Ferroelectric lead zirconate titanate thin films, Pb(ZrxTi 1-x)0 3 or PZT, have aroused considerable interest in recent years for the application in nonvolatile electronic memories because of their excellent ferroelectric properties. In this research, PZT thin films were studied from two aspects: the scientific aspect and the technical aspect. The optical properties of PZT solid solutions and the structure development in PZT films were extensively investigated in the scientific aspect. The PZT films used in this part of study were prepared by metalorganic decomposition (MOD) process. The envelope method, with consideration of light intensity loss from the back surface of the substrate, was demonstrated to be a simple and convenient tool for obtaining the optical properties of the PZT films in the medium and weak absorption regions. In the near optical band gap region, both the transmission and reflection spectra were used to successfully calculate the optical constants of the films. The film thickness derived from the envelope method was cross checked by a computer simulation method and was found to have an accuracy better than 2%. An effective, versatile, and nondestructive optical method was developed for the study of the structure development in MOD PZT films. Also, the models for the structure development were proposed and were verified by this optical method. Using this method, the characteristic temperatures (i.e., the initiation and completion temperatures) of each phase can be easily identified. In addition, the volume fraction of the perovskite phase in the pyrochlore-perovskite phase transformation region was obtained from this optical method. From the technical point of view, ferroelectric PZT films were successfully and reproducibly deposited for the first time by hot-wall metalorganic chemical vapor deposition (MOCVD). One of the problems associated with the MOCVD technique is the availability of the precursors. After intensive studies searching for the most suitable precursors for MOCVD PZT thin films, the safe and stable precursors, namely lead tetramethylheptadione [Pb(thd)2)], zirconium tetramethylheptadione [Zr(thd)4], and titanium ethoxide [Ti(OEt)4] were chosen. The films were deposited at temperatures as low as 55QOC and had pure perovskite phase in the as-deposited state. Also, the films were smooth, specular, crack-free, uniform, and adhered well on the substrates. The stoichiometry of the films can be easily controlled either by varying the individual precursor temperature and/or the flow rate of the carrier gas. Auger electron spectroscopic (AES) depth profile showed good uniformity through the thickness of the films. The AES spectra also showed no carbon contamination in the bulk of the films. As-deposited films were dense and showed uniform and fine grains. The film (Pb/Zr/Ti = 50/41/9) annealed at 6QQOC showed a spontaneous polarization of23.3 pC/cm² and a coercive field of 64.5 kV /em. / Ph. D.

Lead zirconate titanate (PZT) is a ferroelectric material which has many interesting properties. Recently, PZT thin films have been considered as one of the most promising materials for the application of nonvolatile electronic memories. In this study, a sol-gel process for PZT film preparation was adopted and greatly modified. PZT films with very desirable electrical properties have been successfully prepared by this modified sol-gel process. One of the problems of incorporating PZT films into the DRAM devices is the need of high post-deposition annealing temperatures which complicates their integration into the existing semiconductor manufacturing process. In this work, formation kinetics of PZT films were studied and the nucleation was found to be the rate-limiting step in the formation of the perovskite phase. Based on this finding, a seeding process was invented to encourage the nucleation of the perovskite phase. As a result of this seeding process, the transformation temperature has been lowered by as much as 100°C. The seeded PZT films also have good ferroelectric properties. The ferroelectric domain structures, and the metastable pyrochlore phase including its transformation to the perovskite phase have been investigated by transmission electron microscopy (TEM). The domain structures of the PZT films had the {lID} <110> orientation and most of them were 90° domains. The TEM study of the pyrochlore to perovskite transformation provides valuable insight on the formation of the perovskite phase. Among all the processing steps, the drying process of the sol-gel films created the highest growth stress. In addition, the thin film stress study was also used to determine the transformation stress and Curie temperature. The effects of composition, thermal processing conditions, and film thickness on electrical properties have been studied. Some of the notable results are as follow: (1) PZT films with a Zr/Ti ratio of 53/47, the morphotropic boundary (MPB) composition, have the highest remanent polarization and the lowest coercive field. (2) The optimum annealing temperatures for most of the PZT compositions are found to be about 50°C higher than the completion temperature of the perovskite formation (T_c^per) of the same composition. (3) PZT films with film thicknesses greater than or equal to 170 nm have electrical properties very close to those of the thicker films and are not susceptible to dielectric breakdown at an applied voltage of 5 V. / Ph. D.

Thesis (doctoral)--Helsinki University of Technology, 2009. / Includes bibliographical references. Also available on the World Wide Web.

No description available.

Thesis (Ph.D.)--Hong Kong University of Science and Technology, 2008. / Includes bibliographical references. Also available in electronic version.

Thesis (Ph.D.)--University of Nebraska-Lincoln, 2008. / Title from title screen (site viewed July 22, 2008). PDF text: ix, 169 p. : ill. (some col.) ; 8 Mb. UMI publication number: AAT 3299685. Includes bibliographical references. Also available in microfilm and microfiche formats.

Thesis (M.Sc.)--City University of Hong Kong, 2005. / At head of title: City University of Hong Kong, Department of Physics and Materials Science, Master of Science in materials engineering & nanotechnology dissertation. Title from title screen (viewed on Sept. 4, 2006) Includes bibliographical references.

