Thermodynamic Re-modeling of the Sb-Te System Using Associate and Ionic Models

The Sb-Te system is re-modeled using the calculation of phase diagram (CALPHAD) technique. The liquid phase is modeled as (Sb, Sb₂Te₃, Te) using the associate model and as (Sb³⁺) _p (Te^2?,Te,Va) _q using the ionic model. The solution phases rhom(Sb) and hex(Te) are described as substitutional solutions. Two compounds, delta and gamma, are treated as (Sb)_0.4(Sb,Te)_0.6 according to their homogeneity ranges, while the compound Sb₂Te₃ follows a strict stoichiometry. A set of self-consistent thermodynamic parameters is obtained. Using these thermodynamic parameters, the experimental Sb-Te phase diagram, mixing enthalpies of liquid at 911 K and 935 K, activities of Sb and Te in liquid at 911 K and 1023 K, and Gibbs energy of liquid at 911 K, is well reproduced by the calculations. And the calculated enthalpy of formation, enthalpy of fusion, and heat capacity of Sb₂Te₃ are also in fairly good agreement with all the available experimental data.     

Interface Microstructure and Performance of Sb Contacts in Bismuth Telluride-Based Thermoelectric Elements

A thermoelectric joint composed of p-type Bi_0.5Sb_1.5Te₃ (BiSbTe) material and an antimony (Sb) interlayer was fabricated by spark plasma sintering. The reliability of the thermoelectric joints was investigated using electron probe microanalysis for samples with different accelerated isothermal aging time. After aging for 30 days at 300°C in vacuum, the thickness of the diffusion layer at the BiSbTe/Sb interface was about 30 μm, and Sb₂Te₃ was identified to be the major interfacial compound by element analysis. The contact resistivity was 3 × 10^?6 ohm cm² before aging and increased to 8.5 × 10^?6 ohm cm² after aging for 30 days at 300°C, an increase associated with the thickness of the interfacial compound. This contact resistivity is very small compared with that of samples with solder alloys as the interlayer. In addition, we have also investigated the interface behavior of Sb layers integrated with n-type Bi₂Se_0.3Te_2.7 (BiSeTe) material, and obtained similar results as for the p-type semiconductor. The present study suggests that Sb may be useful as a new interlayer material for bismuth telluride-based power generation devices.     

Low Thermal Conductivity in High-Z Thermoelectric Materials with Controlled Nanodispersions

We report wet chemical synthesis of a hierarchical nanocomposite thermoelectric material, (Bi,Sb)₂Te₃ + 2 vol.% Sb₂O₃, which exhibits a very high ZT value of 1.5 at 333 K. The key to such a high ZT value is to design the interfacial density (ID) of the nanodispersion and the mean diameter of the matrix (d) in the nanocomposite. To this end, (Bi,Sb)₂Te₃ with Sb₂O₃ nanodispersion was developed using in situ precipitation during solvothermal treatment. Nanocomposite structure was observed in sintered specimens. By evaluation of thermoelectric properties, it was confirmed that phonon scattering on the surface of Sb₂O₃ dispersion and κ _ph correspondingly decreased with ID. The formation of a well-controlled Sb₂O₃ dispersion (mean diameter of dispersion: D = 1.5 nm, ID = 0.06 nm^?1) and fine grains (d = 38 nm) led to an extremely low lattice thermal conductivity of 0.28 W m^?1 K^?1, while reducing the electrical conductivity moderately according to the conventional mixture rule.     

Mechanisms of incorporation of an antimony impurity into cadmium telluride crystals

The results of electrical studies of CdTe crystals grown by the Bridgman-Stockbarger method and doped with Sb impurity to concentrations of 10¹⁷–3×10¹⁹ cm^?3 were considered. An analysis of the temperature dependences of the Hall coefficient, the charge-carrier mobility, and photoconductivity under the intrinsic-absorption excitation for various portions of the ingots made it possible to conclude that Sb_Te and Sb_Cd centers and Sb_TeSb_Cd associations are introduced upon doping CdTe crystals with Sb impurity. The hole conduction in the doped crystals is controlled by A ₃ (Sb_Te) acceptors whose concentration is no higher than 5×10¹⁶ cm^?3 and is much lower than the actual Sb concentration. The ionization energy of the A ₃ acceptors is 0.28±0.01 eV. Under nonequilibrium conditions, these acceptors act as attachment centers for holes (at high temperatures) and as slow-rate recombination centers for electrons (at low temperatures).     

