Evanescent-field spectroscopy using structured optical fibers: Detection of charge-transfer at the porphyrin-silica interface

Martelli, C; Canning, J; Reimers, JR; Sintic, M; Stocks, D; Khoury, T; Crossley, MJ

Evanescent-field spectroscopy using structured optical fibers: Detection of charge-transfer at the porphyrin-silica interface

Martelli, C Canning, J

Reimers, JR

Sintic, M Stocks, D Khoury, T Crossley, MJ

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Publication Type:: Journal Article
Citation:: Journal of the American Chemical Society, 2009, 131 (8), pp. 2925 - 2933
Issue Date:: 2009-03-04

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Field	Value	Language
dc.contributor.author	Martelli, C	en_US
dc.contributor.author	Canning, J https://orcid.org/0000-0001-8281-7783	en_US
dc.contributor.author	Reimers, JR https://orcid.org/0000-0001-5157-7422	en_US
dc.contributor.author	Sintic, M	en_US
dc.contributor.author	Stocks, D	en_US
dc.contributor.author	Khoury, T	en_US
dc.contributor.author	Crossley, MJ	en_US
dc.date.issued	2009-03-04	en_US
dc.identifier.citation	Journal of the American Chemical Society, 2009, 131 (8), pp. 2925 - 2933	en_US
dc.identifier.issn	0002-7863	en_US
dc.identifier.uri	http://hdl.handle.net/10453/28173
dc.description.abstract	The fabrication of porphyrin thin films derived from dichloro[5,10,15,20- tetra(heptyl)porphyrinato]tin(IV) [CI-Sn(THP)-CI] in the holes of photonic crystal fibers over 90 cm in length is described. Evanescent field spectroscopy (EFS) is used to investigate the interfacial properties of the films, with the high surface optical intensity and the long path length combining to produce significant absorption. By comparison with results obtained for similar films formed from CI-Sn(THP)-CI inside fused-silica cuvettes and on glass slides, the film is shown to be chemisorbed as a surface Si-O-Sn(THP)-X (X = Cl or OH) species. In addition to the usual porphyrin Q and Soret bands, new absorptions in the in-fiber films are observed by EFS at 445 nm and between 660-930 nm. The 660-930 nm band is interpreted as a porphyrin to silicon charge-transfer transition and postulated to arise following chemisorption at mechanical-strain induced defect sites on the silica surface. Such defect sites are caused by the optical fiber production process and are less prevalent on other glass surfaces. EFS within optical fibers therefore offers new ways for understanding interface phenomena such as surface adsorbates on glass. Such understanding will benefit all devices that exploit interface phenomena, both in optical fibers and other integrated waveguide forms. They may be directly exploited to create ultrasensitive molecular detectors and could yield novel photonic devices. © 2009 American Chemical Society.	en_US
dc.relation.ispartof	Journal of the American Chemical Society	en_US
dc.relation.isbasedon	10.1021/ja8081473	en_US
dc.subject.classification	General Chemistry	en_US
dc.subject.mesh	Tin	en_US
dc.subject.mesh	Silicon Dioxide	en_US
dc.subject.mesh	Metalloporphyrins	en_US
dc.subject.mesh	Microscopy, Electron, Scanning	en_US
dc.subject.mesh	Spectrum Analysis	en_US
dc.subject.mesh	Surface Properties	en_US
dc.subject.mesh	Models, Molecular	en_US
dc.subject.mesh	Fiber Optic Technology	en_US
dc.subject.mesh	Optical Fibers	en_US
dc.title	Evanescent-field spectroscopy using structured optical fibers: Detection of charge-transfer at the porphyrin-silica interface	en_US
dc.type	Journal Article
utslib.citation.volume	8	en_US
utslib.citation.volume	131	en_US
utslib.for	0306 Physical Chemistry (incl. Structural)	en_US
utslib.for	03 Chemical Sciences	en_US
pubs.embargo.period	Not known	en_US
pubs.organisational-group	/University of Technology Sydney
pubs.organisational-group	/University of Technology Sydney/Faculty of Engineering and Information Technology
pubs.organisational-group	/University of Technology Sydney/Faculty of Engineering and Information Technology/School of Electrical and Data Engineering
pubs.organisational-group	/University of Technology Sydney/Faculty of Science
pubs.organisational-group	/University of Technology Sydney/Faculty of Science/School of Mathematical and Physical Sciences
pubs.organisational-group	/University of Technology Sydney/Strength - GBDTC - Global Big Data Technologies
utslib.copyright.status	closed_access
pubs.issue	8	en_US
pubs.publication-status	Published	en_US
pubs.volume	131	en_US

Abstract:

The fabrication of porphyrin thin films derived from dichloro[5,10,15,20- tetra(heptyl)porphyrinato]tin(IV) [CI-Sn(THP)-CI] in the holes of photonic crystal fibers over 90 cm in length is described. Evanescent field spectroscopy (EFS) is used to investigate the interfacial properties of the films, with the high surface optical intensity and the long path length combining to produce significant absorption. By comparison with results obtained for similar films formed from CI-Sn(THP)-CI inside fused-silica cuvettes and on glass slides, the film is shown to be chemisorbed as a surface Si-O-Sn(THP)-X (X = Cl or OH) species. In addition to the usual porphyrin Q and Soret bands, new absorptions in the in-fiber films are observed by EFS at 445 nm and between 660-930 nm. The 660-930 nm band is interpreted as a porphyrin to silicon charge-transfer transition and postulated to arise following chemisorption at mechanical-strain induced defect sites on the silica surface. Such defect sites are caused by the optical fiber production process and are less prevalent on other glass surfaces. EFS within optical fibers therefore offers new ways for understanding interface phenomena such as surface adsorbates on glass. Such understanding will benefit all devices that exploit interface phenomena, both in optical fibers and other integrated waveguide forms. They may be directly exploited to create ultrasensitive molecular detectors and could yield novel photonic devices. © 2009 American Chemical Society.

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http://hdl.handle.net/10453/28173