Rozprawy doktorskie na temat „Oxide thin films and heterostructure”

Doutoramento em Engenharia Física
O presente trabalho de doutoramento é um estudo de propriedades físicas e aspectos estruturais de filmes de óxidos e heteroestruturas multiferróicas, englobando técnicas de caracterização do nível macroscópico ao microscópico. O objectivo principal é a compreensão de novas heteroestruturas epitaxiais multifuncionais e as suas interfaces para junções de túnel magnetoelétricas e filtros de spin. Os principais materiais em estudo foram manganitas à base de La dopadas com iões divalentes (ba, Sr), apresentando efeito magnetoelétrico, sendo preparadas em diferentes substratos e diferentes técnicas de crescimento, optimizadas para epitaxia e qualidade de interface. O estudo combinado de propriedades eléctricas e magnéticas permitiu estabelecer as condições necessárias para a aplicação dos materiais multiferróicos em estudo, por técnicas experimentais apresentadas neste trabalho. O trabalho consistiu no estudo sistemático de microestrutura de filmes finos de La0:7Sr0:3MnO3 em substratos de SrTiO3, preparados por pulsed laser deposition, o filme fino de La0:9Ba0:1MnO3 e a heteroestrutura La0:9Ba0:1MnO3/BaTiO3/La0:9Ba0:1MnO3 em substrato de Al2O3, e filme fino de La0:9Ba0:1MnO3, BaTiO3 e heteroestrutura de La0:9Ba0:1MnO3/BaTiO3/La0:9Ba0:1MnO3 em substrato de Si, preparado por RF magnetron sputtering. A caracterização estrutural das amostras foi feita principalmente por difracção de raio-X (XRD) convencional e de alta resolução e Microscopia de Transmissão de Alta Resolução (HRTEM). A composição química foi analisada por Electron Dispersion Spectroscopy (EDS), Rutherford backscattering spectroscopy (RBS) e energy filtered transmission electron microscopy (EFTEM). As medidas de magnetização forram realizada com a um magnetómetro superconducting quantum interference device (SQUID). A análise da topografia e efeitos locais foi realizada por microscopia de varimento de ponta usando microscopia da Força Atómica (AFM) e de resposta piezoeléctronica (PFM). Os resultados mostram claramente uma evolução da microestrutura dos filmes finos de La0:7Sr0:3MnO3, á medida que aumenta a sua espessura, passando de uma estrutura policristalina no filme mais fino (13.5 nm) a colunar inclinado (45 nm e 200 nm), a uma estrutura ramificada no filme mais espesso (320 nm). A alteração na estrutura do filme é devida à tensão pelo substrato e deformação da estrutura nas etapas iniciais de crescimento, onde se detectaram fronteiras anti-phase e maclas. A evolução da estrutura modificou as propriedades magnéticas dos filmes a baixa temperatura (abaixo da temperatura de transição estrutural do substrato de SrTiO3), mostrando magnetização em excesso e defeito, para espessuras abaixo e acima de 100 nm, respectivamente. Análises STEM-EELS e EFTEM mostraram a diferença em composição elementar dos filmes perto das fronteiras e na interface com o substrato.No âmbito do plano de trabalhos de doutoramento, o segundo substrato consiste em estudar as propriedades físicas e estruturais de filmes finos de La0:9Ba0:1MnO3 e heteroestruturas La0:9Ba0:1MnO3/BaTiO3/La0:9Ba0:1MnO3 em substratos de Al2O3, revelando estruturas altamente orientadas. A razão La/Ba do filme e heteroestrutura é drasticamente diferente do alvo providenciado, La0:7Ba0:3MnO3, como provado por XRD, RBS e transições de fase magnéticas. As propriedades magnéticas e eléctricas das estruturas mostraram uma forte dependência na cristalinidade do filme e da heteroestrutura. A parte final do trabalho é dedicada aos filmes de La0:9Ba0:1MnO3, BaTiO3 e a heteroestrutura de La0:9Ba0:1MnO3/BaTiO3/La0:9Ba0:1MnO3 em substrato de Si, que em comparação com as estruturas em substrato de ALO, provaram o efeito da cristalinidade nas propriedades magnéticas, eléctricas e de magneto-resistência do filme e heteroestrutura. Foi mostrado que um grau superior de cristalinidade leva a uma mais elevada magnetização, reduzindo a resistividade das estruturas. Pela primeira vez, um estudo de deformação de topografia por aplicação de uma tensão dc externa foi feito num filme fino de BaTiO3 em Si, usando uma técnica de poling num microscópio de força piezoresponse. Os resultados mostraram a capacidade de uma modificação controlada da superfície, por aplicação de uma voltagem externa nointervalo 14V < Vapp < 20V. Abaixo destes valores, não se observou alguma deformação na topografia, enquanto acima deste intervalo, a 30V, a superfície foi completamente danificada. A mudança topográfica produzida mostrou estabilidade no tempo, onde após a aplicação de 20V, a área modificada alcançou 83% da altura as-poled ( 9 nm) em 90 minutos, a 7,4 nm. A resposta assimétrica de piezoresponse da área poled foi associada à existência de um campo eléctrico interno na amostra, que foi também provado através de medidas de espectroscopia de switching no filme fino. A heteroestrutura no substrato de Si mostraram o mesmo fenómeno que a mono-camada de BaTiO3, onde o arranjo de heteroestrutura realça o efeito de voltagem aplicada na topografia. Aplicando 10V, a estrutura da superfície foi alterada na heteroestrutura e houve uma modificação visível da camada de BaTiO3, alterando também a topografia da camada superior de La0:9Ba0:1MnO3.
This present PhD work made a study of structural aspects and physical properties of the oxide films and multiferroic heterostructures, encompassing the techniques from macroscopic level to microscopic description. The understanding of novel multifunctional epitaxial heterostructures and their interfaces for magneto-electrically driven tunnel junctions and spin-filters is the central objective. The main materials in study were La based doped manganites with magnetoelectric effect prepared on different substrates and growth conditions, optimized for epitaxy and interface quality. The combined study of electric and magnetic properties allowed us examining the conditions required for application of the studied multiferroic materials and experimental techniques are presented in this work. The work consists of three main substrates, a systematic study of microstructure of La0:7Sr0:3MnO3 thin films on SrTiO3 substrate, prepared by pulsed laser deposition, the La0:9Ba0:1MnO3 thin film and La0:9Ba0:1MnO3/BaTiO3/La0:9Ba0:1MnO3 heterostructure on Al2O3 substrate, and the La0:9Ba0:1MnO3 thin film, BaTiO3 and La0:9Ba0:1MnO3/BaTiO3/La0:9Ba0:1MnO3 heterostructure on Si substrate, prepared by RF magnetron sputtering. Main structural characterization of samples was performed by conventional and high resolution X-Ray Diffraction (XRD), High Resolution Transmission Electron Microscopy (HRTEM); chemical composition was determined by Electron Dispersion Spectroscopy (EDS), Rutherford Backscattering Spectroscopy (RBS) and Energy Filtered Transmission Electron Microscopy (EFTEM); Magnetization measurements done with a Superconducting Quantum Interface Device (SQUID) magnetometer. Surface probing of topography and local effects was performed, using Atomic Force (AFM) and Piezo-Response (PFM) Microscopy. Results clearly showed that there is an evolution in the microstructure of the La0:7Sr0:3MnO3 thin films, by increasing their thickness, changing from polycrystalline structure in the thinnest film (13.5 nm) to tilted columnar structure(45 nm and 200 nm) and to a branched structure in the thickest film (320 nm). The change in the structure of the film is due to the strain from the substrate and deformation of the structure in the early stages of the growth, where anti-phase boundaries and twinning were detected. The evolution of the structure modified the low temperature (below structural phase transition of SrTiO3 substrate) magnetic properties of the films, showing in-excess and in-defect magnetization, below and above 100 nm thickness, respectively. Also, STEM-EELS and EFTEM analysis showed the difference in the elemental composition of the films near the boundaries and interface with the substrate.In the scope of the PhD work plan, the second substrate consists of studying the structural and physical properties of La0:9Ba0:1MnO3 thin film and La0:9Ba0:1MnO3/BaTiO3/La0:9Ba0:1MnO3 heterostructure on Al2O3 substrate, where they showed highly oriented structure. The La/Ba ratio of the single layer film and heterostructure is drastically different from the target, La0:7Ba0.3MnO3, proven by XRD, RBS, and magnetic phase transitions. The magnetic and electrical properties of the structures showed strong dependence on the crystallinity of the samples. The final part of the work is devoted to the La0:9Ba0:1MnO3 and BaTiO3 thin films and La0:9Ba0:1MnO3/BaTiO3/La0:9Ba0:1MnO3 heterostructure on Si substrate, which in comparison with the structures on Al2O3 substrate, highlights the influence of crystallinity on magnetic, ferro-electrical and magnetoresistance properties of the film and heterostructure. It is shown that higher degree of crystallinity leads to higher magnetization and lowers the resistivity. For the first time, a study of the topography deformation by applying a dcexternal voltage was done on BaTiO3 thin film on Si, using a poling technique in a piezoresponse force microscope. The results show the ability of controlled modification of the surface, by applying an external voltage/electric field in the range of 14V< Vapp<20V. Below this range, no deformation is observed on the topography, and above this interval, at 30V, the surface is completely damaged. The produced topographical change show stabilization in respect to time, where after applying 20V, the modified area reaches its 83% of the as-poled height ( 9nm) in 90 minutes, to 7.4 nm. The asymmetrical response in the piezoresponse of the poled area is related to the existence of an internal built-in electric field in the sample, which is also confirmed by performing switching spectroscopy measurements on the single layer. The heterostructure on the Si substrate shows the same phenomena, as the BTO single layer, where the heterostructure arrangement enhances the applied voltage effect on the topography. With applying 10V, the structure of the surface changes in the heterostructure and a visible modification of BaTiO3 layer, changing also the topography of La0:9Ba0:1MnO3 top layer is observed.

