Structure and electrical properties of Sb2Te3 and Bi0.4Sb1.6Te3 metastable phases obtained by HPHT treatment

We have obtained the metastable phase of the thermoelectric alloy Bi_0.4Sb_1.6Te₃ with electron type conductivity for the first time using the method of quenching under pressure after treatment at P=4.0 GPa and T=400–850 °C. We have consequently performed comparative studies with the similar phase of Sb₂Te₃. The polycrystalline X-ray diffraction patterns of these phases are similar to the known monoclinic structure α-As₂Te₃ (C2/m) with less monoclinic distortion, β ≈ 92°. We have measured the electrical resistivity and the Hall coefficient in the temperature range of T=77?450 K and we have evaluated the Hall mobility and density of charge carriers. The negative Hall coefficient indicates the dominant electron type of carriers at temperatures up to 380 K in the metastable phase of Sb₂Te₃ and up to 440 K in the metastable state of Bi_0.4Sb_1.6Te₃. Above these temperatures, the p-type conductivity proper to the initial phases dominates.     

Thermoelectric properties of p-Bi2 ? xSbxTe3 solid solutions under pressure

This paper reports on a study of the Seebeck coefficient and power factor κ of p-Bi_{2 − x} Sb _x Te₃ solid solutions with different contents of antimony atoms in the bismuth sublattice for x = 0, 1.4, 1.5, and 1.6 under variation of pressure of up to 15 GPa. The magnitude of κ has been found to grow nonmonotonically within the pressure region of 2–4 GPa. The effective mass of the density of states m/m ₀ and the mobility μ₀ have been calculated with due account of degeneracy within the parabolic model of the energy spectrum assuming isotropic charge carrier scattering. It has been shown that application of pressure brings about a decrease of the effective mass m/m ₀ and an increase of carrier mobility. The power factor κ of the p-Bi_0.6Sb_1.4Te₃ composition exhibits at the pressure P ≈ 4 GPa the largest increase of the power factor κ as a result of a weak decrease of the effective mass m/m ₀ and an increase of carrier mobility as compared to the other solid solution compositions. The specific feature of the variation of the power factor κ with a change of the pressure in bismuth telluride near P ≈ 3 GPa, which is accompanied by formation of a knee in the m/m ₀ vs. P dependence, can be assigned to an electronic topological transition.     

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)     

Electrophysical properties and electronic structure of tin-doped antimony telluride

The effect of Sn atoms on the electrophysical properties and x-ray photoelectron spectra of Czochralski-grown Sb₂Te₃ single crystals is studied. The character of the temperature dependences of the kinetic coefficients is shown to depend noticeably on the structure of the valence band, which consists of two valence subbands. Estimates of the effective density-of-states masses of holes and of the gap between the valence-band extrema in Sb₂Te₃: Sn agree with the data available for the Sb₂Te₃ not doped with tin. X-ray photoelectron spectra of Sb₂Te₃: Sn single crystals do not exhibit noticeable core-level shifts and electron density redistribution in the valence band.     

Experimental and theoretical study of silicon-doped Sb2Te3 thin films: Structure and phase stability

The influence of Si in Sb₂Te₃ on structure and phase stability was studied by experiments and ab initio calculations. With the increase of Si content in Sb₂Te₃ samples, the crystallization temperature increases and the crystalline grain size decreases. The incorporation of Si atoms into Sb₂Te₃ lattice is energetically unfavorable and hence Si atoms most probably accumulated in the boundaries of Sb₂Te₃ grains.     

Features of the electron density distribution in antimony telluride Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript>

Based on the results of electron density functional calculations of the electronic band structure of semiconductors Sb₂Te₃, Ge, Te, and semimetal Sb, the parameters of critical points in the electron density distribution (maxima, minima, and saddle points) in the lattices of the above materials are found. The data obtained are used to analyze the chemical bond nature in Sb₂Te₃.     

Phase stability and electronic structure of Si2Sb2Te5 phase-change material

On the basis of an ab initio computational study, the present work provide a full understanding on the atomic arrangements, phase stability as well as electronic structure of Si₂Sb₂Te₅, a newly synthesized phase-change material. The results show that Si₂Sb₂Te₅ tends to decompose into Si₁Sb₂Te₄ or Si₁Sb₄Te₇ or Sb₂Te₃, therefore, a nano-composite containing Si₁Sb₂Te₄, Si₁Sb₄Te₇ and Sb₂Te₃ may be self-generated from Si₂Sb₂Te₅. Hence Si₂Sb₂Te₅ based nano-composite is the real structure when Si₂Sb₂Te₅ is used in electronic memory applications. The present results agree well with the recent experimental work.     

