Dissertationen zum Thema „Perovskity“

Method, so called “glycin- nitrate process”, combined with high temperature solid state reaction, of preparation multi- component ceramic perovskite materials was studied. Two types of perovskite systems were prepared by this method. Firs one, based on LaNiO3 doped by calcium and aluminium and second one, based on SmFeO3 doped by calcium and nickel or cobalt. This method made possible preparation of one phase perovskite or perovskites with few percent of nickel in form of oxide. In systems containing both nickel and calcium another phases rich in calcium and nickel appeared.

Research was curried out on the perovskite systems with general formula A1-xA‘xB1-yB‘yO3± (where A=La, Sm, A´=Ca, B´=Al, B=Co,Fe,Mn and Cr). Perovskite oxides were sythesized by polymerisation methods and characterised by RTG analysis, BET method, SEM and EDX. TPD spectra and catalyst testing were measured in high temperature plug flow reactor and products were analysed by mass spectrometry. It was found, that metane oxidation at ratio O2/CH40,5 depended on the temperature. Total oxidation proceeded at the temperature betwen 300-700oC to the carbon dioxide and water, while the partial oxidation of metane (POM) occured at above 700oC to the hydrogen and carbon oxid (syngas). This was ascribed by equilibrium of O2 betwen gas phase and solid perovskite. There was used 12 perovskite systems, which catalysed methane oxidation by the same way. Dry reforming of methane run above temperature 700oC. Cobaltite and ferite type perovskites were found as the most active catalytic systems. On the base of obtained results the Mars van Krevelen mechanism was established for explanation of oxidation and reformation of methane by perovskite systems. It was showed, that POM was running by two steps mechanism. Products of total oxidation was occured in the first step, which were passed over to the syngas (H2+CO) in the second step.

Synthesis and bulk analysis of composite ceramic oxide materials and materials with perovskite-defect structure is presented within this work. Syntheses of these advanced ceramics materials were carroed out by using of nonconventional techniques (microwave-assisted hydrothermal synthesis and polycondensation techniques) and by conventional mechanochemical activation followed by high temperature solid state reaction. X-Ray difraction (XRD), Rietveld analysis, scaning microscopy (SEM), microalysis EDS-SEM, thermal analysis (TG), infrared spectroscopy (IR), determination of particles size and specific surface area were used for description of synthesized products. In case of perovskite system based on La-Sr-Fe-Ti-O electrochemical properties were studied. Part of work was focused on chemical analysis of synthesized composite oxide materials and decomposition hard structured products by using of nonconventional fields.

This thesis is focused on the study of the detection of electromagnetic radiation using monocrystalline perovskites. Theoretical part deals with basic principles of detections and possible applications of hybrid perovskite crystals in the field of ultraviolet and visible spectrum detection. Parameters of the recently published perovskite photodetectors are also presented. Experimental part describes synthesis, structural and optical properties of MAPbBr3 single crystals and electrical characterization of the Au/MAPbBr3/Au photodetector. Photodetector parameters (responsivity, external quantum efficiency and specific detectivity) are calculated based on the spectral and switching (on/off) current responses.

Nanočástice perovskitů halogenidů kovů vykazují unikátní vlastnosti, především výjimečně vysoké hodnoty kvantových výtěžků fluorescence, které předurčují tyto materiály pro aplikace v optoelektronických a fotonických zařízeních. Tato práce popisuje přípravu nanočástic perovskitů halogenidů kovů pomocí stabilizačních činidel inspirovaných přírodou. Stabilizační činidla zde slouží nejen ke stabilizaci, ale i k modifikaci povrchu nanočástic za účelem zvýšení funkčnosti výsledných nanostruktur. Úvod práce popisuje optimalizaci přípravy nanočástic precipitační technikou za použití stabilizačních činidel; jako stabilizační činidlo byl zvolen adamantan-1-amin spolu s hexanovou kyselinou. Bylo prokázáno, že klíčový vliv na optické vlastnosti výsledných koloidních roztoků má volba rozpouštědel a teploty při precipitaci. Mimo jiné byl zkoumán vliv koncentrace prekurzorů na výslednou morfologii a optické vlastnosti nanočástic a jejich koloidních roztoků. V neposlední řadě byly nanočástice stabilizovány adamantan-1-aminem spolu s různými karboxylovými kyselinami a byly studovány optické vlastnosti a koloidní stabilita výsledných koloidních roztoků. V dalším kroku byly nanočástice perovskitů stabilizovány pomocí proetogenních aminokyselin L-lysinu and L-argininu. Takto stabilizované nanočástice vykazovaly úzká emisní spektra ve viditelné oblasti a kvantové výtěžky fluorescence dosahující hodnot téměř 100 %. Stabilizace nanočástic prostřednictvím postranních skupin aminokyselin byla prokázána navázáním chránící terc-butoxykarbonylové skupiny na -amino skupinu. Nanočástice stabilizované modifikovaným lysinem v průběhu jejich přípravy vykazovaly závislost optických vlastností na přítomnosti vody. Předpokládá se, že molekuly vody jsou schopné kontrolovat růst krystalové mřížky po navázání na prekurzory perovskitů a ovlivňovat tak výslednou velikost nanočástic, což vede k projevení kvantových jevů. Spojení nanočástic perovskitů s peptidy představuje nový typ materiálů kombinujících výjimečné optické vlastnosti se samoorganizačními a senzorickými vlastnostmi. Tento koncept byl představen přípravou nanočástic perovskitů stabilizovaných cyklo(RGDFK) pentapeptidem. Vzhledem k citlivosti peptidů na jejich byly nanočástice stabilizovány peptidovými nukleovými kyselinami, robustními analogy nukleových kyselin. Ke stabilizaci nanočástic byl připraven monomer a trimer peptidové nukleové kyseliny obsahující thymin jako dusíkatou bázi. Thymin byl na povrchu nanočástic dostupný k interakci s adeninem přes vodíkové můstky umožňující přenos náboje. Kombinace peptidových nukleových kyselin a perovskitů s unikátními optickými vlastnostmi otevírá aplikační možnosti zejména v oblasti optických senzorů.

Advanced nanomaterials show a significant improvement in certain physical or functional properties compared to conventional materials. Such advanced materials are, for example, lead halide perovskites (LHP). It is a group of hybrid organic-inorganic materials with a direct bandgap exhibiting unique optical properties. The high quantum efficiency of photoluminescence makes nanocrystals or thin films of LHP suitable candidates for the production of light-emitting diodes, solar cells and LCD displays. Their inexpensive and simple fabrication together with their unique optical properties makes LHP one of the most developed materials of the last decade. This diploma thesis aims to study the optical properties of CsPbBr3 perovskite nanocrystals using high lateral resolution methods. CsPbBr3 perovskite nanocrystals show intense anti-Stokes photoluminescence. These nanocrystals can emit light with a lower wavelength than that of the light that causes their photoluminescence. The nanocrystals are prepared in two different ways: by evaporation or by crystallization of the precursor in a solution of dimethylformamide. The morphology, photoluminescence properties and chemical composition of individual nanocrystals are studied. Each nanocrystal is studied individually and its size, shape, photoluminescence properties and chemical compounds are determined, which leads to a deeper understanding of the anti-Stokes photoluminescence of perovskite nanocrystals.

The Master´s thesis deals with the preparation of perovskite oxides by glycine synthesis with following characterization and analysis of catalytic activity. Especially is discussed crystallographic structure. In the theoretical part were first summarized the available information of the properties and usage of perovskite oxides. In the experimental part of the work was carried out the preparation of perovskite oxides and were made chemical analysis. Moreover a catalytic activity of selected perovskites has been studied and have been illustrated their crystal structure.

The presented diploma thesis deals with the preparation of perovskite single crystals by inverse thermal crystallization and subsequent study of the basic properties of these hybrid organic-inorganic materials that can be used in various optoelectronic (photodetectors, transistors, lasers, LEDs) or photovoltaic applications. Their behavior in the electric field was studied by impedance spectroscopy. Impedance and capacitance-voltage (C-V) characteristics (frequency dependences) were measured in the dark and in the light. From the impedance dependences for measurements at 0 V voltage in the dark, the equivalent circuit was modeled and its parameters and dielectric constant were determined. From the C-V dependence, Mott-Schottky analysis determined the parameters – "flat-band" potential U_"fb" and charge carrier density N_"C-V" , the parameter – the so-called Warburg coefficient was found, which together with the parameter N_"C-V" was used to calculate the diffusion coefficient D.

Orientador: Pascoal José Giglio Pagliuso
Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin
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Resumo: Há muitas décadas os óxidos de metais de transição são tema de grande interesse científico devido à grande variedade de propriedades físicas interessantes que apresentam, com suas possíveis aplicações tecnológicas. Mais recentemente, por exemplo, os óxidos de metais de transição com propriedades multiferróicas ganharam destaque na comunidade científica como potenciais dispositivos magneto-eletrônicos. Muitos óxidos de metais de transição se formam na estrutura cristalina chamada perovskita simples, com simetria cúbica ou distorcida. Muitos outros óxidos podem se cristalizar numa variante da perovskita simples, a chamada perovskita dupla ordenada (PDO), que possui fórmula geral A2B¿B¿¿O6, onde o íon A ocupa os vértices do cubo enquanto os cátions B¿ e B¿¿ se alternam nos centros dos octaedros de oxigênio. Dois compostos com estrutura PDO bastante estudados são o Sr2FeReO6 e Sr2FeMoO6 devido ao fato de apresentarem, entre outras propriedades interessantes, comportamento meio-metálico (halfmetal), magnetrorresistência por tunelamento à temperatura ambiente, ferrimagnetismo com TC acima de 400K em ambos os compostos. As propriedades estruturais, eletrônicas e magnéticas dessas PDOs estão altamente conectadas e são fortemente dependentes do grau de hibridização dos orbitais d dos cátions B¿¿. Assim, se fazem importantes os estudos de novos compostos PDO a fim de se investigar as idéias correntes propostas em literatura e, nesse contexto, reportamos aqui os resultados da síntese e caracterização das séries inéditas Ca2-xLaxFeIrO6 e Sr2-xLaxFeIrO6, onde o Ir, assim como o Re e Mo, é metal de transição, no caso com caráter 5d, e pode assumir diferentes estados de valência. As medidas de magnetização indicaram que estes sistemas tendem a evoluir de antiferromagnéticos nas extremidades das séries, x = 0 e x = 2, para ferrimagnéticos em regiões intermediárias da série. Medidas realizadas no composto de maior magnetização da série de Sr, o Sr1.2La0.8FeIrO6, indicaram que este composto se ordena ferrimagneticamente em torno de 700 K, sendo esta a mais elevada TC já reportada para perovskitas duplas. Medidas de resistividade em função da temperatura indicaram que os compostos apresentam comportamento isolante e praticamente nenhum efeito magneto-resistivo. No composto antiferromagnético Sr2FeIrO6 foi estudada a resistividade sob efeito de pressão e, embora não tenha ocorrido nenhuma transição metal-isolante, ocorre uma diminuição sistemática da resistência do material e da inclinação da curva à medida que a pressão aumenta, indicando um comportamento do tipo isolante de Mott nesse composto. Neste trabalho são apresentados também resultados dos estudos realizados na perovskita TbMnO3. Realizamos neste óxido medidas de susceptibilidade magnética, calor específico, Ressonância Paramagnética Eletrônica (EPR) e absorção de microondas para várias temperaturas. A susceptibilidade magnética e o calor específico confirmaram para a amostra estudada as temperaturas de transição de fase magnética (TN = 41 K) e ferroelétrica (Tlock) já reportadas em literatura. Os espectros de EPR mostraram para todo o intervalo de temperatura uma única linha consistente com uma forma de linha Lorentziana e um valor de g independente da temperatura g = 1.96(3) consistente com Mn3+ em um meio isolante. A largura de linha sofreu um alargamento com a temperatura seguindo uma lei do tipo C/T. Esse alargamento impediu a observação dos espectros de ressonância em torno das regiões de temperaturas das transições de fase magnética e ferroelétrica. Devido à forte dependência da constante dielétrica com a freqüência, as medidas realizadas com a cavidade de campo elétrico não permitiram a observação de qualquer anomalia em torno das temperaturas de transições
Abstract: For many decades the transition metal oxides are subject of great scientific interest because of the wide variety of interesting physical properties and their potential technological applications. More recently, for example, oxides of transition metals with multiferroic properties have been considered as potential magneto-electronic devices. Many transition metal oxides form in the perovskite crystalline structure, with cubic or distorted symmetry. Many other oxides can crystallize in a variant of the simple perovskite, called the ordered double perovskite (ODP), which has the general formula A2B'B''O6, where the A ion occupies the vertices of the cube while the cations B 'and B'' alternate in the centers of the oxygen octahedra. Sr2FeReO6 and Sr2FeMoO6 are two compounds with the ODP structure which were extensively studied due to their interesting properties such as half-metal behavior, tunneling magnetoresistance at room temperature and ferrimagnetic order (TC above 400 K). The structural, electronic and magnetic properties of these ODPs are highly correlated and are strongly dependent on the strong d orbitals hybridization of the of the B'' cations. Therefore, studies of new ODP compounds are important in order to investigate the current ideas proposed in the literature and improve the understanding of their physical properties. We report here our results of synthesis and characterization of the unpublished series Ca2-xLaxFeIrO6 and Sr2-xLaxFeIrO6, where the Ir such as Re and Mo are transition metal, with d character that can assume different valence states. The magnetic measurements indicated that those systems tend to evolve from antiferromagnetics at the ends of the series, x = 0 and x = 2, to ferrimagnetic for intermediate regions of the series. Measurements performed in the compound of higher magnetization in the Sr serie, Sr1.2La0.8FeIrO6 indicated that this compound orders ferrimagnetic around 700 K, which is the highest TC ever reported for double perovskites. Resistivity measurements as a function of temperature indicated that these compounds also exhibit insulating behavior and virtually no magneto-resistive effect. In the antiferromagnetic compound Sr2FeIrO6, the effect of pressure on the resistivity was investigated, and although no metal-insulator transition was seen, there is a systematic decrease of the resistance and the slope of the curve as the pressure increases, indicating a Mott insulator-like behavior in this compound. This work also presents results on the TbMnO3 perovskite. We have performed magnetic susceptibility, specific heat, Electron Paramagnetic Resonance (EPR) and microwave absorption measurements at various temperatures. Magnetic susceptibility and specific heat data confirmed the ocurrence of a magnetic (TN = 41 K) and ferroelectric (Tlock) phase transition. The EPR spectra showed, for the entire temperature range measured, a single Lorentzian line shape and T independent g-value = 1.96 (3), consistent with the resonance of Mn3+ in an insulating environment. The width line broadens with the decreasing temperature following a C/T law. This broadening prevented the observation of the resonance spectra near the magnetic and ferroelectric phase transitions. Because of the strong frequency dependence of the dielectric constant, the measurements performed with the electric field cavity also did not allow observation of any anomaly around the ferroelectric transition
Doutorado
Física da Matéria Condensada
Doutor em Ciências

Uma tecnologia importante para reduzir a quantidade de poluentes atmosféricos lançados na atmosfera, é a utilização de catalisadores, que convertem os gases altamente poluentes como o NO, para outros gases inofensivos ao meio ambiente. Neste trabalho, os óxidos do tipo perovskitas La2CuO4, LaNiO3, LaMnO3, La1,4Sr0,6CuO4, La0,7Sr0,3NiO3 e La0,7Sr0,3MnO3 foram preparados através do método da co-precipitação, caracterizados por difração de raios-X, redução a temperatura programada, fisissorção de nitrogênio e análise química, e, posteriormente avaliados frente as reações de redução de NO com CO, e decomposição direta de NO. Ambas as reações foram testadas nas temperaturas de 400oC e 500oC e o tempo de reação foi de 7 à 10 horas. Através dos ensaios catalíticos verificou-se que o catalisador La2CuO4 apresentou a maior atividade para a reação de redução, e quando substituiu-se parcialmente o lantânio pelo estrôncio, houve uma melhora significativa para todos os catalisadores. As análises de DRX indicaram que, mesmo após os ensaios catalíticos, a estrutura cristalina dos catalisadores foi preservada.
A important technology to reduce the atmospheric pollution is the use of catalysts, to transform high pollutant as NO in other inoffensive gases to the environment. In this work, the perovskite oxides La2CuO4, LaNiO3, LaMnO3, La1,4Sr0,6CuO4, La0,7Sr0,3NiO3 e La0,7Sr0,3MnO3 were prepared through co-precipitation method and characterized by X-ray diffraction and temperature programmed reduction, nitrogen physsisorption and subsequent valued on the reduction of NO by CO and the direct decomposition of NO. These reaction were tested at 400oC and 500oC temperatures and times of reaction between 7 and 10 hours. Through the catalytic tests the La2CuO4 catalyst shown the best activity to the reduce reaction, and when the La is partially substituted by strontium all the catalyst showed a better significant for all the catalysts. The XRD analysis shown that the catalytic structure of the catalysts were preserved after the catalytic test yet.

