Epitaxial Graphene Surface Research Articles

Nanoscale mapping of relativistic photocarrier transports in epitaxial graphene surface and edge states

We report the direct mapping of photo-transport properties of relativistic carriers generated on terrace-surface and terrace-edge structures of epitaxial graphene grown on silicon carbide. In this method, a conductive probe made a direct contact with epitaxial graphene and scanned the surface, allowing us to map the topography, current, and noise of graphene with nanoscale resolutions via a scanning noise microscopy. The maps were further analyzed by a two-dimensional network model to obtain the sheet-conductance (S□) and noise-source density (neff) distributions of epitaxial graphene. The topography image showed the formation of terraces, which could be attributed to the different decomposition rate of silicon atoms during the graphene growth. The terraces of graphene exhibited uniform S□, being separated by one-dimensional terrace-edges. Interestingly, terrace-edges exhibited a rather large neff with a power-law relationship of S□ ∝ neff−0.5, indicating a typical hopping conduction. However, in terrace-surfaces, sheet-conductance was nearly independent on neff, which was attributed to the relativistic nature of charge carriers unaffected by charge-trapping potential. Notably, under illumination, we observed the relativistic behavior of photocarriers in overall graphene terraces, presumably because photocarriers were generated through charge-transfer complexes formation at epitaxial graphene/substrate interface without the participation of noise-sources. Interestingly, we observed nearly homogeneous photoconductance and neff, which could be possibly due to the merger of one-dimensional edge-states into two-dimensional surface-states. The mapping of photoconductance and photo-traps provides valuable insights into the generation of relativistic photocarriers in epitaxial graphene.

Electron transfer characteristics of amino acid adsorption on epitaxial graphene FETs on SiC substrates

Clarifying the adsorption characteristics of biomolecules on graphene surfaces is critical for the development of field-effect transistor (FET)-based biosensors for detecting pH, DNA, proteins, and other biomarkers. Although there are many reports on biomolecule detection using graphene FETs, the detection mechanism has not yet been clarified. In this study, the adsorption behavior and electron transfer characteristics of 20 proteinogenic amino acids on graphene field-effect transistors are investigated. Large single-crystal graphene films were epitaxially grown on SiC substrates by a resist-free metal stencil mask lithography process then patterned by air plasma etching to form FET devices. Amino acids with different charge conditions (positive or negative charge) were introduced onto the epitaxial graphene surface in solution. The charge neutral points of the drain current vs gate voltage curves shifted in the negative gate voltage direction after the introduction of all amino acids, regardless of the type of amino acid and its charge condition. These amino acid adsorption characteristics agree well with previously reported protein adsorption characteristics on epitaxial graphene surfaces, indicating that the adsorption of proteins in the liquid phase occurs by electron doping to the graphene surface. These results indicate that non-specific protein binding always leads to electron doping of epitaxial graphene FETs.

The effect of Cl- and N-doped MoS2 and WS2 coated on epitaxial graphene in gas-sensing applications

In this study, epitaxial graphene (EG) was grown on a 6H-SiC (0001) substrate via the thermal decomposition of SiC. Undoped and Cl- or N-doped molybdenum disulfide (MoS2) and tungsten disulfide (WS2) ultrathin films were spin-coated on the graphene surface. The scanning electron microscopy (SEM) images and topological atomic force microscopy (AFM) analysis showed good distribution of thin MoS2 and WS2 flakes on the EG surface. The X-ray photoelectron spectroscopy (XPS) confirmed the presence of Mo-related peaks of 3d5/2 and 3d3/2 at ~ 232.2 eV and 235.1 eV, respectively. It also represented peaks of W 4f7/2 and 5p5/2 at around 36.1 eV and 37.9 eV, respectively. Moreover, XPS results showed peaks at around 167.4 eV and 168.4 eV corresponding to S 2p for MoS2 and WS2, respectively. The XPS results also confirmed the presence of dopant elements in MoS2 and WS2 flakes. We fabricated sensors using undoped and chlorine- or nitrogen-doped MoS2 and WS2 ultrathin films for gas-sensing applications. These sensors were surveyed for ammonia (NH3) and nitrogen dioxide (NO2) gas sensing. As in NO2, both undoped sensors react with a decrease in relative sensor responses to NH3, hence showing n-type behavior. Doping MoS2 and WS2 with chlorine led to a higher response vis-à-vis the nitrogen-doped sensors. The absolute relative response of Cl-doped WS2 and MoS2 was about 3.5 and 1.8 times more than that of their undoped counterparts toward NH3. A change of direction with a slightly smaller response (approximately × 0.8), however, could also be observed in the doping of MoS2 and WS2 with nitrogen. When exposed to NO2, the Cl-doped WS2 sensor response was 1.2 more than the N-doped one, while for MoS2 these values changed in the range of 1.2 – 1.6 for different flows of gas.

