M. F. Crommie

Graphene at the Edge: Stability and Dynamics

Although the physics of materials at surfaces and edges has been extensively studied, the movement of individual atoms at an isolated edge has not been directly observed in real time. With a transmission electron aberration–corrected microscope capable of simultaneous atomic spatial resolution and 1-second temporal resolution, we produced movies of the dynamics of carbon atoms at the edge of a hole in a suspended, single atomic layer of graphene. The rearrangement of bonds and beam-induced ejection of carbon atoms are recorded as the hole grows. We investigated the mechanism of edge reconstruction and demonstrated the stability of the “zigzag” edge configuration. This study of an ideal low-dimensional interface, a hole in graphene, exhibits the complex behavior of atoms at a boundary.

Direct imaging of lattice atoms and topological defects in graphene membranes.

We present a transmission electron microscopy investigation of graphene membranes, crystalline foils with a thickness of only 1 atom. By using aberration-correction in combination with a monochromator, 1-A resolution is achieved at an acceleration voltage of only 80 kV. The low voltage is crucial for the stability of these membranes. As a result, every individual carbon atom in the field of view is detected and resolved. We observe a highly crystalline lattice along with occasional point defects. The formation and annealing of Stone-Wales defects is observed in situ. Multiple five- and seven-membered rings appear exclusively in combinations that avoid dislocations and disclinations, in contrast to previous observations on highly curved (tube- or fullerene-like) graphene surfaces.

Strain-induced Pseudo-Magnetic Fields Greater Than 300 Tesla in Graphene Nanobubbles

Straining Graphenes Electronic States The conduction electrons in graphene, single sheets of graphite, can have very high mobilities. Under the influence of an applied magnetic field, a series of energy steps, or Landau levels, can be observed that correspond to the conduction electrons traveling in cyclotron orbits. Recent theoretical work has indicated that if graphene layers are strained, the strain field creates a pseudomagnetic field that should also lead to observable Landau levels. Levy et al. (p. 544) used scanning tunneling microscopy to probe the energy levels of graphene grown on a platinum surface, which forms highly strained “nanobubbles.” The strain is equivalent to applying very high magnetic fields (in excess of 300 tesla). Thus, the electronic properties of graphene can indeed be modified using applied strain. Strain creates energy levels in graphene that are similar to those seen in very high applied magnetic fields. Recent theoretical proposals suggest that strain can be used to engineer graphene electronic states through the creation of a pseudo–magnetic field. This effect is unique to graphene because of its massless Dirac fermion-like band structure and particular lattice symmetry (C3v). Here, we present experimental spectroscopic measurements by scanning tunneling microscopy of highly strained nanobubbles that form when graphene is grown on a platinum (111) surface. The nanobubbles exhibit Landau levels that form in the presence of strain-induced pseudo–magnetic fields greater than 300 tesla. This demonstration of enormous pseudo–magnetic fields opens the door to both the study of charge carriers in previously inaccessible high magnetic field regimes and deliberate mechanical control over electronic structure in graphene or so-called “strain engineering.”

Grain Boundary Mapping in Polycrystalline Graphene

We report direct mapping of the grains and grain boundaries (GBs) of large-area monolayer polycrystalline graphene sheets, at large (several micrometer) and single-atom length scales. Global grain and GB mapping is performed using electron diffraction in scanning transmission electron microscopy (STEM) or using dark-field imaging in conventional TEM. Additionally, we employ aberration-corrected TEM to extract direct images of the local atomic arrangements of graphene GBs, which reveal the alternating pentagon-heptagon structure along high-angle GBs. Our findings provide a readily adaptable tool for graphene GB studies.

Raman Spectroscopy Study of Rotated Double-Layer Graphene: Misorientation-Angle Dependence of Electronic Structure

We present a systematic Raman study of unconventionally stacked double-layer graphene, and find that the spectrum strongly depends on the relative rotation angle between layers. Rotation-dependent trends in the position, width and intensity of graphene 2D and G peaks are experimentally established and accounted for theoretically. Our theoretical analysis reveals that changes in electronic band structure due to the interlayer interaction, such as rotational-angle dependent Van Hove singularities, are responsible for the observed spectral features. Our combined experimental and theoretical study provides a deeper understanding of the electronic band structure of rotated double-layer graphene, and leads to a practical way to identify and analyze rotation angles of misoriented double-layer graphene.

