Thermal Conductivity in Bi1−x Sb x Solid Solutions

Bi_1?x Sb _x solid solutions have attracted much attention as promising low-temperature thermoelectric materials. Previously, we observed distinct extrema in the isotherms of the transport and mechanical properties of polycrystalline Bi_1?x Sb _x and attributed their presence to the transition from diluted to concentrated solid solutions and to the reconstruction of the energy band structure under increasing Sb concentration. The goal of the present work is a detailed study of the concentration dependences of the thermal conductivity λ for Bi_1?x Sb _x polycrystalline solid solutions (x = 0 to 0.09) in the temperature range of 170 K to 300 K. It is established that the λ(x) dependences exhibit a nonmonotonic behavior: in certain concentration ranges an anomalous increase in λ with increasing x is observed. It is shown that the concentration dependences of the thermoelectric figure of merit calculated on the basis of the measured λ values are also nonmonotonic. The obtained data represent additional evidence in favor of our assumptions stated earlier about a significant effect of electronic phase transitions observed in Bi_1?x Sb _x solid solutions on the concentration dependences of their thermoelectric properties. These results should be taken into account when developing new Bi_1?x Sb _x -based materials.     

Erratum to: First-Principles Investigation of Electronic Properties of GaAsxSb1 – x Ternary Alloys

Semiconductors - erratum     

Thermoelectric Properties of (Bi1−x Sb x )2S3 with Orthorhombic Structure

Thermoelectric properties of the substitution system (Bi_1?x Sb _x )₂S₃ have been investigated, where binary Bi₂S₃ and Sb₂S₃ are narrow-gap semiconductors. It is confirmed that metallic conduction, originating from mobile electrons due to production of sulfur vacancies, is observed in Bi₂S₃ over a wide temperature range below room temperature. In Sb₂S₃, mobile carriers are not created and insulating behavior is observed because of the considerably wide bandgap. Change of the carrier number by substitution of antimony contributes strongly to the thermoelectric properties (resistivity and Seebeck coefficient). As a result, the nondimensional figure of merit, ZT, decreases monotonically with increasing antimony content. The maximum value of ZT is obtained in Bi₂S₃ as ZT ≈ 0.1 at room temperature. It is pointed out that control of the carrier number, which is achieved by production of sulfur vacancies, is important to achieve high thermoelectric performance in the (Bi_1?x Sb _x )₂S₃ system. It is possible that the thermoelectric efficiency could be improved by control of the carrier concentration in the bismuth-rich region, including pure binary Bi₂S₃.     

Effect of Surface Preparation on Mechanical Properties of Ni Contacts on Polycrystalline (Bi1?x Sb x )2(Te1?y Se y )3 Alloys

We present a comparison of different surface preparation techniques for hot-extruded (Bi_1?x Sb _x )₂(Te_1?y Se _y )₃ alloys prior to Ni plating and their consequences on adhesion. The surface preparation is carried out by a relatively fast and well-controlled electrochemical etching procedure that provides morphologies with homogeneous flat surfaces on a scale of tens of micrometers. This procedure is not optimal for Ni metallization since it does not ensure enough roughness on the surface. Applying wet chemical etching with hypochlorite and nitric acid after the electrochemical etching changes the morphology, and the surface roughness increases, as evidenced by scanning electron microscopy and atomic force microscopy. Tensile tests carried out on n-type and p-type 1-mm-thick specimens, covered with a 12-??m Ni layer followed by Sn-Pb soldered joints, confirm a significant improvement in the ultimate adhesion strength, with fracture occurring within the thermoelectric material. Use of this two-step surface treatment, after slicing and prior to metallization, leads to maximum adhesion strength of around 38?MPa for either type of thermoelectric material. These results are consistent with the morphological changes observed by scanning electron microscopy on the surface after chemical etching.     

