Indiana University-Purdue University Indianapolis (IUPUI) / Fabrication and analysis of Copper Indium Gallium di-Selenide (CIGS) nanoparticles-based thin film solar cells are presented and discussed. This work explores non-traditional fabrication processes, such as spray-coating for the low-cost and highly-scalable production of CIGS-based solar cells. CIGS nanoparticles were synthesized and analyzed, thin CIGS films were spray-deposited using nanoparticle inks, and resulting films were used in low-cost fabrication of a set of CIGS solar cell devices. This synthesis method utilizes a chemical colloidal process resulting in the formation of nanoparticles with tunable band gap and size. Based on theoretical and experimental studies, 100 nm nanoparticles with an associated band gap of 1.33 eV were selected to achieve the desired film characteristics and device performances. Scanning electron microcopy (SEM) and size measurement instruments (Zetasizer) were used to study the size and shape of the nanoparticles. Electron dispersive spectroscopy (EDS) results confirmed the presence of the four elements, Copper (Cu), Indium (In), Gallium (Ga), and Selenium (Se) in the synthesized nanoparticles, while X-ray diffraction (XRD) results confirmed the tetragonal chalcopyrite crystal structure. The ultraviolet-visible-near infra-red (UV-Vis-NIR) spectrophotometry results of the nanoparticles depicted light absorbance characteristics with good overlap against the solar irradiance spectrum. The depositions of the nanoparticles were performed using spray-coating techniques. Nanoparticle ink dispersed in ethanol was sprayed using a simple airbrush tool. The thicknesses of the deposited films were controlled through variations in the deposition steps, substrate to spray-nozzle distance, size of the nozzle, and air pressure. Surface features and topology of the spray-deposited films were analyzed using atomic force microscopy (AFM). The deposited films were observed to be relatively uniform with a minimum thickness of 400 nm. Post-annealing of the films at various temperatures was studied for the photoelectric performance of the deposited films. Current density and voltage (J/V) characteristics were measured under light illumination after annealing at different temperatures. It was observed that the highest photoelectric effect resulted in annealing temperatures of 150-250 degree centigrade under air atmosphere. The developed CIGS films were implemented in solar cell devices that included Cadmium Sulfide (CdS) and Zinc Oxide (ZnO) layers. The CdS film served as the n-type layer to form a pn junction with the p-type CIGS layer. In a typical device, a 300 nm CdS layer was deposited through chemical bath deposition on a 1 $mu$m thick CIGS film. A thin layer of intrinsic ZnO was spray coated on the CdS film to prevent shorting with the top conductor layer, 1.5 μm spray-deposited aluminum doped ZnO layer. A set of fabricated devices were tested using a Keithley semiconductor characterization instrument and micromanipulator probe station. The highest measured device efficiency was 1.49%. The considered solar cell devices were simulated in ADEPT 2.0 solar cell simulator based on the given fabrication and experimental parameters. The simulation module developed was successfully calibrated with the experimental results. This module can be used for future development of the given work.

Cellulose is the most abundant biopolymer on Earth as it is found in every plant cell wall; therefore, it represents one of the most promising natural resources for the fabrication of sustainable materials. In plants, cellulose is mainly used for structural integrity, however, some species organise cellulose in helicoidal nano-architectures generating strong iridescent colours. Recent research has shown that cellulose nanocrystals, CNCs, isolated from natural fibres, can spontaneously self-assemble into architectures that resemble the one producing colouration in plants. Therefore, CNCs are an ideal candidate for the development of new photonic materials that can find use to substitute conventional pigments, which are often harmful to humans and to the environment. However, various obstacles still prevent a widespread use of cellulose-based photonic structures. For instance, while the CNC films can display a wide range of colours, a precise control of the optical appearance is still difficult to achieve. The intrinsic low thermal stability and brittleness of cellulose-based films strongly limit their use as photonic pigments at the industrial scale. Moreover, it is challenging to integrate them into composites to obtain further functionality while preserving their optical response. In this thesis, I present a series of research contributions that make progress towards addressing these challenges. First, I use an external magnetic field to tune the CNC films scattering response. Then, I demonstrate how it is possible to tailor the optical appearance and the mechanical properties of the films as well as to enhance their functionality, by combining CNCs with other polymers. Finally, I study the thermal properties of CNC films to improve the retention of the helicoidal arrangement at high temperatures and to explore the potential use of this material in industrial fabrication processes, such as hot-melt extrusion.

