Javier Sanchez-Yamagishi

Scanning tunnelling microscopy and spectroscopy of ultra-flat graphene on hexagonal boron nitride

Graphene has demonstrated great promise for future electronics technology as well as fundamental physics applications because of its linear energy-momentum dispersion relations which cross at the Dirac point. However, accessing the physics of the low-density region at the Dirac point has been difficult because of disorder that leaves the graphene with local microscopic electron and hole puddles. Efforts have been made to reduce the disorder by suspending graphene, leading to fabrication challenges and delicate devices which make local spectroscopic measurements difficult. Recently, it has been shown that placing graphene on hexagonal boron nitride (hBN) yields improved device performance. Here we use scanning tunnelling microscopy to show that graphene conforms to hBN, as evidenced by the presence of Moiré patterns. However, contrary to predictions, this conformation does not lead to a sizeable band gap because of the misalignment of the lattices. Moreover, local spectroscopy measurements demonstrate that the electron-hole charge fluctuations are reduced by two orders of magnitude as compared with those on silicon oxide. This leads to charge fluctuations that are as small as in suspended graphene, opening up Dirac point physics to more diverse experiments.Graphene has demonstrated great promise for future electronics technology as well as fundamental physics applications because of its linear energy-momentum dispersion relations which cross at the Dirac point[1, 2]. However, accessing the physics of the low density region at the Dirac point has been difficult because of the presence of disorder which leaves the graphene with local microscopic electron and hole puddles[3–5], resulting in a finite density of carriers even at the charge neutrality point. Efforts have been made to reduce the disorder by suspending graphene, leading to fabrication challenges and delicate devices which make local spectroscopic measurements difficult[6, 7]. Recently, it has been shown that placing graphene on hexagonal boron nitride (hBN) yields improved device performance[8]. In this letter, we use scanning tunneling microscopy to show that graphene conforms to hBN, as evidenced by the presence of Moiré patterns in the topographic images. However, contrary to recent predictions[9, 10], this conformation does not lead to a sizable band gap due to the misalignment of the lattices. Moreover, local spectroscopy measurements demonstrate that the electron-hole charge fluctuations are reduced by two orders of magnitude as compared to those on silicon oxide. This leads to charge fluctuations which are as small as in suspended graphene[6], opening up Dirac point physics to more diverse experiments than are possible on freestanding devices. ∗Electronic address: leroy@physics.arizona.edu

Massive Dirac Fermions and Hofstadter Butterfly in a van der Waals Heterostructure

Graphene, Gapped and Butterflied The remarkable transport properties of graphene, such as the high electron mobility, make it a promising material for electronics. However, unlike semiconductors such as silicon, graphenes electronic structure lacks a band gap, and a transistor made out of graphene would not have an “off” state. Hunt et al. (p. 1427, published online 16 May; see the Perspective by Fuhrer) modulated the electronic properties of graphene by building a heterostructure consisting of a graphene flake resting on hexagonal boron nitride (hBN), which has the same honeycomb structure as graphene, but consists of alternating boron and nitrogen atoms instead of carbons. The natural mismatch between the graphene and hBN lattices led to a moire pattern with a large wavelength, causing the opening of a band gap, the formation of an elusive fractional quantum Hall state, and, at high magnetic fields, a fractal phenomenon in the electronic structure called the Hofstadter butterfly. A band gap is observed in a monolayer graphene–hexagonal boron nitride heterostructure. [Also see Perspective by Fuhrer] van der Waals heterostructures constitute a new class of artificial materials formed by stacking atomically thin planar crystals. We demonstrated band structure engineering in a van der Waals heterostructure composed of a monolayer graphene flake coupled to a rotationally aligned hexagonal boron nitride substrate. The spatially varying interlayer atomic registry results in both a local breaking of the carbon sublattice symmetry and a long-range moiré superlattice potential in the graphene. In our samples, this interplay between short- and long-wavelength effects resulted in a band structure described by isolated superlattice minibands and an unexpectedly large band gap at charge neutrality. This picture is confirmed by our observation of fractional quantum Hall states at ±53 filling and features associated with the Hofstadter butterfly at ultrahigh magnetic fields.

