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A vortex is a universal and significant phenomenon that has been known for centuries. However, creating vortices to the atomic limit has remained elusive. Very recently, it was demonstrated that intervalley scattering induced by the single carbon defect of graphene leads to phase winding over a closed path surrounding the defect. Motivated by this, we demonstrate that the single carbon defects at A and B sublattices of graphene can be regarded as pseudospin-mediated atomic-scale vortices with angular momenta l = +2 and -2, respectively. The quantum interference measurements of the vortices indicate that the vortices cancel each other, resulting in zero total angular momentum, in the |A| = |B| case, and they show aggregate chirality and angular momenta similar to a single vortex of the majority in the |A| ≠ |B| case, where |A| (|B|) is the number of vortices with angular momenta l = +2 (l = -2).

Led to significant capacity improvement to 1800 mA/h after 100 cycles for nano-graphene-N4, which is the first report for a carbonaceous materials anode. In addition, the doping level, id est, number of nitrogen atoms, had a significant influence on the molecular self-assembled structures through hierarchical self-assembly. As the nitrogen concentration increased, the d-space between the nanosheets increased from 3.4 to 4.3. The capacity of the nano-graphene increased greatly from 500 mAh/g for nano-graphene without N-doping to 1800 mAh/g for nano-graphene with nanographene-N4, indicating that the capacity is related to the structures, and was defined and the relationship between performance and structure was determined.

Creating a single-carbon vacancy introduces (quasi-)localized states for both σ and π electrons in graphene. Theoretically, interactions between the localized σ electrons and quasilocalized π electrons of a single-carbon vacancy in graphene are predicted to control its magnetism. However, experimentally confirming this prediction through manipulating the interactions remains an outstanding challenge. Here we report the manipulation of magnetism in the vicinity of an individual single-carbon vacancy in graphene by using a scanning tunnelling microscopy (STM) tip. Our spin-polarized STM measurements, complemented by density functional theory calculations, indicate that the interactions between the localized σ and quasilocalized π electrons could split the π electrons into two states with opposite spins even when they are well above the Fermi level. Via the STM tip, we successfully manipulate both the magnitude and direction of magnetic moment of the π electrons with respect to that of the σ electrons. Three different magnetic states of the single-carbon vacancy, exhibiting magnetic moments of about 1.6 μB, 0.5 μB, and 0 μB respectively, are realized in our experiment.

Graphene quantum dots (GQDs) not only have potential applications on spin qubit,but also serve as essential platforms to study the fundamental properties of Dirac fermions, such as Klein tunneling and Berry phase. By now, the study of quantum confinement in GQDs still attract much attention in condensed matter physics. In this article, we review the experimental progresses on quantum confinement in GQDs mainly by using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS). Here, the GQDs are divided into Klein GQDs, bound-state GQDs and edge-terminated GQDs according to their different confinement strength. Based on the realization of quasi-bound states in Klein GQDs, external perpendicular magnetic field is utilized as a manipulation approach to trigger and control the novel properties by tuning Berry phase and electron-electron (e-e) interaction. The tip induced edge-free GQDs can serve as an intuitive mean to explore the broken symmetry states at nanoscale and single-electron accuracy, which are expected to be used in studying physical properties of different two-dimentional materials. Moreover, high-spin magnetic ground states are successfully introduced in edge-terminated GQDs by designing and synthesizing triangulene zigzag nanographenes., Comment: https://rdcu.be/cBFYq

Shubnikov-de Haas oscillations are the most well-known magneto-oscillations in transport measurements. They are caused by Landau quantization of two-dimensional (2D) electron systems in the presence of a magnetic field. Here we demonstrate that a scanning tunneling microscope (STM) can locally measure similar magneto-oscillations in 2D systems. In Landau level spectroscopy measurements with fine magnetic-field increments, we observed fixed-energy magnetic-field-dependent oscillations of the local density of states. From the measured tunneling magneto-conductance oscillations acquired by STM, energy-momentum dispersions and Berry phases of a monolayer, Bernal-stacked bilayer, and ABC-stacked trilayer graphene were obtained. The reported method is applicable to a wide range of materials because it can obtain the magneto-oscillations of 2D systems larger than the magnetic length; importantly, it also requires no gate electrode.

Graphene nanobubbles (GNBs) have attracted much attention due to the ability to generate large pseudo-magnetic fields unattainable by ordinary laboratory magnets. However, GNBs are always randomly produced by the reported protocols, therefore, their size and location are difficult to manipulate, which restricts their potential applications. Here, using the functional atomic force microscopy (AFM), we demonstrate the ability to form programmable GNBs. The precision of AFM facilitates the location definition of GNBs, and their size and shape are tuned by the stimulus bias of AFM tip. With tuning the tip voltage, the bubble contour can gradually transit from parabolic to Gaussian profile. Moreover, the unique three-fold symmetric pseudo-magnetic field pattern with monotonous regularity, which is only theoretically predicted previously, is directly observed in the GNB with an approximately parabolic profile. Our study may provide an opportunity to study high magnetic field regimes with the designed periodicity in two dimensional materials., Presence of nano-bubbles within an atomically thin material generates potentially large pseudo-magnetic fields. Here, the authors report an innovative technique to induce nano-bubbles in graphene with desirable features and high precision through energized AFM tips, and experimentally measure three-fold symmetric pseudo-magnetic fields up to 120 T.

