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Large-area single-crystal monolayers of two-dimensional (2D) materials such as graphene1-3, hexagonal boron nitride (hBN)4-6 and transition metal dichalcogenides7,8 have been grown. hBN is considered to be the 'ideal' dielectric for 2D-materials-based field-effect transistors (FETs), offering the potential for extending Moore's law9,10. Although hBN thicker than a monolayer is more desirable as substrate for 2D semiconductors11,12, highly uniform and single-crystal multilayer hBN growth has yet to be demonstrated. Here we report the epitaxial growth of wafer-scale single-crystal trilayer hBN by a chemical vapour deposition (CVD) method. Uniformly aligned hBN islands are found to grow on single-crystal Ni (111) at early stage and finally to coalesce into a single-crystal film. Cross-sectional transmission electron microscopy (TEM) results show that a Ni23B6 interlayer is formed (during cooling) between the single-crystal hBN film and Ni substrate by boron dissolution in Ni. There are epitaxial relationships between hBN and Ni23B6 and between Ni23B6 and Ni. We also find that the hBN film acts as a protective layer that remains intact during catalytic evolution of hydrogen, suggesting continuous single-crystal hBN. This hBN transferred onto the SiO2 (300 nm)/Si wafer acts as a dielectric layer to reduce electron doping from the SiO2 substrate in MoS2 FETs. Our results demonstrate high-quality single-crystal multilayered hBN over large areas, which should open up new pathways for making it a ubiquitous substrate for 2D semiconductors.
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Chemical vapour deposition of carbon-containing precursors on metal substrates is currently the most promising route for the scalable synthesis of large-area, high-quality graphene films1. However, there are usually some imperfections present in the resulting films: grain boundaries, regions with additional layers (adlayers), and wrinkles or folds, all of which can degrade the performance of graphene in various applications2-7. There have been numerous studies on ways to eliminate grain boundaries8,9 and adlayers10-12, but graphene folds have been less investigated. Here we explore the wrinkling/folding process for graphene films grown from an ethylene precursor on single-crystal Cu-Ni(111) foils. We identify a critical growth temperature (1,030 kelvin) above which folds will naturally form during the subsequent cooling process. Specifically, the compressive stress that builds up owing to thermal contraction during cooling is released by the abrupt onset of step bunching in the foil at about 1,030 kelvin, triggering the formation of graphene folds perpendicular to the step edge direction. By restricting the initial growth temperature to between 1,000 kelvin and 1,030 kelvin, we can produce large areas of single-crystal monolayer graphene films that are high-quality and fold-free. The resulting films show highly uniform transport properties: field-effect transistors prepared from these films exhibit average room-temperature carrier mobilities of around (7.0 ± 1.0) × 103 centimetres squared per volt per second for both holes and electrons. The process is also scalable, permitting simultaneous growth of graphene of the same quality on multiple foils stacked in parallel. After electrochemical transfer of the graphene films from the foils, the foils themselves can be reused essentially indefinitely for further graphene growth.
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Over the past decade, lithium metal has been considered the most attractive anode material for high-energy-density batteries. However, its practical application has been hindered by its high reactivity with organic electrolytes and uncontrolled dendritic growth, resulting in poor Coulombic efficiency and cycle life. In this paper, we propose a design strategy for interface engineering using a conversion-type reaction of metal fluorides to evolve a LiF passivation layer and Li-M alloy. Particularly, we propose a LiF-modified Li-Mg-C electrode, which demonstrates stable long-term cycling for over 2000 h in common organic electrolytes with fluoroethylene carbonate (FEC) additives and over 700 h even without additives, suppressing unwanted side reactions and Li dendritic growth. With the help of phase diagrams, we found that solid-solution-based alloying not only facilitates the spontaneous evolution of a LiF layer and bulk alloy but also enables reversible Li plating/stripping inward to the bulk, compared with intermetallic compounds with finite Li solubility.
