A pair of studies investigating the deposition and surface chemical properties of ultrathin metal films were pursued: (i) Pt-Co alloys on Mo(110); and (ii) Pd on Pt(111). Experimental measurement was based on a combination of electron spectroscopy (low energy ion scattering spectroscopy, X-ray photoelectron spectroscopy, Auger electron spectroscopy, and low energy electron diffraction) and electrochemistry (voltage efficiency, voltammetry, and coulometry). Mixed-metal preparation of Pt-Co films by thermal vapor deposition (TVD) resulted in a thin-film binary alloy. Careful analysis revealed a substantial divergence between the composition at the interface and that in the interior. This outcome was observed for all compositions and allowed for the construction of a ?surface phase diagram?. The proclivities of the alloys of pre-selected compositions towards enhanced catalysis of the oxygen-reduction reaction were assessed in terms of their voltage efficiencies, as manifested by the open-circuit potential (OCP) in O2-saturated dilute sulfuric acid electrolyte. The particular alloy surface, Pt3Co (XPt=3,XCo=1), whether from the thin film or a bulk single crystal, exhibited the highest OCP, a significant improvement over pure Pt but still appreciably lower than the thermodynamic limit. Under test conditions, the degradation of thusly-prepared films was primarily due to Co corrosion. Ultrathin Pd films on well-defined Pt(111) surfaces, with coverages from 0.5 to 8 monolayers (ML), were prepared by surface-limited redox replacement reaction (galvanic exchange) of underpotentially deposited Cu. Spectroscopic data revealed that films prepared in this manner are elementally pure, pseudomorphic to the substrate, and stable, independent of the surface coverage (?) of palladium. Analysis of the voltammetric profiles in the hydrogen evolution region revealed unique properties of hydrogen adsorption unseen in bulk electrodes. Notably, at 1 ML coverage, a step-free film was produced that did not exhibit hydrogen absorption. At higher coverages, digital (layer-by-layer) deposition gave way to 3D islands in a Stranski- Krastanov growth mode; under these conditions, onset of bulk-like behavior was observed. This method makes possible the synthesis of well-ordered noble-metal films in the absence of high-temperature treatment

This diploma thesis deals with the preparation of the very thin films and their investigation by scanning probe microscopy methods. The ultrathin films of Pt on Pt(111) were created by pulsed laser deposition and the ultrathin films of Co on Pt(111) were deposited by thermal evaporation. The coverage of the substrate was much smaller than one monolayer (in order of hundredths of monolayer). The nucleation theory was verified by these experiments using so-called Onset method. Further graphene sheets were prepared on layer of Si/SiO2 by the mechanical exfoliation from the graphite crystal. The fabricated graphene sheets were studied by micro-Raman spectroscopy, microreflectometry, atomic force microscopy and similar techniques. These methods proved the thinnest graphite layers were consisted of two graphene monolayers.

This diploma thesis studies magneto-optical (MO) response of epitaxial thin films of Co-doped ceria. Thin films were characterized by XPS, LEED, STM, spectroscopic ellipsometry and measurement of MO activity. The work focuses on studying MO response of the films depending on film thickness, cobalt concentration, oxidation state of cerium and chemical state of cobalt. Spectra of MO response consist of low energy region where the MO activity is mediated by transitions from defect induced states to conduction band and high energy region where a peak of MO activity appears which we attribute to transitions from valence band to conduction band. In this work we qualitatively explain the effects of the physico- chemical states of the thin films on the structure of the obtained MO spectra, mainly on the appearance of the MO activity in the low energy region, and on the changes of the position of the MO peak. Compared to other preparation methods the epitaxial thin films allow achieving a shift of the MO peak in the direction of higher photon energy.

