Resolving the Structure of a Well-Ordered Hydroxyl Overlayer on In 2 O 3 (111): Nanomanipulation and Theory
Abstract
Changes in chemical and physical properties resulting from water adsorption play an important role in the characterization and performance of device-relevant materials. Studies of model oxides with well-characterized surfaces can provide detailed information that is vital for a general understanding of water–oxide interactions. In this work, we study single crystals of indium oxide, the prototypical transparent contact material that is heavily used in a wide range of applications and most prominently in optoelectronic technologies. Water adsorbs dissociatively already at temperatures as low as 100 K, as confirmed by scanning tunneling microscopy (STM), photoelectron spectroscopy, and density functional theory. This dissociation takes place on lattice sites of the defect-free surface. While the In2O3(111)-(1 × 1) surface offers four types of surface oxygen atoms (12 atoms per unit cell in total), water dissociation happens exclusively at one of them together with a neighboring pair of 5-fold coordinated In atoms. These O–In groups are symmetrically arranged around the 6-fold coordinated In atoms at the surface. At room temperature, the In2O3(111) surface thus saturates at three dissociated water molecules per unit cell, leading to a well-ordered hydroxylated surface with (1 × 1) symmetry, where the three water OWH groups plus the surface OSH groupsmore »
- Authors:
-
- Institute of Applied Physics, TU Wien, Wiedner Hauptstraße 8-10/134, 1040 Vienna, Austria
- Interdisciplinary Center for Molecular Materials and Computer-Chemistry-Center, Friedrich-Alexander-Universität Erlangen-Nürnberg, Nägelsbachstraße 25, 91052 Erlangen, Germany
- MAX IV Laboratory, Lund University, Ole Römers väg 1, 223 63 Lund, Sweden
- Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1408068
- Alternate Identifier(s):
- OSTI ID: 1421789; OSTI ID: 1426584
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Published Article
- Journal Name:
- ACS Nano
- Additional Journal Information:
- Journal Name: ACS Nano Journal Volume: 11 Journal Issue: 11; Journal ID: ISSN 1936-0851
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; density functional theory; hydroxylation; indium oxide; scanning tunneling microscopy; water dissociation
Citation Formats
Wagner, Margareta, Lackner, Peter, Seiler, Steffen, Brunsch, Achim, Bliem, Roland, Gerhold, Stefan, Wang, Zhiming, Osiecki, Jacek, Schulte, Karina, Boatner, Lynn A., Schmid, Michael, Meyer, Bernd, and Diebold, Ulrike. Resolving the Structure of a Well-Ordered Hydroxyl Overlayer on In 2 O 3 (111): Nanomanipulation and Theory. United States: N. p., 2017.
Web. doi:10.1021/acsnano.7b06387.
Wagner, Margareta, Lackner, Peter, Seiler, Steffen, Brunsch, Achim, Bliem, Roland, Gerhold, Stefan, Wang, Zhiming, Osiecki, Jacek, Schulte, Karina, Boatner, Lynn A., Schmid, Michael, Meyer, Bernd, & Diebold, Ulrike. Resolving the Structure of a Well-Ordered Hydroxyl Overlayer on In 2 O 3 (111): Nanomanipulation and Theory. United States. https://doi.org/10.1021/acsnano.7b06387
Wagner, Margareta, Lackner, Peter, Seiler, Steffen, Brunsch, Achim, Bliem, Roland, Gerhold, Stefan, Wang, Zhiming, Osiecki, Jacek, Schulte, Karina, Boatner, Lynn A., Schmid, Michael, Meyer, Bernd, and Diebold, Ulrike. Wed .
"Resolving the Structure of a Well-Ordered Hydroxyl Overlayer on In 2 O 3 (111): Nanomanipulation and Theory". United States. https://doi.org/10.1021/acsnano.7b06387.
