Prof. Ulrike Diebold Oxide Surfaces at the Atomic Scale

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Prof. Ulrike Diebold Oxide Surfaces at the Atomic Scale

Graz Advanced School of Science PHYSICS COLLOQUIUM OF THE UNIVERSITY OF GRAZ AND THE GRAZ UNIVERSITY OF TECHNOLOGY Prof. Ulrike Diebold Institute of Applied Physics, TU Wien, Vienna, Austria [email protected] Oxide Surfaces at the Atomic Scale Abstract: Our understanding of metal oxides has benefitted tremendously from the application of surface science techniques. Particularly useful has been Scanning Probe Microscopy, which allows to directly inspect, and even manipulate, atomic-size defects and defect-related surface chemistry. Equally important has been the development of suitable model systems, i.e., (ultra)thin films and well-prepared oxide single crystals that allow a reliable experimental and theoretical modeling with crisp and unequivocal insights into fundamental processes and mechanisms. In the talk, recent developments in the field will be illustrated by examples including our group’s recent research results on binary and ternary metal oxides [1-4]. Emphasis will be laid on giving an overview of different aspects, such as the importance of the relationship between bulk and surface defects [5], the opportunities and the challenges of extending surface science to more complex materials and to high- pressure and aqueous environments [6]. References: [1] R. Bliem, et al., Angew. Chemie Intl. Ed., 54, 13999 (2015) [4] M. Setvin, et al., Science, 359, 572 (2018) [2] D. Halwidl, et al., Nature Mater., 15, 450 (2016) [5] M. Setvin, et al., Chem. Soc. Rev. 46, 1772 (2017) [3] M. Setvin, et al., Proc. Natl. Acad. Sci., 114 E2556 (2017) [6] J. Balajka, et al., Science 361, 786 (2019) Fig.1 Atomically-resolved AFM image (20 x 20 nm2) of the (001) surface of the ternary compound KTaO . Fig.1 Atomically 3 This self-organized, labyrinth-like structure forms to alleviate the intrinsic polarity of this system [4]. How this works, and what other paths nature is taking, will be one topic of the talk. Date: Tuesday, October 23, 2018, 17:00 Location: Lecture Hall 05.01, Institute of Physics, University of Graz, Universitätsplatz 5 16:30 meet the speaker tea, Library of Experimental Physics, Institute of Physics, Universitätsplatz 5, 1st floor, room 122 Host: Prof. M. Sterrer – Institute of Physics – Experimental Physics – Surface Science For a regularly updated colloquium program see: http://www.if.tugraz.at/colloquium.html .

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Ulrike Diebold
Ulrike Diebold Institute of Applied Physics Vienna University of Technology (TU Vienna) Wiedner Hauptrasse 8-130/134 1040 Vienna, Austria [email protected], http://iap.tuwien.ac.at, Tel: +43-1-58801-13425, Fax: +43-1-58801-13499 Professional Objectives: Interdisciplinary research in surface science, physical chemistry, condensed matter physics, materials science, and nanoscience. Investigating the atomic-scale geometric and electronic surface structure of pure and doped oxide materials; adsorption of gases and metals; correlating nanoscopic measurements with materials applications in nanocatalysis, photocatalysis, gas sensing, (opto) electronics, and spintronics. Growth of epitaxial thin films and supported nanoclusters. Teaching and mentoring. Professional Experience: Institute of Applied Physics, TU Vienna Professor of Surface Science (2010 - ) Deputy Department Head (2010 - ) Department of Physics, Tulane University, New Orleans Research Professor (2010 -) Yahoo! Founder Chair in Science and Engineering (2006 -2009); Associate Department Chair (2002 -2009); Professor of Physics (2001 -2009); Associate Professor (1999 – 2001); Assistant Professor (1993 – 1999); Adjunct Professor of Chemistry (1993 - 2009) Visiting and Short-Term Appointments: 6/2008: Fellow, Research Center Dresden-Rossendorf, Dresden, Germany Fall 2005 (displaced by Hurricane Katrina) Visiting Professor, Rutgers, The State University of New Jersey, and Visiting Research Collaborator, Princeton University Summer 2004: Professor, Institute of Materials Chemistry,
