Effect of nanocrystallinity on lattice dynamics in Bi2Te3 based thermoelectrics

The lattice dynamics in as‐cast and nanocrystalline thermoelectric Bi₂Te₃ based p‐type and n‐type material were investigated using inelastic neutron scattering. Generalized densities of phonon states show substantial agreement between the lattice dynamics in as‐cast samples and previous studies. The lattice dynamics in the nanocrystalline materials differ significantly from its as‐cast counterparts in the acoustic phonon regime. In nanocrystalline p‐type and n‐type compounds, the average acoustic phonon group velocity was found to be reduced to 80(5)% and 95(2)% of the value in as‐cast material. It is argued that point‐defect and strain contrast scattering may play an important role for the understanding of lattice thermal conductivity in (nanocrystalline) Bi₂Te₃ based thermoelectrics beside the observed decrease of sound velocity. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Effective phonon scattering and enhancement of thermoelectric performance in Ga-excess Bi0.4Sb1.6Te3 compounds

We investigate the thermoelectric properties on Ga-excess p-type Ga_xBi_0.4Sb_1.6Te₃ compounds. Even though the random distribution of Ga-doping increases electrical resistivity giving rise to the decrease of power factor, the significant decrease of lattice thermal conductivity by the excess Ga-doping induces significant enhancement of ZT value (1.13 at 350 K) for the Ga x = 0.03 doped compound. From the X-ray diffraction and elemental mapping by energy dispersive X-ray spectroscopy, we observed Sb and Ga phase separation leading to the phonon scattering. The Sb precipitation implies atomic defect in the matrix which can induce short wavelength phonon scattering. The synergetic phonon scatterings from various scattering sources such as point defect, alloy scattering, and grain boundary phonon scattering have an important role in the enhancement of thermoelectric performance.     

Temperature dependence of the Raman spectra of Bi2Te3 and Bi0.5Sb1.5Te3 thermoelectric films

The temperature dependence of the Raman spectra of Bi₂Te₃ and Bi_0.5Sb_1.5Te₃ thermoelectric films was investigated. The temperature coefficients of the E_g(2) peak positions were determined as –0.0137 cm^–1/°C and –0.0156 cm^–1/°C, respectively. The thermal expansion of the crystal caused a linear shift of the Raman peak induced by the temperature change. Based on the linear relation, a reliable and noninvasive micro‐Raman scattering method was shown to measure the thermal conductivity of the thermoelectric films. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

High pressure transport characteristics of Bi2Te3, Sb2Te3, and BiSbTe3

This paper presents ambient and high pressure measurements of transport properties of the Bi₂Te₃–Sb₂Te₃ series of materials. The electrical resistivity, thermal conductivity, and Seebeck coefficient have been measured on both end compounds and the direct solid solution of the two at pressure up to 10 GPa. An additional discussion involving the high pressure structure will be presented. From this, it was determined that these materials undergo at least two structural phase transitions between 0 and 20 GPa and a discussion is presented regarding this and the changes in the transport properties.     

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.     

Energy formation of antisite defects in doped Sb2Te3 and Bi2Te3 crystals

The free carrier concentration of the Sb_2−xIn_xTe₃, Bi_2−xIn_xTe₃ and Bi₂Te_3−xS_x crystals has been determined from the values of the Hall constants and the free carrier concentration of the Sb_2−xTl_xTe₃ has been calculated from the plasma resonance frequency; with increasing value of x, the hole concentration decreases. As the incorporation of the elements In, Tl and S into the lattice Sb₂Te₃ or Bi₂Te₃, respectively, gives rise to the uncharged defects In^x_Sb, Tl^x_Sb, In^x_Bi and S^x_Te, the x causes the decrease of the antisite defects concentration. The proven effect is explained in the following way: the antisite defects can be created only in crystals whose atoms are bound by weakly polarized bonds. The incorporation of In, Tl and S atoms into the crystal lattice of Sb₂Te₃ or Bi₂Te₃ increases the bond polarity, the ionicity of ternary crystals increases. This unfavorably affects the increase of antisite defects whose concentration decreases. The change of the bond polarity is considered from the changes discovered in the formation energy of antisite defects of the above mentioned ternary crystals.     

