Ag-ZnO纳米复合热电材料的制备及其性能研究

ZnO是一类具有潜力的热电材料, 但其较大声子热导率影响了热电性能的进一步提高. 纳米复合是降低热导率的有效途径. 本文以醋酸盐为前驱体, 溶胶-凝胶法制备了Ag-ZnO纳米复合热电材料. 扫描电镜照片显示ZnO颗粒呈现多孔结构, Ag纳米颗粒分布于ZnO的晶粒之间. Ag-ZnO纳米复合材料的电导率比未复合ZnO材料高出100倍以上, 而热导率是未复合ZnO材料的1/2. 同时, 随着Ag添加量的增加, 赛贝克系数的绝对值逐渐减小. 综合以上原因, 添加7.5%mol Ag的Ag-ZnO纳米复合材料在700 K时的热电优值达到0.062, 是未复合ZnO材料的约25倍. 在ZnO基体中添加导电金属颗粒有利于产生导电逾渗通道, 提高材料体系的电导率, 但同时导致赛贝克系数的绝对值减小. 总热导率的差异来源于声子热导率的差异. 位于ZnO晶界的纳米Ag颗粒, 有利于降低声子热导率. 关键词： 热电材料 ZnO 纳米复合 热导率     

The effect of strontium doping on densification and electrical properties of Ce<Subscript>0.8</Subscript>Gd<Subscript>0.2</Subscript>O<Subscript>2−<Emphasis Type="Italic">δ</Emphasis></Subscript> electrolyte for IT-SOFC application

The effect of strontium doping on densification and ionic conductivity of gadolinium-doped ceria (GDC) was investigated. Doped (Sr-GDC) and un-doped GDC green specimens were subjected to dilatometric measurements to evaluate their sintering behavior and to identify the sintering temperature regimes. XRD spectra show the crystal structure of the sintered samples to be cubic. Strontium doping has exhibited a relatively larger grain size as is evident by the microstructural characterization. AC impedance analysis exhibited a threefold increase in ionic conductivity for Sr-GDC (0.072 S/cm) in comparison to GDC (0.028 S/cm) samples which can be attributed to improved density and increased grain size, resulting in enhancement of total conductivity. Additionally, strontium doping to GDC lattice not only increases the oxygen vacancies but also decreases the lattice binding energy, leading to increase in oxygen ion mobility which is also confirmed by the lower activation energy exhibited by the Sr-GDC formulation. Our experimental results established that co-doping is very effective in identifying new materials with remarkably high ionic conductivity with substantial reduction in the cost for solid oxide fuel cell application.     

Ca2+掺杂对CdO多晶热电性能的影响

以CaCO₃作为Ca²⁺源, 利用传统固相烧结法制备了Cd_1-xCa_xO (x=0, 0.01, 0.03, 0.05) 多晶块体样品并研究了Ca²⁺掺杂对CdO高温热电性能的影响. CaCO₃的掺入会导致CdO多晶载流子浓度降低, 使Cd_1-xCa_xO的电阻率ρ和塞贝克系数的绝对值|S|增大、电子热导率κ_e减小. 同时, 在CdO中掺入CaCO₃会引入点缺陷和气孔并可抑制CdO晶粒长大、晶界增多, 从而增加了对声子的散射, 使样品的声子热导率κ_p减小. 由于总热导率的大幅降低, Cd_0.99Ca_0.01O多晶样品在1000 K时的热电优值ZT可达0.42, 比本征CdO提高了约27%, 为迄今n型氧化物热电材料报道的最好结果之一.     

