Uta Schlickum

Chiral kagome lattice from simple ditopic molecular bricks

Self-assembly techniques allow for the fabrication of highly organized architectures with atomic-level precision. Here, we report on molecular-level scanning tunneling microscopy observations demonstrating the supramolecular engineering of complex, regular, and long-range ordered periodic networks on a surface atomic lattice using simple linear molecular bricks. The length variation of the employed de novo synthesized linear dicarbonitrile polyphenyl molecules translates to distinct changes of the bonding motifs that lead to hierarchic order phenomena and unexpected changes of the surface tessellations. The achieved 2D organic networks range from a close-packed chevron pattern via a rhombic network to a hitherto unobserved supramolecular chiral kagomé lattice.

High-Quality 2D Metal-Organic Coordination Network Providing Giant Cavities within Mesoscale Domains

A surface-supported open metal-organic nanomesh featuring a 24 nm(2) cavity size and extending to mum domains was fabricated by Co-directed assembly of para-hexaphenyl-dicarbonitrile linker molecules in two dimensions. The metallosupramolecular lattice is thermally robust and resides fully commensurate on the employed Ag(111) substrate as directly verified by high-resolution scanning tunneling microscopy observations.

Temperature and magnetic field dependence of a Kondo system in the weak coupling regime

The Kondo effect arises due to the interaction between a localized spin and the electrons of a surrounding host. Studies of individual magnetic impurities by scanning tunneling spectroscopy have renewed interest in Kondo physics; however, a quantitative comparison with theoretical predictions remained challenging. Here we show that the zero-bias anomaly detected on an organic radical weakly coupled to a Au (111) surface can be described with astonishing agreement by perturbation theory as originally developed by Kondo 60 years ago. Our results demonstrate that Kondo physics can only be fully conceived by studying both temperature and magnetic field dependence of the resonance. The identification of a spin 1/2 Kondo system is of relevance not only as a benchmark for predictions for Kondo physics but also for correlated electron materials in general.

Does the Surface Matter? Hydrogen‐Bonded Chain Formation of an Oxalic Amide Derivative in a Two‐ and Three‐Dimensional Environment

We report on a multi-technique investigation of the supramolecular organisation of N,N-diphenyl oxalic amide under differently dimensioned environments, namely three-dimensional (3D) in the bulk crystal, and in two dimensions on the Ag(111) surface as well as on the reconstructed Au(111) surface. With the help of X-ray structure analysis and scanning tunneling microscopy (STM) we find that the molecules organize in hydrogen-bonded chains with the bonding motif qualitatively changed by the surface confinement. In two dimensions, the chains exhibit enantiomorphic order even though they consist of a racemic mixture of chiral entities. By a combination of the STM data with near-edge X-ray absorption fine-structure spectroscopy, we show that the conformation of the molecule adapts such that the local registry of the functional group with the substrate is optimized while avoiding steric hindrance of the phenyl groups. In the low coverage case, the length of the chains is limited by the Au(111) reconstruction lines restricting the molecules into fcc stacked areas. A kinetic Monte Carlo simulated annealing is used to explain the selective assembly in the fcc stacked regions.

Molecular Orbital Gates for Plasmon Excitation

Future combinations of plasmonics with nanometer-sized electronic circuits require strategies to control the electrical excitation of plasmons at the length scale of individual molecules. A unique tool to study the electrical plasmon excitation with ultimate resolution is scanning tunneling microscopy (STM). Inelastic tunnel processes generate plasmons in the tunnel gap that partially radiate into the far field where they are detectable as photons. Here we employ STM to study individual tris-(phenylpyridine)-iridium complexes on a C60 monolayer, and investigate the influence of their electronic structure on the plasmon excitation between the Ag(111) substrate and an Ag-covered Au tip. We demonstrate that the highest occupied molecular orbital serves as a spatially and energetically confined nanogate for plasmon excitation. This opens the way for using molecular tunnel junctions as electrically controlled plasmon sources.