Development of heteroatom-doped porous carbon frameworks derived from renewable biomaterials is highly desirable. Here we report phytic acid-chitosan (PA-CS) hydrogel as a platform for facile preparation of N, P dual-doped porous carbon networks via direct pyrolysis. The hydrogel system shows great versatility towards incorporating graphene oxide or metal ions, providing a way to introduce graphene sheets or metal nanoparticles into carbon matrix as needed. After the incorporation of graphene, the obtained N, P dual-doped carbon/graphene (NPC/G) sample shows a large specific surface area (1824 m2 g−1), with a mixed meso- and micro-pore volume of 1.04 cm3 g−1. Importantly, the NPC/G sample exhibits high activity towards electrochemical oxygen reduction reaction in both alkaline and acidic electrolyte, ensuring a high-performance air catalyst of primary zinc-air batteries. Hopefully, this work provides a new method for the preparation of porous carbon materials with desired properties for catalysis.

Ordered atomic-scale superlattices on a surface hold great interest both for basic science and for potential applications in advanced technology. However, controlled fabrication of superlattices down to the atomic scale has proven exceptionally challenging. Here we develop a segregation method to realize self-organization of S superlattices at the interface of graphene and S-rich Cu substrates. Via scanning tunneling microscope measurements, we directly image well-ordered identical nanocluster superlattices and atomic superlattices under the cover of graphene. Scanning tunneling spectra show that the superlattices in turn could modulate the electronic structure of top-layer graphene. Importantly, a special-ordered S monatomic superlattice commensurate with a graphene lattice is found to drive semimetal graphene into a symmetry-broken phase-the electronic Kekulé distortion phase-which opens a bandgap of ∼245 meV.

Magnetism of graphene can be created by atomic defects, either hydrogen adsorption or single-carbon vacancy formation, owing to the unpaired $\ensuremath{\pi}$ electrons around the defects. Here we explore, based on rigorous first principles calculations, the possibility of voltage manipulation of two such types of $\ensuremath{\pi}$ magnetism in graphene via a scanning tunneling microscope tip. We find a remarkably different behavior. For the hydrogen, the magnetic moment can be switched on and off with voltage-induced doping, whereas, for the carbon vacancy, the spin splitting of the $\ensuremath{\pi}$ bands persists, almost independent of the extent of doping, due to the coupling between the $\ensuremath{\pi}$ and the $\ensuremath{\sigma}$ bonds. Furthermore, the local atomic structures near the vacancy can be reversibly manipulated by a coordination mechanism between an intermediate tip-defect distance and a moderate tip voltage, consequently leading to the reversal of spin polarization of the $\ensuremath{\pi}$ bands. Voltage control of the local magnetic states may open a new avenue for potential applications in spintronics.

The relativistic massless charge carriers with a Fermi velocity of about c/300 in graphene enable us to realize two distinct types of resonances (here, c is the speed of light in vacuum). One is the electron whispering-gallery mode in graphene quantum dots arising from the Klein tunneling of the massless Dirac fermions. The other is the atomic collapse state, which has never been observed in experiment with real atoms due to the difficulty of producing heavy nuclei with charge Z > 170; however, they can be realized near a Coulomb impurity in graphene with a charge Z ≥ 1 because of the “small” velocity of the Dirac excitations. Here we demonstrate that both the electron whispering-gallery modes and atomic collapse states coexist in graphene/WSe2 heterostructure quantum dots due to the Coulomb-like potential near their edges. By applying a perpendicular magnetic field, we explore the evolution from the atomic collapse states to unusual Landau levels in the collapse regime.

Wafer-scale growth of the unidirectional graphene monolayer on Ge surfaces has rejuvenated the intense study of the surfaces and interfaces of semiconductors underneath graphene. Recently, it was reported that the Ge atoms in the Ge(110) surface beneath a graphene monolayer underwent a rearrangement and formed an ordered (6 × 2) reconstruction. However, a plausible atomic model related to this (6 × 2) reconstruction is still lacking. Here, by using scanning tunnelling microscopy/spectroscopy (STM/S) and density functional theory (DFT) calculations, we deeply investigated the structural and electronic properties of the Ge(110) (6 × 2) surface encapsulated by a graphene monolayer. The (6 × 2) surface reconstruction was confirmed for the post-annealing-graphene-covered Ge(110) surface via STM, and was found to be quite air-stable, owing to the protection of the graphene monolayer against surface oxidation. Our study disclosed that the topographic features of the topmost graphene monolayer and the Ge(110) surface could be selectively imaged by utilizing suitable scanning biases. According to the STM results and DFT calculations, a rational ball-and-stick model of the (6 × 2) reconstruction was successfully provided, in which an elemental building block comprising two Ge triangles and two isolated Ge atoms adsorbed on the unreconstructed ideal Ge(110) surface. Local density of states of the graphene/Ge surface was explored via scanning tunneling spectroscopy (STS), presenting four well-defined differential conductance (dI/dV) peaks, protruding at energies of 0.2, 0.4, 0.6 and 0.8 eV, respectively. The four peaks predominantly originated from the surface states of the reconstructing adatoms and were well reproduced by our theoretical simulation. This result means that the Ge surface is very robust after being encapsulated by the epitaxial graphene, which could be advantageous for directly fabricating graphene/Ge-hybrid high-speed electronics and optoelectronics based on conventional microelectronics technology.

