Effects of double filling of Pb and Ba on thermoelectric properties of PbxBayCo4Sb11.5Te0.5 compounds by HPHT

Skutterudite compounds Pb_xBa_yCo₄Sb_11.5Te_0.5 (x≤0.23,y≤0.27) with bcc crystal structure have been prepared by the high pressure and high temperature (HPHT) method. The study explored a chemical method for filling Pb and Ba atoms into the voids of CoSb₃ to optimize the thermoelectric figure of merit ZT in the system of Pb_yBa_xCo₄Sb_11.5Te_0.5. The structure of Pb_xBa_yCo₄Sb_11.5Te_0.5 skutterudites was evaluated by means of X-ray diffraction. The Seebeck coefficient, electrical resistivity and power factor were performed from room temperature to 710 K. Compared with Co₄Sb_11.5Te_0.5, the thermal conductivity of Pb and Ba double-filled samples was reduced evidently. Among all filled samples, Pb_0.03Ba_0.27Co₄Sb_11.5Te_0.5 showed the highest power factor of 31.64 μW cm⁻¹ K⁻² at 663 K. Pb_0.05Ba_0.25Co₄Sb_11.5Te_0.5 showed the lowest thermal conductivity of 2.73 W m⁻¹ K⁻¹ at 663 K, and its maximum ZT value reached 0.63 at 673 K.     

Structural and optical properties of In35Sb45Se20−xTex phase-change thin films

Physical properties of In₃₅Sb₄₅Se_20−xTe_x thin films with different compositions (x=2.5, 5, 7.5, 10, 12.5 and 15 at %) prepared by electron beam evaporation method are studied. X-ray diffraction results indicate that the as-evaporated films depend on the Te content and the crystallized compounds consist mainly of Sb₂Se₃ with small amount of Sb₂SeTe₂. Transmittance and reflectance of the films are found to be thickness dependent. Optical-absorption data indicate that the absorption mechanism is direct transition. Optical band gap values decrease with increase in Te content as well as with increase in film thickness.     

Temperature dependence of thermoelectric properties of Ni-doped CoSb3

Temperature dependences of the Hall coefficient, Hall mobility and thermoelectric properties of Ni-doped CoSb₃ have been characterized over the temperature range from 20 to 773 K. Ni-doped CoSb₃ is an n-type semiconductor and the conduction type changes from n-type to p-type at around 450 K. The temperature for the transition from n-type to p-type increased with increasing Ni content x. The Seebeck coefficient reaches a maximum value near the transition temperature. The electrical resistivity indicates that Co_1−xNi_xSb₃ is a typical semiconductor when x≤0.03 and a degenerate semiconductor when x>0.03. Thermal conductivity analyses show that the lattice component is predominant at lower temperatures and carrier and bipolar components become large at temperatures higher than the transition temperature. The thermoelectric figure of merit reaches a maximum value close to the transition temperature and the largest value, 4.67×10⁻⁴ K⁻¹ at 600 K, was obtained for x=0.05.     

Thermoelectric properties of SnzCo8Sb24 skutterudites

Sn-filled CoSb₃ skutterudite compounds were synthesized by the induction melting process. Formation of a single δ-phase of the synthesized materials was confirmed by X-ray diffraction analysis. The temperature dependences of the Seebeck coefficient, electrical resistivity and thermal conductivity were examined in the temperature range of 300-700 K. Positive Seebeck and Hall coefficients confirmed p-type conductivity. Electrical resistivity increased with increasing temperature, which shows that the Sn-filled CoSb₃ skutterudite is a degenerate semiconductor. The thermal conductivity was reduced by Sn-filling because the filler atoms acted as phonon scattering centers in the skutterudite lattice. The lowest thermal conductivity was achieved in the composition of Sn_0.25Co₈Sb₂₄.     

