As silicon-based electronics are reaching the nanosize limits of the semiconductor roadmap, carbon-based nanoelectronics has become a rapidly growing field, with great interest in tuning the properties of carbon-based materials. Chemical functionalization is a proposed route, but syntheses of graphene oxide (G-O) produce disordered, nonstoichiometric materials with poor electronic properties. We report synthesis of an ordered, stoichiometric, solid-state carbon oxide that has never been observed in nature and coexists with graphene. Formation of this material, graphene monoxide (GMO)[1], is achieved by annealing multilayered G-O. A combination of transmission electron microscopy and infrared microspectroscopy have provided critical experimental evidence to identify the novel structure. These results indicate that the resulting thermally reduced G-O (TRG-O) consists of a two-dimensional nanocrystalline phase segregation: unoxidized graphitic regions are separated from highly oxidized regions of GMO. GMO has a quasi-hexagonal unit cell, an unusually high 1:1 O:C ratio, and a calculated direct band gap of approximately 0.9 eV.

This work was supported by the NSF (CMMI-0856753 and CMMI-0900509). This work is based upon experiments performed at the Synchrotron Radiation Center. The SRC is funded by the University of Wisconsin-Madison and the University of Wisconsin-Milwaukee. Work performed at the SRC IRENI beamline been done with support from an NSF Major Research Instrumentation grant (DMR-0619759). The authors thank Bruker Technologies for the Grazing Angle Objective used for this work.

[1] Mattson, E.C. et al., ACSNano (2011) 5 (2011) 9710-9717.

Intercalation of gases between epitaxial graphene and its substrate has become a topic of interest for studies due to, for example, the unique opportunities to modify the graphene-substrate interaction and the possibilities to perform chemistry under the graphene layer. Further, a profound knowledge about graphenes stability in gases at elevated temperatures and pressures is essential for, among other things, the correct interpretation of gas adsorption studies on graphene supported metal cluster arrays.

We have studied intercalation and etching of Ir(111) supported graphene upon gas exposure to common gasses such as O₂ and CO in the entire pressure interval from 10^-8 to 0.1 mbar. Comparing perfect graphene layers without holes with graphene films, that only covers a fraction of the Ir(111) surface, we reveal that the holes - or more specific the graphene edges - are essential for intercalation.

For oxygen exposed graphene we develop a coherent picture of temperature dependent oxygen etching and intercalation. Using X-ray photoemission spectroscopy (XPS) and scanning tunnelling microscopy (STM) we show that a perfect graphene layer is stable against etching and intercalation up to 700 K, whereas at higher temperatures etching, but no intercalation, takes place. In contrast, a partial graphene coverage on Ir(111) enables dissociative oxygen adsorption on the bare Ir and subsequent intercalation underneath graphene flakes at 355 K and above. Intercalated oxygen remains stable up to a temperature of 600 K, above this temperature it desorbs in the form of CO or CO₂. We have determined XPS and STM fingerprints for the intercalated oxygen structure and we unambiguous assign it to a p(2x1)-O structure similar to the one observed on clean Ir(111). The decoupling of the intercalated graphene film from the metal substrate is directly visualized through the inability to form well-ordered Pt cluster arrays on the O-intercalated areas of graphene on Ir(111). Further, we have identified the rate limiting step for oxygen intercalation to be unlocking of the graphene edge and propose that this takes place through bond breaking between graphene edge bonds and the Ir substrate.

Using a combination of high pressure X-ray photoemission spectroscopy (HP-XPS) and STM we also show that CO intercalation takes place at room temperature and pressures in the 1 mbar range. The adsorption structure of intercalated CO is determined to be (3√3 × 3√3)R30^o, identical to the structure observed on clean Ir(111) upon high pressure CO exposure.

The work at Sandia National Laboratories was supported by LDRD and by the US DOE Office of Basic Energy Sciences, Division of Materials Science and Engineering. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000. The work at NRL was funded by the Office of Naval Research.

