Structural and mechanical properties of spark plasma sintered n‐ and p‐type bismuth telluride alloys

Spark Plasma Sintering (SPS) is used for the fabrication of wafers of n‐ and p‐type thermoelectric V₂VI₃ materials. The SPS process did not change the overall chemical composition. X‐ray diffraction analysis and the electron backscattered selected area diffraction prove the preferential orientation after the SPS procedure expecting anisotropic thermoelectric prop‐ erties. The mechanical properties of the SPS material are enormously enhanced, so that the fabrication of thin wafers with only 100 µm thickness suitable for the development of Peltier devices with high cooling power density will be possible. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thermoelectric properties in Mn-doped Bi2Se3

Using n-type and p-type Mn-doped Bi₂Se₃ single crystals, a thin-film-type thermoelectric (TE) module was fabricated and the TE characteristics were investigated. The Seebeck coefficient at room temperature was about 100 μV K⁻¹ with different sign for both materials. From the Seebeck coefficient and resistivity values, the electric power of our TE module was evaluated to be 90 μW for a single couple at the temperature difference of 10 K. This value is compared to that (∼21 μW) of commercialized TE device. Nevertheless, the actual power was measured to be quite small around 0.74 μW, which is much higher than other homemade TE power level. This small power is attributed to the high electrical contact resistance between the TE material and the heat source and sink. Assuming the contact resistance level ∼0.1 Ω similar to that of commercialized TE devices, the electric power should be about 41 μW, which is almost 2 times higher than that in commercialized TE devices. These results propose that the Mn-doped Bi₂Se₃ system is another promising TE material, which can be replaced with the commercialized Bi₂Te₃ system.     

Thermoelectric properties of pressed bismuth nanoparticles

Theory predicts a substantial increase in the dimensionless figure of merit as the dimensionality and characteristic size of a material are decreased. We explore the use of bismuth nanoparticles pressed into pellets as potential increased efficiency thermoelectric materials. The figure of merit of these pellets is determined by independently measuring the electrical conductivity, thermal conductivity and Seebeck coefficient. The results from the nanoparticle sample are compared to microparticle-based samples. Both sample types show a slight reduction in thermal conductivity relative to bulk bismuth and a Seebeck coefficient near or slightly larger in magnitude than bulk bismuth. These changes are dwarfed by a hundred-fold decrease in the electrical conductivity due to porosity and an oxide layer on the particles. The low conductivity leads to figures of merit at least two orders of magnitude smaller than bulk bismuth. Oxide layer removal and reduced pellet porosity will be required to increase the figure of merit.     

Characteristics of electrodeposited bismuth telluride thin films with different crystal growth by adjusting electrolyte temperature and concentration

Bismuth telluride (Bi₂Te₃) thin films were prepared with various electrolyte temperatures (10°C–70 °C) and concentrations [Bi(NO₃)₃ and TeO₂: 1.25–5.0 mM] in this study. The surface morphologies differed significantly between the experiments in which these two electrodeposition conditions were separately adjusted even though the applied current density was in the same range in both cases. At higher electrolyte temperatures, a dendrite crystal structure appeared on the film surface. However, the surface morphology did not change significantly as the electrolyte concentration increased. The dendrite crystal structure formation in the former case may have been caused by the diffusion lengths of the ions increasing with increasing electrolyte temperature. In such a state, the reactive points primarily occur at the tops of spiked areas, leading to dendrite crystal structure formation. In addition, the in-plane thermoelectric properties of Bi₂Te₃ thin films were measured at approximately 300 K. The power factor decreased drastically as the electrolyte temperature increased because of the decrease in electrical conductivity due to the dendrite crystal structure. However, the power factor did not strongly depend on the electrolyte concentration. The highest power factor [1.08 μW/(cm·K²)] was obtained at 3.75 mM. Therefore, to produce electrodeposited Bi₂Te₃ films with improved thermoelectric performances and relatively high deposition rates, the electrolyte temperature should be relatively low (30 °C) and the electrolyte concentration should be set at 3.75 mM.     

