Controlling the type and density of charge carriers by doping is the key step for developing graphene electronics. However, direct doping of graphene is rather a challenge. Based on first-principles calculations, a concept of overcoming doping difficulty in graphene via substrate is reported.We find that doping could be strongly enhanced in epitaxial graphene grown on silicon carbide substrate. Compared to free-standing graphene, the formation energies of the dopants can decrease by as much as 8 eV. The type and density of the charge carriers of epitaxial graphene layer can be effectively manipulated by suitable dopants and surface passivation. More importantly, contrasting to the direct doping of graphene, the charge carriers in epitaxial graphene layer are weakly scattered by dopants due to the spatial separation between dopants and the conducting channel. Finally, we show that a similar idea can also be used to control magnetic properties, for example, induce a half-metallic state in the epitaxial graphene without magnetic impurity doping.
Generally, it is supposed that the Fermi level in epitaxial graphene is controlled by two effects: p-type polarization doping induced by the bulk of the hexagonal SiC(0001) substrate and overcompensation by donor-like states related to the buffer layer. In this work, we evidence that this effect is also related to the specific underlying SiC terrace. We fabricated a periodic sequence of non-identical SiC terraces, which are unambiguously attributed to specific SiC surface terminations. A clear correlation between the SiC termination and the electronic graphene properties is experimentally obse…
We study electron transport in nanostructures patterned in bilayer graphene patches grown epitaxially on SiC as a function of doping, magnetic field, and temperature. Away from charge neutrality transport is only weakly modulated by changes in carrier concentration induced by a local side-gate. At low n-type doping close to charge neutrality, electron transport resembles that in exfoliated graphene nanoribbons and is well described by tunnelling of single electrons through a network of Coulomb-blockaded islands. Under the influence of an external magnetic field, Coulomb blockade resonances flu…
We determine conditions for the formation of compressible stripes near the quantum Hall effect (QHE) edges of top-gated epitaxial graphene on Si-terminated SiC (G/SiC) and compare those to graphene exfoliated onto insulating substrate in the field-effect-transistor (GraFET) geometry. For G/SiC, a large density of localised surface states on SiC just underneath graphene layer and charge transfer between them lead both to doping of graphene and to screening of potential profile near its edge. This suppresses formation of compressible stripes near QHE edges in graphene, making them much narrower …
Monolayer epitaxial graphene (EG) grown on hexagonal Si-terminated SiC substrates is intrinsically electron-doped (carrier density is about 10^13 cm^(-2)). We demonstrate a clean device fabrication process using a precious-metal protective layer, and show that etching with aqua regia results in p-type (hole) molecular doping of our un-gated, contamination-free EG. Devices fabricated by this simple process can reach a carrier density in the range of 10^10 cm^(-2) to 10^11 cm^(-2) with mobility about 8000 cm^2/V/s or higher. In a moderately doped device with a carrier density n = 2.4 x 10^11 cm^…
We show that the $d^{0}$ ferromagnetism with high Curie temperature ($T_c$) can be achieved in the electron doped hydrogenated epitaxial graphene on some certain SiC substrates through first-principles calculations. The pristine systems are found to be a Mott insulator independent of SiC polytypes (2$H$, 4$H$ or 6$H$) which, however, play a significant role in the modulation of magnetic interaction. Carrier doping enhances the ferromagnetic coupling due to the double exchange mechanism and thus realizes the phase transition from antiferromagnetism to ferromagnetism. A $T_c$ of around 400 K is …
We use angle-resolved photoemission spectroscopy to investigate the electronic structure of bilayer graphene at high n-doping and extreme displacement fields, created by intercalating epitaxial monolayer graphene on silicon carbide with magnesium to form quasi-freestanding bilayer graphene on magnesium-terminated silicon carbide. Angle-resolved photoemission spectroscopy reveals that upon magnesium intercalation, the single massless Dirac band of epitaxial monolayer graphene is transformed into the characteristic massive double-band Dirac spectrum of quasi-freestanding bilayer graphene. Analys…
We found an intrinsic redistribution of charge arises between epitaxial graphene, which has intrinsically n-type doping, and an undoped substrate. In particular, we studied in detail epitaxial graphene layers thermally elaborated on C-terminated $4H$-$SiC$ ($4H$-$SiC$ ($000{\bar{1}}$)). We have investigated the charge distribution in graphene-substrate systems using Raman spectroscopy. The influence of the substrate plasmons on the longitudinal optical phonons of the $SiC$ substrates has been detected. The associated charge redistribution reveals the formation of a capacitance between the grap…
