Rozprawy doktorskie na temat „HIGH-RESOLUTION TRANSMISSION ELECTON MICROSCOPE”

Thermoelectric device has ability to modify thermal energy into electrical energy or vice versa, and such devices may propose a fabulous possibility in settling of energy problem from an environmental-sustainable aspect. Climate change issue and worldwide shortage of energy is creating exaggerated interests in other new spectacular contrivance of power generation with translucent energy sources. Whenever, the absence of any liquid media or other moving parts, a temperature gradient imposed between the hot and cold junction. A thermoelectric material plays an important role in primary power generation (i.e., combustion, chemical reactions, and nuclear decay), and energy conservation both. Several thermoelectric materials are reported. However, among all of these Tin Telluride (SnTe) displays exclusive features like low-toxicity and eco-friendly behaviour etc. The current prevalence illustrates that at temperature 300 K nano-structuring and band engineering may provide a high thermoelectric performance device of SnTe, which offers a substitute for toxic PbTe in similar operational temperature. The huge area competence and innateness of scaling up with comprehensive constraint of material handling provides possible application of sintering in industrial manufacture of coatings and optoelectronic devices. However, metal chalcogenides of the group IV-VI are gained significant attention due to its fascinating physical properties. These narrow bandgap semiconductors are enormously useful for thermoelectric devices, thermo-voltaic, photovoltaic and as well as various optical applications. Whereas, SnTe semiconductor possesses a cubic rock salt structure with a direct band gap 0.18 eV, which is responsible to make it more attractive. Many more applications such as photo detectors, mid-infrared (3-14 μm) detection and thermoelectric devices of SnTe is a proof of its capacity in material research. A Tin Telluride (SnTe) vacuum evaporated thin films has been synthesized at room temperature (RT) on a glass substrate, which has been proven as a significant enhancement in the figure of merit (ZT) value as p-type material. Moreover, a high-resolution X-ray diffraction (HRXRD) outlines indicated towards a polycrystalline nature in bulk solids as well as in thin films both. Surface morphology of composed grains of variable sizes of these films also investigated using scanning electron microscopy (SEM), which has been further supported by atomic force microscopy (AFM) wherein, the surface parameters (like roughness, skewness, and kurtosis) were measured and analyzed to determine topography of the thin film surface. High-resolution transmission electron microscope (HRTEM) also touches to local microstructural features and crystalline structure, which another level investigation has been confirmed using selected area electron diffraction (SAED) pattern analysis. Four probes method has also been used to determine electrical measurements, which confirm that the thin films behave as a semi-metallic nature. We observed that figure of merit of thin films increases with thickness of the film. The maximum ZT value of ∼ 1.02 for the SnTe thin film with thickness 275 nm and ∼ 1.04 for In-doped SnTe thin film of thickness 450 nm has been observed at room temperature measurement. A detailed analyzes of SnTe is indicated that SnTe is the utmost promising material for thin film photovoltaics, thermoelectric device and IR detector. Whereas, present research work also deals with a comparative study of bulk solids and thin films of SnTe and In-doped SnTe compound semiconducting material. Whereas, it has been observed that optical, electrical and thermoelectric properties of thin films alter with the thickness of thin film. The present thesis has been discussed into seven chapters, which brief discussion has been indicated in the following paragraphs. Chapter 1 introduces to the fundamental aspects of thermoelectric materials. Various kinds of thermoelectric materials such as Metal chalcogenides, Superionic conductors, Metal oxides, Silicon-based materials, PGEC thermoelectric materials categorized as Skutterudites, clathrates, half- Heusler alloys, and SnTe has been discussed in this segment (introduction) of the thesis. Literature review of SnTe compound is discussed thoroughly including the detailed explanation about crystalline structures, phase diagrams and related applications. The effect of doping in pure SnTe has also been discussed in detail with an optimal literature survey. Overall, the semiconducting compound materials discussed in this part. This chapter ends with the motivation for the present work. Finally, the objectives of the thesis based on the review of the literature have been incorporated. Chapter 2 describes a brief description of experimental and characterization techniques used in the present investigation for the synthesis of bare SnTe and Indium doped SnTe bulk and thin films. Whereas, a primarily, vertical directional solidification (VDS) and subsequently thermal evaporation technique have been used for the synthesis of the bulk SnTe, In-doped SnTe and their thin films. This chapter includes the details of sophisticated analytical experimental tools like, XRD/ HRXRD, VP-SEM, EDS, TEM/HRTEM, AFM, FTIR, micro-Raman, PL, UV-NIR, TOF-SIMS, EPR, Four probe method (-T) and Herman method (ZT) measurements for different properties. Bulk SnTe and In-doped SnTe in the form of ingot was prepared by the physical route via VDS technique in a vertical muffle furnace. The thin film deposition has been performed on glass, silicon, and NaCl substrate using the thermal vapor deposition instrument and discussed in detail in this chapter. Chapter 3 provides the detailed investigation of the bulk SnTe ingot. This chapter emphasized that SnTe material was prepared by vertical directional solidification (VDS) technique at high temperature via the physical route. Bulk SnTe pallets were used for the structural characterization (XRD). XRD pattern of bulk SnTe confirms the formation of polycrystalline SnTe as well as its atomic-scale range of structural periodicity. From the XRD analysis it is established that both cubic and orthorhombic phases co-exist in bulk SnTe compound. Rietveld refinement of four-time repeated XRD data indicates all best-fitting parameters for analysis of bulk SnTe. SEM and EDX analyses show the existence of cleavage planes on the morphological surface of the bulk SnTe compound. The results obtained from the EDX revealed that the stoichiometry of Sn and Te is maintained perfectly. The microstructural investigations were achieved by employing HRTEM and SAED, which confirm that inter-planar spacing values correlate with XRD data, and various sizes of grains are present in the material. Some grain boundaries have been occurred, establishing about the formations of imperfections in the material. HRTEM micrographs show the disorder in the grain boundaries of different grains, and hence here in most cases, lattice fringes of different grains were merged with each other. FTIR and Micro - Raman spectra revealed that the SnTe is a suitable compound for IR applications. EPR results revealed that holes are present in an abundant concentration, and voids presence makes the material highly paramagnetic. As SIMS spectra revealed the presence of unreacted Tin, Tellurium, SnTe compound, and impurities in the ingot up to ppm level, therefore this may be an appropriate reason for paramagnetic behavior. The confirmation of the p-type nature of SnTe indicates the presence of holes or vacancies in the material, which is also responsible for paramagnetic resonance. The reaction of very – very few oxygen atoms with the material may also be responsible for free electrons in the material, which seems a strongly correlated with Micro-Raman and FTIR results. Electrical properties confirmed that P-type SnTe is semi-metallic, and resistivity is temperature-dependent. These studies explore the feasibility of employing the material in the industrial production line of infrared detectors. Chapter 4 reports the detailed study of SnTe thin films of different thickness deposited on various substrates. By using thermal evaporation equipment, a series of Tin Telluride (SnTe) thin films of varied thicknesses are deposited onto different substrates at 300 K. The morphology, microstructure, topology, optical, elemental mass isotope spectrum, electrical, and thermoelectric properties of SnTe thin films having thicknesses 33 nm to 275 nm have reported here. High-resolution x-ray diffraction (HRXRD) patterns of SnTe thin films revealed the polycrystalline nature with [200], which orientation possessed a cubic structure. Rietveld refinement of XRD data of these thin films indicates all best-fitting parameters for the analysis of crystalline features. The microstructural and morphological structures of all thin films were examined using HRTEM and SEM-EDS, respectively. The distribution of isotopes of various elements in the thin film along with facet and longitudinal channels was expolred by using depth profile determination through the TOF – SIMS technique. Fourier transform infrared spectroscopy spectra reveal the molecular vibrations, narrow bandgap property of material, and suitability of materials in infrared applications. Longitudinal – optical phonon scattering due to the [222] plane orientation is also observed in the micro-Raman spectra at room temperature, which corresponds to a peak in the range 120–130 Raman shift/cm−1. Hence, the change in optical and microstructural properties at the nano-regime resulted in a shift towards the near-infrared region with an enhancment in the thickness of the thin films. Electrical properties enhance with the decrease of thin-film thickness. Whereas, figure of merit (ZT) equal to 1.02 is the highest value for a thin film of thickness 275 nm among all four thin films. Chapter 5 reports the detailed study of doping of the Indium (In) element in SnTe bulk compound and In-doped SnTe thin films with thickness of 50 nm, 245 nm and 450 nm. Rietveld refinement of XRD data of bulk In0.1Sn0.9Te compound and thin films indicates the formation of polycrystalline bulk and thin films. Rietveld refinement of XRD data indicates all best-fitting parameters for analysis of In-doped SnTe thin films. Morphological, microstructural, topological, optical, and thermoelectric properties have also described in this chapter. SEM, TEM and AFM micrographs revealed that nanoparticles (NPs) of different size from 50 nm to 500 nm have been spread along the whole of surface of thin film. These different size NPs can affect the optical properties of these thin films, because due to absorption of light in visible region the variable size of NPs can emit diverse colors radiations. However, the metallic NPs show dissimilar physical and chemical properties in comparison of bulk metals. It is clear that NPs have large surface area to volume ratio hence in the case of NPs huge interactive interface exist between the adjacent particle and thier local surroundings. As per use of any compound rather in the form of bulk material or in the form of nanomaterials the properties of similar chemical compositional material changed significantly. Thermoelectric properties (figure of merit) revealed that ZT = 1.04 is highest for the film of thickness 450 nm. Chapter 6 describes the detailed study of Ultra-fast spectroscopy for SnTe and In-doped SnTe thin films. This chapter describes relationship about the study of optical properties with dynamics of thin film. Ultrafast laser spectroscopy is a sophisticated technique in which ultrashort pulse lasers generally used to study the dynamics of reaction mechanism up to tremendously small-time scales. Various techniques are practiced for the study of the dynamics of holes and electrons, atoms or molecules. The time domain part of frequency-resolved spectroscopy is the main component of ultrafast molecular spectroscopy. In the case of ultrafast spectroscopy, coherent quantum levels lead to time-dependent dynamics which is belongs to the traditional mechanical movement. In ultrafast spectroscopy, a 70-fs pulse is applied to pump the specimen, which is generated as a result of a mode-locked laser beam, amplifier, and optical parametric amplifier (OPA). The mode-locked laser is of MICRA, which generates a 35-fs pulse of 800 nm with a 320mW average power. The pulsed laser is then amplified using a COHERENT amplifier in which the Ti: Sapphire crystal is used to amplifies the pulse laser to 4 W. This laser pulse is then split into 70:30 using a beam splitter in which 30% of the laser beam is passed through the delay stage to provide a 6 ns long delay. The delayed beam is then passed through the Ti: Sapphire crystal to generate a continuum in the NIR range of 800-1600 nm. Simultaneously, the remaining 70% of the laser beam is passed through TOPAs, which is an OPA. The HELIOS spectrometer is used to detect the differential reflectance in which the InGaAs detector is used. The system is calibrated through the in-house built BND in CSIR-NPL. Chapter 7 provides a summary of the research work done in this thesis. It also suggests and outlines open issues and the future course of research in the area of Chalcogenide materials and compound semiconductors.

Thesis: S.B., Massachusetts Institute of Technology, Department of Materials Science and Engineering, 2018.
Cataloged from PDF version of thesis.
Includes bibliographical references (pages 47-50).
III-V materials have great potential for integration into future complementary metal-oxide-semiconductor technology due to their outstanding electron transport properties. InGaAs n-channel metal-oxide-semiconductor field-effect transistors have already demonstrated promising characteristics, and the antimonide material system is emerging as a candidate for p-channel devices. As transistor technology scales down to the sub-10-nm regime, only devices with a 3D configuration can deliver the necessary performance. III-V fin field-effect transistors (finFETs) have displayed impressive characteristics but have shown degradation in performance as the fin width is scaled to the sub-10-nm regime. In this work, we use high-resolution transmission electron microscopy (HRTEM) in an effort to understand how interfacial properties between the channel and high-k dielectric affect device performance. At the interface between the channel material, such as InGaSb or InGaAs, and the high-k gate dielectric, properties of interest include defect density, interdiffusion between the semiconductor and dielectric, and roughness of the dielectric - semiconductor interface. Using HRTEM, we can directly study this interface and try to understand how it is affected by different processing conditions and its correlation with device characteristics. In this thesis, we have analyzed both InGaAs and InGaSb finFETs with state-of-the-art fin widths. Analysis of TEM images was combined with electrical data to correlate interfacial properties with device performance. We compared the materials properties of InGaAs and InGaSb and also explored the impact of processing steps on interfacial properties.
by Lisa Kong.
S.B.