A remarkable property of twisted bilayer graphene (TBG) with small twist angle is the presence of a well-defined and conserved low-energy valley degrees of freedom1, which can potentially bring about new types of valley-associated spontaneous-symmetry breaking phases. Electron-electron (e-e) interactions in the TBG near the magic angle 1.1 degree can lift the valley degeneracy, allowing for the realization of orbital magnetism and topological phases2-11. However, direct measurement of the orbital-based magnetism in the TBG is still lacking up to now. Here we report evidence for orbital magnetic moment generated by the moire-scale current loops in a TBG with a twist angle {\theta} ~ 1.68 degree. The valley degeneracy of the 1.68 degree TBG is removed by e-e interactions when its low-energy van Hove singularity (VHS) is nearly half filled. A large and linear response of the valley splitting to magnetic fields is observed, attributing to coupling to the large orbital magnetic moment induced by chiral current loops circulating in the moire pattern. According to our experiment, the orbital magnetic moment is about 10.7 uB per moire supercell. Our result paves the way to explore magnetism that is purely orbital in slightly twisted graphene system., Comment: 4 figures in main text

The electronic properties of van der Waals (vdW) structures can be substantially modified by the moire superlattice potential, which strongly depends on the twist angle among the compounds. In twisted bilayer graphene (TBG), two low-energy Van Hove singularities (VHSs) move closer with decreasing twist angles and finally become highly non-dispersive flat bands at the magic angle (~ 1.1 degree). When the Fermi level lies within the flat bands of the TBG near the magic angle, Coulomb interaction is supposed to exceed the kinetic energy of the electrons, which can drive the system into various strongly correlated phases. Moreover, the strongly correlated states of flat bands are also realized in other graphene-based vdW structures with an interlayer twist. In this article, we mainly review the recent experimental advances on the strongly correlated physics of the magic-angle TBG (MATBG) and the small-angle twisted multilayer graphene. Lastly we will give out a perspective of this field., Comment: Invited review

Coulomb interaction is of central importance in localized energy levels (bound states) or electronic flat bands and can result in many exotic quantum phases. In a graphene monolayer, the relativistic massless Dirac fermion nature of the charge carriers enables us to realize unprecedented quasibound states, which are trapped temporarily via whispering-gallery modes (WGMs), in circular graphene quantum dots (GQDs). Here we show that Coulomb interaction still plays a dominating role in determining the electronic properties of the temporarily confined quasibound states with the lifetime (trapping time) of \ensuremath{\sim}10 fs. Our scanning tunneling microscopy and spectroscopy measurements demonstrate that the discrete quasibound state in a GQD will split into two peaks when it is partially filled. The energy separation of the two split peaks increases linearly with inverse effective radius of the GQDs, indicating that the splitting arises from the Coulomb interaction. Moreover, we show that the real-space distribution of the two split states separates in different regions of the GQD to reduce the Coulomb interaction, leading to the breaking of the WGM of the quasibound states.

Chiral quasiparticles in Bernal-stacked bilayer graphene have valley-contrasting Berry phases of $\ifmmode\pm\else\textpm\fi{}2\ensuremath{\pi}$. This nontrivial topological structure, associated with the pseudospin winding along a closed Fermi surface, is responsible for various novel electronic properties. Here we show that the quantum interference due to intervalley scattering induced by single-atom vacancies or impurities provides insights into the topological nature of the bilayer graphene. The scattered chiral quasiparticles between distinct valleys with opposite chirality undergo a rotation of pseudospin that results in the Friedel oscillation with wavefront dislocations. The number of dislocations reflects the information about pseudospin texture and hence can be used to measure the Berry phase. As demonstrated both experimentally and theoretically, the Friedel oscillation, depending on the single-atom vacancy or impurity at different sublattices, can exhibit $N=4$, 2, or 0 additional wavefronts, characterizing the $2\ensuremath{\pi}$ Berry phase of the bilayer graphene. Our results provide a comprehensive study of the intervalley quantum interference in bilayer graphene and can be extended to multilayer graphene, shedding light on the pseudospin physics.

N-doped graphene (NG)/TiO2 composites were prepared by a hydrothermal method using HF as the surface etchant and urea as the nitrogen source. The morphology and structure of the NG /TiO2 composites were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), UV-visible diffuse reflectance spectroscopy (UV-Vis DRS) and specific surface area (BET). The pore size distribution of the composite and the effect of NG addition on the photocatalytic properties were studied. The photocatalytic properties of the composite were evaluated under UV and sunlight conditions respectively. The results show that TiO2 is uniformly loaded on the surface of NG, and NG/TiO2 is mesoporous material. The introduction of NG can effectively improve the photocatalytic properties, 5wt% NG/TiO2 has the best photocatalytic degradation effect on methylene blue. The degradation rate of methylene blue is 96.30% at 30 min under UV and 99.87% at 180 min under sunlight.

