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Les avancées technologiques et l'intégration massive de dispositifs électroniques nanométriques dans les objets de notre vie quotidienne ont généré une explosion des coûts de R&D, de conception et de production, ainsi que des inquiétudes sociétales quant à l'impact environnemental des déchets électroniques. En raison de procédés de production moins coûteux et à faible impact environnemental, de leur souplesse d’utilisation et de la possibilité de moduler leurs propriétés à l’infini, les molécules et polymères organiques constituent une classe de matériaux prometteuse pour la mise au point de nouveaux dispositifs électroniques. L’électronique organique couvre ainsi un vaste domaine d’applications, parmi lesquelles se trouvent les diodes électroluminescentes, les transistors à effet de champ ou les cellules photovoltaïques. Bien que la plupart de ces dispositifs soient déjà commercialisés, les processus gouvernant leur efficacité à l’échelle atomique sont loin d’être entièrement compris et maîtrisés. C’est en particulier le cas des processus de transport de charge, qui interviennent dans tous ces dispositifs.L'objectif de cette thèse est d’apporter une compréhension fondamentale des processus de transport de charge dans les semiconducteurs organiques, à partir d'approches théoriques combinant dynamique moléculaire, calculs quantiques et simulations Monte Carlo. Ce travail est développé suivant trois axes principaux:(I) Etude des relations liant l'organisation structurale et les propriétés de transport de cristaux moléculaires, et du rôle des fluctuations énergétiques dans des matériaux polymères amorphes. Des simulations Monte Carlo Cinétique (KMC) couplés au formalisme de Marcus-Levich-Jortner pour le calcul des taux de transfert ont été effectués afin de déterminer les mobilités des électrons et des trous au sein de dix structures cristallines de dérivés phtalocyanines. Dans une deuxième étude, une approche similaire a été employée afin de décrire les propriétés de transport de charge au sein d'un copolymère amorphe de fluorène-triphénylamine, ainsi que l'impact des fluctuations énergétiques sur ces dernières. La méthodologie développée permet d'obtenir, pour un faible coût calculatoire, une estimation semi-quantitative des mobilités des porteurs de charge dans ce type de système.(II) Etude de l'impact de contraintes mécaniques sur les propriétés de transport de matériaux organiques cristallins. La réponse électronique et les propriétés de transport de matériaux organiques soumis à une contrainte mécanique ont été étudiés à l'aide de simulations de dynamique moléculaire et de calculs DFT. Le rubrène cristallin et ses polymorphes, ainsi que les dérivés du BTBT, ont été considérés pour cette étude, qui révèle un couplage électromécanique inhabituel entre les différents axes cristallographiques. Les résultats démontrent en particulier que l'anisotropie structurale des monocristaux organiques conduit à une anisotropie du couplage électromécanique.(III) Etude du rôle du polyélectrolyte dans la conductivité des complexes conducteurs. Le polystyrène substitué par du bis(sulfonyl)imide est utilisé comme un contre-ion et un dopant dans les complexes conducteurs PEDOT-polyélectrolytes. En complément des analyses expérimentales, des simulations de dynamique moléculaire couplées à des calculs DFT ont été effectuées dans ces systèmes afin d'analyser l'impact de la conformation et de l'état de protonation du polyélectrolyte sur la conductivité du complexe formé avec le PEDOT.Les études décrites ci-dessus, réalisées sur différents types de matériaux en couplant différents types d'approches théoriques, ont permis d'apporter une compréhension fondamentale des propriétés de transport dans les semiconducteurs organiques. Elles mettent en particulier en évidence l'impact de l'organisation structurale, des interactions intermoléculaires et de l'application de contraintes mécaniques sur la mobilité des porteurs de charges dans ces matériaux. / With the advancement of technology, miniaturized electronic devices are progressively integrated into our everyday lives, generating concerns about cost, efficiency and environmental impact of electronic waste. Organic electronics offers a tangible solution paving the way for low-cost, flexible, transparent and environment friendly devices. However, improving the functionalities of organic (opto) electronic devices such as light emitting diodes and photovoltaics still poses technological challenges due to factors like low efficiencies, performance stability, flexibility etc. Although more and more organic materials are being developed to meet these challenges, one of the fundamental concerns still arises from the lack of established protocols that correlate the inherent properties