Band lineup in amorphous/crystalline silicon heterojunctions and the impact of hydrogen microstructure and topological disorder

We determine the band offsets in amorphous/crystalline silicon [a-Si:H/c-Si{111}] heterojunctions using combined data from photoelectron spectroscopy and surface photovoltage measurements on structures comprising a-Si:H layers with device-relevant thickness (10 nm). Altering the a-Si:H hydrogen (H) content C-H by the choice of deposition conditions, we observe a systematic retreat of the a-Si:H valence band edge leading to an increase of the band gap and the valence band offset Delta E-V with C-H by about 13 meV/at.% H. The discrepancy with the 30-40 meV/at.% H predicted by theory can be consistently explained by the compensating effect of enhanced topological disorder imposed by the increasing density of microvoids as revealed by an analysis of the H microstructure. Thus we highlight the necessity of explicitly including the details of the H configuration in a theoretical treatment of the a-Si:H/c-Si heterojunction.