Quasi-freestanding Graphene Research Articles

Freestanding n-Doped Graphene via Intercalation of Calcium and Magnesium into the Buffer Layer–SiC(0001) Interface

The intercalation of epitaxial graphene on SiC(0001) with Ca has been studied extensively, yet precisely where the Ca resides remains elusive. Furthermore, the intercalation of Mg underneath epitaxial graphene on SiC(0001) has not been reported. Here, we use low energy electron diffraction, x-ray photoelectron spectroscopy, secondary electron cut-off photoemission and scanning tunneling microscopy to elucidate the physical and electronic structure of both Ca- and Mg-intercalated epitaxial graphene on 6H-SiC(0001). We find that Ca intercalates underneath the buffer layer and bonds to the Si-terminated SiC surface, breaking the C-Si bonds of the buffer layer i.e. 'freestanding' the buffer layer to form Ca-intercalated quasi-freestanding bilayer graphene (Ca-QFSBLG). The situation is similar for the Mg-intercalation of epitaxial graphene on SiC(0001), where an ordered Mg-terminated reconstruction at the SiC surface and Mg bonds to the Si-terminated SiC surface are formed, resulting in Mg-intercalated quasi-freestanding bilayer graphene (Mg-QFSBLG). Ca-intercalation underneath the buffer layer has not been considered in previous studies of Ca-intercalated epitaxial graphene. Furthermore, we find no evidence that either Ca or Mg intercalates between graphene layers. However, we do find that both Ca-QFSBLG and Mg-QFSBLG exhibit very low workfunctions of 3.68 and 3.78 eV, respectively, indicating high n-type doping. Upon exposure to ambient conditions, we find Ca-QFSBLG degrades rapidly, whereas Mg-QFSBLG remains remarkably stable.

A new approach for synthesis of epitaxial nano-thin [formula omitted] alloy via intercalation underneath a graphene

In the present study we synthesized nano-thin epitaxial PtxGd alloys on Pt(111) single crystal surface covered with well-oriented graphene and investigated their electronic and atomic structure at different stages of synthesis. Low-energy electron diffraction, photoelectron spectroscopy and scanning tunneling microscopy data suggest that deposition of Gd on the graphene/Pt(111) system and its further intercalation at 1080 °C lead to formation of nano-thin Pt5Gd alloy covered with a quasi-freestanding graphene. We demonstrate that atomically flat alloy surface is terminated by Pt atomic layer with “kagome” structure. Control of graphene doping through variation of the alloy stoichiometry may open up new opportunities in developing advanced electronics. Owing to a well-known catalytic activity of Pt5Gd alloy, our thin-film system is promising for low-cost production of catalysts in the near future.

Raman 2D Peak Line Shape in Epigraphene on SiC

We measured a 2D peak line shape of epitaxial graphene grown on SiC in high vacuum, argon and graphene prepared by hydrogen intercalation from the so called buffer layer on a silicon face of SiC. We fitted the 2D peaks by Lorentzian and Voigt line shapes. The detailed analysis revealed that the Voigt line shape describes the 2D peak line shape better. We have determined the contribution of the homogeneous and inhomogeneous broadening. The homogeneous broadening is attributed to the intrinsic lifetime. Although the inhomogeneous broadening can be attributed to the spatial variations of the charge density, strain and overgrown graphene ribbons on the sub-micrometer length scales, we found dominant contribution of the strain fluctuations. The quasi free-standing graphene grown by hydrogen intercalation is shown to have the narrowest linewidth due to both homogeneous and inhomogeneous broadening.

Advanced graphene recording device for spin–orbit torque magnetoresistive random access memory

The non-volatile spin–orbit torque magnetic random access memory (SOT-MRAM) is a very attractive memory technology for near future computers because it has various advantages such as non-volatility, high density and scalability. In the present work we propose a model of a graphene recording device for the SOT-MRAM unit cell, consisting of a quasi-freestanding graphene intercalated with Au and an ultra-thin Pt layer sandwiched between graphene and a magnetic tunnel junction. As a result of using the claimed graphene recording memory element, a faster operation and lower energy consumption will be achieved under the recording information by reducing the electric current required to record. The efficiency of the graphene recording element was confirmed by the experimental results and the theoretical estimations.

