Michael F. Crommie

Direct observation of a widely tunable bandgap in bilayer graphene.

The electronic bandgap is an intrinsic property of semiconductors and insulators that largely determines their transport and optical properties. As such, it has a central role in modern device physics and technology and governs the operation of semiconductor devices such as p–n junctions, transistors, photodiodes and lasers. A tunable bandgap would be highly desirable because it would allow great flexibility in design and optimization of such devices, in particular if it could be tuned by applying a variable external electric field. However, in conventional materials, the bandgap is fixed by their crystalline structure, preventing such bandgap control. Here we demonstrate the realization of a widely tunable electronic bandgap in electrically gated bilayer graphene. Using a dual-gate bilayer graphene field-effect transistor (FET) and infrared microspectroscopy, we demonstrate a gate-controlled, continuously tunable bandgap of up to 250 meV. Our technique avoids uncontrolled chemical doping and provides direct evidence of a widely tunable bandgap—spanning a spectral range from zero to mid-infrared—that has eluded previous attempts. Combined with the remarkable electrical transport properties of such systems, this electrostatic bandgap control suggests novel nanoelectronic and nanophotonic device applications based on graphene.

Gate-Variable Optical Transitions in Graphene

Two-dimensional graphene monolayers and bilayers exhibit fascinating electrical transport behaviors. Using infrared spectroscopy, we find that they also have strong interband transitions and that their optical transitions can be substantially modified through electrical gating, much like electrical transport in field-effect transistors. This gate dependence of interband transitions adds a valuable dimension for optically probing graphene band structure. For a graphene monolayer, it yields directly the linear band dispersion of Dirac fermions, whereas in a bilayer, it reveals a dominating van Hove singularity arising from interlayer coupling. The strong and layer-dependent optical transitions of graphene and the tunability by simple electrical gating hold promise for new applications in infrared optics and optoelectronics.

High-resolution EM of colloidal nanocrystal growth using graphene liquid cells.

Liquid Nanocrystals In high-resolution transmission electron microscopy, grid materials are used to support solid samples while providing a means for preventing a build-up of static charge. Liquids are difficult to study at the same atomic resolution and require encapsulation to prevent excess sample movement, sample damage, or evaporation. Materials that have been used for liquid cells, like silicon nitride or silicon oxide, need thick layers and have poor electron transmittance at the thicknesses required because they contain high atomic number elements. Yuk et al. (p. 61; see the Perspective by Colliex) show that liquids can be encapsulated in graphene sheets, and through this technique, they studied the formation of platinum nanocrystals with atomic resolution. The crystals could be tracked as they selectively coalesced, modified their shape, and formed surface facets. Encapsulating a liquid film between two graphene layers allows the film and growing crystals from the graphene sheets to be studied at an atomic scale. We introduce a new type of liquid cell for in situ transmission electron microscopy (TEM) based on entrapment of a liquid film between layers of graphene. The graphene liquid cell facilitates atomic-level resolution imaging while sustaining the most realistic liquid conditions achievable under electron-beam radiation. We employ this cell to explore the mechanism of colloidal platinum nanocrystal growth. Direct atomic-resolution imaging allows us to visualize critical steps in the process, including site-selective coalescence, structural reshaping after coalescence, and surface faceting.

O rigin of spatial charge inhomogeneity in graphene

In an ideal graphene sheet, charge carriers behave as two-dimensional Dirac fermions 1 . This has been confirmed by the discovery of a half-integer quantum Hall effect in graphene flakes placed on a SiO2 substrate. The Dirac fermions in graphene, however, are subject to microscopic perturbations that include topographic corrugations and electron-density inhomogeneities (that is, charge puddles). Such perturbations profoundly alter Dirac-fermion behaviour, with implications for their fundamental physics as well as for future graphene device applications. Here we report a new technique of Diracpoint mapping that we have used to determine the origin of charge inhomogeneities in graphene. We find that fluctuations in graphene charge density are caused not by topographical corrugations, but rather by charge-donating impurities below the graphene. These impurities induce surprising standing wave patterns due to unexpected backscattering of Dirac fermions. Such wave patterns can be continuously modulated by electric gating. Our observations provide new insight into impurity scattering of Dirac fermions and the microscopic mechanisms limiting electronic mobility in graphene. Topographic corrugations and charge puddles in graphene are two of the most significant types of disorder in this new material. Topographic corrugations 24 , for example, have been suggested as a cause for the suppression of anticipated antilocalization 5 . Electron and hole puddles 6 have similarly been blamed for obscuring universal conductivity in graphene 7 . These issues are part of a puzzle regarding the factors that limit graphene’s mobility 812 . In order for graphene to fulfil its promise as a next-generation nanodevice substrate it is important to understand the origin of the disorder and the influence it has on Dirac fermions. We have made new progress in this direction by using the techniques of scanning tunnelling microscopy (STM) and spectroscopy to simultaneously probe topographic and electronic disorder in graphene with an electron-density spatial resolution two orders of magnitude higher than previous scanning single-electron transistor microscopy measurements 6 . Figure 1a shows the STM topography of a typical 30 30nm 2 area of a graphene monolayer on SiO2. We observe random corrugations with lateral dimension of a few nanometres and a vertical dimension of1:5¯ (r.m.s.), probably due to roughness in the underlying SiO2 surface and/or intrinsic ripples of the graphene sheet 24,13 . STM imaging at the atomic scale clearly resolves the graphene honeycomb lattice on top of the broader surfacecorrugationalloverthesamplesurface(inset).

