There are multiple requirements for maximizing the efficiency of photoelectrochemical overall water splitting using a single n‐type semiconducting photoanode. Many visible‐light‐responsive photoanode materials have been developed but overall water splitting by such materials without external bias has hardly been demonstrated. Herein, the aim is to scale the impact of performance improvement by an n–n heterojunction photoanode comprising an n‐type thin modification surface layer over an n‐type photon absorber, using a finite element method. For the n‐type photon absorber, the semiconductor properties are initially set to those of a well‐studied visible–light‐absorbing Ta3N5, and key properties are varied. It is demonstrated that an appropriate donor density and thickness of the thin surface layer induce adequate energy band bending in the photon absorber, resulting in a dramatic reduction of the onset potential of the photoanode. Thus, even though the quality of the photoanode is poor (e.g., the donor density is high (≈1 × 1019 cm−3)), the optimized surface layer enables the n–n heterojunction photoanode to facilitate bias‐free solar water splitting. These exhaustive investigations could provide design guidelines for obtaining effective photoanodes using an n‐type surface modification layer, such as cocatalysts and hole collection layers.

Zinc telluride (ZnTe)-based photocathodes with appropriate modifications showed incident-photon-to-current conversion efficiencies (IPCEs) higher than 30% at 420–520 nm, reached 40% IPCE at 460 nm, and were not zero up to 710 nm because of photoexcitation related to the intermediate-band. ZnTe films were prepared by productive close-spaced sublimation. After surface modification with CdS and Pt, the photocathode showed clear cathodic photoresponse in the phosphate buffer solution. The modulation of substrate temperature, incorporation of Cu, and further surface modification with very thin Mo and Ti layers significantly enhanced cathodic photocurrent which contributes to hydrogen evolution from water. Through the measurement of IPCEs, photoelectrochemical hydrogen evolution from water utilizing photoexcitation related to the intermediate-band was first confirmed. The photocathode showed advantageous durability under simulated sunlight: during irradiation of about 50 min, the stabilized photocurrent slightly decreased from 1.6 mA cm−2 to 1.5 mA cm−2.