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.     

Mass spectroscopy of sputtered neutrals and its application for surface analysis

Mass spectroscopic studies of the neutral particles sputtered by Ar⁺ions at energies around 1 keV from polycrystalline targets of 11 different metals have been performed, using a hf plasma maintained in pure argon at some 10^?4 Torr by electron cyclotron wave resonance as an ionizing medium as well as an effective ion source. Besides sputtered atoms Me₁ and molecules Me₂ with intensity ratios R₂₁ between Me₂ and Me₁ in the order of 10^?2 to 10^?1, neutral triatomic complexes Me₃ with corresponding ratios R₃₁ of some 10^?4 are found. Possible applications of the experimental method for surface analysis are discussed for previously air exposed polycrystalline Ta and Nb surfaces.     

Kinetic energy distributions of neutral In and In2 sputtered by polyatomic ion bombardment

Kinetic energy distributions of neutral In monomers and In₂ dimers sputtered from a polycrystalline indium surface under bombardment with 5 keV/atom Au₁⁻ and Au₂⁻ projectiles have been investigated by means of laser postionization time-of-flight mass spectrometry. Results show that 5 keV Au₁ bombardment leads to results in full compliance with linear cascade sputtering theory. For polyatomic ion bombardment, we find a clear transition to a collisional spike dominated emission process. The spike contribution appears as a low-energy part in the sputtered flux which increases with increasing projectile nuclearity and energy. We show that, the velocity spectrum associated with the low-energy contribution is virtually identical for sputtered monomers and dimers. This finding has important implications with respect to the particle emission mechanism under polyatomic projectile bombardment.     

Sputtering of Cu and Zn atoms from elemental and alloy targets

The energy distributions of Cu and Zn atoms sputtered from elements and Cu_xZn_1-x alloys (x=0.80, 0.24) with a 6 keV Ar⁺ beam have been measured. It was found that the collision-cascade theory properly described the flux of sputtered atoms. From the spectra the binding energies of Cu and Zn atoms in the elemental and alloy surfaces were determined. The collision-cascade theory and the experimentally adjusted values of the binding energies allowed for calculation of the total and partial sputtering yields, and the equilibrium surface composition of the ion bombarded alloys. This work was carried out as a part of Research Project M.R. I/5.     

Effect of helium/argon gas ratio in a He-Ar-Cu<Superscript>+</Superscript> IR hollow-cathode discharge laser: modeling study and comparison with experiments

The He-Ar-Cu⁺ IR laser operates in a hollow-cathode discharge, typically in a mixture of helium with a few-% Ar. The population inversion of the Cu⁺ ion levels, responsible for laser action, is attributed to asymmetric charge transfer between He⁺ ions and sputtered Cu atoms. The Ar gas is added to promote sputtering of the Cu cathode. In this paper, a hybrid modeling network consisting of several different models for the various plasma species present in a He-Ar-Cu hollow-cathode discharge is applied to investigate the effect of Ar concentration in the gas mixture on the discharge behavior, and to find the optimum He/Ar gas ratio for laser operation. It is found that the densities of electrons, Ar⁺ ions, Ar_m ^* metastable atoms, sputtered Cu atoms and Cu⁺ ions increase upon the addition of more Ar gas, whereas the densities of He⁺ ions, He₂ ⁺ ions and He_m ^* metastable atoms drop considerably. The product of the calculated Cu atom and He⁺ ion densities, which determines the production rate of the upper laser levels, and hence probably also the laser output power, is found to reach a maximum around 1–5 % Ar addition. This calculation result is compared to experimental measurements, and reasonable agreement has been reached. Received: 14 October 2002 / Revised version: 28 November 2002 / Published online: 19 March 2003 RID="*" ID="*"Corresponding author. Fax: +32-3/820-23-76, E-mail: annemie.bogaerts@ua.ac.be     

Indium sputtering upon bombardment with cluster ions

A surface-ionization method is developed for measuring the integral yields of neutral particles sputtered under the effect of ion bombardment. An investigation is performed to compare the integral yield of particles sputtered upon bombarding indium with Bi _m ⁺ cluster ions (m = 1?C7) in the energy range of 2?C10 keV and the secondary ion emission under bombardment with Bi _m ⁺ cluster ions (m = 1?C5) in the energy range of 6?C18 keV. A nonadditive increase in the indium sputtering coefficient is observed with an increasing number of atoms in the bombarding clusters.     

A Mössbauer study of amorphous ytterbium — Noble metal alloys: Short-range order versus dense random packing

Amorphous alloys Yb₈₀X₂₀ (X=Cu,Ag,Au) have been investigated by¹⁷⁴Yb Mössbauer spectroscopy. Samples have been prepared by sputtering and by roller quenching for all 3 alloys. For the materials studied, the distribution of the quadrupole splitting parameter δ_Q and of the asymmetry parameter η, corresponds to the distribution expected for a dense random packing model. No significant differences between the results for quenched and for sputtered samples were found.     

