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Propriétés de surfaces et interfaces de couches minces ferroélectriques de BaTiO3 étudiées par spectroscopie de photoémission in-situ / Surface and interface properties of ferroelectrics BaTiO3 thin film studied by in-situ photoemission spectroscopyArveux, Emmanuel Michel 08 December 2009 (has links)
Cette thèse porte sur l’étude de couches minces ferroélectriques à base de BaTiO3 déposées par pulvérisation cathodique. Ces matériaux permettent par exemple de réaliser des condensateurs accordables ou encore des mémoires non-volatiles pour le stockage d’informations. Cependant, leurs propriétés diélectriques sont considérablement dégradées par des effets extrinsèques d’interfaces; film/substrat ou encore film/électrode. Dans ce contexte, la spectroscopie de photoémission (XPS) a été utilisée pour quantifier les états électroniques et chimiques de ces interfaces avec une approche in-situ. L’étude sur la formation du contact film/électrode a permis de mesurer la hauteur de barrière de Schottky partiellement responsable des caractéristiques capacités – tensions des couches. Des phénomènes de ségrégation ont été mis en évidence révélant une profonde instabilité de la stoechiométrie de surface. Enfin, la conséquence d’un dopage au niobium dans les couches minces de BaTiO3 est discutée du point de vue des modes de compensation, de la solubilité du dopant et des propriétés diélectriques. / The aim of this work was to better understand the surface and interface properties of sputtered ferroelectric BaTiO3 thin films. They are typically used as dielectrics in integrated capacitors, electromechanical sensors and so. This thesis studies the chemical and electronic structures of the interface of BaTiO3 in order to understand basic mechanisms of contact formation with the substrate and the electrode like the Schottky barrier height. Furthermore, the surface stoichiometry of such films has been investigated under different thermal preparation revealing significant instability through segregation phenomenon. Finally, the doping effect with niobium is studied regarding compensation mode, dopant solubility and dielectric properties. The experimental setup allows for in-situ analysis of surface and interface properties using photoelectron spectroscopy.
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Synthèse de nouveaux matériaux multiferroïques au sein de la famille des bronzes quadratiques de formule Ba2LnFeNb4O15 / Synthesis of new multiferroic materials in the family of Ba2LnFeNb4O15 Tetragonal Tungsten BronzesCastel, Elias 03 November 2009 (has links)
Les multiferroïques sont des matériaux dans lesquels plusieurs propriétés ferroïques peuvent coexister, e. g. ferromagnétisme et ferroélectricité. La recherche de tels matériaux fait l'objet d'une activité croissante en raison de l’enjeu majeur qu’ils représentent dans de nombreux domaines (mémoires, spintronique…). Les matériaux qui possèdent les propriétés nécessaires pour des applications futures sont cependant peu nombreux. Des niobates de formule Ba2LnFeNb4O15 (Ln = lanthanide), de structure bronze quadratique (TTB) susceptibles de présenter un ordre ferroélectrique et un ordre magnétique ont été synthétisés. Les propriétés magnétiques des céramiques proviennent d'une phase secondaire, faisant d’eux des composites multiferroïques. Leur souplesse cristallochimique permet de contrôler les propriétés composites par substitutions cationiques dans la matrice TTB. Afin de compléter l'étude cristallochimique, la croissance de monocristaux de TTB a été entreprise avec succès. / Multiferroics are materials which possess several ferroic properties, e.g. ferroelectricity, ferromagnetism. The search for multiferroics arises a growing activity, due to their potential applications in memories, spintronic… Yet the materials displaying the adequate properties for future application are very few. Niobates with the formula Ba2LnFeNb4O15, potentially ferroelectric and ferromagnetic, have been synthesized. The magnetic properties of the ceramics are related to a secondary phase, thus making them composite multiferroics. Their crystal-chemical flexibility allows for the composites properties tuning by cationic substitutions into the TTB framework. To complete the crystal-chemical study, the growth of TTB single-crystals was successfully engaged.
