Resonant light trapping in ultrathin films for water splitting

Semiconductor photoelectrodes for solar hydrogen production by water photoelectrolysis must employ stable, non-toxic, abundant and inexpensive visible-light absorbers. Iron oxide (α-Fe₂O₃) is one of few materials meeting these requirements, but its poor transport properties present challenges for efficient charge-carrier generation, separation, collection and injection. Here we show that these challenges can be addressed by means of resonant light trapping in ultrathin films designed as optical cavities. Interference between forward- and backward-propagating waves enhances the light absorption in quarter-wave or, in some cases, deeper subwavelength films, amplifying the intensity close to the surface wherein photogenerated minority charge carriers (holes) can reach the surface and oxidize water before recombination takes place. Combining this effect with photon retrapping schemes, such as using V-shaped cells, provides efficient light harvesting in ultrathin films of high internal quantum efficiency, overcoming the trade-off between light absorption and charge collection. A water photo-oxidation current density of 4 mA cm^-2 was achieved using a V-shaped cell comprising ∼ 26-nm-thick Ti-doped α-Fe₂O₃ films on back-reflector substrates coated with silver-gold alloy.