Person:

Simeone, Felice

This paper describes rates of charge tunneling across self-assembled monolayers (SAMs) of compounds containing oligophenyl groups, supported on gold and silver, using Ga2O3/EGaIn as the top electrode. It compares the injection current, J0, and the attenuation constant, β, of the simplified Simmons equation, across oligophenyl groups (R = Phn; n = 1, 2, 3), with three different anchoring groups (thiol, HSR; methanethiol, HSCH2R; and acetylene, HC≡CR) that attach R to the template-stripped gold and silver substrates. The results demonstrate that the structure of the molecules between the anchoring group (-S- or -C≡C-) and the oligophenyl moiety significantly influences charge transport. SAMs of SPhn, and C≡CPhn on gold show similar values of β and log|J0| (β = 0.28 ± 0.03 Å-1 and log|J0| = 2.7 ± 0.1 for Au/SPhn; β = 0.30 ± 0.02 Å-1 and log|J0| = 3.0 ± 0.1 for Au/C≡CPhn). The introduction of a single intervening methylene (CH2) group, between the anchoring sulfur atom and the aromatic units to generate SAMs of SCH2Phn, increases β to ~0.6 Å-1 on both gold and silver substrates. (For n-alkanethiolates on gold the corresponding values are β = 0.76 Å-1 and log|J0| = 4.2). As a generalization, based on this and other work, it seems that increasing the height of the tunneling barrier in the region of the interfaces increases β, and may decrease J0; by contrast, it appears that lowering the height of the barrier at these interfaces has little influence on β or J0.

This paper compares rates of charge transport by tunneling across junctions with the structures (Ag^{TS}X(CH_2)_{2n}CH_3 //Ga_2O_3 /EGaIn \space) (n=1–8 and (X= -SCH_2-) and (O_2C-)); here (Ag^{TS}) is template-stripped silver, and EGaIn is the eutectic alloy of gallium and indium. Its objective was to compare the tunneling decay coefficient ((\beta), Å(^{−1})) and the injection current ((J_0), A cm(^{−2})) of the junctions comprising SAMs of n-alkanethiolates and n-alkanoates. Replacing (Ag^{TS}SCH_2-R) with (Ag^{TS}O_2C-R) (R=alkyl chains) had no significant influence on (J_0) (ca. (3\times10^3 A cm^{−2})) or (\beta) (0.75–0.79 Å(^{−1}))—an indication that such changes (both structural and electronic) in the (Ag^{TS}XR) interface do not influence the rate of charge transport. A comparison of junctions comprising oligo(phenylene)carboxylates and n-alkanoates showed, as expected, that (\beta) for aliphatic (0.79 Å(^{−1})) and aromatic (0.60 Å(^{−1})) SAMs differed significantly.