Studium interakce atomů kovů s metastabilními rekonstrukcemi povrchu Si(111) pomocí STM

Metódou STM je skúmaný proces rekonštrukcie povrchu Si(111) po naparení tália a jeho následnej desorbcii. Je nameraná závislosť pokrytia povrchu táliom na teplote a z určenej závislosti sú vyvodené vhodné podmienky pre tvorbu povrchu s čo najvyšším zastúpením metastabilných rekonštrukcií (hlavne (5x5) a (9x9)). Na takto vytvorený povrch sú následne naparené rôzne množstvá Al a je pozorovaná možnosť vzniku magických klastrov a iných zaujímavých štruktúr. Sú navrhnuté možné štruktúrne modely pre magické klastre na rekonštrukcii (5x5). V rámci práce je popísaná aparatúra použitá pri meraniach, sú popísané jednotlivé meracie postupy a fyzikálne princípy spojené s prevádzkou STM.Process of reconstruction of Si(111) surface after vapor deposition of thallium and subsequent desorption is studied by STM. Dependency of surface coverage on temperature is determined and this dependency is afterwards used for determination of ideal conditions for creation of surface with the biggest possible part with metastable reconstructions (mostly (5x5) and (9x9)). This surface is then covered by vapor deposition by different amounts of Al and possibility of creation of magic clusters and other interesting structures is investigated. Structural models for magic clusters on (5x5) are proposed. The work includes description of experimental devices used in measurements as well as description of procedures and physical principles connected with functioning of STM.Department of Surface and Plasma ScienceKatedra fyziky povrchů a plazmatuFaculty of Mathematics and PhysicsMatematicko-fyzikální fakult

Studium interakce adsorbátu s pasivovanými povrchy Si pomocí STM

Skenovacia tunelová mikroskopia bola použitá na štúdium morfolgie táliovej vrstvy v rôznych štádiách desorbcie Tl z povrchu Si(111) a na štúdium správania sa rôznych adsorbátov na povrchu Si(111)/Tl-(1 × 1). Využitie táliovej vrstvy na pasivásiu povrchu Si(111) bolo bližšie skúmané pre rôzne druhy adsorbátov. Mangánové, hliníkové, indiové a cínové vrstvy, ktoré boli priamo deponované na Si(111)-(7 × 7), boli porovnané s vrstvami pripravenými depozíciou adsorbátu na pasivačnú vrstvu po následnej termálnej desorbcii tália z povrchu (po ohreve na teplote ≈ 400◦ C). Skúmané adsorbáty vykazovali známky extrémne vysokej difuzivity a slabej väzby k Si(111)/Tl-(1 × 1). Pasivačná vrstva bola voči ad- sorbátom stabilná. Aplikácia tália ako surfaktantu spôsobovala zníženie teploty a pokrytia potrebného na prípravu rekonštrukcií pozorovaných na povrchoch pripravených priamou depozíciou adsorbátu. 1The scanning tunneling microscopy is used to study the morphology of Tl adlayer in various stages of Tl desorption from the Si(111) surface and to study behaviour of various adsorbates on the Si(111)/Tl-(1 × 1). The utilization of thallium layer for passivation of the Si(111) was examined closely for various adsorbates. Manganese, aluminium, indium and tin layers which were directly deposited onto the Si(111)-(7 × 7) were compared with the layers prepared by deposition of adsorbate onto the passivating layer after the subsequent thermal desorption of Tl (after annealing at ≈ 400◦ C). Examined adsorbates exhibited signs of extremely high diffusivity and weak bond with the surface Si(111)/Tl- (1 × 1). The passivating layer was stable against the adsorbates.The application of thallium in the role of surfactant caused lowering of temperature and coverage needed for the preparation of reconstructions which were observed on the surfaces prepared by the direct deposition of adsorbate. 1Katedra fyziky povrchů a plazmatuDepartment of Surface and Plasma ScienceFaculty of Mathematics and PhysicsMatematicko-fyzikální fakult

Hot ductility of TiNb IF steel slab after hot torsion testing

The aim of the work was to evaluate the hot ductility loss in TiNb stabilized IF steel directly from the continuously-cast slab using hot torsion testing (plastometry) in the temperature range 600-1250 degrees C according to the basic programme, and also after temperature cycling. A good match of the temperature dependences of number of turns to failure (N-f) and intensity of deformation Se was confirmed. In both cases, the existence of three temperature areas with decrease in plasticity to a minimum was confirmed. The two-stage temperature cycling according to the CT1150 and CT900 programmes mostly resulted in a decrease in plasticity compared to the basic programme. The most significant effect of cycling was related to the CT900 programme below the maximum plasticity in the base programme at 850 degrees C. A less pronounced decrease was observed for CT1150 cycling below the maximum plasticity in the base program at 1050 degrees C. In the case of CT1150 cycling, more complex particles were observed at the fractures compared with the basic programme, namely carbonitrides of Ti and Nb in combination with oxisulfides respectively, then Ti nitrides with oxisulfides or oxides and, in addition, complex (Fe,Nb)P-4, (Ti,Nb)(3)S-4 type particles. Their mean size determined statistically using TEM was much finer, only 20 nm versus 42 nm in the basic programme. Similarly, CT900 cycling revealed finer particles with an average size of 37 nm compared to 105 nm in the basic programme. The observed particles were Al oxides, Ti(N, C) and (Ti, Nb) 2S, in contrast to the particles probably of TiFe and FeMnS in the basic programme. The decrease in plasticity corresponded to the finer particles, newly created in the temperature cycling.Web of Science97art. no. 75