Thermoelectric properties of Li-doped Sr_(0.7)Ba_(0.3)Nb_2O_(6-δ) ceramics

Thermoelectric properties of Li-dopedSr_(0.7)Ba_(0.3)Nb_2O_(6-δ)ceramics were investigated in the temperature range from 323 K to 1073 K. The electrical conductivity increases significantly after lithium interstitial doping. However, both of the magnitudes of Seebeck coefficient and electrical conductivity vary non-monotonically but synchronously with the doping contents, indicating that doped lithium ions may not be fully ionized and oxygen vacancy may also contribute to carriers. The lattice thermal conductivity increases firstly and then decreases as the doping content increases, which is affected by competing factors.Thermoelectric performance is enhanced by lithium interstitial doping due to the increase of the power factor and the thermoelectric figure of merit reaches maximum value(0.21 at 1073 K) in the sample Sr_(0.70)Ba_(0.30)Li_(0.10)Nb_2O_6.     

Effect of tellurium on electrical and structural properties of sintered silicon nitride ceramics

The effects of tellurium (Te) additives on electrical conductivity, dielectric constant and structural properties of sintered silicon nitride ceramics have been studied. Different amounts of Te (10% and 20%) were added as sintering additives to silicon nitride ceramic powders and sintering was performed. Microstructure and composition were investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The electrical conductivity and dielectric constant (ε′) increase exponentially with temperature greater than 800 K. The electrical conductivity and dielectric constant increase but activation energy decreases from 0.72 to 0.33 eV with the increase of Te concentration. However, the conductivity increases five orders of magnitude at the concentration of 10% of Te in Si₃N₄. As the Te concentration increases the sintered silicon nitride ceramics become denser. These types of samples can be used as high temperature semiconducting materials.     

低维纳米材料热电性能测试方法研究

通过近几十年的研究,人们对于块体及薄膜材料的热电性能已经有了较全面的认识,热电优值ZT的提高取得了飞速的进展,比如碲化铋相关材料、硒化亚铜相关材料、硒化锡相关材料的最大ZT值都突破了2.但是,这些体材料的热电优值距离大规模实用仍然有较大的差距.通过理论计算得知,当块体热电材料被制作成低维纳米结构材料时,比如二维纳米薄膜、一维纳米线,热电性能会得到显著的改善,具有微纳米结构材料的热电性能研究引起了科研人员的极大兴趣.当块体硅被制作成硅纳米线时,热电优值改善了将近100倍.然而,微纳米材料的热电参数测量极具挑战,因为块体材料的热电参数测量方法和测试平台已经不再适用于低维材料,需要开发出新的测量方法和测试平台用来研究低维材料的热导率、电导率和塞贝克系数.本文综述了几种用于精确测量微纳米材料热电参数的微机电结构,包括双悬空岛、单悬空岛、悬空四探针结构,详细介绍了每一种微机电结构的制备方法、测量原理以及对微纳米材料热电性能测试表征的实例.     

Effect of carbon nanotubes addition on thermoelectric properties of Ca3Co4O9 ceramics

Increasing the phonon scattering center by adding nanoparticles to thermoelectric materials is an effective method of regulating the thermal conductivity. In this study, a series of Ca$_{3}$Co$_{4}$O$_{9}/x$ wt.% CNTs ($x=0$, 3, 5, 7, 10) polycrystalline ceramic thermoelectric materials by adding carbon nanotubes (CNTs) were prepared with sol-gel method and cold-pressing sintering technology. The results of x-ray diffraction and field emission scanning electron microscopy show that the materials have a single-phase structure with high orientation and sheet like microstructure. The effect of adding carbon nanotubes to the thermoelectric properties of Ca$_{3}$Co$_{4}$O$_{9}$ was systematically measured. The test results of thermoelectric properties show that the addition of carbon nanotubes reduces the electrical conductivity and Seebeck coefficient of the material. Nevertheless, the thermal conductivity of the samples with carbon nanotubes addition is lower than that of the samples without carbon nanotubes. At 625 K, the thermal conductivity of Ca$_{3}$Co$_{4}$O$_{9}$/10 wt.% CNTs sample is reduced to 0.408 W$\cdot$m$^{-1}\cdot$K$^{-1}$, which is about 73% lower than that of the original sample. When the three parameters are coupled, the figure of merit of Ca$_{3}$Co$_{4}$O$_{9}$/3 wt.% CNTs sample reaches 0.052, which is 29% higher than that of the original sample. This shows that an appropriate amount of carbon nanotubes addition can reduce the thermal conductivity of Ca$_{3}$Co$_{4}$O$_{9}$ ceramic samples and improve their thermoelectric properties.     

