Microstructures and thermoelectric properties of GeSbTe based layered compounds

Microstructures and thermoelectric properties of Ge₁Sb₂Te₄ and Ge₂Sb₂Te₅ chalcogenide semiconductors have been investigated to explore the possibility of their thermoelectric applications. The phase transformation from the face-centered cubic to hexagonal structure was observed in Ge₂Sb₂Te₅ compounds prepared by the melt spinning technique. The Seebeck coefficient and electrical resistivity of the alloys were increased due to the enhanced scattering of charge carriers at grain boundaries. The maximum power factors of the rapidly solidified Ge₁Sb₂Te₄ and Ge₂Sb₂Te₅ attained 0.975×10^-3 W m^-1K^-2 at 750 K and 0.767×10^-3 W m^-1K^-2 at 643 K respectively, higher than those of water quenched counterparts, implying that thermoelectric properties of GeSbTe based layered compounds can be improved by grain refinement. The present results show this class of chalcogenide semiconductors is promising for thermoelectric applications. PACS  84.60.Rb; 81.05.Hd; 72.20.Pa; 64.70.Kb; 61.66.Fn     

Bi-Sb-Te基热电薄膜温差电池离子束溅射制备与表征

本文采用离子束溅射Bi/Te和Sb/Te二元复合靶,直接制备n型Bi₂Te₃热电薄膜和p型Sb₂Te₃热电薄膜.在退火时间同为1 h的条件下,对所制备的Bi₂Te₃薄膜和Sb₂Te₃薄膜进行不同温度的退火处理,并对其热电性能进行表征.结果表明,在退火温度为150 ℃时,制备的n型Bi₂Te₃关键词： 薄膜温差电池 2Te₃薄膜')" href="#">Sb₂Te₃薄膜 2Te₃薄膜')" href="#">Bi₂Te₃薄膜 离子束溅射     

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.     

Annealing effects on the structural and electrical transport properties of n-type Bi2Te2.7Se0.3 thin films deposited by flash evaporation

N-type Bi₂Te_2.7Se_0.3 thermoelectric thin films with thickness 800 nm have been deposited on glass substrates by flash evaporation method at 473 K. Annealing effects on the thermoelectric properties of Bi₂Te_2.7Se_0.3 thin films were examined in the temperature range 373-573 K. The structures, morphology and chemical composition of the thin films were characterized by X-ray diffraction, field emission scanning electron microscope and energy dispersive X-ray spectroscopy, respectively. Thermoelectric properties of the thin films have been evaluated by measurements of the electrical resistivity and Seebeck coefficient at 300 K. The Hall coefficients were measured at room temperature by the Van der Pauw method. The carrier concentration and mobility were calculated from the Hall coefficient. The films thickness of the annealed samples was measured by ellipsometer. When annealed at 473 K, the electrical resistivity and Seebeck coefficient are 2.7 mΩ cm and −180 μV/K, respectively. The maximum of thermoelectric power factor is enhanced to 12 μW/cm K².     

Annealing temperature influence on electrical properties of ion beam sputtered Bi2Te3 thin films

Ion beam sputtering process was used to deposit n-type fine-grained Bi₂Te₃ thin films on BK7 glass substrates at room temperature. In order to enhance the thermoelectric properties, thin films are annealed at the temperatures ranging from 100 to 400 °C. X-ray diffraction (XRD) shows that the films have preferred orientations in the c-axis direction. It is confirmed that grain growth and crystallization along the c-axis are enhanced as the annealing temperature increased. However, broad impurity peaks related to some oxygen traces increase when the annealing temperature reached 400 °C. Thermoelectric properties of Bi₂Te₃ thin films were investigated at room temperature. The Bi₂Te₃ thin films, including as-deposited, exhibit the Seebeck coefficients of −90 to −168 μV K⁻¹ and the electrical conductivities of 3.92×10²-7.20×10² S cm⁻¹ after annealing. The Bi₂Te₃ film with a maximum power factor of 1.10×10⁻³ Wm⁻¹ K⁻² is achieved when annealed at 300 °C. As a result, both structural and transport properties have been found to be strongly affected by annealing treatment. It was considered that the annealing conditions reduce the number of potential scattering sites at grain boundaries and defects, thus improving the thermoelectric properties.     

