Ce travail visait à explorer les interactions supramoléculaires comme un outil dans les domaines de la chimie hôte-invité, les nanomatériaux et les nanotechnologies en général, afin de parvenir à des objectifs différents. D'abord, une interaction classique hôte-invité a été étudiée, au moyen d'une technique innovante telle que l'ITC, puis nous avons exploité les interactions supramoléculaires afin de maitriser la production de graphène exfolié en phase liquide, en mettant un accent particulier sur l'amélioration de la qualité et la quantité du matériau produit. Enfin, nous avons étendu l'utilisation de la chimie supramoléculaire à un dispositif réel par la fonctionnalisation des électrodes d'or avec des molécules photochromiques, ouvrant alors la voie à des dispositifs organiques multifonctionnels, pouvant être contrôlés par la lumière. / This work was aimed at exploring supramolecular interactions as a tool in the fields of host-guest chemistry, nanomaterials and in general nanotechnology, in order to achieve different goals. First, a classical host-guest interaction was studied by means of the ITC technique, then we exploited supramolecular interactions in order to harness the production of liquid-phase exfoliated graphene, with a particular focus on improving the quality and quantity of material produced. Finally, we extended the use of supramolecular chemistry to a real device by functionalization of gold electrodes with photochromic molecules, hence paving the way towards multifunctional organic devices and in prospective to graphene based light-controlled multifunctional devices.

Cette thèse a pour but d’étudier le transport de porteur de charge au sein de polymères conjugués, avec comme finalité d’identifier les propriétés des appareils d’électronique organique appropriées pour des applications dans la spintronique organique. Nous avons analysé des échantillons planaires, de géométries latérales, qui offrent la possibilité d’étudier les propriétés de transport sous l’application de différents stimulus et la détection le transport de longue distance du moment angulaire (spin), au sein de semi-conducteurs organiques (OSC). Dans cette configuration, des critères bien établis doivent être satisfait pour réaliser le transport diffusif d’un courant de spin polarisé au travers d’un matériel organique. Nous avons analysé ces diffèrent critères et trouvé des matériaux dont les propriétés physiques fournissent une solution satisfaisante. Le résultat de ce travail fut la création de transistors à effet de champ organiques dont les propriétés répondent au besoin des applications de spintronique. / In this thesis, charge carrier transport in conjugated polymers is studied with the aim to identify organic electronics devices properties suitable for applications in organic spintronics. We investigate planar samples, in a lateral geometry, which offer the possibility to study transport properties under the application of different stimuli and to detect long-range spin transport in OSCs. In this configuration, well-established criteria must be satisfied to realize diffusive-like transport of a spin-polarized current through an organic material. We analyse these criteria and find possible materials properties solutions. The outcome is the realization of organic field-effect transistors with properties ad hoc for spintronics applications.

Le lien entre la structure semi-cristalline et les propriétés d’usage (mécaniques, diélectriques et électro-actives) de films de copolymères fluorés électro-actifs développés pour des applications en électronique organique imprimée a été étudié. Les matériaux investigués sont des copolymères poly(VDF-co-TrFE) et des terpolymères poly(VDF-ter-TrFE-ter-CTFE) à base de fluorure de vinylidène (VDF), trifluoroéthylène (TrFE) et chlorotrifluoroéthylène (CTFE).Les films de polymères obtenus par évaporation du solvant sont étudiés par diffraction des rayons X (SAXS-WAXS), DSC, FTIR, DMA, spectroscopie diélectrique et cycles de polarisation afin de mettre en évidence l’impact de la composition et de la mise en forme (recuit, polarisation) sur la structure et les propriétés finales du matériau. Nous montrons ainsi qu’au sein des films de copolymères, la phase ferroélectrique (FE) coexiste avec une phase ferroélectrique défective (DFE). La fraction croissante de cette phase DFE avec la teneur en TrFE permet d’expliquer l’évolution des propriétés thermiques dont la transition de Curie. Une transition structurale continue, de la phase DFE vers la phase paraélectrique (PE), en température a été mise en évidence.La teneur en termonomère CTFE influence fortement la structure cristalline et les propriétés électro-actives des films de terpolymères (disparition du caractère ferroélectrique au profit du caractère ferroélectrique relaxeur (RFE)). Nous prouvons pour la première fois l’existence d’une transition structurale continue entre la phase RFE et la phase PE au voisinage de la température ambiante. Cette transition permet d’expliquer les propriétés exacerbées de ces matériaux (constante diélectrique et déformation sous champ électrique). Enfin, des analogies de comportement entre les copolymères et les terpolymères sont discutées, notamment l’évolution des phases cristallines sous champ électrique, afin de mieux comprendre le fonctionnement de ces polymères électro-actifs pour leur futur développement au niveau industriel. / The relationship between semi-crystalline structure and properties of use (mechanical, dielectric and electroactive) of fluorinated copolymer films was studied for applications in organic electronics. Investigated materials are poly(VDF-co-TrFE) copolymers and poly(VDF-ter-TrFE-ter-CTFE) terpolymers based on vinylidene fluoride (TrFE), trifluoroethylene (TrFE) and chlorotrifluoroethylene (CTFE). Polymer films, obtained after solvent evaporation, are studied by X-ray diffraction (SAXS-WAXS), DSC, FTIR, DMA, dielectric spectroscopy and polarization cycles in order to highlight the impact of composition and processing (annealing, poling) on structure and final properties of material. We showed that the ferroelectric (FE) phase coexists with the defective ferroelectric (DFE) phase in copolymer films. The increasing fraction of DFE phase with TrFE content allows explaining the evolution of thermal properties. A continuous structural transition, from DFE phase to paraelectric (PE) phase was highlighted. The CTFE termonomer content highly influences the crystalline structure and the electro-actives properties of terpolymer films (loss of ferroelectric behavior in favor of relaxor ferroelectric (RFE) behavior).We proved for the first time the existence of a continuous structural transition between RFE phase and PE phase around room temperature. This transition allows explaining exacerbated properties of these materials (dielectric constant and deformation under electric field).Finally, analogies of behavior between copolymers and terpolymers are discussed, especially the evolution of crystalline phases under electric field, in order to better understand how these electro-active materials work for their future development at industrial level.

