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.     

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 (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.     

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.     

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.     

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.     

Enhanced Thermoelectric Properties of Hole-Doped Bi2−x Ba x Sr2Co2O y Ceramics

The influence of Ba doping on the thermoelectric properties of Bi_2?x Ba _x Sr₂ Co₂O _y (x = 0.00, 0.025, 0.05, 0.075, 0.10, 0.125, and 0.15) samples prepared by the solid-state reaction method was investigated from 333 K to 973 K. For the samples with x ≤ 0.075, the electrical resistivity decreased with increase of the Ba doping amount due to p-type doping and they exhibited metallic electrical conductivity behavior, whereas the samples with x ≥ 0.10 exhibited semiconductor-like electrical conductivity behavior. The Seebeck coefficients of all the samples decreased with increase of the Ba doping amount. The thermal conductivity first decreased for x ≤ 0.075, then increased with higher Ba doping amounts. As an overall result, the dimensionless figure of merit (ZT) of Bi_1.925Ba_0.075Sr₂Co₂O _y reached the maximum value of 0.245 at 973 K, being 41% higher than that of the undoped sample.     

Solid-State Synthesis and Thermoelectric Properties of Mg2Si1−x Sn x

Mg₂Si_1?x Sn _x (0 ≤ x ≤ 1) solid solutions have been successfully prepared by mechanical alloying and hot pressing as a solid-state synthesis route. All specimens were identified as phases with antifluorite structure. The electrical conduction changed from n-type to p-type at room temperature for x ≥ 0.5 due to the intrinsic properties of Mg₂Sn. The absolute value of the Seebeck coefficient decreased with increasing temperature, and the electrical conductivity increased with increasing temperature; this is indicative of nondegenerate semiconducting behavior. The thermal conductivity was reduced by Mg₂Si-Mg₂Sn solid solution due to phonon scattering by the alloying effect.     

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.     

Effect of Fe Substitution on Thermoelectric Properties of Fe x In4−x Se3 Compounds

Starting from elemental powder mixtures of Fe _x In_4?x Se₃ (x = 0, 0.05, 0.1, 0.15), polycrystalline In₄Se₃-based compounds with homogeneous microstructures were prepared by mechanical alloying (MA) and hot pressing (HP). With the increase of x from 0 to 0.15, the electrical resistivity and the absolute value of the Seebeck coefficient increased, while the thermal conductivity first decreased and then increased. The maximal dimensionless figure of merit ZT of 0.44 was obtained for the Fe _x In_4?x Se₃ (x = 0.05) sample at 723 K.     

Transport and Mechanical Properties of High-ZT Mg2.08Si0.4−x Sn0.6Sb x Thermoelectric Materials

Mg₂(Si,Sn) compounds are promising candidate low-cost, lightweight, nontoxic thermoelectric materials made from abundant elements and are suited for power generation applications in the intermediate temperature range of 600 K to 800 K. Knowledge on the transport and mechanical properties of Mg₂(Si,Sn) compounds is essential to the design of Mg₂(Si,Sn)-based thermoelectric devices. In this work, such materials were synthesized using the molten-salt sealing method and were powder processed, followed by pulsed electric sintering densification. A set of Mg_2.08Si_0.4?x Sn_0.6Sb _x (0 ≤ x ≤ 0.072) compounds were investigated, and a peak ZT of 1.50 was obtained at 716 K in Mg_2.08Si_0.364Sn_0.6Sb_0.036. The high ZT is attributed to a high electrical conductivity in these samples, possibly caused by a magnesium deficiency in the final product. The mechanical response of the material to stresses is a function of the elastic moduli. The temperature-dependent Young’s modulus, shear modulus, bulk modulus, Poisson’s ratio, acoustic wave speeds, and acoustic Debye temperature of the undoped Mg₂(Si,Sn) compounds were measured using resonant ultrasound spectroscopy from 295 K to 603 K. In addition, the hardness and fracture toughness were measured at room temperature.     

