Phthalocyanine arrangements on Ag(100): From pure overlayers of CoPc and F16CuPc to bimolecular heterostructure

Abstract

We have utilized scanning tunneling microscopy (STM) and low energy electron diffraction to determine the structural properties of two types of metal-phthalocyanines (MPcs), i.e., cobalt-phthalocyanine (CoPc) and hexadecafluorinated copper-phthalocyanine (F16CuPc) on the Ag(100) surface. For coverage close to one monolayer, both systems form long-range ordered structures with square unit cells. The size and rotation of the unit cell with respect to the silver lattice depend on the chemical composition of MPc. Both types of molecules prefer adsorption with around a 30° angle between the molecular axis and the [011] silver direction. The CoPcs mainly arrange in a (5 × 5)R0 phase; however, two additional local arrangements, a 26×26R11○ and a (7 × 7)R0, were detected by STM. The F16CuPcs form a 29×29R22○ structure. The co-adsorption of CoPc and F16CuPc on the Ag(100) surface in a 1:1 ratio leads to the formation of a compositionally ordered chessboard-like 52×52R45○ structure. During filled states imaging, the different appearance of the central part of each MPc allows us to distinguish CoPcs from F16CuPcs. Regardless of the applied voltage polarity, the ligands of F16CuPcs appear brighter than the ligands of CoPcs.

Stability of Partially Fluorinated Phthalocyanine Monolayers: Influence of Hydrogen Bonding Revisited

“…Formation of perfect chessboard-like superstructures of perfluorinated and nonfluorinated PC molecules was attributed to the directional interaction between partly charged F and H atoms. Following the first observation on highly oriented pyrolytic graphite, , analogous structures have been observed on Ag(111) or Ag(100) …”

“…Following the first observation on highly oriented pyrolytic graphite, 29,30 analogous structures have been observed on Ag(111) 31 or Ag(100). 32 In our previous works we studied room-temperature behavior of F 0 CuPC 33 and F 16 CuPC 34 molecules deposited on the Si(111)-Tl 1 × 1 surface. We found that the F 0 CuPC molecules form ordered structures at full ML coverage.…”

Extended iron phthalocyanine islands self-assembled on a Ge(001):H surface

“…Moreover, they are ideal candidates to study the influence of the interaction between the central metal atom and the surrounding ligands on the overall properties. Commonly, metal phthalocyanines and their derivatives have been investigated on crystalline metal surfaces [43][44][45][46][47][48][49][50][51][52][53][54][55][56][57]. However, the need to electronically decouple organic moieties from the underlying substrates directed the attention towards insulators and/or semiconductors.…”

Self-Assembly and Magnetic Order of Bi-Molecular 2D Spin Lattices of M(II,III) Phthalocyanines on Au(111)

“…In the first step of the aforementioned investigations, the procedure for preparation of alternating assemblies of two phthalocyanine molecules was adapted in line with Sabik et al [51][52][53]. We departed from our previously established procedure, where two molecular species, namely MnPc and FeFPc were co-evaporated onto the substrate of choice, kept at room temperature [5,55].…”

“…Similarly, a supramolecular checkerboard structure was described by Yoshimoto et al for a ZnPc and octaethylporphyrin ZnOEP system deposited on Au(111) and Au(100), whereby the study also emphasized the role of the atomic arrangement of the underlying substrate [50]. Moreover, Sabik et al studied CoPc + CuF 16 Pc arrangements on Ag(100) for selected ratios between the two molecular components [51][52][53]. Note that bi-component checkerboards also emerged by the site-specific adsorption of nonfunctionalized porphyrins on a reconstructed Bi on Cu(100) substrate [54].…”