Energy transfer in Y3Al5O12:Ce, Pr and CaMoO4:Sm, Eu phosphors

Non-radiative energy transfers (ET) from Ce³⁺ to Pr³⁺ in Y₃Al₅O₁₂:Ce³⁺, Pr³⁺ and from Sm³⁺ to Eu³⁺ in CaMoO₄:Sm³⁺, Eu³⁺ are studied based on photoluminescence spectroscopy and fluorescence decay patterns. The result indicates an electric dipole-dipole interaction that governs ET in the LED phosphors. For Ce³⁺ concentration of 0.01 in YAG:Ce³⁺, Pr³⁺, the rate constant and critical distance are evaluated to be 4.5×10⁻³⁶ cm⁶ s⁻¹ and 0.81 nm, respectively. An increase in the red emission line of Pr³⁺ relative to the yellow emission band of Ce³⁺, on increasing Ce³⁺ concentration is observed. This behavior is attributed to the increase of spectral overlap integrals between Ce³⁺ emission and Pr³⁺ excitation due to the fact that the yellow band shifts to the red spectral side with increasing Ce³⁺ concentration. In CaMoO₄:Sm³⁺, Eu³⁺, Sm³⁺-Eu³⁺ transfer occurs from ⁴G_5/2 of Sm³⁺ to ⁵D₀ of Eu³⁺. The rate constant of 8.5×10⁻⁴⁰ cm⁶ s⁻¹ and the critical transfer distance of 0.89 nm are evaluated.     

Low-temperature high-resolution VUV spectroscopy of Ce doped LiYF4, LiLuF4 and LuF3 crystals

For LiYF₄:Ce³⁺, LiLuF₄:Ce³⁺ and LuF₃:Ce³⁺ crystals UV/visible emission and time-resolved VUV/UV excitation spectra were recorded at liquid helium temperature with spectral resolution of 0.1 nm for excitation spectra and better than 0.3 nm for emission spectra. Well resolved fine structures due to zero-phonon lines were clearly observed in both excitation and emission spectra for LiYF₄:Ce³⁺ and LiLuF₄:Ce³⁺. For LuF₃:Ce³⁺ crystal no fine structure was detected in the spectra even at the highest spectral resolution. Under the host excitation, the fine structure for high-energy emission band of Ce³⁺ (5d-²F_5/2) in LiLuF₄:Ce³⁺ becomes well pronounced because of weaker reabsorption effect, as compared to Ce³⁺ 4f-5d absorption, due to small penetration depth for exciting radiation. As a result the crystal-field splitting for ²F_7/2 and ²F_5/2 levels of Ce³⁺ in LiLuF₄ crystal was measured. First observation of zero-phonon lines at ∼81,550 and ∼82,900 cm⁻¹ as well as vibronic side bands due to interconfigurational 4f¹⁴-4f¹³5d transitions in Lu³⁺ is reported for excitation spectrum of LiLuF₄:Ce³⁺.     

Methanol adsorption on a CeO2(1 1 1)/Cu(1 1 1) thin film model catalyst

Adsorption and desorption of methanol on a CeO₂(1 1 1)/Cu(1 1 1) thin film surface was investigated by XPS and soft X-ray synchrotron radiation PES. Resonance PES was used to determine the occupancy of the Ce 4f states with high sensitivity. Methanol adsorbed at 110 K formed adsorbate multilayers, which were partially desorbed at 140 K. Low temperature desorption was accompanied by formation of chemisorbed methoxy groups. Methanol strongly reduced cerium oxide by forming hydroxyl groups at first, which with increasing temperature was followed by creation of oxygen vacancies in the topmost cerium oxide layer due to water desorption. Dissociative methanol adsorption and creation of oxygen vacancies was observed as a Ce⁴⁺ → Ce³⁺ transition and an increase of the Ce 4f electronic state occupancy.     

