Tunneling across SAMs Containing Oligophenyl Groups
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CitationBowers, Carleen M., Dmitrij Rappoport, Mostafa Baghbanzadeh, Felice C. Simeone, Kung-Ching Liao, Sergey N. Semenov, Tomasz Żaba, Piotr Cyganik, Alan Aspuru-Guzik, and George M. Whitesides. 2016. Tunneling Across SAMs Containing Oligophenyl Groups. The Journal of Physical Chemistry C 120, no. 21: 11331–11337. doi:10.1021/acs.jpcc.6b01253. http://dx.doi.org/10.1021/acs.jpcc.6b01253.
AbstractThis 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.
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