Efficient product separation is an essential requirement for the safe operation and implementation of solar water splitting devices. Ion exchange membranes are typically used, but for a device that requires...

Recently, significant progress in the development of III–V/Si dual-junction solar cells has been achieved. This not only boosts the efficiency of Si-based photovoltaic solar cells but also offers the possibility of highly efficient green hydrogen production via solar water splitting. Using such dual-junction cells in a highly integrated photoelectrochemical approach and aiming for upscaled devices with solar-to-hydrogen (STH) efficiencies beyond 20%, however, the following frequently neglected contrary effects become relevant: (i) light absorption in the electrolyte layer in front of the top absorber and (ii) the impact of this layer on the Ohmic and transport losses. Here, we initially model the influence of the electrolyte layer thickness on the maximum achievable solar-to-hydrogen efficiency of a device with an Si bottom cell and show how the top absorber bandgap has to be adapted to minimize efficiency losses. Then, the contrary effects of increasing Ohmic and transport losses with the decreasing electrolyte layer thickness are evaluated. This allows us to estimate an optimum electrolyte layer thickness range that counterbalances the effects of parasitic absorption and Ohmic/transport losses. We show that fine-tuning of the top absorber bandgap and the water layer thickness can lead to an STH efficiency increase of up to 1% absolute. Our results allow us to propose important design rules for high-efficiency photoelectrochemical devices based on multi-junction photoabsorbers.