En esta memoria se describe el crecimiento, mediante pulverización catódica rf, de capas delgadas de NiFe2O4 y CoCr2O4 sobre distintos substratos y la subsiguiente caracterización magnética y eléctrica. El objetivo es integrar dichas capas en dispositivos magnetoelectrónicos tales como uniones túnel o filtros de spin.
Hemos descubierto que el crecimiento epitaxial permite estabilizar fases nuevas del óxido NiFe2O4, fases que no existen en la forma másiva, y que tienen propiedades remarcablemente distintas. Como por ejemplo: un aumento dramático de la magnetización o la posibilidad de modificar drásticamente sus propiedades de transporte, pudiéndose obtener capas aislantes -como es en forma cerámica- o conductivas. Se ha realizado un estudio sistemático de los efectos del espesor de la capa y de las condiciones de crecimiento sobre las propiedades de magnetotransporte y los mecanismos de crecimiento.
Argumentamos que el aumento de la magnetización es debido a la estabilización de una fase NiFe2O4 espinela que es parcialmente inversa, en la que los iones Ni2+ están distribuidos entre las dos posiciones disponibles (tetraédrica y octaédrica) de la estructura. En la forma masiva del material los iones Ni solo se encuentran en los sitios octaédricos. La introducción adicional de vacantes de oxígeno es probablemente la causa de la existencia de una configuración electrónica mixta Fe2+/3+ en la subred octaédrica y de la alta conductividad de las capas.
Hemos aprovechado la capacidad de obtener epitaxias de NiFe2O4 ferrimagnéticas conductoras o aislantes para integrarlas en dos distintos dispositivos magnetoelectrónicos: una unión túnel magnética y un filtro de spin.
Las capas conductoras de NiFe2O4 se han empleado como electrodos ferrimagnéticos-metálicos en uniones túnel. El otro electrodo magnético es (La,Sr)MnO3 y la barrera túnel SrTiO3. Se ha podido medir una magnetoresistencia túnel importante hasta temperaturas tan altas como 280K. Los valores de magnetoresistencia corresponden a una polarización de spin del NiFe2O4 de aproximadamente un 40%, que es prácticamente independiente de la temperatura. Estos resultados sugieren que la nueva fase conductora que hemos estabilizado es un candidato interesante como fuente de corriente polarizada en spin.
Por otra parte, el NiFe2O4 aislante se ha implementado, por primera vez, como barrera túnel en una heteroestructura de filtro de spin. El electrodo magnético es (La,Sr)MnO3 y el electrodo no magnético Au. Hemos observado una magnetoresistencia túnel que alcanza valores de hasta un 50%. A partir de estas medidas, hemos deducido detalles relevantes de la estructura electrónica de la fase parcialmente inversa de NiFe2O4.
Hemos crecido el óxido CoCr2O4 sobre distintos substratos, tales como MgO(001) y MgAl2O4(001). Hemos podido comprobar que este óxido presenta una pronunciada tendencia a un crecimiento 3D. Por esta razón, las superficies de la capa no son nunca suficientemente planas y no se pueden usar en heteroestructuras túnel.
Sin embargo hemos aprovechado esta característica para controlar el crecimiento de estas estructuras 3D y hemos conseguido la formación de objetos submicrónicos, autoorganizados con formas piramidales muy bien definidas. El estudio detallado del efecto de los parámetros de crecimiento nos ha permitido por una parte, dilucidar cuales son los mecanismos que llevan a una autoorganización tan perfecta y por otra determinar que, en las condiciones adecuadas, se pueden obtener templates totalmente faceteados con múltiples posibilidades para futuras aplicaciones.
In this thesis the growth of thin films of NiFe2O4 and CoCr2O4 by RF sputtering on different oxide substrates and the characterization of their magnetic and electric properties is reported. The aim is to integrate the films into spintronic devices namely magnetic tunnel junctions and spin filter.
It was found that the epitaxial growth of these films permits to stabilize new phases of NiFe2O4, which are not found for the bulk material and which show remarkably distinct properties. A strong enhancement of the saturation magnetization was found as well as the possibility to tune the electric behaviour of the films from insulating - like in bulk NiFe2O4 - to conducting. A systematic study of the influence of the film thickness and growth parameters on the properties of the films was carried out.
The enhancement of the saturation magnetization can be explained by a partially inversed spinel structure, where the Ni2+ ions are distributed over both available sites (octahedral and tetrahedral) of the structure, whereas in bulk NiFe2O4 the Ni2+ ions are only located on the octahedral sites of the structure. An additional introduction of oxygen vacancies causes the formation of mixed valence Fe2+/3+ chains on the octahedral sites and thus a hopping conductivity.
We have taken advantage of our ability to obtain epitaxial ferromagnetic NiFe2O4 films of insulating or conducting character to integrate them in two different spintronic devices: the magnetic tunnel junction and the spin filter.
The conducting NiFe2O4 was integrated in a magnetic tunnel junction as a magnetic electrode, with a (La,Sr)MnO3 counterelectrode and a SrTiO3 barrier. A magnetoresistance was measured up to a temperature of 280K. The values of the magnetoresistance correspond to a spin-polarization of 40%, which is basically constant in temperature. This results show that the conductive phase of NiFe2O4 is an interesting candidate for the application as a source of highly spin-polarized current.
On the other hand the insulating NiFe2O4 has been integrated into a spin filter as the magnetic barrier. The magnetic electrode was again (La,Sr)MnO3 and the counter electrode Au. A magnetoresistance up to 50% was observed. It was possible to deduce the band structure of NiFe2O4 from these measurements.
Thin films of CoCr2O4 were grown on different substrates like MgO(001) or MgAl2O4(001). It was found that the material shows a pronounced tendency to grow in a three dimensional manner. Thus the surface of these films is not sufficiently smooth to integrate them into tunnel contacts.
However, we were able to control the growth and morphology of the three dimensional structures leading to the formation of submicron self-organized pyramids with a square or elongated base. By a detailed study of the influence of the growth parameters it was possible to elucidate the underlying growth mechanisms and to obtain a fully faceted surface, which can be used in different applications.

