Effect of oxide surface metallization under ion-beam irradiation

Changes in the surface chemical composition of WO₃, Ta₂O₅, MoO₃, and Nb₂O₅ oxides after Ar⁺ ion irradiation and those of the WO₃ surface after He⁺ ion irradiation under high vacuum were investigated by X-ray photoelectron spectroscopy. Upon Ar⁺ ion irradiation with an energy of 3 keV, the pronounced effect of ion-beam metallization was observed on the WO₃ oxide surface; a moderate effect was found for the Ta₂O₅ oxide surface; a weak one for the MoO₃ oxide surface; and no effect was discovered for the Nb₂O₅ oxide surface. At the saturation dose, 44 at % W, 12 at % Ta, and 2 at % Mo form on the oxide surfaces. Irradiation by light He⁺ ions with energies of 1 and 3 keV results in WO₃ surface metallization. At the saturation dose, 2 and 10 at % W (at 1 and 3 keV, respectively) forms on the oxide surface. The nature, mechanisms, and features of the oxide surface metallization effect induced by ion-beam irradiation are discussed.     

Desorption of cluster ions from adsorbed methane under cryogenic condition by low-energy ion irradiation

We have investigated ion desorption from adsorbed methane following keV He⁺ ion irradiation. The thickness of the adsorbed layer was precisely controlled. For mono-layered methane, only monomer ions (CH_x⁺) were desorbed by 1 keV He⁺ ion irradiation. On the other hand, a large number of cluster ions (C_nH_x⁺) up to n = 20 were desorbed from multi-layered film. Among cluster ions, molecular ions with CC bonds were found, which indicates that chemical bonds are newly formed by ion irradiation. Based on the results for thickness dependences of the mass spectral patterns, it was elucidated that the monomer ions are desorbed from the top surface layer through single electron excitation. While the cluster ions are formed mainly in the inside of the layers along the nuclear track due to the high-density electronic excitation, which is produced by nuclear collision between incident He⁺ ions and frozen molecules.     

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     

Theoretical study of charge-exchange and excitation processes in collisions of He<Superscript>+</Superscript> ions with C<Superscript>5+</Superscript>, N<Superscript>6+</Superscript>, and O<Superscript>7+</Superscript> hydrogen-like ions

Data on the cross sections for single-electron charge exchange and excitation in collisions of He⁺ ions with C⁵⁺, N⁶⁺, and O⁷⁺ ions in the He⁺ ion energy range of 0.2–3.0 MeV are obtained for the first time. The cross sections for the single-electron charge transfer into the singlet and triplet 1snl states of C⁴⁺, N⁵⁺, and O⁶⁺ (2≤n≤5) ions and for the 1s → 2p _{0, ±1} electronic excitation of He⁺(1s) ions are calculated. The calculations were performed by solving close-coupling equations on the basis of ten two-electron quasi-molecular states.     

Ion-beam reduction of the surface of higher oxides of molybdenum and tungsten

The process of reduction of the surface of oxides MoO₃ and WO₃ under irradiation by Ar⁺ and O ₂ ⁺ ions with an energy of 3 keV in high vacuum is investigated by X-ray photoelectron spectroscopy. It is shown that upon irradiation by Ar⁺ ions, lower and intermediate oxides and unoxidized metals are formed in the surface layers of higher oxides. Irradiation by O ₂ ⁺ ions mainly leads to formation of intermediate oxides with an insignificant content of lower oxides. It is found that the process of ion-beam reduction of the surface of oxides MoO₃ and WO₃ substantially depends on the ion type, irradiation dose, and difference in energy of the metal-oxygen bond in oxides.     

H<Superscript>+</Superscript> and He<Superscript>2+</Superscript> impact charge transfer cross sections of magnesium

H⁺ impact single and He²⁺ impact single and double electron capture cross sections of magnesium atoms have been calculated in the modified binary encounter approximation (BEA). The accurate expressions of ion impact s_DE\sigma _{\Delta {E}} (cross section for energy transfer DE\Delta E) and Hartree-Fock momentum distributions of the target electrons have been used throughout the calculations. On the basis of the present work it is concluded that inner shell captures by H⁺ and He²⁺ ions incident on magnesium atoms contribute partly to single electron capture and partly to transfer ionization cross sections. The calculated He²⁺ impact double electron capture cross sections of magnesium are in reasonably good agreement with the experimental observations. This indicates the success of the present theoretical approach in study of charge transfer cross sections of atoms as indirect mechanisms do not interfere with double electron capture processes in this case.     

