Static displacement of a guest atom in filled skutterudites MFe<Subscript>4</Subscript>Sb<Subscript>12</Subscript> (M = La,Ca, Na)

The properties of filled skutterudites MFe₄Sb₁₂ (M = La, Ca, Na) have been analyzed using the nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) methods. Two lines have been observed on the ¹³⁹La NMR spectrum of the LaFe₄Sb₁₂ compound and a substructure has been revealed in the ¹²¹Sb and ¹²³Sb lines in the NQR spectra of LaFe₄Sb₁₂ and CaFe₄Sb₁₂. The concept of the partial static displacement of guest atoms (M) in LaFe₄Sb₁₂ and CaFe₄Sb₁₂ has been proposed. The ab initio calculations confirm this assumption as well as give the displacement of a guest atom and indicate the absence of the splitting of the ¹³⁹La NMR line in the LaFe₄Sb₁₂ spectrum.     

Sm填充skutterudite化合物中填充原子扰动效应研究

结合Rietveld结构解析和拉曼光谱对单相多晶的Sm原子填充的skutterudite化合物Sm_yFe_xCo_4-xSb₁₂进行了分析.Rietveld精确化结果表明：Sm_yFe_xCo_4-xSb₁₂化合物具有填充式skutterudite结构,Sm原 关键词： 方钴矿 Rietveld结构解析 拉曼散射 扰动     

Mössbauer studies on impactites from Lonar impact crater

The partly filled skutterudites A _x Fe₄Sb₁₂ (A = La, Pr, Nd, Eu, Yb, and the monovalent homologue Tl) were investigated at 4.2 K by ⁵⁷Fe Mössbauer spectroscopy in external fields up to 13.5 T. Two Fe sites were identified. The observed relative spectral areas are not for all compounds in agreement with filling factors for the A-atoms determined from X-ray experiments. The change in sign and the small value of the induced hyperfine fields for magnetically ordered compounds are strong hints for itinerant ferromagnetism with small ordered moments.     

Ga填充n型方钴矿化合物的结构及热电性能

用熔融退火结合放电等离子烧结(SPS)技术制备了具有不同Ga填充含量的Ga_xCo₄Sb₁₂方钴矿化合物,研究了不同Ga含量对其热电传输特性的影响规律. Rietveld结构解析表明,Ga占据晶体学2a空洞位置,Ga填充上限约为0.22,当Ga的名义组成x≤0.25时,样品的电导率、室温载流子浓度N_p随Ga含量的增加而增加,Seebeck系数随Ga含量的增加而减小. 室温下霍尔测试表明,每一个Ga授予框架0.9个电子,比Ga的氧化价态Ga³⁺小得多. 由于Ga离子半径相对较小,致使Ga填充方钴矿化合物的热导率κ及晶格热导率κ_L较其他元素填充的方钴矿化合物低. 当x＝0.22时对应的样品在300K时的热导率和晶格热导率分别为3.05Wm^-1·K^-1和 2.86Wm^-1·K^-1.在600K下Ga_0.22Co_4.0Sb_12.0样品晶格热导率达到最小,为1.83Wm^-1·K^-1,最大热电优值Z,在560K处达1.31×10^-3K^-1. 关键词： skutterudite化合物 Ga原子填充 结构 热电性能     

Thermoelectric properties of n-type Sr x M y Co4Sb12 (M=Yb, Ba) double-filled skutterudites