Graphene, a one-atom thick sheet of carbon, is the thinnest, strongest and most electrically conductive material ever discovered. Alongside carbon nanotubes it is part of the group of nanocarbons whose unique properties have sparked huge interest in possible applications, including electronic devices, solar cells and biosensors. Doping of these materials allows for the modification of their optical and electronic properties,which is crucial to realising these applications. Studying the properties of these doped materials at atomic resolution and finding controllable and industrially scalable routes to doping, such as low energy ion implantation, are thus essential if they are to becomethe materials of the future. In this thesis, highly localised optical enhancements in metal doped graphene are studied using energy-filtered transmission electron microscopy in a monochromated and aberration corrected electron microscope. The ideal conditions for imaging the low energy loss region of graphene using EFTEM are discussed and new methods to compensate for image artifacts when using this technique at high resolution are presented. Density functional theory is used to reveal new visible spectrum plasmon excitations in the electron energy loss spectra of boron and nitrogen doped nanocarbons. Atomic resolution scanning transmission electron microscopy and nanoscale electron energy loss spectroscopy are used to investigate controllable and defect-free substitutional doping of suspended graphene films through low energy ion implantation. Computational methods for filtering high angle annular dark field images are shown and software for the automated processing and spectroscopic analysis of these images is developed.

This thesis concerns the application of aberration corrected scanning transmission electron microscopy (STEM) to the quantitative analysis of industrial Pd-Pt core-shell catalyst nanoparticles. High angle annular dark field imaging (HAADF), an incoherent imaging mode, is used to determine particle size distribution and particle morphology of various particle designs with differing amounts of Pt coverage. The limitations to imaging, discrete tomography and spectral analysis imposed by the sample’s sensitivity to the beam are also explored. Since scattered intensity in HAADF is strongly dependent on both thickness and composition, determining the three dimensional structure of a particle and its bimetallic composition in each atomic column requires further analysis. A quantitative method was developed to interpret single images, obtained from commercially available microscopes, by analysis of the cross sections of HAADF scattering from individual atomic columns. This technique uses thorough detector calibrations and full dynamical simulations in order to allow comparison between experimentally measured cross section to simulated ones and is shown to be robust to many experimental parameters. Potential difficulties in its applications are discussed. The cross section approach is tested on model materials before applying it to the identification of column compositions of core-shell nanoparticles. Energy dispersive X-ray analysis is then used to provide compositional sensitivity. The potential sources of error are discussed and steps towards optimisation of experimental parameters presented. Finally, a combination of HAADF cross section analysis and EDX spectrum imaging is used to investigate the core-shell nanoparticles and the results are correlated to findings regarding structure and catalyst activity from other techniques. The results show that analysis by cross section combined with EDX spectrum mapping shows great promise in elucidating the atom-by-atom composition of individual columns in a core-shell nanoparticle. However, there is a clear need for further investigation to solve the thickness / composition dualism.

This thesis considers the theory and calculations of image formation mechanisms for various modes of three-dimensional imaging in aberration-corrected scanning transmission electron microscopy. Discrete tomography is used to determine and refine the three-dimensional structure of molecular nanowire bundles. The structure determination is expedited by the use of annular dark-field imaging, an incoherent imaging mode which provides directly interpretable images. The development of spherical aberration correctors and the subsequent reduction in probe sizes, including the depth of field, has made optical depth sectioning a feasible technique. The localisation in three dimensions of substitutional impurity atoms in zone-axis imaging is discussed. Both the channelling of the probe and the pre-focussing effect of the atomic column play an important role in determining the depth response of the impurity atom. Interband scattering within a sample is shown to be influential in imaging crystals containing dislocations and optical depth sectioning is explored as a possible option for overcoming surface relaxation effects in the imaging of screw dislocations end-on. The possibility of extending the optical depth sectioning approach using aberration-corrected scanning confocal electron microscopy is discussed. The coherent and incoherent imaging modes, involving elastically and inelastically scattered electrons respectively, are investigated.

PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO
COORDENAÇÃO DE APERFEIÇOAMENTO DO PESSOAL DE ENSINO SUPERIOR
CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO
PROGRAMA DE SUPORTE À PÓS-GRADUAÇÃO DE INSTS. DE ENSINO
Apesar do bismuto cristalino e do níquel não serem supercondutores, as bicamadas Bi/Ni mostram uma transição supercondutora a 4 K, o que tem atraído muita atenção. Existem diferentes interpretações para a supercondutividade (SC) em Bi/Ni, por exemplo: a presença de Ni induz a transformação de estrutura de Bi, originalmente romboédrica torna-se cúbica de face centrada (CFC); as flutuações magnéticas na interface Ni/Bi poderiam gerar a SC; a formação do intermetálico NiBi3 na interface; a SC induzida por Bi na camada de Ni e a formação de uma camada de Bi amorfa fina na interface Ni/Bi. Neste trabalho foram estudadas a SC e as modificações estruturais, tanto em sistemas de bicamadas quanto em sistemas de nanopartículas de Bi/Ni, por meio de medidas de transporte elétrico, medições magnéticas e microscopia eletrônica de transmissão em alta resolução (HRTEM). Foram observadas transições de duas etapas nas bicamadas Bi/Ni. Os resultados estruturais mostram que duas fases intermetálicas, NiBi e NiBi3, formaram-se durante a preparação da amostra por deposição a laser pulsado. A formação destes intermetálicos constitui-se na origem da SC em sistemas Bi/Ni. Um fenômeno interessante foi a observação da fase rica em Bi (NiBi3) na proximidade da camada de Ni. Entretanto, a fase rica em Ni (NiBi) é formada após a camada NiBi3. Os resultados de espectroscopia por energia característica de raios-X (EDXS) com resolução nanométrica mostram claramente um aumento incomum da concentração de Ni próximo à interface Bi/Substrato, o que foi confirmado por HRTEM. Foram igualmente estudados sistemas constituídos por filmes de Bi/nanopartículas de Ni e filmes de Ni/nanopartículas de Bi, preparados a temperatura ambiente, não tendo sido observada a transição supercondutora completa nestes sistemas. Por outro lado, as bicamadas Bi/Ni e, mesmo, as tricamadas Bi/Ni/Bi, quando preparadas a 4,2 K por evaporação térmica, não revelaram formação de intermetálicos, mesmo após o recozimento a 300K, e não exibem SC. Com estes resultados, a SC em filmes finos Bi/Ni se explica pela formação do NiBi e NiBi3 devido a interdifusão na interface.
Despite crystalline bismuth and nickel being not superconducting, Bi/Ni bi-layers show a superconducting transition at about 4 K and this has been attracting attention. There are different interpretations for the superconductivity (SC) in Bi/Ni, for example: the presence of Ni induces the modification of Bismuth structure from rhombohedral to face centered cubic (FCC); magnetic fluctuations at the interface of Ni/Bi would induce SC; formation of intermetallic NiBi3 at the interface; Bi induced superconductivity in Ni layer and formation of a very thin amorphous Bi layer formed at the interface of Ni/Bi. The present work studies the SC and microstructure modifications of the Bi/Ni bilayer and nanoparticle systems by means of electric transport and magnetic measurements, and high resolution electron microscopy (HRTEM). Two-step transitions have been observed in Bi/Ni bilayers. The observed microstructure shows that two intermetallic phases (NiBi and NiBi3) have been formed during the sample preparation by pulsed laser deposition. The formation of the two intermetallic compounds constitutes the origin of the superconductivity in Bi/Ni systems. One interesting phenomenon is the observation of Bi-rich phase (NiBi3) formed near the Ni layer. However, the Ni-rich phase (NiBi) is formed after the NiBi3 layer. Energy dispersive X-ray spectroscopy (EDXS) results at nanometer scale clearly show an unusual increase of Ni concentration near the interface of Bi/Substrate, which was confirmed by HRTEM observation. Bilayers of Bi/Ni nanoparticles and Ni/Bi nanoparticles have been studied as well and the samples do not show a full superconducting transition. On the other hand, Bi/Ni bilayers and Bi/Ni/Bi trilayers have been prepared at 4.2 K by thermal evaporation do not reveal formation of intermetallic compounds even after annealing at 300 K, and they are not superconducting down to 1.8 K . With this result, The SC in Ni/Bi thin films can be explained by the formation of NiBi and NiBi3 due to interdiffusion at the interface.

Titanium nitride (TiN) films are widely applied as diffusion barrier layers in microelectronic devices. The continued miniaturization of such devices not only poses new challenges to material systems design, but also puts high demands on characterization techniques. To gain understanding of diffusion processes that can eventually lead to failure of the barrier layer and thus of the whole device, it is essential to develop routines to chemically and structurally investigate these layers down to the atomic scale. In the present study, model TiN diffusion barriers with a Cu overlayer acting as the diffusion source were grown by reactive magnetron sputtering on MgO(001) and thermally oxidized Si(001) substrates. Cross-sectional transmission electron microscopy (XTEM) of the pristine samples revealed epitaxial, single-crystalline growth of TiN on MgO(001), while the polycrystalline TiN grown on Si(001) exhibited a [001]-oriented columnar microstructure. Various annealing treatments were carried out to induce diffusion of Cu into the TiN layer. Subsequently, XTEM images were recorded with a high-angle annular dark field detector, which provides strong elemental contrast, to illuminate the correlation between the structure and the barrier efficiency of the single- and polycrystalline TiN layers. Particular regions of interest were investigated more closely by energy dispersive X-ray (EDX) mapping. These investigations are completed by atom probe tomography (APT) studies, which provide a three-dimensional insight into the elemental distribution at the near-interface region with atomic chemical resolution and high sensitivity. In case of the single-crystalline barrier, a uniform Cu-enriched diffusion layer of 12 nm could be detected at the interface after an annealing treatment at 1000 °C for 12 h. This excellent barrier performance can be attributed to the lack of fast diffusion paths such as grain boundaries. Moreover, density-functional theory calculations predict a stoichiometry-dependent atomic diffusion mechanism of Cu in bulk TiN, with Cu diffusing on the N-sublattice for the experimental N/Ti ratio. In comparison, the polycrystalline TiN layers exhibited grain boundaries reaching from the Cu-TiN interface to the substrate, thus providing direct diffusion paths for Cu. However, the microstructure of these columnar layers was still dense without open porosity or voids, so that the onset of grain boundary diffusion could only be found after annealing at 900 °C for 1 h. The present study shows how to combine two high resolution state-of-the-art methods, TEM and APT, to characterize model TiN diffusion barriers. It is shown how to correlate the microstructure with the performance of the barrier layer by two-dimensional EDX mapping and three-dimensional APT. Highly effective Cu-diffusion barrier function is thus demonstrated for single-crystal TiN(001) (up to 1000 °C) and dense polycrystalline TiN (900 °C).

