A spectroscopic and DFT study of the electronic properties of carbazole-based D-A type copolymers

Matthew E. Reish, Sanghun Nam, Wonho Lee, Han Young Woo, Keith C. Gordon

Research output: Contribution to journalArticle

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Abstract

The structural and electronic properties of three carbazole containing copolymers used in organic photovoltaic applications, poly[N-1-octylnonyl-2,7- carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′, 3′-benzothiadiazole)] (PCDTBT), poly[N-1-octylnonyl-2,7-carbazole-alt-4,7- (2′,1′,3′-benzothiadiazole)] (PCBT), and poly[N-1-octylnonyl- 2,7-carbazole-alt-4,7-(2′,1′,3′-benzoselenadiazole)] (PCBSe) have been studied using resonance Raman (RR) and transient absorption (TA) spectroscopies and density functional theory (DFT) calculations. Enhancement of Raman modes centered on the acceptor unit when a Raman excitation wavelength is coincident with lowest energy electronic excitation suggests that the excitation involves charge transfer from the carbazole donor to the varying benzodiazole acceptors. The pattern of the enhancement when the excitation wavelength is coincident with the higher energy transition indicates that this transition is π to π* in nature; this is consistent with TD-DFT calculations. Nanosecond transient absorption studies show long-lived excited state signals for PCDTBT (126 ± 4 ns and 1.56 ± 0.1 μs) and PCBSe (1.82 ± 0.1 μs), suggesting that population of the triplet state is appreciable. No transient signal could be detected in PCBT. B3LYP TD-DFT calculations of the monomer through to the hexamer indicate a broadly delocalized excited state orbital for PCDTBT as indicated by the linear decrease in excitation energy with an increased number of repeat units, while for PCBSe and PCBT, the reduction in excitation is sublinear. The highest occupied (HOMO) and lowest unoccupied molecular orbitals (LUMO) of PCBSe and PCBT polymers compared to PCDTBT are similarly diffuse, but the population of higher order orbitals is decreased when compared with PCDTBT. CAM-B3LYP calculations reduce the delocalization of the frontier orbitals and show less reduction in excitation energy with additional repeat units for each polymer.

Original languageEnglish
Pages (from-to)21255-21266
Number of pages12
JournalJournal of Physical Chemistry C
Volume116
Issue number40
DOIs
Publication statusPublished - 2012 Oct 11
Externally publishedYes

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carbazoles
Electronic properties
Density functional theory
copolymers
Copolymers
density functional theory
Excitation energy
electronics
Excited states
excitation
Polymers
Wavelength
Molecular orbitals
Computer aided manufacturing
Absorption spectroscopy
Charge transfer
Structural properties
orbitals
Monomers
carbazole

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

A spectroscopic and DFT study of the electronic properties of carbazole-based D-A type copolymers. / Reish, Matthew E.; Nam, Sanghun; Lee, Wonho; Woo, Han Young; Gordon, Keith C.

In: Journal of Physical Chemistry C, Vol. 116, No. 40, 11.10.2012, p. 21255-21266.

Research output: Contribution to journalArticle

Reish, Matthew E. ; Nam, Sanghun ; Lee, Wonho ; Woo, Han Young ; Gordon, Keith C. / A spectroscopic and DFT study of the electronic properties of carbazole-based D-A type copolymers. In: Journal of Physical Chemistry C. 2012 ; Vol. 116, No. 40. pp. 21255-21266.
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