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.     

A photoemission study of the interaction of Ni(100), (110) and (111) surfaces with oxygen

Photoelectron spectroscopic studies of the oxidation of Ni(111), Ni(100) and Ni(110) surfaces show that the oxidation process proceeds at 295 and 485 K in two distinct steps: a fast dissociative chemisorption of oxygen followed by oxide nucleation and lateral oxide growth to a limiting coverage of 3 NiO layers. The oxygen concentration in the 295 K saturated oxygen layer on Ni(111) was confirmed by ¹⁶O(d,p) ¹⁷O nuclear microanalysis. At 295 and 485 K the oxide growth rates are in the order Ni(110) > Ni(111) > Ni(100). At 77 K the oxygen uptake proceeds at the same rate on all three surfaces and shows a continually decreasing sticking coefficient to saturation at ~2.1 layers (based upon NiO). An O 1sb.e. = 529.7 eV is associated with NiO, and O ls b.e.'s of ~531.5 and 531.3 eV can be associated, respectively, with defect oxide (Ni₂O₃) or (in the presence of H₂O) with an NiO(H) species. The binding energies (Ni 2p, O 1s) of this NiO(H) species are similar to those for Ni(OH)₂. Defect oxides are produced by oxidation at 485 K, or by oxidation of damaged films (e.g. from Ar⁺ sputtering) and evaporated films. Wet oxidation (or exposure to air) of clean nickel surfaces and oxides, and exposure of thick oxide to hydrogen at high temperature results in an O 1s b.e. ~531.3 eV species. Nuclear microanalysis ²H(³He,p) ⁴He indicates the presence of protonated species in the latter samples. Oxidation at 77 K yields O 1s b.e.'s of 529.7 and ~531 eV; the nature of the high b.e. species is not known. Both clean and oxidised nickel surfaces show a low reactivity towards H₂O; clean nickel surfaces are ~10³ times less reactive to H₂O than to oxygen.     

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.     

Effect of alkali leaching on the surface structure of Ni3Al catalyst

The surface structure of the alkali-leached single-phase Ni₃Al powder was investigated by X-ray diffraction, BET (Brunauer-Emmett-Teller) surface area analysis, electron microscopy, X-ray photoelectron spectroscopy, and temperature-programmed reduction. It was found that fine Ni particles of several nm in diameter were formed on the outer surface layer of the Ni₃Al powder after the alkali leaching process. The surface of the Ni particles was covered with a thin layer of Ni oxides and hydroxide, Ni₂O₃, NiO and Ni(OH)₂, and these Ni oxides and hydroxide can be easily reduced by hydrogen to the metallic nickel that is catalytically active. The inside of the Ni₃Al powder remained as the original Ni₃Al ordered structure after alkali leaching. Having heat resistant properties, the Ni₃Al phase can serve as a support of the fine Ni particles and provide the structural and thermal stabilities to the fine Ni particles.     

Influence of argon ion bombardment on the formation of intermetallic compounds in the nickel-aluminum system

The formation of Ni _x Al _y intermetallic compounds in two-layer (Ni/Al) structures (nickel films deposited on aluminum substrates in vacuum) under bombardment by Ar⁺ ions has been studied experimentally. The method based on Rutherford backscattering of He⁺ ions is used to demonstrate that argon ion bombardment causes the formation of intermetallic compounds in the near-surface layer. The thickness of the intermetallic layer formed in the near-surface region substantially exceeds the projective ion path. The composition and thickness of the intermetallic layer depend mainly on the implantation dose and the substrate temperature, rather than on the ion current density. In the intermetallic layer, the content of nickel increases with increasing temperature. It has been established that, in the absence of bombardment, intermetallic phases are not observed at temperatures lower than T = 400°C and that, in the presence of bombardment, the Ni₃Al intermetallic layer arises at a temperature of 320°C.     