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Etude des propriétés diélectriques et structurales de monocristaux et céramiques de structure TTB / Study of dielectric and structural properties of single crystals and ceramics structure TTBHeijboer, Pierre 20 June 2014 (has links)
Les travaux présentés dans ce manuscrit concernent des niobates de formulation Ba2LnNb4O15 (Ln = La ou Nd) et de structure "Tetragonal Tungsten Bronze" (TTB). Ces travaux se situent à la charnière de la chimie et de la physique des matériaux diélectriques et visent à mettre en relation structure cristalline et propriétés diélectriques. L'étude a été menée sur des TTB élaborés sous forme céramique et monocristalline. Après détermination de conditions optimales de croissance, par fusion de zone en four à image, des sections monocristallines ont été obtenues et caractérisées. Les résultats obtenus suggèrent des liens étroits entre composition, modulations structurales apériodiques et comportement diélectrique. Dans le même temps, deux nouvelles solutions solides céramiques ont été explorées, avec des schémas de substitution différents menant notamment à une réflexion très large sur les liens cristallochimie-ferroélectricité dans cette famille de TTB. Ces solutions solides présentent un crossover relaxeur-ferroélectrique, un comportement original et déjà observé dans d'autres solutions solides issues de cette famille de TTB. Des caractérisations avancées (mesures pyro- et piézoélectriques, cycles de polarisation) et des études structurales résolues en composition et en température ont permis d'établir des diagrammes de phases diélectriques montrant l'existence d'un état ferroélectrique métastable. Finalement, la présence d’une modulation structurale bidimensionnelle a pu être confirmée, dans les monocristaux et dans les céramiques, et l'ensemble des résultats obtenus pointent son implication dans les comportements cristallochimiques originaux rencontrés dans ces TTB. / The present work deals with Ba2LnNb4O15 (Ln = La ou Nd) niobates crystallizing with the "Tetragonal Tungsten Bronze" (TTB) structure. These researches, at the interface of chemistry and physics of dieletrics, aim at establishing structure / dielectric properties relationships. They were performed on TTB materials elaborated in ceramic and single crystal forms. Following optimization of growth parameters with an image furnace, single crystals were obtained and characterized. The results obtained suggest that composition, aperiodically modulated structure and dielectric behavior are closely tied in TTBs. Meanwhile, two new ceramic solid solutions with different substitutions schemes were investigated, deepening the insight on crystal-chemistry and ferroelectricity of TTBs. These solid solutions exhibit a relaxor-ferroelectric crossover, an original behaviour previously observed in solid solutions derived from the same family of TTB niobates. Advanced physical characterization (ferro-, pyro- and piezoelectric measurements, polarization loops), and composition/temperature resolved structural studies, allowed for the determination of a dielectric phase diagrams showing the presence of a metastable ferroelectric state. Finally, the existence of a two-dimensional structural modulation in single crystals and ceramics has been confirmed, and the whole set of experimental results points towards its implication in the original dielectric behavior observed in these TTBs.
