Defect chemistry and VUV optical properties of the BaMgAl10O17:Eu-Ba0.75Al11O17.25:Eu solid solution

The optical properties of the BaMgAl₁₀O₁₇:Eu²⁺ (BAM)-Ba_0.75Al₁₁O_17.25:Eu²⁺ (BAL) solid solution have been studied using VUV excitation, emission and reflectance spectroscopy. Three unique Eu²⁺ emission centers are observed in a ratio that depends on the composition of the host and the dopant concentration. Two of the emission centers are assigned to Eu on normal Beevers-Ross sites and Eu on anti Beevers-Ross sites. The defect chemistry of this system is modeled based on the known behavior of the spinel (MgO·nAl₂O₃) system. Based on this model, the third Eu center can be assigned either to Eu near Al vacancies or to Eu associated with O atoms in the cation layer. In undoped materials exciton emission is observed, peaking at 263 nm in BAM and 285 nm in BAL. This emission may be the mechanism of host-to-activator energy transfer in these phosphors.     

Morphology control and luminescence properties of BaMgAl10O17:Eu phosphors prepared by spray pyrolysis

Starting from the aqueous solutions of metal nitrates with citric acid and polyethylene glycol (PEG) as additives, BaMgAl₁₀O₁₇:Eu²⁺ (BAM:Eu²⁺) phosphors were prepared by a two-step spray pyrolysis (SP) method. X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence spectra were used to characterize the resulted BAM:Eu²⁺ phosphors. The obtained BAM:Eu²⁺ phosphor particles have spherical shape, submicron size (0.5-3 μm). The effects of process conditions of the spray pyrolysis, such as molecular weight and concentration of PEG, on the morphology and luminescence properties of phosphor particles were investigated. Adequate amount of PEG was necessary for obtaining spherical particles, and the optimum emission intensity could be obtained when the concentration of PEG was 0.03 g/ml in the precursor solution. Moreover, the emission intensity of the phosphors increased with increasing of metal ion concentration in the solution. Compared with the BAM:Eu²⁺ phosphor prepared by citrate-gel method, spherical BAM:Eu²⁺ phosphor particles showed a higher emission intensity.     

Synthesis and characterization of Gd2O3:Eu phosphor nanoparticles by a sol-lyophilization technique

The characterization and luminescence properties of nanostructured Gd₂O₃:Eu³⁺ phosphors synthesized by a sol-lyophilization process are presented. After preparation of gadolinium-based sols from gadolinium nitrate and ammonium hydroxide, the so-prepared sols were freeze dried at −10°C and calcinated at different temperatures. For temperatures lower than 1300 K, highly crystalline samples with the cubic structure can be obtained without concomitant grain growth of the particles (<50 nm). The luminescence spectra contain all possible transitions of Eu³⁺ with C₂ symmetry and present two major features: an increase of the luminescence efficiencies of the phosphors in comparison with that obtained by solid-state reaction and the presence of an additional peak at about 609 nm at the vicinity of the ⁵D₀→⁷F_0…4 transition.     

Solvothermal synthesis and luminescence properties of monodisperse Gd2O3:Eu and Gd2O3:Eu@SiO2 nanospheres

A series of uniform, monodispersed Gd(OH)³:Eu³⁺ nanospheres less than 100 nm were successfully synthesized with iron ions as catalyst and DMF as solvent under the solvothermal condition. Cetyltrimethyl ammonium bromide (CTAB) and Polyvinylpyrrolidone (PVP) were performed as co-surfactant during this facile procedure should be changed as A series of uniform, monodisperse Gd(OH)³:Eu³⁺ nanospheres less than 100 nm in diameter were successfully synthesized with solvothermal method. Iron ion was used as catalyst and Dimethylformamide (DMF) as solvent, Cetyltrimethyl Ammonium Bromide (CTAB) and Polyvinylpyrrolidone (PVP) were performed as surfactants. Further calcination process was applied to prepare Gd₂O₃:Eu³⁺ nanoshpheres during this facile procedure.     

