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Lookup NU author(s): Professor Andrew Hamnett, Professor Paul ChristensenORCiD
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A new fast electrochemical ellipsometer has been constructed using a Stokesmeter configuration, and applied to the study of poly[Pd(MeOSalen)] films during growth from acetonitrile solutions and subsequent electrochemical cycling. Growth of the films does not take place until a critical potential is reached, after which nucleation on the electrode surface takes place. Earlier work has emphasised the importance of metal- metal interactions in these systems, and it is suggested that initial formation of stacked oligomers may take place in solution, and these then nucleate on the surface to give a film of approximately 40 nm initial thickness. As growth continues through cycling, the nature of the film changes, becoming relatively close packed near the electrode surface, but less close packed at the film/electrolyte interface. Even when growth is complete, the resultant films remain inhomogeneous, and show substantial swelling on anodic cycling. Evidence for this swelling is also provided by in situ FTIR studies, and it is suggested that the morphology of the films is dominated at low potentials by stacking interactions, and that inter-chain repulsions at high potentials disrupt these interactions, giving rise to substantial ingress of solvent and counter-ions.
Author(s): Hamnett A, Abel J, Eameaim J, Christensen P, Timonov A, Vasilyeva S
Publication type: Article
Publication status: Published
Journal: Physical Chemistry Chemical Physics
Year: 1999
Volume: 1
Issue: 22
Pages: 5147-5156
Print publication date: 15/11/1999
ISSN (print): 1463-9076
ISSN (electronic): 1463-9084
Publisher: Royal Society of Chemistry
URL: http://dx.doi.org/10.1039/a906632b
DOI: 10.1039/a906632b
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