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Nanosecond optical parametric oscillators and amplifiers based on periodically poled KTiOPO4Hellström, Jonas January 2001 (has links)
Optical parametric oscillators (OPOs) and optical parametricamplifiers (OPAs) constitute a class of optical frequencyconverting devices that have many possible applications, e.g.in range finding, molecular spectroscopy and medicine. They canconvert the frequency of the incident pump field with highefficiency, and generate two waves at new frequencies that willbe continuously tuneable over a wide spectral range. Virtuallyany wavelengths within the transparency region of the nonlinearmaterial can be generated if the material can bequasi-phasematched (QPM). In addition, QPM gives thepossibility to utilise the largest nonlinear tensor element ofthe material and allows walk-off free interaction between thewaves. The aims of this thesis have been to investigate thepossibility to use QPM KTiOPO4crystals as nonlinear material in nanosecond OPOsand OPAs operating at room-temperature, and to explore theadvantages and shortcomings of these devices. The technique ofelectric field poling has been employed to implement the QPMstructure in flux grown KTiOPO4(KTP). The main conclusion is that periodically poled KTP (PPKTP)is a suitable material to use in nanosecond OPOs and OPAs. Thematerial properties that foremost make KTP into an attractivenonlinear material are: The large value of the nonlinearcoefficient d33, the high resistance to optically inducedbreakdown, the low susceptibility to grey-track formation, theinsensitivity to the photorefractive effect, the widetransparency and the low coercive field. The thesis shows that it is possible to pole large volumesof KTP with a high quality of the QPM structure. Highlyefficient nanosecond OPOs have been constructed during thisproject. Maximum conversion efficiencies have reached 45 % inthe case of a singly resonant OPO (SRO) built around a 3 mmthick PPKTP crystal. Total pulse energies for both the signal(1.72 µm) and the idler (2.8 µm) of up to 18 mJ wasreached and an average output power of 2 W was obtained forthis sample. However, up to 24 W was produced in a doublyresonant OPO operating close to degeneracy. The efficiencyreached 48 % for that case. Truly continuous and very widespectral tuning has also been demonstrated, as well as a narrowbandwidth OPO operating on one single longitudinal mode. <b>Keywords:</b>optical parametric oscillators, opticalparametric amplifiers, quasi-phasematching, KTiOPO4, nonlinear optics, frequency conversion, periodicelectric field poling, ferroelectrics, high-order secondharmonic generation, electro-optic effect.
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Processing and On-Wafer Test of Ferroelectric Film Microwave VaractorsKim, Jang-Yong January 2006 (has links)
Microwave materials have been widely used in a variety of applications ranging from communication devices to military satellite services, and the study of materials properties at microwave frequencies and the development of functional microwave materials have always been among the most active areas in solid-state physics, materials science, electrical and electronic engineering. In recent years, the increasing requirements for the development of high speed, high frequency circuits and systems require complete understanding of the properties of materials function at microwave frequencies. Ferroelectric materials usually have high dielectric constant, and their dielectric properties are temperature and electric field dependent. The change in permittivity as a function of electric field is the key to a wide range of applications. Ferroelectric materials can be used to fabricate capacitors for electronic industry because of their high dielectric constant, and this is important in the trend toward miniaturization and high functionality of electronic products. The simple tunable passive component based on ferroelectric films is a varactor which can be made as a planar structure and used for electrically tunable microwave integrated circuits. It is an important task to sinter highly tunable and low loss ferroelectrics, fabricate and test the properties of microwave ferroelectric components. This thesis shows experimental results on