The coupling of water-splitting catalysts to silicon photovoltaics enables direct solar-to-fuel conversion. Critical to the performance of such devices is the use of interfaces to protect silicon from the oxygen-evolving reaction (OER) and at the same time to provide Ohmic contact between the buried silicon junction and the immobilised OER catalyst. Presented herein are guidelines for constructing the Si|catalyst interface, which is a crucial building block for efficient direct solar-to-fuel conversion devices. We show that fluorinated-tin-oxide is an especially attractive interface for buried-junction devices.