“Confinement changes graphene’s behavior,” said An-Ping Li, a physicist at the Department of Energy’s Oak Ridge National Laboratory (ORNL). Graphene in sheets is an excellent electrical conductor, but narrowing graphene can turn the material into a semiconductor if the ribbons are made with a specific edge shape.
Previous efforts to make graphene nanoribbons employed a metal substrate that hindered the ribbons’ useful electronic properties.
Now, scientists at ORNL and North Carolina State University report in the journal Nature Communications that they are the first to grow graphene nanoribbons without a metal substrate. Instead, they injected charge carriers that promote a chemical reaction that converts a polymer precursor into a graphene nanoribbon. At selected sites, this new technique can create interfaces between materials with different electronic properties. Such interfaces are the basis of semiconductor electronic devices from integrated circuits and transistors to light-emitting diodes and solar cells.
“Graphene is wonderful, but it has limits,” said Li. “In wide sheets, it doesn’t have an energy gap – an energy range in a solid where no electronic states can exist. That means you cannot turn it on or off.”
When a voltage is applied to a sheet of graphene in a device, electrons flow freely as they do in metals, severely limiting graphene’s application in digital electronics.
“When graphene becomes very narrow, it creates an energy gap,” Li said. “The narrower the ribbon is, the wider is the energy gap.”
In very narrow graphene nanoribbons, with a width of a nanometer or even less, how structures terminate at the edge of the ribbon is important too. For example, cutting graphene along the side of a hexagon creates an edge that resembles an armchair; this material can act like a semiconductor. Excising triangles from graphene creates a zigzag edge – and a material with metallic behavior.
To grow graphene nanoribbons with controlled width and edge structure from polymer precursors, previous researchers had used a metal substrate to catalyze a chemical reaction. However, the metal substrate suppresses useful edge states and shrinks the desired band gap.
Li and colleagues set out to get rid of this metal substrate. At the Center for Nanophase Materials Sciences, a DOE Office of Science User Facility at ORNL, they used the tip of a scanning tunneling microscope to inject either negative charge carriers (electrons) or positive charge carriers (“holes”) to try to trigger the key chemical reaction. They discovered that only holes triggered it. They were subsequently able to make a ribbon that was only seven carbon atoms wide – less than one nanometer wide – with edges in the armchair conformation.
Next, the researchers will make heterojunctions with different precursor molecules and explore functionalities.
The title of the current paper is “Controllable conversion of quasi-freestanding polymer chains to graphene nanoribbons.”