Alkaline-earth (AE) and rare-earth (RE) atoms are usually used as void fillers in the caged compound CoSb₃ to improve the thermoelectric performance of the filled system. Polycrystalline single-filled Sr_0.21Co₄Sb₁₂, double-filled Sr _x Yb _y Co₄Sb₁₂, and Sr _x Ba _y Co₄Sb₁₂ skutterudites have been synthesized. Rietveld structure refinement confirms that both Sr and Yb occupy the Sb-icosaedron voids in skutterudite frame work. In this paper, we report the high-temperature thermoelectric properties including electrical conductivity, Seebeck coefficient, and thermal conductivity. Double filling of the Sr–Yb combinations shows a stronger suppression on lattice thermal conductivity than that of Sr–Ba combination. Furthermore, the double-filled Sr _x Yb _y Co₄Sb₁₂ skutterudites exhibit a much higher power factor than the Sr-filled system. The maximum power factor for Sr_0.22Yb_0.03Co₄Sb_12.12 reaches 41 μW cm⁻¹ K⁻² at room temperature and 57.5 μW cm⁻¹ K⁻² at 850 K, respectively. The enhanced thermoelectric figures of merit are 1.32 for Sr _x Yb _y Co₄Sb₁₂ and 1.22 for Sr _x Ba _y Co₄Sb₁₂ at 850 K, respectively.     

Low temperature elastic behaviour of As-Sb-Se and Ge-Sb-Se glasses

The ternary glasses of arsenic and germanium with antimony and selenium can be prepared in large sizes for optical purposes. The elastic behaviour of eight compositions of each glass has been studied down to 4.2 K using a 10 MHz ultrasonic pulse echo interferometer. The glasses have a normal elastic behaviour, with the velocities gradually increasing as the temperature is lowered. An anharmonic solid model of Lakkad satisfactorily explains the temperature variations. The elastic moduli of Ge _x Sb₁₀Se_90?x glasses increase linearly as the Ge content is increased up to 25 at. % and beyond this the increase is nonlinear. (AsSb)₄₀Se₆₀ glasses show a linear increase in elastic moduli with increasing Sb content. The elastic moduli of As _x Sb₁₅Se_85?x glasses exhibit a drastic change near the stoichiometric composition As₂₅Sb₁₅Se₆₀. These behaviours have been qualitatively explained on the basis of the structural changes in glasses.     

High resolution XPS study of the large-band-gap semiconductor stibnite (Sb2S3): Structural contributions and surface reconstruction

Conventional X-ray photoelectron spectroscopy (XPS) and synchrotron radiation XPS (SRXPS) were used to probe the chemical state properties of stibnite (Sb₂S₃), a large-band-gap semiconductor of complex structure. The conventional spectra were obtained with a Kratos Axis Ultra XPS with magnetic confinement charge neutralization, which is very effective in minimizing both uniform charging and differential charging on this large-band-gap semiconductor. The narrow linewidths (much narrower than previously obtained) for single doublet fits (e.g. Sb 4d_5/2 of 0.57 eV and S 2p_3/2 of 0.63 eV) enabled the observation of a small peak on the low binding energy side of the Sb 3d and Sb 4d lines. With the aid of the very surface-sensitive Sb 4d SRXPS spectra, these low energy peaks are assigned to small Sb metal clusters at the surface after cleavage; the signal for these clusters increases with X-ray dose on the sample.A detailed analysis of the Sb 4d and S 2p linewidths concludes that the Sb 4d_5/2 linewidth is larger than expected based on the inherent linewidth of the instrument and the Sb 4d lifetime width, and on comparison with the As 3d linewidth (0.52 eV) for the analogous As₂S₃. Also, the S 2p_3/2 linewidth is substantially broader than the Sb 4d_5/2 linewidth. These larger than expected linewidths are due to two structurally distinct Sb atoms and three structurally distinct S atoms in the Sb₂S₃ crystal structure. Accordingly, the Sb 4d and S 2p spectra have been fitted to two and three doublets respectively, and the linewidth for all peaks is 0.53 eV. Using recent molecular orbital calculations, the doublets have been assigned to the different structural Sb and S sites.     

Thermoelectric power and phase transition of polycrystalline As2Te3 under pressure

The pressure dependence of the thermoelectric power of monoclinic As₂Te₃ is measured up to 10 GPa using a Mao-Bell diamond anvil cell. The thermoelectric power never reaches an absolute value greater than the ambient pressure value of 242 μV/K. Evidence of a phase transition is present between 6 and 8 GPa where the thermoelectric power reaches an absolute value of 225 μV/K after passing through a minimum of S≈75 μV/K. X-ray diffraction experiments confirm that the resulting structure is β-As₂Te₃, which is isostructural with Bi₂Te₃ and Sb₂Te₃.     