We have performed scanning tunneling microscope (STM) and angle-resolved photoemission spectroscopy (ARPES) in Pb-deposited bilayer Graphene (BLG) on SiC(0001) substrate to investigate the dependence of the electronic structures on Pb-deposition amount. We have observed that the Pb atoms form islands by STM and the $π$ bands of the BLG shift toward the Fermi level by ARPES. This hole-doping-like energy shift is enhanced as the amount of Pb is increased, and we were able to tune the Dirac gap to the Fermi level by 4 ML deposition. Considering the band dispersion, we suggest that hole-doping-lik…
In this letter we report on transport measurements of epitaxial graphene on SiC(0001) with oxygen adsorption. In a $50\times 50 μ\mathrm{m^2}$ size Hall bar we observe the half-integer quantum Hall effect with a transverse resistance plateau quantized at filling factor around $ν= 2$, an evidence of monolayer graphene. We find low electron concentration of $9\times 10^{11} \textrm{cm}^{-2}$ and we show that a doping of $10^{13}\textrm{cm}^{-2}$ which is characteristic of intrinsic epitaxial graphene can be restored by vacuum annealing. The effect of oxygen adsorption on carrier density is confi…
Intercalation of Au can produce giant Rashba-type spin-orbit splittings in graphene but this has not yet been achieved on a semiconductor substrate. For graphene/SiC(0001), Au intercalation yields two phases with different doping. Here, we report the preparation of an almost pure p-type graphene phase after Au intercalation. We observe a 100 meV Rashba-type spin-orbit splitting at 0.9 eV binding energy. We show that this giant splitting is due to hybridization and much more limited in energy and momentum space than for Au-intercalated graphene on Ni.
We discuss, based on first principles calculations, the possibility to tune the magnetism of oxygen vacancies at the (001) surface of strontium titanate $(\mathrm{SrTiO_3}\!)$. The magnetic moment of single and clustered vacancies stemming from Ti-O broken bonds can be both quenched and stabilized controllably by chemical potential adjustment associated with doping the system with electrons or holes. We discuss to what extent this route to magnetization state control is robust against other external influences like chemical doping, mechanical action and electric field. Such control of vacancy …
Using high temperature annealing conditions with a graphite cap covering the C-face of an 8deg off-axis 4H-SiC sample, large and homogeneous single epitaxial graphene layers have been grown. Raman spectroscopy shows evidence of the almost free-standing character of these monolayer graphene sheets, which was confirmed by magneto-transport measurements. We find a moderate p-type doping, high carrier mobility and half integer Quantum Hall effect typical of high quality graphene samples. This opens the way to a fully compatible integration of graphene with SiC devices on the wafers that constitute…
Graphene monolayer grown by Si evaporation from the 0001 surface of SiC displays a moiré pattern of corrugation whose structure is ambiguous: different measurements and theoretical studies show either protruding bumps surrounded by valleys, or, reversely, wells surrounded by crests. Here we address the fine structure of monolayer graphene on SiC by means of Density Functional Theory, using a model including the full symmetry of the system and the substrate (1648 atoms) and therefore realistically reproducing the experimental sample. We find that accurate treatment of the vdW interactions betwe…
The thermoelectric properties of cubic zincblend silicon carbide nanowires (SiCNWs) with nitrogen impurities and vacancies along [111] direction are theoretically studied by means of atomistic simulations. It is found that the thermoelectric figure of merit ZT of SiCNWs can be significantly enhanced by doping N impurities together with making Si vacancies. Aiming at obtaining a large ZT, we study possible energetically stable configurations, and disclose that, when N dopants locate at the center, a small number of Si vacancies at corners are most favored for n-type nanowires, while a large num…
The electrical properties of graphene depend sensitively on the substrate. For example, recent measurements of epitaxial graphene on SiC show resistance arising from steps on the substrate. Here we calculate the deformation of graphene at substrate steps, and the resulting electrical resistance, over a wide range of step heights. The elastic deformations contribute only a very small resistance at the step. However, for graphene on SiC(0001) there is strong substrate-induced doping, and this is substantially reduced on the lower side of the step where graphene pulls away from the substrate. The…
Tuning the charge carrier density of two-dimensional (2D) materials by incorporating dopants into the crystal lattice is a challenging task. An attractive alternative is the surface transfer doping by adsorption of molecules on 2D crystals, which can lead to ordered molecular arrays. However, such systems, demonstrated in ultra-high vacuum conditions (UHV), are often unstable in ambient conditions. Here we show that air-stable doping of epitaxial graphene on SiC - achieved by spin-coating deposition of 2,3,5,6-tetrafluoro-tetracyano-quino-dimethane (F4TCNQ) incorporated in poly (methyl-methacr…
