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Volume 13
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Article

Optical and Electrophysical Properties of Vinylidene Fluoride/Hexafluoropropylene Ferroelectric Copolymer Films: Effect of Doping with Porphyrin Derivatives

by
Valentin V. Kochervinskii
1,*,
Margaret A. Gradova
2,
Oleg V. Gradov
2,
Andrey I. Sergeev
2,
Anton V. Lobanov
2,
Evgeniya L. Buryanskaya
2,3,
Tatiana S. Ilina
3,
Dmitry A. Kiselev
3,
Inna A. Malyshkina
4,5 and
Gayane A. Kirakosyan
6,7
1
Laboratory of Polymer Composite Materials, JSC Scientific Research Institute of Chemical Technology, Moscow 111524, Russia
2
N.N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, Moscow 119991, Russia
3
Laboratory of Physics of Oxide Ferroelectrics, Department of Materials Science of Semiconductors and Dielectrics, National University of Science and Technology MISIS, Moscow 119049, Russia
4
Faculty of Physics, M.V. Lomonosov Moscow State University, Moscow 119991, Russia
5
Faculty of Fundamental Physical and Chemical Engineering, M.V. Lomonosov Moscow State University, Moscow 119991, Russia
6
Laboratory of Coordination Chemistry of Alkali and Rare Metals, N.S. Kurnakov Institute of General and Inorganic Chemistry RAS, Moscow 119991, Russia
7
A.N. Frumkin Institute of Physical Chemistry and Electrochemistry RAS, Moscow 119071, Russia
*
Author to whom correspondence should be addressed.
Nanomaterials 2023, 13(3), 564; https://doi.org/10.3390/nano13030564
Submission received: 26 November 2022 / Revised: 23 January 2023 / Accepted: 26 January 2023 / Published: 30 January 2023
(This article belongs to the Special Issue Advanced Polymers-Based Nanocomposites for Artificial Muscles-Like Actuators and Sensors)
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Abstract

Polymer films doped by different porphyrins, obtained by crystallization from the acetone solutions, differ in absorption and fluorescence spectra, which we attribute to the differences in the structuring and composition of the rotational isomers in the polymer chains. According to the infrared spectroscopy data, the crystallization of the films doped with tetraphenylporphyrin (TPP) proceeds in a mixture of α- and γ-phases with TGTG− and T3GT3G− conformations, respectively. Three bonds in the planar zigzag conformation ensures the contact of such segments with the active groups of the porphyrin macrocycle, significantly changing its electronic state. Structuring of the films in the presence of TPP leads to an increase in the low-voltage AC-conductivity and the registration of an intense Maxwell-Wagner polarization. An increased conductivity by an order of magnitude in TPP-doped films was also observed at high-voltage polarization. The introduction of TPP during the film formation promotes the displacement of the chemical attachment defects of “head-to-head” type in the monomeric units into the surface. This process is accompanied by a significant increase in the film surface roughness, which was registered by piezo-force microscopy. The latter method also revealed the appearance of hysteresis phenomena during the local piezoelectric coefficient d33 measurements.
Keywords: polymers; ferroelectricity; porphyrins; piezoelectricity; conductivity; relaxation polymers; ferroelectricity; porphyrins; piezoelectricity; conductivity; relaxation
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MDPI and ACS Style

Kochervinskii, V.V.; Gradova, M.A.; Gradov, O.V.; Sergeev, A.I.; Lobanov, A.V.; Buryanskaya, E.L.; Ilina, T.S.; Kiselev, D.A.; Malyshkina, I.A.; Kirakosyan, G.A. Optical and Electrophysical Properties of Vinylidene Fluoride/Hexafluoropropylene Ferroelectric Copolymer Films: Effect of Doping with Porphyrin Derivatives. Nanomaterials 2023, 13, 564. https://doi.org/10.3390/nano13030564

AMA Style

Kochervinskii VV, Gradova MA, Gradov OV, Sergeev AI, Lobanov AV, Buryanskaya EL, Ilina TS, Kiselev DA, Malyshkina IA, Kirakosyan GA. Optical and Electrophysical Properties of Vinylidene Fluoride/Hexafluoropropylene Ferroelectric Copolymer Films: Effect of Doping with Porphyrin Derivatives. Nanomaterials. 2023; 13(3):564. https://doi.org/10.3390/nano13030564

Chicago/Turabian Style

Kochervinskii, Valentin V., Margaret A. Gradova, Oleg V. Gradov, Andrey I. Sergeev, Anton V. Lobanov, Evgeniya L. Buryanskaya, Tatiana S. Ilina, Dmitry A. Kiselev, Inna A. Malyshkina, and Gayane A. Kirakosyan. 2023. "Optical and Electrophysical Properties of Vinylidene Fluoride/Hexafluoropropylene Ferroelectric Copolymer Films: Effect of Doping with Porphyrin Derivatives" Nanomaterials 13, no. 3: 564. https://doi.org/10.3390/nano13030564

APA Style

Kochervinskii, V. V., Gradova, M. A., Gradov, O. V., Sergeev, A. I., Lobanov, A. V., Buryanskaya, E. L., Ilina, T. S., Kiselev, D. A., Malyshkina, I. A., & Kirakosyan, G. A. (2023). Optical and Electrophysical Properties of Vinylidene Fluoride/Hexafluoropropylene Ferroelectric Copolymer Films: Effect of Doping with Porphyrin Derivatives. Nanomaterials, 13(3), 564. https://doi.org/10.3390/nano13030564

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