ge. In contrast, very little is known about plasma synthesis of compound nanocrystals and the time is ripe to extend this synthesis approach to nanocrystals comprised of two or more elements such as metal sulfides, oxides and nitrides. Towards this end, we studied, in an argon-sulfur plasma, the synthesis of ZnS, Cu2S and SnS nanocrystals from metalorganic precursors diethyl Zn(II), hexafluoroacetylacetonate Cu(I) vinyltrimethylsilane, and tetrakis(dimethylamido) Sn(IV), respectively. In situ optical emission spectroscopy was used to observe changes in relative concentrations of various plasma species during synthesis, while ex situ material characterization was used to examine the crystal structure, elemental composition and optical absorption of these nanocrystals. For a constant metalorganic vapor feed rate, the elemental composition of the nanocrystals was found to be independent of the sulfur flow rate into the plasma, above a small threshold value. At constant sulfur flow rate, the nanocrystal composition depended on the metalorganic vapor feed rate. Specifically, the ensemble metal atomic fraction in the nanocrystals was found to increase with increasing metalorganic vapor flow rates, resulting in more metal-rich crystal phases. The metalorganic feed rate can be used to control the composition and crystal phase of the metal-sulfide nanocrystals synthesized using this plasma process.

  16. Remote electronic control of DNA hybridization through inductive coupling to an attached metal nanocrystal antenna

    NASA Astrophysics Data System (ADS)

    Hamad-Schifferli, Kimberly; Schwartz, John J.; Santos, Aaron T.; Zhang, Shuguang; Jacobson, Joseph M.

    2002-01-01

    Increasingly detailed structural and dynamic studies are highlighting the precision with which biomolecules execute often complex tasks at the molecular scale. The efficiency and versatility of these processes have inspired many attempts to mimic or harness them. To date, biomolecules have been used to perform computational operations and actuation, to construct artificial transcriptional loops that behave like simple circuit elements and to direct the assembly of nanocrystals. Further development of these approaches requires new tools for the physical and chemical manipulation of biological systems. Biomolecular activity has been triggered optically through the use of chromophores, but direct electronic control over biomolecular `machinery' in a specific and fully reversible manner has not yet been achieved. Here we demonstrate remote electronic control over the hybridization behaviour of DNA molecules, by inductive coupling of a radio-frequency magnetic field to a metal nanocrystal covalently linked to DNA. Inductive coupling to the nanocrystal increases the local temperature of the bound DNA, thereby inducing denaturation while leaving surrounding molecules relatively unaffected. Moreover, because dissolved biomolecules dissipate heat in less than 50picoseconds (ref. 16), the switching is fully reversible. Inductive heating of macroscopic samples is widely used, but the present approach should allow extension of this concept to the control of hybridization and thus of a broad range of biological functions on the molecular scale.

  17. Nanocrystal structures

    SciTech Connect

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

    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.

  18. 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.

  19. Synthesis of metal selenide colloidal nanocrystals by the hot injection of selenium powder.

    PubMed

    Flamee, Stijn; Dierick, Ruben; Cirillo, Marco; Van Genechten, Dirk; Aubert, Tangi; Hens, Zeger

    2013-09-21

    We describe the synthesis of metal selenide nanocrystals, including CdSe, ZnSe, CuInSe2 and Cu2(Zn,Sn)Se4, by the hot injection of selenium powder dispersed in a carrier solvent. Since this results in a fast and high yield nanocrystal formation, we argue that the approach is well suited for the low cost, large volume production of nanocrystals. PMID:23657539

  20. Galvanic Exchange in Colloidal Metal/Metal-Oxide Core/Shell Nanocrystals

    PubMed Central

    2016-01-01

    While galvanic exchange is commonly applied to metallic nanoparticles, recently its applicability was expanded to metal-oxides. Here the galvanic exchange is studied in metal/metal-oxide core/shell nanocrystals. In particular Sn/SnO2 is treated by Ag+, Pt2+, Pt4+, and Pd2+. The conversion dynamics is monitored by in situ synchrotron X-ray diffraction. The Ag+ treatment converts the Sn cores to the intermetallic AgxSn (x ∼ 4) phase, by changing the core’s crystal structure. For the analogous treatment by Pt2+, Pt4+, and Pd2+, such a galvanic exchange is not observed. This different behavior is caused by the semipermeability of the naturally formed SnO2 shell, which allows diffusion of Ag+ but protects the nanocrystal cores from oxidation by Pt and Pd ions.

  1. On the Dynamic Stoichiometry of Metal Chalcogenide Nanocrystals: Spectroscopic Studies of Metal Carboxylate Binding and Displacement

    PubMed Central

    Anderson, Nicholas C.; Hendricks, Mark P.; Choi, Joshua J.; Owen, Jonathan S.

    2013-01-01

    We demonstrate that metal carboxylate complexes (L–M(O2CR)2, R = oleyl, tetradecyl, M = Cd, Pb) are readily displaced from carboxylate-terminated ME nanocrystals (ME = CdSe, CdS, PbSe, PbS) by various Lewis bases (L = tri-n-butylamine, tetrahydrofuran, tetradecanol, N,N-dimethyl-n-butylamine, tri-n-butylphosphine, N,N,N',N'-tetramethylbutylene-1,4-diamine, pyridine, N,N,N',N'-tetramethylethylene-1,2-diamine, n-octylamine). The relative displacement potency is measured by 1H NMR spectroscopy and depends most strongly on geometric factors like sterics and chelation, though also on the hard/soft match with the cadmium ion. The results suggest that ligands displace L–M(O2CR)2 by cooperatively complexing the displaced metal ion as well as the nanocrystal. Removal of up to 90% of surface bound Cd(O2CR)2 from CdSe and CdS nanocrystals decreases the Cd:Se ratio from 1.1 ± 0.06 to 1.0 ± 0.05, broadens the 1Se-2S3/2h absorption and decreases the photoluminescence quantum yield (PLQY) from 10% to <1% (CdSe) and 20% to <1% (CdS). These changes are partially reversed upon rebinding of M(O2CR)2 at room temperature (~60 %) and fully reversed at elevated temperature. A model is proposed where electron accepting M(O2CR)2 complexes (Z-type ligands) reversibly bind to nanocrystals leading to a range of stoichiometries for a given core size. The results demonstrate that nanocrystals lack a single chemical formula, but are instead dynamic structures with concentration-dependent compositions. The importance of these findings to the synthesis and purification of nanocrystals as well as ligand exchange reactions is discussed. PMID:24199846

  2. Contact Radius and the Insulator-Metal Transition in Films Comprised of Touching Semiconductor Nanocrystals.

    PubMed

    Lanigan, Deanna; Thimsen, Elijah

    2016-07-26

    Nanocrystal assemblies are being explored for a number of optoelectronic applications such as transparent conductors, photovoltaic solar cells, and electrochromic windows. Majority carrier transport is important for these applications, yet it remains relatively poorly understood in films comprised of touching nanocrystals. Specifically, the underlying structural parameters expected to determine the transport mechanism have not been fully elucidated. In this report, we demonstrate experimentally that the contact radius, between touching heavily doped ZnO nanocrystals, controls the electron transport mechanism. Spherical nanocrystals are considered, which are connected by a circular area. The radius of this circular area is the contact radius. For nanocrystals that have local majority carrier concentration above the Mott transition, there is a critical contact radius. If the contact radius between nanocrystals is less than the critical value, then the transport mechanism is variable range hopping. If the contact radius is greater than the critical value, the films display behavior consistent with metallic electron transport. PMID:27398597

  3. Noble-Metal Nanocrystals with Controlled Facets for Electrocatalysis.

    PubMed

    Hong, Jong Wook; Kim, Yena; Kwon, Yongmin; Han, Sang Woo

    2016-08-19

    Noble-metal nanocrystals (NCs) show excellent catalytic performance for many important electrocatalysis reactions. The crystallographic properties of the facets by which the NCs are bound, closely associated with the shape of the NCs, have a profound influence on the electrocatalytic function of the NCs. To develop an efficient strategy for the synthesis of NCs with controlled facets as well as compositions, understanding of the growth mechanism of the NCs and their interaction with the chemical species involved in NC synthesis is quite important. Furthermore, understanding the facet-dependent catalytic properties of noble-metal NCs and the corresponding mechanisms for various electrocatalysis reactions will allow for the rational design of robust electrocatalysts. In this review, we summarize recently developed synthesis strategies for the preparation of mono- and bimetallic noble-metal NCs by classifying them by the type of facets through which they are enclosed and discuss the electrocatalytic applications of noble-metal NCs with controlled facets, especially for reactions associated with fuel-cell applications, such as the oxygen reduction reaction and fuel (methanol, ethanol, and formic acid) oxidation reactions. PMID:27258679

  4. 1/f noise in semiconductor and metal nanocrystal solids

    SciTech Connect

    Liu, Heng Lhuillier, Emmanuel 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 with a similar temperature dependence.

  5. Structure stabilities and transitions in polyhedral metal nanocrystals: An atomic-bond-relaxation approach

    NASA Astrophysics Data System (ADS)

    Zhang, Ai; Zhu, Ziming; He, Yan; Ouyang, Gang

    2012-04-01

    We present an atomic-bond-relaxation (ABR) method to illustrate a deeper insight on structure stabilities and transitions of metal nanocrystals with polyhedral structure based on the thermodynamic consideration. It has been found that the end effects in polyhedral nanocrystals induced by the atoms located at edges, side facets, and vertexes play the dominant roles for their structure performances. The theoretical predictions are well consistent with the experimental measurements and simulations, which suggest the ABR model can be an effective method to understand solid-solid phase transition of polyhedral metal nanocrystals.

  6. Direct observation of narrow mid-infrared plasmon linewidths of single metal oxide nanocrystals

    PubMed Central

    Johns, Robert W.; Bechtel, Hans A.; Runnerstrom, Evan L.; Agrawal, Ankit; Lounis, Sebastien D.; Milliron, Delia J.

    2016-01-01

    Infrared-responsive doped metal oxide nanocrystals are an emerging class of plasmonic materials whose localized surface plasmon resonances (LSPR) can be resonant with molecular vibrations. This presents a distinctive opportunity to manipulate light–matter interactions to redirect chemical or spectroscopic outcomes through the strong local electric fields they generate. Here we report a technique for measuring single nanocrystal absorption spectra of doped metal oxide nanocrystals, revealing significant spectral inhomogeneity in their mid-infrared LSPRs. Our analysis suggests dopant incorporation is heterogeneous beyond expectation based on a statistical distribution of dopants. The broad ensemble linewidths typically observed in these materials result primarily from sample heterogeneity and not from strong electronic damping associated with lossy plasmonic materials. In fact, single nanocrystal spectra reveal linewidths as narrow as 600 cm−1 in aluminium-doped zinc oxide, a value less than half the ensemble linewidth and markedly less than homogeneous linewidths of gold nanospheres. PMID:27174681

  7. Direct observation of narrow mid-infrared plasmon linewidths of single metal oxide nanocrystals.

    PubMed

    Johns, Robert W; Bechtel, Hans A; Runnerstrom, Evan L; Agrawal, Ankit; Lounis, Sebastien D; Milliron, Delia J

    2016-01-01

    Infrared-responsive doped metal oxide nanocrystals are an emerging class of plasmonic materials whose localized surface plasmon resonances (LSPR) can be resonant with molecular vibrations. This presents a distinctive opportunity to manipulate light-matter interactions to redirect chemical or spectroscopic outcomes through the strong local electric fields they generate. Here we report a technique for measuring single nanocrystal absorption spectra of doped metal oxide nanocrystals, revealing significant spectral inhomogeneity in their mid-infrared LSPRs. Our analysis suggests dopant incorporation is heterogeneous beyond expectation based on a statistical distribution of dopants. The broad ensemble linewidths typically observed in these materials result primarily from sample heterogeneity and not from strong electronic damping associated with lossy plasmonic materials. In fact, single nanocrystal spectra reveal linewidths as narrow as 600 cm(-1) in aluminium-doped zinc oxide, a value less than half the ensemble linewidth and markedly less than homogeneous linewidths of gold nanospheres. PMID:27174681

  8. Hydrogen storage in Pd nanocrystals covered with a metal-organic framework.

    PubMed

    Li, Guangqin; Kobayashi, Hirokazu; Taylor, Jared M; Ikeda, Ryuichi; Kubota, Yoshiki; Kato, Kenichi; Takata, Masaki; Yamamoto, Tomokazu; Toh, Shoichi; Matsumura, Syo; Kitagawa, Hiroshi

    2014-08-01

    Hydrogen is an essential component in many industrial processes. As a result of the recent increase in the development of shale gas, steam reforming of shale gas has received considerable attention as a major source of H2, and the more efficient use of hydrogen is strongly demanded. Palladium is well known as a hydrogen-storage metal and an effective catalyst for reactions related to hydrogen in a variety of industrial processes. Here, we present remarkably enhanced capacity and speed of hydrogen storage in Pd nanocrystals covered with the metal-organic framework (MOF) HKUST-1 (copper(II) 1,3,5-benzenetricarboxylate). The Pd nanocrystals covered with the MOF have twice the storage capacity of the bare Pd nanocrystals. The significantly enhanced hydrogen storage capacity was confirmed by hydrogen pressure-composition isotherms and solid-state deuterium nuclear magnetic resonance measurements. The speed of hydrogen absorption in the Pd nanocrystals is also enhanced by the MOF coating. PMID:25017188

  9. Hydrogen storage in Pd nanocrystals covered with a metal-organic framework

    NASA Astrophysics Data System (ADS)

    Li, Guangqin; Kobayashi, Hirokazu; Taylor, Jared M.; Ikeda, Ryuichi; Kubota, Yoshiki; Kato, Kenichi; Takata, Masaki; Yamamoto, Tomokazu; Toh, Shoichi; Matsumura, Syo; Kitagawa, Hiroshi

    2014-08-01

    Hydrogen is an essential component in many industrial processes. As a result of the recent increase in the development of shale gas, steam reforming of shale gas has received considerable attention as a major source of H2, and the more efficient use of hydrogen is strongly demanded. Palladium is well known as a hydrogen-storage metal and an effective catalyst for reactions related to hydrogen in a variety of industrial processes. Here, we present remarkably enhanced capacity and speed of hydrogen storage in Pd nanocrystals covered with the metal-organic framework (MOF) HKUST-1 (copper(II) 1,3,5-benzenetricarboxylate). The Pd nanocrystals covered with the MOF have twice the storage capacity of the bare Pd nanocrystals. The significantly enhanced hydrogen storage capacity was confirmed by hydrogen pressure-composition isotherms and solid-state deuterium nuclear magnetic resonance measurements. The speed of hydrogen absorption in the Pd nanocrystals is also enhanced by the MOF coating.

  10. Direct observation of narrow mid-infrared plasmon linewidths of single metal oxide nanocrystals

    NASA Astrophysics Data System (ADS)

    Johns, Robert W.; Bechtel, Hans A.; Runnerstrom, Evan L.; Agrawal, Ankit; Lounis, Sebastien D.; Milliron, Delia J.

    2016-05-01

    Infrared-responsive doped metal oxide nanocrystals are an emerging class of plasmonic materials whose localized surface plasmon resonances (LSPR) can be resonant with molecular vibrations. This presents a distinctive opportunity to manipulate light-matter interactions to redirect chemical or spectroscopic outcomes through the strong local electric fields they generate. Here we report a technique for measuring single nanocrystal absorption spectra of doped metal oxide nanocrystals, revealing significant spectral inhomogeneity in their mid-infrared LSPRs. Our analysis suggests dopant incorporation is heterogeneous beyond expectation based on a statistical distribution of dopants. The broad ensemble linewidths typically observed in these materials result primarily from sample heterogeneity and not from strong electronic damping associated with lossy plasmonic materials. In fact, single nanocrystal spectra reveal linewidths as narrow as 600 cm-1 in aluminium-doped zinc oxide, a value less than half the ensemble linewidth and markedly less than homogeneous linewidths of gold nanospheres.

  11. A simple route to alloyed quaternary nanocrystals Ag-In-Zn-S with shape and size control.

    PubMed

    Gabka, Grzegorz; Bujak, Piotr; Giedyk, Kamila; Ostrowski, Andrzej; Malinowska, Karolina; Herbich, Jerzy; Golec, Barbara; Wielgus, Ireneusz; Pron, Adam

    2014-05-19

    A convenient method of the preparation of alloyed quaternary Ag-In-Zn-S nanocrystals is elaborated, in which a multicomponent mixture of simple and commercially available precursors, namely, silver nitrate, indium(III) chloride, zinc stearate, 1-dodecanethiol, and sulfur, is used with 1-octadecene as a solvent. The formation of quaternary nanocrystals necessitates the use of an auxiliary sulfur precursor, namely, elemental sulfur dissolved in oleylamine, in addition to 1-dodecanethiol. Without this additional precursor binary ZnS nanocrystals are formed. The optimum reaction temperature of 180 °C was also established. In these conditions shape, size, and composition of the resulting nanocrystals can be adjusted in a controlled manner by changing the molar ratio of the precursors in the reaction mixture. For low zinc stearate contents anisotropic rodlike (ca.3 nm x 10 nm) and In-rich nanocrystals are obtained. This is caused by a significantly higher reactivity of the indium precursor as compared to the zinc one. With increasing zinc precursor content the reactivities of both precursors become more balanced, and the resulting nanocrystals are smaller (1.5-4.0 nm) and become Zn-rich as evidenced by transmission electron microscopy, X-ray diffraction, and energy-dispersive spectrometry investigations. Simultaneous increases in the zinc and sulfur precursor content result in an enlargement of nanocrystals (2.5 to 5.0 nm) and further increase in the molar ZnS content (up to 0.76). The prepared nanoparticles show stable photoluminescence with the quantum yield up to 37% for In and Zn-rich nanocrystals. Their hydrodynamic diameter in toluene dispersion, determined by dynamic light scattering, is roughly twice larger than the diameter of their inorganic core. PMID:24786548

  12. Control of metal nanocrystal size reveals metal-support interface role for ceria catalysts.

    PubMed

    Cargnello, Matteo; Doan-Nguyen, Vicky V T; Gordon, Thomas R; Diaz, Rosa E; Stach, Eric A; Gorte, Raymond J; Fornasiero, Paolo; Murray, Christopher B

    2013-08-16

    Interactions between ceria (CeO2) and supported metals greatly enhance rates for a number of important reactions. However, direct relationships between structure and function in these catalysts have been difficult to extract because the samples studied either were heterogeneous or were model systems dissimilar to working catalysts. We report rate measurements on samples in which the length of the ceria-metal interface was tailored by the use of monodisperse nickel, palladium, and platinum nanocrystals. We found that carbon monoxide oxidation in ceria-based catalysts is greatly enhanced at the ceria-metal interface sites for a range of group VIII metal catalysts, clarifying the pivotal role played by the support. PMID:23868919

  13. Control of Metal Nanocrystal Size Reveals Metal-Support Interface Role for Ceria Catalysts

    SciTech Connect

    Cargnello, M; Doan-Nguyen, VVT; Gordon, TR; Diaz, RE; Stach, EA; Gorte, RJ; Fornasiero, P; Murray, CB

    2013-08-15

    Interactions between ceria (CeO2) and supported metals greatly enhance rates for a number of important reactions. However, direct relationships between structure and function in these catalysts have been difficult to extract because the samples studied either were heterogeneous or were model systems dissimilar to working catalysts. We report rate measurements on samples in which the length of the ceria-metal interface was tailored by the use of monodisperse nickel, palladium, and platinum nanocrystals. We found that carbon monoxide oxidation in ceria-based catalysts is greatly enhanced at the ceria-metal interface sites for a range of group VIII metal catalysts, clarifying the pivotal role played by the support.

  14. Dynamics of formation of Ru, Os, Ir and Au metal nanocrystals on doped graphitic surfaces.

    PubMed

    Pitto-Barry, Anaïs; Sadler, Peter J; Barry, Nicolas P E

    2016-03-11

    The fabrication of precious metal (ruthenium, osmium, gold, and iridium) nanocrystals from single atoms has been studied in real-time. The dynamics of the first stage of the metal nanocrystallisation on a doped (B,S)-graphitic surface are identified, captured, and reported. PMID:26698913

  15. Modification of SiO2 nanowires with metallic nanocrystals from supercritical CO2.

    PubMed

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

    2004-01-01

    Through hydrogen reduction of metal precursors in supercritical CO2, Cu, and Pd, nanocrystals were deposited onto SiO2 nanowires to form different types of nanostructured materials, including nanocrystal-nanowire, spherical aggregation-nanowire, shell-nanowire composites, and "mesoporous" metals supported by the framework of nanowires. This supercritical fluid deposition technique is an attractive approach for modifying nanowires because of its generality and simplicity; the modified nanowires could be useful as catalysts and for further fabrication of multifunctional composites. PMID:15112546

  16. A simple route to Bi2Se3 and Bi2Te3 nanocrystals

    NASA Astrophysics Data System (ADS)

    Mntungwa, Nhlakanipho; Rajasekhar, Pullabhotla V. S. R.; Ramasamy, Karthik; Revaprasadu, Neerish

    2014-05-01

    Monodisperse nanocrystals of Bi2Se3 and Bi2Te3 capped with alkylamines have been synthesized via facile solution based method. The method involves reduction of selenium or tellurium using sodium borohydride, followed by thermolysis in an alkylamine at high temperature. Spherical shaped Bi2Se3 nanocrystals were obtained at 190 °C, whereas the reaction at 270 °C, yielded faceted nanocrystals. Similarly, spherical Bi2Te3 nanocrystals were obtained at all temperatures with hexadecylamine and oleylamine capping agents.

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

    SciTech Connect

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

    2015-04-01

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

  18. Synthesis and characterization of transition-metal nanocrystals and their application in catalysis

    NASA Astrophysics Data System (ADS)

    Cheng, Guangjun

    Extended X-ray absorption fine structure (EXAFS) spectroscopy and transmission electron microscopy (TEM) have been used to investigate Ni/Co bimetallic nanoparticles (bi-MNPs) produced via laser vaporization of a carbon-metal mixture. Results show that the structures of these nanoparticles are face-center-cubic, and each of the nanoparticles examined contains 50% of Ni and Co. A detailed analysis of the EXAFS data using Fourier filtering and single scattering theory has revealed that the surface of the nanoparticles is predominantly occupied by Ni atoms. In order to further study the application of the transition-metal nanocrystals in catalysis, different sizes of Co nanocrystals are synthesized using thermo-decomposition. Extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) are used as tools, theoretically and experimentally, for studying the structures and dynamics of these Co nanocrystals. These Co nanocrystals are used as catalysts to grow self-aligned one-dimensional CoSi2 nanostructures on Si substrates by chemical vapor deposition (CVD). Scanning electron microscopy (SEM), atomic force microscopy (AFM), and transmission electron microscopy (TEM) are used to characterize as-prepared nanostructures. The effects of reaction temperature, Si substrates, flow rates of the feeding gases and nanocrystal size on the growth of CoSi2 have been studied systematically. The nanostructure so produced are of high quality and are well arranged, making them available to many applications. We also expand the Co nanocrystals synthesis to Ni nanocrystals and Ni/Co bimetallic nanocrystals. Transmission electron microscope (TEM) and X-ray diffraction (XRD) and energy dispersive x-ray spectroscopy (EDX) have been used to characterize as-prepared nanocrystals. A high repetition rate, compact terawatt Ti: Sapphire laser system is presented. The oscillator produces an 82-MHz pulse train consisting of broad bandwidth pulses of 0.5 n

  19. Nonexponential relaxation in a simple liquid metal.

    PubMed

    Demmel, F; Morkel, C

    2012-05-01

    A hallmark of the changes in dynamics towards the glass transition is the stretched exponential structural relaxation. Quasielastic neutron scattering results on liquid rubidium demonstrate such a nonexponential relaxation process in a simple liquid metal above the melting point. The nonexponential decay is an indication of non-Markovian dynamics and points to the collective character of the relaxation process. Describing the relaxation dynamics by a two-step process, the long lasting part of the decay process is in remarkable quantitative agreement with predictions from mode coupling theory. The feedback mechanism of the slowing down process in the theoretical description suggests that this contribution is at the origin of the structural arrest. With rising temperature the intermediate scattering function transforms into a simple exponential decay at a temperature range which indicates the end of the highly viscous solidlike behavior in the liquid. PMID:23004742

  20. Colloidal metal oxide nanocrystal catalysis by sustained chemically driven ligand displacement

    NASA Astrophysics Data System (ADS)

    de Roo, Jonathan; van Driessche, Isabel; Martins, José C.; Hens, Zeger

    2016-05-01

    Surface chemistry is a key enabler for colloidal nanocrystal applications. In this respect, metal oxide nanocrystals (NCs) stand out from other NCs as carboxylic acid ligands adsorb on their surface by dissociation to carboxylates and protons, the latter proving essential in electron transfer reactions. Here, we show that this binding motif sets the stage for chemically driven ligand displacement where the binding of amines or alcohols to HfO2 NCs is promoted by the conversion of a bound carboxylic acid into a non-coordinating amide or ester. Furthermore, the sustained ligand displacement, following the addition of excess carboxylic acid, provides a catalytic pathway for ester formation, whereas the addition of esters leads to NC-catalysed transesterification. Because sustained, chemically driven ligand displacement leaves the NCs--including their surface composition--unchanged and preserves colloidal stability, metal oxide nanocrystals are thus turned into effective nanocatalysts that bypass the tradeoff between colloidal stability and catalytic activity.

  1. Colloidal metal oxide nanocrystal catalysis by sustained chemically driven ligand displacement.

    PubMed

    De Roo, Jonathan; Van Driessche, Isabel; Martins, José C; Hens, Zeger

    2016-05-01

    Surface chemistry is a key enabler for colloidal nanocrystal applications. In this respect, metal oxide nanocrystals (NCs) stand out from other NCs as carboxylic acid ligands adsorb on their surface by dissociation to carboxylates and protons, the latter proving essential in electron transfer reactions. Here, we show that this binding motif sets the stage for chemically driven ligand displacement where the binding of amines or alcohols to HfO2 NCs is promoted by the conversion of a bound carboxylic acid into a non-coordinating amide or ester. Furthermore, the sustained ligand displacement, following the addition of excess carboxylic acid, provides a catalytic pathway for ester formation, whereas the addition of esters leads to NC-catalysed transesterification. Because sustained, chemically driven ligand displacement leaves the NCs-including their surface composition-unchanged and preserves colloidal stability, metal oxide nanocrystals are thus turned into effective nanocatalysts that bypass the tradeoff between colloidal stability and catalytic activity. PMID:26808460

  2. Floating gate memory-based monolayer MoS2 transistor with metal nanocrystals embedded in the gate dielectrics.

    PubMed

    Wang, Jingli; Zou, Xuming; Xiao, Xiangheng; Xu, Lei; Wang, Chunlan; Jiang, Changzhong; Ho, Johnny C; Wang, Ti; Li, Jinchai; Liao, Lei

    2015-01-14

    Charge trapping layers are formed from different metallic nanocrystals in MoS2 -based nanocrystal floating gate memory cells in a process compatible with existing fabrication technologies. The memory cells with Au nanocrystals exhibit impressive performance with a large memory window of 10 V, a high program/erase ratio of approximately 10(5) and a long retention time of 10 years. PMID:25115804

  3. Photocatalytic properties of zinc sulfide nanocrystals biofabricated by metal-reducing bacterium Shewanella oneidensis MR-1.

    PubMed

    Xiao, Xiang; Ma, Xiao-Bo; Yuan, Hang; Liu, Peng-Cheng; Lei, Yu-Bin; Xu, Hui; Du, Dao-Lin; Sun, Jian-Fan; Feng, Yu-Jie

    2015-05-15

    Accumulation and utilization of heavy metals from wastewater by biological treatment system has aroused great interest. In the present study, a metal-reducing bacterium Shewanella oneidensis MR-1 was used to explore the biofabrication of ZnS nanocrystals from the artificial wastewater. The biogenic H2S produced via the reduction of thiosulfate precipitated the Zn(II) as sulfide extracellularly. Characterization by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), and field emission scanning electron microscope (FESEM) confirmed the precipitates as ZnS nanocrystals. The biogenic ZnS nanocrystals appeared spherical in shape with an average diameter of 5 nm and mainly aggregated in the medium and cell surface of S. oneidensis MR-1. UV-vis DRS spectra showed ZnS nanoparticles appeared a strong absorption below 360 nm. Thus, the photocatalytic activity of ZnS was evaluated by the photodegradation of rhodamine B (RhB) under UV irradiation. The biogenic ZnS nanocrystals showed a high level of photodegradation efficiency to RhB coupled with a significant blue-shift of maximum adsorption peak. A detailed analysis indicated the photogenerated holes, rather than hydroxyl radicals, contributed to the photocatalytic decolorization of RhB. This approach of coupling biosynthesis of nanoparticles with heavy metal removal may offer a potential avenue for efficient bioremediation of heavy metal wastewater. PMID:25698574

  4. Decoration of size-tunable CuO nanodots on TiO2 nanocrystals for noble metal-free photocatalytic H2 production

    NASA Astrophysics Data System (ADS)

    Moon, Geon Dae; Joo, Ji Bong; Lee, Ilkeun; Yin, Yadong

    2014-09-01

    We report a simple yet effective approach for the decoration of the TiO2 nanocrystal surface with size-tunable CuO nanodots for high-performance noble metal-free photocatalytic H2 production. Modification with polyacrylic acid enables the surface of TiO2 nanocrystals to be selectively deposited with Cu(OH)2 nanodots, which can be subsequently converted to CuO through dehydration without changing their morphologies. UV irradiation of the nanocomposite solution in the presence of a hole scavenger produces photogenerated electrons which reduce CuO to metallic Cu nanodots, making them effective co-catalysts in a role similar to Pt for promoting photocatalytic H2 production. Due to the considerably high work function of Cu, the formation of a metal-semiconductor Schottky junction induces efficient charge separation and transfer. As a result, the TiO2 nanocrystals decorated with an optimal amount of CuO nanodots (1.7 wt%) could reach ~50% of the photocatalytic activity achievable by the Pt-TiO2 counterparts (1 wt%), clearly demonstrating the great potential of such composite catalysts for efficient noble metal-free photocatalytic H2 production.We report a simple yet effective approach for the decoration of the TiO2 nanocrystal surface with size-tunable CuO nanodots for high-performance noble metal-free photocatalytic H2 production. Modification with polyacrylic acid enables the surface of TiO2 nanocrystals to be selectively deposited with Cu(OH)2 nanodots, which can be subsequently converted to CuO through dehydration without changing their morphologies. UV irradiation of the nanocomposite solution in the presence of a hole scavenger produces photogenerated electrons which reduce CuO to metallic Cu nanodots, making them effective co-catalysts in a role similar to Pt for promoting photocatalytic H2 production. Due to the considerably high work function of Cu, the formation of a metal-semiconductor Schottky junction induces efficient charge separation and transfer. As a

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

    PubMed

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

    2015-07-01

    This Perspective provides a contemporary understanding of the shape evolution of colloidal metal nanocrystals under thermodynamically and kinetically controlled conditions. It has been extremely challenging to investigate this subject in the setting of one-pot synthesis because both the type and number of seeds involved would be changed whenever the experimental conditions are altered, making it essentially impossible to draw conclusions when comparing the outcomes of two syntheses conducted under different conditions. Because of the uncertainty about seeds, most of the mechanistic insights reported in literature for one-pot syntheses of metal nanocrystals with different shapes are either incomplete or ambiguous, and some of them might be misleading or even wrong. Recently, with the use of well-defined seeds for such syntheses, it became possible to separate growth from nucleation and therefore investigate the explicit role(s) played by a specific thermodynamic or kinetic parameter in directing the evolution of colloidal metal nanocrystals into a specific shape. Starting from single-crystal seeds enclosed by a mix of {100}, {111}, and {110} facets, for example, one can obtain colloidal nanocrystals with diversified shapes by adjusting various thermodynamic or kinetic parameters. The mechanistic insights learnt from these studies can also be extended to account for the products of conventional one-pot syntheses that involve self-nucleation only. The knowledge can be further applied to many other types of seeds with twin defects or stacking faults, making it an exciting time to design and synthesize colloidal metal nanocrystals with the shapes sought for a variety of fundamental studies and technologically important applications. PMID:26020837

  6. Metal-organic framework-immobilized polyhedral metal nanocrystals: reduction at solid-gas interface, metal segregation, core-shell structure, and high catalytic activity.

    PubMed

    Aijaz, Arshad; Akita, Tomoki; Tsumori, Nobuko; Xu, Qiang

    2013-11-01

    For the first time, this work presents surfactant-free monometallic and bimetallic polyhedral metal nanocrystals (MNCs) immobilized to a metal-organic framework (MIL-101) by CO-directed reduction of metal precursors at the solid-gas interface. With this novel method, Pt cubes and Pd tetrahedra were formed by CO preferential bindings on their (100) and (111) facets, respectively. PtPd bimetallic nanocrystals showed metal segregation, leading to Pd-rich core and Pt-rich shell. Core-shell Pt@Pd nanocrystals were immobilized to MIL-101 by seed-mediated two-step reduction, representing the first example of core-shell MNCs formed using only gas-phase reducing agents. These MOF-supported MNCs exhibited high catalytic activities for CO oxidation. PMID:24138338

  7. Design of metal/dielectric/nanocrystals core/shell/shell nano-structures for the fluorescence enhancement of cadmium-free semiconductor nanocrystals

    NASA Astrophysics Data System (ADS)

    Chevallier, Théo.; Le Blevennec, Gilles; Chandezon, Frédéric

    2015-10-01

    AgInS2-ZnS (ZAIS) quaternary semiconductors nanocrystals are versatile cadmium-free luminescent nanomaterials. Their broad emission spectrum and strong absorption make them ideal for the development of new white-LED devices taking advantage of nano-optical phenomena. We recently found strategies to increase the photoluminescence quantum yield of ZAIS nanocrystals up to 80%. In a second step toward high efficiency luminescent materials, we aim at increasing the net conversion efficiency of ZAIS nanocrystals by coupling them with metallic nano-antennae. Indeed, by grafting ZAIS nanocrystals onto carefully chosen metal/dielectric core/shell nanoparticles, both the absorption and emission processes can be tuned and enhanced. A finite-element simulation based on the discrete dipole approximation (DDA) was used to predict the nano-optical behavior of silver@oxide@ZAIS nanostructures. Desirable combinations of materials and geometry for the antennae were identified. A chemical method for the synthesis of the simulated nanostructures was developed. The coupling of ZAIS nanocrystals emission with the plasmonic structure is experimentally observed and is in accordance with our predictions.

  8. Process for making surfactant capped metal oxide nanocrystals, and products produced by the process

    DOEpatents

    Alivisatos, A. Paul; Rockenberger, Joerg

    2006-01-10

    Disclosed is a process for making surfactant capped nanocrystals of metal oxides which are dispersable in organic solvents. The process comprises decomposing a metal cupferron complex of the formula MXCupX, wherein M is a metal, and Cup is a N-substituted N-Nitroso hydroxylamine, in the presence of a coordinating surfactant, the reaction being conducted at a temperature ranging from about 150 to about 400.degree. C., for a period of time sufficient to complete the reaction. Also disclosed are compounds made by the process.

  9. Effects of nanocrystal formation on the soft magnetic properties of Fe-based bulk metallic glasses

    NASA Astrophysics Data System (ADS)

    Gao, J. E.; Li, H. X.; Jiao, Z. B.; Wu, Y.; Chen, Y. H.; Yu, T.; Lu, Z. P.

    2011-08-01

    We developed several Fe-based bulk metallic glasses with a unique combination of large glass-forming ability and excellent soft magnetic properties by minor doping of Cu in the Fe76C7.0Si3.3B5.0P8.7 alloy. Proper additions of the non-magnetic copper element which has a positive heat of mixing with Fe, coupled with adequate annealing, can stimulate formation of ˜5 nm αFe ferromagnetic nanocrystals, which results in the increment in the saturation magnetization. Over-annealing which induced coarsening of the α-Fe nanocrystals reduces the ferromagnetic exchange interaction between the nanosized α-Fe crystals and increases the effective magneto-crystalline anisotropy, thereby deteriorating the soft magnetic properties.

  10. 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.

  11. A Simple MO Treatment of Metal Clusters.

    ERIC Educational Resources Information Center

    Sahyun, M. R. V.

    1980-01-01

    Illustrates how a qualitative description of the geometry and electronic characteristics of homogeneous metal clusters can be obtained using semiempirical MO (molecular orbital theory) methods. Computer applications of MO methods to inorganic systems are also described. (CS)

  12. Electrocatalysis using transition metal carbide and oxide nanocrystals

    NASA Astrophysics Data System (ADS)

    Regmi, Yagya N.

    Carbides are one of the several families of transition metal compounds that are considered economic alternatives to catalysts based on noble metals and their compounds. Phase pure transition metal carbides of group 4-6 metals, in the first three periods, were synthesized using a common eutectic salt flux synthesis method, and their electrocatalytic activities compared under uniform electrochemical conditions. Mo2C showed highest hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) activities among the nine metal carbides investigated, but all other metal carbides also showed substantial activities. All the metal carbides showed remarkable enhancement in catalytic activities as supports, when compared to traditional graphitic carbon as platinum support. Mo2C, the most active transition metal carbide electrocatalyst, was prepared using four different synthesis routes, and the synthesis route dependent activities compared. Bifunctional Mo 2C that is HER as well as oxygen evolution reaction (OER) active, was achieved when the carbide was templated on a multiwalled carbon nanotube using carbothermic reduction method. Bimetallic carbides of Fe, Co, and Ni with Mo or W were prepared using a common carbothermic reduction method. Two different stoichiometries of bimetallic carbides were obtained for each system within a 60 °C temperature window. While the bimetallic carbides showed relatively lower electrocatalytic activities towards HER and ORR in comparison to Mo2C and WC, they revealed remarkably higher OER activities than IrO2 and RuO2, the state-of-the-art OER catalysts. Bimetallic oxides of Fe, Co, and Ni with Mo and W were also prepared using a hydrothermal synthesis method and they also revealed OER activities that are much higher than RuO2 and IrO2. Additionally, the OER activities were dependent on the degree and nature of hydration in the bimetallic oxide crystal lattice, with the completely hydrated, as synthesized, cobalt molybdate and nickel

  13. Design of a multi-coordinating polymer as a platform for functionalizing metal, metal oxide and semiconductor nanocrystals

    NASA Astrophysics Data System (ADS)

    Wang, Wentao; Ji, Xin; Kapur, Anshika; Mattoussi, Hedi

    2016-03-01

    We introduce a new set of amphiphilic polymers as multifunctional, metal-coordinating ligands adapted to surfacefunctionalize quantum dots (QDs), iron oxide nanoparticles (IONPs) and gold nanoparticles/nanorods (AuNPs/AuNRs). The ligand design relies on the introduction of several anchoring groups, hydrophilic moieties and reactive functionalities into a polymer chain, via one-step nucleophilic addition reaction. Such synthetic scheme also allows the insertion of target biomolecules during the ligand synthesis. This functionalization strategy yields nanocrystals that exhibit long-term colloidal stability over a broad range of biological conditions, such as pH changes and when mixed with growth media. When zwitterion groups are used as hydrophilic motifs, this provides compact nanocrystals that are compatible with conjugation to proteins via metal-polyhistidine self-assembly. In addition, we show that QDs ligated with these polymers can engage in energy or charge transfer interactions. Furthermore, nanocrystals coated with folic acid-modified polymers could promote the delivery of nanoparticle-conjugates into cancer cells via folate receptormediated endocytosis.

  14. Coupling of single InGaAs quantum dots to the plasmon resonance of a metal nanocrystal

    SciTech Connect

    Urbanczyk, A.; Hamhuis, G. J.; Noetzel, R.

    2010-07-26

    The authors report the coupling of single InGaAs quantum dots (QDs) to the surface plasmon resonance of a metal nanocrystal. Clear enhancement of the photoluminescence (PL) in the spectral region of the surface plasmon resonance is observed which splits up into distinct emission lines from single QDs in micro-PL. The hybrid metal-semiconductor structure is grown by molecular beam epitaxy on GaAs (100) utilizing the concept of self-organized anisotropic strain engineering for realizing ordered arrays with nanometer-scale precise positioning of the metal nanocrystals with respect to the QDs.

  15. In situ capping for size control of monochalcogenides (ZnS, CdS, and SnS) nanocrystals produced by anaerobic metal-reducing bacteria

    SciTech Connect

    Jang, Gyoung Gug; Jacobs, Christopher B.; Ivanov, Ilia N.; Joshi, Pooran C.; Meyer, III, Harry M.; Kidder, Michelle; Armstrong, Beth L.; Datskos, Panos G.; Graham, David E.; Moon, Ji -Won

    2015-07-24

    Metal monochalcogenide quantum dot nanocrystals of ZnS, CdS and SnS were prepared by anaerobic, metal-reducing bacteria using in situ capping by oleic acid or oleylamine. Furthermore, the capping agent preferentially adsorbs on the surface of the nanocrystal, suppressing the growth process in the early stages, thus leading to production of nanocrystals with a diameter of less than 5 nm.

  16. In situ capping for size control of monochalcogenide (ZnS, CdS and SnS) nanocrystals produced by anaerobic metal-reducing bacteria

    NASA Astrophysics Data System (ADS)

    Gug Jang, Gyoung; Jacobs, Christopher B.; Ivanov, Ilia N.; Joshi, Pooran C.; Meyer, Harry M., III; Kidder, Michelle; Armstrong, Beth L.; Datskos, Panos G.; Graham, David E.; Moon, Ji-Won

    2015-08-01

    Metal monochalcogenide quantum dot nanocrystals of ZnS, CdS and SnS were prepared by anaerobic, metal-reducing bacteria using in situ capping by oleic acid or oleylamine. The capping agent preferentially adsorbs on the surface of the nanocrystal, suppressing the growth process in the early stages, thus leading to production of nanocrystals with a diameter of less than 5 nm.

  17. Term rules for simple metal clusters

    NASA Astrophysics Data System (ADS)

    Yoshida, Daisuke; Raebiger, Hannes

    2015-10-01

    Hund’s term rules are only valid for isolated atoms, but have no generalization for molecules or clusters of several atoms. We present a benchmark calculation of Al2 and Al3, for which we find the high and low-spin ground states 3Πu and , respectively. We show that the relative stabilities of all the molecular terms of Al2 and Al3 can be described by simple rules pertaining to bonding structures and symmetries, which serve as guiding principles to determine ground state terms of arbitrary multi-atom clusters.

  18. Term rules for simple metal clusters

    PubMed Central

    Yoshida, Daisuke; Raebiger, Hannes

    2015-01-01

    Hund’s term rules are only valid for isolated atoms, but have no generalization for molecules or clusters of several atoms. We present a benchmark calculation of Al2 and Al3, for which we find the high and low-spin ground states 3Πu and , respectively. We show that the relative stabilities of all the molecular terms of Al2 and Al3 can be described by simple rules pertaining to bonding structures and symmetries, which serve as guiding principles to determine ground state terms of arbitrary multi-atom clusters. PMID:26497089

  19. Metal semiconductor phase transition in vanadium dioxide nanocrystals

    NASA Astrophysics Data System (ADS)

    Lopez Noriega, Rene

    The goal of this research was to improve the understanding of the submicron VO2 formation in the near surface of a host material and to explore the possibility of size effects in the mechanics of the semiconductor to metal phase transition as well as in the optical properties of VO2. By means of ion implantation and thermal processing, we were able to produce variable-sized nanoscale VO2 precipitates embedded in SiO 2. The transition temperatures were found to be correlated with the size of the precipitates, in such a way that for smaller particles, both transitions were thermally delayed. A review of the energy barriers and other features involved in the transition, led us to conclude that regardless of that exact mechanism, the phase transition must proceed in a heterogeneous fashion. Smaller particles were expected to have a lower chance of containing a nucleation site and thus, they need a greater thermal driving force in order to activate them. VO2 precipitates were not only controlled in size but as an unexpected result they turned out to be produced in elongated shapes oriented mainly along the implanted surface. This morphology, which was explained in terms of the Bravais-Friedel law of crystal growth, allowed us to understand the optical properties of the precipitates. We concluded that the optical behavior shown by the particles in the SiO2 matrix, was result of a surface plasmon resonance due to the dielectric confinement and metallic character of the VO2 in the high temperature phase. Beside these contributions to material and physical sciences, we have shown that established results for VO2 doping can be applicable to our submicron particles. We were able to successfully control the width of the hysteresis loop by adding Ti ions before the precipitation. We also reached lower switching temperatures by implanting small quantities of W. Ion implantation also proved to be an easy and convenient way to incorporate VO2 nanoparticles into an optical fiber

  20. Well-faceted noble-metal nanocrystals with nonconvex polyhedral shapes.

    PubMed

    Chen, Qiaoli; Jia, Yanyan; Xie, Shuifen; Xie, Zhaoxiong

    2016-06-01

    Precise engineering of noble-metal nanocrystals (NCs) is not only an important fundamental research topic, but also has great realistic significance in improving their performances required by the poor reserve and high cost of noble metals. Well-faceted noble-metal NCs with nonconvex polyhedral shapes could be promising candidates to optimize their performance and thus minimize their usage, as they may integrate a well-defined surface structure and a large surface area together, enabling them to have outstanding performance and high efficiency of atomic utilization. Moreover, undesirable aggregation and ripening phenomena could be avoided. This review provides a comprehensive summary of the unique characteristics and corresponding models of well-faceted nonconvex polyhedral noble-metal NCs by classifying the cases into four distinct types, namely the concave polyhedral structure, excavated polyhedral structure, branched structure and nanocage structure, respectively. Due to the complexity of nonconvex morphologies and the thermodynamic antipathy for the growth of nonconvex shaped NCs, we firstly demonstrate the structure characterization and synthetic methodology in detail. Subsequently, typical applications in electrocatalysis and plasmonic fields are presented to demonstrate the unique surface and morphological effects generated from the well-faceted nonconvex NCs. To promote further development in this field, the perspectives and challenges concerning well-faceted noble-metal NCs with nonconvex shapes are put forward in the end. PMID:27086861

  1. Structural, Optical and Electrical Properties of PbSe Nanocrystal Solids Treated Thermally or with Simple Amines

    SciTech Connect

    Law, M.; Luther, J. M.; Song, Q.; Hughes, B. K.; Perkins, C. L.; Nozik, A. J.

    2008-01-01

    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 {approx}200 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.

  2. 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

    2008-05-01

    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. PMID:18396872

  3. Enhanced ethylene separation and plasticization resistance in polymer membranes incorporating metal-organic framework nanocrystals.

    PubMed

    Bachman, Jonathan E; Smith, Zachary P; Li, Tao; Xu, Ting; Long, Jeffrey R

    2016-08-01

    The implementation of membrane-based separations in the petrochemical industry has the potential to reduce energy consumption significantly relative to conventional separation processes. Achieving this goal, however, requires the development of new membrane materials with greater selectivity, permeability and stability than available at present. Here, we report composite materials consisting of nanocrystals of metal-organic frameworks dispersed within a high-performance polyimide, which can exhibit enhanced selectivity for ethylene over ethane, greater ethylene permeability and improved membrane stability. Our results suggest that framework-polymer interactions reduce chain mobility of the polymer while simultaneously boosting membrane separation performance. The increased stability, or plasticization resistance, is expected to improve membrane utility under real process conditions for petrochemical separations and natural gas purification. Furthermore, this approach can be broadly applied to numerous polymers that encounter aggressive environments, potentially making gas separations possible that were previously inaccessible to membranes. PMID:27064528

  4. Enhanced ethylene separation and plasticization resistance in polymer membranes incorporating metal-organic framework nanocrystals

    NASA Astrophysics Data System (ADS)

    Bachman, Jonathan E.; Smith, Zachary P.; Li, Tao; Xu, Ting; Long, Jeffrey R.

    2016-08-01

    The implementation of membrane-based separations in the petrochemical industry has the potential to reduce energy consumption significantly relative to conventional separation processes. Achieving this goal, however, requires the development of new membrane materials with greater selectivity, permeability and stability than available at present. Here, we report composite materials consisting of nanocrystals of metal-organic frameworks dispersed within a high-performance polyimide, which can exhibit enhanced selectivity for ethylene over ethane, greater ethylene permeability and improved membrane stability. Our results suggest that framework-polymer interactions reduce chain mobility of the polymer while simultaneously boosting membrane separation performance. The increased stability, or plasticization resistance, is expected to improve membrane utility under real process conditions for petrochemical separations and natural gas purification. Furthermore, this approach can be broadly applied to numerous polymers that encounter aggressive environments, potentially making gas separations possible that were previously inaccessible to membranes.

  5. Impact of metal nano layer thickness on tunneling oxide and memory performance of core-shell iridium-oxide nanocrystals

    SciTech Connect

    Banerjee, W.; Maikap, S.; Tien, T.-C.; Li, W.-C.; Yang, J.-R.

    2011-10-01

    The impact of iridium-oxide (IrO{sub x}) nano layer thickness on the tunneling oxide and memory performance of IrO{sub x} metal nanocrystals in an n-Si/SiO{sub 2}/Al{sub 2}O{sub 3}/IrO{sub x}/Al{sub 2}O{sub 3}/IrO{sub x} structure has been investigated. A thinner (1.5 nm) IrO{sub x} nano layer has shown better memory performance than that of a thicker one (2.5 nm). Core-shell IrO{sub x} nanocrystals with a small average diameter of 2.4 nm and a high density of {approx}2 x 10{sup 12}/cm{sup 2} have been observed by scanning transmission electron microscopy. The IrO{sub x} nanocrystals are confirmed by x-ray photoelectron spectroscopy. A large memory window of 3.0 V at a sweeping gate voltage of {+-}5 V and 7.2 V at a sweeping gate voltage of {+-} 8 V has been observed for the 1.5 nm-thick IrO{sub x} nano layer memory capacitors with a small equivalent oxide thickness of 8 nm. The electrons and holes are trapped in the core and annular regions of the IrO{sub x} nanocrystals, respectively, which is explained by Gibbs free energy. High electron and hole-trapping densities are found to be 1.5 x 10{sup 13}/cm{sup 2} and 2 x 10{sup 13}/cm{sup 2}, respectively, due to the small size and high-density of IrO{sub x} nanocrystals. Excellent program/erase endurance of >10{sup 6} cycles and good retention of 10{sup 4} s with a good memory window of >1.2 V under a small operation voltage of {+-} 5 V are obtained. A large memory size of >10 Tbit/sq. in. can be designed by using the IrO{sub x} nanocrystals. This study is not only important for the IrO{sub x} nanocrystal charge-trapping memory investigation but it will also help to design future metal nanocrystal flash memory.

  6. Nature of Pressure-induced Insulating States in Simple Metals

    NASA Astrophysics Data System (ADS)

    Naumov, Ivan; Hemley, Russell

    As experimentally established, all the alkali metals and heavy alkaline earth metals (Ca, Sr and Ba) become progressively less conductive on compression, at least up to some critical limit over a broad pressure range. Of these metals, Li and Na clearly undergo pressure-induced metal-insulator transitions, which may also be called reverse Mott transitions. Here, using group theory arguments and first-principles calculations, we show that such transitions can be understood in terms of band representations introduced by Zak. The valence bands in the insulating states are described by simple and composite band representations constructed from localized Wannier functions centered on points unoccupied by atoms. The character of the Wannier functions is closely related to the degree of s-p(-d) hybridization and reflects multi-center chemical bonding in these insulating states. The conditions under which an insulating state is allowed for structures having an integer number of atoms per primitive unit cell as well as re-entrant (i.e., metal-insulator-metal) transition sequences are detailed, resulting in predictions of semimetallic phases with flat surface states. The general principles developed are tested and applied to the alkali and alkaline earth metals, including elements where high-pressure insulating phases have been identified or reported (e.g., Li, Na, and Ca). This research was supported by EFree, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award DESC0001057.

  7. Controllable synthesis of metal selenide heterostructures mediated by Ag2Se nanocrystals acting as catalysts.

    PubMed

    Zhou, Jiangcong; Huang, Feng; Xu, Ju; Wang, Yuansheng

    2013-10-21

    Ag2Se nanocrystals were demonstrated to be novel semiconductor mediators, or in other word catalysts, for the growth of semiconductor heterostructures in solution. This is a result of the unique feature of Ag2Se as a fast ion conductor, allowing foreign cations to dissolve and then to heterogrow the second phase. Using Ag2Se nanocrystals as catalysts, dimeric metal selenide heterostructures such as Ag2Se-CdSe and Ag2Se-ZnSe, and even multi-segment heterostructures such as Ag2Se-CdSe-ZnSe and Ag2Se-ZnSe-CdSe, were successfully synthesized. Several interesting features were found in the Ag2Se based heterogrowth. At the initial stage of heterogrowth, a layer of the second phase forms on the surface of an Ag2Se nanosphere, with a curved junction interface between the two phases. With further growth of the second phase, the Ag2Se nanosphere tends to flatten the junction surface by modifying its shape from sphere to hemisphere in order to minimize the conjunct area and thus the interfacial energy. Notably, the crystallographic relationship of the two phases in the heterostructure varies with the lattice parameters of the second phase, in order to reduce the lattice mismatch at the interface. Furthermore, a small lattice mismatch at the interface results in a straight rod-like second phase, while a large lattice mismatch would induce a tortuous product. The reported results may provide a new route for developing novel selenide semiconductor heterostructures which are potentially applicable in optoelectronic, biomedical, photovoltaic and catalytic fields. PMID:24056899

  8. Simple and efficient separation of atomically precise noble metal clusters.

    PubMed

    Ghosh, Atanu; Hassinen, Jukka; Pulkkinen, Petri; Tenhu, Heikki; Ras, Robin H A; Pradeep, Thalappil

    2014-12-16

    There is an urgent need for accessible purification and separation strategies of atomically precise metal clusters in order to promote the study of their fundamental properties. Although the separation of mixtures of atomically precise gold clusters Au25L18, where L are thiolates, has been demonstrated by advanced separation techniques, we present here the first separation of metal clusters by thin-layer chromatography (TLC), which is simple yet surprisingly efficient. This method was successfully applied to a binary mixture of Au25L18 with different ligands, as well as to a binary mixture of different cluster cores, Au25 and Au144, protected with the same ligand. Importantly, TLC even enabled the challenging separation of a multicomponent mixture of mixed-monolayer-protected Au25 clusters with closely similar chemical ligand compositions. We anticipate that the realization of such simple yet efficient separation technique will progress the detailed investigation of cluster properties. PMID:25395064

  9. Nanoscale Transformations in Covellite (CuS) Nanocrystals in the Presence of Divalent Metal Cations in a Mild Reducing Environment

    PubMed Central

    2015-01-01

    We studied the structural and compositional transformations of colloidal covellite (CuS) nanocrystals (and of djurleite (Cu1.94S) nanocrystals as a control) when exposed to divalent cations, as Cd2+ and Hg2+, at room temperature in organic solvents. All the experiments were run in the absence of phosphines, which are a necessary ingredient for cation exchange reactions involving copper chalcogenides, as they strongly bind to the expelled Cu+ ions. Under these experimental conditions, no remarkable reactivity was indeed seen for both CuS and Cu1.94S nanocrystals. On the other hand, in the covellite structure 2/3 of sulfur atoms form covalent S–S bonds. This peculiarity suggests that the combined presence of electron donors and of foreign metal cations can trigger the entry of both electrons and cations in the covellite lattice, causing reorganization of the anion framework due to the rupture of the S–S bonds. In Cu1.94S, which lacks S–S bonds, this mechanism should not be accessible. This hypothesis was proven by the experimental evidence that adding ascorbic acid increased the fraction of metal ions incorporated in the covellite nanocrystals, while it had no noticeable effect on the Cu1.94S ones. Once inside the covellite particles, Cd2+ and Hg2+ cations engaged in exchange reactions, pushing the expelled Cu+ ions toward the not-yet exchanged regions in the same particles, or out to the solution, from where they could be recaptured by other covellite nanoparticles/domains. Because no good solvating agent for Cu ions was present in solution, they essentially remained in the nanocrystals. PMID:26617434

  10. Fabrication of hollow metal oxide nanocrystals by etching cuprous oxide with metal(II) ions: approach to the essential driving force.

    PubMed

    Sohn, Jong Hwa; Cha, Hyun Gil; Kim, Chang Woo; Kim, Do Kyoung; Kang, Young Soo

    2013-11-21

    Hollow metal oxide nanocrystals were prepared by etching cuprous oxide with metal ions and were applied as photoelectrodes. As a hard template, polyvinylpyrrolidone stabilized cuprous oxide (PVP-Cu2O) and non-stabilized cuprous oxide (nPVP-Cu2O) were synthesized by a precipitation method. Hollow iron oxide and cobalt oxide nanocrystals with a truncated octahedral morphology were fabricated by an etching reaction with transition metal(II) ions (Fe(2+) or Co(2+)). In the etching reaction process, a cationic exchange reaction occurs between the divalent metal ion and Cu(+) due to the higher Lewis acidity. Facet selective etching of cuprous oxide has been observed during the ionic exchange reaction of Cu(+) and O(2-) ions in PVP-Cu2O complexes with transition metal(II) ions (Fe(2+) or Co(2+)) at the surface of a (110) facet. Amorphous states of hollow metal oxide products were annealed to form α-Fe2O3 (hematite) and Co3O4 and their crystal structure was examined with X-ray diffraction and HR-TEM. The optical absorption behavior of semiconductor nanocrystals was measured with UV-vis spectroscopy to define band gap energy. The hollow hematite structure has a 2.08 eV band gap and Co3O4 (Co(II,III) oxide) has a 1.80 eV indirect band gap. Using these hollow nanocrystals, a metal oxide monolayer film was fabricated with a secondary growth approach and was studied for its photocatalytic properties. PMID:24084833

  11. Evaluation of Metal Phosphide Nanocrystals as Anode Materials for Na-ion Batteries.

    PubMed

    Walter, Marc; Bodnarchuk, Maryna I; Kravchyk, Kostiantyn V; Kovalenko, Maksym V

    2015-01-01

    Sodium-ion batteries (SIBs) are potential low-cost alternatives to lithium-ion batteries (LIBs) because of the much greater natural abundance of sodium salts. However, developing high-performance electrode materials for SIBs is a challenging task, especially due to the ∼50% larger ionic radius of the Na(+) ion compared to Li(+), leading to vastly different electrochemical behavior. Metal phosphides such as FeP, CoP, NiP(2), and CuP(2) remain unexplored as electrode materials for SIBs, despite their high theoretical charge storage capacities of 900-1300 mAh g(-1). Here we report on the synthesis of metal phosphide nanocrystals (NCs) and discuss their electrochemical properties as anode materials for SIBs, as well as for LIBs. We also compare the electrochemical characteristics of phosphides with their corresponding sulfides, using the environmentally benign iron compounds, FeP and FeS(2), as a case study. We show that despite the appealing initial charge storage capacities of up to 1200 mAh g(-1), enabled by effective nanosizing of the active electrode materials, further work toward optimization of the electrode/electrolyte pair is needed to improve the electrochemical performance upon cycling. PMID:26842319

  12. Hopping conductivity and insulator-metal transition in films of touching semiconductor nanocrystals

    NASA Astrophysics Data System (ADS)

    Fu, Han; Reich, K. V.; Shklovskii, B. I.

    2016-03-01

    This paper is focused on the variable-range hopping of electrons in semiconductor nanocrystal (NC) films below the critical doping concentration nc at which it becomes metallic. The hopping conductivity is described by the Efros-Shklovskii law, which depends on the localization length of electrons. We study how the localization length grows with the doping concentration n in the film of touching NCs. For that we calculate the electron transfer matrix element t (n ) between neighboring NCs for two models when NCs touch by small facets or just one point. We study two sources of disorder: variations of NC diameters and random Coulomb potentials originating from random numbers of donors in NCs. We use the ratio of t (n ) to the disorder-induced NC level dispersion to find the localization length of electrons due to the multistep elastic co-tunneling process. We found three different phases at n metal" where the localization length periodically diverges. The first two phases were seen experimentally and we discuss how one can see the more exotic third one. In all three, the localization length diverges at n =nc . This allows us to find nc.

  13. X-Ray Absorption Studies of Vanadium-Containing Metal Oxide Nanocrystals

    SciTech Connect

    Hohn, Keith, L.

