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.     

In situ FTIR study of oxygen adsorption on nanostructured RuO2 thin-film electrode

In situ Fourier transform spectroscopy (FTIR) was used to study interactions of nanostructured ruthenium oxide (RuO₂) thin-film sensing electrode with O₂ at room temperature. RuO₂ nanostructures were pretreated at 1,000 °C for 1 h in order to obtain good crystallinity of amorphous RuO₂ nanoparticles. Morphology and properties of nanostructured RuO₂ were characterized by X-ray diffraction, thermo-gravimetric/differential thermal analysis, scanning electron microscopy, and FTIR. It was shown that pretreated RuO₂ is quite active for O₂ ⁻, O₂ ²⁻, and O²⁻ adsorption with clear 722 cm⁻¹ band for superoxide ions (O₂ ⁻) adsorption for the different oxygen concentrations. The results of in situ FTIR measurements revealed that the active sites for oxygen adsorption are not limited to the triple boundaries, but extended to surfaces of RuO₂ electrodes. Fundamental vibration frequencies of ruthenium–oxygen bond at a temperature of 23 °C as well as region above fundamental frequencies for the nanostructured RuO₂ were identified.     

An electrochromic device (ECD) cell characterization on electron beam evaporated MoO3 films by intercalating/deintercalating the H+ ions

Thin films of molybdenum oxide (MoO₃) is one of the most interesting layered intercalation materials because of its excellent application in solid state batteries, large-area window and display systems. In recent years there has been considerable interest in variable transmittance electrochromic devices (ECD) based on Li⁺, H⁺ and K⁺ intercalation in transition metal oxide (MoO₃) thin films. In the present investigation, thin films of MoO₃ were prepared by electron beam evaporation technique on microscopic glass and fluorine doped tin oxide (FTO) coated glass substrates for the application in electrochromic device cells. The compositional stoichiometry of the films was studied by X-ray photoelectron spectroscopy (XPS). The electrochromic nature of the films has been analyzed by inserting H⁺ ions from the H₂SO₄ electrolyte solution using the cyclic-voltammetry (CV) technique. We studied the electrochromic device cells (ECD) incorporating an evaporated MoO₃ thin films as electrochromic layers. The devices exhibit good optical properties with low transmittance values in the colored state, which make them suitable for large-area window applications. The maximum coloration efficiency of the cell was observed at about 70 cm²/C.     

Stoichiometric and oxygen deficient MoO3(010) surfaces

The (010) surface of single crystal MoO₃ has been prepared and examined using LEED, XPS, UPS, and ELS. Three methods yield the stoichiometric surface: scraping in UHV and annealing, ion etching followed by reoxidation (770 K, 10² Pa O₂), or oxygen treatment to remove carbon contamination. LEED shows the surface periodicity is the same as that of the bulk (010). The MoO₃ valence band is 7 eV wide with density of states maxima at 1.5, 3.6, and 5.6 eV below the top of the valence band. Heating MoO₃ in vacuum reduces the surface region. XPS indicates the O/Mo atomic ratio decreases to 2.85 ± 0.12 on heating to 600 K. Ar ion bombardment disorders the surface and reduces the surface O/Mo atomic ratio to 1.6. Annealing of reduced surfaces at > 770 K incompletely reoxidizes them by diffusion of oxygen from the bulk. UPS of reduced and annealed MoO₃ exhibits two new emission features in the bandgap at 0.9 and 2.0 eV above the top of the valence band. These features originate from Mo derived states of a defect involving two or more Mo atoms, such as crystallographic shear planes. Because of the insulating nature of MoO₃, surface charging and electron beam induced damage were substantial hindrances to electron spectroscopic examination.     

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.     

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.     

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.     

Induced crystallization and the physical properties of PbO–Sb2O3–As2O3: MoO3 glass system

PbO–Sb₂O₃–As₂O₃ glasses mixed with different concentrations of MoO₃ (ranging from 0 to 1.0 mol%) were crystallized. The samples were characterized by X-ray diffraction, scanning electron microscopy and differential thermal analysis techniques. The X-ray diffraction and the scanning electron microscopic studies have revealed the presence of Pb₅Sb₂O₈, PbSb₂O₆, SbAsO₄, Sb₂MoO₆, Sb₄Mo₁₀O₃₁, As₄Mo₃O₁₅, Pb₅Sb₄O₁₁ crystalline phases in these samples. The differential thermal analysis indicated that the surface crystallization prevails over the bulk crystallization as the concentration of the crystallizing agent is increased. The infrared (IR) spectral studies exhibit bands due to MoO₄ structural units in addition to the conventional bands due to various antimonate and arsenate structural groups. The studies on PbO–Sb₂O₃–As₂O₃: MoO₃ glass-ceramics with respect to various physical properties viz., dielectric properties over a range of frequency and temperature, optical absorption, electron spin resonance (ESR) and magnetic susceptibility at room temperature have also been reported. The optical absorption, ESR and magnetic susceptibility studies indicated that the molybdenum ions exist in Mo⁵⁺ state in addition to Mo⁶⁺ state in these samples. The redox ratio found to increase as the concentration of the MoO₃ is increased. The variations observed in all these properties with the concentration of the crystallizing agent have been analyzed in the light of different oxidation states and environment of molybdenum ions in the glass ceramic network.     

