Yanlin Huang

Emission Red Shift and Unusual Band Narrowing of Mn2+ in NaCaPO4 Phosphor

Concentration dependence of Mn(2+) luminescence in NaCaPO(4)/Mn(2+) is investigated by structural analyses and optical and laser excitation spectroscopies in the temperature range 19-300 K. NaCaPO(4)/Mn(2+) forms solid solution over the Mn(2+) concentration range 1.0-22 mol %. We observe the red shift and unusual band narrowing of Mn(2+) emission by increasing Mn(2+) concentration in NaCaPO(4). The lifetime of Mn(2+) emission lengthens unexpectedly for higher Mn(2+) concentration. The results are discussed in relation with crystal structure, photon reabsorption, exchange interaction, and energy transfer and energy migration in NaCaPO(4)/Mn(2+).

The thermal stabilities of luminescence and microstructures of Eu2+-doped KBaPO4 and NaSrPO4 with β-K2SO4 type structure.

Eu(2+)-doped monophosphates NaSrPO(4) and KBaPO(4) with the β-K(2)SO(4) structure were synthesized using the conventional high temperature solid state reaction. The X-ray powder diffraction, photoluminescence excitation, and emission spectra and decay curves were measured. The phosphors can be efficiently excited by UV-visible light from 220 to 430 nm to realize emission in the visible range. The natures of the Eu(2+) emission, e.g., the chromaticity coordinates, the Stokes shifts, and the luminescence absolute quantum efficiencies, were reported. The luminescence quenching temperatures and the thermal activation energies for NaSrPO(4):Eu(2+) and KBaPO(4):Eu(2+) were obtained from the temperature dependent (10-435 K) luminescence intensities and decay curves. KBaPO(4):Eu(2+) presents only one emission center; however, Eu(2+) ions have a disordered environment in NaSrPO(4) lattices. The relationship between the luminescence thermal stabilities and the crystal structures was discussed. The crystallographic occupations of rare earth ions doped in these hosts were analyzed by the site-selective emission spectra and the excitation spectra of Eu(3+) ions in the (7)F(0)→(5)D(0) transitions using a pulsed, tunable, and narrow-band dye laser. In KBaPO(4), the Eu(3+) ions could be distributed in the host with a high ordered state in only one site in the lattices. However, the multiple site structure of Eu(3+) ions with highly disordered distributions in NaSrPO(4) lattices was suggested.

Abnormal Reduction, Eu3+ → Eu2+, and Defect Centers in Eu3+-Doped Pollucite, CsAlSi2O6, Prepared in an Oxidizing Atmosphere

Eu-doped pollucite CsAlSi2O6 was synthesized by the sol-gel method and heated in an air atmosphere. The crystal structure and the microstructure of the phosphors were investigated by X-ray powder diffraction and SEM images, respectively. The photoluminescence spectra and temperature dependent decay curves were measured. An abnormal reduction phenomenon of Eu(3+) → Eu(2+) was reported when Eu(3+) ions were doped in alkaline metal cation sites in CsAlSi2O6 prepared in an oxidizing atmosphere. The abnormal mechanism was discussed on the basis of the charge compensation model and a rigid three-dimensional framework structure of CsAlSi2O6. The luminescence color centers were investigated by luminescence decay lifetimes and thermal stabilities of Eu(2+) ions. The defect complexes of [(Eu(3+)Cs)(••)-2VCs] or [(Eu(3+)Cs)(••)-Oi″] induced by the substitution of Eu(3+) on Cs(+) were suggested in the lattices. Eu(2+) ions could be regarded as Eu(3+) ions combining with the released electrons from defects Oi″ or VCs in close vicinity of Eu(3+) (Eu(3+) + e); the electrons cannot enter the atom track of Eu(2+) presenting luminescence of Eu(2+) ions. The results indicate that several defect traps can be attributed to the abnormal reduction mechanism of Eu(3+) to Eu(2+) ions in a matrix.