Synthesis and thermoelectric properties of YbSb2Te4

The study of the ternary phase diagram Yb–Sb–Te has led to the synthesis of YbSb₂Te₄ as a pure phase by way of high energy ball milling followed by annealing, whereas typical high temperature powder metallurgy leads to multiphase sample with impurities of the very stable YbTe. The Hall mobility, Seebeck coefficient, electrical resistivity and thermal conductivity of the layered compound YbSb₂Te₄ were measured in the range of 20–550 °C. The thermoelectric figure of merit peaks at 525 K and reaches 0.5. Of particular interest is the very low lattice thermal conductivity (as low as a glass) which makes YbSb₂Te₄ and related compounds promising thermoelectric materials. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Investigation of the possibilities for increasing the thermoelectric figure of merit of nanostructured materials based on Bi2Te3-Sb2Te3 solid solutions

The transport coefficients and thermoelectric figure of merit ZT for bulk nanostructured materials based on Bi₂Te₃-Sb₂Te₃ solid solutions have been investigated theoretically. Similar materials prepared by rapid quenching of the melt with the subsequent grinding and sintering contain amorphous and nanocrystalline regions with different sizes of particles. According to the performed estimations, the thermoelectric figure of merit of the amorphous phase can exceed the value of ZT for the initial solid solution by a factor of 2?C3 primarily due to the significant decrease in the thermal conductivity. The effective transport coefficients of the medium as a whole have also been investigated as a function of the parameters of each phase, and the concentration range of the amorphous phase, which corresponds to the effective values ZT > 1, has been determined.     

The effect of (00l) crystal plane orientation on the thermoelectric properties of Bi2Te3 thin film

Highly (00l)-oriented pure Bi₂Te₃ films with in-plane layered grown columnar nanostructure have been fabricated by a simple magnetron co-sputtering method. Compared with ordinary Bi₂Te₃ film and bulk materials, the electrical conductivity and Seebeck coefficient of such films have been greatly increased simultaneously due to raised carrier mobility and electron scattering parameter, while the thermal conductivity has been decreased due to phonon scattering by grain boundaries between columnar grains and interfaces between each layers. The power factor has reached as large as 33.7 μW cm⁻¹ K⁻², and the out-of-plane thermal conductivity is reduced to 0.86 W m⁻¹ K⁻¹. Our results confirm that tailoring nanoscale structures inside thermoelectric films effectively enhances their performances.     

Doping effects on the thermoelectric properties of Cu-intercalated Bi2Te2.7Se0.3

We herein report an enhancement of the thermoelectric performance of spark plasma sintered polycrystalline n-type Bi₂Te_2.7Se_0.3 by the intercalation of Cu and the doping of Al on Bi-sites. Through the intercalation of a small amount of Cu (0.008), the reproducibility could be significantly improved, with ZT was enhanced from 0.64 to 0.73 at 300 K due to the reduced lattice thermal conductivity benefiting from intensified point-defect phonon scattering. We also found that Al is an effective doping element for power factor enhancement and for reducing the lattice thermal conductivity of Cu-intercalated Bi₂Te_2.7Se_0.3. With these synergetic effects, an enhanced ZT values of 0.78 at 300 K and 0.81 at 360 K were obtained in 1 at% Al-doped Cu_0.008Bi₂Te_2.7Se_0.3 (Cu_0.008Bi_1.98Al_0.02Te_2.7Se_0.3).     

A significant enhancement in thermoelectric power factor of In2Te3 thin films by Se doping and Te composition tuning

Thermoelectric power factor of a material significantly relies on its electrical conductivity, thermal conductivity, and Seebeck coefficient. Herein, an attempt has been made to enhance the thermoelectric power factor of In₂Te₃ thin films by tuning their Te composition and via Se doping. The optimum Se-doping concentration and Te composition enhanced the power factor of pristine In₂Te₃ films by 14 and 7.4 times, respectively. The modified chemical composition, structural characteristics, and surface morphological features of In₂Te₃ films are observed to be pivotal in improving their thermoelectric power factor. Overall, this study offers a facile approach to control the thermoelectric power factor of In₂Te₃ thin films which is significant for their futuristic applications.     

