O presente trabalho apresenta os resultados de preparação e caracterização de cinco dispositivos eletrocrômicos (DEC) compostos por filmes finos de óxidos de metais de transição, tais como WO3, WO3:Ta, Nb2O5:Mo e NiOx como camadas eletrocrômicas e CeO2-TiO2 como contra-eletrodo transparente. Os eletrólitos usados nestes dispositivos foram à base de amido plastificado com glicerol e contendo LiClO4 ou KOH dependendo da camada eletrocrômica. Todos os filmes finos foram preparados pelo processo sol-gel e depositados sobre FTO pela técnica de dip-coating. Os dispositivos foram caracterizados através da técnica de voltametria cíclica, espectroscopia na região do UV-visível-NIR (300–1100 nm) e densidade de carga inserida/extraída ao longo dos ciclos cronoamperométricos. A partir dos valores obtidos para a densidade de carga inserida e a transmitância em 550 nm e em 633 nm e com o uso de uma equação apropriada obtiveram-se os valores de eficiência eletrocrômica dos dispositivos eletrocrômicos. Foram feitas também medidas de densidade ótica em função do potencial e transmitância em função do tempo. Os resultados de densidade de carga para os dispositivos eletrocrômicos com WO3, WO3:Ta e Nb2O5:Mo mostraram que os processos de inserção/extração dos íons lítio são reversíveis, sendo que a extração é muito rápida da ordem de 10s. Através dos espectros de transmissão observou-se uma boa variação na transmitância entre os estados coloridos e descoloridos (T), sendo que o DEC com WO3 e eletrólito com concentração de LiClO4, [O]/[Li]=10 obteve a maior variação de T = 38,4% em 633 nm. Isso resultou num alto valor de eficiência eletrocrômica de 77,5 cm2/C. O DEC com NiOx apresentou uma menor variação na transmitância, 23,8% em 550 nm para o ciclo 3000, resultando num menor valor de eficiência eletrocrômica, 24,9 cm2/C. O presente trabalho apresenta também os resultados da preparação e caracterização de eletrólitos sólidos poliméricos contendo amido, glicerol e hidróxido de potássio, os quais foram caracterizados através da técnica de espectroscopia de impedância eletroquímica e a partir destes resultados os valores das suas condutividades iônicas foram calculadas. Fez-se também medidas de transmissão ótica na região do UV-visível-NIR (300-1100 nm). O melhor valor de condutividade iônica foi obtido para o filme com 25% de glicerina e 35% de KOH em relação à massa do amido, sendo 4,92∙10-5 S∙cm-1 a 30oC. Os resultados obtidos neste trabalho mostram que os eletrólitos sólidos poliméricos à base de amido podem ser muito interessantes para aplicação em dispositivos eletrocrômicos como, por exemplo, janelas eletrocrômicas em arquitetura. / This dissertation presents the results of preparation and characterization of five electrochromic devices (DEC) composed of thin films of transition metal oxides, such as WO3, WO3:Ta, Nb2O5:Mo and NiOx as electrochromic layers and CeO2-TiO2 as a transparent counter-electrode. The electrolytes used in these devices were starch-based plasticized with glycerol containing LiClO4 or KOH, depending on the electrochromic layer. All the thin films were prepared by sol-gel process and deposited onto FTO by dip-coating technique. The devices were characterized by means of cyclic voltametry, spectroscopy in the region of UV-visible-NIR (300-1100 nm) and the inserted/extracted charge density along the chronoamperometric cycles. From the values obtained for the inserted charge density and the transmittance in 550 nm and 633 nm and using an appropriate equation the values of electrochromic efficiency of the electrochromic devices were obtained. Measurements of optical density in function of the potential and transmittance in function of the time were also taken. The results of charge density for the electrochromic devices with WO3, WO3:Ta and Nb2O5:Mo showed that the processes of insertion/extraction of the lithium ions are reversible and the extraction is very fast, i.e., of the order of 10s. Through the transmission spectra it was possible to observe a good variation in the transmittance between the coloured and bleached states (T), given that the DEC with WO3 and electrolyte with concentration of LiClO4, [O]/[Li]=10 obtained the largest variation of T = 38.4% in 633 nm. This resulted in a high value (77.5 cm2/C) of electrochromic efficiency. The DEC with NiOx presented a smaller variation in the transmittance, i.e., 23.8% in 550 nm for cycle 3000, resulting in a lower value of electrochromic efficiency, 24.9 cm2/C. This work also presents the results of the preparation and characterization of solid polymeric electrolytes containing starch, glycerol and potassium hydroxide characterized by the technique of electrochemical impedance spectroscopy. From these results the values of their ionic conductivities were calculated. Measurements of optical transmission in the region of UV-visible-NIR (300-1100 nm) were also taken. The best value of ionic conductivity, i.e., 4.9210-5 Scm-1 at 30oC was obtained for the film with 25% of glycerol and 35% of KOH in relation to the mass of starch. The results presented in this work show that starch-based solid polymeric electrolytes can be very interesting for application in electrochromic devices as, for example, smart windows in architecture.

