为了充分利用石墨烯或其他二维材料的扭转双层结构，必须精确控制堆叠层之间的扭转角，因为该参数决定了异质结的性质。在此背景下，已有研究报道了一种在SiC(0001)表面上使用硼吖嗪作为表面活性剂分子的生长方案，该方案促成了非常规取向的高质量外延石墨烯层的形成，即与衬底晶格对齐（G-$R0^\circ$）[Bocquet et al. Phys. Rev. Lett. 125, 106102 (2020)]。由于G-$R0^\circ$层位于缓冲层（也称为第零层石墨烯，ZLG）之上，该缓冲层相对于SiC衬底旋转了$30^\circ$且仍与其共价键合，因此将ZLG-$R30^\circ$与衬底解耦即可获得高质量的扭转双层石墨烯（tBLG）。在此我们报道了通过在硼吖嗪气氛中升高退火温度来实现ZLG-$R30^\circ$的解耦。虽然这会将ZLG-$R30^\circ$转化为G-$R30^\circ$从而生成tBLG，但在高温下的生长过程不再自限制，导致表面被不同厚度的石墨烯多层结构拼凑覆盖。我们发现ZLG上有20%的面积被tBLG覆盖，而在表面其余部分，tBLG则位于一个或多个额外的石墨烯层之上。为了实现仅由tBLG完全覆盖，采用其他解耦ZLG的替代方法（例如通过插入合适的原子进行插层）可能更具优势。
英文摘要：
To take full advantage of twisted bilayers of graphene or other two-dimensional materials, it is essential to precisely control the twist angle between the stacked layers, as this parameter determines the properties of the heterostructure. In this context, a growth routine using borazine as a surfactant molecule on SiC(0001) surfaces has been reported, leading to the formation of high-quality epitaxial graphene layers that are unconventionally oriented, i.e., aligned with the substrate lattice (G-$R0^\circ$) [Bocquet et al. Phys. Rev. Lett. 125, 106102 (2020)]. Since the G-$R0^\circ$ layer sits on a buffer layer, also known as zeroth-layer graphene (ZLG), which is rotated $30^\circ$ with respect to the SiC substrate and still covalently bonded to it, decoupling the ZLG-$R30^\circ$ from the substrate can lead to high-quality twisted bilayer graphene (tBLG). Here we report the decoupling of ZLG-$R30^\circ$ by increasing the temperature during annealing in a borazine atmosphere. While this converts ZLG-$R30^\circ$ to G-$R30^\circ$ and thus produces tBLG, the growth process at elevated temperature is no longer self-limiting, so that the surface is covered by a patchwork of graphene multilayers of different thicknesses. We find a 20% coverage of tBLG on ZLG, while on the rest of the surface tBLG sits on one or more additional graphene layers. In order to achieve complete coverage with tBLG only, alternative ways of decoupling the ZLG, e.g., by intercalation with suitable atoms, may be advantageous.
Raman spectra were measured for mono-, bi- and trilayer graphene grown on SiC by solid state graphitization, whereby the number of layers was pre-assigned by angle-resolved ultraviolet photoemission spectroscopy. It was found that the only unambiguous fingerprint in Raman spectroscopy to identify the number of layers for graphene on SiC(0001) is the linewidth of the 2D (or D*) peak. The Raman spectra of epitaxial graphene show significant differences as compared to micromechanically cleaved graphene obtained from highly oriented pyrolytic graphite crystals. The G peak is found to be blue-shift…
We propose a table-top method to obtain bilayer quasi-free-standing epitaxial-graphene (QFSEG) on SiC(0001). By applying a microwave annealing in air to a monolayer epitaxial graphene (EG) grown on SiC(0001), the buffer layer is decoupled from the SiC substrate and becomes the second EG layer as confirmed by the low energy electron diffraction, high-resolution transmission electron microscopy, Raman scattering spectroscopy, X-ray photoelectron spectroscopy, and angle-resolved photoelectron spectroscopy. The most likely mechanism of the decoupling is given by the oxidation of the SiC surface, w…
