Photocatalytic Activity of Pulsed Laser Deposited TiO2 Thin Films

TL;DR

This study investigates how pulsed laser deposition parameters influence the structural and photoelectrochemical properties of TiO2 thin films, revealing that buffer gas pressure controls oxygen vacancies, phase composition, and photoelectrochemical efficiency.

Contribution

It demonstrates that adjusting deposition pressure and temperature can tailor TiO2 thin films' electronic structure and PEC performance, a novel insight for optimizing photoanodes.

Findings

Lower deposition pressure increases oxygen vacancies.

Anatase phase persists at high temperatures under certain pressures.

Photoelectrochemical efficiency varies with deposition conditions.

Abstract

Nanostructured TiO2 thin films were prepared by pulsed laser deposition (PLD) on indium doped tin oxide (ITO) substrates. Results from X-ray photoelectron spectroscopy (XPS) show that Ti 2p core level peaks shift toward the lower binding energy with decrease in the buffer gas pressure (O2:Ar = 1:1). This suggests that oxygen vacancies are created under insufficient oxygen conditions. Anatase to rutile ratio is also found to be system pressure dependent. Under deposition pressure of 750 mTorr only anatase phase was observed even at 1073 K substrate temperature which is much higher that the bulk anatase to rutile phase transformation temperature. The deposited TiO2 thin films were fabricated as photoanodes for photoelectrochemical (PEC) studies. PEC measurements on TiO2 photoanodes show that the flatband potential (Vfb) increases by 0.088 eV on absolute vacuum energy scale (AVS) with decrease in the deposition pressure, from 750 to 250 mTorr at 873K. The highest incident photon to current conversion efficiency [IPCE(lambda)] of 2.5 to 6 % was obtained from the thin films prepared at substrate temperature of 873K. Combining the results from XPS and PEC studies, we conclude that the deposition pressure affects the concentration of the oxygen vacancies which changes the electronic structure of the TiO2. With reference to photoelectrochemical catalytic performance, our results suggest that it is possible to adjust the Fermi energy level and structure of TiO2 thin films by controlling the buffer gas pressure and temperature to align the energy of the flatband potential (Vfb) with respect to specific redox species in the electrolyte.