Low-Temperature,Solution-Based,Scalable Synthesis of Sb2Te3 Nanoparticles with an Enhanced Power Factor

Nanostructured thermoelectric (TE) materials, for example Sb₂Te₃, PbTe, and SiGe-based semiconductors, have excellent thermoelectric transport properties and are promising candidates for next-generation TE commercial application. However, it is a challenge to synthesize the corresponding pure nanocrystals with controlled size by low-temperature wet-chemical reaction. Herein, we report an alternative versatile solution-based method for synthesis of plate-like Sb₂Te₃ nanoparticles in a flask using SbCl₃ and Te powders as raw materials, EDTA-Na₂ as complexing agent, and NaBH₄ as reducing agent in the solvent (distilled water). To investigate their thermoelectric transport properties, the obtained powders were cold compacted into cuboid prisms then annealed under a protective N₂ atmosphere. The results showed that both the electrical conductivity (σ) and the power factor (S ² σ) can be enhanced by improving the purity of the products and by increasing the annealing temperature. The highest power factor was 2.04 μW cm^?1 K^?2 at 140°C and electrical conductivity remained in the range 5–10 × 10³ S m^?1. This work provides a simple and economic approach to preparation of large quantities of nanostructured Sb₂Te₃ with excellent TE performance, making it a fascinating candidate for commercialization of cooling devices.     

Thermal Conductivity of Exfoliated p-Type Bismuth Antimony Telluride

A bulk p-type thermoelectric compound with nominal composition Bi_0.5Sb_1.5 Te₃ has been exfoliated using dimethyl sulfoxide as a solvent. Samples have been prepared from the exfoliated platelets by pressing followed by sintering or hot pressing. The exfoliated nanoplatelets have been characterized for size distribution and composition using scanning electron microscopy and energy-dispersive spectrometry. The smallest size platelet was 40 nm, and the maximum in the size distribution was near 80 nm. The exfoliated platelets and sintered sample showed significant deficiency in Sb and Te. The nonstoichiometry in the composition of the exfoliated platelets indicates that the mechanism of exfoliation may not be between quintuplets only, with other layers also being active. The composition of the hot-pressed sample remained closer to that of the bulk. Results of x-ray diffraction indicated the presence of Bi₂Te₃ and Bi_0.5Sb_1.5Te₃ phases and pure Te and Sb. Residual porosity was observed in the hot-pressed and sintered samples. The thermal conductivity of the samples was measured by transient thermoreflectance. The results showed that the thermal conductivity of the hot-pressed sample was reduced by a factor of two compared with that of the bulk as a result of the presence of a high density of interfaces and residual porosity. The thermal conductivity of the sintered sample showed an increase above that of the bulk sample, which is explained by the change in composition due to loss of Sb and Te.     

Dielectric Properties of Au/PVA (Cobalt-Doped)/n-Si Photoconductive Diodes

The voltage (V) and frequency (f) dependence of dielectric parameters such as the dielectric constant (ε′), dielectric loss (ε″), dielectric loss tangent (tan δ), real and imaginary parts of electrical modulus (M′ and M″), and alternating-current (AC) electrical conductivity (σ _AC) of Au/PVA (cobalt-doped)/n-Si structures have been investigated by using experimental admittance measurements conducted at room temperature. The values of ε′, ε″, and tan δ were found to be strong functions of voltage and frequency, especially at low frequencies in the positive voltage region. It was observed that the values of ε′ and ε″ increase as the frequency decreases. The M′ values increase with increasing frequency due to increasing dielectric relaxation, while M″ values, in general, remain stable as frequency is changed. The σ _AC values at each bias voltage increase with increasing frequency.     

Electrical Conductivity and Dielectric Properties of Se85Te15−x Sb x (x = 0 at.%, 2 at.%, 4 at.%, and 6 at.%) Thin Films

The alternating-current (ac) conductivity and dielectric properties of Se₈₅Te_15?x Sb _x (x = 0 at.%, 2 at.%, 4 at.%, and 6 at.%) films are reported in this work. Thin films were deposited by thermal evaporation under base pressure of 10^?5 Torr. The films were well characterized by x-ray diffraction, differential scanning calorimetry, and energy-dispersive x-ray spectroscopy. The ac conductivity and dielectric properties have been investigated for the studied films in the temperature range from 297 K to 333 K and over the frequency range from 10² Hz to 10⁵ Hz. The experimental results indicate that the ac conductivity $ \sigma_{\rm{ac}} (\omega ) $ and the dielectric constant depend on temperature, frequency, and Sb content. The frequency dependence of $ \sigma_{\rm{ac}} (\omega ) $ was found to be linear with a slope lying very close to unity and is independent of temperature. This behavior can be explained in terms of correlated barrier hopping between centers forming intimate valence-alternation pairs. The density of localized states N(E _F) at the Fermi level is estimated. The activation energy $ \Updelta E(\omega ) $ was found to decrease with increasing frequency. The dielectric constant ε ₁ and dielectric loss ε ₂ were found to decrease with increasing frequency and increased with increasing temperature over the ranges studied. The maximum barrier height W _m for the studied films was calculated from an analysis of the dielectric loss ε ₂ according to the Guintini equation. The values agree with that proposed by the theory of hopping of charge carriers over a potential barrier as suggested by Elliott for chalcogenide glasses. The variation of the studied properties with Sb content was also investigated.     

