Theory of multiphoton photoemission disclosing excited states in conduction band of individual TiO2 nanoparticles

A theory of multiphoton photoemission is derived to explain the experimentally observed monotonic decrease with the wavelength in the electron yield of TiO₂ nanoparticles (NPs) by as large as four orders of magnitude. It is found that the fitting parameter corresponds to the energy position of Ti3d e_g and t_2g states, and the derived theory is a novel diagnostic of excited states in the conduction band, very importantly, applicable to individual NPs. The difference between four-photon slope NPs and three-photon slope NPs is attributed to the difference in defect density. The success of the theory in solving the puzzling result shows that thermal emission from high-lying levels may dominate over direct multiphoton ionization in solids when the photon number larger than four is required.