Photoluminescence Properties of Eu3+-Doped Glaserite-Type Orthovanadates CsK2Gd[VO4]2

Undoped and Eu(3+)-doped glaserite-type orthovanadates CsK2Gd1-xEux[VO4]2 with various Eu(3+) concentrations of x = 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1.0 were synthesized via the solid-state reaction. The formation of a single phase compound was verified through the X-ray diffraction studies. The photoluminescence (PL) and PL excitation (PLE) spectra, PL decay curves, and absolute quantum efficiency (QE) were investigated. Unlike the conventional Eu(3+)-doped vanadates, these Eu(3+)-doped samples showed not only several sharp emission lines due to Eu(3+) but also a broad emission band with a maximum at 530 nm due to the [VO4](3-) host. The intensities of the host and Eu(3+) emissions increased when the Eu(3+) concentration was increased from x = 0 to x = 0.6 and decreased above x = 0.6. Similar concentration dependence was observed for QE. The host emission, even if in the Eu(3+)-condensed host of CsK2Eu(VO4), was never quenched indicating inefficient energy transfer from the host [VO4](3-) to Eu(3+). This inefficient energy transfer is understood by suppression of the energy transfer by the V-O-Eu bond angle deviated from 180° and the separation of Eu(3+) ions at the Gd(3+) site from [VO4](3-). Like the 530 nm charge transfer [VO4](3-) emission, two broad and intense PLE bands with maxima at 330 and 312 nm were observed for the Eu(3+) emission. A maximum QE of 38.5% was obtained from CsK2Gd1-xEux[VO4]2 (x = 0.6). A white-colored emission was obtained by the combination of the broad 530 nm emission band and the intense sharp lines due to Eu(3+) at 590-620 nm.

Multisite Structure of PbWO4:Eu3+Crystals Investigated by Site-Selective Laser-Excitation Spectroscopy

Defect structures of Eu(3+)-doped PbWO(4) crystals are investigated by site-selective laser-excitation spectroscopy. The excitation spectrum of the (7)F(0) --> (5)D(0) transition shows a strong dependence on Eu(3+)-concentration in PbWO(4) crystals. Only one substitution site for Eu(3+) is identified in the PbWO(4):Eu(3+) (0.01 at.%) crystal, while at least six inequivalent sites are observed in the PbWO(4):Eu(3+) (0.05 and 0.5 at.%) crystals. The charge compensation mechanisms for the observed sites are discussed in relation with annealing effects and temperature-dependent decay curves. The dominant site for Eu(3+) in the PbWO(4) lattice seems to be due to a formation of Eu(Pb)(3+)-V(Pb) dipole by charge compensation. The minor sites for Eu(3+) are attributable to the Eu(Pb)(3+)-O(i) dipole, a site perturbed by Eu(Pb)(3+*)-V(Pb) dipole, and a clustering of Eu(3+) in the PbWO(4) lattice. The energy transfer and site distribution of Eu(3+) are discussed in PbWO(4):Eu(3+) (0.01, 0.05, and 0.5 at.%).

Spectroscopic properties of Pr3+ ions in a PbWO4 single crystal.

Site-selective fluorescence laser spectroscopy of Pr (3+) ions in lead tungstate single crystal were investigated at temperatures from 10 to 300 K. The site-selective emission spectra and fluorescence decays from the (3)P J ( J = 0, 1, 2) and (1)D 2 states were analyzed. The (3)P J ( J = 0, 1, 2) level shows its predominantly radioactive character with the typical greenish-blue luminescence ascribed to (3)P J transition. The emission from the (1)D 2 level is only observed when this level is directly excited. The decay kinetic of the (1)D 2 level was measured under site-selective excitation and discussed in terms of cross-relaxation. The up-conversion emission from levels (3)P 1 and (3)P 0 following excitation of the (1)D 2 state was observed in the PbWO 4 crystal between 10 and 300 K. The main up-conversion mechanism, together with the understanding the quenching of the (1)D 2 fluorescence in this Pr (3+) heavily doped PbWO 4 were discussed. The presence of the complex structures of the emission spectra and different decay profiles indicate that several processes contribute to the quenching of the (1)D 2 fluorescence of Pr (3+) ions. It was found that the up-conversion fluorescence intensity had a quadratic dependence on the laser input power. The temporal behavior of the up converted emission indicates that an energy-transfer up-conversion is the dominant process.

