Preferential sputtering of TIC under keV Ar+ ion bombardment: Simultaneous sputtering-ISS measurement with He+ and Ar+ ions

The composition change of the outermost atom layer of TiC(110) under ion bombardment with 1.5–3 keV He⁺ and He⁺ + Ar⁺ ions has been measured by ion scattering spectroscopy with He⁺ ions at different sample temperatures. It has been found that the preferential sputtering of C atoms takes place for both the He⁺ and Ar⁺ ion bombardment, however the preferred sputtering is more pronounced for Ar⁺ ions than for He⁺ ions. The ion bombardment with He⁺ ions at elevated sample temperatures hardly results in any change in surface composition below ～800°C, while Ar⁺ ion bombardment results in C enrichment for elevated temperatures as reported so far.     

AES analysis of nitridation of Si(100) by 2–10 keV N+2 ion beams

Ion beam nitridation of Si(100) as a function of N⁺₂ ion energy in the range of 2–10 keV has been investigated by in-situ Auger electron spectroscopy (AES) analysis and Ar⁺ depth profiling. The AES measurements show that the nitride films formed by 4–10 keV N⁺₂ ion bombardment are relatively uniform and have a composition of near stoichiometric silicon nitride (Si₃N₄), but that formed by 2 keV N⁺₂ ion bombardment is N-rich on the film surface. Formation of the surface N-rich film by 2 keV N⁺₂ ion bombardment can be attributed to radiation-enhanced diffusion of interstitial N atoms and a lower self-sputtering yield. AES depth profile measurements indicate that the thicknesses of nitride films appear to increase with ion energy in the range from 2 to 10 keV and the rate of increase of film thickness is most rapid in the 4–10 keV range. The nitridation reaction process which differs from that of low-energy (< 1 keV) N⁺₂ ion bombardment is explained in terms of ion implantation, physical sputtering, chemical reaction and radiation-enhanced diffusion of interstitial N atoms.     

ISS measurement of surface composition of AuCu alloys by simultaneous ion bombardments with Ar+ and He + ions

Surface composition of Au-Cu(43 at%) alloy under 1.5–5 keV argon ion bombardment has been investigated by ion scattering spectroscopy (ISS). In this experiment, we adopted a specific technique to use mixed He⁺ and Ar⁺ ions as primary beam in order to perform sputtering (Ar⁺) and ISS measurement (He⁺) simultaneously. The outermost atom layer of Au-Cu alloys under Ar⁺ ion bombardment is Au-rich leading to the conclusion that Ar⁺ ion bombardment of AuCu alloys causes the preferential sputtering of Cu atoms, resulting in a Au-rich outermost atom layer and a depletion layer of Au atoms beneath the outermost atom layer due to ion-beam-enhanced surface segregation. This result explains the experimental results obtained by AES as well.     

离子束增强沉积制备p型氧化锌薄膜及其机理研究

采用离子束增强沉积方法在Si和SiO₂/Si衬底上制备In-N共掺杂ZnO薄膜(INZO)，溅射靶是用ZnO和2 atm% In₂O₃粉体均匀混合并压制而成，在氩离子溅射ZnO靶的同时，氮、氩混合离子束垂直注入沉积的薄膜.实验结果显示INZO薄膜具有(002)的择优取向，并且为p型导电，电阻率最低为0.9Ωcm.薄膜在氮气、氧气气氛下退火，对薄膜的结构和电学特性与成膜和退火条件的关系进行了分析. 关键词： 氧化锌薄膜 p型掺杂 离子束增强沉积     

The unexpected formation of Au-Si by the resonance neutralization of Ar during the low energy bombardment of Au nanoparticles on c-Si

