Tunable ElectronicStructure and Carrier DynamicsModulation via Ferroelectric Polarization in a CuInP₂S₆/C₇N₆ Heterostructure

Enhancing the transfer and separation efficiency of photogenerated carriers in heterostructures is critical for the development of high-efficiency photocatalysts. In this study, we propose a novel ferroelectric-based van der Waals heterostructure (CuInP₂S₆/C₇N₆) and investigate its electronic properties and carrier dynamics using first-principles calculations and nonadiabatic molecular dynamics (NAMD) simulations. The results revealed that the incorporation of CuInP₂S₆ significantly modulated the electronic structure and enabled efficient separation of photogenerated carriers. NAMD simulations indicated that carrier transfer and recombination in the CuInP₂S₆/C₇N₆ system followed a Type-II mechanism, with the Up-CuInP₂S₆/C₇N₆ configuration meeting the potential requirements for overall water splitting. Moreover, switching the polarization direction of CuInP₂S₆ effectively tunes its interfacial properties, electronic structure, and nonadiabatic coupling, thereby controlling the carrier transfer dynamics. Notably, the Up-CuInP₂S₆/C₇N₆ system exhibits superior photogenerated carrier separation efficiency, making it a promising candidate for photocatalytic applications. This work provides a novel strategy for regulating carrier dynamics and offers valuable insights into designing ferroelectric-based heterostructures for high-performance photocatalytic and optoelectronic devices.