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.     

Photoluminescence properties of color-tunable SrMgAl10O17:Eu2+,Mn2+ phosphors for UV LEDs

Aluminate phosphors SrMgAl₁₀O₁₇ codoped with Eu²⁺ and Mn²⁺ ions were prepared by solid-state reaction. The phase structure and photoluminescence properties of the as-prepared phosphors were characterized by powder X-ray diffraction, photoluminescence excitation and emission spectra. Upon excitation of UV light, two broad emission bands centered at 470 and 515 nm were observed, and they were assigned to Eu²⁺ and Mn²⁺ emissions, respectively. The emission color of the phosphors can be tuned from blue to cyan and finally to green by adjusting the concentration ratios of Eu²⁺ and Mn²⁺. Effective energy transfer occurs from Eu²⁺ to Mn²⁺ in the host due to the spectral overlap between the emission band of Eu²⁺ and the excitation bands of Mn²⁺. The energy transfer mechanism was demonstrated to be electric dipole–quadrupole interaction. The energy transfer efficiency and critical distance were also calculated. The phosphors exhibit strong absorption in near UV spectral region and therefore they are potentially useful as UV-convertible phosphors for white LEDs.     

Structural,photoluminescent, and dielectric properties of Eu3+-doped Ba0.7Sr0.3TiO3 thin films

Eu³⁺-doped Ba_0.7Sr_0.3TiO₃ thin films were prepared by a chemical solution deposition method and characterized by X-ray diffraction, field emission scanning electron microscopy, photoluminescence and dielectric measurements. The thin films were well crystallized with a pure perovskite structure. A contraction of the unit cell was observed upon incorporation of Eu³⁺ ions below 2 mol%, while an expansion occurred as the Eu³⁺ concentration was further increased above 2 mol%, indicating that Eu³⁺ ions with different concentrations occupied different lattice sites. Photoluminescence spectra showed two prominent transitions of Eu³⁺ ions at 594 nm (⁵D₀ → ⁷F₁) and 618 nm (⁵D₀ → ⁷F₂) upon excitation at 395 nm (⁷F₀ → ⁵L₆). There existed two quenching concentrations at 2 mol% and 4 mol% due to different lattice sites of the Eu³⁺ ions. We also investigated the dielectric properties of the thin films. Our study suggests that Eu³⁺-doped Ba_0.7Sr_0.3TiO₃ thin films have potential applications in multifunctional optoelectronic devices.     

Luminescence and scintillation of Eu2+‐doped high silica glass

High silica glass doped with Eu²⁺ ions was prepared as a scintillating material by impregnation of Eu ions into a porous silica glass followed by reduction sintering in CO atmosphere. A dominant emission band of the Eu²⁺ 5d–4f transition peaking around 430 nm was observed in the luminescence spectrum with the excitation peak around 280 nm and no emission from Eu³⁺ was present. Photoluminescence decay kinetics was governed by decay times of a few microseconds. The Eu²⁺‐doped high silica glass exhibited comparable energy resolution and slightly higher photoelectron yield with respect to the Bi₄Ge₃O₁₂ crystal in the pulse height spectra for X‐ray photon energies within 22–60 keV. Furthermore, a factor of 1.2 higher radioluminescence intensity was observed as well. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation and photoluminescence properties of the Eu2+, Sm3+ co-doped Li2SrSiO4 phosphors

A series of Eu²⁺ and Sm³⁺ co-doped Li₂SrSiO₄ phosphors are prepared by the high temperature solid-state reaction. The morphology, structure and spectroscopic properties of the prepared samples are characterized by scanning electron microscopy, X-ray diffraction, diffuse reflection spectra, photoluminescence spectra and electron paramagnetic resonance spectra, respectively. The effect of Sm³⁺ doping concentration on the photoluminescence intensity of the prepared samples is also investigated. The results indicate that the crystal structure of Li₂SrSiO₄ is not changed with the Eu²⁺, Sm³⁺ co-doping. The spherical-like particle size of the obtained product is about 20–30 nm in diameter. When the Sm³⁺ concentration is 0.3 mol% and the Eu²⁺ concentration is 0.7 mol%, the phosphors show the maximum emission intensity, which is 50% higher than that of Eu²⁺ doped Li₂SrSiO₄. Excited at 420 nm, the phosphor presents a single broad emission band peaking at 558 nm, which is ascribed to the 4f⁶5d¹ → 4f⁷ transitions of Eu²⁺ and ⁴G_5/2 → ⁶H_5/2 and ⁴G_5/2 → ⁶H_7/2 transitions of Sm³⁺. The Commission International de I′Eclairage chromaticity coordinates of Li₂SrSiO₄:0.7 mol% Eu²⁺, 0.3 mol% Sm³⁺ are x = 0.28, y = 0.28.     

