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Epitaxial graphene on SiC is the most promising substrate for the next generation 2D electronics, due to the possibility to fabricate 2D heterostructures directly on it, opening the door to the use of all technological processes developed for silicon electronics. To obtain a suitable material for large scale applications, it is essential to achieve perfect control of size, quality, growth rate and thickness. Here we show that this control on epitaxial graphene can be achieved by exploiting the face-to-face annealing of SiC in ultra-high vacuum. With this method, Si atoms trapped in the narrow space between two SiC wafers at high temperatures contribute to the reduction of the Si sublimation rate, allowing to achieve smooth and virtually defect free single graphene layers. We analyse the products obtained on both on-axis and off-axis 4H-SiC substrates in a wide range of temperatures (1300 °C–1500 °C), determining the growth law with the help of x-ray photoelectron spectroscopy (XPS). Our epitaxial graphene on SiC has terrace widths up to 10 μm (on-axis) and 500 nm (off-axis) as demonstrated by atomic force microscopy and scanning tunnelling microscopy, while XPS and Raman spectroscopy confirm high purity and crystalline quality.

Epitaxial growth on transition metal surfaces is an effective way to prepare large-area and high-quality graphene. However, the strong interaction between graphene and metal substrates suppresses the intrinsic excellent properties of graphene and the conductive metal substrates also hinder its applications in electronics. Here we demonstrate the decoupling of graphene from metal substrates by germanium oxide intercalation. Germanium is firstly intercalated into the interface between graphene and Ir(111) substrate. Then oxygen is subsequently intercalated, leading to the formation of a GeO x layer, which is confirmed by x-ray photoelectron spectroscopy. Low-energy electron diffraction and scanning tunneling microscopy studies show intact carbon lattice of graphene after the GeO x intercalation. Raman characterizations reveal that the intercalated layer effectively decouples graphene from the Ir substrate. The transport measurements demonstrate that the GeO x layer can act as a tunneling barrier in the fabricated large-area high-quality vertical graphene/GeO x /Ir heterostructure.

Graphene is considered as a promising candidate for manufacturing of sensors due to its extreme sensitivity to molecule absorption. In this work, we show the connection between the electrical and optical properties of epitaxial graphene chips grown on 4H-SiC and intended for the production of protein-based sensors. Using of a complex of techniques, including Raman spectroscopy, atomic force microscopy, Kelvin probe microscopy, study of I-V characteristics and low-frequency noise, it is shown that the character of frequency dependence of the spectral density of voltage fluctuations and its value at a frequency of 1 Hz can be used for classification and selection of graphene chips for their application as sensors. Classification of the graphene chips will allow more efficient development of graphene-based biosensors.

2D material of graphene has inspired huge interest in fabricating of solid state gas sensors. In this work, epitaxial graphene, quasi-free-standing graphene, and CVD epitaxial graphene samples on SiC substrates are used to fabricate gas sensors. Defects are introduced into graphene using SF6 plasma treatment to improve the performance of the gas sensors. The epitaxial graphene shows high sensitivity to NO2 with response of 105.1% to 4 ppm NO2 and detection limit of 1 ppb. The higher sensitivity of epitaxial graphene compared to quasi-free-standing graphene, and CVD epitaxial graphene was found to be related to the different doping types of the samples.

Van der Waals surface polariton nanostructures are promising candidates for miniaturisation of electromagnetic devices through the nanoscale confinement of infrared light. To fully exploit these nanoresonators, a computationally efficient model is necessary to predict polariton behaviour in complex geometries. Here, we develop a general wave model of surface polaritons in 2D geometries smaller than the polariton wavelength. Using geometric approximation widely tuneable infrared nanoimaging and local work function microscopy, we test this model against complex mono-/bi-layer graphene plasmon nanoresonators. Direct imaging of highly resonant graphene plasmon hotspots confirms that the model provides quantitatively accurate, analytical predictions of nanoresonator behaviour. The insights built with such models are crucial to the development of practical plasmonic nanodevices.