Growth of epitaxial graphene on the C-face of SiC has been investigated. Using a confinement controlled sublimation (CCS) method, we have achieved well controlled growth and been able to observe propagation of uniform monolayer graphene. Surface patterns uncover two important aspects of the growth, i.e. carbon diffusion and stoichiometric requirement. Moreover, a new "stepdown" growth mode has been discovered. Via this mode, monolayer graphene domains can have an area of hundreds of square micrometers, while, most importantly, step bunching is avoided and the initial uniformly stepped SiC surf…
We present an orbital-resolved density functional theory study on the electronic properties of hydrogen and lithium intercalated graphene grown on the Si face of SiC. Starting from the $(6\sqrt3\times6\sqrt3)R30^{\circ}$ surface reconstruction of the graphene/SiC heterosystem, we find that both H and Li can restore the ideal structural characteristics of the two nonequivalent junction parts (i.e. graphene and the SiC substrate) when inserted at the interface. However, the chemical/electrostatic interactions remain different for the two cases. Hence, H-intercalated epitaxial graphene is subject…
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…
We present electronic structure calculations of few-layer epitaxial graphene nanoribbons on SiC(0001). Trough an atomistic description of the graphene layers and the substrate within the extended Hückel Theory and real/momentum space projections we argue that the role of the heterostructure's interface becomes crucial for the conducting capacity of the studied systems. The key issue arising from this interaction is a Fermi level pinning effect introduced by dangling interface bonds. Such phenomenon is independent from the width of the considered nanostructures, compromising the importance of c…
We review progress in developing epitaxial graphene as a material for carbon electronics. In particular, improvements in epitaxial graphene growth, interface control and the understanding of multilayer epitaxial graphene's electronic properties are discussed. Although graphene grown on both polar faces of SiC is addressed, our discussions will focus on graphene grown on the (000-1) C-face of SiC. The unique properties of C-face multilayer epitaxial graphene have become apparent. These films behave electronically like a stack of nearly independent graphene sheets rather than a thin Bernal-stack…
We investigate the magnetotransport properties of quasi-free standing epitaxial graphene bilayer on SiC, grown by atmospheric pressure graphitization in Ar, followed by H$_2$ intercalation. At the charge neutrality point the longitudinal resistance shows an insulating behavior, which follows a temperature dependence consistent with variable range hopping transport in a gapped state. In a perpendicular magnetic field, we observe quantum Hall states (QHSs) both at filling factors ($ν$) multiple of four ($ν=4, 8, 12$), as well as broken valley symmetry QHSs at $ν=0$ and $ν=6$. These results unamb…
An in vacuo thermal desorption process has been accomplished to form epitaxial graphene (EG) on 4H- and 6H-SiC substrates using a commercial chemical vapor deposition reactor. Correlation of growth conditions and the morphology and electrical properties of EG are described. Raman spectra of EG on Si-face samples were dominated by monolayer thickness. This approach was used to grow EG on 50 mm SiC wafers that were subsequently fabricated into field effect transistors with fmax of 14 GHz.