Crystallization mechanism in Sb:Te thin films

The aim of this work is to study the mechanism of crystallization in Sb:Te thin films using differential scanning calorimetry (DSC), four-probe resistivity and X-ray diffraction (XRD) measurements.The DSC showed that the Sb_70+xTe_30−x films with x in the range of −3⩽x⩽3 show one exothermic reaction at 110 °C, whereas the films with x in the range of 3⩽x⩽13 present an additional one at about 70 °C. XRD measurements and Rietveld analysis have shown that the first exothermal peak can be associated to the formation of crystalline Sb and the second to the process of transformation of the Sb and the remaining material into a more stable Sb_2nTe₃ crystalline phase. Appearance of additional Sb phase decreases the crystallization temperature of Sb_70+xTe_30−x films.These structural transformations are also observed in the four-probe resistivity measurements: a one-step crystallization process in the Sb_70+xTe_30−x films with x in the range of −3⩽x⩽3and a two-steps crystallization process in films with x in the range of 3⩽x⩽13.The results of this investigation have shown that the amorphous-to-crystalline phase transformation in eutectic Sb:Te depended on the films composition.     

Transport coefficients and defect structure of Sb2−xAgxTe3 single crystals

Incorporation of Ag in the crystal lattice of Sb₂Te₃ creates structural defects that have a strong influence on the transport properties. Single crystals of Sb_2−xAg_xTe₃ (x=0.0; 0.014; 0.018 and 0.022) were characterized by measurements of the temperature dependence of the electrical resistivity, Hall coefficient, Seebeck coefficient and thermal conductivity in the temperature range of 5-300 K. With an increasing content of Ag the electrical resistance, the Hall coefficient and the Seebeck coefficient all decrease. This implies that the incorporation of Ag atoms in the Sb₂Te₃ crystal structure results in an increasing concentration of holes. However, the doping efficiency of Ag appears to be only about 50% of the expected value. We explain this discrepancy by a model based on the interaction of Ag impurity with the native defects in the Sb_2−xAg_xTe₃ crystal lattice. Defects have a particularly strong influence on the thermal conductivity. We analyze the temperature dependence of the lattice thermal conductivity in the context of the Debye model. Of the various phonon scattering contributions, the dominant influence of Ag incorporation in the crystal lattice of Sb₂Te₃ is revealed to be point-defect scattering where both the mass defect and elastic strain play a pivotal role.     

Electronic structure of the Co4Sn6Te6 ternary skutterudite phase

The electronic structure of Co₄Sn_6–x Te_6+x (x = 0, 1) ternary skutterudite systems has been investigated using ab ‐initio band structure computation. The x = 0 system is a semiconductor like the binary Co₄Sb₁₂, but with a lower band gap. The best dopant concentration for Co₄Sn₆Te₆ is estimated to be lower than that of Co₄Sb₁₂, with the highest electronic fig‐ ure‐of‐merit Z_eT for the n‐doped system. Finally, the increased charge transfer between the 8c Co and 24g Sn and Te atoms in Co₄Sn₆Te₆ compared to that of Co₄Sb₁₂ could be one reason for the observed decrease of thermal conductivity in ternary skutterudite systems. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

DC and AC conductivities of (As2S3)100−x(AsSe0.5Te0.5I)x chalcogenide glasses

The DC and AC conductivities of samples from the system (As₂S₃)_100−x(AsSe_0.5Te_0.5I)_x, where x=0, 5, 10, 15, 20, 25, 30, 35, 50, 70 and 90 mol%, were measured as a function of temperature. Besides, the AC conductivities of the samples with x=10 and 30 were measured as a function of frequency from room temperature to the glass transition temperature. The DC conductivity dependence on temperature is of the Arrhenius type, whereas the value of the pre-exponential factor suggests the electrical conduction by localized states in the band tails and by localized states near the Fermi level. The small values of the conduction activation energy (10⁻²-10⁻¹ eV) obtained at higher frequencies suggest that the conduction in these materials is due to hopping of charge carriers between close defect states near the Fermi level.     

