An alternative radiolytic route for synthesizing conducting polymers in an organic solvent

A new and simple promising method for synthesizing conducting polymers in organic solvents was successfully achieved for the first time thanks to the oxidative polymerization of 3,4-ethylenedioxythiophene (EDOT) monomers dissolved in dichloromethane by means of gamma-radiolysis. The EDOT polymerization was controlled and optimized thanks to the study of the dose effect under an inert atmosphere. UV-Vis absorption spectroscopy was used to follow the polymerization process and to estimate both the radiolytic yield of EDOT oxidation and the required irradiation dose for quantitative poly(3,4-ethylenedioxythiophene) (PEDOT) preparation. Size exclusion chromatography (SEC) was used to determine the molar mass of the PEDOT polymers and thus their degree of polymerization. Polymers containing up to 20 EDOT units were detected. After deposition, ATR-FTIR spectroscopy and Energy-Dispersive X-ray (EDX) analysis highlighted the in situ doping of PEDOT polymers with chloride ions generated during dichloromethane radiolysis, while XRD analysis demonstrated the amorphous structure of the polymers. The morphology of the radiosynthesized PEDOT polymers was characterized in solution by Cryo-TEM microscopy and after deposition by SEM microscopy as well as by high-resolution AFM-IR microscopy coupled with infrared nanospectroscopy. In all cases, aggregated and packed spheroidal PEDOT particles with diameters comprising between 100 nm and 1.5 μm were observed. Besides, cyclic voltammetry (CV), four-point probe measurements and thermogravimetric analysis (TGA) showed that the PEDOT polymers radiosynthesized in dichloromethane are characterized by interesting electrical properties and good thermal stability. The present study bears witness to the tremendous potential of our radiation-based methodology and gives us a glimpse of future promising syntheses of different kinds of conducting polymers in organic solvents and even in complex matrices

Radiation-induced polymerization of 3-hexylthiophene in oxygen-free and oxygen-saturated dichloromethane solvent

We thank Jean-Michel Guigner (IMPMC, Université Pierre et Marie Curie, France) for Cryo-TEM experiments.As alternative radiolytic approach, the synthesis of P3HT was made possible thanks to the oxidation of 3HT monomers by chloromethyl and dichloromethyl radicals or by their corresponding peroxyl radicals in situ produced by dichloromethane solvent radiolysis. Under two different experimental conditions, in oxygen-free solution and in oxygen-saturated solution, two different polymers, “P3HTN2” and “P3HTO2” respectively, were successfully synthesized. Both produced materials were discerned by several analytical and spectroscopic techniques. UV–Vis absorption spectroscopy results showed that the radiolytic yield of 3HT oxidation in dichloromethane solvent is higher under O2 atmosphere. Indeed, a dose of 75 kGy was needed to polymerize 10 mM in 3HT under N2 atmosphere, meanwhile a dose of 35 kGy was sufficient to polymerize the same amount of 3HT under O2. The average molecular weight of P3HTO2was found higher than that of P3HTN2 as revealed by SEC chromatography analysis. Also, P3HTO2exhibits better thermal stability than P3HTN2. ATR-FTIR spectroscopy revealed the specific presence into P3HTO2 polymers of some functional groups such as carbonyl, hydroxyl and carboxyl moieties, which clearly explains the difference between the morphological structures of P3HTN2 and P3HTO2 as highlighted by cryo-TEM, SEM and AFM microscopies. Finally, both radio-synthesized P3HTN2 and P3HTO2 polymers were found characterized by remarkably significant conductive, electronic and optical properties

Optimal strategy based on radiation chemistry for facile and direct synthesis of poly(3-thiophene acetic acid) polymers in water and dichloromethane

In this work, synthesis of nanostructured conducting poly(3-thiophene acetic acid) (PTAA) polymers was developed by means of γ-induced oxidative polymerization of TAA monomers dissolved either in water or in dichloromethane. This synthesis was shown to be facile and directly feasible without any prior esterification of TAA and in the absence of oxidizing agents. Radiolytic yields of TAA oxidation as well as irradiation doses required for quantitative PTAA preparation were determined for each solvent. UV-Vis and ATR-FTIR spectroscopies demonstrated the successful formation of two PTAA polymers, so-called "PTAAH2O"and "PTAACH2Cl2". Size exclusion chromatography (SEC) highlighted convergent molecular weight values corresponding to approximately 13 monomer units. A similar behavior for both radio-synthesized PTAAs was monitored by thermogravimetric analysis (TGA). The morphological structures of PTAAH2O and PTAACH2Cl2 were analyzed in solution by Cryo-TEM and after deposition by SEM and AFM. Microscopic observations revealed the presence of two distinguishable nanostructures: nano-spherules of several hundreds of nanometers made of PTAAH2O and nano-granules of several tens of nanometers made of PTAACH2Cl2. Cyclic voltammetry analysis and the Tauc plot method were employed to calculate the electrical and optical band gaps. Both polymers possess similar electrical band gaps. However, PTAACH2Cl2 affords a lower optical band gap than PTAAH2O. Four-point probe measurements showed that the radio-synthesized PTAA polymers are characterized by interesting electrical properties: a higher electrical conductivity was nevertheless recorded for PTAACH2Cl2. This study highlights the powerful ability of the radiation chemistry-based methodology to lead, as a simple, versatile and reliable method, to nanostructured PTAA conducting polymers either in aqueous or organic solutions