Specific features in the behavior of the effective mass and mobility in n-(Bi, Sb)2(Te, Se, S)3 solid solutions

The thermoelectric properties of the multicomponent solid solutions Bi_2?x Sb_xTe_3?y?z Se_yS_z with substitutions of atoms in both sublattices of Bi₂Te₃ were studied. The data obtained in studies of the galvanomagnetic effects in weak magnetic fields were used to properly take into account the change in the carrier scattering mechanisms due to the substitutions Sb → Bi, Se, and S → Te in the solid solutions. The mobility μ₀ with inclusion of the degeneracy, the effective density-of-states mass m/m ₀, and the lattice thermal conductivity κ_L were calculated. An analysis was carried out for the quantities μ₀, m/m ₀, and κ_L in the solid solutions under study as functions of the composition, carrier concentration, and temperature.     

Transport coefficients and defect structure of Sb2−xAgxTe3 single crystals

Incorporation of Ag in the crystal lattice of Sb₂Te₃ creates structural defects that have a strong influence on the transport properties. Single crystals of Sb_2−xAg_xTe₃ (x=0.0; 0.014; 0.018 and 0.022) were characterized by measurements of the temperature dependence of the electrical resistivity, Hall coefficient, Seebeck coefficient and thermal conductivity in the temperature range of 5-300 K. With an increasing content of Ag the electrical resistance, the Hall coefficient and the Seebeck coefficient all decrease. This implies that the incorporation of Ag atoms in the Sb₂Te₃ crystal structure results in an increasing concentration of holes. However, the doping efficiency of Ag appears to be only about 50% of the expected value. We explain this discrepancy by a model based on the interaction of Ag impurity with the native defects in the Sb_2−xAg_xTe₃ crystal lattice. Defects have a particularly strong influence on the thermal conductivity. We analyze the temperature dependence of the lattice thermal conductivity in the context of the Debye model. Of the various phonon scattering contributions, the dominant influence of Ag incorporation in the crystal lattice of Sb₂Te₃ is revealed to be point-defect scattering where both the mass defect and elastic strain play a pivotal role.     

Thermoelectric performance of monolayer Bi2Te2Se of ultra low lattice thermal conductivity

The electronic structure and thermoelectric properties of monolayer Bi₂Te₂Se were studied by density functional theory and semi-classical Boltzmann transport equation. The band gap with TB-mBJ can be improved for monolayer Bi₂Te₂Se. Monolayer Bi₂Te₂Se have ultra-low thermal conductivity comparing with other well-known two-dimensional materials. The monolayer Bi₂Te₂Se can improve electrical conductivities. ZT increases with increasing temperature for monolayer Bi₂Te₂Se. Comparing to GGA, TB-mBJ has larger ZT value in p-type doping. Monolayer Bi₂Te₂Se have larger ZT comparing with other well-known two-dimensional materials. Our calculated results show that our calculation greatly underestimates ZT value, therefore, monolayer Bi₂Te₂Se should have a higher ZT value.     

Effect of boundary scattering on the thermal conductivity of a nanostructured semiconductor material based on the BixSb2 ? xTe3 solid solution

This paper reports on a theoretical and experimental investigation of the behavior of the electrical and thermal conductivities of a nanostructured material based on Bi _x Sb_{2 − x} Te₃ solid solutions. The effect of boundary scattering has been taken into account by introducing the scattering mechanism with a constant mean free path equal to the nanoparticle size. A comparison with the results of the measurements has demonstrated that one can describe satisfactorily the experimental dependences of the electrical and thermal conductivities on the nanoparticle size by using only the parameters of the initial solid solution and its pure constituents. The estimates have revealed that the lattice thermal conductivity of nanostructured materials can be reduced by 20–30% as compared to the initial solid solution with nanoparticle sizes of the order of 20 nm, which should produce a favorable effect on the magnitude of the thermoelectric figure-of-merit.     

TeI4掺杂量对n型Bi2Te3基烧结材料热电性能的影响

采用区熔法结合放电等离子体快速烧结(SPS)技术制备了n型Bi₂Te₃基热电材料.在300—500K的温度范围内测量了各热电性能参数，包括电导率(σ)、塞贝克系数(α)和热导率(κ)，研究了掺杂剂TeI₄的含量(质量百分比分别为0，0.05，0.08，0.10，0.13和0.15wt%)对热电性能的影响.结果表明：试样的载流子浓度(n)随TeI₄含量增加而增大，使电导率增大、塞贝克系数的绝对值先增大而后减小，从而导致品质因子(α²σ)呈先增加后降低的变化趋势；同时，由于异质离子(I^-)以及载流子对声子的散射作用增强，可显著降低其晶格热导率.烧结材料的性能优值(ZT=α²σT/κ)对应于TeI₄含量为0.08wt%有其最大值，约为0.92.此外，烧结材料的抗弯强度增加至80MPa左右，从而可以显著改善材料的可加工性以及元器件的使用可靠性. 关键词： 2Te₃')" href="#">Bi₂Te₃ 放电等离子体快速烧结 热电性能     

