In this study, barium strontium titanate (BST) thin films with different compositions (Ba0.9Sr0.1TiO3, Ba0.8Sr0.2TiO3, Ba0.7Sr0.3TiO3, Ba0.5Sr0.5TiO3) were produced by chemical solution deposition technique. BST solutions were prepared by dissolving barium acetate, strontium acetate and titanium isopropoxide in acetic acid and adding ethylene glycol as a chelating agent and stabilizer to this solution, at molar ratio of acetic acid/ethylene glycol, 3:1. The solution was then coated on Si and Pt//Ti/SiO2/Si substrates at 4000 rpm for 30 seconds. Crack-free films were obtained up to 600 nm thickness after 3 coating &amp / #8211 / pyrolysis cycles by using 0.4M solutions. Crystal structure of the films was determined by x-ray diffraction while morphological properties of the surface and the film-substrate interface was examined by scanning electron microscope (SEM). Dielectric constant, dielectric loss and ferroelectric parameters of the films were measured. Sintering temperature, film composition and the thickness of the films were changed in order to observe the effect of these parameters on the measured electrical properties. The dielectric constant of the films was decreased slightly in 1kHz-1 MHz range. It was seen that dielectric constant and loss of the films was comparable to chemical solution deposition derived films on literature. Maximum dielectric constant was obtained for the Ba0.7Sr0.3TiO3 composition at a sintering temperature of 800&amp / #730 / C for duration of 3 hours. Dielectric constant increased whereas dielectric loss decreased with increasing film thickness. BST films have composition dependent Curie temperature. For Ba content greater than 70 %, the material is in ferroelectric state. However, fine grain size of the films associated with chemical solution deposition and Sr doping causes the suppression of ferroelectric behaviour in BST films. Therefore, only for Ba0.9Sr0.1TiO3 composition, slim hysteresis loops with very low remanent polarization values were obtained.

ABSTRACT PREPARATION OF PLZT THIN FILMS BY CHEMICAL SOLUTION DEPOSITION AND THEIR CHARACTERIZATION Kaplan, Burkan M.S., Department of Metallurgical and Materials Engineering Supervisor: Prof. Dr. Macit &Ouml / zenbaS November 2005, 125 pages In this study, La3+ was substituted into lead zirconate titanate (PZT) system by Pb1-xLax(ZryTi1-y)1-x/4O3 nominal stochiometry and it was processed via chemical solution deposition on (111)-Pt/Ti/SiO2/Si-(100) substrate.PLZT solutions were prepared by mixing two solutions, one of which was obtained by dissolving lead acetate and lanthanum acetate hydrate in 2 methoxyethanol at high temperature. This solution was then mixed with the second solution containing zirconium propoxide and titanium isopropoxide. 40ml/0.4M solution was prepared and spin coated on Pt/Ti/SiO2/Si substrates at 3000 rpm for 30 seconds. After 4 coating cycles, film thickness was reached to 600 nm. A systematic study was carried out in different regions of PLZT phase diagram tetragonal, rhombohedral and on the morphotropic phase boundry (MPB) to obtain optimized results of ferroelectric, dielectric and optical properties of the material. During the period of the work, effect of parameters on these properties such as heat treatment conditions, chemical composition of the film, microstructure and thickness of the film was investigated. The films were characterized structurally and electrically. For structural properties, X-ray diffraction technique (XRD), energy dispersive spectrometry (EDS) and Scanning Electron Microscope (SEM) were used to observe phases and surface characterization. For electrical measurements, ferroelectric tester was used to obtain dielectric constant, loss tangent and hysteresis curves. Optical transmittance of the films was also investigated by UV-VIS Spectrophotometer and optical film constants were calculated by modified envelope method. It was observed that the optimum heat treatment conditions were achieved at 7500C for 3 hours. The highest ferroelectric and dielectric properties such as remanent polarization and dielectric constant were obtained using that temperature. The dielectric constant of the films was measured in the frequency range of 1kHz-1MHz and remained almost constant in this region. The change of dielectric constant and ferroelectric hysteresis loops were obtained as a function of Zr/Ti ratio and La content. The grain size as a function of sintering temperature and La content was investigated. It was seen that as the sintering temperature was increased, the grain size of the films increased. The same tendency was also observed when the La content was increased. Fatigue behavior of PLZT thin films was also investigated by Radiant Ferroelectric Tester at 50 kHz and &plusmn / 15V. Change of remanent polarization (Pr) as a function of cumulative switching cycles (N) was drawn with the log scale of x-axis. Furthermore, leakage current characteristics of the films were also obtained by the ferroelectric tester at &amp / #61617 / 15V. It has been observed that as the La content of the film was increased, leakage current of the PLZT films decreased. Keywords: PLZT, (111)-Pt/Ti/SiO2/Si-(100) substrate, Chemical Solution Deposition.

