Cation Substitution in Earth‐Abundant Kesterite Photovoltaic Materials

As a promising candidate for low-cost and environmentally friendly thin-film photovoltaics, the emerging kesterite-based Cu₂ZnSn(S,Se)₄ (CZTSSe) solar cells have experienced rapid advances over the past decade. However, the record efficiency of CZTSSe solar cells (12.6%) is still significantly lower than those of its predecessors Cu(In,Ga)Se₂ (CIGS) and CdTe thin-film solar cells. This record has remained for several years. The main obstacle for this stagnation is unanimously attributed to the large open-circuit voltage (V_OC) deficit. In addition to cation disordering and the associated band tailing, unpassivated interface defects and undesirable energy band alignment are two other culprits that account for the large V_OC deficit in kesterite solar cells. To capture the great potential of kesterite solar cells as prospective earth-abundant photovoltaic technology, current research focuses on cation substitution for CZTSSe-based materials. The aim here is to examine recent efforts to overcome the V_OC limit of kesterite solar cells by cation substitution and to further illuminate several emerging prospective strategies, including: i) suppressing the cation disordering by distant isoelectronic cation substitution, ii) optimizing the junction band alignment and constructing a graded bandgap in absorber, and iii) engineering the interface defects and enhancing the junction band bending.