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Electron transporting perylene diimide-based random terpolymers with variable co-monomer feed ratio: a route to all-polymer-based photodiodes

Electron transporting perylene diimide-based random terpolymers with variable co-monomer feed ratio: a route to all-polymer-based photodiodes
Electron transporting perylene diimide-based random terpolymers with variable co-monomer feed ratio: a route to all-polymer-based photodiodes

A route toward processable n-type terpolymers is presented herein based on the random donor-acceptor-donor-acceptor (D-A1)-(D-A2) molecular configuration. Carbazole is utilized as the electron donating unit (D) combined with perylene diimide (PDI) as the first electron acceptor (A1) and either one of two different benzothiadiazole (BTZ) derivatives (di-thienyl substituted-BTZ and di-3,4-ethylenedioxythienyl substituted-BTZ) as the second electron accepting unit (A2). Increasing the content of the PDI co-monomer resulted in terpolymers of higher molecular weights, enhanced solubility, and stronger n-type character. The physicochemical properties of the random PDI-Cz-BTZ derivatives are fine-tuned based on the feed ratio of the co-monomers. Photodiode devices were demonstrated, having photoactive layers composed of the rich in PDI terpolymer, namely, P4 having a 75% PDI content, and the PCE10 electron donor, under various ratios. For a range of P4 blend compositions, UV-Vis, is spectroscopy confirmed the strong absorption of the blend films across the 350-800 nm spectral region, and AFM imaging verified their low surface roughness. The study of the electro-optical device properties identified the 1:2 blending ratio as the optimum PCE10:P4 combination for maximum charge photogeneration efficiency. Despite the relatively deep LUMO energy of the n-type P4 terpolymer (ELUMO = -4.04 eV), trap-induced charge recombination losses were found to limit the PCE10:P4 photodiode performance. Unipolar devices of the P4-alone exhibited hole and electron mobility values of 2.2 × 10-4 and 6.3 × 10-5 cm2 V-1 s-1, respectively.

672-683
Aivali, Stefania
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Yuan, Peisen
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Panidi, Ioulianna
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Georgiadou, Dimitra
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Prodromakis, Themistoklis
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Kallitsis, Joannis
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Keivanidis, Panagiotis
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Andreopoulou, Aikaterini
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Aivali, Stefania
d572ecab-9d5c-4356-b87a-33f55a59e1d6
Yuan, Peisen
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Panidi, Ioulianna
c98ba267-2648-4fc7-804d-f4cb95bf2484
Georgiadou, Dimitra
84977176-3678-4fb3-a3dd-2044a49c853b
Prodromakis, Themistoklis
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Kallitsis, Joannis
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Keivanidis, Panagiotis
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Andreopoulou, Aikaterini
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Aivali, Stefania, Yuan, Peisen, Panidi, Ioulianna, Georgiadou, Dimitra, Prodromakis, Themistoklis, Kallitsis, Joannis, Keivanidis, Panagiotis and Andreopoulou, Aikaterini (2022) Electron transporting perylene diimide-based random terpolymers with variable co-monomer feed ratio: a route to all-polymer-based photodiodes. Macromolecules, 55 (2), 672-683. (doi:10.1021/acs.macromol.1c02159).

Record type: Article

Abstract

A route toward processable n-type terpolymers is presented herein based on the random donor-acceptor-donor-acceptor (D-A1)-(D-A2) molecular configuration. Carbazole is utilized as the electron donating unit (D) combined with perylene diimide (PDI) as the first electron acceptor (A1) and either one of two different benzothiadiazole (BTZ) derivatives (di-thienyl substituted-BTZ and di-3,4-ethylenedioxythienyl substituted-BTZ) as the second electron accepting unit (A2). Increasing the content of the PDI co-monomer resulted in terpolymers of higher molecular weights, enhanced solubility, and stronger n-type character. The physicochemical properties of the random PDI-Cz-BTZ derivatives are fine-tuned based on the feed ratio of the co-monomers. Photodiode devices were demonstrated, having photoactive layers composed of the rich in PDI terpolymer, namely, P4 having a 75% PDI content, and the PCE10 electron donor, under various ratios. For a range of P4 blend compositions, UV-Vis, is spectroscopy confirmed the strong absorption of the blend films across the 350-800 nm spectral region, and AFM imaging verified their low surface roughness. The study of the electro-optical device properties identified the 1:2 blending ratio as the optimum PCE10:P4 combination for maximum charge photogeneration efficiency. Despite the relatively deep LUMO energy of the n-type P4 terpolymer (ELUMO = -4.04 eV), trap-induced charge recombination losses were found to limit the PCE10:P4 photodiode performance. Unipolar devices of the P4-alone exhibited hole and electron mobility values of 2.2 × 10-4 and 6.3 × 10-5 cm2 V-1 s-1, respectively.

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ma-2021-02159x.R1_Proof_hi - Accepted Manuscript
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Accepted/In Press date: 21 December 2021
e-pub ahead of print date: 3 January 2022
Published date: 25 January 2022
Additional Information: Funding Information: S.A. was financially supported by General Secretariat for Research and Technology (GSRT) and the Hellenic Foundation for Research and Innovation (H.F.R.I) Code: 2358. J.D, D.G.G., and T.P. acknowledge the support of EPSRC Programme Grant FORTE (EP/R024642/1) and the RAEng Chair in Emerging Technologies (CiET1819/2/93). Publisher Copyright: © 2022 American Chemical Society. Copyright: Copyright 2022 Elsevier B.V., All rights reserved.

Identifiers

Local EPrints ID: 456117
URI: http://eprints.soton.ac.uk/id/eprint/456117
PURE UUID: d1e0e37c-90b1-4fbd-a1cb-daa1ba4cbbf3
ORCID for Dimitra Georgiadou: ORCID iD orcid.org/0000-0002-2620-3346
ORCID for Themistoklis Prodromakis: ORCID iD orcid.org/0000-0002-6267-6909

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Date deposited: 26 Apr 2022 14:53
Last modified: 03 Jan 2023 05:01

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Contributors

Author: Stefania Aivali
Author: Peisen Yuan
Author: Ioulianna Panidi
Author: Themistoklis Prodromakis ORCID iD
Author: Joannis Kallitsis
Author: Panagiotis Keivanidis
Author: Aikaterini Andreopoulou

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