Multiply folded graphene

The folding of paper, hide, and woven fabric has been used for millennia to achieve enhanced articulation, curvature, and visual appeal for intrinsically flat, two-dimensional materials. For graphene, an ideal twodimensional material, folding may transform it to complex shapes with new and distinct properties. Here, we present experimental results that folded structures in graphene, termed grafold, exist, and their formations can be controlled by introducing anisotropic surface curvature during graphene synthesis or transfer processes. Using pseudopotential-density-functional-theory calculations, we also show that double folding modifies the electronic band structure of graphene. Furthermore, we demonstrate the intercalation of C60 into the grafolds. Intercalation or functionalization of the chemically reactive folds further expands grafold’s mechanical, chemical, optical, and electronic diversity.

Ripping graphene: preferred directions.

The understanding of crack formation due to applied stress is key to predicting the ultimate mechanical behavior of many solids. Here we present experimental and theoretical studies on cracks or tears in suspended monolayer graphene membranes. Using transmission electron microscopy, we investigate the crystallographic orientations of tears. Edges from mechanically induced ripping exhibit straight lines and are predominantly aligned in the armchair or zigzag directions of the graphene lattice. Electron-beam induced propagation of tears is also observed. Theoretical simulations account for the observed preferred tear directions, attributing the observed effect to an unusual nonmonotonic dependence of graphene edge energy on edge orientation with respect to the lattice. Furthermore, we study the behavior of tears in the vicinity of graphene grain boundaries, where tears surprisingly do not follow but cross grain boundaries. Our study provides significant insights into breakdown mechanisms of graphene in the presence of defective structures such as cracks and grain boundaries.

Atomically perfect torn graphene edges and their reversible reconstruction

The atomic structure of graphene edges is critical in determining the electrical, magnetic and chemical properties of truncated graphene structures, notably nanoribbons. Unfortunately, graphene edges are typically far from ideal and suffer from atomic-scale defects, structural distortion and unintended chemical functionalization, leading to unpredictable properties. Here we report that graphene edges fabricated by electron beam-initiated mechanical rupture or tearing in high vacuum are clean and largely atomically perfect, oriented in either the armchair or zigzag direction. We demonstrate, via aberration-corrected transmission electron microscopy, reversible and extended pentagon-heptagon (5-7) reconstruction at zigzag edges, and explore experimentally and theoretically the dynamics of the transitions between configuration states. Good theoretical-experimental agreement is found for the flipping rates between 5-7 and 6-6 zigzag edge states. Our study demonstrates that simple ripping is remarkably effective in producing atomically clean, ideal terminations, thus providing a valuable tool for realizing atomically tailored graphene and facilitating meaningful experimental study.

Tuning negative differential resistance in a molecular film

We have observed variable negative differential resistance (NDR) in scanning tunneling spectroscopy measurements of a double layer of C60 molecules on a metallic surface. Minimum to maximum current ratios in the NDR region are tuned by changing the tunneling barrier width. The multilayer geometry is critical, as NDR is not observed when tunneling into a C60 monolayer. Using a simple model, we show that the observed NDR behavior is explained by voltage-dependent changes in the tunneling barrier height.

Graphene electrostatic microphone and ultrasonic radio

Significance Humans and other animals effectively use acoustic waves to communicate with each other. Ultrasonic acoustic waves are intriguing because they do not interfere with normal voice communication and can be highly directional with long range. Therefore, wireless ultrasonic radio is a useful communications method. Here we find that graphene has mechanical properties that make it ideally suited for wide-band ultrasonic transduction. Using simple and low-cost fabrication methods we have produced an ultrasonic microphone and ultrasonic radio prototypes. When acting as loudspeaker/microphone alone, the graphene-based acoustic devices also show ideal flat-band frequency response spanning the whole audible region as well as ultrasonic region to at least 0.5 MHz; such flat frequency response has significant acoustic applications implications. We present a graphene-based wideband microphone and a related ultrasonic radio that can be used for wireless communication. It is shown that graphene-based acoustic transmitters and receivers have a wide bandwidth, from the audible region (20∼20 kHz) to the ultrasonic region (20 kHz to at least 0.5 MHz). Using the graphene-based components, we demonstrate efficient high-fidelity information transmission using an ultrasonic band centered at 0.3 MHz. The graphene-based microphone is also shown to be capable of directly receiving ultrasound signals generated by bats in the field, and the ultrasonic radio, coupled to electromagnetic (EM) radio, is shown to function as a high-accuracy rangefinder. The ultrasonic radio could serve as a useful addition to wireless communication technology where the propagation of EM waves is difficult.