Emergence of superlattice Dirac points in graphene on hexagonal boron nitride

It is well known that graphene deposited on hexagonal boron nitride produces moire patterns in scanning tunnelling microscopy images. The interaction that produces this pattern also produces a commensurate periodic potential that generates a set of Dirac points that are different from those of the graphene lattice itself.

Anisotropic Etching and Nanoribbon Formation in Single-Layer Graphene

We demonstrate anisotropic etching of single-layer graphene by thermally activated nickel nanoparticles. Using this technique, we obtain sub-10-nm nanoribbons and other graphene nanostructures with edges aligned along a single crystallographic direction. We observe a new catalytic channeling behavior, whereby etched cuts do not intersect, resulting in continuously connected geometries. Raman spectroscopy and electronic measurements show that the quality of the graphene is resilient under the etching conditions, indicating that this method may serve as a powerful technique to produce graphene nanocircuits with well-defined crystallographic edges.

Understanding and controlling the substrate effect on graphene electron-transfer chemistry via reactivity imprint lithography

Graphene has exceptional electronic, optical, mechanical and thermal properties, which provide it with great potential for use in electronic, optoelectronic and sensing applications. The chemical functionalization of graphene has been investigated with a view to controlling its electronic properties and interactions with other materials. Covalent modification of graphene by organic diazonium salts has been used to achieve these goals, but because graphene comprises only a single atomic layer, it is strongly influenced by the underlying substrate. Here, we show a stark difference in the rate of electron-transfer reactions with organic diazonium salts for monolayer graphene supported on a variety of substrates. Reactions proceed rapidly for graphene supported on SiO(2) and Al(2)O(3) (sapphire), but negligibly on alkyl-terminated and hexagonal boron nitride (hBN) surfaces, as shown by Raman spectroscopy. We also develop a model of reactivity based on substrate-induced electron-hole puddles in graphene, and achieve spatial patterning of chemical reactions in graphene by patterning the substrate.The chemical functionalization of graphene enables control over electronic properties and sensor recognition sites. However, its study is confounded by an unusually strong influence of the underlying substrate. In this paper, we show a stark difference in the rate of electron transfer chemistry with aryl diazonium salts on monolayer graphene supported on a broad range of substrates. Reactions proceed rapidly when graphene is on SiO_2 and Al_2O_3 (sapphire), but negligibly on alkyl-terminated and hexagonal boron nitride (hBN) surfaces. The effect is contrary to expectations based on doping levels and can instead be described using a reactivity model accounting for substrate-induced electron-hole puddles in graphene. Raman spectroscopic mapping is used to characterize the effect of the substrates on graphene. Reactivity imprint lithography (RIL) is demonstrated as a technique for spatially patterning chemical groups on graphene by patterning the underlying substrate, and is applied to the covalent tethering of proteins on graphene.

Tunable symmetry breaking and helical edge transport in a graphene quantum spin Hall state

Low-dimensional electronic systems have traditionally been obtained by electrostatically confining electrons, either in heterostructures or in intrinsically nanoscale materials such as single molecules, nanowires and graphene. Recently, a new method has emerged with the recognition that symmetry-protected topological (SPT) phases, which occur in systems with an energy gap to quasiparticle excitations (such as insulators or superconductors), can host robust surface states that remain gapless as long as the relevant global symmetry remains unbroken. The nature of the charge carriers in SPT surface states is intimately tied to the symmetry of the bulk, resulting in one- and two-dimensional electronic systems with novel properties. For example, time reversal symmetry endows the massless charge carriers on the surface of a three-dimensional topological insulator with helicity, fixing the orientation of their spin relative to their momentum. Weakly breaking this symmetry generates a gap on the surface, resulting in charge carriers with finite effective mass and exotic spin textures. Analogous manipulations have yet to be demonstrated in two-dimensional topological insulators, where the primary example of a SPT phase is the quantum spin Hall state. Here we demonstrate experimentally that charge-neutral monolayer graphene has a quantum spin Hall state when it is subjected to a very large magnetic field angled with respect to the graphene plane. In contrast to time-reversal-symmetric systems, this state is protected by a symmetry of planar spin rotations that emerges as electron spins in a half-filled Landau level are polarized by the large magnetic field. The properties of the resulting helical edge states can be modulated by balancing the applied field against an intrinsic antiferromagnetic instability, which tends to spontaneously break the spin-rotation symmetry. In the resulting canted antiferromagnetic state, we observe transport signatures of gapped edge states, which constitute a new kind of one-dimensional electronic system with a tunable bandgap and an associated spin texture.

