61. Structural, morphological and chemical properties of metal/topological insulator interfacesKatja Ferfolja, 2021, doktorska disertacija Opis: 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. Najdeno v: osebi Ključne besede: topological insulators, topological surface states, Bi2Se3, thin films, Ag, Ti, Pt, morphology, interfaces, solid-state reaction, metal selenides, reactivity, stability, electron microscopy, dissertations Objavljeno: 09.06.2021; Ogledov: 2117; Prenosov: 150
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63. Improved photocatalytic activity of SnO[sub]2-TiO[sub]2 nanocomposite thin films prepared by low-temperature sol-gel methodUrška Lavrenčič Štangar, Giovanni Palmisano, Matjaž Valant, Mattia Fanetti, Samar Al Jitan, Iztok Arčon, Ksenija Maver, 2021, izvirni znanstveni članek Opis: The objective of this research was to investigate how the photocatalytic activity of pure TiO2 can be improved by
SnO2 modification. Different molar ratios of tin to titanium were prepared. The correlation between tin concentration
and structural properties was investigated to explain the mechanism of photocatalytic efficiency and
to optimize the synthesis conditions to obtain enhanced activity of the SnO2-modified TiO2 photocatalysts under
UV-irradiation. The SnO2-modified TiO2 photocatalysts were prepared by a low-temperature sol-gel method
based on organic tin and titanium precursors. The precursors underwent sol-gel reactions separately to form
SnO2-TiO2 sol. The sol-gels were deposited on a glass substrate by a dip-coating technique and dried at 150 ◦C to
obtain the photocatalysts in the form of a thin film. To test the thermal stability of the material, an additional set
of photocatalysts was prepared by calcining the dried samples in air at 500 ◦C. The photocatalytic activity of the
samples was determined by measuring the degradation rate of an azo dye. An increase of up to 30% in the
photocatalytic activity of the air-dried samples was obtained when the TiO2 was modified with the SnO2 in a
concentration range of 0.1–1 mol.%. At higher SnO2 loadings, the photocatalytic activity of the photocatalyst
was reduced compared to the unmodified TiO2. The calcined samples showed an overall reduced photocatalytic
activity compared to the air-dried samples. Various characterization techniques (UV-Vis, XRD, N2-physisorption,
TEM, EDX, SEM, XAS and photoelectrochemical characterization) were used to explain the mechanism for the
enhanced and hindered photocatalytic performances of the SnO2-modified TiO2 photocatalysts. The results
showed that the nanocrystalline cassiterite SnO2 is attached to the TiO2 nanocrystallites through the Sn-O-Ti
bonds. In this way, the coupling of two semiconductors, SnO2 and TiO2, was demonstrated. Compared to
single-phase photocatalysts, the coupling of semiconductors has a beneficial effect on the separation of charge
carriers, which prolongs their lifetime for accessibility to participate in the redox reactions. The maximum increase
in activity of the thin films was achieved in the low concentration range (0.1–1 mol.%), which means that
an optimal ratio and contact of the two phases is achieved for the given physical parameters such as particle size,
shape and specific surface area of the catalyst. Najdeno v: osebi Ključne besede: photocatalytic activity, Sn-modified TiO2, low-temperature, thin films, XAS analysis Objavljeno: 05.07.2021; Ogledov: 1280; Prenosov: 0
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64. Room-temperature solid-state reaction at the Ag/Bi[sub]2Se[sub]3 interfaceMatjaž Valant, Iuliia Mikulska, Sandra Gardonio, Katja Ferfolja, Mattia Fanetti, 2017, objavljeni povzetek znanstvenega prispevka na konferenci Opis: Topological insulators (TI) are materials that, while having a forbidden bandgap in bulk, are conductors at their surface due to presence of surface-localized electronic states crossing the band gap. [1] TIs are possible because of a time reversal symmetry and spin-orbit coupling, which invert bulk band states in their energy positions and make the bulk band structure non trivial. Consequently, the topological surface states (TSS) emerge on the surface of these materials. Unlike ordinary surface states, TSS cannot be destroyed by contamination or defects on the surface. Additionally, TSS are also spin polarized, which means that when applying current to TI, the current will have a well defined direction of the electron spins.
The topological insulators - a relatively new class of materials - are being widely studied not only from fundamental aspects, but also from their applicative perspectives. It has been predicted that TIs could be used in fields of spintronics, electronics and catalysis. [2,3] Interestingly, only a few studies about metal/TI interfaces have been reported. This is surprising since integration of TI in the applications will often necessitate an interface with the metal, therefore, detailed knowledge on chemistry and electrical conditions at the interface will be required.
