Electrons in two-dimensional hexagonal materials have valley degree of freedom, which can be used to encode and process quantum information. The valley-selective excitations, governed by the circularly polarised light resonant with the material's band-gap, continues to be the foundation of valleytronics. It is often assumed that achieving valley selective excitation in pristine graphene with all-optical means is not possible due to the inversion symmetry of the system. Here we demonstrate that both valley-selective excitation and valley-selective high-harmonic generation can be achieved in pristine graphene by using the combination of two counter-rotating circularly polarized fields, the fundamental and its second harmonic. Controlling the relative phase between the two colours allows us to select the valleys where the electron-hole pairs and higher-order harmonics are generated. We also describe an all-optical method for measuring valley polarization in graphene with a weak probe pulse. This work offers a robust recipe to write and read valley-selective electron excitations in materials with zero bandgap and zero Berry curvature.
We discuss the valley-orbit interaction (VOI) and the concept of VOI based valleytronics. Potential of such valleytronics is illustrated, with graphene as an example material, in several frontier applications comprising FETs, quantum computing, and quantum communications. Two important devices are discussed as examples, namely, 1) valley pair qubits in coupled graphene quantum dots, to build quantum networks consisting of graphene and photons, and 2) valleybased FETs consisting of graphene quantum wires (channels) and armchair graphene nanoribbons (sources and drains), to build graphene-based,…
Graphene's outstanding mechanical properties lend to strain engineering, allowing for future valleytronics and nanoelectromechanic applications. In this work, we have found that a Gaussian-shaped strain on a graphene p-n junction results in quantum Hall conductance oscillations due to the rotated angle between valley isospins at the graphene armchair edges. Furthermore, additional Fano resonances were observed as the value of the strain-induced pseudo-magnetic field approaches that of the external magnetic field. The lifted valley degeneracy, stemming from the interplay between the real and ps…
Probing and controlling the valley degree of freedom in graphene systems by transport measurements has been a major challenge to fully exploit the unique properties of this two-dimensional material. In this theoretical work, we show that this goal can be achieved by a quantum-wire geometry made of gapped graphene that acts as a valley filter with the following favorable features: i) all electrical gate control, ii) electrically switchable valley polarity, iii) robustness against configuration fluctuation, and iv) potential for room temperature operation. This valley filtering is accomplished b…
We study the states localized near an interface between conducting and insulating bilayer graphene (BLG) and show that they have highly unusual properties that have no analog in conventional systems. Moreover, the states belonging to the two independent valleys in the Brillouin zone of BLG show contrasting properties that allows a relatively easier experimental realization of various valley based functionalities desired in valleytronics without requiring any sophisticated techniques.
Two dimensional (2D) materials provide a unique platform for spintronics and valleytronics due to the ability to combine vastly different functionalities into one vertically-stacked heterostructure, where the strengths of each of the constituent materials can compensate for the weaknesses of the others. Graphene has been demonstrated to be an exceptional material for spin transport at room temperature, however it lacks a coupling of the spin and optical degrees of freedom. In contrast, spin/valley polarization can be efficiently generated in monolayer transition metal dichalcogenides (TMD) suc…
We describe an angularly asymmetric interface-scattering mechanism which allows to spatially separate the electrons in the two low-energy valleys of bilayer graphene. The effect occurs at electrostatically defined interfaces separating regions of different pseudospin polarization, and is associated with the helical winding of the pseudospin vector across the interface, which breaks the reflection symmetry in each valley. Electrons are transmitted with a preferred direction of up to 60 degree over a large energetic range in one of the valleys, and down to -60 degree in the other. In a Y-junctio…
We propose a scheme to trap and filter electrons, valley dependently, on a scale beyond the diffraction limit, in a gapped Dirac system using a circularly polarized light beam and a microscale metallic resonator. The main mechanism allowing the selection is the valley dependent break of the time reversal symmetry. Indeed in one valley, the light partially closes the already existing gap while it opens it in the other one. This difference in the band structure close to the Dirac points, induces a change in the dynamics of the electrons, leading to a valley router behaviour of the system.
