Thermoelectric properties of Bi2Se3/Bi2Te3/Bi2Se3 and Sb2Te3/Bi2Te3/Sb2Te3 quantum well systems

In this work, we develop a theory of thermoelectric transport properties in two-dimensional semiconducting quantum well structures. Calculations are performed for n-type 0.1 wt.% CuBr-doped Bi₂Se₃/Bi₂Te₃/Bi₂Se₃ and p-type 3 wt.% Te-doped Sb₂Te₃/Bi₂Te₃/Sb₂Te₃ quantum well systems in the temperature range 50–600 K. It is found that reducing the well thickness has a pronounced effect on enhancing the thermoelectric figure of merit (ZT). For the n-type Bi₂Se₃/Bi₂Te₃/Bi₂Se₃ with 7 nm well width, the maximum value of ZT is estimated to be 0.97 at 350 K and for the p-type Sb₂Te₃/Bi₂Te₃/Sb₂Te₃ with well width 10 nm the highest value of the ZT is found to be 1.945 at 440 K. An explanation is provided for the resulting higher ZT value of the p-type system compared to the n-type system.     

Effect of heat treatment on the structure and the thermoelectric properties of Sb<Subscript>0.9</Subscript>Bi<Subscript>1.1</Subscript>Te<Subscript>2.9</Subscript>Se<Subscript>0.1</Subscript> thin films and composites based on them

This work considers the effect of vacuum annealing on the thermoelectric properties of Sb_0.9Bi_1.1Te_2.9Se_0.1 thin film and Sb_0.9Bi_1.1Te_2.9Se_0.1–C composites with various carbon contents produced by ion-beam deposition in an argon atmosphere. The electrical resistivity and the thermopower of Sb_0.9Bi_1.1Te_2.9Se_0.1–C nanocomposites are found to be dependent on not only the carbon concentration but also the type and the concentration of intrinsic point defects of the Sb_0.9Bi_1.1Te_2.9Se_0.1 solid solution, which determine the type of conductivity of Sb_0.9Bi_1.1Te_2.9Se_0.1 granules. The power factors are estimated for films of Sb_0.9Bi_1.1Te_2.9Se_0.1 solid solution and films of Sb_0.9Bi_1.1Te_2.9Se_0.1–C composites and found to have values comparable with the values for nanostructured materials on the basis of (Bi,Sb)₂(Te,Se)₃ solid solutions.     

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.     

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.     

Electrochemical deposition of Bi2Te3-based thin films

The electrochemical reduction processes on stainless-steel substrates from an aqueous electrolyte composed of nitric acid, Bi³⁺, HTeO₂⁺, SbO⁺ and H₂SeO₃ systems were investigated using cyclic voltammetry. The thin films with a stoichiometry of Bi₂Te₃, Bi_0.5Sb_1.5Te₃ and Bi₂Te_2.7Se_0.3 have been prepared by electrochemical deposition at selected potentials. The structure, composition, and morphology of the films were studied by X-ray diffraction (XRD), environmental scanning electron microscopy (ESEM) and electron microprobe analysis (EMPA). The results showed that the films were single phase with the rhombohedral Bi₂Te₃ structure. The morphology and growth orientation of the films were dependent on the deposition potentials.     

An analysis of the thermoelectric efficiency of n-(Bi,Sb)2(Te,Se,S)3 solid solutions within an isotropic scattering model

A study is reported on the thermoelectric properties of n-type solid solutions Bi₂Te_3?y Se_y (y=0.12, 0.3, 0.36), Bi_2?x Sb_xTe_3?y Se_y (x=0.08, 0.12; y=0.24, 0.36), and Bi₂Te_3?z S_z (z=0.12, 0.21) as functions of carrier concentration within the 80-to 300-K range. It has been established that the highest thermoelectric efficiency Z is observed in the Bi₂Te_3?y Se_y (y=0.3) solid solution containing excess Te at optimum carrier concentrations (0.35×10¹⁹ cm^?3) and at temperatures from 80 to 250 K. The increase in Z in the Bi₂Te_3?y Se_y solid solution compared with Bi_2?x Sb_xTe_3?y Se_y and Bi₂Te_3?z S_z is accounted for by the high mobility μ₀, an increase in the effective mass m/m ₀ with decreasing temperature, the low lattice heat conductivity κ_L, and the weak anisotropy of the constant-energy surface in a model assuming isotropic carrier scattering.     

