Tuning Intermediate Bands of Protective Coatings to Reach the Bulk‐Recombination Limit of Stable Water‐Oxidation GaP Photoanodes

Abstract

AbstractStable photoelectrochemical solar fuel production requires protective coatings to achieve effective charge separation, transport, and injection at the semiconductor–liquid interfaces, implying that the coating should energetically align its intermediate band (IB) with both the photoabsorber's band edge and co‐catalyst's potentials. Yet approaches to adjust coating IB positions to accommodate various semiconductor light absorbers for constructing efficient and stable photoelectrodes have not been developed. Herein, three types of transition metal (M = Mn2+, Mn3+, and Cr3+ ions) alloyed TiO2 coatings are discovered using atomic layer deposition (ALD). The IB energetics of these coatings are characterized by X‐ray photoelectron spectroscopy and are found to be tunable inside the TiO2 bandgap, through varying ALD growth conditions. By applying these coatings to n‐type GaP and integrating with IrOx co‐catalysts, the water‐oxidation J–E performance is comparable to an uncoated corroding GaP photoanode. It reaches the bulk recombination limit of the GaP and achieves ≈28% absorbed photon to current efficiency under 475‐nm light excitation (6.48 mW cm−2) and 100‐h stable water oxidation. The outstanding performance and stability are attributed to the efficient charge separation and hole transport, as allowed by the energy alignment of the coating IB and the GaP valence band edge.