Luminescence spectroscopy and energy transfer in Eu2+/Mn2+-doped KCaPO4 phosphors

Eu²⁺/Mn²⁺-doped KCaPO₄ phosphors were prepared by conventional solid-state reaction. X-ray powder diffraction (XRD), SEM, photoluminescence excitation, and emission spectra, and the luminescence decay curves were measured. Mn²⁺ singly doped KCaPO₄ shows the weak origin-red luminescence band peaked at about 590 nm. The Eu²⁺/Mn²⁺ co-doped phosphors emit two distinctive luminescence bands: a blue one centered at 480 nm originating from Eu²⁺ ions and a broad red-emitting one peaked at 590 nm from Mn²⁺ ions. The luminescence intensity from Mn²⁺ ions can be greatly enhanced with the co-doping of Eu²⁺ ions. The efficient energy transfer from Eu²⁺ to Mn²⁺ was verified by the photoluminescence spectra together with the luminescence decay curves. The resonance-type energy transfer via a dipole–quadrupole interaction mechanism was supported by the decay lifetimes. The emission colors could be tuned by changing the Mn²⁺-doping concentration.     

Synthesis and photoluminescence properties of the high-brightness Eu3+-doped Sr3Bi(PO4)3 phosphors

A series of orange reddish emitting phosphors Eu³⁺-doped Sr₃Bi(PO₄)₃ have been successfully synthesized by conventional solid-state reaction, and its photoluminescence (PL) properties have been investigated. The excitation spectra reveal strong excitation bands at 392 nm, which match well with the popular emissions from near-UV light-emitting diode chips. The emission spectra of Sr₃Bi(PO₄)₃:Eu³⁺ phosphors invariably exhibit five peaks assigned to the ⁵D₀→⁷F_J (J=0, 1, 2, 3, 4) transitions of Eu³⁺ and have dominating emission peak at 612 nm under 392 nm excitation. The luminescence intensity was enhanced with increasing Eu³⁺ content and the emission reached the maximum intensity at x=0.05 in Sr₃Bi(PO₄)₃:xEu³⁺. The energy transfer behavior in the phosphors was discussed. The Commission Internationale de lEclairage (CIE) chromaticity coordinates, the quantum efficiencies, and the decay curves of the entitled phosphors excited under 392 nm are also investigated. The experimental results indicate that the Eu³⁺-doped Sr₃Bi(PO₄)₃ phosphors are promising orange reddish-emitting phosphors pumped by near-UV light.     

Synthesis, luminescence and crystallographic structure of Eu-doped garnet-type yafsoanite Ca3Te2(ZnO4)3

A red-emitting phosphor of Eu³⁺-doped calcium–tellurium–zinc oxide, Ca₃Te₂(ZnO₄)₃, with a garnet-type structure was synthesized by high temperature solid-state reactions. This phosphor exhibited a strong red emission. The photoluminescence excitation spectrum showed that Ca₃Te₂(ZnO₄)₃:Eu³⁺ can be effectively excited by UV–visible light. The property of long-wavelength excitation for this material has a benefit as a red phosphor in application of white light-emitting diodes. The colour coordinates were calculated. The excitation and emission spectra and luminescence decay curves were obtained using a pulsed, tunable, narrowband dye laser. Crystallographic sites and charge compensation mechanism of Eu³⁺ ions were discussed. The emission line from Eu³⁺ in intrinsic crystallographic site in the lattice was located at 579.56 nm. The emission line from Eu³⁺ in another disturbed site, which is created by the defects created by the charge-compensation, was located at 580.88 nm. The disordered crystallographic sites of Eu³⁺ are benefit for their strong red luminescence corresponding to the ⁵D₀→⁷F₂ transition.     

