Transmissio electron microscopy

Aquest treball vol oferir una visió general de la microscòpia electrònica de transmissió, partint d’un repàs històric des dels inicis de la tècnica els anys 30 del segle xx fins arribar als darrers avenços i la seva rellevància en el context de la recerca actual. Es posa l’èmfasi en intentar explicar els diferents mecanismes físics que permeten obtenir informació estructural i composicional de l’objecte observat a partir de la seva interacció amb un feix d’electrons accelerats. This works aims at giving a general overview of transmission electron microscopy, from the beginnings of the technique in the 1930s to the latest technological advances and their relevance to current research. The focus is an attempt at explaining the different physical mechanisms that allow obtaining structural and compositional information from the observed object by studying its interaction with a beam of accelerated electrons

Advanced TEM imaging tools for materials science

[eng] Being able to directly relate the final properties with the intimate structure provides a unique insight into the functionality of materials and devices, especially when compared to the necessarily statistical nature of the information that can be retrieved by macroscopic measurements. In particular, the scale reduction associated with the Nanoscience and Nanotechnology revolution demands characterization tools capable of reaching an unprecedented resolution, in a wide range of fields, not only for standard quality control, but in order to understand the properties of matter at the nanoscale. Going from bigger to smaller devices, but also from elemental building blocks (even atoms) to bigger assemblies, basic properties and device functionalities meet. With its ability to provide different kinds of information at a very high spatial resolution, state-of-the-art TEM and related techniques are in the core of this multidisciplinary and rapidly growing field. The first major topic is related to the assessment of local atomic ordering/disordering phenomena in functional materials. A series of rare earth niobates (RE3NbO7) will be studied in order to understand the microstructural origin of their proton conduction properties, that make them excellent candidates to be used as electrode materials in solid oxide fuel cells. Also, single crystals of the tetragonal tungsten bronze (TTB) Sr0.33Ba0.66Nb2O6 (SBN-67) will be studied by different TEM techniques in order to assess the possible short range structural and/or chemical disorder. These features are thought to be responsible for the observed macroscopic uniaxial polarization vector of the material as well as its relaxor properties. A second major topic of interest will be the phenomena taking place at interfaces. This includes the characterization of a set of LaNiO3 perovskite thin films grown on different substrates (LAO, LSAT, STO, YAO). The effect of the substrate-induced compressive/tensile strain, given by lattice mismatch, on the structure of the films will be assessed and related to the observed electric transport properties. The interfaces in a GaN/InAlN multilayered system designed as a Bragg reflector for laser cavities applications will be investigated in order to account for a lower than expected reflectivity of the devices. The presence of structural defects and the detection of intergrowth of wurtzite and zinc blende phases of GaN in thin films will be addressed. Also regarding interfaces and strain conditions, the characterization of the free surface of Nb2O5 nanorods, as a key point for their humidity sensing properties. Expanding on this, the strain state of Nb2O5 when grown on SnO2 nanowires will also be studied. The coupling of the sensing capabilities of Nb2O5 with the electrical transport properties of SnO2 is of particular interest for functional sensing devices. Therefore, defects at the interface and strain state are of capital interest in order to understand the band structure alignment of the system. Interfaces in lower dimensionality systems will also be studied, as in the case of Ag@Fe3O4 dimers for applications in magnetoplasmonics. The epitaxial quality, strain, and the possible chemical diffusion through the contact surface of the two phases of the dimer are key aspects in order to properly tailor their optical properties. The last major topic is the mapping of magnetic fields at the nanoscale. The magnetic configurations of different geometric arrangements of magnetite Fe3O4 nanocubes will be studied. This characterization is aimed at obtaining enhanced responses in magnetic hyperthermia treatments for cancer. Given the strong interrelationship between the problems under study, the chapter structure follows the dimensionality of the systems under study (3D, 2D, 1D and 0D systems).[cat] La reducció en l'escala espacial associada a la revolució de la Nanociència i la Nanotecnologia fa necessari comptar amb una sèrie d'eines capaces d'assolir una resolució sense precedents en una gran varietat d'àress, ja no tan sols com a control de qualitat, sinó per tal d'entendre les propietats de la matèria a la nanoescala. La correlació de la configuració estructural, la composició química i les distribucions de càrrega amb les propietats funcionals és imprescindible pel disseny de nous dispositius, tant des de la perspectiva 'top down' (reducció de les dimensions dels dispositius) com de la perspectiva 'bottom up' (fabricació d'estructures complexes a partir de blocs més petits, fins i tot àtoms). La capacitat de la Microscòpia Electrònica de Transmissió (TEM) de proporcionar diferents tipus d'informació amb una alta resolució espacial, situa les tècniques avançades de TEM com a peça clau en el desenvolupament d'aquest camp multidisciplinari i creixent. L'objectiu principal d'aquesta tesi ha estat l'aplicació de tècniques quantitatives d'imatge TEM per la resolució de problemes en ciència dels materials. La tesi cobreix un espectre ampli pel que fa al tipus de materials estudiats i els seus camps d'aplicació. El Capítol 1 presenta una introducció general a la teoria de formació d'imatge aplicada a la microscopia TEM. S'hi exposen els diferents fenòmens d'interacció electró-matèria que són responsables dels diferents tipus de contrast que es poden trobar a les imatges TEM. El Capítol 2 presenta les tècniques experimentals que es faran servir en la caracterització dels materials, en concret la simulació d'imatges d'alta resolució (HRTEM), l'holografia electrònica i l'anàlisi de la fase geomètrica (GPA). S'hi pot trobar una descripció del marc teòric i dels fonaments experimentals, juntament amb un resum dels resultats més recents en aquests camps. Els resultats experimentals s'agrupen en els capítols posteriors segons la dimensionalitat dels sistemes estudiats. En ordre decreixent de dimensionalitat s'hi inclouen: materials massius (3D), capes primes (2D), nanofils (1D) i nanopartícules (1D)

