Search

Realizing high-performance nanoelectronics requires control of materials at the nanoscale. Methods to produce high quality epitaxial graphene (EG) nanostructures on silicon carbide are known. The next step is to grow Van der Waals semiconductors on top of EG nanostructures. Hexagonal boron nitride (h-BN) is a wide bandgap semiconductor with a honeycomb lattice structure that matches that of graphene, making it ideally suited for graphene-based nanoelectronics. Here, we describe the preparation and characterization of multilayer h-BN grown epitaxially on EG using a migration-enhanced metalorganic vapor phase epitaxy process. As a result of the lateral epitaxial deposition (LED) mechanism, the grown h-BN/EG heterostructures have highly ordered epitaxial interfaces, as desired in order to preserve the transport properties of pristine graphene. Atomic scale structural and energetic details of the observed row-by-row, growth mechanism of the 2D epitaxial h-BN film are analyzed through first-principles simulations, demonstrating one-dimensional nucleation-free-energy-barrierless growth. This industrially relevant LED process can be applied to a wide variety of van der Waals materials.

Large-scale atomically thin metals can be stabilized through confinement epitaxy at graphene / SiC interface, which exhibit a gradient bonding type and are air stable, providing a compelling platform for quantum and optoelectronic technologies.

Graphene's original promise to succeed silicon faltered due to pervasive edge disorder in lithographically patterned deposited graphene and the lack of a new electronics paradigm. Here we demonstrate that the annealed edges in conventionally patterned graphene epitaxially grown on a silicon carbide substrate (epigraphene) are stabilized by the substrate and support a protected edge state. The edge state has a mean free path that is greater than 50 microns, 5000 times greater that the bulk states and involves a theoretically unexpected Majorana-like zero-energy non-degenerate quasiparticle that does not produce a Hall voltage. In seamless integrated structures, the edge state forms a zero-energy one-dimensional ballistic network with essentially dissipationless nodes at ribbon-ribbon junctions. Seamless device structures offer a variety of switching possibilities including quantum coherent devices at low temperatures. This makes epigraphene a technologically viable graphene nanoelectronics platform that has the potential to succeed silicon nanoelectronics., Comment: File contains article and supplementary. Nature Communications (in print)

The study of the nanomechanics of graphene $-$ and other 2D materials $-$ has led to the discovery of exciting new properties in 2D crystals, such as their remarkable in-plane stiffness and out of plane flexibility, as well as their unique frictional and wear properties at the nanoscale. Recently, nanomechanics of graphene has generated renovated interest for new findings on the pressure-induced chemical transformation of a few-layer thick epitaxial graphene into a new ultra-hard carbon phase, named diamene. In this work, by means of a machine learning technique, we provide a fast and efficient tool for identification of graphene domains (areas with a defined number of layers) in epitaxial and exfoliated films, by combining data from Atomic Force Microscopy (AFM) topography and friction force microscopy (FFM). Through the analysis of the number of graphene layers and detailed \r{A}-indentation experiments, we demonstrate that the formation of ultra-stiff diamene is exclusively found in 1-layer plus buffer layer epitaxial graphene on silicon carbide (SiC) and that an ultra-stiff phase is not observed in neither thicker epitaxial graphene (2-layer or more) nor exfoliated graphene films of any thickness on silicon oxide (SiO$_{2}$)., Comment: 30 pages, 7 figures

Recent pump-probe experiments performed on graphene in a perpendicular magnetic field have revealed carrier relaxation times ranging from picoseconds to nanoseconds depending on the quality of the sample. To explain this surprising behavior, we propose a novel symmetry-breaking defect-assisted relaxation channel. This enables scattering of electrons with single out-of-plane phonons, which drastically accelerate the carrier scattering time in low-quality samples. The gained insights provide a strategy for tuning the carrier relaxation time in graphene and related materials by orders of magnitude.