Structural, magnetic and magnetocaloric properties of the Gd5Si4−xSbx (x=0.5-3.5) phases

Substitution of Sb for Si in the Gd₅Si₄ phase results in the formation of ternary Gd₅Si_4−xSb_x phases with three different structure types. For x≤0.38 the Gd₅Si₄-type structure (Pnma space group) with all interslab T-T dimers intact exists (T is Si or Si/Sb mixture), in the x=1.21-1.79 region the Sm₅Ge₄-type structure (Pnma) with all interslab dimers broken is found. A further increase in the Sb concentration (x=2.27-3.1) leads to the appearance of the Eu₅As₄-type structure (Cmca) with broken but equivalent interslab T?T bonds. The Gd₅Si_4−xSb_x phases with 1.21≤x≤3.1 undergo ferromagnetic transitions in the temperature range from 164 to 295 K. Magnetocaloric effect in terms of the isothermal entropy change, ΔS, reaches the maximum values of -3.7(4), -4.2(6) and -4.6(7) J/kg K for the Gd₅Si₂Sb₂, Gd₅Si_1.5Sb_2.5 and Gd₅SiSb₃ samples, respectively.     

Raman spectroscopic studies on matrix-isolated arsenic and antimony molecules As4 and Sb4 in noble gas matrices

The Raman spectra of As₄ and Sb₄ molecules have been studied in neon, argon, krypton, and xenon matrices at 7 K. The vibrational frequencies of the As₄ molecule are up to 17 cm⁻¹ higher than the experimental gas phase data. This evident blue-shift is not caused by matrix effects but originates from an underestimation of the fundamentals in the gas phase as a course of the elevated temperatures. The observed frequencies of As₄ and Sb₄ show a linear dependence toward the matrix host polarizability. Extrapolated values for zero polarizability which best represent a free molecule, are considered fundamental frequencies. The general valence force fields of As₄ and Sb₄ were calculated from the extrapolated frequencies.     

Synchrotron X-ray study of filled skutterudites CeFe4Sb12 and Ce0.8Fe3CoSb12

In situ synchrotron X-ray diffraction measurements are carried out on filled skutterudites CeFe₄Sb₁₂ and Ce_0.8Fe₃CoSb₁₂ up to 32 and 20 GPa, respectively, at room temperature. No phase transformation was observed for both samples in the pressure range. Fitting the pressure-volume data (up to 10 GPa) to the third-order Birch-Murnaghan equation of state, the bulk modulus B₀ is determined to be 74(4) GPa, with the pressure derivative B′₀=7(2) for CeFe₄Sb₁₂, and B₀=71(2) GPa and B′₀=8(2) for Ce_0.8Fe₃CoSb₁₂. The bulk moduli of filled skutterudites CeFe₄Sb₁₂ and Ce_0.8Fe₃CoSb₁₂ in our study are smaller than those from previous studies on unfilled skutterudite CoSb₃. The P-V curves of the unfilled skutterudite CoSb₃ and filled skutterudites Ce_yFe_4−xCo_xSb₁₂ showed good agreement, indicating that the Ce filling fraction and the replacement of Fe with Co have little effect on their compression behaviors.     

Synthesis technique for and certain properties of AsxSb1-xSI crystals

A technique for synthesizing As_xSb_1-xSI is described. The system is shown to form crystals of a limited solid solution. In the region in which a solid solution is formed, the crystals are ferroelectric photoconductors. An arsenic admixture reduces the Curie point from 295°K (SbSI) to 243 °K (As_0.1(Sb_0.9SI). A study of the basic electrophysical properties of these crystals is reported.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 28–33, September, 1969.In conclusion the authors thank professor V. M. Fridkin for interest in the study and for participation in discussion of the results.     

