Cette thèse a exploré comment, en introduisant des interfaces nanostructurées dans des systèmes supramoléculaires pour l'électronique, il est possible de moduler, ajouter et étudier les propriétés des nano-objets. Sur ces applications de fonctionnalisation auto-assemblée des limites, le contrôle thermique sur les propriétés intrinsèques, la modulation lumineuse des structures chimiques et physiques ont été trouvés comme étant des techniques adaptées pour affecter le système supramoléculaire fonctionnalisé nano-structuré pour l'électronique organique. Des nanoparticules d'or ont été utilisées pour générer des interfaces qui ont été fonctionnalisés afin d'étudier l'effet de transport de charge dans un transistor à couche mince organique. Par conséquent, cette approche a été intensifiée en employant des molécules photochromiques et par le contrôle du piégeage de charge par irradiation de lumière. Le même principe a été utilisé pour moduler l'injection de charge dans les transistors à haute performances, par fonctionnalisation des électrodes appropriées avec des diaryléthènes. Enfin, une approche différente pour contrôler le dépôt de flocons de graphène sur surface diélectrique a été employée avec succès pour concevoir de nouveaux éléments de mémoire par ajustement de l'alignement des niveaux énergétiques du graphène après recuit thermique. / This thesis explored how, by introducing nanostructured interfaces in supramolecular system for electronics, is possible to modulate, tune, add and study properties arising from nano-objects. On these purposes self-assembled functionalization of boundaries, thermal control on intrinsic properties, light modulation of chemical and physical structures have been found as tailored techniques to affect nano-structured functionalized supramolecular system for organic electronics. Gold nanoparticles have been used to generate interfaces that have been functionalized in order to study charge transport effect in organic thin film transistor. Therefore this approach has been stepped up employing photochromic molecules and controlling charge trapping with light irradiation. The same principle has been used to modulate charge injection in high performance transistors, by functionalizing electrodes with appropriate diarylethenes. Finally, a different approach of controlling deposition of graphene flakes on dielectric surface has been successfully employed to design new memory elements by tuning energetic level alignment of graphene with thermal annealing.

Cette thèse a exploré comment, en mélangeant des matériaux avec des propriétés électriques différentes, il est possible de fabriquer des transistors avec des performances accrues. Des transistors organiques à effet de champ basés sur un oligothiophène (DH4T) ont été fabriqués et optimisés jusqu’à ce que les mobilités mesurées fussent supérieures à celles observées dans des films évaporés. Ces résultats ont été obtenus par le contrôle précis des interfaces et de la vitesse d’évaporation. Des polymères de type p ont été mélangés à des polymères de type n. Chaque solution obtenue a été utilisée pour la fabrication de transistors ambipolaires. Les transistors ont été caractérisés et il a été possible de fabriquer des transistors avec des mobilités équilibrées pour chaque paire de polymères. Des transistors à effet de champ basés sur un mélange de P3HT et d’une molécule photochromique (DAE-Me) ont été fabriqués. Le courant a été mesuré pendant et entre les irradiations et il a été démontré qu’une mémoire non-volatile à multiple niveaux peut être fabriquée / This thesis explored how, by blending of materials with different electrical characteristics, it is possible to fabricate transistors with new or improved performances. First, organic field-effect transistors based on a single oligothiophene, DH4T, were fabricated and optimized until the measured mobility was superior to that observed in vacuum deposited films. This was achieved through careful tuning of the interfaces using self-assembled monolayers and by strong control of the solvent- evaporation rate. P-type polymers were blended with an n-type polymer. Each resulting solution was used for the fabrication of ambipolar field-effect transistors. These devices were characterized and it was found that for each pair of p- and n-type polymers, a transistor with balanced mobilities and high Ion/Ioff could be fabricated. Finally field-effect transistors based on a blend of P3HT and a photoswitchable diarylethene (DAE-Me) were fabricated. The current was measured during and between irradiations and it was demonstrated that a non-volatile multilevel memory could be fabricated.

