Giant orbital magnetic moments and paramagnetic shift in artificial relativistic atoms and molecules.

Materials such as graphene and topological insulators host massless Dirac fermions that enable the study of relativistic quantum phenomena. Single quantum dots and coupled quantum dots formed with massless Dirac fermions can be viewed as artificial relativistic atoms and molecules, respectively. Such structures offer a unique testbed to study atomic and molecular physics in the ultrarelativistic regime (particle speed close to the speed of light). Here we use a scanning tunnelling microscope to create and probe single and coupled electrostatically defined graphene quantum dots to unravel the magnetic-field responses of artificial relativistic nanostructures. We observe a giant orbital Zeeman splitting and orbital magnetic moment up to ~70 meV T-1 and ~600µB (µB, Bohr magneton) in single graphene quantum dots. For coupled graphene quantum dots, Aharonov-Bohm oscillations and a strong Van Vleck paramagnetic shift of ~20 meV T-2 are observed. Our findings provide fundamental insights into relativistic quantum dot states, which can be potentially leveraged for use in quantum information science.

Gate-Tunable Magnetism and Giant Magnetoresistance in Suspended Rhombohedral-Stacked Few-Layer Graphene.

Conventionally, magnetism arises from the strong exchange interaction among the magnetic moments of d- or f-shell electrons. It can also emerge in perfect lattices from nonmagnetic elements, such as that exemplified by the Stoner criterion. Here we report tunable magnetism in suspended rhombohedral-stacked few-layer graphene (r-FLG) devices with flat bands. At small doping levels (n ∼ 1011 cm-2), we observe prominent conductance hysteresis and giant magnetoconductance that exceeds 1000% as a function of magnetic fields. Both phenomena are tunable by density and temperature and disappear at n > 1012 cm-2 or T > 5 K. These results are confirmed by first-principles calculations, which indicate the formation of a half-metallic state in doped r-FLG, in which the magnetization is tunable by electric field. Our combined experimental and theoretical work demonstrate that magnetism and spin polarization, arising from the strong electronic interactions in flat bands, emerge in a system composed entirely of carbon atoms.

Ultrasharp Lateral p-n Junctions in Modulation-Doped Graphene.

We demonstrate ultrasharp (≲10 nm) lateral p-n junctions in graphene using electronic transport, scanning tunneling microscopy, and first-principles calculations. The p-n junction lies at the boundary between differentially doped regions of a graphene sheet, where one side is intrinsic and the other is charge-doped by proximity to a flake of α-RuCl3 across a thin insulating barrier. We extract the p-n junction contribution to the device resistance to place bounds on the junction width. We achieve an ultrasharp junction when the boundary between the intrinsic and doped regions is defined by a cleaved crystalline edge of α-RuCl3 located 2 nm from the graphene. Scanning tunneling spectroscopy in heterostructures of graphene, hexagonal boron nitride, and α-RuCl3 shows potential variations on a sub 10 nm length scale. First-principles calculations reveal that the charge-doping of graphene decays sharply over just nanometers from the edge of the α-RuCl3 flake.

Control of Giant Topological Magnetic Moment and Valley Splitting in Trilayer Graphene.

Bloch states of electrons in honeycomb two-dimensional crystals with multivalley band structure and broken inversion symmetry have orbital magnetic moments of a topological nature. In crystals with two degenerate valleys, a perpendicular magnetic field lifts the valley degeneracy via a Zeeman effect due to these magnetic moments, leading to magnetoelectric effects which can be leveraged for creating valleytronic devices. In this work, we demonstrate that trilayer graphene with Bernal stacking (ABA TLG), hosts topological magnetic moments with a large and widely tunable valley g factor (g_{ν}), reaching a value g_{ν}∼1050 at the extreme of the studied parametric range. The reported experiment consists in sublattice-resolved scanning tunneling spectroscopy under perpendicular electric and magnetic fields that control the TLG bands. The tunneling spectra agree very well with the results of theoretical modeling that includes the full details of the TLG tight-binding model and accounts for a quantum-dot-like potential profile formed electrostatically under the scanning tunneling microscope tip.

Imaging Quantum Interference in Stadium-Shaped Monolayer and Bilayer Graphene Quantum Dots.

