Active oxidation of Cu3Au(1 1 0) using hyperthermal O2 molecular beam

Oxidation of Cu₃Au(1 1 0) using a hyperthermal O₂ molecular beam (HOMB) was investigated by X-ray photoemission spectroscopy in conjunction with a synchrotron light source. From the incident energy dependence of the O-uptake curve, the precursor-mediated dissociative adsorption occurs, where the trapped O₂ molecule can migrate and dissociate at the lower activation-barrier sites, dominantly at thermal O₂ exposures. Dissociative adsorption of O₂ on Cu₃Au(1 1 0) is as effective at the thermal O₂ exposure as on Cu(1 1 0). On the other hand, at the incident energies of HOMB where the direct dissociative adsorption is dominant, it was determined that the dissociative adsorption of O₂ implies a higher activation barrier and therefore less reactivity due to the Au alloying in comparison with the HOMB oxidation of Cu(1 1 0). The dissociative adsorption progresses with the Cu segregation on Cu₃Au(1 1 0) similarly as on Cu₃Au(1 0 0). The growth of Cu₂O for 2 eV HOMB suggests that the diffusion of Cu atoms also contribute to the oxidation process through the open face, which makes the difference from Cu₃Au(1 0 0).     

Electron affinity study of adamantane on Si(1 1 1)

Recently, tetramantane, a member of diamondoid series (C_4n+6H_4n+12), has shown to exhibit negative-electron-affinity effect which has a potential use for efficient electron emitting devices. Here, we explore the electronic property of adamantane (C₁₀H₁₆), the smallest member of the series. We prepare adamantane films on Si(1 1 1) substrates and then study their electronic structure with photoemission spectroscopy. Photoelectron spectra of adamantane on Si(1 1 1) have shown a peak at low-kinetic energy which could be a generic property of diamondoids. The possibility of the negative-electron-affinity effect in adamantane is further discussed.     

Growth of ultra-thin cerium oxide layers on Cu(1 1 1)

The reactive vacuum deposition of CeO₂ on Cu(1 1 1) surface in oxygen atmosphere provides high quality epitaxial ceria overlayers. We report the growth characteristics of Ce oxide, the structures, and the temperature stability of the oxide phases as investigated by low-energy electron diffraction (LEED) and X-ray photoelectron spectroscopy. We find that Ce oxide on the Cu(1 1 1) grows initially in the form of islands giving sharp hexagonal LEED pattern of the CeO₂(1 1 1) structure corresponding to the (1.5 × 1.5) structure. The CeO₂-Cu(1 1 1) films exhibited mixed valence states and temperature dependent CeO₂-Ce₂O₃ transition above 900 K due to the vacuum annealing. The transition progressed more rapidly at the surface, probably by formation of oxygen vacancies.     

Surface charging at the (1 0 0) surface of Cu doped and undoped Li2B4O7

We have compared the photovoltaic charging of the (1 0 0) surface termination for Cu doped and undoped Li₂B₄O₇. While the surface charging at the (1 0 0) surface of Li₂B₄O₇ is significantly greater than observed at (1 1 0) surface, the Cu doping plays a role in reducing the surface photovoltage effects. With Cu doping of Li₂B₄O₇, the surface photovoltaic charging is much diminished at the (1 0 0) surface. The density of states observed with combined photoemission and inverse photoemission remains similar to that observed for the undoped material, except in the vicinity of the conduction band edge.     

Pressure tuned crystal structure in NdBa2Cu3O6+δ superconductor

The high-pressure angle-dispersive X-ray diffraction experiments on the NdBa₂Cu₃O_6+δ superconductor were performed from ambient to above 30 GPa at room temperature. The structure analysis based on the Rietveld refinement methods shows the different pressure dependence for the bond length between the basal-plane copper of the pyramids to the apical oxygen (denoted Cu(2)–O(1)) and bond length between basal-plane copper to plane oxygen (denoted Cu(2)–O(2,3)). The ambient bulk modulus B₀ is derived as 127 GPa. A possible correlation between Cu(2)–O(1) and T_c was discussed.     

