Intrinsic Seebeck Coefficient of Quantum Dots

The Seebeck coefficient S is an important performance characteristic of thermoelectric materials. In this paper we establish the fact that quantum dots and single-electron tunneling devices with narrow, well-spaced energy levels and sharp transmission resonances have a Seebeck coefficient independent of material parameters. By employing a delta function for the transmission resonances we arrive at an intrinsic expression for S in terms of the fundamental electronic charge e. We further confirm the validity of our result in the case of a transmission resonance with finite width.     

Al-doped ZnO and N-doped CuxO thermoelectric thin films for self-powering integrated devices

With the use of a thermoelectric material, terrestrial heat can be harvested then converted to electrical power. The advent of these devices has led to the idea of self-powering wherein devices are driven by heat from their working environment. The focus of this study is to fabricate low cost thermoelectric materials, such as aluminum-doped ZnO (ZnO:Al) and nitrogen-doped Cu_xO (Cu_xO:N) that can effectively harvest heat for power generation.ZnO:Al (n-type) and Cu_xO:N (p-type) thin films with nanocrystallites were deposited in (1.27×0.64) cm² glass substrates via spray pyrolysis technique. These materials exhibit significantly high thermoelectric properties, which is comparable to previous works on thermoelectric materials. ZnO:Al showed to have a maximum Seebeck coefficient (S) of 448 μV/K ranging from 300 to 330 K. Cu_xO:N exhibited a significantly much larger |S| of 1002 μV/K at the same temperature range. A prototype of a thermoelectric device was constructed based from these grown thin films and showed to generate a maximum of 32.8 mV at 28 K temperature difference.     

Low-Temperature Transport Properties of Sn<Subscript>24</Subscript>P<Subscript>19.3</Subscript>Br<Subscript>8</Subscript> and Sn<Subscript>17</Subscript>Zn<Subscript>7</Subscript>P<Subscript>22</Subscript>Br<Subscript>8</Subscript>

We report on temperature-dependent thermal conductivity, resistivity, and Seebeck coefficient of two polycrystalline Br-containing Sn-clathrate compounds with the type I crystal structure. Interstitial Br atoms reside inside the polyhedral cavities formed by the framework, resulting in hole conduction. The framework bonding directly influences the transport properties of these two compositions. The transport properties of these two clathrates are compared with those of other Sn-clathrates. We also discuss our results in terms of the potential for thermoelectric applications.     

p型方钴矿化合物BayFeCo3Sb12的热电性能研究

用两步固相反应法合成了单相的p型BayFeCo3Sb12化合物,并系统地研究了Ba不同填充分数对方钴矿化合物热电性能的影响:化合物载流子浓度强烈地依赖于填充原子的填充分数,随Ba填充分数y的增加,载流子浓度及电导率降低;塞贝克系数随温度T的上升而增加,比CoSb3的塞贝克系数有一定程度的提高,尤其是在中温部分有大幅度提高,得到的最大塞贝克系数由CoSb3的107μVK-1提高到Ba1.0FeCo3Sb12的235μVK-1晶格热导率随Ba的填充分数y的增加而进一步下降,Ba08FeCo3Sb12甚至降到2.2 Wm1K1;Ba08FeCo3Sb12化合物显示最大热电性能指数,在850K左右其最大无量纲热电性能指数ZT值达0.75.     

I-型硅基笼合物Ba8Ga16ZnxSi30-x的合成及电传输特性

用固相反应法结合熔融法合成Zn掺杂单相n型Ba8Ga16ZnxSi30-x化合物,探索Zn在Si位的取代对其结构及电传输特性的影响规律. 研究结果表明：x=1时化合物的平均键角畸变Δθ最大为4.4. ;当取代分数x＝0, 2, 4时,对应样品的电导率明显高于x＝1, 3时对应样品的电导率,在室温附近,Ba8Ga16Zn2Si28化合物表现出较高的电导率,约为3.0e5S/m,当x=1时,对应化合物的电导率在测试温度范围内最低;当取代分数x＝0, 2, 4时对应样品的Seebeck系数明显高于x＝1, 3时对应样品的Seebeck系数,且随着填充分数的增加,Seebeck系数分别逐渐降低;Ba8Ga16Zn2Si28化合物在测试温度范围内表现出较好的电性能,在1000K处具有最大的功率因子1.03e-3W/ (m·K2) .     

