AI 中文总结
该研究用密度泛函理论及mBJ+U方法，研究Mn取代Ni对Cu2NiXY4（X = Sn，Ge，Si；Y = S，Se）结构和电子性质的影响，发现其能保持四方结构并改变电子结构，带隙变窄，为光电器件应用提供策略。
AI 中文摘要
在本工作中，使用密度泛函理论（DFT）研究了用Mn部分取代Ni对类晶石体系Cu2NiXY4（X = Sn，Ge，Si；Y = S，Se）的结构和电子性质的影响。采用mBJ+U方法更准确地表征带隙。此前尚未对整个Cu2NiXY4（X = Sn，Ge，Si；Y = S，Se）族中Mn取代进行系统比较研究。由于类晶石晶胞的晶体学限制，用Mn取代单个Ni原子相当于50%。选择此构型研究Mn取代对Cu2NiXY4（X = Sn，Ge，Si；Y = S，Se）化合物结构和电子性质的影响，而低浓度研究需用超胞，是进一步研究的主题。计算结果表明，用Mn部分取代Ni保持了类晶石的四方结构并显著改变电子结构。在所研究的所有化合物中，带隙从1.028 - 3.397降至1.007 - 3.333 eV。例如，在Cu2NiSnS4体系中，带隙宽度从1.59 eV降至1.49 eV。带隙变窄是由于带边附近Mn - 3d、Cu - 3d和S/Se - p轨道的杂化，导致费米能级附近电子态重新分布。结果表明，Mn取代是控制Cu2NiXY4类晶石电子性质的有效策略，在需要可调带隙的光电器件中有很大应用前景。
英文摘要
In this work, the effect of partial substitution of Mn by Ni on the structural and electronic properties of kesterite systems Cu2NiXY4 (X = Sn, Ge, Si; Y = S, Se) was studied using density functional theory (DFT). The mBJ+U method was used to characterize the bandgap more accurately. To the best of our knowledge, a systematic comparative study of Mn substitution in the entire Cu2NiXY4 (X = Sn, Ge, Si; Y = S, Se) family has not been previously performed. Due to crystallographic constraints of the kesterite unit cell, the substitution of a single Ni atom with Mn corresponds to 50%. This configuration was chosen to study the effect of Mn substitution on the structural and electronic properties of Cu2NiXY4 (X = Sn, Ge, Si; Y = S, Se) compounds, whereas the study of lower concentrations requires the use of a supercell and is the subject of further research. The calculation results show that the partial substitution of Ni with Mn preserves the tetragonal structure of kesterite and significantly alters the electronic structure. In all the compounds studied, the bandgap decreases from 1.028-3.397 to 1.007-3.333 eV. For example, in the Cu2NiSnS4 system, the bandgap width decreases from 1.59 eV to 1.49 eV. The narrowing of the bandgap results from hybridization between the Mn-3d, Cu-3d, and S/Se-p orbitals near the band edges, leading to a redistribution of electronic states around the Fermi level. The results demonstrate that Mn substitution is an effective strategy for controlling the electronic properties of Cu2NiXY4 kesterites, offering great promise for use in optoelectronic devices where adjustable bandgaps are required.
Journal refFunctional Thin Films and Energy Materials,2026,2,59-65
DOI：10.66000/3110-9772.2026.02.04
