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.     

ESCA studies of oxygen adsorption on nickel

A metallic nickel foil was studied by ESCA. The Ni 2p electron spectrum was characteristic of a mixture of nickel oxide and metallic nickel. Two ox     

ESCA studies of fracture surfaces in welded metals

A fracture device for ESCA studies of internal surfaces in metals is described. By fracturing a specimen under UHV, an uncontaminated surface is obtain The specimen is cooled to produce cleavage or intergranular fracture, depending upon the type of information sought.The technique has been applied to weldments in steels of composition C 0.020, Mn 1.15. In the as-welded state, fracture surfaces yield signals of C, N, and O as well as iron in oxidized state beside metallic iron. Antimony is found on the fracture surface of specimens embrittled by long annealing in ox A strong chemical shift indicates that it is present in the oxidized state.     

ESCA studies of Cr-Co alloys

ESCA examination of films formed on Cr-Co alloys after immersion in 0.1M NaCl for 24 h has shown that the thickness of passive films decreased with an increase in chromium content. Surface films consisted of chromium and cobalt oxides as Cr₂O₃ and CoO. The amount of CoO in the surface film of the alloy was decreased with an increase in chromium but Cr₂O₃ was found at a greater depth in the passive film at any composition. Cr₂O₃ was a major component of the surface film when the chromium content in the alloy was 10% or higher. Electrochemical techniques according to ASTM G59 and ASTM G5 were used for the determination of the relative corrosion rate. Both Co-10 wt.% Cr and Co-30 wt.% Cr alloys investigated showed a lower corrosion rate than the Co-5 wt.% Cr alloy. Corrosion rate measured could be correlated to the surface film composition and structure as determined by ESCA.     

ESCA studies of Fe-Ti alloys

Fe-Ti alloys containing 5 to 47% Ti have been studied by ESCA. The alloys were exposed to 0.1 M NaCl for 24 h under open-circuit potential (OCP) during which passive films were formed. The passive film consisted of FeO and TiO₂ in the inner layer while Fe₂O₃, water, and hydroxyl groups were present in the outermost monolayers, irrespective of composition. The thickness of the passive layer was reduced from 4.4 nm to 1.0 nm with increasing Ti content. The amount of iron oxide in the passive layer also decreased with increasing Ti. Electrochemical techniques according to ASTM G59 and ASTM G5 were used for the determination of the relative corrosion rate of the alloys. Alloys with 5–28% Ti showed a relatively high corrosion rate but that with 47 wt.% Ti had a much lower corrosion rates.     

ESCA studies of Ni-Cr alloys

ESCA examination on Ni-Cr alloys has shown that a thin passive film was formed after 24 h immersion in 0.1 M NaCl. The film contained only chromium oxide in the form of Cr₂O₃. Electrochemical techniques according to ASTM G59 and ASTM G5 were used for the determination of the relative corrosion rate of the alloys. Both Ni-10 wt. % Cr and Ni-20 wt. % Cr alloys showed a slightly higher corrosion rate than the Ni-40 wt. % Cr alloy.The present ESCA study of the Ni-Cr system is part of our programme which involves an examination of the four binary alloy systems Fe-Si, Cr-Co, Ni-Cr, and Mo-Ni [1]. The aim is to correlate the structure and composition of the passive films formed in 0.1 M NaCl to the corrosion behaviour in the same solution.     

ESCA studies of Si-Fe alloys

ESCA examination of films formed on Si-Fe alloys after immersion in 0.1 M NaCl for 24 h has hown that the thickness of passive films decreased with an increase in silicon content. A thick passive film containing oxidized silicon and oxidized iron was formed on Fe-20 wt% Si and the oxidized iron was about three times higher than the oxidized silicon in the passive film. However, an obvious reduction in the oxidized iron in the film on Fe-30 wt % Si was observed. Oxidized iron was detected up to a depth of 1.0 nm and at a depth greater than 1.0 nm from the surface, the film was exclusively in oxidized silicon. The film was exclusively silicon oxide when the silicon content was increased to 50 wt %. Electrochemical techniques according to ASTM G59 and ASTM G5 were used for the determination of the relative corrosion rate. Fe-50 wt % Si was found to have a corrosion rate smaller than those lower silicon alloys. This relates to the surface film composition and structure as determined by ESCA.     

XPS studies of ion-bombardment damage of transition metal sulfides

Radiation damage to the surface of transition metal sulfides under ～1-keV ion bombardment has been investigated by photoelectron spectroscopy. Under     

ESCA studies of nitrogen-containing stainless steels

ESCA examination of films formed on nitrogen-containing stainless steels after immersion in 0.1 M NaCl revealed that nitrogen was enriched in the outer 0.5 nm of the film at a concentration a few times higher than in the substrate. The N(1s) binding energy varied from 399.6–399.7 eV at the outermost surface of the film to 398.3–398.8 eV in the film at a depth of about 0.5 nm. This indicates a change in the chemical state of nitrogen upon exposure of the nitrogen-containing stainless steels to the solution, and furthermore, that the surface nitrogen enrichment could be of significance in the improved pitting resistance.     

ESCA studies of some niobium compounds

Binding energies of $\text{3d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$ level of niobium in some of its compounds have been investigated using X-ray photoelectron spectroscopy. The shift ΔBE in binding energy of $\text{3d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$ level of niobium in its several compounds with respect to that in niobium metal can be expressed by the relation ΔBE = i[B_5s + (m ? 1)B_4d], where i and m are the overall ionicity and valence of niobium in a compound.     