Dendrimerai tai naujai dendritinių polimerų klasei priskiriamos makromolekulės. Jų dydis, funkcinių grupių skaičius yra tiksliai apibrėžti ir gali būti kontroliuojami sintezės metu. Dėl išskirtinių struktūrinių savybių, dendrimerai jau keletą dešimtmečių yra intensyviai tyrinėjamos medžiagos. Pagrindinis disertacijos tikslas yra ištirti PPI ir PAMAM dendrimerų, funkcionalizuotų CAzPA ir ESA fotochrominiais junginiais optines savybes bei šviesa inicijuotų fotocheminių reakcijų dinamiką panaudojus kelias tyrimų metodikas. Kadangi CAzPA ir ESA junginių fotochromizmas yra susijęs su šviesa indukuota izomerizacijos bei tautomerizacijos fotocheminėmis reakcijomis, todėl darbe buvo siekiama ištirti šiais junginiais funkcionalizuotų dendrimerų dinaminių savybių priklausomybę nuo dendrimero tipo bei jo generacijos. Ištyrus PPI ir PAMAM dendrimerų funkcionalizuotų CAzPA junginiais plėvelių ir tirpalų dinamines savybes, buvo nustatyta, kad izomerizacijos sparta nepriklauso nuo dendrimero tipo, tirpiklio ir žadinančios spinduliuotės energijos. Dendrimerų plėvelių sužadintos būsenos relaksacijos trukmė yra apie 15 ps, o tai apie 7 kartus lėčiau nei tirpaluose. Eksperimentiškai ir teoriškai ištyrus skirtingų generacijų PPI dendrimerų funkcionalizuotų ESA fotochrominiais junginiais optines savybes, buvo nustatytos keturios stabilios ESA funkcinių grupių tautomerinės formos, kurių pagrindinės būsenos energijos yra skirtingos. Skirtingų dendrimero generacijų sužadintos būsenos dinamikos... [toliau žr. visą tekstą] / Dendrimers are multivalent, well-defined materials that constitute a new class of polymer macromolecules. They have been extensively studied over the past several decades mainly due to their exceptional structure properties. The size of molecule, number of terminal groups, molecular weight and several other properties of dendrimers could be precisely controlled during synthesis. The main goal of this thesis is to investigate the optical properties and light induced photochemical reaction dynamics within the PPI and PAMAM dendrimers functionalized by CAzPA and ESA type terminal groups by means of several spectroscopic techniques. Because photochromism of CAzPA and ESA type terminal groups is associated with light induced isomerization and tautomerization photochemical reactions, the main attention of present thesis was devoted to investigate dynamical properties of functionalized dendrimers as an influence of dendrimer type and its generation. Investigations of dynamic properties of PPI and PAMAM dendrimers functionalized with the CAzPA terminal groups have shown that isomerization rate is insensitive to dendrimer type, solvent and excitation wavelength. The isomerization rate of the dendrimer films take place in about 15 ps and it is only seven times slower than in dendrimer solvent. Both experimental and theoretical optical studies performed on PPI dendrimers functionalized with the ESA type terminal groups reveal four stable tautomeric forms with different energy in the... [to full text]

Dendrimers are multivalent, well-defined materials that constitute a new class of polymer macromolecules. They have been extensively studied over the past several decades mainly due to their exceptional structure properties. The size of molecule, number of terminal groups, molecular weight and several other properties of dendrimers could be precisely controlled during synthesis. The main goal of this thesis is to investigate the optical properties and light induced photochemical reaction dynamics within the PPI and PAMAM dendrimers functionalized by CAzPA and ESA type terminal groups by means of several spectroscopic techniques. Because photochromism of CAzPA and ESA type terminal groups is associated with light induced isomerization and tautomerization photochemical reactions, the main attention of present thesis was devoted to investigate dynamical properties of functionalized dendrimers as an influence of dendrimer type and its generation. Investigations of dynamic properties of PPI and PAMAM dendrimers functionalized with the CAzPA terminal groups have shown that