Effect of thermal annealing on microstructural properties of Ti/Ge2Sb2Te5/Ti thin films deposited on SiO2/Si substrates by a sputtering method

Ti/Ge₂Sb₂Te₅/Ti thin films deposited by a sputtering method on SiO₂/Si substrates were annealed at 400 °C in N₂ atmosphere and characterized by using transmission electron microscopy (TEM) and Auger electron spectroscopy (AES) in order to investigate the inter-diffusion of the Ti/Ge₂Sb₂Te₅/Ti system due to annealing. The TEM and AES results showed that the interface between the Ti and the Ge₂Sb₂Te₅ layers was unstable and Ti atoms were incorporated into the Ge₂Sb₂Te₅ thin film upon annealing. The Te and Sb atoms of the Ge₂Sb₂Te₅ layer diffused into the Ti layer. The intermixing layers between the Ge₂Sb₂Te₅ layer and two Ti layers were formed. These results indicate that the microstructural properties of the Ti/Ge₂Sb₂Te₅/Ti systems can be degraded by the postgrowth thermal annealing.     

Investigation of Sb-rich Si2Sb2+x Te6 material for phase change random access memory application

Sb-rich Si₂Sb_2+x Te₆ (x=0, 1.4, 10) thin films are proposed to present the feasibility for electronic phase change memory application. The crystallization behavior is improved by adding Sb into the material. The crystallization temperature is about 506, 502, and 450 K for Si₂Sb₂Te₆, Si₂Sb_3.4Te₆, and Si₂Sb₁₂Te₆ films, respectively, and the corresponding activation energy is in the range from 2.70 to 1.69 eV, which is expected for a low-power and high-speed SET operation. In addition, maximum temperature for a 10 year data lifetime is estimated to be 133, 127, and 98°C, respectively. The memory devices are successfully fabricated employing these films, promising that the stability of the low-resistance crystalline state is improved by adding Sb into the stoichiometric Si₂Sb₂Te₆ material, and the reversibility of the device is also realized for the Si₂Sb₁₂Te₆-based cell.     

Local atomic structure in molten Si3Sb2Te3 phase change material

By means of ab initio molecular dynamics calculations, we have studied the local structures of liquid and amorphous Si₃Sb₂Te₃. The results show that all the constitute elements in liquid Si₃Sb₂Te₃ are octahedrally coordinated. While in amorphous state, Sb and Te atoms are mainly octahedrally coordinated and Si atoms are mainly tetrahedrally coordinated. In both states, Si is mainly homo-bonded by Si. Finally, we proposed a phase separation model for liquid and amorphous Si₃Sb₂Te₃, which is responsible for the good performance of Si₃Sb₂Te₃ alloy as a phase change material.     

Improving the thermoelectric properties of thick Sb2Te3 film via Cu doping and annealing deposited by DC magnetron sputtering using a mosaic target

Thick Cu-doped Sb₂Te₃ films were deposited on flexible substrate by DC magnetron sputtering from a mosaic Cu–Sb₂Te₃ target. The Cu-doped Sb₂Te₃ films were vacuum annealed to improve their thermoelectric properties. Density functional theory was used to clarify the internal mechanism of the Cu doped into the Sb₂Te₃ system. The results showed that Cu substitution on a Sb site induced electronic states or impurity peaks of Sb₂Te₃ at a valence band maximum. The carrier concentration of the Cu-doped Sb₂Te₃ films increased as the Cu-doped concentration increased. However, the crystallite size and Seebeck coefficient of the Cu-doped Sb₂Te₃ films decreased as the Cu-doped concentration increased. Post-annealing treatment improved the microstructure and thermoelectric properties of the Cu-doped Sb₂Te₃ films. The maximum electrical conductivity and power factor values of 754.20 S/cm at 50 °C and 1.56 10⁻³ W/mK² at 100 °C were obtained in the annealed film with a Cu-doped concentration of 3 at%.     

On the origin of two-dimensional electron gas states at the surface of topological insulators

The ab initio calculations of the electronic structure in the bulk and at the (0001) surface of narrow-band Bi₂Se₃, Sb₂Te₃, Sb₂STe₃, and Sb₂SeTe₂ semiconductors have been performed. It has been shown that ternary compounds Sb₂STe₂ and Sb₂SeTe₂, as well as the previously known compounds Bi₂Se₃ and Sb₂Te₃, are three-dimensional topological insulators. The influence of the subsurface van der Waals gap expansion on the surface electronic structure of these compounds has been analyzed. It has been shown that this expansion leads to the formation of new (trivial) surface states, namely a parabolic state in the conduction band and an M-shaped state in the valence band. These results explain the phenomena discovered recently in photoemission experiments and reveal the nature of new states that are caused by the adsorption of atoms on the surfaces of the layered topological insulators.     