Spectra of the C1s core hole, created in XPS and screened by electronic excitations in pristine and doped graphene, are calculated and discussed. We find that singular effects in the lineshapes are not possible in the pristine graphene, and their observation should be connected with the doping. However, the structure of the low energy excitation spectrum in the region where the singular behaviour is expected leads to asymmetries in the core hole lineshapes in pristine graphene similar to those in doped graphene. This makes the analysis more complex than in the case of metals and may lead to in…
Strain engineering is a promising approach for suppressing the OFF-state conductance in graphene-based devices that arises from Klein tunnelling. In this work, we derive a comprehensive tight-binding Hamiltonian for strained graphene that incorporates strain-induced effects that have been neglected hitherto, such as the distortion of the unit cell under strain, the effect of strain on the next-nearest neighbor coupling, and the second-order contributions of the strain tensor. We derive the corresponding low-energy effective Hamiltonian about the Dirac points and reformulate the boundary condit…
Due to its strong bonds graphene can stretch up to 25% of its original size without breaking. Furthermore, mechanical deformations lead to the generation of pseudo-magnetic fields (PMF) that can exceed 300 T. The generated PMF has opposite direction for electrons originating from different valleys. We show that valley-polarized currents can be generated by local straining of multi-terminal graphene devices. The pseudo-magnetic field created by a Gaussian-like deformation allows electrons from only one valley to transmit and a current of electrons from a single valley is generated at the opposi…
Local electrical imaging using microwave impedance microscope is performed on graphene in different modalities, yielding a rich hierarchy of the local conductivity. The low-conductivity graphite oxide and its derivatives show significant electronic inhomogeneity. For the conductive chemical graphene, the residual defects lead to a systematic reduction of the microwave signals. In contrast, the signals on pristine graphene agree well with a lumped-element circuit model. The local impedance information can also be used to verify the electrical contact between overlapped graphene pieces.
We investigate the ballistic electron transport in a monolayer graphene with configurational averaged impurities, located between two clean graphene leads. It is shown that the electron transmission are strongly dependent on the concentration of impurities and the incident energy. In turn, the conductance computed using the Landauer formalism shows a similar behavior to those found in experimental works as a function of the applied voltage for different concentrations of impurities in the limit of low temperatures. In the limit of zero bias voltage, the conductance shows a minimum value which …
We present a first principles method for calculating the inelastic electron tunneling spectroscopy (IETS) on gated graphene. We reproduce experiments on pristine graphene and point out the importance of including several phonon modes to correctly estimate the local doping from IETS. We demonstrate how the IETS of typical imperfections in graphene can yield characteristic fingerprints revealing e.g. adsorbate species or local buckling. Our results show how care is needed when interpreting STM images of defects due to suppression of the elastic tunneling on graphene.