It is quite easy to control spin polarization and spin direction of a system via magnetic fields. However, there is no such a direct and efficient way to manipulate valley pseudospin degree of freedom. Here, we demonstrate experimentally that it is possible to realize valley polarization and valley inversion in graphene by using both strain-induced pseudomagnetic fields and real magnetic fields. The pseudomagnetic fields, which are quite different from real magnetic fields, pointing in opposite directions at the two distinct valleys of graphene. Therefore, coexistence of the pseudomagnetic fields and the real magnetic fields leads to imbalanced effective magnetic fields at two distinct valleys of graphene. This allows us to control the valley in graphene as convenient as the electron spin. In this work, we report consistent observation of valley polarization and inversion in strained graphene via pseudo-Landau levels, splitting of real Landau levels and valley splitting of confined states using scanning tunneling spectroscopy. Our results highlight a pathway to valleytronics in strained graphene-based platforms., 4 figures in main text, accepted by Phys. Rev. Lett

Theoretically, coupling of phonons with quasiparticles in the Landau levels (LLs) of graphene was predicted to generate a new sequence of discrete states in the density of states, i.e., phonon peaks. However, it was believed that these phonon peaks are extremely weak due to weak electron-phonon coupling in graphene. Here, we report the experimental observation of giant phonon peaks in a graphene monolayer induced by enhanced electron-phonon coupling. We demonstrate that emission or absorption of phonons of quasiparticles in the LLs of graphene generates the phonon peaks, which even exhibits fine structures corresponding to bound states of an electron and of a phonon. We also show that it is possible to tune the relative strength of the phonon peaks at nanoscale by controlling interactions between graphene and the supporting substrate. The local strain in graphene may play a vital role in enhancing the electron-phonon coupling, which results in the observed giant phonon peaks. Our experiment indicates that it is possible to explore interesting emergent phenomena, such as superconductivity, induced by electron-phonon coupling in graphene.

Coupled quantum dots (QDs), usually referred to as artificial molecules, are important not only in exploring fundamental physics of coupled quantum objects, but also in realizing advanced QD devices. However, previous studies have been limited to artificial molecules with nonrelativistic fermions. Here, we show that relativistic artificial molecules can be realized when two circular graphene QDs are coupled to each other. Using scanning tunneling microscopy (STM) and spectroscopy (STS), we observe the formation of bonding and antibonding states of the relativistic artificial molecule and directly visualize these states of the two coupled graphene QDs. The formation of the relativistic molecular states strongly alters distributions of massless Dirac fermions confined in the graphene QDs. Because of the relativistic nature of the molecular states, our experiment demonstrates that the degeneracy of different angular-momentum states in the relativistic artificial molecule can be further lifted by external magnetic fields. Then, both the bonding and antibonding states are split into two peaks.

Twisted graphene bilayers (TGBs) have low-energy van Hove singularities (VHSs) that are strongly localized around AA-stacked regions of the moire pattern. Therefore, they exhibit novel many-body electronic states, such as Mott-like insulator and unconventional superconductivity. Unfortunately, these strongly correlated states were only observed in magic angle TGBs with the twist angle theta~1.1{\deg}, requiring a precisely tuned structure. Is it possible to realize exotic quantum phases in the TGBs not limited at the magic angle? Here we studied electronic properties of a TGB with theta~1.64{\deg} and demonstrated that a VHS splits into two spin-polarized states flanking the Fermi energy when the VHS is close to the Fermi level. Such a result indicates that localized magnetic moments emerge in the AA-stacked regions of the TGB. Since the low-energy VHSs are quite easy to be reached in slightly TGBs, our result therefore provides a facile direction to realize novel quantum phases in graphene system., Comment: 4 figures

This study examined the characteristics of small molecular structure nano-graphene in a dynamic hierarchical self-assembly and found that graphene is rearranged under its own pressure during dynamic aggregation and water ripples are formed by the d-spacing. The composition and structure were studied using a range of material characterization techniques. No covalent bonds were observed between molecules, and the self-assembled driving force was the only intermolecular interaction: Van der Waals’ force in the intra-layer and π–π interactions between layers. The arranged-rearranged structures provided a range of lithium ion shuttle channels, including the space between layers and diffusing through the nanosheets, which decrease the diffusion distance of lithium ions remarkably and reduce the irreversible capacity of the battery. Electronic supplementary material The online version of this article (10.1186/s11671-019-2903-4) contains supplementary material, which is available to authorized users.

Very recently, twisted graphene bilayers (TGBs) around the first magic angle $\ensuremath{\theta}\ensuremath{\approx}1.{1}^{\ensuremath{\circ}}$ have attracted much attention for the realization of exotic quantum states, such as correlated insulator behavior and unconventional superconductivity. Here we elaborately study a series of TGBs around the first magic angle engineered by heterostrain, where each layer is strained independently. Our experiment indicates that a moderate heterostrain enables the structural evolution from the small-angle TGB (\ensuremath{\theta} \ensuremath{\sim} 1.5\ifmmode^\circ\else\textdegree\fi{}) to the strained magic-angle TGB (\ensuremath{\theta} \ensuremath{\sim} 1.1\ifmmode^\circ\else\textdegree\fi{}), exhibiting the characteristic low-energy flat bands. The heterostrain can even drive the system into highly strained tiny-angle TGBs (\ensuremath{\theta}$\ensuremath{\ll}1.1$\ifmmode^\circ\else\textdegree\fi{}) with large deformed tetragonal superlattices, where a unique network of topological helical edge states emerges. Furthermore, the predicted domain wall modes, which are strongly localized and result in a hexagon-triangle-mixed frustrated lattice derived from the Kagome lattice, are observed in the strained tiny-angle TGBs.

