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Terahertz time-domain spectroscopy (THz-TDS) can be used to map spatial variations in electrical properties such as sheet conductivity, carrier density, and carrier mobility in graphene. Here, we consider wafer-scale graphene grown on germanium by chemical vapor deposition with non-uniformities and small domains due to reconstructions of the substrate during growth. The THz conductivity spectrum matches the predictions of the phenomenological Drude-Smith model for conductors with non-isotropic scattering caused by backscattering from boundaries and line defects. We compare the charge carrier mean free path determined by THz-TDS with the average defect distance assessed by Raman spectroscopy, and the grain boundary dimensions as determined by transmission electron microscopy. The results indicate that even small angle orientation variations below 5° within graphene grains influence the scattering behavior, consistent with significant backscattering contributions from grain boundaries.
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The integration of dissimilar materials in heterostructures has long been a cornerstone of modern materials science-seminal examples are 2D materials and van der Waals heterostructures. Recently, new methods have been developed that enable the realization of ultrathin freestanding oxide films approaching the 2D limit. Oxides offer new degrees of freedom, due to the strong electronic interactions, especially the 3d orbital electrons, which give rise to rich exotic phases. Inspired by this progress, a new platform for assembling freestanding oxide thin films with different materials and orientations into artificial stacks with heterointerfaces is developed. It is shown that the oxide stacks can be tailored by controlling the stacking sequences, as well as the twist angle between the constituent layers with atomically sharp interfaces, leading to distinct moiré patterns in the transmission electron microscopy images of the full stacks. Stacking and twisting is recognized as a key degree of structural freedom in 2D materials but, until now, has never been realized for oxide materials. This approach opens unexplored avenues for fabricating artificial 3D oxide stacking heterostructures with freestanding membranes across a broad range of complex oxide crystal structures with functionalities not available in conventional 2D materials.
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The purity and morphology of the copper surface is important for the synthesis of high-quality, large-grained graphene by chemical vapor deposition. We find that atomically smooth copper foils-fabricated by physical vapor deposition and subsequent electroplating of copper on silicon wafer templates-exhibit strongly reduced surface roughness after the annealing of the copper catalyst, and correspondingly lower nucleation and defect density of the graphene film, when compared to commercial cold-rolled copper foils. The "ultrafoils"-ultraflat foils-facilitate easier dry pickup and encapsulation of graphene by hexagonal boron nitride, which we believe is due to the lower roughness of the catalyst surface promoting a conformal interface and subsequent stronger van der Waals adhesion between graphene and hexagonal boron nitride.
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In this work, we use atomic force microscopy (AFM) to investigate the long-term evolution of oxidative defects of tungsten diselenide (WSe2) in ambient conditions over a period of 75 months, which is the longest such study performed on any layered material. In particular, we find that phase-imaging AFM of mechanically exfoliated WSe2 crystals provides convenient, direct identification of exposed and covered step-edges, and together with topographic thickness measurements allows complete determination of the layer arrangement in a multilayer flake. Step-edges with low or no phase-contrast consistently exhibit long-term stability in ambient conditions, indicating that they are covered and effectively protected by above-lying WSe2 layers. On the contrary, step-edges with initial high phase-contrast are clearly degraded after medium- to long-term exposure to ambient conditions (up to six months), indicating that these are not covered by other layers. Similar behaviour was observed for MoTe2 and MoS2. The correlation between phase-contrast and step order was confirmed by cross-sectional transmission electron microscopy. By comparing the phase-contrast line-traces in different locations and at different times, we find that long-term storage in ambient conditions led to evolution of a distinct ring-like pattern resembling the tree-lines arising from seasonal changes. Indeed the phase-contrast showed correlation with the average amount of sun-hours registered at the storage location. Storage in darkness slowed down the evolution of the tree-ring lines, in accordance with this explanation. Our work provides a unique dataset on long-term degradation of one of the most stable transition metal dichalcogenides, as well as insights into the conditions causing acceleration or inhibition of the degradation process.
