Research reported this week shows that electrical resistance in nanoribbons of epitaxial graphene changes in discrete steps following quantum mechanical principles. The research shows that the graphene nanoribbons act more like optical waveguides or quantum dots, allowing electrons to flow smoothly along the edges of the material. In ordinary conductors such as copper, resistance increases in proportion to the length as electrons encounter more and more impurities while moving through the conductor.

The ballistic transport properties, similar to those observed in cylindrical carbon nanotubes, exceed theoretical conductance predictions for graphene by a factor of 10. The properties were measured in graphene nanoribbons approximately 40 nanometers wide that had been grown on the edges of three-dimensional structures etched into silicon carbide wafers.

“This work shows that we can control graphene electrons in very different ways because the properties are really exceptional,” said Walt de Heer, a Regent’s professor in the School of Physics at the Georgia Institute of Technology. “This could result in a new class of coherent electronic devices based on room temperature ballistic transport in graphene. Such devices would be very different from what we make today in silicon.”

The research, which was supported by the National Science Foundation, the Air Force Office of Scientific Research and the W.M. Keck Foundation, was reported February 5 in the journal Nature. The research was done through a collaboration of scientists from Georgia Tech in the United States, Leibniz Universität Hannover in Germany, the Centre National de la Recherche Scientifique (CNRS) in France and Oak Ridge National Laboratory – supported by the Department of Energy – in the United States.

For nearly a decade, researchers have been trying to use the unique properties of graphene to create electronic devices that operate much like existing silicon semiconductor chips. But those efforts have met with limited success because graphene – a lattice of carbon atoms that can be made as little as one layer thick – cannot be easily given the electronic bandgap that such devices need to operate.

De Heer argues that researchers should stop trying to use graphene like silicon, and instead use its unique electron transport properties to design new types of electronic devices that could allow ultra-fast computing – based on a new approach to switching. Electrons in the graphene nanoribbons can move tens or hundreds of microns without scattering.

“This constant resistance is related to one of the fundamental constants of physics, the conductance quantum,” de Heer said. “The resistance of this channel does not depend on temperature, and it does not depend on the amount of current you are putting through it.”

What does disrupt the flow of electrons, however, is measuring the resistance with an electrical probe. The measurements showed that touching the nanoribbons with a single probe doubles the resistance; touching it with two probes triples the resistance.

“The electrons hit the probe and scatter,” explained de Heer. “It’s a lot like a stream in which water is flowing nicely until you put rocks in the way. We have done systematic studies to show that when you touch the nanoribbons with a probe, you introduce a method for the electrons to scatter, and that changes the resistance.”

The nanoribbons are grown epitaxially on silicon carbon wafers into which patterns have been etched using standard microelectronics fabrication techniques. When the wafers are heated to approximately 1,000 degrees Celsius, silicon is preferentially driven off along the edges, forming graphene nanoribbons whose structure is determined by the pattern of the three-dimensional surface. Once grown, the nanoribbons require no further processing.

The advantage of fabricating graphene nanoribbons this way is that it produces edges that are perfectly smooth, annealed by the fabrication process. The smooth edges allow electrons to flow through the nanoribbons without disruption. If traditional etching techniques are used to cut nanoribbons from graphene sheets, the resulting edges are too rough to allow ballistic transport.

“It seems that the current is primarily flowing on the edges,” de Heer said. “There are other electrons in the bulk portion of the nanoribbons, but they do not interact with the electrons flowing at the edges.”

The electrons on the edge flow more like photons in optical fiber, helping them avoid scattering. “These electrons are really behaving more like light,” he said. “It is like light going through an optical fiber. Because of the way the fiber is made, the light transmits without scattering.”

The researchers measured ballistic conductance in the graphene nanoribbons for up to 16 microns. Electron mobility measurements surpassing one million correspond to a sheet resistance of one ohm per square that is two orders of magnitude lower than what is observed in two-dimensional graphene – and ten times smaller than the best theoretical predictions for graphene.

“This should enable a new way of doing electronics,” de Heer said. “We are already able to steer these electrons and we can switch them using rudimentary means. We can put a roadblock, and then open it up again. New kinds of switches for this material are now on the horizon.”

Theoretical explanations for what the researchers have measured are incomplete. De Heer speculates that the graphene nanoribbons may be producing a new type of electronic transport similar to what is observed in superconductors.  

“There is a lot of fundamental physics that needs to be done to understand what we are seeing,” he added. “We believe this shows that there is a real possibility for a new type of graphene-based electronics.”

Georgia Tech researchers have pioneered graphene-based electronics since 2001, for which they hold a patent, filed in 2003. The technique involves etching patterns into electronics-grade silicon carbide wafers, then heating the wafers to drive off silicon, leaving patterns of graphene.

