Isotopic fractionation in sputtering

Isotopic fractionation due to sputtering has been investigated via a collector type experiment in which targets of known isotopic composition have been bombarded with several keV Ar⁺ and Xe⁺ ions with fluences down to 3.0x10¹⁴ ions/cm² , believed to be the lowest fluences for which such detailed measurements have ever been made. The isotopes were sputtered onto carbon collectors and analyzed with Secondary Ion Mass Spectroscopy (SIMS.) There is clear indication of preferential effects several times that predicted by the dominant analytical theory. Results also show a fairly strong angular variation in the fractionation. The maximum effect is usually seen in the near normal direction, measured from the target surface, falling continuously, by a few percent in some cases, to a minimum in the oblique direction. Measurements have been made using Mo isotopes: ¹⁰⁰Mo and ⁹²Mo and a liquid metal system of In:Ga eutectic. The light isotope of Mo is found to suffer a 53 ± 5‰ (note: 1.0‰ ≡ 0.1%) enrichment in the sputtered flux in the near normal direction, compared to the steady state near normal sputtered composition, under 5.0 keV Xe⁺ bombardment of 3.0 x 10¹⁴ ions/cm². In the liquid metal study only the angular dependence of the fractionation could be measured due to the lack of a well defined reference and the nature of the liquid surface, which is able to 'repair' itself during the course of a bombardment. The results show that ¹¹³In is preferentially sputtered over ¹¹⁵In in the near normal direction by about 8.7 ± 2.7‰ compared to the oblique direction. ⁶⁹Ga, on the other hand, is sputtered preferentially over ⁷¹Ga in the oblique direction by about 13 ± 4.4‰ with respect to the near normal direction.

Investigations into electronic stopping regime sputtering of uranium tetrafluoride

Yields were measured for ²³⁵U sputtered from UF₄ by ¹⁶O, ¹⁹F, and ³⁵Cl over the energy range ~.12 to 1.5 MeV/ amu sing a charge equilibrated beam in the stripped beam arrangement for all the incident ions and in the transmission arrangement for ¹⁹F and ³⁵Cl. In addition, yields were measured for ¹⁹F incident in a wide range of discrete charge states. The angular dependence of all the measured yields were consistent with cosʋ. The stripped beam and transmission data were well fit by the form (Az²eqln(BƐ)/Ɛ)⁴ (where Ɛ was the ion energy in MeV/amu and z_eq(Ɛ) was taken from Zeigler(80). The fitted values of B for the various sets of data were consistent with a constant B₀, equal to 36.3 ± 2.7, independent of incident ion. The fitted values of A show no consistent variation with incident ion although a difference can be noted between the stripped beam and transmission values, the transmission values being higher.

The incident charge data were well fit by the assumptions that the sputtering yield depended locally on a power of the incident ion charge and that the sputtering from the surface is exponentially correlated to conditions in the bulk. The equilibrated sputtering yields derived from these data are in agreement with the stripped beam yields.

In addition, to aid in the understanding of these data, the data of Hakansson(80,81a,81b) were examined and contrasted with the UF₄ results. The thermal models of Seiberling(80) and Watson(81) were discussed and compared to the data.

Sputtering of insulators in the electronic stopping region

Using track detectors we have measured sputtering yields induced by MeV light ions incident on a uranium containing glass, UO₂ and UF₄. No deviation from the behavior predicted by the Sigmund theory was detected in the glass or the UO₂. The same was true for UF₄ bombarded with ⁴He at 1 MeV and with ¹⁶O and ²⁰Ne at 100 keV. In contrast to this, 4.75 MeV ¹⁹F(+2) sputters uranium from UF₄ with a yield of 5.6 ± 1.0, which is about 3 orders of magnitude larger than expected from the Sigmund theory. The energy dependence of the yield indicates that it is generated by electronic rather than nuclear stopping processes. The yield depends on the charge state of the incident fluorine but not on the target temperature. We have also measured the energy spectrum of the uranium sputtered from the UF₄. Ion explosions, thermal spikes, chemical rearrangement and induced desorption are considered as possible explanations for the anomalous yields.

