Luminescence properties of Ce and/or Mn activated Ca10K(PO4)7 under ultraviolet and vacuum ultraviolet excitation

New Ce³⁺ and/or Mn²⁺ activated Ca₁₀K(PO₄)₇ phosphors were prepared by solid-state reaction, and their photoluminescence properties upon ultraviolet and vacuum ultraviolet excitation were investigated. Under 254 nm excitation, a series of Ca₁₀K(PO₄)₇:xMn²⁺ samples exhibit two emission bands at 463 and 650 nm, which could be attributed to oxygen defects and ⁴T₁–⁶A₁ transition of Mn²⁺, respectively. And an energy transfer from defects to Mn²⁺ has been observed. With the Mn²⁺ content increased, the emitting hues of Ca₁₀K(PO₄)₇:Mn²⁺ can range from blue to red. By co-doping Ce³⁺ to Ca₁₀K(PO₄)₇:Mn²⁺, the emission intensity of Mn²⁺ is strongly enhanced due to an efficient energy transfer by [Ce³⁺ → Mn²⁺] and [defects → Ce³⁺ → Mn²⁺]. But under 147 nm excitation, the emission intensity of Mn²⁺ in Ca₁₀K(PO₄)₇:0.25Mn²⁺ decreases slightly compared with that in Ca₁₀K(PO₄)₇:025Mn²⁺, 0.1Ce³⁺, 0.1K⁺ due to the host sensitization competition between Ce³⁺ and Mn²⁺.     

Synthesis,tunable luminescence and thermal stability of Mg<Subscript>2</Subscript>Al<Subscript>4</Subscript>Si<Subscript>5</Subscript>O<Subscript>18</Subscript>:Ce<Superscript>3+</Superscript>/Mn<Superscript>2+</Superscript> phosphors

Ce³⁺/Mn²⁺ singly doped and codoped Mg₂Al₄Si₅O₁₈ phosphors were synthesized by a solid state reaction. The phase, luminescent properties and thermal stability of the synthesized phosphors were investigated. Ce³⁺ and Mn²⁺ singly doped Mg₂Al₄Si₅O₁₈ phosphors show emission bands locating in blue and yellow–red regions, respectively. In Ce³⁺ and Mn²⁺ codoped Mg₂Al₄Si₅O₁₈, tunable luminescence was obtained because of the energy transfer from Ce³⁺ to Mn²⁺. In Mg₂Al₄Si₅O₁₈:Ce³⁺/Mn²⁺ phosphors with a fixed Ce³⁺ concentration, energy transfer efficiency increases with the increasing Mn²⁺ concentration, which is confirmed by the continually decreasing intensity and shortening decay time of Ce³⁺ emission. Moreover, the luminescent properties and thermal stability provide a great significance on the applications in the field of light emitting diodes.     

Thermally stable luminescence and energy transfer in Ce, Mn doped Sr2Mg(BO3)2 phosphor

Sr₂Mg(BO₃)₂:Ce³⁺,Li⁺ and Sr₂Mg(BO₃)₂:Ce³⁺,Li⁺,Mn²⁺ phosphors have been synthesized by conventional solid state reaction technology at 900 °C for 12 h in reducing atmosphere. The phase purity, photoluminescence (PL) properties, thermal stability, energy transfer and luminescent decay curves have been investigated. Sr₂Mg(BO₃)₂:Ce³⁺,Li⁺,Mn²⁺ phosphors show blue and deep-red¹ emission bands. The deep-red emission band is attributed to the energy transfer from Ce³⁺ to Mn²⁺. The fluorescence lifetimes of Ce³⁺ in co-doped sample are shorter than that in single doped one, which confirms that the energy transfer takes place. The phosphors have weak thermal quenching. The luminescence properties of Sr₂Mg(BO₃)₂:Ce³⁺,Li⁺,Mn²⁺ make the phosphor a new bicolor emitting material.     