Thermoelectric properties of indium-filled skutterudites prepared by combining solvothermal synthesis and melting

Indium-filled skutterudites with nominal compositions of In _x Co₄Sb₁₂ (x=0,0.1,0.2,0.3) were prepared by combining solvothermal synthesis and melting. The bulk samples were characterized by X-ray diffraction and scanning electron microscopy, respectively. The Seebeck coefficient, electrical conductivity, and thermal conductivity were measured from room temperature up to ∼773 K. Hall effect measurements were performed at room temperature. The thermoelectric properties of the samples were significantly influenced by filling In into CoSb₃. The dimensionless thermoelectric figure of merit, ZT, increased with increasing temperature and reached a maximum value of ∼0.79 for In_0.1Co₄Sb₁₂ at 573 K.     

Controlling anisotropy of GaSb(As)/GaAs quantum dots by self-assembled molecular beam epitaxy

A systematic study was performed to control the geometrical anisotropy of GaSb(As)/GaAs quantum dot structures formed by the Stranski–Krastanov growth mode of molecular beam epitaxy. In particular, effects of both the Sb₄ beam flux and the As₄ background pressure on the geometrical anisotropy were clarified and elongated QDs with lateral aspect ratio greater than 3 were successfully formed. Under a low As₄ background pressure, As₄ is found to act as surfactant to influence the adatom diffusion and change the density of QDs. By contrast, under high As₄ background pressure, the intermixing of As and Sb takes place and reduces strains induced by the lattice mismatch.     

Effect of replacement of Se by S on structural and physical properties of Ge–Sb–As–Se–S chalcogenide glasses

In the present study, the structural and opto-mechanical properties of Ge–Sb–As–Se–S chalcogenide glasses have been investigated. For this purpose, different bulk glasses of Ge₂₀Sb₅As₁₅Se_60?xS_x (0 ≤ x≤50) were prepared by conventional melt quenching technique in quartz ampoule and different characteristics of prepared glasses such as glass transition temperature, density, hardness, transmittance, optical band gap energy and refractive index were determined. The value of hardness and glass transition temperature of prepared glasses were found to increase with increasing the sulfur content as a result of formation of GeS₄ tetrahedral units and increasing the network connectivity and average bonding energy. The optical energy gap (according to Tauc’s relation), transmittance and refractive index of prepared glasses are in direct relation with sulfur content. In this study, the highest value of transmittance (about 70%) and lowest value of refractive index (2–2.3) was achieved in Ge₂₀Sb₅As₁₅Se₄₀S₂₀ and Ge₂₀Sb₅As₁₅Se₁₀S₅₀ glasses, respectively.     

Thermoelectric properties in p-type nanostructured Ge-doped Sb100GeTe150 alloy

Ge-doped Sb₁₀₀GeTe₁₅₀ alloy were prepared using spark plasma sintering technique, and its thermoelectric properties were evaluated over the temperature range 318–492 K. Through XRD analysis, we observed the same single phase as Sb₂Te₃ and weakened diffraction peaks. Rietveld refinement reveals that there is 0.96 at.% Ge that occupies in the Sb sites, leading to the lattice distortion in the Sb–Te crystal. High-resolution TEM images show that there are many nanodomains randomly distributed in the matrix with a large amount of amorphous phase adjoined. Measurements indicated that the Seebeck coefficients (α) increase and the electrical and thermal conductivities decrease with temperature in the entire temperature range. The maximum α value reaches 135 μV/K at 492 K, and the thermal conductivities are about 0.3 W/mK lower than those of present Sb₂Te₃ for the corresponding temperatures. The highest thermoelectric figure of merit ZT for the nanostructured alloy Sb₁₀₀GeTe₁₅₀ is 0.84 at 492 K, whereas that of the currently prepared Sb₂Te₃ is 0.74 at the corresponding temperature.     

Nanoscale order in GaAs:(B, Sb)

Nanoscale order caused by self-assembling of 1B4Sb and 4B10Sb clusters in GaAs:(B, Sb) is described. Self-assembling occurs in wide ranges of temperature and impurity concentration. Co-doping with boron and Sb isoelectronic impurities transforms GaAs into GaAs-rich B_xGa_1−xSb_yAs_1−y quaternary alloy. The self-assembling conditions are obtained from 0 to 800 °C with boron and Sb concentrations from x=1×10^–5 to x=2×10^–4 and from y=5×10^–4 to y=0.01, respectively. If Sb content is much larger than that of boron almost all boron atoms are in 1B4Sb clusters up to 800 °C and other boron impurities are isolated. If boron content is nearly equal or larger than that of Sb the formation of 4B10Sb clusters is preferential.     

