Buta-1,3-diyne-Based π-Conjugated Polymers for Organic Transistors and Solar Cells

Brian J. Eckstein, Ferdinand S. Melkonyan, Nanjia Zhou, Eric F. Manley, Jeremy Smith, Amod Timalsina, Robert P. H. Chang, Lin X. Chen, Antonio Facchetti, Tobin J Marks

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

We report the synthesis and characterization of new alkyl-substituted 1,4-di(thiophen-2-yl)buta-1,3-diyne (R-DTB) donor building blocks, based on the −CC-CC- conjugative pathway, and their incorporation with thienyl-diketopyrrolopyrrole (R'-TDPP) acceptor units into π-conjugated PTDPP-DTB polymers (P1-P4). The solubility of the new polymers strongly depends on the DTB and DPP solubilizing (R and R', respectively) substituents. Thus, solution processable and high molecular weight PDPP-DTB polymers are achieved for P3 (R = n-C12H25, R' = 2-butyloctyl) and P4 (R = 2-ethylhexyl, R' = 2-butyloctyl). Systematic studies of P3 and P4 physicochemical properties are carried using optical spectroscopy, cyclic voltammetry, and thermal analysis, revealing characteristic features of the dialkynyl motif. For the first time, optoelectronic devices (OFETs, OPVs) are fabricated with 1,3-butadiyne containing organic semiconductors. OFET hole mobilities and record OPV power conversion efficiencies for acetylenic organic materials approach 0.1 cm2/(V s) and 4%, respectively, which can be understood from detailed thin-film morphology and microstructural characterization using AFM, TEM, XRD, and GIWAXS methodologies. Importantly, DTB-based polymers (P3 and P4) exhibit, in addition to stabilization of frontier molecular orbitals and to −CC-CC- relief of steric torsions, discrete morphological pliability through thermal annealing and processing additives. The advantageous materials properties and preliminary device performance reported here demonstrate the promise of 1,3-butadiyne-based semiconducting polymers.

Original languageEnglish
Pages (from-to)1430-1441
Number of pages12
JournalMacromolecules
Volume50
Issue number4
DOIs
Publication statusPublished - Feb 28 2017

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Conjugated polymers
Solar cells
Polymers
Transistors
Organic field effect transistors
Semiconducting polymers
Hole mobility
Semiconducting organic compounds
Molecular orbitals
Optoelectronic devices
Torsional stress
Thermoanalysis
Conversion efficiency
Cyclic voltammetry
Materials properties
Stabilization
Solubility
Molecular weight
Annealing
Transmission electron microscopy

ASJC Scopus subject areas

  • Organic Chemistry
  • Materials Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry

Cite this

Eckstein, B. J., Melkonyan, F. S., Zhou, N., Manley, E. F., Smith, J., Timalsina, A., ... Marks, T. J. (2017). Buta-1,3-diyne-Based π-Conjugated Polymers for Organic Transistors and Solar Cells. Macromolecules, 50(4), 1430-1441. https://doi.org/10.1021/acs.macromol.6b02702

Buta-1,3-diyne-Based π-Conjugated Polymers for Organic Transistors and Solar Cells. / Eckstein, Brian J.; Melkonyan, Ferdinand S.; Zhou, Nanjia; Manley, Eric F.; Smith, Jeremy; Timalsina, Amod; Chang, Robert P. H.; Chen, Lin X.; Facchetti, Antonio; Marks, Tobin J.

In: Macromolecules, Vol. 50, No. 4, 28.02.2017, p. 1430-1441.

Research output: Contribution to journalArticle

Eckstein, BJ, Melkonyan, FS, Zhou, N, Manley, EF, Smith, J, Timalsina, A, Chang, RPH, Chen, LX, Facchetti, A & Marks, TJ 2017, 'Buta-1,3-diyne-Based π-Conjugated Polymers for Organic Transistors and Solar Cells', Macromolecules, vol. 50, no. 4, pp. 1430-1441. https://doi.org/10.1021/acs.macromol.6b02702
Eckstein BJ, Melkonyan FS, Zhou N, Manley EF, Smith J, Timalsina A et al. Buta-1,3-diyne-Based π-Conjugated Polymers for Organic Transistors and Solar Cells. Macromolecules. 2017 Feb 28;50(4):1430-1441. https://doi.org/10.1021/acs.macromol.6b02702
Eckstein, Brian J. ; Melkonyan, Ferdinand S. ; Zhou, Nanjia ; Manley, Eric F. ; Smith, Jeremy ; Timalsina, Amod ; Chang, Robert P. H. ; Chen, Lin X. ; Facchetti, Antonio ; Marks, Tobin J. / Buta-1,3-diyne-Based π-Conjugated Polymers for Organic Transistors and Solar Cells. In: Macromolecules. 2017 ; Vol. 50, No. 4. pp. 1430-1441.
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abstract = "We report the synthesis and characterization of new alkyl-substituted 1,4-di(thiophen-2-yl)buta-1,3-diyne (R-DTB) donor building blocks, based on the −CC-CC- conjugative pathway, and their incorporation with thienyl-diketopyrrolopyrrole (R'-TDPP) acceptor units into π-conjugated PTDPP-DTB polymers (P1-P4). The solubility of the new polymers strongly depends on the DTB and DPP solubilizing (R and R', respectively) substituents. Thus, solution processable and high molecular weight PDPP-DTB polymers are achieved for P3 (R = n-C12H25, R' = 2-butyloctyl) and P4 (R = 2-ethylhexyl, R' = 2-butyloctyl). Systematic studies of P3 and P4 physicochemical properties are carried using optical spectroscopy, cyclic voltammetry, and thermal analysis, revealing characteristic features of the dialkynyl motif. For the first time, optoelectronic devices (OFETs, OPVs) are fabricated with 1,3-butadiyne containing organic semiconductors. OFET hole mobilities and record OPV power conversion efficiencies for acetylenic organic materials approach 0.1 cm2/(V s) and 4{\%}, respectively, which can be understood from detailed thin-film morphology and microstructural characterization using AFM, TEM, XRD, and GIWAXS methodologies. Importantly, DTB-based polymers (P3 and P4) exhibit, in addition to stabilization of frontier molecular orbitals and to −CC-CC- relief of steric torsions, discrete morphological pliability through thermal annealing and processing additives. The advantageous materials properties and preliminary device performance reported here demonstrate the promise of 1,3-butadiyne-based semiconducting polymers.",
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AU - Smith, Jeremy

AU - Timalsina, Amod

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