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We have designed and fabricated a TEM (transmission electron microscopy) liquid cell with hundreds of graphene nanocapsules arranged in a stack of two Si3N4-x membranes. These graphene nanocapsules are formed on arrays of nanoholes patterned on the Si3N4-x membrane by focused ion beam milling, allowing for better resolution than for the conventional graphene liquid cells, which enables the observation of light elements, such as atomic structures of silicon. We suggest that multiple nanocapsules provide opportunities for consecutive imaging under the same conditions in a single liquid cell. The use of single-crystal graphene windows offers an excellent signal-to-noise ratio and high spatial resolution. The motion of silicon nanoparticles (a low atomic number (Z) material) interacting with nanobubbles was observed, and analyzed, in detail. Our approach will help advance liquid-phase TEM observations by providing a straightforward method to encapsulate liquid between monolayers of various 2-dimensional materials.
Assuntos
Grafite , Nanocápsulas , Nanopartículas , Grafite/química , Microscopia Eletrônica de Transmissão , Nanopartículas/química , SilícioRESUMO
The authors report the growth of micrometer-long single-crystal graphene ribbons (GRs) (tapered when grown above 900 °C, but uniform width when grown in the range 850 °C to 900 °C) using silica particle seeds on single crystal Cu(111) foil. Tapered graphene ribbons grow strictly along the Cu<101> direction on Cu(111) and polycrystalline copper (Cu) foils. Silica particles on both Cu foils form (semi-)molten Cu-Si-O droplets at growth temperatures, then catalyze nucleation and drive the longitudinal growth of graphene ribbons. Longitudinal growth is likely by a vapor-liquid-solid (VLS) mechanism but edge growth (above 900 °C) is due to catalytic activation of ethylene (C2 H4 ) and attachment of C atoms or species ("vapor solid" or VS growth) at the edges. It is found, based on the taper angle of the graphene ribbon, that the taper angle is determined by the growth temperature and the growth rates are independent of the particle size. The activation enthalpy (1.73 ± 0.03 eV) for longitudinal ribbon growth on Cu(111) from ethylene is lower than that for VS growth at the edges of the GRs (2.78 ± 0.15 eV) and for graphene island growth (2.85 ± 0.07 eV) that occurs concurrently.
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Folded graphene in which two layers are stacked with a twist angle between them has been predicted to exhibit unique electronic, thermal, and magnetic properties. We report the folding of a single crystal monolayer graphene film grown on a Cu(111) substrate by using a tailored substrate having a hydrophobic region and a hydrophilic region. Controlled film delamination from the hydrophilic region was used to prepare macroscopic folded graphene with good uniformity on the millimeter scale. This process was used to create many folded sheets each with a defined twist angle between the two sheets. By identifying the original lattice orientation of the monolayer graphene on Cu foil, or establishing the relation between the fold angle and twist angle, this folding technique allows for the preparation of twisted bilayer graphene films with defined stacking orientations and may also be extended to create folded structures of other two-dimensional nanomaterials.
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We present an electrochemical method to functionalize single-crystal graphene grown on copper foils with a (111) surface orientation by chemical vapor deposition (CVD). Graphene on Cu(111) is functionalized with 4-iodoaniline by applying a constant negative potential, and the degree of functionalization depends on the applied potential and reaction time. Our approach stands out from previous methods due to its transfer-free method, which enables more precise and efficient functionalization of single-crystal graphene. We report the suggested effects of the Cu substrate facet by comparing the reactivity of graphene on Cu(111) and Cu(115). The electrochemical reaction rate changes dramatically at the potential threshold for each facet. Kelvin probe force microscopy was used to measure the work function, and the difference in onset potentials of the electrochemical reaction on these two different facets are explained in terms of the difference in work function values. Density functional theory and Monte Carlo calculations were used to calculate the work function of graphene and the thermodynamic stability of the aniline functionalized graphene on these two facets. This study provides a deeper understanding of the electrochemical behavior of graphene (including single-crystal graphene) on Cu(111) and Cu(115). It also serves as a basis for further study of a broad range of reagents and thus functional groups and of the role of metal substrate beneath graphene.