Luminescence of Ce and Pr doped Sr2Mg(BO3)2 under VUV-UV and X-ray excitation

This report presents the luminescence properties of Ce³⁺ and Pr³⁺ activated Sr₂Mg(BO₃)₂ under VUV-UV and X-ray excitation. The five excitation bands of crystal field split 5d states are observed at about 46 729, 44 643, 41 667, 38 314 and 29 762 cm⁻¹ (i.e. 214, 224, 240, 261 and 336 nm) for Ce³⁺ in the host lattice. The doublet Ce³⁺ 5d→4f emission bands were found at about 25 840 and 24 096 cm⁻¹ (387 and 415 nm). The influence of doping concentration and temperature on the emission characteristics and the decay time of Ce³⁺ in Sr₂Mg(BO₃)₂ were investigated. For Pr³⁺ doped samples, the lowest 5d excitation band was observed at about 42017 cm⁻¹ (238 nm), a dominant band at around 35714 cm⁻¹ (280 nm) and two shoulder bands were seen in the emission spectra. The excitation and emission spectra of Ce³⁺ and Pr³⁺ were compared and discussed. The X-ray excited luminescence studies show that the light yields are ∼3200±230 and ∼1400±100 photons/MeV of absorbed X-ray energy for the samples Sr_1.86Ce_0.07Na_0.07Mg(BO₃)₂ and Sr_1.82Pr_0.09Na_0.09Mg(BO₃)₂ at RT, respectively.     

Sn interaction with the CeO2(1 1 1) system: Bimetallic bonding and ceria reduction

A tin layer 0.8 nm thick was deposited onto the CeO₂(1 1 1) surface by molecular beam deposition at a temperature of 520 K. The interaction of tin with cerium oxide (ceria) was investigated by X-ray photoelectron spectroscopy (XPS), ultra-violet photoelectron spectroscopy (UPS) and resonant photoelectron spectroscopy (RPES). The strong tin-ceria interaction led to the formation of a homogeneous bulk Ce-Sn-O mixed oxide system. The bulk compound formation is accompanied by partial Ce⁴⁺ → Ce³⁺ reduction, observed as a giant 4f resonance enhancement of the Ce³⁺ species. CeO₂ and SnO₂ oxides were formed after oxygen treatment at 520 K. The study proved the existence of strong Ce-Sn interaction and charge transfer from Sn to the Ce-O complex that lead to a weakening of the cerium-oxygen bond, and consequently, to the formation of oxygen deficient active sites on the ceria surface. This behavior can be a key for understanding the higher catalytic activity of the SnO_x/CeO_x mixed oxide catalysts as compared with the individual pure oxides.     

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.     

A new synthetic pathway of Sr2CeO4 phosphor and its characterization

A blue-white emitting Sr₂CeO₄ phosphor was synthesized via a simple sol-gel poly vinyl alcohol (PVA)-complexing process using strontium nitrate and cerium nitrate as raw materials. The samples were characterized by TG/DTA, XRD, FTIR, SEM and photoluminescence spectroscopy. The X-ray diffraction study confirms the structure of the system to be orthorhombic. The emission spectra when excited at 267 nm peaks at ∼470 nm. The emission band is assigned to the energy transfer between the molecular orbital of the ligand and charge transfer state of the Ce⁴⁺ ion. The Commission International de l'Eclairage (CIE) co-ordinates for the Sr₂CeO₄ sample were also calculated.     

Photoluminescence characterization of Ce and Dy doped Li2CaGeO4 phosphors

Ce³⁺ and Dy³⁺ activated Li₂CaGeO₄ phosphors were prepared by a solid-state reaction method, and characterized by XRD (X-ray diffraction) and photoluminescence techniques. The characteristic emission bands of Dy³⁺ due to ⁴F_9/2→⁶H_15/2 (blue) and ⁴F_9/2→⁶H_13/2 (yellow) transitions were detected in the emission spectra of Li₂CaGeO₄:Dy³⁺. Ce³⁺ broad band emission was observed in Li₂CaGeO₄:Ce³⁺ phosphors at 372 and 400 nm due to 5d→4f transition when excited at 353 nm. Co-doping of Ce³⁺ enhanced the luminescence of Dy³⁺ significantly and concentration quenching occurs when Dy³⁺ is beyond 0.04 mol%. White-light with different hues can be realized by tuning Dy³⁺ concentration in the phosphors.     

