Two-particle spectroscopy with correlated electron pairs is used to establish the causal link between the secondary electron spectrum, the $(π+σ)-$plasmon peak and the unoccupied band structure of highly oriented pyrolitic graphite. The plasmon spectrum is resolved with respect to the involved interband transitions and clearly exhibits final state effects, in particular due to the energy gap between the interlayer resonances along the $Γ$A-direction. The corresponding final state effects can also be identified in the secondary electron spectrum. Interpretation of the results is performed on the basis of density functional theory and tight binding calculations. Excitation of the plasmon perturbs the symmetry of the system and leads to hybridisation of the interlayer resonances with atom-like $σ^*$ bands along the $ΓA$-direction. These hybrid states have a high density of states as well as sufficient mobility along the graphite $c$-axis leading to the sharp $\sim$3\ eV resonance in the spectrum of emitted secondary electrons reported throughout the literature.
Mechanical exfoliation is a widely used method to isolate high quality graphene layers from bulk graphite. In our recent experiments, some ordered microstructures, consisting of a periodic alternation of kinks and stripes, were observed in thin graphite flakes that were mechanically peeled from highly oriented pyrolytic graphite (HOPG). A theoretical model is presented in this paper to understand the formation of such ordered microstructures, based on elastic buckling of a graphite flake being subjected to a bending moment. The width of the stripes predicted from this model agrees reasonably w…
We investigate the optical properties of bromine intercalated highly orientated pyrolytic graphite (Br-HOPG) and provide a novel interpretation of the data. We observe new absorption features below 620 meV which are absent in the absorption spectrum of graphite. Comparing our results with those of theoretical studies on graphite, single and bilayer graphene as well as recent optical studies of multilayer graphene, we conclude that Br-HOPG contains the signatures of ultrapure bilayer, single layer graphene, and graphite. The observed supermetallic conductivity of Br-HOPG is identified with the …
Highly oriented pyrolytic graphite (HOPG) has been widely used as monochromators, analyzers and filters at neutron and X-ray scattering facilities. In this Letter we report the first observation of an anomalous neutron Halo scattering of HOPG. The scattering projects a ring onto the detector with half cone angle of 12.4 degree that surprisingly persists to incident neutron wavelengths far beyond the Bragg cutoff for graphite (6.71 A). At longer wavelengths the ring is clearly a doublet with a splitting roughly proportional to wavelength. While the ring centers at the beam position if the beam …
We have investigated the variation in the magnetization of highly ordered pyrolytic graphite (HOPG) after neutron irradiation, which introduces defects in the bulk sample and consequently gives rise to a large magnetic signal. We observe strong paramagnetism in HOPG, increasing with the neutron fluence. We correlate the induced paramagnetism with structural defects by comparison with density-functional theory calculations. In addition to the in-plane vacancies, the trans-planar defects also contribute to the magnetization. The lack of any magnetic order between the local moments is possibly du…
We investigated the influence of thickness reduction on the transport properties of graphite microflakes. Using oxygen plasma etching we decreased the thickness of highly oriented pyrolytic graphite (HOPG) microflakes from $\sim 100$~nm to $\sim 20$~nm systematically. Keeping current and voltage electrodes intact, the electrical resistance $R(T)$, the magnetoresistance (MR) and Raman spectra were measured in every individual sample and after each etching step of a few nm. The results show that $R(T)$ and MR can increase or decrease with the sample thickness in a non-systematic way. The results…
Highly oriented pyrolitic graphite (HOPG) is an inert substrate with a structural honeycomb lattice, well suited for the growth of two-dimensional (2D) silicene layer. It was reported that when Si atoms are deposited on HOPG surface at room temperature, they arrange in two configurations: silicene nanosheets and three dimensional clusters. In this work we demonstrate, by using scanning tunneling microscopy (STM) and Raman spectroscopy, that a third configuration stabilizes in the form of Si 2D nanosheets intercalated below the first top layer of carbon atoms. The Raman spectra reveal a structu…
We manipulate the transient terahertz (THz) waves emitted from metal-graphite interfaces, where potential barriers were formed because of work function differences. To adaptively control the phase of the THz waves, two distinct groups of metals were evaporated on n-type doped highly oriented pyrolytic graphite (HOPG): group A, which consisted of Pt, Au, and Ag with work functions larger than that of HOPG and group B, which consisted of Al and Ti with work functions smaller than that of HOPG. The phase of the transient THz lineshapes from group A was opposite to that of group B under infrared l…
