热压工艺参数对n型和p型Bi2Te3基赝三元热电材料电学性能的影响

通过熔炼/研磨/热压方法制备了n型和p型赝三元Bi₂Te₃基的热压合 金样品，测量了由不同工艺参数(热压温度、热压压力)制备的样品Seebeck系数和电导率.分析了热压参数对热电性能产生的影响.特别是发现了增加热压压力和热压温度会使n型和p型热压样品的Seebeck系数和电导率都有所提高，这与单晶和取向晶体材料的Seebeck系数和电导率变化趋势相反的规律显然不同，其结果对热压样品的电学性能提高有积极的影响. 关键词： 热电材料 热压 Seebeck系数 工艺参数     

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.     

改善Te基热电材料与复合电极界面性能

Te基热电材料以其优异的热电性能得到科研工作者的广泛关注,但该领域关于器件制备和连接界面方面的研究尚属空白.本研究基于成分梯度、载流子浓度梯度构成的多元梯度势场对界面粒子传输过程的协同调控机制,在热电材料Te和电极Fe之间引入b(FeTe)作为阻隔层,设计制备了Te/b(FeTe)/Fe梯度连接结构,并对界面新相、接触电阻和机械性能进行了研究.研究结果表明,中间合金层b(FeTe)与热电材料和电极材料的界面组织结构致密,有效阻隔了界面元素间严重的交互扩散.该b(FeTe)-Te间形成了约40μm的反应层, b(FeTe)与Fe和Te间的接触电阻分别为4.1和7.54μW·cm2,剪切强度分别为16.11和15.63 MPa.时效温度对梯度连接结构的服役寿命和性能影响显著, Te/b(FeTe)/Fe的界面组织在553 K温度下时效15 d,界面性能保持稳定;当时效温度升至573 K时,由于高温下材料的不稳定性,导致性能随着退火时间的延长急剧下降,并在10 d之后完全破坏,这表明其最佳工作温度不得高于553 K.该梯度连接结构成功实现了抑制界面元素过度扩散、降低界面残余应力以及提升界面工...     

Bi2Te3 基花状纳米片粉体的制备及热电性能研究

本文通过选用不同乙二胺四乙酸(EDTA) 的用量采用水热法制备出了具有花状纳米片形貌的碲化铋(Bi2Te3 ) 纳米粉体, 研究了不同 EDTA 的用量对 Bi2Te3 纳米粉体花状纳米片形貌的影响, 结果表明 EDTA 的用量对粉体的成相和形貌有很大的影响. EDTA 用量为0.2 g 是最佳值, 有助于形成纯相的 Bi2Te3 花状纳米片. 并以 Y元素掺杂为例, 研究了 EDTA 用量对元素掺杂 Bi2Te3 纳米粉体花状形貌的影响, 研究发现元素掺杂后对 Bi2Te3粉体的微观形貌有一定的影响. 为了保持元素掺杂 Bi2Te3 纳米粉体的花状形貌,EDTA 合适的用量至关重要. 以Y0 .2Bi1 .8Te3 为例, 研究了 EDTA 用量对样品的热电性能的影响. 结果表明, 花状纳米片形貌有利于在降低样品电阻率的同时有效降低样品的热导率, 从而大大增加了样品的ZT 值.     

双掺杂锰酸钙基热电陶瓷的制备及电学性能研究

利用传统固相反应法成功制备出Nb掺杂量x不同的Ca_0.9Yb_0.1Mn_1-xNb_xO₃热电陶瓷. X射线衍射分析和扫描电子显微镜分析表明: 样品均形成了单一的钙钛矿正交结构,空间群为Pnma. 晶格常数a和晶胞体积随着Nb掺杂量x的增加而增大,陶瓷样品具有很好的结晶度和很高的致密性, 相对密度达到97%左右. 在3 关键词： 3陶瓷')" href="#">CaMnO₃陶瓷 电阻率 Seebeck系数     

一种测量热电材料塞贝克系数的新方法

本文提出了一种新颖、可靠的测量微纳米尺度热电转换材料塞贝克系数的2ω自加热法.给被测样品通一频率为ω的交变电流,焦耳效应会在样品上产生一个频率为2ω的温度振荡.对于热电材料,由于塞贝克效应,将会产生频率为2ω的塞贝克电压.获取2ω电压信号,同时理论求解得到2ω的温度振荡量,将可得到被测热电材料的塞贝克系数.通过直径为2...     