Quasiharmonic Vibrational Properties of TiNiSn from Ab?Initio Phonons

We report an ab?initio study of vibrational and thermodynamic properties of TiNiSn, a half-Heusler alloy that has been investigated in the context of thermoelectrics, based on density functional theory and density functional perturbation theory. The quasiharmonic approximation, where the Helmholtz free energy obtained from phonons of multiple strained structures is fitted to a model equation of state, is employed to estimate thermodynamic properties. Good quantitative correspondence is achieved between experimental observations and our theoretical calculation for various thermodynamic quantities: lattice parameter, thermal expansion coefficient, and heat capacity. Estimates of lattice thermal conductivity are also provided by using a semianalytic model previously proposed in the literature. Though this yields good qualitative agreement, a more accurate ab?initio approach that explicitly includes anharmonic interactions between atoms should be employed for quantitative predictions of thermal conductivity.     

Thermoelectric Performance of p-Type (Bi85Sb15)1?x Sn x Materials Prepared by a Pressureless Sintering Technique

In this study, a series of Sn-doped (Bi₈₅Sb₁₅)_1?x Sn _x (x?=?0, 0.025, 0.05, 0.1, 0.2, 0.3) thermoelectric materials was fabricated through mechanical alloying followed by pressureless sintering. The crystal structure was characterized by x-ray diffraction. The electrical transport properties and thermal properties were measured in the temperature range from 77?K to 300?K. The electrical transport as a function of temperature appeared to be characteristic of a semimetal. The Seebeck coefficient gradually changed from negative to positive with increasing Sn doping, showing p-type electrical transport properties. It is found that the Seebeck coefficients of the p-type Bi-Sb alloys decrease with increasing dopant concentration of Sn, which may be due to increasing carrier concentration. Among the p-type alloys, the power factor of (Bi₈₅Sb₁₅)_0.975Sn_0.025 reached a maximum value of 1.3?×?10^?3?W/mK² at 265?K, and the optimum figure of merit value of 0.13 was obtained at 240?K. The results indicate that good p-type Bi-Sb alloys can be prepared by this synthesis procedure.     

Physicochemical Properties of Sn-Zn and SAC + Bi Alloys

Applying the discharge crucible (DC) method, the viscosity, density, and surface tension were determined for Sn-9Zn and Sn-2.92Ag-0.4Cu-3.07Bi (SAC + Bi) alloys. For comparison, the dilatometric, maximum bubble pressure, and capillary flow methods were used for measurements of these same physicochemical properties for the Sn-2.92Ag-0.4Cu-3.07Bi (SAC + Bi) alloy. The measurements were performed for Sn-9Zn and SAC + Bi alloys in the temperature range from 513 K to 723 K and 530 K to 1180 K, respectively. The experimental data obtained show that addition of Bi to SAC increases the density and decreases the surface tension and viscosity in comparison with SAC solder. Additionally it was found that the properties studied by different methods (maximum bubble pressure, dilatometric, capillary flow, and discharge crucible) were almost identical.     

Electrochemical Deposition and Characterization of Thermoelectric Ternary (Bi x Sb1?x )2Te3 and Bi2(Te1?y Se y )3 Thin Films

Thermoelectric thin films of the ternary compounds (Bi _x Sb_1?x )₂Te₃ and Bi₂(Te_1?y Se _y )₃ were synthesized using potentiostatic electrochemical deposition on gold-coated silicon substrates from aqueous acidic solutions at room temperature. The surface morphology, elemental composition, and crystal structure of the deposited films were studied and correlated with preparation conditions. The thermoelectric properties of (Bi _x Sb_1?x )₂Te₃ and Bi₂(Te_1?y Se _y )₃ films, i.e., Seebeck coefficient and electrical resistivity, were measured after transferring the films to a nonconductive epoxy support. (Bi _x Sb_1?x )₂Te₃ thin films showed p-type semiconductivity, and the highest power factor was obtained for film deposited at a relatively large negative potential with composition close to Bi_0.5Sb_1.5Te₃. In addition, Bi₂(Te_1?y Se _y )₃ thin films showed n-type semiconductivity, and the highest power factor was obtained for film deposited at a relatively small negative potential, having composition close to Bi₂Te_2.7Se_0.3. In contrast to Bi₂Te_2.7Se_0.3 thin films, an annealing treatment was required for Bi_0.5Sb_1.5Te₃ thin films to achieve the same magnitude of power factor as Bi₂Te_2.7Se_0.3. Therefore, Bi₂Te_2.7Se_0.3 thin films appear to be good candidates for multilayer preparation using electrochemical deposition, but the morphology of the films must be further improved.     