In addition to de Heer, the paper’s authors included Jens Baringhaus, Frederik Edler and Christoph Tegenkamp from the Institut für Festkörperphysik, Leibniz Universität, Hannover in Germany; Edward Conrad, Ming Ruan and Zhigang Jiang from the School of Physics at Georgia Tech; Claire Berger from Georgia Tech and Institut Néel at the Centre National de la Recherche Scientifique (CNRS) in France; Antonio Tejeda and Muriel Sicot from the Institut Jean Lamour, Universite de Nancy, Centre National de la Recherche Scientifique (CNRS) in France; An-Ping Li from the Center for Nanophase Materials Sciences at Oak Ridge National Laboratory, and Amina Taleb-Ibrahimi from the CNRS Synchotron SOLEIL in France.

This research was supported by the National Science Foundation (NSF) Materials Research Science and Engineering Center (MRSEC) at Georgia Tech through award DMR-0820382; the Air Force Office of Scientific Research (AFOSR); the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy, and the Partner University Fund from the Embassy of France. Any conclusions or recommendations are those of the authors and do not necessarily represent the official views of the NSF, DOE or AFOSR.

CITATION: Jens Baringhaus, et al., “Exceptional ballistic transport in epitaxial graphene nanoribbons,” (Nature 2013). (http://dx.doi.org/10.1038/nature12952).

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A method is proposed to extract pure Raman spectrum of epitaxial graphene on SiC by using a Non-negative Matrix Factorization. It overcomes problems of negative spectral intensity and poorly resolved spectra resulting from a simple subtraction of a SiC background from the experimental data. We also show that the method is similar to deconvolution, for spectra composed of multiple sub- micrometer areas, with the advantage that no prior information on the impulse response functions is needed. We have used this property to characterize the Raman laser beam. The method capability in efficient data smoothing is also demonstrated

Spin information processing is a possible new paradigm for post-CMOS (complementary metal-oxide semiconductor) electronics and efficient spin propagation over long distances is fundamental to this vision. However, despite several decades of intense research, a suitable platform is still wanting. We report here on highly efficient spin transport in two-terminal polarizer/analyser devices based on high-mobility epitaxial graphene grown on silicon carbide. Taking advantage of high-impedance injecting/detecting tunnel junctions, we show spin transport efficiencies up to 75%, spin signals in the mega-ohm range and spin diffusion lengths exceeding 100 {\mu}m. This enables spintronics in complex structures: devices and network architectures relying on spin information processing, well beyond present spintronics applications, can now be foreseen.

Epitaxial graphene mesas and ribbons are investigated using terahertz (THz) nearfield microscopy to probe surface plasmon excitation and THz transmission properties on the sub-wavelength scale. The THz near-field images show variation of graphene properties on a scale smaller than the wavelength, and excitation of THz surface waves occurring at graphene edges, similar to that observed at metallic edges. The Fresnel reflection at the substrate SiC/air interface is also found to be altered by the presence of graphene ribbon arrays, leading to either reduced or enhanced transmission of the THz wave depending on the wave polarization and the ribbon width.

The development of graphene electronics requires the integration of graphene devices with Si-CMOS technology. Most strategies involve the transfer of graphene sheets onto silicon, with the inherent difficulties of clean transfer and subsequent graphene nano-patterning that degrades considerably the electronic mobility of nanopatterned graphene. Epitaxial graphene (EG) by contrast is grown on an essentially perfect crystalline (semi-insulating) surface, and graphene nanostructures with exceptional properties have been realized by a selective growth process on tailored SiC surface that requires no graphene patterning. However, the temperatures required in this structured growth process are too high for silicon technology. Here we demonstrate a new graphene to Si integration strategy, with a bonded and interconnected compact double-wafer structure. Using silicon-on-insulator technology (SOI) a thin monocrystalline silicon layer ready for CMOS processing is applied on top of epitaxial graphene on SiC. The parallel Si and graphene platforms are interconnected by metal vias. This method inspired by the industrial development of 3d hyper-integration stacking thin-film electronic devices preserves the advantages of epitaxial graphene and enables the full spectrum of CMOS processing.

Graphene electronics has motivated much of graphene science for the past decade. A primary goal was to develop high mobility semiconducting graphene with a band gap that is large enough for high performance applications. Graphene ribbons were thought to be semiconductors with these properties, however efforts to produce ribbons with useful bandgaps and high mobility has had limited success. We show here that high quality epitaxial graphene nanoribbons 40 nm in width, with annealed edges, grown on sidewall SiC are not semiconductors, but single channel room temperature ballistic conductors for lengths up to at least 16 micrometers. Mobilities exceeding one million corresponding to a sheet resistance below 1 Ohm have been observed, thereby surpassing two dimensional graphene by 3 orders of magnitude and theoretical predictions for perfect graphene by more than a factor of 10. The graphene ribbons behave as electronic waveguides or quantum dots. We show that transport in these ribbons is dominated by two components of the ground state transverse waveguide mode, one that is ballistic and temperature independent, and a second thermally activated component that appears to be ballistic at room temperature and insulating at cryogenic temperatures. At room temperature the resistance of both components abruptly increases with increasing length, one at a length of 160 nm and the other at 16 micrometers. These properties appear to be related to the lowest energy quantum states in the charge neutral ribbons. Since epitaxial graphene nanoribbons are readily produced by the thousands, their room temperature ballistic transport properties can be used in advanced nanoelectronics as well.

