Atomic layer deposition of photoactive CoO/SrTiO{sub 3} and CoO/TiO{sub 2} on Si(001) for visible light driven photoelectrochemical water oxidation
Cobalt oxide (CoO) films are grown epitaxially on Si(001) by atomic layer deposition (ALD) using a thin (1.6 nm) buffer layer of strontium titanate (STO) grown by molecular beam epitaxy. The ALD growth of CoO films is done at low temperature (170–180 °C), using cobalt bis(diisopropylacetamidinate) and water as co-reactants. Reflection high-energy electron diffraction, X-ray diffraction, and cross-sectional scanning transmission electron microscopy are performed to characterize the crystalline structure of the films. The CoO films are found to be crystalline as-deposited even at the low growth temperature with no evidence of Co diffusion into Si. The STO-buffered Si (001) is used as a template for ALD growth of relatively thicker epitaxial STO and TiO{sub 2} films. Epitaxial and polycrystalline CoO films are then grown by ALD on the STO and TiO{sub 2} layers, respectively, creating thin-film heterostructures for photoelectrochemical testing. Both types of heterostructures, CoO/STO/Si and CoO/TiO{sub 2}/STO/Si, demonstrate water photooxidation activity under visible light illumination. In-situ X-ray photoelectron spectroscopy is used to measure the band alignment of the two heterojunctions, CoO/STO and CoO/TiO{sub 2}. The experimental band alignment is compared to electronic structure calculations using density functional theory.