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.     

Enhanced thermal stability of VCSEL array by thermoelectric analysis-based optimization of mesas distribution

The thermal stability of a vertical-cavity surface-emitting laser(VCSEL) array is enhanced by redesigning the mesa arrangement. Based on a thermoelectric coupling three-dimensional(3D) finite-element model, an optimized VCSEL array is designed. The effects of this optimization are studied experimentally. Power density characteristics of VCSEL arrays with different mesa configuration are obtained under different thermal stress in which the optimized device shows improved performance. Optimized device also shows better stability from measured spectra and calculated thermal resistances. The experimental results prove that our simulation model and optimization is instructive for VCSEL array design.     

Nanostructuration for thermoelectricity: The path to an unlimited reduction of phonon transport

Improvements of the thermoelectric properties in bulk materials have very often relied on the reduction of thermal conductivity, which is mostly based on phonon propagation. Reducing further phonon transport has remained a difficult task due to the fact that current thermoelectric materials are already efficient thermal insulators, and also because of the broadness of the Planckian phonon spectrum. Nanostructuring has provided new paths for decreasing thermal conduction, especially by means of scatterers, be them nano-objects, surfaces, or interfaces. In this chapter, the physics of demonstrated nanoscale methodologies for the reduction of thermal conduction will be proposed together with illustrations from direct simulations.     

低维纳米材料量子热输运与自旋热电性质 ——非平衡格林函数方法的应用

低维材料不断涌现的新奇性质吸引着科学研究者的目光. 除了电子的量子输运行为之外, 人们也陆续发现和确认了热输运中显著的量子行为, 如 热导低温量子化、声子子带、尺寸效应、瓶颈效应等. 这些小尺度体系的热输运性质可以很好地用非平衡格林函数来描述. 本文首先介绍了量子热输运的特性、声子非平衡格林函数方法及其在低维纳米材料中的研究进展; 其次回顾了近年来在 一系列低维材料中发现的热-自旋输运现象. 这些自旋热学现象展现了全新的热电转换机制, 有助于设计新型的热电转换器件, 同时也给出了用热产生自旋流的新途径; 最后介绍了线性响应理论以及在此理论框架下结合声子、电子非平衡格林函数方法进行的一些有益的探索. 量子热输运的研究对热效应基础研究以及声子学器件、能量转换器件的发展有着不可替代的重要作用.     

Calculation and optimization of thermoelectric cooling modes of thermally loaded elements

The results of calculating the characteristics of the heat-transfer process in thermoelectric cooling and temperature control are presented. The influence of the inhomogeneity of the heat flux and thermal contacts on the temperature increase of the heat-loaded element has been defined. The analysis of the cooling efficiency depending on the operating characteristics and the current strength of the power supply of thermoelectric modules, parameters of the heat-loaded element and the individual components of the system, and the conditions of the heat exchange with the external environment has been performed. It has been shown that, under certain conditions, the use of the thermoelectric modules cannot lead to a cooling of the element, but rather to heating. The possibility of optimizing the cooling to reduce the temperature of the heat-loaded element and power consumption of the thermoelectric module has been considered.     

Investigation of the thermoelectric properties of one-layer transition metal dichalcogenides

Transition metal dichalcogenides (TMDCs) have attracted various research interests as one of the priorities of materials research due to their promising properties, especially in the field of thermoelectricity. The efficiency or performance of thermoelectric devices is expressed in terms of the thermoelectric figure-of-merit (ZT) – a standard indicator of a material's thermoelectric properties for use in cooling systems. The evaluation of ZT is principally determined by the thermoelectric characteristics of the nanomaterials. In this paper, a set of investigative computations was performed to study the thermoelectric properties of monolayer TMDCs according to the semiclassical treatment of the Boltzmann transport equation. It was confirmed that the thermoelectric properties of 2D materials can be greatly improved compared with their bulk properties. Calculations show an improvement in the power factor for the TMDCs under consideration, and, thus, the ZT compared to the bulk state due to an improvement in the Seebeck modulus and electrical conductivity, without significantly affecting the thermal conductivity and negatively affecting the ZT. These materials show clear characteristic variations at room temperature, with the highest ZT values of 2.919 and 2.873 obtained for WSe2 and WS2, respectively.     

