Rozprawy doktorskie na temat „Perovskite thin films”

>Magister Scientiae - MSc
Organic-inorganic lead-based perovskite has exhibited great performance in the past few years. However, the lead (Pb) embedded in those compounds is a significant drawback to further progress, due to its environmental toxicity. As an alternative, tin (Sn) based-perovskites have demonstrated promising results in terms of electrical and optical properties for photovoltaic devices, but the oxidation of tin ion- from stannous ion (Sn2+) to stannic ion (Sn4+) presents a problem in terms of performance and stability when exposed to ambient conditions. A more feasible approach may be in a Pb-Sn binary metal perovskite in pursuit of efficient, stable perovskite solar cells (PSCs) with reduced Pb-content, as compared to pure Pb- or Sn-based PSCs. Here, we report on the deposition of a Pb-Sn binary perovskite by sequential chemical vapor deposition.

>Magister Scientiae - MSc
Tin dioxide (SnO2) thin films are a worthy candidate for an electron transport layer (ETL) in perovskite solar cells, due to its suitable energy level, high electron mobility of 240 cm2 v-1 s- 1, desirable band gap of 3.6 - 4.0 eV, and ultimately proves to be suited for a low temperature thermal oxidation technique for ETL production. A variety of methods are available to prepare SnO2 thin films such as spin and dip coating and chemical bath deposition. However, the customary solid-state method, which incorporates thermal decomposition and oxidation of a metallic Sn precursor compound in an oxygen abundant atmosphere prevails to be low in cost, is repeatable and allows for large-scale processing.

Intensive research interests in condensed matter physics have been focused at the strongly correlated electron systems. Most of the efforts were devoted in hole-doped manganites with a double exchange interaction between Mn3+/Mn4+. Recently, tetravalent ions substitution has also stimuli much attention as a supplement for the hole-doping. Such electron-doped manganites may be of great potential for the development of all-manganites devices. Manganites are extremely sensitive to external disturbances, such as magnetic fields, electric fields, currents, mechanical strain, and photo illumination, etc. These extraordinary properties make manganites promising for practical applications. In this thesis, the field modulation on physical properties in electron/hole-doped manganites films and heterojunctions were investigated. The effects of tetravalent hafnium doping on the structural, transport, and magnetic properties of polycrystalline La1-xHfxMnO3(LHMO) (0.05 ≤x ≤0.3) were studied systematically. A phase diagram was obtained for the first time through magnetization and resistance measurements in a broad temperature range. An abnormal enhancement of magnetization was observed at about 42 K. It was further confirmed that the second magnetic phase MnO2in LHMO gives rise to such a phenomenon. The dynamic magnetic properties of LHMO, such as relaxation and aging processes, were studied, demonstrating a spin-glass state at low temperature accompanied by a ferromagnetic phase. Heterojunctions composed of n-type SrTiO3-δand p-type GaAs exhibited excellent rectifying behavior from 40K to room temperature. The photocarrier injection effect and a colossal photo-resistance were observed. Strong dependences on both temperature and bias voltage were found as well, which might be under stood by considering the band structure of the formed p-njunction. By employing an ultrathin SrTiO3buffer layer,La0.8Ca0.2MnO3films could be epitaxially grown on GaAs substrates. The heterostructures exhibit good rectifying behavior with a paramagnetic-ferromagnetic transition at ~200K. The variation of diffusion voltage with temperature in these heterostructures could be explained by the effects of the Hund’s rule coupling between the La0.8Ca0.2MnO3and the buffer layer. The effects of the strain induced by ferroelectric poling on the magnetic and electric properties have been investigated by using 0.67Pb(Mg1/3Nb2/3)O3-0.33PbTiO3(PMN-PT) substrates. The polarization of the PMN-PT crystal reduces the biaxial tensile strain in the formed La0.9Hf0.1MnO3layer.It results in a significant decrease in resistance and an enhancement of the phase transition temperature as well as the magnetization. The impact of the lattice strain on the charge/orbital ordering state was also been studied. The modification of charge/orbital ordering phase by the electric fields and ferroelectric polarization suggested that the unstable states in the manganites are sensitive to the strain. Heterojunctions of La1-xHfxMnO3/Nb:SrTiO3 were fabricated and investigated under different fields (electric, magnetic and optic). These heterojunctions exhibited excellent rectifying behavior in a wide temperature range. Their properties could be significantly modulated by magnetic fields. Prominent photovoltaic effect was also observed in the formed junctions.
published_or_final_version
Physics
Doctoral
Doctor of Philosophy

El desenvolupament de nous dispositius, cada cop més complexes, que s’adeqüin a les necessitats del mercat s’està convertint en una tasca cada cop més complicada deguda a la gairebé completa explotació de les propietats ofertes pels materials actuals. No obstant, és possible desenvolupar dispositius que ofereixin noves funcionalitats a través de la fabricació d’heteroestructures epitaxials (a l’escala nano-mètrica) compostes per diferents materials, on les propietats de cadascun dels compostos emprats són alterades degut a la seva interacció mútua. Quan aquestes estructures estan formades per òxids del tipus “perovskita”, existeix una forta interacció entre els diferents graus de llibertat dels electrons (xarxa cristal·lina, espín, òrbita i càrrega) donant lloc a un gran ventall de propietats físiques fascinants, que, a més, poden ser modificades a mida mitjançant la subtil alteració de les seves propietats estructurals a través de la tensions. Per tal d’entendre els fenòmens físics que donen lloc a aquest tipus d’efectes, és necessari conèixer l’estructura real dels defectes i/o distorsions que apareixen en aquestes estructures. Per aquesta raó, és indispensable l’ús de noves tècniques de caracterització capaces d’analitzar en l’espai real i amb resolució atòmica aquests sistemes. El desenvolupament de la tècnica de la microscòpia electrònica de transmissió d’escaneig corregida d’aberracions, combinada amb la espectroscòpia EELS (STEM-EELS), va significar un avanç notable ja que aquesta tècnica permet la observació directe d’estructures complexes i no periòdiques (així com defectes o interfases) en l’espai real i amb resolució subatòmica, sense la necessitat d’emprar simulacions numèriques. En aquest treball, s’aborden tres casos paradigmàtics de distorsions estructurals derivades de les tensions en capes fines epitaxials d’òxids tipus perovskita. En primer lloc, s’ investiga la forta interacció entre la microestructura, els tipus de defectes i les propietats superconductores de les capes fines de YBa2Cu3O7 del tipus nanocompost, on nanopartícules orientades aleatòriament resten atrapades dins de la pròpia matriu del YBCO. A més, s’ estudia en detall totes les distorsions que apareixen al voltant d’un dels defectes més comuns observats en aquest tipus de capes, que també tenen una influencia rellevant en les seves propietats superconductores. En segon lloc, s’ estudien els mecanismes estructurals que ajuden en l’acomodació de la tensió epitaxial, tan compressiva con expansiva, en les capes fines de LaNiO3 (LNO) i NdNiO3 (NNO), crescudes sobre monocristalls de LAO i LSAT, respectivament. S’observa la formació de dos tipus diferents de defectes en funció del compostos emprats, tant en la capa com en el substrat. Les propietats de transport elèctric de les capes són també investigades per tal de correlacionar els defectes generats i les propietats macroscòpiques de les capes. Finalment s’ investiguen els efectes de disminuir el gruix de les capes de La0.7Sr0.3MnO3 fins a l’ordre d’uns pocs nanòmetres. S’observa l’aparició d’una transició des d’un estat ferromagnètic i metàl·lic cap a un altre ferromagnètic i aïllant quan el gruix de les capes és reduït per sota d’un gruix crític, fet que contradiu el mecanisme de transport elèctric esperat en aquest compost: el conegut com a intercanvi doble o “double-exchange mechanism”. S’aporta una nova visió d’aquest fenomen a través de la caracterització de les modificacions estructurals que tenen lloc en aquestes capes, que apareixen degut a la tensió epitaxial i al confinament espacial. Es creu que les propietats estructurals mostrades poden ajudar en l’entesa de les alteracions de les propietats físiques observades en les capes de LSMO quan aquestes són reduïdes a uns pocs nanòmetres.
The continuous development of novel and complex devices for fulfilling the market demands is becoming more complex over time because of the wholly exploitation of the available bulk materials. One possibility to accomplish novel devices possessing new functionalities is by engineering epitaxial heterostrucutres, in the nanometric scale, where the properties of the used compounds can be modified because of their mutual interaction. When these heterostructures are made of perovskite oxides, the strong interplay between the lattice, spin, orbit and charge degrees of freedom lead to a huge range of fascinating properties that can be tailored by the subtle structural modifications induced by strains. In order to understand the underlying physics behind these phenomena, it is crucial to know the real structure of the emerging lattice defects or distortions within these kind of structures. For this reason, new techniques capable of analyzing these systems in the real space with atomic resolution are required. The development of the aberration-corrected scanning transmission electron microscopy, combined with the electron energy loss spectroscopy, technique (STEM-EELS) marked a notable breakthrough as it permits to directly see, without the need of simulations, the real structure of complex non-periodical structures, such as defects or interfaces, in real space and with sub-atomic resolution. In this work, we address three paradigmatic examples of strain-driven structural distortions appearing in one of the most studied family of functional oxides materials, this is, the case of perovskite oxides. First, we investigate the strong interplay between the microstructure, the defect landscape and the superconducting properties of YBa2Cu3O7 nanocomposite films, where randomly oriented nanoparticles are trapped within the YBCO host matrix. Besides, we analyze in detail all the emerging distortions around one of the most common defect found in YBCO nanocomposite films, which will also ultimately impinge on its superconducting properties. Second, we study in detail the structural mechanisms that help on the accommodation of the epitaxial strain, either compressive or tensile, in LaNiO3 (LNO) and NdNiO3 (NNO) thin films grown onto LAO and LSAT single crystal substrates, respectively. Two different kind of defects are identified in the studied heterostructures, which are observed to appear depending on the used compound and substrate. The electrical transport properties are also under investigation in order to find out the implications of the generated defect landscapes in the macroscopic properties of the films. Finally, we investigate the effect of reducing the film thickness of La0.7Sr0.3MnO3 thin films down to few nanometers. A transition from a ferromagnetic-metallic to a ferromagnetic-insulating phase is identified when films are reduced below a critical thickness, which contradicts the electrical transport mechanism expected for this compound. We provide new insights on the structural modifications generated by the epitaxial strain and the spatial confinement effects in these ultrathin films, which might help to understand the observed modifications on the LSMO physical properties.

