. 2021 Apr 28;7(18):eabe5280.

doi: 10.1126/sciadv.abe5280. Print 2021 Apr.

Charge transport physics of a unique class of rigid-rod conjugated polymers with fused-ring conjugated units linked by double carbon-carbon bonds

Mingfei Xiao¹, Remington L Carey¹, Hu Chen², Xuechen Jiao^{3

4}, Vincent Lemaur⁵, Sam Schott¹, Mark Nikolka¹, Cameron Jellett⁶, Aditya Sadhanala^{1

7}, Sarah Rogers⁸, Satyaprasad P Senanayak^{1

9}, Ada Onwubiko⁶, Sanyang Han¹, Zhilong Zhang¹, Mojtaba Abdi-Jalebi^{1

10}, Youcheng Zhang¹, Tudor H Thomas¹, Najet Mahmoudi⁸, Lianglun Lai^{1

11}, Ekaterina Selezneva¹, Xinglong Ren¹, Malgorzata Nguyen¹, Qijing Wang¹, Ian Jacobs¹, Wan Yue¹², Christopher R McNeill³, Guoming Liu^{1

13

14}, David Beljonne⁵, Iain McCulloch^{2

6}, Henning Sirringhaus¹⁵

Affiliations

¹ Optoelectronics Group, Cavendish Laboratory, JJ Thomson Avenue, Cambridge CB3 0HE, UK.
² KSC, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia.
³ Department of Materials Science and Engineering, Monash University, Clayton, Victoria 3800, Australia.
⁴ Australian Synchrotron, 800 Blackburn Road, Clayton, VIC 3168, Australia.
⁵ Laboratory for Chemistry of Novel Materials, University of Mons, BE-7000 Mons, Belgium.
⁶ Department of Chemistry, Imperial College London, South Kensington SW7 2AZ, UK.
⁷ Centre for Nano Science and Engineering, Indian Institute of Science, Bangalore 560012, India.
⁸ ISIS Pulsed Neutron Source, Rutherford Appleton Laboratory, Didcot OX11 0QX, UK.
⁹ School of Physical Sciences, National Institute of Science Education and Research, HBNI, Jatni 752050, India.
¹⁰ Institute for Materials Discovery, University College London, Torrington Place, London WC1E 7JE, UK.
¹¹ Cambridge Graphene Centre, University of Cambridge, Cambridge CB3 0FA, UK.
¹² Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education, School of Materials Science and Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
¹³ Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Engineering Plastics, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
¹⁴ University of Chinese Academy of Sciences, Beijing 100049, China.
¹⁵ Optoelectronics Group, Cavendish Laboratory, JJ Thomson Avenue, Cambridge CB3 0HE, UK. hs220@cam.ac.uk.

PMID: 33910909
PMCID: PMC8081371
DOI: 10.1126/sciadv.abe5280

Charge transport physics of a unique class of rigid-rod conjugated polymers with fused-ring conjugated units linked by double carbon-carbon bonds

Mingfei Xiao et al. Sci Adv. 2021.

. 2021 Apr 28;7(18):eabe5280.

doi: 10.1126/sciadv.abe5280. Print 2021 Apr.

Authors

Affiliations

¹ Optoelectronics Group, Cavendish Laboratory, JJ Thomson Avenue, Cambridge CB3 0HE, UK.
² KSC, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia.
³ Department of Materials Science and Engineering, Monash University, Clayton, Victoria 3800, Australia.
⁴ Australian Synchrotron, 800 Blackburn Road, Clayton, VIC 3168, Australia.
⁵ Laboratory for Chemistry of Novel Materials, University of Mons, BE-7000 Mons, Belgium.
⁶ Department of Chemistry, Imperial College London, South Kensington SW7 2AZ, UK.
⁷ Centre for Nano Science and Engineering, Indian Institute of Science, Bangalore 560012, India.
⁸ ISIS Pulsed Neutron Source, Rutherford Appleton Laboratory, Didcot OX11 0QX, UK.
⁹ School of Physical Sciences, National Institute of Science Education and Research, HBNI, Jatni 752050, India.
¹⁰ Institute for Materials Discovery, University College London, Torrington Place, London WC1E 7JE, UK.
¹¹ Cambridge Graphene Centre, University of Cambridge, Cambridge CB3 0FA, UK.
¹² Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education, School of Materials Science and Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
¹³ Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Engineering Plastics, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
¹⁴ University of Chinese Academy of Sciences, Beijing 100049, China.
¹⁵ Optoelectronics Group, Cavendish Laboratory, JJ Thomson Avenue, Cambridge CB3 0HE, UK. hs220@cam.ac.uk.