Synthesis and Local Probe Gating of a Monolayer Metal‐Organic Framework

AbstractAchieving large‐area uniform 2D metal‐organic frameworks (MOFs) and controlling their electronic properties on inert surfaces is a big step toward future applications in electronic devices. Here a 2D monolayer Cu‐dicyanoanthracene MOF with long‐range order is successfully fabricated on an epitaxial graphene surface. Its structural and electronic properties are studied by low‐temperature scanning tunneling microscopy and spectroscopy complemented by density‐functional theory calculations. Access to multiple molecular charge states in the 2D MOF is demonstrated using tip‐induced local electric fields. It is expected that a similar strategy could be applied to fabricate and characterize 2D MOFs with exotic, engineered electronic states.

Liquid metal intercalation of epitaxial graphene: Large-area gallenene layer fabrication through gallium self-propagation at ambient conditions

We demonstrate the fabrication of an ultra thin gallium film, also known as gallenene, beneath epitaxial graphene on 6H-SiC under ambient conditions triggered by liquid gallium intercalation. Gallenene has been fabricated using the liquid metal intercalation, achieving lateral intercalation and diffusion of Ga atoms at room temperature on square centimeter areas limited only by the graphene samples' size. The stepwise self-propagation of the gallenene film below the epitaxial graphene surface on the macroscopic scale was observed by optical microscopy shortly after the initial processing without further physical or chemical treatment. Directional Ga diffusion of gallenene occurs on SiC terraces since the terrace steps form an energetic barrier (Ehrlich-Schwoebel barrier),retarding the gallenene propagation. The subsequent conversion of the epitaxial graphene into quasi free-standing bilayer graphene (QFBLG) and the graphene-gallenene heterostack interactions have been analyzed by XPS and Raman measurements. The results reveal a novel approach for controlled fabrication of wafer-scale gallenene as well as for two-dimensional heterostructures and stacks based on the interaction between liquid metal and epitaxial graphene. Please note, this work was also titled as Graphene meets gallenene -- A straightforward approach to developing large-area heterostacks by gallium self-propagation https://www.researchgate.net/publication/333451130_Graphene_meets_gallenene_-_A_straightforward_approach_to_developing_large-area_heterostacks_by_gallium_self-propagation

RF-MBE growth and orientation control of GaN on epitaxial graphene

GaN is proven as the most important modern semiconductor with many potential applications. Although GaN growth is matured enough, unfortunately, it is still very difficult to obtain this material with the same quality as the Si crystal, either in heteroepitaxy or homoepitaxy. GaN has recently been proposed to grow on two-dimensional (2D) layered material. This paper reports the van der Waals epitaxy (vdWE) and orientation control of GaN on epitaxial graphene (EG) by means of RF-MBE. A single crystalline GaN with a smooth surface on the EG is successfully obtained. It is found that the incorporation of an AlN intermediate layer on the EG surface significantly improves the GaN on EG. The AlN/EG structure can control the a-axis orientation of the nitride growth layer and improve the epitaxial layer quality. The GaN layers fabricated on the AlN/EG structure are also found to be free from interfacial stress. The quality of the GaN layer obtained on the AlN/EG structure is comparable to that of the GaN layer on the sapphire substrate. This research paves the way for the expansion of high-quality GaN on EG.

