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.     

Structural and Thermoelectric Properties of Bi1−x Sb x Nanoalloys Prepared by Mechanical Alloying

Bi_1?x Sb _x nanoparticles were prepared by mechanical alloying and compacted using different techniques. The influence of the composition as well as the pressing conditions on the thermoelectric performance was investigated. A strong dependence of the thermoelectric properties on the composition was found, which deviates from the behavior of single crystals. The results indicate a significant change in the band structure of the material induced by the reduced size. The influence of the pressing conditions on the thermoelectric properties also showed composition dependence. The results show that the compacting method has to be chosen carefully.     

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.     

Thermoelectric Properties of CdTe1−x Cl x Material Prepared by Spark Plasma Sintering Method

CdTe compound is a prospective thermoelectric material due to its high Seebeck coefficient and low thermal conductivity. In the present study, we optimized its carrier concentration by substituting Cl on the Te site in order to improve the electrical conductivity and decrease the lattice thermal conductivity. The polycrystalline CdTe_1?x Cl _x (x = 0.005, 0.01, 0.03, 0.05) samples were fabricated by solid state reaction followed with spark plasma sintering, and the relative densities of the sintered samples were higher than 98%. Thermoelectric properties, including Seebeck coefficient (α), electrical conductivity (σ). and thermal conductivity (κ), were measured in the temperature range of 300–700 K. The increase of Cl content (x) caused an increase of σ, and the maximum ZT value of 0.2 was obtained at about 630 K for the CdTe_0.97Cl_0.03 sample.     

Thermoelectric Properties of Nanostructured Bismuth-Doped Lead Telluride Bi x (PbTe)1−x Prepared by Co-Ball-Milling

In this work we present a simple method to synthesize nanostructured, bismuth-doped lead telluride by co-ball-milling. The obtained nanopowders were compacted via either a cold pressing/annealing approach or by hot pressing. The two compacting methods were compared regarding sample density. Series with bismuth content up to 6 at.% were characterized by measuring the thermoelectric transport properties over a wide temperature range between 123 K and 773 K using two different techniques for the Seebeck coefficient and electrical conductivity. A decreasing thermal conductivity and increasing electrical conductivity were found with increasing doping level. The best results were obtained for samples with 5 at.% and 6 at.% bismuth, showing a maximum ZT value of 1.1 at 773 K. Transmission electron microscopy study was performed to analyze the microstructure of the nanopowders, suggesting that, in addition to n-type doping of the lead telluride matrix, segregation effects occur and the samples consist of multiple phases.     

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.     

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.     

Thermoelectric Properties of Skutterudites Co4−x Ni x Sb11.9−y Te y Se0.1

CoSb₃-based skutterudites with substitution of Ni atoms for Co, and substitution of Te and Se atoms for Sb were successfully prepared by solid-state reaction and spark plasma sintering. According to x-ray diffraction analysis the major phase of all the samples had a CoSb₃-type structure, although back-scattered electron images showed that small amounts of impurity phases were present in all the samples. The temperature-dependent transport properties were characterized over the temperature range 300–800 K for all the samples. It was found that appropriate substitution with Ni, Te, and Se effectively improved the power factor and reduced the thermal conductivity. As a result, Ni, Te, and Se-tri-doped CoSb₃ materials with enhanced thermoelectric figures of merit, ZT, were obtained. The highest ZT was greater than 1.1 at high temperature.     

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.     

Reinvestigation of Thermoelectric Properties of n- and p-Type Ba8−d Au x Si46−x−y Clathrate

We have synthesized n- and p-type clathrates Ba_8?d Au _x Si_46?x?y with various Au contents (4.6 < x < 6.0) by arc-melting, annealing at 1173 K, and spark plasma sintering at 1073 K. The Au compositions found by wavelength-dispersive x-ray spectrometry for the synthesized samples were slightly lower than the nominal compositions. Ba_7.8Au_4.6Si_41.4 and Ba_7.7Au_4.9Si_41.1 samples showed n- and p-type conduction, respectively. According to the electron count (Ba²⁺)₈Au(^3?)_5.33Si_40.67, the clathrate composition with x = 5.33 is expected to be an intrinsic semiconductor. Our experimental results show that increase of the Au composition causes a transition from n-type to p-type conduction between x = 4.6 and 4.9. We have also calculated the band structures of the Ba₈Au _x Si_46?x clathrate including a vacancy by ab initio calculation based on density functional theory with structure optimization. It was found that the vacancy behaves like an electron acceptor and the numbers of vacancies at 24k sites for the synthesized Ba₈Au _x Si_46?x?y clathrates can be estimated as ～0.4 in a unit cell.     