Preparation and optical properties of Cu2O hollow microsphere film and hollow nanosphere powder via a simple liquid reduction approach

In this work, we report a simple liquid reduction approach to prepare Cu₂O hollow microsphere film and hollow nanosphere powder with Cu(OH)₂ nanorods as precursor and ascorbic acid as the reductant at 60 °C. When Cu(OH)₂ nanorod array film grown on a copper foil is used as the precursor, Cu₂O thin film made up of hollow microspheres with average diameter of 1.2 μm is successfully prepared. When the Cu(OH)₂ nanorods are scraped from the copper foil and then used as the precursor, Cu₂O hollow nanosphere powder with the average diameter of 270 nm is obtained. The samples are characterized by X-ray powder diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and ultraviolet-vis light (UV-vis) absorption spectra. A possible formation mechanism of Cu₂O hollow spheres is discussed.     

A study of the interaction between perylene and the TiO2(1 1 0)-(1 × 1) surface-based on XPS, UPS and NEXAFS measurements

The interaction between a semi-large aromatic hydrocarbon compound (perylene) and the TiO₂(1 1 0)-(1 × 1) surface under ultra high vacuum conditions has been probed by X-ray photoemission spectroscopy (XPS), ultraviolet photoemission spectroscopy (UPS) and near-edge X-ray absorption fine structure (NEXAFS) methods. UPS measurements of the adsorbate system have been compared with an experimental UPS spectrum of perylene in the gas phase and a calculated spectrum obtained by means of density functional theory (DFT) methods. NEXAFS results of perylene molecules adsorbed on TiO₂(1 1 0)-(1 × 1) were compared with data from an α-phase perylene single crystal. A novel analysis of the valence data has been employed to show that no strong chemical interaction takes place between perylene and the TiO₂(1 1 0)-(1 × 1) surface. Furthermore, angle-dependent NEXAFS measurements and the growth curve results suggest that the perylene molecules are oriented flat down onto the TiO₂ substrate due to weak van der Waals interactions.     

Thermal reactions of 2-iodoethanol on Cu(1 0 0)

Temperature-programmed reaction/desorption, X-ray photoelectron spectroscopy, and reflection-absorption infrared spectroscopy have been employed to investigate the reactions of ICH₂CH₂OH on Cu(1 0 0) under ultrahigh-vacuum conditions. ICH₂CH₂OH can dissociate on Cu(1 0 0) at 100 K, forming a -CH₂CH₂OH surface intermediate. Density functional theory calculations predict that the -CH₂CH₂OH is most probably adsorbed on atop site. -CH₂CH₂OH on Cu(1 0 0) further decomposes to yield C₂H₄ below 270 K. No evidence shows the formation of -CH₂CH₂O- intermediate in the reactions of ICH₂CH₂OH on Cu(1 0 0) in contrast to the decomposition of BrCH₂CH₂OH on Cu(1 0 0) and ICH₂CH₂OH on Ag(1 1 1) and Ag(1 1 0), exhibiting the effects of carbon-halogen bonds and metal surfaces.     

Low energy Ar-ion bombardment effects on the CeO2 surface

The structure and electronic properties of epitaxial grown CeO₂(1 1 1) thin films before and after Ar⁺ bombardment have been comprehensively studied with synchrotron radiation photoemission spectroscopy (SRPES). Ar⁺ bombardment of the surface causes a new emission appearing at 1.6 eV above the Fermi edge which is related to the localized Ce 4f¹ orbital in the reduced oxidation state Ce³⁺. Under the condition of the energy of Ar ions being 1 keV and a constant current density of 0.5 μA/cm², the intensity of the reduced state Ce³⁺ increases with increasing time of sputtering and reaches a constant value after 15 min sputtering, which corresponds to the surface being exposed to 2.8 × 10¹⁵ ions/cm². The reduction of CeO₂ is attributed to a preferential sputtering of oxygen from the surface. As a result, Ar⁺ bombardment leads to a gradual buildup of an, approximately 0.69 nm thick, sputtering altered layer. Our studies have demonstrated that Ar⁺ bombardment is an effective method for reducing CeO₂ to CeO_2−x and the degree of the reduction is related to the energy and amount of Ar ions been exposed to the CeO₂ surface.     