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.     

Emerging Theory,Materials, and Screening Methods: New Opportunities for Promoting Thermoelectric Performance

High‐performance thermoelectric materials have attracted immense interest due to the capability of directly converting thermal energy into electrical energy. The correlation and inherent complexity between the thermoelectric parameters pose serious challenges to improving the materials’ thermoelectric performance. Herein, the emerging novel theories in the field of thermoelectrics are summarized, such as the coherent phonon, nanophononic metamaterial, rattling effect, topological phonon, and topological electron. The impacts of these new concepts on thermoelectric performance are then reviewed. Finally, a number of promising thermoelectric materials such as one‐dimensional nanowires, two‐dimensional layered materials, and nanomesh structures are discussed. The advanced understanding of thermal and electrical transport properties in thermoelectric materials is presented herein, providing new opportunities for improving thermoelectric performance.     

Energy band and charge-carrier engineering in skutterudite thermoelectric materials

The binary CoSb₃ skutterudite thermoelectric material has high thermal conductivity due to the covalent bond between Co and Sb, and the thermoelectric figure of merit, ZT, is very low. The thermal conductivity of CoSb₃ materials can be significantly reduced through phonon engineering, such as low-dimensional structure, the introduction of nano second phases, nanointerfaces or nanopores, which greatly improves their ZT values. The phonon engineering can optimize significantly the thermal transport properties of CoSb₃-based materials. However, the improvement of the electronic transport properties is not obvious, or even worse. Energy band and charge-carrier engineering can significantly improve the electronic transport properties of CoSb₃-based materials while optimizing the thermal transport properties. Therefore, the decoupling of thermal and electronic transport properties of CoSb₃-based materials can be realized by energy band and charge-carrier engineering. This review summarizes some methods of optimizing synergistically the electronic and thermal transport properties of CoSb₃ materials through the energy band and charge-carrier engineering strategies. Energy band engineering strategies include band convergence or resonant energy levels caused by doping/filling. The charge-carrier engineering strategy includes the optimization of carrier concentration and mobility caused by doping/filling, forming modulation doped structures or introducing nano second phase. These strategies are effective means to improve performance of thermoelectric materials and provide new research ideas of development of high-efficiency thermoelectric materials.     

Nonlinear phenomena in quantum thermoelectrics and heat

We review recent developments in nonlinear quantum transport through nanostructures and mesoscopic systems driven by thermal gradients or in combination with voltage biases. Low-dimensional conductors are excellent platforms for analyzing both the thermoelectric and heat dynamics beyond the linear response because, due to their small size, a small temperature difference applied across regions gives rise to large thermal biases. We offer a theoretical discussion based on the scattering approach to highlight the differences between the linear and the nonlinear regimes of transport. We discuss recent experiments on quantum dots and molecular junctions subjected to strong temperature differences. Theoretical predictions concerning the Kondo effect and heat rectification proposals are briefly examined. An important issue is the calculation of thermoelectric efficiencies including nonlinearities. Cross Seebeck effects and nonlinear spin filtering arise in superconductors and topological insulators, while mixed noises between charge and heat currents are also considered. Finally, we provide an outlook on the possible future directions of the field.     

Recent advances in non-Pb-based group-Ⅳ chalcogenides for environmentally-friendly thermoelectric materials

Pb-based group-IV chalcogenides including Pb Te and Pb Se have been extensively studied as high performance thermoelectric materials during the past few decades.However,the toxicity of Pb inhibits their applications in vast fields due to the serious harm to the environment.Recently the Pb-free group-IV chalcogenides have become an extensive research subject as promising thermoelectric materials because of their unique thermal and electronic transport properties as well as the enviromentally friendly advantage.This paper briefly summarizes the recent research advances in Sn-,Ge-,and Sichalcogenides thermoelectrics,showing the unexceptionally high thermoelectric performance in Sn Se single crystal,and the significant improvement in thermoelectric performance for those polycrystalline materials by successfully modulating the electronic and thermal transport through using some well-developed strategies including band engineering,nanostructuring and defect engineering.In addition,some important issues for future device applications,including N-type doping and mechanical and chemical stabilities of the new thermoelectrics,are also discussed.     

