The building sector is one of the largest consumers of energy, where the cooling of buildings accounts for a large portion of the total energy consumption. Electrochromic (EC) smart windows have a great potential for increasing indoor comfort and saving large amounts of energy for buildings. An EC device can be viewed as a thin-film electrical battery whose charging state is manifested in optical absorption, i.e. the optical absorption increases with increased state-of-charge (SOC) and decreases with decreased state-of-charge. It is the EC technology's unique ability to control the absorption (transmittance) of solar energy and visible light in windows with small energy effort that can reduce buildings' cooling needs. Today, the EC technology is used to produce small windows and car rearview mirrors, and to reach the construction market it is crucial to be able to produce large area EC devices with satisfactory performance. A challenge with up-scaling is to design the EC device system with a rapid and uniform coloration (charging) and bleaching (discharging). In addition, up-scaling the EC technology is a large economic risk due to its expensive production equipment, thus making the choice of EC material and system extremely critical. Although this is a well-known issue, little work has been done to address and solve these problems. This thesis introduces a cost-efficient methodology, validated with experimental data, capable of predicting and optimizing EC device systems' performance in large area applications, such as EC smart windows. This methodology consists of an experimental set-up, experimental procedures and a twodimensional current distribution model. The experimental set-up, based on camera vision, is used in performing experimental procedures to develop and validate the model and methodology. The two-dimensional current distribution model takes secondary current distribution with charge transfer resistance, ohmic and time-dependent effects into account. Model simulations are done by numerically solving the model's differential equations using a finite element method. The methodology is validated with large area experiments. To show the advantage of using a well-functioning current distribution model as a design tool, some EC window size coloration and bleaching predictions are also included. These predictions show that the transparent conductor resistance greatly affects the performance of EC smart windows. / Byggnadssektorn är en av de största energiförbrukarna, där kylningen av byggnader står för en stor del av den totala energikonsumtionen. Elektrokroma (EC) smarta fönster har en stor potential för att öka inomhuskomforten och spara stora mängder energi för byggnader. Ett elektrokromt fönster kan ses som ett tunnfilmsbatteri vars laddningsnivå yttrar sig i dess optiska absorption, d.v.s. den optiska absorptionen ökar med ökad laddningsnivå och vice versa. Det är EC-teknologins unika egenskaper att kunna kontrollera absorptionen (transmittansen) av solenergi och synligt ljus i fönster med liten energiinsats som kan minska byggnaders kylningsbehov. EC-teknologin används idag till att producera små fönster och bilbackspeglar, men för att nå byggnadsmarknaden är det nödvändigt att kunna producera stora EC-anordningar med fullgod prestanda. En välkänd utmaning med uppskalning är att utforma EC-systemet med snabb och jämn infärgning (laddning) och urblekning (urladdning), vilket även innebär att uppskalning är en stor ekonomisk risk på grund av den dyra produktionsutrustningen. Trots att detta är välkända problem har lite arbete gjorts för att lösa dessa. Denna avhandling introducerar ett kostnadseffektivt tillvägagångssätt, validerat med experimentella data, kapabelt till att förutsäga och optimera ECsystems prestanda för anordningar med stor area, såsom elektrokroma smarta fönster. Detta tillvägagångssätt består av en experimentell uppställning, experiment och en tvådimensionell strömfördelningsmodell. Den experimentella uppställningen, baserad på kamerateknik, används i de experimentella tillvägagångssätten så att modellen kan utvecklas och valideras. Den tvådimensionella strömfördelningsmodellen inkluderar sekundär strömfördelning med laddningsöverföringsmotstånd, ohmska och tidsberoende effekter. Modellsimuleringarna görs genom att numeriskt lösa en modells differentialekvationer med hjälp av en finita-element-metod. Tillvägagångssättet är validerat med experiment gjorda på stora EC anordningar. För att visa fördelarna med att använda en väl fungerande strömfördelningsmodell som ett designverktyg, har några prediktioner av infärgning och urblekning av EC-fönster inkluderats. Dessa prediktioner visar att den transparenta strömtilledarresistansen har stor påverkan på EC-fönsters prestanda.

Groundbreaking progress in molecule-based optoelectronic devices for lighting, display and energy-harvesting technologies demands highly efficient and easily processable functional materials with tunable properties governed by their molecular/supramolecular structure variations. To date, functional coordination compounds whose function is governed by non-covalent weak forces (e.g., metallophilic, dπ-acid/dπ-base stacking, halogen/halogen and/or d/π interactions) remain limited. This is unlike the situation for metal-free organic semiconductors, as most metal complexes incorporated in optoelectronic devices have their function determined by the properties of the monomeric molecular unit (e.g., Ir(III)-phenylpyridine complexes in organic light-emitting diodes (OLEDs) and Ru(II)-polypyridyl complexes in dye-sensitized solar cells (DSSCs)). This dissertation represents comprehensive results of both experimental and theoretical studies, descriptions of synthetic methods and possible application allied to monovalent coinage metal-based functional materials. The main emphasis is given to the design and synthesis of functional materials with preset material properties such as light-emitting materials, light-harvesting materials and conducting materials. In terms of advances in fundamental scientific phenomena, the major highlight of the work in this dissertation is the discovery of closed-shell polar-covalent metal-metal bonds manifested by ligand-unassisted d10-d10 covalent bonds between Cu(I) and Au(I) coinage metals in the ground electronic state (~2.87 Å; ~45 kcal/mol). Moreover, this dissertation also reports pairwise intermolecular aurophilic interactions of 3.066 Å for an Au(I) complex, representing the shortest ever reported pairwise intermolecular aurophilic distances among all coinage metal(I) cyclic trimetallic complexes to date; crystals of this complex also exhibit gigantic luminescence thermochromism of 10,200 cm-1 (violet to red). From applications prospective, the work herein presents monovalent coinage metal-based functional optoelectronic materials such as heterobimetallic complexes with near-unity photoluminescence quantum yield, metallic or semiconducting integrated donor-acceptor stacks and a new class of Au(III)-based black absorbers with cooperative intermolecular iodophilic (I…I) interactions that sensitize the harvesting of all UV, all visible, and a broad spectrum of near-IR regions of the solar spectrum. These novel functional materials of cyclic trimetallic coinage metal complexes have been characterized by a broad suit of spectroscopic and structural analysis methods in the solid state and solution.

