Adsorption of D(H) atoms on Ar ion bombarded (0 0 0 1) graphite surfaces

Adsorption of thermal (2000 K) D (H) atoms on HOPG surfaces prior to and after bombardment with 500 eV Ar ions was studied with thermal desorption and vibrational spectroscopies. Ion bombardment of HOPG generates vacancy (VD, displaced surface C atoms) and interstitial (ID, Ar captured between 1st and 2nd C plane) defects. These defects remove the ability of the surface to adsorb D like on virgin HOPG surfaces and to form C_gr–D bonds. After a dose of 0.1 Ar per C surface atom, D adsorption is markedly suppressed. Annealing of bombarded surfaces at 1350 K, connected with desorption of trapped Ar and removal of ID, recovers a large fraction of the adsorption capacity for D. Therefore, the long range stress in the surface plane introduced by ID must be responsible for a significant fraction of D adsorption blocking. It is suggested that ID prevent reconstruction of the C surface which is required for the formation of C_gr–D bonds. For ion doses above 0.5 Ar/C, adsorption of D on the surface is negligible. After annealing at 1350 K, D can be adsorbed in quantities comparable to the virgin HOPG surface, however forming C–D bonds which are similar to those observed in hydrogenated amorphous carbon instead of those which are normally formed on HOPG. Instationary etching via release of deuterocarbon species occurs primarily in the C₁ and C₂ channels. It is only observed at bombarded HOPG prior to annealing and probably due to the presence of isolated C₁ and C₂ species on the surface generated upon VD formation.     

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.     

Observation of the Damage on HOPG Surface Induced by Ar+8 Ions

Highly oriented pyrolytic graphite (HOPG) samples were bombarded by Ar+8 ions with energy range from 10.1 to 112MeV. After bombardment the sample surfaces were observed using a STM and NanoScope. The resultS show that the energetic ion could cause observable praotrusionlike damage on the HOPG surface.The relationship betWeen damage and energy loss, and the possible mechanism of damage process are discussed.     

高能氮离子轰击对四面体非晶碳膜的表面改性和摩擦系数影响的研究

利用过滤阴极真空电弧技术制备了sp³键含量不小于80%的四面体非晶碳(ta-C)膜.利用冷阴极潘宁离子源产生不同能量的氮离子对制备的ta-C薄膜进行轰击,通过X射线光电子能谱和原子力显微镜对薄膜表面结构与形貌进行分析研究.研究表明,随着氮离子的轰击能量的增大,薄膜中的CN键结构略有增大,形成了轻N掺杂;同时,在薄膜表层发生了sp³键结构向sp²键结构的转化;薄膜的表面粗糙度在经过氮离子轰击后从0.2 nm减小至0.18 nm,然后随着轰击能 关键词： 四面体非晶碳 X射线光电子能谱 摩擦系数     

Electron spectroscopy measurements on hydrogen implanted graphite and comparison to amorphous hydrogenated carbon films (a-C:H)

Highly oriented pyrolytic graphite (HOPG) as well as polycrystalline graphite (pc-graphite) were bombarded with 3.5 keV H⁺ ions by means of a Penning ion source. The implanted graphite was characterized by in situ electron spectroscopy techniques such as UPS, XPS and EELS. Our UPS valence band measurements of the hydrogen saturated graphite reveal it to be an insulating phase, and XPS measurements show a shift of the C1s core level to higher binding energy with respect to pristine graphite. This behavior is explained by a Fermi energy shift upon hydrogen bombardment of graphite.In addition, a close resemblance in the electronic structure of hydrogen bombarded graphite and amorphous hydrogenated carbon films (a-C:H) is shown which suggests the modification of pristine graphite to an amorphous network [1] of mostly tetrahedrally bonded carbon atoms by hydrogen implantation.     

Transmission of low-energy (< 10 eV) O ions through Au films on TiO2(110)

In an attempt to identify the fundamental processes that influence ion transport through metallic surface layers, we have studied the transmission of O⁺ ions through discontinuous Au films adsorbed on TiO₂(110). A low energy (< 10 eV) O⁺ ion beam is generated via electron stimulated desorption when an Au-dosed TiO₂(110) substrate is bombarded with a focused 250 eV electron beam. Low energy ion scattering data indicate that Au evaporated under ultrahigh vacuum conditions at 300 K forms three-dimensional clusters on TiO₂(110). As the Au coverage increases, the formation of Au clusters on TiO₂(110) blocks a fraction of the TiO₂ surface and the O⁺ yield is attenuated. However, for high coverages (≥30% Au covered substrate) the O⁺ signal decreases at a faster rate than the TiO₂ open area fraction. We attribute the attenuation of the O⁺ yield for high Au coverages mainly to blocking of O⁺ by Au clusters, to deflection of trajectories by the image force between ions and Au clusters, and to charge transfer between desorbing O⁺ and neighboring Au clusters.     

