Failure Modes of Platinized pn + -GaInP Photocathodes for Solar-Driven H 2 Evolution.

The long-term stability for the hydrogen-evolution reaction (HER) of homojunction pn + -Ga 0.52 In 0.48 P photocathodes (band gap = 1.8 eV) with an electrodeposited Pt catalyst (pn + -GaInP/Pt) has been systematically evaluated in both acidic and alkaline electrolytes. Electrode dissolution during chronoamperometry was correlated with changes over time in the current density-potential ( J - E ) behavior to reveal the underlying failure mechanism. Pristine pn + -GaInP/Pt photocathodes yielded an open-circuit photopotential ( E oc ) as positive as >1.0 V vs the potential of the reversible hydrogen electrode (RHE) and a light-limited current density ( J ph ) of >12 mA cm -2 (1-sun illumination). However, E oc and J ph gradually degraded at either pH 0 or pH 14. The performance degradation was attributed to three different failure modes: (1) gradual thinning of the n + -emitter layer due to GaInP dissolution in acid; (2) active corrosion of the underlying GaAs substrate at positive potentials causing delamination of the upper GaInP epilayers; and (3) direct GaAs/electrolyte contact compromising the operational stability of the device. This work reveals the importance of both substrate stability and structural integrity of integrated photoelectrodes toward stable solar fuel generation.