The structural, electronic, elastic and optical properties of AlCu(Se1−xTex)2 compounds from first-principle calculations

The structural, electronic structure, elastic and optical properties of the AlCu(Se_1−xTe_x)₂ compounds have been investigated by using a first-principles method based on density functional theory. The lattice constants of the quaternary compounds AlCu(Se_1−xTe_x)₂ increase with the increasing of Te composition. The calculated lattice constants for the ternary compounds i.e. AlCuSe₂ and AlCuTe₂ are in good agreement with the experimental data. The band structures show that the compounds have direct band gap and the band gaps are found to vary nonlinearly with composition. The total and part density of states of the quaternary AlCu(Se_1−xTe_x)₂ compounds are discussed. The calculated elastic constants indicate that all of the AlCu(Se_1−xTe_x)₂ compounds are mechanically stable. The bulk modulus B, shear modulus G, Young’s modulus E and Poisson’s ratio ν can be obtained by using the Voigt-Reuss-Hill averaging scheme. The B/G ratios of the AlCu(Se_1−xTe_x)₂ compounds indicate that AlCu(Se_0.8Te_0.2)₂ is ductile and the others are brittle. The Debye temperature of the AlCu(Se_1−xTe_x)₂ compounds decreases a little with increasing Te content except the compound with x = 0.4. The dielectric functions, refractive index, extinction coefficient, absorption spectrums and energy-loss function of the AlCuSe₂ and AlCuTe₂ are also calculated and discussed in this work.     

The dependence of the structural and optical properties on the Te mole fraction in ZnS1−xTex/GaAs heterostructures

Lattice-mismatched ZnS_1−xTe_x epilayers with various Te mole fractions on GaAs (100) substrates were grown by double well temperature gradient vapor deposition. X-ray diffraction patterns showed that the grown ZnS_1−xTe_x layers were epitaxial films. The photoluminescence spectra showed that the peak position of the acceptor-bound exciton (A⁰, X) varied dramatically with changing the Te mole fraction and that the behavior of the (A⁰, X) peak position of the ZnS_1−xTe_x epilayers with a small amount of the Te mole fraction was attributed to a bowing effect. The reflectivity and ellipsometry spectra showed that the absorption energy peak was significantly affected due to the Stoke's effect. These results provide important information on the structural and optical properties of ZnS_1−xTe_x/GaAs heterostructures for improving optoelectronic device efficiencies operating in the spectral range between near ultraviolet and visible regions.     

Electrodeposition of BixSb2−xTey thermoelectric thin films from nitric acid and hydrochloric acid systems

The electrochemical behaviors of Bi^III, Te^IV and Sb^III single ions and their mixtures were investigated in nitric acid and hydrochloric acid system separately. Based on which, Bi_xSb_2−xTe_y thermoelectric films were prepared by potentiostatic electrodeposition from the solutions with different concentrations of Bi^III, Te^IV and Sb^III in the two acid systems. The morphologies, compositions, structures, Seebeck coefficients and resistivities of the deposited thin films were characterized and compared by ESEM (or FESEM), EDS, XRD, Seebeck coefficient measurement system and four-probe resistivity measuring device respectively. The results show that although Bi_xSb_2−xTe_y thermoelectric thin film which structure is consistent with the standard pattern of Bi_0.5Sb_1.5Te₃ can be gained in both of the two acid solutions by adjusting the deposition potential, their morphologies and thermoelectric properties have big differences in different acid solutions.     

Model of magnetic anisotropy in disordered semimagnetic semiconductors

We propose a model explaining the origin of cubic magnetic anisotropy in disordered semiconductor. We show that the magnetic anisotropy changes with the position of the Fermi energy in the valence band and the level of disorder in the crystal. The method is applied to Pb_1−x−ySn_yMn_xTe and Sn_1−xMn_xTe ferromagnetic semiconductor crystals.     