New interpretations of XPS spectra of nickel metal and oxides

A current interpretation of XPS spectra of Ni metal assumes that the main 6 eV satellite is due to a two hole c3d⁹4s² (c is a core hole) final state effect. We report REELS observation in AES at low voltages of losses (plasmons and inter-band transitions) corresponding to the satellite structures in Ni metal 2p spectra. The satellite near 6 eV is attributed to a predominant surface plasmon loss. A current interpretation of Ni 2p spectra of oxides and other compounds is based on charge transfer assignments of the main peak at 854.6 eV and the broad satellite centred at around 861 eV to the cd⁹L and the unscreened cd⁸ final-state configurations, respectively (L is a ligand hole). Multiplet splittings have been shown to be necessary for assignment of Fe 2p and Cr 2p spectral profiles and chemical states. The assignments of Ni 2p states are re-examined with intra-atomic multiplet envelopes applied to Ni(OH)₂, NiOOH and NiO spectra. It is shown that the free ion multiplet envelopes for Ni²⁺ and Ni³⁺ simulate the main line and satellite structures for Ni(OH)₂ and NiOOH. Fitting the NiO Ni 2p spectral profile is not as straightforward as the hydroxide and oxyhydroxide. It may involve contributions from inter-atomic, non-local electronic coupling and screening effects with multiplet structures significantly different from the free ions as found for MnO. A scheme for fitting these spectra using multiplet envelopes is proposed.     

ESCA studies of metal-oxygen surfaces using argon and oxygen ion-bombardment

ESCA has been used to monitor alterations of catalytically and electrochemically important metal-oxygen surfaces following exposure to Ar⁺ and O₂⁺ ion bombardment. This treatment resulted not only in sputtering, but also, in many cases, in reduction to the corresponding metal or lower oxide. A model based on bulk thermodynamic free energy considerations Is proposed to explain this phenomenon. We have also exploited this approach to obtain an in-depth concentration profile of various oxidation states of an element, to selectively prepare desired surface oxide compositio and to aid in interpreting complex O ls spectra. Results obtained from metal-oxygen surfaces for Ni, Ru and Mo are presented. Ni₂O₃ and RuO₃, which are gross defect structures of the bulk species, are present on NiO and RuO₂ respectively, with the former being confined to the surface layers. The MoO₂, on the other hand, is covered with a surface layer of MoO₃ present as a regular crystal structure.     

The anomalous behaviour of the ESID O+ yield from a Ni(110) surface during oxygen adsorption

The behaviour of the ESID O⁺ yield is studied as a function of the exposure of a Ni(110) surface to oxygen. Measurements performed during the adsorption process reveal a contribution to the ESID O⁺ yield, which is ascribed to a precursor state. If there is a time lapse between exposure and the measurement, the precursor state is not observed. For this situation the O⁺ ions, generated by electron impact, are shown to originate from NiO islands. The disappearance of the precursor state is explained as a transition into a chemisorption state and a depletion by ESD. The behaviour of the O⁺ yield from the NiO islands during adsorption is assumed to be due to the formation of Ni₂O₃ on top of the NiO islands.     

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.     

Ionized physical vapor deposited Al2O3 films: Does subplantation favor formation of α‐Al2O3?

The broad energy distributions of the condensing particles typically encountered in ion assisted vapor deposition techniques are often a drawback when attempting to understand the effect of the energetic bombardment on the film properties. In the current study, a monoenergetic Al⁺ beam generated by a filtered cathodic arc discharge is employed for the deposition of alumina (Al₂O₃) films at well defined Al⁺ ion energies between 4 eV and 200 eV at a substrate temperature of 720 °C. Structural analysis shows that Al⁺ energies of 40 eV or larger favor the formation of the thermodynamically stable α‐Al₂O₃ phase at the expense of other metastable Al₂O₃ polymorphs. The well defined ion energies are used as input for Monte‐Carlo based simulations of the ion–surface interactions. The results of these simulations reveal that the increase of the Al⁺ ion energy leads to an increase in the fraction of ions subplanted into the growing film. These findings underline the previously not considered role of subsurface processes on the phase formation of ionized physical vapor deposited Al₂O₃ films. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A SIMS study of ion beam induced migration of nitrogen in thermally oxidized silicon

The potential use of thin silicon nitroxide films as gate dielectrics in VLSI MOS devices has motivated much recent work. The present study shows that positive ion bombardment, as encountered in sputter depth profiling or ion implantation, can induce considerable movement of nitrogen in thin thermal oxide films on silicon. Low energy N⁺₂ implants are performed in-situ in a SIMS apparatus and are subsequently depth profiled. The effect of implant dose and oxide thickness are examined and comparisons are made to films prepared by rapid thermal nitridation and LPCVD. Profiles obtained under O⁺₂, O^-, and Cs⁺ bombardment are also compared. SIMS depth profiles of implanted 200 Å oxides using positive ion bombardment show a depletion of nitrogen near the surface, a shoulder in the nitrogen concentration near the Si-SiO₂ interface, and a peak in this concentration at the interface. Negative ion bombardment did not induce a shoulder-peak structure at the interface. The implications of these results are discussed.     

