Dynamics of photo‐induced surface oxygen vacancies in metal‐oxide semiconductors studied under ambient conditions

Glass, D., Cortés, E., Ben‐Jaber, S., Brick, T., Peveler, W. J. , Blackman, C. S., Howle, C. R., Quesada‐Cabrera, R., Parkin, I. P. and Maier, S. A. (2019) Dynamics of photo‐induced surface oxygen vacancies in metal‐oxide semiconductors studied under ambient conditions. Advanced Science, (doi:10.1002/advs.201901841) (Early Online Publication)

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Abstract

Surface‐enhanced Raman spectroscopy (SERS) is a powerful analytical technique commonly used in the detection of traces of organic molecules. The mechanism of SERS is of a dual nature, with Raman scattering enhancements due to a combination of electromagnetic (EM) and chemical contributions. In conventional SERS, the EM component is largely responsible for the enhancement, with the chemical contribution playing a less significant role. An alternative technique, called photo‐induced enhanced Raman spectroscopy (PIERS) has been recently developed, using a photo‐activated semiconductor substrate to give additional chemical enhancement of Raman bands over traditional SERS. This enhancement is assigned to surface oxygen vacancies (Vo) formed upon pre‐irradiation of the substrate. In this work, the exceptional chemical contribution in PIERS allows for the evaluation of atomic Vo dynamics in metal oxide surfaces. This technique is applied to study the formation and healing rates of surface‐active Vo in archetypical metal‐oxide semiconductors, namely, TiO2, WO3, and ZnO. Contrary to conventional analytical tools, PIERS provides intuitive and valuable information about surface stability of atomic defects at ambient pressure and under operando conditions, which has important implications in a wide range of applications including catalysis and energy storage materials.

Item Type:Articles
Additional Information:D.G., T.B., E.C., and S.A.M. acknowledge the EPSRC through the Reactive Plasmonics Programme (EP/M013812/1), ONR and ONR Global, Solar Technologies Go Hybrid (SOLTECH) programme, and the Lee‐Lucas Chair in Physics. S.A.M. acknowledges funding from Air Force Office of Scientific Research/EOARD (FA9550‐17‐1‐0300) and the Nanoscience Initiative Munich. I.P.P. acknowledges the EPSRC Eng.D Centre (EP/L015862/1). E.C. acknowledges financial support from the European Commission through ERC Starting Grant CATALIGHT 802989. D.G. acknowledges funding from DSTL for the PhD programme under contract DSTLX‐1000116630. W.J.P. acknowledges the University of Glasgow for a Lord Kelvin Adam Smith Fellowship.
Status:Early Online Publication
Refereed:Yes
Glasgow Author(s) Enlighten ID:Peveler, Dr William
Authors: Glass, D., Cortés, E., Ben‐Jaber, S., Brick, T., Peveler, W. J., Blackman, C. S., Howle, C. R., Quesada‐Cabrera, R., Parkin, I. P., and Maier, S. A.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Advanced Science
Publisher:Wiley
ISSN:2198-3844
ISSN (Online):2198-3844
Published Online:30 September 2019
Copyright Holders:Copyright © 2019 The Authors
First Published:First published in Advanced Science 2019
Publisher Policy:Reproduced under a Creative Commons License

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