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The practical use of silicon anodes is interfered by the following key factors: volume expansion, slow kinetics, and low electrical and ionic conductivities. Many studies have focused on surface engineering from the particle to electrode level to achieve stability and energy density. Herein, simple nitrogen gas plasma is introduced as a surface treatment method for silicon-based electrodes to avoid the problems of material synthesis-based functionalizations (e.g., high cost, time consuming, and low quality). The introduction of activated nitrogen gas on electrode surfaces changes the binding energy and resistance of silicon, increasing the reversibility of the charge/discharge reaction of silicon-based anodes. In addition, such doping and dehydrogenation of the electrode surface improve reaction kinetics to 876 mA h g-1 specific capacity at 8.5 A g-1 in silicon/graphite anodes even with a high silicon content of 40%. The proposed strategy, through nitrogen plasma, offers advantages for direct functionalization on electrode surfaces by a simple method.
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In humid conditions, water vapor can easily neutralize the surface active sites of metal oxide sensors, leading to a lowering in the sensitivity of the gas sensor and a resultant inaccurate signal in practical applications. Herein, we present a new hybrid sensor by introducing a two-dimensional calcium silicate (CS) nanosheet as a water-trapping layer in SnO2 nanowires. Unlike the heavily wrinkled and aggregated morphology of conventional CS nanosheets, our nanosheet in the hybrid material is ultrathin and flat. Moreover, it was grown in the empty spaces between the spider-web-like networks of SnO2 nanowires without covering the nanowire surface. These two morphological features improve moisture trapping with minimal reduction in the active sensing area. Consequently, stable and sensitive gas detection under humid conditions was achieved in this hybrid sensor. The superior humidity-independent sensing is ascribed to the preferential adsorption of water molecules on hydroscopic CS nanosheets through the hydrogen bond. Based on density functional theory calculations, we determined that the improved gas response is driven by the additional formation of oxygen vacancy in SnO2 due to the diffusion of aliovalent Ca ions from the CS nanosheet.
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A single-crystal graphene film grown on a Cu(111) foil by chemical vapor deposition (CVD) has ribbon-like fold structures. These graphene folds are highly oriented and essentially parallel to each other. Cu surface steps underneath the graphene are along the <110> and <211> directions, leading to the formation of the arrays of folds. The folds in the single-layer graphene (SLG) are not continuous but break up into alternating patterns. A "joint" (an AB-stacked bilayer graphene) region connects two neighboring alternating regions, and the breaks are always along zigzag or armchair directions. Folds formed in bilayer or few-layer graphene are continuous with no breaks. Molecular dynamics simulations show that SLG suffers a significantly higher compressive stress compared to bilayer graphene when both are under the same compression, thus leading to the rupture of SLG in these fold regions. The fracture strength of a CVD-grown single-crystal SLG film is simulated to be about 70 GPa. This study greatly deepens the understanding of the mechanics of CVD-grown single-crystal graphene and such folds, and sheds light on the fabrication of various graphene origami/kirigami structures by substrate engineering. Such oriented folds can be used in a variety of further studies.
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The wet-oxidation of a single crystal Cu(111) foil is studied by growing single crystal graphene islands on it followed by soaking it in water. 18 O-labeled water is also used; the oxygen atoms in the formed copper oxides in both the bare and graphene-coated Cu regions come from water. The oxidation of the graphene-coated Cu regions is enabled by water diffusing from the edges of graphene along the bunched Cu steps, and along some graphene ripples where such are present. This interfacial diffusion of water can occur because of the separation between the graphene and the "step corner" of bunched Cu steps. Density functional theory simulations suggest that adsorption of water in this gap is thermodynamically stable; the "step-induced-diffusion model" also applies to graphene-coated Cu surfaces of various other crystal orientations. Since bunched Cu steps and graphene ripples are diffusion pathways for water, ripple-free graphene is prepared on ultrasmooth Cu(111) surfaces and it is found that the graphene completely shields the underlying Cu from wet-oxidation. This study greatly deepens the understanding of how a graphene-coated copper surface is oxidized, and shows that graphene completely prevents the oxidation when that surface is ultrasmooth and when the graphene has no ripples or wrinkles.
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Notwithstanding the numerous density functional studies on the chemically induced transformation of multilayer graphene into a diamond-like film carried out to date, a comprehensive convincing experimental proof of such a conversion is still lacking. We show that the fluorination of graphene sheets in Bernal (AB)-stacked bilayer graphene grown by chemical vapour deposition on a single-crystal CuNi(111) surface triggers the formation of interlayer carbon-carbon bonds, resulting in a fluorinated diamond monolayer ('F-diamane'). Induced by fluorine chemisorption, the phase transition from (AB)-stacked bilayer graphene to single-layer diamond was studied and verified by X-ray photoelectron, UV photoelectron, Raman, UV-Vis and electron energy loss spectroscopies, transmission electron microscopy and density functional theory calculations.