The potential of graphene to impact the development of the next generation of electronics has renewed interest in its growth and structure. The graphitization of hexagonal SiC surfaces provides a viable alternative for the synthesis of graphene, with wafer-size epitaxial graphene on SiC(0001) now possible. Despite this recent progress, the exact nature of the graphene-SiC interface and whether the graphene even has a semiconducting gap remain controversial. Using scanning tunneling microscopy with functionalized tips and density functional theory calculations, here we show that the interface i…
A simple, non-invasive method using Raman spectroscopy for the estimation of the thickness of graphene layers grown epitaxially on silicon carbide (SiC) is presented, enabling simultaneous determination of thickness, grain size and disorder using the spectra. The attenuation of the substrate Raman signal due to the graphene overlayer is found to be dependent on the graphene film thickness deduced from X-ray photoelectron spectroscopy and transmission electron microscopy of the surfaces. We explain this dependence using an absorbing overlayer model. This method can be used for mapping graphene …
We present a minimal but crucial microscopic theory for epitaxial graphene and graphene nanoribbons on the 4H-SiC(0001) surface -- protopypical materials to explore physical properties of graphene in large scale. Coarse-grained model Hamiltonians are constructed based on the atomic and electronic structures of the systems from first-principles calculations. From the theory, we unambiguously uncover origins of several intriguing experimental observations such as broken-symmetry states around the Dirac points and new energy bands arising throughout the Brillouin zone, thereby establishing the ro…
Interest in the use of graphene in electronic devices has motivated an explosion in the study of this remarkable material. The simple, linear Dirac cone band structure offers a unique possibility to investigate its finer details by angle-resolved photoelectron spectroscopy (ARPES). Indeed, ARPES has been performed on graphene grown on metal substrates but electronic applications require an insulating substrate. Epitaxial graphene grown by the thermal decomposition of silicon carbide (SiC) is an ideal candidate for this due to the large scale, uniform graphene layers produced. The experimental …
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…
Pentacene has been used widely in organic devices, and the interface structure between pentacene and a substrate is known to significantly influence device performances. Here we demonstrate that molecular ordering of pentacene on graphene depends on the interaction between graphene and its underlying SiC substrate. The adsorption of pentacene molecules on zero-layer and single-layer graphene, which were grown on a Sifaced 6H-SiC(0001) wafer, was studied using scanning tunneling microscopy (STM). Pentacene molecules form a quasi-amorphous layer on zero-layer graphene which interacts strongly wi…
We investigated the electroluminescent properties of the epitaxial graphene/SiC junction. The temperature and current dependence of electroluminescence from the epitaxial graphene/SiC is measured within a temperature range of 50-300 K. The result of electroluminescence at 300~K is compared with the electroluminescent spectra from aluminium/SiC junction. The difference between the spectra is explained by the different band bending, which could lead to the tunable LED due to the semi-metal character of the graphene. We observed the electroluminescence at both bias polarities and we described the…
Quasi-free standing epitaxial graphene is obtained on SiC(0001) by hydrogen intercalation. The hydrogen moves between the 6root3 reconstructed initial carbon layer and the SiC substrate. The topmost Si atoms which for epitaxial graphene are covalently bound to this buffer layer, are now saturated by hydrogen bonds. The buffer layer is turned into a quasi-free standing graphene monolayer with its typical linear pi-bands. Similarly, epitaxial monolayer graphene turns into a decoupled bilayer. The intercalation is stable in air and can be reversed by annealing to around 900 degrees Celsius.
The effect of oxygen adsorption on the local structure and electronic properties of monolayer graphene grown on SiC(0001) has been studied by means of Low Energy Electron Microscopy (LEEM), microprobe Low Energy Electron Diffraction (\muLEED) and microprobe Angle Resolved Photoemission (\muARPES). We show that the buffer layer of epitaxial graphene on SiC(0001) is partially decoupled after oxidation. The monitoring of the oxidation process demonstrates that the oxygen saturates the Si dangling bonds, breaks some Si-C bonds at the interface and intercalates the graphene layer. Accurate control …
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 me…
We have measured optical absorption in mid-infrared spectral range on hydrogen intercalated epitaxial graphene grown on silicon face of SiC. We have used attenuated total reflection geometry to enhance absorption related to the surface and SiC/graphene interface. The samples of epitaxial graphene have been intercalated in the temperature range of 790 to 1250$^\circ$C and compared to the reference samples of hydrogen etched SiC. We have found that although the Si-H bonds form at as low temperatures as 790$^\circ$C, the well developed bond order has been reached only for epitaxial graphene inter…
We present an innovative method of selective epitaxial growth of few layers graphene (FLG) on a pre-patterned SiC substrate. The methods involves, successively, the sputtering of a thin AlN layer on top of a mono-crystalline SiC substrate and, then, patterning it with e-beam lithography (EBL) and wet etching. The sublimation of few atomic layers of Si from the SiC substrate occurs only through the selectively etched AlN layer. The presence of the Raman G-band at ~1582 cm-1 in the AlN-free areas is used to validate the concept, it gives absolute evidence of the selective FLG growth.
