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

Le développement de piles à combustibles capables de fonctionner à des températures intermédiaires de l’ordre de 400-600°C présente un grand intérêt tant du point de vue du vieillissement des matériaux que des différents éléments du système complet. Une des technologies envisagées est basée sur l’utilisation d’électrolyte céramique possédant une conduction protonique élevée (Protonic Ceramic Fuel Cell PCFC). A ce jour, un des problèmes principaux concerne les fortes surtensions observées au niveau de la cathode lors du passage d’un courant. Dans ce cadre, le but de nos recherche a été de concevoir de nouveaux matériaux de cathode pour pile PCFC présentant de bonnes propriétés de conduction mixte ionique et électronique ainsi qu’une activité catalytique élevée vis-à-vis de la réaction de réduction de l’oxygène, entre 400 et 600°C. Plusieurs matériaux à conduction mixte ont été synthétisés à l’ICMCB, notamment des perovskites et des oxydes de structure de type Ruddlesden-Popper (en particulier les oxydes A2MO4+?). Des analyses thermogravimétriques ont été réalisées pour étudier la stabilité de ces phases sous air humide, ainsi qu’une éventuelle insertion d’eau dans la structure. Des demi-cellules symétriques ont été élaborées pour les caractérisations éléctrochimiques par spectroscopie d’impédance complexe et voltampérométrie (mesures de résistances spécifiques de surface, courbes de polarisation cathodique). Les caractérisations physico-chimiques et électrochimiques ont permit de sélectionner les meilleurs composés et ont conduit à la réalisation de la première monocellule PCFC utilisant le matériau de cathode Pr2NiO4+?. Des densités de puissance de 100 mW/cm² ont été mesurées pour une température de fonctionnement de 600°C. / Development of Fuel Cell operating at intermediate temperatures (400-600°C) is more and more interesting regarding ageing of materials. One of these technologies is based on ceramic electrolytes with high protonic conductivity (Protonic Ceramic Fuel Cell, PCFC). Nowadays, the major problem is overpotential at the cathode side, under polarization. In this context, our researches aimed to elaborate new cathode materials for PCFC with high mixed conductivity and good electrocatalytic property toward oxygen reduction, between 400 and 600°C. Several materials have been synthesised at the ICMCB, like perovskites and Ruddlesden-Popper type phase (A2MO4+?). Thermogramvimetric analyses have been realised in order to study phase stability under moist air and a possible insertion of water in the structure. Symmetrical half-cells have been elaborated for Electrochemical Impedance Spectroscopy and voltametric measurements (measure of Area Specific Resistance, cathodic polarization curves). The physico-chemical and electrochemical characterizations were useful to choose the best compounds and lead to fabrication of the first cell PCFC with Pr2NiO4+? as cathode materials. Power densities of 100mW/cm² have been reached for a working temperature of 600°C.

