Low-Cost, Efficient, and Durable H2 Production by Photoelectrochemical Water Splitting with CuGa3Se5 Photocathodes.

Photoelectrochemical (PEC) water splitting is an elegant method of converting sunlight and water into H2 fuel. To be commercially advantageous, PEC devices must become cheaper, more efficient, and much more durable. This work examines low-cost polycrystalline chalcopyrite films, which are successful as photovoltaic absorbers, for application as PEC absorbers. In particular, Cu-Ga-Se films with wide band gaps can be employed as top cell photocathodes in tandem devices as a realistic route to high efficiencies. In this report, we demonstrate that decreasing Cu/Ga composition from 0.66 to 0.31 in Cu-Ga-Se films increased the band gap from 1.67 to 1.86 eV and decreased saturated photocurrent density from 18 to 8 mA/cm2 as measured by chopped-light current-voltage (CLIV) measurements in a 0.5 M sulfuric acid electrolyte. Buffer and catalyst surface treatments were not applied to the Cu-Ga-Se films, and they exhibited promising stability, evidenced by unchanged CLIV after 9 months of storage in air. Finally, films with Cu/Ga = 0.36 (approximately stoichiometric CuGa3Se5) and 1.86 eV band gaps had exceptional durability and continuously split water for 17 days (∼12 mA/cm2 at -1 V vs RHE). This is equivalent to ∼17 200 C/cm2, which is a world record for any polycrystalline PEC absorber. These results indicate that CuGa3Se5 films are prime candidates for cheaply achieving efficient and durable PEC water splitting.

Antimony(III) Sulfide Thin Films as a Photoanode Material in Photocatalytic Water Splitting.

For the first time, we present exploratory investigations on the performance of thermally evaporated Sb2S3 thin film photoanodes for solar-assisted water-splitting applications. With a band gap of 1.72 eV, a 250 nm thick Sb2S3 photoanode showed a saturation photocurrent density of ∼600 µA cm(-2) measured at 1.0 V reversible hydrogen electrode (RHE) in 0.1 M Na2SO4 under 1-sun illumination, with an onset potential of ∼0.25 V RHE. However, subsequent photodegradation studies revealed that the material dissolves relatively quickly with the application of both illumination and bias. Nonetheless, Sb2S3 does have the advantage of having a relatively low optimal fabrication temperature of 300 °C and thus may have utility as a top cell absorber of a tandem device where the bottom cell is temperature sensitive, if protected from corrosion. Therefore, we characterized relevant aspects of the material in an attempt to explain the large difference between the theoretical maximum and measured current density. From our characterization it is believed that the photocatalytic efficiency of this material can be improved by modifying the surface to reduce optical reflection and addressing inherent issues such as high electrical resistivity and surface defects.