Atomically thin graphene exhibits fascinating mechanical properties, although its hardness and transverse stiffness are inferior to those of diamond. To date, there hasn't been any practical demonstration of the transformation of multi-layer graphene into diamond-like ultra-hard structures. Here we show that at room temperature and after nano-indentation, two-layer graphene on SiC(0001) exhibits a transverse stiffness and hardness comparable to diamond, resisting to perforation with a diamond indenter, and showing a reversible drop in electrical conductivity upon indentation. Density functional theory calculations suggest that upon compression, the two-layer graphene film transforms into a diamond-like film, producing both elastic deformations and sp2-to-sp3 chemical changes. Experiments and calculations show that this reversible phase change is not observed for a single buffer layer on SiC or graphene films thicker than 3 to 5 layers. Indeed, calculations show that whereas in two-layer graphene layer-stacking configuration controls the conformation of the diamond-like film, in a multilayer film it hinders the phase transformation., Comment: Published online on Nature Nanotechnology on December 18, 2017

This article presents a review of epitaxial graphene on silicon carbide, from fabrication to properties, put in the context of other forms of graphene., Comment: 46 pages, 322 references, 35 figures. Submitted December 2015

Epitaxial graphene grown on SiC by the confinement controlled sublimation method is reviewed, with an emphasis on multilayer and monolayer epitaxial graphene on the carbon face of 4H-SiC and on directed and selectively grown structures under growth-arresting or growth-enhancing masks. Recent developments in the growth of templated graphene nanostructures are also presented, as exemplified by tens of micron long very well confined and isolated 20-40nm wide graphene ribbons. Scheme for large scale integration of ribbon arrays with Si wafer is also presented., Comment: 19 pages, 9 figures

We report the growth of high-quality triangular GaN nanomesas, 30-nm thick, on the C-face of 4H-SiC using nano selective area growth (NSAG) with patterned epitaxial graphene grown on SiC as an embedded mask. NSAG alleviates the problems of defective crystals in the heteroepitaxial growth of nitrides, and the high mobility graphene film can readily provide the back low-dissipative electrode in GaN-based optoelectronic devices. The process consists in first growing a 5-8 graphene layers film on the C-face of 4H- SiC by confinement-controlled sublimation of silicon carbide. The graphene film is then patterned and arrays of 75-nanometer-wide openings are etched in graphene revealing the SiC substrate. 30-nanometer-thick GaN is subsequently grown by metal organic vapor phase epitaxy. GaN nanomesas grow epitaxially with perfect selectivity on SiC, in openings patterned through graphene, with no nucleation on graphene. The up-or-down orientation of the mesas on SiC, their triangular faceting, and cross-sectional scanning transmission electron microscopy show that they are biphasic. The core is a zinc blende monocrystal surrounded with single-crystal hexagonal wurtzite. The GaN crystalline nanomesas have no threading dislocations, and do not show any V-pit. This NSAG process potentially leads to integration of high-quality III-nitrides on the wafer scalable epitaxial graphene / silicon carbide platform., Comment: 7 pages, 5 figures

In van der Waals bonded or rotationally disordered multilayer stacks of two-dimensional (2D) materials, the electronic states remain tightly confined within individual 2D layers. As a result, electron-phonon interactions occur primarily within layers and interlayer electrical conductivities are low. In addition, strong covalent in-plane intralayer bonding combined with weak van der Waals interlayer bonding results in weak phonon-mediated thermal coupling between the layers. We demonstrate here, however, that Coulomb interactions between electrons in different layers of multilayer epitaxial graphene provide an important mechanism for interlayer thermal transport even though all electronic states are strongly confined within individual 2D layers. This effect is manifested in the relaxation dynamics of hot carriers in ultrafast time-resolved terahertz spectroscopy. We develop a theory of interlayer Coulomb coupling containing no free parameters that accounts for the experimentally observed trends in hot-carrier dynamics as temperature and the number of layers is varied., Comment: 54 pages, 15 figures, uses documentclass{achemso}, M.T.M. and J.R.T. contributed equally to this work

Refined infrared magnetotransmission experiments have been performed in magnetic fields B up to 35 T on a series of multilayer epitaxial graphene samples. Following the main optical transition involving the n=0 Landau level (LL), we observe a new absorption transition increasing in intensity with magnetic fields B>26 T. Our analysis shows that this is a signature of the breaking of the SU(4) symmetry of the n=0 LL. Using a quantitative model, we show that the only symmetry-breaking scheme consistent with our experiments is a charge density wave (CDW).

