Molecular dynamics study of sputtering of Cu (111) under Ar ion bombardment

Abstract

We have used the molecular dynamics (MD) technique using many-body interaction potentials to analyse in detail the processes leading to sputter emission, in order to gain a microscopic understanding of low energy bombardment phenomena. Calculations were performed for a Cu (111) single crystal surface bombarded with Ar atoms in the energy range from 10–1000 eV. The results presented for low bombarding energies are mainly concerned with the near sputtering threshold behaviour, yields and depth of origin of sputtered atoms. Furthermore, it is found, that in addition to sputtered atoms, a large number of ad-atoms at the surface are generated during the evolution of the collision cascade. At higher energies the question of cluster emission and especially their energy distribution and angular distribution are addressed. It was found that the energy distributions for the dimers and monomer atoms exhibit a similar dependence on emission energy as has been observed recently also experimentally. For atoms good agreement with the theoretical Sigmund-Thompson energy distribution was observed. However, for dimers we found that the energy distributions exhibit an asymptotic behaviour at high energies with E^?3 rather than with E^?5, as predicted in previous modelling of cluster emission. Concerning the angular distributions six emission spots, three strong ones in the <110> and three weak ones in the <100> direction were found for atoms, but for dimers only emission spots in the <110> direction were observed, in agreement with experimental results.     

Energy deposition,reflection and sputtering in hyperthermal rare-gas→Cu bombardment

Using molecular-dynamics simulation, we study the scattering and penetration of normally incident hyperthermal (5–400 eV) Ne, Ar, and Xe atoms off a Cu crystal. We find that between 80% and 98% of the incident energy is deposited in the solid; the fraction depends primarily on the projectile mass, and — for not too low energies — only slightly on the bombarding energy. At low energy, the major part of the non-deposited energy is carried away by the reflected projectile. At energies above the sputter threshold, an increasingly important contribution of between 2% and 6% of the incident energy is carried away by sputtered particles. These results compare well with experiment. Electronic inelastic losses show only little influence on this behaviour. We demonstrate that the inclusion of a realistic attractive interaction between the projectile and the target atoms influences the energy deposition considerably at energies below around 100 eV.     

Angular-resolved energy distribution of secondary ions emitted from a silicon target sputtered by a xenon ion beam

This paper reports preliminary results obtained on an experimental apparatus dedicated to the study of angular resolved energy distribution of particles emitted from a sputtered target. Secondary ions emitted during the bombardment of a silicon target by xenon ions at a primary energy of 10keV have been studied. In its low energy part the distribution reaches a maximum around 8eV, and then decreases according to an E ^–1 law. In the range 200eV to 1000eV, a second maximum appears whose height depends on the emission angle. Apart from this range, the angular distributions have a cosine square-like shape. On the contrary, the angular distribution of ions with energy between 200eV and 1000eV is pointed in a forward direction near the specular reflection direction of the ion beam. It is assumed that the measured ions correspond to two ionic populations: secondary ions sputtered according to the linear cascade theory and recoil silicon target ions.     

Energieverteilungen bei der Festkörperzerstäubung durch Ionenbeschuß

The energy distributions of the neutral particles sputtered from polycrystalline targets of Al, Ti, Ni, Cu and Ag by normally incident Ar⁺-ions in the 1 keV region have been determined for ejection energies below 20 eV in a direction close to the normal to the target surface. The experimental method employed is strongly connected to the characteristic properties of a low pressure electrodeless hf plasma used as an effective ion source as well as an ionizing medium for the ejected target atoms. The resulting curves always show a maximum at most probable ejection energies between 1 and 5 eV, being approximately half of the surface binding energy. These curves are converted to the corresponding energy distributions for the recoil atoms within the target by an energy dependent factor. It is found that the energy distribution within the bombarded solid decreases monotonically with the inverse square of the energy of the recoils.     

