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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
151

Crystal structure and magnetic properties of geometrically frustrated face centered cubic (f.c.c.) double perovskites,La₂LiMO₆ and Ba₂YMO₆ (M= Mo, Re and Ru)

Aharen, Tomoko 09 1900 (has links)
<p> This thesis reports a systematic study of geometrically frustrated f.c.c. double perovskites with both monoclinic (P2₁/n) La₂LiMO₆ and cubic (Fm3m) Ba₂YMO₆ symmetries, where M=Mo (S=1/2), Re (S=1) and Ru (S=3/2). The roles of both the spin quantum number, i.e. quantum spin fluctuations, and the local site symmetry, i.e. orbital ordering, on the determination of the ground magnetic state were studied. All the compounds were prepared by solid state reaction and the structural information and magnetic properties of the compounds were collected using diffraction techniques (X-ray and neutron), de susceptibility, heat capacity, muon spin relaxation (μSR) and solid state NMR. </p> <p> The S=3/2 materials, La₂LiRuO₆ and Ba₂YRuO₆, while highly frustrated with frustration indices f ~ 16 and 8, respectively, both show antiferromagnetic (AF) long range ordering at 24K and 37K, respectively. The Neel temperature of the latter compound was determined for the first time by the heat capacity and neutron diffraction. This compound shows an unusual AF transition as two broader peaks were observed in the susceptibility while La₂LiRuO₆ shows a typical AF behavior. There is about 1 % of Y/Ru site mixing observed by 89Y MAS NMR in Ba₂YRuO₆. </p> <p> For the S=1 materials, monoclinic La₂LiReO₆ shows collective singlet like behavior as zero magnetization was observed in the ZFC susceptibility and a static and diluted spin system was indicated by μSR. On the other hand, the cubic phase, Ba₂YReO₆ surprisingly shows a spin glass behavior confirmed by μSR while no Y/Re site mixing was observed by MAS NMR. It is also a surprising observation that this compound retains cubic symmetry down to 3K where it would have a structure transition subject to the Jahn-Teller theorem. </p> <p> Finally, the S=1/2 compounds, La₂LiMoO₆ and Ba₂YMoO₆, show quite different magnetic behavior. Monoclinic La₂LiMoO₆ shows the presence of at least short range order achieved at 18K according to the heat capacity and μSR measurements. Ba₂YMoO₆ retains cubic symmetry down to 3K and no Jahn-Teller distortion was observed at the limit of the resolution of neutron diffraction. This compound surprisingly appears to remain paramagnetic down to 2K, yet evidence for a collective singlet state was observed by a paramagnetic Knight shift measurement in NMR. This is consistent with an existing theoretical prediction. </p> <p> An extended study on other S=1/2 Mo analogues, Ba₂LuMoO₆ and Ba₂ScMoO₆ is also presented. Both compounds show cubic structure confirmed by X-ray diffraction and paramagnetic behavior down to 2K in the susceptibility. </p> / Thesis / Doctor of Philosophy (PhD)
152

The Chemistry of solution processed photovoltaics: synthesis approaches for metal chalcogenide semiconductors

