Stability, electronic structures and thermoelectric properties of binary Zn–Sb materials

DOE PAGES

He, Xin; Fu, Yuhao; Singh, David J.; ...

2016-11-03

We report first principles studies of the binary Zn–Sb phases in relation to thermoelectric properties and chemical stability. We identify the unknown structure of the Zn 3Sb 2 phase using particle swarm optimization, finding a tetragonal structure different from the hexagonal Mg 3Sb 2 and the hexagonal or cubic Ca 3Sb 2 phases. All the phases are found to be semiconducting with bandgaps in the range of 0.06–0.77 eV. This semiconducting behavior is understood in Zintl terms as a balance between the Zn:Sb and Sb 3-:½(Sb 2) 4- ratios in the stable crystal structures. With the exception of Zn 3Sbmore » 2, which has a small gap, all the compounds have electronic properties favorable for thermoelectric performance.« less

Synthesis and structural characterization of the Zintl phases Na{sub 3}Ca{sub 3}TrPn{sub 4}, Na{sub 3}Sr{sub 3}TrPn{sub 4}, and Na{sub 3}Eu{sub 3}TrPn{sub 4} (Tr=Al, Ga, In; Pn=P, As, Sb)

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

Wang, Yi; Suen, Nian-Tzu; College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002

15 new quaternary Zintl phases have been synthesized by solid-state reactions from the respective elements, and their structures have been determined by single-crystal X-ray diffraction. Na{sub 3}E{sub 3}TrPn{sub 4} (E=Ca, Sr, Eu; Tr=Al, Ga, In; Pn=P, As, Sb) crystallize in the hexagonal crystal system with the non-centrosymmetric space group P6{sub 3}mc (No. 186). The structure represents a variant of the K{sub 6}HgS{sub 4} structure type (Pearson index hP22) and features [TrPn{sub 4}]{sup 9–} tetrahedral units, surrounded by Na{sup +} and Ca{sup 2+}, Sr{sup 2+}, Eu{sup 2+} cations. The nominal formula rationalization [Na{sup +}]{sub 3}[E{sup 2+}]{sub 3}[TrPn{sub 4}]{sup 9–} follows themore » octet rule, suggesting closed-shell configurations for all atoms and intrinsic semiconducting behavior. However, structure refinements for several members hint at disorder and mixing of cations that potentially counteract the optimal valence electron count. - Graphical abstract: The hexagonal, non-centrosymmetric structure of Na{sub 3}E{sub 3}TrPn{sub 4} (E=Ca, Sr, Eu; Tr=Al, Ga, In; Pn=P, As, Sb) features [TrPn{sub 4}]{sup 9–} tetrahedral units, surrounded by Na{sup +} and Ca{sup 2+}, Sr{sup 2+}, Eu{sup 2+} cations. - Highlights: • 15 quaternary phosphides, arsenides, and antimonides are synthesized and structurally characterized. • The structure is a variant of the hexagonal K{sub 6}HgS{sub 4}-type, with distinctive pattern for the cations. • Occupational and/or positional disorder of yet unknown origin exists for some members of the series.« less

High efficiency thermoelectric power generation using Zintl-type materials

NASA Technical Reports Server (NTRS)

Brown, Shawna (Inventor); Snyder, G. Jeffrey (Inventor); Gascoin, Franck (Inventor); Kauzlarich, Susan (Inventor)

2010-01-01

The invention disclosed herein relates to thermoelectrically-active p-type Zintl phase materials as well as devices utilizing such compounds. Such thermoelectric materials and devices may be used to convert thermal energy into electrical energy, or use electrical energy to produce heat or refrigeration. Embodiments of the invention relate to p-type thermoelectric materials related to the compound Yb.sub.14MnSb.sub.11.

Synthesis, energy transfer and tunable emission properties of SrSb2O6:Eu3 +, Bi3 + phosphor

NASA Astrophysics Data System (ADS)

Cao, Renping; Fu, Ting; Peng, Dedong; Cao, Chunyan; Ruan, Wen; Yu, Xiaoguang

2016-12-01

Host SrSb2O6, SrSb2O6:Bi3 +, SrSb2O6:Eu3 +, and SrSb2O6:Eu3 +, Bi3 + phosphors are synthesized by solid state reaction method in air. Host SrSb2O6 with excitation 254 nm shows weak green-yellow emission in the range of 320-780 nm due to Sb5 + → O2- transition. SrSb2O6:Bi3 + phosphor with excitation 365 nm emits green light within the range 400-650 nm owing to the 3P1 → 1S0 transition of Bi3 + ion. SrSb2O6:Eu3 + phosphor with excitation 254 nm exhibits a systematically varied hue from green to orange-red light by increasing Eu3 + concentration from 0 to 7 mol%, and that with excitation 394 nm only shows orange-red light. The optimal Eu3 + concentration is 4 mol% in SrSb2O6:Eu3 + phosphor. SrSb2O6:Eu3 +, Bi3 + phosphor with excitation 254 and 394 nm emits orange-red light. Emission intensity of SrSb2O6:Eu3 + phosphor may be enhanced > 2 times by co-doping Bi3 + ion because of the fluxing agent and energy transfer roles of Bi3 + ion in SrSb2O6:Eu3 +, Bi3 + phosphor. The luminous mechanism of SrSb2O6:Eu3 +, Bi3 + phosphor is analyzed and explained by the simplified energy level diagrams of Sb2O62 - group, Bi3 + and Eu3 + ions, and energy transfer processes between them.

Bonding in Some Zintl Phases: A Study by Tin-119 Mössbauer Spectroscopy

NASA Astrophysics Data System (ADS)

Asbrand, M.; Berry, F. J.; Eisenmann, B.; Kniep, R.; Smart, L. E.; Thied, R. C.

1995-09-01

The 119Sn Mössbauer parameters for a range of Zintl phase compounds are reported. The compounds containing tetrahedrally coordinated tin of composition M5SnX3 (M = Na, K; X = P, As, Sb) have chemical isomer shifts close to that of grey-tin and can be considered to be covalently bonded species. The layer structures of composition KSnX (X = As, Sb) and double-layer compounds M Sn2X2 (M = Na, Sr; X = As, Sb) have tin in a distorted octahedral environment. The chemical isomer shifts are closer to that of white-tin and can be interpreted in terms of metallic bonding.

Zn3Sb4O6F6: Hydrothermal synthesis, crystal structure and nonlinear optical properties

NASA Astrophysics Data System (ADS)

Ali, Sk Imran; Zhang, Weiguo; Halasyamani, P. Shiv; Johnsson, Mats

2017-12-01

Zn3Sb4O6F6 has been synthesized hydrothermally at 230 °C. The crystal structure was determined from single crystal X-ray diffraction data. It crystallizes in the cubic non-centrosymmetric space group I-43m with the unit cell parameter a = 8.1291(4) Å and is isostructural with M3Sb4O6F6 (M = Co, Ni). The new compound is the first oxofluoride containing Zn2+ and a p-element cation with a stereochemically active lone pair. The crystal structure is made up by [ZnO2F4] octahedra forming a network via corner sharing at F-atoms and [SbO3] trigonal pyramids that form [Sb4O6] cages that connect via the O-atoms to the Zn-atoms. Powder second-harmonic generation (SHG) measurements using 1064 nm radiation on Zn3Sb4O6F6 indicate an SHG intensity of approximately 40 × α-SiO2.

New insights into the application of the valence rules in Zintl phases—Crystal and electronic structures of Ba{sub 7}Ga{sub 4}P{sub 9}, Ba{sub 7}Ga{sub 4}As{sub 9}, Ba{sub 7}Al{sub 4}Sb{sub 9}, Ba{sub 6}CaAl{sub 4}Sb{sub 9}, and Ba{sub 6}CaGa{sub 4}Sb{sub 9}

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

He, Hua; Stoyko, Stanislav; Bobev, Svilen, E-mail: bobev@udel.edu

Crystals of three new ternary pnictides—Ba{sub 7}Al{sub 4}Sb{sub 9}, Ba{sub 7}Ga{sub 4}P{sub 9}, and Ba{sub 7}Ga{sub 4}As{sub 9} have been prepared by reactions of the respective elements in molten Al or Pb fluxes. Single-crystal X-ray diffraction studies reveal that the three phases are isotypic, crystallizing in the orthorhombic Ba{sub 7}Ga{sub 4}Sb{sub 9}-type structure (space group Pmmn, Pearson symbol oP40, Z=2), for which only the prototype is known. The structure is based on TrPn{sub 4} tetrahedra (Tr=Al, Ga; Pn=P, As, Sb), connected in an intricate scheme into 1D-ribbons. Long interchain Pn–Pn bonds (d{sub P–P}>3.0 Å; d{sub As–As}>3.1 Å; d{sub Sb–Sb}>3.3 Å)more » account for the realization of 2D-layers, separated by Ba{sup 2+} cations. Applying the classic valance rules to rationalize the bonding apparently fails, and Ba{sub 7}Ga{sub 4}Sb{sub 9} has long been known as a metallic Zintl phase. Earlier theoretical calculations, both empirical and ab-initio, suggest that the possible metallic properties originate from filled anti-bonding Pn–Pn states, and the special roles of the “cations” in this crystal structure. To experimentally probe this hypothesis, we sought to synthesize the ordered quaternary phases Ba{sub 6}CaTr{sub 4}Sb{sub 9} (Tr=Al, Ga). Single-crystal X-ray diffraction work confirms Ba{sub 6.145(3)}Ca{sub 0.855}Al{sub 4}Sb{sub 9} and Ba{sub 6.235(3)}Ca{sub 0.765}Ga{sub 4}Sb{sub 9}, with Ca atoms preferably substituting Ba on one of the three available sites. The nuances of the five crystal structures are discussed, and the chemical bonding in Ba{sub 7}Ga{sub 4}As{sub 9} is interrogated by tight-binding linear muffin-tin orbital calculations. - Graphical abstract: The new Zintl phases—Ba{sub 7}Al{sub 4}Sb{sub 9}, Ba{sub 7}Ga{sub 4}P{sub 9}, and Ba{sub 7}Ga{sub 4}As{sub 9}, and their quaternary variants Ba{sub 6}CaTr{sub 4}Sb{sub 9} (Tr=Al, Ga)—crystallize in the Ba{sub 7}Ga{sub 4}Sb{sub 9} structure type. The structures

Eu2P7X and Ba2As7X (X = Br, I): Chiral double-Zintl salts containing heptapnictotricyclane clusters

NASA Astrophysics Data System (ADS)

Dolyniuk, Juli-Anna; Lee, Shannon; Tran, Nhon; Wang, Jian; Wang, Lin-Lin; Kovnir, Kirill

2018-07-01

Chiral double Zintl salts present tunable crystal structures with enhanced structural flexibilities and potential for applications requiring chiral control and enantioselectivity. To accompany the chiral Sr2P7I and Sr2P7Br double Zintl salts reported by us previously, six new chiral Zintl salts of the form Ba2-ySryAs7I (y = 0, 0.23, 2), Eu2P7I, Eu2P7Br, and Eu1.3Ba0.7P7Br have been synthesized and characterized by single crystal X-ray diffraction and SEM-EDS analyses. All new compounds crystallize in the Sohncke space group P213 (No. 198) with variations of P73- (heptaphosphanortricyclane) or As73- (heptaarsanortricyclane) clusters surrounded by alkaline-earth or Eu cations and halogen anions. Band structure calculations predict semiconducting properties for all synthesized compounds. Diffuse reflectance UV-vis spectroscopy indicates that Eu2P7I is a direct bandgap semiconductor with Eg of 1.7 eV.

Structural phase transition and phonon instability in Cu 12Sb 4S 13

DOE PAGES

May, Andrew F.; Delaire, Olivier A.; Niedziela, Jennifer L.; ...

2016-02-08

In this study, a structural phase transition has been discovered in the synthetic tetrahedrite Cu 12Sb 4S 13 at approximately 88 K. Upon cooling, the material transforms from its known cubic symmetry to a tetragonal unit cell that is characterized by an in-plane ordering that leads to a doubling of the unit cell volume. Specific heat capacity measurements demonstrate a hysteresis of more than two degrees in the associated anomaly. A similar hysteresis was observed in powder x-ray diffraction measurements, which also indicate a coexistence of the two phases, and together these results suggest a first-order transition. This structural transitionmore » coincides with a recently-reported metal-insulator transition, and the structural instability is related to the very low thermal conductivity κ in these materials. Inelastic neutron scattering was used to measure the phonon density of states in Cu 12Sb 4S 13 and Cu 10Zn 2Sb 4S 13, both of which possess a localized, low-energy phonon mode associated with strongly anharmonic copper displacements that suppress κ. In Cu 12Sb 4S 13, signatures of the phase transition are observed in the temperature dependence of the localized mode, which disappears at the structural transition. In contrast, in the cubic Zn-doped material, the mode is at slightly higher-energy but observable for all temperatures, though it softens upon cooling.« less

Structural and thermoelectric properties of zintl-phase CaLiPn (Pn=As, Sb, Bi)

NASA Astrophysics Data System (ADS)

Chandran, Anoop K.; Gudelli, Vijay Kumar; Sreeparvathy, P. C.; Kanchana, V.

2016-11-01

First-principles calculations were carried out to study the structural, mechanical, dynamical and transport properties of zintl phase materials CaLiPn (Pn=As, Sb and Bi). We have used two different approaches to solve the system based on density functional theory. The plane wave pseudopotential approach has been used to study the structural and dynamical properties whereas, full potential linear augment plane wave method is used to examine the electronic structure, mechanical and thermoelectric properties. The calculated ground-state properties agree quite well with experimental values. The computed electronic structure shows the investigated compounds to be direct band gap semiconductors. Further, we have calculated the thermoelectric properties of all the investigated compounds for both the carriers at various temperatures. We found a high thermopower for both the carriers, especially n-type doping to be more favourable, which enabled us to predict that CaLiPn might have promising applications as a good thermoelectric material. Further, the phonon dispersion curves of the investigated compounds showed flat phonon modes and we also find lower optical and acoustic modes to cut each other at the lower frequency range, which further indicate the investigated compounds to possess reasonably low thermal conductivity. We have also analysed the low value of the thermal conductivity through the empirical relations and discussions are presented here.

Efficient optical activation of Eu3+ ions doped in ZnGa2O4 thin films: Correlation between crystalline phase and photoluminescence

NASA Astrophysics Data System (ADS)

Akazawa, Housei; Shinojima, Hiroyuki

2018-06-01

The physicochemical properties of Eu-doped zinc gallate (ZnGaxO1+1.5x:Eu) (1 < x < 6) thin films were investigated by means of photoluminescence (PL) triggered by band-to-band transitions of the host crystal at λ = 325 nm. Close correspondence between PL spectra and crystalline phases was verified by performing combinatorial measurements over four-inch substrates on which there was a spread of Ga/Zn composition ratios. The phase formation kinetics for deposition with H2O as an oxygen source gas followed by post annealing were similar to those of hydrothermal synthesis. ZnGa2O4 preferentially formed for a wide range of compositions between 1 < x < 4 and post annealing temperatures between 400 and 800 °C; intense emissions from Eu3+ ions were observed from the films. In contrast, the phase formation kinetics for deposition with O2 gas followed by post annealing were similar to those of solid-state reactions. Vacuum annealing above 500 °C caused preferential losses of Ga atoms and precipitation of Zn2Ga2O5 crystallites at x < 4, whereas ZnGa2O4 formed when a large amount of Ga (x > 6) was initially contained in the as-deposited state. The resulting PL spectra from Zn2Ga2O5 exhibited only a broad emission band from 450 to 700 nm, which was ascribed to defects in the poorly crystallized Zn:Ga = 1:1 phase. When the films deposited with O2 were post annealed in an O2 ambient, Zn atoms were lost, producing β-Ga2O3 as the primary phase accompanied with ZnGa2O4. The resulting Eu3+ emission was very weak, possibly because the Eu3+ ions attached to Ga2O3 domains were not emission-active and/or could not be efficiently excited due to wide bandgap (5 eV). When ZnGa2O4:Eu films were crystallized during deposition at elevated temperatures, weak emissions only from Eu3+ ions were observed. Taken together, these experimental results indicate that Eu3+ ions attached to ZnGa2O4 are highly emission-active; i.e., ZnGa2O4 is a particularly good host crystal with which to secure

Ferrimagnetism in EuFe4Sb12 due to the interplay of f-electron moments and a nearly ferromagnetic host

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

Krishnamurthy, Vemuru; Lang, J. C.; Haskel, D.

2007-03-01

We combine x-ray magnetic circular dichroism spectroscopy at Fe L-2,L-3 edges, at Eu M-4,M-5 edges, x-ray absorption spectroscopy (XAS) investigation of Eu valence, and local spin density calculations, to show that the filled skutterudite Eu0.95Fe4Sb12 is a ferrimagnet in which the Fe 3d moment and the Eu2+ 4f moment are magnetically ordered with dominant antiferromagnetic coupling. From Eu L-3 edge XAS, we find that about 13% of the Eu have a formal valence of 3+. We ascribe the origin of ferrimagnetism at a relatively high transition temperature T-C of 85 K in Eu0.95Fe4Sb12 to f-electron interaction with the nearly ferromagneticmore » [Fe4Sb12](2.2-) host lattice.« less

Structurally complex Zintl compounds for high temperature thermoelectric power generation

NASA Astrophysics Data System (ADS)

Zevalkink, Alexandra; Pomrehn, Gregory; Gibbs, Zachary; Snyder, Jeffrey

2014-03-01

Zintl phases, characterized by covalently-bonded substructures surrounded by highly electropositive cations, exhibit many of the characteristics desired for thermoelectric applications. Recently, we demonstrated promising thermoelectric performance (zT values between 0.4 and 0.9) in a class of Zintl antimonides that share a common structural motif: anionic moieties resembling infinite chains of linked tetrahedra. These compounds (A5M2 Sb6 and A3 M Sb3 compounds where A = Ca or Sr and M = Al, Ga and In) crystallize as four distinct, but closely related chain-forming structure types. Their large unit cells lead to exceptionally low lattice thermal conductivity due to the containment of heat in low velocity optical phonon modes. Here, we show that chemical substitutions on the A and M sites can be used to control the electronic and thermal transport properties and optimize the thermoelectric figure of merit. Doping with alio-valent elements allows for rational control of the carrier concentration, while isoelectronic substitutions can be used to fine-tune the intrinsic properties. A combination of Density Functional calculations and classical transport models was used to explain the experimentally observed transport properties of these compounds.

Synthesis and characterization of the divalent samarium Zintl-phases SmMg 2Bi 2 and SmMg 2Sb 2

DOE PAGES

Ramirez, D.; Gallagher, A.; Baumbach, R.; ...

2015-08-29

Here, single crystals of LnMg 2Bi 2 (Ln = Yb, Eu, Sm) and SmMg 2Sb 2 were synthesized using Mg-Bi metal and Mg-Sb metal fluxes, respectively. The crystal structures are of the CaAl 2Si 2 type with space group P3 m1 (#164, Z = 1): SmMg 2Bi 2 ( a = 4.7745(1)Å, c = 7.8490(2)Å), EuMg 2Bi 2 ( a = 4.7702(1)Å, c = 7.8457(2) Å), YbMg 2Bi 2 ( a = 4.7317(2)Å, c = 7.6524(3) Å), and SmMg 2Sb 2 ( a = 4.6861(1) Å, c = 7.7192(2) Å). Heat capacity, electrical transport, and magnetization of all bismuth containingmore » phases were measured. The materials behave as “poor metals” with resistivity between 2 and 10 mΩ·cm. Temperature independent Van Vleck paramagnetism is observed in SmMg 2Bi 2 indicative of divalent samarium (Sm 2+) ions.« less

An impurity intermediate band due to Pb doping induced promising thermoelectric performance of Ca5In2Sb6.

PubMed

Feng, Zhenzhen; Wang, Yuanxu; Yan, Yuli; Zhang, Guangbiao; Yang, Jueming; Zhang, Jihua; Wang, Chao

2015-06-21

Band engineering is one of the effective approaches for designing ideal thermoelectric materials. Introducing an intermediate band in the band gap of semiconducting thermoelectric compounds may largely increase the carrier concentration and improve the electrical conductivity of these compounds. We test this hypothesis by Pb doping in Zintl Ca5In2Sb6. In the current work, we have systematically investigated the electronic structure and thermoelectric performances of substitutional doping with Pb on In sites at a doping level of 5% (0.2 e per cell) for Ca5In2Sb6 by using density functional theory combined with semi-classical Boltzmann theory. It is found that in contrast to Zn doping, Pb doping introduces a partially filled intermediate band in the band gap of Ca5In2Sb6, which originates from the Pb s states by weakly hybridizing with the Sb p states. Such an intermediate band dramatically increases the electrical conductivity of Ca5In2Sb6 and has little detrimental effect on its Seebeck coefficient, which may increase its thermoelectric figure of merit, ZT. Interestingly, a maximum ZT value of 2.46 may be achieved at 900 K for crystalline Pb-doped Ca5In2Sb6 when the carrier concentration is optimized. Therefore, Pb-doped Ca5In2Sb6 may be a promising thermoelectric material.

Unusual Phase Diagram of CeOs 4Sb 12

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

Ho, P. -C.; Goddard, P. A.; Maple, M. B.

2017-03-01

Filled skutterudite compounds, with the formula MT 4X 12, where M is an alkali metal, alkaline-earth, lanthanide, or actinide, T is Fe, Ru, or Os, and X is P, As, or Sb, display a wide variety of interesting phenomena caused by strong electron correlations [1]. Among these, the three compounds CeOs 4Sb 12, PrOs 4Sb 12, and NdOs 4Sb 12, formed by employing Periodic Table neighbors for M, span the range from an antiferromagnetic (AFM) semimetal (M = Ce) via a 1.85 K unconventional (quadrupolar-fluctuation mediated) superconductor (M = Pr) to a 1 K ferromagnet (FM; M = Nd). Inmore » the course of an extended study of these compounds, we uncovered an unusual phase diagram for CeOs 4Sb 12.« less

Modeling the thermal conductivities of the zinc antimonides ZnSb and Zn4Sb3

NASA Astrophysics Data System (ADS)

Bjerg, Lasse; Iversen, Bo B.; Madsen, Georg K. H.

2014-01-01

ZnSb and Zn4Sb3 are interesting as thermoelectric materials because of their low cost and low thermal conductivity. We introduce a model of the lattice thermal conductivity which is independent of fitting parameters and takes the full phonon dispersions into account. The model is found to give thermal conductivities with the correct relative magnitudes and in reasonable quantitative agreement with experiment for a number of semiconductor structures. The thermal conductivities of the zinc antimonides are reviewed and the relatively large effect of nanostructuring on the zinc antimonides is rationalized in terms of the mean free paths of the heat carrying phonons. The very low thermal conductivity of Zn4Sb3 is found to be intrinsic to the structure. However, the low-lying optical modes are observed in both Zn-Sb structures and involve both Zn and Sb vibrations, thereby strongly questioning dumbbell rattling. A mechanism for the very low thermal conductivity observed in Zn4Sb3 is identified. The large Grüneisen parameter of this compound is traced to the Sb atoms which coordinate only Zn atoms.

Photoluminescence of rare-earth ion (Eu3+, Tm3+, and Er3+)-doped and co-doped ZnNb2O6 for solar cells

NASA Astrophysics Data System (ADS)

Gao, Sen-Pei; Qian, Yan-Nan; Wang, Biao

2015-08-01

Visible converted emissions produced at an excitation of 286 nm in ZnNb2O6 ceramics doped with rare-earth ions (RE = Eu3+, Tm3+, Er3+ or a combination of these ions) were investigated with the aim of increasing the photovoltaic efficiency of solar cells. The structure of RE:ZnNb2O6 ceramics was confirmed by x-ray diffraction patterns. The undoped ZnNb2O6 could emit a blue emission under 286-nm excitation, which is attributed to the self-trapped excitons’ recombination of the efficient luminescence centers of edge-shared NbO6 groups. Upon 286-nm excitation, Eu:ZnNb2O6, Tm:ZnNb2O6, and Er:ZnNb2O6 ceramics showed blue, green, and red emissions, which correspond to the transitions of 5D0 → 7FJ (J = 1-4) (Eu3+), 1G4 → 3H6 (Tm3+), and 2H11/2/4S3/2 → 4I15/2 (Er3+), respectively. The calculated CIE chromaticity coordinates of Eu:ZnNb2O6, Tm:ZnNb2O6, and Er:ZnNb2O6 are (0.50, 0.31), (0.14, 0.19), and (0.29, 0.56), respectively. RE ion-co-doped ZnNb2O6 showed a combination of characteristic emissions. The chromaticity coordinates of Eu/Tm:ZnNb2O6, Eu/Er:ZnNb2O6, and Tm/Er:ZnNb2O6 were calculated to be (0.29, 0.24), (0.45, 0.37), and (0.17, 0.25). Project supported by the National Natural Science Foundation of China (Grant Nos. 10572155 and 10732100) and the Research Fund for the Doctoral Program of Ministry of Education, China (Grant No. 20130171130003).

Fabrication of Lanthanum Telluride 14-1-11 Zintl High-Temperature Thermoelectric Couple

NASA Technical Reports Server (NTRS)

Ravi, Vilupanur A.; Li, Billy Chun-Yip; Fleurial, Pierre; Star, Kurt

2010-01-01

The development of more efficient thermoelectric couple technology capable of operating with high-grade heat sources up to 1,275 K is key to improving the performance of radioisotope thermoelectric generators. Lanthanum telluride La3-xTe4 and 14-1-11 Zintls (Yb14MnSb11) have been identified as very promising materials. The fabrication of advanced high-temperature thermoelectric couples requires the joining of several dissimilar materials, typically including a number of diffusion bonding and brazing steps, to achieve a device capable of operating at elevated temperatures across a large temperature differential (up to 900 K). A thermoelectric couple typically comprises a heat collector/ exchanger, metallic interconnects on both hot and cold sides, n-type and ptype conductivity thermoelectric elements, and cold-side hardware to connect to the cold-side heat rejection and provide electrical connections. Differences in the physical, mechanical, and chemical properties of the materials that make up the thermoelectric couple, especially differences in the coefficients of thermal expansion (CTE), result in undesirable interfacial stresses that can lead to mechanical failure of the device. The problem is further complicated by the fact that the thermoelectric materials under consideration have large CTE values, are brittle, and cracks can propagate through them with minimal resistance. The inherent challenge of bonding brittle, high-thermal-expansion thermoelectric materials to a hot shoe material that is thick enough to carry the requisite electrical current was overcome. A critical advantage over prior art is that this device was constructed using all diffusion bonds and a minimum number of assembly steps. The fabrication process and the materials used are described in the following steps: (1) Applying a thin refractory metal foil to both sides of lanthanum telluride. To fabricate the n-type leg of the advanced thermoelectric couple, the pre-synthesized lanthanum

Effect of Varying Pnictogen Elements (Pn=N, P, As, Sb, Bi) on the Optoelectronic Properties of SrZn2Pn2

NASA Astrophysics Data System (ADS)

Murtaza, G.; Yousaf, N.; Laref, A.; Yaseen, M.

2018-03-01

Pnictogen-based Zintl compounds have fascinating properties. Nowadays these compounds have gained exceptional interest in thermoelectric and optoelectronic fields. Therefore, in this work the structural, electronic and optical properties of SrZn2Pn2 (Pn=N, P, As, Sb, Bi) compounds were studied using state-of-the-art density functional theory. The optimised lattice parameters (ɑ, c, c/ɑ and bond lengths) are consistent with the experimental results. The bulk moduli and c/a showed a decrease when changing the Pnictogen (Pn) anion from N to Bi in SrZn2Pn2 (Pn=N, P, As, Sb, Bi). The modified Becke-Johnson potential is used for band structure calculations. All compounds show semiconducting behaviour except SrZn2Bi2, which is metallic. Pn-p, Zn-d and Sr-d play an important role in defining the electronic structure of the compounds. The optical conductivity and absorption coefficient strength are high in visible and ultraviolet regions. These band structures and optical properties clearly show that SrZn2Pn2 compounds are potential candidates in the fields of optoelectronic and photonic devices.

Interplay between magnetism and relativistic fermions in Eu doped (Sr/Ba)MnSb2

NASA Astrophysics Data System (ADS)

Liu, Jinyu; Hu, Jin; Zhu, Yanglin; Chuang, Alyssa; Graf, David; Jaime, Marcelo; Balakirev, Fedor; Weickert, Franziska; Zhang, Qiang; Ditusa, John; Wu, Yan; Cao, Huibo; Mao, Zhiqiang

Layered compounds AMnBi2 (A =Ca, Sr, Ba, Eu, and Yb) have been established as Dirac materials with fascinating properties. In our previous work, we have demonstrated that Sr1-y Mn1-z Sb2 (y, z <0.1), isostructural to AMnBi2, not only host relativistic fermions, but also exhibit ferromagnetic properties, with its ferromagnetism being coupled to the relativistic fermions' transport. To gain further insight into the relativistic fermion-magnetism coupling, we have synthesized a series of Eu doped (Sr/Ba)MnSb2 single crystals and found Eu moments order antiferromagnetically. Through neutron scattering experiments, we determined the magnetic structures for Sr1-xEuxMnSb2 with x = 0.2, 0.5, and 0.8. From magnetotransport measurements, we find the Eu antiferromagnetism is also coupled to relativistic fermion transport. More importantly, we observed a novel quantum phase with saturated magnetoresistivity near the quantum limit for the 10% Eu doped BaMnSb2 sample. We will discuss possible mechanisms for this novel phase.

High temperature neutron powder diffraction study of the Cu12Sb4S13 and Cu4Sn7S16 phases

NASA Astrophysics Data System (ADS)

Lemoine, Pierric; Bourgès, Cédric; Barbier, Tristan; Nassif, Vivian; Cordier, Stéphane; Guilmeau, Emmanuel

2017-03-01

Ternary copper-containing sulfides Cu12Sb4S13 and Cu4Sn7S16 have attracted considerable interest since few years due to their high-efficiency conversion as absorbers for solar energy and promising thermoelectric materials. We report therein on the decomposition study of Cu12Sb4S13 and Cu4Sn7S16 phases using high temperature in situ neutron powder diffraction. Our results obtained at a heating rate of 2.5 K/min indicate that: (i) Cu12Sb4S13 decomposes above ≈792 K into Cu3SbS3, and (ii) Cu4Sn7S16 decomposes above ≈891 K into Sn2S3 and a copper-rich sulfide phase of sphalerite ZnS-type structure with an assumed Cu3SnS4 stoichiometry. Both phase decompositions are associated to a sulfur volatilization. While the results on Cu12Sb4S13 are in fair agreement with recent published data, the decomposition behavior of Cu4Sn7S16 differs from other studies in terms of decomposition temperature, thermal stability and products of reaction. Finally, the crystal structure refinements from neutron powder diffraction data are reported and discussed for the Cu4Sn7S16 and tetrahedrite Cu12Sb4S13 phases at 300 K, and for the high temperature form of skinnerite Cu3SbS3 at 843 K.

Real structure of (Sb1/3Zn2/3)GaO3(ZnO)3, a member of the homologous series ARO3(ZnO)m with ordered site occupation

NASA Astrophysics Data System (ADS)

Garling, Jennifer; Assenmacher, Wilfried; Schmid, Herbert; Longo, Paolo; Mader, Werner

2018-02-01

The hitherto unknown compound (Sb1/3Zn2/3)GaO3(ZnO)3, a member of the homologous series with general formula ARO3(ZnO)m (A,R = trivalent metal cation), was prepared by solid state methods from the binary oxides in sealed Pt-tubes. The structure of (Sb1/3Zn2/3)GaO3(ZnO)3 has been determined by X-ray diffraction from flux-grown single crystals (R 3 ̅ m , Z = 3, aR = 3.2387(7) Å, cR = 41.78(1) Å. The analysis revealed that (Sb1/3Zn2/3)GaO3(ZnO)m is isostructural with InGaO3(ZnO)m, where In3+ on octahedral sites is replaced by Sb5+ and Zn2+ in a ratio of 1:2, preserving an average charge of 3+. (Sb1/3Zn2/3)GaO3(ZnO)3 was furthermore analyzed by electron diffraction, High Angle Annular Dark Field (HAADF) scanning TEM, and high precision EELS spectroscopic imaging, where a periodic ordering of SbO6 octahedra connected via edge sharing to six ZnO6 octahedra in the octahedral layers in a honeycomb motif is found. Due to the large lateral distance of ca. 1.4 nm between adjacent octahedral layers, electrostatic interaction might hardly dictate Sb and Zn positions in neighbouring layers, and hence is a characteristic of the real structure of (Sb1/3Zn2/3)GaO3(ZnO)3. A structure model of the compound in space group P3112 (Nr. 151) with strictly ordered and discrete Sb and Zn positions is derived by crystallographic transformations as closest approximant for the real structure of (Sb1/3Zn2/3)GaO3(ZnO)3. UV-vis measurements confirm this compound to be a transparent oxide with an optical band gap in the UV region with Eg = 3.15 eV.

Fermi-surface topologies and low-temperature phases of the filled skutterudite compounds CeOs 4 Sb 12 and NdOs 4 Sb 12

DOE PAGES

Ho, Pei Chun; Singleton, John; Goddard, Paul A.; ...

2016-11-28

We use MHz conductivity, torque magnetometer, and magnetization measurements to report on single crystals of CeOs 4 Sb 12 and NdOs 4 Sb 12 using temperatures down to 0.5 K and magnetic fields of up to 60 tesla. The field-orientation dependence of the de Haas-van Alphen and Shubnikov-de Haas oscillations is deduced by rotating the samples about the [ 010 ] and [ 0more » $$\\bar{1}$$ 1 1 ] directions. Our results indicate that NdOs 4 Sb 12 has a similar Fermi surface topology to that of the unusual superconductor PrOs 4 Sb 12 , but with significantly smaller effective masses, supporting the importance of local phonon modes in contributing to the low-temperature heat capacity of NdOs 4 Sb 12 . By contrast, CeOs 4 Sb 12 undergoes a field-induced transition from an unusual semimetal into a high-field, high-temperature state characterized by a single, almost spherical Fermi-surface section. Furthermore, the behavior of the phase boundary and comparisons with models of the band structure lead us to propose that the field-induced phase transition in CeOs 4 Sb 12 is similar in origin to the well-known α - γ transition in Ce and its alloys.« less

Heterogeneous in-situ nanostructure contributes to the thermoelectric performance of Zn{sub 4}Sb{sub 3}

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

Lin, Jianping; Ma, Lingzhi; Yang, Baifeng

Single-phase Zn{sub 4}Sb{sub 3} and ZnSb-containing samples were prepared by Plasma Activated Sintering. An abrupt decrease of thermal conductivity was found at about 400 K, which is attributed to the microstructure change of Zn{sub 4}Sb{sub 3}. Nanoscale inclusions and compositional inhomogeneities were found in Zn{sub 4}Sb{sub 3} sample at 473 K by high-resolution transmission electron microscopy. The phonon scattering is enhanced by increasing grain boundaries and chaotic structure, which reduces the thermal conductivity and increases the thermoelectric performance of Zn{sub 4}Sb{sub 3} at elevated temperature. The Rietveld refinement results show that large ZnSb grains in ZnSb-containing samples will accommodate excessmore » Zn atoms, and then reduce thermoelectric performance.« less

Synthesis and Optimization of Thermoelectric Properties of Zn(x)Sb3

NASA Technical Reports Server (NTRS)

Doan-Nguyen, Vicky V.

2005-01-01

High-performance thermoelectric materials are studied to investigate their abilities to optimize electrical and minimize thermal conductivities. A stoichiometric range of p-type zinc antimonide compounds was synthesized to analyze the trends in their thermoelectric properties. Zn(x)Sb3 (x=3.80, 3.85, 3.90, 3.95, 4.00, 4.05, 4.10) was reacted at 750 C and annealed at 300 C for 24 hours at each temperature. Electronic transport properties such as Seebeck and Hall Effect were measured to analyze possible trends in the set of compositions. SEM, EDS, and XRD were used to quantify both ingots and hot-pressed samples to confirm that they were single-phase and of the expected stoichiometries. Recent SEM data indicated that Zn(3.90)Sb3 and Zn(4.00)Sb3 samples were actually Zn3Sb2. In hopes of further improving the figure-of-merit (ZT) of the binary system, V, Cr, Mn, Fe, Co, In, and Sn were used to dope (Zn(0.95)M(0.05))(3.95)Sb3.

Chemical Substitution-Induced and Competitive Formation of 6H and 3C Perovskite Structures in Ba3-xSrxZnSb2O9: The Coexistence of Two Perovskites in 0.3 ≤ x ≤ 1.0.

PubMed

Li, Jing; Jiang, Pengfei; Gao, Wenliang; Cong, Rihong; Yang, Tao

2017-11-20

6H and 3C perovskites are important prototype structures in materials science. We systemically studied the structural evolution induced by the Sr 2+ -to-Ba 2+ substitution to the parent 6H perovskite Ba 3 ZnSb 2 O 9 . The 6H perovskite is only stable in the narrow range of x ≤ 0.2, which attributes to the impressibility of [Sb 2 O 9 ]. The preference of 90° Sb-O-Sb connection and the strong Sb 5+ -Sb 5+ electrostatic repulsion in [Sb 2 O 9 ] are competitive factors to stabilize or destabilize the 6H structure when chemical pressure was introduced by Sr 2+ incorporation. Therefore, in the following, a wide two-phase region containing 1:2 ordered 6H-Ba 2.8 Sr 0.2 ZnSb 2 O 9 and rock-salt ordered 3C-Ba 2 SrZnSb 2 O 9 was observed (0.3 ≤ x ≤ 1.0). In the final, the successive symmetry descending was established from cubic (Fm3̅m, 1.3 ≤ x ≤ 1.8) to tetragonal (I4/m, 2.0 ≤ x ≤ 2.4), and finally to monoclinic (I2/m, 2.6 ≤ x ≤ 3.0). Here we proved that the electronic configurations of B-site cations, with either empty, partially, or fully filled d-shell, would also affect the structure stabilization, through the orientation preference of the B-O covalent bonding. Our investigation gives a deeper understanding of the factors to the competitive formation of perovskite structures, facilitating the fine manipulation on their physical properties.

Antiferromagnetism in EuCu 2As 2 and EuCu 1.82Sb 2 single crystals

DOE PAGES

Anand, V. K.; Johnston, D. C.

2015-05-07

Single crystals of EuCu 2As 2 and EuCu 2Sb 2 were grown from CuAs and CuSb self-flux, respectively. The crystallographic, magnetic, thermal, and electronic transport properties of the single crystals were investigated by room-temperature x-ray diffraction (XRD), magnetic susceptibility χ versus temperature T, isothermal magnetization M versus magnetic field H, specific heat C p(T), and electrical resistivity ρ(T) measurements. EuCu 2As 2 crystallizes in the body-centered tetragonal ThCr 2Si 2-type structure (space group I4/mmm), whereas EuCu 2Sb 2 crystallizes in the related primitive tetragonal CaBe 2Ge 2-type structure (space group P4/nmm). The energy-dispersive x-ray spectroscopy and XRD data for themore » EuCu 2Sb 2 crystals showed the presence of vacancies on the Cu sites, yielding the actual composition EuCu 1.82Sb 2. The ρ(T) and C p(T) data reveal metallic character for both EuCu 2As 2 and EuCu 1.82Sb 2. Antiferromagnetic (AFM) ordering is indicated from the χ(T),C p(T), and ρ(T) data for both EuCu 2As 2 (T N = 17.5 K) and EuCu 1.82Sb 2 (T N = 5.1 K). In EuCu 1.82Sb 2, the ordered-state χ(T) and M(H) data suggest either a collinear A-type AFM ordering of Eu +2 spins S = 7/2 or a planar noncollinear AFM structure, with the ordered moments oriented in the tetragonal ab plane in either case. This ordered-moment orientation for the A-type AFM is consistent with calculations with magnetic dipole interactions. As a result, the anisotropic χ(T) and isothermal M(H) data for EuCu 2As 2, also containing Eu +2 spins S = 7/2, strongly deviate from the predictions of molecular field theory for collinear AFM ordering and the AFM structure appears to be both noncollinear and noncoplanar.« less

High temperature neutron powder diffraction study of the Cu{sub 12}Sb{sub 4}S{sub 13} and Cu{sub 4}Sn{sub 7}S{sub 16} phases

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

Lemoine, Pierric, E-mail: pierric.lemoine@univ-rennes1.fr; Bourgès, Cédric; Barbier, Tristan

Ternary copper-containing sulfides Cu{sub 12}Sb{sub 4}S{sub 13} and Cu{sub 4}Sn{sub 7}S{sub 16} have attracted considerable interest since few years due to their high-efficiency conversion as absorbers for solar energy and promising thermoelectric materials. We report therein on the decomposition study of Cu{sub 12}Sb{sub 4}S{sub 13} and Cu{sub 4}Sn{sub 7}S{sub 16} phases using high temperature in situ neutron powder diffraction. Our results obtained at a heating rate of 2.5 K/min indicate that: (i) Cu{sub 12}Sb{sub 4}S{sub 13} decomposes above ≈792 K into Cu{sub 3}SbS{sub 3}, and (ii) Cu{sub 4}Sn{sub 7}S{sub 16} decomposes above ≈891 K into Sn{sub 2}S{sub 3} and amore » copper-rich sulfide phase of sphalerite ZnS-type structure with an assumed Cu{sub 3}SnS{sub 4} stoichiometry. Both phase decompositions are associated to a sulfur volatilization. While the results on Cu{sub 12}Sb{sub 4}S{sub 13} are in fair agreement with recent published data, the decomposition behavior of Cu{sub 4}Sn{sub 7}S{sub 16} differs from other studies in terms of decomposition temperature, thermal stability and products of reaction. Finally, the crystal structure refinements from neutron powder diffraction data are reported and discussed for the Cu{sub 4}Sn{sub 7}S{sub 16} and tetrahedrite Cu{sub 12}Sb{sub 4}S{sub 13} phases at 300 K, and for the high temperature form of skinnerite Cu{sub 3}SbS{sub 3} at 843 K. - Graphical abstract: In situ neutron powder diffraction data (heating rate of 2.5 K/min) indicates that (i) the ternary Cu{sub 12}Sb{sub 4}S{sub 13} phase is stable up to 792 K and decomposes at higher temperature into Cu{sub 3}SbS{sub 3} and Cu{sub 1.5}Sb{sub 0.5}S{sub 2}, and (ii) the Cu{sub 4}Sn{sub 7}S{sub 16} phase is stable up to 891 K and decomposes at higher temperature into Sn{sub 2}S{sub 3} and a cubic phase of sphalerite ZnS-type structure. Sulfur volatilization likely occurs in order to balance the overall stoichiometry.« less

Internally consistent database for sulfides and sulfosalts in the system Ag 2S-Cu 2S-ZnS-Sb 2S 3-As 2S 3

NASA Astrophysics Data System (ADS)

Sack, Richard O.

