Mixed Sulfur/Selenium Anions Weaken Electron-Vibrational Interaction in Cu2ZnSn(S,Se)4 Photoabsorber

Kesterite Cu2ZnSn­(S,Se)4 (CZTSSe) solar absorbers have attracted intensive investigations for next-generation photovoltaic applications. Here, by using ab initio static and molecular dynamics simulations, we investigated the anion compositional dependence of electron-vibration interaction in CZTSSe materials. We found that the conduction band fluctuates more than the valence band, and as a result, the band gap variation is more sensitive to the change of the former, which can be understood in terms of p–d hybridization in the valence bands. Electron–phonon coupling is smaller in CZTSSe alloy compared to pure S- or Se-containing structures, as evidenced by the smaller fluctuation of excitation energy, and can be attributed to the weaker structural dynamics of the metal–anion bond. Small electron–phonon coupling strength may lead to better charge transport in these materials. We also elucidated the interplay between disordered structures and S/Se stoichiometry through analysis of optical line width. The results highlight the importance of anion composition engineering and provide new insights into the rational design of high-performing kesterite absorbers for solar cells.