of organic materials like the chemical structure, molecular conformation, supra-molecular arrangement to their resulting charge-transport characteristics.In this context, this thesis addresses the prediction of charge transport properties of organic semiconductors through theoretical and computational studies at the atomistic scale, developed along three main axes :(I) Structure-charge transport relationships of crystalline organic materials and the role of energetic fluctuations in amorphous polymeric organic semiconductors. Kinetic Monte-Carlo (KMC) studies employing the Marcus-Levich-Jortner rate formalism are performed on ten crystalline Group IV phthalocyanine derivatives and trends linking the crystalline arrangement to the anisotropic mobility of electrons and holes are obtained. Subsequently, KMC simulations based on the simpler Marcus formalism are performed on an amorphous semiconducting fluorene-triphenylamine (TFB) copolymer, to highlight the impact of energetic fluctuations on charge transport characteristics. A methodology is proposed to include these fluctuations towards providing a semi-quantitative estimate of charge-carrier mobilities at reduced computational cost.(II) Impact of a mechanical strain on the electronic and charge transport properties of crystalline organic materials. Crystalline rubrene and its polymorphs, as well as BTBT derivatives (well studied high mobility organic materials) are subjected to mechanical strain and their electronic response is analyzed. Employing tools like Molecular Dynamic (MD) simulations and plane wave DFT (PW-DFT) calculations, unusual electro-mechanical coupling between different crystallographic axes is demonstrated, highlighting the role of inherent anisotropy that is present in the organic single crystals which translates in an anisotropy of their electro-mechanical coupling.(III) Protonation-dependent conformation of polyelectrolyte and its role in governing the conductivity of polymeric conducting complexes. Polymeric bis(sulfonyl)imide substituted polystyrenes are currently employed as counter-ions and dopants for conducting poly(3,4-ethylenedioxythiophene) (PEDOT), resulting in PEDOT-polyelectrolyte conducting complexes. Employing MD simulations and DFT calculations, inherent characteristics of the polyelectrolyte like its acid-base behavior, protonation state and conformation, are analyzed in conjunction with available experimental data and the role of these characteristics in modulating the conductivity of resulting PEDOT-polyelectrolyte conducting complexes is highlighted.The above studies, performed on different organic electronic systems, emphasize the importance of inherent characteristics of organic materials in governing the charge transport behavior in these materials. By considering the inherent characteristics of organic electronic materials and systematically incorporating them into simulation models, accuracy of simulation predictions can be greatly improved, thereby serving not only as a tool to design new, stable and high performance organic materials but also for optimizing device performances.

The determination of complexes formed in weakly acidic aqueous solutions containing pentavalent vanadium as well as hexavalent molybdenum has proved diffi cui t due to slow equilibria and 1 imi ted sol ubi 1 i ty of especially the vanadium species. The formation of several different polynuclear complexes with a very varied molybdenum/vanadium ratio also complicates the interpretation of Potentiometrie data. In order to clarify the picture of complexes formed and provide starting points for equilibrium calculations single-crystal X-ray studies were made on crystals obtained from âqueous solutions. In addition, these studies can provide information on bonding conditions and possibly formation mechanisms for molybdovanadate polyanions. Crystals were synthesized by slow evaporation of aqueous solutions. Solutions with varied molybdenum/vanadium ratios and also varied pH values were prepared and used in the synthesis experiments. The X-ray measurements were performed with Philips PAILRED, Syntex P21 and Syntex R3 automatic diffractometers. All data sets were corrected for absorption. Five of the structures were solved with heavy-atom methods and one by direct methods. The structures were refined by computer-performed least-squares methods. The following crystals were obtained and structurally determined: NaV03•1.89H2O, which contains chains of VO5 trigonal bipyramids. Na4V2O7 (H2O)18 , containing discrete V2O74- anions which are completely surrounded by sodium-coordinated water molecules. Discrete molybdovanadate polyanions were found in the structures of the compounds Na6Mo6\/2O26 (H2O)16 , K7Mo8V5O40 • 8H2O, K8Mo4,V8O36 - 12H20 and K6 (V2 , Mo10) VO40 • 13H20. The last