2000-11-01

An updated thermodynamic database for Ag 2S-Cu 2S-ZnS-Sb 2S 3-As 2S 3 sulfides and sulfosalts applicable to temperatures above 119°C is developed to calculate phase relations for polybasite-pearceite- and fahlore-bearing assemblages. It is based on pre-existing and new constraints on activity-composition, Ag-Cu and As-Sb partitioning, and other relations, and on experiments (200-300°C, evacuated silica tubes) conducted to define the stability of the polybasite-pearceite [(Ag 1- x,Cu x) 16(Sb 1- y,As y) 2S 11] + ZnS sphalerite assemblage with respect to assemblages containing (Ag,Cu) 2S sulfides coexisting with (Cu, Ag) 10Zn 2(Sb,As) 4S 13 fahlore sulfosalts. It was found that the thermodynamics of mixing of bcc- and hcp-(Ag,Cu) 2S solutions, which are fast-ion conductors, may be described by using site multiplicities of metals α Ag,Cu > 2 and temperature-dependent regular solution parameters. We obtained estimates for the Gibbs energies of formation for Ag 16Sb 2S 11 and Cu 16Sb 2S 11 polybasite endmembers from the simple sulfides (Ag 2S, Cu 2S, and Sb 2S 3) of -30.79 and -4.07 kJ/gfw at 200°C, and -32.04 and -0.59 kJ/gfw at 400°C, respectively, that are about one half kJ/gfw more positive and about 6 kJ/gfw more negative than those estimated by Harlov and Sack (1995b). The corresponding estimates for formation energies of Ag 10Zn 2Sb 4S 13 and Cu 10Zn 2Sb 4S 13 fahlores (-20.29 and -105.29 kJ/gfw at 200°C and -23.72 and -105.76 kJ/gfw at 400°C) are comparable to, and roughly 110 kJ/gfw more positive than, the corresponding estimates of Ebel and Sack (1994). We also determined that the Gibbs energies of the As-Sb exchange reactions: 1/4Ag 10Zn2Sb4S13+1/2Ag 16As2S11=1/2Ag 16Sb2S11+1/4Ag 10Zn2As4S13Sb-fahlorepearceitepolybasiteAs-fahlore and Ag3SbS3+1/2Ag 16As2S11=1/2Ag 16Sb2S11+Ag3AsS3pyrargyritepearceitepolybasiteproustite are, respectively, 8.75 and 0.40 kJ/gfw in the range 150-350°C, and these predictions are consistent with As-Sb partitioning relations

Sol–gel synthesis, structure and luminescence properties of Ba{sub 2}ZnMoO{sub 6}:Eu{sup 3+} phosphors

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

Li, Yuntong; Liu, Xiaohua, E-mail: xhliuxhliu@tom.com

2015-04-15

Graphical abstract: The phosphor powders of Ba{sub 2}ZnMoO{sub 6}:Eu{sup 3+} were prepared by sol–gel method. The dependence of luminescence intensity on the Eu{sup 3+} concentration was investigated. - Highlights: • We synthesize Ba{sub 2}ZnMoO{sub 6}:Eu{sup 3+} phosphors by the sol–gel method. • The effect of temperature on the crystallinity and morphology is investigated. • The phosphor presents an intense CT band in near UV range (370–410 nm). • The concentration quenching mechanism is the exchange interaction. - Abstract: Double-perovskite Ba{sub 2}Zn{sub 1−x}MoO{sub 6}:xEu{sup 3+} (x = 0, 0.02, 0.04, 0.06, 0.08, 0.1) orange–red emitting phosphors were synthesized by using themore » sol–gel method. The crystalline structure and photoluminescence properties of the phosphors were investigated. The X-ray diffraction (XRD) patterns indicate that the structure of matrix Ba{sub 2}ZnMoO{sub 6} is cubic double-perovskite with space group Fm-3m. The Ba{sub 2}ZnMoO{sub 6}:Eu{sup 3+} phosphors present an intense broad charge transfer (CT) band absorption in near UV range (370–410 nm), which attributes to the charge transfer state of MoO{sub 6}, and performs orange–red emission of Eu{sup 3+} ({sup 5}D{sub 0} → {sup 7}F{sub 1} transition) at around 596 nm. A low concentration quenching occurs in Ba{sub 2}ZnMoO{sub 6}:Eu{sup 3+} and the optimal doping concentration is about 6 mol%. The Ba{sub 2}ZnMoO{sub 6}:Eu{sup 3+} phosphors are considered to be a promising orange–red emitting phosphor for near ultraviolet GaN-based white light emitting diode.« less

Hydrides of Alkaline Earth–Tetrel (AeTt) Zintl Phases: Covalent Tt–H Bonds from Silicon to Tin

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

Auer, Henry; Guehne, Robin; Bertmer, Marko

Zintl phases form hydrides either by incorporating hydride anions (interstitial hydrides) or by covalent bonding of H to the polyanion (polyanionic hydrides), which yields a variety of different compositions and bonding situations. Hydrides (deuterides) of SrGe, BaSi, and BaSn were prepared by hydrogenation (deuteration) of the CrB-type Zintl phases AeTt and characterized by laboratory X-ray, synchrotron, and neutron diffraction, NMR spectroscopy, and quantum-chemical calculations. SrGeD4/3–x and BaSnD4/3–x show condensed boatlike six-membered rings of Tt atoms, formed by joining three of the zigzag chains contained in the Zintl phase. These new polyanionic motifs are terminated by covalently bound H atoms withmore » d(Ge–D) = 1.521(9) Å and d(Sn–D) = 1.858(8) Å. Additional hydride anions are located in Ae4 tetrahedra; thus, the features of both interstitial hydrides and polyanionic hydrides are represented. BaSiD2–x retains the zigzag Si chain as in the parent Zintl phase, but in the hydride (deuteride), it is terminated by H (D) atoms, thus forming a linear (SiD) chain with d(Si–D) = 1.641(5) Å.« less

Solid Liquid Interdiffusion Bonding of Zn4Sb3 Thermoelectric Material with Cu Electrode

NASA Astrophysics Data System (ADS)

Lin, Y. C.; Lee, K. T.; Hwang, J. D.; Chu, H. S.; Hsu, C. C.; Chen, S. C.; Chuang, T. H.

2016-10-01

The ZnSb intermetallic compound may have thermoelectric applications because it is low in cost and environmentally friendly. In this study, a Zn4Sb3 thermoelectric element coated with a Ni barrier layer and a Ag reaction layer was bonded with a Ag-coated Cu electrode using a Ag/Sn/Ag solid-liquid interdiffusion bonding process. The results indicated that a Ni5Zn21 intermetallic phase formed easily at the Zn4Sb3/Ni interface, leading to sound adhesion. In addition, Sn film was found to react completely with the Ag layer to form a Ag3Sn intermetallic layer having a melting point of 480°C. The resulting Zn4Sb3 thermoelectric module can be applied at the optimized operation temperature (400°C) of Zn4Sb3 material as a thermoelectric element. The bonding strengths ranged from 14.9 MPa to 25.0 MPa, and shear tests revealed that the Zn4Sb3/Cu-joints fractured through the interior of the thermoelectric elements.

Geology, S-Pb isotopes, and 40Ar/39Ar geochronology of the Zhaxikang Sb-Pb-Zn-Ag deposit in Southern Tibet: implications for multiple mineralization events at Zhaxikang

NASA Astrophysics Data System (ADS)

Sun, Xiang; Zheng, Youye; Pirajno, Franco; McCuaig, T. Campbell; Yu, Miao; Xia, Shenlan; Song, Qingjie; Chang, Huifang

2018-03-01

Several Au, Sb, Sb-Au, Pb-Zn, and Sb-Pb-Zn-Ag deposits are present throughout the North Himalaya in southern Tibet, China. The largest Sb-Pb-Zn-Ag deposit is Zhaxikang (18 Mt at 0.6 wt% Sb, 2.0 wt% Pb, 3.5 wt% Zn, and 78 g/t Ag). Zhaxikang veins are hosted within N-S trending faults, which crosscut the Early-Middle Jurassic Ridang Formation consisting of shale interbedded with sandstone and limestone deposited on a passive continental margin. Ore paragenesis indicates that Zhaxikang mineralization occurred in two main phases composed of six total stages. The initial phase was characterized by assemblages of fine-grained Mn-Fe carbonate + arsenopyrite + pyrite + sphalerite (stage 1), followed by relatively coarse-grained Mn-Fe carbonate + Fe-rich sphalerite + galena + pyrite (stage 2). The second phase was marked by assemblages of quartz + pyrite + Fe-poor sphalerite and Ag-rich galena + tetrahedrite + sericite (stage 3), quartz + Sb-Pb sulfosalt minerals mainly composed of boulangerite and jamesonite (stage 4), quartz + stibnite ± cinnabar (stage 5), and quartz ± calcite (stage 6). Sulfides of stage 2 have δ34SV-CDT of 8.4-12.0‰, 206Pb/204Pb ratios of 19.648 to 19.659, 207Pb/204Pb ratios of 15.788 to 15.812, and 208Pb/204Pb ratios of 40.035 to 40.153. Sulfides of stage 3 have similar δ34SV-CDT of 6.1-11.2‰ and relatively more radiogenic lead isotopes (206Pb/204Pb = 19.683-19.792). Stage 4 Sb-Pb sulfosalt minerals have δ34SV-CDT of 5.0-7.2‰ and even more radiogenic lead (206Pb/204Pb = 19.811-19.981). By contrast, stibnite of stage 5 has δ34SV-CDT of 4.5-7.8‰ and less radiogenic lead (206Pb/204Pb = 18.880-18.974). Taken together with the geological observations that the Pb-Zn-bearing Mn-Fe carbonate veins were crosscut by various types of quartz veins, sphalerite and galena of stage 2 underwent dissolution and remobilization, and that Sb-Pb(-Fe) sulfosalts formed at the expense of Pb from stage 2 galena and of Fe from stage 2 sphalerite, we argue that

Enhancement of thermoelectric figure of merit in β-Zn{sub 4}Sb{sub 3} by indium doping control

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

Wei, Pai-Chun, E-mail: pcwei68@gmail.com, E-mail: cheny2@phys.sinica.edu.tw; Hsu, Chia-Hao; Chang, Chung-Chieh

2015-09-21

We demonstrate the control of phase composition in Bridgman-grown β-Zn{sub 4}Sb{sub 3} crystals by indium doping, an effective way to overcome the difficulty of growing very pure β-Zn{sub 4}Sb{sub 3} thermoelectric material. The crystal structures are characterized by Rietveld refinement with synchrotron X-ray diffraction data. The results show an anisotropic lattice expansion in In-doped β-Zn{sub 4}Sb{sub 3} wherein the zinc atoms are partially substituted by indium ones at 36f site of R-3c symmetry. Through the elimination of ZnSb phase, all the three individual thermoelectric properties are simultaneously improved, i.e., increasing electrical conductivity and Seebeck coefficient while reducing thermal conductivity. Undermore » an optimal In concentration (x = 0.05), pure phase β-Zn{sub 4}Sb{sub 3} crystal can be obtained, which possesses a high figure of merit (ZT) of 1.4 at 700 K.« less

Improvement of antimony sulfide photo absorber performance by interface modification in Sb2S3-ZnO hybrid nanostructures

NASA Astrophysics Data System (ADS)

Ali, Asad; Hasanain, Syed Khurshid; Ali, Tahir; Sultan, Muhammad

2017-03-01

Metal-oxide chalcogenide nanostructures as part of hybrid systems are very important for photovoltaic and optoelectronic applications. It is however known that the various interfaces within the hybrid structures play a crucial role in limiting the efficiency of these devices. Here we report on the improvement of Sb2S3 structure through modification of interface between Zn-oxide nanostructures and chalcogenides. ZnO nanorods were grown on fluorine doped tin oxide (FTO) substrate by chemical bath deposition (CBD) method. X-ray diffraction (XRD) and SEM analysis confirmed the single phase wurtzite structure and c-axis orientation of the ZnO nanorod arrays. Antimony tri-sulfide (Sb2S3) was deposited on ZnO nanords by CBD and subsequently annealed at 300 °C in argon environment for 30 min. XRD and the XPS analysis of ZnO-Sb2S3 system showed the dominant presence of Sb2O3 rather than Sb2S3. Since oxidation of Sb2S3 is understood to proceed mainly from the ZnO-Sb2S3 interface, a ZnS interlayer was introduced between ZnO nanorods and Sb2S3 by chemical route. The subsequent structural and optical properties of the ZnO-ZnS-Sb2S3 system are analyzed in detail. The introduction of sulfide interlayer prevents the oxidation of Sb2S3 which is evident from reduced oxide phase in Sb2S3. Significant improvement in the structural and optical properties of Sb2S3 are reported as compared to the parent ZnO-Sb2S3 system. This gain in the optical properties of hybrid ZnO-ZnS-Sb2S3 nanostructures is explained as being related to successful prevention of Sb2O3 formation at the Sb-ZnO interface and stabilization of the desired Sb2S3.

First-principles study of amorphous Ga4Sb6Te3 phase-change alloys

NASA Astrophysics Data System (ADS)

Bouzid, Assil; Gabardi, Silvia; Massobrio, Carlo; Boero, Mauro; Bernasconi, Marco

2015-05-01

First-principles molecular dynamics simulations within the density functional theory framework were performed to generate amorphous models of the Ga4Sb6Te3 phase change alloy by quenching from the melt. We find that Ga-Sb and Ga-Te are the most abundant bonds with only a minor amount of Sb-Te bonds participating to the alloy network. Ga and four-coordinated Sb atoms present a tetrahedral-like geometry, whereas three-coordinated Sb atoms are in a pyramidal configuration. The tetrahedral-like geometries are similar to those of the crystalline phase of the two binary compounds GaTe and GaSb. A sizable fraction of Sb-Sb bonds is also present, indicating a partial nanoscale segregation of Sb. Despite the fact that the composition Ga4Sb6Te3 lies on the pseudobinary Ga Sb -Sb2Te3 tie line, the amorphous network can be seen as a mixture of the two binary compounds GaTe and GaSb with intertwined elemental Sb.

Multistage hydrothermal silicification and Fe-Tl-As-Sb-Ge-REE enrichment in the Red Dog Zn-Pb-Ag district, northern Alaska: Geochemistry, origin, and exploration applications

USGS Publications Warehouse

Slack, J.F.; Kelley, K.D.; Anderson, V.M.; Clark, J.L.; Ayuso, R.A.

2004-01-01

Geochemical analyses of major, trace, and rare earth elements (REE) in more than 200 samples of variably silicified and altered wall rocks, massive and banded sulfide, silica rock, and sulfide-rich and unmineralized barite were obtained from the Main, Aqqaluk, and Anarraaq deposits in the Red Dog Zn-Pb-Ag district of northern Alaska. Detailed lithogeochemical profiles for two drill cores at Aqqaluk display an antithetic relationship between SiO2/Al2O3 and TiO2/Zr which, together with textural information, suggest preferential silicification of carbonate-bearing sediments. Data for both drill cores also show generally high Tl, Sb, As, and Ge and uniformly positive Eu anomalies (Eu/Eu* > 1.0). Similar high Tl, Sb, As, Ge, and Eu/Eu* values are present in the footwall and shallow hanging wall of Zn-Pb-Ag sulfide intervals at Anarraaq but are not as widely dispersed. Net chemical changes for altered wall rocks in the district, on the basis of average Al-normalized data relative to unaltered black shales of the host Kuna Formation, include large enrichments (>50%) of Fe, Ba, Eu, V, S, Co, Zn, Pb, Tl, As, Sb, and Ge at both Red Dog and Anarraaq, Si at Red Dog, and Sr, U, and Se at Anarraaq. Large depletions (>50%) are evident for Ca at both Red Dog and Anarraaq, for Mg, P, and Y at Red Dog, and for Na at Anarraaq. At both Red Dog and Anarraaq, wall-rock alteration removed calcite and minor dolomite during hydrothermal decarbonation reactions and introduced Si, Eu, and Ge during silicification. Sulfidation reactions deposited Fe, S, Co, Zn, Pb, Tl, As, and Sb; barite mineralization introduced Ba, S, and Sr. Light REE and U were mobilized locally. This alteration and mineralization occurred during Mississippi an hydrothermal events that predated the Middle Jurassic-Cretaceous Brookian orogeny. Early hydrothermal silicification at Red Dog took place prior to or during massive sulfide mineralization, on the basis of the dominantly planar nature of Zn-Pb veins, which suggests

Effect of tungsten on the phase-change properties of Ge8Sb2Te11 thin films for the phase-change device

NASA Astrophysics Data System (ADS)

Park, Cheol-Jin; Kong, Heon; Lee, Hyun-Yong; Yeo, Jong-Bin

2017-07-01

In this study, the electrical, optical, and structural properties of tungsten (W)-doped Ge8Sb2Te11 thin films were investigated. Previously, GeSbTe alloys were doped with various materials in an attempt to improve the thermal stability. Ge8Sb2Te11 and W-doped Ge8Sb2Te11 films with a thickness of 200 nm were fabricated by using an RF magnetron reactive co-sputtering system at room temperature on Si ( p-type, 100) and glass substrate. The fabricated thin films were annealed in a furnace in the 0 - 400 ° C temperature range. The optical properties were analyzed using a UV-Vis-IR spectrophotometer, and by using Beer's Law equation, the optical-energy band gap ( E op ), slope B 1/2, and slope 1/ F were calculated. For the crystalline materials, an increase in the slope B 1/2 and 1/ F was observed, exhibiting a good effect on the thermal stability in the amorphous state after the phase change. The structural properties were analyzed by X-ray diffraction, and the result showed that the W-doped Ge8Sb2Te11 had a face-centered-cubic (fcc) crystalline structure increased crystallization temperature ( T c ). An increase in the T c increased the thermal stability in the amorphous state. The electrical properties were analyzed using a 4-point probe, exhibiting an increase in the sheet resistance ( R s ) in the amorphous and the crystalline states indicating a reduced programming current in the memory device.

Synthesis, characterization and photocatalysis enhancement of Eu2O3-ZnO mixed oxide nanoparticles

NASA Astrophysics Data System (ADS)

Mohamed, W. S.; Abu-Dief, Ahmed M.

2018-05-01

Pure ZnO nanoparticles (NPs) and mixed Eu2O3 and ZnO NPs with different Eu2O3 ratios (5%, 10%, and 15%) were synthesized by a precipitation method under optimum conditions. The synthesized samples were characterized by means of X-ray diffraction, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy, transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, and UV-vis diffuse reflectance spectroscopy. The as-synthesized ZnO NPs exhibit high phase purity and a highly crystalline wurtzite ZnO structure. The mixed Eu2O3 and ZnO NPs exhibit a Eu2O3 zinc blend phase in addition to the wurtzite phase of pure ZnO, confirming the high purity and good crystallinity of the as-synthesized samples. The high-purity formation of ZnO and Eu2O3 phases was confirmed by FTIR and Raman spectra. Microstructural analysis by SEM and TEM confirmed the sphere-like morphology with different particle sizes (29-40 nm) of the as-synthesized samples. The photocatalytic activities of pure ZnO NPs and mixed Eu2O3 and ZnO NPs for the degradation of methylene blue were evaluated under ultraviolet (UV) irradiation. The results show that Eu2O3 plays an important role in the enhancement of the photocatalytic properties of ZnO NPs. We found that mixed 5% Eu2O3 and ZnO NPs exhibit the highest photocatalytic activity (degradation efficiency of 96.5% after 180 min of UV irradiation) as compared with pure ZnO NPs (degradation efficiency of 80.3% after 180 min of UV irradiation). The increased photocatalytic activity of the optimum mixed Eu2O3 and ZnO NPs is due to the high crystallinity, high surface area with small particle size, and narrow energy gap.

Sb content dependent thermoelectric properties of the p-type ZnO:Sb films fabricated by oxidation method

NASA Astrophysics Data System (ADS)

Li, Guojian; Lin, Xiao; Liu, Shiying; Jia, Baohai; Wang, Qiang

2018-05-01

It is important to fabricate stable p-type ZnO:Sb thermoelectric (TE) films for the p-n homojunction TE devices that convert waste heat directly into electricity. In this study, the ZnO:Sb films with different Sb contents were prepared by oxidizing evaporated Zn-Sb films in oxygen. The film with a high Sb content (5.32%) is easy to form Zn4Sb3 and ZnSb compound in the wurtzite ZnO. The resistivity has a sharply reduction with the Sb content from 0.228 Ω·m of 3.95% Sb to 4.68 × 10-5 Ω·m of 5.32% Sb. The lowest resistivity is lower at least one order of magnitude than the results of others with the similar Sb content. The Seebeck coefficient indicates that the 5.32% Sb film remains stable p-type conduction. The carrier concentration is about 1020 cm-3 and is higher at least one order of magnitude than the other results. Raman analysis indicates that the peak of E2high related O sublattice vibrations indicates that the O sites are substituted by Sb3+ ions, which increases the carrier concentration. However, the mobility is relatively weak because the intrinsic host lattice defects activated as vibrating complexes. The power factor of the p-type ZnO:Sb of the 5.32% Sb film at 427 °C is 46.79 μW/m·K2.

Roles of cations, electronegativity difference, and anionic interlayer interactions in the metallic versus nonmetallic character of Zintl phases related to arsenic.

PubMed

Alemany, Pere; Llunell, Miquel; Canadell, Enric

2008-10-01

A first-principles Density Functional Theory study of several layered solids structurally related to rhombohedral arsenic has been carried out. The electronic structures of rhombohedral arsenic, CaSi(2), CaAl(2)Si(2), KSnSb, and SrSn(2)As(2) are discussed in detail, emphasizing on the origins of their metallic or nonmetallic behaviours. It is found that all of these systems are metallic except KSnSb. Electronegativity differences between the elements in the anionic sublattice and/or direct interlayer interactions play the main role in controlling the conductivity behavior. CaSi(2) exhibits a peculiar feature since the cation directly influences the conductivity but is not essential for its appearance. Cation-anion interactions are shown to have an important covalent contribution, but despite this fact and the metallic character found for most of these phases, the Zintl approach still provides a valid approximation to their electronic structure. (c) 2008 Wiley Periodicals, Inc.

Sb-related defects in Sb-doped ZnO thin film grown by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Luo, Caiqin; Ho, Lok-Ping; Azad, Fahad; Anwand, Wolfgang; Butterling, Maik; Wagner, Andreas; Kuznetsov, Andrej; Zhu, Hai; Su, Shichen; Ling, Francis Chi-Chung

2018-04-01

Sb-doped ZnO films were fabricated on c-plane sapphire using the pulsed laser deposition method and characterized by Hall effect measurement, X-ray photoelectron spectroscopy, X-ray diffraction, photoluminescence, and positron annihilation spectroscopy. Systematic studies on the growth conditions with different Sb composition, oxygen pressure, and post-growth annealing were conducted. If the Sb doping concentration is lower than the threshold ˜8 × 1020 cm-3, the as-grown films grown with an appropriate oxygen pressure could be n˜4 × 1020 cm-3. The shallow donor was attributed to the SbZn related defect. Annealing these samples led to the formation of the SbZn-2VZn shallow acceptor which subsequently compensated for the free carrier. For samples with Sb concentration exceeding the threshold, the yielded as-grown samples were highly resistive. X-ray diffraction results showed that the Sb dopant occupied the O site rather than the Zn site as the Sb doping exceeded the threshold, whereas the SbO related deep acceptor was responsible for the high resistivity of the samples.

The magnetic structure of EuCu 2Sb 2

DOE PAGES

Ryan, D. H.; Cadogan, J. M.; Anand, V. K.; ...

2015-05-06

Antiferromagnetic ordering of EuCu 2Sb 2 which forms in the tetragonal CaBe 2Ge 2-type structure (space group P4/nmm #129) has been studied using neutron powder diffraction and 151Eu Mössbauer spectroscopy. The room temperature 151Eu isomer shift of –12.8(1) mm/s shows the Eu to be divalent, while the 151Eu hyperfine magnetic field (B hf) reaches 28.7(2) T at 2.1 K, indicating a full Eu 2+ magnetic moment. B hf(T) follows a smoothmore » $$S=\\frac{7}{2}$$ Brillouin function and yields an ordering temperature of 5.1(1) K. Refinement of the neutron diffraction data reveals a collinear A-type antiferromagnetic arrangement with the Eu moments perpendicular to the tetragonal c-axis. As a result, the refined Eu magnetic moment at 0.4 K is 7.08(15) μ B which is the full free-ion moment expected for the Eu 2+ ion with $$S=\\frac{7}{2}$$ and a spectroscopic splitting factor of g = 2.« less

Electronic structure and chemical bonding of the electron-poor II-V semiconductors ZnSb and ZnAs

NASA Astrophysics Data System (ADS)

Benson, Daryn; Sankey, Otto F.; Häussermann, Ulrich

2011-09-01

The binary compounds ZnSb and ZnAs with the CdSb structure are semiconductors (II-V), although the average electron concentration (3.5 per atom) is lower than that of the tetrahedrally bonded III-V and II-VI archetype systems (four per atom). We report a detailed electronic structure and chemical bonding analysis for ZnSb and ZnAs based on first-principles calculations. ZnSb and ZnAs are compared to the zinc blende-type semiconductors GaSb, ZnTe, GaAs, and ZnSe, as well as the more ionic, hypothetical, II-V systems MgSb and MgAs. We establish a clearly covalent bonding scenario for ZnSb and ZnAs where multicenter bonded structural entities (rhomboid rings Zn2Sb2 and Zn2As2) are connected to each other by classical two-center, two-electron bonds. This bonding scenario is only compatible with a weak ionicity in II-V semiconductor systems, and weak ionicity appears as a necessary condition for the stability of the CdSb structure type. It is argued that a chemical bonding scenario with mixed multicenter and two-center bonding resembles that of boron and boron-rich compounds and is typical of electron-poor sp-bonded semiconductors with average valence electron concentrations below four per atom.

Study on anisotropy of n-type Mg3Sb2-based thermoelectric materials

NASA Astrophysics Data System (ADS)

Song, Shaowei; Mao, Jun; Shuai, Jing; Zhu, Hangtian; Ren, Zhensong; Saparamadu, Udara; Tang, Zhongjia; Wang, Bo; Ren, Zhifeng

2018-02-01

The recent discovery of a high thermoelectric figure of merit (ZT) in an n-type Mg3Sb2-based Zintl phase triggered an intense research effort to pursue even higher ZT. Based on our previous report on Mg3.1Nb0.1Sb1.5Bi0.49Te0.01, we report here that partial texturing in the (001) plane is achieved by double hot pressing, which is further confirmed by the rocking curves of the (002) plane. The textured samples of Mg3.1Nb0.1Sb1.5Bi0.49Te0.01 show a much better average performance in the (00l) plane. Hall mobility is significantly improved to ˜105 cm2 V-1 s-1 at room temperature in the (00l) plane due to texturing, resulting in higher electrical conductivity, a higher power factor of ˜18 μW cm-1 K-2 at room temperature, and also higher average ZT. This work shows that texturing is good for higher thermoelectric performance, suggesting that single crystals of n-type Mg3Sb2-based Zintl compounds are worth pursuing.

Yb5Ga2Sb6: a mixed valent and narrow-band gap material in the RE5M2X6 family.

PubMed

Subbarao, Udumula; Sarkar, Sumanta; Gudelli, Vijay Kumar; Kanchana, V; Vaitheeswaran, G; Peter, Sebastian C

2013-12-02

A new compound Yb5Ga2Sb6 was synthesized by the metal flux technique as well as high frequency induction heating. Yb5Ga2Sb6 crystallizes in the orthorhombic space group Pbam (no. 55), in the Ba5Al2Bi6 structure type, with a unit cell of a = 7.2769(2) Å, b = 22.9102(5) Å, c = 4.3984(14) Å, and Z = 2. Yb5Ga2Sb6 has an anisotropic structure with infinite anionic double chains (Ga2Sb6)(10-) cross-linked by Yb(2+) and Yb(3+) ions. Each single chain is made of corner-sharing GaSb4 tetrahedra. Two such chains are bridged by Sb2 groups to form double chains of 1/∞ [Ga2Sb6(10-)]. The compound satisfies the classical Zintl-Klemm concept and is a narrow band gap semiconductor with an energy gap of around 0.36 eV calculated from the electrical resistivity data corroborating with the experimental absorption studies in the IR region (0.3 eV). Magnetic measurements suggest Yb atoms in Yb5Ga2Sb6 exist in the mixed valent state. Temperature dependent magnetic susceptibility data follows the Curie-Weiss behavior above 100 K and no magnetic ordering was observed down to 2 K. Experiments are accompanied by all electron full-potential linear augmented plane wave (FP-LAPW) calculations based on density functional theory to calculate the electronic structure and density of states. The calculated band structure shows a weak overlap of valence band and conduction band resulting in a pseudo gap in the density of states revealing semimetallic character.

Mobilization of Ag, heavy metals and Eu from the waste deposit of the Las Herrerias mine (Almería, SE Spain)

NASA Astrophysics Data System (ADS)

Navarro, A.; Cardellach, E.

2009-02-01

We studied the mobility of silver, heavy metals and europium in waste from the Las Herrerías mine in Almería (SE Spain). The most abundant primary mineral phases in the mine wastes are hematite, hydrohematite, barite, quartz, muscovite, anorthite, calcite and phillipsite. The minor phase consisted of primary minerals including ankerite, cinnabar, digenite, magnesite, stannite, siderite and jamesonite, and secondary minerals such as glauberite, szomolnokite, thenardite and uklonscovite. The soils show high concentrations of Ag (mean 21.6 mg kg-1), Ba (mean 2.5%), Fe (mean 114,000 mg kg-1), Sb (mean 342.5 mg kg-1), Pb (mean 1,229.8 mg kg-1), Zn (mean 493 mg kg-1), Mn (mean 4,321.1 mg kg-1), Cd (mean 1.2 mg kg-1) and Eu (mean 4.0 mg kg-1). The column experiments showed mobilization of Ag, Al, Ba, Cu, Cd, Eu, Fe, Mn, Ni, Sb, Pb and Zn, and the inverse modelling showed that the dissolution of hematite, hausmannite, pyrolusite and anglesite can largely account for the mobilization of Fe, Mn and Pb in the leaching experiment. The mobility of silver may be caused by the presence of kongsbergite and chlorargyrite in the waste, while the mobility of Eu seems to be determined by Eu(OH)3, which controls the solubility of Eu in the pH-Eh conditions of the experiments. The mineralogy, pH, Eh and geochemical composition of the mine wastes may explain the possible mobilization of heavy metals and metalloids. However, the absence of contaminants in the groundwater may be caused by the carbonate-rich environment of “host-rocks” that limits their mobility.

Effects of Ge and Sn substitution on the metal-semiconductor transition and thermoelectric properties of Cu12Sb4S13 tetrahedrite.

PubMed

Kosaka, Yasufumi; Suekuni, Koichiro; Hashikuni, Katsuaki; Bouyrie, Yohan; Ohta, Michihiro; Takabatake, Toshiro

2017-03-29

The synthetic tetrahedrites Cu 12-y Tr y Sb 4 S 13 (Tr: Mn, Fe, Co, Ni, Zn) have been extensively studied due to interest in metal-semiconductor transition as well as in superior thermoelectric performance. We have prepared Ge- and Sn-bearing tetrahedrites, Cu 12-x M x Sb 4 S 13 (M = Ge, Sn; x ≤ 0.6), and investigated the effects of the substitutions on the phase transition and the thermoelectric properties. The substitutions of Ge and Sn for Cu suppress the metal-semiconductor transition and increase the electrical resistivity ρ and the positive thermopower S. This finding suggests that the phase transition is prevented by electron doping into the unoccupied states of the valence band. The variations of ρ, S, and magnetic susceptibility for the present systems correspond well with those for the system with Tr = Zn 2+ , confirming the tetravalent states for Ge and Sn. The substitution of M 4+ for Cu 1+ decreases the power factor S 2 /ρ but enhances the dimensionless thermoelectric figure of merit ZT, due to reductions in both the charge carrier contribution and lattice contribution to the thermal conductivity. As a result, ZT has a maximum value of ∼0.65 at 665 K for x = 0.3-0.5 in Cu 12-x M x Sb 4 S 13 with M = Ge and Sn.

SB6.0: The 6th International meeting on Synthetic Biology, July 9-11, 2013

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

Kahl, Linda J.

The Synthetic Biology conference series (SBx.0) is the preeminent academic meeting in synthetic biology. Organized by the BioBricks Foundation, the SBx.0 conference series brings together leading researchers, students, industry executives, and policy makers from around the world to share, consider, debate, and plan efforts to make biology easier to engineer. Historically held every two years, the SBx.0 conferences are held in alternating locations in the United States, Europe, and Asia to encourage global participation and collaboration so that the ramifications of synthetic biology research and development are most likely to be safe ethical, and beneficial. On 9-11 July 2013, themore » 6th installment of the synthetic biology conference series (SB6.0) was held on the campus of Imperial College London (http://sb6.biobricks.org). The SB6.0 conference was attended by over 700 people, and many more were able to participate via video digital conference (http://sb6.biobricks.org/digital-conference/). Over the course of three days, the SB6.0 conference agenda included plenary sessions, workshops, and poster presentations covering topics ranging from the infrastructure needs arising when “Systematic Engineering Meets Biological Complexity” and design-led considerations for “Connecting People and Technologies” to discussions on “Engineering Biology for New Materials,” “Assessing Risk and Managing Biocontainment,” and “New Directions for Energy and Sustainability.” The $10,150 grant awarded by the U.S. Department of Energy (DE-SC0010233) to the BioBricks Foundation was used to provide partial reimbursement for the travel expenses of leading researchers from the United States to speak at the SB6.0 conference. A total of $9,450 was used to reimburse U.S. speakers for actual expenses related to the SB6.0 conference, including airfare (economy or coach only), ground transportation, hotel, and registration fees. In addition, $700 of the grant was used to

Detection of Cu2Zn5SnSe8 and Cu2Zn6SnSe9 phases in co-evaporated Cu2ZnSnSe4 thin-films

NASA Astrophysics Data System (ADS)

Schwarz, Torsten; Marques, Miguel A. L.; Botti, Silvana; Mousel, Marina; Redinger, Alex; Siebentritt, Susanne; Cojocaru-Mirédin, Oana; Raabe, Dierk; Choi, Pyuck-Pa

2015-10-01

Cu2ZnSnSe4 thin-films for photovoltaic applications are investigated using combined atom probe tomography and ab initio density functional theory. The atom probe studies reveal nano-sized grains of Cu2Zn5SnSe8 and Cu2Zn6SnSe9 composition, which cannot be assigned to any known phase reported in the literature. Both phases are considered to be metastable, as density functional theory calculations yield positive energy differences with respect to the decomposition into Cu2ZnSnSe4 and ZnSe. Among the conceivable crystal structures for both phases, a distorted zinc-blende structure shows the lowest energy, which is a few tens of meV below the energy of a wurtzite structure. A band gap of 1.1 eV is calculated for both the Cu2Zn5SnSe8 and Cu2Zn6SnSe9 phases. Possible effects of these phases on solar cell performance are discussed.

Controlled synthesis of Eu 2+ and Eu 3+ doped ZnS quantum dots and their photovoltaic and magnetic properties

DOE PAGES

Horoz, Sabit; Yakami, Baichhabi; Poudyal, Uma; ...

2016-04-27

Eu-doped ZnS quantum dots (QDs) have been synthesized by wet-chemical method and found to form in zinc blende (cubic) structure. Both Eu 2+ and Eu 3+ doped ZnS can be controllably synthesized. The Eu 2+ doped ZnS QDs show broad photoluminescence emission peak around 512 nm, which is from the Eu2+ intra-ion transition of 4f 6d1 – 4f 7, while the Eu 3+ doped samples exhibit narrow emission lines characteristic of transitions between the 4f levels. The investigation of the magnetic properties shows that the Eu 3+ doped samples exhibit signs of ferromagnetism, on the other hand, Eu 2+ dopedmore » samples are paramagnetic of Curie-Weiss type. The incident photon to electron conversion efficiency is increased with the Eu doping, which suggests the QD solar cell efficiency can be enhanced by Eu doping due to widened absorption windows. This is an attractive approach to utilize benign and environmentally friendly wide band gap ZnS QDs in solar cell technology.« less

Preparation, characterization of Sb-doped ZnO nanocrystals and their excellent solar light driven photocatalytic activity

NASA Astrophysics Data System (ADS)

Nasser, Ramzi; Othmen, Walid Ben Haj; Elhouichet, Habib; Férid, Mokhtar

2017-01-01

In the present study, undoped and antimony (Sb) doped ZnO nanocrystals (NCs) were prepared by a simple and economical sol-gel method. X-ray diffraction (XRD) and transmission electron microscopy (TEM) revealed the purity of the obtained phase and its high crystallinity. Raman analysis confirms the hexagonal Wurtzite ZnO structure. According to the diffuse reflectance results, the band gap was found to decrease up to 3% of Sb doping (ZSb3 sample). The results of X-ray photoelectron spectroscopy (XPS) measurements reveal that Sb ions occupied both Zn and interstitials sites. The successful substitution of antimony in ZnO lattice suggests the formation of the complex (SbZn-2 VZn) acceptor level above the valence band. Particularly for ZSb3 sample, the UV photoluminescence (PL) band presents an obvious red-shift attributed to the formation of this complex. Rhodamine B (RhB) was used to evaluate the photocatalytic activity of Sb-doped ZnO NCs under sunlight irradiation. It was found that oxygen vacancies play a major role in the photocatalytic process by trapping the excited electrons and inhibiting the radiative recombination. During the photocatalytic mechanism, the Sb doping, expressed through the apparition of the (SbZn-2 VZn) correspondent acceptor level, enhances the sunlight absorption within the ZnO band gap, which stimulates the generation of hydroxyl radicals and promotes the photocatalytics reaction rates. Such important contribution of the hydroxyl radicals was confirmed experimentally when using ethanol as scavenger in the photocatalytic reaction. The photodegradation experiments reveal that ZSb3 sample exhibits the highest photocatalytic activity among all the prepared samples and presents a good cycling stability and reusability. The influence of the initial pH in the photodegradation efficiency was also monitored and discussed.

Tuning the luminescence of ZnO:Eu nanoparticles for applications in biology and medicine

NASA Astrophysics Data System (ADS)

Kaszewski, Jarosław; Kiełbik, Paula; Wolska, Ewelina; Witkowski, Bartłomiej; Wachnicki, Łukasz; Gajewski, Zdzisław; Godlewski, Marek; Godlewski, Michał M.

2018-06-01

Zinc oxide nanoparticles were synthesized with microwave hydrothermal technique and tested as luminescent contrast for biological imaging. Luminescence was activated by Eu3+ ions embedded in the nanoparticle matrix in the increasing concentrations of 1, 5 and 10 %mol. It was found that europium did not create a separate crystalline phase up to the concentration as high as 5 %mol. However, Eu3+ ions did not substitute Zn2+ in the host lattice, but allocated in the low symmetry environment. It was proposed that europium was locating in the inter-grain space or on the surface of nanoparticles. The luminescence intensity in ZnO:Eu, as well as the size of particles, increased with the Eu ion concentration. Moreover, in 10 %mol Eu sample, the separate phase of Eu-hydroxide was identified with crystals of micrometre length. Interestingly, in vivo study revealed, that contrary to the in silico experiments, following gastric gavage, the brightest nanoparticle-related luminescence signal was observed at 1 %mol. concentration of Eu. Since the alimentary uptake of nanoparticles was related to their size, we concluded that the increase in luminescence at 5 and 10 %mol. Eu concentrations was associated with the largest ZnO:Eu and Eu-hydroxide particles that did not cross the gastrointestinal barrier.

Stibiconite (Sb3O6OH), senarmontite (Sb2O3) and valentinite (Sb2O3): Dissolution rates at pH 2-11 and isoelectric points

NASA Astrophysics Data System (ADS)

Biver, M.; Shotyk, W.

2013-05-01

Batch reactor experiments were carried out in order to derive rate laws for the proton promoted dissolution of the main natural antimony oxide phases, namely stibiconite (idealized composition SbSb2O6OH), senarmontite (cubic Sb2O3) and (metastable) valentinite (orthorhombic Sb2O3) over the range 2 ⩽ pH ⩽ 11, under standard conditions and ionic strength I = 0.01 mol l-1. The rates of antimony release by stibiconite were r = (2.2 ± 0.2) × 10-9 a(H+)0.11±0.01 mol m-2 s-1 for 2.00 ⩽ pH ⩽ 4.74 and r = (4.3 ± 0.2) × 10-10 a(H+)-0.030±0.003 mol m-2 s-1 for 4.74 ⩽ pH ⩽ 10.54. The rates of dissolution of senarmontite were r = (5.3 ± 2.2) × 10-7 a(H+)0.54±0.05 mol m-2 s-1 for 2.00 ⩽ pH ⩽ 6.93 and r = (1.4 ± 0.3) × 10-14 a(H+)-0.53±0.07 mol m-2 s-1 for 6.93 ⩽ pH ⩽ 10.83. The rates of dissolution of valentinite were r = (6.3 ± 0.2) × 10-8 a(H+)0.052±0.003 mol m-2 s-1 for 1.97 ⩽ pH ⩽ 6.85. Above pH = 6.85, valentinite was found to dissolve at a constant rate of r = (2.79 ± 0.05) × 10-8 mol m-2 s-1. Activation energies were determined at selected pH values in the acidic and basic domain, over the temperature range 25-50 °C. The values for stibiconite are -10.6 ± 1.9 kJ mol-1 (pH = 2.00) and 53 ± 14 kJ mol-1 (pH = 8.7). For senarmontite, we found 46.6 ± 4.7 kJ mol-1 (pH = 3.0) and 68.1 ± 6.1 kJ mol-1 (pH = 9.9) and for valentinite 41.9 ± 1.1 kJ mol-1 (pH = 3.0) and 39.0 ± 4.6 kJ mol-1 (pH = 9.9). These activation energies are interpreted in the text. The solubility of stibiconite at 25 °C in the pH domain from 2 to 10 was determined; solubilities decrease from 452.0 μg l-1 (as Sb) at pH = 2.00 to 153.2 μg l-1 at pH = 7.55 and increase again in the basic region, up to 176.6 μg l-1 at pH = 9.92. A graphical synopsis of all the kinetic results, including those of stibnite (Sb2S3) from earlier work, is presented. This allows an easy comparison between the dissolution rates of stibnite and the minerals examined in the present work

Low temperature Zn diffusion for GaSb solar cell structures fabrication

NASA Technical Reports Server (NTRS)

Sulima, Oleg V.; Faleev, Nikolai N.; Kazantsev, Andrej B.; Mintairov, Alexander M.; Namazov, Ali

1995-01-01

Low temperature Zn diffusion in GaSb, where the minimum temperature was 450 C, was studied. The pseudo-closed box (PCB) method was used for Zn diffusion into GaAs, AlGaAs, InP, InGaAs and InGaAsP. The PCB method avoids the inconvenience of sealed ampoules and proved to be simple and reproducible. The special design of the boat for Zn diffusion ensured the uniformality of Zn vapor pressure across the wafer surface, and thus the uniformity of the p-GaSb layer depth. The p-GaSb layers were studied using Raman scattering spectroscopy and the x-ray rocking curve method. As for the postdiffusion processing, an anodic oxidation was used for a precise thinning of the diffused GaSb layers. The results show the applicability of the PCB method for the large-scale production of the GaSb structures for solar cells.

Europium gallium garnet (Eu3Ga5O12) and Eu3GaO6: Synthesis and material properties

NASA Astrophysics Data System (ADS)

Sawada, Kenji; Nakamura, Toshihiro; Adachi, Sadao

2016-10-01

Eu-Ga-O ternary compounds were synthesized from a mixture of cubic (c-) Eu2O3 and monoclinic Ga2O3 (β-Ga2O3) raw powders using the solid-state reaction method by calcination at Tc = 1200 °C. The structural and optical properties of the Eu-Ga-O ternary compounds were investigated using X-ray diffraction analysis, photoluminescence (PL) analysis, PL excitation (PLE) spectroscopy, and Raman scattering measurements. Stoichiometric compounds such as cubic Eu3Ga5O12 (EGG) and orthorhombic Eu3GaO6 were synthesized using molar ratios of x = 0.375 and 0.75 [x≡Eu2O3/(Eu2O3 + Ga2O3)], respectively, together with the end-point binary compounds β-Ga2O3 (x = 0) and monoclinic (m-) Eu2O3 (x = 1.0). The structural change from "cubic" to "monoclinic" in Eu2O3 is due to the structural phase transition occurring at Tc ≥ 1050 °C. In principle, the perovskite-type EuGaO3 and monoclinic Eu4Ga2O9 can also be synthesized at x = 0.5 and 0.667, respectively; however, such stoichiometric compounds could not be synthesized in this study. The PL and PLE properties of EGG and Eu3GaO6 were studied in detail. The temperature dependence of the PL spectra was observed through measurements carried out between T = 20 and 300 K and explained using a newly developed model. Raman scattering measurements were also performed on the Eu-Ga-O ternary systems over the entire composition range from x = 0 (β-Ga2O3) to 1.0 (m-Eu2O3).

Study of energy transfer mechanism from ZnO nanocrystals to Eu(3+) ions.

PubMed

Mangalam, Vivek; Pita, Kantisara; Couteau, Christophe

2016-12-01

In this work, we investigate the efficient energy transfer occurring between ZnO nanocrystals (ZnO-nc) and europium (Eu(3+)) ions embedded in a SiO2 matrix prepared using the sol-gel technique. We show that a strong red emission was observed at 614 nm when the ZnO-nc were excited using a continuous optical excitation at 325 nm. This emission is due to the radiative (5)D0 → (7)F2 de-excitation of the Eu(3+) ions and has been conclusively shown to be due to the energy transfer from the excited ZnO-nc to the Eu(3+) ions. The photoluminescence excitation spectra are also examined in this work to confirm the energy transfer from ZnO-nc to the Eu(3+) ions. Furthermore, we study various de-excitation processes from the excited ZnO-nc and their contribution to the energy transfer to Eu(3+) ions. We also report the optimum fabrication process for maximum red emission at 614 nm from the samples where we show a strong dependence on the annealing temperature and the Eu(3+) concentration in the sample. The maximum red emission is observed with 12 mol% Eu(3+) annealed at 450 °C. This work provides a better understanding of the energy transfer mechanism from ZnO-nc to Eu(3+) ions and is important for applications in photonics, especially for light emitting devices.

Synthesis and isolation of [Fe@Ge(10)](3-): a pentagonal prismatic Zintl ion cage encapsulating an interstitial iron atom.

PubMed

Zhou, Binbin; Denning, Mark S; Kays, Deborah L; Goicoechea, Jose M

2009-03-04

Reaction of an ethylenediamine (en) solution of the Zintl phase precursor K(4)Ge(9) with FeAr(2) (Ar = 2,6-Mes(2)C(6)H(3)) in the presence of 2,2,2-crypt (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane) yielded the endohedral Zintl ion [Fe@Ge(10)](3-) (1) which was crystallographically characterized as a [K(2,2,2-crypt)](+) salt in [K(2,2,2-crypt)](3)[Fe@Ge(10)]*2en. This unprecedented Zintl ion exhibits a pentagonal prismatic 10-atom germanium cage with an interstitial iron atom in the central cavity. Confirmation of the existence of the cluster anion in solution was corroborated by positive and negative ion mode electrospray mass spectrometry.