Electron stimulated desorption of H3O from 316L stainless steel

Surface ions generated by electron stimulated desorption from mass spectrometer ion source grids are frequently observed, but often misidentified. For example, in the case of mass 19, the source is often assumed to be surface fluorine, but since the metal oxide on grid surfaces has been shown to form water and hydroxides, a more compelling case can be made for the formation of hydronium. Further, fluorine is strongly electronegative, so it is rarely generated as a positive ion. A commonly used metal for ion source grids is 316L stainless steel. Thermal vacuum processing by bakeout or radiation heating from the filament typically alters the surface composition to predominantly Cr₂O₃. X-ray photoelectron spectral shoulders on the O 1s and Cr 2p_3/2 peaks can be attributed to adsorbed water and hydroxides, the intensity of which can be substantially increased by hydrogen dosing. On the other hand, the sub-peak intensities are substantially reduced by heating and/or by electron bombardment. Electron bombardment diode measurements show an initial work function increase corresponding to predominant hydrogen desorption (H₂) and a subsequent work function decrease corresponding to predominant oxygen desorption (CO). The fraction of hydroxide concentration on the surface was determined from X-ray photoelectron spectroscopy and from the deconvolution of temperature desorption spectra. Electron stimulated desorption yields from the surface show unambiguous H₃O⁺ peaks that can be significantly increased by hydrogen dosing. Time of flight secondary ion mass spectrometry sputter yields show small signals of H₃O⁺, as well as its constituents (H⁺, O⁺ and OH⁺) and a small amount of fluorine as F⁻, but no F⁺ or F⁺ complexes (HF⁺, etc.). An electron stimulated desorption cross-section of σ⁺ ∼ 1.4 × 10⁻²⁰ cm² was determined for H₃O⁺ from 316L stainless steel for hydrogen residing in surface chromium hydroxide.     

Composition depth profiles of Bi3.15Nd0.85Ti3O12 thin films studied by X-ray photoelectron spectroscopy

In the present work, X-ray photoelectron spectroscopy (XPS) was used to investigate the composition depth profiles of Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) ferroelectric thin film, which was prepared on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by chemical solution deposition (CSD). It is shown that there are three distinct regions formed in BNT film, which are surface layer, bulk film and interface layer. The surface of film is found to consist of one outermost Bi-rich region. High resolution spectra of the O 1s peak in the surface can be decomposed into two components of metallic oxide oxygen and surface adsorbed oxygen. The distribution of component elements is nearly uniform within the bulk film. In the bulk film, high resolution XPS spectra of O 1s, Bi 4f, Nd 3d, Ti 2p are in agreement with the element chemical states of the BNT system. The interfacial layer is formed through the interdiffusion between the BNT film and Pt electrode. In addition, the Ar⁺-ion sputtering changes lots of Bi³⁺ ions into Bi⁰ due to weak Bi-O bond and high etching energy.     

Ion-beam reduction of the surface of higher niobium oxide

X-ray photoelectron spectroscopy is used to study the process of reduction of the surface of the higher oxide Nb₂O₅ upon bombardment with inert gas ions (Ar⁺) and reactive gas ions (O₂⁺) with an energy of 1 and 3 keV in high vacuum at room temperature. It is found that, upon bombardment with Ar⁺ ions, the lower oxide NbO and the intermediate oxide NbO₂ are formed in the surface layers of the oxide Nb₂O₅. Bombardment with O₂⁺ ions leads to the formation of an extremely insignificant amount of the intermediate oxide NbO₂ in the surface layers of the oxide Nb₂O₅. It is revealed that the process of ion-beam reduction of the surface of the oxide Nb₂O₅ depends on the ion type, dose, and energy of exposure.     