用于白光LED的单一基质白光荧光粉Ca2SiO3Cl2:Eu2+，Mn2+的发光性质

用高温固相法合成了Eu²⁺，Mn²⁺共激活的Ca₂SiO₃Cl₂高亮度白色发光材料，并对其发光性质进行了研究. 该荧光粉在近紫外光激发下发出强的白色荧光，Eu^{2+中心形成峰值为419 nm和498 nm的特征宽带，通过Eu2+中心向Mn2+中心的能量传递导致了峰值为578 nm的发射，三个谱带叠加从而在单一基质中得到了白光. 激发光谱均分布在250—415 nm的波长范围，红绿蓝三个发射带的激发谱峰值分别位于385 nm，412 nm，370 nm和396 nm处，可以被InGaN管芯产生的紫外辐射有效激发. Ca₂SiO₃Cl₂:Eu2+，Mn2+是一种很有前途的单一基质白光LED荧光粉.}     

Photoluminescence properties of Eu and Mn-activated BaMgP2O7 as a potential red phosphor for white-emission

A phosphate compound, BaMgP₂O₇ was co-doped with Eu²⁺ and Mn²⁺ for making a red-emitting phosphor. The phosphor was prepared by a solid-state reaction at high temperature. The photoluminescence properties were investigated under ultraviolet (UV) ray excitation. From a powder X-ray diffraction (XRD) analysis, the formation of single-phased BaMgP₂O₇ with a monoclinic structure was confirmed. In the photoluminescence spectra, the BaMgP₂O₇:Eu,Mn phosphor emits two distinctive colors: a blue band centered at 409 nm originating from Eu²⁺ and a red band at 615 nm caused by Mn²⁺. Also, efficient energy transfer from Eu²⁺ to Mn²⁺ in the BaMgP₂O₇:Eu,Mn system was verified by observing that the excitation spectra of BaMgP₂O₇:Eu,Mn emitted at 409 and 615 nm by Eu²⁺ emission and Mn²⁺ emission, respectively, are almost the same as that of BaMgP₂O₇:Eu monitored at 409 nm. The optimum concentration of Eu²⁺ ions in BaMgP₂O₇:0.015Eu excited at 309 nm wavelength is 1.5 mol%. With an increase of Mn²⁺ content up to 17.5 mol%, a systematic decline in the intensity of the excitation spectrum by Eu²⁺ and a gradual growth in the intensity of emission band by Mn²⁺ were observed. Accordingly, the optimum concentration of Mn²⁺ in BaMgP₂O₇:0.015Eu,Mn is 17.5 mol%. The maximum spectral overlap between emission of Eu²⁺ and excitation of Mn²⁺ is achieved in a composition of BaMgP₂O₇:0.015Eu,0.175Mn, resulting in considerable red-emission at 615 nm.     

Structural and optical properties of the nanopowder of the Eu3+ doped LiLaP4O12 produced by sol gel route

Structural and optical properties of nanopowders of Eu³⁺-doped LiLaP₄O₁₂ (LiLaPO) were studied. The samples were synthetized via polyvinyl alcohol assisted sol gel method. Powder X-ray diffraction (XRD) results showed that the samples have the LiLaPO crystalline phase and scanning electron microscopy (SEM) showed that the particles are in the nanometer scale, mostly as isolated particles with same aggregates. Photoluminescence (PL) properties were evaluated via excitation and emission spectra. The excitation spectra, in the range 2.6–13.8 eV, allowed the identification of the charge transfer band, 4f → 4f5d excitation, exciton formation and the interband excitation of the Eu³⁺ ions in the matrix. The emission spectra revealed that Eu³⁺ is located in two different sites in the samples, one of them being at the bulk and the other close to the surface of the nanoparticles, result confirmed by the CT excitation band.     

