A Novel Ge-Doping Approach for Grain Growth and Recombination Suppression in Buffer-Free CIGSe Solar Cells

Ge-doped CIGSe absorbers were fabricated using a two-step process of depositing sputtered stacked Ge-doped CIGSe precursors and selenization annealing. The effects of Ge doping on the crystallinity as well as defects of CIGSe absorbers and the performance of CIGSe buffer-free solar cells were investigated. The results show that Ge doping significantly promotes the grain growth of CIGSe absorbers. Due to Ge loss via volatilization during selenization annealing, Ge residue is undetectable in Ge-doped absorbers. Ge doping offers an effective approach to improve CIGSe crystallinity without introducing notable impurity phases or Ge-related defects. However, Ge doping also induces Se loss, and excessive Se vacancy defects adversely affect the performance of the absorber. In addition, Ge doping increases the contact potential difference at CIGSe grain boundaries and is beneficial for reducing carrier recombination at these sites. Analysis of recombination rates in Ge-doped CIGSe buffer-free solar cells reveals that the combined effects of enhanced crystallinity and optimized electrical properties at grain boundaries effectively suppress the recombination in the space charge region, at the interface, and in the quasi-neutral region, leading to improved device performance.