有机金属化学气相沉积法制备的Ni/Al2O3纳米复合材料的氢吸附

研究了通过有机金属化学气相沉积技术及单源分子前躯体方法制备的Ni/Al₂O₃纳米复合材料的氢吸附(存储). 在冷壁的有机金属化学气相沉积反应器中,通过降解Ni(acac)₂粉末基底上的[H₂Al(OtBu)]₂制备的Ni/Al₂O₃纳米复合材料. 通过X射线粉末衍射、扫描电镜、透射电镜以及能量色散型X射线荧光光谱等技术表征该复合材料. 采用自制Sievert's设备研究该复合材料的氢吸附(存储),可以储存约2.9%(重量比)的氢.     

Chemical effects in TiO2 and titanates due to bombardment with Ar+ and O 2 + ions of different energies (3.5-10 keV)

Compositional and chemical changes in TiO₂ and Ph, Ni, Al and Ba titanates induced by bombardment with Ar⁺ and O ₂ ⁺ ons of different energies have been studied quantitatively by XPS. An increase of preferential loss of oxygen and, in case of PbTiO₃, of lead has been observed when increasing the Ar+ ion energy from 3.5 to 10 keV. Because of oxygen loss, Ti⁴⁺ species reduce to Ti³⁺ and Ti²⁺. In addition, the loss of oxygen from PbTiO₃ and NiTiO₃ leads to the metallic state of nickel and lead, whereas aluminium and barium in Al₂TiO₅ and BaTiO₃ maintain their chemical state (i.e., Al³⁺ and Ba²⁺). Bombardment with OZ ions of PbTiO₃ and NiTiO₃ leads to a partial reduction of Pb and Ni. This metallization and the preferential loss of lead are more efficient at higher ion energies for both, O ₂ ⁺ and Ar⁺ bombardment. The results are discussed in terms of chemical stabilities and the possibility of oxygen diffusion in the bombarded oxides.     

X-ray stimulated luminescence in MgO

Studies have been made of the emission spectrum of MgO crystals induced by X-irradiation at 90 K. Two bands (half-widths ～0.8 eV) were observed to peak at 4.95 and 3.2 eV, respectively, in high purity crystals. Doping with 100 ppm or greater of Fe, Co, Cr, Cu, Mn, and Ni suppressed the luminescence, though in the MgO:Ni crystal the 2.3 eV Ni²⁺ band due to the ¹T_2g→³A_2g transition was observed. In deuterium-doped crystals the ratio of the intensity of 3.2–4.95 eV emission was found to be 1.2 as compared to 8 for the undoped crystals. Prior exposure of the pure crystals to ionizing radiation enhances the 4.95 eV band by a factor of three while not affecting the 3.2 eV band. This enhancement of intensity decays in several stages upon standing at room temperature in a way that reflects the thermal stability of the various components of the composite V-band absorption. These facts together with the observation that the 210 K thermoluminescence peak is composed entirely of 4.95 eV emission indicate that this luminescence band is associated with the recombination of an electron with a hole located in a V-type center, i.e. O?□ + e → (O²?□)1 → O²?□ + 4.95 eV, where the square indicates that the perturbing positive ion vacancy is adjacent to the oxugen ion which has captured the hole. In MgO:Li⁺, which exhibits no V-type centers upon irradiation, the 4.95 eV band was absent and a 2.9 eV emission which may be associated with recombination at the [Li]⁰ center was observe.     

Electron energy loss spectra from polycrystalline Cr and Cr2O3 before and after surface reduction by Ar bombardment