Electrodeposition of BixSb2−xTey thermoelectric thin films from nitric acid and hydrochloric acid systems

The electrochemical behaviors of Bi^III, Te^IV and Sb^III single ions and their mixtures were investigated in nitric acid and hydrochloric acid system separately. Based on which, Bi_xSb_2−xTe_y thermoelectric films were prepared by potentiostatic electrodeposition from the solutions with different concentrations of Bi^III, Te^IV and Sb^III in the two acid systems. The morphologies, compositions, structures, Seebeck coefficients and resistivities of the deposited thin films were characterized and compared by ESEM (or FESEM), EDS, XRD, Seebeck coefficient measurement system and four-probe resistivity measuring device respectively. The results show that although Bi_xSb_2−xTe_y thermoelectric thin film which structure is consistent with the standard pattern of Bi_0.5Sb_1.5Te₃ can be gained in both of the two acid solutions by adjusting the deposition potential, their morphologies and thermoelectric properties have big differences in different acid solutions.     

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)     

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.     

Phase-change behavior in Si/Sb80Te20 nanocomposite multilayer films

Phase-change behavior in Si/Sb₈₀Te₂₀ nanocomposite multilayer films were investigated by utilizing in situ resistance measurements. It was found that the crystallization temperature increased firstly with increasing Si layer thickness within the multilayer films, and then remained almost unchanged at 170°C. The multilayer films have the merits of both good thermal stability and fast phase-change speed. An increase in crystallization temperature by around 95°C was observed for the multilayer films when the Sb₈₀Te₂₀ layer thickness was reduced to 3 nm. Cross-sectional transmission electron microscopy (TEM) observations revealed that Si/Sb₈₀Te₂₀ nanocomposite multilayer films had layered structures with clear interfaces. The reversible phase change between set and reset states was verified in phase-change random access memory (PCRAM) cell based on [Si (1 nm)/Sb₈₀Te₂₀ (5 nm)]₁₇ multilayer film.     

Thermoelectric properties in p-type nanostructured Ge-doped Sb100GeTe150 alloy

Ge-doped Sb₁₀₀GeTe₁₅₀ alloy were prepared using spark plasma sintering technique, and its thermoelectric properties were evaluated over the temperature range 318–492 K. Through XRD analysis, we observed the same single phase as Sb₂Te₃ and weakened diffraction peaks. Rietveld refinement reveals that there is 0.96 at.% Ge that occupies in the Sb sites, leading to the lattice distortion in the Sb–Te crystal. High-resolution TEM images show that there are many nanodomains randomly distributed in the matrix with a large amount of amorphous phase adjoined. Measurements indicated that the Seebeck coefficients (α) increase and the electrical and thermal conductivities decrease with temperature in the entire temperature range. The maximum α value reaches 135 μV/K at 492 K, and the thermal conductivities are about 0.3 W/mK lower than those of present Sb₂Te₃ for the corresponding temperatures. The highest thermoelectric figure of merit ZT for the nanostructured alloy Sb₁₀₀GeTe₁₅₀ is 0.84 at 492 K, whereas that of the currently prepared Sb₂Te₃ is 0.74 at the corresponding temperature.     

Investigation of Sb-rich Si2Sb2+x Te6 material for phase change random access memory application

Sb-rich Si₂Sb_2+x Te₆ (x=0, 1.4, 10) thin films are proposed to present the feasibility for electronic phase change memory application. The crystallization behavior is improved by adding Sb into the material. The crystallization temperature is about 506, 502, and 450 K for Si₂Sb₂Te₆, Si₂Sb_3.4Te₆, and Si₂Sb₁₂Te₆ films, respectively, and the corresponding activation energy is in the range from 2.70 to 1.69 eV, which is expected for a low-power and high-speed SET operation. In addition, maximum temperature for a 10 year data lifetime is estimated to be 133, 127, and 98°C, respectively. The memory devices are successfully fabricated employing these films, promising that the stability of the low-resistance crystalline state is improved by adding Sb into the stoichiometric Si₂Sb₂Te₆ material, and the reversibility of the device is also realized for the Si₂Sb₁₂Te₆-based cell.     

