Potassium Postdeposition Treatment-Induced Band Gap Widening at Cu(In,Ga)Se₂ Surfaces – Reason for Performance Leap?

Direct and inverse photoemission were used to study the impact of alkali fluoride postdeposition treatments on the chemical and electronic surface structure of Cu­(In,Ga)­Se₂ (CIGSe) thin films used for high-efficiency flexible solar cells. We find a large surface band gap (E_g^Surf, up to 2.52 eV) for a NaF/KF-postdeposition treated (PDT) absorber significantly increases compared to the CIGSe bulk band gap and to the E_g^Surf of 1.61 eV found for an absorber treated with NaF only. Both the valence band maximum (VBM) and the conduction band minimum shift away from the Fermi level. Depth-dependent photoemission measurements reveal that the VBM decreases with increasing surface sensitivity for both samples; this effect is more pronounced for the NaF/KF-PDT CIGSe sample. The observed electronic structure changes can be linked to the recent breakthroughs in CIGSe device efficiencies