Monolayer Epitaxial Graphene Research Articles

Epitaxial graphene thermistor for cryogenic temperatures

The thermal responsivity of monolayer epitaxial graphene grown on the Si-face surface of semi-insulating SiC substrate is investigated as a function of temperature below 300 K. The measurements showed that adsorption/desorption of atmospheric adsorbates can randomly modify the electrical characteristics of graphene which is indeed undesirable for consistent temperature sensing operations. Therefore, in order to avoid the interaction between graphene layer and adsorbates, the grown graphene layer is encapsulated with a thin SiO2 film deposited by Pulsed Electron Deposition technique. Temperature dependent resistance measurement of encapsulated graphene exhibited a clear thermistor type behavior with negative temperature coefficient resistance character. Both the sensitivity and transient thermal responsivity of the SiO2/graphene/SiC sample were found to be enhanced greatly especially for the temperatures lower than 225 K. The experimentally obtained results suggest that SiO2 encapsulated epitaxial graphene on SiC can be used readily as an energy efficient and stable temperature sensing element in cryogenic applications.

Calcium intercalation underneath N-layer graphene on 6H-SiC(0001)

Calcium intercalation underneath epitaxial graphene on 6H-SiC(0001) were investigated by scanning tunneling microcopy (STM) and density functional theory (DFT) calculations. After the preparation of calcium-adsorbed graphene on 6H-SiC(0001), annealing the sample to 900 °C activated the intercalation of the adsorbed calcium into buffer layer (BL), monolayer (1L) and bilayer epitaxial (2L) graphene. Subsequent DFT modeling show the dependence of the most stable intercalation sites for calcium underneath BL, 1L and 2L graphene on the intercalation density. Further DFT calculations indicate charge transfer from the intercalant into graphene layers, leading to the n-type doping of the calcium-intercalated BL, 1L and 2L graphene.

Growth of atomically thick transition metal sulfide filmson graphene/6H-SiC(0001) by molecular beam epitaxy

We report the growth and characterization of atomically thick NbS2, TaS2, and FeS films on a 6H-SiC(0001) substrate terminated with monolayer or bilayer epitaxial graphene. The crystal and electronic structures are studied by scanning tunneling microscopy and reflection high-energy electron diffraction. The NbS2 monolayer is solely in the 2H structure, while the TaS2 monolayer contains both 1T and 2H structures. Charge-density waves are observed in all phases. For the FeS films, the tetragonal structure coexists with the hexagonal one and no superconductivity is observed.

Examining epitaxial graphene surface conductivity and quantum Hall device stability with Parylene passivation

Homogeneous, single-crystal, monolayer epitaxial graphene (EG) is the one of most promising candidates for the advancement of quantized Hall resistance (QHR) standards. A remaining challenge for the electrical characterization of EG-based quantum Hall devices as a useful tool for metrology is that they are electrically unstable when exposed to air due to the adsorption of and interaction with atmospheric molecular dopants. The resulting changes in the charge carrier density become apparent by variations in the surface conductivity, the charge carrier mobility, and may result in a transition from n-type to p-type conductivity. This work evaluates the use of Parylene C and Parylene N as passivation layers for EG. Electronic transport of EG quantum Hall devices and non-contact microwave perturbation measurements of millimeter-sized areas of EG are both performed on bare and Parylene coated samples to test the efficacy of the passivation layers. The reported results, showing a significant improvement in passivation due to Parylene deposition, suggest a method for the mass production of millimeter-scale graphene devices with stable electrical properties.

Minimum Resistance Anisotropy of Epitaxial Graphene on SiC.

We report on electronic transport measurements in rotational square probe configuration in combination with scanning tunneling potentiometry of epitaxial graphene monolayers which were fabricated by polymer-assisted sublimation growth on SiC substrates. The absence of bilayer graphene on the ultralow step edges of below 0.75 nm scrutinized by atomic force microscopy and scanning tunneling microscopy result in a not yet observed resistance isotropy of graphene on 4H- and 6H-SiC(0001) substrates as low as 2%. We combine microscopic electronic properties with nanoscale transport experiments and thereby disentangle the underlying microscopic scattering mechanism to explain the remaining resistance anisotropy. Eventually, this can be entirely attributed to the resistance and the number of substrate steps which induce local scattering. Thereby, our data represent the ultimate limit for resistance isotropy of epitaxial graphene on SiC for the given miscut of the substrate.

