Ultraviolet upconversion luminescence of Gd3+ and Eu3+ in nano-structured glass ceramics

Ultraviolet multiphoton upconversion emissions of Eu³⁺ (⁵H_3–7, ⁵G_2–6, ⁵L₆ → ⁷F₀) and Gd³⁺ (⁶I_J, ⁶P_J → ⁸S_7/2) are studied in the Eu³⁺ (or Gd³⁺) doped SiO₂–Al₂O₃–NaF–YF₃ precursor glasses and glass ceramics containing β-YF₃ nanocrystals, under continuous-wavelength 976 nm laser pumping. It is experimentally demonstrated that energy transfer from Yb³⁺ to Tm³⁺, then further to Eu³⁺ or Gd³⁺ is responsible for the upconversion process. Compared to those in the precursor glasses, the upconversion emission intensities in the glass ceramics are greatly enhanced, owing to the participation of rare earth ions into the low-phonon-energy environment of β-YF₃ nanocrystals. Hopefully, the studied glass ceramics may find potential applications in the field of ultraviolet solid-state lasers.     

Visible quantum cutting through downconversion in Eu3+-doped K2GdZr(PO4)3 phosphor

K₂Gd_1?xZr(PO₄)₃:Eu_x³⁺ (0.02 ≤ x ≤ 0.1, x is in mol.%) were prepared by solid-state reaction method and their photoluminescence properties were investigated in ultra-violet (UV) and vacuum ultra-violet (VUV) region. The phenomenon of visible quantum cutting through downconversion was observed for the Gd³⁺–Eu³⁺ couple in this Eu³⁺-doped K₂GdZr(PO₄)₃ system. Visible quantum cutting, the emission of two visible light photons per absorbed VUV photon, occurred upon the 186 nm excitation of Gd³⁺ at the ⁶G_J level via two-step energy transfer from Gd³⁺ to Eu³⁺ by cross-relaxation and sequential transfer of the remaining excitation energy. The results revealed that the efficiency of the energy transfer process from Gd³⁺ to Eu³⁺ in the Eu³⁺-doped K₂GdZr(PO₄)₃ system could reach to 155% and K₂GdZr(PO₄)₃:Eu³⁺ was effective quantum cutting material.     

Spectroscopic investigations on Eu3+ ions in Li–K–Zn fluorotellurite glasses

Eu³⁺ ions incorporated Li–K–Zn fluorotellurite glasses, (70 − x)TeO₂ + 10Li₂O + 10K₂O + 10ZnF₂ + xEu₂O₃, (0 ⩽ x ⩽ 2 mol%) were prepared via melt quenching technique. Optical absorption from ⁷F₀ and ⁷F₁ levels of the Eu³⁺-doped glass has been studied to examine the covalent bonding characteristics, energy band gap and Judd–Ofelt intensity parameters. The emission spectra (⁵D₀ → ⁷F_0,1,2,3,4) of the glasses were used to estimate the luminescence enhancement, asymmetric environment in the vicinity of Eu³⁺ ions, stimulated emission cross section and branching ratios. The phonon side band mechanism of ⁵D₂ level of the Eu³⁺ ions in the prepared glass was examined by considering the excitation and Raman spectra. The radiative lifetime calculated using Judd–Ofelt parameters was compared with the experimental lifetime to estimate the quantum efficiency of ⁵D₀ level of Eu³⁺ ions in Li–K–Zn fluorotellurite glass.     

Photoluminescence of Eu3+-doped LaPO4 nanocrystals synthesized by combustion method

Eu³⁺-doped LaPO₄ nanocrystals were synthesized for the first time by a combustion method with urea as a fuel calcined at 700 °C. The diffraction profile of the obtained sample was indexed as a monoclinic monazite-structure by X-ray diffraction (XRD) data. The obtained nanocrystals appeared to be short rod-like with diameters of 5–10 nm and lengths of 20–70 nm. The luminescence intensities of Eu³⁺-doped LaPO₄ nanocrystals were found to be strongly dependent on the quantities of urea added and the concentration of Eu³⁺.     