La compréhension et l'étude du système nerveux est un des grands enjeux du XXIème siècle à la fois pour la recherche fondamentale, mais également pour la mise au point de neuroprothèses implantables pour la réhabilitation fonctionnelle (exemple : implants rétiniens, implants cochléaires). Depuis quelques années, des systèmes basés sur l'utilisation de multi-électrodes (MEA : Multi-Electrode-Array) offrent la possibilité d'enregistrer des milliers de cellules interconnectées entre-elles sur plusieurs jours sur des tranches de tissu nerveux ou des systèmes nerveux complets. Mais une des limites de cette technique est le faible nombre de voies de ces systèmes (64 voies). Les travaux de cette thèse ont consisté à développer une technologie de fabrication permettant la réalisation d'un système multiélectrode s « haute densité 3D ». Cela passe par le développement d'une nouvelle technologie dans la réalisation de micro pointes basée sur la gravure profonde du silicium (DRIE), qui permet d'obtenir des pointes en silicium de 80 µm de haut espacées de 50 µm. Des matrices 60, 256 et 1024 voies ont été fabriquées par cette technique. L'utilisation de la stimulation est aussi un point important dans l'étude de ces grands réseaux, mais il n'est pas possible actuellement de disposer de système permettant une stimulation focale. Pour résoudre ce problème, nous avons développé des matrices spécifiques permettant d'obtenir des stimulations focales du tissu. Nous avons également dans ces travaux de thèse étudié le comportement de l'interface métal/liquide, qui est cruciale pour la réalisation de MEA, en utilisant des techniques d'électrochimie / One challenge of the XXIème century will be to understand dynamics of large neural networks for research and to develop neuroprothesis implant (ex retinal implant, cochlear implant). Today microelectrodes arrays (MEAs) positioned in contact with the neural tissue offer the opportunity to record and simulate neuronal tissue. But the main drawback of his technique is low number of recording sites (typically 64). During this thesis, we have developed a specific process using deep reactive ions etching (DRIE), to achieve high density 3D MEAs containing several hundreds of microelectrodes. We have fabricated microneedles 80 µm of height with spacing of 50 µm and MEAs with 60 – 256 and 1024 microelectrodes have been built with this process. Microstimulation, which makes use of electrodes on the micron scale, is gaining increasing interest in both fundamental and clinical research, opening the possibility to stimulate small groups of neurons instead of large regions. However, controlling the spatial extent of microstimulation to achieve focal activation of neuron networks is a challenge. We have proposed a new configuration of MEA specifically designed to achieve a local stimulation. We have also characterised the interface metal/liquid, that was very important for MEA and we have used electrochemistry techniques

A plethora of novel scientific phenomena and practical applications, such as solid-state molecular solar cells and other optoelectronic devices for energy harvesting and lighting technologies, have catalyzed us to synthesize novel compounds with tunable properties. Synthetic routes, single crystal structures, and spectral and materials properties are described. Reactions of Ag(I) and Cu(I) precursors with various types of ligands -- including the azolates, diimines, and diiphosphines -- lead to the corresponding complexes in high yield. Varying the metal ions, ligands, synthetic methods, solvents, and/or stoichiometric ratio can change the properties including the molecular geometry or packing structure, reactivity, photophysical and photochemical properties, semiconducting behavior, and/or porosity of the functional coordination polymers obtained. For solar cells purposes, the absorption energy can be extended from the ultraviolet (UV) region, through the entire visible (Vis) region, onto a significant portion of the near-infrared (NIR) portion of the solar spectrum with high absorption coefficients due to the infinite conjugation of Cu(I) with diimine ligands. Twenty-eight crystal structures were obtained by conventional crystal growth methods from organic solvents, whereas their bulk product syntheses also included "green chemistry" approaches that precluded the use of hazardous organic solvents. The resulting products are characterized by powder x-ray diffraction (PXRD), Fouriertransform infrared (FTIR), nuclear magnetic resonance (NMR), UV/Vis/NIR absorption/diffuse reflectance/photoluminescence spectroscopies, and thermogravimetric analysis (TGA). Regarding the scientific phenomena investigated, the highlighting work in this dissertation is the discovery of novel bonding/photophysical/optoelectronic properties of the following materials: a black absorber with absorption from 200- 900 nm, a very stable compound with a bright green luminescence obtained by a solventless reaction, and a novel coordination polymer showing uncommon interaction of Ag(I) with three different types of diimine ligands simultaneously.

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