The icosahedral (i-) AlPdRe is the most resistive quasicrystalline alloy discovered so far. Resistivities ($\rho$) of $1\Omega cm$ at 4K and correlated resistance ratios ($RRR = \rho_{4K}/\rho_{300K}$) of more than 200 are observed in polycrystalline samples. These values are two orders of magnitude larger than for the isomorphous i-AlPdMn phase. We discuss here the controversial microscopic origin of the i-AlPdRe alloy electrical specificity. It has been proposed that the high resistivity values are due to extrinsic parameters, such as secondary phases or oxygen contamination. From comprehensive measurements and data from the literature including electronic transport correlated with micro structural and micro chemical analysis, we show that on the contrary there is mounting evidence in support of an origin intrinsic to the i-phase. Similarly to the other quasicrystalline alloys, the electrical resistivity of the i-AlPdRe samples depends critically on minute changes in the structural quality and chemical composition. The low resistivity in i-AlPdRe single-grains compared to polycrystaline samples can be explained by difference in chemical composition, heterogeneity and thermal treatment., Comment: 19 pages, 17 figures

Structured growth of high quality graphene is necessary for technological development of carbon based electronics. Specifically, control of the bunching and placement of surface steps under epitaxial graphene on SiC is an important consideration for graphene device production. We demonstrate lithographically patterned evaporated amorphous carbon corrals as a method to pin SiC surface steps. Evaporated amorphous carbon is an ideal step-flow barrier on SiC due to its chemical compatibility with graphene growth and its structural stability at high temperatures, as well as its patternability. The amorphous carbon is deposited in vacuum on SiC prior to graphene growth. In the graphene furnace at temperatures above 1200$^\circ$C, mobile SiC steps accumulate at these amorphous carbon barriers, forming an aligned step free region for graphene growth at temperatures above 1330$^\circ$C. AFM imaging and Raman spectroscopy support the formation of quality step-free graphene sheets grown on SiC with the step morphology aligned to the carbon grid.

We investigate the polarization dependence of the carrier excitation and relaxation in epitaxial multilayer graphene. Degenerate pump-probe experiments with a temporal resolution of 30 fs are performed for different rotation angles of the pump-pulse polarization with respect to the polarization of the probe pulse. A pronounced dependence of the pump-induced transmission on this angle is found. It reflects a strong anisotropy of the pump-induced occupation of photogenerated carriers in momentum space even though the band structure is isotropic. Within 150 fs after excitation an isotropic carrier distribution is established. Our observations imply the predominant role of collinear scattering preserving the initially optically generated anisotropy in the carrier distribution. The experiments are well described by microscopic time-, momentum, and angle-resolved modelling, which allows us to unambiguously identify non-collinear carrier-phonon scattering to be the main relaxation mechanism giving rise to an isotropic distribution in the first hundred fs after optical excitation., Comment: Submitted to Nano Letters

The development of graphene electronics requires the integration of graphene devices with Si-CMOS technology. Most strategies involve the transfer of graphene sheets onto silicon, with the inherent difficulties of clean transfer and subsequent graphene nano-patterning that degrades considerably the electronic mobility of nanopatterned graphene. Epitaxial graphene (EG) by contrast is grown on an essentially perfect crystalline (semi-insulating) surface, and graphene nanostructures with exceptional properties have been realized by a selective growth process on tailored SiC surface that requires no graphene patterning. However, the temperatures required in this structured growth process are too high for silicon technology. Here we demonstrate a new graphene to Si integration strategy, with a bonded and interconnected compact double-wafer structure. Using silicon-on-insulator technology (SOI) a thin monocrystalline silicon layer ready for CMOS processing is applied on top of epitaxial graphene on SiC. The parallel Si and graphene platforms are interconnected by metal vias. This method inspired by the industrial development of 3d hyper-integration stacking thin-film electronic devices preserves the advantages of epitaxial graphene and enables the full spectrum of CMOS processing., Comment: 15 pages, 7 figures