Transition metal compounds, especially the oxides, containing dn (0 ≤ n ≤ 10) electronic configuration, constitute the backbone of solid state/materials chemistry aimed at realization of novel materials properties of technological importance. Some of the significant materials properties of current interest are spin-polarized metallic ferromagnetism, negative thermal expansion, second harmonic nonlinear optical (NLO) susceptibility, fast ionic and mixed electronic/ionic conductivity for application in solid state batteries, and last but not the least, high-temperature superconductivity. Typical examples for each one of these properties could be found among transition metal oxides. Thus, alkaline-earth metal (A) substituted rare-earth (Ln) manganites, Lnı.xAxMnΟ3, are currently important examples for spin-polarized magnetotransport, ZrV2O7 and ZrW2O8 for negative thermal expansion coefficient, KTiOPO4 and LiNbO3 for second harmonic NLO susceptibility, (Li, La) TiO3 and LiMn2O4 for fast-ionic and mixed electronic/ionic conductivity respectively, and the whole host of cuprates typified by YBa2Cu3O7 for high Tc superconductivity. Solid state chemists constantly endeavour to obtain structure-property relations of solids so as to be able to design better materials towards desired properties. Synthesis coupled with characterization of structure and measurement of relevant properties is a common strategy that chemists adopt for this task. The work described in this thesis is based on such a broad-based chemists' approach towards understanding and realization of novel materials properties among the family of metal oxides. A search for metallic ferro/ferrimagnetism among the transition metal perovskite oxides, metallicity and possibility of superconductivity among transition-metal substituted cuprates and second order NLO susceptibility among metal oxides containing d° cations such as Ti(IV), V(V) and Nb(V) - constitute the main focus of the present thesis. New synthetic strategies that combine the conventional ceramic approach with the chemistry-based 'soft1 methods have been employed wherever possible to prepare the materials. The structures and electronic properties of the new materials have been probed by state-of-the art techniques that include powder X-ray diffraction (XRD) together with Rietveld refinement, electron diffraction, thermogravimetry, measurement of magnetic susceptibility (including magnetoresistance), Mossbauer spectroscopy and SHG response (towards 1064 nm laser radiation), besides conventional analytical techniques for determination of chemical compositions. Some of the highlights of the present thesis are: (i) synthesis of new mixed valent [Mn(III)/Mn(IV)] perovskite-type manganites, ALaMn2O6-y (A = K, Rb) and ALaBMn3O9_y (A = Na, K; B = Ca, Sr) that exhibit ferromagnetism and magnetoresistance; (ii) investigation of a variety of ferrimagnetic double-perovskites that include ALaMnRuO6 (A = Ca, Sr, Ba) and ALaFeVO6 (A = Ca, Sr) and A2FeReO6 (A = Ca, Sr, Ba) providing new insights into the occurrence of metallic and nonmetallic ferrimagnetic behaviour among this family of oxides; (iii) synthesis of new K2NiF4-type oxides, La2-2xSr2XCui.xMxO4 (M = Ti, Mn, Fe, Ru) and investigation of Cu-O-M interaction in two dimension and (iv) identification of the structural rnotif(s) that gives rise to efficient second order NLO optical (SHG) response among d° oxides containing Ti(IV), V(V), Nb(V) etc., and synthesis of a new SHG material, Ba2-xVOSi2O7 having the fresnoite structure. The thesis consists of five chapters and an appendix, describing the results of the investigations carried out by the candidate. A brief introduction to transition metaloxides, perovskite oxides in particular, is presented in Chapter 1. Attention is focused on the structure and properties of these materials. Chapter 2 describes the synthesis and investigation of two series of anion-deficient perovskite oxides, ALaMn2O6-y (A = K, Rb, Cs) and ALaBMn3O9_y (A = Na, K; B = Ca, Sr). ALaMn2O6-y (A = K, Rb, Cs) series of oxides adopt 2 ap x 2 ap superstructure for K and Rb phases and √2 av x √2 ap x 2 ap superstructure (ap = perovskite subcell) for the Cs phase. Among ALaBMn3O9-y phases, the A = Na members adopt a new kind of