Adsorption configurations of Co-phthalocyanine on In2O3(111)

TL;DR

This study investigates how Co-phthalocyanine molecules adsorb on the In2O3(111) surface, revealing two distinct adsorption sites that influence molecular structure and electronic properties, using microscopy and density functional theory.

Contribution

It provides detailed atomic-scale insights into the adsorption behavior and electronic effects of CoPc on In2O3(111), highlighting the impact of adsorption site on molecular configuration.

Findings

CoPc molecules adsorb at two distinct sites with a 7:3 ratio.

Adsorption site affects molecular bending and electronic structure.

Different domain structures form depending on the adsorption site.

Abstract

Indium oxide offers optical transparency paired with electric conductivity, a combination required in many optoelectronic applications. The most-stable In2O3(111) surface has a large unit cell (1.43 nm lattice constant). It contains a mixture of both bulk-like and undercoordinated O and In atoms and provides an ideal playground to explore the interaction of surfaces with organic molecules of similar size as the unit cell. Non-contact atomic force microscopy (nc-AFM), scanning tunneling microscopy (STM), and density functional theory (DFT) were used to study the adsorption of Co-phthalocyanine (CoPc) on In2O3(111). Isolated CoPc molecules adsorb at two adsorption sites in a 7:3 ratio. The Co atom sits either on top of a surface oxygen ('F configuration') or indium atom ('S configuration'). This subtle change in adsorption site induces bending of the molecules, which is reflected in their electronic structure. According to DFT the lowest unoccupied molecular orbital of the undistorted gas-phase CoPc remains mostly unaffected in the F configuration but is filled by one electron in S configuration. At coverages up to one CoPc molecule per substrate unit cell, a mixture of domains with molecules in F and S configuration are found. Molecules at F sites first condense into a F-(2x2) structure and finally rearrange into a F-(1x1) symmetry with partially overlapping molecules, while S-sited molecules only assume a S-(1x1) superstructure.