Synthesis and photoluminescence study of La1.8Eu0.2O3 coating on nanometric α-Al2O3

In this work the La_1.8Eu_0.2O₃ coating on nanometric alpha-alumina, α-Al₂O₃@La_1.8Eu_0.2O₃, was prepared for the first time by a soft chemical method. The powder was heat-treated at 100, 400, 800 and 1200 °C for 2 h. X-ray powder diffraction patterns (XRD), transmission electronic microscopy (TEM), emission and excitation spectra, as well as Eu³⁺ lifetime were used to characterize the material and to follow the changes in structure as the heating temperature increases. The Eu³⁺ luminescence data revealed the characteristic transitions ⁵D₀ → ⁷F_J (J = 0, 1 and 3) of Eu³⁺ at around 580, 591 and 613 nm, respectively, when the powders were excited by 393 nm. The red color of the samples changed to yellow when the powder was annealed at 1200 °C. The decrease in the (⁵D₀ → ⁷F₂)/(⁵D₀ → ⁷F₁) ratio from around 5.0 for samples heated at lower temperatures to 3.1 for samples annealed at 1200 °C is consistent with a higher symmetry of the Eu³⁺ at higher temperature. The excitation spectra of the samples also confirms this change by the presence of a more intense and broad band at around 317 nm, instead of the presence of the characteristic peak at 393 nm, which corresponds to the ⁷F₀ → ⁵L₆ transition of the Eu³⁺. The lifetimes of the ⁵D₀ → ⁷F₂ transition of Eu³⁺ for the samples heat-treated at 100, 400, 800 and 1200 °C was evaluated as 0.57, 0.72, 0.43 and 0.31 ms, respectively.     

VUV–UV luminescence of Ce3+, Tb3+, Eu3+, and Dy3+ doped GdOCl

The vacuum ultraviolet spectroscopic properties of GdOCl:Re³⁺ (Re³⁺ = Ce³⁺, Tb³⁺, Eu³⁺, and Dy³⁺) are investigated in detail for the first time. The host absorption band is determined to be around 179 nm, and the f–d transition bands as well as the charge transfer bands are assigned. Upon 179 nm excitation, Re³⁺ (Re³⁺ = Ce³⁺, Tb³⁺, Eu³⁺, Dy³⁺) ions shown their characteristic emissions. Energy transfers from Gd³⁺ to Re³⁺ ion were observed. A broad band ranging from 350 to 400 nm corresponding to the d–f transition of Ce³⁺ is observed. Eu³⁺ has typical red emission with the strongest peak at 620 nm; Tb³⁺ shows characteristic transition of ⁵D_3,4 → ⁷F_j, and its spin-forbidden and spin-allowed f–d transitions in VUV region are calculated with Dorenbos’ equations, these calculated values agree well with the experimental results. Dy³⁺ presents yellow emission (⁴F_9/2 → ⁶H_13/2) with the strongest peak at 573 nm.     

Synthesis and photoluminescence properties of NaLaMgWO6:RE3+ (RE = Eu,Sm, Tb) phosphor for white LED application

Single phase of NaLa_1?xMgWO₆:xRE³⁺ (0 < x ≤1) (RE = Eu, Sm, Tb) phosphors were prepared by solid-state reaction method. X-ray diffraction, scanning electron microscopy, the morphology energy-dispersive X-ray spectroscopy, UV–vis diffuse reflectance spectra and photoluminescence were used to characterize the samples. Under the light excitation, NaLaMgWO₆:Eu³⁺, NaLaMgWO₆:Sm³⁺ and NaLaMgWO₆:Tb³⁺, phosphors showed the characteristic emissions of Eu³⁺ (⁵D₀ → ⁷F_{4, 3, 2, 1}), Sm³⁺ (⁴G_5/2 → ⁶H_{5/2, 7/2, 9/2}), and Tb³⁺ (⁵D₄ → ⁷F_{6, 5, 4, 3}), respectively. The intensity of the red emission for Na(La_0.6Eu_0.4)MgWO₆ is 2.5 times higher than that of (Y_0.95Eu_0.05)₂O₃ under blue light irradiation. The quantum efficiencies of the entitled phosphors excited under 394 nm and 464 nm are also investigated and compared with commercial phosphors Y₂O₃:Eu³⁺, Sr₂Si₅N₈:Eu²⁺ and Y₃A₅G₁₂:Ce³⁺. The results demonstrated NaLaMgWO₆:RE³⁺ phosphors as potential candidates for white light emitting diode pumped by UV or blue chip.     

Improved optical photoluminescence by charge compensation in the phosphor system CaMoO4:Eu3+

It has been found that charge compensated CaMoO₄:Eu³⁺ phosphors show greatly enhanced red emission under 393 and 467 nm-excitation, compared with CaMoO₄:Eu³⁺ without charge compensation. Two approaches to charge compensation, (a) 2Ca²⁺ → Eu³⁺ + M⁺, where M⁺ is a monovalent cation like Li⁺, Na⁺ and K⁺ acting as a charge compensator; (b) 3Ca²⁺ → 2Eu³⁺ + vacancy, are investigated. The influence of sintering temperature and Eu³⁺ concentration on the luminescent property of phosphor samples is also discussed.     