Luminescent properties and energy transfer of double-emitting NaSrPO4:Eu2+,Tb3+ phosphor for near-UV white LEDs

Novel blue/green NaSrPO₄ phosphors co-doped with Eu²⁺ and Tb³⁺ were synthesized by a conventional solid-state reaction. Their luminescent properties were characterized by using powder X-ray diffraction, photoluminescence excitation and emission spectra, lifetime, and temperature dependent emission spectra, respectively. The NaSrPO₄:Eu²⁺,Tb³⁺,Na⁺ phosphor showed an intense broad excitation band between 250 and 430 nm, which was in agreement with the near-UV chip (350–420 nm), and it exhibited two dominating emission bands at 445 and 545 nm, corresponding to the allowed 4f⁶5d¹→4f⁷(⁸S_7/2) transition of Eu²⁺ ion and the ⁵D₄→⁷F₅ transition of Tb³⁺ ion, respectively. The emission intensity and lifetime of Eu²⁺ ion decreased with the increasing concentration of Tb³⁺ ion, which strongly indicated that an effective energy transfer occurred from Eu²⁺ to Tb³⁺ in NaSrPO₄ host. The principle of the energy transfer should be the combined effect of the non-radiative resonant energy transfer and the phonon-assisted non-radiative process.     

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.     

Luminescent properties of Eu2+and Dy3+ ions in Ba4Al2O7 phosphor for solid state lighting

In this paper we report the combustion synthesis of rare earth (RE=Eu, Dy) doped Ba₄Al₂O₇ phosphors. Prepared phosphors were characterized by X-ray powder diffraction (XRD), scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), CIE color co-ordinates and their photoluminescence (PL) properties were also investigated. In case of Ba₄Al₂O₇: Eu²⁺, the emission spectra show unique band centered at 495 nm, which corresponds to the 4f⁶5d¹→4f⁷ transition of Eu²⁺, and PL emission spectra of Dy³⁺ ion under 348 nm excitation give two bands centered at 478 nm (blue) and 575 nm (yellow), which originate from the transitions of ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 of Dy³⁺, respectively. The results indicate that the Eu²⁺ and Dy³⁺ activated Ba₄Al₂O₇ phosphor could find application in solid state lighting.     

Synthesis and photoluminescent behavior of Eu3+-doped alkaline-earth tungstates

Eu³⁺-doped alkaline-earth tungstates MWO₄ (M=Ca²⁺, Sr²⁺, Ba²⁺) were prepared by a polymeric precursor method based on the Pechini process. The polymeric precursors were calcined at 700 °C for 2 h in order to obtain well-crystallized powders and then characterized by X-ray diffraction (XRD), thermogravimetric analysis (TG), scanning electron microscopy (SEM), Fourier-transform infrared (FTIR) spectroscopy and photoluminescence spectroscopy (PL). All prepared samples showed a pure crystalline phase with scheelite-type structure confirmed by XRD. It was noted that the charge-transfer band shifted from 260 to 283 nm when calcium is replaced by strontium. However, this band was not observed for Eu³⁺-doped barium tungstate. Upon excitation at 260 nm, the emission spectra are dominated by the red ⁵D₀→⁷F₂ transition at 618 nm. By analyzing of the emission lines, it was inferred that Eu³⁺ ions occupy low symmetry sites in the host lattice. It was also found that Eu³⁺-doped SrWO₄ displays better chromaticity coordinates and greater luminescence intensity than the other samples.     

Synthesis, characterization, thermo- and photoluminescence properties of Bi3+ co-doped Gd2O3:Eu3+ nanophosphors

