Semiconducting materials have emerged as the cornerstone of modern electronics owing to their extensive device applications. There is a continuous quest to find cost-effective and low-temperature compatible materials for future electronics. The recent reemergence of solution processable halide perovskites have taken the optoelectronics research to new paradigms. Apart from photovoltaics, the versatile characteristics of halide perovskites have resulted in a multitude of applications. This dissertation focuses on various properties and emerging applications particularly, photodetection and thermoelectrics of both hybrid and all-inorganic halide perovskites. It is important to understand the underlying properties of perovskites to further develop this class of materials. One of the major hurdles restricting the practical devices of perovskites is their sensitivity to moisture. A systematic investigation on the effect of humidity on hybrid perovskites revealed different degree of moisture uptake behaviour for micropatterns, films, and single crystals. Degradation pathways and processing limitations of hybrid perovskites are discussed which will aid in designing strategies to overcome these impediments for future large scale device integration. There is a recent surge of reports on doping hybrid perovskites to control its optoelectronic properties but in-depth understanding of these dopants and their ramifications remain unexplored. The effect of doping on the optoelectronic properties of hybrid perovskites is studied and a model is proposed for the observed behavior. Leveraging on the rapid growth of microcrystalline perovskite films, for the first time tunable bifacial perovskite photodetectors were fabricated, operating in both broadband and narrowband regimes. Furthermore, self-biased single crystalline photodetectors based on all-inorganic perovskite were developed with high on-off ratio and low dark current. Halide perovskites are emerging as a new class of materials for thermoelectric applications owing to their ultralow thermal conductivity and decent Seebeck coefficient. Here, halide perovskites are evaluated in terms of composition, stability, and performance tunability to understand their thermoelectric efficacy. Finally, as an alternative to Pb and Sn-based perovskites, a new hybrid was discovered with ultralow thermal conductivity and a general synthetic route to design such hybrids is proposed.

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Perovskite solar cells have attracted much attention both in research and industrial domains. An unprecedented progress in development of hybrid perovskite solar cells (HPSCs) has been seen in past few years. The power conversion efficiencies of HPSCs has been improved from 3.8% to 24.2% in less than a decade, rivaling that of silicon solar cells which currently dominate the solar cell market. Hybrid perovskite materials have exceptional opto-electrical properties and can be processed using cost-effective solution-based methods. In contrast, fabrication of silicon solar cells requires high-vacuum, high-temperature, and energy intensive processes. The combination of excellent opto-electrical properties and cost-effective manufacturing makes hybrid perovskite a winning candidate for solar cells. As power conversion efficiencies of HPSCs improves beyond that of the established solar cell technology and their long-term stability increases, one of the crucial hurdles in the path to commercialization remaining to be adequately addressed is the cost-effective scalable fabrication. Spin-coating is the prevailing method for fabrication of HPSCs in laboratories. However, this technique is limited to small areas and results in excessive material waste. Two types of scalable manufacturing methods have been successfully demonstrated to fabricate HPSCs: (i) meniscus-assisted coating such as doctor-blade coating and slot-die coating; and (ii) dispersed deposition based on the coalescence of individual droplets, such as inkjet printing and spray coating. Electrospray printing belongs to the second category with advantages of high material utilization rate and patterning capability along with the scalability and roll-to-roll compatibility. In Chapter 3 of this dissertation, electrospray printing process is described for manufacturing of HPSCs in ambient conditions below 150 C. All three functional layers were printed using electrospray printing including perovskite layer, electron transport layer, and hole transport layer. Strategies for successful electrospray printing of HPSCs include formulation of the precursor inks with solvents of low vapor pressures, judicial choice of droplet flight