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Ultrafast electron diffraction is a novel pump-probe technique which aims to determine transient structures during photoinduced chemical reactions and other structural transitions. This technique provides structural information at the atomic level of inspection by using an electron pulse as a diffractive probe. The atomic motions of interest happen on the 100 fs = 10^(−13) s time scale. To observe these atomic motions, a probe which matches this time scale is required. In this thesis, I describe the development of an electron diffractometer which is capable of 200 fs temporal resolution while maintaining high signal level per electron pulse. This was made possible by the construction of an ultra-compact photoactivated 60 keV femtosecond electron gun. Traditional electron pulse characterization methods are unsuitable for high number density femtosecond electron pulses such as the pulses produced by this electron gun. I developed two techniques based on the laser ponderomotive force to reliably determine the duration of femtosecond electron pulses into the sub-100 fs range. These techniques produce a direct cross-correlation trace between the electron pulse and a laser pulse. The results of these measurements confirmed the temporal resolution of the newly developed femtosecond electron diffractometer. This cross-correlation technique was also used to calibrate a method for the determination of the temporal overlap of electron and laser pulses. These techniques provide the pulse diagnostics necessary to utilize the temporal resolution provided by femtosecond electron pulses. Owing to their high charge-to-mass ratio, electrons are a sensitive probe for electric fields. I used femtosecond electron pulses in an electron deflectometry experiment to directly observe the transient charge distributions produced during femtosecond laser ablation of a silicon (100) surface. We found an electric field strength of 3.5 × 10^6 V/m produced by the emission of 5.3 × 10^11 electrons/cm^2 just 3 ps after an excitation pulse of 5.6 J/cm^2 . This observation allowed us to rule out Coulomb explosion as the mechanism for ablation under the conditions present in this experiment.

L'objectif principal de ce travail est l'étude fondamentale de nanostructures à base de carbone individuelles dans le but d'améliorer la compréhension de leurs propriétés vibrationnelles et optiques intrinsèques ainsi que d'estimer et de quantifier les effets d'environnement. Dans ce but, nous avons synthétisé des nanotubes de carbone mono- et multi-feuillets par décomposition catalytique en phase vapeur sur des substrats dédiés. L'aspect principal du travail est basé sur l'utilisation combinée de plusieurs sondes expérimentales sur la même nanostructure carbonée individuelle. Nous avons effectué une analyse structurale complète par diffraction électronique et microscopie électronique haute résolution et mesuré les spectres Raman de ces nanostructures individuelles. Plusieurs effets environnementaux importants ont été mis en évidence pour la première fois, comme par exemple l'effet d'un couplage mécanique (due à l'interaction de van-der-Waals) entre les parois des nanotubes bi-feuillets conduisant à une modification des modes Raman de basse fréquence et des conditions de résonances optiques. De plus, le comportement des modes de haute fréquence des nanotubes bi-feuillets a été analysé. Suite à ce travail plusieurs critères expérimentaux permettant un diagnostic de la structure des nanotubes multi-feuillets ont été proposés. / The main objective of this work is the fundamental physical study of individual isolated carbon nanostructures in order to address their intrinsic vibrational and optical properties and also to estimate and quantify the environmental effects. For these purposes, we synthesized individual single- and multi-walled carbon nanotubes by chemical vapour deposition method on dedicated substrates. The main aspect of the work involves the combined use of different experimental probes on the same individual nanostructures. We performed a complete structure analysis by electron diffraction and high-resolution electron microscopy and the measurement of the Raman spectra on these individual nanostructures. Several important environmental effects were evidenced for the first time, e.g. the effect of mechanical coupling (van-der-Waals interaction) between the layers of double-walled carbon nanotubes leading to the change in the low-frequency Raman modes and the optical resonance conditions. Moreover the behaviour of high-frequency modes of double-walled tubes was also analysed and described. As a result of this work several experimental criteria for structure diagnostics of multi-walled carbon nanotubes were proposed.