    2006-01-09

    Metal oxide nanocrystals offer significant potential for use as catalysts or catalyst supports due to their high surface areas and unique chemical properties that result from the high number of exposed corners and edges. However, little is known about the catalytic activity of these materials, especially as oxidation catalysts. This research focused on the preparation, characterization and use of vanadium-containing nanocrystals as selective oxidation catalysts. Three vanadium-containing nanocrystals were prepared using a modified sol-gel procedure: V/MgO, V/SiO2, and vanadium phosphate (VPO). These represent active oxidation catalysts for a number of industrially relevant reactions. The catalysts were characterized by x-ray diffraction and Raman, UV-VIS, infrared and x-ray absorption spectroscopies with the goal of determining the primary structural and chemical differences between nanocrystals and microcrystals. The catalytic activity of these catalysts was also studied in oxidative dehydrogenation of butane and methanol oxidation to formaldehyde. V/MgO nanocrystals were investigated for activity in oxidative dehydrogenation of butane and compared to conventional V/MgO catalysts. Characterization of V/MgO catalysts using Raman spectroscopy and x-ray absorption spectroscopy showed that both types of catalysts contained magnesium orthovanadate at vanadium loadings below 15 weight%, but above that loading, magnesium pyrovanadate may have been present. In general, MgO nanocrystals had roughly half the crystal size and double the surface area of the conventional MgO. In oxidative dehydrogenation of butane, nanocrystalline V/MgO gave higher selectivity to butene than conventional V/MgO at the same conversion. This difference was attributed to differences in vanadium domain size resulting from the higher surface areas of the nanocrystalline support, since characterization suggested that similar vanadium phases were present on both types of catalysts. Experiments in

  14. Luminescent small-diameter 3C-SiC nanocrystals fabricated via a simple chemical etching method

    NASA Astrophysics Data System (ADS)

    Zhu, J.; Liu, Z.; Wu, X. L.; Xu, L. L.; Zhang, W. C.; Chu, Paul K.

    2007-09-01

    Up to now, it is still a great challenge to obtain bulk quantities of luminescent 3C-SiC nanocrystals with sizes smaller than 10 nm, which have quantum confinement effect. We report in this paper on the fabrication of 3C-SiC nanocrystals via a chemical etching of microscale 3C-SiC grains and ultrasonic vibration. The sizes of the as-prepared 3C-SiC nanocrystals are smaller than 6.5 nm and have a centric distribution with the maximal probability of 3.6 nm. Due to the quantum confinement effect, the suspension of the 3C-SiC nanocrystals exhibits a tunable photoluminescence (PL), which is visible with the naked eye. As the excitation line increases from 260 to 480 nm, the PL peak position changes from 420 to 512 nm. Spectral analysis and microstructural observations show that the chemical etching leads to the formation of a weakly interconnected nanostructure network in the large 3C-SiC grains and subsequent ultrasonic vibration crumbles the interconnected network, forming small-size 3C-SiC nanocrystals.

  15. Graphene oxide/metal nanocrystal multilaminates as the atomic limit for safe and selective hydrogen storage

    NASA Astrophysics Data System (ADS)

    Cho, Eun Seon; Ruminski, Anne M.; Aloni, Shaul; Liu, Yi-Sheng; Guo, Jinghua; Urban, Jeffrey J.

    2016-02-01

    Interest in hydrogen fuel is growing for automotive applications; however, safe, dense, solid-state hydrogen storage remains a formidable scientific challenge. Metal hydrides offer ample storage capacity and do not require cryogens or exceedingly high pressures for operation. However, hydrides have largely been abandoned because of oxidative instability and sluggish kinetics. We report a new, environmentally stable hydrogen storage material constructed of Mg nanocrystals encapsulated by atomically thin and gas-selective reduced graphene oxide (rGO) sheets. This material, protected from oxygen and moisture by the rGO layers, exhibits exceptionally dense hydrogen storage (6.5 wt% and 0.105 kg H2 per litre in the total composite). As rGO is atomically thin, this approach minimizes inactive mass in the composite, while also providing a kinetic enhancement to hydrogen sorption performance. These multilaminates of rGO-Mg are able to deliver exceptionally dense hydrogen storage and provide a material platform for harnessing the attributes of sensitive nanomaterials in demanding environments.

  16. Graphene oxide/metal nanocrystal multilaminates as the atomic limit for safe and selective hydrogen storage

    DOE PAGESBeta

    Cho, Eun Seon; Ruminski, Anne M.; Aloni, Shaul; Liu, Yi-Sheng; Guo, Jinghua; Urban, Jeffrey J.

    2016-02-23

    Interest in hydrogen fuel is growing for automotive applications; however, safe, dense, solid-state hydrogen storage remains a formidable scientific challenge. Metal hydrides offer ample storage capacity and do not require cryogens or exceedingly high pressures for operation. However, hydrides have largely been abandoned because of oxidative instability and sluggish kinetics. We report a new, environmentally stable hydrogen storage material constructed of Mg nanocrystals encapsulated by atomically thin and gas-selective reduced graphene oxide (rGO) sheets. This material, protected from oxygen and moisture by the rGO layers, exhibits exceptionally dense hydrogen storage (6.5 wt% and 0.105 kg H2 per litre in themore » total composite). As rGO is atomically thin, this approach minimizes inactive mass in the composite, while also providing a kinetic enhancement to hydrogen sorption performance. In conclusion, these multilaminates of rGO-Mg are able to deliver exceptionally dense hydrogen storage and provide a material platform for harnessing the attributes of sensitive nanomaterials in demanding environments.« less

  17. Surface passivation of lead sulfide nanocrystals with low electron affinity metals: photoluminescence and photovoltaic performance.

    PubMed

    Tavakoli, Mohammad Mahdi; Mirfasih, Mohammad Hassan; Hasanzadeh, Soheil; Aashuri, Hossein; Simchi, Abdolreza

    2016-04-28

    During the last decade, solution-processed colloidal quantum dots (CQDs) have attracted significant attention for low-cost fabrication of optoelectronic devices. In this study, lead sulfide (PbS) CQDs were synthesized via the hot injection method and the effect of doping elements with low electron affinity, including cadmium, calcium and zinc, on the passivation of trap states was investigated. A red-shift in the luminescence emission was observed by doping through passivation of lead dangling bonds. Time-resolved photoluminescence measurements showed that the lifetime of charged carriers was significantly enhanced by cadmium doping (∼80%) which is quite noticeable compared with calcium- and zinc-doped nanocrystals. External quantum efficiency measurements on thin solid films (∼300 nm) prepared by spin coating supported improved lifetime of carriers through passivation of mid-gap trap states. In order to show the potential application of the doping process, bulk heterojunction CQD solar cells were fabricated. It was found that the power conversion efficiency (PCE) was improved up to ∼40%; the highest improvement was observed with the Cd treatment. Finally, density functional theory (DFT) and electrochemical impedance spectroscopy (EIS) were employed to study the effect of doping on the density of states. The results showed that doping with low electron affinity metals effectively reduced the deep trap states of PbS QDs. PMID:27075607

  18. Graphene oxide/metal nanocrystal multilaminates as the atomic limit for safe and selective hydrogen storage

    PubMed Central

    Cho, Eun Seon; Ruminski, Anne M.; Aloni, Shaul; Liu, Yi-Sheng; Guo, Jinghua; Urban, Jeffrey J.

    2016-01-01

    Interest in hydrogen fuel is growing for automotive applications; however, safe, dense, solid-state hydrogen storage remains a formidable scientific challenge. Metal hydrides offer ample storage capacity and do not require cryogens or exceedingly high pressures for operation. However, hydrides have largely been abandoned because of oxidative instability and sluggish kinetics. We report a new, environmentally stable hydrogen storage material constructed of Mg nanocrystals encapsulated by atomically thin and gas-selective reduced graphene oxide (rGO) sheets. This material, protected from oxygen and moisture by the rGO layers, exhibits exceptionally dense hydrogen storage (6.5 wt% and 0.105 kg H2 per litre in the total composite). As rGO is atomically thin, this approach minimizes inactive mass in the composite, while also providing a kinetic enhancement to hydrogen sorption performance. These multilaminates of rGO-Mg are able to deliver exceptionally dense hydrogen storage and provide a material platform for harnessing the attributes of sensitive nanomaterials in demanding environments. PMID:26902901

  19. Graphene oxide/metal nanocrystal multilaminates as the atomic limit for safe and selective hydrogen storage.

    PubMed

    Cho, Eun Seon; Ruminski, Anne M; Aloni, Shaul; Liu, Yi-Sheng; Guo, Jinghua; Urban, Jeffrey J

    2016-01-01

    Interest in hydrogen fuel is growing for automotive applications; however, safe, dense, solid-state hydrogen storage remains a formidable scientific challenge. Metal hydrides offer ample storage capacity and do not require cryogens or exceedingly high pressures for operation. However, hydrides have largely been abandoned because of oxidative instability and sluggish kinetics. We report a new, environmentally stable hydrogen storage material constructed of Mg nanocrystals encapsulated by atomically thin and gas-selective reduced graphene oxide (rGO) sheets. This material, protected from oxygen and moisture by the rGO layers, exhibits exceptionally dense hydrogen storage (6.5 wt% and 0.105 kg H2 per litre in the total composite). As rGO is atomically thin, this approach minimizes inactive mass in the composite, while also providing a kinetic enhancement to hydrogen sorption performance. These multilaminates of rGO-Mg are able to deliver exceptionally dense hydrogen storage and provide a material platform for harnessing the attributes of sensitive nanomaterials in demanding environments. PMID:26902901

  20. Synthesis and characterization of some metal oxide nanocrystals by microwave irradiation

    SciTech Connect

    Rashad, M.; Gaber, A.; Abdelrahim, M. A.; Abdel-Baset, A. M.; Moharram, A. H.

    2013-12-16

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

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

    SciTech Connect

    Yun, Min Ju; Kim, Hee-Dong; Man Hong, Seok; Hyun Park, Ju; Su Jeon, Dong; Geun Kim, Tae

    2014-03-07

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

  2. General synthetic approach to heterostructured nanocrystals based on noble metals and I-VI, II-VI, and I-III-VI metal chalcogenides.

    PubMed

    Liu, Minghui; Zeng, Hua Chun

    2014-08-19

    Solid metal precursors (alloys or monometals) can serve both as a starting template and as a source material for chemical transformation to metal chalcogenides. Herein, we develop a simple solution-based strategy to obtain highly monodisperse noble-metal-based heterostructured nanocrystals from such precursor seeds. By utilizing chemical and structural inhomogeneity of these metal seeds, in this work, we have synthesized a total of five I-VI (Ag2S, Ag2Se, Ag3AuS2, Ag3AuSe2, and Cu9S5), three II-VI (CdS, CdSe, and CuSe), and four I-III-VI (AgInS2, AgInSe2, CuInS2, and CuInSe2) chalcogenides, together with their fifteen associated heterodimers (Au-Ag2S, Au-Ag2Se, Au-Ag3AuS2, Au-Ag3AuSe2, Au-AgInS2, Au-AgInSe2, Au-CdS, Au-CdSe, Ag-Ag2S, Ag-AgInS2, Au-Cu9S5, Au-CuInS2, Au-CuSe, Au-CuInSe2, and Pt-AgInS2) to affirm the process generality. Briefly, by adding elemental sulfur or selenium to AuAg alloy seeds and tuning the reaction conditions, we can readily obtain phase-pure Au-Ag2S, Au-Ag2Se, Au-Ag3AuS2, and Au-Ag3AuSe2 heterostructures. Similarly, we can also fabricate Au-AgInS2 and Au-AgInSe2 heterostructures from the AuAg seeds by adding sulfur/selenium and indium precursors. Furthermore, by partial or full conversion of Ag seeds, we can prepare both single-phase Ag chalcogenide nanocrystals and Ag-based heterostructures. To demonstrate wide applicability of this strategy, we have also synthesized Au-based binary and ternary Cu chalcogenide (Au-Cu9S5, Au-CuSe, Au-CuInS2, and Au-CuInSe2) heterostructures from alloy seeds of AuCu and Pt chalcogenides (e.g., Pt-AgInS2) from alloy seeds of PtAg. The structure and composition of the above products have been confirmed with X-ray diffraction, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and energy-dispersive X-ray spectroscopy methods. A kinetic investigation of the formation mechanism of these heterostructures is brought forward using Au-AgInS2 and Ag-CuInS2 as model examples. PMID

  3. A first principles study of noble metal-doped silicon nanocrystals Sin-1M (n = 75 and 150 and M = Cu, Ag, Au)

    NASA Astrophysics Data System (ADS)

    Mayfield, Cedric; Huda, Muhammad

    2010-10-01

    Silicon nano-structures can have important roles in many useful applications, such as in nano-scale energy conversion materials, as nano-detectors of gas particles or as thermoelectric materials. To achieve efficient performance of these nano-devices, electronically tailored nano-materials are needed. For this a thorough understanding of both doped and undoped nano-structures is essential. Here we will present results of our first principles spin polarized electronic structure calculations of noble metal atom doped silicon nanocrystals using a hybrid density functional theory method (B3LYP-DFT) and a LanL2DZ basis set. The nanocrystals are used here as a test group, and are based on three different isomers of bulk silicon: diamond, wurtzite, and BC8. Geometry optimizations of the pure Sin nanocrystals were performed for spin magnetic moments of s=0 μB and s=2 μB for each isomer. Then the substitutional doping of M atom was done separately at the inside and at the surface of the nanocrystals. The doped nanocrystals' geometries were also optimized for spin magnetic moments s=1 μB and s=3 μB. For the bigger nanocrystals, the energy differences between the two spin states are very small. Binding energies and HOMO-LUMO gaps were calculated and a comparative analysis of the pure and doped silicon nanocrystals will be presented.

  4. Property trends in simple metals: An empirical potential approach

    NASA Astrophysics Data System (ADS)

    Nichol, A.; Ackland, G. J.

    2016-05-01

    We demonstrate that the melting points and other thermodynamic quantities of the alkali metals can be calculated based on static crystalline properties. To do this we derive analytic interatomic potentials for the alkali metals fitted precisely to cohesive and vacancy energies, elastic moduli, the lattice parameter, and crystal stability. These potentials are then used to calculate melting points by simulating the equilibration of solid and liquid samples in thermal contact at ambient pressure. With the exception of lithium, remarkably good agreement is found with experimental values. The instability of the bcc structure in Li and Na at low temperatures is also reproduced and, unusually, is not due to a soft T1N phonon mode. No forces or finite-temperature properties are included in the fit, so this demonstrates a surprisingly high level of intrinsic transferability in the simple potentials. Currently, there are few potentials available for the alkali metals, so in addition to demonstrating trends in behavior, we expect that the potentials will be of broad general use.

  5. Copper metal-organic framework nanocrystal for plane effect nonenzymatic electro-catalytic activity of glucose.

    PubMed

    Liu, Yuanying; Zhang, Youjuan; Chen, Jing; Pang, Huan

    2014-10-01

    This work describes the first demonstration of nanocrystal plane dependent nonenzymatic electro-catalytic glucose activity of [Cu3(btc)2] nanocrystals with different shapes (nanocube, truncated cube, cuboctahedron, and octahedron). From electrochemical results, the obtained [Cu3(btc)2] nanocube modified electrode shows the best nonenzymatic electro-catalytic glucose activity. Interestingly, decreasing the {100} crystal planes from cubes to octahedra, changes the nonenzymatic electro-catalytic activity from highly sensitive to general. PMID:25123202

  6. Tuning the Magnetic Properties of Metal Oxide Nanocrystal Heterostructures by Cation Exchange

    PubMed Central

    2013-01-01

    For three types of colloidal magnetic nanocrystals, we demonstrate that postsynthetic cation exchange enables tuning of the nanocrystal’s magnetic properties and achieving characteristics not obtainable by conventional synthetic routes. While the cation exchange procedure, performed in solution phase approach, was restricted so far to chalcogenide based semiconductor nanocrystals, here ferrite-based nanocrystals were subjected to a Fe2+ to Co2+ cation exchange procedure. This allows tracing of the compositional modifications by systematic and detailed magnetic characterization. In homogeneous magnetite nanocrystals and in gold/magnetite core shell nanocrystals the cation exchange increases the coercivity field, the remanence magnetization, as well as the superparamagnetic blocking temperature. For core/shell nanoheterostructures a selective doping of either the shell or predominantly of the core with Co2+ is demonstrated. By applying the cation exchange to FeO/CoFe2O4 core/shell nanocrystals the Neél temperature of the core material is increased and exchange-bias effects are enhanced so that vertical shifts of the hysteresis loops are obtained which are superior to those in any other system. PMID:23362940

  7. Rescaling of metal oxide nanocrystals for energy storage having high capacitance and energy density with robust cycle life

    PubMed Central

    Jeong, Hyung Mo; Choi, Kyung Min; Cheng, Tao; Lee, Dong Ki; Zhou, Renjia; Ock, Il Woo; Milliron, Delia J.; Goddard, William A.; Kang, Jeung Ku

    2015-01-01

    Nanocrystals are promising structures, but they are too large for achieving maximum energy storage performance. We show that rescaling 3-nm particles through lithiation followed by delithiation leads to high-performance energy storage by realizing high capacitance close to the theoretical capacitance available via ion-to-atom redox reactions. Reactive force-field (ReaxFF) molecular dynamics simulations support the conclusion that Li atoms react with nickel oxide nanocrystals (NiO-n) to form lithiated core–shell structures (Ni:Li2O), whereas subsequent delithiation causes Ni:Li2O to form atomic clusters of NiO-a. This is consistent with in situ X-ray photoelectron and optical spectroscopy results showing that Ni2+ of the nanocrystal changes during lithiation–delithiation through Ni0 and back to Ni2+. These processes are also demonstrated to provide a generic route to rescale another metal oxide. Furthermore, assembling NiO-a into the positive electrode of an asymmetric device enables extraction of full capacitance for a counter negative electrode, giving high energy density in addition to robust capacitance retention over 100,000 cycles. PMID:26080421

  8. Assembling metal oxide nanocrystals into dense, hollow, porous nanoparticles for lithium-ion and lithium-oxygen battery application

    NASA Astrophysics Data System (ADS)

    Ming, Jun; Wu, Yingqiang; Park, Jin-Bum; Lee, Joong Kee; Zhao, Fengyu; Sun, Yang-Kook

    2013-10-01

    New dense hollow porous (DHP) metal oxide nanoparticles that are smaller than 100 nm and composed of Co3O4, FeOx, NiO and MnOx were prepared by densely assembling metal oxide nanocrystals based on the hard-template method using a carbon colloid as a sacrificial core. These nanoparticles are quite different from the traditional particles as their hollow interior originates from the stacking of nanocrystals rather than a spherical shell. The DHP nanoparticles preserve the intriguing properties of nanocrystals and possess desirable surface area and pore volume that enhance the active surface, which ultimately benefits applications such as lithium-ion batteries. The DHP Co3O4 nanoparticles demonstrated an enhanced capacity of 1168 mA h g-1 at 100 mA g-1vs. 590 mA h g-1 of powders and stable cycling performance greater than 250 cycles when used as an anode material. Most importantly, the electrochemical performance of DHP Co3O4 nanoparticles in a lithium-O2 battery was also investigated for the first time. A low charge potential of ~4.0 V, a high discharge voltage near 2.74 V and a long cycle ability greater than 100 cycles at a delivered capacity of 2000 mA h g-1 (current density, 200 mA g-1) were observed. The performances were considerably improved compared to recent results of mesoporous Co3O4, Co3O4 nanoparticles and a composite of Co3O4/RGO and Co3O4/Pd. Therefore, it would be promising to investigate such properties of DHP nanoparticles or other hollow metal (oxide) particles for the popular lithium-air battery.New dense hollow porous (DHP) metal oxide nanoparticles that are smaller than 100 nm and composed of Co3O4, FeOx, NiO and MnOx were prepared by densely assembling metal oxide nanocrystals based on the hard-template method using a carbon colloid as a sacrificial core. These nanoparticles are quite different from the traditional particles as their hollow interior originates from the stacking of nanocrystals rather than a spherical shell. The DHP

  9. Study of simple CFRP-metal joint failure

    NASA Astrophysics Data System (ADS)

    Cheng, Jingquan; Rodriguez, Antonio; Emerson, Nicolas; Symmes, Arthur

    2008-07-01

    In millimeter wavelength telescope design and construction, there have been a number of mysterious failures of simple CFRF-metal joints. Telescope designers have not had satisfactory interpretations of these failures. In this paper, factors which may influence the failure of joints are discussed. These include stress concentration, material creep, joint fatigue, reasons related to chemical process and manufacture process. Extrapolation formulas for material creep, joint fatigue, and differential thermal stresses are derived in this paper. Detailed chemical and manufacturing factors are also discussed. All these issues are the causes of a number of early failures under a loading which is significantly lower than the strength of adhesives used. For ensuring reliability of a precision instrument structure joint, the designer should have a thorough understanding of all these factors.

  10. Assembling metal oxide nanocrystals into dense, hollow, porous nanoparticles for lithium-ion and lithium-oxygen battery application.

    PubMed

    Ming, Jun; Wu, Yingqiang; Park, Jin-Bum; Lee, Joong Kee; Zhao, Fengyu; Sun, Yang-Kook

    2013-11-01

    New dense hollow porous (DHP) metal oxide nanoparticles that are smaller than 100 nm and composed of Co3O4, FeOx, NiO and MnOx were prepared by densely assembling metal oxide nanocrystals based on the hard-template method using a carbon colloid as a sacrificial core. These nanoparticles are quite different from the traditional particles as their hollow interior originates from the stacking of nanocrystals rather than a spherical shell. The DHP nanoparticles preserve the intriguing properties of nanocrystals and possess desirable surface area and pore volume that enhance the active surface, which ultimately benefits applications such as lithium-ion batteries. The DHP Co3O4 nanoparticles demonstrated an enhanced capacity of 1168 mA h g(-1) at 100 mA g(-1)vs. 590 mA h g(-1) of powders and stable cycling performance greater than 250 cycles when used as an anode material. Most importantly, the electrochemical performance of DHP Co3O4 nanoparticles in a lithium-O2 battery was also investigated for the first time. A low charge potential of ∼4.0 V, a high discharge voltage near 2.74 V and a long cycle ability greater than 100 cycles at a delivered capacity of 2000 mA h g(-1) (current density, 200 mA g(-1)) were observed. The performances were considerably improved compared to recent results of mesoporous Co3O4, Co3O4 nanoparticles and a composite of Co3O4/RGO and Co3O4/Pd. Therefore, it would be promising to investigate such properties of DHP nanoparticles or other hollow metal (oxide) particles for the popular lithium-air battery. PMID:24056975

  11. Thermal nitridation synthesis of MN (M=Ti, V and Cr) nanocrystals from metals and NH{sub 4}Cl

    SciTech Connect

    Yang Xiaogang; Li Cun; Yang Baojun; Wang Wei; Qian Yitai

    2004-06-08

    Nanocrystalline TiN, VN and CrN have been synthesized by a thermal nitridation reaction between the corresponding metal powder and NH{sub 4}Cl at 600 deg. C in an autoclave. X-ray powders diffraction (XRD) indicated that these nanocystallites had a NaCl-type structure with lattice parameters: a=4.236 A for TiN, 4.133 A for VN, 4.145 A for CrN. Transmission electron microscopy (TEM) showed these products consisted of cubic nanocrystals. X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA) techniques revealed that all the products were almost pure nitrides.

  12. A tunable library of substituted thiourea precursors to metal sulfide nanocrystals

    NASA Astrophysics Data System (ADS)

    Hendricks, Mark P.; Campos, Michael P.; Cleveland, Gregory T.; Jen-La Plante, Ilan; Owen, Jonathan S.

    2015-06-01

    Controlling the size of colloidal nanocrystals is essential to optimizing their performance in optoelectronic devices, catalysis, and imaging applications. Traditional synthetic methods control size by terminating the growth, an approach that limits the reaction yield and causes batch-to-batch variability. Herein we report a library of thioureas whose substitution pattern tunes their conversion reactivity over more than five orders of magnitude and demonstrate that faster thiourea conversion kinetics increases the extent of crystal nucleation. Tunable kinetics thereby allows the nanocrystal concentration to be adjusted and a desired crystal size to be prepared at full conversion. Controlled precursor reactivity and quantitative conversion improve the batch-to-batch consistency of the final nanocrystal size at industrially relevant reaction scales.

  13. Properties of silicon dioxide layers with embedded metal nanocrystals produced by oxidation of Si:Me mixture

    PubMed Central

    2011-01-01

    A two-dimensional layers of metal (Me) nanocrystals embedded in SiO2 were produced by pulsed laser deposition of uniformly mixed Si:Me film followed by its furnace oxidation and rapid thermal annealing. The kinetics of the film oxidation and the structural properties of the prepared samples were investigated by Rutherford backscattering spectrometry, and transmission electron microscopy, respectively. The electrical properties of the selected SiO2:Me nanocomposite films were evaluated by measuring C-V and I-V characteristics on a metal-oxide-semiconductor stack. It is found that Me segregation induced by Si:Me mixture oxidation results in the formation of a high density of Me and silicide nanocrystals in thin film SiO2 matrix. Strong evidence of oxidation temperature as well as impurity type effect on the charge storage in crystalline Me-nanodot layer is demonstrated by the hysteresis behavior of the high-frequency C-V curves. PMID:21711632

  14. Copper metal-organic framework nanocrystal for plane effect nonenzymatic electro-catalytic activity of glucose

    NASA Astrophysics Data System (ADS)

    Liu, Yuanying; Zhang, Youjuan; Chen, Jing; Pang, Huan

    2014-09-01

    This work describes the first demonstration of nanocrystal plane dependent nonenzymatic electro-catalytic glucose activity of [Cu3(btc)2] nanocrystals with different shapes (nanocube, truncated cube, cuboctahedron, and octahedron). From electrochemical results, the obtained [Cu3(btc)2] nanocube modified electrode shows the best nonenzymatic electro-catalytic glucose activity. Interestingly, decreasing the {100} crystal planes from cubes to octahedra, changes the nonenzymatic electro-catalytic activity from highly sensitive to general.This work describes the first demonstration of nanocrystal plane dependent nonenzymatic electro-catalytic glucose activity of [Cu3(btc)2] nanocrystals with different shapes (nanocube, truncated cube, cuboctahedron, and octahedron). From electrochemical results, the obtained [Cu3(btc)2] nanocube modified electrode shows the best nonenzymatic electro-catalytic glucose activity. Interestingly, decreasing the {100} crystal planes from cubes to octahedra, changes the nonenzymatic electro-catalytic activity from highly sensitive to general. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr03396e

  15. A Simple Model for Solidification of Undercooled Metallic Samples

    NASA Astrophysics Data System (ADS)

    Saleh, Abdala M.; Clemente, Roberto A.

    2004-06-01

    A simple model for reproducing temperature recalescence behaviour in spherical undercooled liquid metallic samples, undergoing crystallization transformations, is presented. The model is applied to constant heat extraction rate, uniform but time dependent temperature distribution inside the sample (even after the start of crystallization), a classical temperature dependent rate of nucleation (including contributions from different specific heats for different phases and also a catalytic factor to model the possibility of heterogeneous distributed impurities) and the solidified grain interface velocity is taken proportional to the temperature undercooling. Different assumptions are considered for the sample transformed fraction as function of the extended volume of nuclei, like the classical Kolmogoroff, Johnson-Mehl, Avrami one (corresponding to random distribution of nuclei), the Austin-Rickett one (corresponding to some kind of clusterized distribution) and also an empirical one corresponding to some ordering in the distribution of nuclei. As an example of application, a published experimental temperature curve for a zirconium sample in the electromagnetic containerless facility TEMPUS, during the 2nd International Microgravity Laboratory Mission in 1994, is modeled. Some thermo-physical parameters of interest for Zr are discussed.

  16. Synthesis and characterization of transition metal arsenide nanocrystals and the metastability and magneto-structural phase transition behavior of manganese arsenide nanocrystals

    NASA Astrophysics Data System (ADS)

    Zhang, Yanhua

    This dissertation study focuses on (1) probing the magneto-structural phase transformation in nanoscale MnAs; (2) evaluation of the size-dependent phase stability of type-B MnAs (prepared by rapid injection); and (3) developing a general synthetic method for transition metal arsenide nanoparticles. Discrete MnAs nanoparticles that adopt different structures at room temperature (type-A, α-structure and type-B, beta-structure) have been prepared by the solution-phase arrested precipitation method. Atomic pair distribution and Rietveld refinement were employed on synchrotron data to explore the structural transitions of the bulk and nanoparticle samples, and these results were compared to AC magnetic susceptibility measurements of the samples. The results confirm that the structural transition and the magnetic transition are highly correlated in bulk MnAs and suggest that for type-A MnAs nanoparticles, there is a similar magneto-structural phase transition occurring in the same temperature region as that for bulk MnAs. However, for type-B MnAs nanoparticles, there is no magneto-structural phase transition, consistent with that type-B MnAs nanoparticles being kinetically trapped in the beta-structure. Type-B MnAs nanoparticles adopting the beta-strucuture undergo a transformation from beta to α upon cooling. Temperature dependent XRD studies and magnetic measurements suggest that the TP for α → beta conversion is suppressed to lower temperatures relative to bulk and type-A MnAs nanoparticles and that the transformation is reversible but has an enhanced hysteresis, which results in a large coexistence temperature range for the α and beta structure. The transformation temperature correlated with the compression of the lattice parameters of the type-B MnAs nanoparticles due to the decrease in the particle size or the presence of chemical doping, or both. A new general synthetic method for transition metal arsenide (Ni 11As8, FeAs and CoAs) nanocrystals synthesis was

  17. Promotion of the halide effect in the formation of shaped metal nanocrystals via a hybrid cationic, polymeric stabilizer: Octahedra, cubes, and anisotropic growth

    NASA Astrophysics Data System (ADS)

    Sneed, Brian T.; Golden, Matthew C.; Liu, Yejing; Lee, Hiang K.; Andoni, Ilektra; Young, Allison P.; McMahon, Greg; Erdman, Natasha; Shibata, Masateru; Ling, Xing Yi; Tsung, Chia-Kuang

    2016-06-01

    To promote the effect of halide ions (Cl-, Br-, and I-) in facet-selective growth of {111} and {100} of shaped metal nanocrystals, we utilize PDADMAC, a hybrid cationic, polymeric stabilizer. SERS and synthesis experiments provide evidence supporting that the higher amount of PDADMA+ at surfaces promotes the local adsorption of halides, allowing the creation of Pd cubes, octahedra, and cuboctopods.

  18. From Impurity Doping to Metallic Growth in Diffusion Doping: Properties and Structure of Silver-Doped InAs Nanocrystals.

    PubMed

    Amit, Yorai; Li, Yuanyuan; Frenkel, Anatoly I; Banin, Uri

    2015-11-24

    Tuning of the electronic properties of presynthesized colloidal semiconductor nanocrystals (NCs) by doping plays a key role in the prospect of implementing them in printed electronics devices such as transistors and photodetectors. While such impurity doping reactions have already been introduced, the understanding of the doping process, the nature of interaction between the impurity and host atoms, and the conditions affecting the solubility limit of impurities in nanocrystals are still unclear. Here, we used a postsynthesis diffusion-based doping reaction to introduce Ag impurities into InAs NCs. Optical absorption spectroscopy and analytical inductively coupled plasma mass spectroscopy (ICP-MS) were used to present a two-stage doping model consisting of a "doping region" and a "growth region", depending on the impurity to NC ratio in the reaction vessel. X-ray absorption fine-structure (XAFS) spectroscopy was employed to determine the impurity location and correlate between the structural and electronic properties for different sizes of InAs NCs and dopant concentrations. The resulting structural model describes a heterogeneous system where the impurities initially dope the NC, by substituting for In atoms near the surface of the NC, until the "solubility limit" is reached, after which the rapid growth and formation of metallic structures are identified. PMID:26390173

  19. 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.

  20. Nanocrystal-Powered Nanomotor

    SciTech Connect

    Regan, B.C.; Aloni, S.; Jensen, K.; Ritchie, R.O.; Zettl, A.

    2005-07-05

    We have constructed and operated a nanoscale linear motorpowered by a single metal nanocrystal ram sandwiched between mechanicallever arms. Low-level electrical voltages applied to the carbon nanotubelever arms cause the nanocrystal to grow or shrink in a controlledmanner. The length of the ram is adjustable from 0 to more than 150 nm,with extension speeds exceeding 1900 nm/s. The thermodynamic principlesgoverning motor operation resemble those driving frost heave, a naturalsolid-state linear motor.

  1. Origin of Transitions between Metallic and Insulating States in Simple Metals

    NASA Astrophysics Data System (ADS)

    Naumov, Ivan I.; Hemley, Russell J.

    2015-04-01

    Unifying principles that underlie recently discovered transitions between metallic and insulating states in elemental solids under pressure are developed. Using group theory arguments and first-principles calculations, we show that the electronic properties of the phases involved in these transitions are controlled by symmetry principles. The valence bands in these systems are described by simple and composite band representations constructed from localized Wannier functions centered on points unoccupied by atoms, and which are not necessarily all symmetrical. The character of the Wannier functions is closely related to the degree of s -p (-d ) hybridization and reflects multicenter chemical bonding in these insulating states. The conditions under which an insulating state is allowed for structures having an integer number of atoms per primitive unit cell as well as reentrant (i.e., metal-insulator-metal) transition sequences are detailed, resulting in predictions of behavior such as phases having band-contact lines. The general principles developed are tested and applied to the alkali and alkaline earth metals, including elements where high-pressure insulating phases have been reported (e.g., Li, Na, and Ca).

  2. A Simple Method for Drawing Chiral Mononuclear Octahedral Metal Complexes

    ERIC Educational Resources Information Center

    Mohamadou, Aminou; Haudrechy, Arnaud

    2008-01-01

    Octahedral transition-metal complexes are involved in a number of reactions and octahedral coordination geometry, frequently observed for metallic centers, includes important topographical stereochemistry. Depending on the number and nature of different ligands, octahedral coordination units with at least two different monodentate ligands give…

  3. Functionalization of Cellulose Nanocrystals with PEG-Metal-Chelating Diblock Copolymers via Controlled Conjugation in Aqueous Medium

    NASA Astrophysics Data System (ADS)

    Guo, Melinda

    The surface of cellulose nanocrystals (CNCs) was successfully functionalized with metal chelating diblock copolymers via HyNic-4FB conjugation. Two types of PEG-metal-chelating block polymers with hydrazinonicotinate acetone hydrazine (HyNic) end groups were synthesized: mPEG-PGlu(DTPA) 18-HyNic and mPEG-PGlu(DTPA)25-HyNic. These two polymers both had a methoxy PEG (M ˜ 2000 Da) block that differed in the mean degree of polymerization of the metal-chelating block. They were characterized by 1H NMR spectroscopy and gel-permeation chromatography (GPC). 4-Formylbenzamide (4FB) groups were introduced onto the surface of CNCs and quantified through their reaction with 2-hydrazinopyridine. The polymers were grafted onto the surface of CNCs via bis-aryl hydrazone bond formation, and the kinetics of this reaction was explored by UV/Vis spectroscopy. The CNCs were also labeled with rhodamine and Alexa FluorRTM 488 dyes. Students in our collaborator's group in Pharmacy are examining applications of these materials as radiotherapeutic agents for cancer treatment.

  4. 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.

  5. Chelating ligands for nanocrystals' surface functionalization.

    PubMed

    Querner, Claudia; Reiss, Peter; Bleuse, Joël; Pron, Adam

    2004-09-22

    A new family of ligands for the surface functionalization of CdSe nanocrystals is proposed, namely alkyl or aryl derivatives of carbodithioic acids (R-C(S)SH). The main advantages of these new ligands are as follows: they nearly quantitatively exchange the initial surface ligands (TOPO) in very mild conditions; they significantly improve the resistance of nanocrystals against photooxidation because of their ability of strong chelate-type binding to metal atoms; their relatively simple preparation via Grignard intermediates facilitates the development of new bifunctional ligands containing, in addition to the anchoring carbodithioate group, a second function, which enables the grafting of molecules or macromolecules of interest on the nanocrystal surface. To give an example of this approach, we report, for the first time, the grafting of an electroactive oligomer from the polyaniline family-aniline tetramer-on CdSe nanocrystals after their functionalization with 4-formyldithiobenzoic acid. The grafting proceeds via a condensation reaction between the aldehyde group of the ligand and the terminal primary amine group of the tetramer. The resulting organic/inorganic hybrid exhibits complete extinction of the fluorescence of its constituents, indicating efficient charge or energy transfer between the organic and the inorganic semiconductors. PMID:15366904

  6. Carboxylic-Acid-passivated metal oxide nanocrystals: ligand exchange characteristics of a new binding motif.

    PubMed

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

    2015-05-26

    Ligand exchange is central in the processing of inorganic nanocrystals (NCs) and requires understanding of surface chemistry. Studying sterically stabilized HfO2 and ZrO2 NCs using (1) H solution NMR and IR spectroscopy as well as elemental analysis, this paper demonstrates the reversible exchange of initial oleic acid ligands for octylamine and self-adsorption of oleic acid at NC surfaces. Both processes are incompatible with an X-type binding motif of carboxylic acids as reported for sulfide and selenide NCs. We argue that this behavior stems from the dissociative adsorption of carboxylic acids at the oxide surface. Both proton and carboxylate moieties must be regarded as X-type ligands yielding a combined X2 binding motif that allows for self-adsorption and exchange for L-type ligands. PMID:25866095

  7. A simple approach to metal hydride alloy optimization

    NASA Technical Reports Server (NTRS)

    Lawson, D. D.; Miller, C.; Landel, R. F.

    1976-01-01

    Certain metals and related alloys can combine with hydrogen in a reversible fashion, so that on being heated, they release a portion of the gas. Such materials may find application in the large scale storage of hydrogen. Metal and alloys which show high dissociation pressure at low temperatures, and low endothermic heat of dissociation, and are therefore desirable for hydrogen storage, give values of the Hildebrand-Scott solubility parameter that lie between 100-118 Hildebrands, (Ref. 1), close to that of dissociated hydrogen. All of the less practical storage systems give much lower values of the solubility parameter. By using the Hildebrand solubility parameter as a criterion, and applying the mixing rule to combinations of known alloys and solid solutions, correlations are made to optimize alloy compositions and maximize hydrogen storage capacity.

  8. A simple approach to metal hydride alloy optimization

    NASA Technical Reports Server (NTRS)

    Lawson, D. D.; Miller, C. G.; Landel, R. F.

    1976-01-01

    Hildebrand-Scott (1950) solubility parameters can be obtained for metals and alloys by calculating the cohesive energy density (CED), equal to the square of the solubility parameter, and a function of the heat of sublimation and the atomic volume. It is suggested that the solubility parameter permits estimation of the hydrogen storage capacity of an alloy and that alloys with a solubility parameter approximately equal to the parameter for hydrogen will have greater hydrogen storage capacity than other alloys. Equilibrium pressure - temperature relationships for some metal hydrides are presented in conjunction with the calculated solubility parameter and correlated with characteristics which would be useful in hydrogen-powered vehicles. Alloy properties which increase the amount of nonstoichiometric reversible hydrogen absorption are discussed.

  9. Exploiting the colloidal nanocrystal library to construct electronic devices

    NASA Astrophysics Data System (ADS)

    Choi, Ji-Hyuk; Wang, Han; Oh, Soong Ju; Paik, Taejong; Sung, Pil; Sung, Jinwoo; Ye, Xingchen; Zhao, Tianshuo; Diroll, Benjamin T.; Murray, Christopher B.; Kagan, Cherie R.

    2016-04-01

    Synthetic methods produce libraries of colloidal nanocrystals with tunable physical properties by tailoring the nanocrystal size, shape, and composition. Here, we exploit colloidal nanocrystal diversity and design the materials, interfaces, and processes to construct all-nanocrystal electronic devices using solution-based processes. Metallic silver and semiconducting cadmium selenide nanocrystals are deposited to form high-conductivity and high-mobility thin-film electrodes and channel layers of field-effect transistors. Insulating aluminum oxide nanocrystals are assembled layer by layer with polyelectrolytes to form high–dielectric constant gate insulator layers for low-voltage device operation. Metallic indium nanocrystals are codispersed with silver nanocrystals to integrate an indium supply in the deposited electrodes that serves to passivate and dope the cadmium selenide nanocrystal channel layer. We fabricate all-nanocrystal field-effect transistors on flexible plastics with electron mobilities of 21.7 square centimeters per volt-second.

  10. Exploiting the colloidal nanocrystal library to construct electronic devices.

    PubMed

    Choi, Ji-Hyuk; Wang, Han; Oh, Soong Ju; Paik, Taejong; Sung, Pil; Sung, Jinwoo; Ye, Xingchen; Zhao, Tianshuo; Diroll, Benjamin T; Murray, Christopher B; Kagan, Cherie R

    2016-04-01

    Synthetic methods produce libraries of colloidal nanocrystals with tunable physical properties by tailoring the nanocrystal size, shape, and composition. Here, we exploit colloidal nanocrystal diversity and design the materials, interfaces, and processes to construct all-nanocrystal electronic devices using solution-based processes. Metallic silver and semiconducting cadmium selenide nanocrystals are deposited to form high-conductivity and high-mobility thin-film electrodes and channel layers of field-effect transistors. Insulating aluminum oxide nanocrystals are assembled layer by layer with polyelectrolytes to form high-dielectric constant gate insulator layers for low-voltage device operation. Metallic indium nanocrystals are codispersed with silver nanocrystals to integrate an indium supply in the deposited electrodes that serves to passivate and dope the cadmium selenide nanocrystal channel layer. We fabricate all-nanocrystal field-effect transistors on flexible plastics with electron mobilities of 21.7 square centimeters per volt-second. PMID:27124455

  11. A simple, general route to 2-pyridylidene transition metal complexes.

    PubMed

    Roselló-Merino, Marta; Díez, Josefina; Conejero, Salvador

    2010-12-28

    Pyridinium 2-carboxylates decompose thermally in the presence of a variety of late transition metal precursors to yield the corresponding 2-pyridylidene-like complexes. The mild reaction conditions and structural diversity that can be generated in the heterocyclic ring make this method an attractive alternative for the synthesis of 2-pyridylidene complexes. IR spectra of the Ir(i) carbonyl compounds [IrCl(NHC)(CO)(2)] indicate that these N-heterocyclic carbene ligands are among the strongest σ-electron donors. PMID:21052586

  12. Simple Molecular Reactive Force Field for Metal-Organic Synthesis.

    PubMed

    Andrejevic, Jovana; Stevenson, James; Clancy, Paulette

    2016-02-01

    For colloidal quantum dots to transition from research laboratories to deployment as optical and electronic products, there will be a need to scale-up their production to large-scale manufacturing processes. This demand increases the need to understand their formation via a molecular representation of the nucleation of lead sulfide (PbS) quantum dot systems passivated by lead oleate complexes. We demonstrate the effectiveness of a new type of reactive potential, custom-made for this system, that is drawn from simple Morse, Lennard-Jones, and Coulombic components, which can reproduce reactions across a broad range of PbS quantum dot sizes with good accuracy. We validate the capability of this model to capture reactive systems by comparison to ab initio calculations for a reaction between two dots. PMID:26745239

  13. Effect of nanoscale size and medium on metal work function in oleylamine-capped gold nanocrystals

    NASA Astrophysics Data System (ADS)

    Abdellatif, M. H.; Ghosh, S.; Liakos, I.; Scarpellini, A.; Marras, S.; Diaspro, A.; Salerno, M.

    2016-02-01

    The work function is an important material property with several applications in photonics and optoelectronics. We aimed to characterize the work function of clusters resulting from gold nanocrystals capped with oleylamine surfactant and drop-casted onto gold substrate. We used scanning Kelvin probe microscopy to investigate the work function, and complemented our study mainly with X-ray diffraction and X-ray photoelectron spectroscopy. The oleylamine works as an electron blocking layer through which the electrical conduction takes place by tunneling effect. The surface potential appears to depend on the size of the clusters, which can be ascribed to their difference in effective work function with the substrate. The charge state of gold clusters is discussed in comparison with theory, and their capacitance is calculated from a semi-analytical equation. The results suggest that at the nanoscale the work function is not an intrinsic property of a material but rather depends on the size and morphology of the clusters, including also effects of the surrounding materials.

  14. Metal nanocrystal formation in magnesium aluminate spinel and silicon dioxide with high-flux Cu - ions

    NASA Astrophysics Data System (ADS)

    Kishimoto, N.; Takeda, Y.; Umeda, N.; Gritsyna, V. T.; Lee, C. G.; Saito, T.

    2000-05-01

    Intense Cu- ions of 60 keV spontaneously grow nanospheres embedded within a shallow depth in insulators, which exhibit optical nonlinearity. The in-beam growth of nanoparticles is preferred but subjected to phase instability. Spinel oxides may be a candidate substrate to realize the phase stability, because of good radiation resistance and sufficient transparency. Spinel of MgAl2O4 and amorphous(a-) SiO2 were irradiated with Cu- at dose rates up to 100 μA/cm2, at a total dose of 3.0 × 1016 ions/cm2. Nanocrystal morphology and optical absorption (hν=0.5 - 5 eV) varied depending on dose rate. At high dose rates, a-SiO2 showed a strong tendency of depth-dependent rearrangement and particle coarsening. The MgAl2O4 also showed spontaneous precipitation of nanoparticles but, in contrast, neither long-range rearrangement of implants nor particle coarsening, up to high dose rates. Therefore, the MgAl2O4 spinel is a promising substrate to realize fine and stable nanostructures.

  15. a Simple Method to Prepare Nanoporous Sn:Pb Composite Metal Foam

    NASA Astrophysics Data System (ADS)

    Zandi, Majid; Amirhoseiny, Maryam; Mosayyebi, Abolghasem

    2015-03-01

    A novel and simple approach for preparing nanoporous binder free Sn:Pb composite metal foam has been demonstrated. The anodized metallic composite block was functionalized and also found a nanoporous structure. A scanning electron microscopy (SEM) result shows that the nanoflake-like arrangement has synthesized. The X-ray diffraction (XRD) results confirm the nanoporous structure of the Sn/Pb foam after etching with 6 M NaOH. The prepared Sn:Pb metal foam is able to be used as a super capacitors electrode to offer large areal capacitance with regards to the synergic integration of Sn and Pb metals and the unique nanoporous structure.

  16. Pulsed-Laser-Induced Simple Synthetic Route for Tb(3)Al(5)O(12):Ce Colloidal Nanocrystals and Their Luminescent Properties.

    PubMed

    Mhin, Sung Wook; Ryu, Jeong Ho; Kim, Kang Min; Park, Gyeong Seon; Ryu, Han Wool; Shim, Kwang Bo; Sasaki, Takeshi; Koshizaki, Naoto

    2009-01-01

    Cerium-doped Tb(3)Al(5)O(12) (TAG:Ce(3+)) colloidal nanocrystals were synthesized by pulsed laser ablation (PLA) in de-ionized water and lauryl dimethylaminoacetic acid betain (LDA) aqueous solution for luminescent bio-labeling application. The influence of LDA molecules on the crystallinity, crystal morphology, crystallite size, and luminescent properties of the prepared TAG:Ce(3+) colloidal nanocrystals was investigated in detail. When the LDA solution was used, smaller average crystallite size, narrower size distribution, and enhanced luminescence were observed. These characteristics were explained by the effective role of occupying the oxygen defects on the surface of TAG:Ce(3+) colloidal nanocrystal because the amphoteric LDA molecules were attached by positively charged TAG:Ce(3+) colloidal nanocrystals. The blue-shifted phenomena found in luminescent spectra of the TAG:Ce(3+) colloidal nanocrystals could not be explained by previous crystal field theory. We discuss the 5d energy level of Ce(3+) with decreased crystal size with a phenomenological model that explains the relationship between bond distance with 5d energy level of Ce(3+) based on the concept of crystal field theory modified by covalency contribution. PMID:20596420

  17. Pulsed-Laser-Induced Simple Synthetic Route for Tb3Al5O12:Ce3+ Colloidal Nanocrystals and Their Luminescent Properties

    NASA Astrophysics Data System (ADS)

    Mhin, Sung Wook; Ryu, Jeong Ho; Kim, Kang Min; Park, Gyeong Seon; Ryu, Han Wool; Shim, Kwang Bo; Sasaki, Takeshi; Koshizaki, Naoto

    2009-08-01

    Cerium-doped Tb3Al5O12 (TAG:Ce3+) colloidal nanocrystals were synthesized by pulsed laser ablation (PLA) in de-ionized water and lauryl dimethylaminoacetic acid betain (LDA) aqueous solution for luminescent bio-labeling application. The influence of LDA molecules on the crystallinity, crystal morphology, crystallite size, and luminescent properties of the prepared TAG:Ce3+ colloidal nanocrystals was investigated in detail. When the LDA solution was used, smaller average crystallite size, narrower size distribution, and enhanced luminescence were observed. These characteristics were explained by the effective role of occupying the oxygen defects on the surface of TAG:Ce3+ colloidal nanocrystal because the amphoteric LDA molecules were attached by positively charged TAG:Ce3+ colloidal nanocrystals. The blue-shifted phenomena found in luminescent spectra of the TAG:Ce3+ colloidal nanocrystals could not be explained by previous crystal field theory. We discuss the 5d energy level of Ce3+ with decreased crystal size with a phenomenological model that explains the relationship between bond distance with 5d energy level of Ce3+ based on the concept of crystal field theory modified by covalency contribution.

  18. Hollow Alveolus-Like Nanovesicle Assembly with Metal-Encapsulated Hollow Zeolite Nanocrystals.

    PubMed

    Dai, Chengyi; Zhang, Anfeng; Liu, Min; Gu, Lin; Guo, Xinwen; Song, Chunshan

    2016-08-23

    Inspired by the vesicular structure of alveolus which has a porous nanovesicle structure facilitating the transport of oxygen and carbon dioxide, we designed a hollow nanovesicle assembly with metal-encapsulated hollow zeolite that would enhance diffusion of reactants/products and inhibit sintering and leaching of active metals. This zeolitic nanovesicle has been successfully synthesized by a strategy which involves a one-pot hydrothermal synthesis of hollow assembly of metal-containing solid zeolite crystals without a structural template and a selective desilication-recrystallization accompanied by leaching-hydrolysis to convert the metal-containing solid crystals into metal-encapsulated hollow crystals. We demonstrate the strategy in synthesizing a hollow nanovesicle assembly of Fe2O3-encapsulated hollow crystals of ZSM-5 zeolite. This material possesses a microporous (0.4-0.6 nm) wall of hollow crystals and a mesoporous (5-17 nm) shell of nanovesicle with macropores (about 350 nm) in the core. This hierarchical structure enables excellent Fe2O3 dispersion (3-4 nm) and resistance to sintering even at 800 °C; facilitates the transport of reactant/products; and exhibits superior activity and resistance to leaching in phenol degradation. Hollow nanovesicle assembly of Fe-Pt bimetal-encapsulated hollow ZSM-5 crystals was also prepared. PMID:27429013

  19. Kinetic description of metal nanocrystal oxidation: a combined theoretical and experimental approach for determining morphology and diffusion parameters in hollow nanoparticles by the nanoscale Kirkendall effect

    NASA Astrophysics Data System (ADS)

    Watanabe, Yoshiki; Mowbray, Ryan W.; Rice, Katherine P.; Stoykovich, Mark P.

    2014-10-01

    The oxidation of colloidal metal nanocrystals to form hollow shells via the nanoscale Kirkendall effect has been investigated using a combined theoretical and experimental approach. A generalized kinetic model for the formation of hollow nanoparticles describes the phenomenon and, unlike prior models, is applicable to any material system and accounts for the effect of surface energies. Phase diagrams of the ultimate oxidized nanoparticle morphology and the time to achieve complete oxidation are calculated, and are found to depend significantly upon consideration of surface energy effects that destabilize the initial formation of small voids. For the oxidation of Cu nanocrystals to Cu2O nanoparticles, we find that the diffusion coefficients dictate the morphological outcomes: the ratio of ? to ? controls the void size, ? determines the time of oxidation and ? is largely irrelevant in the kinetics of oxidation. The kinetic model was used to fit experimental measurements of 11 nm diameter Cu nanocrystals oxidized in air from which temperature-dependent diffusivities of ? and ? for 100 ≤ T ≤ 200 °C were determined. In contrast to previous interpretations of the nanoscale Kirkendall effect in the Cu/Cu2O system, these results are obtained without any a priori assumptions about the relative magnitudes of ? and ?. The theoretical and experimental approaches presented here are broadly applicable to any nanoparticle system undergoing oxidation, and can be used to precisely control the final nanoparticle morphology for applications in catalysis or optical materials.

  20. Aggregation Kinetics of Metal Chalcogenide Nanocrystals: Generation of Transparent CdSe(ZnS) Core(Shell) Gels

    SciTech Connect

    Korala, Lasantha; Brock, Stephanie

    2012-08-16

    Transparent CdSe (ZnS) core (shell) sol–gel materials have potential uses in optoelectronic applications such as light-emitting diodes (LEDs) due to their strong luminescence properties and the potential for charge transport through the prewired nanocrystal (NC) network of the gel. However, typical syntheses of metal chalcogenide gels yield materials with poor transparency. In this work, the mechanism and kinetics of aggregation of two sizes of CdSe (ZnS) core (shell) NCs, initiated by removal of surface thiolate ligands using tetranitromethane (TNM) as an oxidant, were studied by means of time-resolved dynamic light scattering (TRDLS); the characteristics of the resultant gels were probed by optical absorption, transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS). At low concentrations of NCs (ca. 4 × 10{sup –7} M), the smaller, green-emitting NCs aggregate faster than the larger, orange-emitting NCs, for a specific oxidant concentration. The kinetics of aggregation have a significant impact on the macroscopic properties (i.e., transparency) of the resultant gels, with the transparency of the gels decreasing with the increase of oxidant concentration due the formation of larger clusters at the gel point and a shift away from a reaction-limited cluster-aggregation (RLCA) mechanism. This is further confirmed by analyses of the gel structures by SAXS and TEM. Likewise, the larger orange-emitting particles also produce larger aggregates at the gel point, leading to lower transparency. The ability to control the transparency of chalcogenide gels will enable their properties to be tuned in order to address application-specific needs in optoelectronics.

  1. Composite materials with metal oxide attached to lead chalcogenide nanocrystal quantum dots with linkers

    DOEpatents

    Fuke, Nobuhiro; Koposov, Alexey Y; Sykora, Milan; Hoch, Laura

    2014-12-16

    Composite materials useful for devices such as photoelectrochemical solar cells include a substrate, a metal oxide film on the substrate, nanocrystalline quantum dots (NQDs) of lead sulfide, lead selenide, and lead telluride, and linkers that attach the NQDs to the metal oxide film. Suitable linkers preserve the 1s absorption peak of the NQDs. A suitable linker has a general structure A-B-C where A is a chemical group adapted for binding to a MO.sub.x and C is a chemical group adapted for binding to a NQD and B is a divalent, rigid, or semi-rigid organic spacer moiety. Other linkers that preserve the 1s absorption peak may also be used.

  2. Facet-dependent electrochemical properties of Co3O4 nanocrystals toward heavy metal ions

    PubMed Central

    Yu, Xin-Yao; Meng, Qiang-Qiang; Luo, Tao; Jia, Yong; Sun, Bai; Li, Qun-Xiang; Liu, Jin-Huai; Huang, Xing-Jiu

    2013-01-01

    We revealed an interesting facet-dependent electrochemical behavior toward heavy metal ions (HMIs) based on their adsorption behaviors. The (111) facet of Co3O4 nanoplates has better electrochemical sensing performance than that of the (001) facet of Co3O4 nanocubes. Adsorption measurements and density-functional theory (DFT) calculations reveals that adsorption of HMIs is responsible for the difference of electrochemical properties. Our combined experimental and theoretical studies provide a solid hint to explain the mechanism of electrochemical detection of HMIs using nanoscale metal oxides. Furthermore, this study not only suggests a promising new strategy for designing high performance electrochemical sensing interface through the selective synthesis of nanoscale materials exposed with different well-defined facets, but also provides a deep understanding for a more sensitive and selective electroanalysis at nanomaterials modified electrodes. PMID:24097175

  3. Metal-semiconductor phase transition of order arrays of VO2 nanocrystals

    NASA Astrophysics Data System (ADS)

    Lopez, Rene; Suh, Jae; Feldman, Leonard; Haglund, Richard

    2004-03-01

    The study of solid-state phase transitions at nanometer length scales provides new insights into the effects of material size on the mechanisms of structural transformations. Such research also opens the door to new applications, either because materials properties are modified as a function of particle size, or because the nanoparticles interact with a surrounding matrix material, or with each other. In this paper, we describe the formation of vanadium dioxide nanoparticles in silicon substrates by pulsed laser deposition of ion beam lithographically selected sites and thermal processing. We observe the collective behavior of 50 nm diameter VO2 oblate nanoparticles, 10 nm high, and ordered in square arrays with arbitrary lattice constant. The metal-semiconductor-transition of the VO2 precipitates shows different features in each lattice spacing substrate. The materials are characterized by electron microscopy, x-ray diffraction, Rutherford backscattering. The features of the phase transition are studied via infrared optical spectroscopy. Of particular interest are the enhanced scattering and the surface plasmon resonance when the particles reach the metallic state. This resonance amplifies the optical contrast in the range of near-infrared optical communication wavelengths and it is altered by the particle-particle coupling as in the case of noble metals. In addition the VO2 nanoparticles exhibit sharp transitions with up to 50 K of hysteresis, one of the largest values ever reported for this transition. The optical properties of the VO2 nanoarrays are correlated with the size of the precipitates and their inter-particle distance. Nonlinear and ultra fast optical measurements have shown that the transition is the fastest known solid-solid transformation. The VO2 nanoparticles show the same bulk property, transforming in times shorter than 150 fs. This makes them remarkable candidates for ultrafast optical and electronic switching applications.

  4. ENHANCING DAMAGE VISIBILITY ON METALLIC BEARING SURFACES: A SIMPLE TECHNIQUE FOR PHOTOGRAPHY AND VIEWING

    PubMed Central

    Heiner, Anneliese D.; Kruger, Karen M.; Baer, Thomas E.; Brown, Thomas D.

    2012-01-01

    Damage to metallic bearing surfaces typically involves scratches, scrapes, metal transfer, and organic deposits. This damage can cause accelerated wear of the opposing surface and subsequent implant failure. Photography and viewing of metallic bearing surfaces, for documenting this damage, is hindered by optical reflectivity. This note demonstrates a simple, practical technique for metallic bearing surface photography and viewing that minimizes this reflectivity problem, that does not involve any modification of the bearing surface, and that allows for improved observation and documentation of overall damage. When the metallic bearing surface is placed within a tube of translucent material, the appearance of damage on that bearing surface is dramatically enhanced, showing up against a smooth, even background with excellent contrast and with fine detail achievable. PMID:23333257

  5. Binding in pair potentials of liquid simple metals from nonlocality in electronic kinetic energy

    NASA Technical Reports Server (NTRS)

    Perrot, F.; March, N. H.

    1990-01-01

    The paper presents an explicit expression for the pair potential in liquid simple metals from low-order density-gradient theory when the superposition of single-center displaced charges is employed. Numerical results are presented for the gradient expansion pair interaction in liquid Na and Be. The low-order density-gradient equation for the pair potential is presented.

  6. Enhancement of dielectric constant in transition metal doped ZnO nanocrystals

    NASA Astrophysics Data System (ADS)

    Singh, Swati; Dey, P.; Roy, J. N.; Mandal, S. K.

    2014-09-01

    We have presented dielectric studies on Zn1-xCoxO, Zn1-xFexO, and Zn1-xFex/2Cox/2O (x = doping level) semiconducting nanoparticles (˜2-40 nm). For all those samples, dielectric constant (є) is found to exhibit a maximum with x. Enhancement of є is found to be ˜250 times for Zn0.85Co0.15O and ˜400 times for Zn0.8Fe0.1Co0.1O from that of ZnO. Presence of effective higher oxidation state of transition metals ions in ZnO due to Fe/Co doping resulting in space charge polarization possibly yields this effect. The simultaneous existence of high є, semiconducting, and ferromagnetic like behaviour at 300 K seems to propose Zn0.8Fe0.1Co0.1O, promising for technological application.

  7. 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.

  8. Thermophysical properties of simple liquid metals: A brief review of theory

    NASA Technical Reports Server (NTRS)

    Stroud, David

    1993-01-01

    In this paper, we review the current theory of the thermophysical properties of simple liquid metals. The emphasis is on thermodynamic properties, but we also briefly discuss the nonequilibrium properties of liquid metals. We begin by defining a 'simple liquid metal' as one in which the valence electrons interact only weakly with the ionic cores, so that the interaction can be treated by perturbation theory. We then write down the equilibrium Hamiltonian of a liquid metal as a sum of five terms: the bare ion-ion interaction, the electron-electron interaction, the bare electron-ion interaction, and the kinetic energies of electrons and ions. Since the electron-ion interaction can be treated by perturbation, the electronic part contributes in two ways to the Helmholtz free energy: it gives a density-dependent term which is independent of the arrangement of ions, and it acts to screen the ion-ion interaction, giving rise to effective ion-ion pair potentials which are density-dependent, in general. After sketching the form of a typical pair potential, we briefly enumerate some methods for calculating the ionic distribution function and hence the Helmholtz free energy of the liquid: monte Carlo simulations, molecular dynamics simulations, and thermodynamic perturbation theory. The final result is a general expression for the Helmholtz free energy of the liquid metal. It can be used to calculate a wide range of thermodynamic properties of simple metal liquids, which we enumerate. They include not only a range of thermodynamic coefficients of both metals and alloys, but also many aspects of the phase diagram, including freezing curves of pure elements and phase diagrams of liquid alloys (including liquidus and solidus curves). We briefly mention some key discoveries resulting from previous applications of this method, and point out that the same methods work for other materials not normally considered to be liquid metals (such as colloidal suspensions, in which the

  9. Structure Map for Embedded Binary Alloy Nanocrystals

    SciTech Connect

    Yuan, C.W.; Shin, S.J.; Liao, C.Y.; Guzman, J.; Stone, P.R.; Watanabe, M.; Ager III, J.W.; Haller, E.E.; Chrzan, D.C.

