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Complex Oxides possess a vast range of materials properties that will allow them to have a lasting impact on device architecture. To incorporated thin films of complex oxides into devices, a fundamental understanding of the mechanisms involved with thin film nucleation, growth, and interface formation must be achieved. For many complex oxide researchers, the deposition technique of choice is pulsed laser deposition (PLD). Our PLD chamber, installed at the G3 hutch in the Cornell High Energy Synchrotron Source, was specifically designed to study the growth kinetics during deposition. Chapter 1 of this thesis provides an introduction to complex oxide materials and pulsed laser deposition. Chapter 2 describes the x-ray scattering techniques used to study the thin film surface kinetics throughout this thesis. Chapter 3 presents a novel, in situ, x-ray scattering study of the PLD of the prototypic system: homoepitaxial SrTiO3 001 . The data provides a direct measurement of island nucleation, aggregation, and coarsening during PLD. Detailed analysis of these data lead to quantitative measurements of both in-plane and downhill diffusion. The same diffusion rate is found for these two processes, suggesting that the Ehrlich-Schwoebel barrier for downhill diffusion is negligible. This technique significantly increases the time resolution over other methods of measuring surface diffusion, such as scanning tunneling microscopy. In Chapter 4, we apply the methodology of Chapter 3 to a heteroepitaxial system: LaAlO3 on SrTiO3 001 . This materials system has received considerable attention in the literature due to the formation of a quasi-two-dimensional electron gas at the interface [1]. Conceptually, one might expect diffusion processes of the first monolayer, i.e. LaAlO3 on SrTiO3 , to differ from those of subsequent monolayers that involve diffusion of LaAlO3 constituents on the LaAlO3 film. We therefore measure the activation energy for diffusion as a function of the number of heteroepitaxial monolayers deposited. We find that the activation barrier for in-plane diffusion of LaAlO3 on SrTiO3 is larger than that for downhill diffusion of LaAlO3 to the SrTiO3 substrate. Additionally, we show that the downhill diffusion barrier is further decreased after the second LaAlO3 monolayer. In Chapter 5 we use in situ x-ray diffraction in a different configuration: as a probe to detect phase transformations at burred films. This chapter reports on the discovery of a new method to form brownmillerite structures in thin films of four different manganite materials: La0.7 Sr0.3 MnO3 , Pr0.7 Ca0.3 MnO3 , La0.7 Ca0.3 MnO3 , and LaMnO3 . These pseudomorphic, single crystal brownmillerite films form epitaxially on the most commonly used complex oxide substrate, SrTiO3 001 . The method involves the epitaxial deposition of an oxygen getter material (SrTiO3[-][delta] or LaAlO3[-][delta] ) on the manganite film. The getter layer removes oxygen from the buried manganite film, and when a critical thickness is reached, the buried manganite film phase transforms into an ordered brownmillerite structure. A provisional patent was provided for this technique1 . Chapter 6 provides the closing remarks, as well as suggesting future directions for the PLD/ x-ray diffraction experiment. "Epitaxial Getter Layer for a Complex Oxide Brownmillerite Phase Transformation in Maganite Films." U.S. Patent Application #6129690 (2010) 1
Despite its limitation in terms of surface covered area, the PLD technique still gathers interest among researchers by offering endless possibilities for tuning thin film composition and enhancing their properties of interest due to: (i) the easiness of a stoichiometric transfer even for very complex target materials, (ii) high adherence of the deposited structures to the substrate, (iii) controlled degree of phase, crystallinity, and thickness of deposited coatings, (iv) versatility of the experimental set-up which allows for simultaneous ablation of multiple targets resulting in combinatorial maps or consecutive ablation of multiple targets producing multi-layered structures, and (v) adjustment of the number of laser pulses, resulting in either a spread of nanoparticles, islands of materials or a complete covering of a surface. Moreover, a variation of PLD, known as Matrix Assisted Pulsed Laser Evaporation, allows for deposition of organic materials, ranging from polymers to proteins and even living cells, otherwise difficult to transfer unaltered in the form of thin films by other techniques. Furthermore, the use of laser light as transfer agent ensures purity of films and pulse-to-pulse deposition allows for an unprecedented control of film thickness at the nm level. This Special Issue is a collection of state-of-the art research papers and reviews in which the topics of interest are devoted to thin film synthesis by PLD and MAPLE, for numerous research and industry field applications, such as bio-active coatings for medical implants and hard, protective coatings for cutting and drilling tools withstanding high friction and elevated temperatures, sensors, solar cells, lithography, magnetic devices, energy-storage and conversion devices, controlled drug delivery and in situ microstructuring for boosting of surface properties.
The behavior of nanoscale materials can change rapidly with time either because the environment changes rapidly or because the influence of the environment propagates quickly across the intrinsically small dimensions of nanoscale materials. Extremely fast time resolution studies using X-rays, electrons and neutrons are of very high interest to many researchers and is a fast-evolving and interesting field for the study of dynamic processes. Therefore, in situ structural characterization and measurements of structure-property relationships covering several decades of length and time scales (from atoms to millimeters and femtoseconds to hours) with high spatial and temporal resolutions are crucially important to understand the synthesis and behavior of multidimensional materials. The techniques described in this book will permit access to the real-time dynamics of materials, surface processes and chemical and biological reactions at various time scales. This book provides an interdisciplinary reference for research using in situ techniques to capture the real-time structural and property responses of materials to surrounding fields using electron, optical and x-ray microscopies (e.g. scanning, transmission and low-energy electron microscopy and scanning probe microscopy) or in the scattering realm with x-ray, neutron and electron diffraction.