time, and tailoring the wetting property of the substrate to suppress coffee ring effects. Implementation of these strategies leads to pin-hole free, low surface roughness, and uniform perovskite layer, hole transport layer and electron transport layer. The power conversion efficiency of the all electrospray printed device reached up to 15.0%, which is among the highest to date for fully printed HPSCs. The most efficient HPSCs rely on gold and organic hole-transport materials (HTMs) for achieving high performance. Gold is also chosen for its high stability. Unfortunately, the high price of gold and high-vacuum along with high-temperature processing requirements for gold film is not suitable for the large-scale fabrication of HPSCs. Carbon is a cheap alternative electrode material which is inert to hybrid perovskite layer. Due to the ambipolar transport property of hybrid perovskite, perovskite itself can act as a hole conductor, and the extra hole transport layer can be left out. Carbon films prepared by doctor-blade coating method have been reported as the top electrode in HPSCs. The efficiencies of these devices suffer from the poor interface between the doctor-blade coated carbon and the underlying perovskite layer. In Chapter 4, electrospray printing was applied for the fabrication of carbon films and by optimizing the working distance during electrospray printing, the interface between carbon and the underlying perovskite layer was greatly improved compared to the doctor-blade coated carbon film. The resulting HPSCs based on the electrospray printed carbon electrode achieved higher efficiency than that based on doctor-blade method and remarkably, this performance is close to that of gold based devices. In Chapter 5, preliminary results are provided on the laser annealing of hybrid perovskite films to further advance their scalable manufacturing. All layers of HPSCs require thermal annealing at temperature over 150 C for about half an hour or longer. The time-consuming conventional thermal annealing complicates the fabrication process and is not suitable for continuous production. High temperature over150 C is also not compatible with flexible substrates such as PET. Laser annealing is a promising method for overcoming these issues. It has several other advantages including compatibility with continuous roll-to-roll printing, minimal influence on non-radiated surrounding area, and rapid processing. Laser annealing can be integrated with the electrospray process to realize the continuous fabrication of hybrid perovskite film. Rapid laser annealing process with optimized power density and scanning pattern is demonstrated here for annealing perovskite films. The resulting hybrid perovskite film is highly-crystalline and pin-hole free, similar to that obtained from conventional thermal annealing. / Doctor of Philosophy / Hybrid perovskite solar cell (HPSC) is a promising low-cost and high efficiency photovoltaic technology. One of the big challenges for it to be commercially competitive is scalable fabrication method. This dissertation focuses on developing electrospray printing technology for HPSCs. This is a scalable method with high material usage rate that naturally lead to large scale fabrication of HPSCs. Electrospray printing parameter space was systematically studied and optimized to synthesize high-quality perovskite films and other functional layers including hole transport layer and electron transport layer. All electrospray printed high-efficiency perovskite solar cell devices were successfully demonstrated under the ambient condition and low temperature. Another achievement of this thesis is the electrospray printing of carbon film to replace the costly gold electrode in perovskite solar cells. Laser annealing technique is demonstrated for HPSCs, which is compatible with continuous fabrication and integrates easily with electrospray printing.

There is a critical need for materials with very high dielectric constant to be integrated in the next generation of 64- and 256-Mb ULSI DRAMs. Materials in the Pb-based perovskite family have high relative permittivities and have consequently attracted a world wide attention. Cubic Lead Lanthanum Titanate (PLT) is one of the prime candidates in this respect and its structure and properties in the thin film form were investigated in the present study, for potential application in the ULSI DRAMs. Thin films of Lead Lanthanum Titanate corresponding to 28 atomic percentage of lanthanum were prepared by metalorganic decomposition (MOD) process. Solutions were prepared from lead acetate, lanthanum acetate and titanium iso-propoxide and thin films were then spin-coated from these