Epitaxial graphene mesas and ribbons are investigated using terahertz (THz) nearfield microscopy to probe surface plasmon excitation and THz transmission properties on the sub-wavelength scale. The THz near-field images show variation of graphene properties on a scale smaller than the wavelength, and excitation of THz surface waves occurring at graphene edges, similar to that observed at metallic edges. The Fresnel reflection at the substrate SiC/air interface is also found to be altered by the presence of graphene ribbon arrays, leading to either reduced or enhanced transmission of the THz wave depending on the wave polarization and the ribbon width., Comment: accepted for publication in Applied Physics Letter

Patterning of graphene is key for device fabrication. We report a way to increase or reduce the number of layers in epitaxial graphene grown on the C-face (000-1) of silicon carbide by the deposition of a 120 nm to 150nm-thick silicon nitride (SiN) mask prior to graphitization. In this process we find that areas covered by a Si-rich SiN mask have one to four more layers than non-masked areas. Conversely N-rich SiN decreases the thickness by three layers. In both cases the mask decomposes before graphitization is completed. Graphene grown in masked areas show good quality as observed by Raman spectroscopy, atomic force microscopy (AFM) and transport data. By tailoring the growth parameters selective graphene growth and sub-micron patterns have been obtained.

Spin information processing is a possible new paradigm for post-CMOS (complementary metal-oxide semiconductor) electronics and efficient spin propagation over long distances is fundamental to this vision. However, despite several decades of intense research, a suitable platform is still wanting. We report here on highly efficient spin transport in two-terminal polarizer/analyser devices based on high-mobility epitaxial graphene grown on silicon carbide. Taking advantage of high-impedance injecting/detecting tunnel junctions, we show spin transport efficiencies up to 75%, spin signals in the mega-ohm range and spin diffusion lengths exceeding 100 {\mu}m. This enables spintronics in complex structures: devices and network architectures relying on spin information processing, well beyond present spintronics applications, can now be foreseen.

A method is proposed to extract pure Raman spectrum of epitaxial graphene on SiC by using a Non-negative Matrix Factorization. It overcomes problems of negative spectral intensity and poorly resolved spectra resulting from a simple subtraction of a SiC background from the experimental data. We also show that the method is similar to deconvolution, for spectra composed of multiple sub- micrometer areas, with the advantage that no prior information on the impulse response functions is needed. We have used this property to characterize the Raman laser beam. The method capability in efficient data smoothing is also demonstrated., Comment: 3 figures, regular paper

The maximum oscillation frequency (fmax) quantifies the practical upper bound for useful circuit operation. We report here an fmax of 70 GHz in transistors using epitaxial graphene grown on the C-face of SiC. This is a significant improvement over Si-face epitaxial graphene used in the prior high frequency transistor studies, exemplifying the superior electronics potential of C-face epitaxial graphene. Careful transistor design using a high {\kappa} dielectric T-gate and self-aligned contacts, further contributed to the record-breaking fmax.