Researchers have measured a bandgap of approximately 0.5 electron-volts in 1.4-nanometer bent sections of graphene nanoribbons. The development could provide new direction to the field of graphene electronics, which has struggled with the challenge of creating bandgap necessary for operation of electronic devices.

“This is a new way of thinking about how to make high-speed graphene electronics,” said Edward Conrad, a professor in the School of Physics at the Georgia Institute of Technology. “We can now look seriously at making fast transistors from graphene. And because our process is scalable, if we can make one transistor, we can potentially make millions of them.”

The findings were reported November 18 in the journal Nature Physics. The research, done at the Georgia Institute of Technology in Atlanta and at SOLEIL, the French national synchrotron facility, has been supported by the National Science Foundation Materials Research Science and Engineering Center (MRSEC) at Georgia Tech, the W.M. Keck Foundation and the Partner University Fund from the Embassy of France.

Researchers don’t yet understand why graphene nanoribbons become semiconducting as they bend to enter tiny steps – about 20 nanometers deep – that are cut into the silicon carbide wafers. But the researchers believe that strain induced as the carbon lattice bends, along with the confinement of electrons, may be factors creating the bandgap. The nanoribbons are composed of two layers of graphene.

Production of the semiconducting graphene structures begins with the use of e-beams to cut “trenches” into silicon carbide wafers, which are normally polished to create a flat surface for the growth of epitaxial graphene. Using a high-temperature furnace, tens of thousands of graphene ribbons are then grown across the steps, using photolithography.

During the growth, the sharp edges of trenches become smoother as the material attempts to regain its flat surface. The growth time must therefore be carefully controlled to prevent the narrow silicon carbide features from melting too much.

The graphene fabrication also must be controlled along a specific direction so that the carbon atom lattice grows into the steps along the material’s “armchair” direction. “It’s like trying to bend a length of chain-link fence,” Conrad explained. “It only wants to bend one way.”

The new technique permits not only the creation of a bandgap in the material, but potentially also the fabrication of entire integrated circuits from graphene without the need for interfaces that introduce resistance. On either side of the semiconducting section of the graphene, the nanoribbons retain their metallic properties.

“We can make thousands of these trenches, and we can make them anywhere we want on the wafer,” said Conrad. “This is more than just semiconducting graphene. The material at the bends is semiconducting, and it’s attached to graphene continuously on both sides. It’s basically a Shottky barrier junction.”

By growing the graphene down one edge of the trench and then up the other side, the researchers could in theory produce two connected Shottky barriers – a fundamental component of semiconductor devices. Conrad and his colleagues are now working to fabricate transistors based on their discovery.

Confirmation of the bandgap came from angle-resolved photoemission spectroscopy measurements made at the Synchrotron CNRS in France. There, the researchers fired powerful photon beams into arrays of the graphene nanoribbons and measured the electrons emitted.

“You can measure the energy of the electrons that come out, and you can measure the direction from which they come out,” said Conrad. “From that information, you can work backward to get information about the electronic structure of the nanoribbons.”

Theorists had predicted that bending graphene would create a bandgap in the material. But the bandgap measured by the research team was larger than what had been predicted.

Beyond building transistors and other devices, in future work the researchers will attempt to learn more about what creates the bandgap – and how to control it. The property may be controlled by the angle of the bend in the graphene nanoribbon, which can be controlled by altering the depth of the step.

“If you try to lay a carpet over a small imperfection in the floor, the carpet will go over it and you may not even know the imperfection is there,” Conrad explained. “But if you go over a step, you can tell. There are probably a range of heights in which we can affect the bend.”

He predicts that the discovery will create new activity as other graphene researchers attempt to utilize the results.

“If you can demonstrate a fast device, a lot of people will be interested in this,” Conrad said. “If this works on a large scale, it could launch a niche market for high-speed, high-powered electronic devices.”

In addition to Conrad, the research team included J. Hicks, M.S. Nevius, F. Wang, K. Shepperd, J. Palmer, J. Kunc, W.A. De Heer and C. Berger, all from Georgia Tech; A. Tejeda from the Institut Jean Lamour, CNES – Univ. de Nancy and the Synchrotron SOLEIL; A. Taleb-Ibrahimi from the CNRS/Synchrotron SOLEIL, and F. Bertran and P. Le Fevre from Synchrotron SOLEIL.

This research was supported by the National Science Foundation Materials Research Science and Engineering Center (MRSEC) at Georgia Tech under Grants DMR-0820382 and DMR-1005880, the W.M. Keck Foundation, and the Partner University Fund from the Embassy of France. The content of the article is the responsibility of the authors and does not necessarily represent the views of the National Science Foundation.

CITATION: Hicks, J., A wide-bandgap metal-semiconductor-metal nanostructure made entirely from graphene, Nature Physics (2012). http://dx.doi.org/10.1038/NPHYS2487.