Eu2+、Mn2+、Sr2+掺杂BaMgAl10O17的燃烧法合成及光致发光性能

在600℃温度下,采用液相燃烧法合成了Sr²⁺、Eu²⁺和Mn²⁺三掺的BaMgAl₁₀O₁₇（BAM）蓝绿荧光粉。用XRD、SEM和荧光光谱仪分别分析和表征该荧光粉的物相、形貌和光致发光性能。结果表明,液相燃烧法合成BAM的温度明显低于传统的高温固相合成法;合成的纳米棒均匀、无团聚现象;荧光光谱仪分析表明Eu²⁺、Mn²⁺离子间存在能量传递,且Sr²⁺能有效提高BAM的发光强度,约为固相法制备荧光强度的1.8倍。BAM：0.1Eu²⁺,0.04Mn²⁺,0.05Sr²⁺色坐标为（0.146,0.250）,属于蓝绿光。     

A potential red phosphor ZnMoO4:Eu for light-emitting diode application

Motivated by the need for new red phosphors for solid-state lighting applications Eu³⁺-doped ZnMoO₄ was prepared by solid-state reaction and its photoluminescence properties were investigated. Compared with Ca_0.80MoO₄:Eu_0.20³⁺, the obtained Zn_0.80MoO₄:Eu_0.20³⁺ phosphor shows a stronger excitation band near 400 nm as well as enhanced red emissions (under 393 nm excitation). The strong red-emission lines at 616 nm correspond to the forced electric dipole ⁵D₀→⁷F₂ transitions on Eu³⁺. The chromaticity coordinates (x=0.63, y=0.37) are close to the standard of National Television Standard Committee (NTSC). The optical properties suggest that Zn_0.80MoO₄:Eu_0.20³⁺ is an efficient red-emitting phosphor for LED applications.     

First-principle Studies on Enhanced Optical Stability of BaMgAl10O17:Eu2+ Phosphor by SiN Doping

Using density functional theory, we studied band structure, density of states, optical proper-ties and Mulliken population of the pure and SiN doped BaMgAl₁₀O₁₇:Eu²⁺(BAM:Eu²⁺) phosphors. Calculation results showed that the bands of BAM:Eu²⁺ were of low band en-ergy dispersion, indicating large joint density of states, hence high performance of optical absorption and luminescence. BAM:Eu²⁺ showed stronger absorption intensity while Eu²⁺ occupied the BR sites instead of the mO sites. The concentration of Eu²⁺ at BR sites increased while that at mO sites decreased after Si-N doping. The influence of the vari-ation of Eu²⁺ distribution on the spectra was stronger than the influence of the decrease of Eu²⁺ PDOS when SiN concentration was lower than 0.25, therefore the absorption andluminescence intensity of BAM:Eu²⁺ were enhanced. Mulliken population of Si-N bond was higher than Al-O bond, while that of Eu-N bond was higher than Eu-O bond as well, indicating that Si-N bonds and Eu-N bonds possessed higher covalence than Al-O bonds and Eu-N bonds respectively. The existence of Si-N bonds and Eu-N bonds enhanced the local covalence of Eu²⁺, hence the optical stability of BAM:Eu²⁺.     

Continuous hydrothermal synthesis of CoFe2O4 nanoparticles

We have investigated the continuous hydrothermal synthesis and crystallization of spinel CoFe₂O₄ via the reaction of ferric nitrate and cobalt nitrate with sodium hydroxide. The reaction was carried out in water at temperatures ranging from 475 to 675 K and pressures of 25 MPa. The relative solubility of the precipitating cations was found to play a critical role in attaining the correct product. It was found necessary to control pH and temperature in order to prevent premature precipitation of iron in the reactor. Two variations of the continuous hydrothermal technique were examined—cold mixing and hot mixing. The cold mixing experiments produced a product with less impurity than the hot mixing experiments. Furthermore, the cold mixing configuration was successful in producing uniform nanoparticles of CoFe₂O₄. A mechanism of particle formation was postulated involving the precipitation of metal hydroxides at ambient conditions, dissolution of the hydroxides as temperature is increased followed by rapid precipitation of metal oxides at elevated temperatures. The hot mixing experiments, on the other hand, simply involve the precipitation of metal oxides due to the addition of the hot hydroxide solution. In both cases, very fine particles of CoFe₂O₄ are produced in the range of the processing conditions investigated.     