Des couches minces à base de NiFe2O4 et CoCr2O4 ont été réalisées par pulvérisation cathodique sur des substrats d'oxydes, dans le but de les intégrer dans des hétérostructures pour l'électronique de spin.
Il a été montré que la croissance épitaxiale permet la stabilisation de nouvelles phases de NiFe2O4 qui n'existent pas sous forme massive. Ces phases présentent une augmentation forte du moment magnétique ou la possibilité d'ajuster les propriétés électriques du matériaux. Nous expliquons l'augmentation du moment magnétique par une inversion partielle des sites cationiques du NiFe2O4, matériau dans lequel les ions Ni2+ sont répartis entre les deux sites de la structure spinelle. Les lacunes en oxygène sont susceptibles de favoriser un comportement conducteur en induisant des états de valence mixte Fe2+/3+ dans les sites octaédriques.
Des couches minces de NiFe2O4 conducteur ont été utilisées comme électrodes ferrimagnétiques dans des jonctions tunnel. Une magnétorésistance significative a été mesurée, correspondant à une polarisation de spin de 40% du NiFe2O4 pratiquement constante en température. Le NiFe2O4 isolant a été incorporé avec succès en tant que barrière tunnel ferrimagnétique au sein de jonctions de type "filtre à spin", ce qui en fait la première structure de ce type réalisée avec des oxydes complexes.
Il a été mis en évidence que les couches minces de CoCr2O4 ont une tendance forte à croître de manière tridimensionnelle de la forme des objets pyramidaux aux facettes parfaitement définies. Cette croissance auto-organisée de nano-objets et sa dépendance à l'égard des conditions de dépôt été étudie en detail.

2016 - 2017
The main goal of this dissertation is the study of the effects induced by quantum confinement in transition-metal oxides quantum wells (QWs). The field of possible applications of oxide-based heterostructures (oxide-based nanoelectronics, spintronics, quantum computation, excitonic devices, energy conversion in solar cells, etc.) is very ample and growing, thanks to the many fascinating and exotic properties of transition-metal oxides and their versatility as well. p-type SrMnO3/La0.7Sr0.3MnO3/SrMnO3 QWs and n-type SrCuO2/Sr0.9La0.1CuO2/SrCuO2 QWs have been studied. The first part of my work has been devoted to the investigation of quantum confinement achievement using a Mott insulator with a small band gap. The observed results suggest that this type of material can be successfully used in QWs. As a final result of my work, the achievement of dimensional effects induced by the layering on the normal state of both investigated systems (n and p-doped) has been assessed. In addition, the layering has been shown to influence the superconducting state of the investigated n-doped QWs and on the metal-to-insulator transition of the p-doped QWs. The investigation of the behavior of each layer constituent the QW (both n and p-doped) is relevant in view of future growth of proximate p-n doped systems. Part of my work, therefore, has been devoted to the study of the properties of (Sr,La)CuO2 thin films. The study of electrical transport properties of SLCO thin films as a function of the doping has allowed to relate the presence of the low temperature upturn in the (Sr,La)CuO2 resistivity versus temperature curves the quantum interference effects produced by weak localization effects. Furthermore, the presence of low temperature Fermi liquid behaviors in SLCO thin films has also been observed... [edited by Author]
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Els òxids conductors transparents (TCO) són essencials en dispositius tecnològics. La seva capacitat per combinar una alta conductivitat elèctrica i transparència òptica a la llum visible, els fa particularment útils en una gran varietat de dispositius: pantalles, cèl·lules solars, finestres intel·ligents, etc. L’òxid d’indi i estany (ITO) és fins ara el TCO més estès. Un gran inconvenient de l’ITO és el seu alt cost ja que l’indi, el seu component principal, és un material escàs. D’altra banda, alguns òxids metàl·lics intrínsecs de metalls de transició també són transparents. En aquests materials, la banda (3,4)d és estreta i parcialment plena. És la responsable de l’alta densitat de portadors lliures i la seva massa efectiva gran fa que la llum no es reflecteixi en el visible i que el llindar de reflexió (freqüència de plasma) estigui a la regió de l’IR proper. En aquesta tesi, hem explorat les propietats de les pel·lícules primes d’òxids metàl·lics (SrVO3 (SVO; 3d1) i SrNbO3 (SNO; 4d1)) crescudes per deposició de làser polsat (PLD). Atès que la qualitat epitaxial és fonamental per obtenir bones propietats funcionals, el primer pas va consistir en optimitzar els paràmetres de creixement de les pel·lícules SVO/SNO. Les pel·lícules han de créixer en ultra alt buit (UHV) per estabilitzar l’estat d’oxidació 4+ de V/Nb i usar temperatures de dipòsit altes (700-800° C) per permetre la mobilitat de les espècies sobre el substrat. No obstant això, l’ablació a UHV i l’expansió de la ploma del PLD, molt enèrgica, provoquen la creació de defectes puntuals en les pel·lícules. Hem resolt aquest problema utilitzant un gas inert durant el creixement, que controla l’expansió de la ploma. Finalment, hem estudiat l’impacte de la deformació epitaxial en la conductivitat elèctrica i transparència òptica. Es van obtenir pel·lícules amb una conductivitat més gran que ITO i una transparència similar. D’altra banda, l’observació que la freqüència de plasma en aquests materials estigui a l’IR proper, s’atribueix comunament a un augment de la massa efectiva dels electrons degut les correlacions e-e dins de la banda estreta 3d. Després d’una anàlisi sistemàtica de les dades de transport de SVO vam arribar a la conclusió que la teoria del líquid de Fermi no pot explicar l’augment de la massa efectiva dels portadors. En canvi, hem suggerit que l’acoblament electró-fonó i el caràcter 2D de la superfície de Fermi són molt importants. A més, hem demostrat que la imatge clàssica de banda rígida, d’un electró lliure que evoluciona en una banda 3d-t2g, és només una aproximació, com ho demostra la hibridació observada dels orbitals V 3d i O 2p. Hem observat també que la tensió epitaxial, afecta la hibridació, l’ordre orbital i últimament a la resistivitat de les capes. Hem pogut observar i explicar que a la freqüència de plasma s’exciten, en les condicions d’il·luminació adequades, plasmons de volum. Una observació i descripció poc freqüents i que, en essència, estan relacionades amb la component π de la polarització de la llum i el gradient de càrrega en la superfície del material. Finalment, hem provat la idoneïtat de SVO com elèctrode en heteroestructures fotoabsorbents “tot-òxids”. Hem observat la resposta fotovoltaica, usant capes epitaxials de LaFeO3 com absorbent, i hem posat en relleu el paper de la funció de treball de l’elèctrode en el rendiment del dispositiu. Com perspectiva, hem demostrat que els elèctrodes transparents desenvolupats (SVO i SNO), en tenir funcions de treball diferents, poden permetre ajustar i optimitzar els dispositius. Aquest treball aporta un nou coneixement fonamental de les propietats d’òxids i demostra la seva versatilitat en component fotovoltaics.
