Comparison of DC and AC Transport in 1.5–7.5 nm Oligophenylene Imine Molecular Wires across Two Junction Platforms: Eutectic Ga–In versus Conducting Probe Atomic Force Microscope Junctions

We have utilized DC and AC transport measurements to measure the resistance and capacitance of thin films of conjugated oligophenyleneimine (OPI) molecules ranging from 1.5 to 7.5 nm in length. These films were synthesized on Au surfaces utilizing the imine condensation chemistry between terephthalaldehyde and 1,4-benzenediamine. Near edge X-ray absorption fine structure (NEXAFS) spectroscopy yielded molecular tilt angles of 33–43°. To probe DC and AC transport, we employed Au–S–OPI//GaO_x/EGaIn junctions having contact areas of 9.6 × 10² μm² (10⁹ nm²) and compared to previously reported DC results on the same OPI system obtained using Au–S–OPI//Au conducting probe atomic force microscopy (CP-AFM) junctions with 50 nm² areas. We found that intensive observables agreed very well across the two junction platforms. Specifically, the EGaIn-based junctions showed: (i) a crossover from tunneling to hopping transport at molecular lengths near 4 nm; (ii) activated transport for wires >4 nm in length with an activation energy of 0.245 ± 0.008 eV for OPI-7; (iii) exponential dependence of conductance with molecular length with a decay constant β = 2.84 ± 0.18 nm^–1 (DC) and 2.92 ± 0.13 nm^–1 (AC) in the tunneling regime, and an apparent β = 1.01 ± 0.08 nm^–1 (DC) and 0.99 ± 0.11 nm^–1 (AC) in the hopping regime; (iv) previously unreported dielectric constant of 4.3 ± 0.2 along the OPI wires. However, the absolute resistances of Au–S–OPI//GaO_x/EGaIn junctions were approximately 100 times higher than the corresponding CP-AFM junctions due to differences in metal–molecule contact resistances between the two platforms.