The optoelectronic properties of new dyes based on thienopyrazine

International audienceIn this article, we present the quantum result of six dyes based on thienopyrazine (D1–D6) with donor–π–acceptor structure (D–π–A) using DFT/B3LYP/6-31G(d,p) and TD-DFT/CAM-B3LYP/6-31G(d,p) levels. The donor unit varied and the influence was investigated. The study of structural, electronic, and optical properties of these dyes could help design more efficient functional photovoltaic organic materials. Key parameters in close connection with the short-circuit current density (J sc ) including light harvesting efficiency, injection driving force (ΔG inject ), and total reorganization energy (λ total ) are discussed in this work

A new growth process for crystalline ultra-thin layers of conjugated oligomers used in field-effect transistor applications

Most organic semiconductor materials dewet on silicon wafers with thermal oxide layers. While Si-wafers represent convenient substrates for building a field effect transistor (FET), dewetting largely destroys the possibility for obtaining a compact and continuous crystalline thin organic semiconductor film and thus limits the mobility in these systems. Using oligothiophenes, we present an approach where the initial dewetting process can be turned into an advantage for generating very thin but large crystalline domains of a size up to the millimetres with all molecules sharing a single orientation. Our approach can be easily extended to other molecules, which have strongly differing growth velocities in the various directions of the crystal, for example due to directional π-stacking interactions. FETs devices based on such large crystalline domains showed charge carrier mobilities that were two orders of magnitude higher compared to non-crystallized films

Développement de capteurs chimiques d'explosifs basés sur la détection par fluorescence

Face à la menace croissante du terrorisme, il est essentiel de mettre en place des mesures de précaution et des moyens de surveillance permettant d'assurer la sécurité dans les lieux publics. Dans ce cadre, le CEA Le Ripault développe des systèmes de détection portatifs et autonomes dédiés àla détection d'explosifs en phase gazeuse. Cette thèse s'inscrit dans ce projet. L'objectif de cette étude est de concevoir et d'étudier les propriétés de matériaux sensibles fluorescents dédiés àla détection de composés nitroaromatiques tel que le TNT. Ainsi, les propriétés de mise en forme et de détection de différents matériaux, sensibles aux composés nitroaromatiques, ont été étudiées. Après identification du matériau le plus efficace pour cette application, nous avons étudié sa stabilité et nous avons cherché àcomprendre le mécanisme de détection associé àce matériau fluorescent. Les performances du détecteur de composés nitroaromatiques, intégrant ce matériau, ont ensuite été évaluées.In order to overcome the growing threat of terrorism, it is essential to put into operation preventive measures and means of monitoring to ensure security in public areas. In this context, the CEA Le Ripault develops portable and self-contained detection systems dedicated to the detection of explosives in the gas phase. This PhD work is part of this project. The objective of this study is to design and to assess the properties of fluorescent sensitive materials dedicated to the detection of nitroaromatic compounds such as TNT. Consequently, the ease of deposition, thin films properties and detection performances of several sensitive materials have been considered. After identification of the most effective material for this application, we studied its stability and we searched to understand the detection mechanism associated with this fluorescent material. Then, the performances of the device which incorporate this sensitive material have been evaluated for the detection of nitroaromatic compounds.MONTPELLIER-Ecole Nat.Chimie (341722204) / SudocSudocFranceF

Molécules pi-conjuguées fonctionnelles (synhèse et application à l'élaboration de nanomatériaux)

