Towards molecular electronic devices based on ‘all-carbon’ wires

Abstract

Nascent molecular electronic devices based on linear 'all-carbon' wires attached to gold electrodes through robust and reliable C-Au contacts are prepared via efficient in situ sequential cleavage of trimethylsilyl end groups from an oligoyne, Me₃Si-(C[triple bond, length as m-dash]C)₄-SiMe₃ (1). In the first stage of the fabrication process, removal of one trimethylsilyl (TMS) group in the presence of a gold substrate, which ultimately serves as the bottom electrode, using a stoichiometric fluoride-driven process gives a highly-ordered monolayer, Au|C[triple bond, length as m-dash]CC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CSiMe₃ (Au|C₈SiMe₃). In the second stage, treatment of Au|C₈SiMe₃ with excess fluoride results in removal of the remaining TMS protecting group to give a modified monolayer Au|C[triple bond, length as m-dash]CC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CH (Au|C₈H). The reactive terminal C[triple bond, length as m-dash]C-H moiety in Au|C₈H can be modified by 'click' reactions with (azidomethyl)ferrocene (N₃CH₂Fc) to introduce a redox probe, to give Au|C₆C₂N₃HCH₂Fc. Alternatively, incubation of the modified gold substrate supported monolayer Au|C₈H in a solution of gold nanoparticles (GNPs), results in covalent attachment of GNPs on top of the film via a second alkynyl carbon-Au σ-bond, to give structures Au|C₈|GNP in which the monolayer of linear, 'all-carbon' C₈ chains is sandwiched between two macroscopic gold contacts. The covalent carbon-surface bond as well as the covalent attachment of the metal particles to the monolayer by cleavage of the alkyne C-H bond is confirmed by surface-enhanced Raman scattering (SERS). The integrity of the carbon chain in both Au|C₆C₂N₃HCH₂Fc systems and after formation of the gold top-contact electrode in Au|C₈|GNP is demonstrated through electrochemical methods. The electrical properties of these nascent metal-monolayer-metal devices Au|C₈|GNP featuring 'all-carbon' molecular wires were characterised by sigmoidal I-V curves, indicative of well-behaved junctions free of short circuits.