Thesis (M.Sc.)--City University of Hong Kong, 2005. / At head of title: City University of Hong Kong, Department of Physics and Materials Science, Master of Science in materials engineering & nanotechnology dissertation. Title from title screen (viewed on Sept. 4, 2006) Includes bibliographical references.

Fatigue and electrical degradation including low voltage breakdown of ferroelectric lead zirconate titanate Pb(Zr_xTi₁)O₃ (i.e. PZT) thin films are the major limitations for commercial memory applications of these films. It is noted that the presence of oxygen vacancies and their entrapment at the electrode-ferroelectric interfaces are the sources of the degradation phenomena. Attempts were made in this study to solve these problems: 1) by minimizing oxygen vacancy entrapment at the interfaces by employing RuO₂ electrodes; 2) by lowering the oxygen vacancy concentration in PZT films using donor doping (e.g. La³⁺ at Pb²⁺ site and Nb⁵⁺ at Ti/Zr⁴⁺ site). For this study, PZT thin films were prepared by a sol-gel method and deposited on both Pt/Ti/SiO₂/Si and RuO₂/SiO₂/Si substrates. The microstructure and electrical properties, such as hysteresis properties, fatigue, leakage current, time-dependent dielectric breakdown (TDDB), and retention, were studied with regard to the Zr/Ti ratio, the excess lead, the annealing temperature, the electrode material, and the doping amount. Furthermore, the pyrochlore to perovskite phase transformation of PZT on RuO₂ electrodes was also investigated. It was shown that PZT films (Zr/Ti=50/50) with 10 at.% excess lead annealed at 650°C for 30 min possessed the best electrical properties for ferroelectric memory application. In confirmation with earlier theoretical and experimental results, no polarization loss was observed up to 10¹¹ switching cycles for the PZT films deposited on RuO₂ electrodes. However, the low Schottky barrier at the interfaces between RuO₂ and PZT films resulted in a higher leakage current at a high electric fields. Donor doping of PZT films decreased carrier concentrations in PZT films, and thus, decreased the leakage current to acceptable limits. In addition, it was also noted that the pyrochlore to perovskite phase transformation of PZT on RuO₂ was similar to that of PZT on Pt electrodes. It can be concluded that the combination of RuO₂ electrodes and donor doping produced PZT films with high fatigue endurance and low leakage currents which are suitable for memory applications. / Master of Science

Orientador: Alexandre Zirpoli Simoes / Banca: José Vitor Candido de Souza / Banca: Mauricio Antonio Algatti / Banca: Francisco Moura Filho / Banca: Filiberto González Garcia / Resumo: Os elementos de memórias de múltiplos estados nos quais a informação pode ser armazenada tanto nos estados de polarização quanto no estado de magnetização espontânea do elemento, podem ser obtidos, através da fabricação de filmes finos texturizados de BiFeO3 (BFO) dopados com Cálcio, sobre eletrodo de (Pt/TiO2/SiO2/Si), visando otimizar as propriedades ferroeletromagnêticas. O método Pechini ou percursores poliméricos, depositados por "Spin-Coating", é relativamente de fácil controle e baixo custo para a deposição de filmes finos texturizados. O cristal do BiFeO3 possui uma estrutura perovskita distorcida em um sistema romboédrica, mas em formato de filme fino encontramos uma fase pseudo tetragonal favorável as propriedades de memorias de múltiplos estados, como a diminuição da degradação, aumento da polarização espontânea e remanescente, diminuição na corrente de fuga, diminuição do tempo de resposta ao impulso, crescimento epitaxial, controle de vacâncias de oxigênio e diminuição de fases secundarias. Tudo isso é atingido, através de variações das resinas, controlando a volatização excessiva do Bismuto e de parâmetros no crescimento do filme, como, o tempo e temperatura de cristalização, da quantidade de dopante Ca, na variação de diferentes eletrodos óxidos de base para produção do filme fino. Apesar das excelentes propriedades dos filmes finos de BiFeO3 (BFO), dois sérios problemas são comumente encontrados para imediata aplicação deste material em memórias multiferróica... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The multi-state memory elements in which the information can be stored in both the polarization states and the spontaneous magnetization state of the element can be obtained by the production of calcium-doped thin films of BiFeO3 (BFO) on electrode (Pt / TiO2 / SiO2 / Si), in order to optimize ferroelectromagnetic properties. The Pechini method or polymer precursors, deposited by Spin-Coating, is relatively easy to control and low cost for the deposition of textured thin films. The crystal of the BiFeO3 has a perovskite structure distorted in a rhombohedral system, but in thin film format we find a pseudo tetragonal phase favorable to the properties of memories of multiple states, such as the decrease of the degradation, increase of the spontaneous and remaining polarization, decrease in the current reduction of impulse response time, epitaxial growth, control of oxygen vacancies and decrease of secondary phases. All of this is achieved through variations of the resins, controlling the excessive volatilization of Bismuth and parameters in the growth of the film, such as the time and temperature of crystallization, the amount of dopant Ca, in the variation of different base oxides electrodes for production of the thin film. Despite the excellent properties of the BiFeO3 (BFO) thin films, two serious problems are commonly encountered for the immediate application of this material in multiferroic memories: high current density, resulting in Fe (Fe3 + to Fe2 +) valence fluctuatio... (Complete abstract click electronic access below) / Doutor