Electronic structure of Cr1−δS (δ=0, 0.17) with NiAs-type crystal structure

Valence-band and conduction-band the electronic structure of the CrS (δ=0) and Cr₅S₆ (δ=0.17) has been investigated by means of photoemission and inverse-photoemission spectroscopies. The bandwidth of the valence bands of Cr₅S₆ (8.5 eV) is wider than that of CrS (8.1 eV), though the Cr 3d partial density of states evaluated from the Cr 3p-3d resonant photoemission spectroscopy is almost unchanged between the two compounds concerning shapes as well as binding energies. The Cr 3d (t_2g) exchange splitting energies of CrS and Cr₅S₆ are determined to be 3.9 and 3.3 eV, respectively.     

Induced spin polarization of copper spin 1/2 molecular layers

Thin films of the metal organic molecule bis(4-cyano-2,2,6,6-tetramethyl-3,5-heptanedionato)copper(II) (or Cu(CNdpm)₂), (C₂₄H₃₆N₂O₄Cu, Cu(II)), deposited on ferromagnetic Co(111) at 40 K, exhibit a finite electron spin polarization. The spin polarization magnitude and sign for Cu(CNdpm)₂ deposited on Co(111) is coverage dependent, but deviates from the mean field expectations for a simple paramagnet on a ferromagnetic substrate. The spin asymmetry is seen to favor select molecular orbitals, consistent with the predicted single molecule density of states. The overlayer polarization observed indicates a strong influence of the ferromagnetic Co(111) substrate and some extra-molecular magnetic coupling.     

Work function of sol-gel indium tin oxide (ITO) films on glass

Indium tin oxide (ITO) films (physical thickness, 250-560 ± 25 nm) were deposited on soda lime silica (SLS) glass and silica layer coated (∼200 nm physical thickness) SLS glass substrates by sol-gel technique using alcohol based precursors containing different In:Sn atomic percentages, namely, 90:10, 70:30, 50:50, 30:70. Cubic phase of In₂O₃ was observed up to 50 at.% Sn while cassiterite SnO₂ phase was observed for 70 at.% Sn. Work function of the films was evaluated from inelastic secondary electron cutoff of ultraviolet photoelectron spectroscopy (UPS) energy distribution curve (EDC) obtained under two experimental conditions (i) as-introduced (ii) after the cleaning of the surface by sputtering. Elemental distribution and the presence of oxygen containing contaminant and carbon contaminant of the samples were done by XPS analysis under same conditions. The work function changed little due to the presence of surface contaminants. It was in the range, 3.9-4.2 eV (±0.1 eV).     

Crystalline and photoluminescence characteristics of YVO4:Sm thin films grown by pulsed laser deposition under oxygen pressure

YVO₄:Sm³⁺ films were deposited on Al₂O₃ (0 0 0 1) substrates at various oxygen pressures changing from 13.3 to 46.6 Pa by using the pulsed laser deposition method. The crystallinity and surface morphology of these films were investigated by means of X-ray diffraction (XRD) and atomic force microscopy (AFM), respectively. The XRD pattern confirmed that YVO₄:Sm³⁺ film has zircon structure and the AFM study revealed that the films consist of homogeneous grains ranging from 100 to 400 nm. The room temperature photoluminescence (PL) spectra showed that the emitted radiation was dominated by a reddish-orange emission peak at 602 nm radiating from the transition of (⁴G_5/2→⁶H_7/2). The crystallinity, surface morphology, and photoluminescence spectra of thin-film phosphors were highly dependent on the deposition conditions, in particular, the substrate temperature. The surface roughness and photoluminescence intensity of these films showed similar behavior as a function of oxygen pressure.     

