Ursel Bangert

Free-standing graphene at atomic resolution

Research interest in graphene, a two-dimensional crystal consisting of a single atomic plane of carbon atoms, has been driven by its extraordinary properties, including charge carriers that mimic ultra-relativistic elementary particles. Moreover, graphene exhibits ballistic electron transport on the submicrometre scale, even at room temperature, which has allowed the demonstration of graphene-based field-effect transistors and the observation of a room-temperature quantum Hall effect. Here we confirm the presence of free-standing, single-layer graphene with directly interpretable atomic-resolution imaging combined with the spatially resolved study of both the pi --> pi* transition and the pi + sigma plasmon. We also present atomic-scale observations of the morphology of free-standing graphene and explore the role of microstructural peculiarities that affect the stability of the sheets. We also follow the evolution and interaction of point defects and suggest a mechanism by which they form ring defects.

Macroscopic graphene membranes and their extraordinary stiffness.

The properties of suspended graphene are currently attracting enormous interest, but the small size of available samples and the difficulties in making them severely restrict the number of experimental techniques that can be used to study the optical, mechanical, electronic, thermal, and other characteristics of this one-atom-thick material. Here, we describe a new and highly reliable approach for making graphene membranes of a macroscopic size (currently up to 100 microm in diameter) and their characterization by transmission electron microscopy. In particular, we have found that long graphene beams supported by only one side do not scroll or fold, in striking contrast to the current perception of graphene as a supple thin fabric, but demonstrate sufficient stiffness to support extremely large loads, millions of times exceeding their own weight, in agreement with the presented theory. Our work opens many avenues for studying suspended graphene and using it in various micromechanical systems and electron microscopy.

Graphene Reknits Its Holes

Nanoholes, etched under an electron beam at room temperature in single-layer graphene sheets as a result of their interaction with metal impurities, are shown to heal spontaneously by filling up with either nonhexagon, graphene-like, or perfect hexagon 2D structures. Scanning transmission electron microscopy was employed to capture the healing process and study atom-by-atom the regrown structure. A combination of these nanoscale etching and reknitting processes could lead to new graphene tailoring approaches.

Metal-graphene interaction studied via atomic resolution scanning transmission electron microscopy

Distributions and atomic sites of transition metals and gold on suspended graphene were investigated via high-resolution scanning transmission electron microscopy, especially using atomic resolution high angle dark field imaging. All metals, albeit as singular atoms or atom aggregates, reside in the omni-present hydrocarbon surface contamination; they do not form continuous films, but clusters or nanocrystals. No interaction was found between Au atoms and clean single-layer graphene surfaces, i.e., no Au atoms are retained on such surfaces. Au and also Fe atoms do, however, bond to clean few-layer graphene surfaces, where they assume T and B sites, respectively. Cr atoms were found to interact more strongly with clean monolayer graphene, they are possibly incorporated at graphene lattice imperfections and have been observed to catalyze dissociation of C-C bonds. This behavior might explain the observed high frequency of Cr-cluster nucleation, and the usefulness as wetting layer, for depositing electrical contacts on graphene.

Direct experimental evidence of metal-mediated etching of suspended graphene.

Atomic resolution high angle annular dark field imaging of suspended, single-layer graphene, onto which the metals Cr, Ti, Pd, Ni, Al, and Au atoms had been deposited, was carried out in an aberration-corrected scanning transmission electron microscope. In combination with electron energy loss spectroscopy, employed to identify individual impurity atoms, it was shown that nanoscale holes were etched into graphene, initiated at sites where single atoms of all the metal species except for gold come into close contact with the graphene. The e-beam scanning process is instrumental in promoting metal atoms from clusters formed during the original metal deposition process onto the clean graphene surface, where they initiate the hole-forming process. Our observations are discussed in the light of calculations in the literature, predicting a much lowered vacancy formation in graphene when metal ad-atoms are present. The requirement and importance of oxygen atoms in this process, although not predicted by such previous calculations, is also discussed, following our observations of hole formation in pristine graphene in the presence of Si-impurity atoms, supported by new calculations which predict a dramatic decrease of the vacancy formation energy, when SiO(x) molecules are present.

Graphene as a transparent conductive support for studying biological molecules by transmission electron microscopy

We demonstrate the application of graphene as a support for imaging individual biological molecules in transmission electron microscope (TEM). A simple procedure to produce free-standing graphene membranes has been designed. Such membranes are extremely robust and can support practically any submicrometer object. Tobacco mosaic virus has been deposited on graphene samples and observed in a TEM. High contrast has been achieved even though no staining has been applied.

Indium segregation in InGaN quantum-well structures

Direct evidence for In-segregation in InGaN/GaN quantum-well structures is given via highly spatially resolved energy dispersive x-ray analysis performed in a dedicated scanning transmission electron microscope. The In fluctuations become increasingly pronounced in the vicinity of dislocations. The latter assist In diffusion and cause severe Ga/In intermixing.

Probing the bonding and electronic structure of single atom dopants in graphene with electron energy loss spectroscopy

A combination of scanning transmission electron microscopy, electron energy loss spectroscopy, and ab initio calculations reveal striking electronic structure differences between two distinct single substitutional Si defect geometries in graphene. Optimised acquisition conditions allow for exceptional signal-to-noise levels in the spectroscopic data. The near-edge fine structure can be compared with great accuracy to simulations and reveal either an sp(3)-like configuration for a trivalent Si or a more complicated hybridized structure for a tetravalent Si impurity.

Interaction of Metals with Suspended Graphene Observed by Transmission Electron Microscopy

In this Perspective, we present an overview of how different metals interface with suspended graphene, providing a closer look into the metal-graphene interaction by employing high-resolution transmission electron microscopy, especially using high-angle dark field imaging. All studied metals favor sites on the omnipresent hydrocarbon surface contamination rather than on the clean graphene surface and present nonuniform distributions, which never result in continuous films but instead in clusters or nanocrystals, indicating a weak interaction between the metal and graphene. This behavior can be altered to some degree by surface pretreatment (hydrogenation) and high-temperature vacuum annealing. Graphene etching is observed in a scanning transmission electron microscope (STEM) under high vacuum and 60 kV electron beam acceleration voltage conditions for all metals, except for Au. This unusual metal-mediated etching sheds new light on the metal-graphene interaction; it might explain the observed higher frequency of cluster nucleation for certain transition metals and might have implications regarding controlled nanomanipulation, that is, for self-assembly and sculpturing of future graphene-based devices.

Ion implantation of graphene-toward IC compatible technologies.

Doping of graphene via low energy ion implantation could open possibilities for fabrication of nanometer-scale patterned graphene-based devices as well as for graphene functionalization compatible with large-scale integrated semiconductor technology. Using advanced electron microscopy/spectroscopy methods, we show for the first time directly that graphene can be doped with B and N via ion implantation and that the retention is in good agreement with predictions from calculation-based literature values. Atomic resolution high-angle dark field imaging (HAADF) combined with single-atom electron energy loss (EEL) spectroscopy reveals that for sufficiently low implantation energies ions are predominantly substitutionally incorporated into the graphene lattice with a very small fraction residing in defect-related sites.