Uncooled EuSbTe3 photodetector highly sensitive from ultraviolet to terahertz frequencies

NASA Astrophysics Data System (ADS)

Niu, Ying Y.; Wu, Dong; Su, Yu Q.; Zhu, Hai; Wang, Biao; Wang, Ying X.; Zhao, Zi R.; Zheng, Ping; Niu, Jia S.; Zhou, Hui B.; Wei, Jian; Wang, Nan L.

2018-01-01

Light probe from Uv to THz is critical in photoelectronics and has great applications ranging from imaging, communication to medicine (Woodward et al 2002 Phys. Med. Biol. 47 3853-63 Pospischil et al 2013 Nat. Photon. 7 892-6 Martyniuk and Rogalski 2003 Prog. Quantum Electron. 27 59-210). However, the room temperature ultrabroadband photodetection across visible down to far-infrared is still challenging. The challenging arises mainly from the lack of suitable photoactive materials. Because that conventional semiconductors, such as silicon, have their photosensitive properties cut off by the bandgap and are transparent to spectrum at long-wavelength infrared side (Ciupa and Rogalski 1997 Opto-Electron. Rev. 5 257-66 Tonouchi 2007 Nat. Photon. 1 97-105 Sizov and Rogalski 2010 Prog. Quantum Electron. 34 278-347 Kinch 2000 J. Electron. Mater. 29 809-17). Comparatively, the dielectrics with very narrow band-gap but maintain the semiconductor-like electrical conduction would have priorities for ultrabroadband photodetection. Here we report on EuSbTe3 is highly sensitive from ultraviolet directly to terahertz (THz) at room temperature. High photoresponsivities 1-8 A W-1 reached in our prototype EuSbTe3 detectors with low noise equivalent power (NEP) recorded, for instances ~150 pW · Hz-1/2 (at λ  =  532 nm) and ~0.6 nW · Hz-1/2 (at λ  =  118.8 µm) respectively. Our results demonstrate a promising system with direct photosensitivity extending well into THz regime at room temperature, shed new light on exploring more sophisticated multi-band photoelectronics.

Eu2+ -induced enhancement of defect luminescence of ZnS.

PubMed

Xiao-Bo, Zhang; Fu-Xiang, Wei

2016-12-01

The Eu 2 + -induced enhancement of defect luminescence of ZnS was studied in this work. While photoluminescence (PL) spectra exhibited 460 nm and 520 nm emissions in both ZnS and ZnS:Eu nanophosphors, different excitation characteristics were shown in their photoluminescence excitation (PLE) spectra. In ZnS nanophosphors, there was no excitation signal in the PLE spectra at the excitation wavelength λ ex  > 337 nm (the bandgap energy 3.68 eV of ZnS); while in ZnS:Eu nanophosphors, two excitation bands appeared that were centered at 365 nm and 410 nm. Compared with ZnS nanophosphors, the 520 nm emission in the PL spectra was relatively enhanced in ZnS:Eu nanophosphors and, furthermore, in ZnS:Eu nanophosphors the 460 nm and 520 nm emissions increased more than 10 times in intensity. The reasons for these differences were analyzed. It is believed that the absorption of Eu 2 + intra-ion transition and subsequent energy transfer to sulfur vacancy, led to the relative enhancement of the 520 nm emission in ZnS:Eu nanophosphors. In addition, more importantly, Eu 2 + acceptor-bound excitons are formed in ZnS:Eu nanophosphors and their excited levels serve as the intermediate state of electronic relaxation, which decreases non-radiative electronic relaxation and thus increases the intensity of the 460 nm and 520 nm emission dramatically. In summary, the results in this work indicate a new mechanism for the enhancement of defect luminescence of ZnS in Eu 2 + -doped ZnS nanophosphors. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Growth of Lattice-Matched ZnTeSe Alloys on (100) and (211)B GaSb

NASA Astrophysics Data System (ADS)

Chai, J.; Lee, K.-K.; Doyle, K.; Dinan, J. H.; Myers, T. H.

2012-10-01

A key issue with the current HgCdTe/Si system is the high dislocation density due to the large mismatch between HgCdTe and Si. An alternative system that has superior lattice matching is HgCdSe/GaSb. A buffer layer to mitigate issues with direct nucleation of HgCdSe on GaSb is ZnTe1- x Se x . We have performed preliminary studies into the growth of lattice-matched ZnTe1- x Se x on both (100) and (211)B GaSb. The effects of substrate orientation, substrate temperature, and growth conditions on the morphology and crystallography of ZnTe0.99Se0.01 alloys were investigated. The lattice-matching condition yielded minimum root-mean-square (rms) roughness of 1.1 nm, x-ray rocking curve full-width at half-maximum (FWHM) value of ~29 arcsec, and density of nonradiative defects of mid-105 cm-2 as measured by imaging photoluminescence.

Controlled synthesis of Eu{sup 2+} and Eu{sup 3+} doped ZnS quantum dots and their photovoltaic and magnetic properties

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

Horoz, Sabit; Poudyal, Uma; Wang, Wenyong

2016-04-15

Eu-doped ZnS quantum dots (QDs) have been synthesized by wet-chemical method and found to form in zinc blende (cubic) structure. Both Eu{sup 2+} and Eu{sup 3+} doped ZnS can be controllably synthesized. The Eu{sup 2+} doped ZnS QDs show broad photoluminescence emission peak around 512 nm, which is from the Eu{sup 2+} intra-ion transition of 4f{sup 6}d{sup 1} – 4f{sup 7}, while the Eu{sup 3+} doped samples exhibit narrow emission lines characteristic of transitions between the 4f levels. The investigation of the magnetic properties shows that the Eu{sup 3+} doped samples exhibit signs of ferromagnetism, on the other hand, Eu{supmore » 2+} doped samples are paramagnetic of Curie-Weiss type. The incident photon to electron conversion efficiency is increased with the Eu doping, which suggests the QD solar cell efficiency can be enhanced by Eu doping due to widened absorption windows. This is an attractive approach to utilize benign and environmentally friendly wide band gap ZnS QDs in solar cell technology.« less

Effect of C6+ Ion Irradiation on structural and electrical properties of Yb and Eu doped Bi1.5 Zn0.92 Nb1.5 O6.92 pyrochlores

NASA Astrophysics Data System (ADS)

Yumak, Mehmet; Mergen, Ayhan; Qureshi, Anjum; Singh, N. L.

2015-03-01

Pyrochlore general formula of A2B2X7 where A and B are cations and X is an anion Pyrochlore compounds exhibit semiconductor, metallic or ionic conduction properties, depending on the doping, compositions/ substituting variety of cations and oxygen partial pressure. Ion beam irradiation can induce the structural disordering by mixing the cation and anion sublattices, therefore we aim to inevestigate effects of irradiation in pyrochlore compounds. In this study, Eu and Yb-doped Bi1.5Zn0.92Nb1.5O6.92 (Eu-BZN, Yb-BZN) Doping effect and single phase formation of Eu-BZN, Yb-BZN was characterized by X-ray diffraction technique (XRD). Radiation-induced effect of 85 MeV C6+ ions on Eu-BZN, Yb-BZN was studied by XRD, scanning electron microscopy (SEM) and temperature dependent dielectric measurements at different fluences. XRD results revealed that the ion beam-induced structural amorphization processes in Eu-BZN and Yb-BZN structures. Our results suggested that the ion beam irradiation induced the significant change in the temprature depndent dielectric properties of Eu-BZN and Yb-BZN pyrochlores due to the increased oxygen vacancies as a result of cation and anion disordering. Department of Metallurgical and Materials Eng., Marmara University, Istanbul-81040, Turkey.

Effect of p–d hybridization, structural distortion and cation electronegativity on electronic properties of ZnSnX{sub 2} (X=P, As, Sb) chalcopyrite semiconductors

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

Mishra, S.; Ganguli, B., E-mail: biplabg@nitrkl.ac.in

2013-04-15

Significant effects of p–d hybridization, structural distortion and cation-electro-negativity are found on band gap in ZnSnX{sub 2} (X=P, As, Sb). Our study suggests these compounds to be direct band gap semiconductors with band gaps of 1.23, 0.68 and 0.19 eV respectively. Lattice constants, tetragonal distortion (η), anion displacement, bond lengths and bulk moduli are calculated by Density Functional Theory based on Tight binding Linear Muffin-Tin orbital method. Our result of structural properties is in good agreement with the available experimental and other theoretical results. Calculated band gaps also agree well with the experimental works within LDA limitation. Unlike other semiconductorsmore » in the group II–IV–V{sub 2}, there is a reduction in the band gap of 0.22, 0.20 and 0.24 eV respectively in ZnSnX{sub 2} (X=P, As, Sb) due to p–d hybridization. Structural distortion decreases band gap by 0.20, 0.12 and 0.10 eV respectively. We find that cation electronegativity effect is responsible for increasing the band gap relative to their binary analogs GaInP{sub 2}, InGaAs{sub 2} and GaInSb{sub 2} respectively and increment are 0.13, 0.04 and 0.13 eV respectively. - Graphical abstract: One unit cell of ZnSnX{sub 2} (X=P, As, Sb) chalcopyrite semiconductor. Semiconductors ZnSnX{sub 2} (X=P, As, Sb) are found to be direct band gap semiconductors with band gaps 1.23, 0.68 and 0.19 eV respectively. The quantitative estimate of effects of p–d hybridization, structural distortion and cation electronegativity shows band gaps change significantly due to these effects. Highlights: ► ZnSnX{sub 2} (X=P, As, Sb) are direct band gap semiconductors. ► These have band gaps of 1.23 eV, 0.68 eV and 0.19 eV respectively. ► The band gap reduction due to p–d hybridization is 13.41%, 18.51% and 40% respectively. ► Band gap reduction due to structural distortion is 12.12%, 11.11% and 16.66% respectively. ► Band gap increases 8.38%, 3.70% and 21

A Versatile Low Temperature Synthetic Route to Zintl Phase Precursors: Na4Si4, Na4Ge4 and K4Ge4 as Examples

PubMed Central

Ma, Xuchu; Xu, Fen; Atkins, Tonya; Goforth, Andrea M.; Neiner, Doinita; Navrotsky, Alexandra; Kauzlarich, Susan M.

2010-01-01

Na4Si4 and Na4Ge4 are ideal chemical precursors for inorganic clathrate structures, clusters, and nanocrystals. The monoclinic Zintl phases, Na4Si4 and Na4Ge4, contain isolated homo-tetrahedranide [Si4]4− and [Ge4]4− clusters surrounded by alkali metal cations. In this study, a simple scalable route has been applied to prepare Zintl phases of composition Na4Si4 and Na4Ge4 using the reaction between NaH and Si or Ge at low temperature (420 °C for Na4Si4 and 270 °C for Na4Ge4). The method was also applied to K4Ge4, using KH and Ge as raw materials, to show the versatility of this approach. The influence of specific reaction conditions on the purity of these Zintl phases has been studied by controlling five factors: the method of reagent mixing (manual or ball milled), the stoichiometry between raw materials, the reaction temperature, the heating time and the gas flow rate. Moderate ball-milling and excess NaH or KH facilitate the formation of pure Na4Si4, Na4Ge4 or K4Ge4 at 420 °C (Na4Si4) or 270 °C (both M4Ge4 compounds, M = Na, K). TG/DSC analysis of the reaction of NaH and Ge indicates that ball milling reduces the temperature for reaction and confirms the formation temperature. This method provides large quantities of high quality Na4Si4 and Na4Ge4 without the need for specialized laboratory equipment, such as Schlenk lines, niobium/tantalum containers, or an arc welder, thereby expanding the accessibility and chemical utility of these phases by making them more convenient to prepare. This new synthetic method may also be extended to lithium-containing Zintl phases (LiH is commercially available) as well as to alkali metal-tetrel Zintl compounds of other compositions, e.g. K4Ge9. PMID:19921060

Luminescence properties of rare earth doped metal oxide nanostructures: A case of Eu-ZnO

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

Sahu, D.; Acharya, B. S.; Panda, N. R., E-mail: nihar@iitbbs.ac.in

2016-05-06

The present study reports the growth and luminescence properties of Eu doped ZnO nanostructures. The experiment has been carried out by synthesizing the materials by simple wet-chemical method. X-ray diffraction (XRD) studies show expansion of ZnO lattice with the incorporation of Eu ions which has been confirmed from the appearance of Eu{sub 2}O{sub 3} as a minor phase in the XRD pattern. The estimation of crystallite size from XRD results matches closely with the results obtained from transmission electron microscopy. Further, these results show the formation of nanosized Eu-ZnO particles of average size around 60 nm stacked on each other. FTIRmore » studies show the presence of both Zn-O and Eu-O modes in the spectra supporting the results obtained from XRD. The interesting results obtained from photoluminescence (PL) measurements show the presence of both band edge emission in UV region and the defect emissions in violet, blue and green region. The appearance of {sup 5}D{sub 0}→{sup 7}F{sub J} transitions of Eu{sup 3+} ions in red region clearly suggests the possible occurrence of energy transfer between the energy states of ZnO host and Eu{sup 3+} ions.« less

Effect of charge and composition on the structural fluxionality and stability of nine atom tin-bismuth Zintl analogues.

PubMed

Gupta, Ujjwal; Reber, Arthur C; Clayborne, Penee A; Melko, Joshua J; Khanna, Shiv N; Castleman, A W

2008-12-01

Synergistic studies of bismuth doped tin clusters combining photoelectron spectra with first principles theoretical investigations establish that highly charged Zintl ions, observed in the condensed phase, can be stabilized as isolated gas phase clusters through atomic substitution that preserves the overall electron count but reduces the net charge and thereby avoids instability because of coulomb repulsion. Mass spectrometry studies reveal that Sn(8)Bi(-), Sn(7)Bi(2)(-), and Sn(6)Bi(3)(-) exhibit higher abundances than neighboring species, and photoelectron spectroscopy show that all of these heteroatomic gas phase Zintl analogues (GPZAs) have high adiabatic electron detachment energies. Sn(6)Bi(3)(-) is found to be a particularly stable cluster, having a large highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap. Theoretical calculations demonstrate that the Sn(6)Bi(3)(-) cluster is isoelectronic with the well know Sn(9)(-4) Zintl ion; however, the fluxionality reported for Sn(9)(-4) is suppressed by substituting Sn atoms with Bi atoms. Thus, while the electronic stability of the clusters is dominated by electron count, the size and position of the atoms affects the dynamics of the cluster as well. Substitution with Bi enlarges the cage compared with Sn(9)(-4) making it favorable for endohedral doping, findings which suggest that these cages may find use for building blocks of cluster assembled materials.

Mechanical and Wear Properties of Sb- and Y-Added Mg-9Al-1Zn (AZ91) Alloy

NASA Astrophysics Data System (ADS)

Boby, Arun; Srinivasan, A.; Pillai, U. T. S.; Pai, B. C.

2015-09-01

This paper studies the effect of Sb and Y additions on the microstructure and mechanical properties of the AZ91 alloy. The results indicate that the Sb and Y additions lead to the formation of Mg3Sb2 and Al2Y phases. These phases modify the morphology of the β-Mg17Al12 phase, and hence refine the microstructure. The effects of Sb and Y additions on the aging behavior have also been investigated. Aging of the AZ91 alloy results in the formation of continuous and discontinuous types of precipitates. Whereas Sb and Y additions to AZ91 alloy suppresses the formation of discontinuous precipitate. The paper also reports the mechanical properties of as-cast and aged Sb-added AZ91-xY alloys for room and high temperatures. The optimum tensile properties are obtained with the alloy having the combined addition of 0.5 wt pct Sb and 0.6 wt pct Y. The fracture surface of AZ91-0.5Sb-0.6Y alloy reveals more quasi-cleavage type of failure with a cleavage fracture than the base alloy. At HT, the AZ91-0.5Sb-0.6Y alloy displays more cleavage facets connected with tearing ridges and shallow dimples than AZ91 alloy. Furthermore, it observed the improvement in wear resistance through the addition of Y. The worn surface reveals abrasion, oxidation, delamination, and plastic deformation wear mechanisms.

Electrical Transport Properties of Single-Crystalline β-Zn4Sb3 Prepared Through the Zn-Sn Mixed-Flux Method

NASA Astrophysics Data System (ADS)

Liu, Hongxia; Deng, Shuping; Shen, Lanxian; Wang, Jinsong; Feng, Cheng; Deng, Shukang

2017-03-01

β-Zn4Sb3 is a promising p-type thermoelectric material for utilization in moderate temperatures. This study prepares a group of single-crystalline β-Zn4Sb3 samples using the Zn-Sn mixed-flux method based on the stoichiometric ratios of Zn4+ x Sb3Sn y . The effect of Zn-to-Sn proportion in the flux on the structure and electrical transport properties is investigated. All samples are strip-shaped single crystals of different sizes. The actual Zn content of the present samples is improved (>3.9) compared with that of the samples prepared through the Sn flux method. Larger lattice parameters are also obtained. The carrier concentration of all the samples is in the order of over 1019 cm-3. With increasing Sn rate in the flux, this carrier concentration decreases, whereas mobility is significantly enhanced. The electrical conductivity and Seebeck coefficients of all the samples exhibit a behavior that of a degenerate semiconductor transport. Electrical conductivity initially increases and then decreases as the Sn ratio in the flux increases. The electrical conductivity of the x: y = 5:1 sample reaches 6.45 × 104 S m-1 at 300 K. Benefitting from the electrical conductivity and Seebeck coefficient, the flux proportion of the x: y = 7:1 sample finally achieves the highest power factor value of 1.4 × 10-3 W m-1 K-2 at 598 K.

Enhanced luminescence in Eu-doped ZnO nanocrystalline films

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

Suzuki, Keigo, E-mail: ksuzuki@murata.com; Murayama, Koji; Tanaka, Nobuhiko

We found an enhancement of Eu{sup 3+} emissions in Eu-doped ZnO nanocrystalline films fabricated by microemulsion method. The Eu{sup 3+} emission intensities were increased by reducing annealing temperatures from 633 K to 533 K. One possible explanation for this phenomenon is that the size reduction enhances the energy transfer from ZnO nanoparticles to Eu{sup 3+} ions. Also, the shift of the charge-transfer band into the low-energy side of the absorption edge is found to be crucial, which seems to expedite the energy transfer from O atoms to Eu{sup 3+} ions. These findings will be useful for the material design of Eu-doped ZnOmore » phosphors.« less

Chemical and structural arrangement of the trigonal phase in GeSbTe thin films.

PubMed

Mio, Antonio M; Privitera, Stefania M S; Bragaglia, Valeria; Arciprete, Fabrizio; Bongiorno, Corrado; Calarco, Raffaella; Rimini, Emanuele

2017-02-10

The thermal and electrical properties of phase change materials, mainly GeSbTe alloys, in the crystalline state strongly depend on their phase and on the associated degree of order. The switching of Ge atoms in superlattice structures with trigonal phase has been recently proposed to develop memories with reduced switching energy, in which two differently ordered crystalline phases are the logic states. A detailed knowledge of the stacking plane sequence, of the local composition and of the vacancy distribution is therefore crucial in order to understand the underlying mechanism of phase transformations in the crystalline state and to evaluate the retention properties. This information is provided, as reported in this paper, by scanning transmission electron microscopy analysis of polycrystalline and epitaxial Ge 2 Sb 2 Te 5 thin samples, using the Z-contrast high-angle annular dark field method. Electron diffraction clearly confirms the presence of compositional mixing with stacking blocks of 11, 9 or 7 planes corresponding to Ge 3 Sb 2 Te 6 , Ge 2 Sb 2 Te 5 , and GeSb 2 Te 4 , alloys respectively in the same trigonal phase. By increasing the degree of order (according to the annealing temperature, the growth condition, etc) the spread in the statistical distribution of the blocks reduces and the distribution of the atoms in the cation planes also changes from a homogenous Ge/Sb mixing towards a Sb-enrichment in the planes closest to the van der Waals gaps. Therefore we show that the trigonal phase of Ge 2 Sb 2 Te 5 , the most studied chalcogenide for phase-change memories, is actually obtained in different configurations depending on the distribution of the stacking blocks (7-9-11 planes) and on the atomic occupation (Ge/Sb) at the cation planes. These results give an insight in the factors determining the stability of the trigonal phase and suggest a dynamic path evolution that could have a key role in the switching mechanism of interfacial phase change memories

Preparation and Thermoelectric Properties of Semiconcucting Zn(sub 4) Sb(sub 3)

NASA Technical Reports Server (NTRS)

Caillat, T.; Fleurial, J. P.; Barshchevsky, A.

1996-01-01

Hot-pressed samples fothe semiconducting compound Beta - Zn(sub 4) Sb(sub 3) were prepared and characterized by x-ray and microprobe analysis. Some physical properties of Beta - Zn(sub 4) Sb(sub 3) were determined and its thermoelectric properties measured between room temperature and 650K.

Effect of Eu3+ doping on the structural, morphological and luminescence properties ZnO nanostructures

NASA Astrophysics Data System (ADS)

Vinoditha, U.; Balakrishna, K. M.; Sarojini, B. K.; Narayana, B.; Kumara, K.

2018-05-01

Pure and Eu3+ ions (1, 3, 5 atomic wt%) doped ZnO nanostructures are synthesized by a surfactant assisted hydrothermal method. The effect of doping concentrations on structural, morphological and optical properties of ZnO nanostructures is studied. The XRD analysis shows good crystallinity and the phase purity of the ZnO nanostructures. A shift in the standard Zn-O stretching mode after Eu3+ doping is observed in the FTIR spectra. The images of FESEM demonstrate the morphological variations from hexagonal nanorods to nanoflowers on varying the dopant concentrations. Substitution of Eu3+ ions into Zn2+ sites is confirmed by EDX analysis. The dominance of particle shape over the UV-Visible absorption properties of the prepared samples is noticed. The photoluminescence (PL) emission of undoped and doped ZnO nanostructures show dominant near band edge emission (NBE) in the UV region and minor defect induced deep level emissions in the visible region.

The synthesis of CaZn2Sb2 and its thermoelectric properties

NASA Technical Reports Server (NTRS)

Snyder, J.; Starkll, D.

2002-01-01

CaZn2Sb2 was prepared and examined for use as a hightemperature thermoelectric material. It has a high Seebeck coefficient and high electrical conductivity-comparable to B-Zn4Sb3. These two properties are vital in determining the ability of the compound to change heat into electricity isentropically.

Thermoelectric properties of Zn4Sb3/CeFe(4-x)CoxSb12 nano-layered superlattices modified by MeV Si ion beam

NASA Astrophysics Data System (ADS)

Budak, S.; Guner, S.; Minamisawa, R. A.; Muntele, C. I.; Ila, D.

2014-08-01

We prepared multilayers of superlattice thin film system with 50 periodic alternating nano-layers of semiconducting half-Heusler β-Zn4Sb3 and skutterudite CeFe2Co2Sb12 compound thin films using ion beam assisted deposition (IBAD) with Au layers deposited on both sides as metal contacts. The deposited multilayer thin films have alternating layers about 5 nm thick. The total thickness of the multilayer system is 275 nm. The superlattices were then bombarded by 5 MeV Si ion at six different fluences to form nano-cluster structures. The film thicknesses and composition were monitored by Rutherford backscattering spectrometry (RBS) before and after MeV ion bombardment. We have measured the thermoelectric efficiency, Figure of Merit ZT, of the fabricated device by measuring the cross plane thermal conductivity by the 3rd harmonic (3ω) method, the cross plane Seebeck coefficient, and the electrical conductivity using the van der Pauw method before and after the MeV ion bombardments. We reached the remarkable thermoelectric Figure of Merit results at optimal fluences.

Disordered Zinc in Zn4Sb3 with Phonon-Glass and Electron-Crystal Thermoelectric Properties

NASA Technical Reports Server (NTRS)

Snyder, G. Jeffrey; Christensen, Mogens; Nishibori, Eiji; Caillat, Thierry; Brummerstedt Iversen, Bo

2004-01-01

By converting waste heat into electricity, thermoelectric generators could be an important part of the solution to today's energy challenges. The compound Zn4Sb3 is one of the most efficient thermoelectric materials known. Its high efficiency results from an extraordinarily low thermal conductivity in conjunction with the electronic structure of a heavily doped semiconductor. Previous structural studies have been unable to explain this unusual combination of properties. Here, we show through a comprehensive structural analysis using single-crystal X-ray and powder-synchrotron-radiation diffraction methods, that both the electronic and thermal properties of Zn4Sb3 can be understood in terms of unique structural features that have been previously overlooked. The identification of Sb3- ions and Sb-2(4-) dimers reveals that Zn4Sb3 is a valence semiconductor with the ideal stoichiometry Zn13Sb10. In addition, the structure contains significant disorder, with zinc atoms distributed over multiple positions. The discovery of glass-like interstitial sites uncovers a highly effective mechanism for reducing thermal conductivity. Thus Zn4Sb3 is in many ways an ideal 'phonon glass, electron crystal' thermoelectric material.

Structural and optical properties of ZnSe:Eu/ZnS quantum dots depending on interfacial residual europium

NASA Astrophysics Data System (ADS)

Park, Ji Young; Lee, Chan Gi; Seo, Han Wook; Jeong, Da-Woon; Kim, Min Young; Kim, Woo-Byoung; Kim, Bum Sung

2018-01-01

A multimodal emitter comprising of ZnSe:Eu/ZnS (core/shell) quantum dots (QDs) by adding a ZnS precursor in situ during synthesis. ZnSe/Eu2+/Eu3+/ZnS actives both core and core/shell. QDs prepared with the ZnS precursor displayed a luminescence intensity three times that of ZnSe QDs due to the passivation effect of the Shell. While the core QDs display the 450-550 nm emission of Eu2+ (4F65D1 → 4F7), the core/shell system showed no Eu2+ emission but only the sharp peaks in the red at 579, 592, 615, 651, and 700 nm due to the electronic transitions of 5D0 → 7Fn (n = 0-4) depending on leisurely decreased with increased reaction time. These results are in agreement with Eu 3d spectra of XPS analysis results. Microscopic analyses show that the core and core/shell QDs both have a zinc blende structure, and their respective sizes were about 3.19 and 3.44 nm. The lattice constant in the central portion of the core/shell QDs are around d111 = 3.13 Å, which is between the outside and inside ring patterns (d111 = 3.27 and 3.07 Å, respectively). This shows the effective over-capping of shell onto the core QDs. The core/shell structure may contain Eu2O3 bonding the over-coated ZnS surface on the Eu3+-doped ZnSe core.

Crystal structure, energy transfer and tunable luminescence properties of Ca8ZnCe(PO4)7:Eu2+,Mn2+ phosphor

NASA Astrophysics Data System (ADS)

Ding, Chong; Tang, Wanjun

2018-02-01

Single-phased Ca8ZnCe(PO4)7:Eu2+,Mn2+ phosphors with whitlockite-type structure have been prepared via the combustion-assisted synthesis technique. The XRD pattern show that the as-obtained phosphors crystallize in a trigonal phase with space group of R-3c (161). Ca8ZnCe(PO4)7 host is full of sensitizers (Ce3+) and the Ce3+ emission at different lattice sites has been discussed. The efficient energy transfers from Ce3+ ions to Eu2+/Mn2+ ions and from Eu2+ to Mn2+ have been validated. Under UV excitation, the emitting color of Ca8ZnCe(PO4)7:Eu2+/Mn2+ samples can be modulated from violet blue to green and from violet blue to red-orange by the energy transfers of Ce3+→Eu2+ and Ce3+→Mn2+, respectively. Additionally, white emission has been obtained through adjusting the relative concentrations of Eu2+ and Mn2+ ions in the Ca8ZnCe(PO4)7 host under UV excitation. These results indicate that as-prepared Ca8ZnCe(PO4)7:Eu2+,Mn2+ may be a potential candidate as color-tunable white light-emitting phosphors.

Enhanced photoluminescence property and broad color emission of ZnGa2O4 phosphor due to the synergistic role of Eu3+ and carbon dots

NASA Astrophysics Data System (ADS)

Huo, Qiuyue; Tu, Weixia; Guo, Lin

2017-10-01

ZnGa2O4 phosphors co-composited with nanoscale carbon dots (CDs) and Eu3+ were presented for the tunable color emission. Novel single phase CDs or/and Eu3+ composited ZnGa2O4 phosphors were synthesized by microwave hydrothermal method and their optical properties were investigated. The ZnGa2O4 phosphors composited with CDs exhibited an intense broad blue light emission at 421 nm and a more enhanced photoluminescence intensity than those without CDs. The Eu3+ composited ZnGa2O4 phosphors gave an ideal red color emission. The CDs/Eu3+ co-composited ZnGa2O4 phosphors exhibited a wide emission band peak at 450 nm and narrow emission peak at 618 nm. Furthermore, the tunable color emissions of CDs/Eu3+ co-composited ZnGa2O4 phosphors from blue to the white light region, and then to red were obtained with the increasing Eu3+ concentration, which can be a promising single phased phosphor candidate in light emitting diodes. Broadly tunable emission single phased phosphor is tuned firstly through the synergistic role of the non-metal element and the rare earth metal ions.

Cross-section imaging and p-type doping assessment of ZnO/ZnO:Sb core-shell nanowires by scanning capacitance microscopy and scanning spreading resistance microscopy

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

Wang, Lin, E-mail: lin.wang@insa-lyon.fr; Brémond, Georges; Sallet, Vincent

2016-08-29

ZnO/ZnO:Sb core-shell structured nanowires (NWs) were grown by the metal organic chemical vapor deposition method where the shell was doped with antimony (Sb) in an attempt to achieve ZnO p-type conduction. To directly investigate the Sb doping effect in ZnO, scanning capacitance microscopy (SCM) and scanning spreading resistance microscopy (SSRM) were performed on the NWs' cross-sections mapping their two dimensional (2D) local electrical properties. Although no direct p-type inversion in ZnO was revealed, a lower net electron concentration was pointed out for the Sb-doped ZnO shell layer with respect to the non-intentionally doped ZnO core, indicating an evident compensating effectmore » as a result of the Sb incorporation, which can be ascribed to the formation of Sb-related acceptors. The results demonstrate SCM/SSRM investigation being a direct and effective approach for characterizing radial semiconductor one-dimensional (1D) structures and, particularly, for the doping study on the ZnO nanomaterial towards its p-type realization.« less

Contents and leachability of heavy metals (Pb, Cu, Sb, Zn, As) in soil at the Pantex firing range, Amarillo, Texas.

PubMed

Basunia, S; Landsberger, S

2001-10-01

Pantex firing range soil samples were analyzed for Pb, Cu, Sb, Zn, and As. One hundred ninety-seven samples were collected from the firing range and vicinity area. There was a lack of knowledge about the distribution of Pb in the firing range, so a random sampling with proportional allocation was chosen. Concentration levels of Pb and Cu in the firing range were found to be in the range of 11-4675 and 13-359 mg/kg, respectively. Concentration levels of Sb were found to be in the range of 1-517 mg/kg. However, the Zn and As concentration levels were close to average soil background levels. The Sn concentration level was expected to be higher in the Pantex firing range soil samples. However, it was found to be below the neutron activation analysis (NAA) detection limit of 75 mg/kg. Enrichment factor analysis showed that Pb and Sb were highly enriched in the firing range with average magnitudes of 55 and 90, respectively. Cu was enriched approximately 6 times more than the usual soil concentration levels. Toxicity characteristic leaching procedure (TCLP) was carried out on size-fractionated homogeneous soil samples. The concentration levels of Pb in leachates were found to be approximately 12 times higher than the U.S. Environmental Protection Agency (EPA) regulatory concentration level of 5 mg/L. Sequential extraction (SE) was also performed to characterize Pb and other trace elements into five different fractions. The highest Pb fraction was found with organic matter in the soil.

Luminescence of Eu:Y3Al5O12, Eu:Lu3Al5O12, and Eu:GdAlO3 Nanocrystals Synthesized by Solution Combustion

NASA Astrophysics Data System (ADS)

Vilejshikova, E. V.; Khort, A. A.; Podbolotov, K. B.; Loiko, P. A.; Shimanski, V. I.; Shashkov, S. N.; Yumashev, K. V.

2017-11-01

Nanocrystals of rare-earth garnets Y3Al5O12 and Lu3Al5O12 and perovskite GdAlO3 highly doped (10-20 at%) with Eu3+ are synthesized by the solution combustion technique and subsequent annealing in air at 800 and 1300oC. Their structure, morphology, and phase composition are studied. These materials exhibit intense red luminescence under UV excitation. Eu:GdAlO3 luminescence has CIE 1931 color coordinates (0.632, 0.368); dominant wavelength, 599.6 nm; and color purity, >99%. Judd-Ofelt parameters, luminescence branching ratios, and lifetimes of the Eu3+ 5D0 state are determined. The luminescence quantum yield for Eu:GdAlO3 (10 at%) reaches 74% with a lifetime of 1.4 ms for the 5D0 state. The synthesized materials are promising for red ceramic phosphors.

ZnGeSb2: a promising thermoelectric material with tunable ultra-high conductivity.

PubMed

Sreeparvathy, P C; Kanchana, V; Vaitheeswaran, G; Christensen, N E

2016-09-21

First principles calculations predict the promising thermoelectric material ZnGeSb 2 with a huge power factor (S 2 σ/τ) on the order of 3 × 10 17 W m -1 K -2 s -1 , due to the ultra-high electrical conductivity scaled by a relaxation time of around 8.5 × 10 25 Ω -1 m -1 s -1 , observed in its massive Dirac state. The observed electrical conductivity is higher than the well-established Dirac materials, and is almost carrier concentration independent with similar behaviour of both n and p type carriers, which may certainly attract device applications. The low range of thermal conductivity is also evident from the phonon dispersion. Our present study further reports the gradual phase change of ZnGeSb 2 from a normal semiconducting state, through massive Dirac states, to a topological semi-metal. The maximum power factor is observed in the massive Dirac states compared to the other two states.

Yb14MgBi11: structure, thermoelectric properties and the effect of the structure on low lattice thermal conductivity.

PubMed

Hu, Yufei; Kauzlarich, Susan M

2017-03-21

Zintl phases Yb 14 MnSb 11 and Yb 14 MgSb 11 , which share the same complex structure type, have been demonstrated as the best p-type thermoelectric materials for the high temperature region (800-1200 K). A new iso-structural compound, Yb 14 MgBi 11 , was synthesized in order to investigate the structure and thermoelectric properties of the Bi analogs. Yb 14 MgBi 11 crystallizes in the Ca 14 AlSb 11 structure-type with the space group I4 1 /acd [a = 16.974(2) Å, c = 22.399(4) Å, V = 6454(2) Å 3 , R 1 /wR 2 = 0.0238/0.0475]. The structure follows the previous description of this structure type and the trend observed in previous analogs. Thermoelectric properties of Yb 14 MgBi 11 are measured together with Yb 14 MnBi 11 and both compounds are metallic. Compared to Yb 14 MgSb 11 , Yb 14 MgBi 11 has a higher carrier concentration with a similar mobility and effective mass. The lattice thermal conductivity of Yb 14 MgBi 11 is extremely low, which is as low as 0.16-0.36 W(mK) -1 . The zT values of Yb 14 MgBi 11 and Yb 14 MnBi 11 reach 0.2 at 875 K.

Distribution and mobility of lead (Pb), copper (Cu), zinc (Zn), and antimony (Sb) from ammunition residues on shooting ranges for small arms located on mires.

PubMed

Mariussen, Espen; Johnsen, Ida Vaa; Strømseng, Arnljot Einride

2017-04-01

An environmental survey was performed on shooting ranges for small arms located on minerotrophic mires. The highest mean concentrations of Pb (13 g/kg), Cu (5.2 g/kg), Zn (1.1 g/kg), and Sb (0.83 g/kg) in the top soil were from a range located on a poor minerotrophic and acidic mire. This range had also the highest concentrations of Pb, Cu, Zn, and Sb in discharge water (0.18 mg/L Pb, 0.42 mg/L Cu, 0.63 mg/L Zn, and 65 μg/L Sb) and subsurface soil water (2.5 mg/L Pb, 0.9 mg/L Cu, 1.6 mg/L Zn, and 0.15 mg/L Sb). No clear differences in the discharge of ammunition residues between the mires were observed based on the characteristics of the mires. In surface water with high pH (pH ~7), there was a trend with high concentrations of Sb and lower relative concentrations of Cu and Pb. The relatively low concentrations of ammunition residues both in the soil and soil water, 20 cm below the top soil, indicates limited vertical migration in the soil. Channels in the mires, made by plant roots or soil layer of less decomposed materials, may increase the rate of transport of contaminated surface water into deeper soil layers and ground water. A large portion of both Cu and Sb were associated to the oxidizable components in the peat, which may imply that these elements form inner-sphere complexes with organic matter. The largest portion of Pb and Zn were associated with the exchangeable and pH-sensitive components in the peat, which may imply that these elements form outer-sphere complexes with the peat.

Effect of laser irradiation on Ag4In12Sb56Te28

NASA Astrophysics Data System (ADS)

Chinnusamy, Rangasami

2018-04-01

Ag4In12Sb56Te28 has been synthesized by melt-quench method. Phase homogeneity, crystal structure and effect of laser irradiation have been investigated using X-ray diffraction (XRD) and Raman spectroscopy. Rietveld refinement of crystal structure revealed that Ag4In12Sb56Te28 is a multiphase system with AgIn3Te5, Sb8Te3 and Sb phases. Combined optical microscopy and Raman spectroscopy have been used to understand the distribution of different phases on the surface of the samples, which substantiated the results of Rietveld analysis. Interaction of 20 mW laser beam with samples has been investigated using Raman measurements. The results have shown that regions with large phase fraction of AgIn3Te5 become amorphous during laser-sample interaction, but the starting phase remains nearly same after the interaction. Regions with AgIn3Te5 and nearly equal or larger amount of Sb8Te3 have shown significant growth of α-Sb2O3 during and after laser-sample interaction. Regions rich in Sb have shown formation of AgIn3Te5 and growth of α-Sb2O3 during and after interaction. These observations have been explained based on the maximum temperature rise at different regions during laser-sample interaction.

Eu 3+-doped wide band gap Zn 2SnO 4 semiconductor nanoparticles: Structure and luminescence

DOE PAGES

Dimitrievska, Mirjana; Ivetić, Tamara B.; Litvinchuk, Alexander P.; ...

2016-08-03

Nanocrystalline Zn 2SnO 4 powders doped with Eu 3+ ions were synthesized via a mechanochemical solid-state reaction method followed by postannealing in air at 1200 °C. X-ray diffraction (XRD), energy-dispersive X-ray (EDX), and Raman and photoluminescence (PL) spectroscopies provide convincing evidence for the incorporation of Eu 3+ ions into the host matrix on noncentrosymmetric sites of the cubic inverse spinel lattice. Microstructural analysis shows that the crystalline grain size decreases with the addition of Eu 3+. Formation of a nanocrystalline Eu 2Sn 2O 7 secondary phase is also observed. Luminescence spectra of Eu 3+-doped samples show several emissions, including narrow-bandmore » magnetic dipole emission at 595 nm and electric dipole emission at 615 nm of the Eu 3+ ions. Excitation spectra and lifetime measurements suggest that Eu 3+ ions are incorporated at only one symmetry site. According to the crystal field theory, it is assumed that Eu 3+ ions participate at octahedral sites of Zn 2+ or Sn 4+ under a weak crystal field, rather than at the tetrahedral sites of Zn2+, because of the high octahedral stabilization energy for Eu 3+. Activation of symmetry forbidden (IR-active and silent) modes is observed in the Raman scattering spectra of both pure and doped samples, indicating a disorder of the cation sublattice of Zn 2SnO 4 nanocrystallites. These results were further supported by the first principle lattice dynamics calculations. The spinel-type Zn 2SnO 4 shows effectiveness in hosting Eu 3+ ions, which could be used as a prospective green/red emitter. As a result, this work also illustrates how sustainable and simple preparation methods could be used for effective engineering of material properties.« less

Density functional simulations of Sb-rich GeSbTe phase change alloys.

PubMed

Gabardi, S; Caravati, S; Bernasconi, M; Parrinello, M

2012-09-26

We generated models of the amorphous phase of Sb-rich GeSbTe phase change alloys by quenching from the melt within density functional molecular dynamics. We considered the two compositions Ge(1)Sb(1)Te(1) and Ge(2)Sb(4)Te(5). Comparison with previous results on the most studied Ge(2)Sb(2)Te(5) allowed us to draw some conclusions on the dependence of the structural properties of the amorphous phase on the alloy composition. Vibrational and electronic properties were also scrutinized. Phonons at high frequencies above 200 cm(-1) are localized in tetrahedra around Ge atoms in Sb-rich compounds as well as in Ge(2)Sb(2)Te(5). All compounds are semiconducting in the amorphous phase, with a band gap in the range 0.7-1.0 eV.

Density functional simulations of Sb-rich GeSbTe phase change alloys

NASA Astrophysics Data System (ADS)

Gabardi, S.; Caravati, S.; Bernasconi, M.; Parrinello, M.

2012-09-01

We generated models of the amorphous phase of Sb-rich GeSbTe phase change alloys by quenching from the melt within density functional molecular dynamics. We considered the two compositions Ge1Sb1Te1 and Ge2Sb4Te5. Comparison with previous results on the most studied Ge2Sb2Te5 allowed us to draw some conclusions on the dependence of the structural properties of the amorphous phase on the alloy composition. Vibrational and electronic properties were also scrutinized. Phonons at high frequencies above 200 cm-1 are localized in tetrahedra around Ge atoms in Sb-rich compounds as well as in Ge2Sb2Te5. All compounds are semiconducting in the amorphous phase, with a band gap in the range 0.7-1.0 eV.

Theoretical Study on Structural Stability of Fully Filled p-Type Skutterudites RETM4Sb12 ( RE = Rare Earth; TM = Fe, Ru)

NASA Astrophysics Data System (ADS)

Chen, Zhuo; Yang, Jiong; Liu, Ruiheng; Xi, Lili; Zhang, Wenqing; Yang, Jihui

2013-08-01

The structural stability of filled p-type skutterudites RETM4Sb12 ( RE = rare earth; TM = Fe, Ru) was studied via ab initio calculations. Most of the RE metals (La-Ho and Yb) could be filled into the cages (voids) of Fe4Sb12 to form stable filled skutterudites. However, only a few RE metals (La-Nd and Eu) could be stably filled into the cage of Ru4Sb12-based skutterudites. Systematic analysis of bonding energy showed that the structural stability could be attributed to ionic radius and effective charge state differences of the RE fillers. Resonant rattling frequencies of the fillers in both Fe4Sb12- and Ru4Sb12-based skutterudites were also studied.

Suppression of Red Luminescence in Wire Explosion Derived Eu:ZnO

NASA Astrophysics Data System (ADS)

Pallavi, Bandi; Sathyan, Sneha; Yoshimura, Takuya; Kumar, Praveen; Anbalagan, Kousika; Talluri, Bhusankar; Ramanujam, Sarathi; Ranjan, Prem; Thomas, Tiju

2018-03-01

Europium oxide (Eu2O3) is coated on zinc (Zn) wire using the electrophoretic deposition process. The coated Zn wire is subjected to the wire explosion process (WEP) which is rapid (< 15 min), and chimie douce (soft chemical, low temperature), in nature; this results in the formation of Eu doped ZnO. The explosion chamber contains oxygen (99.9%) at atmospheric pressure. Electron micrographs indicate that the particle sizes are ˜ 80 nm. Diffractogram-based analysis suggests that the crystallite size is 18-20 nm in the as-prepared doped ZnO nanoparticles. Electron paramagnetic resonance shows the presence of Zn vacancies and the cryo-photoluminescence spectrum indicates that Eu exists in the + 3 state. A combined Williamson-Hall plot and Kisielowski's model based analysis indicates that Eu is a substitutional dopant in WEP derived Eu:ZnO particles. It is estimated that this material has ˜ 0.24 at.% doping. This analysis also shows that, unlike another popular material GaN, in the case of ZnO, Eu3+ strictly substitutes for Zn2+ (i.e., dopant replacing a cation-anion pair does not seem possible). It may be noted that Eu3+ in a suitable host is oftentimes reported to be an efficient luminophore. The IR spectra show a band shift from 486 cm-1 to 493 cm-1; with peak shifts from 436 cm-1 to 430 cm-1 in Raman spectra. These too indicate the presence of Eu in the samples. However, at room temperature, only green luminescence (centered at 534 nm) is observed from the sample indicating (1) high concentrations of OZn anti-site defects and Zn vacancies, and (2) concomitant quenching of the luminescence at room temperature. Our results suggest that WEP is viable for synthesizing rare earth doped ceramic materials. However, obtaining efficient phosphors using this approach will likely require, (1) reduction of defect densities, and (2) appropriate passivation using post-processing.

Eu-doped ZnO nanoparticles: Sonochemical synthesis, characterization, and sonocatalytic application.