Foram estudados os filmes finos eletrocrômicos de WO3, MoO3 e PEDOT:PSS e aplicados em pequenos dispositivos eletrocrômicos. Os filmes finos de WO3 foram produzidos por meio do processo de eletrodeposição galvanostática a partir de um sol de ácido peroxotungstênico. Realizaram-se dois estudos de eletrodeposição dos filmes de WO3: 1º) produziu-se filmes em diferentes correntes -0,45 -0,50, -0,60 e -1,0 mA com tempo de 600 segundos; 2º) produziu-se filmes variando os tempos de eletrodeposição de 100, 200, 300, 400, 500 e 600 s com corrente de -0,45 mA. O tratamento térmico foi efetuado a 120 ºC por 1 hora. Os filmes de WO3 eletrodepositados com corrente -0,45 mA no tempo de 600 s foram estudados com maiores detalhes. Os filmes com espessura de 140 nm apresentaram mudança na coloração de transparente para azul em resposta a aplicação de potencial de -1,0 a 1,0 V. A variação em transmitância foi medida no visível (λ = 633 nm) resultando em ΔT = 61 %. A densidade de carga foi de 35 mC/cm2 e a estabilidade eletroquímica foi de até 3.000 ciclos. As medidas de difração de raios-X mostraram que a estrutura dos filmes de WO3 é amorfa e as imagens de microscopia eletrônica de varredura (MEV) evidenciaram uma superfície homogênea e sem rachaduras. O filme de PEDOT:PSS depositado por dip-coating apresentou uma espessura em torno de 400 nm, mudança de coloração de azul para transparente com a aplicação do potencial de -1,0 a 1,0 V e ΔT= 50 % para o filme de uma camada. Os filmes de MoO3 foram depositados pela técnica de spin-coating e avaliados conforme o número de camadas (1 a 10 camadas) sendo os melhores resultados foram obtidos para a amostra composta por 9 camadas. Este filme apresentou densidade de carga em torno de 25 mC/cm2 e uma mudança de cor de transparente (T= 80%) para azul (T=38%) após a aplicação de potencial de 1,5 e -1,5 V, respectivamente. Foram confeccionados e estudados dispositivos eletrocrômicos (ECDs) com os filmes finos de WO3 e PEDOT:PSS, eletrólitos poliméricos a base de hidroxipropilcelulose (HPC) e goma gelana (GGLA) e contra eletrodo de CeO2-TiO2. As melhores respostas óticas foram obtidas com o dispositivo eletrocrômico WO3/HPC/CeO2-TiO2, sendo ΔT=29% e a densidade de carga de 12 mC/cm2. A melhor estabilidade em função do número de ciclos de coloração/descoloração de 5.500 foi obtido com o dispositivo eletrocrômico WO3|GGLA-PVP-NHS|CeO2-TiO2 com glicerol. / Electrochromic WO3, MoO3 and PEDOT: PSS thin films were deposited and characterized. WO3 thin films were produced using the galvanostatic electrodeposition process from peroxotungstic acid sol. There were two studies of electrodeposition of WO3 films: 1) films were produced in different streams -0.45 -0.50, -0.60 and -1.0 mA with a time of 600 seconds, and 2) produced films were electrodeposited varying times 100, 200, 300, 400, 500 and 600 s with a current of -0.45 mA. The heat treatment was performed at 120 °C for 1 hour. The WO3 films electrodeposited with -0.45 mA current for 600 s were chosen and studied deeply. These films with a thickness of 140 nm showed change in color from transparent to blue in response to applied potential of -1.0 to 1.0 V. The variation in transmittance was measured at λ = 633 nm, resulting in ΔT = 61%, charge density of about 35 mC/cm2 and electrochemical stability up to 3,000 cycles. X-ray diffractograms showed that the structure of the films is amorphous and scanning electron microscopy (SEM) images showed a homogeneous surface without cracks. The film of PEDOT: PSS deposited by dip-coating had a thickness around 400 nm, color change from blue to transparent upon applied potential of -1.0 to 1.0 V and ΔT = 50% for the one layer film. The MoO3 films were deposited by spin-coating and evaluated as the number of layers (1 to 10 layers) appointing the best results for the sample with 9 layers. This displayed the charge density of around 25 mC/cm2 