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.

En aquesta tesi es planteja fabricar una cel·la solar nano-estructurada de perovskita utilitzant alúmina nano-porosa anoditzada (NAA en les seves sigles en anglès) com a suport. Es va escollir la perovskita perquè les cel·les solars d'aquest material han assolit una eficiència molt similar a les cel·les existents de silici. A més a més, són barates i fàcils de preparar. El fet que la cel·la estigui nano-estructurada aportarà estabilitat davant la radiació, la temperatura i la humitat, sent aquest el principal problema d'aquests dispositius. Els nano-porus de la NAA tenen una forma cilíndrica molt ben definida on la grandària es pot controlar fàcilment sent tots els nano-porus iguals, el qual permetrà un major control sobre l'homogeneïtat del material infiltrat. Per tant l'objectiu de la tesi és aplicar la tecnologia de NAA a les cel·les solars de perovskita (CSP). Per això, primer va tenir lloc un procés de familiarització amb la fabricació i caracterització de NAA, així com dels CPSs d'alta eficiència, mitjançant mètodes estàndards coneguts. Un cop es va aconseguir la fabricació de NAA amb diferents mides de porus, la capa barrera d'alúmina que existeix entre l'alumini i el fons del porus va haver de ser eliminada, per poder aprofitar l'alumini (base de la NAA) com a contacte elèctric. Pel qual es va investigar i desenvolupar un nou mètode, ja que els mètodes existents no són adequats per eliminar la capa de barrera de gruixos superiors als 200 nm. Finalment es va estudiar la infiltració dels materials que formen una CSP en els nano-porus, mitjançant mètodes simples de deposició. Es va obtenir una cel·la solar nano-estructurada de perovskita utilitzant com a suport NAA, dels quals resultats d'eficiència són humils, pel fet que l'estructura plantejada en aquest treball és totalment innovadora. Fet que obre un ampli camí per futurs treballs.
En esta tesis se plantea fabricar una celda solar nano-estructurada de perovskita utilizando alúmina nano-porosa anodizada (NAA de sus siglas en inglés) como soporte. Se eligió la perovskita ya que las celdas solares de este material han alcanzado una eficiencia muy similar a las celdas existentes de silicio. Además, son baratas y fáciles de preparar. El hecho de que la celda este nano-estructurada aportará estabilidad frente a la radiación, temperatura y humedad, siendo este el principal problema de estos dispositivos. Los nano-poros de la NAA tienen una forma cilíndrica muy bien definida cuyo tamaño se puede controlar fácilmente siendo todos los nano-poros iguales, lo cual permitirá un mayor control sobre la homogeneidad del material infiltrado. Por lo que el objetivo de esta tesis es aplicar la tecnología de NAA a las celdas solares de perovskita (CSP). Para ello primero tuvo lugar el proceso de familiarización con la fabricación y caracterización de NAA, así como de CSPs de alta eficiencia, mediante métodos estándar conocidos. Una vez se consiguió la fabricación de NAA con diferentes tamaños de poro, la capa barrera de alúmina que existe entre el aluminio y el fondo del poro tuvo que ser eliminada, para poder aprovechar el aluminio (base de la NAA) como contacto eléctrico. Para lo cual se investigó y desarrolló un nuevo método, ya que los métodos existentes no son adecuados para eliminar capa de barrera de espesores superiores a los 200 nm. Finalmente se estudió la infiltración de los materiales que forman una CSP en los nano-poros, mediante métodos simples de deposición. Se obtuvo una celda solar nano-estructurada de perovskita utilizando como soporte NAA, cuyos resultados de eficiencia son humildes, debido a que la estructura planteada en este trabajo es totalmente novedosa. Lo cual abre un amplio camino para futuros trabajos.
In this thesis, the nanostructured perovskite solar cell manufacture using nanoporous anodic alumina (NAA) as a scaffold is proposed. The perovskite was chosen since the solar cells made with this material have achieved very similar efficiency to silicon cells. Also, they are cheap and easy to prepare. The fact that the cell will be nanostructured will provide stability against radiation, temperature and humidity, this being the main problem of these devices. The NAA nanopores have a very well defined cylindrical shape, whose size can be easily controlled, all nanopores being ident, which will allow greater control over the homogeneity of the infiltrated material. Therefore, this thesis aims to apply NAA technology to perovskite solar cells (PSCs). First, the familiarization process with the manufacture and characterization of NAA, as well as of high-efficiency PSCs, through known standard methods were carried out. Once the manufacture of NAA with different pore sizes was achieved, the alumina barrier layer that exists between the aluminium and the bottom of the nanopores had to be removed, to take advantage of the aluminium (base of the NAA) as an electrical contact. For which a new method was investigated and developed since existing methods are not suitable for removing barrier layer thicknesses greater than 200 nm. Finally, the infiltration of the materials that form a PSC within the nanopores was studied, utilizing simple deposition methods. A full working nanostructured perovskite solar cell was obtained using NAA as a scaffold, whose efficiency results are modest because the structure proposed in this work is novel. Which opens a wide path for future work.

Les perovskita orgàniques/inorgàniques híbrides han atret molta atenció des que es van introduir per primera vegada en un dispositiu fotovoltaic fa deu anys, obtenint una eficiència de el 3%. Des de llavors, l’eficiència de les cel·les solars de perovskita ha augmentat fins a gairebé igualar l’eficiència de les cel·les fotovoltaiques comercials de silici. A més, permet la fabricació de dispositius flexibles a un preu reduït. A causa de les seves propietats optoelectròniques excepcionalment bones, també s’està duent a terme una intensa recerca per trobar diferents aplicacions d’aquest tipus de materials, ja sigui com a sensors, làsers o díodes emissors de llum. No obstant això, encara s’han d’abordar alguns problemes que presenten, com la inestabilitat química o estructural en condicions ambientals. Per tal de comprendre millor l’estabilitat estructural i el paper exercit per la interacció entre el catió orgànic i la xarxa inorgànica, estudiem les propietats estructurals i optoelectròniques de les perovskita de la família FAxMA1-xPbI3 a diferents pressions (fins a 15 GPa) i temperatures (de 10 a 385 K). La nostra investigació d’aquest material és realitzada per mitjà d’espectroscòpia òptica no invasiva, com fotoluminiscència (PL), Raman i elipsometría. En els articles aquí recopilats es mostra el primer diagrama de fase complet de perovskita de iodur de plom de cations mixtes (formamidinio i metilamonio), en funció de la temperatura i la composició. Aquest diagrama pot servir per avaluar la concentració relativa òptima dels cations orgànics per estabilitzar la fase cúbica pel que fa als canvis de temperatura. Aquests materials també presenten una dependència atípica del bandgap amb temperatura, que en la literatura s’atribueix exclusivament a la renormalització del gap causa de la interacció electró-fonó. No obstant això, és aquest treball mostrem que els efectes d’expansió tèrmica també juguen un paper decisiu en la dependència del gap amb temperatura. De totes les combinacions de la família de perovskita d’halur organometàl·lic, MAPbI3 és probablement el més estudiat a causa de les seves excel·lents propietats. Se sap que la interacció entre el moviment dels cations orgànics i la gàbia inorgànica rígida té un paper decisiu en l’estructura cristal·lina d’aquest material. Per exemple, a causa de el desordre dinàmic de les molècules de metilamonio, la perovskita MAPbI3 adopta una fase cúbica altament simètrica a altes temperatures. Quan es refreda, tant la contracció de la xarxa com la reducció de la simetria a causa d’una transició a una fase ortorrómbica bloquegen les molècules de MA en els buits de la xarxa inorgànica. En els articles aquí compilats observem per primera vegada un efecte similar però a temperatura ambient, aplicant pressió hidrostàtica a el material. En ambdós casos, el bloqueig dels cations de MA es pot observar indirectament a través d’una reducció dràstica dels amples de línia de fonons en els mesuraments Raman. Demostrant, d’aquesta manera, que és possible alterar les propietats vibratòries del material aplicant una pressió controlada. Finalment, la modificació del valor del bandgap i la variació de l’estructura de bandes de sistema mixt FAxMA1-xPbI3 s’avalua en funció de la composició de FA amb elipsometría i fotoluminiscència.
Las perovskitas orgánicas/inorgánicas híbridas han atraído mucha atención desde que se introdujeron por primera vez en un dispositivo fotovoltaico hace diez años, obteniendo una eficiencia de alrededor del 3%. Desde entonces, la eficiencia de las celdas solares de perovskita ha aumentado hasta casi igualar la eficiencia de las celdas fotovoltaicas comerciales de silicio. Además, permite la fabricación de dispositivos flexibles a un precio reducido. Debido a sus propiedades optoelectrónicas excepcionalmente buenas, también se está llevando a cabo una intensa investigación para encontrar diferentes aplicaciones de este tipo de materiales, ya sea como sensores, láseres o diodos emisores de luz. Sin embargo, todavía deben abordarse algunos problemas que presentan, como la inestabilidad química o estructural en condiciones ambientales. Con el fin de comprender mejor la estabilidad estructural y el papel desempeñado por la interacción entre el catión orgánico y la red inorgánica, estudiamos las propiedades estructurales y optoelectrónicas de las perovskitas de la familia FAxMA1-xPbI3 a diferentes presiones (hasta 15 GPa) y temperaturas (de 10 a 385 K). Nuestra investigación de este material es realizada por medio de espectroscopía óptica no invasiva, como fotoluminiscencia (PL), Raman y elipsometría. En los artículos aquí recopilados se muestra el primer diagrama de fase completo de perovskitas de yoduro de plomo de cationes mixtos (formamidinio y metilamonio), en función de la temperatura y la composición. Este diagrama puede servir para evaluar la concentración relativa óptima de los cationes orgánicos para estabilizar la fase cúbica con respecto a los cambios de temperatura. Estos materiales también presentan una dependencia atípica del bandgap con temperatura, que en la literatura se atribuye exclusivamente a la renormalización del gap debido a la interacción electrón-fonón. Sin embargo, es éste trabajo mostramos que los efectos de expansión térmica también juegan un papel decisivo en la dependencia del gap con temperatura. De todas las combinaciones de la familia de perovskitas de haluro organometálico, MAPbI3 es probablemente el más estudiado debido a sus excelentes propiedades. Se sabe que la interacción entre el movimiento de los cationes orgánicos y la jaula inorgánica rígida tiene un papel decisivo en la estructura cristalina de este material. Por ejemplo, debido al desorden dinámico de las moléculas de metilamonio, la perovskita MAPbI3 adopta una fase cúbica altamente simétrica a altas temperaturas. Cuando se enfría, tanto la contracción de la red como la reducción de la simetría debido a una transición a una fase ortorrómbica bloquean las moléculas de MA en los huecos de la red inorgánica. En los artículos aquí compilados observamos por primera vez un efecto similar pero a temperatura ambiente, aplicando presión hidrostática al material. En ambos casos, el bloqueo de los cationes de MA se puede observar indirectamente a través de una reducción drástica de los anchos de línea de fonones en las mediciones Raman. Demostrando, de ésta manera, que es posible alterar las propiedades vibratorias del material aplicando una presión controlada. Finalmente, la modificación del valor del bandgap y la variación de la estructura de bandas del sistema mixto FAxMA1-xPbI3 se evalúa en función de la composición de FA con elipsometría y fotoluminiscencia.
Hybrid organic/inorganic perovskites have attracted a lot of attention since they were first introduced in a working photovoltaic device ten years ago, yielding an efficiency of around 3%. Since then, the efficiency of the perovskite solar cells has risen to almost stand toe to toe with that of commercial silicon photovoltaics. Besides, it allows the fabrication of flexible devices at an inexpensive cost. Due to its exceptionally good optoelectronic properties, there is also an intense research for different applications of this type of materials, such as sensors, lasers or light-emitting diodes. However, they still present some issues that need to be addressed, such as chemical or structural instabilities under ambient conditions. In order to better understand the structural stability, and the role played by the interaction between the organic cation and the inorganic framework, we studied the structural and optoelectronic properties of perovskites of the family FAxMA1-xPbI3 at different pressures (up to 15 GPa) and temperatures (10 to 385 K). We investigated this material by noninvasive optical spectroscopy means, such as photoluminescence (PL), Raman and ellipsometry. In the articles here compiled, the first complete phase diagram of mixed cation (formamidinium and methylammonium) lead iodide perovskites is provided as a function of temperature and composition. This serves to assess the best relative concentration of the organic cations to stabilize the cubic phase with respect to temperature changes. These materials also present an atypical dependence of the bandgap with temperature, which in the literature is ascribed exclusively to a huge electron-phonon renormalization. However, here we show that thermal expansion effects also play a decisive role in the temperature behavior of the fundamental gap. From all the combinations in the family of organometal halide perovskites, MAPbI3 is probably the most studied due to its outstanding optoelectronic properties. It is known that the interplay between the movement of the organic cations and the rigid inorganic cage has a decisive role in the crystalline structure of this material. For instance, due to the dynamic disorder of the methylammonia, MAPbI3 adopts a highly symmetric cubic phase at high temperatures. When cooling down, both the contraction of the lattice and the reduction of symmetry due to a transition to an orthorhombic phase lock the MA molecules in the cage voids. We are able to observe for the first time a similar effect but at room temperature, by applying hydrostatic pressure to the material. In both cases, the locking of the MA cations can be indirectly observed through a drastic reduction of the phonon linewidths in Raman experiments. We have shown, in this way, that it is possible to alter the vibrational properties of the material by applying a controlled hydrostatic pressure. Finally, the tuning of the bandgap and the variation of the band structure of the mixed-system FAxMA1-xPbI3 is evaluated as a function of FA composition with ellipsometry and photoluminescence.

