Unassisted Water Splitting Using a GaSb_xP_(1−x) Photoanode

Abstract Here, unbiased water splitting with 2% solar‐to‐hydrogen efficiency under AM 1.5 G illumination using new materials based on GaSb_0.03P_0.97 alloy is reported. Freestanding GaSb_xP_1−x is grown using halide vapor phase epitaxy. The native conductivity type of the alloy is modified by silicon doping, resulting in an open‐circuit potential (OCP) of 750 mV, photocurrents of 7 mA cm⁻² at 10 sun illumination, and corrosion resistance in an aqueous acidic environment. Alloying GaP with Sb at 3 at% improves the absorption of high‐energy photons above 2.68 eV compared to pure GaP material. Electrochemical Impedance Spectroscopy and illuminated OCP measurements show that the conduction band of GaSb_xP_1−x is at −0.55 V versus RHE irrespective of the Sb concentration, while photocurrent spectroscopy indicates that only radiation with photon energies greater than 2.68 eV generate mobile and extractable charges, thus suggesting that the higher‐laying conduction bands in the Γ 1 valley of the alloys are responsible for exciton generation.