Experiments on the sputtering of neutral Cu2 dimers from Cu by Ar+ ions (60–300 eV)

A planar polycrystalline copper target was bombarded normally by Ar⁺ ions with energies ranging from 60 to 300 eV. in the source of a mass spectrometer. The neutral particles sputtered normally from the target were post-ionized and analyzed in the mass spectrometer. A thermionically sustained, magnetically confined low pressure arc plasma was used to supply the bombarding ions, and for post-ionization of the neutral sputtered species. It was found that the relative yields of the sputtered neutral post-ionized Cu₂ dimers are linearly proportional to S², where S is the total sputtering yield for Ar⁺ -Cu. The results support the recombination model for the formation of neutral dimers in sputtering.     

Low energy ion impact phenomena on single crystal surfaces

The dynamics of a solid bombarded by a 600 eV Ar⁺ ion have been studied classically by computer simulation. The model uses a crystallite of about 250 atoms described by pair potentials derived from elastic constants and which reproduce the surface binding energy of the solid. The relative calculated yield of secondary atom emission from the three low index faces of Cu follow the previously determined experimental order (111) > (100) > (110). We find major differences in the sputtering mechanisms for these faces. On (110), the impacted atom is ejected most frequently, while on (111) and (100) it almost never leaves the solid. We report the energy distribution of the sputtered particles for each face. The simulation successfully predicts the shape of the curve including the low energy maximum which is observed experimentally near 2 eV. In addition our model shows that many low energy atoms attempt to leave the crystal but are subsequently trapped to the solid at large distances from their original sites. This mechanism of radiation enhanced diffusion inevitably occurs in conjunction with sputtering or any other heavy secondary particle emission or scattering process.     

C2团簇在金刚石(111)表面吸附结构的分子动力学模拟

利用Brenner(#2)半经验多体相互作用势和分子动力学模拟方法研究荷能的C₂在金刚石(111)表面的化学吸附过程.模拟300 K时,初始入射动能分别为1,20,30 eV的C₂团簇从6个不同位置轰击金刚石(111)表面,观察到C₂团簇在金刚石(111)表面形成的吸附结构,表面C原子键的打开以及C₂团簇与表面C原子成键等物理过程,并讨论不同入射位置和入射能量对沉积团簇的结构特性的影响.结果表明,对于表面不同的局部构型,C₂团簇发生不同的碰撞过程,C₂团簇入射能量的提高有利于成键过程的发生,从原子尺度模拟沉积机制.     

Resputtering effects by measurements of angular distributions

Angular distributions of copper atoms sputtered at bombarding energies between 100 and 1000 keV from polycrystalline targets are measured by a collector method. The deposit was detected immediately after bombardment with a photometer placed in the sputtering chamber. This arrangement allowed to perform series of measurements at different ion doses without oxidation of the film. Because of the fastness of this method we obtained a large number of distribution profiles showing principle errors of the collector method effected by condensation coefficients lower than one. The angular distributions are described without influence of these errors by the angle of maximum emission and the base width of the distributions.     

Yields and ionization probabilities of sputtered Inn particles under atomic and polyatomic Aum ion bombardment

The emission of neutral and charged atoms and clusters from a polycrystalline indium surface under bombardment with 5 and 10 keV Au, Au₂, Au₃ and Au₅ projectiles was investigated. Single photon laser postionization was utilized for the detection of sputtered neutral particles. Secondary ions were detected without the laser under otherwise exactly the same experimental conditions. The relative cluster yields were found to be enhanced under polyatomic projectile bombardment, more so the larger the number of atoms in the sputtered cluster. The ionization probability strongly increases with increasing cluster size, but is essentially independent of the projectile impact energy. At a fixed impact energy, the ionization probability of sputtered monomers was found to decrease with increasing number of constituent gold atoms per projectile, but there was no detectable effect for sputtered dimers and larger clusters.     

Low energy sputtering of neutral Cu2 molecules

The ratios of relative yields of neutral sputtered Cu₂ molecules to neutral sputtered Cu atoms were found to be linearly proportional to the sputtering yield of Cu, from a Cu target under bombardment by Ar⁺ ions (energy 50–90 eV), as determined by secondary neutral mass spectrometry.     

The formation of excited states of sputtered yttrium atoms

Optical spectra of ion-photon emission of atoms sputtered by bombarding the yttrium target surface with 40-keV Xe⁺ ions are studied experimentally. It is found that the levels corresponding to transitions from the 4d shell are excited more efficiently in the sputtering process. Possible new mechanisms for the excitation of atomic levels in the sputtering of a solid are considered.     

