Electrochemical Polymerization of 6-(N-Allyl-1,1,2,2-tetrahydroperfluorodecyl)amino-1,3,5-triazine-2,4-dithiol Monosodium on Aluminum

Abstract

ABSTRACT:Polymer thin films are prepared by electrochemical polymerization of 6-(N-allyl-1,1,2,2-tetrahydroperfluorodecyl)amino-1,3,5-triazine-2,4-dithiol monosodium on an aluminum plate. The steric and chemical structures of films are characterized by optical ellipsometry, contact angle goniometry, Fourier transform infrared spectroscopy (FT-IR) and impedance spectroscopy. Polymer film thickness and potential applied to the films during electrochemical polymerization, a measure of packing density, increase proportionally to the square root of electrochemical polymerization time following a parabolic law. From FT-IR spectra of the polymer films formed on aluminum plates, only the C-F stretching vibration peak of CF 3 -groups at 1345 cm À1 is observed, indicating extremely oriented polymer thin film. C1s, N1s and S2p peaks in the XPS spectra indicate that the chemical structure of polymer thin film is poly(6-(N-allyl-1,1,2,2-tetrahydroperfluorodecyl)amino-1,3,5-triazine-2,4-disulfide) (PATP) and allyl, tetrahydroperfluorodecyl amino chain axes are perpendicular to the surface, but the triazine ring is aligned parallel to the surface. The contact angle of polymer thin films was 123, on which a top layer thought to be composed of CF 3 -groups exists. Polymer films on aluminum plates were used to produce parallel plate capacitors having capacitances of 1.33 to 2.06 mF/cm 2 . The dielectric constants of polymer films were calculated to range from 142 to 175, the highest reported for organic dielectrics to date. Nano-scale polymer films in polymer/metal assemblies are of special interest as microelectronics including capacitors. [8][9][10][11][12][13][14] Polymer thin films are mainly prepared by the Langmuir-Blodgett, 15,16 vacuum vapor deposition 17 and self-assembly 18 techniques. Langmuir-Blodgett and self-assembly techniques are very effective when highly ordered arranged monolayers are required, but functionalized compounds and specialized equipment are needed. However, in principle, these two techniques are not suitable on an industrial scale for preparing multilayer polymer thin films on complicated metal surfaces. In vapor-deposition, controlling the orientation and arrangement of films is difficult, but the techniques are suitable for the preparation of multilayer films on metal surfaces.The polymerization of extremely oriented ordered thin monomer films has been reported. 19,20 Electrochemical polymerization is very effective for preparing multilayer polymer films on complicated metal surfaces without functionalized compounds or specialized equipment. However, little attention has been paid to the formation of ordered and packing polymer films on metal surfaces by electrochemical polymerization. [21][22][23][24] In this paper, 6-(N-allyl-1,1,2,2-tetrahydroperfluorodecyl)amino-1,3,5-triazine-2,4-dithiol monosodium was polymerized electrochemically on aluminum plates and the chemical structures of polymer thin films were investigated. Parallel plate capacitors having high capacitance were made. EXPERIMENTAL M...

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