O mundo moderno é extremamente dependente de combustíveis fósseis como fonte de energia primária e essa forte dependência leva a problemas políticos, econômicos e ambientais. Como possível solução a esses problemas tem-se as células combustíveis, pois são dispositivos que geram energia elétrica limpa diretamente de reações eletroquímicas produzindo, além da energia elétrica, apenas calor e água. Logo, percebe-se que essas células são fontes de energia confiáveis, renováveis e não poluentes, que contribuem para o desenvolvimento sustentável. Devido a isso, este trabalho teve como objetivo principal a síntese (por um método inédito) e a caracterização de materiais porosos a base de cromita de lantânio, LaxSr1-xCryFe1-y(Mn1-y)O3-?, para possível implementação como material de anodo e catodo de célula a combustível de óxido sólido (SOFC). Particularmente, estudos com anodos nos quais o transporte eletrônico é feito por materiais cerâmicos ao invés de metais são a área mais promissora na pesquisa recente. Além disso, materiais a base de manganita de lantânio dopadas com estrôncio são na atualidade os materiais mais usados na construção do catodo da SOFC. Nesta tese os materiais foram sintetizados pelo método sol-gel com agentes direcionador e dilatador de estrutura, resultando em materiais porosos em forma de esponja e com a estrutura perovskita, porém com fases espúrias. Foi estudada a influência do processamento de calcinação e de dopagem sobre as estruturas cristalográficas e porosas dos materiais. A maior temperatura de calcinação favoreceu a formação da estrutura perovskita com a retenção da fase romboédrica e reduziu a presença das fases espúrias, porém reduziu a porosidade, principalmente dos menores mesoporos, e a área superficial dos materiais. Por outro lado, ao dopar o sítio B os materiais com 75 %mol de La e calcinação a 1000 °C, observou-se a formação de um maior volume de mesoporos, ao mesmo tempo, que produziu uma maior quantidade de mesoporos menores e favoreceu a retenção da fase romboédrica da estrutura perovskita. Quanto ao comportamento eletrocatalítico, as células com eletrodos confeccionados a partir de La0,33Sr0,66Cr0,33Mn0,33O3-? apresentaram os melhores resultados tanto para anodo como para catodo entre as amostras avaliadas na tese. Além do mais, foram obtidos dois materiais, um cerâmico (La0,33Sr0,66Cr0,33Mn0,33O3-?) e um compósito cerâmico (La0,33Sr0,66Cr0,33Mn0,33O3-? + ZrO2 8%mol Y2O3) bons candidatos a catodo da SOFC. Esses materiais possuem uma composição química não encontrada na literatura para tal finalidade, ou seja, são inéditos.
The modern world is extremely dependent on fossil combustibles as primary source of energy and, this dependence brings political, economic and ambient problems. As a possible solution to these problems are the fuel cells, because they are devices that generate clean electric energy directly from electrochemical reactions, producing besides electric energy, heat and water. Therefore, these cells are reliable, renewable and non-pollutant sources, that contribute to the sustainable development. Related to it, this work had the main goal the synthesis (by a new method) and characterization of porous materials based on lanthanum chromite, LaxSr1-xCryFe1-y(Mn1-y)O3-?, for possible use as anode and cathode material of Solid Oxide Fuel Cell (SOFC). In particular, studies of anodes in which the electronic transport is performed by ceramic materials instead of metals are the most promising recent research area. Moreover, materials based on lanthanum manganite doped with strontium are now a days the more used materials for SOFC cathodes. In this thesis, the materials were synthesized by the sol-gel method with directing and swelling structure agents, resulting in porous sponge materials with perovskite structure, but having spurious phases. The influence of the calcination and doping of the materials upon the crystallographic and porous structures were studied. Higher calcination temperature favored the formation of the perovskite structure and reduced the presence of spurious phases, but reduced the porosity, mainly of smaller mesopores and the surface area. On the other hand, doping the B site in materials with 75 %mol of La and the calcination at 1000 oC produced a higher mesopore volume, a higher amount of small mesopores and favored the retention of the rhombohedral perovskite structure. Regarding the catalytic behavior, the cells with electrodes of La0,33Sr0,66Cr0,33Mn0,33O3-? presented the best results as anode and cathode among the evaluate samples. Moreover, two materials were obtained, a ceramic one, (La0,33Sr0,66Cr0,33Mn0,33O3-?) and a ceramic composite, (La0,33Sr0,66Cr0,33Mn0,33O3-? + ZrO2 8%mol Y2O3), good candidates as SOFC cathodes. These materials have a chemical composition, which were not reported in the literature for this application, being unique.

Perovskites and perovskite related materials are materials that are candidates for applications such as oxygen permeable membranes, cathodes for SOFC and high-temperature oxygen sensors. This arises from the potential high ionic conductivity and the chemical stability even at low partial pressures of oxygen. From an application point of view, it is important to have knowledge about the oxygen transport properties in these materials. Oxygen transport in mixed conducting oxides involves two inherently different processes; oxygen exchange between bulk gas and surface and solid state diffusion. The objective of this work has been to obtain fundamental understanding of these transport properties in mixed ionic and electronic conductors. For that purpose two materials systems with significant differences in electronic conductivty and oxygen vacancy concentration were chosen as objectives for the investigation, viz.: Sr-substituted LaCoO₃ and Al-substituted SrTiO₃.

All transport properties (diffusion and surface exchange) have been assessed by electrical conductivity relaxation, and the work also evaluate the pros and cons using this specific method to obtain transport data for the materials in question.

In the first two papers (Paper 1 and Paper 2) transport properties are derived for La_1-xSr_xCoO_3-δ (x=0 (LC), 0.2 (LSC-02) and 0.5 (LSC-05)). In Paper 1 “chemical transport coefficients”, D_chem and k_chem, are reported. More fundamental transport coefficients, such as oxygen component diffusion coefficient (D_O) and vacancy diffusion coefficients (D_V), are also deduced and discussed. Activation energies for D_O and D_V, were determined. The activation energies for D_O varies from 279 kJ/mol for LC to 174-222 kJ/mol for LSC-02 and 90-105 kJ/mol for LSC-05, decreasing with increasing Srcontent. The activation energies for the vacancy diffusion coefficient, DV, are smaller than for the component diffusion coefficients and typical values are 77 kJ/mol for LC, 85 kJ/mol for LSC-02 and 75 kJ/mol for LSC-05, that is, almost independent of Sr-content. The enthalpies of vacancy formation decreases with increasing Sr content. The values are 206 kJ/mol for LC, 75 kJ/mol for LSC-02 and 15 kJ/mol for LSC-05, which agrees well with values reported in the literature. However, the vacancy diffusion coefficient showed an unexpected increase at high concentrations of oxygen vacancies, corresponding to δ=0.27-0.30. The phenomena with a PO₂ dependent D_V is discussed.

In Paper 2, the oxygen surface exchange coefficient, k₀, is derived from “chemical values” reported in Paper 1, and used as a basis to deduce probable reaction mechanisms associated with surface exchange. The temperature dependency plots showed that for the composition with x = 0.5, the k0 made a shift in activation energy from ~120 kJ/mol to ~15 kJ/mol above 950 °C. It is suggested that this significant shift in activation energy might be due to an oxygen adsorption/desorption mechanism on the surface becoming rate controlling at high temperatures. The composition with x=0.2 did not show this shift in activation energy. Relations between possible rate controlling reactions and reaction rates (k₀) were established, and formed the basis for discussions on probable rate controlling processes. There are reasons to assume that for oxidation prosesses a rate controlling reaction involving a direct “installation” of an oxygen molecule into two vacancies is dominating, while a dissociation of an oxygen molecule generally gives a better description for a reduction process.

In Paper 3 the oxygen transport properties in SrTi_1-xAl_xO₃ (x=0 (ST), 0.02 (STA-02) and 0.05 (STA-05)) were determined in O2/N2 mixtures. In this contribution the electrical conductivity is also presented in a large P_O2- interval (O₂/N₂- and CO/CO₂-mixtures). Electrical conductivity for pure SrTiO₃ (ST) in terms of P_O2 applied well with defect chemistry reported in the literature. For the two Al-substituted compositions the electrical conductivity followed predicted behaviour at high and low P_O2’s. However, in the medium P_O2 range we were not able to describe the conductivity behaviour in terms of classical defect chemistry. Reasons for the discrepancy is discussed.

D_chem for ST and STA-02 are reported and are, along with their corresponding activation energies, 187 and 104-180 kJ/mol, respectively, in good accordance with values from literature. Furthermore, values for the component diffusion coefficient, D_O, and the vacancy diffusion coefficient, D_V, are reported for ST at 950 °C, the only composition where oxygen vacancy concentrations are available in the literature. Values for kchem in STA-02 and STA-05 are also reported, and show pronounced P_O2 dependencies. For STA-05 the activation energy for k_chem is found to vary between 90 and 105 kJ/mol. Due to a high uncertainty, activation energies are not reported for STA-02.

Reported D_chem and k_chem values for related materials in literature indicate increasing numeric values with decreasing concentration of oxygen vacancies. It is reasoned that this is due to an ever increasing thermodynamic factor with decreasing population of vacancies. The implications for the component diffusion coefficient is discussed.

In Paper 4 the oxygen transport properties in SrTiO₃ pure and with Al were investigated in mixtures of CO/CO₂. D_chem are reported for ST and STA-02 while k_chem are reported for ST, STA-02 and STA-05. The D_chem showed a P_O2-dependency, which can be explained by the variation in the thermodynamic factor. The introduction of Al in the sample increases the value of D_chem, probably due to the introduction of more oxygen vacancies. STA-02 showed a discrete increase in D_chem in the CO-rich atmospheres, this may be due to phase transition or phase separation at P_O2 ~10^-17 atm. The k_chem showed a maximum at P_CO/P_CO2 = 1 for STA-02 and STA-05. This behaviour corresponds well with a rate controlling reaction involving a charged and adsorbed CO₂ molecule. The same maximum is also reported in the literature for BaTiO₃ wihtout and with 1.8 % Al and for La_0.9Sr_0.1FeO₃.

This work has examined chemical diffusion and surface exchange coefficients with electrical conductivity relaxation in two material systems with distinct differences in electrical conductivity and oxygen vacancy concentrations. The main focus has been to elucidate properties of the transport coefficients based on own measurements, but also include transport coefficients from other material systems from literature as references. The vacancy diffusion coefficients have been examined, showing that they increase with increasing concentration of oxygen vacancies in materials where the concentration of vacancies is high. No obvious reason for this behaviour has been found, however, it may be related to a change in activation energy. It is rather well established in the literature that for materials where the concentration of vacancies may be characterized as dilute, we should expect a D_V independent of the population of vacancies. Finally, based on own results and data reported in the literature it appears that with respect to the oxygen surface flux the oxygen vacancy concentration seems to be the property of most importance. That is, for oxidation processes the oxygen exchange flux will increase with vacancy population.

Orientador: Pascoal Jose Giglio Pagliuso
Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin
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Resumo: Um grande número de óxidos de metais de transição se forma em estrutura perovskita simples ou em uma de suas variantes, e muitos deles apresentam propriedades físicas interessantes, como supercondutividade, magneto-resistência colossal e ferroeletricidade. Uma das variantes da estrutura perovskita simples, a perovskita dupla ordenada (PDO), pode se cristalizar em simetria cúbica ou em variantes distorcidas, e possui fórmula geral A2B¿B" O6, em que o íon A ocupa os vértices do cubo enquanto os cátions B¿ e B¿¿ se alternam nos centros dos octaedros de oxigênio. Dentre os compostos com estrutura perovskita dupla já reportados na literatura, Sr2FeRe O6e Sr2FeMoO6são particularmente interessantes devido à suas interessantes propriedades físicas e à sua potencialidade como dispositivos magneto-eletrônicos. As propriedades estruturais, de transporte e magnéticas desses materiais estão altamente conectadas, e acredita-se que essas propriedades das PDO sejam fortemente dependentes do grau de hibridização dos orbitais d dos cátions B" (ex.: Re e Mo). Portanto, para se comprovar a potencialidade dos compostos PDO como dispositivos magnetoeletrônicos, além entender os mecanismos microscópicos responsáveis por suas propriedades magnéticas e eletrônicas, é essencial que se investigue em detalhes outros exemplos de PDOs que possam confirmar as idéias correntes propostas na literatura. Nesse trabalho descrevemos o processo de síntese e as propriedades físicas da série inédita Ca2-xL axFeIrO6, onde o Ir, assim como o Re e o Mo, é metal de transição, no caso com caráter 5d, e pode possuir diferentes estados de valência. Espectros de difração de raios-x e Refinamento Rietveld mostraram que os compostos da série se cristalizam em uma estrutura monoclínica, com grupo espacial P21/n, com uma grande presença de desordem catiônica nos sítios Fe/Ir. Medidas de magnetização indicaram que, aparentemente, os compostos tendem a evoluir de antiferromagnéticos nas extremidades da série, x = 0 e x = 2, para ferromagnéticos em regiões intermediárias da série. Medidas de espectroscopia Mössbauer mostraram que a valência do ferro é +3 ao longo da toda série, de modo que, possivelmente, a mudança na natureza das interações magnéticas estaria sendo causada pela alteração da valência do Ir devido a dopagem com La. Medidas de calor específico revelaram uma anomalia característica de uma transição magnética somente para a mostra de x = 0. Foram feitas medidas de resistividade em função da temperatura, em que se observou que os materiais apresentam comportamento isolante e praticamente nenhum efeito magneto-resistivo. Para as amostras no centro da série (em torno de x = 1,0) a presença de loops de histerese nas curvas MxH e um comportamento irreversível nas curvas de MxT sugerem uma competição entre fases ferrimagnéticas e antiferromagnética para esta região de concentração. Qualitativamente, nossos resultados podem ser interpretados considerando-se a mudança de valência do Ir, as regras de Goodenough-Kanamori-Anderson e a presença de desordem catiônica
Abstract: Perovskite structure and its variants host a great number of transition metals oxides that present a variety of interesting physical properties such as superconductivity, ferroelectricity and colossal magneto-resistance. A variant of the simple perovskite structure, the ordered double perovskite (ODP), also can grow in cubic (or lower) symmetry, with a general formula A2B¿B" O6, where the cation A occupies the vertices of the cube while B¿ and B" sits alternately at the center of the oxygen-octahedron. Among the compounds with ordered double-perovskite structure, Sr2FeReO6 and Sr2FeMoO6 are particularly interesting due to their interesting physical properties and their potentiality as magneto-electronic devices, having highly connected structural, transport and magnetic properties. It has been proposed that the magnetic and conducting ground states of ODP systems are strongly dependent on the delocalization level of the cation B" 5d electrons (ex: Re, Mo). However in order to prove the potentiality of composites ODP as magnetoeletronics devices, and to understand the microscopical mechanisms responsible for its magnetic and electronic properties, it is necessary to further investigate other examples of ODP that can confirm the current ideas proposed in literature. In this work we have synthesized and studied the Ca2-xLaxFeIrO6 series, where Ir, as well as Re and Mo, is transition metal with a 5d character which can possess different valence states. X-rays diffraction spectra and Rietveld Refinement analyses have shown that the Ca2-xLaxFeIrO6 compounds series crystallized in a monoclinic structure, space group P21/n, with an unavoidable cationic Fe/Ir site disorder. Measurements of temperature/field dependent magnetization have indicated that the magnetic interactions in these compounds evolves from antiferromagnetic in the extremities of the series, x = 0 and x = 2, for ferromagnetics in intermediate regions of the series. Mössbauer spectroscopy measurements revealed that the valence of the Fe is +3 in the whole series, in a way that the change in the nature of the magnetic interactions can be possibly caused by the variation of Ir valence due the La doping. Specific heat measurements have revealed an anomaly associated to a magnetic phase transition only for the x = 0 compound while measurements of electrical resistivity as a function of the temperature have shown insulating behavior and absence of magneto resistance for all studied samples. For the samples with x ~ 1.0, the presence of ferromagnetic loops and ZFC and FC hysteresys in the MxT curves indicates the competition between ferrimagnetic and antiferromagnetic phases in a disordered system. Qualitatively, all our results can be understood in terms of a valence changes in the Ir ions, the Goodenough-Kanamori-Anderson rules and the role of cationic disorder
Mestrado
Física da Matéria Condensada
Mestre em Física

