Role of Molecular Dipoles in Charge Transport across Large Area Molecular Junctions Delineated Using Isomorphic Self-Assembled Monolayers
journal contributionposted on 13.10.2017, 00:00 authored by Jiahao Chen, Symon Gathiaka, Zhengjia Wang, Martin Thuo
Delineating the role of dipoles in large area junctions that are based on self-assembled monolayers (SAMs) is challenging due to molecular tilt, surface defects, and interchain coupling among other features. To mitigate SAM-based effects in study of dipoles, we investigated tunneling rates across carboranesisostructural molecules that orient along the surface normal on Au (but bear different dipole moments) without changing the thickness, packing density, or morphology of the SAM. Using the Au-SAM//Ga2O3-EGaIn junction (where “//” = physisorption, “–” = chemisorption, and EGaIn is eutectic gallium–indium), we observe that molecules with dipole moments oriented along the surface normal (with dipole moment, p = 4.1D for both M9 and 1O2) gave lower currents than when the dipole is orthogonal (p = 1.1 D, M1) at ±0.5 V applied bias. Similarly, from transition voltage spectroscopy, the transition voltages, VT (volt), are significantly different. (0.5, 0.43, and 0.4 V for M1, M9, and 1O2, respectively). We infer that the magnitude and direction of a dipole moments significantly affect the rate of charge transport across large area junctions with Δ log|J| ≅ 0.4 per Debye. This difference is largely due to effect of the dipole moment on the molecule-electrode coupling strength, Γ, hence effect of dipoles is likely to manifest in the contact resistance, Jo, although in conformational flexible molecules field-induced effects are expected.