It has been shown that the first C layer on the SiC(0001)(2{\times}2)C surface already exhibits graphene-like electronic structure, with linear pi bands near the Dirac point. Indeed, the (2{\times}2)C reconstruction, with a Si adatom and C restatom structure, efficiently passivates the SiC(0001) surface thanks to an adatom/restatom charge transfer mechanism. Here, we study the effects of interface modifications on the graphene layer using density functional theory calculations. The modifications we consider are inspired from native interface defects observed by scanning tunneling microscopy. O…
The minimization of electronics makes heat dissipation of related devices an increasing challenge. When the size of materials is smaller than the phonon mean free paths, phonons transport without internal scatterings and laws of diffusive thermal conduction fail, resulting in significant reduction in the effective thermal conductivity. This work reports, for the first time, the temperature dependent thermal conductivity of doped epitaxial 6H-SiC and monocrystalline porous 6H-SiC below room temperature probed by time-domain thermoreflectance. Strong quasi-ballistic thermal transport was observe…
Recently the graphene/SiC interface has emerged as a versatile platform for the epitaxy of otherwise unstable, monoelemental, two-dimensional (2D) layers via intercalation. Intrinsically capped into a van der Waals heterostructure with overhead graphene, they compose a new class of quantum materials with striking properties contrasting their parent bulk crystals. Intercalated silver presents a prototypical example where 2D quantum confinement and inversion symmetry breaking entail a metal-to-semiconductor transition. However, little is known about the associated unoccupied states, and control …
We present a study of quasi-free-standing monolayer graphene obtained by intercalation of Au atoms at the interface between the carbon buffer layer (Bu-L) and the silicon-terminated face (0001) of 4H-silicon carbide. Au intercalation is achieved by deposition of atomically thin Au on the Bu-L followed by annealing at 850 °C in an Argon atmosphere. We explore the intercalation of Au and decoupling of the Bu-L into quasi-free-standing monolayer graphene by surface science characterizations and electron transport in top-gated electronic devices. By gate-dependent magnetotransport we find that the…
Nitrogen-doped epitaxial graphene grown on SiC(000?1) was prepared by exposing the surface to an atomic nitrogen flux. Using Scanning Tunneling Microscopy (STM) and Spectroscopy (STS), supported by Density Functional Theory (DFT) calculations, the simple substitution of carbon by nitrogen atoms has been identified as the most common doping configuration. High-resolution images reveal a reduction of local charge density on top of the nitrogen atoms, indicating a charge transfer to the neighboring carbon atoms. For the first time, local STS spectra clearly evidenced the energy levels associated …
We compute the nonlinear optical response of doped mono- and bilayer graphene using the full dispersion based on tight-binding models. The response is derived with the density matrix formalism using the length gauge and is valid for any periodic system, with arbitrary doping. By collecting terms that define effective nonlinear response tensors, we identify all nonlinear Drude-like terms (up to third-order) and show that all additional spurious divergences present in the induced current vanish. The nonlinear response of graphene comprises a large Drude-like divergence and three resonances that …
In recent years, various doping methods for epitaxial graphene have been demonstrated through atom substitution and adsorption. Here we observe by angle-resolved photoemission spectroscopy (ARPES) a coupling-induced Dirac cone renormalization when depositing small amounts of Ti onto epitaxial graphene on SiC. We obtain a remarkably high doping efficiency and a readily tunable carrier velocity simply by changing the amount of deposited Ti. First-principles theoretical calculations show that a strong lateral (non-vertical) orbital coupling leads to an efficient doping of graphene by hybridizing …
We investigate the screening effects of excess electrons in the doped layer on the mobility of a GaAs two-dimensional electron system (2DES) with a modern architecture using short-period superlattice (SL) doping. By controlling the density of excess electrons in the SL with a top gate while keeping the 2DES density constant with a back gate, we are able to compare 2DESs with the same density but different degrees of screening using one sample. Using a field-penetration technique and circuit-model analysis, we determine the density of states and excess electron density in the SL, quantities dir…
We investigate the electronic structure of terraces of single layer graphene (SLG) by scanning tunneling microscopy (STM) on samples grown by thermal decomposition of 6H-SiC(0001) crystals in ultra-high vacuum. We focus on the perturbations of the local density of states (LDOS) in the vicinity of edges of SLG terraces. Armchair edges are found to favour intervalley quasiparticle scattering, leading to the (\surd3\times\surd3)R30° LDOS superstructure already reported for graphite edges and more recently for SLG on SiC(0001). Using Fourier transform of LDOS images, we demonstrate that the intrin…
Chalmers University of Technology（查尔姆斯理工大学）；KTH Royal Institute of Technology（瑞典皇家理工学院）；Clemson University（克莱姆森大学）；RISE (Research Institutes of Sweden)（瑞典研究院）；Gothenburg University（哥德堡大学）；Stockholm University（斯德哥尔摩大学）；Nordita（北欧理论天体物理学中心）
