CeO2/Nb2O5界面效应对提高CeO2氧敏特性的XPS研究

用射频/直流磁控溅射法制备了CeO₂/Nb₂O₅双层氧敏薄膜，利用X射线光电子能谱(XPS)，描述并解释了单层CeO₂薄膜中氧随温度变化的动力学行为，以及CeO₂/Nb₂O₅薄膜界面对氧敏特性的影响.通过对Ce3d XPS谱的高斯拟合，计算了Ce³⁺浓度并给出了判定Ce⁴⁺还原的标志.结果表明，界面效应可以提高CeO₂/Nb₂O₅薄膜中Ce⁴⁺的还原能力，使之远远高于单层CeO₂薄膜，这对薄膜的氧敏特性是极为有利的. 关键词：     

CO<Subscript>2</Subscript> activation on single crystal based ceria and magnesia/ceria model catalysts

Novel multifunctional ceria based materials may show an improved performance in catalytic processes involving CO₂ activation and reforming of hydrocarbons. Towards a more detailed understanding of the underlying surface chemistry, we have investigated CO₂ activation on single crystal based ceria and magnesia/ceria model catalysts. All model systems are prepared starting from well-ordered and fully stoichiometric CeO₂(111) films on a Cu(111) substrate. Samples with different structure, oxidation state and compositions are generated, including CeO_2-x/Cu(111) (reduced), MgO/CeO_2-x/Cu(111) (reduced), mixed MgO-CeO₂/Cu(111) (stoichiometric), and mixed MgO-CeO_2-x/Cu(111) (reduced). The morphology of the model surfaces is characterized by means of scanning tunneling microscopy (STM), whereas the electronic structure and reactivity is probed by X-ray photoelectron spectroscopy (XPS). The experimental approach allows us to compare the reactivity of samples containing different types of Ce³⁺, Ce⁴⁺, and Mg²⁺ ions towards CO₂ at a sample temperature of 300 K. Briefly, we detect the formation of two CO₂-derived species, namely carbonate (CO₃ ^2-) and carboxylate (CO₂ ^-) groups, on the surfaces of all investigated samples after exposure to CO₂ at 300 K. In parallel to formation of the carbonate species, slow partial reoxidation of reduced CeO_2-x/Cu(111) occurs at large doses of CO₂. The reoxidation of the reduced ceria is largely suppressed on MgO-containing samples. The tendency for reoxidation of Ce³⁺ to Ce⁴⁺ by CO₂ decreases with increasing degree of intermixing between MgO and CeO_2-x. Additionally, we have studied the stability of the formed carbonate species as a function of annealing temperature.     

Synthesis,characterization, and ecotoxicity of CeO<Subscript>2</Subscript> nanoparticles with differing properties

CeO₂ nanoparticles with various characteristics find an increasing number of applications in the electronic, medical, and other industries and are therefore likely released in the environment. This calls for investigations linking the physicochemical properties of these particles with their potential environmental impacts. In this study, CeO₂ nanoparticle powders were prepared using three different precursors [Ce(NO₃)₃, CeCl₃, and Ce(CH₃COO)₃] and annealing temperatures (300, 500, and 700 °C). This procedure resulted in nine different types of nanoparticles with differing size (5–90 nm), morphology, surface Ce³⁺/Ce⁴⁺ ratio, and slightly different crystal structures as characterized using transmission electron microscopy, dynamic light scattering, X-ray photoelectron spectroscopy, and X-ray diffraction measurements with Rietveld refinement. These CeO₂ nanoparticles underwent toxicity testing at concentrations up to 64 mg L^?1 using Daphnia magna. Toxic effects were observed for three particle types with EC50 values between 5 and 64 mg L^?1. No clear correlation was observed between the physicochemical properties (size, shape, oxygen occupancy, Ce³⁺/Ce⁴⁺ ratio) of the nanoparticles and their toxicity. However, toxicity was correlated with the amount of Ce remaining suspended in the test medium after 24 h. This indicated that toxic effects may depend on the colloidal stability of CeO₂ nanoparticles during the first day of exposure. Therefore, being readily suspended and remaining stable for several days in the aquatic media increases the likelihood that CeO₂ nanoparticles will cause unwanted adverse effects.     

