Two-dimensional (2D) membranes are emerging candidates for osmotic energy conversion. However, the trade-off between ion selectivity and conductivity remains the key bottleneck. Here we demonstrate a fully crystalline imine-based 2D polymer (2DPI) membrane capable of combining excellent ionic conductivity and high selectivity for osmotic energy conversion. The 2DPI can preferentially transport cations with Na+ selectivity coefficient of 0.98 (Na+/Cl− selectivity ratio ~84) and K+ selectivity coefficient of 0.93 (K+/Cl− ratio ~29). Moreover, the nanometer-scale thickness (~70 nm) generates a substantially high ionic flux, contributing to a record power density of up to ~53 W m−2, which is superior to most of nanoporous 2D membranes (0.8~35 W m−2). Density functional theory unveils that the oxygen and imine nitrogen can both function as the active sites depending on the ionization state of hydroxyl groups, and the enhanced interaction of Na+ versus K+ with 2DPI plays a significant role in directing the ion selectivity.

A highly effective electrocatalyst is the central component of advanced electrochemical energy conversion. Recently, two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have emerged as a class of promising electrocatalysts due to their advantages including 2D layered structure with high in-plane conjugation, intrinsic electrical conductivity, permanent pores, large surface area, chemical stability, and structural diversity. In this review, we summarize the recent advances of 2D c-MOF electrocatalysts for electrochemical energy conversion. Firstly, we introduce the chemical design principles and synthetic strategies of the reported 2D c-MOFs, as well as the functional design for the electrocatalysis. Subsequently, we present the representative 2D c-MOF electrocatalysts in various electrochemical reactions, such as hydrogen/oxygen evolution, and reduction reactions of oxygen, carbon dioxide and nitrogen. We highlight the strategies for the structural design and property tuning of 2D c-MOF electrocatalysts to boost the catalytic performance, and offer our perspectives in regard to the challenges to be overcome.

Dans un contexte où l’approvisionnement énergétique mondial du 21e siècle est un enjeu majeur, le développement de sources d’énergie renouvelables suscite l’attention croissante de la communauté scientifique et industrielle. L’énergie solaire est définitivement l’une des meilleures alternatives aux combustibles fossiles en tant que source d’énergie du monde de demain. Ce mémoire traite donc du développement de nouveaux matériaux organométalliques pour des applications de photorécoltage d’énergie en photovoltaïque et en production d’hydrogène. Le premier chapitre présente la synthèse assistée par microondes de quatre nouveaux complexes de Co(II), Ni(II), Cu(II) et Zn(II) basés sur le ligand tétra-p-méthoxyphényl-azadipyrrométhène (ADPM) avec des rendements variant de 89% à quantitatif. Ces complexes sont mis en relation avec d’autres complexes homoleptiques connus portant le tétraphényl-ADPM comme ligand ainsi qu’avec leurs chélates de BF2+ pour une meilleure compréhension des tendances engendrées par la substitution de l’agent coordonnant et/ou des substituants p-méthoxy. Pour ce faire, le comportement électrochimique et photophysique est présenté. De façon générale, la présence des quatre groupements p-méthoxy semble rendre les dérivés de cet ADPM plus susceptibles à la dégradation électrochimique en conditions d’oxydation et induire un déplacement bathochromique des propriétés optiques d’absorption et d’émission. Les structures rayons X du ligand tétra-p-méthoxyphényl-ADPM et de son complexe homoleptique de Co(II) sont aussi discutées. Cette étude a été effectuée dans l’espoir de fournir des informations utiles sur la stabilité des ADPM aux chercheurs du domaine photovoltaïque en quête de nouveaux chromophores dans le proche infrarouge (NIR). Le deuxième chapitre présente quant à lui les propriétés de senseur envers les anions F-, OAc- et H2PO4- de deux nouveaux complexes neutres de Re(I) de type mono- et dinucléaire basés sur une phénanthroline substituée en position 5 contenant un récepteur thio-urée. Ces composés ont été obtenus dans des rendements de 81% et 60%, respectivement. L’effet de la formation de ponts hydrogène lors de l’ajout d’anions