Comparison of the heat-treatment effect on carrier dynamics in TiO₂ thin films deposited by different methods

Polycrystalline titanium dioxide thin films are routinely used in a broad range of applications where charge carrier lifetime is essential for their performance but the effects of the fabrication method are rarely considered. Here we compare three popular deposition methods, atomic layer deposition (ALD), ion beam sputtering (IBS), and spray pyrolysis deposition (SPD). In all three cases, 30 nm thin films of TiO₂ are prepared, and the as-deposited films show no defined crystal structure and can be classified as amorphous films. Heat treatment (HT) of the films converts all of them to polycrystalline anatase TiO₂ as revealed by XRD measurements. A photophysical study was carried out by pico- to nano-second transient absorption pump-probe spectroscopy in transmittance and reflectance modes which allows taking into account the effects due to the photoinduced refractive index changes. This study shows that the HT increases the lifetime of the photo-carriers gradually to a nanosecond time domain (approx. 4 ns) as compared to a few picoseconds of the as-deposited samples. The photo-carrier dynamics of the samples become very similar after heat-treatment, though the topographical features and texture of the films observed with AFM and XRD are quite different. The measured transient absorption spectra of the samples also indicate that the photo-carrier relaxation pathway involves electron and hole trap states with the longest-lived being the hole traps. To evaluate the photoactivity of thin films, methylene blue (MB) photodegradation was tested for all the as-deposited and HT samples and the results showed a 20% higher degradation rate for the IBS HT sample due to the more textured surface.