The current work is part of the EPSRC MUZIC project, which established the collaboration among several universities to carry out a multidiscipline study on the breakaway oxidation of zirconium alloys. The overall goal of the project is to further understand the mechanisms of the oxidation and breakaway process of zirconium alloys. This thesis describes the nano/micro-structural study and nano-analysis of the corroded zirconium alloys using up-to-date TEM and 3D focused ion beam (FIB) slicing and reconstruction techniques. The work mainly focused on the characterization of ZIRLO. The oxide morphology in general comprises an inner columnar layer and an outer equiaxed layer, except for a post-second transition oxide grown on a Zr-Nb-Ti test alloy with a very poor corrosion resistance, which exhibits generally only equiaxed grains throughout the whole oxide scale. Detailed investigation reveals oxides in a slower oxidation stage exhibit better developed columnar grain structure. All the oxides, independent of different corrosion stages and alloy types, contain predominantly monoclinic oxide and a small amount of tetragonal oxide. Defects at different length scales were examined. In stead of a sudden burst of crack nucleation at the kinetic transition, a gradual introduction of cracks parallel to the metal/oxide interface throughout the pre-transition stage is found, suggesting no direction correlation between the formation of cracks and the transition. Besides cracks, the oxide also contains different forms of nano-porosity: isolated pores of 1-3 nm or interconnected pores at grain boundaries. The density of interconnected porosity, especially those along the oxide growth direction, increases towards the oxide surface, evolving over time. It is suggested that the kinetic transition is related to the development of an interconnected porosity down to the metal/oxide interface, providing easy pathways for the transportation of oxidation species. The metal-oxide interface has a wavy morphology both in the micrometer and nanometer scale. The roughness develops to a maximum just before the first kinetic transition. An intermediate suboxide layer with complex 3D morphology between the bulk oxide and the metal substrate is found. Quantitative EELS analysis shows the composition of this layer to be 40-50 at. % oxygen. The suboxide appears to develop in thickness with increasing oxidation time for the pre-transition oxides, while is very thin or absent in the post-, and post-second transition oxides. In the suboxide region, multiple phases including α-Zr, ω-Zr, tetragonal oxide and a phase with an unidentified structure were found, suggesting different structures can coexist in the suboxide layer. Second-phase particles (SSPs) of β-Nb and hexagonal Zr(Fe,Nb)₂ types were found in ZIRLO samples and FCC Zr(Fe,Cr)₂ was the predominant type in Zircaloy-4. The SPPs showed delayed oxidation compared to surrounding Zr. In ZIRLO, those containing high Fe contents were found to be oxidized and transform into an amorphous state much earlier than β-Nb. Hydrides of different types (γ, σ and ε) were observed in the metal and metal/oxide region for both Zircaloy-4 and ZIRLO samples. A higher density of hydrides was seen in post-transition oxides of ZIRLO than in pre-transition oxides.

Three-dimensional porous single crystals (PSCs) are a recent development in the growing world of mesoporous material. The mesoporosity allows for the material to retain their nanoproperties whilst being bulk in size. The current work concentrates on chromium oxide and cobalt oxide PSCs formed in the templates SBA-15 and KIT-6. HRTEM is the main technique used in this investigation, looking at the morphology and single crystallinity of these materials. A growth mechanism for the PSC material is proposed based on HRTEM observations. XRD studies revealed that the confinement effect, caused by the mesopores, reduces the temperature for both cobalt and chromium oxide crystallisation, as well as a different intermediate route from the metal nitrates. The properties of chromium oxide PSC are also investigated magnetically and catalytically. Some metal oxides in different templates are also presented, despite no PSC forming. HRTEM work on other nanomaterials, based on collaboration, is also presented.

Orientador: Antonio Jose Ramirez Londono
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica
Made available in DSpace on 2018-08-19T15:09:29Z (GMT). No. of bitstreams: 1 GrandoStroppa_Daniel_D.pdf: 7882693 bytes, checksum: 21824c021c6088d93bb5e17e9b0386ff (MD5) Previous issue date: 2011
Resumo: O desenvolvimento de tecnologias baseadas em nanoestruturas é dependente da criação de modelos confiáveis que possam suportar a obtenção de materiais com características controladas. Neste contexto, o aprimoramento de técnicas de caracterização quantitativa e com alta resolução espacial é fundamental para o melhor entendimento das correlações entre a configuração de síntese, a morfologia e as propriedades resultantes de materiais nanoestruturados. Esta tese apresenta a avaliação e a aplicação de diferentes técnicas de Microscopia Eletrônica de Transmissão de Alta Resolução Quantitativa (QHRTEM) visando a extração de informações relacionadas à estrutura tridimensional e à segregação de espécies dopantes em nanocristais individuais de óxidos semicondutores dopados (Sb:SnO2 e Gd:CeO2). Os resultados experimentais combinados a cálculos teóricos proporcionaram a obtenção de informações referentes à distribuição de energia superficial e aos mecanismos de crescimento de cristais envolvidos na evolução temporal dos sistemas estudados. A descrição de tais aspectos de sistemas nanocristalinos explicita a importância das técnicas QHRTEM, tanto no contexto do desenvolvimento e aplicação do modelamento de nanocristais, quanto para o avanço das teorias fundamentais que descrevem o comportamento dos materiais em escala nanométrica. Neste sentido, os resultados presentes nesta tese constituem significativos avanços para o entendimento das características dos materiais em escala atômica e para a posterior manipulação destas segundo o preceito da engenharia de materiais no desenvolvimento de novas tecnologias
Abstract: Technologies based on nanostructured materials depend on the development of reliable models which can support the fabrication of nanocrystals with highly controlled features. In this scenario, advances on high resolution quantitative techniques are required in order to improve the description of the nanostructured systems, especially the correlations among the nanocrystals synthesis parameters, the resultant morphology and the system properties. This PhD thesis presents the evaluation and use of different Quantitative High Resolution Transmission Electron Microscopy (QHRTEM) techniques aiming the three-dimensional morphology and the dopant species segregation characterization of individual oxide nanocristals (Sb:SnO2 e Gd:CeO2). In addition, the combined use of such techniques and theoretical calculations provided valuable insights on the surface energy distribution and growth mechanisms present on the analyzed nanocrystalline systems. The obtained high resolution quantitative characterization results indicate that QHRTEM techniques are priceless tools for both the nanocrystal modeling procedures development and application, and for the improvement of fundamental theories that describe the materials features at nanoscale. In this scenario, this thesis presents significant advances on the nanomaterials characteristics description and, consequently, on their further manipulation aiming novel technologies development according to the materials engineering approach
Doutorado
Materiais e Processos de Fabricação
Doutor em Engenharia Mecânica

Transmission Electron Microscopy (TEM) on light element materials and soft matters is problematic due to electron irradiation damage and low contrast. In this doctoral thesis techniques were developed to address some of those issues and successfully characterize these materials at high resolution. These techniques were demonstrated on graphene flakes, DNA/magnetic beads and a number of water containing biomaterials. The details of these studies are given below. A TEM based method was presented for thickness characterization of graphene flakes. For the thickness characterization, the dynamical theory of electron diffraction is used to obtain an analytical expression for the intensity of the transmitted electron beam as a function of thickness. From JEMS simulations (experiments) the absorption constant λ in a low symmetry orientation was found to be ~ 208 nm (225 ± 9 nm). When compared to standard techniques for thickness determination of graphene/graphite, the method has the advantage of being relatively simple, fast and requiring only the acquisition of bright-field (BF) images. Using the proposed method, it is possible to measure the thickness change due to one monolayer of graphene if the flake has uniform thickness over a larger area. A real-space TEM study on magnetic bead-DNA coil interaction was conducted and a statistical analysis of the number of beads attached to the DNA-coils was performed. The average number of beads per DNA coil was calculated around 6 and slightly above 2 for samples with 40 nm and 130 nm beads, respectively. These results are in good agreement with magnetic measurements. In addition, the TEM analysis supported an earlier hypothesis that 40 nm beads are preferably attached interior of the DNA-coils while 130 nm beads closer to the exterior of the coils. A focused ion-beam in-situ lift-out technique for hydrated biological specimens was developed for cryo-TEM. The technique was demonstrated on frozen Aspergillus niger spores which were frozen with liquid nitrogen to preserve their cellular structures. A thin lamella was prepared, lifted out and welded to a TEM grid. Once the lamella was thinned to electron transparency, the grid was cryogenically transferred to the TEM using a cryo-transfer bath. The structure of the cells was revealed by BF imaging. Also, a series of energy filtered images was acquired and C, N and Mn elemental maps were produced. Furthermore, 3 Å lattice fringes of the underlying Al support were successfully resolved by high resolution imaging, confirming that the technique has the potential to extract structural information down to the atomic scale. The experimental protocol is ready now to be employed on a large variety of samples e.g. soft/hard matter interfaces.

The acidic, non-oxidative dissolution of galena nanocrystals has been studied using both microscopic and wet-chemical methods. The effects of particle size, shape, aggregation state, and grain proximity on dissolution rates were investigated. Nearly monodisperse galena nanocrystals with an average diameter of 14.4 nm and a truncated cubic shape were synthesized. In the dissolution experiments of dispersed nanocrystals, galena nanocrystals attached on the surface of a TEM grid were exposed to deoxygenated HCl solutions (pH 3) at 25 °C. Capping groups on nanocrystals were removed via a washing process, and chemistry of nanocrystals was examined using X-ray photoelectron spectroscopy (XPS). The evolution of the size and shape of the pre- and post-dissolution nanocrystals were studied using transmission electron microscopy (TEM), and the dissolution rate was calculated directly according to the size shrinking of galena nanocrystals. To assess the size effect, galena microcrystals (~ 3 μm) were synthesized and dissolved under similar conditions to the dispersed nanocrystals. The results showed that the nanocrystals dissolved at a surface area normalized rate of one order of magnitude faster than the microcrystals. In addition, dissolution rate is orientationdependent on a single nanocrystal. High-resolution TEM (HRTEM) images indicated the {111} and {110} faces dissolve faster than {100} faces on galena nanocrystals, rationalized by the average coordination number of ions on each of these faces. To assess the aggregation effect, dissolution experiments of aggregated galena nanocrystals were conducted using a wet-chemical method, and the results were compared with the rates of microcrystals and dispersed nanocrystals. These experiments showed that the rate of aggregated nanocrystals is in the same order of magnitude as the rate of microcrystals, but one order of magnitude smaller than that of dispersed nanocrystals. Finally, the effect of the close proximity between nanocrystals on dissolution was observed by HRTEM. Dissolution was greatly inhibited on nanocrystal surfaces that were closely adjacent (1-2nm, or less) to other nanocrystals, which is probably relevant to the slow dissolution of aggregated nanocrystals. The dissolution phenomena of galena nanocrystals observed in this study is likely important for understanding the environmental fate and behavior of nanoparticles in aquatic systems.
Ph. D.

Semiconductor nanostructures have attracted great interest owing to their unique physical properties and potential applications in nanoscale functional devices. The enhancement of the physical properties of semiconductor nanostructures and their performance in devices requires a deeper understanding of their fundamental microstructural properties. Thus this thesis is focused on the experimental and theoretical studies of the microstructural properties of two important semiconductor nanostructures: axial heterostructured silicon nanowires with varying doping and indium nitride colloidal nanoparticles. In this thesis, axial heterostructured silicon nanowires with varying doping were synthesized on an oxide-removed Si{111} substrate using a vapour-liquid-solid approach. Their fundamental microstructural properties, including the crystalline structure, wire growth direction and morphologies, were studied using various characterization techniques. It is found that a very small fraction of the silicon nanowires crystallize in a hexagonal (wurtzite) phase, which is thermodynamically unstable in bulk silicon under ambient conditions, while a large majority of the synthesized silicon nanowires exhibit the expected diamond cubic crystalline structure. About 75% of the diamond cubic silicon nanowires synthesized grow in a single <111> direction, while the rest contain growth-related kinks, where the nanowire switches to another direction during the growth. The ~109° silicon nanowire kinks are the most commonly observed, and the growth direction before and after such ~109° kink are both <111>. The sidewalls of silicon nanowires do not change abruptly at the ~109° kink, but exhibit an elbow-shaped structure. It is also found that the nanowire sidewalls exhibit periodic nanofaceting, which is strongly doping-dependent. The nanofaceting is found to occur during the enhanced sidewall growth that arises when the diborane dopant gas is introduced. A thermodynamic model predicting the dependence of nanofacet period on the wire diameter is developed. Another semiconductor nanostructure studied in this thesis is indium nitride colloidal nanoparticles, which were grown using a solution-phase chemical method. The formation of such indium nitride colloidal nanoparticles is confirmed by studying their compositions, crystalline structures and shape using various electron microscopy techniques. The size of the indium nitride colloidal nanoparticles was controlled by varying the time of solution-phase reactions. The most probable size of the colloidal nanoparticles increases and the size distribution broadens with the increase of reaction time. The crystalline structures of the indium nitride colloidal nanoparticles are found to be particle size dependent. The observed dependence of the band gap blueshift of the indium nitride colloidal nanoparticles on the reaction time (hence the particle size) is explained by the quantum-size effect.