Thermoelectric Characteristics of <Emphasis Type="Italic">p</Emphasis>-Type (Bi,Sb)<Subscript>2</Subscript>Te<Subscript>3</Subscript>/(Pb,Sn)Te Functional Gradient Materials with Variation of the Segment Ratio

The p-type (Bi,Sb)₂Te₃/(Pb,Sn)Te functional gradient materials (FGMs) were fabricated by hot-pressing mechanically alloyed (Bi_0.2Sb_0.8)₂Te₃ and 0.5 at.% Na₂Te-doped (Pb_0.7Sn_0.3)Te powders together at 500°C for 1 h in vacuum. Segment ratios of (Bi,Sb)₂Te₃ to (Pb,Sn)Te were varied as 3:1, 1.3:1, and 1:1.6. A reaction layer of about 350-μm thickness was formed at the (Bi,Sb)₂Te₃/(Pb,Sn)Te FGM interface. Under temperature differences larger than 340°C applied across a specimen, superior figures of merit were predicted for the (Bi,Sb)₂Te₃/(Pb,Sn)Te FGMs to those of (Bi_0.2Sb_0.8)₂Te₃ and (Pb_0.7Sn_0.3)Te. With a temperature difference of 320°C applied across a specimen, the (Bi,Sb)₂Te₃/(Pb,Sn)Te FGMs with segment ratios of 3:1 and 1.3:1 exhibited the maximum output powers of 72.1 mW and 72.6 mW, respectively, larger than the 63.9 mW of (Bi_0.2Sb_0.8)₂Te₃ and the 26 mW of 0.5 at.% Na₂Te-doped (Pb_0.7Sn_0.3)Te.     

Effect of Heat Treatment on the Thermoelectric Properties of Bismuth–Antimony–Telluride Prepared by Mechanical Deformation and Mechanical Alloying

In this work, p-type 20%Bi₂Te₃–80%Sb₂Te₃ bulk thermoelectric (TE) materials were prepared by mechanical deformation (MD) of pre-melted ingot and by mechanical alloying (MA) of elemental Bi, Sb, and Te granules followed by cold-pressing. The dependence on annealing time of changes of microstructure and TE properties of the prepared samples, including Seebeck coefficient, electrical resistivity, thermal conductivity, and figure-of-merit, was investigated. For both samples, saturation of the Seebeck coefficient and electrical resistivity were observed after annealing for 1 h at 380°C. It is suggested that energy stored in samples prepared by both MA and MD facilitated their recrystallization within short annealing times. The 20%Bi₂Te₃–80%Sb₂Te₃ sample prepared by MA followed by heat treatment had higher a Seebeck coefficient and electrical resistivity than specimens fabricated by MD. Maximum figures-of-merit of 3.00 × 10^?3/K and 2.85 × 10^?3/K were achieved for samples prepared by MA and MD, respectively.     

Enhanced Thermoelectric Properties of Antimony Telluride Thin Films with Preferred Orientation Prepared by Sputtering a Fan-Shaped Binary Composite Target

p-Type antimony telluride (Sb₂Te₃) thermoelectric thin films were deposited on BK7 glass substrates by ion beam sputter deposition using a fan-shaped binary composite target. The deposition temperature was varied from 100°C to 300°C in increments of 50°C. The influence of the deposition temperature on the microstructure, surface morphology, and thermoelectric properties of the thin films was systematically investigated. x-Ray diffraction results show that various alloy composition phases of the Sb₂Te₃ materials are grown when the deposition temperature is lower than 200°C. Preferred c-axis orientation of the Sb₂Te₃ thin film became obvious when the deposition temperature was above 200°C, and thin film with single-phase Sb₂Te₃ was obtained when the deposition temperature was 250°C. Scanning electron microscopy reveals that the average grain size of the films increases with increasing deposition temperature and that the thin film deposited at 250°C shows rhombohedral shape corresponding to the original Sb₂Te₃ structure. The room-temperature Seebeck coefficient and electrical conductivity range from 101 μV K^?1 to 161 μV K^?1 and 0.81 × 10³ S cm^?1 to 3.91 × 10³ S cm^?1, respectively, as the deposition temperature is increased from 100°C to 300°C. An optimal power factor of 6.12 × 10^?3 W m^?1 K^?2 is obtained for deposition temperature of 250°C. The thermoelectric properties of Sb₂Te₃ thin films have been found to be strongly enhanced when prepared using the fan-shaped binary composite target method with an appropriate substrate temperature.     

