Electronic Properties of III-V Semiconductor Photocathode-Water Interfaces: Predictions from First-Principles Calculations

Photoelectrochemical (PEC) cells based on III-V semiconductor photocathodes offer a promising avenue for hydrogen production from water and sunlight. The efficiency of these devices depends on the electronic structure of the interface between the photocathode and liquid water, including the alignment between the semiconductor band edges and the water redox potential. Accurate theoretical predictions of this quantity remain a challenging task, as conventional electronic structure methods such as density functional theory (DFT) often yield substantial errors [1]. In this talk, we present calculations of the electronic properties of two representative III-V semiconductor electrodes, i.e. GaP and InP, at the interface with water using a combination of first-principles molecular dynamics simulations and many-body perturbation theory (MBPT). We show that the use of MBPT is key to obtain band alignments in agreement with experimental measurements. In addition, we describe the relationship between interfacial structure, electronic properties of semiconductors and their reactivity in aqueous solutions.

1. T. A. Pham, D. Lee, E. Schwegler and G. Galli, J. Am. Chem. Soc. in press (2014).

This work was supported by the U.S. Department of Energy at the Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.