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Small Polarons in Transition Metal Oxides
Small polarons in transition metal oxides Michele Reticcioli, Ulrike Diebold, Georg Kresse and Cesare Franchini Abstract The formation of polarons is a pervasive phenomenon in transition metal oxide compounds, with a strong impact on the physical properties and functionali- ties of the hosting materials. In its original formulation the polaron problem consid- ers a single charge carrier in a polar crystal interacting with its surrounding lattice. Depending on the spatial extension of the polaron quasiparticle, originating from the coupling between the excess charge and the phonon field, one speaks of small or large polarons. This chapter discusses the modeling of small polarons in real ma- terials, with a particular focus on the archetypal polaron material TiO2. After an introductory part, surveying the fundamental theoretical and experimental aspects of the physics of polarons, the chapter examines how to model small polarons us- ing first principles schemes in order to predict, understand and interpret a variety of polaron properties in bulk phases and surfaces. Following the spirit of this hand- book, different types of computational procedures and prescriptions are presented with specific instructions on the setup required to model polaron effects. Cite as: [1] Reticcioli M., Diebold U., Kresse G., Franchini C. (2019) Small Polarons in Transition Metal Oxides. In: Andreoni W., Yip S. (eds) Handbook of Materials Modeling. Springer, Cham. DOI:10.1007/978-3-319-50257-1 52-1 Michele Reticcioli University of Vienna, Austria Ulrike Diebold Institute of Applied Physics, Technische Universitat¨ Wien, Vienna, Austria Georg Kresse University of Vienna, Austria Cesare Franchini University of Vienna, Austria, e-mail: [email protected] arXiv:1902.04183v2 [cond-mat.mtrl-sci] 15 Feb 2019 1 2 Michele Reticcioli, Ulrike Diebold, Georg Kresse and Cesare Franchini 1 Introduction Electrons in perfect crystals are adequately described in terms of periodic wave functions.
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Methanol on Anatase Tio2 (101): Mechanistic Insights Into Photocatalysis Martin Setvin,*,† Xiao Shi,‡ Jan Hulva,† Thomas Simschitz,† Gareth S
This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. Research Article pubs.acs.org/acscatalysis Methanol on Anatase TiO2 (101): Mechanistic Insights into Photocatalysis Martin Setvin,*,† Xiao Shi,‡ Jan Hulva,† Thomas Simschitz,† Gareth S. Parkinson,† Michael Schmid,† Cristiana Di Valentin,*,§ Annabella Selloni,‡ and Ulrike Diebold† † Institute of Applied Physics, TU Wien, Wiedner Hauptstrasse 8-10/134, 1040 Vienna, Austria ‡ Department of Chemistry, Princeton University, Frick Laboratory, Princeton, New Jersey 08544, United States § Dipartimento di Scienza dei Materiali, Universitàdi Milano-Bicocca, Via Cozzi 55, 20125 Milano, Italy *S Supporting Information ABSTRACT: The photoactivity of methanol adsorbed on the anatase TiO2 (101) surface was studied by a combination of scanning tunneling microscopy (STM), temperature-programmed desorption (TPD), X-ray photoemission spectroscopy (XPS), and density functional theory (DFT) calculations. Isolated methanol molecules adsorbed at the anatase (101) surface show a negligible photoactivity. Two ways of methanol activation were found. First, methoxy groups formed by reaction of methanol with coadsorbed O2 molecules or terminal OH groups are photoactive, and they turn into formaldehyde upon UV illumination. The methoxy species show an unusual C 1s core-level shift of 1.4 eV compared to methanol; their chemical assignment was verified by DFT calculations with inclusion of final-state effects. The second way of methanol activation opens at methanol coverages above 0.5 monolayer (ML), and methyl formate is produced in this reaction pathway. The adsorption of methanol in the coverage regime from 0 to 2 ML is described in detail; it is key for understanding the photocatalytic behavior at high coverages.