Los óxidos conductores transparentes (TCO) son esenciales en dispositivos tecnológicos. Su capacidad para combinar alta conductividad eléctrica y transparencia óptica a la luz visible los hace particularmente útiles en una gran variedad de dispositivos: pantallas, células solares, ventanas inteligentes, etc. El óxido de indio y estaño (ITO) es hasta ahora el TCO más extendido. Un gran inconveniente del ITO es su alto coste ya que el indio, su componente principal, es un material escaso. Por otro lado, algunos óxidos metálicos intrínsecos de metales de transición también son transparentes. En estos materiales, la banda (3,4)d es estrecha y parcialmente llena. Es la responsable de la alta densidad de portadores libres y su masa efectiva grande hace que la luz no se refleje en el visible y que el borde de reflexión (frecuencia de plasma) esté en la región del IR cercano. En esta tesis, hemos explorado las propiedades de las películas delgadas de óxidos metálicos (SrVO3 (SVO; 3d1) y SrNbO3 (SNO; 4d1)) crecidas por deposición de láser pulsado (PLD). Dado que la calidad epitaxial es fundamental para obtener buenas propiedades funcionales, el primer paso consistió en optimizar los parámetros de crecimiento de las películas SVO/SNO. Las películas deben crecerse en ultra alto vacío (UHV) para estabilizar el estado de oxidación 4+ de V/Nb y usar temperaturas de depósito altas (700-800°C) para permitir la movilidad de las especies sobre el sustrato. Sin embargo, la ablación en UHV y la expansión de la pluma del PLD, muy enérgica, provocan la creación de defectos puntuales en las películas. Hemos resuelto este problema utilizando un gas inerte durante el crecimiento, que controla la expansión de la pluma. Finalmente, hemos estudiado el impacto de la deformación epitaxial en la conductividad eléctrica y la transparencia óptica. Se obtuvieron películas con una conductividad mayor que ITO y una transparencia similar. Por otra parte, la observación de que la frecuencia de plasma en estos materiales esté en el IR cercano, se atribute comúnmente a un aumento de la masa efectiva de los electrones debido a las correlaciones e-e dentro de la banda estrecha 3d. Tras un análisis sistemático de los datos de transporte de SVO llegamos a la conclusión de que la teoría del líquido de Fermi no puede explicar el aumento de la masa efectiva de los portadores. En cambio, hemos sugerido que el acoplamiento electrón-fonón y el carácter 2D de la superficie de Fermi juegan un papel importante. Además, hemos demostrado que la imagen clásica de banda rígida, de un electrón libre que evoluciona en una banda 3d-t2g es solo una aproximación, como lo demuestra la hibridación observada de los orbitales V-3d y O-2p. Hemos observado también que la tensión epitaxial, afecta a la hibridación, el orden orbital y últimamente a la resistividad de las capas. Hemos podido observar y explicar que a la frecuencia de plasma se excitan, en las condiciones de iluminación adecuadas, pasmones de volumen. Una observación y descripción poco frecuentes y que, en esencia, están relacionadas con la componente π de la polarización de la luz y el gradiente de carga en la superficie del material. Finalmente, hemos probado la idoneidad de SVO como electrodo en heteroestructuras fotoabsorbentes “todo-óxido”. Hemos observado la respuesta fotovoltaica, usando capas epitaxiales de LaFeO3 como absorbente y hemos puesto de relieve el papel de la función de trabajo del electrodo en el rendimiento del dispositivo. Como perspectiva, hemos demostrado que los electrodos transparentes SVO y SNO, al tener funciones de trabajo distintas, podrán permitir ajustar y optimizar los dispositivos. Este trabajo aporta un nuevo conocimiento fundamental de las propiedades de óxidos y demuestra su versatilidad en componentes fotovoltaicos.
Transparent conducting oxides (TCOs) are key elements to many technological devices. Their ability to combine high electrical conductivity and high optical transparency to visible light, make them particularly useful in a myriad of devices such as displays, solar cells, smart windows, etc. Indium tin oxide (ITO) is so far the most widespread TCO. By Sn-doping, this wide band gap In2O3 semiconductor can reach low resistivity (only about two orders of magnitude above conventional metals) while preserving its transparency. A major drawback of ITO is its high cost as indium, its main component, is a scarce material. Moreover, due to its nature of doped-semiconductor, some physical limits impose that its properties cannot be further improved. On the other hand, some intrinsic metallic oxides composed of early transition metals also turn out to be transparent. In these materials, the partially filled narrow d band is responsible for high density of free carriers with increased effective mass, thus bringing the reflection edge down to the near-IR region. In this thesis, we were interested in exploring the properties of metallic oxide thin films grown by pulsed laser deposition (PLD), namely SrVO3 (SVO; 3d1) and SrNbO3 (SNO; 4d1). As high epitaxial quality is essential to obtain good functional properties, the first step consisted in optimizing the growth parameters for single phase and flat SVO/SNO films, displaying high crystallinity, conductivity and transparency. As anticipated, films need to be grown in ultra-high vacuum (UHV) to stabilize the 4+ oxidation state of V/Nb and using a high substrate temperature (700-800°C) to allow good mobility of the species on the substrate. However, the deposition in UHV and its subsequent highly energetic PLD plasma plume lead to a high concentration of point defects. We have solved this issue by using an inert background gas. Finally, we have studied the impact of epitaxial strain on the electrical conductivity and optical transparency window. All in all, it turned out that optimal films display larger conductivity than ITO, for a similar transparency. Conventional wisdom would suggest that a low plasma frequency would be due to the electron-electron correlations within the narrow nd1 band. In a systematic analysis of SVO transport data (temperature-dependent resistivity, etc.), we have concluded that the Fermi liquid theory alone cannot account for the carrier mass enhancement. Instead, we have suggested that the 2D-like Fermi surface and the electron-phonon coupling play a major role. In addition, we have shown that the classical rigid band picture, of one free electron evolving in a 3d-t2g band is only a rough approximation, as attested by the observed hybridization of the V 3d and O 2p orbitals. Moreover, strain affects this hybridization by modifying the orbital hierarchy and covalency which could be responsible for the observed strain-dependent resistivity and effective mass. By appropriate optical measurements, we have also discussed the nature of the plasmonic excitations at plasma frequency in SNO and SVO films. Interestingly, the possibility of exciting volume plasmons in these TCOs gives a glimpse on their potential applications in the field of plasmonics. Finally, we have tested the suitability of SVO as electrode in photoabsorbing all-oxide heterostructures. In particular, we have successfully observed a photovoltaic effect in LaFeO3-based capacitors and disclosed the important role of the electrode work function on the device performances. As outlook, we have concluded that SVO and SNO, by having distinct work functions, could allow to tune any device properties. This work demonstrates the suitability and high potential of this whole new category of TCOs as electrode material in all-oxide devices. We are convinced that it opens the way to a plethora of possible devices, photovoltaic-wise or other.
Universitat Autònoma de Barcelona. Programa de Doctorat en Física

