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.     

Fundamental band edge optical absorption in Bi<Subscript>0.5</Subscript>Sb<Subscript>1.5</Subscript>Te<Subscript>3</Subscript>

Spectra of optical absorption in Bi_0.5Sb_1.5Te₃ films grown on mica and KBr substrates have been investigated for T = 145 and 300 K. The data obtained have been analyzed together with the data of investigations on the fundamental absorption edge for Bi₂Te₃ available in the scientific literature. It has been revealed that the interband absorption spectra for both Bi_0.5Sb_1.5Te₃ and Bi₂Te₃ represent a superposition of two components corresponding to direct and indirect allowed optical transitions. In this case, the least energy gap separating the valence band and the conduction band is direct for Bi_2−xSb_xTe₃ (x ≤ 1.5, T = 300 K). For Bi_0.5Sb_1.5Te₃ the temperature variation rates have been estimated for the thresholds of direct and indirect interband transitions. It has been shown that this solid solution is direct gap solution at T ≥ 145 K. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 50–52, July, 2008.     

Thermal sensors based on Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript> and (Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript>)<Subscript>70</Subscript>(Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>)<Subscript>30</Subscript> thin films

Thin films of Sb₂Te₃ and (Sb₂Te₃)₇₀(Bi₂Te₃)₃₀ alloy and have been deposited on precleaned glass substrate by thermal evaporation technique in a vacuum of 2?×?10^?6 Torr. The structural study was carried out by X-ray diffractometer, which shows that the films are polycrystalline in nature. The grain size, microstrain and dislocation density were determined. The Seebeck coefficient was determined as the ratio of the potential difference across the films to the temperature difference. The power factor for the (Sb₂Te₃)₇₀ (Bi₂Te₃)₃₀ and (Sb₂Te₃) is found to be 19.602 and 1.066 of the film of thickness 1,500 Å, respectively. The Van der-Pauw technique was used to measure the Hall coefficient at room temperature. The carrier concentration was calculated and the results were discussed.     

Weak antilocalization in thin films of the Bi<Subscript>2</Subscript>Te<Subscript>2.7</Subscript>Se<Subscript>0.3</Subscript> solid solution

A technology has been developed for the preparation of thin films of the Bi₂Te_2.7Se_0.3 solid solution through the thermal evaporation in a vacuum using the “hot-wall” method. The high quality of the thin films thus prepared has been confirmed by the X-ray diffraction and Raman scattering data. The electron transport has been investigated over wide ranges of temperatures (1.4–300 K) and magnetic fields (up to 8 T). It has been assumed that the observed weak antilocalization is associated with the dominant contribution from the surface states of a topological insulator. The dephasing length has been estimated.     

Effect of conditions of preparation on the thermoelectric properties of solid solutions of Bi<Subscript>0.5</Subscript>Sb<Subscript>1.5</Subscript>Te<Subscript>3</Subscript>

The effect the conditions of preparing thermoelectric solid solutions of Bi_0.5Sb_1.5Te₃ + 0.06 wt % Pb by hardening from the liquid state with subsequent hot pressing have on their thermoelectric properties is studied. It is found that the optimum thermoelectric quality factors are achieved at a 2200–2800 rpm rate of copper disc rotation.     

Specific features of the electronic,spin, and atomic structures of a topological insulator Bi<Subscript>2</Subscript>Te<Subscript>2.4</Subscript>Se<Subscript>0.6</Subscript>

The specific features of the electronic and spin structures of a triple topological insulator Bi₂Te_2.4Se_0.6, which is characterized by high-efficiency thermoelectric properties, have been studied with the use of angular- and spin-resolved photoelectron spectroscopy and compared with theoretical calculations in the framework of the density functional theory. It has been shown that the Fermi level for Bi₂Te_2.4Se_0.6 falls outside the band gap and traverses the topological surface state (the Dirac cone). Theoretical calculations of the electronic structure of the surface have demonstrated that the character of distribution of Se atoms on the Te–Se sublattice practically does not influence the dispersion of the surface topological electronic state. The spin structure of this state is characterized by helical spin polarization. Analysis of the Bi₂Te_2.4Se_0.6 surface by scanning tunnel microscopy has revealed atomic smoothness of the surface of a sample cleaved in an ultrahigh vacuum, with a lattice constant of ~4.23 Å. Stability of the Dirac cone of the Bi₂Te_2.4Se_0.6 compound to deposition of a Pt monolayer on the surface is shown.     

