Thieno[3,4- c ]pyrrole-4,6-dione-based polymer semiconductors

Toward high-performance, air-stable organic thin-film transistors

Xugang Guo, Rocio Ponce Ortiz, Yan Zheng, Myung Gil Kim, Shiming Zhang, Yan Hu, Gang Lu, Antonio Facchetti, Tobin J Marks

Research output: Contribution to journalArticle

173 Citations (Scopus)

Abstract

We report a new p-type semiconducting polymer family based on the thieno[3,4-c]pyrrole-4,6-dione (TPD) building block, which exhibits good processability as well as good mobility and lifetime stability in thin-film transistors (TFTs). TPD homopolymer P1 was synthesized via Yamamoto coupling, whereas copolymers P2-P8 were synthesized via Stille coupling. All of these polymers were characterized by chemical analysis as well as thermal analysis, optical spectroscopy, and cyclic voltammetry. P2-P7 have lower-lying HOMOs than does P3HT by 0.24-0.57 eV, depending on the donor counits, and exhibit large oscillator strengths in the visible region with similar optical band gaps throughout the series (∼1.80 eV). The electron-rich character of the dialkoxybithiophene counits in P8 greatly compresses the band gap, resulting in the lowest Egopt in the series (1.66 eV), but also raising the HOMO energy to -5.11 eV. Organic thin-film transistor (OTFT) electrical characterization indicates that device performance is very sensitive to the oligothiophene conjugation length, but also to the solubilizing side chain substituents (length, positional pattern). The corresponding thin-film microstructures and morphologies were investigated by XRD and AFM to correlate with the OTFT performance. By strategically varying the oligothiophene donor conjugation length and optimizing the solubilizing side chains, a maximum OTFT hole mobility of ∼0.6 cm2 V-1 s-1 is achieved for P4-based devices. OTFT environmental (storage) and operational (bias) stability in ambient was investigated, and enhanced performance is observed due to the low-lying HOMOs. These results indicate that the TPD is an excellent building block for constructing high-performance polymers for p-type transistor applications due to the excellent processability, substantial hole mobility, and good device stability.

Original languageEnglish
Pages (from-to)13685-13697
Number of pages13
JournalJournal of the American Chemical Society
Volume133
Issue number34
DOIs
Publication statusPublished - Aug 31 2011

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Semiconductors
Thin film transistors
Polymers
Air
Semiconductor materials
Equipment and Supplies
Temperature programmed desorption
Hole mobility
Spectrum Analysis
Semiconducting polymers
Hot Temperature
Electrons
Optical band gaps
Homopolymerization
Chain length
Thermoanalysis
Cyclic voltammetry
Transistors
Energy gap
Copolymers

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Thieno[3,4- c ]pyrrole-4,6-dione-based polymer semiconductors : Toward high-performance, air-stable organic thin-film transistors. / Guo, Xugang; Ortiz, Rocio Ponce; Zheng, Yan; Kim, Myung Gil; Zhang, Shiming; Hu, Yan; Lu, Gang; Facchetti, Antonio; Marks, Tobin J.

In: Journal of the American Chemical Society, Vol. 133, No. 34, 31.08.2011, p. 13685-13697.

Research output: Contribution to journalArticle

Guo, Xugang ; Ortiz, Rocio Ponce ; Zheng, Yan ; Kim, Myung Gil ; Zhang, Shiming ; Hu, Yan ; Lu, Gang ; Facchetti, Antonio ; Marks, Tobin J. / Thieno[3,4- c ]pyrrole-4,6-dione-based polymer semiconductors : Toward high-performance, air-stable organic thin-film transistors. In: Journal of the American Chemical Society. 2011 ; Vol. 133, No. 34. pp. 13685-13697.
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abstract = "We report a new p-type semiconducting polymer family based on the thieno[3,4-c]pyrrole-4,6-dione (TPD) building block, which exhibits good processability as well as good mobility and lifetime stability in thin-film transistors (TFTs). TPD homopolymer P1 was synthesized via Yamamoto coupling, whereas copolymers P2-P8 were synthesized via Stille coupling. All of these polymers were characterized by chemical analysis as well as thermal analysis, optical spectroscopy, and cyclic voltammetry. P2-P7 have lower-lying HOMOs than does P3HT by 0.24-0.57 eV, depending on the donor counits, and exhibit large oscillator strengths in the visible region with similar optical band gaps throughout the series (∼1.80 eV). The electron-rich character of the dialkoxybithiophene counits in P8 greatly compresses the band gap, resulting in the lowest Egopt in the series (1.66 eV), but also raising the HOMO energy to -5.11 eV. Organic thin-film transistor (OTFT) electrical characterization indicates that device performance is very sensitive to the oligothiophene conjugation length, but also to the solubilizing side chain substituents (length, positional pattern). The corresponding thin-film microstructures and morphologies were investigated by XRD and AFM to correlate with the OTFT performance. By strategically varying the oligothiophene donor conjugation length and optimizing the solubilizing side chains, a maximum OTFT hole mobility of ∼0.6 cm2 V-1 s-1 is achieved for P4-based devices. OTFT environmental (storage) and operational (bias) stability in ambient was investigated, and enhanced performance is observed due to the low-lying HOMOs. These results indicate that the TPD is an excellent building block for constructing high-performance polymers for p-type transistor applications due to the excellent processability, substantial hole mobility, and good device stability.",
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