Spin-polarized scanning tunneling microscope for imaging the in-plane magnetization

We present a spin-polarized scanning tunneling microscope (Sp–STM) for imaging the magnetic in-plane component of magnetic surfaces. Magnetic in-plane sensitivity is obtained by using a ferromagnetic ring as a Sp–STM tip. By periodically switching the magnetization of the ring, the spin-dependent tunnelingcurrent between the ring and a spin-polarized sample is measured. The topography and the spin polarization can be imaged at the same time. We resolved the 180° domain wall of Fe whiskers and antiferromagnetic coupled Mn layers on Fe(001).

Restoring the Co magnetic moments at interfacial Co-porphyrin arrays by site-selective uptake of iron.

Magnetochemistry recently emerged as a promising approach to control addressable spin arrays on surfaces. Here we report on the binding, spatial ordering, and magnetic properties of Fe on a highly regular Co-tetraphenylporphyrin (Co-TPP) template and highlight how the Fe controls the magnetism of the Co centers. As evidenced by scanning tunneling microscopy (STM) single Fe atoms attach to the saddle-shape conformers site-selectively in a unique coordination environment offered through a heptamer defined by the Co-N-C-C-C-N cyclic subunit. While the magnetic moment of Co is quenched for bare Co-TPP/Ag(111), the Fe presence revives it. Our X-ray magnetic circular dichroism (XMCD) experiments, complemented by density functional theory (DFT) calculations, evidence a ferromagnetic coupling between the Fe and the Co center concomitant with a complex charge redistribution involving the porphyrin ligand. Thus, we demonstrate an unusual metalloporphyrin coordination geometry that opens pathways to spatially order and engineer magnetic moments in surface-based nanostructures.

Dynamic control of plasmon generation by an individual quantum system.

Controlling light on the nanoscale in a similar way as electric currents has the potential to revolutionize the exchange and processing of information. Although light can be guided on this scale by coupling it to plasmons, that is, collective electron oscillations in metals, their local electronic control remains a challenge. Here, we demonstrate that an individual quantum system is able to dynamically gate the electrical plasmon generation. Using a single molecule in a double tunnel barrier between two electrodes we show that this gating can be exploited to monitor fast changes of the quantum system itself and to realize a single-molecule plasmon-generating field-effect transistor operable in the gigahertz range. This opens new avenues toward atomic scale quantum interfaces bridging nanoelectronics and nanophotonics.

Electric-Field-Driven Direct Desulfurization

The ability to elucidate the elementary steps of a chemical reaction at the atomic scale is important for the detailed understanding of the processes involved, which is key to uncover avenues for improved reaction paths. Here, we track the chemical pathway of an irreversible direct desulfurization reaction of tetracenothiophene adsorbed on the Cu(111) closed-packed surface at the submolecular level. Using the precise control of the tip position in a scanning tunneling microscope and the electric field applied across the tunnel junction, the two carbon-sulfur bonds of a thiophene unit are successively cleaved. Comparison of spatially mapped molecular states close to the Fermi level of the metallic substrate acquired at each reaction step with density functional theory calculations reveals the two elementary steps of this reaction mechanism. The first reaction step is activated by an electric field larger than 2 V nm-1, practically in absence of tunneling electrons, opening the thiophene ring and leading to a transient intermediate. Subsequently, at the same threshold electric field and with simultaneous injection of electrons into the molecule, the exergonic detachment of the sulfur atom is triggered. Thus, a stable molecule with a bifurcated end is obtained, which is covalently bound to the metallic surface. The sulfur atom is expelled from the vicinity of the molecule.

Strong paramagnon scattering in single atom Pd contacts

Among all transition metals, palladium (Pd) has the highest density of states at the Fermi energy at low temperatures yet does not fulfill the Stoner criterion for ferromagnetism. However, close proximity to magnetism renders it a nearly ferromagnetic metal, which hosts paramagnons, strongly damped spin fluctuations. Here we compare the total and the differential conductance of monoatomic contacts consisting of single Pd and cobalt (Co) atoms between Pd electrodes. Transport measurements reveal a conductance for Co of