Not All Aggregates Are Made the Same: Distinct Structures of Solution Aggregates Drastically Modulate Assembly Pathways, Morphology, and Electronic Properties of Conjugated Polymers

Xu, Zhuang; Park, Kyung Sun; Kwok, Justin J.; Lin, Oliver; Patel, Bijal B.; Kafle, Prapti; Davies, Daniel W.; Chen, Qian; Diao, Ying

doi:10.1002/adma.202203055

Not All Aggregates Are Made the Same: Distinct Structures of Solution Aggregates Drastically Modulate Assembly Pathways, Morphology, and Electronic Properties of Conjugated Polymers

Journal Article · Mon Jul 11 00:00:00 EDT 2022 · Advanced Materials

DOI:https://doi.org/10.1002/adma.202203055· OSTI ID:1875593

Xu, Zhuang ^[1]; Park, Kyung Sun ^[2]; Kwok, Justin J. ^[3]; Lin, Oliver ^[1]; Patel, Bijal B. ^[2]; Kafle, Prapti ^[2]; Davies, Daniel W. ^[2]; Chen, Qian ^[4]; ^[4]

Department of Chemistry University of Illinois at Urbana‐Champaign 600 S. Mathews Avenue Urbana IL 61801 USA
Department of Chemical and Biomolecular Engineering University of Illinois at Urbana‐Champaign 600 S. Mathews Avenue Urbana IL 61801 USA
Department of Materials Science and Engineering University of Illinois at Urbana‐Champaign 1304 W. Green Street Urbana IL 61801 USA
Department of Chemistry University of Illinois at Urbana‐Champaign 600 S. Mathews Avenue Urbana IL 61801 USA; Department of Chemical and Biomolecular Engineering University of Illinois at Urbana‐Champaign 600 S. Mathews Avenue Urbana IL 61801 USA; Department of Materials Science and Engineering University of Illinois at Urbana‐Champaign 1304 W. Green Street Urbana IL 61801 USA; Materials Research Laboratory University of Illinois at Urbana‐Champaign 104 South Goodwin Avenue; MC‐230 Urbana IL 61801 USA; Beckman Institute for Advanced Science and Technology University of Illinois at Urbana‐Champaign 405 N. Mathews Avenue Urbana IL 61801 USA

Abstract

Tuning structures of solution‐state aggregation and aggregation‐mediated assembly pathways of conjugated polymers is crucial for optimizing their solid‐state morphology and charge‐transport property. However, it remains challenging to unravel and control the exact structures of solution aggregates, let alone to modulate assembly pathways in a controlled fashion. Herein, aggregate structures of an isoindigo–bithiophene‐based polymer (PII‐2T) are modulated by tuning selectivity of the solvent toward the side chain versus the backbone, which leads to three distinct assembly pathways: direct crystallization from side‐chain‐associated amorphous aggregates, chiral liquid crystal (LC)‐mediated assembly from semicrystalline aggregates with side‐chain and backbone stacking, and random agglomeration from backbone‐stacked semicrystalline aggregates. Importantly, it is demonstrated that the amorphous solution aggregates, compared with semicrystalline ones, lead to significantly improved alignment and reduced paracrystalline disorder in the solid state due to direct crystallization during the meniscus‐guided coating process. Alignment quantified by the dichroic ratio is enhanced by up to 14‐fold, and the charge‐carrier mobility increases by a maximum of 20‐fold in films printed from amorphous aggregates compared to those from semicrystalline aggregates. This work shows that by tuning the precise structure of solution aggregates, the assembly pathways and the resulting thin‐film morphology and device properties can be drastically tuned.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: US Air Force Office of Scientific Research (AFOSR); US Department of the Navy, Office of Naval Research (ONR); USDOE; USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1875593

Alternate ID(s):: OSTI ID: 1875594
OSTI ID: 1981357

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Journal Issue: 32 Vol. 34; ISSN 0935-9648

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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