PubMed

Khataee, Alireza; Karimi, Atefeh; Zarei, Mahmoud; Joo, Sang Woo

2015-03-30

Undoped and europium (III)-doped ZnO nanoparticles were prepared by a sonochemical method. The prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) analysis. The crystalline sizes of undoped and 3% Eu-doped ZnO were found to be 16.04 and 8.22nm, respectively. The particle size of Eu-doped ZnO nanoparticles was much smaller than that of pure ZnO. The synthesized nanocatalysts were used for the sonocatalytic degradation of Acid Red 17. Among the Eu-doped ZnO catalysts, 3% Eu-doped ZnO nanoparticles showed the highest sonocatalytic activity. The effects of various parameters such as catalyst loading, initial dye concentration, pH, ultrasonic power, the effect of oxidizing agents, and the presence of anions were investigated. The produced intermediates of the sonocatalytic process were monitored by GC-Mass (GC-MS) spectrometry. Copyright © 2015 Elsevier B.V. All rights reserved.

Hydrogenation properties of KSi and NaSi Zintl phases.

PubMed

Tang, Wan Si; Chotard, Jean-Noël; Raybaud, Pascal; Janot, Raphaël

2012-10-14

The recently reported KSi-KSiH(3) system can store 4.3 wt% of hydrogen reversibly with slow kinetics of several hours for complete absorption at 373 K and complete desorption at 473 K. From the kinetics measured at different temperatures, the Arrhenius plots give activation energies (E(a)) of 56.0 ± 5.7 kJ mol(-1) and 121 ± 17 kJ mol(-1) for the absorption and desorption processes, respectively. Ball-milling with 10 wt% of carbon strongly improves the kinetics of the system, i.e. specifically the initial rate of absorption becomes about one order of magnitude faster than that of pristine KSi. However, this fast absorption causes a disproportionation into KH and K(8)Si(46), instead of forming the KSiH(3) hydride from a slow absorption. This disproportionation, due to the formation of stable KH, leads to a total loss of reversibility. In a similar situation, when the pristine Zintl NaSi phase absorbs hydrogen, it likewise disproportionates into NaH and Na(8)Si(46), indicating a very poorly reversible reaction.

The Bi{sub 2}O{sub 3}–Fe{sub 2}O{sub 3}–Sb{sub 2}O{sub 5} system phase diagram refinement, Bi{sub 3}FeSb{sub 2}O{sub 11} structure peculiarities and magnetic properties

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

Egorysheva, A.V., E-mail: anna_egorysheva@rambler.ru; Ellert, O.G.; Gajtko, O.M.

2015-05-15

The refinement of the Bi{sub 2}O{sub 3}–Fe{sub 2}O{sub 3}–Sb{sub 2}O{sub 5} system phase diagram has been performed and the existence of the two ternary compounds has been confirmed. The first one with a pyrochlore-type structure (sp. gr. Fd 3-barm) exists in the wide solid solution region, (Bi{sub 2−x}Fe{sub x})Fe{sub 1+y}Sb{sub 1−y}O{sub 7±δ}, where x=0.1–0.4 and y=−0.13–0.11. The second one, Bi{sub 3}FeSb{sub 2}O{sub 11}, corresponds to the cubic KSbO{sub 3}-type structure (sp. gr. Pn 3-bar) with unit cell parameter a=9.51521(2) Å. The Rietveld structure refinement showed that this compound is characterized by disordered structure. The Bi{sub 3}FeSb{sub 2}O{sub 11} factor groupmore » analysis has been carried out and a Raman spectrum has been investigated. According to magnetization measurements performed at the temperature range 2–300 K it may be concluded that the Bi{sub 3}FeSb{sub 2}O{sub 11} magnetic properties can be substantially described as a superposition of strong short-range antiferromagnetic exchange interactions realizing inside the [(FeSb{sub 2})O{sub 9}] 3D-framework via different pathways. - Graphical abstract: The refinement of the Bi{sub 2}O{sub 3}–Fe{sub 2}O{sub 3}–Sb{sub 2}O{sub 5} system phase diagram has been performed and the existence of the solid solution with a pyrochlore-type structure (sp. gr. Fd 3-barm) and Bi{sub 3}FeSb{sub 2}O{sub 11}, correspond of the cubic KSbO{sub 3}-type structure (sp. gr. Pn 3-bar has been confirmed. The structure refinement, Raman spectroscopy as well as magnetic measurements data of Bi{sub 3}FeSb{sub 2}O{sub 11} are presented. - Highlights: • The Bi{sub 2}O{sub 3}–Fe{sub 2}O{sub 3}–Sb{sub 2}O{sub 5} system phase diagram refinement has been performed. • The Bi{sub 3}FeSb{sub 2}O{sub 11} existence along with pyrochlore structure compound is shown. • It was determined that the Bi{sub 3}FeSb{sub 2}O{sub 11} is of disordered cubic KSbO{sub 3}-type structure. • Factor group

Peculiarities of thermoelectric half-Heusler phase formation in Gd-Ni-Sb and Lu-Ni-Sb ternary systems

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

Romaka, V.V., E-mail: romakav@lp.edu.ua; Romaka, L.; Horyn, A.

The phase equilibria in the Gd–Ni–Sb and Lu-Ni-Sb ternary systems were studied at 873 K by X-ray and metallographic analyses in the whole concentration range. The interaction of the elements in the Gd–Ni–Sb system results the formation of five ternary compounds at investigated temperature: Gd{sub 5}Ni{sub 2}Sb (Mo{sub 5}SiB{sub 2}-type), Gd{sub 5}NiSb{sub 2} (Yb{sub 5}Sb{sub 3}-type), GdNiSb (MgAgAs-type), Gd{sub 3}Ni{sub 6}Sb{sub 5} (Y{sub 3}Ni{sub 6}Sb{sub 5}-type), and GdNi{sub 0.72}Sb{sub 2} (HfCuSi{sub 2}-type). At investigated temperature the Lu-Ni-Sb system is characterized by formation of the LuNiSb (MgAgAs-type), Lu{sub 5}Ni{sub 2}Sb (Mo{sub 5}SiB{sub 2}-type), and Lu{sub 5}Ni{sub 0.56}Sb{sub 2.44} (Yb{sub 5}Sb{sub 3}-type)more » compounds. The disordering in the crystal structure of half-Heusler GdNiSb and LuNiSb was revealed by EPMA and studied by means of Rietveld refinement and DFT modeling. The performed electronic structure calculations are in good agreement with electrical transport property studies. - Graphical abstract: Crystal structure model and electron localization function of Lu{sub 5}Ni{sub 2}Sb. Display Omitted - Highlights: • Gd-Ni-Sb and Lu-Ni-Sb phase diagrams were constructed at 873 K. • GdNiSb and LuNiSb are characterized by disordered crystal structure. • Crystal structure optimization with DFT calculations confirmed crystal structure disorder in GdNiSb and LuNiSb.« less

Pressure-Induced Phase Transitions in GeTe-Rich Ge-Sb-Te Alloys across the Rhombohedral-to-Cubic Transitions.

PubMed

Krbal, Milos; Bartak, Jaroslav; Kolar, Jakub; Prytuliak, Anastasiia; Kolobov, Alexander V; Fons, Paul; Bezacier, Lucile; Hanfland, Michael; Tominaga, Junji

2017-07-17

We demonstrate that pressure-induced amorphization in Ge-Sb-Te alloys across the ferroelectric-paraelectric transition can be represented as a mixture of coherently distorted rhombohedral Ge 8 Sb 2 Te 11 and randomly distorted cubic Ge 4 Sb 2 Te 7 and high-temperature Ge 8 Sb 2 Te 11 phases. While coherent distortion in Ge 8 Sb 2 Te 11 does not prevent the crystalline state from collapsing into its amorphous counterpart in a similar manner to pure GeTe, the pressure-amorphized Ge 8 Sb 2 Te 11 phase begins to revert to the crystalline cubic phase at ∼9 GPa in contrast to Ge 4 Sb 2 Te 7 , which remains amorphous under ambient conditions when gradually decompressed from 40 GPa. Moreover, experimentally, it was observed that pressure-induced amorphization in Ge 8 Sb 2 Te 11 is a temperature-dependent process. Ge 8 Sb 2 Te 11 transforms into the amorphous phase at ∼27.5 and 25.2 GPa at room temperature and 408 K, respectively, and completely amorphizes at 32 GPa at 408 K, while some crystalline texture could be seen until 38 GPa (the last measurement point) at room temperature. To understand the origins of the temperature dependence of the pressure-induced amorphization process, density functional theory calculations were performed for compositions along the (GeTe) x - (Sb 2 Te 3 ) 1-x tie line under large hydrostatic pressures. The calculated results agreed well with the experimental data.

Sr(1.7)Zn(0.3)CeO4: Eu3+ novel red-emitting phosphors: synthesis and photoluminescence properties.

PubMed

Li, Haifeng; Zhao, Ran; Jia, Yonglei; Sun, Wenzhi; Fu, Jipeng; Jiang, Lihong; Zhang, Su; Pang, Ran; Li, Chengyu

2014-03-12

A series of novel red-emitting Sr1.7Zn0.3CeO4:Eu(3+) phosphors were synthesized through conventional solid-state reactions. The powder X-ray diffraction patterns and Rietveld refinement verified the similar phase of Sr1.7Zn0.3CeO4:Eu(3+) to that of Sr2CeO4. The photoluminescence spectrum exhibits that peak located at 614 nm ((5)D0-(7)F2) dominates the emission of Sr1.7Zn0.3CeO4:Eu(3+) phosphors. Because there are two regions in the excitation spectrum originating from the overlap of the Ce(4+)-O(2-) and Eu(3+)-O(2-) charge-transfer state band from 200 to 440 nm, and from the intra-4f transitions at 395 and 467 nm, the Sr1.7Zn0.3CeO4:Eu(3+) phosphors can be well excited by the near-UV light. The investigation of the concentration quenching behavior, luminescence decay curves, and lifetime implies that the dominant mechanism type leading to concentration quenching is the energy transfer among the nearest neighbor or next nearest neighbor activators. The discussion about the dependence of photoluminescence spectra on temperature shows the better thermal quenching properties of Sr1.7Zn0.3CeO4:0.3Eu(3+) than that of Sr2CeO4:Eu(3+). The experimental data indicates that Sr1.7Zn0.3CeO4:Eu(3+) phosphors have the potential as red phosphors for white light-emitting diodes.

Growth and photocatalytic properties of Sb-doped ZnO nanoneedles by hydrothermal process

NASA Astrophysics Data System (ADS)

Abaker, M.; Umar, Ahmad; Al-Sayari, S. A.; Dar, G. N.; Faisal, M.; Kim, S. H.; Hwang, S. W.

2011-10-01

This paper reports a facile hydrothermal synthesis of Sb-doped ZnO nanoneedles by using aqueous mixtures of zinc chloride, antimony (Sb) chloride, hexamethylenetetramine (HMTA) and ammonium hydroxide at low temperature of 110 °C. The morphological characterizations of as-synthesized nanoneedles were done by field emission scanning electron microscopy (FESEM) which reveals that the nanoneedles are grown in large-quantity and arranged in such a special manner that they made flower-like morphologies. The structural characterization of as-synthesized nanoneedles was investigated by X-ray diffraction (XRD) pattern which confirm the well-crystalline and wurtzite hexagonal phase of as-synthesized products. The compositional characterization of as-synthesized nanoneedles was characterized by energy dispersive spectroscopy (EDS), which verify that the synthesized nanoneedles are composed of zinc, Sb and oxygen. For application point of view, the synthesized nanoneedles were used as photocatalyst for photocatalytic degradation of methylene blue (MBB) and it was found that it exhibit good photocatalytic properties towards the photocatalytic degradation of methylene blue.

Effect of MultiSubstitution on the Thermoelectric Performance of the Ca11-xYbxSb10-yGez (0 ≤ x ≤ 9; 0 ≤ y ≤ 3; 0 ≤ z ≤ 3) System: Experimental and Theoretical Studies.

PubMed

Nam, Gnu; Choi, Woongjin; Lee, Junsu; Lim, Seong-Ji; Jo, Hongil; Ok, Kang Min; Ahn, Kyunghan; You, Tae-Soo

2017-06-19

The Zintl phase solid-solution Ca 11-x Yb x Sb 10-y Ge z (0 ≤ x ≤ 9; 0 ≤ y ≤ 3; 0 ≤ z ≤ 3) system with the cationic/anionic multisubstitution has been synthesized by molten Sn metal flux and arc-melting methods. The crystal structure of the nine title compounds were characterized by both powder and single-crystal X-ray diffractions and adopted the Ho 11 Ge 10 -type structure with the tetragonal space group I4/mmm (Z = 4, Pearson Code tI84). The overall isotypic structure of the nine title compounds can be illustrated as an assembly of three different types of cationic polyhedra sharing faces with their neighboring polyhedra and the three-dimensional cage-shaped anionic frameworks consisting of the dumbbell-shaped Sb 2 units and the square-shaped Sb 4 or (Sb/Ge) 4 units. During the multisubstitution trials, interestingly, we observed a metal-to-semiconductor transition as the Ca and Ge contents increased in the title system from Yb 11 Sb 10 to Ca 9 Yb 2 Sb 7 Ge 3 (nominal compositions) on the basis of a series of thermoelectric property measurements. This phenomenon can be elucidated by the suppression of a bipolar conduction of holes and electrons via an extra hole-carrier doping. The tight-binding linear muffin-tin orbital calculations using four hypothetical structural models nicely proved that the size of a pseudogap and the magnitude of the density of states at the Fermi level are significantly influenced by substituting elements as well as their atomic sites in a unit cell. The observed particular cationic/anionic site preferences, the historically known abnormalities of atomic displacement parameters, and the occupation deficiencies of particular atomic sites are further rationalized by the QVAL value criterion on the basis of the theoretical calculations. The results of SEM, EDS, and TGA analyses are also provided.

Synthesis and White-Light Emission of ZnO/HfO2: Eu Nanocables

PubMed Central

2010-01-01

ZnO/HfO2:Eu nanocables were prepared by radio frequency sputtering with electrospun ZnO nanofibers as cores. The well-crystallized ZnO/HfO2:Eu nanocables showed a uniform intact core–shell structure, which consisted of a hexagonal ZnO core and a monoclinic HfO2 shell. The photoluminescence properties of the samples were characterized. A white-light band emission consisted of blue, green, and red emissions was observed in the nanocables. The blue and green emissions can be attributed to the zinc vacancy and oxygen vacancy defects in ZnO/HfO2:Eu nanocables, and the yellow–red emissions are derived from the inner 4f-shell transitions of corresponding Eu3+ ions in HfO2:Eu shells. Enhanced white-light emission was observed in the nanocables. The enhancement of the emission is ascribed to the structural changes after coaxial synthesis. PMID:20730130

Initial Transient in Zn-doped InSb Grown in Microgravity

NASA Technical Reports Server (NTRS)

Ostrogorsky, A G.; Marin, C.; Volz, M.; Duffar, T.

2009-01-01

Three Zn-doped InSb crystals were directionally solidified under microgravity conditions at the International Space Station (ISS) Alpha. The distribution of the Zn was measured using SIMS. A short diffusion-controlled transient, typical for systems with k greater than 1 was demonstrated. Static pressure of approximately 4000 N/m2 was imposed on the melt, to prevent bubble formation and dewetting. Still, partial de-wetting has occurred in one experiment, and apparently has disturbed the diffusive transport of Zn in the melt.

Correlation of structural properties with energy transfer of Eu-doped ZnO thin films prepared by sol-gel process and magnetron reactive sputtering

PubMed Central

Petersen, Julien; Brimont, Christelle; Gallart, Mathieu; Schmerber, Guy; Gilliot, Pierre; Ulhaq-Bouillet, Corinne; Rehspringer, Jean-Luc; Colis, Silviu; Becker, Claude; Slaoui, Abdelillah; Dinia, Aziz

2010-01-01

We investigated the structural and optical properties of Eu-doped ZnO thin films made by sol-gel technique and magnetron reactive sputtering on Si (100) substrate. The films elaborated by sol-gel process are polycrystalline while the films made by sputtering show a strongly textured growth along the c-axis. X-ray diffraction patterns and transmission electron microscopy analysis show that all samples are free of spurious phases. The presence of Eu2+ and Eu3+ into the ZnO matrix has been confirmed by x-ray photoemission spectroscopy. This means that a small fraction of Europium substitutes Zn2+ as Eu2+ into the ZnO matrix; the rest of Eu being in the trivalent state. This is probably due to the formation of Eu2O3 oxide at the surface of ZnO particles. This is at the origin of the strong photoluminescence band observed at 2 eV, which is characteristic of the 5D0→7F2 Eu3+ transition. In addition the photoluminescence excitonic spectra showed efficient energy transfer from the ZnO matrix to the Eu3+ ion, which is qualitatively similar for both films although the sputtered films have a better structural quality compared to the sol-gel process grown films. PMID:20644657

Luminescence enhancement of (Sr1-x Mx )2 SiO4 :Eu2+ phosphors with M (Ca2+ /Zn2+ ) partial substitution for white light-emitting diodes.

PubMed

Wang, Yulong; Zhang, Wentao; Gao, Yang; Long, Jianping; Li, Junfeng

2017-02-01

Eu 2 + -doped Sr 2 SiO 4 phosphor with Ca 2 + /Zn 2 + substitution, (Sr 1-x M x ) 2 SiO 4 :Eu 2 + (M = Ca, Zn), was prepared using a high-temperature solid-state reaction method. The structure and luminescence properties of Ca 2 + /Zn 2 + partially substituted Sr 2 SiO 4 :Eu 2 + phosphors were investigated in detail. With Ca 2 + or Zn 2 + added to the silicate host, the crystal phase could be transformed between the α-form and the β-form of the Sr 2 SiO 4 structure. Under UV excitation at 367 nm, all samples exhibit a broad band emission from 420 to 680 nm due to the 4f 6 5d 1  → 4f 7 transition of Eu 2 + ions. The broad emission band consists of two peaks at 482 and 547 nm, which correspond to Eu 2 + ions occupying the ten-fold oxygen-coordinated Sr.(I) site and the nine-fold oxygen-coordinated Sr.(II) site, respectively. The luminescence properties, including the intensity and lifetime of Sr 2 SiO 4 :Eu 2 + phosphors, improved remarkably on Ca 2 + /Zn 2 + addition, and promote its application in white light-emitting diodes. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Effect of structural evolution of ZnO/HfO2 nanocrystals on Eu2+/Eu3+ emission in glass-ceramic waveguides for photonic applications.

PubMed

Ghosh, Subhabrata; Bhaktha B N, Shivakiran

2018-06-01

Eu-doped 70SiO 2 -23HfO 2 -7ZnO (mol%) glass-ceramic waveguides have been fabricated by sol-gel method as a function of heat-treatment temperatures for on-chip blue-light emitting source applications. Structural evolution of spherical ZnO and spherical as well as rod-like HfO 2 nanocrystalline structures have been observed with heat-treatments at different temperatures. Initially, in the as-prepared samples at 900 ◦ C, both, Eu 2+ as well as Eu 3+ ions are found to be present in the ternary matrix. With controlled heat-treatments of up to 1000 ◦ C for 2 h, local environment of Eu-ions become more crystalline in nature and the reduction of Eu 3+ to Eu 2+ takes place in such ZnO/HfO 2 crystalline environments. In these ternary glass-ceramic waveguides, heat-treated at higher temperatures, the blue-light emission characteristic, which is the signature of 4f 6 5d [Formula: see text] 4f 7 energy level transition of Eu 2+ ions is found to be greatly enhanced. The as-prepared glass-ceramic waveguides exhibit a propagation loss of 0.4 ± 0.2 dB cm -1 at 632.8 nm. Though the propagation losses increase with the growth of nanocrystals, the added functionalities achieved in the optimally heat-treated Eu-doped 70SiO 2 -23HfO 2 -7ZnO (mol%) waveguides, make them a viable functional optical material for the fabrication of on-chip blue-light emitting sources for integrated optic applications.

Phase transitions in the (Ni,Zn)TiF 6 · 6H 2O system

NASA Astrophysics Data System (ADS)

Lichti, R. L.; Jan, I.-Yuan; Casey, K. G.

1989-02-01

Measurements of the transformation rates and the characteristic temperatures of the trigonal ≡ monoclinic structural change in (Ni 1- xZn x)TiF 6 · 6H 2O show a double transition up to x = 0.5. The relationships between the phase changes generally observed in the ABF 6 · 6H 2O system and the internal motions of the octahedral ionic complexes are discussed, and a phase diagram for the mixed nickel/zinc fluorotitanate is established.

On the tin impurity in the thermoelectric compound ZnSb: Charge-carrier generation and compensation

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

Prokofieva, L. V., E-mail: lprokofieva496@gmail.com; Konstantinov, P. P.; Shabaldin, A. A.

2016-06-15

The technique for measuring the Hall coefficient and electrical conductivity in the thermal cycling mode is used to study the effect of the Sn impurity on the microstructure and properties of pressed ZnSb samples. Tin was introduced as an excess component (0.1 and 0.2 at %) and as a substitutional impurity for Zn and Sb atoms in a concentration of (2–2.5) at % The temperature dependences of the parameters of lightly doped samples are fundamentally like similar curves for ZnSb with 0.1 at % of Cu. The highest Hall concentration, 1.4 × 10{sup 19} cm{sup –3} at 300 K, ismore » obtained upon the introduction of 0.1 at % of Sn; the dimensionless thermoelectric figure of merit attains its maximum value of 0.85 at 660 K. The experimental data are discussed under the assumption of two doping mechanisms, which are effective in different temperature ranges, with zinc vacancies playing the decisive role of acceptor centers. In two ZnSb samples with SnSb and ZnSn additives, the charge-carrier compensation effect is observed; this effect depends on temperature and markedly changes with doping type. As in p-type A{sup IV}–B{sup VI} materials with a low Sn content, hole compensation can be attributed to atomic recharging Sn{sup 2+} → Sn{sup 4+}. Types of compensating complexes are considered.« less

Engineering half-Heusler thermoelectric materials using Zintl chemistry

NASA Astrophysics Data System (ADS)

Zeier, Wolfgang G.; Schmitt, Jennifer; Hautier, Geoffroy; Aydemir, Umut; Gibbs, Zachary M.; Felser, Claudia; Snyder, G. Jeffrey

2016-06-01

Half-Heusler compounds based on XNiSn and XCoSb (X = Ti, Zr or Hf) have rapidly become important thermoelectric materials for converting waste heat into electricity. In this Review, we provide an overview on the electronic properties of half-Heusler compounds in an attempt to understand their basic structural chemistry and physical properties, and to guide their further development. Half-Heusler compounds can exhibit semiconducting transport behaviour even though they are described as ‘intermetallic’ compounds. Therefore, it is most useful to consider these systems as rigid-band semiconductors within the framework of Zintl (or valence-precise) compounds. These considerations aid our understanding of their properties, such as the bandgap and low hole mobility because of interstitial Ni defects in XNiSn. Understanding the structural and bonding characteristics, including the presence of defects, will help to develop different strategies to improve and design better half-Heusler thermoelectric materials.

Photoluminescence properties and structure of double perovskite Ba2ZnWO6:Eu3+, Li+ as a novel red emitting phosphor

NASA Astrophysics Data System (ADS)

Chen, Peng; Yang, Dingming; Hu, Wenyuan; Zhang, Jing; Wu, Yadong

2017-12-01

Novel red-emitting Ba2Zn1-x-yWO6:xEu3+, yLi+ phosphors were prepared using a high-temperature solid-state method, and the crystal structure, the photoluminescence properties and the doping concentrations of Eu3+ and Li+ were investigated. The results show that these phosphors can be excited by near-ultraviolet light (250-400 nm) and co-doped Li+ can significantly enhance their PL performance. An intense red emission peak at 598 nm (5D0-7F1 transitions) was observed with an excitation wavelength of 316 nm. The CIE chromaticity coordinates of the phosphors are located in the red region, indicating that the BZW:Eu3+, Li+ phosphor holds promise as a red phosphor for near-ultraviolet excited WLEDs.

Multilayer SnSb4-SbSe Thin Films for Phase Change Materials Possessing Ultrafast Phase Change Speed and Enhanced Stability.

PubMed

Liu, Ruirui; Zhou, Xiao; Zhai, Jiwei; Song, Jun; Wu, Pengzhi; Lai, Tianshu; Song, Sannian; Song, Zhitang

2017-08-16

A multilayer thin film, comprising two different phase change material (PCM) components alternatively deposited, provides an effective means to tune and leverage good properties of its components, promising a new route toward high-performance PCMs. The present study systematically investigated the SnSb 4 -SbSe multilayer thin film as a potential PCM, combining experiments and first-principles calculations, and demonstrated that these multilayer thin films exhibit good electrical resistivity, robust thermal stability, and superior phase change speed. In particular, the potential operating temperature for 10 years is shown to be 122.0 °C and the phase change speed reaches 5 ns in the device test. The good thermal stability of the multilayer thin film is shown to come from the formation of the Sb 2 Se 3 phase, whereas the fast phase change speed can be attributed to the formation of vacancies and a SbSe metastable phase. It is also demonstrated that the SbSe metastable phase contributes to further enhancing the electrical resistivity of the crystalline state and the thermal stability of the amorphous state, being vital to determining the properties of the multilayer SnSb 4 -SbSe thin film.

Preparation and photoluminescence properties of red-emitting phosphor ZnAl2O4:Eu3+ with an intense 5D0 → 7F2 transition

NASA Astrophysics Data System (ADS)

He, Can; Ji, Haipeng; Huang, Zhaohui; Zhang, Xiaoguang; Liu, Haitao; Liu, Silin; Liu, Yangai; Fang, Minghao; Wu, Xiaowen; Min, Xin

2018-02-01

A series of ZnAl2-x O4:xEu3+ phosphors was synthesized by a modified co-precipitation method. The phase structure and photoluminescence properties were examined and extensively discussed. Composition-optimized ZnAl1.97O4:0.03Eu3+ exhibited sharp, intense red characteristic emissions with the Commission Internationale de l’Eclairage coordinates of (0.62, 0.33) peaking at 620 nm under an excitation at 394 nm, corresponding to the 5D0 → 7F2 transition of Eu3+. The quenching concentration of Eu3+ in ZnAl2-x O4:xEu3+ phosphors was approximately 0.03. In addition, the concentration quenching mechanism, fluorescence decay curves, and thermally stable luminescence properties of ZnAl2-x O4:xEu3+ phosphors were investigated. The results indicated that ZnAl2-x O4:xEu3+ phosphors demonstrate potential applications in near-ultraviolet light-emitting diode pumped white light lamps.

Effects of Eu doping and O vacancy on the magnetic and optical properties of ZnO

NASA Astrophysics Data System (ADS)

Ling-Feng, Qu; Qing-Yu, Hou; Xiao-Fang, Jia; Zhen-Chao, Xu; Chun-Wang, Zhao

2018-02-01

We calculated the electronic structure and optical properties of Eu mono-doped ZnO systems with or without O vacancy. We also determined the relative energy of ferromagnetic and antiferromagnetic orders of Eu-double-doped ZnO systems. The double-doped systems possess high Curie temperature and achieve room temperature ferromagnetism. The magnetism in the Eu mono-doped system without O vacancy is caused by the -Eu3+-O2--Eu3+- bound magnetopolaron (BMP) model. The magnetism of Eu mono-doped ZnO systems with O vacancy is more stable than that without O vacancy, and such magnetism is attributed to the -Eu3+-VO++-Eu3+- BMP model. The absorption spectrum for mono-doped systems is red shifted, and this finding confirms that Eu-mono-doped ZnO is a candidate photocatalyst for various applications. Therefore, Eu-double-doped ZnO can be practically used as an unambiguous diluted magnetic semiconductor.

Using the Semiconductors Materials of InSb-ZnTe System in Sensors for Gas Control

NASA Astrophysics Data System (ADS)

Shubenkova, E. G.

2017-04-01

The samples of thin film semiconductor compounds InSb, ZnTe and solid solutions based on them were obtained by vapor deposition of components on a dielectric substrate in a vacuum, followed by annealing and their surface properties in CO, O2 and NH3 gas atmospheres were investigated. Identification of the samples was carried out by X-ray diffraction techniques. In the temperature range 253 ÷ 403 K and a pressure range of 1÷12 Pa the gas adsorption was measured by piezoelectric microbalance technique. In order to establish the basic regularities of processes flowing on samples surface in addition to the electrophisical were used Infrared and Raman spectroscopic measurements. The resulting addiction “surface property - composition” is extreme and have allowed to determine solid solution InSb0,95-ZnTe0,05 as the most sensitive to the presence of ammonia, selective and this sample exhibits a negligible oxidation of surface.

Photoluminescent properties of Eu-doped ZnLiNbO4

NASA Astrophysics Data System (ADS)

Huang, Meng-Hsi; Lin, Ming-Hong; Fang, Te-Hua; Chang, Chia-Wei

2018-04-01

In this study, fluorescent Eu3+-doped ZnLiNbO4 materials were prepared via a vibrating milled solid-state reaction method. The objective was to develop new fluorescent oxide materials and study their fluorescent properties. The ZnLiNbO4 tetragonal spinel structure was formed with a single phase at a sintering temperature of 800 °C and with a regular shape at 1000 °C. The main exciton band was at 466 nm (7F0 → 5D2), and the main emission band was at 615 nm (5D0 → 7F2), which was an orange–red light band. The emission intensity was approximately 5% when the doping concentration reached 7%. The decay time was 2.96 ms.

Fluoride ion donor properties of cis-OsO(2)F(4): synthesis, raman spectroscopic study, and X-ray crystal structure of [OsO(2)F(3)][Sb(2)F(11)].

PubMed

Hughes, Michael J; Mercier, Hélène P A; Schrobilgen, Gary J

2010-01-04

The salt, [OsO(2)F(3)][Sb(2)F(11)], has been synthesized by dissolution of cis-OsO(2)F(4) in liquid SbF(5), followed by removal of excess SbF(5) at 0 degrees C to yield orange, crystalline [OsO(2)F(3)][Sb(2)F(11)]. The X-ray crystal structure (-173 degrees C) consists of an OsO(2)F(3)(+) cation fluorine bridged to an Sb(2)F(11)(-) anion. The light atoms of OsO(2)F(3)(+) and the bridging fluorine atom form a distorted octahedron around osmium in which the osmium atom is displaced from its center toward an oxygen atom and away from the trans-fluorine bridge atom. As in other transition metal dioxofluorides, the oxygen ligands are cis to one another and the fluorine bridge atom is trans to an oxygen ligand and cis to the remaining oxygen ligand. The Raman spectrum (-150 degrees C) of solid [OsO(2)F(3)][Sb(2)F(11)] was assigned on the basis of the ion pair observed in the low-temperature crystal structure. Under dynamic vacuum, [OsO(2)F(3)][Sb(2)F(11)] loses SbF(5), yielding the known [mu-F(OsO(2)F(3))(2)][Sb(2)F(11)] salt with no evidence for [OsO(2)F(3)][SbF(6)] formation. Attempts to synthesize [OsO(2)F(3)][SbF(6)] by the reaction of [OsO(2)F(3)][Sb(2)F(11)] with an equimolar amount of cis-OsO(2)F(4) or by a 1:1 stoichiometric reaction of cis-OsO(2)F(4) with SbF(5) in anhydrous HF yielded only [mu-F(OsO(2)F(3))(2)][Sb(2)F(11)]. Quantum-chemical calculations at the SVWN and B3LYP levels of theory and natural bond orbital analyses were used to calculate the gas-phase geometries, vibrational frequencies, natural population analysis charges, bond orders, and valencies of OsO(2)F(3)(+), [OsO(2)F(3)][Sb(2)F(11)], [OsO(2)F(3)][SbF(6)], and Sb(2)F(11)(-). The relative thermochemical stabilities of [OsO(2)F(3)][SbF(6)], [OsO(2)F(3)][Sb(2)F(11)], [OsO(2)F(3)][AsF(6)], [mu-F(OsO(2)F(3))(2)][SbF(6)], [mu-F(OsO(2)F(3))(2)][Sb(2)F(11)], and [mu-F(OsO(2)F(3))(2)][AsF(6)] were assessed using the appropriate Born-Haber cycles to account for the preference for [mu-F(OsO(2)F(3

Crystallization kinetics of the phase change material GeSb 6Te measured with dynamic transmission electron microscopy

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

Winseck, M. M.; Cheng, H. -Y.; Campbell, G. H.

2016-03-30

GeSb 6Te is a chalcogenide-based phase change material that has shown great ptoential for use in solid-state memory devices. The crystallization kinetics of amorphous thin films of GeSb 6Te during laser crystallization were followed with dynamic transmission electron microscopy, a photo-emission electron microscopy technique with nanosecond-scale time resolution. Nine-frame movies of crystal growth were taken during laser crystallization. The nucleation rate is observed to be very low and the growth rates are very high, up to 10.8 m s –1 for amorphous as-deposited films and significantly higher for an amorphous film subject to sub-threshold laser annealing before crystallization. The measuredmore » growth rates exceed any directly measured growth rate of a phase change material. Here, the crystallization is reminiscent of explosive crystallization of elemental semiconductors both in the magnitude of the growth rate and in the resulting crystalline microstructures.« less

Pulsed laser deposited GeTe-rich GeTe-Sb2Te3 thin films

PubMed Central

Bouška, M.; Pechev, S.; Simon, Q.; Boidin, R.; Nazabal, V.; Gutwirth, J.; Baudet, E.; Němec, P.

2016-01-01

Pulsed laser deposition technique was used for the fabrication of Ge-Te rich GeTe-Sb2Te3 (Ge6Sb2Te9, Ge8Sb2Te11, Ge10Sb2Te13, and Ge12Sb2Te15) amorphous thin films. To evaluate the influence of GeTe content in the deposited films on physico-chemical properties of the GST materials, scanning electron microscopy with energy-dispersive X-ray analysis, X-ray diffraction and reflectometry, atomic force microscopy, Raman scattering spectroscopy, optical reflectivity, and sheet resistance temperature dependences as well as variable angle spectroscopic ellipsometry measurements were used to characterize as-deposited (amorphous) and annealed (crystalline) layers. Upon crystallization, optical functions and electrical resistance of the films change drastically, leading to large optical and electrical contrast between amorphous and crystalline phases. Large changes of optical/electrical properties are accompanied by the variations of thickness, density, and roughness of the films due to crystallization. Reflectivity contrast as high as ~0.21 at 405 nm was calculated for Ge8Sb2Te11, Ge10Sb2Te13, and Ge12Sb2Te15 layers. PMID:27199107

Lattice dynamics of A Sb2O6 (A =Cu , Co) with trirutile structure

NASA Astrophysics Data System (ADS)

Maimone, D. T.; Christian, A. B.; Neumeier, J. J.; Granado, E.

2018-03-01

Raman spectroscopy experiments on single crystals of CuSb2O6 and CoSb2O6 quasi-one-dimensional antiferromagnets with trirutile crystal structure were performed, with a focus on the first material. The observed Raman-active phonon modes and previously reported infrared-active modes were identified with the aid of ab initio lattice dynamics calculations. The structural transition between monoclinic β -CuSb2O6 and tetragonal α -CuSb2O6 phases at Ts=400 K is manifested in our spectra by a "repulsion" of two accidentally quasidegenerate symmetric modes below Ts, caused by a phonon mixing effect that is only operative in the monoclinic β -CuSb2O6 phase due to symmetry restrictions. Also, two specific phonons, associated with CuO6 octahedra rotation and with a Jahn-Teller elongation mode, soften and broaden appreciably as T →Ts . A crossover from a displacive to an order-disorder transition at Ts is inferred.

Single crystals of the fluorite nonstoichiometric phase Eu{0.916/2+}Eu{0.084/3+}F2.084 (conductivity, transmission, and hardness)

NASA Astrophysics Data System (ADS)

Sobolev, B. P.; Turkina, T. M.; Sorokin, N. I.; Karimov, D. N.; Komar'kova, O. N.; Sulyanova, E. A.

2010-07-01

The nonstoichiometric phase EuF2+ x has been obtained via the partial reduction of EuF3 by elementary Si at 900-1100°C. Eu{0.916/2+}Eu{0.084/3+}F2.084 (EuF2.084) single crystals have been grown from melt by the Bridgman method in a fluorinating atmosphere. These crystals belong to the CaF2 structure type (sp. gr. Fm bar 3 m) with the cubic lattice parameter a = 5.8287(2) Å, are transparent in the spectral range of 0.5-11.3 μm, and have microhardness H μ = 3.12 ± 0.13 GPa and ionic conductivity σ = 1.4 × 10-5 S/cm at 400°C with the ion transport activation energy E a = 1.10 ± 0.05 eV. The physicochemical characteristics of the fluorite phases in the EuF2 - EuF3 systems are similar to those of the phases in the SrF2 - EuF3 and SrF2 - GdF3 systems due to the similar lattice parameters of the EuF2 and SrF2 components. Europium difluoride supplements the list of fluorite components MF2 ( M = Ca, Sr, Ba, Cd, Pb), which are crystal matrices for nonstoichiometric (nanostructured) fluoride materials M 1 - x R x F2 + x ( R are rare earth elements).

The structure of Na{sub 3}SbTe{sub 3}: How ionic and covalent bonding forces work together

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

Lin, Jianhua; Miller, G.J.

1994-12-01

The compound Na{sub 3}SbTe{sub 3} has been synthesized from the elements and characterized by single crystal X-ray diffraction. Na{sub 3}SbTe{sub 3} is cubic, crystallizing in the cP28 structure type (isomorphous with Na{sub 3}AsS{sub 3}); space group P2{sub 1}3 (No. 198); a=9.6114(9) {angstrom}; Z = 4; R1 = 0.0324; wR2 = 0.0561 (I {le} 2{sigma}(I)). The structure consists of isolated sodium cations and trigonal pyramidal [SbTe{sub 3}]{sup {minus}3} anions with a Sb-Te bond length of 2.787(1) {angstrom} and a Te-Sb-Te bond angle of 100.0(1){degrees}. The structure is related to both the Li{sub 3}Bi and K{sub 3}AsS{sub 4}-type structures. Both lattice energymore » and semiempirical electronic structure calculations are utilized to evaluate various local and long-range structural aspects of this Zintl phase.« less

Efficiencies of Eu{sup 3+} ions and hydrogen atoms as donors in ZnO thin films

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

Akazawa, Housei, E-mail: akazawa.housei@lab.ntt.co.jp

2016-09-15

The donor efficiencies of Eu{sup 3+} ions and hydrogen atoms in ZnO crystalline films were investigated with reference to that of Ga{sup 3+} ions. It was found that Eu{sup 3+} ions acted as extrinsic donors in ZnO:Eu films, yielding a resistivity of 1.8 × 10{sup −3} Ω cm at a doping level of 1 at. %. This value is comparable to one for intrinsic donors in undoped ZnO films. The conductivity was maintained as the deposition temperature was increased to 200 °C, and this is evidence for the contribution of extrinsic donors. Deposition of Ga-doped and Eu-doped ZnO films in an H{sub 2}O gasmore » flow produced oxyhydrogenated ZnO:(Ga, H) and ZnO:(Eu, H) films in which the Ga{sup 3+} and Eu{sup 3+} donors were deactivated by oxidization. Nevertheless, hydrogen donors contributed to electrical conduction yielding a resistivity of 1 × 10{sup −2} Ω cm. Postannealing in an H{sub 2} gas ambient alleviated the excessive oxidization of the films and thereby reactivated the donor action of Ga{sup 3+} and Eu{sup 3+} ions, causing the resistivity to recover to 10{sup −3} Ω cm for ZnO:(Ga, H) and 10{sup −2} Ω cm for ZnO:(Eu, H). In contrast, vacuum annealing of ZnO:(Ga, H) and ZnO:(Eu, H) films increased resistivity through removal of hydrogen donors while not affecting the oxidized condition of the samples.« less

Structure and physical properties of EuTa{sub 2}O{sub 6} tungsten bronze polymorph

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

Kolodiazhnyi, T., E-mail: kolodiazhnyi.taras@nims.go.jp; Sakurai, H.; Vasylkiv, O.

A tetragonal tungsten bronze (TTB) polymorph of EuTa{sub 2}O{sub 6} was prepared and analyzed. EuTa{sub 2}O{sub 6} crystallizes in the centrosymmetric Pnam space group (with unit cell: a = 12.3693, b = 12.4254, and c = 7.7228 Å) isomorphous with orthorhombic β-SrTa{sub 2}O{sub 6}. In contrast to early reports, we see no evidence of deviation from paramagnetic Curie-Weiss behavior among the Eu{sup 2+} 4f{sup 7}spins in EuTa{sub 2}O{sub 6} down to 2 K. Dielectric constant shows a broad peak at ca. 50 K with dielectric dispersion resembling diffuse phase transition. The relaxation time, however, follows a simple (non-freezing) thermally activated process with an activation energy of 92 meV and anmore » attempt frequency of f{sub 0} = 5.79 × 10{sup 12 }Hz. A thermal conductivity of EuTa{sub 2}O{sub 6} shows a low-temperature (T ≈ 30 K) “plateau” region reminiscent of a glass-like behaviour in Nb-based TTB compounds. This behaviour can be attributed to the loosely bound Eu{sup 2+} ions occupying large tricapped trigonal prismatic sites in the EuTa{sub 2}O{sub 6} structure.« less

Organo-Zintl-based superatoms: [Ge9(CHO)3] and [Ge9(CHO)

NASA Astrophysics Data System (ADS)

Reddy, G. Naaresh; Jena, Puru; Giri, Santanab

2017-10-01

A systematic study, based on density functional theory and different hybrid functionals for exchange-correlation potential, shows that the electron affinities of organo-zintl clusters [Ge9(R)n] [R = CHO; n = 1, 3] are close to that of chlorine (3.6 eV) and iodine (3.0 eV). A detailed study of the molecular orbitals of these complexes, when compared to those of Al13-, Cl- and I-, confirm that they behave as superatoms, mimicking the chemistry of halogens. This study expands the scope of superatoms by including a new class of pseudo-halogens based on ligated organo-Zintl ions.

Systematic study of electronic and magnetic properties for Cu{sub 12–x}TM{sub x}Sb{sub 4}S{sub 13} (TM = Mn, Fe, Co, Ni, and Zn) tetrahedrite

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

Suekuni, K., E-mail: ksuekuni@hiroshima-u.ac.jp; Tomizawa, Y.; Ozaki, T.

2014-04-14

Substitution effects of 3d transition metal (TM) impurities on electronic and magnetic properties for Cu{sub 12}Sb{sub 4}S{sub 13} tetrahedrite are investigated by the combination of low-temperature experiments and first-principles electronic-structure calculations. The electrical resistivity for the cubic phase of Cu{sub 12}Sb{sub 4}S{sub 13} exhibits metallic behavior due to an electron-deficient character of the compound. Whereas that for 0.5 ≤ x ≤ 2.0 of Cu{sub 12−x}Ni{sub x}Sb{sub 4}S{sub 13} exhibits semiconducting behavior. The substituted Ni for Cu is in the divalent ionic state with a spin magnetic moment and creates impurity bands just above the Fermi level at the top of the valence band. Therefore,more » the semiconducting behavior of the electrical resistivity is attributed to the thermal excitation of electrons from the valence band to the impurity band. The substitution effect of TM on the electronic structure and the valency of TM for Cu{sub 11.0}TM{sub 1.0}Sb{sub 4}S{sub 13} are systematically studied by the calculation. The substituted Mn, Fe, and Co for Cu are found to be in the ionic states with the spin magnetic moments due to the large exchange splitting of the 3d bands between the minority- and majority-spin states.« less

The crystal structure of the new ternary antimonide Dy 3Cu 20+xSb 11-x ( x≈2)

NASA Astrophysics Data System (ADS)

Fedyna, L. O.; Bodak, O. I.; Fedorchuk, A. O.; Tokaychuk, Ya. O.

2005-06-01

New ternary antimonide Dy 3Cu 20+xSb 11-x ( x≈2) was synthesized and its crystal structure was determined by direct methods from X-ray powder diffraction data (diffractometer DRON-3M, Cu Kα-radiation, R=6.99%,R=12.27%,R=11.55%). The compound crystallizes with the own cubic structure type: space group F 4¯ 3m, Pearson code cF272, a=16.6150(2) Å,Z=8. The structure of the Dy 3Cu 20Sb 11-x ( x≈2) can be obtained from the structure type BaHg 11 by doubling of the lattice parameter and subtraction of 16 atoms. The studied structure was compared with the structures of known compounds, which crystallize in the same space group with similar cell parameters.

Assembly of a new inorganic-organic frameworks based on [Sb4Mo12(OH)6O48]10- polyanion

NASA Astrophysics Data System (ADS)

Thabet, Safa; Ayed, Meriem; Ayed, Brahim; Haddad, Amor

2014-10-01

A new organic-inorganic hybrid material, (C4N2H7)8[K(H2O)]2[Sb4Mo12(OH)6O48]ṡ16H2O (1) has been isolated by the conventional solution method and characterized by elemental analysis, single-crystal X-ray diffraction, infrared spectroscopy, UV-visible spectroscopies, cyclic voltammetry and TG-DTA analysis. The compound crystallizes in the triclinic space group P - 1 with a = 13.407(6) Å, b = 13.906(2) Å, c = 14.657(7) Å, α = 77.216(9)°, β = 71.284(6)°, γ = 71.312(3)° and Z = 1. The crystal structure exhibits an infinite 1D inorganic structure built from [Sb4Mo12(OH)6O48]10- clusters and potassium cations; adjacent chains are further joined up hydrogen bonding interactions between protonated 2-methylimidazolim cations, water molecules and polyoxoanions to form a 3D supramolecular architecture.

