Michael Frei

Van der Waals interactions at metal/organic interfaces at the single-molecule level

Van der Waals (vdW) interaction, and its subtle interplay with chemically specific interactions and surface roughness at metal/organic interfaces, is critical to the understanding of structure-function relations in diverse areas, including catalysis, molecular electronics and self-assembly. However, vdW interactions remain challenging to characterize directly at the fundamental, single-molecule level both in experiments and in first principles calculations with accurate treatment of the non-local, London dispersion interactions. In particular, for metal/organic interfaces, efforts so far have largely focused on model systems consisting of adsorbed molecules on flat metallic surfaces with minimal specific chemical interaction. Here we show, through measurements of single-molecule mechanics, that pyridine derivatives can bind to nanostructured Au electrodes through an additional binding mechanism beyond the chemically specific N-Au donor-acceptor bond. Using density functional theory simulations we show that vdW interactions between the pyridine ring and Au electrodes can play a key role in the junction mechanics. These measurements thus provide a quantitative characterization of vdW interactions at metal/organic interfaces at the single-molecule level.

Linker Dependent Bond Rupture Force Measurements in Single-Molecule Junctions

We use a modified conducting atomic force microscope to simultaneously probe the conductance of a single-molecule junction and the force required to rupture the junction formed by alkanes terminated with four different chemical link groups which vary in binding strength and mechanism to the gold electrodes. Molecular junctions with amine, methylsulfide, and diphenylphosphine terminated molecules show clear conductance signatures and rupture at a force that is significantly smaller than the measured 1.4 nN force required to rupture the single-atomic gold contact. In contrast, measurements with a thiol terminated alkane which can bind covalently to the gold electrode show conductance and force features unlike those of the other molecules studied. Specifically, the strong Au-S bond can cause structural rearrangements in the electrodes, which are accompanied by substantial conductance changes. Despite the strong Au-S bond and the evidence for disruption of the Au structure, the experiments show that on average these junctions also rupture at a smaller force than that measured for pristine single-atom gold contacts.

Correlating structure, conductance, and mechanics of silver atomic-scale contacts.

We measure simultaneously force and conductance of Ag metal point-contacts under ambient conditions at room temperature. We observe the formation of contacts with a conductance close to 1 G0, the quantum of conductance, which can be attributed to a single-atom contact, similar to those formed by Au. We also find two additional conductance features at ∼0.4 G0 and ∼1.3 G0, which have been previously ascribed to contacts with oxygen contaminations. Here, using a conductance cross-correlation technique, we distinguish three different atomic-scale structural motifs and analyze their rupture forces and stiffness. Our results allow us to assign the ∼0.4 G0 conductance feature to an Ag-O-Ag contact and the ∼1.3 G0 feature to an Ag-Ag single-atom contact with an oxygen atom in parallel. Utilizing complementary information from force and conductance, we thus demonstrate the correlation of conductance with the structural evolution at the atomic scale.

Temperature dependent tunneling conductance of single molecule junctions

We perform temperature dependent conductance measurements on sub-nanometer sized single molecules bound to gold electrodes using a scanning tunneling microscope-based break junction technique in Ultra-High Vacuum (UHV). We find a threefold increase in the conductance of amine-terminated conjugated molecules when the temperature increases from 4 K to 300 K in UHV. Furthermore, the conductance measured at 300 K in UHV is consistent with solution-based measurements under ambient conditions where the transport mechanism corresponds to off-resonant electron tunneling across the molecule. Our measurements indicate that at 300 K, conductance is largely independent of pressure or solvent around the junction. In addition, our data unambiguously show that temperature can affect the tunneling conductance of single molecule-metal junctions. We show that the structure of the metal electrodes that form in these junctions varies systematically with temperature, and hypothesize that this changing structure of the interfa...

Simultaneous Measurement of Force and Conductance Across Single Molecule Junctions

Measurement of electronics and mechanics of single molecules provides a fundamental understanding of conductance as well as bonding at the atomic scale. To study the mechanics at these length scales, we have built a conducting atomic force microscope (AFM) optimized for high displacement and force resolution. Here, we simultaneously measure conductance and force across single Au-molecule-Au junctions in order to obtain complementary information about the electronics and structure in these systems. First we show that single-atom Au contacts, which have a conductance of G0 (2e2/h), have a rupture force of about 1.4 nN, in excellent agreement with previous theoretical and experimental studies. For a series of amine and pyridine linked molecules which are bound to Au electrodes through an Au-N donor-acceptor bond, we observe that the rupture force depends on the backbone chemistry and can range from 0.5 to 0.8 nN. We also study junctions formed with molecules that bind through P-Au and S-Au interactions. We find that both the conductance signatures and junction evolution of covalent S-Au bond (thiolate) and a donor-acceptor S-Au bond (thiol) are dramatically different. Finally, we perform density functional theory based adiabatic molecular junction elongation and rupture calculations which give us an insight into the underlying mechanisms in these experiments.