Avec le développement de nouvelles sources d’énergie, les technologies dédiées à son stockage ont un rôle capital. Le zirconate de Plomb (PZ de structure Pérovskite) présente un grand intérêt pour les futures capacités rapides permettant le stockage de forte densité d’énergie. Cette propriété est associée à la transition de phase ferroélectrique – anti ferroélectrique induite par le champ électrique et qui s’accompagne d’une grande capacité de stockage. Le PZ a été déposé par pulvérisation cathodique RF sur différents types de substrats et notamment le SrTiO3, les cibles sont obtenues par mélange des poudres et pressage à froid. L’étude s’est focalisée sur les effets d’interfaces entre le film et l’électrode inférieure (LaNiO3 dans notre cas), l’orientation préférentielle des films et la réalisation de films épitaxiés de PZ. La structure, la micro structure des films ainsi que leurs épaisseurs ont un impact sur les contraintes existantes dans le film et nous avons évalué ces effets sur la capacité de stockage du PZ dans la phase anti ferroélectrique. L’optimisation des propriétés des interfaces et de l’ingénierie des contraintes permettent d’améliorer la densité d’énergie stockée dans un film anti ferroélectrique. C’est une voie sérieuse pour les supers condensateurs à base de matériaux fonctionnels de type PZ. / With the development of new energy resources, the advanced energy storage technologies are also becoming more and more important. Perovskite lead zirconate PbZrO3 is of great interest for future high-energy and fast-speed storage capacitors, due to the field-forced phase transition into the ferroelectric state accompanied by large charge storage. The material is deposited on SrTiO3 by RF magnetron sputtering from cold pressed target made in laboratory. The study focuses on the effect of interface between films and electrodes, preferred orientations, epitaxial strain and measuring conditions on the energy storage properties of PbZrO3-based antiferroelectric films. The improvement of interface properties and strain engineering enhance the energy storage density of antiferroelectric film, which may open a route to advance studies on PbZrO3-based antiferroelectric functional devices.

In the presented thesis, lead-free Ba(Ti0.8Zr0.2)O3-(Ba0.7Ca0.3)TiO3 (BZT-BCT) thin films were deposited on Pt/TiO2/SiO2/Si substrates using chemical solution deposition method and then the effect of process parameters were investigated to obtain optimum parameters of these lead-free thin films. The phase was selected near to the morphotropic phase boundary (MPH) to increase the number of polarization directions where rhombohedral and tetragonal phases exist together. In this study, the effect of sintering temperatures on microstructure, dielectric and ferroelectric properties were studied systematically. Among the various high-quality BZT-BCT thin films with uniform thickness, the optimum dielectric and ferroelectric responses were observed for films annealed at 800 oC for 1 h sintering time. The thickness was kept constant for all measurements as 500 nm (triple layered films). Therefore, the average grain sizes were found around 60 nm for samples sintered at 700,750 and 800 oC. BZT-BCT thin films sintered at 800 oC showed effective remnant polarization and coercive field values of 2.9 &micro / C/cm2 and 49.4 kV/cm, together with a high dielectric constant and low loss tangent of 365.6 and 3.52 %, respectively, at a frequency of 600 kHz due to pure perovskite phase showing full crystallization and minimum surface porosity obtained at this temperature.