高压烧结对n型PbTe基材料热电性能的影响

 采用高压烧结技术制备了按偏离化学计量比配制的PbTe基热电材料（Pb_0.55Te_0.45），重点研究了烧结压力对材料热电性能的影响。研究结果表明：高压烧结过程能有效降低材料中的晶格缺陷，从而显著改变样品中的载流子浓度及其迁移率。与未经烧结的常压熔融样品相比，高压烧结样品的Seebeck系数得到大幅提高，电导率略有降低，室温热导率降低了50%，所以高压烧结样品的品质因子得到较大提高。当烧结压力为2 GPa时，所得样品在700 K时其品质因子达到0.59，相比未经烧结的常压熔融样品提高了150%。     

粗糙界面对Bi2Te3/PbTe超晶格热电优值影响的理论分析

以Bi2Te3/PbTe超晶格薄膜为例,分析电子在Bi2Te3量子阱中的输运过程,综合了薄膜的经典散射效应和理想量子效应,并以此混合效应为基础,在PbTe障碍层厚度一定时,模拟计算了两种混合效应中量子效应占不同比例时,Bi2Te3/PbTe超晶格热电优值的变化.在镜面反射占混合效应的0 3时,得到的热电优值与当前报道的量子阱超晶格的实验值接近.     

过量Zn对β-Zn4Sb3热电性能影响的研究

采用真空熔融缓冷方法制备了单相β-Zn4Sb3以及含有过量Zn的β-Zn4Sb3块体热电材料.在300—700K的温度范围内测试了材料的电导率、Seebeck系数和热导率,研究了β-Zn4Sb3化合物中过量Zn的分布状态及其对材料热电性能的影响规律.结果表明：过量的Zn作为第二相较均匀的分布在β-Zn4Sb3的晶界上,随着Zn含量增加,材料电导率和热导率上升,Seebeck系数下降,Zn第二相的引入能有效提高材料的功率因子,Zn过量2at%的材料在700K时其ZT值达到1.10.     

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.     

Probing the thermoelectric transport properties of n-type Bi2Te3 close to the limit of constitutional undercooling

Bulk n-type Bi2Te3 single crystals with optimized chemical composition were successfully prepared by a high temperature-gradient directional solidification method. We investigate the influence of alloy microstructure, chemical composition, and growth orientation on the thermoelectric transport properties. The results show that the composition of single-crystal Bi2Te3 alloy, along the c axis direction, could be slightly tuned by changing the growth rate of the crystal. At a rate of 18 mm/h, the formed Bi2Te3 crystal exhibits good thermoelectric properties. At 300 K, a maximum Seebeck coefficient of -245 μV/K and an electrical conductivity of 5.6 × 10 4 S/m are acquired. The optimal power factor is ob- tained as 3.3 × 10 -3 W/K2m, with a figure of merit of 0.74. It can be attributed to the increased tellurium allocation in the Bi2Te3 alloys, as verified well by the density functional theory caLculations.     

Influence of grain size distribution on the lattice thermal conductivity of Bi2Te3-Sb2Te3-based nanostructured materials

The change of the lattice thermal conductivity of bulk nanostructured materials based on Bi₂Te₃-Sb₂Te₃ solid solutions with grain size distribution has been studied. These materials have a polycrystalline structure with grain sizes ranging from a few tens of a nanometer to a few micrometers. Large grains may contain inclusions or consist of several smaller parts which can be identified with coherent scattering regions seen in X-ray diffraction. The change of the lattice thermal conductivity mediated by additional scattering by inclusions and grain boundaries has been calculated. This calculation allows for the effect of nanoparticle size distribution. The calculated estimates are compared with the available experimental data.     