This diploma thesis studies magneto-optical (MO) response of epitaxial thin films of Co-doped ceria. Thin films were characterized by XPS, LEED, STM, spectroscopic ellipsometry and measurement of MO activity. The work focuses on studying MO response of the films depending on film thickness, cobalt concentration, oxidation state of cerium and chemical state of cobalt. Spectra of MO response consist of low energy region where the MO activity is mediated by transitions from defect induced states to conduction band and high energy region where a peak of MO activity appears which we attribute to transitions from valence band to conduction band. In this work we qualitatively explain the effects of the physico- chemical states of the thin films on the structure of the obtained MO spectra, mainly on the appearance of the MO activity in the low energy region, and on the changes of the position of the MO peak. Compared to other preparation methods the epitaxial thin films allow achieving a shift of the MO peak in the direction of higher photon energy.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第20787号 / 理博第4331号 / 新制||理||1622(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 松本 吉泰, 教授 谷村 吉隆, 教授 寺嶋 正秀 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Die vorliegende Arbeit widmet sich der Untersuchung von 4 Modellsystemen der Oberflächenforschung. Die verwendeten experimentellen Methoden sind Summenfrequenzerzeugungsspekroskopie (SFG), Thermische Desorptionsspektroskopie (TDS), Beugung niederenergetischer Elektronen (LEED), Augerelektronenspektroskopie (AES), Infrarotadsorptionsspektrokopie (IRAS) und Rastertunnelmikroskopie (STM). Durch die Verwendung von SFG waren Messungen bis zu 50 mbar möglich. Die untersuchten Systeme sind: CO auf Pt(111), Wasser auf Ag(001) und MgO/Ag(001), CO auf Au/MgO/Ag(001) und CO auf Au-Pd/MgO/Ag(001). Bei den Messungen von CO auf Pt(111) tritt unter bestimmten Druck- und Temperaturbedingungen eine bisher nicht näher untersuchte Doppelpeakstruktur auf, die genauer charakterisiert wurde. Die Untersuchungen von Wasser auf MgO/Ag(001) und Ag(001) zeigen, dass sich auf MgO/Ag(001) zuerst eine Monolage Wasser mit einer darauffolgenden Multilage ausbildet, wohingegen es auf Ag(001) von Beginn an in einer Multilagenschicht wächst. Die Monolage kann unter der Multilage gemessen werden und einige Resonanzen identifiziert werden. Für Au/MgO/Ag(001) zeigte sich mittels STM eine Abhängigkeit des Au-Wachstums von der Schichtdicke, die allerdings nicht spektroskopisch in Erscheinung tritt. Bei den Messungen an gemischten Au-Pd-Teilchen auf MgO/Ag(001) zeigen sich Unterschiede im Adsorptionsverhalten zwischen reinen Metallteilchen und gemischten Teilchen, die auf eine Wechselwirkung zwischen den beiden Metallen zurückzuführen ist. Nach Heizschritten auf 600 K reichern sich die Au-Atome im Mantel des Teilchens an, das Pd bildet den Kern. Die Ergebnisse aller Messungen werden unter Berücksichtigung neuer Veröffentlichungen diskutiert. / This thesis focuses on 4 different model systems of surface science. The experimental techniques used for the measurements include sum frequency generation (SFG), thermal desorption spectroscopy (TDS), low energy electron diffraction (LEED), Auger electron spectroscopy (AES), infrared adsorption spectrosocopy (IRAS) and scanning tunneling microscopy (STM). By using SFG, measurements could be performed up to a pressure of 50 mbar. The systems under investigation were: CO on Pt(111), water on Ag(001) and on MgO/Ag(001), CO on Au/MgO/Ag(001), and CO on Au-Pd/MgO/Ag(001). The system of CO on Pt(111) exhibits a two peak-pattern under certain pressure and temperature conditions which has not been studied so far. Various experiments helped to elucidate the origin of this distinct behaviour. The measurements of water on Ag(001) and MgO/Ag(001) show that on MgO, water first adsorbs as a monolayer with a following multilayer, whereas on Ag(001) it adsorbs as a multilayer from the beginning. The monolayer can be studied below the multilayer and some resonances can be identified. For the case of Au/MgO/Ag(001), STM shows that the growth mode of Au depends on the thickness of the supporting MgO film, which can not be seen with spectroscopic methods. For mixed Au-Pd particles on MgO/Ag(001) a clear difference in the adsorption behaviour between pure metal particles and mixed particles can be seen, which is explained by an interaction between these metals. Annealing the mixed particles to 600 K leads to a segregation of the metals, where the Au atoms diffuse to the shell and the Pd atoms make up the core. The results of all these measurements are discussed in the light of recent publications.

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