We use the tip of the scanning tunneling microscope (STM) to manipulate single weakly bound nanometer-sized sheets on the the highly oriented pyrolytic graphite (HOPG) surface through artifically increasing the tip and sample interaction in humid environment. By this means it is possible to tear apart a graphite sheet againt a step and fold this part onto the HOPG surface and thus generate the gaphene superlattices with hexagonal symmetry. The tip and sample surface interactions, including the van der Waals force, eletrostatic force and capillary attraction force originating from the Laplace p…
Highly oriented pyrolytic graphite (HOPG) is an important substrate in many technological applications and is routinely used as a standard in Scanning Tunnelling Microscopy (STM) calibration, which makes the accurate interpretation of the HOPG STM contrast of great fundamental and applicative importance. We demonstrate by STM simulations based on electronic structure obtained from first principles that the relative local orientation of the STM-tip apex with respect to the HOPG substrate has a considerable effect on the HOPG STM contrast. Importantly for experimental STM analysis of HOPG, the s…
We report the successful growth of high-quality SrO films on highly-ordered pyrolytic graphite (HOPG) and single-layer graphene by molecular beam epitaxy. The SrO layers have (001) orientation as confirmed by x-ray diffraction (XRD) while atomic force microscopy measurements show continuous pinhole-free films having rms surface roughness of <1.5 Å. Transport measurements of exfoliated graphene after SrO deposition show a strong dependence between the Dirac point and Sr oxidation. Subsequently, the SrO is leveraged as a buffer layer for more complex oxide integration via the demonstration of (0…
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…
We report on an extensive investigation to figure out the origin of room-temperature ferromagnetism that is commonly observed by SQUID magnetometry in highly-oriented pyrolytic graphite (HOPG). Electron backscattering and X-ray microanalysis revealed the presence of micron-size magnetic clusters (predominantly Fe) that are rare and would be difficult to detect without careful search in a scanning electron microscope in the backscattering mode. The clusters pin to crystal boundaries and their quantities match the amplitude of typical ferromagnetic signals. No ferromagnetic response is detected …
Superperiodic patterns were observed by STM on two kinds of finite-sized graphene sheets. One is nanographene sheets inclined from a highly oriented pyrolitic graphite (HOPG) substrate and the other is several-layer-thick graphene sheets with dislocation-network structures against a HOPG substrate. As for the former, the in-plane periodicity increased gradually in the direction of inclination, and it is easily changed by attachment of a nanographite flake on the nanographene sheets. The oscillation pattern can be explained by the interference of electron waves confined in the inclined nanograp…
Here we report the experimental evidence of the interactions between the excitations of the $π\toπ^*$ optical transition and the image potential states (IPS) of highly oriented pyrolitic graphite (HOPG). By using non-linear angle resolved photoelectron spectroscopy (NL-ARPES) we show that the IPS photoemission intensity, the effective mass, and the linewidth exhibit a strong variation when the photon energy is tuned across the $π\toπ^*$ saddle points in the 3.1 - 4.5 eV photon energy range. A model based on the self-energy formalism is proposed to correlate the effective mass and the linewidth…
We present a comprehensive study of the adsorption of bis(phthalocyaninato)lutetium(III) (LuPc$_2$) on highly oriented pyrolytic graphite(0001) (HOPG). The growth and self-assembly of the molecular layers as well as the electronic structure has been investigated systematically using scanning tunnelling microscopy and scanning tunnelling spectroscopy combined with density functional theory (DFT) calculations and molecular mechanics simulations. We reveal that the adsorption of LuPc$_2$ leads to the formation of a square-like close-packed structure on the almost inert surface of HOPG, which is c…
We explore the structural evolution of highly oriented pyrolytic graphite (HOPG) under detonation-induced shock conditions using in-situ synchrotron X-ray diffraction in the ns time scale. We observe the formation of hexagonal diamond (lonsdaleite) at pressures above 50 GPa, in qualitative agreement with recent gas gun experiments. First-principles density functional calculations reveal that under uniaxial compression the energy barrier for the transition towards hexagonal diamond is lower than cubic diamond. Finally, no indication of cubic diamond formation was observed up to >70 GPa.
