We report on scanning tunneling microscopy and spectroscopy of grain boundaries in highly oriented pyrolytic graphite. Grain boundaries showed a periodic structure and an enhanced charge density compared to the bare graphite surface. Two possible periodic structures have been observed along grain boundaries. A geometrical model producing periodically distributed point defects on the basal plane of graphite has been proposed to explain the structure of grain boundaries. Scanning tunneling spectroscopy on grain boundaries revealed two strong localized states at -0.3 V and 0.4 V.
It has been found that periodically closely spaced vacancies on a graphite sheet cause a significant rearrange-ment of its electronic spectrum: metallic waveguides with a high density of states near the Fermi level are formed along the vacancy lines. In the direction perpendicular to these lines, the spectrum exhibits a semimetal or semiconductor character with a gap where a vacancy miniband is degenerated into impurity levels.
Employing graphites having distinctly different mean grain sizes, we study the effects of polycrystallinity on the pattern formation by ion-beam-sputtering. The grains influence the growth of the ripples in highly anisotropic fashion; Both the mean uninterrupted ripple length along its ridge and the surface width depend on the mean size of the grains, which is attributed to the large sputter yield at the grain boundary compared with that on terrace. In contrast, the ripple wavelength does not depend on the mean size of the grains. Coarsening of the ripples-accompanying the mass transport acros…
Dislocations are a central concept in materials science, which dictate the plastic deformation and damage evolution in materials. Layered materials such as graphite admit two general types of interlayer dislocations: basal and prismatic dislocations, of which prismatic dislocations have been relatively less studied. Using density functional theory (DFT) calculations, we have examined different prismatic core structures in graphite and evaluated their structure, energetics and mobility. We find close energetic interplay between bonded and "free-standing" core structures in both zigzag and armch…
We demonstrate direct evidence for ferromagnetic order at defect structures in highly oriented pyrolytic graphite with magnetic force microscopy at room temperature. Magnetic impurities have been excluded as the origin of the magnetic signal after careful analysis supporting an intrinsic magnetic behavior of carbon-based materials. The observed ferromagnetism has been attributed to originate from unpaired electron spins localized at grain boundaries. Scanning tunneling spectroscopy of grain boundaries showed intense localized states and enhanced charge density compared to bare graphite.
The grain boundaries (GBs) of a graphene surface were extensively studied because GBs with specific defect configurations result in the formation of new curved structures, which can be treated as new carbon allotropes. We studied the structures and electronic spectra of two periodic GBs in graphene on highly oriented pyrolytic graphite (HOPG) surfaces using scanning tunneling microscopy and spectroscopy (STM/S). Our results demonstrated that a GB consisting of dual parallel periodic dislocation cores of pentagonal-heptagonal (5-7) carbon rings gives rise to an enhanced localized state at 0.45 …
Trying to dope graphite flakes we found that the magnetization of pure, several tens of micrometers grain size graphite powder and after a simple treatment with pure water shows clear and reproducible granular superconducting behavior with a critical temperature above 300K. The observed magnetic characteristics as a function of temperature, magnetic field and time, provide evidence for weakly coupled grains through Josephson interaction, revealing the existence of superconducting vortices.
A method to produce suspensions of graphene sheets by combining solution-based bromine intercalation and mild sonochemical exfoliation is presented. Ultrasonic treatment of graphite in water leads to the formation of suspensions of graphite flakes. The delamination is dramatically improved by intercalation of bromine into the graphite before sonication. The bromine intercalation was verified by Raman spectroscopy as well as by x-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations show an almost ten times lower interlayer binding energy after introducing Br2 i…
Ferromagnetism in carbon-based materials is appealing for both applications and fundamental science purposes because carbon is a light and bio-compatible material that contains only s and p electrons in contrast to traditional ferromagnets based on 3d or 4f electrons. Here we demonstrate direct evidence for ferromagnetic order locally at defect structures in highly oriented pyrolytic graphite (HOPG) with magnetic force microscopy and in bulk magnetization measurements at room temperature. Magnetic impurities have been excluded as the origin of the magnetic signal after careful analysis support…
Experiments with multiwalled carbon nanotubes and graphite as targets in a source of negative ions with cesium sputtering have shown that nanotubes with nanometer radii and micrometer length can be compared with micrometer size graphite grains to understand the irradiation effects that include the formation, sputtering of carbon clusters and the resulting structural changes. The simultaneous adsorption of cesium on the surface and bombardment by energetic cesium ions is shown to play its role in the cluster formation and sputtering of carbon atoms and clusters and the cesium substituted carbon…
The transport properties of highly oriented pyrolitic graphite (HOPG) and polycrystal graphite have been studied. The electric conductivity of HOPG is several times larger than that of the polycrystal graphite. Along with the large magnetoresistances (MR), the polycrystal graphite show the accordant semiconductor-like character in a wide temperature (roughly range from 20K to 120K) under 0, 4, 8, 12 T applied magnetic field, while the magnetic-field-induced metal-semiconductor-like transition was only found in HOPG. The difference of transport properties originates from the Coulomb interaction…