and a color change from transparent (T = 80%) to blue (T = 38%) after applying the potential of 1.5 and -1.5 V, respectively. Furthermore, the electrochromic devices containing WO3 and/or PEDOT: PSS thin films, polymer electrolytes based cellulose and/or gellan gum and counter electrode of CeO2-TiO2 were assembled and characterized. The best responses of ΔT = 29% and charge density of 12 mC/cm2 were obtained for the electrochromic device with WO3/cellulose/CeO2-TiO2 configuration. However, the best coloring/bleaching stability of 5,500 cycles was obtained with the electrochromic device WO3|GGLA-PVP-NHS|CeO2-TiO2 with glycerol configuration.

Au cours de cette thèse, des dispositifs électrochromes à base de polymères conducteurs électroniques ont été développés pour obtenir des systèmes pouvant passer d’un état coloré cyan, magenta ou jaune à un état incolore. Les polymères électrochromes sont des dérivés du poly(3,4-propylènedioxythiophène) (PProDOT) et du poly(3,4-éthylènedioxythiophène) (PEDOT). Un réseau de polyéthylène glycol incorporant un liquide ionique 1-éthyl-3-méthylimidazolium bis(trifluorométhylsulfonylimide) (EMITFSI) a été utilisé en tant que gel d’électrolyte. Dans un premier temps, les polymères cyan, magenta et jaunes ont été étudiés. La relation entre structure et propriétés colorimétriques des polymères cyan et jaunes a été étudiés par des calculs théoriques avec la théorie de fonctionnelle de densité, la spectroscopie UV/Vis et la colorimétrie. Ces deux dernières techniques ont également été utilisées pour l’étude des polymères magenta. Les polymères présentant les meilleures propriétés optiques ont ensuite été intégrés dans des dispositifs à deux électrodes. Ceux-ci ont été étudiées par des mesures électrochimiques pour évaluer les effets sur le fonctionnement du système et sa durée de vie. Grâce aux données obtenues, nous avons pu montrer que la stabilité des dispositifs était liée à l’efficacité coulombique des polymères cyan, magenta ou jaunes. Pour contourner l’effet de l’efficacité coulombique sur les systèmes en 2 électrodes, nous avons développé des dispositifs intégrant une pseudo-référence. L’application de ces systèmes à 3 électrodes avec un polymère cyan permet de multiplier la gamme de stabilité par 7. Finalement des démonstrateurs ont été produits avec plusieurs dispositifs de chaque couleur. / During the course of this work, electrochromic devices integrating electronically conductive polymers have been developed to obtain systems that could switch from a cyan, magenta or yellow color to an almost colorless one. The electrochromic polymers are derivatives of poly(3,4-propylenedioxythiophene) (PProDOT) and poly(3,4-ethylenedioxythiphene) (PEDOT). A network of polyethyleneglycol swollen with an ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonylimide) (EMITFSI) was used as a gel polymer electrolyte. As a first step, the cyan, magenta and yellow polymers were studied. The relationship between structure and colorimetric properties of the cyan and yellow polymers have been studied with theoretical calculation using the density functional theory, UV/Vis spectroscopy and colorimetry. These last two techniques have also been used to study the magenta polymers. The polymers with the best optical properties have then been integrated inside two electrode devices. They have been characterized with electrochemical measurement to evaluate the effects on the system and its lifetime. The data showed that the stability of the devices was linked to the reversibility of the cyan magenta or yellow polymers. As a workaround to the coulombic efficiency limitation on the 2 electrode systems, we have developed devices with a pseudo-reference. The application of those 3 electrode systems with a cyan polymer leads to a 7 fold increase of the device lifetime. Finally demonstrators have been produced with several devices of each color.