纳米结构碲化铋合金的制备及电热输运特性

采用惰性气体保护蒸发-冷凝法制备了纳米Bi及Te粉末, 结合机械合金化和放电等离子烧结技术, 在不同烧结温度下制备出了单一物相且具有纳米层状结构及孪晶亚结构的n型Bi₂Te₃块体材料, 并系统研究了块体材料的晶粒尺度、微结构及其对电热传输特性的影响. SEM, TEM分析结果表明, 以纳米粉末为原料, 通过有效控制工艺条件, 可以制备出具有纳米层状结构Bi₂Te₃合金块体材料, 同时纳米层状结构中存在孪晶亚结构; 热电性能测试结果表明, 具有纳米层状结构及孪晶亚结构的块体试样与粗晶材料相比, 热导率大幅度降低, 在423 K附近, 热导率由粗晶材料的1.80 W/mK降至1.19 W/mK, 晶格热导率从1.16 W/mK降至0.61 W/mK, 表明纳米层状结构与孪晶亚结构共存, 有利于进一步提高声子散射, 降低晶格热导率. 其中在693 K放电等离子烧结后的试样于423K附近取得最大值的无量纲热电优值(ZT), 达到0.74.     

Thermoelectric properties of gated graphene ribbons in the ballistic regime

We investigate the thermoelectric properties of gated graphene ribbons in the ballistic transport limit using linear response theory and the Landauer formalism. The dependence of the electronic conductance, thermopower as well as electronic thermal conductance on both Fermi level and temperature are clarified and the validity of Wiedemann-Franz law is examined. The electronic part of thermoelectric figure of merit _ZTel${\mathit{ZT}}_{\mathit{el}}$ which gives an upper bound for the thermoelectric efficiency of the gated ribbons, is also calculated. It is shown that _ZTel${\mathit{ZT}}_{\mathit{el}}$ of wide and short gated ribbons is directly related to geometric aspect ratio of the graphene ribbon and for very short ribbons can exceed unity at room temperature. Our results could be useful in the design of efficient graphene-based thermoelectric devices.     

Thermoelectric properties of one-dimensional graphene antidot arrays

We investigate the thermoelectric properties of one-dimensional (1D) graphene antidot arrays by nonequilibrium Green?s function method. We show that by introducing antidots to the pristine graphene nanoribbon the thermal conductance can be reduced greatly while keeping the power factor still high, thus leading to an enhanced thermoelectric figure of merit (ZT). Our numerical results indicate that ZT values of 1D antidot graphene arrays can be up to unity, which means the 1D graphene antidot arrays may be promising for thermoelectric applications.     

B4C in ex-situ spark plasma sintered MgB2

Powder mixtures of MgB₂ and B₄C with composition ((MgB₂) + (B₄C)_x, x = 0.005, 0.01, 0.03) were consolidated by Spark Plasma Sintering at 1150 °C for 3 min. The average particle size of B₄C raw powder was relatively high of 4 μm. Despite this, it is shown that processing processes are fast and, as in the case of the in-situ routes, for our ex-situ method carbon substitutes for the boron in the crystal lattice of MgB₂. Specifics of microstructure are discussed based on electron microscopy observations. Carbon substitution and microstructure contribute to enhancement of the critical current density J_c at high magnetic fields and of the irreversibility field H_irr. Samples are shown to be in the point pinning limit with some tendency toward the grain boundary pinning depending on B₄C doping amount and temperature. An optimum composition is found for x = 0.01: for this sample, at 20 K, a J_c of 100 A/cm² is obtained at 5.35 T. This value is higher than for the pristine MgB₂ sample and for an optimum ex-situ nano-SiC-doped sample obtained for the same SPS processing conditions.     

Thermoelectric properties of the trigonal and orthorhombic modifications of zinc telluride

Thermoelectric measurements are performed to study the phase transformations occurring in ZnTe under high pressure. It is shown that the thermoelectric power S of the cinnabar trigonal phase corresponds to a semiconductor with a hole-type conduction. In the Cmcm orthorhombic phase, the value of S≈+10 μV/K and the sign of the thermoelectric power testify to the metallic hole-type conduction, as in the high-pressure phases of other Group II chalcogenides (HgSe, HgTe, CdTe) with similar crystal lattices. In the transition region between the trigonal and orthorhombic phases, the pressure dependence of the thermoelectric power is found to exhibit an anomaly (a sharp dip), which leads to a change in the sign of S under decreasing pressure. This feature may presumably be related to the formation of the intermediate phase with the NaCl structure, which has an electron-type conduction in other zinc and cadmium chalcogenides.     