In0.3Co4Sb12-xSex 方钴矿热电材料的制备和热电性能

用熔融退火结合放电等离子烧结法制备了In_0.3Co₄Sb_12-xSe_x(x=0—0.3)方钴矿热电材料,探讨了In的存在形式,系统研究了Se掺杂量对结构和热电性能的影响.结果表明:In可以填充到方钴矿二十面体空洞处,过量In在晶界处形成InSb第二相,Se对Sb的置换使晶格常数减小,In填充上限降低;In_0.3Co₄Sb_12-xSe_x样品呈n型传导,随着Se掺杂量的增大,载流子浓度降低,电导率下降,Seebeck系数增大,功率因子有所降低;由于在结构中引入了质量波动及晶格畸变,适量的Se掺杂可以大幅降低材料晶格热导率;样品In_0.3Co₄Sb₁₂和In_0.3Co₄Sb_11.95Se_0.05的最大ZT值均达到1.0以上. 关键词： 掺杂 填充式方钴矿 热电性能     

Contactless electroreflectance spectroscopy of Ga(In)NAs/GaAs quantum well structures containing Sb atoms

Contactless electroreflectance (CER) spectroscopy has been applied to investigate the optical transitions in Ga(In)NAs/GaAs quantum well (QW) structures containing Sb atoms. The identification of the optical transitions has been carried out in accordance with theoretical calculations which have been performed within the framework of the effective mass approximation. Using this method, the bandgap discontinuity for GaN_0.027As_0.863Sb_0.11/GaAs, Ga_0.62In_0.38As_0.954N_0.026Sb_0.02/GaAs, and Ga_0.61In_0.39As_0.963N_0.017Sb_0.02/GaN_0.027As_0.973/GaAs QW structures has been determined. It has been found that the conduction-band offset is ∼50 and ∼80% for GaN_0.027As_0.863Sb_0.11/GaAs and Ga_0.62In_0.38As_0.954N_0.026Sb_0.02/GaAs QWs, respectively. It corresponds to 264 and 296 meV depth QW for electrons and heavy-holes in GaN_0.027As_0.863Sb_0.11/GaAs QW; and 520 and 146 meV depth QW for electrons and heavy-holes in Ga_0.62In_0.38As_0.954N_0.026Sb_0.02/GaAs QW. In the case of the Ga_0.61In_0.39As_0.963N_0.017Sb_0.02/GaN_0.027As_0.973/GaAs step-like QW structure it has been shown that the depth of electron and heavy-hole Ga_0.61In_0.39As_0.963N_0.017Sb_0.02/GaN_0.027As_0.973 QW is ∼144 and ∼127 meV, respectively.     

Laser-induced forward transfer of intact chalcogenide thin films: resultant morphology and thermoelectric properties

We present a laser-based transfer method for the novel application of fabricating elements for planar thermoelectric devices. Thin films of thermoelectric chalcogenides (Bi₂Te₃, Bi₂Se₃ and Bi_0.5Sb_1.5Te₃) were printed via laser-induced forward transfer (LIFT) onto polymer-coated substrates over large areas of up to ～15 mm² in size. A morphological study showed that it was possible to partially preserve the polycrystalline structure of the transferred films. The films’ Seebeck coefficients after LIFT transfer were measured and resulted in ?49±1 μV/K, ?93±8 μV/K and 142±3 μV/K for Bi₂Te₃, Bi₂Se₃ and Bi_0.5Sb_1.5Te₃, respectively, which were found to be ～23±6 % lower compared to their initial values. This demonstration shows that LIFT is suitable to transfer sensitive, functional semiconductor materials over areas up to ～15 mm² with minimal damage onto a non-standard polymer-coated substrate.