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.     

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.     

Preparation and characterization of the antimony telluride hexagonal nanoplates

Nanostructured thermoelectric materials are of much interest for improving the thermoelectric figure of merit. In the present work, Sb₂Te₃ hexagonal nanoplates were successfully fabricated via a facile hydrothermal method. The products were characterized by means of X-ray diffraction, field-emission scanning electron microscope, transmission electron microscope and energy-dispersive X-ray spectroscopy. The results show that the typical Sb₂Te₃ crystal is hexagonal in shape with about 35 nm in thickness and 300 nm in edge length. The mechanism for formation of Sb₂Te₃ hexagonal nanoplates is primarily discussed.     

Effects of double filling of Pb and Ba on thermoelectric properties of PbxBayCo4Sb11.5Te0.5 compounds by HPHT

Skutterudite compounds Pb_xBa_yCo₄Sb_11.5Te_0.5 (x≤0.23,y≤0.27) with bcc crystal structure have been prepared by the high pressure and high temperature (HPHT) method. The study explored a chemical method for filling Pb and Ba atoms into the voids of CoSb₃ to optimize the thermoelectric figure of merit ZT in the system of Pb_yBa_xCo₄Sb_11.5Te_0.5. The structure of Pb_xBa_yCo₄Sb_11.5Te_0.5 skutterudites was evaluated by means of X-ray diffraction. The Seebeck coefficient, electrical resistivity and power factor were performed from room temperature to 710 K. Compared with Co₄Sb_11.5Te_0.5, the thermal conductivity of Pb and Ba double-filled samples was reduced evidently. Among all filled samples, Pb_0.03Ba_0.27Co₄Sb_11.5Te_0.5 showed the highest power factor of 31.64 μW cm⁻¹ K⁻² at 663 K. Pb_0.05Ba_0.25Co₄Sb_11.5Te_0.5 showed the lowest thermal conductivity of 2.73 W m⁻¹ K⁻¹ at 663 K, and its maximum ZT value reached 0.63 at 673 K.     

Thermoelectric properties and electronic structure of Te-doped CoSb3 compounds

Co₄Sb_12−xTe_x compounds were prepared by mechanical alloying combined with cold isostatic pressing, and the effects of Te doping on the thermoelectric properties were studied. The electronic structure of Te-doped and undoped CoSb₃ compounds has been calculated using the first-principles plane-wave pseudo-potential based on density functional theory. The experimental and calculated results show that the value of the solution limit x of Te in Co₄Sb_12−xTe_x compounds is between 0.5 and 0.7. The Fermi surface of CoSb₃ is located between the conduction band and the valence band, and its electrical resistivity decreases with increasing temperature. The density of states is mainly composed of Co 3d and Sb 5p electrons for intrinsic CoSb₃.The Fermi surface of Te-doped compounds moves to the conduction band and its electrical resistivity increases with increasing temperature, exhibiting n-type degenerated semiconductor character. Under the conditions of the experiment, the maximum value 2.67 mW/m K² of the power factor for Co₄Sb_11.7Te_0.3 is obtained at 600 K; this is about 14 times higher than that of CoSb₃.     

Band gap tunable and improved microstructure characteristics of Cu2ZnSn(S1−x,Sex)4 thin films by annealing under atmosphere containing S and Se