perovskite superstructure, ap x 3 ap, while the A = K phases do not reveal an obvious superstructure of the perovskite. All these oxides are ferromagnetic (Tc ~ 260-325 K) and metallic exhibiting a giant magnetoresistance behaviour similar to alkaline earth metal substituted lanthanum manganites, Lai_xAxMnO3. However, unlike the latter, the resistivity peak temperature Tp for all the anion-deficient manganites is significantly lower than Tc. In Chapter 3, we have investigated structure and electronic properties of double-perovskite oxides, A2FeReO6 (A = Ca, Sr and Ba). The A = Sr, Ba phases are cubic (Fm3m) and metallic, while the A = Ca phase is monoclinic (P2yn) and nonmetallic. All the three oxides are ferrimagnetic with Tcs 315-385 K as reported earlier. A = Sr, Ba phases show a negative magnetoresistance (MR) (10-25 % at 5 T), while the Ca member does not show an MR effect. 57Fe Mossbauer spectroscopy shows that iron is present in the high-spin Fe3+ (S = 5/2) state in Ca compound, while it occurs in an intermediate state between high-spin Fe2+ and Fe3+ in the Ba compound. Monoclinic distortion and high covalency of Ca-O bonds appear to freeze the oxidation states at Fe+3/Re5+ in Ca2FeRe O6, while the symmetric structure and ionic Ba-O bonds render the FeReO6 array highly covalent and Ba2FeReO6 metallic. Mossbauer data for Sr2FeReO6 shows that the valence state of iron in this compound is intermediate between that in Ba and Ca compounds. It is likely that Sr2FeReO6 which lies at the boundary between metallic and insulating states is metastable, phase-seperating into a percolating mixture of different electronic states at the microscopic level. In an effort to understand the occurrence of metallicity and ferrimagnetism among double perovskites, we have synthesized several new members : ALaMnFeO6 (A = Ca, Sr, Ba), ALaMnRuO6 (A = Ca, Sr, Ba) and ALaVFeO6 (A = Ca, Sr) (Chapter 3). Electron diffraction reveals an ordering of Mn and Ru in ALaMnRuO6 showing a doubling of the primitive cubic perovskite cell, while ALaVFeO6 do not show an ordering. ALaMnRuOs are ferrimagnetic (Tcs ~ 200-250 K) semiconductors, but ALaVFeO6 oxides do not show a long range magnetic ordering . The present work together with the previous work on double perovskites shows that only a very few of them exhibit both metallicity and ferrimagnetism, although several of them are ferrimagnetic. For example, among the series Ba2MReO6 (M = Mn, Fe, Co, Ni), only the M = Fe oxide is both metallic and ferrimagnetic, while M = Mn and Ni oxides are ferrimagnetic semiconductors. Similarly, A2CrMoO6 (A = Ca, Sr), A2CrRe06 (A = Ca, Sr), and ALaMnRuO6 (A = Ca, Sr, Ba) are all ferrimagnetic but not metallic. While ferrimagnetism of double perovskites arise from an antiferromagnetic coupling of B and B' spins through the B-O-B' bridges, the occurrence of metallicity seems to require precise matching of the energies of d-states of B and B' cations and a high covalency in the BB'O6 array that allows a facile electron-transfer between B and B', Bn++B’m+↔B(n+1)++B’(m-1)+ without an energy cost, just as occurs in ReO3 and other metallic ABO3 perovskites. In an effort to understand the Cu-O-M (M = Ti, Mn, Fe, Ru) electronic interaction in two dimension, we have investigated K2N1F4 oxides of the general formula La2-2xSr2XCui.xMxO4 (M = Ti, Mn, Fe or Ru). These investigations are described in Chapter 4. For M = Ti, only the x = 0.5 member could be prepared, while for M = Mn and Fe, the composition range is 0 < x < 1.0, and for M = Ru, the composition range is 0 < x ≤ 0.5. There is no evidence for ordering of Cu(II) and M(IV) in the x = 0.5 members. While the members of the M = Ti, Mn and Ru series are semiconducting/insulating, the members of the M = Fe series are metallic, showing a broad metal-semiconductor transition around 100 K for 0 < x ≤ 0.15 that is possibly related to a Cu(II)-O-Fe(IV) < > Cu(III)-O-Fe(III) valence degeneracy. Increasing the strontium content at the expense of lanthanum in La2-2xSr2XCui.xFexO4 for x ≤ 0.20 renders the samples metallic but not superconducting. In a search for inorganic oxide materials showing second order nonlinear optical (NLO) susceptibility, we have investigated several borates, silicates and phosphates containing /ram-connected MO6 octahedral chains or MO5 square-pyramids, where M = d°: Ti(IV), Nb(V) or Ta(V). Our investigations, which are described in Chapter 5, have identified two new NLO structures: batisite, Na2Ba(TiO)2Si4O12, containing trans-connectd TiO6 octahedral chains, and fresnoite, Ba2TiOSi2O7, containing square-pyramidal T1O5. Investigation of two other materials containing square-pyramidal TiO5, viz., Cs2TiOP2O7 and Na4Ti2Si8O22. 