Transformation of the buffer layer grown on 4H-SiC to single-layer graphene by ex situ hydrogen intercalation

The buffer layer samples grown on the Si-face of the 4H- and 6H-SiC substrates were heated in a hydrogen flow at different temperatures (600–900 °C) and heating times (40–60 min) in order to obtain quasi-freestanding monolayer graphene. Their structural properties were characterized before and after heating by using the methods of Raman spectroscopy, atomic force microscopy, Kelvin probe force microscopy, and low-energy electron diffraction. The dependence of the degree of coverage of the sample with quasi-freestanding graphene and the number of defects in the resulting films on the heating temperature was studied. As a result of optimization of the technological parameters, it is shown that the highest quality of the resulting quasi-freestanding graphene can be achieved by using the following parameters: heating time of 40 minutes and temperature of 800 °C.

Iron- and Silicon-Intercalated Graphene on Silicon Carbide: from Hybridization to Quasi-Freestanding Bilayer Graphene

Iron- and Silicon-Intercalated Graphene on Silicon Carbide: from Hybridization to Quasi-Freestanding Bilayer Graphene

Probing the structural transition from buffer layer to quasifreestanding monolayer graphene by Raman spectroscopy

The structural transition of a graphene buffer layer epitaxially grown on $6H$ silicon carbide (SiC) to quasifreestanding monolayer graphene by intercalation of oxygen and water molecules at low concentrations is studied by temperature-dependent Raman spectroscopy. We present a detailed investigation of the defect density and strain and doping evolution in the graphene crystal lattice. The structural transition from the buffer layer to monolayer graphene with high defect densities occurs at temperatures from 400 to 500 \ifmmode^\circ\else\textdegree\fi{}C, revealing the nanocrystalline regime of stage 2 of the amorphization trajectory, followed by the transition into stage 1 as evidenced by a gradual reduction of defects in graphene during subsequent annealing up to 900 \ifmmode^\circ\else\textdegree\fi{}C.

Homogeneous Large-Area Quasi-Free-Standing Monolayer and Bilayer Graphene on SiC

In this study, we first show that the argon flow during epitaxial graphene growth is an important parameter to control the quality of the buffer and the graphene layer. Atomic force microscopy (AFM) and low-energy electron diffraction (LEED) measurements reveal that the decomposition of the SiC substrate strongly depends on the Ar mass flow rate while pressure and temperature are kept constant. Our data are interpreted by a model based on the competition of the SiC decomposition rate, controlled by the Ar flow, with a uniform graphene buffer layer formation under the equilibrium process at the SiC surface. The proper choice of a set of growth parameters allows the growth of defect-free, ultra-smooth and coherent graphene-free buffer layer and bilayer-free monolayer graphene sheets which can be transformed into large-area high-quality quasi-freestanding monolayer and bilayer graphene (QFMLG and QFBLG) by hydrogen intercalation. AFM, scanning tunneling microscopy (STM), Raman spectroscopy and electronic transport measurements underline the excellent homogeneity of the resulting quasi-freestanding layers. Electronic transport measurements in four-point probe configuration reveal a homogeneous low resistance anisotropy on both {\mu}m- and mm scales.

Formation of graphene-capped cobalt silicides

Intercalation synthesis of graphene-capped cobalt silicides has been studied in situ by core-level photoelectron spectroscopy with synchrotron radiation and low-energy electron diffraction. It is found that at 400 °C the intercalation of graphene/Ni(1 1 1) with cobalt takes place in a wide range of coverage up to 17 ML Co. Graphene is strongly coupled with the upper layer of Co atoms and stabilizes the fcc structure of the intercalated Co(1 1 1) film. Subsequent intercalation of graphene/Co/Ni(1 1 1) with silicon results in the formation of an ordered Co3Si surface phase of the (√3 × √3)R30° structure and then of Co2Si silicide and Co-Si solid solution. Our experimental data and DFT calculations have shown that the coupling between the graphene layer and the surface silicide is rather weak and the properties of quasi-freestanding graphene are preserved.

Electrical Homogeneity Mapping of Epitaxial Graphene on Silicon Carbide.

Epitaxial graphene is a promising route to wafer-scale production of electronic graphene devices. Chemical vapor deposition of graphene on silicon carbide offers epitaxial growth with layer control but is subject to significant spatial and wafer-to-wafer variability. We use terahertz time-domain spectroscopy and micro four-point probes to analyze the spatial variations of quasi-freestanding bilayer graphene grown on 4 in. silicon carbide (SiC) wafers and find significant variations in electrical properties across large regions, which are even reproduced across graphene on different SiC wafers cut from the same ingot. The dc sheet conductivity of epitaxial graphene was found to vary more than 1 order of magnitude across a 4 in. SiC wafer. To determine the origin of the variations, we compare different optical and scanning probe microscopies with the electrical measurements from nano- to millimeter scale and identify three distinct qualities of graphene, which can be attributed to the microstructure of the SiC surface.