Effect of Dielectric Material Films on Crystallization Characteristics of Ge2Sb2Te5 Phase-Change Memory Film

NASA Astrophysics Data System (ADS)

Nishiuchi, Kenichi; Yamada, Noboru; Kawahara, Katsumi; Kojima, Rie

2007-11-01

Reduction of the film thickness of phase-change film and the adoption of GeN- or ZrO2-based dielectric films are both effective in achieving good thermal stability in phase-change optical disks. It was experimentally confirmed that, at a heating rate of 10 °C/min, the crystallization temperature Tx of the Ge2Sb2Te5 amorphous film when sandwiched by ZnS-SiO2 films markedly increases from 162 to 197 °C, while the thickness of the Ge2Sb2Te5 film decreases from 10 to 3 nm. Tx also slightly increases when ZnS-SiO2 films are substituted for GeN-based films (from 162 to 165 °C) and ZrO2-based films (from 162 to 167 °C). At the same time, the activation energy of crystallization is 2.4 eV for both GeN- and ZrO2-based films, and is higher than 2.2 eV for ZnS-SiO2 films.

Hierarchical ZnO Nanowires-loaded Sb-doped SnO2-ZnO Micrograting Pattern via Direct Imprinting-assisted Hydrothermal Growth and Its Selective Detection of Acetone Molecules.

PubMed

Choi, Hak-Jong; Choi, Seon-Jin; Choo, Soyoung; Kim, Il-Doo; Lee, Heon

2016-01-08

We propose a novel synthetic route by combining imprinting transfer of a Sb-doped SnO2 (ATO)-ZnO composite micrograting pattern (MP), i.e., microstrip lines, on a sensor substrate and subsequent hydrothermal growth of ZnO nanowires (NWs) for producing a hierarchical ZnO NW-loaded ATO-ZnO MP as an improved chemo-resistive sensing layer. Here, ATO-ZnO MP structure with 3-μm line width, 9-μm pitch, and 6-μm height was fabricated by direct transfer of mixed ATO and ZnO nanoparticle (NP)-dispersed resists, which are pre-patterned on a polydimethylsiloxane (PDMS) mold. ZnO NWs with an average diameter of less than 50 nm and a height of 250 nm were quasi-vertically grown on the ATO-ZnO MP, leading to markedly enhanced surface area and heterojunction composites between each ATO NP, ZnO NP, and ZnO NW. A ZnO NW-loaded MP sensor with a relative ratio of 1:9 between ATO and ZnO (1:9 ATO-ZnO), exhibited highly sensitive and selective acetone sensing performance with 2.84-fold higher response (R air/R gas = 12.8) compared to that (R air/R gas = 4.5) of pristine 1:9 ATO-ZnO MP sensor at 5 ppm. Our results demonstrate the processing advantages of direct imprinting-assisted hydrothermal growth for large-scale homogeneous coating of hierarchical oxide layers, particularly for applications in highly sensitive and selective chemical sensors.

Hierarchical ZnO Nanowires-loaded Sb-doped SnO2-ZnO Micrograting Pattern via Direct Imprinting-assisted Hydrothermal Growth and Its Selective Detection of Acetone Molecules

PubMed Central

Choi, Hak-Jong; Choi, Seon-Jin; Choo, Soyoung; Kim, Il-Doo; Lee, Heon

2016-01-01

We propose a novel synthetic route by combining imprinting transfer of a Sb-doped SnO2 (ATO)-ZnO composite micrograting pattern (MP), i.e., microstrip lines, on a sensor substrate and subsequent hydrothermal growth of ZnO nanowires (NWs) for producing a hierarchical ZnO NW-loaded ATO-ZnO MP as an improved chemo-resistive sensing layer. Here, ATO-ZnO MP structure with 3-μm line width, 9-μm pitch, and 6-μm height was fabricated by direct transfer of mixed ATO and ZnO nanoparticle (NP)-dispersed resists, which are pre-patterned on a polydimethylsiloxane (PDMS) mold. ZnO NWs with an average diameter of less than 50 nm and a height of 250 nm were quasi-vertically grown on the ATO-ZnO MP, leading to markedly enhanced surface area and heterojunction composites between each ATO NP, ZnO NP, and ZnO NW. A ZnO NW-loaded MP sensor with a relative ratio of 1:9 between ATO and ZnO (1:9 ATO-ZnO), exhibited highly sensitive and selective acetone sensing performance with 2.84-fold higher response (Rair/Rgas = 12.8) compared to that (Rair/Rgas = 4.5) of pristine 1:9 ATO-ZnO MP sensor at 5 ppm. Our results demonstrate the processing advantages of direct imprinting-assisted hydrothermal growth for large-scale homogeneous coating of hierarchical oxide layers, particularly for applications in highly sensitive and selective chemical sensors. PMID:26743814

Hierarchical ZnO Nanowires-loaded Sb-doped SnO2-ZnO Micrograting Pattern via Direct Imprinting-assisted Hydrothermal Growth and Its Selective Detection of Acetone Molecules

NASA Astrophysics Data System (ADS)

Choi, Hak-Jong; Choi, Seon-Jin; Choo, Soyoung; Kim, Il-Doo; Lee, Heon

2016-01-01

We propose a novel synthetic route by combining imprinting transfer of a Sb-doped SnO2 (ATO)-ZnO composite micrograting pattern (MP), i.e., microstrip lines, on a sensor substrate and subsequent hydrothermal growth of ZnO nanowires (NWs) for producing a hierarchical ZnO NW-loaded ATO-ZnO MP as an improved chemo-resistive sensing layer. Here, ATO-ZnO MP structure with 3-μm line width, 9-μm pitch, and 6-μm height was fabricated by direct transfer of mixed ATO and ZnO nanoparticle (NP)-dispersed resists, which are pre-patterned on a polydimethylsiloxane (PDMS) mold. ZnO NWs with an average diameter of less than 50 nm and a height of 250 nm were quasi-vertically grown on the ATO-ZnO MP, leading to markedly enhanced surface area and heterojunction composites between each ATO NP, ZnO NP, and ZnO NW. A ZnO NW-loaded MP sensor with a relative ratio of 1:9 between ATO and ZnO (1:9 ATO-ZnO), exhibited highly sensitive and selective acetone sensing performance with 2.84-fold higher response (Rair/Rgas = 12.8) compared to that (Rair/Rgas = 4.5) of pristine 1:9 ATO-ZnO MP sensor at 5 ppm. Our results demonstrate the processing advantages of direct imprinting-assisted hydrothermal growth for large-scale homogeneous coating of hierarchical oxide layers, particularly for applications in highly sensitive and selective chemical sensors.

Cation vacancies and electrical compensation in Sb-doped thin-film SnO2 and ZnO

NASA Astrophysics Data System (ADS)

Korhonen, E.; Prozheeva, V.; Tuomisto, F.; Bierwagen, O.; Speck, J. S.; White, M. E.; Galazka, Z.; Liu, H.; Izyumskaya, N.; Avrutin, V.; Özgür, Ü.; Morkoç, H.

2015-02-01

We present positron annihilation results on Sb-doped SnO2 and ZnO thin films. The vacancy types and the effect of vacancies on the electrical properties of these intrinsically n-type transparent semiconducting oxides are studied. We find that in both materials low and moderate Sb-doping leads to formation of vacancy clusters of variable sizes. However, at high doping levels cation vacancy defects dominate the positron annihilation signal. These defects, when at sufficient concentrations, can efficiently compensate the n-type doping produced by Sb. This is the case in ZnO, but in SnO2 the concentrations appear too low to cause significant compensation.

Rhombohedrally Distorted γ-Au 5–x Zn 8+y Phases in the Au–Zn System

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

Thimmaiah, Srinivasa; Miller, Gordon J.

2013-02-04

The region of the Au–Zn phase diagram encompassing γ-brass-type phases has been studied experimentally from 45 to 85 atom % Zn. The γ phases were obtained directly from the pure elements by heating to 680 °C in evacuated silica tubes, followed by annealing at 300 °C. Powder X-ray and single-crystal diffraction studies show that γ-“Au5Zn8” phases adopt a rhombohedrally distorted Cr5Al8 structure type rather than the cubic Cu5Zn8 type. The refined compositions from two single crystals extracted from the Zn- and Au-rich loadings are Au4.27(3)Zn8.26(3)γ0.47 (I) and Au4.58(3)Zn8.12(3)γ0.3 (II), respectively (γ = vacancy). These (I and II) refinements indicated bothmore » nonstatistical mixing of Au and Zn atoms as well as partially ordered vacancy distributions. The structures of these γ phases were solved in the acentric space group R3m (No. 160, Z = 6), and the observed lattice parameters from powder patterns were found to be a = 13.1029(6) and 13.1345(8) Å and c = 8.0410(4) and 8.1103(6) Å for crystals I and II, respectively. According to single-crystal refinements, the vacancies were found on the outer tetrahedron (OT) and octahedron (OH) of the 26-atom cluster. Single-crystal structural refinement clearly showed that the vacancy content per unit cell increases with increasing Zn, or valence-electron concentration. Electronic structure calculations, using the tight-binding linear muffin-tin orbital method with the atomic-sphere approximation (TB-LMTO-ASA) method, indicated the presence of a well-pronounced pseudogap at the Fermi level for “Au5Zn8” as the representative composition, an outcome that is consistent with the Hume–Rothery interpretation of γ brass.« less

Facile synthesis and luminescence characteristics of high-quality CdS: Eu/ZnS core/shell nanocrystals with biocompatibility.

PubMed

Zhang, Kexin; Zhang, Rui; Yu, Yaxin; Sun, Shuqing

2012-04-01

In this paper, we report a facile method to synthesize high quality CdS: Eu nanocrystals (NCs) and CdS: Eu/ZnS NCs with strong photoluminescence (PL). The influence of various experimental variables including the concentration of Eu3+ ions, the reaction time and the reaction temperature were investigated systematically. In addition, the PL properties of CdS: Eu NCs exhibited pH sensitive. Under the acid condition, pH value of the CdS: Eu NCs solution played an important role in determining PL emission intensity. However, under the alkaline condition, the obtained CdS: Eu NCs exhibited a tunable PL emission wavelength (from 490 nm to 610 nm) when pH value was adjusted from pH 7 to 10. After coating with ZnS shell, the CdS: Eu/ZnS NCs showed enhanced PL intensity compare with one of the CdS: Eu NCs. The CdS: Eu NCs and CdS: Eu/ZnS NCs were characterized by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). In addition, the biocompatibility of these NCs was measured by hemolytic test, which indicated that CdS: Eu/ZnS NCs were more biocompatible than CdS: Eu NCs at the same conditions. It can be expected that CdS: Eu/ZnS NCs are promising biolabeling materials.

Safety, immunogenicity and efficacy after switching from reference infliximab to biosimilar SB2 compared with continuing reference infliximab and SB2 in patients with rheumatoid arthritis: results of a randomised, double-blind, phase III transition study

PubMed Central

Choe, Jung-Yoon; Prodanovic, Nenad; Niebrzydowski, Jaroslaw; Staykov, Ivan; Dokoupilova, Eva; Baranauskaite, Asta; Yatsyshyn, Roman; Mekic, Mevludin; Porawska, Wieslawa; Ciferska, Hana; Jedrychowicz-Rosiak, Krystyna; Zielinska, Agnieszka; Lee, Younju; Rho, Young Hee

2018-01-01

Objectives Efficacy, safety and immunogenicity results from the phase III study of SB2, a biosimilar of reference infliximab (INF), were previously reported through 54 weeks. This transition period compared results in patients with rheumatoid arthritis (RA) who switched from INF to SB2 with those in patients who maintained treatment with INF or SB2. Methods Patients with moderate to severe RA despite methotrexate treatment were randomised (1:1) to receive SB2 or INF at weeks 0, 2 and 6 and every 8 weeks thereafter until week 46. At week 54, patients previously receiving INF were rerandomised (1:1) to switch to SB2 (INF/SB2 (n=94)) or to continue on INF (INF/INF (n=101)) up to week 70. Patients previously receiving SB2 continued on SB2 (SB2/SB2 (n=201)) up to week 70. Efficacy, safety and immunogenicity were assessed up to week 78. Results Efficacy was sustained and comparable across treatment groups. American College of Rheumatology (ACR) 20 responses between weeks 54 and 78 ranged from 63.5% to 72.3% with INF/SB2, 66.3%%–69.4% with INF/INF and 65.6%–68.3% with SB2/SB2. Treatment-emergent adverse events during this time occurred in 36.2%, 35.6% and 40.3%, respectively, and infusion-related reactions in 3.2%, 2.0% and 3.5%. Among patients who were negative for antidrug antibodies (ADA) up to week 54, newly developed ADAs were reported in 14.6%, 14.9% and 14.1% of the INF/SB2, INF/INF and SB2/SB2 groups, respectively. Conclusions The efficacy, safety and immunogenicity profiles remained comparable among the INF/SB2, INF/INF and SB2/SB2 groups up to week 78, with no treatment-emergent issues or clinically relevant immunogenicity after switching from INF to SB2. Trial registration number NCT01936181; EudraCT number: 2012-005733-37. PMID:29042358

Na(23)K(9)Tl(15.3): An Unusual Zintl Compound Containing Apparent Tl(5)(7)(-), Tl(4)(8)(-), Tl(3)(7)(-), and Tl(5)(-) Anions.

PubMed

Dong, Zhen-Chao; Corbett, John D.

1996-05-22

Reaction of the neat elements in tantalum containers at 400 degrees C and then 150 degrees C gives the pure title phase. X-ray crystallography shows that the hexagonal structure (P6(3)/mmc, Z = 2, a = 11.235(1) Å, b = 30.133(5) Å) contains relatively high symmetry clusters Tl(5)(7)(-) (D(3)(h)()), Tl(4)(8)(-) (C(3)(v)(), approximately T(d)), and the new Tl(3)(7)(-) (D(infinity)(h)()) plus Tl(5)(-), the last two disordered over the same elongated site in 1:2 proportions. Cation solvation of these anions is tight and specific, providing good Coulombic trapping of weakly bound electrons on the isolated cluster anions. The observed disorder makes the compound structurally a Zintl phase with a closed shell electron count. EHMO calculations on the novel Tl(3)(7)(-) reveal some bonding similarities with the isoelectronic CO(2), with two good sigma(s,p) bonding and two weakly bonding pi MO's. The Tl-Tl bond lengths therein (3.14 Å) are evidently consistent with multiple bonding. The weak temperature-independent paramagnetism and metallic conductivity (rho(293) approximately 90 &mgr;Omega.cm) of the phase are discussed.

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

NASA Astrophysics Data System (ADS)

Ghosh, Subhabrata; N, Shivakiran Bhaktha B.

2016-03-01

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

Ice-core based assessment of historical anthropogenic heavy metal (Cd, Cu, Sb, Zn) emissions in the Soviet Union.

PubMed

Eichler, Anja; Tobler, Leonhard; Eyrikh, Stella; Malygina, Natalia; Papina, Tatyana; Schwikowski, Margit

2014-01-01

The development of strategies and policies aiming at the reduction of environmental exposure to air pollution requires the assessment of historical emissions. Although anthropogenic emissions from the extended territory of the Soviet Union (SU) considerably influenced concentrations of heavy metals in the Northern Hemisphere, Pb is the only metal with long-term historical emission estimates for this region available, whereas for selected other metals only single values exist. Here we present the first study assessing long-term Cd, Cu, Sb, and Zn emissions in the SU during the period 1935-1991 based on ice-core concentration records from Belukha glacier in the Siberian Altai and emission data from 12 regions in the SU for the year 1980. We show that Zn primarily emitted from the Zn production in Ust-Kamenogorsk (East Kazakhstan) dominated the SU heavy metal emission. Cd, Sb, Zn (Cu) emissions increased between 1935 and the 1970s (1980s) due to expanded non-ferrous metal production. Emissions of the four metals in the beginning of the 1990s were as low as in the 1950s, which we attribute to the economic downturn in industry, changes in technology for an increasing metal recovery from ores, the replacement of coal and oil by gas, and air pollution control.

Structural, electronic, and thermal properties of indium-filled InxIr4Sb12 skutterudites

NASA Astrophysics Data System (ADS)

Wallace, M. K.; Li, Jun; Subramanian, M. A.

2018-06-01

The "phonon-glass/electron-crystal" approach has been implemented through incorporation of "rattlers" into skutterudite void sites to increase phonon scattering and thus increase the thermoelectric efficiency. Indium filled IrSb3 skutterudites are reported for the first time. Polycrystalline samples of InxIr4Sb12 (0 ≤ x ≤ 0.2) were prepared by solid-state reaction under a gas mixture of 5% H2 and 95% Ar. The solubility limit of InxIr4Sb12 was found to be close to 0.18. Synchrotron X-ray diffraction refinements reveal all InxIr4Sb12 phases crystallized in body-centered cubic structure (space group : Im 3 bar) with ∼8% antimony site vacancy and with indium partially occupying the 16f site. Unlike known rattler filled skutterudites, under synthetic conditions employed, indium filling in IrSb3 significantly increases the electrical resistivity and decreases the Seebeck coefficient (n-type) while reducing the thermal conductivity by ∼30%. The resultant power factor offsets the decrease in total thermal conductivity giving rise to a substantial decrease in ZT. Principal thermoelectric properties of InxM4Sb12 (M = Co, Rh, Ir) phases are compared. As iridium is a 5d transition metal, zero field cooled (ZFC) magnetization were performed to unravel the effect of spin-orbit interaction on the electronic properties. These results serve to advance the understanding of filled skutterudites, and provide additional insight on the less explored smaller "rattlers" and their influence on key thermoelectric properties.

Surface Phase Stability and Surfactant Behavior on InAsSb

NASA Astrophysics Data System (ADS)

Anderson, Evan M.

InAsSb and related III-As/III-Sb heterostructures are of technological interest for applications in long wavelength infrared optoelectronic devices. However, there remain challenges to growing high quality material for these devices due to the complex interaction between As and Sb. While this interaction has been the subject of intense study, little work has focused on how As and Sb behave at the material surface with even fewer investigations into the atomic scale details of the InAsSb surface. This is a major gap in current knowledge because these materials are typically grown via vapor deposition methods, one atomic layer at a time. Thus, all processes impacting the growth of the crystal and its resultant properties occur at the surface. Despite this, the atomic scale details of the surface phases and processes impacting the Sb-As interaction have not previously been reported. This dissertation investigates the surface As-Sb interaction at an atomistic scale and its modification through different surface chemistry to be used as a guide for future experiments to improve the quality InAsSb of heterostructures by manipulating the surface phase during growth. In order to accomplish this, first principles calculations and experiments are used to investigate this system from three complimentary vantage points. First, the influence of Sb on the InAs surface and the stable surface phases of this system are investigated. Next, a similar approach is used on the opposite compositional extreme of the InAsSb system: As on the surface of InSb. Finally, the interaction of As and Sb is modified by the use of Bi as a surfactant during growth of InAsSb films. The interaction between As and Sb is found to be driven through the formation of surface phases and Bi is found to alter this interaction. Phase diagrams of both Sb on InAs and As on InSb show that As and Sb are driven to intermix through the formation of alloyed surface phases. Additionally, these phases range from having

Photorefractive splicing device with double phase conjugate mirror using Sn2P2S6:Sb crystal

NASA Astrophysics Data System (ADS)

Wakayama, Yuta; Okamoto, Atsushi; Shimayabu, Kohei; Kojima, Yasunori; Grabar, Alexander A.

2009-02-01

We develop a splicing device for photonic crystal fibers (PCFs) based on a double phase conjugate mirror (DPCM) using a novel photorefractive (PR) Sn2P2S6:Sb 1.5% crystal. This PR splicer has many attractive characteristics including modal field compensation and the automatic reconfiguration of the optical path. Utilizing a DPCM as the splicer, our device can adapt to misalignments automatically since the incident beams continuously rewrite an index grating which formed in the crystal. By the implementation of the Sn2P2S6:Sb crystal, the response time for the characteristic of dynamic reconfiguration is improved several-hundred-fold compared with conventional materials, e.g. BaTiO3. We demonstrate that the high angular tolerance is provided using the DPCM with the Sn2P2S6:Sb crystal. When the misalignment of the incident angle is from -7° to 8°, the increment of coupling loss is less than 0.6dB. This is several-ten-fold compared with the fusion splicing. We reveal the dependence of the coupling loss on the position of the incident beams and also the dependence of the energy flow on the propagation distance for the first time with the two-dimensional finite-difference beampropagation method. Using our numerical simulation tool, we can visually investigate the beam propagation property considering the influence of the fanning effect in the Sn2P2S6 crystals.

The role of Sb in solar cell material Cu 2ZnSnS 4

DOE PAGES

Zhang, Xiaoli; Han, Miaomiao; Zeng, Zhi; ...

2017-03-03

In this paper, based on first-principles calculations we report a possible mechanism of the efficiency improvement of the Sb-doped Cu 2ZnSnS 4 (CZTS) solar cells from the Sb-related defect point of view. Different from Sb in CuInSe 2 which substituted the Cu atomic site and acted as group-13 elements on the Cu-poor growth condition, we find out that Sb prefers to substitute Sn atomic site and acts as group-14 elements on the Cu-poor growth condition in CZTS. At low Sb concentration, Sb Sn produces a deep defect level which is detrimental for the solar cell application. At high Sb concentration,more » Sb 5s states form an isolated half-filled intermediate band at 0.5 eV above the valence band maximum which will increase the photocurrent as well as the solar cell efficiency.« less

Phonon Instability and Broken Long-Ranged p Bond in Ge-Sb-Te Phase-Change Materials from First Principles

NASA Astrophysics Data System (ADS)

Song, Young-Sun; Kim, Jeongwoo; Jhi, Seung-Hoon

2018-05-01

Ge-Sb-Te (GST) compounds exhibit substantial electrical and optical contrast between the amorphous and crystalline phases. Despite extensive studies of GST compounds, the underlying mechanism for fast transitions between the amorphous and crystalline phases is yet to be revealed. In this paper, we study the properties of phonons and a long-ranged p -orbital network of hexagonal GST compounds using first-principles calculations. By investigating volume-dependent phonon dispersions, we observe the structural instability at elevated temperature due to the spontaneous softening of a specific in-plane vibrational mode (Eu ). We find that the atomic distortion by the Eu mode is associated with weakening of delocalized p bonding inducing large structural and electrical changes. We also discuss how to manipulate the Eu mode to control the device performance. Our finding helps deepen the understanding of the phase-change mechanism and improve the device performance, especially the switching power and operating temperature.

Life Testing of Yb14MnSb11 for High Performance Thermoelectric Couples

NASA Technical Reports Server (NTRS)

Paik, Jong-Ah; Brandon, Erik; Caillat, Thierry; Ewell, Richard; Fleurial, Jean-Pierre

2011-01-01

The goal of this study is to verify the long term stability of Yb14MnSb11 for high performance thermoelectric (TE) couples. Three main requirements need to be satisfied to ensure the long term stability of thermoelectric couples: 1) stable thermoelectric properties, 2) stable bonding interfaces, and 3) adequate sublimation suppression. The efficiency of the couple is primarily based on the thermoelectric properties of the materials selected for the couple. Therefore, these TE properties should exhibit minimal degradation during the operating period of the thermoelectric couples. The stability of the bonding is quantified by low contact resistances of the couple interfaces. In order to ensure high efficiency, the contact resistances of the bonding interfaces should be negligible. Sublimation suppression is important because the majority of thermoelectric materials used for power generation have peak figures of merit at temperatures where sublimation rates are high. Controlling sublimation is also essential to preserve the efficiency of the couple. During the course of this research, three different life tests were performed with Yb14MnSb11 coupons. TE properties of Yb14MnSb11 exhibited no degradation after 6 months of aging at 1273K, and the electrical contact resistance between a thin metallization layer and the Yb14MnSb11 remained negligible after 1500hr aging at 1273K. A sublimation suppression layer for Yb14MnSb11 was developed and demonstrated for more than 18 months with coupon testing at 1273K. These life test data indicate that thermoelectric elements based on Yb14MnSb11 are a promising technology for use in future high performance thermoelectric power generating couples.

The phase relations in the In 2O 3Fe 2ZnO 4ZnO system at 1350°C

NASA Astrophysics Data System (ADS)

Nakamura, Masaki; Kimizuka, Noboru; Mohri, Takahiko

1990-05-01

The phase relations in the In 2O 3Fe 2ZnO 4ZnO system at 1350°C are determined by means of a classical quenching method. There are a series of homologous solid solutions, In 1.28Fe 0.72O 3(ZnO)InFeO 3(ZnO), In 1.69Fe 0.31O 3(ZnO) 2InFeO 3(ZnO) 2In 0.85Fe 1.15O 3(ZnO) 2, In 2O 3(ZnO) 3InFeO 3(ZnO) 3In 0.78Fe 1.22O 3(ZnO) 3, In 2O 3(ZnO) 4InFeO 3(ZnO) 4In 0.62Fe 1.38O 3(ZnO) 4, In 2O 3(ZnO) 5InFeO 3(ZnO) 5In 0.67Fe 1.33O 3(ZnO) 5, In 2O 3(ZnO) 6InFeO 3(ZnO) 6In 0.60Fe 1.40O 3(ZnO) 6, In 2O 3(ZnO) 7InFeO 3(ZnO) 7In 0.51Fe 1.49O 3(ZnO) 7, In 2O 3(ZnO) 8InFeO 3(ZnO) 8In 1- xFe 1+ xO 3(ZnO) 8 (0.44 ≦ x ≦ 0.64), In 2O 3(ZnO) 9InFeO 3(ZnO) 9In 0.20Fe 1.80O 3(ZnO) 9, In 2O 3(ZnO) 10InFeO 3(ZnO) 10In 1- xFe 1+ xO 3(ZnO) 10 (0.74 ≦ x ≦ 0.89), In 2O 3(ZnO) 11InFeO 3(ZnO) 11In 1- xFe 1+ xO 3(ZnO) 11 (0.60 ≦ x < 1.00), and In 2O 3(ZnO) 13InFeO 3(ZnO) 13Fe 2O 3(ZnO) 13 having the layered structures with space group R overline3m (m = odd) or {P6 3}/{mmc} (m = even) for m in the InFeO 3(ZnO) m. We conclude that there are a series of homologous phases, (Fe 2O 3)(ZnO) m (m ≧ 12) , in the binary ZnOFe 2O 3 system. The lattice constants for these solid solutions are presented as a hexagonal crystal system. It is also concluded that the crystal structures for each solid solution consist of three kinds of layers which are stacked perpendicular to the c-axis in the hexagonal crystal system. In 1+ xFe 1- xO 3(ZnO) m (0 ≦ x ≦ 1) is composed of the InO 1.5, (In xFe 1- xZn)O 2.5, and ZnO layers, and In 1- xFe 1+ xO 3(ZnO) m (0 ≦ x ≦ 1) is composed of (In 1- xFe x)O 1.5, (FeZn)O 2.5, and ZnO layers, respectively. The solid solution range between Fe 2ZnO 4 and In xFe 2- xZnO 4 ( x = 0.40 ± 0.02) with a spinel structure is observed.

Surface phase stability and surfactant behavior of InAsSb alloy surfaces.

NASA Astrophysics Data System (ADS)

Anderson, Evan M.; Lundquist, Adam M.; Pearson, Chris; Millunchick, Joanna M.

InAsSb has the narrowest bandgap of any of the conventional III-V semiconductors: low enough for long wavelength infrared applications. Such devices are sensitive to point defects, which can be detrimental to performance. To control these defects, all aspects of synthesis must be considered, especially the atomic bonding at the surface. We use an ab initio statistical mechanics approach that combines density functional theory with a cluster expansion formalism to determine the stable surface reconstructions of Sb (As) on InAs (InSb) substrates. The surface phase diagram of Sb on InAs is dominated by Sb-dimer termination α2(2x4) and β2(2x4) and c(4x4). Smaller regions of mixed Sb-As dimers appear for high Sb chemical potentials and intermediate As chemical potential. We propose that InAsSb films could be grown on (2x4), which maintain bulk-like stoichiometry, to eliminate the formation of typically observed n-type defects. Scanning tunneling microscopy and reflection high energy electron diffraction confirm the calculated phase diagram. Based on these calculations, we propose a new mechanism for the surfactant behavior of Sb in these materials. We gratefully acknowledge Chakrapani Varanasi and the support of the Department of Defense, Army Research Office via the Grant Number W911NF-12-1-0338.

Magnetic ground state of the two isostructual polymeric quantum magnets [ Cu ( HF 2 ) ( pyrazine ) 2 ] SbF 6 and [ Co ( HF 2 ) ( pyrazine ) 2 ] SbF 6 investigated with neutron powder diffraction

DOE PAGES

Brambleby, J.; Goddard, P. A.; Johnson, R. D.; ...

2015-10-07

The magnetic ground state of two isostructural coordination polymers, (i) the quasi-two-dimensional S=1/2 square-lattice antiferromagnet [Cu(HF 2)(pyrazine) 2]SbF 6 and (ii) a related compound [Co(HF 2)(pyrazine)2]SbF6, was examined with neutron powder diffraction measurements. We find that the ordered moments of the Heisenberg S=1/2 Cu(II) ions in [Cu(HF 2)(pyrazine) 2]SbF 6 are 0.6(1)μ b, while the ordered moments for the Co(II) ions in [Co(HF 2)(pyrazine) 2]SbF 6 are 3.02(6)μ b. For Cu(II), this reduced moment indicates the presence of quantum fluctuations below the ordering temperature. We also show from heat capacity and electron spin resonance measurements that due to the crystalmore » electric field splitting of the S=3/2 Co(II) ions in [Co(HF 2)(pyrazine) 2]SbF 6, this isostructual polymer also behaves as an effective spin-half magnet at low temperatures. Furthermore, the Co moments in [Co(HF 2)(pyrazine) 2]SbF 6 show strong easy-axis anisotropy, neutron diffraction data, which do not support the presence of quantum fluctuations in the ground state, and heat capacity data, which are consistent with 2D or close to 3D spatial exchange anisotropy.« less

Alumina Paste Sublimation Suppression Barrier for Thermoelectric Device

NASA Technical Reports Server (NTRS)

Caillat, Thierry (Inventor); Paik, Jong-Ah (Inventor)

2014-01-01

Alumina as a sublimation suppression barrier for a Zintl thermoelectric material in a thermoelectric power generation device operating at high temperature, e.g. at or above 1000K, is disclosed. The Zintl thermoelectric material may comprise Yb.sub.14MnSb.sub.11. The alumina may be applied as an adhesive paste dried and cured on a substantially oxide free surface of the Zintl thermoelectric material and polished to a final thickness. The sublimation suppression barrier may be finalized by baking out the alumina layer on the Zintl thermoelectric material until it becomes substantially clogged with ytterbia.

Safety, immunogenicity and efficacy after switching from reference infliximab to biosimilar SB2 compared with continuing reference infliximab and SB2 in patients with rheumatoid arthritis: results of a randomised, double-blind, phase III transition study.

PubMed

Smolen, Josef S; Choe, Jung-Yoon; Prodanovic, Nenad; Niebrzydowski, Jaroslaw; Staykov, Ivan; Dokoupilova, Eva; Baranauskaite, Asta; Yatsyshyn, Roman; Mekic, Mevludin; Porawska, Wieslawa; Ciferska, Hana; Jedrychowicz-Rosiak, Krystyna; Zielinska, Agnieszka; Lee, Younju; Rho, Young Hee

2018-02-01

Efficacy, safety and immunogenicity results from the phase III study of SB2, a biosimilar of reference infliximab (INF), were previously reported through 54 weeks. This transition period compared results in patients with rheumatoid arthritis (RA) who switched from INF to SB2 with those in patients who maintained treatment with INF or SB2. Patients with moderate to severe RA despite methotrexate treatment were randomised (1:1) to receive SB2 or INF at weeks 0, 2 and 6 and every 8 weeks thereafter until week 46. At week 54, patients previously receiving INF were rerandomised (1:1) to switch to SB2 (INF/SB2 (n=94)) or to continue on INF (INF/INF (n=101)) up to week 70. Patients previously receiving SB2 continued on SB2 (SB2/SB2 (n=201)) up to week 70. Efficacy, safety and immunogenicity were assessed up to week 78. Efficacy was sustained and comparable across treatment groups. American College of Rheumatology (ACR) 20 responses between weeks 54 and 78 ranged from 63.5% to 72.3% with INF/SB2, 66.3%%-69.4% with INF/INF and 65.6%-68.3% with SB2/SB2. Treatment-emergent adverse events during this time occurred in 36.2%, 35.6% and 40.3%, respectively, and infusion-related reactions in 3.2%, 2.0% and 3.5%. Among patients who were negative for antidrug antibodies (ADA) up to week 54, newly developed ADAs were reported in 14.6%, 14.9% and 14.1% of the INF/SB2, INF/INF and SB2/SB2 groups, respectively. The efficacy, safety and immunogenicity profiles remained comparable among the INF/SB2, INF/INF and SB2/SB2 groups up to week 78, with no treatment-emergent issues or clinically relevant immunogenicity after switching from INF to SB2. NCT01936181; EudraCT number: 2012-005733-37. © Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2018. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

Crystal and electronic structures, luminescence properties of Eu 2+-doped Si 6-zAl zO zN 8-z and M ySi 6-zAl z-yO z+yN 8-z-y ( M=2Li, Mg, Ca, Sr, Ba)

NASA Astrophysics Data System (ADS)

Li, Y. Q.; Hirosaki, N.; Xie, R. J.; Takeda, T.; Mitomo, M.

2008-12-01

The crystal structure, electronic structure, and photoluminescence properties of Eu xSi 6-zAl z-xO z+xN 8-z-x ( x=0-0.1, 0< z<1) and Eu xM ySi 6-zAl z-x-yO z+x+yN 8-z-x-y ( M=2Li, Mg, Ca, Sr, Ba) have been studied. Single-phase Eu xSi 6-zAl z-xO z+xN 8-z-x can be obtained in very narrow ranges of x⩽0.06 ( z=0.15) and z<0.5 ( x=0.3), indicating that limited Eu 2+ ions can be incorporated into nitrogen-rich Si 6-zAl zO zN 8-z. The Eu 2+ ion is found to occupy the 2 b site in a hexagonal unit cell ( P6 3/ m) and directly connected by six adjacent nitrogen/oxygen atoms ranging 2.4850-2.5089 Å. The calculated host band gaps by the relativistic DV-X α method are about 5.55 and 5.45 eV (without Eu 2+ 4 f5 d levels) for x=0 and 0.013 in Eu xSi 6-zAl z-xO z+xN 8-z-x ( z=0.15), in which the top of the 5 d orbitals overlap with the Si-3 s3 p and N-2 p orbitals within the bottom of the conduction band of the host. Eu xSi 6-zAl z-xO z+xN 8-z-x shows a strong green emission with a broad Eu 2+ band centered at about 530 nm under UV to near-UV excitation range. The excitation and emission spectra are hardly modified by Eu concentration and dual-doping ions of Li and other alkaline-earth ions with Eu. Higher Eu concentrations can significantly quench the luminescence of Eu 2+ and decrease the thermal quenching temperature. In addition, the emission spectrum can only be slightly tuned to the longer wavelengths (˜529-545 nm) by increasing z within the solid solution range of z<0.5. Furthermore, the luminescence intensity of Eu xSi 6-zAl z-xO z+xN 8-z-x can be improved by increasing z and the dual-doping of Li and Ba.

Low-energy inelastic response in the superconducting phases of PrOs4Sb12

NASA Astrophysics Data System (ADS)

Setty, Chandan; Wang, Yuxuan; Phillips, Philip W.

2017-08-01

Recent ac susceptibility and polar Kerr effect measurements in the skutterudite superconductor PrOs4Sb12 (POS) (E. M. Levenson-Falk, E. R. Schemm, M. B. Maple, and A. Kapitulnik, arXiv:1609.07535) uncovered the nature of the superconducting double transition from a high-temperature, high-field, time-reversal symmetric phase (or the A phase) to a low-temperature, low-field, time-reversal symmetry-broken phase (or the B phase). Starting from a microscopic model, we derive a Ginzburg-Landau expansion relevant to POS that describes this entrance into the time-reversal symmetry-broken phase along the temperature axis. We also provide a study of the low-energy inelastic (Raman) response in both the A and B phases of POS, and seek additional signatures which could help reveal the exact form of the gap functions previously proposed in these phases. By appropriately manipulating the incoming and scattered light geometries, along with additional subtraction procedures and suitable assumptions, we show that one can access the various irreducible representations contained in the point group describing POS. We demonstrate how to use this technique on example order parameters proposed in POS. Depending on whether there exist nodes along the c axis, we find additional low-energy spectral weight within the superconducting gap in the Eg geometry, a feature that could pinpoint the location of nodes on the Fermi surface.

Zincovelesite-6N6S, Zn3(Fe3+,Mn3+,Al,Ti)8O15(OH), a new högbomite-supergroup mineral from Jacupica mountains, Republic of Macedonia

NASA Astrophysics Data System (ADS)

Chukanov, Nikita V.; Krzhizhanovskaya, Maria G.; Jančev, Simeon; Pekov, Igor V.; Varlamov, Dmitry A.; Göttlicher, Jörg; Rusakov, Vyacheslav S.; Polekhovsky, Yury S.; Chervonnyi, Alexandr D.; Ermolaeva, Vera N.

2018-02-01

A new mineral species zincovelesite-6N6S with the simplified formula Zn3(Fe3+,Mn3+,Al,Ti)8O15(OH) was discovered in the orogenetic zone related to the "Mixed Series" metamorphic complex near the Nežilovo village, Jacupica Mountains, Pelagonia mountain range, Republic of Macedonia. In oxide Zn-Fe-Mn ore, zincovelesite-6N6S forms lenticular aggregates up to 2 × 2 × 0.5 mm consisting of thin near-coplanar platelets up to 70 × 70 × 1 µm3 and associated with franklinite, gahnite, hetaerolite, zincochromite, ferricoronadite, baryte, As-rich fluorapatite, dolomite, Zn-bearing talc, almeidaite, hydroxycalcioroméite, zircon, quartz, and scheelite. In silicate-baryte zones of the metasomatic rock, uniaxial intergrowths of zincovelesite-6N6S with nežilovite are observed. The new mineral is opaque, black, with brownish-black streak. The lustre is strong submetallic to metallic. The micro-indentation hardness is 1118 kg/mm2 which corresponds to Mohs' hardness ca. 6½. Zincovelesite-6N6S is brittle, with uneven fracture. No cleavage or parting is observed. The density calculated from the empirical formula is 5.158 g/cm3. In reflected light zincovelesite-6N6S is light grey. The reflectance values [R max/R min, % (λ, nm)] are: 17.1/13.4 (470), 16.5/12.8 (546), 16.2/12.6 (589), 15.6/12.2 (650). The IR spectrum shows the presence of OH groups. According to the Mössbauer spectrum, all iron is trivalent. The Mn K-edge XANES spectroscopy shows that Mn is predominantly or completely trivalent. The average chemical composition is (wt%; electron microprobe, H2O determined by gas chromatography of ignition products): MgO 0.97, CuO 0.50, ZnO 30.80, Al2O3 8.17, Mn2O3 21.31, Fe2O3 29.44, TiO2 5.28, Sb2O5 3.74, H2O 1.1, total 101.31. The empirical formula based on 16 O atoms is H1.05Zn3.26Mg0.21Cu0.05Fe3+ 3.18Mn3+ 2.32Al1.38Ti0.57Sb0.20O16. Zincovelesite-6N6S is trigonal, probable space group P-3m1, a = 5.902(2) Å, c = 55.86(1) Å, V = 1684.8(9) Å3, Z = 6. The strongest lines of

Mechano-luminescence studies of nano ZnMgAl10O17:Eu phosphor under UV irradiation

NASA Astrophysics Data System (ADS)

Verma, Akshkumar; Verma, Ashish; Panda, Maheswar

2018-05-01

ZnMgAl10O17:Eu nano phosphors were prepared successfully, using the combustion route by employing urea as a fuel. The structural, and Morphological, properties were measured using x-ray diffraction (XRD) Scanning electron microscopy (SEM) transition electron microscopy. The BET surface area of sample were found to be of ˜13.92 m2/g. The ML (Mechano-luminescence) were measured to the home made instrument. The phosphor showed more strong and high ML intensity to the without UV irradiated material. Therefore ZnMgAl10O17:Eu2+ phosphor may use as a damage sensor and dosimetry material. The ML emission spectra of the Zn0.99MgAl10O17:Eu0.01 phosphor showed the characteristic Eu2+ emission peaks ˜453nm (blue) originating from the transitions 4f65d1→4f7, Therefore ZnMgAl10O17:Eu2+ phosphor may use as a blue phosphor material.

Coexistence of charge order and antiferromagnetism in (TMTTF)2SbF6: NMR study

NASA Astrophysics Data System (ADS)

Nomura, K.; Yamamoto, M.; Matsunaga, N.; Hirose, S.; Shimohara, N.; Satoh, T.; Isome, T.; Liu, Y.; Kawamoto, A.

2015-03-01

The electronic state of (TMTTF)2SbF6 was investigated by the 1H and 13C NMR measurements. The temperature dependence of T1-1 in 1H NMR shows a sharp peak associated with the antiferromagnetic transition at TAF=6 K. The temperature dependence of T1-1 is described by the power law T2.4 below TAF. This suggests the nodal gapless spin wave excitation in antiferromagnetic phase. In 13C NMR, two sharp peaks at high temperature region, associated with the inner and the outer carbon sites in TMTTF dimer, split into four peaks below 150 K. It indicates that the charge disproportionation occurs. The degree of charge disproportionation Δρ is estimated as (0.25±0.09)e from the chemical shift difference. This value of Δρ is consistent with that obtained from the infrared spectroscopy. In the antiferromagnetic state (AFI), the observed line shape is well fitted by eight Lorentzian peaks. This suggests that the charge order with the same degree still remains in the AF state. From the line assignment, the AF staggered spin amplitude is obtained as 0.70 μB and 0.24 μB at the charge rich and the poor sites, respectively. These values corresponding to almost 1 μB per dimer are quite different from 0.11 μB of another AF (AFII) state in (TMTTF)2Br with effective higher pressure. As a result, it is understood that the antiferromagnetic staggered spin order is stabilized on the CO state in the AFI phase of (TMTTF)2SbF6.

Remarkably Enhancing Green-Excitation Efficiency for Solar Energy Utilization: Red Phosphors Ba2ZnS3:Eu2+, X- Co-Doped Halide Ions (X = Cl, Br, I).

PubMed

Luo, Tingting; Du, Yun; Qiu, Zhongxian; Li, Yanmei; Wang, Xiaofang; Zhou, Wenli; Zhang, Jilin; Yu, Liping; Lian, Shixun

2017-05-15

Eu 2+ -activated Ba 2 ZnS 3 has been reported as a red phosphor with a broad emission band peaking at 650 nm under blue excitation for white-LED. In this study, Ba 2 ZnS 3 :Eu 2+ , X - (X = F, Cl, Br, I) phosphors doped with halide ions were prepared by traditional high-temperature solid-state reaction. Phase identification of powders was performed by X-ray powder diffraction analysis, confirming the existence of single-phase Ba 2 ZnS 3 crystals without dopant. The corresponding excitation spectra showed an additional broad band in the green region peaking at 550 nm when the phosphor was halogenated except by the smallest F - . It was proved that the green-excitation efficiency successively strengthened from Cl - , to Br - , to I - , which suggested larger halide ions made a greater contribution to the further splitting of the t 2g energy level of the doped Eu 2+ ions in the host Ba 2 ZnS 3 , and the optimized formula Ba 1.995 ZnS 2.82 :Eu 2+ 0.005 , I - 0.18 showed a potential application in solar spectral conversion for agricultural greenhouse and solar cell. Defect chemistry theory and crystal field theory provided insights into the key role of halide ions in enhancing green-excitation efficiency.

Charge compensation mechanisms in favor of the incorporation of the Eu3+ ion into the ZnO host lattice

NASA Astrophysics Data System (ADS)

Baira, M.; Bekhti-Siad, A.; Hebali, K.; Bouhani-Benziane, H.; Sahnoun, M.

2018-05-01

Eu3+ doped phosphors with charge compensation are potential candidates of red emitting phosphors for lamp applications. Charge compensation improves the luminescence performance of the material. The charge compensation can most probably be achieved by three possible mechanisms: (a) two Zn2+ ions are replaced by one Eu3+ ions and one monovalent cation, 2Zn2+ →Eu3++ Li+, where Li+ is acting as a charge compensator; (b) the charge compensation is provided by a zinc vacancy (VZn) defects, 3Zn2+ → 2Eu3++ VZn, the subscript Zn denotes an ion in a normal zinc site in the lattice; (c) two Zn2+ ions are replaced by one Eu3+ ions with the presence of interstitial oxygen (Oi), 2Zn2+ → 2Eu3++ Oi. Electronic structures of the crystals corresponding to the three models are evaluated by the first-principles quantum mechanical calculations based on the density functional theory. It is found that the charge compensator defects make Eu3+ doping in ZnO energetically more favorable. They break the local symmetry around the Eu3+ ion and lead to deep states below the empty upper band, the conduction band that could facilitate intra-4f shell transitions, which can obviously improve the emission intensity of Eu3+-doped ZnO. Therefore, the effect of these defects on the host crystals electronic band states relative to the Eu3+ states is reported, since both electron transfer and electronically energy transfer processes enhance the performance of optoelectronic devices based on this material. These theoretical insights are helpful for designing rare-earth doped oxide materials with high photoluminescence (PL) performance.