Die Geschwindigkeitsverteilung von kathodenzerstäubtem Kalium

The differential sputtering ratio (energy spectrum) of polycrystalline potassium sputtered by Ar and Xe ions of 28 keV energy has been measured using surface ionization detection. The spectrum shows a maximum at 0.5 eV and drops to half the maximum value at 2.0 eV. The total sputtering ratio for incident Xe ions is found to be 2.7±1.3 atoms/ion. To check what influence the detector might have on the measured spectrum, different materials and temperatures were used. Below 3 eV the detection probability is energy independent, if the detector is properly heated. Above that energy the measured spectra become uncertain, probably because of the onset of reflexion. Therefore the “focussing energy” of sputtering theory cannot be deduced.     

Momenta of the particles emitted by a target heavily irradiated with low-energy ions

The total momenta of the particles emitted by a target intensely sputtered with heavy noble-gas ions with an energy of E ₀≈0.5 keV are measured. For liquid Ga targets and Ga targets at the premelting temperature, the measured momenta are close to the expected values for the sputtered metal atoms and reflected ions, whereas for Cu and Zr targets, the measured momenta are significantly higher. It is assumed that these excessive momenta are related to the sputtering of the noble gas atoms implanted into the target. The average energy of these atoms is estimated as 〈E〉≈20 eV. When gallium is irradiated, the implanted atoms diffuse predominantly to the surface and then are desorbed.     

Sputtering—a review of some recent experimental and theoretical aspects

After a brief outline of the present sputtering theory for a random solid, recent results of the sputtering yieldS for polycrystalline targets are discussed, in particular in view of the influence of the projectile mass and the bombarding angle. The angle dependence ofS at low bombarding energies, and results on the angular distribution of sputtered particles for oblique ion incidence point out necessary modifications of present sputtering theories with respect to the anisotropy of the collision cascades in the solid and the influence of the target surface. The energy distribution of the neutral particles ejected along the target normals is related to the theoretically predictedE ^?2-distribution of low energy recoils in the Recent mass spectrometric studies of postionized sputtered neutrals are discussed in view of the formation of sputtered molecules and the application of sputtered neutral mass spectroscopy for surface analysis. Finally, the paper deals with ion-induced surface effects on non-elementary sputtering targets, and the protracted removal of foreign atoms from a matrix.     

Interaction of low-energy Cu2 dimers with copper clusters on the graphite surface

The sputtering of clusters consisting of 13, 27, and 75 copper atoms from the (0001) graphite surface under bombardment by Cu₂ dimers with energies of 100, 200, and 400 eV has been simulated using the molecular dynamics method. A comparative analysis of the distributions of backscattered particles and their energies over polar angles and the energy distributions of sputtered atoms has been performed. The factors responsible for the large sputtering yield from surface clusters under their bombardment with dimers as compared to copper and xenon monomers have been discussed. It has been demonstrated that, in the case of bombardment with dimers, the substantial role in the sputtering of surface clusters is played by the overlap of collision cascades initiated by each atom of the incident dimer. The differences in the sputtering under cluster and atom bombardments are especially pronounced in the case of large surface clusters.     

Quantitative Auger electron spectroscopy analysis with co-evaporated AuCu films

A method for the quantitative Auger electron spectroscopy (AES) analysis by using a co-evaporation technique is extended to the AuCu system following the previous work. The calibration curves for lower Auger energy have peaks at 60 eV for Cu and at 69 eV for Au, and for higher Auger energy peaks at 239 eV for Au and at 920 eV for Cu. It is found that a simple linear relation does not exist in the results for AES measurements and the bulk analysis by atomic absorption spectroscopy (AAS) because of the back-scattering effect and the overlap of the spectra at lower energies in the Au-Cu system. It is also found that the adsorption of oxygen caused by electron beam bombardment has a significant influence on the AES results. The calibration curves obtained after a correction for oxygen adsorption are successfully applied to the determination of the composition at the surface of a sputtered AuCu alloy.     

