Research Progress on Transition Metals Substitution in Cu2ZnSnS4-Based Thin Film Solar Cells

铜锌锡硫基(Cu2ZnSnS4-based)光伏材料因其优异的性能在太阳能电池中具有广泛的应用前景。然而由于CZTS体系中阳离子大小接近，Cu+和Zn2+化学失配较小，导致大量的点缺陷和缺陷簇存在，致使CZTS中有大的开路电压赤字限制了其效率的提升。过渡金属Cd、Fe、Mn、Co、Ni等元素的掺杂对于铜锌锡硫基(Cu2ZnSnS4-based)薄膜光电性能的改善具有重要意义，适当的阳离子取代能够克服CZTS材料中大的开路电压Voc赤字，同时改变阳离子取代浓度可以调节带隙结构。通过不同元素的掺杂，可实现光电性能更优的需求。本文通过分析不同掺杂元素及掺杂浓度对CZTS基薄膜光电性能的影响，综述了近年来利用过渡金属(Cd, Fe, Mn, Co, Ni)离子掺杂改性Cu2ZnSnS4基薄膜太阳电池的研究进展，并提出了CZTS基薄膜电池的应用前景、存在问题和发展方向。 Cu2ZnSnS4-based photovoltaic materials have a wide range of application prospects in solar cells due to its excellent properties. However, the close size of the cations in the CZTS system and the small chemical mismatch between Cu+ and Zn2+ result in a large number of point defects and defect clusters, leading to a large open-circuit voltage(Voc) deficit in the CZTS that limits its efficiency. The substitution of transition metals Cd, Fe, Mn, Co, Ni and other elements is of great significance for the improvement of the photoelectric properties of Cu2ZnSnS4-based thin film. Proper cation substitution can overcome the large open-circuit voltage (Voc) deficit in CZTS ma-terials, while changing the cation substitution concentration can adjust the bandgap structure. Through the substitution of different elements, better photoelectric properties can be achieved. By analyzing the influence of different substitution elements and substitution concentration on the photoelectric properties of CZTS-based thin film, the recent research progresses on transition metals (Cd, Fe, Mn, Co, Ni) substitution in Cu2ZnSnS4-based thin film solar cells are reviewed. Furthermore we put forward the application prospect, existing problems and development direction of CZTS-based thin film battery.