Thermoelectric Properties of Co<Subscript>4</Subscript>Sb<Subscript>12</Subscript> Skutterudite Materials with Partial In Filling and Excess In Additions

The properties of Co₄Sb₁₂ with various In additions were studied. X-ray diffraction revealed the presence of the pure δ-phase of In_0.16Co₄Sb₁₂, whereas impurity phases (γ-CoSb₂ and InSb) appeared for x = 0.25, 0.40, 0.80, and 1.20. The homogeneity and morphology of the samples were observed by Seebeck microprobe and scanning electron microscopy, respectively. All the quenched ingots from which the studied samples were cut were inhomogeneous in the axial direction. The temperature dependence of the Seebeck coefficient (S), electrical conductivity (σ), and thermal conductivity (κ) was measured from room temperature up to 673 K. The Seebeck coefficient of all In-added Co₄Sb₁₂ materials was negative. When the filler concentration increases, the Seebeck coefficient decreases. The samples with In additions above the filling limit (x = 0.22) show an even lower Seebeck coefficient due to the formation of secondary phases: InSb and CoSb₂. The temperature variation of the electrical conductivity is semiconductor-like. The thermal conductivity of all the samples decreases with temperature. The central region of the In_0.4Co₄Sb₁₂ ingot shows the lowest thermal conductivity, probably due to the combined effect of (a) rattling due to maximum filling and (b) the presence of a small amount of fine-dispersed secondary phases at the grain boundaries. Thus, regardless of the non-single-phase morphology, a promising ZT (S ² σT/κ) value of 0.96 at 673 K has been obtained with an In addition above the filling limit.     

Thermoelectric Properties of TlCu3Te2 and TlCu2Te2

We performed thermoelectric characterizations on TlCu₃Te₂: (Tl¹⁺)(Cu¹⁺)₃ (Te²⁻)₂ and TlCu₂Te₂: (Tl¹⁺)(Tl³⁺)(Cu¹⁺)₄(Te²⁻)₄, in order to understand the relationship between the thermoelectric properties (especially the lattice thermal conductivity κ _lat) and the valence states of Tl. The thermal conductivity of TlCu₂Te₂ is high (about 8 W m⁻¹ K⁻¹), while that of TlCu₃Te₂ is extremely low (around 0.5 W m⁻¹ K⁻¹) like other thallium tellurides. This high κ of TlCu₂Te₂ was caused not only by its large electronic contribution but also by its intrinsically high κ _lat. The present study implies that the valence states of Tl would play some important roles in determining the magnitude of κ _lat.     

Phase composition of CuInSe2 in different annealing process

CuInSe₂ was synthesized by a low cost, non-vacuum hydrothermal solution method using copper chloride, indium chloride and Se powder as raw materials. The reaction schemes of CuInSe₂ in different annealing processes were investigated by in-situ X-ray diffraction measurements. Its phase composition, crystal structure and morphology properties of CuInSe₂ were studied. The results show that CuInSe₂ has chalcopyrite crystal structure and it remains stable below the temperature of 773 K, but it decomposes to CuSe and InSe at temperature above 773 K in vacuum annealing. While in oxygen annealing, CuInSe₂ is oxidized to CuO, In₂O₃ and SeO₂ at the temperature of 523 K. Therefore, the temperature of selenization or annealing must be lower than 773 K in order to reduce the amount of CuSe and InSe in large production scale. The results were demonstrated by energy dispersive spectrometer as well. The process of its reaction mechanism was discussed based on the experimental data.     

Thermoelectric Properties of In<Subscript>0.3</Subscript>Ga<Subscript>0.7</Subscript>N Alloys

We report on the experimental investigation of the potential of InGaN alloys as thermoelectric (TE) materials. We have grown undoped and Si-doped In_0.3Ga_0.7N alloys by metalorganic chemical vapor deposition and measured the Seebeck coefficient and electrical conductivity of the grown films with the aim of maximizing the power factor (P). It was found that P decreases as electron concentration (n) increases. The maximum value for P was found to be 7.3 × 10⁻⁴ W/m K² at 750 K in an undoped sample with corresponding values of Seebeck coefficient and electrical conductivity of 280 μV/K and 93␣(Ω cm)⁻¹, respectively. Further enhancement in P is expected by improving the InGaN material quality and conductivity control by reducing background electron concentration.     