We report scanning tunneling microscopy (STM) and spectroscopy (STS) of twisted graphene bilayer on SiC substrate. For twist angle ~ 4.5o the Dirac point ED is located about 0.40 eV below the Fermi level EF due to the electron doping at the graphene/SiC interface. We observed an unexpected result that the local Dirac point around a nanoscaled defect shifts towards the Fermi energy during the STS measurements (with a time scale about 100 seconds). This behavior was attributed to the decoupling between the twisted graphene and the substrate during the measurements, which lowers the carrier densi…
Controlling doping is essential for a successful integration of semiconductor materials into device technologies. However, the assessment of doping levels and the distribution of charge carriers in carbon nanotubes or other nanoscale semiconductor materials is often either limited to a qualitative attribution of being 'high' or 'low' or it is entirely absent. Here, we describe efforts toward a quantitative characterization of doping in redox- or electrochemically doped semiconducting carbon nanotubes (s-SWNTs) using VIS-NIR absorption spectroscopy. We discuss how carrier densities up to about …
The allure of all carbon electronics stems from the spread in physical properties, across all its allotropes. The scheme also harbours unique challenges, like tunability of band-gap, variability of doping and defect control. Here, we explore the technique of scanning probe tip induced nanoscale reduction of graphene oxide (GO), which nucleates conducting, sp2 rich graphitic regions on the insulating GO background. Flexibility of direct writing is supplemented with control over degree of reduction and tunability of bandgap, through macroscopic control parameters. The fabricated reduced - GO cha…
One notable manifestation of the peculiar edge-localized states in zigzag graphene nanoribbons (zGNRs) is the p-type (n-type) characteristics of nitrogen (boron) edge-doped GNRs, and such behavior was so far considered to be exclusive for zGNRs. Carrying out first-principles electronic structure and quantum transport calculations, we herein show that the donor-acceptor transition behavior can also arise in the B/N edge-doped armchair GNRs (aGNRs) by introducing a bipolar P codopant atom into the energetically most favorable nearest neighbor edge sites. The n-type (p-type) transport properties …
The buffer carbon layer obtained in the first instance by evaporation of Si from the Si-rich surfaces of silicon carbide (SiC) is often studied only as the intermediate to the synthesis of SiC supported graphene. In this work, we explore its intrinsic potentialities, addressing its structural and electronic properties by means Density Functional Theory. While the system of corrugation crests organized in a honeycomb super-lattice of nano-metric side returned by calculations is compatible with atomic microscopy observations, our work reveals some possible alternative symmetries, which might coe…
In metal/degenerately doped silicon bilayer structure, the interfacial flexoelectric effect due to strain gradient leads to charge carrier transfer from metal layer to the silicon layer. This excess charge carrier concentration is called flexoelectronic doping or flexoelectronic charge transfer, which gives rise to an electronically polarized (order of magnitude larger than ferroelectric materials) silicon layer. In the transport measurements, the charge carrier concentration in silicon is found to increase by two orders of magnitude due to flexoelectronic doping, which changes the Fermi level…
Controlling extra charge carriers is pivotal in manipulating electronic, optical, and magnetic properties of various two-dimensional (2D) materials. Nonetheless, the ubiquitous hole doping of 2D materials in the air and acids has been controversial in its mechanistic details. Here we show their common origin is an electrochemical reaction driven by redox couples of oxygen and water molecules. Using real-time photoluminescence imaging of WS2 and Raman spectroscopy of graphene, we capture molecular diffusion through the 2D nanoscopic space between 2D materials and hydrophilic substrates, and sho…
The continuous reduction of magnetic units to ultra small length scales inspires efforts to look for a suitable means of controlling magnetic states. In this study we show two surface charge alteration techniques for tuning the interlayer exchange coupling (IEC) of ferromagnetic layers separated by paramagnetic spacers. Our study reveals that already a modest amount of extra charge can switch the mutual alignment of the magnetization from anti-ferromagnetic to ferromagnetic or vice verse. We also propose adsorption of alkali metals as an alternative way of varying the electronic and chemical p…
Quantized magnetotransport is observed in 5.6 x 5.6 mm^2 epitaxial graphene devices, grown using highly constrained sublimation on the Si-face of SiC(0001) at high temperature (1900 °C). The precise quantized Hall resistance of Rxy = h/2e^2 is maintained up to record level of critical current Ixx = 0.72 mA at T = 3.1 K and 9 T in a device where Raman microscopy reveals low and homogeneous strain. Adsorption-induced molecular doping in a second device reduced the carrier concentration close to the Dirac point(n ~ 1E10 (1/cm^2)), where mobility of 43700 cm^2/Vs is measured over an area of 10 mm^…
