Electrosynthesis of poly(3-methylthiophene) films: salt effect on the electrochemical and impedance properties

We studied the electrosynthesis of poly(3-methylthiophene) films in different electrolytes, i.e. 0.1?M quaternary ammonium salt solutions in acetonitrile. The analysis of the different results enabled us to explain the role of the cations and the anions of the electrolyte (doping agents) in the electrochemical synthesis and film properties. The films obtained with tetramethylammonium hexafluorophosphate (TMAPF₆) are more electroactive than those prepared using tetramethylammonium tetrafluoroborate (TMABF₄). This unexpected difference of behavior is due to the difference of hygroscopic properties of the two salts. We then characterized the films by electrochemical impedance spectroscopy. This technique, used to investigate the electrochemical properties, allowed us to virtually design identical electrical-equivalent circuits for the two types of film (prepared either with TMAPF₆ or with TMABF₄). We noted dissimilarities in the values of the components of those equivalent circuits. The different components were separately studied and their differences were explained by the salt effects.     

The effect of morphology on the transport of dichloromethane in poly(aryl-ether-ether-ketone)

A study of the transport of the dichloromethane in neat poly(aryl-ether-ether-ketone) (PEEK) samples with thicknesses from 0.08 to 3.0 mm with different morphologies was conducted at 35°C. Both sorption and desorption of the solvent were studied. Thermal annealing was used to vary the sample morphology, and density measurements were used to determine the crystallinity of the samples. The equilibrium concentration of solvent and rate of solvent sorption were found to vary with sample morphology. The density of the dichloromethane when in the PEEK resin was found to be 1.65 g/cm³. Solvent desorption was independent of sample morphology or any previous sample treatment and depended only upon desorption temperature. Solvent sorption appears to alter the morphology of amorphous samples by increasing the crystallinity to about 20% after one sorption/desorption cycle. Small amounts of the solvent, less than 0.5 wt.%, remain trapped in fully desorbed samples. The micromorphology of solvent-induced crystallization appears to be different from that induced by thermal treatment.     

Tuning of the charge and energy transfer in ternary CdSe/poly(3-methylthiophene)/poly(3-hexylthiophene) nanocomposite system

Composite CdSe:poly(3-methylthiophene) (P3MT) nanoparticles have been synthesized via polymerization of 3-methylthiophene (3MT) in the presence of CdSe particles of nanorod or dot-like morphology and dispersed in the poly(3-hexylthiophene) (P3HT) matrix. The effect of the P3MT layer to mediate charge and energy transfer between CdSe and P3HT in the ternary nanocomposite system has been studied using electronic absorption, photoluminescence spectroscopy, and current–voltage measurements. The energy level diagram of the composite system has been deduced based on optical and electrochemical data of the separate components of the system. The contribution of the low- and high-molecular fractions of P3MT to control the charge transfer in order to optimize the intermediary role of P3MT is analyzed. Particularly, it was shown that excitation of the low-molecular P3MT leads to energy transfer to both CdSe and P3HT components, and it also serves as a barrier against recombination of electrons and holes separated at CdSe and P3HT, respectively. Thus, the role of the P3MT interlayer in assisting the charge separation and increasing an open-circuit voltage in the photovoltaic cell based on the ternary system is demonstrated.     

Electrocatalytic activity of poly(3-methylthiophene) electrodes

Poly 3-methylthiophene (P3MT) modified electrodes have shown an improvement for detecting catecholamines when compared to classical ones. Past work with this polymer electrode suggested the possible presence of “active sites,” which are believed to be the polymer’s center of electrocatalytic activity. The interaction of 1,5-anthroquinone-disolfonic acid (1,5-AQDS) at the P3MT electrode showed a nonreversible behavior resulting in the blocking of “the active sites,” suggesting the specific electcatalytical activity of this polymer is limited to catechol and similar compounds. In order to improve catecholamine detection, two methods of electropolymerization for P3MT were compared under similar conditions; (1) a constant potential for a specific length of time, and (2) potential cycling. It was found that cycling provided a more sensitive CV, i.e. increased number of active sites. Under a controlled pH study (pH range 2–9), the polymer electrode maintained its superior performance, manifested as lower ΔE and higher i, toward catechol over the traditional electrodes. Two different supporting electrolytes were used, sulfate and phosphate, and it was found that in neutral or basic solutions containing phosphate, the oxidation and reduction potentials of catechol shifted to lower values. Solutions containing sulfate exhibited no shift in the oxidation potential at any pH value.     

