Ga填充n型方钴矿化合物的结构及热电性能

用熔融退火结合放电等离子烧结(SPS)技术制备了具有不同Ga填充含量的Ga_xCo₄Sb₁₂方钴矿化合物,研究了不同Ga含量对其热电传输特性的影响规律. Rietveld结构解析表明,Ga占据晶体学2a空洞位置,Ga填充上限约为0.22,当Ga的名义组成x≤0.25时,样品的电导率、室温载流子浓度N_p随Ga含量的增加而增加,Seebeck系数随Ga含量的增加而减小. 室温下霍尔测试表明,每一个Ga授予框架0.9个电子,比Ga的氧化价态Ga³⁺小得多. 由于Ga离子半径相对较小,致使Ga填充方钴矿化合物的热导率κ及晶格热导率κ_L较其他元素填充的方钴矿化合物低. 当x＝0.22时对应的样品在300K时的热导率和晶格热导率分别为3.05Wm^-1·K^-1和 2.86Wm^-1·K^-1.在600K下Ga_0.22Co_4.0Sb_12.0样品晶格热导率达到最小,为1.83Wm^-1·K^-1,最大热电优值Z,在560K处达1.31×10^-3K^-1. 关键词： skutterudite化合物 Ga原子填充 结构 热电性能     

致密度对填充skutterudite化合物La0.75Fe3CoSb12热电性能的影响

研究了致密度对填充skutterudite化合物La_0.75Fe₃CoSb₁₂热电性能的影响.La_0.75Fe₃CoSb₁₂表现为p型传导，载流子迁移率随着致密度的增加而升高.由于样品中空洞的散射作用，致使电阻率ρ随着致密度的降低而升高，同时造成热导率κ的下降，但塞贝克系数α与致密度关系不大，致密度造成电阻率ρ升高的比率与热导率κ下降的比率相当，致密度不同的样品具有相当的ZT 关键词： 致密度 填充式skutterudite化合物 热电性能     

热电材料与发电器件的进展和挑战

热电/温差电效应是一种能够实现热能和电能直接相互转换的环境友好型能源技术,基于该技术的热电发电器件的应用,有望成为缓解能源问题的可行方案。文章主要介绍了中高温区p型和n型热电材料的最新研究进展,重点论述了可能应用于热电发电器件的几种典型热电材料体系的相关优缺点。此外,还回顾了目前中高温区热电发电器件的研究现状,尝试给出了目前亟待突破的壁垒,最后讨论并展望了热电发电器件的发展前景与未来研究方向。     

热电材料的热输运调控及其在微型器件中的应用

热电能量转换技术是一种利用材料实现热能和电能直接相互转换的清洁能源技术。热电材料的性能是决定热电转换效率的关键因素,而热电材料的性能优化涉及电输运和热输运性能的协同优化。文章介绍了近期热电材料中热输运的调控机制和方法,其中重点论述了基于原子分子层次调控热传导的宽频声子散射效应和横波阻尼效应,以及低维结构和复合材料中的基于纳米微米尺度的微结构调控。最后介绍了室温附近热传导的调控机制及其在高效微型热电器件研发中的应用和进展。     

Sm和Ce复合掺杂Skutterudite化合物的制备及热电性能

用熔融法结合放电等离子快速烧结(SPS)制备出了单相的Sm和Ce复合掺杂的Skutterudite化合物Sm_mCe_nFe_1.5Co_2.5Sb₁₂，研究了Sm和Ce复合掺杂总量对其热电性能的影响规律.结果表明：随着Sm和Ce复合掺杂总量的增加，p型Sm_mCe_nFe_1.5Co_2.5Sb₁₂化合物的Seebeck系数增加、电导率和热导率降低.当掺杂总量相近时，和Sm、Ce单原子掺杂相比，Sm和Ce复合掺杂使Skutterudite化合物的热导率低10%—40%.Sm_0.22Ce_0.20Fe_1.54Co_2.46Sb_11.89化合物的最大热电性能指数ZT_max值在775K时为0.84. 关键词： 复合掺杂 方钴矿 热电性能     

The temperature dependence of thermal expansion for p-type Ce0.9Fe3.5Co0.5Sb12 and n-type Co0.95Pd0.05Te0.05Sb3 skutterudite thermoelectric materials

