Charge carrier mapping for Z-scheme photocatalytic water-splitting sheet via categorization of microscopic time-resolved image sequences.

Photocatalytic water splitting system using particulate semiconductor materials is a promising strategy for converting solar energy into hydrogen and oxygen. In particular, visible-light-driven 'Z-scheme' printable photocatalyst sheets are cost-effective and scalable. However, little is known about the fundamental photophysical processes, which are key to explaining and promoting the photoactivity. Here, we applied the pattern-illumination time-resolved phase microscopy for a photocatalyst sheet composed of Mo-doped BiVO4 and Rh-doped SrTiO3 with indium tin oxide as the electron mediator to investigate photo-generated charge carrier dynamics. Using this method, we successfully observed the position- and structure-dependent charge carrier behavior and visualized the active/inactive sites in the sheets under the light irradiation via the time sequence images and the clustering analysis. This combination methodology could provide the material/synthesis optimization methods for the maximum performance of the photocatalyst sheets.

Lifetime mapping of photo-excited charge carriers by the transient grating imaging technique for nano-particulate semiconductor films.

The transient grating (TG) imaging technique has been developed, where the refractive index change due to the photoexcited charge carriers excited with a stripe patterned light can be visualized. The spatiotemporal imaging of photoexcited charge carriers was demonstrated for a nanoparticulate TiO2 film. In the analytical procedures to map out the time constant distribution, the averaged response of photoexcited carriers in each image was obtained from the Fourier transform of the TG images since the image has a spatial modulation with a stripe pattern of light. The oscillation response due to the acoustic grating, the decay of the surface trapped electrons (until 1 µs), and thermal diffusion (until 100 µs) were observed. In order to obtain the lifetime imaging of the photoexcited electrons, the target time region (0-1 µs) for the response was selected and fitted with an exponential function, and the time constants were mapped out. We found that the time constants showed a wide range of distribution (68-920 ns), dependent on the sample positions.