Theoretical Determination of Band Edge Alignments at the Water–CuInS2(112) Semiconductor Interface

Knowledge of a semiconductor electrode’s band edge alignment is essential for optimizing processes that occur at the semiconductor/electrolyte interface. Photocatalytic processes are particularly sensitive to such alignments, as they govern the transfer of photoexcited electrons or holes from the surface to reactants in the electrolyte solution. Reconstructions of a semiconductor surface during operation, as well as its interaction with the electrolyte solution, must be considered when determining band edge alignment. Here, we employ density functional theory + U theory to assess the stability of reconstructed CuInS2 surfaces, a system which has shown promise for the active and selective photoelectrocatalytic reduction of CO2 to CH3OH. Using many-body Green’s function theory combined with calculations of surface work functions, we determine band edge positions of explicitly solvated, reconstructed CuInS2 surfaces. We find that there is a linear relationship between band edge position and net surface dipole, with the most stable solvent/surface structures tending to minimize this dipole because of generally weak interactions between the surface and solvating water molecules. We predict a conduction band minimum (CBM) of the solvated, reconstructed CuInS2 surface of −2.44 eV vs vacuum at the zero-dipole intercept of the dipole/CBM trendline, in reasonable agreement with the experimentally reported CBM position at −2.64 eV vs vacuum. This methodology offers a simplified approach for approximating the band edge positions at complex semiconductor/electrolyte interfaces.