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.     

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.     

Power Generator Modules of Segmented Bi2Te3 and ErAs:(InGaAs)1−x (InAlAs) x

The thermoelectric properties of ErAs:InGaAlAs were characterized by variable-temperature measurements of thermal conductivity, electrical conductivity, and Seebeck coefficient from 300 K to 600 K, which shows that the ZT(, where and T are the Seebeck coefficient, electrical conductivity, thermal conductivity, and absolute temperature, respectively) of the material is greater than 1 at 600 K. Power generator modules of segmented elements of 300 μm Bi₂Te₃ and 50 μm thickness ErAs:(InGaAs)_1−x (InAlAs) _x were fabricated and characterized. The segmented element is 1 mm × 1 mm in area, and each segment can work at different temperature ranges. An output power up to 5.5 W and an open-circuit voltage over 10 V were measured. Theoretical calculations were carried out and the results indicate that the performance of the thermoelectric generator modules can be improved further by improving the thermoelectric properties of the element material, and reducing the electrical and thermal parasitic losses.     

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.     

Study of lifetimes and photoconductivity relaxation in heterostructures with Hg x Cd1 ? x Te/Cd y Hg1 ? y Te quantum wells

Carrier lifetimes in the continuum of the quantum well of a Hg _x Cd_{1 ? x} Te/Cd _y Hg_{1 ? y} Te hetero-structure were studied by terahertz pump-probe spectroscopy. It is found that the relaxation duration of the transmission signal is ??65 ps and is independent of the pump power. Such rapid relaxation in these structures is most likely determined by the interaction of holes with acoustic phonons due to a high density of states in the valence band and a larger effective mass compared with electrons. By the obtained data, the times of the interband nonradiative recombination of holes are determined. In this publication, we report the results of numerical calculation of the energy spectrum of the model structure, in which the possibility of obtaining population inversion at specified concentrations of nonequilibrium carriers is analyzed.     

Vanadium deep impurity level in diluted magnetic semiconductors Pb1 ? x ? y Sn x V y Te

The crystal structure, Sn and V distribution over the length of single-crystal ingots, and galvanomagnetic effects in low magnetic fields (4.2 K ?? T ?? 300 K, B ?? 0.07 T) in Pb_1?x?y Sn _x V _y Te alloys (x = 0.05?0.21, y ?? 0.015) are studied. It is shown that all the samples are single-phase, while the Sn and V concentrations exponentially increase from the beginning to the end of the ingots. Upon doping with V, a decrease in the concentration of free holes and a metal-insulator transition are found. They are related to the appearance of a deep impurity level of V in the band gap, electron redistribution between the level and the valence band, and pinning of the Fermi-level to the impurity level. The shift rate of the V level relative to the conduction band bottom is determined and a diagram of the reconstruction of the electronic structure of the Pb_{1 ? x ? y} Sn _x V _y Te alloy upon varying the host composition is suggested.     

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.     

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.     

Growth,structure, and properties of GaAs-based (GaAs)1–x–y (Ge2) x (ZnSe) y epitaxial films

The possibility of growing the (GaAs)_1–x–y (Ge₂) _x (ZnSe) _y alloy on GaAs substrates by the method of liquid-phase epitaxy from a tin solution–melt is shown. X-ray diffraction shows that the grown film is single-crystal with the (100) orientation and has the sphalerite structure. The crystal-lattice parameter of the film is a _f = 0.56697 nm. The features of the spectral dependence of the photosensitivity are caused by the formation of various complexes of charged components. It is established that the I–V characteristic of such structures is described by the exponential dependence I = I ₀exp(qV/ckT) at low voltages (no higher than 0.4 V) and by the power dependence J ~ V ^α, where the exponent α varies with increasing voltage at high voltages (V > 0.5 V). The results are treated within the framework of the theory of the drift mechanism of current transfer taking into account the possibility of the exchange of free carriers within the recombination complex.     

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.     

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.     

