e junction and induces rectification in a temperature-independent charge-transport regime.25:T4d6,Charge transport across self-assembled monolayers (SAMs) has been widely studied. Discrepancies of charge tunneling data that arise from various studies, however, call for efforts to develop new statistical analytical approaches to understand charge tunneling across SAMs. Structure-property studies on charge tunneling across SAM-based junctions have largely been through comparison of average tunneling rates and associated variance. These early moments (especially the average) are dominated by barrier width-a static property of the junction. In this work, we show that analysis of higher statistical moments (skewness and kurtosis) reveals the dynamic nature of the tunnel junction. Intramolecular Keesom (dipole-dipole) interactions dynamically fluctuate with bias as dictated by stereoelectronic limitations. Analyzing variance in the distribution of tunneling data instead of the first statistical moment (average), for a series of n-alkanethiols containing internal amide and aromatic terminal groups, we observe that the direction of dipole moments affects molecule-electrode coupling. An applied bias induces changes in the tunneling probability, affecting the distribution of tunneling paths in large-area molecular junctions.26:T472,This paper describes Li-ion intercalation into a pyrenyl-terminated self-assembled monolayer (SAM) on gold, inspired by the graphite anode in a Li-ion battery, and its effect on tunneling performance in a molecular junction incorporating the SAM. As the concentration of the Li-ion precursor ([LiPF₆]) increased from 0 to 10^-2 M, the rectification ratio increased to ∼10². Further experiments revealed that the intercalation-induced changes in the orientation of PYR group and in the HOMO energy level account for the enhanced rectification. Treatment with high concentrations of LiPF₆ (from 10^-2 to 10⁰ M) yielded a considerable solid electrolyte interphase (SEI), mainly composed of LiF, on the surface of the SAM, resulting in the disappearance of rectification. This was attributed to renormalization of the HOMO level back to that of the intact SAM, caused by the SEI layer. Our work demonstrates the interplay among Li-ion intercalation, SEI, and tunneling in the molecular junction, benefiting the research of molecular electronics as well as SAM-based batteries.

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2	Applied Physics	2	2	406
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5	Natural Sciences	1	1	57

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