Chemical treatment and Fermi-level pinning of CuInS2 and InP photocathodes

Abstract
The photovoltage variation with redox potential ERed is investigated on p‐InP and p‐CuInS2 for various surface treatments. Etching and ion chemisorption are shown to successively improve CuInS2 photovoltages VPh resulting in a slope of ∼1 of VPh vs ERed. The respective densities of states are determined using a model calculation yielding Ds ≊6×1011 states cm2 eV1 and Ds ≊1.2×1014 states cm2 eV1 for the unpinned and pinned situation, respectively. Good agreement between the calculated voltage drop in the Helmholtz layer due to CuInS2 Fermi‐level pinning (FLP) and the missing photovoltage is obtained in a simple model calculation based on the surface state charge density. InP photocathodes show a VPh vs ERed dependence in the dark, depending on pretreatment which is attributed to a chemical reaction that inhibits Fermi level equilibration. Positive from −0.4 V (SCE) VPh is independent of ERed for polished and etched surfaces. The independence is explained assuming a dynamic equilibrium between semiconductor and solution without band‐edge shifting. At the potential where p‐InP solar cells are operated (−0.47 V vs SCE), the electrodes behave as unpinned.