Large scale tetraoctylammonium-assisted electrochemical transfer of graphene grown on single-crystalline Ir(1 1 1) films by chemical vapour deposition is reported. The transferred samples are characterized in air with optical microscopy, Raman spectroscopy and four point transport measurements, providing the sheet resistance and the Hall carrier concentration. In vacuum we apply low energy electron diffraction and photoelectron spectroscopy that indicate transferred large-scale single orientation graphene. Angular resolved photoemission reveals a Fermi surface and a Dirac point energy which are consistent with charge neutral graphene., Journal of Physics: Condensed Matter, 29 (47), ISSN:0953-8984, ISSN:1361-648X

© 2017 IOP Publishing Ltd. Epitaxial growth of graphene on SiC is a scalable procedure that does not require any further transfer step, making this an ideal platform for graphene nanostructure fabrication. Focused ion beam (FIB) is a very promising tool for exploring the reduction of the lateral dimension of graphene on SiC to the nanometre scale. However, exposure of graphene to the Ga+ beam causes significant surface damage through amorphisation and contamination, preventing epitaxial graphene growth. In this paper we demonstrate that combining a protective silicon layer with FIB patterning implemented prior to graphene growth can significantly reduce the damage associated with FIB milling. Using this approach, we successfully achieved graphene growth over 3C-SiC/Si FIB patterned nanostructures.

We report experimental results on variable range hopping (VRH) and nonlinear transport in monolayer epitaxial graphene. In the linear regime in which the conductance is independent of voltage, the resistance curve derivative analysis method can be used to unequivocally determine whether Mott VRH or Efros–Shklovskii VRH is the dominant transport mechanism in our devices. In the nonlinear regime in which the conductance shows a strong dependence on voltage, we find that our experimental results can be successfully described by existing theoretical models. We suggest that the observed vastly different exponents in the threshold voltage–temperature dependence require further experimental and theoretical studies.

We studied the growth of Si at the surface of epitaxial graphene on 6H-SiC(0001). Characteristic flower-like islands with a thickness of 2 to 3 nm nucleated during the growth from 290 to 420 K. The islands became featureless in growth at higher temperatures. The growth was predominantly governed by diffusion-limited aggregation. The diffusion energy was evaluated to be 0.21 eV from the temperature-dependent decrease in the density of the islands.

We directly correlate the local (20-nm scale) and global electronic properties of a device containing mono-, bi- and tri-layer epitaxial graphene (EG) domains on 6H-SiC(0001) by simultaneously performing local surface potential measurements using Kelvin probe force microscopy and global transport measurements. Using well-controlled environmental conditions, where the starting state of the surface can be reproducibly defined, we investigate the doping effects of N2, O2, water vapour and NO2 at concentrations representative of the ambient air. We show that presence of O2, water vapour and NO2 leads to p-doping of all EG domains. However, the thicker layers of EG are significantly less affected by the atmospheric dopants. Furthermore, we demonstrate that the general consensus of O2 and water vapour present in ambient air providing majority of the p-doping to graphene is a common misconception. We experimentally show that even the combined effect of O2, water vapour, and NO2 at concentrations higher than typically present in the atmosphere does not fully replicate the state of the EG surface in ambient air. All doping effects can be reproducibly reversed by vacuum annealing. Thus, for EG gas sensors it is essential to consider naturally occurring environmental effects and properly separate them from those coming from targeted species., 4 Figures, 1 Table

We have studied weak localization (WL) and microwave-irradiated transport in multilayer graphene grown on SiC(0001). Different scattering channels are identified by analyzing the WL data. Moreover, we have shown that at a fixed ambient temperature, irradiating graphene with a microwave appears to be equivalent to changing the ambient temperature without microwave. We find that both the zero-field resistance of graphene and the WL correction term can be used as reliable thermometers which agree well with each other.

The quality of pentacene films in pentacene-based devices significantly affects their performance. In this report, the effects of various defects in graphene on a pentacene film were studied with scanning tunneling microscopy. The two most common defects found in the epitaxial graphene grown on SiC(0 0 0 1) substrates were subsurface carbon nanotube (CNT) defects and step edges. The most significant perturbation of the pentacene films was induced by step edges between single-layer and bilayer graphene domains, while the effect of step edges between single-layer domains was marginal. The subsurface CNT defects slightly distorted the structure of the single-layer pentacene, but the influence of such defects decreased as the thickness of the pentacene film increased. These results suggest that the uniformity of the graphene layer is the most important parameter in the growth of high-quality pentacene films on graphene.

High-quality epitaxial graphene is produced on silicon carbide by flash annealing of 6H-SiC in a lead (Pb) atmosphere at ∼1400 °C for 30 s. Nearly three top bilayers of SiC are decomposed due to fast heating and cooling, and sublimation of Si atoms from SiC is retarded by the Pb atmosphere. The synergetic effects promote the growth of continuous single-layered graphene sheets on the SiC terraces, and a model is established to elucidate the effects and growth mechanism.