Facile synthesis of thiol-stabilized CdSexTe1−x nanocrystals

CdSe_xTe_1−x nanocrystals (x=0.25, 0.40, 0.50, 0.60 and 0.75) were synthesized using thioglycerol as a stabilizing agent. The composition of the CdSe_xTe_1−x nanocrystals was precisely controlled by tuning the precursor (Se/Te) ratio. The structural, morphological and optical properties of the nanocrystals were analyzed using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), diffused reflectance spectroscopy (DRS) and photoluminescence (PL) measurements. It is found that the Se/Te ratio significantly affects the properties of the resultant CdSe_xTe_1−x nanocrystals. XRD pattern of the CdSe_xTe_1−x nanocrystals revealed cubic, hexagonal and mixed phases depending on the ratio of Se:Te. Surface morphology of the CdSe_xTe_1−x nanocrystals showed nanoclusters of sizes ∼50 nm, with the adjacent cluster interlinking each other. DRS revealed the size dependence band gap energy prevailing in the CdSe_xTe_1−x nanocrystals from 1.52 to 2.66 eV due to the optical bowing effect. PL measurements exhibited band edge emission in the visible spectral region, and are red shifted with increase in Se concentration. The facile route employed in the present work to synthesis the CdSe_xTe_1−x nanocrystals in an aqueous medium is simple and controllable, and the strategy presented will be handy in preparing diverse semiconducting nanocrystals.     

First-principle study of electronic structure and stability of Sn0.5Sb0.5O2

A theoretical study on Sb-doped SnO₂ has been carried out by means of periodic density functional theory (DFT) at generalized gradient approximation (GGA) level. Stability and conductivity analyses were performed based on the formation energy and electronic structures. The results show that Sn_0.5Sb_0.5O₂ solid solution is stable because the formation energy of Sn_0.5Sb_0.5O₂ is −0.06 eV. The calculated energy band structure and density of states showed that the band gap of SnO₂ narrowed due to the presence of the Sb impurity energy levels in the bottom of the conduction band, namely there is Sb 5s distribution of electronic states from the Fermi level to the bottom of conduction band after the doping of antimony. The studies provide a theoretical basis to the development and application of Sn_1−xSb_xO₂ solid solution electrode.     

Influence of silver on the galvanomagnetic properties and energy spectrum of mixed (Bi1− x Sbx)2Te3 crystals

An investigation is made of the temperature dependences of the resistivity in the range 4.2–300 K, the Hall effect, and the Shubnikov-de Haas effect in magnetic fields up to 40 T in (Bi_{1? x} Sb_x)₂Te₃Ag_y single crystals (0 ≤ x ≤ 0.75). Doping (Bi_{1? x} Sb_x)₂Te₃ crystals with silver showed that in Sb₂Te₃ and (Bi_{1? x} Sb_x)₂Te₃ crystals unlike Bi₂Te₃ silver exhibits acceptor properties. The angular and concentration dependences of the Shubnikov-de Haas effect were studied in (Bi_{1? x} Sb_x)₂Te₃Ag_y. It was established that the anisotropy of the ellipsoids of the upper valence band in Bi_0.5Sb_1.5Te₃ remains unchanged as a result of silver doping.     

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.     

Characteristics of Si-doped Sb2Te3 thin films for phase-change random access memory

The characteristics of Si-doped Sb₂Te₃ thin films were investigated using differential scanning calorimetry (DSC), four-point probe technique, X-ray diffraction (XRD) analysis and high resolution transmission electron microscopy (HRTEM). It is found that the as-deposited Sb₂Te₃ film in our study is partly crystallized. Silicon doping increases the crystallization temperature and resistivity of Sb₂Te₃ film significantly. XRD and HRTEM analyses indicated that some of the doped Si atoms substitute for Sb or Te in the lattice, while others exists at the grain boundaries in the form of amorphous phase, which may be responsible for grain size reduction and high crystalline resistivity of Si-doped specimens. Compared with the conventional Ge₂Sb₂Te₅ film, Si-doped Sb₂Te₃ films exhibit lower melting temperature and higher crystalline resistivity, which is beneficial to RESET current reduction of phase-change random access memory (PRAM). These results show the feasibility of Si-doped Sb₂Te₃ films in PRAM application.     