Atomic Layer Deposition of High-k Insulators on Epitaxial Graphene: A Review

Due to its excellent physical properties and availability directly on a semiconductor substrate, epitaxial graphene (EG) grown on the (0001) face of hexagonal silicon carbide is a material of choice for advanced applications in electronics, metrology and sensing. The deposition of ultrathin high-k insulators on its surface is a key requirement for the fabrication of EG-based devices, and, in this context, atomic layer deposition (ALD) is the most suitable candidate to achieve uniform coating with nanometric thickness control. This paper presents an overview of the research on ALD of high-k insulators on EG, with a special emphasis on the role played by the peculiar electrical/structural properties of the EG/SiC (0001) interface in the nucleation step of the ALD process. The direct deposition of Al2O3 thin films on the pristine EG surface will be first discussed, demonstrating the critical role of monolayer EG uniformity to achieve a homogeneous Al2O3 coverage. Furthermore, the ALD of several high-k materials on EG coated with different seeding layers (oxidized metal films, directly deposited metal-oxides and self-assembled organic monolayers) or subjected to various prefunctionalization treatments (e.g., ozone or fluorine treatments) will be presented. The impact of the pretreatments and of thermal ALD growth on the defectivity and electrical properties (doping and carrier mobility) of the underlying EG will be discussed.

Growth Mechanism of InN Nucleation Layers on Epitaxial Graphene Using Metal Organic Vapor Phase Epitaxy and Radio-Frequency Molecular Beam Epitaxy

This paper presents a growth mechanism and a comparative study of the InN nucleation layers grown on epitaxial graphene (EG) by metal organic vapor phase epitaxy (MOVPE) and radio-frequency molecular beam epitaxy (RF-MBE). Before growing InN nucleation layers, the EG surface was formed on 4° off 6H-SiC substrates (both Si- and C-faces) by thermal annealing in Ar ambient. The MOVPE grown InN nucleation layers show three-dimensional (3D) growth from the very beginning due to lack of nucleation centers and for the long migration length on the EG surface. The MOVPE InN on the EG formed on Si-face SiC is nucleated with the step edge, while it is nucleated randomly over the entire EG surface on C-face SiC. In contrast, the RF-MBE InN nucleation layers grown on EG formed on Si-face SiC show a two-dimensional growth mode up to 3 ML, and then a further increase of nucleation layer changes the growth mode to 3D mode. The formation of adsorption sites on the graphene surface by introduction of defects plays a signif...

Manipulation of epitaxial graphene towards novel properties and applications

Abstract The integration of epitaxial graphene on 4H-SiC with different metals may allow tunability of electronic and optical properties of graphene, enabling novel high-performance devices. Here we present a Raman spectroscopy study on epitaxial graphene decorated with electrodeposited Pb and Li adatoms and with magnetron sputtered 5 nm-thick Ag nano-island films. We find that the presence of metals on the epitaxial graphene surface generates defects and induces n-type doping, which is evidenced by the observation of the defect related Raman modes (namely D, D′ and D + G) and systematic red-shift of the main characteristic modes of graphene. In-depth statistical analysis of the Raman data before and after metal deposition complemented by density functional theory (DFT) calculations allowed to link the interaction strength between the three selected metals and graphene with the metal-induced changes in the vibrational/electronic properties of graphene. Large-area uniform electron doping of epitaxial graphene and surface-enhanced Raman scattering (SERS) effect are reached by room temperature deposition of Ag nano-island films. Very promising results have been obtained from graphene subjected to electrochemical intercalation by Li, which can serve as prerequisites of the construction of Li batteries. The strong interaction between Li or Pb with graphene implies the possibility to exploit the epitaxial graphene as an efficient material for energy storage or for heavy metal sensing, while predominant van der Waals interaction between Ag and graphene favors the formation of extremely thin silver coatings towards two-dimensional metal systems. The present results give better understanding of the nature of epitaxial graphene response to metal deposition and can be useful to design high-performance energy storage devices, optical sensors and heavy metal detection systems.