Electronic modifications and surface reactivity of an ion bombarded graphite surface

The first steps of structural and electronic modifications of a graphite surface bombarded with argon, hydrogen and deuterium ions were investigated using high resolution electron energy loss spectroscopy (HREELS). The energy and the damping of the low energy plasmon mode of graphite (E//C mode) were studied with respect to the bombardment settings. We show that argon bombardment affects the energy of the plasmon mode, while no similar change is observed after hydrogen (deuterium) bombardments. This can be related to the variation of inter-planar distance between two graphene layers. Moreover, the damping of the plasmon mode can be correlated with the interstitial defect concentration. Concerning the reactivity of the bombarded surfaces, we demonstrate that deuterium bombardment produce a non-deuterated surface. This last is very reactive to a further atomic deuterium exposure, as it is shown by the formation of C-D bondings. The deuterated sites can be removed after thermal annealings between 473 and 783 K. The occurrence of a chemical erosion mechanism accompanying this deuteration is discussed.     

Surface modifications of PADC polymeric material by ion beam bombardment for high technology applications

Surface modification of Poly (allyl diglycol carbonate) (PADC) is induced by 150 keV Ag ions of different fluences. The pristine as well as bombarded samples were investigated by UV–Vis spectroscopy, Fourier transform-infrared analysis (FTIR) and micro-hardness tester. The variations of wettability and surface free energy were determined by the contact angle measurements. The obtained results showed that ion beam bombardment induced increase in the absorption spectra of the UV–Vis with increase of ion fluence as well. The direct and indirect optical band gap decreased from 4.2 to 3.6 eV for pristine sample to 3.2 and 2.5 eV for those bombarded with Ag ion beam at the highest fluence, respectively. Changes in chemical properties were observed by Fourier transform infrared spectroscopy. Increase in the wettability, surface free energy and work of adhesion with increase the ion fluence were observed. Ion bombardment inducing increasing in a micro-hardness surface due to the high carbon surface concentration and cross-linking effects in the polymeric chains. The bombarded PADC surfaces may find special applications to the field of the micro-electronic devices and printing process.     

Adsorption of oxygen on Au(111) by exposure to ozone

Atomic oxygen coverages of up to 1.2 ML may be cleanly adsorbed on the Au(111) surface by exposure to O₃ at 300 K. We have studied the adsorbed oxygen layer by AES, XPS, HREELS, LEED, work function measurements and TPD. A plot of the O(519 eV)/Au(239 eV) AES ratio versus coverage is nearly linear, but a small change in slope occurs at Θ_O=0.9 ML. LEED observations show no ordered superlattice for the oxygen overlayer for any coverage studied. One-dimensional ordering of the adlayer occurs at low coverages, and disordering of the substrate occurs at higher coverages. Adsorption of 1.0 ML of oxygen on Au(111) increases the work function by +0.80 eV, indicating electron transfer from the Au substrate into an oxygen adlayer. The O(1s) peak in XPS has a binding energy of 530.1 eV, showing only a small (0.3 eV) shift to a higher binding energy with increasing oxygen coverage. No shift was detected for the Au 4f_7/2 peak due to adsorption. All oxygen is removed by thermal desorption of O₂ to leave a clean Au(111) surface after heating to 600 K. TPD spectra initially show an O₂ desorption peak at 520 K at low Θ_O, and the peak shifts to higher temperatures for increasing oxygen coverages up to Θ_O=0.22 ML. Above this coverage, the peak shifts very slightly to higher temperatures, resulting in a peak at 550 K at Θ_O=1.2 ML. Analysis of the TPD data indicates that the desorption of O₂ from Au(111) can be described by first-order kinetics with an activation energy for O₂ desorption of 30 kcal mol⁻¹ near saturation coverage. We estimate a value for the Au–O bond dissociation energy D(Au–O) to be 56 kcal mol⁻¹.     

