RESUMEN
The electrochemical polymerization of 3,4-ethylenedioxythiophene (EDOT) was performed in the presence of a water-soluble anionic copper and zinc octa(3',5'-dicarboxyphenoxy)phthalocyaninate containing 16 ionogenic carboxylate groups. The influences of the central metal atom in the phthalocyaninate and EDOT-to-carboxylate group ratio (1:2, 1:4, and 1:6) on the course of electropolymerization were studied using electrochemical methods. It has been shown that the polymerization of EDOT in the presence of phthalocyaninates proceeds at a higher rate compared to that in the presence of a low-molecular-weight electrolyte (sodium acetate). Studies of the electronic and chemical structure using UV-Vis-NIR and Raman spectroscopies showed that the use of copper phthalocyaninate leads to a higher content of the latter in PEDOT composite films. The 1:2 EDOT-to-carboxylate group ratio was found to be optimal for a higher content of phthalocyaninate in the composite film.
RESUMEN
In this review, we have summarized the main advantages of the method of spectroelectrochemistry as applied to recent studies on electrosynthesis and redox processes of electroactive polymer composite materials, which have found wide application in designing organic optoelectronic devices, batteries and sensors. These polymer composites include electroactive polymer complexes with large unmovable dopant anions such as polymer electrolytes, organic dyes, cyclodextrins, poly(ß-hydroxyethers), as well as polymer-inorganic nanocomposites. The spectroelectrochemical methods reviewed include in situ electron absorption, Raman, infrared and electron spin resonance spectroscopies.
RESUMEN
The electrochemical synthesis of poly(3,4-ethylenedioxythiophene) (PEDOT) was first carried out in the presence of mixtures of flexible-chain and rigid-chain polyacids and their Na-salts. Earlier on with the example of polyaniline, we have shown the non-additive effect of the rigid-chain component of polyacid mixtures on the electrodeposition of polyaniline films, their morphology and spectroelectrochemical properties. In this study, we confirmed the non-additive effect and showed that such mixed PEDOT-polyelectrolyte films possess unique morphology, spectroelectrochemical and ammonia sensing properties. The electrosynthesis was carried out in potential cycling, galvanostatic and potentiostatic regimes and monitored by in situ UV-Vis spectroscopy. UV-Vis spectroelectrochemistry of the obtained PEDOT-polyelectrolyte films revealed the dominating influence of the rigid-chain polyacid on the electronic structure of the mixed complexes. The mixed PEDOT-polyacid films demonstrated the best ammonia sensing performance (in the range of 5 to 25 ppm) as compared to the films of individual PEDOT-polyelectrolyte films.
RESUMEN
Electrochemically synthesized poly(3,4,-ethylenedioxythiophene) (PEDOT) films obtained in the presence of eight different polysulfonate dopants are comparatively studied by means of electrochemical quartz crystal microbalance (EQCM) and X-ray Photoelectron Spectroscopy (XPS). Differences with respect to oxidation and doping levels (OL and DL), polymerization efficiency and redox behavior are revealed based on the interplay of three factors: the type of the dopant (acid or salt form), flexibility of the polysulfonate chains and molecular weight of the polysulfonate species. For the rigid- and semi-rigid-chain dopants, use of the salt form results in higher OL and DL values and substantial involvement of solvent molecules in the course of polymerization and redox transitions whereas in the presence of their acid form compact PEDOT films with minor ionic-solvent fluxes upon redox transitions are formed. In contrast, use of the salt form of the flexible chain polysulfonates results in PEDOT with lower OL and DL in comparison to the corresponding acid form. Significant effects are observed when comparing flexible chain dopants with different molecular weights. From a practical point of view the present investigations demonstrate the large scope of possibilities to influence some basic properties of PEDOT (Ol and DL, intensity and type of the ionic and solvent fluxes upon redox transition) depending on the used polysulfonate dopants.
RESUMEN
The structure of experimentally designed solar cells was optimized in terms of the photoactive layer thickness for both organic bulk heterojunction and hybrid perovskite solar cells. The photoactive layer thickness had a totally different behavior on the performance of the organic and hybrid solar cells. Analysis of the optical parameters using transfer matrix modeling within the Maxwell-Garnett effective refractive index model shows that light absorbance and exciton generation rate in the photoactive layer can be used to optimize the thickness range of the photoactive layer. Complete agreement between experimental and simulated data for solar cells with photoactive materials that have very different natures proves the validity of the proposed modeling method. The proposed simple method which is not time-consuming to implement permits to obtain a preliminary assessment of the reasonable range of layer thickness that will be needed for designing experimental samples.
RESUMEN
Polyaniline (PANI) layers are electrochemically obtained in the presence of four polysulfonic acids with different rigidities of the polymer backbone-iso-(and tere-)poly-(4,4'-(2,2'-disulfonic acid)-diphenylene-iso(tere)-phthalamide (i-PASA and t-PASA), polystyrenesulfonic acid (PSSA) and poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPSA). Combined microgravimetric (EQCM) and electrochemical measurements are carried out in the course of polymerization and repetitive redox switching. It is found that after synthesis PASA-doped PANIs shows good stability with low exchange of mass in the course of voltammetric scans, while PAMPSA-doped PANI contains a large amount of water that gradually becomes expelled in the repetitive redox switching. PANI obtained in the presence of PSSA takes an intermediate position with respect to mass exchanged in the electrochemical redox process. XPS studies are used to obtain data for the extent of doping of the different PANI materials. The results show high doping level (about 0.5) for PASA- and PAMPSA- and lower level (0.32) for PSSA-doped PANI layers. Repeated electrochemical studies carried out with the specimens investigated by XPS after long-term storage in the dry state give evidence for structural rearrangement, perfect recuperation of the initial electrochemical activity and high stability of the electrochemical response.
RESUMEN
Fabricating plasmon-enhanced organic nanomaterials with technologically relevant supporting architectures on planar solids remains a challenging task in the chemistry of thin films and interfaces. In this work, we report a bottom-up assembly of ultrathin layered composites of conductive polymers with photophysical properties enhanced by gold nanoparticles. The polydiacetylene component was formed by photopolymerization of a catanionic mixture of pentacosadiynoic surfactants on a surface of citrate-stabilized gold hydrosol monitored by a fiber optic spectrometer. Microscopic examination of the 3 nm thick solid-immobilized film showed that gold nanoparticles (AuNPs) do not aggregate within the monolayer upon polymerization. This polydiacetylene/AuNPs monolayer was coupled with 60 nm thick polyaniline-based layer deposited atop. The resulting polymer composite with an integrated 4-stripe electric cell showed nonadditive electric behavior due to the formation of electron-hole pairs with increased charge carrier mobility at the interface between the polymer layers. Under visible light irradiation of the composite film, a plasmonic effect of the gold nanoparticles was observed at the onset of photoconductivity, although neither polydiacetylene nor the polyaniline component alone are photoconductive polymers. The results indicate that our bottom-up strategy can be expanded to design other plasmon-enhanced ultrathin polymer composites with potential applications in optoelectronics and photovoltaics.