growth, crystalline and microwave properties of Na0.5K0.5NbO3 (NKN), AgTa0.5Nb0.5O3 (ATN), Ba0.5Sr0.5TiO3 (BST) as well as AgTaO3 (ATO), and AgNbO3 (ANO) thin films. The films were grown by Pulsed Laser Deposition (PLD) and rf-magnetron sputtering techniques from stoichiometric high density ceramic NKN, ATN, ATO, ANO and BST targets onto LaAlO3 (LAO), Al2O3 (r-cut sapphire), Nd:YAlO3 single crystals and amorphous glass substrates. Advanced X-ray diffraction examinations showed NKN, ATN, BST films on LAO substrates grow epitaxially, whereas films on r-cut sapphire were found to be preferentially (00l) oriented. Coplanar waveguide 2 µm finger gap interdigital capacitor (CPWIDC) structures were fabricated by photolithography process and metal lift-off technique. On-wafer tests up to 40 GHz were performed to characterize microwave properties of the ferromagnetic film CPWIDC devices. The measurement setup is composed of network analyzer, probe station, and microwave G-S-G probes. External electric field was applied to planar capacitors to measure tunability. Original de-embedding technique has been developed to calculate capacitance, loss tan δ, and tunability of varactors from the measured S-parameters. NKN film interdigital capacitors on Nd:YAlO3 showed superior performance compared to ATN in the microwave range from 1 to 40 GHz. Within this range, the voltage tunability (40V, 200 kV/cm) was about 29%, loss tangent ~ 0.13, K-factor = tunability/tan δ from 152% @ 10GHz to 46% @ 40GHz. The ATN/sapphire CPWIDCs showed the lowest dispersion ~ 4.3% in whole frequency range from 1 to 40 GHz, voltage tunability 4.7% @ 20GHz and 200 kV/cm, lowest loss tangent ~ 0.068 @ 20GHz, K-factor = tunability/tan δ ranged from 124% @ 10GHz to 35% @ 40GHz. BST film CPWIDCs on sapphire showed frequency about 17%, the highest voltage tunability ~ 22.2%, loss tangent ~ 0.137 @ 20GHz, and K-factor = 281% @ 10GHz to 95% @ 40GHz. / QC 20100906
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Electro-Optical Na0.5K0.5NbO3 FilmsBlomqvist, Mats January 2005 (has links)
Ferroelectric oxides are a group of advanced electronic materials with a wide variety of properties useful in applications such as memory devices, resonators and filters, infrared sensors, microelectromechanical systems, and optical waveguides and modulators. Among the oxide perovskite-structured ferroelectric thin film materials, sodium potassium niobate or Na0.5K0.5NbO3 (NKN) has recently emerged as one of the most promising materials in radio frequency (rf) and microwave applications due to high dielectric tenability and low dielectric loss. This thesis presents results on growth and structural, optical, and electrical characterization of NKN thin films. The films were deposited by rf-magnetron sputtering of a stoichiometric, high density, ceramic Na0.5K0.5NbO3 target onto single crystal LaAlO3 (LAO), Al2O3 (sapphire), SrTiO3, and Nd:YAlO3, and polycrystalline Pt80Ir20 substrates. By x-ray diffractometry, NKN films on c-axis oriented LaAlO3, SrTiO3 and Nd:YAlO3 substrates were found to grow epitaxially, whereas films on r-cut sapphire and polycrystalline Pt80Ir20 substrates were found to be preferentially (00l) oriented. The surface morphology was explored using atomic force microscopy. Optical and waveguiding properties of the Na0.5K0.5NbO3/substrate heterostructures were characterized using prism-coupling technique. Sharp and distinguishable transverse magnetic and electric propagation modes were observed for NKN thicknesses up to 2.0 μm. The extraordinary and ordinary refractive indices were calculated together with the birefringence of the NKN material. The electro-optic effect in transverse geometry was measured in transmission, where the effective linear electro-optic response was determined to reff = 28 pm/V for NKN/Al2O3 with an applied dc field up to 18 kV/cm. The ferroelectric state in NKN films on Pt80Ir20 at room temperature was indicated by a polarization loop with saturated polarization as high as 33.4 μC/cm2 at 700 kV/cm, remnant polarization of 10 μC/cm2, and coercive field of 90 kV/cm. Current-voltage characteristics of vertical Au/NKN/PtIr capacitive cells and planar Au/NKN/LAO interdigital capacitors (IDCs) showed very good insulating properties, with the leakage current density for an NKN IDC on the order of 30 nA/cm2 at 400 kV/cm. Rf dielectric spectroscopy demonstrated low loss, low frequency dispersion, and high voltage tunability. At 1 MHz, NKN/LAO showed a dissipation factor tan δ = 0.010 and a tunability of 16.5 % at 200 kV/cm. For the same structure the frequency dispersion was Δεr = 8.5 % between 1 kHz and 1 MHz. / QC 20100928