Metal-support interaction and charge distribution in ceria-supported Au particles exposed to CO

Understanding how reaction conditions affect metal-support interactions in catalytic materials is one of the most challenging tasks in heterogeneous catalysis research. Metal nanoparticles and their supports often undergo changes in structure and oxidation state when exposed to reactants, hindering a straightforward understanding of the structure-activity relations using only ex situ or ultrahigh vacuum techniques. Overcoming these limitations, we explored the metal-support interaction between gold nanoparticles and ceria supports in ultrahigh vacuum and after exposure to CO. A combination of in situ methods (on powder and model Au/CeO2 samples) and theoretical calculations was applied to investigate the gold/ceria interface and its reactivity toward CO exposure. X-ray photoelectron spectroscopy measurements rationalized by first-principles calculations reveal a distinctly inhomogeneous charge distribution, with Au+ atoms in contact with the ceria substrate and neutral Au0 atoms at the surface of the Au nanoparticles. Exposure to CO partially reduces the ceria substrate, leading to electron transfer to the supported Au nanoparticles. Transferred electrons can delocalize among the neutral Au atoms of the particle or contribute to forming inert Auδ− atoms near oxygen vacancies at the ceria surface. This charge redistribution is consistent with the evolution of the vibrational frequencies of CO adsorbed on Au particles obtained using diffuse reflectance infrared Fourier transform spectroscopy

Selective electrooxidation of 2-propanol on Pt nanoparticles supported on Co3O4: an in-situ study on atomically defined model systems

2-Propanol and its dehydrogenated counterpart acetone can be used as a rechargeable electrofuel. The concept involves selective oxidation of 2-propanol to acetone in a fuel cell coupled with reverse catalytic hydrogenation of acetone to 2-propanol in a closed cycle. We studied electrocatalytic oxidation of 2-propanol on complex model Pt/Co3O4(111) electrocatalysts prepared in ultra-high vacuum and characterized by scanning tunneling microscopy. The electrocatalytic behavior of the model electrocatalysts has been investigated in alkaline media (pH 10, phosphate buffer) by means of electrochemical infrared reflection absorption spectroscopy and ex-situ emersion synchrotron radiation photoelectron spectroscopy as a function of Pt particle size and compared with the electrocatalytic behavior of Pt(111) and pristine Co3O4(111) electrodes under similar conditions. We found that the Co3O4(111) film is inactive towards electrochemical oxidation of 2-propanol under the electrochemical conditions (0.3–1.1 VRHE). The electrochemical oxidation of 2-propanol readily occurs on Pt(111) yielding acetone at an onset potential of 0.4 VRHE. The reaction pathway does not involve CO but yields strongly adsorbed acetone species leading to a partial poisoning of the surface sites. On model Pt/Co3O4(111) electrocatalysts, we observed distinct metal support interactions and particle size effects associated with the charge transfer at the metal/oxide interface. We found that ultra-small Pt particles (around 1 nm and below) consist of partially oxidized Pt δ + species which show minor activity towards 2-propanol oxidation. In contrast, conventional Pt particles (particle size of a few nm) are mainly metallic and show high activity toward 2-propanol oxidation