General solution-based route to V–VI semiconductors nanorods from hydrolysate

V–VI (Bi₂Se₃, Bi₂Te₃, Sb₂Se₃, and Sb₂Te₃) semiconductors nanorods with the diameters of 40–90 nm have been synthesized starting from BiCl₃ (or SbCl₃) and Na₂SeO₃ (or Na₂TeO₃) by using NaH₂PO₂·H₂O as the reduced agent at 140°C for 24 h. The samples were characterized by XRD, SEM and TEM. XPS spectra of the products show the obtained samples are close to stoichiometry. The hydrolysate of the starting materials could be served as the precursor and sharply decreases the growth of the samples; a possible hydrolyzation–reduction–crystallization process was also proposed to explore the formation mechanism of these nanorods.     

Switching phenomena in amorphous thin films of Ge,Cd x Te y and Sb x Se y

The threshold and memory switching effects in amorphous thin films of Ge, Cd _x Te _y and Sb _x Se _y , prepared by cathodic sputtering and vacuum evaporation are investigated. The switching is dependent on the polarity and the material of the contacts. The memory effect is typical for Ge and Cd _x Te _y films whilst the threshold effect sustaining a repeating frequency of about 0·1 Hz was found with Sb _x Se _y , films. The proper switching time was 0·2–0·4 s for the samples under consideration. A considerable variance of the critical intensity of the electric field when the switching set in was observed, as well as a variance of its dependence on the temperature and the surface properties of the substrate. With Ge samples the switching depended on the total amount of energy accumulated in them. A simple model is proposed on the ground of the achieved results assuming electronic processes in the first phase of the duration of the switching (i.e. injection from electrodes into the amorphous film) and bulk thermal processes leading to the creatin of a conduction channel in the second phase.     

Crystallization kinetics in new Sb14As29Se52Te5 amorphous glass

Differential scanning calorimetry (DSC) under non-isothermal conditions is used to study the crystallization kinetics of Sb₁₄As₂₉Se₅₂Te₅ chalcogenide glass. In addition, two approaches are used to analyze the dependence of glass transition temperature (T_g) on the heating rate (α). One is empirical linear relationship between (T_g) and ln(α). The second approach is the use of straight line vs. 1/T_g for the evaluation of the activation energy for glass transition. The phases at which the alloy crystallizes after the thermal treatment have been identified by using X-ray diffraction. The diffractogram of the transformed material shows the presence of some crystallites of As, Te, AsSb, As₂Se₃, Sb₂Se₃ and AsSe_.5Te_.5 in the residual amorphous matrix.     

Effect of thermal treatment on the thermoelectric properties of Sb<Subscript>0.9</Subscript>Bi<Subscript>1.1</Subscript>Te<Subscript>2.9</Subscript>Se<Subscript>0.1</Subscript> solid solution thin films

The effect thermal treatment in a vacuum has on the thermoelectric properties of Sb_0.9Bi_1.1Te_2.9Se_0.1 solid solution thin films obtained via ion-beam sputtering in an argon atmosphere is considered. It is established that the specific resistance and thermopower are determined by the type and concentration of intrinsic point defects of the Sb_0.9Bi_1.1Te_2.9Se_0.1 solid solution. The power factor values are found to be comparable to those of nanostructured materials based on (Bi,Sb)₂(Te,Se)₃ solid solutions.     

Three- and two-dimensional topological insulators in Pb2Sb2Te5, Pb2Bi2Te5, and Pb2Bi2Se5 layered compounds

The electronic structure of ternary compounds Pb₂Sb₂Te₅, Pb₂Bi₂Te₅, and Pb₂Bi₂Se₅, which have a layered structure that consists of nine-layer atomic blocks separated by van der Waals gaps, has been theoretically studied. It has been shown that all studied compounds are three-dimensional topological insulators. The possibility of the existence of a two-dimensional topological insulator has been found in ultrathin (0001) Pb₂Sb₂Te₅ and Pb₂Bi₂Te₅ films. Oscillations of the ℤ₂ topological invariant with an increase in the film thickness have been observed in the latter compound.     

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.     

