Ferroelectric polymers exhibiting behaviour reminiscent of a morphotropic phase boundary

Yang Liu, Haibibu Aziguli, Bing Zhang, Wenhan Xu, Wenchang Lu, J. Bernholc, Qing Wang

Research output: Contribution to journalLetter

17 Citations (Scopus)

Abstract

Piezoelectricity—the direct interconversion between mechanical and electrical energies—is usually remarkably enhanced at the morphotropic phase boundary of ferroelectric materials 1–4 , which marks a transition region in the phase diagram of piezoelectric materials and bridges two competing phases with distinct symmetries 1,5 . Such enhancement has enabled the recent development of various lead and lead-free piezoelectric perovskites with outstanding piezoelectric properties for use in actuators, transducers, sensors and energy-harvesting applications 5–8 . However, the morphotropic phase boundary has never been observed in organic materials, and the absence of effective approaches to improving the intrinsic piezoelectric responses of polymers 9,10 considerably hampers their application to flexible, wearable and biocompatible devices. Here we report stereochemically induced behaviour in ferroelectric poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) copolymers, which is similar to that observed at morphotropic phase boundaries in perovskites. We reveal that compositionally tailored tacticity (the stereochemical arrangement of chiral centres related to the TrFE monomers 11,12 ) can lead to intramolecular order-to-disorder evolution in the crystalline phase and thus to an intermediate transition region that is reminiscent of the morphotropic phase boundary, where competing ferroelectric and relaxor properties appear simultaneously. Our first-principles calculations confirm the crucial role of chain tacticity in driving the formation of this transition region via structural competition between the trans-planar and 3/1-helical phases. We show that the P(VDF-TrFE) copolymer with the morphotropic composition exhibits a longitudinal piezoelectric coefficient of −63.5 picocoulombs per newton, outperforming state-of-the-art piezoelectric polymers 10 . Given the flexibility in the molecular design and synthesis of organic ferroelectric materials, this work opens up the way for the development of scalable, high-performance piezoelectric polymers.

Original languageEnglish (US)
Pages (from-to)96-100
Number of pages5
JournalNature
Volume562
Issue number7725
DOIs
StatePublished - Oct 4 2018

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Polymers
Synthetic Chemistry Techniques
Transducers
Equipment and Supplies
polyvinylidene fluoride
Lead
vinylidene fluoride-trifluoroethylene copolymer

All Science Journal Classification (ASJC) codes

  • General

Cite this

Liu, Yang ; Aziguli, Haibibu ; Zhang, Bing ; Xu, Wenhan ; Lu, Wenchang ; Bernholc, J. ; Wang, Qing. / Ferroelectric polymers exhibiting behaviour reminiscent of a morphotropic phase boundary. In: Nature. 2018 ; Vol. 562, No. 7725. pp. 96-100.
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abstract = "Piezoelectricity—the direct interconversion between mechanical and electrical energies—is usually remarkably enhanced at the morphotropic phase boundary of ferroelectric materials 1–4 , which marks a transition region in the phase diagram of piezoelectric materials and bridges two competing phases with distinct symmetries 1,5 . Such enhancement has enabled the recent development of various lead and lead-free piezoelectric perovskites with outstanding piezoelectric properties for use in actuators, transducers, sensors and energy-harvesting applications 5–8 . However, the morphotropic phase boundary has never been observed in organic materials, and the absence of effective approaches to improving the intrinsic piezoelectric responses of polymers 9,10 considerably hampers their application to flexible, wearable and biocompatible devices. Here we report stereochemically induced behaviour in ferroelectric poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) copolymers, which is similar to that observed at morphotropic phase boundaries in perovskites. We reveal that compositionally tailored tacticity (the stereochemical arrangement of chiral centres related to the TrFE monomers 11,12 ) can lead to intramolecular order-to-disorder evolution in the crystalline phase and thus to an intermediate transition region that is reminiscent of the morphotropic phase boundary, where competing ferroelectric and relaxor properties appear simultaneously. Our first-principles calculations confirm the crucial role of chain tacticity in driving the formation of this transition region via structural competition between the trans-planar and 3/1-helical phases. We show that the P(VDF-TrFE) copolymer with the morphotropic composition exhibits a longitudinal piezoelectric coefficient of −63.5 picocoulombs per newton, outperforming state-of-the-art piezoelectric polymers 10 . Given the flexibility in the molecular design and synthesis of organic ferroelectric materials, this work opens up the way for the development of scalable, high-performance piezoelectric polymers.",
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Liu, Y, Aziguli, H, Zhang, B, Xu, W, Lu, W, Bernholc, J & Wang, Q 2018, 'Ferroelectric polymers exhibiting behaviour reminiscent of a morphotropic phase boundary', Nature, vol. 562, no. 7725, pp. 96-100. https://doi.org/10.1038/s41586-018-0550-z

Ferroelectric polymers exhibiting behaviour reminiscent of a morphotropic phase boundary. / Liu, Yang; Aziguli, Haibibu; Zhang, Bing; Xu, Wenhan; Lu, Wenchang; Bernholc, J.; Wang, Qing.

In: Nature, Vol. 562, No. 7725, 04.10.2018, p. 96-100.

Research output: Contribution to journalLetter

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AB - Piezoelectricity—the direct interconversion between mechanical and electrical energies—is usually remarkably enhanced at the morphotropic phase boundary of ferroelectric materials 1–4 , which marks a transition region in the phase diagram of piezoelectric materials and bridges two competing phases with distinct symmetries 1,5 . Such enhancement has enabled the recent development of various lead and lead-free piezoelectric perovskites with outstanding piezoelectric properties for use in actuators, transducers, sensors and energy-harvesting applications 5–8 . However, the morphotropic phase boundary has never been observed in organic materials, and the absence of effective approaches to improving the intrinsic piezoelectric responses of polymers 9,10 considerably hampers their application to flexible, wearable and biocompatible devices. Here we report stereochemically induced behaviour in ferroelectric poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) copolymers, which is similar to that observed at morphotropic phase boundaries in perovskites. We reveal that compositionally tailored tacticity (the stereochemical arrangement of chiral centres related to the TrFE monomers 11,12 ) can lead to intramolecular order-to-disorder evolution in the crystalline phase and thus to an intermediate transition region that is reminiscent of the morphotropic phase boundary, where competing ferroelectric and relaxor properties appear simultaneously. Our first-principles calculations confirm the crucial role of chain tacticity in driving the formation of this transition region via structural competition between the trans-planar and 3/1-helical phases. We show that the P(VDF-TrFE) copolymer with the morphotropic composition exhibits a longitudinal piezoelectric coefficient of −63.5 picocoulombs per newton, outperforming state-of-the-art piezoelectric polymers 10 . Given the flexibility in the molecular design and synthesis of organic ferroelectric materials, this work opens up the way for the development of scalable, high-performance piezoelectric polymers.

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Liu Y, Aziguli H, Zhang B, Xu W, Lu W, Bernholc J et al. Ferroelectric polymers exhibiting behaviour reminiscent of a morphotropic phase boundary. Nature. 2018 Oct 4;562(7725):96-100. https://doi.org/10.1038/s41586-018-0550-z