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The study also found that after the material is produced, its structural and chemical properties continue to evolve for more than a month as a result of continuing chemical reactions with hydrogen.

Understanding the properties of graphene oxide – and how to control them – is important to realizing potential applications for the material. To make it useful for nano-electronics, for instance, researchers must induce both an electronic band gap and structural order in the material. Controlling the amount of hydrogen in graphene oxide may be the key to manipulating the material properties.

“Graphene oxide is a very interesting material because its mechanical, optical and electronic properties can be controlled using thermal or chemical treatments to alter its structure,” said Elisa Riedo, an associate professor in the School of Physics at the Georgia Institute of Technology. “But before we can get the properties we want, we need to understand the factors that control the material’s structure. This study provides information about the role of hydrogen in the reduction of graphene oxide at room temperature.”

The research, which studied graphene oxide produced from epitaxial graphene, was reported on May 6 in the journal Nature Materials. The research was sponsored by the National Science Foundation, the Materials Research Science and Engineering Center (MRSEC) at Georgia Tech, and by the U.S. Department of Energy.

Graphene oxide is formed through the use of chemical and thermal processes that mainly add two oxygen-containing functional groups to the lattice of carbon atoms that make up graphene: epoxide and hydroxyl species. The Georgia Tech researchers began their studies with multilayer expitaxial graphene grown atop a silicon carbide wafer, a technique pioneered by Walt de Heer and his research group at Georgia Tech. Their samples included an average of ten layers of graphene.

After oxidizing the thin films of graphene using the established Hummers method, the researchers examined their samples using X-ray photo-emission spectroscopy (XPS). Over about 35 days, they noticed the number of epoxide functional groups declining while the number of hydroxyl groups increased slightly. After about three months, the ratio of the two groups finally reached equilibrium.

“We found that the material changed by itself at room temperature without any external stimulation,” said Suenne Kim, a postdoctoral fellow in Riedo’s laboratory. “The degree to which it was unstable at room temperature was surprising.”

Curious about what might be causing the changes, Riedo and Kim took their measurements to Angelo Bongiorno, an assistant professor who studies computational materials chemistry in Georgia Tech’s School of Chemistry and Biochemistry. Bongiorno and graduate student Si Zhou studied the changes using density functional theory, which suggested that hydrogen could be combining with oxygen in the functional groups to form water. That would favor a reduction in the epoxide groups, which is what Riedo and Kim were seeing experimentally.

“Elisa’s group was doing experimental measurements, while we were doing theoretical calculations,” Bongiorno said. “We combined our information to come up with the idea that maybe there was hydrogen involved.”

The suspicions were confirmed experimentally, both by the Georgia Tech group and by a research team at the University of Texas at Dallas. This information about the role of hydrogen in determining the structure of graphene oxide suggests a new way to control its properties, Bongiorno noted.

“During synthesis of the material, we could potentially use this as a tool to change the structure,” he said. “By understanding how to use hydrogen, we could add it or take it out, allowing us to adjust the relative distribution and concentration of the epoxide and hydroxyl species which control the properties of the material.”

Riedo and Bongiorno acknowledge that their material – based on epitaxial graphene – may be different from the oxide produced from exfoliated graphene. Producing graphene oxide from flakes of the material involves additional processing, including dissolving in an aqueous solution and then filtering and depositing the material onto a substrate. But they believe hydrogen plays a similar role in determining the properties of exfoliated graphene oxide.

“We probably have a new new form of graphene oxide, one that may be more useful commercially, although the same processes should also be happening within the other form of graphene oxide,” said Bongiorno.

The next steps are to understand how to control the amount of hydrogen in epitaxial graphene oxide, and what conditions may be necessary to affect reactions with the two functional groups. Ultimately, that may provide a way to open an electronic band gap and simultaneously obtain a graphene-based material with electron transport characteristics comparable to those of pristine graphene.

“By controlling the properties of graphene oxide through this chemical and thermal reduction, we may arrive at a material that remains close enough to graphene in structure to maintain the order necessary for the excellent electronic properties, while having the band gap needed to create transistors,” Riedo said. “It could be that graphene oxide is the way to arrive at that type of material.”

Beyond those already mentioned, the paper’s authors included Yike Hu, Claire Berger and Walt de Heer from the School of Physics at Georgia Tech, and Muge Acik and Yves Chabal from the Department of Materials Science and Engineering at the University of Texas at Dallas.

This research was supported by the National Science Foundation under grants CMMI-1100290, DMR-0820382 and DMR-0706031, and by the U.S. Department of Energy’s Office of Basic Energy Sciences under grants DE-FG02-06ER46293 and DE-SC001951. The content is solely the responsibility of the principal investigators and does not necessarily represent the official views of the National Science Foundation or the Department of Energy.