Vliv pasivace povrchů Si na růst a uspořádávání nanostruktur

Kremík je v súčasnosti najpoužívanejší polovodičový materiál, ktorého aplikácie siahajú od solárnych článkov a senzorov po elektronické zariadenia. Funkcionalizácia povrchu pomocou molekulárnych vrstiev môže vylepšiť vlastnosti kremíkového povrchu a môže zmenšiť veľkosť funkčných prvkov elektronických zariadení. Avšak, nájdenie spôsobu akým molekuly naviazať na konkrétne miesta na povrchu a nájdenie spôsobu akým molekuly usporiadať na kremíkových povrchoch nie je ľahké kvôli vysokej reaktivite kremíku. V tejto práci používame skenovací tunelový mikroskop, ab-initio výpočty a kinetické Monte Carlo simulácie a študujeme adsorpciu organických molekúl na čistom a táliom pasivovanom povrchu Si(111). Ukazujeme, že polarita molekúl má veľký dopad na spôsob naviazania molekúl na čistý povrch. Naše pozorovania dokazujú, že v porovnaní s čistým povrchom sú molekuly a jedno-atomárne adsorbáty na pasivovanom povrchu výrazne mobilnejšie. Zvýšená mobilita molekúl spôsobuje vytvorenie 2D plynu na povrchu a umožňuje tvorbu samousporiadaných molekulárnych štruktúr. V práci navrhujeme novú metódu pre priame pozorovanie 2D molekulárneho plynu a ukazujeme, že pomocou nehomogénneho elektrického poľa je možné kontrolovať fázu molekúl na povrchu, v prípade že tieto molekuly na seba viažu dipólový moment. 1Silicon is currently the most widely used semiconductor material with applications ranging from solar cells and sensors to electronic devices. Surface functionalization of silicon with molecular monolayers can be used to tune properties of the material toward a desired application. However, site-specific adsorption of molecules or molecular patterning on silicon surfaces is a difficult task due to the high reactivity of silicon. In this work, we use scanning tunneling microscopy, ab-initio calculations and kinetic Monte Carlo simulations to study adsorption of organic molecules on a bare and thallium-passivated Si(111) surface. We show that the polarity of molecules has a large impact on bonding of the molecules with the bare surface. We demonstrate that, in comparison with the bare surface, molecules or single-atom adsorbates deposited on the Tl-passivated surface have significantly higher mobility. The increased mobility induces formation of 2D gases on the surface and enables formation of self-assembled molecular structures. We propose a novel method to directly visualize the 2D surface gases and we show that a phase of surface gases containing molecule-bound dipoles can be controlled by a non-homogeneous electric field. 1Katedra fyziky povrchů a plazmatuDepartment of Surface and Plasma ScienceMatematicko-fyzikální fakultaFaculty of Mathematics and Physic

Influence of Si surface passivation on growth and ordering of nanostructures

Silicon is currently the most widely used semiconductor material with applications ranging from solar cells and sensors to electronic devices. Surface functionalization of silicon with molecular monolayers can be used to tune properties of the material toward a desired application. However, site-specific adsorption of molecules or molecular patterning on silicon surfaces is a difficult task due to the high reactivity of silicon. In this work, we use scanning tunneling microscopy, ab-initio calculations and kinetic Monte Carlo simulations to study adsorption of organic molecules on a bare and thallium-passivated Si(111) surface. We show that the polarity of molecules has a large impact on bonding of the molecules with the bare surface. We demonstrate that, in comparison with the bare surface, molecules or single-atom adsorbates deposited on the Tl-passivated surface have significantly higher mobility. The increased mobility induces formation of 2D gases on the surface and enables formation of self-assembled molecular structures. We propose a novel method to directly visualize the 2D surface gases and we show that a phase of surface gases containing molecule-bound dipoles can be controlled by a non-homogeneous electric field.

Interaction of metal atoms with metastable reconstructions of the Si(111) surface studied by STM

Process of reconstruction of Si(111) surface after vapor deposition of thallium and subsequent desorption is studied by STM. Dependency of surface coverage on temperature is determined and this dependency is afterwards used for determination of ideal conditions for creation of surface with the biggest possible part with metastable reconstructions (mostly (5x5) and (9x9)). This surface is then covered by vapor deposition by different amounts of Al and possibility of creation of magic clusters and other interesting structures is investigated. Structural models for magic clusters on (5x5) are proposed. The work includes description of experimental devices used in measurements as well as description of procedures and physical principles connected with functioning of STM

Interaction of metal atoms with metastable reconstructions of the Si(111) surface studied by STM

Process of reconstruction of Si(111) surface after vapor deposition of thallium and subsequent desorption is studied by STM. Dependency of surface coverage on temperature is determined and this dependency is afterwards used for determination of ideal conditions for creation of surface with the biggest possible part with metastable reconstructions (mostly (5x5) and (9x9)). This surface is then covered by vapor deposition by different amounts of Al and possibility of creation of magic clusters and other interesting structures is investigated. Structural models for magic clusters on (5x5) are proposed. The work includes description of experimental devices used in measurements as well as description of procedures and physical principles connected with functioning of STM

Studium interakce adsorbátu s pasivovanými povrchy Si pomocí STM

The scanning tunneling microscopy is used to study the morphology of Tl adlayer in various stages of Tl desorption from the Si(111) surface and to study behaviour of various adsorbates on the Si(111)/Tl-(1 × 1). The utilization of thallium layer for passivation of the Si(111) was examined closely for various adsorbates. Manganese, aluminium, indium and tin layers which were directly deposited onto the Si(111)-(7 × 7) were compared with the layers prepared by deposition of adsorbate onto the passivating layer after the subsequent thermal desorption of Tl (after annealing at ≈ 400◦ C). Examined adsorbates exhibited signs of extremely high diffusivity and weak bond with the surface Si(111)/Tl- (1 × 1). The passivating layer was stable against the adsorbates.The application of thallium in the role of surfactant caused lowering of temperature and coverage needed for the preparation of reconstructions which were observed on the surfaces prepared by the direct deposition of adsorbate.