Photoluminescence study of anatase TiO2 photocatalysts at the pico- and nanosecond timescales

We studied the photoluminescence decay kinetics of three nanosized anatase TiO2 photocatalysts (particle diameter: 7, 25, or 200 nm) at the pico- and nanosecond timescales for elucidating the origin of the luminescence. Luminescence spectra from these photocatalysts obtained under steady-state excitation conditions comprised green luminescence that decayed on the picosecond timescale and red luminescence that persisted at the nanosecond timescale. Among the photocatalysts with different sizes, there were marked differences in the rate of luminescence decay at the picosecond timescale (<600 ps), although the spectral shapes were comparable. The similarity in the spectral shape indicated that self-trapped excitons (STEs) directly populated in the bulk of the particle by light excitation emit the luminescence in a picosecond timescale, and the difference in the rate of luminescence decay originated from the quenching at the particle surface. Furthermore, we theoretically considered excitation light intensity dependence on the quantum yield of the luminescence and found that the quenching reaction was not limited by the diffusion of the STEs but by the reaction at the particle surface. Both the spectral shape and time-evolution of the red luminescence from the deep trapped excitons in the nanosecond timescale varied among the photocatalysts, suggesting that the trap sites in different photocatalysts have different characteristics with respect to luminescence. Therefore, the relation between trap states and photocatalytic activity will be elucidated from the red luminescence study.