Substitution Solid Solutions FeGa3−x E x and Their Thermoelectric Properties

In this study we performed substitution experiments on the gallium site of the intermetallic semiconductor FeGa₃, to adjust the charge carrier concentration, and determined the thermoelectric (TE) properties of the resulting products. Isoelectronic species aluminium and indium, hole-doping zinc, and electron-doping germanium were chosen to find suitable substituent elements. The samples FeGa_3?x E _x (E = Al, In, Zn, Ge; x = 0.03, 0.05, 0.06, 0.10, 0.20) were prepared by liquid–solid–reaction with subsequent spark plasma sintering treatment. X-ray diffraction, metallographic, and microstructure analysis were used to determine chemical composition and to evaluate the suitability of the substitution element. For solid solutions FeGa_3?x Al _x and FeGa_3?x In _x the substitution concentrations were very low (x ≤ 0.02) and did not improve the TE properties of FeGa₃. The samples FeGa_3?x Zn _x had the expected p-type behaviour and slightly lower thermal conductivity than the binary compound. A substantial increase in the TE figure of merit was achieved for the solid solution FeGa_3?x Ge _x for which transition from semiconducting to metal-like behaviour was observed, with an additional decrease of thermal conductivity. The maximum ZT value of 0.21 was achieved for the composition FeGa_2.80Ge_0.20.     

Thermoelectric Properties of the Entire Composition Range in Mg2Si0.9925−x Sn x Sb0.0075

Eleven samples of nominal composition Mg_2.2Si_0.9925?x Sn _x Sb_0.0075 with x = 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 0.9925 were prepared by induction melting, ball milling, and spark plasma sintering. Hall effect, resistivity, Seebeck coefficient, and thermal conductivity measurements were conducted from room temperature to 400°C. Six of the samples were investigated for thermal stability by measuring powder x-ray diffraction while heating to 400°C. All samples were stable in air during the ～12-h-long data collection, except for Mg_2.2Sn_0.9925Sb_0.0075, which showed development of an elemental Sn phase after heating. The lattice parameter of each sample was extracted through Rietveld refinement and revealed a linear dependency on nominal composition. Measurement of top and bottom of the pellets exhibited systematic differences in lattice parameter and Seebeck coefficient, indicating that stoichiometry gradients are created during sintering.     

Nanostructuring and Thermoelectric Characterization of (GaSb)3(1−x)(Ga2Te3) x

GaSb is a promising thermoelectric material that exhibits good electrical properties. However, it has a high lattice thermal conductivity (κ _lat). Nanostructured bulk materials have been attracting interest because they effectively scatter phonons, significantly reducing κ _lat. AgPb _m SbTe _m+2 (LAST-m) compounds have recently been reported to have low κ _lat. These compounds have a NaCl structure, similar to that of binary PbTe, where Ag and Sb occupy the Pb site. In these compounds, two divalent Pb atoms are replaced with a monovalent Ag atom and a trivalent Sb atom to maintain charge compensation. In the present study, we reduced κ _lat of GaSb by applying the same principle as in LAST-m. Specifically, we substituted Te for Sb and generated vacancies at the Ga site to maintain charge compensation. This produced compounds with chemical compositions of (GaSb)_3(1?x)(Ga₂Te₃) _x (x = 0, 0.05, 0.10, and 0.25), where GaSb and Ga₂Te₃ both have the zincblende crystal structure. We employed two different annealing conditions: annealing at 833 K followed by quenching, and annealing at 833 K followed by cooling to room temperature over 3 days. The former annealed samples with compositions of x = 0.05 and 0.10 had nanoscale Ga-rich precipitates and exhibited a large reduction in κ _lat.     

Effects of Synthesis and Spark Plasma Sintering Conditions on the Thermoelectric Properties of Ca3Co4O9+δ

Ca₃Co₄O_9+δ samples were synthesized by solid-state (SS) and sol–gel (SG) reactions, followed by spark plasma sintering under different processing conditions. The synthesis process was optimized and the resulting materials characterized with respect to their microstructure, bulk density, and thermoelectric transport properties. High power factors of about 400 μW/m·K² and 465 μW/m·K² (at 800°C) were measured for SS and SG samples, respectively. The improved thermoelectric performance of the SG sample is believed to originate from the smaller particle sizes and better grain alignment. The SG method is suggested to be a beneficial means of obtaining high-performance thermoelectric materials of Ca₃Co₄O_9+δ type.