Effect of Se Substitution on Structural and Electrical Transport Properties of Bi0.4Sb1.6Se3x Te3(1−x) Hexagonal Rods

In the current study, novel hexagonal rods based on Bi_0.4Sb_1.6Te₃ ingots dispersed with x amount of Se (x = 0.0, 0.2, 0.4, 0.6, 0.8, and 1.0) in the form Bi_0.4Sb_1.6Se_3x Te_3(1?x) were synthesized via a standard solid-state microwave route. The morphologies of these rods were explored using field-emission scanning electron microscopy (FESEM). The crystal structure of the powders was examined by x-ray diffraction (XRD) analysis, which showed that powders of the 0.0 ≤ x ≤ 0.8 samples could be indexed to the rhombohedral phase, whereas the sample with x = 1.0 had an orthorhombic phase structure. The influence of variations in the Se content on the thermoelectric properties was studied in the temperature range from 300 K to 523 K. Alloying of Se into Bi_0.4Sb_1.6Te₃ effectively caused a decrease in the hole concentration and, thus, a decrease in the electrical conductivity and an increase in the Seebeck coefficient. The maximal power factor measured in the present work was 7.47 mW/mK² at 373 K for the x = 0.8 sample.     

Effect of Nonlinearity of the Phonon Spectrum on the Thermal Conductivity of Nanostructured Materials Based on Bi–Sb–Te

A theoretical investigation of the lattice thermal conductivity of nanostructured materials based on Bi–Sb–Te is presented. The calculations were based on relaxation time approximation and took into account both the real phonon spectra, obtained from first-principles by use of density functional theory, and the anisotropy of phonon relaxation time. Phonon relaxation time data were determined from experimental values of the lattice thermal conductivity. The decrease of the thermal conductivity caused by the nanostructure was compared with results from calculations based on the linear Debye approach. Estimation showed that phonon boundary scattering can lead to a 55% decrease of thermal conductivity for a grain size of ~20 nm in the Debye approximation. Taking the nonlinearity of the acoustic phonon spectrum into account leads to a 20% larger decrease of the thermal conductivity because of boundary scattering. The reason is that consideration of the real phonon spectrum increases the relative contribution to thermal conductivity of acoustic phonons with low frequencies that are scattered more strongly at nanograin boundaries. Similarly, estimation of lattice thermal conductivity reduction as a result of phonon scattering by nanoinclusions gave an 8% larger decrease when the real phonon spectrum was used rather than the linear Debye approximation. For such a substantial decrease of lattice thermal conductivity, the effect of the optical phonons was estimated; it was shown that optical phonons can reduce the change of thermal conductivity as a result of grain boundary scattering by no more than 10%. Finally, the minimum lattice thermal conductivity was estimated to be 0.07 W/m K because of acoustic modes (0.09 W/m K in the Debye approach) and 0.14 W/m K when the contribution of optical modes was also taken into consideration.     

In As1–x Sb x heteroepitaxial structures on compositionally graded GaInSb and AlGaInSb buffer layers

Semiconductors - Unrelaxed InAs1–x Sb x (x = 0.43 and 0.38) alloy layers are produced by molecular-beam epitaxy on compositionally graded GaInSb and AlGaInSb buffer layers. The high quality...     

Structure and Transport Properties of Bulk Nanothermoelectrics Based on Bi x Sb2−x Te3 Fabricated by SPS Method

Ball milling with subsequent spark plasma sintering (SPS) was used to fabricate bulk nanothermoelectrics based on Bi _x Sb_2?x Te₃. The SPS technique enables reduced size of grains in comparison with the hot-pressing method. The electrical and thermal conductivities, Seebeck coefficient, and thermoelectric figure of merit as functions of temperature and alloy composition were measured for different sintering temperatures. The greatest value of the figure of merit ZT = 1.25 was reached at the temperature of 90°C to 100°C in Bi_0.4Sb_1.6Te₃ for sintering temperature of 450°C to 500°C. The volume and quantitative distributions of size of coherent dispersion areas (CDA) were calculated for different sintering temperatures. The phonon thermal conductivity of nanostructured Bi _x Sb_2?x Te₃ was investigated theoretically taking into account phonon scattering on grain boundaries and nanoprecipitates.     