A table-top formation of bilayer quasi-free-standing epitaxial-graphene on SiC(0001) by microwave annealing in air

We propose an ultrafast synthesis method to obtain quasi-free-standing bilayer epitaxial-graphene (QFSEG) on SiC(0001). By applying a microwave annealing (MWA) in air to a monolayer epitaxial graphene (EG) grown on SiC(0001), the EG's (6√3 × 6√3) R30° reconstructed buffer layer is decoupled from the SiC substrate and becomes the second graphene layer. Oxidation of the SiC surface is suggested as the most likely mechanism of the decoupling, and the electrical properties of this MWA-QFSEG are actually quite similar to those of the QFSEGs formed by conventional annealing in air. The process time has however been reduced by more than one order of magnitude, which will surely contribute to the betterment of the productivity of the EG-based devices.

High-frequency rectification in graphene lateral p-n junctions

We observe a dc electric current in response to terahertz radiation in lateral inter-digitated double-comb graphene p-n junctions. The junctions were fabricated by selective ultraviolet irradiation inducing p-type doping in intrinsic n-type epitaxial monolayer graphene. The photocurrent exhibits a strong polarization dependence and is explained by electric rectification in p-n junctions.

Polarized Raman Scattering of Epitaxial Graphene Prepared by Thermal Decomposition of SiC

Epitaxial graphene prepared by thermal decomposition of silicon carbide (SiC) can be applied to graphene-based electrical devices directly without transferring for the advantages of high electron mobility and easily compatible with the existing semiconductor technology. Characterizing the polarization dependence of epitaxial graphene favors the selection of device materials. However, the second-order polarized Raman spectra of 4H-SiC wafer were measured and found to exhibit polarization dependency, which would affect the polarization analysis of the G band of epitaxial graphene. In this paper, the polarization dependence of non-exfoliated monolayer and bilayer epitaxial graphene grown on 4H-SiC substrates were obtained after subtracting the second-order polarized Raman spectra of SiC wafer under the identical test conditions. Results indicated that the G band of epitaxial graphene shows non-polarization, while the 2D band shows strong polarization dependency.

Measuring the dielectric and optical response of millimeter-scale amorphous and hexagonal boron nitride films grown on epitaxial graphene

Monolayer epitaxial graphene (EG), grown on the Si face of SiC, is an advantageous material for a variety of electronic and optical applications. EG forms as a single crystal over millimeter-scale areas and consequently, the large scale single crystal can be utilized as a template for growth of other materials. In this work, we present the use of EG as a template to form millimeter-scale amorphous and hexagonal boron nitride (a-BN and h-BN) films. The a-BN is formed with pulsed laser deposition and the h-BN is grown with triethylboron (TEB) and NH3 precursors, making it the first metal organic chemical vapor deposition (MOCVD) process of this growth type performed on epitaxial graphene. A variety of optical and non-optical characterization methods are used to determine the optical absorption and dielectric functions of the EG, a-BN, and h-BN within the energy range of 1 eV–8.5 eV. Furthermore, we report the first ellipsometric observation of high-energy resonant excitons in EG from the 4H polytype of SiC and an analysis on the interactions within the EG and h-BN heterostructure.

Probing the dielectric response of the interfacial buffer layer in epitaxial graphene via optical spectroscopy.

Monolayer epitaxial graphene (EG) is a suitable candidate for a variety of electronic applications. One advantage of EG growth on the Si face of SiC is that it develops as a single crystal, as does the layer below, referred to as the interfacial buffer layer (IBL), whose properties include an electronic band gap. Though much research has been conducted to learn about the electrical properties of the IBL, not nearly as much work has been reported on the optical properties of the IBL. In this work, we combine measurements from Mueller matrix ellipsometry, differential reflectance contrast, atomic force microscopy, and Raman spectroscopy, as well as calculations from Kramers-Kronig analyses and density functional theory (DFT), to determine the dielectric function of the IBL within the energy range of 1 eV to 8.5 eV.