Tunneling Spectra of a Quasifreestanding Graphene Monolayer

With considering the great success of scanning tunnelling microscopy (STM) studies of graphene in the past few years, it is quite surprising to notice that there is still a fundamental contradiction about the reported tunnelling spectra of quasi-free-standing graphene monolayer. Many groups observed V-shape spectra with linearly vanishing density-of-state (DOS) at the Dirac point, whereas, the others reported spectra with a gap of 60 meV pinned to the Fermi level in the quasi-free-standing graphene monolayer. Here we systematically studied the two contradicted tunnelling spectra of the quasi-free-standing graphene monolayer on several different substrates and provided a consistent interpretation about the result. The gap in the spectra arises from the out-of-plane phonons in graphene, which mix the Dirac electrons at the Brillouin zone corners with the nearly free-electron states at the zone center. Our experiment indicated that interactions with substrates could effectively suppress effects of the out-of-plane phonons in graphene and enable us to detect only the DOS of the Dirac electrons in the spectra. We also show that it is possible to switch on and off the out-of-plane phonons of graphene at the nanoscale, i.e., the tunnelling spectra show switching between the two distinct features, through voltage pulses applied to the STM tip.

Excitation and characterization of image potential state electrons on quasi-free-standing graphene

We investigate the band structure of image potential states in quasi-free-standing graphene (QFG) monolayer islands using angle-resolved two-photon-photoemission spectroscopy. Direct probing by low-energy electron diffraction shows that QFG is formed following oxygen intercalation into the graphene-Ir(111) interface. Despite the apparent decoupling of the monolayer graphene from the Ir substrate, we find that the binding energy of the $\mathit{n}=1$ image potential state on these QFG islands increases by 0.17 eV, as compared to the original Gr/Ir(111) interface. We use calculations based on density-functional theory to construct an empirical, one-dimensional potential that quantitatively reproduces the image potential state binding energy and links the changes in the interface structure to the shift in energy. Specifically, two factors contribute comparably to this energy shift: a deeper potential well arising from the presence of intercalated oxygen adatoms and a wider potential well associated with the increase in the graphene-Ir distance. While image potential states have not been observed previously on QFG by photoemission, our paper now demonstrates that they may be strongly excited in a well-defined QFG system produced by oxygen intercalation. This opens an opportunity for studying the surface electron dynamics in QFG systems, beyond those found in typical nonintercalated graphene-on-substrate systems.

Energy-Dependent Chirality Effects in Quasifree-Standing Graphene.

We present direct experimental evidence of broken chirality in graphene by analyzing electron scattering processes at energies ranging from the linear (Dirac-like) to the strongly trigonally warped region. Furthermore, we are able to measure the energy of the van Hove singularity at the M point of the conduction band. Our data show a very good agreement with theoretical calculations for free-standing graphene. We identify a new intravalley scattering channel activated in case of a strongly trigonally warped constant energy contour, which is not suppressed by chirality. Finally, we compare our experimental findings with T-matrix simulations with and without the presence of a pseudomagnetic field and suggest that higher order electron hopping effects are a key factor in breaking the chirality near to the van Hove singularity.

Narrow plasmon resonances enabled by quasi-freestanding bilayer epitaxial graphene

Exploiting the underdeveloped terahertz range (~1012–1013 Hz) of the electromagnetic spectrum could advance many scientific fields (e.g. medical imaging for the identification of tumors and other biological tissues, non-destructive evaluation of hidden objects or ultra-broadband communication). Despite the benefits of operating in this regime, generation, detection and manipulation have proven difficult, as few materials have functional interactions with THz radiation. In contrast, graphene supports resonances in the THz regime through structural confinement of surface plasmons, which can lead to enhanced absorption. In prior work, the achievable plasmon resonances in such structures have been limited by multiple electron scattering mechanisms (i.e. large carrier scattering rates) which greatly broaden the resonance (>100 cm−1; 3 THz). We report the narrowest room temperature Drude response to-date, 30 cm−1 (0.87 THz), obtained using quasi-free standing bilayer epitaxial graphene (QFS BLG) synthesized on (0 0 0 1)6H–SiC. This narrow response is due to a 4-fold increase in carrier mobility and improved thickness and electronic uniformity of QFS BLG. Moreover, QFS BLG samples patterned into microribbons targeting 1.8–5.7 THz plasmon resonances also exhibit low scattering rates (37–53 cm−1). Due to the improved THz properties of QFS BLG, the effects of e-beam processing on carrier scattering rates was determined and we found that fabrication conditions can be tuned to minimize the impact on optoelectronic properties. In addition, electrostatic gating of patterned QFS BLG shows narrow band THz amplitude modulation. Taken together, these properties of QFS BLG should facilitate future development of THz optoelectronic devices for monochromatic applications.

