Showing papers by "Gerhard Meyer published in 2017"

Synthesis and characterization of triangulene

Abstract: Triangulene, the smallest triplet-ground-state polybenzenoid (also known as Clar's hydrocarbon), has been an enigmatic molecule ever since its existence was first hypothesized. Despite containing an even number of carbons (22, in six fused benzene rings), it is not possible to draw Kekule-style resonant structures for the whole molecule: any attempt results in two unpaired valence electrons. Synthesis and characterization of unsubstituted triangulene has not been achieved because of its extreme reactivity, although the addition of substituents has allowed the stabilization and synthesis of the triangulene core and verification of the triplet ground state via electron paramagnetic resonance measurements. Here we show the on-surface generation of unsubstituted triangulene that consists of six fused benzene rings. The tip of a combined scanning tunnelling and atomic force microscope (STM/AFM) was used to dehydrogenate precursor molecules. STM measurements in combination with density functional theory (DFT) calculations confirmed that triangulene keeps its free-molecule properties on the surface, whereas AFM measurements resolved its planar, threefold symmetric molecular structure. The unique topology of such non-Kekule hydrocarbons results in open-shell π-conjugated graphene fragments that give rise to high-spin ground states, potentially useful in organic spintronic devices. Our generation method renders manifold experiments possible to investigate triangulene and related open-shell fragments at the single-molecule level.

Heavy Oil Based Mixtures of Different Origins and Treatments Studied by Atomic Force Microscopy

Abstract: Heavy oil molecular mixtures were investigated on the basis of single molecules resolved by atomic force microscopy. The eight different samples analyzed include asphaltenes and other heavy oil fractions of different geographic/geologic origin and processing steps applied. The collected AFM data of individual molecules provide information about the molecular geometry, aromaticity, the content of nonhexagonal rings, typical types and locations of heterocycles, occurrence, length and connectivity of alkyl side chains, and ratio of archipelago- vs island-type architectures. Common and distinguishing structural motifs for the different samples could be identified. The measured size distributions and the degree of unsaturation by scanning probe microscopy is consistent with mass spectrometry data presented herein. The results obtained reveal the complexity, properties and specifics of heavy oil fractions with implications for upstream oil production and downstream oil processing. Moreover, the identified molec...

Characterizing aliphatic moieties in hydrocarbons with atomic force microscopy

Abstract: We designed and studied hydrocarbon model compounds by high-resolution noncontact atomic force microscopy. In addition to planar polycyclic aromatic moieties, these novel model compounds feature linear alkyl and cycloaliphatic motifs that exist in most hydrocarbon resources - particularly in petroleum asphaltenes and other petroleum fractions - or in lipids in biological samples. We demonstrate successful intact deposition by sublimation of the alkyl-aromatics, and differentiate aliphatic moieties from their aromatic counterparts which were generated from the former by atomic manipulation. The characterization by AFM in combination with atomic manipulation provides clear fingerprints of the aromatic and aliphatic moieties that will facilitate their assignment in a priori unknown samples.

Generation and Characterization of a meta-Aryne on Cu and NaCl Surfaces.

Abstract: We describe the generation of a meta-aryne at low temperature (T = 5 K) using atomic manipulation on Cu(111) and on bilayer NaCl on Cu(111). We observe different voltage thresholds for dehalogenation of the precursor and different reaction products depending on the substrate surface. The chemical structure is resolved by atomic force microscopy with CO-terminated tips, revealing the radical positions and confirming a diradical rather than an anti-Bredt olefin structure for this meta-aryne on NaCl.

Tip-induced passivation of dangling bonds on hydrogenated Si(100)-2 × 1

Abstract: Using combined low temperature scanning tunneling microscopy and atomic force microscopy (AFM), we demonstrate hydrogen passivation of individual, selected dangling bonds (DBs) on a hydrogen-passivated Si(100)-2 × 1 surface (H–Si) by atom manipulation. This method allows erasing of DBs and thus provides a promising scheme for error-correction in hydrogen lithography. Both Si-terminated tips (Si tips) for hydrogen desorption and H-terminated tips (H tips) for hydrogen passivation are created by deliberate contact to the H–Si surface and are assigned by their characteristic contrast in AFM. DB passivation is achieved by transferring the H atom that is at the apex of an H tip to the DB, reestablishing a locally defect-free H–Si surface.

Passivation of dangling bonds on hydrogenated Si(100)-2$\times$1: a possible method for error correction in hydrogen lithography

Abstract: Using combined low temperature scanning tunneling microscopy (STM) and atomic force microscopy (AFM), we demonstrate hydrogen passivation of individual, selected dangling bonds (DBs) on a hydrogen-passivated Si(100)-2$\times$1 surface (H-Si) by atom manipulation. This method allows erasing of DBs and thus provides an error-correction scheme for hydrogen lithography. Si-terminated tips (Si tips) for hydrogen desorption and H-terminated tips (H tips) for hydrogen passivation are both created by deliberate contact to the H-Si surface and are assigned by their characteristic contrast in AFM. DB passivation is achieved by transferring the H atom that is at the apex of an H tip to the DB, reestablishing a locally defect-free H-Si surface.

Interactions between two C60 molecules measured by scanning probe microscopies

Abstract: C60-functionalized tips are used to probe C60 molecules on Cu(111) with scanning tunneling and atomic force microscopy. Distinct and complex intramolecular contrasts are found. Maximal attractive forces are observed when for both molecules a [6,6] bond faces a hexagon of the other molecule. Density functional theory calculations including parameterized van der Waals interactions corroborate the observations.

Atomic and Electronic Structure of Si Dangling Bonds in Quasi-Free-Standing Monolayer Graphene

Abstract: Si dangling bonds without H termination at the interface of quasi-free standing monolayer graphene (QFMLG) are known scattering centers that can severely affect carrier mobility. In this report, we study the atomic and electronic structure of Si dangling bonds in QFMLG using low-temperature scanning tunneling microscopy/spectroscopy (STM/STS), atomic force microscopy (AFM), and density functional theory (DFT) calculations. Two types of defects with different contrast were observed on a flat terrace by STM and AFM. Their STM contrast varies with bias voltage. In STS, they showed characteristic peaks at different energies, 1.1 and 1.4 eV. Comparison with DFT calculations indicates that they correspond to clusters of 3 and 4 Si dangling bonds, respectively. The relevance of these results for the optimization of graphene synthesis is discussed.