Synthesis and Optical Properties of a Series of Push-Pull Dyes Based on Pyrene as the Electron Donor

Fifteen push-pull dyes comprising the tetracyclic polyaromatic pyrene have been designed and synthesized. The optical properties of the fifteen dyes have been examined in twenty-two solvents of different polarities. Surprisingly, contrarily to what is classically observed for push-pull dyes of D-π-A structures, a negative solvatochromism could be found for numerous dyes. The photoluminescence and thermal properties of the dyes were also examined. Theoretical calculations were carried out to support the experimental results

Synthesis and Optical Properties of a Series of Push-Pull Dyes Based on Pyrene as the Electron Donor

International audienceFifteen push-pull dyes comprising the tetracyclic polyaromatic pyrene have been designed and synthesized. The optical properties of the fifteen dyes have been examined in twenty-two solvents of different polarities. Surprisingly, contrarily to what is classically observed for push-pull dyes of D-π-A structures, a negative solvatochromism could be found for numerous dyes. The photoluminescence and thermal properties of the dyes were also examined. Theoretical calculations were carried out to support the experimental results

Humidity Sensing Applications of Lead-Free Halide Perovskite Nanomaterials

Over the past decade, perovskite-based nanomaterials have gained notoriety within the scientific community and have been used for a variety of viable applications. The unique structural properties of these materials, namely good direct bandgap, low density of defects, large absorption coefficient, high sensitivity, long charge carrier lifetime, good selectivity, acceptable stability at room temperature, and good diffusion length have prompted researchers to explore their potential applications in photovoltaics, light-emitting devices, transistors, sensors, and other areas. Perovskite-based devices have shown very excellent sensing performances to numerous chemical and biological compounds in both solid and liquid mediums. When used in sensing devices, Perovskite nanomaterials are for the most part able to detect O2, NO2, CO2, H2O, and other smaller molecules. This review article looks at the use of lead-free halide perovskite materials for humidity sensing. A complete description of the underlying mechanisms and charge transport characteristics that are necessary for a thorough comprehension of the sensing performance will be provided. An overview of considerations and potential recommendations for the creation of new lead-free perovskite nanostructure-based sensors is presented

Push-pull dyes based on Michler's aldehyde: Design and characterization of the optical and electrochemical properties

International audienceFifteen dyes based on Michler's aldehyde used as the electron donating group and differing by the electron accepting groups have been designed and synthesized. Interestingly, all dyes showed a broad absorption extending over the visible range. Examination of the solvatochromism in twenty-three solvents of different polarities revealed these dyes to give remarkable linear correlations using the Kamlet-Taft solvent polarity scale or the SPP Catalan empirical scales. The different dyes were also characterized by photoluminescence spectroscopy as well as cyclic voltammetry. To get a deeper insight into the optical properties of the different dyes, theoretical calculations were also carried out

Thermally Activated Delayed Fluorescence Emitters for Deep Blue Organic Light Emitting Diodes: A Review of Recent Advances

Organic light-emitting diodes offer attractive perspectives for the next generation display and lighting technologies. The potential is huge and the list of potential applications is almost endless. So far, blue emitters still suffer from noticeably inferior electroluminescence performances in terms of efficiency, lifespan, color quality, and charge injection/transport when compared to that of the other colors. Emitting materials matching the NTSC standard blue of coordinates (0.14, 0.08) are extremely rare and still constitutes the focus of numerous academic and industrial researches. In this context, we review herein the recent developments on highly emissive deep-blue thermally activated delayed fluorescence emitters that constitute the third-generation electroluminescent materials

Carbazole-based material: Synthesis, Characterization and Application as hole transporting material in perovskite solar cells

International audienceThe synthesis and characterization of a novel oligomeric cyclic carbazole-based material (Pcz1) for an application as hole transporter (HTM) in hybrid perovskite photovoltaic devices is reported. Its preliminary application in Cs0.08FA0.80MA0.12Pb(I0.88Br0.12)3 mixed perovskite solar cell (PSC) lead to a device power conversion efficiency of 18.04 % which is comparable to that of the Spiro-OMeTAD reference cells (17.94 %). In addition, the novel HTM is proved to act as a good barrier and protect satisfactorily the perovskite surface giving highly stable PSC devices

Nanostructured conjugated polymer for solar cell applications

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