Multiferroic materials exhibit unique properties such as simultaneous existence of two or more of coupled ferroic order parameters (ferromagnetism, ferroelectricity, ferroelasticity or their anti-ferroic counterparts) in a single material. Recent years have seen a huge research interest in multiferroic materials for their potential application as high density non-volatile memory devices. However, the scarcity of these materials in single phase and the weak coupling of their ferroic components have directed the research towards multiferroic heterostructures. These systems operate by coupling the magnetic and electric properties of two materials, generally a ferromagnetic material and a ferroelectric material via strain. In this work, horizontal heterostructures of composite multiferroic materials were grown and characterized using pulsed laser ablation technique. Alternate magnetic and ferroelectric layers of cobalt ferrite and lead zirconium titanate, respectively, were fabricated and the coupling effect was studied by X-ray stress analysis. It was observed that the interfacial stress played an important role in the coupling effect between the phases. Doped zinc oxide (ZnO) heterostructures were also studied where the ferromagnetic phase was a layer of manganese doped ZnO and the ferroelectric phase was a layer of vanadium doped ZnO. For the first time, a clear evidence of possible room temperature magneto-elastic coupling was observed in these heterostructures. This work provides new insight into the stress mediated coupling mechanisms in composite multiferroics.

The scope of this Thesis is the study of the electronic structure of two Ti-based oxide systems, TiO2 thin films and the ultra-thin LaAlO3-SrTiO3 (LAO-STO) heterojunctions, which display remarkable physical phenomena, so far not completely understood. In both cases, the titanium-related electronic states are expected to play a fundamental role and thus have been probed by means of X-ray photoemission spectroscopies. A weak room-temperature ferromagnetism (FM) has been recently detected in slightly reduced TiO2 thin film and in other oxides, such as HfO2 and CaO; since these materials are insulating closed-shell systems, this phenomenon has been classified as "d0 magnetism". Magnetism in these compounds seems to be related to the growth methodology and ultimately to the presence of structural defects, such as oxygen vacancies. Therefore, a thorough analysis of titanium electronic states, and especially of the defect-related Ti3+ energy levels, is needed in order to understand the origin of magnetic interactions. In the first part of this Thesis, a comprehensive magnetic characterization of a set of TiO2 samples is given, together with the analysis of Ti 3d-related states carried out with X-ray photoemission (XPS) and resonant photoemission (ResPES). A set of N-doped TiO2 thin films have also been grown, in order to verify the effect of doping on the TiO2 magnetism. The hypothesis of a clustered oxygen-vacancies origin of FM is then discussed in the light of the experimental and theoretical results. Another interesting oxide system in which the stoichiometry of Ti ions play a fundamental role is the LAO-STO interface. LAO and STO, separately, are two band insulators, with an empty shell electronic structure (3d0 for STO, 4f0 for LAO) and a similar perovskite structure; however, the interface created by growing LAO on the top of STO (001) has found to become metallic, hosting a 2D electron gas. This heterostructure becomes conductive only when the STO is terminated with a TiO2 layer; therefore, the Ti-related electronic states are expected to host the metallic states. The second part of this Thesis is devoted to the study of conductive and insulating LAO-STO interfaces, carried out by XPS, X-ray absorption (XAS) and with ResPES techniques. The stoichiometry of each atomic species has been evaluated through a comparison with LAO and STO single crystals. A resonance enhancement of the conductive Ti states, associated to a small fraction of Ti3+ ions is reported and compared to theoretical calculations. On the basis of these results, the origin of metallic states in ultra-thin LAO-STO interfaces is properly addressed. In addition, a characterization of the intermixing and the disorder at the LAO-STO interface has been done through angle-resolved XPS, providing important information on the intermixing of light cations (Al, Ti) otherwise missed by X-ray diffraction techniques.

Les oxydes de métaux de transitions possèdent une large gamme de fonctionnalités (supraconductivité, magnétisme, ferroélectricité, multiferroicité) découlant de l’interaction d’effets structuraux et de corrélations fortes. De plus, des travaux récents ont mis en lumière une physique propre à leurs interfaces, incluant de la supraconductivité ainsi que de la conductivité classique dans le système bidimensionnel (2DES) créé à l’interface de deux isolants de bande, LaAlO₃ et SrTiO₃. Malgré cela pour couvrir l’immense potentiel des interfaces d’oxydes et leur phases électroniques sans précédent, il est nécessaire de combiner des oxydes plus fortement corrélés. Cette thèse à la croisée des chemins entre la physique des électrons fortement corrélés, du magnétisme et de la spintronique a pour but de combiner les instabilités magnétique et électronique pour créer de nouvelles phases électronique contrôlable par stimulus externe. Pour cela nous nous sommes intéressés à la famille relativement inexplorée des titanates de terres rares dont l’ordre magnétique ferro ou antiferro est contrôlé par la taille de la terre rare. Contrairement aux travaux existants, nous nous somme concentrés sur les membres ferrimagnétiques de la famille et leur intégration dans des 2DES. Cette thèse se développera autour de deux axes principaux. Dans un premier temps nous avons étudié plusieurs membres de la famille des titanates de terres rares sous la forme de couches minces épitaxiées. Nous avons aussi mis en évidence la présence d’une couche morte magnétiquement active à la surface de ces échantillons et expliqué sa présence par une suroxydation des ions titane de la surface. Nous avons aussi étudié la présence inattendue d’un moment orbital porté par le titane dans certains des composés étudiés et l’avons corrélé à leur structure magnétique non-colinéaire en conjonction avec un gradient structural observé en microscopie électronique en transmission. Dans un second temps nous avons combiné DyTiO₃ avec SrTiO₃ pour obtenir une interface conductrice possédant des propriétés de magnetrotransport complexes que nous avons interprété avec l’aide d’un modèle faisant intervenir le couplage spin-orbite ainsi qu’un magnétisme induit
Transition metal oxides possess a broad range of functionalities (superconductivity, magnetism, ferroelectricity, multiferroicity) stemming from the interplay between structural effects and electronic correlations. Recent work has revealed exciting physics at their interfaces, including conductivity and superconductivity in the two-dimensional electron system (2DES) that forms at the interface between two band insulators, LaAlO₃ and SrTiO₃. However, to embrace the immense potential of oxide interfaces and unveil unprecedented electronic phases, combining insulators with stronger electronic correlations is necessary. At the crossroad between strongly correlated electron physics, magnetism and spintronics, the present thesis project aims to harness electronic and magnetic instabilities in correlated oxides to craft new electronic phases controllable by external stimuli. We investigated rareearth titanates RTiO₃, a relatively unexplored family of Mott insulating perovskites with a crossover between antiferromagnetic and ferromagnetic orders upon changing the rare-earth size. Contrary to most previous works, we focused on ferromagnetic compounds, and their integration in 2DES. The thesis developed along two main axes. First, we explored several members of the rare-earth titanates family in epitaxial thin film form. We highlighted the presence of a magnetically active dead layer at the surface of thin films and established its origin as due to the overoxidation of titanium ions. We also studied the presence of an unexpected orbital moment carried by the titanium in some compounds, and discussed it in the light of the non-collinear spin arrangement promoted by the rare-earth orbital moment and of a structural gradient evidenced by transmission electron microscopy. In a second stage, we combined DyTiO₃ with SrTiO₃ to stabilize a conducting interface with puzzling magnetotransport properties that we interpreted with a model involving spin-orbit coupling as well as induced magnetism

Oxide ultra-thin film surfaces have properties and structures that are significantly different from the terminations of the corresponding bulk crystals. For example, surface structures of epitaxial ultra-thin oxide films are highly influenced by the crystallinity and electronegativity of the metal substrates they grown on. Some enhanced properties of the novel reconstructions are related to catalysis, sensing and microelectronics, which has resulted in an increasing interest in this field. Ultra-thin TiO_x films were grown on Au(111) substrates in this work. Two well-ordered structures within monolayer coverage - honeycomb (HC) and pinwheel - were generated and investigated. Special attention has been paid to the uniform (2 x 2) Ti₂O₃ HC phase including its regular structure and imperfections such as domain boundaries (DBs) and point defects. Linear DBs with long-range repeating units have been observed; density functional theory (DFT) modelling has been used to simulate their atomic structures and calculate their formation energies. Rotational DBs/defects show up less frequently, however a six-fold symmetrical 'snowflake' DB loop stands out. Two types of point defects have been discovered and assigned to Ti vacancies and oxygen vacancies/hydroxyl groups. Their diffusion manners and pairing habits have been discussed within an experimental context. The results of growing NbO_x ultra-thin films on Au(111) are also presented in this thesis. An identical looking (2 x 2) HC structure to the Ti₂O₃ ultra-thin film has been formed; a stoichiometry of Nb2O3 is suggested. Another interesting reconstruction is a hollow triangle structure. Various sizes have been found, and sides of these equilateral triangles all show a double-line feature aligned along the { 1 ₁⁻ } directions of the Au(111) lattice. Chemical composition characterisations of NbO_x thin films are still required as is DFT modelling. Experimental techniques used in this thesis include scanning tunnelling microscopy (STM), low energy electron diffraction (LEED), and X-ray photoelectron spectroscopy (XPS). Ultra-thin oxide films were created by physical vapour deposition (PVD) in ultra-high vacuum (UHV) systems.