VUV spectroscopic properties of Ce and Pr-doped AREP2O7-type alkali rare earth diphosphates (A=Na, K, Rb, Cs; RE=Y, Lu)

Spectroscopic properties of Ce³⁺ and Pr³⁺-doped AREP₂O₇-type alkali rare earth diphosphates (A=Na, K, Rb, Cs; RE=Y, Lu) have been investigated using VUV spectroscopy technique. Ce³⁺-doped samples show typical Ce³⁺ emission in the range of 325-450 nm. The strong host absorption band starting at around 160 nm indicates that the optical band gap of AREP₂O₇ hosts is at least 7.7 eV, and the host→Ce³⁺ energy transfer process is rather efficient. However, AREP₂O₇:Pr³⁺ samples show less efficient host→Pr³⁺ energy transfer. The direct Pr³⁺ 4f²→4f¹5d¹ excitation, which are 12160±640 cm⁻¹ higher respect to that of Ce³⁺, leads to strong 4f¹5d¹→4f² emission bands in the range of 230-325 nm but no obvious 4f²→4f² emission lines.     

A re-evaluation of the heat capacity of cerium zirconate (Ce2Zr2O7)

The heat capacity of cerium zirconate pyrochlore, Ce₂Zr₂O₇, was measured from 0.4 to 305 K by hybrid adiabatic relaxation method for various magnetic field strengths. Magnetisation measurements were performed on the sample also. The results revealed a low-temperature anomaly that showed Schottky-type characteristics with increasing magnetic field strength. The estimated entropy due to the magnetic ordering of the two Ce³⁺ moments is 1.37R, close to the theoretical value for a doublet ground state (1.39R). The enthalpy increments relative to 298.15 K were measured by drop calorimetry from 531 to 1556 K. The obtained results significantly differ from those reported in the literature; the origin of the discrepancy is due to the probable oxidation of the pyrochlore structure into fluorite.     

Preparation and optical properties of Ce activated (Ca1 − x,Srx)Al2Si2O8 phosphors

(Ca_1 − x, Sr_x)Al₂Si₂O₈:0.06Ce³⁺, M⁺ (M⁺ = Li⁺, Na⁺, K⁺) phosphors have been prepared by conventional solid-state reaction method. The structural and optical properties of the phosphors were characterized by X-ray diffraction (XRD) technique and spectrophotometer, respectively. A regular variation was found among the XRD patterns of (Ca_1 − x, Sr_x)Al₂Si₂O₈:0.06Ce³⁺ phosphors based on the changing of Sr content. With the increase of Sr content, the maximum of emission band presented slight blue shifts (~ 15 nm). The luminescence intensity of CaAl₂Si₂O₈:0.06Ce³⁺ and SrAl₂Si₂O₈:0.06Ce³⁺ were significantly enhanced when K⁺ and Li⁺ were incorporated, respectively.     

Enhanced hydrogen production by doping Pr into Ce0.9Hf0.1O2 for thermochemical two-step water-splitting cycle

We synthesized (Ce_0.9Hf_0.1)_1−xPr_xO_2−δ (x=0, 0.05 and 0.1) using the polymerized complex method. The synthesized samples, as well as the samples after thermochemical two-step water-splitting cycles have a fluorite structure and Pr exists in the solid solutions with both trivalent and tetravalent states, as suggested by powder X-ray Diffraction (XRD) Patterns. The reduction fraction of Ce⁴⁺ in redox cycles (oxidation step in air) and two-step water-splitting cycles (oxidation step in steam) indicates that the addition of Pr into Ce–Hf oxide solid solution cannot improve the reduction fraction of Ce⁴⁺ during the redox cycles but both the reduction fraction of Ce⁴⁺ and H₂ yield are significantly enhanced during two-step water-splitting cycles. The chemical composition of 10 mol% Pr doped Ce_0.9Hf_0.1O₂ exhibits the highest reactivity for hydrogen production in H₂-generation step by yielding an average amount of 5.72 ml g⁻¹ hydrogen gas, which is much higher than that evolved by Ce_0.9Hf_0.1O₂ (4.50 ml g⁻¹). The enhancement effect of doping Pr on the performance during two-step water-splitting cycles is because of the multivalent properties of Pr, which can: (1) reduce the amount of Ce³⁺ oxidized by contamination air (contamination air eliminated by partial oxidation of Pr³⁺ to Pr⁴⁺) in H₂-generation step; (2) enhance the reaction rate in H₂-generation step by improving the ionic conductivity (extrinsic oxygen vacancies created by the substitution of Ce⁴⁺ by Pr³⁺).     