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Nanosecond optical parametric oscillators and amplifiers based on periodically poled KTiOPO4Hellström, Jonas January 2001 (has links)
<p>Optical parametric oscillators (OPOs) and optical parametricamplifiers (OPAs) constitute a class of optical frequencyconverting devices that have many possible applications, e.g.in range finding, molecular spectroscopy and medicine. They canconvert the frequency of the incident pump field with highefficiency, and generate two waves at new frequencies that willbe continuously tuneable over a wide spectral range. Virtuallyany wavelengths within the transparency region of the nonlinearmaterial can be generated if the material can bequasi-phasematched (QPM). In addition, QPM gives thepossibility to utilise the largest nonlinear tensor element ofthe material and allows walk-off free interaction between thewaves.</p><p>The aims of this thesis have been to investigate thepossibility to use QPM KTiOPO<sub>4</sub>crystals as nonlinear material in nanosecond OPOsand OPAs operating at room-temperature, and to explore theadvantages and shortcomings of these devices. The technique ofelectric field poling has been employed to implement the QPMstructure in flux grown KTiOPO<sub>4</sub>(KTP).</p><p>The main conclusion is that periodically poled KTP (PPKTP)is a suitable material to use in nanosecond OPOs and OPAs. Thematerial properties that foremost make KTP into an attractivenonlinear material are: The large value of the nonlinearcoefficient d<sub>33</sub>, the high resistance to optically inducedbreakdown, the low susceptibility to grey-track formation, theinsensitivity to the photorefractive effect, the widetransparency and the low coercive field.</p><p>The thesis shows that it is possible to pole large volumesof KTP with a high quality of the QPM structure. Highlyefficient nanosecond OPOs have been constructed during thisproject. Maximum conversion efficiencies have reached 45 % inthe case of a singly resonant OPO (SRO) built around a 3 mmthick PPKTP crystal. Total pulse energies for both the signal(1.72 µm) and the idler (2.8 µm) of up to 18 mJ wasreached and an average output power of 2 W was obtained forthis sample. However, up to 24 W was produced in a doublyresonant OPO operating close to degeneracy. The efficiencyreached 48 % for that case. Truly continuous and very widespectral tuning has also been demonstrated, as well as a narrowbandwidth OPO operating on one single longitudinal mode.</p><p><b>Keywords:</b>optical parametric oscillators, opticalparametric amplifiers, quasi-phasematching, KTiOPO<sub>4</sub>, nonlinear optics, frequency conversion, periodicelectric field poling, ferroelectrics, high-order secondharmonic generation, electro-optic effect.</p>
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Off-axis Holografie im aberrationskorrigierten Transmissionselektronenmikroskop / Off-axis electron holography in an aberration-corrected transmission electron microscopeLinck, Martin 15 July 2010 (has links) (PDF)
Die off-axis Elektronenholografie im Transmissionselektronenmikroskop (TEM) erlaubt die quantitative Rekonstruktion der komplexen Objektaustrittswelle mit atomarer Auflösung. Die Auswertung der Phase dieser Welle ermöglicht die Unterscheidung der Atomsorten bzw. das Zählen der Atome in Projektionsrichtung sowie die Bestimmung von Atompositionen. Damit ist ein TEM über die einfache Abbildung hinaus ein sehr leistungsstarkes Messgerät zur quantitativen Analyse kleinster Strukturen bis hin zur atomaren Skala.
Die Prozedur von der Aufnahme eines hochaufgelösten Elektronenhologramms über die Rekonstruktion bis zur bildfehlerkorrigierten Objektwelle ist jedoch sehr umfangreich und teils sehr anfällig für Artefakte. Diese Arbeit zeigt unter kritischer Betrachtung der einzelnen Einflüsse, wie dieser Weg zu beschreiten ist, um schlussendlich zu einer artefaktfreien, interpretierbaren Objektwelle zu gelangen.