Crystal growth,luminescence and scintillation properties of Eu2+:CeBr3 crystals

Eu²⁺:CeBr₃ crystals were grown by vertical Bridgman growth method and slight aliovalent doping of Eu²⁺ in the CeBr₃ crystal did not change the crystal structure. The X-ray stimulated luminescence, photoluminescence, decay kinetics and scintillation properties were investigated at room temperature. The X-ray stimulated luminescence spectra exhibited wide broad emission bands from 3.54 eV to 2.95 eV in the Eu²⁺:CeBr₃ crystal with high content of 620 ppm of Eu²⁺, which were the overlap of the emission bands ascribed to 5d → 4f transition of Ce³⁺ and 4f⁶5 d¹ → 4f⁷ transition of Eu²⁺, respectively. When the content of Eu²⁺ was decreased to 70 ppm, another emission band centered at 2.29 eV was observed. The photoluminescence spectra showed the energy transfer from Ce³⁺ to Eu²⁺. This decreased the Ce³⁺ emission intensity but enhanced the Eu²⁺ emission intensity. The photoluminescence decay time of Ce³⁺ emission decreased from 14 ns to 10 ns when the content of Eu²⁺ increased from 70 ppm to 620 ppm. The decay time of the emission of 525 nm did not change with the excitation wavelength and Eu²⁺ content, which could be assigned to the excitons that were bound on Eu²⁺ related centers. The light output of the Eu:CeBr₃ crystal under the excitation of ²⁴¹Am radioactive source was less than 20.2% of Tl:NaI crystal.     

Luminescence properties of NaGd(PO3)4:Eu3+ and energy transfer from Gd3+ to Eu3+

The luminescence properties of polyphosphates NaEu _x Gd_(1?x)(PO₃)₄ (x = 0–1.00) and the energy transfer from Gd³⁺ to Eu³⁺ were studied. In undoped NaGd(PO₃)₄ sample, the photon cascade emission of Gd³⁺ was observed under ⁸S_7/2 → ⁶G_J excitation (201 nm) in which the emission of a red photon due to ⁶G_J → ⁶P_J transition is followed by an ultraviolet photon emission due to ⁶P_J → ⁸S_7/2 transition. When part of Gd³⁺ ions in the host NaGd(PO₃)₄ were substituted by Eu³⁺ ions, the NaGd(PO₃)₄:Eu³⁺ sample showed intensive red emission under 172-nm vacuum-ultraviolet (VUV) excitation which is suitable for mercury-free fluorescent lamps and plasma display panel applications. Based on the VUV–visible spectroscopic characteristics and the luminescence decay properties of NaGd(PO₃)₄:Eu³⁺, it was found that the quantum cutting by a two-step energy transfer from Gd³⁺ to Eu³⁺ can improve the red emission of Eu³⁺ ions under VUV excitation but only a part of the excitation energy in the excited ⁶P_J states within Gd³⁺ ions can be transferred to Eu³⁺ ions for its red emission, and the nonradiative energy transfer efficiencies from the excited ⁶P_J states within Gd³⁺ to Eu³⁺ were calculated.     

Sol-gel method and luminescence properties of the ZrO<Subscript>2</Subscript>:Eu<Superscript>3+</Superscript> phosphors with different charge compensation

Eu³⁺-doped ZrO₂ phosphors with different charge compensators (Li⁺, Na⁺, K⁺) were prepared by the sol-gel method. The properties of the as-obtained samples are characterized by X-ray diffraction, scanning electron microscope, photoluminescence spectra, and decay curve. The results show that ZrO₂:Eu³⁺ phosphors with different charge compensation are mixed phase of tetragonal and monoclinic phase, and the volume fraction of tetragonal phase of ZrO₂:Eu³⁺/Na⁺ phosphor is bigger than the other phosphors. The phosphors can emit strong red light at 606~616 nm (⁵D₀ → ⁷F₂) excited by ultraviolet light (395 nm). Compared with two charge compensation patterns in the ZrO₂:Eu³⁺, it has been found that ZrO₂:Eu³⁺ phosphors used Na⁺ as charge compensator show greatly enhanced red emission under 395 nm excitation and longer luminescence lifetime.     

Unusual luminescence of octahedrally coordinated divalent europium ion in Cs2MP2O7 (M=Ca, Sr)

The excitation and emission spectra of octahedrally coordinated europium ion (Eu²⁺) ions in Cs₂M²⁺P₂O₇ (M²⁺=Ca, Sr) are reported and discussed. The remarkable features of the Eu²⁺ luminescence in these phosphate materials include (a) very large Stokes shift of emission (∼1 eV), (b) high luminescence quenching temperature, and (c) unusually low energy of the emitted photons for Eu²⁺ luminescence in phosphate-based materials. The broad emission bands of Eu²⁺ in Cs₂CaP₂O₇ and Cs₂SrP₂O₇ peak at 607 and 563 nm, respectively. The Stokes shift, crystal field splitting, centroid shift and the red shift of the Eu²⁺ 4f⁶5d¹ electronic configuration have been estimated from the relevant optical data. The radiative lifetime of the Eu²⁺ emission in Cs₂M²⁺P₂O₇ is ∼1.2 μs. The nature of the Eu²⁺ emission in Cs₂M²⁺P₂O₇ is discussed and arguments are presented to associate the luminescence with an extreme case of normal 4f⁶5d¹→4f⁷[⁸S_7/2] emission.     