White light generation in Al2O3:Ce:Tb:Mn films deposited by ultrasonic spray pyrolysis

Aluminium oxide (Al₂O₃) films doped with CeCl₃, TbCl₃ and MnCl₂ were deposited at 300 °C with the ultrasonic spray pyrolysis technique. The films were analysed using the X-ray diffraction technique and they exhibited a very broad band without any indication of crystallinity, typical of amorphous materials. Sensitization of Tb³⁺ and Mn²⁺ ions by Ce³⁺ ions gives rise to blue, green and red simultaneous emission when the film activated by such ions is excited with UV radiation. The overall efficiency of such energy transfer results to be about 85% upon excitation at 312 nm. Energy transfer from Ce³⁺ to Tb³⁺ ions through an electric dipole-quadrupole interaction mechanism appears to be more probable than the electric dipole-dipole one. A strong white light emission for the Al₂O₃:Ce³⁺(1.3 at.%):Tb³⁺(0.2 at.%):Mn²⁺(0.3 at.%) film under UV excitation is observed. The high efficiency of energy transfer from Ce³⁺ to Tb³⁺ and Mn²⁺ ions, resulting in cold white light emission (x = 0.30 and y = 0.32 chromaticity coordinates) makes the Ce³⁺, Tb³⁺ and Mn²⁺ triply doped Al₂O₃ film an interesting material for the design of efficient UV pumped phosphors for white light generation.     

The luminescence of bismuth and manganese in LaMgB5O10

The luminescences of Bi³⁺ and Mn²⁺ in LaMgB₅O₁₀ are reported. The emission of the Bi₃₊ ion shows a small Stokes shift and is situated in the ultraviolet. From the decay times the ³P₀ and ³P₁ levels appear to be mixed. At 4.2 K no energy transfer between Bi³⁺ ions occurs, but at room temperature the critical distance for this energy transfer amounts to some 25 Å. This knowledge is used to explain energy transfer between Bi³⁺ and Tb³⁺ in LaMgB₅O₁₀, which is compared with that between Ce³⁺ and Tb³⁺ in the same lattice. The Mn²⁺ ion shows a red emission in LaMgB₅O₁₀. The Bi₃₊ ion acts as a sensitizer for this emission, whereas the Ce³⁺ ion does not.     

Studies on blue and red photoluminescence from Al2O3:Ce:Mncoatings synthesized by spray pyrolysis technique

Al₂O₃:Ce³⁺:Mn²⁺ films deposited by the spray pyrolysis technique show blue and red emissions under ultraviolet light excitation. The blue emission is due to the de-excitation of Ce³⁺ ions from their excited state 5d to the split ground state ²F. The usually weak red emission attributed to 3d→3d de-excitation of Mn²⁺ is enhanced through an efficient energy transfer from Ce³⁺ to Mn²⁺ ions. The quantum efficiency of this transfer is near to 100%. SEM and RBS have been used to analyze the surface morphology and chemical composition of Ce- and Mn-doped Al₂O₃ films. The films were also characterized by the X-ray photoelectron spectroscopy technique, and it was found that a considerable amount of Mn ions remains linked to chlorine while Ce is mostly in an oxidized state.     

Synthesis and tunable luminescence of RbCaGd(PO4)2:Ce3+, Mn2+ phosphors

RbCaGd(PO₄)₂ doped with Ce³⁺, Mn²⁺ was synthesized by the sol-gel method. The crystal structure and crystallographic location of Ce³⁺ in RbCaGd(PO₄)₂ were identified by Rietveld refinement. Powder X-ray diffraction (XRD) revealed that the structure of RbCaGd(PO₄)₂:Ce³⁺ compounds is hexagonal structure which is similar to that of hexagonal LnPO₄ with the lattice constant of a = b = 7.005(57) Å, c = 6.352(05) Å, and V (cell volume) = 269.980 Å³. The photoluminescence behavior and emission mechanism were studied systematically by doping activators in the RbCaGd(PO₄)₂ host. The Mn²⁺ incorporated RbCaGd(PO₄)₂:Ce³⁺, Mn²⁺ compounds exhibited blue emission from the parity- and spin-allowed f-d transition of Ce³⁺ and orange-to-red emission from the forbidden ⁴T₁ → ⁶A₁ transition of Mn²⁺. The emission chromaticity coordinates of RbCaGd(PO₄)₂:0.10Ce³⁺, xMn²⁺ (x = 0.16, 0.25) are close to the white region due to an energy transfer process and the energy transfer mechanism from Ce³⁺ to Mn²⁺ in the RbCaGd(PO₄)₂ host was dominated by dipole-dipole interactions.     