During waste heat recovery applications, thermoelectric (TE) materials experience thermal gradients and thermal transients, which produce stresses that scale with the TE material's coefficient of thermal expansion (CTE). Thus, the temperature-dependent CTE is an important parameter for the design of mechanically robust TE generators. For three skutterudite thermoelectric compositions, n-type Co_0.95Pd_0.05Te_0.05Sb₃ (with and without 0.1 at. % cerium doping) and p-type Ce_0.9Fe_3.5Co_0.5Sb₁₂, the CTE was measured using two methods, i.e. X-ray diffraction on powder and bulk specimens and dilatometry on bulk specimens. Each bulk specimen was hot pressed using powders milled from cast ingots. Between 300?K and 600?K, the mean CTE values were 9.8–10.3?×?10^?6 K^?1 for the non-cerium-doped n-type, 11.6?×?10^?6 K^?1 for the 0.1 at. % cerium-doped n-type and from 12.7 to 13.3?×?10^?6 K^?1 for the p-type. In the literature, similar CTE values are reported for other Sb-based skutterudites. For temperatures >600?K, an unrecovered dilatational strain (perhaps due to bloating) was observed, which may impact applications. Also, the submicron particle sizes generated by wet milling were pyrophoric; thus, during both processing and characterization, exposure of the powders to oxygen should be limited.     

二维材料的新奇物理及异质结的能带调控

以石墨烯为代表的层状材料具备显著区别于三维材料的新奇物理特性。更为重要的是,原子级平整的二维材料使得科学家们可以将不同的二维材料通过堆垛或者把相同的二维材料通过堆垛加扭转构成范德瓦耳斯异质结。通过层间耦合作用,可对异质结的能带结构和物理性质进行有效调控,从而衍生出单个二维材料所不具备的新奇物性。范德瓦耳斯异质结的能带调控极大地拓宽了二维材料的科学研究和应用前景。     

Ca和Ce双原子复合填充p型CamCenFexCo4－xSb12化合物的合成及热电性能

用高温熔融法合成了Ca和Ce复合填充的单相p型Ca_mCe_nFe_{xCo4-xSb12化合物，探索了两种原子复合填充对其热电性能的影 响规律.研究结果表明，填充分数相同时，Ca和Ce两种原子复合填充的p型CamCe nFexCo4-xSb12化合物的载流子浓度和电 导率介于Ca或Ce一种原子单独填充的化合物之间，且随两种原子填充分数m+n的增加而降低 ；赛贝克系数随两种原子填充总量，尤其是Ce填充分数m的增加以及温度的上升而增加；在 相同填充分数时，两种原子复合填充的p型CamCenFexC o4-xSb12化合物的晶格热导率较Ca或Ce一种原子单独填充的化合物 的晶格热导率低，当总填充分数m+n为0.3左右，且Ca和Ce的填充量大致相等时，化合物的晶 格热导率最低.p型Ca0.18Ce0.12Fe1.45Co2.55Sb12.21化合物的最大热电性能指数ZT值在750K时达到1.17. 关键词： skutterudite化合物 双原子复合填充 合成 热电性能}     

利用晶体结构工程提升GeSe化合物热电性能的研究

在热电研究领域, Ge Se是一种二维层状结构具有较大带隙的半导体,本征载流子浓度低,热电性能差.在本工作中,采用熔融淬火结合放电等离子活化烧结工艺制备了一系列的Ge Se_1–x Te_x (x=0, 0.05, 0.15, 0.25,0.35, 0.45)多晶样品,研究了Te含量对Ge Se化合物物相结构和热电输运性能的影响规律.结果表明:随着Te含量的增加, Ge Se的晶体结构逐渐由正交相向菱方相转变,使得材料的带隙降低,载流子浓度和迁移率同步增加;同时,晶体对称性的提高增加了化合物的能带简并度,有效提高了载流子有效质量.在这些因素的共同作用下,菱方相Ge Se的功率因子比正交相Ge Se提高约2—3个数量级.此外,菱方相Ge Se具有丰富的阳离子空位缺陷以及铁电特性所导致的声子软化现象,这导致其晶格热导率比正交相Ge Se降低近60%.当Te含量为0.45时,样品在573 K取得最大热电优值ZT为0.75,是本征Ge Se样品的19倍.晶体结构工程是提升Ge Se化合物热电性能的有效途径.     