Synthesis and luminescent properties of Eu<Superscript>3+</Superscript>- and Eu<Superscript>2+</Superscript>-activated sodium pyrophosphate Na<Subscript>4</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>

The luminescent properties of Eu³⁺ and Eu²⁺ ions in sodium pyrophosphate, Na₄P₂O₇, have been studied. The excitation spectrum of the Eu³⁺ emission in Na₄P₂O₇ consists of several sets of bands in the range 280–535 nm due to 4f–4f transitions of Eu³⁺ ions and a broad band with a maximum at about 240 nm interpreted to be due to a charge transfer (CT) transition from oxygen 2p states to empty states of the Eu³⁺ 4f⁶-configuration. Although the CT band energy is large enough, the quantum efficiency (η) of the Eu³⁺ emission in Na₄P₂O₇ under CT excitation was estimated to be very low (η ≤ 0.01). In terms of a configurational coordinate model, this fact is interpreted as a result of the high efficiency of a radiationless relaxation from the CT state to the ⁷F₀ ground state of Eu³⁺ ions occupying sodium sites in Na₄P₂O₇. A strong reducing agent is required in order to stabilize Eu²⁺ ions in Na₄P₂O₇ during the synthesis. Several nonequivalent Eu²⁺ luminescence centers in Na₄P₂O₇ were found.     

Effect of Na+ co-dopant and activator concentration on luminescent properties of CaGa4O7:Eu3+

Two series of calcium gallate phosphors: Ca_1?xEu_xGa₄O₇ and Ca_1?2xEu_xNa_xGa₄O₇ (x=0, 0.002, 0.01, 0.02, 0.03, 0.05) were synthesized by a modified Pechini method and their optical properties at 298 and 77 K were investigated. In undoped CaGa₄O₇ upon 255 nm excitation a bluish white emission (λ_max=500 nm) followed by an afterglow of the same color lasting for 10–20 s was observed. Eu³⁺-doping quenched the host-related luminescence and the characteristic red emission of the dopant with maximum at 613 nm appeared. Its excitation spectrum consisted of a broad band assigned to ligand to metal, O^2?→Eu³⁺, charge transfer absorption and narrow lines arising from intraconfigurational transitions within the 4f⁶ states of Eu³⁺ ion. The effects of Eu³⁺ concentration and Na⁺ co-doping on the luminescence properties and decay kinetics were studied. Low temperature emission spectra showed that Eu³⁺ ions are positioned in environments of different symmetries. Their relative populations changed with the activator content. Co-doping with Na⁺ ions led to a remarkable reduction of the number of Eu³⁺ sites as well as to noticeable improvement of the luminescence brightness though it did not affect the decay time of the emission. The quantum efficiencies of singly doped CaGa₄O₇:Eu³⁺ were very low (in the range of 1–3.7%). Na⁺ co-doping improved this parameter leading to the highest efficiency of 11% for CaGa₄O₇:3%Eu³⁺,3%Na⁺.     

Persistent luminescence properties of SrMg2(PO4)2:Eu2+,Tb3+

We investigate the persistent luminescence in europium-doped SrMg₂(PO₄)₂ upon codoping with auxiliary terbium. Luminescence properties of the phosphors, including photoluminescence, luminescence decay and thermoluminescence, are systematically studied. SrMg₂(PO₄)₂:Eu²⁺ shows only a weak persistent luminescence, and codoping with Tb³⁺ is necessary to obtain considerable persistent luminescence. An energy level scheme is constructed to convey reasonable trapping and detrapping processes in the material.     

Luminescence properties of SrSi2O2N2 doped with divalent rare earth ions

The optical properties of SrSi₂O₂N₂ doped with divalent Eu²⁺ and Yb²⁺ are investigated. The Eu²⁺ doped material shows efficient green emission peaking at around 540 nm that is consistent with 4f⁷→4f⁶5d transitions of Eu²⁺. Due to the high quantum yield (90%) and high quenching temperature (>500 K) of luminescence, SrSi₂O₂N₂:Eu²⁺ is a promising material for application in phosphor conversion LEDs. The Yb²⁺ luminescence is markedly different from Eu²⁺ and is characterized by a larger Stokes shift and a lower quenching temperature. The anomalous luminescence properties are ascribed to impurity trapped exciton emission. Based on temperature and time dependent luminescence measurements, a schematic energy level diagram is derived for both Eu²⁺ and Yb²⁺ relative to the valence and conduction bands of the oxonitridosilicate host material.     