>Magister Scientiae - MSc
Perovskite solar cells have gained tremendous attention within the past decade, due to its rapid improvement in power conversion e ciency (PCE), with the current record cell at 25%. The aim of this study is to create a repeatable and scalable chemical vapour deposition technique that can be used to construct perovskite solar cells with a high PCE while maintaining long-term stability. The technique requires the formation of a uniform and compact lead halide layer, either PbI2 or PbCl2 that is sequentially converted into the perovskite structure with the exposure of Methylammonium iodide (MAI) vapour. The use of CVD with a 5 cm diameter quartz tube was successfully used to deposit uniform thin lms of both PbI2 and PbCl2 over an area of 6 cm2 with a thickness deviation of 5%. Thickness control was obtained by varying the amount of source material which allows for repeatable control within 5% error, without the need for a crystal thickness monitor.

Les pérovskites hybrides célèbrent cette année leurs 10e anniversaire dans le domaine du photovoltaïque. En plus de la progression inégalée des rendements des cellules solaires, les pérovskites ont des propriétés optoélectroniques ajustables et peuvent être fabriquées par des procédés bas coûts, ce qui en fait de sérieuses candidates pour les cellules solaires multijunctions. Le réseau cristallin caractéristique des pérovskites hybrides offre une certaine liberté, supportant l’introduction partielle de cations et d’ions halogénures multiples. L’ajustement de la composition d’un matériau pérovskite se traduit par un ajustement de ces propriétés électroniques dont notamment sa structure de bandes. En adaptant la composition il est possible d’obtenir un matériau pérovskite avec une bande interdite de 1,7 eV qui serait parfaitement adapté pour une cellule tandem à base de Silicium cristallin. Les films minces de pérovskites peuvent être fabriqués par une grande diversité de techniques de dépôt, à partir de précurseurs ‘bon marché’ (CH3NH3I et PbI2 par exemple), par des procédés à basse température. Même si la grande majorité des films de pérovskites sont obtenus par la méthode d’enduction centrifuge, celle-ci ne permet pas l’obtention de films homogènes, sur grandes surfaces et de façon répétable. Etant donné l’enjeu industriel qui attend les pérovskites et l’intérêt croissant pour les structures tandems Silicium/Pérovskite, les méthodes sans solvant semblent plus adaptées. Déjà très largement utilisé dans l’industrie des OLEDs, le procédé de coévaporation thermique semble constituer une solution commercialement viable. Publiée pour la première fois en 2013, la synthèse par coévaporation des pérovskites est pour le moment encore étudiée par peu de groupes, car nécessitant des équipements plus coûteux. La présente thèse vise à mettre en place et développer la technique de coévaporation pour la fabrication de films de pérovskites hybrides pour des applications en cellules solaires.Afin d’évaluer la faisabilité du procédé, nous avons commencé notre travail sur un réacteur de démonstration, ce qui nous a permis d’appréhender la réponse à la sublimation des deux précurseurs. Nous avons très vite identifié le comportement du sel organique CH3NH3I comme étant problématique car difficilement contrôlable (s’évaporant sous forme de « nuage »), comme nous l’avions lu dans la littérature. En six mois d’utilisation de ce réacteur, nous avons fabriqué des films de pérovskites ayant permis d’atteindre des rendements de 9% sur des cellules solaires, malheureusement avec une faible reproductibilité (que nous expliquons en partie par le caractère aléatoire de l’évaporation du composé organique CH3NH3I). Nous nous sommes trouvés dans l’incapacité de comprendre plus en profondeur le procédé à cause d’un manque de fonctionnalités de l’équipement. Grâce à ces différents retours d’expérience nous avons pu concevoir, en étroite collaboration avec l’équipementier, un réacteur semi-industriel dédié à la fabrication de films de perovskites par coévaporation. Suite à sa mise en place, nous nous somme focalisé sur la problématique de la reproductibilité dans nos expériences en essayant de diminuer l’impact du nuage organique. Bien que les efficacités atteintes en cellules solaires pour des films coévaporés fussent moindres que pour des films déposés par la technique classique d’enduction centrifuge, nous soupçonnions néanmoins une meilleure homogénéité des films obtenus par voie sèche. Nous avons ainsi intégré à cette thèse une étude comparative voie liquide/voie sèche par le biais d’une technique de spectromicroscopie rayons X en Synchrotron
Hybrid perovskites celebrate this year their 10-year anniversary in the photovoltaic field. Besides the unprecedented rise in solar cells efficiencies, perovskite materials have tunable optical properties and can be manufactured at low cost, making them very promising candidates for the high efficiency, multijunction solar cells strategy. Perovskite crystal structure offers a relative degree of freedom, allowing the partial integration of multiple cations and halide ions. This chemical composition tuning translates into a bandgap tuning. Through fine chemical engineering, the 1.7 eV requirement for a c-Si-based tandem device can be achieved. Perovskite thin films can be prepared by a large variety of deposition techniques, from low cost precursors (CH3NH3I and PbI2 for instance), through low-temperature processes. While most of the reported works on perovskite thin films are based on the basic wet-process spincoating technique, this latter hardly allows large scale, homogeneous and reproducible deposition. With the future challenge of industrialization and the increasing interest for the Silicon/Perovskite tandem approach, solvent-free methods appear more suitable. Already widely implemented in the OLED industry, coevaporation stands as a viable option for perovskites’ future. Reported for the first time in 2013, coevaporated perovskites are still scarcely studied compared to wet-based techniques, requiring more expensive set ups. In the present thesis, we implemented and developed the coevaporation process to fabricate perovskite thin films for solar cells applications.Starting off on a proof-of-concept reactor to assess the feasibility of the technique, we got accustomed to the perovskite precursors behaviour and identify very early on the organic precursor to be hardly manageable, as reported in the literature. In six months, we were nonetheless able to obtain nice perovskite films leading to 9% efficient photovoltaic devices, unfortunately with a poor reproducibility that we think to be partially due to the cloud vapour behaviour of CH3NH3I. We eventually found ourselves missing some features on the equipment, preventing us from accurately get a grasp on the process. From this feedback we then designed, hand in hand with the manufacturer, a dedicated semi-industrial equipment for perovskite coevaporation. Following its implementation, we then focused on establishing the reproducibility of the method, trying to mitigate the parasitic effect of the organic compound. Even though the efficiencies in solar cells were still slightly lower for coevaporated perovskites, with respect to classical spincoated ones, we expected the material homogeneity to be in favour of the vacuum-based process. We then eventually integrated to this thesis a comparative study between wet- and dry-processed perovskite films using a Synchrotron-based X-ray spectromicroscopy technique

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

The aim of this Phd is to investigate the properties of micro-cantilevers, containing BaTiO\(_3\) based capacitors on their top and verify if they can be used as energy harvesting devices. SrRuO\(_3\)/BaTiO\(_3\) systems behaving as high quality (i.e. with an impedance phase between -80° and -90°) capacitive structures, in the frequency range 6KHz - 50KHz and with a residual polarization equal to 2.5 µC/cm\(^2\) have been fabricated on 400 nm thick MgO sacrificial layer. These structures allow to design micro-cantilevers with a minimum resonance frequency of 6KHz. Two piezoelectric modes are generally used in energy harvesting devices, they are the 33 and the 31 piezoelectric mode. X-ray diffraction analysis shows that the polar axis of BaTiO\(_3\) is perpendicular to the surface of the film when this layer is grown on SrRuO\(_3\) and SrTiO\(_3\). This configuration fits the 31 energy harvesting mode. When BaTiO\(_3\) is grown on MgO the polar axis is parallel to the surface of the film so this configuration fits the33 energy harvesting mode. Micro-cantilevers employing YBa\(_2\)Cu\(_3\)O\(_7\) and MgO sacrificial layers have been fabricated with a technology developed for the fabrication of Nb/Au/YBa\(_2\)Cu\(_3\)O\(_7\) ramp type Josephson junctions.

Die Anpassung der Bandlücke und die Herstellung mittels lösungsbasierter Prozesse charakterisieren Metallhalogenid-Perowskite. Sie sind vielversprechend für die Anwendung in optoelektronischen Bauteilen, die die Abscheidung von hochwertigen Dünnschichten erfordern. Deren Qualität hängt stark vom Kristallisationsverhalten ab, welches durch die Komposition der Lösung bestimmt ist. Ziel dieser Arbeit ist es, Korrelationen im Präkursor-Prozess-Eigenschaftsraum von Metallhalogenid-Perowskit zu bewerten und Formierungsprozesse zu rationalisieren. Phasenreinheit, Morphologie und Absorptionseigenschaften zeichnen die Qualität der Perowskit-Dünnschichten aus. Die Optimierung der Herstellung von hochwertigen Filmen über einen breiten Bandlückenbereich wird zuerst beleuchtet. Die Rationalisierung der Formierungsprozesse erweist sich als fundamental, um reproduzierbare Präparationsroutinen für hochwertige Filme zu entwickeln. Anschließend wird ein optischer in-situ Aufbau zur Rationalisierung von Formierungsprozessen vorgestellt. Abhängig vom Halogenidverhältnis in der MAPb(IxBr1-x)3-Reihe werden verschiedene Formierungswege eingeschlagen. Während sich das reine Bromid direkt und Iodid reiche Perowskite über die intermediäre Solvatphase (MA)2(DMSO)2Pb3I8 bilden, bilden sich gemischte Halogenide zwischen 0.1 ≤ x ≤ 0.6 über beide Wege. Die Formierung über konkurrierende Wege erklärt die kompositorische Heterogenität der gemischten Halogenidproben. Zuletzt werden Formierungsprozesse von Bromid-Perowskiten rationalisiert und Abhängigkeiten der Kinetik von der Lösungskonzentration zeigen sich. Niedrige Konzentrationen führen zu einer beschleunigten Kristallisation und Schichtdickenabnahme des Nassfilms. Dieser Trend wird durch geringere Kolloidwechselwirkungen und niedriger koordinierte Blei-Bromid-Komplexe in verdünnten Lösungen erklärt. Die Korrelation im Präkursor-Prozess-Eigenschaftsraum hebt die Herstellung von Perowskiten aus chemischer Sicht zu einem nicht-trivialen Prozess.
Bandgap tunability by ion substitution and the fabrication due to solution-based processes characterize metal halide perovskites. They are promising for application in various thin-film opto-electronic devices, which require the deposition of high-quality thin-films. The quality strongly depends on the crystallization behavior predetermined by the precursors in solution. This thesis aims to evaluate correlations in the vast precursor-process-property space of metal halide perovskite and rationalizes formation processes. Phase purity, morphology, and absorption properties determine the perovskite thin-film quality. The first part focuses on optimizing the perovskite fabrication to obtain high-quality films over a wide bandgap range. From high-quality films, the exciton binding energy is determined. The rationalization of formation processes proves essential to design reproducible preparation routines for high-quality films. The second part presents an optical in-situ setup to rationalize perovskite formation processes. Different formation pathways are taken, depending on the halide ratio in the MAPb(IxBr1-x)3 series. While the pure bromide forms directly and iodide-rich perovskites form via the intermediate solvate phase (MA)2(DMSO)2Pb3I8, mixed halides between 0.1 ≤ x ≤ 0.6 form via both. Such a heterogeneous formation process via two competing pathways rationalizes the compositional heterogeneity of mixed halide samples. The third part focuses on rationalizing the formation process of pure bromide perovskites and reveals a dependency of the formation kinetics on the solution concentration. Lower concentrations lead to accelerated crystallization kinetics and increase wet-film thinning. Lower colloid interaction and lower coordinated lead-bromide complexes in diluted solutions explain this trend. The strong correlation in the precursor-process-property space raises the preparation of perovskites via spin-coating to a non-trivial process from a chemical point of view.