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Surface Structure of Tio2 Rutile (011) Exposed to Liquid Water
This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. Article pubs.acs.org/JPCC Surface Structure of TiO2 Rutile (011) Exposed to Liquid Water Jan Balajka,† Ulrich Aschauer,‡ Stijn F. L. Mertens,† Annabella Selloni,§ Michael Schmid,† and Ulrike Diebold*,† † Institute of Applied Physics, TU Wien, Wiedner Hauptstraße 8-10/134, 1040 Vienna, Austria ‡ Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012, Bern, Switzerland § Department of Chemistry, Princeton University, Frick Laboratory, Princeton, New Jersey 08544, United States *S Supporting Information × ABSTRACT: The rutile TiO2(011) surface exhibits a (2 1) reconstruction when prepared by standard techniques in ultrahigh vacuum (UHV). Here we report that a restructuring occurs upon exposing the surface to liquid water at room temperature. The experiment was performed in a dedicated UHV system, equipped for direct and clean transfer of samples between UHV and liquid environment. After exposure to liquid water, an overlayer with a (2 × 1) symmetry was observed containing two dissociated water molecules per unit cell. The two OH groups yield an apparent “c(2 × 1)” symmetry in scanning tunneling microscopy (STM) images. On the basis of STM analysis and density functional theory (DFT) calculations, this overlayer is attributed to dissociated water on top of the unreconstructed (1 × 1) surface. Investigation of possible adsorption structures and analysis of the domain boundaries in this structure provide strong evidence that the original (2 × 1) reconstruction is lifted. Unlike the (2 × 1) reconstruction, the (1 × 1) surface has an appropriate density and symmetry of adsorption sites.
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Pulsed Laser Deposition Combined with Scanning Tunneling Microscopy
Surface Science 651 (2016) 76–83 Contents lists available at ScienceDirect Surface Science journal homepage: www.elsevier.com/locate/susc Adjusting island density and morphology of the SrTiO3(110)-(4 × 1) surface: Pulsed laser deposition combined with scanning tunneling microscopy Stefan Gerhold a, Michele Riva a,⁎, Bilge Yildiz a,b, Michael Schmid a, Ulrike Diebold a a Institute of Applied Physics, TU Wien, Wiedner Hauptstrasse 8-10/E134, A-1040 Vienna, Austria b Laboratory for Electrochemical Interfaces, Department of Nuclear Science and Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139, United States article info abstract Article history: The first stages of homoepitaxial growth of the (4 × 1) reconstructed surface of SrTiO3(110) are probed by a com- Received 15 February 2016 bination of pulsed laser deposition (PLD) with in-situ reflection high energy electron diffraction (RHEED) and Accepted 10 March 2016 scanning tunneling microscopy (STM). Considerations of interfacing high-pressure PLD growth with ultra- Available online 16 March 2016 high-vacuum surface characterization methods are discussed, and the experimental setup and procedures are described in detail. The relation between RHEED intensity oscillations and ideal layer-by-layer growth is con- Keywords: fi STM rmed by analysis of STM images acquired after deposition of sub-monolayer amounts of SrTiO3. For a quantita- Oxides tive agreement between RHEED and STM results one has to take into account two interfaces: the steps at the Growth circumference of islands, as well as the borders between two different reconstruction phases on the islands them- RHEED selves. Analysis of STM images acquired after one single laser shot reveals an exponential decrease of the island PLD density with increasing substrate temperature.