ABC-stacked trilayer graphene (TLG) was predicted to exhibit novel many-body phenomena due to the existence of almost dispersionless flat bands near the charge neutrality point. Here, using high-magnetic-field scanning tunneling microscopy, we present Landau Level (LL) spectroscopy measurements of high-quality ABC-stacked TLG on graphite. We observe an approximately linear magnetic-field scaling of valley splitting and spin splitting in the ABC-stacked TLG. Our experiment indicates that the spin splitting decreases dramatically with increasing the LL index. When the lowest LL is partially filled, we find an obvious enhancement of the spin splitting, attributing to strong many-body effects. Moreover, we observe linear energy scaling of the inverse lifetime of quasiparticles, providing an additional evidence for the strong electron-electron interactions in the ABC-stacked TLG. These results imply that interesting broken-symmetry states and novel electron correlated effects could emerge in the ABC-stacked TLG in the presence of high magnetic fields.

The dream of graphene modified to have a spin-polarized semiconducting band structure has remained elusive for over a decade. This study uses spin-polarized scanning tunneling microscopy to reveal that the strong interaction between graphene and Ni(111) substrate generates a large gap in graphene, and simultaneously leads to a relative shift of majority- and minority-spin bands. This band structure persists even at room temperature, which is promising for graphene-based spintronic information technologies.

Fast and effective methods for the removal of pollutants are crucial for the development of new sustainable water treatment technologies. In this work, we have reported the electrically accelerated removal of some typical organic pollutants by a three-dimensional graphene aerogel (3DG). The porous 3DG was fabricated by chemical reduction of graphene oxide. The morphology and structure of 3DG were characterized by microscopic and spectroscopic approaches. The experiments indicated that 3DG-based electrosorption could accelerate the removal of positively and negatively charged pollutants, such as Acid Red 88, Orange II, and Methylene Blue, as well as enhance the maximum adsorption capacity toward these contaminants. The interaction mechanisms between these organic pollutants and 3DG surface were further elucidated by Dispersion corrected Density Functional Theory (DFT-D) calculations. This 3DG-based system offers a potentially effective method for the rapid removal of organic pollutants and provides a new sustainable approach for water and wastewater treatment. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2154–2162, 2016

Very recently, it was demonstrated explicitly that a zigzag graphene nanoribbon (GNR) exhibits a conductance of G 0 /2 ( G 0 = 2 e 2 / h is the quantum of conductance) even along distances as large as 16 μm at room-temperature (Baringhaus et al . 2014). Such a result is puzzling as none of previous theories seem to match the experimental observations. Here, a model was proposed to explain the robust single-channel ballistic transport properties in zigzag GNR. The sp 3 distortion of carbon atoms at the GNR edges induces a large spin-orbit coupling on the edge atoms, which enhances spin-flip scattering of the edge states of the zigzag GNR. With sufficient spin-flip scattering, the wave-function of the edge states becomes a superposition of the spin-up and spin-down components. Then the coupling of the two edges becomes important. This removes the edge degree of freedom and results in the robust conductance of G 0 /2 in the zigzag GNR.

Heterostructures made by stacking different materials on top of each other are expected to exhibit unusual properties and new phenomena. Interface of the heterostructures plays a vital role in determining their properties. Here, we report the observation of a two-dimensional (2D) spinodal interface in graphene-molybdenum carbide ({\alpha}-Mo2C) heterostructures, which arises from spinodal decomposition occurring at the heterointerface, by using scanning tunneling microscopy. Our experiment demonstrates that the 2D spinodal interface modulates graphene into whispering gallery resonant networks filled with quasi-bound states of massless Dirac fermions. Moreover, below the superconducting transition temperature of the underlying {\alpha}-Mo2C, the 2D spinodal interface behaves as disorders, resulting in the breakdown of the proximity-induced superconductivity in graphene. Our result sheds new light on tuning properties of heterostructures based on interface engineering., Comment: 4 figures in main text

Even after a decade of research, a fundamental controversy persists concerning the electronic structure of a suspended graphene monolayer, as revealed by scanning tunneling spectroscopy (STS). Is the spectrum truly gapped, or V-shaped? This study systematically shows that substrate interaction can affect the STS spectrum of graphene crucially, by suppressing out-of-plane phonons and thus eliminating any gap. Switching the tunneling spectrum of graphene with voltage pulses through the probe's tip is also demonstrated. This sort of clear understanding is needed for successful engineering of related graphene devices.

Negative differential conductance (NDC), characterized by the decreasing current with increasing voltage, has attracted continuous attention for its various novel applications. The NDC typically exists in a certain range of bias voltages for a selected system and controlling the regions of NDC in curves of current versus voltage ($I\text{\ensuremath{-}}V$) is experimentally challenging. Here, we demonstrate a magnetic-field-controlled NDC in scanning tunneling spectroscopy of graphene npn junction resonators. The magnetic field not only can switch on and off the NDC, but also can continuously tune the regions of the NDC in the $I\text{\ensuremath{-}}V$ curves. In the graphene npn junction resonators, magnetic fields generate sharp and pronounced Landau-level peaks with the help of the Klein tunneling of massless Dirac fermions. A tip of scanning tunneling microscope induces a relatively shift of the Landau levels in graphene beneath the tip. Tunneling between the misaligned Landau levels results in the magnetic-field-controlled NDC.