Site-Selective Excitation and Luminescence Properties of Eu3 + Ions Doped in SrZn2 ( PO4 ) 2

SrZn 2 (PO 4 ) 2 doped with Eu 3+ ions was prepared by high temperature solid-state reaction. The site-selective excitation and emission spectroscopy and luminescence decay (lifetime) have been investigated in the 5 D 0 → 7 F 0 region by using a pulsed, tunable, and narrowband dye laser. We observed two crystallographic sites for Eu 3+ in SrZn 2 (PO 4 ) 2 below 250 K and energy transfer from Eu 3+ at one site to Eu 3+ at the other site. The Stark energy levels of Eu 3+ at two different sites were assigned from the site-selective emission spectra. The luminescence from Eu 3+ at one of the two sites was quenched at room temperature. The lifetime of Eu 3+ ions at the two sites is compared. The defect structures and charge compensation mechanisms are discussed.

Photoluminescence properties of a blue-emitting phosphor Eu2+-activated Ca3ZnAl4O10

A new aluminate host material Ca3ZnAl4O10 doped with Eu2+ was prepared by a high-temperature solid-state reaction method, and a pure crystalline phase of Ca3ZnAl4O10 was confirmed with X-ray powder diffraction (XRD) measurement. The luminescent property was investigated with excitation and emission spectra. The phosphor could be excited by UV light from 220 nm to 400 nm and emitted a blue luminescence peaked at 450 nm, which corresponded to the 4f65d1→4f7 transition of Eu2+ ions. The dependence of luminescence intensities of Eu2+-doped Ca3ZnAl4O10 on the doping concentrations was investigated. The luminescence decay and the color coordinates were discussed in order to further investigate its potential applications for white light-emitting diode phosphors pumped by a near-UV chip.

Vacuum Ultraviolet and Ultraviolet Spectroscopy of Tb3+- and Eu3+-Doped Na(Sr,Ba)PO4 Phosphate

The Eu3+- and Tb3+-doped NaSr0.65Ba0.35(PO4) phosphors were prepared by high-temperature solid-state reaction. X-ray powder diffraction (XRD) analyses confirm the pure crystalline phase of Olgite mineral. Scanning electron microscopy (SEM) measurements indicate that these phosphors have good surface-crystalline with a narrow size distribution. Vacuum ultraviolet (VUV) synchrotron radiation and ultraviolet (UV) spectroscopy were applied to study the luminescence properties of these phosphors. The bands near 147 nm in the VUV excitation spectra of those doped samples are attributed to the PO43- absorption in the host. The excitation and emission spectra indicate that the phosphors can be effectively excited for NaSr0.65Ba0.35(PO4):Eu3+ and NaSr0.65Ba0.35(PO4):Tb3+ by 147 nm and exhibit a red and green light, respectively. The Commission International de IEclairage (CIE) chromaticity coordinates for Eu3+- and Tb3+-activated phosphors are calculated. Considering the high luminescence intensity, excellent color purity and chemical stability, NaSr0.65Ba0.35(PO4):RE (RE = Eu3+, Tb3+) are attractive red- and green-emitting plasma display panel phosphors.

Yellow-to-violet, blue, and green frequency upconversions in Nd3+-doped PbWO4 single crystal

Upconversion emission properties of Nd3+ ions doped in PbWO4 crystal are investigated by pulsed laser excitation into the G5∕24+G2(1)7∕2 levels at temperatures from 10to295K. The main upconversion emission consists of strong blue emission bands in the wavelength region of 435–447nm corresponding to the P1∕22→I9∕24 transitions. Some UV bands located in the wavelength region of 356–397nm corresponding to the D3∕24→I9∕24, I11∕24, and I13∕24 transitions and weak green emission at 525.2nm corresponding to the G7∕24→I9∕24 transition are observed. Several upconversion blue emissions from the P1∕22 level and the absoprtion lines due to the I9∕24→P1∕22 transition indicate multisite structure of the Nd3+ ions in the PbWO4 lattices. We investigate the excitation spectra of the upconversion emissions and their pump power dependence and lifetimes from which the probable upconversion mechanisms are proposed and analyzed. The dominant mechanisms for the upconversion emission originating from the D3∕24 level (UV emission...