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…
Monolayer Tellurium (Te) or tellurene has been suggested by a recent theory as a new two-dimensional (2D) system with great electronic and optoelectronic promises. Here we present an experimental study of epitaxial Te deposited on highly oriented pyrolytic graphite (HOPG) substrate by molecular-beam epitaxy. Scanning tunneling microscopy of ultrathin layers of Te reveals rectangular surface cells with the cell size consistent with the theoretically predicted beta-tellurene, whereas for thicker films, the cell size is more consistent with that of the (10-10) surface of bulk Te crystal. Scanning…
We report on large exciton tuning in WSe$_2$ monolayers via substrate induced non-degenerate doping. We observe a redshift of $\sim$62 meV for the $A$ exciton together with a 1-2 orders of magnitude photoluminescence (PL) quenching when the monolayer WSe$_2$ is brought in contact with highly oriented pyrolytic graphite (HOPG) compared to the dielectric substrates such as hBN and SiO$_2$. As the evidence of doping from HOPG to WSe$_2$, a drastic increase of the trion emission intensity was observed. Using a systematic PL and Kelvin probe force microscopy (KPFM) investigation on WSe$_2$/HOPG, WS…
We demonstrate the organometallic hexahapto complexation of chromium with graphene, graphite and carbon nanotubes. All of these extended periodic pi-electron systems exhibit some degree of reactivity toward the reagents CrCO)6 and (eta6-benzene)Cr(CO)3, and we are able to demonstrate the formation of (eta6-rene)Cr(CO)3 or (eta6-arene)2Cr, where arene = single-walled carbon nanotubes (SWNT), exfoliated graphene (XG), epitaxial graphene (EG) and highly-oriented pyrolytic graphite (HOPG). We find that the SWNTs are the least reactive presumably as a result of the effect of curvature on the format…
Transport properties of a few hundreds of nanometers thick (in the graphene plane direction) lamellae of highly oriented pyrolytic graphite (HOPG) have been investigated. Current-Voltage characteristics as well as the temperature dependence of the voltage at different fixed input currents provide evidence for Josephson-coupled superconducting regions embedded in the internal two-dimensional interfaces, reaching zero resistance at low enough temperatures. The overall behavior indicates the existence of superconducting regions with critical temperatures above 100 K at the internal interfaces of …
Far infrared(FIR) data on the optical properties of graphite are presently lacking. An important step towards filling this gap was taken by Kuzmenko et al. (2008) who measured, on HOPG (Highly Oriented Pyrolitic Graphite) at normal incidence and from 10 to 300 K, the in-plane dielectric functions from 0.3 to 200 mum, and the reflectance between 0.3 and about 300 mum. We show here how, using recent developments of the electron theory of graphene, extended to graphite, it is possible to properly extrapolate the data farther even than 1000 mum, in effect all the way to Direct Current. The plasma …
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 …
In this paper, we present and analyze measurements of the positron induced electron spectra (PIES) from highly oriented pyrolytic graphite (HOPG). The spectra were obtained using a time of flight spectrometer attached to a variable energy positron beam. In the first measurements presented, the system was configured to obtain high resolution data from the annihilation induced KVV Auger transition of carbon. In the second set of data presented, PIES spectra were obtained for 3 different positron beam energies (1.25 eV, 3.5 eV and 4.5 eV). The resulting time of flight (ToF)-PIES exhibit contribut…
Two-dimensional (2D) platinum diselenide (PtSe$_2$) has received significant attention for 2D transistor applications due to its high mobility. Here, using molecular beam epitaxy, we investigate the growth of 2D PtSe$_2$ on highly oriented pyrolytic graphite (HOPG) and unveil their electronic properties via X-ray photoelectron spectroscopy, Raman spectra, and scanning tunnelling microscopy/spectroscopy as well as density functional theory (DFT) calculations. PtSe$_2$ adopts a layer-by-layer growth mode on HOPG and shows a decreasing band gap with increasing layer number. For the layer numbers …
Ultrasound cavitation and exfoliation dynamics of 2D materials re-vealed in operando by X-ray free electron laser megahertz imaging
University of Hull（赫尔大学）；European XFEL（欧洲X射线自由电子激光装置）；Lund University（隆德大学）；University of Greenwich（格林威治大学）；Oxford Brookes University（牛津布鲁克斯大学）；Brunel University London（布鲁内尔伦敦大学）；University of Oxford（牛津大学）；La Trobe University（拉筹伯大学）；The Diamond Light Source Ltd（钻石光源有限公司）；Deutsches Elektronen-Synchrotron DESY（德国电子同步加速器研究所）
Recent studies show that the electronic structures of graphene can be modified by strain and it was predicted that strain in graphene can induce peaks in the local density of states (LDOS) mimicking Landau levels (LLs) generated in the presence of a large magnetic field. Here we report scanning tunnelling spectroscopy (STS) observation of nine strain-induced peaks in LDOS at 77 K along a graphene ridge created when the graphene layer was cleaved from a sample of highly oriented pyrolytic graphite (HOPG). The energies of these peaks follow the progression of LLs of massless 'Dirac fermions' (DF…
