Electroless patterned assembly of metal nanoparticles on hydrogen-terminated silicon surfaces for applications in photoelectrocatalysis.

The deposition of gold and platinum nanoparticles (NPs) on hydrogen-terminated Si(100) (Si(100)-H) surfaces has been performed by galvanic displacement using fluoride-free sub-millimolar metallic salt solutions. The scanning electron microscopy (SEM) images showed the formation of oblate hemispherical NPs, with an average diameter of ca. 40 nm and an average height of 20 ± 10 and 10 ± 5 nm for Au and Pt, respectively. Furthermore, the calculated number density was (6.0 ± 0.8) × 10(9) Au NPs cm(-2) and (6.6 ± 1.3) × 10(9) Pt NPs cm(-2) with a larger size distribution measured for Au NPs. The Au 4f and Pt 4f X-ray photoelectron spectra of the metallized surfaces were characterized by a principal component corresponding to either the metallic gold or platinum. However, two other components located at higher binding energies were also visible and ascribed to gold or platinum silicides. Using this fluoride-free deposition process and a "reagentless" UV photolithography technique, we have also demonstrated that it was possible to prepare metallic NP micropatterns. Following this approach, single metal (Au) and two metals (Au and Pt) patterns have been produced and characterized by energy-dispersive X-ray spectroscopy (EDS) which revealed the presence of the expected metal(s). Such metallic NP micropatterned surfaces were used as photocathodes for H(2) evolution from water as a proof-of-concept experiment. These electrodes exhibited much higher electrocatalytic performance than that of nonmetallized Si(100)-H, both in the absence of light and under illumination. The overpotential for hydrogen evolution was significantly decreased by ca. 450 mV with respect to Si(100)-H (measured for a current density of 0.1 mA cm(-2)) under identical illumination conditions.