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⁺.     

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.     

Luminescent properties of Sr2P2O7:Eu,Mn phosphor under near UV excitation

The phosphors in the system Sr_2−x−yP₂O₇:xEu²⁺,yMn²⁺ were synthesized by solid-state reactions and their photoluminescence properties were investigated. These phosphors have strong absorption in the near UV region, which is suitable for excitation of ultraviolet light emitting diodes (UVLEDs). The orange-reddish emission of Mn²⁺ in these phosphors can be used as a red component in the tri-color system and may be enhanced by adjusting the Mn²⁺/Eu²⁺ ratio. The energy transfer from Eu²⁺ to Mn²⁺ is observed with a transfer efficiency of ∼0.45 and a critical distance of ∼10 Å. The results reveal that Sr_2−x−yP₂O₇:xEu²⁺,yMn²⁺ phosphors could be used in white light UVLEDs.     

Synthesis and blue to near-infrared quantum cutting of Pr/Yb co-doped Li2TeO4 phosphors

Near-infrared (NIR) quantum cutting luminescent materials Li₂TeO₄ doped with Pr³⁺ and Yb³⁺ were synthesized by solid-state reaction method. The dependence of Yb³⁺ doping concentration on the visible- and NIR-emissions, decay lifetime, and quantum efficiencies of the phosphors are investigated. Quantum cutting down-conversion involving 647 nm red emission and 960-1050 nm broadband near-infrared emission for each 487 nm blue photon absorbed is realized successfully in the resulting phosphors, of which the process of near-infrared quantum cutting could be expressed as ³P₀(Pr³⁺) → ²F_5/2(Yb³⁺) + ²F_5/2(Yb³⁺). The maximum quantum cutting efficiency approaches up to 166.4% in Li₂TeO₄: 0.3 mol%Pr³⁺, 1.8 mol%Yb³⁺ sample corresponding to the 66.4% value of energy transfer efficiency.     

A novel blue-emitting Sr3Al2O5Cl2:Ce,Li phosphor for near UV-excited white-light-emitting diodes

A novel blue-emitting Sr₃Al₂O₅Cl₂:Ce³⁺,Li⁺ phosphor has been synthesized by solid state reaction. The excitation spectrum shows a broad band extending from 300 to 400 nm, and the emission spectrum shows a broad blue band peaking at 450 nm with a half width of about 100 nm. The emission intensity at 250 °C remains at about 50% of that at room temperature. The decay curve at the emission peak consists of fast and slow components. The Sr₃Al₂O₅Cl₂:Ce³⁺,Li⁺ should be a promising blue phosphor for near ultraviolet-based white-light-emitting diodes.     

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.     

A red-emitting heavy doped phosphor Li6Y(BO3)3:Eu for white light-emitting diodes

A series of Eu³⁺ activated Li₆Y_1−xEu_x(BO₃)₃ (0.05 ? x ? 1) phosphors were synthesized by solid-state reaction method. The structures and photoluminescent properties of the phosphors were investigated at room temperature. The results of XRD patterns indicate that these phosphors are isotypic to the monoclinic Li₆Gd(BO₃)₃. The excitation spectra indicate that these phosphors can be effectively excited by near UV (370-410 nm) light. The red emission from transition ⁵D₀→⁷F₂ is dominant. The emission spectra exhibit strong red performance (CIE chromaticity coordinates: x = 0.65, y = 0.35), which is due to the ⁵D₀−⁷F_J transitions of Eu³⁺ ions. The relationship between the structure and the photoluminescent properties of the phosphors was studied. The concentration quenching occurs at x ≈ 0.85 under near UV excitation. Li₆Y(BO₃)₃:Eu³⁺ has potential application as a phosphor for white light-emitting diodes.     