Secondary-ion emission from oxygen and hydrogen-covered beryllium surfaces: I. Coverage dependence

Secondary ion emission from a beryllium surface is studied in the presence of hydrogen and oxygen. For submonolayer coverages of oxygen, the adsorption follows site-exclusion statistics. On this basis, the Be⁺ secondary ion yield and energy distribution can be separated into oxygen-dependent and oxygen-independent processes governed by the local properties of the surface. Ionic molecular species with hydrogen or oxygen present include Be₂O⁺, Be₂O^?, BeO^?, and BeH⁺ but not BeO⁺ or BeOH⁺. This result is inconsistent with emission in which the oxide molecule is formed in the near-surface vacuum region by agglomeration of individually sputtered surface atoms. For BeH⁺emission the opposite conclusion is reached.     

Molecular selection of MoOx species during migration on Al2O3 and zeolites Y and ZSM-5

Surface migration is the basis of the solid state preparation of various materials. In the case of heterogeneous catalysts, it involves the spreading of metal oxides with low Tammann temperature, such as MoO₃, on various refractory supports like γ-Al₂O₃ and zeolites. In spite of its importance, the speciation of oxide surface migration has not been extensively studied. In this work Mo/γ-Al₂O₃, Mo/ZY and Mo/ZSM-5 were prepared from mixtures of MoO₃ and γ-Al₂O₃, or zeolites Y and ZSM-5, subjected to thermal activation. X-Ray diffraction (XRD), Raman and UV-vis diffuse reflectance spectroscopies were used to study the spread of MoO_x species on refractory metal oxide supports. It was found that during thermal activation the formation and migration of different MoO_x species depends strongly on the structure of the support.     

XPS study of ion-induced chemical effect on β-bismuth molybdate catalyst

Ar ion-induced chemical effect on MoO₃, Bi₂O₃, and β-Bi₂O₃·2MoO₃ has been studied by ESCA. It was found that the reduction behavior of Mo(VI) and Bi(III) in the complex oxide is quite different from that in the single oxides. A relative oxygen enrichment of the ion-bombarded and reduced surface was observed. It has been shown that the oxygen on the bombarded surface is in a special chemical state and incapable of reoxidizing the reduced low valent metal ion. But, exposing to air leads to the reoxidation of the reduced surface and leaves the lattice oxygen anion as the only surface oxygen species. The reduction behavior of β-Bi₂O₃·2MoO₃ under Ar ion bombardment seems to be similar to its redox behavior in butene catalytic oxidation. It was suggested that both of them should reflect the effect of crystal structure on the redox potential of the oxides.     

Temperature‐dependent Raman spectroscopic studies of microstructure present in dipotassium molybdate crystals and their melts

Temperature‐dependent Raman spectra of K₂Mo_nO_3n+1 (n = 1, 2, 3) crystals up to and above their melting points were recorded, and their vibration modes in solid and molten states were assigned. Basic structural units and the corresponding cluster forms in molten dipotassium monomolybdates, dimolybdates, and trimolybdates were studied by in situ high‐temperature Raman spectroscopic studies together with theoretical calculations, including density functional theory and quantum chemistry ab initio calculation. Anion units of [MoO₄]²⁻, [Mo₂O₇]²⁻, and [Mo₃O₁₀]²⁻ were shown to principally exist in molten K₂MoO₄, K₂Mo₂O₇, and K₂Mo₃O₁₀, respectively. The mechanisms of the microstructural evolution of K₂Mo_nO_3n+1 (n = 1, 2, 3) crystals while being melted are schematically illustrated. Copyright © 2016 John Wiley & Sons, Ltd.     

Solid state interactions in nano-sized oxides

Comparative study of reactivity of nano- and micro-sized alumina and nickel oxide, obtained by the electrical explosion of metal wires in oxidizing atmosphere, was carried out for the reactions NiO + MoO₃, NiO + Al₂O₃, and Al₂O₃ + Bi₂O₃ by coupled anneals of ceramics, measurements of the conductivity of individual oxides and raw oxide mixtures, X-ray diffraction and differential thermal analysis. The total conductivity of nano-structured oxides was found lower than that of micro-structured ceramics. Mixing bismuth oxide with nano-structured alumina leads to stabilization of the low temperature polymorph α-Bi₂O₃ up to 780 °C. The diffusion permeability of NiMoO₄ layer grown at the surface of NiO ceramics, having submicron grains, was found 2 times lower if compared to NiMoO₄ grown at micro-sized NiO ceramics. NiO and Al₂O₃ nano-powders preserve the high reactivity even when heated up to 1000 °C. The results are discussed in terms of size effects on the solid state reactivity of oxides.     