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Materials Science and Engineering
Materials Science and Engineering Robert R. McCormick School of Engineering and Applied Science Northwestern University SUMMER 2010 Greg Olson Elected to National Academy of Engineering Greg Olson holds a “Dragonslayer bullet-proof” drive gear used to win the Baja 1000 1600-class event. The top five finishers all used commercial Questek-designed steel gears. stainless steel alloy for aircraft landing gears that replaces the cadmium-plated steel, which poses an environmental hazard. Olson is a fellow of ASM and TMS-AIME, and he has authored more than 200 publications. He received a BS and MS in 1970 and ScD in 1974 in materials science from MIT and remained there in a series of senior research positions before joining the faculty of Northwestern in 1988. Beyond ma- terials design, his research interests include phase transformations, structure/property relationships, and applications of high resolution microanaly- sis. Recent awards include the ASM Campbell Memorial Lectureship, the TMS-SMD Distinguished Scientist/Engineer Award, and the Cambridge University Kelly Lectureship. reg Olson, Walter P. Murphy Professor of Materials Science In addition to Olson, McCormick alumnus Sang Yup Lee was and Engineering, has been elected a member of the Na- elected to NAE as a foreign member. Lee, currently dean of the Gtional Academy of Engineering. He is cited for his contri- College of Life Sciences and Bioengineering at the Korea Advanced bution to research, development, implementation and teaching of Institute of Science and Technology (KAIST), received both his MS science-based materials by design. (’87) and PhD (’91) from the Department of Chemical and Biological Olson is considered one of the founders of computational ma- terials design.
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Arxiv:1807.05859V1 [Cond-Mat.Mtrl-Sci] 16 Jul 2018 Sixfold-Coordinated Ti6c Atoms Lying in the Subsurface Polaronic Charge Is Transfered to the CO Molecule
Interplay between adsorbates and polarons: CO on rutile TiO2(110) Michele Reticcioli,1 Igor Sokolović,2 Michael Schmid,2 Ulrike Diebold,2 Martin Setvin,2, ∗ and Cesare Franchini1, y 1University of Vienna, Faculty of Physics and Center for Computational Materials Science, Vienna, Austria 2Institute of Applied Physics, Technische UniversitätWien, Vienna, Austria (Dated: July 17, 2018) Polaron formation plays a major role in determining the structural, electrical and chemical prop- erties of ionic crystals. Using a combination of first principles calculations and scanning tunneling microscpoy/atomic force microscopy (STM/AFM), we analyze the interaction of polarons with CO molecules adsorbed on the rutile TiO2(110) surface. Adsorbed CO shows attractive coupling with polarons in the surface layer, and repulsive interaction with polarons in the subsurface layer. As a result, CO adsorption depends on the reduction state of the sample. For slightly reduced surfaces, many adsorption configurations with comparable adsorption energies exist and polarons reside in the subsurface layer. At strongly reduced surfaces, two adsorption configurations dominante: either inside an oxygen vacancy, or at surface Ti5c sites, coupled with a surface polaron. A wide range of materials form polaronic in-gap states unfavorable but might eventually occur at elevated tem- upon injection of extra charge, as the excess electrons peratures [4,8, 24, 26]. or holes couple to the lattice phonon field. The charge The effect of polarons is usually not considered in ad- carrier generated by defects [1{6], doping [7{9], ad- sorption studies. CO adsorption on the rutile (110) sur- sorbates [10{12], or irradiation [13{16], interact with face is a well-studied phenomenon from both theoretical the lattice field to different extents depending on the and experimental points of view [37{43], yet controversies electron-phonon coupling, which is strongly material- appear even in elementary issues.
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Gareth S. Parkinson Date of Birth: 02 / 06 / 1981 Place of Birth: Darlington, UK Web Site / Google Scholar Profile / ORCID
Gareth S. Parkinson Date of Birth: 02 / 06 / 1981 Place of Birth: Darlington, UK Web Site / Google Scholar Profile / ORCID EDUCATION 2016 Habilitation in Experimental Physics Department of Physics, TU Wien, Vienna, Austria 2007 PhD – Surface Studies Using Medium Energy Ion Scattering (Advisor D. P. Woodruff) Department of Physics, University of Warwick, UK 2004 Masters Degree in Physics (MPhys) Department of Physics, University of Warwick, UK LANGUAGES English (Native speaker), German (Level B1) POSITIONS HELD 2017 - Associate Professor Institute for Applied Physics/ TU Wien, Austria 2015 – 2017 Assistant Professor (Laufbahnstelle) Institute for Applied Physics/ TU Wien, Austria 2010 – 2015 University Assistant Institute for Applied Physics/ TU Wien, Austria 2009 – 2010 Postdoctoral Researcher (supervisor U. Diebold) Department of Physics, Tulane University, New Orleans LA, USA 2007 – 2009 Postdoctoral Researcher (supervisor B.D. Kay) Pacific Northwest National Laboratory (PNNL), Richland WA, USA RESEARCH INTERESTS Since my appointment at the TU Wien in 2010, my research group has utilized a multi-technique approach to understand the atomic-scale processes underlying reactivity on metal-oxide surfaces. My aim is to combine my expertise in surface structure determination (gained in my PhD studies), with the experience in spectroscopy and scanning probe methods, gained during postdocs at PNNL and Tulane University, respectively. The iron oxides are a major focus of my work because they are omnipresent in the natural environment and find widespread applications in technology. In 2012, I was awarded a single investigator funding from the Austrian Science Fund (FWF) to study Fe3O4 surface chemistry. The work has been highly successful including papers in Science, Nature Materials, PNAS; Physical Review Letters, Angewandte Chemie, ACS Nano, JACS, and the Journal of Physical Chemistry.