Mapping the magnetic coupling of self-assembled Fe3O4 nanocubes by electron holography

The nanoscale magnetic configuration of self-assembled groups of magnetite 40 nm cubic nanoparticles has been investigated by means of electron holography in the transmission electron microscope (TEM). The arrangement of the cubes in the form of chains driven by the alignment of their dipoles of single nanocubes is assessed by the measured in-plane magnetic induction maps, in good agreement with theoretical calculations

Electron energy-loss spectroscopic tomography of FexCo(3-x)O4 impregnated Co3O4 mesoporous particles: unraveling the chemical information in three dimensions

Electron energy-loss spectroscopy-spectrum image (EELS-SI) tomography is a powerful tool to investigate the three dimensional chemical configuration in nanostructures. Here, we demonstrate, for the first time, the possibility to characterize the spatial distribution of Fe and Co cations in a complex FexCo(3-x)O4/Co3O4 ordered mesoporous system. This hybrid material is relevant because of the ferrimagnetic/antiferromagnetic coupling and high surface area. We unambiguously prove that the EELS-SI tomography shows a sufficiently high resolution to simultaneously unravel the pore structure and the chemical signal

Quantitative parameters for the examination of InGaN QW multilayers by low-loss EELS

We present a detailed examination of a multiple InxGa1−xN quantum well (QW) structure for optoelectronic applications. The characterization is carried out using scanning transmission electron microscopy (STEM), combining high-angle annular dark field (HAADF) imaging and electron energy loss spectroscopy (EELS). Fluctuations in the QW thickness and composition are observed in atomic resolution images. The impact of these small changes on the electronic properties of the semiconductor material is measured through spatially localized low-loss EELS, obtaining band gap and plasmon energy values. Because of the small size of the InGaN QW layers additional effects hinder the analysis. Hence, additional parameters were explored, which can be assessed using the same EELS data and give further information. For instance, plasmon width was studied using a model-based fit approach to the plasmon peak; observing a broadening of this peak can be related to the chemical and structural inhomogeneity in the InGaN QW layers. Additionally, Kramers-Kronig analysis (KKA) was used to calculate the complex dielectric function (CDF) from the EELS spectrum images (SIs). After this analysis, the electron effective mass and the sample absolute thickness were obtained, and an alternative method for the assessment of plasmon energy was demonstrated. Also after KKA, the normalization of the energy-loss spectrum allows us to analyze the Ga 3d transition, which provides additional chemical information at great spatial resolution. Each one of these methods is presented in this work together with a critical discussion of their advantages and drawbacks

Insight into the compositional and structural nano features of AlN/GaN DBRs by EELS-HAADF

: III-V nitride ~AlGa!N distributed Bragg reflector devices are characterized by combined high-angle annular dark-field ~HAADF! and electron energy loss spectroscopy ~EELS! in the scanning transmission electron microscope. Besides the complete structural characterization of the AlN and GaN layers, the formation of AlGaN transient layers is revealed using Vegard law on profiles of the position of the bulk plasmon peak maximum. This result is confirmed by comparison of experimental and simulated HAADF intensities. In addition, we present an advantageous method for the characterization of nano-feature structures using low-loss EELS spectrum image ~EEL-SI! analysis. Information from the materials in the sample is extracted from these EEL-SI at high spatial resolution.The log-ratio formula is used to calculate the relative thickness, related to the electron inelastic mean free path. Fitting of the bulk plasmon is performed using a damped plasmon model ~DPM! equation. The maximum of this peak is related to the chemical composition variation using the previous Vegard law analysis. In addition, within the context of the DPM, information regarding the structural properties of the material can be obtained from the lifetime of the oscillation. Three anomalous segregation regions are characterized, revealing formation of metallic Al islands

