Electronic excitation in sputtered atoms and the oxygen effect

Bombardment of surfaces by ions gives rise to a variety of inelastic collision events leading to the ejection of excited atoms and ions. Such excited sputtered particles have been studied since more than 80 years through their optical emission, when they decay in front of the target to the electronic ground state, having lifetimes of 10⁻⁹ to 10⁻⁷ s, typically. Information on the energy distribution of such excited states can be obtained by two different techniques: light vs distance measurements (LvD) and by studying line profile broadening in light emission due to the Doppler effect. Only recently it has become possible to study in addition metastable excited atoms using laser induced fluorescence spectroscopy (LIF). Relative sputtering yields and energy distributions have been measured for such metastable states and two types can be distinguished. States with a very low excitation energy (0–0.3 eV), being sublevels of the electronic ground state, were found to have yields and energy distributions comparable to the electronic ground state, while metastable states at higher excitation energies (above 1 eV) seem to behave similar to short lived excited states, typically observed in secondary photon emission (BLE) with excitation energies in the range of 2–6 eV. This behaviour is also clearly visible with respect to oxygen surface coverage or increased near surface oxygen concentration where, similar to secondary ion emission, drastic changes in the yield by orders of magnitude have been found for excited atoms as well as for ions. In addition, under the same conditions a strong decrease in the sputtering yield of neutral ground state atoms has been observed for a number of metals. LIF results for highly excited metastable states are compared with recent results obtained by studying line profile broadening in light emission for Ca, Al and Cr targets. Different mechanisms that have been proposed to account for the observations will be discussed.     

Sputtering from spherical Au clusters by energetic atom bombardment

Using molecular-dynamics simulation, we study the effect of 100 keV Au atom bombardment of spherical Au clusters (radius R=40 Å), containing 15,784 atoms. Results range from projectile transmission with only few atoms sputtered to more or less complete cluster disintegration. During disintegration, besides major fragments of the original cluster, monatomics and a large number of clusters with sizes up to 100 atoms, and even beyond, are created. Angular and energy spectra of sputtered atoms show features of both collisional sputtering and evaporation: particle emission is isotropic with an additional contribution of preferential emission along [1 1 0] directions. Energy spectra show the high-energy E⁻² fall-off typical of linear-cascade sputtering plus an additional low-energy thermal component.     

Angular distributions of Ni and Ti atoms sputtered from a NiTi alloy under He and Ar ion bombardment

The angular distributions of sputtered components were measured for NiTi polycrystalline alloy under 9 keV Ar⁺ and He⁺ ions bombardments with various fluences in ultrahigh vacuum. Combination of Rutherford Backscattering Spectrometry (RBS) and Auger Electron Spectrometry (AES) techniques allowed us to observe enhanced concentration of Ni over a layer with thickness comparable to a primary He⁺ ions penetration depth due to selective sputtering of Ti atoms and radiation-induced diffusion processes. A preferential emission of Ni atoms towards the surface normal was observed during bombardment by both He⁺ and Ar⁺ ions. More forward-peaked “over-cosine” angular distributions of sputtered Ni in comparison with those for Ti atoms have been measured. Nonstoichiometric sputtering of NiTi alloy dependent on emission angle was observed for bombardment fluence of He⁺ well below that needed for the steady-state altered layer formation. To explain the peculiarities of NiTi sputtering, an interpretation is discussed in terms of sputtering due to backscattered He⁺ ions.     

Dynamics of cluster induced sputtering in gold

Impacts of 0.13-1.4 MeV Au₁₃ clusters onto Au(1 1 1) target are investigated in molecular dynamics simulations. The evolution of sputtered Au atoms and clusters are simulated up to 10 ns. The total sputtering yield, angular and velocity distributions of the sputtered material, as well as dimensions of impact induced craters are compared to recent experimental results. It is shown that the experimental observations can be explained by a flow of atoms from the craters. Secondary cluster ejection from crowns formed around the craters is found to be one of the main mechanisms of sputtering. The results are summed up in an empirical model.     

Photon emission produced by particle-surface collisions

Visible, ultraviolet and infrared optical emission results from low-energy (20 eV–10 keV) particle-surface collisions. Several distinct kinds of collision induced optical radiation are discussed which provide fundamental information on particle-solid collision processes. Line radiation arises from excited states of sputtered surface constituents and backscattered beam particles. This radiation uniquely identifies the quantum state of sputtered or reflected particles, provides a method for identifying neutral atoms sputtered from the surface and serves as the basis for a sensitive surface analysis technique. Broadband radiation from the bulk of the solid is attributed to the transfer of projectile energy to the electrons in the solid. Continuum emission observed well in front of transition metal targets is believed to arise from excited atom clusters (diatomic, triatomic etc.) ejected from the solid in the sputtering process. Application of sputtered atom optical radiation for surface and depth profile analysis is demonstrated for the case of submonolayer quantities of chromium on silicon and aluminium implanted in SiO₂.     

