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Monolayer Intermixed Oxide Surfaces: Fe, Ni, Cr, v Oxides on Rutile TiO(011) Sandamali Halpegamage, Zhan-Hui Wen, Xue-qing Gong, and Matthias Batzill J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.6b05186 • Publication Date (Web): 23 Jun 2016 Downloaded from http://pubs.acs.org on June 27, 2016
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The Journal of Physical Chemistry
Monolayer Intermixed Oxide Surfaces: Fe-, Ni-, Cr-, V- Oxides on Rutile TiO2(011) Sandamali Halpegamage,1 Zhan-Hui Wen,2 Xue-Qing Gong,* 2 and Matthias Batzill* 1 1
Department of Physics, University of South Florida, Tampa, FL 33620, USA
2
Key Laboratory for Advanced Materials, Centre for Computational Chemistry and Research Institute of Industrial Catalysis, East China University of Science and Technology, Shanghai 200237, P.R. China *corresponding authors: Xue-Qing Gong:
[email protected]; phone: +86-21-64251101; Matthias Batzill:
[email protected]; phone: +1-813-974-0618
Abstract: The oxide/oxide interface for monolayer oxides on rutile TiO2(011) substrates is investigated for several transition metal (M) oxides, with M= Fe, Ni, Cr, and V. The samples are prepared using ultra-high vacuum sample preparation procedures and are characterized with a combination of photoemission spectroscopy and scanning tunneling microscopy (STM). Furthermore, stable intermixed monolayer oxides are determined by density functional theory (DFT) based simulations and compared to the experimental results. Experimentally we find that for specific oxidation conditions a monolayer intermixed oxide is formed for all M. Although different structures as well as oxides in different oxidation states can be obtained depending on the preparation conditions, one common structure has been identified for all M. This intermixed oxide appears to have a defined composition of MTi2O5. For very small amounts of M the surface segregates into a pure TiO2(011)-2x1 surface and into domains of the MTi2O5 phase, indicating that this intermixed oxide monolayer is a low-energy line phase in a compositional surface phase diagram. The gas-phase oxygen pressure that is required to form the intermixed MTi2O5 surface increases in the order of V