This thesis presents optical characterizations of interfaces in ferromagnetic heterostructures and thin films used for spin polarized electronic devices. In these experiments, femtosecond laser spectroscopies are exploited to investigate the interface magnetization reversal, spin precession, and band offset, which are crucial in determining the performances of spintronic devices.;First, magnetization-induced second-harmonic-generation (MSHG) is applied to study interface magnetism in a hybrid structure containing a noncentrosymmetric semiconductor---Fe/AlGaAs. The reversal process of Fe interface layer magnetization is compared with the bulk magnetization reversal. In Fe/AlGaAs (001), the interface magnetization is found to be decoupled from the bulk magnetization based on the different switching characteristics---single step switching occurs at the interface layer, whereas two-jump switching occurs in the bulk. In contrast, the interface layer in Fe/AlGaAs (110) is rigidly coupled with the bulk Fe, indicating a strong impact of electronic structure on the magnetic interaction despite the same chemical composition. Furthermore, a time-resolved MSHG study demonstrates a coherent interface magnetization precession in Fe/AlGaAs (001), implying the feasibility of fast precessional control of interfacial spin. The interface magnetization precession exhibits a higher frequency and opposite phase for a given applied field compared to the bulk magnetization precession.;Second, uniform magnetization precession in the Lac0.67Ca 0.33MnO3 (LCMO) and La0.67Sr0.33MnO 3 (LSMO) films grown on different substrates are investigated by time-resolved magneto-optic Kerr effect. The parameters of magnetic anisotropy are determined from the field dependence of the precession frequency. The strain-free LCMO films grown on NdGaO3 exhibit a uniaxial in-plane anisotropy induced by the tilting of the oxygen octahedra in NdGaO3 An easy-plane magnetic anisotropy is found in the tensile-strained films grown on SrTiO 3, whereas the compressive-strained film grown on LaAlO3 exhibits an easy normal-to-plane axis.;Third, a table-top internal photoemission system is developed to measure the band offsets across semiconductor heterointerfaces by utilizing an optical parametric amplifier as the bright light source. The conduction band offsets DeltaE c = 660 meV and 530 meV at the CdCr2Se4-GaAs and CdCrZSe4-ZnSe interfaces are determined from the threshold energies of the photocurrent spectrum. The band offset is shown to be reduced by engineering the interface bonding and stoichiometry.

For obtaining of the CuO thin films have used spray pyrolysis method. Glass plates were cleaned in ultrasonic bath and washed with ethanol, used as a substrates. We used an aqueous solution of copper chloride (CuCl22H2O) with a concentration of 0.05 M as a precursor. The substrate temperature range from 570 to 720 K, with step Т=50 K. For atomization of precursor the air flow with a pressure of 0.25 MPa was used.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Mechanical Engineering, 2012.
Cataloged from PDF version of thesis.
Includes bibliographical references.
Searching for active and cost-effective catalysts for oxygen electrocatalysis is essential for the development of efficient clean electrochemical energy technologies. Perovskite oxides are active for surface oxygen exchange at evaluated temperatures and they are used commonly in solid oxide fuel cells (SOFC) or electrolyzers. However, the oxide surface chemistry at high temperatures and near ambient oxygen pressure is poorly understood, which limits the design of highly active catalysts. This work investigates heterostructured interfaces between (Lai. xSrx)CoO 3-3 (where x = 0.2 and 0.4, LSC80-2011 3 and LSC60-40 113 respectively) and (Lao. 5 Sro.5 )2CoO 4 ,3 (LSC2 14) enhanced ORR catalytic activity 1) via electrochemical impedance spectroscopy, atomic force microscopy, scanning electron microscopy, scanning transmission electron microscopy, and high resolution X-ray diffraction (HRXRD) and 2) using in situ ambient pressure X-ray photoelectron spectroscopy (APXPS) and in situ HRXRD. Here we show that the ORR of epitaxial LSC80-20 1 3 and LSC60-40113 is dramatically enhanced (~3-4 orders of magnitude above bulk LSC113) by surface decorations of LSC214 (LSC 1 31214) with coverage in the range from ~0.1 to ~15 nm. Such high surface oxygen kinetics (~ 110-5 cm-s1 at 550 C) are among the most active SOFC cathode materials reported to date. Although the mechanism for ORR enhancement is not yet fully understood, our results to date show that the observed ORR enhancement can be attributed to highly active interfacial LSCn 13/LSC214 regions, which were shown to be atomically sharp. Using in situ HRXRD and APXPS we show that epitaxial LSC80-20n3 thin films have lower coverage of surface secondary phases and higher Strontium enrichment in the perovskite structure, which is attributed to its markedly enhanced activity relative to LSC80-20113 powder. APXPS temperature cycling of epitaxial LSC80-20113 APXPS reveled upon heating to 520 *C the initial Sr enrichment which is irreversible, however subsequent temperature cycling demonstrates a small amount of reversible Sr enrichment. With applied potentials LSC80- 2013/214 shows significant Sr enrichment greater then LSC80-20 113, and the ability to stabilize high concentrations of both lattice and surface Sr which we hypothesize is a very important factor governing LSC80-2011 3214 enhanced ORR activity.
by Ethan Jon Crumlin.
Ph.D.

This thesis reports on the elemental growth of oxide thin films including TiO_x, BaO_x and Ba_xTi_yO_z by Ti/Ba deposition and oxidation. The films were grown on two different substrates, Au(111) and SrTiO₃(001), and studied using a variety of surface characterisation techniques. On the reconstructed Au(111) surface, three different TiO_x structures were obtained with increasing Ti amounts deposited: a (2 × 2) Ti₂O₃ honeycomb structure, a pinwheel structure that is the result of a Moiré pattern, and a triangular island TiO_1.30 structure. The structures arise from raised Ti coverages and have increased Ti densities. Although Ba deposited on the reconstructed Au(111) has a weak interaction with the substrate, the BaO_x thin films can grow epitaxially and lift the Au(111) reconstruction. Two well-ordered phases, a (6 × 6) and a (2√3 × 2√3) BaO_x structure, were obtained which may have octopolar-based surface structures. For Ba & Ti deposition on Au(111), a locally ordered (5 × 5) BaxTiyOz structure was observed in the sub-monolayer regime. What is more interesting is the possible formation of a BaO-TiO surface alloy with short-range ordering achieved by Ba deposition on the (2 × 2) Ti₂O₃-templated Au(111) surface. This is the first time that surface-alloying has been observed for oxides. When Ti is deposited onto the SrTiO₃(001) surface, it is incorporated into the substrate by forming a variety of Ti-rich SrTiO₃ surface reconstructions, such as c(4 × 2), (6 × 2), (9 × 2) and (√5 ×√5)-R26.6°. Ti deposition provides a completely different route to obtaining these reconstructions at much lower anneal temperatures than the previously reported preparation procedures involving sputtering and annealing the SrTiO₃ sample. Anatase islands with (1 × 3) and (1 × 5) periodicities were also formed by increasing the Ti deposition amount and post-annealing. Reconstructed SrTiO₃ substrate surface has a lattice that differs from the bulk crystal and affects the epitaxial growth of BaO, however, a locally ordered BaO_x structure was observed on the sputtered substrate with a growth temperature of 300 °C. Depositing Ba & Ti on SrTiO₃(001) results in the formation of BaO_x clusters and the Ti incorporation into the substrate, forming the familiar Ti-rich SrTiO₃ surface reconstructions.

Thesis (Ph. D.)--University of California, Riverside, 2009.
Includes abstract. Available via ProQuest Digital Dissertations. Title from first page of PDF file (viewed March 12, 2010). Includes bibliographical references. Also issued in print.

When the thickness of an oxide film is below a nm (few atomic layers) the interaction with the metal substrate, together with structural and morphology changes, can lead to completely different chemistry with espect to thicker films and can lead to new and unprecedented phenomena. This thesis focuses on the study of the structure and properties of different ultrathin oxide films epitaxially grown on metal subtrates and their interactions with adsorbed metal atoms and clusters.