isomerization rate is insensitive to dendrimer type, solvent and excitation wavelength. The isomerization rate of the dendrimer films take place in about 15 ps and it is only seven times slower than in dendrimer solvent. Both experimental and theoretical optical studies performed on PPI dendrimers functionalized with the ESA type terminal groups reveal four stable tautomeric forms with different energy in the... [to full text] / Dendrimerai tai naujai dendritinių polimerų klasei priskiriamos makromolekulės. Jų dydis, funkcinių grupių skaičius yra tiksliai apibrėžti ir gali būti kontroliuojami sintezės metu. Dėl išskirtinių struktūrinių savybių, dendrimerai jau keletą dešimtmečių yra intensyviai tiriamos medžiagos. Pagrindinis disertacijos tikslas yra ištirti PPI ir PAMAM dendrimerų, funkcionalizuotų CAzPA ir ESA fotochrominiais junginiais optines savybes bei šviesa inicijuotų fotocheminių reakcijų dinamiką panaudojus kelias tyrimų metodikas. Kadangi CAzPA ir ESA junginių fotochromizmas yra susijęs su šviesa indukuota izomerizacijos bei tautomerizacijos fotocheminėmis reakcijomis, todėl darbe buvo siekiama ištirti šiais junginiais funkcionalizuotų dendrimerų dinaminių savybių priklausomybę nuo dendrimero tipo bei jo generacijos. Ištyrus PPI ir PAMAM dendrimerų funkcionalizuotų CAzPA junginiais plėvelių ir tirpalų dinamines savybes, buvo nustatyta, kad izomerizacijos sparta nepriklauso nuo dendrimero tipo, tirpiklio ir žadinančios spinduliuotės energijos. Dendrimerų plėvelių sužadintos būsenos relaksacijos trukmė yra apie 15 ps, o tai apie 7 kartus lėčiau nei tirpaluose. Eksperimentiškai ir teoriškai ištyrus skirtingų generacijų PPI dendrimerų funkcionalizuotų ESA fotochrominiais junginiais optines savybes, buvo nustatytos keturios stabilios ESA funkcinių grupių tautomerinės formos, kurių pagrindinės būsenos energijos yra skirtingos. Skirtingų dendrimero generacijų sužadintos būsenos dinamikos... [toliau žr. visą tekstą]

Textile UV-radiation sensors has lately been introduced to the field of smart textiles. Inkjet printing has been used as means of application due to the effective and resource efficient process. UV-LED radiation curing has been used in combination with inkjet printing in favour of low energy requirements, solvent free solution and reduced risk of clogging in the print heads. The problems arising when exposing photochromic prints to UV-radiations are that oxygen inhibition during the curing and photo-oxidation in the print reduces the prints ability to develop colour. It is the oxygen in the air in combination with UV-radiation that gives the photo-oxidating behavior. The aim of the study is to with the aid of physical protection reduce the effect of oxygen inhibition and photo-oxidation in the prints. Three types of physical treatments were used, wax coating, protein based impregnation and starch based impregnation. Treatments were applied before curing as well as after curing and the colour development after activation during 1 min of UV-radiation was measured with a spectrophotometer. Multiple activations were also tested to see how the treatments affected the fatigue behaviour of the prints over time. The aim was to have as high colour development as possible reflecting reduced oxygen inhibition and photo-oxidation. Results showed significantly higher colour development for samples treated with wax and whey powder before curing, but reduced colour development for amylose impregnation. Over time whey powder before curing showed highest colour development due to highest initial colour development. Lowest fatigue was seen for washed samples containing the chemical stabiliser HALS, showing an increased colour development. In reference to earlier studies the protective properties of wax and whey powder is due to their oxygen barrier properties protecting the print. The tested treatments have shown that it is possible to reduce the effect of photo-oxidation during curing leading to prints giving higher colour development. This gives a great stand point when improving existing and future application of photochromic prints on textiles.