A novel red emitting phosphor Ca2SnO4: Eu

A novel red emitting phosphor, Eu³⁺-doped Ca₂SnO₄, was prepared by the solid-state reaction. X-ray powder diffraction (XRD) analysis confirmed the formation of Ca₂SnO₄: Eu³⁺. Field-emission scanning electron-microscopy (FE-SEM) observation indicated a narrow size-distribution of about 500 nm for the particles with spherical shape. Photoluminescence measurements indicated that the phosphor exhibits bright red emission at about 615 nm under UV excitation. The excellent luminescence properties make it possible as a good candidate for plasma display panels (PDP) application. Splitting of the ⁵D₀-⁷F_J transitions of Ca₂SnO₄: Eu³⁺ suggests that the Eu³⁺ ions occupied two nonequivalent sites in the crystallite. The luminescence lifetime measurement showed a bi-exponential decay, providing other evidence for the existence of two different environments for Eu³⁺ ions.     

Studies of defects in combustion synthesized europium-doped LiAl5O8 red phosphor

Europium-doped LiAl₅O₈ red phosphor was prepared using a self-propagating (combustion) synthesis. The formation of crystalline LiAl₅O₈ was confirmed by X-ray diffraction. The morphological aspect of the resulting powders was examined by scanning electron microscopy. Electron spin resonance studies have been carried out in order to study the characteristics of the defect centres and the thermoluminescence (TL) peaks observed in this phosphor. Two types of centres (centre I and centre II) have been identified in LiAl₅O₈:Eu. Centre I is characteristic of a species exhibiting an isotropic g-value 2.0089 with a line width of 70 G and is assigned to a V-centre. Centre II is also characterized by an isotropic g-value 2.0059 with a line width of about 10 G. Centre II is ascribed to a F⁺-centre. A room temperature photoluminescence study shows a strong emission line at 613 nm corresponding to the ⁵D₀→⁷F₂ transition of Eu³⁺ ions.     

Seeking the optimal LaTaO4:Eu phosphor

Lanthanum orthotantalate, LaTaO₄, is an excellent host lattice for rare-earth luminescent ions such as Eu³⁺ for red emission. However, there are multiple RETaO₄ (RE=rare earth) polymorphs, and the stability of these is controlled predominantly by the RE-radius. Thus it is difficult to obtain a pure phase of LaTaO₄:Eu as Eu concentration and consequently the RE radius is varied. We recently reported a ‘soft-chemical’ route that allows crystallization of pure-phase LaTaO₄:Eu at temperatures as low as 800 °C. In the current report, we investigate polymorph evolution and Eu emission as a function of Eu concentration and annealing temperature. We obtain a maximum quantum yield (QY) of 83% at the highest Eu substitution (25%) for which the low temperature orthorhombic (Pbca) polymorph is stable. Therefore, QY is not limited necessarily by concentration quenching; rather it is limited by polymorph stability as the RE-radius decreases with increasing Eu substitution.     

Synthesis of SiO2/Y2O3:Eu core-shell materials and hollow spheres

The SiO₂/Y₂O₃:Eu core-shell materials and hollow spheres were first synthesized by a template-mediated method. X-ray diffraction patterns indicated that the broadened diffraction peaks result from nanocrystals of Y₂O₃:Eu shells and hollow spheres. X-ray photoelectron spectra showed that the Y₂O₃:Eu shells are linked with silica cores by Si-O-Y chemical bond. SEM and TEM observations showed that the size of SiO₂/Y₂O₃:Eu core-shell structure is in the range of 140-180 nm, and the thickness of Y₂O₃:Eu hollow spherical shell is about 20-40 nm. The photoluminescence spectra of SiO₂/Y₂O₃:Eu core-shell materials and Y₂O₃:Eu hollow spheres have better red luminescent properties, and the broadened emission bands came from the size effects of nanocrystals composed of Y₂O₃:Eu shell.     

Ce10[Si10O9N17]Br, Nd10[Si10O9N17]Br and Nd10[Si10O9N17]Cl oxonitridosilicate halides with a new layered structure type