This thesis details the use of aerosol assisted chemical vapour deposition to deposit transparent conducting oxide thin films. Transparent conducting oxides are a special class of materials that exhibit high optical transparency as well as good electrical conductivity, two properties usually in contradiction with each other. The combination of these properties in one material has established an essential role for transparent conducting oxides in a range of applications such as flat screen displays, photovoltaic cells, gas sensors, low-emissive coatings and light emitting diodes. Aerosol assisted chemical vapour deposition is increasingly becoming recognised as a simple, low-cost and reliable technique for depositing thin films. It involves generating an aerosol mist from a solution containing the precursors that is transported with the aid of an inert or reactive carrier gas into the reaction chamber where deposition takes place on a heated substrate. Two of the attractive features of this method are its versatility in allowing the use of precursors that are not suitable for conventional chemical vapour deposition methods as the method depends on solubility rather than volatility and the facility to use multiple precursors simultaneously within a single vessel. The focus of this work is on doping and co-doping of metal oxide thin films, namely ZnO and SnO2, to enhance their optoelectronic properties. The ZnO films were doped with group III elements aluminium or gallium, and the SnO2 films were doped with multivalent elements antimony or tungsten. All four systems were co-doped by introducing fluorine to replace the oxygen ion in the lattice. Fluorine was used as the co-dopant because of its established use in fluorine doped tin(IV) oxide transparent conducting oxides, a commercially available product. Co-doping has received less attention compared with single cation doping largely because of the limitations of other deposition methods. The rationale for co-doping is that it would allow greater tuning of the optoelectronic properties of the transparent conducting oxides to suit specific applications. All films synthesised in this investigation were characterised using a wide range of techniques including X-ray diffraction, energy and/or wavelength dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, UV-visible-near infrared spectroscopy and Hall effect measurements.

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

Dans le présent travail, nous montrons comment des couches minces d'oxydes peuvent être utilisées comme surfaces bioactives, un domaine de recherche encore peu exploré. À cet effet, des couches minces de TiO2, Al2O3, VOx et quelques autres oxydes ont été déposés sur des substrats de verre par la technique d'ablation laser pulsé (PLD), et l'adhésion, la prolifération et la différenciation de cellules souches mésenchymateuses humaines dérivées de moelle osseuse ont été évaluées. Le comportement des cellules a été analysé par rapport aux principaux paramètres de surface tels que la chimie, la mouillabilité, la morphologie et l'épaisseur des films. Nos résultats indiquent que les couches minces de TiO2 et Al2O3 peuvent non seulement favoriser l'adhésion et la croissance des cellules souches mésenchymateuses, mais peuvent également être utilisées pour influencer la différenciation ostéogénique et chondrogénique. En outre, l'effet de films minces d'oxydes sur l'adhésion et la croissance de lignées de cellules cancéreuses a été examiné. Nous avons montré que la culture de ces lignées cellulaires sur des films minces affecte leur croissance et, par conséquent, pourrait être une méthode utile pour effectuer des tests de dépistage des drogues.Cette étude fournira une meilleure compréhension de la corrélation entre la chimie de surface et la réponse cellulaire, qui a un role important dans le domaine de la fabrication de biomatériaux
In the present work we demonstrate how oxide thin films can be used as bioactive surfaces, a field of research which is still underexplored. For this purpose, thin films of TiO2, Al2O3, VOx and some others were deposited on glass substrates using the Pulsed Laser Deposition (PLD) technique, and adhesion, proliferation and differentiation of human bone marrow-derived mesenchymal stem cells were evaluated. Cell behavior was analyzed with respect to the various key surface parameters such as chemistry, wettability, morphology and the thickness of films.Our results indicate that thin films of TiO2 and Al2O3 can not only support mesenchymal stem cells adhesion and growth, but also can be used to influence osteogenic and chondrogenic differentiation path. Additionally, effect of oxide thin films on adhesion and growth of cancer cell lines was studied. We showed that culturing these cell lines on thin films affects their growth and, therefore, could be a valuable method to perform screening tests with drugs.This work will provide a better understanding of correlation between surface chemistry and cellular response, which has a high significance in the field of biomaterials fabrication

Cathodic electrodeposition (CELD) is achieved via hydrolysis of metal ions by electrogenerated base to form metal oxideihydroxide films on a cathodic substrate. Hydroxides and peroxides can then be converted to oxides by thermal treatment. In this study, Ti02 thin films (both rutile and anatase phases) and cobalt-doped anatase films were successfully produced through this method. These materials have presented applications in electronic and magnetic devices, such as piezo-ceramics as well as in catalysis. The CELD technology and the characterization of these thin films are described in detail in this thesis. The various parameters (deposition time, current density and annealing temperature etc.) that affect the characteristics ofTi02 films deposited on Pt and Ti substrates have been explored. Focus ion beam imaging (FIB) and scanning electron microscopy (SEM) analysis show that the thickness of the film increases as the deposition time increases. Applying current density greater than 30 mA'cm-2 results in the film having a porous structure, however, little difference between films was observed when the current density was 20 mA'cm-2 or less. XRD data gave an indication that the as-deposited films were amorphous; after annealing at elevated temperatures (400°C ~ 1000°C) anatase and rutile phases were formed successfully. Samples were thermally treated under three different atmospheres: air, argon and argon/hydrogen (10% hydrogen). Different characteristics were observed after annealing. SEM and atomic force microscopy (AFM) show that the particle size increased after annealing in argon and argon/hydrogen. Preferred orientation ofthe films annealed in different atmospheres was observed and further investigated using high temperature in-situ XRD. Ti1-xCOx02-o films were successfully prepared on Ti and Si substrates. When the annealing temperature was above 600°C a CoTi03 phase was detected in the film, whilst maintaining the anneal temperature below 600°C resulted in only anatase peaks ((101) and (200)) being observed. The films annealed at 400°C show room-temperature ferromagnetism as determined by vibrating sample magnetometry, and the magnetization per unit volume was of the right order of magnitude (0.2-0.6JlB/CO) for dilute ferromagnetic oxide thin films. X-ray absorption spectroscopy studies showed that the cobalt was present as Co2+ and the XRD data were consistent with cobalt substituted anatase lattice as the lattice parameter increased from 9.0080(2) to 9.4780 (3)

The rapid progress of n-type metal oxide thin film transistors (TFTs) has motivated research on p-type metal oxide TFTs in order to realise metal oxide-based CMOS circuits which enable low power consumption large-area electronics. Cuprous oxide (Cu2O) has previously been proposed as a suitable active layer for p-type metal oxide TFTs. The two most significant challenges for achieving good quality Cu2O TFTs are to overcome the low field-effect mobility and an unacceptably high off-state current that are a feature of devices that have been reported to date. This dissertation focuses on improving the carrier mobility, and identifying the main origins of the low field-effect mobility and high off-state current in Cu2O TFTs. This work has three major findings. The first major outcome is a demonstration that vacuum annealing can be used to improve the carrier mobility in Cu2O without phase conversion, such as oxidation (CuO) or oxide reduction (Cu). In order to allow an in-depth discussion on the main origins of the very low carrier mobility in as-deposited films and the mobility enhancement by annealing, a quantitative analysis of the relative dominance of the main conduction mechanisms (i.e. trap-limited and grain-boundary-limited conduction) is performed. This shows that the low carrier mobility of as-deposited Cu2O is due to significant grain-boundary-limited conduction. In contrast, after annealing, grain-boundary-limited conduction becomes insignificant due to a considerable reduction in the energy barrier height at grain boundaries, and therefore trap-limited conduction dominates. A further mobility improvement by an increase in annealing temperature is explained by a reduction in the effect of trap-limited conduction resulting from a decrease in tail state density. The second major outcome of this work is the observation that grain orientation ([111] or [100] direction) of sputter-deposited Cu2O can be varied by control of the incident ion-to-Cu flux ratio. Using this technique, a systematic investigation on the effect of grain orientation on carrier mobility in Cu2O thin films is presented, which shows that the [100] Cu2O grain orientation is more favourable for realising a high carrier mobility. In the third and final outcome of this thesis, the temperature dependence of the drain current as a function of gate voltage along with the C-V characteristics reveals that minority carriers (electrons) cause the high off-state current in Cu2O TFTs. In addition, it is observed that an abrupt lowering of the activation energy and pinning of the Fermi energy occur in the off-state, which is attributed to subgap states at 0.38 eV below the conduction band minimum. These findings provide readers with the understanding of the main origins of the low carrier mobility and high off-state current in Cu2O TFTs, and the future research direction for resolving these problems.

