Bulk Photovoltaics in Nanoscale Systems – Origin of Shift Currents in the Many-Body Picture

The shift current in bulk photovoltaics is commonly attributed to a shift in non-interacting charge centres. We show that the origin of shift currents in the many-body picture is fundamentally different. Here the shift current arises largely from a many-body shift vector that also involves shifts in charge centres, but these are associated with pairs of nearly-degenerate excitons overlapping in k-space. The shift current can thus be enhanced by nearly-degenerate, optically-active and tightly-bound excitons, spread out in k-space. Ab initio results are presented for BaTiO_3, NbOCl_2 and MoS_2.