Nature of the diamagnetic maximum in the temperature dependences of the magnetic susceptibility of crystals of (Bi2 ? x Sb x )Te3 alloys (0 < x < 1)

The temperature dependences of the magnetic susceptibility ?? of crystals of (Bi_{2 ? x} Sb _x )Te₃ alloys (0 < x < 1) are studied using a SQUID magnetometer in the temperature range from 2 to 400 K with the parallel and perpendicular orientations of the vector of magnetic field strength H relative to the trigonal axis of the crystal C ₃ (H ?? C ₃ and H ?? C ₃). It is found that the diamagnetic susceptibility of the samples with x = 0.2 (Bi_1.8Sb_0.2Te₃) and x = 0.5 (Bi_1.5Sb_0.5Te₃) increases in the range from 50 K to temperatures preceding the emergence of intrinsic conductivity (250 K). It is found that the diamagnetic maximum manifests itself in the same temperature range, in which an anomalous increase in the Hall coefficient is observed. It is shown that the nature of the diamagnetic maximum is associated with the nonparabolicity of the energy spectrum of light diamagnetic holes, a decrease in whose concentration is accompanied by a decrease in their effective masses, which provides an increase in the diamagnetic susceptibility with increasing temperature. These results are confirmed by the dynamics of the temperature variation in the resonance frequency of plasma oscillations of free charge carriers.     

Conduction- and Valence-Band Energies in Bulk InAs1−x Sb x and Type II InAs1−x Sb x /InAs Strained-Layer Superlattices

The energy gaps were studied in two types of structures: unrelaxed bulk InAs_1?x Sb _x layers with x = 0.2 to 0.46 grown on metamorphic buffers and type II InAs_1?x Sb _x /InAs strained-layer superlattices (SLS) with x = 0.225 to 0.296 in the temperature range from T = 13 K to 300 K. All structures were grown on GaSb substrates. The longest wavelength of photoluminescence (PL) at low temperatures was observed from bulk InAs_0.56Sb_0.44 with a peak at 10.3 μm and full-width at half-maximum (FWHM) of 11 meV. The PL data for the bulk InAs_1?x Sb _x materials of various compositions imply an energy gap bowing parameter of 0.87 eV. A low-temperature PL peak at 9.1 μm with FWHM of 13 meV was observed for InAs_0.704Sb_0.296/InAs SLS. The PL spectrum of InAs_0.775Sb_0.225/InAs SLS under pulsed excitation revealed a second peak associated with recombination of electrons in the three-dimensional (3D) continuum with holes in the InAs_0.775Sb_0.225. This experiment determined the conduction-band offset in the InAs_0.775Sb_0.225/InAs SLS. The energies of the conduction and valence bands in unstrained InAs_1?x Sb _x and their bowing with respect to the Sb composition are discussed.     

On the Thermoelectric Properties of Zintl Compounds Mg3Bi2−x Pn x (Pn = P and Sb)

A series of Zintl compounds Mg₃Bi_2-x Pn _x (Pn = P and Sb) have been synthesized by the solid-state reaction method. While Sb can be substituted to a level as high as x = 1.0, P can be substituted only up to x = 0.5. The thermoelectric potential of these compounds has been evaluated by measuring resistivity (ρ), Seebeck (α) and Hall coefficients, and thermal conductivity between 80 K and 850 K. The measured resistivity and Seebeck coefficient values are consistent with those expected for small-bandgap semiconductors. Hall measurements suggest that the carriers are p type with concentration (p) increasing from ~10¹⁹ cm^?3 to ~10²⁰ cm^?3 as the Bi content is increased. The Hall mobility decreases with increasing temperature (T) and reaches a more or less similar value (~45 cm²/V s) for all substituted compositions at room temperature. Due to mass defect scattering, the lattice thermal conductivity (κ _L) is decreased to a minimum of ~1.2 W/m K in Mg₃BiSb. The power factor (α ²/ρ) is found to be rather low and falls in the range 0.38 mW/m K² to 0.66 mW/m K². As expected, at a high temperature of 825 K, the total thermal conductivity (κ) of Mg₃BiSb reaches an impressive value of ~1.0 W/m K. The highest dimensionless figure of merit (ZT) is realized for Mg₃BiSb and is ~0.4 at 825 K.     