Improved photoluminescence of pulsed-laser-ablated Y<Subscript>1-x</Subscript>Gd<Subscript>x</Subscript>VO<Subscript>4</Subscript>:Eu<Superscript>3+</Superscript> thin film phosphors by Gd substitution

Gd-substituted Y_1-xGd_xVO₄:Eu³⁺ luminescent thin films have been grown on Al₂O₃(0001) substrates using pulsed-laser deposition. The films grown under different deposition conditions have been characterized using microstructural and luminescent measurements. The crystallinity, surface morphology, and photoluminescence (PL) of the films are highly dependent on the amount of Gd. The photoluminescence (PL) brightness data obtained from Y_1-xGd_xVO₄:Eu³⁺ films grown under optimized conditions have indicated that the PL brightness is more dependent on the surface roughness than the crystallinity of the films. In particular, the incorporation of Gd into the YVO₄ lattice could induce a remarkable increase of PL. The highest emission intensity was observed with Y_0.57Gd_0.40Eu_0.03VO₄ thin film whose brightness was increased by a factor of 2.5 and 1.9 in comparison with that of YVO₄:Eu³⁺ and GdVO₄:Eu³⁺ films, respectively. This phosphor have application to flat panel displays. PACS 78.20.-e; 78.55.-m; 78.66.-w     

Morphology-dependent luminescence behavior of Y<Subscript>2-x</Subscript>Gd<Subscript>x</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> thin-film phosphors grown by a laser ablation

Y_2-xGd_xO₃:Eu³⁺ luminescent thin films have been grown on Al₂O₃(0001) substrates using pulsed laser deposition. Films grown under different deposition conditions have been characterized using microstructural and luminescence measurements. The crystallinity, surface morphology and photoluminescence (PL) of the films are highly dependent on the amount of Gd present. The photoluminescence (PL) brightness data obtained from Y_2-xGd_xO₃:Eu³⁺ films grown under optimized conditions have indicated that Al₂O₃(0001) is one of the most promising substrates for the growth of high-quality Y_2-xGd_xO₃:Eu³⁺ thin-film red phosphors. In particular, the incorporation of Gd into the Y₂O₃ lattice could induce a remarkable increase of PL. The highest emission intensity was observed with Y_1.35Gd_0.60Eu_0.05O₃, whose brightness was increased by a factor of 3.1 in comparison with that of Y₂O₃:Eu³⁺ films. This phosphor may be promising for application in flat-panel displays. PACS 78.20.-e; 78.55.-m; 78.66.-w     

PL Properties of Sr<Subscript>2</Subscript>CeO<Subscript>4</Subscript> With Eu<Superscript>3+</Superscript> and Dy<Superscript>3+</Superscript> for Solid State Lighting Prepared by Precipitation Method

Photoluminescence studies of pure and Dy³⁺, Eu³⁺ doped Sr₂CeO₄ compounds are presented by oxalate precipitation method for solid state lighting. The prepared samples also characterized by XRD, SEM (EDS) and FTIR spectroscopy. The pure Sr₂CeO₄ compound displays a broad band in its emission spectrum when excited with 280 nm wavelength, which peaks centered at 488 nm, which is due to the energy transfer between the molecular orbital of the ligand and charge transfer state of the Ce⁴⁺ ions. Emission spectra of Sr₂CeO₄ with different concentration of Dy³⁺ ions under near UV radiation excitation, shows that intensity of luminescence spectra is found to be affected by Dy³⁺ ions, and it increases with adding some percentages of Dy³⁺ ions. The maximum doping concentration for quenching is found to be Dy³⁺?=?0.2 mol % to Sr²⁺ions. The observed broad spectrum from 400 to 560 nm is mainly due to CT transitions in Sr₂CeO₄ matrix and some fractional contribution of transitions between ⁴F_9/2 → ⁶H_15/2 of Dy³⁺ ions. Secondly the effect of Eu³⁺ doping at the Sr²⁺ site in Sr₂CeO₄, have been studied. The results obtained by doping Eu³⁺ concentrations (0.2 mol% to 1.5 mol%), the observed excitation and emission spectra reveal excellent energy transfer between Ce⁴⁺ and Eu³⁺. The phenomena of concentration quenching are explained on the basis of electron phonon coupling and multipolar interaction. This energy transfer generates white light with a color tuning from blue to red, the tuning being dependent on the Eu³⁺ concentration. The results establish that the compound Sr₂CeO₄ with Eu³⁺?=?1 mol% is an efficient “single host lattice” for the generation of white lights under near UV-LED and blue LED irradiation. The commission internationale de I’Eclairage (CIE) coordinates were calculated by Spectrophotometric method using the spectral energy distribution of prepared phosphors.     