Rewritable photochrome-based 3D optical data storage requires photochromic molecules with high two-photon absorption (2PA) cross sections. Currently, the low value of two-photon absorption cross sections of existing photochromes makes them unsuitable for practical application in 3D data storage. Worldwide attempts to increase the cross section of photochromic molecules by altering the chemical structure have yielded poor results. In this work, two ways to increase the two-photon absorption cross sections of photochromes were investigated. In the first method, partial success demonstrated by extending the conjugation of a photochromic molecule, a high two-photon absorption cross section of the closed form isomer and high photoconversion to the closed form were realized. At the same time, a decrease in photoswitching quantum yield and low photoconversion to open form was observed. A discussion is provided to explain the results, suggesting that the proposed method of extending the conjugation may not solve the problem. For this reason a new method for effective two-photon absorption cross section enhancement of photochromes was proposed. As a proof of principle, a new two-photon absorbing dye with a hydrogen bonding moiety was synthesized and used for the formation of supramolecular structures with a photochromic compound. Theoretical reasoning and experimental demonstration of energy transfer from the dye to the photochrome under one and two-photon excitation confirmed the practical value of the method. The effects of a 2PA dye on the photochromic properties of a diarylethene were investigated using a model compound to simplify data analysis. Formation of supramolecular structures was revealed using ¹H NMR spectroscopic methods. The model compound, having the same hydrogen bonding moiety as 2PA dye, has been demonstrated to bind with photochrome molecules at very low concentrations. Photochromic properties of 2,3-bis(2,4,5-trimethyl-3-thienyl)maleimide, including conversions at the photostationary state, extinction coefficients, photoisomerization reaction rates and quantum yields, were shown to be affected by hydrogen bonding with the model compound - 2,6-bis-(acetamido)pyridine. The extent of this change was determined and discussed, demonstrating a balanced supramolecular strategy to modulate photochemical and photophysical properties of this important class of photochromic material.

Le photochromisme se définit comme une transformation réversible d'une espèce entre deux états dont les spectres d'absorption sont différents. La réversibilité de la réaction peut se faire thermiquement et/ou photochimiquement. Cet effet suscite un grand intérêt pour l'utilisation de ses propriétés dans différentes applications (matériaux à transmission optique variable, mémoires optiques…). Parmi les nombreuses familles de photochromes organiques, les chromènes (benzopyranes et naphtopyranes) et les diaryléthènes, dont le photochromisme procède par électrocyclisation, occupent une place privilégiée. Ces dernières années, l'enjeu est d'utiliser ces unités photochromiques pour élaborer de nouveaux systèmes multichromophores. Dans ce projet, des réactions de couplage de la chimie organométallique ont permis de préfonctionnaliser des unités photochromiques monomères, servant de briques moléculaires pour l'architecture de structures complexes. Ainsi, deux séries de nouveaux systèmes photochromiques ont été élaborés autour de la triphénylamine en modifiant la jonction. Ces systèmes ont ensuite été étudiés en spectroscopie d'absorption électronique et de fluorescence, puis des études préliminaires sous irradiation ont été réalisées afin d'évaluer leur propriétés photochromiques. En parallèle, un diaryléthène substitué par un atome de silicium a été synthétisé en utilisant les micro-ondes, ouvrant de nouvelles perspectives pour des systèmes photochromiques bistables. / The photochromism is defined as a reversible transformation between two states of the molecule. The reversibility can occur thermally and/or photochemically. The intrinsic properties make the photochromic molecular system highly promising for various applications such as optical memory and molecular switches. From the large family of organic photochromic compounds, chromenes (benzopyrans and napthopyrans) and diarylethenes, both involving a ring closure/opening electrocyclic isomerisation, are largely used. In the last decades, a renewal of interest in the synthesis of supramolecular structures have been observed in view of application for optoelectronic devices. In this project, the original idea was to design and synthesize novel star-shaped like molecular architecture having triphenylamine as core block bridging several thermoreversible photochromic units in one molecule. In this context, new series of supramolecular assemblies were synthesized by introducing chromenes units on the core and changing the linkage. Then, their spectroscopic properties were studied by absorption and fluorescence spectroscopy before evaluating their photochromic properties. In a second way, a diarylethene substituted by a silicon atom was synthesized under micro-wave to open an interesting perspective in order to access a new photochromic family.

