Some aspects of auger electron spectra of 3d transition metal oxides

Auger electron spectra of the transition metals Cr, Mn, Fe, Co and Ni as well as their oxides have been investigated in the energy range between 0–100 eV. In each case of the clean metal surface the observed spectrum consists essentially of one Auger line identified asM _2,3 VV transition. After oxidation a line doublet is observed revealing two transitions instead of one. Additional new Auger peaks appear in the low energy range between 0–30 eV. The “splitting” of the Auger line can be explained as resulting from aM _2,3 V _dV_d and aM _2,3 V _pV_p transition. The latter is characteristic for the compound and can in a simple way be interpreted as a cross transition.     

Photoredox laser chemistry of transition metal oxides

Received: 26 May 1997/Accepted: 17 July 1997     

Surface states and metal overlayers on the (110) surface of GaAs

We have found new surface states related to Al overlayers on the (110) surface of GaAs. These states play a prominent role in the determination of the electronic structure for metal-semiconductor interfaces. The results are consistent with conjectures of Rowe, Christman and Margaritondo based upon recent experimental results for metal overlayers on semiconductor surfaces.     

Enhancement of pulsed laser removal of metal oxides by electrochemical control

Pulsed laser irradiation of oxidized metallic surfaces in an electrolytic cell under proper voltage conditions is demonstrated to be a promising new approach for effective removal of oxide films. Systematic measurements on simulated corrosion-product films by optical reflectance profile and energy dispersive X-ray spectroscopy are used to study the physical mechanisms of this novel phenomenon, the physical conditions for its observation and its possible generality. It was observed that the utilization of a basic electrolyte solution and the imposition of a certain cathodic potential prior to laser irradiation is an essential requirement for a high removal efficiency. This new technique has potential applications in metallurgy, semiconductor fabrication technology and decontamination of nuclear power plans and is suitable for maskless patterning of oxidized surfaces.     

Laser ablation time-of-flight mass spectrometric probing of the surface states of SiO2-based porous materials

2 -based materials of different porosity and surface states have been studied by time-of-flight mass spectrometry (TOF-MS) under 308 nm excimer laser ablation. Sequences of SiO₂-based negative ion clusters [(SiO₂)_nX]^- are observed and variations of their abundance distributions with sample properties are studied. The unique roles of surface states in cluster formation are discussed. Received: 10 January 1997/Accepted: 23 June 1997     

Effect of Cu adsorption on the tungsten (100) surface resonance

It has recently been observed that adsorbed Au and Hg do not quench the W (100) surface resonance up to monolayer coverage. We report here that Cu does quench the W (100) surface resonance at θ≧0.5 monolayers. This suggests that the effective potential of Cu differs more strongly from that of W than do the effective potentials of Au or Hg.     

Surface enhanced Raman spectroscopic readout on heavy metal ions based on surface self assembly

A new method is reported for detecting heavy metal ions by using the self assembled monolayer (SAM) technique and surface enhanced Raman spectroscopy (SERS). The p‐mercaptobenzoic acid (MBA) served as the SERS readout molecule and the modified tag to attach on the smooth gold substrate as well as the tag of nanoparticles by the SAM method. Two carboxyl groups from MBA molecules which were attached respectively to gold substrate and gold nanoparticles were linked through the heavy metal ions (Cu²⁺, Pb²⁺ and Zn²⁺) as bridge, and thus sandwich structure of ‘MBA modified gold substrate/heavy metal ions/MBA modified gold nanoparticles’ was built for detection. The observation of the oxidation peak of metal nanoparticles from cyclic voltammetry (CV) curve, gold nanoparticles from scanning electron microscopy (SEM) images and SERS signal of MBA from the sandwich structure indicated the existence of heavy metal ions. The difference in the wavenumbers of vibrational modes from MBA in the sandwich structure constructed by different could be used to identify different heavy metal ions. The assembled structure was rinsed by strong chelator of EDTA solution to remove the heavy metal ions from the sandwich structure and thus to obtain a fresh gold substrate modified with MBA for the cyclic detection. Copyright © 2007 John Wiley & Sons, Ltd.     

Oxygen adsorption on the surface of In2O3 and β-(Ga0.8In0.2)2O3 mixed oxides porous structure

The paper is devoted to the oxygen sensing properties of In_1.2Ga_0.8Se₃ own oxide. The results are compared with theoretical adsorption kinetics. Temperature and time dependences of adsorption mechanisms are discussed.     