Perowskite und Perowskit-artige Materialien sind von großem Interesse, da sie eine Vielzahl von strukturellen und physikalischen Eigenschaften haben, welche die Möglichkeit bieten, sie für unterschiedliche Anwendungen einzusetzen. Die Methode der Liquid-Delivery Metal Organic Chemical Vapour Deposition (LD-MOCVD) wurde gewählt, da sie eine gute Kontrolle über die Zusammensetzung ternärer Oxide und eine hohe Homogenität der Filme ermöglicht. Darüber hinaus können mit dieser Methode Filme hergestellt werden, die aus Elementen bestehen, für welche nur feste Precursor oder welche mit niedrigem Dampfdruck zur Verfügung stehen. Ziel dieser Arbeit war es, mit Hilfe der LD-MOCVD Filme aus SrRuO3, Bi4Ti3O12 und (Na,Bi)4Ti3O12 abzuscheiden und den Einfluss der Wachstumsbedingungen auf die Eigenschaften der Filme zu untersuchen. Zusätzlich wurde die Wirkung der Verspannung, die durch die Gitterfehlanpassung zwischen Substrat und Film entsteht, auf die physikalischen Eigenschaften der Schichten untersucht. SrRuO3 Filme wurden auf gestuften SrTiO3(001), NdGaO3(110) und DyScO3(110) Substraten gewachsen, deren Oberflächenterminierung durch oberflächensensitive Proton-induzierte Auger-Elektronen-Spektroskopie (AES) bestimmt wurde. Die Substrate wurden unter verschiedenen Bedingungen durch Änderung der Temperdauer und -atmosphäre präpariert. Die systematische Untersuchung der Beziehung zwischen Verspannung und Curie-Temperatur von dünnen SrRuO3(100) Filmen erfolgte unter Verwendung von Substraten mit unterschiedlichen Gitterkonstanten. Die beobachtete Curie-Temperatur sank mit erhöhter kompressiver Verspannung und nahm mit erhöhter tensiler Verspannung zu. Um stöchiometrische und epitaktische Bi4Ti3O12(001) Filme zu wachsen, war aufgrund der Flüchtigkeit des Bismuts ein Bi Überschuss in der Precursor-Lösung notwendig. Die Substitution von Bi durch Na in Bi4Ti3O12 wurde zum ersten Mal in LD-MOCVD-Filmen erreicht.
Perovskites and perovskite-like materials are actually of great interest since they offer a wide range of structural and physical properties giving the opportunity to employ these materials for different applications. Liquid-Delivery Metal Organic Chemical Vapour deposition (LD-MOCVD) was chosen due to the easy composition control for ternary oxides, high uniformity and good conformal step coverage. Additionally, it allows growing the films, containing elements, for which only solid or low vapour pressure precursors, having mainly thermal stability problems over long heating periods, are available. The purpose of this work was to grow SrRuO3, Bi4Ti3O12 and (Na, Bi)4Ti3O12 films by LD-MOCVD and to investigate the influence of the deposition conditions on the properties of the films. Additionally, the effect of the strain due to the lattice mismatch between substrates and films on the physical properties of the films was also investigated. SrRuO3 films were grown on stepped SrTiO3(001), NdGaO3(110) and DyScO3(110) substrates, which were prepared under different conditions by changing the annealing time and atmosphere. The termination of the substrates was measured by surface sensitive proton-induced Auger Electron Spectroscopy (p-AES) technique. Another systematic study of the relation between epitaxial strain and Curie temperature of thin SrRuO3(100) films was performed by using substrates with different lattice constants. The observed Curie temperature decreased with compressive and increased with tensile strain. Thin films of Bi4Ti3O12 as well as (Na, Bi)4Ti3O12 were successfully deposited. In order to grow stoichiometric and epitaxial Bi4Ti3O12(001) films, Bi excess in the precursor solution was necessary, due to the volatility of Bi. Substitution of Bi with Na in Bi4Ti3O12 was achieved for the first time for the films deposited by LD-MOCVD.

Philosophiae Doctor - PhD
The organic-inorganic hybrid perovskites such as methyl ammonium lead iodide (MAPbI3) or mixed halide MAPbI3-xClx (x is usually very small) have emerged as an interesting class of semiconductor materials for their application in photovoltaic (PV) and other semiconducting devices. A fast rise in PCE of this material observed in just under a decade from 3.8% in 2009 to over 25.2% recently is highly unique compared to other established PV technologies such as c-Si, GaAs, and CdTe. The high efficiency of perovskites solar cells has been attributed to its excellent optical and electronic properties. Perovskites thin film solar cells are usually deposited via spin coating, vacuum thermal evaporation, and chemical vapour deposition (CVD).

Orientador: Francisco das Chagas Marques
Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin
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Resumo: Perovskitas híbridas orgânica-inorgânica tem sido objeto de intensa investigação devido as suas atrativas propriedades ópticas e eletrônicas, por exemplo, banda de energia proibida direta, alto coeficiente de absorção e transporte ambipolar de cargas. Tais propriedades possibilitaram a aplicação desse material em células solares e em diodos emissores de luz de forma eficiente. Assim, o desenvolvimento de novas rotas de síntese que permitam produzir materiais com as características adequadas para cada aplicação é de extrema importância para o desenvolvimento dessa área de pesquisa. Portanto, neste trabalho de doutoramento apresentaremos resultados sobre a síntese e caraterização de filmes e nanocristais de perovskita obtidos a partir de novas metologias, baseadas na conversão de filmes finos de sulfeto de chumbo (PbS) e iodeto de chumbo (PbI2) depositados por rf-sputtering e em pontos quânticos de PbS. Na primeira rota de síntese, filmes finos amorfos de PbS, depositados por sputtering, foram convertidos em filmes finos de PbI2 através do processo de iodação em temperatura ambiente. Esse procedimento resultou em uma completa mudança estrutural, conforme atestado pelos resultados de difração de raios-x. A conversão desses filmes de PbI2 em CH3NH3PbI3 foi realizada por meio da imersão dos mesmos em uma solução de iodeto de metilamônio (CH3NH3I). Na segunda rota de síntese, filmes finos de PbI2 foram diretamente depositados por sputtering. A conversão desses filmes em CH3NH3PbI3 também foi realizada através do mergulho dos mesmo em uma solução de CH3NH3I. Esses dois métodos, permitiram-nos sintetizar filmes finos de CH3NH3PbI3 com boas propriedades ópticas e estruturais e também com uma completa cobertura do substrato, sem evidências de fissuras ou buracos, conforme indicado por microscopia eletrônica de varredura. Essas metodologias têm o potencial de abrir caminho para a produção em larga escala de células solares de CH3NH3PbI3 reprodutíveis e com alta eficiência. Como terceira rota de síntese, nanocristais de perovskita foram sintetizados utilizando pontos quânticos de PbS como precursores. Esse procedimento foi realizado através da iodação dos pontos quânticos de PbS, o que produziu nanofios de PbI2 com comprimento da ordem de 5 ?m e diâmetro de aproximadamente 200 nm. Os nanofios de PbI2 foram então convertidos em nanocristais de perovskita através de seu mergulho em uma solução de CH3NH3I, o que resultou em nanocristais de perovskita com comprimento da ordem de 5 ?m e largura de 400 nm
Abstract: Organic-inorganic hybrid perovskite has been subject of intense investigation due to their attractive optical and electronic properties, e.g., direct bandgap, high absorption coefficient and ambipolar charge transport. Such properties allowed the application of this material in solar cells and light emitting diodes efficiently. Thus, the development of new synthesis routes that allow the production of materials with the appropriate characteristics for each application is extremely important for the development of this area of research. Therefore, in this PhD work we¿ll present results on the synthesis and characterization of perovskite films and nanocrystals obtained from new methodologies, which are based on thin films of lead sulphide (PbS) and lead iodide (PbI2) deposited by rf-sputtering and on quantum dots of PbS. In the first synthesis route, amorphous PbS thin films deposited by sputtering were converted to PbI2 thin films by the iodination process at room temperature. This procedure resulted in a complete structural change, as attested by XRD measurements. The PbI2 films were converted into CH3NH3PbI3 by immersing them in a solution of methylammonium iodide (CH3NH3I). The second route consisted in depositing directly films of PbI2 by sputtering. The conversion into CH3NH3PbI3 also was performed by immersing the films in a CH3NH3I solution. These two methods allowed us to synthesize CH3NH3PbI3 thin films with good optical and structural properties and with complete substrate coverage, without evidence of cracks or holes, as verified by scanning electron microscopy images. Such methodologies have the potential to pave the way for the large-scale production of reproducible and high efficiency CH3NH3PbI3 solar cells. The third route was devoted to produce perovskite nanocrystals using PbS quantum dots as precursors. This approach was performed through iodination of PbS quantum dots. This produced PbI2 nanowires of about 5 ?m in length and 200 nm in diameter. The conversion in perovskite nanocrystals was accomplished through dip of the PbI2 nanowires into a solution of CH3NH3I. This procedure generated perovskite nanocrystals of about 5 ?m in length and 400 nm in width
Doutorado
Física
Doutor em Ciências
165756/2014-4
CNPQ