Phase stability and lattice thermal conductivity reduction in CoSb{sub 3} skutterudites, doped with chalcogen atoms

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

Battabyal, M., E-mail: manjusha.battabyal@project.arci.res.in; Priyadarshini, B.; Gopalan, R.

We report a significant reduction in the lattice thermal conductivity of the CoSb{sub 3} skuttertudites, doped with chalcogen atoms. Te/Se chalcogen atoms doped CoSb{sub 3} skutterudite samples (Te{sub 0.1}Co{sub 4}Sb{sub 12}, Se{sub 0.1}Co{sub 4}Sb{sub 12}, Te{sub 0.05}Se{sub 0.05}Co{sub 4}Sb{sub 12}) are processed by ball milling and spark plasma sintering. X-ray diffraction data combined with energy dispersive X-ray spectra indicate the doping of Te/Se chalcogen atoms in the skutterudite. The temperature dependent X-ray diffraction confirms the stability of the Te/Se doped CoSb{sub 3} skutterudite phase and absence of any secondary phase in the temperature range starting from 300 K to 773more » K. The Raman spectroscopy reveals that different chalcogen dopant atoms cause different resonant optical vibrational modes between the dopant atom and the host CoSb{sub 3} skutterudite lattice. These optical vibrational modes do scatter heat carrying acoustic phonons in a different spectral range. It was found that among the Te/Se chalcogen atoms, Te atoms alter the host CoSb{sub 3} skutterudite lattice vibrations to a larger extent than Se atoms, and can potentially scatter more Sb related acoustic phonons. The Debye model of lattice thermal conductivity confirms that the resonant phonon scattering has important contributions to the reduction of lattice thermal conductivity in CoSb{sub 3} skutterudites doped with Te/Se chalcogen atoms. Lattice thermal conductivity ∼ 0.9 W/mK at 773 K is achieved in Te{sub 0.1}Co{sub 4}Sb{sub 12} skutterudites, which is the lowest value reported so far in CoSb{sub 3} skutterudites, doped with single Te chalcogen atom.« less

Ti-Sb-Te alloy: a candidate for fast and long-life phase-change memory.

PubMed

Xia, Mengjiao; Zhu, Min; Wang, Yuchan; Song, Zhitang; Rao, Feng; Wu, Liangcai; Cheng, Yan; Song, Sannian

2015-04-15

Phase-change memory (PCM) has great potential for numerous attractive applications on the premise of its high-device performances, which still need to be improved by employing a material with good overall phase-change properties. In respect to fast speed and high endurance, the Ti-Sb-Te alloy seems to be a promising candidate. Here, Ti-doped Sb2Te3 (TST) materials with different Ti concentrations have been systematically studied with the goal of finding the most suitable composition for PCM applications. The thermal stability of TST is improved dramatically with increasing Ti content. The small density change of T0.32Sb2Te3 (2.24%), further reduced to 1.37% for T0.56Sb2Te3, would greatly avoid the voids generated at phase-change layer/electrode interface in a PCM device. Meanwhile, the exponentially diminished grain size (from ∼200 nm to ∼12 nm), resulting from doping more and more Ti, enhances the adhesion between phase-change film and substrate. Tests of TST-based PCM cells have demonstrated a fast switching rate of ∼10 ns. Furthermore, because of the lower thermal conductivities of TST materials, compared with Sb2Te3-based PCM cells, T0.32Sb2Te3-based ones exhibit lower required pulse voltages for Reset operation, which largely decreases by ∼50% for T0.43Sb2Te3-based ones. Nevertheless, the operation voltages for T0.56Sb2Te3-based cells dramatically increase, which may be due to the phase separation after doping excessive Ti. Finally, considering the decreased resistance ratio, TixSb2Te3 alloy with x around 0.43 is proved to be a highly promising candidate for fast and long-life PCM applications.

First-principles study of the amorphous In3SbTe2 phase change compound

NASA Astrophysics Data System (ADS)

Los, Jan H.; Kühne, Thomas D.; Gabardi, Silvia; Bernasconi, Marco

2013-11-01

Ab initio molecular dynamics simulations based on density functional theory were performed to generate amorphous models of the phase change compound In3SbTe2 by quenching from the melt. In-Sb and In-Te are the most abundant bonds with only a minor fraction of Sb-Te bonds. The bonding geometry in the amorphous phase is, however, strongly dependent on the density in the range 6.448-5.75 g/cm3 that we investigated. While at high density the bonding geometry of In atoms is mostly octahedral-like as in the cubic crystalline phase of the ternary compound In3SbTe2, at low density we observed a sizable fraction of tetrahedral-like geometries similar to those present in the crystalline phase of the two binary compounds InTe and InSb that the ternary system can be thought to be made of. We show that the different ratio between octahedral-like and tetrahedral-like bonding geometries has fingerprints in the optical and vibrational spectra.

Facile construction of vertically aligned EuS-ZnO hybrid core shell nanorod arrays for visible light driven photocatalytic properties

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

Ranjith, K. S.; Kumar, D. Ranjith; Kumar, R. T. Rajendra, E-mail: rtrkumar@buc.edu.in

2015-06-24

We demonstrated the development of coupled semiconductor in the form of hybrid heterostructures for significant advancement in catalytic functional materials. In this article, we report the preparation of vertically aligned core shell ZnO-EuS nanorod photocatalyst arrays by a simple chemical solution process followed by sulfudation process. The XRD pattern confirmed formation of the hexagonal wurtzite structure of ZnO and cubic nature of the EuS. Cross sectional FESEM images show vertical rod array structure, and the size of the nanorods ranges from 80 to 120 nm. UV-Vis DRS spectra showed that the optical absorption of ZnO was significantly enhanced to the visiblemore » region by modification with EuS surfaces. TEM study confirmed that the surface of ZnO was drastically improved by the modification with EuS nanoparticle. The catalytic activity of EuS−ZnO core shell nanorod arrays were evaluated by the photodegradation of Methylene Blue (MB) dye under visible irradiation. The results revealed that the photocatalytic activity of EuS−ZnO was much higher than that of ZnO under natural sunlight. EuS−ZnO was found to be stable and reusable without appreciable loss of catalytic activity up to four consecutive cycles.« less

Effect of structural evolution of ZnO/HfO2 nanocrystals on Eu2+/Eu3+ emission in glass-ceramic waveguides for photonic applications

NASA Astrophysics Data System (ADS)

Ghosh, Subhabrata; N, Shivakiran Bhaktha B.

2018-06-01

Eu-doped 70SiO2–23HfO2–7ZnO (mol%) glass-ceramic waveguides have been fabricated by sol-gel method as a function of heat-treatment temperatures for on-chip blue-light emitting source applications. Structural evolution of spherical ZnO and spherical as well as rod-like HfO2 nanocrystalline structures have been observed with heat-treatments at different temperatures. Initially, in the as-prepared samples at 900 ◦C, both, Eu2+ as well as Eu3+ ions are found to be present in the ternary matrix. With controlled heat-treatments of up to 1000 ◦C for 2 h, local environment of Eu-ions become more crystalline in nature and the reduction of Eu3+ to Eu2+ takes place in such ZnO/HfO2 crystalline environments. In these ternary glass-ceramic waveguides, heat-treated at higher temperatures, the blue-light emission characteristic, which is the signature of 4f 65d \\to 4f 7 energy level transition of Eu2+ ions is found to be greatly enhanced. The as-prepared glass-ceramic waveguides exhibit a propagation loss of 0.4 ± 0.2 dB cm‑1 at 632.8 nm. Though the propagation losses increase with the growth of nanocrystals, the added functionalities achieved in the optimally heat-treated Eu-doped 70SiO2–23HfO2–7ZnO (mol%) waveguides, make them a viable functional optical material for the fabrication of on-chip blue-light emitting sources for integrated optic applications.

Investigation of nanoscale voids in Sb-doped p-type ZnO nanowires.

PubMed

Pradel, Ken C; Uzuhashi, Jun; Takei, Toshiaki; Ohkubo, Tadakatsu; Hono, Kazuhiro; Fukata, Naoki

2018-08-17

While it has multiple advantageous optoelectronic and piezoelectric properties, the application of zinc oxide has been limited by the lack of a stable p-type dopant. Recently, it was discovered that antimony doping can lead to stable p-type doping in ZnO, but one curious side effect of the doping process is the formation of voids inside the nanowire. While previously used as a signifier of successful doping, up until now, little research has been performed on these structures themselves. In this work, the effect of annealing on the size and microstructure of the voids was investigated using TEM and XRD, finding that the voids form around a region of Zn 7 Sb 2 O 12 . Furthermore, using Raman spectroscopy, a new peak associated with successful doping was identified. The most surprising finding, however, was the presence of water trapped inside the nanowire, showing that this is actually a composite structure. Water was initially discovered in the nanowires using atom probe tomography, and verified using Raman spectroscopy.

Near-UV and blue wavelength excitable Mg{sub 0.6}Ca{sub 2.16}Mo{sub 0.2}W{sub 0.8}O{sub 6}: Eu{sub 0.12}{sup 3+}/Na{sub 0.12}{sup +} high efficiency red phosphors

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

Khanna, A.; Electrical Computer and Systems Engineering, Rensselaer Polytechnic Institute, Troy, NY 12180; Dutta, P.S., E-mail: duttap@rpi.edu

Red phosphors with narrow emission around 615 nm (with FWHM~5–10 nm) having chemical compositions of A{sub 0.6}Ca{sub 2.16}Mo{sub 0.2}W{sub 0.8}O{sub 6}: Eu{sub 0.12}{sup 3+}/Na{sub 0.12}{sup +} (A=Mg, Sr) have been found to exhibit the highest luminescence amongst the molybdate–tungstate family when excited by sources in the 380–420 nm wavelength range. Thus they are most suitable for enhancing color rendering index and lowering color temperature in phosphor converted white LEDs (pc-WLEDs) with near-UV/blue LED excitation sources. The excitation band edge in the near UV/blue wavelength in the reported phosphor has been attributed to the coordination environment of the transition metal ionmore » (Mo{sup 6+}, W{sup 6+}) and host crystal structure. Furthermore the quantum efficiency of the phosphors has been enhanced by adjusting activator concentration, suitable compositional alloying using substitutional alkaline earth metal cations and charge compensation mechanisms. - Graphical abstract: The charge transfer excitation of orthorhombic Mg{sub 0.6}Ca{sub 2.16}Mo{sub 0.2}W{sub 0.8}O{sub 6}: Eu{sub 0.12}{sup 3+}/Na{sub 0.12}{sup +} is significantly higher than tetragonal CaMoO{sub 4}: Eu{sup 3+} phosphors making Mg{sub 0.6}Ca{sub 2.16}Mo{sub 0.2}W{sub 0.8}O{sub 6}: Eu{sub 0.12}{sup 3+}/Na{sub 0.12}{sup +} prime candidates for fabrication of warm white phosphor-converted LEDs. - Highlights: • LED excitable Mg{sub 0.6}Ca{sub 2.16}Mo{sub 0.2}W{sub 0.8}O{sub 6}: Eu{sub 0.12}{sup 3+}/Na{sub 0.12}{sup +} phosphors were synthesized. • These phosphors are 10 times more intense than CaMoO{sub 4}: Eu{sup 3+} red phosphors. • Their intensity and efficiency were enhanced by materials optimization techniques. • Such techniques include compositional alloying, charge compensation, etc.« less

Field-temperature phase diagram and entropy landscape of CeAuSb 2

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

Zhao, Lishan; Yelland, Edward A.; Bruin, Jan A. N.

2016-05-12

Here, we report a field-temperature phase diagram and an entropy map for the heavy-fermion compound CeAuSb 2. CeAuSb 2 orders antiferromagnetically below T N = 6.6 K and has two metamagnetic transitions, at 2.8 and 5.6 T. The locations of the critical end points of the metamagnetic transitions, which may play a strong role in the putative quantum criticality of CeAuSb 2 and related compounds, are identified. The entropy map reveals an apparent entropy balance with Fermi-liquid behavior, implying that above the Neel transition the Ce moments are incorporated into the Fermi liquid. High-field data showing that the magnetic behaviormore » is remarkably anisotropic are also reported.« less

Effect of SiC addition to the characteristics of Al-11Zn-6.7Mg composite produced by squeeze casting for ballistic application

NASA Astrophysics Data System (ADS)

Adiputra, R. F.; Wijanarko, R.; Angela, I.; Sofyan, B. T.

2018-01-01

Aluminium composite material as an alternative to steel used in body of tactical vehicles has been studied. Addition of SiC was expected to have strengthening effect on the composite matrix therefore improving its ballistic performance. Composites of Al-11Zn-6.7Mg matrix and SiC strengthening particles with the fraction of 0, 10, and 15 vol. % were fabricated through squeeze casting process. Composite samples were then precipitation strengthened at 130 °C for 102 h to further improve their toughness. Final products were characterized by using chemical composition testing, optical microscopy, Scanning Electron Microscope - Energy Dispersive Spectroscopy (SEM-EDS) and quantitative metallography to calculate porosity, hardness test, impact test, and type III ballistic test in accordance with NIJ 0108.04 standard. The results showed that increase in SiC volume fraction from 0 to 10 and 15 vol. % managed to improve the hardness from 73 to 85 and 87 HRB, respectively, while on the other hand reduced the impact values from 12,278.69 to 11,290.35 and 9,924.54 J/m2. SEM-EDS observation confirmed the presence of Mg3Zn3Al2 intermetallic compound which formed during solidification and indicated the precipitation of MgZn2 precipitates during ageing. The ballistic testing demonstrated a promising result of the potential of Al-11Zn-6.7Mg composite strengthened by 15 vol. % SiC to withstand penetration of type III bullet (7.62 mm).

Revealing the optoelectronic and thermoelectric properties of the Zintl quaternary arsenides ACdGeAs{sub 2} (A = K, Rb)

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

Azam, Sikander; Khan, Saleem Ayaz; Goumri-Said, Souraya, E-mail: Souraya.Goumri-Said@chemistry.gatech.edu

Highlights: • Zintl tetragonal phase ACdGeAs{sub 2} (A = K, Rb) are chalcopyrite and semiconductors. • Their direct band gap is suitable for PV, optolectronic and thermoelectric applications. • Combination of DFT and Boltzmann transport theory is employed. • The present arsenides are found to be covalent materials. - Abstract: Chalcopyrite semiconductors have attracted much attention due to their potential implications in photovoltaic and thermoelectric applications. First principle calculations were performed to investigate the electronic, optical and thermoelectric properties of the Zintl tetragonal phase ACdGeAs{sub 2} (A = K, Rb) using the full potential linear augmented plane wave method andmore » the Engle–Vosko GGA (EV–GGA) approximation. The present compounds are found semiconductors with direct band gap and covalent bonding character. The optical transitions are investigated via the dielectric function (real and imaginary parts) along with other related optical constants including refractive index, reflectivity and energy-loss spectrum. Combining results from DFT and Boltzmann transport theory, we reported the thermoelectric properties such as the Seebeck’s coefficient, electrical and thermal conductivity, figure of merit and power factor as function of temperatures. The present chalcopyrite Zintl quaternary arsenides deserve to be explored for their potential applications as thermoelectric materials and for photovoltaic devices.« less

Phase stabilization in transparent Lu2O3:Eu ceramics by lattice expansion

NASA Astrophysics Data System (ADS)

Seeley, Z. M.; Dai, Z. R.; Kuntz, J. D.; Cherepy, N. J.; Payne, S. A.

2012-11-01

Gadolinium lutetium oxide transparent ceramics doped with europium (Gd,Lu)2O3:Eu were fabricated via vacuum sintering and hot isostatic pressing (HIP). Nano-scale starting powder with the composition GdxLu1.9-xEu0.1O3 (x = 0, 0.3, 0.6, 0.9, 1.0, and 1.1) were uniaxially pressed and sintered under high vacuum at 1625 °C to obtain ˜97% dense structures with closed porosity. Sintered compacts were then subjected to 200 MPa argon gas at temperatures between 1750 and 1900 °C to reach full density. It was observed that a small portion of the Eu3+ ions were exsolved from the Lu2O3 cubic crystal lattice and concentrated at the grain boundaries, where they precipitated into a secondary monoclinic phase creating optical scattering defects. Addition of Gd3+ ions into the Lu2O3 cubic lattice formed the solid solution (Gd,Lu)2O3:Eu and stretched the lattice parameter allowing the larger Eu3+ ions to stay in solid solution, reducing the secondary phase and improving the transparency of the ceramics. Excess gadolinium, however, resulted in a complete phase transformation to monoclinic at pressures and temperatures sufficient for densification. Light yield performance was measured and all samples show equal amounts of the characteristic Eu3+ luminescence, indicating gadolinium addition had no adverse effect. This material has potential to improve the performance of high energy radiography devices.

Enhanced thermoelectric performance driven by high-temperature phase transition in the phase change material Ge 4SbTe 5

DOE PAGES

Williams, Jared B.; Lara-Curzio, Edgar; Cakmak, Ercan; ...

2015-05-15

Phase change materials are identified for their ability to rapidly alternate between amorphous and crystalline phases and have large contrast in the optical/electrical properties of the respective phases. The materials are primarily used in memory storage applications, but recently they have also been identified as potential thermoelectric materials. Many of the phase change materials researched today can be found on the pseudo-binary (GeTe) 1-x(Sb 2Te 3) x tie-line. While many compounds on this tie-line have been recognized as thermoelectric materials, here we focus on Ge 4SbTe 5, a single phase compound just off of the (GeTe) 1-x(Sb 2Te 3) xmore » tie-line, that forms in a stable rocksalt crystal structure at room temperature. We find that stoichiometric and undoped Ge 4SbTe 5 exhibits a thermal conductivity of ~1.2 W/m-K at high temperature and a large Seebeck coefficient of ~250 μV/K. The resistivity decreases dramatically at 623 K due to a structural phase transition which lends to a large enhancement in both thermoelectric power factor and thermoelectric figure of merit at 823 K. In a more general sense the research presents evidence that phase change materials can potentially provide a new route to highly efficient thermoelectric materials for power generation at high temperature.« less

The Phase Relations in the In 2O 3-Al 2ZnO 4-ZnO System at 1350°C

NASA Astrophysics Data System (ADS)

Nakamura, Masaki; Kimizuka, Noboru; Mohri, Takahiko; Isobe, Mitsumasa

1993-08-01

Phase relations in the In 2O 3-Al 2ZnO 4-ZnO system at 1350°C are determined by a classical quenching method. This system consists of In 2O 3, Al 2ZnO 4, ZnO, and homologous phases InAlO 3(ZnO) m ( m = 2, 3, …) having solid solutions with LuFeO 3(ZnO) m-type crystal structures. These solid solution ranges are as follows: In 1+ x1Al 1- x1O 3(ZnO) 2 ( x1 = 0.70)-In 1+ x2Al 1- x2O 3(ZnO) 2 ( x2 = 0.316-0.320), In 2O 3(ZnO) 3-In 1+ xAl 1- xO 3(ZnO) 3 ( x = 0.230), In 2O 3(ZnO) 4-In 1+ xAl 1- xO 3(ZnO) 4 ( x = 0.15-0.16), In 2O 3(ZnO) 5-In 1+ xAl 1- xO 3(ZnO) 5 ( x = 0.116-0.130), In 2O 3(ZnO) 6-In 1+ xAl 1- xO 3(ZnO) 6 ( x = 0.000-0.111), In 2O 3(ZnO) 7-In 1+ xAl 1- xO 3(ZnO) 7 ( x = 0.08), In 2O 3(ZnO) 8-In 1+ xAl 1- xO 3(ZnO) 8 ( x: undetermined), and In 2O 3(ZnO) m-InAlO 3(ZnO) m ( m = 9, 10, 11, 13, 15, 17, and 19). The space groups of these homologous phases belong to R3¯ m for m = odd or P6 3/ mmc for m = even. Their crystal structures, In 1+ xAl 1- xO 3(ZnO) m (0 < x < 1), consist of three kinds of layers: an InO 1.5 layer, an (In xAl 1- xZn)O 2.5 layer, and ZnO layers. A comparison of the phase relations in the In 2O 3- M2ZnO 4-ZnO systems ( M = Fe, Ga, or Al) is made and their characteristic features are discussed in terms of the ionic radii and site preferences of the M cations.

Synthesis and Thermoelectric Properties of Charge-Compensated SyPdxCo4-xSb12 Skutterudites.

PubMed

Wan, Shun; Qiu, Pengfei; Huang, Xiangyang; Song, Qingfeng; Bai, Shengqiang; Shi, Xun; Chen, Lidong

2018-01-10

Recently, the electronegative elements (e.g., S, Se, Cl, and Br) filled skutterudites have attracted great attention in thermoelectric community. Via doping of some electron donors at the Sb sites, these electronegative elements can be filled into the voids of CoSb 3 forming thermodynamically stable compounds, which greatly extends the scope of filled skutterudites. In this study, we show that doping appropriate elements at the Co sites can also stabilize the electronegative elements in the voids of CoSb 3 . A series of S y Pd x Co 4-x Sb 12 compounds were successfully fabricated by a traditional solid state reaction method combined with a spark plasma sintering technique. The phase composition and electrical and thermal transport properties were systematically characterized, and the related mechanisms were deeply discussed. It is found that the charge compensation between Pd doping and S filling is the main reason for the formation of thermodynamically stable S y Pd x Co 4-x Sb 12 compounds. Filling S element in the voids of CoSb 3 provides additional holes to reduce the carrier concentration while scarcely affecting the carrier mobility. However, doping Pd at the Co sites not only changes the carrier scattering mechanism but also deteriorates the carrier mobility. Low lattice thermal conductivities are observed in these S y Pd x Co 4-x Sb 12 compounds, which are attributed to the low resonant frequency of the S element. Finally, a maximal figure of merit of 0.85 is obtained for S 0.05 Pd 0.25 Co 3.75 Sb 12 at 700 K.

Synthesis and Thermoelectric Properties of Partially Double-Filled (Ce1- z Pr z ) y Fe4- x Co x Sb12 Skutterudites

NASA Astrophysics Data System (ADS)

Cha, Ye-Eun; Shin, Dong-Kil; Kim, Il-Ho

2018-06-01

Partially double-filled p-type (Ce1- z Pr z ) y Fe4- x Co x Sb12 ( z = 0.25, 0.75; y = 0.8; x = 0, 0.5, 1.0) skutterudites were synthesized by encapsulated melting and consolidated by hot pressing. The microstructure, phase, charge transport characteristics, and thermoelectric properties of the hot-pressed specimens were analyzed. Detailed measurements indicated that the skutterudite phase was successfully synthesized, but a small amount of a secondary phase (FeSb2) was also identified. However, the amount of the FeSb2 phase decreased with an increase in the Co substitution. Unlike for the filled Ce1- z Pr z Fe4- x Co x Sb12 skutterudites with y = 1, the (Ce,Pr)Sb2 phases were not formed by partial filling with Ce/Pr. The electrical conductivity decreased with increasing temperature, similar to the behavior shown by degenerate semiconductors. The Hall coefficient and the Seebeck coefficients were positive, indicating that all specimens exhibited p-type characteristics. The electrical conductivity and the electronic thermal conductivity decreased with increasing Pr filling and Co substitution because of the decreased carrier concentration caused by charge compensation. A maximum dimensionless figure of merit, ZTmax = 0.84, was obtained at 623 K for (Ce0.75Pr0.25)0.8Fe3CoSb12.

Oxidation Studies of Cu12Sb3.9Bi0.1S10Se3 Tetrahedrite

NASA Astrophysics Data System (ADS)

Gonçalves, António P.; Lopes, Elsa B.; Montemor, Maria F.; Monnier, Judith; Lenoir, Bertrand

2018-02-01

Tetrahedrites are widespread minerals with general formula Cu10 M 2Sb4S13 (M = Cu, Mn, Fe, Co, Ni, Zn). Their thermoelectric properties can be tuned through proper doping and reach zT values as high as 1, being considered promising low-cost thermoelectric materials. However, for practical application in thermoelectric devices, it is necessary to establish their ability to operate for long periods under working temperatures and atmospheres. We present herein studies of oxidation in air of Cu12Sb3.9Bi0.1S10Se3 tetrahedrite at four different temperatures between 230°C and 375°C, together with preliminary corrosion studies in aggressive NaCl electrolyte. Surface oxidation already occurs at the lower studied temperatures, but a strong decrease of the oxidation rate is observed for materials treated at intermediate temperature (275°C), where a continuous surface layer of Cu2-x S forms, pointing to a protective effect of this layer that could be applied in devices operating at such temperatures. For the material treated at higher temperatures (350°C and 375°C), no tetrahedrite phases were seen after 1500 h, which can be related to the (tetrahedrite + chalcostibite + antimony → skinnerite) reaction that occurs above 280°C. Corrosion studies indicated that increasing the oxidation temperature unfortunately leads to a decrease of the corrosion resistance of tetrahedrite-based phases.

Energy Transfer Efficiency from ZnO-Nanocrystals to Eu3+ Ions Embedded in SiO₂ Film for Emission at 614 nm.

PubMed

Mangalam, Vivek; Pita, Kantisara

2017-08-10

In this work, we study the energy transfer mechanism from ZnO nanocrystals (ZnO-nc) to Eu 3+ ions by fabricating thin-film samples of ZnO-nc and Eu 3+ ions embedded in a SiO₂ matrix using the low-cost sol-gel technique. The time-resolved photoluminescence (TRPL) measurements from the samples were analyzed to understand the contribution of energy transfer from the various ZnO-nc emission centers to Eu 3+ ions. The decay time obtained from the TRPL measurements was used to calculate the energy transfer efficiencies from the ZnO-nc emission centers, and these results were compared with the energy transfer efficiencies calculated from steady-state photoluminescence emission results. The results in this work show that high transfer efficiencies from the excitonic and Zn defect emission centers is mostly due to the energy transfer from ZnO-nc to Eu 3+ ions which results in the radiative emission from the Eu 3+ ions at 614 nm, while the energy transfer from the oxygen defect emissions is most probably due to the energy transfer from ZnO-nc to the new defects created due to the incorporation of the Eu 3+ ions.

In-Filled La0.5Co4Sb12 Skutterudite System with High Thermoelectric Figure of Merit

NASA Astrophysics Data System (ADS)

Bashir, Mohamed Bashir Ali; Said, Suhana Mohd; Sabri, Mohd Faizul Mohd; Miyazaki, Yuzuru; Shnawah, Dhafer Abdulameer; Shimada, Masanori; Salleh, Mohd Faiz Mohd; Mahmood, Mohamad Syafie; Salih, Ethar Yahya; Fitriani, Fitriani; Elsheikh, Mohamed Hamid

2018-04-01

The contribution of In addition to the La0.5Co4Sb12 skutterudite structure to improve its thermoelectric properties has been demonstrated. In x La0.5Co4Sb12 (0 ≤ x ≤ 0.3) samples were prepared through mechanical alloying followed by spark plasma sintering. Characterization of the phase structure and morphology of the sintered In x La0.5Co4Sb12 bulk samples was carried out using x-ray diffraction (XRD) analysis, scanning electron microscopy, and energy-dispersive x-ray spectroscopy. Rietveld analysis of the XRD spectra indicated that double filling at the 2a (000) interstitial site with La and In was successfully achieved, significantly improving the thermoelectric performance of the La0.5Co4Sb12 compound through simultaneous increase in the electrical conductivity and Seebeck coefficient. A maximum power factor of 3.39 × 10-3 W/ m-K2 was recorded at 644 K for the In0.3La0.5Co4Sb12 sample, more than 96% of that of the La0.5Co4Sb12 sample. Double filling also effectively reduced the lattice thermal conductivity by about 46%, thus demonstrating that the overall improvement in ZT was primarily due to the reduced thermal conductivity. A maximum ZT value of 1.15 was achieved at 692 K for In0.3La0.5Co4Sb12.

Superelectrophilic tetrakis(carbonyl)palladium(II)- and -platinum(II) undecafluorodiantimonate(V), [Pd(CO)4][Sb(2)F(11)]2 and [Pt(CO)4][Sb(2)F(11)]2: syntheses, physical and spectroscopic properties, their crystal, molecular, and extended structures, and density functional calculations: an experimental, computational, and comparative study .

PubMed

Willner, H; Bodenbinder, M; Bröchler, R; Hwang, G; Rettig, S J; Trotter, J; von Ahsen, B; Westphal, U; Jonas, V; Thiel, W; Aubke, F

2001-01-31

The salts [M(CO)(4)][Sb(2)F(11)](2), M = Pd, Pt, are prepared by reductive carbonylation of Pd[Pd(SO(3)F)(6)], Pt(SO(3)F)(4) or PtF(6) in liquid SbF(5), or HF-SbF(5). The resulting moisture-sensitive, colorless solids are thermally stable up to 140 degrees C (M = Pd) or 200 degrees C (M = Pt). Their thermal decompositions are studied by differential scanning calorimetry (DSC). Single crystals of both salts are suitable for an X-ray diffraction study at 180 K. Both isostructural salts crystallize in the monoclinic space group P2(1)/c (No. 14). The unit cell volume of [Pt(CO)(4)][Sb(2)F(11)](2) is smaller than that of [Pd(CO)(4)][Sb(2)F(11)](2) by about 0.4%. The cations [M(CO)(4)](2+), M = Pd, Pt, are square planar with only very slight angular and out-of-plane deviations from D(4)(h)() symmetry. The interatomic distances and bond angles for both cations are essentially identical. The [Sb(2)F(11)](-) anions in [M(CO)(4)][Sb(2)F(11)](2,) M = Pd, Pt, are not symmetry-related, and both pairs differ in their Sb-F-Sb bridge angles and their dihedral angles. There are in each salt four to five secondary interionic C- -F contacts per CO group. Of these, two contacts per CO group are significantly shorter than the sum of the van der Waals radii by 0.58 - 0.37 A. In addition, structural, and spectroscopic details of recently synthesized [Rh(CO)(4)][Al(2)Cl(7)] are reported. The cations [Rh(CO)(4)](+) and [M(CO)(4)](2+), M = Pd, Pt, are characterized by IR and Raman spectroscopy. Of the 16 vibrational modes (13 observable, 3 inactive) 10 (Pd, Pt) or 9 (Rh), respectively, are found experimentally. The vibrational assignments are supported by DFT calculations, which provide in addition to band positions also intensities of IR bands and Raman signals as well as internal force constants for the cations. (13)C NMR measurements complete the characterization of the square planar metal carbonyl cations. The extensive characterization of [M(CO)(4)][Sb(2)F(11)](2), M = Pd, Pt, reported

W-Sb-Te phase-change material: A candidate for the trade-off between programming speed and data retention

NASA Astrophysics Data System (ADS)

Peng, Cheng; Wu, Liangcai; Rao, Feng; Song, Zhitang; Yang, Pingxiong; Song, Hongjia; Ren, Kun; Zhou, Xilin; Zhu, Min; Liu, Bo; Chu, Junhao

2012-09-01

W-Sb-Te phase-change material has been proposed to improve the performance of phase-change memory (PCM). Crystallization temperature, crystalline resistance, and 10-year data retention of Sb2Te increase markedly by W doping. The Wx(Sb2Te)1-x films crystallize quickly into a stable hexagonal phase with W uniformly distributing in the crystal lattice, which ensures faster SET speed and better operation stability for the application in practical device. PCM device based on W0.07(Sb2Te)0.93 shows ultrafast SET operation (6 ns) and good endurance (1.8 × 105 cycles). W-Sb-Te material is a promising candidate for the trade-off between programming speed and data retention.

The Co-Sb-Ga System: Isoplethal Section and Thermodynamic Modeling

NASA Astrophysics Data System (ADS)

Gierlotka, Wojciech; Chen, Sinn-wen; Chen, Wei-an; Chang, Jui-shen; Snyder, G. Jeffrey; Tang, Yinglu

2015-04-01

The Co-Sb-Ga ternary system is an important thermoelectric material system, and its phase equilibria are in need of further understanding. The CoSb3-GaSb isoplethal section is experimentally determined in this study. Phase equilibria of the ternary Co-Sb-Ga system are assessed, and the system's thermodynamic models are developed. In addition to the terminal phases and liquid phase, there are six binary intermediate phases and a ternary Co3Sb2Ga4 phase. The Ga solution in the CoSb3 compound is described by a dual-site occupation (GaVF) x Co4Sb12- x/2(GaSb) x/2 model. Phase diagrams are calculated using the developed thermodynamic models, and a reaction scheme is proposed based on the calculation results. The calculated results are in good agreement with the experimentally determined phase diagrams, including the CoSb3-GaSb isoplethal section, the liquidus projection, and an isothermal section at 923 K (650 °C). The dual-site occupation (GaVF) x Co4Sb12- x/2(GaSb) x/2 model gives good descriptions of both phase equilibria and thermoelectric properties of the CoSb3 phase with Ga doping.

The in vitro biocompatibility and macrophage phagocytosis of Mg17Al12 phase in Mg-Al-Zn alloys.

PubMed

Liu, Chen; He, Peng; Wan, Peng; Li, Mei; Wang, Kehong; Tan, Lili; Zhang, Yu; Yang, Ke

2015-07-01

Mg alloys are gaining interest for applications as biodegradable medical implant, including Mg-Al-Zn series alloys with good combination of mechanical properties and reasonable corrosion resistance. However, whether the existence of second phase particles in the alloys exerts influence on the biocompatibility is still not clear. A deeper understanding of how the particles regulate specific biological responses is becoming a crucial requirement for their subsequent biomedical application. In this work, the in vitro biocompatibility of Mg17Al12 as a common second phase in biodegradable Mg-Al-Zn alloys was investigated via hemolysis, cytotoxicity, cell proliferation, and cell adhesion tests. Moreover, osteogenic differentiation was evaluated by the extracellular matrix mineralization assay. The Mg17Al12 particles were also prepared to simulate the real situation of second phase in the in vivo environment in order to estimate the cellular response in macrophages to the Mg17Al12 particles. The experimental results indicated that no hemolysis was found and an excellent cytocompatibility was also proved for the Mg17Al12 second phase when co-cultured with L929 cells, MC3T3-E1 cells and BMSCs. Macrophage phagocytosis co-culture test revealed that Mg17Al12 particles exerted no harmful effect on RAW264.7 macrophages and could be phagocytized by the RAW264.7 cells. Furthermore, the possible inflammatory reaction and metabolic way for Mg17Al12 phase were also discussed in detail. © 2014 Wiley Periodicals, Inc.

Counter-current acid leaching process for the removal of Cu, Pb, Sb and Zn from shooting range soil.

PubMed

Lafond, Stéphanie; Blais, Jean-François; Mercier, Guy; Martel, Richard

2013-01-01

This research explores the performance of a counter-current leaching process (CCLP) for Cu, Pb, Sb and Zn extraction in a polluted shooting range soil. The initial metal concentrations in the soil were 1790 mg Cu/kg, 48,300 mg Pb/kg, 840 mg Sb/kg and 368 mg Zn/kg. The leaching process consisted of five one-hour acid leaching steps, which used 1 M H2SO4 + 4 M NaCl (20 degrees C, soil suspension = 100 g/L) followed by two water rinsing steps. Ten counter-current remediation cycles were completed and the average metal removal yields were 98.3 +/- 0.3% of Cu, 99.5 +/- 0.1% of Pb, 75.5 +/- 5.1% of Sb and 29.1 +/- 27.2% of Zn. The quality of metal leaching did not deteriorate throughout the 10 remediation cycles completed for this study. The CCLP reduced acid and salt use by approximately 68% and reduced water consumption by approximately 60%, exceeding reductions achieved by a standard acid leaching process.

Evaluation of anti-melanoma activities of (1S,2E,4R,6E,8R,11S,12R)-8,12-epoxy-2,6-cembradiene-4,11-diol, (1S,2E,4R,6E,8S,11R,12S)-8,11-epoxy-4,12-epoxy-2,6-cembradiene and (1S,4R,13S)-cembra-2E,7E,11E-trien-4,13-diol from the Red Sea soft coral Sarcophyton glaucum.

PubMed

Szymanski, Pawel T; Ahmed, Safwat A; Radwan, Mohamed M; Khalifa, Sherief I; Fahmy, Hesham

2014-08-01

Three natural cembranoids from the Red Sea soft coral Sarcophyton glaucum namely (1S,2E,4R,6E,8R,11S,12R)-8,12-epoxy-2,6-cembradiene-4,11-diol, (1S,2E,4R,6E,8S,11R,12S)-8,11-epoxy-4,12-epoxy-2,6-cembradiene and (1S,4R,13S)-cembra-2E,7E,11E-trien-4,13-diol were evaluated for their inhibitory effects on mouse melanoma B16F10 cell growth. Results show that all the cembranoids strongly inhibit viability of melanoma cells particularly during 48 -72 hrs treatment and also inhibit de novo DNA synthesis and PARP activity and stimulate fragmentation of DNA. (1S,2E,4R,6E,8R,11S,12R)-8,12-epoxy-2,6-cembradiene-4,11-diol was not cytotoxic to monkey kidney CV-1 cells at the concentration that produces the anti-melanoma effects which indicates that this compound may be a good candidate for further development. (1S,2E,4R,6E,8S,11R,12S)-8,11-epoxy-4,12-epoxy-2,6-cembradiene and (1S,4R,13S)-cembra-2E,7E,11E-trien-4,13-diol were found to be cytotoxic to healthy cells.

Phase Transitions in MIITiF6 · 6H2O (M = Cd, Zn, Co): An EPR Study

NASA Astrophysics Data System (ADS)

Jayaram, Geetha

1994-05-01

Paramagnetic Mn2+ ions have been incorporated into CdTiF6 · 6H2O, ZnTiF6 · 6H2O and CoTiF6 · 6H2O single crystals, and EPR spectra have been utilized to investigate the structural phase transitions in these crystals. They are first order in nature with a marked hysteresis in the case of CoTiF6 · 6H2O and are attributed to hindering of rotation of the [M(H2O)6] as well as (TiF6) groups.

Hard X-ray photoemission study of the Fabre salts (TMTTF)2X (X = SbF6 and PF6)

NASA Astrophysics Data System (ADS)

Medjanik, Katerina; de Souza, Mariano; Kutnyakhov, Dmytro; Gloskovskii, Andrei; Müller, Jens; Lang, Michael; Pouget, Jean-Paul; Foury-Leylekian, Pascale; Moradpour, Alec; Elmers, Hans-Joachim; Schönhense, Gerd

2014-11-01

Core-level photoemission spectra of the Fabre salts with X = SbF6 and PF6 were taken using hard X-rays from PETRA III, Hamburg. In these salts TMTTF layers show a significant stack dimerization with a charge transfer of 1 e per dimer to the anion SbF6 or PF6. At room temperature and slightly below the core-level spectra exhibit single lines, characteristic for a well-screened metallic state. At reduced temperatures progressive charge localization sets in, followed by a 2nd order phase transition into a charge-ordered ground state. In both salts groups of new core-level signals occur, shifted towards lower kinetic energies. This is indicative of a reduced transverse-conductivity across the anion layers, visible as layer-dependent charge depletion for both samples. The surface potential was traced via shifts of core-level signals of an adsorbate. A well-defined potential could be established by a conducting cap layer of 5 nm aluminum which appears "transparent" due to the large probing depth of HAXPES (8-10 nm). At the transition into the charge-ordered phase the fluorine 1 s line of (TMTTF)2SbF6 shifts by 2.8 eV to higher binding energy. This is a spectroscopic fingerprint of the loss of inversion symmetry accompanied by a cooperative shift of the SbF6 anions towards the more positively charged TMTTF donors. This shift does not occur for the X = PF6 compound, most likely due to smaller charge disproportion or due to the presence of charge disorder.

Dewetting and Segregation of Zn-Doped InSb in Microgravity Experiments

NASA Technical Reports Server (NTRS)

Ostrogorsky, A. G.; Marin, C.; Duffar, T.; Volz, M.

2009-01-01

In directional solidification, dewetting is characterized by the lack of contact between the crystal and the crucible walls, due to the existence of a liquid meniscus at the level of the solid-liquid interface. This creates a gap of a few tens of micrometers between the crystal and the crucible. One of the immediate consequences of this phenomenon is the dramatic improvement of the quality of the crystal. This improvement is partly due to the modification of the solid-liquid interface curvature and partly to the absence of sticking and spurious nucleation at the crystal-crucible interface. Dewetting has been, commonly observed during the growth of semiconductors in crucibles under microgravity conditions where it appears to be very stable: the gap between the crystal and the crucible remains constant along several centimetres of growth. The physical models of the phenomenon are well established and they predict that dewetting should not occur in microgravity, if sufficient static pressure is imposed on the melt, pushing it towards the crucible. We present the results of InSb(Zn) solidification experiments conducted at the International Space Station (ISS) where, in spite of a spring exerting a pressure on the liquid, partial dewetting did occur. This surprising result is discussed in terms of force exerted .by the spring on the liquid and of possibility that the spring did not work properly. Furthermore, it appears that the segregation of the Zn was not affected by the occurrence of the dewetting. The data suggest that there was no significant interference of convection with segregation of Zn in InSb.

Superspin glass phase and hierarchy of interactions in multiferroic PbFe1/2Sb1/2O3: an analog of ferroelectric relaxors?

NASA Astrophysics Data System (ADS)

Laguta, V. V.; Stephanovich, V. A.; Savinov, M.; Marysko, M.; Kuzian, R. O.; Kondakova, I. V.; Olekhnovich, N. M.; Pushkarev, A. V.; Radyush, Yu V.; Raevski, I. P.; Raevskaya, S. I.; Prosandeev, S. A.

2014-11-01

We have fabricated new perovskite multiferroic PbFe1/2Sb1/2O3 with a high degree (up to 0.9) of chemical ordering and unexpectedly high-temperature magnetic relaxor properties, which can barely be described within concepts of conventional spin glass physics. Notably, we found that the field-temperature phase diagram of this material, in the extremely wide temperature interval, contains the de Almeida-Thouless-type critical line, which has been the subject of long debates regarding its possible experimental realization. We explain our findings by the creation, at high temperatures of not less than 250 K, of giant superspins (SSs), owing, curiously enough, to the antiferromagnetic superexchange interaction. We show that these SSs are capable of strong high-temperature magnetic relaxation in the relaxor phase, down to about 150 K, where they transform into a SS glass phase. On further cooling, the material experiences another striking transition, this time, into an ordinary (single-spin) antiferromagnetic phase. We comprehensively analyze the above complex physical picture in terms of three complimentary theoretical approaches. Namely, the ab initio calculations elucidate the microscopic mechanism of giant SS formation, the high-temperature expansion accounts for the morphology of these clusters, and the random field approach provides the description of disorder-related characteristics.

The effects of gamma irradiation on electrical characteristics of Zn/ZnO/n-Si/Au-Sb structure

NASA Astrophysics Data System (ADS)

Salari, M. Abdolahpour; Güzeldir, B.; Saǧlam, M.

2018-02-01

In this research, we have investigated the electrical characteristics of Zn/ZnO/n-Si/Au-Sb structure before and after 60Co gamma (γ)-ray source irradiation with the total dose range of 0-500 kGy at room temperature. Electrical measurements of this structure have been performed using current-voltage (I-V) and capacitance-voltage (C-V) techniques. Experimental results show that the values of the ideality factor obtained from I-V measurements increased and the values of the barrier height obtained from reverse-bias C-V measurements decreased after gamma-irradiation. The results show that the main effect of the radiation is the generation of laterally inhomogeneous defects near the semiconductor surface.

Room temperature enhanced red emission from novel Eu(3+) doped ZnO nanocrystals uniformly dispersed in nanofibers.

PubMed

Zhang, Yongzhe; Liu, Yanxia; Li, Xiaodong; Wang, Qi Jie; Xie, Erqing

2011-10-14

Achieving red emission from ZnO-based materials has long been a goal for researchers in order to realize, for instance, full-color display panels and solid-state light-emitting devices. However, the current technique using Eu(3+) doped ZnO for red emission generation has a significant drawback in that the energy transfer from ZnO to Eu(3+) is inefficient, resulting in a low intensity red emission. In this paper, we report an efficient energy transfer scheme for enhanced red emission from Eu(3+) doped ZnO nanocrystals by fabricating polymer nanofibers embedded with Eu(3+) doped ZnO nanocrystals to facilitate the energy transfer. In the fabrication, ZnO nanocrystals are uniformly dispersed in polymer nanofibers prepared by the high electrical field electrospinning technique. Enhanced red emission without defect radiation from the ZnO matrix is observed. Three physical mechanisms for this observation are provided and explained, namely a small ZnO crystal size, uniformity distribution of ZnO nanocrystals in polymers (PVA in this case), and strong bonding between ZnO and polymer through the -OH group bonding. These explanations are supported by high resolution transmission emission microscopy measurements, resonant Raman scattering characterizations, photoluminescence spectra and photoluminescence excitation spectra measurements. In addition, two models exploring the 'accumulation layer' and 'depletion layer' are developed to explain the reasons for the more efficient energy transfer in our ZnO nanocrystal system compared to that in the previous reports. This study provides an important approach to achieve enhanced energy transfer from nanocrystals to ions which could be widely adopted in rare earth ion doped materials. These discoveries also provide more insights into other energy transfer problems in, for example, dye-sensitized solar cells and quantum dot solar cells.

