Effect of Sample Geometry on Graphitization of Polyacrylonitrile.

In this study, it is analyzed how sample geometry (spheres, nanofibers, or films) influences the graphitization behavior of polyacrylonitrile (PAN) molecules. The chemical bonding and changes in the composition of these three geometries are studied at the oxidation, carbonization, and graphitization stages via scanning electron microscopy (SEM), in situ thermogravimetric-infrared (TGA-IR) analysis, elemental analysis, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The influence of molecular alignment on the graphitization of the three sample geometries is investigated using synchrotron wide-angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM). The effects of molecular alignment at different draw rates during spinning are explored in detail.

Growth of diamond in liquid metal at 1 atm pressure.

Natural diamonds were (and are) formed (thousands of million years ago) in the upper mantle of Earth in metallic melts at temperatures of 900-1,400 °C and at pressures of 5-6 GPa (refs. 1,2). Diamond is thermodynamically stable under high-pressure and high-temperature conditions as per the phase diagram of carbon3. Scientists at General Electric invented and used a high-pressure and high-temperature apparatus in 1955 to synthesize diamonds by using molten iron sulfide at about 7 GPa and 1,600 °C (refs. 4-6). There is an existing model that diamond can be grown using liquid metals only at both high pressure and high temperature7. Here we describe the growth of diamond crystals and polycrystalline diamond films with no seed particles using liquid metal but at 1 atm pressure and at 1,025 °C, breaking this pattern. Diamond grew in the subsurface of liquid metal composed of gallium, iron, nickel and silicon, by catalytic activation of methane and diffusion of carbon atoms into and within the subsurface regions. We found that the supersaturation of carbon in the liquid metal subsurface leads to the nucleation and growth of diamonds, with Si playing an important part in stabilizing tetravalently bonded carbon clusters that play a part in nucleation. Growth of (metastable) diamond in liquid metal at moderate temperature and 1 atm pressure opens many possibilities for further basic science studies and for the scaling of this type of growth.

3D microprinting of inorganic porous materials by chemical linking-induced solidification of nanocrystals.

Three-dimensional (3D) microprinting is considered a next-generation manufacturing process for the production of microscale components; however, the narrow range of suitable materials, which include mainly polymers, is a critical issue that limits the application of this process to functional inorganic materials. Herein, we develop a generalised microscale 3D printing method for the production of purely inorganic nanocrystal-based porous materials. Our process is designed to solidify all-inorganic nanocrystals via immediate dispersibility control and surface linking-induced interconnection in the nonsolvent linker bath and thereby creates multibranched gel networks. The process works with various inorganic materials, including metals, semiconductors, magnets, oxides, and multi-materials, not requiring organic binders or stereolithographic equipment. Filaments with a diameter of sub-10 µm are printed into designed complex 3D microarchitectures, which exhibit full nanocrystal functionality and high specific surface areas as well as hierarchical porous structures. This approach provides the platform technology for designing functional inorganics-based porous materials.

Protocol for the electrochemical polymerization of polyhydrocarbons from chlorinated methanes and an analysis of its polymerization reaction pathway.

The mass production of polyhydrocarbons (PHCs) is achieved through electrochemical polymerization and its synthetic pathway is investigated using a combination of electrochemical techniques, NMR, and Fourier transform infrared (FTIR) spectroscopy. Here, we present a protocol for the electrochemical polymerization of PHCs from chlorinated methanes and an analysis of its polymerization reaction pathway. We describe steps for large-scale synthesis and characterization of PHCs and studying electrochemical polymerization reactions using cyclic voltammetry and chronoamperometry techniques along with NMR and FTIR spectroscopy using isotope-labeled reactants. For complete details on the use and execution of this protocol, please refer to Seo et al.,1 Lee et al.,2 and Seo et al.3.

Direct Electrochemical Functionalization of Graphene Grown on Cu Including the Reaction Rate Dependence on the Cu Facet Type.

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.

Growth Mechanism and Kinetics of Diamond in Liquid Gallium from Quantum Mechanics Molecular Dynamics Simulations.

Ruoff and co-workers recently demonstrated low-temperature (1193 K) homoepitaxial diamond growth from liquid gallium solvent. To develop an atomistic mechanism for diamond growth underlying this remarkable demonstration, we carried out density functional theory-based molecular dynamics (DFT-MD) simulations to examine the mechanism of single-crystal diamond growth on various low-index crystallographic diamond surfaces (100), (110), and (111) in liquid Ga with CH4. We find that carbon linear chains form in liquid Ga and then react with the growing diamond surface, leading first to the formation of carbon rings on the surface and then initiation of diamond growth. Our simulations find faster growth on the (110) surface than on the (100) or (111) surfaces, suggesting the (110) surface as a plausible growth surface in liquid Ga. For (110) surface growth, we predict the optimum growth temperature to be ∼1300 K, arising from a balance between the kinetics of forming carbon chains dissolved in Ga and the stability of carbon rings on the growing surface. We find that the rate-determining step for diamond growth is dehydrogenation of the growing hydrogenated (110) surface of diamond. Inspired by the recent experimental studies by Ruoff and co-workers demonstrating that Si accelerates diamond growth in Ga, we show that addition of Si into liquid Ga significantly increases the rate of dehydrogenating the growing surface. Extrapolating from the DFT-MD predicted rates at 2800 to 3500 K, we predict the growth rate at the experimental growth temperature of 1193 K, leading to rates in reasonable agreement with the experiment. These fundamental mechanisms should provide guidance in optimizing low-temperature diamond growth.