The discovery of superconductivity in ceramic materials by Bednorz and Müller [2, 3] in early 1987, immediately followed by Wu et al. [4, 5] who showed that YBa2Cu3O7−x (YBCO) becomes superconducting (92K) well above the boiling point of nitrogen (77K) created a great excitement in superconductivity research. Potential applications of high Tc-superconductors require large critical currents and high-applied magnetic fields. Effective ways to increase the critical current density at high magnetic fields in YBCO are the introduction of nanoparticles and chemical substitution of yttrium by other rare earth elements. Since low costs and environmental compatibility are essential conditions for the preparation of long length YBCO films, the cost effective chemical solution deposition (CSD) procedure was selected, given that no vacuum technology is required. To reveal the flexibility and the good optimization possibilities of the CSD approach two main processes were chosen for comparison: a fluorine-free method, namely the polymer-metal precursor technique, and a fluorine-based method, the metalorganic deposition (MOD) using the trifluoroacetates (TFA) technique. Sharp transition temperature widths DTc of 1.1K for the polymer metal method, 0.8K for TFA method and critical current densities Jc of _3.5MA/cm2 shows that high quality YBCO thin films can be produced using both techniques. Especially interesting is the magnetic field dependence of the critical current density Jc(B) of the Y(Dy)BCO (80 %) films showing that for the lower magnetic fields the critical current density Jc(B) is higher for a standard YBCO film, but at fields higher than 4.5T the critical current density Jc(B) of Y(Dy)BCO is larger than that for the YBCO. Above 8T, Jc(B) of the Y(Dy)BCO film is more than one order of magnitude higher than in pure YBCO film. / Die Entdeckung der Supraleitung in keramischen Materialien durch Bednorz und Müller 1987 und die kurz darauf folgende Beobachtung von Wu et al., dass YBa2Cu3O7−x (YBCO) supraleitende Eigenschaften deutlich oberhalb (92K) des Siedepunktes von Stickstoff (77K) aufweist, führten zu einer enormen Intensivierung der Forschung hinsichtlich neuer supraleitender Materialien sowie deren Eigenschaften und möglichen Einsatzgebieten. Potentielle Anwendungsgebiete für diese neuen Hochtemperatur-Supraleiter erfordern hohe kritische Stromdichten und hohe kritische Feldstärken. Effektive Wege zur Erhöhung der kritischen Stromdichte in starken Magnetfeldern in YBCO sind der Einbau von Nanoteilchen oder die chemische Substitution von Yttrium durch ein anderes Seltenerd-Element. Da niedrige Kosten und gute Umweltverträglichkeit wichtige Voraussetzungen für die Herstellung von YBCO-Schichten großer Länge darstellen, werden in dieser Arbeit die Vorteile und Einsatzmöglichkeiten der Chemischen Lösungsabscheidung (chemical solution deposition - CSD) untersucht. CSD Prozesse sind besonders gut geeignet, weil sie keine Vakuum-Technologie erfordern und einen hohen Grad an Flexibilität garantieren. Zur Demonstration der guten Optimierbarkeit werden zwei wichtige CSD-Verfahren miteinander verglichen: die Polymer-Metall Precursor Technik - eine Fluor-freie Methode - und die metallorganische Abscheidung mittels Trifluoroacetat (TFA-MOD), bei der Fluor zum Einsatz kommt. Scharfe supraleitende Übergänge (Polymer-Metall Precursor Technik: DTc = 1.1K; TFA -MOD: DTc = 0.8K) sowie hohe kritische Stromdichten von ca. 3.5MA/cm2 (B= 0 T) zeigen, dass mit beiden Verfahren dünne YBCO-Schichten hoher Qualität hergestellt werden können. Außerdem bieten CSD-Verfahren durch die hervorragende Kontrollierbarkeit der Stöchiometrie des Precursors die Möglichkeit Yttrium teilweise oder vollständig durch andere Seltenerd-Metalle zu ersetzen und damit die kritische Stromdichte in hohen Magnetfeldern deutlich zu erhöhen. In dieser Arbeit wird gezeigt, dass besonders die TFA-Methode besonders geeignet ist, um (RE)BCO-Schichten (RE: rare earth) herzustellen. Untersucht wurden verschiedene Zusammensetzungen mit Sm, Dy und Ho. Außerordentlich interessant sind dabei die Ergebnisse für Y(Dy)BCO-Schichten. Schichten mit einem Dy-Gehalt von 80 % zeigen oberhalb von 4.5T deutlich höhere kritische Stromdichten als reine YBCO Schichten. Bei Magnetfeldern größer als 8T beträgt der Unterschied mehr als eine Größenordnung.