The effect of the nature of the dopant on the sensor response of poly(3-methylthiophene) films

The effect of the nature of the dopant on the response of a sensor array based on films of poly(3-methylthiophene) under the influence of various organic solvents was studied. It was established that the electroconductivity of the polymer can both increase and decrease under the influence of the analytes. It was suggested that the main factors determining the magnitude of the response of poly(3-methylthiophene) are the ratio of the number of radical-cationic and dicationic states in the polymer, which depends on the nature of the dopant-anion, and also the polarity of the analyte. It was shown that the polymer has high sensitivity to chloroform vapor, which makes sensor arrays based on poly(3-methylthiophene) selective with respect to this analyte. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 6, pp. 331–338, November–December, 2006.     

ESR and optical measurement on poly(3-methylthiophene)

The elementary excitations of poly(3-methyl-thiophene) in a doping range up to 7.5% have been found to be polarons as evidenced by ESR-measurements. Above 7.5% doping Pauli susceptibility indicates metallic behaviour. In contrast, at 5% doping the optical absorption spectra show a transition from the three peak structure due to polarons to one with two peaks and commonly assigned to the formation of bipolarons. It is argued that a widening of the polaron levels gives rise to this phenomenon and not the induction of bipolarons. Above 20% doping the formation of a new phase of the material is observed, which is characterized by the disappearance of the peak at 1.6 eV and a well defined isosbestic point at 1.4 eV.     

Enhanced photoresponse of poly(3-methylthiophene) supported on TiO2

We have investigated the photoelectrochemical behavior of poly(3-methylthiophene) supported on nanostructured n-TiO₂ in a solid-state photoelectrochemical device. As electrolyte we employed the elastomer poly(epichlorohydrin-co-ethylene oxide) filled with NaI/I₂. Under polychromatic light irradiation (60 mW cm⁻²) the device exhibits an open circuit voltage, a short-circuit current and fill factor of 10 μA cm⁻², 0.048 V and 0.29, respectively. The overall efficiency of the cell is 2.3×10⁻²%.     

Electrosynthesis and characterization of poly(3-methylthiophene) on different substrates

 We report on the study of the electropolymerization of 3-methylthiophene onto Pt, p-Si and indium-tin oxide deposited on polyester using quartz crystal microgravimetry, electrochemical and spectroelectrochemical measurements. We observe that potential variation during the galvanostatic electrodeposition is correlated with the nucleation process. The mass variation of poly(3-methylthiophene) is linear with the amount of the electrochemical charge whereas the absorbance variation curve shows two distinct slopes. The latter result has been explained in terms of conjugation length variation during polymer growth. Scanning electron microscopy analysis allowed the detection of morphological changes from a dense and compact structure to an open morphology when the poly(3-methylthiophene) film thickness increases. The roughness of the films did not change considerably with the substrate, as observed by atomic force microscopy. Absorption and photocurrent spectra at different film thicknesses show a shift of the peaks to lower wavelengths when the thickness increased, thus confirming the decrease of mean conjugation length in thicker films. Received: 1 September 1998 / Accepted: 11 November 1998     

Surface-initiated synthesis of poly(3-methylthiophene) from indium tin oxide and its electrochemical properties

Poly(3-methylthiophene) (P3MT) was synthesized directly from indium tin oxide (ITO) electrodes modified with a phosphonic acid initiator, using Kumada catalyst transfer polymerization (KCTP). This work represents the first time that polymer thickness has been controlled in a surface initiated KCTP reaction, highlighting the utility of KCTP in achieving controlled polymerizations. Polymer film thicknesses were regulated by the variation of the solution monomer concentration and ranged from 30 to 265 nm. Electrochemical oxidative doping of these films was used to manipulate their near surface composition and effective work function. Doped states of the P3MT film are maintained even after the sample is removed from solution and potential control confirming the robustness of the films. Such materials with controllable thicknesses and electronic properties have the potential to be useful as interlayer materials for organic electronic applications.     