Nanoscale Au layers, with irregular porosities, have been formed by the low energy Ar⁺ bombardment of Au nanoparticles that were sputter-deposited onto native oxide-covered Si surfaces. High-resolution field emission scanning electron microcopy (FE-SEM) and X-ray photoelectron spectroscopy (XPS) have been used to characterize the formation and evolution of the nanoporous layer. Under Ar⁺ bombardment, the Au nanoparticles that were initially deposited were observed to flatten and spread across the native oxide surface, without diffusing, finally coalescing at their edges to form a nanoporous film having irregular pore dimensions. XPS showed that this evolution was accompanied by the loss of Au as a result of sputtering. The formation of such porous films necessitates strong interfacial bonding to avoid the lateral diffusion of the Au nanoparticles, and their ultimate coalescence into larger nanoparticles.We demonstrated that Ar⁺ beam bombardment invariably caused the formation of Au^δ+-Si^δ− bonding, rather than the expected Au^δ−-Si^δ+ bonding, and we explain this to be due to the resonance neutralization of the Ar⁺ beam on impacting the Au layer. We also reveal that the presumed formation of AuSi_x is not quantifiable by XPS, due to the superposition of the chemical shift of the Au nanoparticles with that of the quantum size effect, during Au loss on sputtering.     

低能氩离子束对多孔铝阳极氧化膜表面的刻蚀效应研究

用低能氩离子束(Ar⁺)处理了多孔铝阳极氧化膜(AAO)表面.扫描电子显微镜和原 子力显微镜结果表明，Ar⁺束刻蚀不仅可以有效地去除AAO反面阻挡层，还可使A AO表面产生多种特殊的形貌，如采用倾角入射可使其表面产生波纹，倾角入射同时旋转样品 台，可实现表面抛光.并结合Bradley和Harper提出的无定形材料表面波纹的形成和演化理论 解释了AAO表面波纹的特征. 关键词： 多孔铝阳极氧化膜 离子束刻蚀     

Carbon sputtering yield measurements at grazing incidence

In this investigation, carbon sputtering yields were measured experimentally at varying angles of incidence under Xe⁺ bombardment. The measurements were obtained by etching a coated quartz crystal microbalance (QCM) with a low energy ion beam. The material properties of the carbon targets were characterized with a scanning electron microscope (SEM) and Raman spectroscopy. C sputtering yields measured under Ar⁺ and Xe⁺ bombardment at normal incidence displayed satisfactory agreement with previously published data over an energy range of 200 eV-1 keV. For Xe⁺ ions, the dependence of the yields on angle of incidence θ was determined for 0° ≤ θ ≤ 80°. Over this range, an increase in C sputtering yield by a factor of 4.8 was observed, with the peak in yield occurring at 70°. This is a much higher variation compared to Xe⁺ → Mo yields under similar conditions, a difference that may be attributed to higher scattering of the incident particles transverse to the beam direction than in the case of Xe⁺ → C. In addition, the variation of the yields with θ was not strongly energy dependent. Trapping of Xe in the surface was observed, in contrast to observations using the QCM technique with metallic target materials. Finally, target surface roughness was characterized using atomic force microscope measurements to distinguish between the effects of local and overall angle of incidence of the target.     

Low energy Ar-ion bombardment effects on the CeO2 surface

The structure and electronic properties of epitaxial grown CeO₂(1 1 1) thin films before and after Ar⁺ bombardment have been comprehensively studied with synchrotron radiation photoemission spectroscopy (SRPES). Ar⁺ bombardment of the surface causes a new emission appearing at 1.6 eV above the Fermi edge which is related to the localized Ce 4f¹ orbital in the reduced oxidation state Ce³⁺. Under the condition of the energy of Ar ions being 1 keV and a constant current density of 0.5 μA/cm², the intensity of the reduced state Ce³⁺ increases with increasing time of sputtering and reaches a constant value after 15 min sputtering, which corresponds to the surface being exposed to 2.8 × 10¹⁵ ions/cm². The reduction of CeO₂ is attributed to a preferential sputtering of oxygen from the surface. As a result, Ar⁺ bombardment leads to a gradual buildup of an, approximately 0.69 nm thick, sputtering altered layer. Our studies have demonstrated that Ar⁺ bombardment is an effective method for reducing CeO₂ to CeO_2−x and the degree of the reduction is related to the energy and amount of Ar ions been exposed to the CeO₂ surface.     