In-situ XAS study on the Cu and Ce local structural changes in a CuO-CeO2/Al2O3 catalyst under propane reduction and re-oxidation

The redox behaviour of a CuO-CeO₂/Al₂O₃ catalyst is studied under propane reduction and re-oxidation. The evolution of the local Cu and Ce structure is studied with in-situ transmission X-ray absorption spectroscopy (XAS) at the Cu K and Ce L₃ absorption edges.CuO and CeO₂ structures are present in the catalyst as such. No structural effect on the local Cu structure is observed upon heating in He up to 873 K or after pre-oxidation at 423 K.Exposure to propane at reaction temperature (600-763 K) fully reduces the Cu²⁺ cations towards metallic Cu⁰. Quick EXAFS spectra taken during reduction show a small amount of intermediate Cu¹⁺ species. Parallel to the CuO reduction, CeO₂ is also reduced in the same temperature range. About 25% of the Ce⁴⁺ reduces rapidly to Ce³⁺ in the 610-640 K temperature interval, while beyond 640 K a further slower reduction of Ce⁴⁺ to Ce³⁺ occurs. At 763 K, Ce reduction is still incomplete with 32% of Ce³⁺.Re-oxidation of Cu and Ce is fast and brings back the original oxides.The propane reduction of the CuO-CeO₂/Al₂O₃ catalyst involves both CuO and CeO₂ reduction at similar temperatures, which is ascribed to an interaction between the two compounds.     

Luminescence properties of Ce and Tb co-activated ZnAl2O4 phosphor

In this study, a solution combustion method was used to prepare green emitting Ce³⁺–Tb³⁺ co-activated ZnAl₂O₄ phosphor. The samples were annealed at 700 °C in air or hydrogen atmosphere to improve their crystallinity and optical properties. X-ray diffraction study confirmed that both as-prepared and post-preparation annealed samples crystallized in the well known cubic spinel structure of ZnAl₂O₄. An agglomeration of irregular platelet-like particles whose surfaces were encrusted with smaller spheroidal particles was confirmed by scanning electron microscopy (SEM). The fluorescence data collected from the annealed samples with different concentrations of Ce³⁺ and Tb³⁺ show the enhanced green emission at 543 nm associated with ⁵D₄→⁷F₅ transitions of Tb³⁺. The enhancement was attributed to energy transfer from Ce³⁺ to Tb³⁺. Possible mechanism of energy transfer via a down conversion process is discussed. Furthermore, cathodoluminescence (CL) intensity degradation of this phosphor was also investigated and the degradation data suggest that the material was chemically stable and the CL intensity was also stable after 10 h of irradiation by a beam of high energy electrons.     

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.     

Enhanced luminescent properties of Y3Al5O12:Tb,Ce phosphor prepared by spray pyrolysis

Yttrium aluminum garnet (YAG) particles doped with Tb³⁺ or double doped with Tb³⁺ and Ce³⁺ were prepared by spray pyrolysis and characterized by photo- and cathode-luminescence. It was tried to incorporate a broad band of Ce³⁺ activator into the line peaks of Tb³⁺ in YAG host without the reduction of emission intensity. Ce-codoped YAG:Tb particles showed a broad band emission due to the d-f transition of Ce³⁺ and a reduction in the intensity of emission peaks due to ⁵D₃-⁷F_j (j=3, 4, 5, 6) transition of Tb³⁺ when they were excited by the ultraviolet light of 270 nm. These results supported that an effective energy transfer occurs from Tb³⁺ to Ce³⁺ in YAG host. Codoping Ce³⁺ ions greatly intensified the excitation peak at 270 nm for the emission at 540 nm of Tb³⁺, which means that more lattice defects, involving in the energy absorption and transfer to Tb³⁺, are formed by the Ce³⁺ codoping. The finding gives a promising approach for enhancing the luminescence efficiency.     

