We demonstrate a method by which few-layer graphene samples can be etched along crystallographic axes by thermally activated metallic nanoparticles. The technique results in long (>1 micron) crystallographic edges etched through to the insulating substrate, making the process potentially useful for atomically precise graphene device fabrication. This advance could enable atomically precise construction of integrated circuits from single graphene sheets with a wide range of technological applications.
Graphene is one of the most promising 2D materials for various applications due to its unique electronic properties and high thermal stability. In previous studies, it was shown that when graphene is deposited onto some transition metal substrates, small molecules, such as O$_2$, intercalate between the graphene and the substrate and react to partially etch the graphene film when heated to desorb the intercalates. Here, carbon vacancy defects are intentionally formed on Gr/Ru(0001) and their effect on the intercalation of oxygen and etching of the graphene layer are investigated. 50 eV Ar$^+$ …
In most envisioned applications, full utilization of a graphene-carbon nanotube (CNT) construct requires maintaining the integrity of the graphene layer during the CNT growth step. In this work, we exhibit an approach towards controlled CNT growth atop graphene substrates where the reaction equilibrium between source hydrocarbon decomposition and carbon saturation into and precipitation from the catalyst nanoparticles shifts towards CNT growth rather than graphene consumption. By utilizing C2H4 feedstock, we demonstrate that the low temperature growth permissible with this gas suppresses undes…
Patterned graphene shows substantial potential for applications in future molecular-scale integrated electronics. Environmental effects are a critical issue in a single layer material where every atom is on the surface. Especially intriguing is the variety of rich chemical interactions shown by molecular oxygen with aromatic molecules. We find that O2 etching kinetics vary strongly with the number of graphene layers in the sample. Three-layer-thick samples show etching similar to bulk natural graphite. Single-layer graphene reacts faster and shows random etch pits in contrast to natural graphi…
Single-layer graphene structures and devices are commonly defined using reactive ion etching and plasma etching with O2 or Ar as the gaseous etchants. Although optical microscopy and Raman spectroscopy are widely used to determine the appropriate duration of dry etching, additional characterization with atomic force microscopy (AFM) reveals that residual graphene and/or etching byproducts persist beyond the point where the aforementioned methods suggest complete graphene etching. Recognizing that incomplete etching may have deleterious effects on devices and/or downstream processing, AFM chara…
Low-energy electron microscopy (LEEM) reveals a new mode of graphene growth on Ru(0001) in which Ru atoms are etched from a step edge and injected under a growing graphene sheet. Based on density functional calculations, we propose a model wherein injected Ru atoms form metastable islands under the graphene. Scanning tunneling microscopy (STM) reveals that dislocation networks exist near step edges, consistent with some of the injected atoms being incorporated into the topmost Ru layer, thereby increasing its density.
We report the hydrogenation of single and bilayer graphene by an argon-hydrogen plasma produced in a reactive ion etching (RIE) system. Electronic transport measurements in combination with Raman spectroscopy are used to link the electric mean free path to the optically extracted defect concentration. We emphasize the role of the self-bias of the graphene in suppressing the erosion of the akes during plasma processing. We show that under the chosen plasma conditions the process does not introduce considerable damage to the graphene sheet and that hydrogenation occurs primarily due to the hydro…
We demonstrate anisotropic etching of single-layer graphene by thermally-activated nickel nanoparticles. Using this technique, we obtain sub-10nm nanoribbons and other graphene nanostructures with edges aligned along a single crystallographic direction. We observe a new catalytic channeling behavior, whereby etched cuts do not intersect, resulting in continuously connected geometries. Raman spectroscopy and electronic measurements show that the quality of the graphene is resilient under the etching conditions, indicating that this method may serve as a powerful technique to produce graphene na…
We describe a technique for making one-dimensional ohmic contacts to individual graphene layers encapsulated in hexagonal boron nitride (h-BN) using CF4 and O2 plasmas. The high etch selectivity of h-BN against graphene (>1000) is achieved by increasing the plasma pressure, which enables etching of h-BN, while graphene acts as an etch stop to protect underlying h-BN. A low-pressure O2 plasma anisotropically etches graphene in the vertical direction, which exposes graphene edges at h-BN sidewalls. Despite the O2 plasma bombardment, the lower h-BN layer functions as an insulating layer. Thus, th…
We report on the etching of graphene devices with a helium ion beam, including in situ electrical measurement during lithography. The etching process can be used to nanostructure and electrically isolate different regions in a graphene device, as demonstrated by etching a channel in a suspended graphene device with etched gaps down to about 10 nm. Graphene devices on silicon dioxide (SiO2) substrates etch with lower He ion doses and are found to have a residual conductivity after etching, which we attribute to contamination by hydrocarbons.