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"We can now make very narrow, conductive nanoribbons that have quantum ballistic properties," said Walt de Heer, a professor in the School of Physics at the Georgia Institute of Technology. "These narrow ribbons become almost like a perfect metal. Electrons can move through them without scattering, just like they do in carbon nanotubes."

De Heer discussed recent results of this graphene growth process March 21st at the American Physical Society’s March 2011 Meeting in Dallas. The research was sponsored by the National Science Foundation-supported Materials Research Science and Engineering Center (MRSEC).

First reported Oct. 3 in the advance online edition of the journal Nature Nanotechnology, the new fabrication technique allows production of epitaxial graphene structures with smooth edges. Earlier fabrication techniques that used electron beams to cut graphene sheets produced nanoribbon structures with rough edges that scattered electrons, causing interference. The resulting nanoribbons had properties more like insulators than conductors.

"In our templated growth approach, we have essentially eliminated the edges that take away from the desirable properties of graphene," de Heer explained. "The edges of the epitaxial graphene merge into the silicon carbide, producing properties that are really quite interesting."

The templated growth technique begins with etching patterns into the silicon carbide surfaces on which epitaxial graphene is grown. The patterns serve as templates directing the growth of graphene structures, allowing the formation of nanoribbons and other structures of specific widths and shapes without the use of cutting techniques that produce the rough edges.

In creating these graphene nanostructures, de Heer and his research team first use conventional microelectronics techniques to etch tiny "steps" -- or contours -- into a silicon carbide wafer whose surface has been made extremely flat. They then heat the contoured wafer to approximately 1,500 degrees Celsius, which initiates melting that polishes any rough edges left by the etching process.

Established techniques are then used for growing graphene from silicon carbide by driving the silicon atoms from the surface. Instead of producing a consistent layer of graphene across the entire surface of the wafer, however, the researchers limit the heating time so that graphene grows only on portions of the contours.

The width of the resulting nanoribbons is proportional to the depth of the contours, providing a mechanism for precisely controlling the nanoribbon structures. To form complex structures, multiple etching steps can be carried out to create complex templates.

"This technique allows us to avoid the complicated e-beam lithography steps that people have been using to create structures in epitaxial graphene," de Heer noted. "We are seeing very good properties that show these structures can be used for real electronic applications."

Since publication of the Nature Nanotechnology paper, de Heer's team has been refining its technique. "We have taken this to an extreme -- the cleanest and narrowest ribbons we can make," he said. "We expect to be able to do everything we need with the size ribbons that we are able to make right now, though we probably could reduce the width to 10 nanometers or less."

While the Georgia Tech team is continuing to develop high-frequency transistors -- perhaps even at the terahertz range -- its primary effort now focuses on developing quantum devices, de Heer said. Such devices were envisioned in the patents Georgia Tech holds on various epitaxial graphene processes.

"This means that the way we will be doing graphene electronics will be different," he explained. "We will not be following the model of using standard field-effect transistors (FETs), but will pursue devices that use ballistic conductors and quantum interference. We are headed straight into using the electron wave effects in graphene."

Taking advantage of the wave properties will allow electrons to be manipulated with techniques similar to those used by optical engineers. For instance, switching may be carried out using interference effects -- separating beams of electrons and then recombining them in opposite phases to extinguish the signals.

Quantum devices would be smaller than conventional transistors and operate at lower power. Because of its ability to transport electrons with virtually no resistance, epitaxial graphene may be the ideal material for such devices, de Heer said.

"Using the quantum properties of electrons rather than the standard charged-particle properties means opening up new ways of looking at electronics," he predicted. "This is probably the way that electronics will evolve, and it appears that graphene is the ideal material for making this transition."

De Heer's research team hopes to demonstrate a rudimentary switch operating on the quantum interference principle within a year.

Epitaxial graphene may be the basis for a new generation of high-performance devices that will take advantage of the material's unique properties in applications where higher costs can be justified. Silicon, today's electronic material of choice, will continue to be used in applications where high-performance is not required, de Heer said.

"This is an important step in the process," he added. "There are going to be a lot of surprises as we move into these quantum devices and find out how they work. We have good reason to believe that this can be the basis for a new generation of transistors based on quantum interference."

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That material, the focus of the 2010 Nobel Prize in physics, is graphene -- a fancy name for extremely thin layers of ordinary carbon atoms arranged in a "chicken-wire" lattice. These layers, sometimes just a single atom thick, conduct electricity with virtually no resistance, very little heat generation -- and less power consumption than silicon.

With silicon device fabrication approaching its physical limits, many researchers believe graphene can provide a new platform material that would allow the semiconductor industry to continue its march toward ever-smaller and faster electronic devices -- progress described in Moore's Law. Though graphene will likely never replace silicon for everyday electronic applications, it could take over as the material of choice for high-performance devices.

And graphene could ultimately spawn a new generation of devices designed to take advantage of its unique properties.

Since 2001, Georgia Tech has become a world leader in developing epitaxial graphene, a specific type of graphene that can be grown on large wafers and patterned for use in electronics manufacturing. In a recent paper published in the journal Nature Nanotechnology, Georgia Tech researchers reported fabricating an array of 10,000 top-gated transistors on a 0.24 square centimeter chip, an achievement believed to be the highest density reported so far in graphene devices.