Sputtering of the gallium-indium eutectic alloy in the liquid phase

We have measured sputtering yields and angular distributions of sputtered atoms from both the solid and liquid phases of gallium, indium, and the gallium-indium eutectic alloy. This was done by Rutherford backscattering analysis of graphite collector foils. The solid eutectic target shows a predominance of indium crystallites on its surface which have to be sputtered away before the composition of the sputtered atoms equals the bulk target composition. The size of the crystallites depends upon the conditions under which the alloy is frozen. The sputtering of the liquid eutectic alloy by 15 keV Ar⁺ results in a ratio of indium to gallium sputtering yields which is 28 times greater than would be expected from the target stoichiometry. Furthermore, the angular distribution of gallium is much more sharply peaked about the normal to the target surface than the indium distribution. When the incident Ar⁺ energy is increased to 25 keV, the gallium distribution broadens to the same shape as the indium distribution. With the exception of the sharp gallium distribution taken from the liquid eutectic at 15 keV, all angular distributions from liquid targets fit a cos² θ function. An ion-scattering-spectroscopy analysis of the liquid eutectic alloy reveals a surface layer of almost pure indium. A thermodynamic explanation for this highly segregated layer is discussed. The liquid eutectic alloy provides us with a unique target system which allows us to estimate the fraction of sputtered material which comes from the first monolayer of the surface.

Studies of noble gases in meteorites and in the earth

The isotopic and elemental abundances of noble gases in the solar system are investigated, using simple mixing models and mass-spectrometric measurements of the noble gases in meteorites and terrestrial rocks and minerals.

Primordial neon is modeled by two isotopically distinct components from the interstellar gas and dust. Neon from the gas dominates solar neon, which contains about ten times more ²⁰Ne than ²²Ne. Neon from the dust is represented in meteorites by neon-E, with ²⁰Ne/²²Ne less than 0.6. Isotopic variations in meteorites require neon from both dust and gas to be present. Mixing dust and gas without neon loss generates linear correlation lines on three-isotope and composition-concentration diagrams. A model for solar wind implantation predicts small deviations from linear mixing, due to preferential sputtering of the lighter neon isotopes.

Neon in meteorites consists of galactic cosmic ray spallation neon and at least two primordial components, neon-E and neon-S. Neon was measured in several meteorites to investigate these end- members. Cosmogenic neon produced from sodium is found to be strongly enriched in ²²Ne. Neon measurements on sodium-rich samples must be interpreted with care so not to confuse this source of ²²Ne with neon-E, which is also rich in ²²Ne.

Neon data for the carbonaceous chondrite Mokoia show that the end member composition of neon-Si in meteorites is ²⁰Ne/²²Ne = 13.7, the same as the present solar wind. The solar wind composition evidently has remained constant since before the compaction of Mokoia.

Ca, Al-rich inclusions from the Allende meteorite were examined for correlation between neon-E and oxygen or magnesium isotopic anomalies. ²²Ne and ³⁶Ar enrichments found in some inclusions are attributed to cosmic- ray-induced reactions on Na and Cl, not to a primordial component. Neon-E is not detectably enriched in Allende.

Measurements were made to determine the noble gas contents of various terrestrial rocks and minerals, and to investigate the cycling of noble gases between different terrestrial reservoirs. Beryl crystals contain a characteristic suite of magmatic gases including nucleogenic ²¹Ne and ²²Ne from (α,n) reactions, radiogenic ⁴⁰Ar, and fissiogenic ^131-136Xe from the decay of K and U in the continental crust. Significant concentrations of atmospheric noble gases are also present in beryl.

Both juvenile and atmospheric noble gases are found in rocks from the Skaergaard intrusion. The ratio ⁴⁰Ar/³⁶Ar (corrected for in situ decay of ⁴⁰K) correlates with δ¹⁸O in plagioclase. Atmospheric argon has been introduced into samples that have experienced oxygen-isotope exchange with circulating meteoric hydrothermal fluids. Unexchanged samples contain juvenile argon with ⁴⁰Ar/³⁶Ar greater than 6000 that was trapped from the Skaergaard magma.

Juvenile and atmospheric gases have been measured in the glassy rims of mid-ocean ridge (MOR) pillow basalts. Evidence is presented that three samples contain excess radiogenic ¹²⁹Xe and fission xenon, in addition to the excess radiogenic ⁴⁰Ar found in all samples. These juvenile gases are being outgassed from the upper-mantle source region of the MOR magma. No isotopic evidence has been found here for juvenile primordial noble gases accompanying the juvenile radiogenic gases in the MOR glasses. Large argon isotopic variations in a single specimen provide a clear indication of the late-stage addition of atmospheric argon, probably from seawater.

