Thermal and thermoelectric properties of metal-doped zinc oxide ceramics

Aliaksei V. Pashkevich, A. Fedotov, Eugen N. Poddenezhny, L. Bliznyuk, V. Khovaylo, V. Fedotova, A. A. Kharchenko
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Abstract

The thermal, electrical and thermoelectric properties of ZnO–MexOy ceramics with 1 ≤ x, y ≤ 3, where Me = Al, Co, Fe, Ni, Ti, have been studied. The specimens have been synthesized using the ceramic sintering technology from two or more oxides in an open atmosphere with annealing temperature and time variation. The structural and phase data on the ceramics have shown that post-synthesis addition of MexOy doping powders to wurtzite-structured ZnO powder causes Znx (Mе)yO4 spinel-like second phase precipitation and a 4-fold growth of ceramics porosity. Room temperature heat conductivity studies have testified to predominant lattice contribution. A decrease in the heat conductivity upon doping proves to be caused by phonon scattering intensification due to the following factors: size factor upon zinc ion substitution in the ZnO lattice (wurtzite) by MexOy doping oxide metal ions; defect formation, i.e., point defects, grain boundaries (microstructure refinement); porosity growth (density decline); secondary phase particle nucleation (Znx (Mе)yO4 spinel-like ones). The above listed factors entailed by zinc ion substitution for metal ions (Co, Al, Ti, Ni, Fe) increase the figure-of-merit ZT by four orders of magnitude (due to a decrease in the electrical resistivity and heat conductivity coupled with a moderate thermo-emf decline). The decrease in the electrical resistivity originates from a more homogeneous distribution of doping metal ions in the wurtzite lattice upon longer annealing which increases the number of donor centers.
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金属掺杂氧化锌陶瓷的热电性能
研究了1≤x, y≤3 (Me = Al, Co, Fe, Ni, Ti) ZnO-MexOy陶瓷的热学、电学和热电性能。采用两种或多种氧化物在开放气氛中随退火温度和时间变化的陶瓷烧结技术合成了样品。陶瓷的结构和物相数据表明,合成后在纤锌矿结构的ZnO粉末中加入MexOy掺杂粉末,导致Znx (m -)yO4尖晶石样第二相析出,陶瓷孔隙率增加4倍。室温热传导性研究证实了晶格的主要贡献。掺杂后导热系数的降低被证明是由以下因素引起的声子散射增强引起的:锌离子在ZnO晶格(纤锌矿)中被MexOy掺杂的氧化物金属离子取代的尺寸因素;缺陷形成,即点缺陷、晶界(微观结构细化);孔隙度增长(密度下降);二次相颗粒形核(Znx (m_)yO4尖晶石样)。上面列出的锌离子取代金属离子(Co, Al, Ti, Ni, Fe)所涉及的因素使ZT的品质系数增加了四个数量级(由于电阻率和导热率的降低以及适度的热电动势下降)。电阻率的降低是由于经过长时间退火后,掺杂金属离子在纤锌矿晶格中的分布更加均匀,从而增加了供体中心的数量。
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