Solvation/desolvation during the redox transformation of poly(3-methylthiophene)

Solvation/desolvation effects were studied during the redox transformation of poly(3-methylthiophene) by electrochemical quartz crystal microbalance technique. The effect was demonstrated by studying the phenomenon in different solvents, and comparing the results after a solution change. From the data obtained with the same film transferred between nitrobenzene and acetonitrile in both directions, the solvation effect was directly evidenced, and the virtual molar mass of the moving species in and from the same film was determined to illustrate semi-quantitatively the effect of the solvation.This paper is dedicated to Professor G. Horányi on the occasion of his 70th birthday and in recognition of his outstanding contribution of electrochemistryCsaba Visy, Emese Kriván are ISE members     

Effects of packing structure on the optoelectronic and charge transport properties in poly(9,9-di-n-octylfluorene-alt-benzothiadiazole)

Spin-coated poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) films of different molecular weights (Mn= 9-255 kg/mol), both in the pristine and annealed state, were studied in an effort to elucidate changes in the polymer packing structure and the effects this structure has on the optoelectronic and charge transport properties of these films. A model based on quantum chemical calculations, wide-angle X-ray scattering, atomic force microscopy, Raman spectroscopy, photoluminescence, and electron mobility measurements was developed to describe the restructuring of the polymer film as a function of polymer chain length and annealing. In pristine high molecular weight films, the polymer chains exhibit a significant torsion angle between the F8 and BT units, and the BT units in neighboring chains are close to one another. Annealing films to sufficiently high transition temperatures allows the polymers to adopt a lower energy configuration in which the BT units in one polymer chain are adjacent to F8 units in a neighboring chain ("alternating structure"), and the torsion angle between F8 and BT units is reduced. This restructuring, dictated by the strong dipole on the BT unit, subsequently affects the efficiencies of interchain electron transfer and exciton migration. Films exhibiting the alternating structure show significantly lower electron mobilities than those of the pristine high molecular weight films, due to a decrease in the efficiency of interchain electron transport in this structure. In addition, interchain exciton migration to low energy weakly emissive states is also reduced for these alternating structure films, as observed in their photoluminescence spectra and efficiencies.     

Voltammetric detection of sulfonamides at a poly(3-methylthiophene) electrode

Detection of sulfonamide compounds in a mixture of standards at a poly(3-methylthiophene) coated on glassy carbon (GC) electrode is reported. The polymer, poly(3-methylthiophene), was electrochemically synthesized at a GC rotating disk-working electrode versus Ag/AgCl using cyclic voltammetry (+0.5 to +2.0 V). Square wave voltammetry (SQWV) with cathodic reduction (0 to -4.0 V) was used for the detection of seven sulfonamide compounds in a mixture. The working concentration ranges (curvilinear) established for different compounds in Britton-Robinson (BR) buffer (pH 6.26), were: 5.0x10(-6)-3.2x10(-3) M sulfamerazine, 5.0x10(-6)-3.2x10(-3) M sulfadiazine, 7.5x10(-7)-3.2x10(-4) M sulfasalazine, 9.0x10(-7)-5.0x10(-4) M sulfamethazine, 6.5x10(-8)-3.5.0x10(-5) M sulfamethoxazole, 9.7x10(-8)-5.0x10(-5) M sulfathiazole, and 9.0x10(-8)-3.2x10(-5) M 5-sulfaminouracil. Detection limits were calculated as: 3.9x10(-6) M for sulfamerazine; 4.0x10(-6) M sulfadiazine; 2.5x10(-7) M sulfasalazine; 3.7x10(-7) M sulfamethazine; 4.0x10(-8) M sulfamethoxazole; 6.4x10(-8) M sulfathiazole and 6.0x10(-9) M 5-sulfaminouracil. The data suggests a potential application of the poly(3-methylthiophene) (P3MT) electrode for determination of sulfonamides in veterinary and other applications.     

Potentiometric response of poly(3-octylthiophene), poly(3-methylthiophene) and polythiophene in aqueous solutions