We report electron-beam activated motion of a catalytic nanoparticle along a graphene step edge and associated etching of the edge. This approach enables beam-controlled etching of matter through activated electrocatalytic processes. The applications of electron-beam control as a paradigm for molecular-scale robotics are discussed.
Graphene is attracting vast interest due to its superior electronic and mechanical properties. However, structure and electronic properties of its edge are often neglected, although they are important for nanoscale devices because the edge ratio becomes larger by decreasing the device size. In this study, we suggest a way to fabricate a graphene with atomically aligned zigzag edges by applying hydrogen-plasma etching (HPE) technique. By patterning a graphene prior to HPE, it is succeeded to shape a graphene in desired structure. Both atomic force microscopy and Raman spectroscopy confirm that …
The chemical reactivity of graphene under ultraviolet (UV) light irradiation is investigated under positive and negative gate electric fields. Graphene edges are selectively etched when negative gate voltages are applied, while the reactivity is significantly suppressed for positive gate voltages. Oxygen adsorption onto graphene is significantly affected by the Fermi level of the final state achieved during previous electrical measurements. UV irradiation after negative-to-positive gate sweeps causes predominant oxygen desorption, while UV irradiation after gate sweeps in the opposite directio…
A wide range of approaches have been explored to meet the challenges of graphene nanostructure fabrication, all requiring complex and high-end nanofabrication platform and suffering from surface contaminations, potentially giving electrical noise and increasing the thickness of the atomically thin graphene membrane. Here, with the use of an electrical pulse on a low capacitance graphene-on-glass (GOG) membrane, we fabricated clean graphene nanopores on commercially available glass substrates with exceptionally low electrical noise. In situ liquid AFM studies and electrochemical measurements re…
We present the effect of oxidative etching in FLG/TiO$_2$ hybrids on FLG edges chemistry/morphology addressing also the catalytic activity of TiO$_2$ NPs. According to the XPS and TGA analysis the oxidation degree strongly depends on TiO$_2$:FLG ratio. The preparation of two series of FLG/TiO$_2$ hybrids via sol-gel method and in-situ oxidation permitted to correctly describe and distinguish the chemical composition, core shift and charge distribution in C1s XPS with Tip peak as reference. Such analysis is challenging in carbon materials due the overlapping of C1s peaks from the sample and adv…
We present a systematic study of the Raman spectra of optical phonons in graphene monolayers under tunable uniaxial tensile stress. Both the G and 2D bands exhibit significant red shifts. The G band splits into two distinct sub-bands (G+, G-) because of the strain-induced symmetry breaking. Raman scattering from the G+ and G- bands shows a distinctive polarization dependence that reflects the angle between the axis of the stress and the underlying graphene crystal axes. Polarized Raman spectroscopy therefore constitutes a purely optical method for the determination of the crystallographic orie…
We report on suspended single-layer graphene deposition by a transfer-printing approach based on polydimethylsiloxane stamps. The transfer printing method allows the exfoliation of graphite flakes from a bulk graphite sample and their residue-free deposition on a silicon dioxide substrate. This deposition system creates a blistered graphene surface due to strain induced by the transfer process itself. Single-layer-graphene deposition and its "blistering" on the substrate are demonstrated by a combination of Raman spectroscopy, scanning electron microscopy and atomic-force microscopy measuremen…
Large scale graphene electronics desires lithographic patterning of narrow graphene nanoribbons (GNRs) for device integration. However, conventional lithography can only reliably pattern ~20nm wide GNR arrays limited by lithography resolution, while sub-5nm GNRs are desirable for high on/off ratio field-effect transistors (FETs) at room temperature. Here, we devised a gas phase chemical approach to etch graphene from the edges without damaging its basal plane. The reaction involved high temperature oxidation of graphene in a slightly reducing environment to afford controlled etch rate (\leq ~1…
