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Abstract: We report the crystallisation of three forms of copper(II) isonicotinate-N-oxide complex and their phase interconversion via solvent-mediated crystal to crystal transformation. The different forms of copper complex have been isolated and characterised by single crystal X-ray diffraction. Gel phase crystallisation performed in hydrogels, low molecular weight gels and gels of tailored gelator showed crystal habit modification. Crystallisation in aqueous ethanol resulted in concomitant formation of blue (form-I) and green (form-II/IV) crystals while use of low molecular weight gel results in selective crystallization of the blue form-I under identical conditions. Comparison of gel phase and the solution state crystallisation in various solvent compositions reveals that the blue form-I is the thermodynamically stable form under ambient conditions.
Found in: osebi
Keywords: copper(II) complex, gel phase crystallisation, crystal habit modification, isonicotinate-N-oxide, X-ray diffraction
Published: 08.11.2018; Views: 2650; Downloads: 0
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Found in: osebi
Keywords: metal contact, topological insulator contact, growth mode, electronic properties, chemical properties, photoemission spectroscopy, microscopy
Published: 05.12.2018; Views: 2779; Downloads: 0
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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: osebi
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: 2075; Downloads: 147
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Abstract: In recent years a classification of materials based on their topological order gained popularity due to the discovery of materials with special topological character – topological insulators (TI). TI have different band structure than regular insulators or conductors. They are characterized by a band gap in the bulk of the material, but at the surface they possess conductive topological surface states (TSS) that cross the Fermi level. TSS are a consequence of the non-trivial bulk band structure and have properties that differ from ordinary surface states. They are robust toward contamination and deformation of the surface. Additionally, they are also spin polarized, which means that an electron spin is locked to a crystal momentum and, therefore, backscattering during transport is suppressed [1]. Due to their specific properties the TI could be used in fields of spintronics, quantum computing and catalysis [2]. The investigation of the interfaces between metals and the TI has not been given much attention even though its characterization is interesting from fundamental physics and applicative point of view. (In)stability of the contacts with metal electrodes, in a form of a chemical reaction or diffusion, has to be taken into account since it can affect the transport properties of the material or increase the contact resistance. Our research is dedicated to the study of the metal/TI interfaces, in particular to Bi2Se3 with deposited metals that are relevant for electrical contacts (Au, Ag, Pt, Cr, Ti). The thermal and chemical stability of the interfaces are of fundamental importance for understanding the contact behavior, therefore, we focused our work to the characterization of these properties. The metal/TI interfaces are investigated mainly with an electron microscopy (SEM, TEM, STM), EDX microanalysis and XRD. Our previous studies showed that the interface between Bi2Se3, and Ag deposited either chemically or from a vapor phase, results in the formation of new phases already at room temperature [3]. On the contrary, Au deposited on the Bi2Se3 surface shows very limited reactivity and is stable at RT, but diffusion and coalescence of the metal are observed starting from 100 °C [4]. In this contribution, we will present further characterization on the evolution of the Ag/Bi2Se3 and Au/Bi2Se3 interfaces, show preliminary results about recently investigated systems (Pt/Bi2Se3, Ti/Bi2Se3) and compare the thermal and chemical stability of the systems under investigation.
Found in: osebi
Keywords: thermal lens spectrometry, photothermal beam deflection spectroscopy, dye remediation, photothermal technique, photocatalytic degradation, reactive blue 19, TiO2 modification
Published: 20.08.2021; Views: 1342; Downloads: 0
Fulltext (100,42 KB)

Abstract: Binary bismuth chalcogenides, Bi2Se3 and Bi2Te3, have been extensively studied as reference topological insulators (TIs). These materials are bulk insulators with topological surface states (TSS) crossing the Fermi level. In contrast to conventional surface states of metals, the TSS are extremely robust against local modifications at the surface, such as adsorbed adatoms, localized defects or changes in the surface termination. This aspect makes the TIs attractive for applications in spintronics, plasmonics, quantum computing and catalysis. A theoretical model of charge transport by the TI surface states predicts that the TSS survive, provided that bonding at the metal/TI interface is weak. Ab-initio calculations have been done to understand the electronic properties of Au, Ni, Pt, Pd and graphene layers in a contact with Bi2Se3. These calculations showed that for Au and graphene the spin-momentum locking of TSS is maintained at the interface. In another theoretical study, Ag and Au thin layers on Bi2Se3 have been predicted to show a large Rashba splitting and a high spin polarization of the Ag quantum wells, providing a great potential for development of the spintronic devices. Finally, the calculations have foreseen that the presence of the robust TSS affects the adsorption properties of metals (Au bi-layer and clusters of Au, Ag, Cu, Pt, and Pd) supported on TI, in some cases resulting in the enhancement of the catalytic processes. Despite the fundamental importance of the metal/TI interfaces and a number of theoretical studies predicting exotic interfacial phenomena, the experimental knowledge about the metals on the TI surfaces is surprisingly limited, especially concerning combined study of morphology, growth mode, electronic and chemical properties. In order to exploit the predicted physical properties of such systems, it is especially important to extend the study above the diluted coverage regime and to understand what is the growth morphology of the metal on the TI surface, to what extent the metal overlayer interacts with the TI substrate, how the TSS change with the presence of the metal overlayer and what is the reactivity of the system at the different stages of the overlayer growth. Within this frame, we present a comprehensive surface sensitive study, of Au and Ag on Bi2Se3 by means of ARPES, XPS, SEM, LEED and XRD. The obtained results allow us to discuss the relation between electronic and physical properties at two of the most important model metal/TI interfaces
Found in: osebi
Keywords: topological insulator, electronic properties, synchrotron radiation
Published: 27.06.2019; Views: 2495; Downloads: 0
Fulltext (5,72 MB)