Luminescence properties of phosphors based on Tb<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> (TbAG) terbium-aluminum garnet

The processes of excitation energy transfer in phosphors based on single-crystal Tb₃Al₅O₁₂:Ce (TbAG:Ce) and Tb₃Al₅O₁₂:Ce,Eu (TbAG:Ce,Eu) garnet films have been investigated. These films are considered to be promising materials for screens for X-ray images and luminescence converters of blue LED radiation. The conditions for excitation energy transfer from the matrix (Tb³⁺ cations) to Ce³⁺ and Eu³⁺ ions in TbAG:Ce and TbAG:Ce,Eu phosphors have been analyzed in detail. It is established that a cascade process of excitation energy transfer from Tb³⁺ ions to Ce³⁺ and Eu³⁺ ions and from Ce³⁺ ions to Eu³⁺ ions is implemented in TbAG:Ce,Eu via dipole-dipole interaction and through the Tb³⁺ cation sublattice.     

Effects of citric acid additive on photoluminescence properties of YAG:Ce nanoparticles synthesized by glycothermal reaction

We synthesize Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce³⁺) nanoparticles in the presence of citric acid by glycothermal method. Fourier transform infrared absorption spectroscopy measurement indicates that the intensity of the peak corresponding to carboxyl groups coordinating to the nanoparticles increases with increasing amount of citric acid. At the same time, the primary particle diameter decreases from 10.2 to 4.0 nm. In addition, the internal quantum efficiency of the photoluminescence (PL) due to the 4f-5d transition of Ce³⁺ increases from 22.0% to 40.1% with increasing amount of citric acid. Two kinds of PL decay lifetimes, 16-26 and 72-112 ns, are detected for YAG:Ce³⁺ nanoparticles, whereas the micron sized YAG:Ce³⁺ bulk shows the lifetime of 57 ns. We discuss these phenomena from the aspects of the coordination of citric acid and the incorporation of Ce³⁺ ions into the nanoparticles.     

Investigation of luminescence spectra of the Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> and Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce single-crystal films

The luminescence spectra of single-crystal films and bulk crystals of yttrium-aluminum garnet Y₃Al₅O₁₂ and Ce³⁺-activated Y₃Al₅O₁₂ were investigated. It was shown that the room-temperature luminescence intensity of the Ce³⁺-free single-crystal Y₃Al₅O₁₂ film was considerably lower than that of the bulk crystals, while the luminescence intensity of the Ce³⁺ ions in the Y₃Al₅O₁₂:Ce films was considerably higher than that one for the corresponding bulk crystal.     

Crystal structure and photoluminescence of (Y1−xCex)2Si3O3N4

Oxonitridosilicate phosphors with compositions of (Y_1−xCe_x)₂Si₃O₃N₄ (x=0−0.2) have been synthesized by solid state reaction method. The structures and photoluminescence properties have been investigated. Ce³⁺ ions have substituted for Y³⁺ ions in the lattice. The emission and excitation spectra of these phosphors show the characteristic photoluminescence spectra of Ce³⁺ ions. Based on the analyses of the diffuse reflection spectra and the PL spectra, a systematic energy diagram of Ce³⁺ ion in the forbidden band of sample with x=0.02 is given. The best doping Ce content in these phosphors is ∼2 mol%. The quenching temperature is ∼405 K for the 2 mol% Ce content sample. The luminescence decay properties were investigated. The primary studies indicate that these phosphors are potential candidates for application in three-phosphor-converted white LEDs.     