4H2O, revealed that isolated TiO5 square-pyramids alone do not cause a second harmonic generation (SHG) response; rather, the orientation of T1O5 units to produce -Ti-O-Ti-O- chains with alternating long and short Ti-0 distances in the fresnoite structure is most likely the origin of a strong SHG response in fresnoite. Indeed, we have been able to prepare a new fresnoite type oxide, Ba2.xVOSi2O7 (x ~ 0.5) that shows a strong SHG response, confirming this hypothesis. In the Appendix, we have described three synthetic strategies that enabled us to prepare magnetic and NLO materials. We have shown that the reaction CrO3 + 2 NH4X > CrO2 + 2 NH3 + H2O + X2 (X = Br, I), which occurs quantitatively at 120-150 °C, provides a convenient method for the synthesis of CrO2. Unlike conventional methods, the method described here does not require the use of high pressure for the synthesis of this technologically important material. For the synthesis of magnetic double perovskites, we have developed a method that involves reaction of basic alkali metal carbonates with the acidic oxides (e.g. Re2O7) first, followed by reaction of this precursor oxide with the required transition metal/transition metal oxide (e.g. Fe/Fe2O3). By this method we have successfully prepared single-phase perovskite oxides, A2FeReO6, ACrMoO6 and ALaFeVO6. We have prepared the new NLO material Ba2_xV0Si207 from Ba2VOSi2O7 by a soft chemical redox reaction involving the oxidation of V(IV) to V(V) using Br2 in CH3CN/CHCI3. Ba2V0Si207 + 1/2 Br2 > Bai.5V0Si207 + 1/2 BaBr2. The work presented in this thesis was carried out by the candidate as part of the Ph.D. training programme. He hopes that the studies reported here will constitute a worthwhile contribution to the solid state chemistry of transition metal oxides and related materials.

Ein großes Hindernis für die Anwendbarkeit von oxidischen Perowskiten in elektrotechnischen oder spintronischen Applikationen, ist die Größe der spezifischen Temperaturen, bei der die physikalischen Phänomene, wie Ferromagnetismus oder Hochtemperatur-Supraleitung, beobachtet werden können. Die physikalischen Eigenschaften der Perowskite zeigen eine Abhängigkeit von der Ordnung der verschiedenartigen Metallionen in mehrkomponentigen Systemen. Die Abhängigkeit ergibt sich durch den Einfluss der Metallionen auf die Elektronenkonfiguration und elastischen Verspannung innerhalb des Materials. Man spricht in diesem Zusammenhang auch von der Kontrolle der Füllung und der Bandbreite der elektronischen Bänder im Material durch die Wahl der Metallionen. Die Zielsetzung dieser Arbeit ist die Präparation und Charakterisierung von künstlich A-Platz geordneten schmal- und breitbandigen Manganat Dünnfilmen als auch von natürlich B-Platz geordneten ferro-/ferrimagnetischen doppelperowskitischen Dünnfilmen. Für die Präparation der dünnen Schichten wurde die unkonventionelle Metallorganischen Aerosol Deposition (MAD) verwendet. Es konnte gezeigt werden, dass diverse künstlich oder natürlich Kationengeordnete Perowskite mit der MAD Technologie präpariert werden können. Die lagenweise A-Platz Ordnung in Manganaten führt, über die Modulation der Gitterverspannung und der Elektronenbesetzung im eg-Band der Manganionen, zu modifizierten elektronischen und magnetischen Eigenschaften. In schmalbandigen CMR Manganaten wurde die PS und somit der CMR über die Ordnung beeinflusst, während in breitbandigen CMR Manganaten ein Weg aufgezeigt werden konnte, der zu Übergangstemperaturen TC > 370K führen kann. In geordneten, ferromagnetischen Doppelperowskiten wurde der Einfluss und die Anwesenheit von Antiphasen-Grenzen dargelegt. Über die Einführung einer aktiven Valenz-Kontrolle, konnte die Präparation von halbmetallischen, ferrimagnetischen Doppelperowskiten mit der MAD Technologie ermöglicht werden.