The heterostructure and electrical properties of Sb2Se3/Bi2Se3 grown by molecular beam epitaxy

We report the growth and characterization of Sb₂Se₃/Bi₂Se₃ bilayer films fabricated by molecular beam epitaxy. High quality heterostructures are obtained as evidenced from the X-ray diffraction (XRD), atomic force microscopy and high-resolution transmission electron microscopic (HRTEM) analysis. Interestingly, Sb₂Se₃ grows as a (120) hexacrystal film in orthorhombic phase on rhombohedral Bi₂Se₃ (0001) plane, as verified by the out-of-plane and in-plane XRD scans. The cross-sectional TEM studies indicate a sharp interface between Sb₂Se₃ and Bi₂Se₃, which is important for the protection of surface states Bi₂Se₃. The ultraviolet photoelectron spectroscopy indicates that the Fermi level located 0.95 eV above the valence band maximum in Sb₂Se₃. The insulating nature of Sb₂Se₃ is confirmed by the nonlinear current-voltage curve via the vertical junction electrical measurement. By four point probe measurements, we confirm the charge transfer effect from Sb₂Se₃ into Bi₂Se₃, and such effect can be reduced in the Sb₂Se₃/(Bi_0.7Sb_0.3)₂Se₃ bilayer. This work opens a new avenue for the synthesis of multilayers consisting of topological insulators and ordinary insulator, which is important for harvesting of the multiple surface states for advanced electronic and spintronic applications.     

Specific features in the behavior of the effective mass and mobility in n-(Bi, Sb)2(Te, Se, S)3 solid solutions

The thermoelectric properties of the multicomponent solid solutions Bi_2?x Sb_xTe_3?y?z Se_yS_z with substitutions of atoms in both sublattices of Bi₂Te₃ were studied. The data obtained in studies of the galvanomagnetic effects in weak magnetic fields were used to properly take into account the change in the carrier scattering mechanisms due to the substitutions Sb → Bi, Se, and S → Te in the solid solutions. The mobility μ₀ with inclusion of the degeneracy, the effective density-of-states mass m/m ₀, and the lattice thermal conductivity κ_L were calculated. An analysis was carried out for the quantities μ₀, m/m ₀, and κ_L in the solid solutions under study as functions of the composition, carrier concentration, and temperature.     

Growth behavior of Bi2Te3 and Sb2Te3 thin films on graphene substrate grown by plasma‐enhanced chemical vapor deposition

A comparative study of the substrate effect on the growth mechanism of chalcogenide Bi₂Te₃ and Sb₂Te₃ thin films was carried out. Obvious microstructural discrepancy in both the as‐deposited Bi₂Te₃ and Sb₂Te₃ thin films was observed when grown on graphene or SiO₂/Si substrate. Bi₂Te₃ and Sb₂Te₃ thin films deposited on the graphene substrate were observed to be grown epitaxially along c‐axis and show very smooth surface compared to that on SiO₂/Si substrate. Based on the experimental results of this study, the initial adsorption sites on graphene substrate during deposition process, which had been discussed theoretically, could be demonstrated empirically.     

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.     

A transmission electron microscopy study on the atomic arrangement and grain growth of hexagonal structured Ge2Sb2Te5

The atomic arrangement and grain growth of the hexagonal structured Ge₂Sb₂Te₅ were investigated by a transmission electron microscopy study. Unlike the isotropic crystallization of face-centered-cubic (fcc) structured Ge₂Sb₂Te₅, the hexagonal structured Ge₂Sb₂Te₅ grain was preferably grown to a large degree with a specific direction. As a result, we have revealed that the grain growth occurred parallel to the (0 0 0 1) plane, and identified the atomic arrangement of the hexagonal structured Ge₂Sb₂Te₅ having nine cyclic layers by analyzing the high-resolution transmission electron microscopy images and simulated images obtained in the direction of zone axis.     

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.     

Magnetic and transport properties of Mn-doped Bi2Se3 and Sb2Se3

We report on the single crystal growth and thermoelectric and magnetic properties of Mn-doped Bi₂Se₃ and Sb₂Se₃ single crystals prepared by the temperature gradient solidification method. The composition and crystal structure were determined using electron probe microanalysis and θ–2θ powder X-ray diffraction studies, respectively. The lattice constants of several percent Mn-doped Bi₂Se₃ and Sb₂Se₃ were slightly smaller than those of the undoped sample due to the smaller Mn atomic radius (1.40 Å) than those of Bi (1.60 Å) and Sb (1.45 Å). Mn-doped Bi₂Se₃ and Sb₂Se₃ showed spin-glass and paramagnetic properties, respectively.