Creation of high-quality $p\ensuremath{-}n$ junctions in graphene monolayer is vital in studying many exotic phenomena of massless Dirac fermions. However, even with the fast progress of graphene technology for more than ten years, it remains conspicuously difficult to generate nanoscale and atomically sharp $p\ensuremath{-}n$ junctions in graphene. Here, we realized nanoscale $p\ensuremath{-}n$ junctions with atomically sharp boundaries in graphene monolayer by using monolayer vacancy island of Cu surface. The generated sharp $p\ensuremath{-}n$ junctions with the height as high as 660 meV isolate the graphene above the Cu monolayer vacancy island as nanoscale graphene quantum dots (GQDs) in a continuous graphene sheet. Massless Dirac fermions are confined by the $p\ensuremath{-}n$ junctions for a finite time to form quasibound states in the GQDs. By using scanning tunneling microscopy, we observe resonances of quasibound states in the GQDs with various sizes and directly visualize effects of geometries of the GQDs on the quantum interference patterns of the quasibound states, which allow us to test the quantum electron optics based on graphene in atomic scale.

It is of keen interest to researchers understanding different approaches to confine massless Dirac fermions in graphene, which is also a central problem in making electronic devices based on graphene. Here, we studied spatial confinement, magnetic localization and their interactions on massless Dirac fermions in an angled graphene wedge formed by two linear graphene p-n boundaries with an angle 34. Using scanning tunneling microscopy, we visualized quasibound states temporarily confined in the studied graphene wedge. Large perpendicular magnetic fields condensed the massless Dirac fermions in the graphene wedge into Landau levels (LLs). The spatial confinement of the wedge affects the Landau quantization, which enables us to experimentally measure the spatial extent of the wave functions of the LLs. The magnetic fields induce a sudden and large increase in energy of the quasibound states because of a pi Berry phase jump of the massless Dirac fermions in graphene. Such a behavior is the hallmark of the Klein tunneling in graphene. Our experiment demonstrated that the angled wedge is a unique system with the critical magnetic fields for the pi Berry phase jump depending on distance from summit of the wedge., Comment: 4 Figures in main text

Twist, as a simple and unique degree of freedom, could lead to enormous novel quantum phenomena in bilayer graphene. A small rotation angle introduces low-energy van Hove singularities (VHSs) approaching the Fermi level, which result in unusual correlated states in the bilayer graphene. It is reasonable to expect that the twist could also affect the electronic properties of few-layer graphene dramatically. However, such an issue has remained experimentally elusive. Here, by using scanning tunneling microscopy/spectroscopy (STM/STS), we systematically studied a twisted trilayer graphene (TTG) with two different small twist angles between adjacent layers. Two sets of VHSs originating from the two twist angles were observed in the TTG, indicating that the TTG could be simply regarded as a combination of two different twisted bilayer graphene. By using high-resolution STS, we observed split of the VHSs and directly imaged spatial symmetry breaking of electronic states around the VHSs. These results suggest that electron-electron interactions play an important role in affecting the electronic properties of graphene systems with low-energy VHSs., 4 Figures in main text

Finite-size twisted bilayer graphene (TBG, where here the TBG is of nanoscale size) is quite unstable and will change its structure to a Bernal (or $AB$-stacking) bilayer with a much lower energy. Therefore, the lack of finite-size TBG makes its electronic properties difficult to access in experiments. In this paper, a special confined TBG is obtained in the overlaid area of two continuous misoriented graphene sheets. The width of the confined region of the TBG changes gradually from about 22 to 0 nm. By using scanning tunneling microscopy, we study carefully the structure and the electronic properties of finite-size TBG. Our results indicate that the low-energy electronic properties, including twist-induced Van Hove singularities (VHSs) and spatial modulation of the local density of states, are strongly affected by the translational symmetry breaking of the finite-size TBG. However, the electronic properties above the energy of the VHSs are almost not influenced by quantum confinement even when the width of the TBG is reduced to only a single moir\'e spot.

Optical tweezers integrated with Raman spectroscopy allows analyzing a single trapped micro-particle, but is generally less effective for individual nano-sized objects in the 10-100 nm range. The main challenge is the weak gradient force on nanoparticles that is insufficient to overcome the destabilizing effect of scattering force and Brownian motion. Here, we present standing-wave Raman tweezers for stable trapping and sensitive characterization of single isolated nanostructures with a low laser power by combining a standing-wave optical trap (SWOT) with confocal Raman spectroscopy. This scheme has stronger intensity gradients and balanced scattering forces, and thus is more stable and sensitive in measuring nanoparticles in liquid with 4-8 fold increase in the Raman signals. It can be used to analyze many nanoparticles that cannot be measured with single-beam Raman tweezers, including individual single-walled carbon nanotubes (SWCNT), graphene flakes, biological particles, polystyrene beads (100 nm), SERS-active metal nanoparticles, and high-refractive semiconductor nanoparticles with a low laser power of a few milliwatts. This would enable sorting and characterization of specific SWCNTs and other nanoparticles based on their increased Raman fingerprints.

Massless Dirac fermions in graphene provide unprecedented opportunities to realize the Klein paradox, which is one of the most exotic and striking properties of relativistic particles. In the seminal theoretical work [Katsnelson et al., Nat. Phys. 2 620 (2006)], it was predicted that the massless Dirac fermions can pass through one-dimensional (1D) potential barriers unimpededly at normal incidence. Such a result seems to preclude confinement of the massless Dirac fermions in graphene by using 1D potential barriers. Here, we demonstrate, both experimentally and theoretically, that massless Dirac fermions can be trapped in quasi-1D npn junction of a continuous graphene monolayer. Because of highly anisotropic transmission of the massless Dirac fermions at n-p junction boundaries (the so-called Klein tunneling in graphene), charge carries incident at large oblique angles will be reflected from one edge of the junction with high probability and continue to bounce from the opposite edge. Consequently, these electrons are trapped for a finite time to form quasi-bound states in the quasi-1D npn junction. The quasi-bound states seen as pronounced resonances are probed and the quantum interference patterns arising from these states are directly visualized in our scanning tunneling microscope measurements., 4 Figures in main text