Experimental realizations of graphene-based stadium-shaped quantum dots (QDs) have been few and have been incompatible with scanned probe microscopy. Yet, the direct visualization of electronic states within these QDs is crucial for determining the existence of quantum chaos in these systems. We report the fabrication and characterization of electrostatically defined stadium-shaped QDs in heterostructure devices composed of monolayer graphene (MLG) and bilayer graphene (BLG). To realize a stadium-shaped QD, we utilized the tip of a scanning tunneling microscope to charge defects in a supporting hexagonal boron nitride flake. The stadium states visualized are consistent with tight-binding-based simulations but lack clear quantum chaos signatures. The absence of quantum chaos features in MLG-based stadium QDs is attributed to the leaky nature of the confinement potential due to Klein tunneling. In contrast, for BLG-based stadium QDs (which have stronger confinement) quantum chaos is precluded by the smooth confinement potential which reduces interference and mixing between states.

Sublattice Dependence and Gate Tunability of Midgap and Resonant States Induced by Native Dopants in Bernal-Stacked Bilayer Graphene.

The properties of semiconductors can be crucially impacted by midgap states induced by dopants, which can be native or intentionally incorporated in the crystal lattice. For Bernal-stacked bilayer graphene (BLG), which has a tunable band gap, the existence of midgap states induced by dopants or adatoms has been investigated theoretically and observed indirectly in electron transport experiments. Here, we characterize BLG midgap states in real space, with atomic-scale resolution with scanning tunneling microscopy and spectroscopy. We show that the midgap states in BLG-for which we demonstrate gate tunability-appear when the dopant is hosted on the nondimer sublattice sites. We further evidence the presence of narrow resonances at the onset of the high-energy bands (valence or conduction, depending on the dopant type) when the dopants lie on the dimer sublattice sites. Our results are supported by tight-binding calculations that agree remarkably well with the experimental findings.

Direct Visualization of Native Defects in Graphite and Their Effect on the Electronic Properties of Bernal-Stacked Bilayer Graphene.

Graphite crystals used to prepare graphene-based heterostructures are generally assumed to be defect free. We report here scanning tunneling microscopy results that show graphite commonly used to prepare graphene devices can contain a significant amount of native defects. Extensive scanning of the surface allows us to determine the concentration of native defects to be 6.6 × 108 cm-2. We further study the effects of these native defects on the electronic properties of Bernal-stacked bilayer graphene. We observe gate-dependent intravalley scattering and successfully compare our experimental results to T-matrix-based calculations, revealing a clear carrier density dependence in the distribution of the scattering vectors. We also present a technique for evaluating the spatial distribution of short-scale scattering. Finally, we present a theoretical analysis based on the Boltzmann transport equation that predicts that the dilute native defects identified in our study are an important extrinsic source of scattering, ultimately setting the charge carrier mobility at low temperatures.

Visualization and Manipulation of Bilayer Graphene Quantum Dots with Broken Rotational Symmetry and Nontrivial Topology.

Electrostatically defined quantum dots (QDs) in Bernal stacked bilayer graphene (BLG) are a promising quantum information platform because of their long spin decoherence times, high sample quality, and tunability. Importantly, the shape of QD states determines the electron energy spectrum, the interactions between electrons, and the coupling of electrons to their environment, all of which are relevant for quantum information processing. Despite its importance, the shape of BLG QD states remains experimentally unexamined. Here we report direct visualization of BLG QD states by using a scanning tunneling microscope. Strikingly, we find these states exhibit a robust broken rotational symmetry. By using a numerical tight-binding model, we determine that the observed broken rotational symmetry can be attributed to low energy anisotropic bands. We then compare confined holes and electrons and demonstrate the influence of BLG's nontrivial band topology. Our study distinguishes BLG QDs from prior QD platforms with trivial band topology.

Comprehensive Electrostatic Modeling of Exposed Quantum Dots in Graphene/Hexagonal Boron Nitride Heterostructures.

