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 β that depicts a divided electric field.