Bi2Ru2O7+WO3复合陶瓷的制备及热电性能

用RuCl_3·6H_2O、Bi(NO_3)3·5H_2O、WO_3及氨水为原料,通过沉淀反应制备水合二氧化钌和氢氧化铋混合包覆的WO_3粉体;再采用传统烧结工艺制备了Bi_2Ru_2O_7+WO_3复合陶瓷,并对其微观结构、形貌、热电性能进行了研究。结果表明,Ru、Bi形成了Bi_2Ru_2O_7第二相分散于体系中,陶瓷样品的电导率随着钌元素浓度的提高而增大。当钌元素的摩尔分数低于5%时,陶瓷样品的Seebeck系数为负值,样品为n型热电材料。该陶瓷具有明显的热电性能,在573K下,浓度为5%的样品的功率因子可达0.125 66μW/(m·K~2)。     

键合界面对面发射激光器的光、热性质影响

分析了采用双面键合长波长面发射激光器时,键合界面光吸收系数和电、热导率的变化对器件的光、热性质的影响。对于1λ光学腔的面发射激光器,键合界面吸收系数对器件光学性能影响较大,而对于1.5λ光学腔的面发射激光器,其光学性能基本不受键合界面吸收系数的影响。由有限元方法对面发射激光器的温度分布计算结果可知,当键合界面电、热导率小于GaAs电、热导率的1%时,激光器有源层的温度会有较大的上升。     

<Emphasis Type="Italic">p</Emphasis>-Type PbTe Thermoelectric Bulk Materials with Nanograins Fabricated by Attrition Milling and Spark Plasma Sintering

This work reports a manufacturing process that combines attrition milling and spark plasma sintering (SPS) in the preparation of PbTe bulk materials with nanosize grains. The process involves milling raw PbTe ingots into nanocrystalline powders and subsequent compacting of these powders into dense bulk materials by spark plasma sintering. Sintered samples with relative densities of over 95% and grain sizes as small as 80 nm to 1 μm were obtained through this process. The thermoelectric properties of the samples were measured and compared with those of raw ingots at temperatures from 300 K to 400 K to demonstrate the influence of grain size on thermoelectric properties. The results reveal that reducing the grain size improved thermoelectric performance.     

Approach to the Practical Use of Thermoelectric Power Generation

The results of research and development in the Japanese national project “Development for Advanced Thermoelectric Conversion Systems” are summarized, and the approaches to practical use of advanced thermoelectric modules and power generation systems are presented. The 5-year national project was successfully completed in March 2007. Three kinds of high-efficiency cascaded thermoelectric modules and two kinds of innovative Bi-Te thermoelectric modules were successfully developed. Heat cycle tests for three types of modules were also completed. Moreover, four types of advanced thermoelectric power generation systems were experimentally demonstrated for recovery of waste heat from the industrial and private sectors. In order to proceed further, thermoelectric power generation systems using practical heat sources were followed after installation of the developed modules. In parallel, various approaches for practical use by private companies, as well as plans for the next-phase project by the National Institute of Advanced Industrial Science and Technology (AIST) and the Engineering Advancement Association (ENAA), were also followed. The scenarios to proceed to the commercial phase of thermoelectric power generation are discussed on the basis of the results of the national project.     

Off-Center Guest Vibrations and Their Effect on Lattice Thermal Conductivity in <Emphasis Type="Italic">n</Emphasis>- and <Emphasis Type="Italic">p</Emphasis>-Type β-Ba<Subscript>8</Subscript>Ga<Subscript>16</Subscript>Sn<Subscript>30</Subscript>

We report on thermoelectric and Raman scattering studies of single crystalline samples of a type I clathrate Ba₈Ga₁₆Sn₃₀. The n- and p-type samples have a thermopower of −300 μV/K and +270 μV/K, and electrical resistivity of 20 mΩ cm and 40 mΩ cm at room temperature, respectively. Regardless of the charge carrier type, the lattice thermal conductivity κ _L shows typical glass-like behavior. The low-energy vibration of Ba(2) in the tetrakaidecahedron is manifested in the Raman scattering spectrum as a peak at 15 cm⁻¹. This energy agrees with the characteristic vibrational temperature of 20 K derived from the analysis of the specific heat data with a soft-potential model. The fact that both the vibrational energy and the magnitude of κ _L for Ba₈Ga₁₆Sn₃₀ are lowest among the type I clathrates is evidence that off-center vibrations are responsible for the strong reduction of κ _L. Analysis of κ _L(T) revealed that the positional disorder associated with the off-center vibrations acts as the Rayleigh scattering center, and the coupling between guest vibrational modes and acoustic phonons is stronger than that in Sr₈Ga₁₆Ge₃₀ and Eu₈Ga₁₆Ge₃₀.