Recent experimental advancements have enabled the creation of tunable localized electrostatic potentials in graphene/hexagonal boron nitride (hBN) heterostructures without concealing the graphene surface. These potentials corral graphene electrons yielding systems akin to electrostatically defined quantum dots (QDs). The spectroscopic characterization of these exposed QDs with the scanning tunneling microscope (STM) revealed intriguing resonances that are consistent with a tunneling probability of 100% across the QD walls. This effect, known as Klein tunneling, is emblematic of relativistic particles, underscoring the uniqueness of these graphene QDs. Despite the advancements with electrostatically defined graphene QDs, a complete understanding of their spectroscopic features still remains elusive. In this study, we address this lapse in knowledge by comprehensively considering the electrostatic environment of exposed graphene QDs. We then implement these considerations into tight binding calculations to enable simulations of the graphene QD local density of states. We find that the inclusion of the STM tip's electrostatics in conjunction with that of the underlying hBN charges reproduces all of the experimentally resolved spectroscopic features. Our work provides an effective approach for modeling the electrostatics of exposed graphene QDs. The methods discussed here can be applied to other electrostatically defined QD systems that are also exposed.

Visualizing the Effect of an Electrostatic Gate with Angle-Resolved Photoemission Spectroscopy.

Electrostatic gating is pervasive in materials science, yet its effects on the electronic band structure of materials has never been revealed directly by angle-resolved photoemission spectroscopy (ARPES), the technique of choice to noninvasively probe the electronic band structure of a material. By means of a state-of-the-art ARPES setup with submicron spatial resolution, we have investigated a heterostructure composed of Bernal-stacked bilayer graphene (BLG) on hexagonal boron nitride and deposited on a graphite flake. By voltage biasing the latter, the electric field effect is directly visualized on the valence band as well as on the carbon 1s core level of BLG. The band gap opening of BLG submitted to a transverse electric field is discussed and the importance of intra layer screening is put forward. Our results pave the way for new studies that will use momentum-resolved electronic structure information to gain insight on the physics of materials submitted to the electric field effect.

Nanowrinkled Carbon Aerogels Embedded with FeN x Sites as Effective Oxygen Electrodes for Rechargeable Zinc-Air Battery.

Rational design of single-metal atom sites in carbon substrates by a flexible strategy is highly desired for the preparation of high-performance catalysts for metal-air batteries. In this study, biomass hydrogel reactors are utilized as structural templates to prepare carbon aerogels embedded with single iron atoms by controlled pyrolysis. The tortuous and interlaced hydrogel chains lead to the formation of abundant nanowrinkles in the porous carbon aerogels, and single iron atoms are dispersed and stabilized within the defective carbon skeletons. X-ray absorption spectroscopy measurements indicate that the iron centers are mostly involved in the coordination structure of FeN4, with a minor fraction (ca. 1/5) in the form of FeN3C. First-principles calculations show that the FeN x sites in the Stone-Wales configurations induced by the nanowrinkles of the hierarchically porous carbon aerogels show a much lower free energy than the normal counterparts. The resulting iron and nitrogen-codoped carbon aerogels exhibit excellent and reversible oxygen electrocatalytic activity, and can be used as bifunctional cathode catalysts in rechargeable Zn-air batteries, with a performance even better than that based on commercial Pt/C and RuO2 catalysts. Results from this study highlight the significance of structural distortions of the metal sites in carbon matrices in the design and engineering of highly active single-atom catalysts.

Visualization and Control of Single-Electron Charging in Bilayer Graphene Quantum Dots.

Graphene p-n junctions provide an ideal platform for investigating novel behavior at the boundary between electronics and optics that arise from massless Dirac Fermions, such as whispering gallery modes and Veselago lensing. Bilayer graphene also hosts Dirac Fermions, but they differ from single-layer graphene charge carriers because they are massive, can be gapped by an applied perpendicular electric field, and have very different pseudospin selection rules across a p-n junction. Novel phenomena predicted for these massive Dirac Fermions at p-n junctions include anti-Klein tunneling, oscillatory Zener tunneling, and electron cloaked states. Despite these predictions there has been little experimental focus on the microscopic spatial behavior of massive Dirac Fermions in the presence of p-n junctions. Here we report the experimental manipulation and characterization of massive Dirac Fermions within bilayer graphene quantum dots defined by circular p-n junctions through the use of scanning tunneling microscopy-based (STM) methods. Our p-n junctions are created via a flexible technique that enables realization of exposed quantum dots in bilayer graphene/hBN heterostructures. These quantum dots exhibit sharp spectroscopic resonances that disperse in energy as a function of applied gate voltage. Spatial maps of these features show prominent concentric rings with diameters that can be tuned by an electrostatic gate. This behavior is explained by single-electron charging of localized states that arise from the quantum confinement of massive Dirac Fermions within our exposed bilayer graphene quantum dots.

