A1 Refereed original research article in a scientific journal
The Nature of the Charge Carriers in Polyazulene as Studied by in Situ Electron Spin Resonance-UV-Visible-Near-Infrared Spectroscopy
Authors: Osterholm A, Petr A, Kvarnstrom C, Ivaska A, Dunsch L
Publisher: AMER CHEMICAL SOC
Publication year: 2008
Journal:Journal of Physical Chemistry B
Journal name in sourceJOURNAL OF PHYSICAL CHEMISTRY B
Journal acronym: J PHYS CHEM B
Volume: 112
Issue: 45
First page : 14149
Last page: 14157
Number of pages: 9
ISSN: 1520-6106
DOI: https://doi.org/10.1021/jp805813s
Abstract
In situ spectroelectrochemistry is of high importance for the characterization of doping reactions in pi-conjugated polymers. In this paper we present the results of simultaneous ESR and UV-vis-NIR measurements performed in situ during electrochemical p- and n-doping of polyazulene (PAz). In previous studies on p-doping of PAz the assignment of the optical absorption bands to specific charge carriers have been somewhat controversial, therefore the aim of this study is to clarify the nature of the doping-induced charge carriers and their corresponding optical absorption bands by in situ ESR-UV-vis-NIR spectroelectrochemistry. PAz was polymerized in two different potential ranges in order to obtain films with different structures and morphologies. On the basis of our spectroelectrochemical results we propose that polarons and polaron pairs are formed during p-doping in the two different types of PAz films electrodeposited on ITO. For studying n-doping of PAz, a Pt electrode was used. The ESR signal first decreased in intensity at low doping levels and then increased in intensity at higher doping levels pointing to the formation of new paramagnetic species. At high negative potentials there occurred an additional line broadening of the ESR signal indicating the existence of rather localized negative charge carriers.
In situ spectroelectrochemistry is of high importance for the characterization of doping reactions in pi-conjugated polymers. In this paper we present the results of simultaneous ESR and UV-vis-NIR measurements performed in situ during electrochemical p- and n-doping of polyazulene (PAz). In previous studies on p-doping of PAz the assignment of the optical absorption bands to specific charge carriers have been somewhat controversial, therefore the aim of this study is to clarify the nature of the doping-induced charge carriers and their corresponding optical absorption bands by in situ ESR-UV-vis-NIR spectroelectrochemistry. PAz was polymerized in two different potential ranges in order to obtain films with different structures and morphologies. On the basis of our spectroelectrochemical results we propose that polarons and polaron pairs are formed during p-doping in the two different types of PAz films electrodeposited on ITO. For studying n-doping of PAz, a Pt electrode was used. The ESR signal first decreased in intensity at low doping levels and then increased in intensity at higher doping levels pointing to the formation of new paramagnetic species. At high negative potentials there occurred an additional line broadening of the ESR signal indicating the existence of rather localized negative charge carriers.
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