No description available.

In this study three different 3-ester substituted thiophene monomers were synthesized via esterification reaction of 3-thiophene ethanol with adipoyl chloride or sebacoyl chloride or octanoyl chloride in the presence of triethylamine at 00C. Characterizations of the monomers were performed by 1H-NMR, 13C-NMR, FTIR, DSC, TGA techniques. Electrochemical behavior of the monomers both in presence or absence of BFEE were studied by cyclic voltammetry. Results showed the astonishing effect of BFEE on the polymerization, where free standing films of the homopolymers could be synthesized. Copolymers of the monomers with thiophene or 3-methyl thiophene were synthesized at constant potential electrolysis and the resultant polymers were characterized by FTIR, DSC, TGA, SEM and conductivity measurements. Second part of the study was devoted to investigate the one of most interesting property of conducting polymers, the ability to switch reversibly between the two states of different optical properties, &lsquo / electrochromism&rsquo / . In recent years there has been a growing interest in application of conducting polymers in electrochromic devices. Thus, electrochromic properties of the synthesized conducting polymers were investigated by several methods like spectroelectrochemistry, kinetic and colorimetry studies. Spectroelectrochemistry experiments were performed in order to investigate key properties of conjugated polymers such as band gap, maximum absorption wavelength, the intergap states that appear upon doping and evolution of polaron and bipolaron bands. Switching time and optical contrast of the homopolymers and copolymers were evaluated via kinetic studies. Results implied the possible use of these materials in electrochromic devices due to their satisfactory electrochromic properties like short switching time and stability. Generally the homopolymers displayed color changes between yellow, green and blue colors upon variation of applied potentials. Fine tuning of the colors of the polymers were accomplished by techniques like copolymerization and lamination. These studies were supported with experiments like spectroelectrochemistry and FTIR. Results showed the possible control of the color of the electrochromic material in a predictable, controlled and reproducible manner. Yet, it was possible to achieve different tones of yellow, green, orange color in neutral state of these materials. As the last part of the study, dual type electrochromic devices based on polymers of 3-ester substituted thiophenes with poly(3,4-ethylenedioxythiophene) were constructed, where the former and the later functioned as anodically and cathodically coloring layers respectively. Spectroelectrochemistry, switching ability, stability, open circuit memory and color of the devices were investigated and the results revealed that these devices have satisfactory electrochromic parameters.