Work function of graphene multilayers on SiC(0001)

The work function and electronic structure of epitaxial graphene as well as of quasi-freestanding graphene multilayer samples were studied by Kelvin probe and angle resolved photoelectron spectroscopy. The work function converges towards the value of graphite as the number of layers is increased. Thereby, n-type doped epitaxial graphene layers have a work function lower than graphite and p-type doped quasi-freestanding graphene layers exhibit a work function higher than graphite. We explain the behaviour by the filling of the -bands due to substrate interactions.

Synthesis of Freestanding Graphene on SiC by a Rapid-Cooling Technique.

Graphene has a negative thermal expansion coefficient; that is, when heated, the graphene lattice shrinks. On the other hand, the substrates typically used for graphene growth, such as silicon carbide, have a positive thermal expansion coefficient. Hence, on cooling graphene on SiC, graphene expands but SiC shrinks. This mismatch will physically break the atomic bonds between graphene and SiC. We have demonstrated that a graphenelike buffer layer on SiC can be converted to a quasifreestanding monolayer graphene by a rapid-cooling treatment. The decoupling of graphene from the SiC substrate was actually effective for reducing the electric carrier scattering due to interfacial phonons. In addition, the rapidly cooled graphene obtained in this way was of high-quality, strain-free, thermally stable, and strongly hole doped. This simple, classical, but quite novel technique for obtaining quasifreestanding graphene could open a new path towards a viable graphene-based semiconductor industry.

Quasi-freestanding graphene on Ni(111) by Cs intercalation.

A possible approach to achieve quasi-freestanding graphene on a substrate for technological purpose is the intercalation of alkali metal atoms. Cs intercalation between graphene and Ni(111) therefore is investigated using density functional theory, incorporating van der Waals corrections. It is known that direct contact between graphene and Ni(111) perturbs the Dirac states. We find that Cs intercalation restores the linear dispersion characteristic of Dirac fermions, which agrees with experiments, but the Dirac cone is shifted to lower energy, i.e., the graphene sheet is n-doped. Cs intercalation therefore decouples the graphene sheet from the substrate except for a charge transfer. On the other hand, the spin polarization of Ni(111) does not extend through the intercalated atoms to the graphene sheet, for which we find virtually spin-degeneracy.

Quasi-freestanding graphene on Ni(110): A graphene/metal contact with suppressed interface states

Graphene/Ni(110) has been studied by time-resolved X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure. The C 1s core level shows a splitting typical of periodically rippled interfaces. The analysis of the C K-edge reveals that the interface states previously observed for graphene/Ni(111) are suppressed in graphene/Ni(110). This suppression is due to the reduced hybridization of the Dirac-cone electrons in graphene with the d-bands of the (110)-oriented nickel contacts. Our results show that, contrary to commensurate growth of graphene on Ni(111), epitaxially grown graphene on Ni(110) behaves as a quasi-freestanding sheet, as the lattice mismatch gives rise to a moire reconstruction.

Structural and Electronic Properties of Nitrogen-Doped Graphene.

We investigate the structural and electronic properties of nitrogen-doped epitaxial monolayer graphene and quasifreestanding monolayer graphene on 6H-SiC(0001) by the normal incidence x-ray standing wave technique and by angle-resolved photoelectron spectroscopy supported by density functional theory simulations. With the location of various nitrogen species uniquely identified, we observe that for the same doping procedure, the graphene support, consisting of substrate and interface, strongly influences the structural as well as the electronic properties of the resulting doped graphene layer. Compared to epitaxial graphene, quasifreestanding graphene is found to contain fewer nitrogen dopants. However, this lack of dopants is compensated by the proximity of nitrogen atoms at the interface that yield a similar number of charge carriers in graphene.

Coincident-site lattice matching during van der Waals epitaxy.

Van der Waals (vdW) epitaxy is an attractive method for the fabrication of vdW heterostructures. Here Sb2Te3 films grown on three different kind of graphene substrates (monolayer epitaxial graphene, quasi freestanding bilayer graphene and the SiC (6√3 × 6√3)R30° buffer layer) are used to study the vdW epitaxy between two 2-dimensionally (2D) bonded materials. It is shown that the Sb2Te3 /graphene interface is stable and that coincidence lattices are formed between the epilayers and substrate that depend on the size of the surface unit cell. This demonstrates that there is a significant, although relatively weak, interfacial interaction between the two materials. Lattice matching is thus relevant for vdW epitaxy with two 2D bonded materials and a fundamental design parameter for vdW heterostructures.