Ferroelectric and antiferroelectric ultrathin films have attracted a lot of attention recently due to their remarkable properties and their potential to allow for device miniaturization in numerous applications. However, when the ferroelectric films are scaled down, it brings about an unavoidable depolarizing field. A partial surface charge compensation allows to control the residual depolarizing field and manipulate the properties of ultrathin ferroelectric films. In this dissertation we take advantage of atomistic first-principles-based simulations to expand our understanding of the role of the partial surface charge compensation in the properties of ferroelectric and antiferroelectric ultrathin films. The application of our computational methodology to study the effect of the partial surface charge compensation in ferroelectric ultrathin films led to the prediction that, depending on the quality of the surface charge compensation, ferroelectric thin films respond to an electric field in a qualitatively different manner. They can be tuned to behave like a linear dielectric, a ferroelectric or even an antiferroelectric. This effect was shown to exist in films with different mechanical boundary conditions and different crystal symmetries. There are a number of potential applications where such properties of ferroelectric thin films can be used. One of these potential applications is energy storage. We will show that, in the antiferroelectric regime, ferroelectric thin films exhibit drastic enhancement of energy storage density which is a desirable property. One of the most promising applications of ferroelectric ultrathin films that emerged only recently is the harvesting of the giant electrocaloric effect. Interestingly, despite numerous studies of the electrocaloric effect in ferroelectric thin films, it is presently unknown how a residual depolarizing field affects the electrocaloric properties of such films. Application of state-of-the-art computational methods to investigate the electrocaloric effect in ferroelectric films with partial surface charge compensation led to the prediction that the residual depolarizing field can perform a dual role in the electrocaloric effect in these films. When the depolarizing field creates competition between the monodomain and nanodomain states, we predict an enhancement of the electrocaloric effect due to the frustration that increases the entropy of the state and therefore the electrocaloric temperature change. On the other hand, when the depolarizing field leads to a formation of nanodomains, thin films either exhibit a small electrocaloric effect or lose their electrocaloric properties altogether to the irreversible nanodomain motion. When the residual depolarizing field is weak enough to permit the formation of monodomain phases, the electrocaloric effect is significantly reduced as compared to bulk. We believe that our findings could potentially reveal additional opportunities to optimize solid state cooling technology. While the electrocaloric effect has been a popular topic of interest in recent years [12], there still exists numerous gaps in the fundamental understanding of the effect. In particular, it is presently unknown whether the scaling laws, known to exist for magnetocaloric materials, can be applied to ferroelectric and antiferroelectric electrocalorics. We predict the existence of scaling laws for low-field electrocaloric temperature change in antiferroelectric and ferroelectric materials. With the help of first-principles-based simulations, we showed computationally that the scaling laws exist for antiferroelectric PbZrO3 along with ferroelectrics PbTiO3, BaTiO3 and KNbO3. Additional evidence of the scaling laws existence are provided using experimental data from the literature. Interestingly, our studies on ferroelectric films predicted the existence of antiferroelectric behavior in ultrathin films with partial surface charge compensation. One may wonder whether it is possible to stabilize the ferroelectric phase in antiferroelectric films and what role the surface charge screening would play in such a transition. Motivated to address these fundamental questions, we used computational experiments to study antiferroelectric ultrathin films with a residual depolarizing field. Our studies led to the following predictions. We found that PbZrO3 thin films exhibit the ferroelectric phase upon scaling down and under the condition of efficient surface charge compensation. We also found a strong competition between the antiferroelectric and ferroelectric phases for the thin films of the critical size associated with antiferroelectric-ferroelectric phase transition. This finding motivated us to study the electrocaloric effect in PbZrO3 thin films with antiferroelectric-ferroelectric phase competition. We found that high tunability of the phase transition by the electric field leads to a wide range of temperatures associated with a strong electrocaloric effect. In addition, we found that epitaxial strain provides further tunability to the electrocaloric properties. In summary, our studies led to a broader and deeper understanding of the abundantly many roles surface charge compensation plays in ultrathin ferroelectrics and antiferroelectrics.

Thesis (S.M.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2007.
Includes bibliographical references (leaves 145-156).
In this thesis, we discuss the motivation for integrated magneto-optical isolators and explain why the orthoferrite is such an attractive materials class for this purpose. We then derive from first physical principles the dependence of Faraday rotation, absorption, and certain figures of merit on the material's dielectric tensor elements. Next, we use pulsed laser deposition to grow thin films of BiFeO3 on MgO (001) and SrTiO3 (001) substrates. After optimizing growth conditions to obtain high quality films, we characterize the films' crystal structure with two-dimensional x-ray diffraction. We then examine the magnetic, optical, and magneto-optical properties of these films. We find that the highly textured films grown on SrTiO3 are monoclinic with an out-of-plane c-axis aligned with the (001) direction of the substrate and approximate pseudocubic lattice parameters of a = b = 4.04 A, c = 3.95 A, and 90° - [beta] = -0.88°. These films are weakly magnetic, with a magnetization of 1.2 emu/cm3 at an applied field of 10 kOe; highly absorptive, with an average absorption coefficient of 910 cm-1; and possess a low specific Faraday rotation of 320/cm at 1.8 kOe of applied field. As expected, we find that the magneto-optical figure of merit is negligible for this material due to its high absorption, which we attribute to a thin surface layer of phase separated bismuth and iron oxides caused by bismuth segregation during growth. We offer additional explanations for these values and show the first results of newer, more promising work with mixed cation perovskite.
by Alexander R. Taussig.
S.M.

Thesis: Ph. D., Massachusetts Institute of Technology, Department of Mechanical Engineering, 2014.
Cataloged from PDF version of thesis.
Includes bibliographical references.
Discovering highly active and stable catalysts for electrochemical energy conversion and storage is essential to envision a new generation of renewable energy applications. Mixed ionic and electronic conductors (MIECs) such as Lai.xSrxCoO₃-[delta] (LSC₁₁₃) and Lai-xSrxCo1-yFeyO3-[delta] (LSCF₁₁₃) are currently utilized for applications including oxygen permeation membranes and solid oxide fuel cells (SOFCs), but alternative materials with higher catalytic activity and stability are required for intermediate temperature (500 - 700 °C) oxide electrocatalysts. In this thesis, two promising strategies, 1) Ruddlesden-Popper (RP) oxides and 2) surface decoration on the MIEC oxides are proposed to design highly active oxide materials and improve the fundamental understanding of the oxygen electrocatalysis at intermediate temperature. The oxygen surface exchange kinetics of a-axis-oriented La2NiO4+[delta] (LNO) thin films increases with decreasing film thickness. Increasing volumetric strains in the LNO films at elevated temperatures are correlated with increasing surface exchange kinetics and decreasing film thickness. Volumetric strains may alter the formation energy of interstitial oxygen and influence on the surface oxygen exchange kinetics of the LNO films. The effect of strontium (Sr) substitution on the oxygen electrocatalysis of RP oxides is also investigated using La2-xSrxNiO4+/-[delta] (LSNO, 0.0 by Dongkyu Lee.
Ph. D.

This research presents thin film deposition and characterization of metal oxides using industrially viable Physical Vapour Deposition (PVD) techniques. The research examines low temperature processed electron and hole transport metal oxides for high performance and stable perovskite solar cells. The physical, chemical, optical and electronic properties of the films were investigated and their device performance has been evaluated. The performance of the device improved and the materials cost reduced by replacing the expansive organic materials with more stable inorganic metal oxides.

Control of growth and surface morphology of perovskite oxide thin films is essential for future electronic devices based on such materials. Uncommon crystallographic orientations, like (111), are particularly interesting in order to control domain formations, but have been shown to grow in a rough manner, because of their polar surfaces. This work aims to elucidate the growth mode of (111) oriented systems, to enable smooth surface structured films. We have investigated the growth of La_{0.7}Sr_{0.3}MnO_3 (LSMO) thin films by pulsed laser deposition (PLD) on (111)oriented SrTiO_3 (STO), characterized by AFM and x-ray diffraction. Substrate surface preparation has been optimized to yield uniform straight step-and-terrace surface structures, as well as the ability to tune the surface structure by different surface preparations. The film surface structure is observed to duplicate the substrate surface; hence, control of the film surface structure is obtained. A detailed description of the growth mode, from thin films of only a few mono layers to thick films of 70nm is presented. The growth mode is complex showing in principle an unstable growth. For the first 20 mono layers (2nm) a roughening transition from step-flow to layer-by-layer is observed. At higher thicknesses a second transition is seen, where the surface breaks up to a 3D surface structure. The critical thickness of the second transition is delayed by reducing the deposition temperature, as expected for strained surfaces, resulting in epitaxial thin films of step-and-terraces structure at least 70nm thick. The crystallinity of the films has been confirmed by XRD measurements. The transition to 3D growth is shown to initiate at the step-edges, and stabilizes with step-bunched steps. A speculative discussion of step-induced strain, and consequently the surface breakup is presented. Furthermore magnetic measurements by VSM in room temperature are presented. The saturation magnetic moment is measured to be $330 emu/cm^3$ at room temperature, which is 100 emu/cm3 larger than other reported values for LSMO/STO(111). The improved understanding of substrate preparation and growth mode in LSMO/STO(111) is important for further work on oxide interfaces, as we believe these results can be expanded to other (111) systems. The magnetic measurements give a preliminary indication that high quality films are necessary to exploit the full potential of these materials.

