Enabling Efficient Charge Separation for Optoelectronic Conversion via an Energy-Dependent Z‑Scheme n‑Semiconductor–Metal–p-Semiconductor Schottky Heterojunction

Achieving good charge separation while maintaining energetic electronic states in heterostructures is a challenge in designing efficient photocatalyst materials. Using first-principles calculations, we propose a Z-scheme Sn–m–Sp (n-semiconductor–metal–p-semiconductor) heterojunction as a viable avenue for achieving broad-spectrum sunlight absorption and, importantly, energy-dependent charge separation. As a proof-of-concept investigation, we investigated two ternary heterostructures, CdS–Au–PdO and SnO2–W–Ag2O, in which the electronic Fermi levels line up by virtue of the presence of an intermediate metal layer. A cascade of work functions in the relative order Wn < Wm < Wp drives electrons flowing from Sn to m and from m to Sp. The inner electric fields established at the Sn–m and m–Sp Schottky junctions selectively guide low-energy photoexcited electrons from Sn (CdS/SnO2) and low-energy holes from Sp (PdO/Ag2O) to the interposing Au or W metal, respectively. Importantly, relatively low Schottky barriers enforce charge separation by constraining high-energy photogenerated charges to the individual semiconductor layers. Operating together, these two mechanisms enable the achievement of highly efficient optoelectronic conversion.