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High-quality AB-stacked bilayer or multilayer graphene larger than a centimetre has not been reported. Here, we report the fabrication and use of single-crystal Cu/Ni(111) alloy foils with controllable concentrations of Ni for the growth of large-area, high-quality AB-stacked bilayer and ABA-stacked trilayer graphene films by chemical vapour deposition. The stacking order, coverage and uniformity of the graphene films were evaluated by Raman spectroscopy and transmission electron microscopy including selected area electron diffraction and atomic resolution imaging. Electrical transport (carrier mobility and band-gap tunability) and thermal conductivity (the bilayer graphene has a thermal conductivity value of about 2,300 W m-1 K-1) measurements indicated the superior quality of the films. The tensile loading response of centimetre-scale bilayer graphene films supported by a 260-nm thick polycarbonate film was measured and the average values of the Young's modulus (478 GPa) and fracture strength (3.31 GPa) were obtained.
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Epitaxial graphene grown on single crystal Cu(111) foils by chemical vapor deposition is found to be free of wrinkles and under biaxial compressive strain. The compressive strain in the epitaxial regions (0.25-0.40%) is higher than regions where the graphene is not epitaxial with the underlying surface (0.20-0.25%). This orientation-dependent strain relaxation is through the loss of local adhesion and the generation of graphene wrinkles. Density functional theory calculations suggest a large frictional force between the epitaxial graphene and the Cu(111) substrate, and this is therefore an energy barrier to the formation of wrinkles in the graphene. Enhanced chemical reactivity is found in epitaxial graphene on Cu(111) foils as compared to graphene on polycrystalline Cu foils for certain chemical reactions. A higher compressive strain possibly favors lowering the formation energy and/or the energy gap between the initial and transition states, either of which can lead to an increase in chemical reactivity.
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Camphor is used to transfer centimeter-scale ultrathin films onto custom-designed substrates for mechanical (tensile) testing. Compared to traditional transfer methods using dissolving/peeling to remove the support-layers, camphor is sublimed away in air at low temperature, thereby avoiding additional stress on the as-transferred films. Large-area ultrathin films can be transferred onto hollow substrates without damage by this method. Tensile measurements are made on centimeter-scale 300 nm-thick graphene oxide film specimens, much thinner than the ≈2 µm minimum thickness of macroscale graphene-oxide films previously reported. Tensile tests were also done on two different types of large-area samples of adlayer free CVD-grown single-layer graphene supported by a ≈100 nm thick polycarbonate film; graphene stiffens this sample significantly, thus the intrinsic mechanical response of the graphene can be extracted. This is the first tensile measurement of centimeter-scale monolayer graphene films. The Young's modulus of polycrystalline graphene ranges from 637 to 793 GPa, while for near single-crystal graphene, it ranges from 728 to 908 GPa (folds parallel to the tensile loading direction) and from 683 to 775 GPa (folds orthogonal to the tensile loading direction), demonstrating the mechanical performance of large-area graphene in a size scale relevant to many applications.