Generation of singlet oxygen on the surface of metal oxides

Generation of singlet oxygen on the surface of metal oxides is studied. It is shown that, under conditions of heterogeneous photo-catalysis, along with the conventional mechanism of singlet oxygen formation due to the formation of electron–hole pairs in the oxide structure, there is an additional and more efficient mechanism involving direct optical excitation of molecular oxygen adsorbed on the oxide surface. The excited adsorbate molecule then interacts with the surface or with other adsorbate molecules. It is shown that, with respect to singlet oxygen generation, yttrium oxide is more than an order of magnitude more efficient than other oxides, including titanium dioxide.     

Alkali metal oxides: Occupied,unoccupied and excited states

The occupied and unoccupied electronic states of NaO₂ and KO₂ have been investigated by UV photoemission spectroscopy and inverse photoemission spectroscopy, respectively. In addition single electron excitations from occupied into empty levels have been probed by x-ray absorption and electron energy loss spectroscopy. The experimental data are augmented by LCGTO-X model cluster calculations. A detailed assignment of initial and final states is given. The excitation cross sections and an inversion of the ligand field induced3d level splitting in NaO₂ are discussed.     

Comment on “On the mechanism of liquid metal electron and ion sources”

The electric field near the anode of an electrohydrodynamic ion source is analytically discussed. For the field at the anode apex a rigorous analytical treatment results in the simple expressionE ₀ ≅V _AC/(P₀R₀)^1/2 differing by a factor of 1/2/32 from that by Gomer. Here,V _AC is the applied potential to the cathode with regard to the anode,R ₀ the cathode distance from the anode center, andP ₀ the radius of curvature at the apex of the anode surface. The analytical forms for the radius of curvature and the electric field direction as well as the electric field itself at arbitrary points on the anode are derived.     

Isotope effects in the interaction of hydrogen and deuterium with a rhodium (110) surface

The adsorption of H₂ and D₂ on a Rh (110) surface at 100 K leads to a sequence of ordered phases, among others 1×2 phases at _H =0.5 and at _H =1.5 which likely involve a partial surface reconstruction consisting of a small perpendicular displacement of Rh surface atoms. The structure of the adsorbate phases is strongly correlated with the binding energy of the adsorbed phases. Three H (D) binding states (₁,₂ and) are populated at saturation as determined by thermal desorption spectroscopy (TDS). Whereas the peak temperature of the state is invariant with the hydrogen isotope, the D ₁ state appears at a 8 Klower and theD ₂ state at a 5 Khigher temperature than the respective H states. Generally the D phases exhibit a better long-range order than the H phases. The rate of adsorption is identical for the first three adsorbed phases but D₂ adsorbs appreciably faster in the 1×2–3H and the final l×1–2H phases.Zero point energy effects as well as a H coverage dependent local interaction model could account for the observed effects.     

On the mechanism of liquid metal electron and ion sources

The mechanisms of electron and ion generation from Taylor cones of liquid metals are discussed. In the case of electron emission the vacuum arcing mechanism of Swanson and Schwind, which accounts for the observed high current repetitive pulsing is briefly reviewed. For ion emission mechanisms from onset to the high current regime are proposed. It is concluded that at onset ions are generated exclusively by field desorption. A theory to account for the observed emitter heating is advanced, and it is concluded that high currents result from field ionization of thermally evaporated atoms. It is shown that space charge becomes important even at very low ion currents and'is instrumental in providing stabilization in all regimes of ion emission.     

Pressure effect on the surface enhanced resonance Raman effect

Abstract

Surface enhanced resonance Raman spectra are presented for iron phenanthroline and ferricytochrome c up to 3 kbar. The frequency shifts are similar to those of the free species in solution. High pressure induces an irreversible loss of the scattering intensity.     