Improvement of Thermoelectric Properties in (Bi0.5Sb0.5)2Te3 Films of Nanolayered Pillar Arrays

In this work, it is found that unique pillar arrays with nanolayered structure can favorably influence the carrier and phonon transport properties of films. p-(Bi_0.5Sb_0.5)₂Te₃ pillar array film with (0 1 5) orientation was successfully achieved by a simple ion-beam-assisted technique at deposition temperature of 400°C, owing to the enhanced mobility of deposited atoms for more sufficient growth along the in-plane direction. The pillar diameter was about 250 nm, and the layered nanostructure was clear, with each layer in the pillar array being <30 nm. The properties of the oriented (Bi_0.5Sb_0.5)₂Te₃ pillar array were greatly enhanced in comparison with those of ordinary polycrystalline films synthesized at deposition temperature of 350°C and 250°C. The (Bi_0.5Sb_0.5)₂Te₃ pillar array film with (0 1 5) preferred orientation exhibited a thermoelectric dimensionless figure of merit of ZT = 1.25 at room temperature. The unique pillar array with nanolayered structure is the main reason for the observed improvement in the properties of the (Bi_0.5Sb_0.5)₂Te₃ film.     

Temperature Stability of V2O5-Doped KNN-LS-BF Lead-Free Piezoelectric Ceramics

V₂O₅-doped Na_0.5K_0.5NbO₃-LiSbO₃-BiFeO₃ (KNN-LS-BF) lead-free piezoelectric ceramics were prepared by the traditional sintering method, and their temperature stability was studied. Characterization of the temperature dependences of dielectric and piezoelectric properties of the V₂O₅-doped KNN-LS-BF ceramics showed that V₂O₅ doping could significantly improve the temperature stability in the temperature range of 30°C to 420°C and cause a downward shift in the orthorhombic–tetragonal phase transition to below room temperature. It was also found that the V₂O₅-doped KNN-LS-BF ceramics possess good dielectric and piezoelectric properties (ε _r > 1066, tan δ < 4%, d ₃₃ > 185 pC/N, k _p > 0.25) in the temperature range of 30°C to 300°C.     

Enhanced Thermoelectric Properties of (PbTe)0.88(PbS)0.12 Composites by Sb Doping

The effects of Sb doping on (PbTe)_0.88(PbS)_0.12 composites prepared by melting, ball milling, and spark plasma sintering were investigated. The x-ray diffraction results indicate that all samples Sb _x Pb_1?x Te_0.88S_0.12 with x = 0, 0.002, 0.004, 0.006 and 0.008 are composites containing PbTe with NaCl-type structure as the major phase and PbS with NaCl-type structure as the minor phase. The electrical resistivity is reduced with increasing Sb doping, from 1.95 × 10^?5 Ωm for Sb content x = 0 to 5.55 × 10^?6 Ωm for x = 0.008 at 298 K, showing that Sb is an efficient electron donor. However, the absolute Seebeck coefficient decreases, from 196 μV/K for x = 0 to 57.0 μV/K for x = 0.008 at 298 K, and the thermal conductivity increases, from 0.989 W/m K for x = 0 to 1.64 W/m K for x = 0.008, with Sb doping. The power factor and figure of merit ZT can be enhanced by proper Sb doping. The maximum dimensionless figure of merit ZT of 1.20 was obtained in the sample Sb_0.004Pb_0.996Te_0.88S_0.12 at 773 K.     

Optical Properties of Tellurium-Based Chalcogenide Alloys in the Far Infrared Region (λ &gt; 30 μm)

Ternary telluride alloys of Ge–Se(Sb)–Te and Si–Ge(Ga)–Te systems are synthesized in glassy and crystalline states for use in the terahertz frequency range. The transmission spectra of the obtained alloys are measured and studied in a wide wavelength range from 0.75 to 300 μm. The possible mechanisms of their formation are discussed. A comparative analysis of the results shows that the Ge₁₄Sb₂₈Te₅₆ alloy of the GST system is most promising. Its phonon spectrum is in the range of 40–280 cm^–1, limiting the long-wavelength transmission window of this alloy by 35 μm. Optimization of the Ge₁₄Sb₂₈Te₅₆ composition, the removal of impurities, and heat treatment will promote a further decrease in the absorbance in the far-infrared spectrum of this alloy.     

