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中国物理学会期刊

    铜掺杂Cu2SnSe4的热电输运性能

    Thermoelectric properties of Cu-doped Cu2SnSe4compounds

    CSTR: 32037.14.aps.69.20200861
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    • Cu 2SnSe 4化合物具有本征的低热导率和可调控的电导率, 同时不含稀贵元素、无毒和价格低廉, 具有作为中温区热电材料的潜力. 本文通过高能球磨结合放电等离子烧结制备了Cu 2SnSe 4以及Cu掺杂的Cu 2+xSnSe 4块体材料( 0.2\leqslant x \leqslant 1 ). 研究了Cu掺杂填充Cu/Sn位置上1/4本征空位对Cu 2+xSnSe 4热电性能的影响, 发现Cu/Sn中1/4空位能够被Cu完全填满( x= 1), 且Cu掺杂能够大幅度地提升(可达两个数量级)样品的电导率, 从而显著提高了功率因子. 同时, 发现在大Cu掺杂量范围( 0.1 \leqslant x \leqslant 0.8 )内, Cu 2+xSnSe 4电导率增长与掺杂量增加呈线性关系, 且载流子迁移率随Cu掺杂量的增加而增加. 进一步的研究发现, 载流子在Cu 2+xSnSe 4中的电输运行为遵循电子-声子耦合的小极化子模型.

      Cu 2SnSe 4compound, as a non-toxic inexpensive thermoelectric material, has low thermal conductivity and adjustable conductivity, which promises to have a high-efficiency thermoelectric application in a medium-temperature range. The Cu-doped bulk samples of Cu 2+ xSnSe 4(0 ≤ x≤ 1) compounds are synthesized by a fast method, i.e. by combining high energy ball milling with spark plasma sintering. In this work, the thermoelectric properties of Cu-doped Cu 2SnSe 4compound are investigated. The experimental results reveal that the intrinsic vacancy at Cu/Sn site of Cu 2SnSe 4can be completely filled by Cu (i.e. x= 1 in Cu 2+ xSnSe 4). The crystal structures of all Cu 2+ xSnSe 4samples have the same space group F3 mas that of the undoped Cu 2SnSe 4. The electrical conductivity of Cu 2+ xSnSe 4increases rapidly with the content of Cu doped at intrinsic vacancy increasing, concretely, it increases by two orders of magnitude and reaches a maximum value at x= 0.8. The increase in electrical conductivity results in the significant improvement in power factor. The observed results display that the increase in electrical conductivity is a nonlinear relationship with Cu-doping content in a range of 0 < x< 0.1, but is linearly related to the Cu-doping content in a range of 0.1 ≤ x≤ 0.8. Meanwhile, the carrier (hole) concentration is observed to reach a maximum value at x= 0.2 and then slightly decreases at x= 0.8. The rapid increase in electrical conductivity with Cu-doping content increasing may be attributed to the intensifying of Cu-Se bond network that plays a dominant role in controlling hole transport in Cu 2SnSe 4. The carrier mobility also increases with the Cu-doping content increasing in the range of 0 ≤ x≤ 0.8, which is in contrast to the common scenarios in thermoelectric materials that the carrier mobility decreases with the increase in the carrier concentration. Furthermore, the carrier transport mechanism of Cu 2+ xSnSe 4sample is revealed to be able to be described by the small polaron hopping model, which means the strong coupling between electron and phonon. The analysis of thermal conductivities of the Cu 2+ xSnSe 4samples reveals that the relationship between the electronic thermal conductivity and the electrical conductivity cannot be described by the classical Wiedemanmn-Franz law, which may be attributed to the formation of electron-phonon coupled small polaron. Therefore, the coupling between electron and phonon inside the Cu 2+ xSnSe 4structure strongly influences the behaviors of carrier transmission and thermal conductivity.

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