Thermoelectric properties of Bi2Se3/Bi2Te3/Bi2Se3 and Sb2Te3/Bi2Te3/Sb2Te3 quantum well systems

In this work, we develop a theory of thermoelectric transport properties in two-dimensional semiconducting quantum well structures. Calculations are performed for n-type 0.1 wt.% CuBr-doped Bi₂Se₃/Bi₂Te₃/Bi₂Se₃ and p-type 3 wt.% Te-doped Sb₂Te₃/Bi₂Te₃/Sb₂Te₃ quantum well systems in the temperature range 50–600 K. It is found that reducing the well thickness has a pronounced effect on enhancing the thermoelectric figure of merit (ZT). For the n-type Bi₂Se₃/Bi₂Te₃/Bi₂Se₃ with 7 nm well width, the maximum value of ZT is estimated to be 0.97 at 350 K and for the p-type Sb₂Te₃/Bi₂Te₃/Sb₂Te₃ with well width 10 nm the highest value of the ZT is found to be 1.945 at 440 K. An explanation is provided for the resulting higher ZT value of the p-type system compared to the n-type system.     

高温高压下掺杂N型PbTe的热电性能

 以Sb₂Te₃作为掺杂剂,利用高温高压技术,成功合成出N型PbTe。在常温下对其热电性能的测试结果表明：掺杂微量的Sb₂Te₃后,PbTe的赛贝克系数绝对值和电阻率大幅度下降,热导率随掺杂浓度的增加缓慢升高。掺杂后PbTe的品质因子先大幅度增加,后逐渐降低,最高达到8.7×10^-4 K^-1,它比常压合成的PbTe掺杂PbI₂高一倍以上。结果表明,将高温高压方法与掺杂相结合,能有效地改善PbTe的热电性能。     

Structural phase transition in Bi2Te3 under high pressure

Structural change in Bi₂Te₃ under high pressure up to 16.6 GPa has been studied by powder x-ray diffraction. We observed two times of phase transitions at room temperature at the pressures of 8 and 14 GPa, respectively. According to our preliminary result on electrical resistance, it is reasonable to suppose that superconducting transition with T _c =2.8 K at the pressures of 10.2 GPa is observed in phase II. On the other hand, we found anomalies of the pressure dependences of lattice parameters and volume at around 2 GPa, which probably means the change in electrical structure on the Fermi surface.     

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)     

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.     

Thickness-dependent electrical and optical properties of Ge8Sb2Te11 thin films

The amorphous Ge₈Sb₂Te₁₁thin films with varying thickness are thermally deposited on well-cleaned glass substrate from its polycrystalline bulk. Absence of any sharp peak confirms the amorphous nature of deposited films. Thickness-dependent electrical and optical properties including dc-activation energy, sheet resistivity, optical band gap, band tailing parameter, etc. of Ge₈Sb₂Te₁₁thin films have been studied. The optical parameters have been calculated from transmission, reflection and absorbance data in the spectral range of 200–1100 nm. It has been found that optical band gap and band tailing parameter decreases with the increase in Ge₈Sb₂Te₁₁thin films thickness. The dc-activation energy and sheet resistivity decreases while the crystallization temperature of the amorphous Ge₈Sb₂Te₁₁ films increases with the increase in thickness of the films. The decrease of the sheet resistivity has been substantiated quantitatively using the classical size-effect theory. These results have been explained on the basis of rearrangements of defects and disorders in the amorphous chalcogenide system.     

(Sb2Te3)0.75(1－x)(Bi2Te3)0.25(1－x)(Sb2Se3)x机械合金化粉体的制备及其冷压烧结样品的热电性能研究

采用机械合金化法制备了p型赝三元(Sb₂Te₃-Bi₂Te₃-Sb₂Se₃)合金粉体，对其进行XRD分析表明Te，Bi，Sb，Se单质粉末，经100h球磨后实现了合金化；SEM分析表明所得机械合金化粉体材料颗粒均匀、细小，颗粒尺寸在10nm到100nm量级.使用这种粉体制备了冷压烧结块体样品，在室温下测量了温差电动势率(α)和电导率(σ)，研究了烧结温度对材料热电性能的影响，结果表明在低于300℃的烧结温区，样品室温下的热电性能随烧结温度的升高不断提高，功率因子(α²σ)由未烧结样品的0.59μW cm^-1K^-2升高到在300℃下烧结样品的15.9μW cm^-1K^-2，这一结果对确定材料的最佳烧结温度具有重要意义. 关键词： 赝三元热电材料 机械合金化 冷压 烧结     

Characterization of Mn-doped Sb1.5Bi0.5Te3 single crystals

Abstract

Single crystals of (Sb_0.75Bi_0.25)_2-xMn_xTe₃ (x = 0.0–0.05) were characterized by X-ray diffraction, measurements of reflectance in the plasma resonance frequency region, Hall coefficient, electrical conductivity, and Seebeck coefficient. It was found that Mn atoms in the crystal structure of Sb_1.5Bi_0.5Te₃ behave like acceptors; the increase in the hole concentration is explained by the formation of substitutional defects of Mn'_Sb and Mn'_Bi in the crystal lattice of the studied crystals.     

