Bi₂Te₃/Bi₂Se₃/Bi₂S₃ Cascade Heterostructure for Fast‐Response and High‐Photoresponsivity Photodetector and High‐Efficiency Water Splitting with a Small Bias Voltage

Large-scale multi-heterostructure and optimal band alignment are significantly challenging but vital for photoelectrochemical (PEC)-type photodetector and water splitting. Herein, the centimeter-scale bismuth chalcogenides-based cascade heterostructure is successfully synthesized by a sequential vapor phase deposition method. The multi-staggered band alignment of Bi₂ Te₃ /Bi₂ Se₃ /Bi₂ S₃ is optimized and verified by X-ray photoelectron spectroscopy. The PEC photodetectors based on these cascade heterostructures demonstrate the highest photoresponsivity (103 mA W⁻¹ at -0.1 V and 3.5 mAW⁻¹ at 0 V under 475 nm light excitation) among the previous reports based on two-dimensional materials and related heterostructures. Furthermore, the photodetectors display a fast response (≈8 ms), a high detectivity (8.96 × 10⁹ Jones), a high external quantum efficiency (26.17%), and a high incident photon-to-current efficiency (27.04%) at 475 nm. Due to the rapid charge transport and efficient light absorption, the Bi₂ Te₃ /Bi₂ Se₃ /Bi₂ S₃ cascade heterostructure demonstrates a highly efficient hydrogen production rate (≈0.416 mmol cm⁻² h⁻¹ and ≈14.320 µmol cm⁻² h⁻¹ with or without sacrificial agent, respectively), which is far superior to those of pure bismuth chalcogenides and its type-II heterostructures. The large-scale cascade heterostructure offers an innovative method to improve the performance of optoelectronic devices in the future.