Establishing Multiple‐Order Built‐In Electric Fields Within Heterojunctions to Achieve Photocarrier Spatial Separation

Abstract Hybridizing two heterocomponents to construct a built‐in electric field (BIEF) at the interface represents a significant strategy for facilitating charge separation in carbon dioxide (CO 2 )‐photoreduction. However, the unidirectional nature of BIEFs formed by various low‐dimensional materials poses challenges in adequately segregating the photogenerated carriers produced in bulk. In this study, leveraging zinc oxide (ZnO) nanodisks, a sulfurization reaction is employed to fabricate Z‐scheme ZnO/zinc sulfide (ZnS) heterojunctions featuring a multiple‐order BIEF. These heterojunctions reveal distinctive interfacial structures characterized by two semicoherent phase boundaries. The cathodoluminescence 2D maps and density functional theory calculation results demonstrate that the direction of the multiple‐order BIEF spans from ZnS to ZnO. This directional alignment significantly fosters the spatial separation of photogenerated electrons and holes within ZnS nanoparticles and enhances CO 2 ‐to‐carbon monoxide photoreduction performance (3811.7 µmol h −1 g −1 ). The findings present a novel pathway for structurally designing BIEFs within heterojunctions, while providing fresh insights into the migratory behavior of photogenerated carriers across interfaces.