New basic insights into the low hot electron injection efficiency of gold-nanoparticle-photosensitized titanium dioxide.

The low hot electrons injection efficiency (HEIE) from plasmonic metal to semiconductor significantly affects the performance of metal-semiconductor composite. However, there are few reports about the origin of this low HEIE. In the present work, the factors affecting the transfer process and generation efficiency of hot electron in Au@TiO2 composite are investigated using first-principles calculations and Maxwell's electrodynamics theory. The occupation of surface oxygen vacancies of TiO2 by gold atoms is found to increase the hot electrons transfer barrier and expand the space charge region, which decrease the HEIE. In addition, the existing Au@TiO2 structure going against the generation of large amount of hot electrons may also lead to low HEIE. Our results reveal that the replacement of divalent host oxygen atoms with monovalent atoms can decrease the HEIE and comparison with experimental results allows us to validate our predictions. Furthermore, proper surface treatment of semiconductor before depositing metal particles and structure optimization of the composite are suggested to improve the HEIE.