Neste trabalho, foram desenvolvidos filmes finos de composição SrTi1-xFexO3 (0,00≤ x ≤0,150) nanoestruturados visando sua aplicação como sensor de gás ozônio. Os filmes finos foram depositados através da técnica de deposição por feixe de elétrons (EBD) cujo alvo utilizado foram pastilhas obtidas a partir do pó cristalino SrTi1-xFexO3 (0,00≤ x ≤0,150) sintetizadas através do método dos precursores poliméricos. Foi observado a partir das analises termogravimétrica e térmica diferencial que a incorporação de ferro no sistema diminui a temperatura de queima do pó precursor, sugerindo que o ferro atua como catalisador na cadeia polimérica. Os filmes depositados por DFE apresentam-se no estado amorfo sendo necessário um tratamento térmico ex-situ para que a fase cristalina desejada seja obtida. Todos os filmes apresentaram uma boa aderência aos diferentes tipos de substratos utilizados. Após o processo de cristalização, os filmes depositados sobre diferentes substratos foram caracterizados através das técnicas de difração de raios-X, espectroscopia UV-Vis e microscopia de força atômica (MFA). Foi observado que um aumento na temperatura de tratamento térmico dos filmes leva a um aumento no grau de cristalização e a uma diminuição no valor da energia de gap, calculada a partir dos espectros UV-VIS. A analise por MFA mostrou que a mudança do tipo de substrato utilizado não influencia as propriedades estruturais e microestruturais dos filmes. Através da realização de medidas de resistência elétrica, observou-se que os filmes cristalinos submetidos a um tratamento térmico ex-situ a 500oC por 4 horas apresentaram uma boa sensibilidade ao gás ozônio sendo possível detectar a presença de até 75 ppb de ozônio.
In this study, nanostructured thin films of SrTi1-xFexO3 (0.00 ≤ x ≤ 0.150) compositions were prepared looking their application as ozone gas sensor. The thin films were deposited using the technique of electron beam deposition (EBD) whose targets were obtained from polycrystalline SrTi1-xFexO3 (0.00 ≤ x ≤ 0.150) powders synthesized by the polymeric precursor method. It was observed from the thermogravimetric and differential thermal analysis that the incorporation of iron in the system decreases the calcination temperature of the precursor powders, suggesting that the iron acts as a catalyst in the polymer chain. The as obtained films deposited by EBD present an amorphous state being necessary a ex-situ heat treatment to obtain the desired crystalline phase. All films showed good adhesion to different substrates. After the crystallization process, the films deposited on different substrates were characterized through X-ray diffraction, UV-Vis spectroscopy and atomic force microscopy (AFM) trechniques. It was observed that an increase in the annealing temperature of the film results in an increase in the degree of crystallization and a decrease in the value of band gap energy, which was calculated from the UV-VIS spectra. The AFM analysis showed that changing the type of substrate does not influence the structural properties and microstructure of the films. By carrying out measurements of electrical resistance, it was observed that the crystalline films subjected to a ex-situ heat treatment at 500oC for 4 hours showed a good sensitivity to the ozone gas being possible to detect the presence of up to 75 ppb ozone.

[ES] El objetivo principal de esta tesis es contribuir al avance de nuevas técnicas de elaboración con bajo coste, utilizando materiales tipo de cobre, indio, galio y selenio CIGS y Perovskita para aplicaciones en energía solar fotovoltaica. CIGS parecen ser adecuadas ya que son de bajo costo de producción y se han reportado eficiencias de conversión del 23,35%. Por otro lado, las perovskitas híbridas de haluros de plomo orgánicos-inorgánicos han aparecido como nuevos materiales excepcionales para celdas solares, especialmente porque la eficiencia de las celdas solares basadas en perovskita ha aumentado del 3.8% al 22.7% en menos de un lustro. Este trabajo se ha dedicado a experimentar sobre la elaboración y caracterización de CIGS y los perovskitas de metilamonio de yoduro de plomo de (MAPbI3) y formamidinio de yoduro de plomo (FAPbI3), que se utilizo tanto en la aplicación a las células solares de perovskitas y en las células Tándem CIGS-perovskita. Las películas se caracterizaron por difracción de rayos X, espectroscopía Raman, microscopía electrónica de barrido, análisis de espectroscopía de energía dispersiva, microscopía de fuerza atómica, transmisión electrónica microscopía, fotoluminiscencia y espectroscopia UV-Vis. En las capas de CIGS depositadas por electrodeposición se investigó el efecto de diferentes parámetros, También investigamos en detalle el efecto del contacto posterior en las propiedades estructurales y ópticas de CIGS. Constatamos que el tipo de contacto posterior tiene un efecto significativo en el rendimiento posterior de las películas delgadas CIGS. Además, estudiamos la técnica de espray pirólisis para producir películas CIGS. Se estudió el proceso de recocido, que es el factor clave para mejorar el rendimiento de las células solares. Se elaboraron diferentes películas delgadas constituidas de nuestro dispositivo CdZnS/CdS/CIGS/Mo eso utilizó una capa conductora transparente de CdZnS para minimizar la alineación de la interfaz. Por otro lado, se analizó el proceso de cristalización y la estabilidad de las capas MAPbI3. Las capas de MAPbI3 se trataron añadiendo antisolvente a diferentes velocidades. Durante el tratamiento se producen intercambios complejos que influencian muchas propiedades fisicoquímicas. Se investigaron las propiedades ópticas y eléctricas de las películas de MAPbI3. Para mejorar la estabilidad de MAPbI3, se incorporó tetrabutilamonio (TBA), observando una mejora en la formación de la estructura perovskita que crece en la dirección preferente (110). La fase cristalina de MAPbI3 dopada con TBA presenta mejor cristalinidad, gran tamaño de grano, morfología superficial sin poros lo que es adecuado para la fabricación de dispositivos optoelectrónicas con mayor rendimiento. Además, hemos identificado el impacto de TBA en las propiedades foto físicas de MAPbI3. En las muestras de TBA:MAPbI3 aumenta la intensidad de la fotoluminiscencia al reducir la densidad de los estados de trampa y la absorción óptica muestra un cambio significativo hacia longitudes de onda más largas y la banda prohibida óptica varió de 1.8 a 1.52 eV. Finalmente, las muestras dopadas con 5% TBA mejoraron su estabilidad y se encontró que después de 15 días la estabilidad permanecía excelente en una humedad de ~ 60%. Por otra parte, investigamos el efecto de guanidinio (GA) sobre las propiedades estructurales y ópticas de FAPbI3. La relación entre la fase a de perovskita deseable y la fase indeseable y se ha estudiado en función del contenido de GA. Se comprobó que el dopaje con GA es eficaz en el control de la relación de fases a/y y luego en la estabilización de la fase a. Los resultados muestran que añadiendo una cantidad adecuada del 10% GA conduce a una mejora de película de perovskita que se evidencia en la homogeneidad de la fase a estable, granos de mayor tamaño y capas libres de poros. Además, 10% GA:FaPbI3 demostraron una excelente estabilidad después de ser envejecidas durante 15 días en un ambiente con humedad relativa del 60%.
[EN] The thesis work presented is part of the work in the Laboratory of New Materials for Photovoltaic Energy in the main target to use low cost techniques for elaboration of Perovskite and Copper, indium, gallium, and selenium CIGS materials for photovoltaic application. Organic-inorganic lead halides perovskites have currently and exceptionally appeared as new materials for low cost thin film solar cells specially that the efficiency of perovskite based solar cell have jumped from 3.8% to 22.7% in short time.in other hand, CIGS solar cells record 23.35% efficiency and still can be boosted. Here, we report the elaboration and characterization of CIGS as well as methylammonium lead iodide perovskites MAPbI3 and formamidinuim iodide lead iodide perovskites FAPbI3 absorbers for perovskite-based solar cells and Tandem Perovskites/ CIGS. The thin films prepared were characterized by X-ray diffraction (XRD), Raman spectroscopy (RS), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) analysis, atomic force microscopy (AFM), transmission electron microscopy (TEM), Photoluminescence analysis (PL) and UV-Vis spectroscopy. The first stage was devoted for the effect of different parameters on the growth of CIGS by electrodeposition and we investigate the impact of different back contact in structural and optical proprieties. In a second stage, we report the growth of CIGS films by spray pyrolysis, we studied the effect of experimental parameter also the annealing process which is the key factor for improving the performance of solar cells,subsequently we elaborated different films constituted CdZnS/CdS/CIGS/Mo solar cells, the approach is to change the toxic ZnO by using a transparent, conductive CdZnS layer. In other hand, MAPbI3 film was investigated in order to optimize the chemical composition and to study the crystallization process also to get sight about the stability of perovskite materials to meet the requirement of their application as an active layer in perovskite solar cell. For this purpose. the MAPbI3 film surface was treated by adding diethyl ether antisolvent with different rates. during the treatment complex exchanges are appearing at the same time under the influence of quite a lot of physicochemical properties. A whole understanding of this topic is critically important for improving solar cell performance. MAPbI3 doped by the tetrabutylammonium TBA is boosting the formation of perovskite structure, leading to a higher orientation along the (110) and shows better crystallinity, large grain size, pinhole-free, which is suitable for the manufacturing of the optoelectronic devices with higher performance. Also, we have identified the impact of TBA in the photo-physical properties, we have noticed that the TBA improve the photoluminescence emission by reducing the density of trap states and the optical absorption indicates a significant shift to the lower wavelength and optical bandgap varied from 1.8 to 1.52 eV. Finally, the stability was explored for 5% TBA, it found that after 15 days the stability remained excellent in relative humidity of ~60%. These results would be helpful for realizing stable and high performance MAPbI3-based devices. Furthermore, we inspect the effect of monovalent cation substitution of Guanidinium (GA) on the structural and optical properties of FAPbI3 thin films perovskites. The ratio between the desirable a-phase and the undesirable y yellow phase is studied as a function of GA content. GA doping is shown to be efficient in the control of a/y phases ratio and then in the stabilization of the a-FaPbI3 phase. We qualitatively evaluate the impact of 10% of guanidinium on the phase composition and microstructure of films. The results show that an adequate amount of 10% GA:FaPbI3 leads to a homogeneous perovskite film with stable a phase, large grains, and free pinholes. 10% GA: FaPbI3 films demonstrate excellent stability after aging for 15 days in relative humidity of~60%.
[CA] L'objectiu principal d'aquesta tesi és contribuir a l'avanç de noves tècniques d'elaboració de baix cost, fent servir materials d'aliatges del tipus de coure, indi, gal·li i seleni (CIGS) i perovskites, per a aplicacions en energia solar fotovoltaica. El CIGS sembla ser adequat ja que són de baix cost de producció i s'han reportat eficiències de conversió del 23,35%. D'altra banda, les perovskites híbrides d'halurs de plom orgànics-inorgànics han aparegut com a nous materials excepcionals per cel·les solars, especialment perquè l'eficiència de les cel·les solars basades en perovskites ha augmentat del 3.8% al 22.7% en menys d'un lustre. En el present treball, reportem l'elaboració i caracterització de CIGS y de perovskitas de iodur de plom de metilamoni (MAPbI3) i de iodur de plom de formamidini (FaPbI3) per a les cèl·lules solars de CIGS i tàndem Perovskites/CIGS. En les capes de CIGS dipositades per electrodeposició es va investigar l'efecte dels diferents paràmetres sobre el procés d'electrodeposició, així com l'efecte del contacte posterior sobre les propietats estructurals i òptiques del CIGS. Ens trobem que el tipus de contacte posterior té un efecte significatiu en la posterior interpretació de pel·lícules primes CIGS. A més, vam estudiar la tècnica de polvorització de la piròlisi per produir pel·lícules de CIGS. Es va estudiar el procés de recuit, que és el factor clau per millorar el rendiment de les cèl·lules solars. Es van produir diferents pel·lícules fines formades pel nostre dispositiu CdZnS/CdS/CIGS/Mo que utilitzaven una capa conductiva CdZnS transparent per minimitzar l'alineació de la interfície. D'altra banda, es van investigar perovskites MAPbI3, amb la finalitat d'optimitzar la composició química i estudiar el procés de cristal·lització també per a conèixer l'estabilitat dels materials de perovskita. la cristal·lització s'aconsegueix alentint la solubilitat en una solució saturada mitjançant l'addició d'una quantitat diferent de l'antisolvent d'èter dietílic. Durant el tractament apareixen al mateix temps intercanvis complexos sota la influència de moltes propietats fisicoquímiques. Una comprensió completa d'aquest tema és de vital importància per a millorar el rendiment. Amb l'objectiu principal d'augmentar l'estabilitat de MAPbI3, el tetrabutilamoni (TBA) es pot incorporar a MAPbI3, impulsant la formació de l'estructura de perovskita, la qual cosa porta a una major orientació al llarg de (110). MAPbI3 dopades amb TBA presenten una millora de la cristalinitat, major grandària, la qual cosa és adequada per a la fabricació de dispositius optoelectròniques de major rendiment. A més, hem identificat l'impacte de TBA en les propietats foto físiques de MAPbI3. Hem notat que el dopatge amb TBA millora tant l'emissió de la fotoluminiscència en reduir la densitat dels estats de trampes com l'absorció òptica on apareix un canvi significatiu de la banda òptica prohibida cap a longituds d'ona més llargues que significa disminuir l'energia del gap, que va variar de 1.8 a 1.52 eV. Finalment, es va explorar l'estabilitat per les perovsquites dopades amb 5%TBA. Es va trobar que després de 15 dies l'estabilitat romania excel·lent en un humitat de 60%. A més, hem estudiat FAPbI3 com un dels materials de perovskita més atractius. Hem investigat l'efecte de la substitució de guanidini (GA) sobre les propietats estructurals i òptiques de FAPbI3. La relació entre la fase a de perovskita desitjable i la fase indesitjable y es va estudiar en funció del contingut de GA. Es mostra que el dopatge amb GA és eficaç en el control de la relació de fases a /y i després en l'estabilització de la fase a-FaPbI3. Els resultats mostren que una quantitat adequada de 10% GA condueix a una pel·lícula homogènia amb fase a estable, grans grans lliures de porus i forats. Les pel·lícules de 10% GA:FaPbI3 demostraren una excel·lent estabilitat després de l'envelliment durant 15 dies en un ambient humit (humitat relativa de 60%).
Bouich, A. (2020). Study and Characterization of Hybrid Perovskites and Copper-Indium-Gallium Selenide thin films for Tandem Solar Cells [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/160621
TESIS

