Liu Tao, Huang Yuxuan, Wang Shixia, Wang Yalin, Cheng Ping, Wu Jia
Department of Chemistry, University of Shanghai for Science and Technology, Shanghai, 200093, People's Republic of China.
State Key Laboratory of Petroleum Resources and Prospecting, China University of Petroleum (Beijing), Beijing, 102249, People's Republic of China.
Sci Rep. 2025 Feb 12;15(1):5227. doi: 10.1038/s41598-025-89795-3.
The structural parameters and enthalpies of pure ZnSe and different concentrations of V/Mn:ZnSe at high pressures were calculated using the first principles calculation method based on density functional theory. The lattice constants and bond lengths of all the systems decrease under pressure, and the respective phase transition pressures are obtained from the enthalpy-pressure relationship curves, which show that V/Mn elemental doping reduces the phase transition pressure of ZnSe, and the phase transition pressure further decreases with the increase of the doping concentration. The doping formation energies and the elastic constant criterion at atmospheric and high pressures confirm the structural stability of all the systems within the pressures of this study, and the pugh ratio confirms that they are all ductile structures.The results of electrical properties study show that at atmospheric pressure, all V:ZnSe systems have metallic properties, and a metal to semiconductor transition occurs at high pressure when the doping concentration is 12.5%. However, the Mn:ZnSe systems are semiconductors at both atmospheric and high pressures. Pressure significantly influences the degeneracy and position of the impurity bands: the impurity bands of V:ZnSe move toward higher energy under pressure, while the impurity bands of the Mn:ZnSe system shift toward lower energy. The element doping concentration also affects the d orbital degeneracy of V/Mn:ZnSe under atmospheric pressure, the degeneracy of V/Mn-d orbital decreases with the increase in doping concentration. Under high pressure, the degeneracy of the V/Mn-d orbital decreases further when the doping concentration is 3.13%, but the degeneracy is enhanced when the doping concentration is 6.25 and 12.5%. Doping can effectively change the phase transition pressure of ZnSe, and the pressure can effectively modulate the properties of this material.
采用基于密度泛函理论的第一性原理计算方法，计算了纯ZnSe以及不同浓度V/Mn:ZnSe在高压下的结构参数和焓。所有体系的晶格常数和键长在压力作用下均减小，并从焓-压力关系曲线获得了各自的相变压力，结果表明V/Mn元素掺杂降低了ZnSe的相变压力，且相变压力随掺杂浓度的增加而进一步降低。常压和高压下的掺杂形成能及弹性常数判据证实了本研究压力范围内所有体系的结构稳定性，且普格比证实它们均为延性结构。电学性质研究结果表明，常压下所有V:ZnSe体系均具有金属性质，当掺杂浓度为12.5%时，在高压下会发生金属-半导体转变。然而，Mn:ZnSe体系在常压和高压下均为半导体。压力显著影响杂质带的简并度和位置：V:ZnSe的杂质带在压力作用下向高能方向移动，而Mn:ZnSe体系的杂质带向低能方向移动。元素掺杂浓度也影响常压下V/Mn:ZnSe的d轨道简并度，V/Mn-d轨道的简并度随掺杂浓度的增加而降低。在高压下，当掺杂浓度为3.13%时，V/Mn-d轨道的简并度进一步降低，但当掺杂浓度为6.25%和12.5%时简并度增强。掺杂可有效改变ZnSe的相变压力，压力可有效调制该材料的性能。
