Giant Negative Photoresponse in van der Waals Graphene/AgBiP₂Se₆/Graphene Trilayer Heterostructures

Abstract The positive photoconductive (PPC) effect is a well‐established primary detection mechanism employed by photodetectors. In contrast, the negative photoconductive (NPC) effect is not extensively investigated thus far, and research on the NPC effect is still in its early stage. Herein, a quaternary van der Waals material, AgBiP₂Se₆ atomic layers, is discovered to achieve a giant NPC effect. Through experimental observations in a Graphene/AgBiP₂Se₆/ Graphene‐based vertical photodetector, an irreversible conversion is identified from common PPC photoresponse to atypical NPC photoresponse. Notably, this device demonstrates an exceptionally high negative responsivity (R) of 4.9 × 10⁵ A W⁻¹, surpassing the previous records for NPC photodetectors. Additionally, it exhibits remarkable optoelectronic performances, including an external quantum efficiency of 1.3 × 10⁸% and a detectivity (D) of 3.60 × 10¹² Jones. The exceptionally high NPC photoresponse observed in this device can be attributed to the swift suppression of photogenerated free carriers at robust recombination centers situated at significant depths, induced by the elevated drain‐source voltage bias. The remarkably high NPC photoresponse also positions AgBiP₂Se₆ as a promising 2D material for multifunctional optoelectronic devices and an excellent platform for systematic exploration of the NPC effect.