We have observed periodically repeated steps in the resistance vs. temperature characteristics of doped Highly Oriented Pyrolytic Graphite and exfoliated doped multi-layer graphene. The observations consist of a series of regularly spaced steps in the resistance vs. temperature curves. The lowest step is observed at a temperature of from 50 to 60 K. Additional steps are observed at multiples of that basic temperature with the highest step temperature being at approximately 270 K. Quenching by a modest applied magnetic field has been observed. The sizes and widths of the observed steps appear t…
Of the ``presolar particles'' extracted from carbonaceous chondrite dissolution residues, i.e. of those particles which show isotopic evidence of solidification in the neighborhood of other stars prior to the origin of our solar system, one subset has an interesting concentric graphite-rim/graphene-core structure. We show here that single graphene sheet defects in the onion cores (e.g. cyclopentane loops) may be observable edge-on by HREM. This could allow a closer look at models for their formation, and in particular strengthen the possibility that growth of these assemblages proceeds atom-by…
We describe the results of atomic-level stick-slip friction measurements performed on chemically-modified graphite, using atomic force microscopy (AFM). Through detailed molecular dynamics simulations, coarse-grained simulations, and theoretical arguments, we report on complex indentation profiles during AFM scans involving local reversible exfoliation of the top layer of graphene from the underlying graphite sample and its effect on the measured friction force during retraction of the scanning tip. In particular, we report nearly constant lateral stick-slip magnitudes at decreasing loads, whi…
We have investigated atomic and electronic structure of grain boundaries in monolayer MoS2, where relative angles between two different grains are 0 and 60 degree. The grain boundaries with specific relative angle have been formed with chemical vapor deposition growth on graphite and hexagonal boron nitride flakes; van der Waals interlayer interaction between MoS2 and the flakes restricts the relative angle. Through scanning tunneling microscopy and spectroscopy measurements, we have found that the perfectly stitched structure between two different grains of MoS2 was realized in the case of th…
In the last decades severe plastic deformation techniques have gained increasing interest as they allow the production of bulk nanostructured materials with superior mechanical and functional properties. However, because of mechanically induced grain boundary migration, the achievable grain size reduction is not indefinite but tends to stagnate once sufficient strain has been applied. Consequently, addition of solute elements or second phase particles offers the possibility to access the true nanocrystalline regime. Due to their low solubility and high mobility, interstitial elements are extre…
We reveal that phononic thermal transport in graphene is not immune to grain boundaries (GBs) aligned along the direction of the temperature gradient. Non-equilibrium molecular dynamics simulations uncover a large reduction in the phononic thermal conductivity ($κ_p$) along linear ultra-narrow GBs comprising periodically-repeating pentagon-heptagon dislocations. Green's function calculations and spectral energy density analysis indicate that $κ_p$ is the complex manifestation of the periodic strain field, which behaves as a reflective diffraction grating with both diffuse and specular phonon r…
Despite the structures and properties of tilt grain boundaries of graphite surface and graphene have been extensively studied, their effect on the structures and electronic spectra of graphene layers has not been fully addressed. Here we study effects of one-dimensional tilt grain boundaries on structures and electronic spectra of graphene multilayers by scanning tunneling microscopy and spectroscopy. A tilt grain boundary of a top graphene sheet in graphene multilayers leads to a twist between consecutive layers and generates superstructures (Moiré patterns) on one side of the boundary. Our r…
The architectures of biological hard materials reveal finely tailored complex assemblies of mineral crystals. Numerous recent studies associate the design of these local assemblies with impressive macroscopic response. Reproducing such exquisite control in technical ceramics conflicts with commonly used processing methods. Here, we circumvent this issue by combining the recently developed Magnetically-Assisted Slip Casting (MASC) technique with the well-established process of Templated Grain Growth (TGG). MASC enables the local control over the orientation of platelets dispersed among smaller …
We present an ultra-high vacuum scanning tunneling microscopy (STM) study of structural defects in molybdenum disulfide thin films grown on silicon substrates by chemical vapor deposition. A distinctive type of grain boundary periodically arranged inside an isolated triangular domain, along with other inter-domain grain boundaries of various types, is observed. These periodic defects, about 50 nm apart and a few nanometers in width, remain hidden in optical or low-resolution microscopy studies. We report a complex growth mechanism that produces 2D nucleation and spiral growth features that can…
We use molecular dynamics simulations to explore the impact of a non-ionic solvent on the structural and capacitive properties of supercapacitors based on an ionic liquid electrolyte and carbon electrodes. The study is focused on two pure ionic liquids, namely 1-butyl-3-methylimidazolium hexafluorophosphate and 1-butyl-3-methylimidazolium tetrafluoroborate, and their 1.5 M solutions in acetonitrile. The electrolytes, represented by coarse-grained models, are enclosed between graphite electrodes. We employ a constant potential methodology which allows us to gain insight into the influence of so…
In this study, the impurity concentration and magnetic response of nine highly oriented pyrolytic graphite (HOPG) samples with different grades and from different providers were determined using ion beam microscopy and SQUID magnetometry. Apart from sideface contaminations in the as-received state, bulk contamination of the samples in most cases consists of disk-shaped micron-sized particles made of Ti and V with an additional Fe contamination around the grain perimeter. The saturation magnetization typically increases with Fe concentration, however, there is no simple correlation between Fe c…