De nouveaux matériaux p-conjugués fonctionnels ont été élaborés selon deux approches. La première a consisté à préparer des molécules p-conjuguées fonctionnelles basées sur un segment central de type 1,4-bis(phénylène-éthynyl)benzène permettant de développer des nano-objets et des nanomatériaux hybrides associant les segments conjugués organiques à d'autres composantes : des nanotubes de carbone et de la silice sous la forme de nanoparticules ou de nanomatériaux. Le segment conjugué de base a été fonctionnalisé soit directement, soit par le biais de ses chaînes solubilisantes. La seconde approche a permis de développer une nouvelle famille d'oligomères conjugués organiques et solubles basés sur des motifs de type thiénopyrazine de faible gap énergétique entre les orbitales HOMO et LUMO. Les propriétés électro-optiques de ces composés exclusivement organiques ont été confrontées à des calculs prédictifs obtenus par des méthodes de la chimie théorique (DFT, TDFFT). Ces matériaux hybrides fonctionnels ont pu être valorisés. La fonctionnalisation des chaînes solubilisantes par des groupements ioniques imidazolium ont permis la conception de nouveaux matériaux polyélectrolytes pour accéder à des ionogels. La fonctionnalisation du segment conjugué en lui-même a pu être mis à profit pour la fonctionnalisation covalente de nanotubes de carbone ou de nanoparticules de silice.New p-conjugated functional materials were elaborated in two ways. The first one consisted in the preparation of p-conjugated functional molecules based on a 1,4-bis(phenylene-ethynyl)benzene central segment in order to develop hybrid nano-objects and nanomaterials which combine organic conjugated segments with other components : carbon nanotubes or silica (nanoparticules, nanomaterials). The central conjugated unit is functionalized either on this p-conjugated system or at the end of the side chains. The second approach allows the development of a new family of organic soluble conjugated oligomers based on thienopyrazine units characterized by a low band gap between HOMO and LUMO orbitals. The electronic and optic properties of these organic compounds were compared to theoretical calculations (DFT, TDFFT). The functionalization of the side chains by ionic imidazolium units could permit the conception of new polyelectrolyte materials and open the access to new ionogel materials. The functionalization of the conjugated segment was used with advantage for the covalent functionalization of carbon nanotubes or silica nanoparticules.MONTPELLIER-Ecole Nat.Chimie (341722204) / SudocSudocFranceF

Conception, synthèse et caractérisation de matériaux fluorescents pour l'élaboration d'un capteur chimique d'explosifs

Dans le cadre de la lutte antiterroriste, il est crucial d'être en mesure de détecter la présence d'explosifs dans des lieux publics. De même, le déminage des anciennes zones de conflits nécessite également de développer des outils adaptés à la détection d'explosifs. Cette thèse est consacrée à l'étude de matériaux organiques fluorescents pour la détection de nitroaromatiques qui figurent parmi les explosifs les plus courants. L'objectif de cette thèse est triple puisqu'il s'agit à la fois de concevoir de nouveaux matériaux sensibles aux nitroaromatiques par inhibition de fluorescence, de développer un prototype et de mieux cerner les mécanismes de détection des nitroaromatiques. Nous explorons la synthèse et l'utilisation de nouveaux co-polymères alternés comportant des segments conjugués fluorescents de type phénylèneéthynylène et des unités chirales de possédant un axe de symétrie C2. La présence de cette unité est susceptible de limiter les interactions pi-pi entre les fluorophores et de conférer au matériau des propriétés adéquates. Dans le but d'obtenir une sensibilité optimale, nous étudions l'incidence de la nature du segment conjugué d'une part et le type d'unité chirale d'autre part. Nous nous intéressons également aux interactions entre les nitroaromatiques et les matériaux sensibles. Les polymères alternés développés dans ce cadre conduisent à des dépôts homogènes et reproductibles. Leur bonne sensibilité et leur excellente sélectivité pour la détection des nitroaromatiques en fait d'excellents candidats pour la réalisation de capteurs. L'aboutissement de ce travail de recherche est le développement d'un prototype de détection miniaturiséTo be able to detect explosives ultra-traces has become a societal need particularly to anticipate terrorist attacks and for land mine detection. During the last decade, despite well studied heavy analytical techniques, more sensitive, rapid and portable new chemical gas sensors have been developed. This thesis is devoted to the study of fluorescent organic materials used for nitroaromatics detection which appears among the most current explosives. Three objectives concern the present work: we have to design new sensitive materials towards nitroaromatics via fluorescence quenching, to develop a portable integrated sensor and to focus on the understanding of the detection process involved in nitroaromatics sensing. We explore the synthesis and the use of new alternate copolymers bearing fluorescent conjugated segments (phenyleneethynylene type) and chiral units with a C2 symmetry axis. This chiral unit is designed in order to avoid pi-stacking between fluorophores. The effect of the conjugated segment nature and the type of chiral unit are studied in order to obtain an optimal sensitivity. The interactions between nitroaromatics and sensitive fluorescent materials are also investigated. The deposition of alternate polymers leads to homogeneous and smooth thin layers. Their good sensitivity and their excellent selectivity for nitroaromatics detection are well fitted for the development of chemical sensors. The result of this leads to the development of a miniaturized integrated prototype of detectionMONTPELLIER-BU Sciences (341722106) / SudocSudocFranceF