Electron energy loss spectra (ELS) have been obtained from polycrystalline Cr and Cr₂O₃ before and after surface reduction by 2 keV Ar⁺ bombardment. The primary electron energy used in the ELS measurements was systematically varied from 100 to 1150 eV in order to distinguish surface versus bulk loss processes. Two predominant loss features in the ELS spectra obtained from Cr metal at 9.0 and 23.0 eV are assigned to the surface and bulk plasmon excitations, respectively, and a number of other features arising from single electron transitions from both the bulk and surface Cr 3d bands to higher-lying states in the conduction band are also present. The ELS spectra obtained from Cr₂O₃ exhibit features that originate from both interband transitions and charge-transfer transitions between the Cr and O ions as well as the bulk plasmon at 24.4 eV. The ELS feature at 4.0 eV arises from a charge-transfer transition between the oxygen and chromium ions in the two surface layers beneath the chemisorbed oxygen layer, and the ELS feature at 9.8 eV arises from a similar transition involving the chemisorbed oxygen atoms. The intensity of the ELS peak at 9.8 eV decreases after Ar⁺ sputtering due to the removal of chemisorbed oxygen atoms. Sputtering also increases the number of Cr²⁺ states on the surface, which in turn increases the intensity of the 4.0 eV feature. Furthermore, the ELS spectra obtained from the sputtered Cr₂O₃ surface exhibit features characteristic of both Cr⁰ and Cr₂O₃, indicating that Ar⁺ sputtering reduces Cr₂O₃. The fact that neither the surface- nor the bulk-plasmon features of Cr⁰ can be observed in the ELS spectra obtained from sputtered Cr₂O₃ while the loss features due to Cr⁰ interband transitions are clearly present indicates that Cr⁰ atoms form small clusters lacking a bulk metallic nature during Ar⁺ bombardment of Cr₂O₃.     

Electrochemical behavior of Li intercalation processes into a Li[NixLi(1/3−2x/3)Mn(2/3−x/3)]O2 cathode

Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ (X=0.17, 0.25, 0.33, 0.5) compounds are prepared by a simple combustion method. The Rietvelt analysis shows that these compounds could be classified as having the α-NaFeO₂ structure. The initial charge-discharge and irreversible capacity increases with the decrease of x in Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂. Indeed, Li[Ni_0.50Mn_0.50]O₂ compound shows relatively low initial discharge capacity of 200 mAh/g and large capacity loss during cycling, with Li[Ni_0.17Li_0.22Mn_0.61]O₂ and Li[Ni_0.25Li_0.17Mn₀.₅₈]O₂ compounds exhibit high initial discharge capacity over 245 mAh/g and stable cycle performance in the voltage range of 4.8 -2.0 V. On the other hand, XANES analysis shows that the oxidation state of Ni ion reversibly changes between Ni²⁺ and about Ni³⁺, while the oxidation state of Mn ion sustains Mn⁴⁺ during charge-discharge process. This result does not agree with the previously reported ‘electrochemistry model’ of Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂, in which Ni ion changes between Ni²⁺ and NI⁴⁺. Based on these results, we modified oxidation-state change of Mn and Ni ion during charge-discharge process.     

射频溅射微晶NiOxHy膜电致变色性能及其机理研究

研究了射频溅射制备的NiO_x膜的电致变色性能,发现富氧非理想化学配比的NiO _x(x>1)膜具有变色活性,这种膜出现Ni³⁺和Ni²⁺的混 合价态,当H^＋注入并占据Ni空位时,导致Ni³⁺的t_2g 能级被填满,Ni³⁺被阴极还原为Ni²⁺引起光学透明,即为漂白态; 反之,H⁺被萃取出NiO 关键词： xH_y膜')" href="#">NiO_xH_y膜 电致变色     

Surface composition modification of tungsten higher oxide under He<Superscript>+</Superscript> ion bombardment

The surface reduction of higher oxide WO₃ under irradiation by He⁺ ions with the energies 1 and 3 keV in a high vacuum is investigated by X-ray photoelectron spectroscopy. It is found that lower WO₂ and intermediate WO _x (2 < x < 3) oxides form first in WO₃ surface layers under He⁺ ion bombardment, and with an increase in the irradiation dose metallic tungsten forms. It is shown that the degree of irradiated oxide surface metallization increases with an increase in the energy of the bombarding He⁺ ions. A comparison of WO₃ oxide surface composition modification under He⁺ and Ar⁺ ion irradiation is presented.     

Initial oxidation of polycrystalline Permalloy surface

X-ray photoelectron spectroscopy (XPS) and work-function measurements were used in combination to investigate the initial steps of Permalloy (Ni₈₀Fe₂₀) oxidation at room temperature. They showed that, after oxygen saturation, the surface is covered by nickel oxide (NiO), nickel hydroxide (Ni(OH)₂) and iron oxides (Fe_xO_y), and there is no preferential oxidation. Iron oxidation proceeds through the formation of FeO (Fe²⁺) followed with Fe₂O₃ growth (Fe³⁺). The oxidation is governed by a dissociative Langmuir-type oxidation: the sticking coefficient is decreasing over oxygen exposure. Oxidation continues by oxygen dissolution into the first layers to form a nano-oxide of about 8 Å in thickness.