<p>At Acreo AB located in Norrköping, Sweden, research and development in the field of organic electronics have been conducted since 1998. Several electronic devices and systems have been realized. In late 2003 a commercial printing press was installed to test large scale production of these devices. Prior to the summer of 2005 the project made significant progress. As a step towards industrialisation, the variability and yield of the printing process needed to bee studied. A decision to implement Statistical Process Control (SPC) and Design of Experiments (DOE) to evaluate and improve the process was taken.</p><p>SPC has been implemented on the EC-patterning step in the process. A total of 26 Samples were taken during the period October-December 2005. An - and s-chart were constructed from these samples. The charts clearly show that the process is not in statistical control. Investigations of what causes the variation in the process have been performed. The following root causes to variation has been found: </p><p>PEDOT:PSS-substrate sheet resistance and poorly cleaned screen printing drums. </p><p>After removing points affected by root causes, the process is still not in control. Further investigations are needed to get the process in control. Examples of where to go next is presented in the report. In the DOE part a four factor full factorial experiment was performed. The goal with the experiment was to find how different factors affects switch time and life length of an electrochromic display. The four factors investigated were: Electrolyte, Additive, Web speed and Encapsulation. All statistical analysis was performed using Minitab 14. The analysis of measurements from one day and seven days after printing showed that:</p><p>- Changing Electrolyte from E230 to E235 has small effect on the switch time</p><p>- Adding additives Add1 and Add2 decreases the switch time after 1 and 7 days</p><p>- Increasing web speed decreases the switch time after 1 and 7 days </p><p>- Encapsulation before UV-step decreases the switch time after 7 days</p>

<p>In this thesis we explore in particular the dynamics of a special type of quasi-particle in pi-conjugated materials termed polaron, the origin of which is intimately related to the strong interactions between the electronic and the vibrational degrees of freedom within these systems. In order to conduct such studies with the particular focus of each appended paper, we simultaneously solve the time-dependent Schrödinger equation and the lattice equation of motion with a three-dimensional extension of the famous Su-Schrieffer-Heeger (SSH) model Hamiltonian. In particular, we demonstrate in Paper I the applicability of the method to model transport dynamics in molecular crystals in a region were neither band theory nor perturbative treatments such as the Holstein model and extended Marcus theory apply. In Paper II we expand the model Hamiltonian to treat the revolution of phenylene rings around the sigma-bonds and demonstrate the great impact of stochastic ring torsion on the intra-chain mobility in conjugated polymers using poly[phenylene vinylene] (PPV) as a model system. Finally, in Paper III we go beyond the original purpose of the methodology and utilize its great flexibility to study radiationless relaxations of hot excitons.</p> / Report code: LiU-TEK-LIC-2007:4.