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.     

Influence of annealing at temperatures above the solidus temperature on the structure and galvanomagnetic properties of Bi<Subscript>92</Subscript>Sb<Subscript>8</Subscript> solid-solution thin films

The influence of the annealing temperature from the interval between the solidus and liquidus temperatures of Bi₉₂Sb₈ solid solution on its structure and galvanomagnetic and thermoelectric properties has been studied. It has been shown that films of bismuth–antimony solid solution grown by thermal evaporation in a vacuum will have a large-grained structure after annealing at temperatures higher than the solidus temperature of the solid solution. It has been found that these films offer the lowest resistivity, the highest relative magnetoresistance, and the highest mobility of charge carriers. As the annealing temperature approaches the liquidus temperature, the probability that a dendritic structure will form and antimony-enriched regions will appear grows. This causes an increase in the charge carrier concentration and a decrease in the resistivity with a decrease in the relative magnetoresistance and charge carrier mobility.     

Stratification of Bi<Subscript>0.5</Subscript>Sb<Subscript>1.5</Subscript>Te<Subscript>3</Subscript> Single Crystals and Sintering of the Obtained Micro- and Nanoscale Plates

The use of surface active liquids facilitates intense stratification of mechanically strained Bi_0.5Sb_1.5Te₃ crystallites. A Bi_0.5Sb_1.5Te₃ heat element with specified thickness and structure is formed by layer-by-layer deposition of “thermoelectric ink” on its free surface. A heat treatment of the formed thermoelectric element in argon at a temperature of 800 K makes it possible to minimize radically the resistance of the grain boundaries introduced into its bulk.     

Impact of Ultrathin Pb Films on the Topological Surface and Quantum-Well States of Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript> and Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript> Topological Insulators

The effect of an ultrathin Pb film deposited on the surface of Bi₂Se₃ and Sb₂Te₃ compounds on the electronic state structure of topological insulators is studied experimentally by the angle-resolved photoemission spectroscopy (ARPES) technique. The following features are revealed: formation of two-dimensional quantum-well states in the near-surface region, an increase in the binding energy of the Dirac cone and the core levels, and a simultaneous electronic states intensity redistribution in the system in photoemission spectra. The results obtained show that topological states may coexist at the interface between studied materials and a superconductor, which seems to be promising for application in quantum computers.     

Electrophysical parameters of <Emphasis Type="Italic">c</Emphasis>-oriented Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> films with a low concentration of antistructural defects

Epitaxial c-oriented Bi₂Te₃ films 1.2 μm in thickness are grown by the hot wall method for a low supersaturation of the vapor phase over the surface of mica substrates. The hexagonal unit cell parameters a = 4.386 Å and c = 30.452 Å of the grown films almost coincide with the corresponding parameters of stoichiometric bulk Bi₂Te₃ crystals. At T = 100 K, the Hall concentration of electrons in the films is on the order of 8 × 10¹⁸ cm^?3, while the highest values of the thermoelectric coefficient (α ≈ 280 μV K^?1) are observed at temperatures on the order of 260 K. Under impurity conduction conditions, conductivity σ of the films increases upon cooling in inverse proportion to the squared temperature. In the temperature range 100–200 K, thermoelectric power parameter α²σ of Bi₂Te₃ films has values of 80–90 μW cm^?1 K^?2.     