Im letzten Jahrzehnt haben Bildfehler-Korrektoren die höchstauflösende Transmissions-elektronenmikroskopie auf instrumenteller Seite revolutioniert. Auch die off-axis Holografie kann eine ganze Reihe von Vorteilen aus diesem elektronenoptischen Zusatzsystem ziehen. Neben der Analyse dieser einzelnen Verbesserungen, insbesondere der Phasensignalauflösung, wird gezeigt, wie es das Cs-korrigierte TEM zu optimieren gilt, um schließlich bestmögliche Ergebnisse für quantitative Objektanalyse zu erzielen.
Zwei Anwendungsbeispiele zeigen experimentelle Ergebnisse der Elektronenholografie mit Cs-korrigierten Mikroskopen. Bei der Analyse ferroelektrischer Nanoschichten erweisen sich die einzigartigen Möglichkeiten der holografischen Auswertung im Zusammenspiel mit der nunmehr hervorragenden Signalauflösung als äußerst nützlich, um die ferroelektrische Polarisation zu ermitteln. Die Objektwellenrekonstruktion der Korngrenze in einer Goldfolie demonstriert weitere Verbesserungen für die Holografie, wenn zusätzlich eine neuartige Elektronenquelle mit höherem Richtstrahlwert zum Einsatz kommt. Einzelne Goldatome werden mit einem Signal-Rausch-Verhältnis von ca. 10 in Amplitude und Phase messbar. / Off-axis electron holography in a transmission electron microscope (TEM) allows reconstructing the complex object exit-wave quantitatively with atomic resolution. Analyzing the phase shift of this wave gives access to the atomic species and enables counting the number of atoms in projection direction as well as determining atom positions. Therefore, a TEM is a very powerful measuring device for quantitative analysis of smallest structures down to the atomic scale beyond simple microscopic imaging.
The procedure of the recording of a high-resolution electron hologram, its reconstruction, and after numerical aberration correction finally ending up with the object-exit wave, is quite comprehensive and partially susceptible to artifacts. This work shows how to manage this procedure in order to obtain an interpretable object exit-wave, which is free of artifacts.
In instrumentation within the last decade aberration correctors have revolutionized high-resolution electron microscopy. Also off-axis holography can benefit from this electron optical add-on module. Besides the exploration of each improvement, in particular the phase detection limit, this work demonstrates, how to optimize the Cs-corrected TEM in order to get best possible results for quantitative object analysis.
Two application examples show experimental results of electron holography with Cs-corrected microscopes. For the investigation of ferroelectric nanolayers, the unique possibilities of the holographic evaluation together with the strongly improved signal resolution turn out to be very useful when determining the ferroelectric polarization. The object wave reconstruction of the grain boundary in a gold film demonstrates further improvements for holography, when additionally using a new electron gun with improved brightness. Single gold atoms become measurable with a signal-noise-ratio of about 10 in amplitude and phase.
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Domains and functionality in multiferroic BiFeO3 filmsWaterfield Price, Noah January 2017 (has links)
For over half a century, the technological promise of spins manipulable by a small voltage has captivated the interest of experimental and theoretical researchers alike. However, if thin-film multiferroics are to be incorporated into future data storage devices, a much greater understanding of their behaviour and how they differ from their bulk counterparts is required. In this thesis, we probe the fundamental multiferroic properties of BiFeO<sub>3</sub> films through a combination of state-of-the-art diffraction and microscopy techniques. We investigate the coupling between magnetic, ferroelectric, and structural order, with a focus on domains, and how the domain structure may be manipulated in order to tailor the multiferroic properties of the material. Using non-resonant magnetic x-ray scattering (NXMS) and neutron diffraction, we study the magnetic and structural properties of (111)<sub>pc</sub>-oriented BiFeO<sub>3</sub> films. Contrary to the general belief that to they grow as a rhombohedral monodomain, we find that they comprise a sub-micron texture of monoclinic domains. The magnetic structure is found to be intimately coupled to the structure, resulting in the propagation vector being locked to the monoclinic b-axis. This magnetoelastic coupling opens up a route to strain-engineer the magnetic domains via epitaxial strain. By growing BiFeO<sub>3</sub> films on a lower-symmetry, TbScO<sub>3</sub> substrate, we are able to engineer a magnetic, structural and ferroelectric monodomain, coherent over the entire film, constituting an increase in the domain size by over five orders of magnitude. We directly demonstrate the coupling between ferroelectric and magnetic order parameters of the cycloidal magnetic structure. Using NXMS polarimetry to measure directly the magnetic polarity, we show that upon switching the ferroelectric polarisation, the magnetic polarity switches accordingly---a major rearrangement of the magnetic structure, with each spin rotating by 90 degrees on average. This goes counter to idea that magnetic and ferroelectric order parameters are only weakly coupled in type-I multiferroics. Finally, using photoemission electron microscopy we are able to directly image the sub-micron magnetostructural domain structure. We further show that there is a strong interfacial coupling between the magnetostructural domains of BiFeO<sub>3</sub> with a ferromagnetic overlayer. The BiFeO<sub>3</sub> domains are found to impose a uniaxial anisotropy in the overlayer, opening up a route to control ferromagnetic domains.