versus la déprotonation du récepteur a été évalué par des titrations UV/Vis et RMN 1H et semble indiquer que la formation de la base conjuguée du récepteur est favorisée pour ce type de système. De plus, la structure rayons X d’un des précurseurs est présentée et permet une discussion sur la chiralité des complexes mono- et dinucléaire obtenus. L’obtention d’un complexe bimétallique par autoassemblage ouvre la voie à la préparation d’antennes moléculaires pour des systèmes de photosynthèse artificielle. / The world's energy supply is rapidly becoming the major issue of the 21st century. Instead of the status quo approach of finding and extracting more hydrocarbons from the ground, the development of renewable energy sources is attracting much interest from both the scientific and industrial communities. Solar energy is definitively one of the best sources to power the World of tomorrow. In such a framework, this dissertation discusses the development of new organometallic materials able to harvest solar energy for photovoltaic or H2 photoproduction applications. The first chapter presents the synthesis by a microwaves-assisted methodology of four new homoleptic complexes of Co(II), Ni(II), Cu(II) and Zn(II) based on the tetra-p-methoxyphenyl-azadipyrromethene (ADPM) ligand in yields ranging from 89% to quantitative. Those complexes are put in relation with already known ADPM homoleptic complexes of the same M(II) series and related BF2+ chelates (Aza-BODIPY) for a better understanding of trends arising from substitution of the chelate and/or electron-donating effect of the p-methoxy substituents. This is achieved by the study of electrochemical behavior of the compounds and their photophysical properties. From a general point of view, the presence of the four p-methoxy substituents leads to an electrochemical decomposition of the derivatives based on that ADPM in oxidative conditions, along with a bathochromic shift of the optical properties. X-Ray structures for the tetra-p-methoxyphenyl-ADPM ligand and related Co(II) complex are also discussed. Hopefully, this study will provide useful insights to researchers on the substituents to install for stable ADPM derivatives in their quest for NIR chromophores utilizable for photovoltaic application. The second chapter report anion sensing properties toward F-, OAc- and H2PO4- of new neutral mononuclear and dinuclear Re(I) complexes based on a 5-substituted phenanthroline moiety bearing a thiourea hydrogen-bonding receptor. Those complexes were obtained in 81% and 60% yields, respectively. The effect of hydrogen-bonding versus deprotonation of the thiourea receptor upon addition of the anions was also evaluated by UV/vis and 1H NMR titration techniques. Observations made support the hypothesis that formation of the conjugated base of the receptor is favored. In addition, an X-ray structure of the Re(I) precursor complex is reported and the chirality of the mononuclear and dinuclear complexes is discussed. Achievement of a bimetallic complex by self-assembly paves the way for the preparation of light-harvesting molecular antennae utilizable in artificial photosynthesis systems.

The development of a numeric simulation for predicting the performance of an Ocean Current Energy Conversion System is presented in this thesis along with a control system development using a PID controller for the achievement of specified rotational velocity set-points. In the beginning, this numeric model is implemented in MATLAB/Simulink® and it is used to predict the performance of a three phase squirrel single-cage type induction motor/generator in two different cases. The first case is a small 3 meter rotor diameter, 20 kW ocean current turbine with fixed pitch blades, and the second case a 20 meter, 720 kW ocean current turbine with variable pitch blades. Furthermore, the second case is also used for the development of a Voltage Source Variable Frequency Drive for the induction motor/generator. Comparison among the Variable Frequency Drive and a simplified model is applied. Finally, the simulation is also used to estimate the average electric power generation from the 720 kW Ocean Current Energy Conversion System which consists of an induction generator and an ocean current turbine connected with a shaft which modeled as a mechanical vibration system.

