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Odd–Even Effects in Charge Transport across n-Alkanethiolate-Based SAMs

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Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, United States
Department of Statistics, Shiraz University, Shiraz, Iran
§ Department of Chemistry and Biochemistry, University of Windsor, 401 Sunset Avenue, Windsor, Ontario Canada, N9B3P4
Wyss Institute of Biologically Inspired Engineering, 60 Oxford Street, Cambridge, Massachusetts 02138, United States
Cite this: J. Am. Chem. Soc. 2014, 136, 48, 16919–16925
Publication Date (Web):November 7, 2014
https://doi.org/10.1021/ja509436k
Copyright © 2014 American Chemical Society
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Abstract

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This paper compares rates of charge transport across self-assembled monolayers (SAMs) of n-alkanethiolates having odd and even numbers of carbon atoms (nodd and neven) using junctions with the structure MTS/SAM//Ga2O3/EGaIn (M = Au or Ag). Measurements of current density, J(V), across SAMs of n-alkanethiolates on AuTS and AgTS demonstrated a statistically significant odd–even effect on AuTS, but not on AgTS, that could be detected using this technique. Statistical analysis showed the values of tunneling current density across SAMs of n-alkanethiolates on AuTS with nodd and neven belonging to two separate sets, and while there is a significant difference between the values of injection current density, J0, for these two series (log|J0Au,even| = 4.0 ± 0.3 and log|J0Au,odd| = 4.5 ± 0.3), the values of tunneling decay constant, β, for nodd and neven alkyl chains are indistinguishable (βAu,even = 0.73 ± 0.02 Å–1, and βAu,odd= 0.74 ± 0.02 Å–1). A comparison of electrical characteristics across junctions of n-alkanethiolate SAMs on gold and silver electrodes yields indistinguishable values of β and J0 and indicates that a change that substantially alters the tilt angle of the alkyl chain (and, therefore, the thickness of the SAM) has no influence on the injection current density across SAMs of n-alkanethiolates.

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The experimental procedures, synthesis characterization of the alkanethiols, histograms of J(V) data, and statistical analysis details. This material is available free of charge via the Internet at http://pubs.acs.org.

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