Physical and Spectral Investigations of Cu<Superscript>2+</Superscript>-Doped Alkali Zinc Borate Glasses

Physical and spectral studies on 20ZnO + xLi₂O + (30-x)Na₂O + 50B₂O₃ (5 ≤ x ≥ 25) doped with 0.1 mol% of paramagnetic CuO impurity are carried out. Powder X-ray diffraction patterns of the glass samples confirm the amorphous nature. The physical parameters of all the glasses were also evaluated with respect to the composition. The electron paramagnetic resonance spectra of all these glasses exhibit resonance signals that are characteristic of Cu²⁺ ions. The optical absorption spectra also confirm the Cu²⁺ ion in tetragonally elongated octahedral site. Various crystal field, spin-Hamiltonian and bonding parameters are evaluated. It is observed that the mixed alkali effect is significant.     

Effect of high doses of N<Superscript>+</Superscript>, N<Superscript>+</Superscript> + Ni<Superscript>+</Superscript>, and Mo<Superscript>+</Superscript> + W<Superscript>+</Superscript> ions on the physicomechanical properties of TiNi

The surface layer of an equiatomic TiNi alloy, which exhibits the shape memory effect in the martensitic state, is modified with high-dose implantation of 65-keV N⁺ ions (the implantation dose is varied from 10¹⁷ to 10¹⁸ ions/cm²). TiNi samples are implanted by N⁺, Ni⁺-N⁺, and Mo⁺-W⁺ ions at a dose of 10¹⁷–10¹⁸ cm⁻² and studied by Rutherford backscattering, scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction (glancing geometry), and by measuring the nanohardness and the elastic modulus. A Ni⁺ concentration peak is detected between two maxima in the depth profile of the N⁺ ion concentration. X-ray diffraction (glancing geometry) of TiNi samples implanted by Ni⁺ and N⁺ ions shows the formation of the TiNi (B2), TiN, and Ni₃N phases. In the initial state, the elastic modulus of the samples is E = 56 GPa at a hardness of H = 2.13 ± 0.30 GPa (at a depth of 150 nm). After double implantation by Ni⁺-N⁺ and W⁺-Mo⁺ ions, the hardness of the TiNi samples is ∼2.78 ± 0.95 GPa at a depth of 150 nm and 4.95 ± 2.25 GPa at a depth of 50 nm; the elastic modulus is 59 GPa. Annealing of the samples at 550°C leads to an increase in the hardness to 4.44 ± 1.45 GPa and a sharp increase in the elastic modulus to 236 ± 39 GPa. A correlation between the elemental composition, microstructure, shape memory effect, and mechanical properties of the near-surface layer in TiNi is found.     

Ion-beam reduction of the surface of tantalum higher oxide

The process of reduction of the surface of higher oxide Ta₂O₅ under irradiation by inert gas (Ar⁺) and chemically active gas (O₂⁺) ions with an energy of 3 keV in high vacuum is investigated by X-ray photoelectron spectroscopy at room temperature. It is found that intermediate oxide TaO₂, lower oxide TaO, and metallic Ta form in the surface layers of Ta₂O₅ under Ar⁺ ion bombardment. An insignificant amount of intermediate oxide TaO₂ forms in the surface layers of Ta₂O₅ under O₂⁺ ion bombardment. Ion-beam-induced reduction of the Ta₂O₅ surface is shown to depend on the type of ion and irradiation dose.     

Interaction of <Superscript>3</Superscript>He<Superscript>2+</Superscript> and Ar<Superscript>6+</Superscript> ions with acetylene,ethylene, and ethane molecules

Time-of-flight mass spectroscopy methods are employed for studying processes occurring during capture of electrons by ³He²⁺ and Ar⁶⁺ multiply charged ions with energy 6z keV (z is the ion charge) from C₂H _n molecules (n = 2, 4, 6) with different multiplicities of C-C bonds. Fragmentation schemes of the molecular ions formed in such processes are established from analysis of correlations of recording times for all fragment ions. The absolute values of the cross sections of capture of an electron and capture with ionization are measured, as well as the cross sections of formation of fragment ions in these processes. The absolute values of total capture cross sections for several electrons are determined.     

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.     