The thesis reports on fabricating alternative solid phase extraction (SPE) sorbents and colorimetric probes based on electrospun nanofibers for alkylphenols (APs). Hydroxyl methylated styrene [poly(co-styrene-CH₃OH)] and 3-oxobutanoate styrene [poly(co-styrene-OCOCH₃COCH₃)] copolymers were synthesized and fabricated into sorbent materials by electro-spinning/spraying. The fabricated morphologies consisting of bead free fibers, beaded fibers and particles were evaluated as SPE sorbents using batch experiments. Electropun fibers proved to be better sorbents as they exhibited extraction efficiency that exceeded 95% compared to 60% for beaded fibers and 40% for particles. In view to reduce sample and solvent volumes, smooth fibers were packed into pipette tips as SPE devices that yielded quantitative recoveries of APs from spiked wastewater samples. Recoveries ranged from 70% to 125% with LOD of 0.008, 0.01 and 0.1 μg mL⁻¹ for 4-tert octylphenol (4-t-OP), 4-octylphenol (4-OP) and 4-nonylphenol (4-NP) respectively, when using high performance liquid chromatography-fluorescence detector (HPLC-FLD). Furthermore, amino functionalised polydiacetylene polymers (PDAs), citrate capped gold (AuNPs) and silver nanoparticles (AgNPs) were evaluated as colorimetric probes for visual detection of APs. In colloidal studies, AuNPs probe showed a colour change from wine red to green upon introduction of analyte. UV-vis spectroscopy revealed the shifting of the surface plasmon resonance (SPR) peak from 525 nm to 729 nm induced by aggregation of AuNPs. For AgNPs probe, a colour change was observed from yellowish green to brown. Transmission electron microscopy (TEM) studies showed growth of AgNPs. A presumed oxidation of the analyte, forming an absorbing compound at 279 nm in both AgNPs and PDAs probes was also observed. For PDAs probe the colour change was from purple to pink. Concentrations as low as 30 μg mL⁻¹ were detectable in all colloidal based probes. Further colorimetric investigations were conducted with electrospun AuNPs-nylon 6 fiber mat. A colour change from purplish red to navy blue at concentrations of 1000 μg mL⁻¹ was observed. Electrospun AgNPs –nylon 6 fiber mat did not show a distinct colour change. High resolution scanning electron microscopy (HRSEM) revealed the analyte inducing the assembly of AuNPs and AgNPs as they covered the surface of the nanofiber mat. Electrospun nanofibers are a platform for analysis and thus tuning their chemistry will lead to sensitive and selective methods

Ce mémoire porte sur la synthèse et la caractérisation de composés hexaferrites dans le système Ca-Fe-O. Ce travail a permis d’isoler quatre composés sous forme polycristalline ayant pour composition (Ca4Fe5O13)1-x(Fe9O12)1+x (x= 0,334 ; 0,301 et 0,128) et (Ca4Fe5O13)(Fe4O4). Leur structure cristalline a été déterminée à partir de données de diffraction électronique acquises en mode tomographie par précession des électrons et validée à l’aide de l’imagerie haute résolution (HREM et HAADF). Les différents modèles structuraux ont également été confirmés par diffraction des rayons X et des neutrons sur poudre. L’analyse fine des défauts d’intercroissance en imagerie HAADF a révélée des écarts significatifs de composition par rapport à la composition idéale (Ca4Fe5O13)(Fe9O12) à l’origine des trois polymorphes observés. En complément des études menées sur des cristaux de taille micrométrique dans les années 80, l’obtention d’échantillons polycristallins a rendu possible l’étude des propriétés physiques de ces composés. Malgré la complexité de ces structures et la présence de défauts étendus, la spectrométrie Mössbauer a mis en exergue un degré d’oxydation unique pour les atomes de fer (+3) et de confirmer les nombreuses transitions magnétiques initialement détectées par les mesures d’aimantation, ainsi que leur évolution en fonction de l’écart à la stœchiométrie x. Les composés ont également été caractérisés par des mesures de résistivité électrique et de coefficient Seebeck
This thesis reports on the synthesis and the characterization of hexaferrite compounds in the Ca-Fe-O system. This work has allowed to isolate four polycrystalline compounds presenting the chemical formula (Ca4Fe5O13)1-x(Fe9O12)1+x (x= 0.334; 0.301 and 0.128) and (Ca4Fe5O13)(Fe4O4). Their crystalline structure has been determined using the precession electron diffraction tomography and has been validated through high resolution imaging microscopy (HREM/HAADF). X-ray diffraction and neutron diffraction studies on polycrystalline samples have confirmed the different structural models. Fine analysis of intergrowth defects in HAADF imaging revealed significant deviations in composition with respect to the ideal composition (Ca4Fe5O13)(Fe9O12) at the origin of the three observed polymorphs. In addition to the studies on micron-sized crystals in the 80s, obtaining polycrystralline samples allowed the measurement of their physical properties. Despite the complexity of these structures and the presence of extensive defects, the Mössbauer spectroscopy has highlighted a unique oxidation degree of iron (+3) and confirmed as well the various magnetic transitions initially detected by magnetization measurements, as well as their evolution versus the x deviation value. Electrical resistivity and Seebeck coefficient measurements were performed on the samples

Orientador: Daniel Mario Ugarte
Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin
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Resumo: O estudo de fios metálicos de tamanho atômico (NF's) tem atraído grande interesse devido aos novos efeitos químicos e físicos neles observados. Entre esses novos fenômenos podemos destacar a quantização da condutância, efeito que deve ser fundamental no desenho dos novos nanodispositivos eletrônicos. NF's são usualmente gerados através de um procedimento simples de deformação mecânica: duas superfícies metálicas são colocadas em contato e depois afastadas. Nos últimos estágios do estiramento antes da ruptura, um fio de alguns átomos de diâmetro é gerado enquanto a condutância é medida. Os NF's têm sido estudados por diferentes grupos e, em diversas condições de temperatura (4 - 300 K) e pressão (de ambiente a UHV). Os resultados apresentam importantes variações e, têm gerado interpretações muito controversas. Devemos enfatizar que muitas interpretações têm sido feitas sem considerar que a deformação estrutural dos NF's deve depender fortemente da temperatura. Nesta tese estudamos as propriedades estruturais e eletrônicas NF's e, em particular analisamos a influência de efeitos térmicos no arranjo atômico, e sua manifestação na condutância. A estrutura dos NF's foi estudada por microscopia eletrônica de transmissão de alta resolução resolvidas no tempo. A condutância foi medida utilizando um sistema de quebra controlada de junções operado em ultra-alto-vácuo. Os experimentos foram realizados a ~150 e 300 K. Nossos resultados mostraram que, à temperatura ambiente os NF's são sempre cristalinos e livre de defeitos nas regiões mais finas; e deformam unicamente ao longo dos eixos cristalográficos [111], [100] e [110]. A baixa temperatura duas importantes diferenças foram observadas: (i) NF's de ouro apresentam defeitos, principalmente falhas de empilhamento e maclas. (ii) NF's alongados na direção [110] evoluem em cadeias atômicas, de comportamento mecânico muito diferente da temperatura ambiente, onde quebram abruptamente. Segundo as imagens de microscopia eletrônica, discordâncias parciais (Shockley) geram falhas de empilhamento; e cadeias de átomos suspensos são observados a ~150 e 300 K. Histogramas globais de condutância adquiridos a baixa temperatura revelaram: (i) aumento da intensidade do pico ~1 Go; (ii) leve diminuição da condutância devido ao aumento de defeitos; e (iii) a existência de uma sub-estrutura no pico ~2 Go, indicando a formação de dois arranjos atômicos estáveis. Resumidamente, nossos resultados mostram que a formação de defeitos é um evento freqüente a ~150 K. Provavelmente, mais defeitos na estrutura devem acontecer para temperaturas menores (4 - 10 K). Portanto, uma importante mudança na evolução da condutância durante a elongação de NF's deve ser esperado a baixa temperatura. Assim, a comparação direta de medidas de transporte de NF's realizadas a diferentes temperaturas pode levar a sérias discrepâncias. Esperamos ter contribuído a melhorar a compreensão e interpretação de experimentos de transporte realizados em diferentes condições, de modo tal, a gerar um modelo único e coerente que explique as propriedades físicas de NF's metálicos
Abstract: The study of atomic-size metal nanowires (NW's) is attracting a great interest due to occurrence a novel physical and chemical phenomena. Among these new phenomena, we can mention conductance quantization that will certainly influence the design of nanodevices. NW's are usually generated by means of a simple procedure: two metallic surfaces are put into contact and, then retracted. Just before rupture atomic-size NW's are formed, and the conductance is measured during the wire elongation. The interpretation of the results is troublesome, because conductance is measured during the modification of the atomic structure. This kind of experimental study has been performed by many research groups and, a quite wide range of temperatures (4 - 300 K) and vacuum condition have been used (from ambient to UHV). In fact, the results display significant variation, what has generated several controversial interpretations. It must be emphasized that many models have been derived without taking into account that the NW structural deformation should be significantly dependent on temperature. In this Thesis research work, we have studied the structural and electronic properties of gold NW's, in particular addressing how thermal effects influence the atomistic aspects of the NW deformation and how this influences the quantum conductance behavior. The structure of NW's has been studied by means of time-resolved high resolution transmission electron microscopy; the NWs transport measurements were based on a mechanically controlled break junction operated in ultra-high-vacuum. The experiments were performed at ~150 and 300 K. Our results have shown that at room temperature the atomic-size NW's. are always crystalline and free of defects, and the atomic structure is spontaneously deformed such that one of the [111]/[100]/[110] crystallographic axis becomes approximately parallel to the stretching direction. Low temperature observations revealed two important differences: i) Au NWs show extended defects, mainly stacking faults and, twinning; ii) NWs elongated along the [110] axis evolve to suspended atomic chains, while at room temperature they break abruptly. Partial Schockley dislocations generate the staking faults; suspended atoms chains are both observed at ~150 and 300 K. The global histograms of conductance at ~150 K showed that: i) a increase of the 1 Go peak intensity; ii) slight reduction of the NWs conductance due to scattering at defects and; iii) the peak at ~2 Go shows a sub structure, what is due to the occurrence of two different atomic arrangements with similar conductance. Briefly, our results revealed that the formation of defects is very frequent in NWs generated at ~150 K; the occurrence of more defects should be expected when NWs are studied at cryogenic temperatures. Then, a significant modification of the NW conductance behavior should be expected at low temperature. In these terms, the direct comparison of conductance measurements realized at different temperature regimes can lead to serious discrepancies. We hope that this work contribute to improve the interpretation and understanding of NW transport studies in order to develop a coherent and complete model that explain the physical properties of atomic-size metal NWs
Mestrado
Física da Matéria Condensada
Mestre em Física