Les principaux défis pour le déploiement de systèmes de conversion de l'énergie éolienne est de maximiser la puissance électrique produite, malgré les variations des conditions météorologiques, tout en minimisant les coûts de fabrication et de maintenance du système. L'efficacité de la turbine éolienne est fortement dépendante des perturbations de l'environnement et des paramètres variables du système, tels que la vitesse du vent et l'angle de tangage. Les incertitudes sur le système sont difficiles à modéliser avec précision alors qu'ils affectent sa stabilité.Afin d'assurer un état de fonctionnement optimal, malgré les perturbations, le commande adaptative peut jouer un rôle déterminant. D'autre part, la synthèse de commandes tolérantes aux défauts, capables de maintenir les éoliennes connectées au réseau après la survenance de certains défauts est indispensable pour le bon fonctionnement du réseau. Le travail de cette thèse porte sur la mise en place de lois de commande adaptatives et tolérantes aux défauts appliqués aux systèmes de conversion de l'énergie éolienne. Après un état de l'art, les contributions de la thèse sont :Dans la première partie de la thèse, un modèle incertain non linéaire du système de conversion d'énergie éolienne avec un générateur à induction à double alimentation est proposé. Une nouvelles approches de commande adaptative par mode glissant est synthétisée et ensuite appliquée pour optimiser l'énergie issue de l'éolienne.Dans la deuxième partie, une nouvelle commande par modes glissants tolérante aux défauts et basée sur les modes glissants intégrales est présentée. Puis, cette méthode est appliquée afin de forcer la vitesse de la turbine éolienne à sa valeur optimale en prenant en compte des défauts qui surviennent sur l'actionneur. / The main challenges for the deployment of wind energy conversion systems (WECS) are to maximize the amount of good quality electrical power extracted from wind energy over a significantly wide range of weather conditions and minimize both manufacturing and maintenance costs. Wind turbine's efficiency is highly dependent on environmental disturbances and varying parameters for operating conditions, such as wind speed, pitch angle, tip-speed ratio, sensitive resistor and inductance. Uncertainties on the system are hard to model exactly while it affects the stability of the system. In order to ensure an optimal operating condition, with unknown perturbations, adaptive control can play an important role. On the other hand, a Fault Tolerant Control (FTC) with control allocation that is able to maintain the WECS connected after the occurrence of certain faults can avoid major economic losses. The thesis work concerns the establishment of an adaptive control and fault diagnosis and tolerant control of WECS. After a literature review, the contributions of the thesis are:In the first part of the thesis, a nonlinear uncertain model of the wind energy conversion system with a doubly fed induction generator (DFIG) is proposed. A novel Lyapunov-based adaptive Sliding Mode (HOSM) controller is designed to optimize the generated power.In the second part, a new output integral sliding mode methodology for fault tolerant control with control allocation of linear time varying systems is presented. Then, this methodology has been applied in order to force the wind turbine speed to its optimal value the presence of faults in the actuator.

Dans un contexte où l’approvisionnement énergétique mondial du 21e siècle est un enjeu majeur, le développement de sources d’énergie renouvelables suscite l’attention croissante de la communauté scientifique et industrielle. L’énergie solaire est définitivement l’une des meilleures alternatives aux combustibles fossiles en tant que source d’énergie du monde de demain. Ce mémoire traite donc du développement de nouveaux matériaux organométalliques pour des applications de photorécoltage d’énergie en photovoltaïque et en production d’hydrogène. Le premier chapitre présente la synthèse assistée par microondes de quatre nouveaux complexes de Co(II), Ni(II), Cu(II) et Zn(II) basés sur le ligand tétra-p-méthoxyphényl-azadipyrrométhène (ADPM) avec des rendements variant de 89% à quantitatif. Ces complexes sont mis en relation avec d’autres complexes homoleptiques connus portant le tétraphényl-ADPM comme ligand ainsi qu’avec leurs chélates de BF2+ pour une