Colossal shift current response in elemental two-dimensional ferroelectrics

Abstract A bulk material without inversion symmetry can generate a direct current under uniform illumination. This interface-free current generation mechanism, referred to as the bulk photovoltaic effect (BPVE), has the potential to overcome the Shockley-Queisser limit of traditional solar cells based on $p$-$n$ junctions. Here, we explore the shift current generation, a major mechanism responsible for the BPVE, in single-element two-dimensional ferroelectrics represented by phosphorene-like monolayers of As, Sb, and Bi. The strong covalency and large joint density of states afforded by these elemental 2D materials give rise to colossal shift currents, outperforming many state-of-the-art materials over a wide range of wavelengths including the visible light spectrum. For a given frequency and polarization of an incoming light, we find that the shift current, due to its topological nature, depends sensitively on the details of the Bloch wave functions. It is crucial to consider the electronic exchange-correlation potential beyond the generalized gradient approximation as well as the spin-orbit interaction in density functional theory calculations to obtain reliable photon frequency-dependent shift current responses.