Designing intrinsically photostable low band gap polymers: a smart tool combining EPR spectroscopy and DFT calculations

Hugo Santos Silva, Isabel Fraga Domínguez, Anthony Perthué, Paul D. Topham, Pierre Olivier Bussière, Roger C. Hiorns, Christian Lombard, Agnès Rivaton, Didier Bégué, Brigitte Pépin-Donat

Research output: Contribution to journalArticle

Abstract

A rapid and efficient method to identify the weak points of the complex chemical structure of low band gap (LBG) polymers, designed for efficient solar cells, when submitted to light exposure is reported. This tool combines Electron Paramagnetic Resonance (EPR) using the 'spin trapping method' coupled with density functional theory modelling (DFT). First, the nature of the short life-time radicals formed during the early-stages of photo-degradation processes are determined by a spin-trapping technique. Two kinds of short life-time radical (R and R′O) are formed after 'short-duration' illumination in an inert atmosphere and in ambient air, respectively. Second, simulation allows the identification of the chemical structures of these radicals revealing the most probable photochemical process, namely homolytical scission between the Si atom of the conjugated skeleton and its pendent side-chains. Finally, DFT calculations confirm the homolytical cleavage observed by EPR, as well as the presence of a group that is highly susceptible to photooxidative attack. Therefore, the synergetic coupling of a spin trapping method with DFT calculations is shown to be a rapid and efficient method for providing unprecedented information on photochemical mechanisms. This approach will allow the design of LBG polymers without the need to trial the material within actual solar cell devices, an often long and costly screening procedure.

LanguageEnglish
Pages15647-15654
Number of pages8
JournalJournal of Materials Chemistry A
Volume4
Issue number40
Early online date15 Sep 2016
DOIs
Publication statusPublished - 28 Oct 2016

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Density functional theory
Paramagnetic resonance
Polymers
Energy gap
Spectroscopy
Solar cells
Photodegradation
Screening
Lighting
Atoms
Air

Bibliographical note

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

Cite this

Silva, Hugo Santos ; Domínguez, Isabel Fraga ; Perthué, Anthony ; Topham, Paul D. ; Bussière, Pierre Olivier ; Hiorns, Roger C. ; Lombard, Christian ; Rivaton, Agnès ; Bégué, Didier ; Pépin-Donat, Brigitte. / Designing intrinsically photostable low band gap polymers : a smart tool combining EPR spectroscopy and DFT calculations. In: Journal of Materials Chemistry A. 2016 ; Vol. 4, No. 40. pp. 15647-15654.
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Silva, HS, Domínguez, IF, Perthué, A, Topham, PD, Bussière, PO, Hiorns, RC, Lombard, C, Rivaton, A, Bégué, D & Pépin-Donat, B 2016, 'Designing intrinsically photostable low band gap polymers: a smart tool combining EPR spectroscopy and DFT calculations' Journal of Materials Chemistry A, vol. 4, no. 40, pp. 15647-15654. https://doi.org/10.1039/c6ta05455b

Designing intrinsically photostable low band gap polymers : a smart tool combining EPR spectroscopy and DFT calculations. / Silva, Hugo Santos; Domínguez, Isabel Fraga; Perthué, Anthony; Topham, Paul D.; Bussière, Pierre Olivier; Hiorns, Roger C.; Lombard, Christian; Rivaton, Agnès; Bégué, Didier; Pépin-Donat, Brigitte.

In: Journal of Materials Chemistry A, Vol. 4, No. 40, 28.10.2016, p. 15647-15654.

Research output: Contribution to journalArticle

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AU - Domínguez, Isabel Fraga

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AU - Bussière, Pierre Olivier

AU - Hiorns, Roger C.

AU - Lombard, Christian

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AU - Bégué, Didier

AU - Pépin-Donat, Brigitte

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