Probing Energy-Level Alignment in Molecular Multilayers by Frequency-Modulation Electrostatic Force Microscopy under Tapping-Mode-Combined Fowler-Nordheim Tunneling Spectroscopy.

The alignment of molecular electronic levels in a molecular multilayer is of crucial importance to realize desired functions for molecular devices. Amplitude-modulation-feedback frequency-modulation electrostatic force microscopy combined with Fowler-Nordheim tunneling spectroscopy is utilized as a probe for the energy-level alignment in an organic multilayer. Bias-dependent electrostatic force spectra were examined for bilayers including a Ru complex as a benchmark multilayer system. Electrostatic properties in the low-bias region were captured well by a single-capacitor model, which indicates weak coupling at the bilayer interface between the Ru complex and self-assembled monolayer. In contrast, in the high-bias region, significant disagreement with the expected electrostatic force was recognized for the bilayers and evaluated as the loss of electrostatic energy through the Fowler-Nordheim tunneling process. Alignment of the lowest unoccupied molecular orbital (LUMO) level of the Ru complex was determined by Fowler-Nordheim emission through resonant tunneling. These results indicate an effective method to probe level alignment at interfaces inside multilayers and to provide the partition factor ß that depicts a divided electric field.

Visualization of Charge Migration in Conductive Polymers via Time-Resolved Electrostatic Force Microscopy.

Charge dynamics play an important role in numerous natural phenomena and artificial devices, and tracking charge migration and recombination is crucial for understanding the mechanism and function of systems involving charge transfer. Tip-synchronized pump-probe electrostatic force microscopy simultaneously permits highly sensitive detection, microsecond time resolution, and nanoscale spatial resolution, where the spatial distribution in static measurement (usual EFM) reflects differences in the carrier density and the time evolution reveals the surface carrier mobility. By using this method, carrier injection and ejection in sulfonated polyaniline (SPAN) thin films were visualized. Comparison of tr-EFM results of SPAN thin films with different doping levels revealed the individual differences in carrier density and mobility.

Chemical Control of Electronic Coupling between a Ruthenium Complex and Gold Electrode for Resonant Tunneling Conduction.

Current-voltage (I-V) nonlinearity is essential for information processing in molecular electronics. We used a nanoparticle bridge junction to investigate the effect of electronic coupling between a Ru complex and electrodes on nonlinear electrical properties. Two types of molecular layers, in which the Ru complex forms different chemical bondings to the electrode, were used for electrical measurements. The chemical bond and the surface potential of the Ru complex on Au electrodes were examined by X-ray photoelectron spectroscopy, infrared ray reflection absorbance spectroscopy and Kelvin probe force microscopy, respectively. The device, in which the Ru complex is directly bound to the Au electrode, indicated the nonlinear I-V characteristics with zero-bias conductance because of the direct tunneling conduction. Another device fabricated by inserting a spacer molecule between the Ru complex and the Au electrode realized nonlinear I-V characteristics with a clear threshold voltage and little zero-bias conductance. The I-V curves were well fitted by the resonant tunneling conduction model. The present results show the significance of controlling the electronic coupling for nonlinear I-V characteristics.

Resonant tunneling via a Ru-dye complex using a nanoparticle bridge junction.

Nonlinear current-voltage (I-V) characteristics is an important property for the realization of information processing in molecular electronics. We studied the electrical conduction through a Ru-dye complex (N-719) on a 2-aminoethanethiol (2-AET) monolayer in a nanoparticle bridge junction system. The nonlinear I-V characteristics exhibited a threshold voltage at around 1.2 V and little temperature dependence. From the calculation of the molecular states using density functional theory and the energy alignment between the electrodes and molecules, the conduction mechanism in this system was considered to be resonant tunneling via the HOMO level of N-719. Our results indicate that the weak electronic coupling of electrodes and molecules is essential for obtaining nonlinear I-V characteristics with a clear threshold voltage that reflect the intrinsic molecular state.