Research status and performance optimization of medium-temperature thermoelectric material SnTe

Thermoelectric materials have the ability to directly convert heat into electricity, which have been extensively studied for decades to solve global energy shortages and environmental problems. As a medium temperature (400-800 K) thermoelectric material, SnTe has attracted extensive attention as a promising substitute for PbTe due to its non-toxic characteristics. In this paper, the research status of SnTe thermoelectric materials is reviewed, and the strategies to improve its performance are summarized and discussed in terms of electrical and thermal transport properties. This comprehensive discussion will provides guidance and inspiration for the research on SnTe.     

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.     

Theoretical study of the lattice thermal conductivity in Ge framework semiconductors

The lattice thermal conductivity of Ge clathrates is investigated by evaluating the linear response theory heat current correlation functions using molecular dynamics. Clathrate crystals with and without guest atoms in their fullerane cages are studied. In comparison with that of diamond-phase Ge, the clathrate conductivity is reduced by approximately 1 order of magnitude due to the open framework itself. The addition of an encapsulated (rattling) Sr guest atom produces a further order of magnitude reduction in the conductivity, making it comparable to that of amorphous Ge. Our results are consistent with experiments, and have impact on the search for improved thermoelectric materials.     

Strategies for optimizing the thermoelectricity of PbTe alloys

The thermoelectric materials have been considered as a potential candidate for the new power generation technology based on their reversible heat and electricity conversion.Lead telluride(Pb Te) is regarded as an excellent mid-temperature thermoelectric material due to its suitable intrinsic thermoelectric properties.So tremendous efforts have been done to improve the thermoelectric performance of Pb Te,and figures of merit,z_T 2.0,have been reported.Main strategies for optimizing the thermoelectric performance have been focused as the main line of this review.The band engineering and phonon scattering engineering as two main effective strategies are systemically summarized here.The band engineering,like band convergence,resonant levels,and band flatting have been addressed in improving the power factor.Additionally,phonon scattering engineerings,such as atomic-scale,nano-scale,meso-scale,and multi-scale phonon scatterings have been applied to reduce the thermal conductivity.Besides,some successful synergistic effects based on band engineerings and phonon scatterings are illustrated as a simultaneous way to optimize both the power factor and thermal conductivity.Summarizing the above three main parts,we point out that the synergistic effects should be effectively exploited,and these may further boost the thermoelectric performance of Pb Te alloys and can be extended to other thermoelectric materials.     

Structural principles and amorphouslike thermal conductivity of Na-doped Si clathrates

The postulated low thermal conductivity and the possibility of altering the electronic conductivity of metal-doped clathrates with semiconducting host elements have stimulated great interest in exploring these compounds as promising thermoelectric materials. The electronic and thermal properties of the prototypical Na xSi (46) system are studied in detail here. It is shown that, despite the fact that the Na/Si clathrate is metallic, its thermal conductivity resembles that of an amorphous solid. A theoretical model is developed to rationalize the structural stability of the peculiar structural topology, and a general scheme for rational design of high efficiency thermoelectric materials is presented.     

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.     

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.     

Nonlinear thermoelectric response due to energy-dependent transport properties of a quantum dot

Quantum dots are useful model systems for studying quantum thermoelectric behavior because of their highly energy-dependent electron transport properties, which are tunable by electrostatic gating. As a result of this strong energy dependence, the thermoelectric response of quantum dots is expected to be nonlinear with respect to an applied thermal bias. However, until now this effect has been challenging to observe because, first, it is experimentally difficult to apply a sufficiently large thermal bias at the nanoscale and, second, it is difficult to distinguish thermal bias effects from purely temperature-dependent effects due to overall heating of a device. Here we take advantage of a novel thermal biasing technique and demonstrate a nonlinear thermoelectric response in a quantum dot which is defined in a heterostructured semiconductor nanowire. We also show that a theoretical model based on the Master equations fully explains the observed nonlinear thermoelectric response given the energy-dependent transport properties of the quantum dot.     

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.