Pulsed Laser Deposition of Epitaxial and Polycrystalline Bismuth Vanadate Thin Films

• Published in: Journal of physical chemistry. C Vol. 118; no. 46; pp. 26543 - 26550
• Main Authors: Rettie, Alexander J. E, Mozaffari, Shirin, McDaniel, Martin D, Pearson, Kristen N, Ekerdt, John G, Markert, John T, Mullins, C. Buddie
• Format: Journal Article
• Language: English
• Published: American Chemical Society 20.11.2014
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/jp5082824

We report pulsed laser deposition (PLD) synthesis of epitaxial and polycrystalline monoclinic bismuth vanadate (BiVO4, BVO) thin films. X-ray diffraction (XRD), atomic force microscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy were used to characterize the samples. Epitaxial, c-axis oriented growth was achieved using single crystal yttria-stabilized zirconia (100), a substrate temperature of 575–600 °C, and an oxygen pressure of 7.8 mTorr. The volatility of Bi necessitated a large excess (Bi:V = ∼6:1) of this element in the ceramic targets to obtain stoichiometric films. XRD confirmed a BVO (001)||YSZ (001) and BVO [100]||YSZ [100] epitaxial relationship. Film growth was 3-D, and the morphology was discontinuous, consisting of irregular, smooth grains. Additionally, dense, continuous polycrystalline films were deposited on fluorine-doped tin oxide (FTO) on glass substrates at room temperature with stoichiometric targets and postdeposition annealing in air. Evaluation of these samples as photoanodes yielded photocurrents of ∼0.15 and ∼0.05 mA cm–2 at 1.23 V vs RHE under backside AM1.5G illumination with and without a hole scavenger (Na2SO3), respectively. We argue that the photocurrents are due to the high oxygen content inherent in the PLD process and suggest that these continuous films may be well-suited to investigating oxygen-related defects in BVO.