solutions on PtlTilSi0₂/Si and sapphire substrates. The films were fabricated from two solutions of different compositions. The composition of the first solution was determined assuming that the incorporation of La³⁺ in the PbTi0₃ structure gives rise to A-site or Pb vacancies whereas for the composition of the other solution the creation of B-site or Ti vacancies was assumed. The effect of excess lead on the structure and the properties was also studied for 0% to 20% of excess PbO. The x-ray diffraction patterns of all films at room temperature indicated a cubic structure with lattice constant of 3.92 A. Optical and electrical measurements showed that the films made assuming B-site vacancies had better properties. In general, excess PbO was found to improve the optical as well as the electrical properties of films. However, in films with Bsite vacancies this improvement occurred only up to 5-10% of excess PbO, while higher PbO additions had a deleterious effect. The films had high resistivity, good relative permittivity, low loss, very low leakage current density, and high charge storage density. A type-B film with 10 % excess Pb had a permittivity of 1336 at 100 kHz. It also had a charge storage density at room temperature of around 16.1 μC/cm² at a field of 200 kV/cm and no sign of polarization loss or breakdown was observed up to 10¹⁰ cycles under the accelerated degradation breakdown test. / Master of Science

Vários compostos de fórmula AMO3 (A = Sr, Ca, Ba; M = Ru, Ti, Hf), com estrutura de perovskita foram sintetizados. Realizou-se uma análise estrutural dos compostos, usando difração de raios X, de fonte convencional e síncrotron, e difração de nêutrons em material policristalino. Para esta análise usaram-se dois dos programas mais reconhecidos internacionalmente para o método de Rietveld: DBWS e GSAS. Todas as estruturas analisadas foram classificadas segundo o sistema de inclinação dos octaedros de Glazer e representadas graficamente com o programa Atoms. A estrutura do SrHfO3 foi determinada por difração de nêutrons e raios X em material policristalino. Foi estudada a dependência da estrutura desses compostos com a temperatura e, com a composição, no caso das soluções sólidas SrTi1-xRuxO3 (O≤ x≤1). Duas transições estruturais de fase com a temperatura foram encontradas nos compostos SrRuO3 e SrHfO3. Nas soluções sólidas SrTi1-xRuO3 foi estudada a correlação da estrutura com as propriedades elétricas e com a estrutura eletrônica / Several compounds whose general formula was AMO3 (A = Sr, Ca, Ba; M = Ru, Ti, Hf) and which present the perovskite structure were synthesized. A structural analysis of the compounds by conventional and synchrotron X ray and neutron powder diffraction was performed. For this study was used the internationally accepted software for Rietveld analysis DBWS and GSAS. A11 of the structures analyzed were classified according to the octahedral tilt classification system of Glazer and represented with the program Atoms. The structure of SrHfO3 was determined by neutron and X ray powder diffraction. The dependence of the structure of severa1 compounds with temperature was studied. Two different structural phase transitions were found in the compounds SrRuO3 and SrHfO3. In the case of the solid solutions SrTi1-xRuxO3 (O≤ x ≤1) the dependence of the structure with the composition and the correlation with electric properties and the electronic structure was studied

Les recherches sur les nanocristaux semiconducteur (NCs) ont conduit à des résultats scientifiques fascinants, spécialement pour l'application en dispositifs optoelectroniques. Afin de répondre à certaines exigences comme des coûts mineurs, des gains d'efficacité, des composants respectueux de l'environnement, etc., des nouvelles méthodes sont explorées: dans les procédés en solution, dans l'ingénierie de bande et des niveaux d'énergie. En particulier, la méthode de synthèse peut influencer les propriétés optoélectroniques. Par conséquent, une meilleure compréhension des facteurs complexes pendant la synthèse entraînera une amélioration des performances.La microscopie électronique avancée fournit un moyen précis de recueillir des informations sur la morphologie, la structure cristalline et la composition chimique des matériaux avec une résolution spatiale au niveau atomique. La première partie de cette thèse traite de la synthèse et de la préparation des échantillons pour la microscopie électronique à transmission en haute résolution (HRTEM).La deuxième partie traite du mécanisme de croissance des NCs Cu2ZnSnS4 synthétisés par une méthode colloïdale. La morphologie et la stoechiométrie des intermédiaires de réaction extraits après différents