In this contribution results on research on the chemistry of the Ag/Bi2Se interface will be presented, in particularonthesolid-statereactionbetweennanoparticles.IthasbeenobservedthatwhenBi2Se3 andAgare put in contact a chemical reaction occurs at the interface, producing AgBiSe2 and Ag2Se. Interestingly, the reaction already occurs at room temperature, which is not usual for solid-state reactions. In literature this reaction has not been properly described. The authors rather described it as intercalation of the silver atoms, which we have disproved and showed that recrystallization of the new phases occurs. [3,4,5] The results will alsobediscussedincomparisonwithothertwoAg/Bi2Se3 systemsunderourinvestigation:i)Agdepositedby achemicalrouteonBi2Se3 nanoflakesandii)AgdepositedfromavapourphaseinvacuumonaBi2Se3.single crystal Najdeno v: osebi Ključne besede: topological insulators, topological surface states, solid-state reaction, TI/metal interface Objavljeno: 20.08.2021; Ogledov: 1119; Prenosov: 0
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65. Chemical (in)stability of interfaces between different metals and Bi[sub]2Se[sub]3 topological insulatorSandra Gardonio, Matjaž Valant, Katja Ferfolja, Mattia Fanetti, 2018, objavljeni povzetek znanstvenega prispevka na konferenci Opis: 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. Najdeno v: osebi Ključne besede: thermal lens spectrometry, photothermal beam deflection spectroscopy, dye remediation, photothermal technique, photocatalytic degradation, reactive blue 19, TiO2 modification Objavljeno: 20.08.2021; Ogledov: 1353; Prenosov: 0
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66. Chemical (in)stability of an interface between metals and Bi[sub]2Se[sub]3 topological insulatorSandra Gardonio, Matjaž Valant, Katja Ferfolja, Mattia Fanetti, 2019, objavljeni povzetek znanstvenega prispevka na konferenci Opis: Our research is dedicated to a study of an interface between a Bi2Se3 topological insulator (TI) and various metals due to the essential need for providing a metal contact for devices. The main objective is to characterize structural and chemical properties at the interface, where the electronic properties of the TI can be affected. The structure of the interface and processes happening at it are investigated by microscopy (SEM, TEM, STM) and spectroscopy techniques (EDX, XPS).
The research started with the noble metals: Ag, Au and Pt. A good stability was observed for Au and Pt, whereas Ag reacted with Bi2Se3 already at room temperature, producing Ag2Se and AgBiSe2 phase. Interface stability was also checked at high temperature and results showed that the Au coating undergoes a coalescence process starting from 100 °C whereas the interface with Pt does not show any change at least up to 350 °C.
At present we are focused on the interface with Ti, a metal which is regularly used as an adhesive layer in electrical contacts. At low coverage (<30 nm) Ti forms an extremely flat film, smoother than Au, Ag or Pt. At higher coverage the film undergoes buckle delamination, likely induced by stress release. The observed morphology indicates that a chemical interaction leads to the growth of the initial smooth Ti epitaxial film. Se interdiffusion and formation of interfacial TixSey phase is envisaged, as suggested from preliminary TEM observations of the interface structure.
The presented results show the importance of the processes happening at the interface, especially solid-state chemical reactions, which are often neglected in the study of systems with metal/TI interfaces. Such instability has to be taken into account since the produced phases can affect transport properties of the material, increase a contact resistance or affect functionality of devices. Najdeno v: osebi Ključne besede: Bi2Se3, interface, topological insulator, chemical instability Objavljeno: 20.08.2021; Ogledov: 1058; Prenosov: 7
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67. Silica coated Bi[sub]2Se[sub]3 topological insulator nanoplateletsMatjaž Valant, Mattia Fanetti, Sandra Gardonio, Slavko Kralj, Sebastjan Nemec, Blaž Belec, Nina Kostevšek, 2021, objavljeni povzetek znanstvenega prispevka na konferenci Najdeno v: osebi Ključne besede: topological insulator, optical properties, topological surface states, silica-coated Objavljeno: 27.09.2021; Ogledov: 1190; Prenosov: 0
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68. Tracking the reversibility of Ni redox states in Ni(OH)[sub]2 oxygen evolution electrocatalyst at high current densityAndraž Mavrič, Mattia Fanetti, Matjaž Valant, Chunhua Cui, 2021, objavljeni povzetek znanstvenega prispevka na konferenci Najdeno v: osebi Ključne besede: oxygen evolution reaction, spectroelectrochemistry, nickel hydroxide, stability, amorphization Objavljeno: 29.11.2021; Ogledov: 914; Prenosov: 0
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69. Enhancing the mechanical properties of biodegradable Mg alloys processed by warm HPT and thermal treatmentsAndrea Mizelli-Ojdanic, Jelena Horky, Bernhard Mingler, Mattia Fanetti, Sandra Gardonio, Matjaž Valant, Bartosz Sulkowski, Erhard Schafler, Dmytro Orlov, Michael J. Zehetbauer, 2021, izvirni znanstveni članek Najdeno v: osebi Ključne besede: severe plastic deformation, SPD, precipitates, vacancy agglomerates, magnesium alloys, biodegradability Objavljeno: 03.12.2021; Ogledov: 837; Prenosov: 36
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70. The role of substrate on thermal evolution of Ag/TiO[sub]2 nanogranular thin filmsVincenzo Balzano, Emanuele Cavaliere, Mattia Fanetti, Sandra Gardonio, Luca Gavioli, 2021, izvirni znanstveni članek Najdeno v: osebi Ključne besede: nanogranular composite thin film, substrate driven properties, morphology, optical absorption, Ag/TiO2 Objavljeno: 03.12.2021; Ogledov: 866; Prenosov: 66
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