The influence of the number of pulses on the morphological and photoluminescence properties of SrAl2O4:Eu,Dy thin films prepared by pulsed laser deposition

The current work reports on the influence of the number of laser pulses on the morphological and photoluminescence properties of SrAl₂O₄:Eu²⁺,Dy³⁺ thin films prepared by the pulsed laser deposition (PLD) technique. Atomic force microscopy (AFM) was used to study the surface topography and morphology of the films. The AFM data showed that the film deposited using a higher number of laser pulses was packed with a uniform layer of coarse grains. In addition, the surface of this film was shown to be relatively rougher than the films deposited at a lower number of pulses. Photoluminescence (PL) data were collected using the Cary Eclipse fluorescence spectrophotometer equipped with a monochromatic xenon lamp. An intense green photoluminescence was observed at 517 nm from the films prepared using a higher number of laser pulses. Consistent with the PL data, the decay time of the film deposited using a higher number of pulses was characteristically longer than those of the other films. The effects of laser pulses on morphology, topography and photoluminescence intensity of the SrAl₂O₄:Eu²⁺,Dy³⁺ thin films are discussed.     

luminescence of BaGa<Subscript>2</Subscript>Se<Subscript>4</Subscript> crystals activated by Eu<Superscript>2+</Superscript> and Ce<Superscript>3+</Superscript> ions

We have studied the effect of doping with Eu²⁺ and Ce³⁺ ions on the photoluminescence (PL) of BaGa₂Se₄ crystals in the temperature range 77–300 K. We have established that the broad bands with maxima at wavelengths 456 nm and 506 nm observed in the photoluminescence spectra of BaGa₂Se₄:Ce³⁺ crystals are due to intracenter transitions 5d → ²F_7/2 and 5d →²F_5/2 of the Ce³⁺ ions, while the broad photoluminescence band with maximum at 521 nm in the spectrum of BaGa₂Se₄:Eu²⁺ is associated with 4f⁶ 5d → 4f⁷ (⁸S_7/2) transitions of the Eu²⁺ ion. We show that in BaGa₂Se₄:Eu²⁺,Ce³⁺ crystals, excitation energy is transferred from the Ce³⁺ ions to the Eu²⁺ ions.     

The effect of argon gas pressure on structural,morphological and photoluminescence properties of pulsed laser deposited KY<Subscript>3</Subscript>F<Subscript>10</Subscript>:Ho<Superscript>3+</Superscript> thin films

KY₃F₁₀:Ho³⁺ thin films were deposited by a pulsed laser deposition technique with Nd–YAG laser radiation (λ = 266 nm) on (100) silicon substrate. The XRD and FE-SEM results show improved crystalline structure for the film deposited at a pressure of 1 Torr. The AFM results show that the RMS roughness of the films increases with rise in argon gas pressure. The EDS elemental mapping shows Y-excess for all the films deposited under all pressures, and this is attributed to its higher mass and low volatility as compared to K and F. XPS analysis further confirmed Y-excess in the deposited films. Green PL emission at 540 nm was investigated at three main excitation wavelengths, namely 362, 416 and 454 nm. The PL emission peaks increase with rise in background argon gas pressure for all excitation wavelengths. The highest PL intensity occurred at excitation of 454 nm for all the thin films. In addition, faint red (near infrared) emission was observed at 750 nm for all the excitations. The green emission at 540 nm is ascribed to the ⁵F₄–⁵I₈ and ⁵S₂–⁵I₈ transitions, and the faint red emission at 750 nm is due to the ⁵F₄–⁵I₇ and ⁵S₂–⁵I₇ transitions of Ho³⁺.     

Swift heavy ion irradiation-induced modifications of tris-(8-hydroxyquinoline)aluminum thin films

Tris-(8-hydroxyquinoline)aluminum (Alq₃), one of the most widely used light emitting and electron transport materials in organic luminescent devices, has been synthesized. Alq₃ thin films have been deposited by a thermal evaporation process on glass substrates. The effect of swift heavy ion (SHI) irradiation using 40 MeV Li³⁺ on the Alq₃ thin films has been studied by UV-visible, infrared, photoluminescence (PL) and time-resolved photoluminescence (TRPL) spectroscopy. From TRPL studies, it is found that the PL of Alq₃ thin films arises from two species corresponding to its two geometrical isomers, namely facial and meridional having two different life times. It is also confirmed that the PL and lifetimes of excitons decrease with the increase of ion fluences of SHI of 40 MeV Li³⁺, indicating a transfer of exciton energy to unstable cationic Alq₃ species generated by SHI irradiation.     