Epitaxial graphene growth on SiC by Si selective etching using tetrafluorosilane (SiF4) is introduced, where SiF4 in Ar ambient selectively etches Si from the SiC surface at temperatures 1400 °C or above, leaving the C as graphene. Raman spectra of SiC treated in Ar for 60 min at 300 Torr did not show a graphene G-peak. However, with the addition of SiF4, a clear G-peak was observed for the surface treated for only 1 min, demonstrating faster Si removal using SiF4. Si selective etching of SiC is explained by the Gibbs free energy, where Si removal is more favorable compared to C removal by SiF4.

We produced epitaxial graphene under a moderate pressure of 4 mbar (about 400 Pa) at temperature 1600 °C. Raman spectroscopy and optical microscopy were used to confirm that epitaxial graphene has taken shape continually with slight thickness variations and regularly with a centimeter order of magnitude on 4H-SiC (0001) substrates. Then using X-ray photoelectron spectroscopy and Auger electron spectroscopy, we analyzed the chemical compositions and estimated the layer number of epitaxial graphene. Finally, an atomic force microscope and a scanning force microscope were used to characterize the morphological structure. Our results showed that under 4-mbar pressure, epitaxial graphene could be produced on a SiC substrate with a large area, uniform thickness but a limited morphological property. We hope our work will be of benefit to understanding the formation process of epitaxial graphene on SiC substrate in detail.

Epitaxial graphene (EG) on SiC has been proven to be an excellent material to investigate the fundamental physical properties of graphene and also to directly implement new findings into devices realized on the versatile platform of SiC. Within this framework, this work aims to review some of the recent major achievements accomplished in the field of EG on SiC, related to the growth of EG on the SiC(0 0 0 1) surface, the control of its doping level, the decoupling of the graphene from the substrate and the intercalation of foreign atomic species at the interface.

National Natural Science Foundation of China [11204232, 11074196, 51271156]; Natural Science Foundation of Fujian Province of China [2013J06002]; Xi'an Jiaotong University.

Intercalations of metals and silicon between epitaxial graphene and its substrates are reviewed. For metal intercalation, seven different metals have been successfully intercalated at the interface of graphene/Ru(0001) and form different intercalated structures. Meanwhile, graphene maintains its original high quality after the intercalation and shows features of weakened interaction with the substrate. For silicon intercalation, two systems, graphene on Ru(0001) and on Ir(111), have been investigated. In both cases, graphene preserves its high quality and regains its original superlative properties after the silicon intercalation. More importantly, we demonstrate that thicker silicon layers can be intercalated at the interface, which allows the atomic control of the distance between graphene and the metal substrates. These results show the great potential of the intercalation method as a non-damaging approach to decouple epitaxial graphene from its substrates and even form a dielectric layer for future electronic applications.

A graphene quantum dot provides a solid state analogue of the as yet unobserved charged vacuum predicted by quantum electrodynamics. The magnetic field affects the energy levels that contribute to the vacuum charge and either discharges a vacuum that is already charged or adds charge to it, depending on the position of the affected level relative to the Fermi level. These effects occur in external potentials of a few hundred meV and magnetic fields of a few T, an experimentally realisable regime.

The atomic and electronic structures of Cl-intercalated epitaxial graphene on SiC are studied by first-principles calculations. By increasing the Cl concentration, doping levels from n-type to slightly p-type are achieved on the SiC(0001) surface, while a wider range of doping levels is possible on the SiC(000) surface. We find that the Cl atoms prefer bonding to the substrate rather than to the graphene. By varying the Cl concentration the doping level can be tailored. Consideration of van der Waals forces improves the distance between the graphene and the substrate as well as the binding energy, but it is not essential for the formation energy. For understanding the doping mechanism the introduction of non-local van der Waals contributions to the exchange correlation functional is shown to be essential.

We report on temperature-programmed growth of graphene islands on Ru (0001) at annealing temperatures of 700 °C, 800 °C, and 900 °C. The sizes of the islands each show a nonlinear increase with the annealing temperature. In 700 °C and 800 °C annealings, the islands have nearly the same sizes and their ascending edges are embedded in the upper steps of the ruthenium substrate, which is in accordance with the etching growth mode. In 900 °C annealing, the islands are much larger and of lower quality, which represents the early stage of Smoluchowski ripening. A longer time annealing at 900 °C brings the islands to final equilibrium with an ordered moire pattern. Our work provides new details about graphene early growth stages that could facilitate the better control of such a growth to obtain graphene with ideal size and high quality.

