Mei, Bastian Timo2; Seger, Brian1; Pedersen, Thomas3; Malizia, Mauro1; Hansen, Ole2; Chorkendorff, Ib1; Vesborg, Peter Christian Kjærgaard1
1 Department of Physics, Technical University of Denmark2 Experimental Surface and Nanomaterials Physics, Department of Physics, Technical University of Denmark3 Department of Micro- and Nanotechnology, Technical University of Denmark4 Silicon Microtechnology, Department of Micro- and Nanotechnology, Technical University of Denmark
Sputter deposition of Ir/IrOx on p+-n-Si without interfacial corrosion protection layers yielded photoanodes capable of efficient water oxidation (OER) in acidic media (1 M H2SO4). Stability of at least 18 h was shown by chronoamperomety at 1.23 V versus RHE (reversible hydrogen electrode) under 38.6 mW/cm2 simulated sunlight irradiation (λ > 635 nm, AM 1.5G) and measurements with quartz crystal microbalances. Films exceeding a thickness of 4 nm were shown to be highly active though metastable due to an amorphous character. By contrast, 2 nm IrOx films were stable, enabling OER at a current density of 1 mA/cm2 at 1.05 V vs. RHE. Further improvement by heat treatment resulted in a cathodic shift of 40 mV and enabled a current density of 10 mA/cm2 (requirements for a 10% efficient tandem device) at 1.12 V vs. RHS under irradiation. Thus, the simple IrOx/Ir/p+-n-Si structures not only provide the necessary overpotential for OER at realistic device current, but also harvest ∼100 mV of free energy (voltage) which makes them among the best-performing Si-based photoanodes in low-pH media.
Journal of Physical Chemistry Letters, 2014, Vol 5, Issue 11, p. 1948-1952