Variations in the structural, optical and electrochemical properties of CeO2-TiO2 films as a function of TiO2 content

Alcohol based sols of cerium chloride (CeCl₃·7H₂O) and titanium propoxide (Ti(OPr)₄) in ethanol mixed in different mole ratios have yielded mixed oxide films on densification at 500 °C. The reversibility of the intercalation/deintercalation reactions has shown electrochemical stability of the films. Addition of TiO₂ in an equivalent mole ratio manifests in producing highly transparent films with appreciable ion storage capacity. The electrochemical studies have revealed the significant role of TiO₂ in controlling the ion storage capacity of the films, as it tends to induce the disorder. In addition, the films prepared from an aged sol are observed to exhibit a much higher ion storage capacity than the films deposited using the as-prepared sol. The X-ray photoelectron spectroscopic studies have provided information on the variation of Ce⁴⁺/Ce³⁺ ratio as a function of increased TiO₂ content in the films. This study has led to a better understanding of the increased ion storage capacity with the increased TiO₂ proportion. The transmission electron microscopic study has demonstrated the presence of CeO₂ nanograins even in films, which are amorphous to X-rays. Elucidation of the structural, optical and electrochemical features of the films has yielded information on aspects relevant to their usage in transmissive electrochromic devices. The films have been found to exhibit properties that can find application as counter electrode in electrochromic smart windows in which they are able to retain their transparency under charge insertion, high enough for practical uses. Also, the fastest coloration-bleaching kinetics for the primary electrochromic electrode (WO₃) working in combination with Ce/Ti (1:1) electrode stimulates the use of latter in electrochromic windows (ECWs).     

A resonant photoemission study of the Ce and Ce-oxide/Pd(1 1 1) interfaces

We have investigated the Ce 4f electronic states in the Ce/Pd(1 1 1) and Ce-oxide/Pd(1 1 1) systems, using resonant photoemission (Ce 4d → 4f transitions), and XPS to understand Pd-Ce interactions in ultra thin layers of cerium and ceria deposited on Pd(1 1 1). Cerium deposited on Pd(1 1 1) at room temperature forms surface Ce-Pd alloys with Ce rich character, while a Pd rich Ce-Pd alloy is formed by heating to 700 °C. A modification of the chemical state of Ce can also be seen after oxygen exposure. RPES provides evidence that Ce-oxide layers deposited on Pd(1 1 1) have a CeO₂ (Ce⁴⁺) character, however a net contribution of the Ce³⁺ states is also revealed. The Ce³⁺ states have surface character and are accompanied by oxygen vacancies. Heating to 600 °C causes Ce-oxide reduction. A significant shift of Pd 4d-derived states, induced by Pd 4d and Ce 4f hybridization, was observed. The resonant features in the valence band corresponding to Ce⁴⁺, Ce³⁺ and Ce⁰ states have been investigated for various Pd−Ce(CeO_x) coverages.     

Influence of a dopant source on the structural and optical properties of Mn doped ZnGa<Subscript>2</Subscript>O<Subscript>4</Subscript> thin films

Thin films of ZnGa₂O₄:Mn²⁺ were deposited on quartz substrates using an rf magnetron sputtering technique. The sputtering target, ZnGa₂O₄ doped with 2 at. % manganese, was synthesized by a high temperature solid state reaction. Two different dopant sources were used to incorporate the dopant ions into the target, namely, manganese acetate and manganese oxide. The structural and optical properties of the thin films were studied using XRD, PL and transmission spectra. Polycrystalline ZnGa₂O₄:Mn with a spinel structure could be grown at an optimized substrate–target distance even at room temperature. No luminescence was observed in the as-deposited films grown using (CH₃COO)₂Mn as the dopant source in the target. Substrate heating or post-deposition annealing in the reducing ambient didn’t impart any luminescence to the films, ruling out the possibility of Mn²⁺ incorporation in the films. However, when using MnO as the manganese source in the target, the as-deposited films exhibited green photoluminescent emission (peak maximum at 508 nm) for substrate temperatures at and above 500 °C. This suggests that, in thin films, Mn incorporation and subsequent luminescent outcome is strongly influenced by the dopant source, which is quite different from the bulk phosphor behavior. PACS 81.15.Cd; 78.55.-m; 85.60.-q     