Correlation of the Optical and Magnetic Properties of Bi2Te3–Sb2Te3 Crystals

Semiconductors - The magnetic and optical properties of Bi2Te3–Sb2Te3 crystals are investigated depending on the ratio of Bi2Te3 and Sb2Te3 components in the solid-solution composition and...     

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.     

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.     

Microwave Synthesis and Characterization of the Series Co1−x Fe x Sb3 High Temperature Thermoelectric Materials

The use of microwave energy for materials processing has a major potential and real advantages over conventional heating such as (1) time and energy savings, (2) rapid heating rates (volumetric heating vs. conduction), (3) considerably reduced processing time and temperature, (4) fine microstructures and hence improved mechanical properties and better product performance, and (5) finally lower environmental impact. In this study, we investigated the use of microwave-assisted synthesis to synthesize a series of Co_1?x Fe _x Sb₃ using this novel approach, which gave high quality materials with little or no impurities in a fraction of the time needed for conventional synthesis. X-ray diffraction analysis was used to examine the structure and the lattice parameters of the samples, while scanning electron microscopy with energy dispersive x-ray spectroscopy was used to study the morphology of the compounds. The samples were sintered by spark plasma sintering, and the highest ZT of 0.33 was obtained for x = 0.2 at 700 K.     

Effect of Excess Na on the Morphology and Thermoelectric Properties of Na x Pb1−x Te0.85Se0.15

The thermoelectric properties of p-Na _x Pb_1?x Te_0.85Se_0.15, which possesses a high thermoelectric figure of merit due to band convergence, have been systematically investigated for increasing Na concentration (x = 0.01, 0.02, 0.03, 0.05, and 0.07) from room temperature to 773 K. For x values up to 0.03, the hole concentration increases with the Na concentration; however, for x ≥ 0.03, excess Na forms separate microstructures with needle- and plate-like shapes. At high concentrations (x = 0.05 and 0.07) both the number and size of these structures increase (over 10 μm). Differential scanning calorimetry identifies a phase change near 660 K in samples with x = 0.05 and 0.07, confirming the formation of microstructures; this phase change leads to a decrease in electrical resistivity. However, these microstructures do not significantly affect thermal transport, probably because they are too large to scatter phonons. The highest thermoelectric figure of merit, zT, value is 1.6, which is obtained at 760 K for x = 0.05, due to the low thermal conductivity and electrical resistivity.     

Compositional Sensitivity of Microstructures and Thermoelectric Properties of Ag1−x Pb18Sb1+y Te20 Compounds

This study reports microstructural investigations of Ag_1?x Pb₁₈Sb_1+y Te₂₀, i.e., Ag-deficient and Sb-excess lead-antimony-silver-tellurium-18 (LAST-18: x ≠ 0, y ≠ 0). Two different length scales are explored. The micrometer scale was evaluated by scanning electron microscopy (SEM) to analyze the number of secondary phases as well as composition. Site-specific focused ion-beam liftout of transmission electron microscopy (TEM) lamellae from thermoelectrically characterized samples was accomplished to investigate the structure on the nanometer scale. TEM was performed to reveal the shape and orientation relationship of nanoprecipitates. The study is completed with results for the thermoelectric properties for different values of x and y.     

Thermoelectric Properties of Hot-Pressed β-K2Bi8Se13−x S x Materials

In this work, hot-pressed pellets of the K₂Bi₈Se₁₃ family of compounds were prepared for the first time. The pellet fabrication of selected members of the K₂Bi₈Se_13?x S _x series was studied. Sintering parameters, such as temperature, pressure, and duration, were investigated based on a statistical design- of-experiments approach to identify the optimum conditions for fabrication of high-quality pellets. These optimum conditions were then applied for the K₂Bi₈Se_13?x S _x series, and the thermoelectric properties of the stoichiometric members for x = 0, 4, 6, and 8 were studied. Doping experiments were also investigated using sulfur excess in the x = 6 member in an attempt to modify its properties.