Els òxids amb estructura perovskita són molt interessants causa del seu ampli rang de possibles en aplicacions en espintrònica, dispositius magneto-òptics o catàlisi. La majoria d'aquestes aplicacions requereixen de la utilització de capes primes o heteroestructures. Les propietats electròniques de les perovskita estan determinades per les propietats físiques associades amb els metalls de transició i amb els anions oxigen dels vèrtexs dels octahedres BO6. Les tècniques de creixement a partir de dissolucions químiques són molt prometedores per a la consecució de capes epitaxials d'òxids, degut al seu elevat rendiment, fàcil escalat, baix cost i al fet que poden ser més respectuoses amb el medi ambient. Primerament, presentem els conceptes bàsics relatives als òxids metàl·lics tipus perovskita, incloent la seva estructura i propietats magnètiques, i els mètodes utilitzats en general per al seu creixement. Seguidament presentem els detalls del mètode de creixement per deposició assistida per polímers (DAP), i les tècniques de caracterització de les propietats estructurals i físiques de les capes crescudes. La tercera part consisteix en la compilació dels articles ja publicats sobre capes epitaxials de La0.92MnO3, La2CoMnO6 i La2NiMnO6 crescudes per DAP. El comportament tèrmic de les solucions precursores s'ha analitzat per mitjà de mesures combinades d'anàlisi termogravimètrica i calorimetria diferencial. La propietats estructurals es van analitzar a partir de la difracció de raigs-x. El gruix de les capes es estajo a partir de mesures de reflectivitat de raigs-x. La microscòpia de forces atòmiques va servir per estudiar la rugositat de les capes. Les propietats magnètiques estàtiques es van estudiar utilitzant un magnetòmetre SQUID. Mesures de microscòpia electrònica de rastreig combinades espectrocopia de pèrdua d'energia d'electrons van confirmar l'ordenament catiònic Co / Mn en capes de La2CoMnO6, i mesures amb radiació de sincrotró (sincrotró ALBA) es van utilitzar per determinar el grau de desordre en capes de La2NiMnO6. Les propietats de dinàmica de magnetisme en capes de La0.92MnO3 i en bicapes de La0.92MnO3/Pt en funció de la temperatura, van ser estudiades per mesures de ressonància ferromagnètica. Els resultats mostren que les condicions de creixement pròpies de de la DAP (condicions de creixement lentes i pròximes a l'equilibri termodinàmic) promouen la formació de capes d'alta qualitat amb una elevada cristal·linitat, a el mateix temps que afavoreixen l'ordenament catiònic. D'aquesta manera, s'han obtingut capes de La2CoMnO6 completament ordenades, i capes de La2NiMnO6 amb un ordre proper al 80%. D'altra banda, les mesures de ressonància ferromagnètica en capes de La0.92MnO3 i en bicapes de La0.92MnO3 / Pt, indiquen un clar augment de l'eixamplament ferromagnètic a les bicapes, la qual cosa indica una transferència de el moment d'espín de la capa d'La0 .92MnO3 a la cap de Pt per bombament d'espines. Aquest fet demostra que la tècnica DAP permet l'obtenció de capes d'òxids complexos d'una qualitat microestuctural elevada i adequades per a aplicacions en espintrònica. Els resultats obtinguts demostren que la DAP és competitiva comparada amb els mètodes físics de creixement de capes, i permet obtenir capes epitaxials d'òxids complexos de gran qualitat. En particular, les condicions de creixement pròpies de la DAP són propícies a facilitar l'ordenament catiònic en CAAPS d'òxids amb estructura doble perovskita.
Los óxidos con estructura perovskita son muy interesantes debido a su amplio rango de posibles aplicaciones en espintrónica, dispositivos magneto-ópticos o catálisis. La mayoría de estas aplicaciones requieren de la utilización de capas delgadas o heterostructuras. Las propiedades electrónicas de las perovskitas están determinadas por las propiedades físicas asociadas con los metales de transición y con los aniones oxígeno de los vértices de los octaehdros BO6. Las técnicas de crecimiento a partir de disoluciones químicas son muy prometedoras para la consecución de capas epitaxiales de óxidos, debido a su elevado rendimiento, fácil escalado, bajo coste y a que pueden ser más respetuosas con el medio ambiente. En esta Tesis, se ha utilizado la deposición asistida por polímeros (DAP), utilizando disoluciones acuosas para preparar capas de compuestos derivados de las manganitas de lantano, como son La0.92MnO3, La0.7Sr0.3MnO3, La2CoMnO6 y La2NiMnO6 sobre substratos de SrTiO3 y LaAlO3. El La0.92MnO3 y el La0.7Sr0.3MnO3 son ferromagnéticos y metálicos a bajas temperaturas, mientras que el La2CoMnO6 y el La2NiMnO6 son ferromagnéticos y aislantes. Todos estos compuestos poseen una temperatura de Curie cercana a temperatura ambiente. Primeramente, presentamos los conceptos básicos relativas a los óxidos metálicos tipo perovskita, incluyendo su estructura y propiedades magnéticas, y los métodos utilizados en general para su crecimiento. Seguidamente presentamos los detalles del método de crecimiento por DAP, y las técnicas de caracterización de las propiedades estructurales y físicas de las capas crecidas. La tercera parte consiste en la compilación de los artículos ya publicados sobre capas epitaxiales de La0.92MnO3, La2CoMnO6 y La2NiMnO6 crecidas por DAP. El comportamiento térmico de las soluciones precursoras se ha analizado por medio de medidas combinadas de análisis termogravimétrico y calorimetría diferencial. La propiedades estructurales se analizaron a partir de la difracción de rayos-x. El espesor de las capas se estajo a partir de medidas de reflectividad de rayos-x. La microscopia de fuerzas atómicas sirvió para estudiar la rugosidad de las capas. Las propiedades magnéticas estáticas se estudiaron utilizando un magnetómetro SQUID. Medidas de microscopia electrónica de rastreo combinadas espectrocopía de pérdida de energía de electrones confirmaron el ordenamiento catiónico Co/Mn en capas de La2CoMnO6, y medidas con radiación de sincrotrón (ALBA) se utilizaron para determinar el grado de desorden en capas de La2NiMnO6. Las propiedades de dinámica de magnetismo en capas de La0.92MnO3 y en bicapas de La0.92MnO3/Pt en función de la temperatura, fueron estudiadas por medidas de resonancia ferromagnética. Los resultados muestran que las condiciones de crecimiento propias de la DAP (condiciones de crecimiento lentas y próximas al equilibrio termodinámico) promueven la formación de capas de alta calidad con una elevada cristalinidad, al mismo tiempo que favorecen el ordenamiento catiónico. De esta forma, se han obtenido capas de La2CoMnO6 completamente ordenadas, y capas de La2NiMnO6 ordeadas 80%. Por otra parte, las medidas de resonancia ferromagnética en capas de La0.92MnO3 y en bicapas de La0.92MnO3/Pt, indican un claro aumento del ensanchamiento ferromagnético en las bicapas, lo cual indica una trasferencia del momento de espín de la capa de La0.92MnO3 a la cap de Pt por bombeo de espines. Este hecho demuestra que la técnica DAP permite la obtención de capas de óxidos complejos de una calidad microestuctural elevada y adecuadas para aplicaciones espintrónicas. Los resultados obtenidos demuestran que la DAP es competitiva comparada con los métodos físicos de crecimiento de capas, y permite obtener capas epitaxiales de óxidos complejos de gran calidad. En particular, las condiciones de crecimiento propias de la DAP son propicias a facilitar el ordenamiento catiónico en capas de óxidos con estructura doble perovskita.
Perovskites oxides are of strong interest due the huge potential range of applications they offer with a particularly simple structure, such as spintronics, magneto-optic devices, or catalysis, and most of these applications require the use of thin films and heterostructures. Most of the electronic properties of perovskites are determined by the physics associated with the transition metal and the corner-sharing oxygen anions of the BO6 octahedra therefore, in double perovskite structures, the ordered arrangement of cations in the B-site position is of major relevance. Chemical solution deposition (CSD) techniques are promising methodologies to achieve epitaxial oxide thin films combining high performance with high easy scalability, environment friendly fabrication and low cost. In this thesis, the polymer-assisted deposition (PAD), an aqueous CSD method, is used to prepare derivatives of lanthanum manganite perovskite films, including La0.92MnO3, La0.7Sr0.3MnO3, La2CoMnO6 and La2NiMnO6 films on SrTiO3 and LaAlO3 substrates. La0.92MnO3 and La0.7Sr0.3MnO3 display ferromagnetic metallic conducting properties, La2CoMnO6 and La2NiMnO6 are ferromagnetic insulating. All these films have Curie temperatures near room temperature. Firstly, we introduced the basic concepts related to perovskite oxides, including the structure and the magnetic properties, and the methods to grow oxide thin films. Secondly, more detailed processes of PAD method and characterizations will be presented. The third part is a compilation of articles of the La0.92MnO3, La2CoMnO6 and La2NiMnO6 films. All the films were prepared by PAD method. The thermal behavior of the mixed metal polymer precursor solution was traced by combining differential scanning calorimetry and thermogravimetric analysis. The structural features were studied by X-ray diffraction. The thickness was measured with X-ray reflectivity. The surface topography of the films was measured by AFM. Static magnetic properties were measured using a SQUID magnetometer. The scanning transmission electron microscopy (STEM) measurements together with electron energy loss spectroscopy (EELS) was used to confirm the full Co/Mn cationic ordering in La2CoMnO6 films, and ALBA synchrotron radiation facilities were used to investigate the disordering in La2NiMnO6 films. The dynamic magnetic properties of La0.92MnO3 thin films and La0.92MnO3/Pt bilayers as a function of temperature were studied by using a ferromagnetic resonance spectrometer. The results show that the particular crystallization and growth process conditions of PAD (very slow rate, close to thermodynamic equilibrium conditions) promote high crystallinity and quality of the films, as well as favors spontaneous B-site cationic ordering, almost full B-site cationic ordering can be achieved in La2CoMnO6 while the ordering factor in La2NiMnO6 films is around 80%. The La2CoMnO6 and La2NiMnO6 samples prepared by rapid thermal annealing (RTA) have similar magnetic properties to the counterpart films prepared by using conventional annealing processes, showing only slight differences in the microstructure. On the other hand, ferromagnetic resonance (FMR) measurements in La0.92MnO3 films and La0.92MnO3/Pt bilayers indicate a clear increase of the magnetic damping in the later, which may be indicative of the transfer of spin momentum from La0.92MnO3 to the Pt layer by spin pumping. This fact demonstrates that PAD technique allows obtaining complex oxide thin films of high microstructural quality suitable for spintronics applications. Our results make evident the CSD-PAD method can be competitive with physical methods allowing obtaining complex oxide epitaxial thin films of high quality. In particular, the growth conditions of PAD are prone to promote spontaneous B-site cationic ordering in double perovskite oxide.