Room temperature deposition of amorphous SiC thin films using low energy ion bombardment

Silicon carbide (SiC) films are prepared by single- and dual-ion beam sputtering deposition at room temperature, respectively. An assisting argon ion beam (ion energy Ei=150 eV) bombards directly the substrate surface to modify the SiC film surface. The thin films are characterized by the Fourier transform infrared spectroscopy (FTIR) and the Raman spectra. With assisting ion beam bombardment, the density of the Si–C bond in the film increases. Meanwhile, the excess carbon or the size of the sp² bonded clusters and the amorphous Si (a-Si) phase decrease. These results indicate that the composition of the films is mainly Si–C bond. UV-vis transmission shows that the E_opt increases steadily from 1.85 eV for the amorphous SiC (a-SiC) films without bombardment to about 2.29 eV for those with assisting ion beam bombardment.     

Effect of the plasma parameters on the properties of titanium nitride thin films grown by laser ablation

Titanium nitride thin films were deposited at low temperatures (less than 250 °C) using the laser ablation technique. The effect of both the laser beam energy density and the gas pressure on the plasma parameters was studied. The film structure, mechanical properties and surface morphology were investigated as a function of the plasma parameters. The results showed a strong dependence of these properties on the ion kinetic energy and plasma density. The gas pressure was seen to control the preferred orientation of the films in the (200) and (111) directions. At 1×10^-2 Torr only the (200) direction was observed. In addition, the crystal size for all the films was found to depend on the plasma parameters; generally, an increase of ion energy and plasma density resulted in a decrease of the crystal size. TiN films with hardness as high as 24.0 GPa, which is suitable for many mechanical applications, were obtained. The hardness was strongly affected by the ion energy, increasing as the ion energy increased. These results show that the properties of the deposited material are controlled in part by the degree of ion bombardment and the plasma density. PACS 81.15.Fg; 81.05.Je; 68.55.Jk; 52.70.Ds     

Cone formation from Mo thin films

It is demonstrated that Ar⁺-ion bombardment of a polycrystalline Mo film in the conventional sputtering mode generates conical protrusions with microscopic dimensions. Typical conical structures were observed in the vicinity of the lower edge of the crater produced by an ion beam, and their precursors are believed to be Mo grains grown at a lower ion dose. The cones were comparable with the precursors in average dimension, suggesting that a particle supply process compensated for the sputter removal of Mo atoms during the cone evolution. Evidence is also presented that Ar⁺ ions accelerated to a few keV produce a heating effect strong enough to melt isolated cones.     

kinetic energy reflection from polycrystals bombarded with Ar+, Kr+, and Xe+ ions

When the surface of a solid is bombarded with ions a fraction of the primary energy is reemitted by ion reflection and sputtering. The contribution of ion reflection or sputtering to energy reflection is determined by the mass ratio of the bombarding ions to the target atoms.^1,2 In the case of light ions the contribution of reflected ions is dominant. Results for He⁺ and Ne⁺ bombardment were described in a previous paper.³ The present paper deals with results for Ar⁺, Kr⁺, and Xe⁺ bombardment of the same targets as investigated before.³ The energies of the mass selected bombarding ions range from 9 to 16 keV. The measurements were carried out by means of the thermic detector described in a separate paper.⁴ For the given mass ratios most of the reemitted energy is related to sputtering.     