Theoretical and experimental investigations of the properties of Ge2Sb2Te5 and indium-doped Ge2Sb2Te5 phase change material

We have carried out comprehensive computational and experimental study on the face-centered cubic Ge₂Sb₂Te₅ (GST) and indium (In)-doped GST phase change materials. Structural calculations, total density of states and crystal orbital Hamilton population have been calculated using first-principle calculation. 5 at.% doping of In weakens the Ge–Te, Sb–Te and Te–Te bond lengths. In element substitutes Sb to form In–Te-like structure in the GST system. In–Te has a weaker bond strength compared with the Sb–Te bond. However, both GST and doped alloy remain in rock salt structure. It is more favorable to replace Sb with In than with any other atomic position. X-ray diffraction (XRD) analysis has been carried out on thin film of In-doped GST phase change materials. XRD graph reveals that In-doped phase change materials have rock salt structure with the formation of In₂Te₃ crystallites in the material. Temperature dependence of impedance spectra has been calculated for thin films of GST and doped material. Thickness of the as-deposited films is calculated from Swanepoel method. Absorption coefficient (α) has been calculated for amorphous and crystalline thin films of the alloys. The optical gap (indirect band gap) energy of the amorphous and crystalline thin films has also been calculated by the equation \( \alpha h\nu = \beta (h\nu - E_{\text{g }} )^{2} \) . Optical contrast (C) of pure and doped phase change materials have also been calculated. Sufficient optical contrast has been found for pure and doped phase change materials.     

Enhanced thermoelectric performance of P-type Sb2Te3 thin films through organic-inorganic hybridization on flexible substrate

In this work, a new idea of organic-inorganic hybridization was proposed to fabricate flexible p-type - Sb₂Te₃/CH₃NH₃I thin films. The CH₃NH₃I has a strong adsorption which can promote the growth of organic molecules, improve the crystallization, and finally increase electrical conductivity. Post-annealing of the fabricated films increased the phonon scattering, thus resulting in a reduction of thermal conductivity and an increased ZT value. The annealed hybrid-composite film showed a significant enhancement in thermoelectric performance, with a maximum ZT value of 0.94 at a temperature of 413 K, which is twice as large as that of the as-deposited film.     

Anomalous thermal conductivity of single crystal Cu2Te2O5Cl2

A strong increase of the thermal conductivity is observed at the phase transition (T _c=18.2 K) in Cu₂Te₂O₅Cl₂ single crystal. This behavior is compared with that of the spin-Peierls system NaV₂O₅, where a similar experimental observation has been made, and the conventional spin-Peierls system CuGeO₃, where a modest kink in the thermal conductivity curve has been observed. The strong increase of the thermal conductivity atT _c in Cu₂Te₂O₅Cl₂ could be partially attributed to the opening of the energy gap in the magnetic excitation spectrum evident from the magnetic susceptibility measurements. However, the main reason for the anomaly of the thermal conductivity could be explained by a strong spin-lattice coupling in this system, which what is in agreement with the preliminary X-band electron spin resonance measurement.     

Preferential growth of Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> films with a nanolayer structure: enhancement of thermoelectric properties induced by nanocrystal boundaries

Preferential growth of different crystal planes in layered Bi₂Te₃ thin films with each layer <40 nm has been achieved by a simple magnetron co-sputtering method. The preferential growth of (015) plane or (001) was achieved at special depositing conditions due to the more sufficient growth along the in-plane direction induced by the enhanced diffusion of atoms and lower deposition rate. The Bi₂Te₃ film with preferential growth of (001) plane possesses about two times higher electrical conductivity and Seebeck coefficient as compared to the film with preferential growth of (015) plane, due to the greatly enhanced carrier mobility. Furthermore, the thermal conductivity has been suppressed due to more phonon scattering at grain boundaries, compared with ordinary Bi₂Te₃ alloys and films.