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note
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The electron transport data in refs 15 and 17 were analyzed using the Schottky thermionic emission model, including an empirical correction for the organic monolayer. We find, though, that data in the low bias regime can be characterized by a single mechanism, thermionic emission, without the need to include a term for the monolayer.
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note
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+-Si was due to the formation of metallic filamentary pathways formed during evaporation of metal onto the SAM. Indeed, we encountered this problem of shorting in (unpublished) experiments with indirectly evaporated Au contacts on alkyl monolayers. However, we never saw evidence for it with our Hg/alkylC-Si junctions. This is not surprising because formation of filamentary shorts with the high surface tension Hg contact and the very smooth substrates that we use is rather improbable, unless large pinholes are present. Simple wetting calculations, using a 150° Hg/alkyl monolayer contact angle and a 2 nm thick monolayer, show that only if the (circular) pinhole is well over 5 nm in diameter, can we get direct Hg-substrate contact. Naturally, at some distance between Hg and substrate, before direct Hg/substrate contact is reached, tunneling through vacuum (between the Hg surface and the pinhole bottom) can become favored over transport through the molecules. The distance where this will occur will depend on the mechanism of tunneling through the molecular monolayer.
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33747203649
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note
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Assuming a densely packed monolayer with fully extended (all trans bonds) chains, the thickness, d, of the monolayer as deduced from ellipsometry, is given by d = 1.86 Å + L cos α, where L is the length of the alkyl chain and a is the tilt angle of the chain from surface normal. 1.86 Å is the length of the Si-C bond, which is normal to the surface for Si(111). The length L of the alkyl chain was calculated based on standard bond lengths (C-C, 1.53 Å; C-H 1.11 A) and angles (111°), using the formula L = 1.26(n-1) + 0.9, where n is the number of carbons in the alkyl chain.
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2 or water). We can then subtract the contribution of the oxygen (% O1s) in the thickness calculation. We note, though, that even considering the 0 in the calculation gives less than 0.1 nm extra thickness for the organic monolayer.
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The barrier height of GaAs semiconductors can be controlled by incomplete monolayers. See the Supporting Information for a more detailed discussion and references.
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