In the past decade, tremendous progress has been made in organic field effecttransistors. Fused oligothiophenes and anthracene molecules are fascinatingmacromolecules having unique optoelectronic properties. These compounds are successfully employed as active components in optoelectronic devices including field effect transistors. Our goal is to design and synthesize conjugated molecular materials, which are highly functionalized through structural modifications in order to enhance their electronic, photonic, and morphological properties. The main desire is to synthesize novel organic fused-arenes having efficient charge carrier mobilities, as well as to optimize optical properties for organic field effect transistors (OFETs). Novel series of fused arene molecules of 9,10-di(thiophen-3-yl)anthracene (1), trans-2,5-(dianthracene-9- vinyl)thiophene (2), trans-5,5’-(dianthracene-9-yl)vinyl)- 2,2’-bithiophene (3), 5,5’-di(2 thiophene)-2,2’-bithiophene (4) , 9,10-(divinyl)anthracene core with 1- phenylcarboxypyrene (6) and polymers of poly(anthracene-co-bithiophene) (5) and poly(anthracene) (7) have been synthesized as promising materials for organic field effect transistors (OFETs). These compounds were confirmed and characterized by 1H-NMR, FT-IR, and elemental analysis. Their optical, thermal, and electronic properties were investigated using UV-Vis and photoluminescence spectroscopy, and thermogravimetric analysis respectively. Future studies will focus on evaluating OFETs performance of these material.

This thesis examines strategies to exploit existing materials and techniques to advance organic thin film transistor (OTFT) technology in device performance, device manufacture, and device integration. To enhance device performance, optimization of plasma enhanced chemical vapor deposited (PECVD) gate dielectric thin film and investigation of interface engineering methodologies are explored. To advance device manufacture, OTFT fabrication strategies are developed to enable organic circuit integration. Progress in device integration is achieved through demonstration of OTFT integration into functional circuits for applications such as active-matrix displays and radio frequency identification (RFID) tags. OTFT integration schemes featuring a tailored OTFT-compatible photolithography process and a hybrid photolithography-inkjet printing process are developed. They enable the fabrication of fully-patterned and fully-encapsulated OTFTs and circuits. Research on improving device performance of bottom-gate bottom-contact poly(3,3'''-dialkyl-quarter-thiophene) (PQT-12) OTFTs on PECVD silicon nitride (SiNx) gate dielectric leads to the following key conclusions: (a) increasing silicon content in SiNx gate dielectric leads to enhancement in field-effect mobility and on/off current ratio; (b) surface treatment of SiNx gate dielectric with a combination of O2 plasma and octyltrichlorosilane (OTS) self-assembled monolayer (SAM) delivers the best OTFT performance; (c) an optimal O2 plasma treatment duration exists for attaining highest field-effect mobility and is linked to a “turn-around” effect; and (d) surface treatment of the gold (Au) source/drain contacts by 1-octanethiol SAM limits mobility and should be omitted. There is a strong correlation between the electrical characteristics and the interfacial characteristics of OTFTs. In particular, the device mobility is influenced by the interplay of various interfacial mechanisms, including surface energy, surface roughness, and chemical composition. Finally, the collective knowledge from these investigations facilitates the integration of OTFTs into organic circuits, which is expected to contribute to the development of new generation of all-organic displays for communication devices and other pertinent applications. A major outcome of this work is that it provides an economical means for organic transistor and circuit integration, by enabling use of the well-established PECVD infrastructure, yet not compromising the performance of electronics.

At Acreo AB located in Norrköping, Sweden, research and development in the field of organic electronics have been conducted since 1998. Several electronic devices and systems have been realized. In late 2003 a commercial printing press was installed to test large scale production of these devices. Prior to the summer of 2005 the project made significant progress. As a step towards industrialisation, the variability and yield of the printing process needed to bee studied. A decision to implement Statistical Process Control (SPC) and Design of Experiments (DOE) to evaluate and improve the process was taken. SPC has been implemented on the EC-patterning step in the process. A total of 26 Samples were taken during the period October-December 2005. An - and s-chart were constructed from these samples. The charts clearly show that the process is not in statistical control. Investigations of what causes the variation in the process have been performed. The following root causes to variation has been found: PEDOT:PSS-substrate sheet resistance and poorly cleaned screen printing drums. After removing points affected by root causes, the process is still not in control. Further investigations are needed to get the process in control. Examples of where to go next is presented in the report. In the DOE part a four factor full factorial experiment was performed. The goal with the experiment was to find how different factors affects switch time and life length of an electrochromic display. The four factors investigated were: Electrolyte, Additive, Web speed and Encapsulation. All statistical analysis was performed using Minitab 14. The analysis of measurements from one day and seven days after printing showed that: - Changing Electrolyte from E230 to E235 has small effect on the switch time - Adding additives Add1 and Add2 decreases the switch time after 1 and 7 days - Increasing web speed decreases the switch time after 1 and 7 days - Encapsulation before UV-step decreases the switch time after 7 days