Les milieux réactionnels issus de l’étude de la réactivité de deux types de polyols, le glycérol et le diglycérol par réaction d’estérification directe avec l’acide undécylénique, catalysée par l’acide dodécylbenzène sulfonique (ADBS). Les résultats montrent que les ystèmes polyol/acide undécylénique donnent une émulsion eau dans huile (E/H). L’ajout de l’ADBS et de l’eau formée in-situ aux systèmes polyol/acide undécylénique ont permis de réduire la taille des gouttelettes de 50 μm à moins de 1 μm et d’obtenir un système organisé (micro-réacteur). L’augmentation de la température contribue à favoriser le transfert de matière dans les systèmes émulsionnés et / ou gélifiés et d’obtenir un système monophasique, homogène et structurés. L’étude de la réaction de ces systèmes avec une approche site à site (site OH / site COOH) a montré que lorsque le nombre de sites acides carboxyliques est inférieur à celui des sites hydroxyles, la synthèse est totalement sélective en esters partiels des deux polyols (glycérol et diglycérol). Les rendements sont supérieurs respectivement à 60% en esters partiels de glycérol et à 70% en esters partiels de diglycérol. La modélisation de la cinétique de synthèses et la régression des données cinétiques ont montré que la réaction est réversible d’ordre 2 et athermique. Les énergies d’activation calculées sont de 17 kcal/mol et 16 kcal/mol respectivement pour le monoundécénoate de glycérol (MUG) et le diundécénoate de glycérol (DUG). De plus, la méthodologie de recherche expérimentale a montrée que les variables (concentration en catalyseur ADBS et température) permettent d’obtenir le MUG avec un rendement de plus de 60% et une sélectivité en MUG de 80%. Ensuite, l’étude de la réactivité de la double liaison terminale du MUG en présence de deux agents oxydants pour engendrer des molécules bolaamphiphiles simples a été réalisée par H2O2 / acide formique et acide métachloroperbenzoïque (m-CPBA). Les résultats ont montré le 10,11-dihydroxy-monoundécénoate de glycérol (MUGDiol) est obtenu par oxydation au H2O2 / acide formique et le 10,11-époxy-monoundécénoate de glycérol (MUGE) par réaction d’époxydation avec la m-CPBA. L’ouverture de la fonction époxyde par des molécules aminées permet l’observation de nouvelles molécules bolaamphiphiles : le 10-hydroxy-N-11-((2-hydroxyéthyl)amino)monoundécénoate de glycérol(bola éthanolamineglycérol) et le N,N-11-(diaminobutan)-10-hydroxymonoundecanoate de glycérol (bola diaminobutaneglycérol). L’étude des propriétés physico-chimiques de ces molécules amphiphiles et bolaamphiphiles a permis de monter que toutes ces molécules sont de solvo-surfactants actifs aux interfaces et elles réduisent la tension interfaciale de l’eau jusqu’à la limite de la solubilité dans l’eau. L’adsorption des molécules ne vérifie pas le modèle de Gibbs. Le MUG et le MUDG s’auto-assemblent dans l’eau et donnent des nano-objets (vésicules et agrégats plats) et s’adsorbent sur des surfaces polaires et solides (silice et ciment). Ces deux molécules retiennent 30% et 56% molécules d’eau et le nombre de molécules d’eau fortement liée aux têtes polaires est de 21 et 49 respectivement pour le MUG et le MUDG. Pour es molécules bolaamphiphiles pures (MUGE et bola éthanolamineglycérol), elles retiennent plus de 56% de molécules d’eau et se lient à plus 53 molécules d’eau. L’ensemble de ces propriétés physico-chimiques a permis de répondre aux problématiques industrielles et de formuler un produit de cure, un agent de démoulage et un produit anti-adhérent. / This study is of the reactivity of two types of polyols (glycerol and diglycerol) by direct esterification reaction with undecylenic acid from castor oil. This reaction was catalyzed by dodecylbenzene sulfonic acid (DBSA). The first step was to study of polyol / undecylenic acid reaction systems by physico-chemical approach. The result have shown that these systems give water-in-oil (W / O) emulsion. Adding DBSA and water formed in-situ in polyol/undecylenic acid systems have reduced droplet size from 50 microns to less than 1 μm and form an organized system (micro-reactor). Increasing temperature can simplify transfers in emulsified systems and / or melted gel and to get a monophasic and homogeneous system. The only systems and aided by water formed in-situ assists the organization and structuring of gels. The reaction study of these systems was analyzed by gas chromatography. This showed that when the number of carboxylic acid function sites is less than the hydroxyl function site, synthesis is totally selective to partial esters of the two polyols (glycerol and diglycerol). The yields are higher than 60% in partial glycerol esters and 70% in partial diglycerol esters. The kinetic modeling of this synthesis and regression of kinetic data by the software GEPASI showed that the reaction follows the reversible 2 order and it is athermic. The calculated activation energy is 17 kcal/mol for the synthesis of glycerol monoundecenoate (GMU) and 16 kcal/mol for glycerol diundecenoate (GDU), these values are close to the theoretical values and they show that the reaction is happening at room temperature. Moreover, the response of the surface methodology shows that the variables chosen for the present study are temperature and catalyst concentration have a positive effect on the yield of the GMU. This approach was used to determine the optimum conditions for producing the GMU. Second study performed was of the reactivity of the terminal double bond of the GMU in presence of two oxidizing agents H 2 O 2 / formic acid and metachloroperbenzoic acid (m-CPBA), for synthesized bolaamphiphiles molecules was performed. The H 2 O 2 /formic acid was used to oxidize the double bond of GMU in diol function of glycerol 10,11-dihydroxymonoundecenoate (GMUDiol). The m-CPBA epoxidizes the double bond of GMU to give glycerol 10,11-epoxymonoundécénoate (GMUE). The opening of the epoxide function by aminoalcohol molecules are used to generate the new molecules bolaamphiphiles molecules: the bola ethanolamineglycerol and the bola diaminobutaneglycerol. The third step was the stady of the physico-chemical properties of pure amphiphilic and bolaamphiphiles molecules. The result was shown that all molecules are solvo-surfactants molecules and they are active in the interfaces (liquid/air and liquid/solid). The curves of surface tension of water do not respect the Gibbs rule. GMU and DGMU self- assemble in water and give nano-objects (vesicles and aggregates) in diluted solutions. In hydrogel, the molecules self-assemble in lamellar phase. In this lamellar phase, the amount of water retained is 56% and the number of water molecules strongly linked to the polar heads is 49 moles of water/diglycerol monoundecenoate molecule (DGMU). All these physico-chemical properties have permit to respond to industrial problems such as water retention for the curing product, self-assembly for demoulding concrete and for surface anti-adhesion and adsorption and finally foaming required for the aged bitumen regeneration. For pure bolaamphiphiles molecules (GEMU and ethanolamineglycerol bola) reduce the interfacial tension of water to the limit of the solubility of this bola molecules in water but do not provide a critical aggregation concentration (CAC). They retain more water molecules respectively between 56% and 63% water and the number of water molecules strongly bound with two polar heads groups pure bolaamphiphiles molecules is between 42 and 53.