The Skaergaard data demonstrate that atmospheric noble gases dissolved in ground water can be transferred into crustal rocks. Subduction of oceanic crust altered by seawater can transport atmospheric noble gases into the upper mantle. A substantial portion of the noble gases in mantle derived rocks may represent subducted gases, not a primordial component as is often assumed.

Thermodynamic and kinetic behavior of an argon plasma jet. Decomposition of nitric oxide between 1300 - 1750 degrees K in an argon plasma

In the first part of the study, an RF coupled, atmospheric pressure, laminar plasma jet of argon was investigated for thermodynamic equilibrium and some rate processes.

Improved values of transition probabilities for 17 lines of argon I were developed from known values for 7 lines. The effect of inhomogeneity of the source was pointed out.

The temperatures, T, and the electron densities, n_e , were determined spectroscopically from the population densities of the higher excited states assuming the Saha-Boltzmann relationship to be valid for these states. The axial velocities, v_z, were measured by tracing the paths of particles of boron nitride using a three-dimentional mapping technique. The above quantities varied in the following ranges: 10¹² ˂ n_e ˂ 10¹⁵ particles/cm³, 3500 ˂ T ˂ 11000 °K, and 200 ˂ v_z ˂ 1200 cm/sec.

The absence of excitation equilibrium for the lower excitation population including the ground state under certain conditions of T and n_e was established and the departure from equilibrium was examined quantitatively. The ground state was shown to be highly underpopulated for the decaying plasma.

Rates of recombination between electrons and ions were obtained by solving the steady-state equation of continuity for electrons. The observed rates were consistent with a dissociative-molecular ion mechanism with a steady-state assumption for the molecular ions.

In the second part of the study, decomposition of NO was studied in the plasma at lower temperatures. The mole fractions of NO denoted by x_NO were determined gas-chromatographically and varied between 0.0012 ˂ x_NO ˂ 0.0055. The temperatures were measured pyrometrically and varied between 1300 ˂ T ˂ 1750°K. The observed rates of decomposition were orders of magnitude greater than those obtained by the previous workers under purely thermal reaction conditions. The overall activation energy was about 9 kcal/g mol which was considerably lower than the value under thermal conditions. The effect of excess nitrogen was to reduce the rate of decomposition of NO and to increase the order of the reaction with respect to NO from 1.33 to 1.85. The observed rates were consistent with a chain mechanism in which atomic nitrogen and oxygen act as chain carriers. The increased rates of decomposition and the reduced activation energy in the presence of the plasma could be explained on the basis of the observed large amount of atomic nitrogen which was probably formed as the result of reactions between excited atoms and ions of argon and the molecular nitrogen.

The structure of liquid argon as determined by x-ray diffraction

X-ray diffraction measurements and subsequent data analyses have been carried out on liquid argon at five states in the density range of 0.91 to 1.135 gm/cc and temperature range of 127 to 143°K. Duplicate measurements were made on all states. These data yielded radial distribution and direct correlation functions which were then used to compute the pair potential using the Percus-Yevick equation. The potential minima are in the range of -105 to -120°K and appear to substantiate current theoretical estimates of the effective pair potential in the presence of a weak three-body force.

The data analysis procedure used was new and does not distinguish between the coherent and incoherent absorption factors for the cell scattering which were essentially equal. With this simplification, the argon scattering estimate was compared to the gas scattering estimate on the laboratory frame of reference and the two estimates coincided, indicating the data normalized. The argon scattering on the laboratory frame of reference was examined for the existence of the peaks in the structure factor and the existence of an observable third peak was considered doubtful.

Numerical studies of the effect of truncation, normalization, the subsidiary peak phenomenon in the radial distribution function, uncertainties in the low angle data relative to errors in the direct correlation function and the distortion phenomenon are presented.

The distortion phenomenon for this experiment explains why the Mikolaj-Pings argon data yielded pair potential well depths from the Percus-Yevick equation that were too shallow and an apparent slope with respect to density that was too steep compared to theoretical estimates.