PMID: 33910909
PMCID: PMC8081371
DOI: 10.1126/sciadv.abe5280

Abstract

We investigate the charge transport physics of a previously unidentified class of electron-deficient conjugated polymers that do not contain any single bonds linking monomer units along the backbone but only double-bond linkages. Such polymers would be expected to behave as rigid rods, but little is known about their actual chain conformations and electronic structure. Here, we present a detailed study of the structural and charge transport properties of a family of four such polymers. By adopting a copolymer design, we achieve high electron mobilities up to 0.5 cm² V^-1 s^-1 Field-induced electron spin resonance measurements of charge dynamics provide evidence for relatively slow hopping over, however, long distances. Our work provides important insights into the factors that limit charge transport in this unique class of polymers and allows us to identify molecular design strategies for achieving even higher levels of performance.

Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).

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Figures

**Fig. 1. Chemical structures and thin-film UV-Vis-NIR absorption spectra.**
(A) Chemical structure of NN1, NN2, AN1, AN2, and P(NDI2OD-T2) polymers. (B) Thin-film UV-Vis-NIR absorption spectra of the polymers. The films were spun from hot 1,2,4-trichlorobenzene solution.

**Fig. 2. SANS of NN1, NN2, AN2, and P(NDI2OD-T2) in hot, dichlorobenzene solution.**
The NN1, NN2, and AN2 fused polymers adopt a rigid-rod shape with a scaling of I ≈ q⁻¹ over a large region, while the semiflexible P(NDI2OD-T2) polymer shows a characteristic worm-like chain behavior. The curves have been shifted vertically for clarity. The incoherent scattering background was subtracted.

**Fig. 3. Structural characterization of the representative rigid-rod polymer thin films.**
(A) 2D GIWAXS patterns of NN1, NN2, and AN2 thin-film samples. (B) In-plane and out-of-plane 1D linecuts of NN1, NN2, and AN2’s 2D GIWAXS patterns.

**Fig. 4. PDS of rigid-rod polymer thin films.**
Absorbance of the NN1, NN2, AN1, and AN2 thin films measured by PDS. Dotted lines represent exponential tail fits for extraction of the Urbach energies E_u (inset).

**Fig. 5. Temperature-dependent and molecular weight–dependent charge transport investigation of rigid-rod polymer FETs.**
(A) Transfer curves measured on top-gate, bottom-contact FETs (L = 20 μm, W = 1 mm) fabricated from the spin-coated AN2 film. (B) Linear and saturation mobility extracted from transfer curves measured on the same device. (C) Molecular weight–dependent saturation mobility for spin-coated NN1, NN2, AN1, and AN2 top-gate, bottom-contact FETs (L = 20 μm, W = 1 mm). (D) Temperature-dependent saturation electron mobility (at V_G = 60 V, V_D = 60 V) for spin-coated NN1, NN2, AN1, and AN2 top-gate, bottom-contact FETs (L = 20 μm, W = 1 mm).

**Fig. 6. Environmental and stress stability investigation of rigid-rod polymer FETs.**
(A) Saturation electron mobility of NN1, NN2, AN1, AN2, and P(NDI2OD-T2) top-gate, bottom-contact OFETs (L = 20 μm, W = 1 mm) measured under various air exposure time, highlighting the air stability of electron transport of fused polymer OFETs in comparison to the P(NDI2OD-T2) OFET. (B) Saturation transfer curves (with p- and n-channel accumulation) for a representative AN2 OFET measured in the air after 450-hour continuous air exposure to demonstrate the operational stability of the sufficiently air-exposed device.

**Fig. 7. FI-ESR characterization of rigid-rod polymers.**
FI-ESR spectra of the top-gate, bottom-contact sample (L = 100 μm, W = 243 mm) fabricated from spin-coated (A) NN1 and (D) AN2 film at 5 and 170 K. Spin lifetimes T₁ and T₂ for electron polarons in (B) NN1 and (E) AN2 FI-ESR sample at V_G = 60 V. Motion frequency of charges determined from T₂ (left axis) and saturation mobilities from FET measurements at V_G = 60 V (right axis) of (C) NN1 and (F) AN2 FI-ESR samples. Labels show the calculated hopping distances in the motional narrowing regime by relating the motion frequency and saturation electron mobility with the Einstein relation for charge transport.

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Charge transport physics of a unique class of rigid-rod conjugated polymers with fused-ring conjugated units linked by double carbon-carbon bonds

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Charge transport physics of a unique class of rigid-rod conjugated polymers with fused-ring conjugated units linked by double carbon-carbon bonds

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