Both LiCoO2 and LiNi1/3Mn1/3Co1/3O2 layered cathode materials are investigated in our studies. P3 phase of CoO2, the end member of the LixCoO2, is found in both chemically and electrochemically delithiated materials. Delithiated LixCoO2 specimens decompose into fine Co3O4 and LiCoO2 particles starting at around 200 °C. This decomposing reaction is proved by in-situ X-ray diffraction and in-situ transmission electron microscopy investigations. The structures of pristine and cycled LiNi1/3Mn1/3Co1/3O2 are investigated by electron diffraction. Single and polycrystalline crystals are found in this material. The partial substitution of Co by Ni and Mn in LiNi1/3Mn1/3Co1/3O2 opens up the possibility of different cation configurations in the crystal lattice. Both 3Rm symmetry and superlattices are identified in this material. The number of particles with superlattices in pristine material (40%) is much bigger than cycled material at discharge state (10%).

Zeolites are crystalline microporous aluminosilicates with well-defined cavities or channels of molecular dimensions. They are widely used for applications such as gas adsorption, gas storage, ion exchange and catalysis. The size of the pore opening allows zeolites to be categorized into small, medium, large and extra-large pore zeolites. A typical zeolite is the small pore silicoaluminophosphate SAPO-34, which is an important catalyst in the MTO (methanol-to-olefin) process. The properties of zeolite catalysts are determined mainly by their structures, and it is therefore important to know the structures of these materials in order to understand their properties and explore new applications. Single crystal X-ray diffraction has been the main technique used to determine the structures of unknown crystalline materials such as zeolites. This technique, however, can be used only if crystals larger than several micrometres are available. Powder X-ray diffraction (PXRD) is an alternative technique to determine the structures if only small crystals are available. However, peak overlap, poor crystallinity and the presence of impurities hinder the solution of structures from PXRD data. Electron crystallography can overcome these problems. We have developed a new method, which we have called “rotation electron diffraction” (RED), for the automated collection and processing of three-dimensional electron diffraction data. This thesis describes how the RED method has been applied to determine the structures of several zeolites and zeolite-related materials. These include two interlayer expanded silicates (COE-3 and COE-4), a new layered zeolitic fluoroaluminophosphate (EMM-9), a new borosilicate (EMM-26), and an aluminosilicate (ZSM-25). We have developed a new approach based on strong reflections, and used it to determine the structure of ZSM-25, and to predict the structures of a series of complex zeolites in the RHO family. We propose a new structural principle that describes a series of structurally related zeolites known as “embedded isoreticular zeolite structures”, which have expanding unit cells. The thesis also summarizes several common structural features of zeolites in the Database of Zeolite Structures. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 3: Manuscript.</p>

The interest in two-dimensional materials and materials physics has grown dramatically over the past decade. The family of two-dimensional materials, which includes graphene, transition metal dichalcogenides, phosphorene, hexagonal boron nitride, etc., can be fabricated into atomically thin films since the intralayer bonding arises from their strong covalent character, while the interlayer interaction is mediated by weak van der Waals forces. Among them, molybdenum disulfide (MoS₂) has attracted much interest for its potential applications in opto-electronic and valleytronics devices. Previously, much of the experimental studies have concentrated on optical and transport measurements while neglecting direct experimental determination of the electronic structure of MoS₂, which is crucial to the full understanding of its distinctive properties. In particular, like other atomically thin materials, the interactions with substrate impact the surface structure and morphology of MoS₂, and as a result, its structural and physical properties can be affected. In this dissertation, the electronic structure and surface structure of MoS₂ are directly investigated using angle-resolved photoemission spectroscopy and cathode lens microscopy. Local-probe angle-resolved photoemission spectroscopy measurements of monolayer, bilayer, trilayer, and bulk MoS₂ directly demonstrate the indirect-to-direct bandgap transition due to quantum confinement as the MoS₂ thickness is decreased from multilayer to monolayer. The evolution of the interlayer coupling in this transition is also investigated using density functional theory calculations. Also, the thickness-dependent surface roughness is characterized using selected-area low energy electron diffraction (LEED) and the surface structural relaxation is investigated using LEED I-V measurements combined with dynamical LEED calculations. Finally, bandgap engineering is demonstrated via tuning of the interlayer interactions in van der Waals interfaces by twisting the relative orientation in bilayer-MoS₂ and graphene-MoS₂-heterostructure systems.