Cu₂ZnSn(S_xS_1?x)₄ (CZTSSe) thin films were prepared by annealing a stacked precursor prepared on Mo coated glass substrates by the sputtering technique. The stacked precursor thin films were prepared from Cu, SnS₂, and ZnS targets at room temperature with stacking orders of Cu/SnS₂/ZnS. The stacked precursor thin films were annealed using a tubular two zone furnace system under a mixed N₂ (95%) + H₂S (5%) + Se vaporization atmosphere at 580 °C for 2 h. The effects of different Se vaporization temperature from 250 °C to 500 °C on the structural, morphological, chemical, and optical properties of the CZTSSe thin films were investigated. X-ray diffraction patterns, Raman spectroscopy, and X-ray photoelectron spectroscopy results showed that the annealed thin films had a single kesterite crystal structure without a secondary phase. The 2θ angle position for the peaks from the (112) plane in the annealed thin films decreased with increasing Se vaporization temperature. Energy dispersive X-ray results showed that the presence of Se in annealed thin films increased from 0 at% to 42.7 at% with increasing Se vaporization temperatures. UV–VIS spectroscopy results showed that the absorption coefficient of all the annealed thin films was over 10⁴ cm^?1 and that the optical band gap energy decreased from 1.5 eV to 1.05 eV with increasing Se vaporization temperature.     

Ge/Sb2Te3 nanocomposite multilayer films for high data retention phase-change random access memory application

The amorphous-to-crystalline transition of Ge/Sb₂Te₃ nanocomposite multilayer films with various thickness ratios of Ge to Sb₂Te₃ were investigated by utilizing in situ temperature-dependent film resistance measurements. The crystallization temperature and activation energy for the crystallization of the multilayer films increased with the increase in thickness ratio of Ge to Sb₂Te₃. The difference in sheet resistance between amorphous and crystalline states could reach as high as 10⁴ Ω/□. The crystallization temperature and activation energy for the crystallization of Ge/Sb₂Te₃ nanocomposite multilayer films was proved to be larger than that of conventional Ge₂Sb₂Te₅ film, which ensures a better data retention for phase-change random access memory (PCRAM) use. A data retention temperature for 10 years of the amorphous state [Ge (2 nm)/Sb₂Te₃ (3 nm)]₄₀ film was estimated to be 165 °C. Transmission electron microscopy (TEM) images revealed that Ge/Sb₂Te₃ nanocomposite multilayer films had layered structures with clear interfaces.     

Cu掺杂AgSbTe2化合物的相稳定、晶体结构及热电性能

利用熔融快淬结合放电等离子烧结(SPS), 制备了Cu_xAg_1-xSbTe₂(x= 0---0.3)样品. 粉末X射线衍射(XRD)分析结果显示, SPS处理以前, 含Cu样品形成NaCl型结构的固溶体, 而未加入Cu的样品析出Ag₂Te第二相. 根据热分析和XRD测量结果, Cu的加入能够有效抑制Ag₂Te的析出, 但同时会在快淬样品中产生少量非晶相. 在温度升高到540 K左右时, 非晶相发生晶化, 形成Sb₇Te亚稳相, 并最终转变成Sb₂Te₃稳定相. 对快淬样品进行低温SPS快速处理后, x =0.1样品为面心立方结构的单相化合物, 但是x =0.2, 0.3的样品分别析出第二相Sb₇Te和Sb₂Te₃. 由于析出第二相, x=0.2, 0.3样品的电导率增大, Seebeck系数减小, 热导率相应升高, 综合热电性能降低. x=0.1单相样品的功率因子与文献报道的AgSbTe₂化合物相当. 元素替代的合金化效应 增强了Cu_0.1Ag_0.9SbTe₂化合物的声子散射, 有效降低了样品的热导率. 因此, 单相样品Cu_0.1Ag_0.9SbTe₂表现出较佳的热电性能, 在620 K时热电优值达到1.     

Electrodeposition of thermoelectric Bi2Te3 thin films with added surfactant

Bismuth telluride (Bi₂Te₃) thin films were electrodeposited at room temperature from nitric baths in the presence of a surfactant, cetyltrimethylammonium bromide (CTAB). Nearly stoichiometric Bi₂Te₃ thin films were obtained from electrolytes containing 7.5 mM Bi(NO₃)₃. The surface morphology and mechanical properties of the electrodeposited thin film were improved by the addition of CTAB to the electrolyte, while the electrical and thermoelectric properties were preserved. Post-deposition annealing in a reducing environment did not improve the electrical and thermoelectric properties, possibly because the change in the microstructure of the Bi₂Te₃ thin film was too small.