Fabrication of InN on epitaxial graphene using RF-MBE

This paper reports the fabrication of InN layers on the epitaxial graphene (EG) using radio-frequency plasma-assisted molecular beam epitaxy (RF-MBE). Prior to the fabrication of InN, single crystalline EG with step and terrace structure was formed on 6H-SiC (0001) substrate in an Ar ambient by the Si sublimation method. Single crystalline epitaxial layers of InN with smooth surfaces are successfully fabricated on the EG using RF-MBE. InN layers with terrace and step structure are grown on the graphene surface up to 2MLs, and InN are grown in a layer by layer 2D growth mode. If the number of layers is increased above 3 MLs, the terrace and steps disappear, and the growth mode changes to 3D mode. The Raman spectroscopy analysis shows that the interfacial stress is reduced for the InN layer grown on the EG surface. The quality of the grown InN layer on the EG surface achieved at present is comparable to the InN film grown on sapphire. This work opens the possibility of growing high-quality InN layers on the EG surface in the near future.

Direct Formation of Solution-based Al2O3 on Epitaxial Graphene Surface for Sensor Applications

Direct Formation of Solution-based Al2O3 on Epitaxial Graphene Surface for Sensor Applications

Effect of epitaxial graphene morphology on adsorption of ambient species

This work illustrates the impact of atmospheric gases on the surface of epitaxial graphene. The different rate of adsorption on different parts of graphene samples provides a concrete evidence that the surface morphology of graphene plays a significant role in this process. The uneven adsorption occurs only on the surface of the monolayer graphene and not on bilayer graphene. The second monolayer is distinguished and verified by the phase contrast mode of atomic force microscopy and the low energy electron microscopy, respectively. Raman spectroscopy is used to study the strain on the surface of graphene; results indicate that monolayer and bilayer graphene exhibit different types of strain. The bilayer is under more compressive strain in comparison with monolayer graphene that hinders the process of adsorption. However, the wrinkles and edges of steps of the bilayer are under tensile strain, hence, facilitate adsorption. Samples were subjected to X-ray photoelectron spectroscopy which confirms that the adsorbates on the epitaxial graphene are carbon clusters with nitrogen and oxygen contamination. For reversing the adsorption process the samples are annealed and a method for the removal of these adsorbates is proposed.

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.

Enhancement of CO2 adsorption on oxygen-functionalized epitaxial graphene surface under near-ambient conditions.

The functionalization of graphene is important in practical applications of graphene, such as in catalysts. However, the experimental study of the interactions of adsorbed molecules with functionalized graphene is difficult under ambient conditions at which catalysts are operated. Here, the adsorption of CO2 on an oxygen-functionalized epitaxial graphene surface was studied under near-ambient conditions using ambient-pressure X-ray photoelectron spectroscopy (AP-XPS). The oxygen-functionalization of graphene is achieved in situ by the photo-induced dissociation of CO2 with X-rays on graphene in a CO2 gas atmosphere. The oxygen species on the graphene surface is identified as the epoxy group by XPS binding energies and thermal stability. Under near-ambient conditions of 1.6 mbar CO2 gas pressure and 175 K sample temperature, CO2 molecules are not adsorbed on the pristine graphene, but are adsorbed on the oxygen-functionalized graphene surface. The increase in the adsorption energy of CO2 on the oxygen-functionalized graphene surface is supported by first-principles calculations with the van der Waals density functional (vdW-DF) method. The adsorption of CO2 on the oxygen-functionalized graphene surface is enhanced by both the electrostatic interactions between the CO2 and the epoxy group and the vdW interactions between the CO2 and graphene. The detailed understanding of the interaction between CO2 and the oxygen-functionalized graphene surface obtained in this study may assist in developing guidelines for designing novel graphene-based catalysts.