Ab-initio calculations of Co-based diluted magnetic semiconductors Cd1−xCoxX (X=S, Se, Te)

Ab-initio calculations are performed to investigate the structural, electronic and magnetic properties of spin-polarized diluted magnetic semiconductors composed of II-VI compounds Cd_1−xCo_xX (X=S, Se, Te) at x=0.25. From the calculated results of band structure and density of states, the half-metallic character and stability of ferromagnetic state for Cd_1−xCo_xS, Cd_1−xCo_xSe and Cd_1−xCo_xTe alloys are determined. It is found that the tetrahedral crystal field gives rise to triple degeneracy t_2g and double degeneracy e_g. Furthermore, we predict the values of spin-exchange splitting energies Δ_x(d) and Δ_x(p−d) and exchange constants N₀α and N₀β produced by the Co 3d states. Calculated total magnetic moments and the robustness of half-metallicity of Cd_1−xCo_xX (X=S, Se, Te) with respect to the variation in lattice parameters are also discussed. We also extend our calculations to x=0.50, 0.75 for S compounds in order to observe the change due to increase in Co.     

Crystal structure, electronic and transport properties of AgSbSe2 and AgSbTe2

Undoped and p- and n-doped AgSbX₂ (X=Se and Te) materials were synthesized by direct fusion technique. The structural properties were investigated by X-ray diffraction and SEM microscopy. The electrical conductivity, thermal conductivity and Seebeck coefficient have been measured as a function of temperature in the range from 300 to 600 K.To enlighten electron transport behaviours observed in AgSbSe₂ and AgSbTe₂ compounds, electronic structure calculations have been performed by the Korringa-Kohn-Rostoker method as well as KKR with coherent potential approximation (KKR-CPA) for ordered (hypothetical AgX and SbX as well as AgSbX₂ approximates) and disordered systems (Ag_1−xSb_xX), respectively. The calculated density of states in the considered structural cases shows apparent tendencies to opening the energy gap near the Fermi level for the stoichiometric AgSbX₂ compositions, but a small overlap between valence and conduction bands is still present. Such electronic structure behaviour well agrees with the semimetallic properties of the analyzed samples.     

The effect of Fe substitution on the electrical and thermal conductivity and thermopower of Ca3(FexCo1−x)4O9 synthesised by a sol–gel process

The effect of Fe substitution for Co on direct current (DC) electrical and thermal conductivity and thermopower of Ca₃(Co_1−xFe_x)₄O₉ (x = 0, 0.05, 0.08), prepared by a sol–gel process, was investigated in the temperature range from 380 down to 5K. The results indicate that the substitution of Fe for Co results in an increase in thermopower and DC electrical resistivity and substantial (14.9–20.4% at 300K) decrease in lattice thermal conductivity. Experiments also indicated that the temperature dependence of electrical resistivity ρ for heavily substituted compounds Ca₃(Co_1−xFe_x)₄O₉ (x = 0.08) obeyed the relation lnρ ∝ T^−1/3 at low temperatures, T < ~55K, in agreement with Mott’s two-dimensional (2D) variable range hopping model. The enhancement of thermopower and electrical resistivity was mainly ascribed to a decrease in hole carrier concentration caused by Fe substitution, while the decrease of thermal conductivity can be explained as phonon scattering caused by the impurity. The thermoelectric performance of Ca₃Co₄O₉ was not improved in the temperature range investigated by Fe substitution largely due to great increase in electrical resistivity after Fe substitution.