The luminescent properties of CaYBO4:Ln(Ln=Eu, Tb) under UV-VUV range

The luminescent properties of CaYBO₄:Ln(Ln=Eu³⁺, Tb³⁺) were investigated under ultraviolet (UV) and vacuum ultraviolet (VUV) region. The CT band of Eu³⁺ at about 245 nm blue-shifted to 230 nm in VUV excitation spectrum; the band with the maximum at 183 nm was considered as the host lattice absorption. For the sample of CaYBO₄:0.08Tb³⁺, the bands at about 235 and 263 nm were assigned to the f-d transitions of Tb³⁺ and the CT band of Tb³⁺ was calculated according to Jφrgensen's theory. Under UV and VUV excitation, the main emission of Eu³⁺ corresponding to the ⁵D₀-⁷F₂ transition located at about 610 nm and two intense emission of Tb³⁺ from the ⁵D₄-⁷F₅ transition had been observed at about 542 and 552 nm, respectively. With the incorporation of Gd³⁺ into the host lattice of CaYBO₄, the luminescence of Tb³⁺ was enhanced while that of Eu³⁺ was decreased because of their different excitation mechanism.     

High-pressure and optical properties of lanthanum magnesium hexa-aluminate doped with Mn (LMA:Mn) laser material

The effect of hydrostatic pressure on the emission spectra and fluorescence lifetime (τ) of Mn²⁺ in LaMgAl₁₁O₁₉ (LMA) crystals up to 101 kbar has been studied at room temperature. From the position of the peak (⁴T₁ → ⁶A₁ transition) in the emission spectra, we estimated that the pressure induced red-shift. A variation, slowly decreasing, in the fluorescence lifetime (τ) values for ⁴T₁ → ⁶A₁ transition was observed. The pressure-induced red-shift and lifetime variation could be described by simple models. In the considered pressure range (0-101 kbar), a good agreement between the experimental values and theoretically predicted values was obtained.     

Synthesis and luminescence investigation of RE (Eu, Tb and Ce)-doped lithium silicate (Li2SiO3)

Synthesis and photoluminescence (PL) investigations of lithium metasilicate doped with Eu³⁺, Tb³⁺ and Ce³⁺ were carried out. PL spectra of Eu-doped sample showed peaks corresponding to the ⁵D₀→⁷F_j (j=1, 2, 3 and 4) transitions under ultraviolet excitation. Strong red emission coming from the hypersensitive ⁵D₀→⁷F₂ transition of Eu³⁺ ion suggested the presence of the dopant ion in structurally disordered environment. Tb³⁺-doped silicate sample showed blue-green emission corresponding to the ⁵D₄→⁷F_j (j=6, 5 and 4) transitions. Ce-doped sample under excitation from UV, showed a broad emission band in the region 350-370 nm with shoulders around 410 nm. The fluorescence lifetimes of Eu³⁺ and Tb³⁺ ions were found out to be 790 and 600 μs, respectively. For Ce³⁺, the lifetime was of the order of 45 ns. PL spectra of the europium- and terbium-doped samples were compared with commercial red (Y₂O₃:Eu³⁺) and green (LaPO₄:Tb³⁺) phosphors, respectively. It was found that the emission from the doped silicate sample was 37% of the commercial phosphor in case of the Tb-doped sample and 8% of the commercial phosphor in case of the Eu-doped sample.     

Multiphoton ultraviolet and visible upconversion luminescence of TmYb co-doped oxyfluoride glass

The ultraviolet upconversion luminescence of Tm³⁺ ions sensitized by Yb³⁺ ions in oxyfluoride glass when excited by a 975 nm diode laser was studied in this paper. One typical ultraviolet upconversion luminescence lines positioned at 362.3 nm was found. It can be attributed to the five-photon upconversion luminescence transition of ¹D₂ → ³H₆. Several visible upconversion luminescence lines at 451.1 nm, (477.9 nm, 462.5 nm), 648.7 nm, (680.5 nm, 699.5 nm) and (777.5 nm, 800.7 nm) were found also, which results from the fluorescence transitions of five-photon ¹D₂ → ³F₄, three-photon ¹G₄ → ³H₆, three-photon ¹G₄ → ³F₄, two-photon ³F₃ → ³H₆ and two-photon ³H₄ → ³H₆ of Tm³⁺ ion, respectively. The theoretical analysis suggests that the upconversion mechanism of the 362.3 nm ¹D₂ → ³H₆ upconversion luminescence is the cross energy transfer of {³H₄(Tm³⁺) → ³F₄(Tm³⁺), ¹G₄(Tm³⁺) → ¹D₂(Tm³⁺)} and {¹G₄(Tm³⁺) → ³F₄(Tm³⁺), ³H₄(Tm³⁺) → ¹D₂(Tm³⁺)} between Tm³⁺ ions. In addition, the upconversion luminescence of ¹G₄ and ³H₄ state results from the sequential energy transfer {²F_5/2(Yb³⁺) → ²F_7/2(Yb³⁺), ³H₄(Tm³⁺) → ¹G₄(Tm³⁺)} and {²F_5/2(Yb³⁺) → ²F_7/2(Yb³⁺), ³F₄(Tm³⁺) → ³F₂(Tm³⁺)} from Yb³⁺ ions to Tm³⁺ions, respectively.     