@article{osti_1408068,
title = {Resolving the Structure of a Well-Ordered Hydroxyl Overlayer on In 2 O 3 (111): Nanomanipulation and Theory},
author = {Wagner, Margareta and Lackner, Peter and Seiler, Steffen and Brunsch, Achim and Bliem, Roland and Gerhold, Stefan and Wang, Zhiming and Osiecki, Jacek and Schulte, Karina and Boatner, Lynn A. and Schmid, Michael and Meyer, Bernd and Diebold, Ulrike},
abstractNote = {Changes in chemical and physical properties resulting from water adsorption play an important role in the characterization and performance of device-relevant materials. Studies of model oxides with well-characterized surfaces can provide detailed information that is vital for a general understanding of water–oxide interactions. In this work, we study single crystals of indium oxide, the prototypical transparent contact material that is heavily used in a wide range of applications and most prominently in optoelectronic technologies. Water adsorbs dissociatively already at temperatures as low as 100 K, as confirmed by scanning tunneling microscopy (STM), photoelectron spectroscopy, and density functional theory. This dissociation takes place on lattice sites of the defect-free surface. While the In2O3(111)-(1 × 1) surface offers four types of surface oxygen atoms (12 atoms per unit cell in total), water dissociation happens exclusively at one of them together with a neighboring pair of 5-fold coordinated In atoms. These O–In groups are symmetrically arranged around the 6-fold coordinated In atoms at the surface. At room temperature, the In2O3(111) surface thus saturates at three dissociated water molecules per unit cell, leading to a well-ordered hydroxylated surface with (1 × 1) symmetry, where the three water OWH groups plus the surface OSH groups are imaged together as one bright triangle in STM. Manipulations with the STM tip by means of voltage pulses preferentially remove the H atom of one surface OSH group per triangle. The change in contrast due to strong local band bending provides insights into the internal structure of these bright triangles. The experimental results are further confirmed by quantitative simulations of the STM image corrugation.},
doi = {10.1021/acsnano.7b06387},
journal = {ACS Nano},
number = 11,
volume = 11,
place = {United States},
year = {2017},
month = {11}
}
https://doi.org/10.1021/acsnano.7b06387
Web of Science
Works referenced in this record:
Surface Electron Accumulation and the Charge Neutrality Level in
journal, September 2008
- King, P. D. C.; Veal, T. D.; Payne, D. J.
- Physical Review Letters, Vol. 101, Issue 11
The interaction of water with solid surfaces: Fundamental aspects
journal, October 1987
- Thiel, Patricia A.; Madey, Theodore E.
- Surface Science Reports, Vol. 7, Issue 6-8, p. 211-385
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Identification of adsorbed molecules via STM tip manipulation: CO, H 2 O, and O 2 on TiO 2 anatase (101)
journal, January 2014
- Setvin, Martin; Daniel, Benjamin; Aschauer, Ulrich
- Phys. Chem. Chem. Phys., Vol. 16, Issue 39
The oxidation and surface speciation of indium and indium oxides exposed to atmospheric oxidants
journal, June 2016
- Detweiler, Zachary M.; Wulfsberg, Steven M.; Frith, Matthew G.
- Surface Science, Vol. 648
F Centers versus Dimer Vacancies on ZnO Surfaces: Characterization by STM and STS Calculations
journal, June 2007
- Kováčik, Roman; Meyer, Bernd; Marx, Dominik
- Angewandte Chemie International Edition, Vol. 46, Issue 26
Observation of the Dynamical Change in a Water Monolayer Adsorbed on a ZnO Surface
journal, September 2005
- Dulub, Olga; Meyer, Bernd; Diebold, Ulrike
- Physical Review Letters, Vol. 95, Issue 13
XPS and AFM studies of surface chemistry and morphology of In 2 O 3 ultrathin films deposited by rheotaxial growth and vacuum oxidation after air exposure: XPS and AFM studies of In 2 O 3
journal, September 2015
- Kościelniak, P.; Grzeszczak, A.; Szuber, J.
- Crystal Research and Technology, Vol. 50, Issue 11
Water adsorption on ZnO(101̄0): from single molecules to partially dissociated monolayers
journal, January 2006
- Meyer, Bernd; Rabaa, Hassan; Marx, Dominik
- Physical Chemistry Chemical Physics, Vol. 8, Issue 13
Indium Oxide as a Superior Catalyst for Methanol Synthesis by CO 2 Hydrogenation
journal, March 2016
- Martin, Oliver; Martín, Antonio J.; Mondelli, Cecilia
- Angewandte Chemie, Vol. 128, Issue 21
Basic Steps of Lateral Manipulation of Single Atoms and Diatomic Clusters with a Scanning Tunneling Microscope Tip
journal, July 1997
- Bartels, L.; Meyer, G.; Rieder, K. -H.
- Physical Review Letters, Vol. 79, Issue 4
Transparent Conducting Oxides for Photovoltaics: Manipulation of Fermi Level, Work Function and Energy Band Alignment
journal, November 2010
- Klein, Andreas; Körber, Christoph; Wachau, André
- Materials, Vol. 3, Issue 11
Electron Microscopy for the Fine Needle Aspiration of Tumours: A Primer
journal, November 1998
- Sarraf, C.
