Giant bulk photovoltaic effect driven by interfacial symmetry breaking in MoS2/Ta2NiSe5 heterostructures.

Van der Waals (vdW) heterostructures offer a versatile platform for engineering unconventional bulk photovoltaic (BPV) effect through interfacial symmetry breaking. However, the coexistence of multiple photophysical mechanisms, driven by structural complexity, spontaneous charge transfer, and strong interlayer coupling, often obscures the microscopic origin of the BPV response and hinders its rational optimization. Here, we demonstrate a pronounced BPV effect localized at the overlap region of a cross-bar MoS2/Ta2NiSe5 vdW heterostructure, where symmetry breaking induced by vertical stacking lifts the inversion center of MoS2. The orthogonal device geometry enables the independent probing of intralayer and interfacial photoresponse pathways, facilitating clear separation of competing mechanisms. Spontaneous interfacial charge transfer between MoS2 and Ta2NiSe5 further establishes a strong interlayer electronic coupling. By modulating the interlayer potential landscape through gate voltage and vertical electric fields, we achieve an optimized zero-bias photocurrent density of 247 A/cm2 and a BPV coefficient of 0.99 V-1. Supported by theoretical modeling, our results illustrate how minimalist device geometry can transform complex heterostructures into experimentally tractable platforms. This strategy paves the way for analyzing and optimizing interface-driven BPV effect, with implications for self-powered optoelectronics, broadband photodetection, and energy-harvesting nanodevices.