    2008-09-20

    The equilibrium structure of embedded nanocrystals formed from strongly segregating binary-alloys is considered within a simple thermodynamic model. The model identifies two dimensionlessinterface energies that dictate the structure, and allows prediction of the stable structure for anychoice of these parameters. The resulting structure map includes three distinct nanocrystal mor-phologies: core/shell, lobe/lobe, and completely separated spheres.

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

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

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

  11. Formamide: an efficient solvent to synthesize water-soluble and sub-ten-nanometer nanocrystals

    NASA Astrophysics Data System (ADS)

    Xu, Biao; Zhang, Zhicheng; Wang, Xun

    2013-05-01

    Nanocrystals have drawn lots of attention in many fields. The main-stream synthetic routes usually produced hydrophobic nanocrystals (NCs). Organometallic precursors and long-alkyl-chain ligands are adopted and for further use surface modification to render them water-soluble is needed. A direct protocol to synthesize water-soluble NCs in an environmental-friendly and convenient way is still quite deficient, especially for sub-10 nm NCs. We report here a formamide solvent-system to prepare high-quality metal, metal alloy, metal sulfide, metal selenide and ternary sulfide NCs in the sub-10 nm region, with simple inorganic metal salts as precursors. The as-obtained NCs exhibit monodisperse size and can be dispersed in aqueous solution for further applications.Nanocrystals have drawn lots of attention in many fields. The main-stream synthetic routes usually produced hydrophobic nanocrystals (NCs). Organometallic precursors and long-alkyl-chain ligands are adopted and for further use surface modification to render them water-soluble is needed. A direct protocol to synthesize water-soluble NCs in an environmental-friendly and convenient way is still quite deficient, especially for sub-10 nm NCs. We report here a formamide solvent-system to prepare high-quality metal, metal alloy, metal sulfide, metal selenide and ternary sulfide NCs in the sub-10 nm region, with simple inorganic metal salts as precursors. The as-obtained NCs exhibit monodisperse size and can be dispersed in aqueous solution for further applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr00643c

  12. METALLICITY GRADIENTS THROUGH DISK INSTABILITY: A SIMPLE MODEL FOR THE MILKY WAY'S BOXY BULGE

    SciTech Connect

    Martinez-Valpuesta, Inma; Gerhard, Ortwin E-mail: gerhard@mpe.mpg.de

    2013-03-20

    Observations show a clear vertical metallicity gradient in the Galactic bulge, which is often taken as a signature of dissipative processes in the formation of a classical bulge. Various evidence shows, however, that the Milky Way is a barred galaxy with a boxy bulge representing the inner three-dimensional part of the bar. Here we show with a secular evolution N-body model that a boxy bulge formed through bar and buckling instabilities can show vertical metallicity gradients similar to the observed gradient if the initial axisymmetric disk had a comparable radial metallicity gradient. In this framework, the range of metallicities in bulge fields constrains the chemical structure of the Galactic disk at early times before bar formation. Our secular evolution model was previously shown to reproduce inner Galaxy star counts and we show here that it also has cylindrical rotation. We use it to predict a full mean metallicity map across the Galactic bulge from a simple metallicity model for the initial disk. This map shows a general outward gradient on the sky as well as longitudinal perspective asymmetries. We also briefly comment on interpreting metallicity gradient observations in external boxy bulges.

  13. A simple urea-based route to ternary metal oxynitride nanoparticles

    SciTech Connect

    Gomathi, A.; Reshma, S.; Rao, C.N.R.

    2009-01-15

    Ternary metal oxynitrides are generally prepared by heating the corresponding metal oxides with ammonia for long durations at high temperatures. In order to find a simple route that avoids use of gaseous ammonia, we have employed urea as the nitriding agent. In this method, ternary metal oxynitrides are obtained by heating the corresponding metal carbonates and transition metal oxides with excess urea. By this route, ternary metal oxynitrides of the formulae MTaO{sub 2}N (M=Ca, Sr or Ba), MNbO{sub 2}N (M=Sr or Ba), LaTiO{sub 2}N and SrMoO{sub 3-x}N{sub x} have been prepared successfully. The oxynitrides so obtained were generally in the form of nanoparticles, and were characterized by various physical techniques. - Graphical abstract: Nanoparticles of ternary metal oxynitrides can be synthesized by means of urea route. Given is the TEM image of the nanoparticles of CaTaO{sub 2}N so obtained and the insets show the SAED pattern and HREM image of the nanoparticles.

  14. "Nanocrystal bilayer for tandem catalysis"

    SciTech Connect

    Yamada, Yusuke; Tsung, Chia Kuang; Huang, Wenyu; Huo, Ziyang; E.Habas, Susan E; Soejima, Tetsuro; Aliaga, Cesar E; Samorjai, Gabor A; Yang, Peidong

    2011-01-24

    Supported catalysts are widely used in industry and can be optimized by tuning the composition and interface of the metal nanoparticles and oxide supports. Rational design of metal-metal oxide interfaces in nanostructured catalysts is critical to achieve better reaction activities and selectivities. We introduce here a new class of nanocrystal tandem catalysts that have multiple metal-metal oxide interfaces for the catalysis of sequential reactions. We utilized a nanocrystal bilayer structure formed by assembling platinum and cerium oxide nanocube monolayers of less than 10 nm on a silica substrate. The two distinct metal-metal oxide interfaces, CeO2-Pt and Pt-SiO2, can be used to catalyse two distinct sequential reactions. The CeO2-Pt interface catalysed methanol decomposition to produce CO and H2, which were subsequently used for ethylene hydroformylation catalysed by the nearby Pt-SiO2 interface. Consequently, propanal was produced selectively from methanol and ethylene on the nanocrystal bilayer tandem catalyst. This new concept of nanocrystal tandem catalysis represents a powerful approach towards designing high-performance, multifunctional nanostructured catalysts

  15. A simple evolutional model of Habitable Zone around host stars with various mass and low metallicity

    NASA Astrophysics Data System (ADS)

    Oishi, Midori; Kamaya, Hideyuki

    2016-02-01

    Habitable Zone (HZ) is defined as a life existence area, where water at the surface of the terrestrial planet is in liquid phase. This is caused by the balance of flux from the host star and effective radiative cooling with greenhouse effect of the planet. However, the flux varies according to evolutional phase of the host star. So, a simple but newest HZ model considering stellar mass range from 0.08 to 4.00 M⊙ has been proposed. It studies both at zero-age main sequence (ZAMS) and terminal-age main sequence (TMS) phases to examine persistence of HZ. By the way, it discusses the case of the metallicity like the Sun. Actually, it is interesting to study a HZ model considering host stars with low metallicity. So, we examine the effect of metallicity, following the precedent simple model. In our analysis, metallicity affects little for HZ orbital range at ZAMS, while it affects clearly in case of TMS. Since the inner and outer HZ boundaries at TMS are shifted outward especially in the mass range from 1.5 to 2.0 M⊙, we find persistent HZ is allowed above about 1.8 M⊙. The age of the universe is 13.8 Gyr, which is comparable to main sequence life time of about 0.8 M⊙ for the low metallicity case. Then, the effect of metallicity to estimate HZ of low metallicity host stars is important for the mass range from 0.8 to 1.8 M⊙.

  16. Optoperforation of Intact Plant Cells, Spectral Characterization of Alloy Disorder in InAsP Alloys, and Bimetallic Concentric Surfaces for Metal-Enhanced Fluorescence in Upconverting Nanocrystals

    NASA Astrophysics Data System (ADS)

    Merritt, Travis R.

    The techniques of optoperforation, spectral characterization of alloy disorder, and metal-enhanced uorescence were applied to previously unconsidered or disregarded systems in order to demonstrate that such applications are both feasible and consequential. These applications were the subject of three disparate works and, as such, are independently discussed. Despite being ostensibly restricted to mammalian cells, optoperforation was demonstrated in intact plant cells by means of successful femtosecond-laser-mediated infiltration of a membrane impermeable dextran-conjugated dye into cells of vital Arabidopsis seedling stems. By monitoring the rate of dye uptake, and the reaction of both CFP-expressing vacuoles and nanocellulose substrates, the intensity and exposure time of the perforating laser were adjusted to values that both preserved cell vitality and permitted the laser-assisted uptake of the uorophore. By using these calibrated laser parameters, dye was injected and later observed in targeted cells after 72 hours, all without deleteriously affecting the vital functions of those cells. In the context of alloy disorder, photoluminescence of excitonic transitions in two InAsxP1--x alloys were studied through temperature and magnetic field strength dependencies, as well as compositionally-dependent time-resolved behavior. The spectral shape, behavior of the linewidths at high magnetic fields, and the divergence of the peak positions from band gap behavior at low temperatures indicated that alloy disorder exists in the x=0.40 composition while showing no considerable presence in the x=0.13 composition. The time-resolved photoluminescence spectrum for both compositions feature a fast and slow decay, with the slow decay lifetime in x=0.40 being longer than that of x=0.13, which may be due to carrier migration between localized exciton states in x=0.40. In order to achieve broadband metal-enhanced uorescence in upconverting NaYF4:Yb,Er nanocrystals, two nanocomposite

  17. Electric relaxation processes in chemodynamics of aqueous metal complexes: from simple ligands to soft nanoparticulate complexants.

    PubMed

    van Leeuwen, Herman P; Buffle, Jacques; Town, Raewyn M

    2012-01-10

    The chemodynamics of metal complexes with nanoparticulate complexants can differ significantly from that for simple ligands. The spatial confinement of charged sites and binding sites to the nanoparticulate body impacts on the time scales of various steps in the overall complex formation process. The greater the charge carried by the nanoparticle, the longer it takes to set up the counterion distribution equilibrium with the medium. A z+ metal ion (z > 1) in a 1:1 background electrolyte will accumulate in the counterionic atmosphere around negatively charged simple ions, as well as within/around the body of a soft nanoparticle with negative structural charge. The rate of accumulation is often governed by diffusion and proceeds until Boltzmann partition equilibrium between the charged entity and the ions in the medium is attained. The electrostatic accumulation proceeds simultaneously with outer-sphere and inner-sphere complex formation. The rate of the eventual inner-sphere complex formation is generally controlled by the rate constant of dehydration of the metal ion, k(w). For common transition metal ions with moderate to fast dehydration rates, e.g., Cu(2+), Pb(2+), and Cd(2+), it is shown that the ionic equilibration with the medium may be the slower step and thus rate-limiting in their overall complexation with nanoparticles. PMID:22126743

  18. Efficient hydrogen evolution in transition metal dichalcogenides via a simple one-step hydrazine reaction.

    PubMed

    Cummins, Dustin R; Martinez, Ulises; Sherehiy, Andriy; Kappera, Rajesh; Martinez-Garcia, Alejandro; Schulze, Roland K; Jasinski, Jacek; Zhang, Jing; Gupta, Ram K; Lou, Jun; Chhowalla, Manish; Sumanasekera, Gamini; Mohite, Aditya D; Sunkara, Mahendra K; Gupta, Gautam

    2016-01-01

    Hydrogen evolution reaction is catalysed efficiently with precious metals, such as platinum; however, transition metal dichalcogenides have recently emerged as a promising class of materials for electrocatalysis, but these materials still have low activity and durability when compared with precious metals. Here we report a simple one-step scalable approach, where MoOx/MoS2 core-shell nanowires and molybdenum disulfide sheets are exposed to dilute aqueous hydrazine at room temperature, which results in marked improvement in electrocatalytic performance. The nanowires exhibit ∼100 mV improvement in overpotential following exposure to dilute hydrazine, while also showing a 10-fold increase in current density and a significant change in Tafel slope. In situ electrical, gate-dependent measurements and spectroscopic investigations reveal that hydrazine acts as an electron dopant in molybdenum disulfide, increasing its conductivity, while also reducing the MoOx core in the core-shell nanowires, which leads to improved electrocatalytic performance. PMID:27282871

  19. Efficient hydrogen evolution in transition metal dichalcogenides via a simple one-step hydrazine reaction

    NASA Astrophysics Data System (ADS)

    Cummins, Dustin R.; Martinez, Ulises; Sherehiy, Andriy; Kappera, Rajesh; Martinez-Garcia, Alejandro; Schulze, Roland K.; Jasinski, Jacek; Zhang, Jing; Gupta, Ram K.; Lou, Jun; Chhowalla, Manish; Sumanasekera, Gamini; Mohite, Aditya D.; Sunkara, Mahendra K.; Gupta, Gautam

    2016-06-01

    Hydrogen evolution reaction is catalysed efficiently with precious metals, such as platinum; however, transition metal dichalcogenides have recently emerged as a promising class of materials for electrocatalysis, but these materials still have low activity and durability when compared with precious metals. Here we report a simple one-step scalable approach, where MoOx/MoS2 core-shell nanowires and molybdenum disulfide sheets are exposed to dilute aqueous hydrazine at room temperature, which results in marked improvement in electrocatalytic performance. The nanowires exhibit ~100 mV improvement in overpotential following exposure to dilute hydrazine, while also showing a 10-fold increase in current density and a significant change in Tafel slope. In situ electrical, gate-dependent measurements and spectroscopic investigations reveal that hydrazine acts as an electron dopant in molybdenum disulfide, increasing its conductivity, while also reducing the MoOx core in the core-shell nanowires, which leads to improved electrocatalytic performance.

  20. Efficient hydrogen evolution in transition metal dichalcogenides via a simple one-step hydrazine reaction

    PubMed Central

    Cummins, Dustin R.; Martinez, Ulises; Sherehiy, Andriy; Kappera, Rajesh; Martinez-Garcia, Alejandro; Schulze, Roland K.; Jasinski, Jacek; Zhang, Jing; Gupta, Ram K.; Lou, Jun; Chhowalla, Manish; Sumanasekera, Gamini; Mohite, Aditya D.; Sunkara, Mahendra K.; Gupta, Gautam

    2016-01-01

    Hydrogen evolution reaction is catalysed efficiently with precious metals, such as platinum; however, transition metal dichalcogenides have recently emerged as a promising class of materials for electrocatalysis, but these materials still have low activity and durability when compared with precious metals. Here we report a simple one-step scalable approach, where MoOx/MoS2 core-shell nanowires and molybdenum disulfide sheets are exposed to dilute aqueous hydrazine at room temperature, which results in marked improvement in electrocatalytic performance. The nanowires exhibit ∼100 mV improvement in overpotential following exposure to dilute hydrazine, while also showing a 10-fold increase in current density and a significant change in Tafel slope. In situ electrical, gate-dependent measurements and spectroscopic investigations reveal that hydrazine acts as an electron dopant in molybdenum disulfide, increasing its conductivity, while also reducing the MoOx core in the core-shell nanowires, which leads to improved electrocatalytic performance. PMID:27282871

  1. Synthesis of colloidal uranium-dioxide nanocrystals.

    PubMed

    Wu, Huimeng; Yang, Yongan; Cao, Y Charles

    2006-12-27

    In this paper, we have developed an organic-phase synthesis method for producing size-controlled, nearly monodispersed, colloidal uranium-dioxide nanocrystals. These UO2 nanocrystals are potentially important to applications such as nuclear fuel materials, catalysts, and thermopower materials. In addition, we have systematically mapped out the functions of the solvents (oleic acid, oleylamine, and 1-octadecene) in the synthesis, and we found that N-(cis-9-octadecenyl)oleamide-a product of the condensation of oleic acid and oleylamine-can substantially affect the formation of UO2 nanocrystals. Importantly, these results provide fundamental insight into the mechanisms of UO2 nanocrystal synthesis. Moreover, because a mixture of oleic acid and oleylamine has been widely used in synthesizing a variety of high-quality metal or metal-oxide nanocrystals, the results herein should also be important for understanding the detailed mechanisms of these syntheses. PMID:17177400

  2. Doped semiconductor nanocrystal junctions

    NASA Astrophysics Data System (ADS)

    Borowik, Ł.; Nguyen-Tran, T.; Roca i Cabarrocas, P.; Mélin, T.

    2013-11-01

    Semiconductor junctions are the basis of electronic and photovoltaic devices. Here, we investigate junctions formed from highly doped (ND≈1020-1021cm-3) silicon nanocrystals (NCs) in the 2-50 nm size range, using Kelvin probe force microscopy experiments with single charge sensitivity. We show that the charge transfer from doped NCs towards a two-dimensional layer experimentally follows a simple phenomenological law, corresponding to formation of an interface dipole linearly increasing with the NC diameter. This feature leads to analytically predictable junction properties down to quantum size regimes: NC depletion width independent of the NC size and varying as ND-1/3, and depleted charge linearly increasing with the NC diameter and varying as ND1/3. We thus establish a "nanocrystal counterpart" of conventional semiconductor planar junctions, here however valid in regimes of strong electrostatic and quantum confinements.

  3. New metal phthalocyanines/metal simple hydroxide multilayers: experimental evidence of dipolar field-driven magnetic behavior.

    PubMed

    Bourzami, Riadh; Eyele-Mezui, Séraphin; Delahaye, Emilie; Drillon, Marc; Rabu, Pierre; Parizel, Nathalie; Choua, Sylvie; Turek, Philippe; Rogez, Guillaume

    2014-01-21

    A series of new hybrid multilayers has been synthesized by insertion-grafting of transition metal (Cu(II), Co(II), Ni(II), and Zn(II)) tetrasulfonato phthalocyanines between layers of Cu(II) and Co(II) simple hydroxides. The structural and spectroscopic investigations confirm the formation of new layered hybrid materials in which the phthalocyanines act as pillars between the inorganic layers. The magnetic investigations show that all copper hydroxide-based compounds behave similarly, presenting an overall antiferromagnetic behavior with no ordering down to 1.8 K. On the contrary, the cobalt hydroxide-based compounds present a ferrimagnetic ordering around 6 K, regardless of the nature of the metal phthalocyanine between the inorganic layers. The latter observation points to strictly dipolar interactions between the inorganic layers. The amplitude of the dipolar field has been evaluated from X-band and Q-band EPR spectroscopy investigation (Bdipolar ≈ 30 mT). PMID:24400974

  4. Simple metal under tensile stress: layer-dependent herringbone reconstruction of thin potassium films on graphite

    NASA Astrophysics Data System (ADS)

    Yin, Feng; Kulju, Sampo; Koskinen, Pekka; Akola, Jaakko; Palmer, Richard E.

    2015-05-01

    While understanding the properties of materials under stress is fundamentally important, designing experiments to probe the effects of large tensile stress is difficult. Here tensile stress is created in thin films of potassium (up to 4 atomic layers) by epitaxial growth on a rigid support, graphite. We find that this “simple” metal shows a long-range, periodic “herringbone” reconstruction, observed in 2- and 3- (but not 1- and 4-) layer films by low-temperature scanning tunneling microscopy (STM). Such a pattern has never been observed in a simple metal. Density functional theory (DFT)simulations indicate that the reconstruction consists of self-aligned stripes of enhanced atom density formed to relieve the tensile strain. At the same time marked layer-dependent charging effects lead to substantial variation in the apparent STM layer heights.

  5. Zinc oxide formation in galvanized metallic wire by simple selective growth method

    NASA Astrophysics Data System (ADS)

    Sivanantham, A.; Abinaya, C.; Vishnukanthan, V.; Jayabal, P.; Boobalan, K.; Mohanraj, S.; Mayandi, J.

    2015-06-01

    ZnO nanostructures were synthesized by a simple method of oxidizing metallic wire by direct electrical heating. A galvanized iron wire was used as the source of zinc. Several optical techniques were employed on the synthesized ZnO nanostructure such as photoluminescence, Raman and FTIR spectroscopy. The formation of ZnO nanostructures was confirmed from the spectra of different optical studies and also determined by XRD. SEM analysis shows the signature of nanorod formation on the surface of the wire. The oxidation state and ferromagnetic property of these oxidized metallic wires were discussed with the help of EPR spectrum. In summation to the properties studied, a growth mechanism was suggested based on the observations and method of the oxidation procedure.

  6. Simple metal under tensile stress: layer-dependent herringbone reconstruction of thin potassium films on graphite

    PubMed Central

    Yin, Feng; Kulju, Sampo; Koskinen, Pekka; Akola, Jaakko; Palmer, Richard E.

    2015-01-01

    While understanding the properties of materials under stress is fundamentally important, designing experiments to probe the effects of large tensile stress is difficult. Here tensile stress is created in thin films of potassium (up to 4 atomic layers) by epitaxial growth on a rigid support, graphite. We find that this “simple” metal shows a long-range, periodic “herringbone” reconstruction, observed in 2- and 3- (but not 1- and 4-) layer films by low-temperature scanning tunneling microscopy (STM). Such a pattern has never been observed in a simple metal. Density functional theory (DFT)simulations indicate that the reconstruction consists of self-aligned stripes of enhanced atom density formed to relieve the tensile strain. At the same time marked layer-dependent charging effects lead to substantial variation in the apparent STM layer heights. PMID:25959681

  7. Building thiol and metal-thiolate functions into coordination nets: Clues from a simple molecule

    NASA Astrophysics Data System (ADS)

    He, Jun; Yang, Chen; Xu, Zhengtao; Zeller, Matthias; Hunter, Allen D.; Lin, Jianhua

    2009-07-01

    The simple and easy-to-prepare bifunctional molecule 2,5-dimercapto-1,4-benzenedicarboxylic acid (H 4DMBD) interacts with the increasingly harder metal ions of Cu +, Pb 2+ and Eu 3+ to form the coordination networks of Cu 6(DMBD) 3(en) 4(Hen) 6 ( 1), Pb 2(DMBD)(en) 2 ( 2) and Eu 2(H 2DMBD) 3(DEF) 4 ( 3), where the carboxyl and thiol groups bind with distinct preference to the hard and soft metal ions, respectively. Notably, 1 features uncoordinated carboxylate groups and Cu 3 cluster units integrated via the thiolate groups into an extended network with significant interaction between the metal centers and the organic molecules; 2 features a 2D coordination net based on the mercapto and carboxylic groups all bonded to the Pb 2+ ions; 3 features free-standing thiol groups inside the channels of a metal-carboxylate-based network. This study illustrates the rich solid state structural features and potential functions offered by the carboxyl-thiol combination.

  8. 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

  9. A simple practical protocol for care of metal-skin interface of external fixation.

    PubMed

    Saw, A; Chan, C K; Penafort, R; Sengupta, S

    2006-02-01

    Patients treated with external fixation for limb reconsturciton or fracture stabilization equire regular and prolongedperiod of pin-tract care involving frequent visits to clinic and dressing traditionally carried out by trained nurses or medical assistants. A simple method of do-it-yourself dressing was introduced in our institution and this study was undertaken to evaluate the effectiveness of the protocol. Sixty patients (40 trauma-related problems and 20 congenital or developmental disorders) were enrolled into the study. Following application of external fixation, the patients and/or their caretakers were taught on how to do pin-site dressing using normal saline or drinking water as cleansing solution on daily basis. Patients were discharged on the second or third post-operative day and were followed-up every two weeks for an average 182 days (range 66 to 379 days) with special attention on identifying pin-tract infection. A simple grading system for pin-tract infections was proposed. Of 40 patients with trauma-related problems. 65% were post-traumatic infections. There were 788 metal-skin interfaces (239 half-pin fixations and 549 tensioned wire fixations. A total 143 metal-skin interface infections (18.1%) involving half-pin sites (41.3%) and tensioned wire sites (58.7%) was noted. Majority were grade I infections (79.7%), 18.8% grade II and only 1.4% grade III. Most infections (81%)were caused by Staphylococcus aureus. Grade I infections were successfully treated with frequent dressing, grade II by adjunctive oral antibiotic but grade III infections required removal of fixator. All eventually healed. Do yourself non-sterile dressing of metal-skin interfaces is a cost-effective method of pin-site care with a low infection rate. The infections were sucessfully treated using guidelines according to the proposed classification of pin-tract infections. PMID:17042233

  10. How simple is too simple? Computational perspective on importance of second-shell environment for metal-ion selectivity.

    PubMed

    Gutten, Ondrej; Rulíšek, Lubomír

    2015-06-14

    The metal-ion selectivity in biomolecules represents one of the most important phenomena in bioinorganic chemistry. The open question to what extent is the selectivity in the complex bioinorganic structures such as metallopeptides determined by the first-shell ligands of the metal ion is answered herein using six model peptides complexed with the set of divalent metal ions (Mn(2+), Fe(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), and Hg(2+)) and their various first-shell representations. By calculating the differences among the free energies of complexation of metal ions in these peptides and their model (truncated) systems it is quantitatively shown that the definition of the first shell is paramount to this discussion and revolves around the chemical nature of the binding site. Despite the vast conceivable diversity of peptidic structures, that suggest certain fluidity of this definition, major contributing factors are identified and assessed based on their importance for capturing metal-ion selectivity. These factors include soft/hard character of ligands and various non-covalent interactions in the vicinity of the binding site. The relative importance of these factors is considered and specific suggestions for effective construction of the models are made. The relationship of first-shell models and their corresponding parent peptides is discussed thoroughly, both with respect to their chemical similarity and potential disparity introduced by generally "non-alignable" conformational flexibility of the two systems. It is concluded that, in special cases, this disparity can be negligible and that heeding the chemical factors contributing to selectivity during construction of the model can successfully result in models that retain the affinity profile for various metal ions with high fidelity. PMID:25785686

  11. Efficient removal of heavy metal ions from aqueous systems with the assembly of anisotropic layered double hydroxide nanocrystals@carbon nanosphere.

    PubMed

    Gong, Jingming; Liu, Ting; Wang, Xiaoqing; Hu, Xianluo; Zhang, Lizhi

    2011-07-15

    We report on the efficient removal of heavy metal ions from simulated wastewater with a nanostructured assembly. The nanoassembly was obtained via direct assembling the performed anisotropic layered double hydroxide nanocrystals (LDH-NCs) onto the surface of carbon nanospheres (labeled as LDH-NCs@CNs). It was found that the maximum adsorption capacity of the nanoassembly toward Cu(2+) was ∼ 19.93 mg g(-1) when the initial Cu(2+) concentration was 10.0 mg L(-1), displaying a high efficiency for the removal of heavy metal ions. The Freundlich adsorption isotherm was applicable to describe the removal processes. Kinetics of the Cu(2+) removal was found to follow pseudo-second-order rate equation. Furthermore, the as-prepared building unit of the assembly, including LDH-NCs, CNs, and the assembly, as well as Cu(2+)-adsorbed assembly, were carefully examined by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), nitrogen sorption measurements, and X-ray photoelectron spectroscopy (XPS). Based on the characterization results, a possible mechanism of Cu(2+) removal with the assembly of LDH-NCs@CNs was proposed. Comparison experiments show that the adsorption capacity of the resulting LDH-NCs@CNs assembly was much higher than its any building unit alone (CNs or LDH-NCs), exhibiting the deliberation of the assembly on water decontamination. This work provides a very efficient, fast and convenient approach for exploring promising nanoassembly materials for water treatment. PMID:21692502

  12. Enhanced photophysical properties of plasmonic magnetic metal-alloyed semiconductor heterostructure nanocrystals: a case study for the Ag@Ni/Zn1-xMgxO system.

    PubMed

    Paul, Sumana; Ghosh, Sirshendu; Saha, Manas; De, S K

    2016-05-14

    Understanding the effect of homovalent cation alloying in wide band gap ZnO and the formation of metal-semiconductor heterostructures is very important for maximisation of the photophysical properties of ZnO. Nearly monodisperse ZnO nanopyramid and Mg alloyed ZnO nanostructures have been successfully synthesized by one pot decomposition of metal stearate by using oleylamine both as activating and capping agent. The solid solubility of Mg(ii) ions in ZnO is limited to ∼30% without phase segregation. An interesting morphology change is found on increasing Mg alloying: from nanopyramids to self-assembled nanoflowers. The morphology change is explained by the oriented attachment process. The introduction of Mg into the ZnO matrix increases the band gap of the materials and also generates new zinc interstitial (Zni) and oxygen vacancy related defects. Plasmonic magnetic Ag@Ni core-shell (Ag as core and Ni as shell) nanocrystals are used as a seed material to synthesize Ag@Ni/Zn1-xMgxO complex heterostructures. Epitaxial growth is established between Ag(111) and ZnO(110) planes in the heterostructure. An epitaxial metal-semiconductor interface is very crucial for complete electron-hole (e-h) separation and enhancement of the exciton lifetime. The alloyed semiconductor-metal heterostructure is observed to be highly photocatalytically active for dye degradation as well as photodetection. Incorporation of magnetic Ni(0) makes the photocatalyst superparamagnetic at room temperature which is found to be helpful for catalyst regeneration. PMID:27113320

  13. Patterning nanocrystals using DNA

    SciTech Connect

    Williams, Shara Carol

    2003-09-01

    One of the goals of nanotechnology is to enable programmed self-assembly of patterns made of various materials with nanometer-sized control. This dissertation describes the results of experiments templating arrangements of gold and semiconductor nanocrystals using 2'-deoxyribonucleic acid (DNA). Previously, simple DNA-templated linear arrangements of two and three nanocrystals structures have been made.[1] Here, we have sought to assemble larger and more complex nanostructures. Gold-DNA conjugates with 50 to 100 bases self-assembled into planned arrangements using strands of DNA containing complementary base sequences. We used two methods to increase the complexity of the arrangements: using branched synthetic doublers within the DNA covalent backbone to create discrete nanocrystal groupings, and incorporating the nanocrystals into a previously developed DNA lattice structure [2][3] that self-assembles from tiles made of DNA double-crossover molecules to create ordered nanoparticle arrays. In the first project, the introduction of a covalently-branched synthetic doubler reagent into the backbone of DNA strands created a branched DNA ''trimer.'' This DNA trimer templated various structures that contained groupings of three and four gold nanoparticles, giving promising, but inconclusive transmission electron microscopy (TEM) results. Due to the presence of a variety of possible structures in the reaction mixtures, and due to the difficulty of isolating the desired structures, the TEM and gel electrophoresis results for larger structures having four particles, and for structures containing both 5 and 10 nm gold nanoparticles were inconclusive. Better results may come from using optical detection methods, or from improved sample preparation. In the second project, we worked toward making two-dimensional ordered arrays of nanocrystals. We replicated and improved upon previous results for making DNA lattices, increasing the size of the lattices to a length greater than

  14. Simple accurate approximations for the optical properties of metallic nanospheres and nanoshells.

    PubMed

    Schebarchov, Dmitri; Auguié, Baptiste; Le Ru, Eric C

    2013-03-28

    This work aims to provide simple and accurate closed-form approximations to predict the scattering and absorption spectra of metallic nanospheres and nanoshells supporting localised surface plasmon resonances. Particular attention is given to the validity and accuracy of these expressions in the range of nanoparticle sizes relevant to plasmonics, typically limited to around 100 nm in diameter. Using recent results on the rigorous radiative correction of electrostatic solutions, we propose a new set of long-wavelength polarizability approximations for both nanospheres and nanoshells. The improvement offered by these expressions is demonstrated with direct comparisons to other approximations previously obtained in the literature, and their absolute accuracy is tested against the exact Mie theory. PMID:23358525

  15. Structural expansions for the ground state energy of a simple metal

    NASA Technical Reports Server (NTRS)

    Hammerberg, J.; Ashcroft, N. W.

    1973-01-01

    A structural expansion for the static ground state energy of a simple metal is derived. An approach based on single particle band structure which treats the electron gas as a non-linear dielectric is presented, along with a more general many particle analysis using finite temperature perturbation theory. The two methods are compared, and it is shown in detail how band-structure effects, Fermi surface distortions, and chemical potential shifts affect the total energy. These are of special interest in corrections to the total energy beyond third order in the electron ion interaction, and hence to systems where differences in energies for various crystal structures are exceptionally small. Preliminary calculations using these methods for the zero temperature thermodynamic functions of atomic hydrogen are reported.

  16. A simple scheme to determine potential aquatic metal toxicity from mining wastes

    USGS Publications Warehouse

    Wildeman, T.R.; Smith, K.S.; Ranville, J.F.

    2007-01-01

    A decision tree (mining waste decision tree) that uses simple physical and chemical tests has been developed to determine whether effluent from mine waste material poses a potential toxicity threat to the aquatic environment. For the chemical portion of the tree, leaching tests developed by the United States Geological Survey, the Colorado Division of Minerals and Geology (Denver, CO), and a modified 1311 toxicity characteristic leaching procedure (TCLP) test of the United States Environmental Protection Agency have been extensively used as a surrogate for readily available metals that can be released into the environment from mining wastes. To assist in the assessment, element concentration pattern graphs (ECPG) are produced that compare concentrations of selected groups of elements from the three leachates and any water associated with the mining waste. The MWDT makes a distinction between leachates or waters with pH less than or greater than 5. Generally, when the pH values are below 5, the ECPG of the solutions are quite similar, and potential aquatic toxicity from cationic metals, such as Pb, Cu, Zn, Cd, and Al, is assumed. Below pH 5, these metals are mostly dissolved, generally are not complexed with organic or inorganic ligands, and hence are more bioavailable. Furthermore, there is virtually no carbonate alkalinity at pH less than 5. All of these factors promote metal toxicity to aquatic organisms. On the other hand, when the pH value of the water or the leachates is above 5, the ECPG from the solutions are variable, and inferred aquatic toxicity depends on factors in addition to the metals released from the leaching tests. Hence, leachates and waters with pH above 5 warrant further examination of their chemical composition. Physical ranking criteria provide additional information, particularly in areas where waste piles exhibit similar chemical rankings. Rankings from physical and chemical criteria generally are not correlated. Examples of how this

  17. Simple preparation of aminothiourea-modified chitosan as corrosion inhibitor and heavy metal ion adsorbent.

    PubMed

    Li, Manlin; Xu, Juan; Li, Ronghua; Wang, Dongen; Li, Tianbao; Yuan, Maosen; Wang, Jinyi

    2014-03-01

    By a simple and convenient method of using formaldehyde as linkages, two new chitosan (CS) derivatives modified respectively with thiosemicarbazide (TSFCS) and thiocarbohydrazide (TCFCS) were synthesized. The new compounds were characterized and studied by Fourier transform infrared spectroscopy, elemental analysis, thermal gravity analysis and differential scanning calorimetry, and their surface morphologies were determined via scanning electron microscopy. These CS derivatives could form pH dependent gels. The behavior of 304 steel in 2% acetic acid containing different inhibitors or different concentrations of inhibitor had been studied by potentiodynamic polarization test. The preliminary results show that the new compound TCFCS can act as a mixed-type metal anticorrosion inhibitor in some extent; its inhibition efficiency is 92% when the concentration was 60 mg/L. The adsorption studies on a metal ion mixture aqueous solution show that two samples TSFCS and TCFCS can absorb As (V), Ni (II), Cu (II), Cd (II) and Pb (II) efficiently at pH 9 and 4. PMID:24407668

  18. Silver(I)-directed growth of metal-organic complex nanocrystals with bidentate ligands of hydroquinine anthraquinone-1,4-diyl diethers as linkers at the water-chloroform interface

    PubMed Central

    2014-01-01

    Immiscible liquid-liquid interfaces provide unique double phase regions for the design and construction of nanoscale materials. Here, we reported Ag(I)-directed growth of metal-organic complex nanocrystals by using AgNO3 as a connector in the aqueous solution and bidentate ligand of 1,4-bis(9-O-dihydroquininyl)anthraquinone [(DHQ)2AQN] and its enantiomer of (DHQD)2AQN in the chloroform solutions as linkers. The Ag-(DHQ)2AQN and Ag-(DHQD)2AQN complex nanocrystals were formed at the liquid-liquid interfaces and characterized by using UV-vis absorption and fluorescence spectroscopy and X-ray photoelectron spectroscopy, as well as by using scanning electron microscopy. Screw-like nanocrystals were formed at the initial 30 min after the interfacial coordination reaction started, then they grew into nanorods after several days, and finally became cubic microcrystals after 2 weeks. The pure ligand showed two emission bands centered at about 363 and 522 nm in the methanol solution, the second one of which was quenched and shifted to about 470 nm in the Ag-complex nanocrystals. Two couples of reversible redox waves were recorded for the Ag-complex nanocrystals; one centered at about -0.25 V (vs. Ag/AgCl) was designated to one electron transfer process of Ag - (DHQ)2AQN and Ag - (DHQ)2AQN+, and the other one centered at about 0.2 V was designated to one electron transfer process of Ag - (DHQ)2AQN and Ag+ - (DHQ)2AQN. PMID:25246874

  19. Building robust architectures of carbon and metal oxide nanocrystals toward high-performance anodes for lithium-ion batteries.

    PubMed

    Jia, Xilai; Chen, Zheng; Cui, Xia; Peng, Yiting; Wang, Xiaolei; Wang, Ge; Wei, Fei; Lu, Yunfeng

    2012-11-27

    Design and fabrication of effective electrode structure is essential but is still a challenge for current lithium-ion battery technology. Herein we report the design and fabrication of a class of high-performance robust nanocomposites based on iron oxide spheres and carbon nanotubes (CNTs). An efficient aerosol spray process combined with vacuum filtration was used to synthesize such composite architecture, where oxide nanocrystals were assembled into a continuous carbon skeleton and entangled in porous CNT networks. This material architecture offers many critical features that are required for high-performance anodes, including efficient ion transport, high conductivity, and structure durability, therefore enabling an electrode with outstanding lithium storage performance. For example, such an electrode with a thickness of ∼35 μm could deliver a specific capacity of 994 mA h g(-1) (based on total electrode weight) and high recharging rates. This effective strategy can be extended to construct many other composite electrodes for high-performance lithium-ion batteries. PMID:23046380

  20. General synthesis of noble metal (Au, Ag, Pd, Pt) nanocrystal modified MoS2 nanosheets and the enhanced catalytic activity of Pd-MoS2 for methanol oxidation

    NASA Astrophysics Data System (ADS)

    Yuwen, Lihui; Xu, Fei; Xue, Bing; Luo, Zhimin; Zhang, Qi; Bao, Biqing; Su, Shao; Weng, Lixing; Huang, Wei; Wang, Lianhui

    2014-05-01

    A general and facile method for water-dispersed noble metal (Au, Ag, Pd, Pt) nanocrystal modified MoS2 nanosheets (NM-MoS2 NSs) has been developed. By using sodium carboxymethyl cellulose as a stabilizer, well-dispersed NM-MoS2 NSs with homogeneously deposited noble metal nanocrystals (NM NCs) can be synthesized in aqueous solutions. Due to the transition from the semiconducting 2H phase to the metallic 1T phase, the chemically exfoliated MoS2 (ce-MoS2) NSs have improved electrochemical activity. The partially metallic nature of the ce-MoS2 NSs and the catalytic activity of the NM NCs synergistically make NM-MoS2 NSs a potential electrochemical catalyst. For the first time, Pd-MoS2 NSs were used as an electrocatalyst for methanol oxidation in alkaline media. The results showed that Pd-MoS2 NSs have enhanced catalytic activity with 2.8-fold anodic peak current mass density compared to a commercial Pd/C catalyst, suggesting potential for application in direct methanol fuel cells (DMFCs).A general and facile method for water-dispersed noble metal (Au, Ag, Pd, Pt) nanocrystal modified MoS2 nanosheets (NM-MoS2 NSs) has been developed. By using sodium carboxymethyl cellulose as a stabilizer, well-dispersed NM-MoS2 NSs with homogeneously deposited noble metal nanocrystals (NM NCs) can be synthesized in aqueous solutions. Due to the transition from the semiconducting 2H phase to the metallic 1T phase, the chemically exfoliated MoS2 (ce-MoS2) NSs have improved electrochemical activity. The partially metallic nature of the ce-MoS2 NSs and the catalytic activity of the NM NCs synergistically make NM-MoS2 NSs a potential electrochemical catalyst. For the first time, Pd-MoS2 NSs were used as an electrocatalyst for methanol oxidation in alkaline media. The results showed that Pd-MoS2 NSs have enhanced catalytic activity with 2.8-fold anodic peak current mass density compared to a commercial Pd/C catalyst, suggesting potential for application in direct methanol fuel cells (DMFCs

  1. Determination of active doping in highly resistive boron doped silicon nanocrystals embedded in SiO2 by capacitance voltage measurement on inverted metal oxide semiconductor structure

    NASA Astrophysics Data System (ADS)

    Zhang, Tian; Puthen-Veettil, Binesh; Wu, Lingfeng; Jia, Xuguang; Lin, Ziyun; Yang, Terry Chien-Jen; Conibeer, Gavin; Perez-Wurfl, Ivan

    2015-10-01

    We investigate the Capacitance-Voltage (CV) measurement to study the electrically active boron doping in Si nanocrystals (ncSi) embedded in SiO2. The ncSi thin films with high resistivity (200-400 Ω cm) can be measured by using an inverted metal oxide semiconductor (MOS) structure (Al/ncSi (B)/SiO2/Si). This device structure eliminates the complications from the effects of lateral current flow and the high sheet resistance in standard lateral MOS structures. The characteristic MOS CV curves observed are consistent with the effective p-type doping. The CV modeling method is presented and used to evaluate the electrically active doping concentration. We find that the highly boron doped ncSi films have electrically active doping of 1018-1019 cm-3 despite their high resistivity. The saturation of doping at about 1.4 × 1019 cm-3 and the low doping efficiency less than 5% are observed and discussed. The calculated effective mobility is in the order of 10-3 cm2/V s, indicating strong impurity/defect scattering effect that hinders carriers transport.

  2. One-pot synthesis of CdS nanocrystals hybridized with single-layer transition-metal dichalcogenide nanosheets for efficient photocatalytic hydrogen evolution.

    PubMed

    Chen, Junze; Wu, Xue-Jun; Yin, Lisha; Li, Bing; Hong, Xun; Fan, Zhanxi; Chen, Bo; Xue, Can; Zhang, Hua

    2015-01-19

    Exploration of low-cost and earth-abundant photocatalysts for highly efficient solar photocatalytic water splitting is of great importance. Although transition-metal dichalcogenides (TMDs) showed outstanding performance as co-catalysts for the hydrogen evolution reaction (HER), designing TMD-hybridized photocatalysts with abundant active sites for the HER still remains challenge. Here, a facile one-pot wet-chemical method is developed to prepare MS2-CdS (M=W or Mo) nanohybrids. Surprisedly, in the obtained nanohybrids, single-layer MS2 nanosheets with lateral size of 4-10 nm selectively grow on the Cd-rich (0001) surface of wurtzite CdS nanocrystals. These MS2-CdS nanohybrids possess a large number of edge sites in the MS2 layers, which are active sites for the HER. The photocatalytic performances of WS2-CdS and MoS2-CdS nanohybrids towards the HER under visible light irradiation (>420 nm) are about 16 and 12 times that of pure CdS, respectively. Importantly, the MS2-CdS nanohybrids showed enhanced stability after a long-time test (16 h), and 70% of catalytic activity still remained. PMID:25470356

  3. Growth and characterization of well-aligned densely-packed rutile TiO(2) nanocrystals on sapphire substrates via metal-organic chemical vapor deposition.

    PubMed

    Chen, C A; Chen, Y M; Korotcov, A; Huang, Y S; Tsai, D S; Tiong, K K

    2008-02-20

    Well-aligned densely-packed rutile TiO(2) nanocrystals (NCs) have been grown on sapphire (SA) (100) and (012) substrates via metal-organic chemical vapor deposition (MOCVD), using titanium-tetraisopropoxide (TTIP, Ti(OC(3)H(7))(4)) as a source reagent. The surface morphology as well as structural and spectroscopic properties of the as-deposited NCs were characterized using field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), selected-area electron diffractometry (SAED), x-ray diffraction (XRD) and micro-Raman spectroscopy. FESEM micrographs reveal that vertically aligned NCs were grown on SA(100), whereas the NCs on the SA(012) were grown with a tilt angle of ∼33° from the normal to substrates. TEM and SAED measurements showed that the TiO(2) NCs on SA(100) with square cross section have their long axis directed along the [001] direction. The XRD results reveal TiO(2) NCs with either (002) orientation on SA(100) substrate or (101) orientation on SA(012) substrate. A strong substrate effect on the alignment of the growth of TiO(2) NCs has been demonstrated and the probable mechanism for the formation of these NCs has been discussed. PMID:21817648

  4. Growth and characterization of well-aligned densely-packed rutile TiO2 nanocrystals on sapphire substrates via metal organic chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Chen, C. A.; Chen, Y. M.; Korotcov, A.; Huang, Y. S.; Tsai, D. S.; Tiong, K. K.

    2008-02-01

    Well-aligned densely-packed rutile TiO2 nanocrystals (NCs) have been grown on sapphire (SA) (100) and (012) substrates via metal-organic chemical vapor deposition (MOCVD), using titanium-tetraisopropoxide (TTIP, Ti(OC3H7)4) as a source reagent. The surface morphology as well as structural and spectroscopic properties of the as-deposited NCs were characterized using field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), selected-area electron diffractometry (SAED), x-ray diffraction (XRD) and micro-Raman spectroscopy. FESEM micrographs reveal that vertically aligned NCs were grown on SA(100), whereas the NCs on the SA(012) were grown with a tilt angle of ~33° from the normal to substrates. TEM and SAED measurements showed that the TiO2 NCs on SA(100) with square cross section have their long axis directed along the [001] direction. The XRD results reveal TiO2 NCs with either (002) orientation on SA(100) substrate or (101) orientation on SA(012) substrate. A strong substrate effect on the alignment of the growth of TiO2 NCs has been demonstrated and the probable mechanism for the formation of these NCs has been discussed.

  5. Determination of active doping in highly resistive boron doped silicon nanocrystals embedded in SiO{sub 2} by capacitance voltage measurement on inverted metal oxide semiconductor structure

    SciTech Connect

    Zhang, Tian Puthen-Veettil, Binesh; Wu, Lingfeng; Jia, Xuguang; Lin, Ziyun; Yang, Terry Chien-Jen; Conibeer, Gavin; Perez-Wurfl, Ivan

    2015-10-21

    We investigate the Capacitance-Voltage (CV) measurement to study the electrically active boron doping in Si nanocrystals (ncSi) embedded in SiO{sub 2}. The ncSi thin films with high resistivity (200–400 Ω cm) can be measured by using an inverted metal oxide semiconductor (MOS) structure (Al/ncSi (B)/SiO{sub 2}/Si). This device structure eliminates the complications from the effects of lateral current flow and the high sheet resistance in standard lateral MOS structures. The characteristic MOS CV curves observed are consistent with the effective p-type doping. The CV modeling method is presented and used to evaluate the electrically active doping concentration. We find that the highly boron doped ncSi films have electrically active doping of 10{sup 18}–10{sup 19 }cm{sup −3} despite their high resistivity. The saturation of doping at about 1.4 × 10{sup 19 }cm{sup −3} and the low doping efficiency less than 5% are observed and discussed. The calculated effective mobility is in the order of 10{sup −3} cm{sup 2}/V s, indicating strong impurity/defect scattering effect that hinders carriers transport.

  6. Formation of a new archetypal Metal-Organic Framework from a simple monatomic liquid

    NASA Astrophysics Data System (ADS)

    Metere, Alfredo; Oleynikov, Peter; Dzugutov, Mikhail; O'Keeffe, Michael

    2014-12-01

    We report a molecular-dynamics simulation of a single-component system of particles interacting via a spherically symmetric potential that is found to form, upon cooling from a liquid state, a low-density porous crystalline phase. Its structure analysis demonstrates that the crystal can be described by a net with a topology that belongs to the class of topologies characteristic of the Metal-Organic Frameworks (MOFs). The observed net is new, and it is now included in the Reticular Chemistry Structure Resource database. The observation that a net topology characteristic of MOF crystals, which are known to be formed by a coordination-driven self-assembly process, can be reproduced by a thermodynamically stable configuration of a simple single-component system of particles opens a possibility of using these models in studies of MOF nets. It also indicates that structures with MOF topology, as well as other low-density porous crystalline structures can possibly be produced in colloidal systems of spherical particles, with an appropriate tuning of interparticle interaction.

  7. Formation of a new archetypal Metal-Organic Framework from a simple monatomic liquid

    SciTech Connect

    Metere, Alfredo Oleynikov, Peter; Dzugutov, Mikhail; O’Keeffe, Michael

    2014-12-21

    We report a molecular-dynamics simulation of a single-component system of particles interacting via a spherically symmetric potential that is found to form, upon cooling from a liquid state, a low-density porous crystalline phase. Its structure analysis demonstrates that the crystal can be described by a net with a topology that belongs to the class of topologies characteristic of the Metal-Organic Frameworks (MOFs). The observed net is new, and it is now included in the Reticular Chemistry Structure Resource database. The observation that a net topology characteristic of MOF crystals, which are known to be formed by a coordination-driven self-assembly process, can be reproduced by a thermodynamically stable configuration of a simple single-component system of particles opens a possibility of using these models in studies of MOF nets. It also indicates that structures with MOF topology, as well as other low-density porous crystalline structures can possibly be produced in colloidal systems of spherical particles, with an appropriate tuning of interparticle interaction.

  8. Trends in the properties and structures of the simple metals from a universal local pseudopotential

    NASA Astrophysics Data System (ADS)

    Nogueira, Fernando; Fiolhais, Carlos; Perdew, John P.

    1999-01-01

    The properties of simple metals are fixed primarily by the equilibrium average valence-electron density parameter rs, and secondarily by the valence z. The simplest level of theory that can account quantitatively for these trends invokes a ``universal'' local electron-ion pseudopotential, defined for each pair (rs,z) and treated as a second-order perturbation. We construct this pseudopotential from two conditions: (1) The total energy should minimize at the equilibrium Wigner-Seitz radius z1/3rs. (2) The bulk modulus should equal the realistic rs-dependent prediction of the stabilized jellium model with effective valence z*=1. These conditions can be satisfied by an analytic local pseudopotential depending upon two parameters other than z; we show that the choice of the two-parameter form (evanescent core vs Heine-Abarenkov) is not important. Our universal local pseudopotential is applied to calculate realistic bulk binding energies, pressure derivatives of bulk moduli, Voigt shear moduli, and interstitial electron numbers, revealing their trends as functions of rs and z. Equilibrium crystal structures are mapped in the rs-z plane, where the Hume-Rothery rules for substitutional alloys are manifest. The effect of pressure on crystal structure is also examined.

  9. Doped semiconductor nanocrystal junctions

    SciTech Connect

    Borowik, Ł.; Mélin, T.; Nguyen-Tran, T.; Roca i Cabarrocas, P.

    2013-11-28

    Semiconductor junctions are the basis of electronic and photovoltaic devices. Here, we investigate junctions formed from highly doped (N{sub D}≈10{sup 20}−10{sup 21}cm{sup −3}) silicon nanocrystals (NCs) in the 2–50 nm size range, using Kelvin probe force microscopy experiments with single charge sensitivity. We show that the charge transfer from doped NCs towards a two-dimensional layer experimentally follows a simple phenomenological law, corresponding to formation of an interface dipole linearly increasing with the NC diameter. This feature leads to analytically predictable junction properties down to quantum size regimes: NC depletion width independent of the NC size and varying as N{sub D}{sup −1/3}, and depleted charge linearly increasing with the NC diameter and varying as N{sub D}{sup 1/3}. We thus establish a “nanocrystal counterpart” of conventional semiconductor planar junctions, here however valid in regimes of strong electrostatic and quantum confinements.

  10. Bright White Light Emission from Ultrasmall Cadmium Selenide Nanocrystals

    SciTech Connect

    Rosson, Teresa; Claiborne, Sarah; McBride, James; Stratton, Benjamin S; Rosenthal, Sandra

    2012-01-01

    A simple treatment method using formic acid has been found to increase the fluorescence quantum yield of ultrasmall white light-emitting CdSe nanocrystals from 8% to 45%. Brighter white-light emission occurs with other carboxylic acids as well, and the magnitude of the quantum yield enhancement is shown to be dependent on the alkyl chain length. Additionally, the nanocrystal luminescence remains enhanced relative to the untreated nanocrystals over several days. This brightened emission opens the possibility for even further quantum yield improvement and potential for use of these white-light nanocrystals in solid-state lighting applications.

  11. Growth of platinum nanocrystals

    SciTech Connect

    2009-01-01

    Movie showing the growth of platinum nanocrystals in a liquid cell observed in situ using the JEOL 3010 TEM at the National Center for Electron Microscopy. This is the first ever-real time movie showing nucleation and growth by monomer attachment or by smaller nanocrystals coalescing to form larger nanocrystals. All the nanocrystals end up being roughly the same shape and size. http://newscenter.lbl.gov/feature-stories/2009/08/04/growth-spurts/

  12. Infrared colloidal lead chalcogenide nanocrystals: synthesis, properties, and photovoltaic applications.

    PubMed

    Fu, Huiying; Tsang, Sai-Wing

    2012-04-01

    Simple solution phase, catalyst-free synthetic approaches that offer monodispersed, well passivated, and non-aggregated colloidal semiconductor nanocrystals have presented many research opportunities not only for fundamental science but also for technological applications. The ability to tune the electrical and optical properties of semiconductor nanocrystals by manipulating the size and shape of the crystals during the colloidal synthesis provides potential benefits to a variety of applications including photovoltaic devices, light-emitting diodes, field effect transistors, biological imaging/labeling, and more. Recent advances in the synthesis and characterization of colloidal lead chalcogenide nanocrystals and the achievements in colloidal PbS or PbSe nanocrystals solar cells have demonstrated the promising application of infrared-emitting colloidal lead chalcogenide nanocrystals in photovoltaic devices. Here, we review recent progress in the synthesis and optical properties of colloidal lead chalcogenide nanocrystals. We focus in particular upon the size- and shape-controlled synthesis of PbS, PbSe, and PbTe nanocrystals by using different precursors and various stabilizing surfactants for the growth of the colloidal nanocrystals. We also summarize recent advancements in the field of colloidal nanocrystals solar cells based on colloidal PbS and PbSe nanocrystals. PMID:22382898

  13. Inorganic Chemistry Solutions to Semiconductor Nanocrystal Problems

    SciTech Connect

    Alvarado, Samuel R.; Guo, Yijun; Ruberu, T. Purnima A.; Tavasoli, Elham; Vela, Javier

    2014-03-15

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

  14. Influence of Nano-Crystal Metals on Texture and Biological Properties of Water Soluble Polysaccharides of Medicinal Plants

    NASA Astrophysics Data System (ADS)

    Churilov, G.; Ivanycheva, J.; Kiryshin, V.

    2015-11-01

    When treating the plants seeds with nano-materials there are some quality and quantity changes of polysaccharides, the molecular mass increase and monosaccharides change that leads to the increase of physiological and pharmacological activity of carbohydrates got from medicinal plants. We have got water soluble polysaccharides and nano-metals combinations containing 0.000165-0.000017 mg/dm3 of the metal. In a case of induced anemia the blood composition has practically restored on the 10th day of the treatment with nanocomposites. The use of pectin polysaccharides (that are attributed to modifiers of biological respond) to get nano-structured materials seems to be actual relative to their physiological activity (radio nuclides persorption, heavy metals ions, bacteria cells and their toxins; lipids metabolism normalization; bowels secreting and motor functions activation and modulation of the endocrine system.

  15. All-inorganic Germanium nanocrystal films by cationic ligand exchange

    DOE PAGESBeta

    Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.; Anderson, Nicholas C.; Beard, Matthew C.; Neale, Nathan R.

    2016-01-21

    In this study, we introduce a new paradigm for group IV nanocrystal surface chemistry based on room temperature surface activation that enables ionic ligand exchange. Germanium nanocrystals synthesized in a gas-phase plasma reactor are functionalized with labile, cationic alkylammonium ligands rather than with traditional covalently bound groups. We employ Fourier transform infrared and 1H nuclear magnetic resonance spectroscopies to demonstrate the alkylammonium ligands are freely exchanged on the germanium nanocrystal surface with a variety of cationic ligands, including short inorganic ligands such as ammonium and alkali metal cations. This ionic ligand exchange chemistry is used to demonstrate enhanced transport inmore » germanium nanocrystal films following ligand exchange as well as the first photovoltaic device based on an all-inorganic germanium nanocrystal absorber layer cast from solution. This new ligand chemistry should accelerate progress in utilizing germanium and other group IV nanocrystals for optoelectronic applications.« less

  16. All-Inorganic Germanium Nanocrystal Films by Cationic Ligand Exchange.

    PubMed

    Wheeler, Lance M; Nichols, Asa W; Chernomordik, Boris D; Anderson, Nicholas C; Beard, Matthew C; Neale, Nathan R

    2016-03-01

    We introduce a new paradigm for group IV nanocrystal surface chemistry based on room temperature surface activation that enables ionic ligand exchange. Germanium nanocrystals synthesized in a gas-phase plasma reactor are functionalized with labile, cationic alkylammonium ligands rather than with traditional covalently bound groups. We employ Fourier transform infrared and (1)H nuclear magnetic resonance spectroscopies to demonstrate the alkylammonium ligands are freely exchanged on the germanium nanocrystal surface with a variety of cationic ligands, including short inorganic ligands such as ammonium and alkali metal cations. This ionic ligand exchange chemistry is used to demonstrate enhanced transport in germanium nanocrystal films following ligand exchange as well as the first photovoltaic device based on an all-inorganic germanium nanocrystal absorber layer cast from solution. This new ligand chemistry should accelerate progress in utilizing germanium and other group IV nanocrystals for optoelectronic applications. PMID:26796765

  17. Synthesis and Characterization of Wurtzite Cu2ZnSnS4 Nanocrystals

    NASA Astrophysics Data System (ADS)

    Jao, Meng-Huan; Liao, Hsueh-Chung; Wu, Ming-Chung; Su, Wei-Fang

    2012-10-01

    Copper-zinc-tin-chalcogenide (CZTSSe) with earth abundant elements has attracted increasing attention due to large absorption coefficient and band gap of ˜1.5 eV which is near the optimum band gap of single-junction photovoltaic devices. In this study, we used commercially available precursors to produce wurtzite Cu2ZnSnS4 nanocrystals by simple solvothermal synthesis. Different from the typical kesterite or stannite phases of CZTS, the nanocrystals synthesized in this study are in wurtzite phase with hexagonal crystal cell. The n-dodecanethiol was used to control the reactivity of metal ions, leading to the controlled size of CZTS nanoparticle by simply varying the reaction time. Furthermore, the as synthesized CZTS nanocrystals have novel wurtzite crystal structure. As a result, a red shift of absorption band edge between the CZTS nanoparticles with different size was obtained. Our study provides an extending method of CZTS nanocrystal ink preparation awaiting for further photovoltaic device application.

  18. A simple route utilizing surfactant-assisted templating sol-gel process for synthesis of mesoporous Dy2O3 nanocrystal.

    PubMed

    Sreethawong, Thammanoon; Chavadej, Sumaeth; Ngamsinlapasathian, Supachai; Yoshikawa, Susumu

    2006-08-01

    A simple route of combined sol-gel process with surfactant-assisted templating technique was successfully employed for the first time to synthesize nanocrystalline mesoporous Dy(2)O(3) with narrow monomodal pore size distribution under mild conditions. The nanocrystalline Dy(2)O(3) with monomodal mesoporous characteristic was ultimately achieved by controlling the hydrolysis and condensation steps of dysprosium n-butoxide modified with acetylacetone in the presence of laurylamine hydrochloride surfactant aqueous solution. The synthesized material was methodically characterized by thermogravimetry and differential thermal analysis (TG-DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), selected-area electron diffraction (SAED), N(2) adsorption-desorption, Brunauer-Emmett-Teller (BET) surface area analysis, and Barrett-Joyner-Halenda (BJH) pore size distribution analysis. The particle size of the synthesized Dy(2)O(3) in nanosized range obtained from the SEM and HRTEM micrographs was in good accordance with the crystallite size estimated from the XRD result. The N(2) adsorption-desorption result exhibited hysteresis pattern with single loop, indicating the existence of monomodal mesopore. The extremely narrow pore size distribution with mean pore diameter in the mesopore region of the synthesized Dy(2)O(3) was also confirmed by the BJH result. PMID:16647076

  19. Micellization of pH-responsive Amphiphilic Diblock Copolymers in Aqueous Media and the Formation of Metal Nanocrystals

    NASA Astrophysics Data System (ADS)

    Anastasiadis, Spiros H.