Influence of excitation wavelengths on luminescent properties of Sr3Al2O6:Eu, Dy phosphors prepared by sol-gel-combustion processing

Eu²⁺ and Dy³⁺ ion co-doped Sr₃Al₂O₆ red-emitting long afterglow phosphor was synthesized by sol-gel-combustion methods using Sr(NO₃)₂, Al(NO₃)₃·9H₂O, Eu₂O₃, Dy₂O₃, H₃BO₃ and C₆H₈O₇·H₂O as raw materials. The crystalline structure of the phosphors were characterized by X-ray diffraction, luminescent properties of phosphors were analyzed by fluorescence spectrophotometer. The effect of excitation wavelengths on the luminescent properties of Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphors was discussed. The emission peak of Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphor lays at 516 nm under the excitation of 360 nm, and at 612 nm under the excitation of 468 nm. The results reveal that the Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphor will emit a yellow-green light upon UV illumination, and a bright red light upon visible light illumination. The emission mechanism was discussed according to the effect of nephelauxetic and crystal field on the 4f⁶5d¹ → 4f⁷ transition of the Eu²⁺ ions in Sr₃Al₂O₆. The afterglow time of (Sr_0.94Eu_0.03Dy_0.03)₃ Al₂O₆ phosphors lasts for over 600s after the excited source was cut off.     

Enhanced red emission in ZnB2O4:Eu by charge compensation

Eu³⁺ doped ZnB₂O₄ without or with different charge compensation (CC) approaches (co-doping Li⁺, Na⁺, K, decreasing the content of Zn²⁺) were prepared by solid state reactions. The phosphors can strongly absorb 393 nm ultraviolet (UV) light which is coupled well with the emission of currently used InGaN-based near UV light emitting diodes (LEDs) and emit red light with a good color purity. The luminescent intensity of phosphors can be remarkably enhanced with any of CC methods. However, the shape and position of excitation and emission spectra keep unchanged. The introduction of Li⁺ can enhance the red emission intensity of Eu³⁺ by ∼4 times with the optimal effect. Red emission of Eu³⁺ can also be enhanced with the other three CC approaches but the effects are not as good as Li⁺ because the volume unbalance in Li⁺ compensation approach is the smallest while net positive charge was offset. The results of this work suggest that volume compensation and equilibrium of mole number should also be taken into account when a CC approaches is selected.     

Synthesis and photoluminescence of new phosphors M2(Mg, Zn)Si2O7:Mn (M = Ca, Sr, Ba)

New phosphors M₂(Mg, Zn)Si₂O₇:Mn²⁺ (M = Ca, Sr, Ba) were prepared by sol-gel process, and their luminescent properties in ultraviolet and vacuum ultraviolet region were investigated. The results showed that the (Ca, Sr, Ba)₂MgSi₂O₇:Mn²⁺ samples did not emit any visible light; the Sr₂ZnSi₂O₇:Mn²⁺ and Ca₂ZnSi₂O₇:Mn²⁺ samples showed green light. The Ba₂ZnSi₂O₇:Mn²⁺ sample mainly showed green light under 254 nm excitation and red light under 147 nm excitation. The different emission was due to the Mn²⁺ ions occupied different sites, which were excited selectively. Among the three phosphors Sr₂ZnSi₂O₇:Mn²⁺ showed the highest green emission intensity, and its decay time was shorter than that of Zn₂SiO₄:Mn²⁺ under 147 nm excitation.     

Photoluminescence and radioluminescence of pure and Ce activated Na3Gd(PO4)2

The spectroscopic properties of Na₃Gd(PO₄)₂ and Na₃Gd(PO₄)₂:Ce³⁺ phosphors in the VUV-UV spectral range were investigated. Five excitation bands of Ce³⁺ ions at Gd³⁺ sites are observed at wavelengths of 205, 246, 260, 292, and 321 nm. Doublet Ce³⁺ 5d → 4f emission bands are observed at 341 and 365 nm with a decay constant τ_1/e around 26 ns. The X-ray excited luminescence of Na₃Gd_0.99Ce_0.01(PO₄)₂ at room temperature shows a photon yield of ∼17,000 photons/MeV of absorbed X-ray energy.     

