Mechanism of rectification in tunneling junctions based on molecules with asymmetric potential drops.

Autor: Nijhuis CA; Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, USA., Reus WF, Whitesides GM
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2010 Dec 29; Vol. 132 (51), pp. 18386-401. Date of Electronic Publication: 2010 Dec 02.
DOI: 10.1021/ja108311j
Abstrakt: This paper proposes a mechanism for the rectification of current by self-assembled monolayers (SAMs) of alkanethiolates with Fc head groups (SC(11)Fc) in SAM-based tunneling junctions with ultra-flat Ag bottom electrodes and liquid metal (Ga(2)O(3)/EGaIn) top electrodes. A systematic physical-organic study based on statistically large numbers of data (N = 300-1000) reached the conclusion that only one energetically accessible molecular orbital (the HOMO of the Fc) is necessary to obtain large rectification ratios R ≈ 1.0 × 10(2) (R = |J(-V)|/|J(V)| at ±1 V). Values of R are log-normally distributed, with a log-standard deviation of 3.0. The HOMO level has to be positioned spatially asymmetrically inside the junctions (in these experiments, in contact with the Ga(2)O(3)/EGaIn top electrode, and separated from the Ag electrode by the SC(11) moiety) and energetically below the Fermi levels of both electrodes to achieve rectification. The HOMO follows the potential of the Fermi level of the Ga(2)O(3)/EGaIn electrode; it overlaps energetically with both Fermi levels of the electrodes only in one direction of bias.
Databáze: MEDLINE