Far-infrared spectroscopy investigation of sulfur-oxygen interactions in pi-conjugated oligomers

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Self-Organized Ureido Substituted Diacetylenic Organogel. Photopolymerization of One-Dimensional Supramolecular Assemblies to Give Conjugated Nanofibers

International audienceThe introduction of the urea function as structure directing agent of diacetylene organogels (DA-OGs) has been achieved. Despite the urea function being one of the most frequently used structure directing agents for the formation of organogels, it has never been exploited in the fabrication and photopolymerization of DA-OGs. The self-association of ureas involving two hydrogen bonds is much stronger than that of urethanes or amides, and the resulting supramolecular assemblies are completely insoluble. In this context, 1,1'-(hexa-2,4-diyne-1,6-diyl)bis(3-(10-(triethoxysilyl)decyl)urea) 2 was synthesized. Compound 2 was soluble owing to the triethoxysilane function that we recently used in the fabrication of a silylated bis-urea-stilbene organogel. It formed an organogel, and its photopolymerization was studied in cyclohexane. The loss of the gel state and the formation of a red solution resulting from the polymerization were found to be the result of the constraints introduced by the urea function in close vicinity to the polymerizable function. To obtain an ureido substituted diacetylenic organogelator affording a blue highly conjugated polydiacetylene (PDA) without a sol-gel transition, a propylene spacer was introduced to move the urea function away from the polymerizable function (derivative 3). The thermochromism exhibited by the latter in the solid state was studied. Using the same setup and the same sample, UV-vis and FTIR spectra were simultaneously recorded as a function of the temperature to highlight a relation between color changes and urea association mode changes. The data showed that the reversible thermochromic transition must be associated with a reversible supramolecular modification and, conversely, that irreversible chromic transitions are the result of irreversible structural modifications. The chromic effects of the acidic hydrolysis-polycondensation of the trialkoxysilyl groups to form a siloxane network were studied on a thin film of 3. In the same way, solvent effects on the color of the organogels of 3 were also investigated. Correlations could be established between the different stimuli. These results provide a deeper understanding of the precise molecular mechanism of the blue to red transition and of the reversibility of the purple to red transition generally encountered in PDA thermochromism

Characterization and simulation study of organic solar cells based on donor–acceptor (D–π–A) molecular materials

International audienceIn this study, the analysis of microelectronic and photonic structure in a one dimension program [AMPS-1D] has been successfully used to study organic solar cells. The program was used to optimize the performance of organic solar cells based on (carbazole-methylthiophene), benzothiadiazole and thiophene [(Cbz-Mth)-B-T]2 as electron donors, and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) as an electron acceptor. The optoelectronic properties of these dyes were investigated by using the Density Functional Theory DFT/B3LYP/6-31G(d,p) method. We studied the influence of the variation of the thickness of the active layer, the temperature, and the density of the effective states of the electrons and the holes in the conduction and valence bands respectively on the performance of the solar cells based on [(Cbz-Mth)-BT]2-PCBM as a photoactive material, sandwiched between a transparent indium tin oxide (ITO) and an aluminum (Al) electrode. The addition of other thiophene units in the copolymer or the deposition of a layer of PEDOT between the anode (ITO) and the active layer, improves the performances of the cell, especially resulting in a remarkable increase in the value of the power conversion efficiency (PC

Spontaneous assembly of silylethane-thiol derivatives on Au(111): a chemically robust thiol protecting group as the precursor for the direct formation of aromatic gold thiolate monolayers

International audienceSelf-assembled monolayers (SAMs) on gold were obtained by the direct absorption of a fully conjugated phenylenethienylene derivative (4) presenting robust silylethane-thiol protecting groups as anchoring agents. The thiol deprotection and SAM formation have been evidenced by quartz crystal microbalance (QCM) measurements and X-ray photoelectron spectroscopy (XPS), and have been compared to the SAM obtained from its thioacetate analog (5). The chemically robust silylethane-thiol protecting group appeared as a surprisingly effective anchoring agent for the preparation of aromatic SAMs on Au(111), suitable for subsequent post-functionalization