Spatially resolving edge states of chiral graphene nanoribbons

Edge effects matter in graphene, particularly in nanoribbons. A study using scanning tunnelling microscopy and spectroscopy reveals how chirality at the atomically well-defined edges of a graphene nanoribbon affects its electronic structure.

Imaging and dynamics of light atoms and molecules on graphene

Observing the individual building blocks of matter is one of the primary goals of microscopy. The invention of the scanning tunnelling microscope revolutionized experimental surface science in that atomic-scale features on a solid-state surface could finally be readily imaged. However, scanning tunnelling microscopy has limited applicability due to restrictions in, for example, sample conductivity, cleanliness, and data acquisition rate. An older microscopy technique, that of transmission electron microscopy (TEM), has benefited tremendously in recent years from subtle instrumentation advances, and individual heavy (high-atomic-number) atoms can now be detected by TEM even when embedded within a semiconductor material. But detecting an individual low-atomic-number atom, for example carbon or even hydrogen, is still extremely challenging, if not impossible, via conventional TEM owing to the very low contrast of light elements. Here we demonstrate a means to observe, by conventional TEM, even the smallest atoms and molecules: on a clean single-layer graphene membrane, adsorbates such as atomic hydrogen and carbon can be seen as if they were suspended in free space. We directly image such individual adatoms, along with carbon chains and vacancies, and investigate their dynamics in real time. These techniques open a way to reveal dynamics of more complex chemical reactions or identify the atomic-scale structure of unknown adsorbates. In addition, the study of atomic-scale defects in graphene may provide insights for nanoelectronic applications of this interesting material.

Local Electronic Properties of Graphene on a BN Substrate via Scanning Tunneling Microscopy

The use of boron nitride (BN) as a substrate for graphene nanodevices has attracted much interest since the recent report that BN greatly improves the mobility of charge carriers in graphene compared to standard SiO(2) substrates. We have explored the local microscopic properties of graphene on a BN substrate using scanning tunneling microscopy. We find that BN substrates result in extraordinarily flat graphene layers that display microscopic Moiré patterns arising from the relative orientation of the graphene and BN lattices. Gate-dependent dI/dV spectra of graphene on BN exhibit spectroscopic features that are sharper than those obtained for graphene on SiO(2). We observe a significant reduction in local microscopic charge inhomogeneity for graphene on BN compared to graphene on SiO(2).

Controlling inelastic light scattering quantum pathways in graphene

Inelastic light scattering spectroscopy has, since its first discovery, been an indispensable tool in physical science for probing elementary excitations, such as phonons, magnons and plasmons in both bulk and nanoscale materials. In the quantum mechanical picture of inelastic light scattering, incident photons first excite a set of intermediate electronic states, which then generate crystal elementary excitations and radiate energy-shifted photons. The intermediate electronic excitations therefore have a crucial role as quantum pathways in inelastic light scattering, and this is exemplified by resonant Raman scattering and Raman interference. The ability to control these excitation pathways can open up new opportunities to probe, manipulate and utilize inelastic light scattering. Here we achieve excitation pathway control in graphene with electrostatic doping. Our study reveals quantum interference between different Raman pathways in graphene: when some of the pathways are blocked, the one-phonon Raman intensity does not diminish, as commonly expected, but increases dramatically. This discovery sheds new light on the understanding of resonance Raman scattering in graphene. In addition, we demonstrate hot-electron luminescence in graphene as the Fermi energy approaches half the laser excitation energy. This hot luminescence, which is another form of inelastic light scattering, results from excited-state relaxation channels that become available only in heavily doped graphene.

Graphene as a Long-Term Metal Oxidation Barrier: Worse Than Nothing

Anticorrosion and antioxidation surface treatments such as paint or anodization are a foundational component in nearly all industries. Graphene, a single-atom-thick sheet of carbon with impressive impermeability to gases, seems to hold promise as an effective anticorrosion barrier, and recent work supports this hope. We perform a complete study of the short- and long-term performance of graphene coatings for Cu and Si substrates. Our work reveals that although graphene indeed offers effective short-term oxidation protection, over long time scales it promotes more extensive wet corrosion than that seen for an initially bare, unprotected Cu surface. This surprising result has important implications for future scientific studies and industrial applications. In addition to informing any future work on graphene as a protective coating, the results presented here have implications for graphenes performance in a wide range of applications.

Boron nitride substrates for high mobility chemical vapor deposited graphene

Chemical vapor deposited (CVD) graphene is often presented as a scalable solution to graphene device fabrication, but to date such graphene has exhibited lower mobility than that produced by exfoliation. Using a boron nitride underlayer, we achieve mobilities as high as 37 000 cm2/V s, an order of magnitude higher than commonly reported for CVD graphene and better than most exfoliated graphene. This result demonstrates that the barrier to scalable, high mobility CVD graphene is not the growth technique but rather the choice of a substrate that minimizes carrier scattering.