Gd₂O₃:Eu³⁺ (4 mol%) co-doped with Bi³⁺ (Bi = 0, 1, 3, 5, 7, 9 and 11 mol%) ions were synthesized by a low-temperature solution combustion method. The powders were calcined at 800°C and were characterized by powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), Fourier transform infrared and UV–Vis spectroscopy. The PXRD profiles confirm that the calcined products were in monoclinic with little cubic phases. The particle sizes were estimated using Scherrer’s method and Williamson–Hall plots and are found to be in the ranges 40–60 nm and 30–80 nm, respectively. The results are in good agreement with TEM results. The photoluminescence spectra of the synthesized phosphors excited with 230 nm show emission peaks at ～590, 612 and 625 nm, which are due to the transitions ⁵D₀→⁷F₀, ⁵D₀→⁷F₂ and ⁵D₀→⁷F₃ of Eu³⁺, respectively. It is observed that a significant quenching of Eu³⁺ emission was observed under 230 nm excitation when Bi³⁺ was co-doped. On the other hand, upon 350 nm excitation, the luminescent intensity of Eu³⁺ ions was enhanced by incorporation of Bi³⁺ (5 mol%) ions. The introduction of Bi³⁺ ions broadened the excitation band of Eu³⁺ of which a new strong band occurred ranging from 320 to 380 nm. This has been attributed to the 6s²→6s6p transition of Bi³⁺ ions, implying a very efficient energy transfer from Bi³⁺ ions to Eu³⁺ ions. The gamma radiation response of Gd₂O₃:Eu³⁺ exhibited a dosimetrically useful glow peak at 380°C. Using thermoluminescence glow peaks, the trap parameters have been evaluated and discussed. The observed emission characteristics and energy transfer indicate that Gd₂O₃:Eu³⁺, Bi³⁺ phosphors have promising applications in solid-state lighting.     

Optical absorption and emission from irradiated RbMgF3:Eu2+ and KMgF3:Eu2+

The optical properties of irradiated RbMgF₃:Eu²⁺ and KMgF₃:Eu²⁺ have been investigated. Previous research has shown that Eu²⁺ ions in unirradiated RbMgF₃ give rise to broad band absorption around 250 nm and sharp intense line emission at 360 nm. When this material is irradiated little or no change occurs in the 250 nm absorption, but the lifetime of the Eu²⁺ 360 nm transition is reduced. In addition, new emission is observed at 680 nm. In the case of irradiated KMgF₃:Eu²⁺ two new emission bands are observed at 600 and 800 nm. All of these transitions have short lifetimes and are not due to Eu³⁺ ions.     

Photoluminescence characteristics and energy transfer between Bi3+ and Eu3+ in Gd2O3: Eu3+, Bi3+ nanophosphors

Bi³⁺ and Eu³⁺ codoped cubic Gd₂O₃ nanocrystals were prepared by the Pechini sol-gel method. Their photoluminescent properties were investigated under ultraviolet light excitation. The introduction of Bi³⁺ ions broadened the excitation band of Eu³⁺ emission, of which a new strong band occurred ranging from 320 to 380 nm due to the 6s²→6s6p transition of Bi³⁺ ions, implying a very efficient energy transfer from Bi³⁺ ions to Eu³⁺ ions. Upon 325 and 355 nm light excitation, the luminescent intensity of Eu³⁺ ions was remarkably improved by the incorporation of Bi³⁺ ions. But a significant quenching of Eu³⁺ emission was observed under 266 nm light excitation when Bi³⁺ was codoped. The possible energy transfer processes between Bi³⁺ and Eu³⁺ were discussed. The decay curves of Eu³⁺ emission under the excitation of 266 nm pulsed laser were measured and gave further evidence for our discussion.     

Photoluminescence properties of Eu2+–Mn2+ codoped Ca-α-SiAlON phosphors

Eu²⁺–Mn²⁺ codoped Ca-α-SiAlON phosphors, Ca_0.736?ySi_9.6Al_2.4O_0.8N_15.2:0.064 Eu²⁺, yMn²⁺, were firstly synthesized by the high temperature solid state reaction method. The effects of doped Eu²⁺ and Eu²⁺–Mn²⁺ concentrations on the photoluminescence properties of the as-prepared phosphors were investigated systematically. Powder X-ray diffraction shows that pure Ca-α-SiAlON phase is synthesized after sintering at 1700 °C for 2 h under 0.5 MPa N₂ atmosphere. The excitation spectra of Eu²⁺-doped Ca-α-SiAlON phosphors are characterized by two dominant bands centered at 286 nm and 395 nm, respectively. The photoluminescent spectrum of Eu²⁺-doped Ca-α-SiAlON phosphor exhibits an intense emission band centered at 580 nm due to the allowed 4f ⁶5d→4f ⁷ transition of Eu²⁺, showing that the phosphor is a good candidate for creating white light when coupled to a blue LED chip. The intensities of both excitation and emission spectra monotonously decrease with the increment of codoped Mn²⁺ content (i.e. y value), indicating that energy transfer between Eu²⁺ and Mn²⁺ is inefficient in the case of Eu²⁺–Mn²⁺ codoped Ca-α-SiAlON phosphors.     