- British Journal of Cancer, Vol. 78, Issue 10
Interaction of indium oxide nanoparticle film surfaces with ozone, oxygen and water: Interaction of indium oxide nanoparticle film surfaces with O 3 , O 2 and H 2 O
journal, January 2016
- Himmerlich, M.; Eisenhardt, A.; Berthold, T.
- physica status solidi (a), Vol. 213, Issue 3
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009
- Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
- Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
Structural motifs of water on metal oxide surfaces
journal, January 2017
- Mu, Rentao; Zhao, Zhi-jian; Dohnálek, Zdenek
- Chemical Society Reviews, Vol. 46, Issue 7
High Stability, High Activity Pt/ITO Oxygen Reduction Electrocatalysts
journal, December 2012
- Liu, Ying; Mustain, William E.
- Journal of the American Chemical Society, Vol. 135, Issue 2
Surface structure of Sn-doped In 2 O 3 (111) thin films by STM
journal, December 2008
- Morales, Erie H.; He, Yunbin; Vinnichenko, Mykola
- New Journal of Physics, Vol. 10, Issue 12
X‐ray photoemission spectroscopy studies of Sn‐doped indium‐oxide films
journal, August 1977
- Fan, John C. C.; Goodenough, John B.
- Journal of Applied Physics, Vol. 48, Issue 8
Edge reactivity and water-assisted dissociation on cobalt oxide nanoislands
journal, January 2017
- Fester, J.; García-Melchor, M.; Walton, A. S.
- Nature Communications, Vol. 8, Issue 1
Experimental electronic structure of In 2 O 3 and Ga 2 O 3
journal, August 2011
- Janowitz, Christoph; Scherer, Valentina; Mohamed, Mansour
- New Journal of Physics, Vol. 13, Issue 8
Phosphonate- and Carboxylate-Based Self-Assembled Monolayers for Organic Devices: A Theoretical Study of Surface Binding on Aluminum Oxide with Experimental Support
journal, June 2013
- Bauer, Thilo; Schmaltz, Thomas; Lenz, Thomas
- ACS Applied Materials & Interfaces, Vol. 5, Issue 13
Characterization of Indium−Tin Oxide Interfaces Using X-ray Photoelectron Spectroscopy and Redox Processes of a Chemisorbed Probe Molecule: Effect of Surface Pretreatment Conditions
journal, January 2002
- Donley, Carrie; Dunphy, Darren; Paine, David
- Langmuir, Vol. 18, Issue 2
Indium and Gallium: long-term supply
journal, July 2008
- Phipps, Gregory; Mikolajczak, Claire; Guckes, Terry
- Renewable Energy Focus, Vol. 9, Issue 4
Formation of the cyclic ice hexamer via excitation of vibrational molecular modes by the scanning tunneling microscope
journal, April 2002
- Morgenstern, Karina; Rieder, Karl-Heinz
- The Journal of Chemical Physics, Vol. 116, Issue 13
Aggregation and electronically induced migration of oxygen vacancies in anatase
journal, May 2015
- Setvin, Martin; Schmid, Michael; Diebold, Ulrike
- Physical Review B, Vol. 91, Issue 19
Tunneling dynamics of a hydroxyl group adsorbed on Cu(110)
journal, January 2009
- Kumagai, T.; Kaizu, M.; Okuyama, H.
- Physical Review B, Vol. 79, Issue 3
X-ray photoelectron spectroscopy of surface-treated indium-tin oxide thin films
journal, December 1999
- Kim, J. S.; Ho, P. K. H.; Thomas, D. S.
- Chemical Physics Letters, Vol. 315, Issue 5-6
Following the Reduction of Oxygen on TiO 2 Anatase (101) Step by Step
journal, July 2016
- Setvin, Martin; Aschauer, Ulrich; Hulva, Jan
- Journal of the American Chemical Society, Vol. 138, Issue 30
Thermally-driven processes on rutile TiO2(110)-(1×1): A direct view at the atomic scale
journal, May 2010
- Dohnálek, Zdenek; Lyubinetsky, Igor; Rousseau, Roger
- Progress in Surface Science, Vol. 85, Issue 5-8
State-selective dissociation of a single water molecule on an ultrathin MgO film
journal, April 2010
- Shin, Hyung-Joon; Jung, Jaehoon; Motobayashi, Kenta
- Nature Materials, Vol. 9, Issue 5
Investigation on ozone-sensitive In2O3 thin films
journal, October 1999
- Atashbar, M. Z.; Gong, B.; Sun, H. T.
