Optical probes of molecules as nano-mechanical switches

Molecular electronics promises a new generation of ultralow-energy information technologies, based around functional molecular junctions. Here, we report optical probing that exploits a gold nanoparticle in a plasmonic nanocavity geometry used as one terminal of a well-defined molecular junction, deposited as a self-assembled molecular monolayer on flat gold. A conductive transparent cantilever electrically contacts individual nanoparticles while maintaining optical access to the molecular junction. Optical readout of molecular structure in the junction reveals ultralow-energy switching of similar to 50zJ, from a nano-electromechanical torsion spring at the single molecule level. Real-time Raman measurements show these electronic device characteristics are directly affected by this molecular torsion, which can be explained using a simple circuit model based on junction capacitances, confirmed by density functional theory calculations. This nanomechanical degree of freedom is normally invisible and ignored in electrical transport measurements but is vital to the design and exploitation of molecules as quantum-coherent electronic nanodevices. The development of molecular electronics at single molecule level calls for new tools beyond electrical characterisation. Kos et al. show an optical probe of molecular junctions in a plasmonic nanocavity geometry, which supports in situ interrogation of molecular configurations.