Graphene electronics has motivated much of graphene science for the past decade. A primary goal was to develop high mobility semiconducting graphene with a band gap that is large enough for high performance applications. Graphene ribbons were thought to be semiconductors with these properties, however efforts to produce ribbons with useful bandgaps and high mobility has had limited success. We show here that high quality epitaxial graphene nanoribbons 40 nm in width, with annealed edges, grown on sidewall SiC are not semiconductors, but single channel room temperature ballistic conductors for lengths up to at least 16 micrometers. Mobilities exceeding one million corresponding to a sheet resistance below 1 Ohm have been observed, thereby surpassing two dimensional graphene by 3 orders of magnitude and theoretical predictions for perfect graphene by more than a factor of 10. The graphene ribbons behave as electronic waveguides or quantum dots. We show that transport in these ribbons is dominated by two components of the ground state transverse waveguide mode, one that is ballistic and temperature independent, and a second thermally activated component that appears to be ballistic at room temperature and insulating at cryogenic temperatures. At room temperature the resistance of both components abruptly increases with increasing length, one at a length of 160 nm and the other at 16 micrometers. These properties appear to be related to the lowest energy quantum states in the charge neutral ribbons. Since epitaxial graphene nanoribbons are readily produced by the thousands, their room temperature ballistic transport properties can be used in advanced nanoelectronics as well.

Graphene is generally considered to be a strong candidate to succeed silicon as an electronic material. However, to date, it actually has not yet demonstrated capabilities that exceed standard semiconducting materials. Currently demonstrated viable graphene devices are essentially limited to micron size ultrahigh frequency analog field effect transistors and quantum Hall effect devices for metrology. Nanoscopically patterned graphene tends to have disordered edges that severely reduce mobilities thereby obviating its advantage over other materials. Here we show that graphene grown on structured silicon carbide surfaces overcomes the edge roughness and promises to provide an inroad into nanoscale patterning of graphene. We show that high quality ribbons and rings can be made using this technique. We also report on progress towards high mobility graphene monolayers on silicon carbide for device applications., Comment: J. Phys D - Epitaxial Graphene special issue (submitted)

Most experimental studies to date of multilayer epitaxial graphene on C-face SiC have indicated that the electronic states of different layers are decoupled as a consequence of rotational stacking. We have measured the third order nonlinear tensor in epitaxial graphene as a novel approach to probe interlayer electronic coupling, by studying THz emission from coherently controlled photocurrents as a function of the optical pump and THz beam polarizations. We find that the polarization dependence of the coherently controlled THz emission expected from perfectly uncoupled layers, i.e. a single graphene sheet, is not observed. We hypothesize that the observed angular dependence arises from weak coupling between the layers; a model calculation of the angular dependence treating the multilayer structure as a stack of independent bilayers with variable interlayer coupling qualitatively reproduces the polarization dependence, providing evidence for coupling., Comment: submitted to Nano Letters

We study the carrier dynamics in epitaxially grown graphene in the range of photon energies from 10 - 250 meV. The experiments complemented by microscopic modeling reveal that the carrier relaxation is significantly slowed down as the photon energy is tuned to values below the optical phonon frequency, however, owing to the presence of hot carriers, optical phonon emission is still the predominant relaxation process. For photon energies about twice the value of the Fermi energy, a transition from pump-induced transmission to pump-induced absorption occurs due to the interplay of interband and intraband processes.

The thermoelectric response of high mobility single layer epitaxial graphene on silicon carbide substrates as a function of temperature and magnetic field have been investigated. For the temperature dependence of the thermopower, a strong deviation from the Mott relation has been observed even when the carrier density is high, which reflects the importance of the screening effect. In the quantum Hall regime, the amplitude of the thermopower peaks is lower than a quantum value predicted by theories, despite the high mobility of the sample. A systematic reduction of the amplitude with decreasing temperature suggests that the suppression of the thermopower is intrinsic to Dirac electrons in graphene., Comment: 5 pages, 4 figures

