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Issue 19, 2018
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Why one can expect large rectification in molecular junctions based on alkane monothiols and why rectification is so modest

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Abstract

Many attempts to obtain high current rectification ratios (RRs) in molecular electronics are triggered by a potentiometer rule argument, which predicts that a strongly asymmetric location of the dominant molecular orbital yields large RR-values. Invoking this argument, molecular junctions based on alkane monothiols (CnT) can be expected to exhibit high RRs; the HOMO of these molecules is localized on the thiol terminal group bonded to one electrode. The extensive current–voltage (IV) results for CP-AFM (conducting probe atomic force microscope) CnT junctions of various molecular lengths (n = 7, 8, 9, 10, and 12) and different metallic contacts (Ag, Au, and Pt) are consistent with conduction dominated by the HOMO, but the measured RR ∼ 1.5 is much smaller than that predicted by the potentiometer rule framework. Further, the linear shift in the HOMO position with applied bias, γ, which gives rise to rectification, is also smaller than expected, and critically, γ has the opposite sign from potentiometer rule predictions. Companion ab initio OVGF (outer valence Green's function) quantum chemical calculations provide important insight. Namely, a linear Stark shift γm is calculated for the HOMO of CnT molecules for electric field strengths (106–107 V cm−1) typical of molecular junctions, and the sign of γm matches the sign of the experimental γ for junctions derived from transport measurements, suggesting that the Stark effect plays an important role. However, the magnitude of the measured γ is only 10–15% of the computed value γm. We propose that this implies that the contacts are far from optimal; they substantially screen the effect of the applied bias, possibly via molecule–electrode interface states. We predict that, with optimized contacts, the rectification ratios in CnT-based junctions can reach reasonably high values (RR ≈ 500). We believe that Stark shifts and limited current rectification due to non-ideal contacts discussed here for the specific case of alkane monothiol junctions are issues of general interest for molecular electronics that deserve further consideration.

Graphical abstract: Why one can expect large rectification in molecular junctions based on alkane monothiols and why rectification is so modest

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Publication details

The article was received on 27 Feb 2018, accepted on 07 Apr 2018 and first published on 09 Apr 2018


Article type: Edge Article
DOI: 10.1039/C8SC00938D
Citation: Chem. Sci., 2018,9, 4456-4467
  • Open access: Creative Commons BY license
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    Why one can expect large rectification in molecular junctions based on alkane monothiols and why rectification is so modest

    Z. Xie, I. Bâldea and C. D. Frisbie, Chem. Sci., 2018, 9, 4456
    DOI: 10.1039/C8SC00938D

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