In creating that array, they also demonstrated a clever new approach for growing complex graphene patterns on templates etched into silicon carbide. The new technique offered the solution to one of the most difficult issues that had been facing graphene electronics.

"This is a significant step toward electronics manufacturing with graphene," said Walt de Heer, a professor in Georgia Tech's School of Physics who pioneered the development of graphene for high-performance electronics. "This is another step showing that our method of working with epitaxial graphene grown on silicon carbide is the right approach and the one that will probably be used for making graphene electronics."

Unrolled Carbon Nanotubes

For de Heer, the story of graphene begins with carbon nanotubes, tiny cylindrical structures considered miraculous when they first began to be studied by scientists in 1991. De Heer was among the researchers excited about the properties of nanotubes, whose unique arrangement of carbon atoms gave them physical and electronic properties that scientists believed could be the foundation for a new generation of electronic devices.

Carbon nanotubes still have attractive properties, but the ability to grow them consistently -- and to incorporate them in high-volume electronics applications -- has so far eluded researchers. De Heer realized before others that carbon nanotubes would probably never be used for high-volume electronic devices.

But he also realized that the key to the attractive electronic properties of the nanotubes was the lattice created by the carbon atoms. Why not simply grow that lattice on a flat surface, and use fabrication techniques proven in the microelectronics industry to create devices in much the same way as silicon integrated circuits?

By heating silicon carbide -- a widely-used electronic material -- de Heer and his colleagues were able to drive silicon atoms from the surface, leaving just the carbon lattice in thin layers of graphene large enough to grow the kinds of electronic devices familiar to a generation of electronics designers.

That process was the basis for a patent filed in 2003, and for initial research support from chip-maker Intel. Since then, de Heer's group has published dozens of papers and helped spawn other research groups also using epitaxial graphene for electronic devices. Though scientists are still learning about the material, companies such as IBM have launched research programs based on epitaxial graphene, and agencies such as the National Science Foundation (NSF) and Defense Advanced Research Projects Agency (DARPA) have invested in developing the material for future electronics applications.

Georgia Tech's work on developing epitaxial graphene for manufacturing electronic devices was recognized in the background paper produced by the Royal Swedish Academy of Sciences as part of the Nobel Prize documentation.

The race to find commercial applications for graphene is intense, with researchers from the United States, Europe, Japan and Singapore engaged in well-funded efforts. Since awarding of the Nobel to a group from the United Kingdom, the flood of news releases about graphene developments has grown.

"Our epitaxial graphene is now used around the world by many research laboratories," de Heer noted. "We are probably at the stage where silicon was in the 1950s. This is the beginning of something that is going to be very large and important."

Silicon "Running Out of Gas"

A new electronics material is needed because silicon is running out of miniaturization room.

"Primarily, we've gotten the speed increases from silicon by continually shrinking feature sizes and improving interconnect technology," said Dennis Hess, director of the National Science Foundation-sponsored Materials Research Science and Engineering Center (MRSEC) established at Georgia Tech to study future electronic materials, starting with epitaxial graphene. "We are at the point where in less than 10 years, we won't be able to shrink feature sizes any farther because of the physics of the device operation. That means we will either have to change the type of device we make, or change the electronic material we use."

It's a matter of physics. At the very small size scales needed to create ever more dense device arrays, silicon generates too much resistance to electron flow, creating more heat than can be dissipated and consuming too much power.

Graphene has no such restrictions, and in fact, can provide electron mobility as much as 100 times better than silicon. De Heer believes his group has developed the roadmap for the future of high-performance electronics -- and that it is paved with epitaxial graphene.

"We have basically developed a whole scheme for making electronics out of graphene," he said. "We have set down what we believe will be the ground rules for how that will work, and we have the key patents in place."

Silicon, of course, has matured over many generations through constant research and improvement. De Heer and Hess agree that silicon will always be around, useful for low-cost consumer products such as iPods, toasters, personal computers and the like.

De Heer expects graphene to find its niche doing things that couldn't otherwise be done.

"We're not trying to do something cheaper or better; we're going to do things that can't be done at all with silicon," he said. "Making electronic devices as small as a molecule, for instance, cannot be done with silicon, but in principle could be done with graphene. The key question is how to extend Moore's Law in a post-CMOS world."

Unlike the carbon nanotubes he studied in the 1990s, de Heer sees no major problems ahead for the development of epitaxial graphene.

"That graphene is going to be a major player in the electronics of the future is no longer in doubt," he said. "We don't see any real roadblocks ahead. There are no flashing red lights or other signs that seem to say that this won't work. All of the issues we see relate to improving technical issues, and we know how to do that."

Making the Best Graphene

Since beginning the exploration of graphene in 2001, de Heer and his research team have made continuous improvements in the quality of the material they produce, and those improvements have allowed them to demonstrate a number of physical properties -- such as the Quantum Hall Effect -- that verify the unique properties of the material.