Recent advances on thermoelectric materials

By converting waste heat into electricity through the thermoelectric power of solids without producing greenhouse gas emissions, thermoelectric generators could be an important part of the solution to today’s energy challenge. There has been a resurgence in the search for new materials for advanced thermoelectric energy conversion applications. In this paper, we will review recent efforts on improving thermoelectric efficiency. Particularly, several novel proof-of-principle approaches such as phonon disorder in phonon-glass-electron crystals, low dimensionality in nanostructured materials and charge-spin-orbital degeneracy in strongly correlated systems on thermoelectric performance will be discussed.      

Energy band engineering of flexible gallium arsenide through substrate cracking with pre‐tensioned films

Flexible electronics based on the otherwise rigid conventional crystalline semiconductors is emerging as a new class of technology. However, the existing layer‐transfer approaches for implementing such technologies is mostly focused on maintaining the performance of the original device. Here we show that layer transfer through substrate cracking with a pre‐tensioned nickel film readily enables the manipulation of the electronic band structure in flexible gallium arsenide (GaAs) devices. We empirically and theoretically quantify the effect of ‘engineered' residual strain on the electronic band structure in these flexible GaAs devices. Photoluminescence and quantum efficiency measurements indicate the widening of the GaAs energy bandgap due to the residual compressive strain. The experimental results are in good agreement with our theoretical calculations. This study introduces a new way for strain engineering in flexible compound semiconductors with important implications for electronic and optoelectronic applications. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

In0.3Co4Sb12-xSex 方钴矿热电材料的制备和热电性能

用熔融退火结合放电等离子烧结法制备了In_0.3Co₄Sb_12-xSe_x(x=0—0.3)方钴矿热电材料,探讨了In的存在形式,系统研究了Se掺杂量对结构和热电性能的影响.结果表明:In可以填充到方钴矿二十面体空洞处,过量In在晶界处形成InSb第二相,Se对Sb的置换使晶格常数减小,In填充上限降低;In_0.3Co₄Sb_12-xSe_x样品呈n型传导,随着Se掺杂量的增大,载流子浓度降低,电导率下降,Seebeck系数增大,功率因子有所降低;由于在结构中引入了质量波动及晶格畸变,适量的Se掺杂可以大幅降低材料晶格热导率;样品In_0.3Co₄Sb₁₂和In_0.3Co₄Sb_11.95Se_0.05的最大ZT值均达到1.0以上. 关键词： 掺杂 填充式方钴矿 热电性能     

能源效率、热电效应和纳米技术

文章介绍了能源效率、热电效应以及纳米技术这三者之间的关系。文章首先讨论了能源效率的重要性以及余热浪费对能源效率的影响,然后介绍了材料的热电效应以及利用热电效应使余热发电的可能性和实际应用中的主要障碍。最后阐明了近年来纳米技术的发展使得这一技术有可能取得突破性进展的主要原因。     

能源效率、热电效应和纳米技术

文章介绍了能源效率、热电效应以及纳米技术这三者之间的关系。文章首先讨论了能源效率的重要性以及余热浪费对能源效率的影响,然后介绍了材料的热电效应以及利用热电效应使余热发电的可能性和实际应用中的主要障碍。最后阐明了近年来纳米技术的发展使得这一技术有可能取得突破性进展的主要原因。     

PbSe-MnSe纳米复合热电材料的微结构和电热输运性能

相比于常见的热电材料PbTe, 另一种硫族铅化合物PbSe具有熔点高、Se储量更丰富等优势, 从而越来越受到科学界的关注. 本文采用熔融淬火结合快速热压烧结工艺制备了Pb_0.98-xMn_xNa_0.02Se(0 ≤x ≤ 0.12)纳米复合热电材料, 系统地研究了不同Mn含量对材料微纳结构、机械性能和热电性能的影响规律. 发现纳米复合样品中有面心立方结构的MnSe球状和薄层状析出物, 显微硬度得到显著增强. 少量固溶的Mn增加了能带简并度, 使功率因子提高, 球状析出物使声子散射增强、热导率降低, 体系的热电优值ZT得到优化; 但是当Mn含量更高时, 赛贝克系数趋于饱和, 连续析出物使晶格热导率反常增大, ZT 没有得到进一步改善. 通过进一步调节Na含量优化了载流子浓度, 获得了ZT=0.65的PbSe-MnSe纳米复合热电材料.     