Neste trabalho foram avaliadas as atividades de catalisadores do tipo perovskita LaNi1-xCoxO3 frente à reação de reforma a vapor de etanol. Devido à baixa área superficial, característica de óxidos do tipo perovskita, esses foram suportados em SiO2, Al2O3 e ZrO2, a fim de verificar o efeito do suporte na atividade catalítica.
Os catalisadores foram preparados pelo método da co-precipitação e caracterizados por espectrometria de emissão atômica por plasma induzido, difração de raios X pelo método do pó, adsorção de nitrogênio pelo método B.E.T, redução a temperatura programada e espectroscopia de absorção de raios X.
Para estudar o processo de redução e a possibilidade de oxidação durante a reação catalítica, foram realizados estudos in situ da reação de reforma a vapor, através da espectroscopia de absorção de raios X. Estes dados foram comparados com os resultados de aplicação das técnicas de RTP e DRX às amostras parcial e totalmente reduzidas e foi proposto um mecanismo de redução do óxido do tipo perovskita durante o processo de ativação do catalisador.
Todos os catalisadores mostraram-se ativos nas reações de reforma a vapor de etanol e a seletividade dos produtos foi dependente do tipo do catalisador avaliado. De acordo com os resultados obtidos, destaca-se o catalisador não suportado LaNiO3, com conversão de etanol de 99% e seletividade para H2, CO e CO2 de 4,8; 1,1 e 1,3, respectivamente. Além disso, o ensaio com dois catalisadores simultâneos (LaNiO3 + LaCoO3) foi o que apresentou melhor estabilidade na reação, com 100% de conversão de etanol e seletividade semelhante à obtida pelo catalisador LaNiO3.
In this work, the catalytic activity of perovskite oxides, LaNi1-xCoxO3, was evaluated in the ethanol steam reforming. Due to the low surface area, characteristic of perovskite oxides, these catalysts were supported on SiO2, AI2O3 and ZrO2 and the effect of the support was evaluated. The catalysts were prepared by the co-precipitation method and characterized by Atomic Induced Plasma Spectroscopy, X-Ray Powder Diffraction (XRD), Nitrogen adsorption by B.E.T. method, Temperature Programmed Reduction (TPR) and X-ray Absorption Near Edge Structure (XANES).
The catalytic process was accompanied by XANES in situ to verify changes in the oxidation state of the active phase during the activation process with H2 and also during the process of steam reforming of ethanol. By relation of these results with TPR and XRD, for samples partially and fully reduced, it was proposed a mechanism for the reduction of the perovskite oxides during the conditions of activation.
All catalysts showed activity for the ethanol steam reforming with the selectivity dependent of the catalyst evaluated. Summarizing, the results showed that the unsupported catalyst LaNiO3 presented the better performance, with the ethanol conversion of 99% and selectivity for H2, CO and CO2 of 4.8; 1.1 and 1.3, respectively. Moreover, the test using two simultaneous catalysts (LaNiO3 + LaCoO3), showed better stability in the reaction, presenting ethanol conversion of 100% and selectivity to H2, CO and CO2 similar to the LaNiO3 catalyst.

Orientador: Alexandre Mesquita
Resumo: O titanato de cálcio CaTiO3 é um material com estrutura de tipo perovskita que tem sido aplicado como luminóforo. É bem estabelecido que a inserção de íons de terra rara no sítio ocupado pelo Ca2+ provoca mudanças significativas nas suas propriedades estruturais e produz efeitos luminescentes na faixa do visível. Entretanto não existem trabalhos reportando a inserção do La3+ no sítio do Ca2+ no que se refere às características estruturais e luminescentes desses materiais. Portanto, o presente trabalho estuda as propriedades fotoluminescentes apresentadas pela matriz à base de titanato de cálcio dopada com praseodímio, lantânio e alumínio. O material foi sintetizado a partir do método Pechini, que se mostrou um método eficaz na preparação de acordo com a caracterização estrutural realizada. A técnica de difração de raio X permitiu identificar que todas as amostras de CaTiO3 apresentam-se na fase cristalina com simetria ortorrômbica. Através da espectroscopia de absorção de raio X na borda K do Ti4+ constatamos a ocorrência de maior simetria do Ti4+ em relação aos átomos ao seu redor quando aumentamos a temperatura de calcinação e que a substituição de íons no sítio do Ca2+ não altera essa simetria. Em razão do aumento da concentração dos dopantes, tanto no sítio do Ca2+ quanto no sitio do Ti4+, foram observados alterações nos modos de vibração dos espectros Raman. Constatou-se o aumento da torção entre os octaedros de TiO6 em relação ao aumento da concentração dos dopantes. No... (Resumo completo, clicar acesso eletrônico abaixo)
Abstract: The calcium titanate CaTiO3 is a perovskite structure material which has been used as phosphor. It is well established that the incorporation of rare earth ions in the place occupied by Ca2+ cause significant changes in their structural properties and produce luminescent effects in the visible range. However, there are no studies reporting the insertion of La3+ on the Ca2+ site with respect to structural and luminescent characteristics of these materials. So, this work studies the photoluminescent properties presented by the matrix based on calcium titanate doped with praseodymium, lanthanum and aluminum. The material was synthesized by the Pechini method, which proved an effective method of preparation according to the structural characterization performed. The technique of X-ray diffraction showed that all samples are organized and exhibit orthorhombic symmetry. Using X-ray absorption spectroscopy at the K edge of Ti4+, we found that the occurrence of major symmetry of Ti4+ with respect to the neighbor atoms when the calcination temperature was increased and that the substitution of ions Ca2+ by Pr3+ does not change this symmetry. With the concentration of dopants increasing at the Ca2+ and Ti4+ sites, changes of the vibration modes in the Raman spectra were observed. It was found an increased torque between the TiO6 octahedra as a function of the increase in concentration of dopants. In the luminescence spectra, increasing the structural defect density enhanced the light e... (Complete abstract click electronic access below)
Mestre

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES
Oxides with perovskite structure have been objects of intense study since their discovery in 1839 and are still being widely studied due to richness and diversity of physical properties present in these materials, including a wide range of important magnetic properties both from a scientific point of view as technological. It is known that the magnetic properties of these materials are very sensitive to the effects of substitution of chemical doping elements and their structure as well as the preparation method used to obtain it. In this work, we do a detailed study of the effects of heat treatment on structural and magnetic properties of the compound pure and doped LaCrO3 with Sr and Mn. The compounds studied here were obtained by the combustion method. It was possible by XRD measurements to identify peaks of desired phase on some samples after combustion. However, heat treatments were conducted at 300 ° C / 1h, 400 ° C / 1h, 500 ° C / 1h, 600 ° C / 1h, 700 ° C / 1h and 800 ° C / 1h in order to eliminate the peaks of the secondary phases and to evaluate the effects of heat treatment on structural and magnetic properties. Through the magnetization as a function of temperature and the magnetic field can be seen that the inclusion of Sr and Mn induces an increase in spontaneous magnetization at 5K and may lead to positive values Weiss temperature, suggesting a shift in antiferromagnetic (AFM ) order present in LaCrO3 compound to a ferromagnetic order (FM). We also show a large dependence of the magnetic properties of these materials with annealing temperature.
Os óxidos com estrutura perovskitas já foram objetos de intensos estudos desde a sua descoberta em 1839 e ainda continuam sendo muito estudados devido a riqueza e diversidade das propriedades físicas presentes nestes materiais, incluindo uma vasta gama de propriedades magnéticas importantes tanto do ponto de vista científico quanto tecnológico. Já é conhecido que as propriedades magnéticas destes materiais são muito sensíveis aos efeitos de substituição e dopagem dos elementos químicos de sua estrutura bem como ao método de preparação usado para obtê-lo. Neste trabalho fazemos um estudo detalhado dos efeitos do tratamento térmico nas propriedades estruturais e magnéticas do composto LaCrO3 puro e dopado com Sr e Mn. Os compostos aqui estudados foram obtidos pelo método da combustão. Foi possível através de medidas de DRX identificar picos da fase desejada em algumas amostras logo após a combustão. No entanto, foram realizados tratamentos térmicos a 300°C/1h, 400°C/1h, 500°C/1h, 600°C/1h, 700°C/1h e 800°C/1h com o objetivo de eliminar os picos referentes às fases secundárias e avaliar os efeitos dos tratamentos térmicos nas propriedades estruturais e magnéticas. Através das medidas de magnetização como função da temperatura e do campo magnético podemos verificar que a inclusão do Sr e do Mn induz um aumento da magnetização espontânea a 5K e podem levar a valores positivos da temperatura de Weiss, sugerindo uma mudança de ordenamento antiferromagnético (AFM) presente no composto LaCrO3 para um ordenamento ferromagnético (FM). Mostramos ainda uma grande dependência das propriedades magnéticas destes materiais com a temperatura de tratamento térmico.

Depuis 5 ans, les pérovskites hybrides organiques-inorganiques sont apparues comme une nouvelle classe de semiconducteurs possédant des propriétés optoélectroniques très intéressantes pour les dispositifs photovoltaïques et émetteurs de lumière. Cette thèse porte sur une étude expérimentale de spectroscopie optique, qui s’inscrit dans le champ d’exploration des propriétés optiques et des effets excitoniques des pérovskites hybrides CH3NH3PbX3 avec X = I ou Br. Nous avons étudié les propriétés optiques de couches minces déposées par spin-coating et de monocristaux élaborés en solution. Les couches minces présentent une structure granulaire et une densité élevée de défauts qui induisent une grande variabilité des propriétés optiques. L’étude des monocristaux nous a permis de mettre en évidence les propriétés intrinsèques du matériau : émission d’excitons libres, couplage électron-phonon, dynamique de recombinaison des porteurs de charge. De plus, nous avons exploré l’impact de la transition de phase orthorhombique-tétragonale sur les propriétés optiques de CH3NH3PbI3. Enfin, nous avons quantifié l’effet de la réabsorption sur les propriétés d’émission des pérovskites hybrides. L’estimation précise de cet effet est particulièrement importante pour l’interprétation des propriétés optiques des pérovskites hybrides et explique la grande hétérogénéité des résultats dans la littérature
In the last five years, hybrid organic-inorganic perovskites have emerged as a novel class of semiconductors owing to their interesting electronic and optical properties for photovoltaic and light-emitting devices. This thesis reports an experimental study using optical spectroscopy to explore the optical properties and excitonic effects of hybrid perovskites such as CH3NH3PbX3 with X = I or Br.We studied the optical properties of spin-coated thin films and solution processed single crystals. Thin films present a granular structure and a high density of defects which induce a great variability of the optical properties. The study of single crystals allows us to highlight the intrinsic properties of material: free exciton emission, electron-phonon coupling and charge carriers recombination dynamics. Besides, we have investigated the impact of the orthorhombic-tetragonal phase transition on the optical properties of CH3NH3PbI3. Finally, we have quantified the effect of reabsorption on the emission properties of hybrid perovskites. The accurate estimate of this effect is particularly important for the interpretation of the optical properties of hybrid perovskites and explains the great heterogeneity of the results in the literature

El análisis químico de los meteoritos que más se parecen a la materia que dio lugar a la formación de la Tierra revela que la concentración del gas xenón en la atmósfera de nuestro planeta es menor de la que se debería esperar. Investigaciones recientes parecen indicar que el origen de esta deficiencia podría estar relacionado con la solubilidad de los gases nobles en las vacantes de oxígeno de la estructura perovskita del silicato de magnesio, MgSiO3, principal componente del manto terrestre.
The chemical analysis of the meteorites considered to resemble closely the primordial matter which led to the formation of the Earth indicates that the concentration of xenon gas in our atmosphere is lower than expected. It seems that this deficiency is related to the noble gases’ solubility in the oxygen vacancies present in the perovskite structure of magnesium silicate, MgSiO3, the main constituent of the Earth’s mantle.

Orientador: Eduardo Granado Monteiro da Silva
Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin
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Resumo: Essa dissertação de Mestrado descreve medidas de Espectroscopia Raman realizadas em dois sistemas de perovskitas, Sr2CrReO6 e Ba1-xLaxTi0,5Mn0,5O3. Na perovskita Sr2CrReO6 dupla foram feitas medidas em um intervalo de temperaturas entre 30 K e 700 K. Foi observado um endurecimento anômalo e recorde do modo de respiração dos octaedros de oxigênio sobre os metais de transição abaixo da temperatura de ordenamento ferrimagnético dos spins de Cr e Re, Tc~600K. Tal fenômeno é explicado em termos de uma nova excitação coletiva à qual atribuímos o nome de ¿spin-elétron-fônon¿. No sistema Ba1-xLaxTi0,5Mn0,5O3 é feita uma série de medidas para x=0.0, 0.2, 0.3, 0.4 e 0.5. Para cada valor de x foi variada a temperatura de 30 K até 300 K e o mostramos que a mudança de temperatura não induz nenhuma transição de fase estrutural. No entanto, o espectro Raman mostra uma evolução em função de x que é interpretada como uma transição de fase causada por um aumento da desordem ocupacional nos sítios de Ti e Mn induzida pela dopagem de La
Abstract: This Master¿s thesis describes Raman spectroscopy measurements performed on two perovskitas systems, Sr2CrReO6 and Ba1-xLaxTi0,5Mn0,5O3. In the double perovskite Sr2CrReO6 Raman spectra were measured as a function of temperature in the range from 30 K to 700 K. A record-high anomalous hardening at the frequency of breathing mode of the oxygen octaedra over the transition-metals ions was observed below the ferrimagnetic ordering temperature of the Cr and Re spins. This phenomenon is explained in terms of a new collective excitation which we term \\\"spin-electronphonon\\\". In the system Ba1-xLaxTi0,5Mn0,5O3 a series of Raman spectra was measured for x = 0.0; 0.2; 0.3; 0.4 and 0.5. For each composition the temperature was varied from 30 K to 300 K and we showed that, at least in the studied range temperature variation does not induce any structural transition. However, the Raman spectrum shows an evolution with x which is interpreted as a phase transition caused by increase in occupational disorder in the Ti and Mn sites induced by La dopping
Mestrado
Física
Mestre em Física

