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  • Nanocircuit Switch Found?
Mar 2009
BERKELEY, Calif., March 4, 2009 – Simply pushing or pulling a molecular junction turns the electrical resistance flowing through the nanometer-scale circuit on or off, researchers have discovered. The feature could be exploited as a switch in future nanoscale electronics devices.

Researchers at Lawrence Berkeley National Laboratory (Berkeley Lab) and Columbia University were studying how electrons flow through such a molecular junction – a tiny circuit element that contacts gold atoms with a single molecule – when they discovered the potential on-off switch.
Jeffrey Neaton, director of the Theory of Nanostructured Materials facility at The Molecular Foundry. (Photo: Roy Kaltschmidt, Berkeley Lab Public Affairs)
“To design circuit elements at the molecular scale, we need to understand how the intrinsic properties of a molecule or junction are actually connected to its measured resistance,” said Jeff Neaton, facility director of the Theory of Nanostructured Materials Facility in the Molecular Foundry at Berkeley Lab. “Knowing where each and every atom is in a single-molecule junction is simply beyond what’s possible with experiments at this stage. For these subnanometer scale junctions – just a handful of atoms – theory can be valuable in helping interpret and understand resistance measurements.”

In traditional electronic devices, charge-carrying electrons diffuse through circuits in a well-understood fashion, gaining or losing energy through transactions with impurities or other particles they encounter. Electrons at the nanoscale, however, can travel by a mechanism called quantum tunneling in which, due to the small length scales involved, it becomes possible for a particle to disappear through an energy barrier and suddenly appear on the other side, without expending energy. Tracking such "tunneling" of electrons through individual molecules in nanoscale devices has proven difficult.

“For more than a decade, researchers have been ‘wiring up’ individual molecules and measuring their electrical conductance,” said Neaton. “Forming reliable contacts between nanostructures and 'alligator clip' electrical leads is extremely challenging. This made experiments difficult to interpret, and as a result, reported conductance values – in experiment and theory – often varied by an order of magnitude or more. The time was ripe for a quantitative comparison between theory and an experiment with well-defined contacts."
These schematics illustrate the "vertical" and "angled" molecular junction configurations for mechanically-induced switching. A study has revealed that electrical resistance through such a junction can be turned "on" and "off" simply by pushing (left) so that the configuration is vertical or and by pulling the junction so that the configuration is angled. (Image: The Molecular Foundry, Lawrence Berkeley National Laboratory)
Through the Molecular Foundry user program, Su Ying Quek, a postdoctoral researcher, worked with Neaton and Latha Venkataraman, an experimental researcher at Columbia University, using a scanning tunneling microscope (STM), which probes changes in current across a material's surface with a conductive gold tip.

Previous work had shown a gold STM tip could be repeatedly be plunged into a gold surface containing a solution of molecules and retracted, until the contact area between the tip and gold surface reduces to a single strand, like a necklace. When this strand finally breaks, nearby molecules can hop into the gap between strands and contact the gold electrodes, resulting in a sudden change in conductance.

Using this technique, Venkataraman and colleagues, including Mark Hybertsen at Brookhaven National Lab, had recently discovered that the conductance of molecules containing amines (a group of molecules related to ammonia) in contact with gold electrodes could be reliably measured.

"We now had a reproducible and consistent data set to benchmark our theory," said Quek. "Comparing with this data set, we discovered important electron correlation effects previously missing. When we added these, we found – for the first time – quantitative agreement with experimental results."

Using their new theoretical approach, Quek and Neaton, together with Hybertsen and collaborators Steven G. Louie of University of California Berkeley and Hyoung Joon Choi of Yonsei University in Korea, began to study the conductance of a junction between gold electrodes and bipyridine — a benzene-like ring molecule containing nitrogen. The experimental data showed two stable conductance states, unlike anything seen previously.

Working closely with Venkataraman and collaborators, Quek hypothesized the peaks corresponded to two states with different structures within the junction. During the next year, Quek and Neaton meticulously constructed a theory that could describe the conductance of junctions arranged vertically between two gold molecules and sandwiched at angles.

The story that emerged was surprisingly detailed: if bipyridine bonded at an angle, more current could flow compared with when the bipyridine bonded vertically. This suggests the conductance of bipyridine was linked to the molecule's orientation in the junction, Quek said. In the STM experiment, as you pull, just after the final strand of gold atoms breaks and snaps back, the vertical gap is not big enough for bipyridine, so it bonds at an angle. As the gap increases, the molecule jumps to a vertical configuration, causing the conductance to plummet abruptly. Eventually, the molecule straightens even more, and the contact breaks.

"Once we determined this, we wondered, 'could you reverse this behavior?'" he said.

Teaming with Venkataraman and collaborators, Quek and Neaton demonstrated why pushing the junction to an angle and pulling it straight could repeatedly alter the conductance, creating a mechanical switch with well defined 'on' and 'off' states. "One of the fascinating things about this experiment is the degree to which it is possible to control the 'alligator clips'," said Neaton. "For this particular molecule, bipyridine, experiments can reproducibly and reliably alter these atomic-scale features back and forth to switch the conductance of the junction."

Quek and Neaton hope to refine and apply their theoretical framework to more complex molecular junctions for study of systems promising for solar energy conversion, such as organic photovoltaics.

"Understanding how electrons move through single-molecule junctions is the first step," said Neaton. "Organic-inorganic interfaces are everywhere in nanoscience, and developing a better picture of charge transport in hybrid materials systems will certainly lead to the discovery of new and improved electronic devices."

Portions of this work were supported by the US Department of Energy Office of Science, through its Office of Basic Energy Sciences, and by the National Science Foundation through its Nanoscale Science and Engineering Initiative.

A paper on the research appears in the March 1 edition of Nature Nanotechnology.

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A material property that is the inverse of its resistance to the flow of electricity.
That branch of science involved in the study and utilization of the motion, emissions and behaviors of currents of electrical energy flowing through gases, vacuums, semiconductors and conductors, not to be confused with electrics, which deals primarily with the conduction of large currents of electricity through metals.
The technology of generating and harnessing light and other forms of radiant energy whose quantum unit is the photon. The science includes light emission, transmission, deflection, amplification and detection by optical components and instruments, lasers and other light sources, fiber optics, electro-optical instrumentation, related hardware and electronics, and sophisticated systems. The range of applications of photonics extends from energy generation to detection to communications and...
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