Theoretical maximum photogeneration efficiency and performance characterization of InxGa1-xN/Si tandem water-splitting photoelectrodes

InxGa1-xN is a promising material for flexible and efficient water-splitting photoelectrodes since the bandgap is tunable by modifying the indium content. We investigate the potential of an InxGa1-xN/Si tandem used as a water-splitting photoelectrode. We predict a maximum theoretical photogeneration efficiency of 27% for InxGa1-xN/Si tandem photoelectrodes by computing electromagnetic wave propagation and absorption. This maximum is obtained for an indium content between 50% and 60% (i.e., a bandgap between 1.4 eV and 1.2 eV, respectively) and a film thickness between 280 nm and 560 nm. We then experimentally assess InxGa1-xN photoanodes with the indium content varying between 9.5% and 41.4%. A Mott-Schottky analysis indicates doping concentrations (which effectively represent defect density, given there was no intentional doping) above 8.1 x 10(20) cm(-3) (with a maximum doping concentration of 1.9 x 10(22) cm(-3) for an indium content of 9.5%) and flatband potentials between -0.33 V-RHE for x = 9.5% and -0.06 V-RHE for x = 33.3%. Photocurrent-voltage curves of InxGa1-xN photoanodes are measured in 1M H2SO4 and 1M Na2SO4, and the incident photon-to-current efficiency spectra in 1M Na2SO4. The incident photon-to-current efficiency spectra are used to computationally determine the diffusion length, the diffusion optical number, as well as surface recombination and transfer currents. A maximum diffusion length of 262 nm is obtained for an indium content of 23.5%, in part resulting from the relatively low doping concentration (9.8 x 10(20) cm(-3) at x = 23.5%). Nevertheless, the relatively high surface roughness (rms of 7.2 nm) and low flatband potential (-0.1 V-RHE) at x = 23.5% cause high surface recombination and affect negatively the overall photoelectrode performance. Thus, the performance of InxGa1-xN photoelectrodes appears to be a tradeoff between surface recombination (affected by surface roughness and flatband potential) and diffusion length (affected by doping concentration/defect density). The performance improvements of the InxGa1-xN photoanodes are most likely achieved through modification of the doping concentration (defect density) and reduction of the surface recombination (e.g., by the deposition of a passivation layer and co-catalysts). The investigations of the ability to reach high performance by nanostructuring indicate that reasonable improvements through nanostructuring might be very challenging.