Materiais dielétricos para operação em microondas constituem um ponto importante para usos em sistemas de comunicação móvel/via satélite, incluindo sistemas de monitoramento terrestres, internet/telefonia para celulares, internet das coisas, além do interesse militar para elaboração de radares. Avanços importantes nesse setor tecnológico só foram outorgados, graças ao emprego ostensivo de ressoadores dielétricos (RDs). Esses dispositivos constituem cerâmicas óxidas com baixa perda dielétrica em microondas, com demanda para sua miniaturização. O sistema deverá possuir alta constante dielétrica nesse intervalo e o dispositivo deve ser termicamente estável, ou seja, suas propriedades dielétricas não se alterarão com a temperatura. A busca por materiais de alto desempenho resultou na descoberta das perovskitas ordenadas 1:1 e 1:2, com estequiometria A2BBO6 e A3BB2O9, respectivamente. Tais sistemas ordenam o sítio B, da perovskita ABO3, gerando o empilhamento dos planos cristalinos com B e B, intercalados e na direção [1 1 1]c. Os resultados da literatura mostram que o ordenamento possui papel fundamental na obtenção de ressoadores de baixa perda dielétrica. Ademais, poucos estudos reportam as propriedades dos sistemas contendo os cátions Ca e Nb, no sítio B. Portanto, essa tese dedicou-se à investigação das propriedades dielétricas do sistema Ba3CaNb2O9 e, posteriormente, a modificação desse com a substituição dos cátions Ba2+ por Sr2+ e La3+. As amostras foram preparadas pelo método de reação do estado sólido e, posteriormente, caracterizadas pela difração de raios X, espalhamento Raman, espectroscopia de impedância e desempenho em microondas, além de técnicas complementares como análise térmica, densidade por imersão e microscopia eletrônica de varredura. Os resultados demonstraram a coexistência dos domínios 1:1 e 1:2 no sistema Ba3CaNb2O9, sendo possível manipulá-los mediante condições da sinterização. Microestruturalmente, esses domínios são regiões no cristalito com diferentes ordens catiônicas e, assim, com propriedades cristalográficas e vibracionais diferentes. Pela impedância, notou-se que o ressoador Ba3CaNb2O9 tende a conduzir mais quando possui uma tendência para o domínio 1:1. Tal resultado foi confirmado em microondas, onde a redução da perda dielétrica foi correlacionada à diminuição do domínio 1:1 na estrutura cristalina dos ressoadores. Na solução sólida com Sr2+, uma transição da fase trigonal D3d3 para monoclínica C2h3 foi detectada nos pós-calcinados, sendo oriunda das inclinações octaédricas do sistema de Glazer a0b-b-. As cerâmicas desse sistema foram sinterizadas a 1500 °C por 26 h, cujo resultado ilustrou uma tendência à ordem 1:1 para x ≥ 0,30. No sistema com La3+, observou-se, além da coexistência, os monodomínios 1:1 e 1:2. O sistema com monodomínios 1:1, BaLaCaNbO6 (y = 0,50), evidenciou uma distorção monoclínica intrínseca. Esta distorção foi associada às inclinações octaédricas do sistema de Glazer a0b-b-, reduzindo a simetria da fase cúbica Oh5 para monoclínica C2h3. Por fim, o desempenho como ressoador dielétrico dos sistemas BaLaCaNbO6 e Ba3CaNb2O9 foi avaliado. O primeiro sistema mostrou os seguintes valores: permissividade relativa εg ∼ 26, Qu × fR ∼ 10.506 GHz e coeficiente τf ∼ -55 ppm.K-1. O segundo sistema revelou os dados: permissividade εg ∼ 43, Qu × fR ∼ 15.752 GHz e o coeficiente τf ∼ 278 ppm.K-1.
Dielectric materials for microwave applications play an important role in mobile and satellite communication systems, including terrestrial monitoring, internet/mobile devices, internet of things, as well as the military uses as the radar developments. Advances in this technological field were only possible due to the ostensive use of dielectric resonators (DRs). These devices constitute oxide ceramics with a low dielectric loss in microwave frequency. The system must have high dielectric constant and such a device must be thermally stable. The search for highperformance materials granted the discovery of 1:1 and 1:2 ordered perovskites, with general formula A2BBO6 and A3BB2O9, respectively. These systems depict the B-site ordering of ABO3 perovskite, inducing the crystalline planes stacking in the [1 1 1]c direction. The literature results showed that the ordering plays an essential role in the low loss ceramics. Moreover, few studies reported the features of the systems containing the Ca and Nb cations at the B-site. Therefore, our work drives the dielectric properties of the Ba3CaNb2O9 system and, then, the modification induced by Ba2+ substitution by Sr2+ and La3+. The samples were prepared by the conventional solid-state reaction method and probed by X-ray diffraction, Raman scattering, impedance spectroscopy and microwave performance, as well as other techniques such as thermal analysis, density measurement, and electron microscopy. Our findings elucidated the coexistence of 1:1 and 1:2 domains in Ba3CaNb2O9 ceramics, being possible to manipulate them by sintering conditions. Such an ordered domain denotes regions in the crystallites with different cationic order and with different crystallographic and vibrational behavior. By the impedance spectroscopy, it was observed that Ba3CaNb2O9 ceramics tend to conduct more when they present a tendency towards the 1:1 domains. The earlier result was also confirmed in microwave frequency, in which the dielectric loss decreasing was correlated to the decrease of the 1:1 domain in the crystal structure. In the strontium solid solution, a transition from the D3d3 trigonal phase to the C2h3 monoclinic one was noted in powder samples, being derived from octahedral tilting (a0b-b- Glazer system). In the lanthanum system, besides the coexistence, the monodomains 1:1 and 1:2 were observed. Otherwise, the 1:1 monodomain system, BaLaCaNbO6 (y = 0.50), exhibited an intrinsic monoclinic distortion. This distortion was ascribed to the octahedral tilting (a0b-b- Glazer system), lowering the crystal symmetry from Oh5 cubic phase to the C2h3 monoclinic phase. The dielectric resonator performances of the BaLaCaNbO6 and Ba3CaNb2O9 systems were evaluated. The first system showed the following values: permittivity εg ∼ 26, Qu × fR ∼ 10.506 GHz and coefficient τf ∼ -55 ppm.K-1. The second system exhibited the data: permittivity εg ∼ 43, Qu × fR ∼ 15.752 GHz and coefficient τf ∼ 278 ppm.K-1.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
Recentemente, vem sendo desenvolvido o uso de catalisadores de metais preciosos suportados por óxidos do tipo perovskita em automóveis. Tais sistemas catalíticos são conhecidos como catalisadores Inteligentes. A tecnologia dos catalisadores inteligentes aponta para um novo futuro na catálise automotiva e surge como um promissor substituinte para os catalisadores convencionais. O entendimento dos principais fatores que levam a auto regeneração destes catalisadores é um passo fundamental no processo de evolução desta tecnologia. O mecanismo de auto regeneração é responsável diretamente pelo aumento considerável do tempo de vida útil destes catalisadores perante aos convencionais. Consequentemente, o seu custo é bem mais baixo comparado ao convencional. Outro fator relevante é a durabilidade estrutural e o grande número de possibilidade de combinações possíveis das perovskita que fazem delas excelentes estruturas para estudo. O objetivo do trabalho é entender o processo auto regenerativo do catalisador automotivo a base de perovskita dopadas com um átomo de cobalto, manganês e níquel e quando expostas a um ambiente com uma molécula de NO e CO , através da análise da interação desses átomos dopantes em relação a estrutura da perovskita e como se comportará o átomo de paládio ao entrar em contato com a molécula de NO e CO
Has been recently developed the use of precious metal catalysts supported on perovskite oxides in automobiles . Such catalyst systems are known as Smart catalysts. The technology of smart catalysts points to a new future in automotive catalysis and appears promising as a replacement for conventional catalysts . The understanding of the main factors that lead to self regeneration of these catalysts is a key step in the evolution of this technology process. The mechanism of self regeneration is directly responsible for the substantial increase in the lifetime of these catalysts towards the conventional . Consequently , the cost is much lower compared to the conventional . Another relevant factor is the structural durability and the possibility of large number of possible combinations of perovskite structures that make them excellent for estudo.o objective is to understand the self regenerative process of the automotive catalyst based perovskite doped with a cobalt atom , MN and nickel and when exposed to an environment with a molecule of NO and CO , by analyzing the interaction of these dopant atoms relative to the perovskite structure and behaves as the palladium atom on contact with the molecule of NO and CO

This work deals with preparation of layers of ceramic materials – perovskites. The introductory part includes general characteristics concerning structure, properties and use of this materials. In details then there is described method of their preparation, namely Pechini´s syntheses, which are most widely used. Optimum molar ratio of components is discussed, in the sense of what compositions lead to creation of perovskite structures. Influence of this parameter on rheological properties of precursory gels is described in the end of the first part of work. In experimental section there are described preparations of gels, which are prepared via reaction between citric acid and ethylene glycol and gels, which are prepared by Pechini´s synthesis. Rheological properties of prepared gels (density, viscosity and surface tension) and besides determination of amount of nitrates in gels are characterized. Temperature dependence of viscosity of gels, that are prepared by reaction of citric acid and ethylene glycol are determined. In final part successful preparations of perovskite layers is shown on ceramic substrate. This layers are observed by means of light optical microscope and scanning electron microscope.

The world is facing a climate crisis and to be able to solve it society needs to decrease the use of fossil fuels and find renewable alternatives. Solar energy is a great contender for a renewable energy source since it can be harvested for eternal time. One of the problems with the solar cells available today is that they are more expensive than fossil alternatives, and the process of making them still uses a lot of resources and energy. However, in the last decade an alternative has arisen; perovskite solar cells. Due to the fact that perovskite solar cell production uses less energy and resources than the current silicon solar cell, perovskite solar cells are more cost effective. The main problem with perovskite solar cells is that they are too unstable and do not last very long. One way to stabilize them is to introduce one more cation and make hybrid perovskites. The purpose of this project was to synthesize a perovskite material with the chemical formula AA’PbI3 (A = Cs, A’ = dimethylammonium or ethylammonium) to see if any of the compositions would generate a stable black cubic phase, which is the optimal phase of the perovskite. Mesoporous N-I-P solar cells were created by a layer by layer deposition method. The perovskite layer was added using a spin-coater to deposit the perovskite solution. The films were then characterized using XRD and UV/Vis absorption spectroscopy. Due to the coronavirus pandemic of 2020, the hole transport material and gold electrode were not added to the solar cell. As a consequence of this, not all of the compositions were synthesised which also means that the results are not conclusive. It was observed that all of the films were yellow, which indicates that none of the perovskites achieved a cubic structure. An explanation could be that some parts of the synthesis needs to be done inside a glove box where the environmental variables like humidity could be controlled. The XRDs show that some films had the expected perovskite composition, while some perovskites had decomposed into its starting materials. For hybrid components and pure ethylammonium perovskite film it was harder to confirm our conclusion since no characterization of single crystals was available for these components. However, it was determined that the addition of cesium did make the perovskites more stable.

The Master‘s thesis deals with the topic of perovskite solar cells with the main focus on the materials used for the active layer. In the introductory part, the electrical and optical properties of halide perovskites are described and specific examples of perovskite crystals are introduced. The description of impedance and photoimpedance measurement methods used for characterization of perovskite solar cells is also included in the thesis. The measurement of electrochemical impedance spectroscopy was conducted on four perovskite crystals and equivalent circuit was formed to fit the obtained data. Parameters of the circuit elements were acquired using the fitting method and were further evaluated in experimental part of this thesis.

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In recent years, research has increased in order to develop new materials processing methods have more advantages over conventional methods currently used which are quicker and cheaper. It has become common to use ceramics to obtain electronic devices, dielectric or piezoelectric. The CaTiO3 ceramic material has been widely used in electronic devices. The objective of this study was to synthesize and characterize perovskite ceramic-based CaTiO3 (Titanate Calcium) replaced with rare earths. The synthesis and replacement of perovskite were made from the starting materials Ca(OH)2, TiO2, Er2O3 and Yb2O3 by mechanical milling in a ball mill for 30 min at 250 rpm to homogenization and then was taken calcination in a muffle furnace. The obtained material powder showed perovskite phase to the orthorhombic space group Pbnm 62. The unit cell of the crystal lattice parameters showed a = 5.378 Å, b = 5.441 Å and c = 7.640 Å for the CaTiO3, which has four per unit cell formula. The number and type of modes provided for each frame can be given by the factor groups having a total of 24 vibrational modes Raman for CaTiO3 with said structure. The morphological characteristics were observed for the samples CTO (calcium titanate) prepared by solid state reaction, demonstrating the formation of small, round grain vacancies, which may be caused by distortions in the crystal lattice. The CTO replaced with Er2O3 and Yb2O3 showed typical bands of green light at 525 and 547 nm corresponding to the transition 4H11/2 → 4I15/2. The two smaller emission bands in the red, correspond to transition 4F9/2 to the ground state 4I15/2. The results obtained for the ceramic systems were satisfactory as the method used for synthesis, who presented with lower cost compared to existing processes.
Nos últimos anos, as pesquisas têm aumentado com o propósito de desenvolver novos métodos de processamento de materiais que apresentem mais vantagens em relação aos processos convencionais utilizados atualmente e que sejam mais rápidos e baratos. Tem se tornado comum utilizar cerâmicas para a obtenção de dispositivos eletrônicos, dielétricos ou piezoelétricos. O material cerâmico CaTiO3 tem sido amplamente utilizado em dispositivos eletrônicos. O objetivo deste trabalho foi sintetizar e caracterizar cerâmicas perovskitas à base de CaTiO3 (Titanato de Cálcio) substituída com terras raras. A síntese e a substituição da perovskita foram feitas à partir dos materiais de partida Ca(OH)2, TiO2, Er2O3 e Yb2O3 por moagem mecânica em um moinho de bolas por 30 min, a 250 rpm para homogeneização e em seguida, foi feita calcinação em um forno tipo mufla. O pó obtido do material apresentou fase de perovskita com grupo espacial ortorrômbica Pbnm 62. A célula unitária da rede cristalina apresentou os parâmetros a=5,378 Å, b=5,441 Å e c=7,640 Å para o CaTiO3, a qual possui quatro fórmulas por célula unitária. O número e tipo de modos previstos para cada estrutura pode ser dado pelo fator de grupos, havendo um total de 24 modos vibracionais Raman para o CaTiO3 com a estrutura citada. Foram observadas as características morfológicas para as amostras de CTO (Titanato de Cálcio), preparadas por reação no estado sólido, demonstrando a formação de grãos pequenos e redondos com vacâncias, que podem ser causadas por distorções na rede cristalina. O CTO substituído com Er2O3 e Yb2O3 apresentou bandas típicas da luz verde em 525 e 547 nm que correspondem à transição 4H11/2→4I15/2. As duas bandas menores de emissão no vermelho, correspondem à transição 4F9/2 para o estado fundamental 4I15/2. Os resultados obtidos para os sistemas cerâmicos mostraram-se satisfatórios quanto ao método utilizado para síntese, que, apresentou-se com menor custo comparado aos processos existentes.

BARBOSA, R. de L. Propriedades dielétricas intrínsecas de perovskitas duplas RE2CoMnO6 (RE = íon terra-rara). 2017. 69 f. Dissertação (Mestrado em Física) – Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2017.
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Dielectric ceramics with ordered double perovskite structure and RE2CoMnO6 stoichiometry, in which RE is a rare-earth ion, are usually multiferroic with critical magnetic and electrical transition temperatures depending on the RE ion. This family of materials crystallizes in the P21/n symmetry when there is ordering of the Mn and Co ions. This monoclinic structure has a distortion directly dependent on the RE ionic size, influencing directly the properties of these materials. In this work, we investigate the intrinsic dielectric properties of these samples for RE = Tb, Dy, Ho, Yb and Tm. These properties were investigated by infrared reflection spectroscopy, allowing to estimate both the intrinsic static dielectric constant and the dielectric losses due to the polar phonons, which allows estimating the maximum microwave quality factor obtained when a resonator is formed with the respective materials. Our results show that, as obtained for La2CoMnO6 (LaCMO), the main compound of this family, the intrinsic static dielectric constant is reduced. In the case of LaCMO, dielectric measurements performed by other authors showed a colossal effect, whose origin was extrinsic effects. Therefore, our result allows to predict that any effect that leads to very high dielectric constants is extrinsic in this family of materials. In addition, the analysis of the quality factor showed that such ceramics have a quality factor compatible with those employed in microwave dielectric resonators since the low dielectric constant is not a problem.
As cerâmicas dielétricas com estrutura perovskita dupla ordenada com estequiometria RE2CoMnO6, na qual RE é um íon terra-rara, são usualmente multiferróicas com temperaturas críticas de transição magnética e elétrica dependendo do íon RE. Esta família de materiais cristaliza-se na simetria P21/n quando há o ordenamento dos íons Mn e Co. Esta estrutura monoclínica, tem um distorção diretamente ligada ao tamanho do íon RE, o que influencia diretamente suas propriedades. Neste trabalho investigamos as propriedades dielétricas intrínsecas destas amostras para RE = Tb, Dy, Ho, Yb e Tm. Tais propriedades foram investigadas por espectroscopia de reflexão especular no infravermelho, permitindo estimar tanto a constante dielétrica estática intrínseca devido aos fônons polares, como as perdas dielétricas devido a estes fônons, o que permite estimar o fator de qualidade em micro-ondas máximo obtido quando se conforma um ressonador dielétrico com o respectivo material. Nossos resultados mostram que, assim como obtido para o La2CoMnO6 (LaCMO), principal composto desta família, a constante dielétrica estática intrínseca é reduzida. No caso do LaCMO , medidas dielétricas realizadas por outros pesquisadores mostraram efeito colossal, cuja origem eram efeitos extrínsecos. Portanto, nosso resultado permite prever que qualquer efeito que leve a obter constantes dielétricas muito altas tem natureza extrínseca nesta família de materiais. Além disso, a análise do fator de qualidade mostrou que tais cerâmicas tem fator de qualidade compatível com aqueles empregados em ressonadores dielétricos para micro-ondas desde que a constante dielétrica baixa não seja um problema.