Assessment of approximations for efficient topography simulation of ion beam processes: 10 keV Ar on Si

The main assumption of existing efficient topography simulations is that sputtering is a local process that depends only on the angle of incidence and not on the detailed shape of the surface. If redeposition is considered, sputtered atoms are redeposited and cause no further sputtering when they hit another part of the surface. Furthermore the angular distribution of sputtered atoms follows a cosine law. If ion reflection is considered, ions do not lose energy during backscattering. Using binary collision simulations (IMSIL) and comparing them with results obtained by a topography simulator (IonShaper^®) we show that all these assumptions need refinement for the simulation of nanostructures except the neglect of sputtering by sputtered atoms. In addition we show that a nonlocal model is essential for ion beam induced deposition of narrow structures.     

Modelling the erosion of beryllium carbide surfaces

Redeposition of beryllium eroded from main chamber plasma facing components of ITER onto the divertor material carbon creates a mixed material, beryllium carbide Be₂C, whose interaction with the plasma is not well known. In this study, we have investigated the erosion of Be₂C by deuterium using molecular dynamics simulations and ERO impurity modelling. We found that beryllium sputters preferentially over carbon and identified the sputtering mechanism in the ion energy range 10-100 eV to be both physical and swift chemical sputtering. In addition to single atoms, different types of small molecules/clusters were sputtered, the most frequently occurring molecules being BeD, Be₂D, and CD. The sputtering threshold was found to lie between 10 and 15 eV. The MD sputtering yields were used in plasma impurity simulations, serving as a replacement for input data obtained with TRIM. This changes the accumulation rate of impurity Be in the divertor region compared to previous estimates.     

Synergism in sputtering of copper nanoclusters on graphite substrate at low energy Cu2 bombardment

Molecular dynamics simulation of Cu cluster sputtering by 50-200 eV/atom Cu₂ dimers and Cu single atoms has been performed. The clusters were located on a (0 0 0 1) graphite surface and consisted of 13-195 atoms. Synergy features were identified in the sputtering yield and energy distributions of sputtered particles calculated for the cases of cluster bombardment with Cu dimers and monomers at the same velocity. The reason for the nonlinear effects in surface cluster sputtering is the overlapping of collision cascades generated by each of the dimer atoms.     

20—80keV Ar~+离子对稀释Si(Co,Ta)合金的溅射

荷能离子对单元素的溅射已有较好的理论解释,但是对多元合金或化合物溅射的研究才开始不久,目前尚无一个能够成功地解释实验现象的理论。 溅射后合金样品近表面组成的改变,是一种有趣的实验现象。实验中发现三元合金的现象比二元合金更为复杂,例如,元素的近表面改变与溅射离子的能量有关,这是用现有的择优溅射理论无法解释的。为研究这种现象,我们选取了Si(Co,Ta)三元合金,在分别用20到     

Light emission from oxygen covered Al and Cu surfaces

Ion beam induced light emission is used to investigate the sputtering yield, S_O, of oxygen atoms on the surfaces of a polycrystalline copper and an Al(1 1 1) target. Under Ar⁺ and Ne⁺ ion bombardment of Al(1 1 1) and polycrystalline copper targets, spectral lines of Cu I and Al I emitting from sputtered excited atoms are measured as a function of the oxygen partial pressure, wavelength and beam energy. The light emission for two Al I lines (3082 and 3962 Å) and Cu I lines (3247 and 3274 Å) are proportional to the oxygen partial pressure (1×10⁻⁴ Torr). Above 2×10⁻⁴ Torr, the light intensities start to decrease which is consistent with other measurements. From saturated-oxygen covered target surfaces, light intensities of Al I and Cu I lines are measured as a function of time and oxygen partial pressures. The sputtering yields could be determined from the curves of spectral lines directly. For 10 and 20 keV Ar⁺ ions bombarding the copper surface, the oxygen sputtering yields are 0.34 and 0.22 (atoms/ion), respectively. The same copper target was bombarded by Ne⁺ ions at 5 and 10 keV, the oxygen sputtering yields are 0.87 and 0.59, respectively. For 10, 15, and 20 keV Ar⁺ bombarding an Al(1 1 1) target, the obtained sputtering yields are 0.44, 0.31, and 0.2 (atoms/ion), respectively.     

Sputtering and Ion-Source Technology

Sputtering is dependent on a number of projectile and target parameters. It is shown that the dependence of the sputtering yield on projectile energy, angle of incidence and atomic number is well understood. Also, the dependence on the bulk properties of the target is described reasonably well by theory, while the dependence on the actual surface topography of the target is difficult to quantify. Positive-ion sources mainly depend on the number of atoms sputtered per incoming ion (sputtering yield), while also energy- and angular-distributions of the sputtered material are of primary importance for negative-ion sources. These distributions are reasonably well known and allow a direct calculation of the emittance of some negative-ion sources.     