meilleure compréhension des tendances engendrées par la substitution de l’agent coordonnant et/ou des substituants p-méthoxy. Pour ce faire, le comportement électrochimique et photophysique est présenté. De façon générale, la présence des quatre groupements p-méthoxy semble rendre les dérivés de cet ADPM plus susceptibles à la dégradation électrochimique en conditions d’oxydation et induire un déplacement bathochromique des propriétés optiques d’absorption et d’émission. Les structures rayons X du ligand tétra-p-méthoxyphényl-ADPM et de son complexe homoleptique de Co(II) sont aussi discutées. Cette étude a été effectuée dans l’espoir de fournir des informations utiles sur la stabilité des ADPM aux chercheurs du domaine photovoltaïque en quête de nouveaux chromophores dans le proche infrarouge (NIR). Le deuxième chapitre présente quant à lui les propriétés de senseur envers les anions F-, OAc- et H2PO4- de deux nouveaux complexes neutres de Re(I) de type mono- et dinucléaire basés sur une phénanthroline substituée en position 5 contenant un récepteur thio-urée. Ces composés ont été obtenus dans des rendements de 81% et 60%, respectivement. L’effet de la formation de ponts hydrogène lors de l’ajout d’anions versus la déprotonation du récepteur a été évalué par des titrations UV/Vis et RMN 1H et semble indiquer que la formation de la base conjuguée du récepteur est favorisée pour ce type de système. De plus, la structure rayons X d’un des précurseurs est présentée et permet une discussion sur la chiralité des complexes mono- et dinucléaire obtenus. L’obtention d’un complexe bimétallique par autoassemblage ouvre la voie à la préparation d’antennes moléculaires pour des systèmes de photosynthèse artificielle. / The world's energy supply is rapidly becoming the major issue of the 21st century. Instead of the status quo approach of finding and extracting more hydrocarbons from the ground, the development of renewable energy sources is attracting much interest from both the scientific and industrial communities. Solar energy is definitively one of the best sources to power the World of tomorrow. In such a framework, this dissertation discusses the development of new organometallic materials able to harvest solar energy for photovoltaic or H2 photoproduction applications. The first chapter presents the synthesis by a microwaves-assisted methodology of four new homoleptic complexes of Co(II), Ni(II), Cu(II) and Zn(II) based on the tetra-p-methoxyphenyl-azadipyrromethene (ADPM) ligand in yields ranging from 89% to quantitative. Those complexes are put in relation with already known ADPM homoleptic complexes of the same M(II) series and related BF2+ chelates (Aza-BODIPY) for a better understanding of trends arising from substitution of the chelate and/or electron-donating effect of the p-methoxy substituents. This is achieved by the study of electrochemical behavior of the compounds and their photophysical properties. From a general point of view, the presence of the four p-methoxy substituents leads to an electrochemical decomposition of the derivatives based on that ADPM in oxidative conditions, along with a bathochromic shift of the optical properties. X-Ray structures for the tetra-p-methoxyphenyl-ADPM ligand and related Co(II) complex are also discussed. Hopefully, this study will provide useful insights to researchers on the substituents to install for stable ADPM derivatives in their quest for NIR chromophores utilizable for photovoltaic application. The second chapter report anion sensing properties toward F-, OAc- and H2PO4- of new neutral mononuclear and dinuclear Re(I) complexes based on a 5-substituted phenanthroline moiety bearing a thiourea hydrogen-bonding receptor. Those complexes were obtained in 81% and 60% yields, respectively. The effect of hydrogen-bonding versus deprotonation of the thiourea receptor upon addition of the anions was also evaluated by UV/vis and 1H NMR titration techniques. Observations made support the hypothesis that formation of the conjugated base of the receptor is favored. In addition, an X-ray structure of the Re(I) precursor complex is reported and the chirality of the mononuclear and dinuclear complexes is discussed. Achievement of a bimetallic complex by self-assembly paves the way for the preparation of light-harvesting molecular antennae utilizable in artificial photosynthesis systems.

