X-ray photoelectron spectroscopic studies of nickel-oxygen surfaces using oxygen and argon ion-bombardment

We have studied the surface chemistry of the nickel-oxygen system using both temperature changes and ion bombardment as techniques for elucidating the surface structure. The spectra of metallic Ni, NiO and Ni₂O₃ were characterized from samples prepared directly in the spectrometer. The Ni₂O₃ species could be distinguished from an authentic Ni(OH)₂ sample from both the X-ray photoelectron lines and the Auger transitions. The oxides of NiO and Ni₂O₃ could be prepared by bombardment with low energy (400eV) O₂⁺ ions as well as by exposure of Ni to oxygen at reduced pressure (～ 100 torr). The Ni₂O₃ was found to be present on most nickel-oxygen surfaces except those prepared by exposing Ni to air for many hours at high temperature (> 600°C), indicating that the stability of Ni₂O₃ decreased as the temperature increased. Exposure of both NiO and Ni₂O₃ to 400 eV Ar⁺ ion bombardment caused reduction to metallic Ni. This observation has also been noted for several other oxides and a prediction of whether or not reduction should be observed is presented by examining the free energy of formation of the molecule.     

Influence of the magnetic phase transition on secondary ion emission from disordered Ni-Pd compounds of various compositions

Variations in secondary ion emission (SIE) from polycrystals of ferromagnetic disordered Ni-Pd compounds irradiated by argon ions with energy of 10 keV are studied experimentally. A considerable reduction in Ni⁺ and Pd⁺ ion emission upon transitioning from the ferromagnetic to the paramagnetic state is revealed for the following Ni-Pd compounds with various Curie points T _C: NiPd (T _C = 190°C), Ni₅Pd (T _C = 315°C), and NiPd₅ (T _C = 110°C). The observed reduction in SIE is attributed to variations in the surface binding energy and the density of electron states near the Fermi level.     

Ion beam synthesis and investigation of nanocomposite multiferroics based on barium titanate with 3d metal nanoparticles

Samples of nanocomposite multiferroics have been synthesized by implantation of Co⁺, Fe⁺, and Ni⁺ ions with an energy of 40 keV into ferroelectric barium titanate plates to doses in the range (0.5–1.5) × 10¹⁷ ions/cm². It has been found that nanoparticles of metallic iron, cobalt, or nickel are formed in the barium titanate layer subjected to ion bombardment. With an increase in the implantation dose, the implanted samples sequentially exhibit superparamagnetic, soft magnetic, and, finally, strong ferromagnetic properties at room temperature. The average sizes of ion-synthesized 3d-metal nanoparticles vary in the range from 5 to 10 nm depending on the implantation dose. Investigation of the orientation dependence of the magnetic hysteresis loops has demonstrated that the samples show a uniaxial (“easy plane”) magnetic anisotropy typical of thin granular magnetic films. Ferromagnetic BaTiO₃: 3d metal samples are characterized by a significant shift of the ferromagnetic resonance signal in an external electric field, as well as by a large (in magnitude) magnetodielectric effect at room temperature. These results indicate that there is a strong magnetoelectric coupling between the ferroelectric barium titanate matrix and ion-synthesized nanoparticles of magnetic metals.     

Interpretation of secondary ion mass spectra by means of fingerprint spectra and secondary ion imaging

A passive layer, of several thousand ? thickness, formed on a polycrystalline nickel electrode, has been examined using secondary ion mass spectrometry (SIMS) by spottering with a 5.5 keV, 13μA·cm⁻²,⁴⁰Ar⁺ primary beam. Concentration profiles were detived by monitoring the intensities of atomic and molecular mass peaks as a function of sputtering time (i.e. depth). Nickel was present throughout the layer but not as the element since the relative intensities of the Ni _n ⁺ (n=1, 2, 3, 4) peaks, constituting part of its fingerprint spectrum, differed from those in the fingerprint spectrum of elemental nickel. These values were eventually reached, signifying piercing of the layer and thus providing a means of estimating its thickness. Imaging of⁵⁸Ni⁺ showed the presence of nickel in at least two different modifications in the layer, both with higher Ni⁺ yields than the bulk nickel. Their fractional coverages were estimated from the images taken at various depths. The resulting profile of the Ni⁺ originating from one of these modifications was found to be proportional to the¹⁶O⁻ profile, indicating that these ions originate from the same molecule. This example demonstrates the advantage of combining different SIMS modes (viz. depth profiles, fingerprint spectra and imaging) in tackling certain analytical problems.     