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.

L’objectif de cette thèse a été axé sur le développement des systèmes capable de répondre à des stimuli externes, basés sur des unités photochromiques. Le but d’une telle quête est d’augmenter la complexité des dispositifs et des machines moléculaires synthétiques. Avec l’objectif de développer des dispositifs et des machines artificiels plus complexes, nous avons réalisé de systèmes comprenant de multiples interrupteurs moléculaires. En vue de la réalisation de cette thèse, des nouveaux systèmes multi-photochromiques, où hybrides photochrome/nanomatériaux contenant des fragments azobenzène, diaryléthène ou spiropyrane ont été réalisés et étudiés. D’abord, on s’est focalisés sur des systèmes multi-azobenzènes capables de subir de grands réarrangements géométriques lors de la photoisomérisation, ils pourraient être utilisés à l'avenir comme éléments constitutifs des matériaux host-guest ou metal-organic frameworks contrôlables par des stimuli lumineux. Dans un second exemple, des commutateurs photochromiques de type dithiényléthène ont été utilisés pour déclencher l'émission d'une porphyrine. Cette dyade à montré une modulation réversible de son émission, affichant un contraste particulièrement élevé. Comme dernier exemple, un dérivé de spiropyrane a été combiné avec des nanoparticules d’or anisotropes. En induisant l'isomérisation de l’interrupteur moléculaire dans les dispersions colloïdales des nanorods d’or en liquide, nous avons visualisé une grande variation du spectre d'extinction des colloïdes, dépendante de la longueur d’onde du mode LSPR et du recouvrement spectrale avec le photoswitch. / The aim of this thesis has been to develop systems capable of responding to external stimuli, based on photochromic units. The goal of such a quest is to increase the complexity of devices and synthetic molecular machines. With the goal of developing more complex artificial devices and machines, we have realised systems containing multiple molecular switches. For the realisation of this thesis, new multi-photochromic systems, or photochromes/nanomaterials hybrids containing azobenzene, diarylethene or spiropyran moieties have been realised and studied. Firstly, we focused on multi-azobenzene systems capable of undergoing large geometric rearrangements during photoisomerisation, as they may be used in the future as constituent elements of host-guest or metal-organic frameworks controllable by luminous stimuli. In a second example, dithienylethene-type photochromic switches have been used to trigger the emission of a porphyrin. This dyad exhibited a reversible modulation of its emission, displaying a particularly highly contrasted response. As a final example, a spiropyran derivative has been combined with anisotropic gold nanoparticles. By inducing the isomerisation of the molecular switch in the AuNR colloidal liquid dispersions, we visualised a large variation of the colloid extinction spectrum, dependent on the LSPR mode wavelength and the spectral overlap with the photoswitch.

