Optical and Electrophysical Properties of Vinylidene Fluoride/Hexafluoropropylene Ferroelectric Copolymer Films: Effect of Doping with Porphyrin Derivatives
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 spec...
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2023-01-01
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| author | Valentin V. Kochervinskii Margaret A. Gradova Oleg V. Gradov Andrey I. Sergeev Anton V. Lobanov Evgeniya L. Buryanskaya Tatiana S. Ilina Dmitry A. Kiselev Inna A. Malyshkina Gayane A. Kirakosyan |
| author_facet | Valentin V. Kochervinskii Margaret A. Gradova Oleg V. Gradov Andrey I. Sergeev Anton V. Lobanov Evgeniya L. Buryanskaya Tatiana S. Ilina Dmitry A. Kiselev Inna A. Malyshkina Gayane A. Kirakosyan |
| author_sort | Valentin V. Kochervinskii |
| collection | DOAJ |
| description | 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<sup>−</sup> and T<sub>3</sub>GT<sub>3</sub>G<sup>−</sup> 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 <i>d</i><sub>33</sub> measurements. |
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| last_indexed | 2024-03-11T09:31:10Z |
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| series | Nanomaterials |
| spelling | doaj.art-39cd49b3e7aa453e8721389d6282b9632023-11-16T17:36:37ZengMDPI AGNanomaterials2079-49912023-01-0113356410.3390/nano13030564Optical and Electrophysical Properties of Vinylidene Fluoride/Hexafluoropropylene Ferroelectric Copolymer Films: Effect of Doping with Porphyrin DerivativesValentin V. Kochervinskii0Margaret A. Gradova1Oleg V. Gradov2Andrey I. Sergeev3Anton V. Lobanov4Evgeniya L. Buryanskaya5Tatiana S. Ilina6Dmitry A. Kiselev7Inna A. Malyshkina8Gayane A. Kirakosyan9Laboratory of Polymer Composite Materials, JSC Scientific Research Institute of Chemical Technology, Moscow 111524, RussiaN.N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, Moscow 119991, RussiaN.N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, Moscow 119991, RussiaN.N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, Moscow 119991, RussiaN.N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, Moscow 119991, RussiaN.N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, Moscow 119991, RussiaLaboratory of Physics of Oxide Ferroelectrics, Department of Materials Science of Semiconductors and Dielectrics, National University of Science and Technology MISIS, Moscow 119049, RussiaLaboratory of Physics of Oxide Ferroelectrics, Department of Materials Science of Semiconductors and Dielectrics, National University of Science and Technology MISIS, Moscow 119049, RussiaFaculty of Physics, M.V. Lomonosov Moscow State University, Moscow 119991, RussiaLaboratory of Coordination Chemistry of Alkali and Rare Metals, N.S. Kurnakov Institute of General and Inorganic Chemistry RAS, Moscow 119991, RussiaPolymer 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<sup>−</sup> and T<sub>3</sub>GT<sub>3</sub>G<sup>−</sup> 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 <i>d</i><sub>33</sub> measurements.https://www.mdpi.com/2079-4991/13/3/564polymersferroelectricityporphyrinspiezoelectricityconductivityrelaxation |
| spellingShingle | Valentin V. Kochervinskii Margaret A. Gradova Oleg V. Gradov Andrey I. Sergeev Anton V. Lobanov Evgeniya L. Buryanskaya Tatiana S. Ilina Dmitry A. Kiselev Inna A. Malyshkina Gayane A. Kirakosyan Optical and Electrophysical Properties of Vinylidene Fluoride/Hexafluoropropylene Ferroelectric Copolymer Films: Effect of Doping with Porphyrin Derivatives Nanomaterials polymers ferroelectricity porphyrins piezoelectricity conductivity relaxation |
| title | Optical and Electrophysical Properties of Vinylidene Fluoride/Hexafluoropropylene Ferroelectric Copolymer Films: Effect of Doping with Porphyrin Derivatives |
| title_full | Optical and Electrophysical Properties of Vinylidene Fluoride/Hexafluoropropylene Ferroelectric Copolymer Films: Effect of Doping with Porphyrin Derivatives |
| title_fullStr | Optical and Electrophysical Properties of Vinylidene Fluoride/Hexafluoropropylene Ferroelectric Copolymer Films: Effect of Doping with Porphyrin Derivatives |
| title_full_unstemmed | Optical and Electrophysical Properties of Vinylidene Fluoride/Hexafluoropropylene Ferroelectric Copolymer Films: Effect of Doping with Porphyrin Derivatives |
| title_short | Optical and Electrophysical Properties of Vinylidene Fluoride/Hexafluoropropylene Ferroelectric Copolymer Films: Effect of Doping with Porphyrin Derivatives |
| title_sort | optical and electrophysical properties of vinylidene fluoride hexafluoropropylene ferroelectric copolymer films effect of doping with porphyrin derivatives |
| topic | polymers ferroelectricity porphyrins piezoelectricity conductivity relaxation |
| url | https://www.mdpi.com/2079-4991/13/3/564 |
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