The content of this thesis is about preparation and processing of lead-free piezoceramic materials with perovskite structure. Potassium sodium niobate (KNN) powder was prepared by solid state reaction (SSR) and liquid phase reaction (sol-gel reaction). The powders were formed by uniaxial and isostatic pressing and further sintered. The density, grain size and morphology were determined on the sintered samples. The powder, synthesised by SSR and sintered in a conventional furnace, was chosen as a standard. The maximum density achieved on samples after optimization of sintering cycle was 93 %TD. The sintering optimization involved a homogenization step at 950 °C, which promotes the correct development of the phase composition and microstructure, followed by sintering at 1120 °C. The same approach and sintering cycle were used for sintering the samples, prepared by sol-gel synthesis. The maximum density of the samples prepared by sol-gel reaction and sintered in a conventional way, was 92 %TD. For further comparison, both of the synthesised powders were sintered using SPS (spark plasma sintering), which increased their final density up to 97 %TD. The approximate value of the piezoelectric coefficient d33 (pC/N) has been measured on selected SSR samples with pure phase composition ((K0,5Na0,5)NbO3). The best measured value of d33 was around 100 pC/N.

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

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES
In this work we describe the synthesis of the novel series La2−xCaxCoIrO6 and its structural, electronic and magnetic characterization. The main objective of this project is to investigate the magnetic evolution of the system when modified due to the chemical substitution of Ca at La site, which can induce changes in the magnetic interactions. The policristaline samples were synthesized by Solid State Reaction process, and studied combining global characterization techniques as powder x-ray diffraction, temperature dependence of magnetic susceptibility and magnetization as a function of applied magnetic field. All compounds crystallize in monoclinic structure, with space group P21/n. Magnetic susceptibility results indicate that the superexchange antiferromagnetic interaction between Co2+ and Ir4+ in La2CoIrO6 lead to ferrimagnetic behavior due to the different magnetic moment of the transition metal ions. For the Ca2+ doped at La3+ site compounds, a magnetic evolution is observed with doping, induced by Co and Ir valence changes. As expected, this system presents a strong correlation between its structural, electronic and magnetic properties, in a way that combining the different results of each compound we can explain its behavior and understand the big picture of this system.
Neste trabalho descrevemos a síntese e a caracterização estrutural, eletrônica e magnética dos compostos policristalinos da série inédita La2−xCaxCoIrO6. O principal objetivo deste projeto foi investigar a evolução da magnetização do sistema quando os materiais são modificados a partir da substituição química do Ca no sítio do La, o que pode induzir mudanças na natureza das interações magnéticas. As amostras policristalinas foram sintetizadas pela técnica de Reação de Estado Sólido convencional, e estudadas combinando-se técnicas de caracterização globais como difração de raios X de pó, magnetização em função da temperatura e em função do campo magnético aplicado, e também calor específico em função da temperatura. Todos os compostos da série cristalizam-se em estrutura monoclínica, com grupo espacial P21/n. As medidas de susceptibilidade magnética indicaram que a interação de supertroca antiferromagnética entre os metais de transição Co2+ e Ir4+ leva o composto La2CoIrO6 a apresentar comportamento ferrimagnético devido aos diferentes momentos magnéticos apresentados pelos dois íons, com TC em torno de 100K. Para os compostos dopados com Ca2+ no sítio do La3+, observou-se mudanças nas propriedades magnéticas, induzidas pelas alterações nas valências dos íons de Co e Ir. Como esperado, este sistema apresenta uma forte correlação entre as suas propriedades estruturais, eletrônicas e magnéticas, de modo que a partir da interpretação conjunta dos dados acerca da estrutura e da magnetização, podemos entender o comportamento de cada composto da série.

Les perovskites organiques-inorganiques en halogénures de plomb sont des matériaux très prometteurs pour la prochaine génération de cellules solaires avec des avantages intrinsèques tels que leur faible coût de fabrication (grande disponibilité des matériaux de base et leur mise en œuvre à basse température) et leur bon rendement de conversion photovoltaïque. Cependant, les cellules solaires pérovskites sont encore instables et montrent des effets d'hystérésis courant-tension délétères. Dans cette thèse, des résultats de l’analyse physique de couches minces de pérovskite à base de CH3NH3PbI3-xClx et de cellules solaires ont été présentés. Les caractéristiques de transport électrique et les processus de vieillissement ont été étudiés avec différentes approches.Dans une première étape, la synthèse du matériau pérovskite a été optimisée en contrôlant les conditions de dépôt des films en une seule étape telles que la vitesse de rotation (6000 rpm) de la tournette et la température de recuit des films (80 °C). Dans un second temps, des cellules solaires perovskites à base de CH3NH3PbI3-xClx ont été fabriquées en utilisant la structure planaire inversée et caractérisées optiquement et électriquement.Grace à l’utilisation de la spectroscopie optique à décharge luminescente (GDOES), un déplacement des ions halogénures a été observé expérimentalement et de façon directe sous l’application d’une tension électrique. Une longueur de diffusion ionique de 140 nm et un rapport de 65% d'ions mobiles ont été déduits. Il est montré que l'hystérésis courant-tension dans l'obscurité est fortement affectée par la migration des ions halogénures provoquant un écrantage substantiel du champ électrique appliqué. Nous avons donc trouvé sous obscurité un décalage de la tension à courant nul jusque 0,25 V et un courant de fuite jusque 0,1 mA / cm2 en fonction des conditions de mesure. Grâce aux courbes courant-tension en fonction de la température, nous avons déterminé la température de transition de la conductivité ions/électrons à 260K et analysé les résultats expérimentaux en utilisant l'équation de Nernst- Einstein donnant une énergie d'activation de 0.253 eV pour les ions mobiles.Enfin, le processus de vieillissement de la cellule solaire a été étudié avec des mesures optiques et électriques. Nous avons déduit que le processus de vieillissement apparaît d'abord à la surface des cristaux de pérovskite ainsi qu’aux joints de grains. Les mesures GDOES nous indiquent que les caractéristiques électriques des cellules pérovskites sont perdues par une corrosion progressive de l'électrode supérieure en argent causée par la diffusion des ions iodures
Organic-inorganic lead halide perovskites are very promising materials for the next generation of solar cells with intrinsic advantages such as a low-cost material due to the availability of source materials and low-temperature solution processing as well as a high power conversion efficiency of the sunlight. However, perovskite solar cells are still unstable and show deleterious current-voltage hysteresis effects. Inthis thesis, analyses of CH3NH3PbI3-xClx based perovskite thin films and solar cells are presented. The electrical transport characteristics and the ageing processes are investigated using different approaches.The synthesis of the halide perovskite materials is optimized in a first step by controlling the deposition conditions such as annealing temperature (80°C) and spinning rate (6000 rpm) in the one step-spin-casted process. CH3NH3PbI3-xClx based perovskite solar cells are then fabricated in the inverted planar structure and characterized optically and electrically in a second step.Direct experimental evidence of the motion of the halide ions under an applied voltage has been observed using glow discharge optical emission spectroscopy (GDOES). Ionic diffusion length of 140 nm and ratio of mobile iodide ions of 65 % have been deduced. It is shown that the current-voltage hysteresis in the dark is strongly affected by the halide migration which causes a substantial screening of the applied electric field. Thus we have found a shift of voltage at zero current (< 0.25 V) and a leakage current (< 0.1 mA/cm2) in the dark versus measurement condition. Through the current-voltage curves as a function of temperature we have identified the freezing temperature of the mobile iodides at 260K. Using the Nernst-Einstein equation we have deduced a value of 0.253 eV for the activation energy of the mobile ions.Finally, the ageing process of the solar cell has been investigated with optical and electrical measurements. We deduced that the ageing process appear at first at the perovskite grain surface and boundaries. The electrical characteristics are degraded through a deterioration of the silver top-electrode due to the diffusion of iodides toward the silver as shown by GDOES analysis

Metal-halide perovskites show great promise as solution-processable semiconductors for efficient solar cells and LEDs. In particular, the diffusion range of photogenerated carriers is unexpectedly long and the luminescence yield is remarkably high. While much effort has been made to improve device performance, the barriers to improving charge transport and recombination properties remain unidentified. I first explore charge transport by investigating a back-contact architecture for measurement. In collaboration with the Snaith group at Oxford, we develop a new architecture to isolate charge carriers. We prepare thin films of perovskite semiconductors over laterally-separated electron- and hole-selective materials of SnOₓ and NiOₓ, respectively. Upon illumination, electrons (holes) generated over SnOₓ (NiOₓ) rapidly transfer to the buried collection electrode, leaving holes (electrons) to diffuse laterally as majority carriers in the perovskite layer. We characterise charge transport parameters of electrons and holes, separately, and demonstrate that grain boundaries do not prevent charge transport. Our results show that the low mobilities found in applied-field techniques do not reflect charge diffusivity in perovskite solar cells at operating conditions. We then use the back-contact architecture to investigate recombination under large excess of one charge carrier type. Recombination velocities under these conditions are found to be below 2 cm s⁻¹, approaching values of high quality silicon and an order of magnitude lower than under common bipolar conditions. Similarly, diffusion lengths of electrons and holes exceed 12 μm, an order of magnitude higher than reported in perovskite devices to date. We report back-contact solar cells with short-circuit currents as high as 18.4 mA cm⁻², giving 70% external charge-collection efficiency. We then explore the behaviour of charge carriers in continuously illuminated metal-halide perovskite devices. We show that continuous illumination of perovskite devices gives rise to a segregated charge carrier population, and we find that the distance photo-induced charges travel increases significantly under these conditions. Finally, we examine intermittancy in the photoluminescence intensity of metal-halide perovskite films.

Šiame darbe vienfazis perovskito struktūros gadolinio aliuminatas GdAlO3 zolių-gelių metodu buvo gautas 1000 oC temperatūroje, gadolinio jonų šaltiniu naudojant Gd2O3, kompleksus sudarančiu reagentu – 1,2 etandiolį, natūralią vyno rūgštį, citrinų rūgštį arba citrinų rūgšties ir etanolamino mišinį. Sintetinant GdAlO3, gautų tyrimų rezultatai parodė, kaip yra svarbu zolių gelių procese pasirinkti tinkamas pradines medžiagas bei kompleksus su metalais sudarančius reagentus: gadolinio jonų šaltiniu naudojant Gd2O3 buvo gauti geresni rezultatai nei naudojant Gd(NO3)3•6H2O, vienfazis GdAlO3 gali būti sėkmingai susintetintas kompleksus sudarančiu reagentu naudojant tiek natūralią vyno rūgštį, tiek 1,2 etandiolį, tiek citrinų rūgštį, tiek citrinų rūgšties ir etanolamino mišinį. Nustatyta, kad sintetinant stronciu pakeistus gadolinio aliuminatus Gd1–xSrxAlO3– (x = 0,10, 0,25, 0,50, 0,75), tinkamesnis gadolinio jonų šaltinis yra gadolinio oksidas nei gadolinio nitratas heksahidratas, kompleksus sudarantis reagentas – EDTA nei natūrali vyno rūgštis. Vienfazis perovskito struktūros stronciu pakeistas gadolinio aliuminatas Gd0,90Sr0,10AlO3– buvo susintetintas zolių-gelių metodu 1000 oC temperatūroje, gadolinio jonų šaltiniu naudojant Gd2O3, stroncio jonų šaltiniu – Sr(NO3)2, kompleksus sudarančiu reagentu – EDTA. Be to, 800 ºC iškaitinimo temperatūra yra per maža šiems junginiams sintetinti. Pirmą kartą pasiūlytas vandeninis zolių gelių metodas lantano ir gadolinio kobaltatams... [toliau žr. visą tekstą]
In the present thesis the reported results let us to conclude that the developed aqueous sol–gel procedure could be successfully used for the low-temperature synthesis of monophasic perovskite gadolinium aluminate ceramics. It was also demonstrated that the selection of raw materials for the sol–gel processing should be done with care. Monophasic perovskite structure gadolinium aluminate GdAlO3 has been synthesized by sol gel synthesis method at 1000 oC, using gadolinium oxide as gadolinium raw material and 1.2 ethanediol, natural tartaric acid, citric acid or mixture of citric acid and ethanolamine as complexing agent. According to the XRD results, the Gd2O3 instead of Gd(NO3)36H2O preferably should be used as starting material for the preparation of GdAlO3. Monophasic perovskite structure strontium substituted gadolinium aluminate Gd0.90Sr0.10AlO3– was synthesized by the same sol gel synthesis method at 1000 oC, using gadolinium oxide as gadolinium raw material, strontium nitrate as strontium ion source and EDTA as complexing agent. It was proved that better gadolinium ion source is gadolinium oxide than gadolinium nitate hexahydrate, better complexing agent – EDTA than natural tartaric acid in the synthesis of GdAlO3 and strontium substituted Gd1–xSrxAlO3– (x = 0.10, 0.25, 0.50, 0.75) samples. According to the XRD results, increasing amount of strontium reduces amount of peaks of perovskite structure gadolinium aluminate. Besides, 800 ºC temperature is too low for the... [to full text]