    2005-03-01

    External-stimuli responsive block copolymers, usually known as double-hydrophilic copolymers, respond to changes in their environment such as pH, temperature and salt concentration and undergo micellization in aqueous media. Micellization induced by controlling the solution pH is advantageous for certain applications in particular when fully hydrophobic cores are required. A category of such systems comprise a pH-sensitive (weak) basic or acidic block that forms the micelle core surrounded by a corona formed by a neutral hydrophilic block. In this work we investigate the micellization behavior and the metal-nanoparticle formation in poly(2-(diethylamino)ethyl methacrylate)-block-poly(hexa(ethylene glycol) methacrylate), PDEAEMA-b-PHEGMA, amphiphilic block copolymers in aqueous media. The hydrophobic PDEAEMA block is pH-sensitive: at low pH it can be protonated and it becomes partially or completely hydrophilic, leading to molecular solubility, whereas at higher pH micelles are formed; the behavior is studied by dynamic light scattering, 1H-NMR and atomic force microscopy. The micelles consist of a PDEAEMA core and a PHEGMA corona, where the core can dissolve metal compounds due to coordination. In all these micellar nanoreactors, metal nanoparticles nucleate and grow upon reduction with sizes in the range of a few nanometers as observed by transmission electron microscopy whereas X-ray diffraction verifies their nanocrystalline structure. These particles exhibit significantly enhanced catalytic properties for hydrogenation and oxidation reactions.

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

    PubMed

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

    2015-07-21

    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), Ba(x)Sr(1-x)TiO3 (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

  1. One-step facile synthesis of noble metal nanocrystals with tunable morphology in a nematic liquid crystalline medium

    NASA Astrophysics Data System (ADS)

    Dan, Kaustabh; Satpati, Biswarup; Datta, Alokmay

    2016-05-01

    The present study describes in-situ synthesis of noble metal nano structures (MNCs) (Au and Ag) within a nematic liquid crystalline medium MBBA [N-(4-methoxybenzylidene)-4-butylaniline] without using any seed mediated growth protocol or without using any external stabilizing or reducing agent. Detailed Transmission Electron Microscopy (TEM) study indicates that apart from Kinetic based mechanism, the thermodynamical parameters also influence greatly the morphological evolution of these MNCs. The MNCs are of diverse shapes including nano prisms, hexagons, urchins, cubes, and rods which depend on the time of reaction and the choice of nanoparticle precursor.

  2. Quantitative tunneling spectroscopy of nanocrystals

    SciTech Connect

    First, Phillip N; Whetten, Robert L; Schaaff, T Gregory

    2007-05-25

    The proposed goals of this collaborative work were to systematically characterize the electronic structure and dynamics of 3-dimensional metal and semiconducting nanocrystals using scanning tunneling microscopy/spectroscopy (STM/STS) and ballistic electron emission spectroscopy (BEES). This report describes progress in the spectroscopic work and in the development of methods for creating and characterizing gold nanocrystals. During the grant period, substantial effort also was devoted to the development of epitaxial graphene (EG), a very promising materials system with outstanding potential for nanometer-scale ballistic and coherent devices ("graphene" refers to one atomic layer of graphitic, sp2 -bonded carbon atoms [or more loosely, few layers]). Funding from this DOE grant was critical for the initial development of epitaxial graphene for nanoelectronics

  3. 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

  4. Rational design and synthesis of excavated trioctahedral Au nanocrystals

    NASA Astrophysics Data System (ADS)

    Chen, Qiaoli; Jia, Yanyan; Shen, Wei; Xie, Shuifen; Yang, Yanan; Cao, Zhenming; Xie, Zhaoxiong; Zheng, Lansun

    2015-06-01

    Excavated polyhedral nanostructures, possessing the features of high surface area and well-defined surface structure with a specific crystal facet and avoidance of aggregation, could be one of the best choices for the purpose of reducing consumption and improving performance of noble metals in many application fields. However, the formation of the excavated structures is thermodynamically unfavourable and its rational synthesis is far beyond our knowledge. In this work, taking overgrowth of Pd onto trioctahedral Au nanocrystals as a model, we present a deep insight study for synthesizing an excavated structure relying on the protection role of surfactants under suitable crystal growth kinetics. Based on the abovementioned understanding, we designed a simple and effective strategy to synthesize Au nanocrystals with excavated trioctahedral structure in one step. Due to the novel feature of the excavated structure and exposed high energy {110} facets, excavated trioctahedral Au NCs exhibited optical extinction at the near-infrared region and showed high catalytic activity towards the reduction of p-nitrophenol. Moreover, the synthetic strategy can be extended to the synthesis of excavated Au-Pd alloys.Excavated polyhedral nanostructures, possessing the features of high surface area and well-defined surface structure with a specific crystal facet and avoidance of aggregation, could be one of the best choices for the purpose of reducing consumption and improving performance of noble metals in many application fields. However, the formation of the excavated structures is thermodynamically unfavourable and its rational synthesis is far beyond our knowledge. In this work, taking overgrowth of Pd onto trioctahedral Au nanocrystals as a model, we present a deep insight study for synthesizing an excavated structure relying on the protection role of surfactants under suitable crystal growth kinetics. Based on the abovementioned understanding, we designed a simple and effective

  5. Simple Methods for Production of Nanoscale Metal Oxide Films from Household Sources

    ERIC Educational Resources Information Center

    Campbell, Dean J.; Baliss, Michelle S.; Hinman, Jordan J.; Ziegenhorn, John W.; Andrews, Mark J.; Stevenson, Keith J.

    2013-01-01

    Production of thin metal oxide films was recently explored as part of an outreach program with a goal of producing nanoscale structures with household items. Household items coated with various metals or titanium compounds can be heated to produce colorful films with nanoscale thicknesses. As part of a materials chemistry laboratory experiment…

  6. Fabrication and electronic transport studies of single nanocrystal systems

    SciTech Connect

    Klein, D L

    1997-05-01

    Semiconductor and metallic nanocrystals exhibit interesting electronic transport behavior as a result of electrostatic and quantum mechanical confinement effects. These effects can be studied to learn about the nature of electronic states in these systems. This thesis describes several techniques for the electronic study of nanocrystals. The primary focus is the development of novel methods to attach leads to prefabricated nanocrystals. This is because, while nanocrystals can be readily synthesized from a variety of materials with excellent size control, means to make electrical contact to these nanocrystals are limited. The first approach that will be described uses scanning probe microscopy to first image and then electrically probe surfaces. It is found that electronic investigations of nanocrystals by this technique are complicated by tip-sample interactions and environmental factors such as salvation and capillary forces. Next, an atomic force microscope technique for the catalytic patterning of the surface of a self assembled monolayer is described. In principle, this nano-fabrication technique can be used to create electronic devices which are based upon complex arrangements of nanocrystals. Finally, the fabrication and electrical characterization of a nanocrystal-based single electron transistor is presented. This device is fabricated using a hybrid scheme which combines electron beam lithography and wet chemistry to bind single nanocrystals in tunneling contact between closely spaced metallic leads. In these devices, both Au and CdSe nanocrystals show Coulomb blockade effects with characteristic energies of several tens of meV. Additional structure is seen the transport behavior of CdSe nanocrystals as a result of its electronic structure.

  7. 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.

  8. Encapsulation of redox polysulphides via chemical interaction with nitrogen atoms in the organic linkers of metal-organic framework nanocrystals

    PubMed Central

    Park, Jung Hyo; Choi, Kyung Min; Lee, Dong Ki; Moon, Byeong Cheul; Shin, Sang Rim; Song, Min-Kyu; Kang, Jeung Ku

    2016-01-01

    Lithium polysulphides generated during discharge in the cathode of a lithium-sulphur redox cell are important, but their dissolution into the electrolyte from the cathode during each redox cycle leads to a shortened cycle life. Herein, we use in situ spectroelectrochemical measurements to demonstrate that sp2 nitrogen atoms in the organic linkers of nanocrystalline metal-organic framework-867 (nMOF-867) are able to encapsulate lithium polysulphides inside the microcages of nMOF-867, thus helping to prevent their dissolution into the electrolyte during discharge/charge cycles. This encapsulation mechanism of lithiated/delithiated polysulphides was further confirmed by observations of shifted FTIR spectra for the C = N and C-N bonds, the XPS spectra for the Li-N bonds from nMOF-867, and a visualization method, demonstrating that nMOF-867 prevents lithium polysulphides from being dissolved in the electrolyte. Indeed, a cathode fabricated using nMOF-867 exhibited excellent capacity retention over a long cycle life of 500 discharge/charge cycles, with a capacity loss of approximately 0.027% per cycle from a discharge capacity of 788 mAh/g at a high current rate of 835 mA/g. PMID:27149405

  9. Encapsulation of redox polysulphides via chemical interaction with nitrogen atoms in the organic linkers of metal-organic framework nanocrystals.

    PubMed

    Park, Jung Hyo; Choi, Kyung Min; Lee, Dong Ki; Moon, Byeong Cheul; Shin, Sang Rim; Song, Min-Kyu; Kang, Jeung Ku

    2016-01-01

    Lithium polysulphides generated during discharge in the cathode of a lithium-sulphur redox cell are important, but their dissolution into the electrolyte from the cathode during each redox cycle leads to a shortened cycle life. Herein, we use in situ spectroelectrochemical measurements to demonstrate that sp(2) nitrogen atoms in the organic linkers of nanocrystalline metal-organic framework-867 (nMOF-867) are able to encapsulate lithium polysulphides inside the microcages of nMOF-867, thus helping to prevent their dissolution into the electrolyte during discharge/charge cycles. This encapsulation mechanism of lithiated/delithiated polysulphides was further confirmed by observations of shifted FTIR spectra for the C = N and C-N bonds, the XPS spectra for the Li-N bonds from nMOF-867, and a visualization method, demonstrating that nMOF-867 prevents lithium polysulphides from being dissolved in the electrolyte. Indeed, a cathode fabricated using nMOF-867 exhibited excellent capacity retention over a long cycle life of 500 discharge/charge cycles, with a capacity loss of approximately 0.027% per cycle from a discharge capacity of 788 mAh/g at a high current rate of 835 mA/g. PMID:27149405

  10. Encapsulation of redox polysulphides via chemical interaction with nitrogen atoms in the organic linkers of metal-organic framework nanocrystals

    NASA Astrophysics Data System (ADS)

    Park, Jung Hyo; Choi, Kyung Min; Lee, Dong Ki; Moon, Byeong Cheul; Shin, Sang Rim; Song, Min-Kyu; Kang, Jeung Ku

    2016-05-01

    Lithium polysulphides generated during discharge in the cathode of a lithium-sulphur redox cell are important, but their dissolution into the electrolyte from the cathode during each redox cycle leads to a shortened cycle life. Herein, we use in situ spectroelectrochemical measurements to demonstrate that sp2 nitrogen atoms in the organic linkers of nanocrystalline metal-organic framework-867 (nMOF-867) are able to encapsulate lithium polysulphides inside the microcages of nMOF-867, thus helping to prevent their dissolution into the electrolyte during discharge/charge cycles. This encapsulation mechanism of lithiated/delithiated polysulphides was further confirmed by observations of shifted FTIR spectra for the C = N and C-N bonds, the XPS spectra for the Li-N bonds from nMOF-867, and a visualization method, demonstrating that nMOF-867 prevents lithium polysulphides from being dissolved in the electrolyte. Indeed, a cathode fabricated using nMOF-867 exhibited excellent capacity retention over a long cycle life of 500 discharge/charge cycles, with a capacity loss of approximately 0.027% per cycle from a discharge capacity of 788 mAh/g at a high current rate of 835 mA/g.

  11. Synthesis and characterization of luminescent oxide nanocrystals

    NASA Astrophysics Data System (ADS)

    Seo, Sooyeon

    Oxide nanocrystals with controlled geometries exhibit unique shape dependent optical and structural properties. Shape-controlled synthesis of rare earth doped gadolinium oxide (Gd2O3: Eu3+, Tb3+ or Er3+) and zinc gallate (ZnGa2O 4:Eu3+) nanocrystals by non-hydrolytic high temperature (˜300°C) methods are reported. Various shapes of Gd2O 3 nanocrystals were synthesized, including spheres and plates and advanced shapes such as curved rods and triangles. The nanocrystal shape was shown to be a function of the synthesis parameters, such as metal precursors (acetate, acetyl acetonate, chloride or octanoate) and surfactant type (tri-octyl phosphine oxide-TOPO, or hexadecanediol-HDD) and concentration (metal precursor: surfactant molar ratios of 1:2 to 1:5), as well as heating rate (5-25°C/min.) between pre-heat (200°C) and reaction (290°C) temperatures. The effects of these parameters upon nanocrystal shape were explained based on nucleation and growth of oxide nanocrystals. The photoluminescence intensity from Gd 2O3:Eu3+ was shown to increase as the concentration of dopant incorporated into the nanocrystals increased. The doping efficiency, defined to be the percentage of dopant incorporated into the nanocrystals, ranged from 0.57-6.1 mol%, was a function of shape of the Gd2O 3: Eu3 and was discussed in terms of the rate of reaction, product yield and crystal structure. To be used for labeling biomolecules such as DNA, RNA, or proteins, water soluble luminescent nanocrystals are required. Doped Gd2O 3 nanocrystals prepared by the non-hydrolytic hot solution method are hydrophobic and are not soluble in water due to organic surfactant encapsulation. A general strategy to convert hydrophobic luminescent nanocrystals (e.g. Gd 2O3) to water soluble particles by over-coating the hydrophobic surface with amphiphilic polymers is reported. Specifically, octylamine modified surfaces were coated with poly (acrylic acid) and water dispersions of Gd 2O3: Eu3+ were still

  12. Electrochromic nanocrystal quantum dots.

    PubMed

    Wang, C; Shim, M; Guyot-Sionnest, P

    2001-03-23

    Incorporating nanocrystals into future electronic or optoelectronic devices will require a means of controlling charge-injection processes and an understanding of how the injected charges affect the properties of nanocrystals. We show that the optical properties of colloidal semiconductor nanocrystal quantum dots can be tuned by an electrochemical potential. The injection of electrons into the quantum-confined states of the nanocrystal leads to an electrochromic response, including a strong, size-tunable, midinfrared absorption corresponding to an intraband transition, a bleach of the visible interband exciton transitions, and a quench of the narrow band-edge photoluminescence. PMID:11264530

  13. a Simple Interpretation of the Rice Spectral Indices Space for Assessment of Heavy Metal Stress

    NASA Astrophysics Data System (ADS)

    Wang, P.; Huang, F.; Liu, X. N.

    2016-06-01

    Heavy metal stress will induce the change of the bio-parameters like chlorophyll, nitrogen and water content of rice. In this paper, we analyzed the traditional spectral index which has strong relationship in general with the three bio-parameters using hyperspectral data acquired by ASD. It is found that some indies do not work well when the heavy metal stress exists, however, some indies still has ability to estimate the above three bio-parameters. A new interpretation is proposed to classify the stress level based on both the physical mechanism analysis and the statistic model after we describe and discuss studies on the expression of spectral indices of rice under heavy metal stress. The 3-axes spectral indices spaces, which are constructed of 3 spectral indices sensitive to rice's chlorophyll concentration, nitrogen concentration and water concentration respectively, are used to visualize the linkage between heavy metal stress and spectrum of rice canopy.

  14. Size-controlled simple fabrication of free-standing, ultralong metal nanobelt array.

    PubMed

    Kubo, Wakana; Hayakawa, Harumi; Miyoshi, Kentaro; Fujikawa, Shigenori

    2011-01-01

    Free-standing, ultralong (up to several millimeters) nanobelts of gold, silver, and copper were fabricated by a template approach. Firstly, a metal nanofin array was prepared on a substrate via metal nanocoating of the template surface and selective removal of the metal top layer and template. Electroless plating and sputtering were employed for the metal nanocoating. In this approach, the minimum width and thickness of the Au nanobelt were 95 and 30 nm, respectively. Systematic control of the nanobelt width (from 95 to 350 nm) was successfully achieved by adjusting the template height. Free-standing nanobelts of several millimeters in length were fabricated and maintained their unique structure and alignment, even on a mesh grid. PMID:21446416

  15. Jingle-bell-shaped ferrite hollow sphere with a noble metal core: Simple synthesis and their magnetic and antibacterial properties

    SciTech Connect

    Li Siheng; Wang Enbo Tian Chungui; Mao Baodong; Kang Zhenhui; Li Qiuyu; Sun Guoying

    2008-07-15

    In this paper, a simple strategy is developed for rational fabrication of a class of jingle-bell-shaped hollow structured nanomaterials marked as Ag(MFe{sub 2}O{sub 4}) (M=Ni, Co, Mg, Zn), consisting of ferrite hollow shells and metal nanoparticle cores, using highly uniform colloidal Ag(C) microspheres as template. The final composites were obtained by direct adsorption of metal cations Fe{sup 3+} and M{sup 2+} on the surface of the Ag(C) spheres followed by calcination process to remove the middle carbon shell and transform the metal ions into pure phase ferrites. The as-prepared composites were characterized by X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray analysis (EDX), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-vis spectroscopy and SQUID magnetometer. The results showed that the composites possess the magnetic property of the ferrite shell and the optical together with antibacterial property of the Ag core. - Graphical abstract: MFe{sub 2}O{sub 4} (M=Ni, Co, Mg, Zn) hollow spheres with a noble metal nanoparticle core were successfully prepared by using colloidal metal(C) core-shell spheres as templates with no need of surface modification. The shell thickness and magnetic properties of the ferrite hollow spheres could be controlled by varying the synthetic parameters.

  16. The use of molecular dynamics for the thermodynamic properties of simple and transition metals

    SciTech Connect

    Straub, G.K.

    1987-04-01

    The technique of computer simulation of the molecular dynamics in metallic systems to calculate thermodynamic properties is discussed. The nature of a metal as determined by its electronic structure is used to determine the total adiabatic potential. The effective screened ion-ion interaction can then be used in a molecular dynamics simulation. The method for the construction of a molecular dynamics ensemble, its relation to the canonical ensemble, and the definition of thermodynamic functions from the Helmholtz free energy is given. The method for the analysis of the molecular dynamics results from quasiharmonic lattice dynamics and the decomposition in terms of harmonic and anharmonic contributions is given for solids. For fluid phase metals, procedures for calculating the thermodynamics and determining the constant of entropy are presented. The solid-fluid phase boundary as a function of pressure and temperature is determined using the results of molecular dynamics. Throughout, examples and results for metallic sodium are used. The treatment of the transition metal electronic d-states in terms of an effective pair-wise interaction is also discussed and the phonon dispersion curves of Al, Ni, and Cu are calculated.

  17. Nanocrystal Bioassembly: Asymmetry, Proximity, and Enzymatic Manipulation

    SciTech Connect

    Claridge, Shelley A.

    2008-05-01

    Research at the interface between biomolecules and inorganic nanocrystals has resulted in a great number of new discoveries. In part this arises from the synergistic duality of the system: biomolecules may act as self-assembly agents for organizing inorganic nanocrystals into functional materials; alternatively, nanocrystals may act as microscopic or spectroscopic labels for elucidating the behavior of complex biomolecular systems. However, success in either of these functions relies heavily uponthe ability to control the conjugation and assembly processes.In the work presented here, we first design a branched DNA scaffold which allows hybridization of DNA-nanocrystal monoconjugates to form discrete assemblies. Importantly, the asymmetry of the branched scaffold allows the formation of asymmetric2assemblies of nanocrystals. In the context of a self-assembled device, this can be considered a step toward the ability to engineer functionally distinct inputs and outputs.Next we develop an anion-exchange high performance liquid chromatography purification method which allows large gold nanocrystals attached to single strands of very short DNA to be purified. When two such complementary conjugates are hybridized, the large nanocrystals are brought into close proximity, allowing their plasmon resonances to couple. Such plasmon-coupled constructs are of interest both as optical interconnects for nanoscale devices and as `plasmon ruler? biomolecular probes.We then present an enzymatic ligation strategy for creating multi-nanoparticle building blocks for self-assembly. In constructing a nanoscale device, such a strategy would allow pre-assembly and purification of components; these constructs can also act as multi-label probes of single-stranded DNA conformational dynamics. Finally we demonstrate a simple proof-of-concept of a nanoparticle analog of the polymerase chain reaction.

  18. A simple model for large-scale simulations of fcc metals with explicit treatment of electrons

    NASA Astrophysics Data System (ADS)

    Mason, D. R.; Foulkes, W. M. C.; Sutton, A. P.

    2010-01-01

    The continuing advance in computational power is beginning to make accurate electronic structure calculations routine. Yet, where physics emerges through the dynamics of tens of thousands of atoms in metals, simplifications must be made to the electronic Hamiltonian. We present the simplest extension to a single s-band model [A.P. Sutton, T.N. Todorov, M.J. Cawkwell and J. Hoekstra, Phil. Mag. A 81 (2001) p.1833.] of metallic bonding, namely, the addition of a second s-band. We show that this addition yields a reasonable description of the density of states at the Fermi level, the cohesive energy, formation energies of point defects and elastic constants of some face-centred cubic (fcc) metals.

  19. Theory of ion-stimulated electron emission from simple metals: Explicit calculations

    SciTech Connect

    Gaspar, J.A. |; Eguiluz, A.G. |; Mills, D.L.

    1995-05-15

    We apply a description of ion-stimulated electron emission from metals developed earlier by one of us [D. L. Mills, Surf. Sci. 294, 161 (1993)] to ions which strike aluminum metal at both grazing and normal incidence. The electronic response of the substrate is modeled within the jellium picture. For grazing incidence, we employ realistic ion trajectories which allow penetration of the ions into the metal. The substrate response is described microscopically, so a proper description of short-wavelength aspects is incorporated fully in our calculations. Response functions employed are those for a jellium slab, so that electron emission mediated by bulk plasmons is described. Our results reproduce very well the experimental data reported by Rau, for the case of grazing incidence. In addition, we present calculations for the case of normal incidence.

  20. A flexible method for depositing dense nanocrystal thin films: impaction of germanium nanocrystals

    SciTech Connect

    Holman, Zachary C.; Kortshagen, Uwe R.

    2010-07-27

    Nanomaterials are exciting candidates for use in new optical and electronic devices ranging from solar cells to gas sensors. However, to reach their full potential, nanomaterials must be deposited as dense thin films on flexible substrates using inexpensive processing technologies such as roll-to-roll printing. We report a new, flexible technique for depositing aerosolized nanocrystals that lends itself to roll-to-roll processes. Germanium nanocrystals produced in a plasma are accelerated through a slit orifice by a supersonic gas jet and are impacted onto a translated substrate. A uniform nanocrystal film is quickly deposited over large areas, and features as small as 2 µm can then be patterned using conventional lift-off photolithography. The density of a deposited film depends on the pressures upstream and downstream of the orifice, their ratio, and the distance between the orifice and the substrate. Nanocrystal film densities exceeding 50% of the density of bulk germanium are routinely achieved with several sizes of nanocrystals, approaching the theoretical limit for randomly packed spheres. A simple model is presented that shows that the calculated nanocrystal velocity upon impaction is strongly correlated with the resulting film density.

  1. Biomineralization: Nanocrystals by design

    NASA Astrophysics Data System (ADS)

    Shang, Li; Nienhaus, Gerd Ulrich

    2015-10-01

    Nanocrystals with precisely defined structures offer promise as components of advanced materials yet they are challenging to create. Now, a nanocrystal made up of seven cadmium and twelve chloride ions has been synthesized via a biotemplating approach that uses a de novo designed protein.

  2. Doping semiconductor nanocrystals.

    PubMed

    Erwin, Steven C; Zu, Lijun; Haftel, Michael I; Efros, Alexander L; Kennedy, Thomas A; Norris, David J

    2005-07-01

    Doping--the intentional introduction of impurities into a material--is fundamental to controlling the properties of bulk semiconductors. This has stimulated similar efforts to dope semiconductor nanocrystals. Despite some successes, many of these efforts have failed, for reasons that remain unclear. For example, Mn can be incorporated into nanocrystals of CdS and ZnSe (refs 7-9), but not into CdSe (ref. 12)--despite comparable bulk solubilities of near 50 per cent. These difficulties, which have hindered development of new nanocrystalline materials, are often attributed to 'self-purification', an allegedly intrinsic mechanism whereby impurities are expelled. Here we show instead that the underlying mechanism that controls doping is the initial adsorption of impurities on the nanocrystal surface during growth. We find that adsorption--and therefore doping efficiency--is determined by three main factors: surface morphology, nanocrystal shape, and surfactants in the growth solution. Calculated Mn adsorption energies and equilibrium shapes for several nanocrystals lead to specific doping predictions. These are confirmed by measuring how the Mn concentration in ZnSe varies with nanocrystal size and shape. Finally, we use our predictions to incorporate Mn into previously undopable CdSe nanocrystals. This success establishes that earlier difficulties with doping are not intrinsic, and suggests that a variety of doped nanocrystals--for applications from solar cells to spintronics--can be anticipated. PMID:16001066

  3. Self-Organized Ultrathin Oxide Nanocrystals

    SciTech Connect

    Huo, Ziyang; Tsung, Chia-kuang; Huang, Wenyu; Fardy, Melissa; Yan, Ruoxue; Li, Yadong; Yang, Piedong; Zhang, Xiaofeng

    2009-01-08

    Sub-2-nm (down to one-unit cell) uniform oxide nanocrystals and highly ordered superstructures were obtained in one step using oleylamine and oleic acid as capping and structure directing agents. The cooperative nature of the nanocrystal growth and assembly resulted in mesoscopic one-dimensional ribbon-like superstructures made of these ultrathin nanocrystals. The process reported here is general and can be readily extended to the production of many other transition metal (TiO2, ZnO, Nb2O5) and rare earth oxide (Eu2O3, Sm2O3, Er2O3, Y2O3, Tb2O3, and Yb2O3) systems.

  4. Universal Quake Statistics: From Compressed Nanocrystals to Earthquakes.

    PubMed

    Uhl, Jonathan T; Pathak, Shivesh; Schorlemmer, Danijel; Liu, Xin; Swindeman, Ryan; Brinkman, Braden A W; LeBlanc, Michael; Tsekenis, Georgios; Friedman, Nir; Behringer, Robert; Denisov, Dmitry; Schall, Peter; Gu, Xiaojun; Wright, Wendelin J; Hufnagel, Todd; Jennings, Andrew; Greer, Julia R; Liaw, P K; Becker, Thorsten; Dresen, Georg; Dahmen, Karin A

    2015-01-01

    Slowly-compressed single crystals, bulk metallic glasses (BMGs), rocks, granular materials, and the earth all deform via intermittent slips or "quakes". We find that although these systems span 12 decades in length scale, they all show the same scaling behavior for their slip size distributions and other statistical properties. Remarkably, the size distributions follow the same power law multiplied with the same exponential cutoff. The cutoff grows with applied force for materials spanning length scales from nanometers to kilometers. The tuneability of the cutoff with stress reflects "tuned critical" behavior, rather than self-organized criticality (SOC), which would imply stress-independence. A simple mean field model for avalanches of slipping weak spots explains the agreement across scales. It predicts the observed slip-size distributions and the observed stress-dependent cutoff function. The results enable extrapolations from one scale to another, and from one force to another, across different materials and structures, from nanocrystals to earthquakes. PMID:26572103

  5. Analysis of hardening behavior of sheet metals by a new simple shear test method taking into account the Bauschinger effect

    NASA Astrophysics Data System (ADS)

    Bang, Sungsik; Rickhey, Felix; Kim, Minsoo; Lee, Hyungyil; Kim, Naksoo

    2013-12-01

    In this study we establish a process to predict hardening behavior considering the Bauschinger effect for zircaloy-4 sheets. When a metal is compressed after tension in forming, the yield strength decreases. For this reason, the Bauschinger effect should be considered in FE simulations of spring-back. We suggested a suitable specimen size and a method for determining the optimum tightening torque for simple shear tests. Shear stress-strain curves are obtained for five materials. We developed a method to convert the shear load-displacement curve to the effective stress-strain curve with FEA. We simulated the simple shear forward/reverse test using the combined isotropic/kinematic hardening model. We also investigated the change of the load-displacement curve by varying the hardening coefficients. We determined the hardening coefficients so that they follow the hardening behavior of zircaloy-4 in experiments.

  6. Comparison of Residual Stresses in Inconel 718 Simple Parts Made by Electron Beam Melting and Direct Laser Metal Sintering

    NASA Astrophysics Data System (ADS)

    Sochalski-Kolbus, L. M.; Payzant, E. A.; Cornwell, P. A.; Watkins, T. R.; Babu, S. S.; Dehoff, R. R.; Lorenz, M.; Ovchinnikova, O.; Duty, C.

    2015-03-01

    Residual stress profiles were mapped using neutron diffraction in two simple prism builds of Inconel 718: one fabricated with electron beam melting (EBM) and the other with direct laser metal sintering. Spatially indexed stress-free cubes were obtained by electrical discharge machining (EDM) equivalent prisms of similar shape. The (311) interplanar spacings from the EDM sectioned sample were compared to the interplanar spacings calculated to fulfill stress and moment balance. We have shown that applying stress and moment balance is a necessary supplement to the measurements for the stress-free cubes with respect to accurate stress calculations in additively manufactured components. In addition, our work has shown that residual stresses in electron beam melted parts are much smaller than that of direct laser metal sintered parts most likely due to the powder preheating step in the EBM process.

  7. Catalytic Addition of Simple Alkenes to Carbonyl Compounds Using Group 10 Metals

    PubMed Central

    Schleicher, Kristin D.

    2011-01-01

    Recent advances using nickel complexes in the activation of unactivated monosubstituted olefins for catalytic intermolecular carbon–carbon bond-forming reactions with carbonyl compounds, such as simple aldehydes, isocyanates, and conjugated aldehydes and ketones, are discussed. In these reactions, the olefins function as vinyl- and allylmetal equivalents, providing a new strategy for organic synthesis. Current limitations and the outlook for this new strategy are also discussed. PMID:21904421

  8. One-step electrochemical synthesis of preferentially oriented (111) Pd nanocrystals supported on graphene nanoplatelets for formic acid electrooxidation

    NASA Astrophysics Data System (ADS)

    Chen, Qing-Song; Xu, Zhong-Ning; Peng, Si-Yan; Chen, Yu-Min; Lv, Dong-Mei; Wang, Zhi-Qiao; Sun, Jing; Guo, Guo-Cong

    2015-05-01

    Pd nanocrystals supported on graphene nanoplatelets (Pd/GNP) have been successfully synthesized by simultaneously electrochemical milling of Pd wire and graphite rod. It should be stressed that without the assistance of graphite rod, the Pd nanocrystals are unable to be obtained individually from Pd wire under the same conditions. Investigations of SEM and TEM demonstrate that Pd/GNP are preferentially decorated with (111) faceted nanocrystals. XPS studies confirm the strong metal-support interaction in Pd/GNP and reveal the surface is almost composed of Pd(0) species. Electrochemical measurements show that the prepared Pd based catalyst exhibits superior electrocatalytic activity towards formic acid oxidation, which may be attributed to the combined effects involving the preferentially oriented (111) surface structure, specific electronic structure and high dispersion of Pd nanocrystals as well as the support effects of graphene nanoplatelets. The synthesis method is simple and effective to prepare excellent new carbon-supported electrocatalysts, which is of great significance for direct organic molecule fuel cell.

  9. The age-metallicity-velocity dispersion relation in the solar neighborhood and a simple evolution model

    NASA Astrophysics Data System (ADS)

    Meusinger, H.; Stecklum, B.; Reimann, H.-G.

    1991-05-01

    An analysis of the age-metallicity relation (AMR) based on previous data is conducted again and the age-velocity relation (AVR) is estimated for some nearby stars to examine connections between the relations. In the period of evolution of the galactic disk, an important relationship with age is determined for both AMR and AVR. The observed metallicity-velocity relation is compared to the predicted relation to verify the AVR and AMR derivations. A model is presented in which the star formation rate, the infall rate of gas, and the initial mass function are constant. The model is found to agree with observed constraints on star counts in the solar neighborhood and constraints on the chemical and kinematical evolution of the local disk. A theory regarding the primary heating mechanism of the galactic disk is developed in terms of the AVR, and possible explanations - massive gas clouds and transient spiral waves - are discussed.

  10. A simple composite protective layer coating that enhances the cycling stability of lithium metal batteries

    NASA Astrophysics Data System (ADS)

    Lee, Hongkyung; Lee, Dong Jin; Kim, Yun-Jung; Park, Jung-Ki; Kim, Hee-Tak

    2015-06-01

    Metallic lithium is the most promising negative electrode for high-energy rechargeable batteries due to its extremely high specific capacity and its extremely low redox potential. However, the low cycle efficiency and lithium dendrite formation during the charge/discharge processes consistently hinder its practical application. In this report, we present a stabilized Li electrode on which a Li+ ion conductive inorganic/organic composite protective layer (CPL) is coated. With the introduction of the CPL, the Li dendrite growth and electrolyte decomposition are effectively suppressed; consequently, stable Li plating/stripping at high current densities up to 10 mA cm-2 is possible. Nanoindentation tests demonstrate that the shear modulus of the CPL at narrow indentations is 1.8 times higher than that of the Li metal, which provides a theoretical understanding for its efficacy. Moreover, the LiCoO2/Li cell incorporating CPL exhibits excellent cycling stability up to 400 cycles at 1 mA cm-2 (1 C-rate), which demonstrates practical applicability in Li ion batteries through replacing the graphite anode with a CPL-coated Li metal anode.

  11. Steroid nanocrystals prepared using the nano spray dryer B-90.

    PubMed

    Baba, Koichi; Nishida, Kohji

    2013-01-01

    The Nano Spray Dryer B-90 offers a new, simple, and alternative approach for the production of drug nanocrystals. In this study, the preparation of steroid nanocrystals using the Nano Spray Dryer B-90 was demonstrated. The particle size was controlled by selecting the mesh aperture size. Submicrometer steroid particles in powder form were successfully obtained. These nanoparticles were confirmed to have a crystal structure using powder X-ray diffraction pattern analysis. Since drug nanocrystals have recently been considered as a novel type of drug formulation for drug delivery systems, this study will be useful for nano-medical applications. PMID:24300400

  12. Steroid Nanocrystals Prepared Using the Nano Spray Dryer B-90

    PubMed Central

    Baba, Koichi; Nishida, Kohji

    2013-01-01

    The Nano Spray Dryer B-90 offers a new, simple, and alternative approach for the production of drug nanocrystals. In this study, the preparation of steroid nanocrystals using the Nano Spray Dryer B-90 was demonstrated. The particle size was controlled by selecting the mesh aperture size. Submicrometer steroid particles in powder form were successfully obtained. These nanoparticles were confirmed to have a crystal structure using powder X-ray diffraction pattern analysis. Since drug nanocrystals have recently been considered as a novel type of drug formulation for drug delivery systems, this study will be useful for nano-medical applications. PMID:24300400

  13. Formation of hollow nanocrystals through the nanoscale kirkendall effect

    SciTech Connect

    Yin, Yadong; Rioux, Robert M.; Erdonmez, Can K.; Hughes, Steven; Somorjai, Gabor A.; Alivisatos, A. Paul

    2004-03-11

    We demonstrate that hollow nanocrystals can be synthesized through a mechanism analogous to the Kirkendall Effect, in which pores form due to the difference in diffusion rates between two components in a diffusion couple. Cobalt nanocrystals are chosen as a primary example to show that their reaction in solution with oxygen, sulfur or selenium leads to the formation of hollow nanocrystals of the resulting oxide and chalcogenides. This process provides a general route to the synthesis of hollow nanostructures of large numbers of compounds. A simple extension of this process yields platinum-cobalt oxide yolk-shell nanostructures which may serve as nanoscale reactors in catalytic applications.

  14. Metal-assisted chemical etching using sputtered gold: a simple route to black silicon

    NASA Astrophysics Data System (ADS)

    Kurek, Agnieszka; Barry, Seán T.

    2011-08-01

    We report an accessible and simple method of producing 'black silicon' with aspect ratios as high as 8 using common laboratory equipment. Gold was sputtered to a thickness of 8 nm using a low-vacuum sputter coater. The structures were etched into silicon substrates using an aqueous H2O2/HF solution, and the gold was then removed using aqua regia. Ultrasonication was necessary to produce columnar structures, and an etch time of 24 min gave a velvety, non-reflective surface. The surface features after 24 min etching were uniformly microstructured over an area of square centimetres.

  15. Nanocrystal powered nanomotor

    DOEpatents

    Regan, Brian C.; Zettl, Alexander K.; Aloni, Shaul

    2011-01-04

    A nanoscale nanocrystal which may be used as a reciprocating motor is provided, comprising a substrate having an energy differential across it, e.g. an electrical connection to a voltage source at a proximal end; an atom reservoir on the substrate distal to the electrical connection; a nanoparticle ram on the substrate distal to the atom reservoir; a nanolever contacting the nanoparticle ram and having an electrical connection to a voltage source, whereby a voltage applied between the electrical connections on the substrate and the nanolever causes movement of atoms between the reservoir and the ram. Movement of the ram causes movement of the nanolever relative to the substrate. The substrate and nanolever preferably comprise multiwalled carbon nanotubes (MWNTs) and the atom reservoir and nanoparticle ram are preferably metal (e.g. indium) deposited as small particles on the MWNTs. The substrate may comprise a silicon chip that has been fabricated to provide the necessary electrodes and other electromechanical structures, and further supports an atomic track, which may comprise an MWNT.

  16. Atomic transport and surface properties of some simple liquid metal using one component plasma system

    NASA Astrophysics Data System (ADS)

    Sonvane, Yogeshkumar A.; Thakor, Pankajsinh B.; Jani, Ashwin R.

    2012-12-01

    In the present paper, we have calculated diffusion coefficient, viscosity coefficient, and surface tension of liquid metals near melting point (Li, Na, K, Rb, Cs, Mg, Al, Pb, and Bi). We have applied our newly constructed model potential to describe electron ion interaction with one component plasma reference system. We have also investigated the effect of different correction functions such as those of Hartree, Hubbard and Sham, Vashista and Singwi, Taylor, Ichimaru and Utsumi, Farid et al., and Sarkar et al. on the above-said properties. It is observed that the present results are found to be in good agreement with those of experimental data as well as with other theoretical results.

  17. Slow light in a simple metamaterial structure constructed by cut and continuous metal strips

    NASA Astrophysics Data System (ADS)

    Kang, M.; Li, Y. N.; Chen, J.; Chen, J.; Bai, Q.; Wang, H. T.; Wu, P. H.

    2010-09-01

    Recently, slow light in metamaterials has been investigated based on the coupling between two quasi-bound states, in classic analogue of electromagnetically induced transparency in atomic systems. Here we demonstrate the feasibility in achieving slow light in metamaterials, based on the mechanism of coupling between a quasi-bound state and a continuum state. The theoretical prediction by a two-particle model is in good agreement with the experimental result in the metamaterial composed of the cut and continuous metal strips. The present work illustrates the versatility of metamaterials, implying the great potential in many applications.

  18. A simple approach to obtain hybrid Au-loaded polymeric nanoparticles with a tunable metal load

    NASA Astrophysics Data System (ADS)

    Luque-Michel, Edurne; Larrea, Ane; Lahuerta, Celia; Sebastian, Víctor; Imbuluzqueta, Edurne; Arruebo, Manuel; Blanco-Prieto, María J.; Santamaría, Jesús

    2016-03-01

    A new strategy to nanoengineer multi-functional polymer-metal hybrid nanostructures is reported. By using this protocol the hurdles of most of the current developments concerning covalent and non-covalent attachment of polymers to preformed inorganic nanoparticles (NPs) are overcome. The strategy is based on the in situ reduction of metal precursors using the polymeric nanoparticle as a nanoreactor. Gold nanoparticles and poly(dl-lactic-co-glycolic acid), PLGA, are located in the core and shell, respectively. This novel technique enables the production of PLGA NPs smaller than 200 nm that bear either a single encapsulated Au NP or several smaller NPs with tunable sizes and a 100% loading efficiency. In situ reduction of Au ions inside the polymeric NPs was achieved on demand by using heat to activate the reductive effect of citrate ions. In addition, we show that the loading of the resulting Au NPs inside the PLGA NPs is highly dependent on the surfactant used. Electron microscopy, laser irradiation, UV-Vis and fluorescence spectroscopy characterization techniques confirm the location of Au nanoparticles. These promising results indicate that these hybrid nanomaterials could be used in theranostic applications or as contrast agents in dark-field imaging and computed tomography.A new strategy to nanoengineer multi-functional polymer-metal hybrid nanostructures is reported. By using this protocol the hurdles of most of the current developments concerning covalent and non-covalent attachment of polymers to preformed inorganic nanoparticles (NPs) are overcome. The strategy is based on the in situ reduction of metal precursors using the polymeric nanoparticle as a nanoreactor. Gold nanoparticles and poly(dl-lactic-co-glycolic acid), PLGA, are located in the core and shell, respectively. This novel technique enables the production of PLGA NPs smaller than 200 nm that bear either a single encapsulated Au NP or several smaller NPs with tunable sizes and a 100% loading

  19. Diorganyl dichalcogenides as useful synthons for colloidal semiconductor nanocrystals.

    PubMed

    Brutchey, Richard L

    2015-11-17

    The ability to synthesize colloidal semiconductor nanocrystals in a well-controlled manner (i.e., with fine control over size, shape, size dispersion, and composition) has been mastered over the past 15 years. Much of this success stems from careful studies of precursor conversion and nanocrystal growth with respect to phosphine chalcogenide precursors for the synthesis of metal chalcogenide nanocrystals. Despite the high level of success that has been achieved with phosphine chalcogenides, there has been a longstanding interest in exploring alternate chalcogenide precursors because of issues associated with phosphine chalcogenide cost, purity, toxicity, etc. This has resulted in a large body of literature on the use of sulfur and selenium dissolved in octadecene or amines, thio- and selenoureas, and silyl chalcogenides as alternate chalcogenide precursors for metal chalcogenide nanocrystal synthesis. In this Account, emerging work on the use of diorganyl dichalcogenides (R-E-E-R, where E = S, Se, or Te and R = alkyl, allyl, benzyl, or aryl) as alternate chalcogenide precursors for the synthesis of metal chalcogenide nanocrystals is summarized. Among the benefits of these dichalcogenide synthons are the following: (i) they represent the first and only common precursor type that can function as chalcogen transfer reagents for each of the group VI elements (i.e., to make metal oxide, metal sulfide, metal selenide, and metal telluride nanocrystals); (ii) they possess relatively weak E-E bonds that can be readily cleaved under mild thermolytic or photolytic conditions; and (iii) the organic substituents can be tuned to affect the reactivity. These combined attributes have allowed dichalcogenide precursors to be employed for a wide range of metal chalcogenide nanocrystal syntheses, including those for In2S3, SnxGe1-xSe, SnTe, Cu2-xSySe1-y, ZnSe, CdS, CdSe, MoSe2, WSe2, BiSe, and CuFeS2. Interestingly, a number of metastable phases of compositionally complex

  20. A simple approach to obtain hybrid Au-loaded polymeric nanoparticles with a tunable metal load.

    PubMed

    Luque-Michel, Edurne; Larrea, Ane; Lahuerta, Celia; Sebastian, Víctor; Imbuluzqueta, Edurne; Arruebo, Manuel; Blanco-Prieto, María J; Santamaría, Jesús

    2016-03-28

    A new strategy to nanoengineer multi-functional polymer-metal hybrid nanostructures is reported. By using this protocol the hurdles of most of the current developments concerning covalent and non-covalent attachment of polymers to preformed inorganic nanoparticles (NPs) are overcome. The strategy is based on the in situ reduction of metal precursors using the polymeric nanoparticle as a nanoreactor. Gold nanoparticles and poly(DL-lactic-co-glycolic acid), PLGA, are located in the core and shell, respectively. This novel technique enables the production of PLGA NPs smaller than 200 nm that bear either a single encapsulated Au NP or several smaller NPs with tunable sizes and a 100% loading efficiency. In situ reduction of Au ions inside the polymeric NPs was achieved on demand by using heat to activate the reductive effect of citrate ions. In addition, we show that the loading of the resulting Au NPs inside the PLGA NPs is highly dependent on the surfactant used. Electron microscopy, laser irradiation, UV-Vis and fluorescence spectroscopy characterization techniques confirm the location of Au nanoparticles. These promising results indicate that these hybrid nanomaterials could be used in theranostic applications or as contrast agents in dark-field imaging and computed tomography. PMID:26612770

  1. A simple route to diverse noble metal-decorated iron oxide nanoparticles for catalysis.

    PubMed

    Walker, Joan M; Zaleski, Jeffrey M

    2016-01-21

    Developing facile synthetic routes to multifunctional nanoparticles combining the magnetic properties of iron oxides with the optical and catalytic utility of noble metal particles remains an important goal in realizing the potential of hybrid nanomaterials. To this end, we have developed a single route to noble metal-decorated magnetic nanoparticles (Fe3O4@SiO2-M; M = Au, Pd, Ag, and PtAg) and characterized them by HRTEM and STEM/EDX imaging to reveal their nanometer size (16 nm Fe3O4 and 1-5 nm M seeds) and uniformity. This represents one of the few examples of genuine multifunctional particles on the nanoscale. We show that these hybrid structures have excellent catalytic activity for the reduction of 4-nitrophenol (knorm = 2 × 10(7) s(-1) mol(Pd)(-1); 5 × 10(6) s(-1) mol(Au)(-1); 5 × 10(5) s(-1) mol(PtAg)(-1); 7 × 10(5) s(-1) mol(Ag)(-1)). These rates are the highest reported for nano-sized comparables, and are competitive with mesoparticles of similar composition. Due to their magnetic response, the particles are also suitable for magnetic recovery and maintain >99% conversion for at least four cycles. Using this synthetic route, Fe3O4@SiO2-M particles show great promise for further development as a precursor to complicated anisotropic materials or for applications ranging from nanocatalysis to biomedical sensing. PMID:26681072

  2. Amorphization of embedded Cu nanocrystals by ion irradiation

    NASA Astrophysics Data System (ADS)

    Johannessen, B.; Kluth, P.; Llewellyn, D. J.; Foran, G. J.; Cookson, D. J.; Ridgway, M. C.

    2007-02-01

    While bulk crystalline elemental metals cannot be amorphized by ion irradiation in the absence of chemical impurities, the authors demonstrate that finite-size effects enable the amorphization of embedded Cu nanocrystals. The authors form and compare the atomic-scale structure of the polycrystalline, nanocrystalline, and amorphous phases, present an explanation for the extreme sensitivity to irradiation exhibited by nanocrystals, and show that low-temperature annealing is sufficient to return amorphized material to the crystalline form.

  3. A simple route to diverse noble metal-decorated iron oxide nanoparticles for catalysis

    NASA Astrophysics Data System (ADS)

    Walker, Joan M.; Zaleski, Jeffrey M.

    2016-01-01

    Developing facile synthetic routes to multifunctional nanoparticles combining the magnetic properties of iron oxides with the optical and catalytic utility of noble metal particles remains an important goal in realizing the potential of hybrid nanomaterials. To this end, we have developed a single route to noble metal-decorated magnetic nanoparticles (Fe3O4@SiO2-M M = Au, Pd, Ag, and PtAg) and characterized them by HRTEM and STEM/EDX imaging to reveal their nanometer size (16 nm Fe3O4 and 1-5 nm M seeds) and uniformity. This represents one of the few examples of genuine multifunctional particles on the nanoscale. We show that these hybrid structures have excellent catalytic activity for the reduction of 4-nitrophenol (knorm = 2 × 107 s-1 mol(Pd)-1 5 × 106 s-1 mol(Au)-1 5 × 105 s-1 mol(PtAg)-1 7 × 105 s-1 mol(Ag)-1). These rates are the highest reported for nano-sized comparables, and are competitive with mesoparticles of similar composition. Due to their magnetic response, the particles are also suitable for magnetic recovery and maintain >99% conversion for at least four cycles. Using this synthetic route, Fe3O4@SiO2-M particles show great promise for further development as a precursor to complicated anisotropic materials or for applications ranging from nanocatalysis to biomedical sensing.Developing facile synthetic routes to multifunctional nanoparticles combining the magnetic properties of iron oxides with the optical and catalytic utility of noble metal particles remains an important goal in realizing the potential of hybrid nanomaterials. To this end, we have developed a single route to noble metal-decorated magnetic nanoparticles (Fe3O4@SiO2-M M = Au, Pd, Ag, and PtAg) and characterized them by HRTEM and STEM/EDX imaging to reveal their nanometer size (16 nm Fe3O4 and 1-5 nm M seeds) and uniformity. This represents one of the few examples of genuine multifunctional particles on the nanoscale. We show that these hybrid structures have excellent catalytic

  4. Simple and low cost method for metal-based micro-capillary channels for heat exchanger use

    NASA Astrophysics Data System (ADS)

    Ogbonnaya, E.; Champagne, C.; Weiss, L.

    2013-11-01

    In this work, we present an alternative, low cost method for the fabrication of a heat exchanger utilizing metal-based microchannels using the UV-LiGA technique. Lithography is used to pattern dry film negative photoresist (Ordyl P-50100) on the substrate. The resist is laminated over the substrate and exposed with a UV source. The use of dry film resist allows for simple and inexpensive microchannel patterns without requiring advanced cleanroom equipment. Following the lithography process, electrodeposition of metals is used to fill the recesses patterned in the resist. In this work, nickel has been electroplated into the bounding resist structure. After electroplating, the remaining resist is dissolved leaving free standing metal structures. The fabricated exchanger is then evaluated based on thermal absorption of simulated waste heat sources and capillary action of the metal channels themselves. Channels are fabricated to heights of 60, 70 and 90 μm respectively on copper substrate using these methods. Working fluid mass transfer rate from the heated microchannel heat exchanger (MHE) is utilized as a basic metric of operation. The mass transfer rate recorded from the nickel-based MHE is 2.19, 2.81 and 3.20 mg s-1 respectively for the different channel heights. This implies an effective thermal power consumption rate of 1.66, 2.13 and 2.42 kW m-2 respectively. By contrast, an MHE fabricated with 115 and 142 μm tall channels on silicon substrate is shown to evaporate up to 2.84 and 3.04 mg s-1 respectively, giving an effective thermal power consumption of 2.15 and 2.31 kW m-2 respectively. An investigation of working fluid contact angle with the electroplated nickel surface is also presented. The surface is found to be a porous structure stemming from the electroplating process.

  5. Analysis of simple 2-D and 3-D metal structures subjected to fragment impact

    NASA Technical Reports Server (NTRS)

    Witmer, E. A.; Stagliano, T. R.; Spilker, R. L.; Rodal, J. J. A.

    1977-01-01

    Theoretical methods were developed for predicting the large-deflection elastic-plastic transient structural responses of metal containment or deflector (C/D) structures to cope with rotor burst fragment impact attack. For two-dimensional C/D structures both, finite element and finite difference analysis methods were employed to analyze structural response produced by either prescribed transient loads or fragment impact. For the latter category, two time-wise step-by-step analysis procedures were devised to predict the structural responses resulting from a succession of fragment impacts: the collision force method (CFM) which utilizes an approximate prediction of the force applied to the attacked structure during fragment impact, and the collision imparted velocity method (CIVM) in which the impact-induced velocity increment acquired by a region of the impacted structure near the impact point is computed. The merits and limitations of these approaches are discussed. For the analysis of 3-d responses of C/D structures, only the CIVM approach was investigated.

  6. A simple method for understanding the triangular growth patterns of transition metal dichalcogenide sheets

    NASA Astrophysics Data System (ADS)

    Zhu, Siya; Wang, Qian

    2015-10-01

    Triangular nanoflake growth patterns have been commonly observed in synthesis of transition metal dichalcogenide sheets and their hybrid structures. Triangular nanoflakes not only show exceptional properties, but also can serve as building blocks for two or three dimensional structures. In this study, taking the MoS2 system as a test case, we propose a Matrix method to understand the mechanism of such unique growth pattern. Nanoflakes with different edge types are mathematically described with configuration matrices, and the total formation energy is calculated as the sum of the edge formation energies and the chemical potentials of sulfur and molybdenum. Based on energetics, we find that three triangular patterns with the different edge configurations are energetically more favorable in different ranges of the chemical potential of sulfur, which are in good agreement with experimental observations. Our algorithm has high efficiency and can deal with nanoflakes in microns which are beyond the ability of ab-initio method. This study not only elucidates the mechanism of triangular nanoflake growth patterns in experiment, but also provides a clue to control the geometric configurations in synthesis.

  7. A simple method for understanding the triangular growth patterns of transition metal dichalcogenide sheets

    SciTech Connect

    Zhu, Siya; Wang, Qian

    2015-10-15

    Triangular nanoflake growth patterns have been commonly observed in synthesis of transition metal dichalcogenide sheets and their hybrid structures. Triangular nanoflakes not only show exceptional properties, but also can serve as building blocks for two or three dimensional structures. In this study, taking the MoS{sub 2} system as a test case, we propose a Matrix method to understand the mechanism of such unique growth pattern. Nanoflakes with different edge types are mathematically described with configuration matrices, and the total formation energy is calculated as the sum of the edge formation energies and the chemical potentials of sulfur and molybdenum. Based on energetics, we find that three triangular patterns with the different edge configurations are energetically more favorable in different ranges of the chemical potential of sulfur, which are in good agreement with experimental observations. Our algorithm has high efficiency and can deal with nanoflakes in microns which are beyond the ability of ab-initio method. This study not only elucidates the mechanism of triangular nanoflake growth patterns in experiment, but also provides a clue to control the geometric configurations in synthesis.

  8. SIMPLE MODELS OF METAL-LINE ABSORPTION AND EMISSION FROM COOL GAS OUTFLOWS

    SciTech Connect

    Prochaska, J. Xavier; Rubin, Kate

    2011-06-10

    We analyze the absorption and emission-line profiles produced by a set of simple, cool gas wind models motivated by galactic-scale outflow observations. We implement Monte Carlo radiative transfer techniques that track the propagation of scattered and fluorescent photons to generate one-dimensional spectra and two-dimensional spectral images. We focus on the Mg II {lambda}{lambda}2796, 2803 doublet and Fe II UV1 multiplet at {lambda} {approx} 2600 A, but the results are applicable to other transitions that trace outflows (e.g., Na I, H I Ly{alpha}, Si II). By design, the resonance transitions show blueshifted absorption but one also predicts strong resonance and fine-structure line emission at roughly the systemic velocity. This line-emission 'fills in' the absorption, reducing the equivalent width by up to 50%, shifting the absorption-line centroid by tens of km s{sup -1}, and reducing the effective opacity near systemic. Analysis of cool gas outflows that ignores this line emission may incorrectly infer that the gas is partially covered, measure a significantly lower peak optical depth, and/or conclude that gas at systemic velocity is absent (e.g., an interstellar or slowly infalling component). Because the Fe II lines are connected by optically thin transitions to fine-structure levels, their profiles more closely reproduce the intrinsic opacity of the wind. Together these results naturally explain the absorption and emission-line characteristics observed for star-forming galaxies at z < 1. We also study a scenario promoted to describe the outflows of z {approx} 3 Lyman break galaxies and find profiles inconsistent with the observations due to scattered photon emission. Although line emission complicates the analysis of absorption-line profiles, the surface brightness profiles offer a unique means of assessing the morphology and size of galactic-scale winds. Furthermore, the kinematics and line ratios offer powerful diagnostics of outflows, motivating deep

  9. Simple Models of Metal-line Absorption and Emission from Cool Gas Outflows

    NASA Astrophysics Data System (ADS)

    Prochaska, J. Xavier; Kasen, Daniel; Rubin, Kate

    2011-06-01

    We analyze the absorption and emission-line profiles produced by a set of simple, cool gas wind models motivated by galactic-scale outflow observations. We implement Monte Carlo radiative transfer techniques that track the propagation of scattered and fluorescent photons to generate one-dimensional spectra and two-dimensional spectral images. We focus on the Mg II λλ2796, 2803 doublet and Fe II UV1 multiplet at λ ≈ 2600 Å, but the results are applicable to other transitions that trace outflows (e.g., Na I, H I Lyα, Si II). By design, the resonance transitions show blueshifted absorption but one also predicts strong resonance and fine-structure line emission at roughly the systemic velocity. This line-emission "fills in" the absorption, reducing the equivalent width by up to 50%, shifting the absorption-line centroid by tens of km s-1, and reducing the effective opacity near systemic. Analysis of cool gas outflows that ignores this line emission may incorrectly infer that the gas is partially covered, measure a significantly lower peak optical depth, and/or conclude that gas at systemic velocity is absent (e.g., an interstellar or slowly infalling component). Because the Fe II lines are connected by optically thin transitions to fine-structure levels, their profiles more closely reproduce the intrinsic opacity of the wind. Together these results naturally explain the absorption and emission-line characteristics observed for star-forming galaxies at z < 1. We also study a scenario promoted to describe the outflows of z ~ 3 Lyman break galaxies and find profiles inconsistent with the observations due to scattered photon emission. Although line emission complicates the analysis of absorption-line profiles, the surface brightness profiles offer a unique means of assessing the morphology and size of galactic-scale winds. Furthermore, the kinematics and line ratios offer powerful diagnostics of outflows, motivating deep, spatially extended spectroscopic

  10. Comparison of residual stresses in Inconel 718 simple parts made by electron beam melting and direct laser metal sintering

    DOE PAGESBeta

    Kolbus, Lindsay M.; Payzant, E. Andrew; Cornwell, Paris A.; Watkins, Thomas R.; Babu, Sudarsanam Suresh; Dehoff, Ryan R.; Duty, Chad E.; Lorenz, M.; Ovchinnikova, O. S.

    2015-01-10

    Residual stress profiles were mapped using neutron diffraction in two simple prism builds of Inconel 718: one fabricated with electron beam melting and the other with direct laser sintering. Spatially indexed stress-free cubes were obtained by EDM sectioning equivalent prisms of similar shape. The (311) interplanar spacing examined for the EDM sectioned sample was compared to the interplanar spacings calculated to fulfill force and moment balance. We have shown that Applying force and moment balance is a necessary supplement to the measurements for the stress-free cubes with respect to accurate stress calculations in additively manufactured components. Furthermore, our work hasmore » shown that residual stresses in electron beam melting parts are much smaller than that of direct laser metal sintering parts.« less

  11. Comparison of residual stresses in Inconel 718 simple parts made by electron beam melting and direct laser metal sintering

    SciTech Connect

    Kolbus, Lindsay M.; Payzant, E. Andrew; Cornwell, Paris A.; Watkins, Thomas R.; Babu, Sudarsanam Suresh; Dehoff, Ryan R.; Duty, Chad E.; Lorenz, M.; Ovchinnikova, O. S.

    2015-01-10

    Residual stress profiles were mapped using neutron diffraction in two simple prism builds of Inconel 718: one fabricated with electron beam melting and the other with direct laser sintering. Spatially indexed stress-free cubes were obtained by EDM sectioning equivalent prisms of similar shape. The (311) interplanar spacing examined for the EDM sectioned sample was compared to the interplanar spacings calculated to fulfill force and moment balance. We have shown that Applying force and moment balance is a necessary supplement to the measurements for the stress-free cubes with respect to accurate stress calculations in additively manufactured components. Furthermore, our work has shown that residual stresses in electron beam melting parts are much smaller than that of direct laser metal sintering parts.

  12. Some characteristics of Ureaplasma urealyticum. Urease activity in a simple buffer: effect of metal ions and sulphydryl inhibitors.

    PubMed

    Swanberg, S L; Masover, G K; Hayflick, L

    1978-10-01

    Urealytic activity of the cytoplasmic fraction of Ureaplasma urealyticum prepared by digitonin lysis was assayed in a simple buffer system (HEPES plus EDTA) by measuring the release of 14CO2 from [14C]urea. The Km of this preparation agreed with our previous observations of the same activity measured in a more complex reaction mixture. The substrate concentration at which maximum velocity occurred was approximately 20 mM. The activity was sensitive to heavy metals and inhibitors which react with sulphydryl groups such as N-ethylmaleimide and p-chloromercuribenzoate. It was not inhibited by Ca2+ or Mg2+ or by the reaction products, ammonia and carbon dioxide. PMID:31413

  13. Photocatalytic Solar Fuel Generation on Semiconductor Nanocrystals

    NASA Astrophysics Data System (ADS)

    Feldmann, Jochen

    2015-03-01

    I will review our scientific work on photocatalytic solar fuel generation utilizing colloidal semiconductor nanocrystals decorated with catalytic metal clusters. In particular, nanocrystals made of CdS, TiO2 and organo-metal halide perovskites will be discussed. Key issues are the role of hole scavangers (M. Berr et al., Appl. Phys. Lett. 100, 223903 (2012)), the size and density of catalytic clusters (M. Berr et al.: Appl. Phys. Lett. 97, 093108 (2010) and Nano Letters 12, 5903 (2012) , and dependencies on external parameters such as pH (T. Simon et al., Nature Mat. 13, 1013 (2014)). Financially supported by the Bavarian Research Cluster ``Solar Technologies Go Hybrid: SolTech''.