The potentiometric response of some polythiophenes in aqueous solutions has been investigated. Polythiophene (PT), poly(2,2'-bithiophene) (PBT), poly(3-methylthiophene) (PMT), poly(3-octylthiophene) (POT) and poly(4,4'-dioctyl2,2'-bithiophene) (POTd) were electrochemically deposited on platinum in 0.1M LiBF(4)-propylene carbonate solution containing the corresponding monomer or dimer. Polymer electrodes were also prepared by solution casting of chemically synthesized poly(3-octylthiophene) (POTc) dissolved in chloroform. After film deposition (electrochemical or chemical) the polymer coated electrodes were used as indicator electrodes in potentiometric measurements. The open-circuit potential of the polymer electrodes was measured in aqueous solutions containing inorganic salts (10(-1)-10(-4)M). Interestingly, all the polythiophenes studied were found to give a cationic response to monovalent cations such as H(+), Li(+), Na(+), K(+) and NH(+)(4) (Cl(-) salts). The slope, calculated from the linear part of the response curve, was found to depend on the polythiophene used but always remained lower than that predicted for a Nernstian response. The polythiophenes also showed some sensitivity to divalent cations such as Mg(2+) and Ca(2+) (Cl(-)-salts). POT was used as the polymer to study the influence of the polymerization conditions on the potentiometric response. By investigating different polymers from the polythiophene family it was possible to evaluate how the starting material (monomer or dimer) and the presence of alkyl side-chains influence the potentiometric response of the polymer membranes.     

The effect of morphology on sorption and transport of carbon dioxide in poly(4,4'-oxydiphenylene pyromellitimide)

Sorption and transport of carbon dioxide were investigated for poly(4,4'-oxydiphenylene-pyromellitimide) films (PI-1, PI-2, and PI-3) imidized at 160, 200, and 400°C, respectively, as well as for a chemically identical commercial polyimide film, Kapton-H. The solubility, permeability, and diffusion coefficients (S, P, and \[ \overline D \] , respectively) at 80°C and 20 atm in PI-3 were 67, 25, and 37%, respectively, as large as those in PI-2. These significant reductions are attributed to a higher degree of segmental aggregation in PI-3 caused by a 1.7% increase in the density (d) as compared with PI-2. The differences in S, P, \[ \overline D \] , and d between PI-3 and Kapton-H were rather small as compared with those between PI-3 and PI-2, suggesting that the in-plane orientation has a minor effect on the sorption and transport in Kapton-H as compared with the aggregation. Influence of the morphology on the dual-mode sorption and transport parameters was also investigated. With increasing density, the Langmuir capacity constant and the diffusion coefficients for the Henry's law and Langmuir populations decreased by higher rates than the Henry's law solubility constant, being contrary to the results reported for a typical semicrystalline glassy polymer, polyethylene terephthalate. This may suggest that the nonaggregated or less-aggregated regions taking an important part in the sorption and transport are denser for the sample having a higher overall density.     

Sulfonated polyaniline/poly(3-methylthiophene)-based photovoltaic devices.

A sulfonated polyaniline (SPAN) film as an intermediate layer between the electrode, tin oxide (TO) and the active layer improves the efficiency of photovoltaic devices based on poly(3-methylthiophene), PMT. In TO/SPAN/PMT/Al devices, the incident-photon-to-collected-electron efficiency reaches 12.1% and power conversion efficiency 0.8% under monochromatic irradiation (λ = 580 nm; 0.8 W/m²). Under AM 1.5 conditions 1000 W/m², a power conversion efficiency of 0.04% is reached.     

Analytical applications of poly(3-methylthiophene)-coated cylindrical carbon fiber microelectrodes

Some analytical applications of carbon fiber microelectrodes (CFMEs) modified with cyclic voltammetric electrogenerated poly(3-methylthiophene) (P3MT) coatings are described. Cyclic voltammograms in aqueous solutions of the phenolic antioxidants tert-butylhydroxyanisole (BHA), tert-butylhydroquinone (TBHQ), propylgallate (PG), and tert-butylhydroxytoluene (BHT) showed that electrocatalytic effects and an improved electrode kinetics occurred at the modified microelectrodes when compared with GC electrodes of conventional size. Moreover, reproducible voltammograms were obtained, obviating the need of cleaning or pretreatment of the coated microelectrode. Another important analytical advantage was the greatly improved resolution for mixtures of analytes. The behavior of P3MT-CFMEs in organized media was tested by considering their voltammetric response towards the electrochemical oxidation of PG. The nonionic surfactant Pluronic F 68 was selected as the most suitable to form micellar solutions of PG, as well as the emulsifying agent for the preparation of oil-in-water emulsions. A 20:80 ethyl acetate:n-hexane mixture was used as the organic phase and a 0.05 mol L⁻¹ H₃PO₄/H₂PO₄⁻ buffer solution of pH 2.0 as the aqueous continuous phase. Cyclic voltammetry demonstrated that the PG oxidation current was purely diffusion-controlled in the organized medium. The analytical characteristics obtained by using differential pulse voltammetry were slightly better than those obtained in aqueous solution. Furthermore, the improved resolution for mixtures of analytes is retained in the oil-in-water emulsified medium. The proposed method was applied with good results to the determination of PG in spiked commercial dehydrated soup samples by direct emulsification of aliquots of the sample extract in the ethyl acetate:n-hexane mixture.     

