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Structural, morphological and chemical properties of metal/topological insulator interfaces
Katja Ferfolja, 2021, doctoral dissertation

Abstract: Topological insulators (TIs) represent a new state of matter that possess a different band structure than regular insulators or conductors. They are characterized with a band gap in the bulk and conductive topological states on the surface, which are spin polarized and robust toward contamination or deformation of the surface. Since the intriguing properties of the TIs are localized at the surface, it is important to obtain knowledge of the possible phenomena happening at the interface between TIs and other materials. This is especially true in the case of metals, due to the fact that such interfaces will be present in the majority of foreseen TI applications. The presented study combines microscopy and spectroscopy techniques for characterization of morphology, stability and chemical interaction at the interface between TI and metals deposited by means of physical vapor deposition. Our research is based on the interface of Bi2Se3 topological insulator with Ag, Ti and Pt – metals that can be encountered in devices or applications predicted to utilize the special properties of topological insulators. STM and SEM imaging of Ag/Bi2Se3 interface showed that Ag atoms arrange on the surface in the form of islands, whereas significantly bigger agglomerates are found at the surface steps. The interface was found to be unstable in time and resulted in the absorption of the metal into the crystal at room temperature. Evidences of a chemical reaction at the Ag/Bi2Se3 interface are presented, showing that new phases (Ag2Se, AgBiSe2 and metallic Bi) are formed. Deposition of Ti on Bi2Se3 resulted in different morphologies depending on the film thickness. At a very low coverage (<1 Å) islands are formed. However, the islands growth is hindered before the completion of a full layer due to the occurrence of a chemical reaction. No surface features could be detected by SEM for Ti coverage up to 20 nm. In contrary, when Ti thickness reached 40 nm, compressive stress triggered buckling of the deposited film. XPS analysis revealed that a redox solid-state reaction occurs at the Ti/Bi2Se3 interface at room temperature forming titanium selenides and metallic Bi. The reaction has significant kinetics even at cryogenic temperature of 130 K. Pt forms a homogenous film over the whole substrate surface, which is stable in time at room temperature. Although the interface of Pt with Bi2Se3 was found to be i less reactive compared to Ag and Ti, an interfacial phase formed upon annealing to ∼90 °C was detected by TEM cross section experiment. A model for prediction of interfacial reactions between a metal and Bi2Se3 based on the standard reduction potential of the metals and Gibbs free energy for a model reaction is presented. Based on these two values the reaction can be expected to result in the formation of binary and/or ternary selenides and Bi. Presented work shows on the importance of metal/topological insulator interfaces characterization taking into account the possibility of a chemical reaction with all of its consequences. Results should be considered for future theoretical and applicative studies involving such interfaces as well as for the possible engineering of 2D TI heterostructures.
Found in: ključnih besedah
Keywords: topological insulators, topological surface states, Bi2Se3, thin films, Ag, Ti, Pt, morphology, interfaces, solid-state reaction, metal selenides, reactivity, stability, electron microscopy, dissertations
Published: 09.06.2021; Views: 1232; Downloads: 82
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Sn-modified TiO[sub]2 thin film photocatalysts prepared by low-temperature sol-gel processing
Ksenija Maver, 2021, doctoral dissertation

