A highly transparent thin film hematite with multi-element dopability for an efficient unassisted water splitting system

A tandem system consisting of a combined hematite photoanode/perovskite solar cell is a novel configuration enabling unbiased solar-driven water splitting in a cost-efficient way. However, similar light absorption spectrums between hematite and perovskite, causing significant optical loss of the solar cell located behind the photoelectrochemical cell, have been a critical issue, resulting in a substantial reduction in the overall photoelectrochemical performance in the bias-free tandem system. Herein, we report an efficient thin film hematite/perovskite tandem cell optimized with consideration of both quantum efficiency of the hematite photoanode and optical loss of the solar cell. Ti,Si co-doping with controlled dopability and deposition of transparent NiFeOx co-catalyst on hematite (NiFeOx@Ti:Si–Fe2O3(t)) allowed for highly improved surface reaction kinetics and charge transport behaviors, endowing our thin film with state-of-the-art performance among thin film hematite photoanodes reported to date, with a photocurrent density of 2.62mAcm−2 at 1.23VRHE and an onset potential of 0.71V. The perovskite solar cell in the thin hematite/solar cell exhibited an anodic shift of Voc from 1.08V to 1.16V and a three-fold increased photocurrent density (15.5mAcm−2) compared to the solar cell of the conventional thick hematite/solar cell system. The assembled dual photoanodes (dual NiFeOx@Ti:Si–Fe2O3) reached a maximum photocurrent density of 4.0mAcm−2 at 1.23VRHE. Our tandem photoelectrochemical system comprising assembled dual thin film NiFeOx@Ti:Si–Fe2O3/solar cell showed outstanding performance of an unbiased solar-to-hydrogen (STH) conversion efficiency of 4.49%, which is the highest recorded value in the hematite/perovskite tandem cell systems. This work provides a great potential for further development of an unassisted solar water splitting system with the thin film hematite.