In the present thesis the reported results let us to conclude that the developed aqueous sol–gel procedure could be successfully used for the low-temperature synthesis of monophasic perovskite gadolinium aluminate ceramics. It was also demonstrated that the selection of raw materials for the sol–gel processing should be done with care. Monophasic perovskite structure gadolinium aluminate GdAlO3 has been synthesized by sol gel synthesis method at 1000 oC, using gadolinium oxide as gadolinium raw material and 1.2 ethanediol, natural tartaric acid, citric acid or mixture of citric acid and ethanolamine as complexing agent. According to the XRD results, the Gd2O3 instead of Gd(NO3)36H2O preferably should be used as starting material for the preparation of GdAlO3. Monophasic perovskite structure strontium substituted gadolinium aluminate Gd0.90Sr0.10AlO3– was synthesized by the same sol gel synthesis method at 1000 oC, using gadolinium oxide as gadolinium raw material, strontium nitrate as strontium ion source and EDTA as complexing agent. It was proved that better gadolinium ion source is gadolinium oxide than gadolinium nitate hexahydrate, better complexing agent – EDTA than natural tartaric acid in the synthesis of GdAlO3 and strontium substituted Gd1–xSrxAlO3– (x = 0.10, 0.25, 0.50, 0.75) samples. According to the XRD results, increasing amount of strontium reduces amount of peaks of perovskite structure gadolinium aluminate. Besides, 800 ºC temperature is too low for the... [to full text]
Šiame darbe vienfazis perovskito struktūros gadolinio aliuminatas GdAlO3 zolių-gelių metodu buvo gautas 1000 oC temperatūroje, gadolinio jonų šaltiniu naudojant Gd2O3, kompleksus sudarančiu reagentu – 1,2 etandiolį, natūralią vyno rūgštį, citrinų rūgštį arba citrinų rūgšties ir etanolamino mišinį. Sintetinant GdAlO3, gautų tyrimų rezultatai parodė, kaip yra svarbu zolių gelių procese pasirinkti tinkamas pradines medžiagas bei kompleksus su metalais sudarančius reagentus: gadolinio jonų šaltiniu naudojant Gd2O3 buvo gauti geresni rezultatai nei naudojant Gd(NO3)3•6H2O, vienfazis GdAlO3 gali būti sėkmingai susintetintas kompleksus sudarančiu reagentu naudojant tiek natūralią vyno rūgštį, tiek 1,2 etandiolį, tiek citrinų rūgštį, tiek citrinų rūgšties ir etanolamino mišinį. Nustatyta, kad sintetinant stronciu pakeistus gadolinio aliuminatus Gd1–xSrxAlO3– (x = 0,10, 0,25, 0,50, 0,75), tinkamesnis gadolinio jonų šaltinis yra gadolinio oksidas nei gadolinio nitratas heksahidratas, kompleksus sudarantis reagentas – EDTA nei natūrali vyno rūgštis. Vienfazis perovskito struktūros stronciu pakeistas gadolinio aliuminatas Gd0,90Sr0,10AlO3– buvo susintetintas zolių-gelių metodu 1000 oC temperatūroje, gadolinio jonų šaltiniu naudojant Gd2O3, stroncio jonų šaltiniu – Sr(NO3)2, kompleksus sudarančiu reagentu – EDTA. Be to, 800 ºC iškaitinimo temperatūra yra per maža šiems junginiams sintetinti. Pirmą kartą pasiūlytas vandeninis zolių gelių metodas lantano ir gadolinio kobaltatams... [toliau žr. visą tekstą]

L'energia fotovoltaica s'ha convertit en una de les alternatives més populars com a font d'energia renovable. Es basa en la transformació directa de radiació solar en electricitat. Es troba disponible a escala global i a més no necessita de cap transformador per convertir l'energia mecànica en energia elèctrica, el que fa que sigui fàcil d'implementar. Avui en dia, el material més utilitzat per a aplicacions fotovoltaiques segueix sent el silici. En canvi, el desenvolupament de noves tecnologies, més barates, fàcils de processar i que a més poden utilitzar-se en substrats flexibles, ha sorgit com a alternativa al silici. De totes elles, les perovskita basades en halurs de plom s'han convertit en una de les millors opcions per a la comunitat científica a causa de les excel·lents propietats fotovoltaiques que presenta. Tot i que les eficiències dels dispositius preparats amb perovskita han arribat al 25%, un valor que es troba molt proper al seu màxim teòric, els processos que tenen lloc en aquests dispositius encara no són del tot coneguts. En aquesta tesi es tracta d'obtenir informació sobre els processos dels transportadors de càrrega, des de com es generen fins a la recombinació, tant en les interfícies com a l'interior del propi material. Per això, s'han utilitzat diferents tècniques de caracterització avançades com el fotovoltatge transitori (TPV), la fotocorrent transitòria (TPC), l'extracció de càrrega (CE) i l’espectroscòpia d'absorció transitòria en l'escala del femtosegon (FSTA), obtenint importants conclusions sobre pèrdues i processos que afecten la recombinació de transportadors de càrrega que porten a pitjors eficiències
La energía fotovoltaica se ha convertido en una de las alternativas más populares como fuente de energía renovable. Se basa en la transformación directa de radiación solar en electricidad. Se encuentra disponible a escala global y además no precisa de ningún transformador para convertir la energía mecánica en energía eléctrica, lo que hace que sea fácil de implementar. Hoy en día, el material más utilizado para aplicaciones fotovoltaicas sigue siendo el silicio. En cambio, el desarrollo de nuevas tecnologías, más baratas, fáciles de procesar y que además pueden utilizarse en sustratos flexibles, ha surgido como alternativa al silicio. De todas ellas, las perovskitas basadas en haluros de plomo se han convertido en una de las mejores opciones para la comunidad científica debido a las excelentes propiedades fotovoltaicas que presenta. Aunque las eficiencias de los dispositivos preparados con perovskitas han alcanzado el 25%, un valor que se encuentra muy cercano a su máximo teórico, los procesos que tienen lugar en estos dispositivos aún no son del todo conocidos. En esta tesis se trata de obtener información acerca de los procesos de los transportadores de carga, desde cómo se generan hasta la recombinación, tanto en las interfaces como en el interior del propio material. Para ello, se han utilizado distintas técnicas de caracterización avanzadas como el fotovoltaje transitorio (TPV), fotocorriente transitoria (TPC), la extracción de carga (CE) y la espectrocopía de absorción transitoria en la escala del femtosegundo (fsTA), obteniendo importantes conclusiones sobre pérdidas
Photovoltaics have become one of the most popular renewable source of energy. Photovoltaic technologies transform sunlight into electricity, and they are also available worldwide, and they do not depend on the conversion of motive power, making this technology quite easy to implement. Nowadays, silicon is still the most used material for photovoltaics. Anyway, new photovoltaic technologies have emerged as alternatives to silicon, as they are cheaper, easier to process, and, they are possible to use on flexible substrates. Among them, lead halide perovskites have become one of the most popular choice in the scientific community, due to the great properties that this material presents. While efficiencies have risen above 25%, which is close to their maximum theoretical limit, there is still debate about the processes happening in the device. In this thesis, we try to gain insight into charge carrier processes from their generation to their recombination at both perovskite interfaces, and also in the bulk of the material. Using advanced characterization techniques, such as transient photovoltage (TPV), transient photocurrent (TPC), charge extraction (CE), and femtosecond transient absorption spectroscopy (fsTA) we obtained important findings about charge carrier losses, and artifacts affecting charge carrier recombination in functional devices that lead to lower power conversion efficiencies.

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Strontium titanate, SrTiO3 (ST) is a mixed oxide from the group of perovskites, has a cubic structure and a band gap of 3.2 eV. In this study systems SrTiO3(ST), SrTi0,90Fe0,10O3(STF), Sr0,90Ag0,10TiO3(SAT) and Sr0,95Ag0,05Ti0,90Fe0,10O3(SATF) were synthesized by the Pechini method in which the same, favor the production of nanostructured materials with a high stoichiometric accordingly. The precursors used were titanium isopropoxide, citric acid, strontium nitrate, ferric nitrate, silver nitrate and ethylene glycol. For the formation of the precursor powder, the resin is calcined at 300 °C for 1 hour with a ramp of 10 °C min-1. The precursor powder was characterized by TG/DTA. For the formation of calcined systems we used different temperatures of 400 °C / 500 °C/ 600 °C/ 700 °C/ 2h with a ramp of 10 °C min-1. The sample composition was calcined in ST 550 °C/ 2h to examine the formation of the phase. The samples were characterized by X-Ray Diffraction (XRD) spectroscopy, FTIR, UV-Vis spectroscopy, Raman spectroscopy and B.E.T. the sample STF showed a peak shift DTA higher intensity to lower temperature, resulting in a more rapid decomposition. The x-ray diffractograms show the formation of perovskite phase at low temperature of 600 °C with secondary phase SrCO3 and TiO2, the SAT and SATF samples occurred and formation of metal pranta as a secondary phase. Infrared spectra show that the material exhibits short-range organization and having SrCO3 as a secondary phase. Raman spectra show first order band which is characteristic of tetragonal structure ST. The samples are mesoporous, the substitution Ti / Fe and Sr / Ag promoted the reduction of the surface area of the samples. The addition of iron as a substituent ST caused a reduction of the optical band gap 3.21(2) to 2.31(2) in PBS and 2.16(1) composition in SATF composition. It can be concluded that the method is efficient in the synthesis of structural organization samples with short and long range, using calcination temperatures above 600 °C, and that the substitution by Ti/Fe promotes the reduction of the band gap and the surface area of the ST.
O Titanato de estrôncio, SrTiO3 (ST) é um óxido misto do grupo das perovskitas, apresenta estrutura cúbica e um “band gap” de 3,2 eV. Neste estudo, os sistemas SrTiO3(ST), SrTi0,90Fe0,10O3(STF), Sr0,90Ag0,10TiO3(SAT) e Sr0,95Ag0,05Ti0,90Fe0,10O3(SATF) foram sintetizados pelo método Pechini, o mesmo favorece a obtenção de materiais com alta conformidade estequiométrica. Os precursores utilizados foram: isopropóxido de titânio, ácido cítrico, nitrato de estrôncio, nitrato férrico, nitrato de prata e etileno glicol. Para a formação do pó precursor, calcinou-se a resina a 300ºC por 1 hora com rampa de 10 ºC.min-1. O pó precursor foi caracterizado por TG/DTA. Para a formação dos sistemas calcinados utilizou-se diferentes temperaturas de 400 ºC/500 ºC/600 ºC/700 ºC/2h com rampa de 10 ºC.min-1. A amostra com composição ST foi calcinada em 550 ºC/2h para analisar a formação da fase. As amostras foram caracterizadas por Difração de Raios-X (DRX), Espectroscopia FTIR, Espectroscopia UV-VIS, Espectroscopia Raman e B.E.T. A amostra STF apresentou um deslocamento do pico DTA de maior intensidade, para temperatura menor, resultando em uma decomposição mais rápida. Os difratogramas de Raios-x comprovam a formação da fase perovskita a partir da temperatura de 600ºC, com fase secundaria de SrCO3 e TiO2, nas amostras SAT e SATF ocorreu e formação de pranta metálica como fase secundaria. Os espectros infravermelhos mostram que o material apresenta organização a curto alcance e que apresenta SrCO3 como fase secundária. Os espectros Raman apresentam banda de primeira ordem que é característico da fase tetragonal da estrutura ST. As amostras são mesoporosas, as substituições Ti/Fe e Sr/Ag promoveram a redução da área superficial das amostras. A adição de ferro como substituinte promoveu a redução do band gap óptico do ST de 3,21(2) para 2,31(2) na composição STF e 2,16(1) na composição SATF. Pode se concluir que o método é eficiente na síntese das amostras com organização estrutural a curto e longo alcance, utilizando temperaturas de calcinação acima de 600 ºC, e que a substituição Ti por Fe promove a redução do “band gap” e da área superficial do ST.

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Universidade Federal de Sao Carlos
This paper assesses the catalytic activities of LaCoO3 perovskite towards the steam reforming oxidative reaction of ethanol . Due to the low surface area which is commonly found on perovskite-type oxides , these were supported onAl2O3 , ZrO2 and ZrO2-Al2O3. The unsupported catalysts were prepared by precipitation and citrate methods whilst the supported catalysts were prepared by deposition -precipitation . The techniques employed to characterize the solids were: X -ray diffraction by the powder method (DRX) , X-Ray Fluorescence (FRX) Programmed Temperature Reduction with H2 (RTP-H2) Nitrogen Adsorption by B.E.T. method, X-ray Diffraction in situ, Raman spectroscopy, transmission electronic microscopy, scanning electronic microscopy, hydrogen desorption at programmed temperature TPD-H2 and Thermogravimetric Analysis. The preparation of the catalysts by precipitation and citrate routes proved to be efficient to obtain the perovskite type oxides .The supported catalysts showed surface area values larger than the unsupported ones, as there was the formation of other oxidase phases due to stand- perovskite or metal support interactions , as observed by the decreasing of reduction degree , through RTP analysis .The unsupported catalysts calcined at 700 , 800 and 900 ° C presented the best activity for oxidative reforming reaction than the supported ones. These, in turn, showed better catalytic activity towards the oxidative reforming reaction in relation to steam reforming of ethanol. By the X-ray Diffraction analysis in situ performed during the RTP-H2 and reaction tests, it was observed that the 20LaCoO3/Al2O3 catalyst prepared by method 2 - deposition -precipitation - showed lower size of crystallite of cobalt during the steam reforming reactions and oxidation in situ, therefore suggesting a better metal dispersion . The unsupported LaCoO3 catalyst prepared by precipitation method and calcined at 700ºC showed less coke formation towards the oxidative reaction of reforming of ethanol . Among the supported compounds the 20LaCoO3/ZrO2 showed the lowest coke formation in the same reaction. The analysis of scanning electron microscopy performed after the oxidative reaction, Raman spectroscopy the and Thermogravimetric Analysis, suggests that the unsupported LaCoO3 catalyst prepared by precipitation and calcined at 700ºC and the supported 20LaCoO3/ZrO2 catalyst showed lower carbon formation.
Neste trabalho foram avaliadas as atividades dos catalisadores do tipo perovskita LaCoO3, frente à reação de reforma a vapor e oxidativa do etanol. Devido à baixa área superficial, característica esta dos óxidos do tipo perovskita, esses catalizadores foram suportados em Al2O3, ZrO2 e ZrO2-Al2O3. Os catalisadores não suportados foram preparados pelos métodos citrato e precipitação, já os suportados receberam o preparo necessário pelo método deposição-precipitação. Para a caracterização dos sólidos, as técnicas utilizadas foram as seguintes: Difração de Raios-X pelo método do pó (DRX), Fluorescência de Raios X (FRX), Redução à Temperatura Programada com H2 (RTP-H2), Adsorção de Nitrogênio pelo método B.E.T., Difração de Raios X in situ, Espectroscopia Raman, Microscopia eletrônica de transmissão, Microscopia eletrônica de varredura e Dessorção de hidrogênio a temperatura programada TPD-H2 e Análises Termogravimétricas. A preparação dos catalisadores pelas rotas de precipitação e citrato apresentou resultados eficientes para a obtenção dos óxidos do tipo perovskita. Os catalisadores suportados apresentaram valores de área superficial maiores do que os não suportados, uma vez que nesses últimos houve a formação de outras fases óxidas, devido às interações suporte-perovskita ou suporte-metal, verificadas pela diminuição no grau de redução, via análises de RTP. Os catalisadores não suportados, calcinados a 700, 800 e 900°C, apresentaram melhor atividade para a reação de reforma oxidativa, se comparados aos suportados. Estes últimos, por sua vez, apresentaram melhor atividade catalítica diante da reação de reforma oxidativa em relação à reforma a vapor do etanol. Por meio das análises obtidas pela Difração de Raios X in situ, realizadas durante a RTP-H2 e durante ensaios reacionais, observou-se que o catalisador 20LaCoO3/Al2O3, preparado pelo método 2 - deposição-precipitação apresentou tamanho menor de cristalito de cobalto durante as reações de reforma a vapor e oxidativa in situ, sugerindo uma melhor dispersão metálica. O catalisador não suportado LaCoO3, preparado pelo método de precipitação e calcinado a 700ºC, apresentou menor formação de coque diante da reação de reforma oxidativa do etanol. Entre os suportados, o composto 20LaCoO3/ZrO2 foi o que apresentou menor formação de coque nessa mesma reação. Os resultados das análises de microscopia eletrônica de varredura, realizadas após a reação oxidativa de espectroscopia Raman e Análises Termogravimétrica, sugerem que o catalisador não suportado LaCoO3 preparado por precipitação e calcinado a 700ºC, assim como o catalisador suportado 20LaCoO3/ZrO2 apresentaram menor formação de carbono.

