Hot-electron transfer from the semiconductor domain to the metal domain in CdSe@CdS{Au} nano-heterostructures

Abstract

Semiconductor–metal hybrid nanostructures are recognized as great materials due to their high level of light-induced charge separation, which has direct relevance in photocatalysis and solar energy conversion. To understand the mechanism of charge separation processes, hybrid CdSe@CdS{Au} nano-heterostructures containing Au nanoparticles (NPs) with different sizes were synthesized, and the ultrafast charge-transfer dynamics were monitored using femtosecond transient absorption spectroscopy. Steady-state optical absorption studies suggest the formation of charge-transfer complexes between core shell nanocrystals (NCs) and Au NPs. Steady-state and time-resolved luminescence spectroscopy suggest electron transfer from the photo-excited CdSe@CdS core shell QDs NCs to the Au NPs within the heterostructure. The ultrafast interfacial electron-transfer dynamics in the heterostructures were monitored by femtosecond transient absorption spectroscopy. The results revealed that both hot and thermalized electrons are transferred from the core shell QDs to the metal NPs with time constants of 150 and 300 fs, respectively. Hot-electron transfer from QDs to Au NPs was found to take place predominantly in the heterostructures depending on the sizes of the metal NPs. The photo-degradation of rhodamin B in the presence of the CdSe@CdS{Au} heterostructures under visible-light radiation suggests that the hot electrons in the heterostructures play a major role in photocatalytic degradation.