Cette thèse s'inscrit dans le cadre du projet collaboratif MICROSOL, mené par Schneider Electric, et qui oeuvre pour le développement de micros centrales solaires thermodynamiques destinées à la production d'électricité en sites isolés (non connectés au réseau électrique) en exploitant l'énergie thermique du soleil. Le but de cette thèse étant le développement de lois de commande innovantes et efficaces pour la gestion de l'énergie de deux types de micros centrales solaires thermodynamiques : à base de moteur à cycle de Stirling et à base de machines à Cycle de Rankine Organique (ORC). Dans une première partie, nous considérons une centrale solaire thermodynamique à base de machine à cycle de Stirling hybridée à un supercondensateur comme moyen de stockage d'énergie tampon. Dans ce cadre, nous proposons une première loi de commande validée expérimentalement, associée au système de conversion d'énergie du moteur Stirling, qui dote le système de performances quasi optimales en termes de temps de réponse ce qui permet de réduire la taille du supercondensateur utilisé. Une deuxième loi de commande qui gère explicitement les contraintes du système tout en dotant ce dernier de performances optimales en terme de temps de réponse, est également proposée. Cette dernière loi de commande est en réalité plus qu'un simple contrôleur, elle constitue une méthodologie de contrôle applicable pour une famille de systèmes de conversion de l'énergie.Dans une deuxième partie, nous considérons une centrale solaire thermodynamique à base de machine à cycle de Rankine Organique (ORC) hybridée à un banc de batteries comme moyen de stockage d'énergie tampon. Etant donné que ce système fonctionne à vitesse de rotation fixe pour la génératrice asynchrone qui est connectée à un système de conversion d'énergie commercial, nous proposons une loi de commande prédictive qui agit sur la partie thermodynamique de ce système afin de le faire passer d'un point de fonctionnement à un autre, lors des appels de puissance des charges électriques, le plus rapidement possible (pour réduire le dimensionnement des batteries) tout en respectant les contraintes physiques du système. La loi de commande prédictive développée se base sur un modèle dynamique de la machine ORC identifié expérimentalement grâce à un algorithme d'identification nonlinéaire adéquat. / This Ph.D thesis was prepared in the scope of the MICROSOL project, ledby Schneider Electric, that aims at developing Off-grid solar thermodynamic micro powerplants exploiting the solar thermal energy. The aim of this thesis being the development of innovative and efficient control strategies for the energy management of two kinds of solar thermodynamic micro power plants: based on Stirling engine and based and Organic RankineCycle (ORC) machines.In a first part, we consider the Stirling based solar thermodynamic micro power planthybridized with a supercapacitor as an energy buffer. Within this framework, we propose afirst experimentally validated control strategy, associated to the energy conversion system ofthe Stirling engine, that endows the system with quasi optimal performances in term of settlingtime enabling the size reduction of the supercapacitor. A second control strategy that handlesexplicitly the system constraints while providing the system with optimal performances interm of settling time , is also proposed. This control strategy is in fact more than a simplecontroller, it is a control framework that holds for a family of energy conversion systems.In a second part, we consider the Organic Rankine Cycle (ORC) based thermodynamicmicro power plant hybridized with a battery bank as an energy buffer. Since this system worksat constant speed for the asynchronous generator electrically connected to a commercial energyconversion system, we propose a model predictive controller that acts on the thermodynamicpart of this system to move from an operating point to another, during the load power demandtransients, as fast as possible (to reduce the size of the battery banks) while respecting thephysical system constraints. The developed predictive controller is based upon a dynamicmodel, for the ORC power plant, identified experimentally thanks to an adequate nonlinearidentification algorithm.

