Resolving the Structure of a Well-Ordered Hydroxyl Overlayer on In2O3(111): Nanomanipulation and Theory

M. Wagner, P. Lackner, S. Seiler, A. Brunsch, R. Bliem, S. Gerhold, Z. Wang, J. Osiecki, K. Schulte, L. A. Boatner, M. Schmid, B. Meyer, U. Diebold

Institut für Angewandte Physik, TU Wien, 1040 Wien, Austria
Interdisciplinary Center for Molecular Materials and Computer-Chemistry-Center, Friedrich-Alexander-Universität Erlangen-Nürnberg, 91052 Erlangen, Germany
MAX IV Laboratory, Lund University, 223 63 Lund, Sweden
Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, U. S. A.

ACS Nano 11 (2017) 11531–11541

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 (PES), and density functional theory (DFT). 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 oxygen atoms that are symmetrically arranged around the six-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, were 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.

Corresponding author: Margareta Wagner (wagner at iap_tuwien_ac_at).

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