The isotypic oxonitridosilicate halides Ce₁₀[Si₁₀O₉N₁₇]Br, Nd₁₀[Si₁₀O₉N₁₇]Br and Nd₁₀[Si₁₀O₉N₁₇]Cl were obtained by the reaction of the respective lanthanide metals, their oxides and halides with “Si(NH)₂” in a radiofrequency furnace at temperatures around 1800 °C, using CsBr, resp. CsCl, as a flux. The crystal structures were determined by single-crystal X-ray diffraction (Pbam, no. 55, Z=2; Ce/Br: a=10.6117(9) Å, b=11.2319(10) Å, c=11.688(8) Å, R1=0.0356; Nd/Br: a=10.523(2) Å, b=11.101(2) Å, c=11.546(2) Å, R1=0.0239; Nd/Cl: a=10.534(2) Å, b=11.109(2) Å, c=11.543(2) Å, R1=0.0253) and represent a new layered structure type. The structure refinements were performed utilizing an O/N-distribution model according to Paulings rules, i.e. nitrogen was positioned on all bridging sites and mixed O/N-occupation was assumed on the terminal sites resulting in charge neutrality of the compounds. The layers consist of condensed [SiN₂(O/N)₂] and [SiN₃(O/N)] tetrahedra of Q² and Q³ type. The chemical composition of the compounds was derived from chemical analyses for Nd₁₀[Si₁₀O₉N₁₇]Br and electron probe micro analyses (EPMA) for all three compounds. The results of IR spectroscopic investigations are reported.     

A new BaB2Si2O8:Eu/Eu, Tb phosphor - Synthesis and photoluminescence properties

In the present work, we have synthesized maleevite mineral phase BaB₂Si₂O₈ for the first time, which is isostructural with the pekovite mineral SrB₂Si₂O₈. In these europium doped host lattices, we observed the partial reduction of Eu³⁺ to Eu²⁺ at high temperature during the synthesis in air. Tb³⁺ co-doping in MB₂Si₂O₈:0.01(Eu³⁺/Eu²⁺) [M=Sr, Ba] improves the emission properties towards white light. The emission color varies from bluish white to greenish white under UV lamp excitation when the host cation changes from Sr to Ba.     

Crystal structure of Ca12Al14O32Cl2 and luminescence properties of Ca12Al14O32Cl2:Eu

The crystal structure of Ca₁₂Al₁₄O₃₂Cl₂ was determined from laboratory X-ray powder diffraction data (CuKα₁) using the Rietveld method, with the anisotropic displacement parameters being assigned for all atoms. The crystal structure is cubic (space group , Z=2) with lattice dimensions a=1.200950(5) nm and V=1.73211(1) nm³. The reliability indices calculated from the Rietveld method were R_wp=8.48% (S=1.21), R_p=6.05%, R_B=1.27% and R_F=1.01%. The validity of the structural model was verified by the three-dimensional electron density distribution, the structural bias of which was reduced as much as possible using the maximum-entropy methods-based pattern fitting (MPF). The reliability indices calculated from the MPF were R_B=0.75% and R_F=0.56%. In the structural model there are one Ca site, two Al sites, two O sites and one Cl site. This compound is isomorphous with Ca₁₂Al_10.6Si_3.4O₃₂Cl_5.4. Europium-doped sample Ca₁₂Al₁₄O₃₂Cl₂:Eu²⁺ was prepared and the photoluminescence properties were presented. The excitation spectrum consisted of two wide bands, which were located at about 268 and 324 nm. The emission spectrum, when excited at 324 nm, resulted in indigo light with a peak at about 442 nm.     

Sol-gel deposition and luminescent properties of LaMgAl11O19:Ce/Tb phosphor films

Rare earth ions (Ce³⁺, Tb³⁺)-doped LaMgAl₁₁O₁₉ phosphor films were deposited on quartz glass substrates by Pechini sol-gel and dip coating method. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric and differential thermal analysis (TG-DTA), atomic force microscopy (AFM), field emission scanning electronic microscopy (FESEM), photoluminescence (PL) spectra, and lifetimes were used to characterize the resulting films. The results of XRD indicated that the magnetoplumbite structure LaMgAl₁₁O₁₉ phase can be obtained at 1200 °C on quartz glass substrates. This was further verified by the results of FT-IR and TG-DTA. AFM study showed that uniform films have an average grain size of 150 nm and a root mean square (RMS) roughness of 4 nm. The thickness of the films characterized by FESEM is about 340 nm. LaMgAl₁₁O₁₉:Ce³⁺ film showed the parity and spin allowed 5d-4f band emission of Ce³⁺ with a maximum at 350 nm. Ce³⁺, Tb³⁺-codoped LaMgAl₁₁O₁₉ films showed the band emission of Ce³⁺ and characteristic emission of Tb³⁺, namely, ⁵D_3,4-⁷F_J (J=6, 5, 4, 3) due to an efficient energy transfer from Ce³⁺ to Tb³⁺ in the host.     