Orientador: Daniel Mario Ugarte
Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin
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Resumo: Fios metálicos de tamanho atômico (NF's) apresentam novos efeitos químicos e físicos devido ao seu tamanho reduzido, onde pode-se destacar a condutância quântica. NF's são usualmente gerados através de um procedimento simples: duas superfícies metálicas são colocadas em contato e depois afastadas. Nos últimos estágios do estiramento antes da ruptura, um fio de alguns átomos de diâmetro é gerado enquanto a condutância é medida. Este tipo de abordagem apresenta um cenário que permite o estudo da condutância e do processo de deformação mecânica do NF. O objetivo desta tese consiste no estudo dos efeitos do arranjo atômico na condutância quântica e deformação mecânica de NF's gerados por alongamento. O arranjo atômico dos NF's foi estudado por microscopia eletrônica de transmissão de alta resolução resolvida no tempo. A condutância foi medida utilizando um sistema de quebra controlada de junções operado em ultra alto vácuo. Os experimentos foram realizados a ~ 150 K e 300 K. Neste trabalho de tese NF's de diversos tipos de morfologia, tamanho e composição química foram estudados. O estudo do efeito do arranjo atômico no processo de deformação mecânica foi realizado, principalmente, em nanotarugos (NR's) de ouro de ~ 1 nm de diâmetro. Foi verificado que a temperatura modifica drasticamente o comportamento mecânico dos NR's. Também, foi mostrado que o tamanho e a forma do NR sob deformação têm um papel determinante no processo de deformação mecânica. Além disso, foi realizado o estudo detalhado da formação de uma estrutura anômala que consiste em um nanotubo de seção transversal quadrada. Isto mostra a importância de considerar os efeitos de superfície no arranjo atômico de NF's sob deformação. O estudo da influência do arranjo atômico na deformação mecânica de NF's de ligas de ouro e cobre também foi realizada, onde foram observados eventos de segregação na escala atômica, devido a efeitos de superfície, e variações significativas no comportamento mecânico em relação a NF's puros. A origem na formação de distâncias anômalas em cadeias suspensas de ouro também foi analisada. Os resultados obtidos indicam que o carbono é o agente contaminante que induz a formação de distancias 3.2 Å. Finalmente, estudos dos efeitos do arranjo atômico na condutância de NF's de ouro e prata em função da temperatura foram realizados. Os resultados experimentais mostraram que a temperatura modifica significativamente o comportamento estrutural dos NF's formando defeitos estruturais a baixas temperaturas. As medidas de condutância a ~ 150 K também mostraram variações significativas. A partir da informação estrutural de microscopia, modelos geométricos foram estabelecidos para correlacionar a informação de condutância com o arranjo atômico através de cálculos teóricos de condutância
Abstract: Atomic-size metallic nanowires (NWs) display new physical and chemical effects, for example the quantum conductance. NWs can be usually generated by means of a simple experimental procedure: two metallic surfaces are put into contact and then they are retracted in a controlled way. During the last stages before the rupture, a wire containing a few atoms is created and its conductance can be measured simultaneously during the elongation process. This approach represents a scenario which allows us to study its conductance and mechanical properties. This thesis aims to study the thermal energy effects on NW's atomic arrangement and the corresponding influence on quantum conductance and mechanical deformation. The atomic arrangement was studied using time-resolved high resolution transmission electron microscopy. The conductance was measured using an experimental technique called mechanically controllable break junctions. Experiments were performed at ~ 150 K and 300 K. In this work were studied NW's that exhibit different morphologies, sizes and chemical composition. Firstly, the study of the atomic arrangement influence on the mechanical deformation was developed on one-nm wide gold nanorods (NRs). It was found that temperature induces drastic changes in the NR mechanical behavior. Moreover, it was shown that the NR size and shape play an essential role during the process of mechanical deformation. Second, the detailed study of the formation of anomalous silver square-cross section nanotube was performed. This revealed the strong influence of surface effects on atomic arrangement. Third, the study of atomistic aspects associated with mechanical deformation of gold-copper alloy NWs was also developed. Segregation events at atomic scale, induced by surface effects, and significant variations of the nanoalloy mechanical behavior were observed. Fourth, the analysis of the origin of formation of anomalous interatomic distances in suspended gold atom chains was performed. Our results indicate that carbon represents the most probable contaminant which induces the generation of anomalous distances (3.2 Å). Finally, the study of the atomic arrangement effects on conductance of gold and silver NWs as function of temperature was developed. Our experimental results revealed that thermal energy induces drastic changes of structural behavior, generating planar defects at low temperatures. Conductance measurements obtained at ~150 K also display significant variations. Considering structural information derived from microscopy observations, simple geometric models were defined and the conductance was calculated theoretically in order to correlate the gold and silver NW conductance and structural information
Doutorado
Física da Matéria Condensada
Doutor em Ciências

Zr cladding alloys have been used for many years as the first safety barrier layer of a nuclear reactor. However, the recent Fukushima accidents and industrial demands to increase the burnup of fuels have led to increasing interest in a detailed mechanistic understanding of aqueous corrosion and hydrogen pickup and the performance at high temperatures. As part of an international MUZIC-2 programme (Mechanistic Understanding of Zr Corrosion and Hydrogen pickup), I have used a range of advanced microscopy techniques to study the microstructure, the nanoscale chemistry and the porosity in a series of zirconium alloys at different stages of corrosion and hydrogen pickup. Samples from both autoclave and in-reactor conditions were available to compare, I have focussed on RXA (recrystallised 580°C) Zr-1.0Nb and annealed (720°C) Zr-1.0Nb alloys. A set of samples from different exposures times were chosen to represent early, pre-transition and post-transition samples in order to compare the microstructure and microchemistry of the oxides, the metal-oxide interface and the metal. (Scanning) Transmission Electron Microscopy ((S)TEM), Transmission Kikuchi Diffraction (TKD) and automated crystal orientation mapping with TEM (ASTAR mapping) were used to study the grain structure and phase distribution. Significant differences in grain morphology were observed between samples oxidised in the autoclave with different corrosion rates, with more uneven metal-oxide interface, more parallel cracks and less organised oxide grains in the fast corroding samples. Comparing with autoclave samples, the in-reactor samples have shorter, less well-aligned monoclinic grains and more tetragonal grains. The rapidly oxidising annealed Zr-1.0Nb alloy also have much higher tetragonal grain fraction comparing with the slow corrosion rate RXA Zr-1.0Nb alloys. Porosity in the oxide is predicted to have a major influence on the overall rate of corrosion and hydrogen pickup, and there is much more porosity in the annealed Zr-1.0Nb alloy than found in either the RXA alloy or the similar alloy exposed to neutron irradiation. A combination of Energy Dispersion X-ray (EDX) mapping in STEM and Electron Energy Loss Spectroscopy (EELS) analysis of second phase particles can reveal the main and the minor element distributions respectively. The annealed Zr-1.0Nb alloys have Î2-Zr SPPs with nano crystalline structure and much larger size. Although they does not relate with the higher density of cracks in the oxide, the large SPP size can connect together all the small cracks that are generated by the huge amount of tetragonal to monoclinic phase transformation during corrosion and provides pathway for corrosion and hydrogen pickup. Two kinds of SPPs are found in the RXA Zr-1.0Nb alloys, one is Î2-Nb and another one is Zr-Nb-Fe Laves phase. Neutron irradiation seems to have little effect on promoting fast oxidation or dissolution of Î2-Nb precipitates, but encourages dissolution of Fe from Laves phase precipitates. Electron Energy Loss Spectroscopy (EELS) analysis of the oxidation state of Nb in Î2-Nb SPPs in the oxide revealed the fully oxidised Nb⁵⁺ state in the SPPs deep into the oxide, but Nb²⁺ in the crystalline SPPs near the metal-oxide interface. EELS, TKD and ASTAR mapping have also revealed the presence of suboxide layers with the hexagonal ZrO structure predicted by ab initio modelling. The combined thickness of the ZrO suboxide and oxygen-saturated layers at the metal-oxide interface correlates well to the estimated instantaneous oxidation rate, suggesting that the presence of this oxygen- rich zone combining with the part where porosity is not interconnected is the protective oxide that is rate limiting in the key in the transport processes involved in corrosion and hydrogen pickup.

Au cours de ce travail, nous avons étudié deux types de défauts interfaciaux: domaines d’inversion (DI) et joints de grains (JG) dans des semiconducteurs de structure wurtzite (nitrures- d’éléments III, ZnO et l’hétérostructure ZnO/GaN) en utilisant le MET haute résolution et la modélisation ab initio. Dans le cas des DI, nos analyses théoriques montrent qu'une configuration tête-à-tête avec une séquence d'empilement à l’interface AaBbAa-AcCaA (H4) est la structure la plus stable dans les composés binaires (nitrures et ZnO wurtzites). De plus, un gaz d’électrons (2DEG) ou de trous (2DHG) à 2 dimensions est formé pour les configurations « tête-à-tête » ou queue-à-queue. A l’interface ZnO/GaN, l'observation de MET très haute résolution a confirmé la configuration H4 avec une interface -Zn-O-Ga-N. Notre modélisation théorique a mis en évidence la formation d’un gas de trous à 2 dimensions à cette hétérointerface. Nous avons aussi réalisé l’étude topologique, théorique et par MET des joints de grains de rotation autour de l’axe [0001] dans ces matériaux. Dans le GaN, nous avons trouvé que les plans du joint sont simplement formés par des dislocations de type a déjà connues pour le matériau en couche mince. Par contre, dans ZnO, la théorie topologique est complétement démontrée, et la dislocation [101 ̅0] est une brique de base dans la constitution des joints de grains avec des cycles d’atomes 6-8-4-
In this work, we investigated two kinds of interfacial defects: inversion domain boundaries (IDBs) and grain boundaries (GB) in wurtzite semiconductors (III-nitrides, ZnO and ZnO/GaN heterostructure) using high-resolution TEM and first-principle calculations. For IDBs, theoretical calculation indicated that a head-to-head IDB with an interfacial stacking sequence of AaBbAa-AcCaA (H4) is the most stable structure in wurtzite compounds. Moreover, 2-dimensional electron gas (2DEG) and 2-dimensional hole gas (2DHG) build up in head-to-head and tail-to-tail IDBs, respectively. Considering the IDB at the ZnO/GaN heterointerface, TEM observations unveiled the H4 configuration with a -Zn-O-Ga-N interface. Moreover the theoretical investigation also confirmed stability of this interface along with the corresponding formation of a 2DHG. A detailed topological, TEM and theoretical investigation of [0001] tilt Grain Boundaries (GBs) in wurtzite symmetry has also been carried out. In GaN, it is shown that the GBs are only made of separated a edge dislocations with 4, 5/7 and 8 atoms rings. For ZnO, a new structural unit: the [101 ̅0] edge dislocation made of connected 6-8-4-atom rings is reported for the first time, in agreement with an early theoretical report on dislocations and jogs in the wurtzite symmetry

Novel semiconductor nanostructures possess a range of notable properties that have the potential to be harnessed in the next generation of optical devices. Electron microscopy is uniquely suited to characterising the complex microstructure, the results of which may be related to the growth conditions and optical properties. This thesis investigates three such novel materials: (1) GaN/InGaN core/shell nanowires, (2) n-GaN/InGaN/p-GaN core/multi-shell microrods and (3) Zn₃N₂ nanoparticles, all of which were grown at Sharp Laboratories of Europe. GaN nanowires were grown by a Ni-catalysed VLS process and were characterised by various techniques before and after InGaN shells were deposited by MOCVD. The majority of the core wires were found to have the expected wurtzite structure and completely defect free – reflected in the strong strain-free photoluminescence peak –with a- and m- axis orientations identified with shadow imaging. A small component, <5%, were found to have the cubic zinc-blende phase and a high density of planar faults running the length of the wires. The deposited shells were highly polycrystalline, partially attributed to a layer of silicon at the core shell interface identified through FIB lift-out of cross section samples, and accordingly the PL was very broad likely due to recombination at defects and grain boundaries. A high throughput method of identifying the core size indirectly via the catalyst particle EDX signal is described which may be used to link the shell microstructure to core size in further studies. An n-GaN/InGaN/p-GaN shell structure was deposited by MOCVD on the side walls of microrods etched from c-axis GaN film on sapphire, which offers the possibility of achieving non-polar junctions without the issues due to non-uniformity found in nanowires. Threading dislocations within the core related to the initial growth on sapphire were shown to be confined to this region, therefore avoiding any harmful effect on the junction microstructure. The shell defect density showed a surprising relationship to core size with the smaller diameter rods having a high density of unusual 'flag' defects in the junction region whereas the larger diameter sample shells appeared largely defect free, suggesting the geometry of the etched core has an impact on the strain in the shell layers. The structure of unusual 'flag' defects in the m-plane junctions was characterised via diffraction contrast TEM, weak beam and atomic resolution ADF STEM and were shown to consist of a basal plane stacking faults meeting a perfect or partial dislocation loop on a pyramidal plane, the latter likely gliding in to resolve residual strain due to the fault formed during growth. Zn₃N₂ has the required bandgap energy to be utilised as a phosphor with the additional advantage over conventional materials of its constituent elements not being toxic or scarce. The first successful synthesis of Zn₃N₂ nanoparticles appropriate to this application was confirmed via SAD, EDX and HRTEM, with software developed to fit experimental polycrystalline diffraction patterns to simulated components suggesting a maximum Zn₃N₂ composition of ~30%. There was an apparent decrease in crystallinity with decreasing particle size evidenced in radial distribution function studies with the smallest particles appearing completely amorphous in 80kV HRTEM images. A rapid change in the particles under the electron beam was observed, characterised by growth of large grains of Zn₃N₂ and ZnO which increased with increasing acceleration voltage suggesting knock-on effects driving the change. PL data was consistent with the bandgap of Zn₃N₂ blue shifted from 1.1eV to around 1.8eV, confirming the potential of the material for application as a phosphor.