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.     

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.     

Near-ultraviolet excitable Ca4Y6(SiO4)6O: Ce,Tb white phosphors for light-emitting diodes

The present investigation aims to demonstrate the potentiality of Tb³⁺ and Ce³⁺ co-doped Ca₄Y₆(SiO₄)₆O phosphors. By incorporation of Ce³⁺ into Ca₄Y₆(SiO₄)₆O: Tb³⁺, the excitation band was extended from short-ultraviolet to near-ultraviolet region. The energy transfer from Ce³⁺ to Tb³⁺ in Ca₄Y₆(SiO₄)₆O host was investigated and demonstrated to be a resonant type via a dipole–dipole mechanism with the critical distance of 10.2 Å. When excited by 352 nm, Ca₄Y₆(SiO₄)₆O: Ce³⁺, Tb³⁺ exhibited a brighter and broader violet-blue emission (421 nm) from the Ce³⁺ and an intense green emission (542 nm) from the Tb³⁺. Combining the two emissions whose intensities were adjusted by changing the doping levels of the co-activator, an optimized white light with chromaticity coordinates of (0.278, 0.353) is generated in Ca₄Y₆(SiO₄)₆O: 2% Ce³⁺, 8% Tb³⁺, and this phosphor could be potentially used in near-ultraviolet light-emitting diodes.     

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.     

Sr3Bi(PO4)3:Eu2+, Mn2+: Single-phase and color-tunable phosphors for white-light LEDs

Sr₃Bi(PO₄)₃:Eu²⁺, Sr₃Bi(PO₄)₃:Mn²⁺, and Sr₃Bi(PO₄)₃:Eu²⁺, Mn²⁺ phosphors were synthesized by solid state reaction. The structure and luminescent characteristics were investigated by X-ray powder diffraction and fluorescent spectrophotometer. All samples have the structural type of eulytine. The excitation and emission spectra of Sr₃Bi(PO₄)₃:0.01Eu²⁺ sample show characteristic bands of Eu²⁺ ions. Also, the excitation and emission spectra of Sr₃Bi(PO₄)₃:0.06Mn²⁺ sample show characteristic bands of Mn²⁺ ions. The emission color of Sr₃Bi(PO₄)₃:Eu²⁺, Mn²⁺ sample could be tuned through tuning the co-dopant concentration of Mn²⁺ ions. The decay times for the Eu²⁺ ions decrease with the increase of Mn²⁺ dopant concentration, but the energy transfer efficiency increases with the increase of Mn²⁺ dopant concentration. On the basis of the luminescent spectra and fluorescence decay curves, we confirm that the energy transfer process from the Eu²⁺ to Mn²⁺ ions takes place in the co-doped Sr₃Bi(PO₄)₃ phosphor. Sr₃Bi(PO₄)₃:Eu²⁺, Mn²⁺ sample shows the good thermostability. The emission intensity of the sample at 400 K is about 60% of the value at 300 K. These results show Sr₃Bi(PO₄)₃:Eu²⁺, Mn²⁺ phosphors could be anticipated for UV-pumped white-light-emitting diodes.     

Influence of Ce on the luminescence properties of Er/Yb:YVO4 crystals

YVO₄ single crystals doped with Ce³⁺, Er³⁺ and Yb³⁺ ions were grown by the Czochralsski technology. The luminescence properties of Er³⁺/Yb³⁺:YVO₄ single crystals with different concentration of Ce³⁺ were studied, and the energy transfer mechanism between Er³⁺, Yb³⁺ and Ce³⁺ was discussed based on their energy level properties. The branching ratios of the ⁴I_11/2 → ⁴I_13/2 transition in different samples were calculated. The results indicate that codopants of Ce³⁺ greatly enhance the population rate of the ⁴I_13/2 level due to the fast resonant energy transfer between Er³⁺ and Ce³⁺, i.e., ⁴I_11/2(Er³⁺) + ²F_7/2(Ce³⁺) → ⁴I_13/2(Er³⁺) + ²F_5/2(Ce³⁺).     