  14. Electron-Phonon Coupling and Energy Flow in a Simple Metal beyond the Two-Temperature Approximation

    NASA Astrophysics Data System (ADS)

    Waldecker, Lutz; Bertoni, Roman; Ernstorfer, Ralph; Vorberger, Jan

    2016-04-01

    The electron-phonon coupling and the corresponding energy exchange are investigated experimentally and by ab initio theory in nonequilibrium states of the free-electron metal aluminium. The temporal evolution of the atomic mean-squared displacement in laser-excited thin freestanding films is monitored by femtosecond electron diffraction. The electron-phonon coupling strength is obtained for a range of electronic and lattice temperatures from density functional theory molecular dynamics simulations. The electron-phonon coupling parameter extracted from the experimental data in the framework of a two-temperature model (TTM) deviates significantly from the ab initio values. We introduce a nonthermal lattice model (NLM) for describing nonthermal phonon distributions as a sum of thermal distributions of the three phonon branches. The contributions of individual phonon branches to the electron-phonon coupling are considered independently and found to be dominated by longitudinal acoustic phonons. Using all material parameters from first-principles calculations except the phonon-phonon coupling strength, the prediction of the energy transfer from electrons to phonons by the NLM is in excellent agreement with time-resolved diffraction data. Our results suggest that the TTM is insufficient for describing the microscopic energy flow even for simple metals like aluminium and that the determination of the electron-phonon coupling constant from time-resolved experiments by means of the TTM leads to incorrect values. In contrast, the NLM describing transient phonon populations by three parameters appears to be a sufficient model for quantitatively describing electron-lattice equilibration in aluminium. We discuss the general applicability of the NLM and provide a criterion for the suitability of the two-temperature approximation for other metals.

  15. A simple synthesis method to produce metal oxide loaded carbon paper using bacterial cellulose gel and characterization of its electrochemical behavior in an aqueous electrolyte

    NASA Astrophysics Data System (ADS)

    Miyajima, Naoya; Jinguji, Ken; Matsumura, Taiyu; Matsubara, Toshihiro; Sakane, Hideto; Akatsu, Takashi; Tanaike, Osamu

    2016-04-01

    A simple synthetic chemical process to produce metal oxide loaded carbon papers was developed using bacterial cellulose gel, which consisted of nanometer-sized fibrous cellulose and water. Metal ions were successfully impregnated into the gel via aqueous solution media before drying and carbonization methods resulting in metal oxide contents that were easy to control through variations in the concentration of aqueous solutions. The papers loaded by molybdenum oxides were characterized as pseudocapacitor electrodes preliminary, and the large redox capacitance of the oxides was followed by a conductive fibrous carbon substrate, suggesting that a binder and carbon black additive-free electrode consisting of metal oxides and carbon paper was formed.

  16. Colloidal Nanocrystals Fluoresced by Surface Coordination Complexes

    PubMed Central

    Wang, Guan; Ji, Jianwei; Zhang, Xinwen; Zhang, Yan; Wang, Qiangbin; You, Xiaozeng; Xu, Xiangxing

    2014-01-01

    Colloidal Nanocrystals (NCs) with fluorescence originating from surface complexes are successfully prepared. The components of these NCs range from insulator, semiconductor to metal, with either pure phase, doped or core/shell structures. The photoluminescence of these NCs can be reversibly tuned across the visible to infrared spectrum, and even allow multi-color emission. A light emitting device is fabricated and a new in vivo cell imaging method is performed to demonstrate the power of this technology for emerging applications. PMID:24970242

  17. Inhibition of palm oil oxidation by zeolite nanocrystals.

    PubMed

    Tan, Kok-Hou; Awala, Hussein; Mukti, Rino R; Wong, Ka-Lun; Rigaud, Baptiste; Ling, Tau Chuan; Aleksandrov, Hristiyan A; Koleva, Iskra Z; Vayssilov, Georgi N; Mintova, Svetlana; Ng, Eng-Poh

    2015-05-13

    The efficiency of zeolite X nanocrystals (FAU-type framework structure) containing different extra-framework cations (Li(+), Na(+), K(+), and Ca(2+)) in slowing the thermal oxidation of palm oil is reported. The oxidation study of palm oil is conducted in the presence of zeolite nanocrystals (0.5 wt %) at 150 °C. Several characterization techniques such as visual analysis, colorimetry, rheometry, total acid number (TAN), FT-IR spectroscopy, (1)H NMR spectroscopy, and Karl Fischer analyses are applied to follow the oxidative evolution of the oil. It was found that zeolite nanocrystals decelerate the oxidation of palm oil through stabilization of hydroperoxides, which are the primary oxidation product, and concurrently via adsorption of the secondary oxidation products (alcohols, aldehydes, ketones, carboxylic acids, and esters). In addition to the experimental results, periodic density functional theory (DFT) calculations are performed to elucidate further the oxidation process of the palm oil in the presence of zeolite nanocrystals. The DFT calculations show that the metal complexes formed with peroxides are more stable than the complexes with alkenes with the same ions. The peroxides captured in the zeolite X nanocrystals consequently decelerate further oxidation toward formation of acids. Unlike the monovalent alkali metal cations in the zeolite X nanocrystals (K(+), Na(+), and Li(+)), Ca(2+) reduced the acidity of the oil by neutralizing the acidic carboxylate compounds to COO(-)(Ca(2+))1/2 species. PMID:25897618

  18. Plasmonic engineering of spontaneous emission from silicon nanocrystals

    PubMed Central

    Goffard, Julie; Gérard, Davy; Miska, Patrice; Baudrion, Anne-Laure; Deturche, Régis; Plain, Jérôme

    2013-01-01

    Silicon nanocrystals offer huge advantages compared to other semi-conductor quantum dots as they are made from an abundant, non-toxic material and are compatible with silicon devices. Besides, among a wealth of extraordinary properties ranging from catalysis to nanomedicine, metal nanoparticles are known to increase the radiative emission rate of semiconductor quantum dots. Here, we use gold nanoparticles to accelerate the emission of silicon nanocrystals. The resulting integrated hybrid emitter is 5-fold brighter than bare silicon nanocrystals. We also propose an in-depth analysis highlighting the role of the different physical parameters in the photoluminescence enhancement phenomenon. This result has important implications for the practical use of silicon nanocrystals in optoelectronic devices, for instance for the design of efficient down-shifting devices that could be integrated within future silicon solar cells. PMID:24037020

  19. Synthesis of single-crystalline anisotropic gold nano-crystals via chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Manna, Sohini; Kim, Jong Woo; Takahashi, Yukiko; Shpyrko, Oleg G.; Fullerton, Eric E.

    2016-05-01

    We report on a novel one-step catalyst-free, thermal chemical vapor deposition procedure to synthesize gold nanocrystals on silicon substrates. This approach yields single-crystal nanocrystals with various morphologies, such as prisms, icosahedrons, and five-fold twinned decahedrons. Our approach demonstrates that high-quality anisotropic crystals composed of fcc metals can be produced without the need for surfactants or templates. Compared with the traditional wet chemical synthesis processes, our method enables direct formation of highly pure and single crystalline nanocrystals on solid substrates which have applications in catalysis. We investigated the evolution of gold nanocrystals and established their formation mechanism.

  20. One-Step Facile Surface Engineering of Hydrophobic Nanocrystals with Designer Molecular Recognition

    PubMed Central

    Chen, Tao; Öçsoy, Ismail; Yuan, Quan; Wang, Ruowen; You, Mingxu; Zhao, Zilong; Song, Erqun; Zhang, Xiaobing; Tan, Weihong

    2013-01-01

    High quality nanocrystals have demonstrated substantial potential for biomedical applications. However, being generally hydrophobic, their use has been greatly limited by complicated and inefficient surface engineering that often fails to yield biocompatible nanocrystals with minimal aggregation in biological fluids and active targeting toward specific biomolecules. Using chimeric DNA molecules, we developed a one-step facile surface engineering method for hydrophobic Nanocrystals. The procedure is simple and versatile, generating individual nanocrystals with multiple ligands. In addition, the resulting nanocrystals can actively and specifically target various molecular addresses, varying from nucleic acids to cancer cells. Together, the strategy developed here holds great promise in generating critical technologies needed for biomedical applications of nanocrystals. PMID:22793667

  1. From ligands to binding motifs and beyond; the enhanced versatility of nanocrystal surfaces.

    PubMed

    De Roo, J; De Keukeleere, K; Hens, Z; Van Driessche, I

    2016-09-14

    Surface chemistry bridges the gap between nanocrystal synthesis and their applications. In this respect, the discovery of complex ligand binding motifs on semiconductor quantum dots and metal oxide nanocrystals opens a gateway to new areas of research. The implications are far-reaching, from catalytic model systems to the performance of solar cells. PMID:27461488

  2. Nanocrystal Solar Cells

    SciTech Connect

    Gur, Ilan

    2006-12-15

    This dissertation presents the results of a research agenda aimed at improving integration and stability in nanocrystal-based solar cells through advances in active materials and device architectures. The introduction of 3-dimensional nanocrystals illustrates the potential for improving transport and percolation in hybrid solar cells and enables novel fabrication methods for optimizing integration in these systems. Fabricating cells by sequential deposition allows for solution-based assembly of hybrid composites with controlled and well-characterized dispersion and electrode contact. Hyperbranched nanocrystals emerge as a nearly ideal building block for hybrid cells, allowing the controlled morphologies targeted by templated approaches to be achieved in an easily fabricated solution-cast device. In addition to offering practical benefits to device processing, these approaches offer fundamental insight into the operation of hybrid solar cells, shedding light on key phenomena such as the roles of electrode-contact and percolation behavior in these cells. Finally, all-inorganic nanocrystal solar cells are presented as a wholly new cell concept, illustrating that donor-acceptor charge transfer and directed carrier diffusion can be utilized in a system with no organic components, and that nanocrystals may act as building blocks for efficient, stable, and low-cost thin-film solar cells.

  3. Synthesis of Doped Semiconductor Nanocrystals and Conductive Coatings

    NASA Astrophysics Data System (ADS)

    Wills, Andrew Wilke

    measurements reveal that the nanocrystal Fermi level rises with increasing Al content. The third thrust is achieved by the use of primary dithiocarbamates as ligands to stabilize CdSe, and PbSe / CdSe core/shell nanoparticles. Primary dithiocarbamates bind well to metals but include a weak chemical bond that can be broken with gentle heating. This enables us to bind them to nanoparticles, process the particles into devices, then remove the ligand via gentle heating. Characterization of the ligand-particle interactions show excellent ligand binding to the particle surface and easy ligand removal with heating. After ligand removal, the inter-particle spacing shrinks. Transistor measurements reveal that this reduces the barrier to interparticle electron transport, enhancing the conductivity of the film.

  4. The surface structure of silver-coated gold nanocrystals and its influence on shape control

    DOE PAGESBeta

    Padmos, J. Daniel; Personick, Michelle L.; Tang, Qing; Duchesne, Paul N.; Jiang, De-en; Mirkin, Chad A.; Zhang, Peng

    2015-07-08

    Understanding the surface structure of metal nanocrystals with specific facet indices is important due to its impact on controlling nanocrystal shape and functionality. However, this is particularly challenging for halide-adsorbed nanocrystals due to the difficulty in analysing interactions between metals and light halides (for example, chloride). Here we uncover the surface structures of chloride-adsorbed, silver-coated gold nanocrystals with {111}, {110}, {310} and {720} indexed facets by X-ray absorption spectroscopy and density functional theory modelling. The silver–chloride, silver–silver and silver–gold bonding structures are markedly different between the nanocrystal surfaces, and are sensitive to their formation mechanism and facet type. A uniquemore » approach of combining the density functional theory and experimental/simulated X-ray spectroscopy further verifies the surface structure models and identifies the previously indistinguishable valence state of silver atoms on the nanocrystal surfaces. Overall, this work elucidates the thus-far unknown chloride–metal nanocrystal surface structures and sheds light onto the halide-induced growth mechanism of anisotropic nanocrystals.« less

  5. The surface structure of silver-coated gold nanocrystals and its influence on shape control

    PubMed Central

    Padmos, J. Daniel; Personick, Michelle L.; Tang, Qing; Duchesne, Paul N.; Jiang, De-en; Mirkin, Chad A.; Zhang, Peng

    2015-01-01

    Understanding the surface structure of metal nanocrystals with specific facet indices is important due to its impact on controlling nanocrystal shape and functionality. However, this is particularly challenging for halide-adsorbed nanocrystals due to the difficulty in analysing interactions between metals and light halides (for example, chloride). Here we uncover the surface structures of chloride-adsorbed, silver-coated gold nanocrystals with {111}, {110}, {310} and {720} indexed facets by X-ray absorption spectroscopy and density functional theory modelling. The silver–chloride, silver–silver and silver–gold bonding structures are markedly different between the nanocrystal surfaces, and are sensitive to their formation mechanism and facet type. A unique approach of combining the density functional theory and experimental/simulated X-ray spectroscopy further verifies the surface structure models and identifies the previously indistinguishable valence state of silver atoms on the nanocrystal surfaces. Overall, this work elucidates the thus-far unknown chloride–metal nanocrystal surface structures and sheds light onto the halide-induced growth mechanism of anisotropic nanocrystals. PMID:26153854

  6. The surface structure of silver-coated gold nanocrystals and its influence on shape control

    SciTech Connect

    Padmos, J. Daniel; Personick, Michelle L.; Tang, Qing; Duchesne, Paul N.; Jiang, De-en; Mirkin, Chad A.; Zhang, Peng

    2015-07-08

    Understanding the surface structure of metal nanocrystals with specific facet indices is important due to its impact on controlling nanocrystal shape and functionality. However, this is particularly challenging for halide-adsorbed nanocrystals due to the difficulty in analysing interactions between metals and light halides (for example, chloride). Here we uncover the surface structures of chloride-adsorbed, silver-coated gold nanocrystals with {111}, {110}, {310} and {720} indexed facets by X-ray absorption spectroscopy and density functional theory modelling. The silver–chloride, silver–silver and silver–gold bonding structures are markedly different between the nanocrystal surfaces, and are sensitive to their formation mechanism and facet type. A unique approach of combining the density functional theory and experimental/simulated X-ray spectroscopy further verifies the surface structure models and identifies the previously indistinguishable valence state of silver atoms on the nanocrystal surfaces. Overall, this work elucidates the thus-far unknown chloride–metal nanocrystal surface structures and sheds light onto the halide-induced growth mechanism of anisotropic nanocrystals.

  7. Nonvolatile memory devices based on self-assembled nanocrystals

    NASA Astrophysics Data System (ADS)

    Lee, Jang-Sik

    2013-06-01

    Nonvolatile memory devices are one of the most important components in modern electronic devices. Many efforts have been made to fabricate high-density, low-cost, nonvolatile solid-state memory devices for use in portable/mobile electronic devices such as laptop computers, tablet devices, smart phones, etc. Among the many available nonvolatile memory devices, flash memory devices are of great interest to the electronics industry owing to their simple device structure, enabling high-density memory applications. Flash memory devices in which nanoparticles or nanocrystals are used as the charge-trapping elements have advantages over conventional flash memory devices because the charge-trapping layer and memory performance of the former can be readily optimized. Active research has recently been conducted to fabricate and characterize self-assembled-nanocrystal-based nonvolatile memory devices. We reviewed various strategies for fabricating nanocrystal-based nonvolatile memory devices and discussed the programmable memory properties and the device reliability characteristics of nanocrystal-based memory devices to possibly apply nanocrystal-based memory devices to those used in portable/mobile electronic devices. Finally, novel device applications such as printed/flexible/transparent electronic devices were explored based on nanocrystal-based memory devices.

  8. Synthesis and applications of heterostructured semiconductor nanocrystals

    NASA Astrophysics Data System (ADS)

    Khon, Elena

    Semiconductor nanocrystals (NCs) have been of great interest to researchers for several decades due to their unique optoelectronic properties. These nanoparticles are widely used for a variety of different applications. However, there are many unresolved issues that lower the efficiency and/or stability of devices which incorporate these NCs. Our research is dedicated to addressing these issues by identifying potential problems and resolving them, improving existing systems, generating new synthetic strategies, and/or building new devices. The general strategies for the synthesis of different nanocrystals were established in this work, one of which is the colloidal growth of gold domains onto CdS semiconductor nanocrystals. Control of shape and size was achieved simply by adjusting the temperature and the time of the reaction. Depending on the exact morphology of Au and CdS domains, fabricated nano-composites can undergo evaporation-induced self-assembly onto a substrate, which is very useful for building devices. CdS/Au heterostructures can assemble in two different ways: through end-to-end coupling of Au domains, resulting in the formation of one-dimensional chains; and via side-by-side packing of CdS nanorods, leading to the onset of two-dimensional superlattices. We investigated the nature of exciton-plasmon interactions in Au-tipped CdS nanorods using femtosecond transient absorption spectroscopy. The study demonstrated that the key optoelectronic properties of electrically coupled metal and semiconductor domains are significantly different from those observed in systems with weak inter-domain coupling. In particular, strongly-coupled nanocomposites promote mixing of electronic states at semiconductor-metal domain interfaces, which causes a significant suppression of both plasmon and exciton carrier excitations. Colloidal QDs are starting to replace organic molecules in many different applications, such as organic light emmiting diods (OLEDs), due to their

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

    PubMed

    Caliandro, Rocco; Sibillano, Teresa; Belviso, B Danilo; Scarfiello, Riccardo; Hanson, Jonathan C; Dooryhee, Eric; Manca, Michele; Cozzoli, P Davide; Giannini, Cinzia

    2016-03-01

    We have developed a general X-ray powder diffraction (XPD) methodology for the simultaneous structural and compositional characterization of inorganic nanomaterials. The approach is validated on colloidal tungsten oxide nanocrystals (WO3-x NCs), as a model polymorphic nanoscale material system. Rod-shaped WO3-x NCs with different crystal structure and stoichiometry are comparatively investigated under an inert atmosphere and after prolonged air exposure. An initial structural model for the as-synthesized NCs is preliminarily identified by means of Rietveld analysis against several reference crystal phases, followed by atomic pair distribution function (PDF) refinement of the best-matching candidates (static analysis). Subtle stoichiometry deviations from the corresponding bulk standards are revealed. NCs exposed to air at room temperature are monitored by XPD measurements at scheduled time intervals. The static PDF analysis is complemented with an investigation into the evolution of the WO3-x NC structure, performed by applying the modulation enhanced diffraction technique to the whole time series of XPD profiles (dynamical analysis). Prolonged contact with ambient air is found to cause an appreciable increase in the static disorder of the O atoms in the WO3-x NC lattice, rather than a variation in stoichiometry. The time behavior of such structural change is identified on the basis of multivariate analysis. PMID:26756645

  10. Protein-Nanoreactor-Assisted Synthesis of Semiconductor Nanocrystals for Efficient Cancer Theranostics.

    PubMed

    Yang, Tao; Wang, Yong; Ke, Hengte; Wang, Qiaoli; Lv, Xiaoyan; Wu, Hong; Tang, Yongan; Yang, Xiangliang; Chen, Chunying; Zhao, Yuliang; Chen, Huabing

    2016-07-01

    Transition metal sulfide nanocrystals are developed as a theranostic platform through the protein-nanoreactor approach with facile functionalization for multimodal NIRF/PA/SPECT/CT imaging and photothermal tumor ablation. PMID:27165472

  11. 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

  12. Stabilizing Agents for Drug Nanocrystals: Effect on Bioavailability.

    PubMed

    Tuomela, Annika; Hirvonen, Jouni; Peltonen, Leena

    2016-01-01

    Drug nanocrystals are a versatile option for drug delivery purposes, and while the number of poorly soluble drug materials is all the time increasing, more research in this area is performed. Drug nanocrystals have a simple structure-a solid drug core is surrounded by a layer of stabilizing agent. However, despite the considerably simple structure, the selection of an appropriate stabilizer for a certain drug can be challenging. Mostly, the stabilizer selection is based purely on the requirement of physical stability, e.g., maintaining the nanosized particle size as long as possible after the formation of drug nanocrystals. However, it is also worth taking into account that stabilizer can affect the bioavailability in the final formulation via interactions with cells and cell layers. In addition, formation of nanocrystals is only one process step, and for the final formulation, more excipients are often added to the composition. The role of the stabilizers in the final formulation can be more than only stabilizing the nanocrystal particle size. A good example is the stabilizer's role as cryoprotectant during freeze drying. In this review, the stabilizing effect, role of stabilizers in final nanocrystalline formulations, challenges in reaching in vitro-in vivo correlation with nanocrystalline products, and stabilizers' effect on higher bioavailability are discussed. PMID:27213435

  13. Stabilizing Agents for Drug Nanocrystals: Effect on Bioavailability

    PubMed Central

    Tuomela, Annika; Hirvonen, Jouni; Peltonen, Leena

    2016-01-01

    Drug nanocrystals are a versatile option for drug delivery purposes, and while the number of poorly soluble drug materials is all the time increasing, more research in this area is performed. Drug nanocrystals have a simple structure—a solid drug core is surrounded by a layer of stabilizing agent. However, despite the considerably simple structure, the selection of an appropriate stabilizer for a certain drug can be challenging. Mostly, the stabilizer selection is based purely on the requirement of physical stability, e.g., maintaining the nanosized particle size as long as possible after the formation of drug nanocrystals. However, it is also worth taking into account that stabilizer can affect the bioavailability in the final formulation via interactions with cells and cell layers. In addition, formation of nanocrystals is only one process step, and for the final formulation, more excipients are often added to the composition. The role of the stabilizers in the final formulation can be more than only stabilizing the nanocrystal particle size. A good example is the stabilizer’s role as cryoprotectant during freeze drying. In this review, the stabilizing effect, role of stabilizers in final nanocrystalline formulations, challenges in reaching in vitro–in vivo correlation with nanocrystalline products, and stabilizers’ effect on higher bioavailability are discussed. PMID:27213435

  14. X-ray diffraction and Raman scattering study of thermal-induced phase transformation in vertically aligned TiO 2 nanocrystals grown on sapphire(1 0 0) via metal organic vapor deposition

    NASA Astrophysics Data System (ADS)

    Chen, C. A.; Chen, K. Y.; Huang, Y. S.; Tsai, D. S.; Tiong, K. K.; Chien, F. Z.

    2008-07-01

    We report a detailed study of thermal-induced phase transformation in TiO 2 nanocrystals (NCs) via X-ray diffraction (XRD) and Raman scattering (RS) spectroscopy. Vertically aligned anatase TiO 2(1 1 0) NCs were grown on the sapphire (SA)(1 0 0) substrate at 550 °C by metal organic chemical vapor deposition, using titanium-tetraisopropoxide (TTIP, Ti[OCH(CH 3) 2] 4), as the source reagent. The effects of thermal annealing of TiO 2 NCs in oxygen atmosphere between 600 and 1000 °C were investigated. XRD and RS spectra showed the onset of the phase transformation process from the as-grown anatase TiO 2(1 1 0) NCs into rutile TiO 2(0 0 1) at the annealing temperature of 800 °C. At annealing temperature higher than 900 °C, pure rutile phase of TiO 2(0 0 1) NCs were formed and the crystalline quality of TiO 2 NCs could be further improved upon higher annealing temperature.

  15. Soluble precursors for CuInSe2, CuIn(1-x)Ga(x)Se2, and Cu2ZnSn(S,Se)4 based on colloidal nanocrystals and molecular metal chalcogenide surface ligands.

    PubMed

    Jiang, Chengyang; Lee, Jong-Soo; Talapin, Dmitri V

    2012-03-21

    We report a new platform for design of soluble precursors for CuInSe(2) (CIS), Cu(In(1-x)Ga(x))Se(2) (CIGS), and Cu(2)ZnSn(S,Se)(4) (CZTS) phases for thin-film potovoltaics. To form these complex phases, we used colloidal nanocrystals (NCs) with metal chalcogenide complexes (MCCs) as surface ligands. The MCC ligands both provided colloidal stability and represented essential components of target phase. To obtain soluble precursors for CuInSe(2), we used Cu(2-x)Se NCs capped with In(2)Se(4)(2-) MCC surface ligands or CuInSe(2) NCs capped with {In(2)Cu(2)Se(4)S(3)}(3-) MCCs. A mixture of Cu(2-x)Se and ZnS NCs, both capped with Sn(2)S(6)(4-) or Sn(2)Se(6)(4-) ligands was used for solution deposition of CZTS films. Upon thermal annealing, the inorganic ligands reacted with NC cores forming well-crystallized pure ternary and quaternary phases. Solution-processed CIS and CZTS films featured large grain size and high phase purity, confirming the prospects of this approach for practical applications. PMID:22329720

  16. Preliminary design of a simple passive toe exercise apparatus with a flexible metal hydride actuator for pressure ulcer prevention.

    PubMed

    Ino, Shuichi; Sato, Mitsuru; Hosono, Minako; Nakajima, Sawako; Yamashita, Kazuhiko; Izumi, Takashi

    2010-01-01

    In an aging society, social demands for home-based rehabilitation and assistive technologies by healthcare and welfare services are globally increasing. The progress of quality-of-life technologies and rehabilitation science is a very important and urgent issue for elderly and disabled individuals as well as for their caregivers. Thus, there is a substantial need to develop simple bedside apparatuses for both continuous exercise of joints and for power assistance for standing to prevent and manage disuse syndromes (e.g., pressure ulcers, joint contractures and muscular atrophy). Unfortunately, there are currently no commercially-available actuators compatible with the human requirements of flexibility, quietness, lightness and a high power-to-weight ratio. To fulfill the above demands, we have developed a novel actuation device using a metal hydride (MH) alloy and a laminate film, called the flexible MH actuator, as a human-friendly force generator for healthcare and welfare services. In this paper, we show the basic structure and characteristics of the flexible MH actuator used to create a passive exercise system for preventing disuse syndromes. To evaluate the efficiency of passive exercise for bedsore prevention, subcutaneous blood flow during passive exercise at common pressure-ulcer sites is measured by a laser blood flow meter. The force and range-of-motion angle required for a passive exercise apparatus is also examined with the help of a professional physical therapist. Based on these findings, a prototype of a passive exercise apparatus is fabricated using the flexible MH actuator technology, and its operation characteristics are preliminarily verified using a thermoelectric control system. PMID:21096304

  17. Nanocrystal Inks without Ligands: Stable Colloids of Bare Germanium Nanocrystals

    SciTech Connect

    Holman, Zachary C.; Kortshagen, Uwe R.

    2011-05-11

    Colloidal semiconductor nanocrystals typically have ligands attached to their surfaces that afford solubility in common solvents but hinder charge transport in nanocrystal films. Here, an alternative route is explored in which bare germanium nanocrystals are solubilized by select solvents to form stable colloids without the use of ligands. A survey of candidate solvents shows that germanium nanocrystals are completely solubilized by benzonitrile, likely because of electrostatic stabilization. Films cast from these dispersions are uniform, dense, and smooth, making them suitable for device applications without postdeposition treatment.

  18. 2009 Clusters, Nanocrystals & Nanostructures GRC

    SciTech Connect

    Lai-Sheng Wang

    2009-07-19

    For over thirty years, this Gordon Conference has been the premiere meeting for the field of cluster science, which studies the phenomena that arise when matter becomes small. During its history, participants have witnessed the discovery and development of many novel materials, including C60, carbon nanotubes, semiconductor and metal nanocrystals, and nanowires. In addition to addressing fundamental scientific questions related to these materials, the meeting has always included a discussion of their potential applications. Consequently, this conference has played a critical role in the birth and growth of nanoscience and engineering. The goal of the 2009 Gordon Conference is to continue the forward-looking tradition of this meeting and discuss the most recent advances in the field of clusters, nanocrystals, and nanostructures. As in past meetings, this will include new topics that broaden the field. In particular, a special emphasis will be placed on nanomaterials related to the efficient use, generation, or conversion of energy. For example, we anticipate presentations related to batteries, catalysts, photovoltaics, and thermoelectrics. In addition, we expect to address the controversy surrounding carrier multiplication with a session in which recent results addressing this phenomenon will be discussed and debated. The atmosphere of the conference, which emphasizes the presentation of unpublished results and lengthy discussion periods, ensures that attendees will enjoy a valuable and stimulating experience. Because only a limited number of participants are allowed to attend this conference, and oversubscription is anticipated, we encourage all interested researchers from academia, industry, and government institutions to apply as early as possible. An invitation is not required. We also encourage all attendees to submit their latest results for presentation at the poster sessions. We anticipate that several posters will be selected for 'hot topic' oral

  19. Sorting fluorescent nanocrystals with DNA

    SciTech Connect

    Gerion, Daniele; Parak, Wolfgang J.; Williams, Shara C.; Zanchet, Daniela; Micheel, Christine M.; Alivisatos, A. Paul

    2001-12-10

    Semiconductor nanocrystals with narrow and tunable fluorescence are covalently linked to oligonucleotides. These biocompounds retain the properties of both nanocrystals and DNA. Therefore, different sequences of DNA can be coded with nanocrystals and still preserve their ability to hybridize to their complements. We report the case where four different sequences of DNA are linked to four nanocrystal samples having different colors of emission in the range of 530-640 nm. When the DNA-nanocrystal conjugates are mixed together, it is possible to sort each type of nanoparticle using hybridization on a defined micrometer -size surface containing the complementary oligonucleotide. Detection of sorting requires only a single excitation source and an epifluorescence microscope. The possibility of directing fluorescent nanocrystals towards specific biological targets and detecting them, combined with their superior photo-stability compared to organic dyes, opens the way to improved biolabeling experiments, such as gene mapping on a nanometer scale or multicolor microarray analysis.

  20. A one-step green route to synthesize copper nanocrystals and their applications in catalysis and surface enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Zhang, Pinhua; Sui, Yongming; Wang, Chao; Wang, Yingnan; Cui, Guangliang; Wang, Chunzhong; Liu, Bingbing; Zou, Bo

    2014-04-01

    A nontoxic, simple, inexpensive, and reproducible strategy, which meets the standard of green chemistry, is introduced for the synthesis of copper nanocrystals (Cu NCs) with olive oil as both reducing agent and capping agent. By changing the reaction parameters, the shape, size and surface structure of the Cu NCs can be well controlled. The obtained Cu nanocubes show excellent catalytic properties for the catalytic reduction of dyes and CO oxidation. Moreover, the prepared Cu nanocubes as substrates exhibit surface enhanced Raman scattering (SERS) activity for 4-mercaptopyridine (4-Mpy). Therefore, this facile route provides a useful platform for the fabrication of Cu NCs which have the potential to replace noble metals for certain applications.A nontoxic, simple, inexpensive, and reproducible strategy, which meets the standard of green chemistry, is introduced for the synthesis of copper nanocrystals (Cu NCs) with olive oil as both reducing agent and capping agent. By changing the reaction parameters, the shape, size and surface structure of the Cu NCs can be well controlled. The obtained Cu nanocubes show excellent catalytic properties for the catalytic reduction of dyes and CO oxidation. Moreover, the prepared Cu nanocubes as substrates exhibit surface enhanced Raman scattering (SERS) activity for 4-mercaptopyridine (4-Mpy). Therefore, this facile route provides a useful platform for the fabrication of Cu NCs which have the potential to replace noble metals for certain applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr00412d

  1. Selective decoration of nickel and nickel oxide nanocrystals on multiwalled carbon nanotubes

    SciTech Connect

    Martis, P.; Venugopal, B.R.; Delhalle, J.; Mekhalif, Z.

    2011-05-15

    A simple route to selective decoration of nickel and nickel oxide nanocrystals on multiwalled carbon nanotubes (MWCNTs) using nickel acetylacetonate (NAA) was successfully achieved for the first time. The homogeneously decorated nanocrystals on MWCNTs were investigated for their structure and morphology by various techniques, such as powder X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, field emission scanning electron microscopy and thermogravimetric analysis. It was found that the size distributions of the nanocrystals on MWCNTs ranged from 8 to 15 nm and they were well resolved. The precursor, NAA, was effectively employed to impregnate the MWCNTs, which on calcination at suitable temperatures and in the presence of hydrogen and nitrogen atmosphere gave rise to nickel and nickel oxide nanocrystals, respectively. -- Graphical abstract: Nickel and nickel oxide nanocrystals were selectively and homogeneously decorated on multiwalled carbon nanotubes using nickel acetylacetonate, as a precursor in a simple and efficient route. Display Omitted Highlights: {yields} A simple route for decoration of nickel and nickel oxide nanocrystals on MWCNTs. {yields} Nickel acetylacetonate used as nickel source for the first time to impregnate on MWCNTs. {yields} Selective decoration was achieved by calcination in hydrogen and nitrogen atmospheres. {yields} The as-decorated nickel and nickel oxide nanocrystals are in the range of 8-15 nm.

  2. Calpain inhibitor nanocrystals prepared using Nano Spray Dryer B-90

    PubMed Central

    2012-01-01

    The Nano Spray Dryer B-90 offers a new, simple, and alternative approach for the production of drug nanocrystals. Among attractive drugs, calpain inhibitor that inhibits programmed cell death ‘apoptosis’ is a candidate for curing apoptosis-mediated intractable diseases such as Alzheimer’s disease and Parkinson’s disease. In this study, the preparation of calpain inhibitor nanocrystals using Nano Spray Dryer B-90 was demonstrated. The particle sizes were controlled by means of selecting mesh aperture sizes. The obtained average particle sizes were in the range of around 300 nm to submicron meter. PMID:22863139

  3. Calpain inhibitor nanocrystals prepared using Nano Spray Dryer B-90

    NASA Astrophysics Data System (ADS)

    Baba, Koichi; Nishida, Kohji

    2012-08-01

    The Nano Spray Dryer B-90 offers a new, simple, and alternative approach for the production of drug nanocrystals. Among attractive drugs, calpain inhibitor that inhibits programmed cell death `apoptosis' is a candidate for curing apoptosis-mediated intractable diseases such as Alzheimer's disease and Parkinson's disease. In this study, the preparation of calpain inhibitor nanocrystals using Nano Spray Dryer B-90 was demonstrated. The particle sizes were controlled by means of selecting mesh aperture sizes. The obtained average particle sizes were in the range of around 300 nm to submicron meter.

  4. Calpain inhibitor nanocrystals prepared using Nano Spray Dryer B-90.

    PubMed

    Baba, Koichi; Nishida, Kohji

    2012-01-01

    The Nano Spray Dryer B-90 offers a new, simple, and alternative approach for the production of drug nanocrystals. Among attractive drugs, calpain inhibitor that inhibits programmed cell death 'apoptosis' is a candidate for curing apoptosis-mediated intractable diseases such as Alzheimer's disease and Parkinson's disease. In this study, the preparation of calpain inhibitor nanocrystals using Nano Spray Dryer B-90 was demonstrated. The particle sizes were controlled by means of selecting mesh aperture sizes. The obtained average particle sizes were in the range of around 300 nm to submicron meter. PMID:22863139

  5. Nanocrystal waveguide (NOW) laser

    DOEpatents

    Simpson, John T.; Simpson, Marcus L.; Withrow, Stephen P.; White, Clark W.; Jaiswal, Supriya L.

    2005-02-08

    A solid state laser includes an optical waveguide and a laser cavity including at least one subwavelength mirror disposed in or on the optical waveguide. A plurality of photoluminescent nanocrystals are disposed in the laser cavity. The reflective subwavelength mirror can be a pair of subwavelength resonant gratings (SWG), a pair of photonic crystal structures (PC), or a distributed feedback structure. In the case of a pair of mirrors, a PC which is substantially transmissive at an operating wavelength of the laser can be disposed in the laser cavity between the subwavelength mirrors to improve the mode structure, coherence and overall efficiency of the laser. A method for forming a solid state laser includes the steps of providing an optical waveguide, creating a laser cavity in the optical waveguide by disposing at least one subwavelength mirror on or in the waveguide, and positioning a plurality of photoluminescent nanocrystals in the laser cavity.

  6. Growth of gold nanoclusters and nanocrystals induced by lysozyme protein in thin film conformation

    NASA Astrophysics Data System (ADS)

    Bhowal, Ashim Chandra; Kundu, Sarathi

    2016-08-01

    Structures and growth behavior of gold nanoclusters and nanocrystals have been explored on thin films of globular protein lysozyme by using UV-vis and photoluminescence spectroscopy, X-ray diffraction (XRD) and atomic force microscopy (AFM). A simple and one-step environment friendly method has been used to grow nanocrystals on protein surface from HAuCl4 solution. It has been found that if different interaction times are provided between lysozyme films and HAuCl4 solution, then initially formed tiny gold nanoclusters on protein surface transform into nanocrystals with the passage of time. XRD analysis shows the formation of faced-centered cubic lattice along (1 1 1) crystalline direction and AFM images confirm the presence of circular, rod-like, triangular and hexagonal crystal structures. Langmuir-like growth behavior has been identified for both the gold nanoclusters and nanocrystals formation induced by the lysozyme films, however, nanocrystal growth is relatively slower than nanocluster.

  7. Atomic Structure of Self-Assembled Monolayer of Thiolates on a Tetragonal Au92 Nanocrystal.

    PubMed

    Zeng, Chenjie; Liu, Chong; Chen, Yuxiang; Rosi, Nathaniel L; Jin, Rongchao

    2016-07-20

    Unveiling the ligand binding mode on the crystalline surfaces is important for deciphering the long-standing structural enigma in self-assembled monolayers (SAMs). Here, the binding and patterning structures of thiolates (SR) on the Au(100) crystalline facet are revealed on the basis of the atomic structure of a highly regular, single crystalline Au92(SR)44 nanocrystal. The six exposed facets of this tetragonal nanocrystal give rise to six pieces of "nanoSAMs". We found that thiolates bind to the planar (100) facets of the nanocrystal via a simple bridge-like mode and are assembled into an overlayer with c(2 × 2) symmetry. The Au-S binding mode and translational symmetry in the kernel and on the surface of the Au92 nanocrystal can be generalized infinitely to construct the bulk two-dimensional SAMs and various tetragonal nanocrystals. PMID:27355843

  8. A simple laminate theory using the orthotropic viscoplasticity theory based on overstress. I - In-plane stress-strain relationships for metal matrix composites

    NASA Technical Reports Server (NTRS)

    Krempl, Erhard; Hong, Bor Zen

    1989-01-01

    A macromechanics analysis is presented for the in-plane, anisotropic time-dependent behavior of metal matrix laminates. The small deformation, orthotropic viscoplasticity theory based on overstress represents lamina behavior in a modified simple laminate theory. Material functions and constants can be identified in principle from experiments with laminae. Orthotropic invariants can be repositories for tension-compression asymmetry and for linear elasticity in one direction while the other directions behave in a viscoplastic manner. Computer programs are generated and tested for either unidirectional or symmetric laminates under in-plane loading. Correlations with the experimental results on metal matrix composites are presented.

  9. Seed-mediated growth of palladium nanocrystals: the effect of pseudo-halide thiocyanate ions.

    PubMed

    Zhang, Ling; Niu, Wenxin; Xu, Guobao

    2011-02-01

    In synthesis in a solution phase, adsorbates such as halides can interact selectively with different metal crystal facets and affect the final morphology of nanocrystals. Pseudo-halide thiocyanate ions (SCN-) can also adsorb on the metal surface, but they have never been used for the synthesis of shape-controlled colloidal metal nanocrystals. In this study, we first investigated the effect of SCN- on the morphology of palladium nanocrystals through a seed-mediated growth method. The presence of 1 µM SCN- in the growth solutions could lead to the formation of palladium polyhedra: truncated rhombic dodecahedra enclosed by twelve {110}, eight {111} and six {100} facets. The products were nanocubes enclosed with six {100} facets if cetyltrimethylammonium bromide (CTAB) was the only capping agent. Meanwhile, the mechanism of the effect of SCN- on the morphology of Pd nanocrystals is discussed. PMID:21170425

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

    PubMed

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

    2016-08-24

    Hydrophobic colloidal nanocrystals are typically synthesized and manipulated with commercially available ligands, and surface functionalization is therefore typically limited to a small number of molecules. Here, we report the use of polycatenar ligands derived from polyalkylbenzoates for the direct synthesis of metallic, chalcogenide, pnictide, and oxide nanocrystals. Polycatenar molecules, branched structures bearing diverging chains in which the terminal substitution pattern, functionality, and binding group can be independently modified, offer a modular platform for the development of ligands with targeted properties. Not only are these ligands used for the direct synthesis of monodisperse nanocrystals, but nanocrystals coated with polycatenar ligands self-assemble into softer bcc superlattices that deviate from conventional harder close-packed structures (fcc or hcp) formed by the same nanocrystals coated with commercial ligands. Self-assembly experiments demonstrate that the molecular structure of polycatenar ligands encodes interparticle spacings and attractions, engineering self-assembly, which is tunable from hard sphere to soft sphere behavior. PMID:27472457

  11. Formation of Si nanocrystals utilizing a Au nanoscale island etching mask

    SciTech Connect

    Kang, Y.M.; Lee, S.J.; Kim, D.Y. . E-mail: dykim@dongguk.edu; Kim, T.W.; Woo, Y.-D.; Wang, K.L.

    2005-01-04

    Si nanocrystals were formed by using a Au nanoscale island etching mask. A high-resolution transmission electron microscopy image showed that the Si nanocrystals were created on a SiO{sub x} layer, and the luminescence peak related to Si nanocrystals was observed in the cathodoluminescence spectrum. Capacitance-voltage measurements demonstrate a metal-insulator-semiconductor behavior with a flatband voltage shift for the Al/SiO{sub 2}/nanocrystalline Si/SiO{sub 2}/p-Si structures, indicative of the existence of the Si nanocrystals embedded into the SiO{sub x} layer. These results indicate that Si nanocrystals embedded into the SiO{sub x} layer can be formed by using a Au island etching mask.

  12. Seed-mediated growth of palladium nanocrystals: The effect of pseudo-halide thiocyanate ions

    NASA Astrophysics Data System (ADS)

    Zhang, Ling; Niu, Wenxin; Xu, Guobao

    2011-02-01

    In synthesis in a solution phase, adsorbates such as halides can interact selectively with different metal crystal facets and affect the final morphology of nanocrystals. Pseudo-halide thiocyanate ions (SCN-) can also adsorb on the metal surface, but they have never been used for the synthesis of shape-controlled colloidal metal nanocrystals. In this study, we first investigated the effect of SCN- on the morphology of palladium nanocrystals through a seed-mediated growth method. The presence of 1 µM SCN- in the growth solutions could lead to the formation of palladium polyhedra: truncated rhombic dodecahedra enclosed by twelve {110}, eight {111} and six {100} facets. The products were nanocubes enclosed with six {100} facets if cetyltrimethylammonium bromide (CTAB) was the only capping agent. Meanwhile, the mechanism of the effect of SCN- on the morphology of Pd nanocrystals is discussed.In synthesis in a solution phase, adsorbates such as halides can interact selectively with different metal crystal facets and affect the final morphology of nanocrystals. Pseudo-halide thiocyanate ions (SCN-) can also adsorb on the metal surface, but they have never been used for the synthesis of shape-controlled colloidal metal nanocrystals. In this study, we first investigated the effect of SCN- on the morphology of palladium nanocrystals through a seed-mediated growth method. The presence of 1 µM SCN- in the growth solutions could lead to the formation of palladium polyhedra: truncated rhombic dodecahedra enclosed by twelve {110}, eight {111} and six {100} facets. The products were nanocubes enclosed with six {100} facets if cetyltrimethylammonium bromide (CTAB) was the only capping agent. Meanwhile, the mechanism of the effect of SCN- on the morphology of Pd nanocrystals is discussed. Electronic supplementary information (ESI) available: Additional SEM, TEM and XRD data. See DOI: 10.1039/c0nr00622j

  13. Broadband enhancement of infrared absorption in microbolometers using Ag nanocrystals

    SciTech Connect

    Hyun, Jerome K.; Ahn, Chi Won; Kim, Woo Choong; Kim, Tae Hyun; Hyun, Moon Seop; Kim, Hee Yeoun E-mail: jhpark@nnfc.re.kr; Park, Jae Hong E-mail: jhpark@nnfc.re.kr; Lee, Won-Oh

    2015-12-21

    High performance microbolometers are widely sought for thermal imaging applications. In order to increase the performance limits of microbolometers, the responsivity of the device to broadband infrared (IR) radiation needs to be improved. In this work, we report a simple, quick, and cost-effective approach to modestly enhance the broadband IR response of the device by evaporating Ag nanocrystals onto the light entrance surface of the device. When irradiated with IR light, strong fields are built up within the gaps between adjacent Ag nanocrystals. These fields resistively generate heat in the nanocrystals and underlying substrate, which is transduced into an electrical signal via a resistive sensing element in the device. Through this method, we are able to enhance the IR absorption over a broadband spectrum and improve the responsivity of the device by ∼11%.

  14. Selectivity on Etching: Creation of High-Energy Facets on Copper Nanocrystals for CO2 Electrochemical Reduction.

    PubMed

    Wang, Zhenni; Yang, Guang; Zhang, Zhaorui; Jin, Mingshang; Yin, Yadong

    2016-04-26

    Creating high-energy facets on the surface of catalyst nanocrystals represents a promising method for enhancing their catalytic activity. Herein we show that crystal etching as the reverse process of crystal growth can directly endow nanocrystal surfaces with high-energy facets. The key is to avoid significant modification of the surface energies of the nanocrystal facets by capping effects from solvents, ions, and ligands. Using Cu nanocubes as the starting material, we have successfully demonstrated the creation of high-energy facets in metal nanocrystals by controlled chemical etching. The etched Cu nanocrystals with enriched high-energy {110} facets showed significantly enhanced activity toward CO2 reduction. We believe the etching-based strategy could be extended to the synthesis of nanocrystals of many other catalysts with more active high-energy facets. PMID:26974506

  15. Solution-Processed Large-Area Nanocrystal Arrays of Metal-Organic Frameworks as Wearable, Ultrasensitive, Electronic Skin for Health Monitoring.

    PubMed

    Fu, Xiaolong; Dong, Huanli; Zhen, Yonggang; Hu, Wenping

    2015-07-15

    Pressure sensors based on solution-processed metal-organic frameworks nanowire arrays are fabricated with very low cost, flexibility, high sensitivity, and ease of integration into sensor arrays. Furthermore, the pressure sensors are suitable for monitoring and diagnosing biomedical signals such as radial artery pressure waveforms in real time. PMID:25760306

  16. Simple Machines Made Simple.

    ERIC Educational Resources Information Center

    St. Andre, Ralph E.

    Simple machines have become a lost point of study in elementary schools as teachers continue to have more material to cover. This manual provides hands-on, cooperative learning activities for grades three through eight concerning the six simple machines: wheel and axle, inclined plane, screw, pulley, wedge, and lever. Most activities can be…

  17. 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. PMID:27444048

  18. Electronic spectra of semiconductor nanocrystals

    SciTech Connect

    Alivisatos, A.P.

    1993-12-31

    Semiconductor nanocrystals smaller than the bulk exciton show substantial quantum confinement effects. Recent experiments including Stark effect, resonance Raman, valence band photoemission, and near edge X-ray adsorption will be used to put together a picture of the nanocrystal electronic states.

  19. Photoemission studies of semiconductor nanocrystals

    SciTech Connect

    Hamad, K. S.; Roth, R.; Alivisatos, A. P.

    1997-04-01

    Semiconductor nanocrystals have been the focus of much attention in the last ten years due predominantly to their size dependent optical properties. Namely, the band gap of nanocrystals exhibits a shift to higher energy with decreasing size due to quantum confinement effects. Research in this field has employed primarily optical techniques to study nanocrystals, and in this respect this system has been investigated extensively. In addition, one is able to synthesize monodisperse, crystalline particles of CdS, CdSe, Si, InP, InAs, as well as CdS/HgS/CdS and CdSe/CdS composites. However, optical spectroscopies have proven ambiguous in determining the degree to which electronic excitations are interior or surface admixtures or giving a complete picture of the density of states. Photoemission is a useful technique for understanding the electronic structure of nanocrystals and the effects of quantum confinement, chemical environments of the nanocrystals, and surface coverages. Of particular interest to the authors is the surface composition and structure of these particles, for they have found that much of the behavior of nanocrystals is governed by their surface. Previously, the authors had performed x-ray photoelectron spectroscopy (XPS) on CdSe nanocrystals. XPS has proven to be a powerful tool in that it allows one to determine the composition of the nanocrystal surface.

  20. 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.

  1. Nanocrystal/sol-gel nanocomposites

    DOEpatents

    Petruska, Melissa A.; Klimov, Victor L.

    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

  2. Nanocrystal/sol-gel nanocomposites

    DOEpatents

    Petruska, Melissa A.; Klimov, Victor L.

    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.

  3. Surface effects in atomistic mechanical simulations of Al nanocrystals

    NASA Astrophysics Data System (ADS)

    Munilla, Javier; Castro, Mario; Carnicero, Alberto

    2009-07-01

    Detailed knowledge of the mechanical properties of nanocrystals is crucial for understanding the behavior of micromachining devices. Determining experimentally the elastic and plastic properties of nanocrystals can be very challenging. In this work, we present molecular-dynamics simulations of mechanical properties of Al nanocrystals, both using Lennard-Jones and embedded-atom method potentials. We show that this kind of tests borrowed from mechanical engineering provide helpful insight on the mechanical behavior of nanocrystals. We also provide evidence suggesting that the small scale effects, mainly due to the small surface-to-volume ratio of nanocrystals, are crucial. The main results of our work are the failure of the thermodynamical relations connecting the applied stress and the material strain (additionally, we introduce a simple mathematical framework to account for this effect), the nonequilibrium behavior at the onset of the plastic deformation related to the appearance of long tails (power law) in the distribution of dissipated heat and, finally, the existence of conditions under which the system can experience reversible load-unload cycles in the plastic state.

  4. Excavated Cubic Platinum-Tin Alloy Nanocrystals Constructed from Ultrathin Nanosheets with Enhanced Electrocatalytic Activity.

    PubMed

    Chen, Qiaoli; Yang, Yanan; Cao, Zhenming; Kuang, Qin; Du, Guifen; Jiang, Yaqi; Xie, Zhaoxiong; Zheng, Lansun

    2016-07-25

    Excavated polyhedral noble-metal materials that were built by the orderly assembly of ultrathin nanosheets have both large surface areas and well-defined facets, and therefore could be promising candidates for diverse important applications. In this work, excavated cubic Pt-Sn alloy nanocrystals (NCs) with {110} facets were constructed from twelve nanosheets by a simple co-reduction method with the assistance of the surface regulator polyvinylpyrrolidone. The specific surface area of the excavated cubic Pt-Sn NCs is comparable to that of commercial Pt black despite their larger particle size. The excavated cubic Pt-Sn NCs exhibited superior electrocatalytic activity in terms of both the specific area current density and the mass current density towards methanol oxidation. PMID:27325395

  5. 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.

  6. Mechanical Properties of Nanocrystal Supercrystals

    SciTech Connect

    Tam, Enrico; Podsiadlo, Paul; Shevchenko, Elena; Ogletree, D. Frank; Delplancke-Ogletree, Marie-Paule; Ashby, Paul D.

    2009-12-30

    Colloidal nanocrystals attract significant interest due to their potential applications in electronic, magnetic, and optical devices. Nanocrystal supercrystals (NCSCs) are particularly appealing for their well ordered structure and homogeneity. The interactions between organic ligands that passivate the inorganic nanocrystal cores critically influence their self-organization into supercrystals, By investigating the mechanical properties of supercrystals, we can directly characterize the particle-particle interactions in a well-defined geometry, and gain insight into both the self-assembly process and the potential applications of nanocrystal supercrystals. Here we report nanoindentation studies of well ordered lead-sulfide (Pbs) nanocrystal supercrystals. Their modulus and hardness were found to be similar to soft polymers at 1.7 GPa and 70 MPa respectively and the fractures toughness was 39 KPa/m1/2, revealing the extremely brittle nature of these materials.

  7. Germanium Nanocrystals Embedded in Sapphire

    SciTech Connect

    Xu, Q.; Sharp, I.D.; Liao, C.Y.; Yi, D.O.; Ager III, J.W.; Beeman, J.W.; Yu, K.M.; Chrzan, D.C.; Haller, E.E.

    2005-04-15

    {sup 74}Ge nanocrystals are formed in a sapphire matrix by ion implantation followed by damage. Embedded nanocrystals experience large compressive stress relative to bulk, as embedded in sapphire melt very close to the bulk melting point (Tm = 936 C) whereas experience considerably lower stresses. Also, in situ TEM reveals that nanocrystals ion-beam-synthesized nanocrystals embedded in silica are observed to be spherical and measured by Raman spectroscopy of the zone center optical phonon. In contrast, reveals that the nanocrystals are faceted and have a bi-modal size distribution. Notably, the matrix remains crystalline despite the large implantation dose and corresponding thermal annealing. Transmission electron microscopy (TEM) of as-grown samples those embedded in silica exhibit a significant melting point hysteresis around T{sub m}.

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

    PubMed

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

    2015-11-15

    decreasing the mole fraction of [Ant(6)]-RU006 against the total concentration of [Ant(6)]-RU006 and [Phe(6)]-RU006: absorption spectra similar to that for RU006 were obtained. Differences in the redox properties of the anthracene and naphthalene moieties scarcely affected morphology. We propose that construction of an appropriate hydrophobic cavity is important for templating gold nanocrystal architectures by peptide self-assembly. This mechanism would be applicable for developing simple, low toxicity, mild synthetic methods for constructing metallic nanomaterials for therapeutic use. PMID:26521037

  9. Size-Controlled TiO2 nanocrystals with exposed {001} and {101} facets strongly linking to graphene oxide via p-Phenylenediamine for efficient photocatalytic degradation of fulvic acids.

    PubMed

    Yan, Wen-Yuan; Zhou, Qi; Chen, Xing; Yang, Yong; Zhang, Yong; Huang, Xing-Jiu; Wu, Yu-Cheng

    2016-08-15

    Photocatalytic degradation is one of the most promising methods for removal of fulvic acids (FA), which is a typical category of natural organic contamination in groundwater. In this paper, TiO2/graphene nanocomposites (N-RGO/TiO2) were prepared via simple chemical functionalization and one-step hydrothermal method for efficient photodegradation of FA under illumination of a xenon lamp as light source. Here, p-phenylenediamine was used as not only the linkage chemical agent between TiO2 nanocrystals and graphene, but also the nitrogen dopant for TiO2 nanocrystals and graphene. During the hydrothermal process, facets of TiO2 nanocrystals were modulated with addition of HF, and sizes of TiO2 nanocrystals were controlled by the contents of graphene oxide functionalized with p-phenylenediamine (RGO-NH2). The obtained N-RGO/TiO2 nanocomposites exhibited a much higher photocatalytic activity and stability for degradation of methyl blue (MB) and FA compared with other TiO2 samples under xenon lamp irradiation. For the third cycle, the 10wt%N-RGO/TiO2 catalyst maintains high photoactivity (87%) for the degradation of FA, which is much better than the TiO2-N/F (61%) in 3h. This approach supplies a new strategy to design and synthesize metal oxide and graphene oxide nanocomposites with highly efficient photocatalytic performance. PMID:27107234

  10. 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. PMID:23651396

  11. Silicon nanocrystal inks, films, and methods

    DOEpatents

    Wheeler, Lance Michael; Kortshagen, Uwe Richard

    2015-09-01

    Silicon nanocrystal inks and films, and methods of making and using silicon nanocrystal inks and films, are disclosed herein. In certain embodiments the nanocrystal inks and films include halide-terminated (e.g., chloride-terminated) and/or halide and hydrogen-terminated nanocrystals of silicon or alloys thereof. Silicon nanocrystal inks and films can be used, for example, to prepare semiconductor devices.

  12. Labelling of silica microspheres with fluorescent lanthanide-doped LaF3 nanocrystals

    NASA Astrophysics Data System (ADS)

    Zhang, Yong; Lu, Meihua

    2007-07-01

    Fluorescent microspheres have been demonstrated to be useful in a variety of biological applications. Fluorescent silica or polymer microspheres have been produced by incorporation of chromophores into the microspheres, which usually produces microspheres with nonuniform sizes and reduced fluorescence. Here we present a simple and straightforward method to produce silica microspheres with fluorescent lanthanide-doped LaF3 nanocrystals grown on the surface. LaF3 nanocrystals are in situ grown on silica microspheres of different sizes to form a raspberry-like structure. The microspheres exhibit strong fluorescence and the colour could be altered by changing the lanthanide ions doped in LaF3 nanocrystals.

  13. Universal Quake Statistics: From Compressed Nanocrystals to Earthquakes

    SciTech Connect

    Uhl, Jonathan T.; Pathak, Shivesh; Schorlemmer, Danijel; Liu, Xin; Swindeman, Ryan; Brinkman, Braden A. W.; LeBlanc, Michael; Tsekenis, Georgios; Friedman, Nir; Behringer, Robert; Denisov, Dmitry; Schall, Peter; Gu, Xiaojun; Wright, Wendelin J.; Hufnagel, Todd; Jennings, Andrew; Greer, Julia R.; Liaw, P. K.; Becker, Thorsten; Dresen, Georg; Dahmen, Karin A.

    2015-11-17

    Slowly-compressed single crystals, bulk metallic glasses (BMGs), rocks, granular materials, and the earth all deform via intermittent slips or “quakes”. We find that although these systems span 12 decades in length scale, they all show the same scaling behavior for their slip size distributions and other statistical properties. Remarkably, the size distributions follow the same power law multiplied with the same exponential cutoff. The cutoff grows with applied force for materials spanning length scales from nanometers to kilometers. The tuneability of the cutoff with stress reflects “tuned critical” behavior, rather than self-organized criticality (SOC), which would imply stress-independence. A simple mean field model for avalanches of slipping weak spots explains the agreement across scales. It predicts the observed slip-size distributions and the observed stressdependent cutoff function. In conclusion, the results enable extrapolations from one scale to another, and from one force to another, across different materials and structures, from nanocrystals to earthquakes.

  14. Universal Quake Statistics: From Compressed Nanocrystals to Earthquakes

    NASA Astrophysics Data System (ADS)

    Uhl, Jonathan T.; Pathak, Shivesh; Schorlemmer, Danijel; Liu, Xin; Swindeman, Ryan; Brinkman, Braden A. W.; Leblanc, Michael; Tsekenis, Georgios; Friedman, Nir; Behringer, Robert; Denisov, Dmitry; Schall, Peter; Gu, Xiaojun; Wright, Wendelin J.; Hufnagel, Todd; Jennings, Andrew; Greer, Julia R.; Liaw, P. K.; Becker, Thorsten; Dresen, Georg; Dahmen, Karin A.

    2015-11-01

    Slowly-compressed single crystals, bulk metallic glasses (BMGs), rocks, granular materials, and the earth all deform via intermittent slips or “quakes”. We find that although these systems span 12 decades in length scale, they all show the same scaling behavior for their slip size distributions and other statistical properties. Remarkably, the size distributions follow the same power law multiplied with the same exponential cutoff. The cutoff grows with applied force for materials spanning length scales from nanometers to kilometers. The tuneability of the cutoff with stress reflects “tuned critical” behavior, rather than self-organized criticality (SOC), which would imply stress-independence. A simple mean field model for avalanches of slipping weak spots explains the agreement across scales. It predicts the observed slip-size distributions and the observed stress-dependent cutoff function. The results enable extrapolations from one scale to another, and from one force to another, across different materials and structures, from nanocrystals to earthquakes.

  15. Universal Quake Statistics: From Compressed Nanocrystals to Earthquakes

    PubMed Central

    Uhl, Jonathan T.; Pathak, Shivesh; Schorlemmer, Danijel; Liu, Xin; Swindeman, Ryan; Brinkman, Braden A. W.; LeBlanc, Michael; Tsekenis, Georgios; Friedman, Nir; Behringer, Robert; Denisov, Dmitry; Schall, Peter; Gu, Xiaojun; Wright, Wendelin J.; Hufnagel, Todd; Jennings, Andrew; Greer, Julia R.; Liaw, P. K.; Becker, Thorsten; Dresen, Georg; Dahmen, Karin A.

    2015-01-01

    Slowly-compressed single crystals, bulk metallic glasses (BMGs), rocks, granular materials, and the earth all deform via intermittent slips or “quakes”. We find that although these systems span 12 decades in length scale, they all show the same scaling behavior for their slip size distributions and other statistical properties. Remarkably, the size distributions follow the same power law multiplied with the same exponential cutoff. The cutoff grows with applied force for materials spanning length scales from nanometers to kilometers. The tuneability of the cutoff with stress reflects “tuned critical” behavior, rather than self-organized criticality (SOC), which would imply stress-independence. A simple mean field model for avalanches of slipping weak spots explains the agreement across scales. It predicts the observed slip-size distributions and the observed stress-dependent cutoff function. The results enable extrapolations from one scale to another, and from one force to another, across different materials and structures, from nanocrystals to earthquakes. PMID:26572103

  16. Nanocrystals and quantum dots formed by high-dose ion implantation

    SciTech Connect

    White, C.W.; Budai, J.D.; Zhu, J.G.; Withrow, S.P.; Hembree, D.M.; Henderson, D.O.; Ueda, A.; Tung, Y.S.; Mu, R.

    1996-01-01

    Ion implantation and thermal annealing have been used to produce a wide range of nanocrystals and quantum dots in amorphous (SiO{sub 2}) and crystalline (Al{sub 2}O{sub 3}) matrices. Nanocrystals of metals (Au), elemental semiconductors (Si and Ge), and even compound semiconductors (SiGe, CdSe, CdS) have been produced. In amorphous matrices, the nanocrystals are randomly oriented, but in crystalline matrices they are three dimensionally aligned. Evidence for photoluminescence and quantum confinement effects are presented.