La réfrigération magnétique attire beaucoup d’attention ces dernières années parce qu’elle est considérée comme une technologie respectueuse de l’environnement et énergétiquement économique. Aujourd’hui, cette technologie avancée est encore en phase de recherche que des dispositifs de réfrigérations magnétiques soient déjà opérationnels. Ce travail de thèse consiste à étudier la potentialité de résistance à la corrosion de différents types de matériaux magnétocaloriques (Gd6Co1.67Si3, Ni2Mn0.75Cu0.25Ga et Pr0.66Sr0.34MnO3) en contact avec un fluide caloporteur. Afin de comprendre les propriétés magnétocaloriques des matériaux, nos recherches se sont aussi focalisées sur les relations entre la transition magnéto-structurales d’alliages Heusler Ni2Mn0.75Cu0.25Ga et (i) la distribution cationique au sein de la structure cristalline et/ou (ii) la microstructure. Finalement, le diagramme de phase magnétique et nucléaire en lien avec les effets magnétocalorique obtenu grâce à la diffraction de neutrons et de pérovskite Pr1-xSrxMnO3 (0.25≤x≤0.45) est également présenté. / Magnetic refrigeration has gained lot of importance and attention as they are highlighted to be environmental friendly, energy efficient. Presently, though at research stage, the magnetic refrigerators are pushed towards realization in domestic application with extensive work on materials and with few working models. One critical issue, the potential resistance to corrosion in case of different class of magnetocaloric materials (Gd6Co1.67Si3, Ni2Mn0.75Cu0.25Ga and Pr0.66Sr0.34MnO3) against the heat transport fluid is addressed. To better understand and improve the observed magnetocaloric properties in Heulser alloys Ni2Mn0.75Cu0.25Ga and to elaborate the same with the magneto-structural relation, studies on (i) cation distribution with in crystal structure and/or (ii) microstructural dependence are presented. Nuclear and magnetic phase diagram based on detailed neutron diffraction and magnetism studies for magnetocaloric perovskite oxide Pr1-xSrxMnO3 (0.25≤x≤0.45) is also presented

Les détecteurs de rayon-X utilisés pour l'imagerie à haute résolution (micromètrique ou submicronique) utilisés aux synchrotrons sont pour la plupart basés sur un système de détection indirecte. Les rayons X ne sont pas directement convertis en signal électrique. Ils sont absorbés par un scintillateur qui est un matériau émettant de la lumière à la suite de l'absorption d'un rayonnement ionisant. L'image émise sous forme de lumière visible est ensuite projetée par des optiques de microscopie sur une camera 2D de type CCD ou CMOS. De nos jours, il existe différents types des scintillateurs. On distingue entre autres des scintillateurs en poudre compactée, micro structurés, céramique poly-cristalline et monocristalline. L’obtention d’une image de très bonne qualité avec une résolution spatiale au-dessous du micromètre requiert le choix d’une couche mince (1-20 µm) monocristalline. Ces types des scintillateurs peuvent être déposes sur un substrat par épitaxie en phase liquide. La très faible efficacité d’absorption dans une couche mince en fait sa faiblesse, surtout pour des énergies au-dessus de 20 keV. A l’ESRF (le synchrotron européen) des énergies jusqu'à 120 keV peuvent être exploitées pour l’imagerie. Des nouveaux scintillateurs sont donc toujours recherchés pour pouvoir améliorer le compromis entre l’efficacité d’absorption et la résolution spatiale. Dans la première partie de cet travail, un model qui décrit les détecteurs indirects pour la haute résolution, est présenté. Cet model permet de calculer la MTF (fonction de transfert de modulation) du système et peut être utilisé pour trouver la combinaison optimal de scintillateur et d’optique selon l’énergie des rayons X. Les simulations ont guidées le choix des scintillateurs à développer par épitaxie.Dans la deuxième partie, deux nouveaux types de scintillateurs développés et caractérisés dans le cadre de ce projet de thèse sont introduits : les couches minces basées sur des monocristaux de gadolinium lutétium aluminium pérovskite (GdLuAP:Eu) et d’oxyde de lutétium (Lu2O3:Eu) / X-ray detectors for high spatial resolution imaging are mainly based on indirect detection. The detector consists of