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This thesis describes laboratory measurements of the complex refractive index of volcanic ash particles. These measurements are needed to model the radiative impact of volcanic ash, vital for accurate satellite remote sensing. Three experimental methods have been developed, and the results for the complex refractive index and optical properties of a wide range of volcanic ash samples are presented. Measurements were made of the spectral transmission of radiation through suspended volcanic ash particles inside an aerosol cell, using a Fourier transform spectrometer at infrared wavelengths and two diffraction grating spectrometers covering ultraviolet, visible, and near-infrared wavelengths. In addition to the optical measurements, a suite of sampling and sizing instruments were connected downstream of the aerosol cell to measure the particle size distribution. The method was calibrated using two quartz samples. Mass extinction coefficients for nine volcanic ash samples, at 0.3-14 μm, are presented and show considerable variation. These variations are linked to the composition of the samples, measured using X-ray fluorescence (XRF) analysis. The complex refractive index, at 0.3-14 μm, of the two quartz samples and two samples of volcanic ash from the 2010 Eyjafjallajökull eruption were retrieved from the extinction measurements. The forward model used Mie theory and a classical damped harmonic oscillator (CDHO) model to represent the complex refractive index of the samples in terms of a finite set of band parameters, as well as the real refractive index of the sample in the small wavelength limit. Previous studies have shown that there is a redundancy in the retrievals between the band strength parameters and the real refractive index in the small wavelength limit, which can lead to spurious values for the retrieved complex refractive index. This problem was overcome by using an independent measurement of the real refractive index at a visible wavelength, to constrain the model parameter of the real refractive index in the short wavelength limit. Independent measurements of the complex refractive index at visible wavelengths are also important because the extinction produced at these wavelengths is highly sensitive to the particle size distribution, and any uncertainty in the measured size distribution will contribute to significant systematic error in the refractive index retrieved from extinction. The retrieved spectral complex refractive index of Eyjafjallajökull ash was applied using the ORAC retrieval scheme to measurements of the 2010 Eyjafjallajökull eruptionmade by theMODIS instrument aboard NASA's Terra satellite. Significant difference were found in the retrieved plume parameters of optical path, effective radius, and plume altitude, compared to assuming a literature measurement for the refractive index of pumice. For three discrete visible wavelengths (450, 546.7, and 650 nm) an optical microscope was used to make measurements of the complex refractive index of the volcanic ash samples. The long-established Becke line method was used to measure the real refractive index of the samples. For the imaginary refractive index, a new and novelmethod was developed involving measurements of the attenuation of light in individual particles. A strong linear correlation was found between the SiO₂ content of the samples and both their real and imaginary refractive indices at the visible wavelengths investigated. Furthermore, from the XRF compositional analysis of the samples values were calculated for the ratio of non-bridging oxygen atoms per tetrahedral cation (NBO/T), and it was found that NBO/T was an even stronger predictor of real refractive index at visible wavelengths. The optical microscope measurements could only be applied to particles with a radius larger than 10 μm. A new refractometer method was investigated for retrieving the real refractive index of submicron particles from colloidal reflectance measurements close to the critical angle in an internal reflection configuration. A coherent scattering model (CSM) was used to model the coherent reflection from a half-space of monodisperse or polydisperse particles, and a simple extension of the model is presented to properly account for the modified size distribution at the interface in an internal reflection set-up. A rigorous sensitivity analysis was performed to determine how experimental uncertainties propagate into uncertainty associated with the retrieved real refractive index, and the uncertainty due to non-spherical effects was estimated using T-matrix methods. Experimental reflectance data at a wavelength of 635 nm were obtained for spherical monodisperse polystyrene calibration particles, a polydisperse sand sample, and a polydisperse volcanic ash sample. The retrieved values for the real refractive index agreed, within propagated uncertainties, with values measured using other techniques. The method is shown to be a viable technique for measuring the real refractive index of small quantities of submicron particles, and can also retrieve the concentration and size of particles.