Ar+8轰击石墨表面损伤的扫描隧道显微镜观测研究

报道了用10—112MeV能量的Ar+8离子轰击高定向石墨造成损伤的原子水平观测结果,给出了损伤形貌、损伤大小和损伤数密度.讨论了损伤与表面核能损的关系及损伤过程的可能机制.     

Transmission measurement based on STM observation to detect the penetration depth of low-energy heavy ions in botanic samples

The penetration depth of low-energy heavy ions in botanic samples was detected with a new transmission measurement. In the measurement, highly oriented pyrolytic graphite (HOPG) pieces were placed behind the botanic samples with certain thickness. During the irradiation of heavy ions with energy of tens of keV, the energetic particles transmitted from those samples were received by the HOPG pieces. After irradiation, scanning tunneling microscope (STM) was applied to observe protrusion-like damage induced by these transmitted ions on the surface of the HOPG. The statistical average number density of protrusions and the minimum transmission rate of the low-energy heavy ions can be obtained. The detection efficiency of the new method for low-energy heavy ions was about 0.1-1 and the background in the measurement can be reduced to as low as 1.0 x 10(8) protrusions/cm2. With this method, the penetration depth of the energetic particles was detected to be no less than 60 micrometers in kidney bean slices when the slices were irradiated by 100 keVAr+ ion at the fluence of 5 x 10(16) ions/cm2.     

Pinning of size-selected Co clusters on highly ordered pyrolytic graphite

Deposition and implantation of size-selected Co⁺ _50±5 cluster ions on/in highly ordered pyrolytic graphite (HOPG) have been performed. Cobalt clusters were produced by laser ablation using the second harmonic (532 nm) of a Nd:YAG laser. They were deposited/implanted with energies of 250–4850 eV/cluster and examined using scanning tunneling microscopy (STM). For the highest energies the clusters created craters and wells with residual clusters at the bottom of the wells. Decrease of the impact energy led to formation of bumps whichconsist of damaged graphite areas mixed with fragmented cobalt clusters. Further decrease of the impact energy to 250–450 eV/cluster probably corresponds to the so-called pinning regime, when the impacting cluster creates defects in the surface layer and becomes bound to them. The transition from implantation to pinning with a decrease of impact energy was confirmed by etching experiments showing the depth of the damage introduced by the cluster collisions with HOPG.     

Band-reject-filtering X-ray spectra by mosaic structures of pyrolytic graphite

The possibility of effective band-reject filtration of intense spectral lines in X-ray spectra and the creation of deep spectral valleys in the continuous spectrum by diffraction extinction was shown. Optimum material for band-reject filters in the energy range E > 6 keV is highly oriented pyrolytic graphite (HOPG). The filtering scheme in the form of an echelon arrangement of HOPG films is proposed, which suppresses the negative effect of multiple reflections due to diffraction extinction. The full width at half minimum of the spectral valleys can vary from tens of electronvolt to several kiloelectron volt depending on the HOPG mosaic spread, HOPG filters arrangement, and rejected energy region. At the energy range E of ~10 keV, the spectral density attenuation value may be of order 10⁻³ and lower. The obtained results can be used in various fields of X-ray spectrometry, as well as in static energy dispersive diffractometry and reflectometry.     

UV photoemission study on fullerene molecules deposited on defect-rich carbon surfaces

Submonolayers of C₆₀ molecules have been deposited on different carbon substrates (pristine HOPG, argon-ion irradiated HOPG and amorphous carbon) and investigated by means of Ultraviolet Photoelectron Spectroscopy. The desorption behavior and spectral changes in the valence band were examined as a function of the sample temperature. Strong fullerene-substrate interaction (chemisorption) was observed on defect-rich surfaces (irradiated HOPG, a-C), indicated by binding energy shifts and broadening of C₆₀ VB features. These chemisorbed species proved to be more resistant against temperature-induced desorption than usually observed for physisorbed molecules on pristine HOPG. The results presented here suggest that deposition of fullerenes on heated substrates might be a feasible method of surface nanostructuring by preferential chemisorption on defects.     

双甘氨肽与高定向热解石墨的散射动力学研究

本文通过反应力场来研究中性双甘氨肽与高取向热解石墨的碰撞动力学过程,分别模拟初始入射角度为0o、20o、45o和70o以及入射能量为481.5 kJ/mol和表面温度为677 K的情况,并且确定和分析了散射产物的角度分布、平动能分布、内能分布和表面滞留时间分布. 双甘氨肽是一种多原子分子,具有较多的低频振动模式和较强的表面吸附相互作用,这些使得碰撞过程的表面滞留时间较长和容易造成能量损失,尤其是表面法线方向. 由于碰撞分子的动量沿表面法线方向上明显地发生损失,而沿表面平行方向上的动量则会大部分保留,因此,其散射角通常会呈现出超镜面反射分布,并且末态的平动能要远小于所谓硬立方模型的预测值. 本文加深了多肽分子与高取向热解石墨碰撞及其能量转移过程的认识和理解,有助于设计在稀薄大气中收集这类大分子的中性气体浓缩器.     

The Magnetic Order in Ion Irradiated Graphite

The magnetism of highly oriented pyrolytic graphite(HOPG) induced by ion implantation is investigated with electron spin resonance(ESR) spectroscopy and magnetization measurements.The results indicate that the ESR spectra of the HOPG sample correlate with ion species,incident energy and dose of implantation.The correlation of the ESR spectra and magnetism of the HOPG sample with ~(12)C~+ ion implantation and H~+ ion implantation are studied in detail.The ferromagnetism of the HOPG sample is likely related to the asymmetric L1 line,which may be attributed to the interaction between localized defects and itinerant electrons occupied in the 'impurity'band induced by ion implantation.     