intervalles de temps sont déterminés par HRTEM et analyse dispersive en énergie (EDS).Deux méthodes complémentaires, la diffraction par nanofaisceau d’électrons en précession (NPED) et la microscope électronique en transmission par balayage à haute résolution avec imagerie en champ sombre avec détecteur annulaire à grand angle (HRSTEM-HAADF) permettent une profonde caractérisation de la structure cristalline.En outre, la structure cristalline de NCs CsPbBr3 est résolue avec simulations de STEM-HAADF. Cet approche peut différencier entre structures cristallines cubiques et orthorhombiques, impossible avec techniques de diffraction traditionnelles. Enfin, l'influence des méthodes de synthèse sur la morphologie et sur la structure cristalline de NCs CuFeS2 pour applications dans le domaine de la thermoélectricité est analysée par HRTEM. / The investigations of semiconductor nanocrystals (NCs) led to fascinating scientific results in optoelectronic devices. In order to fulfill certain requirements, i.e. cheaper costs, higher efficiencies, environmental friendly components etc., new methods are explored in solution-processing, band gap and energy level engineering. Particularly, the method of synthesis can alter the optoelectronic properties. Therefore, a better understanding of the intricate factors during synthesis will lead to improved performances. Advanced electron microscopy provides a precise way to gather information about morphology, crystal structure and chemical composition of materials with a spatial resolution down to the atomic level. The first part of this thesis deals with the optimization of the synthesis and sample preparation for high resolution transmission electron microscopy (HRTEM).The second part deals with the growth mechanism of Cu2ZnSnS4 NCs synthesized by a colloidal method. The morphology and stoichiometry of the samples extracted after different time intervals are characterized by HRTEM and electron dispersion spectroscopy (EDS). Two complementary methods, Nanobeam Precession Electron Diffraction (NPED) and High Resolution Scanning Transmission Electron Microscopy by High Angle Annular Dark-Field Imaging (HRSTEM-HAADF), provide an in-depth crystal structure characterization.Moreover, the crystal structure of CsPbBr3 NCs is solved by probing STEM-HAADF simulations. This approach is able to differentiate cubic and orthorhombic crystal structures, which is otherwise impossible by diffraction techniques. Finally, the influence of synthesis methods on the morphology and crystal structure of CuFeS2 NCs is investigated by HRTEM for thermoelectric applications.

La thèse a pour but d’élaborer et d’étudier les potentialités des semi-conducteurs organiques, transporteurs de trous (HTMs) pour l’application photovoltaïque à l’aide de cellules solaires à base de pérovskite (PSCs). Plusieurs familles de molécules HTM ont été préparées et déposées en solution pour l’élaboration des cellules solaires. L'objectif principal étant d'étudier et d’apporter des informations sur la relation entre la structure moléculaire des nouveaux matériaux de transport de trous et les performances photovoltaïques obtenues, cette étude contribue à une meilleure compréhension fondamentale des propriétés requises des matériaux de transport de trous pour de meilleures performances photovoltaïques.La première étude concerne l’élaboration d’une molécule de type p à base de thieno [3,2-b] thiophène comme élément central avec des dérivés de dimethoxytriphenylamine comme donneurs d’électrons aux extrémités. Différentes conformations sont proposées et révèlent des performances photovoltaïques significativement différentes dans les dispositifs PSC. Notons par exemple, qu’une conformation de structure planaire favorisent la conjugaison avec des valeurs élevées de mobilités et conductivités obtenues.Dans la seconde étude, des molécules donneur-accepteurs à base de dérivés d’acridone 9 (10H) comme accepteur ont été élaborés. En y associant différents fragments donneurs d'électrons, on obtient des structures présentant des caractéristiques favorables à la fois pour de bons transferts de charge intramoléculaire (ICT) et des niveaux d’énergie HOMO-LUMO adaptés et favorisant l’injection des trous de la pérovskite vers l’électrode métallique via le HTM. Des études similaires ont été effectuées avec la thioxanthone.A partir d’un précurseur bon marché et d’une préparation aisée, la troisième étude a permis de synthétiser un dérivé de 9,9’-biacridone, molécule push-pull de type p révélant une structure tridimensionnelle, similaire à celle du Spiro-OMeTAD, molécule référence pour les PSCs.Enfin, la dernière étude concerne l’élaboration de molécules donneur-accepteur