Electrochemistry, Polymers And Opto-electronic Devices: A Combination With A Future

Electrochemistry came into life with the invention of the pile, by Volta in 1800. He combined different metal discs with a piece of tissue, swollen with an aqueous salt solution. The so-called Pila di Volta used a polymer for the first time in an electrochemical device and can be seen as a powerful idea to create new devices. Recently, polymers became an alternative to make thin and flexible devices. Thus, we find transparent plastic electrodes based on poly(ethylene terephtalate) coated with a transition metal oxide. There are also polymer electrolytes based on complexes of inorganic salts and poly(ethylene oxide) derivatives, with reasonable ionic conductivity in the absence of solvents. Finally, the electroactive polymers are efficient substitutes for the inorganic semiconductors because they can be synthetically tailored to produce the desired electronic answer. 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Photoelectrochemical Properties Of Poly(3,4-ethylenedioxythiophene)

The photoelectrochemical properties of poly(3,4-ethylene dioxythiophene)/ poly(styrene sulfonate) in contact with an electrolytic solution containing a redox couple were studied using the theories for the semiconductor-electrolyte interface. When this polymer-electrolyte interface is illuminated with hv > Eg (gap energy) it exhibits cathodic photocurrent typical of p-type semiconductors, and the flat band potential, density of majority carriers, and the depletion layer thickness can be determined. To complete the band energy diagram of this polymer-electrolyte interface we obtained the band gap energy through the absorption and photocurrent spectra. The relatively low band gap energy (1.5 eV) and the photoeffects observed at the interface suggest its use as the absorbing material in photoelectrochemical cells. © 2000 American Chemical Society.1042661246127Koryta, J., Dvorak, J., Kavan, L., (1993) Principles of Electrochemistry, 2nd Ed., , John Wiley: New YorkBard, A.J., Faulkner, L.R., (1980) Electrochemical Methods - Fundamentals and Applications, , John Wiley: New YorkBantikassegn, W., Inganäs, O., (1995) Thin Solid Films, 293, p. 138Camaioni, N., Casalbore-Miceli, G., Geri, A., Zotti, G., (1998) J. Phys. D: Appl. Phys., 31, p. 1245Gerischer, H., (1990) Electrochim. Acta, 35, p. 1677Miquelino, F.L.C., De Paoli, M.-A., Geniès, E.M., (1994) Synth. Met., 68, p. 91Martini, M., De Paoli, M.-A., (2000) Sol. Energy Mater. Sol. Cells, 60, p. 73Das Neves, S., De Paoli, M.-A., (1998) Synth. Met., 96, p. 48Maia, D.J., Das Neves, S., Alves, O.L., De Paoli, M.-A., (1999) Electrochim. Acta, 44, p. 1945Gazotti, W.A., Faez, R., De Paoli, M.-A., (1996) J. Electroanal. Chem., 415, p. 107Micaroni, L., De Paoli, M.-A., (1996) Sol. Energy Mater. Sol. Cells, 46, p. 79Pei, Q., Zucarello, G., Ahlskog, M., Inganäs, O., (1994) Polymer, 35, p. 1347Dietrich, M., Heinze, J., Heywang, G., Jonas, F., (1994) J. Electroanal. Chem., 369, p. 87De Paoli, M.-A., Casalbore-Miceli, G., Gazotti, W.A., Girotto, E.M., (1999) Electrochim. Acta, 44, p. 2983Micaroni, L., Polo Da Fonseca, C.N., Decker, F., De Paoli, M.-A., (2000) Sol. Energy Mater. Sol. Cells, 60, p. 127Abrantes, L.M., Castillo, L.M., Fleischmann, M., Hill, I.R., Peter, L.M., Mengoli, G., Zotti, G., (1984) J. Electroanal. Chem., 177, p. 129Li, Z., Dong, S., (1992) Electrochim. Acta, 37, p. 1003Glenis, S., Tourillon, G., Garnier, F., (1986) Thin Solid Films, 139, p. 221Butler, M.A., (1977) J. Appl. Phys., 48, p. 1914Finklea, H., (1988) Semiconductors Electrodes, , Elsevier: New YorkSunde, S., Hagen, G., Odegard, R., (1993) J. Electroanal. Chem., 345, p. 59Glenis, S., Tourillon, G., Garnier, F., (1984) Thin Solid Films, 122, p. 9Wilson, R.H., (1977) J. Appl. Phys., 48, p. 4292Skotheim, T., (1981) Appl. Phys. Lett., 38, p. 9Gerischer, H., (1981) Photovoltaic and Photoelectrochemical Solar Energy Conversion, , Cordon, S., Gomes, W. P., Dekeyser, W., Eds.Plenum Press: New YorkWöhrle, D., Meissner, D., (1991) Adv. Mater., 3, p. 12

