Tuning the synthesis of fully conjugated block copolymers to minimize architectural heterogeneity

Youngmin Lee, Melissa P. Aplan, Zach D. Seibers, S. Michael Kilbey, Qing Wang, Enrique D. Gomez

Research output: Contribution to journalArticlepeer-review

18 Scopus citations


Conjugated block copolymers simultaneously control the mesoscale morphology and interfacial structure of the active layer in organic electronic devices. Fully conjugated block copolymers, where both backbones are conjugated, are commonly synthesized in two steps. First, poly(3-alkylthiophene-2,5-diyl) (P3HT) is synthesized by Kumada catalyst transfer/Grignard metathesis polymerization. The second block, typically a push-pull alternating copolymer, is added on to the P3HT macroreagent in a chain-extension reaction using either a Suzuki or a Stille polycondensation. Consequently, products can be a mixture of homopolymers, diblock copolymers, and multi-block copolymers. We demonstrate the optimum reaction conditions for the two-step synthesis of poly(3-hexylthiophene-2,5-diyl)-block-poly((9,9-bis-(2-octyl)fluorene-2,7-diyl)-alt-(4,7-di(thiophene-2-yl)-2,1,3-benzothiadiazole)-5′,5′′-diyl) (P3HT-b-PFTBT), a block copolymer that can be used as the sole active-layer material in organic photovoltaic devices. In the first reaction, preventing excess Grignard reagent to avert excess in the stoichiometry between Grignard reagent and monomer ensures end-group control of the P3HT macroreagent. In the second reaction, asymmetric monomer feed ratios with excess fluorene promotes coupling of PFTBT to P3HT. Using P3HT-b-PFTBT as an example, we demonstrate the synthetic parameters that are important to produce diblock copolymers with minimal impurities. This, in turn, promotes microphase separation in block copolymer films and leads to enhanced power conversion efficiencies in block copolymer solar cell devices.

Original languageEnglish (US)
Pages (from-to)20412-20421
Number of pages10
JournalJournal of Materials Chemistry A
Issue number38
StatePublished - 2017

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Renewable Energy, Sustainability and the Environment
  • Materials Science(all)


Dive into the research topics of 'Tuning the synthesis of fully conjugated block copolymers to minimize architectural heterogeneity'. Together they form a unique fingerprint.

Cite this