Molecular Arrangement and Charge Transfer in C60/Graphene Heterostructures.

Charge transfer at the interface between dissimilar materials is at the heart of electronics and photovoltaics. Here we study the molecular orientation, electronic structure, and local charge transfer at the interface region of C60 deposited on graphene, with and without supporting substrates such as hexagonal boron nitride. We employ ab initio density functional theory with van der Waals interactions and experimentally characterize interface devices using high-resolution transmission electron microscopy and electronic transport. Charge transfer between C60 and the graphene is found to be sensitive to the nature of the underlying supporting substrate and to the crystallinity and local orientation of the C60. Even at room temperature, C60 molecules interfaced to graphene are orientationally locked into position. High electron and hole mobilities are preserved in graphene with crystalline C60 overlayers, which has ramifications for organic high-mobility field-effect devices.

Nanoscale Control of Rewriteable Doping Patterns in Pristine Graphene/Boron Nitride Heterostructures.

Nanoscale control of charge doping in two-dimensional (2D) materials permits the realization of electronic analogs of optical phenomena, relativistic physics at low energies, and technologically promising nanoelectronics. Electrostatic gating and chemical doping are the two most common methods to achieve local control of such doping. However, these approaches suffer from complicated fabrication processes that introduce contamination, change material properties irreversibly, and lack flexible pattern control. Here we demonstrate a clean, simple, and reversible technique that permits writing, reading, and erasing of doping patterns for 2D materials at the nanometer scale. We accomplish this by employing a graphene/boron nitride heterostructure that is equipped with a bottom gate electrode. By using electron transport and scanning tunneling microscopy (STM), we demonstrate that spatial control of charge doping can be realized with the application of either light or STM tip voltage excitations in conjunction with a gate electric field. Our straightforward and novel technique provides a new path toward on-demand graphene p-n junctions and ultrathin memory devices.

Automatic segmentation of Potyviridae family polyproteins.

We describe an automatic segmentation method for polyproteins of the viruses belonging to the Potyviridae family. It uses machine learning techniques in order to predict the cleavage site which define the segments in which said polyproteins are cut in their process of functional maturation. The segmentation application is publicly available for use on a website and it can be accessed through the web service interface too. The prediction models have an average sensitivity of 0.79 and a Matthews correlation coefficient average of 0.23. This method is capable of predicting correctly (coinciding with previously published segmentation) the segmentation of sequences which come from Potyvirus and Rymovirus, genera. However accurate prediction capabilities are affected when faced with either atypical sequences or viruses belonging to less common genera in the Potyviridae family. Future work will focus on establishing greater flexibility in this sense.

Characterization and manipulation of individual defects in insulating hexagonal boron nitride using scanning tunnelling microscopy.

Defects play a key role in determining the properties and technological applications of nanoscale materials and, because they tend to be highly localized, characterizing them at the single-defect level is of particular importance. Scanning tunnelling microscopy has long been used to image the electronic structure of individual point defects in conductors, semiconductors and ultrathin films, but such single-defect electronic characterization remains an elusive goal for intrinsic bulk insulators. Here, we show that individual native defects in an intrinsic bulk hexagonal boron nitride insulator can be characterized and manipulated using a scanning tunnelling microscope. This would typically be impossible due to the lack of a conducting drain path for electrical current. We overcome this problem by using a graphene/boron nitride heterostructure, which exploits the atomically thin nature of graphene to allow the visualization of defect phenomena in the underlying bulk boron nitride. We observe three different defect structures that we attribute to defects within the bulk insulating boron nitride. Using scanning tunnelling spectroscopy we obtain charge and energy-level information for these boron nitride defect structures. We also show that it is possible to manipulate the defects through voltage pulses applied to the scanning tunnelling microscope tip.

Fabrication of Gate-tunable Graphene Devices for Scanning Tunneling Microscopy Studies with Coulomb Impurities.