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Structure and properties of some triangular lattice materialsDownie, Lewis James January 2014 (has links)
This thesis is concerned with the study of two families of materials which contain magnetically frustrated triangular lattices. Each material is concerned with a different use; the first, analogues of YMnO₃, is from a family of materials called multiferroics, the second, A₂MCu₃F₁₂ (where A = Rb¹⁺, Cs¹⁺, M = Zr⁴⁺, Sn⁴⁺, Ti⁴⁺, Hf⁴⁺), are materials which are of interest due to their potentially unusual magnetic properties deriving from a highly frustrated Cu²⁺-based kagome lattice. YFeO₃, YbFeO₃ and InFeO₃ have been synthesised as their hexagonal polymorphs. YFeO₃ and YbFeO₃ have been studied in depth by neutron powder diffraction, A.C. impedance spectroscopy, Mössbauer spectroscopy and magnetometry. It was found that YFeO₃ and YbFeO₃ are structurally similar to hexagonal YMnO₃ but there is evidence for a subtle phase separation in each case. Low temperature magnetic properties are also reported, and subtle correlations between the structural, electrical and magnetic properties of these materials have been found. InFeO₃ was found to adopt a higher symmetry and is structurally similar to the high temperature phase of YMnO₃. TbInO₃ and DyInO₃ have also been synthesised and studied at various temperatures. The phase behaviour of TbInO₃ was analysed in detail using neutron powder diffraction and internal structural changes versus temperature were mapped out – there is also evidence for a subtle isosymmetric phase transition. Neither DyInO₃ nor TbInO₃ show long-range magnetic order between 2 and 300 K, or any signs of ferroelectricity at room temperature. The new compounds Cs₂TiCu₃F₁₂ and Rb₂TiCu₃F₁₂ have both been synthesised and shown to be novel kagome lattice based materials. The former shows a transition from rhombohedral to monoclinic symmetry in the powder form and from rhombohedral to a larger rhombohedral unit cell in the single crystal – a particle size based transition pathway is suggested. For Rb₂TiCu₃F₁₂ a complex triclinic unit cell is found, which distorts with lowering temperature. Both materials show magnetic transitions with lowering temperature. The solid solution Cs₂₋ₓRbₓSnCu₃F₁₂ (x = 0, 0.5, 1.0, 1.5, 2.0) was synthesised and investigated crystallographically, demonstrating a range of behaviours. Rb₂SnCu₃F₁₂ displays a rare re-entrant structural phase transition. In contrast, Cs₀.₅Rb₁.₅SnCu₃F₁₂ shows only the first transition found in the Rb⁺ end member. CsRbSnCu₃F₁₂ adopts a lower symmetry at both room temperature and below. Cs₁.₅Rb₀.₅SnCu₃F₁₂ and Cs₂SnCu₃F₁₂ show a rhombohedral - monoclinic transition, which is similar to that found in Cs₂TiCu₃F₁₂.
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