Variable-Temperature Resonance Raman Studies to Probe Interchain Ordering for Semiconducting Conjugated Polymers with Different Chain Curvature

Joshua J. Sutton, Thanh Luan Nguyen, Han Young Woo, Keith C. Gordon

Research output: Contribution to journalArticlepeer-review

7 Citations (Scopus)


The morphology and crystallinity of the polymers used to fabricate bulk heterojuction (BHJ) solar cells significantly influences the efficiency of the cells. We have used variable-temperature (VT) spectroscopy techniques, namely VT emission and VT resonance Raman spectroscopy (VT-RRS), to examine how the backbone linearity of a conducting polymer affects its electronic response to temperature and variations in solution behavior. We have studied two types of donor–acceptor polymers used in BHJ cells with differing backbone structures; they are poly-{5,6-bis(tetradecyloxy)-4-(thiophen-2-yl)benzo[c]-1,2,5-thiadiazole} (PTBT) which has a curved backbone and poly-{5,6-bis(tetradecyloxy)-4-(thieno[3,2-b]-thiophen-2-yl)benzo[c]-1,2,5-thiadiazole} (PTTBT) which has a linear chain structure. Time-dependent density functional theory (TD-DFT) calculations and resonance Raman spectra (RRS) of PTTBT revealed the presence of three electronic transitions, with character that varies between π to π*, mixed π to π*/charge transfer and pure charge transfer in nature. Emission spectra of PTTBT showed spectral changes at 650 and 710 nm with varied temperature (−10 to 60 °C). Variable-temperature RRS was measured in resonance with the lowest and highest energy electronic transitions. The changes were interpreted using two-dimensional correlation spectroscopy (2DCOS) analysis. PTTBT showed gradual shifts to lower wavenumbers of modes at around 1425, 1450 and 1500 cm −1 . For PTBT larger and more rapid spectral changes are observed at 1440 and 1460 cm −1 consistent with greater variation in the electronic nature upon heating. Further study into the influence of polymer linearity on crystallinity and long range order was carried out using low-frequency Raman (LFR) to examine drop cast films under a variety of different conditions. LFR spectra showed that PTTBT has a band at 73 cm −1 . This is observed under a variety of film-forming conditions. PTBT does not show distinct low frequency modes, consistent with its low crystallinity.

Original languageEnglish
Pages (from-to)1175-1183
Number of pages9
JournalChemistry - An Asian Journal
Issue number8
Publication statusPublished - 2019 Apr 15

Bibliographical note

Funding Information:
J.J.S thanks the University of Otago for PhD funding. J.J.S and K.C.G acknowledge support from the MacDiarmid Institute for Advanced Materials and Nanotechnology and Dodd-Walls Centre for Photonic and Quantum Technologies. H.Y.W. are grateful to the financial support from the NRF of Korea (2015M1A2A2057506, 2017K2A9A2A12000315) The authors wish to acknowledge the contribution of NeSI high-performance computing facilities to the results of this research. URL

Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


  • conducting polymers
  • long range order
  • low-frequency Raman
  • resonance Raman spectroscopy
  • variable temperature

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry


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