Photoelectrochemical water splitting cells comprising the alloys of III-V semiconductors hold record solar-to-hydrogen efficiencies. However, the performance of state-of-the art III-V alloy-based single absorber devices, particularly of InGaP₂, InGaAs, GaPN, and GaAsN, comes short of unassisted water due to a) inadequate alignment of band edges with respect to the HER and OER redox potentials, b) insufficient photovoltage to favor charge separation at the solid electrolyte liquid junction, and/or iii) recombination. In order to circumvent these limitations considerable research efforts have been directed at creating more complex architectures involving e.g. tandem cells, nanostructures, and buried junctions to correctly position the bands and provide enough driving force to surmount overpotentials and the 1.23 eV energetic barrier of the water splitting reactions. Therefore, developing novel III-V photoabsorbers with adequate band energetics is key to conceiving simpler, yet efficient single semiconductor PEC cells for production of solar fuels at a competitive cost.

First-principles DFT+U calculations incorporating the local density approximation and generalized gradient approximation have shown that incorporation of Sb narrows the band gap in Ga(Sb_x)N_1-x and changes the electronic band gap from indirect to direct in GaSbP. Theoretical computations predict that, with band gaps in the order of 2 eV, these materials straddle the potential window for water oxidation and proton reduction in acidic solution.

Single crystalline films of these two materials have been deposited by halide/hydride vapor phase epitaxy and metalorganic chemical vapor deposition systems, in a wide range of Sb incorporation without phase segregation. Experimental results corroborate the significant band gap reduction in GaSbN from 3.4 to 1.5 eV(Fig 1a) and suggest the conversion of excitonic transitions in the electronic band structure of GaSbP (Fig 1b) as determined by Tauc plot analysis of diffuse reflectance data and low temperature photoluminescence spectroscopy.

Electrodes comprising Ga(Sb_x)N_1-x and Ga(Sb_x)P_1-x have been benchmarked employing 2- and 3-electrode standard methods for assessment of their characteristic attributes, i.e. flat-band and onset potentials, photovoltage, zero-bias photocurrent density, fill factors, carrier concentrations, and most importantly, their ability for gas evolution by in situ fluorescence probing. This presentation will highlight recent advances in the understanding of the inter-relationship of processing/synthesis, material structure and photoelectrochemical properties of this new class of materials. Also, preliminary data on un-assisted photoactivity involving p-Si cathode and n-type GaSbP anode will be presented.

Acknowledgements: Financial support from US Department of Energy (DE-FG02-07ER46375) and NSF (DMS1125909). Collaborations with Dr. Todd Deutsch & Dr. James Young of NREL, and Dr. Madhu Menon of Univ. of Kentucky are acknowledged. Also acknowledge contributions of prior PhD students (Alejandro Garcia and Swathi Sunkara).

References:

1. R.M. Sheetz, E. Richter, A.N. Andriotis, C. Pendyala, M.K. Sunkara and M. Menon, “Visible light absorption and large band gap bowing in dilute alloys of gallium nitride with antimony”, Phys. Rev. B, 84, 075304 (2011)
2. S. Sunkara, V.K. Vendra, J.B. Jasinski, T. Deutsch, A.N. Andriotis, K. Rajan, M. Menon and M.K. Sunkara, "New Visible Light Absorbing Materials for Solar Fuels, Ga(Sbx)N1-x”, Adv. Mater., 26 (18), 2878-2882 (2014)
3. H. Russell et al., “Direct Band Gap Gallium Antimony Phosphide GaSb_xP_1-x Alloys”, Scientific Reports 6, (2016).