单晶石墨、多晶石墨电导行为的差异

报道了单晶石墨、多晶石墨电导行为的差异.在8.15T磁场下，4.5K处单、多晶石墨的正磁电阻效应分别为69400%，170%，同时在0T，8T磁场作用下，多晶石墨的电导行为呈现类绝缘体型性质，但在单晶石墨中我们发现了与磁场相关的类半金属-绝缘体型转变，通过分析，我们认为：单、多晶石墨电导行为存在较大差异的原因可能来源于库仑相互作用在高定向热解石墨中变得不可忽视，而多晶石墨样品却存在晶界散射. 关键词： 半金属石墨 类半金属-绝缘体型转变     

Humidity Effects on Imaging and Nanomanipulation of Individual DNA Molecules on HOPG Surface

Single DNA molecules are aligned on highly ordered pyrolytic graphite （HOPG） surface in ambient air. It is shown that environmental humidity has a remarkable influence on the measured height of DNA by atomic force microscopy （AFM）, probably due to the conformation transition of DNA. We also demonstrate that DNA molecules deposited on HOPG surface can be ＇pushed＇ much more easily by AFM tip at high humidity than at 10W one.     

Superconductive CaC6 prepared from flexible graphite sheets

The host graphite material of choice for most CaC₆ studies is highly oriented pyrolytic graphite (HOPG), which can affect the resulting properties of prepared graphite intercalation compounds (GICs). In order to gain a better understanding of the superconductivity of CaC₆, we examined CaC₆ prepared from Grafoil and PGS. To confirm their superconductivity, the dependences of the magnetic moment on temperature under a constant magnetic field were measured over 2–20 K. The resulting CaC₆ transitioned to a superconducting state at around 11 K, independent of purity and homogeneity, while slight differences that depended on the host materials were observed. The transition to a superconducting state at 11.5 K occurred provided that a small amount of CaC₆ was present. The co-existence of LiC₆ and other GICs, and the residual Li atoms in the CaC₆ had little effect on the transition temperature. The transition temperature of the CaC₆ prepared from PGS was slightly lower than that of the CaC₆ prepared from HOPG and Grafoil.     

碳纳米管和高取向热解石墨的拉曼光谱对比研究

同时测量了碳纳米管（Ｄ－ＣＮＴ）和高取向热解石墨（ＨＯＰＧ）的拉曼光谱，第一次分别在ＨＯＰＧ和Ｄ－ＣＮＴ中观察到了位于４２６５ｃｍ－１和４２４８ｃｍ－１的（Ｇ＋Ｄ＊）三级模的拉曼散射；拉曼谱的研究显示，Ｄ－ＣＮＴ的结构比ＨＯＰＧ的无序，同时也进一步表明此无序程度主要来源于结构的缺陷，而非石墨层卷曲成筒状之故     

Few-layer graphene film fabricated by femtosecond pulse laser deposition without catalytic layers

The films of few-layer graphene are formed through laser exfoliation of a highly ordered pyrolytic graphite(HOPG), without a catalytic layer for the growth process. The femtosecond(fs) laser exfoliation process is investigated at different laser fluences and substrate temperature. For fs laser exfoliation of HOPG, the few-layer graphene is obtained at 473 K under an optimal laser fluence. The formation of few-layer graphene is explained by removal of intact graphite sheets occurred by an optimal laser fluence ablation. The new insights may facilitate the controllable synthesis of large area few-layer graphene.     

Highly oriented pyrolitic graphite anomalous structures and fullerenes self-assembly

Scanning tunneling microscopy (STM) was used to look for unusual self-structures on highly oriented pyrolitic graphite (HOPG) that can mimic fullerenes assemblies. HOPG features that may be taken as C₆₀ molecular structures were found on this surface. The HOPG self-structures have been presented earlier as anomalies of the bare HOPG surface in the literature. The experimental results are in agreement with earlier STM reports on bare and modified HOPG.     