After the pioneering investigations into graphene-based electronics at Georgia Tech (GT), great strides have been made developing epitaxial graphene on silicon carbide (EG) as a new electronic material. EG has not only demonstrated its potential for large scale applications, it also has become an invaluable material for fundamental two-dimensional electron gas physics showing that only EG is on route to define future graphene science. It was long known that graphene mono and multilayers grow on SiC crystals at high temperatures in ultra-high vacuum. At these temperatures, silicon sublimes from the surface and the carbon rich surface layer transforms to graphene. However the quality of the graphene produced in ultrahigh vacuum is poor due to the high sublimation rates at relatively low temperatures. The GT team developed growth methods involving encapsulating the SiC crystals in graphite enclosures, thereby sequestering the evaporated silicon and bringing growth process closer to equilibrium. In this confinement controlled sublimation (CCS) process, very high quality graphene is grown on both polar faces of the SiC crystals. Since 2003, over 50 publications used CCS grown graphene, where it is known as the "furnace grown" graphene. Graphene multilayers grown on the carbon-terminated face of SiC, using the CCS method, were shown to consist of decoupled high mobility graphene layers. The CCS method is now applied on structured silicon carbide surfaces to produce high mobility nano-patterned graphene structures thereby demonstrating that EG is a viable contender for next-generation electronics. Here we present the CCS method and demonstrate several of epitaxial graphene's outstanding properties and applications.

Since its inception in 2001, the science and technology of epitaxial graphene on hexagonal silicon carbide has matured into a major international effort and is poised to become the first carbon electronics platform. A historical perspective is presented and the unique electronic properties of single and multilayered epitaxial graphenes on electronics grade silicon carbide are reviewed. Early results on transport and the field effect in Si-face grown graphene monolayers provided proof-of-principle demonstrations. Besides monolayer epitaxial graphene, attention is given to C-face grown multilayer graphene, which consists of electronically decoupled graphene sheets. Production, structure, and electronic structure are reviewed. The electronic properties, interrogated using a wide variety of surface, electrical and optical probes, are discussed. An overview is given of recent developments of several device prototypes including resistance standards based on epitaxial graphene quantum Hall devices and new ultrahigh frequency analog epitaxial graphene amplifiers., Comment: 18 pages, 10 figures to be published in J. Phys. D, special Issue on Carbon Related Materials Cluster

The materials science of graphene grown epitaxially on the hexagonal basal planes of SiC crystals is reviewed. We show that the growth of epitaxial graphene on Si-terminated SiC(0001) is much different than growth on the C-terminated SiC(000 -1) surface, and discuss the physical structure of these graphenes. The unique electronic structure and transport properties of each type of epitaxial graphene is described, as well as progress toward the development of epitaxial graphene devices. This materials system is rich in subtleties, and graphene grown on the two polar faces differs in important ways, but all of the salient features of ideal graphene are found in these epitaxial graphenes, and wafer-scale fabrication of multi-GHz devices already has been achieved., Comment: To appear in the April 2010 issue of the MRS Bulletin

The quantum Hall effect, with a Berry's phase of $\pi$ is demonstrated here on a single graphene layer grown on the C-face of 4H silicon carbide. The mobility is $\sim$ 20,000 cm$^2$/V$\cdot$s at 4 K and ~15,000 cm$^2$/V$\cdot$s at 300 K despite contamination and substrate steps. This is comparable to the best exfoliated graphene flakes on SiO$_2$ and an order of magnitude larger than Si-face epitaxial graphene monolayers. These and other properties indicate that C-face epitaxial graphene is a viable platform for graphene-based electronics., Comment: Some modifications in the text and figures, 7 pages, 2 figures

The observation of the anomalous quantum Hall effect in exfoliated graphene flakes triggered an explosion of interest in graphene. It was however not observed in high quality epitaxial graphene multilayers grown on silicon carbide substrates. The quantum Hall effect is shown on epitaxial graphene monolayers that were deliberately grown over substrate steps and subjected to harsh processing procedures, demonstrating the robustness of the epitaxial graphene monolayers and the immunity of their transport properties to temperature, contamination and substrate imperfections. The mobility of the monolayer C-face sample is 19,000 cm^2/Vs. This is an important step towards the realization of epitaxial graphene based electronics., Comment: Two pages, 1 figure. Submitted to Science Brevia