Jonathan William Turnley (17141164) 17 October 2023 (has links)
<p dir="ltr">With climate change creating the need for renewable energy to replace fossil fuels, solar energy technologies are primed to dominate the energy sector. And while photovoltaics have improved significantly in recent decades, continued evolution of this technology requires research into new fabrication techniques and new materials. The solution processing of metal chalcogenide semiconductors offers an opportunity to fabricate photovoltaics in a low-cost and high-throughput way. However, for this methodology to make a commercial impact a variety of challenges around the fundamental chemistry and materials science need to be addressed. Furthermore, while solution processing has been applied heavily to the Cu(In,Ga)(S,Se)<sub>2</sub> family of materials, these techniques can also open doors for emerging materials like Cu<sub>2</sub>ZnSnSe<sub>4</sub>, Ag<sub>2</sub>ZnSnSe<sub>4</sub>, and the chalcogenide perovskites.</p><p dir="ltr">In solution processed Cu(In,Ga)(S,Se)<sub>2</sub> devices, researcher have generally started with a Cu(In,Ga)S<sub>2</sub> film that is then selenized to form the final Cu(In,Ga)(S,Se)<sub>2</sub> material. However, this process has been connected to the formation of a problematic “fine-grain” layer. To solve this issue, the molecular precursors from amine-thiol chemistry were modified to produce soluble molecules with metal selenium bonding. This enabled direct solution deposition of CuInSe<sub>2</sub> films that could be processed without forming a fine grain layer.</p><p dir="ltr">Reactive dissolution chemistry (or “alkahest” chemistry) is useful for solution processing because it can enable the direct use of metal or metal chalcogenide precursors, bypassing the potential impurities from metal salt precursors. However, the commonly used amine-thiol reactive solvent system is better suited to making metal sulfides than metal selenides because the thiol acts as a sulfur source. To address this limitation, a new alkahest based on alkylammonium polyselenide solutions was developed which could reactively dissolve a wide range of metals, metal chalcogenides, and metal oxides. This generalizable chemistry enabled the synthesis of a wide range of binary and multinary metal chalcogenides including Cu(In,Ga)Se<sub>2</sub>, Cu<sub>2</sub>ZnSnSe<sub>4</sub>, and Ag<sub>2</sub>ZnSnSe<sub>4</sub>.</p><p dir="ltr">Emerging metal chalcogenide semiconductors composed of earth-abundant and non-toxic elements that can exhibit strong optoelectronic properties and high stability are a target of significant interest. Chalcogenide perovskites like BaZrS<sub>3</sub> and BaHfS<sub>3</sub> are an intriguing option to satisfy these requirements but have rarely been studied because of synthesis difficulties, historically being made by solid-state reactions or the sulfurization of oxides around 1000 °C. Here a solution-based approach that only requires moderate temperatures of 550-575 °C was developed utilizing a hybrid ink containing soluble metal thiolates and nanoparticulate metal hydrides.</p><p dir="ltr">The hybrid ink was an important proof of concept that chalcogenide perovskites could be synthesized at these moderate temperatures. However, it relies on complex and difficult to handle precursors. A simpler route would be to use air-stable precursors to make an oxide perovskite and subsequently sulfurize the material. However, this route has historically used excessively high temperatures. Therefore, a new sulfurization step was conceived based on thermodynamic arguments that includes both sulfur and hafnium sulfide as an oxygen sink. This redesigned sulfurization enabled the conversion of BaZrO<sub>3</sub> into BaZrS<sub>3</sub> at temperatures around 575 °C.</p><p dir="ltr">Finally, an energy systems and economic analysis was performed to consider how photovoltaics might be incorporated into agricultural lands. This work showed that when compared with traditional photovoltaics or a PV Aglectric concept, using corn for ethanol is an inefficient way to generate both food and energy from a given unit of land.</p>
153

Epitaxial Growth of Functional Barium Stannate Heterostructures by Pulsed Laser Deposition