  17. Biopolymer coated gold nanocrystals prepared using the green chemistry approach and their shape-dependent catalytic and surface-enhanced Raman scattering properties.

    PubMed

    Chou, Chih-Wei; Hsieh, Hui-Hsuan; Hseu, You-Cheng; Chen, Ko-Shao; Wang, Gou-Jen; Chang, Hsien-Chang; Pan, Yong-Li; Wei, Yi-Syuan; Chang, Ko Hsin; Harn, Yeu-Wei

    2013-07-21

    This study deals with the preparation of multi-shaped nanoscale gold crystals under synthetically simple, green, and efficient conditions using a seed-mediated growth approach in the presence of hyaluronic acid (HA). These highly biocompatible multi-shaped gold nanocrystals were examined to evaluate their catalytic and surface enhanced Raman scattering (SERS) properties. The results show that the size and shape of the nanocrystals are mainly correlated to the amount of seed, seed size, HA concentration, and reaction temperature. Gold seeds accelerate the reduction of the gold precursor to form gold nanocrystals using HA. The HA serves as a reducing agent and a growth template for the reduction of Au(III) and nanocrystal stabilization. The multi-shaped gold nanocrystals showed superior catalytic properties and higher SERS performance. The simple, green approach efficiently controls the nanocrystals and creates many opportunities for future applications. PMID:23728083

  18. Synthesis and characterizations of nanoribbons and monodispersed nanocrystals of CuBr

    SciTech Connect

    Yang Ming; Zhu Junjie . E-mail: jjzhu@nju.edu.cn

    2005-02-15

    Nanoribbons and monodispersed nanocrystals of CuBr have been prepared by a simple reaction between CuO suspension, NH{sub 2}OH.HCl and KBr in the presence of deionized gelatin at 10 deg. C. The products were characterized by X-ray powder diffraction, transmission electron microscopy and UV-vis absorption spectroscopy. The sizes of the monodispersed nanocrystals of CuBr were estimated by Debye-Scherrer formula according to XRD spectrum.

  19. Theoretical and experimental investigation of bonding of simple ligands to metal complexes as reflected in their photoelectron spectra

    NASA Astrophysics Data System (ADS)

    Loubriel, G. M.

    1980-03-01

    The interaction between small molecules and transition metal atoms is investigated. Nitric oxide adsorbed on clean metal surfaces and transition metal complexes like Cr(NO)4, Cr(CO)6 and Ni(CO)4 were studied. The approach used was to learn as much as possible about the electronic structure and bonding in carbonyls and nitrosyls where the atomic positions were known and use this knowledge to help determine the bonding geometry of NO adsorbed on Ni(100). In addition to the analysis of photoemission, theoretical calculations of electronic structure via the self-consistent field X alpha multiple scattering technique were performed. The bonding of NO to transition metal atoms occurs mainly through the interaction of the levels of the metal atom and the 2 pi level of NO. In Cr(NO)4 this bonding is reflected in a charge transfer of about half an electron into the 2 pi level of each one of the NO molecules. The results of first principles calculations of shakeup energies and shakeup intensities for the photo-electron spectra of carbonyls and nitrosyls are reported. The mechanisms by which core holes produced by the photo-excitation are screened are discussed. The results for Ni(CO)4 and Cr(NO)4 are in excellent agreement with experiment.

  20. Biomolecular Assembly of Gold Nanocrystals

    SciTech Connect

    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 in 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.

  1. Heavy metals binding to biosorbents. Insights into Non-competitive models from a simple pH-dependent model.

    PubMed

    Plazinski, Wojciech; Rudzinski, Wladyslaw

    2010-10-15

    The possible explanation for the applicability of NCAMs (Non-Competitive Adsorption Models, i.e. the models corresponding to the Langmuir model in which the maximum uptake value is pH-dependent) for biosorption systems is proposed. Both the metal ion speciation in the bulk solution and the formation of multidentate surface complexes are taken into account. This combined effect can be responsible for the specific behaviour of experimental metal sorption isotherms, measured at different pHs and described well by NCAMs. This concept finds its support in the numerical investigations performed by using the model biosorbent and Cu, Cd and Pb as heavy metals. Acid-base properties of typical biosorbent surfaces are also considered. PMID:20580211

  2. Size control and quantum confinement in Cu2ZnSnS4 nanocrystals.

    PubMed

    Khare, Ankur; Wills, Andrew W; Ammerman, Lauren M; Norris, David J; Aydil, Eray S

    2011-11-14

    Starting with metal dithiocarbamate complexes, we synthesize colloidal Cu(2)ZnSnS(4) (CZTS) nanocrystals with diameters ranging from 2 to 7 nm. Structural and Raman scattering data confirm that CZTS is obtained rather than other possible material phases. The optical absorption spectra of nanocrystals with diameters less than 3 nm show a shift to higher energy due to quantum confinement. PMID:21952415

  3. Pyramidal and Chiral Groupings of Gold Nanocrystals Assembled Using DNA Scaffolds

    SciTech Connect

    Mastroianni, Alexander; Claridge, Shelley; Alivisatos, A. Paul

    2009-03-30

    Nanostructures constructed from metal and semiconductor nanocrystals conjugated to, and organized by DNA are an emerging class of material with collective optical properties. We created discrete pyramids of DNA with gold nanocrystals at the tips. By taking small angle X-ray scattering (SAXS) measurments from solutions of these pyramids we confirmed that this pyramidal geometry creates structures which are more rigid in solution than linear DNA. We then took advantage of the tetrahedral symmetry to demonstrate construction of chiral nanostructures.

  4. Separation of single-walled carbon nanotubes into metallic and semiconducting groups: a simple and large-scale method

    NASA Astrophysics Data System (ADS)

    Lu, Jing; Maeda, Y.

    2006-03-01

    Separation of a large number of single-walled carbon nanotubes (SWNTs) into groups each with specifically metallic and semiconducting properties is an extremely important task for technology application. Even though effective methods (1, 2) have been devised, they suffer from drawbacks such as either the yield is low (3) or expense is high (4). In this work, we study the problem from a theoretical approach, we notice that based on the first principles calculations the binding strengths of methylamine to the semiconducting [13, 0] SWNT are only 36˜61% of that to the metallic [7, 7] SWNT, which suggests that the amines is much more attractive toward the pure metallic than the semiconducting SWNTs. Therefore starting from as-prepared SWNTs and with the assistance of amines, we achieved SWNTs with enriched metallic properties over semiconducting in a convenient and large-scale manner. References: (1) D. Chattopadhyay, L. Galeska, F. Papadimitrakopoulos, Journal of the American Chemical Society 125, 3370 (MAR 19, 2003). (2) H. P. Li et al., Journal of the American Chemical Society 126, 1014 (FEB 4, 2004). (3) R. Krupke, F. Hennrich, H. von Lohneysen, M. Kappes, SCIENCE 301, 344 (JUL 18, 2003). (4) M. Zheng et al., Science 302, 1545 (NOV 28, 2003).

  5. The simulation of a criticality accident excursion occurring in a simple fast metal system using the coupled neutronic-hydrodynamic method

    SciTech Connect

    Myers, W.L.

    1996-12-31

    Analysis of a criticality accident scenario occuring in a simple fast metal system using the coupled neutronic-hydrodynamic method is demonstrated by examining the last Godiva-I criticality accident. The basis tools and information for creating a coupled neutronic-hydrodynamic code are presented. Simplifying assumptions and approximations for creating an idealized model for the Godiva-I system are discussed. Estimates of the total energy generation and the maximum attainable kinetic energy yield are the most important results that are obtained from the code. With modifications, the methodology presented in this paper can be extended to analyze criticality accident excursions in other kinds of nuclear systems.

  6. Nanocrystal solids: Order and progress

    NASA Astrophysics Data System (ADS)

    Delerue, Christophe

    2016-05-01

    Quantification of structural disorder and electron localization in superlattices of colloidal nanocrystals shows that minimizing variations in size and epitaxial connections is key to enhance the electronic properties of these materials.

  7. A simple solution combustion route for the preparation of metal-doped TiO2 nanoparticles and their photocatalytic degradation properties.

    PubMed

    Ni, Yonghong; Zhu, Yan; Ma, Xiang

    2011-04-14

    In this paper, we report the successful synthesis of metal ion-doped TiO(2) nanoparticles via a simple solution combustion method employing a mixture of ethanol and ethyleneglycol (v/v = 30/20) as the solvent, tetra-n-butyl titanate [Ti(OC(4)H(9))(4), TBOT] as the titanium source and oxygen gas in the atmosphere as the oxygen source, in the presence of small amounts of metal ions such as Cu(2+), Mn(2+), Ce(3+) and Sn(4+). The as-obtained products were characterized by means of powder X-ray diffraction (XRD), energy dispersive X-ray spectrometry (EDS) and scanning electron microscopy (SEM). The UV-vis diffuse reflectance spectra (DRS) and photoluminescence (PL) spectra of various metal ion-doped products were investigated. Experiments showed that the metal ion-doped TiO(2) nanoparticles presented a stronger photocatalytic ability for the degradation of organic dyes, including Pyronine B, Safranine T and Methylene blue (MB), under visible light/254 nm UV light irradiation than commercial P25 within the same time. PMID:21369610

  8. Simple whole-cell biodetection and bioremediation of heavy metals based on an engineered lead-specific operon.

    PubMed

    Wei, Wei; Liu, Xiangzhi; Sun, Peiqing; Wang, Xin; Zhu, Hong; Hong, Mei; Mao, Zong-Wan; Zhao, Jing

    2014-03-18

    A lead-specific binding protein, PbrR, and promoter pbr from the lead resistance operon, pbr, of Cupriavidus metallidurans CH34 was incorporated into E. coli in conjunction with an engineered downstream RFP (red fluorescence protein), which allowed for highly sensitive and selective whole-cell detection of lead ions. The subsequent display of PbrR on the E. coli cell surface permitted selective adsorption of lead ions from solution containing various heavy metal ions. The surface-engineered E. coli bacteria effectively protected Arabidopsis thaliana seed germination from the toxicity of lead ions at high concentrations. Engineering the E. coli bacteria harboring these lead-specific elements from the pbr operon may potentially be a valuable general strategy for biodetection and bioremediation of toxic heavy metal ions in the environment. PMID:24564581

  9. Nanocrystal Optoelectronic Devices in Plasmonic Nanojunctions

    NASA Astrophysics Data System (ADS)

    Evans, Kenneth Mellinger

    Optical trapping is an important tool for studying and manipulating nanoscale objects. Recent experiments have shown that subwavelength control of nanoparticles is possible by using patterned plasmonic nanostructures, rather than using a laser directly, to generate the electric fields necessary for particle trapping. In this thesis we present a theoretical model and experimental evidence for plasmonic optical trapping in nanoscale metal junctions. Further, we examine the use of the resultant devices as ultrasmall photodectors. Electromigrated nanojunctions, or "nanogaps", have a well-established plasmon resonance in the near-IR, leading to electric field enhancements large enough for single-molecule sensitivity in Surface-Enhance Raman (SERS) measurements. While molecule-based devices have been carefully studied, optically and electrically prob- ing individual quantum dots in nanoscale metal junctions remains relatively unex- plored. Plasmon-based optical trapping of quantum dots into prefabricated struc- tures could allow for inexpensive, scalable luminescent devices which are fully integrable into established silicon-based fabrication techniques. Additionally, these metal-nanocrystal-metal structures are ideal candidates to study optoelectronics in ultrasmall nanocrystals-based structures, as well as more exotic nanoscale phenom- ena such as blinking, plasmon-exciton interactions, and surface-enhanced fluorescence (SEF). We present experimental data supporting plasmon-based optical trapping in the nanogap geometry, and a corresponding numerical model of the electric field-generated forces in the nanogap geometry. Further, we give proof-of-concept measurements of photoconductance in the resultant quantum dot-based devices, as well as challenges and improvements moving forward.

  10. Early stage of nanocrystal growth

    SciTech Connect

    2012-01-01

    Berkeley Lab researchers at the Molecular Foundry have elucidated important mechanisms behind oriented attachment, the phenomenon that drives biomineralization and the growth of nanocrystals. This electron microscopy movie shows the early stage of nanocrystal growth. Nanoparticles make transient contact at many points and orientations until their lattices are perfectly matched. The particles then make a sudden jump-to-contact to form attached aggregates. (Movie courtesy of Jim DeYoreo)

  11. Effects of aqueous stable fullerene nanocrystal (nC60) on copper (trace necessary nutrient metal): Enhanced toxicity and accumulation of copper in Daphnia magna.

    PubMed

    Tao, Xianji; He, Yiliang; Fortner, John D; Chen, Yongsheng; Hughes, Joseph B

    2013-08-01

    Our focus herein is to evaluate the potential interaction between nC60 and copper, a trace necessary metal, in light of the impact on toxicity. The non-observable effects concentration (NOEC) of nC60 was confirmed as 100μgL(-1) before. When Daphnia magna was exposed to the mixture of copper solution and nC60 suspension (100μgL(-1)), LC50 of 48h was lower than that when they were exposed to copper solution alone. This result clearly showed the decrease in NOEC of copper at the presence of nC60. Cu(2+)-ATPase activity was enhanced at the presence of nC60, indicating that copper transport involved with the uptake, distribution and depuration in body was increased. We further conducted experiments on accumulation of copper in D. magna. The observed equilibrium copper concentration in D. magna in the mixture of 100μgL(-1) nC60 and 1μgL(-1) copper solution reached 131μg (kg wet weight)(-1), which was more than twice that in copper solution only: 60μg (kg wet weight)(-1). This result demonstrated that the accumulation of copper in D. magna was significantly enhanced at the presence of even low nC60 concentration. Experiments also showed that copper was quickly adsorbed onto nC60. The absorption of copper onto D. magna was statistically correlated to the absorption of nC60 onto D. magna; this might be caused by nC60 facilitating the transfer of copper into D. magna. The absorption and desorption of copper to nC60 (pH=5.0) reached equilibrium quickly, which may be involved with the co-bioaccumulation and decrease in NOEC of Cu(2+) and nC60. PMID:23755985

  12. Assemblies of Cellulose Nanocrystals

    NASA Astrophysics Data System (ADS)

    Kumacheva, Eugenia

    The entropically driven coassembly of nanorods (cellulose nanocrystals, CNCs) and different types of nanoparticles (NPs), including dye-labeled latex NPs, carbon dots and plasmonic NPs was experimentally studied in aqueous suspensions and in solid films. In mixed CNC-NP suspensions, phase separation into an isotropic NP-rich and a chiral nematic CNC-rich phase took place; the latter contained a significant amount of NPs. Drying the mixed suspension resulted in CNC-NP films with planar disordered layers of NPs, which alternated with chiral nematic CNC-rich regions. In addition, NPs were embedded in the chiral nematic domains. The stratified morphology of the films, together with a random distribution of NPs in the anisotropic phase, led to the films having close-to-uniform fluorescence, birefringence, and circular dichroism properties.

  13. Mixed semiconductor nanocrystal compositions

    DOEpatents

    Maskaly, Garry R.; Schaller, Richard D.; Klimov, Victor I.

    2011-02-15

    Composition comprising one or more energy donors and one or more energy acceptors, wherein energy is transferred from the energy donor to the energy acceptor and wherein: the energy acceptor is a colloidal nanocrystal having a lower band gap energy than the energy donor; the energy donor and the energy acceptor are separated by a distance of 40 nm or less; wherein the average peak absorption energy of the acceptor is at least 20 meV greater than the average peak emission energy of the energy donor; and wherein the ratio of the number of energy donors to the number of energy acceptors is from about 2:1 to about 1000:1.

  14. Luminescent nanocrystal stress gauge

    PubMed Central

    Choi, Charina L.; Koski, Kristie J.; Olson, Andrew C. K.; Alivisatos, A. Paul

    2010-01-01

    Microscale mechanical forces can determine important outcomes ranging from the site of material fracture to stem cell fate. However, local stresses in a vast majority of systems cannot be measured due to the limitations of current techniques. In this work, we present the design and implementation of the CdSe-CdS core-shell tetrapod nanocrystal, a local stress sensor with bright luminescence readout. We calibrate the tetrapod luminescence response to stress and use the luminescence signal to report the spatial distribution of local stresses in single polyester fibers under uniaxial strain. The bright stress-dependent emission of the tetrapod, its nanoscale size, and its colloidal nature provide a unique tool that may be incorporated into a variety of micromechanical systems including materials and biological samples to quantify local stresses with high spatial resolution. PMID:21098301

  15. Relaxation of the structure of simple metal ion complexes in aqueous solutions at up to supercritical conditions

    USGS Publications Warehouse

    Mayanovic, Robert A.; Jayanetti, Sumedha; Anderson, Alan J.; Bassett, William A.; Chou, I.-Ming

    2003-01-01

    Recently x-ray absorption fine structure (XAFS) studies of various ions in aqueous solutions showed a variation of cation-ligand bond lengths, often coupled with other structure changes, with increasing temperatures. Thus, the variations of the structure of several metal ion complexes with temperature based on observations from the X-ray absorption fine structure (XAFS) studies in the hope that it will stimulate the development of either first- principles theory or molecular dynamics simulations that might adequately describes these results are discussed.

  16. Demixion in simple liquid metals alloys comparative investigation of non local and local pseudopotentials: example of LiNa

    NASA Astrophysics Data System (ADS)

    Takhloukh, A.; Grosdidier, B.; Hellal, S.; Regnaut, C.

    2008-02-01

    Using perturbation theory and classical molecular dynamics simulations, we study the static structure and demixing behaviour of the liquid LiNa alloy from the pseudopotential approach and different classes of models. We find that the norm conserving pseudopotential does not lead to demixing while various local models, with few adjustable parameters correctly predict the structure and spinodal unstability in the alloy. Transferability of the pseudopotential to the alloy is improved if the parameters are fitted to some bulk or structural properties of the pure metal. We find that demixion can be predicted when the structure factors of the pure liquid Li and Na are reasonably reproduced from such pseudopotentials.

  17. The solvothermal synthesis of magnetic iron oxide nanocrystals and the preparation of hybrid poly(L-lactide)-polyethyleneimine magnetic particles.

    PubMed

    Stojanović, Zoran; Otoničar, Mojca; Lee, Jongwook; Stevanović, Magdalena M; Hwang, Mintai P; Lee, Kwan Hyi; Choi, Jonghoon; Uskoković, Dragan

    2013-09-01

    We report a simple and green procedure for the preparation of magnetic iron oxide nanocrystals via solvothermal synthesis. The nanocrystal synthesis was carried out under mild conditions in the water-ethanol-oleic acid solvent system with the use of the oleate anion as a surface modifier of nanocrystals and glucose as a reducing agent. Specific conditions for homogenous precipitation achieved in such a reaction system lead to the formation of uniform high-quality nanocrystals down to 5 nm in diameter. The obtained hydrophobic nanocrystals can easily be converted to hydrophilic magnetic nanoparticles by being immobilized in a poly(L-lactide)-polyethyleneimine polymeric matrix. These hybrid nano-constructs may find various biomedical applications, such as magnetic separation, gene transfection and/or magnetic resonance imaging. PMID:23660309

  18. Polymer nanocomposite photovoltaics utilizing CdSe nanocrystals capped with a thermally cleavable solubilizing ligand

    NASA Astrophysics Data System (ADS)

    Seo, Jangwon; Kim, Won Jin; Kim, Sung Jin; Lee, Kwang-Sup; Cartwright, A. N.; Prasad, Paras N.

    2009-03-01

    We demonstrate a relative improvement in power conversion efficiency of polymer nanocomposite photovoltaic cells consisting of poly(3-hexylthiophene) (P3HT) functionalized CdSe nanocrystals. Thermal deprotection processing of the tert-buthoxycarbonyl moiety in the carbamate ligand surrounding the surface of CdSe nanocrystal significantly shortened the length of the ligand between nanocrystals and between the nanocrystal and the polymer matrix. The resulting device performance was investigated as a function of the composition ratio of P3HT/CdSe and the heating temperature. This simple and straightforward ligand deprotection strategy resulted in a significant increase in current density due to improvement of charge transport between the constituent materials.

  19. Preparation of ZnSe Nanocrystals Using Water-in-Oil Microemulsions

    NASA Astrophysics Data System (ADS)

    Kim, Hyun Soo; Kim, Jong Sung; Park, Sang Joon

    2010-06-01

    ZnSe nanocrystals were prepared using a safe and simple synthetic method by employing a sodium bis(2-ethylhexyl) sulfosuccinate (AOT)/water/oil microemulsion system with aqueous ZnSO4 and Se2- solutions, and characterized by X-ray diffraction (XRD) analysis, photoluminescence (PL) spectroscopy, and transmission electron microscopy (TEM). To control the diameter of nanocrystals in the quantum confinement region, the synthesis was performed with different oil phases (heptane and cyclohexane) and various water-to-surfactant ratios, W ([H2O]/[surfactant]). Cubic zinc blende ZnSe nanocrystals were synthesized and their size was controlled in the range from 2.5 to 17 nm. The maximum PL efficiency was 14% for the smallest ZnSe nanocrystal.

  20. A simple method to make an electrical connection between ZnO microwire and substrate through nanoscale metal evaporation

    NASA Astrophysics Data System (ADS)

    Kim, Hakseong; Lee, Jinkyung; Yun, Hoyeol; Lee, Sang; Nano Electonics and Nano Mechanics Team

    2013-03-01

    We developed a simple method to make an electrical connection with nanoscale electrodes on microscale wire using suspended Poly(methyl methacrylate) (PMMA) strings. Less than 90 nm height of Ti/Au made a complete electrical connection on the ZnO microwires of which diameter is around 2 μm. A cross linked PMMA string was bridged between ZnO microwire and substrate for making good electrical connection. The contact resistance of ZnO microwire fabricated by this method was much lower than that of device fabricated by standard E-beam lithography and evaporation. This fabrication method is readily extendible to prepare nano scale electrodes on various micro sized materials and serves as a pathway for studying their mesoscopic transport phenomena. This work is supported by WCU, BK21 and NRF.

  1. Micro-structural Evolution in Metals Subjected to Simple Shear by a Particular Severe Plastic Deformation Method

    NASA Astrophysics Data System (ADS)

    Li, Jinghui; Li, Fuguo; Li, Pan; Ma, Zhanchao; Wang, Chengpeng; Wang, Lei

    2015-08-01

    Simple shear (SS) has been considered an optimal deformation method of severe plastic deformation (SPD). To achieve SS, a particular SPD method known as mutative channel torsion extrusion (MCTE) was designed based on the geometric equivalence of SS, and the cavity parameters of a die were calculated according to strain equivalence. To investigate the characteristics of micro-structural evolution subjected to MCTE, simulated and experimental investigations were conducted. The simulated results indicate that equivalent strain distribution on the cross section is relatively uniform, and the metallographic observations confirm the simulated phenomenon. Transmission electron microscopy investigations show that the process of grain refinement undergoes the formation of shear bands, dislocation cells, dislocation forests, large-angle grain boundaries, and recrystallization nuclei. Two types of mechanisms are proposed in view of the different effects of SS on grain refinement. Eventually, MCTE is ensured as an effective method for grain refinement.

  2. 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.

  3. Nanocrystal-polymer solar cells

    NASA Astrophysics Data System (ADS)

    Huynh, Wendy Uyen

    The ability to structure materials on a nanometer dimension enables the processes of solar energy conversion to be optimized at their most fundamental length scale. In semiconducting nanocrystals, optical absorption and electrical transport can be tailored by changing their radius and length, respectively. The unique features of quantum confinement and shape manipulation characteristic for inorganic nanocrystals can be utilized to fabricate solar cells with properties not observed in organic or conventional inorganic solar cells. Furthermore, their solution processibility provides fabrication advantages in the production of low cost, large area, and flexible solar cells. By blending organic conjugated polymers with CdSe nanocrystals efficient thin film solar cells have been constructed. Intimate contact for efficient charge transfer between the polymer and nanocrystal components of the blend was achieved by removing the organic ligands on the surface of the nanocrystal and by using solvent mixtures. Control of the nanocrystal length and therefore the distance on which electrons are transported directly through a thin film device enabled the creation of direct pathways for the transport of electrons. In addition, tuning the band gap by altering the nanocrystal radius as well as using alternate materials such as CdTe the overlap between the absorption spectrum of the cell and the solar emission spectrum could be optimized. A photovoltaic device consisting of 7nm by 60nm CdSe nanorods and the conjugated polymer poly-3(hexylthiophene) was assembled from solution with an external quantum efficiency of over 54% and a monochromatic power conversion efficiency of up to 7% under illumination at low light intensity. Under AM 1.5 Global solar conditions, we obtained a power conversion efficiency of 1.7%.

  4. Efficient thermolysis route to monodisperse Cu₂ZnSnS₄ nanocrystals with controlled shape and structure.

    PubMed

    Zhang, Xiaoyan; Guo, Guobiao; Ji, Cheng; Huang, Kai; Zha, Chenyang; Wang, Yifeng; Shen, Liming; Gupta, Arunava; Bao, Ningzhong

    2014-01-01

    Monodisperse Cu2ZnSnS4 (CZTS) nanocrystals with tunable shape, crystalline phase, and composition are synthesized by efficient thermolysis of a single source precursor of mixed metal-oleate complexes in hot organic solvents with dissolved sulfur sources. Suitable tuning of the synthetic conditions and the Cu/(Zn + Sn) ratio of the precursor has enabled precise control of the crystalline phase in the form of kesterite, or a newly observed wurtzite structure. Nanocrystals with morphology in the form of spherical, rice-like, or rod-like shapes are obtained over a wide range of compositions (0.5 ≤ Cu/(Zn + Sn) ≤ 1.2). Both the final products and intermediates for each shape exhibit consistent composition and structure, indicating homogenous nucleation and growth of single-phase nanocrystals. Thin films prepared from colloidal nanocrystal suspensions display interesting shape-dependent photoresponse behavior under white light illumination from a solar simulator. PMID:24866987

  5. Symmetry-controlled colloidal nanocrystals: nonhydrolytic chemical synthesis and shape determining parameters.

    PubMed

    Jun, Young-wook; Lee, Jae-Hyun; Choi, Jin-sil; Cheon, Jinwoo

    2005-08-11

    Since inorganic nanocrystals exhibit unique shape-dependent nanoscale properties and can be utilized as basic building blocks for futuristic nanodevices, a systematic study on the shape control of these nanocrystals remains an important subject in materials and physical chemistry. In this feature article, we overview the recent progress on the synthetic development of symmetry-controlled colloidal nanocrystals of semiconductor and metal oxide, which are prepared through nonhydrolytic chemical routes. We describe their shape-guiding processes and illustrate the detailed key factors controlling their growth by examining various case studies of zero-dimensional spheres and cubes, one-dimensional rods, and quasi multidimensional structures such as disks, multipods, and stars. Specifically, the crystalline phase of nucleating seeds, surface energy, kinetic vs thermodynamic growth, and selective adhesion processes of capping ligands are found to be most crucial for the determination of the nanocrystal shape. PMID:16852873

  6. 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. PMID:25682881

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

    PubMed

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

    2016-06-01

    Metal-semiconductor hybrid nanocrystals have received extensive attention owing to their multiple functionalities which can find wide technological applications. The utilization of low-cost non-noble metals to construct novel metal-semiconductor hybrid nanocrystals is important and meaningful for their large-scale applications. In this study, a facile solution approach is developed for the synthesis of Cu-ZnO hybrid nanocrystals with well-controlled morphologies, including nanomultipods, core-shell nanoparticles, nanopyramids and core-shell nanowires. In the synthetic strategy, Cu nanocrystals formed in situ serve as seeds for the heterogeneous nucleation and growth of ZnO, and it eventually forms various Cu-ZnO hetero-nanostructures under different reaction conditions. These hybrid nanocrystals possess well-defined and stable heterostructure junctions. The ultraviolet-visible-near infrared spectra reveal morphology-dependent surface plasmon resonance absorption of Cu and the band gap absorption of ZnO. Furthermore, we construct a novel Cu@CuNi-ZnO ternary hetero-nanostructure by incorporating the magnetic metal Ni into the pre-synthesized colloidal Cu nanocrystals. Such hybrid nanocrystals possess a magnetic Cu-Ni intermediate layer between the ZnO shell and the Cu core, and exhibit ferromagnetic/superparamagnetic properties which expand their functionalities. Finally, enhanced photocatalytic activities are observed in the as-prepared non-noble metal-ZnO hybrid nanocrystals. This study not only provides an economical way to prepare high-quality morphology-controlled Cu-ZnO hybrid nanocrystals for potential applications in the fields of photocatalysis and photovoltaic devices, but also opens up new opportunities in designing ternary non-noble metal-semiconductor hybrid nanocrystals with multifunctionalities. PMID:27216552

  8. A Radiation-Tolerant, Low-Power Non-Volatile Memory Based on Silicon Nanocrystal Quantum Dots

    NASA Technical Reports Server (NTRS)

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

    2001-01-01

    Nanocrystal nonvolatile floating-gate memories are a good candidate for space applications - initial results suggest they are fast, more reliable and consume less power than conventional floating gate memories. In the nanocrystal based NVM device, charge is not stored on a continuous polysilicon layer (so-called floating gate), but instead on a layer of discrete nanocrystals. Charge injection and storage in dense arrays of silicon nanocrystals in SiO2 is a critical aspect of the performance of potential nanocrystal flash memory structures. The ultimate goal for this class of devices is few- or single-electron storage in a small number of nanocrystal elements. In addition, the nanocrystal layer fabrication technique should be simple, 8-inch wafer compatible and well controlled in program/erase threshold voltage swing was seen during 100,000 program and erase cycles. Additional near-term goals for this project include extensive testing for radiation hardness and the development of artificial layered tunnel barrier heterostructures which have the potential for large speed enhancements for read/write of nanocrystal memory elements, compared with conventional flash devices. Additional information is contained in the original extended abstract.

  9. 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

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

    EPA Science Inventory

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

  11. A Simple Hydrogen Electrode

    ERIC Educational Resources Information Center

    Eggen, Per-Odd

    2009-01-01

    This article describes the construction of an inexpensive, robust, and simple hydrogen electrode, as well as the use of this electrode to measure "standard" potentials. In the experiment described here the students can measure the reduction potentials of metal-metal ion pairs directly, without using a secondary reference electrode. Measurements…

  12. Hydrothermal Gelation of Aqueous Cellulose Nanocrystal Suspensions.

    PubMed

    Lewis, Lev; Derakhshandeh, Maziar; Hatzikiriakos, Savvas G; Hamad, Wadood Y; MacLachlan, Mark J

    2016-08-01

    We report the facile preparation of gels from the hydrothermal treatment of suspensions of cellulose nanocrystals (CNCs). The properties of the hydrogels have been investigated by rheology, electron microscopy, and spectroscopy with respect to variation in the temperature, time, and CNC concentration used in preparation. Desulfation of the CNCs at high temperature appears to be responsible for the gelation of the CNCs, giving highly porous networks. The viscosity and storage modulus of the gels was shown to increase when samples were prepared at higher treatment temperature. Considering the wide natural abundance and biocompatibility of CNCs, this simple, green approach to CNC-based hydrogels is attractive for producing materials that can be used in drug delivery, insulation, and as tissue scaffolds. PMID:27467200

  13. A simple robust method for synthesis of metallic copper nanoparticles of high antibacterial potency against E. coli

    NASA Astrophysics Data System (ADS)

    Chatterjee, Arijit Kumar; Sarkar, Raj Kumar; Prasun Chattopadhyay, Asoke; Aich, Pulakesh; Chakraborty, Ruchira; Basu, Tarakdas

    2012-03-01

    A method for preparation of copper nanoparticles (Cu-NPs) was developed by simple reduction of CuCl2 in the presence of gelatin as a stabilizer and without applying stringent conditions like purging with nitrogen. The NPs were characterized by spectrophotometry, dynamic light scattering, x-ray diffraction, transmission electron microscopy, atomic force microscopy and x-ray photoelectron spectroscopy. The particles were about 50-60 nm in size and highly stable. The antibacterial activity of this Cu-NP on Gram-negative Escherichia coli was demonstrated by the methods of agar plating, flow cytometry and phase contrast microscopy. The minimum inhibitory concentration (3.0 µg ml-1), minimum bactericidal concentration (7.5 µg ml-1) and susceptibility constant (0.92) showed that this Cu-NP is highly effective against E. coli at a much lower concentration than that reported previously. Treatment with Cu-NPs made E. coli cells filamentous. The higher the concentration of Cu-NPs, the greater the population of filamentous cells; average filament size varied from 7 to 20 µm compared to the normal cell size of ˜2.5 µm. Both filamentation and killing of cells by Cu-NPs (7.5 µg ml-1) also occurred in an E. coli strain resistant to multiple antibiotics. Moreover, an antibacterial effect of Cu-NPs was also observed in Gram-positive Bacillus subtilis and Staphylococcus aureus, for which the values of minimum inhibitory concentration and minimum bactericidal concentration were close to that for E. coli.

  14. Nanocrystal targeting in vivo

    NASA Astrophysics Data System (ADS)

    Åkerman, Maria E.; Chan, Warren C. W.; Laakkonen, Pirjo; Bhatia, Sangeeta N.; Ruoslahti, Erkki

    2002-10-01

    Inorganic nanostructures that interface with biological systems have recently attracted widespread interest in biology and medicine. Nanoparticles are thought to have potential as novel intravascular probes for both diagnostic (e.g., imaging) and therapeutic purposes (e.g., drug delivery). Critical issues for successful nanoparticle delivery include the ability to target specific tissues and cell types and escape from the biological particulate filter known as the reticuloendothelial system. We set out to explore the feasibility of in vivo targeting by using semiconductor quantum dots (qdots). Qdots are small (<10 nm) inorganic nanocrystals that possess unique luminescent properties; their fluorescence emission is stable and tuned by varying the particle size or composition. We show that ZnS-capped CdSe qdots coated with a lung-targeting peptide accumulate in the lungs of mice after i.v. injection, whereas two other peptides specifically direct qdots to blood vessels or lymphatic vessels in tumors. We also show that adding polyethylene glycol to the qdot coating prevents nonselective accumulation of qdots in reticuloendothelial tissues. These results encourage the construction of more complex nanostructures with capabilities such as disease sensing and drug delivery.

  15. Optical Properties of Semiconductor Nanocrystals

    NASA Astrophysics Data System (ADS)

    Gaponenko, S. V.

    1998-10-01

    Low-dimensional semiconductor structures, often referred to as nanocrystals or quantum dots, exhibit fascinating behavior and have a multitude of potential applications, especially in the field of communications. This book examines in detail the optical properties of these structures, gives full coverage of theoretical and experimental results, and discusses their technological applications. The author begins by setting out the basic physics of electron states in crystals (adopting a "cluster-to-crystal" approach), and goes on to discuss the growth of nanocrystals, absorption and emission of light by nanocrystals, optical nonlinearities, interface effects, and photonic crystals. He illustrates the physical principles with references to actual devices such as novel light-emitters and optical switches. The book covers a rapidly developing, interdisciplinary field. It will be of great interest to graduate students of photonics or microelectronics, and to researchers in electrical engineering, physics, chemistry, and materials science.

  16. Injected nanocrystals for targeted drug delivery

    PubMed Central

    Lu, Yi; Li, Ye; Wu, Wei

    2016-01-01

    Nanocrystals are pure drug crystals with sizes in the nanometer range. Due to the advantages of high drug loading, platform stability, and ease of scaling-up, nanocrystals have been widely used to deliver poorly water-soluble drugs. Nanocrystals in the blood stream can be recognized and sequestered as exogenous materials by mononuclear phagocytic system (MPS) cells, leading to passive accumulation in MPS-rich organs, such as liver, spleen and lung. Particle size, morphology and surface modification affect the biodistribution of nanocrystals. Ligand conjugation and stimuli-responsive polymers can also be used to target nanocrystals to specific pathogenic sites. In this review, the progress on injected nanocrystals for targeted drug delivery is discussed following a brief introduction to nanocrystal preparation methods, i.e., top-down and bottom-up technologies. PMID:27006893

  17. Semiconductor Nanocrystals for Biological Imaging

    SciTech Connect

    Fu, Aihua; Gu, Weiwei; Larabell, Carolyn; Alivisatos, A. Paul

    2005-06-28

    Conventional organic fluorophores suffer from poor photo stability, narrow absorption spectra and broad emission feature. Semiconductor nanocrystals, on the other hand, are highly photo-stable with broad absorption spectra and narrow size-tunable emission spectra. Recent advances in the synthesis of these materials have resulted in bright, sensitive, extremely photo-stable and biocompatible semiconductor fluorophores. Commercial availability facilitates their application in a variety of unprecedented biological experiments, including multiplexed cellular imaging, long-term in vitro and in vivo labeling, deep tissue structure mapping and single particle investigation of dynamic cellular processes. Semiconductor nanocrystals are one of the first examples of nanotechnology enabling a new class of biomedical applications.

  18. Metal colloids and quantum dots: linear and nonlinear optical properties

    SciTech Connect

    Henderson, Don O.

    1997-05-12

    Nanophase materials have found a wide application in a variety of technological areas which include ultrafast optical switching high density information storage and retrieval, electronics, and catalysts, to mention a few. Nanocrystal science has also drawn considerable interest from the fundamental perspective engaging physicists, chemists, and material scientists into this area of rapidly expanding and challenging research. Basic questions concerning how matter evolves from atomic like behavior to molecular and onto bulk lie at the center nanocrystal research. In addition, because of the high surface to volume ratio of the nanocrystals, the interaction potential between a nanocrystal and its surrounding environment becomes an important issue in determining its properties. While significant progress has been made in nanocrystal research, there are many problems concerned with their fabrication. In particular, the difficulty of incorporating nanocrystals into a matrix that is appropriate for ultimate device development has hindered some aspects of nanocrystal research. Ion implantation is a method that is now established as a technique for fabricating metal and semiconductor nanocrystals. It is highly versatile in that one may select nearly any host material for incorporating the nanocrystals of interest. The flexibility of being able to select the host matrix is also interesting from the point of view that it opens the opportunity to investigate matrix-nanocrystal interactions. We summarize in the following sections results on metal and semiconductor nanocrystals formed by ion implantation into dielectric hosts.

  19. Building Structural Complexity in Semiconductor Nanocrystals through Chemical Transformations

    SciTech Connect

    Sadtler, Bryce F

    2009-05-01

    Methods are presented for synthesizing nanocrystal heterostructures comprised of two semiconductor materials epitaxially attached within individual nanostructures. The chemical transformation of cation exchange, where the cations within the lattice of an ionic nanocrystal are replaced with a different metal ion species, is used to alter the chemical composition at specific regions ofa nanocrystal. Partial cation exchange was performed in cadmium sulfide (CdS) nanorods of well-defined size and shape to examine the spatial organization of materials within the resulting nanocrystal heterostructures. The selectivity for cation exchange to take place at different facets of the nanocrystal plays an important role in determining the resulting morphology of the binary heterostructure. The exchange of copper (I) (Cu+) cations in CdS nanorods occurs preferentially at the ends of the nanorods. Theoretical modeling of epitaxial attachments between different facets of CdS and Cu2S indicate that the selectivity for cation exchange at the ends of the nanorods is a result of the low formation energy of the interfaces produced. During silver (I) (Ag+) cation exchange in CdS nanorods, non-selective nucleation of silver sulfide (Ag2S), followed by partial phase segregation leads to significant changes in the spatial arrangement of CdS and Ag2S regions at the exchange reaction proceeds through the nanocrystal. A well-ordered striped pattern of alternating CdS and Ag2S segments is found at intermediate fractions of exchange. The forces mediating this spontaneous process are a combination of Ostwald ripening to reduce the interfacial area along with a strain-induced repulsive interaction between Ag2S segments. To elucidate why Cu+ and Ag+ cation exchange with CdS nanorods produce different morphologies, models for epitaxial attachments between various facets of CdS with Cu2S or

  20. Near-Monodisperse Ni-Cu Bimetallic Nanocrystals of Variable Composition: Controlled Synthesis and Catalytic Activity for H2 Generation

    SciTech Connect

    Zhang, Yawen; Huang, Wenyu; Habas, Susan E.; Kuhn, John N.; Grass, Michael E.; Yamada, Yusuke; Yang, Peidong; Somorjai, Gabor A.

    2008-07-22

    Near-monodisperse Ni{sub 1-x}Cu{sub x} (x = 0.2-0.8) bimetallic nanocrystals were synthesized by a one-pot thermolysis approach in oleylamine/1-octadecene, using metal acetylacetonates as precursors. The nanocrystals form large-area 2D superlattices, and display a catalytic synergistic effect in the hydrolysis of NaBH{sub 4} to generate H{sub 2} at x = 0.5 in a strongly basic medium. The Ni{sub 0.5}Cu{sub 0.5} nanocrystals show the lowest activation energy, and also exhibit the highest H{sub 2} generation rate at 298 K.

  1. Determination of the structure factor of simple liquid metals from the pseudopotential theory and optimized random-phase approximation: Application to Al and Ga

    NASA Astrophysics Data System (ADS)

    Bretonnet, J. L.; Regnaut, C.

    1985-04-01

    We present the results of calculations of the static structure factor S(q) of liquid Al and Ga at the melting point. These calculations were motivated because many simple liquid metals exhibit structure anomalies taking the form of a shoulder on the main peak or even an asymmetry in the peak itself, while other liquid metals are correctly predicted by the standard models of liquid structure. Al and Ga have similar valence, electronic density, and size of their ionic radius; therefore, their pair potentials are somewhat similar. Despite this, their structure factors display most of the differences that can be observed among the variety of liquid metals. Starting from the Shaw optimized model potential [Phys. Rev. 174, 769 (1968)], a pair potential is constructed. A comparative examination of the electron-gas response function of Vashishta and Singwi [Phys. Rev. B 6, 875 (1972)] and of Ichimaru and Utsumi [Phys. Rev. B 24, 7385 (1981)] is carried out. Different depletion hole distributions are also used and full nonlocality is taken into account through effective masses. So S(q) is calculated by means of the optimized random-phase approximation. Particular attention is also devoted to the low-q region. By comparison with Monte Carlo computation, we show the limitation of various thermodynamic perturbation methods, such as the random-phase approximation or the soft-sphere model. The study of S(q) provides a stringent test of the model potential, where the electron-ion pseudopotential and the local-field correction are of prime importance, but where effective masses and depletion hole distribution may also have a role to play.

  2. Use of reduction rate as a quantitative knob for controlling the twin structure and shape of palladium nanocrystals.

    PubMed

    Wang, Yi; Peng, Hsin-Chieh; Liu, Jingyue; Huang, Cheng Zhi; Xia, Younan

    2015-02-11

    Kinetic control is a powerful means for maneuvering the twin structure and shape of metal nanocrystals and thus optimizing their performance in a variety of applications. However, there is only a vague understanding of the explicit roles played by reaction kinetics due to the lack of quantitative information about the kinetic parameters. With Pd as an example, here we demonstrate that kinetic parameters, including rate constant and activation energy, can be derived from spectroscopic measurements and then used to calculate the initial reduction rate and further have this parameter quantitatively correlated with the twin structure of a seed and nanocrystal. On a quantitative basis, we were able to determine the ranges of initial reduction rates required for the formation of nanocrystals with a specific twin structure, including single-crystal, multiply twinned, and stacking fault-lined. This work represents a major step forward toward the deterministic syntheses of colloidal noble-metal nanocrystals with specific twin structures and shapes. PMID:25629786

  3. A graphene dispersed CdS-MoS2 nanocrystal ensemble for cooperative photocatalytic hydrogen production from water.

    PubMed

    Jia, Tiantian; Kolpin, Amy; Ma, Chensheng; Chan, Ruth Chau-Ting; Kwok, Wai-Ming; Tsang, S C Edman

    2014-02-01

    We report a simple but highly cooperative ensemble with CdS and MoS2 nanocrystals dispersed on graphene sheets: it is demonstrated that CdS nanocrystals can capture light energy and facilitate excited electron transfer to MoS2 for catalytic hydrogen production via the 2-D graphene which plays a key role as an efficient electron mediator. PMID:24326768

  4. Polysulfide ligand exchange on zinc sulfide nanocrystal surfaces for improved film formation

    NASA Astrophysics Data System (ADS)

    Herron, Steven M.; Lawal, Qudus O.; Bent, Stacey F.

    2015-12-01

    The physical and chemical properties of nanocrystals can be modified by changing the ligands attached at their surfaces. A ligand exchange procedure with ammonium polysulfides has been developed to replace the native ligands on cubic zinc sulfide nanocrystals. Several mixtures of polysulfides in formamide and other solvents were prepared with different average chain lengths and used to achieve high yield ligand exchange, as confirmed by UV-vis spectroscopy, infrared spectroscopy and X-ray photoelectron spectroscopy. The results show that polysulfide content can be increased with longer surface ligands and that the exchange process yields compositionally pure surfaces before and after high temperature anneals. X-ray diffraction and scanning electron microscopy show that, when annealed in nitrogen at 525 °C, polysulfide ligands lead to average crystal sizes 2-3 times larger than in the un-exchanged control sample. The ligand exchange procedure itself does not alter nanocrystal size. Nanocrystal inks prepared from the exchanged samples form thin films that exhibit superior grain growth, morphology, mass retention, and composition compared to the un-exchanged material. Overall, polysulfide species are demonstrated as alternative ligands for the surfaces of metal chalcogenide nanocrystals which, when incorporated in an efficient ligand-exchange procedure, can improve the quality of ZnS nanocrystal inks.

  5. Synthesis and thermal stability of W-doped VO{sub 2} nanocrystals

    SciTech Connect

    Kong, F.Y.; Li, M.; Pan, S.S.; Zhang, Y.X.; Li, G.H.

    2011-11-15

    Highlights: {yields} The VO{sub 2} nanocrystals with a nearly spherical morphology with size ranging from 50 to 100 nm were synthesized by using V{sub 2}O{sub 5} and oxalic acid as precursors via a thermolysis method. {yields} The W dopant is in the W{sup 6+} form, and there is a small amount of V{sup 3+} in the VO{sub 2} nanocrystals. VO{sub 2} (R) nanocrystals with phase transition temperature at room temperature were obtained with 2.5 at% W-doing. {yields} A high stability upon heating-cooling cycles was observed with respect to MIT temperature, peak temperature and latent heat of the phase transition due to both the size effect and the existence of V{sup 3+} in the VO{sub 2} nanocrystals. -- Abstract: Pure and W-doped vanadium dioxide nanocrystals have been synthesized by using V{sub 2}O{sub 5} and oxalic acid as precursors via a thermolysis method. The VO{sub 2} nanocrystals have a nearly spherical morphology with size ranging from 50 to 100 nm. The metal-insulator transition (MIT) temperature of the nanocrystals decreases with increasing W-doping content. The successive heat-induced fatigue character of the MIT in W-doped VO{sub 2} nanocrystals was investigated by DSC analysis together with structural study, and a high stability upon heating-cooling cycles was found with respect to MIT temperature, peak temperature and latent heat of the phase transition.

  6. Additive-assisted synthesis of boride, carbide, and nitride micro/nanocrystals

    SciTech Connect

    Chen, Bo; Yang, Lishan; Heng, Hua; Chen, Jingzhong; Zhang, Linfei; Xu, Liqiang; Qian, Yitai; Yang, Jian

    2012-10-15

    General and simple methods for the syntheses of borides, carbides and nitrides are highly desirable, since those materials have unique physical properties and promising applications. Here, a series of boride (TiB{sub 2}, ZrB{sub 2}, NbB{sub 2}, CeB{sub 6}, PrB{sub 6}, SmB{sub 6}, EuB{sub 6}, LaB{sub 6}), carbide (SiC, TiC, NbC, WC) and nitride (TiN, BN, AlN, MgSiN{sub 2}, VN) micro/nanocrystals were prepared from related oxides and amorphous boron/active carbon/NaN{sub 3} with the assistance of metallic Na and elemental S. In-situ temperature monitoring showed that the reaction temperature could increase quickly to {approx}850 Degree-Sign C, once the autoclave was heated to 100 Degree-Sign C. Such a rapid temperature increase was attributed to the intense exothermic reaction between Na and S, which assisted the formation of borides, carbides and nitrides. The as-obtained products were characterized by XRD, SEM, TEM, and HRTEM techniques. Results in this report will greatly benefit the future extension of this approach to other compounds. - Graphical abstract: An additive-assisted approach is successfully developed for the syntheses of borides, carbides and nitrides micro/nanocrystals with the assistance of the exothermic reaction between Na and S. Highlights: Black-Right-Pointing-Pointer An additive-assisted synthesis strategy is developed for a number of borides, carbides and nitrides. Black-Right-Pointing-Pointer The reaction mechanism is demonstrated by the case of SiC nanowires. Black-Right-Pointing-Pointer The formation of SiC nanowires is initiated by the exothermic reaction of Na and S.

  7. A facile arrested precipitation method for synthesis of pure wurtzite Cu{sub 2}ZnSnS{sub 4} nanocrystals using thiourea as a sulfur source

    SciTech Connect

    Li, Chunya; Ha, Enna; Wong, Wing-Leung; Li, Cuiling; Ho, Kam-Piu; Wong, Kwok-Yin

    2012-11-15

    Graphical abstract: High-resolution TEM image of wurtzite Cu{sub 2}ZnSnS{sub 4} nanocrystals. Highlights: ► Wurtzite Cu{sub 2}ZnSnS{sub 4} nanocrystals were synthesized by arrested precipitation method. ► XRD, EDX, TEM demonstrate that the CZTS nanocrystals are purely wurtzite structure. ► The average diameter of the bulk CZTS products is found to be 10 ± 1.1 nm. ► The estimated direct bandgap energy is 1.56 eV for wurtzite CZTS nanocrystals. ► The electrical resistivity of the wurtzite CZTS nanocrystals is low. -- Abstract: A facile route for the synthesis of wurtzite Cu{sub 2}ZnSnS{sub 4} (CZTS) nanocrystals was developed by an arrested precipitation method at 240 °C under simple reaction conditions with diethanolamine as the solvent and thiourea as sulfur source. The structure and morphology of the CZTS nanocrystals were characterized by X-ray diffraction and transmission electron microscopy. Control experiments demonstrated that CZTS nanocrystals which are purely wurtzite structure are readily obtained. The average diameter of the bulk CZTS products is found to be 10 ± 1.1 nm. The estimated direct bandgap energy is 1.56 eV, which indicates that the CZTS nanocrystals produced by this method possess promising applications in photovoltaic devices.

  8. Biomineralization of a Cadmium Chloride Nanocrystal by a Designed Symmetrical Protein.

    PubMed

    Voet, Arnout R D; Noguchi, Hiroki; Addy, Christine; Zhang, Kam Y J; Tame, Jeremy R H

    2015-08-17

    We have engineered a metal-binding site into the novel artificial β-propeller protein Pizza. This new Pizza variant carries two nearly identical domains per polypeptide chain, and forms a trimer with three-fold symmetry. The designed single metal ion binding site lies on the symmetry axis, bonding the trimer together. Two copies of the trimer associate in the presence of cadmium chloride in solution, and very high-resolution X-ray crystallographic analysis reveals a nanocrystal of cadmium chloride, sandwiched between two trimers of the protein. This nanocrystal, containing seven cadmium ions lying in a plane and twelve interspersed chloride ions, is the smallest reported to date. Our results indicate the feasibility of using rationally designed symmetrical proteins to biomineralize nanocrystals with useful properties. PMID:26136355

  9. Nanocrystals Research for Energy Efficient and Clean Energy Technologies:

    SciTech Connect

    Rosenthal, Sandra J

    2013-12-17

    Efforts centered on: nanocrystal photovoltaic fabrication, ultrafast dynamics and aberration-corrected STEM characterization of II-VI core, core/shell and alloyed nanocrystals, and fundamental investigation and applications of ultrasmall white light-emitting CdSe nanocrystal.

  10. Electrospinnability of bionanocomposites with high nanocrystal loadings: The effect of nanocrystal surface characteristics.

    PubMed

    Naseri, Narges; Mathew, Aji P; Oksman, Kristiina

    2016-08-20

    This paper deals with the effect of solution properties and nanoparticle surface chemistry on the spinnability of a chitosan/polyethylene oxide (PEO) with high concentration (50wt%) of chitin and cellulose nanocrystals and the properties of the resultant nanocomposite fibers/fiber mats. Electrospinning dispersions with cellulose nanocrystals having sulphate surface groups showed poor spinnability compared to chitin nanocrystals with amide and amino groups. Chitin nanocrystal based dispersions showed good spinnability and continuous fiber formation whereas cellulose nanocrystal system showed discontinuous fibers and branching. The viscosity and surface tension are shown to impact this behavior, but conductivity did not. Poor spinnability observed for cellulose nanocrystal based fibers was attributed to the coagulation of negatively charged cellulose nanocrystals and positively charged chitosan. The study showed that the nanocrystal surface charge and interactions with the chitosan/PEO matrix have a significant impact on the spinnability of bionanocomposites. PMID:27178953

  11. Benefitting from Dopant Loss and Ostwald Ripening in Mn Doping of II-VI Semiconductor Nanocrystals.

    PubMed

    Zhai, You; Shim, Moonsub

    2015-12-01

    Annealing or growth at high temperatures for an extended period of time is considered detrimental for most synthetic strategies for high-quality Mn-doped II-VI semiconductor nanocrystals. It can lead to the broadening of size distribution and, more importantly, to the loss of dopants. Here, we examine how ripening can be beneficial to doping in a simple "heat-up" approach, where high dopant concentrations can be achieved. We discuss the interplay of the loss of dopants, Ostwald ripening, and the clustering of Mn near the surface during nanocrystal growth. Smaller nanocrystals in a reaction batch, on average, exhibit higher undesirable band-edge photoluminescence (PL) and lower desirable dopant PL. The optimization of dopant loss and the removal of such smaller undesirable nanocrystals through Ostwald ripening along with surface exchange/passivation to remove Mn clustering lead to high Mn PL quantum yields (45 to 55 %) for ZnSxSe1-x, ZnS, CdS, and CdSxSe1-x host nanocrystals. These results provide an improved understanding of the doping process in a simple and potentially scalable synthetic strategy for achieving "pure" and bright dopant emission. PMID:26510444

  12. Benefitting from Dopant Loss and Ostwald Ripening in Mn Doping of II-VI Semiconductor Nanocrystals

    NASA Astrophysics Data System (ADS)

    Zhai, You; Shim, Moonsub

    2015-10-01

    Annealing or growth at high temperatures for an extended period of time is considered detrimental for most synthetic strategies for high-quality Mn-doped II-VI semiconductor nanocrystals. It can lead to the broadening of size distribution and, more importantly, to the loss of dopants. Here, we examine how ripening can be beneficial to doping in a simple "heat-up" approach, where high dopant concentrations can be achieved. We discuss the interplay of the loss of dopants, Ostwald ripening, and the clustering of Mn near the surface during nanocrystal growth. Smaller nanocrystals in a reaction batch, on average, exhibit higher undesirable band-edge photoluminescence (PL) and lower desirable dopant PL. The optimization of dopant loss and the removal of such smaller undesirable nanocrystals through Ostwald ripening along with surface exchange/passivation to remove Mn clustering lead to high Mn PL quantum yields (45 to 55 %) for ZnSxSe1-x, ZnS, CdS, and CdSxSe1-x host nanocrystals. These results provide an improved understanding of the doping process in a simple and potentially scalable synthetic strategy for achieving "pure" and bright dopant emission.

  13. Safety Investigation of Liquid-Metal-Cooled Nuclear Systems with Heat Exchanger in the Risers of Simple Flow-Path Pool Design

    SciTech Connect

    Carlsson, Johan; Wider, Hartmut U.

    2005-12-15

    Safety investigations were performed on 600- and 1426-MW(thermal) liquid-metal-cooled reactors with the heat exchangers (HXs) located in the risers of simple flow-path pool designs. This includes both critical reactors and accelerator-driven systems (ADSs) using liquid-metal coolants. For the 600-MW(thermal) ADS, the safety implications were examined for vessel sizes of two heights (11 and 15 m) and two diameters (6 and 10 m). Then, the reference design of 11-m height and 6-m diameter was compared with a similar design, but with the HXs located in the downcomers. The transients investigated were total-loss-of-power (TLOP), unprotected-loss-of-flow (ULOF), protected-loss-of-flow, and unprotected loss-of-heat-sink accidents. The 600-MW(thermal) ADS of 11-m height and 6-m diameter peaks at 1041 K after 29 h during a TLOP accident. If the diameter is increased to 10 m, it will peak after 55 h at a 178 K lower temperature thanks to its larger thermal inertia. The difference between locating the HXs in the risers and the downcomers is insignificant for this accident type. With the HXs in the risers, the temperature peaks at 1045 K after 28 h. During a ULOF accident in an ADS at full power, the core outlet temperature stabilizes at 1010 K, which is 337 K above the nominal outlet temperature. When the vessel height is increased to 15 m, the natural convection is improved, and the core outlet temperature stabilizes at 911 K. A Pb-cooled 1426-MW(thermal) reactor of 11-m height and 12-m diameter is also shown to be sufficiently coolable during a TLOP accident; i.e., it peaks at 1093 K after 49 h. In a pool-type design with a simple flow path, the use of HXs in the risers and flaps at their inlets that prevent a flow reversal will have significant safety advantages in case of HX tube failures. Steam or gas bubbles exiting from the secondary circuit cannot be dragged into the core region by the liquid-metal coolant. Instead, they would rise with the coolant and exit through the

  14. Aqueous-phase synthesis of monodisperse plasmonic gold nanocrystals using shortened single-walled carbon nanotubes.

    PubMed

    Kim, Jin-Woo; Moon, Hyung-Mo; Benamara, Mourad; Sakon, Joshua; Salamo, Gregory J; Zharov, Vladimir P

    2010-10-14

    Monodisperse gold nanocrystals with unique near-infrared optical properties were synthesized by simple mixing of highly shortened and well disperse single-walled carbon nanotubes and chloroauric acid in water at ambient conditions with a step-wise increase of gold ion concentration. PMID:20737105

  15. Spatial co-localization of multi-enzymes by inorganic nanocrystal-protein complexes.

    PubMed

    Li, Zhixian; Zhang, Yifei; Su, Yechao; Ouyang, Pingkai; Ge, Jun; Liu, Zheng

    2014-10-25

    We report a simple precipitation method for the construction of spatially co-localized multi-enzyme systems based on inorganic nanocrystal-protein complexes. A spatially controlled multi-enzyme system exhibits enhanced overall catalytic performance, allowing for sensitive detection of glucose in solution. PMID:25192430

  16. Cellulose nanocrystals: synthesis, functional properties, and applications.

    PubMed

    George, Johnsy; Sabapathi, S N

    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

  17. Phase transitions and doping in semiconductor nanocrystals

    NASA Astrophysics Data System (ADS)

    Sahu, Ayaskanta

    Colloidal semiconductor nanocrystals are a promising technological material because their size-dependent optical and electronic properties can be exploited for a diverse range of applications such as light-emitting diodes, bio-labels, transistors, and solar cells. For many of these applications, electrical current needs to be transported through the devices. However, while their solution processability makes these colloidal nanocrystals attractive candidates for device applications, the bulky surfactants that render these nanocrystals dispersible in common solvents block electrical current. Thus, in order to realize the full potential of colloidal semiconductor nanocrystals in the next-generation of solid-state devices, methods must be devised to make conductive films from these nanocrystals. One way to achieve this would be to add minute amounts of foreign impurity atoms (dopants) to increase their conductivity. Electronic doping in nanocrystals is still very much in its infancy with limited understanding of the underlying mechanisms that govern the doping process. This thesis introduces an innovative synthesis of doped nanocrystals and aims at expanding the fundamental understanding of charge transport in these doped nanocrystal films. The list of semiconductor nanocrystals that can be doped is large, and if one combines that with available dopants, an even larger set of materials with interesting properties and applications can be generated. In addition to doping, another promising route to increase conductivity in nanocrystal films is to use nanocrystals with high ionic conductivities. This thesis also examines this possibility by studying new phases of mixed ionic and electronic conductors at the nanoscale. Such a versatile approach may open new pathways for interesting fundamental research, and also lay the foundation for the creation of novel materials with important applications. In addition to their size-dependence, the intentional incorporation of

  18. 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

  19. Facile Synthesis of Curcumin Nanocrystals and Validation of Its Antioxidant Activity Against Circulatory Toxicity in Wistar Rats.

