Single atom lithography in graphene

March 4, 2011 — A little zinc can do a lot of damage to graphene. Rice University researchers have taken advantage of that to create single-atomic-layer lithography. The Rice lab of chemist James Tour sputtered zinc onto multilayered graphene, enabling the team to remove a single layer at a time without disturbing the layers beneath.

A microscopic checkerboard pattern shows the ability of Rice University’s new technique, as reported in Science, to remove single layers of graphene without disturbing the layers beneath. (Credit: Tour Lab/Rice University)

The discovery could be useful as researchers explore graphene’s electrical properties for new generations of microcircuitry and other graphene-based devices. Graphene, the one-atom-thick form of carbon, won its discoverers the most recent Nobel Prize in physics.

The researchers created a graphene checkerboard by removing horizontal and vertical layers to create a three-dimensional pattern. The researchers were able to create a 100nm line in a sheet of graphene, which suggests the only horizontal limit to the resolution of the process is the resolution of the metal patterning method.

"The next step will be to control the horizontal patterning with similar precision to what we have attained in the vertical dimension," Tour said. "Then there’s no more room at the bottom at any dimension, at least if we call single atoms our endpoint — which it is, for practical purposes."

"The removal of a single sheet of graphene or graphene oxide was a surprise," said Tour, Rice’s T.T. and W.F. Chao Chair in Chemistry as well as a professor of mechanical engineering and materials science and of computer science. "We thought multiple layers would be removed by this protocol, but to see single layers removed is one of those exciting events in science where nature gives us far more than we expected."

The Rice U. researchers printed a micro owl, Rice’s mascot, about 15 millionths of a meter wide. For the owl, Dimiev cut a stencil in PMMA with an electron beam and placed it on graphene oxide. He sputter-coated zinc through the stencil and then washed the zinc away with dilute hydrochloric acid, leaving the embedded owl behind. (Credit: Tour Lab/Rice University)

Tour said the ability to remove single layers of graphene in a controlled manner "affords the most precise level of device-patterning ever known, or ever to be known, where we have single-atom resolution in the vertical dimension. This will forever be the limit of vertical patterning — we have hit the bottom of the scale."

Ayrat Dimiev, a postdoctoral scientist in Tour’s lab, discovered the technique and figured out why graphene is so amenable to patterning. He sputtered zinc onto graphene oxide and other variants created through chemical conversion, chemical vapor deposition (CVD) and micromechanically (the "Scotch-tape" method). Bathing the graphene in dilute hydrochloric acid removed graphene wherever the zinc touched it, leaving the layers underneath intact. The graphene was then rinsed with water and dried in a stream of nitrogen.

Investigation of the sputtered surface before applying the acid wash revealed that the metals formed defects in the graphene, breaking bonds with the surrounding sheet like a cutter through chicken wire. Sputtering zinc, aluminum, gold and copper all produced similar effects, though zinc was best at delivering the desired patterning.

Sputter-coating graphene with aluminum showed similar effects. But when Dimiev tried applying zinc via thermal evaporation, the graphene stayed intact.

Results are reported this week in the journal Science. Read the abstract at: 

A team of Rice University researchers has developed a way to remove layers of graphene from a stack leaving underlying layers in a pristine state. Co-authors of a new Science paper on the research include, from left: Ayrat Dimiev, Alexander Slesarev, Professor James Tour, Zhengzong Sun and Alexander Sinitskii. Missing from the photo is former Rice postdoctoral researcher Dmitry Kosynkin. (Jeff Fitlow/Rice University) Co-authors include research associate Dmitry Kosynkin, postdoctoral research associate Alexander Sinitskii and graduate students Alexander Slesarev and Zhengzong Sun, all of Rice.

The Air Force Office of Scientific Research, the Air Force Research Lab through the University Technology Corporation, the Office of Naval Research Graphene MURI Program, and M-I SWACO funded the research.

Video of the researchers discussing their work is available at:

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