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Doorway states spotted in graphene-based materials
Low-energy electrons escape from some materials via distinct “doorway” states, according to a study done by physicists at Austria’s Vienna Institute of Technology. The team studied graphene-based materials and found that the nature of the doorway states depended on the number of graphene layers in the sample.
Low-energy electron (LEE) emission from solids is used across a range of materials analysis and processing applications including scanning electron microscopy and electron-beam induced deposition. However, the precise physics of the emission process is not well understood.
Electrons are ejected from a material when a beam of electrons is fired at its surface. Some of these incident electrons will impart energy to electrons residing in the material, causing some resident electrons to be emitted from the surface. In the simplest model, the minimum energy needed for this LEE emission is the electron binding energy of the material.
Frog in a box
In this new study, however, researchers have shown that exceeding the binding energy is not enough for LEE emission from graphene-based materials. Not only does the electron need this minimum energy, it must also be in a specific doorway state or it is unlikely to escape. The team compare this phenomenon to the predicament of a frog in a cardboard box with a window. Not only must the frog hop a certain height to escape the box, it must also begin its hop from a position that will result in it travelling through the hole (see figure).
For most materials, the energy spectrum of LEE electrons is featureless. However, it was known that graphite’s spectrum has an “X state” at about 3.3 eV, where emission is enhanced. This state could be related to doorway states.
To search for doorway states, the Vienna team studied LEE emission from graphite as well as from single-layer and bi-layer graphene. Graphene is a sheet of carbon just one atom thick. Sheets can stick together via the relatively weak Van der Waals force to create multilayer graphene – and ultimately graphite, which comprises a large number of layers.
Because electrons are mostly confined within the graphene layers, the electronic states of single-layer, bi-layer and multi-layer graphene are broadly similar. As a result, it was expected that these materials would have similar LEE emission spectra . However, the Vienna team found a surprising difference.
Emission and reflection
The team made their discovery by firing a beam of relatively low energy electrons (173 eV) incident at 60° to the surface of single-layer and bi-layer graphene as well as graphite. The scattered electrons are then detected at the same angle of reflection. Meanwhile, a second detector is pointed normal to the surface to capture any emitted electrons. In quantum mechanics electrons are indistinguishable, so the modifiers scattered and emitted are illustrative, rather than precise.
The team looked for coincident signals in both detectors and plotted their results as a function of energy in 2D “heat maps”. These plots revealed that bi-layer graphene and graphite each had doorway states – but at different energies. However, single-layer graphene did not appear to have any doorway states. By combining experiments with calculations, the team showed that doorway states emerge above a certain number of layers. As a result the researchers showed that graphite’s X state can be attributed in part to a doorway state that appears at about five layers of graphene.
“For the first time, we’ve shown that the shape of the electron spectrum depends not only on the material itself, but crucially on whether and where such resonant doorway states exist,” explains Anna Niggas at the Vienna Institute of Technology.
As well as providing important insights in how the electronic properties of graphene morph into the properties of graphite, the team says that their research could also shed light on the properties of other layered materials.
The research is described in Physical Review Letters.
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