TY - JOUR
T1 - Processable High Electron Mobility π-Copolymers via Mesoscale Backbone Conformational Ordering
AU - Eckstein, Brian J.
AU - Melkonyan, Ferdinand S.
AU - Wang, Gang
AU - Wang, Binghao
AU - Manley, Eric F.
AU - Fabiano, Simone
AU - Harbuzaru, Alexandra
AU - Ponce Ortiz, Rocio
AU - Chen, Lin X.
AU - Facchetti, Antonio
AU - Marks, Tobin J.
N1 - Funding Information:
This research was supported by the Center for Light Energy Activated Redox Processes (LEAP), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award DE-SC0001059 (B.J.E., L.X.C. copolymer synthesis, characterization), by AFOSR grant FA9550-18-1-0044 (A.F., synthetic design), and by the Department of Energy under contract no. DE-AC02-05CH11231, and at beamline 8-ID-E of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. F.S.M. and G.W. were supported by award 70NANB14H012 from U.S. Department of Commerce, National Institute of Standards and Technology, as part of the Center for Hierarchical Materials Design (CHiMaD), and E.F.M. by Qatar NPRP grant 7286-1-046 (GIWAXS). A.F. thanks the Shenzhen Peacock Plan project (KQTD-20140630110339343) for financial support. S.F. thanks VINNOVA (2015-04859) and the Swedish Research Council (2016-03979) for financial support. Finally, B.J.E. thanks J.N.E. for invaluable support and discussion. This work made use of the MatCI Facility which receives support from the MRSEC Program (NSF DMR- 1720139) of the Materials Research Center at Northwestern University. The authors thank the Integrated Molecular Structure Education and Research Center (IMSERC) for characterization facilities supported by Northwestern University, National Science Foundation (NSF) under NSF CHE-1048773, Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205), the State of Illinois, and International Institute for Nanotechnology (IIN). The work at University of Malaga was financially supported by Junta de Andaluc?a (projects UMA18-FEDERJA-080 and P18-FR-4559) and MICINN (project PID2019-110305GB-I00).
Funding Information:
This research was supported by the Center for Light Energy Activated Redox Processes (LEAP), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award DE‐SC0001059 (B.J.E., L.X.C. copolymer synthesis, characterization), by AFOSR grant FA9550‐18‐1‐0044 (A.F., synthetic design), and by the Department of Energy under contract no. DE‐AC02‐05CH11231, and at beamline 8‐ID‐E of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE‐AC02‐06CH11357. F.S.M. and G.W. were supported by award 70NANB14H012 from U.S. Department of Commerce, National Institute of Standards and Technology, as part of the Center for Hierarchical Materials Design (CHiMaD), and E.F.M. by Qatar NPRP grant 7286‐1‐046 (GIWAXS). A.F. thanks the Shenzhen Peacock Plan project (KQTD‐20140630110339343) for financial support. S.F. thanks VINNOVA (2015‐04859) and the Swedish Research Council (2016‐03979) for financial support. Finally, B.J.E. thanks J.N.E. for invaluable support and discussion. This work made use of the MatCI Facility which receives support from the MRSEC Program (NSF DMR‐ 1720139) of the Materials Research Center at Northwestern University. The authors thank the Integrated Molecular Structure Education and Research Center (IMSERC) for characterization facilities supported by Northwestern University, National Science Foundation (NSF) under NSF CHE‐1048773, Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI‐1542205), the State of Illinois, and International Institute for Nanotechnology (IIN). The work at University of Malaga was financially supported by Junta de Andalucía (projects UMA18‐FEDERJA‐080 and P18‐FR‐4559) and MICINN (project PID2019‐110305GB‐I00).
Publisher Copyright:
© 2021 Wiley-VCH GmbH
PY - 2021/4/8
Y1 - 2021/4/8
N2 - The synthesis and experimental/theoretical characterization of a new series of electron-transporting copolymers based on the naphthalene bis(4,8-diamino-1,5-dicarboxyl)amide (NBA) building block are reported. Comonomers are designed to test the emergent effects of manipulating backbone torsional characteristics, and density functional theory (DFT) analysis reveals the key role of backbone conformation in optimizing electronic delocalization and transport. The NBA copolymer conformational and electronic properties are characterized using a broad array of molecular/macromolecular, thermal, optical, electrochemical, and charge transport techniques. All NBA copolymers exhibit strongly aggregated morphologies with significant nanoscale order. Copolymer charge transport properties are investigated in thin-film transistors and exhibit excellent electron mobilities ranging from 0.4 to 4.5 cm2 V−1 s−1. Importantly, the electron transport efficiency correlates with the film mesoscale order, which emerges from comonomer-dependent backbone planarity and extension. These results illuminate the key NBA building block structure–morphology–bulk property design relationships essential for processable, electronics-applicable high-performance polymeric semiconductors.
AB - The synthesis and experimental/theoretical characterization of a new series of electron-transporting copolymers based on the naphthalene bis(4,8-diamino-1,5-dicarboxyl)amide (NBA) building block are reported. Comonomers are designed to test the emergent effects of manipulating backbone torsional characteristics, and density functional theory (DFT) analysis reveals the key role of backbone conformation in optimizing electronic delocalization and transport. The NBA copolymer conformational and electronic properties are characterized using a broad array of molecular/macromolecular, thermal, optical, electrochemical, and charge transport techniques. All NBA copolymers exhibit strongly aggregated morphologies with significant nanoscale order. Copolymer charge transport properties are investigated in thin-film transistors and exhibit excellent electron mobilities ranging from 0.4 to 4.5 cm2 V−1 s−1. Importantly, the electron transport efficiency correlates with the film mesoscale order, which emerges from comonomer-dependent backbone planarity and extension. These results illuminate the key NBA building block structure–morphology–bulk property design relationships essential for processable, electronics-applicable high-performance polymeric semiconductors.
KW - n-type transport
KW - organic transistors
KW - polymer semiconductors
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U2 - 10.1002/adfm.202009359
DO - 10.1002/adfm.202009359
M3 - Article
AN - SCOPUS:85100954576
VL - 31
JO - Advanced Functional Materials
JF - Advanced Functional Materials
SN - 1616-301X
IS - 15
M1 - 2009359
ER -