Bi2Te3热电材料研究现状

Bi2Te3热电材料是半导体材料,室温下具有良好的热电特性,能够实现热能和电能的相互转化,应用前景十分广阔。Bi2Te3热电材料的转换效率低是影响其应用的瓶颈之一,目前世界范围内的研究热点主要集中在如何提高热电材料的能量转换效率上。综述了热电材料的种类、国内外关于Bi2Te3热电薄膜的制备方法和性能研究,对多种典型制备方法进行分析对比,探讨了影响Bi2Te3热电薄膜质量的因素及机制。结合Bi2Te3热电薄膜在温差发电和热电制冷方面的应用,如果微型热电制冷器实现与大功率LED芯片集成封装,那么芯片级低温散热问题有望解决。     

Structural and spectral features of MOCVD Al x Ga y In1 ? x ? y As z P1 ? z /GaAs (100) alloys

The study is concerned with MOCVD epitaxial heterostructures grown on the basis of Al _x Ga _y In_{1 ? x ? y} As _z P_{1 ? z} quinary alloys in the region of alloy compositions isoperiodic to GaAs. By the X-ray diffraction technique and atomic force microscopy, it is shown that, on the surface of the heterostructures, there are nanometric objects capable of lining up along a certain direction. From calculations of the crystal lattice parameters with consideration for internal strains, it can be inferred that the new compound is a phase based on the Al _x Ga _y In_{1 ? x ? y} As _z P_{1 ? z} alloy.     

(Bi2Te3)0.90(Sb2Te3)0.05(Sb2Se3)0.05热压合金微观结构和电学性能相关性研究

通过熔炼,研磨制备N型(Bi2Te3)0．90(Sb2Te3)0．05(Sb2Se3)0．05热电材料的粉末,热压制备混合粉末热压合金。通过SEM和XRD研究热压合金的微观结构,在室温测量热压合金样品的电学性能。结果表明热压合金在微观结构和电学性能上存在各向异性,从而预示能够在增强材料机械强度的同时提高其热电性能。     

电场激活压力辅助烧结对(Bi2Te3)0.2(Sb2Te3)0.8热电材料微观结构及热电性能的影响

采用电场激活压力辅助烧结（FAPAS）技术制备了(Bi2Te3)0.2(Sb2Te3)0.8热电材料,采用无电场、低电场强度和高电场强度三种烧结方式作为对比实验,研究了烧结过程中施加电场强度对(Bi2Te3)0.2(Sb2Te3)0.8热电材料微观结构和热电性能的影响。研究结果表明,在烧结过程中施加电场,可明显提高(Bi2Te3)0.2(Sb2Te3)0.8热电材料的电导率和Seebeck系数,从而提高其综合电功率因子;而采用大电场强度烧结则会使(Bi2Te3)0.2(Sb2Te3)0.8材料出现层状结构择优取向,在电性能相对较高的情况下亦使其热导率明显减低,从而获得较高ZT值。     

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.     

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.     

Bi2Te3热电材料改性研究及其进展

随着全球经济对高效、无污染能源转换的强劲需求,Bi2Te3半导体作为最优异的室温热电材料取得了长足稳步的发展。本文在简述Bi2Te3热电材料的结构和性能的基础上,重点介绍了掺杂、纳米化、掺杂与纳米化相结合的方法对Bi2Te3热电性能的影响,详细分析了其影响机制。结果表明,以上方法均能很大程度上提升Bi2Te3热电材料的热电性能,尤其是掺杂与纳米化相结合对热电性能的提高更为显著。最后,对Bi2Te3热电材料改性的研究方向进行了展望。     

Features of ecological control in nanotechnologies in view of features of Ca y La1 − y F3 − y and La x Ca1 − x F2 + x structuring

General features of ecological control in nanotechnologies were found. Based on the study of structural-morphological characteristics of nanoprecipitates with ordered structure in Ca _y La_{1 ? y} F_{3 ? y} and La _x Ca_{1 ? x} F_{2 + x} , it was shown that it is necessary to additionally control the formation of ordered states, the presence of antiphase domains, and the degree of order in ecological control of solution-based materials.

     

On the resonant level of chromium in the rhombohedral and cubic phases of Pb1 − x − y Ge x Cr y Te alloys

The temperature dependences of the Hall coefficient (4.2 K ≤ T ≤ 300 K, B ≤ 0.07 T) in Pb_{1 ? x ? y} Ge _x Cr _y Te alloys (x = 0.03–0.08, y ≤ 0.01) are studied. An increase in the absolute value of the Hall coefficient with an increase in temperature is found. This fact is indicative of a decrease in the concentration of free electrons as a result of the motion of the resonant level of chromium stabilizing the Fermi level relative to the conduction-band bottom. The temperature dependences of the Hall coefficient, in satisfactory agreement with the experimental ones, are calculated in the context of the two-band Kane dispersion law allowing for the structural phase transition upon increasing temperature. The energy position and temperature coefficients of the motion of the resonant level of chromium relative to the middle of the band gap in the rhombohedral and cubic phases are determined.