Magnetoresistance studies of MeV ranged H and C ion irradiated HOPG flakes

2 MeV protons and 1 MeV carbon ions are bombarded on highly oriented pyrolytic graphite (HOPG) samples and their electronic transport measurements are carried out in the presence of magnetic field. The Magneto-Resistance (MR) measurements show measurable hysteresis in the resistance value after ion beam irradiation for the in-plane magnetic field direction as well as for the out-of-plane field direction. The MR depends on the thickness of the flake and the method of its separation from the bulk HOPG. The results substantiate that the ferromagnetic coupling between the magnetic moments at the vacancy defect sites in HOPG sensitively depends on the average defect separation. The average defect separation range of 1.7–0.5 nm allows only a part of the 40 μm thick proton beam irradiated sample to go for ferromagnetic ordering. Similar conclusions are drawn from carbon ion irradiated HOPG flake. The irradiation increases the resistance of the flake as well.     

Structure modification of highly ordered pyrolytic graphite by Ar plasma beam scanning at different incident angles

The surface of highly ordered pyrolytic graphite (HOPG) was modified by Ar plasma beam scanning at a controllable angle of incidence. The characteristics of plasma modified HOPG were investigated by atomic force microscope (AFM), micro-Raman, X-ray photoemission spectroscopy (XPS), and grazing incident angle of X-ray diffraction (GIAXRD). A smooth surface of HOPG can be obtained by adjusting the incident angles of Ar plasma beam scanning. The surfaces of HOPG become smoother with increasing angle of incidence after Ar plasma beam scanning. Raman spectra indicate that the plasma beam scanning breaks the hexagonal structures of sp² C=C bonds near the surface of HOPG. The broken hexagonal network structures can form C–O bonds that increase the amount of oxygen on the surface of HOPG, supported by C_1s and O_1s XPS spectra. GIAXRD data support that the co-existence of both crystalline structures of 2H and 3R in HOPG. The carbon bond breaking in 2H and 3R is different and depends on the angle of incidence. Most broken carbon bonds form damaged aromatic rings near the surface of HOPG.     

Influence of molecular-substrate interaction on the self-assembly of discotic liquid crystals

We compare by scanning tunnelling microscopy the structure of hexakis-2,3,6,7,10,11-alkyloxytriphenylene self-assembled at the liquid-solid interface with either gold (1 1 1) or graphite (HOPG) as the substrate. The symmetry-breaking transition previously observed on graphite, when the length of the side-chains is increased, is observed to take place also on gold. However, it corresponds to a more drastic reduction of symmetry and is associated to a decrease of the molecular area. We interpret this change in terms of a variation in the adsorption energy of the conjugated core with the substrate.     

Electronic and structural properties of graphene-based transparent and conductive thin film electrodes

We demonstrate that graphene-based transparent and conductive thin films (GTCFs), fabricated by thermal reduction of graphite oxide, have very similar electronic and structural properties as highly oriented pyrolytic graphite (HOPG). Electron spectroscopy results suggest that the GTCFs are also semi-metallic and that the individual graphene sheets of the film are predominantly oriented parallel to the substrate plane. These films may therefore be considered as a technologically relevant analogue to HOPG electrodes, which cannot be easily processed into thin films.     

Magnetism at single isolated iron atoms implanted in graphite

M?ssbauer spectra obtained after implantation of 57Fe into highly oriented pyrolytic graphite (HOPG) show a combined magnetic and quadrupole interaction with a magnetic hyperfine field Bhf = 32.6 T at 14 K. Though magnetic effects in nominally diamagnetic HOPG have been reported recently, no experiment has previously shown the existence of magnetism at the atomic scale. The results suggest that magnetic ordering occurs by coupling of the Fe magnetic moment to structural and/or electronic magnetic defects induced by the probe atoms' implantation damage.     