This thesis examines strategies to exploit existing materials and techniques to advance organic thin film transistor (OTFT) technology in device performance, device manufacture, and device integration. To enhance device performance, optimization of plasma enhanced chemical vapor deposited (PECVD) gate dielectric thin film and investigation of interface engineering methodologies are explored. To advance device manufacture, OTFT fabrication strategies are developed to enable organic circuit integration. Progress in device integration is achieved through demonstration of OTFT integration into functional circuits for applications such as active-matrix displays and radio frequency identification (RFID) tags. OTFT integration schemes featuring a tailored OTFT-compatible photolithography process and a hybrid photolithography-inkjet printing process are developed. They enable the fabrication of fully-patterned and fully-encapsulated OTFTs and circuits. Research on improving device performance of bottom-gate bottom-contact poly(3,3'''-dialkyl-quarter-thiophene) (PQT-12) OTFTs on PECVD silicon nitride (SiNx) gate dielectric leads to the following key conclusions: (a) increasing silicon content in SiNx gate dielectric leads to enhancement in field-effect mobility and on/off current ratio; (b) surface treatment of SiNx gate dielectric with a combination of O2 plasma and octyltrichlorosilane (OTS) self-assembled monolayer (SAM) delivers the best OTFT performance; (c) an optimal O2 plasma treatment duration exists for attaining highest field-effect mobility and is linked to a “turn-around” effect; and (d) surface treatment of the gold (Au) source/drain contacts by 1-octanethiol SAM limits mobility and should be omitted. There is a strong correlation between the electrical characteristics and the interfacial characteristics of OTFTs. In particular, the device mobility is influenced by the interplay of various interfacial mechanisms, including surface energy, surface roughness, and chemical composition. Finally, the collective knowledge from these investigations facilitates the integration of OTFTs into organic circuits, which is expected to contribute to the development of new generation of all-organic displays for communication devices and other pertinent applications. A major outcome of this work is that it provides an economical means for organic transistor and circuit integration, by enabling use of the well-established PECVD infrastructure, yet not compromising the performance of electronics.

The efficiency of an organic photovoltaic cell depends mainly on its morphology where an exciton has to migrate to a p-n junction to create a photocurrent. Therefore the distance from the bulk of the cell to a junction interface should not exceed the diffusion length of the exciton. In this thesis, two novel lithographical methods, to produce specific polymer morphologies, were developed and evaluated. In the first method, called embedded annealing, self-assembled polystyrene colloids were embedded in a polydimethylsiloxane (PDMS) film and annealed under an electric field to produce a bi-polymer structure consisting of polymer columns in a thin film of PDMS. Polymer colloids were successfully assembled into two dimensional hexagonally close packed arrays. However, the annealing process was unsuccessful. The second method, imprint annealing, aimed to increase the aspect ratio (height/width) of thermally imprinted micrometer sized polystyrene features by annealing them in uniform electric fields. The results showed that the aspect ratio of imprinted features can be significantly increased, 21-fold, while maintaining the periodicity of the original imprint. This is in contrast to previous results where smooth polymer films annealed in uniform fields where the periodicity of the resulting structures cannot be independently controlled, and are highly sensitive to the electrode spacing. Feature sizes down to 1 µm and aspect ratios up to 4.5 were achieved using imprint annealing. / Verkningsgraden hos en hos en solcell beror, för givna material, framförallt på dess uppbyggnad. För att bidra till fotoströmmen måste en genererad exciton vandra till en pn-övergång. På grund av detta bör det längsta avståndet till närmaste pn-övergång i solcellen inte vara längre än excitonens diffusionslängd. I detta examensarbete testas två olika litografiska metoder för att åstadkomma en specifik filmgeometri lämpad för organiska solceller. Den första metoden, kallad embedded annealing, går ut på att bädda in spontant ordnade sfäriska polystyrenkolloider i en polydimetylsiloxan (PDMS) -film för att sedan vid förhöjd temperatur applicera ett elektiskt fält över filmen. Förhoppningen var att på detta sätt töja ut kolloiderna till pelare genom PDMS-filmen. I det första steget ordnades kolloiderna sponant i tätpackade hexagonala tvådimensionella gitter på kiselsubstrat. Experimenten lyckades inte med hjälp av elektriska fält töja ut kolloiderna. Den andra metoden, imprint annealing, syftar till att öka höjd/bredd -förhållandet och minska diametern hos präglade polystyrenstrukturer. Dessa ursprungliga topografiska stukturer skapas med hjälp av en tryckpressmetod kallad nanoimprinting. Dessa strukturer värmdes upp, och ett uniformt elekrisk fält applicerades över dem. Mina resultat visar att man med elektriska fält avsevärt kan öka höjd-breddförhållandet hos polymerstrukturer och samtidigt bevara periodiciteten hos de ursprungliga strukturerna. Detta står i kontrast mot tidigare resultat på släta filmer, där periodiciteten inte kan kontrolleras oberonde av andra parametrar. Med imprint annealing ökades höjd-breddförhållandet hos enskilda strukturer upp till 21 gånger. Diametrar ner till 1 µm och höjd/breddförhållanden upp till 4,5 uppnåddes.