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Nanostructuring allows altering of the electronic and photonic properties of two-dimensional (2D) materials. The efficiency, flexibility, and convenience of top-down lithography processes are, however, compromised by nanometer-scale edge roughness and resolution variability issues, which especially affect the performance of 2D materials. Here, we study how dry anisotropic etching of multilayer 2D materials with sulfur hexafluoride (SF6) may overcome some of these issues, showing results for hexagonal boron nitride (hBN), tungsten disulfide (WS2), tungsten diselenide (WSe2), molybdenum disulfide (MoS2), and molybdenum ditelluride (MoTe2). Scanning electron microscopy and transmission electron microscopy reveal that etching leads to anisotropic hexagonal features in the studied transition metal dichalcogenides, with the relative degree of anisotropy ranked as: WS2 > WSe2 > MoTe2 â¼ MoS2. Etched holes are terminated by zigzag edges while etched dots (protrusions) are terminated by armchair edges. This can be explained by Wulff constructions, taking the relative stabilities of the edges and the AA' stacking order into account. Patterns in WS2 are transferred to an underlying graphite layer, demonstrating a possible use for creating sub-10 nm features. In contrast, multilayer hBN exhibits no lateral anisotropy but shows consistent vertical etch angles, independent of crystal orientation. Using an hBN crystal as the base, ultrasharp corners can be created in lithographic patterns, which are then transferred to a graphite crystal underneath. We find that the anisotropic SF6 reactive ion etching process makes it possible to downsize nanostructures and obtain smooth edges, sharp corners, and feature sizes significantly below the resolution limit of electron beam lithography. The nanostructured 2D materials can be used themselves or as etch masks to pattern other nanomaterials.
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The barrier properties of graphene coating are highly correlated with its microstructure which is then determined by the chemical vapor deposition (CVD) growth history on metals. We demonstrate here an unrevealed selective area oxidation of copper under graphene, which is derived from the implicit-etching-controlled CVD growth mode of graphene. By charactering and analyzing the selective area patterns of Cu oxidation, an etched pattern trace with nano/microvoids during graphene growth has been proposed to account for this. Based on such selective oxidation of Cu, distributed galvanic corrosion will be triggered and proceed locally at the interface of graphene-Cu system to coalescence together under a continuous corrosion environment, eventually presenting a homogeneous oxidation of Cu and gradual decoupling of graphene-Cu system. This discovery will assist our understanding of the barrier properties of two-dimensional materials and can be extended to other applications related to quality monitoring of grown materials and defects-based chemical modifications.
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The correlation between the crystal structure of chemical vapor deposition (CVD)-grown graphene and the crystal structure of the Cu growth substrate and their mutual effect on the oxidation of the underlying Cu are systematically explored. We report that natural oxygen or water intercalation along the graphene-Cu interface results in an orientation-dependent oxidation rate of the Cu surface, particularly noticeable for bicrystal graphene domains on the same copper grain, suggesting that the relative crystal orientation of subgrains determines the degree of Cu oxidation. Atomistic force field calculations support these observations, showing that graphene domains have preferential alignment with the Cu(111) with a smaller average height above the global Cu surface as compared to intermediate orientations, and that this is the origin of the heterogeneous oxidation rate of Cu. This work demonstrates that the natural oxidation resistance of Cu coated by graphene is highly dependent on the crystal orientation and lattice alignment of Cu and graphene, which is key information for engineering the interface configuration of the graphene-Cu system for specific functionalities in mechanical, anticorrosion, and electrical applications of CVD-grown graphene.
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Only a few of the vast range of potential two-dimensional materials (2D) have been isolated or synthesised to date. Typically, 2D materials are discovered by mechanically exfoliating naturally occurring bulk crystals to produce atomically thin layers, after which a material-specific vapour synthesis method must be developed to grow interesting candidates in a scalable manner. Here we show a general approach for synthesising thin layers of two-dimensional binary compounds. We apply the method to obtain high quality, epitaxial MoS2 films, and extend the principle to the synthesis of a wide range of other materials-both well-known and never-before isolated-including transition metal sulphides, selenides, tellurides, and nitrides. This approach greatly simplifies the synthesis of currently known materials, and provides a general framework for synthesising both predicted and unexpected new 2D compounds.
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Graphene field-effect transistors (GFETs) offer a possibility of exploiting unique physical properties of graphene in realizing novel electronic circuits. However, graphene circuits often lack the voltage swing and switchability of Si complementary metal-oxide-semiconductor (CMOS) circuits, which are the main building block of modern electronics. Here we introduce graphene in Si CMOS circuits to exploit favorable electronic properties of both technologies and realize a new class of simple oscillators using only a GFET, Si CMOS D latch, and timing RC circuit. The operation of the two types of realized oscillators is based on the ambipolarity of graphene, i.e., the symmetry of the transfer curve of GFETs around the Dirac point. The ambipolarity of graphene also allowed to turn the oscillators into pulse-width modulators (with a duty cycle ratio â¼1 : 4) and voltage-controlled oscillators (with a frequency ratio â¼1 : 8) without any circuit modifications. The oscillation frequency was in the range from 4 kHz to 4 MHz and limited only by the external circuit connections, rather than components themselves. The demonstrated graphene-Si CMOS hybrid circuits pave the way to the more widespread adoption of graphene in electronics.
