Enhanced shift current bulk photovoltaic effect in ferroelectric Rashba semiconductor α-GeTe: ab initio study from three- to two-dimensional van der Waals layered structures

Abstract

The ferroelectric Rashba semiconductors (FERSCs) are endowed with a unique combination of ferroelectricity and the spin degree of freedom, resulting in a long carrier lifetime and impressive bulk photovoltaic (BPV) efficiency that reached 25% in organometal halide perovskites. The BPV efficiency can be further improved by using low-dimensional ferroelectrics however, it is inhibited by the ferroelectric instability in low-dimensional perovskites and toxicity along with phase instability of the lead-halide perovskites. To address these challenges, the α-GeTe could be of great importance which is the simplest known lead-free FERSC with an intrinsic layered structure. Therefore, in this work, we investigate the BPV properties of three- to two-dimensional van der Waals structures of α-GeTe by calculating the shift current (SHC). We predict that the mono (1.56 Å) and bi-layers (5.44–6.14 Å) α-GeTe with the buckled honeycomb structure are dynamically stable and possess the characteristic features of the bulk up to the nanoscale limit. The SHC of ∼70 μA V−2 is calculated in bulk α-GeTe which is 20 times larger than that obtained in organometal halides in the visible light. The SHC increases with decreasing the number of layers, reaching a maximum amplitude of ∼300 μA V−2 at 2.67 eV in the monolayer which is more than double that obtained in monolayer GeS. We find that the SHC in monolayer α-GeTe can be further enhanced and redshifted by applying a compressive strain; which is correlated with the strong absorption of the xx-polarized light, stimulated by the more delocalized p x /y orbital character of the density of states. Furthermore, in the bilayer structures, the magnitude of the SHC is sensitive to the layers’ stacking arrangement and a maximum SHC (∼250 μA V−2) can be achieved with an AB-type stacking arrangement. Combining these results with the benefits of being environmental-friendly material makes α-GeTe a good candidate for next-generation solar cells application.