In this work, thin and compact films of TiO2, Nb2O5 and WO3 nanoparticles were prepared to be used as contact/blocking layer in dye sensitized solar cells (DSCs). The films were produced by deposition of 30 bilayers of TiO2(ac)/TiO2(bas), TiO2(ac)/Nb2O5(bas) and TiO2(ac)/WO3(bas) using the layer-by-layer technique (LbL) from nanoparticle sols of TiO2 (pH = 2 and 10), Nb2O5 (pH = 10) and WO3 (pH 10) prepared by sol-gel method. The TiO2/TiO2 and TiO2/Nb2O5 underlayers resulted in an increase of 25% and 87% respectively, in the efficiency of DSCs when compared to those without the contact/blocking layers. The application of TiO2/WO3 films did not result in any improvement of DSC efficiency. Factors such as thickness, nanoparticles homogeneity, oxides concentration on the films and roughness directly influence on the efficiency of such films as contact/blocking layer. Field Emission Scanning Electron Microscopy (FESEM) and Atomic Force Microscopy (AFM) images, confirmed that all films are constituted by spherical nanoparticles with homogeneous diameters smaller than 20 nm, resulting on compact and low porous surfaces. This morphology ensures a physical barrier between the electrolyte and the conductive glass used as electrode in DSCs. The TiO2/TiO2 and TiO2/Nb2O5 films also exhibited higher roughness than the surface of the conductive glass without the bilayers, which increases the interaction with the mesoporous TiO2 film. The molar ratios of the species present on the films are controlled by the pH employed during deposition, and were determined by X- ray photoelectron spectroscopy (XPS). The Ti4+/Nb5+ and Ti4+/W6+ ratios were 1.6 and 19 respectively, which evidences a higher concentration of TiO2 nanoparticles on the films. For a better understanding of the role of the bilayers on the charge transfer processes, the substrates were analyzed by Electrochemical Impedance Spectroscopy (EIS). The electronic properties of the oxides also influence the efficiency of the LbL films as contact/blocking layers. Due to its higher band gap, Nb2O5 nanoparticles impose an electronic barrier to the electrons transfer from the conductive substrate to the electrolyte, additionally to the physical barrier. / Neste trabalho foram preparados filmes finos e compactos de óxidos nanoparticulados de TiO2, Nb2O5 e WO3 para a aplicação como camada de contato/bloqueio em células solares sensibilizadas por corante (DSCs). Os filmes foram produzidos pela deposição de 30 bicamadas de TiO2(ác)/TiO2(bás), TiO2(ác/Nb2O5(bás) e TiO2(ác)/WO3(bás) utilizando a técnica de automontagem (Layer-by-Layer ou LbL), a partir dos sóis nanoparticulados de TiO2 (pH = 2 e 10), Nb2O5 (pH = 10) e WO3 (pH = 10) sintetizados pelo método sol-gel. A presença das bicamadas de TiO2/TiO2, TiO2/Nb2O5 gerou aumentos relativos na eficiência das DSCs de 25% e 87% respectivamente, quando comparadas às DSCs sem as bicamadas. Já o filme de TiO2/WO3 não gerou nenhuma melhoria na eficiência das DSCs. Fatores como a espessura, homogeneidade das nanopartículas, concentração dos óxidos nos filmes e a rugosidade influenciam diretamente na eficiência dos filmes como camada de contato/bloqueio. Imagens de Microscopia Eletrônica de Varredura com Emissão de Campo (MEV-FEG) e Microscopia de Força Atômica (MFA) confirmaram que todos os filmes apresentaram nanopartículas esféricas com diâmetros homogêneos e menores que 20 nm, o que acarreta na formação de superfícies compactas e pouco porosas. Esta morfologia garante uma barreira física entre o eletrólito e a superfície do vidro condutor utilizado como eletrodo nas DSCs. Os filmes de TiO2/TiO2 e TiO2/Nb2O5 apresentaram também rugosidades maiores que a da superfície do vidro condutor sem as bicamadas, o que aumenta a interação entre com o filme de TiO2 mesoporoso. As razões molares das espécies presentes nos filmes são controladas pelo pH empregado durante as deposições, e foram determinadas por Espectroscopia de Fotoelétrons Excitados por raios-X (XPS). As razões Ti4+/Nb5+ e Ti4+/W6+ foram de 1,6 e 19 respectivamente, o que evidencia uma maior quantidade de nanopartículas de TiO2 nos filmes. Para melhor entender o papel das bicamadas nos processos de transferência de cargas, os substratos foram analisados por Espectroscopia de Impedância Eletroquímica (EIE). As propriedades eletrônicas dos óxidos também influenciam na eficiência dos filmes automontados como camada de contato/bloqueio. Devido ao seu maior valor de band gap, as nanopartículas de Nb2O5 impõem, além de uma barreira física, uma barreira eletrônica para a transferência dos elétrons do substrato condutor para o eletrólito. / Mestre em Química

Currently conventional sources like coal, petroleum and natural gas meet the energy requirements of developing and undeveloped countries. Over a period of time there is high risk of these energy sources getting depleted. Hence an alternate source of energy i.e. renewable energy is the need of the hour. The advantages of renewable energy like higher sustainability, lesser maintenance, low cost of operation, and minimal impact on the environment make the role of renewable energy sources significant. Out of the various renewable energy sources like solar energy, wind energy, hydropower, biogas, tidal and geothermal, usage of solar energy is gradually increasing. Among various solar energy sources, Photovoltaics has dominated over the past two decades since it is free clean energy and availability of abundant sunlight on earth. Over the past few decades, thin film solar cells (TFSC) have gained considerable interest as an economically feasible alternative