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Polaron-Driven Surface Reconstructions
PHYSICAL REVIEW X 7, 031053 (2017) Polaron-Driven Surface Reconstructions Michele Reticcioli,1 Martin Setvin,2,* Xianfeng Hao,1,3 Peter Flauger,1 Georg Kresse,1 † Michael Schmid,2 Ulrike Diebold,2 and Cesare Franchini1, 1University of Vienna, Faculty of Physics and Center for Computational Materials Science, A-1090 Vienna, Austria 2Institute of Applied Physics, Technische Universität Wien, A-1040 Vienna, Austria 3Key Laboratory of Applied Chemistry, Yanshan University, Qinhuangdao 066004, People’s Republic of China (Received 24 May 2017; revised manuscript received 7 July 2017; published 25 September 2017) Geometric and electronic surface reconstructions determine the physical and chemical properties of surfaces and, consequently, their functionality in applications. The reconstruction of a surface minimizes its surface free energy in otherwise thermodynamically unstable situations, typically caused by dangling bonds, lattice stress, or a divergent surface potential, and it is achieved by a cooperative modification of the atomic and electronic structure. Here, we combined first-principles calculations and surface techniques (scanning tunneling microscopy, non-contact atomic force microscopy, scanning tunneling spectroscopy) to report that the repulsion between negatively charged polaronic quasiparticles, formed by the interaction between excess electrons and the lattice phonon field, plays a key role in surface reconstructions. As a paradigmatic example, we explain the (1 × 1)to(1 × 2) transition in rutile TiO2ð110Þ. DOI: 10.1103/PhysRevX.7.031053 Subject Areas: Condensed Matter Physics, Physical Chemistry, Semiconductor Physics I. INTRODUCTION lattice, and spins [1,12]. In this work, we find that charge trapping can cause surface reconstructions as well. The majority of surfaces undergo significant structural Excess charge in a flexible and ionic lattice is and electronic modifications with respect to the ideal bulk often present in the form of small polarons, i.e., trapped phase in order to minimize their surface free energy [1].
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Chem Soc Rev View Article Online TUTORIAL REVIEW View Journal | View Issue Surface point defects on bulk oxides: atomically-resolved scanning probe microscopy Cite this: Chem. Soc. Rev., 2017, 46, 1772 Martin Setvıń, Margareta Wagner, Michael Schmid, Gareth S. Parkinson and Ulrike Diebold* Metal oxides are abundant in nature and they are some of the most versatile materials for applications ranging from catalysis to novel electronics. The physical and chemical properties of metal oxides are dramatically influenced, and can be judiciously tailored, by defects. Small changes in stoichiometry introduce so-called intrinsic defects, e.g., atomic vacancies and/or interstitials. This review gives an overview of using Scanning Probe Microscopy (SPM), in particular Scanning Tunneling Microscopy (STM), to study the changes in the local geometric and electronic structure related to these intrinsic point defects at the surfaces of metal oxides. Three prototypical systems are discussed: titanium dioxide (TiO2), iron oxides (Fe3O4), and, as an example for a post-transition-metal oxide, indium oxide (In2O3). Creative Commons Attribution 3.0 Unported Licence. Received 1st February 2017 Each of these three materials prefers a different type of surface point defect: oxygen vacancies, cation DOI: 10.1039/c7cs00076f vacancies, and cation adatoms, respectively. The different modes of STM imaging and the promising capabilities of non-contact Atomic Force Microscopy (nc-AFM) techniques are discussed, as well as the rsc.li/chem-soc-rev capability of STM to manipulate single point defects. Key learning points On metal oxide surfaces, small changes in stoichiometry give rise to point defects. These can be ideally studied with local probes such as Scanning Tunneling Microscopy (STM) and non-contact Atomic Force Microscopy (nc-AFM).
