Interfacial Connections between Organic Perovskite/n+ Silicon/Catalyst that Allow Integration of Solar Cell and Catalyst for Hydrogen Evolution from Water

The rapidly increasing solar conversion efficiency (PCE) of hybrid organic–inorganic perovskite (HOIP) thin‐film semiconductors has triggered interest in their use for direct solar‐driven water splitting to produce hydrogen. However, application of these low‐cost, electronic‐structure‐tunable HOIP tandem photoabsorbers has been hindered by the instability of the photovoltaic‐catalyst‐electrolyte (PV+E) interfaces. Here, photolytic water splitting is demonstrated using an integrated configuration consisting of an HOIP/n+silicon single junction photoabsorber and a platinum (Pt) thin film catalyst. An extended electrochemical (EC) lifetime in alkaline media is achieved using titanium nitride on both sides of the Si support to eliminate formation of insulating silicon oxide, and as an effective diffusion barrier to allow high‐temperature annealing of the catalyst/TiO2‐protected‐n+silicon interface necessary to retard electrolytic corrosion. Halide composition is examined in the (FA1‐xCsx)PbI3 system with a bandgap suitable for tandem operation. A fill factor of 72.5% is achieved using a Spiro‐OMeTAD‐hole‐transport‐layer (HTL)‐based HOIP/n+Si solar cell, and a high photocurrent density of −15.9 mA cm−2 (at 0 V vs reversible hydrogen electrode) is attained for the HOIP/n+Si/Pt photocathode in 1 m NaOH under simulated 1‐sun illumination. While this thin‐film design creates stable interfaces, the intrinsic photo‐ and electro‐degradation of the HOIP photoabsorber remains the main obstacle for future HOIP/Si tandem PEC devices. Using a TiN/TiO2‐bilayer to prevent diffusion enables connecting a hybrid‐organic–inorganic‐perovskite photoabsorber to both a n+Si‐conductor and a Pt‐catalyst to create an integrated photocathode for hydrogen evolution. This allows thermal processing needed to achieve a relatively high fill factor of 72.5% and high current density at 0 V versus reversible‐hydrogen‐electrode of −15.9 mA cm−2 for the resulting solar cell and photocathode, respectively.