We calculate core-level spectra for pristine and doped free-standing graphene sheets. Instructions for how to perform the calculations are given in detail. Although pristine graphene is not metallic the core-level spectrum presents low-energy tailing which is characteristic of metallic systems. The peak shapes vary with doping level in a characteristic way. The spectra are compared to experiments and show good agreement. We compare to two different pristine samples and to one doped sample. The pristine samples are one with quasi-free-standing epitaxial graphene on SiC obtained by hydrogen inte…
In a pristine monolayer graphene subjected to a constant electric field along the layer, the Bloch oscillation of an electron is studied in a simple and efficient way. By using the electronic dispersion relation, the formula of a semi-classical velocity is derived analytically, and then many aspects of Bloch oscillation, such as its frequency, amplitude, as well as the direction of the oscillation, are investigated. It is interesting to find that the electric field affects the component of motion, which is non-collinear with electric field, and leads the particle to be accelerated or oscillate…
We show that vapors of different chemicals produce distinguishably different effects on the low-frequency noise spectra of graphene. It was found in a systematic study that some gases change the electrical resistance of graphene devices without changing their low-frequency noise spectra while other gases modify the noise spectra by inducing Lorentzian components with distinctive features. The characteristic frequency fc of the Lorentzian noise bulges in graphene devices is different for different chemicals and varies from fc=10 - 20 Hz to fc=1300 - 1600 Hz for tetrahydrofuran and chloroform va…
Van der Waals heterostructures made of graphene and transition metal dichalcogenides (TMD) are an emerging platform for opto-electronic, -spintronic and -valleytronic devices that could benefit from (i) strong light-matter interactions and spin-valley locking in TMDs and (ii) exceptional electron and spin transport in graphene. The operation of such devices requires significant valley polarization and valley coherence, ideally up to room temperature. Here, using a comprehensive Mueller polarimetry analysis, we report \textit{artifact-free} room temperature degrees of valley polarization up to …
Atomically thin two-dimensional materials such as graphene and hexagonal boron nitride have recently been found to exhibit appreciable permeability to thermal protons, making these materials emerging candidates for separation technologies [S. Hu et al., Nature 516, 227 (2014); M. Lozada-Hidalgo et al., Science 351, 68 (2016).]. These remarkable findings remain unexplained by density-functional electronic structure calculations, which instead yield barriers that exceed by 1.0 eV those found in experiments. Here we resolve this puzzle by demonstrating that the proton transfer through pristine gr…
We present Raman spectroscopy measurements of non-etched graphene nanoribbons, with widths ranging from 15 to 160 nm, where the D-line intensity is strongly dependent on the polarization direction of the incident light. The extracted edge disorder correlation length is approximately one order of magnitude larger than on previously reported graphene ribbons fabricated by reactive ion etching techniques. This suggests a more regular crystallographic orientation of the non-etched graphene ribbons here presented. We further report on the ribbons width dependence of the line-width and frequency of …
The understanding of atomic adsorption on graphene is of high importance for many advanced technologies. Here we present a complete database of the atomic adsorption energies for the elements of the Periodic Table up to the atomic number 86 (excluding lanthanides) on pristine graphene. The energies have been calculated using the projector augmented wave (PAW) method with PBE, long-range dispersion interaction corrected PBE (PBE+D2, PBE+D3) as well as non-local vdW-DF2 approach. The inclusion of dispersion interactions leads to an exothermic adsorption for all the investigated elements. Dispers…
Ultrafast carrier dynamics of pristine bilayer graphene (BLG) and bilayer graphene intercalated with FeCl3 (FeCl3-G), were studied using time-resolved transient differential reflection (delta R/R). Compared to BLG, the FeCl3-G data showed an opposite sign of delta R/R, a slower rise time, and a single (instead of double) exponential relaxation. We attribute these differences in dynamics to the down-shifting of the Fermi level in FeCl3-G, as well as the formation of numerous horizontal bands arising from the d-orbitals of Fe. Our work shows that intercalation can dramatically change the electro…
Proximity of two different materials leads to an intricate coupling of quasiparticles so that an unprecedented electronic state is often realized at the interface. Here, we demonstrate a resonance-type many-body ground state in graphene, a non-magnetic two-dimensional Dirac semimetal, when grown on SmB6, a Kondo insulator, via thermal decomposition of fullerene molecules. This ground state is typically observed in three-dimensional magnetic materials with correlated electrons. Above the characteristic Kondo temperature of the substrate, the electron band structure of pristine graphene remains …
