• electrochemistry;
  • photochemistry;
  • silicon;
  • solar cells;
  • water splitting


A hybrid photovoltaic/photoelectrochemical (PV/PEC) water-splitting device with a benchmark solar-to-hydrogen conversion efficiency of 5.2 % under simulated air mass (AM) 1.5 illumination is reported. This cell consists of a gradient-doped tungsten–bismuth vanadate (W:BiVO4) photoanode and a thin-film silicon solar cell. The improvement with respect to an earlier cell that also used gradient-doped W:BiVO4 has been achieved by simultaneously introducing a textured substrate to enhance light trapping in the BiVO4 photoanode and further optimization of the W gradient doping profile in the photoanode. Various PV cells have been studied in combination with this BiVO4 photoanode, such as an amorphous silicon (a-Si:H) single junction, an a-Si:H/a-Si:H double junction, and an a-Si:H/nanocrystalline silicon (nc-Si:H) micromorph junction. The highest conversion efficiency, which is also the record efficiency for metal oxide based water-splitting devices, is reached for a tandem system consisting of the optimized W:BiVO4 photoanode and the micromorph (a-Si:H/nc-Si:H) cell. This record efficiency is attributed to the increased performance of the BiVO4 photoanode, which is the limiting factor in this hybrid PEC/PV device, as well as better spectral matching between BiVO4 and the nc-Si:H cell.