ESCA studies of some copper and silver selenides

Photoelectron and Auger spectra have been obtained for the copper and silver selenides CuSe, Cu ₂Se, Ag ₂Se, and AgCuSe as well as from CuS, Ag ₂O, Ag ₂S, Cu, and Ag. Binding-energy values, chemical shifts, and peak-shapes are reported for the Cu 3 d, Ag 4 d and Se 3 p electrons. Absence of multiplet splitting and shake-up structure is discussed in relation to the magnetic properties. It is shown that chemical shifts are much better revealed in the Auger spectra (Cu L₃M_4,5M_{4, 5} and Ag M₅N_{4, 5}N_{4, 5}) than in the direct photoelectron ones. In addition the use of the Auger parameter to characterize the series under study is emphasized. Finally the valence-band spectra have been examined and the electronic structures are interpreted.     

ESCA study of carbon monoxide and oxygen adsorption on tungsten

The chemisorption of both CO and O₂ on a clean tungsten ribbon has been studied using an ultrahigh vacuum X-ray photoelectron spectrometer. For CO, the energy and intensity of photoemission from O(1s) and C(1s) core levels have been studied for various adsorption temperatures.At adsorption temperatures of ～100 K., the “virgin”-CO state was the dominant adsorbed species. Conversion of this state to more strongly-bound β-CO is observed upon heating the adsorbed layer to ～320K. Thermal desorption of CO at 300?T?640 K causes sequential loss of α₁-CO and α₂-CO as judged by the disappearance of O(1s) and C(1s) photoelectron peaks characteristic of these states.Oxygen adsorption at 300K gives a single main O(ls) peak at all coverages, although at high oxygen coverages there exist small auxiliary peaks at ～2eV lower kinetic energy. The photoelectron C(1s) and O(1s) binding energies observed for these adsorbed species are all lower than for gaseous molecules containing C and O atoms. For CO adsorption states there is a systematic decrease in photoelectron binding energy as the strength of adsorption increases. These observations are in general accord with expectations based on electronic relaxation effects in condensed materials.     

Recent progress in ESCA studies of gases

The development during the most recent years of ESCA applied to free molecules is reviewed. The advantages of studying, when possible, a substance in t     

Gallium and oxygen accumulations on gallium nitride surfaces following argon ion milling in ultra-high vacuum conditions

Metallic gallium was observed on the surfaces of GaN commercial samples following argon ion milling. SIMS measurements confirmed that the commercial GaN had approximately 0.02% bulk oxygen present. The SIMS signal was standardized using a specimen of known oxygen content, as determined by elastic recoil detection analysis using 200 MeV heavy ions of ¹⁹⁷Au. Despite this 2–5% oxygen was observed by XPS in the bulk of the GaN after the argon ion milling. This oxygen is believed to be from the original surface oxide that re-cycles on the GaN surface during the ion milling.     

ESCA studies of chemical shifts for metal oxides

The binding energy shifts of some 35 elements on formation of an oxide have been measured by X-Ray Photoelectron Spectroscopy. When these are plotted against the atomic numbers of the elements or against the heat of formation of the oxides, characteristic trends can be observed, for the interpretation of which a number of rules of general validity may be drawn up.     

Superficial defects induced by argon and oxygen bombardments on (110) TiO2 surfaces

Compositional and chemical changes of titanium dioxide monocrystalline surfaces induced by bombardment with 4 keV argon and oxygen ions have been studied by AES, XPS and AFM. Argon ion bombardment induced strong changes in the composition and chemical state of the surface: loss of oxygen due to preferential sputtering occurred, and, related to this, Ti⁴⁺ species were reduced to Ti³⁺ and Ti²⁺. During oxygen bombardment, competition between preferential sputtering of oxygen ions of the oxide surface and oxygen implantation was observed. This phenomenon was found to be strongly dependent upon the incidence angle of the oxygen ions. Moreover, an oxygen bombardment with normal incidence of the surface that had been previously submitted to an argon ion bombardment led to a restoichiometrization of the surface: no further Ti³⁺ or Ti²⁺ was found by XPS, only Ti⁴⁺.     

Valence band studies of clean and oxygen exposed GaAs(100) surfaces

We found, by correlating band bending, ultraviolet photoemission spectroscopy, and partial yield spectroscopy measurements, that Fermi level pinning at midgap of n-type GaAs(110) is caused by extrinsic states. The exact nature of these states is not yet clear, but the surfaces with Fermi level pinning were strained as evidence by a smeared valence band emission. This smearing was removed by as little as one oxygen per 10⁴ to 10⁵ surface atoms. This implies that the oxygen has very long range effects in causing spontanesous but small rearrangement of the surface lattice and removing surface strains. When about 5% of a monolayer of oxygen is adsorbed, a major change in the electronic structure takes place. Again, the oxygen coverage is very small, which suggests long range effects now leading to a fairly large rearrrangement of the surface lattice. Finally, from comparing the oxygen induced emission for exposures greater than 10⁷ L O₂, with the spectra from gas photoemission measurements on molecular oxygen, we suggest that the oxygen is chemisorbed as a molecule on the (110) surface of GaAs.