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A Ḿ-SAM/Hg junction can also be formed but is less stable. We will report studies of this junction separately.
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45
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Short-chain alkanethiols (C4-C6) form mechanically stable junctions but immediately breakdown when a small potential (10 mV) is applied.
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A Hg-HDT/HDT-Ag junction was assembled and left for 1 h in contact. After disassembly of the junction, the contact area on the Ag-HDT surface was analyzed by XPS spectroscopy; no detectable levels of Hg were observed. In contrast a sample of Ag-HDT exposed to mercury vapor (in a closed chamber for 30 min), followed by successive washing with ethanol, showed significant levels of Hg on the Ag-HDT surface in the XPS spectrum.
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The absolute value of the current for the junction depends on the surrounding solvent and is higher in acetonitrile, water, and ethanol than in isooctane or hexadecane and perfluorononane. A larger separation of the two electrodes (cf. Figure 3) by an unpolar solvent can also be the cause for this observation.
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48
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85069138347
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note
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Another explanation for a slope lower than the theoretical slope in the capacitance vs contact area plot (Figure 3) might be that we have overestimated the contact area, based on the visual measurement of the contact diameter.
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49
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The addition of electrolytes might enhance electrochemical processes on the metal surfaces, such as cathodic stripping of the thiol; compare ref 7a,e.
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th-HDT surface was significantly higher: 2.2 ± 0.5 V. We attribute this observation to the effect of thermal annealing on of the gold surface, generating larger grains and fewer pinholes in the Au-SAM surface.
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For shorter alkanethiols (
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Theoretically the dependence of the current on the voltage is determined by the mechanism of conductivity, which is different for different voltage regimes. The complexity of the junction does not allow us to study this relationship.
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Silver provides a good surface for densly packed monolayers studied by various techniques; compare refs 5c, 6, 36.
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