Design, synthesis and photoelectrochemical properties of hexagonal metallomacrocycles based on triphenylamine: [M6(4,4'-bis(2,2':6',2''-terpyridinyl)triphenylamine)6(X)12]; [M = Fe(II), PF6- and Zn(II), BF4-].

PubMed

Hwang, Seok-Ho; Moorefield, Charles N; Wang, Pingshan; Fronczek, Frank R; Courtney, Brandy H; Newkome, George R

2006-08-07

Synthesis of a novel bis(terpyridine) ligand, 4,4'-bis(2,2':6',2''-terpyridinyl)triphenylamine, utilizing triphenylamine, as a specific angle controller, has led to the self-assembly of a unique hexagonal metallomacrocycle family, [Fe6(2)6(PF6)12] and [Zn6(2)6(BF4)12], utilizing terpyridine-metal(II)-terpyridine connectivity. The crystal structure of the novel ligand shows that the angle between the two terpyridinyl moieties is 119.69 degrees , which enabled the formation of the hexagonal-shaped macrocycles. The crystal packing architectures of this starting ligand revealed channels induced by solvent encapsulation. Following complexation of this ligand with transition metals [Fe(II) or Zn(II)] in a one-pot reaction, the resultant structures were characterized by (1)H and (13)C NMR, UV/Vis and mass spectroscopies. The expected metal-to-ligand charge transfer (MLCT; lambda(max) = 582 nm) and emission (lambda(em) = 575 nm) characteristics were exhibited by both [Fe6(2)6(PF6)12] and[Zn6(2)6(BF4)12]. The photoelectrochemical characteristics of these hexagonal metallomacrocycles demonstrate that they can be used as sensitizers in dye-sensitized solar cells.

AsSb energetics in argentian sulfosalts

NASA Astrophysics Data System (ADS)

Ghosal, Subhabrata; Sack, Richard O.

1995-09-01

Experimental brackets on As-Sb partitioning between polybasite-pearceite {Pbp; (Cu, Ag) 16(Sb, As) 2S 11} and pyrargyrite-proustite {Ppr; (Cu, Ag) 3(Sb, As)S 3}, and between pyrargyrite-proustite, and miargyrite and smithite {αMi, βMi, Smt; Ag(Sb, As)S 2} (350-400°C; evacuated silica tubes) define standard state Gibbs energies of theAsSb exchange reactions {Ag 16As 2S 11+Ag 3SbS 3=Ag 16Sb 2S 11 + Ag 3AsS 3, Δ Gro Pbp-Ppr = 0.65 ± 0.60 kJ/gfw; Ag 3AsS 3, + AgSbS 2 = Ag 3SbS 3 + AgASS 2, Δ overlineGro Ppr-α Mi = 3.10 ± 0.50 kJ/gfw, Δ Gro PPr-Smt = 1.70 ± 0.50 kJ/gfw and the nonidealities associated with the AsSb substitutions in these minerals (measured by symmetric regular-solution parameters for formula units on a one AsSb site basis; WAsSbPbp = 4.00 ± 0.25 kJ/gfw; WAsSbPpr =6.00 ± 0 .60 kJ/gfw; WAsSbαMi = WAsSbSmt = 7.00 ± 0.50 kJ/gfw). The above constraints applied to the miscibility gap between Ag (Sb, As) S 2 solutions with α-miargyrite and smithite structures at 350°C determine the relative stabilities of these structures in the As and Sb endmembers to be: ( GSbo, α Mi - GSbo, Smt) ˜ -0.63 kJ/gfw; ( GAso, α Mi - GAsSmt) ˜ 0.77 kJ/gfw. Combining these constraints with the calorimetric data of Bryndzia and Kleppa (1988, 1989) and our melting point determinations we have constructed a phase diagram for the AgSbS 2AgAsS 2 subsystem. The salient features of this diagram are (1) eutectic behaviour ( T ˜ 396°C, XAs ˜ 0.50), (2) modest increase in the temperature of the α → β miargyrite transition with As substitution (˜380°C in Sb-subsystem; 386.6°C at XAsMi ˜ 0.36), (3) a 42.5°C depression of the trechmannite-smithite transition with preferential incorporation of Sb in smithite { smithite ( XAs ˜ 0.62) → α-miargyrite ( XAs ˜ 0.34) + trechmannite (X As ˜ 1.00) at ˜277.5°C}, and (4) widening of the miargyrite-trechmannite gap at lower temperatures. The latter feature is consistent with the inference that the most As

Zn-Ge-Sb glass composite mixed with Ba2+ ions: a high capacity anode material for Na-ion batteries

NASA Astrophysics Data System (ADS)

Ravuri, Balaji Rao; Gandi, Suman; Chinta, Srinivasa Rao

2018-06-01

(100-x)(0.7[0.625ZnO-0.375GeO2]-0.3Sb2O3)-xBaO (x = 0, 2, 4 and 6 mol%, labeled as ZGSB x ) glass anode samples are synthesized using a high-energy ball-milling method and employed as anode material for Na-ion batteries. The results on microstructures (XRD, SEM) and electrochemical properties (constant current charge/discharge tests, CV and EIS) indicated that the optimum concentration of Ba2+ ions in the Zn-Ge-Sb glass anode network exhibits the pillaring effect, which would lead to increased electrical conductivity, minimize the volume changes, cracks and voids to boost up electrochemical performance. The ZGSB4 glass anode sample exhibits good capacity retention even after 20 cycles with 95% coulombic efficiency, which is a significant trend for a successful anode network. Electrochemical performance is considerably enhanced by reducing the cut-off voltage from 2 to 1.25 V due to the disassembly of amorphous intermediate domains, optimum volume changes and increased electrical conductivity in this ZGSB x glass network.

The unusual chemical bonding and thermoelectric properties of a new type Zintl phase compounds Ba3Al2As4

NASA Astrophysics Data System (ADS)

Yang, Gui; Zhang, Guangbiao; Wang, Chao; Wang, Yuanxu

2016-07-01

Ba3Al2As4 exhibits an unusual anisotropic electrical conductivity, that is, the electrical conductivity along the chain is smaller than those along other two directions. The results is conflict with previous conclusion for Ca5M2Pn6. Earlier studies on Ca5M2Pn6 showed that a higher electrical conductivity could be obtained along the chain. The band decomposed charge density is used to explain such unusual behavior. Our calculations indicate the existence of a conductive pathway near the Fermi level is responsible for the electrons transport. Further, the Ba-As bonding of Ba3Al2As4 has some degree covalency which is novel for the Zintl compounds.

Effects of phase transformation on the microstructures and magnetostriction of Fe-Ga and Fe-Ga-Zn ferromagnetic shape memory alloys

NASA Astrophysics Data System (ADS)

Lin, Yin-Chih; Lin, Chien-Feng

2015-05-01

The phase transformation and magnetostriction of bulk Fe73Ga27 and Fe73Ga18Zn9 (at. %) ferromagnetic shape memory alloys (FSMs) were investigated by transmission electron microscopy (TEM), x-ray diffraction (XRD), and a magnetostrictive-meter setup. For the Fe73Ga27 FSM alloy solution treated at 1100 °C for 4 h and quenched in ice brine, the antiphase boundary segments of the D03 domain were observed in the A2 (disordered) matrix, and the Fe73Ga27 FSM alloy had an optimal magnetostriction (λ‖s = 71 × 10-6 and λ⊥s = -31 × 10-6). In Fe73Ga27 FSM alloy as-quenched, aged at 700 °C for 24 h, and furnace cooled, D03 nanoclusters underwent phase transformation to an intermediate tetragonal phase (i.e., L10-like martensite) via Bain distortion, and finally L12 (Fe3Ga) structures precipitated, as observed by TEM and XRD. The L10-like martensite and L12 phases in the aged Fe73Ga27 FSM alloy drastically decreased the magnetostriction from positive to negative (λ‖s = -20 × 10-6 and λ⊥s = -8 × 10-6). However, in Fe73Ga18Zn9 FSM alloy as-quenched and aged, the phase transformation of D03 to an intermediate tetragonal martensite phase and precipitation of L12 structures were not found. The results indicate that the aged Fe73Ga18Zn9 FSM alloy maintained stable magnetostriction (λ‖s = 36 × 10-6 and λ⊥s = -31 × 10-6). Adding Zn can improve the ferromagnetic shape memory effect of aged Fe73Ga18Zn9 alloy, which may be useful in application of the alloy in high temperature environments.

Quantum dots grown in the InSb/GaSb system by liquid-phase epitaxy

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

Parkhomenko, Ya. A.; Dement’ev, P. A.; Moiseev, K. D., E-mail: mkd@iropt2.ioffe.rssi.ru

2016-07-15

The first results of the liquid-phase epitaxial growth of quantum dots in the InSb/GaSb system and atomic-force microscopy data on the structural characteristics of the quantum dots are reported. It is shown that the surface density, shape, and size of nanoislands depend on the deposition temperature and the chemical properties of the matrix surface. Arrays of InSb quantum dots on GaSb (001) substrates are produced in the temperature range T = 450–465°C. The average dimensions of the quantum dots correspond to a height of h = 3 nm and a base dimension of D = 30 nm; the surface densitymore » is 3 × 10{sup 9} cm{sup –2}.« less

Laser-induced phase transitions of Ge2Sb2Te5 thin films used in optical and electronic data storage and in thermal lithography.

PubMed

Chu, Cheng Hung; Shiue, Chiun Da; Cheng, Hsuen Wei; Tseng, Ming Lun; Chiang, Hai-Pang; Mansuripur, Masud; Tsai, Din Ping

2010-08-16

Amorphous thin films of Ge(2)Sb(2)Te(5), sputter-deposited on a ZnS-SiO(2) dielectric layer, are investigated for the purpose of understanding the structural phase-transitions that occur under the influence of tightly-focused laser beams. Selective chemical etching of recorded marks in conjunction with optical, atomic force, and electron microscopy as well as local electron diffraction analysis are used to discern the complex structural features created under a broad range of laser powers and pulse durations. Clarifying the nature of phase transitions associated with laser-recorded marks in chalcogenide Ge(2)Sb(2)Te(5) thin films provides useful information for reversible optical and electronic data storage, as well as for phase-change (thermal) lithography.

Biodegradation of the ZnO:Eu nanoparticles in the tissues of adult mouse after alimentary application.

PubMed

Kielbik, Paula; Kaszewski, Jaroslaw; Rosowska, Julita; Wolska, Ewelina; Witkowski, Bartłomiej S; Gralak, Mikolaj A; Gajewski, Zdzisław; Godlewski, Marek; Godlewski, Michal M

2017-04-01

Biodegradable zinc oxide nanoparticles (ZnO NPs) are considered promising materials for future biomedical applications. To fulfil this potential, biodistribution and elimination patterns of ZnO NPs in the living organism need to be resolved. In order to investigate gastrointestinal absorption of ZnO NPs and their intra-organism distribution, water suspension of ZnO or fluorescent ZnO:Eu (Europium-doped zinc oxide) NPs (10mg/ml; 0.3ml/mouse) was alimentary-administered (IG: intra-gastric) to adult mice. Internal organs collected at key time-points after IG were evaluated by AAS for Zn concentration and analysed by cytometric techniques. We found that Zn-based NPs were readily absorbed and distributed (3 h post IG) in the nanoparticle form throughout the organism. Results suggest, that liver and kidneys were key organs responsible for NPs elimination, while accumulation was observed in the spleen and adipose tissues. We also showed that ZnO/ZnO:Eu NPs were able to cross majority of biological barriers in the organism (including blood-brain-barrier). Copyright © 2016 Elsevier Inc. All rights reserved.

Thermoluminescence of pure and Eu-doped NaZnF3

NASA Astrophysics Data System (ADS)

Furetta, C.; Graziani, M.; Sanipoli, C.; Scacco, A.

Thermoluminescence of pure and Eu-doped NaZnF3 fluoroperovskite is studied in order to determine nature of emitting centres and possible dosimetric properties. Intrinsic and extrinsic defects, some of them due to surface oxidation processes, are related to peaks in the glow curves of the two systems.

Canted antiferromagnetism in phase-pure CuMnSb

NASA Astrophysics Data System (ADS)

Regnat, A.; Bauer, A.; Senyshyn, A.; Meven, M.; Hradil, K.; Jorba, P.; Nemkovski, K.; Pedersen, B.; Georgii, R.; Gottlieb-Schönmeyer, S.; Pfleiderer, C.

2018-05-01

We report the low-temperature properties of phase-pure single crystals of the half-Heusler compound CuMnSb grown by means of optical float zoning. The magnetization, specific heat, electrical resistivity, and Hall effect of our single crystals exhibit an antiferromagnetic transition at TN=55 K and a second anomaly at a temperature T*≈34 K. Powder and single-crystal neutron diffraction establish an ordered magnetic moment of (3.9 ±0.1 ) μB/f .u . , consistent with the effective moment inferred from the Curie-Weiss dependence of the susceptibility. Below TN, the Mn sublattice displays commensurate type-II antiferromagnetic order with propagation vectors and magnetic moments along <111 > (magnetic space group R [I ]3 c ). Surprisingly, below T*, the moments tilt away from <111 > by a finite angle δ ≈11∘ , forming a canted antiferromagnetic structure without uniform magnetization consistent with magnetic space group C [B ]c . Our results establish that type-II antiferromagnetism is not the zero-temperature magnetic ground state of CuMnSb as may be expected of the face-centered cubic Mn sublattice.

Influence of Surrounding Dielectrics on the Data Retention Time of Doped Sb2Te Phase Change Material

NASA Astrophysics Data System (ADS)

Jedema, Friso; in `t Zandt, Micha; Wolters, Rob; Gravesteijn, Dirk

2011-02-01

The crystallization properties of as-deposited and laser written amorphous marks of doped Sb2Te phase change material are found to be only dependent on the top dielectric layer. A ZnS:SiO2 top dielectric layer yields a higher crystallization temperature and a larger crystal growth activation energy as compared to a SiO2 top dielectric layer, leading to superior data retention times at ambient temperatures. The observed correlation between the larger crystallization temperatures and larger crystal growth activation energies indicates that the viscosity of the phase change material in the amorphous state is dependent on the interfacial energy between the phase change material and the top dielectric layer.

Color-tunable photoluminescence and energy transfer properties of single-phase Ba{sub 10}(PO{sub 4}){sub 6}O:Eu{sup 2+}, Mn{sup 2+} phosphors

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

Guo, Qingfeng; Liao, Libing, E-mail: clayl@cugb.edu.cn; Mei, Lefu, E-mail: mlf@cugb.edu.cn

2015-12-15

Single-phase Ba{sub 10−x−y}(PO{sub 4}){sub 6}O:xEu{sup 2+},yMn{sup 2+} samples with apatite structure have been synthesized via a solid-state reaction method. The phase structure, luminescence properties, lifetime, PL thermal stability, as well as fluorescence decay curves of the samples were investigated. Effective energy transfer occurs from Eu{sup 2+} to Mn{sup 2+} in Ba{sub 10}(PO{sub 4}){sub 6}O and a possible mechanism of the energy-transfer from Eu{sup 2+} to Mn{sup 2+} is proposed. The critical distances R{sub c} was calculated by concentration quenching and turned out to be about 0.817 nm (x{sub c}=0.21). The CIE and thermally stable luminescence behaviors of Ba{sub 9.94}(PO{sub 4}){submore » 6}O:0.06Eu{sup 2+} phosphor were also studied in detail. All the results indicate that Ba{sub 10−x−y}(PO{sub 4}){sub 6}O:xEu{sup 2+}, yMn{sup 2+} phosphors have potential applications as near UV-convertible phosphors for white light-emitting diodes. - Graphical abstract: Crystal structure and luminescence property of Ba{sub 10−x−y}(PO{sub 4}){sub 6}O:xEu{sup 2+},yMn{sup 2+} have been discussed. - Highlights: • Ba{sub 10−x−y}(PO{sub 4}){sub 6}O:xEu{sup 2+},yMn{sup 2+} was firstly reported. • Ba{sub 9.94}(PO{sub 4}){sub 6}O:0.06Eu{sup 2+} exhibits high thermal quenching resistance. • The energy transfer between Eu{sup 2+} and Mn{sup 2+} was investigated.« less

Dielectric and varistor properties of rare-earth-doped ZnO and CaCu3Ti4O12 composite ceramics

NASA Astrophysics Data System (ADS)

Lu, Huafei; Lin, Yuanhua; Yuan, Jiancong; Nan, Cewen; Chen, Kexin

2013-02-01

To investigate the multi-functional ceramics with both high permittivity and large nonlinear coefficient, we have prepared rare-earth Tb-and-Co doped ZnO and TiO2-rich CaCu3Ti4O12 (TCCTO) powders by chemical co-precipitation and sol-gel methods respectively, and then obtained the TCCTO/ZnO composite ceramics, sintered at 1100°C for 3 h in air. Analyzing the composite ceramics of the microstructure and phase composition indicated that the composite ceramics were composed of the main phases of ZnO and CaCu3Ti4O12 (CCTO). Our results revealed that the TCCTO/ZnO composite ceramics showed both high dielectric and good nonlinear electrical behaviors. The composite ceramic of TCCTO: ZnO = 0.3 exhibited a high dielectric constant of 210(1 kHz) with a nonlinear coefficient of 11. The dielectric behavior of TCCTO/ZnO composite could be explained by the mixture rule. With the high dielectric permittivity and tunable varistor behaviors, the composite ceramics has a potential application for the higher voltage transportation devices.

Effects of the copper content on the structural and electrical properties of Cu2ZnSnSe4 bulks

NASA Astrophysics Data System (ADS)

Tsega, Moges; Dejene, F. B.; Koao, L. F.

2016-01-01

We have investigated the concept of defect in CuxZnSnSe4 (x=1.6-2.0) and Cuy(Zn0.9Sn1.1)Se4 (y= 1.6-2.0) bulks prepared by liquid-phase sintering at 600 °C for 2 h with soluble sintering aids of Sb2S3 and Te. All samples were found to exhibit p-type semiconductor for CuxZnSnSe4, while n-type of behavior obtained at y= 1.8-2.0 for Cuy(Zn0.9Sn1.1)Se4 pellets. The Cu vacancy acts as an acceptor point defect to form the p-type semiconductor, and Sn4+ acts as a donor to form the n-type behavior for the Sn-rich CZTSe. SEM images of pellets show dense surface morphology, and increase in grain size upon Cu inclusion. The largely increased Hall mobility and the slightly changed carrier concentration for Cuy(Zn0.9Sn1.1)Se4 with increasing the Cu content is related to the types of its defects. At y=2.0 with carrier concentration of 4.88×1017 cm-3 showed the highest mobility of around 58 cm2/V s. Based upon the proposed point defects, the CZTSe property can be consistently explained.

Phase relations in the pseudo ternary system In2O3-TiO2-BO (B: Zn, Co and Ni) at 1200 °C in air

NASA Astrophysics Data System (ADS)

Brown, Francisco; Jacobo-Herrera, Ivan Edmundo; Alvarez-Montaño, Victor Emmanuel; Kimizuka, Noboru; Hirano, Tomonosuke; Sekine, Ryotaro; Denholme, Saleem J.; Miyakawa, Nobuaki; Kudo, Akihiko; Iwase, Akihide; Michiue, Yuichi

2018-02-01

Phase relations in the pseudo ternary systems In2O3-TiO2-ZnO, In2O3-TiO2-CoO and In2O3-TiO2-NiO at 1200 °C in air were determined by means of a classic quenching method. In6Ti6BO22 (B: Zn, Co and Ni) which has the monoclinic In(Fe1/4Ti3/4)O27/8-type of structure with a 4-dimensional super space group exists in a stable form. There exist homologous phases In1+x(Ti1/2Zn1/2)1-xO3(ZnO)m (m: natural number, 0ZnO)m-type of the layered crystal structures such as In1+x(Ti1/2Zn1/2)1-xO3(ZnO) (0.12 ≤ x ≤ 0.29), In1+x(Ti1/2Zn1/2)1-x(ZnO)2 (0.12 ≤ x ≤ 0.50), In1+x(Ti1/2Zn1/2)1-xO3(ZnO)3 (0.15 ≤ x ≤ 0.84), In1+x(Ti1/2Zn1/2)1-x(ZnO)4 (0.15 ≤ x ≤ 1), In1+x(Ti1/2Zn1/2)1-xO3(ZnO)5 (0.15 ≤ x ≤ 1), In1+x(Ti1/2Zn1/2)1-x(ZnO)6 (0.15 ≤ x ≤ 1), In1+x(Ti1/2Zn1/2)1-xO3(ZnO)7 (0.15 ≤ x ≤ 1), In1+x(Ti1/2Zn1/2)1-x(ZnO)8 (?1/2Zn1/2)1-xO3(ZnO)9 (0.15 ≤ x ≤ 1), In1+x(Ti1/2Zn1/2)1-x(ZnO)10 (?1/2Zn1/2)1-xO3(ZnO)11 (0.15 ≤ x ≤ 1)… without an upper limit of m in the pseudo ternary system In2O3-TiO2-ZnO. All the ions are on the trigonal lattice points, the In(III) is in the octahedral coordination with the oxygen and the {Inx(Ti1/2Zn1/2)1-xZnm} is in the trigonalbipyramidal coordination with oxygen in the crystal structures of each homologous compound. They have R 3 bar m (No. 166) for m = odd or P63/mmc (No. 194) for m = even in space group. Lattice constants for each of the homologous compounds as a hexagonal setting and In6Ti6BO22 as the monoclinic system were determined by means of the powder X-ray diffraction method at room temperature. The temperature dependence of resistivity for In1+x(Ti1/2Zn1/2)1-x(ZnO)4 (0.15 ≤ x ≤ 1) showed semiconducting-like behavior for all samples examined at T(K) = 2-300. The resistivity increased systematically with decreasing x (0.7 ≤ x ≤ 1), and it was found that samples where x ≤ 0.7 became insulators. The optical band gap Eg (eV) of In1+x(Ti1/2Zn

MOVPE of GaSb/InGaAsSb Multilayers and Fabrication of Dual Band Photodetectors

NASA Technical Reports Server (NTRS)

Xiao, Ye-Gao; Bhat, Ishwara; Refaat, Tamer F.; Abedin, M. Nurul; Shao, Qing-Hui

2005-01-01

Metalorganic vapor phase epitaxy (MOVPE) of GaSb/InGaAsSb multilayer thin films and fabrication of bias-selectable dual band photodetectors are reported. For the dual band photodetectors the short wavelength detector, or the upper p- GaSb/n-GaSb junction photodiode, is placed optically ahead of the long wavelength one, or the lower photodiode. The latter is based on latticed-matched In0.13Ga0.87As0.11Sb0.89 with bandgap near 0.6 eV. Specifically, high quality multilayer thin films are grown sequentially from top to bottom as p+-GaSb/p-GaSb/n-GaSb/n-InGaAsSb/p-InGaAsSb/p-GaSb on undoped p-type GaSb substrate, and as n-GaSb/p-GaSb/p-InGaAsSb/n-InGaAsSb/n-GaSb on Te-doped n-type GaSb substrate respectively. The multilayer thin films are characterized by optical microscope, atomic force microscope (AFM), electron microprobe analyses etc. The photodiode mesa steps are patterned by photolithography with wet chemical etching and the front metallization is carried out by e-beam evaporation with Pd/Ge/Au/Ti/Au to give ohmic contact on both n- and p-type Sb based layer surfaces. Dark I-V measurements show typical diode behavior for both the upper and lower photodiodes. The photoresponsivity measurements indicate that both the upper and lower photodiodes can sense the infrared illumination corresponding to their cutoff wavelengths respectively, comparable with the simulation results. More work is underway to bring the long wavelength band to the medium infrared wavelength region near 4 micrometers.

Performance of Ge-Sb-Bi-Te-B Recording Media for Phase-Change Optical Disks

NASA Astrophysics Data System (ADS)

Lee, Chain-Ming; Yen, Wen-Shin; Liu, Ren-Haur; Chin, Tsung-Shune

2001-09-01

We investigated the physical properties of GeSbBiTeB materials and examined the feasibility for phase change recording. The studied compositions were Ge4Sb0.5Bi0.5Te5 and Ge2Sb1.5Bi0.5Te5 with B doping. The coexistence of Bi and B atoms into both Ge4SbTe5 and Ge2Sb2Te5 lattice maintains single fcc structure without phase separation. The Bi substitution shows benefits in decreasing crystallization temperature and activation energy, however the reflectivity is slightly reduced. 3 With small amount addition of boron about 1 at.%, the reflectivity can be increased. 2 Conventional 4-layer structure of digital versatile disk-random access memory (DVD-RAM) 2.6 GB format was used to prepare the disks for dynamic characterization and overwrite cyclability evaluations. The disk with Ge4Sb0.5Bi0.5Te5(B) recording layer shows large noise fluctuation and low overwrite erase ratio, suggesting that the crystallization speed is still insufficient. While the disk with Ge2Sb1.5Bi0.5Te5(B) recording layer shows lower writing and erasing powers, stable noise level and high overwrite erase ratio, indicating the capability for DVD-RAM applications. The effect of B doping was verified to enhance the signal amplitude and modulation.

Geospatial Mapping of Pb, Cr, Cu, Zn, Cd, and Sb in Urban Soil, Cd. Juarez, Chihuahua, Mexico

NASA Astrophysics Data System (ADS)

Amaya, M. A.; Grimida, S. E.; Elkekli, A. R.; Aldouri, R. K.; Benedict, B. A.; Pingitore, N. E., Jr.

2015-12-01

Population-based random stratified sampling of the city of Cd. Juarez, Chihuahua, Mexico provided 500 city blocks for study. We collected soil from the public space (where present) in front of each house on a selected block; equal measured small volumes of these were combined to produce a composite sample for analysis. Such composite samples (1) decrease, by an order of magnitude, laboratory processing and analysis costs, and (2) smooth the data to represent blocks as averages of individual houses. Retention of the unanalyzed samples of the individual houses permits their later analysis should the composites suggest further study of individual houses on an anomalous block. Elemental analysis of 10 mg pressed powders was performed on a Panalytical Epsilon5 EDS-XRF, via 8 secondary targets and 12 USGS and NIST multi-element rock standards. The mean and (range) of concentration for Pb was 43 (13-550) ppm; for Cr, 31 (1.8-76); for Cu, 22 (6-550); for Zn 84 (42-415) ppm; for Cd, 1.9 (0.1-6.2); and for Sb, 5.9 (2.7-29). The old urban core of Cd. Juarez was marked by high levels of Pb, Cr, Cu, and Zn, and, to a smaller degree, of Cd and Sb. This pattern mirrors that of contiguous El Paso, Texas, USA, directly across the narrow Rio Grande. Businesses, industrial facilities, transportation (both railroads and highways), traditional "downtown" shopping, and old residential districts cluster in this urban core. A Pb-Cu-Zn smelter, which operated for more than a century until 1999, is present in the US adjacent to the Rio Grande, about two km away from downtown Cd. Juarez. Thus the city has been subject to both traditional metal sources (e.g., leaded gasoline, highway debris) and smelter emissions. The poplation of Cd. Juarez has exploded in the last few decades to some 1.5 million inhabitants due both to natural growth and in-migration from rural districts for economic opportunity. Most of this growth has been accommodated by radial expansion of the city into the surrounding

Phase Change Characteristics of InxSb40-xTe60 Chalcogenide Alloy for Phase Change Random Access Memory

NASA Astrophysics Data System (ADS)

Yun, Jae-Jin; Lee, Won-Jong

2011-07-01

The InxSb40-xTe60 alloy was selected as a new alternative phase change material for Ge2Sb2Te5 (GST) for phase change random access memory (PRAM). The crystal structure of InxSb40-xTe60 was an α(Sb2Te3) rhombohedral (a=b=c, α=β=γ≠90°) single phase with identical lattice parameters in a wide composition range of In (0-28 at. %). The crystallization temperature and melting point of InxSb40-xTe60 were in the ranges of 149-219 °C and 608-614 °C, respectively, and similar to those of GST. The electric properties of InxSb40-xTe60 with a wide composition range of In contents showed the typical PRAM properties such as current-voltage (I-V), resistance-voltage (R-V), and switching behavior. The reset current of InxSb40-xTe60 decreased with increasing In content and the low power consumption and good retention can be realized by controlling In content. The ratio of the cell resistance and sheet resistance of amorphous InxSb40-xTe60 to those crystalline InxSb40-xTe60 were almost the same as or larger than those of GST. The cycling endurance test of InxSb40-xTe60 with a wide range of In contents showed the comparable results to GST. InxSb40-xTe60 was concluded to be a very promising phase change material for PRAM.

Electrical transport property, thermal stability and oxidation resistance of single crystalline β-Zn4Sb3 prepared using the Bi-Sn mixed-flux method

NASA Astrophysics Data System (ADS)

Deng, Shuping; Li, Decong; Chen, Zhong; Tang, Yu; Shen, Lanxian; Deng, Shukang

2017-12-01

Single crystal samples β-Zn4Sb3 have been prepared by using Bi-Sn mixed-flux method. The obtained crystals exhibit p-type conduction behavior with carrier concentration varying from 4.40 × 1019 to 18.12 × 1019 cm-3 as carrier mobility changes from 25.8 to 61.5 cm2 V-1 s-1 at room temperature. Electrical transport properties of the samples were optimized by Bi-Sn co-doped, which brought by Bi-Sn mixed-flux. And the maximal power factor of 1.45 × 10-3 W m-1 K-2 is achieved at 510 K for the sample with Bi flux content x = 0.5. Consequently, the oxidation resistance of the sample was determined by exploring the effects of heat treatment in air on electrical transport properties and thermal stability, which the single crystalline β-Zn4Sb3 still possess an excellent oxidation resistance and thermal stability after the heat treatment process.

Inelastic neutron scattering investigation of low temperature phase transition in Rb2ZnCl4 and K2ZnCl4

NASA Astrophysics Data System (ADS)

Quilichini, M.; Dvořák, V.; Boutrouille, P.

1991-09-01

Inelastic scattering of neutrons has revealed soft optic modes at the T point frac{1}{2}({b}^*+{c}^*) of the Brillouin zone both in Rb2ZnCl4 and K2ZnCl4 which are responsible for the phase transition from the ferroelectric to the lowest temperature phase of these materials. Moreover, in K2ZnCl4 near the T point a minimum on the soft optic branch in the direction (μ{b}^*+frac{1}{2}{c}^*) has been found which confirms the existence of a new incommensurate phase recently discovered by Gesi. The origin of this incommensurate phase is discussed from a phenomenological point of view and formulae for elastic constants are derived describing their behaviour near transition into incommensurate phase. Des mesures de diffusion inélastique des neutrons ont mis en évidence l'existence d'un mode optique mou au point T(frac{1}{2}({b}^*+{c}^*)) de la zone de Brillouin responsable de la transition de la phase ferroélectrique vers la phase basse température dans les deux composés Rb2ZnCl4 and K2ZnCl4. Pour K2ZnCl4 on montre que la branche optique molle présente un minimum au voisinage de T dans la direction (μ{b}^*+frac{1}{2}{c}^*), ce qui confirme l'existence de la nouvelle phase incommensurable récemment trouvée par Gesi. L'origine de cette phase est discutée sur la base d'un modèle phénoménologique dont on dérive aussi les formules des constantes élastiques et leur comportement au voisinage de la transition vers la phase incommensurable.

AlGaAsSb Vapor Phase Epitaxy and Laser Program.

DTIC Science & Technology

1983-06-01

graded or step-graded ternary film structures to fulfill the role of a sub- strate. One of the objectives of the program, however, was to determine the...0.02 ur/mmn. 27 MRDC81-14083 Fig. 11 RED pattern of the ( iaSb sample of Fig. 6. 28 7- 7 crystal. No samples from this group were submitted to SEM

The effect of cooling rate on the phase formation and magnetocaloric properties in La0.6Ce0.4Fe11.0Si2.0 alloys

NASA Astrophysics Data System (ADS)

Yang, Jian; Shao, Yanyan; Feng, Zaixin; Liu, Jian

2018-04-01

In this work, the microstructure, phase formation behavior of the NaZn13-type 1:13 phase and related magnetocaloric effect have been investigated in La0.6Ce0.4Fe11.0Si2.0 as-cast bulk and melt-spun ribbons with different cooling rates. A multi-phase structure consisting of 1:13, α-Fe and La-rich phases is observed in the induction-melted sample with slow cooling. By fast cooling in the melt spinning processing, the La-rich phase can be almost eliminated and thus 1:13 phases with volume fraction as high as 74.4% directly form in the absence of further heat treatment. The resulting maximum magnetic entropy change of 3.1 J/kg K in 2 T field appears at its Curie temperature of 210 K for the La0.6Ce0.4Fe11.0Si2.0 ribbon prepared in 25 m/s.

Temperature-driven topological quantum phase transitions in a phase-change material Ge2Sb2Te5.

PubMed

Eremeev, S V; Rusinov, I P; Echenique, P M; Chulkov, E V

2016-12-13

The Ge 2 Sb 2 Te 5 is a phase-change material widely used in optical memory devices and is a leading candidate for next generation non-volatile random access memory devices which are key elements of various electronics and portable systems. Despite the compound is under intense investigation its electronic structure is currently not fully understood. The present work sheds new light on the electronic structure of the Ge 2 Sb 2 Te 5 crystalline phases. We demonstrate by predicting from first-principles calculations that stable crystal structures of Ge 2 Sb 2 Te 5 possess different topological quantum phases: a topological insulator phase is realized in low-temperature structure and Weyl semimetal phase is a characteristic of the high-temperature structure. Since the structural phase transitions are caused by the temperature the switching between different topologically non-trivial phases can be driven by variation of the temperature. The obtained results reveal the rich physics of the Ge 2 Sb 2 Te 5 compound and open previously unexplored possibility for spintronics applications of this material, substantially expanding its application potential.

Highly textured and transparent RF sputtered Eu2O3 doped ZnO films

PubMed Central

Sreedharan, Remadevi Sreeja; Ganesan, Vedachalaiyer; Sudarsanakumar, Chellappan Pillai; Bhavsar, Kaushalkumar; Prabhu, Radhakrishna; Mahadevan Pillai, Vellara Pappukutty Pillai

2015-01-01

Background Zinc oxide (ZnO) is a wide, direct band gap II-VI oxide semiconductor. ZnO has large exciton binding energy at room temperature, and it is a good host material for obtaining visible and infrared emission of various rare-earth ions. Methods Europium oxide (Eu2O3) doped ZnO films are prepared on quartz substrate using radio frequency (RF) magnetron sputtering with doping concentrations 0, 0.5, 1, 3 and 5 wt%. The films are annealed in air at a temperature of 773 K for 2 hours. The annealed films are characterized using X-ray diffraction (XRD), micro-Raman spectroscopy, atomic force microscopy, ultraviolet (UV)-visible spectroscopy and photoluminescence (PL) spectroscopy. Results XRD patterns show that the films are highly c-axis oriented exhibiting hexagonalwurtzite structure of ZnO. Particle size calculations using Debye-Scherrer formula show that average crystalline size is in the range 15–22 nm showing the nanostructured nature of the films. The observation of low- and high-frequency E2 modes in the Raman spectra supports the hexagonal wurtzite structure of ZnO in the films. The surface morphology of the Eu2O3 doped films presents dense distribution of grains. The films show good transparency in the visible region. The band gaps of the films are evaluated using Tauc plot model. Optical constants such as refractive index, dielectric constant, loss factor, and so on are calculated using the transmittance data. The PL spectra show both UV and visible emissions. Conclusion Highly textured, transparent, luminescent Eu2O3 doped ZnO films have been synthesized using RF magnetron sputtering. The good optical and structural properties and intense luminescence in the ultraviolet and visible regions from the films suggest their suitability for optoelectronic applications. PMID:25765728

UV excited downconversion luminescence properties of Eu3+: NaZnPO4 phosphors

NASA Astrophysics Data System (ADS)

Mukhopadhyay, Lakshmi; Rai, Vineet Kumar

2018-05-01

The structural and optical properties of Eu3+: NaZnPO4 phosphors prepared by chemical coprecipitation method have been studied. The phase formation and morphology of the phosphors have been confirmed by the X-ray diffraction (XRD) and Field emission scanning electron microscopy (FESEM) analysis. The downconversion emission spectra upon 392 nm excitation exhibit five emission bands centred at ˜ 575 nm, ˜ 590 nm, ˜ 612 nm, ˜ 660 nm and ˜ 702 nm corresponding to the 5D0→7F0, 5D0→7F1, 5D0→7F2, 5D0→7F3 and 5D0→7F4 transitions of Eu3+ ions respectively. The observed downconversion emission peaks can be explained with the help of suitable energy level diagram. The CIE chromaticity diagram shows the purity of the emitted colour from the prepared phosphors. The present phosphors emit in intense red region which shows the applicability of the phosphors in red light emitting display devices.

A new photoluminescence emission peak of ZnO SiO2 nanocomposites and its energy transfer to Eu3+ ions

NASA Astrophysics Data System (ADS)

Hong, Jian-He; Cong, Chang-Jie; Zhang, Zhi-Guo; Zhang, Ke-Li

2007-07-01

This work reports a new photoluminescence (PL) emission peak at about 402 nm from amorphous ZnO nanoparticles in a silica matrix, and the energy transfer from it to Eu3+ ions. The amorphous ZnO SiO2 nanocomposites were prepared by the sol gel method, which is verified by X-ray diffraction (XRD) profiles and FT IR spectra. The luminescence emission spectra are fitted by four Gauss profiles, two of which at longer wavelength are due to the defects of the material and the others to amorphous ZnO nanoparticles and the Zn O Si interface state. With the reduction of Zn/Si ratio and diethanolamine, the relative intensities of visible emission decrease. The weak visible emission is due to the reduction of defects after calcined at high temperature. The new energy state at the Zn O Si interface results in strong emission at about 402 nm. When Eu3+ ions are co-doped, weak energy transfer from ZnO SiO2 nanocomposites to Eu3+ emission are observed in the excitation spectra.

Direct modulation of tracheal Cl--channel activity by 5,6- and 11,12-EET.

PubMed

Salvail, D; Dumoulin, M; Rousseau, E

1998-09-01

Using microelectrode potential measurements, we tested the involvement of Cl- conductances in the hyperpolarization induced by 5,6- and 11,12-epoxyeicosatrienoic acid (EET) in airway smooth muscle (ASM) cells. 5,6-EET and 11,12-EET (0.75 microM) caused -5.4 +/- 1.1- and -3.34 +/- 0.95-mV hyperpolarizations, respectively, of rabbit tracheal cells (from a resting membrane potential of -53.25 +/- 0.44 mV), with significant residual repolarizations remaining after the Ca2+-activated K+ channels had been blocked by 10 nM iberiotoxin. In bilayer reconstitution experiments, we demonstrated that the EETs directly inhibit a Ca2+-insensitive Cl- channel from bovine ASM; 1 microM 5,6-EET and 1.5 microM 11,12-EET lowered the unitary current amplitude by 40 (n = 6 experiments) and 44.7% (n = 4 experiments), respectively. Concentration-dependent decreases in channel open probability were observed, with estimated IC50 values of 0.26 microM for 5,6- and 1.15 microM for 11,12-EET. Furthermore, pharmacomechanical tension measurements showed that both regioisomers induced significant bronchorelaxations in epithelium-denuded ASM strips. These results suggest that 5,6- and 11,12-EET can act in ASM as epithelium-derived hyperpolarizing factors.

Thermoelectric properties of Co4Sb12 with Bi2Te3 nanoinclusions

NASA Astrophysics Data System (ADS)

Ghosh, Sanyukta; Bisht, Anuj; Karati, Anirudha; Rogl, Gerda; Rogl, Peter; Murty, B. S.; Suwas, Satyam; Mallik, Ramesh Chandra

2018-03-01

The figure of merit (zT) of a thermoelectric material can be enhanced by incorporation of nanoinclusions into bulk material. The presence of bismuth telluride (Bi2Te3) nanoinclusions in Co4Sb12 leads to lower phonon thermal conductivity by introducing interfaces and defects; it enhances the average zT between 300-700 K. In the current study, Bi2Te3 nanoparticles were dispersed into bulk Co4Sb12 by ball-milling. The bulk was fabricated by spark plasma sintering. The presence of Bi2Te3 dispersion in Co4Sb12 was confirmed by x-ray diffraction, scanning electron microscopy, transmission electron microscopy and electron back scattered diffraction technique. Energy dispersive spectroscopy showed antimony (Sb) as an impurity phase for higher contents of Bi2Te3 in the sample. The Seebeck coefficient (S) and electrical conductivity (σ) were measured in the temperature range of 350-673 K. The negative value of S indicates that most of the charge carriers were electrons. A decrease in S and increase in σ with Bi2Te3 content are due to the increased carrier concentration, as confirmed by Hall measurement. The thermal conductivity, measured between 423-673 K, decreased due to the increased phonon scattering at interfaces. A maximum zT of 0.17 was achieved at 523 K and it did not vary much throughout the temperature range. The experimental results of composites were compared by using effective medium theories.

Thermoelectric properties of Co4Sb12 with Bi2Te3 nanoinclusions.

PubMed

Ghosh, Sanyukta; Bisht, Anuj; Karati, Anirudha; Rogl, Gerda; Rogl, Peter; Murty, B S; Suwas, Satyam; Mallik, Ramesh Chandra

2018-02-12

The figure of merit (zT) of a thermoelectric material can be enhanced by incorporation of nanoinclusions into bulk material. The presence of bismuth telluride (Bi 2 Te 3 ) nanoinclusions in Co 4 Sb 12 leads to lower phonon thermal conductivity by introducing interfaces and defects; it enhances the average zT between 300-700 K. In the current study, Bi 2 Te 3 nanoparticles were dispersed into bulk Co 4 Sb 12 by ball-milling. The bulk was fabricated by spark plasma sintering. The presence of Bi 2 Te 3 dispersion in Co 4 Sb 12 was confirmed by x-ray diffraction, scanning electron microscopy, transmission electron microscopy and electron back scattered diffraction technique. Energy dispersive spectroscopy showed antimony (Sb) as an impurity phase for higher contents of Bi 2 Te 3 in the sample. The Seebeck coefficient (S) and electrical conductivity (σ) were measured in the temperature range of 350-673 K. The negative value of S indicates that most of the charge carriers were electrons. A decrease in S and increase in σ with Bi 2 Te 3 content are due to the increased carrier concentration, as confirmed by Hall measurement. The thermal conductivity, measured between 423-673 K, decreased due to the increased phonon scattering at interfaces. A maximum zT of 0.17 was achieved at 523 K and it did not vary much throughout the temperature range. The experimental results of composites were compared by using effective medium theories.

In-situ crystallization of GeTe\\GaSb phase change memory stacked films

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

Velea, A., E-mail: alin.velea@psi.ch; National Institute of Materials Physics, RO-077125 Magurele, Ilfov; Borca, C. N.

2014-12-21

Single and double layer phase change memory structures based on GeTe and GaSb thin films were deposited by pulsed laser deposition (PLD). Their crystallization behavior was studied using in-situ synchrotron techniques. Electrical resistance vs. temperature investigations, using the four points probe method, showed transition temperatures of 138 °C and 198 °C for GeTe and GaSb single films, respectively. It was found that after GeTe crystallization in the stacked films, Ga atoms from the GaSb layer diffused in the vacancies of the GeTe crystalline structure. Therefore, the crystallization temperature of the Sb-rich GaSb layer is decreased by more than 30 °C. Furthermore, at 210 °C,more » the antimony excess from GaSb films crystallizes as a secondary phase. At higher annealing temperatures, the crystalline Sb phase increased on the expense of GaSb crystalline phase which was reduced. Extended X-ray absorption fine structure (EXAFS) measurements at the Ga and Ge K-edges revealed changes in their local atomic environments as a function of the annealing temperature. Simulations unveil a tetrahedral configuration in the amorphous state and octahedral configuration in the crystalline state for Ge atoms, while Ga is four-fold coordinated in both as-deposited and annealed samples.« less

Competition behaviour of metal uptake in cementitious systems: An XRD and EXAFS investigation of Nd- and Zn-loaded 11 Å tobermorite

NASA Astrophysics Data System (ADS)

Vespa, M.; Dähn, R.; Wieland, E.