à base de thiéno [3,4-c] pyrrole-4,6-dione (TPD). La motivation de cette partie est le développement de la molécule à structure planaire améliorant l’empilement π-π dans la fabrication de dispositifs sans joints de grains. Ces molécules possèdent également un fort caractère ICT, une conjugaison π étendue sur toute la structure et une bonne solubilité ce qui en fait un candidat HTM idéal pour la réalisation d’un dispositif PSCs sans dopant. / The aim of the thesis is to develop and study the potential of organic hole transporting materials (HTMs) for photovoltaic applications using perovskite-based solar cells (PSCs). Several families of HTM molecules have been prepared and deposited in solution for the fabrication of solar cells. Since the main objective is to study and provide information on the relationship between the molecular structure of new hole transport materials and the photovoltaic performances obtained, this study contributes to a better fundamental understanding of the required properties of hole transport materials for better photovoltaic performance.The first study concerns the development of p-type molecules based on Thieno [3,2-b] thiophene as a central unit and π-linker with dimethoxytriphenylamine as end-capping electron donors. Different configurations are designed and revealed significantly different photovoltaic performances in the PSC devices. Remarkable, a planar structure with linear conjugation shows higher values of mobility and conductivity than others, thus it improved device performances.In the second study, donor-acceptor molecules based on 9(10H)Acridone derivatives as an acceptor were developed. By incorporating different electron-donating fragments, we obtain structures with favorable characteristics for both good intramolecular charge transfer (ICT) character and adequate HOMO-LUMO energy levels. Their energy levels are suitable for collecting and injecting the holes from perovskite to the metal electrode through the HTM. Similar studies have been done with Thioxanthone.Using a cheap precursor and facile preparation, the third study synthesized a 9.9'-biacridone derivative. These p-type molecules possess a three-dimensional structure which is similar to that of Spiro-OMeTAD, state-of-the-art molecule for PSCs.Finally, the last study focus on the development of donor-acceptor molecules based on thieno [3,4-c] pyrrole-4,6-dione (TPD). The objective is elaboration of the planar structure molecule which could be improved the π-π stacking effect in the device fabrication without grain boundaries. These molecules also own a strong ICT character, an extended π-conjugation on the whole structure and a good solubility which makes it an ideal candidate for the dopant-free HTM in PSCs.

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he extent of BiInO₃ substitution in the perovskite system xBiInO(₃)-(1 - x)PbTiO₃ and the corresponding raise in the transition temperature were investigated using thermal analysis, dielectric measurements, x-ray diffraction, and electron microscopy. Maximum tetragonal perovskite distortion (c/a = 1.082) was obtained for x = 0.20, with a corresponding Curie temperature of 582°C. Phase-pure tetragonal perovskite was obtained for x less than or equal to 0.25. Compound formation after calcining mixed oxide powders resulted in agglomerated cube-shaped tetragonal perovskite particles, which could be fired to 94.7% of theoretical density (TD). Niobium-modified BIPT ceramics with PT contents of 80% and 85% were found to possess significantly lower dielectric loss at elevated temperatures, making it possible to polarize the materials. Piezoelectric properties were measured for a 1.5 mol% Nb -0.15BI-0.85PT composition with a transition temperature of 542°C; the longitudinal piezoelectric coefficient and coercive field were found to be 60 pC/N and 125 kV/cm, respectively. Compositions of xBiLaO₃-(1 − x)PbTiO₃ over the range 0 < x < 0.225 were calcined and sintered. Dielectric constant with temperature and differential scanning calorimetry measurements were in excellent agreement with respect to a Curie-like tetragonal to cubic transformations starting at 495°C for pure PbTiO₃, shifting to lower temperatures with increasing x. For compositions of x > 0.05, a second higher-temperature (∼600°C) endotherm, and matching dielectric anomaly, were consistently observed, for which there were no structural changes indicated by hot-stage x-ray diffraction. This transformation was interpreted to be similar to a Curie transformation in relaxor ferroelectrics in which localized segregation of B-site cations (below the resolution limit of x-ray diffraction) facilitated ferroelectric behavior.