Two-dimensional layered ferroelectric materials, such as CuInP2S6 (CIPS), are promising candidates for novel and high-performance photocatalysts, owing to their ultrathin layer thickness, strong interlayer coupling, and intrinsic spontaneous polarization, while how to control the photocatalytic activity in layered CIPS remains unexplored. In this work, we report for the first time, the photocatalytic activity of ferroelectric CIPS for the chemical deposition of silver nanostructures (AgNSs). The results show that the shape and spatial distribution of AgNSs on CIPS are tunable by controlling layer thickness, environmental temperature, and light wavelength. The ferroelectric polarization in CIPS plays a critical role in tunable AgNS photodeposition, as evidenced by layer thickness and temperature dependence experiments. We further reveal that AgNS photodeposition process starts from active site creation, selective nanoparticle nucleation/aggregation, to continuous film formation. Moreover, AgNS/CIPS heterostructures prepared by photodeposition exhibit excellent resistance switching behavior and good surface enhancement Raman Scattering activity. Our findings provide new insight into the photocatalytic activity of layered ferroelectrics and offer a new material platform for advanced functional device applications in smart memristors and enhanced chemical sensors.

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