Abstract:Understanding metal–semiconductor interfaces is
critical
to the advancement of photocatalysis and sub-bandgap solar energy
harvesting where electrons in the metal can be excited by sub-bandgap
photons and extracted into the semiconductor. In this work, we compare
the electron extraction efficiency across Au/TiO2 and titanium
oxynitride (TiON)/TiO2–x
interfaces,
where in the latter case the spontaneously forming oxide layer (TiO2–x
) creates a metal–semiconductor
contact. Time-resolved pump–probe spectroscopy … Show more
“…The observed relaxation occurred in the order of tens to hundreds of picoseconds (ps), suggesting strong electron–phonon coupling leading to rapid lattice heating. 38,39 This demonstrates excellent light-to-heat conversion by neat TiN. The result aligns with the observed increase in catalyst bed temperature with decreased Ni loading under inert conditions amongst the prepared (NiO loaded) samples.…”
Effectively engaging light to induce catalytic activity requires the careful selection of a catalyst support with appropriate and beneficial properties. On this basis, black, plasmonic TiN was employed as a...
“…The observed relaxation occurred in the order of tens to hundreds of picoseconds (ps), suggesting strong electron–phonon coupling leading to rapid lattice heating. 38,39 This demonstrates excellent light-to-heat conversion by neat TiN. The result aligns with the observed increase in catalyst bed temperature with decreased Ni loading under inert conditions amongst the prepared (NiO loaded) samples.…”
Effectively engaging light to induce catalytic activity requires the careful selection of a catalyst support with appropriate and beneficial properties. On this basis, black, plasmonic TiN was employed as a...
The lack of a detailed mechanistic understanding for plasmon-mediated charge transfer at metal-semiconductor interfaces severely limits the design of efficient photovoltaic and photocatalytic devices. A major remaining question is the relative contribution from indirect transfer of hot electrons generated by plasmon decay in the metal to the semiconductor compared to direct metal-to-semiconductor interfacial charge transfer. Here, we demonstrate an overall electron transfer efficiency of 44 ± 3% from gold nanorods to titanium oxide shells when excited on resonance. We prove that half of it originates from direct interfacial charge transfer mediated specifically by exciting the plasmon. We are able to distinguish between direct and indirect pathways through multimodal frequency-resolved approach measuring the homogeneous plasmon linewidth by single-particle scattering spectroscopy and time-resolved transient absorption spectroscopy with variable pump wavelengths. Our results signify that the direct plasmon-induced charge transfer pathway is a promising way to improve hot carrier extraction efficiency by circumventing metal intrinsic decay that results mainly in nonspecific heating.
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