    PubMed

    Rajasekar, A; Devasena, T

    2015-06-01

    Our investigation was carried out in two phases. First we synthesized curcumin nanocrystals using a simple precipitation method and characterized their absorbance, crystallinity, size, and morphology by UV-visible spectroscopy, X-ray diffraction (XRD) spectroscopy, High Resolution Transmission Electron Microscopy (HRTEM) and Particle size Analyzer (PSA), in comparison with bulk curcumin. Characterization studies revealed that the protocol we standardized resulted in Curcumin nanocrystals with 10-200 nm size which was fairly soluble in water in contrast to bulk curcumin. Due to its crystallinity, nanocurcumin that we synthesized was also referred as Curcumin Nanocrystals. In Phase 2, we have assessed the comparative antioxidant efficacy of Curcumin nanocrystals and bulk Curcumin in the circulation of 1,2-dimethyl hydrazine-treated rats by investigating lipid peroxidation, antioxidant enzymes (superoxide dismutase, catalase), GSH and GSH-dependent detoxification enzymes (glutathione peroxidase, gIutathione-S-transferase). Curcumin nanocrystals exerted its antioxidant effect by decreasing lipid peroxidation, and by enhancing the activities of antioxidant and detoxification enzymes studied. Curcumin nanocrystals exhibited its antioxidant action at 40 mg dose whereas the bulk curcumin exerted its effect at 80 mg dose. This may be due to enhanced solubility, dispersibility, and crystallinity of the nanocrystals, which might have enhanced its bioavailability when compared to poorly soluble bulk curcumin. PMID:26369020

  20. Synthesis and photocatalytic properties of multi-morphological AuCu3-ZnO hybrid nanocrystals

    NASA Astrophysics Data System (ADS)

    Zeng, Deqian; Chen, Yuanzhi; Peng, Jian; Xie, Qingshui; Peng, Dong-Liang

    2015-10-01

    Noble metal-semiconductor hybrid nanocrystals represent an important class of materials for many potential applications, especially for photocatalysis. The utilization of transition metals to form alloys with noble metals can not only reduce the preparation costs, but may also offer tunable optical and catalytic properties for a broader range of applications. In this study, we report on the solution synthesis of AuCu3-ZnO hybrid nanocrystals with three interesting morphologies, including urchin-like, flower-like and multipod-like nanocrystals. In the synthetic strategy, Au-Cu bimetallic alloy seeds formed in situ are used to induce the heteroepitaxial growth of ZnO nanocrystals on the surface of bimetallic alloy cores; thus different types of morphologies can be achieved by controlling the reaction conditions. Through high-resolution transmission electron microscopy observations, well-defined interfaces between ZnO and AuCu3 are observed, which indicate that ZnO has a (0001) orientation and prefers to grow on AuCu3 {111} facets. The as-prepared hybrid nanocrystals demonstrate morphology- and composition-dependent surface plasmon resonance (SPR) absorption bands. In addition, much higher photocatalytic efficiency than pure ZnO nanocrystals is observed for the hybrid nanocrystals in the degradation of methylene blue. In particular, the multipod-like AuCu3-ZnO hybrid nanocrystals show the highest catalytic performance, as well as more than three times higher photocurrent density than the pure ZnO sample. The reported synthetic strategy provides a facile route to the effective combination of a plasmonic alloy with semiconductor components at the nanoscale in a controlled manner.

  1. Interaction potentials of anisotropic nanocrystals from the trajectory sampling of particle motion using in situ liquid phase transmission electron microscopy

    DOE PAGESBeta

    Chen, Qian; Cho, Hoduk; Manthiram, Karthish; Yoshida, Mark; Ye, Xingchen; Alivisatos, A. Paul

    2015-03-23

    We demonstrate a generalizable strategy to use the relative trajectories of pairs and groups of nanocrystals, and potentially other nanoscale objects, moving in solution which can now be obtained by in situ liquid phase transmission electron microscopy (TEM) to determine the interaction potentials between nanocrystals. Such nanoscale interactions are crucial for collective behaviors and applications of synthetic nanocrystals and natural biomolecules, but have been very challenging to measure in situ at nanometer or sub-nanometer resolution. Here we use liquid phase TEM to extract the mathematical form of interaction potential between nanocrystals from their sampled trajectories. We show the power ofmore » this approach to reveal unanticipated features of nanocrystal–nanocrystal interactions by examining the anisotropic interaction potential between charged rod-shaped Au nanocrystals (Au nanorods); these Au nanorods assemble, in a tip-to-tip fashion in the liquid phase, in contrast to the well-known side-by-side arrangements commonly observed for drying-mediated assembly. These observations can be explained by a long-range and highly anisotropic electrostatic repulsion that leads to the tip-selective attachment. As a result, Au nanorods stay unassembled at a lower ionic strength, as the electrostatic repulsion is even longer-ranged. Our study not only provides a mechanistic understanding of the process by which metallic nanocrystals assemble but also demonstrates a method that can potentially quantify and elucidate a broad range of nanoscale interactions relevant to nanotechnology and biophysics.« less

  2. Interaction Potentials of Anisotropic Nanocrystals from the Trajectory Sampling of Particle Motion using in Situ Liquid Phase Transmission Electron Microscopy

    PubMed Central

    2015-01-01

    We demonstrate a generalizable strategy to use the relative trajectories of pairs and groups of nanocrystals, and potentially other nanoscale objects, moving in solution which can now be obtained by in situ liquid phase transmission electron microscopy (TEM) to determine the interaction potentials between nanocrystals. Such nanoscale interactions are crucial for collective behaviors and applications of synthetic nanocrystals and natural biomolecules, but have been very challenging to measure in situ at nanometer or sub-nanometer resolution. Here we use liquid phase TEM to extract the mathematical form of interaction potential between nanocrystals from their sampled trajectories. We show the power of this approach to reveal unanticipated features of nanocrystal–nanocrystal interactions by examining the anisotropic interaction potential between charged rod-shaped Au nanocrystals (Au nanorods); these Au nanorods assemble, in a tip-to-tip fashion in the liquid phase, in contrast to the well-known side-by-side arrangements commonly observed for drying-mediated assembly. These observations can be explained by a long-range and highly anisotropic electrostatic repulsion that leads to the tip-selective attachment. As a result, Au nanorods stay unassembled at a lower ionic strength, as the electrostatic repulsion is even longer-ranged. Our study not only provides a mechanistic understanding of the process by which metallic nanocrystals assemble but also demonstrates a method that can potentially quantify and elucidate a broad range of nanoscale interactions relevant to nanotechnology and biophysics. PMID:27162944

  3. Cu₂Se and Cu Nanocrystals as Local Sources of Copper in Thermally Activated In Situ Cation Exchange.

    PubMed

    Casu, Alberto; Genovese, Alessandro; Manna, Liberato; Longo, Paolo; Buha, Joka; Botton, Gianluigi A; Lazar, Sorin; Kahaly, Mousumi Upadhyay; Schwingenschloegl, Udo; Prato, Mirko; Li, Hongbo; Ghosh, Sandeep; Palazon, Francisco; De Donato, Francesco; Mozo, Sergio Lentijo; Zuddas, Efisio; Falqui, Andrea

    2016-02-23

    Among the different synthesis approaches to colloidal nanocrystals, a recently developed toolkit is represented by cation exchange reactions, where the use of template nanocrystals gives access to materials that would be hardly attainable via direct synthesis. Besides, postsynthetic treatments, such as thermally activated solid-state reactions, represent a further flourishing route to promote finely controlled cation exchange. Here, we report that, upon in situ heating in a transmission electron microscope, Cu2Se or Cu nanocrystals deposited on an amorphous solid substrate undergo partial loss of Cu atoms, which are then engaged in local cation exchange reactions with Cu "acceptor" phases represented by rod- and wire-shaped CdSe nanocrystals. This thermal treatment slowly transforms the initial CdSe nanocrystals into Cu(2-x)Se nanocrystals, through the complete sublimation of Cd and the partial sublimation of Se atoms. Both Cu "donor" and "acceptor" particles were not always in direct contact with each other; hence, the gradual transfer of Cu species from Cu2Se or metallic Cu to CdSe nanocrystals was mediated by the substrate and depended on the distance between the donor and acceptor nanostructures. Differently from what happens in the comparably faster cation exchange reactions performed in liquid solution, this study shows that slow cation exchange reactions can be performed at the solid state and helps to shed light on the intermediate steps involved in such reactions. PMID:26816347

  4. Cu2Se and Cu Nanocrystals as Local Sources of Copper in Thermally Activated In Situ Cation Exchange

    PubMed Central

    2016-01-01

    Among the different synthesis approaches to colloidal nanocrystals, a recently developed toolkit is represented by cation exchange reactions, where the use of template nanocrystals gives access to materials that would be hardly attainable via direct synthesis. Besides, postsynthetic treatments, such as thermally activated solid-state reactions, represent a further flourishing route to promote finely controlled cation exchange. Here, we report that, upon in situ heating in a transmission electron microscope, Cu2Se or Cu nanocrystals deposited on an amorphous solid substrate undergo partial loss of Cu atoms, which are then engaged in local cation exchange reactions with Cu “acceptor” phases represented by rod- and wire-shaped CdSe nanocrystals. This thermal treatment slowly transforms the initial CdSe nanocrystals into Cu2–xSe nanocrystals, through the complete sublimation of Cd and the partial sublimation of Se atoms. Both Cu “donor” and “acceptor” particles were not always in direct contact with each other; hence, the gradual transfer of Cu species from Cu2Se or metallic Cu to CdSe nanocrystals was mediated by the substrate and depended on the distance between the donor and acceptor nanostructures. Differently from what happens in the comparably faster cation exchange reactions performed in liquid solution, this study shows that slow cation exchange reactions can be performed at the solid state and helps to shed light on the intermediate steps involved in such reactions. PMID:26816347

  5. 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. PMID:25915094

  6. Controlled Crystallinity and Fundamental Coupling Interactions in Nanocrystals

    NASA Astrophysics Data System (ADS)

    Ouyang, Min

    2009-03-01

    Metal and semiconductor nanocrystals show many unusual properties and functionalities, and can serve as model system to explore fundamental quantum and classical coupling interactions as well as building blocks of many practical applications. However, because of their small size, these nanoparticles typically exhibit different crystalline properties as compared with their bulk counterpart, and controlling crystallinity (and structural defects) within nanoparticles has posed significant technical challenges. In this talk, I will firstly apply silver metal nanoparticles as an example and present a novel chemical synthetic technique to achieve unprecedented crystallinity control at the nanoscale. This engineering of nanocrystallinity enables manipulation of intrinsic chemical functionalities, physical properties as well as nano-device performance [1]. For example, I will highlight that electron- phonon coupling constant can be significantly reduced by about four times and elastic modulus is increased ˜40% in perfect single crystalline silver nanoparticles as compared with those in disordered twinned nanoparticles. One important application of metal nanoparticles is nanoscale sensors. I will thus demonstrate that performance of nanoparticles based molecular sensing devices can be optimized with three times improvement of figure-of-merit if perfect single crystalline nanoparticles are applied. Lastly, I will present our related studies on semiconductor nanocrystals as well as their hybrid heterostructures. These discussions should offer important implications for our understanding of the fundamental properties at nanoscale and potential applications of metal nanoparticles. [4pt] [1] Yun Tang and Min Ouyang, Nature Materials, 6, 754, 2007.

  7. Exporting superconductivity across the gap: Proximity effect for semiconductor valence-band states due to contact with a simple-metal superconductor

    NASA Astrophysics Data System (ADS)

    Moghaddam, A. G.; Kernreiter, T.; Governale, M.; Zülicke, U.

    2014-05-01

    The proximity effect refers to the phenomenon whereby superconducting properties are induced in a normal conductor that is in contact with an intrinsically superconducting material. In particular, the combination of nanostructured semiconductors with bulk superconductors is of interest because these systems can host unconventional electronic excitations such as Majorana fermions when the semiconductor's charge carriers are subject to a large spin-orbit coupling. The latter requirement generally favors the use of hole-doped semiconductors. On the other hand, basic symmetry considerations imply that states from typical simple-metal superconductors will predominantly couple to a semiconductor's conduction-band states and, therefore, in the first instance generate a proximity effect for band electrons rather than holes. In this article, we show how the superconducting correlations in the conduction band are transferred also to hole states in the valence band by virtue of interband coupling. A general theory of the superconducting proximity effect for bulk and low-dimensional hole systems is presented. The interplay of interband coupling and quantum confinement is found to result in unusual wave-vector dependencies of the induced superconducting gap parameters. One particularly appealing consequence is the density tunability of the proximity effect in hole quantum wells and nanowires, which creates new possibilities for manipulating the transition to nontrivial topological phases in these systems.

  8. Bone bonding bioactivity of Ti metal and Ti-Zr-Nb-Ta alloys with Ca ions incorporated on their surfaces by simple chemical and heat treatments.

    PubMed

    Fukuda, A; Takemoto, M; Saito, T; Fujibayashi, S; Neo, M; Yamaguchi, S; Kizuki, T; Matsushita, T; Niinomi, M; Kokubo, T; Nakamura, T

    2011-03-01

    Ti15Zr4Nb4Ta and Ti29Nb13Ta4.6Zr, which do not contain the potentially cytotoxic elements V and Al, represent a new generation of alloys with improved corrosion resistance, mechanical properties, and cytocompatibility. Recently it has become possible for the apatite forming ability of these alloys to be ascertained by treatment with alkali, CaCl2, heat, and water (ACaHW). In order to confirm the actual in vivo bioactivity of commercially pure titanium (cp-Ti) and these alloys after subjecting them to ACaHW treatment at different temperatures, the bone bonding strength of implants made from these materials was evaluated. The failure load between implant and bone was measured for treated and untreated plates at 4, 8, 16, and 26 weeks after implantation in rabbit tibia. The untreated implants showed almost no bonding, whereas all treated implants showed successful bonding by 4 weeks, and the failure load subsequently increased with time. This suggests that a simple and economical ACaHW treatment could successfully be used to impart bone bonding bioactivity to Ti metal and Ti-Zr-Nb-Ta alloys in vivo. In particular, implants heat treated at 700 °C exhibited significantly greater bone bonding strength, as well as augmented in vitro apatite formation, in comparison with those treated at 600 °C. Thus, with this improved bioactive treatment process these advantageous Ti-Zr-Nb-Ta alloys can serve as useful candidates for orthopedic devices. PMID:20883837

  9. Anisotropic Gold Nanocrystals:. Synthesis and Characterization

    NASA Astrophysics Data System (ADS)

    Stiufiuc, R.; Toderas, F.; Iosin, M.; Stiufiuc, G.

    In this letter we report on successful preparation and characterization of anisotropic gold nanocrystals bio-synthesized by reduction of aqueous chloroaurate ions in pelargonium plant extract. The nanocrystals have been characterized by means of Transmission Electron Microscopy (TEM), UV-VIS absorption spectroscopy and tapping mode atomic force microscopy (TM-AFM). Using these investigation techniques, the successful formation of anisotropic single nanocrystals with the preferential growth direction along the gold (111) plane has been confirmed. The high detail phase images could give us an explanation concerning the growth mechanism of the nanocrystals.

  10. Al-doped ZnO nanocrystals

    NASA Astrophysics Data System (ADS)

    Kadam, Pratibha; Agashe, Chitra; Mahamuni, Shailaja

    2008-11-01

    Al3+-doped ZnO nanocrystals were differently obtained by wet chemical and an electrochemical route. An increase in forbidden gap due to change in crystal size and also due to Al3+ doping in ZnO is critically analyzed. The Moss-Burstein type shift in Al3+-doped ZnO nanocrystals provides an evidence of successful Al3+ doping in ZnO nanocrystals. The possibility of varying the carrier concentration in ZnO nanocrystals is the indirect implication of the present investigations.

  11. Electronic structure of cobalt nanocrystals suspended inliquid

    SciTech Connect

    Liu, Hongjian; Guo, Jinghua; Yin, Yadong; Augustsson, Andreas; Dong, Chungli; Nordgren, Joseph; Chang, Chinglin; Alivisatos, Paul; Thornton, Geoff; Ogletree, D. Frank; Requejo, Felix G.; de Groot, Frank; Salmeron, Miquel

    2007-07-16

    The electronic structure of cobalt nanocrystals suspended in liquid as a function of size has been investigated using in-situ x-ray absorption and emission spectroscopy. A sharp absorption peak associated with the ligand molecules is found that increases in intensity upon reducing the nanocrystal size. X-ray Raman features due to d-d and to charge-transfer excitations of ligand molecules are identified. The study reveals the local symmetry of the surface of {var_epsilon}-Co phase nanocrystals, which originates from a dynamic interaction between Co nanocrystals and surfactant + solvent molecules.

  12. Implantation conditions for diamond nanocrystal formation in amorphous silica

    SciTech Connect

    Buljan, Maja; Radovic, Iva Bogdanovic; Desnica, Uros V.; Ivanda, Mile; Jaksic, Milko; Saguy, Cecile; Kalish, Rafi; Djerdj, Igor; Tonejc, Andelka; Gamulin, Ozren

    2008-08-01

    We present a study of carbon ion implantation in amorphous silica, which, followed by annealing in a hydrogen-rich environment, leads to preferential formation of carbon nanocrystals with cubic diamond (c-diamond), face-centered cubic (n-diamond), or simple cubic (i-carbon) carbon crystal lattices. Two different annealing treatments were used: furnace annealing for 1 h and rapid thermal annealing for a brief period, which enables monitoring of early nucleation events. The influence of implanted dose and annealing type on carbon and hydrogen concentrations, clustering, and bonding were investigated. Rutherford backscattering, elastic recoil detection analysis, infrared spectroscopy, transmission electron microscopy, selected area electron diffraction, ultraviolet-visible absorption measurements, and Raman spectroscopy were used to study these carbon formations. These results, combined with the results of previous investigations on similar systems, show that preferential formation of different carbon phases (diamond, n-diamond, or i-carbon) depends on implantation energy, implantation dose, and annealing conditions. Diamond nanocrystals formed at a relatively low carbon volume density are achieved by deeper implantation and/or lower implanted dose. Higher volume densities led to n-diamond and finally to i-carbon crystal formation. This observed behavior is related to damage sites induced by implantation. The optical properties of different carbon nanocrystal phases were significantly different.

  13. Radial pressure measurement in core/shell nanocrystals

    NASA Astrophysics Data System (ADS)

    Ithurria, Sandrine; Guyot-Sionnest, Philippe; Mahler, Benoît; Dubertret, Benoît

    2009-02-01

    Quantum dots are nanometre-sized semiconductor particles exhibiting unique size-dependent electronic properties. In order to passivate the nanocrystals surface and to protect them from oxidation, we grow a shell composed of a second semiconductor with a larger bandgap on the core (for example a core / shell CdS / ZnS). However, the lattice mismatch between the two materials (typically 7% between ZnS and CdS) induces mechanical stress which can lead to dislocations. To better understand these mechanisms, it is important to be able to measure the pressure induced on the semiconductor core. We used a nanocrystal doped with manganese ions Mn2+, which provide a phosphorescence signal depending on the local pressure. A few dopant atoms per nanoparticle were placed at controlled radial positions in a ZnS shell formed layer by layer. The experimental pressure measurements are in very good agreement with a simple spherically symmetric elastic continuum model[1]. Using manganese as a pressure gauge could be used to better understand some structural phenomena observed in these nanocrystals, such as crystalline phases transition, or shell cracking.

  14. Magnetization dynamics in arrays of strongly interacting magnetic nanocrystals

    NASA Astrophysics Data System (ADS)

    Telem-Shafir, Tamar; Markovich, Gil

    2005-11-01

    Arrays of 6.6nm iron oxide nanocrystals coated with fatty acid molecules were produced using the Langmuir-Blodgett technique. The arrays had a varying number of layers stacked together, going from two dimensional to three dimensional and two different in-plane interparticle separations. While temperature-dependent ac susceptibility measurements of the isolated nanocrystals obeyed the Néel-Brown relaxation law, the array relaxation deviated significantly from this simple law. This deviation together with the observed dc field influence on the susceptibility-temperature curves, the large shifts in blocking temperatures and reduction in susceptibility-temperature curve widths on going from isolated particles to the arrays indicated collective magnetization dynamics during magnetization freezing. A scaling law analysis of this freezing dynamics yielded different powers for the two different interparticle separations with no dependence on dimensionality. In spite of the spin-glass-like behavior, it is possible that small, magnetically ordered domains of nanocrystals form at low temperature.

  15. Regioselective placement of alkanethiolate domains on tetrahedral and octahedral gold nanocrystals.

    PubMed

    Wang, Yifeng; Zeiri, Offer; Meshi, Louisa; Stellacci, Francesco; Weinstock, Ira A

    2012-10-01

    Electrostatically stabilized monolayer shells of metal-oxide cluster anions (polyoxometalates, or POMs) on the surfaces of ca. 8 nm tetrahedral and octahedral gold nanocrystals regioselectively direct water-soluble alkanethiolate ligands to the corners and edges of the gold polyhedra. PMID:22918232

  16. Germanium Nanocrystal Solar Cells

    NASA Astrophysics Data System (ADS)

    Holman, Zachary Charles

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

  17. 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

  18. Ferritin-based nanocrystals for solar energy harvesting

    NASA Astrophysics Data System (ADS)

    Colton, John; Erickson, Stephen; Olsen, Cameron; Embley, Jacob; Smith, Trevor; Watt, Richard

    2015-03-01

    Ferritin is a 12 nm diameter hollow protein with an 8 nm cavity that can be filled with a variety of nanocrystals (ferrihydrite being native). We report on several experiments with ferritin-based nanocrystals designed to utilize ferritin for solar energy harvesting. First, we have shown that the native band gap can be altered by controlling nanocrystal size, by replacing the native iron oxide core with other metal oxides, and by depositing halides and oxo-anions with the iron oxide core. This gives available band gaps of 1.6 to 2.3 eV. Theoretical efficiency calculations based on these band gaps show that the efficiency of a multi-junction solar cell based on layered structures of ferritin can be as high as 44.9 %, and up to 63.1 % if a ferritin-based material with band gap of 1.1 eV can be developed. For the latter case, the efficiencies remain quite high even in a current-matched configuration, namely 50.0 %. We have also demonstrated that photo-excitation of these materials can produce charge separation and give rise to usable electrons; we have used photo-excited electrons to reduce gold in solution and thereby produce gold nanoparticles on the surface of the ferritin. This technique can potentially be extended to platinum, whose nanoparticles catalyze water splitting. This research was partially supported by the Utah Office of Energy Development, Governor's Energy Leadership Scholars Program.

  19. Cellulose nanocrystals/cellulose core-in-shell nanocomposite assemblies.

    PubMed

    Magalhães, Washington Luiz Esteves; Cao, Xiaodong; Lucia, Lucian A

    2009-11-17

    We report herein for the first time how a co-electrospinning technique can be used to overcome the issue of orienting cellulose nanocrystals within a neat cellulose matrix. A home-built co-electrospinning apparatus was fabricated that was comprised of a high-voltage power supply, two concentric capillary needles, and one screw-type pump syringe. Eucalyptus-derived cellulose was dissolved in N-methylmorpholine oxide (NMMO) at 120 degrees C and diluted with dimethyl sulfoxide (DMSO) which was used in the external concentric capillary needle as the shell solution. A cellulose nanocrystal suspension obtained by the sulfuric acid hydrolysis of bleached sisal and cotton fibers was used as the core liquid in the internal concentric capillary needle. Three flow rate ratios between the shell and core, four flow rates for the shell dope solution, and four high voltages were tested. The resultant co-electrospun composite fibers were collected onto a grounded metal screen immersed in cold water. Micrometer and submicrometer cellulose fiber assemblies were obtained which were reinforced with cellulose nanocrystals and characterized by FESEM, FTIR, TGA, and XRD. Surprisingly, it was determined that the physical properties for the cellulose controls are superior to the composites; in addition, the crystallinity of the controls was slightly greater. PMID:19731951

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

    PubMed Central

    2015-01-01

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

  1. Lead sulphide nanocrystal photodetector technologies

    NASA Astrophysics Data System (ADS)

    Saran, Rinku; Curry, Richard J.

    2016-02-01

    Light detection is the underlying principle of many optoelectronic systems. For decades, semiconductors including silicon carbide, silicon, indium gallium arsenide and germanium have dominated the photodetector industry. They can show excellent photosensitivity but are limited by one or more aspects, such as high production cost, high-temperature processing, flexible substrate incompatibility, limited spectral range or a requirement for cryogenic cooling for efficient operation. Recently lead sulphide (PbS) nanocrystals have emerged as one of the most promising new materials for photodetector fabrication. They offer several advantages including low-cost manufacturing, solution processability, size-tunable spectral sensitivity and flexible substrate compatibility, and they have achieved figures of merit outperforming conventional photodetectors. We review the underlying concepts, breakthroughs and remaining challenges in photodetector technologies based on PbS nanocrystals.

  2. Phosphate-free synthesis, optical absorption and photoelectric properties of Cu2ZnGeS4 and Cu2ZnGeSe4 uniform nanocrystals.

    PubMed

    Shi, Liang; Yin, Peiqun

    2013-10-01

    Copper-based quaternary chalcogenide semiconductor Cu2ZnGeS4 and Cu2ZnGeSe4 nanocrystals have been synthesized successfully via a simple and convenient one-pot phosphine-free solution approach. Oleylamine was used as both the solvent and reductant for Se or S and benefited the formation of homogeneous quaternary nanocrystals. Scanning transmission electron microscopy-EDS elemental mapping confirms the uniform spatial distribution of four elements in nanocrystals. UV-Vis absorption spectra of Cu2ZnGeS4 and Cu2ZnGeSe4 nanocrystals show strong photon absorption in the entire visible range. The photoresponsive behavior indicates the potential application of Cu2ZnGeSe4 nanocrystals in solar energy conversion systems. PMID:23900582

  3. An ensemble-based method to assess the quality of a sample of nanocrystals as single photon emitters

    NASA Astrophysics Data System (ADS)

    Vezzoli, Stefano; Shojaii, Seyedruhollah; Cialdi, Simone; Cipriani, Daniele; Castelli, Fabrizio; Paris, Matteo G. A.; Carbone, Luigi; Davide Cozzoli, P.; Giacobino, Elisabeth; Bramati, Alberto

    2013-07-01

    Colloidal semiconductor nanocrystals are among the best candidates for realizing a nano-structured single photon source at room temperature. In this paper we present a new and efficient optical method to assess the quality of a sample of nanocrystals as single-photon emitters, by an ensemble measurement of photoluminescence. We relate the ensemble photoluminescence measurements to the photon statistics of single emitters by a simple theoretical model. As an example we compare two different kinds of CdSe/CdS dot-in-rods, showing a similar degree of single photon emission when observed on a selection of single nanocrystals. The results are compared with anti-bunching measurements realized on single nanocrystals of the two kinds.

  4. Inorganic colloidal nanocrystals: Synthesis and bioapplications

    NASA Astrophysics Data System (ADS)

    Wu, Huimeng

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

  5. Efficient Thermolysis Route to Monodisperse Cu2ZnSnS4 Nanocrystals with Controlled Shape and Structure

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaoyan; Guo, Guobiao; Ji, Cheng; Huang, Kai; Zha, Chenyang; Wang, Yifeng; Shen, Liming; Gupta, Arunava; Bao, Ningzhong

    2014-05-01

    Monodisperse Cu2ZnSnS4 (CZTS) nanocrystals with tunable shape, crystalline phase, and composition are synthesized by efficient thermolysis of a single source precursor of mixed metal-oleate complexes in hot organic solvents with dissolved sulfur sources. Suitable tuning of the synthetic conditions and the Cu/(Zn + Sn) ratio of the precursor has enabled precise control of the crystalline phase in the form of kesterite, or a newly observed wurtzite structure. Nanocrystals with morphology in the form of spherical, rice-like, or rod-like shapes are obtained over a wide range of compositions (0.5 <= Cu/(Zn + Sn) <= 1.2). Both the final products and intermediates for each shape exhibit consistent composition and structure, indicating homogenous nucleation and growth of single-phase nanocrystals. Thin films prepared from colloidal nanocrystal suspensions display interesting shape-dependent photoresponse behavior under white light illumination from a solar simulator.

  6. Cytotoxicity and cellular uptake of ZnS:Mn nanocrystals biofunctionalized with chitosan and aminoacids

    NASA Astrophysics Data System (ADS)

    Sajimol Augustine, M.; Anas, Abdulaziz; Das, Ani V.; Sreekanth, S.; Jayalekshmi, S.

    2015-02-01

    Highly luminescent, manganese doped, zinc sulphide (ZnS:Mn) nanocrystals biofunctionalized with chitosan and various aminoacids such as L-citrulline, L-lysine, L-arginine, L-serine, L-histidine and glycine were synthesized by chemical capping co-precipitation method at room temperature, which is a simple and cost effective technique. The synthesized nanocrystals were structurally characterized by TEM, XRD, EDXS and FT-IR spectroscopy techniques. They possess high colloidal stability with strong orange red photoluminescence emission at 598 nm. The intensity of orange red emission has been observed to be maximum in L-citrulline capped ZnS:Mn nanocrystals in which the emission at 420 nm is effectively quenched by surface passivation due to capping. Taking into consideration the prospects of these highly luminescent, bio-compatible ZnS:Mn nanocrystals in bio-imaging applications, cytotoxicity studies were conducted to identify the capping combination which would accomplish minimum toxic effects. ZnS:Mn nanocrystals biofunctionalized with chitosan, L-citrulline, glycine, L-artginine, L-serine and L-histidine showed least toxicity up to 10 nM concentrations in mouse fibroblast L929 cells, which further confirms their cytocompatibility. Also the ZnS:Mn nanocrystals biofunctionalized with L-arginine showed maximum uptake in in vitro studies carried out in human embryonic kidney cells, HEK-293T, which shows the significant role of this particular amino acid in fetoplacental nutrition. The present study highlights the suitability of aminoacid conjugated ZnS:Mn nanocrystals, as promising candidates for biomedical applications.

  7. Faceting of Nanocrystals during Chemical Transformation: FromSolid Silver Spheres to Hollow Gold Octahedra

    SciTech Connect

    Yin, Yadong; Erdonmez, Can; Alivisatos, A. Paul

    2006-06-23

    Sustained progress in nanocrystal synthesis has enabled recent use of these materials as inorganic, macromolecular precursors that can be chemically transformed into new nanostructures. The literature now contains several cases with chemical transformations being accompanied by varying degrees of modification of properties, including crystal structure and particle shape. As a recent example, we demonstrated that as-synthesized metallic nanocrystals yield, upon oxidation, nanostructures with modified morphologies such as hollow particles. This morphological change derives from directional material flows due to differing diffusivities for the reacting atomic species, in a nanoscale version of the well-known Kirkendall Effect. This general methodology has since been extended by other groups to produce nanostructures with various compositions and shapes. We demonstrate that performing a replacement reaction on single crystalline Ag nanospheres of {approx}10 nm in diameter in an organic solvent produces hollow Au nanocrystals with an octahedral shape. Different from those Au shells made by starting with Ag particles about one order of magnitude larger, which largely reproduce that of the sacrificial Ag counterparts, the hollow nanocrystals obtained in this work show significant changes in the external morphology from the spherical Ag precursors. This evolution of a faceted external morphology during chemical transformation is made possible by the enhanced role of surface effects in our smaller nanocrystals. The competition between the Au atom deposition and Ag atom dissolution on various nanocrystal surfaces is believed to determine the final octahedral shape of the hollow Au nanocrystals. Simultaneous achievement of surface-mediated shape control and a hollow morphology in a one-pot, single-step synthetic procedure in this study promises an avenue to finer tuning of particle morphology, and thus physical properties such as surface plasmon resonance.

  8. Analytical modeling of localized surface plasmon resonance in heterostructure copper sulfide nanocrystals

    SciTech Connect

    Caldwell, Andrew H.; Ha, Don-Hyung; Robinson, Richard D.; Ding, Xiaoyue

    2014-10-28

    Localized surface plasmon resonance (LSPR) in semiconductor nanocrystals is a relatively new field of investigation that promises greater tunability of plasmonic properties compared to metal nanoparticles. A novel process by which the LSPR in semiconductor nanocrystals can be altered is through heterostructure formation arising from solution-based cation exchange. Herein, we describe the development of an analytical model of LSPR in heterostructure copper sulfide-zinc sulfide nanocrystals synthesized via a cation exchange reaction between copper sulfide (Cu{sub 1.81}S) nanocrystals and Zn ions. The cation exchange reaction produces dual-interface, heterostructure nanocrystals in which the geometry of the copper sulfide phase can be tuned from a sphere to a thin disk separating symmetrically-grown sulfide (ZnS) grains. Drude model electronic conduction and Mie-Gans theory are applied to describe how the LSPR wavelength changes during cation exchange, taking into account the morphology evolution and changes to the local permittivity. The results of the modeling indicate that the presence of the ZnS grains has a significant effect on the out-of-plane LSPR mode. By comparing the results of the model to previous studies on solid-solid phase transformations of copper sulfide in these nanocrystals during cation exchange, we show that the carrier concentration is independent of the copper vacancy concentration dictated by its atomic phase. The evolution of the effective carrier concentration calculated from the model suggests that the out-of-plane resonance mode is dominant. The classical model was compared to a simplified quantum mechanical model which suggested that quantum mechanical effects become significant when the characteristic size is less than ∼8 nm. Overall, we find that the analytical models are not accurate for these heterostructured semiconductor nanocrystals, indicating the need for new model development for this emerging field.

  9. Light-Harvesting Systems Based on Organic Nanocrystals To Mimic Chlorosomes.

    PubMed

    Chen, Peng-Zhong; Weng, Yu-Xiang; Niu, Li-Ya; Chen, Yu-Zhe; Wu, Li-Zhu; Tung, Chen-Ho; Yang, Qing-Zheng

    2016-02-18

    We report the first highly efficient artificial light-harvesting systems based on nanocrystals of difluoroboron chromophores to mimic the chlorosomes, one of the most efficient light-harvesting systems found in green photosynthetic bacteria. Uniform nanocrystals with controlled donor/acceptor ratios were prepared by simple coassembly of the donors and acceptors in water. The light-harvesting system funneled the excitation energy collected by a thousand donor chromophores to a single acceptor. The well-defined spatial organization of individual chromophores in the nanocrystals enabled an energy transfer efficiency of 95 %, even at a donor/acceptor ratio as high as 1000:1, and a significant fluorescence of the acceptor was observed up to donor/acceptor ratios of 200 000:1. PMID:26799735

  10. Formation of Organic Molecular Nanocrystals under Rigid Confinement with Analysis by Solid State NMR

    PubMed Central

    Yang, X.; Ong, T. C.; Michaelis, V. K.; Heng, S.; Huang, J.; Griffin, R. G.; Myerson, A. S.

    2014-01-01

    Crystallization in rigid confinement is a promising method to obtain organic molecular nanocrystals. However, the crystallization behavior and the related characterization methods are not well studied. Here we present a systematic study of the nucleation of organic molecular nanocrystals in rigid pores. Four different compounds were studied, ibuprofen, fenofibrate, griseofulvin, and indomethacin, which range from simple to complex molecules. Solid-state Nuclear Magnetic Resonance (NMR) was employed to analyse the structure of these compounds inside pores which are difficult to characterize by other analytical methods. We successfully demonstrated the production of nano-crystalline ibuprofen, fenofibrate and griseofulvin in porous silica particles with ~ 40 nm pores. These nanocrystals showed significant enhancement in dissolution rates. These results help advance the fundamental understanding of nucleation under rigid confinement and may lead to potential applications in developing new formulations in the pharmaceutical industry. PMID:25258590

  11. Shape and size controlled synthesis of uniform iron oxide nanocrystals through new non-hydrolytic routes

    NASA Astrophysics Data System (ADS)

    Li, Wenlu; Lee, Seung Soo; Wu, Jiewei; Hinton, Carl H.; Fortner, John D.

    2016-08-01

    New, non-hydrolytic routes to synthesize highly crystalline iron oxide nanocrystals (8–40 nm, magnetite) are described in this report whereby particle size and morphology were precisely controlled through reactant (precursor, e.g. (FeO(OH)) ratios, co-surfactant and organic additive, and/or reaction time. Particle size, with high monodispersivity (<10%), is demonstrated to be a function of precursor concentrations and through the addition of different cosurfactants and/or additives, cubic, octahedral, potato-like, and flower-like iron oxide nanocrystals can be reproducibly synthesized through simple one-pot thermal decomposition methods. High resolution transmission electron microscope, x-ray diffraction, and superconducting quantum interference device were used to characterize the size, structure and magnetic properties of the resulting nanocrystals. For aqueous applications, materials synthesized/purified in organic solvents are broadly water dispersible through a variety of phase (aqueous) transfer method(s).

  12. Shape and size controlled synthesis of uniform iron oxide nanocrystals through new non-hydrolytic routes.

    PubMed

    Li, Wenlu; Lee, Seung Soo; Wu, Jiewei; Hinton, Carl H; Fortner, John D

    2016-08-12

    New, non-hydrolytic routes to synthesize highly crystalline iron oxide nanocrystals (8-40 nm, magnetite) are described in this report whereby particle size and morphology were precisely controlled through reactant (precursor, e.g. (FeO(OH)) ratios, co-surfactant and organic additive, and/or reaction time. Particle size, with high monodispersivity (<10%), is demonstrated to be a function of precursor concentrations and through the addition of different cosurfactants and/or additives, cubic, octahedral, potato-like, and flower-like iron oxide nanocrystals can be reproducibly synthesized through simple one-pot thermal decomposition methods. High resolution transmission electron microscope, x-ray diffraction, and superconducting quantum interference device were used to characterize the size, structure and magnetic properties of the resulting nanocrystals. For aqueous applications, materials synthesized/purified in organic solvents are broadly water dispersible through a variety of phase (aqueous) transfer method(s). PMID:27354334

  13. Bistable Magnetoresistance Switching in Exchange-Coupled CoFe2O4-Fe3O4 Binary Nanocrystal Superlattices by Self-Assembly and Thermal Annealing

    SciTech Connect

    Chen, J; Ye, XC; Oh, SJ; Kikkawa, JM; Kagan, CR; Murray, CB

    2013-02-01

    Self-assembly of multicomponent nanocrystal superlattices provides a modular approach to the design of metamaterials by choosing constituent nanocrystal building blocks with desired physical properties and engineering the interparticle coupling. In this work, we report the self-assembly of binary nanocrystal superlattices composed of magnetically hard CoFe2O4 nanocrystals and magnetically soft Fe3O4 nanocrystals. Both NaZn13- and MgZn2-type CoFe2O4-Fe3O4 binary nanocrystal superlattices have been formed by the liquid-air interfacial assembly approach. Exchange coupling is achieved in both types of binary superlattices after thermal annealing under vacuum at 400 degrees C. The exchange-coupled CoFe2O4-Fe3O4 binary nanocrystal superlattices show single-phase magnetization switching behavior and magnetoresistance switching behavior below 200 K. The NaZn13-type CoFe2O4-Fe3O4 binary nanocrystal superlattices annealed at 500 degrees C even exhibit bistable magnetoresistance switching behavior at room temperature constituting a simple nonvolatile memory function.

  14. Chemical and thermodynamic control of the surface of semiconductor nanocrystals for designer white light emitters.

    PubMed

    Krause, Michael M; Mooney, Jonathan; Kambhampati, Patanjali

    2013-07-23

    Small CdSe semiconductor nanocrystals with diameters below 2 nm are thought to emit white light due to random surface defects which result in a broad distribution of midgap emitting states, thereby preventing rational design of small nanocrystal white light emitters. We perform temperature dependent photoluminescence experiments before and after ligand exchange and electron transfer simulations to reveal a very simple microscopic picture of the origin of the white light. These experiments and simulations reveal that these small nanocrystals can be physically modeled in precisely the same way as normal-sized semiconductor nanocrystals; differences in their emission spectra arise from their surface thermodynamics. The white light emission is thus a consequence of the thermodynamic relationship between a core excitonic state and an optically bright surface state with good quantum yield. By virtue of this understanding of the surface and the manner in which it is coupled to the core excitonic states of these nanocrystals, we show both chemical and thermodynamic control of the photoluminescence spectra. We find that using both temperature and appropriate choice in ligands, one can rationally control the spectra so as to engineer the surface to target color rendering coordinates for displays and white light emitters. PMID:23802709

  15. Electronic displays using optically pumped luminescent semiconductor nanocrystals

    DOEpatents

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

    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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. Plasmon dynamics in colloidal Cu₂-xSe nanocrystals.

    PubMed

    Scotognella, Francesco; Della Valle, Giuseppe; Srimath Kandada, Ajay Ram; Dorfs, Dirk; Zavelani-Rossi, Margherita; Conforti, Matteo; Miszta, Karol; Comin, Alberto; Korobchevskaya, Kseniya; Lanzani, Guglielmo; Manna, Liberato; Tassone, Francesco

    2011-11-01

    The optical response of metallic nanostructures after intense excitation with femtosecond-laser pulses has recently attracted increasing attention: such response is dominated by ultrafast electron-phonon coupling and offers the possibility to achieve optical modulation with unprecedented terahertz bandwidth. In addition to noble metal nanoparticles, efforts have been made in recent years to synthesize heavily doped semiconductor nanocrystals so as to achieve a plasmonic behavior with spectrally tunable features. In this work, we studied the dynamics of the localized plasmon resonance exhibited by colloidal Cu(2-x)Se nanocrystals of 13 nm in diameter and with x around 0.15, upon excitation by ultrafast laser pulses via pump-probe experiments in the near-infrared, with ∼200 fs resolution time. The experimental results were interpreted according to the two-temperature model and revealed the existence of strong nonlinearities in the plasmonic absorption due to the much lower carrier density of Cu(2-x)Se compared to noble metals, which led to ultrafast control of the probe signal with modulation depth exceeding 40% in transmission. PMID:21939261

  3. Tailoring Plasmonic Enhanced Upconversion in Single NaYF4:Yb3+/Er3+ Nanocrystals

    PubMed Central

    Wang, Ya-Lan; Mohammadi Estakhri, Nasim; Johnson, Amber; Li, Hai-Yang; Xu, Li-Xiang; Zhang, Zhenyu; Alù, Andrea; Wang, Qu-Quan; Shih, Chih-Kang (Ken)

    2015-01-01

    By using silver nanoplatelets with a widely tunable localized surface plasmon resonance (LSPR), and their corresponding local field enhancement, here we show large manipulation of plasmonic enhanced upconversion in NaYF4:Yb3+/Er3+ nanocrystals at the single particle level. In particular, we show that when the plasmonic resonance of silver nanolplatelets is tuned to 656 nm, matching the emission wavelength, an upconversion enhancement factor ~5 is obtained. However, when the plasmonic resonance is tuned to 980 nm, matching the nanocrystal absorption wavelength, we achieve an enhancement factor of ~22 folds. The precise geometric arrangement between fluorescent nanoparticles and silver nanoplatelets allows us to make, for the first time, a comparative analysis between experimental results and numerical simulations, yielding a quantitative agreement at the single particle level. Such a comparison lays the foundations for a rational design of hybrid metal-fluorescent nanocrystals to harness the upconversion enhancement for biosensing and light harvesting applications. PMID:25976870

  4. PdCuPt Nanocrystals with Multibranches for Enzyme-Free Glucose Detection.

    PubMed

    Fu, Shaofang; Zhu, Chengzhou; Song, Junhua; Engelhard, Mark; Xia, Haibing; Du, Dan; Lin, Yuehe

    2016-08-31

    By carefully controlling the synthesis condition, branched PtCu bimetallic templates were synthesized in aqueous solution. After the galvanic replacement reaction between PtCu templates and the Pt precursors, PdCuPt trimetallic nanocrystals with branched structures were obtained. Owing to the open structure and the optimized composition, the electrochemical experimental results reveal that the PdCuPt trimetallic nanocrystals possess high electrocatalytic activity, selectivity and stability for the oxidation of glucose in alkaline solution. In detail, a detection limit of 1.29 μM and a sensitivity of 378 μA/mM/cm(2) are achieved. The good electrocatalytic performance should be attributed to the unique branched nanostructure as well as the synergistic effect among metals. The superior catalytic properties suggest that these nanocrystals are promising for enzyme-free detection of glucose. PMID:27494365

  5. Tailoring Plasmonic Enhanced Upconversion in Single NaYF4:Yb(3+)/Er(3+) Nanocrystals.

    PubMed

    Wang, Ya-Lan; Mohammadi Estakhri, Nasim; Johnson, Amber; Li, Hai-Yang; Xu, Li-Xiang; Zhang, Zhenyu; Alù, Andrea; Wang, Qu-Quan; Shih, Chih-Kang Ken

    2015-01-01

    By using silver nanoplatelets with a widely tunable localized surface plasmon resonance (LSPR), and their corresponding local field enhancement, here we show large manipulation of plasmonic enhanced upconversion in NaYF4:Yb(3+)/Er(3+) nanocrystals at the single particle level. In particular, we show that when the plasmonic resonance of silver nanolplatelets is tuned to 656 nm, matching the emission wavelength, an upconversion enhancement factor ~5 is obtained. However, when the plasmonic resonance is tuned to 980 nm, matching the nanocrystal absorption wavelength, we achieve an enhancement factor of ~22 folds. The precise geometric arrangement between fluorescent nanoparticles and silver nanoplatelets allows us to make, for the first time, a comparative analysis between experimental results and numerical simulations, yielding a quantitative agreement at the single particle level. Such a comparison lays the foundations for a rational design of hybrid metal-fluorescent nanocrystals to harness the upconversion enhancement for biosensing and light harvesting applications. PMID:25976870

  6. Chemically directing d-block heterometallics to nanocrystal surfaces as molecular beacons of surface structure

    SciTech Connect

    Rosen, Evelyn L.; Gilmore, Keith; Sawvel, April M.; Hammack, Aaron T.; Doris, Sean E.; Aloni, Shaul; Altoe, Virginia; Nordlund, Dennis; Weng, Tsu -Chien; Sokaras, Dimosthenis; Cohen, Bruce E.; Urban, Jeffrey J.; Ogletree, D. Frank; Milliron, Delia J.; Prendergast, David; Helms, Brett A.

    2015-07-28

    Our understanding of structure and bonding in nanoscale materials is incomplete without knowledge of their surface structure. Needed are better surveying capabilities responsive not only to different atoms at the surface, but also their respective coordination environments. We report here that d-block organometallics, when placed at nanocrystal surfaces through heterometallic bonds, serve as molecular beacons broadcasting local surface structure in atomic detail. This unique ability stems from their elemental specificity and the sensitivity of their d-orbital level alignment to local coordination environment, which can be assessed spectroscopically. Re-surfacing cadmium and lead chalcogenide nanocrystals with iron- or ruthenium-based molecular beacons is readily accomplished with trimethylsilylated cyclopentadienyl metal carbonyls. For PbSe nanocrystals with iron-based beacons, we show how core-level X-ray spectroscopies and DFT calculations enrich our understanding of both charge and atomic reorganization at the surface when beacons are bound.

  7. Chemically directing d-block heterometallics to nanocrystal surfaces as molecular beacons of surface structure

    DOE PAGESBeta

    Rosen, Evelyn L.; Gilmore, Keith; Sawvel, April M.; Hammack, Aaron T.; Doris, Sean E.; Aloni, Shaul; Altoe, Virginia; Nordlund, Dennis; Weng, Tsu -Chien; Sokaras, Dimosthenis; et al

    2015-07-28

    Our understanding of structure and bonding in nanoscale materials is incomplete without knowledge of their surface structure. Needed are better surveying capabilities responsive not only to different atoms at the surface, but also their respective coordination environments. We report here that d-block organometallics, when placed at nanocrystal surfaces through heterometallic bonds, serve as molecular beacons broadcasting local surface structure in atomic detail. This unique ability stems from their elemental specificity and the sensitivity of their d-orbital level alignment to local coordination environment, which can be assessed spectroscopically. Re-surfacing cadmium and lead chalcogenide nanocrystals with iron- or ruthenium-based molecular beacons ismore » readily accomplished with trimethylsilylated cyclopentadienyl metal carbonyls. For PbSe nanocrystals with iron-based beacons, we show how core-level X-ray spectroscopies and DFT calculations enrich our understanding of both charge and atomic reorganization at the surface when beacons are bound.« less

  8. Low-threshold amplified spontaneous emission and lasing from colloidal nanocrystals of caesium lead halide perovskites

    PubMed Central

    Yakunin, Sergii; Protesescu, Loredana; Krieg, Franziska; Bodnarchuk, Maryna I.; Nedelcu, Georgian; Humer, Markus; De Luca, Gabriele; Fiebig, Manfred; Heiss, Wolfgang; Kovalenko, Maksym V.

    2015-01-01

    Metal halide semiconductors with perovskite crystal structures have recently emerged as highly promising optoelectronic materials. Despite the recent surge of reports on microcrystalline, thin-film and bulk single-crystalline metal halides, very little is known about the photophysics of metal halides in the form of uniform, size-tunable nanocrystals. Here we report low-threshold amplified spontaneous emission and lasing from ∼10 nm monodisperse colloidal nanocrystals of caesium lead halide perovskites CsPbX3 (X=Cl, Br or I, or mixed Cl/Br and Br/I systems). We find that room-temperature optical amplification can be obtained in the entire visible spectral range (440–700 nm) with low pump thresholds down to 5±1 μJ cm−2 and high values of modal net gain of at least 450±30 cm−1. Two kinds of lasing modes are successfully observed: whispering-gallery-mode lasing using silica microspheres as high-finesse resonators, conformally coated with CsPbX3 nanocrystals and random lasing in films of CsPbX3 nanocrystals. PMID:26290056

  9. Low-threshold amplified spontaneous emission and lasing from colloidal nanocrystals of caesium lead halide perovskites

    NASA Astrophysics Data System (ADS)

    Yakunin, Sergii; Protesescu, Loredana; Krieg, Franziska; Bodnarchuk, Maryna I.; Nedelcu, Georgian; Humer, Markus; de Luca, Gabriele; Fiebig, Manfred; Heiss, Wolfgang; Kovalenko, Maksym V.

    2015-08-01

    Metal halide semiconductors with perovskite crystal structures have recently emerged as highly promising optoelectronic materials. Despite the recent surge of reports on microcrystalline, thin-film and bulk single-crystalline metal halides, very little is known about the photophysics of metal halides in the form of uniform, size-tunable nanocrystals. Here we report low-threshold amplified spontaneous emission and lasing from ~10 nm monodisperse colloidal nanocrystals of caesium lead halide perovskites CsPbX3 (X=Cl, Br or I, or mixed Cl/Br and Br/I systems). We find that room-temperature optical amplification can be obtained in the entire visible spectral range (440-700 nm) with low pump thresholds down to 5+/-1 μJ cm-2 and high values of modal net gain of at least 450+/-30 cm-1. Two kinds of lasing modes are successfully observed: whispering-gallery-mode lasing using silica microspheres as high-finesse resonators, conformally coated with CsPbX3 nanocrystals and random lasing in films of CsPbX3 nanocrystals.

  10. Nanocrystal technology, drug delivery and clinical applications

    PubMed Central

    Junghanns, Jens-Uwe A H; Müller, Rainer H

    2008-01-01

    Nanotechnology will affect our lives tremendously over the next decade in very different fields, including medicine and pharmacy. Transfer of materials into the nanodimension changes their physical properties which were used in pharmaceutics to develop a new innovative formulation principle for poorly soluble drugs: the drug nanocrystals. The drug nanocrystals do not belong to the future; the first products are already on the market. The industrially relevant production technologies, pearl milling and high pressure homogenization, are reviewed. The physics behind the drug nanocrystals and changes of their physical properties are discussed. The marketed products are presented and the special physical effects of nanocrystals explained which are utilized in each market product. Examples of products in the development pipelines (clinical phases) are presented and the benefits for in vivo administration of drug nanocrystals are summarized in an overview. PMID:18990939

  11. 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

  12. Copper selenide nanocrystals for photothermal therapy.

    PubMed

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

    2011-06-01

    Ligand-stabilized copper selenide (Cu(2-x)Se) 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 × 10(7) cm(-1) M(-1) at 980 nm. When excited with 800 nm light, the Cu(2-x)Se 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 Cu(2-x)Se nanocrystals in the presence of human colorectal cancer cell (HCT-116) led to cell destruction after 5 min of laser irradiation at 33 W/cm(2), demonstrating the viabilitiy of Cu(2-x)Se nanocrystals for photothermal therapy applications. PMID:21553924

  13. Influence of dopant distribution on the plasmonic properties of indium tin oxide nanocrystals.

    PubMed

    Lounis, Sebastien D; Runnerstrom, Evan L; Bergerud, Amy; Nordlund, Dennis; Milliron, Delia J

    2014-05-14

    Doped metal oxide nanocrystals represent an exciting frontier for colloidal synthesis of plasmonic materials, displaying unique optoelectronic properties and showing promise for a variety of applications. However, fundamental questions about the nature of doping in these materials remain. In this article, the strong influence of radial dopant distribution on the optoelectronic properties of colloidal indium tin oxide nanocrystals is reported. Comparing elemental depth-profiling by X-ray photoelectron spectroscopy (XPS) with detailed modeling and simulation of the optical extinction of these nanocrystals using the Drude model for free electrons, a correlation between surface segregation of tin ions and the average activation of dopants is observed. A strong influence of surface segregation of tin on the line shape of the localized surface plasmon resonance (LSPR) is also reported. Samples with tin segregated near the surface show a symmetric line shape that suggests weak or no damping of the plasmon by ionized impurities. It is suggested that segregation of tin near the surface facilitates compensation of the dopant ions by electronic defects and oxygen interstitials, thus reducing activation. A core-shell model is proposed to explain the observed differences in line shape. These results demonstrate the nuanced role of dopant distribution in determining the optoelectronic properties of semiconductor nanocrystals and suggest that more detailed study of the distribution and structure of defects in plasmonic colloidal nanocrystals is warranted. PMID:24786283

  14. Structure-Dependent Spin Polarization in Polymorphic CdS:Y Semiconductor Nanocrystals.

    PubMed

    Wang, Pan; Xiao, Bingxin; Zhao, Rui; Ma, Yanzhang; Zhang, Mingzhe

    2016-03-01

    Searching for the polymorphic semiconductor nanocrystals would provide precise and insightful structure-spin polarization correlations and meaningful guidance for designing and synthesizing high spin-polarized spintronic materials. Herein, the high spin polarization is achieved in polymorphic CdS:Y semiconductor nanocrystals. The high-pressure polymorph of rock-salt CdS:Y nanocrystals has been recovered at ambient conditions synthesized by the wurtzite CdS:Y nanocrystals as starting material under 5.2 GPa and 300 °C conditions. The rock-salt CdS:Y polymorph displays more robust room-temperature ferromagnetism than wurtzite sample, which can reach the ferromagnetic level of conventional semiconductors doped with magnetic transition-metal ions, mainly due to the significantly enhanced spin configuration and defect states. Therefore, crystal structure directly governs the spin configuration, which determines the degree of spin polarization. This work can provide experimental and theoretical methods for designing the high spin-polarized semiconductor nanocrystals, which is important for applications in semiconductor spintronics. PMID:26905093

  15. Influence of Dopant Distribution on the Plasmonic Properties of Indium Tin Oxide Nanocrystals

    SciTech Connect

    Lounis, SD; Runnerstrom, EL; Bergerud, A; Nordlund, D; Milliron, DJ

    2014-05-14

    Doped metal oxide nanocrystals represent an exciting frontier for colloidal synthesis of plasmonic materials, displaying unique optoelectronic properties and showing promise for a variety of applications. However, fundamental questions about the nature of doping in these materials remain. In this article, the strong influence of radial dopant distribution on the optoelectronic properties of colloidal indium tin oxide nanocrystals is reported. Comparing elemental depth-profiling by X-ray photoelectron spectroscopy (XPS) with detailed modeling and simulation of the optical extinction of these nanocrystals using the Drude model for free electrons, a correlation between surface segregation of tin ions and the average activation of dopants is observed. A strong influence of surface segregation of tin on the line shape of the localized surface plasmon resonance (LSPR) is also reported. Samples with tin segregated near the surface show a symmetric line shape that suggests weak or no damping of the plasmon by ionized impurities. It is suggested that segregation of tin near the surface facilitates compensation of the dopant ions by electronic defects and oxygen interstitials, thus reducing activation. A core shell model is proposed to explain the observed differences in line shape. These results demonstrate the nuanced role of dopant distribution in determining the optoelectronic properties of semiconductor nanocrystals and suggest that more detailed study of the distribution and structure of defects in plasmonic colloidal nanocrystals is warranted.

  16. Alternative synthesis of CuFeSe2 nanocrystals with magnetic and photoelectric properties.

    PubMed

    Wang, Wenliang; Jiang, Jun; Ding, Tao; Wang, Chunde; Zuo, Jian; Yang, Qing

    2015-02-01

    Monodisperse CuFeSe2 nanocrystals of high quality have been successfully synthesized for the first time using a hot-solution injection method from the reaction of metallic acetylacetonates with diphenyl diselenide (Ph2Se2) in oleylamine with addition of oleic acid at 255 °C for 90 min. The characterizations of X-ray diffraction, electron microscopy, and compositional analysis reveal that the resulting CuFeSe2 nanocrystals are of tetragonal phase with a stoichiometric composition. The CuFeSe2 nanocrystals exhibit well-defined quasi-cubic shape with an average size of ∼18 nm, and their shape can be tuned from quasi-cubes to quasi-spheres by adjusting the reaction parameters. Magnetic measurement reveals that the as-synthesized CuFeSe2 nanocrystals are ferromagnetic and paramagnetic at 4 and 300 K, respectively. Additionally, the current-voltage (I-V) behavior of the CuFeSe2 nanocrystals suggests that they are promising candidates for application in optoelectronics and solar energy conversion. PMID:25562289

  17. Structural Characterization of Bimetallic Nanocrystal Electrocatalysts

    SciTech Connect

    Cullen, David A

    2016-01-01

    Late transition metal nanocrystals find applications in heterogeneous catalysis such as plasmon-enhanced catalysis and as electrode materials for fuel cells, a zero-emission and sustainable energy technology. Their commercial viability for automotive transportation has steadily increased in recent years, almost exclusively due to the discovery of more efficient bimetallic nanocatalysts for the oxygen reduction reaction (ORR) at the cathode. Despite improvements to catalyst design, achieving high activity while maintaining durability is essential to further enhance their performance for this and other important applications in catalysis. Electronic effects arising from the generation of metal-metal interfaces, from plasmonic metals, and from lattice distortions, can vastly improve sorption properties at catalytic surfaces, while increasing durability.[1] Multimetallic lattice-strained nanoparticles are thus an interesting opportunity for fundamental research.[2,3] A colloidal synthesis approach is demonstrated to produce AuPd alloy and Pd@Au core-shell nanoicosahedra as catalysts for electro-oxidations. The nanoparticles are characterized using aberration-corrected scanning transmission electron microscopy (ac-STEM) and large solid angle energy dispersive X-ray spectroscopy (EDS) on an FEI Talos 4-detector STEM/EDS system. Figure 1 shows bright-field (BF) and high-angle annular dark-field (HAADF) ac-STEM images of the alloy and core-shell nanoicosahedra together with EDS line-scans and elemental maps. These structures are unique in that the presence of twin boundaries, alloying, and core-shell morphology could create highly strained surfaces and interfaces. The shell thickness of the core-shell structures observed in HAADF-STEM images is tuned by adjusting the ratio between metal precursors (Figure 2a-f) to produce shells ranging from a few to several monolayers. Specific activity was measured in ethanol electro-oxidation to examine the effect of shell thickness on

  18. Superconductivity in colloidal lead nanocrystals

    NASA Astrophysics Data System (ADS)

    Zolotavin, Pavlo

    Monodisperse colloidal lead nanoparticles with diameters ranging from 4.4 to 20 nm were prepared by a self-limiting growth method. The nanoparticles are protected from oxidation by an amorphous lead-tin oxide shell of 1.5-2 nm thickness. The magnetic susceptibility of the particles was measured as a function of size, temperature and magnetic field. The Meissner effect was observed indicating the superconducting transition. For the 20 and 16 nm particles, the critical temperature is suppressed to 6.9 K from the bulk value of 7.2 K and is further reduced for smaller particles. Depending on the size of the particles, the critical field is enhanced by 60 to 140 times. The coupling between particles was in situ controlled through the conversion of the oxides present on the surface of the nanoparticles to chalcogenides. This transformation allows for a 109-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 x 103 A/cm 2. In turn, the critical field of the sample shows 50-fold enhancement compared to bulk Pb. A method to convert the original Pb/PbO nanocrystals into colloidal Pb/PbS (Se, Te) particle was developed. This alleviates the necessity of chemical post processing and provides a truly colloidal superconductor. Paramagnetic Meissner effect of abnormally large amplitude is observed for Pb/PbTe nanocrystal assemblies. The material described in this manuscript is the first nanostructured superconductor prepared by the bottom-up approach starting from colloidal nanoparticles.