Pfützenreuter, Daniel 23 June 2022 (has links)
In dieser Arbeit werden das Wachstum und die Charakterisierung der Heterostruktur eines FeFET auf der Grundlage von BaSnO3, LaInO3 und (K,Na)NbO3 Schichten untersucht. Für jedes Material wurden die Wachstumsbedingungen bestimmt und im Hinblick auf die strukturellen und elektrischen Eigenschaften optimiert. Epitaktische BaSnO3 Filme, die auf SrTiO3 Substraten gewachsen sind, weisen eine hohe Dichte an Versetzungen auf, die ihre elektrischen Eigenschaften beeinträchtigen. Die Verwendung von NdScO3 Substraten und Einführung einer SrSnO3 Pufferschicht verbesserten die strukturellen und elektrischen Eigenschaften der BaSnO3 Schichten. Dies ermöglichte schließlich Untersuchungen an der LaInO3/BaSnO3 Grenzfläche. Schon eine geringe La-Dotierung der BaSnO3 Schicht von 0,3 % führte zur Bildung eines 2DEG nach der Grenzflächenbildung und damit zum Einschluss von Elektronen an der Grenzfläche. Dies konnte durch C-V, Van-der-Pauw und Hall-Effekt-Messungen eindeutig nachgewiesen werden. Eine deutliche Verbesserung der strukturellen und elektrischen Eigenschaften der BaSnO3 Schichten wurde durch die Verwendung von LaInO3:Ba Substraten erreicht. Diese sind gitterangepasst an BaSnO3, sodass zum ersten Mal vollständig verspannte Schichten ohne Versetzungen gewachsen werden konnten. Strukturelle und elektrische Eigenschaften von (K,Na)NbO3 Schichten wurden auf SrRuO3/DyScO3 und SrTiO3:Nb-Substraten untersucht. Auf diese Weise wurden der Einfluss der Gitterdehnung auf die kritische Schichtdicke und die Prozesse der plastischen Relaxation des Gitters bestimmt. Die elektrische Charakterisierung ergab einen hohen Leckstrom, der durch strukturelle Defekte verursacht wird. Die gesamte FeFET Heterostruktur wurde auf LaInO3:Ba Substraten gewachsen und untersucht. BaSnO3 und LaInO3 Schichten wuchsen kohärent, während (K,Na)NbO3 Schichten eine plastische Gitterrelaxation aufwiesen. Das führte zur Bildung von Strukturdefekten und zu einer Verschlechterung der ferroelektrischen Eigenschaften. / In this thesis, the design, growth and characterisation of the heterostructure of a FeFET based on BaSnO3, LaInO3 and (K,Na)NbO3 thin films are investigated. For each material, the growth conditions were determined and optimised with respect to their structural and electrical properties. Epitaxial BaSnO3 thin films grown on SrTiO3 substrates exhibit a high density of threading dislocations, which degrade their electrical properties. The use of NdScO3 substrates and the introduction of a SrSnO3 buffer layer improved the structural and electrical properties of the BaSnO3 thin films. This finally allowed investigations on the LaInO3/BaSnO3 heterointerface. Even a low La doping of the BaSnO3 layer of 0.3 % led to the formation of a 2DEG after interface formation and thus to the confinement of electrons at the interface. This could be clearly demonstrated by C-V, Van-der-Pauw and Hall effect measurements. A significant improvement of the structural and electrical properties of the BaSnO3 thin films was achieved by using LaInO3:Ba substrates. These are lattice-matched to BaSnO3 so that, for the first time, fully strained thin films could be grown without dislocations. Structural and electrical properties of (K,Na)NbO3 thin films were investigated on SrRuO3/DyScO3 and SrTiO3:Nb substrates. In this way, the influence of lattice strain on the critical film thickness and plastic lattice relaxation were determined. Their electrical characterisation revealed a high leakage current caused by structural defects. Therefore, the entire FeFET heterostructure was grown and investigated on LaInO3:Ba substrates. The BaSnO3 and LaInO3 thin films were grown coherently, while the (K,Na)NbO3 thin films exhibited plastic lattice relaxation. This led to the formation of structural defects and consequently to a deterioration of their ferroelectric properties.
154

First Principles Study of Electronic and Magnetic Structures in Double Perovskites

Ball, Molly R. 24 May 2017 (has links)
No description available.
155

Bandgap predictive design model for Zero-Dimensional Inorganic Halide A2BX6 perovskite by Machine Learning

Khaliq, Samiya 07 1900 (has links)
Bandgap determines the suitability of materials for device applications such as \cite{lyu2021predictive} light-emitting diodes (LED), solar cells, and photo-detectors. The accuracy of the bandgap predicted using standard LDA or GGA functional is underestimated by density functional theory (DFT) when compared to experimental values. However, DFT combined with Machine Learning (ML) allows computational screening of materials with better accuracy. The training data for the models is obtained from density functional theory calculations which consist of A, B, and X-site elemental properties. The feature importance procedure screens the relative important features among all input features considered in the study. CatBoost(CB) regression model, \cite{Catboost} is an open-source library for gradient boosting. It gives high-perfromance on decision tress as it is based on gradient boosting algorithm and is suitable for small data sets as reduces overfitting, is implemented that can accurately predict the bandgap of $A_2BX_6$ perovskite. Eleven ML techniques were implemented, and their predictions of energy bandgap were compared, such as gradient boosted, random forest, support vector, AdaBoost, linear, K-nearest neighbor, kernel ridge, and decision tree. As per the study, the best performance is achieved by CatBoost regression model.
156

Microwave-Assisted Topochemical Manipulation of Layered Oxide Perovskites: From Inorganic Layered Oxides to Inorganic-Organic Hybrid Perovskites and Functionalized Metal-Oxide Nanosheets

