Carbon-Based Molecular Junctions for Practical Molecular Electronics

The field of molecular electronics has grown rapidly since its experimental realization in the late 1990s, with thousands of publications on how molecules can act as circuit components and the possibility of extending microelectronic miniaturization. Our research group developed molecular junctions (MJs) using conducting carbon electrodes and covalent bonding, which provide excellent temperature tolerance and operational lifetimes. A carbon-based MJ based on quantum mechanical tunneling for electronic music represents the world's first commercial application of molecular electronics, with >3000 units currently in consumer hands. The all-carbon MJ consisting of aromatic molecules and oligomers between vapor-deposited carbon electrodes exploits covalent, C-C bonding which avoids the electromigration problem of metal contacts. The high bias and temperature stability as well as partial transparency of the all-carbon MJ permit a wide range of experiments to determine charge transport mechanisms and observe photoeffects to both characterize and stimulate operating MJs. As shown in the Conspectus figure, our group has reported a variety of electronic functions, many of which do not have analogs in conventional semiconductors. Much of the described research is oriented toward the rational design of electronic functions, in which electronic characteristics are determined by molecular structure.In addition to the fabrication of molecular electronic devices with sufficient stability and operating life for practical applications, our approach was directed at two principal questions: how do electrons move through molecules that are components of an electronic circuit, and what can we do with molecules that we cannot do with existing semiconductor technology? The central component is the molecular junction consisting of a 1-20+ nm layer of covalently bonded oligomers between two electrodes of conducting, mainly sp²-hybridized carbon. In addition to describing the unique junction structure and fabrication methods, this Account summarizes the valuable insights available from photons used both as probes of device structure and dynamics and as prods to stimulate resonant transport through molecular orbitals.Short-range (<5 nm) transport by tunneling and its properties are discussed separately from the longer-range transport (5-60 nm) which bridges the gap between tunneling and transport in widely studied organic semiconductors. Most molecular electronic studies deal with the <5 nm thickness range, where coherent tunneling is generally accepted as the dominant transport mechanism. However, the rational design of devices in this range by changing molecular structure is frustrated by electronic interactions with the conducting contacts, resulting in weak structural effects on electronic behavior. When the molecular layer thickness exceeds 5 nm, transport characteristics change completely since molecular orbitals become the conduits for transport. Incident photons can stimulate transport, with the observed photocurrent tracking the absorption spectrum of the molecular layer. Low-temperature, activationless transport of photogenerated carriers is possible for up to at least 60 nm, with characteristics completely distinct from coherent tunneling and from the hopping mechanisms proposed for organic semiconductors. The Account closes with examples of phenomena and applications enabled by molecular electronics which may augment conventional microelectronics with chemical functions such as redox charge storage, orbital transport, and energy-selective photodetection.