Mechanical stress effect on the crystallization behavior of Ge2Sb2Te5 films studied by electrical resistance measurement

The mechanical stress effect on the crystallization behaviour of Ge₂Sb₂Te₅(GST) thin films is carefully investigated by electrical resistance measurements. It is found that the crystallization temperature of GST films increases as external compressive stress is applied, while the crystallization temperature decreases under tensile stress. We also find that the uneven distribution of extrinsic stress can widen the span of transition temperature. These results clearly demonstrate that mechanical stress plays an important role during the crystallization process of GST films and may further influence the reliability and storage speed of relevant devices. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effective Mass Enhancement and Thermal Conductivity Reduction for Improving the Thermoelectric Properties of Pseudo-Binary Ge2Sb2Te5

Ge₂Sb₂Te₅ is a famous phase-change memory material for rewriteable optical storage, which is widely applied in the information storage field. The stable trigonal phase of Ge₂Sb₂Te₅ shows potential as a thermoelectric material as well, due to its tunable electrical transport properties and low lattice thermal conductivity. In this work, the carrier concentration and effective mass of Ge₂Sb₂Te₅ are modulated by substituting Te with Se. Meanwhile, the thermal conductivity reduces from 2.48 W m⁻¹ K⁻¹ for Ge₂Sb₂Te₅ to 1.37 W m⁻¹ K⁻¹ for Ge₂Sb₂Te_3.5Se_1.5 at 703 K. Therefore, the thermoelectric figure of merit zT increases from 0.24 for Ge₂Sb₂Te₅ to 0.41 for Ge₂Sb₂Te_3.5Se_1.5 at 703 K. This study reveals that Se alloying is an effective way to enhance the thermoelectric properties of Ge₂Sb₂Te₅.     

应用于相变存储器的Cu-Ge3Sb2Te5薄膜的结构及相变特性研究

采用磁控溅射法制备了不同Cu含量的Cu-Ge₃Sb₂Te₅薄膜, 原位测试了薄膜电阻与温度的关系, 并利用X射线衍射仪、透射电镜、透过和拉曼光谱仪分别研究了 Cu-Ge₃Sb₂Te₅薄膜的晶体结构、微结构、禁带宽度及成键情况. 结果表明, Cu-Ge₃Sb₂Te₅薄膜的结晶温度和结晶活化能随着Cu含量的增加而增大, Cu的加入有效改善Ge₃Sb₂Te₅薄膜的热稳定性和10年数据保持力. 随着Cu含量的增加, 非晶态Cu-Ge₃Sb₂Te₅薄膜的禁带宽度逐渐减小. 同时, 拉曼峰从129 cm^-1向127 cm^-1处移动, 这是由于Cu–Te极性键振动增强的缘故. Cu-Ge₃Sb₂Te₅结晶为均匀、相互嵌套的六方Cu₂Te和Ge₂Sb₂Te₅相.     

Sb2Te3 纳米结构的制备与表征

以室温热电性能优异的传统热电材料Sb₂Te₃为研究对象,利用化学气相沉积法制备Sb₂Te₃单晶纳米结构,并研究其生长机理.实验结果表明,不加催化剂时Sb₂Te₃易生长成六方纳米盘,在金催化剂条件下定向生长成纳米线.Sb₂Te₃的形貌与其晶体结构和生长机理有关.Sb₂Te₃为三角结构,Sb和     

相变存储材料Ge1Sb2Te4和Ge2Sb2Te5薄膜的结构和电学特性研究

采用射频磁控溅射方法制备了两种用于相变存储器的Ge₁Sb₂Te₄和Ge₂Sb₂Te₅相变薄膜材料,对其结构、电学输运性质和恒温下电阻随时间的变化关系进行了比较和分析.X射线衍射(XRD)和原子力显微镜(AFM)的结果表明:随着退火温度的升高,Ge₁Sb₂Te₄薄膜逐步晶化,由非晶态转变为多晶态,表面出现均匀的、 关键词： 硫系相变材料 1Sb₂Te₄')" href="#">Ge₁Sb₂Te₄ 2Sb₂Te₅')" href="#">Ge₂Sb₂Te₅     