The electrical transport properties of epitaxial graphene layers are correlated with the SiC surface morphology. In this study we show by atomic force microscopy and Raman measurements that the surface morphology and the structure of the epitaxial graphene layers change significantly when different pretreatment procedures are applied to nearly on-axis 6H-SiC(0001) substrates. It turns out that the often used hydrogen etching of the substrate is responsible for undesirable high macro steps evolving during graphene growth. A more advantageous type of sub-nanometer stepped graphene layers is obta…
We demonstrate hydrogen assisted growth of high quality epitaxial graphene on the C-face of 4H-SiC. Compared with the conventional thermal decomposition technique, the size of the growth domain by this method is substantially increased and the thickness variation is reduced. Based on the morphology of epitaxial graphene, the role of hydrogen is revealed. It is found that hydrogen acts as a carbon etchant. It suppresses the defect formation and nucleation of graphene. It also improves the kinetics of carbon atoms via hydrocarbon species. These effects lead to increase of the domain size and the…
We show using scanning tunneling microscopy, spectroscopy, and ab initio calculations that several intercalation structures exist for Na in epitaxial graphene on SiC(0001). Intercalation takes place at room temperature and Na electron-dopes the graphene. It intercalates in-between single-layer graphene and the carbon-rich interfacial layer. It also penetrates beneath the interfacial layer and decouples it to form a second graphene layer. This decoupling is accelerated by annealing and is verified by direct Na deposition onto the interface layer. Our observations show that intercalation in grap…
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…
Epitaxial graphene layers were grown on the C-face of 4H- and 6H-SiC using an argon-mediated growth process. Variations in growth temperature and pressure were found to dramatically affect the morphological properties of the layers. The presence of argon during growth slowed the rate of graphene formation on the C-face and led to the observation of islanding. The similarity in the morphology of the islands and continuous films indicated that island nucleation and coalescence is the growth mechanism for C-face graphene.
We have measured the electrical response to NO$_2$, N$_2$, NH$_3$ and CO for epitaxial graphene and quasi freestanding epitaxial graphene on 6H-SiC substrates. Quasi freestanding epitaxial graphene shows a 6 fold increase in NO2 sensitivity compared to epitaxial graphene. Both samples show a sensitivity better than the experimentally limited 1 ppb. The strong increase in sensitivity of quasi freestanding epitaxial graphene can be explained by a Fermi-energy close to the Dirac Point leading to a strongly surface doping dependent sample resistance. Both sensors show a negligible sensitivity to N…
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 t…
The evolution in the surface morphology of epitaxial graphene films and 6H-SiC(0001) substrates is studied by electron channeling contrast imaging. Whereas film thickness is determined by growth temperature only, increasing growth times at constant temperature affect both internal stress and film morphology. Annealing times in excess of 8-10 minutes lead to an increase in the mean square roughness of SiC step edges to which graphene films are pinned, resulting in compressively stressed films at room temperature. Shorter annealing times produce minimal changes in the morphology of the terrace e…
The realization of air-stable 2D metals epitaxial to SiC and capped by graphene creates a potentially immense chemical space of 2D metals and alloys that could expand the variety of solid-state excitations unique to 2D metals beyond what is known for graphene and niobium/tantalum chalcogenides. We perform a high-throughput computational survey from first-principles predicting the structures and stabilities of all metals in the periodic table when they intercalate graphene/SiC. Our results not only agrees with all experimentally known metal/SiC structures explored so far, but also reveals consp…
We study the charge transfer between a quasi-free-standing monolayer graphene, produced by hydrogen intercalation, and surface acceptor states. We consider two models of acceptor density of states to explain the high hole densities observed in graphene and find the density responsivity to the gate voltage. By studying magneto-oscillations of the carrier density we provide an experimental way to determine the relevant model.
Local electronic structures of nanometer-sized patches of epitaxial graphene and its interface layer with SiC(0001) have been studied by atomically resolved scanning tunneling microscopy and spectroscopy. Localized states belonging to the interface layer of a graphene/SiC system show to have an essential influence on the electronic structure of graphene. Giant enhancement of inelastic tunneling, reaching 50% of the total tunneling current, has been observed at the localized states on a nanometer-sized graphene monolayer surrounded by defects.