Inverse photoemission spectroscopy of the unoccupied electronic structure of Na/Cu(110)

The unoccupied electronic states of Na thin films on a Cu(110) substrate have been measured by inverse photoemission spectroscopy (IPES). The IPES spectrum provides the intensity of the unoccupied states, which decreases with increasing Na coverage at off-normal incidence of the electron beam. The IPES spectra at 17 and 19 eV incident electron energies show a shift towards the Fermi level with increasing Na coverage for the peak at ∼7.8 eV.     

Effects of substrates on the structure and dielectric properties of Ba(Sn0.15Ti0.85)O3 thin films

Ba(Sn_0.15Ti_0.85)O₃ (BTS) thin films were grown on Pt(1 1 1)/Ti/SiO₂/Si and LaNiO₃(LNO)/Pt(1 1 1)/Ti/SiO₂/Si substrates by a sol-gel processing technique, respectively. The BTS thin films deposited on annealed Pt(1 1 1)/Ti/SiO₂/Si and annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrates exhibited strong (1 1 1) and perfect (1 0 0) orientations, respectively. The BTS thin films grown on un-annealed Pt(1 1 1)/Ti/SiO₂/Si substrates showed random orientation with intense (1 1 0) peak, while the films deposited on un-annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrate exhibited random orientation with intense (1 0 0) peak, respectively. The dielectric constant of the BTS films deposited on annealed Pt(1 1 1)/Ti/SiO₂/Si, annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si, un-annealed Pt(1 1 1)/Ti/SiO₂/Si and un-annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrates was 512, 565, 386 and 437, respectively, measured at a frequency of 100 kHz. A high tunability of 49.7% was obtained for the films deposited on annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrate, measured at the frequency of 100 kHz with an applied electric field of 200 kV/cm. The high tunability has been attributed to the (1 0 0) texture of the films and larger grain sizes.     

Ammonia adsorption and decomposition on silica supported Rh nanoparticles observed by in situ attenuated total reflection infrared spectroscopy

Attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) is applied to study NH₃, adsorbed from the gas phase, and its decomposition products, i.e. NH_x species, on Rh nanoparticles, produced by spincoating from a RhCl₃ solution in water followed by reduction. A silicon ATR crystal with a hydroxilated SiO₂ layer acts as the support for the nanoparticles. Upon exposure to NH₃ in the vacuum chamber, NH₃ adsorbed to both silica and Rh is detected (sensitivity ∼5 × 10⁻⁵ absorbance units). Interaction of the NH₃ with the silica OH groups is observed around ∼2840 cm⁻¹ in combination with peaks showing the disappearance of unperturbed OH vibrations between 3500 and 3700 cm⁻¹. In addition, NH bend vibrations at 1634 cm⁻¹ and NH stretch vibrations at 3065 and 3197 cm⁻¹ are observed for substrate temperatures between 20 and 100 °C. The latter two correspond to NH on Rh, as verified with a sample without Rh, and probably correspond to undecomposed NH₃. Moreover, they remain after evacuation, suggesting strongly bound species. For a substrate temperature of 75 and 100 °C, additional NH stretch peaks at 3354 and 3283 cm⁻¹ are observed, possibly due to NH₂ intermediates, indicating NH₃ decomposition. It is shown that ATR-FTIR can contribute to the sensitive detection of adsorption and decomposition of gaseous species on realistic planar model catalysts.