Abstract: Due to many advantageous physiochemical properties, titanium dioxide (TiO2) is the most widely used photocatalyst in numerous applications, such as wastewater treatment and air purification, self-cleaning surfaces and energy conversion (H2 generation). However, one of its disadvantages is the high electron-hole recombination rate, and coupling with other semiconductors is one of the strategies to improve it. The objective of this dissertation was to investigate how the photocatalytic activity of pure TiO2 can be improved by tin modification and to explain the mechanism of increased or hindered photoactivity in correlation with the structural properties of the modified TiO2 photocatalysts. A new low-temperature sol-gel synthesis route was developed to prepare Sn- or SnO2-modified TiO2 photocatalysts. In both cases, organic tin and titanium precursors were used. Tin in the form of Sn cations was used to prepare Sn-modified TiO2. In this case, the precursors went through the sol-gel reaction together to form a Sn-TiO2 sol. In the case of SnO2 modification, the SnO2 sol was prepared separately and additionally mixed with the TiO2 sol to form a TiO2/SnO2 bicomponent semiconductor system. Different molar ratios of tin to titanium were prepared to investigate the correlation between the tin concentration and the photocatalytic properties of the photocatalysts in the form of thin films. The results were used to optimize the synthesis conditions to obtain an improved activity of the modified TiO2 photocatalysts under UV-irradiation. The photocatalytic activity of the thin films was determined by measuring the degradation rate of an azo dye. An increase of up to 40 % in the photocatalytic activity of the dried samples (at 150 °C) was achieved when the TiO2 was modified with the Sn or SnO2 in a concentration range of 0.1 to 1 mol.%. At higher Sn or SnO2 loadings and after calcination of the samples at 500 °C, the photocatalytic activity of the photocatalyst was reduced compared to the unmodified TiO2. Different characterization techniques (UV-Vis, XRD, nitrogen physisorption, TEM, SEM and XAS) were employed to clarify the mechanism responsible for the enhanced and hindered photocatalytic performance of the Sn- and SnO2-modified TiO2 photocatalysts. The results showed that a nanocrystalline structure is already achieved in the samples by the low-temperature film treatment (drying at 150 °C) and that the photocatalytic efficiency is mainly influenced by the crystalline phase composition: anatase/rutile in the case of Sn-modified and TiO2/SnO2 in the case of SnO2-modified TiO2. The crystal size and specific surface area differ insignificantly between the equally thermally treated samples and partly explain the differences in photoefficiency of the calcined samples compared to the dried samples. The structural study at the atomic level, using the Sn K-edge EXAFS, revealed that Sn cations act as nucleation sites for the anatase to rutile transformation in the Sn-modified TiO2 photocatalysts, while in the SnO2-modified TiO2 samples the nanocrystalline cassiterite SnO2 is bound to the TiO2 nanocrystallites via the Sn-O-Ti bond. In both cases, the advantage of coupling the two semiconductors was achieved by separating the charge carriers and thus prolonging their lifetime for accessibility to participate in the redox reactions. The maximum activity enhancement was achieved in the low concentration range (0.1–1 mol.%), which means that an optimal ratio and contact of the two phases are obtained for the given physical parameters, such as particle size, shape and specific surface area of the catalyst.
Found in: ključnih besedah
Keywords: Sn-modified TiO2, SnO2-modified TiO2, low-temperature sol-gel, thin films, photocatalytic activity, anatase/rutile system, Sn K-edge EXAFS, dissertations
Published: 09.06.2021; Views: 1370; Downloads: 73
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Reading between the lines
Greta Mazzaggio, 2018, doctoral dissertation

Abstract: This thesis' aim is to add some pieces to the complex puzzle on the mechanism behind the comprehension of conversational implicatures. To do so, in a series of experiment we manipulated both the type of implicatures (scalar vs. ad-hoc) and the population under investigation (typical vs. atypical; children vs. adults).
Found in: ključnih besedah
Keywords: scalar implicatures, experimental pragmatics, autism developmental disorder, bilingualism, typically developing children, theory of mind, dissertations
Published: 20.09.2021; Views: 662; Downloads: 0
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Spectroscopic investigation of oxygen vacancies in CeO[sub]2
Thanveer Thajudheen, 2021, doctoral dissertation

Abstract: A unique material, ceria (CeO2), which is widely applied in automobile exhaust catalysts, is functional due to presence of defects in its crystal structure. Furthermore, the structural defects dictate electrical and chemical properties of ceria. The creation of intrinsic oxygen vacancies in ceria is responsible for oxygen-ion conductivity in solid oxide fuel cells. This unfolds the keen interest in ceria defects. Using the analytical technique cathodoluminescence spectroscopy (CLS) we can characterize ceria for its band gap and the defect states within the band gap. Since CLS has a high spatial resolution, high sensitivity to low concentration of defects and ability to obtain depth resolved information it is an obvious technique of choice. The first part of the thesis is an introduction to the topic and description of the experimental techniques. Importance of ceria as a multifaceted material finding applications in areas spanning from energy production and conversion to biomedical applications is detailed. CLS as a tool to understand defect-related optical properties and advancement in the CL detection systems are discussed. To study the relationship between local structure and its impact on CL emission spectra, an X-ray absorption spectroscopy techniques were used. The X-ray absorption near edge structure (XANES) and the Extended x-ray absorption fine structure (EXAFS) techniques are summarized. The second part discusses CL emission from ceria. Initially, CL emission from reduced ceria and its dependence on oxygen vacancy concentration are presented. The origin of emission was attributed to different configurations of the oxygen vacancies and polarons. The recent F center description in ceria was adopted here. The intriguing observation of CL emission quenching as a function of oxygen vacancy concentration was explained on the basis of a relative change in population of F centers in ceria. This demonstrated the relevance of local structure for the CL emission in ceria. In order to have a better understanding of the system, La-doped ceria was proposed as a model system. A precise control over the stoichiometry helped to achieve a desired oxygen vacancy concentration. The CL emission behavior, as observed in reduced ceria, was replicated in the case of La-doped ceria and the analysis revealed that F+ centers favor CL emission whereas F0 centers are disadvantageous. The local structure investigation using EXAFS analysis of both cations Ce and La (K-Edge) showed distortion from the fluorite symmetry and corroborated the F center description of oxygen vacancies in ceria. Our results provide an experimental evidence for F center description involving oxygen vacancies and polarons.
Found in: ključnih besedah
Keywords: ceria, cathodoluminescence spectroscopy, local structure distortion, EXAFS analysis, La doped ceria, luminescence quenching, F centers, dissertations
Published: 25.11.2021; Views: 642; Downloads: 25
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Application of machine learning techniques for cosmic ray event classification and implementation of a real-time ultra-high energy photon search with the surface detector of the Pierre Auger Observatory
Lukas Zehrer, 2021, doctoral dissertation