The thermal decomposition of SiC surface provides, perhaps, the most promising method for the epitaxial growth of graphene on a material useful in the electronics platform. Currently, efforts are focused on a reliable method for the growth of large-area, low-strain epitaxial graphene that is still lacking. We report here a novel method for the fast, single-step epitaxial growth of large-area homogeneous graphene film on the surface of SiC(0001) using an infrared CO2 laser (10.6 μm) as the heating source. Apart from enabling extreme heating and cooling rates, which can control the stacking orde…
We report a Raman study of the so-called buffer layer with $(6\sqrt3\times6\sqrt3)R30^{\circ}$ periodicity which forms the intrinsic interface structure between epitaxial graphene and SiC(0001). We show that this interface structure leads to a nonvanishing signal in the Raman spectrum at frequencies in the range of the D- and G-band of graphene and discuss its shape and intensity. Ab-initio phonon calculations reveal that these features can be attributed to the vibrational density of states of the buffer-layer.
We present a structural analysis of the graphene-4HSiC(0001) interface using surface x-ray reflectivity. We find that the interface is composed of an extended reconstruction of two SiC bilayers. The interface directly below the first graphene sheet is an extended layer that is more than twice the thickness of a bulk SiC bilayer (~1.7A compared to 0.63A). The distance from this interface layer to the first graphene sheet is much smaller than the graphite interlayer spacing but larger than the same distance measured for graphene grown on the (000-1) surface, as predicted previously by ab intio c…
The early stages of epitaxial graphene layer growth on the Si-terminated 6H-SiC(0001) are investigated by Auger electron spectroscopy (AES) and depolarized Raman spectroscopy. The selection of the depolarized component of the scattered light results in a significant increase in the C-C bond signal over the second order SiC Raman signal, which allows to resolve submonolayer growth, including individual, localized C=C dimers in a diamond-like carbon matrix for AES C/Si ratio of $\sim$3, and a strained graphene layer with delocalized electrons and Dirac single-band dispersion for AES C/Si ratio $…
Graphene is a promising contender to succeed the throne of silicon in electronics. To this goal, large-scale epitaxial growth of graphene on substrates should be developed. Among various methods along this line, epitaxial growth of graphene on SiC substrates by thermal decomposition of surface layers has proved itself quite satisfactory both in quality and in process reliability. Even modulation of structural and hence electronic properties of graphene is possible by tuning the graphene/SiC interface structure. The challenges for this graphene-on-SiC technology, however, are the abdication of …
The fabrication of epitaxial graphene (EG) on SiC substrate by annealing has attracted a lot of interest as it may speed up the application of graphene for future electronic devices. The interaction of EG and the SiC substrate is critical to its electronic and physical properties. In this work, Raman spectroscopy was used to study the structure of EG and its interaction with SiC substrate. All the Raman bands of EG blue shift from that of bulk graphite and graphene made by micromechanical cleavage, which was attributed to the compressive strain induced by the substrate. A model containing 13 x…
We present energy filtered electron emission spectromicroscopy with spatial and wave-vector resolution on few layer epitaxial graphene on SiC$(000-1) grown by furnace annealing. Low energy electron microscopy shows that more than 80% of the sample is covered by 2-3 graphene layers. C1s spectromicroscopy provides an independent measurement of the graphene thickness distribution map. The work function, measured by photoelectron emission microscopy (PEEM), varies across the surface from 4.34 to 4.50eV according to both the graphene thickness and the graphene-SiC interface chemical state. At least…
We present a new fabrication method for epitaxial graphene on SiC which enables the growth of ultra-smooth defect- and bilayer-free graphene sheets with an unprecedented reproducibility, a necessary prerequisite for wafer-scale fabrication of high quality graphene-based electronic devices. The inherent but unfavorable formation of high SiC surface terrace steps during high temperature sublimation growth is suppressed by rapid formation of the graphene buffer layer which stabilizes the SiC surface. The enhanced nucleation is enforced by decomposition of polymer adsorbates which act as a carbon …
