Robin Ohmann

Portrait of the potential barrier at metal-organic nanocontacts

Electron transport through metal-molecule contacts greatly affects the operation and performance of electronic devices based on organic semiconductors and is at the heart of molecular electronics exploiting single-molecule junctions. Much of our understanding of the charge injection and extraction processes in these systems relies on our knowledge of the potential barrier at the contact. Despite significant experimental and theoretical advances a clear rationale of the contact barrier at the single-molecule level is still missing. Here, we use scanning tunnelling microscopy to probe directly the nanocontact between a single molecule and a metal electrode in unprecedented detail. Our experiments show a significant variation on the submolecular scale. The local barrier modulation across an isolated 4-[trans-2-(pyrid-4-yl-vinyl)] benzoic acid molecule bound to a copper(111) electrode exceeds 1 eV. The giant modulation reflects the interaction between specific molecular groups and the metal and illustrates the critical processes determining the interface potential. Guided by our results, we introduce a new scheme to locally manipulate the potential barrier of the molecular nanocontacts with atomic precision.

Rational Design of Two-Dimensional Nanoscale Networks by Electrostatic Interactions at Surfaces

The self-assembly of aromatic carboxylic acids and cesium adatoms on a Cu(100) surface at room temperature has been investigated by scanning tunneling microscopy and X-ray photoelectron spectroscopy. The highly ordered molecular nanostructures are comprised of a central ionic coupling motif between the anionic carboxylate moieties and Cs cations that generate distinctive chiral arrangements of the network structures. The primary electrostatic interaction results in highly flexible bond lengths and geometries. The adsorbate-substrate coupling is found to be important for the determination of the structures. With the use of rod-like carboxylic linker molecules, the dimension of the porous networks can be tuned through the variation of the aromatic backbone length.

Moving Nanostructures: Pulse-Induced Positioning of Supramolecular Assemblies

For the development of nanoscale devices, the manipulation of single atoms and molecules by scanning tunneling microscopy is a well-established experimental technique. However, for the construction of larger and higher order structures, it is important to move not only one adsorbate but also several at the same time. Additionally, a major issue in standard manipulation experiments is the strong mechanical interaction of the tip apex and the adsorbate, which can damage the system under investigation. Here, we present a purely electronic excitation method for the controlled movement of a weakly interacting assembly of a few molecules. By applying voltage pulses, this supramolecular nanostructure is moved in a controlled manner without losing its collective integrity. Depending on the polarity and location of the applied voltage, the movement can be driven in predefined directions. Our gentle purely electronic approach for the controlled manipulation of nanostructures opens new ways to construct molecular devices.

Image potential states as a quantum probe of graphene interfaces

Image potential states (IPSs) are electronic states localized in front of a surface in a potential well, formed by the surface projected bulk band gap on one side and the image potential barrier on the other. In the limit of a two-dimensional solid, a double Rydberg series of IPSs has been predicted, which is in contrast to a single series present in three-dimensional solids. Here, we confirm this prediction experimentally for mono- and bilayer graphene. The IPSs of epitaxial graphene on SiC are measured by scanning tunneling spectroscopy and the results are compared with ab-initio band structure calculations. Despite the presence of the substrate, both calculations and experimental measurements show that the first pair of the double series of IPSs survives and eventually evolves into a single series for graphite. Thus, IPSs provide an elegant quantum probe of the interfacial coupling in graphene systems.

Kondo Effect in Single Atom Contacts: The Importance of the Atomic Geometry

Co single atom junctions on copper surfaces are studied by scanning tunneling microscopy and ab initio calculations. The Kondo temperature of single cobalt atoms on the Cu(111) surface has been measured at various tip-sample distances ranging from tunneling to the point contact regime. The experiments show a constant Kondo temperature for a whole range of tip-substrate distances consistently with the predicted energy position of the spin-polarized d levels of Co. This is in striking difference to experiments on Co/Cu(100) junctions, where a substantial increase of the Kondo temperature has been found. Our calculations reveal that the different behavior of the Co adatoms on the two Cu surfaces originates from the interplay between the structural relaxations and the electronic properties in the near-contact regime.