The electronic structures of the core and valence ion states of metal oxides

SCF-Xα SW MO calculations on metal core ion hole states and X-ray emission (XES) and X-ray photoelectron (XPS) transition states of the non- transition metal oxidic clusters MgO₆^10?, AlO₄^5? and SiO₄^4? show relative valence orbital energies to be virtually unaffected by the creation of valence orbital or metal core orbital holes. Accordingly, valence orbital energies derived from XPS and XES are directly comparable and may be correlated to generate empirical MO diagrams. In addition, charge relaxation about the metal core hole is small and valence orbital compositions are little changed in the core hole state. On the other hand, for the transition metal oxidic clusters FeO₆^10?, CrO₆^9? and TiO₆^8? relative valence orbital energies are sharply changed by a metal core orbital or crystal field orbital hole, the energy lowering of an orbital increasing with its degree of metal character. Consequently O 2p nonbonding → M 3d-O 2p antibonding (crystal field) energies are reduced, while M 3d bonding → O 2p nonbonding and M 3d-O 2p antibonding → M 4s,p-O 2p antibonding (conduction band) energies increase. Charge relaxation about the core hole is virtually complete in the transition metal oxides and substantial changes are observed in the composition of those valence orbitals with appreciable M 3d character. This change in composition is greater for e _g than for t_2g orbitals and increases as the separation of the e_g crystal field (CF) orbitals and the O 2p nonbonding orbital set decreases. Based on the hole state MO diagrams the higher energy XPS satellite in TiO₂ (at about 13 eV) is assigned to a valence → conduction band transition. The UV PES satellites at 8.2 eV in Cr₂O₃ and 9.3 eV in FeO are tentatively assigned to similar transitions to conduction band orbitals, although the closeness in energy of the crystal field and O 2p nonbonding orbitals in the valence orbital hole state prevents a definite assignment on energy criteria alone. However the calculations do clearly show that charge transfer transitions of the e_g bonding → e_g crystal field orbital type would generally occur at lower energy than is consistent with observed satellite structure.A core electron hole has little effect upon relative orbital energies and is only slightly neutralized by valence electron redistribution for MgO and SiO₂. For the transition metal oxides a core hole lowers the relative energies of M3d containing orbitals by large amounts, reducing O → M charge transfer and increasing M 3d crystal field → conduction band energies. Large and sometimes overcomplete neutralization of the core hole is observed, increasing from CrO₆^9? to FeO₆^10? to TiO₆^8?. as the O → M charge transfer energy declines.High energy XPS satellites in TiO₂ may be assigned to O 2p nonbonding → conduction band transitions while lower energy UV PES satellites in FeO and Cr₂O₃ arise from crystal field or O 2p nonbonding → conduction band excitations. Our “shake-up” assignment for FeO₆^10?, CrO₆^9? and TiO₆^8? are less than definitive because no procedure has yet been developed to calculate “shake-up” intensities resulting from transitions of the type described. However the results do allow a critical evaluation of earlier qualitative predictions of core and valence hole effects. First, we find that the comparison of hole or valence state ionic systems with equilibrium distance systems of higher nuclear and/or cation charge (e.g. the comparison of the FeO₆^10? Fe 2p core hole state to Co₃O₄) is dangerous. For example, larger MO distances in the ion states substantially reduce crystal field splittings. Second, core and CF orbital holes sharply reduce O → M charge transfer energies, giving 2e_g → 3e_g energy separations which are generally too small to match observed satellite energies. Third, highest occupied CF-conduction band energies are only about 4–5 eV in the ground states, but increase to about 7–11 eV in the core and valence hole states of the transition metal oxides studied. The energetic arguments presented thus support the idea of CF and/or O 2p nonbonding → conduction band excitations as assignments for “shake-up” satellites, at least in oxides of metals near the beginning of the transition series.     

Effect of charged deep states in hydrogenated amorphous silicon on the behavior of iron oxides nanoparticles deposited on its surface

Langmuir-Blodgett technique has been used for the deposition of ordered two-dimensional arrays of iron oxides (Fe₃O₄/Fe₂O₃) nanoparticles onto the photovoltaic hydrogenated amorphous silicon (a-Si:H) thin film. Electric field at the a-Si:H/iron oxides nanoparticles interface was directly in the electrochemical cell modified by light soaking and bias voltage (negative or positive) pretreatment resulting in the change of the dominant type of charged deep states in the a-Si:H layer. Induced reversible changes in the nanoparticle redox behavior have been observed. We suggest two possible explanations of the data obtained, both of them are needed to describe measured electrochemical signals. The first one consists in the electrocatalytical effect caused by the defect states (negatively or positively charged) in the a-Si:H layer. The second one consists in the possibility to manipulate the nanoparticle cores in the prepared structure immersed in aqueous solution via the laser irradiation under specific bias voltage. In this case, the nanoparticle cores are assumed to be covered with surface clusters of heterovalent complexes created onto the surface regions with prevailing ferrous or ferric valency. Immersed in the high viscosity surrounding composed of the wet organic nanoparticle envelope these cores are able to perform a field-assisted pivotal motion. The local electric field induced by the deep states in the a-Si:H layer stabilizes their “orientation ordering” in an energetically favourable position.