Synthesis,crystal structure and luminescence in Ca<Subscript>3</Subscript>Al<Subscript>2</Subscript>O<Subscript>6</Subscript>

Bluish green emitting phosphor, Ca₃Al₂O₆:Ce³⁺, is prepared by low-temperature combustion method. X-ray diffraction, photoluminescence, scanning electron microscopy techniques are used to characterize the synthesized phosphor. The most efficient bluish green (483 nm) emission is observed under the excitation by near UV light. The emission characteristics are credited to 5d → 4f type transitions in Ce³⁺. The luminescence properties of Eu²⁺ are predicted for the first time from those of Ce³⁺. Also, photoluminescence of Eu³⁺ is studied in the same host. The emission spectrum of Ca₃Al₂O₆:Eu³⁺ shows the peak at 592 (orange) and 614 nm (red) wavelengths. Ca₃Al₂O₆:Ce³⁺phosphor can be a potential blue phosphor for field emission display, solid-state lighting and LED.     

Influence of Mn<Superscript>2+</Superscript> on the up-conversion emission performance of Mn<Superscript>2+</Superscript>, Yb<Superscript>3+</Superscript>, Er<Superscript>3+</Superscript>: ZnWO<Subscript>4</Subscript> green phosphors

The Mn²⁺, Yb³⁺, Er³⁺: ZnWO₄ green phosphors are synthesized successfully through the high temperature solid state reaction method. The micro-structure and morphology have been investigated by means of XRD and EDS. The doped concentrations of Mn²⁺, Yb³⁺, Er³⁺ are measured by ICP. The absorption spectra and emission spectra with different doped concentrations of Mn²⁺ are presented to reveal the influence of Mn²⁺ on the green up-conversion performance. Excited with 970 nm LED, the up-conversion emission peak at 547 nm is obtained and the CIE spectra as well as the green light photo are also presented. The results indicate that the Mn²⁺ ions play the role of the luminescence adjustment in the up-conversion process, which can improve the up-conversion green emission intensity effectively. The luminescence adjustment mechanism of Mn²⁺ ions in Mn²⁺, Yb³⁺, Er³⁺: ZnWO₄ green phosphors has been discussed. The crystal parameters of Dq, B and C are calculated to evaluate the energy level split effect.     

Growth and optical properties of (Yb3−xYx)Al5O12:Ce single crystals

To improve the infrared emission of Yb³⁺ ions doped in the garnet host Y₃Al₅O₁₂ (YAG) single crystal through the energy transfer from Ce³⁺ to Yb³⁺ ions, the 〈1 1 1〉-oriented YAG:Ce³⁺, YAG:Yb³⁺, YAG:(Ce³⁺, Yb³⁺) and Yb₃Al₅O₁₂:Ce³⁺ (YbAG:Ce³⁺) single crystals were grown using the Czochralski Method, respectively. The excitation and emission spectra of these garnet single crystals were characterized. In YAG:Ce³⁺ crystal, the yellow emission of Ce³⁺ ions present, but it was completely extinguished in YAG:(Ce³⁺, Yb³⁺) crystal and YbAG:Ce³⁺ crystal. However, the characteristic absorption bands of Ce³⁺ still existed in the excitation spectrum of Yb³⁺ ions, which showed that the energy absorbed by Ce³⁺ ions can be transferred to Yb³⁺ ions for its infrared emission.     

Ca2SiO4:Ln (Ln = Ce3+, Eu2+, Sm3+) tricolor emission phosphors and their application for near-UV white light-emitting diode

Tricolor emission Ca₂SiO₄:Ln (Ln = Ce³⁺, Eu²⁺, Sm³⁺) phosphors were synthesized by the conventional solid-state reaction method, and their photoluminescence properties were investigated. Ce³⁺-, Eu²⁺-, or Sm³⁺-doped Ca₂SiO₄ phosphors showed typical blue, green, or red luminescence in the CIE1931 chromaticity diagram, respectively. In addition, the luminescence efficiency of the tricolor emission Ca₂SiO₄:Ln (Ln = Ce³⁺, Eu²⁺, Sm³⁺) phosphors was evaluated. A series of white light-emitting diode (LED) prototypes were fabricated by combining near-UV LED chip and the as-prepared tricolor emission phosphors with various ratios in weight. White LED prototypes with tunable correlated color temperature and color-rendering index values were realized by controlling the amount of phosphors. The presented results indicated the potential application of Ca₂SiO₄:Ln (Ln = Ce³⁺, Eu²⁺, Sm³⁺) phosphors in near-UV white LED.     