Surveying molecular vibrations during the formation of metal−molecule nanocontacts

Molecular junctions have been characterized to determine the influence of the metal contact formation in the electron transport process through a single molecule. With inelastic electron tunneling spectroscopy and first-principles calculations, the vibration modes of a carbon monoxide molecule have been surveyed as a function of the distance from a copper electrode with unprecedented accuracy. We observe a continuous but nonlinear blue shift of the frustrated rotation mode in tunneling with decreasing distance followed by an abrupt softening upon contact formation. This indicates that the presence of the metal electrode sensibly alters the structural and conductive properties of the junction even without the formation of a strong chemical bond.

STM manipulation of a subphthalocyanine double-wheel molecule on Au(111).

A new class of double-wheel molecules is manipulated on a Au(111) surface by the tip of a scanning tunneling microscope (STM) at low temperature. The double-wheel molecule consists of two subphthalocyanine wheels connected by a central rotation carbon axis. Each of the subphthalocyanine wheels has a nitrogen tag to monitor its intramolecular rolling during an STM manipulation sequence. The position of the tag can be followed by STM, allowing us to distinguish between the different lateral movements of the molecule on the surface when manipulated by the STM tip.

Actuated transitory metal−ligand bond as tunable electromechanical switch

Electrically tunable molecules are highly attractive for the construction of molecular devices, such as switches, transistors, or machines. Here, we present a novel nanomechanical element triggered by an electrical bias as external stimulus. We demonstrate that a transitory chemical bond between a copper atom and coordinating organic molecules adsorbed on a metal surface acts as variable frequency switch, which can be actuated and probed by means of low-temperature scanning tunneling microscopy. Whereas below a threshold bias voltage the bond is permanently either formed or broken the bonding state continuously oscillates at higher voltages. The switching rate of the bistable molecular system can be widely tuned from below 1 Hz up to the kilohertz regime. The quantum yield per tunneling electron to trigger a transition between the two states varies spatially and is related to the local density of states of the bonded and nonbonded configuration.

Influence of Subsurface Layers on the Adsorption of Large Organic Molecules on Close-Packed Metal Surfaces

The asymmetric molecule 4-[trans-2-(pyrid-4-yl-vinyl)] benzoic acid (PVBA) adsorbed on Cu(111) is characterized by scanning tunneling microscopy (STM) and density functional theory (DFT) to determine the influence of subsurface atomic layers on the adsorption. In contrast to the 6-fold symmetry of the first atomic layer of close-packed surfaces, we find that the arrangement of the isolated molecules follows predominantly a 3-fold symmetry. This reduction in symmetry, where the molecule selects a specific orientation along the ⟨-211⟩ axes, reveals the contribution of lower-lying Cu layers to the molecular arrangement. Our calculations rationalize the interaction of the substrate with the molecule in terms of electrostatic screening and local relaxation phenomena.

Supramolecular Rotor and Translator at Work: On-Surface Movement of Single Atoms

A supramolecular nanostructure composed of four 4-acetylbiphenyl molecules and self-assembled on Au (111) was loaded with single Au adatoms and studied by scanning tunneling microscopy at low temperature. By applying voltage pulses to the supramolecular structure, the loaded Au atoms can be rotated and translated in a controlled manner. The manipulation of the gold adatoms is driven neither by mechanical interaction nor by direct electronic excitation. At the electronic resonance and driven by the tunneling current intensity, the supramolecular nanostructure performs a small amount of work of about 8 × 10(-21) J, while transporting the single Au atom from one adsorption site to the next. Using the measured average excitation time necessary to induce the movement, we determine the mechanical motive power of the device, yielding about 3 × 10(-21) W.