Ge-alloyed kesterite thin-film solar cells: previous investigations and current status – a comprehensive review

The incorporation of Ge into kesterite thin-film absorbers for photovoltaic (PV) applications is thoroughly reviewed. Kesterite materials constitute a promising and critical raw material-free alternative to other inorganic thin-film PV compounds such as Cu(In,Ga)Se₂ and CdTe. The interest in Ge alloying is to solve the critical open-circuit voltage (V_oc) deficit for kesterite solar cells, which is still unresolved and under strong debate. First, the substitution of Sn with Ge from 0 to 100% in the composition of Cu₂Zn(Sn_1−x,Ge_x)(S_y,Se_1−y)₄ absorbers is largely discussed, with a complete overview on the existing literature. It is concluded that fine composition tuning is essential to ensure the Ge-induced enhancement of morphology and single-phase growth through a modified reaction pathway. In this regard, choosing between vacuum- and non vacuum-based deposition methods also plays a crucial role, since the former allows further up-scaling whereas the latter leads to higher thin-film quality. Second, at the solar cell level, Se-rich devices with less than 40% Ge currently exhibit the lowest V_oc and fill factor deficits with the highest efficiencies beyond 13%. This is mainly due to defect and band tail compensation as well as a graded bandgap and enlarged crystalline grains. This study unveils encouraging prospects for Ge-boosted kesterite PV devices.