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Fast-growth of single crystal monolayer graphene by CVD using methane and hydrogen has been achieved on "homemade" single crystal Cu/Ni(111) alloy foils over large area. Full coverage was achieved in 5 min or less for a particular range of composition (1.3 at.% to 8.6 at.% Ni), as compared to 60 min for a pure Cu(111) foil under identical growth conditions. These are the bulk atomic percentages of Ni, as a superstructure at the surface of these foils with stoichiometry Cu6Ni1 (for 1.3 to 7.8 bulk at.% Ni in the Cu/Ni(111) foil) was discovered by low energy electron diffraction (LEED). Complete large area monolayer graphene films are either single crystal or close to single crystal, and include folded regions that are essentially parallel and that were likely wrinkles that "fell over" to bind to the surface; these folds are separated by large, wrinkle-free regions. The folds occur due to the buildup of interfacial compressive stress (and its release) during cooling of the foils from 1075 °C to room temperature. The fold heights measured by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) prove them to all be 3 layers thick, and scanning electron microscopy (SEM) imaging shows them to be around 10 to 300 nm wide and separated by roughly 20 µm. These folds are always essentially perpendicular to the steps in this Cu/Ni(111) substrate. Joining of well-aligned graphene islands (in growths that were terminated prior to full film coverage) was investigated with high magnification SEM and aberration-corrected high-resolution transmission electron microscopy (TEM) as well as AFM, STM, and optical microscopy. These methods show that many of the "join regions" have folds, and these arise from interfacial adhesion mechanics (they are due to the buildup of compressive stress during cool-down, but these folds are different than for the continuous graphene films-they occur due to "weak links" in terms of the interface mechanics). Such Cu/Ni(111) alloy foils are promising substrates for the large-scale synthesis of single-crystal graphene film.
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Single-crystal metals have distinctive properties owing to the absence of grain boundaries and strong anisotropy. Commercial single-crystal metals are usually synthesized by bulk crystal growth or by deposition of thin films onto substrates, and they are expensive and small. We prepared extremely large single-crystal metal foils by "contact-free annealing" from commercial polycrystalline foils. The colossal grain growth (up to 32 square centimeters) is achieved by minimizing contact stresses, resulting in a preferred in-plane and out-of-plane crystal orientation, and is driven by surface energy minimization during the rotation of the crystal lattice followed by "consumption" of neighboring grains. Industrial-scale production of single-crystal metal foils is possible as a result of this discovery.
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Commercialization of organic solar cell (OSC) has faltered due to their low power conversion efficiency (PCE) compared to inorganic solar cell. Low electrical conductivity, low charge mobility, and short-range light absorption of most organic materials limit the PCE of OSCs. Carbon nanomaterials, especially carbon nanotubes (CNTs) and graphenes, are of great interest for use in OSC applications due to their high electrical conductivity, mobility, and unique optical properties for enhancing the performance of OSCs. In this review, recent progress toward the integration of carbon nanomaterials into OSCs is described. The role of carbon nanomaterials and strategies for their integration into various layers of OSCs, including the photoactive layer and charge transport layer, are discussed. Based on these, we also discuss the prospects of carbon nanomaterials for specific OSC layers to maximize the PCE.
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Carbon nanotubes (CNTs) and graphene are known to be good conductive fillers due to their favorable electrical properties and high aspect ratios and have been investigated for application as stretchable composite conductors. A stretchable conducting nanocomposite should have a small fraction of conductive filler material to maintain stretchability. Here we demonstrate enhanced electrical networks of nanocomposites via the use of a CNT-graphene hybrid system using a small mass fraction of conductive filler. The CNT-graphene hybrid system exhibits synergistic effects that prevent agglomeration of CNTs and graphene restacking and reduce contact resistance by formation of 1D(CNT)-2D(graphene) interconnection. These effects resulted in nanocomposite materials formed of multiwalled carbon nanotubes (MWCNTs), thermally reduced graphene (TRG), and polydimethylsiloxane (PDMS), which had a higher electrical conductivity compared with MWCNT/PDMS or TRG/PDMS nanocomposites until specific fraction that is sufficient to form electrical network among conductive fillers. These nanocomposite materials maintained their electrical conductivity when 60% strained.
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The CNT-SiO2 core-shell structure is particularly appealing because the insulating SiO2 layer wraps around the CNTs, functioning as a gate dielectric. However, it is still a challenge to expose both end-caps of the structure for enabling them to serve as electrodes, which additionally requires complicated postprocesses. Here, we present a unique CNTs-SiO2 core-shell structure where both ends are uncovered with SiO2 in a "peeled-wire" structure. In this structure, SiO2 particles partially encapsulate the CNTs during the synthesis, resulting in both end-caps of the nanotube being self-exposed and electrically conductive. The field-effect transistor build-up with this structure exhibits p-type characteristics with a linear conductance behavior on Id-Vd output performance. This approach for making self-formed electrodes in the CNT-SiO2 core-shell structure provides a simple and efficient way for applying them to future nanodevices in terms of process simplicity and cost effectiveness.