Positive and negative linear magnetoresistance of graphite

The magnetoresistance (MR) of bulk graphite with different particle sizes is investigated. The MR of the graphite decreases with the particle size decreases. The graphite with micro-sized particles has a positive MR and exhibits positive linear field dependence of MR at about 50 K, whereas the graphite with particle size of 30.2 nm has a negative MR and exhibits negative linear field dependence of MR at about 25 K. The possible mechanism for the MR of graphite can be partially understood using ordinary MR theory, weak localization theory and diffuse scattering theory.     

STS observations of Landau levels at graphite surfaces

Scanning tunneling spectroscopy (STS) measurements were made on surfaces of two different kinds of graphite samples, Kish graphite and highly oriented pyrolytic graphite (HOPG), at very low temperatures and in high magnetic fields. We observed a series of peaks in the tunnel spectra associated with Landau quantization of the quasi-two-dimensional electrons and holes. A comparison with the calculated local density of states at the surface layers allows us to identify Kish graphite as bulk graphite and HOPG as graphite with a finite thickness of 40 layers. This explains the qualitative difference between the two graphites reported in the recent transport measurements which suggested the quantum-Hall effect in HOPG. This work demonstrates how powerful the combined approach between the high quality STS measurement and the first-principles calculation is in material science.     

Adsorption and manipulation of carbon onions on highly oriented pyrolytic graphite studied with atomic force microscopy

Carbon onions produced by DC arc discharge method were deposited on highly oriented pyrolytic graphite (HOPG) surface and their adsorption and manipulation was studied using an atomic force microscopy (AFM). Well-dispersed adsorption of carbon onions on HOPG surface was obtained and aggregations of onions were not observed. The van der Waals interaction between the onion and HOPG surface and that between two onions, were calculated and discussed using Hamaker's theory. The manipulation of adsorbed onions on HOPG surface was realized using the AFM in both the raster mode and the vector mode. The controllability and precision of two manipulation modes were compared and the vector mode manipulation was found superior, and is a useful technique for the construction of nano-scale devices based on carbon onions.     

Intercalation of lithium ions into bulk and powder highly oriented pyrolytic graphite

The electrochemical reactions of highly oriented pyrolytic graphite (HOPG) bulk and powder electrodes in 1 M LiPF₆ 1:1 EC/DMC solution were investigated and the results show that the intercalation reaction of lithium ion into HOPG electrode occurs only at the edge plane and SEI formation reaction on the basal plane is negligible in comparison with that on the edge plane. The active surface area of HOPG powder electrode could be deduced by comparing the peak area (consumed charge for SEI formation) at potential of 0.5 V on voltammograms with that of bulk HOPG edge electrode. The diffusion coefficients of lithium ion in HOPG bulk layers and in HOPG powder was for the first time measured by use of electrochemical impedance spectra and potential step chronamperameter methods. It was found that the diffusion coefficients of lithium in HOPG were in the range of 10⁻¹¹-10⁻¹² cm² s⁻¹ for the lithium-HOPG intercalation compounds at potentials from 0.2 (vs. Li/Li⁺) to 0.02 V, decreasing with the increase of lithium intercalation degree. A good agreement was obtained between the results from bulk and powder HOPG electrodes by electrochemical impedance spectra method.     

STM analysis of triosmium carbonyl cluster adsorption at HOPG

The study of metallic carbonyl clusters as precursors in tailoring the heterogeneous metal catalysts has been of great importance. The catalytic nature of the adsorbed clusters in thin film form depends on the chemical properties of the substrate used. The metal-support interaction will determine various properties such as the surface morphology, adsorption features and the structural orientations. We report a scanning tunneling microscopy (STM) study of an osmium carbonyl cluster (Os₃(CO)₁₁(NCCH₃)) adsorbed on highly oriented pyrolytic graphite (HOPG). STM measurements showed that the osmium carbonyl cluster interacts with HOPG in such a way that it adsorbs on the basal plane showing regular lattice structure, whereas the axial planes of the HOPG surface shows no ordered structure. The regular cluster lattice structure of the carbonyl cluster on the basal plane of the graphite has lattice parameters of a=1.4 nm and b=1.5 nm. We believe that the regular orientation of the cluster indicates a monolayer adsorption of the cluster on the graphite basal planes. Scanning tunneling spectroscopy (STS) measurements also indicated an insulating behavior for the cluster molecules on HOPG, with a significant energy gap value of ca. 300 mV. The cluster interaction at the active sites, i.e. axial planes of the graphite, was also observed by in situ STM measurements.     

