Key to single-molecule electronics is connecting functional molecules to each other using conductive nanowires. This involves two issues: how to create conductive nanowires at designated positions, and how to ensure chemical bonding between the nanowires and functional molecules. Here, we present a novel method that solves both issues. Relevant functional molecules are placed on a self-assembled monolayer of diacetylene compound. A probe tip of a scanning tunneling microscope is then positioned on the molecular row of the diacetylene compound to which the functional molecule is adsorbed, and a conductive polydiacetylene nanowire is fabricated by initiating chain polymerization by stimulation with the tip. Since the front edge of chain polymerization necessarily has a reactive chemical species, the created polymer nanowire forms chemical bonding with an encountered molecular element. We name this spontaneous reaction "chemical soldering". First-principles theoretical calculations are used to investigate the structures and electronic properties of the connection. We demonstrate that two conductive polymer nanowires are connected to a single phthalocyanine molecule. A resonant tunneling diode formed by this method is discussed.
Single functional molecules offer great potential for the development of novel nanoelectronic devices with capabilities beyond today's silicon-based devices. To realise single-molecule electronics, the development of a viable method for connecting functional molecules to each other using single conductive polymer chains is required. The method of initiating chain polymerisation using the tip of a scanning tunnelling microscope (STM) is very useful for fabricating single conductive polymer chains at designated positions and thereby wiring single molecules. In this feature article, developments in the controlled chain polymerisation of diacetylene compounds and the properties of polydiacetylene chains are summarised. Recent studies of "chemical soldering", a technique enabling the covalent connection of single polydiacetylene chains to single functional molecules, are also introduced. This represents a key step in advancing the development of single-molecule electronics.
Spontaneous chain polymerization of molecules initiated by a scanning tunneling microscope tip is studied with a focus on its rate-determining factors. Such chain polymerization that happens in self-assembled monolayers (SAM) of diacetylene compound molecules, which results in a π-conjugated linear polydiacetylene nanowire, varies in its rate P depending on domains in the SAM and substrate materials. While the arrangement of diacetylene molecules is identical in every domain on a graphite substrate, it varies in different domains on a MoS(2) substrate. This structural variation enables us to investigate how P is affected by molecular geometry. An important determining factor of P is the distance between two carbon atoms which are to be bound by polymerization reaction, R; as R decreases by 0.1 nm, P increases ∼2 times. P for a MoS(2) substrate is ∼4 times higher (with the same value of R) than that for a graphite substrate because of higher mobility of molecules. The exciting correlation of the chain polymerization rate to the geometrical structure of the diacetylene molecules brings a deeper understanding of the mechanism of chain polymerization kinetics. In addition, the fabrication of one-dimensional conjugated polymer nanowires on a semiconducting MoS(2) substrate as demonstrated here may be of immense importance in the realization of future molecular devices.
We demonstrate here the wet chemical synthesis of cobalt doped
γ-Fe2O3
nanoparticles and the subsequent effect on magnetic properties with the variation in dopant
concentration. It is observed that cobalt can be homogeneously doped into the
γ-Fe2O3
lattice up to 5 mol% without any appreciable change in the particle size ( nm). Further increase in cobalt concentration (10 mol% here) resulted in an increase in
particle size ( nm) due to possible adsorption of a cobalt layer on the surface of
γ-Fe2O3
nanoparticles rather than complete doping in the iron oxide lattice. The ac
susceptibility measurements revealed an increase in blocking temperature
(TB) with percentage variation in cobalt doping (2–10%), indicating substitution of
Fe3+ ions by
Co2+ ions
in the γ-Fe2O3
lattice. The dc magnetization measurements showed an increase in saturation magnetization
only up to 5%, beyond which it significantly diminished. The reduction in saturation
magnetization is attributed to the contribution from surface anisotropy in cobalt coated
γ-Fe2O3
nanoparticles.
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