Thermal And Photochemical Degradation Of Dodecylsulfate Doped Polypyrrole

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)The authors report on the changes of the electrical, morphological, chemical and electrochemical properties of polypyrrole dodecylsulfate films aged at 100°C or exposed to a solar simulator light source. The thermal aging induces a loss of conductivity and a gradual decrease of the anodic and cathodic peak currents, as measured by cyclic voltammetry. Irradiation does not substantially alter the properties of the films; the conductivity does not change and the electroactivity is slightly modified. Degradation of the properties is attributed to cross-linking, oxidation and evaporation of low molecular weight oligomers. © 1993.423317321FAPESP; São Paulo Research FoundationFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Studt, (1991) R&D Magazine, 10, p. 94Inoue, Yamase, (1983) Bull. Chem. Soc. (Japan), 56, p. 985Peres, Pernaut, De Paoli, (1991) J. Polym. Sci: Part A, Polym., Chem., 29, p. 225Billingham, Calvert, Foot, Mohammad, (1987) Poly. Deg. & Stab., 19, p. 323De Paoli, Panero, Paserini, Scrosati, (1990) Adv. Mater., 2, p. 480Ge, Wallace, (1992) Polymer, 33, p. 2348Neoh, Kang, Tan, (1988) Poly. Deg. & Stab., 21, p. 93Valdez, (1954) Proc. Inst. Radio Engirs., 42, p. 420Tourillon, Garnier, (1982) J. Electroanal. Chem., 135, p. 173Coleman, (1975) Rev. Sci. Instrum., 46, p. 112

Influence Of Dopant, Ph And Potential On The Spectral Changes Of Poly( O-methoxyaniline) : Relationship With The Redox Processes