Li-intercalated graphene on SiC(0001): An STM study

We present a systematical study via scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED) on the effect of the exposure of Lithium (Li) on graphene on silicon carbide (SiC). We have investigated Li deposition both on epitaxial monolayer graphene and on buffer layer surfaces on the Si-face of SiC. At room temperature, Li immediately intercalates at the interface between the SiC substrate and the buffer layer and transforms the buffer layer into a quasi-free-standing graphene. This conclusion is substantiated by LEED and STM evidence. We show that intercalation occurs through the SiC step sites or graphene defects. We obtain a good quantitative agreement between the number of Li atoms deposited and the number of available Si bonds at the surface of the SiC crystal. Through STM analysis, we are able to determine the interlayer distance induced by Li-intercalation at the interface between the SiC substrate and the buffer layer.

Effects of rhenium on graphene grown on SiC(0001)

We study the effects of Rhenium (Re) deposited on epitaxial monolayer graphene grown on SiC(0001) and after subsequent annealing at different temperatures, by performing high resolution photoelectron spectroscopy (PES) and angle resolved photoelectron spectroscopy (ARPES). The graphene-Re system is found to be thermally stable. While no intercalation or chemical reaction of the Re is detected after deposition and subsequent annealing up to 1200°C, a gradual decrease in the binding energy of the Re 4f doublet is observed. We propose that a larger mobility of the Re atoms with increasing annealing temperature and hopping of Re atoms between different defective sites on the graphene sample could induce this decrease of Re 4f binding energy. This is corroborated by first principles density functional theory (DFT) calculations of the Re core-level binding energy shift. No change in the doping or splitting of the initial monolayer graphene electronic band structure is observed after Re deposition and annealing up to 1200°C, only a broadening of the bands.

Crossover from Efros–Shklovskii to Mott variable range hopping in monolayer epitaxial graphene grown on SiC

We report variable range hopping (VRH) transport in monolayer epitaxial graphene grown on SiC. A crossover from Efros–Shklovskii (E-S) VRH to Mott VRH can be observed by increasing the magnetic field applied perpendicular to the plane of graphene or by a low-temperature vacuum annealing process. Our new experimental results suggest that monolayer graphene on SiC is an interesting platform for probing VRH and crossover between different VRH regimes in a strongly disordered system.

Electrical Stabilization of Surface Resistivity in Epitaxial Graphene Systems by Amorphous Boron Nitride Encapsulation.

Homogeneous monolayer epitaxial graphene (EG) is an ideal candidate for the development of millimeter-sized devices with single-crystal domains. A clean fabrication process was used to produce EG-based devices, with n-type doping level of the order of 1012 cm–2. Generally, electrical properties of EG, such as longitudinal resistivity, remain unstable when devices are exposed to air due to adsorption of molecular dopants, whose presence shifts the carrier density close to the Dirac point (<1010 cm–2) or into the p-type regime. Here, we report experimental results on the use of amorphous boron nitride (a-BN) as an encapsulation layer, whereby EG can maintain its longitudinal resistivity and have its carrier density modulated. Furthermore, we exposed 12 devices to controlled temperatures of up to 85 °C and relative humidity of up to 85% and reported that an approximately 20 nm a-BN encapsulation thickness is sufficient to preserve their longitudinal resistivity to within 10% of the previously measured value. We monitored the electronic properties of our encapsulated and nonencapsulated EG samples by magnetotransport measurements, using a neodymium iron boron magnet. Our results have essential importance in the mass production of millimeter-scale graphene devices, with stable electrical properties.

Preservation of Surface Conductivity and Dielectric Loss Tangent in Large-Scale, Encapsulated Epitaxial Graphene Measured by Noncontact Microwave Cavity Perturbations.

Regarding the improvement of current quantized Hall resistance (QHR) standards, one promising avenue is the growth of homogeneous monolayer epitaxial graphene (EG). A clean and simple process is used to produce large, precise areas of EG. Properties like the surface conductivity and dielectric loss tangent remain unstable when EG is exposed to air due to doping from molecular adsorption. Experimental results are reported on the extraction of the surface conductivity and dielectric loss tangent from data taken with a noncontact resonance microwave cavity, assembled with an air-filled, standard R100 rectangular waveguide configuration. By using amorphous boron nitride (a-BN) as an encapsulation layer, stability of EG's electrical properties under ambient laboratory conditions is greatly improved. Moreover, samples are exposed to a variety of environmental and chemical conditions. Both thicknesses of a-BN encapsulation are sufficient to preserve surface conductivity and dielectric loss tangent to within 10% of its previously measured value, a result which has essential importance in the mass production of millimeter-scale graphene devices demonstrating electrical stability.