Energy formation of antisite defects in doped Sb2Te3 and Bi2Te3 crystals

The free carrier concentration of the Sb_2−xIn_xTe₃, Bi_2−xIn_xTe₃ and Bi₂Te_3−xS_x crystals has been determined from the values of the Hall constants and the free carrier concentration of the Sb_2−xTl_xTe₃ has been calculated from the plasma resonance frequency; with increasing value of x, the hole concentration decreases. As the incorporation of the elements In, Tl and S into the lattice Sb₂Te₃ or Bi₂Te₃, respectively, gives rise to the uncharged defects In^x_Sb, Tl^x_Sb, In^x_Bi and S^x_Te, the x causes the decrease of the antisite defects concentration. The proven effect is explained in the following way: the antisite defects can be created only in crystals whose atoms are bound by weakly polarized bonds. The incorporation of In, Tl and S atoms into the crystal lattice of Sb₂Te₃ or Bi₂Te₃ increases the bond polarity, the ionicity of ternary crystals increases. This unfavorably affects the increase of antisite defects whose concentration decreases. The change of the bond polarity is considered from the changes discovered in the formation energy of antisite defects of the above mentioned ternary crystals.     

Sb2Te3 纳米结构的制备与表征

以室温热电性能优异的传统热电材料Sb₂Te₃为研究对象,利用化学气相沉积法制备Sb₂Te₃单晶纳米结构,并研究其生长机理.实验结果表明,不加催化剂时Sb₂Te₃易生长成六方纳米盘,在金催化剂条件下定向生长成纳米线.Sb₂Te₃的形貌与其晶体结构和生长机理有关.Sb₂Te₃为三角结构,Sb和     

Local structure of AlSb2Te3 thin film studied by experimental and theoretical methods

Local structure of AlSb₂Te₃ thin film was studied by experiments and theoretical calculations. Results show that both Sb and Te atoms are likely to be replaced by Al to form Al–Sb and Al–Te covalent bonds. At a smaller dopant concentration, Al atoms presumably incorporate into Sb₂Te₃ matrix by substitute Sb or Te atoms without spoiling its structural unit. Compared together with other reported data, for Al doping Sb₂Te₃ PCM material, optimizing Al content is a key criteria for its phase stability and electric performance.     

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.     

Migration of nitrogen in hexagonal Ge2Sb2Te5: An ab‐initio study

The migration barrier energies of the nitrogen atom and N₂ molecule, and the activation barriers for the dissociation and formation of N₂ in Ge₂Sb₂Te₅ were calculated by ab‐initio methods. Various transition and metastable states were found along the migration pathway. Migration barrier energies up to 1.19 eV for the nitrogen atom suggest that it is difficult for it to move from one site to any other site or diffuse out from Ge₂Sb₂Te₅ although doped nitrogen is energetically less stable with respect to N₂ in vacuum. N₂ in Ge₂Sb₂Te₅ was hardly expected to dissociate into nitrogen atoms and vice versa. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of the atomic composition of the surface on the electron surface states in topological insulators A<Stack><Subscript>2</Subscript><Superscript>V</Superscript></Stack>B<Stack><Subscript>3</Subscript><Superscript>VI</Superscript></Stack>

The results of the theoretical investigation of the surface electronic structure of A₂^VB₃^VI compounds containing topologically protected surface states are reported. The ideal Bi₂Te₃, Bi₂Se₃, and Sb₂Te₃ surfaces and surfaces with an absent external layer of chalcogen atoms, which were observed experimentally as monolayer terraces, have been considered. It has been shown that the discrepancy between the calculated Fermi level and the value measured in the photoemission experiments can be attributed to the presence of the “dangling bond” states on the surface of the terraces formed by semimetal atoms. The fraction of such terraces on the surface has been estimated.     

Investigation on Ge5−x Sb x Te5 phase-change materials by first-principles method

The structure stability and chemical bonding of Ge_5?x Sb _x Te₅ (x=0,1,2) phase-change alloys were studied by ab initio calculations. By analyzing formation energies, density of states and electron localization function, we have shown that the chemical bonding character of Ge₄Sb₁Te₅ is quite similar to that of GeTe and hence a NaCl crystalline state is expected. The introduction of extra electrons by Sb in Ge₄Sb₁Te₅ and Ge₃Sb₂Te₅ results in states at the Fermi Level. With increasing Sb contents as in Ge₃Sb₂Te₅, the chemical bonding becomes rather inhomogeneous.     

Effective Mass Enhancement and Thermal Conductivity Reduction for Improving the Thermoelectric Properties of Pseudo-Binary Ge2Sb2Te5

Ge₂Sb₂Te₅ is a famous phase-change memory material for rewriteable optical storage, which is widely applied in the information storage field. The stable trigonal phase of Ge₂Sb₂Te₅ shows potential as a thermoelectric material as well, due to its tunable electrical transport properties and low lattice thermal conductivity. In this work, the carrier concentration and effective mass of Ge₂Sb₂Te₅ are modulated by substituting Te with Se. Meanwhile, the thermal conductivity reduces from 2.48 W m⁻¹ K⁻¹ for Ge₂Sb₂Te₅ to 1.37 W m⁻¹ K⁻¹ for Ge₂Sb₂Te_3.5Se_1.5 at 703 K. Therefore, the thermoelectric figure of merit zT increases from 0.24 for Ge₂Sb₂Te₅ to 0.41 for Ge₂Sb₂Te_3.5Se_1.5 at 703 K. This study reveals that Se alloying is an effective way to enhance the thermoelectric properties of Ge₂Sb₂Te₅.