熔体旋甩法合成n型(Bi_(0.85)Sb_(0.15))_2(Te_(1-x)Se_x)_3化合物的微结构及热电性能

采用熔体旋甩结合放电等离子烧结(MS-SPS)技术制备了单相n型四元(Bi0.85Sb0.15)2(Te1-xSex)3(x=0.15,0.17,0.19,0.21)化合物,并对所得样品的微结构和热电传输性能进行了系统研究.样品自由断裂面的场发射扫描电子显微镜及抛光面的背散射电子成分分析表明:块体材料晶粒细小,晶粒排列紧密,成分分布均匀且相结构单一,样品中存在大量10—100nm的层状结构.随着Se含量x的增加,样品的电导率和热导率逐渐增加,而Seebeck系数逐渐降低.相比商业应用的区熔材料,MS-SPS方法合成的高Se组成的样品均在425K后表现出更高的ZT值,其中(Bi0.85Sb0.15)2(Te0.83Se0.17)3样品具有最高的ZT值,在360K可达到0.96,并在320—500K均保持较高的ZT值,500K时其ZT值相比区熔材料提高了48%.此外,通过调节Se的含量,可以有效地调控材料的ZT峰值出现的温度段,这对多级或梯度热电器件的制备具有重要意义.     

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)     

Investigation of the possibilities for increasing the thermoelectric figure of merit of nanostructured materials based on Bi2Te3-Sb2Te3 solid solutions

The transport coefficients and thermoelectric figure of merit ZT for bulk nanostructured materials based on Bi₂Te₃-Sb₂Te₃ solid solutions have been investigated theoretically. Similar materials prepared by rapid quenching of the melt with the subsequent grinding and sintering contain amorphous and nanocrystalline regions with different sizes of particles. According to the performed estimations, the thermoelectric figure of merit of the amorphous phase can exceed the value of ZT for the initial solid solution by a factor of 2?C3 primarily due to the significant decrease in the thermal conductivity. The effective transport coefficients of the medium as a whole have also been investigated as a function of the parameters of each phase, and the concentration range of the amorphous phase, which corresponds to the effective values ZT > 1, has been determined.     

Thermoelectric properties of Bi2Se3/Bi2Te3/Bi2Se3 and Sb2Te3/Bi2Te3/Sb2Te3 quantum well systems

In this work, we develop a theory of thermoelectric transport properties in two-dimensional semiconducting quantum well structures. Calculations are performed for n-type 0.1 wt.% CuBr-doped Bi₂Se₃/Bi₂Te₃/Bi₂Se₃ and p-type 3 wt.% Te-doped Sb₂Te₃/Bi₂Te₃/Sb₂Te₃ quantum well systems in the temperature range 50–600 K. It is found that reducing the well thickness has a pronounced effect on enhancing the thermoelectric figure of merit (ZT). For the n-type Bi₂Se₃/Bi₂Te₃/Bi₂Se₃ with 7 nm well width, the maximum value of ZT is estimated to be 0.97 at 350 K and for the p-type Sb₂Te₃/Bi₂Te₃/Sb₂Te₃ with well width 10 nm the highest value of the ZT is found to be 1.945 at 440 K. An explanation is provided for the resulting higher ZT value of the p-type system compared to the n-type system.     

Doping effects on the thermoelectric properties of Cu-intercalated Bi2Te2.7Se0.3

We herein report an enhancement of the thermoelectric performance of spark plasma sintered polycrystalline n-type Bi₂Te_2.7Se_0.3 by the intercalation of Cu and the doping of Al on Bi-sites. Through the intercalation of a small amount of Cu (0.008), the reproducibility could be significantly improved, with ZT was enhanced from 0.64 to 0.73 at 300 K due to the reduced lattice thermal conductivity benefiting from intensified point-defect phonon scattering. We also found that Al is an effective doping element for power factor enhancement and for reducing the lattice thermal conductivity of Cu-intercalated Bi₂Te_2.7Se_0.3. With these synergetic effects, an enhanced ZT values of 0.78 at 300 K and 0.81 at 360 K were obtained in 1 at% Al-doped Cu_0.008Bi₂Te_2.7Se_0.3 (Cu_0.008Bi_1.98Al_0.02Te_2.7Se_0.3).