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Surface Structure of Tio2 Rutile (011) Exposed to Liquid Water Jan Balajka,† Ulrich Aschauer,‡ Stijn F
This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. Article pubs.acs.org/JPCC Surface Structure of TiO2 Rutile (011) Exposed to Liquid Water Jan Balajka,† Ulrich Aschauer,‡ Stijn F. L. Mertens,† Annabella Selloni,§ Michael Schmid,† and Ulrike Diebold*,† † Institute of Applied Physics, TU Wien, Wiedner Hauptstraße 8-10/134, 1040 Vienna, Austria ‡ Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012, Bern, Switzerland § Department of Chemistry, Princeton University, Frick Laboratory, Princeton, New Jersey 08544, United States *S Supporting Information × ABSTRACT: The rutile TiO2(011) surface exhibits a (2 1) reconstruction when prepared by standard techniques in ultrahigh vacuum (UHV). Here we report that a restructuring occurs upon exposing the surface to liquid water at room temperature. The experiment was performed in a dedicated UHV system, equipped for direct and clean transfer of samples between UHV and liquid environment. After exposure to liquid water, an overlayer with a (2 × 1) symmetry was observed containing two dissociated water molecules per unit cell. The two OH groups yield an apparent “c(2 × 1)” symmetry in scanning tunneling microscopy (STM) images. On the basis of STM analysis and density functional theory (DFT) calculations, this overlayer is attributed to dissociated water on top of the unreconstructed (1 × 1) surface. Investigation of possible adsorption structures and analysis of the domain boundaries in this structure provide strong evidence that the original (2 × 1) reconstruction is lifted. Unlike the (2 × 1) reconstruction, the (1 × 1) surface has an appropriate density and symmetry of adsorption sites.
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The Surface Science of Titanium Dioxide
Surface Science Reports 48 (2003) 53±229 The surface science of titanium dioxide Ulrike Diebold* Department of Physics, Tulane University, New Orleans, LA 70118, USA Manuscript received in final form 7 October 2002 Abstract Titanium dioxide is the most investigated single-crystalline system in the surface science of metal oxides, and the literature on rutile (1 1 0), (1 0 0), (0 0 1), and anatase surfaces is reviewed. This paper starts with a summary of the wide varietyof technical ®elds where TiO 2 is of importance. The bulk structure and bulk defects (as far as relevant to the surface properties) are brie¯yreviewed. Rules to predict stable oxide surfaces are exempli®ed on rutile (1 1 0). The surface structure of rutile (1 1 0) is discussed in some detail. Theoreticallypredicted and experimentallydetermined relaxations of surface geometries are compared, and defects (step edge orientations, point and line defects, impurities, surface manifestations of crystallographic shear planesÐCSPs) are discussed, as well as the image contrast in scanning tunneling microscopy(STM). The controversyabout the correct model for the (1 Â 2) reconstruction appears to be settled. Different surface preparation methods, such as reoxidation of reduced crystals, can cause a drastic effect on surface geometries and morphology, and recommendations for preparing different TiO2(1 1 0) surfaces are given. The structure of the TiO2(1 0 0)-(1 Â 1) surface is discussed and the proposed models for the (1 Â 3) reconstruction are criticallyreviewed. Veryrecent results on anatase (1 0 0) and (1 0 1) surfaces are included. The electronic structure of stoichiometric TiO2 surfaces is now well understood.
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