Poly(o-methoxyaniline) films doped with functionalized acids show high solubility in conventional organic solvents and a high optical contrast between the reduced and the oxidized forms. They are also more stable towards thermal treatment than when they are doped with HCl. These characteristics make them suitable for use in electrochromic displays. The electrochromic behavior of this soluble derivative of polyaniline was investigated in detail by comparing the curves obtained by the differentiation of absorbance at fixed wavelengths with simultaneously obtained voltammograms. This analysis allows the chromophore species producing color changes to be related to the redox processes taking place during the electrochemical cycling. Molar absorptivities were calculated and the effect of pH on the absorption spectra of the emeraldine form of the polymer is also reported. © 1997 Elsevier Science S.A.44001/02/15193199Geniès, E.M., Boyle, A., Lapkowski, M., Tsintavis, C., (1990) Synth. Met., 36, p. 139Geniès, E.M., Lapkowski, M., Santier, C., Vieil, E., (1987) Synth. Met., 18, p. 631Lacroix, J.C., Kanazawa, K.K., Diaz, A., (1989) J. Electrochem. Soc., 136, p. 1308Huang, W.S., MacDiarmid, A.G., (1993) Polymer, 34, p. 1833Tassi, E.L., De Paoli, M.-A., (1994) Electrochim. Acta, 39, p. 2481Duek, E.A.R., De Paoli, M.-A., (1992) Adv. Mat., 4, p. 287Duek, E.A.R., De Paoli, M.-A., Mastragostino, M., (1993) Adv. Mat., 5, p. 650Ikkala, O.T., Laakso, J., Väkiparta, K., Virtanen, E., Ruohonen, H., Järvinen, H., Taka, T., Heeger, A.J., (1995) Synth. Met., 69, p. 97Davies, S.J., Ryan, T.G., Wilde, C.J., Beyer, G., Synth. Met., 69 (1995), p. 209Vikki, T., Ikkala, O.T., (1995) Synth. Met., 69, p. 235Ikkala, O.T., Lindholm, T.M., Ruohonen, H., Seläntaus, M., Väkiparta, K., (1995) Synth. Met., 69, p. 135Macinnes, D., Funt, B.L., (1988) Synth. Met., 25, p. 235Gonçalves, D., Matvienko, B., Bulhões, L.O.S., (1994) J. Electroanal. Chem., 37, p. 267Malmonge, L.F., Mattoso, L.H.C., (1995) Polymer, 36, p. 245Gomes, M.A.B., Gonçalves, D., Souza, E.C.P., Valla, B., Aegerter, M.A., Bulhões, L.O.S., (1992) Electrochim. Acta, 37, p. 1653Koziel, K., Lapkowski, M., Lefrant, S., (1995) Synth. Met., 69, p. 217Córdoba De Torresi, S.I., (1995) Electrochim. Acta, 40, p. 1101Servagent, S., (1990), Ph.D. Thesis, Universite Joseph Fourier, Grenoble-FranceNeoh, K.G., Tang, E.T., Tan, K.L., (1993) Polymer, 34, p. 1630Ray, A., Asturias, G.E., Kershner, D.L., Richter, A.F., Macdiarmid, A.G., Epstein, A.J., (1989) Synth. Met., 29, pp. E141Gazotti W.A., Jr., De Paoli, M.-A., (1996) Synth. Met., 80, p. 263Gazotti W.A., Jr., Faez, R., De Paoli, M.-A., (1996) J. Electroanal. Chem., 415, p. 107MacDiarmid, A.G., Epstein, A.J., (1989) Faraday Dicuss. Chem. Soc., 88, p. 317Chang, J.-C., MacDiarmid, A.G., (1986) Synth. Met., 13, p. 193Sotomayor, M.P.T., Gazotti W.A., Jr., De Paoli, M.-A., Oliveira, W.A., (1995) 18th Meeting of Brazilian Chemical Society, pp. QA-140. , Caxambu-BrazilPenneau, J.F., Lapkowski, M., Geniès, E.M., (1989) New J. Chem., 13, p. 449Córdoba De Torresi, S.I., Gorenstein, A., Torresi, R.M., Vásquez, M.V., (1991) J. Electroanal. Chem., 318, p. 131Córdoba De Torresi, S.I., Gorenstein, A., (1992) Electrochim. Acta, 37, p. 2015Gazotti W.A., Jr., Matencio, T., De Paoli, M.-A., Electrochim. Acta, , in pres

Using Poly(o-methoxyaniline) As Thermal Stabilizer For Polymers

Conductive polymer blends are generally prepared to obtain conductive materials with plastic characteristics. To be used in large scale, thermal stability at the working temperature of usual processing methods used in the plastic industry is required for these mixtures. In this work we studied the effect of adding poly(o-methoxyaniline) doped with p-toluene sulfonic acid to different processable polymers which present liberation of acids during their thermal degradation.1021-312071208Prón, A., Österholm, J.E., Smith, P., Heeger, A.J., Laska, J., Zagórska, M., (1993) Synth. Met., 55-57, p. 3520Laska, J., Izak, P., Prón, A., (1996) J. Appl. Polym. Sci., 61, p. 1339Cao, Y., Smith, P., Heeger, A.J., (1993) Synth. Met., 55-57, p. 3514De Paoli, M.-A., Waltman, R.J., Diaz, A.F., Bargon, J., (1984) J. Chem. Soc. Chem. Commun., p. 1015De Paoli, M.-A., (1997) Handbook of Organic Conductive Molecules and Polymers, 2, p. 773. , H.S. Nalwa (ed.), Nalwa, H. S. (ed.), John Wiley & Sons, New YorkGazotti, W.A., De Paoli, M.-A., (1996) Synth. Met., 80, p. 26

A New Configuration Of The Solid-state Battery: Magnesium|polymer Proton Conductor|gold, Based On The Use Of Poly(o-methoxyaniline)