Based on a low temperature scanning tunneling microscopy study, we present a direct visualization of a cycloaddition reaction performed for some specific fluorinated maleimide molecules deposited on graphene. These studies showed that the cycloaddition reactions can be carried out on the basal plane of graphene, even when there are no pre-existing defects. In the course of covalently grafting the molecules to graphene, the sp2 conjugation of carbon atoms was broken and local sp3 bonds were created. The grafted molecules perturbed the graphene lattice, generating a standing-wave pattern with an…
University of Texas at Dallas（德克萨斯大学达拉斯分校）；Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and BIST（加泰罗尼亚纳米科学和纳米技术研究所（ICN2，CSIC和BIST））；Center for Integrated Nanotechnologies, Sandia National Laboratories（桑迪亚国家实验室集成纳米技术中心）；Sandia National Laboratories（桑迪亚国家实验室）
University of Arizona（亚利桑那大学）；Friedrich Schiller University Jena（耶拿弗里德里希·席勒大学）；Nanyang Technological University（南洋理工大学）；Indian Institute of Technology, Kanpur（坎普尔印度理工学院）；University of Crete（克里特大学）；Foundation for Research and Technology-Hellas（希腊研究与技术基金会）；Politecnico di Milano（米兰理工大学）；Fritz Haber Institute of the Max Planck Society（马克斯·普朗克学会弗里茨·哈伯研究所）；Indian Institute of Science（印度科学学院）；University of Regensburg（雷根斯堡大学）；University at Buffalo, State University of New York（纽约州立大学布法罗分校）；Eastern Institute of Technology（东方理工学院）；University of Washington（华盛顿大学）；The University of Hong Kong（香港大学）；Sun Yat-Sen University（中山大学）；University of Denver（丹佛大学）；University of Konstanz（康斯坦茨大学）；ETH Zurich（苏黎世联邦理工学院）；National Research Council Canada（加拿大国家研究委员会）；University of Ottawa（渥太华大学）
We demonstrate a simple and effective technique for dispersing pristine (unfunctionalized) graphene at high concentrations in a wide range of organic solvents by use of a stabilizing polymer (polyvinylpyrrolidone, PVP). These polymer-stabilized graphene dispersions are shown to be highly stable and readily redispersible even after freeze-drying. This technique yields significantly higher graphene concentrations as compared to prior studies. Excellent enhancement in thermal conductivity of the fluid by addition of pristine graphene is also demonstrated. These well-dispersed pristine graphene sh…
Valley polarization in graphene breaks inversion symmetry and therefore leads to second-harmonic generation. We present a complete theory of this effect within a single-particle approximation. It is shown that this may be a sensitive tool to measure the valley polarization created, e.g., by polarized light and, thus, can be used for a development of ultrafast valleytronics in graphene.
We have investigated the way in which the concentration and distribution of adatoms affect the geometric and electronic properties of graphene. Our calculations were based on the use of first principle under the density functional theory which reveal various types of $π$-bonding. The energy band structure of this doped graphene material may be explored experimentally by employing angle-resolved photo-emission spectroscopy (ARPES) for electronic band structure measurements and scanning tunneling spectroscopy (STS) for the density-of-states (DOS) both of which have been calculated and reported i…
Inspired by recent experiments where electron transport was measured across graphene nanoribbons (GNR) suspended between a metal surface and the tip of a scanning tunneling microscope [Koch \textit{et al}., Nat. Nanotechnol. {\bf 7}, 713 (2012)], we present detailed first-principles simulations of inelastic electron tunneling spectroscopy (IETS) of long pristine and defected armchair and zigzag nanoribbons under a range of charge carrier conditions. For the armchair ribbons we find two robust IETS signals around 169 and 196 mV corresponding to the D- and G-modes of Raman spectroscopy as well a…
The thermal conductivity of suspended single-layer graphene was measured as a function of temperature using Raman scattering spectroscopy on clean samples prepared directly on a prepatterned substrate by mechanical exfoliation without chemical treatments. The temperature at the laser spot was monitored by the frequency of the Raman 2$D$ band of the Raman scattering spectrum, and the thermal conductivity was deduced by analyzing heat diffusion equations assuming that the substrate is a heat sink at ambient temperature. The obtained thermal conductivity values range from $\sim$1800 Wm$^{-1}$K$^{…
Graphene-metal contact resistance is governed by both intrinsic and extrinsic factors. Intrinsically, both the density of states bottleneck near the Dirac point and carrier reflection at the graphene-metal interface lead to a high contact resistance. Moreover, graphene exhibits insulating behavior for out-of-the-plane conduction. Extrinsically, surface contamination introduced by photoresist residue or different adsorbed species during standard lithography processing alters graphene's intrinsic properties by uncontrolled doping and increased scattering which results in high and inconsistent co…