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Two-dimensional materials such as graphene allow direct access to the entirety of atoms constituting the crystal. While this makes shaping by lithography particularly attractive as a tool for band structure engineering through quantum confinement effects, edge disorder and contamination have so far limited progress towards experimental realization. Here, we define a superlattice in graphene encapsulated in hexagonal boron nitride, by etching an array of holes through the heterostructure with minimum feature sizes of 12-15 nm. We observe a magnetotransport regime that is distinctly different from the characteristic Landau fan of graphene, with a sizeable bandgap that can be tuned by a magnetic field. The measurements are accurately described by transport simulations and analytical calculations. Finally, we observe strong indications that the lithographically engineered band structure at the main Dirac point is cloned to a satellite peak that appears due to moiré interactions between the graphene and the encapsulating material.
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We study the oxidation of clean suspended mono- and few-layer graphene in real time by in situ environmental transmission electron microscopy. At an oxygen pressure below 0.1 mbar, we observe anisotropic oxidation in which armchair-oriented hexagonal holes are formed with a sharp edge roughness below 1 nm. At a higher pressure, we observe an increasingly isotropic oxidation, eventually leading to irregular holes at a pressure of 6 mbar. In addition, we find that few-layer flakes are stable against oxidation at temperatures up to at least 1000 °C in the absence of impurities and electron-beam-induced defects. These findings show, first, that the oxidation behavior of mono- and few-layer graphene depends critically on the intrinsic roughness, cleanliness and any imposed roughness or additional reactivity from a supporting substrate and, second, that the activation energy for oxidation of pristine suspended few-layer graphene is up to 43% higher than previously reported for graphite. In addition, we have developed a cleaning scheme that results in the near-complete removal of hydrocarbon residues over the entire visible sample area. These results have implications for applications of graphene where edge roughness can critically affect the performance of devices and more generally highlight the surprising (meta)stability of the basal plane of suspended bilayer and thicker graphene toward oxidative environments at high temperature.
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Fast inline characterization of the electrical properties of graphene on polymeric substrates is an essential requirement for quality control in industrial graphene production. Here we show that it is possible to measure the sheet conductivity of graphene on polymer films by terahertz time-domain spectroscopy (THz-TDS) when all internally reflected echoes in the substrate are taken into consideration. The conductivity measured by THz-TDS is comparable to values obtained from four point probe measurements. THz-TDS maps of 25x30 cm2 area graphene films were recorded and the DC conductivity and carrier scattering time were extracted from the measurements. Additionally, the THz-TDS conductivity maps highlight tears and holes in the graphene film, which are not easily visible by optical inspection.
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We show that polar molecules (water, ammonia, and nitrogen dioxide) adsorbed solely at the exposed edges of an encapsulated graphene sheet exhibit ferroelectricity, collectively orienting and switching reproducibly between two available states in response to an external electric field. This ferroelectric molecular switching introduces drastic modifications to the graphene bulk conductivity and produces a large and ambipolar charge bistability in micrometer-size graphene devices. This system comprises an experimental realization of envisioned memory capacitive ("memcapacitive") devices whose capacitance is a function of their charging history, here conceived via confined and correlated polar molecules at the one-dimensional edge of a two-dimensional crystal.
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The pace of two-dimensional materials (2DM) research has been greatly accelerated by the ability to identify exfoliated thicknesses down to a monolayer from their optical contrast. Since this process requires time-consuming and error-prone manual assignment to avoid false-positives from image features with similar contrast, efforts towards fast and reliable automated assignments schemes is essential. We show that by modelling the expected 2DM contrast in digitally captured images, we can automatically identify candidate regions of 2DM. More importantly, we show a computationally-light machine vision strategy for eliminating false-positives from this set of 2DM candidates through the combined use of binary thresholding, opening and closing filters, and shape-analysis from edge detection. Calculation of data pyramids for arbitrarily high-resolution optical coverage maps of two-dimensional materials produced in this way allows the real-time presentation and processing of this image data in a zoomable interface, enabling large datasets to be explored and analysed with ease. The result is that a standard optical microscope with CCD camera can be used as an analysis tool able to accurately determine the coverage, residue/contamination concentration, and layer number for a wide range of presented 2DMs.
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Conductance quantization is the quintessential feature of electronic transport in non-interacting mesoscopic systems. This phenomenon is observed in quasi one-dimensional conductors at zero magnetic field B, and the formation of edge states at finite magnetic fields results in wider conductance plateaus within the quantum Hall regime. Electrostatic interactions can change this picture qualitatively. At finite B, screening mechanisms in narrow, gated ballistic conductors are predicted to give rise to an increase in conductance and a suppression of quantization due to the appearance of additional conduction channels. Despite being a universal effect, this regime has proven experimentally elusive because of difficulties in realizing one-dimensional systems with sufficiently hard-walled, disorder-free confinement. Here, we experimentally demonstrate the suppression of conductance quantization within the quantum Hall regime for graphene nanoconstrictions with low edge roughness. Our findings may have profound impact on fundamental studies of quantum transport in finite-size, two-dimensional crystals with low disorder.