Ion-induced self-organized ripple patterns on graphite and diamond surfaces

In order to investigate the allotropic effect on ripple pattern formation, highly oriented pyrolytic graphite (HOPG) and single crystalline diamond were irradiated with 10-200 keV Xe⁺ at an incident angle of 60° with respective to the surface normal. The irradiation fluence was 2 × 10¹⁷ cm⁻² for all irradiations. Ripple patterns were observed on both HOPG and diamond surfaces. However, large differences in ripple wavelengths, amplitudes and surface roughnesses between HOPG and diamond were recognized. The reason for these differences is discussed.     

Elastic and inelastic scattering components in the angular intensity distribution of He scattered from graphite

The angular intensity distribution of thermal energy He beam scattered from highly oriented pyrolytic graphite (HOPG) surface has been measured by means of supersonic molecular beam scattering technique in the wide surface temperature range. To separate the elastic and inelastic scattering components, simple analysis method has been developed by applying the classical binary collision theory of the hard cube model (HCM). From the extracted elastic scattering component in the scattering distribution, the Debye temperature of the HOPG surface has been derived as 590 ± 30 K. On the basis of the HCM analysis for the extracted inelastic scattering components of He beam, the effective mass for the HOPG surface has been found to be 72 u (six carbon atoms).     

Ripening of subsurface amorphous C clusters formed by low energy He ion bombardment of graphite

Surfaces of highly oriented pyrolytic graphite (HOPG) were bombarded with 100 eV and 500 eV He ions at ion doses of a few 10¹⁵ cm² and temperatures ranging from 300 K to 800 K. AFM images were recorded to investigate the topography of the surfaces after ion bombardment. Supplementary electron energy loss (EEL) and thermal desorption (TD) spectra were measured to determine the C sp² fraction of the bombarded surfaces and the amount of trapped He. The temperature at which He ion bombardment was performed had a drastic effect on the surface structure and topography of the targets on the angstrom-scale and micrometer-scale as well. At 300 K, limited defect atom transport revealed an amorphous but relatively flat HOPG surface. Bombardment at 400 K leads to a granular structure of small protrusions in micrometer-scale AFM images, however, without crystalline order on the surface. The protrusions are due to the formation of subsurface clusters of carbon formed by atoms displaced by ion irradiation. Towards higher temperatures during bombardment the clusters agglomerate and cause the surface layers to bend upwards in dome-like shapes. Simultaneously, the microscopic order of the graphite lattice recovers. At 800 K large areas of the top layer retain their order during bombardment, however, a small number of domes indicate that there still exist some subsurface C clusters. The cluster–cluster distance deduced from the dome distribution indicates that the clusters grow through a ripening process. Annealing of graphite at high temperatures subsequent to ion bombardment at low temperatures is much less effective for recovering the surface crystallinity than ion bombardment at high temperature.     

Interface scattering and spin-dependent transport in granular magnetite

We have prepared nearly monodisperse Fe₃O₄ of ∼50 nm by a chemical route and investigated the electrical and magnetic transports of the composite granular system. A Verwey transition is observed in the vicinity of 113 K. Above and below the Verwey transition, the electrical transport is dominated by electron hopping behavior showing a good linear relation between resistance and T^−1/2. The magnetoresistance (MR) increases with the applied field and does not follow the magnetization to reach the saturation at 10 KOe field. This indicates that the MR is mainly arising from the spin-dependent scattering of electrons through the grain boundaries. The temperature dependence of MR shows it has the highest MR value near the Verwey transition.