Polymorphism of a semi-crystalline diketopyrrolopyrrole-terthiophene polymer

Mengmeng Li (Corresponding author), Pieter J. Leenaers, Junyu Li, Martijn M. Wienk, René A.J. Janssen (Corresponding author)

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Few semiconducting polymers are known that possess more than one semi-crystalline structure. Guidelines for rationalizing or creating polymorphism in these materials do not exist. Two different semi-crystalline polymorphs, β1 and β2, and an amorphous α phase have recently been identified for alternating diketopyrrolopyrrole-quaterthiophene copolymers (PDPP4T). The polymorphs differ structurally by the π–π stacking distance, and electronically by the optical bandgap and charge carrier mobility. Here we investigate the corresponding terthiophene (PDPP3T) derivatives, to study the effect of the relative orientation of adjacent DPP units on the polymorphism. In PDPP3T, the relative orientation of DPP units alternates along the chain, while in PDPP4T it is constant. We show that the two polymorphs, β1 and β2, can also be generated for a PDPP3T polymer in solution and thin film. Interestingly, compared to PDPP4T, more solvents can induce the two distinct semi-crystalline polymorphs for PDPP3T via a β1 → α → β2 polymorphic transition.

Original languageEnglish
Pages (from-to)1285-1292
Number of pages8
JournalJournal of Polymer Science
Issue number12
Publication statusPublished - 15 Jun 2021


FP7 Ideas: European Research Council, Grant/Award Number: 339031; Ministerie van Onderwijs, Cultuur en Wetenschap, Grant/Award Number: 024.001.035; National Key R&D Program of China, Grant/Award Number: 2019YFA0706100; Nederlandse Organisatie voor Wetenschappelijk Onderzoek; National Natural Science Foundation of China, Grant/Award Number: 62074163 Funding information This work is supported by the National Key R&D Program of China (Grant No. 2019YFA0706100) and the National Natural Science Foundation of China (Grant No. 62074163). We further acknowledge funding from the Netherlands Organization for Scientific Research (016.Veni.192.106 and the NWO Spinoza prize) and the Ministry of Education, Culture and Science (Gravity program 024.001.035).

FundersFunder number
Ministerie van Onderwijs, Cultuur en Wetenschap024.001.035
Ministerie van Onderwijs, Cultuur en Wetenschap
Seventh Framework Programme339031
European Research Council
National Natural Science Foundation of China62074163
Ministerie van Onderwijs, Cultuur en Wetenschap
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
National Key Research and Development Program of China2019YFA0706100


    • aggregation
    • chain orientation
    • diketopyrrolopyrrole polymers
    • electronic devices
    • polymorphism


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