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The processes governing multilayer nucleation in the chemical vapour deposition (CVD) of graphene are important for obtaining high-quality monolayer sheets, but remain poorly understood. Here we show that higher-order carbon species in the gas-phase play a major role in multilayer nucleation, through the use of in-situ ultraviolet (UV) absorption spectroscopy. These species are the volatilized products of reactions between hydrogen and carbon contaminants that have backstreamed into the reaction chamber from downstream system components. Consequently, we observe a dramatic suppression of multilayer nucleation when backstreaming is suppressed. These results point to an important and previously undescribed mechanism for multilayer nucleation, wherein higher-order gas-phase carbon species play an integral role. Our work highlights the importance of gas-phase dynamics in understanding the overall mechanism of graphene growth.
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We investigated toxicity of 2-3 layered >1 µm sized graphene oxide (GO) and reduced graphene oxide (rGO) in mice following single intratracheal exposure with respect to pulmonary inflammation, acute phase response (biomarker for risk of cardiovascular disease) and genotoxicity. In addition, we assessed exposure levels of particulate matter emitted during production of graphene in a clean room and in a normal industrial environment using chemical vapour deposition. Toxicity was evaluated at day 1, 3, 28 and 90 days (18, 54 and 162 µg/mouse), except for GO exposed mice at day 28 and 90 where only the lowest dose was evaluated. GO induced a strong acute inflammatory response together with a pulmonary (Serum-Amyloid A, Saa3) and hepatic (Saa1) acute phase response. rGO induced less acute, but a constant and prolonged inflammation up to day 90. Lung histopathology showed particle agglomerates at day 90 without signs of fibrosis. In addition, DNA damage in BAL cells was observed across time points and doses for both GO and rGO. In conclusion, pulmonary exposure to GO and rGO induced inflammation, acute phase response and genotoxicity but no fibrosis.
Assuntos
Reação de Fase Aguda , Grafite/toxicidade , Inflamação/patologia , Pulmão/efeitos dos fármacos , Mutagênicos/toxicidade , Animais , Líquido da Lavagem Broncoalveolar , Feminino , Grafite/química , Camundongos , Camundongos Endogâmicos C57BL , Oxirredução , Óxidos/químicaRESUMO
The assembly of individual two-dimensional materials into van der Waals heterostructures enables the construction of layered three-dimensional materials with desirable electronic and optical properties. A core problem in the fabrication of these structures is the formation of clean interfaces between the individual two-dimensional materials which would affect device performance. We present here a technique for the rapid batch fabrication of van der Waals heterostructures, demonstrated by the controlled production of 22 mono-, bi- and trilayer graphene stacks encapsulated in hexagonal boron nitride with close to 100% yield. For the monolayer devices, we found semiclassical mean-free paths up to 0.9 µm, with the narrowest samples showing clear indications of the transport being affected by boundary scattering. The presented method readily lends itself to fabrication of van der Waals heterostructures in both ambient and controlled atmospheres, while the ability to assemble pre-patterned layers paves the way for complex three-dimensional architectures.
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Carrier mobility and chemical doping level are essential figures of merit for graphene, and large-scale characterization of these properties and their uniformity is a prerequisite for commercialization of graphene for electronics and electrodes. However, existing mapping techniques cannot directly assess these vital parameters in a non-destructive way. By deconvoluting carrier mobility and density from non-contact terahertz spectroscopic measurements of conductance in graphene samples with terahertz-transparent backgates, we are able to present maps of the spatial variation of both quantities over large areas. The demonstrated non-contact approach provides a drastically more efficient alternative to measurements in contacted devices, with potential for aggressive scaling towards wafers/minute. The observed linear relation between conductance and carrier density in chemical vapour deposition graphene indicates dominance by charged scatterers. Unexpectedly, significant variations in mobility rather than doping are the cause of large conductance inhomogeneities, highlighting the importance of statistical approaches when assessing large-area graphene transport properties.
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High resolution nanopatterning of graphene enables manipulation of electronic, optical and sensing properties of graphene. In this work we present a straightforward technique that does not require any lithographic mask to etch nanopatterns into graphene. The technique relies on the damaged graphene to be etched selectively in an oxygen rich environment with respect to non-damaged graphene. Sub-40 nm features were etched into graphene by selectively exposing it to a 100 keV electron beam and then etching the damaged areas away in a conventional oven. Raman spectroscopy was used to evaluate the extent of damage induced by the electron beam as well as the effects of the selective oxidative etching on the remaining graphene.