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.     

Ion beam modification of surface properties of CR-39

The effects of ion-beam bombardment on the physical and chemical properties of poly(allyl diglycol carbonate) (CR-39) polymer have been investigated. CR-39 samples were bombarded with 320 keV Ar and 130 keV He ions at fluences ranging from 1 × 10¹³ to 2 × 10¹⁶ ions/cm². The nature and extent of radiation damage induced were studied by UV–VIS spectrometry, Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) analysis, as well as Vickers' hardness measurements. In addition, the effect of ion fluence on the wetting properties of ion-beam bombarded CR-39 polymer was determined by measuring the contact angle for distilled water. UV–VIS spectra of bombarded samples reveal that the optical band gap decreases with increasing ion fluence for both Ar and He ions. In the FTIR spectra, changes in the intensity of the bands on irradiation relative to pristine samples occurred with the appearance of new bands. XRD analyses showed that the degree of ordering of the CR-39 polymer is dependent on the ion fluence. Changes of surface layer composition and an increase in the number of carbonaceous clusters produced important change in the energy gap and the surface wettability. The surface hardness increased from 10.54 MPa for pristine samples to 28.98 and 23.35 MPa for samples bombarded with Ar and He ions at the highest fluence, respectively.     

Soft X-ray emission study of thermally treated Ni(film)/4H–SiC(substrate) interface

Deposition of Ni as contact on 4H–SiC has been investigated. Ni/4H–SiC samples were annealed at temperatures of 600, 800 and 950 °C for 30 min and were non-destructively characterized by soft X-ray emission spectroscopy (SXES) using synchrotron radiation as excitation. Si L_2,3 SXE showed the formation of Ni₂Si for all annealing temperatures. The C K SXE indicated the formation of graphite and graphitic carbons at annealing temperatures of 950 °C and below 800 °C, respectively.     

Application of the thermal spike model for explanation of variations of surface structure of highly oriented pyrolytic graphite under bombardment by 86Kr and 209Bi fast ions with high ionization energy loss

Temperature effects in the highly oriented pyrolytic graphite (HOPG) under bombardment by ⁸⁶Kr (253 MeV) and ²⁰⁹Bi (710 MeV) heavy ions are studied in the framework of a three-dimensional thermal spike model. It is shown that the surface temperature of an HOPG target under bombardment by bismuth ions can exceed the sublimation temperature at particular values of the electron-phonon interaction coefficient. At the same time, the temperature at the target surface during bombardment of HOPG by krypton ions does not exceed the sublimation temperature over a wide range of variations in the electron-phonon interaction belongs. The calculations allow the explanation of the observed changes in the surface structure of HOPG single crystal under bombardment by ²⁰⁹Bi and ⁸⁶Kr ions.     

A metastable de-excitation spectroscopy (MDS) study on oxygen adsorption on a polycrystalline zirconium surface

The adsorption of oxygen on a polycrystalline zirconium surface at room temperature has been studied by metastable de-excitation spectroscopy (MDS) in conjunction with UPS and AES. From the analysis of the measured spectra, we have shown the following. (1) At the initial stage of oxygen adsorption (exposure <1.2 L), the surface density of states (SDOS) of zirconium changes little at around the Fermi level (E_F), while it decreases appreciably at 1–2 eV below E_F (E_B=1–2 eV) by oxygen adsorption. (2) The SDOS at E_B=0–2 eV decreases with increasing oxygen exposure at >1.2 L and disappears at >8 L. (3) The oxygen 2p states (E_B=5–8 eV) are localized at the subsurface region at oxygen exposure 0–2 L. (4) The ZrO₂ phase appears at the outermost zirconium surface at around 2 L, then grows with increasing exposure, and finally dominates at >8 L. It is suggested that two different phases (ZrO₂ phase and that in which oxygen occupies subsurface sites) coexist at the outermost surface at 2–8 L.     