Epitaxial growth of a graphene single crystal on the Ni(111) surface

The thermally controlled synthesis of graphene from propylene molecules on the Ni(111) surface in ultrahigh vacuum is studied by scanning tunneling microscopy and density functional theory. It is established that the adsorption of propylene on Ni(111) atomic terraces at room temperature results in the dehydration of propylene molecules with the formation of single-atomic carbon chains and in the complete dissociation of propylene at the edges of atomic steps with the subsequent diffusion of carbon atoms below the surface. The annealing of such a sample at 500°С leads to the formation of multilayer graphene islands both from surface atomic chains and by the segregation of carbon atoms collected in the upper nickel atomic layers. The process of formation of an epitaxial graphene monolayer until the complete filling of the nickel surface is controllably observed. Atomic defects seen on the graphene surface are interpreted as individual nickel atoms incorporated into graphene mono- or bivacancies.

Adsorption of CO2on Graphene: A Combined TPD, XPS, and vdW-DF Study

The adsorption of CO2 molecules on monolayer epitaxial graphene on a SiC(0001) surface at 30 K was investigated by temperature-programmed desorption and X-ray photoelectron spectroscopy. The desorption energy of CO2 on graphene was determined to be (30.1–25.1) ± 1.5 kJ/mol at low coverages and approached the sublimation energy of dry ice (27–25 kJ/mol) with increasing the coverage. The adsorption of CO2 on graphene was thus categorized into physisorption, which was further supported by the binding energies of CO2 in core-level spectra. The adsorption states of CO2 on graphene were theoretically examined by means of the van der Waals density functional (vdW-DF) method that includes nonlocal correlation. The experimental desorption energy was successfully reproduced with high accuracy using vdW-DF calculations; the optB86b-vdW functional was found to be most appropriate to reproduce the desorption energy in the present system.

Temperature dependence of electron density and electron–electron interactions in monolayer epitaxial graphene grown on SiC

We report carrier density measurements and electron–electron (e–e) interactions in monolayer epitaxial graphene grown on SiC. The temperature (T)-independent carrier density determined from the Shubnikov–de Haas (SdH) oscillations clearly demonstrates that the observed logarithmic temperature dependence of the Hall slope in our system must be due to e–e interactions. Since the electron density determined from conventional SdH measurements does not depend on e–e interactions based on Kohn’s theorem, SdH experiments appear to be more reliable compared with the classical Hall effect when one studies the T dependence of the carrier density in the low T regime. On the other hand, the logarithmic T dependence of the Hall slope δRxy/δB can be used to probe e–e interactions even when the conventional conductivity method is not applicable due to strong electron–phonon scattering.

The investigation of cobalt intercalation underneath epitaxial graphene on 6H-SiC(0 0 0 1)

The intercalation behaviour of cobalt underneath both epitaxial graphene monolayer and bilayer on 6H-SiC(0001) have been investigated by scanning tunneling microscopy (STM) and density functional theory (DFT). Upon deposition, cobalt atoms prefer to agglomerate into clusters on the epitaxial graphene. After annealing the sample to 850 °C, the intercalation of the adsorbed cobalt atoms into both monolayer and bilayer epitaxial graphene on SiC takes place, as observed by the atomically resolved STM images. Further studies based on DFT modeling and simulated STM images show that, resulting from the interplay between the intercalated cobalt atoms and the carbon layers sandwiching it, the most energetically favourable intercalation sites of cobalt atoms underneath monolayer and bilayer graphene differ. Furthermore, the results show energy barriers of 0.60 eV and 0.41 eV for cobalt penetration through mono-vacancy defects at monolayer and bilayer graphene.

The effect of the SiC(0001) surface morphology on the growth of epitaxial mono-layer graphene nanoribbons

Graphene nanoribbons (GNRs) are promising for applications in nanoelectronics due to their unique properties. Therefore, achieving the controlled and high-quality synthesis of GNRs is anticipated to be of great importance. One of the methods which shows great potential is the growth of GNRs on surface facets of SiC(0001) by the surface graphitization method. In this report we studied the dependency of the GNR width on growth temperature and SiC substrate miscut angle (or initial step height). While a linear growth rate best describes the growth in lower step heights, a nonlinear rate is observed for substrates with higher steps, which is also associated with the formation of few-layer graphene on the step edges. The structural characterization of the samples was performed by means of atomic force microscopy, scanning electron microscopy, and Raman spectroscopy.