Molten metallic nanoparticles have recently been used to construct graphene nanostructures with crystallographic edges. The mechanism by which this happens, however, remains unclear. Here, we present a simple model that explains how a droplet can etch graphene. Two factors possibly contribute to this process: a difference between the equilibrium wettability of graphene and the substrate that supports it, or the large surface energy associated with the graphene edge. We calculate the etching velocities due to either of these factors and make testable predictions for evaluating the significance …
The outstanding electrical and mechanical properties of graphene make it very attractive for several applications, Nanoelectronics above all. However a reproducible and non destructive way to produce high quality, large-scale area, single layer graphene sheets is still lacking. Chemical Vapour Deposition of graphene on Cu catalytic thin films represents a promising method to reach this goal, because of the low temperatures (T < 900 Celsius degrees) involved during the process and of the theoretically expected monolayer self-limiting growth. On the contrary such self-limiting growth is not comm…
Nanofabrication research pursues the miniaturization of patterned feature size. In the current state of the art, micron scale areas can be patterned with features down to ~ 30 nm pitch using electron beam lithography. Our work demonstrates a new nanofabrication technique which allows patterning periodic structures with a pitch down to 16 nm. It is based on focused ion beam milling of suspended membranes, with minimal proximity effects typical to electron beam lithography. The membranes are then transferred and used as hard etching masks. We benchmark our technique by engineering a superlattice…
In this study, we evaluated the sensing performance of silver nanoprism/graphene oxide/silicon nanowires (AgNPr/GO/SiNWs) nanohybrid system for effective detection of organic dye and herbicide residues in freshwater via surface-enhanced Raman scattering (SERS). Homogenous and vertically aligned SiNWs have been successfully synthesized using metal-assisted chemical etching technique by varying the etching time from 10 to 30 min. AgNPr/GO/SiNW hybrids were assembled by spin-coating of GO followed by drop-casting deposition of AgNPr. The microstructures of AgNPr/GO/SiNWs are strongly affected by …
Sculpturing desired shapes in single crystal diamond is ever more crucial in the realization of complex devices for nanophotonics, quantum computing, and quantum optics. The crystallographic orientation dependent wet etch of single crystalline silicon in potassium hydroxide (KOH) allows a range of shapes formed and has significant impacts on MEMS (microelectromechanical systems), AFM (atomic force microscopy), and microfluidics. Here, a crystal direction dependent dry etching principle in an inductively-coupled plasma reactive ion etcher is presented, which allows to selectively reveal desired…
Theory has predicted rich and very distinct physics for graphene devices with boundaries that follow either the armchair or zigzag crystallographic directions. A prerequisite to disclose this physics in experiment is to be able to produce devices with boundaries of pure chirality. Exfoliated flakes frequently exhibit corners with an odd multiple of 30°, which raised expectations that their boundaries follow pure zigzag and armchair directions. The predicted Raman behavior at such crystallographic edges however failed to confirm pure edge chirality. Here, we perform confocal Raman spectroscopy …
We report a two-step process to obtain smooth and vertical {10-10} m-plane facets in AlGaN/GaN separate confinement heterostructures designed to fabricate UV lasers emitting at 355 nm. The process consists in a dry etching by RIE-ICP combined with a crystallographic-selective wet etching process using a KOH-based solution. The anisotropy in the wet etching rates between the different crystallographic planes of the AlGaN structure, allows the fabrication of flat and parallel facets without a degradation of the multilayered ensemble. The optical performance of the lasers display a major improved…