Selective wet etching of Ge<Subscript>2</Subscript>Sb<Subscript>2</Subscript>Te<Subscript>5</Subscript> phase-change thin films in thermal lithography with tetramethylammonium

In this paper, we study Ge₂Sb₂Te₅ phase-change film as a promising inorganic photoresist using organic alkaline: tetramethylammonium hydroxide (TMAH) solution, instead of inorganic alkali or acid as etchant. The basic etching properties are investigated by prior and posterior annealing Ge₂Sb₂Te₅ films. Selectivity is found to be dependent on concentration of TMAH. There is a good selectivity in the 25% TMAH solution, in which the amorphous state is etched away, whereas the crystalline state remains. The etching rate decreases when the concentration of TMAH is diluted; and an opposite selectivity, compared with 25% TMAH solution, is observed in the 0.125% TMAH solution. Selective etching with laser crystallization in different power levels is also studied, and an excellent wet selectivity in the 25% TMAH solution is obtained. The remaining crystalline lines are observed by atomic force microscopy. The surface roughness after etching is at a good level. The selective wet-etching mechanism is also discussed.     

Features of the electronic spectrum and optical absorption of ultrathin Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript> films

The electronic spectra and relative permittivity of ultrathin (1–3 QL) films of Bi₂Se₃ topological insulator have been calculated by the density functional theory. The calculated spectra exhibit a characteristic feature: the range of 0.0–0.9 eV below the Fermi level contains two doubly degenerate valence bands (“U-bands”), which are geometrically congruent to low-lying spectral branches in the conduction band. It has been shown that the saturation of optical absorption can result in a significant rearrangement of the electronic structure and properties in the near infrared spectral range in the considered film. In particular, the semiconductor (in the absence of interaction with light) type of conductivity of the film can be changed to the metallic type of conductivity strongly nonlinear in the intensity of light.     

Energy spectrum of holes in Sb<Subscript>2</Subscript>Te<Subscript>2.9</Subscript>Se<Subscript>0.1</Subscript> solid solution according to the data on the transfer phenomena

The temperature dependence of the Hall coefficient of a single crystal of the p-Sb₂Te_2.9Se_0.1 solid solution grown by the Czochralski technique is studied in the temperature range 77–450 K. The data on the Hall coefficient of the p-Sb₂Te_2.9Se_0.1 are analyzed in combination with the data on the Seebeck and Nernst–Ettingshausen effects and the electrical conductivity with allowance for interband scattering. From an analysis of the temperature dependences of the four kinetic coefficients, it follows that, at T < 200 K, the experimental data are qualitatively and quantitatively described in terms of the one-band model. At higher temperatures, a complex structure of the valence band and the participation of the second-kind additional carriers (heavy holes) in the kinetic phenomena should be taken into account. It is shown that the calculations of the temperature dependences of the Seebeck and Hall coefficients performed in the two-band model agree with the experimental data with inclusion of the interband scattering when using the following parameters: effective masses of the density of states of light holes m_d1^*≈ 0.5m₀ (m₀ is the free electron mass) and heavy holes m_d2^*≈ 1.4m₀, the energy gap between the main and the additional extremes of the valence band ΔE_v ≈ 0.14 eV that is weakly dependent on temperature.     

Role of Ge incorporation in the physical and dielectric properties of Se<Subscript>75</Subscript>Te<Subscript>25</Subscript> and Se<Subscript>85</Subscript>Te<Subscript>15</Subscript> glassy alloys

The effect of Ge additive on the physical and dielectric properties of Se₇₅Te₂₅ and Se₈₅Te₁₅ glassy alloys has been investigated. It is inferred that on adding Ge, the physical properties i.e., average coordination number, average number of constraints and average heat of atomization increase but lone pair electrons, fraction of floppy modes, electronegativity, degree of crosslinking and deviation of stoichiometry (R) decrease. The effect of Ge doping on the dielectric properties of the bulk Se₇₅Te₂₅ and Se₈₅Te₁₅ glassy alloys has also been studied in the temperature range 300–350 K for different frequencies (1 kHz–5 MHz). It is found that, with doping, the dielectric constant ε^′ and dielectric loss ε^″ increase with increase in temperature and decrease with increase in frequency. The role of the third element Ge, as an impurity in the two pure binary Se₇₅Te₂₅ and Se₈₅Te₁₅ glassy alloys has been discussed in terms of the nature of covalent bonding and electronegativity difference between the elements used in making the aforesaid glassy systems.     