Effects of Reaction Temperature on Thermoelectric Properties of p-Type Nanostructured Bi2−x Sb x Te3 Prepared Using Hydrothermal Method and Evacuated-and-Encapsulated Sintering

We report fabrication of nanostructured Bi_2?x Sb _x Te₃ using hydrothermal method followed by cold-pressing and evacuated-and-encapsulated sintering techniques. To obtain lower resistivity, the reaction temperature in the hydrothermal synthesis is investigated, and the effects on the ZT values of Bi_2?x Sb _x Te₃ are reported. Both the x = 1.52 and 1.55 samples hydrothermally synthesized at 160°C show lower resistivity than the x = 1.55 sample hydrothermally synthesized at 140°C. However, the power factor is lower for the samples synthesized at 160°C due to the accompanying smaller thermopower. All three samples exhibit remarkably low thermal conductivity of around 0.41 W m^?1 K^?1 at room temperature. The peak ZT value occurs at 270 K for all three samples, being ZT = 1.75, 1.29, and 1.17 for x = 1.55 (synthesized at 140°C), 1.55 (synthesized at 160°C), and 1.52 (synthesized at 160°C), respectively.     

On the preparation and photoelectric properties of Tl1–x In1–x Sn x Se2 (x = 0.1–0.25) alloys

The technological conditions for growing single crystals of Tl_1–x In_1–x Sn _x Se₂ (x = 0.1–0.25) alloys are developed. The spectral distribution of the photoconductivity of the grown crystals at T = 300 K and thermally stimulated conductivity are studied. The effect of In³⁺cation substitution with Sn⁴⁺ in Tl_1–x In_1–x Sn _x Se₂ (x = 0.1–0.25) alloys on their photoelectric properties is shown.     

Effect of Chromium Doping on the Thermoelectric Properties of Bi2Te3: Cr x Bi2Te3 and Cr x Bi2−x Te3

The thermoelectric (TE) properties of Bi₂Te₃ compounds intercalated and substituted with Cr, namely Cr _x Bi₂Te₃ and Cr _x Bi_2?x Te₃, respectively, have been investigated to study the influence of chromium on the TE properties of Bi₂Te₃. The Seebeck coefficients were found to be positive for all the samples in the temperature range between 300 K and 550 K. Although no effective enhancement of the Seebeck coefficient was observed, doping with Cr by means of either substitution or intercalation clearly not only improved the electrical conductivity but also lowered the thermal conductivity of Bi₂Te₃. As a result of the improvement, the figure of merit ZT is increased up to 0.8 and 0.65 at 300 K for 1% intercalated and 1% substituted Bi₂Te₃, respectively.     

Material Characterization of Ge1−x Sn x Alloys Grown by a Commercial CVD System for Optoelectronic Device Applications

High-quality compressive-strained Ge_1?x Sn _x /Ge films have been deposited on Si(001) substrate using a mainstream commercial chemical vapor deposition reactor. The growth temperature was kept below 450°C to be compatible with Si complementary metal–oxide–semiconductor processes. Germanium tin (Ge_1?x Sn _x ) layers were grown with different Sn composition ranging from 0.9% to 7%. Material characterizations, such as secondary-ion mass spectrometry, Rutherford backscattering spectrometry, and x-ray diffraction analysis, show stable Sn incorporation in the Ge lattice. Comparison of the Sn mole fractions obtained using these methods shows that the bowing factor of 0.166 nm (in Vegard’s law) is in close agreement with other experimental data. High-resolution transmission electron microscopy and atomic force microscopy results show that the films have started to relax through the formation of misfit and threading dislocations. Raman spectroscopy, ellipsometry, and photoluminescence (PL) techniques are used to study the structural and optical properties of the films. Room-temperature PL of the films shows that 7% Sn incorporation in the Ge lattice results in a decrease in the direct bandgap of Ge from 0.8 eV to 0.56 eV.