Atomic resolution high angle annular dark field imaging of suspended, single-layer graphene, onto which the metals Cr, Ti, Pd, Ni, Al and Au atoms had been deposited was carried out in an aberration corrected scanning transmission electron microscope. In combination with electron energy loss spectroscopy, employed to identify individual impurity atoms, it was shown that nano-scale holes were etched into graphene, initiated at sites where single atoms of all the metal species except for gold come into close contact with the graphene. The e-beam scanning process is instrumental in promoting meta…
Edge engineering is important for both fundamental research and applications as the device size decreases to nanometer scale. This is especially the case for graphene because a graphene edge shows totally different electronic properties depending on the atomic structure and the termination. It has recently been shown that an atomically precise zigzag edge can be obtained by etching graphene and graphite using hydrogen (H) plasma. However, edge termination had not been studied directly. In this study, termination of edges created by H-plasma is studied by high-resolution electron energy loss sp…
Graphene has many advantageous properties, but its lack of an electronic band gap makes this two dimensional material impractical for many nanoelectronic applications, for example field effect transistors. This problem can be circumvented by opening up a confinement induced gap, through the patterning of graphene into ribbons having widths of a few nanometres. The electronic properties of such ribbons depend on their size and the crystallographic orientation of the ribbon edges. Therefore, etching processes that are able to differentiate between the zigzag and armchair type edge terminations o…
Crystallographic defects play a key role in determining the properties of crystalline materials. The new class of two-dimensional materials, foremost graphene, have enabled atomically resolved studies of defects, such as vacancies, grain boundaries, dislocations, and foreign atom substitutions. However, atomic resolution imaging of implanted self-interstitials has so far not been reported in any three- but also not in any two-dimensional material. Here, we deposit extra carbon into single-layer graphene at soft landing energies of ~1 eV using a standard carbon coater. We identify all the self-…
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.
We investigate nanoscale local anodic oxidation (LAO) on hydrogen-intercalated graphene grown by controlled sublimation of silicon carbide (SiC). Scanning probe microscopy (SPM) was used as a lithographic and characterization tool in order to investigate the local properties of the nanofabricated structures. The anomalous thickness observed after the graphene oxidation process is linked to the impact of LAO on the substrate. Micro-Raman spectroscopy was employed to demonstrate the presence of two oxidation regimes depending on the applied bias. We show that partial and total etching of monolay…
Realization of a free-standing graphene is always a demanding task. Here we use scanning probe microscopy and spectroscopy to study the crystallographic structure and electronic properties of the uniform free-standing graphene layers obtained by intercalation of oxygen monolayer in the "strongly" bonded graphene/Ru(0001) interface. Spectroscopic data show that such graphene layer is heavily p-doped with the Dirac point located at 552 meV above the Fermi level. Experimental data are understood within DFT and the observed effects are in good agreement with the theoretical data.
Uniform single layer graphene was grown on single-crystal Ir films a few nanometers thick which were prepared by pulsed laser deposition on sapphire wafers. These graphene layers have a single crystallographic orientation and a very low density of defects, as shown by diffraction, scanning tunnelling microscopy, and Raman spectroscopy. Their structural quality is as high as that of graphene produced on Ir bulk single crystals, i.e. much higher than on metal thin films used so far.
Nano-holes, etched under an electron beam at room temperature in singlelayer graphene sheets as a result of their interaction with metalimpurities, are shown to heal spontaneously by filling up with either non-hexagon, graphene-like, or perfect hexagon 2D structures. Scanning transmission electron microscopy was employed to capture the healing process and study atom-by-atom the re-grown structure. A combination of these nano-scale etching and re-knitting processes could lead to new graphene tailoring approaches.