A solid-state battery was constructed by interfacing a pressed pellet of poly(o-methoxyaniline), in the emeraldine form with p-toluene sulfonic acid as doping agent, to a magnesium electrode covered with a film of magnesium perchlorate; the contact on the poly(o-methoxyaniline) was done by means of a gold electrode. The so-obtained cell, Mg|magnesium perchlorate|poly(o-methoxyaniline)|gold, was able to supply energy with a power depending on discharge current and on environmental humidity. Values of power up to 2.5 mW cm-2 at discharge currents of about 2 mA cm-2 were reached. © 1997 Elsevier Science S.A.9013136Gemeay, A.H., Nishiyama, H., Kuwabata, S., Yoneyama, H., (1995) J. Electrochem. Soc., 142, p. 4190Momma, T., Kakuda, S., Yarimizu, H., Osaka, T., (1995) J. Electrochem. Soc., 142, p. 1766Tsutsumi, H., Fukuzawa, S., Ishikawa, M., Morita, M., Matsuda, Y., (1995) J. Electrochem. Soc., 142, pp. L168Morita, M., Miyazaki, S., Ishikawa, M., Matsuda, Y., Tajima, H., Adachi, K., Anan, F., (1995) J. Power Sources, 54, p. 214Barbero, C., Miras, M.C., Schnyder, B., Haas, O., Kotz, R., (1994) J. Mater. Chem., 4, p. 1775Gauthier, M., Belanger, A., Bouchard, P., Kapfer, B., Ricard, S., Vassort, G., Armand, M., Krause, L., (1995) J. Power Sources, 54, p. 163Scrosati, B., Neat, R.J., (1993) Application of Electroactive Polymers, p. 182. , B. Scrosati (ed.), Chapman and Hall, LondonBoinowitz, T., Suden, G.T., Tormin, U., Krohn, H., Beck, F., (1995) J. Power Sources, 56, p. 179Capuano, F., Casalbore-Miceli, G., Giro, G., Scrosati, B., (1994) J. Appl. Electochem., 24, p. 114Camaioni, N., Casalbore-Miceli, G., Martelli, A., Yang, M.J., (1997) J. Appl. Electrochem., 27Kumar, G., Sivashanmugam, A., Muniyandi, N., Dhawan, S.K., Trivedi, D.C., (1996) Synth. Met., 80, p. 279Gazotti W.A., Jr., De Paoli, M.-A., Synth. Met., , in pressPourbaix, M., (1966) Atlas of Electrochemical Equilibria in Aqueous Solutions, p. 101. , Pergamon Press, Oxfor

Electrochemical And Electrochromic Properties Of Poly(4,4″ Dimethoxy 3′-methyl 2,2′:5′,2″ Terthiophene)

This work describes the electrochemical, spectroelectrochemical and electrochromic properties of poly(4,4″ dimethoxy 3′-methyl 2,2′:5′,2″ terthiophene) thin films. The effect of temperature on the electropolymerization was studied by cyclic voltammetry measured in situ. The temperatures used were -10, 0, 10, 20, and 40°C. Results indicate that the electropolymerization temperature directly affect the degree of chain organization. The optical response time for bleaching was 0.8 s and for coloring 0.3 s (for films synthesized at 40°C, 60 nm thick). After 1400 electrochromic cycles, the chromatic contrast at 570 nm changes from 31 to 14%. The coloration efficiency was enhanced as a function of redox cycling. This was probably caused by a decrease in the injected charge necessary for the color change, suggesting that the electroactive losses occurring during the cycles are related to sites not responsible for electrochromic contrast. ©2005 Sociedade Brasileira de Química.164733738Roncali, J., (1992) Chem. Rev., 92, p. 711Tourillon, G., Garnier, F., Lemaire, M., (1982) J. Electroanal Chem., 135, p. 173Pomerantz, M., (1998) Handbook of Conducting Polymers, , Skotheim, T. A.Elsenbaumer, R. L.Reynolds, J. R., eds.Marcel Dekker: New York, ch. 11Roncali, J., (1997) Chem. Rev., 97, p. 173Andersson, M.R., Thomas, O., Mammo, W., Svensson, M., Theander, M., Inganäs, O., (1999) J. Mater. Chem., 9, p. 1993Tsivgoulis, G.M., Lehn, J.M., (1997) Adv. Mater., 9, p. 39Andersson, M.R., Berggren, M., Gustafsson, G., Hjertberg, T., Inganäs, O., Wennerström, O., (1995) Synth. Met., 71, p. 2183Granström, M., (1997) Polym. Adv. 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Conductive Polymer Blends As Electrochromic Materials