Luminescence and scintillation properties of Y<Subscript>3</Subscript>A<Subscript>l5</Subscript>O<Subscript>12</Subscript>:Ce single crystals and single-crystal films

Luminescence and scintillation properties of Y₃A_l5O₁₂:Ce single crystals grown from the melt by the Czochralski and horizontal directed crystallization methods in various gas media and Y₃A_l5O₁₂:Ce single-crystal films grown by liquid-phase epitaxy from a melt solution based on a PbO-B₂O₃ flux have been comparatively analyzed. The strong dependence of scintillation properties of Y₃A_l5O₁₂:Ce single crystals on their growth conditions and concentrations of Y_Al antisite defects and vacancy defects has been established. Vacancy defects are involved in Ce³⁺ ion emission excitation as the centers of intrinsic UV luminescence and trapping centers. It has been shown that Y₃A_l5O₁₂:Ce single-crystal films are characterized by faster scintillation decay kinetics than single crystals and a lower content of slow components in Ce³⁺ ion luminescence decay during high-energy excitation due to the absence of Y_Al antisite defects in them and low concentration of vacancy defects. At the same time, the light yield of Y₃A_l5O₁₂:Ce single-crystal films is comparable to that of single crystals grown by directed crystallization due to the quenching effect of the Pb²⁺ ion impurity as a flux component and is slightly lower (∼25%) than the light yield of single crystals grown by the Czochralski method.     

Synchrotron radiation photoelectron spectroscopy study of metal-oxide thin film catalysts: Pt-CeO2 coated CNTs

The interaction of Pt with CeO₂ layers was investigated by using high resolution hard X-ray photoelectron spectroscopy. Pt doped CeO₂ layers were deposited simultaneously by rf-magnetron sputtering on a SiO₂/Si substrate and carbon nanotubes (CNTs) grown on a carbon diffusion layer of a polymer membrane fuel cell. In the case of the CNT support photoelectron spectra showed the formation of ionic platinum rich cerium oxide with Pt^2+,4+ species, and with the Pt²⁺/Pt⁴⁺ ratio strongly dependent on the amount of platinum. Ce reveals 4+/3+ mixed valent character with Ce³⁺ concentration increasing with Pt content. In the case of the SiO₂/Si substrate the film revealed Ce⁴⁺ and Pt⁴⁺ species only.     

Photoluminescence behavior of pulsed laser deposited ZnGa<Subscript>2</Subscript>O<Subscript>4</Subscript> thin-film phosphors grown on various substrates

ZnGa₂O₄ thin-film phosphors have been grown on Si(100), Al₂O₃(0001) and MgO(100) substrates using pulsed laser deposition. The structural characterization was carried out on a series of ZnGa₂O₄ films grown on various substrates under various substrate temperatures and oxygen pressures. The films grown on these substrates not only have different crystallinity and surface morphology, but also different Zn/Ga composition ratio. The crystallinity and photoluminescence (PL) of the ZnGa₂O₄ films are highly dependent on the deposition conditions, in particular the stoichiometry ratio of Zn/Ga and the kind of substrate. The variation of Zn/Ga in the films also depends on not only the oxygen pressure but also the substrate temperature during deposition. The PL properties of pulsed laser deposited ZnGa₂O₄ thin films have indicated that Al₂O₃(0001) and MgO(100) are promising substrates for the growth of high-quality ZnGa₂O₄ thin films and that the luminescence brightness depends on the substrate. The luminescence spectra show a broad band extending from 350 to 600 nm and peaking at 460 nm. Received: 11 July 2002 / Accepted: 31 July 2002 / Published online: 28 October 2002 RID="*" ID="*"Corresponding author. Fax: +82-51-6206356, E-mail: jhjeong@pknu.ac.kr