Cement-based materials play an important role in multi-barrier concepts developed worldwide for the safe disposal of hazardous and radioactive wastes. Cement is used to condition and stabilize the waste materials and to construct the engineered barrier systems (container, backfill and liner materials) of repositories for radioactive waste. In this study, bulk-X-ray absorption spectroscopy (XAS) was used to investigate the uptake mechanism of Nd on the crystalline C-S-H phase 11 Å tobermorite in the presence of Zn (co-absorbing metal), and vice versa, as potential competitor under strongly alkaline conditions (pH = 12.5-13.3). The Zn and Nd concentration in all samples was 50,000 ppm, whereas the reaction times varied from 1 to 6 months. Extended X-ray absorption fine structure (EXAFS) data of the Nd LIII-edge indicate that the local structural environment of Nd consists of ∼7-8 O atoms at 2.42 Å, ∼7-8 Si at ∼3.67 Å and ∼5-6 Ca at ∼3.8 Å, and that this environment remains unchanged in the presence and absence of Zn. In contrary, Zn K-edge EXAFS data exhibit distinct differences in the presence and absence of Nd as co-absorbing element. Data analysis indicates that Zn is tetrahedrally coordinated (∼4 O at ∼1.96 Å) and the obtained structural data in the simultaneous presence of Nd and Zn are consistent with the formation of mixed Zn surface complexes and Zn bound in the interlayer remaining in these positions also with prolonged reaction times (up to 6 months). However, without the co-absorbing element Nd, strong structural changes in the uptake mechanisms of Zn are observable, e.g., after 3 month reaction time Zn-Zn backscattering pairs can be observed. These findings suggest that Nd has an influence on the incorporation of Zn in the tobermorite structure. In addition, the results of this study indicate that competitive uptake of metal cations with similar sorption behaviour by C-S-H phases can take place, deserving further attention in future

ZnS-Sb2S3@C Core-Double Shell Polyhedron Structure Derived from Metal-Organic Framework as Anodes for High Performance Sodium Ion Batteries.

PubMed

Dong, Shihua; Li, Caixia; Ge, Xiaoli; Li, Zhaoqiang; Miao, Xianguang; Yin, Longwei

2017-06-27

Taking advantage of zeolitic imidazolate framework (ZIF-8), ZnS-Sb 2 S 3 @C core-double shell polyhedron structure is synthesized through a sulfurization reaction between Zn 2+ dissociated from ZIF-8 and S 2- from thioacetamide (TAA), and subsequently a metal cation exchange process between Zn 2+ and Sb 3+ , in which carbon layer is introduced from polymeric resorcinol-formaldehyde to prevent the collapse of the polyhedron. The polyhedron composite with a ZnS inner-core and Sb 2 S 3 /C double-shell as anode for sodium ion batteries (SIBs) shows us a significantly improved electrochemical performance with stable cycle stability, high Coulombic efficiency and specific capacity. Peculiarly, introducing a carbon shell not only acts as an important protective layer to form a rigid construction and accommodate the volume changes, but also improves the electronic conductivity to optimize the stable cycle performance and the excellent rate property. The architecture composed of ZnS inner core and a complex Sb 2 S 3 /C shell not only facilitates the facile electrolyte infiltration to reduce the Na-ion diffusion length to improve the electrochemical reaction kinetics, but also prevents the structure pulverization caused by Na-ion insertion/extraction. This approach to prepare metal sulfides based on MOFs can be further extended to design other nanostructured systems for high performance energy storage devices.

The electronic structure and thermoelectric properties of BiTl{sub 9}Te{sub 6} and SbTl{sub 9}Te{sub 6}: First-principles calculations

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

Guo, Li Bin; Ye, Lingyun; Wang, Yuan Xu, E-mail: wangyx@henu.edu.cn

2015-12-21

The electronic structure and thermoelectric properties of MTl{sub 9}Te{sub 6} (M = Bi, Sb) were studied using density functional theory and the semiclassical Boltzmann theory. It is found that the band gaps of BiTl{sub 9}Te{sub 6} and SbTl{sub 9}Te{sub 6} are equal to 0.59 eV and 0.72 eV, respectively. The relative large band gap and strong coupling between Sb s and Te p are helpful to the thermoelectric properties of SbTl{sub 9}Te{sub 6}. Near the bottom of the conduction bands, the number of band valleys of SbTl{sub 9}Te{sub 6} is four and is larger than that of BiTl{sub 9}Te{sub 6} (two band valleys),more » which will increase its Seebeck coefficient. Although BiTl{sub 9}Te{sub 6} has a larger electrical conductivity relative to relaxation time (σ/τ) along the z-direction than that of SbTl{sub 9}Te{sub 6}, the results show that the transport properties of SbTl{sub 9}Te{sub 6} are better than those of BiTl{sub 9}Te{sub 6} possibly due to its large Seebeck coefficient. The maximum value of power factor relative to relaxation time (S{sup 2}σ/τ) for SbTl{sub 9}Te{sub 6} reaches 4.30 × 10{sup 11 }W/K{sup 2} m s at 900 K, that is, originated from its relatively large Seebeck coefficient, suggesting its promising thermoelectric performance at high temperature.« less

The two-dimensional tunnel structures of K3Sb5O14 and K2Sb4O11

NASA Technical Reports Server (NTRS)

Hong, H. Y.-P.

1974-01-01

The structures of K3Sb5O14 and K2Sb4O11 have been solved by the single-crystal X-ray direct method and the heavy-atom method, respectively. The structure of K3Sb5O14 is orthorhombic, with space group Pbam and cell parameters a = 24.247 (4), b = 7.157 (2), c = 7.334 (2) A, Z = 4. The structure of K2Sb4O11 is monoclinic, with space group C2/m and cell parameters a = 19.473 (4), b = 7.542 (1), c = 7.198 (1) A, beta = 94.82 (2) deg, Z = 4. A full-matrix least-squares refinement gave R = 0.072 and R = 0.067, respectively. In both structures, oxygen atoms form an octahedron around each Sb atom and an irregular polyhedron around each K atom. By sharing corners and edges, the octahedra form a skeleton network having intersecting b-axis and c-axis tunnels. The K(+) ions, which have more than ten oxygen near neighbors, are located in these tunnels. Evidence for K(+)-ion transport within and between tunnels comes from ion exchange of the alkali ions in molten salts and anisotropic temperature factors that are anomalously large in the direction of the tunnels.

Preparation and Thermoelectric Properties of the Skutterudite-Related Phase Ru(0.5)Pd(0.5)Sb3

NASA Technical Reports Server (NTRS)

Caillat, T.; Kulleck, J.; Borshchevsky, A.; Fleurial, J.-P.

1996-01-01

A new skutterudite phase Ru(0.5)Pd(0.5)Sb3 was prepared. This new phase adds to a large number of already known materials with the skutterudite structure which have shown good potential for thermoelectric applications. Single phase, polycrystalline samples were prepared and characterized by x-ray analysis, electron probe microanalysis, density, sound velocity, thermal-expansion coefficient, and differential thermal analysis measurements. Ru(0.5)Pd(0.5)Sb3 has a cubic lattice, space group Im3 (T(sup 5, sub h)), with a = 9.298 A and decomposes at about 920 K. The Seebeck coefficient, the electrical resistivity, the Hall effect, and the thermal conductivity were measured on hot-pressed samples over a wide range of temperatures. Preliminary results show that Ru(0.5)Pd(0.5)Sb3 behaves as a heavily doped semiconductor with an estimated band gap of about 0.6 eV. The lattice thermal conductivity of Ru(0.5)Pd(0.5)Sb3 is substantially lower than that of the binary isostructural compounds CoSb3 and IrSb3. The unusually low thermal conductivity might be explained by additional hole and charge transfer phonon scattering in this material. The potential of this material for thermoelectric applications is discussed.

Structural transition of (InSb)n clusters at n = 6-10

NASA Astrophysics Data System (ADS)

Lu, Qi Liang; Luo, Qi Quan; Huang, Shou Guo; Li, Yi De

2016-10-01

An optimization strategy combining global semi-empirical quantum mechanical search with all-electron density functional theory was adopted to determine the lowest energy structure of (InSb)n clusters with n = 6-10. A new structural growth pattern of the clusters was observed. The lowest energy structures of (InSb)6 and (InSb)8 were different from that of previously reported results. Competition existed between core-shell and cage-like structures of (InSb)8. The structural transition of (InSb)n clusters occurred at size n = 8-9. For (InSb)9 and (InSb)10 clusters, core-shell structure were more energetically favorable than the cage. The corresponding electronic properties were investigated.

Characterization of 1:1 Random Copolymers Obtained from 6-, 7-, 11-, and 12-Carbon Amino Acids.

DTIC Science & Technology

1993-10-22

Random Copolymers Obtained From 6-, 7-, 11-, and 12-Carbon Amino Acids by C. G. Johnson and L. J. Mathias 0 T .... Prepared for Publication r. t in the...NOOOG4-f-j- From 6-, 7-, 11-, and 12-Carbon Amino Acids 1225 ~~~ :: V Co~de 413m(iUK C. G Johnson, and Lo J. Mathias ś RFORMING ORGANIZA7,iCN ;fAMjjS...distribution is unlimited. Copolymers were prepared from the title amino acids by rr ilt condensation under dry nitrogen. The resulting copolymers were

ThE SYnthesis of R z Fe4- x Co x Sb12 (R: Yb, La, Ce) skutterudites and their thermoelectric properties

NASA Astrophysics Data System (ADS)

Park, Kwan-Ho; Lee, Soonil; Seo, Won-Seon; Shin, Dong-Kil; Kim, Il-Ho

2014-03-01

Rare-earth-filled skutterudites R z Fe4- x Co x Sb12 (R: Yb, La, Ce) were prepared, and their transport and thermoelectric properties were examined. All specimens showed p-type conduction and exhibited a degenerate semiconductor behavior. R0.9Fe3CoSb12 had lower electrical conductivities and higher Seebeck coefficients than RFe4Sb12, which meant that Co led to charge compensation through electron donations. All specimens had positive Hall coefficients, and their carrier concentrations were decreased by charge compensation with increasing Co substitution. The thermal conductivities of R0.9Fe3CoSb12 were lower than those of RFe4Sb12 due to the decreased carrier concentration, as well as the lattice scattering induced by the substitution of Co for Fe. Yb-filled and La-filled skutterudites showed enhanced thermoelectric figures of merit through charge compensation with Co, but Ce-filled skutterudites did not. Yb2˜3+ and La3+ ions required charge compensation to stabilize their skutterudite phases, but Ce3˜4+ ions did not.

A novel double perovskite tellurate Eu3+-doped Sr2MgTeO6 red-emitting phosphor with high thermal stability

NASA Astrophysics Data System (ADS)

Liang, Jingyun; Zhao, Shancang; Yuan, Xuexia; Li, Zengmei

2018-05-01

A series of novel double perovskite tellurate red-emitting phosphors Sr2MgTeO6:xEu3+ (x = 0.05-0.40) were successfully synthesized by a high-temperature solid-state reaction method. The phase structure, photoluminescence properties and thermal stability of the phosphor were investigated in detail. The phosphor shows dominant emission peak at 614 nm belonging to the 5D0 → 7F2 electric dipole transition under 465 nm excitation. The luminescence intensity keeps increasing with increasing the content of Eu3+ to 25 mol%, and the critical transfer distance of Eu3+ was calculated to be 12 Å. The quenching temperature for Sr2MgTeO6:0.25Eu3+ was estimated to be above 500 K. This spectral feature reveals high color purity and excellent chromaticity coordinate characteristics. Therefore, Eu3+-doped Sr2MgTeO6 phosphors are potential red phosphors for blue chip-based white light-emitting diode and display devices.

Origin and tectonic implications of the Zhaxikang Pb-Zn-Sb-Ag deposit in northern Himalaya: evidence from structures, Re-Os-Pb-S isotopes, and fluid inclusions

NASA Astrophysics Data System (ADS)

Zhou, Qing; Li, Wenchang; Qing, Chengshi; Lai, Yang; Li, Yingxu; Liao, Zhenwen; Wu, Jianyang; Wang, Shengwei; Dong, Lei; Tian, Enyuan

2018-04-01

The Zhaxikang Pb-Zn-Sb-Ag-(Au) deposits, located in the eastern part of northern Himalaya, totally contain more than 1.146 million tonnes (Mt) of Pb, 1.407 Mt of Zn, 0.345 Mt of Sb, and 3 kilotonnes (kt) of Ag. Our field observations suggest that these deposits are controlled by N-S trending and west- and steep-dipping normal faults, suggesting a hydrothermal rather than a syngenetic sedimentary origin. The Pb-Zn-Sb-Ag-(Cu-Au) mineralization formed in the Eocene as indicated by a Re-Os isochron age of 43.1 ± 2.5 Ma. Sulfide minerals have varying initial Pb isotopic compositions, with (206Pb/204Pb)i of 19.04-19.68, (207Pb/204Pb)i of 15.75-15.88, and (208Pb/204Pb)i of 39.66-40.31. Sulfur isotopic values display a narrow δ34S interval of +7.8-+12.2‰. These Pb-S isotopic data suggest that the Zhaxikang sources of Pb and S should be mainly from the coeval felsic magmas and partly from the surrounding Mesozoic strata including metasedimentary rocks and layered felsic volcanic rocks. Fluid inclusion studies indicate that the hydrothermal fluids have medium temperatures (200-336 °C) but varying salinities (1.40-18.25 wt.% NaCl equiv.) with densities of 0.75-0.95 g/cm3, possibly suggesting an evolution mixing between a high salinity fluid, perhaps of magmatic origin, with meteoric water.

The OsO(3)F(+) and mu-F(OsO(3)F)(2)(+) cations: their syntheses and study by Raman and (19)F NMR spectroscopy and electron structure calculations and X-ray crystal structures of [OsO(3)F][PnF(6)] (Pn = As, Sb), [OsO(3)F][HF](2)[AsF(6)], [OsO(3)F][HF][SbF(6)], and [OsO(3)F][Sb(3)F(16)].

PubMed

Gerken, Michael; Dixon, David A; Schrobilgen, Gary J

2002-01-28

The fluoride ion donor properties of OsO(3)F(2) have been investigated. The salts [OsO(3)F][AsF(6)], [OsO(3)F][HF](2)[AsF(6)], mu-F(OsO(3)F)(2)[AsF(6)], [OsO(3)F][HF](2)[SbF(6)], and [OsO(3)F][HF][SbF(6)] have been prepared by reaction of OsO(3)F(2) with AsF(5) and SbF(5) in HF solvent and have been characterized in the solid state by Raman spectroscopy. The single-crystal X-ray diffraction studies of [OsO(3)F][AsF(6)] (P2(1)/n, a = 7.0001(11) A, c = 8.8629(13) A, beta = 92.270(7) degrees, Z = 4, and R(1) = 0.0401 at -126 degrees C), [OsO(3)F][SbF(6)] (P2(1)/c, a = 5.4772(14) A, b = 10.115(3) A, c = 12.234(3) A, beta = 99.321(5) degrees, Z = 4, and R(1) = 0.0325 at -173 degrees C), [OsO(3)F][HF](2)[AsF(6)] (P2(1)/n, a = 5.1491(9) A, b = 8.129(2) A, c = 19.636(7) A, beta = 95.099(7) degrees, Z = 4, and R(1) = 0.0348 at -117 degrees C), and [OsO(3)F][HF][SbF(6)] (Pc, a = 5.244(4) A, b = 9.646(6) A, c = 15.269(10) A, beta = 97.154(13) degrees, Z = 4, and R(1) = 0.0558 at -133 degrees C) have shown that the OsO(3)F(+) cations exhibit strong contacts to the anions and HF solvent molecules giving rise to cyclic, dimeric structures in which the osmium atoms have coordination numbers of 6. The reaction of OsO(3)F(2) with neat SbF(5) yielded [OsO(3)F][Sb(3)F(16)], which has been characterized by (19)F NMR spectroscopy in SbF(5) and SO(2)ClF solvents and by Raman spectroscopy and single-crystal X-ray diffraction in the solid state (P4(1)m, a = 10.076(6) A, c = 7.585(8) A, Z = 2, and R(1) = 0.0858 at -113 degrees C). The weak fluoride ion basicity of the Sb(3)F(16)(-) anion resulted in an OsO(3)F(+) cation (C(3)(v) point symmetry) that is well isolated from the anion and in which the osmium is four-coordinate. The geometrical parameters and vibrational frequencies of OsO(3)F(+), ReO(3)F, mu-F(OsO(3)F)(2)(+), (FO(3)Os--FPnF(5))(2), and (FO(3)Os--(HF)(2)--FPnF(5))(2) (Pn = As, Sb) have been calculated using density functional theory methods.

Aromaticity and Antiaromaticity in Zintl Clusters

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

Sun, Zhong -Ming; Liu, Chao; Popov, Ivan Aleksandrovich

Originally, the concepts of aromaticity and antiaromaticity were introduced to explain the stability and reactivity of unsaturated organic compounds. Since then, they have been extended to other species with delocalized electrons including various saturated systems, organometallic compounds, and even inorganic clusters and molecules. In this study, we focus on the most recent progress of using these concepts to guide experimental synthesis and rationalize geometrical and electronic structures of a particular family of polyanions composed of Group 14 and 15 elements, namely Zintl clusters.

Aromaticity and Antiaromaticity in Zintl Clusters

DOE PAGES

Sun, Zhong -Ming; Liu, Chao; Popov, Ivan Aleksandrovich; ...

2018-05-18

Originally, the concepts of aromaticity and antiaromaticity were introduced to explain the stability and reactivity of unsaturated organic compounds. Since then, they have been extended to other species with delocalized electrons including various saturated systems, organometallic compounds, and even inorganic clusters and molecules. In this study, we focus on the most recent progress of using these concepts to guide experimental synthesis and rationalize geometrical and electronic structures of a particular family of polyanions composed of Group 14 and 15 elements, namely Zintl clusters.

Luminescent Eu3+ doped Al6Ge2O13 crystalline compounds obtained by the sol gel process for photonics

NASA Astrophysics Data System (ADS)

Maia, Lauro J. Q.; Faria Filho, Fausto M.; Gonçalves, Rogéria R.; Ribeiro, Sidney J. L.

2018-01-01

We synthesized pure and Eu3+ doped Al6Ge2O13 samples by an easy and low-cost sol-gel route using the GeO2, Al(NO3)3·9H2O and Eu(NO3)3·6H2O as precursors, tetramethylammonium hydroxide and ethanol as solvents. The Al6Ge2O13 crystalline phase possesses orthorhombic structure and is a potential host for rare earth ions, especially due to high aluminum concentration. Homogeneous and transparent sols and gels were obtained. The samples containing 1 mol% of Eu3+ were heat-treated at 1000 °C to eliminate organic compounds, providing high optical quality and structural purity. All materials were characterized by thermogravimetric and differential thermal analysis, X-ray diffraction, Fourier transform infrared spectroscopy, high resolution transmission electron microscopy, selected area electron diffraction, diffuse reflectance spectra in the ultraviolet-visible-near infrared regions and photoluminescence measurements. High purity of Eu3+ doped Al6Ge2O13 orthorhombic phase and well crystallized grain dimensions of around 100 nm was obtained with high red photoluminescence emission. The decay lifetime of 5D0 level from Eu3+ (the emission at 612 nm) was determined, being between 0.97 and 2.12 ms, and an average quantum efficiency of 54% was determined (considering the average experimental lifetime of 1.77 ms). Moreover, it was calculated and analyzed some parameters of Judd-Ofelt theory applied to Eu3+ emissions from Al6Ge2O13 host. The results show that Eu3+ doped Al6Ge2O13 crystalline compounds have large potential to be used in displays and LED devices.

A comparison of the transport properties of lithium-stuffed garnets and the conventional phases Li 3Ln3Te 2O 12

NASA Astrophysics Data System (ADS)

Cussen, Edmund J.; Yip, Thomas W. S.; O'Neill, Gemma; O'Callaghan, Michael P.

2011-02-01

The structures of new phases Li 6CaLa 2Sb 2O 12 and Li 6.4Ca 1.4La 2Sb 2O 12 have been characterised using neutron powder diffraction. Rietveld analyses show that both compounds crystallise in the space group la3¯ d and contain the lithium cations in a complex arrangement with occupational disorder across oxide tetrahedra and distorted oxide octahedra, with considerable positional disorder in the latter. Variable temperature neutron diffraction experiments on Li 6.4Ca 1.4La 2Sb 2O 12 show the structure is largely invariant with only a small variation in the lithium distribution as a function of temperature. Impedance spectroscopy measurements show that the total conductivity of Li 6CaLa 2Sb 2O 12 is several orders of magnitude smaller than related lithium-stuffed garnets with σ=10 -7 S cm -1 at 95 °C and an activation energy of 0.82(3) eV. The transport properties of the conventional garnets Li 3Gd 3Te 2O 12, Li 3Tb 3Te 2O 12, Li 3Er 3Te 2O 12 and Li 3Lu 3Te 2O 12 have been evaluated and consistently show much lower values of conductivity, σ≤4.4×10 -6 S cm -1 at 285 °C and activation energies in the range 0.77(4)≤ Ea/eV≤1.21(3).

Li diffusion in epitaxial (11 $bar 2$ 0) ZnO thin films

NASA Astrophysics Data System (ADS)

Wu, P.; Zhong, J.; Emanetoglu, N. W.; Chen, Y.; Muthukumar, S.; Lu, Y.

2004-06-01

Zinc oxide (ZnO) possesses many interesting properties, such as a wide energy bandgap, large photoconductivity, and high excitonic binding energy. Chemical-vapor-deposition-grown ZnO films generally show n-type conductivity. A compensation doping process is needed to achieve piezoelectric ZnO, which is needed for surface acoustic wave (SAW), bulk acoustic wave, and micro-electromechanical system devices. In this work, a gas-phase diffusion process is developed to achieve piezoelectric (11bar 20) ZnO films. Comparative x-ray diffraction (XRD) and scanning electron microscopy (SEM) measurements confirmed that high crystal quality and good surface morphology were preserved after diffusion. Photoluminescence (PL) measurements show a broad band emission with a peak wavelength at ˜580 nm, which is associated with Li doping. The SAW, including both Rayleigh-wave and Love-wave modes, is achieved along different directions in piezoelectric (11bar 20) ZnO films grown on an r-plane sapphire substrate.

Sb-Te Phase-change Materials under Nanoscale Confinement

NASA Astrophysics Data System (ADS)

Ihalawela, Chandrasiri A.

Size, speed and efficiency are the major challenges of next generation nonvolatile memory (NVM), and phase-change memory (PCM) has captured a great attention due to its promising features. The key for PCM is rapid and reversible switching between amorphous and crystalline phases with optical or electrical excitation. The structural transition is associated with significant contrast in material properties which can be utilized in optical (CD, DVD, BD) and electronic (PCRAM) memory applications. Importantly, both the functionality and the success of PCM technology significantly depend on the core material and its properties. So investigating PC materials is crucial for the development of PCM technology to realized enhanced solutions. In regards to PC materials, Sb-Te binary plays a significant role as a basis to the well-known Ge-Sb-Te system. Unlike the conventional deposition methods (sputtering, evaporation), electrochemical deposition method is used due to its multiple advantages, such as conformality, via filling capability, etc. First, the controllable synthesis of Sb-Te thin films was studied for a wide range of compositions using this novel deposition method. Secondly, the solid electrolytic nature of stoichiometric Sb2Te3 was studied with respect to precious metals. With the understanding of 2D thin film synthesis, Sb-Te 1D nanowires (18 - 220 nm) were synthesized using templated electrodeposition, where nanoporous anodic aluminum oxide (AAO) was used as a template for the growth of nanowires. In order to gain the controllability over the deposition in high aspect ratio structures, growth mechanisms of both the thin films and nanowires were investigated. Systematic understanding gained thorough previous studies helped to formulate the ultimate goal of this dissertation. In this dissertation, the main objective is to understand the size effect of PC materials on their phase transition properties. The reduction of effective memory cell size in conjunction with

Comparing biosimilar SB2 with reference infliximab after 54 weeks of a double-blind trial: clinical, structural and safety results.

PubMed

Smolen, Josef S; Choe, Jung-Yoon; Prodanovic, Nenad; Niebrzydowski, Jaroslaw; Staykov, Ivan; Dokoupilova, Eva; Baranauskaite, Asta; Yatsyshyn, Roman; Mekic, Mevludin; Porawska, Wieskawa; Ciferska, Hana; Jedrychowicz-Rosiak, Krystyna; Zielinska, Agnieszka; Choi, Jasmine; Rho, Young Hee

2017-10-01

SB2 is a biosimilar to the reference infliximab (INF). Similar efficacy, safety and immunogenicity between SB2 and INF up to 30 weeks were previously reported. This report investigates such clinical similarity up to 54 weeks, including structural joint damage. In this phase III, double-blind, parallel-group, multicentre study, patients with moderate to severe RA despite MTX were randomized (1:1) to receive 3 mg/kg of either SB2 or INF at 0, 2, 6 and every 8 weeks thereafter. Dose escalation by 1.5 mg/kg up to a maximum dose of 7.5 mg/kg was allowed after week 30. Efficacy, safety and immunogenicity were measured at each visit up to week 54. Radiographic damage evaluated by modified total Sharp score was measured at baseline and week 54. A total of 584 patients were randomized to receive SB2 (n = 291) or INF (n = 293). The rate of radiographic progression was comparable between SB2 and INF (mean modified total Sharp score difference: SB2, 0.38; INF, 0.37) at 1 year. ACR responses, 28-joint DAS, Clinical Disease Activity Index and Simplified Disease Activity Index were comparable between SB2 and INF up to week 54. The incidence of treatment-emergent adverse events and anti-drug antibodies were comparable between treatment groups. Such comparable trends of efficacy, safety and immunogenicity were consistent from baseline up to 54 weeks. The pattern of dose increment was also comparable between SB2 and INF. SB2 maintained similar efficacy, safety and immunogenicity with INF up to 54 weeks in patients with moderate to severe RA. Radiographic progression was comparable at 1 year. ClinicalTrials.gov (http://clinicaltrials.gov; NCT01936181) and EudraCT (https://www.clinicaltrialsregister.eu; 2012-005733-37). © The Author 2017. Published by Oxford University Press on behalf of the British Society for Rheumatology.

Comparing biosimilar SB2 with reference infliximab after 54 weeks of a double-blind trial: clinical, structural and safety results

PubMed Central

Smolen, Josef S.; Choe, Jung-Yoon; Prodanovic, Nenad; Niebrzydowski, Jaroslaw; Staykov, Ivan; Dokoupilova, Eva; Baranauskaite, Asta; Yatsyshyn, Roman; Mekic, Mevludin; Porawska, Wieskawa; Ciferska, Hana; Jedrychowicz-Rosiak, Krystyna; Zielinska, Agnieszka; Choi, Jasmine; Rho, Young Hee

2017-01-01

Abstract Objectives SB2 is a biosimilar to the reference infliximab (INF). Similar efficacy, safety and immunogenicity between SB2 and INF up to 30 weeks were previously reported. This report investigates such clinical similarity up to 54 weeks, including structural joint damage. Methods In this phase III, double-blind, parallel-group, multicentre study, patients with moderate to severe RA despite MTX were randomized (1:1) to receive 3 mg/kg of either SB2 or INF at 0, 2, 6 and every 8 weeks thereafter. Dose escalation by 1.5 mg/kg up to a maximum dose of 7.5 mg/kg was allowed after week 30. Efficacy, safety and immunogenicity were measured at each visit up to week 54. Radiographic damage evaluated by modified total Sharp score was measured at baseline and week 54. Results A total of 584 patients were randomized to receive SB2 (n = 291) or INF (n = 293). The rate of radiographic progression was comparable between SB2 and INF (mean modified total Sharp score difference: SB2, 0.38; INF, 0.37) at 1 year. ACR responses, 28-joint DAS, Clinical Disease Activity Index and Simplified Disease Activity Index were comparable between SB2 and INF up to week 54. The incidence of treatment-emergent adverse events and anti-drug antibodies were comparable between treatment groups. Such comparable trends of efficacy, safety and immunogenicity were consistent from baseline up to 54 weeks. The pattern of dose increment was also comparable between SB2 and INF. Conclusion SB2 maintained similar efficacy, safety and immunogenicity with INF up to 54 weeks in patients with moderate to severe RA. Radiographic progression was comparable at 1 year. Trial registration ClinicalTrials.gov (http://clinicaltrials.gov; NCT01936181) and EudraCT (https://www.clinicaltrialsregister.eu; 2012-005733-37) PMID:28957563

Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups

PubMed Central

Gillett-Kunnath, Miriam M.; Sevov, Slavi C.

2012-01-01

Although the first studies of Zintl ions date between the late 1890's and early 1930's they were not structurally characterized until many years later.1,2 Their redox chemistry is even younger, just about ten years old, but despite this short history these deltahedral clusters ions E9n- (E = Si, Ge, Sn, Pb; n = 2, 3, 4) have already shown interesting and diverse reactivity and have been at the forefront of rapidly developing and exciting new chemistry.3-6 Notable milestones are the oxidative coupling of Ge94- clusters to oligomers and infinite chains,7-19 their metallation,14-16,20-25 capping by transition-metal organometallic fragments,26-34 insertion of a transition-metal atom at the center of the cluster which is sometimes combined with capping and oligomerization,35-47 addition of main-group organometallic fragments as exo-bonded substituents,48-50 and functionalization with various organic residues by reactions with organic halides and alkynes.51-58 This latter development of attaching organic fragments directly to the clusters has opened up a new field, namely organo-Zintl chemistry, that is potentially fertile for further synthetic explorations, and it is the step-by-step procedure for the synthesis of germanium-divinyl clusters described herein. The initial steps outline the synthesis of an intermetallic precursor of K4Ge9 from which the Ge94- clusters are extracted later in solution. This involves fused-silica glass blowing, arc-welding of niobium containers, and handling of highly air-sensitive materials in a glove box. The air-sensitive K4Ge9 is then dissolved in ethylenediamine in the box and then alkenylated by a reaction with Me3SiC≡CSiMe3. The reaction is followed by electrospray mass spectrometry while the resulting solution is used for obtaining single crystals containing the functionalized clusters [H2C=CH-Ge9-CH=CH2]2-. For this purpose the solution is centrifuged, filtered, and carefully layered with a toluene solution of 18-crown-6. Left

Superconductivity in the Narrow Gap Semiconductor RbBi 11/3Te 6

DOE PAGES

Malliakas, Christos D.; Chung, Duck Young; Claus, Helmut; ...

2016-10-16

Superconductivity was discovered in the layered compound RbBi 11/3Te 6, featuring Bi vacancies and a narrow band gap of 0.25(2) eV at room temperature. In addition, a sharp superconducting transition at similar to 3.2 K was observed in polycrystalline ingots. The superconducting volume fraction of oriented single crystals is almost 100%, confirming bulk superconductivity. Systematic Se and Sb substitutions in RbBi 11/3-ySb ySe xTe 6-x, revealed a dependence of the superconducting transition on composition that can increase the T c up to similar to 10%. The RbBi 11/3Te 6 system is the first member of the new homologous series Rb[Bimore » 2n+11/3Te 3n+6] with infinite Bi 2Te 3-like layers. Lastly, the large degree of chemical tunability of the electronic structure of the homology via doping and/or substitution gives rise to a new family of superconductors.« less

Characteristics of surface acoustic waves in (11\\bar 2 0)ZnO film/ R-sapphire substrate structures

NASA Astrophysics Data System (ADS)

Wang, Yan; Zhang, ShuYi; Xu, Jing; Xie, YingCai; Lan, XiaoDong

2018-02-01

(11\\bar 2 0)ZnO film/ R-sapphire substrate structure is promising for high frequency acoustic wave devices. The propagation characteristics of SAWs, including the Rayleigh waves along [0001] direction and Love waves along [1ī00] direction, are investigated by using 3 dimensional finite element method (3D-FEM). The phase velocity ( v p), electromechanical coupling coefficient ( k 2), temperature coefficient of frequency ( TCF) and reflection coefficient ( r) of Rayleigh wave and Love wave devices are theoretically analyzed. Furthermore, the influences of ZnO films with different crystal orientation on SAW properties are also investigated. The results show that the 1st Rayleigh wave has an exceedingly large k 2 of 4.95% in (90°, 90°, 0°) (11\\bar 2 0)ZnO film/ R-sapphire substrate associated with a phase velocity of 5300 m/s; and the 0th Love wave in (0°, 90°, 0°) (11\\bar 2 0)ZnO film/ R-sapphire substrate has a maximum k 2 of 3.86% associated with a phase velocity of 3400 m/s. And (11\\bar 2 0)ZnO film/ R-sapphire substrate structures can be used to design temperature-compensated and wide-band SAW devices. All of the results indicate that the performances of SAW devices can be optimized by suitably selecting ZnO films with different thickness and crystal orientations deposited on R-sapphire substrates.

Synthesis optimisation and characterisation of the organic-inorganic layered materials ZnS(m-xylylenediamine){sub 1/2} and ZnS(p-xylylenediamine){sub 1/2}

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

Luberda-Durnaś, K.; Guillén, A. González; Łasocha, W., E-mail: lasocha@chemia.uj.edu.pl

2016-06-15

Hybrid organic-inorganic layered materials of the type ZnS(amine){sub 1/2}, where amine=m-xylylenediamine (MXDA) or p-xylylenediamine (PXDA), were synthesised using a simple solvothermal method. Since the samples crystallised in the form of very fine powder, X-ray powder diffraction techniques were used for structural characterisation. The crystal structure studies, involving direct methods, show that both compounds crystallised in the orthorhombic crystal system, but in different space groups: ZnS(MXDA){sub 1/2} in non-centrosymmetric Ccm2{sub 1}, ZnS(PXDA){sub 1/2} in centrosymmetric Pcab. The obtained materials are built according to similar orders: semiconducting monolayers with the formula ZnS, parallel to the (010) plane, are separated by diamines. Themore » organic and inorganic fragments are connected by covalent bonds between metal atoms of the layers and nitrogen atoms of the amino groups. The optical properties of the hybrid materials differ from those of their bulk counterpart. In both compounds a blue-shift of about 0.8 or 0.9 eV was observed with reference to the bulk phase of ZnS. - Highlights: • New hybrid compounds: ZnS(MXDA){sub 1/2} and ZnS(PXDA){sub 1/2} were obtained. • Hybrids were studied using XRD, TG/DSC, XRK, SEM, UV–vis spectroscopy. • Structures of both materials were solved by powder diffraction methods.« less

Switching From Reference Adalimumab to SB5 (Adalimumab Biosimilar) in Patients With Rheumatoid Arthritis: Fifty-Two-Week Phase III Randomized Study Results.

PubMed

Weinblatt, Michael E; Baranauskaite, Asta; Dokoupilova, Eva; Zielinska, Agnieszka; Jaworski, Janusz; Racewicz, Artur; Pileckyte, Margarita; Jedrychowicz-Rosiak, Krystyna; Baek, Inyoung; Ghil, Jeehoon

2018-06-01

The 24-week equivalent efficacy and comparable safety results of the biosimilar SB5 and reference adalimumab (ADA) from the phase III randomized study in patients with moderate-to-severe rheumatoid arthritis (RA) have been reported previously. We undertook this transition study to evaluate patients who switched from ADA to SB5 or who continued to receive SB5 or ADA up to 52 weeks. In this phase III study, patients were initially randomized 1:1 to receive SB5 or ADA (40 mg subcutaneously every other week). At 24 weeks, patients receiving ADA were rerandomized 1:1 to continue with ADA (ADA/ADA group) or to switch to SB5 (ADA/SB5 group) up to week 52; patients receiving SB5 continued with SB5 for 52 weeks (SB5 group). Efficacy, safety, and immunogenicity were evaluated up to 52 weeks. The full analysis set population consisted of 542 patients (269 in the SB5 group, 273 in the ADA overall group [patients who were randomized to receive ADA at week 0], 125 in the ADA/SB5 group, and 129 in the ADA/ADA group). The percentages of patients meeting the American College of Rheumatology 20%, 50%, or 70% improvement criteria (achieving an ACR20, ACR50, or ACR70 response) at week 24 were maintained after the transition from ADA to SB5, and these response rates were comparable across treatment groups throughout the study. ACR20 response rates ranged from 73.4% to 78.8% at week 52. Radiographic progression was minimal and comparable across treatment groups. The safety profile and the incidence of antidrug antibodies were comparable across treatment groups after transition. SB5 was well tolerated over 1 year in patients with RA, with efficacy, safety, and immunogenicity comparable to those of ADA. Switching from ADA to SB5 had no treatment-emergent issues such as increased adverse events, increased immunogenicity, or loss of efficacy. © 2018 The Authors. Arthritis & Rheumatology published by Wiley Periodicals, Inc. on behalf of American College of Rheumatology.

Photoluminescence of transparent glass-ceramics based on ZnO nanocrystals and co-doped with Eu3+, Yb3+ ions

NASA Astrophysics Data System (ADS)

Arzumanyan, Grigory M.; Kuznetsov, Evgeny A.; Zhilin, Aleksandr A.; Dymshits, Olga S.; Shemchuk, Daria V.; Alekseeva, Irina P.; Mudryi, Alexandr V.; Zhivulko, Vadim D.; Borodavchenko, Olga M.

2016-12-01

Glasses of the K2Osbnd ZnOsbnd Al2O3sbnd SiO2 system co-doped with Eu2O3 and Yb2O3 were prepared by the melt-quenching technique. Transparent zincite (ZnO) glass-ceramics were obtained by secondary heat-treatments at 680-860 °C. At 860 °C, traces of Eu oxyapatite appeared in addition to ZnO nanocrystals. The average crystal size obtained from the X-ray diffraction data was found to range between 14 and 35 nm. Absorption spectra of the initial glasses are composed of an absorption edge and absorption bands due to electronic transitions of Eu3+ ions. With heat-treatment, the absorption edge pronouncedly shifts to the visible spectral range. The luminescence properties of the glass and glass-ceramics were studied by measuring their excitation and emission spectra at 300, 78, and 4.2 K. Strong red emission of Eu3+ ions dominated by the 5D0-7F2 (612 nm) electric dipole transition was detected. Changes in the luminescence properties of the Eu3+-related excitation and emission bands were observed after heat-treatments at 680 °C and 860 °C. The ZnO nanocrystals showed both broad luminescence (400-850 nm) and free-exciton emission near 3.3 eV at room temperature. The upconversion luminescence spectrum of the initial glass was obtained under excitation of the 976 nm laser source.

Characterization of Sb-doped Bi(2)UO(6) solid solutions by X-ray diffraction and X-ray absorption spectroscopy.

PubMed

Misra, N L; Yadav, A K; Dhara, Sangita; Mishra, S K; Phatak, Rohan; Poswal, A K; Jha, S N; Sinha, A K; Bhattacharyya, D

2013-01-01

The preparation and characterization of Sb-doped Bi(2)UO(6) solid solutions, in a limited composition range, is reported for the first time. The solid solutions were prepared by solid-state reactions of Bi(2)O(3), Sb(2)O(3) and U(3)O(8) in the required stoichiometry. The reaction products were characterized by X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) measurements at the Bi and U L(3) edges. The XRD patterns indicate the precipitation of additional phases in the samples when Sb doping exceeds 4 at%. The chemical shifts of the Bi absorption edges in the samples, determined from the XANES spectra, show a systematic variation only up to 4 at% of Sb doping and support the results of XRD measurements. These observations are further supported by the local structure parameters obtained by analysis of the EXAFS spectra. The local structure of U is found to remain unchanged upon Sb doping indicating that Sb(+3) ions replace Bi(+3) during the doping of Bi(2)UO(6) by Sb.

The atomistic mechanism for Sb segregation and As displacement of Sb in InSb(001) surfaces

NASA Astrophysics Data System (ADS)

Anderson, Evan M.; Millunchick, Joanna M.

2018-01-01

Interfacial broadening occurs in mixed-anion alloy heterostructures such as InAs/InAsSb due to both Sb-segregation and As-for-Sb exchange. In order to determine the atomistic mechanisms for these processes, we conduct ab initio calculations coupled with a cluster expansion formalism to determine the surface reconstructions of the pure and As-exposed InSb(001) surfaces. This approach provides a predicted phase diagram for pure InSb that is in better agreement with experiments. Namely, the α2(2 × 4) and α3c(4 × 4) structures are ultimately stable at 0K, but the α(4 × 3) and α2c(2 × 6) are within 1 meV/Å2. Exposure of the InSb(001) surface to As results in the As atoms infiltrating into the crystal and displacing subsurface Sb, thus providing the atomistic mechanisms for experimental observations of the As-for-Sb exchange reaction and Sb segregation. Experiments show that the widely reported A-(1 × 3) reconstruction is actually comprised of multiple reconstructions, which is consistent with the prediction of several nearly stable possible reconstructions.

Geochemical studies of Fe, Mn, Co, As, Cr, Sb, Zn, Sc and V in surface sediments from Jiaozhou Bay

NASA Astrophysics Data System (ADS)

Wu, Run; Li, Pei-Quan; Miao, Lu-Tian; Zhang, Shu-Xin; Tian, Wei-Zhi

1994-12-01

The contents of nearly forty-elements in surface sediments in Jiaozhou Bay were determined using a Neutron Activation Analysis Technique (Grancini, et al., 1976; Li Peiquan et al., 1985, 1986; Li Xiuxia et al., 1986). This paper's detailed discussion on only nine elements (Fe, Mn, Co, Cr, Sc, As, Sb, Zn and V) includes their distributions, concentrations, correlationships, material sources, background, etc. Based on Zavaristski's classification method, Fe, Mn, Co, Cr and V belong to the second group; As and Sb to the eighth groups: Sc and Zn to the third and sixth groups. It was found that their notably good correlationship is mainly due to the similarity of their ionic structures and that their variation is controlled by the Fe content (except Mn). The source of sediments is mainly terristrial material, and the composition of sediment is similar to that of shale and shale+clay. The contents for a large number of elements are within the scope of the background level, but there still is pollution of Zn and Cr, at least in a few stations.

Carbon-doped Ge2Sb2Te5 phase change material: A candidate for high-density phase change memory application

NASA Astrophysics Data System (ADS)

Zhou, Xilin; Wu, Liangcai; Song, Zhitang; Rao, Feng; Zhu, Min; Peng, Cheng; Yao, Dongning; Song, Sannian; Liu, Bo; Feng, Songlin

2012-10-01

Carbon-doped Ge2Sb2Te5 material is proposed for high-density phase-change memories. The carbon doping effects on electrical and structural properties of Ge2Sb2Te5 are studied by in situ resistance and x-ray diffraction measurements as well as optical spectroscopy. C atoms are found to significantly enhance the thermal stability of amorphous Ge2Sb2Te5 by increasing the degree of disorder of the amorphous phase. The reversible electrical switching capability of the phase-change memory cells is improved in terms of power consumption with carbon addition. The endurance of ˜2.1 × 104 cycles suggests that C-doped Ge2Sb2Te5 film will be a potential phase-change material for high-density storage application.

Development of sputtered CuSbS2 thin films grown by sequential deposition of binary sulfides

NASA Astrophysics Data System (ADS)

Medina-Montes, M. I.; Vieyra-Brito, O.; Mathews, N. R.; Mathew, X.

2018-05-01

In this work, CuSbS2 thin films were developed by annealing binary precursors deposited sequentially by rf magnetron sputtering. The recrystallization process was optimized and the films were extensively characterized using a number of tools such as XRD, Raman, SEM, energy dispersive x-ray spectroscopy, atomic force microscopy, Hall, UV–vis spectroscopy, Ellipsometry, Seebeck, and photoresponse. The influence of annealing temperature on the structure, morphology, elemental composition, optical and electrical properties are reported. Annealing below 350 °C resulted in famatinite (Cu3SbS4) and chalcostibite (CuSbS2) ternaries as well as binary phases. Phase-pure chalcostibite was obtained in the range of 350 °C–375 °C. At 400 °C, although CuSbS2 was predominant, tetrahedrite phase (Cu12Sb4S13) appeared as an additional phase. The elemental composition of the films was slightly sulfur deficient, and the atomic percentages of Cu, Sb and S showed a dependence on annealing temperature. The material properties of the phase-pure CuSbS2 thin films are: optical band gap in the range of 1.5–1.62 eV, absorption coefficient close to 105 cm‑1, atomic ratios of Cu/Sb ∼1 and (Cu + Sb)/S ∼1.2, crystal size 18.3–24.5 nm and grain size 50–300 nm. The films were photo-sensitive, showed p-type semiconductor behavior. Electrical resistivity, carrier density and hole mobility were 94–459 Ω cm, 1.6–7.0 × 1015 cm‑3 and 8.4–9.5 cm2 V‑1 s respectively.

121Sb and 35Cl NQR in RCN · SbCl5 Complexes

NASA Astrophysics Data System (ADS)

Semin, G. K.; Kuznetsov, S. I.; Raevsky, A. M.; Bryukhova, E. V.

1994-05-01

35Cl and 121Sb NQR spectra of RCN · SbCl5 complexes with R = Et, n-Pr, i-Pr, n-Bu, n-C5H11 , Cl(CH2)2, C6H4CH2, Ph, Cl, Me, CCl3 were measured and /or refined at 77 K. Redistribution of the "transferred charge" in the SbCl5 fragment of the complexes under study was investigated. The existence of a specific region of dispersion of the electron-nuclear motions (DENM) in RCN · SbCl5 complexes was established.

Fano Resonance of Eu1">2+ and Eu3+ in (Eu,Gd)Te MBE Layers