Carrier Recombination-Incited Substrate Vibrations after Pulsed UV-Laser Photolysis of TiO 2 Thin Single-Crystal Plate and Nanoparticle Films

Photo-induced carrier generation and recombination have been regarded as important steps in understanding the photocatalytic reactions on the surfaces of semiconductors such as TiO₂. During the investigation of a photocatalytic water-splitting reaction on the surface of semiconductor TiO₂ (rutile) single-crystal plate and sintered-nanoparticle (anatase) films coated on a CaF₂ plate, a pulsed 355 nm laser was used for band-gap excitation and a continuous-working, mid-infrared laser as the probe to trace the kinetics of the photogenerated electrons. Fast oscillations with periods of 10–50 μs were observed. We demonstrated experimentally that these oscillations are neither from the nonlinear carrier recombination dynamics nor surface chemical reactions; instead, they are caused by the thermal-induced flexural vibrations initiated by the fast carrier recombination in the light-absorbing area. The observed oscillations can be well accounted for by thermal stress-induced flexural vibrations of the substrates due to rapid charge recombination, and the observed oscillation frequencies match the flexural vibration frequencies predicted by the Kirchhoff–Love thin-plate theory. Light-interference effect caused by the beam reflecting off the surfaces of the substrate and windows, which can amplify the oscillation signals, is also discussed. Several approaches are proposed to minimize or eliminate the interference from the substrate vibration in the transient kinetic measurement when a coherent laser is used as the probe beam.