Assembling different two-dimensional (2D) crystals, covering a very broad range of properties, into van der Waals (vdW) heterostructures enables unprecedented possibilities for combining the best of different ingredients in one objective material. So far, metallic, semiconducting, and insulating 2D crystals have been used successfully in making functional vdW heterostructures with properties by design. Here, we expand 2D superconducting crystals as a building block of vdW hererostructures. One-step growth of large-scale high-quality vdW heterostructures of graphene and 2D superconducting $\ensuremath{\alpha}\text{\ensuremath{-}}\mathrm{M}{\mathrm{o}}_{2}\mathrm{C}$ by using chemical vapor deposition is reported. The superconductivity and its 2D nature of the heterostructures are characterized by our scanning tunneling microscopy measurements. This adds 2D superconductivity, the most attractive property of condensed matter physics, to vdW heterostructures.

When electrons are confined in a two-dimensional (2D) system, typical quantum–mechanical phenomena such as Landau quantization can be detected. Graphene systems, including the single atomic layer and few-layer stacked crystals, are ideal 2D materials for studying a variety of quantum–mechanical problems. In this article, we review the experimental progress in the unusual Landau quantized behaviors of Dirac fermions in monolayer and multilayer graphene by using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS). Through STS measurement of the strong magnetic fields, distinct Landau-level spectra and rich level-splitting phenomena are observed in different graphene layers. These unique properties provide an effective method for identifying the number of layers, as well as the stacking orders, and investigating the fundamentally physical phenomena of graphene. Moreover, in the presence of a strain and charged defects, the Landau quantization of graphene can be significantly modified, leading to unusual spectroscopic and electronic properties.

Considerable efforts have been made to trap massless Dirac fermions in graphene monolayer, but only quasi-bound states are realized in continuous graphene sheets up to now. Here, we demonstrate the realization of bound states in nanoscale graphene quantum dots (GQDs) in a continuous graphene sheet. The GQDs are electronically isolated from the surrounding continuous graphene sheet by circular boundaries, which are generated by strong coupling between graphene and substrate. By using scanning tunneling microscopy (STM), we observe single-electron charging states of the GQDs, seen as Coulomb oscillations in the tunneling conductance. Evolution of single-electron tunneling of the GQDs between the Coulomb blockade regime and the Coulomb staircase regime is observed by tuning the STM tip-sample distances. Spatial maps of the local electronic densities reveal concentric rings inside the GQDs with each ring corresponding to a single Coulomb oscillation of the tunneling spectra. These results indicate explicitly that the electrons are completely trapped inside the nanoscale GQDs., 4 figures in main text. accepted in Physical Review B Rapid Communications

The interlayer gallery between two adjacent sheets of van der Waals materials is expected to modify properties of atoms and molecules confined at the atomic interfaces. Here, we directly image individual hydrogen atom intercalated between two graphene sheets and investigate its dynamics by scanning tunnelling microscope (STM). The intercalated hydrogen atom is found to be remarkably different from atomic hydrogen chemisorbed on external surface of graphene. Our STM measurements, complemented by first-principles calculations, show that the hydrogen atom intercalated between two graphene sheets has dramatically reduced potential barriers for elementary migration steps. Especially, the confined atomic hydrogen dissociation energy from graphene is reduced to 0.34 eV, which is only about a third of a hydrogen atom chemisorbed on graphene. This offers a unique platform for direct imaging of the atomic dynamics of confined atoms. Our results suggest that the atomic interfaces of van der Waals materials may provide a confined environment to tune the interfacial chemical reactions., Comment: 5 figures

The controlled fabrication of single-crystal twelve-pointed graphene grains is demonstrated for the first time by ambient pressure chemical vapor deposition on a liquid Cu surface. An edge-diffusion limited mechanism is proposed. The highly controllable growth of twelve-pointed graphene grains presents an intriguing case for the fundamental study of graphene growth and should exhibit wide applications in graphene-based electronics.

Hierarchical graphene architectures (HGAs) that grow by stacking of layers are produced on a liquid copper surface using chemical vapor deposition. The stacking mode--for example hexagonal-hexagonal-hexagonal or hexagonal-snowflake-dendritic--can be simply controlled. Measurements of the electrical properties of HGAs indicate that hierarchical stacking of graphene may be a simple and effective way of tailoring their properties without degrading them.

Understanding the interactions between graphene nanomaterials (GNMs) and antibiotics in aqueous solution is critical to both the engineering applications of GNMs and the assessment of their potential impact on the fate and transport of antibiotics in the aquatic environment. In this study, adsorption of one common antibiotic, tetracycline, by graphene oxide (GO) and reduced graphene oxide (RGO) was examined with multi-walled carbon nanotubes (MWCNTs) and graphite as comparison. The results showed that the tetracycline adsorption capacity by the four selected carbonaceous materials on the unit mass basis followed an order of GO>RGO>MWCNTs>graphite. Upon normalization by surface area, graphite, RGO and MWCNTs had almost the same high tetracycline adsorption affinity while GO exhibited the lowest. We proposed π-electron-property dependent interaction mechanisms to explain the observed different adsorption behaviors. Density functional theory (DFT) calculations suggested that the oxygen-containing functional groups on GO surface reduced its π-electron-donating ability, and thus decreased the π-based interactions between tetracycline and GO surface. Comparison of adsorption efficiency at different pH indicated that electrostatic interaction also played an important role in tetracycline-GO interactions. Site energy analysis confirmed a highly heterogeneous distribution of the binding sites and strong tetracycline binding affinity of GO surface.