Two new monomers / 2-benzyl-5,12-dihydro-2Hpyrrolo[ 3&rsquo / ,4&rsquo / :2,3][1,4]dioxocino[6,7-b]quinoxaline (DPOQ) and 5,12- dihydrothieno[3&rsquo / ,4&rsquo / :2,3][1,4]dithiocino[6,7-b]quinoxaline (DTTQ), were synthesized. The chemical structures of the monomers were characterized by Nuclear Magnetic Resonance (1H-NMR), Fourier Transform Infrared (FTIR) and Mass Spectrometry (MS). Copolymer of DPOQ with bithiophene (BT) was synthesized via potentiostatic electrochemical polymerization in acetonitrile (ACN)-tetrabutylammonium tetrafluoroborate (TBAFB) solvent-electrolyte couple. For DTTQ, copolymerization with bithiophene was achieved via potentiodynamic method in dichloromethane (DCM)-tetrabutylammonium hexafluorophosphate (TBAFP) solvent-electrolyte couple. Characterizations of the resulting copolymers were performed by cyclic voltammetry (CV), FTIR, Scanning Electron Microscopy (SEM) and UV-Vis Spectroscopy. Four-probe technique was used to measure the conductivities of the samples. Moreover, the spectroelectrochemical and electrochromic properties of the copolymer films were investigated. In addition, dual type polymer electrochromic devices (ECDs) based on P(DPOQ-co-BT) and P(DTTQ-co-BT) with poly(3,4- ethylenedioxythiophene) (PEDOT) were constructed. Spectroelectrochemistry, electrochromic switching and open circuit stability of the devices were studied. They were found to have good switching times, reasonable contrasts and optical memories.

Este trabalho apresenta os resultados do preparo e caracterização de dispositivos eletrocrômicos (ECD - electrochromic devices) contendo filmes finos de azul da Prússia (PB) como camada eletrocrômica, CeO2-TiO2 como contra-eletrodo e eletrólitos à base de polímeros contendo glicerol, formaldeído e γ-butirolactona. Os filmes finos de azul da Prússia foram preparados pelo método de eletrodeposição galvanostática e usados para montagem de dispositivos eletrocrômicos com eletrólitos de composição polimérica variada. Os filmes finos foram caracterizados através de medidas de densidade de carga, voltametria cíclica e transmitância no UV-Vis, além de análises morfológicas por microscopia de força atômica (AFM) e microscopia de varredura eletrônica (MEV), elipsometria, medidas de espessura, ângulo de contato e eficiência de coloração. O filme eletrodepositado por 300 s apresentou densidade de carga de 1,62 mC.cm-2 e 0,98 de reversibilidade com rugosidade de 17,7 nm, espessura de 315 nm via elipsometria e 216 nm via perfilometria. A eficiência de coloração calculada foi de 131,4 cm2.C-1 e os valores de ângulo de contato e energia livre de superfície também foram calculadas. As análises voltamétricas dos filmes finos revelaram picos característicos dos processos de oxidação e redução e as análises espectroscópicas apresentaram variação de transmitância de 71,6 % em 686 nm em solução eletrolítica de KCL 1 mol.L-1. Foram preparados e caracterizados dispositivos com eletrólitos a base de gelatina comercial com sal LiClO4; poli(vinil butirato) (PVB) com par iônico LiI/I2; PVB com LiClO4; PVB com par iônico LiI/I2+disperse red; ágar com LiClO4; ágar com sal Eu(CF3SO3)3; DNA com LiClO4; DNA com sal Er(CF3SO3)3; pectina com LiClO4; HPC com ácido acético; HPC com LiClO4 e PVDF com LiClO4. Dentre os resultados obtidos, os melhores resultados de densidade de carga de 10,1 e 8,5 mC.cm-2 foram obtidos para os dispositivos com eletrólitos de HPC e pectina, ambas com sal LiClO4. Voltamogramas cíclicos das amostras estudadas revelaram picos anódicos e catódicos referentes à extração e inserção de íons de lítio e/ou prótons, e elétrons no filme de PB. As análises de transmitância em 686 nm entre o estado colorido e descolorido dos dispositivos mostraram os valores de 40,2% para a janela contendo eletrólito à base de gelatina com LiClO4 e 35,2 % para a janela com ágar e sal Eu(CF3SO3). Além disso, também foi verificada a estabilidade dos dispositivos revelando a duração entre 400 a 2200 ciclos cronoamperométricos, dependendo do eletrólito usado. Os resultados obtidos mostram que os dispositivos estudados neste trabalho são potenciais candidatos para aplicações práticas em dispositivos eletrocrômicos. / This work presents the results of the preparation and characterization of electrochromic devices (ECDs) containing a thin film of Prussian blue (PB) as electrochromic layer, CeO2-TiO2 as a counter electrode and electrolytes based on polymers containing glycerol, formaldehyde, and γ-butyrolactone. Thin films of Prussian blue were prepared by galvanostatic electrodeposition method and used for the assembly of electrochromic devices with varying polymer composition of electrolytes. The thin films were characterized by charge density measurements, cyclic voltammetry, transmittance