Abstract Nd-modified lead-zirconate-titanate (PNZT) thin films were deposited on MgO(100), Si(100) and Al2O3(1102) single-crystal substrates using the pulsed-laser-ablation technique with a XeCl excimer laser. The post-annealing heat-treatment technique was used for the crystallisation of the films. The structural characterization, microstructure and the chemical composition of the thin films and of the ceramic Pb0.97Nd0.02(Zr0.55Ti0.45)O3 targets after ablation were studied using x-ray diffraction, scanning electron microscopy and energy-dispersive x-ray spectroscopy, respectively. The formation of the particulates on the target surface during the ablation process and the effect of the particulates on the quality of the thin films were studied. Typically, the ferroelectric PNZT thin films for the capacitor structures were deposited at the laser-beam fluence of around 1.0 J/cm2 and annealed at the temperatures from 600 to 700 °C. The dielectric and, especially, the polarization properties and the residual macroscopic stress state of the PNZT thin films were studied. The relationship between the electrical properties of the films and the nature of the stress state was also investigated. The average growth rate of the PNZT films increased linearly with increasing laser-beam fluence above the threshold value of around 0.4 J/cm2. The composition of the PNZT films varied strongly with the deposition laser-beam fluence and annealing temperature. The phase structure of PNZT films ablated from Pb0.97Nd0.02(Zr0.55Ti0.45)O3 targets could be adjusted between tetragonal and rhombohedral structures by changing the incident laser-beam fluence on the target surface. The surface of the target after ablation was covered by the laser-cone structure and the topmost layer of the target was amorphous having TiO2 and ZrO2 structures with separate segregated lead droplets. On MgO substrates, values of the relative dielectric constant er from 430 to 560 and of the remanent polarization εr of the order of 18 μC/cm2 were achieved in PNZT films which were under a compressive stress of the order of 300 MPa. On silicon substrates, εr was around 100 and the polarization properties of the films were modest due to a strong tensile stress of the order of 400 MPa. The Poole-Frenkel conduction mechanism with the activation energy of around 0.2 eV was found responsible for the leakage conductivity in the capacitor structures with PNZT films.

Los índices de refracción complejos de películas delgadas de perovskitas de haluros mixtos de formamidinio-cesio de plomo (FA0.83Cs0.17Pb(I1 − xBrx)3), con composiciones variando de x = 0 a 0.4, y para topografías planas y de textura rugosa, son reportadas. Las películas se caracterizan por medio de una combinación de elipsometría espectral de ángulo variable y transmitancia espectral en el rango de longitudes de onda de 190 nm a 850 nm. Las constantes ópticas, espesores de las películas y las capas de microrugosidad, son determinadas con un método “punto a punto”, minimizando una función de error global, sin hacer uso de modelos de dispersión, e incluyendo información topográfica proporcionada por un microscopio con focal láser. Para evaluar el potencial de ingeniería del ancho de banda del material, sus anchos de banda y energías de Urbach son determinadas con exactitud haciendo uso de un modelo de fluctuaciones de banda para semiconductores directos. Este considera las colas de Urbach y la región de absorción banda a banda fundamental en una sola ecuación. Con esta información, la composición que brindaría el ancho de banda óptimo de 1.75 eV para una celda solar tándem Siperovskita es determinada.
The complex refractive indices of formamidinium cesium lead mixed-halide (FA0.83Cs0.17Pb(I1 − xBrx)3) perovskite thin films of compositions ranging from x = 0 to 0.4, with both flat and wrinkle-textured surface topographies, are reported. Films are characterized using a combination of variable angle spectroscopic ellipsometry and spectral transmittance in the wavelength range of 190 nm to 850 nm. Optical constants, film thicknesses and roughness layers are obtained point-by-point by minimizing a global error function, without using optical dispersion models, and including topographical information supplied by a laser confocal microscope. To evaluate the bandgap engineering potential of the material, the optical bandgaps and Urbach energies are then accurately determined by applying a band fluctuations model for direct semiconductors, which considers both the Urbach tail and the fundamental band-to-band absorption region in a single equation. With this information, the composition yielding the optimum bandgap of 1.75 eV for a Si-perovskite tandem solar cell is determined.
Tesis

The aim of the present PhD thesis has been the synthesis of novel materials for photovoltaic (PV) technologies. One possible way to increase the conversion efficiency of silicon solar cells is to shift the incident sunlight spectrum, converting photons poorly exploited by the active PV material into more effective photons. The materials studied as energy converters, consist of thin film layers integrated in the PV panel and made of a host material and an active luminescent species. In the present thesis, the energy conversion systems made of lanthanide doped fluorides (CaF2, NaYF4, NaGdF4, KYF4 and YOF) have been synthetized using MOCVD and sol-gel methods and deeply studied for their potential integration in silicon solar cells. Together with the traditional silicon PV technology, a new class of PV materials, based on inorganic multi-junction technology, new hybrid materials and organic dye-sensitized solar cells (DSSC) is subject of interest in the last years. Hybrid metalorganic/inorganic systems of Eu-complex/NiO films have been developed for the DSSC technology and for the potential improvement of the PV material with new functionalities, that combine the semiconductor behavior of the inorganic part to the luminescent properties of the metalorganic component. The all-inorganic halide perovskite CsPbBr3 has been synthetized through a precipitation method. The perovskite CsPbBr3 has a semiconductor behavior, with an energy band gap useful in the PV application and has the advantages to not have any labile or expensive organic components.

Ce travail est né de l'idée d'associer l'ingénierie des matériaux sous forme de couches minces, domaine qui motive depuis de nombreuses années les chercheurs du LMGP, à des substrats piézoélectriques à fort coefficients de déformation. Les matériaux piézoélectriques peuvent convertir une énergie électrique en une énergie mécanique (de déformation) et vice-versa. Il est alors aisé d'imaginer qu'une couche mince synthétisée à la surface d'un substrat piézoélectrique profitera de la déformation de ce dernier quand il est soumit à un champ électrique. Le substrat mis en jeu est le PMN-PT, composé qui présente de forts coefficients de déformation. Dans cette étude le film synthétisé et mis en œuvre est le LaNiO3. Il cristallise dans une structure pérovskite ABO3. Cette structure présente l'avantage de permettre une grande variété de distorsions structurales et peut accueillir un grand nombre d'éléments chimiques.