Les semi-conducteurs III-V à base d’azote et leurs alliages possèdent des propriétés remarquables et sont largement étudiés depuis les années 90. En comparaison à d'autres semi-conducteurs III-V, Les alliages de type ; AlGaN, InGaN et AlInN, ont leurs bandes interdites, directes, du lointain ultra-violet au proche infrarouge. Ainsi, ils sont appropriés pour de nombreuses applications dans des domaines tant civils que militaires tout en montrant de meilleures performances. De plus, l'alliage quaternaire AlGaInN montre des propriétés intéressantes car il peut être épitaxié soit avec un paramètre de maille ou une polarisation ou une bande interdite accordé au GaN. De plus, avec AlInN, ces deux alliages pourraient, à terme, remplacer les barrières conventionnelles AlGaN/GaN pour les applications aux Transistors à Haute Mobilité Électroniques (HEMT) grâce à des performances supérieures prouvées théoriquement.Dans ce travail, nous avons étudié les alliages AlInN et AlGaInN dont la croissance a été faite par épitaxie en phase vapeur d’organométalliques (MOVPE). Pour cela, la microscopie électronique en transmission a été notre principal outil de caractérisation. Le but était de caractériser les défauts et les mécanismes de croissance pendant la MOVPE. Dans cette optique, l'incorporation de gallium dans la barrière en raison de la géométrie de la chambre de croissance menant à un alliage quaternaire a été étudiée. Le contrôle du taux de gallium est réalisé soit par un processus de nettoyage entre les épitaxies soit par les conditions de croissance. Les défauts ont été ensuite différenciés comme extrinsèques et intrinsèques. En effet, les dislocations et les domaines d'inversion dans le GaN produisent des défauts extrinsèques, tandis que, les « pinholes » non connectés aux dislocations et les « hillocks » responsables de la rugosité de surface sont définis comme intrinsèques. Les origines des défauts intrinsèques dépendent fortement des propriétés physiques des composés parents binaires. Ces dégradations systématiques sont observées même lorsque les conditions de croissance sont optimisées et quand la composition du film mince est changée ou son épaisseur augmentée.Notre travail propose des mécanismes différents pour expliquer les processus de dégradation pour les différents défauts observés et constitue donc un pas en avant pour la réalisation de HEMT à base de AlInN et AlGaInN de meilleure qualité
Group III-Nitrides and their alloys exhibit outstanding properties and are being extensively investigated since the 90’s. In comparison to other III-V semiconductors, III-nitrides (AlGaN, InGaN, and AlInN) cover from deep ultraviolet (UV) to near infrared (IR) across the visible range of wavelengths. Thus, they are suitable for numerous applications both in civilian and military fields showing higher performances. Moreover, the quaternary alloy AlGaInN shows versatile properties as it can grow either lattice or polarization or bandgap matched to GaN. Alongside to AlInN, these two alloys are expected to replace conventional AlGaN/GaN High Electron Mobility Transistors (HEMT) barriers as higher performances have been theoretically demonstrated.In this work, we have studied AlInN and AlGaInN grown by metal organic vapor phase epitaxy (MOVPE) using mainly TEM. The aim was to characterize defects and the MOVPE growth alloying process. In this instance, the gallium incorporation in the barrier due to the geometry of the growth chamber leading to a quaternary alloy was studied. The control of the gallium content is achieved by a cleaning process between runs or by the growth condition. Defects were then differentiated as extrinsic and intrinsic. In this way, dislocations and inversion domains from the GaN buffer layer generate extrinsic defects, while, pinhole not connected to dislocations and individual hillocks responsible of surface roughening are termed as intrinsic. The origins of the latter defects depend strongly on the physical mismatches of the end-binary compound. These systematic degradations happen also with optimized growth conditions as soon as the nominal composition is changed and/or the thickness is increased.Our work proposes different mechanisms to explain defects generation processes which constitutes a forward step for higher quality HEMTs

Orientador: Mônica Alonso Cotta
Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin
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Resumo: Neste trabalho estudamos os mecanismos de crescimento durante a epitaxia por feixe químico de nanoestruturas III-V baseadas no sistema InAs/InP. Particularmente, foram estudados nanofios e ilhas de InAs sobre uma camada buffer InP(001) e nanofios de InAs sobre uma matriz de InGaAs/InP (com mesmo parâmetro de rede). Apresentaremos, nesta tese, as diferenças e similaridades destes sistemas quanto a condições de crescimento, distribuição de tamanho, forma e os efeitos de volume da camada de InGaAs sobre as nanoestruturas de InAs quando comparadas ao sistema InAs/InP. Nossa escolha do InGaAs/InP como camada buffer para a nucleação dos fios de InAs, foi feita porque facilitaria a utilização deste sistema em diversas aplicações, proporcionando maior flexibilidade no desenho dos dispositivos. Por outro lado, este material abre a possibilidade de controlar as características das nanoestruturas através das propriedades de bulk e superficiais da liga ternária InGaAs. Além disso, ligas ternárias podem exibir efeitos de volume que afetam suas propriedades superficiais. Estes fenômenos podem afetar a nucleação dos fios quânticos e por isso foram objeto de nosso estudo. Para isso utilizamos e correlacionamos medidas in situ de difração de elétrons de alta energia (RHEED), microscopia de força atômica (AFM) e eletrônica de transmissão (TEM), com os resultados obtidos por difração de raios X com incidência rasante (GIXD). Verificamos, deste modo, tanto a influência das condições de crescimento, como o comportamento da relaxação da energia elástica nas nanoestruturas. Com todos estes resultados mostramos como acontece a evolução da deformação nos nanofios e pontos quânticos de InAs/InP e como acontecem as transições de forma entre estes dois tipos de nanoestruturas, em função das condições de crescimento e tipo de superfície do substrato utilizado. Mostramos, também que a introdução de um composto ternário (InGaAs) entre o InAs e o InP não afeta significativamente a forma e tamanho das nanoestruturas quando comparadas ao caso InAs/InP. Em particular, a interdifusão gerada por variações locais da composição na camada buffer em nanofios de InAs pode ser minimizada através de mudanças nas condições de crescimento do InGaAs
Abstract: In this work we study the growth mechanisms of III-V nanostructures by chemical beam epitaxy (CBE) based on the InAs/InP materials system. Particularly, nanowires and nanodots of InAs on InP (001) and InAs nanowires on InGaAs/InP (lattice matched) buffer layers were studied. The differences and similarities of these systems are presented in this text, as a function of growth conditions, size distribution, as well as the bulk effects of the InGaAs layer on InAs nanostructures when compared to the InAs/InP system. Our choice of InGaAs/InP buffer layer for InAs nanowire nucleation was due to the possible use of this system in many applications, providing greater flexibility in device design. Furthermore, this material opens up the possibility of controlling nanostructures characteristics through bulk and surface properties of the InGaAs ternary alloy. In other hand, ternary alloys may present volume effects that affect their surface properties. These phenomena can affect quantum wires nucleation and thus became one of the subjects of our study. With these goals in mind, we have correlated in situ high-energy electrons diffraction (RHEED) measurements, atomic force microscopy (AFM) and transmission electron microscopy (TEM) images with the results obtained by grazing incidence X-ray diffraction (GIXD). We report here the influence of the growth conditions on nanostructure shape as well as the behavior of elastic energy relaxation within the nanostructures. Our results show how the evolution of deformation within InAs/InP nanowires and quantum dots occur and how the shape transition between these two types of nanostructures depend on the growth conditions and the substrate surface type used. We also show that the introduction of a ternary compound (InGaAs) between InAs and InP does not significantly affect the shape and size of nanostructures as compared to the InAs / InP case. In particular, the interdifusion generated in InAs nanowires by local variations in the buffer layer composition can be minimized through changes in InGaAs growth conditions
Doutorado
Estrutura de Líquidos e Sólidos; Cristalografia
Doutor em Ciências

Scanning transmission electron microscopy (STEM) has been widely used for characterization of materials; to identify micro- and nano-structures within a sample and to analyze crystal and defect structures. High-angle annular dark field (HAADF) STEM imaging using atomic number (Z) contrast has proven capable of resolving atomic structures with better than 2 A lateral resolution. In this work, the HAADF STEM imaging mode is used in combination with multislice simulations. This combination is applied to the investigation of the temperature dependence of the intensity collected by the HAADF detector in silicon, and to convergent beam electron diffraction (CBED) to measure the degree of chemical order in intermetallic nanoparticles. The experimental and simulation results on the high–angle scattering of 300 keV electrons in crystalline silicon provide a new contribution to the understanding of the temperature dependence of the HAADF intensity. In the case of 300 keV, the average high-angle scattered intensity slightly decreases as the temperature increases from 100 K to 300 K, and this is different from the temperature dependence at 100 keV and 200 keV where HAADF intensity increases with temperature, as had been previously reported by other workers. The L10 class of hard magnetic materials has attracted continuous attention as a candidate for high-density magnetic recording media, as this phase is known to have large magnetocrystalline anisotropy, with magnetocrystalline anisotropy constant, Ku, strongly dependent on the long-range chemical order parameter, S. A new method is developed to assess the degree of chemical order in small FePt L10 nanoparticles by implementing a CBED diffraction technique. Unexpectedly, the degree of order of individual particles is highly variable and not a simple function of particle size or sample composition. The particle-to-particle variability observed is an important new aspect to the understanding of phase transformations in nanoparticle systems.
Ph.D.
Department of Physics
Sciences
Physics

The two-dimensional material graphene possesses many impressive properties such asextraordinary carrier mobility, mechanical stiffness and optical transmittance. However,the properties of pristine graphene do not always complement the requirements of applications. Of particular interest, a band gap is needed for electronic logic devices. Recent research shows that using few-layer hexagonal boron nitride as a substrate for graphene-based electronic devices can open a band gap in graphene. Also, introducing impurities such as hydrogen atoms, transition metals or silicon atoms on or within graphene can control the electronic properties according to recent studies. Furthermore, ion irradiation is an alternative option to tailor the properties of graphene by introducing defects. In this thesis, pristine, impure or defective graphene and few-layer boron nitride were characterised by scanning transmission electron microscopy (STEM) and electron energy loss (EEL) spectroscopy. Through STEM and EEL spectroscopy, lattice structures and electronic properties of these two-dimensional materials could be investigated at the atomic scale. This thesis focuses on the frontier studies of theoretical and experimental EEL spectroscopy of graphene and few-layer boron nitride with impurities. In the EEL spectra of pristine graphene and boron nitride two prominent peaks were observed, which are attributed to the plasmon excitations of π- and π+σ-electrons. By introducing impurities such as hydrogen adatoms on graphene and substitutional oxygen and carbon atoms within single-layer boron nitride, our experimental and simulated EEL spectra show that their π-plasmon peaks are modified. The concentrations of these impurities were then evaluated via EEL spectra and atomic-resolution images. If other impurities, such as various transition metals and silicon atoms, are introduced on or within single-layer graphene, our simulated EEL spectra demonstrate that the geometry of these impurity clusters affects the π-plasmon peak in graphene and some impurities even enhance it. Finally, experiments on in-situ transmission electron microscopy and ex-situ STEM and Raman spectroscopy were conducted to investigate ion irradiated graphene. Many topological defects were, for the first time, observed in atomic-resolution STEM images of ion irradiated graphene. Simulated EEL spectra of defective graphene are also reported, which suggests that corrugations and dangling bonds in defects can modify out-of-plane EEL spectra and introduce intraband transitions, respectively.