Long-range ordered porous carbons produced from C60.

Carbon structures with covalent bonds connecting C60 molecules have been reported1-3, but their production methods typically result in very small amounts of sample, which restrict the detailed characterization and exploration necessary for potential applications. We report the gram-scale preparation of a new type of carbon, long-range ordered porous carbon (LOPC), from C60 powder catalysed by α-Li3N at ambient pressure. LOPC consists of connected broken C60 cages that maintain long-range periodicity, and has been characterized by X-ray diffraction, Raman spectroscopy, magic-angle spinning solid-state nuclear magnetic resonance spectroscopy, aberration-corrected transmission electron microscopy and neutron scattering. Numerical simulations based on a neural network show that LOPC is a metastable structure produced during the transformation from fullerene-type to graphene-type carbons. At a lower temperature, shorter annealing time or by using less α-Li3N, a well-known polymerized C60 crystal forms owing to the electron transfer from α-Li3N to C60. The carbon K-edge near-edge X-ray absorption fine structure shows a higher degree of delocalization of electrons in LOPC than in C60(s). The electrical conductivity is 1.17 × 10-2 S cm-1 at room temperature, and conduction at T < 30 K appears to result from a combination of metallic-like transport over short distances punctuated by carrier hopping. The preparation of LOPC enables the discovery of other crystalline carbons starting from C60(s).

Decoupling of CVD-grown epitaxial graphene using NaCl intercalation.

The structural and electronic properties of graphene grown on catalytic metal surfaces are significantly modified via graphene-substrate interaction. To minimize the influence of the metal substrate, a dielectric buffer layer can be introduced between the graphene and metal substrate. However, the catalytic synthesis of graphene limits the potential alternatives for buffer layers. The intercalation of atoms below the graphene layer is a promising method that does not require the chemical treatment of graphene or the substrate. In this study, the electronic and structural properties of single-layer graphene (SLG) on the Cu(111) substrate intercalated with ultrathin NaCl thin films were investigated using scanning tunnelling microscopy. The intercalation of the NaCl monolayer decoupled SLG from the metal substrate, thereby producing quasi-freestanding graphene.

Using Single-Crystal Graphene to Form Arrays of Nanocapsules Enabling the Observation of Light Elements in Liquid Cell Transmission Electron Microscopy.

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.

Epitaxial single-crystal hexagonal boron nitride multilayers on Ni (111).

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.

Silica Particle-Mediated Growth of Single Crystal Graphene Ribbons on Cu(111) Foil.

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.

Single-crystal two-dimensional material epitaxy on tailored non-single-crystal substrates.

The use of single-crystal substrates as templates for the epitaxial growth of single-crystal overlayers has been a primary principle of materials epitaxy for more than 70 years. Here we report our finding that, though counterintuitive, single-crystal 2D materials can be epitaxially grown on twinned crystals. By establishing a geometric principle to describe 2D materials alignment on high-index surfaces, we show that 2D material islands grown on the two sides of a twin boundary can be well aligned. To validate this prediction, wafer-scale Cu foils with abundant twin boundaries were synthesized, and on the surfaces of these polycrystalline Cu foils, we have successfully grown wafer-scale single-crystal graphene and hexagonal boron nitride films. In addition, to greatly increasing the availability of large area high-quality 2D single crystals, our discovery also extends the fundamental understanding of materials epitaxy.

Encoding Enantiomeric Molecular Chiralities on Graphene Basal Planes.

Graphene has demonstrated broad applications due to its prominent properties. Its molecular structure makes graphene achiral. Here, we propose a direct way to prepare chiral graphene by transferring chiral structural conformation from chiral conjugated amino acids onto graphene basal plane through π-π interaction followed by thermal fusion. Using atomic resolution transmission electron microscopy, we estimated an areal coverage of the molecular imprints (chiral regions) up to 64 % on the basal plane of graphene (grown by chemical vapor deposition). The high concentration of molecular imprints in their single layer points to a close packing of the deposited amino acid molecules prior to "thermal fusion". Such "molecular chirality-encoded graphene" was tested as an electrode in electrochemical enantioselective recognition. The chirality-encoded graphene might find use for other chirality-related studies and the encoding procedure might be extended to other two-dimensional materials.

Folding and Fracture of Single-Crystal Graphene Grown on a Cu(111) Foil.

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.

Wafer-scale single-crystal monolayer graphene grown on sapphire substrate.