The implementation of graphene into next-generation electronics will require production high-quality graphene at the wafer scale. One promising route for the production of wafer-scale graphene is to grow epitaxial graphene (EG) via thermal decomposition of Si-terminated SiC (SiC(0001)). This method produces high-quality EG, but is accompanied by the formation of the so-called "buffer layer" at the interface, which is known to affect the electronic properties of the graphene. Despite numerous efforts to determine the nature of the buffer layer, debate persists concerning its atomic and chemical structure. Here, we use the X-ray Standing Wave (XSW) technique to create a precise chemically-sensitive description of the distributions of Si and C at the interface. This technique, which combines X-ray scattering and X-ray Photoelectron Spectroscopy (XPS), is capable of locating coherent distributions of chemically distinct species above a single crystal surface. This allows for a more detailed description of the interface than those afforded by scattering or XPS alone. Our analysis shows that the buffer layer, which is present in both UHV and furnace-grown EG/SiC(0001), contains no substantial non-bulk or oxide silicon component, and is thus purely carbon. We identify two chemically distinct carbon species within the interface layer, each with a distinct location above the Si-terminated surface, and report their positions and distributions with sub-angstrom precision. These results help to clarify long-standing uncertainties about the interfacial structure of graphene/SiC(0001). Further, we also highlight the potential for XSW with XPS as a valuable tool in the structural determination of complex interfaces, such as functionalized, doped, or intercalated epitaxial graphene.

We have prepared graphene on the SiC(000-1) surface (the so-called C-face of the {0001} surfaces), by heating the SiC in a Si-rich environment produced either by using disilane (≈10^-4 Torr) or cryogenically-purified neon (1 atm). With the Si-rich environments, we obtain considerably better uniformity in the thickness for thin, ≈ML-thick graphene on the C-face compared to that observed in samples prepared in vacuum or in an argon environment. We also find that different interface structures occur in these environments. In particular, we find a graphene-like buffer layer forming at the interface, analogous to the well known behavior of the SiC(0001) surface (the Si-face).

Studies are performed using atomic force microscopy (AFM), low-energy electron diffraction (LEED), and low-energy electron microscopy (LEEM). For graphene prepared in vacuum, LEED patterns show a characteristic 3X3 pattern together with graphene streaks. In contrast, for the graphene produced in either the disilane environment (≈10^-4 Torr) or 1 atm of neon, LEED patterns reveals a complex √43X√43-R±7.6° arrangement along with graphene spots. This structure is somewhat similar to the well known 6√3X6√3-R30° “buffer layer” of the Si-face, with satellite spots surrounding the primary Si spots, and is interpreted as arising from a C-rich buffer layer on the SiC. Selected area diffraction on those surface areas reveals a wavevector magnitude precisely equal to that of graphene, thus proving that the buffer layer does indeed have structure very close to that of graphene (the pattern is interpreted as a distortion of the buffer-layer graphene due to bonding to the underlying SiC). Using LEEM, measurements from the buffer layer of the reflected intensity of the electrons as a function of their energy reveal a new characteristic reflectivity curve, not seen for vacuum-prepared graphene.

After oxidation of the samples, the √43X√43-R±7.6° spots disappear and √3X√3-R30° spots appear on the surface. This latter behavior is interpreted as oxidation of the SiC surface beneath the buffer layer. Selected area diffraction on portions of the surface that were previously identified as buffer layer still reveal a wavevector magnitude precisely equal to that of graphene. However, LEEM reflectivity curves on those areas reveal a completely new spectrum, indicative of a "decoupling" of the buffer from the SiC. This decoupling is consistent with our interpretation of this new interface structure as being a graphene buffer layer on C-face SiC.

This work is supported by NSF.

The electronic structure of graphene depends on the number of graphene layers and the stacking sequence between the layers. Therefore, it is important to have a non-destructive technique for analyzing the overlayer coverage of graphene directly on the growth substrate. We have developed a technique using angle-resolved XPS to determine the average graphene thickness directly on metal foil substrates and SiC substrates. Since monolayer graphene films can be grown on Cu substrates, these samples are used as a standard reference for a monolayer of graphene. HOPG is used as a standard reference for bulk graphite. The electron mean free path of the C-1s photoelectron is determined by analyzing the areas under the C-1s peaks of monolayer graphene/Cu and bulk graphite and results in a value of 12.3 ±0.8 Å. With this electron mean free path, the graphene coverage of a film of arbitrary thickness can be determined from the areas under the C-1s peaks of the sample of interest, the monolayer graphene/Cu, and HOPG samples. Analysis of graphene coverages for graphene films grown on Cu-Ni substrates shows that a uniform monolayer is first formed before the growth of a second layer. The thickness of both the graphene overlayer and intermediate buffer layer has been determined on 6H-SiC substrates. Raman spectroscopy data have also been taken on these samples and compared to the overlayer coverages determined with XPS. This research was supported in part by the National Science Foundation (grant no. 1006350/1006411).