in the UV-Vis, and morphological analyzes such as atomic force microscopy (AFM) and scanning electron microscopy (SEM). Moreover, there were subjected to ellipsometry, thickness, contact angle, and coloring efficiency measurements. The electrodeposited film of 300 s had charge density of 1.62 mC.cm-2 and 0.98 of reversibility with roughness of 17.7 nm and thickness of 315 nm via ellipsometry and 216 nm via profilometry. The calculated color efficiency was 131.4 cm2.C-1 and the contact angle values and surface free energy were calculated. The voltammetric analyzes of thin films showed characteristic peaks of oxidation and reduction processes and spectroscopic analysis showed 71.6% transmittance variation at 686 nm in 1 mol.L-1 KCL electrolyte solution. ECD were prepared and characterized, using electrolytes such as commercial gelatin with LiClO4 salt; poly (vinyl butyrate) (PVB) with ion pair LiI/I2; PVB with LiClO4; PVB with ion pair LiI/I2 + disperse red; agar with LiClO4; agar with Eu(CF3SO3)3 salt; DNA with LiClO4; DNA with Er(CF3SO3)3 salt; pectin with LiClO4; HPC with acetic acid; HPC with LiClO4 and PVDF LiClO4. The best results of charge density of 8.5 and 10.1 mC.cm-2 were obtained for devices with HPC electrolytes and pectin, both with LiClO4 salt. Cyclic voltammetry of the studied samples revealed anodic and cathodic peaks relating to the extraction and insertion of lithium ions and/or protons and electrons in the PB film. The transmittance at 686 nm analysis between the colored state and discolored windows showed values of 40.2% for the window containing electrolyte of gelatin with LiClO4 and 35.2% for the window with agar and Eu(CF3SO3) salt. Furthermore, the stability of the devices was also recorded revealing the duration between 400-2200 chronoamperometric cycles, depending on the used electrolyte. The results show that the windows studied in this work are potential candidates for electrochromic devices applications.

Cette thèse s’inscrit dans le cadre d’un Programme d’Étude Amont (PEA) dirigé par la DGA et piloté par l’entreprise Nexter-System, consistant à élaborer des "Systèmes de camouflage adaptatifs Vis et IR". Ce projet concerne l’élaboration de macropixels adaptatifs à réflexion modulable. Le projet de recherche avait pour objectif de réaliser des couches minces de polymères électrochromes de couleur magenta, cyan et jaune pouvant commuter dans un état achromatique, afin de les intégrer dans des dispositifs complets tout organique (collaboration LPPI, Université de Cergy-Pontoise) ou hybrides (collaboration CEA Le Ripault). De plus, ces matériaux doivent être stables électrochimiquement et optiquement, et présenter des temps de commutation relativement courts (inférieurs à 10 secondes dans l’idéal). / This thesis is incorporated in a project which involves developing electro-adjustable reflection macro-pixels for armored vehicle's adaptative camouflage. The purpose of the research project was creating thin layers of magenta, cyan and yellow electrochromic polymers switchable to an achromatic state, in order to incorporate them in organic or hybrid complete devices. Moreover, these materials had to be electrochemically and optially stable, and had to present a short response time. In order to meet the materials color coordinates of the technical specification, the handgap of the organic semi-conductors has been realized by a particular design of the monomers, either by adding electron-rich or electron-poor groups, or by copolymerization between several co-monomers. According to sought properties and the possibilities offered by the monomers, the pi-conjugated polymers had been synthetized by chemical way (by oxydation or Suzuki or Stille reaction) then deposited by spray-casting, or electrodeposited at the surface of a transparent conductor substrate. The electrochromic thin layers had been electrochemically and spectroelectrochemically studied so as to test their cyclic stability and to determine their color coordinates, their opticl contrast and their response time. The use of ionic liquid EMITFSI for synthesis and electrochemical characterization had been explored, and pointed out a significant improvement of the cyclability of the created magenta, cyan and yellow polymers. The preparation of complete electrochromic devices (with organic or inorganic counterelectrode) has been started and has permitted to realize macro-pixels (2x2cm 2) and then demonstrative plates constituted of 16 macro-pixels (4x4cm 2 for each macropixel, with, in particular, yellow pixels including optimized poly(diphenyldithieno[3,2-b;2'3']thiophene)) with electro-control of the color commutation, constituting the fundamental component of an active surface tor the military vehicle's camouflage.