Structure and thermoelectric properties of nanocomposite bismuth telluride prepared by melt spinning or by partially alloying with IV–VI compounds

Bismuth telluride samples are compared with respect to the evolution of their thermoelectric material parameters like thermal and electrical conductivity. The Seebeck coefficient is discussed in dependence on the melt spinning fabrication technique. The melt spinner used is only able to produce small thin ribbon shaped specimens, some as thin as 10 μm. This limits melt spinning to mainly production of research specimens for alloys with high critical cooling rate, which are difficult to fabricate with other techniques. Additional parameters are alloying or doping of the base material by comparing the properties as prepared to different annealing conditions. The intrinsic p‐ and n‐doped material was alloyed with up to 0.5% lead telluride by rapidly cooling the bulk material to improve the thermoelectric properties analysed from RT up to about 600 K. A Seebeck coefficient of well above 200 µV/K could be obtained for p‐ and n‐type materials. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Enhanced thermoelectric performance of spark plasma sintered copper-deficient nanostructured copper selenide

We report the thermoelectric properties of nanostructured Cu-deficient Cu₂Se, which was synthesized by high energy ball milling followed by spark plasma sintering. Our method obtained a significant enhancement in the thermoelectric figure of merit (ZT), i.e., ~1.4 at 973 K, which was ~30% higher than its bulk counterpart. This enhancement in the thermoelectric performance was due mainly to a significant reduction in the lattice thermal conductivity, which was attributed to enhanced phonon scattering at various length scales by nanoscale defects as well as abundant nanograin boundaries. The nanoscale defects were characterized by transmission electron microscopy of the nanostructured Cu_2−xSe samples, which formed the basis of the ZT enhancement.     

Thermoelectric power and magnetic properties of Cu doped NiZn ferrite for technological application

A series of samples in the system Ni_0.65Zn_0.35Cu_xFe_2-xO₄ (x = 0, 0.1, 0.2, 0.3, 0.4 and 0.5) were prepared by the usual ceramic technique. The thermoelectric power and the magnetic susceptibility were measured. The transition from the ferrimagnetic to the paramagnetic state is accompanied by an increase in the thermo EMF. NiZn ferrite shows n-type conductivity due to the presence of Fe²⁺ ions. The addition of Cu²⁺ ions creates lattice vacancies which give rise to p-type conductivity.

The Tawfik coefficient was determined for NiZn ferrite in the paramagnetic state. This coefficient was reduced by addition of Cu up to x < 0.5.     

Thermoelectric and optical properties of CuAlO2 synthesized by direct microwave heating

A single phase of delafossite CuAlO₂ (CAO) was successfully synthesized by a 600 W microwave radiation for 20 min. The CAO sample was composed of quite distorted single-crystalline plates with 200–350 nm thick. Its atomic vibrations were detected at 760 and 550 cm⁻¹ belonging to Al–O and Cu–O stretching, respectively. The direct and indirect energy gaps were respectively determined to be 3.9 and 2.9 eV. The photoluminescence (PL) at room temperature was at 585 nm (2.12 eV) corresponding to the indirect energy gap and at 760 nm (1.63 eV) corresponding to the p-type native defect. For its thermoelectric (TE) properties, the Seebeck coefficient (S) was positive value, with holes as the majority of charge carriers. By increasing of the test temperature, both the electrical resistivity and absolute value of Seebeck coefficient were decreased, but the power factor was in the opposite manner. The dimensionless figure of merit (ZT) of the crystalline CAO was evaluated to be the maximum of 9 × 10⁻³ at 1073 K.     