We compare different growth methods with the aim of optimizing the long-range order of a graphene layer grown on Ru(0001). Combining chemical vapor deposition with carbon loading and segregation of the surface layer leads to autocorrelation lengths of 240 angstrom. We present several routes to band gap and charge carrier mobility engineering for the example of graphene on Ir(111). Ir cluster superlattices self-assembled onto the graphene moire pattern produce a strong renormalization of the electron group velocity close to the Dirac point, leading to highly anisotropic Dirac cones and the enlargement of the gap from 140 to 340 meV. This gap can further be enhanced to 740 meV by Na co-adsorption onto the Ir cluster superlattice at room temperature. This value is close to that of Ge, and the high group velocity of the charge carriers is fully preserved. We also present data for Na adsorbed without the Ir clusters. In both cases we find that the Na is on top of the graphene layer.

Graphene is widely regarded as an important new electronic material with interesting two-dimensional electron gas properties. Not only that, but graphene is widely considered to be an important new material for large-scale integrated electronic devices that may eventually even succeed silicon. In fact, there are countless publications that demonstrate the amazing applications potential of graphene. In order to realize graphene electronics, a platform is required that is compatible with large-scale electronics processing methods. It was clear from the outset that graphene grown epitaxially on silicon carbide substrates was exceptionally well suited as a platform for graphene-based electronics, not only because the graphene sheets are grown directly on electronics-grade silicon carbide (an important semiconductor in its own right), but also because these sheets are oriented with respect to the semiconductor. Moreover, the extremely high temperatures involved in production assure essentially defect-free and contamination-free materials with well-defined interfaces. Epitaxial graphene on silicon carbide is not a unique material, but actually a class of materials. It is a complex structure consisting of a reconstructed silicon carbide surface, which, for planar hexagonal silicon carbide, is either the silicon- or the carbon-terminated face, an interfacial carbon rich layer, followed by one or more graphene layers. Consequently, the structure of graphene films on silicon carbide turns out to be a rich surface-science puzzle that has been intensively studied and systematically unravelled with a wide variety of surface science probes. Moreover, the graphene films produced on the carbon-terminated face turn out to be rotationally stacked, resulting in unique and important structural and electronic properties. Finally, in contrast to essentially all other graphene production methods, epitaxial graphene can be grown on structured silicon carbide surfaces to produce graphene nanostructured without patterning the graphene itself. This method produces graphene nanostructures with atomically smooth edges that ultimately determine the transport properties of these structures. The coherent collection of papers in this special issue of Journal of Physics D: Applied Physics provides a snapshot of the current state of the art, presented by leading experts, highlighting various aspects of the science and technology of epitaxial graphene. This collection systematically addresses the production of epitaxial graphene on the two polar faces of silicon carbide, as well as the structural and electronic properties of the graphene films. Special attention is paid to the rapidly emerging field of chemically modified graphene, which promises to introduce a bandgap into the electronic structure of graphene, which is critical for many electronic applications. Also presented are methods to incorporate properties of the silicon carbide itself, as well as advanced methods to produce high-quality graphene and graphene nanostructures using structured growth methods.

Chemistry will play an increasingly important role in the realization of graphene applications. The chemical formation of covalent carbon–carbon bonds involving the basal plane carbon atoms offers an alternative approach to the control of the electronic properties of graphene, and potentially allows the generation of insulating and semiconducting regions in graphene wafers. This review summarizes recent progress in the covalent modification of epitaxial graphene and the effect that chemistry has on the electronic and magnetic properties of the material.

Graphene electronics was officially invented at the Georgia Institute of Technology in 2003 after experimental and theoretical research on graphene properties starting from 2001. This paper focuses on the motivation and events leading to the invention of graphene electronics, as well as on recent developments. Graphene electronics was originally conceived as a new electronics paradigm to incorporate the room-temperature ballistic and coherent properties of carbon nanotubes in a patternable electronic material. Graphene on silicon carbide was chosen as the most suitable material. Other electronics schemes, involving transferred (exfoliated and chemical vapor deposition-produced) graphitic materials, that operate in the diffusive regime may not be competitive with standard methods and may therefore not significantly impact electronics. In recent years, epitaxial graphene has improved to the point where graphene electronics according to the original concept appears to be within reach. Beyond electronics, epitaxial graphene research has led to important developments in graphene physics in general and has become a leading platform for graphene science as well.

This article investigates the formation mechanism of epitaxial graphene on 6H-SiC (000) substrates under low pressure of 2 mbar environment. It is shown that the growth temperature dramatically affects the formation and quality of epitaxial graphene. The higher growing temperature is of great benefit to the quality of epitaxial graphene and also can reduce the impact of the substrate for graphene. By analyzing Raman data, we conclude that epitaxial graphene grown at 1600 °C has a turbostratic graphite structure. The test from scanning electron microscopy (SEM) indicates that the epitaxial graphene has a size of 10 μm. This research will provide a feasible route for fabricating larger size of epitaxial graphene on SiC substrate.

