Concentric hexagons of graphene grown in a furnace at Rice University represent the first time anyone has synthesized graphene nanoribbons on metal from the bottom up — atom by atom.
This set of hexagonal graphene “onion rings” was grown at Rice University. The rings represent the first example of graphene nanoribbons grown from the bottom up – that is, atom by atom – via chemical vapor deposition. (Credit: Tour Group/Rice University)
As seen under a microscope, the layers brought onions to mind, said Rice chemist James Tour, until a colleague suggested flat graphene could never be like an onion.
“So I said, ‘OK, these are onion rings,’” Tour quipped.
The name stuck, and the remarkable rings that chemists marveled were even possible are described in a new paper in the Journal of the American Chemical Society.
The challenge was to figure out how such a thing could grow, Tour said. Usually, graphene grown in a hot furnace by chemical vapor deposition starts on a seed — a speck of dust or a bump on a copper or other metallic surface. One carbon atom latches onto the seed in a process called nucleation and others follow to form the familiar chicken-wire grid.
Experiments in Tour’s lab to see how graphene grows under high pressure and in a hydrogen-rich environment produced the first rings. Under those conditions, Tour, Rice theoretical physicist Boris Yakobson and their teams found that the entire edge of a fast-growing sheet of graphene becomes a nucleation site when hydrogenated. The edge lets carbon atoms get under the graphene skin, where they start a new sheet.
But because the top graphene grows so fast, it eventually halts the flow of carbon atoms to the new sheet underneath. The bottom stops growing, leaving a graphene ring. Then the process repeats.
“The mechanism relies on that top layer to stop carbon from reaching the bottom so easily,” Tour said. “What we get are a multiple of single crystals growing one on top of the other.”
The Tour lab pioneered the bulk manufacture of single-atom-thick graphene nanoribbons in 2009 with the discovery that carbon nanotubes could be chemically “unzipped” into long, thin sheets. Nanoribbons are being studied for use in batteries and advanced electronics and as heat sinks.
“Usually you make a ribbon by taking a large thing and cutting it down,” Tour said. “But if you can grow a ribbon from the bottom up, you could have control of the edges.” The atomic configuration at the edge helps determine graphene’s electrical properties. The edges of hexagonal graphene onion rings are zigzags, which make the rings metallic.
“The big news here,” he said, “is that we can change relative pressures of the growth environment of hydrogen versus carbon and get entirely new structures. This is dramatically different from regular graphene.”
Graduate student Zheng Yan, a member of Tour’s lab and lead author of the paper, discovered the new route to nanoribbons while experimenting with graphene growth under hydrogen pressurized to varying degrees. The sweet spot for rings was at 500 Torr, he said.
Further testing found the microscopic rings formed underneath and not on top of the sheet, and Yakobson’s lab confirmed the growth mechanism through first-principle calculations. Yan also determined the top sheet of graphene could be stripped away with argon plasma, leaving stand-alone rings.
The width of the rings, which ranged from 10 to 450 nanometers, also affects their electronic properties, so finding a way to control it will be one focus of continued research, Tour said. “If we can consistently make 10-nanometer ribbons, we can begin to gate them and turn them into low-voltage transistors,” he said. They may also be suitable for lithium storage for advanced lithium ion batteries, he said.
Co-authors of the paper are Rice graduate students Yuanyue Liu, Zhiwei Peng, Changsheng Xiang, Abdul-Rahman Raji and Errol Samuel; postdoctoral researchers Jian Lin, Gunuk Wang and Haiqing Zhou; Rice alumna Elvira Pembroke; and Professor Ting Yu of Nanyang Technological University. Tour is the T.T. and W.F. Chao Chair in Chemistry as well as a professor of mechanical engineering and materials science and of computer science at Rice. Yakobson is the Karl F. Hasselmann Professor of Mechanical Engineering and Materials Science and professor of chemistry.
The Singapore National Research Foundation, the Office of Naval Research, the Lockheed Martin LANCER IV program and the Air Force Office of Scientific Research supported the work. Calculations were performed on the National Science Foundation-supported DaVinCI supercomputer at Rice, the National Institute for Computational Sciences’ Kraken and the National Energy Research Scientific Computing Center’s Hopper.
Read the abstract at http://pubs.acs.org/doi/abs/10.1021/ja403915m
David Ruth | EurekAlert!
Molecular evolution: How the building blocks of life may form in space
26.04.2018 | American Institute of Physics
Multifunctional bacterial microswimmer able to deliver cargo and destroy itself
26.04.2018 | Max-Planck-Institut für Intelligente Systeme
Magnetic resonance imaging, or MRI, is a widely used medical tool for taking pictures of the insides of our body. One way to make MRI scans easier to read is...
At the Hannover Messe 2018, the Bundesanstalt für Materialforschung und-prüfung (BAM) will show how, in the future, astronauts could produce their own tools or spare parts in zero gravity using 3D printing. This will reduce, weight and transport costs for space missions. Visitors can experience the innovative additive manufacturing process live at the fair.
Powder-based additive manufacturing in zero gravity is the name of the project in which a component is produced by applying metallic powder layers and then...
Physicists at the Laboratory for Attosecond Physics, which is jointly run by Ludwig-Maximilians-Universität and the Max Planck Institute of Quantum Optics, have developed a high-power laser system that generates ultrashort pulses of light covering a large share of the mid-infrared spectrum. The researchers envisage a wide range of applications for the technology – in the early diagnosis of cancer, for instance.
Molecules are the building blocks of life. Like all other organisms, we are made of them. They control our biorhythm, and they can also reflect our state of...
University of Connecticut researchers have created a biodegradable composite made of silk fibers that can be used to repair broken load-bearing bones without the complications sometimes presented by other materials.
Repairing major load-bearing bones such as those in the leg can be a long and uncomfortable process.
Study published in the journal ACS Applied Materials & Interfaces is the outcome of an international effort that included teams from Dresden and Berlin in Germany, and the US.
Scientists at the Helmholtz-Zentrum Dresden-Rossendorf (HZDR) together with colleagues from the Helmholtz-Zentrum Berlin (HZB) and the University of Virginia...
13.04.2018 | Event News
12.04.2018 | Event News
09.04.2018 | Event News
26.04.2018 | Power and Electrical Engineering
26.04.2018 | Life Sciences
26.04.2018 | Power and Electrical Engineering