TY - JOUR
T1 - Buta-1,3-diyne-Based π-Conjugated Polymers for Organic Transistors and Solar Cells
AU - Eckstein, Brian J.
AU - Melkonyan, Ferdinand S.
AU - Zhou, Nanjia
AU - Manley, Eric F.
AU - Smith, Jeremy
AU - Timalsina, Amod
AU - Chang, Robert P.H.
AU - Chen, Lin X.
AU - Facchetti, Antonio
AU - Marks, Tobin J.
N1 - Funding Information:
For characterization facilities we thank the Northwestern University Materials Research Science and Engineering Center under NSF Grant DMR-1121262 and the Integrated Molecular Structure Education and Research Center (IMSERC) supported by Northwestern University, NSF, under Grants CHE- 0923236 and CHE-9871268, Pfizer, and the State of Illinois. Use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract DE-AC02- 06CH11357. The microscopy work was performed in the EPIC facility of the NUANCE Center at Northwestern University, which is supported by NSF-NSEC, NSF-MRSEC, the Keck Foundation, the State of Illinois, and Northwestern University.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/2/28
Y1 - 2017/2/28
N2 - 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 −CC-CC- 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 −CC-CC- 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.
AB - 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 −CC-CC- 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 −CC-CC- 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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U2 - 10.1021/acs.macromol.6b02702
DO - 10.1021/acs.macromol.6b02702
M3 - Article
AN - SCOPUS:85014084312
VL - 50
SP - 1430
EP - 1441
JO - Macromolecules
JF - Macromolecules
SN - 0024-9297
IS - 4
ER -