An electrochromic (EC) material is able to change colour under the influence of an electric potential. The development of energy efficient smart windows for architectural applications is at present the subject of intense research for both economic and environmental reasons. Thus there is now a considerable research effort to develop smart windows with natural colour switching properties, i.e. shades of grey. In this regard, a promising metal oxide with a brown-black anodic colouring state is NiO or hydrated nickel oxide (also called nickel hydroxide , Ni(OH)2). The present work outlines the preparation and optimisation of EC nickel oxide-based ceramic precursor films onto various conducting substrates towards smart window applications. The literature review chapter outlines the different methods used for generating ceramic materials, a review of electrochromism and history of nickel oxide-based EC materials are also provided. Thins films have been deposited by an electrochemical cathodic deposition and by aerosol assisted chemical vapour deposition (AACVD) technique. For hydrated NiO films prepared by electrochemical cathodic deposition, various deposition factors at small-scale area (30 x 7 mm) have been investigated in order to optimise the films properties towards EC applications. With deposition on fluorine-doped tin oxide (SnO2:F, FTO) on glass, use of nickel nitrate (0.01 mol dm-3) solution at an applied current of -0.2 mA (-0.1 mA cm-2) for 800 s was optimal for preparing uniform deposits with a porous interconnecting flake-like structure, which is generally regarded as favourable for the intercalation/deintercalation of hydroxide ions during redox cycling. The as-deposited hydrated NiO films showed excellent transmittance modulation (Δ%T = 83.2 at 432 nm), with average colouration efficiency (CE) of 29.6 cm2 C-1 and low response times. However, after 50 voltammetric cycles, the cycle life was found to fade by 17.2% from charge measurements, and 28.8 % from in-situ transmittance spectra measurements. In an attempt to prepare films with improved durability, AACVD has been used for the first time in the preparation of thin-film EC nickel(II) oxide (NiO). The as-deposited films were confirmed to be cubic NiO from analysis of powder X-ray diffraction data, with an optical band gap that decreased from 3.61 to 3.48 eV with an increase in film thickness (in the range 330 820 nm). The EC properties of the films were investigated as a function of film thickness, following 50, 100 and 500 conditioning oxidative voltammetric cycles in aqueous KOH (0.1 mol dm-3). Light modulation of the films increased with the number of conditioning cycles. EC response times were < 10 s and generally longer for the colouration than the bleaching process. The films showed excellent stability when tested for up to 10000 colour/bleach cycles. Using a calculation method based on the integration of experimental spectral power distributions derived from in-situ visible region spectra over the CIE 1931 colour-matching functions, the colour stimuli of the NiO-based films, and the changes that take place on reversibly switching between the bleached and coloured forms have been calculated. Films prepared by both deposition techniques gave positive a* and b* values to produce orange. However, in combination with low L* values, the films were perceived as brown-grey. Hydrated NiO prepared via electrochemical cathodic deposition suffers from two well-known limitations; firstly, it shows catalytic properties towards the oxygen evolution reaction (OER), which is a process very close to the Ni(II)/Ni(III) redox process. Secondly, hydrated NiO shows poor cycling durability in alkaline solution. The co-deposition of single or bimetallic additives is an effective way to overcome these problems. Electrochemical studies revealed that the combination of cobalt (10%) with lanthanum (5%) was found to be the optimal composition for preparing hydrated NiO films with improved film durability. Finally, the emphasis of this work was on scale-up of deposition. Therefore, optimised deposition conditions from small scale (3.0 x 0.7 cm) have been used to successfully deposit films on two different sized large-area (10 x 7.5 and 30 x 30 cm) conducting substrates.

Une étude en deux parties a été effectuée sur la préparation et la caractérisation de céramiques de ZnSe et de verres de phosphate à des fins optiques. Pour préparer des poudres de ZnSe, deux voies de synthèse ont été utilisées: i) hydrothermales; ii) le broyage à billes. La taille des particules ainsi que leur morphologie a été analysée par différentes techniques (DRX, MEB…). Ensuite, deux technologies de frittage, pressage à chaud (HP) et frittage flash (SPS), ont été mises en œuvre pour obtenir des échantillons massifs de ZnSe optiquement transparents. La meilleure transmission obtenue dans le domaine du moyen infrarouge, pour les échantillons HP et SPS, est supérieure à 50% et 40% respectivement. Pour obtenir des verres de phosphate avec une grande durabilité chimique, des cations avec une intensité de champ élevée tels que Nb5+ et Ti4+ ont été incorporés dans un verre de phosphate. La transparence dans le domaine du visible a été obtenue en utilisant de petites quantités d'agents d'oxydation tels que les sulfates ou les nitrates. L’utilisation de la spectroscopie par réflectance diffuse a permis de déterminer les coordonnées chromatiques afin d’évaluer le bénéfice de ces ajouts. / A two-part study was conducted on the preparation and characterization of ZnSe ceramic and phosphate glasses for optical applications in the visible and infrared range. To prepare ZnSe powders, two synthetic routes were used: i) hydrothermal; ii) ball milling. The size and morphology of synthesized powders were analyzed using different techniques (XRD, SEM…). Then two sintering technologies, hot pressing (HP) sintering and spark plasma sintering (SPS) sintering have been implemented to obtain optically transparent ZnSe bulk samples. The best transmission obtained in the mid-infrared range, using HP and SPS, is greater than 50% and 40% respectively. To synthesize phosphate glasses with a high chemical durability, cations with high field strength such as Nb5+ and Ti4+ were incorporated into a phosphate matrix. The transparency in the visible range was obtained using small amounts of oxidation agents such as sulfates or nitrates. The use of diffuse reflectance spectroscopy led to determination of the chromaticity coordinates to evaluate the benefit of these additions.