Relativistic quasiparticle self-consistent electronic structure of hybrid halide perovskite photovoltaic absorbers

Abstract: Solar cells based on a light absorbing layer of the organometal halide perovskite CH$_3$NH$_3$PbI$_3$ have recently reached 15% conversion efficiency, though how these materials work remains largely unknown. We analyse the electronic structure and optical properties within the quasiparticle self-consistent GW approximation. While this compound bears some similarity to conventional sp semiconductors, it also displays unique features. Quasiparticle self-consistency is essential for an accurate description of the band structure: bandgaps are much larger than what is predicted by the local density approximation (LDA) or GW based on the LDA. Valence band dispersions are modified in a very unusual manner. In addition, spin orbit coupling strongly modifies the band structure and gives rise to unconventional dispersion relations and a Dresselhaus splitting at the band edges. The average hole mass is small, which accounts for the long diffusion lengths recently observed. The surface ionisation potential (workfunction) is calculated to be 5.7 eV with respect to the vacuum level, explaining efficient carrier transfer to TiO$_2$ and Au electrical contacts.