Electrochromic phenomena in transition metal oxide thin films prepared by thermal evaporation

We present an experimental study on the electrochromic properties of MoO₃, WO₃ and mixed WO₃-MoO₃ thin films prepared by thermal evaporation. We have constructed symmetric and quasi-symmetric electrochromic cells incorporating the evaporated oxide films as electrochromic layers. Li⁺ doped V₂O₅ films served as ion storage layers. The symmetric cells were found to exhibit significantly improved optical properties compared to the quasi-symmetric ones, with very low luminous transmittance values in the colored state, which makes them suitable for large-area window applications. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Characteristics of molybdenum oxide and chromium oxide cathodes in primary and secondary organic electrolyte lithium batteries I. Morphology,structure and their changes during discharge and cycling

Rechargeable positive electrodes for ambient temperature Li-batteries are mainly based on the same general principle: reversible topotactic Li⁺-intercalation into transition metal chalcogenide host lattices, yielding ternary phases Li_nMCh_x. After an intercalation/deintercalation cycle the original host lattice may be retained practically unchanged if the structure of the host matrix is determined by strong covalent bonds and if the concentration of intercalated ions was small. On the other hand, high concentration of unsolvated Li⁺ ions in fairly ionic oxide host lattices such as MoO₃, Cr₂O₅ or Cr₃O₈ (CrO_x) cause significant irreversible structural and also morphological changes of the host matrix. Moreover, ternary oxides Li_nMO_x prepared at room temperature are non-equilibrium phases — their structural parameters and transport properties vary with conditions of preparation, ageing time etc., and elevated temperature finally causes a complete and irreversible breakdown of their original structure. Prolonged cycling of crystalline large particle size MoO₃ leaves quasi-amorphous powders which, however, are still usable for rechargeable cathodes. Failure of Li_nMoO₃ and Li_nCrO_x electrodes is due to recrystallization via solution, forming e.g. Li₂MoO₄ from Li_nMoO₃. To obtain a better understanding of the limitations of MoO₃ and CrO_x cathodes under practical operation conditions changes in structure and morphology during electrochemical and chemical lithiation and after electrochemical cycling were followed by X-ray diffraction and SEM micrographs; supplementary results were obtained by electrochemical methods and by thermal analysis. Electronically conducting preparations of “hexagonal MoO₃” (which is a hydrated MoO₃ modification) were also characterized with respect to their discharge behaviour and reversibility in organic Li⁺-electrolytes ? their “sloping” discharge characteristics disqualify them for practical applications.     

Study of molybdenum coordination state and crystallization behavior in MoO3-La2O3-B2O3 glasses by Raman spectroscopy

The ternary MoO₃-La₂O₃-B₂O₃ glasses containing a large amount of MoO₃ (10-50 mol%) are prepared, and their structure and crystallization behavior are examined from the Raman scattering spectrum measurements and X-ray diffraction analyses. It is found that the glass transition and crystallization temperatures and the thermal stability against crystallization decrease with increasing MoO₃ content. It is suggested that the main coordination state of Mo⁶⁺ ions in the glasses is isolated (MoO₄)²⁻ tetrahedral units giving strong Raman bands at 830-860 and 930 cm⁻¹. It is found that the crystalline phases in the crystallized glasses are mainly LaMoBO₆ and LaB₃O₆, and the main crystallization mechanism in MoO₃-La₂O₃-B₂O₃ glasses is surface crystallization. LaMoBO₆ crystals are found to give strong Raman bands at 810-830 and ∼910 cm⁻¹.     

Effects of oxide coating on the growth of single grain YBCO bulk superconductors

Surface oxide coating and bottom inserting of oxide plates have been conducted to top seeded melt growth (TSMG) processed YBa₂Cu₃O_7−y (Y123) bulk superconductors with an aim of controlling the Y123 nucleation and growth. The coating medium for surfaces was Yb₂O₃ solution and the bottom inserts were Yb₂O₃/Y₂O₃ powder compact. Many vertical cracks were found to develop at the compact/insert interfaces when an Yb₂O₃ insert was used, but the crack evolution was greatly reduced when a (Yb₂O₃ + Y₂O₃) insert was used. The formation of the vertical cracks is ascribed to the difference in thermal expansion between the YBCO compact and bottom insert. Presence of vertical cracks was found to be crucial to the trapped magnetic field and levitation forces of single grain YBCO bulk superconductors. The Y123 nucleation and growth in TSMG-processed YBCO bulk superconductors were successfully controlled by conducting surface coating and bottom plating using a (Yb₂O₃ + Y₂O₃) insert and as a result, the levitation properties were much enhanced.