A facile preparation and the luminescent properties of Eu3+-doped Y2O2SO4 nanopieces

The europium(III)-doped yttrium oxysulfate (Y₂O₂SO₄:Eu³⁺) nanopieces have been prepared via electrospinning followed by calcination at 1000 °C in mixed gas of sulfur dioxide and air. Based on the experimental results, a possible formation mechanism for the nanopieces is that the nanopieces are determined by the directing template of electrospun nanoribbons and the multilayer crystal structure of Y₂O₂SO₄. Besides, the nanopieces show excellent luminescent properties with emissions at 581, 589, 597, 653, 619, and 697 nm resulting from the ⁵D₀ → ⁷F_J (J = 0, 1, 2, 3, 4) transition of Eu³⁺. The peaks of charge transfer and ⁵D₀ → ⁷F₂ transition of Eu³⁺ obviously have red shifts comparing to those of both Y₂O₃:Eu³⁺ nanoribbons and commercial Y₂O₃:Eu³⁺. Moreover, the nanopieces exhibit stronger intensities than the Y₂O₃:Eu³⁺ in excitation and emission spectra. Concentration quenching in the nanopieces occurs when Eu³⁺ concentration is 11 mol%, indicating that the nanopieces have an optimum luminescent intensity under this doping concentration.     

Synthesis and spectroscopic characterization of the K4BaSi3O9:Eu3+

K₄BaSi₃O₉:Eu³⁺ polycrystals were synthesized by solid state method. X-ray powder diffraction measurements confirmed structure of the samples. The excitation and the emission spectra of orthorhombic K₄BaSi₃O₉ doped with Eu³⁺ were investigated. The excitation spectrum exhibits a broad band with maximum at 220 nm corresponding to the charge transfer (CT) transition between O²⁻ and Eu³⁺ ions and smaller 4f–4f transitions. The emission of investigated phosphor was excited at 395 nm and has quantum efficiency (QE) equal 27%. The emission maximum at 616.5 nm was assigned to the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions. The luminescence decay profiles as well as the thermal quenching were measured and analyzed. K₄BaSi₃O₉:Eu³⁺has high temperature quenching of the emission T_0.5 = 335 °C.     

Strong luminescence and efficient energy transfer in Eu3+/Tb3+-codoped ZnO nanocrystals

Single crystalline Eu³⁺/Tb³⁺-codoped ZnO nanocrystals have been synthesized by using a simple co-precipitation method. Successful doping is realized so that strong green and red luminescence can be efficiently excited by ultraviolet and near ultraviolet radiation, demonstrating an efficient energy transfer from ZnO host to rare earth ions. The energy transfer from the ZnO host to Tb³⁺ in ZnO: Tb³⁺ samples and ZnO host to Eu³⁺ in the ZnO: Eu³⁺ samples under UV excitation are investigated. It is found that the red ⁵D₀ → ⁷F₂ emission of Eu³⁺ ions decreases with increasing temperature but the green ⁵D₄ → ⁷F₅ emission of Tb³⁺ ions increases with increasing temperature, implying a different energy transfer processes in the two samples. Moreover, energy transfer from Tb³⁺ ions to Eu³⁺ ions in ZnO nanocrystals is also observed by analyzing luminescence spectra and the decay curves. By adjusting the doping concentration, the Eu³⁺/Tb³⁺-codoped ZnO phosphors emit green and red luminescence with chromaticity coordinates near white light region, high color purity and high intensity, indicating that they are promising light-conversion materials and have potential in field emission display devices and liquid crystal display backlights.     

Synthesis and luminescent properties of SrZnO2:Eu3+,M+ (M = Li,Na, K) phosphor

In this paper, a series of novel luminescent materials, SrZnO₂:Eu³⁺,M⁺ (M = Li, Na, K) have been synthesized by conventional solid-state reaction. X-ray diffraction (XRD) patterns and photoluminescence (PL) spectra were carried out to characterize their structural and luminescent properties. It was found that under ultraviolet excitation with a wavelength of 301 nm, SrZnO₂:Eu³⁺ gives a red luminescence that was attributed to the transitions from ⁵D₀ excited states to ⁷F_J (J = 0–4) ground states of Eu³⁺ ions. The feature and the high intensity of hypersensitive transition ⁵D₀ → ⁷F₂ indicate that Eu³⁺ prefers to occupy a low symmetry site. The incorporation of alkali metal ions greatly enhanced the luminescence intensity and slightly changed the excitation and emission peak position, probably due to the influence of the coordination conditions for Eu³⁺ ions.     