We present an accurate measurement and a quantitative analysis of electron-beam induced displacements of carbon atoms in single-layer graphene. We directly measure the atomic displacement ("knock-on") cross section by counting the lost atoms as a function of the electron beam energy and applied dose. Further, we separate knock-on damage (originating from the collision of the beam electrons with the nucleus of the target atom) from other radiation damage mechanisms (e.g. ionization damage or chemical etching) by the comparison of ordinary (12C) and heavy (13C) graphene. Our analysis shows that …
The simultaneous combination of scanning probe methods (tunnelling and force microscopies, STM and AFM) is a unique way to get an information about crystallographic and electronic structure of the studied surface. Here we apply these methods accompanied by the state-of-the-art density functional theory (DFT) calculations to shed a light on the structure and electronic properties of the strongly-corrugated graphene/Rh(111) system. The atomically resolved images are obtained for both STM and AFM modes and compared with the DFT results showing good agreement between theory and experiment.
A striking feature of bilayer graphene is the induction of a significant band gap in the electronic states by the application of a perpendicular electric field. Thicker graphene layers are also highly attractive materials. The ability to produce a band gap in these systems is of great fundamental and practical interest. Both experimental and theoretical investigations of graphene trilayers with the typical ABA layer stacking have, however, revealed the lack of any appreciable induced gap. Here we contrast this behavior with that exhibited by graphene trilayers with ABC crystallographic stackin…
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…
Nanocontact properties of two-dimensional (2D) materials are closely dependent on their unique nanomechanical systems, such as the number of atomic layers and the supporting substrate. Here, we report a direct observation of toplayer-dependent crystallographic orientation imaging of 2D materials with the transverse shear microscopy (TSM). Three typical nanomechanical systems, MoS2 on the amorphous SiO2/Si, graphene on the amorphous SiO2/Si, and MoS2 on the crystallized Al2O3, have been investigated in detail. This experimental observation reveals that puckering behaviour mainly occurs on the t…
Few-layer graphene (FLG) has been predicted to exist in various crystallographic stacking sequences, which can strongly influence the electronic properties of FLG. We demonstrate an accurate and efficient method to characterize stacking order in FLG using the distinctive features of the Raman 2D-mode. Raman imaging allows us to visualize directly the spatial distribution of Bernal (ABA) and rhombohedral (ABC) stacking in tri- and tetra-layer graphene. We find that 15% of exfoliated graphene tri- and tetra-layers is comprised of micron-sized domains of rhombohedral stacking, rather than of usua…
The performance of graphene-based transistors is often limited by the large electrical resistance across the metal-graphene contact. We report an approach to achieve ultra-low resistance metal contacts to graphene transistors. Through a process of metal-catalyzed etching in hydrogen, multiple nano-sized pits with zigzag edges are created in the graphene that form strong chemical bonds with deposited nickel metallization for source-drain contacts without the need for further annealing. This facile contact treatment prior to electrode metallization results in contact resistance as low as 100 ohm…
A broad variety of defects has been observed in two-dimensional materials. Many of these defects can be created by top-down methods such as electron irradiation or chemical etching, while a few of them are created along bottom-up processes, in particular during the growth of the material, in which case avoiding their formation can be challenging. This occurs e.g. with dislocations, Stone-Wales defects, or atomic vacancies in graphene. Here we address a defect that has been observed repeatedly since 2007 in epitaxial graphene on metal surfaces like Ru(0001) and Re(0001), but whose nature has re…
Free standing silicene is predicted to display comparable electronic properties as graphene. However, the yet synthesized silicene-like structures have been only realized on different substrates which turned out to exhibit versatile crystallographic structures that are very different from the theoretically predicted buckled phase of freestanding silicene. This calls for a different approach where silicene is stabilized using very weakly interacting surfaces. We propose here a novel route by using graphene bilayer as a scaffold. The confinement between the flat graphene layers results in a plan…
In this paper, a method is presented to create and characterize mechanically robust, free standing, ultrathin, oxide films with controlled, nanometer-scale thickness using Atomic Layer Deposition (ALD) on graphene. Aluminum oxide films were deposited onto suspended graphene membranes using ALD. Subsequent etching of the graphene left pure aluminum oxide films only a few atoms in thickness. A pressurized blister test was used to determine that these ultrathin films have a Young's modulus of 154 \pm 13 GPa. This Young's modulus is comparable to much thicker alumina ALD films. This behavior indic…