When the Fermi level matches the Dirac point in graphene, the reduced charge screening can dramatically enhance electron-electron (e-e) scattering to produce a strongly interacting Dirac liquid. While the dominance of e-e scattering already leads to novel behaviors, such as electron hydrodynamic flow, further exotic phenomena have been predicted to arise specifically from the unique kinematics of e-e scattering in massless Dirac systems. Here, we use optoelectronic probes, which are highly sensitive to the kinematics of electron scattering, to uncover a giant intrinsic photocurrent response in…
Intrinsic and extrinsic valley Hall effects are predicted to emerge in graphene systems with uniform or spatially-varying mass terms. Extrinsic mechanisms, mediated by the valley-dependent scattering of electrons at the Fermi surface, can be directly linked to quantum transport simulations. This is a promising route towards more complete experimental investigation of valleytronic phenomena in graphene, but a major obstacle is the difficulty in applying the sublattice-dependent potentials required. Here we show that strongly valley-dependent scattering also emerges from bilayer graphene quantum…
Electron's tunneling through potential barrier in monolayer and bilayer graphene lattices is investigated by using full tight-binding model. Emphasis is placed on the resonance tunneling feature and inter-valley scattering probability. It is shown that normal incidence transmission probabilities for monolayer and bilayer graphene exhibit different properties. Our calculation indicates that valleytronics in graphene systems may be detected, generated and controlled by changing the structure parameters of the external electric potential.
The low energy band structure of graphene has two inequivalent valleys at K and K' points of the Brillouin zone. The possibility to manipulate this valley degree of freedom defines the field of valleytronics, the valley analogue of spintronics. A key requirement for valleytronic devices is the ability to break the valley degeneracy by filtering and spatially splitting valleys to generate valley polarized currents. Here we suggest a way to obtain valley polarization using strain-induced inhomogeneous pseudomagnetic fields (PMF) which act differently on the two valleys. Notably, the suggested me…
Valley degrees of freedom offer a potential resource for quantum information processing if they can be effectively controlled. We discuss an optical approach to this problem in which intense light breaks electronic symmetries of a two-dimensional Dirac material. The resulting quasienergy structures may then differ for different valleys, so that the Floquet physics of the system can be exploited to produce highly polarized valley currents. This physics can be utilized to realize a valley valve whose behavior is determined optically. We propose a concrete way to achieve such valleytronics in gra…
We propose, for the first time, a valley Seebeck effect in gate tunable zigzag graphene nanoribbons as a result of the interplay between thermal gradient and valleytronics. A pure valley current is further generated by the thermal gradient as well as the external bias. In a broad temperature range, the pure valley current is found to be linearly dependent on the temperature gradient while it increases with the increasing temperature of one lead for a fixed thermal gradient. A valley field effect transistor (FET) driven by the temperature gradient is proposed that can turn on and off the pure v…
We have found that the Berry phase of bilayer graphene becomes from 2$π$ estimated by Shubnikov-de Haas oscillations when the A-B stacked pristine bilayer graphene experiences the Li-intercalation and sequential Li-desorption process in ultrahigh vacuum. Furthermore, the mobility of such processed bilayer graphene increases around four times larger, ~ 8,000 cm2/V$\cdot$s, than that of the pristine bilayer graphene. This is mainly due to increment of the scattering time and decrement of the cyclotron mass, which can be interpreted as a result of the change of the stacking structure of bilayer g…
There is an increasing interest to develop nanoscale biocompatible graphene structures due to their desirable physicochemical properties, unlimited application opportunities and scalable production. Here we report the preparation, characterization and biocompatibility assessment of novel graphene flakes and their enabled thin films suitable for a wide range of biomedical and electronic applications. Graphene flakes were synthesized by a chemical vapour deposition method or a liquid-phase exfoliation procedure and then thin films were prepared by transferring graphene onto glass coverslips. Ram…
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, re…
The theoretical results are presented showing that strain-induced anisotropy of graphene spectrum gives rise to the valley currents under the illumination by normally incident light. The currents of the two graphene valleys are mutually compensated providing zero net electric current. The magnitude and direction of the valley currents are determined by the parameters of strain and light polarization. For not too high photon energy strain-induced valley current exceed that due to intrinsic warping of the graphene spectrum which suggests feasibility of strain-mediated valleytronics.