Luminescent and morphological study of Sr2CeO4 blue phosphor prepared from oxalate precursors

Luminescent and morphological studies of Sr₂CeO₄ blue phosphor prepared from cerium-doped strontium oxalate precursor are reported. Powder samples were prepared from 5 and 25 mol% Ce³⁺-doped strontium oxalate as well as from a mechanical mixture of strontium oxalate and cerium oxalate at a 4:1 ratio, respectively. All the samples were characterized by XRD, IR, PLS, and SEM. The luminescent and structural properties of the Sr₂CeO₄ material are little affected by the SrCO₃ remaining from precursors. The Sr₂CeO₄ material consists in one-dimensional chains of edge-sharing CeO₆ octahedra that are linked together by Sr²⁺ ions. The carbonate ion might be associated with oxygen ions of the linear chain, and also with the oxygen atoms located in the equatorial position, which consequently affects the charge transfer bands between O²⁻ and Ce⁴⁺. As observed by SEM, the morphological changes are related to each kind of precursor and thermal treatment, along with irregular powder particles within the size range 0.5-2 μm.     

Synthesis and luminescence properties of Eu, Ce and Tb-activated Sr3La2(BO3)4 under UV excitation

The spectroscopic properties in UV-excitable range for the phosphors of Sr₃La₂(BO₃)₄:RE³⁺ (RE³⁺=Eu³⁺, Ce³⁺, Tb³⁺) were investigated. The phosphors were synthesized by conventional solid-state reactions. The photoluminescence (PL) spectra and commission international de I'Eclairage (CIE) coordinates of Sr₃La₂(BO₃)₄:RE³⁺ were investigated. The f-d transitions of Eu³⁺, Ce³⁺ and Tb³⁺ in the host lattices are assumed and corroborated. The PL and PL excitation (PLE) spectra indicate that the main emission wavelength of Sr₃La₂(BO₃)₄:Eu³⁺ is 611 nm, and Sr₃La₂(BO₃)₄:Ce³⁺ shows dominating emission peak at 425 nm, while Sr₃La₂(BO₃)₄:Tb³⁺ displays green emission at 487, 542, 582 and 620 nm. These phosphors were prepared by simple solid-state reaction at 1000 °C. There are lower reactive temperature and more convenient than commercial phosphors. The Sr₃La₂(BO₃)₄:Tb³⁺ applied to cold cathode fluorescent lamp was found to emit green light and have a major peak wavelength at around 542 nm. These phosphors may provide a new kind of luminescent materials under ultraviolet excitation.     

Effect of Ce on the spectroscopic properties in Er doped TeO2-GeO2-Nb2O5-Li2O glasses

The Ce³⁺ ion was introduced into Er³⁺ doped TeO₂-GeO₂-Nb₂O₅-Li₂O (TGNL) glass to improve the 1.5 μm fluorescence characteristics. As increasing of Ce³⁺ concentration, the lifetime of Er³⁺:⁴I_11/2 level is shortened form 360 to 225 μs, while the Er³⁺:⁴I_13/2 level remains unchanged. Accordingly, the upconversion fluorescence (blue, green and red) was quenched. Improved 1.5 μm emission is obtained and the reason is ascribed to the increase of nonradiative rate between the ⁴I_11/2 and ⁴I_13/2 level of the Er³⁺ ions.     

Synthesis and optical properties of 10 mol% Ce, 5 mol% Tb co-doped KGdF4 and GdF3 submicro/nanocrystals

By controlling the pH values of prepared solutions, the 10 mol% Ce³⁺, 5 mol% Tb³⁺ co-doped KGdF₄ (synthesized with pH = 3) and the 10 mol% Ce³⁺, 5 mol% Tb³⁺ co-doped GdF₃ (synthesized with pH = 1) submicro/nanocrystals have been synthesized based on a citric acid assisted hydrothermal method. For comparison, the samples synthesized by co-precipitation method (without hydrothermal treatment) with pH = 3 and 1 were also collected. The X-ray diffraction data illustrate that the hydrothermal treated KGdF₄ sample crystallizes in the cubic phase and the GdF₃ sample crystallizes in the orthorhombic phase. However, the samples synthesized by co-precipitation method with pH = 3 and 1 are both cubic phase KGdF₄. The field emission scanning electron microscopy images suggest that the hydrothermal treated KGdF₄ submicro/nanocrystals present spherical morphology and the GdF₃ submicrocrystals are rhombic-shaped. And the photoluminescence excitation and emission spectra as well as the luminescent dynamic curves demonstrate the difference in optical properties of the two hydrothermal treated samples.