"The properties that we see in our epitaxial graphene are similar to what we have calculated for an ideal theoretical sheet of graphene suspended in the air," said Claire Berger, a research scientist in the Georgia Tech School of Physics who also has a faculty appointment at the Centre National de la Recherche Scientifique in France. "We see these properties in the electron transport and we see these properties in all kinds of spectroscopy. Everything that is supposed to be occurring in a single sheet of graphene we are seeing in our systems."

Key to the material's future, of course, is the ability to make electronic devices that work consistently. The researchers believe they have almost reached that point.

"All of the properties that epitaxial graphene needs to make it viable for electronic devices have been proven in this material," said Ed Conrad, a professor in Georgia Tech's School of Physics who is also a MRSEC member. "We have shown that we can make macroscopic amounts of this material, and with the devices that are scalable, we have the groundwork that could really make graphene take off."

Reaching higher and higher device density is also important, along with the ability to control the number of layers of graphene produced. The group has demonstrated that in their multilayer graphene, each layer retains the desired properties.

"Multilayer graphene has different stacking than graphite, the material found in pencils," Conrad noted. "In graphite, every layer is rotated 60 degrees and that's the only way that nature can do it. When we grow graphene on silicon carbide, the layers are rotated 30 degrees. When that happens, the symmetry of the system changes to make the material behave the way we want it to."

Epitaxial Versus Exfoliated

Much of the world's graphene research -- including work leading to the Nobel -- involved the study of exfoliated graphene: layers of the material removed from a block of graphite, originally with tape. While that technique produces high-quality graphene, it's not clear how that could be scaled up for industrial production.

While agreeing that the exfoliated material has produced useful information about graphene properties, de Heer dismisses it as "a science project" unlikely to have industrial electronics application.

"Electronics companies are not interested in graphene flakes," he said. "They need industrial graphene, a material that can be scaled up for high-volume manufacturing. Industry is now getting more and more interested in what we are doing."

De Heer says Georgia Tech's place in the new graphene world is to focus on electronic applications.

"We are not really trying to compete with these other groups," he said. "We are really trying to create a practical electronic material. To do that, we will have to do many things right, including fabricating a scalable material that can be made as large as a wafer. It will have to be uniform and able to be processed using industrial methods."

Resolving Technical Issues

Among the significant technical issues facing graphene devices has been electron scattering that occurs at the boundaries of nanoribbons. If the edges aren't perfectly smooth -- as usually happens when the material is cut with electron beams -- the roughness bounces electrons around, creating resistance and interference.

To address that problem, de Heer and his team recently developed a new "templated growth" technique for fabricating nanometer-scale graphene devices. The technique involves etching patterns into the silicon carbide surfaces on which epitaxial graphene is grown. The patterns serve as templates directing the growth of graphene structures, allowing the formation of nanoribbons of specific widths without the use of e-beams or other destructive cutting techniques. Graphene nanoribbons produced with these templates have smooth edges that avoid electron-scattering problems.

"Using this approach, we can make very narrow ribbons of interconnected graphene without the rough edges," said de Heer. "Anything that can be done to make small structures without having to cut them is going to be useful to the development of graphene electronics because if the edges are too rough, electrons passing through the ribbons scatter against the edges and reduce the desirable properties of graphene."

In nanometer-scale graphene ribbons, quantum confinement makes the material behave as a semiconductor suitable for creation of electronic devices. But in ribbons a micron or so wide, the material acts as a conductor. Controlling the depth of the silicon carbide template allows the researchers to create these different structures simultaneously, using the same growth process.

"The same material can be either a conductor or a semiconductor depending on its shape," noted de Heer. "One of the major advantages of graphene electronics is to make the device leads and the semiconducting ribbons from the same material. That's important to avoid electrical resistance that builds up at junctions between different materials."

After formation of the nanoribbons, the researchers apply a dielectric material and metal gate to construct field-effect transistors. While successful fabrication of high-quality transistors demonstrates graphene's viability as an electronic material, de Heer sees them as only the first step in what could be done with the material.

"When we manage to make devices well on the nanoscale, we can then move on to make much smaller and finer structures that will go beyond conventional transistors to open up the possibility for more sophisticated devices that use electrons more like light than particles," he said. "If we can factor quantum mechanical features into electronics, that is going to open up a lot of new possibilities."

Collaborations with Other Groups

Before engineers can use epitaxial graphene for the next generation of electronic devices, they will have to understand its unique properties. As part of that process, Georgia Tech researchers are collaborating with scientists at the National Institute of Standards and Technology (NIST). The collaboration has produced new insights into how electrons behave in graphene.

In a recent paper published in the journal Nature Physics, the Georgia Tech-NIST team described for the first time how the orbits of electrons are distributed spatially by magnetic fields applied to layers of epitaxial graphene. They also found that these electron orbits can interact with the substrate on which the graphene is grown, creating energy gaps that affect how electron waves move through the multilayer material.