(Invited) Electronic and Chemical Structure of 2D Materials

The drive to produce smaller, faster, lower power electronic components for computing is pushing the semiconductor industry to nanometer-scale device structures. Atomically thin two-dimensional (2D) materials such as transitional metal dichalcogenides (TMDs) and graphene are a promising class of materials for nanoelectronics with unique optical and electronic properties. The properties of mono- to few-layer TMDs are highly sensitive and reactive to their local environment (ambient conditions and adsorbates) and the interfaces within a fabricated device structure (gate dielectric, contacts), which can all impact their electronic properties and extrinsic device characteristics. Here, we will present the electronic and chemical structure of doped graphene on silicon carbide and polymorphs of molybdenum telluride. Large area epitaxial graphene (EG) grown on silicon carbide (SiC) provides a feasible route to scalable production of graphene-containing electronic components. EG on SiC display strong n-type (electron) doping due to the interaction of the zero-layer graphene [1] that is directly bonded to SiC. Nitric acid has been shown to be an effective p-doping agent and produce low carrier density of EG [2]. Using laboratory-based ultraviolet (UPS) and x-ray photoelectron (XPS) spectroscopies, we investigate the surface chemical composition and electronic structure of nitric acid exposed EG on SiC. We observe the presence of nitrogen on the surface which provides direct evidence on the role of nitric acid as extrinsic dopant of EG on SiC. The UPS results indicate that the EG surface is that of a semi-metal after exposure to nitric acid. Technological commercialization of graphene for electronic components requires that their electronic properties be engineered for specific device functionality such as the charge carrier density. With the vast elemental phase space of TMDs, TMDs have a range of electronic properties giving rise to metallic, semiconducting, or insulating properties. In addition, some TMDs exhibit polymorphism and different packing geometry or phase can distinctly impact the electronic structure and it will influence optical and transport properties. Molybdenum telluride (MoTe2) can exist in three phases: 2H, 1T, and 1T’. The 2H phase is semiconducting, while the other phases are metallic or semi-metallic. For the bulk 2H MoTe2 crystal, the surface is relatively stable and with little oxidation based on our XPS and UPS results. This is not the case for the 1T’ phase of crystalline MoTe2, where the molybdenum and tellurium atoms at the surface are significantly oxidized. The 1T’ phase can be cleaved at the surface, and we can observe the semi-metallic properties by angle-resolved photoemission. The cleaved 2H MoTe2 surface exhibits dispersion of the valence bands and a valence band maximum consistent with being an n-type semiconductor. MoTe2 is appealing for manufacturing of nanoelectronic components due to tunability in electronic properties in one material system. Continued innovation requires novel nanoelectronic materials and devices, coupled with a thorough understanding of the electronic structure which determines device functionality. [1] P. Mallet, F. Varchon, C. Naud, L. Magaud, C. Berger, and J.-Y. Veuillen, Phys. Rev. B 76, 041403 (2007). [2] Y. Yan, L.-I. Huang, Y. Fukuyama, F.-H. Liu, M. A. Real, P. Barbara, C. -T. Liang, D. B. Newell, and R. E. Elmquist, Small 11, 90 – 95 (2015).

Si growth at graphene surfaces on 6H-SiC(0001) substrates

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.

Wafer-scale homogeneity of transport properties in epitaxial graphene on SiC

Magnetotransport measurements on Hall bar devices fabricated on purely monolayer epitaxial graphene on silicon carbide (SiC/G) show a very tight spread in carrier concentration and mobility across wafer-size dimensions. In contrast, SiC/G devices containing bilayer graphene domains display variations in their electronic properties linked to the amount of bilayer content. The spread in properties among devices patterned on the same SiC/G wafer can thus be understood by considering the inhomogeneous number of layers often grown on the surface of epitaxial graphene on SiC.