to conventional silicon (Si) photovoltaic devices. TFSCs have the potential to be as efficient as Si solar cells both in terms of conversion efficiency as well as cost. The advantages of TFSC are that they are easy to prepare, lesser thickness, requires lesser materials, light weight, low cost and opto-electronic properties can be tuned by varying the process parameters. The present study is focused on the fabrication of AgInS2/ZnS heterojunction thin film solar cell. AgInS2 absorber layer is deposited using both vacuum (sputtering/sulfurization) and non-vacuum (ultrasonic spray pyrolysis) techniques. ZnS window layer is prepared using thermal evaporation technique, detailed experimental investigation has been conducted and the results have been reported in this work. The thesis is divided into 6 chapters. Chapter 1 gives general introduction about solar cells and working principle of solar cell. It also discusses thin film solar cell technology and its advantages. Layers of thin film solar cell structure, Significance of each layers and possible materials to be used are emphasized. A detailed overview of the available literature on both AgInS2 absorber layer and ZnS window layer has been presented. Based on the literature review, objectives of the present work are defined. Chapter 2 explains the theory and experimental details of deposition techniques used for the growth of AgInS2 and ZnS films. Details of characterization techniques to study film properties are described in detail. Chapter 3 presents a systematic study of AgInS2 thin films deposited by sulfurization of sputtered Ag-In metallic precursors. Initially, AgInS2 films are deposited by varying the substrate temperature and properties of as-deposited films are characterized. Structural, morphological, electrical and optical properties of AgInS2 films are explained. From these studies, samples with better properties at particular substrate temperature are optimized. By fixing the substrate temperature, deposition time of silver is varied by keeping other deposition conditions same and the properties of films are discussed. It was observed that deposition time of silver doesn’t have much impact on structural properties of AgInS2 films. However, opto-electric properties of AgInS2 films are enhanced. Based on characterization studies, deposition time of silver is optimized. Deposition time of indium is varied by keeping substrate temperature and silver deposition to optimized value. The properties of as-deposited films are discussed. Based on the above studies, the optimized p type films have a band gap of 1.64 eV, carrier concentration of 1013 ions/cm3 and Resistivity of order 103 Ω-cm. Chapter 4 presents a systematic study of AgInS2 thin films deposited by ultrasonic spray pyrolysis. AgInS2 films are deposited by varying the substrate temperature and properties of as deposited films are characterized. Structural, morphological, electrical and optical properties of AgInS2 films are explained. From these studies, samples with better properties at particular substrate temperature are optimized. By fixing the substrate temperature, concentration of silver molarity in the precursor solution is varied by keeping other deposition conditions same and the properties of films are discussed. Structural, optical and electrical properties of AgInS2 films are enhanced with the increase in silver concentration. Based on characterization studies, concentration of silver is optimized. Similarly concentration of indium molarity in the precursor solution is varied and the properties of as-deposited films are discussed. Finally, sulfur molarity in the precursor solution is varied and properties of films are discussed. It was observed that increasing sulfur after certain limit does not have any effect on the properties of the films. Based on the above studies, this method resulted in the films with resistivity of 103 Ω-cm and band gap of 1.64 eV. These films showed a carrier concentration of 1013 ions/cm3. Chapter 5 describes the growth of ZnS films using thermal evaporation technique. Influence of thickness on the properties of ZnS films is explained. Samples with good crystallinity, high transmission, and wider gap are selected for device fabrication. This p type layer showed a band gap of 3.52 eV. Solar cells have been fabricated using the AgInS2 films developed by both sputtering and ultrasonic spray pyrolysis techniques. A maximum cell efficiency of 0.92 percent has been achieved for the cell with 0.950 µm thick sputtered AgInS2 layer and thermally evaporated 42 nm thick ZnS layer. In comparison, the ultrasonic spray pyrolysis deposited films gave an efficiency of 0.54 percent. These values are comparable to those mentioned in a couple of reports earlier. Chapter 6 summarizes the conclusions drawn from the present investigations and scope of future work is suggested.

MENVSC / Department of Ecology and Resource Management