A Transparent, High‐Performance, and Stable Sb2S3 Photoanode Enabled by Heterojunction Engineering with Conjugated Polycarbazole Frameworks for Unbiased Photoelectrochemical Overall Water Splitting Devices

Developing low-cost, high-performance, and durable photoanodes is essential in solar-driven photoelectrochemical (PEC) energy conversion. Sb₂ S₃ is a low-bandgap (≈1.7 eV) n-type semiconductor with a maximum theoretical solar conversion efficiency of ≈28% for PEC water splitting. However, bulk Sb₂ S₃ exhibits opaque characteristics and suffers from severe photocorrosion, and thus the use of Sb₂ S₃ as a photoanode material remains underexploited. This study describes the design and fabrication of a transparent Sb₂ S₃ -based photoanode by conformably depositing a thin layer of conjugated polycarbazole frameworks (CPF-TCzB) onto the Sb₂ S₃ film. This structural design creates a type-II heterojunction between the CPF-TCzB and the Sb₂ S₃ with a suitable band-edge energy offset, thereby, greatly enhancing the charge separation efficiency. The CPF-TCzB/Sb₂ S₃ hybrid photoanode exhibits a remarkable photocurrent density of 10.1 mA cm^-2 at 1.23 V vs reversible hydrogen electrode. Moreover, the thin CPF-TCzB overlayer effectively inhibits photocorrosion of the Sb₂ S₃ and enables long-term operation for at least 100 h with ≈10% loss in photocurrent density. Furthermore, a standalone unbiased PEC tandem device comprising a CPF-TCzB/Sb₂ S₃ photoanode and a back-illuminated Si photocathode can achieve a record solar-to-hydrogen conversion efficiency of 5.21%, representing the most efficient PEC water splitting device of its kind.