Li/Ag/Cu doping and Zn vacancies have been theoretically and experimentally shown to induce ZnO to have room-temperature ferromagnetism. However, the source and mechanism of magnetic properties of such doped systems remain unclear. Previous researchers believe that all oxygen ions are negative divalent ions, as the basic assumption of the double-exchange interaction model, but no reasonable theoretical explanation has been put forward. Experimental control of Zn vacancies in ZnO is also challenging, but first principles can solve such problems. In this work, based on the generalized gradient approximation plane wave ultrasoft pseudopotential + U method under the framework of spin density functional theory, we used first principles to study the effect of the magnetic source and mechanism of Li/Ag/Cu doping and Zn vacancy on ZnO. We found that in addition to O^2– ions, some O^1– ions also existed in all doping systems. These ions had the dual-nature universality of itinerant electrons (donors) and local electrons (acceptors). The itinerant electrons in the Zn₁₄LiO₁₆, Zn₁₄AgO₁₆, and Zn₁₄CuO₁₆ systems further possessed the same spin. Compared with Zn₁₄LiO₁₆, Zn₁₄AgO₁₆, and Zn₁₄CuO₁₆ systems under the same doping amount, our results showed that the magnetic properties of Zn₂₈Li₂O₃₂, Zn₂₈Ag₂O₃₂, and Zn₂₈Cu₂O₃₂ systems all increased. The Zn₂₈Li₂O₃₂ system was found to be highly advantageous as a ferromagnetic functional material, which can guide the study of the magnetic source and mechanism of ZnO and similar oxide semiconductors through itinerant electrons.

从理论上和实验上已经证明Li / Ag / Cu掺杂和Zn空位会诱导ZnO具有室温铁磁性。但是，这种掺杂系统的磁性能的来源和机理仍不清楚。以前的研究人员认为，所有氧离子都是负二价离子，是双交换相互作用模型的基本假设，但没有提出合理的理论解释。ZnO中锌空位的实验控制也具有挑战性，但首要原理可以解决此类问题。在这项工作中，基于自旋密度泛函理论框架下的广义梯度近似平面波超软伪势+ U方法，我们使用第一原理研究了磁源的影响以及Li / Ag / Cu掺杂和Zn空位的机理在ZnO上。在所有的掺杂系统中都存在^2-离子，一些O ^1-离子。这些离子具有流动电子（施主）和局部电子（受主）的双重性质。Zn ₁₄ LiO ₁₆，Zn ₁₄ AgO ₁₆和Zn ₁₄ CuO ₁₆体系中的巡回电子进一步具有相同的自旋。在相同的掺杂量下，与Zn ₁₄ LiO ₁₆，Zn ₁₄ AgO ₁₆和Zn ₁₄ CuO ₁₆体系相比，我们的结果表明Zn ₂₈ Li ₂ O ₃₂的磁性，Zn ₂₈ Ag ₂ O ₃₂和Zn ₂₈ Cu ₂ O ₃₂体系均增加。锌₂₈ Li ₂ O ₃₂体系作为铁磁功能材料具有很高的优势，可以通过流动电子引导对ZnO和类似氧化物半导体的磁源和机理的研究。