The data presented for each measurement are: empty cell and cell plus argon intensity, absorption factors, argon intensity, smoothed argon intensity, smoothed argon intensity corrected for distortion, structure factor, radial distribution function, direct correlation function and the pair potential from the Percus-Yevick equation.

Thermal, structural and optical properties of NiOx thin films deposited by reactive dc-magnetron sputtering

The NiOx thin films were deposited by reactive dc-magnetron sputtering from a nickel metal target in Ar + O-2 with the relative O-2 content 5%. The as-deposited NiOx, thin films could represent a two-component system comprising crystalline NiO particles dispersed in an amorphous Ni2O3. Decomposition temperature of the as-deposited NiO, thin films was at about 263 degrees C. After annealed at 400 degrees C for 30 min in air, the surface morphology of the films became very rough due to the decomposition of the Ni2O3, leading to the changes of the optical properties of the NiO, thin films. The reflectivity of the films annealed at 400 degrees C was lower than that of the as-deposited one and the optical contrast was 52% at 405 nm. (c) 2006 Elsevier B.V. All rights reserved.

Write-once blue laser recording using silicon doped SbOx thin films prepared by reactive dc-magnetron sputtering

Si:SbOx films have been deposited by reactive dc-magnetron sputtering from a Sb target with Si chips attached in Ar + O-2 with the relative O-2 content 7%. The as-deposited films contained Sb metal, Sb2O3, SiO, Si2O3 and SiO2. The crystallization of Sb was responsible for the changes of optical properties of the films. The results of the blue laser recording test showed that the films had good writing sensitivity for blue laser beam (406.7 nm), and the recording marks were still clear even if the films were deposited in air 60 days, which demonstrated that doping silicon in SbOx films can improve the stability of SbOx films. High reflectivity contrast of about 36% was obtained at a writing power 6 mW and writing pulse width 300 ns. (c) 2007 Elsevier B.V. All rights reserved.

Write-once medium with Fe-Doped BiOx thin films for blue laser recording

Fe:BiOx films are fabricated on K9 glass substrates by rf-magnetron sputtering of a BiFeO target under argon atmosphere with increasing sputtering power from 80 to 200 W at room temperature. It is found that the thin films grown at the sputtering power of 160W can be formed at an appropriate deposition rate and have an improved surface morphology. The XPS result reveals that the films investigated are comprised of Bi, Fe and O elements. A typical XRD pattern shows that no phase transition occurs in the films up to 400 degrees C. The results of the blue laser recording test demonstrate that the Fe:BiOx films have good writing sensitivity for blue laser beam (406.7 nm) and good stability after reading 10000 times. The recording marks of 200nm or less are obtained. These results indicate that the introduction of Fe into BiOx films can reduce the mark size and improve the stability of the films.

Annealing effects of sapphire substrate on properties of ZnO films grown by magnetron sputtering

The annealing effects of sapphire substrates on the quality of epitaxial ZnO films grown by dc reactive magnetron sputtering were studied. The atomic steps formed on (0001) sapphire (alpha-Al2O3) substrates surface by annealing at high temperature were analyzed by atomic force microscopy. Their influence on the growth of ZnO films was examined by X-ray diffraction and photoluminescence measurements. Experimental results indicate that the film quality is strongly affected by annealing treatment of the sapphire substrate surface. The optimum annealing temperature of sapphire substrates for ZnO grown by magnetron sputtering is 1400 degrees C for 1 h in air.

Low temperature growth of c-axis oriented AlN films on gamma-LiAlO2 by radio frequency magnetron sputtering

Aluminum nitride (AlN) films were prepared on gamma-LiAlO2 substrates by radio frequency (rf) magnetron sputtering. The influence of substrate temperature (T-s) and nitrogen (N-2) concentration on film growth was investigated. The X-ray diffraction (XRD) results reveal that highly c-axis oriented AlN films can be obtained in the temperature range from room temperature (RT) to 300 degrees C. A smoother surface and a crystalline quality decrease with increasing N-2 concentration have been observed by XRD and atomic force microscopy (AFM) for the films deposited at lower substrate temperature. On the contrary, the degradation of the surface smoothness and the higher crystalline quality can be observed for the films deposited at a higher substrate temperature with N-2-rich ambient. The growth mechanism which leads to different crystalline quality of the films is discussed. (C) 2008 Elsevier B.V. All rights reserved.