Hydrothermal synthesis and luminescent properties of LuBO3:Tb microflowers

Hexagonal vaterite-type LuBO₃:Tb³⁺ microflower-like phosphors have been successfully prepared by an efficient surfactant- and template-free hydrothermal process directly without further sintering treatment. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectrometry, transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), photoluminescence (PL) and cathodoluminescence (CL) spectra as well as kinetic decays were used to characterize the samples. The as-obtained phosphor samples present flowerlike agglomerates composed of nanoflakes with thickness of 40 nm and high crystallinity in spite of the moderate reaction temperature of 200 °C. The reaction mechanism has been considered as a dissolution/precipitation mechanism; the self-assembly evolution process has been proposed on homocentric layer-by-layer growth style. Under ultraviolet excitation into the 4f⁸→4f⁷5d transition of Tb³⁺ at 248 nm (or 288 nm) and low-voltage electron beam excitation, LuBO₃:Tb³⁺ samples show the characteristic green emission of Tb³⁺ corresponding to ⁵D₄→⁷F_{6, 5, 4, 3} transitions with the ⁵D₄→⁷F₅ transition (542 nm) being the most prominent group, which have potential applications in fluorescent lamps and field emission displays.     

CTAB-assisted hydrothermal synthesis of YVO4:Eu powders in a wide pH range

Rhombus-, rod-, soya bean- and aggregated soya bean-like YVO₄:Eu³⁺ micro- and nanostructures were synthesized by a cetyltrimethylammonium bromide (CTAB)-assisted hydrothermal method at 180 °C for 24 h in a wide pH range. The as-synthesized powders were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and photoluminescence spectroscopy (PL). The XRD results confirmed the formation of phase-pure YVO₄:Eu³⁺ powders with tetragonal structure under hydrothermal process in a wide pH range. Electron microscopic observations evidenced the morphological transformation of YVO₄:Eu³⁺ powders from rhombus-like microstructure to rod-, soya bean, and aggregated soya bean-like nanostructures with an increase in the pH of the synthesis solution. The results from the PL measurements revealed that the intensities of PL emission peaks were significantly affected by the morphologies and crystallinity of samples due to the absence of an inversion symmetry at the Eu³⁺ lattice site, and the highest luminescence intensity was observed for rod-like YVO₄:Eu³⁺ powders.     

Role of crystallite size on the photoluminescence properties of SrIn2O4:Eu phosphor synthesized by different methods

Photoluminescence (PL) of Eu³⁺ was studied in SrIn₂O₄ host lattice. A complete solid solubility of Eu³⁺ has been found in the series SrIn_2−xEu_xO₄ [x=0-2.0]. The phase formation at a relatively low temperature and in a very short duration was achieved by combustion synthesis (CS). Concentration quenching of luminescence has been observed in SrIn_2−xEu_xO₄ [x=0.1-2.0] and the critical concentration for maximum emission was found to be with x=0.3. In order to find the role of crystallite size on the PL properties of SrIn₂O₄:Eu³⁺, the results obtained with phosphors synthesized by solid state reaction (SSR) and CS methods were compared.     

Synthesis and spectral characteristics of Sr2Y8(SiO4)6O2: Eu polycrystals

Spectral-luminescent characteristics of Sr₂Y₈(SiO₄)₆O₂: Eu powder crystal phosphor with the apatite structure and high-intensity luminescence of Eu³⁺ ions have been studied. The charge state of europium in the samples has been characterized by means of X-ray L₃-adsorption spectroscopy. It was established that Eu³⁺ forms two types of optical centers. Besides, luminescence of Eu²⁺ions was found. Reduction Eu³⁺→Eu²⁺ was considered, which may be due to vacancy formation in the 4f crystal lattice position and to negative charge transfer by this vacancy to two ions. Thus, in the silicate lattice there exist inhomogeneously distributed oxygen-deficient centers, which are responsible for nonradiative transfer of excitation energy to Eu³⁺ and Eu²⁺ ions. To study electron-vibrational interactions in the crystal phosphor samples, their IR and Raman spectra were examined. In the luminescence spectrum of Eu²⁺, a series of low-intensity bands caused by interaction of the 4f⁶5d state of Eu²⁺ with silicate lattice vibrations was observed.