The Systeme Internationale dunites (SI) is about to undergo its biggest change in half a century by redefining the units for mass and current in terms of the fundamental constants h and e, respectively. This change crucially relies on the exactness of the relationships that link these constants to measurable quantities. Here we report the first direct comparison of the integer quantum Hall effect (QHE) in epitaxial graphene with that in GaAs/AlGaAs heterostructures. We find no difference in the quantized resistance value within the relative standard uncertainty of our measurement of 8.6 x 10(-11), this being the most stringent test of the universality of the QHE in terms of material independence. Funding Agencies|UK National Measurement Office (NMO)||Swedish Research Council||Foundation for Strategic Research||EU||EPSRC|EP/G041954|Science & Innovation Award|EP/G014787|SINGLE

The growth of epitaxial graphene on the SiC(0001) surface is theoretically studied by assuming silicon (Si) sublimation from the surface. Our results indicate that a new graphene sheet grows from the interface between the old graphene sheets and SiC substrate, as found in our previous study on graphene growth by carbon (C) deposition. Graphene growth requires overcoming rather lower energy barriers until 0-monolayer graphene (buffer layer) is formed. Further growth toward formation of 1-monolayer graphene requires overcoming energy barriers higher by about 0.7 eV, which indicates that the growth preferably stops once when 0-monolayer graphene is formed. Compared with the C deposition case, the growth requires overcoming the energy barrier higher by about 0.7 eV, which indicates that the graphene growth is more difficult. In addition, the nonuniform growth of surface C aggregates is thought to degrade the quality of the grown graphene. The C-rich condition is therefore important for obtaining high-quality graphene. The experimental graphene growth is considered to proceed similarly to the C deposition case rather than the Si sublimation case.

The inverting operation of a logic inverter, using two back-gate epitaxial graphene-on-silicon field-effect transistors (GOSFETs), is demonstrated at room temperature. Thanks to the asymmetric ambipolarity of the fabricated GOSFETs, owing to the undesirable back-gate leakage, the on/off state current has been dramatically reduced. This results in a well matched input/output voltage levels for a wide V DD range from more than 1 V down to 0.5 V. The inverting operation of the device is obtained at as low V DD bias as 0.5 V. Voltage gains higher than the unity are also obtained. The experimental results are in good agreement with the simulation results made for the case of asymmetric ambipolar transistors.

The epitaxial graphene growth at the 4H-SiC(0001) surface with intentionally inserted step-free basal plane regions was performed by high temperature annealing in the range of 1600–1900 °C under ultrahigh vacuum. For fabricating inverted-mesa structures with the step-free regions at SiC surfaces, a combined process consisting of a direct laser digging and a Si-vapor etching at 1900 °C was utilized. The graphitized surfaces were characterized by atomic force microscopy, low acceleration voltage (0.1–1.0 kV) scanning electron microscopy and Raman spectroscopy. It was found that the graphene thickness at the SiC step-free surface tends to be suppressed compared with the thickness at background SiC step-terrace surfaces where the steps are intrinsically introduced from intentional/unintentional substrate miscut angles. From the characterization by Raman mapping, 1 ML graphene was obtained at the SiC step-free surface at 1600 °C graphitization in contrast to the case that multilayer graphene was grown at SiC step-terrace surfaces.

In the solid–vapor phase equilibria between SiC and O2 system, there exists a region where the reaction (2+x)SiC+O2→(2+x)Si↑+ 2CO↑+ xC↓ takes place [Y. W. Song and F. W. Smith: J. Am. Ceram. Soc. 88 (2005) 1864]. By tuning the temperature and the oxygen pressure used in the graphitization annealing into this region, we have succeeded in the growth of epitaxial graphene on SiC crystals at 1000 °C, which is lower, by 250 °C or more, than the conventional epitaxial graphene method. The method is especially useful to formation of epitaxial graphene on silicon (GOS), which requires a lower graphitization temperature because of the Si substrate as well as of its mission to attain compatibility with Si technology.

National Natural Science Foundation of China [10702056, 10774124]; Xiamen University; Academic Award for Doctoral Candidates of China

The atomic structures of graphene islands on SiC(0001) surfaces are studied theoretically together with their growth mechanism. Two types of embedded graphene island structure are proposed. It is shown that these structures actually act as the graphene island electronically, and that those with zigzag edges have the magnetoelectric effect.