Crystallographic alignment between two-dimensional crystals in van der Waals heterostructures brought a number of profound physical phenomena, including observation of Hofstadter butterfly and topological currents, and promising novel applications, such as resonant tunnelling transistors. Here, by probing the electronic density of states in graphene using graphene-hexagonal boron nitride tunnelling transistors, we demonstrate a structural transition of bilayer graphene from incommensurate twisted stacking state into a commensurate AB stacking due to a macroscopic graphene self-rotation. This structural transition is accompanied by a topological transition in the reciprocal space and by pseudospin texturing. The stacking transition is driven by van der Waals interaction energy of the two graphene layers and is thermally activated by unpinning the microscopic chemical adsorbents which are then removed by the self-cleaning of graphene., 13 pages, 6 figures

Pristine graphene is strongly diamagnetic. However, graphene with single carbon atom defects could exhibit paramagnetism. Theoretically, the $\ensuremath{\pi}$ magnetism induced by the monovacancy in graphene is characteristic of two spin-split density-of-states (DOS) peaks close to the Dirac point. Since its prediction, many experiments have attempted to study this $\ensuremath{\pi}$ magnetism in graphene, whereas only a notable resonance peak has been observed around the atomic defects, leaving the $\ensuremath{\pi}$ magnetism experimentally elusive. Here, we report direct experimental evidence of $\ensuremath{\pi}$ magnetism by using a scanning tunneling microscope. We demonstrate that the localized state of the atomic defects is split into two DOS peaks with energy separations of several tens of meV. Strong magnetic fields further increase the energy separations of the two spin-polarized peaks and lead to a Zeeman-like splitting. Unexpectedly, the effective $g$ factor around the atomic defect is measured to be about 40, which is about 20 times larger than the $g$ factor for electron spins.

2D Mo2C has drawn considerable interest recently for its excellent properties in 2D superconductivity and enhanced hydrogen evolution reaction (HER). Liquid metals have been demonstrated to be an ideal substrate for large-area 2D Mo2C growth. However, the growth mechanism of 2D Mo2C on liquid metals has rarely been explored. Here we report the synthesis of high-quality 2D Mo2C crystals and Mo2C/graphene heterostructures on liquid Au by chemical vapor deposition method. A sunk growth mode of 2D Mo2C on liquid Au substrates has revealed, by atomic force microscope characterizations, that some Mo2C crystals grow below the level of Au terraces around tens of nanometers. Furthermore, graphene/Mo2C heterostructure is controllably synthesized by tuning the hydrogen/carbon ratio, which is proven to be an enhanced electrocatalyst for HER against pure Mo2C crystal grown on liquid Au substrates.

Knowing exact nature of broken-symmetry states around individual atomic defects of graphene is very important in understanding the electronic properties. Here, we realize measurement of valley-dependent spin splitting around atomic defects of graphene at nanoscale and single-electron level by using edge-free graphene quantum dots. Our experiments detect large valley-dependent spin splitting around atomic defects of graphene due to the coexistence of sublattice symmetry breaking, enhanced spin–orbit coupling and time reversal symmetry breaking. The spin splitting in the two distinct valleys has opposite direction and almost has the same amplitude. The strategy reported in this work is quite robust and could be extended to measure broken-symmetry states in other 2D systems.

Trilayer graphene (TLG) exhibits rich novel electronic properties and extraordinary quantum Hall phenomena owning to enhanced electronic interactions and tunable chirality of its quasiparticles. Here, we report direct observation of chirality transition of quasiparticles at stacking solitons of TLG via spatial-resolved Landau level spectroscopy. The one-dimensional stacking solitons with width of the order of 10 nm separate adjacent Bernal-stacked TLG and rhombohedral-stacked TLG. By using high field tunneling spectra of scanning tunneling microscopy, we measured Landau quantization in both the Bernal-stacked TLG and the rhombohedral-stacked TLG and, importantly, we observed evolution of quasiparticles between the chiral degree l = 1&2 and l = 3 across the stacking domain wall solitons. Our experiment indicates that such a chirality transition occurs smoothly, accompanying the transition of the stacking orders of TLG, around the domain wall solitons. This result demonstrates the important and hitherto neglected relationship between the crystallographic stacking order and the chirality of quasiparticles in graphene systems., 4 Figures

To generate a moderate band gap in a graphene monolayer is a very important but rather difficult task. A rare working solution of this problem is to cut it into one-dimensional (1D) nanometer-wide ribbons. Here we show that, instead of cutting the graphene monolayer, a wide band gap can be created in a unique 1D strained structure, i.e., a wrinkled graphene-nanoribbon-like (GNR-like) structure, of a continuous graphene sheet via strong hybridization between the graphene and the metal substrate. The wrinkled GNR-like structures with widths of only a few nanometers are observed in a continuous graphene sheet grown on a Rh foil by using thermal strain engineering. Spatially resolved scanning tunneling spectroscopy revealed a band-gap opening of a few hundred meV in the GNR-like structure in an otherwise continuous metallic graphene sheet, directly demonstrating the realization of a metallic-semiconducting-metallic junction entirely in a graphene monolayer.