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     

Unexpected low thermal conductivity and large power factor in Dirac semimetal Cd_3As_2

Thermoelectrics has long been considered as a promising way of power generation for the next decades. So far,extensive efforts have been devoted to the search of ideal thermoelectric materials, which require both high electrical conductivity and low thermal conductivity. Recently, the emerging Dirac semimetal Cd3As2, a three-dimensional analogue of graphene, has been reported to host ultra-high mobility and good electrical conductivity as metals. Here, we report the observation of unexpected low thermal conductivity in Cd3As2, one order of magnitude lower than the conventional metals or semimetals with a similar electrical conductivity, despite the semimetal band structure and high electron mobility. The power factor also reaches a large value of 1.58 m W·m-1·K-2at room temperature and remains non-saturated up to 400 K.Corroborating with the first-principles calculations, we find that the thermoelectric performance can be well-modulated by the carrier concentration in a wide range. This work demonstrates the Dirac semimetal Cd3As2 as a potential candidate of thermoelectric materials.     

Graphene for Thermoelectric Applications: Prospects and Challenges

Thermoelectric power generators require high-efficiency thermoelectric materials to transform waste heat into usable electrical energy. An efficient thermoelectric material should have high Seebeck coefficient and excellent electrical conductivity as well as low thermal conductivity. Graphene, the first truly 2D nanomaterial, exhibits unique properties which suit it for use in thermoelectric power generators, but its application in thermoelectrics is limited by the high thermal conductivity and low Seebeck coefficient resulting from its gapless spectrum. However, with the possibility of modification of graphene's band structure to enhance Seebeck coefficient and the reduction of its thermal conductivity, it is an exciting prospect for application in thermoelectric power generation. This article examines the electronic, optical, thermal, and thermoelectric properties of graphene systems. The factors that contribute to these material properties in graphene systems like charge carriers scattering mechanisms are discussed. A salient aspect of this article is a synergistic perspective on the reduction of thermal conductivity and improvement of Seebeck coefficient of graphene for a higher thermoelectric energy conversion efficiency. In this regard, the effect of graphene nanostructuring and doping, forming of structural defects, as well as graphene integration into a polymer matrix on its thermal conductivity and Seebeck coefficient is elucidated.     

热电材料研究中的基础物理问题

热电转换技术主要包括利用半导体材料的泽贝克（Seebeck）效应将热能直接转化成电能和利用佩尔捷（Peltier）效应直接将电能转化成热能.文章简单回顾了热电转换材料中的物理效应及相关研究进展,重点介绍了常规热电材料（即窄带半导体）中的一些基本物理问题,其中包括一个好的热电材料应该具有的特性,以及提高半导体材料的电导率和泽贝克系数,降低热导率的物理机制和方法.文章还介绍了近年来电子晶体-声子玻璃类材料以及低维热电材料等热点问题的研究进展.最后还简单讨论了非常规热电材料的研究现状与趋势.     

硒化亚铜薄膜热电性能研究进展

热电材料可以实现热能和电能的相互转换,它是一种环境友好的功能性材料.当前,热电材料的热电转换效率低,这严重制约了热电器件的大规模应用,因此寻找更加优异热电性能的新材料或提高传统热电材料的热电性能成为热电研究的主题.与块状材料相比,薄膜具有二维的宏观性质和一维的纳米结构特性,方便研究材料的物理机制与性能的关系,还适用于制备可穿戴电子设备.本文总结了Cu₂Se薄膜5种不同的制备方法,包括电化学沉积、热蒸发、旋涂、溅射以及脉冲激光沉积.另外,结合典型事例,总结了薄膜的表征手段,并从Cu₂Se的电导率、塞贝克系数和热导率等参数出发,讨论了各个参数对热电性能的影响机制.最后介绍了Cu₂Se薄膜热电的热门应用方向.     