The atomic structure of transition metals doped three dimensional (3D) topological insulators (TIs) and the bonding nature of Bi2Te3 with FeSe layers and Ge(111) substrate were studied. Motivation behind transition metal doping of 3D TIs is driven by achieving long range ferromagnetism of Bi2Se3 and Bi2Te3, which is expected to give rise to different spintronic effects that can be utilise in device applications. The nature of this magnetisation depends on the location of the dopants in the Bi chalcogenide matrix. Dopants in Bi based TIs can substitute for Bi, Te, or incorporate between the quintuple layers in the van der Waals gap. Long range ferromagnetism is observed in both Cr doped Bi2Se3 and Mn doped Bi2Te3; however, the main goal of achieving room-temperature ferromagnetism in homogeneously doped TIs has proven to be difficult. In this thesis it is shown that 4.6 at-% of Cr is incorporated substitutionally on Bi sites with no phase segregation. The presences of grain boundaries can cause Cr segregation; hence by controlling the defect density a homogeneous Cr distribution could in principle be achieved even at higher concentrations. In case of Mn as a dopant, we show that the local environment of Mn in Bi2Te3 is heterogeneous. The first principal calculations revealed that the Mn dopants ferromagnetically couple in Bi2Te3 lattice. In addition, we have shown that doping of Bi2Te3 with Mn should be limited to low concentrations (< 6 at-%), higher dopants concentrations results in the formation of secondary phases. Next we have demonstrated that epitaxial growth of FexCu1-xSe on Bi2Te3 is possible regardless of their different lattice symmetries and large lattice mismatch of 19%. First-principles energy calculations revealed that this is realised through van der Waals-like bonding between the Se and Te atomic planes at the interface. Finally, we have shown that the weak van der Waals bonding between the Bi2Te3 and Ge(111) substrate can be strengthen by formation of a Te monolayer at the interface. The electronic band structure calculations revealed that this is due to the stronger atomic p-type orbital hybridization at the interface.

Electrochromic iridium oxide (IrOx) and iridium-tantalum oxide (IrTaOx) thin films were prepared by reactive magnetron sputtering. Composition, density, and structure were determined using Rutherford backscattering spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and electron energy loss spectroscopy. The electronic density of states (DOS) and the solid phase chemical diffusion coefficient (D) were determined for hydrogen in IrOx and IrTaOx by potentiostatic intermittent titration technique (PITT), and electrochemical impedance spectroscopy (EIS). The complex refractive indices were determined for colored and bleached IrOx and IrTaOx by inverting transmission and reflectance, measured using spectrophotometry in the 300-2500 nm wavelength range. A very porous structure, with a stoichiometry of IrO2.2, was found for IrOx. It contained ~4 nm sized grains. The IrTaOx had a denser structure built up by ~4 nm sized grains. The composition of IrTaOx was found to vary on a nanometer scale, with an average composition of IrTa1.4O5.6. It was found that DOS can be measured using PITT and EIS in the presence of spontaneous side reactions, even for systems influenced by non-negligible charge transfer kinetics and Ohmic drops. It was found that the measured DOS is 30-50% of the theoretically calculated DOS and that D is in the 10-10 – 10-11 cm2/s range for both materials. The hydrogen diffusion mechanism was described by an anomalous diffusion model, possibly indicating percolation or diffusion paths described by a fractal network. The refractive indices were found to be ~1.3 and ~2 for IrOx and IrTaOx, respectively, and independent of coloration state, whereas the extinction coefficients were found to modulate by ~30% for IrOx and ~50% for IrTaOx, making IrTaOx more favorable for electrochromic applications. A modulation peak was found at ~660 nm for both IrOx and IrTaOx associated with the removal of intraband transitions within the Ir t2g band.

Epitaxial oxide thin films are used in many technologically important device applications. This work deals with the deposition and characterization of epitaxial WO3 and SrBi2Ta2O9 (SBT) thin films on single crystal oxide substrates. WO3 thin films were chosen as a subject of study because of recent findings of superconductivity at surfaces and twin boundaries in the bulk form of this oxide. Highly epitaxial thin films would be desirable in order to be able to create a device within a film without patterning it, by locally creating superconducting regions (e.g. twins) within an otherwise defect free film by reducing or doping the film with Na. Films were deposited by reactive magnetron sputtering at various temperatures on single crystal SrTiO3 (100) and R-sapphire substrates. X-ray diffraction studies showed that the optimised films were highly (001) oriented, quality of epitaxy improving with decreasing deposition temperature. AFM studies revealed columnar growth of these films. Films were heat treated with Na vapour in order to reduce or dope them with Na. Low temperature measurements of the reduced films did not show existence of any superconductivity. SBT is a ferroelectric oxide and its thin films are attractive candidates for non-volatile ferroelectric random access memory (FRAM) applications. High structural anisotropy leads to a high degree of anisotropy in its ferroelectric properties which makes it essential to study epitaxial SBT films of different orientations. In this study, SBT films of different orientations were deposited on different single crystal substrates by pulsed laser ablation. Highly epitaxial c-axis oriented and smooth SBT films were deposited on SrTiO3 (100) substrates. AFM studies revealed the growth of these films by 3-D Stranski-Krastanov mode. However, these films did not exhibit any ferroelectric activity. Highly epitaxial (116)-oriented films were deposited on SrTiO3 (110) substrates. These films were also very smooth with root mean square (RMS) roughness of 15-20 Å. Films deposited on TiO2 (110) were partially a-/b-axis oriented and showed the formation of c-axis oriented SBT and many impurities. Completely a-/b-axis oriented SBT films were deposited on LaSrAlO4 (110) substrates. Films deposited at non-optimal growth temperatures showed the formation of many impurities. Attempts were also made towards depositing Sr2RuO4 films on LaSrAlO4 (110) substrates, which can act as a bottom electrode for ferroelectric SBT films.

My dissertation research focuses on the investigation of the transport and magnetic properties of transition metal and rare earth doped oxides, particularly SnO2 and HfO2 thin films. Cr- and Fe-doped SnO2 films were deposited on Al2O3 substrates by pulsed-laser deposition. Xray- diffraction patterns (XRD) show that the films have rutile structure and grow epitaxially along the (101) plane. The diffraction peaks of Cr-doped samples exhibit a systematic shift toward higher angles with increasing Cr concentration. This indicates that Cr dissolves in SnO2. On the other hand, there is no obvious shift of the diffraction peaks of the Fe-doped samples. The magnetization curves indicate that the Cr-doped SnO2 films are paramagnetic at 300 and 5 K. The Fe-doped SnO2 samples exhibit ferromagnetic behaviour at 300 and 5 K. Zero-field-cooled and field-cooled curves indicate super paramagnetic behavior above the blocking temperature of 100 K, suggesting that it is possible that there are ferromagnetic particles in the Fe-doped films. It was found that a Sn0.98Cr0.02O2 film became ferromagnetic at room temperature after annealing in H2. We have calculated the activation energy and found it decreasing with the annealing, which is explained by the increased oxygen vacancies/defects due to the H2 treatment of the films. The ferromagnetism may be associated with the presence of oxygen vacancies although AMR was not observed in the samples. Pure HfO2 and Gd-doped HfO2 thin films have been grown on different single crystal substrates by pulsed laser deposition. XRD patterns show that the pure HfO2 thin films are of single monoclinic phase. Gd-doped HfO2 films have the same XRD patterns except that their diffraction peaks have a shift toward lower angles, which indicates that Gd dissolves in HfO2. Transmission electron microscopy images show a columnar growth of the films. Very weak ferromagnetism is observed in pure and Gd-doped HfO2 films on different substrates at 300 and 5 K, which is attributed to either impure target materials or signals from the substrates. The magnetic properties do not change significantly with post deposition annealing of the HfO2 films.

Magnesium oxide seems to be a good candidate regarding its bulk properties: large band gap (7.8 eV), high thermal conductivity and stability and an alternative dielectric to silicon dioxide (SiO2) to reduce the electric field in capacitive networks. MgO, widely used as a substrate for high-temperature superconductor films deposition, has attracted much attention due to its low dielectric constant, low dielectric loss, and less mismatch with YBCO films. With a low dielectric loss, MgO shows a wide application in microwave devices. Due to its low refractive index, MgO is especially a suitable buffer for epitaxial optical waveguide films. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/34844