Effect of Pt particle size and distribution on photoelectrochemical hydrogen evolution by p-Si photocathodes

In this work, we investigate the effect of the average size and density of Pt clusters on silicon on the photoelectrochemical production of hydrogen. The metallization of Si is performed via electroless deposition from aqueous HF solutions and from water-in-oil microemulsions. The first method enables control of the average diameter and density of Pt clusters by properly changing the deposition parameters like HF concentration and immersion times. However, on one hand, size dispersion is relatively wide and particles agglomeration may occur with this deposition technique. On the other hand, Pt islands with smaller dimensions at the nanoscale as well as with a narrower size distribution are deposited from reversed micellar solutions. Photoelectrochemical experiments show that the effect of Pt morphology on photoconversion efficiency strongly depends on light intensity. At low power of illumination (10 mW/cm2), Pt islands with a mean diameter of 100 nm and a density of 15 particles/microm2, which can be obtained via electroless deposition from a HF-based solution, provide the best photoelectrochemical performance. Nevertheless, this configuration of Pt clusters yields an abrupt collapse of photoconversion efficiency from 31% to 11.8% when the light power is increased up to 100 mW/cm2. At this light intensity, Pt islands with a mean size and density of approximately 40 nm and 75 particles/microm2, respectively, obtained via the microemulsion method, allow photoconversion efficiency as high as 20% to be achieved.