Only a few methods are currently available for the measurement of sample thicknesses in Transmission Electron Microscopy (TEM). These methods, Convergent-Beam Electron Diffraction (CBED) and thickness mapping in Energy-Filtered TEM (EFTEM), are either elaborate or complex. In this present work, I have investigated and come up with a simple straight-forward method to measure the local thickness of a TEM sample with the atomic number (Z-contrast) imaging using High-Angle Annular Dark Field (HAADF) Scanning Transmission Electron Microscopy (STEM). HAADF STEM shows atomic number contrast for high scattering angles of the electrons, owing to predominant electron scattering at the potential of the nucleus similar to Rutherford scattering. The characterization of materials by STEM helps to identify microstructures and nanostructures within a sample and to analyze defects in samples. HAADF STEM imaging is capable of resolving atomic structures with better than 2 Å lateral resolution. However, HAADF STEM has so far not been systematically used to measure sample thicknesses. In Z-contrast imaging, it was known that the intensity of the electrons scattered to high angles increases with increase in the atomic number (Z) of the element/compound with increasing thickness of the sample based on the equation, I ~ t.Zα Where t, is the thickness and α, is a parameter between 1 and 2. This project was started with this simple approach, but the experimental results within the thesis show that the relation between the intensity and the atomic number is not well described by this equation. A more reliable parameter, σZ, the interaction coefficient of the material was calculated. Samples containing Ag2Al platelets in Al matrix were used for calibration purposes. Additional samples containing layers of known elements/compounds were obtained from TriQuint Semiconductors and from the Physics department of UCF to calculate σ for various elements/compounds. These experimental values were used to measure the local thicknesses in nanoparticles and also the total volume of the nanoparticles. This quantitative HAADF STEM analysis represents a new method, which can be added to the list of methods used for the purpose of measurement of the local thickness of a sample in the TEM. This method is especially useful for the thickness measurement of nanoparticles. The other two methods, CBED and thickness maps in EFTEM are strongly affected by the sample orientation and therefore not appropriate for the study of nanoparticle thicknesses, whereas orientation effects are negligible for the conditions used in this HAADF STEM analysis.
M.S.
Department of Mechanical, Materials and Aerospace Engineering;
Engineering and Computer Science
Materials Science & Engr MSMSE

Das Hochtemperaturverhalten beeinflusst viele verschiedene Prozesse von der Materialherstellung bis hin zur technologischen Anwendung. In-situ Transmissionselektronenmikroskopie (TEM) bietet die Möglichkeit, die atomaren Prozesse während struktureller Phasenübergänge direkt und in Realzeit zu beobachten. In dieser Arbeit wurde in-situ TEM angewendet, um die Reversibilität des Schmelz- und Kristallisationsprozesses, sowie das anisotropen Sublimationsverhaltens von Ge-Sb-Te (GST) Dünnschichten zu untersuchen. Die gezielte Probenpräparation für die erfolgreiche Beobachtung der Hochtemperatur-Phasenübergänge wird hervorgehoben. Die notwendige Einkapselung für die Beobachtung der Flüssigphase unter Vakuumbedingungen und die erforderliche sauberer Oberfläche für den Sublimationsprozess werden detailliert beschrieben. Außerdem wird die Elektronenenergieverlustspektroskopie eingesetzt um die lokale chemische Zusammensetzung vor und nach den Übergängen zu bestimmen. Die Untersuchung der Grenzflächenstruktur und Dynamik sowohl beim Phasenübergang fest-flüssig als auch flüssig-fest zeigt Unterschiede zwischen den beiden Vorgängen. Die trigonale Phase von GST weist beim Schmelzen eine teilweise geordnete Übergangszone an der fest-flüssig-Grenzfläche auf, während ein solcher Zwischenzustand bei der Erstarrung nicht entsteht. Außerdem läuft der Schmelzvorgang zeitlich linear ab, während die Kristallisation durch eine Wurzelabhängigkeit von der Zeit mit überlagerter Start-Stopp-Bewegung beschrieben werden kann. Der Einfluss der Substrat-Grenzfläche wird diskutiert und die Oberflächenenergie von GST bestimmt. Die anisotrope Dynamik führt beim Phasenübergang fest-gasförmig der kubischen Phase von GST zur Ausbildung stabiler {111} Facetten. Dies erfolgt über die Bildung von Kinken und Stufen auf stabilen Terrassen. Die Keimbildungsrate und die bevorzugten Keimbildungsorte der Kinken wurden identifiziert und stimmen mit den Voraussagen des Terrassen-Stufen-Kinken Modells überein.
High-temperature behavior influence many different processes ranging from material processing to device applications. In-situ transmission electron microscopy (TEM) provides the means for direct observation of atomic processes during structural phase transitions in real time. In this thesis, in-situ TEM is applied to investigate the reversibility of the melting and solidification processes as well as the anisotropic sublimation behavior of Ge-Sb-Te (GST) thin films. The purposeful sample preparation for the successful observation of the high-temperature phase transitions is emphasized. The required encapsulation for the observation of the liquid phase inside the vacuum conditions and the necessary clean surface for sublimation process are discussed in detail. Additionally electron energy-loss spectroscopy in the TEM is used to determine the local chemical composition before and after the phase transitions. The analysis of the interface structure and dynamic during the solid-to-liquid as well as the liquid-to-solid phase transition shows differences between both processes. The trigonal phase of GST exhibits a partially ordered transition zone at the solid-liquid interface during melting while such an intermediate state does not form during solidification. Additionally the melting process proceeds with linear dependence on time, whereas crystallization can be described as having a square-root time-dependency featuring a superimposed start-stop motion. The influence of the interface is addressed and the surface energies of GST are determined. The anisotropic dynamic of the solid-to-gas phase transition of the cubic GST phase leads to the formation of stable {111} facets. This happens via kink and step nucleation on stable terraces. The nucleation rates and the preferred kink nucleation sites are identified and are in accordance with the predictions of terrace-step-kink model.

Les semi-conducteurs nitrures (AlN, GaN, InN) focalisent une activité de recherche intense en raison de nombreuses applications comme les diodes électroluminescentes, les composants de puissance ou hyperfréquence. Dans cette recherche, nous avons abordé le travail sous deux angles: a) la conduction électrique dans les couches d'InN produites par croissance épitaxiale aux jets moléculaires assistée par plasma (PAMBE) et une recherche sur l'origine de la forte émission bleue dans les puits de quantiques d'InGaN/GaN. L'accumulation d'électron en surface dans les couches d'InN constitue une limitation importante pour la fabrication de composants. Au cours de ce travail, nous avons exploré l'utilisation des mesures de bruit de basse fréquence sur les couches d'InN et pu accéder à leur conductivité électrique en volume. L'étude des puits quantiques d'InGaN/GaN, obtenue par croissance épitaxiale aux jets moléculaires (MBE) ou épitaxie en phase vapeurs aux organométalliques (MOVPE) , a été effectuée par analyses de la microstructure par microscopie électronique en transmission (MET, HRTEM et STEM) en corrélation avec les propriétés optiques d'un grand nombre d'échantillons provenant de conditions de croissance différentes. Ce travail nous a permis d'acquérir une vision plus critique du rôle des conditions de fabrication et des paramètres comme la morphologie, les fluctuations de composition et la présence des défauts en V sur les explications actuellement avancées pour la forte efficacité d'émission dans les puits quantiques d' InGaN/GaN
The nitride semiconductors (AlN, GaN, InN) are subject to a large research effort due to their numerous applications, such as light emitting diodes, high power and high frequency components. Following the trend, the aim of this dissertation has been twofold: first, we have probed the bulk electrical conduction in InN layers, second, we investigated the origin of the high emission efficiency in InGaN/GaN Quantum Wells (QWs). The surface electron accumulation in InN layers is still an important limitation to device applications. W have explored this point using low frequency noise measurements on Plasma Assisted Molecular Beam Epitaxy (PAMBE) InN layers and we demonstrated that the bulk electrical conductivity of InN can be accessed. The investigation of quantum wells produced by molecular beam epitaxy (MBE) or matalorganic vapour phase epitaxy (MOVPE), has been carried out through microstructural analyses by transmission electron microscopy techniques(TEM, HRTEM, STEM) in correlation with optica properties on a large number of samples grown in different growth conditions. This experimental work has allowed us to obtain a critical view on the role of the growth conditions and such parameters as the well morphology, composition fluctuations, as well as the V shaped defects on the current explanations of high emission efficiency in InGaN/GaN QWs

Orientador: Daniel Mario Ugarte
Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin
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Resumo: A completa caracterização de novos fenômenos físicos e químicos em sistemas com dimensões nanométricas requer conhecimento detalhado: a) do arranjo atômico; b) de como os diferentes elementos químicos dos materiais se redistribuem nas interfaces/superfícies (rugosidade, interdifusão, etc.); e finalmente c) como os dois primeiros fatores modificam as propriedades eletrônicas do sistema. Neste contexto, o desenvolvimento de novas ferramentas com capacidades específicas e bem adaptadas à análise de nanossistemas é imprescindível; assim técnicas de caracterização e visualização com resolução espacial nanométrica devem ser consideradas uma simples necessidade rotineira. No trabalho de mestrado que apresentamos buscamos implementar técnicas que permitam caracterizar sistemas com resolução espacial atômica. Neste sentido, implementamos um método de análise quantitativa de imagens de microscopia eletrônica de transmissão de alta resolução, que permite uma medida objetiva de variações da composição química. Esta medida é feita com base nas variações da distribuição de intensidades em uma imagem e fornece um mapa da composição química na imagem. Este procedimento de interpretação quantitativa foi aplicado ao estudo da morfologia de interfaces de poços quânticos de InGaP/GaAs crescidos por CBE (Chemical Beam Epitaxy). Estimamos que o limite de detecção de variações de composição química para este sistema seja 15%. Nesta análise, medimos parâmetros estruturais microscópicos que permitem a comparação da morfologia de diferentes poços. Com isso, concluímos que a interface InGaP/GaAs é mais rugosa que a GaAs/InGaP. Além disso, através da caracterização de poços quânticos com diferentes camadas interfaciais, concluímos que a adição de GaP na interface InGaP/GaAs reduz a rugosidade. Os resultados de rugosidade foram comparados com medidas de fotoluminescência a 6K buscando estabelecer uma correlação direta entre a qualidade da interface e a largura de linha de emissão do poço quântico. Esta correlação não foi estabelecida. Mostramos que modelos estruturais simples são ineficazes e que modelos mais elaborados são necessários para interpretação da largura de linha de emissão de um poço quântico
Abstract: The complete characterization of new physical and chemical phenomena in systems of nanometric scale requires the detailed knowledge of: a) atomic structure; b) how chemical composition distribution is redefined by interfaces and surfaces (rougheness, interdiffusion, etc.); and c) how are the electronic properties of the system influenced by those two factors. In this sense, the development of new tools with specific capabilities and well adapted to the analysis of nanosystems is essential. Therefore, characterization and imaging techniques with nanometric spatial resolution must be considered routine necessities. In this graduate work we present, we sought to implement techniques which allow the characterization of small systems with atomic spatial resolution. In this sense, we implemented a method for the qualitative analysis of high resolutions transmission electron microscopy images, which makes possible the objective measurement of chemical composition changes. This measurement is based on changes of the distribution of intensities of an image and results in a map of the chemical composition of the image. This procedure for the quantitative interpretation was used in the study of the morphology of the interfaces of InGaP/GaAs quantum wells (QW) grown by Chemical Beam Epitaxy (CBE). We estimate that our detection limit for chemical variations in this system is 15 %. In this analysis, we measured microscopic structural parameters which allow the comparison of the morphology of different QW. With this data, we concluded that the InGaP/GaAs interface is rougher that the GaAs/InGaP one. Moreover, through the characterization of QWs with different interfacial layers we concluded that the addition of a thin GaP layer reduces roughness. Morphologial results were compared with 6 K photoluminescence experiments, seeking to establish a direct correlation between interface quality and quantum well emission line width. This correlation was not established. We showed that simple structural models are inefficient and that more elaborated models are need for the quantitative interpretation of quantum wells¿ emission line width
Mestrado
Física da Matéria Condensada
Mestre em Física

High-entropy alloys (HEAs) are alloys with multiple (usually ≥5) principal elements. HEAs are attracting increasing interest because of their promising mechanical properties and phase stability, which can be used for various applications, such as high-speed cutting tools, anticorrosive high-strength parts in chemical plants and deep-sea exploration due to the excellent mechanical properties at cryogenic temperatures. Thorough understanding of the structural evolution during deformation of HEAs is a prerequisite for understanding and further improving their superior mechanical properties, which is critical for future production of high-entropy alloys with desirable properties. Many HEAs form a stable single solid-solution phase. However, phase transformation could occur in some HEAs under certain circumstances, including high stress. Because stress concentration usually occurs at crack tips during deformation, it is interesting to check if any deformation-induced phase transformation would occur at crack tips during the deformation processes of HEAs. This thesis aims at using various transmission electron microscopy techniques to investigate the structural evolution of HEAs at room temperature. Research results showed surprisingly crystalline to amorphous phase transformation at crack tips in a FeCoCrNiMn HEA with an ultrafine-grained structure. Details of the phase transformation process was video recorded. The mechanism responsible for the phase transformation is discussed based on the observed microstructural evolution. Toughening introduced by nanobridging and the phase transformation is also briefly discussed.