This thesis focuses on two topics: thermal limitations of volume Bragg gratings (VBGs) employed as laser-cavity mirrors and formation of color centers in KTiOPO4 and its isomorphs. To explore the mechanisms of the thermal limitations of VBGs in high power lasers, I designed and constructed a diode-pumped, solid‑state laser with a VBG as cavity mirror that had a significantly higher absorption than what is typical. Thereby I could study the limiting thermal effects by using only moderate intra-cavity power. Additionally, I designed a computer model to numerically investigate the thermal effects in VBGs. Both the experiments and the simulations showed that the laser became successively more unstable when the power was increased. Absorption of the reflected laser beam causes broadening of the grating spectrum accompanied by decreasing diffraction efficiency. The reduced reflectivity leads to a leakage of the radiation through the grating. Moreover, the simulations showed that this increased instability was due to a reshaping of the intensity distribution profile inside the grating, which, in turn, leads to a sharp reduction of the diffraction efficiency. High-intensity visible radiation induces color centers in KTiOPO4, which can lead to severe decrease in the performance of the crystal and can cause catastrophic breakdown. The formation of color centers was investigated by measuring picosecond, blue-light induced infrared absorption (BLIIRA) in periodically-poled KTiOPO4, Rb:KTiOPO4, RbTiOPO4, KTiOAsO4 and RbTiOAsO4 through thermal lens spectroscopy using a common-path interferometer. This setup is capable of measuring absorption as low as 10-5 cm-1. The dependence of the BLIIRA signal on blue light average power and intensity as well as on the crystal temperature was studied. The results show the presence of at least two different types of color centers. A higher level of remnant absorption was observed in the phosphates compared to that of the arsenates. The largest portion of the induced absorption is attributed to photo-generated electrons and holes being self-trapped in the proximity to the Ti4+ and O2- ions, respectively, forming polaron color centers. Stabilization of these centers is aided by the presence of mobile alkali metal vacancies in the crystal. / Denna avhandling fokuserar på både volymbraggitters (VBGs) termiska begränsningar, i tillämpning som speglar i laserkaviteter, och på bildandet av färgcentra i KTiOPO4 och isomorfa kristaller. För att undersöka de termiska effekterna i VBGer som medför begränsningar på högeffektlasrar utfördes både experiment och simuleringar. För experimenten konstruerades en diod-pumpad Yb:KYW laser med ett VBG som har betydligt högre absorption än vad som är typiskt. Därmed kunde de termiska effekterna studeras vid måttliga intrakavitetseffekter. Simuleringarna bestod av två delmodeller; gitterstrukturen modelerades med överföringsmatriser och värmeflödet med en tredimensionell modell baserad på finita elementmetoden. Både experimenten och simuleringarna visade att en laser blir successivt mer instabil när den optiska effekten ökar. Absorptionen av laserstrålen i VBGt förändrade dess spektrala egenskaper, vilket i sin tur påverkade laserns stabilitet och prestanda. De huvudsakliga effekterna var en breddning av gittrets spektrum med en minskad reflektans. Simuleringarna visade även att den ökade instabiliteten berodde på en förändring av strålningens intensitetsfördelning inuti gittret, vilket accelererade reduktionen av gittrets reflekterande förmåga. I termer av den effekt som faller in mot gittret, har lasern en tydlig övre effektgräns. När den gränsen har uppnåtts leder vidare ökning av pumpeffekten i huvudsak till ökat läckage genom volymbraggittret, i stället för till ökad uteffekt hos laserstrålen. Kortvågigt synlig ljus av hög intensitet inducerar färgcentra i KTiOPO4, vilket kan leda till kraftigt reducerad transparens och kan orsaka permanent skada i kristallen. För att undersöka skapandet av dessa färgcentra mättes den termiska lins som uppstår vid blå-ljus-inducerad infraröd absorption (Eng: blue-light induced infrared absorption = BLIIRA) inducerad av blåa laserpulser vid en våglängd av 398 nm och vid pulslängder i storlek av pikosekunder i periodiskt‑polad KTiOPO4, Rb:KTiOPO4, RbTiOPO4, KTiOAsO4 och RbTiOAsO4. Den termiska linsen mättes med en metod kallad gemensam-vägsträcka-interferometer (Eng: common-path interferometer), en metod känslig nog för att mäta absorption så låg som 10-5 cm-1. Dessutom undersöktes hur nivån av BLIIRA beror på medeleffekten och intensiteten hos den blåa laserstrålen samt på kristalltemperaturen. Resultaten visar att det bildas minst två typer av färgcentra med olika livslängder. Vidare observerades en högre grad av långsamt avklingande absorption i fosfaterna jämfört med arsenaterna. Den största delen av den inducerade absorptionen tillskrivs fotogenererade elektroner och hål som ”självfångas” i närheten av Ti4+ respektive O2- joner, och bildar färgcentra av polaron karaktär. Stabilisering av dessa centra underlättas av lättrörliga alkalivakanser i kristallerna. / <p>QC 20150922</p>