Luminescent properties of Sr2Al2SiO7:Ce3+,Eu2+ phosphors for near UV-excited white light-emitting diodes

The Sr₂Al₂SiO₇:Eu²⁺, Ce³⁺ phosphors were synthesized by a high temperature solid-state reaction. Effective energy transfer occurs in Ce³⁺ and Eu²⁺ co-doped Sr₂Al₂SiO₇ due to large spectral overlap between the emission of Ce³⁺ and excitation of Eu²⁺ ions. Co-doping of Ce³⁺ enhances the emission intensity of Eu²⁺ greatly by transferring its excitation energy to Eu²⁺ ions. The critical distance has been estimated to be about 1.83 nm by spectral overlap method. Furthermore, the developed phosphors can generate lights from blue to green region under the excitation of UV radiation by appropriately tuning the activator content. The Sr₂Al₂SiO₇:Eu²⁺,Ce³⁺ phosphors are promising phosphors for warm-white-light-emitting diode because of its effective excitation in the near ultraviolet range.     

Photoluminescence of Tb and Mn activated Ca8MgGd(PO4)7 under vacuum ultraviolet excitation

Novel Tb³⁺ and Mn²⁺ activated Ca₈MgGd(PO₄)₇ phosphors were synthesized by solid-state reaction and their photoluminescence properties in vacuum ultraviolet region were investigated for the first time. It can be observed from the excitation spectra that the host-related absorption band is located around 170 nm, and it overlaps the O²⁻ → Tb³⁺ charge transfer band of Ca₈MgGd(PO₄)₇:Tb³⁺ around 161 nm and the 3d⁵ → 3d⁴4s transition band of Ca₈MgGd(PO₄)₇:Mn²⁺ near 200 nm. The 4f-4f 5d spin-allowed and spin-forbidden transitions of Tb³⁺ are verified to be located at 170-250 and 257-271 nm, respectively. Upon 147 nm excitation, the dominant emission peak intensity of the Ca₈MgGd_0.1(PO₄)₇:0.9Tb³⁺ phosphor is about 2.7 times stronger than that of the commercial Zn₂SiO₄:Mn²⁺ green phosphor, and the brightness of the former with a short decay time of 2.5 ms is about 98% of the latter’s. The Ca₈MgGd(PO₄):Mn²⁺ phosphor excited at 147 nm exhibits a deep red emission around 650 nm, which could be attributed to the ⁴T₁ → ⁶A₁ transition of Mn²⁺, with the CIE index (0.679, 0.321). In a word, the results above indicate that both Tb³⁺ and Mn²⁺ activated Ca₈MgGd(PO₄)₇ phosphors could be promising for PDP or Hg-free lamp applications.     

Energy transfer processes in Ce and Tb co-doped Ln2Si2O7 (Ln = Y, Gd)

The Ce³⁺ and Tb³⁺ co-doped Ln₂Si₂O₇ (Ln = Y, Gd) samples were prepared by sol-gel method. Structure characterization of the phosphor was carried out by X-ray diffraction. The luminescence properties of samples were analyzed by measuring the excitation and emission spectra. It was observed that excitation energy can transfer mutually between Ce³⁺ and Tb³⁺ in GPS: Ce³⁺, Tb³⁺ samples, while in Y₂Si₂O₇ :Ce³⁺, Tb³⁺ samples the energy transfer only progresses from Ce³⁺ to Tb³⁺. Based on the energy level diagrams of respective Ce³⁺, Tb³⁺ and Gd³⁺ ion, the detailed pathways for energy transfer are explained.