Oligothiophene wires: impact of torsional conformation on the electronic structure.

Charge transport in polymer- and oligomer-based semiconductor materials depends strongly on the structural ordering of the constituent molecules. Variations in molecular conformations influence the electronic structures of polymers and oligomers, and thus impact their charge-transport properties. In this study, we used Scanning Tunneling Microscopy and Spectroscopy (STM/STS) to investigate the electronic structures of different alkyl-substituted oligothiophenes displaying varied torsional conformations on the Au(111) surface. STM imaging showed that on Au(111), oligothiophenes self-assemble into chain-like structures, binding to each other via interdigitated alkyl ligands. The molecules adopted distinct planar conformations with alkyl ligands forming cis- or trans- mutual orientations. For each molecule, by using STS mapping, we identify a progression of particle-in-a-box-like states corresponding to the LUMO, LUMO+1 and LUMO+2 orbitals. Analysis of STS data revealed very similar unoccupied molecular orbital energies for different possible molecular conformations. By using density functional theory calculations, we show that the lack of variation in molecular orbital energies among the different oligothiophene conformers implies that the effect of the Au-oligothiophene interaction on molecular orbital energies is nearly identical for all studied torsional conformations. Our results suggest that cis-trans torsional disorder may not be a significant source of electronic disorder and charge carrier trapping in organic semiconductor devices based on oligothiophenes.

Charging and interaction of individual impurities in a monolayer organic crystal.

We use a scanning tunneling microscope to study the charging of Ag-doping centers in a monolayer of C(60) molecules supported on a thin Al(2)O(3) film grown on the NiAl(110) surface. Differential conductance spectroscopy shows that charging affects the conduction through C(60) molecules located around the doping centers. This effect is used to observe the electrostatic interaction of a pair of centers. Charging of one doping center affects the energy levels of the other, an analogue of the field-effect action.

Tunneling rates in electron transport through double-barrier molecular junctions in a scanning tunneling microscope.

The scanning tunneling microscope enables atomic-scale measurements of electron transport through individual molecules. Copper phthalocyanine and magnesium porphine molecules adsorbed on a thin oxide film grown on the NiAl(110) surface were probed. The single-molecule junctions contained two tunneling barriers, vacuum gap, and oxide film. Differential conductance spectroscopy shows that electron transport occurs via vibronic states of the molecules. The intensity of spectral peaks corresponding to the individual vibronic states depends on the relative electron tunneling rates through the two barriers of the junction, as found by varying the vacuum gap tunneling rate by changing the height of the scanning tunneling microscope tip above the molecule. A simple, sequential tunneling model explains the observed trends.

Vibrational spectroscopy of individual doping centers in a monolayer organic crystal.

A scanning tunneling microscope (STM) is used to study individual Ag doping centers in a monolayer of C60 molecules supported on a thin Al2O3 film grown on the NiAl(110) surface. Vibronic states of the doping centers are observed with differential conductance (dIdV) spectroscopy. The double-barrier nature of the junction results in bipolar transport: same states participate in charge transport at both bias voltage polarities. Identification of the dIdV features corresponding to bipolar conduction enables a new mode of vibrational spectroscopy with STM.

Mechanisms of reversible conformational transitions in a single molecule.

The reversible interconversion between two nonplanar conformations of single Zn(II) Etioporphyrin I molecules adsorbed on a NiAl(110) surface at 13 K was induced by a scanning tunneling microscope (STM). The threshold voltage for the conformational change at negative sample bias depends linearly on the tip-sample distance, suggesting an electrostatic force mechanism. The reverse conversion involves inelastic electron tunneling via a molecular electronic resonance at 1.25 eV. In contrast with the photon-induced conformational changes, an electrically induced mechanism is realized with the STM.

Control of relative tunneling rates in single molecule bipolar electron transport.

The influence of relative electron tunneling rates on electron transport in a double-barrier single-molecule junction is studied. The junction is defined by positioning a scanning tunneling microscope tip above a copper phthalocyanine molecule adsorbed on a thin oxide film grown on the NiAl(110) surface. By tuning the tip-molecule separation, the ratio of tunneling rates through the two barriers, vacuum and oxide, is controlled. This results in dramatic changes in the relative intensities of individual conduction channels, associated with different vibronic states of the molecule.

Vibronic states in single molecule electron transport.

A scanning tunneling microscope was used to study the electron transport through individual copper phthalocyanine molecules adsorbed on an ultrathin Al(2)O(3) film grown on a NiAl(110) surface. The differential conductance spectra display series of equally spaced features, which are attributed to vibronic states of individual molecules. The coupling of the electron current to the vibronic modes was observed to depend on the structures of the adsorbed molecules. Vibronic features were not observed for molecules adsorbed on the bare NiAl(110) surface due to spectral broadening.

Visualization and spectroscopy of a metal-molecule-metal bridge.

Artificial nanostructures, each composed of a copper(II) phthalocyanine (CuPc) molecule bonded to two gold atomic chains with a controlled gap, were assembled on a NiAl(110) surface by manipulation of individual gold atoms and CuPc molecules with a scanning tunneling microscope. The electronic densities of states of these hybrid structures were measured by spatially resolved electronic spectroscopy and systematically tuned by varying the number of gold atoms in the chains one by one. The present approach provides structural images and electronic characterization of the metal-molecule-metal junction, thereby elucidating the nature of the contacts between the molecule and metal in this junction.

Atomic engineering of photon emission with a scanning tunneling microscope.

We present measurements of photon emission from individual several-atom silver chains on the NiAl(110) surface, excited by tunneling electrons in a scanning tunneling microscope (STM). The chains were assembled by manipulating single silver atoms on the NiAl(110) surface with the STM. The photon energy of this emission can be tuned by appending a single atom to the chain. These changes in photon emission result from changes in the electronic structure of the silver chain, each electronic state inside the chain being associated with a distinct channel of emission.

Vibrationally resolved fluorescence excited with submolecular precision.

Tunneling electrons from a scanning tunneling microscope (STM) were used to excite photon emission from individual porphyrin molecules adsorbed on an ultrathin alumina film grown on a NiAl(110) surface. Vibrational features were observed in the light-emission spectra that depended sensitively on the different molecular conformations and corresponding electronic states obtained by scanning tunneling spectroscopy. The high spatial resolution of the STM enabled the demonstration of variations in light-emission spectra from different parts of the molecule. These experiments realize the feasibility of fluorescence spectroscopy with the STM and enable the integration of optical spectroscopy with a nanoprobe for the investigation of single molecules.