Capturing the embryonic stages of self-assembly - design rules for molecular computation.

The drive towards organic computing is gaining momentum. Interestingly, the building blocks for such architectures is based on molecular ensembles extending from nucleic acids to synthetic molecules. Advancement in this direction requires devising precise nanoscopic experiments and model calculations to decipher the mechanisms governing the integration of a large number of molecules over time at room-temperature. Here, we report on ultrahigh-resolution scanning tunnelling microscopic measurements to register the motion of molecules in the absence of external stimulus in liquid medium. We observe the collective behavior of individual molecules within a swarm which constantly iterate their position to attain an energetically favourable site. Our approach provides a consistent pathway to register molecular self-assembly in sequential steps from visualising thermodynamically driven repair of defects up until the formation of a stable two-dimensional configuration. These elemental findings on molecular surface dynamics, self-repair and intermolecular kinetic pathways rationalised by atom-scale simulations can be explored for developing new models in algorithmic self-assembly to realisation of evolvable hardware.

Nanoscale origin of defects at metal/molecule engineered interfaces.

The control and repair of defects at metal/molecule interfaces is central to the realization of molecular electronic circuits with reproducible performance. The fundamental mechanism governing defect (pore) evolution on mica-supported metal surfaces, its propagation in self-assembled molecular layers, and its implications for molecular junction devices are discussed. Pore eradication by replacing mica with halide platforms coupled with elevated substrate temperature during metal deposition yields exceptionally ultraflat metal landscapes. In situ scanning tunneling microscopy further substantiates molecular locking at defect sites and upon defect healing; the emergence of a closely packed 2-D molecular architecture is demonstrated with nanometer-scale spatial resolution in liquids.

Manipulating connectivity and electrical conductivity in metallic nanowire networks.

Connectivity in metallic nanowire networks with resistive junctions is manipulated by applying an electric field to create materials with tunable electrical conductivity. In situ electron microscope and electrical measurements visualize the activation and evolution of connectivity within these networks. Modeling nanowire networks, having a distribution of junction breakdown voltages, reveals universal scaling behavior applicable to all network materials. We demonstrate how local connectivity within these networks can be programmed and discuss material and device applications.

Nanoscale mapping of electrical resistivity and connectivity in graphene strips and networks.

In this article we map out the thickness dependence of the resistivity of individual graphene strips, from single layer graphene through to the formation of graphitic structures. We report exceptionally low resistivity values for single strips and demonstrate that the resistivity distribution for single strips is anomalously narrow when compared to bi- and trilayer graphene, consistent with the unique electronic properties of single graphene layers. In agreement with theoretical predictions, we show that the transition to bulklike resistivities occurs at seven to eight layers of graphene. Moreover, we demonstrate that the contact resistance between graphene flakes in a graphene network scales with the flake thickness and the implications for transparent conductor applications are discussed.

Selective tuning and optimization of the contacts to metallic and semiconducting single-walled carbon nanotubes.

Conductance imaging atomic force microscopy was used to probe the electrical interface between single-walled carbon nanotubes and metal electrodes. The contact resistance was optimized by applying a local voltage pulse (approximately 2 s) using a conductive probe with controlled loading force to the region of the metal electrode contacting the nanotube. Using this technique, we show that Pd forms superior contacts, resulting in contact resistance values that are among the lowest ever reported.

Electrical connectivity in single-walled carbon nanotube networks.

Transport in single-walled carbon nanotubes (SWCNTs) networks is shown to be dominated by resistance at network junctions which scale with the size of the interconnecting bundles. Acid treatment, known to dope individual tubes, actually produces a dramatic reduction in junction resistances, whereas annealing significantly increases this resistance. Measured junction resistances for pristine, acid-treated and annealed SWCNT bundles correlate with conductivities of the corresponding films, in excellent agreement with a model in which junctions control the overall network performance.

Silver Nanowire Networks as Flexible, Transparent, Conducting Films: Extremely High DC to Optical Conductivity Ratios.

We have used aqueous dispersions of silver nanowires to prepare thin, flexible, transparent, conducting films. The nanowires are of length and diameter close to 6.5 µm and 85 nm, respectively. At low thickness, the films consist of networks but appear to become bulk-like for mean film thicknesses above ∼160 nm. These films can be very transparent with optical transmittance reaching as high as 92% for low thickness. The transmittance (550 nm) decreases with increasing thickness, consistent with an optical conductivity of 6472 S/m. The films are also very uniform; the transmittance varies spatially by typically <2%. The sheet resistance decreases with increasing thickness, falling below 1 Ω/◻ for thicknesses above 300 nm. The DC conductivity increases from 2 × 10(5) S/m for very thin films before saturating at 5 × 10(6) S/m for thicker films. Similarly, the ratio of DC to optical conductivity increases with increasing thickness from 25 for the thinnest films, saturating at ∼500 for thicknesses above ∼160 nm. We believe this is the highest conductivity ratio ever observed for nanostructured films and is matched only by doped metal oxide films. These nanowire films are electromechanically very robust, with all but the thinnest films showing no change in sheet resistance when flexed over >1000 cycles. Such results make these films ideal as replacements for indium tin oxide as transparent electrodes. We have prepared films with optical transmittance and sheet resistance of 85% and 13 Ω/◻, respectively. This is very close to that displayed by commercially available indium tin oxide.

Transparent, flexible, and highly conductive thin films based on polymer-nanotube composites.

We have prepared flexible, transparent, and very conducting thin composite films from poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), filled with both arc discharge and HIPCO single-walled nanotubes, at high loading level. The films are of high optical uniformity. The arc discharge nanotube-filled composites were significantly more conductive, demonstrating DC conductivities of >10(5) S/m for mass fractions >50 wt %. The ratio of DC to optical conductivity was higher for composites with mass fractions of 55-60 wt % than for nanotube-only films. For an 80 nm thick composite, filled with 60 wt % arc discharge nanotubes, this conductivity ratio was maximized at sigma(DC)/sigma(Op) = 15. This translates into transmittance (550 nm) and sheet resistance of 75 and 80 Omega/square, respectively. These composites were electromechanically very stable, showing <1% resistance change over 130 bend cycles.