Thermoelectric properties and electronic structure of Al-doped ZnO

Impure ZnO materials are of great interest for high temperature thermoelectric application. In this work, we present the effects of Al-doping on the thermoelectric properties and electronic structures of a ZnO system. We find that, with increasing Al concentrations, the electrical conductivity increases and the thermal conductivity decreases significantly, whereas, the Seebeck coefficient decreases slightly. Nevertheless, the figure of merit (ZT) increases owing to high electrical conductivity and low thermal conductivity. On the other hand, the electronic band structures show that the position of the Fermi level is moved upwards and the bands split near the valence-band top and conduction-band bottom. This is due to the interaction between the Al3p and Zn4s orbitals, which drive the system towards semimetal. Besides, the Density Of States (DOS) analysis shows that the introduction of Al atom obviously reduces the slope d(DOS)/dE near the Fermi level. Based on the calculated band structures, we are able to explain qualitatively the measured transport properties of the Al-doped ZnO system.     

Thermoelectric and topological properties of half-Heusler compounds ZrIrX(As,Sb, Bi)

The strain dependent electronic structures, thermoelectric and topological properties of the half-Heusler compounds ZrIrX(X=As, Sb, Bi) are investigated by the first-principle calculations. At the equilibrium lattice constants, all the three compounds are trivial insulators and good thermoelectric materials with the Seebeck coefficient S and the power factor over relaxation time $S^2\sigma /\tau$ as large as 1180 (μV/K) and 4.1 (${10}^{11}W{m}^{?1}{K}^{?2}{s}^{?1}$), respectively. The compressive strain enhances the band gap, while the tensile strain decreases the band gap. At some specific tensile strains, the compounds become Dirac-semimetals, with the s-type band ${\mathrm{\Gamma }}_6$ below p-type band ${\mathrm{\Gamma }}_8$, in the cubic phase. When we compress the a(b)-axis and elongate the c-axis of the compounds, they become the type-I Weyl semimetals. For ZrIrAs, the eight Weyl-Points (WPS) locate at (± K_x, 0, ± K_z), (0, ± K_y, ± K_z), ${\mathrm{K}}_x={\mathrm{K}}_y=0.008{\mathrm{\AA }}^{?1}$, ${\mathrm{K}}_z=0.043{\mathrm{\AA }}^{?1}$.     

Thermoelectric transport properties through a T-shaped single quantum dot

We study the thermopower, thermal conductance, electric conductance and the thermoelectric figure of merit for a gate-defined T-shaped single quantum dot (QD). The QD is solved in the limit of strong Coulombian repulsion U→∞, inside the dot, and the quantum wire is modeled on a tight-binding linear chain. We employ the X-boson approach for the Anderson impurity model to describe the localized level within the quantum dot. Our results are in qualitative agreement with recent experimental reports and other theoretical researches for the case of a quantum dot embedded into a conduction channel, employing analogies between the two systems. The results for the thermopower sign as a function of the gate voltage (associated with the quantum dot energy) are in agreement with a recent experimental result obtained for a suspended quantum dot. The thermoelectric figure of merit times temperature results indicates that, at low temperatures and in the crossover between the intermediate valence and Kondo regimes, the system might have practical applicability in the development of thermoelectric devices.     

Optical properties of zinc telluride with cadmium telluride submonolayers

Reflection, luminescence, and Raman spectra of epitaxial ZnTe layers nominally incorporating double CdTe submonolayers were studied. The band of an exciton localized at the potential produced by narrow-gap planar inclusions dominated the luminescence of these heterostructures. The emission parameters of localized excitons (specifically, the ratio of integral emission intensity to localization energy) were determined, and it was found that excitons interact with longitudinal optical phonons of the layer enriched with cadmium. Giant amplification of the Stokes component resonant with the localized exciton level was observed in Raman scattering.     

Thermoelectric effects in spin field-effect transistors

We investigate the thermoelectric effects in a spin field-effect transistor with ferromagnetic leads held at different temperatures. The thermopower S and thermoelectric figure of merit ZT oscillate with the increase of the Rashba spin-orbit coupling strength. The oscillation amplitude of ZT decreases with increasing the spin polarization. S and ZT are strongly influenced by the interfacial barrier strength Z, exhibiting a nonmonotonous change with Z. The thermoelectric effects are also manipulated by the magnetization configuration of the ferromagnetic leads. It is expected that the present study of the thermoelectric effects is helpful in the design of thermoelectric devices.