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.     

Microstructure and magnetooptics of silicon oxide with implanted nickel nanoparticles

Metallic nickel nanoparticles of various sizes are formed in a thin near-surface layer in an amorphous SiO₂ matrix during 40-keV Ni⁺ ion implantation at a dose of (0.25−1.0) × 10¹⁷ ions/cm². The micro-structure of the irradiated layer and the crystal structure, morphology, and sizes of nickel particles formed at various irradiation doses are studied by transmission electron microscopy and electron diffraction. The magnetooptical Faraday effect and the magnetic circular dichroism in an ensemble of nickel nanoparticles are studied in the optical range. The permittivity [^(e)]\hat \varepsilon tensor components are calculated for the implanted samples using an effective medium model with allowance for the results of magnetooptical measurements. The spectral dependences of the tensor [^(e)]\hat \varepsilon components are found to be strongly different from those of a continuous metallic nickel film. These differences are related to a disperse structure of the magnetic nickel phase and to a surface plasma resonance in the metal nanoparticles.     

Molecular ion yield enhancement induced by gold deposition in static secondary ion mass spectrometry

Static ToF-SIMS was used to evaluate the effect of gold condensation as a sample treatment prior to analysis. The experiments were carried out with a model molecular layer (Triacontane M = 422.4 Da), upon atomic (In⁺) and polyatomic (Bi₃⁺) projectile bombardment. The results indicate that the effect of molecular ion yield improvement using gold metallization exists only under atomic projectile impact. While the quasi-molecular ion (M+Au)⁺ signal can become two orders of magnitude larger than that of the deprotonated molecular ion from the pristine sample under In⁺ bombardment, it barely reaches the initial intensity of (M−H)⁺ when Bi₃⁺ projectiles are used. The differences observed for mono- and polyatomic primary ion bombardment might be explained by differences in near-surface energy deposition, which influences the sputtering and ionization processes.     

A CEMS investigation of57Fe+Al implanted in Al foil

⁵⁷Fe implanted and post Al implanted in aluminum foil have been performed at low energy of 27keV and the CEMS shows the formation of intermetallic compounds FeAlσ and Fe₂Alσ during the ion bombardment. The results are discussed with the enhanced diffusion by energetic ion bombardment.     

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.     

The use of low energy sims to study the chemisorption of CO on Ni(100) and polycrystalline nickel

Adsorption of CO on Ni(100) has been investigated using secondary ion mass spectrometry (SIMS) and Auger electron spectroscopy at 175 and 295 K. Interaction with polycrystalline nickel was examined at 295, 325 and 365 K. All the secondary ions, Ni⁺, Ni₂⁺, NiCO⁺ and Ni₂CO⁺ show large increases in intensity as CO is adsorbed but there is no simple correlation of the secondary ion species with the sequence of linear and bridge-bonded CO species expected from electron energy loss spectroscopy. Adsorption of CO at 175 K on a hydrogen saturated Ni(100) surface, which is thought to permit only bridge-bonded adsorbed CO, does not result in any enhancement of Ni₂CO⁺. The extent of increases in secondary ion yields after CO adsorption on the nickel surfaces are primarily related to the variations in the heat of adsorption as a function of surface coverage. The presence of more weakly-held species is important in enhancing secondary ion yields.     