The growth of inch-scale high-quality graphene on insulating substrates is desirable for electronic and optoelectronic applications, but remains challenging due to the lack of metal catalysis. Here we demonstrate the wafer-scale synthesis of adlayer-free ultra-flat single-crystal monolayer graphene on sapphire substrates. We converted polycrystalline Cu foil placed on Al2O3(0001) into single-crystal Cu(111) film via annealing, and then achieved epitaxial growth of graphene at the interface between Cu(111) and Al2O3(0001) by multi-cycle plasma etching-assisted-chemical vapour deposition. Immersion in liquid nitrogen followed by rapid heating causes the Cu(111) film to bulge and peel off easily, while the graphene film remains on the sapphire substrate without degradation. Field-effect transistors fabricated on as-grown graphene exhibited good electronic transport properties with high carrier mobilities. This work breaks a bottleneck of synthesizing wafer-scale single-crystal monolayer graphene on insulating substrates and could contribute to next-generation graphene-based nanodevices.

Large-Area Uniform 1-nm-Level Amorphous Carbon Layers from 3D Conformal Polymer Brushes. A "Next-Generation" Cu Diffusion Barrier?

A reliable method for preparing a conformal amorphous carbon (a-C) layer with a thickness of 1-nm-level, is tested as a possible Cu diffusion barrier layer for next-generation ultrahigh-density semiconductor device miniaturization. A polystyrene brush of uniform thickness is grafted onto 4-inch SiO2 /Si wafer substrates with "self-limiting" chemistry favoring such a uniform layer. UV crosslinking and subsequent carbonization transforms this polymer film into an ultrathin a-C layer without pinholes or hillocks. The uniform coating of nonplanar regions or surfaces is also possible. The Cu diffusion "blocking ability" is evaluated by time-dependent dielectric breakdown (TDDB) tests using a metal-oxide-semiconductor (MOS) capacitor structure. A 0.82 nm-thick a-C barrier gives TDDB lifetimes 3.3× longer than that obtained using the conventional 1.0 nm-thick TaNx diffusion barrier. In addition, this exceptionally uniform ultrathin polymer and a-C film layers hold promise for selective ion permeable membranes, electrically and thermally insulating films in electronics, slits of angstrom-scale thickness, and, when appropriately functionalized, as a robust ultrathin coating with many other potential applications.

Proton affinity and gas phase basicity of diamandoid molecules: diamantane to C131H116.

Calculated proton affinities (PAs) and gas phase basicities (GPBs) are reported for diamantane (C14H20), triamantane (C18H24), 'globular and planar' isomers of tetramantane (C22H28) and pentamantane (C26H32), and for one 'globular' isomer of each of the larger diamondoid molecules: C51H58, C78H72, C102H90, and C131H116. Assuming CxHy as the parent diamondoid molecule, we calculated PA and GPB values for a variety of CxHy+1+ isomers, as well as for the reaction CxHy + H+ yielding CxHy-1+ + H2(g); the latter is slightly favored based on GPB values for diamantane through pentamantane, but less favored compared to certain CxHy+1+ isomers of C51H58, C102H90, and C131H116. Indeed, the GPB values of C51H58, C102H90, and C131H116 classifiy them as 'superbases'. Calculations that had the initial location of the proton in an interstitial site inside the diamondoid molecule always showed the H having moved to the outside of the diamondoid molecule; for this reason, we focused on testing a variety of initial configurations with the proton placed in an initial position on the surface. Additional protons were added to determine the limiting number that could be, per these calculations, taken up by the diamondoid molecules and the maximum number of protons are shown in parentheses: C14H20(2), C18H24(3), C22H28(3), C26H32(3), C51H58(4). Bader charge distributions obtained for CxHy+1+ isomers (for diamantane through pentamantane) suggest that the positive charge is essentially completely delocalized over all the H atoms. NMR spectra were calculated for different isomers of C14H19+, and compared to the published NMR spectrum for when diamantane was mixed with magic acid and H2(g) was produced.

Multifunctional Macroassembled Graphene Nanofilms with High Crystallinity.

A "cooling-contraction" method to separate large-area (up to 4.2 cm in lateral size) graphene oxide (GO)-assembled films (of nanoscale thickness) from substrates is reported. Heat treatment at 3000 °C of such free-standing macroscale films yields highly crystalline "macroassembled graphene nanofilms" (nMAGs) with 16-48 nm thickness. These nMAGs present tensile strength of 5.5-11.3 GPa (with ≈3 µm gauge length), electrical conductivity of 1.8-2.1 MS m-1 , thermal conductivity of 2027-2820 W m-1 K-1 , and carrier relaxation time up to ≈23 ps. As a demonstration application, an nMAG-based sound-generator shows a 30 µs response and sound pressure level of 89 dB at 1 W cm-2 . A THz metasurface fabricated from nMAG has a light response of 8.2% for 0.159 W mm-2 and can detect down to 0.01 ppm of glucose. The approach provides a straightforward way to form highly crystallized graphene nanofilms from low-cost GO sheets.

Single-crystal, large-area, fold-free monolayer graphene.

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.