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.     

STM and AFM observations of damage produced by swift Ne and Kr ions in graphite

Radiation damage of highly oriented pyrolitic graphite (HOPG) samples have been investigated following irradiation with 215 MeV Ne and 209 MeV Kr ions, available at U-400 cyclotron, Dubna. A freshly cleaved HOPG surface was irradiated perpendicularly to the sample surface (c plane). A low ion irradiation dose was used (10¹² ions/cm²) in order to avoid damage overlap. Scanning tunneling microscopy (STM) and atomic force microscopy (AFM) are useful methods allowing direct observation of surface defects. The observations were made after irradiation without any further sample preparation. The experimental results are compared to computer simulations (TRIM code) and primary knonked-on atomic spectrum calculations (LET code). Clear distinction can be made between surface features attributed to nuclear stopping effects and defects owing to electronic stopping mechanisms.     

Surface reactivity of oxygen on cleaved and sputtered graphite

The characterization of reactions which occur during the oxidation of highly oriented pyrolytic graphite (HOPG) was performed using high-resolution electron energy loss spectroscopy (HREELS) temperature programmed desorption (TPD), and scanning tunneling microscopy (STM). The results of this investigation provide spectroscopic evidence for the presence of semi-quinone functionalities on sputtered and oxidized HOPG STM images are presented to quantify the increase in defect sites after oxygen ion sputtering, and to correlate defect site density with reactivity.     

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.     

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).     

Structure control of Pt-Sn bimetallic catalysts supported on highly oriented pyrolytic graphite (HOPG)

PtSn bimetallic catalyst nanoparticles were grown on highly oriented pyrolytic graphite (HOPG) surfaces using the sequential deposition and co-deposition of Pt and Sn. The surface morphology and composition of the prepared PtSn catalysts were investigated by scanning tunneling microscopy and CO adsorption experiment. It is found that the structure of the PtSn catalysts can be controlled by the deposition process. The deposition sequence of 1st Pt and 2nd Sn and co-deposition of Pt and Sn produce Sn-shell and Pt-core structure, while the deposition sequence of 1st Sn and 2nd Pt leads to the growth of individual Pt and Sn particles. The formation of various PtSn bimetallic structures was attributed to the different surface energy of Pt and Sn, and the interaction of the metals with the HOPG surfaces.     

Simultaneous observation of the triangular and honeycomb structures on highly oriented pyrolytic graphite at room temperature: An STM study

Scanning tunneling microscopy (STM) was used to study the surface structures of dry-prepared and di-chloroethane-treated HOPG samples. Both triangular and honeycomb structures were simultaneously observed with the same tip at room temperature around a strand (grain boundary) on the HOPG surface. This observation did not support the tip effect in STM imaging explanation for HOPG in literature. A general layer-sliding model was utilized to explain the experimental results: sliding of the HOPG topmost layer was used to explain the origins of the triangular and honeycomb structures, and molecule intercalation into inter-layer spacing between the first and second layers of HOPG induced inhomogeneous deformation of the HOPG topmost layer that accordingly generated the Moiré patterns of the HOPG sample in di-chloroethane.     

Observation and study of latent tracks on the surface of HOPG induced by H ions

The topography and size of damage on the surface of HOPG (Highly Oriented Pyrolitic Graphite) bombarded by high fluence (1×10¹⁶ ions/cm²) of H⁺ ions were observed and studied. In this work, 457 STM images of each one with 9×9 nm² area were obtained. From 163 of these pictures visible damage was found. In these 163 STM images the diameter of most damage is from 0.2 to 0.8 nm. In this study the number density of visible damage is much less than the ion fluence. The probability of damage is only about 1.8×10⁻⁴. The possible mechanism of damage formation is also analyzed and discussed.     

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.     

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.     

A comparative STM study of Ru nanoparticles deposited on HOPG by mass-selected gas aggregation versus thermal evaporation

Scanning tunneling microscopy was used to compare the morphologies of Ru nanoparticles deposited onto highly-oriented graphite surfaces using two different physical vapour deposition methods; (1) pre-formed mass-selected Ru nanoparticles with diameters between 2 nm and 15 nm were soft-landed onto HOPG surfaces using a gas-aggregation source and (2) nanoparticles were formed by e-beam evaporation of Ru films onto HOPG. The particles generated by the gas-aggregation source are round in shape with evidence of facets resolved on the larger particles. Annealing these nanoparticles when they are supported on unsputtered HOPG resulted in the sintering of smaller nanoparticles, while larger particles remained immobile. Nanoparticles deposited onto sputtered HOPG surfaces were found to be stable against sintering when annealed. The size and shape of nanoparticles deposited by e-beam evaporation depend to a large extent on the state of the graphite support and the temperature. Ru deposition onto unsputtered HOPG is characterised by bimodal growth with large flat particles formed on the substrate terraces and smaller diameter particles aligned along the substrate steps. Evaporation onto sputtered HOPG results in the formation of 2 nm round particles with a narrow size distribution. Finally, thermal deposition onto both sputtered and unsputtered HOPG at 660 °C results in larger particles showing a flat Ru(0 0 0 1) top facet.     

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.