Up to two layers of epitaxial graphene have been grown on the Si-face of two-inch SiC wafers exhibiting room-temperature Hall mobilities up to 1800 cm^2/Vs, measured from ungated, large, 160 micron x 200 micron Hall bars, and up to 4000 cm^2/Vs, from top-gated, small, 1 micron x 1.5 micron Hall bars. The growth process involved a combination of a cleaning step of the SiC in a Si-containing gas, followed by an annealing step in Argon for epitaxial graphene formation. The structure and morphology of this graphene has been characterized using AFM, HRTEM, and Raman spectroscopy. Furthermore, top-g…
Strain engineering has attracted great attention, particularly for epitaxial films grown on a different substrate. Residual strains of SiC have been widely employed to form ultra-high frequency and high Q factor resonators. However, to date the highest residual strain of SiC was reported to be limited to approximately 0.6%. Large strains induced into SiC could lead to several interesting physical phenomena, as well as significant improvement of resonant frequencies. We report an unprecedented nano strain-amplifier structure with an ultra-high residual strain up to 8% utilizing the natural resi…
Thick, high-purity semi-insulating (SI)homoepitaxial layers on Si-face 4H-SiC weregrownsystematically, with resistivity \geq 109Ω-cmby maintaining high C/Si ratios 1.3-15 during growth.Comparison of secondary ion mass spectra betweenlow-dopedepilayers grown at C/Si ratio<1.3andSI-epilayers grown at C/Si ratio>1.3 showed little difference in residual impurity concentrations. A reconciliation of impurity concentration with measured resistivity indicated a compensating trap concentration of ~1015cm-3present only in the SI-epilayers. High- resolution photo induced transient spectroscopy (HRPITS) i…
We report the use of a surfactant molecule during the epitaxy of graphene on SiC(0001) that leads to the growth in an unconventional orientation, namely $R0^\circ$ rotation with respect to the SiC lattice. It yields a very high-quality single-layer graphene with a uniform orientation with respect to the substrate, on the wafer scale. We find an increased quality and homogeneity compared to the approach based on the use of a pre-oriented template to induce the unconventional orientation. Using spot profile analysis low energy electron diffraction, angle-resolved photoelectron spectroscopy, and …
We report a direct correlation between carrier mobility and Raman topography of epitaxial graphene (EG) grown on silicon carbide (SiC). We show the Hall mobility of material on the Si-face of SiC [SiC(0001)] is not only highly dependent on thickness uniformity but also on monolayer strain uniformity. Only when both thickness and strain are uniform over a significant fraction (> 40%) of the device active area does the mobility exceed 1000 cm2/V-s. Additionally, we achieve high mobility epitaxial graphene (18,100 cm2/V-s at room temperature) on the C-face of SiC [SiC(000-1)] and show that carrie…
The inability to grow large well ordered graphene with a specific number of layers on SiC(0001) is well known. The growth involves several competing processes (Si desorption, carbon diffusion, island nucleation etc.), and because of the high temperatures, it has not been possible to identify the growth mechanism. Using Scanning tunneling microscopy and an initially vicinal 6H-SiC(0001) sample, we determine the sequence of microscopic processes that result in the formation of bilayer graphene. Adjacent steps retract with different speeds and the carbon released produces characteristic "fingers"…
Thick, high quality 4H-SiC epilayers have been grown in a vertical hot-wall chemical vapor deposition system at a high growth rate on (0001) 80 off-axis substrates. We discuss the use of dichlorosilane as the Si-precursor for 4H-SiC epitaxial growth as it provides the most direct decomposition route into SiCl2, which is the predominant growth species in chlorinated chemistries. A specular surface morphology was attained by limiting the hydrogen etch rate until the system was equilibrated at the desired growth temperature. The RMS roughness of the grown films ranged from 0.5-2.0 nm with very fe…
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 wa…
We present epitaxial graphene (EG) growth on non-polar a-plane and m-plane 6H-SiC faces where material characterization is compared with that known for EG grown on polar faces. Atomic force microscopy (AFM) surface morphology exhibits nanocrystalline graphite like features for non-polar faces, while the polar silicon face shows step like features. This differing behavior is attributed to the lack of a hexagonal template on the non-polar faces. Non-polar faces also exhibit greater disorder and red shift of all Raman peaks (D, G and 2D) with increasing temperature. This is attributed to decreasi…
