Controlling piezoresistance in single molecules through the isomerisation of bullvalenes

Journal Publication ResearchOnline@JCU
Reimers, Jeffrey R.;Li, Tiexin;Birvé, André;Yang, Likun;Aragonès, Albert C.;Fallon, Thomas;Kosov, Daniel S.;Darwish, Nadim
Abstract

Nanoscale electro-mechanical systems (NEMS) displaying piezoresistance offer unique measurement opportunities at the sub-cellular level, in detectors and sensors, and in emerging generations of integrated electronic devices. Here, we show a single-molecule NEMS piezoresistor that operates utilising constitutional and conformational isomerisation of individual diaryl-bullvalene molecules and can be switched at 850 Hz. Observations are made using scanning tunnelling microscopy break junction (STMBJ) techniques to characterise piezoresistance, combined with blinking (current-time) experiments that follow single-molecule reactions in real time. A kinetic Monte Carlo methodology (KMC) is developed to simulate isomerisation on the experimental timescale, parameterised using density-functional theory (DFT) combined with non-equilibrium Green’s function (NEGF) calculations. Results indicate that piezoresistance is controlled by both constitutional and conformational isomerisation, occurring at rates that are either fast (equilibrium) or slow (non-equilibrium) compared to the experimental timescale. Two different types of STMBJ traces are observed, one typical of traditional experiments that are interpreted in terms of intramolecular isomerisation occurring on stable tipped-shaped metal-contact junctions, and another attributed to arise from junction‒interface restructuring induced by bullvalene isomerisation.

Journal

Nature Communications

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Volume

14

ISBN/ISSN

2041-1723

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1

Pages Count

13

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Publisher

Nature Publishing Group

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DOI

10.1038/s41467-023-41674-z