Electronic Structure of the CdS/Cu(In,Ga)Se₂ Interface of KF- and RbF-Treated Samples by Kelvin Probe and Photoelectron Yield Spectroscopy

Ambient-pressure Kelvin probe and photoelectron yield spectroscopy methods were employed to investigate the impact of the KF and RbF postdeposition treatments (KF-PDT, RbF-PDT) on the electronic features of Cu(In,Ga)Se2 (CIGSe) thin films and the CdS/CIGSe interface in a CdS thickness series that has been sequentially prepared during the chemical bath deposition (CBD) process depending on the deposition time. We observe distinct features correlated to the CBD-CdS growth stages. In particular, we find that after an initial CBD etching stage, the valence band maximum (VBM) of the CIGSe surface is significantly shifted (by 180–620 mV) toward the Fermi level. However, VBM positions at the surface of the CIGSe are still much below the VBM of the CIGSe bulk. The CIGSe surface band gap is found to depend on the type of postdeposition treatment, showing values between 1.46 and 1.58 eV, characteristic for a copper-poor CIGSe surface composition. At the CdS/CIGSe interface, the lowest VBM discontinuity is observed for the RbF-PDT sample. At this interface, a thin layer with a graded band gap is found. We also find that K and Rb act as compensating acceptors in the CdS layer. Detailed energy band diagrams of the CdS/CIGSe heterostructures are proposed.