The aim of this thesis is to develop a deeper understanding and the technology in the nascent field of solid-state organic-inorganic perovskite solar cells. In recent years, perovskite materials have emerged as a low-cost, thin-film technology with efficiencies exceeding 16% challenging the quasi-paradigm that high efficiency photovoltaics must come at high costs. This thesis investigates perovskite solar cells in more detail with a focus on incorporating plasmonic nanostructures and perovskite film formation. Chapter 1 motivates the present work further followed by Chapter 2 which offers a brief background for solar cell fabrication and characterisation, perovskites in general, perovskite solar cells in specific, and plasmonics. Chapter 3 presents the field of plasmonics including simulation methods for various core-shell nanostructures such as gold-silica and silver-titania nanoparticles. The following Chapters 4 and 5 analyze plasmonic core-shell metal-dielectric nanoparticles embedded in perovskite solar cells. It is shown that using gold@silica or silver@titania NPs results in enhanced photocurrent and thus increased efficiency. After photoluminescence studies, this effect was attributed to an unexpected phenomenon in solar cells in which a lowered exciton binding energy generates a higher fraction of free charge. Embedding thermally unstable silver NPs required a low-temperature fabrication method which would not melt the Ag NPs. This work offers a new general direction for temperature sensitive elements. In Chapters 6 and 7, perovskite film formation is studied. Chapter 6 shows the existence of a previously unknown crystalline precursor state and an improved surface coverage by introducing a ramped annealing procedure. Based on this, Chapter 7 investigates different perovskite annealing protocols. The main finding was that an additional 130°C flash annealing step changed the film crystallinity dramatically and yielded a higher orientation of the perovskite crystals. The according solar cells showed an increased photocurrent attributed to a decrease in charge carrier recombination at the grain boundaries. Chapter 8 presents on-going work showing noteworthy first results for silica scaffolds, and layered, 2D perovskite structures for application in solar cells.

Os materiais de estrutura perovskita compreendem um vasto grupo de compostos cuja estrutura na sua forma mais simples pode ser representada pela fórmula química ABO3. Uma das principais vantagens que a estrutura perovskita apresenta é o alto grau de flexibilidade em acomodar uma grande variedade de átomos nos sítios A e B, permitindo um maior controle de suas propriedades físicas e químicas bem como a manutenção de sua estrutura básica, mesmo para altas concentrações de átomos substituintes. Devido estas propriedades, estes materiais têm sido aplicados com sucesso como capacitores, varistores, fotoeletrodos, memóriasferroelétricas e sensores de gases. Nas últimas décadas, tem sido reportada a utilização do titanato de estrôncio (SrTiO3, ST) na forma de filmes finos e espessos como sensor de gás oxigênio em altas temperaturas (>500 °C). Recentemente, foi mostrado que o titanato de estrôncio dopado com Fe apresentava uma excelente sensibilidade ao gás ozônio. Entretanto, neste trabalho, somente uma composição foi caracterizada e nem todas as propriedades importantes em relação a esta aplicação foram completamente exploradas. Neste contexto, esta tese de doutorado teve como objetivo verificar o efeito da substituição do átomo de estrôncio pelo lantânio e do titânio pelo Ferro no composto SrTiO3 na forma de pó e filmes finos nanoestruturados com a finalidade de verificar o efeito destas substituições nas propriedades sensoras do material. Inicialmente, com o objetivo de avaliar a influência da adição de La na estrutura do composto ST, amostras na forma de pó do sistema Sr1-xLaxTiO3.(SLT) foram preparadas através do método dos precursores poliméricos. Posteriormente, pelo mesmo método, foram sintetizadas amostras do sistema SrTi1-xFexO3 (STF) e Sr1-XLaxTi1-yFeyO3 (SLTF). A partir das amostras na forma de pó e na forma de solução, filmes finos e espessos foram respectivamente obtidos através das técnicas de deposição por feixe de elétrons (EBD) e spin-coating (SC). As amostras nanoestruturadas na forma de pó e na forma de filmes foram caracterizadas por difração de raios X, espectroscopia de absorção de raios X (XANES) na borda K do Ti e do Fe e espectroscopia de fotoelétrons excitados por raios X (XPS). A análise morfológica foi realizada através das técnicas de microscopia eletrônica de varredura (MEV) e microscopia de força atômica (MFA). As amostras do sistema STF e SLTF na forma de filmes finos foram avaliadas em relação à sensibilidade aos gases O3, NO2, NH3 e CO. Os resultados indicaram que os filmes do sistema SLTF depositados pela técnica de deposição por feixe de elétrons apresentam uma maior sensibilidade ao gás ozônio, enquanto o filme de mesma composição depositado pelo método de spin-coating apresentou uma melhor estabilidade e tempo de recuperação em relação a este mesmo gás.
The perovskite structure materials comprise a large group of compounds with the structure in simple form can be represented by the ABO3. chemical formula. The main advantage that the perovskite structure presents is the high degree of flexibility to accommodate a wide variety of atoms in sites A and B, allowing a greater control of physical and chemical properties of the material, maintaining its structure even for a high concentrations of substituent\'s. Due to these properties, these materials have been successfully applied as capacitors, varistors, photoelectrodes, ferroelectric memories and gas sensors. In the last decade, strontium titanate (SrTiO3, ST) in the form of thin and thick films have been reported as oxygen gas sensor at higher temperatures (> 500 °C). Recently, strontium titanate doped with Fe was used as the first ozone sensor. However, the work was carried out only with a certain composition and some important properties for this application have not been fully exploited. In this context, this PhD thesis aimed to the synthesis of strontium titanate system in powder form and nanostructured thin films with the substitution of Sr for La and Ti for Fe. In order to verify the effect of these substitutions in material properties initially Sr1-xLaxTiO3 (SLT) samples were prepared in powder form by the polymeric precursor method in order to evaluate the influence of the addition of La in the structure of the compound ST. Subsequently, samples were synthesized from SrTi1-x Fex O3 (STF) and Sr1-XLaxTi1-yFeyO3 (SLTF) systems through the polymeric precursors, which were used for the deposition of thin and thick films, which were respectively obtained through electron beam deposition techniques (EBD) and spin-coating (SC). Samples in the form of nanostructured powder and thin films were characterized by X-ray diffraction, X-ray absorption spectroscopy (XANES) at Ti and Fe K-edges and by X-ray photoelectron spectroscopy (XPS). Morphological analysis was performed using the scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques. The STF and SLTF samples in a thin film form were evaluated towards their sensitivity to O3, NO2, NH3 and CO gases. The results indicated that SLTF films deposited by electron beam deposition technique exhibit higher sensitivity to ozone gas. However the same composition deposited by spin-coating showed a better stability and recovery time relative to the same gas.

O objetivo desta tese de doutorado foi estudar a influência da adição do íon estanho (Sn4+) à rede do composto SrTiO3 em substituição ao íon de titânio visando otimizar as propriedades elétricas desse composto e, como consequência, obter uma melhora de seu desempenho como um sensor de gás na forma de filmes finos. Para realizar a deposição destes filmes finos através dos métodos de Deposição por Feixe de Elétrons (EBD), alvos cerâmicos de composição SrTi1-xSnxO3 (STSO) com x = 0; 0,20; 0,40; 0,60; 0,80; 0,85; 0,90; 0,95; 1 foram obtidos através do método dos precursores poliméricos modificado. A sequência de formação de soluções sólidas foi determinada através do refinamento Rietveld das amostras STSO na forma de pó sinterizadas, obtidas através dos métodos dos precursores poliméricos e de reação de estado sólido, mostrando que a transição da fase cúbica Pm3̄m do composto SrTiO3 até a fase ortorrômbica Pnma do composto SrSnO3 não depende do método de síntese. As medidas de espectroscopia Raman e absorção de raios-X (XANES, na borda K do Ti) das amostras tanto na forma de pó, obtidas através do método dos precursores poliméricos e de reação de estado sólido, quanto na forma de filme fino obtidas por EBD revelaram a existência de uma desordem local na rede do composto SrTiO3 que diminui com o aumento da temperatura e com a diminuição da concentração de Sn. Os filmes finos STSO obtidos por EBD foram avaliados como sensores utilizando-se os gases O3 e NH3. Em medidas realizadas com o gás ozônio (O3), os resultados mostraram que os filmes finos de 100 nm de espessura apresentaram uma maior sensibilidade tendo a amostra com 60% de Sn com o melhor desempenho a 350°C para 0,15 ppm do gás. As análises de performance dos filmes STSO quanto a seletividade indicaram que não foram seletivos e que apresentaram uma maior resposta ao gás ozônio quando comparados ao gás NH3.
The objective of this work was to study the influence of the addition of tin ion (Sn4+) into the SrTiO3 compound lattice, to replace the titanium ion (Ti4+). The aim was to optimize the electrical properties of SrTiO3 compound and, as a consequence, to obtain an improvement of its performance as a gas sensor in the thin films samples. To perform the deposition of these thin films through Electron Beam Deposition (EBD), ceramic targets of composition SrTi1-xSnxO3 (STSO) with x = 0; 0.20; 0.40; 0.60; 0.80; 0.85; 0.90; 0.95; and 1 were obtained by the modified polymer precursor method. The solid solution formation sequence was determined by the Rietveld refinement of the STSO sintered powdered samples, obtained by both polymeric precursor and solid-state reaction methods, showing that the transition from the cubic Pm3̄m phase of the SrTiO3 compound to the orthorhombic Pnma phase of the SrSnO3 compound does not depend on the synthesis method. The measurements of Raman spectroscopy and absorption of X-rays (XANES, at Ti K-edge), of the powdered samples obtained by both synthesis methods and of the thin films obtained by EBD, revealed the existence of a local disorder in the SrTiO3 compound lattice which decreases with increasing of temperature and with decreasing of Sn concentration. The STSO thin films were evaluated as sensors using the O3 and NH3 gases. In measurements accomplished with the ozone gas (O3), the results showed that thin films of 100 nm thickness had a higher sensitivity. The sample having 60% of tin showed the best performance at 350°C for 0.15 ppm of ozone gas. The performance analysis related to the selectivity of the STSO films indicated they were not selective and that presented a higher response to the ozone gas when compared to the NH3 gas.