Luminescence and time-resolved spectroscopy properties of (Gd1−xEux)(BO2)3 multicrystals

(Gd_1?xEu_x)(BO₂)₃ (0≤x≤1) phosphors are synthesized by traditional high temperature solid state reaction. The photoluminescence (PL) properties of Gd(BO₂)₃ and Gd(BO₂)₃ activated with Eu³⁺ are investigated. The PL spectra exhibit the typical characteristic emission and excitation of Gd³⁺ and Eu³⁺ ions, and support the energy transfer taking place from Gd³⁺ to Eu³⁺ ions. The relationship between Eu³⁺ doping concentration and emission intensity is also studied. Even if all of the Gd³⁺ ions are substituted by Eu³⁺ ions, the concentration quenching between Eu³⁺ happens. However, the quenching is not complete. The luminescence decay curves are measured, and the lifetimes become short with the Eu³⁺ content increasing. The decreasing Gd³⁺ lifetimes also indicates that there exists efficient energy transfer between Gd³⁺ and Eu³⁺ ions.     

Luminescence and energy transfer in Eu2+,Mn2+ codoped Na2BaMgP2O8 phosphor

Eu²⁺ single-doped and Eu²⁺/Mn²⁺-codoped Na₂BaMgP₂O₈ phosphors were prepared by a combustion-assisted synthesis method. The phase formation was confirmed by X-ray powder diffraction measurement. Na₂BaMgP₂O₈:Eu²⁺,Mn²⁺ shows a broad blue emission band and a red emission band, which originate from Eu²⁺ occupying the Ba²⁺ sites and Mn²⁺ occupying the Mg²⁺ sites, respectively. The efficient energy transfer from Eu²⁺ to Mn²⁺ is verified by the excitation and emission spectra together with the luminescence decay curves. Based on the principle of energy transfer, the relative intensities of blue and red emissions could be tuned by adjusting the contents of Eu²⁺ and Mn²⁺.     

Synthesis and luminescence properties of Na2Ba2Si2O7:Eu2+ phosphor

Green-emitting phosphor Na₂Ba₂Si₂O₇:Eu²⁺ has been synthesized by a conventional high-temperature solid-state reaction. The phase structure and luminescence properties are characterized by the X-ray powder diffraction, diffuse reflectance spectra, photoluminescence excitation and emission spectra, temperature-dependent emission spectra, respectively. It can be efficiently excited in the wavelength range of 325–400 nm and consists of a strong broad green band centered at about 501 nm, which is ascribed to 4f⁶6s⁰5d¹ → 4f⁷6s²5d⁰ transition of Eu²⁺. The critical quenching concentration of Eu²⁺ in the Na₂Ba₂Si₂O₇ host is about 0.8 mol % and corresponding quenching behavior is ascribed to be electric dipole–dipole interaction. Furthermore, the phosphor has good thermal stability property, and the activation energy for thermal quenching is calculated as 0.34 eV.     

KBaPO4:Ln (Ln=Eu, Tb, Sm) phosphors for UV excitable white light-emitting diodes

This letter reports the novel three emission bands based on phosphate host matrix, KBaPO₄ doped with Eu²⁺, Tb³⁺, and Sm³⁺ for white light-emitting diodes (LEDs). The phosphors were synthesized by solid-state reaction and thermal stability was elucidated by measuring photoluminescence at higher temperatures. Eu²⁺-doped KBaPO₄ phosphor emits blue luminescence with a peak wavelength at 420 nm under maximum near-ultraviolet excitation of 360 nm. Tb³⁺-doped KBaPO₄ phosphor emits green luminescence with a peak wavelength at 540 nm under maximum near-ultraviolet excitation of 370 nm. Sm³⁺-doped KBaPO₄ phosphor emits orange-red luminescence with a peak wavelength at 594 nm under maximum near-ultraviolet excitation of 400 nm. The thermal stabilities of KBaPO₄:Ln (Ln=Eu²⁺, Tb³⁺, Sm³⁺), in comparison to commercially available YAG:Ce³⁺ phosphor were found to be higher in a wide temperature range of 25-300 °C.     