Vacancy-type defect distributions near argon sputtered Al(100) surface studied by variable-energy positrons and molecular dynamics simulations

A beam of variable-energy positrons, whose back-diffusion probability is measured as a function of positron implantation energy, is applied to studies of depth distribution of sputtering damage in aluminum. The defects are produced by argon ion bombardment of an Al(110) surface in ultra-high vacuum. We have varied the Ar⁺ energy, incident angle and dose, as well as sputtering and annealing temperatures. The extracted defect profiles have typically a narrow peak at the surface with a width of 10–20 A and a broader tail extending down to 50–100 Å. The shape of the defect profile varies only slightly with the sputtering energy and angle. Defect production at less than 1 keV Ar⁺ energies is typically 1–5 vacancies per incident ion. The defect profiles become fluence-independent at about 2 × 10¹⁶ Ar⁺ cm⁻². The defect density at the outer atomic layers saturates at high argon fluences to a few at%, depending on sputtering conditions. The sputtering temperature (below or above the vacancy migration stage at 250 K) has little effect on vacancy profiles. Defects anneal out gradually between 100 °C and 400 °C. Sputtering damage was also evaluated with the molecular dynamics technique. The shape and depth scale of the simulated collision cascades are in agreement with the experimentally extracted quantities.     

Investigation on surface compositions of CuNi alloy under Ar+ ion bombardment by ISS and in situ AES measurements

Surface compositions of CuNi(50 wt%) alloy under 3 keV Ar⁺ ion bombardment were measured by Auger electron spectroscopy (AES) and ion scattering spectroscopy (ISS). In situ AES measurement of sputter-deposited layer and sputtered sample surface indicated that surface composition became Ni-rich due to Ar⁺ ion sputtering at steady state, in accord with previous reports of preferential sputtering. ISS measurements with 3 keV Ar⁺ ions, however, have suggested that the composition of the outermost atom layer is not Ni-rich but slightly copperrich. This leads to the conclusion that the degree of preferential sputtering is small and that the question of preferential sputtering, particularly, the ratio of the sputtering yields, $\text{S}{}_{\mathrm{<mtext>Cu</mtext>}}\text{S}{}_{\mathrm{<mtext>Ni</mtext>}}$, based on AES measurement requires further examination.     

XPS and AES studies of anodic passive films grown on chromium electrodes in sulphuric acid baths

The surface composition and the thickness of anodic passive films formed on chromium electrodes in sulphuric acid baths have been studied by XPS and AES using Ar⁺—ion sputtering. The results are consistent with a 13–16-Å thick oxide layer of composition close to Cr₂O₃. Some evidence is also given concerning hydrated species located in the outermost part of the passive film.     

Sputter damage in Si surface by low energy Ar+ ion bombardment

The damage distributions in Si(1 0 0) surface after 1.0 and 0.5 keV Ar⁺ ion bombardment were studied using MEIS and Molecular dynamic (MD) simulation. The primary Ar⁺ ion beam direction was varied from surface normal to glancing angle. The MEIS results show that the damage thickness in 1.0 keV Ar ion bombardment is reduced from about 7.7 nm at surface normal incidence to 1.3 nm at the incident angle of 80°. However, the damage thickness in 0.5 keV Ar ion bombardment is reduced from 5.1 nm at surface normal incidence to 0.5 nm at the incident angle of 80°. The maximum atomic concentration of implanted Ar atoms after 1 keV ion bombardment is about 10.5 at% at the depth of 2.5 nm at surface normal incidence and about 2.0 at% at the depth of 1.2 nm at the incident angle of 80°. However, after 0.5 keV ion bombardments, it is 8.0 at% at the depth of 2.0 nm for surface normal incidence and the in-depth Ar distribution cannot be observable at the incident angle of 80°. MD simulation reproduced the damage distribution quantitatively.     