Ultra-fine grained materials with sub-micrometer grain size exhibit superior mechanical properties when compared with conventional fine-grained material as well as coarse-grained materials. Severe plastic deformation (SPD) techniques have been shown to be an effective way to modify the microstructure in order to improve the mechanical properties of the material. Crystalline materials require dislocations to accommodate plastic strain gradients and maintain lattice continuity. The lattice curvature exists due to the net dislocation that left behind in material during deformation. The characterization of such defects is important to understand deformation accumulation and the resulting mechanical properties of such materials. However, traditional techniques are limited. For example, the spatial resolution of EBSD is insufficient to study materials processed via SPD, while high dislocation densities make interpretations difficult using conventional diffraction contrast techniques in the TEM. A new technique, precession electron diffraction (PED) has gained recognition in the TEM community to solve the local crystallography, including both phase and orientation, of nanocrystalline structures under quasi-kinematical conditions. With the assistant of precession electron diffraction coupled ASTARÔ, the structure evolution of equal channel angular pressing processed commercial pure titanium is studied; this technique is also extended to two-phase titanium alloy (Ti-5553) to investigate the existence of anisotropic deformation behavior of the constituent alpha and beta phases.

"May 2002." / Thesis (Ph.D.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web. / Abstracts in English and Chinese.

by So King Lung, Benny. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1996. / Includes bibliographical references (leaves 102-109). / ABSTRACT --- p.v / ACKNOWLEDGEMENTS --- p.vii / LIST OF FIGURES --- p.viii / LIST OF TABLES --- p.xiii / Chapter Chapter 1 --- Background of the study --- p.1 / Chapter 1.1 --- Introduction --- p.1 / Chapter 1.2 --- Surface passivation techniques --- p.3 / Chapter 1.2.1 --- Sulfide solution passivation --- p.3 / Chapter 1.2.2 --- Gas-phase sulfide passivation --- p.4 / Chapter 1.3 --- Surface structure of sulfide-passivated surface --- p.5 / Chapter 1.4 --- Objectives of the present study --- p.7 / Chapter Chapter 2 --- Instrumentation --- p.9 / Chapter 2.1 --- Introduction --- p.9 / Chapter 2.2 --- X-ray photoelectron spectroscopy (XPS) --- p.9 / Chapter 2.2.1 --- The development of XPS --- p.9 / Chapter 2.2.2 --- Basic principle of XPS --- p.9 / Chapter 2.2.3 --- Quantitative analysis of XPS --- p.14 / Chapter 2.2.3.1 --- Atomic concentration of a homogenous material --- p.14 / Chapter 2.2.3.2 --- Layer structure --- p.15 / Chapter 2.2.3.3 --- Simulation of XPS atomic concentration ratios from proposed surface structural models --- p.17 / Chapter 2.2.4 --- XPS experiment --- p.19 / Chapter 2.3 --- Low energy electron diffraction (LEED) --- p.21 / Chapter 2.3.1 --- The development of LEED --- p.21 / Chapter 2.3.2 --- Basic principle of LEED --- p.23 / Chapter 2.3.3 --- LEED experiment --- p.28 / Chapter 2.3.3.1 --- The ultra high vacuum chamber (UHV) --- p.28 / Chapter 2.3.3.2 --- The electron gun --- p.28 / Chapter 2.3.3.3 --- The sample --- p.30 / Chapter 2.3.3.4 --- The detector system --- p.30 / Chapter Chapter 3 --- Surface treatments --- p.31 / Chapter 3.1 --- Semiconductor wafers --- p.31 / Chapter 3.2 --- Cleaning procedure --- p.31 / Chapter 3.3 --- Polysulfide passivation --- p.33 / Chapter Chapter 4 --- Gas-phase polysulfide passivation of the InP(100) surface --- p.37 / Chapter 4.1 --- Introduction --- p.37 / Chapter 4.2 --- Sulfide-assisted reordering at the InP(100) surface --- p.38 / Chapter 4.2.1 --- Gas-phase polysulfide-treated InP( 100) surface --- p.38 / Chapter 4.2.2 --- Further annealing of the gas-phase polysulfide-treated surface --- p.47 / Chapter 4.2.3 --- Comparison with the UV/O3-HF treatment --- p.48 / Chapter 4.2.4 --- Sulfide at the interface of SiNx/InP --- p.49 / Chapter 4.3 --- Conclusions --- p.53 / Chapter Chapter 5 --- Gas-phase polysulfide passivation of the GaAs(lOO) surface --- p.55 / Chapter 5.1 --- Introduction --- p.55 / Chapter 5.2 --- Gas-phase poly sulfide-passivated GaAs( 100) surface --- p.56 / Chapter 5.2.1 --- Surface structure of the as-treated surface --- p.56 / Chapter 5.2.2 --- Surface structure after further annealing --- p.64 / Chapter 5.2.3 --- Mechanism of the gas-phase polysulfide passivation --- p.67 / Chapter 5.3 --- Conclusions --- p.68 / Chapter Chapter 6 --- Gas-phase polysulfide passivation of the GaAs(100) surface --- p.69 / Chapter 6.1 --- Introduction --- p.69 / Chapter 6.2 --- Reordering at the gas-phase polysulfide-passivated GaAs(100) surface --- p.70 / Chapter 6.2.1 --- Adsorption of polysulfide on the GaAs(100) surface --- p.70 / Chapter 6.2.2 --- Ordered sulfide at the GaAs(l 10) surface --- p.73 / Chapter 6.2.3 --- Further analysis of the LEED pattern --- p.80 / Chapter 6.3 --- Conclusions --- p.83 / Chapter Chapter 7 --- Sulfide Solution passivation of the GaAs(100) surface --- p.84 / Chapter 7.1 --- Introduction --- p.84 / Chapter 7.2 --- Sulfide solution passivation on the GaAs(l 10) surface --- p.85 / Chapter 7.2.1 --- Etching of sulfide solution on the GaAs(l 10) surface --- p.85 / Chapter 7.2.2 --- Annealing of sulfide solution-passivated GaAs( 110) surface --- p.88 / Chapter 7.2.3 --- Further analysis of the LEED pattern --- p.92 / Chapter 7.2.4 --- Shift of XPS peak position during annealing --- p.95 / Chapter 7.3 --- Conclusions --- p.97 / Chapter Chapter 8 --- Conclusions and further work --- p.99 / Chapter 8.1 --- Conclusions --- p.99 / Chapter 8.2 --- Further work --- p.100 / References --- p.102