Sputtering of graphite in pulsed and continuous arc and spark discharges

The environment that leads to the sputtering of graphite electrodes and formation of carbonaceous discharge has been studied with emission spectroscopy. Population level densities, excitation & vibrational temperatures and electron densities have been obtained from a set of three ion sources. The sources operate in continuous and pulsed discharge modes. The sputtered species include monatomic, diatomic and higher carbon clusters. The main sputtered species are excited and ionized C₁ (CI, CII, respectively) and C₂. In the continuous arc discharge the vibrational temperature derived from the Swan band of C₂ is ∼10,000 K, whereas, in the pulsed arc the excitation temperature of Neon is ∼11,000 K. The spark discharge yields an average excitation temperature of CI and NI ∼ 5500 K.     

The influence of projectile charge state on ionization probabilities of sputtered atoms

The ionization probability of atoms sputtered from a clean polycrystalline metal surface was measured for different charge states of the projectile used to bombard the sample. More specifically, a polycrystalline indium surface was irradiated with Ar⁺ and Ar⁰ beams of energies between 5 and 15 keV, and In⁺ secondary ions and neutral In atoms emitted from the surface were detected under identical experimental conditions regarding the sampled emission angle and energy. The resulting energy integrated ionization probability of sputtered In atoms is consistently found to be smaller for neutral projectiles, the difference decreasing with decreasing impact energy. The observed trends agree with those measured for kinetic electron emission, indicating that secondary ion formation is at least partly governed by kinetic substrate excitation.     

A SMALL UNBALANCED MAGNETRON SPUTTERING SOURCE WITH MULTIPOLE MAGNETIC FIELD ANODE

A small unbalanced magnetron atom source with multipole cusp magnetic field anode is described.The co-axial magnetron rpinciple is extended to the circular planar magnetron atom source,which raises the efficiency of sputtering target area up to 60%.The multipole magnetic field is put in the anode.which makes the unbalanced magnetron atom source run in a higher discharge current at a lower arc voltage condition.Meanwhile.the sputtering atoms through out the anode can be ionized partially,because the electron reaching the anode have to suffer multiple collisons in order to advance across the multipole magnetic field lines in the anode,which enhances the chemical reactivity of the ejecting atoms in film growth and improve the property of film depositing.     

低能高束流氩离子源的结构及性能

离子源技术是等离子体研究中的一项重要内容,而低能大束流源则是离子源技术研究中的一个重要方向,因为这样的源在离子束刻蚀、离子束溅射镀膜以及荷能粒子与物质相互作用方面都有广泛的应用;本文采用空心阴极空心阳极结构,用热阴极电子发射弧放电驱动并用磁场约束产生等离子体,用曲面发射引出离子束,研制成了氩气放电溅射离子源;研究了灯丝加热电流、弧压对弧流的影响和弧流与工作气体压力对离子束引出的影响规律.离子源的引出电压在0-4.0 kV之间连续可调,最大引出束流为100 mA,束斑面积为φ6.0 cm,以Ti为溅射靶时的最大溅射沉积率为0.45 nm/s,离子源可连续工作160 h.     

The density effects in sputtering of amorphous materials

The effects of the target atomic density on sputtering of amorphous targets under 1 keV Ar ion bombardment have been investigated using binary-collision simulation. Attention was given to the sputtering yield, and the angular and energy distributions of sputtered atoms. A large set of targets, from ³Li to ⁹²U was considered and three interatomic potentials were applied. It has been shown that both the sputtering yield and the angular and energy distributions of sputtered atoms are undoubtedly dependent on the target atomic density. Results are compared with the data from the literature.     

Cu－37at％ Ag共晶合金的离子溅射研究

侧重研究了入射Ａｒ＋离子不同剂量轰击时表面微形貌和溅射原子角分布之间的关联，并建议用“元素按靶点表面微形貌特征局域富集模型”来解释溅射原子角分布形状以及择优溅射曲线的变化；发现其结果与实验相符合。     

Size effects of gas cluster ions on beam transport,amorphous layer formation and sputtering

Size effects of gas cluster ions on beam transport or collisions with residual gases, for amorphous layer formation and for sputtering effects were studied using a size-selected GCIB system. A GCIB releases its constituent atoms by collisions with residual gases, and as a result, it loses its acceleration energy. The number of released atoms is determined by the energy per atom and the cohesive energy of gas. By controlling the cluster size and electron ionization energy to carry out low-energy irradiation, formation of amorphous layer or crater-like damages on surfaces can be reduced. The dependence of the sputtering yield of Au on cluster sizes shows that a linear relationship exists between the number of Au atoms sputtered by one Ar atom and the energy per atom. It is shown that the cluster size, which defines the energy per atom, is the most important parameter affecting beam transport, low-damage processing and sputtering with GCIB.