The plasmon modes of pristine and impurity doped graphene are calculated, using a real-space theory which determines the non-local dielectric response within the random phase approximation. A full diagonalization of the polarization operator is performed, allowing the extraction of all its poles. It is demonstrated how impurities induce the formation of localized modes which are absent in pristine graphene. The dependence of the spatial modulations over few lattice sites and frequencies of the localized plasmons on the electronic filling and impurity strength is discussed. Furthermore, it is s…
The graphene-enhanced Raman scattering of Rhodamine 6G molecules on pristine, fluorinated and 4-nitrophenyl functionalized graphene substrates was studied. The uniformity of the Raman signal enhancement was studied by making large Raman maps. The relative enhancement of the Raman signal is demonstrated to be dependent on the functional groups, which was rationalized by the different doping levels of pristine, fluorinated and 4-nitrophenyl functionalized graphene substrates. The impact of the Fermi energy of graphene and the phonon energy of the molecules was considered together for the first t…
Valleytronics is a rising topic to explore the emergent degree of freedom for charge carriers in energy band edges and has attracted a great interest due to many intriguing quantum phenomena and potential application in information processing industry. Creation of permanent valley polarization, i.e. unbalanced occupation at different valleys, is a chief challenge and also urgent question to be solved in valleytronics. Here we predict that the spin-orbit coupling and magnetic ordering allow spontaneous valley Zeeman-type splitting in pristine monolayer of VAgP2Se6 by using first-principles calc…
The phase space for graphene's minimum conductivity $σ_\mathrm{min}$ is mapped out using Landauer theory modified for scattering using Fermi's Golden Rule, as well as the Non-Equilibrium Green's Function (NEGF) simulation with a Monte Carlo sampling over impurity distributions. The resulting `fan diagram' spans the range from ballistic to diffusive over varying aspect ratios ($W/L$), and bears several surprises. {The device aspect ratio determines how much tunneling (between contacts) is allowed and becomes the dominant factor for the evolution of $σ_{min}$ from ballistic to diffusive regime. …
Here we use pristine graphene samples in order to analyze how the Raman peaks intensity, measured at 2.4 eV and 1.96 eV excitation energy, changes with the amount of doping. The use of pristine graphene allows investigating the intensity dependence close to the Dirac point. We show that the G peak intensity is independent on the doping, while the 2D peak intensity strongly decreases for increasing doping. Analyzing this dependence in the framework of a fully resonant process, we found that the total electron-phonon scattering rate is ~40 meV at 2.4 eV.
We have fabricated transistor structures using fluorinated single-layer graphene flakes and studied their electronic properties at different temperatures. Compared with pristine graphene, fluorinated graphene has very large and strongly temperature dependent resistance in the electro-neutrality region. We show that fluorination creates a mobility gap in graphene's spectrum where electron transport takes place via localised electron states.
We propose a directional switching effect in a metallic device. To such end we exploit a graphene-based device with a three-terminal geometry in the presence of a magnetic field. We show that unidirectional charge and valley currents can be controlled by the Fermi energy and the magnetic field direction in the active device. Interestingly, unidirectional transport of charge and valley is generated between two-terminals at the same bias voltage. Furthermore, we quantify the valley depolarization as a function of disorder concentration. Our results open a way for active graphene-based valleytron…