SIMS and flash desorption studies of nickel oxygen interaction

O₂ exposure of polycrystalline nickel at 300 K results in characteristics changes of secondary ion emission. These can be described by a model which is in good agreement with corresponding LEED, AES, XPS, and ΔΦ results of other authors. According to this model, oxygen can be bonded on Ni in at least five different phases:

1. chemisorption, indicated by a rapid increase of Ni⁺, Ni ₂ ⁺ , and Ni₂O⁺ (≦5 L);
2. a rearranged chemisorption layer, characterized by a drastic decrease of Ni⁺, Ni ₂ ⁺ , and Ni₂O⁺ (5–15 L);
3. nickel oxide (NiO) responsible for a strong NiO^?- and NiO ₂ ^? -emission (≦40 L);
4. oxygen on top of this NiO layer, producing a final increase of Ni⁺ and NiO⁺ and a O₂-flash signal at 400 K (>40 L);
5. bulk dissolved oxygen in thermal equilibrium with a chemisorption layer (after several exposure/heating cycles).

During ion bombardment of a 100 L O₂ exposed Ni surface these different binding states occur in a reversed order of succession. O₂-flash signals at 400 and 1100 K, related to drastic changes in secondary ion emission at 400, 700, and 1100 K, reflect the disappearance of various oxygen binding states. The exchange between different oxygen phases was studied by¹⁶O₂/¹⁸O₂ isotope experiments.     

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.     

Sputtering of metals at ion-electron irradiation

It has been found that, in contrast to the commonly accepted opinion, simultaneous irradiation by 15-keV Ar⁺ ions and 2.5-keV electrons at temperatures above 0.5T _m (T _m is the melting temperature) induces much larger sputtering of metallic copper, nickel, and steel than irradiation only by Ar⁺ ions. The effect increases with the temperature. At T = 0.7T _m, the sputtering coefficients in the case of ion-electron irradiation are more than twice as large as the sputtering coefficients in the case of irradiation by Ar⁺ ions. The experiments on the sublimation of copper show that the sublimation rate in the case of the heating of a sample by an electron beam is higher than that in the case of heating in an electric vacuum oven. The revealed effects are explained by the electron-induced excitation of adatoms (atoms stuck over the surface, which appear owing to ion bombardment). Excited adatoms have a smaller binding energy with the surface and are sputtered more easily.     

Effect of simultaneous helium implantation on the microstructure evolution of Inconel X-750 superalloy during dual-beam irradiation

This study focuses on investigation into the effect of helium implantation on microstructure evolution in Inconel X-750 superalloy during dual-beam (Ni⁺/He⁺) irradiation. The 1 MeV Ni⁺ ions with the damage rate of 10^?3 dpa/s as well as 15 keV He⁺ ions using rate of 200 appm/dpa were simultaneously employed to irradiate specimens at 400 °C to different doses. Microstructure characterization has been conducted using high-resolution analytical transmission electron microscopy (TEM). The TEM results show that simultaneous helium injection has significant influence on irradiation-induced microstructural changes. The disordering of γ′ (Ni₃ (Al, Ti)) precipitates shows noticeable delay in dose level compared to mono heavy ion irradiation, which is attributed to the effect of helium on promoting the dynamic reordering process. In contrast to previous studies on single-beam ion irradiation, in which no cavities were reported even at high doses, very small (2–5 nm) cavities were detected after irradiation to 5 dpa, which proved that helium plays crucial role in cavity formation. TEM characterization also indicates that the helium implantation affects the development of dislocation loops during irradiation. Large 1/3 〈1?1?1〉 Frank loops in the size of 10–20 nm developed during irradiation at 400 °C, whereas similar big loops detected at higher irradiation temperature (500 °C) during sole ion irradiation. This implies that the effect of helium on trapping the vacancies can help to develop the interstitial Frank loops at lower irradiation temperatures.     