a converter screen (scintillator), light microscopy optics and a CCD or CMOS camera. The screen converts part of the absorbed X-rays into visible light image, which is projected onto the camera by means of the optics. The detective quantum efficiency of the detector is strongly influenced by the properties of the converter screen (X-ray absorption, spread of energy deposition, light yield and emission wavelength). To obtain detectors with micrometer and sub-micrometer spatial resolution, thin (1-20 µm) single crystal film scintillators are required. These scintillators are grown on a substrate by liquid phase epitaxy. The critical point for these layers is their weak absorption, especially at energies exceeding 20 keV. At the European Synchrotron radiation Facility (ESRF), X-ray imaging applications can exploit energies up to 120 keV. Therefore, the development of new scintillating materials is currently investigated. The aim is to improve the contradictory compromise between absorption and spatial resolution, to increase the detection efficiency while keeping a good image contrast even at high energies.The first part of this work presents a model describing high-resolution detectors which was developed to calculate the modulation transfer function (MTF) of the system as a function of the X-ray energy. The model can be used to find the optimal combination of scintillator and visible light optics for different energy ranges, and it guided the choice of the materials to be developed as SCF scintillators. In the second part, two new kinds of scintillators for high-resolution are presented: the gadolinium-lutetium aluminum perovskite (Gd0.5Lu0.5AlO3:Eu) and the lutetium oxide (Lu2O3:Eu) SCFs

Gegenstand der vorliegenden Dissertation ist die Untersuchung von Ca-dotierten PrMnO3 (PCMO) als Katalysator für die (photo)elektrochemische Wasseroxidation. Im Fokus der Untersuchungen stehen die folgenden elementaren Schritte des Gesamtprozesses: i) Die optische Absorption in PCMO wird zunächst als Funktion der Ca-Dotierung und der Temperatur untersucht mit dem Ziel, den Einfluß von Korrelationseffekten auf die optischen Eigenschaften zu verstehen. Die präsentierten Ergebnisse zeigen, dass die Bildung kleiner Polaronen im PCMO als Folge starker Korrelationswechselwirkungen in breites Absorptionsmaximum im Nah-Infrarot bis sichtbarem Energiebereich verursacht, welches im Rahmen eines Photonen-assistierten Polaronenhüpfprozesses und einer Anregung zwischen Jahn-Teller-aufgespaltenen Zuständen diskutiert wird. Weiterhin legt die Dotierungsabhängigkeit der Spektren nahe, dass O 2p und Mn 3d Hybridzustände die Fermienergie-nahe elektronische Struktur bestimmen, wobei der relative Anteil von O 2p mit der Ca-Dotierung variiert. ii) Der aktive Zustand von PCMO in Kontakt mit Wasser bzw. Wasserdampf wird mit Hilfe von Zyklovoltammetrie und in situ ‚environmental‘ Transmissionselektronenmikroskopie (ETEM) für verschiedene Dotierlevels untersucht. Die Ergebnisse beider Methoden ergeben, dass die katalysierte Wasseroxidation gemäß $2\text{H}_2\text{O} \rightarrow \text{O}_2 + 4 \text{H}^+$ mit einem Korrosionsprozess in Form einer Pr/Ca Verarmung und Amorphisierung der PCMO-Elektrode konkurriert. Die höchste katalytische Aktivität sowie Korrosionsstabilität werden im mittleren Dotierungsbereich gefunden. Auf Basis der in situ ETEM Ergebnisse wird außerdem gezeigt, dass durch Zufügen von Monosilan zu Wasserdampf-basierten Elektrolyten im ETEM eine Elektronenstrahl-induzierte Wasseroxidation an aktiven PCMO Oberflächen über die Sekundärreaktion $\text{SiH}_4+2\text{O}_2\rightarrow\text{SiO}_2+2\text{H}_2\text{O}$ nachgewiesen werden kann. Elektronenenergieverlustspektroskopie von PCMO vor und nach der Reaktion in Wasserdampf ergeben, dass der aktive Zustand von PCMO die Bildung und Ausheilung von Sauerstoffleerstellen im Rahmen einer Interkalation des bei der Wasseroxidation freiwerdenden Sauerstoffs beinhaltet. Die Rolle des Elektronenstrahls als Triebkraft für die Wasseroxidation im ETEM wird mithilfe von Elektronenholographie und elektrischen Experimenten sowie theoretischer Modellierung basierend auf Sekundärelektronenemissionen als ein positives Elektronenstrahl-induziertes elektrisches Potential identifiziert.