Akbarian-Tefaghi, Sara 19 May 2017 (has links)
Developing new materials with desired properties is a vital component of emerging technologies. Functional hybrid compounds make an important class of advanced materials that let us synergistically utilize the key features of the organic and inorganic counterparts in a single composite, providing a very strong tool to develop new materials with ”engineered” properties. The research presented here, summarizes efforts in the development of facile and efficient methods for the fabrication of three- and two-dimensional inorganic-organic hybrids based on layered oxide perovskites. Microwave radiation was exploited to rapidly fabricate and modify new and known materials. Despite the extensive utilization of microwaves in organic syntheses as well as the fabrication of the inorganic solids, the work herein was among the first reported that used microwaves in topochemical modification of the layered oxide perovskites. Our group specifically was the first to perform rapid microwave-assisted reactions in all of the modification steps including proton exchange, grafting, intercalation, and exfoliation, which decreased the duration of multi-step modification procedures from weeks to only a few hours. Microwave-assisted grafting and intercalation reactions with n-alkyl alcohols and n-alkylamines, respectively, were successfully applied on double-layered Dion-Jacobson and Ruddlesden-Popper phases (HLaNb2O7, HPrNb2O7, and H2CaTa2O7), and with somewhat more limited reactivity, applied to triple-layered perovskites (HCa2Nb3O10 and H2La2Ti3O10). Performing neutron diffraction on n-propoxy-LaNb2O7, structure refinement of a layered hybrid oxide perovskite was then tried for the first time. Furthermore, two-dimensional hybrid oxides were efficiently prepared from HLnNb2O7 (Ln = La, Pr), HCa2Nb3O10, HCa2Nb2FeO9, and HLaCaNb2MnO10, employing facile microwave-assisted exfoliation and post-exfoliation surface-modification reactions for the first time. A variety of surface groups, saturated or unsaturated linear and cyclic organics, were successfully anchored onto these oxide nanosheets. Properties of various functionalized metal-oxide nanosheets, as well as the polymerization of some monomer-grafted nanosheets, were then investigated for the two-dimensional hybrid systems.
157

Ultrafast spectroscopy of charge separation, transport and recombination processes in functional materials for thin-film photovoltaics

Wehrenfennig, Christian January 2014 (has links)
Dye-sensitized solar cells (DSSCs) and perovskite solar cells are emerging as promising potential low-cost alternatives to established crystalline silicon photovoltaics. Of the employed functional materials, however, many fundamental optoelectronic properties governing photovoltaic device operation are not sufficiently well understood. This thesis reports on a series of studies using ultrafast THz and photoluminescence spectroscopy on two classes of such materials, providing insight into the dynamics of charge-transport and recombination processes following photoexcitation. For TiO<sub>2</sub>-nanotubes, which have been proposed as easy-to-fabricate electron transporters for DSSCs, fast, shallow electron trapping is identified as a limiting factor for efficient charge collection. Trapping lifetimes are found to be about an order of magnitude shorter than in the prevalently employed sintered nanoparticles under similar excitation conditions and trap saturation effects are not observed, even at very high excitation densities. In organo-lead halide perovskites - specifically CH<sub>3</sub>NH<sub>3</sub>PbI<sub>3</sub> and CH<sub>3</sub>NH<sub>3</sub>PbI<sub>3-x</sub>Cl<sub>x</sub>, which have only recently emerged as highly efficient absorbers and charge transporters for thin-film solar cells, carrier mobilities and fundamental recombination dynamics are revealed. Extremely low bi-molecular recombination rates at least four orders of magnitude below the prediction of Langevin's model are found as well as relatively high charge-carrier mobilities in comparison to other solution-processable materials. Furthermore a very low influence of trap-mediated recombination channels was observed. Due to a combination of these factors, diffusion lengths reach hundreds of nanometres for CH<sub>3</sub>NH<sub>3</sub>PbI<sub>3</sub> and several microns for CH<sub>3</sub>NH<sub>3</sub>PbI<sub>3-x</sub>Cl<sub>x</sub>. These results are shown to hold for both, solution processed and vapour-deposited CH<sub>3</sub>NH<sub>3</sub>PbI<sub>3-x</sub>Cl<sub>x</sub> and underline the superb suitability of the materials as absorbers in solar cells, even in planar heterojunction architectures. The THz-frequency spectrum of the conductivity of the investigated perovskites is consistent with Drude-like charge transport additionally exhibiting weak signatures of phonon coupling. These coupling effects are also reflected in the luminescence of CH<sub>3</sub>NH<sub>3</sub>PbI<sub>3-x</sub>Cl<sub>x</sub>, where they are believed to be the cause of the observed homogeneous spectral broadening. Further photoluminescence measurements were performed at temperatures between 4 K and room temperature to study the nature of recombination pathways in the material.
158