Owing to its relativistic low-energy charge carriers, the interaction between graphene and various impurities leads to a wealth of new physics and degrees of freedom to control electronic devices. In particular, the behavior of graphene's charge carriers in response to potentials from charged Coulomb impurities is predicted to differ significantly from that of most materials. Scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) can provide detailed information on both the spatial and energy dependence of graphene's electronic structure in the presence of a charged impurity. The design of a hybrid impurity-graphene device, fabricated using controlled deposition of impurities onto a back-gated graphene surface, has enabled several novel methods for controllably tuning graphene's electronic properties. Electrostatic gating enables control of the charge carrier density in graphene and the ability to reversibly tune the charge and/or molecular states of an impurity. This paper outlines the process of fabricating a gate-tunable graphene device decorated with individual Coulomb impurities for combined STM/STS studies. These studies provide valuable insights into the underlying physics, as well as signposts for designing hybrid graphene devices.

Direct Growth of Single- and Few-Layer MoS2 on h-BN with Preferred Relative Rotation Angles.

Monolayer molybdenum disulfide (MoS2) is a promising two-dimensional direct-bandgap semiconductor with potential applications in atomically thin and flexible electronics. An attractive insulating substrate or mate for MoS2 (and related materials such as graphene) is hexagonal boron nitride (h-BN). Stacked heterostructures of MoS2 and h-BN have been produced by manual transfer methods, but a more efficient and scalable assembly method is needed. Here we demonstrate the direct growth of single- and few-layer MoS2 on h-BN by chemical vapor deposition (CVD) method, which is scalable with suitably structured substrates. The growth mechanisms for single-layer and few-layer samples are found to be distinct, and for single-layer samples low relative rotation angles (<5°) between the MoS2 and h-BN lattices prevail. Moreover, MoS2 directly grown on h-BN maintains its intrinsic 1.89 eV bandgap. Our CVD synthesis method presents an important advancement toward controllable and scalable MoS2-based electronic devices.

Topological valley transport at bilayer graphene domain walls.

Electron valley, a degree of freedom that is analogous to spin, can lead to novel topological phases in bilayer graphene. A tunable bandgap can be induced in bilayer graphene by an external electric field, and such gapped bilayer graphene is predicted to be a topological insulating phase protected by no-valley mixing symmetry, featuring quantum valley Hall effects and chiral edge states. Observation of such chiral edge states, however, is challenging because inter-valley scattering is induced by atomic-scale defects at real bilayer graphene edges. Recent theoretical work has shown that domain walls between AB- and BA-stacked bilayer graphene can support protected chiral edge states of quantum valley Hall insulators. Here we report an experimental observation of ballistic (that is, with no scattering of electrons) conducting channels at bilayer graphene domain walls. We employ near-field infrared nanometre-scale microscopy (nanoscopy) to image in situ bilayer graphene layer-stacking domain walls on device substrates, and we fabricate dual-gated field effect transistors based on the domain walls. Unlike single-domain bilayer graphene, which shows gapped insulating behaviour under a vertical electrical field, bilayer graphene domain walls feature one-dimensional valley-polarized conducting channels with a ballistic length of about 400 nanometres at 4 kelvin. Such topologically protected one-dimensional chiral states at bilayer graphene domain walls open up opportunities for exploring unique topological phases and valley physics in graphene.

Broken symmetry quantum Hall states in dual-gated ABA trilayer graphene.

ABA-stacked trilayer graphene is a unique 2D electron system with mirror reflection symmetry and unconventional quantum Hall effect. We present low-temperature transport measurements on dual-gated suspended trilayer graphene in the quantum Hall (QH) regime. We observe QH plateaus at filling factors ν = -8, -2, 2, 6, and 10, which is in agreement with the full-parameter tight binding calculations. In high magnetic fields, odd-integer plateaus are also resolved, indicating almost complete lifting of the 12-fold degeneracy of the lowest Landau level (LL). Under an out-of-plane electric field E(perpendicular), we observe degeneracy breaking and transitions between QH plateaus. Interestingly, depending on its direction, E(perpendicular) selectively breaks the LL degeneracies in the electron-doped or hole-doped regimes. Our results underscore the rich interaction-induced phenomena in trilayer graphene.