Synthesis and photoluminescence properties of a new red emitting phosphor: Ca3(VO4)2:Eu; Mn

A new red emitting phosphor, Ca₃(VO₄)₂:Eu³⁺; Mn²⁺, was synthesized by a citric acid sol-gel combustion method and characterized by XRD, TEM and photoluminescence (PL) spectra. The red emission located at about 613 nm was ascribed to ⁵D₀-⁷F₂ transition of Eu³⁺. And the red luminescence intensity changed with annealing temperature and concentration of Eu³⁺. The effect of the co-doped Mn²⁺ was also investigated systematically.     

Host-sensitized phosphorescence of Mn4+, Pr3+,4+ and Nd3+ in MgAl2Si2O8

Mn⁴⁺ doped and Pr^3+,4+, Nd³⁺ co-doped MgAl₂Si₂O₈-based phosphors were first of all synthesized about 1300 °C. They were characterized by thermogravimetry (TG), differential thermal analysis (DTA), X-ray powder diffraction (XRD), photoluminescence (PL) and scanning electron microscopy (SEM). The luminescence mechanism of the phosphors, which showed broad red emission bands in the range of 610–715 nm and had a different maximum intensity when activated by UV illumination, was discussed. Such a red emission can be attributed to the intrinsic d–d transitions of Mn⁴⁺.     

Synthesis and luminescence of BiPO4:Ln3+ (Ln = Ce3+, Tb3+) phosphors

BiPO₄:Ce³⁺ and BiPO₄:(Ce³⁺, Tb³⁺) powders were synthesized by the method of precipitation. The X-ray diffraction patterns show that BiPO₄:Ce³⁺ and BiPO₄:(Ce³⁺, Tb³⁺) samples have pure hexagonal phases. The transmission electron microscopy results show that the synthesized samples are nanoparticles. Ethylene glycol plays an important role in the formation of nanoparticles. The excitation spectrum of BiPO₄:Ce³⁺ sample shows the transition from the ground ² F _5/2 state to the excited 5d states of the Ce³⁺ ions. The emission spectrum exhibits a strong band centered at 352 nm originating from the 5d → 4f transitions of the Ce³⁺ ions. The emission spectrum of the BiPO₄:(Ce³⁺, Tb³⁺) sample contains both a weak emission band of the Ce³⁺ ions and strong green emission bands of the Tb³⁺ ions. The excitation and emission spectra show that there are energy transfers between Ce³⁺ and Tb³⁺ ions in the BiPO₄:(Ce³⁺, Tb³⁺) sample. The energy transfers between Ce³⁺ and Tb³⁺ ions improve the emission efficiency of BiPO₄:(Ce³⁺, Tb³⁺) sample.     

Spectroscopic properties of the Ce-doped borate glasses

The EPR, optical absorption and photoluminescence (emission and excitation) spectra as well as decay kinetics of a series of the Ce-doped glasses with Li₂B₄O₇, LiKB₄O₇, CaB₄O₇, and LiCaBO₃ compositions have been investigated and analysed. The borate glasses were obtained from the corresponding polycrystalline compounds in the air atmosphere, using standard glass technology. The EPR signals of the isolated Ce³⁺ and pair Ce³⁺–Ce³⁺ centres, coupled by magnetic dipolar and exchange interactions were registered at liquid helium temperatures. The characteristic for glass host broad bands corresponding to the 4f → 5d transitions of the Ce³⁺centres have been observed in the optical absorption and photoluminescence (emission and excitation) spectra. The obtained luminescence decay curves can be satisfactory described by exponential function with lifetimes in the 19.8–26.1 ns range, which depend on the basic glass composition. The local structure of Ce³⁺ centres in the investigated glasses has been considered and discussed.     

Novel blue-emitting phosphor NaMg4(PO4)3:Eu, Ce with energy transfer

A blue-emitting phosphor of NaMg₄(PO₄)₃:Eu²⁺, Ce³⁺ was prepared by a combustion-assisted synthesis method. The phase formation was confirmed by X-ray powder diffraction measurement. Photoluminescence excitation spectrum measurements show that the phosphor can be excited by near UV light from 230 to 400 nm and presents a dominant luminescence band centered at 424 nm due to the 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ ions at room temperature. Effective energy transfer occurs in Ce³⁺/Eu²⁺ co-doped NaMg₄(PO₄)₃ due to large spectral overlap between the emission of Ce³⁺ and excitation of Eu²⁺. Co-doping of Ce³⁺ enhances the emission intensity of Eu²⁺ greatly by transferring its excitation energy to Eu²⁺, and Ce³⁺ plays a role as a sensitizer. Ce³⁺-Eu²⁺ co-doped NaMg₄(PO₄)₃ powders can possibly be applied as blue phosphors in the fields of lighting and display.     