Synthesis and Optical Properties of Novel Red-Emitting PbNb<Subscript>2</Subscript>O<Subscript>6</Subscript>: Eu<Superscript>3+</Superscript> Phosphors

Undoped and PbNb₂O_6:Eu³⁺ (1.0 ≤ x ≤ 6.0 mol%) phosphors were synthesized at 1100 °C for 3.5 h by the conventional solid state reaction method. Synthesized PbNb₂O₆:Eu³⁺ phosphors were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Energy dispersive spectroscopy (EDS) and Photoluminescence (PL) analyses. The PL spectra showed series of excitation peaks between 350 and 430 nm due to the 4f–4f transitions of Eu³⁺. For 395.0 nm excitation, emission spectra of Eu³⁺ doped samples were observed at 591 nm (orange) and 614 nm (red) due to the ⁵D₀ → ⁷F₁ transitions and ⁵D₀ → ⁷F₂ transitions, respectively. PL analysis results also showed that the emission intensity increased by increasing Eu³⁺ ion content. No concentration quenching effect was observed. The CIE chromaticity color coordinates (x,y) of the PbNb₂O₆:Eu³⁺ phosphors were found to be in the red region of the chromaticity diagram.     

White-light generation through Ce3+/Mn2+-codoped and Eu2+-doped Ba1.2Ca0.8SiO4 T-phase phosphors

Hexagonal Ba_1.20Ca_0.8?2x?ySiO₄:xCe³⁺,xLi⁺,yMn²⁺ phosphors exhibit two emission bands peaking near 400 and 600 nm from the allowed f–d transition of Ce³⁺ ions and the forbidden ⁴T₁–⁶A₁ transition of Mn²⁺ ions, respectively. The strong interaction between Ce³⁺/Mn²⁺ ions is investigated in terms of energy transfer, crystal field effect, and microstructure by varying their concentrations. They show a higher quenching temperature of 250 °C than that of a commercially used (Ba,Sr)₂SiO₄:Eu²⁺ phosphor (150 °C). Finally, mixtures of these phosphors with green-emissive Ba_1.20Ca_0.70SiO₄:0.10Eu²⁺ are tested and yielded correlated color temperatures from 3500 to 7000 K, and color rendering indices up to 95%.     

Effect of concentration on the luminescence of Eu ions in nanocrystalline La2O3

Nanocrystalline powders with various Eu³⁺ concentration (from 1 to 10 mol %) doped La₂O₃ were prepared via a combustion route. Their structure and morphology were characterized using X-ray diffraction (XRD) and High-resolution transmission electron microscopy. The emission spectra of the as-synthesized samples show that the strongest emission position is centered at 626 nm corresponding to ⁵D₀→⁷F₂ transition of Eu³⁺ ions and the intensity change of 626 nm emission is considered as a function of ultraviolet (240 nm) irradiation time. The excitation spectra at 626 nm monitoring indicate that the charge transfer state band is varies with different Eu³⁺ ion concentration. These results are attributed to the surface defects of the nanocrystals.     

Upconversion luminescence in Tm3+/Yb3+co-doped lead tungstate tellurite glasses

This work reports the upconversion luminescence properties of Tm³⁺/Yb³⁺ ions in lead tungstate tellurite (LTT) glasses. Judd–Oflet intensity parameters have been obtained from the absorption band intensities of Tm³⁺ singly-doped and Tm³⁺/Yb³⁺ co-doped LTT glasses. The spontaneous emission probabilities, radiative lifetimes and branching ratios for ¹G₄ and ³H₄ emission levels of Tm³⁺ have been determined. Upconversion luminescence has been observed by exciting the samples at 980 nm (Yb³⁺:²F_7/2→²F_5/2) at room temperature. Four upconversion emission bands corresponding to the ¹G₄→³H₆ (477 nm), ¹G₄→³F₄ (651 nm), ¹G₄→³H₅ (702 nm) and ³H₄→³H₆ (810 nm) transitions have been identified. The relative variation in the intensities of upconversion bands, the different channels responsible for upconversion spectra and the effect of Yb³⁺ ions concentration on the upconversion luminescence of Tm³⁺ ions have also been discussed.