Electrical characterization of poly(3-methylthiophene) electrosynthesized onto a tin-oxide substrate

We have investigated poly(3-methylthiophene) (PMeT) thin films electrochemically synthesized directly onto a tin-oxide (TO) electrode. We find that the PMeT film thickness depends linearly on the charge density used during the electropolymerization. We have demonstrated that the current transport in PMeT films (solid phase) is space-charge limited or controlled by thermionic emission, depending on the electrode material. Using TO/PMeT/Ni devices we estimate the positive charge carrier mobility in PMeT to be around 4 × 10⁻⁴ cm² V⁻¹ s⁻¹, and the potential barrier height for positive charge carrier injection at the Al/PMeT interface to be 0.17 eV. Received: 6 December 1999 / Accepted: 24 February 2000     

Photogeneration of charge carriers and their transport properties in poly[bis(p-n-butylphenyl)silane

The photocarrier generation mechanism and mobility in poly[bis(p-n-butylphenyl)silane] (PBPS) thin films doped with a variety of electron acceptors are studied by time-resolved microwave conductivity (TRMC) measurements. It was found that fullerene is a suitable electron acceptor for PBPS as it provides the highest product of photocarrier generation yield phi and mobility Sigmamu under excitation at 532 and 355 nm. The observed high phiSigmamu value of 4.5 x 10(-3) cm(2)/(V s) under excitation at 193 nm (6.39 eV) can be attributed to the direct ionization of PBPS molecules. The photoinduced electron transfer between C(60) and PBPS was investigated in a solution sample by laser flash photolysis under excitation at 532 nm. On the basis of the extinction coefficient of PBPS(*+), transient absorption of PBPS(*+) provides a maximum value of phi of 0.83% for the electron-transfer reaction from PBPS to (3)C(60). On the basis of this value of phi, the intrinsic intrachain mobility of holes on the PBPS backbone is estimated to be higher than 1.7 x 10(-2) cm(2)/(V s), suggesting the presence of a high conducting path along the Si backbone of PBPS.     

Synergistic effect of compatibilizer and sepiolite on the morphology of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/poly(butylene succinate) blends

Blends of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and poly(butylene succinate) (PBS) with different PHBV/PBS weight ratios (100/0, 75/25, 50/50 and 0/100) were elaborated by melt mixing. The morphological investigation of the different samples, in comparison with that of neat PHBV and neat PBS, pointed out that PHBV/PBS blends form a biphasic system over the whole composition range. Low amount of compatibilizing agent (5 wt%), obtained by grafting maleic anhydride (MA) onto PHBV, i.e. PHBV-g-MA, was used for improving the miscibility between the two components of the blend. The incorporation of a fibrous filler as the sepiolite, easily dispersible in a polymer matrix, was also investigated. The morphology of the different blends as well as the evolution of their material properties were discussed in terms of the sepiolite and compatibilizing agent contents. The dispersion of PBS in the PHBV matrix markedly became finer with incorporation of sepiolite and PHBV-g-MA, due to enhanced interactions between the components. This paper highlighted a synergistic effect induced by the presence of both compatibilizer and sepiolite leading to an improved miscibility of the two blend components. The resulting properties were correlated with the morphology observed for the different blends.     

Photovoltaic devices based on electrodeposited poly(3-methylthiophene) with tin oxide as the transparent electrode

We report on the use of electrodeposited poly(3-methylthiophene) (PMeT) in photovoltaic devices. Photocurrent measurements in devices with PMeT as the active conjugated polymer layer were carried out showing that the combination of Ni and tin oxide (TO) as electrode materials presents advantages relative to Al and TO. The choice of these electrode materials permits the carriers with the lowest mobility, the negative charge carriers, to be collected near the exciton generation/dissociation region, i.e. near the transparent TO electrode, avoiding the tendency for space charge accumulation and consequently the reduction of device efficiency. Electronic Publication