Intense green-emitting Sr2LiSiO4F:Eu2+ phosphor for n-UV white LEDs

Eu²⁺-activated Sr₂LiSiO₄F phosphors were synthesized at 900°C by solid-state reaction in reducing atmosphere, and their photoluminescence (PL) properties were systematically investigated by diffuse reflection spectra, PL excitation and emission spectra, and by the fluorescence decay curve. Sr₂LiSiO₄F:Eu²⁺ emits intense green light at 520 nm originating from the 5d¹4f⁶−4f⁷ transition of Eu²⁺ under 365 nm n-UV excitation. The PL excitation spectrum matches the emission from n-UV chips. These materials could be promising green phosphors for use in generating white light in phosphor-converted white light-emitting-diodes (LEDs).     

Near infrared and charge transfer luminescence of Yb-doped LaPO4 at room temperature

The Yb³⁺-doped LaPO₄ was prepared by hydrothermal reaction under fine acidity control and identified by X-ray diffraction and FT-IR spectroscopy. The obtained powders crystallize in the monoclinic phase of LaPO₄. The spectroscopic study at room temperature (RT) of the Yb³⁺-doped LaPO₄ powder was investigated. Thus a wide band, characteristic of the fundamental ²F_5/2↔²F_7/2 transition in near infrared (NIR) range, has been located for La_(1−x)Yb_xPO₄ (x = 5, 10%). Four Stark levels of the ground ²F_7/2 state are located on the emission spectra between 976 nm and 1030 nm, after excitation at 925 nm. Low re-absorption of the 0-phonon transition was registered. Charge transfer band (CTB) luminescence of Yb³⁺, which is not observed in LaPO₄ in later works, was appeared under 266 nm excitation. In the UV–Visible spectra, double band typical for the CTB luminescence of Yb³⁺ are observed. The decay time dependence as a function of the concentration is also reported and compared to other works. The room temperature radiative lifetimes of the IR emission and charge transfer band luminescence are compatible with potential applications of this phosphor respectively as solid-state lasers and scintillators.     

An efficient blue-emitting phosphor LiCaPO4:Eu2+ for white LEDs

A new blue-emitting phosphor LiCaPO₄: Eu²⁺ was synthesized by solid state reaction at a relatively low temperature of 900 °C. It gives a single intense emission band centering at 470 nm, which corresponds to the 4f⁶5d¹→4f⁷ transition of Eu²⁺. The dependence of luminescence intensities on Eu²⁺ concentration was investigated. The phosphor, with a single excitation band extending from 250 to 400 nm, could be efficiently excited by near-ultraviolet light-emitting diodes and is believed to be a promising blue-emitting phosphor for white light-emitting diodes.     

Luminescent properties of SrMg<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>:Eu<Superscript>2+</Superscript>, and Mn<Superscript>2+</Superscript> as a potential phosphor for ultraviolet light-emitting diodes

Eu²⁺ and Mn²⁺ co-doped SrMg₂(PO₄)₂ phosphors with blue and red two emission bands were prepared by the high temperature solid state method and their luminescent properties have been investigated as a function of activator and co-activator concentrations. Resonance-type energy transfers from Eu²⁺ to Mn²⁺ were discovered by directly overlapping the Eu²⁺ emission spectrum and the excitation spectrum of Mn²⁺. Efficiencies of energy transfer were also calculated according to the changes of relative intensities of Eu²⁺ and Mn²⁺ emission. According to the principle of energy transfer, we demonstrated that the phosphor SrMg₂(PO₄)₂:Eu²⁺,Mn²⁺ with double emission bands exhibited a great potential as a phosphor for ultraviolet light-emitting diodes and the relative intensities of blue and red emission could be tuned by adjusting the contents of Eu²⁺ and Mn²⁺. PACS 78.55.-m     

Synthesis and Optical Properties of Eu3+ Ion Doped Nanocrystalline Hydroxyapatites

The Ca₁₀(PO₄)₆(OH)₂ hydroxyapatite (HA) nanopowders doped with Eu³⁺ ions were prepared using a wet synthesis method. Their structure and morphology were investigated. The XRD analysis has proven a single-phase of HA nanocrystallites. The average sizes of HA nanocrystallites calcinated at 400°C and 700°C were determined to be about 20 nm and 30 nm, respectively. The emission and excitation spectra as well as the fluorescence decay rates of Eu³⁺ ion doped HA nanocrystallites were measured. Particular attention was given to the spectroscopic properties of Eu³⁺ ions as a luminescent probe of nanocrystalline HA structure as a result of varying annealing temperature and dopant concentration. The Judd-Ofelt analysis of f-f transitions of Eu³⁺:HA nanocrystallites was performed. The effect of calcination temperatures on grain sizes and luminescence properties is noted and discussed.