- Thin Solid Films, Vol. 354, Issue 1-2
Manipulation of individual water molecules on CeO 2 (111)
journal, February 2012
- Torbrügge, S.; Custance, O.; Morita, S.
- Journal of Physics: Condensed Matter, Vol. 24, Issue 8
Action spectroscopy for single-molecule reactions – Experiments and theory
journal, May 2015
- Kim, Y.; Motobayashi, K.; Frederiksen, T.
- Progress in Surface Science, Vol. 90, Issue 2
Controlling the Charge State of Individual Gold Adatoms
journal, July 2004
- Repp, J.
- Science, Vol. 305, Issue 5683
Chemical reactions of water molecules on Ru(0001) induced by selective excitation of vibrational modes
journal, July 2009
- Mugarza, Aitor; Shimizu, Tomoko K.; Frank Ogletree, D.
- Surface Science, Vol. 603, Issue 13
Band gap, electronic structure, and surface electron accumulation of cubic and rhombohedral
journal, May 2009
- King, P. D. C.; Veal, T. D.; Fuchs, F.
- Physical Review B, Vol. 79, Issue 20
Adsorption of water at the SrO surface of ruthenates
journal, December 2015
- Halwidl, Daniel; Stöger, Bernhard; Mayr-Schmölzer, Wernfried
- Nature Materials, Vol. 15, Issue 4
Well-Ordered In Adatoms at the Surface Created by Fe Deposition
journal, November 2016
- Wagner, Margareta; Lackner, Peter; Seiler, Steffen
- Physical Review Letters, Vol. 117, Issue 20
Soft self-consistent pseudopotentials in a generalized eigenvalue formalism
journal, April 1990
- Vanderbilt, David
- Physical Review B, Vol. 41, Issue 11, p. 7892-7895
Thermodynamic stability, stoichiometry, and electronic structure of bcc-In O surfaces
journal, July 2011
- Agoston, Peter; Albe, Karsten
- Physical Review B, Vol. 84, Issue 4
Water growth on metals and oxides: binding, dissociation and role of hydroxyl groups
journal, January 2009
- Salmeron, M.; Bluhm, H.; Tatarkhanov, M.
- Faraday Discuss., Vol. 141
Adsorbate-induced lifting of substrate relaxation is a general mechanism governing titania surface chemistry
journal, September 2016
- Silber, David; Kowalski, Piotr M.; Traeger, Franziska
- Nature Communications, Vol. 7, Issue 1
Experimental Investigation of the Interaction of Water and Methanol with Anatase−TiO 2 (101)
journal, March 2003
- Herman, G. S.; Dohnálek, Z.; Ruzycki, N.
- The Journal of Physical Chemistry B, Vol. 107, Issue 12
Bulk and surface characterization of In O (001) single crystals
journal, March 2012
- Hagleitner, Daniel R.; Menhart, Manfred; Jacobson, Peter
- Physical Review B, Vol. 85, Issue 11
Microscopic identification of the compensation mechanisms in Si-doped GaAs
journal, October 1996
- Domke, C.; Ebert, Ph.; Heinrich, M.
- Physical Review B, Vol. 54, Issue 15
Valence band and band gap photoemission study of (111) In2O3 epitaxial films under interactions with oxygen, water and carbon monoxide
journal, December 2007
- Brinzari, V.; Korotcenkov, G.; Ivanov, M.
- Surface Science, Vol. 601, Issue 23
Reducing the In 2 O 3 (111) Surface Results in Ordered Indium Adatoms
journal, August 2014
- Wagner, Margareta; Seiler, Steffen; Meyer, Bernd
- Advanced Materials Interfaces, Vol. 1, Issue 8
Water Diffusion and Clustering on Pd(111)
journal, September 2002
- Mitsui, T.
- Science, Vol. 297, Issue 5588
Water Chain Formation on TiO 2 (110)
journal, December 2012
- Lee, Junseok; Sorescu, Dan C.; Deng, Xingyi
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 1
Perspective: Structure and dynamics of water at surfaces probed by scanning tunneling microscopy and spectroscopy
journal, October 2016
- Guo, Jing; Bian, Ke; Lin, Zeren
- The Journal of Chemical Physics, Vol. 145, Issue 16
Partial Dissociation of Water Leads to Stable Superstructures on the Surface of Zinc Oxide
journal, December 2004
- Meyer, Bernd; Marx, Dominik; Dulub, Olga
- Angewandte Chemie International Edition, Vol. 43, Issue 48