Green electroluminescence of Al/Tb/Al/SiO2 devices fabricated by electron beam evaporation

In this work, the fabrication and the structural, optical and electrical properties of Al-Tb/SiO2 nanomultilayers have been studied. The nanomultilayers were deposited by means of electron beam evaporation on top of p-type Si substrates. Optical characterization shows a narrow and strong emission in the green spectral range, indicating the optical activation of Tb3+ ions. The electrical characteriza-tion revealed conduction limited by the electrode, although trapped-assisted mechanisms can also contribute to transport. The electroluminescence analysis revealed also emission from Tb3+ ions, yielded promising results to in-clude this material in future optoelectronics applications as integrated emitting devices

Independent Tuning of Optical Transparency Window and Electrical Properties of Epitaxial SrVO3 Thin Films by Substrate Mismatch

Transparent metallic oxides are pivotal materials in information technology, photovoltaics, or even in architecture. They display the rare combination of metallicity and transparency in the visible range because of weak interband photon absorption and weak screening of free carriers to impinging light. However, the workhorse of current technology, indium tin oxide (ITO), is facing severe limitations and alternative approaches are needed. AMO perovskites, M being a nd transition metal, and A an alkaline earth, have a genuine metallic character and, in contrast to conventional metals, the electron-electron correlations within the nd band enhance the carriers effective mass (m*) and bring the transparency window limit (marked by the plasma frequency, ω*) down to the infrared. Here, it is shown that epitaxial strain and carrier concentration allow fine tuning of optical properties (ω*) of SrVO films by modulating m* due to strain-induced selective symmetry breaking of 3d-t(xy, yz, xz) orbitals. Interestingly, the DC electrical properties can be varied by a large extent depending on growth conditions whereas the optical transparency window in the visible is basically preserved. These observations suggest that the harsh conditions required to grow optimal SrVO films may not be a bottleneck for their future application

Effect of Si3N4-mediated inversion layer on the electroluminescence properties of silicon nanocrystal superlattices

The achievement of an efficient all-Si electrically-pumped light emitter is a major milestone in present optoelectronics still to be fulfilled. Silicon nanocrystals (Si NCs) are an attractive material which, by means of the quantum confinement effect, allow attaining engineered bandgap visible emission from Si by controlling the NC size. In this work, SiO2-embedded Si NCs are employed as an active layer within a light-emitting device structure. It is demonstrated that the use of an additional thin Si3N4 interlayer within the metal-insulator-semiconductor device design induces an enhanced minority carrier injection from the substrate, which in turn increases the efficiency of sequential carrier injection under pulsed electrical excitation. This results in a substantial increase in the electroluminescence efficiency of the device. Here, the effect of this Si3N4 interlayer on the structural, optical, electrical, and electro-optical properties of a Si NC-based light emitter is reported, and the physics underlying these results is discussed

Structural and optical properties of Al-Tb/SiO2 multilayers fabricated by electron beam evaporation

Light emitting Al-Tb/SiO2 nanomultilayers (NMLs) for optoelectronic applications have been produced and characterized. The active layers were deposited by electron beam evaporation onto crystalline silicon substrates, by alternatively evaporating nanometric layers of Al, Tb, and SiO2. After deposition, all samples were submitted to an annealing treatment for 1 h in N2 atmosphere at different temperatures, ranging from 700 to 1100 °C. Transmission electron microscopy confirmed the NML structure quality, and by complementing the measurements with electron energy-loss spectroscopy, the chemical composition of the multilayers was determined at the nanoscopic level. The average composition was also measured by X-ray photoelectron spectroscopy (XPS), revealing that samples containing Al are highly oxidized. Photoluminescence experiments exhibit narrow emission lines ascribed to Tb3+ ions in all samples (both as-deposited and annealed ones), together with a broadband related to SiO2 defects. The Tb-related emission intensity in the sample annealed at 1100 °C is more than one order of magnitude higher than identical samples without Al. These effects have been ascribed to the higher matrix quality, less SiO2 defects emitting, and a better Tb3+ configuration in the SiO2 matrix thanks to the higher oxygen content favored by the incorporation of Al atoms, as revealed by XPS experiments