Effect of Sr<Superscript>2+</Superscript> ion substitution with trivalent ions (Sc<Superscript>3+</Superscript>, In<Superscript>3+</Superscript>, La<Superscript>3+</Superscript>, Bi<Superscript>3+</Superscript>) on its ferroelectric instability in SrTiO<Subscript>3</Subscript>

The vibration frequencies of unstable ferroelectric and antiferrodistortion modes and the dependences of the energy on the ion displacement amplitude have been calculated within the generalized Gordon-Kim model for distortions along eigenvectors of these modes in the mixed compounds Sr_{1 − x} A _x Ti_{1 − x} /₄□ _x/4O₃ and Sr_{1 − y} A _2y /₃□ _y/3TiO₃ (A = Sc³⁺, In³⁺, La³⁺, Bi³⁺; □ is the vacancy). To compensate an excess positive charge, vacancies are introduced into the Ti⁴⁺ or Sr²⁺ site. Calculations have been performed in the “daverage” crystal approximation for impurity concentrations of 0.25 and 0.50. To this end, a set of 40 atomic superlattices with various orderings of heterovalent ions Sr²⁺ and impurity A ³⁺ has been considered. It has been found that each impurity type, independently of charge balance, induces ferroelectric instabilities in doped compounds. In the case of doping with In³⁺ and La³⁺ for concentration x = 0.25, the possibility of rotating the polarization vector has been shown.     

On the nature of ion bombardment-induced phase transformations in films of transition metals

Abstract

Electron diffraction studies have been made of polycrystalline Ni films irradiated with well separated beams of ions of different nature, namely ions of inert (He⁺, Ne⁺, Ar⁺, Kr⁺, Xe⁺) and reactive (N⁺ and O⁺) gases. The Ni films were prepared under vacuum conditions (P? 3·10^?6Pa during evaporation) preventing an appreciable contamination of the films with impurities. The samples were irradiated at T? 300 K with ion beams of energies from 10 to 100 keV in the dose range between 5·10¹⁶ cm^?2 and the value leading to sample destruction.

Irradiation with noble gas ions revealed no phase transitions in the Ni films. A similar result was obtained in irradiation of Fe and Cr films with He⁺ ions. The bombardment of Ni films with reactive gas ions does cause changes in the lattice structure of the samples under study, depending on the nature of the bombarding ions. The N⁺ ion bombardment gives rise to the hcp phase with the lattice parameters typical of the Ni₃N compound, and the O⁺ ion bombardment results in the fcc phase with the NiO-type parameter.

The conclusion is drawn on the chemical origin of the phase transformations in the Ni films under ion bombardment. The necessity of revising the concept about the polymorphous nature of phase transformations induced in the films of transition metals by ion bombardment is substantiated.     

Polymerization of solid C<Subscript>60</Subscript> under C<Stack><Subscript>60</Subscript><Superscript>+</Superscript></Stack> cluster ion bombardment

The structure transformation occurring in fullerene film under bombardment by 50 keV C₆₀⁺ cluster ions is reported. The Raman spectra of the irradiated C₆₀ films reveal a new peak rising at 1458 cm⁻¹ with an increase in the ion fluence. This feature of the Raman spectra suggests linear polymerization of solid C₆₀ induced by the cluster ion impacts. The aligned C₆₀ polymeric chains composing about 5–10 fullerene molecules have been distinguished on the film surface after the high-fluence irradiation using atomic force microscopy (AFM). The surface profiling analysis of the irradiated films has revealed pronounced sputtering during the treatment. The obtained results indicate that the C₆₀ polymerization occurs in a deep layer situated more than 40 nm below the film surface. The deep location of the C₆₀ polymeric phase indirectly confirms the dominant role of shock waves in the detected C₆₀ phase transformation.     

Studies on the analytical potential energy function of diatomic molecular ion XY<Superscript>+</Superscript> using variational method

A new analytical potential energy function for diatomic molecular ion XY⁺ is proposed based on the energy consistent method (ECM). The Coulomb potential included in the new ionic potential contains multipole corrections, converges quickly and is variationally, changeable. The new potential and the ECM are applied to variationally studying the potential energies of eight electronic states of several diatomic molecular ions: the A²π state of CO⁺, the X²∑_g⁺ state of Li₂⁺, the X²∑_g⁺ state of He₂⁺, the 1²∏_u state of Na₂⁺, the A²∏_u state of N₂⁺, the X¹∑⁺ state of KrH⁺, the X²∑⁺ state of SiO⁺ and the A²π state of SO⁺ ion. The present results agree excellently with the experiment-based Rydberg-Klein-Rees (RKR) potentials, and are superior to the commonly used Huxley-Murrell-Sorbie (HMS) analytical potentials, and are better in some cases than some quantum mechanicalab initio potentials in the ionic asymptotic and dissociation regions.     