Spectroscopic properties of Eu3+/Nd3+ co-doped phosphate glasses and opaque glass–ceramics

This paper reports the fabrication and characterization of Eu³⁺/Nd³⁺ co-doped phosphate (PNE) glasses and glass–ceramics as a function of Eu³⁺ concentration. The precursor glasses were prepared by the conventional melt quenching technique and the opaque glass–ceramics were obtained by heating the precursor glasses at 450 °C for 30 h. The structural and optical properties of the glass and glass–ceramics were analyzed by means of X-ray diffraction, Raman spectroscopy, UV–VIS–IR absorption spectroscopy, photoluminescence spectra and lifetimes. The amorphous and crystalline structures of the precursor glass and opaque glass–ceramic were confirmed by X-ray diffraction respectively. The Raman spectra showed that the maximum phonon energy decreased from 1317 cm⁻¹ to 1277 cm⁻¹ with the thermal treatment. The luminescence spectra of the glass and glass–ceramic samples were studied under 396 nm and 806 nm excitation. The emission intensity of the bands observed in opaque glass–ceramic is stronger than that of the precursor glass. The luminescence spectra show strong dependence on the Eu³⁺ ion concentration in the Nd³⁺ ion photoluminescence (PL) intensity, which suggest the presence of energy transfer (ET) and cross-relaxation (CR) processes. The lifetimes of the ⁴F_3/2 state of Nd³⁺ ion in Eu³⁺/Nd³⁺ co-doped phosphate glasses and glass–ceramics under 806 nm excitation were measured. It was observed that the lifetimes of the ⁴F_3/2 level of Nd³⁺ of both glasses and glass–ceramics decrease with the increasing Eu³⁺ concentration. However in the case of opaque glass–ceramics the lifetimes decrease only 16%.     

Effect of symmetry reduction on the electronic transitions in polytypic GdAl3(BO3)4:Eu:Tb crystals

The existence of a recently described monoclinic phase (C2/c, Z = 8) (Beregi et al., 2012) in addition to the well-known Huntite type rhombohedral (R32) polytypic modification of the GdAl₃(BO₃)₄ (GAB) crystal at room temperature provides a unique possibility to investigate the incorporation of rare earth dopants into slightly modified crystal lattice by spectroscopic methods. In these characteristic GAB structures the dopant ions, e.g. Tb³⁺ or Eu³⁺, possess slightly different neighbor geometries and local symmetries. The Tb³⁺: ⁷F₆ → ⁵D₄ and Eu³⁺: ⁷F_0,1,2 → ⁵D_0,1,2 electronic transitions were successfully identified in the absorption spectra using polarization, concentration and temperature dependent measurements in both polytypic modifications. The positions of the investigated Tb lines are shifted by up to 10 cm⁻¹ due to symmetry changes. In addition, some of the Eu lines show splittings of about 4–30 cm⁻¹ as a consequence of the change of the local environment. From the room temperature absorption measurements some of the low energy crystal field levels of ⁷F and ⁵D states of the Eu³⁺ ions were successfully determined for both modifications.     

Synthesis and two-color emission properties of BaGd2(MoO4)4:Eu3+,Er3+,Yb3+ phosphors

Eu³⁺, Er³⁺ and Yb³⁺ co-doped BaGd₂(MoO₄)₄ two-color emission phosphor was synthesized by the high temperature solid-state method. The structure of the sample was characterized by XRD, and its luminescence properties were investigated in detail. Under the excitation of 395 nm ultraviolet light, the BaGd₂(MoO₄)₄:Eu³⁺,Er³⁺,Yb³⁺ phosphor emitted an intense red light at 595 and 614 nm, which can be attributed to ⁵D₀ → ⁷F₁ and ⁵D₀ → ⁷F₂ transitions of Eu³⁺, respectively. The phosphor will also show bright green light under 980 nm infrared light excitation. The green emission peaks centred at 529 and 552 nm, were attributed to ⁴H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2 transitions of Er³⁺, respectively. It indicated that the two-color emission can be achieved from the same BaGd₂(MoO₄)₄:Eu³⁺,Er³⁺,Yb³⁺ host system based on the different pumping source, 395 nm UV light and 980 nm infrared light, respectively. The obtained results showed that this kind of phosphor may be potential in the field of multi-color fluorescence imaging and anti-counterfeiting.     