Moiré superlattices in graphene supported on various substrates have opened a new avenue to engineer graphene's electronic properties. Yet, the exact crystallographic structure on which their band structure depends remains highly debated. In this scanning tunneling microscopy and density functional theory study, we have analysed graphene samples grown on multilayer graphene prepared onto SiC and on the close-packed surfaces of Re and Ir with ultra-high precision. We resolve small-angle twists and shears in graphene, and identify large unit cells comprising more than 1,000 carbon atoms and exhi…
Graphene-derived nanomaterials are emerging as ideal candidates for postsilicon electronics. Elucidating the electronic interaction between an insulating substrate and few-layer graphene (FLG) films is crucial for device applications. Here, we report electrostatic force microscopy (EFM) measurements revealing that the FLG surface potential increases with film thickness, approaching a "bulk" value for samples with five or more graphene layers. This behavior is in sharp contrast with that expected for conventional conducting or semiconducting films, and derives from unique aspects of charge scre…
Graphene-covered copper surfaces have been exposed to borazine, (BH)3(NH)3, with the resulting surfaces characterized by low-energy electron microscopy. Although the intent of the experiment was to form hexagonal boron nitride (h-BN) on top of the graphene, such layers were not obtained. Rather, in isolated surface areas, h-BN is found to form micrometer-size islands that substitute for the graphene. Additionally, over nearly the entire surface, the properties of the layer that was originally graphene is observed to change in a manner that is consistent with the formation of a mixed h-BN/graph…
Graphene on silicon carbide (SiC) bears great potential for future graphene electronic applications because it is available on the wafer-scale and its properties can be custom-tailored by inserting various atoms into the graphene/SiC interface. It remains unclear, however, how atoms can cross the impermeable graphene layer during this widely used intercalation process. Here we demonstrate that, in contrast to the current consensus, graphene layers on SiC are not homogeneous, but instead composed of domains of different crystallographic stacking. We show that these domains are intrinsically for…
Graphene nano-electro-mechanical switches are promising components due to their excellent switching performance such as low pull-in voltage and low contact resistance. Mass fabrication with an appropriate counter electrode remains challenging. In this work, we report the stacking of nanocrystalline graphene (NCG) with a 70-nm dielectric separation layer. The buried NCG layer is contacted through the formation of vias and acts as actuation electrode. After metallization, the top 7.5-nm thin NCG layer is patterned to form double-clamped beams, and the structure is released by hydrofluoric acid e…
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…
The intrinsic resistance peak (ridge) structures were recently found to appear in the carrier density dependence plot of the resistance of the AB-stacked multilayer graphene with even numbers of layers.The ridges are due to topological changes in the Fermi surface. Here, these structures were studied in AB-stacked multilayer graphene with odd numbers of layers (5 and 7 layers) by performing experiments using encapsulated high-quality graphene samples equipped with top and bottom gate electrodes.The intrinsic resistance peaks that appeared on maps plotted with respect to the carrier density and…
We investigated theoretically the phonon thermal conductivity of single layer graphene. The phonon dispersion for all polarizations and crystallographic directions in graphene lattice was obtained using the valence-force field method. The three-phonon Umklapp processes were treated exactly using an accurate phonon dispersion and Brillouin zone, and accouting for all phonon relaxation channels allowed by the momentum and energy conservation laws. The uniqueness of graphene was reflected in the two-dimensional phonon density of states and restrictions on the phonon Umklapp scattering phase-space…
Graphene nanoribbons (GNRs) make up an extremely interesting class of materials. On the one hand GNRs share many of the superlative properties of graphene, while on the other hand they display an exceptional degree of tunability of their optoelectronic properties. The presence or absence of correlated low-dimensional magnetism, or of a widely tunable band gap, is determined by the boundary conditions imposed by the width, crystallographic symmetry and edge structure of the nanoribbons. In combination with additional controllable parame-ters like the presence of heteroatoms, tailored strain, or…