  19. Laser-induced growth of nanocrystals embedded in porous materials

    NASA Astrophysics Data System (ADS)

    Capoen, Bruno; Chahadih, Abdallah; El Hamzaoui, Hicham; Cristini, Odile; Bouazaoui, Mohamed

    2013-06-01

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

  20. Laser-induced growth of nanocrystals embedded in porous materials

    PubMed Central

    2013-01-01

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

  1. Femtosecond Laser Synthesis of Multi-Element Nanocrystals

    SciTech Connect

    Dinh, L N; Trelenberg, T; Torralva, B; Stuart, B C; Balooch, M

    2003-01-08

    We studied the conditions under which short-pulsed laser deposited (PLD) stoichiometric multi-element nanocrystals of GaAs,InP,CoPt and Inconel (an alloy of Cr, Fe and Ni) are formed. The properties of the PLD nanoclusters and the irradiated targets were investigated as a function of the laser pulse-length (150 fs-500 ps) and the inert background gas pressure in the synthesis chamber (microTorr to hundreds of Torr). Our results reveal that the formation of stoichiometric GaAs nanocrystals required ablating a GaAs target with a shorter than 25 ps laser in a {ge} 50 miliTorr of inert background pressure. For InP, a mixture of stoichiometric InP and In nanocrystals with an InP/In ratio of {approx} 1 resulted upon ablating an InP target in Ar at 1 Torr. This InP/In ratio increased to {approx} 5 when ablating the InP target in an Ar pressure of 750 Torr. In case of CoPt alloy, the stoichiometry in the target was not reflected in the collected nanocluster films, independent of the background gas pressure. Interestingly, the stoichiometry of the target was found in the collected nanocluster films when an Inconel target was ablated by a femtosecond laser even in vacuum. It is noted that the constituents of Inconel (Cr, Fe and Ni) have similar vapor pressures while Co and Pt do not. Our experimental results suggest that the stoichiometries of the PLD multi-element nanoclusters are closer with those of the targets when shorter than 25 ps lasers are used. However, this does not imply that simply irradiating a multi-element target in vacuum with a shorter than 25 ps pulse-length laser would automatically result in the formation of stoichiometric nanocrystals. The preservation of the stoichiometry of the irradiated target and the formation of stoichiometric semiconductor nanocrystals require ablating the targets with a shorter than 25 ps laser in a background gas. The minimum background gas pressure is materials dependent. And for metal alloys, the stoichiometry of the ablated

  2. Adsorption of alkali, alkaline-earth, simple and 3d transition metal, and nonmetal atoms on monolayer MoS{sub 2}

    SciTech Connect

    Li, X. D.; Fang, Y. M.; Wu, S. Q. E-mail: wsq@xmu.edu.cn; Zhu, Z. Z. E-mail: wsq@xmu.edu.cn

    2015-05-15

    Single adsorption of different atoms on pristine two-dimensional monolayer MoS{sub 2} have been systematically investigated by using density functional calculations with van der Waals correction. The adatoms cover alkali metals, alkaline earth metals, main group metal, 3d-transition metals, coinage metal and nonmetal atoms. Depending on the adatom type, metallic, semimetallic or semiconducting behavior can be found in direct bandgap monolayer MoS{sub 2}. Additionally, local or long-range magnetic moments of two-dimensional MoS{sub 2} sheet can also attained through the adsorption. The detailed atomic-scale knowledge of single adsorption on MoS{sub 2} monolayer is important not only for the sake of a theoretical understanding, but also device level deposition technological application.

  3. Solution synthesis, optical properties, and bioimaging applications of silicon nanocrystals.

    PubMed

    McVey, Benjamin F P; Tilley, Richard D

    2014-10-21

    Understanding and unlocking the potential of semiconductor nanocrystals (NCs) is important for future applications ranging from biomedical imaging contrast agents to the next generation of solar cells and LEDs. Silicon NCs (Si NCs) have key advantages compared with other semiconductor NCs due to silicon's high natural abundance, low toxicity and strong biocompatibility, and unique size, and surface dependent optical properties. In this Account, we review and discuss the synthesis, surface modification, purification, optical properties, and applications of Si NCs. The synthetic methods used to make Si NCs have improved considerably in the last 5-10 years; highly monodisperse Si NCs can now be produced on the near gram scale. Scaled-up syntheses have allowed scientists to drive further toward the commercial utilization of Si NCs. The synthesis of doped Si NCs, through addition of a simple elemental precursor to a reaction mixture or by the production of a single source precursor, has shown great promise. Doped Si NCs have demonstrated unique or enhanced properties compared with pure Si NCs, for example, magnetism due to the presence of magnetic metals like Fe and Mn. Surface reactions have reached a new level of sophistication where organic (epoxidation and diol formation) and click (thiol based) chemical reactions can be carried out on attached surface molecules. This has led to a wide range of biocompatible functional groups as well as a degree of emission tuneability. The purification of Si NCs has been improved through the use of size separation columns and size selective precipitation. These purification approaches have yielded highly monodisperse and pure Si NCs previously unachieved. This has allowed scientists to study the size and surface dependent properties and toxicity and enabled the use of Si NCs in biomedical applications. The optical properties of Si NCs are complex. Using a combination of characterization techniques, researchers have explored the

  4. Bioaccumulation and biomarker responses of cubic and octahedral Cu2O micro/nanocrystals in Daphnia magna.

    PubMed

    Fan, Wenhong; Shi, Zhiwei; Yang, Xiuping; Cui, Minming; Wang, Xiaolong; Zhang, Dongfeng; Liu, Hong; Guo, Lin

    2012-11-15

    Great progress has been made in the controlled fabrication of nanomaterials with given sizes, shapes, and geometries. However, how such changes in structure potentially affect the bioavailability and toxicity of metal nanoparticles to aquatic organisms remains mostly unknown. The present study reports the different behaviors of two types of Cu(2)O micro/nanocrystals (micro/nano-Cu(2)O) with different shapes (cubic and octahedral) and crystallographies (with exposed surfaces as {100} or {111}). The bioaccumulation, median lethal concentration, and biomarker responses of Daphnia magna exposed to the two micro/nanocrystals are also investigated. The Cu accumulation, production of metallothionein (MT), and inhibition ratio of D. magna increased gradually with increasing micro/nano-Cu(2)O concentration. The two crystals showed slight Cu accumulation differences toward D. magna, and their biomarker responses and toxicities to D. magna differed significantly as well. The octahedral Cu(2)O micro/nanocrystals were more toxic to D. magna compared with the cubic micro/nanocrystals probably because of the higher surface activities of the {111} facets compared with those of the {100} facets for cuprites. Food ingestion was the main entry pathway of the micro/nanocrystals into organisms, and toxicity was consequently determined based on the dissolution behavior of the micro/nanocrystals in vivo. PMID:22999974

  5. FeCo/graphitic-shell nanocrystals as advanced magnetic-resonance-imaging and near-infrared agents

    NASA Astrophysics Data System (ADS)

    Seo, Won Seok; Lee, Jin Hyung; Sun, Xiaoming; Suzuki, Yoriyasu; Mann, David; Liu, Zhuang; Terashima, Masahiro; Yang, Philip C.; McConnell, Michael V.; Nishimura, Dwight G.; Dai, Hongjie

    2006-12-01

    Nanocrystals with advanced magnetic or optical properties have been actively pursued for potential biological applications, including integrated imaging, diagnosis and therapy. Among various magnetic nanocrystals, FeCo has superior magnetic properties, but it has yet to be explored owing to the problems of easy oxidation and potential toxicity. Previously, FeCo nanocrystals with multilayered graphitic carbon, pyrolytic carbon or inert metals have been obtained, but not in the single-shelled, discrete, chemically functionalized and water-soluble forms desired for biological applications. Here, we present a scalable chemical vapour deposition method to synthesize FeCo/single-graphitic-shell nanocrystals that are soluble and stable in water solutions. We explore the multiple functionalities of these core-shell materials by characterizing the magnetic properties of the FeCo core and near-infrared optical absorbance of the single-layered graphitic shell. The nanocrystals exhibit ultra-high saturation magnetization, r1 and r2 relaxivities and high optical absorbance in the near-infrared region. Mesenchymal stem cells are able to internalize these nanoparticles, showing high negative-contrast enhancement in magnetic-resonance imaging (MRI). Preliminary in vivo experiments achieve long-lasting positive-contrast enhancement for vascular MRI in rabbits. These results point to the potential of using these nanocrystals for integrated diagnosis and therapeutic (photothermal-ablation) applications.

  6. Progress in the study of drug nanocrystals.

    PubMed

    Shi, Jing; Guo, Fei; Zheng, Aiping; Zhang, Xiaoyan; Sun, Jianxu

    2015-12-01

    The poor water solubility of many candidate drugs remains a major obstacle to their development and clinical use, especially for oral drug delivery. Nanocrystal technology can improve the solubility and dissolution rates of many poorly water-soluble drugs very effectively, significantly improving their oral bioavailability and decreasing the food effect. For this reason, this technology is becoming a key area of drug delivery research. This review presents much of the recent progress in nanocrystal drug pharmaceuticals, including the characteristics, composition, preparation technology, and clinical applications of these drugs. Finally, the effect of nanocrystal technology on insoluble drugs is quantified and described. PMID:26817271

  7. Engineering Catalytic Contacts and Thermal Stability: Gold/Iron Oxide Binary Nanocrystal Superlattices for CO Oxidation

    SciTech Connect

    Kang, YJ; Ye, XC; Chen, J; Qi, L; Diaz, RE; Doan-Nguyen, V; Xing, GZ; Kagan, CR; Li, J; Gorte, RJ; Stach, EA; Murray, CB

    2013-01-30

    Well-defined surface, such as surface of a single crystal, is being used to provide precise interpretation of catalytic processes, while the nanoparticulate model catalyst more closely represents the real catalysts that are used in industrial processes. Nanocrystal superlattice, which combines the chemical and physical properties of different materials in a single crystalline structure, is an ideal model catalyst, that bridge between conventional models and real catalysts. We identify the active sites for carbon monoxide (CO) oxidation on Au-FeOx catalysts by using Au-FeOx binary superlattices correlating the activity to the number density of catalytic contacts between Au and FeOx. Moreover, using nanocrystal superlattices, we propose a general strategy of keeping active metals spatially confined to enhance the stability of metal catalysts. With a great range of nanocrystal superlattice structures and compositions, we establish that nanocrystal superlattices are useful model materials through which to explore, understand, and improve catalytic processes bridging the gap between traditional single crystal and supported catalyst studies.

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

    PubMed

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

    2015-08-14

    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

  9. Phase-controlled synthesis of Cu2ZnSnS4 nanocrystals: the role of reactivity between Zn and S.

    PubMed

    Zou, Yu; Su, Xiong; Jiang, Jiang

    2013-12-11

    Cu2ZnSnS4 (CZTS) nanocrystals with different morphologies and phases have been synthesized in hot organic solvents such as dodecanethiol and oleylamine. The crystallographic phases could be controlled by the sulfur precursor and the ligand species of the metal salts used for the synthesis. When a highly reactive sulfur precursor and metal acetates were used, wurtzite CZTS nanocrystals were obtained. On the other hand, using a low-reactivity sulfur precursor or metal chlorides produced CZTS nanocrystals in a kesterite phase. The experimental results from systematic investigations indicated that the reaction rate between Zn and S precursors played a determining role for the growth of CZTS nanocrystals with different crystalline phases. A relatively faster reaction between Zn and S precursors in comparison to the Sn-S reaction favored the formation of a metastable wurtzite phase, which could be accelerated by increasing the reactivity of the S precursor. This work provided a safe and economical way to synthesize high-quality phase-controlled Cu2ZnSnS4 nanocrystals, especially wurtzite nanorods, for potential photovoltaic applications. Moreover, preliminary results show that the proposed mechanism also applies to the phase-controlled synthesis of other quaternary Cu2MSnS4 (M = Cd(2+), Mn(2+)) nanocrystals. PMID:24283701

  10. Synthetic Strategies for Semiconductor Nanocrystals Expressing Localized Surface Plasmon Resonance.

    PubMed

    Niezgoda, J Scott; Rosenthal, Sandra J

    2016-03-01

    The field of semiconductor plasmonics has grown rapidly since its outset, only roughly six years ago, and now includes many crystalline substances ranging from GeTe to wide-bandgap transition-metal oxides. One byproduct of this proliferation is the sea of differing synthetic methods to realize localized surface plasmon resonances (LSPRs) based on the studied material. Strategies vary widely from material to material, but all have the common goal of introducing extremely high carrier densities to the semiconductor system. This doping results in tunable, size-quantized, and on/off-switchable LSPR modes, which are a complete departure from traditional metal-nanoparticle-based plasmon resonances. This Minireview will provide an overview of the current state of nanocrystal and quantum-dot plasmonics and the physical basis thereof, however its main purpose is to summarize the methods for realizing LSPRs in the various syntheses and systems that have been reported to date. PMID:26530667

  11. Synthesis of Co-based bimetallic nanocrystals with one-dimensional structure for selective control on syngas conversion

    NASA Astrophysics Data System (ADS)

    Ba, Rongbin; Zhao, Yonghui; Yu, Lujing; Song, Jianjun; Huang, Shuangshuang; Zhong, Liangshu; Sun, Yuhan; Zhu, Yan

    2015-07-01

    Co-based bimetallic nanocrystals with one-dimensional (1D) branches were synthesized by the heterogeneous nucleation of Co atoms onto prenucleated seeds, such as Pd or Cu, through a facile wet-chemical route. The peripheral branches (rod-like) of the Co-Pd and Co-Cu nanocrystals were outspread along the (001) direction and were enclosed by (101) facets. By switching the prenucleated metals to form robust Co-Pd or Co-Cu bimetallic nanocatalysts, the selectivity of CO hydrogenation could be adjusted purposely towards heavy paraffins, light olefins or oxygenates. The Anderson-Schulz-Flory chain-lengthening probabilities for products were up to 0.9 over Co-Pd nanocrystals, showing that long-chain hydrocarbons can be formed with high selectivity using the targeted design of Co-Pd nanocrystal catalysts. These Co-based bimetallic nanocrystals with a 1D structure exhibited superior catalytic activities over the corresponding Co-based nanoparticles for synthesis gas conversion.Co-based bimetallic nanocrystals with one-dimensional (1D) branches were synthesized by the heterogeneous nucleation of Co atoms onto prenucleated seeds, such as Pd or Cu, through a facile wet-chemical route. The peripheral branches (rod-like) of the Co-Pd and Co-Cu nanocrystals were outspread along the (001) direction and were enclosed by (101) facets. By switching the prenucleated metals to form robust Co-Pd or Co-Cu bimetallic nanocatalysts, the selectivity of CO hydrogenation could be adjusted purposely towards heavy paraffins, light olefins or oxygenates. The Anderson-Schulz-Flory chain-lengthening probabilities for products were up to 0.9 over Co-Pd nanocrystals, showing that long-chain hydrocarbons can be formed with high selectivity using the targeted design of Co-Pd nanocrystal catalysts. These Co-based bimetallic nanocrystals with a 1D structure exhibited superior catalytic activities over the corresponding Co-based nanoparticles for synthesis gas conversion. Electronic supplementary

  12. Semiconductor-nanocrystal/conjugated polymer thin films

    DOEpatents

    Alivisatos, A. Paul; Dittmer, Janke J.; Huynh, Wendy U.; Milliron, Delia

    2014-06-17

    The invention described herein provides for thin films and methods of making comprising inorganic semiconductor-nanocrystals dispersed in semiconducting-polymers in high loading amounts. The invention also describes photovoltaic devices incorporating the thin films.

  13. Lifetime blinking in nonblinking nanocrystal quantum dots.

    PubMed

    Galland, Christophe; Ghosh, Yagnaseni; Steinbrück, Andrea; Hollingsworth, Jennifer A; Htoon, Han; Klimov, Victor I

    2012-01-01

    Nanocrystal quantum dots are attractive materials for applications as nanoscale light sources. One impediment to these applications is fluctuations of single-dot emission intensity, known as blinking. Recent progress in colloidal synthesis has produced nonblinking nanocrystals; however, the physics underlying blinking suppression remains unclear. Here we find that ultra-thick-shell CdSe/CdS nanocrystals can exhibit pronounced fluctuations in the emission lifetimes (lifetime blinking), despite stable nonblinking emission intensity. We demonstrate that lifetime variations are due to switching between the neutral and negatively charged state of the nanocrystal. Negative charging results in faster radiative decay but does not appreciably change the overall emission intensity because of suppressed nonradiative Auger recombination for negative trions. The Auger process involving excitation of a hole (positive trion pathway) remains efficient and is responsible for charging with excess electrons, which occurs via Auger-assisted ionization of biexcitons accompanied by ejection of holes. PMID:22713750

  14. Size-Dependent Raman Shifts for nanocrystals

    PubMed Central

    Gao, Yukun; Zhao, Xinmei; Yin, Penggang; Gao, Faming

    2016-01-01

    Raman spectroscopy is a very sensitive tool for probing semiconductor nanocrystals. The underlying mechanism behind the size-dependent Raman shifts is still quite controversial. Here we offer a new theoretical method for the quantum confinement effects on the Raman spectra of semiconductor nanocrystals. We propose that the shift of Raman spectra in nanocrystals can result from two overlapping effects: the quantum effect shift and surface effect shift. The quantum effect shift is extracted from an extended Kubo formula, the surface effect shift is determined via the first principles calculations. Fairly good prediction of Raman shifts can be obtained without the use of any adjustable parameter. Closer analysis shows that the size-dependent Raman shifts in Si nanocrystals mainly result from the quantum effect shifts. For nanodiamond, the proportion of surface effect shift in Raman shift is up to about 40%. Such model can also provide a good baseline for using Raman spectroscopy as a tool to measure size. PMID:27102066

  15. 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.

  16. Semiconductor-nanocrystal/conjugated polymer thin films

    DOEpatents

    Alivisatos, A. Paul; Dittmer, Janke J.; Huynh, Wendy U.; Milliron, Delia

    2010-08-17

    The invention described herein provides for thin films and methods of making comprising inorganic semiconductor-nanocrystals dispersed in semiconducting-polymers in high loading amounts. The invention also describes photovoltaic devices incorporating the thin films.

  17. Colloidal nanocrystals and method of making

    SciTech Connect

    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.

  18. 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.

  19. Composite material including nanocrystals and methods of making

    DOEpatents

    Bawendi, Moungi G.; Sundar, Vikram C.

    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

  20. Tailorable, Visible Light Emission From Silicon Nanocrystals

    SciTech Connect

    Samara, G.A.; Wilcoxon, J.P.

    1999-07-20

    J. P. Wilcoxon and G. A. Samara Crystalline, size-selected Si nanocrystals in the size range 1.8-10 nm grown in inverse micellar cages exhibit highly structured optical absorption and photoluminescence (PL) across the visible range of the spectrum. The most intense PL for the smallest nanocrystals produced This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, make any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof. to induce a useful level of visible photoluminescence (PL) from silicon (Si). The approaches understood. Visible PL has been observed from Si nanocrystals, or quantum dots, produced by a variety of techniques including aerosols,2 colloids,3 and ion implantation.4 However, all of The optical absorption spectra of our nanocrystals are much richer in spectral features spectrum of bulk Si where the spectral features reflect the details of the band structure shown in nanocrystals estimated to have a Si core diameter of 1-2 nm. These measured quantum those in the spectrum of bulk Si in Fig. 1 are striking indicating that nanocrystals of this size 8-Room temperature PL results on an HPLC size-selected, purified 2 nm nanocrystals but blue shifted by -0.4 eV due to quantum confinement. Excitation at 245 nm yields

  1. Charge transport in semiconductor nanocrystal quantum dots

    NASA Astrophysics Data System (ADS)

    Mentzel, Tamar Shoshana

    In this thesis, we study charge transport in arrays of semiconductor nanocrystal quantum dots. Nanocrystals are synthesized in solution, and an organic ligand on the surface of the nanocrystal creates a potential barrier that confines charges in the nanocrystal. Optical absorption measurements reveal discrete electronic energy levels in the nanocrystals resulting from quantum confinement. When nanocrystals are deposited on a surface, they self-assemble into a close-packed array forming a nanocrystal solid. We report electrical transport measurements of a PbSe nanocrystal solid that serves as the channel of an inverted field-effect transistor. We measure the conductance as a function of temperature, source-drain bias and. gate voltage. The data indicates that holes are the majority carriers; the Fermi energy lies in impurity states in the bandgap of the nanocrystal; and charges hop between the highest occupied valence state in the nanocrystals (the 1S h states). At low source-drain voltages, the activation energy for hopping is given by the energy required to generate holes in the 1Sh state plus activation over barriers resulting from site disorder. The barriers from site disorder are eliminated with a sufficiently high source-drain bias. From the gate effect, we extract the Thomas-Fermi screening length and a density of states that is consistent with the estimated value. We consider variable-range hopping as an alternative model, and find no self-consistent evidence for it. Next, we employ charge sensing as an alternative to current measurements for studying transport in materials with localized sites. A narrow-channel MOSFET serves as a charge sensor because its conductance is sensitive to potential fluctuations in the nearby environment caused by the motion of charge. In particular, it is sensitive to the fluctuation of single electrons at the silicon-oxide interface within the MOSFET. We pattern a strip of amorphous germanium within 100 nm of the transistor. The

  2. Optical refrigeration of Yb3+:YAG nanocrystals

    NASA Astrophysics Data System (ADS)

    Nemova, Galina; Kashyap, Raman

    2015-03-01

    We have theoretically investigated the laser cooling process in Yb3+:YAG nanocrystals. We have developed an approach, which permits not only estimate the cooling process in Yb3+:YAG nanocrystals but compare this process with the laser cooling of the Yb3+:YAG bulk samples. The temperature dependences of all parameters of the system are taken into account. The cooperative effects such as re-absorption, the energy migration and cooperative luminescence have been considered.

  3. New self-assembled nanocrystal micelles for biolabels and biosensors.

    SciTech Connect

    Tallant, David Robert; Wilson, Michael C. (University of New Mexico, Albuquerque, NM); Leve, Erik W. (University of New Mexico, Albuquerque, NM); Fan, Hongyou; Brinker, C. Jeffrey; Gabaldon, John (University of New Mexico, Albuquerque, NM); Scullin, Chessa (University of New Mexico, Albuquerque, NM)

    2005-12-01

    The ability of semiconductor nanocrystals (NCs) to display multiple (size-specific) colors simultaneously during a single, long term excitation holds great promise for their use in fluorescent bio-imaging. The main challenges of using nanocrystals as biolabels are achieving biocompatibility, low non-specific adsorption, and no aggregation. In addition, functional groups that can be used to further couple and conjugate with biospecies (proteins, DNAs, antibodies, etc.) are required. In this project, we invented a new route to the synthesis of water-soluble and biocompatible NCs. Our approach is to encapsulate as-synthesized, monosized, hydrophobic NCs within the hydrophobic cores of micelles composed of a mixture of surfactants and phospholipids containing head groups functionalized with polyethylene glycol (-PEG), -COOH, and NH{sub 2} groups. PEG provided biocompatibility and the other groups were used for further biofunctionalization. The resulting water-soluble metal and semiconductor NC-micelles preserve the optical properties of the original hydrophobic NCs. Semiconductor NCs emit the same color; they exhibit equal photoluminescence (PL) intensity under long-time laser irradiation (one week) ; and they exhibit the same PL lifetime (30-ns). The results from transmission electron microscopy and confocal fluorescent imaging indicate that water-soluble semiconductor NC-micelles are biocompatible and exhibit no aggregation in cells. We have extended the surfactant/lipid encapsulation techniques to synthesize water-soluble magnetic NC-micelles. Transmission electron microscopy results suggest that water-soluble magnetic NC-micelles exhibit no aggregation. The resulting NC-micelles preserve the magnetic properties of the original hydrophobic magnetic NCs. Viability studies conducted using yeast cells suggest that the magnetic nanocrystal-micelles are biocompatible. We have demonstrated, for the first time, that using external oscillating magnetic fields to manipulate

  4. Solution synthesis of germanium nanocrystals

    DOEpatents

    Gerung, Henry; Boyle, Timothy J.; Bunge, Scott D.

    2009-09-22

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

  5. Polyimide Cellulose Nanocrystal Composite Aerogels

    NASA Technical Reports Server (NTRS)

    Nguyen, Baochau N.; Meador, Mary Ann; Rowan, Stuart; Cudjoe, Elvis; Sandberg, Anna

    2014-01-01

    Polyimide (PI) aerogels are highly porous solids having low density, high porosity and low thermal conductivity with good mechanical properties. They are ideal for various applications including use in antenna and insulation such as inflatable decelerators used in entry, decent and landing operations. Recently, attention has been focused on stimuli responsive materials such as cellulose nano crystals (CNCs). CNCs are environmentally friendly, bio-renewable, commonly found in plants and the dermis of sea tunicates, and potentially low cost. This study is to examine the effects of CNC on the polyimide aerogels. The CNC used in this project are extracted from mantle of a sea creature called tunicates. A series of polyimide cellulose nanocrystal composite aerogels has been fabricated having 0-13 wt of CNC. Results will be discussed.

  6. A luminescent nanocrystal stress gauge

    SciTech Connect

    Choi, Charina; Koski, Kristie; Olson, Andrew; Alivisatos, Paul

    2010-10-25

    Microscale mechanical forces can determine important outcomes ranging from the site of material fracture to stem cell fate. However, local stresses in a vast majority of systems cannot be measured due to the limitations of current techniques. In this work, we present the design and implementation of the CdSe/CdS core/shell tetrapod nanocrystal, a local stress sensor with bright luminescence readout. We calibrate the tetrapod luminescence response to stress, and use the luminescence signal to report the spatial distribution of local stresses in single polyester fibers under uniaxial strain. The bright stress-dependent emission of the tetrapod, its nanoscale size, and its colloidal nature provide a unique tool that may be incorporated into a variety of micromechanical systems including materials and biological samples to quantify local stresses with high spatial resolution.

  7. Soft epitaxy of nanocrystal superlattices

    NASA Astrophysics Data System (ADS)

    Rupich, Sara M.; Castro, Fernando C.; Irvine, William T. M.; Talapin, Dmitri V.

    2014-12-01

    Epitaxial heterostructures with precise registry between crystal layers play a key role in electronics and optoelectronics. In a close analogy, performance of nanocrystal (NC) based devices depends on the perfection of interfaces formed between NC layers. Here we systematically study the epitaxial growth of NC layers for the first time to enable the fabrication of coherent NC layers. NC epitaxy reveals an exceptional strain tolerance. It follows a universal island size scaling behaviour and shows a strain-driven transition from layer-by-layer to Stranski-Krastanov growth with non-trivial island height statistics. Kinetic bottlenecks play an important role in NC epitaxy, especially in the transition from sub-monolayer to multilayer coverage and the epitaxy of NCs with anisotropic shape. These findings provide a foundation for the rational design of epitaxial structures in a fundamentally and practically important size regime between atomic and microscopic systems.

  8. Interaction potentials of anisotropic nanocrystals from the trajectory sampling of particle motion using in situ liquid phase transmission electron microscopy

    SciTech Connect

    Chen, Qian; Cho, Hoduk; Manthiram, Karthish; Yoshida, Mark; Ye, Xingchen; Alivisatos, A. Paul

    2015-03-23

    We demonstrate a generalizable strategy to use the relative trajectories of pairs and groups of nanocrystals, and potentially other nanoscale objects, moving in solution which can now be obtained by in situ liquid phase transmission electron microscopy (TEM) to determine the interaction potentials between nanocrystals. Such nanoscale interactions are crucial for collective behaviors and applications of synthetic nanocrystals and natural biomolecules, but have been very challenging to measure in situ at nanometer or sub-nanometer resolution. Here we use liquid phase TEM to extract the mathematical form of interaction potential between nanocrystals from their sampled trajectories. We show the power of this approach to reveal unanticipated features of nanocrystal–nanocrystal interactions by examining the anisotropic interaction potential between charged rod-shaped Au nanocrystals (Au nanorods); these Au nanorods assemble, in a tip-to-tip fashion in the liquid phase, in contrast to the well-known side-by-side arrangements commonly observed for drying-mediated assembly. These observations can be explained by a long-range and highly anisotropic electrostatic repulsion that leads to the tip-selective attachment. As a result, Au nanorods stay unassembled at a lower ionic strength, as the electrostatic repulsion is even longer-ranged. Our study not only provides a mechanistic understanding of the process by which metallic nanocrystals assemble but also demonstrates a method that can potentially quantify and elucidate a broad range of nanoscale interactions relevant to nanotechnology and biophysics.

  9. Lanthanide-doped nanocrystals: synthesis, optical-magnetic properties, and applications.

    PubMed

    Wang, Guofeng; Peng, Qing; Li, Yadong

    2011-05-17

    . These binary nanoparticles can be hybridized with a third DNA (target DNA) molecule and separated with the assistance of a magnetic field. In addition, a novel fluorescence resonance energy transfer (FRET) method for nonenzymatic glucose determination has been developed by using the glucose-modified LaF(3):Ce(3+)/Tb(3+) nanocrystals. By using bioconjugated NaYF(4):Yb(3+)/Er(3+) nanoparticles as the energy donor and bioconjugated gold nanoparticles as the energy acceptor, we successfully developed a simple and sensitive fluorescence resonance energy transfer (FRET) biosensor for avidin. Meanwhile, we also carried out preliminary studies to investigate possible applications of lanthanide-doped nanocrystals in catalysis and in dye-sensitized solar cells. PMID:21395256

  10. 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

  11. Synthesis of nanocrystals and nanocrystal self-assembly

    NASA Astrophysics Data System (ADS)

    Chen, Zhuoying

    Chapter 1. A general introduction is presented on nanomaterials and nanoscience. Nanoparticles are discussed with respect to their structure and properties. Ferroelectric materials and nanoparticles in particular are highlighted, especially in the case of the barium titanate, and their potential applications are discussed. Different nanocrystal synthetic techniques are discussed. Nanoparticle superlattices, the novel "meta-materials" built from self-assembly at the nanoscale, are introduced. The formation of nanoparticle superlattices and the importance and interest of synthesizing these nanostructures is discussed. Chapter 2. Advanced applications for high k dielectric and ferroelectric materials in the electronics industry continues to demand an understanding of the underlying physics in decreasing dimensions into the nanoscale. The first part of this chapter presents the synthesis, processing, and electrical characterization of nanostructured thin films (thickness ˜100 nm) of barium titanate BaTiO3 built from uniform nanoparticles (<20 nm in diameter) in diameter. Essential to our approach is an understanding of the nanoparticle as a building block, combined with an ability to integrate them into thin films that have uniform and characteristic electrical properties. We observe the BaTiO3 nanocrystals crystallize with evidence of tetragonality. Electric field dependent polarization measurements show spontaneous polarization and hysteresis, indicating ferroelectric behavior for the BaTiO 3 nanocrystalline films with grain sizes in the range of 10--30 nm. Dielectric measurements of the films show dielectic constants in the range of 85--90 over the 1 kHz--100 kHz, with low loss. We present nanocrystals as initial building blocks for the preparation of thin films which exhibit uniform nanostructured morphologies and grain sizes. In the second part of this chapter, a nonhydrolytic alcoholysis route to study the preparation of well-crystallized size-tunable BaTiO3

  12. Surface treatment of nanocrystal quantum dots after film deposition

    DOEpatents

    Sykora, Milan; Koposov, Alexey; Fuke, Nobuhiro

    2015-02-03

    Provided are methods of surface treatment of nanocrystal quantum dots after film deposition so as to exchange the native ligands of the quantum dots for exchange ligands that result in improvement in charge extraction from the nanocrystals.

  13. Efficiency of the coherent biexciton admixture mechanism for multiple exciton generation in InAs nanocrystals

    NASA Astrophysics Data System (ADS)

    Kowalski, Piotr; Machnikowski, Paweł

    2015-12-01

    We study the coherent mixing between two-particle (single exciton) and four-particle (biexciton) states of a semiconductor nanocrystal resulting from the Coulomb coupling between states with different numbers of electron-hole pairs. Using a simple model of the nanocrystal wave functions and an envelope function approach, we estimate the efficiency of the multiple exciton generation (MEG) process resulting from such coherent admixture mechanism, including all the relevant states in a very broad energy interval. We show that in a typical ensemble of nanocrystals with an average radius of 3nm, the onset of the MEG process appears about 1 eV above the lower edge of the biexciton density of states. This is due to the angular momentum conservation that imposes selection rules and limits the available MEG pathways, thus taking over the role of momentum conservation that hinders this process in bulk. The efficiency of the MEG process reaches 50% for photon energies around 5 eV. The MEG onset shifts to lower energies and therefore the efficiency increases in a certain energy range as the radius grows. The energy dependence of the MEG efficiency differs considerably between ensembles with small and large inhomogeneity of nanocrystal sizes.

  14. 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. PMID:21152569

  15. Homogeneous Cu2ZnSnSe4 nanocrystals/graphene oxide nanocomposites as hole transport layer for polymer solar cells

    NASA Astrophysics Data System (ADS)

    Tan, Licheng; Zhang, Yan; Chen, Yiwang; Chen, Yufeng

    2015-02-01

    Homogeneous Cu2ZnSnSe4 nanocrystals/graphene oxide (CZTSe@GO) nanocomposite as hole transport layer (HTL) applied in polymer solar cells has been fabricated through a simple and solution-processed strategy, which not only arrests the aggregation of nanoparticles caused by ligand-exchanging, but also guarantees the intimate interfacial contact between graphene oxide and semiconductor nanocrystals. Comparing with Cu2ZnSnSe4 nanocrystals, the optimization of interfacial charge carrier transfer pathways for CZTSe@GO nanocomposites makes it more suitable as HTL which shows enhanced charge carrier transport and electron-blocking capacity, and well-matched work function facilitating collection of charges to anode. Besides, it also affords an efficient way to manufacture multifunctional nanocomposites based on nanocrystals.

  16. Electron transport in two-dimensional arrays of gold nanocrystals investigated by scanning electrochemical microscopy.

    PubMed

    Liljeroth, Peter; Vanmaekelbergh, Daniël; Ruiz, Virginia; Kontturi, Kyösti; Jiang, Hua; Kauppinen, Esko; Quinn, Bernadette M

    2004-06-01

    This article reports the use of the scanning electrochemical microscope (SECM) to investigate the electronic properties of Langmuir monolayers of alkane thiol protected gold nanocrystals (NCs). A substantial increase in monolayer conductivity upon mechanical compression of the Au NC monolayer is reported for the first time. This may be the room temperature signature of the insulator to metal transition previously reported for comparable silver NC monolayers. Factors influencing the conductivity of the monolayer NC array are discussed. PMID:15174884

  17. Organization and magnetic properties of cigar-shaped ferrite nanocrystals

    NASA Astrophysics Data System (ADS)

    Ngo, A. T.; Pileni, M. P.

    2002-11-01

    Cigar-shaped maghemite (gamma-Fe2O3) nanocrystals dispersed in aqueous solution are subjected to a magnetic field during the deposition (process) on graphite. The nanocrystals can thus be oriented along their long axis to form ribbons at a mesoscopic scale whereas without a field the nanocrystals remain randomly oriented on the substrate. The magnetic properties markedly depend on the organization of the nanocrystals within the mesostructures.

  18. Band-like transport, high electron mobility and high photoconductivity in all-inorganic nanocrystal arrays.

    PubMed

    Lee, Jong-Soo; Kovalenko, Maksym V; Huang, Jing; Chung, Dae Sung; Talapin, Dmitri V

    2011-06-01

    Flexible, thin-film electronic and optoelectronic devices typically involve a trade-off between performance and fabrication cost. For example, solution-based deposition allows semiconductors to be patterned onto large-area substrates to make solar cells and displays, but the electron mobility in solution-deposited semiconductor layers is much lower than in semiconductors grown at high temperatures from the gas phase. Here, we report band-like electron transport in arrays of colloidal cadmium selenide nanocrystals capped with the molecular metal chalcogenide complex In(2)Se(4)(2-), and measure electron mobilities as high as 16 cm(2) V(-1) s(-1), which is about an order of magnitude higher than in the best solution-processed organic and nanocrystal devices so far. We also use CdSe/CdS core-shell nanoparticles with In(2)Se(4)(2-) ligands to build photodetectors with normalized detectivity D* > 1 × 10(13) Jones (I Jones = 1 cm Hz(1/2) W(-1)), which is a record for II-VI nanocrystals. Our approach does not require high processing temperatures, and can be extended to different nanocrystals and inorganic surface ligands. PMID:21516091

  19. Enhanced ultraviolet photoresponse based on ZnO nanocrystals/Pt bilayer nanostructure

    NASA Astrophysics Data System (ADS)

    Tong, Xiao-Lin; Xia, Xiao-Zhi; Li, Qing-Xia

    2015-06-01

    The development of solution strategies for Zinc oxide (ZnO) quantum dots provides a pathway to utilizing ZnO nanocrystal thin films in optoelectronic devices. In this work, quasi-spherical ZnO quantum dots with a diameter of 5 nm are synthesized by using ethanol as a solvent. ZnO nanocrystal thin film is obtained by spin-coating ZnO quantum dots on a Au interdigital electrode (IDE)/Al2O3 substrate and annealing at different temperatures in order to yield the optimal photosensitive on/off ratio of ZnO. For further enhancing the responsivity, ion sputtering is utilized to deposit Pt nanoparticles on the surface of ZnO nanocrystal thin film, the responsivity of the ZnO/Pt bilayer nanostructure increases from 0.07 A/W to 54 A/W, showing that the metal/inorganic nanocrystal bilayer nanostructure can be used to improve the performance of optoelectronic devices. The excellent properties of ZnO/Pt bilayer nanostructure have important applications in future electronic and optoelectronic devices. Project supported by the National Natural Science Foundation of China (Grant No. 41176156).

  20. Light-emitting diodes made from cadmium selenide nanocrystals and a semiconducting polymer

    NASA Astrophysics Data System (ADS)

    Colvin, V. L.; Schlamp, M. C.; Alivisatos, A. P.

    1994-08-01

    ELECTROLUMINESCENT devices have been developed recently that are based on new materials such as porous silicon1 and semiconducting polymers2,3. By taking advantage of developments in the preparation and characterization of direct-gap semiconductor nanocrystals4-6, and of electroluminescent polymers7, we have now constructed a hybrid organic/inorganic electroluminescent device. Light emission arises from the recombination of holes injected into a layer of semiconducting p-paraphenylene vinylene (PPV)8-10 with electrons injected into a multilayer film of cadmium selenide nanocrystals. Close matching of the emitting layer of nanocrystals with the work function of the metal contact leads to an operating voltage11 of only 4V. At low voltages emission from the CdSe layer occurs. Because of the quantum size effect19-24 the colour of this emission can be varied from red to yellow by changing the nanocrystal size. At higher voltages green emission from the polymer layer predominates. Thus this device has a degree of voltage tunability of colour.

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

    PubMed

    Wang, Junli; Yang, Qing

    2008-11-21

    Group III-V (13-15, III = Ga, In, and V = P, As) semiconductor nanocrystals were effectively obtained via a developed Ullmann reaction route through the reactions of preformed nanoscale metallic indium or commercial gallium with triphenylphosphine (PPh(3)) and triphenylarsine (AsPh(3)) in sealed vacuum quartz tubes under moderate conditions at 320-400 degrees C for 8-24 h. The developed synthetic strategy in sealed vacuum tubes extends the synthesis of III-V semiconductor materials, and the air-stable PPh(3) and AsPh(3) with low toxicity provide good alternative pnicogen precursors for the synthesis of III-V nanocrystals. The analysis of XRD, ED and HRTEM established the production of one-dimensional (1D) metastable wurtzite (W) InP, InAs and GaP nanostructures in the zinc blende (ZB) products. Further investigations showed that 1D W nanostructures resulted from kinetic effects under the moderate synthetic conditions employed and the steric effect of PPh(3) and AsPh(3), and that the tendency for the synthesis of III-V nanocrystals was in the orders of IIIP > IIIAs and GaV > InV on the basis of experiments and thermodynamic calculations. Meanwhile, the microstructures and growth mechanism of the III-V nanocrystals were investigated. PMID:19082064

  2. Tunable near-infrared and visible-light transmittance in nanocrystal-in-glass composites.

    PubMed

    Llordés, Anna; Garcia, Guillermo; Gazquez, Jaume; Milliron, Delia J

    2013-08-15

    Amorphous metal oxides are useful in optical, electronic and electrochemical devices. The bonding arrangement within these glasses largely determines their properties, yet it remains a challenge to manipulate their structures in a controlled manner. Recently, we developed synthetic protocols for incorporating nanocrystals that are covalently bonded into amorphous materials. This 'nanocrystal-in-glass' approach not only combines two functional components in one material, but also the covalent link enables us to manipulate the glass structure to change its properties. Here we illustrate the power of this approach by introducing tin-doped indium oxide nanocrystals into niobium oxide glass (NbOx), and realize a new amorphous structure as a consequence of linking it to the nanocrystals. The resulting material demonstrates a previously unrealized optical switching behaviour that will enable the dynamic control of solar radiation transmittance through windows. These transparent films can block near-infrared and visible light selectively and independently by varying the applied electrochemical voltage over a range of 2.5 volts. We also show that the reconstructed NbOx glass has superior properties-its optical contrast is enhanced fivefold and it has excellent electrochemical stability, with 96 per cent of charge capacity retained after 2,000 cycles. PMID:23955232

  3. A Route to Phase Controllable Cu2ZnSn(S1−xSex)4 Nanocrystals with Tunable Energy Bands

    PubMed Central

    Ji, Shulin; Shi, Tongfei; Qiu, Xiaodong; Zhang, Jian; Xu, Guoping; Chen, Chao; Jiang, Zheng; Ye, Changhui

    2013-01-01

    Cu2ZnSn(S1−xSex)4 nanocrystals are an emerging family of functional materials with huge potential of industrial applications, however, it is an extremely challenging task to synthesize Cu2ZnSn(S1−xSex)4 nanocrystals with both tunable energy band and phase purity. Here we show that a green and economic route could be designed for the synthesis of Cu2ZnSn(S1−xSex)4 nanocrystals with bandgap tunable in the range of 1.5–1.12 eV. Consequently, conduction band edge shifted from −3.9 eV to −4.61 eV (relative to vacuum energy) is realized. The phase purity of Cu2ZnSn(S1−xSex)4 nanocrystals is substantiated with in-depth combined optical and structural characterizations. Electrocatalytic and thermoelectric performances of Cu2ZnSn(S1−xSex)4 nanocrystals verify their superior activity to replace noble metal Pt and materials containing heavy metals. This green and economic route will promote large-scale application of Cu2ZnSn(S1−xSex)4 nanocrystals as solar cell materials, electrocatalysts, and thermoelectric materials. PMID:24061108

  4. A route to phase controllable Cu2ZnSn(S(1-x)Se(x))4 nanocrystals with tunable energy bands.

    PubMed

    Ji, Shulin; Shi, Tongfei; Qiu, Xiaodong; Zhang, Jian; Xu, Guoping; Chen, Chao; Jiang, Zheng; Ye, Changhui

    2013-01-01

    Cu2ZnSn(S(1-x)Se(x))4 nanocrystals are an emerging family of functional materials with huge potential of industrial applications, however, it is an extremely challenging task to synthesize Cu2ZnSn(S(1-x)Se(x))4 nanocrystals with both tunable energy band and phase purity. Here we show that a green and economic route could be designed for the synthesis of Cu2ZnSn(S(1-x)Se(x))4 nanocrystals with bandgap tunable in the range of 1.5-1.12 eV. Consequently, conduction band edge shifted from -3.9 eV to -4.61 eV (relative to vacuum energy) is realized. The phase purity of Cu2ZnSn(S(1-x)Se(x))4 nanocrystals is substantiated with in-depth combined optical and structural characterizations. Electrocatalytic and thermoelectric performances of Cu2ZnSn(S(1-x)Se(x))4 nanocrystals verify their superior activity to replace noble metal Pt and materials containing heavy metals. This green and economic route will promote large-scale application of Cu2ZnSn(S(1-x)Se(x))4 nanocrystals as solar cell materials, electrocatalysts, and thermoelectric materials. PMID:24061108

  5. Phase and Size Controllable Synthesis of NaYbF4 Nanocrystals in Oleic Acid/ Ionic Liquid Two-Phase System for Targeted Fluorescent Imaging of Gastric Cancer

    PubMed Central

    Pan, Liyuan; He, Meng; Ma, Jiebing; Tang, Wei; Gao, Guo; He, Rong; Su, Haichuan; Cui, Daxiang

    2013-01-01

    Upconversion nanocrystals with small size and strong fluorescent signals own great potential in applications such as biomolecule-labeling, in vivo tracking and molecular imaging. Herein we reported that NaYbF4: 25%Gd, 2%Tm upconversion nanocrystals with small size and strong fluorescent signals were controllably synthesized by oleic acid (OA)/ ionic liquid (IL) two-phase system for targeted fluorescent imaging of gastric cancer in vivo. The optimal synthesis condition of NaYbF4: 25%Gd, 2%Tm upconversion nanocrystals by OA/IL two-phase system was established, adding more metal ion such as Na+ ion could facilitate the size control and crystal-phase transition, more importantly, markedly enhancing fluorescent intensity of beta-phase nanocrystals compared with traditional methods. Alpha-phase NaYbF4, 2%Tm upconversion nanocrystals with less than 10nm in diameter and beta-phase NaYbF4: 25%Gd, 2%Tm upconversion nanocrystals with 30 nm or so in diameter and strong fluorescent signals were obtained, these synthesized nanocrystals exhibited very low cytotoxicity. Folic acid-conjugated silica-modified beta-phase NaYbF4: 25%Gd, 2%Tm upconversion nanocrystals were prepared, could actively target gastric cancer tissues implanted into nude mice in vivo, and realized targeted fluorescent imaging. Folic acid-conjugated silica-modified NaYbF4: 25%Gd, 2%Tm upconversion nanocrystals show great potential in applications such as targeted near infared radiation fluorescent imaging, magnetic resonance imaging and targeted therapy of gastric cancer in the near future. PMID:23471455

  6. The effect on the lanthanide luminescence of structurally simple Eu(III) cyclen complexes upon deprotonation of metal bound water molecules and amide based pendant arms.

    PubMed

    Plush, Sally E; Clear, Naomi A; Leonard, Joseph P; Fanning, Ann-Marie; Gunnlaugsson, Thorfinnur

    2010-04-21

    A series of substituted 1,4,7,10-tetraazacylcododecane ligands 1-4, possessing sensitizing nitrobenzene or naphthalene antennae, as one of the amide pendant arms, and their complexes with europium(III) were synthesised. The protonation constants and the metal ion stability constants of two of these ligands were determined by potentiometric titration. The pK(a) of the water molecules coordinated to the complexed metal ion were determined by both luminescent and potentiometric measurements. The luminescence pH dependence of a further three Eu(III) complexes, 5-7, which lack any antennae, were also studied with the aim of gaining a better understanding of the role of the metal bound water molecules in the luminescence properties of such complexes upon direct excitation of the lanthanide ion. The results from these luminescent measurements demonstrate that the Eu(III) emission was significantly modulated as a function of pH for all the complexes, which we assigned to changes occurring in the coordination environment of the ion within the cyclen system, caused by deprotonation of metal bound water molecules and/or deprotonation of pendent amide arms. PMID:20354617

  7. Elucidating the cellular uptake mechanism of aptamer-functionalized graphene-isolated-Au-nanocrystals with dual-modal imaging.

    PubMed

    Wang, Shanshan; Liu, Zhangkun; Zou, Yuxiu; Lai, Xiaofang; Ding, Ding; Chen, Long; Zhang, Liqin; Wu, Yuan; Chen, Zhuo; Tan, Weihong

    2016-05-23

    Elucidating the endocytosis and metabolism of nanoparticles in cells could improve the diagnostic sensitivity and therapeutic efficiency. In this work, we explore the cellular uptake mechanism of a biocompatible nanocrystal nanostructure, graphene-isolated-Au-nanocrystals (GIANs), by monitoring the intrinsic Raman and two-photon luminescence signals of GIANs in live cells. Aptamers functionalized on the GIAN nanostructure through simple, but strong, π-π interactions entered the cells through a clathrin-dependent pathway, while unmodified GIANs mainly entered the cells through a caveolae-mediated endocytosis pathway. Thus, it can be concluded that the mechanism of cellular uptake in these graphene-isolated-Au-nanocrystal nanostructures is determined by the presence or absence of aptamer modification. PMID:27111129

  8. Optical properties of colloidal germanium nanocrystals

    SciTech Connect

    WILCOXON,JESS P.; PROVENCIO,PAULA P.; SAMARA,GEORGE A.

    2000-05-01

    Highly crystalline germanium (Ge) nanocrystals in the size range 2--10 nm were grown in inverse micelles and purified and size-separated by high pressure liquid chromatography with on-line optical and electrical diagnostics. The nanocrystals retain the diamond structure of bulk Ge down to at least 2.0 nm (containing about 150 Ge atoms). The background- and impurity-free extinction and photoluminescence (PL) spectra of these nanocrystals revealed rich structure which was interpreted in terms of the bandstructure of Ge shifted to higher energies by quantum confinement. The shifts ranged from {minus}0.1 eV to over 1 eV for the various transitions. PL in the range 350--700 nm was observed from nanocrystals 2--5 nm in size. The 2.0 nm nanocrystals yielded the most intense PL (at 420 nm) which is believed to be intrinsic and attributed to direct recombination at {Gamma}. Excitation at high energy (250 nm) populates most of the conduction bands resulting in competing recombination channels and the observed broad PL spectra.

  9. Field-effect electroluminescence in silicon nanocrystals.

    PubMed

    Walters, Robert J; Bourianoff, George I; Atwater, Harry A

    2005-02-01

    There is currently worldwide interest in developing silicon-based active optical components in order to leverage the infrastructure of silicon microelectronics technology for the fabrication of optoelectronic devices. Light emission in bulk silicon-based devices is constrained in wavelength to infrared emission, and in efficiency by the indirect bandgap of silicon. One promising strategy for overcoming these challenges is to make use of quantum-confined excitonic emission in silicon nanocrystals. A critical challenge for silicon nanocrystal devices based on nanocrystals embedded in silicon dioxide has been the development of a method for efficient electrical carrier injection. We report here a scheme for electrically pumping dense silicon nanocrystal arrays by a field-effect electroluminescence mechanism. In this excitation process, electrons and holes are both injected from the same semiconductor channel across a tunnelling barrier in a sequential programming process, in contrast to simultaneous carrier injection in conventional pn-junction light-emitting-diode structures. Light emission is strongly correlated with the injection of a second carrier into a nanocrystal that has been previously programmed with a charge of the opposite sign. PMID:15665836

  10. Synthesis of convex hexoctahedral Pt micro/nanocrystals with high-index facets and electrochemistry-mediated shape evolution.

    PubMed

    Xiao, Jing; Liu, Shuo; Tian, Na; Zhou, Zhi-You; Liu, Hai-Xia; Xu, Bin-Bin; Sun, Shi-Gang

    2013-12-18

    Systematic manipulation of nanocrystal shapes is prerequisite for revealing their shape-dependent physical and chemical properties. Here we successfully prepared a complex shape of Pt micro/nanocrystals: convex hexoctahedron (HOH) enclosed with 48 {15 5 3} high-index facets by electrochemical square-wave-potential (SWP) method. This shape is the last crystal single form that had not been achieved previously for face-centered-cubic (fcc) metals. We further realized the shape evolution of Pt nanocrystals with high-index facets from tetrahexahedron (THH) to the HOH, and finally to trapezohedron (TPH) by increasing either the upper (EU) or lower potential (EL). The shape evolution, accompanied by the decrease of low-coordinated kink atoms, can be correlated with the competitive interactions between preferentially oxidative dissolution of kink atoms at high EU and the redeposition of Pt atoms at the EL. PMID:24299234

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  13. High-performance thermoelectric nanocomposites from nanocrystal building blocks

    NASA Astrophysics Data System (ADS)

    Ibáñez, Maria; Luo, Zhishan; Genç, Aziz; Piveteau, Laura; Ortega, Silvia; Cadavid, Doris; Dobrozhan, Oleksandr; Liu, Yu; Nachtegaal, Maarten; Zebarjadi, Mona; Arbiol, Jordi; Kovalenko, Maksym V.; Cabot, Andreu

    2016-03-01

    The efficient conversion between thermal and electrical energy by means of durable, silent and scalable solid-state thermoelectric devices has been a long standing goal. While nanocrystalline materials have already led to substantially higher thermoelectric efficiencies, further improvements are expected to arise from precise chemical engineering of nanoscale building blocks and interfaces. Here we present a simple and versatile bottom-up strategy based on the assembly of colloidal nanocrystals to produce consolidated yet nanostructured thermoelectric materials. In the case study on the PbS-Ag system, Ag nanodomains not only contribute to block phonon propagation, but also provide electrons to the PbS host semiconductor and reduce the PbS intergrain energy barriers for charge transport. Thus, PbS-Ag nanocomposites exhibit reduced thermal conductivities and higher charge carrier concentrations and mobilities than PbS nanomaterial. Such improvements of the material transport properties provide thermoelectric figures of merit up to 1.7 at 850 K.

  14. NIS-catalyzed oxidative cyclization of alcohols with amidines: a simple and efficient transition-metal free method for the synthesis of 1,3,5-triazines.

    PubMed

    Tiwari, Abhishek R; T, Akash; Bhanage, Bhalchandra M

    2015-12-01

    An efficient method for the synthesis of 1,3,5-triazines by NIS-catalyzed oxidative cyclization of alcohols with amidines has been developed. The reaction works smoothly under transition-metal free and phosphine-free conditions to afford a wide range of 1,3,5-triazine derivatives in moderate to good yields. The synthetic methodology was achieved via in situ oxidation of alcohols to aldehydes. PMID:26477749

  15. Influence of reaction conditions on the properties of solution-processed Cu2ZnSnS4 nanocrystals

    NASA Astrophysics Data System (ADS)

    Qu, Yongtao; Zoppi, Guillaume; Miles, Robert W.; Beattie, Neil S.

    2014-12-01

    Cu2ZnSnS4 nanocrystals were fabricated by hot injection of sulphur into a solution of metallic precursors. By careful control of the reaction conditions it was possible to control the elemental composition of the nanocrystals such that they are suitable for earth abundant photovoltaic absorbers. When the reaction temperature increased from 195 °C to 240 °C the energy band gap of the nanocrystals decreased from 1.65 eV to 1.39 eV. This variation is explained by the identification of a mixed wurtzite-kesterite phase at lower reaction temperatures and secondary phase Cu2SnS3 at higher temperatures. Moreover, the existence of wurtzite structure depends critically on the reaction cooling rate. The reaction time was also found to have a strong effect on the nanocrystals which became increasingly copper poor and zinc rich as the reaction evolved. As the reaction time increase from 15 min to 60 min, the energy band gap increased from 1.42 eV to 1.84 eV. This variation is discussed in terms of the sample doping. The results demonstrate the importance of optimizing the reaction conditions to produce high quality Cu2ZnSnS4 nanocrystals.

  16. Designer Nanocrystal Materials for Photovoltaics

    NASA Astrophysics Data System (ADS)

    Kagan, Cherie

    Advances in synthetic methods allow a wide range of semiconductor nanocrystals (NCs) to be tailored in size and shape and to be used as building blocks in the design of NC solids. However, the long, insulating ligands commonly employed in the synthesis of colloidal NCs inhibit strong interparticle coupling and charge transport once NCs are assembled into the solids state as NC arrays. We will describe the range of short, compact ligand chemistries we employ to exchange the long, insulating ligands used in synthesis and to increase interparticle coupling. These ligand exchange processes can have a dramatic influence on NC surface chemistry as well as NC organization in the solids, showing examples of short-range order. Synergistically, we use 1) thermal evaporation and diffusion and 2) wet-chemical methods to introduce extrinsic impurities and non-stoichiometry to passivate surface traps and dope NC solids. NC coupling and doping provide control over the density of states and the carrier type, concentration, mobility, and lifetime, which we characterize by a range of electronic and spectroscopic techniques. We will describe the importance of engineering device interfaces to design NC materials for solar photovoltaics.

  17. Prospects of nanoscience with nanocrystals

    DOE PAGESBeta

    Kovalenko, Maksym V.; Manna, Liberato; Cabot, Andreu; Hens, Zeger; Talapin, Dmitri V.; Kagan, Cherie R.; Klimov, Victor I.; Rogach, Andrey L.; Reiss, Peter; Milliron, Delia J.; et al

    2015-01-22

    Colloidal nanocrystals (NCs, i.e., crystalline nanoparticles) have become an important class of materials with great potential for applications ranging from medicine to electronic and optoelectronic devices. Today's strong research focus on NCs has been prompted by the tremendous progress in their synthesis. Impressively narrow size distributions of just a few percent, rational shape-engineering, compositional modulation, electronic doping, and tailored surface chemistries are now feasible for a broad range of inorganic compounds. Furthermore, the performance of inorganic NC-based photovoltaic and lightemitting devices has become competitive to other state-of-the-art materials. Semiconductor NCs hold unique promise for near- and mid-infrared technologies, where verymore » few semiconductor materials are available. On a purely fundamental side, new insights into NC growth, chemical transformations, and self-organization can be gained from rapidly progressing in situ characterization and direct imaging techniques. New phenomena are constantly being discovered in the photophysics of NCs and in the electronic properties of NC solids. In our Nano Focus, we review the state of the art in research on colloidal NCs focusing on the most recent works published in the last 2 years.« less

  18. Prospects of nanoscience with nanocrystals

    SciTech Connect

    Kovalenko, Maksym V.; Manna, Liberato; Cabot, Andreu; Hens, Zeger; Talapin, Dmitri V.; Kagan, Cherie R.; Klimov, Victor I.; Rogach, Andrey L.; Reiss, Peter; Milliron, Delia J.; Guyot-Sionnnest, Philippe; Konstantatos, Gerasimos; Parak, Wolfgang J.; Hyeon, Taeghwan; Korgel, Brian A.; Murray, Christopher B.; Heiss, Wolfgang

    2015-01-22

    Colloidal nanocrystals (NCs, i.e., crystalline nanoparticles) have become an important class of materials with great potential for applications ranging from medicine to electronic and optoelectronic devices. Today's strong research focus on NCs has been prompted by the tremendous progress in their synthesis. Impressively narrow size distributions of just a few percent, rational shape-engineering, compositional modulation, electronic doping, and tailored surface chemistries are now feasible for a broad range of inorganic compounds. Furthermore, the performance of inorganic NC-based photovoltaic and lightemitting devices has become competitive to other state-of-the-art materials. Semiconductor NCs hold unique promise for near- and mid-infrared technologies, where very few semiconductor materials are available. On a purely fundamental side, new insights into NC growth, chemical transformations, and self-organization can be gained from rapidly progressing in situ characterization and direct imaging techniques. New phenomena are constantly being discovered in the photophysics of NCs and in the electronic properties of NC solids. In our Nano Focus, we review the state of the art in research on colloidal NCs focusing on the most recent works published in the last 2 years.

  19. Colloidal Nanocrystals: A Model System for the Study of Phase Transformations Since 1950

    NASA Astrophysics Data System (ADS)

    Wittenberg, Joshua

    2011-06-01

    Shock waves provide a means of rapidly compressing a condensed phase sample and studying the resulting structural changes. However, shock studies to date have focused on bulk materials, in which multiple uncorrelated nucleation events lead to complex transformation kinetics. An individual nanocrystal, by comparison, can transform completely with ~10ps following nucleation of the daughter phase, reducing the likelihood that a second nucleation event will occur during the transformation time. In a diamond anvil cell, the wurtzite to rocksalt phase transformation in CdSe nanocrystals, for example, has been shown to follow simple first-order kinetics. The slow, ensemble kinetics observed in those experiments, however, obscured the dynamics within each nanocrystal. Rapidly compressing a nanocrystalline sample using a laser-driven shock wave, the pressure around each nanocrystal can rise on a timescale comparable to that for a sound wave to traverse the crystal. Shock experiments on nanoscale materials therefore have the potential to elucidate aspects of the transformation mechanism inaccessible to further quasi-static diamond anvil cell measurements behavior of CdSe nanocrystals under shock stresses of 2--3.75 GPa has been studied. Above 3 GPa a near-complete disappearance of the first excitonic feature and broadening of the low-energy absorption edge were observed, consistent with a wurtzite to rocksalt structural transformation. The transformation pressure was reduced relative to hydrostatic compression in a diamond anvil cell, and the rate increased, attributed to shock induced shear stress along the reaction coordinate. The especially rapid rate observed for a 3.75 GPa shock suggests multiple nucleation events occurring in each particle.

  20. Incorporation of Cu Acceptors in ZnO Nanocrystals

    SciTech Connect

    Oo, W.M.H.; Mccluskey, Matthew D.; Huso, Jesse; Morrison, J.; Bergman, Leah; Engelhard, Mark H.; Saraf, Laxmikant V.

    2010-09-16

    Doping of semiconductor nanocrystals is an important problem in nanomaterials research. Using infrared (IR) and x-ray photoelectron spectroscopy (XPS), we have observed Cu acceptor dopants that were intentionally introduced into ZnO nanocrystals. The incorporation of Cu2+ dopants increased as the diameter of the nanocrystals was increased from ~3 to 5 nm. Etching the nanocrystals with acetic acid revealed a core-shell structure, where a 2-nm lightly doped core is surrounded by a heavily doped shell. These observations are consistent with the trapped dopant model, in which dopant atoms stick to the surface of the core and are overgrown by the nanocrystal material.