具有本征低晶格热导率的硫化银快离子导体的热电性能

硫化银(Ag_2S)是一种典型的快离子导体材料,前期关于Ag_2S的研究主要集中在光电和生物等领域.最近的研究表明, a-Ag_2S具有和金属一样的良好延展性和变形能力.但是, Ag_2S的热电性能尚无公开报道.本工作合成了单相Ag_2S化合物,系统研究了其在300—600 K范围的物相变化、离子迁移特性和电热输运性质.研究发现, Ag_2S在300—600 K温度区间表现出半导体的电输运性质.由于单斜-体心立方相晶体结构转变, Ag_2S的离子电导率、载流子浓度、迁移率、电导率、泽贝克系数等性质在455 K前后出现急剧变化.在550 K, Ag_2S的功率因子最高可达5μW·cm~(–1)·K~(–2). Ag_2S在300—600 K温度区间均表现出本征的低晶格热导率(低于0.6 W·m~(–1)·K~(–1)). S亚晶格中随机分布的类液态Ag离子是导致b-Ag_2S体心立方相具有低晶格热导率的主要原因.在573 K, Ag_2S的热电优值可达0.55,与Ag_2Se, Ag_2Te, CuAgSe等已报道的Ag基快离子导体热电材料的性能相当.     

斜锆石（ZrO2）高温高压相变的Raman光谱研究

 以Ar作压力介质，在0~23 GPa压力范围内，利用金刚石压腔装置（DAC）和激光加温技术，采用显微拉曼光谱进行原位测试，对处于准静水压力条件下的斜锆石开展高温高压相变研究。研究结果表明：室温下斜锆石ZrO₂于3.4 GPa时开始发生相变，到10.4 GPa时其明显转变成一个空间群为Pbca的斜方相。此新相随着压力升高，直到15.3 GPa，仍稳定存在。通过研究，首次获得了Pbca相的拉曼谱图。随后在15.3 GPa压力下进行了激光加温后淬火，结果发现，加热前的Pbca相又转变成了空间群为Pnam的PbCl₂结构类型的高压相，该相直到实验最高压力23 GPa仍稳定存在。     

Se替代Te对BiCuTeO电热输运性能的影响

层状氧硫族化合物由于其本征的低晶格热导率和可观的热电性能吸引了广泛关注,其中以BiCuSeO化合物的热电性能最为优异.但是,其同晶型化合物BiCuTeO,由于带隙较小且存在大量本征Cu空位,导致载流子浓度较高,热电性能较差,从而研究较少.针对BiCuTeO存在的上述问题,本文利用Se替代部分Te,以期能够展宽带隙并减少Cu空位,提高其热电性能.采用固相反应结合快速热压烧结制备了BiCuTe_(1-x)Se_xO(x=0, 0.1, 0.2, 0.3和0.4)块体热电材料,并系统地研究了该体系的电热输运性能.研究结果表明,利用Se替代Te,可以使BiCuTeO导电层化学键强度增加、带隙增大、载流子有效质量增加以及载流子散射增强,从而导致载流子浓度和迁移率同时降低,进而电导率随着Se含量增加而剧烈降低, Seebeck系数则显著增大.由于综合电输运性能恶化,功率因子随着Se含量增加而减小,导致热电优值zT随着Se含量增加而降低.最终,Se含量为x=0.1的样品,在室温和723 K时的zT值分别达到约0.3和0.7,仍然在较宽温区内保持较高的zT值.由于Se替代Te改变了BiCuTeO的能带结构,通过载流子浓度优化,有望进一步提高其热电性能.     

Composition dependence of polymorphism and electrical conductivity in Ce(IV)-doped Bi4V2O11

For the first time, a new member of the BIMEVOX family, namely BICEVOX, has been synthesized by the partial solid-state substitution of Ce(IV) for vanadium in parent Bi₄V₂O₁₁ solid electrolyte. The electrical conductivity in Bi₄Ce _x V_{2? x} O_{11?( x /2)? δ} has been investigated in the compositional range 0 ≤ x ≤ 0.30, using FT-IR, X-ray powder diffraction, differential thermal analysis and ac impedance spectroscopy. Owing to the long-term stabilization of α- and β-polymorphs compared to other members of the BIMEVOX family, the BICEVOX system may be a prospective solid electrolyte for intermediate temperature solid oxide fuel cells due to the significantly increased conductivity at lower temperatures observed for the compositions x > 0.20.     

Density functional study of Bi2Te3 and Bi4Te6 molecules

Results of a density functional study for the molecules Bi₂Te₃ and Bi₄Te₆ are reported here. For Bi₂Te₃, calculations yield eight stable conformations. For Bi₄Te₆, eight stable isomers are identified. Equilibrium geometries, adiabatic ionisation potentials, atomisation energies, and vibrational bands are estimated. The lowest energy conformations in both cases are clusters of C_s symmetry with all Te atoms two-fold coordinated and all Bi atoms three-fold coordinated. The predicted low energy conformation for Bi₄Te₆ has alternating rows of Bi and Te atoms. This molecule seems a reasonable precursor to solid bismuth telluride, which has alternating Bi and Te layers.