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.     

Thermoelectric properties of multicomponent solid solutions based on bismuth and antimony chalcogenides with n-type conduction in the region of impurity and mixed conduction

The thermoelectric properties of Bi_2?x Sb _x Te_{3 ? y ? z} Se _y S _z solid solutions are studied in the temperature range 300–450 K. It is shown that, as the number of atoms involved in substitutions in both sublattices during the formation of a solid solution increases, the maximum in the temperature dependence of the thermopower coefficient and the minimum in the temperature dependence of the thermal conductivity shift toward higher temperatures as a result of an increase in the band gap. As the charge carrier concentration in the sample of a solid solution increases, the onset of mixed conduction shifts toward higher temperatures, which leads to an additional decrease in the thermal conductivity at a fixed temperature. The observed temperature dependences of the thermoelectric properties of the Bi_{2 ? x} Sb _x Te_{3 ? y ? z} Se _y S _z solid solutions bring about a shift of the maximum in the thermoelectric efficiency toward higher temperatures as the number of atoms involved in the substitution increases.     

Anomalous increase of the thermopower and thermoelectric figure of merit in Ga-doped <Emphasis Type="Italic">p</Emphasis>-(Bi<Subscript>0.5</Subscript>Sb<Subscript>0.5</Subscript>)<Subscript>2</Subscript>Te<Subscript>3</Subscript> single crystals

The effect of Ga doping on the temperature dependences (5 K ≤ T ≤ 300 K) of the Seebeck coefficient α, electrical conductivity σ, thermal conductivity coefficient κ, and thermoelectric figure of merit Z of p-(Bi_0.5Sb_0.5)₂Te₃ single crystals has been investigated. It has been shown that, upon Ga doping, the hole concentration decreases, the Seebeck coefficient increases, the electrical conductivity decreases, and the thermoelectric figure of merit increases. The observed variations in the Seebeck coefficient cannot be completely explained by the decrease in the hole concentration and indicate a noticeable variation in the density of states due to the Ga doping.     

Stability of the (0001) surface of the Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript> topological insulator

The inertness of the cleaved (0001) surface of a Bi₂Se₃ single crystal to oxidation has been demonstrated using X-ray photoelectron spectroscopy, as well as atomic-force and scanning tunneling microscopy and spectroscopy. No intrinsic bismuth and selenium oxides are formed on the surface after a month of storage in air. Atomically flat surfaces with macroscopic sizes (∼1 cm²) and rms roughness less than 0.1 nm have been prepared, and (1 × 1)-(0001) Bi₂Se₃ atomic structure has been resolved. The tunneling conductance measurements have shown that the energy dependence of the surface density of states is quasilinear in the band gap of Bi₂Se₃.     

Plasma screening of the fundamental absorption edge in crystals of Bi2Te3-Sb2Te3 solid solutions with more than 80 mol % Sb2Te3

The regularities of changes in the optical properties of crystals of Bi₂Te₃-Sb₂Te₃ solid solutions in the range of the effects caused by free-carrier plasma oscillations at a variation in the ratio of Bi₂Te₃ and Sb₂Te₃ components are investigated. It is established that, when the Sb₂Te₃ content in a solid solution exceeds 80 mol %, the fundamental absorption edge undergoes plasma screening. Doping a Sb₂Te₃ crystal with tin increases the free-carrier concentration and plasma frequencies, thus enhancing the screening effect, whereas introduction of 0.1 mol % selenium reduced the plasma frequency and thus removes the fundamental-absorption-edge screening.