Controlling the spatial arrangement of organic magnetic anions adsorbed on epitaxial graphene on Ru(0001).

Achieving control over the self-organization of functional molecules on graphene is critical for the development of graphene technology in organic electronic and spintronic. Here, by using a scanning tunneling microscope (STM), we show that the electron acceptor molecule 7,7',8,8'-tetracyano-p-quinodimethane (TCNQ) and its fluorinated derivative 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyano-p-quinodimethane (F4-TCNQ), co-deposited on the surface of epitaxial graphene on Ru(0001), transform spontaneously into their corresponding magnetic anions and self-organize in two remarkably different structures. TCNQ forms densely packed linear magnetic arrays, while F4-TCNQ molecules remain as isolated non interacting magnets. With the help of density functional theory (DFT) calculations, we trace back the origin of this behavior in the competition between the intermolecular repulsion experienced by the individual charged anions, which tends to separate the molecules, and the delocalization of the electrons transferred from the surface to the molecules, which promotes the formation of molecular oligomers. Our results demonstrate that it is possible to control the spatial arrangement of organic magnetic anions co-adsorbed on a surface by means of chemical substitution, paving the way for the design of two-dimensional fully organic magnetic structures on graphene and on other surfaces.

Bilayer Graphene Grown on 4H-SiC (0001) Step-Free Mesas

We demonstrate the first successful growth of large-area (200 × 200 μm(2)) bilayer, Bernal stacked, epitaxial graphene (EG) on atomically flat, 4H-SiC (0001) step-free mesas (SFMs) . The use of SFMs for the growth of graphene resulted in the complete elimination of surface step-bunching typically found after EG growth on conventional nominally on-axis SiC (0001) substrates. As a result heights of EG surface features are reduced by at least a factor of 50 from the heights found on conventional substrates. Evaluation of the EG across the SFM using the Raman 2D mode indicates Bernal stacking with low and uniform compressive lattice strain of only 0.05%. The uniformity of this strain is significantly improved, which is about 13-fold decrease of strain found for EG grown on conventional nominally on-axis substrates. The magnitude of the strain approaches values for stress-free exfoliated graphene flakes. Hall transport measurements on large area bilayer samples taken as a function of temperature from 4.3 to 300 K revealed an n-type carrier mobility that increased from 1170 to 1730 cm(2) V(-1) s(-1), and a corresponding sheet carrier density that decreased from 5.0 × 10(12) cm(-2) to 3.26 × 10(12) cm(-2). The transport is believed to occur predominantly through the top EG layer with the bottom layer screening the top layer from the substrate. These results demonstrate that EG synthesized on large area, perfectly flat on-axis mesa surfaces can be used to produce Bernal-stacked bilayer EG having excellent uniformity and reduced strain and provides the perfect opportunity for significant advancement of epitaxial graphene electronics technology.

Optimizing Label-Free DNA Electrical Detection on Graphene Platform

The anodized epitaxial graphene (EG) electrode demonstrates a high level of performance for electrochemical impedance as well as differential pulse voltammetry detection of immobilized DNA and free DNA, respectively, at solid-liquid interfaces. On the anodized EG surface, because of the presence of oxygen functionalities as well as π conjugated domains, the anchoring of the DNA probe can be achieved by either covalent grafting or noncovalent π-π stacking readily. The effect of different binding modes on the sensitivity of the impedimetric sensing was investigated. Equivalent circuit modeling shows that the sensitivity of EG to DNA hybridization is controlled by changes in the resistance of the molecular layer as well as the space charge layer. The linear dynamic detection range of EG for DNA oligonucleotides is in the range of 5.0 × 10(-14) to 1 × 10(-6) M. In addition, with the use of differential pulse voltammetry, single stranded DNA, fully complimentary DNA, as well as single nucleotide polymorphisms can be differentiated on anodized EG by monitoring the oxidation signals of individual nucleotide bases.