Focusing of atoms sputtered from the (001) Ni surface for the Gaussian distribution of ejected atoms

Angular distributions of atoms sputtered from the (001) Ni surface for the Gaussian initial angular distributions of ejected atoms have been studied by the molecular dynamics method using computer simulation. Focusing of ejected atoms has been observed for the relatively wide initial distributions for the emission stage, while the polar angular defocusing has been observed for the narrow distributions. The shift character for the maximum of the polar angular distribution of sputtered atoms being the energy differential has been found to change from monotonous to nonmonotonous with an increase in the initial width of the distribution.     

Structure sensitive factors in molecular cluster formation by ion bombardment of single crystal surfaces

The dynamics of molecular cluster formation from a solid bombarded by a 600 eV Ar⁺ ion have been studied classically by computer simulation. The dimers and trimers are found to establish their identity as clusters within interaction range of the solid, but not by a direct ejection of a bound molecule. The Cu₂/Cu and Cu₃/Cu ratios are found to be strongly dependent on crystal orientation. The (111) face is 2–3 times more likely to produce multimers than the (100) face. We find 9 trimers from (111) but none from (110). The relationship between cluster composition and the original arrangement of those atoms on the surface is presented in detail. We find that each multimer forms from atoms that originate within a roughly circular region of area ～70 Ų or less. This region is not necessarily centered on the ion impact point. A consequence of this observation is that dimers can consist of atoms that were several Ångströms apart on the surface but that most trimers contain at least one nearest neighbor pair of atoms. The calculated energy distribution for the dimers matches well with similar experimental studies.     

Auger-spectrum simulation techniques for surface analysis of alloys with overlapping peaks: sputtered and annealed W—Mo alloys

The surface composition of a 50% W—Mo alloy has been investigated using Auger electron spectroscopy. Problems arising from carbon contamination and the strong overlap of the intense, surface-sensitive low-energy Auger peaks have been solved. Spectra for the alloy were collected digitally and could be simulated satisfactorily using pure-element spectra. The steady-state surface composition under 500 V Ar⁺ ion bombardment shows an enrichment of the surface in W, caused by preferential Mo sputtering. It is observed that the surface composition is uniform over the range of escape depths of the Auger electrons. This is consistent with enhanced diffusion and mixing over the penetration depth of the bombarding Ar⁺ ions. On annealing, the W-enriched sputtered surface becomes Mo-enriched, consistent with surface segregation of the more weakly bonded Mo atoms. However, in contrast with the sputtered surface, it is observed that a single simulation over the range of Auger-electron energies is not possible. The Mo enrichment indicated is largest for the 120 eV peak and decreases with increasing energy (escape depth), becoming a minimum at 220 eV. This is consistent with a monolayer segregation model, which is tested using published values for electron inelastic mean free paths. The calculated monolayer composition is x_Mo 0.94, in agreement with the predicted ideal-solution values of 0.98 ± 0.02 for different orientations.     

Ion-induced secondary electron and negative ion emission from Mo/O

Absolute yields of secondary electrons and negative ions resulting from collisions of Na⁺ with Mo(100) and a polycrystalline molybdenum surface have been measured as a function of the oxygen coverage of the surface for impact energies below 500 eV. The sputtered negative ions have been identified with mass spectroscopy, and O⁻ is found to be the dominant sputtered negative ion for the surfaces at all oxygen coverages and impact energies. Both the electron and O⁻ yields have an impact energy threshold at about 50 eV and exhibit a strong dependence on oxygen coverage. The kinetic energy distributions of the secondary electrons and sputtered O⁻ were determined as functions of the oxygen coverage and impact energy. The distributions for O⁻ are characterized by a narrow low-energy peak (at 1–2 eV) followed by a low-level high-energy tail. The secondary electrons have a narrow (FWHM 1–2 eV) kinetic energy distribution, centered approximately at 1–2 eV. The shapes of the distributions and their most probable energies are essentially invariant with impact energy, oxygen coverage and the nature of the Mo surface. The emission is explained and analyzed in terms of a simple model which involves a collision-induced electronic excitation of the MoO⁻ surface state. The decay of this excited state leads to the production of both secondary electrons and O⁻ with energy distributions and yields comparable to those observed.