Exit angle dependence of charge-state distribution of backscattered He ions

Exit angle and energy dependences of the charge-state distribution of backscattered He ions were investigated when 500 keV He⁺ ions were incident on SiO₂. The energy dependence of the He⁺ fraction was estimated by comparing the measured He⁺ spectra with the simulated spectra of He ions in all charge states at the exit angles of 5-25° with respect to the SiO₂ surface. We found that the He⁺ fraction is almost independent of the exit angle at energies higher than 250 keV and the observed energy dependence of the He⁺ fraction is in good agreement with that for the carbon-foil-transmission experiment. In the low energy region (<250 keV), however, the He⁺ fraction decreases as the exit angle decreases.     

The effects of Xe irradiation on He and H co-implanted Si

A combination of X-ray diffraction, cross-sectional transmission electron microscopy (XTEM), and Raman spectroscopy was used to study the effects of irradiation with swift heavy ions on helium and hydrogen co-implanted silicon.<100>-oriented silicon wafers were co-implanted with 30 keV helium to a dose of 3×10¹⁶He⁺/cm² and 24 keV protons to a dose of 2×10¹⁶ H⁺/cm². Moreover, selected helium and hydrogen co-implanted Si wafers were irradiated with 94 MeV xenon. After He and H co-implantation and Xe-irradiation, the wafers were annealed at a temperature of 673 K for 30 min. The damage region of the wafers was examined by the XTEM analysis. The results reveal that most of the platelets are aligned parallel to the (100) plane in the He and H co-implanted Si. However, majority of the platelets lie in<texlscub>111</texlscub>planes after Xe irradiation. Blisters do not occur on the sample surface after Xe irradiation. Raman results reveal that the intensities of both SiH₂ and V₂H₆ modes increase with the increase in the dose of Xe. A possible explanation is that strong electronic excitation during Xe irradiation produces annealing effect, which reduces both lattice damage and the out-of-plane tensile strain.     

Cluster ion emission from LiF induced by MeV N<Superscript>q+</Superscript> projectiles and <Superscript>252</Superscript>Cf fission fragments

Ion cluster desorption yields from LiF were measured at PUC-Rio with ≈0.1 MeV/u N ^q+ (q = 2,4,5,6) ion beams by means of a time-of-fight (TOF) mass spectrometer. A ²⁵²Cf source mounted in the irradiation chamber allows immediate comparison of cluster emissions induced by ≈65 MeV fission fragments (FF). Emission of (LiF) _n Li⁺ clusters are observed for both the N beams and the ²⁵²Cf fission fragments. The observed cluster size n varies from 1 to 6 for N ^q+ projectiles and from 1 to ≈40 for the ²⁵²Cf-FF. The size dependence of the Y(n) distributions suggests two cluster formation regimes: (i) recombination process in the outgoing gas phase after impact and (ii) emission of pre-formed clusters from the periphery of the impact site. The corresponding distribution of ejected negative cluster ions (LiF) _n F⁻ closely resembles that of the positive secondary (LiF) _n Li⁺ ions. The desorption yields of positive ions scale as Y(n) ∼ q ⁵. A calculation with the CASP code shows that this corresponds to a cubic scaling ∼S _e ³ with the electronic stopping power S _e , as predicted by collective shock wave models for sputtering and models involving multiple excitons (Frenkel pair sputtering). We discuss possible interpretations of the functional dependence of the evolution of the cluster emission yield Y(n) with cluster size n, fitted by a number of statistical distributions.     

Modification of GaAs by medium-energy N<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack> ions

The modification of GaAs with a 2500-eV beam containing N ₂ ⁺ and Ar⁺ ions is examined with Auger electron spectroscopy. Most implanted nitrogen atoms are found to react with the matrix, substituting arsenic atoms to produce a several-nanometer-thick layer of the single-phase GaAs_1−x N_x (x=6%) solid solution. The GaN phase is absent. Displaced arsenic atoms and nitrogen atoms unreacted with the matrix are present in the layer and on its surface. The former segregate, whereas the latter form molecules.