ABSTRACT SYNTHESIS AND ELECTROCHROMIC PROPERTIES OF CONDUCTING POLYMERS OF SUCCINIC ACID BIS-(2-THIOPHEN-3-YL-ETHYL) ESTER AND THEIR USE IN ELECTROCHROMIC DEVICES Sa&ccedil / an, Lale M.Sc., Department of Chemistry Supervisor: Prof. Dr. Levent Toppare June 2006, 59 pages A new monomer / succinic acid bis-(2-thiophen-3-yl-ethyl)ester (SATE) was synthesized through the esterification reaction of 2-thiophen-3-yl-ethanol and succinyl chloride. The chemical structure of monomer was characterized via Nuclear Magnetic Resonance Spectroscopy (NMR) and Fourier Transform Infrared Spectroscopy (FTIR). Electrochemical behaviors of SATE alone and SATE in the presence of thiophene were studied by cyclic voltammetry (CV). The synthesis of homopolymer and copolymer were achieved via constant potential electrolysis. Both homopolymer (PSATE) and copolymer [P(SATE-co-Th)] were characterized by various techniques including cyclic voltammetry, FTIR, Scanning Electron Microscopy (SEM), Differential Scanning Calorimetry (DSC), Thermal Gravimetry Analysis (TGA) and UV-VIS Spectrophotometer. Conductivities of samples were measured by four probe technique. The electrochromic properties of the polymers were investigated via spectroelectrochemistry, colorimetry and switching studies. In addition, dual type electrochromic devices (ECDs) composed of PSATE, P(SATE-co-Th) and poly(3,4-ethylenedioxythiophene) (PEDOT) were constructed and evaluated. Spectroelectrochemistry, switching ability and stability of the devices were investigated by UV-Vis Spectrophotometer and Cyclic Voltammetry. They have shown to possess good switching times, reasonable contrasts, high stabilities and optical memories.

A new monomer / 1-(4-Nitrophenyl)-2,5-di-2-thienyl-1H-pyrrole SNSNO2 was synthesized through the Knorr-Paal condensation reaction of 1,4-di-2-thienyl-1,4-butanedione and p-nitroaniline. The chemical structure of monomer and polymer were characterized via Nuclear Magnetic Resonance Spectroscopy (NMR) and Fourier Transform Infrared Spectroscopy (FTIR). Chemical polymerization produced a polymer which was completely soluble in organic solvents. Electrochemical behaviors of SNSNO2 and SNSNO2 in the presence of EDOT were studied by cyclic voltammetry (CV). The synthesis of homopolymer and copolymer were achieved via constant potential electrolysis. Both homopolymer P(SNSNO2) and copolymer P(SNSNO2-co-EDOT) were characterized by various techniques including cyclic voltammetry, FTIR, Scanning Electron Microscopy (SEM) and UV-VIS Spectrophotometer. Conductivities of samples were measured by four probe technique. The electrochromic properties of the polymers were investigated via spectroelectrochemistry, colorimetry and switching studies. In addition, dual type electrochromic devices (ECDs) composed of P(SNSNO2), P(SNSNO2-co-EDOT) and poly(3,4-ethylenedioxythiophene) (PEDOT) were constructed and evaluated. Spectroelectrochemistry, switching ability and stability of the devices were investigated by UV-Vis Spectrophotometer and Cyclic Voltammetry. They have shown to possess good switching times, reasonable contrasts and high stabilities.