Abstract: Despite their discovery already more than a century ago, Cosmic Rays (CRs) still did not divulge all their properties yet. Theories about the origin of ultra-high energy (UHE, > 10^18 eV) CRs predict accompanying primary photons. The existence of UHE photons can be investigated with the world’s largest ground-based experiment for detection of CR-induced extensive air showers (EAS), the Pierre Auger Observatory, which offers an unprecedented exposure to rare UHE cosmic particles. The discovery of photons in the UHE regime would open a new observational window to the Universe, improve our understanding of the origin of CRs, and potentially uncloak new physics beyond the standard model. The novelty of the presented work is the development of a "real-time" photon candidate event stream to a global network of observatories, the Astrophysical Multimessenger Observatory Network (AMON). The stream classifies CR events observed by the Auger surface detector (SD) array as regards their probability to be photon nominees, by feeding to advanced machine learning (ML) methods observational air shower parameters of individual CR events combined in a multivariate analysis (MVA). The described straightforward classification procedure further increases the Pierre Auger Observatory’s endeavour to contribute to the global effort of multi-messenger (MM) studies of the highest energy astrophysical phenomena, by supplying AMON partner observatories the possibility to follow-up detected UHE events, live or in their archival data.
Found in: ključnih besedah
Keywords: astroparticle physics, ultra-high energy cosmic rays, ultra-high energy photons, extensive air showers, Pierre Auger Observatory, multi-messenger, AMON, machine learning, multivariate analysis, dissertations
Published: 27.10.2021; Views: 766; Downloads: 28
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Galactic dark matter distribution and its implications for experimental searches
Mihael Petač, 2019, doctoral dissertation

Found in: ključnih besedah
Summary of found: ...dwarf spheroidal galaxies, spiral galaxies, Milky Way, dissertations, direct detection, indirect detection...
Keywords: dark matter, phase-space distribution function, dwarf spheroidal galaxies, spiral galaxies, Milky Way, dissertations, direct detection, indirect detection
Published: 01.10.2021; Views: 629; Downloads: 0
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Features of narrative language in fluent aphasia
Sara Andreetta, 2014, doctoral dissertation

Found in: ključnih besedah
Keywords: aphasia, discourse analysis, language evaluation, dissertations
Published: 18.11.2021; Views: 555; Downloads: 0
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Novel analytical approaches in quality and safety control in production of fermented beverages
Jelena Topić, 2022, doctoral dissertation

Abstract: The exploitation of microorganisms for fermentation goes back centuries. Two types of fermentation are usually used in the winemaking process – alcoholic fermentation and malolactic fermentation. Nowadays, inoculated fermentations with the use of starter cultures are commonly used in order to produce wine with more consistent quality. However, wines can lack in flavour complexity, so scientists and the industry are constantly looking for new and improved starters that can be adapted to different types of wine. In this work we focused on the development and implementation of novel analytical methods for wine quality control. In the course of method development native yeasts and lactic acid bacteria isolates were characterized for wine starter properties. We focused on the determination of biologically active compounds that determine wine quality and safety. Yeasts can influence wine colour through their adsorption capacity and synthesis of stable colour pigments pyranoanthocyanins and lactic acid bacteria can produce biogenic amines which can have adverse detrimental health effects on sensitive consumers when they are present in wines.
Found in: ključnih besedah
Keywords: Saccharomyces yeasts, non-Saccharomyces yeasts, pyranoanthocyanins, thermal-lens spectrometry, lactic acid bacteria, biogenic amines, thin layer chromatography, dissertations
Published: 18.02.2022; Views: 383; Downloads: 12
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