substance belongs to a class of compounds named 'heteropoly blues', which contain metal atoms in mixed-valence states, and has one unpaired electron on the polyanion. This compound was also investigated with electron spin resonance spectroscopy. The bonding configurations of oxygen atoms coordinated to molybdenum or vanadium are described and discussed. As the Mo4V8O368-, Mo8V5O407- (which is an isomer of the Keggin anion but has a quite different structure) and Mo6V2O266- anions all contain remnants of mononuclear molybdate and vanadate anions, it seems likely that these polyanions are formed mainly through the condensation of mononuclear species.An electrostatic model for the simulation of bond distances in polyions, starting with perfectly regular idealized models, is presented. / <p>Härtill 6 delar.</p> / digitalisering@umu

Submitted by (lucia.rodrigues@ufrpe.br) on 2016-07-04T12:57:49Z No. of bitstreams: 1 Diego Vandeval Maranhao de Melo.pdf: 1332312 bytes, checksum: 71f89e5f58465c3e66aab445d4c43e39 (MD5) / Made available in DSpace on 2016-07-04T12:57:49Z (GMT). No. of bitstreams: 1 Diego Vandeval Maranhao de Melo.pdf: 1332312 bytes, checksum: 71f89e5f58465c3e66aab445d4c43e39 (MD5) Previous issue date: 2013-02-26 / Water soluble polymers are characterized as efficient flocculating agent whose application in soils with cohesive horizons influence, potentially, improving the physical quality and thus extends the agricultural potential of these soils. In this context, the polyacrylamide (PAM) is characterized by its versatility as a chemical amendment, one of the most important commercial polymers for agricultural purposes. Thus, this research proposed to assess the soils quality of the Coastal Tablelands of Pernambuco State inferred by the reduction of the cohesion and improving physical and hydraulic properties by application of PAM as chemical amendment. Therefore, we evaluated three horizons (one cohesive and two non cohesive) of an cohesive Yellow Argisol and, for comparative purposes, we selected the horizon that expresses the maximum cohesion of a Yellow Latosol. We examined PAM aqueous solutions (12.5, 50.0, 100.0 mg kg-1) and distilled water (control). The attributes avaluated were: aggregate stability and aggregate size distribution, resistance penetration, saturated hydraulic conductivity, porosity (macroporosity + mesoporosity + microporosity), characteristics of the water retention curve, plasticity limit, water dispersible clay, cation exchange capacity and Al3+ exchangeable. Treatment mean comparisons were made using the Scott-Knott honestly significant difference test at a significance level of 0,05. The PAM solutions increased structural stability of cohesive horizons, but the improving physical of cohesive horizons was controlled by the intrinsic characteristics of the horizons and of the PAM molecule used in the research. Studies with other formulations of PAM related cohesive character are necessary for their mitigation and understanding of soil-polymer interactions. / Polímeros solúveis em água caracterizam-se como eficientes agentes floculantes, cuja aplicação em solos com horizontes de caráter coeso condiciona a melhoria da qualidade física e, assim, amplia a aptidão agrícola destes solos. A poliacrilamida (PAM) é caracterizada pela sua versatilidade como condicionador químico, sendo um dos mais importantes polímeros comerciais para fins agrícolas. Assim, essa pesquisa propôs avaliar a qualidade de solos dos Tabuleiros Costeiros de Pernambuco com a aplicação de PAM como condicionador químico. Para isto, foram avaliados três horizontes (sendo um coeso e dois não coesos) de um ARGISSOLO AMARELO e, para fins comparativos, foi selecionado o horizonte que expressa a máxima coesão de um LATOSSOLO AMARELO. Como tratamentos, foram aplicadas soluções aquosas de PAM (12,5; 50,0; 100,0 mg kg-1) e água destilada (controle). Os atributos avaliados foram: estabilidade e distribuição de agregados, resistência do solo à penetração do sistema radicular; condutividade hidráulica do solo saturado; porosidade total (macroporosidade + mesoporosidade + microporosidade), limite de plasticidade, argila dispersa em água, capacidade de troca de cátions e Al3+ trocável. Os dados foram avaliados por meio de estatística descritiva e teste de comparação de médias de Scott-Knott a 5% de probabilidade. As soluções de PAM aumentaram a estabilidade estrutural dos horizontes coesos, porém a melhoria físico-hídrica destes horizontes foi controlada pelas características intrínsecas dos horizontes e da molécula de PAM utilizada na pesquisa. Estudos com outras formulações de PAM relacionados ao caráter coeso fazem-se necessárias para sua atenuação e entendimento das interações polímero-solo. Termos para indexação: Poliânions, floculação-dispersão, horizonte coeso.