Preparation and Characterization of Bi0.4Sb1.6Te3 Bulk Thermoelectric Materials

This work focused on the preparation of p-type Bi_0.4Sb_1.6Te₃ bulk materials by combining mechanical alloying (MA) and hot extrusion, with emphasis on grain refinement and preferred grain orientation. Pure Bi, Sb, and Te powders were mechanically alloyed then hot extruded in the temperature range 360–450°C. Bi_0.4Sb_1.6Te₃ bulk materials were successfully prepared by MA and hot extrusion. All the samples had sound appearance, with single phases and high densities. The hot-extruded samples had small grain sizes, and the lower the extrusion temperature, the smaller the grain sizes. The results indicated that the extrudates had preferred orientation. The basal plane was predominantly oriented parallel to the direction of extrusion. Similar Seebeck coefficients were obtained when extrusion temperature was in the range 380–420°C. Electrical resistivity decreased with increasing extrusion temperature. Thermal conductivity was relatively low, even if the extrusion temperature was 450°C. As a result, a ZT value of 1.2 was obtained at room temperature for the sample extruded at 400°C. Therefore, combination of MA and hot extrusion results in significant improvement of both the thermoelectric and mechanical performance of Bi_0.4Sb_1.6Te₃ bulk materials.     

Evaluation of the Structure and Transport Properties of Nanostructured Antimony Telluride (Sb2Te3)

Antimony telluride, (Sb₂Te₃), and its doped derivatives are considered to be among the best p-type thermoelectric (TE) materials for room temperature (300–400 K) applications. However, it is still desirable to develop rapid and economical routes for large-scale synthesis of Sb₂Te₃ nanostructures. We report herein a high yield, simple and easily scalable synthetic method for polycrystalline Sb₂Te₃ nanostructures. Prepared samples were compacted into dense pellets by use of spark plasma sintering. The products were characterized by x-ray diffraction and scanning electron microscopy. To investigate the anisotropic behavior of Sb₂Te₃ TE transport property measurements were performed along and perpendicular to the direction of compaction. Thermal conductivity, electrical conductivity, and Seebeck coefficient measurement over the temperature range 350–525 K showed that the anisotropy of the material had a large effect on TE performance.     

Fabrication of Highly (0?0?l)-Textured Sb2Te3 Film and Corresponding Thermoelectric Device with Enhanced Performance

An approach for fabrication of highly (0?0?l)-textured Sb₂Te₃ thin film with layered structure by the magnetron sputtering method is reported. The composition, microstructure, and thermoelectric properties of the thin films have been characterized and measured by x-ray diffraction, scanning electron microscopy with energy-dispersive x-ray spectroscopy, and a thermoelectric (TE) measurement system, respectively. The results show that well-oriented (0?0?l) Sb₂Te₃ thin film with layered structure is beneficial for improvement of thermoelectric properties, being a promising choice for planar TE devices. The power generation and cooling performance of a layered p-Sb₂Te₃ film device are superior to those of the ordinary thin-film device. For a typical parallel device with 38 layered Sb₂Te₃ film elements, the output voltage, maximum power, and corresponding power density are up to 10.3?mV, 11.1?μW, and 73?mW/cm², respectively, for a temperature difference of 76?K. The device can produce a 6.1?K maximum temperature difference at current of 45?mA. The results prove that enhanced microdevice performance can be realized by integrating (0?0?l)-oriented Sb₂Te₃ thin films with a layered architecture.     

The Effect of Te Substitution for Sb on Thermoelectric Properties of Tetrahedrite

We present the study of the effect of Te substitution on the thermoelectric properties for Sb in Cu₁₂Sb_4?x Te _x S₁₃ tetrahedrite compounds with x ranging from 0.2 to 1.5 in the temperature range of room temperature to 723 K. Powder x-ray diffraction and electron microscopy results indicate a successful homogenous substitution without the alteration of the crystal structure or the introduction of secondary phases. Thermoelectric property measurements show that the excess electrons from Te during the substitution fill the unoccupied levels near the top of the valence bands in pure Cu₁₂Sb₄S₁₃ compound, moving the Fermi level closer to the top of the valence bands. This leads to an enhancement in thermopower but also to an increase in electrical resistivity. Overall, the reduction in total thermal conductivity gives rise to improved ZT values in all substituted samples. The highest ZT value obtained in this study is 0.92 at 723 K for x = 1, which is comparable to that of other p-type bulk thermoelectric materials.     

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.