Relation between surface structures and sputtering ratios of copper single crystals

Polished (100) Cu crystals have been bombarded at target temperatures of 204 K, 294 K and 456 K by 10 and 20 keV Ne⁺ ions up to a total dose of 1.7 × 10¹⁹ ions/cm². The plane of incidence was chosen to be a {100} plane perpendicular to the surface. Measurements have been performed for incident angles between 36° and 44° with respect to the surface normal. In this angular interval the sputtering ratio and the surface structure have been studied by weightloss and replica electron microscope techniques respectively. At target temperatures of 204 K and 294 K an anomaly was observed in the curve of the sputtering ratio versus angle of incidence. A small peak appears where the curve slopes towards the 〈110〉 minimum. The position and height of the peak is a function of target temperature and ion energy.

This sputtering submaximum is accompanied by the formation of {100} orientated furrows perpendicular to the ion beam. The nucleation of this relief is tentatively discussed in terms of local deviations from perfection of the surface, which might be due to a singularity in the production of focusing collisions influencing the damage structure. The growth of the furrows and the submaximum in the sputtering ratio are discussed in terms of the angle between the ion beam and the characteristic {110} side of the furrows.

These sputtering and faceting phenomena have not been observed at 20 keV Ar⁺ ion bombardment nor generally under bombardment at a target temperature of 456 K.     

Low energy (⩽ 100 eV) sputtering of thin molybdenum nitride films

Molybdenum nitride films formed by 100 eV N⁺₂ bombardment to saturation of polycrystalline Mo have been sputtered to high fluence by normally incident 100 eV Ar⁺ and He⁺ and 15 eV Ne⁺ while the surface nitrogen concentration was monitored by Auger electron spectroscopy (AES). The penetration distance of nitrogen atoms during film formation and subsequent sputtering is assumed to be small enough that AES will detect, to some degree, all of the nitrogen in the film. The nitrogen AES signal decays exponentially to unsputterable levels for the 15 eV Ne⁺ and 100 eV He⁺ cases and decays bi-exponentially to near the bulk contamination level for the 100 eV Ar⁺ case. The results are interpreted according to existing concepts, but the kinetics of nitrogen loss is modeled using a two-layer adaptation of the standard model for adsorbate monolayer sputtering kinetics. Fitting our proposed model to the data yields apparent cross-sections which are interpreted as composites of cross-sections for experimentally indistinguishable elementary processes; these elementary cross-sections for each process are geometrical averages on the polycrystalline surface. Processes considered, in addition to nitrogen sputtering, include bombardment-induced transport of nitrogen within the film and sputtering of the Mo lattice itself.     

Sputtering of metals at ion-electron irradiation

It has been found that, in contrast to the commonly accepted opinion, simultaneous irradiation by 15-keV Ar⁺ ions and 2.5-keV electrons at temperatures above 0.5T _m (T _m is the melting temperature) induces much larger sputtering of metallic copper, nickel, and steel than irradiation only by Ar⁺ ions. The effect increases with the temperature. At T = 0.7T _m, the sputtering coefficients in the case of ion-electron irradiation are more than twice as large as the sputtering coefficients in the case of irradiation by Ar⁺ ions. The experiments on the sublimation of copper show that the sublimation rate in the case of the heating of a sample by an electron beam is higher than that in the case of heating in an electric vacuum oven. The revealed effects are explained by the electron-induced excitation of adatoms (atoms stuck over the surface, which appear owing to ion bombardment). Excited adatoms have a smaller binding energy with the surface and are sputtered more easily.     

Sputtering characteristics of fullerene C60 films under bombardment with 0.1–1-keV argon ions and atoms

The sputtering of fullerene C₆₀ films under bombardment with Ar⁺ ions was studied. In thin films, blistering effects related to diffusion of the implanted argon ions along the layer and substrate interface have been found to occur. A threshold behavior was observed for sputtering at ion energies around 0.2 keV, which is much higher than in graphites. It has been shown that dependence of the work function on ion energy can be described in the framework of Zigmund-Falcone’s approximation, which takes into account anisotropic effects in cascade collisions, and with Yudin’s approximation for the sputtering of elemental materials. The obtained surface binding energy for fullerenes is U _s?6.7 eV, which is less than the value for graphites, U _{s graph}=7.7 eV.