Correlated insulator behaviour at half-filling in magic-angle graphene superlattices

A van der Waals heterostructure is a type of metamaterial that consists of vertically stacked two-dimensional building blocks held together by the van der Waals forces between the layers. This design means that the properties of van der Waals heterostructures can be engineered precisely, even more so than those of two-dimensional materials. One such property is the ‘twist’ angle between different layers in the heterostructure. This angle has a crucial role in the electronic properties of van der Waals heterostructures, but does not have a direct analogue in other types of heterostructure, such as semiconductors grown using molecular beam epitaxy. For small twist angles, the moiré pattern that is produced by the lattice misorientation between the two-dimensional layers creates long-range modulation of the stacking order. So far, studies of the effects of the twist angle in van der Waals heterostructures have concentrated mostly on heterostructures consisting of monolayer graphene on top of hexagonal boron nitride, which exhibit relatively weak interlayer interaction owing to the large bandgap in hexagonal boron nitride. Here we study a heterostructure consisting of bilayer graphene, in which the two graphene layers are twisted relative to each other by a certain angle. We show experimentally that, as predicted theoretically, when this angle is close to the ‘magic’ angle the electronic band structure near zero Fermi energy becomes flat, owing to strong interlayer coupling. These flat bands exhibit insulating states at half-filling, which are not expected in the absence of correlations between electrons. We show that these correlated states at half-filling are consistent with Mott-like insulator states, which can arise from electrons being localized in the superlattice that is induced by the moiré pattern. These properties of magic-angle-twisted bilayer graphene heterostructures suggest that these materials could be used to study other exotic many-body quantum phases in two dimensions in the absence of a magnetic field. The accessibility of the flat bands through electrical tunability and the bandwidth tunability through the twist angle could pave the way towards more exotic correlated systems, such as unconventional superconductors and quantum spin liquids.

Quantum Hall Effect, Screening, and Layer-Polarized Insulating States in Twisted Bilayer Graphene

We investigate electronic transport in dual-gated twisted-bilayer graphene. Despite the subnanometer proximity between the layers, we identify independent contributions to the magnetoresistance from the graphene Landau level spectrum of each layer. We demonstrate that the filling factor of each layer can be independently controlled via the dual gates, which we use to induce Landau level crossings between the layers. By analyzing the gate dependence of the Landau level crossings, we characterize the finite interlayer screening and extract the capacitance between the atomically spaced layers. At zero filling factor, we observe an insulating state at large displacement fields, which can be explained by the presence of counterpropagating edge states with interlayer coupling.

Superlattice-Induced Insulating States and Valley-Protected Orbits in Twisted Bilayer Graphene

Twisted bilayer graphene (TBLG) is one of the simplest van der Waals heterostructures, yet it yields a complex electronic system with intricate interplay between moiré physics and interlayer hybridization effects. We report on electronic transport measurements of high mobility small angle TBLG devices showing clear evidence for insulating states at the superlattice band edges, with thermal activation gaps several times larger than theoretically predicted. Moreover, Shubnikov-de Haas oscillations and tight binding calculations reveal that the band structure consists of two intersecting Fermi contours whose crossing points are effectively unhybridized. We attribute this to exponentially suppressed interlayer hopping amplitudes for momentum transfers larger than the moiré wave vector.

Large Variations of the Raman Signal in the Spectra of Twisted Bilayer Graphene on a BN Substrate.

We report an unusual enhancement of the Raman signal of the G mode in a twisted graphene bilayer (2-LG) on a hexagonal single-crystalline boron nitride substrate. We used an isotopically engineered 2-LG, where the top layer was composed of (13)C atoms and the bottom layer of (12)C atoms. Consequently, it was possible by Raman spectroscopy to distinguish between the enhancement coming from the top and bottom layers. The enhancement of the G mode was, however, found to be similar for the top and bottom layers, and this enhancement effect was observed only at certain locations on the substrate. The experiment with two different laser excitation energies showed that the location of the enhanced spots is dependent on the laser excitation energy. Therefore our results suggest that the enhancement comes from new states in the electronic structure, which are a consequence of a local specific rotation of the grains in graphene layers.