Thermal conversion of precursor polymer to low bandgap conjugated polymer containing isothianaphthene dimer subunits

Tomokazu Umeyama, Kohei Hirose, Kei Noda, Kazumi Matsushige, Tetsuya Shishido, Hironobu Hayashi, Yoshihiro Matano, Noboru Ono, Hiroshi Imahori

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

Thermal conversion strategy has been utilized in the synthesis of a novel low bandgap polymer containing isothianaphthene (ITN) dimer structure and benzodithiophene (BDT) unit in the backbone (PBIBDT). First, a highly soluble precursor polymer with an alternating main chain structure of bicyclo[2.2.2]octadiene-fused thiophene dimer and BDT (PPBIBDT) was synthesized by a palladium(0)-catalyzed Stille coupling reaction. Then, heating of the yellow PPBIBDT film spin-coated on a glass plate yielded a dark blue film of PBIBDT that was insoluble in any organic solvents. Thermogravimetric analysis of PPBIBDT showed 14% weight loss with an onset at 230 °C, corroborating the occurrence of the thermally induced retro-Diels-Alder reaction. The PBIBDT film showed red-shifted, broad absorption in the visible and near-infrared regions with a maximum at 706 nm compared to the precursor polymer PPBIBDT with an absorption peak at 445 nm. The introduction of an ITN dimer unit in the backbone lowered the bandgap owing to the stabilized quinoid resonance structure. The field-effect hole mobility of PBIBDT was determined to be 1.1 × 10 -4 cm 2 V -1 s -1 with an on-off ratio of 2.5 × 10 2, while the PPBIBDT-based device revealed no p- and n-type responses. Organic photovoltaic devices were fabricated based on the planar heterojunction structure of PBIBDT and [6,6]-phenyl-C 61- butyric acid methyl ester (PCBM) and showed a power conversion efficiency of 0.07% under standard AM1.5 sunlight (100 mW cm -2). These results obtained here will provide fundamental information on the design of thermally induced low bandgap polymers for device applications.

Original languageEnglish
Pages (from-to)1256-1264
Number of pages9
JournalJournal of Physical Chemistry C
Volume116
Issue number1
DOIs
Publication statusPublished - 2012 Jan 12
Externally publishedYes

Fingerprint

Conjugated polymers
Dimers
Polymers
Energy gap
dimers
polymers
Thiophenes
Diels-Alder reactions
Hole mobility
Butyric acid
Butyric Acid
butyric acid
hole mobility
Palladium
Thiophene
sunlight
thiophenes
Organic solvents
Conversion efficiency
Thermogravimetric analysis

ASJC Scopus subject areas

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

Cite this

Thermal conversion of precursor polymer to low bandgap conjugated polymer containing isothianaphthene dimer subunits. / Umeyama, Tomokazu; Hirose, Kohei; Noda, Kei; Matsushige, Kazumi; Shishido, Tetsuya; Hayashi, Hironobu; Matano, Yoshihiro; Ono, Noboru; Imahori, Hiroshi.

In: Journal of Physical Chemistry C, Vol. 116, No. 1, 12.01.2012, p. 1256-1264.

Research output: Contribution to journalArticle

Umeyama, T, Hirose, K, Noda, K, Matsushige, K, Shishido, T, Hayashi, H, Matano, Y, Ono, N & Imahori, H 2012, 'Thermal conversion of precursor polymer to low bandgap conjugated polymer containing isothianaphthene dimer subunits', Journal of Physical Chemistry C, vol. 116, no. 1, pp. 1256-1264. https://doi.org/10.1021/jp208775x
Umeyama, Tomokazu ; Hirose, Kohei ; Noda, Kei ; Matsushige, Kazumi ; Shishido, Tetsuya ; Hayashi, Hironobu ; Matano, Yoshihiro ; Ono, Noboru ; Imahori, Hiroshi. / Thermal conversion of precursor polymer to low bandgap conjugated polymer containing isothianaphthene dimer subunits. In: Journal of Physical Chemistry C. 2012 ; Vol. 116, No. 1. pp. 1256-1264.
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AU - Shishido, Tetsuya

AU - Hayashi, Hironobu

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