氩离子轰击对四面体非晶碳膜内应力和摩擦系数影响的研究

利用磁过滤真空阴极电弧技术制备了sp³键大于80%的四面体非晶碳(ta-C)薄膜, 通过冷阴极离子源产生keV能量的氩离子轰击ta-C薄膜,研究了氩离子轰击能量对ta-C薄膜结构, 内应力以及耐磨性的影响.通过X射线光电子能谱和原子力显微镜研究了氩离子轰击对薄膜结构 与表面形貌的改性,研究表明,氩离子轰击诱导了ta-C薄膜中sp³键向sp²键的转化, 并且随着氩离子轰击能量的增大,薄膜中sp²键的含量逐渐增多, 薄膜内应力随着氩离子轰击能量的增大逐渐减小.氩离子轰击对薄膜的表面形貌有较大影响, 在薄膜表面形成刻蚀坑,并且改变了薄膜的表面粗糙度,随着氩离子轰击能量的增大, 薄膜的表面粗糙度也会逐渐增大.通过摩擦磨损仪的测试结果,氩离子轰击对薄膜的初始摩擦系数影响较大, 但是对薄膜的稳定摩擦系数影响较小,经过氩离子轰击前后的ta-C薄膜的摩擦系数为0.1左右, 并且具有优异的耐磨性.     

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.     

Modified π-states in ion-irradiated carbon

CVD polycrystalline diamond film, pulse laser-deposited (PLD) carbon film and highly oriented pirolitical graphite (HOPG) as reference, were modified by means of Ar⁺ ion bombardment and characterized by means of Raman scattering, transmission electron microscopy, electron-diffraction (TEM), reflected electron energy loss specroscopy (REELS) and X-ray photoelectron spectroscopy (XPS) techniques. It was found that the diamond was transferred to a carbon with halo-like morphology and disordered stack of graphene segments. Instead of the well-known electron energy loss peak of graphite at 6.5 eV, a new REELS peak appeared at 4-5 eV energies. The observed effect was explained by the modification of π-system in carbon films as a consequence of the formation of non-planar, nanometer-sized graphitic planes.     

Measurement of the sputter yield after mild ion erosion of a pristine Cu(001) surface

Using the STM technique we have determined the sputter yield on a pristine Cu(001) surface after mild (fluence less than 0.044 ions per surface atom) bombardment of the pristine surface with 800 eV Ar⁺ions at normal incidence. The experiments have been performed at substrate temperatures ranging from 200 to 350 K. Making use of the positional correlation of adatoms and surface vacancies, at 200 K and 325 K, we concluded that about 1/3 of the surface adatoms originate from interstitials arriving at the surface and they give a direct indication of the buried bulk vacancies. A careful analysis of the different areas for surface vacancies and adatom then allowed a quantitative evaluation of the sputter yield at 1.2 Cu atoms per 800 eV Ar⁺ ion.     

Metallization and demetallization of clean and oxygen-covered ultrathin alkali metal films on GaAs(1 0 0)

The structure and the electronic valence state occupation of ultrathin K, Rb, and Cs films grown on a GaAs(1 0 0)-(4×2) surface have been studied by means of metastable He atom scattering (MHAS), He atom scattering (HAS), and low-energy electron diffraction (LEED) at temperatures ranging from 150 to 400 K. From the survival probability of the scattered He^* atoms, detailed information on the coverage-dependent filling of the alkali metal valence states and their emptying upon subsequent exposure to oxygen were derived. These data reveal for K and Rb a nearly linear band filling with increasing coverage starting at about 0.5 ML whereas a more rapid filling is observed for Cs which is almost completed at about 0.7 ML. Subsequent oxygen adsorption causes a demetallization of the metallic alkali metal monolayers. In case of Cs, a distinct minimum of the He^* signal appears at an oxygen exposure of about 0.8 L, presumably indicating the onset of subsurface oxidation.     

Superficial defects induced by argon and oxygen bombardments on (110) TiO2 surfaces

Compositional and chemical changes of titanium dioxide monocrystalline surfaces induced by bombardment with 4 keV argon and oxygen ions have been studied by AES, XPS and AFM. Argon ion bombardment induced strong changes in the composition and chemical state of the surface: loss of oxygen due to preferential sputtering occurred, and, related to this, Ti⁴⁺ species were reduced to Ti³⁺ and Ti²⁺. During oxygen bombardment, competition between preferential sputtering of oxygen ions of the oxide surface and oxygen implantation was observed. This phenomenon was found to be strongly dependent upon the incidence angle of the oxygen ions. Moreover, an oxygen bombardment with normal incidence of the surface that had been previously submitted to an argon ion bombardment led to a restoichiometrization of the surface: no further Ti³⁺ or Ti²⁺ was found by XPS, only Ti⁴⁺.