Published October 18, 2019 | Version v1
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Extension of radiolytic procedure to the preparation of conducting polymers in organic solvents: synthesis, characterization and applications

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The extension of our original radiolytic methodology to the use of organic solvents was an important alternative approach to radiation-induced polymerization of conducting polymers (CPs) in aqueous solutions. The polymerization of CPs was studied by using γ-radiolysis of several organic solvents under different environmental conditions. The optimization of the synthesis conditions of CPs was then conducted into dichloromethane solvent. After optimization of the synthesis conditions (atmosphere, dose, dose rate, concentration of organic monomers, etc.), the use of dichloromethane radiolysis was successfully employed to synthesize various types of conducting polymers: Poly (3,4-ethylene-dioxy-thiophene) (PEDOT), Poly (3-thiophene acetic acid) (PTAA) and Poly (3-hexylthiophene) (P3HT). The radio-synthesized polymers were fully characterized in solution and after deposition by complementary analytical, spectroscopic and microscopic techniques. Also, the simplicity and versatility of radiation induced polymerization of 3-thiophene acetic acid in dichloromethane and in aqueous solutions was demonstrated. The differences between the two radiolysis routes were highlighted. Furthermore, the influence of generating different oxidizing species under different atmospheres (N2, air or O2) upon γ-irradiation of dichloromethane solutions containing organic monomers was also studied in particular in case of P3HT. The electronic and electrochemical properties were checked for all radio-synthesized CPs. Accordingly, these polymers were then incorporated in hybrid organic and inorganic perovskite solar cells (PSCs) and used as hole transport materials (HTMs). Our new radiolytic strategy described and extended in this manuscript opens the way for the preparation of new nanostructured CPs with controlled morphology and enhanced properties by using microemulsion polymerization and also for the preparation of processable conjugated materials through copolymerization. (author)

Abstract (French)

Dans le present travail, nous avons etendu aux solvants organiques notre methodologie radiolytique de synthese de polymeres conducteurs (PCs), initialement developpee en solutions aqueuses. Dans ce contexte, la polymerisation des PCs a ete etudiee par radiolyse gamma dans differents solvants organiques et sous differentes conditions experimentales. La synthese radio-induite a, en particulier, ete optimisee dans le dichloromethane grace a la variation et a l'ajustement de differents parametres: atmosphere, dose, debit de dose, concentration des monomeres, etc. Cette synthese a ainsi pu mener a la preparation de differents types de polymeres conducteurs: poly (3,4-ethylenedioxythiophene) (PEDOT), poly (3-thiophene acetique acide) (PTAA) et poly (3-hexylthiophene) (P3HT). Ces derniers ont ete totalement caracterises en solutions ou apres depot par des techniques analytiques, spectroscopiques et microscopiques complementaires. Nous avons en particulier demontre la simplicite et la versatilite de la polymerisation radio-induite de TAA que ce soit dans le dichloromethane ou dans l'eau, et avons mis en evidence quelques differences notables entre ces deux voies de synthese. Nous avons, par ailleurs, evalue l'influence de la nature des especes radiolytiques oxydantes generees dans le dichloromethane, via la variation de l'atmosphere de travail (N2, air ou O2), sur les proprietes des polymeres conducteurs radio-synthetises, en particulier dans le cas de P3HT. Parmi les nombreuses proprietes physiques chimiques que nous avons sondees dans le cas de tous nos polymeres conducteurs radio-synthetises les proprietes electroniques et electrochimiques ont fait l'objet d'une attention particuliere. Nos materiaux ont alors ete incorpores au sien de cellules solaires a perovskite hybrides organiques-inorganique (PSCs) et y ont ete utilises comme materiaux de transport de trous (HTMs). Notre nouvelle strategie radiolytique de synthese decrite et etende dans le present manuscrit, ouvre sans aucun doute la voie a la preparation de nouveaux PCs nanostructures, de morphologie controlee et aux proprietes augmentees: par exemple grace a l'utilisation d'une polymerisation en microemulsions ou par le developpement d'une copolymerisation raisonnee. (auteur)

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Additional details

Additional titles

Original title (English)
Extension de la procedure radiolytique a la preparation de polymeres conducteurs dans des solvants organiques: synthese, caracterisation et applications

Publishing Information

Imprint Pagination
260 p.
Report number
FRNC-TH--15071

INIS

Country of Publication
France
Country of Input or Organization
France
INIS RN
54123626
Subject category
S36: MATERIALS SCIENCE; S38: RADIATION CHEMISTRY, RADIOCHEMISTRY AND NUCLEAR CHEMISTRY;
Resource subtype / Literary indicator
Thesis
Descriptors DEI
ACETIC ACID; CHEMICAL REACTION KINETICS; CONTROLLED ATMOSPHERES; DOSE-RESPONSE RELATIONSHIPS; ELECTRIC CONDUCTIVITY; GRADED BAND GAPS; METHYLENE CHLORIDE; NANOCOMPOSITES; NANOSTRUCTURES; ORGANIC SOLAR CELLS; PH VALUE; POLYCYCLIC SULFUR HETEROCYCLES; POLYMERIZATION; POLYMERS; RADIOLYSIS; SYNTHESIS; THIN FILMS; VOLTAMETRY
Descriptors DEC
ATMOSPHERES; CARBOXYLIC ACIDS; CHEMICAL RADIATION EFFECTS; CHEMICAL REACTIONS; DECOMPOSITION; DIRECT ENERGY CONVERTERS; ELECTRICAL PROPERTIES; EQUIPMENT; FILMS; HETEROCYCLIC COMPOUNDS; KINETICS; MATERIALS; MONOCARBOXYLIC ACIDS; NANOMATERIALS; ORGANIC ACIDS; ORGANIC CHLORINE COMPOUNDS; ORGANIC COMPOUNDS; ORGANIC HALOGEN COMPOUNDS; ORGANIC SULFUR COMPOUNDS; PHOTOELECTRIC CELLS; PHOTOVOLTAIC CELLS; PHYSICAL PROPERTIES; RADIATION EFFECTS; REACTION KINETICS; SOLAR CELLS; SOLAR EQUIPMENT

Optional Information

Notes
354 refs.; Available from the INIS Liaison Officer for France, see the INIS website for current contact and E-mail addresses