Les mémoires flash non volatiles - utilisées dans les ordinateurs, téléphones portables ou clés USB - peuvent être constituées de nanocristaux semiconducteurs (SC) insérées dans une matrice isolante. Elles nécessitent l'élaboration d'hétérostructures de type "oxyde/SC/oxyde/Si(00l)" et la maîtrise de chaque interface. Dans ce cadre, nous avons étudié les mécanismes de croissance initiale du Si et du Ge (SC) sur des substrats d'oxyde cristallins LaA1O3(001) à forte permittivité (high-k). Les propriétés chimiques et structurales ont été déterminées in-situ par photoémission X (XPS et XPD) et par diffraction d'électrons (RHEED et LEED) puis ex-situ par microscopies en champ proche (AFM) et en transmission (HRTEM). Le substrat LaAlO3(001) propre présente une reconstruction de surface c(2x2) attribuée à des lacunes d'O en surface. Les croissances de Si et Ge ont été réalisées par épitaxie par jet moléculaire (MBE), soit à température ambiante suivies de recuits, soit à haute température. L'épitaxie requiert des températures de dépôt supérieures à 550°C. Le mode de croissance est de type Volmer Weber caractérisé par la formation d'îlots cristallins de dimensions nanométriques et de forte densité. Ces îlots sont relaxés et présentent une interface abrupte avec le substrat. Quant aux îlots de Ge, ils ont majoritairement des orientations aléatoires avec néanmoins une relation d'épitaxie privilégiée, la même que celle du Si. / Non-volatile flash memory used in computers, mobile phones and USB-keys can be made up of nanocrystals (SC) inserted in an insulating matrix. It requires development of "Oxide/SC/oxide/Si (001)" type hetero-structures and the control of each interface. Within this framework, we studied the initial growth mechanisms of Si and Ge (SC) on LaA1O3(001) crystal oxide substrates with high permittivity (high-k). Chemical and structural properties have been studied in-situ by X-Ray photoemission (XPS and XPD) and electron diffraction (RHEED and LEED) technics and ex­ situ by atomic force microscopy (AFM) and high resolution tunneling electron microscopy (HRTEM). Clean LaA1O3(001) substrate contains a c(2x2) surface reconstruction which attributed to gaps of oxygen (O) on the surface. Si and Ge have been deposited by molecular bearn epitaxy (MBE), at room temperature followed by series of annealings at high temperatures. Epitaxy requires temperature more than 550°C for the deposition. Volmer Weber growth mode was characterized by the formation of nanometric densely packed islands. These islands are relaxed and have an abrupt interface with the substrate. Islands of Ge have mostly random orientations with nevertheless epitaxy privileged relationship, same as that of the Si.