Angular distribution of sputtered alloy. Experimental and simulated study

Angular distribution of Cu and Be atoms sputtered from Cu98 Be2 alloy under 5 Kr⁺ ion bombardment were measured at different angle of incidences (0, 30, 70 and 80^○). The sputtered material is collected on a Mylar^TM foil surrounding the target. The used collector was mounted at different ejection angles and analyzed by inductively coupled plasma optical emission spectroscopy (ICP-OES). The SRIM-code program was employed to obtain the sputtering yield of Cu and Be from simulated Cu98 Be2 target. The experiment was combined with simulations and revealed that both of them were in a fairly good agreement. Furthermore, angular distribution of differential sputtering yields of both Cu and Be showed over-cosine tendency.     

Improved resistive switching performance in Cu-cation migrated MoS2 based ReRAM device incorporated with tungsten nitride bottom electrode

The resistive switching characteristics of sputtered deposited molybdenum disulphide (MoS₂) thin film has been investigated in Cu/MoS₂/W₂N stack configuration for Resistive Random Access Memory (ReRAM) application. The benefits of incorporating tungsten nitride (W₂N) as a bottom electrode material were demonstrate by stability in operating voltages, good endurance (10³ cycles) and long non-volatile retention (10³?s) characteristics. Resistive switching properties in Cu/MoS₂/W₂N structure are induced by the formation/disruption of Cu conducting filaments in MoS₂ thin film. Ohmic law and space charge limited current (SCLC) are observed as dominant conduction mechanism in low resistance state (LRS) and high resistance state (HRS) respectively. This study suggests the application of MoS₂ thin films with W₂N bottom electrode for next generation non-volatile ReRAM application.     

Cluster emission under ion bombardment of metallic targets

Mass spectroscopic studies of the neutral particles sputtered by Ar⁺ ions at 8 keV from polycrystaline samples have been performed, using non-resonant laser ionization and subsequent time-of-flight mass spectroscopy. Besides sputtered atoms, also dimer and trimer contributions in the order of 10^–1 to 10^–2 and 10^–3 to 10^–4, respectively, are found in the sputtered flux. The data obtained here together with previously published data by other groups for different bombarding energies provide strong support for the validity of the recombination model.     

Optical emissions of products sputtered from Fe, Fe2O3 and Fe3O4 powders

Powder iron has been bombarded by a 5 keV Kr⁺ ions in a vacuum better than 10^-7 torr and under few 10^-6 torr ultra pure oxygen partial pressure. The optical spectra of the sputtered particles were recorded between 340.0 nm and 410.0 nm. These spectra exhibit discrete lines, which are attributed to neutral excited atoms of iron. Two iron oxides, namely hematite (Fe₂O₃)_{3}) and magnetite (Fe₃O₄)_{4}), in powder form, were studied under the same experimental conditions and identical lines were observed in the obtained spectra. The absolute intensities of the spectral lines in all spectra were measured and the differences in the recorded yield photons were discussed in term of electron-transfer processes between the excited sputtered atom and the bombarded surface. In accordance with the proposed interpretation, we suggest values for the energy gaps and electronic affinities for the studied oxides and for the oxide layer that might be formed by the adsorption of oxygen atoms.     

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.     

Effects of the Chodura sheath on tungsten ionization and emission in tokamak divertors

The decay of the electric potential in the sheath region in tokamak divertors occurs on a scale length on the order of the main ion gyroradius (Chodura sheath) due to magnetic fields lines intersecting the divertor plates at grazing incidence. As a consequence, high-Z impurities like tungsten ionize within the sheath region in attached plasma conditions. The modification of the electron distribution in the sheath region must thus be taken into account to accurately model ionization and emission of impurities within the sheath region. To that end, an analytical expression of the distribution of the vertical ionization path for impurities sputtered from divertor plasma-facing components is derived. This expression is then used to estimate the fraction of neutral impurities ionizing within the sheath and the average vertical ionization path, and to derive an effective SXB (the number of ionizations per emitted photon) coefficient which includes the effects of the variation of the electron distribution in the sheath region. These results are applied to tungsten impurities sputtered from divertor plates. It is shown that the SXB coefficient for neutral tungsten is significantly reduced in high-density attached divertor plasma conditions (n_e ≳ 5 × 10¹³ cm⁻³) because of the ionization of neutral tungsten well within the sheath region.     

Influence of sputtering pressure on the giant magnetoresistance and structure in Fe–Cu–Ni granular thin films

Composition, structure and giant magnetoresistance in Fe_xCu_yNi_z films prepared at different sputtering pressures were investigated. X-ray diffraction studies showed only Cu (1 1 1) peak from the Cu grain. The shifts in the d-spacing d₁₁₁ of Cu indicates a progressive substitution of Ni in the Cu lattice. Similar trends in d₁₁₁ of Cu observed for the samples prepared at different sputtering pressures indicate that the structural behaviour of the samples is nearly independent of the sputtering pressure. A significant enhancement of magnetoresistance (MR) for the samples sputtered at 0.001 mbar as compared to that sputtered at 0.02 mbar is attributed to the reduced role of residual gas impurities in the films upon lowering the sputtering pressure. An interesting observation is that the MR did not significantly decrease even with a large substitution of Ni in the Cu grains.     