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.

<p>Developing the next generation soft optoelectronic materials is of great importance for achieving high-performance, low-cost electronics. These novel material systems bring about new chemistry, physical phenomena, and exciting properties. Organic inorganic hybrid two-dimensional perovskites and organic stable radical molecules are two exciting material systems that bear high expectation and await extensive exploration.</p> <p>Organic inorganic hybrid two-dimensional perovskites are considered one of the solutions to the pressing instability issue of halide perovskites toward commercialization. Moreover, dimension reduction of perovskites creates new opportunities for using two-dimensional perovskites as thermoelectric applications due to the ultralow thermal conductivity. However, two-dimensional perovskite thermoelectric is still at its’ incipient stage of development, therefore a timely proof of potential is required to draw further research interests.</p> <p>In earlier part of this work, the two-dimensional perovskites featuring π-conjugated ligands are synthesized and optimized for high thermoelectric performance. With material design, device engineering, intensive measurements, and careful data analysis, we successfully showed that two-dimensional perovskites are competitive candidate for the emerging thermoelectric materials. Furthermore, temperature and carrier concentration dependencies on thermoelectric properties were also established, giving future researchers a generalized optimization strategy. </p> <p>Organic stable radical molecules are promising for organic electronics as stable radicals don’t require high conjugation for efficient solids-state charge transport. Thanks to their unique redox capability and the unpaired electrons, organic radicals have many unique electronic and magnetic properties that could be useful in spin-related applications. However, the understanding in charge transport mechanisms as well as structure-to-properties correlation remain shallow.</p> <p>In later part of this work, we achieved the highest recorded long channel electrical conductivity of non-conjugated radicals. Meanwhile, the important role of close packing between radical sites was demonstrated by slightly changing chemical design that resulted in drastic change in electrical conductivity. Finally, we concluded that the solid-state charge transport in non-conjugated species is governed by variable range hopping mechanisms. </p>

In dieser Dissertation wird eine umfassende Untersuchung von Perowskit-Tintenformulierungen für die Herstellung von hocheffizienten MAPbI3- und FAPbI3-Bauelementen durchgeführt. Darüber hinaus schlagen wir einen kombinatorischen Slot-Die-Beschichtungsansatz für das Screening und die Herstellung von Perowskit-Zusammensetzungen vor. Diese Ergebnisse zeigen, dass die Slot-Die-Beschichtung eine vielversprechende Technik für die Hochskalierung von Metallhalogenid-Perowskit-Dünnschichten ist. / This dissertation gives a comprehensive investigation into perovskite ink formulations for the fabrication of highly efficient MAPbI3 and FAPbI3 devices. Additionally, we propose a combinatorial slot-die coating approach for screening and fabricating perovskite compositions. These results demonstrate that slot-die coating is a promising technique for the upscaling of metal-halide perovskite thin-films.