Changes of structure and composition of a zinc ion-implanted silicon surface during nanoparticle formation upon thermal treatment

Data from investigating the formation of nanoparticles (NPs) on a surface of silicon wafers after zinc ion implantation and thermal annealing are presented. The investigation is conducted by means of trans-mission electron microscopy, electron diffraction analysis, energy dispersive microanalysis, scanning tunneling microscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy. It is found that on their surfaces, the implanted samples have only films of amorphous silicon containing implanted zinc, oxygen, and carbon contamination. Thermal treatment in the range of 400–800°C leads to the formation NP with 20–50 nm wide and 10 nm tall on a wafer’s surface, plus a silicon oxide layer about 20 nm thick. NPs are composed of zinc compounds of the ZnO, ZnSiO₃, or Zn₂SiO₄ types. These NPs disappear after annealing at 1000°C.     

Dual material insulator SOI-LDMOSFET: A novel device for self-heating effect improvement

The silicon-on-insulator (SOI) power devices show good electrical performance but they suffer from inherent self-heating effect (SHE), which limits their operation at high current levels. The SHE effect is because of low thermal conductivity of the buried oxide layer. In this paper we propose a novel silicon on insulator lateral double diffused MOSFET (SOI-LDMOSFET) where the buried insulator layer under the active region consists of two materials in order to decrease the SHE. The proposed structure is called dual material buried insulator SOI-LDMOSFET (DM-SOI). Using two-dimensional and two-carrier device simulation, we demonstrate that the heat dissipation and the SHE can be improved in a conventional SOI-LDMOSFET by replacement of the buried oxide with dual material buried insulator (silicon nitride and silicon oxide) beneath the active region. The heat generated in the active silicon layer can be flowed through the buried silicon nitride layer to the silicon substrate easily due to high thermal conductivity of silicon nitride. Furthermore, the channel temperature is reduced, negative drain current slope is mitigated and electron and hole mobility is increased during high-temperature operation. The simulated results show that silicon nitride is a suitable alternative to silicon dioxide as a buried insulator in SOI structures, and has better performance in high temperature.     

Near-field-enhanced,off-resonant laser sintering of semiconductor particles for additive manufacturing of dispersed Au–ZnO-micro/nano hybrid structures

Off-resonant near-field enhancement by gold nanoparticles adsorbed on crystalline zinc oxide significantly increases the energy efficiency of infrared laser sintering. In detail, ten different gold mass loads on zinc oxide were exposed to 1,064 nm cw-laser radiation. Variation of scan speed, laser power, and spot size showed that the energy threshold required for sintering decreases and sintering process window widens compared to laser sintering of pure zinc oxide powder. Transmission electron microscope analysis after focused ion beam cross sectioning of the sintered particles reveals that supported gold nanoparticles homogenously resolidify in the sintered semiconductor matrix. The enhanced sintering process with ligand-free gold nanoparticles gives access to metal–semiconductor hybrid materials with potential application in light harvesting or energy conversion.     

Excellent thermal stability and thermoelectric properties of Pnma-phase SnSe in middle temperature aerobic environment