Hétérostructures d'oxydes à gaz d'électrons bidimensionnels pour microélectronique en environnements extrêmes / Two-dimensional electron gas oxide heterostructures for microelectronic in extreme environments

Zaid, Hicham 09 December 2016 (has links)
De nombreuses propriétés étonnantes ont été récemment découvertes à l’interface de deux perovskites isolantes l’une polaire l’autre non polaire. La discontinuité de charge à l’interface LaAlO3/SrTiO3 engendre un gas d’électron quasi-bidimensionnel qui confère un caractère métallique à cette interface. Les mécanismes locaux et la quantification des propriétés ne font pas consensus car l’interdépendance de facteurs structuraux, chimiques et électroniques complexifie la résolution du problème posé. Une catastrophe polaire, des distorsions structurales, des lacunes d’oxygène, une interdiffusion cationique et une non stœchiométrie du film ont été séparément avancées pour expliquer cette conduction. Dans le cadre d’un programme international, nous avons reçu des héterointerfaces conductrices et isolantes élaborées par ablation laser pulsé (PLD). L’origine des porteurs de charge a été recherchée par une approche globale liant procédé, structure et propriétés électriques (mesurées dans le consortium). Nous avons systématiquement analysé les interfaces en combinant imagerie à haute résolution (STEM-HAADF) et spectroscopies électroniques (EELS) et ioniques (MEIS). Une non planéité des couches atomiques, une interdiffusion cationique et un transfert d’électrons permettent de réduire la divergence de potentiel, la catastrophe polaire n’a donc pas lieu. La formation de défauts donneurs à la surface du film devient favorable au-delà d’une épaisseur critique. Les électrons sont transférés à l’interface dans la bande de conduction du STO. Nous avons mis en évidence un mécanisme de compensation concurrentiel de la charge interfaciale par des lacunes de strontium chargées négativement, qui mettent le substrat en compression plane et s’opposent au confinement 2D électrons. La variation des paramètres procédés, tels que la durée du dépôt, la pression partielle en oxygène, la température et la stœchiométrie de la plume déplace l’équilibre des différents mécanismes mis en évidence. Ce travail démontre la relation complexe liant procédé, propriétés électriques et distribution des défauts autour de ces interfaces singulières. / Novel behavior at the interface between two insulating polar/non polar perovskites has been recently discovered. The polarization discontinuity at LaAlO3/SrTiO3 drives the formation of quasi two dimensional electron gas. Both the local mechanism and quantification of such behavior remain unclear due to interplay of structural, chemical and electronic factors. Several mechanisms have been proposed, such as the polar catastrophe, structural distortions, oxygen vacancies, cationic intermixing at the interface and film non-stoichiometry. In the frame of an international project conductive and insulating heterostrucutres have been synthetized by Pulsed-Laser Deposition. In this thesis, we have developed a comprehensive approach to investigate the origin of the charge carriers. The interfaces have been systematically analyzed by combining high resolution imaging (STEM-HAADF) to atomic resolved electron (EELS) and ion (MEIS) spectroscopies. The observed and quantified parameters have been related to the electrical properties of the interfaces measured in the consortium. Buckling of the atomic layers, intermixing and electron transfer reduce the polar divergence. This rules out the polar catastrophe scenario. The formation of donor defects at the film surface is favored above a critical film thickness. Electrons are transferred to interface in the STO conduction band. A competing compensation mechanism of the positive interfacial charge by negatively charged strontium vacancies has been demonstrated that generates an in plane compression of the STO, unfavorable for a strict 2D confinement of the charges. Varying the process parameters such as growth duration, oxygen partial pressure, temperature, and plume stoichiometry shift the equilibrium of the different mechanisms highlighted. This thesis emphasizes the complex relations between the process and the properties through the defects distribution around these singular interfaces.
159