Severe plastic deformation (SPD) techniques have been used to produce bulk nanostructured metallic materials with superior mechanical properties. Among all SPD techniques, high-pressure torsion (HPT) has been proven the most effective in achieving nanostructures. Therefore, extensive efforts have been devoted to studying HPT processing and its effect on the microstructures and properties of materials. This thesis project is part of an ongoing effort to study HPT and, at the same time, expand our knowledge of SPD. In Chapter 1, extensive literature reviews of SPD, HPT and deformation mechanisms under SPD are provided, and three major issues regarding SPD processing materials are identified. Chapter 2 discusses the choice of a duplex stainless steel as a model material to be processed by HPT. A brief review of duplex stainless steel is given in this chapter. After the choice of material, a review of all the materials characterisation techniques used in this thesis project is presented, as well as details of all the relevant experimental procedures. Chapter 3 describes the plan-views and cross-sectional views of shear strain imposed on austenite/ferrite duplex stainless steel discs at different stages of HPT processing. The effect of the shear strain was correlated to the hardness evolution of the discs. Chapter 4 presents the systematic investigation that was carried out into the microstructure and hardness evolutions of the duplex stainless steel. It was found that the microstructures of both phases of the duplex stainless steel evolved concurrently under continuously increasing shear strain imposed by HPT. Chapter 5 presents a detailed investigation of both cold rolling and HPT caused significant grain refinements to a duplex stainless steel. It was found that while conventional cold rolling of a face-centred cubic structure produces a microstructure with a high density of extended dislocations, increasing the applied stress using HPT gives a nanotwinned coarse-grained structure. In Chapter 6, major conclusions are drawn from this thesis project. Some possible future work is proposed as an extension of the project.

Correlative light and electron microscopy (CLEM) is a powerful approach to investigate the molecular ultrastructure of labeled cell compartments. However, quantitative CLEM studies are rare, mainly due to small sample sizes and the sensitivity of fluorescent proteins to strong fixatives and contrasting reagents for EM. Here, we show that fusion of a self-labeling protein to insulin allows for the quantification of age-distinct insulin granule pools in pancreatic beta cells by a combination of super resolution and transmission electron microscopy on Tokuyasu cryosections. In contrast to fluorescent proteins like GFP organic dyes covalently bound to self-labeling proteins retain their fluorescence also in epoxy resin following high pressure freezing and freeze substitution, or remarkably even after strong chemical fixation. This enables for the assessment of age-defined granule morphology and degradation. Finally, we demonstrate that this CLEM protocol is highly versatile, being suitable for single and dual fluorescent labeling and detection of different proteins with optimal ultrastructure preservation and contrast.

The pursuit of high quality, large area graphene has been a major research focus of contemporary materials science research, in the wake of the discovery of the multitude of exceptional properties exhibited by the material. The DPhil project was undertaken with the objective of developing an understanding of the growth of large graphene sheets by chemical vapour deposition (CVD), and also in the subsequent characterisation of their material properties. By conducting atmospheric pressure CVD growth at high methane flow rates, it was found that few-layered graphene (FLG) could be deposited on a copper catalyst. It is demonstrated that the self-limiting property of a copper catalyst is not universal to all deposition conditions, and shown that FLG grows in a terrace-like configuration. In depth transmission electron microscopy (TEM) studies were carried out on FLG. By selective image reconstruction from the inverse power spectrum of the TEM images, it was possible to elucidate the inter-grain connectivity of few-layer graphenes. It was determined that there were two possible inter-grain configurations possible; specifically an overlap of graphene layers or a discrete atomic bonding edge. The perturbation of the few-layer structure when subject to an out of plane distortion was found to incur a shift in the conventional AB-Bernal stacking of FLG. By utilising the aberration corrected TEM (AC-TEM) at Oxford it was possible to resolve atomic detail in CVD synthesised monolayer films, including atomic bond rotations and vacancies. The use of a high current density at low accelerating voltage (80 kV) was demonstrated to allow for the controlled defect creation in graphene sheets. This permitted the creation of monovacancies and iron doped vacancy complexes suitable for further study. The behaviour of these two defect types under electron beam irradiation was subsequently studied.

Le nanotube de carbone double parois représente le cas idéal pour étudier la nature de l'interaction entre parois des tubes multiparois. En partant d'échantillons dispersés de DWNTs synthétisés par CVD, nous avons pu, grâce à la microscopie électronique en transmission haute résolution (METHR), établir une procédure robuste de détermination structurale des configurations. Il apparaît alors que certaines configurations structurales sont privilégiées alors que d'autres sont interdites, mettant en évidence les effets du couplage interparoi. À partir de simulations Monte Carlo réalisées sur des DWNTs de configurations interdites, nous avons montré que le tube interne modifie sa structure pour atteindre une stabilité énergétique, ce que nous avons pu rapprocher d'observations expérimentales. Pour étudier les propriétés électroniques des DWNTs observés expérimentalement, nous avons corrélé les techniques de METHR et d'absorption optique pour analyser des populations différenciées de tubes en nombre de parois, diamètre et nature électronique, grâce à la technique DGU (Ultracentrifugation de Gradient de Densité). À l'issue de trois tris successifs, nous avons pu isoler une population de tubes double parois pure à 95% et dont les tubes extérieurs sont de nature semi-conducteur à 90\%
Double-walled carbon nanotube represents the ideal case to investigate the nature of the interaction between walls of multiwall tubes. Starting with scattered samples of DWNTs synthesized by CVD, we have established a robust procedure for structure determination of configurations based on high resolution electron microscopy transmission (HRTEM). After achieving a statistical study, it appears that some structural configurations have been favored while others are completely forbidden, highlighting the effects of inter-wall coupling. To go beyond, we have performed Monte Carlo simulations at atomic scale on DWNTs with forbidden configurations. As a result, we have shown that the inner tube changes its structure to achieve energy stability, in good agreement with experimental observations. To study the electronic properties of DWNTs observed experimentally, we correlated HRTEM and optical absorption techniques for analyzing differentiated tubes populations by number of walls, diameter and electronic nature, thanks to the technical DGU (Density Gradient Ultracentrifugation ). After three successive sorting, a pure population of double-walled tubes to 95% and of which 90% of the outer tubes are semiconductor has been isolated

Silicon technologyhas been seekingfor a monolithic solution for a chip where data processing and data communication is performed in the CMOS part and the photonic component, respectively. Traditionally, silicon has been widely considered for electronic applications but not for photonic applications due to its indirect bandgap nature. However, band structure engineering and manipulation through alloying Si with Ge and Sn has opened new possibilities. Theoretical calculations show that it is possible to achieve direct transitions from Ge ifit is alloyed with Sn. Therefore, a GeSn system is a choice to get a direct bandgap. Extending to ternary GeSnSi and quaternary GeSnSiCstructures grown on Si wafers not only makes the bandgap engineering possible but also allowsgrowing lattice matched systems with different strain and bandgaps located in the infrared region. Different heterostructures can be designed and fabricated for detecting lightas photonic sensing oremitting the light as lasers. Alloying not only makes engineering possible but it also induces strain which plays an important role for electronic applications. Theoretical and experimental works show that tensile strain could increase the mobility, which is promising for electronic devices where high mobility channels for high performance MOSFETs is needed to speed up the switching rate. On the other hand, high n-doping in tensile strains in p-i-n structures makesΓ band transitions most probable which is promising for detection and emission of the light. As another benefit of tensile strain, the direct bandgap part shrinks faster than the indirect one if the strain amount is increased. To get both electronic and photonic applications of GeSn-based structures, two heterostructures (Ge/GeSn(Si)/GeSi/Ge/Si and Ge/GeSn/Si systems), including relaxed and compressive strained layers used to produce tensile strained layers, were designed in this thesis. The low temperature growth is of key importance in this work because the synthesis of GeSn-based hetrostructures on Si wafers requires low thermal conditions due tothe large lattice mismatch which makes them metastable. RPCVD was used to synthesize theseheterostructures because not only it offers a low temperature growth but also because it is compatible with CMOS technology. For utilization of these structures in devices, n-type and p-type doping of relaxed and compressive strained layers were developed. HRRLMs, HRTEM, RBS, SIMS, and FPP techniques were employed to evaluatestrain, quality, Sn content and composition profile of the heterostructures. The application of GeSn-based heterostructures is not restricted to electronics and photonics. Another application investigated in this work is photovoltaics. In competition with Si-based solar cells, which have, or areexpected to have,high stability and efficiency, thirdgeneration solar cells offer the use of low cost materials and production and can therefore be an alternative for future light energy conversion technology. Particularly, quantum dot sensitized solar cells are associated with favorable properties such as high extrinsic coefficients, size dependent bandgaps and multiple exciton generation and with a theoretical efficiencyof 44%. In this work, two categories of QDs, Cd-free and Cd-based QDs were employed as sensitizers in quantum dot sensitized solar cells (QDSSCs). Cd-based QDs have attracted large interest due to high quantum yield,however, toxicityremains still totheir disadvantage. Mn doping as a bandgap engineering tool for Cd-based type IIZnSe/CdS QDs wasemployed to boostthe solar cell efficiency. Theoretical and experimental investigations show that compared to single coreQDSSCs,typeII core-shells offer higher electron-hole separation due to efficient band alignment where the photogenerated electrons and holes are located in the conduction band of the shell and valence band of the core, respectively. This electron-hole separation suppresses recombination and by carefully designing the band alignment in the deviceit can increase the electron injection and consequently the power conversion efficiency of the device. Considering eco-friendly and commercialization aspects, three different “green” colloidal nanostructures having special band alignments, which are compatible for sensitized solar cells, were designed and fabricated by the hot injection method. Cu2GeS3-InP QDs not only can harvest light energy up to the infraredregion but can also be usedastypeII QDs. ZnS-coating was employed as a strategy to passivate the surface of InP QDs from interaction with air and electrolyte. In addition, ZnS-coating and hybrid passivation was applied for CuInS2QDs to eliminate surface traps.

QC 20151125

Etude des mecanismes d'interaction joint de grain dislocations lors de la deformation du bicristal, mettant en evidence la dissociation des dislocations entrant dans le joint, leur perte d'identite et l'interaction entre eux des residus. Determination des structures des dislocations residuelles. Apparition de precipites lors du recuit du bicristal deforme