Intrinsic point defect structure plays a crucial role in functional ceramics with a grain-grain boundary microstructure. In the present study, a novel method of reversely manipulating intrinsic point defects (oxygen vacancy, V_o and zinc interstitial, Zn_i) in ZnO-based varistor ceramics is proposed, which makes use of Zr-stabilized high ionic conducting β_III-Bi₂O₃ intergranular phase. It is found that Zr-doping not only modifies the grain growth by the formation of secondary Zr-rich phase, but also influences the intrinsic point defect structure via the stabilized β_III-Bi₂O₃ phase, resulting in reduced V_o density but increased Zn_i density. The reverse manipulation is unambiguously demonstrated by broadband dielectric spectroscopy and further confirmed by the accelerated ageing experiment. The proposed intrinsic point defect dynamics unveil an important but usually neglected function of the dopant that has little solid solubility in ZnO grains, which opens up a promising way to tailor the material property.

本征点缺陷结构在具有晶界微结构的功能陶瓷中起着至关重要的作用。在本研究中，反向操纵本征点缺陷的新方法（氧空位，V _ö和锌间质性，锌_我）中的基于ZnO非线性电阻陶瓷，提出了一种利用Zr的稳定化的高离子导电的β _III -Bi ₂ O ₃晶间相。据发现，Zr的掺杂不仅修改由二次富Zr的相的形成的晶粒生长，而且还经由所述稳定化影响的本征点缺陷结构β _III -Bi ₂ ö ₃相，从而降低V_o密度，但Zn _i密度增加。宽带介电谱清楚地证明了这种反向操作，并通过加速老化实验得到了进一步证实。拟议的本征点缺陷动力学揭示了一种重要但通常被忽略的掺杂剂功能，它在ZnO晶粒中几乎没有固溶性，这为定制材料性能开辟了一种有前途的方式。