Advanced techniques for characterizing thin film growth in situ help to develop improved understanding and faster diagnosis of issues with the process. In situ characterization of thin film growth reviews current and developing techniques for characterizing the growth of thin films, covering an important gap in research. Part one covers electron diffraction techniques for in situ study of thin film growth, including chapters on topics such as reflection high-energy electron diffraction (RHEED) and inelastic scattering techniques. Part two focuses on photoemission techniques, with chapters covering ultraviolet photoemission spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS) and in situ spectroscopic ellipsometry for characterization of thin film growth. Finally, part three discusses alternative in situ characterization techniques. Chapters focus on topics such as ion beam surface characterization, real time in situ surface monitoring of thin film growth, deposition vapour monitoring and the use of surface x-ray diffraction for studying epitaxial film growth. With its distinguished editors and international team of contributors, In situ characterization of thin film growth is a standard reference for materials scientists and engineers in the electronics and photonics industries, as well as all those with an academic research interest in this area. Chapters review electron diffraction techniques, including the methodology for observations and measurements Discusses the principles and applications of photoemission techniques Examines alternative in situ characterisation techniques
This handbook provides a comprehensive review of the entire field of laser micro and nano processing, including not only a detailed introduction to individual laser processing techniques but also the fundamentals of laser-matter interaction and lasers, optics, equipment, diagnostics, as well as monitoring and measurement techniques for laser processing. Consisting of 11 sections, each composed of 4 to 6 chapters written by leading experts in the relevant field. Each main part of the handbook is supervised by its own part editor(s) so that high-quality content as well as completeness are assured. The book provides essential scientific and technical information to researchers and engineers already working in the field as well as students and young scientists planning to work in the area in the future. Lasers found application in materials processing practically since their invention in 1960, and are currently used widely in manufacturing. The main driving force behind this fact is that the lasers can provide unique solutions in material processing with high quality, high efficiency, high flexibility, high resolution, versatility and low environmental load. Macro-processing based on thermal process using infrared lasers such as CO2 lasers has been the mainstream in the early stages, while research and development of micro- and nano-processing are becoming increasingly more active as short wavelength and/or short pulse width lasers have been developed. In particular, recent advances in ultrafast lasers have opened up a new avenue to laser material processing due to the capabilities of ultrahigh precision micro- and nanofabrication of diverse materials. This handbook is the first book covering the basics, the state-of-the-art and important applications of the dynamic and rapidly expanding discipline of laser micro- and nanoengineering. This comprehensive source makes readers familiar with a broad spectrum of approaches to solve all relevant problems in science and technology. This handbook is the ultimate desk reference for all people working in the field.
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X-ray diffraction is an invaluable tool in the field of structural dynamics. In the work described in this thesis, time-resolved X-ray diffraction experiments were carried out to investigate ultrafast lattice dynamics. Ultrashort laser pulses were used to induce non-thermal melting and large-amplitude strain waves, and X-rays were used to probe these phenomena. Non-thermal melting was studied in indium antimonide (InSb). It was found that the inertial model, which states that the motion of the atoms is determined by their initial vibrational energy at the time of laser irradiation, accurately describes the process of non-thermal melting. It was demonstrated that the model is valid over a large range of temperatures, from 35 to 500 K, when taking the zero-point energy into account at low temperatures. It was also shown how the process of non-thermal melting can be used as a timing monitor to determine the relative timing of laser and X-ray beams in pump/probe experiments. It was shown how the use of an opto-acoustic transducer could reduce the duration of an Xray pulse. The transducer was made of a thin gold film deposited on the surface of bulk InSb. Upon heating the thin gold film with an ultrashort laser pulse, a strain wave was generated in the semiconductor. This resulted in a modulated phonon spectrum and X-ray reflectivity. It was shown that a 100 ps long X-ray pulse can be transformed to a 20 ps pulse with an 8% efficiency. A large-amplitude strain wave was generated in graphite using an ultrashort laser pulse to elucidate the potential role of strain in phase transitions. The temporal evolution of the strain wave was mapped, and the pressure deduced. It was found that it was possible to induce a pressure and temperature corresponding to the region in the carbon phase diagram in which diamond can form.
This proceedings includes 147 papers covering the latest scientific and technological developments in ferrites and related materials in three broad subject categories: Basic Science, Processing and Applications, and Special Topics and New Horizons. There are two main categories for ferrites: hard ferrites (permanent magnets) and soft ferrites. Topics covered are energy conversion, magnetite biomineralization, microwave ferrites, magneto-optical properties and applications of ferrite films, bonded magnets, physics of electronic superstructures in magnetite, physics of perovskites, nanostructural ferrites, and multilayer chip inductors.