Conductive polymer blends were prepared mixing conductive and insulating polymers and their electrochemical and electrochromic properties were studied. Depending on the insulator matrix used, these properties are not changed. Blend containing polyacrylonitrile and poly(o-methoxyaniline) doped with p-toluene sulfonic acid presents the same electrochemical and electrochromic behavior as the pure conducting polymer. Other blends studied were those obtained by combining poly(epichlorohydrin-co-ethylene oxide) with poly(o-methoxyaniline) and poly(4,4′-dipentoxy-2,2′-bithiophene). An electrochromic device using these polymer blends and a liquid electrolyte was assembled and presented Δ%T620nm=56%. This contrast decreased after 300 double potential steps to 33%.441219651971Echte, A., (1993) Handbuch der Technischen Polymerchemie, p. 663. , VCH Verlag, WeinheimOsaka, T., Ogano, S., Naoi, K., (1989) J. Electrochem. Soc., 136, p. 306Noufi, R., Nozik, A.J., White, J., Warren, L.F., (1982) J. Electrochem. Soc., 129, p. 226Josowiaz, M., Janata, J., (1986) J. Anal. Chem., 58, p. 514Bull, R.A., Fan, F.R., Bard, A.J., (1984) J. Electrochem. Soc., 131, p. 687Heinze, J., (1991) Synth. Met., 41, p. 2085Laakso, J., Osterholm, J-E., Nyholm, P., Stubb, H., Punnka, E., (1990) Synth. Met., 37, p. 145Gonçalves, D., Waddon, A., Karasz, F.E., Akcerlud, L., (1995) Synth. Met., 74, p. 197Chen, Y., Qian, R., Li, G., Li, Y., (1991) Polym. Commun., 32, p. 189De Paoli, M.-A., Peres, R.C.D., Duek, E.A.R., Pandalai, S.G., (1994) Current Topics in Electrochemistry, 3, p. 409. , (Eds.), Council of Scientific Information, TrivandrumMastragostino, M., Scrosati, B., (1993) Applications of Electroactive Polymers, p. 223. , (Eds.), Chapman & Hall, LondonScrosati, B., Scrosati, B., (1993) Applications of Electroactive Polymers, p. 299. , (Eds.), Chapman & Hall, LondonMastragostino, M., Marinangeli, A.M., Corradini, A., Giacobbe, C., (1989) Synth. Met., 28, p. 501Gustafson, J.C., Inganas, O., (1994) Synth. Met., 62, p. 17Roncali, J., Garnier, F., (1988) J. Phys. Chem., 92, p. 833Gazotti Jr, W.A., De Paoli, M-A., (1996) Synth. Met., 80, p. 263De Paoli, M-A., Waltman, R.J., Diaz, A.F., Bargon, J., (1984) J. Chem. Soc. Chem. Commun., 1015Mano, V., Felisberti, M.I., Matencio, T., De Paoli, M-A., (1996) Polymer, 37, p. 5165De Paoli, M-A., Maia, D.J., (1994) J. Mater. Chem., 4, p. 1799Malmonge, L.F., Mattoso, L.H.C., (1995) Polymer, 36, p. 245Geniès, E.M., Boyle, A., Lapkowski, M., Tsintavis, C., (1990) Synth. Met., 36, p. 139Huang, W-S., Humphrey, B.D., MacDiarmid, A.G., (1986) J. Chem. Soc., Faraday Trans. I, 82, p. 2385Watanabe, A., Mori, K., Mikuni, M., Nakamura, Y., Matsuda, M., (1989) Macromolecules, 22, p. 3323Gazotti W.A., Jr., Jannini, M.J.D.M., Córdoba De Torresi, S.I., De Paoli, M.-A., (1998) J. Electroanal. Chem., , in pressGazotti W.A., Jr., Faez, R., De Paoli, M.-A., (1996) J. Electroanal. Chem., 415, p. 107Zotti, G., Gallazzi, M.C., Zerbi, G., Meille, S.V., (1995) Synth. Met., 73, p. 217Arbizzani, C., Mastragostino, M., Meneghello, L., Morselli, M., Zanelli, A., (1996) J. Appl. Electrochem., 26, p. 121Silva, G.G., Lemes, N.H., Polo Da Fonseca, C.M.N., De Paoli, M-A., (1996) Solid State Ionics, 93, p. 105Duek, E.A.R., De Paoli, M-A., Mastragostino, M., (1993) Adv. Mater., 5, p. 650De Paoli, M-A., Zanelli, A., Mastragostino, M., Rocco, A.M., (1997) J. Electroanal. Chem., 435, p. 21