"The regular pattern of magnetically-induced energy gaps in the graphene surface creates regions where electron transport is not allowed," said Phillip N. First, a professor in the Georgia Tech School of Physics and MRSEC member. "Electron waves would have to go around these regions, requiring new patterns of electron wave interference. Understanding this interference would be important for some bi-layer graphene devices that have been proposed."

Earlier NIST collaborations led to improved understanding of graphene electron states, and the way in which low temperature and high magnetic fields can affect energy levels. The researchers also demonstrated that atomic-scale moiré patterns, an interference pattern that appears when two or more graphene layers are overlaid, can be used to measure how sheets of graphene are stacked.

In a collaboration with the U.S. Naval Research Laboratory and University of Illinois at Urbana-Champaign, a group of Georgia Tech professors developed a simple and quick one-step process for creating nanowires on graphene oxide.

"We've shown that by locally heating insulating graphene oxide, both the flakes and the epitaxial varieties, with an atomic force microscope tip, we can write nanowires with dimensions down to 12 nanometers," said Elisa Riedo, an associate professor in the Georgia Tech School of Physics and a MRSEC member. "And we can tune their electronic properties to be up to four orders of magnitude more conductive."

A New Industrial Revolution?

Though graphene can be grown and fabricated using processes similar to those of silicon, it is not easily compatible with silicon. That means companies adopting it will also have to build new fabrication facilities -- an expensive investment. Consequently, de Heer believes industry will be cautious about moving into a new graphene world.

"Silicon technology is completely entrenched and well developed," he admitted. "We can adopt many of the processes of silicon, but we can't easily integrate ourselves into silicon. Because of that, we really need a major paradigm shift. But for the massive electronics industry, that will not happen easily or gently."

He draws an analogy to steamships and passenger trains at the dawn of the aviation age. At some point, it became apparent that airliners were going to replace both ocean liners and trains in providing first-class passenger service. Though the cost of air travel was higher, passengers were willing to pay a premium for greater speed.

"We are going to see a coexistence of technologies for a while, and how the hybridization of graphene and silicon electronics is going to happen remains up in the air," de Heer predicted. "That is going to take decades, though in the next ten years we are probably going to see real commercial devices that involve graphene."

This article originally appeared in Research Horizons, Georgia Tech's research magazine.

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Media Relations Contacts: John Toon (404-894-6986)(jtoon@gatech.edu) or Abby Vogel Robinson (404-385-3364)(abby@innovate.gatech.edu).

Writer: John Toon

Abstract:
Graphene forms moiré structures on lattice mismatched close-packed metal surfaces. These structures involve periodic transitions between three stacking areas. Graphene is most loosely bound in the one where the C-rings are centered on metal atoms and therefore these stacking areas are expected to exhibit an electronic structure coming close to the one of free standing graphene. Indeed sharp linear bands forming Dirac cones have been observed for g-monolayers on Ir(111), but hitherto not on Ru(0001), where only the second layer displayed the characteristic electronic structure of graphene.  We present angle-resolved photoelectron spectroscopy (ARPES) and scanning tunneling microscopy (STM) results on the electronic and real-space structure of graphene mono- and bilayers on Ru(0001) and of graphene monolayers on Ir(111). We find that long-range ordered graphene monolayers on Ru(0001) display sharp Dirac cones. The lateral positions of the C-ring centers in the first monolayer show strong distortions from a hexagonal lattice. Therefore the moiré structure is not the beating of two laterally rigid hexagonal lattices, instead, graphene optimizes its binding to the substrate by strongly adapting the C-C distances. The moiré of g/Ir(111) gives rise to six-fold symmetric replica around the K-point. A super-lattice of Ir islands grown on-top introduces a strongly increases the amplitude of the periodic electron potential leading to three-fold symmetry, a band gap opening and to strongly asymmetric group velocities. In the case of Ru, very similar growth temperatures and identical ethylene dosage give rise to strongly different g coverage and long-range order such that these samples are best assessed by the presented combination of morphology and electronic structure characterization.

2nd International Symposium on the Science and Technology of Epitaxial Graphene (STEG 2)

When: September 14 - 17, 2010

Where: Amelia Island, Florida

Abstract:
The Georgia Tech Materials Research Science and Engineering Center (MRSEC) was established by NSF in September 2008. This Center is funded for 6 years and is a cross-disciplinary effort involving GT as well as The University of California Berkeley, The University of California Riverside, Alabama A&M, and The University of Michigan. Initially, the Center focus is on graphene, a material with the requisite properties and potential to serve as the successor to silicon in ICs, sensors, and MEMS devices. Although research is a major effort of Center activity, substantial efforts are in place for education and outreach. This presentation will describe the organization of the GT MRSEC, the breadth of research that has been undertaken, the educational activities underway and planned, including a Partnership for Research and Education in Materials (PREM) with The Atlanta University Center (Clark Atlanta, Morehouse and Spelman Universities), and the outreach programs. Future plans and goals will be described.