The unique electronic properties of graphene offer the possibility that it could replace silicon when microelectronics evolves to nanoelectronics. Graphene grown epitaxially on silicon carbide is particularly attractive in this regard because SiC is itself a useful semiconductor and, by suitable manipulation of the growth conditions, epitaxial films can be produced that exhibit all the transport properties of ideal, two-dimensional graphene desired for device applications. Nevertheless, there is little or no understanding of the actual kinetics of growth, which is likely to be required for fut…
We use ultra-high vacuum chemical vapor deposition to grow polycrystalline silicon carbide (SiC) on c-plane sapphire wafers which are then annealed between 1250 and 1450°C in vacuum to create epitaxial multilayer graphene (MLG). Despite the surface roughness and small domain size of the polycrystalline SiC, a conformal MLG film is formed. By planarizing the SiC prior to graphene growth, a reduction of the Raman defect band is observed in the final MLG. The graphene formed on polished SiC films also demonstrates significantly more ordered layer-by-layer growth and increased carrier mobility for…
Graphene, consisting of an inert, thermally stable material with an atomically flat, dangling bond-free surface is by essence an ideal template layer for van der Waals heteroepitaxy of two-dimensional materials such as silicene. However, depending on the synthesis method and growth parameters, graphene (Gr) substrates could exhibit, on a single sample, various surface structures, thicknesses, defects, and step heights. These structures noticeably affect the growth mode of epitaxial layers, e.g. turning the layer-by-layer growth into the Volmer-Weber growth promoted by defect-assisted nucleatio…
The crystallographic symmetries and spatial distribution of stacking domains in graphene films on SiC have been studied by low energy electron diffraction (LEED) and dark field imaging in a low energy electron microscope (LEEM). We find that the graphene diffraction spots from 2 and 3 atomic layers of graphene have 3-fold symmetry consistent with AB (Bernal) stacking of the layers. On the contrary, graphene diffraction spots from the buffer layer and monolayer graphene have apparent 6-fold symmetry, although the 3-fold nature of the satellite spots indicates a more complex periodicity in the g…
This paper describes the behavior of top gated transistors fabricated using carbon, particularly epitaxial graphene on SiC, as the active material. In the past decade research has identified carbon-based electronics as a possible alternative to silicon-based electronics. This enthusiasm was spurred by high carbon nanotube carrier mobilities. However, nanotube production, placement, and control are all serious issues. Graphene, a thin sheet of graphitic carbon, can overcome some of these problems and therefore is a promising new electronic material. Although graphene devices have been built bef…
Epitaxial graphene on SiC(0001) suffers from strong intrinsic n-type doping. We demonstrate that the excess negative charge can be fully compensated by non-covalently functionalizing graphene with the strong electron acceptor tetrafluorotetracyanoquinodimethane (F4-TCNQ). Charge neutrality can be reached in monolayer graphene as shown in electron dispersion spectra from angular resolved photoemission spectroscopy (ARPES). In bilayer graphene the band gap that originates from the SiC/graphene interface dipole increases with increasing F4-TCNQ deposition and, as a consequence of the molecular do…
We analyse doping of graphene grown on SiC in two models which differ by the source of charge transfered to graphene, namely, from SiC surface and from bulk donors. For each of the two models, we find the maximum electron density induced in monolayer and bilayer graphene, which is determined by the difference between the work function for electrons in pristine graphene and donor states on/in SiC, and analyse the responsivity of graphene to the density variation by means of electrostatic gates.
One-Step Epitaxial Access to Rhombohedral Graphene Flat-Band States on Step-Bunched SiC
Institute for Advanced Studies, Wuhan University（武汉大学高等研究院）；Department of Physics, Southern University of Science and Technology（南方科技大学物理系）；School of Physics and Technology, Wuhan University（武汉大学物理科学与技术学院）
In recent years, graphene growth optimization has been one of the key routes towards large-scale, high-quality graphene production. We have measured in-situ residual gas content during epitaxial graphene growth on silicon carbide (SiC) to find detrimental factors of epitaxial graphene growth. The growth conditions in high vacuum and purified argon are compared. The grown epitaxial graphene is studied by Raman scattering mapping and mechanical strain, charge density, number of graphene layers and graphene grain size are evaluated. Charge density and carrier mobility has been studied by Hall eff…