Investigation of silicon doped by zinc ions with a large dose

The formation of nanoparticles in СZn-Si(100) implanted with ⁶⁴Zn⁺ ions using a dose of 5 × 10¹⁶ cm^–2 and an energy of 50 keV at room temperature with subsequent thermal processing in oxygen at temperatures ranging from 400 to 900°C is studied. The surface topology is investigated with scanning electron (in the secondary emission mode) and atomic force microscopes. The structure and composition of the near-surface silicon layer are examined using a high-resolution transmission electronic microscope fitted with a device for energy dispersive microanalysis. An amorphized near-surface Si layer up to 130 nm thick forms when zinc is implanted. Amorphous zinc nanoparticles with an average size of 4 nm are observed in this layer. A damaged silicon layer 50 nm thick also forms due to radiation defects. The metallic zinc phase is found in the sample after low-temperature annealing in the range of 400–600°C. When the annealing temperature is raised to 700°C, zinc oxide ZnO phase can form in the near-surface layer. The complex ZnO · Zn₂SiO₄ phase presumably emerges at temperatures of 800°C or higher, and zinc-containing nanoparticles with lateral sizes of 20–50 nm form on the sample’s surface.     

Coexistence of superconductivity and magnetic ordering in the borocarbide superconducting system

The investigation of the intermetallic compounds Y_1−xRE_xNi₂B₂C and Y_1−xRE_xPd₅B₃C_0.4 (RE=Gd, Dy, Ho, Er; 0≤x≤1.0) demonstrates that the coexistence of the long-range-magnetic-ordering and the superconductivity is possible The normal-state magnetic susceptibility shows a Curie-Weiss-like temperature dependence and a small paramagnetic Curie temperature. The value of the effective moment is close to that of the free RE⁺³ ion. Both results suggest that the coupling between the conduction electron and magnetic ion is not strong, but the coupling is still strong enough to cause the depression of superconductivity. The Abrikosov-Gor‘kov magnetic pair-breaking theory can be applied to those systems. The corresponding magnetic-ordering temperature increases with increasing magnetic moment concentration while the superconducting transition temperature decreases. The long-range-magnetic-ordering is mainly caused by the Ruderman-Kittel-Kasuya-Yosida indirect exchange interaction via conduction electrons. This indirect exchange coupling strongly depends on the concentration of RE⁺³-moment and de Gennes factor.     

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.     

Composition and Structure of Ga<Subscript>1 – <Emphasis Type="Italic">x</Emphasis></Subscript>Na<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>As Nanolayers Produced near the GaAs Surface by Na<Superscript>+</Superscript> Implantation

The composition and structure of nanodimensional Ga_{1 – x}Na _x As phases produced by implantation of Na⁺ ions into the near-surface area of GaAs have been studied by Auger electron spectroscopy and fast electron diffraction. It has been found that the thickness of the ternary epitaxial layer is 10–12 nm for ion energy E₀ = 20 keV. The composition of the three-layer nanosystems is GaAs–Ga_0.5Na_0.5As–GaAs.     

Secondary ion emission under the bombardment of Si by multiply charged Si q+ ions

The spectra of secondary ion emission under the bombardment of a B-doped Si target by multiply charged Si ^q+ ions (q = 1?C5) have been studied in the energy range of 1 to 10 keV per unit of charge. A multifold increase in the yield of secondary cluster Sk _n ⁺ ions, multiply charged Si ^q/+ ion (q = 1?C3), and H⁺, C⁺, B⁺, Si₂N⁺, Si₂O⁺ is observed as the charge of the multiply charged ions increases. The increase in the yield of secondary ions with increasing charge of the multiply charged-ion charge is most significant for ions with relatively high ionization potentials.     

A search for a thermal spike effect in sputtering

The temperature dependence of the sputtering yield was measured for lOOkeV per atom bombardment of silver with molecular and atomic antimony ions. No exponential increase of the yield was found in the temperature range from 25° to 775 °C, although a pronounced nonlinear effect is observed when the yield of these projectiles is compared,Y(Sb ₂ ⁺ )≈ 1.5×[2Y(Sb⁺)]. We conclude that there is no influence of the lattice temperature on collision spikes.