Resonance enhanced multi-photon ionization of neutral atoms sputtered with Ga-FIB

Resonance enhanced multi-photon ionization (REMPI) of neutral aluminum atoms sputtered with gallium focused ion beam (Ga-FIB) was studied in terms of substrate temperature and chemical state of the surfaces. Aluminum has the lowest excitation state (3p ²P_3/2) at 112 cm⁻¹ above the ground state (3p ²P_1/2). The results showed that the total REMPI signal intensity of neutral aluminum atoms and the ratio of REMPI signal intensities attributed to ²P_1/2 to ²P_3/2 were increased at higher temperature. On the other hand, the REMPI signal and the ratio were decreased in the case of partially oxidized aluminum surfaces. Considering the result on Al₂O₃, it was confirmed that the REMPI signals of ground state ²P_1/2 and the first excited spate ²P_1/2 could be affected with surface oxidation state.     

Optimum ion implantation and annealing conditions for stimulating secondary negative ion emission

The type, energy, ion dose, and heating temperature required to ensure a stable minimum work function of a surface in one experimental cycle (at least 2–3 min) are determined. Secondary ion mass spectrograms are recorded using Cs⁺, Ba⁺, and Ar⁺ ions. Cu, Al, and Mo samples are studied. The optimum ion implantation conditions and the activation temperature that provide a stable minimum work function of the sample surfaces are found. The samples implanted by Ba⁺ ions withstand higher temperature and current loads than the samples implanted by Cs⁺ ions. However, the work function in the case of Cs⁺ ions decreases stronger (to 1.9 eV). It is shown that neutral sputtered particles do not leave the surface at eφ ≤ 1.85–1.90 eV.     

Energy dependence of the ionization probability of sputtered Cu and Ni

Despite its great sensitivity, the usefulness of secondary ion mass spectrometry (SIMS) for many applications has been limited by an inadequate understanding of the probability of sputtering an atom in an ionized state. To determine this ionization probability for clean Cu and Ni surfaces, I have measured the energy distribution of sputtered neutrals and ions by quadrupole mass filtering and retarding potential analysis using potential modulation differentiation. Analysis of sputtered neutrals was accomplished by electron impact ionization. Because the neutrals outnumber the ions by at least two orders of magnitude, the ratio of sputtered ions to neutrals is an accurate measure of the ionization probability. For energies below 20 eV the dependence of the ionization probability on energy goes as P(E) α Eⁿ, where n = 0.65 for clean Cu. The absorption of oxygen on the Cu surface increases the total ion yield while causing a reduction in the value of the exponent n. Similar results are found for nickel, where n = 0.54 for the clean surface.     

Continuum light emission from sputtered species of graphite during ion beam irradiation

Light emission during sputtering of graphite targets with 1–10 keV Ne⁺, Kr⁺ and Xe⁺ beams has been investigated in the 180-600 nm wavelength range. Beside the characteristic lines of sputtered C₁ and C₁ ⁺, a continuum superimposed with a number of broad structures was observed in the 250-520 nm range, and having a maximum at 386 nm. Mass analysis of the sputtered flux confirmed the presence of negative carbon clusters C _m ^- , C₂ ^- being the dominant one. Ion beam parameters i.e. ion mass, energy, current density and ion dose were varied to identify the origin of the continuum emission. On the basis of the experimental results, it is suggested that the continuum is predominantly due to the overlapping of various band systems of sputtered C₂ with a small contribution from the heavier sputtered carbon clusters C_m (m>2). Received 24 September 1999 and Received in final form 11 February 2000     

Anomalous enhancement of negative sputtered ion emission by oxygen

Enhancement of negative sputtered ion yields by oxygen (either O⁺₂ bombardment or O₂ gas with Ar⁺ bombardment) is demonstrated for Si^?, As^?, P^?, Ga^?, Cu^? and Au^?, sputtered from a variety of matrices. Because oxygen also enhances positive ion yields of the same species, this effect cannot be simply explained on the basis of existing sputtered ion emission models. To rationalize these phenomena, a surface polarization model is developed which invokes localized electron emissive or electron retentive sites associated with differently oriented surface dipoles in the oxygenated surface. Such sites are considered to dominate the emission of negative and positive ions respectively. The model is shown to correctly predict that Au⁺ and Au^? ion yields are much more strongly enhanced by oxygen in dilute Au-Al alloys than in pure gold.     

Production of copper vapor in a pulsed hollow cathode discharge

Spectral emission from a pulsed Cu hollow cathode was investigated in relation to discharge current to gain information on the density of the sputtered Cu vapor and on the persistence time of the metastable and ground-state atoms. The cathode was excited with 250 μsec discharge pulses at current densities up to 1 A/cm², using He, Ne and Ar as buffer gases. The intensities of the emitted Cu I lines were found to depend strongly on the simmer current. In atmospheres of Ne or Ar, the intensities of the resonance lines exhibited characteristic maxima during the initial 20 μsec of the discharge pulses. The density of the sputtered Cu atoms was determined by absorption measurements using a second Cu hollow cathode as alight source.