The persistent energy transfer of Eu and Mn and the thermoluminescence properties of long-lasting phosphor Sr3MgSi2O8:Eu, Mn, Dy

Eu²⁺, Mn²⁺ and Dy³⁺ co-doped long-lasting phosphors Sr₃MgSi₂O₈ were prepared by a solid-state reaction under a reductive atmosphere. Fluorescence spectra demonstrated that the weak red emission resulting from the forbidden transition of Mn²⁺ could be enhanced by the energy transfer from Eu²⁺ to Mn²⁺. The energy transfer between Eu²⁺ and Mn²⁺ was systematically investigated. The phosphorescence spectra revealed that Eu²⁺ could persistently transfer its energy to Mn²⁺ after removing the excitation source. The duration of Mn²⁺ can prolong to more than 2 h. The thermoluminescence spectra were used to characterize the ability of the trap to trapping the carriers. By the analysis of the ionization potentials, the roles of Mn²⁺ and Dy³⁺ in the afterglow process were discussed. A possible afterglow mechanism was presented and discussed.     

Energy transfer phenomena in GdMgB5O10

The luminescence of Mn²⁺, Bi³⁺, Ce³⁺ and Tb³⁺ in GdMgB₅O₁₀ and some codoped materials is reported. Energy transfer rates are derived from the experiments. The Bi³⁺ → Gd³⁺ and Gd³⁺ → Bi³⁺ transfer rates are about equal at room temperature. The excitation energy is able to migrate among the Gd³⁺ sublattice. The Ce³⁺ ion is a good sensitizer for this sublattice. By diluting the Gd³⁺ sublattice with La³⁺ ions, the energy migration in Gd³⁺ zig-zag chains was blocked and interchain energy transfer occurred. Very efficient phosphors can be obtained by using Ce³⁺ as a sensitizer, the Gd³⁺ sublattice as an intermediary and Tb³⁺ as an activator.     

Luminescence properties and energy transfer of a novel bluish-green tunable NaBa4(BO3)3:Ce3+, Tb3+ phosphor

A series of single-phased emission tunable NaBa₄(BO₃)₃:Ce³⁺, Tb³⁺ phosphors were synthesized by solid-state reaction. The crystal structure, photoluminescence properties, concentration quenching and energy transfer of NaBa₄(BO₃)₃:Ce³⁺, Tb³⁺ were systematically investigated. The wavelength-tunable bluish-green light can be realized by coupling the emission bands centered at 425 and 543 nm ascribed to the contribution from Ce³⁺ and Tb³⁺, respectively. The energy transfer from Ce³⁺ to Tb³⁺ in NaBa₄(BO₃)₃ host was studied and demonstrated to be a resonant type via a dipole–dipole interaction mechanism. The energy transfer efficiency (Ce³⁺ → Tb³⁺) obtained by decay curves was consistent with the result calculated by the emission intensity, which gradually increased from 0% to 84.5% by increasing the Tb³⁺ doping content from 0 to 0.45. The results indicate that the NaBa₄(BO₃)₃:Ce³⁺, Tb³⁺ phosphors have potential applications as an ultraviolet-convertible phosphor due to its effective excitation in the ultraviolet rang.     

Synthesis and properties of rare earth doped lamp phosphors

Red, blue and green emitting lamp phosphors such as Eu³⁺ doped Y₂O₃ (red phosphor), Eu²⁺ doped Ba_0·64Al₁₂O_18·64, BaMgAl₁₀O₁₇ and BaMg₂Al₁₆O₂₇ (blue phosphors) and Ce_0·67Tb_0·33MgAl₁₁O₁₉ and Eu²⁺, Mn²⁺ doped BaMgAl₁₀O₁₇ (green phosphors) have been prepared by the combustion of the corresponding metal nitrates (oxidizer) and oxalyl dihydrazide/urea/carbohydrazide (fuel) mixtures at 400°–500°C within 5 min. The formation of these phosphors has been confirmed by their characteristic powder X-ray diffraction patterns and fluorescence spectra. The phosphors showed characteristic emission bands at 611 nm (red emission), 430–450 nm (blue emission) and 515–540 nm (green emission). The fine-particle nature of the combustion derived phosphors has been investigated using powder density, particle size and BET surface area measurements. Paper presented at the poster session of MRSI AGM VI, Kharagpur, 1995