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The present work consisted in the preparation of a ceramic filter, based on a reticulated porous ceramic, used as support for a catalyst with perovskite structure. The interest in these oxides is related to the easy modification of its catalytic properties, as a function of the adequate cation selection as well as to its high temperature stability. The ceramic filter was developed using an aqueous suspension containing natural raw materials (quartz, feldspar and kaolin) impregnated on a polymeric sponge. As catalyst, SrSnO3 was used in pure form or doped with 10 % of Ni (replacing Sr2+, Sn4+ or both), obtained by the polymeric precursor method. The filter was impregnated for 12 h in solution (SrSnO3), with 1, 3 and 5 baths, dried and sintered in O2 (350 oC) and air (700 oC) atmospheres, leading to the formation of the SrSnO3 film on the filter. Samples of pure and impregnated filters (SrSnO3:Ni) were characterized by Xray florescence, X-ray diffraction (XRD), Confocal Raman spectroscopy, infrared spectroscopy, scanning electronic microscopy and EDS (energy dispersive spectroscopy). XRD results for the pure filter presented quartz and mulite. For the supported filter, the presence of the perovskita phase was confirmed, being observed the crystallinity decrease with doping. SEM showed the non homogeneous formation of the film deposited on the filter. Broad bands in Raman and infrared spectra were not easily identified due to superposition of the filter and film peaks. In spite of this, it was possible to observe the Ni2+ presence in Sn4+ site in all samples. Ni2+ doping led to a short and long range disorder, confirmed by Raman and XRD. According to the photocatalytic tests, it was observed that the system filter:film, the so called catalytic filter, presented photocatalytic activity in the discoloration and degradation of the yellow remazol dye, while photolysis and the of the pure filter led only to the discoloration, with a higher half life.
O presente trabalho consistiu na preparação de um filtro cerâmico catalítico, com base em uma cerâmica porosa reticulada usada como suporte para um catalisador com estrutura perovskita. O interesse nesses óxidos é devido à fácil modificação das suas propriedades catalíticas, em função da adequada seleção do cátion e também à sua estabilidade a altas temperaturas. O filtro cerâmico foi desenvolvido utilizando uma suspensão aquosa contendo matérias primas naturais (quartzo, feldspato e caulim) impregnada sobre uma espuma polimérica. Como catalisador foi utilizado o SrSnO3 dopado com 10% Ni (em lugar do Sr2+ , do Sn4+ e em ambos), obtido pelo método dos precursores poliméricos. O filtro foi impregnado por 12 h na solução (SrSnO3), com 1, 3 e 5 banhos, seco e posteriormente queimado em O2 (350 0C) e ar (700 0C), para formação do filme de SrSnO3 sobre o filtro. As amostras do filtro puro e impregnado (SrSnO3:Ni) foram caracterizadas por fluorescência de raios X, difração de raios-X (DRX), espectroscopia Raman confocal, espectroscopia na região do infravermelho (IV), microscopia eletrônica de varredura e EDS (espectroscopia de energia dispersiva). O resultado de DRX para o filtro puro apresentou as fases quartzo e mulita. Para o filtro suportado foi confirmada a presença da fase perovskita, sendo que com a dopagem observa-se diminuição na cristalinidade do filme a longo alcance. O MEV mostrou a deposição do filme sobre o filtro de forma não homogênea. As bandas alargadas (Raman e IV) não são identificadas facilmente, devido à sobreposição de picos tanto da matriz como do filme. Entretanto, é possível observar a entrada do Ni2+ no sítio do Sn4+ em todas as amostras. Com a introdução do Ni2+ no sistema observa-se uma desorganização a curto e longo alcance, confirmado no Raman e DRX. A partir dos testes fotocatalíticos, foi observado que o conjunto filtro:filme que chamamos de filtro catalítico mostrou atividade fotocatalítica na descoloração e na degradação do corante remazol amarelo, enquanto a fotólise e o uso do filtro puro permitem apenas a descoloração e com maior tempo de meia vida.

[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

This work studies the subject of perovskite solar cells. The structure of perovskites is described along with a portion of photovoltaics history that led to the employment of perovskites as absorpsion layers. Further, methods of measurement for solar cells such as impedance spectroscopy, photospectroscopy and load characteristics are summarized. Lastly there is a description of already done analytics of perovskite solar cells with the summary of the results. In the practical part, there are measurements made to find out any effect of cell topology or light source wavelength on the cell performance.

As far as the replacement of fossil fuels with more environmentally friendly options is concerned, hydrogen is considered as the most promising source of energy. Currently, hydrogen is mainly produced through the method of methane reforming. This method requires the utilisation of catalysts made of precious metals. This master's degree thesis therefore investigates perovskite materials SmCoO3, Sm0,8Ca0,2CoO2,9, SmCo0,8Al0,2O3 and Sm0,8Ca0,2Co0,8Al0,2O2,9, which could be utilised as catalysts in the production of hydrogen by methane reforming. Methane reformation occurs on the surface of a catalyst. Therefore, it is desirable to ensure that the specific surface area of a catalyst material is as large as possible. For that reason, the aforementioned perovskite materials were prepared by two sol-gel methods, which are expected to create perovskites with large specific surface areas. It was investigated in the course of the work how the method of synthesis affects the structure and catalytic properties of individual materials. The SmCo0,8Al0,2O3 material prepared by a sol-gel synthesis with propylene oxide as a gelation agent demonstrated the best results - the measurement of catalytic activity showed that the methane conversion had achieved the value of 99%.

Nous avons synthetise et etudie la structure de composes perovskites ferroelectriques pbsc 1 / 2nb 1 / 2o 3, caracterisees par differents degres d'ordre sc/nb et par une stchiometrie differente sur le site du pb. Ces composes sont appeles relaxeurs : leur constante dielectrique est elevee avec une forte valeur sur une gamme de temperatures importante et presente un phenomene de dispersion en frequence. L'etude de l'ordre des cations sc/nb sur le site b par diffraction des rx et des neutrons est mise en relation avec les proprietes dielectriques : il existe toujours un ordre local a courte portee au sein des composes macroscopiquement desordonnes, de meme que l'ordre reste a moyenne portee dans le psn ordonne. La mise en ordre sur le site b a un effet sur la valeur du maximum de la constante dielectrique, alors que la non-stchiometrie (introduction de lacunes, substitution plomb/baryum) augmente fortement la diffusivite de l'anomalie dielectrique. Dans la phase paraelectrique, nos etudes par diffraction ont montre que les atomes de plomb n'occupent jamais leur position ideale cubique et sont statistiquement desordonnes de facon isotrope a des temperatures bien superieures a la temperature de transition. Nous avons montre le meme type de desordre dans la perovskite simple pbtio 3, desordre qui dans ce cas n'est present que juste au-dessus de la temperature de transition. Ce desordre est caracteristique des atomes de plomb car nous avons montre son absence dans batio 3 et basc 1 / 2nb 1 / 2o 3. La phase ferroelectrique rhomboedrique est semblable pour tous les composes de psn. Les deplacements cooperatifs des cations a et b s'averent etre semblables a ceux du pmn/pt, mais differents de batio 3, ainsi que ceux de la phase tetragonale

Aquesta tesis inclou el treball fet en ICIQ sobre fabricació, caracterització, i modelització de cel·les solars de perovskita híbrida. Agafades des de la recerca en altres tipus de cel·les solars, les eines de anàlisi, les metodologies i, més important, la seva interpretació han sigut analitzades i adaptades a aquest nou tipus de dispositiu. Llavors, aquestes tècniques han sigut utilitzades per analitzar i entendre la influència de quatre diferents i nous transportadors de forats electrònics sobre el voltatge de cel·les de perovskita. Un altre estudi ha investigat la acumulació dels electrons en les cel·les per mig de petits canvis en el gruix de cada capa i analitzant les mostres per mig de les mateixes tècniques. Des de la meva estada internacional en els grups de Dr. Piers Barnes i Prof. Jenny Nelson en Imperial College London un altre estudi ha sigut complert sobre la complexa interpretació dels resultats de espectroscòpia de impedància en presència de ions mobles en les cel·les de perovskita. També està exposat tot el programari lliure que ha sigut desenvolupat per la adquisició i processament de dades i per la modelització deriva-difusió de cel·les solars de perovskita. Una versió actualitzada de aquesta tesis es pot trobar en https://github.com/ilario/documents_in_latex-PhD_thesis/
Esta tesis incluye el trabajo hecho en ICIQ sobre fabricación, caracterización, y modelización de celdas solares de perovskita hibrida. Provenientes desde la investigación en otros tipos de celdas solares, las herramientas de análisis, las metodologías, y, aún más importante, su interpretación han sido analizadas y adaptadas a este nuevo tipo de dispositivo. Entonces, estas técnicas han sido utilizadas para analizar y entender la influencia de cuatros diferentes y novedosos transportadores de huecos electrónicos sobre el voltaje de celdas de perovskita. Otro estudio ha investigado la acumulación de electrones en las celdas utilizando pequeños cambios en el grosor de cada capa y analizando las muestras con las mismas técnicas. Desde mi estancia internacional en los grupos del Dr. Piers Barnes y de la Prof. Jenny Nelson en Imperial College London otro estudio ha sido llevado al cabo sobre la complexa interpretación de los resultados de espectroscopia de impedancia en presencia de iones móviles en las celdas de perovskita. Además, se expone todos los programas libres que han sido desarrollados para la adquisición y procesamiento de datos y para la modelización deriva-difusión de celdas solares de perovskita. Una versión actualizada de esta tesis se puede encontrar en https://github.com/ilario/documents_in_latex-PhD_thesis/
This thesis includes the work done in ICIQ about fabrication, characterization, and modelling of hybrid perovskite solar cells. Coming from other kind of solar cells, the analysis tools, the methods, and, most importantly, their interpretation have been analysed and adapted to this new kind of device. Then, these techniques has been employed for analysing and understanding the influence of four different and novel hole transport materials on perovskite solar cells voltage. Another study focussed on the electrons accumulation in devices employing small variations in each stacked layer thickness and analysing the samples using the same techniques. From by international stay in Dr. Piers Barnes and Prof. Jenny Nelson groups in Imperial College London another study was originated exploring the complex interpretation of impedance spectroscopy results when applied on perovskite solar cells with mobile ions. Finally, all the free software that has been developed for data acquisition and processing and for drift-diffusion modelling of perovskite solar cells have been exposed. An updated version of this thesis can be found on https://github.com/ilario/documents_in_latex-PhD_thesis/

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.

Orientador: Silvio Rainho Teixeira
Resumo: Cerâmica com estrutura do tipo perovskita e minério recentemente descoberto, o CaZrO3 se aplica, com destaque, em componentes de circuito para sensores de oxigênio, hidrogênio e umidade, além de poder ser utilizado na adsorção de corantes, como material abrasivo, refratário e como matriz em sólidos fósforos dopados com Eu3+. Devido a este leque de aplicações, torna-se imprescindível o estudo de novos métodos de síntese visando a obtenção deste material, principalmente em escala nanométrica. O método Hidrotermal Assistido por Micro-ondas (HAM) é um excelente candidato para tal, já que é empregado na obtenção de cerâmicas avançadas, utilizando menores tempos e temperaturas durante o processo de síntese. Este trabalho apresenta os primeiros resultados da obtenção do CaZrO3 pelo método HAM, no qual diversos parâmetros de síntese foram variados para uma melhor avaliação de suas características estruturais, morfológicas e ópticas. Partículas CaZrO3 foram nucleados pelo método HAM em 140 ºC durante 1, 10, 40 e 180 min e cristalizados via tratamento térmico de 600 até 1200 ºC. Duas fases principais foram obtidas, uma estequiométrica e outra não estequiométrica, as quais podem ter suas porcentagens modificadas de acordo com os precursores, tempo de síntese e temperatura de tratamento térmico. Três propriedades distintas foram analisadas: (1) sensibilidade à umidade; (2) capacidade de adsorção dos corantes rodamina B, vermelho congo, azul de metileno e alaranjado de metila e; (3) viabi... (Resumo completo, clicar acesso eletrônico abaixo)
Abstract: Ceramic with a perovskite type structure and recently discovered mineral, CaZrO3 is especially used in circuit components for oxygen, hydrogen and humidity sensors, in addition to being able to be used in the adsorption of dyes, as an abrasive, refractory material and as a matrix in solid phosphors doped with Eu3+. Due to this range of applications, it is essential to study new methods of synthesis in order to obtain this material, mainly on a nanometric scale. The Microwave-Assisted Hydrothermal (MAH) method is an excellent candidate for this, since it is usually used to obtain advanced ceramics, using shorter times and temperatures during the synthesis process. This work presents the first results for obtaining CaZrO3 by the MAH method, in which several parameters of synthesis were varied for a better evaluation of its structural, morphological and optical characteristics. CaZrO3 particles were nucleated by the MAH method at 140 ºC for 1, 10, 40 and 180 min and crystallized via heat treatment from 600 to 1200 ºC. Two main phases were obtained, one stoichiometric and the other non-stoichiometric, which can have their percentages modified according to the precursors, synthesis time and heat treatment temperature. Three distinct properties were analyzed: (1) sensitivity to humidity; (2) adsorption capacity of rhodamine B, congo red, methylene blue and methyl orange dyes; (3) viability of this material as an Eu3+ ion matrix (1, 3 and 5%). All these properties were observed, whe... (Complete abstract click electronic access below)
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The synthesis, crystal structures and dielectric properties of perovskite oxynitrides of the type LnTiO2N (Ln = La, Nd and mixtures) and ATaO2N (A = Ca, Sr, Ba and mixtures), have been investigated. The end-member oxynitrides and their associated LaxNd1-xTiO2N, CaxSr1-xTaO2N and BaxSr1-xTaO2N solid solutions were successfully prepared by ammonolysis of the appropriate precursor oxides at temperatures in the range 900-1200ºC. The complete range of LaxNd1-xTiO2N solid solution are orthorhombic perovskites, which show a small increase in unit cell parameters with increasing La content across the range. Compositions in the CaxSr1-xTaO2N series are tetragonal for x < 0.6 and orthorhombic for x > 0.6. BaxSr1-xTaO2N solid solutions are tetragonal for x < 0.5 and cubic for x > 0.5. It was impossible to form any perovskite solid solution in the BaTaO2N-CaTaO2N series. Attempts were made to densify these oxynitrides by hot-pressing and spark plasma sintering, but a characteristic of all these oxynitride structures is that they are stable up to relatively low temperatures (1250oC) with decomposition occurring before any sintering can be achieved. A reducing environment is necessary to prevent oxidation, but this must not be too reducing to promote conversion of the transition metal into a lower oxidation state. As a result, fully dense samples were not obtained and dielectric property measurements could not be made on these samples. As an alternative, pure single phase LaTiO2N, NdTiO2N and LaxNd1-xTiO2N solid solutions were prepared as » 3 μm thick surface layers on dense pellets of the corresponding La2Ti2O7, Nd2Ti2O7 and (LaxNd1-x)2Ti2O7) oxides by ammonolysis. The bulk dielectric properties of these VI coated samples were then measured by LCR bridge techniques. The presence of an oxynitride layer significantly increased the measured dielectric constant of all samples, compared with the pure oxides, but a significantly higher dielectric loss was also observed. This lossy behaviour is believed to be due to the presence of a more conductive region of reduced La2Ti2O7 (of typical composition 2 2 7 La TiIV TiIIIO -x x -z ) situated immediately below the oxynitride layer, produced during synthesis by the presence of hydrogen in the nitriding ammonia atmosphere. The dielectric constant of all these oxynitrides was also measured in particulate form by impedance analysis of slurries and the dielectric constant calculated by a method of mixtures. Compared with the parent oxides, the dielectric constants were noticeably larger, ranging from 100-1500. These values are in reasonable agreement with the limited amount of data available in the literature, and show that this group of materials merits further exploration, providing easier synthesis routes can be developed, which also result in low loss final materials being obtained.