Recent advances in organic,inorganic, and hybrid thermoelectric aerogels

The thermoelectric(TE)materials and corresponding TE devices can achieve direct heat-to-electricity conversion,thus have wide applications in heat energy harvesting(power generator),wearable electronics and local cooling.In recent years,aerogel-based TE materials have received considerable attention and have made remarkable progress because of their unique structural,electrical and thermal properties.In this review,the recent progress in both organic,inorganic,and composite/hybrid TE aerogels is systematically summarized,including the main constituents,preparation method,TE performance,as well as factors affecting the TE performance and the corresponding mechanism.Moreover,two typical aerogel-based TE devices/generators are compared and analyzed in terms of assembly modes and output performance.Finally,the present challenges and some tentative suggestions for future research prospects are provided in conclusion.     

Be1-xMgxO合金的能带特性与相结构稳定性研究

采用基于密度泛函理论的平面波赝势方法,对纤锌矿和岩盐矿结构Be_1-xMg_xO合金的晶格常数、能带特性和形成能进行计算,分析了不同Mg组分下不同结构的Be_1-xMg_xO合金晶格常数和能带差异.结果表明:随着Mg组分的增大,纤锌矿和岩盐矿Be_1-xMg_xO合金的晶格常数都线性增加,但它们的能隙都逐渐减小.对于相同Mg组分的Be_1-xMg_xO合金,岩盐矿结构的能隙要大于纤锌矿结构.当Mg组分为0.89时,Be_1-xMg_xO合金由纤锌矿相转变为岩盐矿相.为了使理论值与实验值相一致,对Be_1-xMg_xO合金的能隙计算值进行修正,得到纤锌矿和岩盐矿Be_1-xMg_xO合金的能隙弯曲系数b值分别为3.451 eV和4.96 eV.对纤锌矿BeO-MgO-ZnO三元合金的能隙和弯曲系数与晶格常数关系做了分析.     

Strategies for discovery and optimization of thermoelectric materials: Role of real objects and local fields

Thermoelectric materials provide a renewable and eco-friendly solution to mitigate energy shortages and to reduce environmental pollution via direct heat-to-electricity conversion. Discovery of the novel thermoelectric materials and optimization of the state-of-the-art material systems lie at the core of the thermoelectric society, the basic concept behind these being comprehension and manipulation of the physical principles and transport properties regarding thermoelectric materials. In this mini-review, certain examples for designing high-performance bulk thermoelectric materials are presented from the perspectives of both real objects and local fields. The highlights of this topic involve the Rashba effect, Peierls distortion, local magnetic field, and local stress field, which cover several aspects in the field of thermoelectric research. We conclude with an overview of future developments in thermoelectricity.     

Superluminal propagation in plasma photonic band gap materials

Electromagnetic wave propagation in one-dimensional plasma photonic crystal (PPC) made of alternate thin layers of two materials namely plasma and dielectric materials is theoretically studied. Dispersion relation is obtained. Group velocity, effective group index, reflectivity and superluminal behavior have been studied. The study of the reflectivity plot shows that the designed structure works as a perfect reflector/mirror in a certain range of frequency. Left-right and up-down symmetries (and flip-flop) are observed when we study the variation of group velocity with frequency. Abnormal behavior of group velocity (negative) inside the PPC structure creates the superluminal propagation of electromagnetic waves. The marked existence of symmetries may be exploited for directional switching in optical circuits.     

Energy band and band-gap properties of deformed single-walled silicon nanotubes

The fantastic physical properties of single-walled silicon nanotubes (SWSiNTs) under mechanical strain make them promising materials for fabricating nanoscale electronic devices or transducers. Here we investigate the energy band and band-gap properties of the SWSiNTs calculated from the tight-binding model approximation. The results show that the band-gap properties are very sensitive to the deformation degree and the helicity of the SWSiNTs. The results can be employed to guide the design of nanoelectronic devices based on silicon nanotubes.