The discovery of superconductivity in ceramic materials by Bednorz and Müller [2, 3] in early 1987, immediately followed by Wu et al. [4, 5] who showed that YBa2Cu3O7−x (YBCO) becomes superconducting (92K) well above the boiling point of nitrogen (77K) created a great excitement in superconductivity research. Potential applications of high Tc-superconductors require large critical currents and high-applied magnetic fields. Effective ways to increase the critical current density at high magnetic fields in YBCO are the introduction of nanoparticles and chemical substitution of yttrium by other rare earth elements. Since low costs and environmental compatibility are essential conditions for the preparation of long length YBCO films, the cost effective chemical solution deposition (CSD) procedure was selected, given that no vacuum technology is required. To reveal the flexibility and the good optimization possibilities of the CSD approach two main processes were chosen for comparison: a fluorine-free method, namely the polymer-metal precursor technique, and a fluorine-based method, the metalorganic deposition (MOD) using the trifluoroacetates (TFA) technique. Sharp transition temperature widths DTc of 1.1K for the polymer metal method, 0.8K for TFA method and critical current densities Jc of _3.5MA/cm2 shows that high quality YBCO thin films can be produced using both techniques. Especially interesting is the magnetic field dependence of the critical current density Jc(B) of the Y(Dy)BCO (80 %) films showing that for the lower magnetic fields the critical current density Jc(B) is higher for a standard YBCO film, but at fields higher than 4.5T the critical current density Jc(B) of Y(Dy)BCO is larger than that for the YBCO. Above 8T, Jc(B) of the Y(Dy)BCO film is more than one order of magnitude higher than in pure YBCO film. / Die Entdeckung der Supraleitung in keramischen Materialien durch Bednorz und Müller 1987 und die kurz darauf folgende Beobachtung von Wu et al., dass YBa2Cu3O7−x (YBCO) supraleitende Eigenschaften deutlich oberhalb (92K) des Siedepunktes von Stickstoff (77K) aufweist, führten zu einer enormen Intensivierung der Forschung hinsichtlich neuer supraleitender Materialien sowie deren Eigenschaften und möglichen Einsatzgebieten. Potentielle Anwendungsgebiete für diese neuen Hochtemperatur-Supraleiter erfordern hohe kritische Stromdichten und hohe kritische Feldstärken. Effektive Wege zur Erhöhung der kritischen Stromdichte in starken Magnetfeldern in YBCO sind der Einbau von Nanoteilchen oder die chemische Substitution von Yttrium durch ein anderes Seltenerd-Element. Da niedrige Kosten und gute Umweltverträglichkeit wichtige Voraussetzungen für die Herstellung von YBCO-Schichten großer Länge darstellen, werden in dieser Arbeit die Vorteile und Einsatzmöglichkeiten der Chemischen Lösungsabscheidung (chemical solution deposition - CSD) untersucht. CSD Prozesse sind besonders gut geeignet, weil sie keine Vakuum-Technologie erfordern und einen hohen Grad an Flexibilität garantieren. Zur Demonstration der guten Optimierbarkeit werden zwei wichtige CSD-Verfahren miteinander verglichen: die Polymer-Metall Precursor Technik - eine Fluor-freie Methode - und die metallorganische Abscheidung mittels Trifluoroacetat (TFA-MOD), bei der Fluor zum Einsatz kommt. Scharfe supraleitende Übergänge (Polymer-Metall Precursor Technik: DTc = 1.1K; TFA -MOD: DTc = 0.8K) sowie hohe kritische Stromdichten von ca. 3.5MA/cm2 (B= 0 T) zeigen, dass mit beiden Verfahren dünne YBCO-Schichten hoher Qualität hergestellt werden können. Außerdem bieten CSD-Verfahren durch die hervorragende Kontrollierbarkeit der Stöchiometrie des Precursors die Möglichkeit Yttrium teilweise oder vollständig durch andere Seltenerd-Metalle zu ersetzen und damit die kritische Stromdichte in hohen Magnetfeldern deutlich zu erhöhen. In dieser Arbeit wird gezeigt, dass besonders die TFA-Methode besonders geeignet ist, um (RE)BCO-Schichten (RE: rare earth) herzustellen. Untersucht wurden verschiedene Zusammensetzungen mit Sm, Dy und Ho. Außerordentlich interessant sind dabei die Ergebnisse für Y(Dy)BCO-Schichten. Schichten mit einem Dy-Gehalt von 80 % zeigen oberhalb von 4.5T deutlich höhere kritische Stromdichten als reine YBCO Schichten. Bei Magnetfeldern größer als 8T beträgt der Unterschied mehr als eine Größenordnung.