Formation and stability of hybrid perovskites

Shargaieva, Oleksandra 07 November 2018 (has links)
Solarzellen auf Basis von hybriden Perowskiten, wie zum Beispiel Methylammoniumbleitriiodid (CH3NH3PbI3), stellen eine der vielversprechendsten Solarzellenkonzepte dar. Dabei wurden Wirkungsgrade über 20 % gezeigt. Perowskite werden durch verschiedene lösungsbasierte Techniken abgeschieden. Daher konzentriert sich der erste Teil dieser Dissertation auf die Bildung von hybriden Perowskiten in der Lösung, während der zweite Teil der Stabilität von hybriden Perowskiten gewidmet ist. Im ersten Teil, wird die Bildung von Polyiodidplumbaten aus PbI2 in Lösung nachgewiesen. Die Bildung dieser Polyiodidplumbate konnte unabhängig von dem gewählten Lösungsmittel sowie unabhängig von der Beigabe von Methylammoniumiodid (CH3NH3I) beobachtet werden. Die Polyiodidplumbate zeigten, ähnlich wie CH3NH3PbI3, ein Photolumineszenzmaximum bei einer Wellenlänge von 760 nm, was auf einen gemeinsamen Ursprung des angeregten Zustands in PbI2-Komplexen und CH3NH3PbI3 hindeutet. Im zweiten Teil wurden darüber hinaus die Lichtbeständigkeit sowie die thermische und kompositionelle Stabilität untersucht. Die Untersuchung der thermischen Stabilität hat gezeigt, dass Tempern bei T <190 °C zu einer Verbesserung der Morphologie und der optoelektronischen Eigenschaften führt. Oberhalb einer Temperatur von 190 °C kam es dabei zur Zersetzung des Materials. Die Stabilität der Komposition wurde anhand von CsPb(I[1-x]Br[x])3-Perowskiten untersucht. Die Herstellung von Perowskiten mit einer großen Bandlücke war zunächst nicht möglich, da es bei den dafür notwendigen Kompositionen (0,3<x<1) zur Phasentrennung kommt. Im Gegensatz dazu konnte durch den Zusatz von Ethylendiammoniumdiodid (EDDI) zu CH3NH3PbI3 die Bandlücke zwischen 1,6 und 1,8 eV variiert werden. Die Lichtstabilität von CH3NH3PbI3, CH(NH2)2PbI3 sowie gemischt Perowskiten wurde mittels in-situ Infrarotspektroskopie analysiert. Die Zersetzung des Materials war durch die lichtinduzierte Spaltung der N-H-Bindungen bei hv ≥ 2,72 eV gekennzeichnet. / Hybrid perovskites such as methylammonium lead iodide, CH3NH3PbI3, are one of the most promising absorber materials for photovoltaic energy conversion with demonstrated power conversion efficiencies beyond 20 %. In addition, hybrid perovskites can be deposited by various solution-based fabrication techniques. Therefore, the first part of this dissertation is focused on the formation of hybrid perovskites in the precursor solution, while the second part is dedicated to the study of the stability of hybrid perovskites. In the first part of this thesis, the formation of polyiodide plumbates between molecules of PbI2 was detected. Importantly, the formation of polyiodide plumbates was observed independently of the solvent choice or the presence of CH3NH3I. The polyiodide plumbates exhibited a photoluminescence peak located at 760 nm, similarly to CH3NH3PbI3, which suggests a common origin of the excited state in PbI2 complexes and CH3NH3PbI3. In the second part of this thesis, the thermal, compositional, and photostability of perovskite thin films were evaluated. The study of the thermal stability has shown that post-annealing at T < 190 °C leads to the improvement of morphology and optoelectronic properties. Above 190 °C, CH3NH3PbI3 was found to degrade. Next, the compositional stability of mixed CsPb(I[1-x]Br[x])3 perovskites was investigated. A fundamental miscibility gap between 0.3 < x <1 was demonstrated, that impedes the preparation of high band-gap perovskites. To overcome this intrinsic instability, a new approach for band-gap engineering was developed. An addition of ethylenediammonium diiodide (EDDI) allowed to alter the band gap of CH3NH3PbI3 from 1.6 to 1.8 eV. Finally, the influence of light on the stability of hybrid perovskites was studied. A degradation of CH3NH3PbI3, CH(NH2)2PbI3, as well as mixed perovskites, was observed through photo-dissociation of N-H bonds with hν ≥ 2.72 eV by means of in-situ Fourier-transform infrared spectroscopy.
160

Liquid-delivery metal-organic chemical vapour deposition of perovskites and perovskite-like compounds

Lukose, Rasuole 14 February 2011 (has links)
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.

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