SnSe is considered to be a promising thermoelectric material due to a high ZT value and abundant and non-toxic composition elements. However, the thermal stability is an important issue for commercial application. In particular,thermoelectric materials are in the high temperature for a long time due to the working condition. The present work investigates the thermal stability and oxidation resistance of single crystal SnSe thermoelectric materials. The scanning electron microscopy(SEM) and transmission electron microscopy(TEM) results show that the internal of SnSe crystal is not easily oxidized, while the x-ray photoelectron spectroscopy(XPS) results indicate that the surface of SnSe is slight oxidized to SnO_2. Even if the surface is oxidized, the SnSe crystal still exhibits stable thermoelectric properties. Meanwhile,the crystallization quality of SnSe samples can be improved after the appropriate heat treatment in the air, which is in favor of the carrier mobility and can improve the electrical conduction properties of SnSe. Moreover, the decrease of defect density after heat treatment can further improve the Seebeck coefficient and electrical transport properties of SnSe. The density functional theory(DFT) calculation verifies the important role of defect on the electrical conductivity and electron configuration. In summary, appropriate temperature annealing is an effective way to improve the transmission properties of SnSe single crystal thermoelectric materials.     

Magnetic and transport properties of some light rare earth tungstates

Measurements relating to molar magnetic susceptibility, dc electrical conductivity and thermoelectric power of Nd, Sm, Eu and Gd are reported. The ac electrical conductivity at a few temperature ranges is also given. It is found that it follows the Curie-Weiss law behaviour and this has been attributed to the crystal field effect. The experimental value of Bohr magneton for the magnetic ions has been found to be in good agreement with theory. Thermoelectric power is negative in the measured temperature range suggesting these materials to bep-type semi-conductors and holes as the dominant charge carriers. The results are explained using band theory.     

高压烧结制备Tb掺杂n型(Bi1–xTbx)2(Te0.9Se0.1)3合金及其微结构和热电性能

采用高压烧结技术制备了稀土元素Tb掺杂的n型Bi2Te2.7Se0.3基纳米晶块体热电材料.将高压烧结成型的样品于633 K真空退火36 h.研究了Tb掺杂量对样品的晶体结构和热电性能的影响.结果表明,高压烧结制备的样品为纳米结构, Tb掺杂使样品的晶胞体积变大,功率因子增大,热导率降低,从而使ZT值提高.Tb掺杂量为x=0.004是最优的掺杂量,该掺杂量的高压烧结样品经退火处理后,于373 K时ZT值达到最大为0.99,并且在323-473 K范围内, ZT值均大于0.8,这对用于温差发电领域具有重要意义.     

Review of electronic transport models for thermoelectric materials

Thermoelectric devices have gained importance in recent years as viable solutions for applications such as spot cooling of electronic components, remote power generation in space stations and satellites etc. These solid-state devices have long been known for their reliability rather than their efficiency; they contain no moving parts, and their performance relies primarily on material selection, which has not generated many excellent candidates. Research in recent years has been focused on developing both thermoelectric structures and materials that have high efficiency. In general, thermoelectric research is two-pronged with (1) experiments focused on finding new materials and structures with enhanced thermoelectric performance and (2) analytical models that predict thermoelectric behavior to enable better design and optimization of materials and structures. While numerous reviews have discussed the importance of and dependence on materials for thermoelectric performance, an overview of how to predict the performance of various materials and structures based on fundamental quantities is lacking. In this paper we present a review of the theoretical models that were developed since thermoelectricity was first observed in 1821 by Seebeck and how these models have guided experimental material search for improved thermoelectric devices. A new quantum model is also presented, which provides opportunities for the optimization of nanoscale materials to enhance thermoelectric performance.     

Evaluation of Morphology and Size Distribution of Silicon and Titanium Oxide Nanoparticles Generated by Laser Ablation

Nanometer-sized particles of silicon and titanium oxide were generated by irradiating solid targets using a nanosecond pulsed-Nd : YAG laser in a low pressure atmosphere. A low pressure differential mobility analyzer (LP-DMA) was used to classify the size of the generated particles. The LP-DMA and electron microscopes (SEM and TEM) were used to measure the change in the size distribution and morphology of the generated particles with laser power density and system pressure. The size distribution of both silicon and titanium oxide ranged from two to one hundred nanometers in diameter depending on the laser power density and pressure. From the high resolution TEM observation and electron diffraction, it was found that the generated titanium oxide nanoparticles were composed of a core of faceted metallic single crystals with an oxide layer 'shell.