Novel red phosphors LaBSiO5 co-doped with Eu3+, Al3+ for near-UV light-emitting diodes

Red-emitting phosphors LaBSiO₅:Eu³⁺ and LaBSiO₅:Eu³⁺, Al³⁺ were synthesized by the conventional solid state method at 1100 °C. The structure and luminescent properties of these phosphors are investigated. LaBSiO₅:Eu³⁺ and LaBSiO₅:Eu³⁺, Al³⁺ could be efficiently excited by near ultraviolet light with the strongest excitation peak at 395 nm. The main emission peak is located at around 616 nm, which corresponds to the transition of ⁵D₀ → ⁷F₂ of Eu³⁺ ions. The emission intensity of LaBSiO₅:Eu³⁺ was enhanced by introducing Al³⁺ ions. Compared with Y₂O₂S:0.05Eu³⁺, the sample La_0.70B_0.75SiO₅:0.30Eu³⁺, 0.25Al³⁺ shares the intense red emission, and its emission intensity is about 3.8 times as strong as that of Y₂O₂S:0.05Eu³⁺ under 395 nm light excitation. Bright red light can be observed from the red LED based on La_0.70B_0.75SiO₅:0.30Eu³⁺, 0.25Al³⁺, hence La_0.70B_0.75SiO₅:0.30Eu³⁺, 0.25Al³⁺ maybe find application on near-UV InGaN-based white LEDs.     

Synthesis and luminescence study of Eu3+ in Zn2SiO4 nanocrystals

The sol–emulsion–gel method is used for the preparation of Eu³⁺ doped Zn₂SiO₄ nanoparticles. The luminescence spectra at 613 nm (⁵D₀ → ⁷F₂) and lifetime of the excited state of Eu³⁺ ions doped Zn₂SiO₄ nanocrystals are also found to be sensitive to the concentration (0.25–2.5 mol%) of ions. In case of 1000 °C annealed sample (0.25 mol% Eu³⁺) showed the single component decay of 2.02 ms. However, with increasing the concentration the decay is biexponential. We attribute this to an inter-ion exchange interaction wherein the more rapid decay is due to pair or cluster formation and the longer-lived emission originates from isolated ions within the insulating host.     

Luminescence properties of nanocrystalline YVO4:Eu3+ under UV and VUV excitation

Single phase of Eu³⁺-doped YVO₄ nanophosphors at different pH values were synthesized by a mild hydrothermal method. Their photoluminescence were evaluated under UV and VUV region, respectively. Monitoring by 619 nm emission, broad bands at around 143 nm, 200 nm, 260 nm were observed in the excitation spectrum of YVO₄:5 mol%Eu³⁺. These peaks could be assigned to host absorption, the overlap of the VO₄³⁻ host absorption and charge transfer transition between Eu³⁺ and O²⁻, respectively. Both 254 nm and 147 nm excitations, the emission spectra were identical, they were all composed of Eu³⁺ emission transitions arising mainly from the ⁵D₀ level to the ⁷F_J (J = 1, 2, 3, 4) manifolds. With the pH values ranging from 7 to 11, the relative intensity of the emission spectra were decreasing, and the position of the predominant peak (⁵D₀ → ⁷F₂) was changed from 619 nm to 615 nm when the pH values changed from 7 to 11.     

Photoluminescence properties of Sr3(PO4)2: Eu2+, Dy3+ double-emitting blue phosphor for white LEDs

Double-emitting blue phosphor Sr₃(PO₄)₂: Eu²⁺, Dy³⁺ was synthesized by solid state reaction under H₂ atmosphere. XRD exhibited the pure hexagonal phase of the prepared phosphor. The photoluminescence results showed that all samples had intense broad absorption band between 250 and 450 nm, which matched well with the near-UV (350–420 nm) emission band of InGaN-based chips. The emission spectrum of Sr₃(PO₄)₂: Eu²⁺, Dy³⁺ consisted of two broad bands, peaked at 485 nm and 410 nm, which originated from two luminescent centers, related to 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ in six-coordinated Sr(I) and ten-coordinated Sr(II) sites respectively. The intensity ratio of two emission bands could be easily tuned by adjusting Dy³⁺ co-doping content, which resulted in color-tunable luminescence in bluish green region to purplish blue region.     

Eu3+ activated novel alkaline earth metal gallium oxide phosphors: Sr(2.92−x)Ca(x)Ga2O6:Eu3+0.08 for light emitting diodes

Present study deals with Eu³⁺ activated novel alkaline earth metal (Sr and Ca) gallium oxide phosphors, Sr_(2.92?x)Ca_(x)Ga₂O₆:Eu³⁺_0.08 (x = 0 to 2.92). Crystal structure, morphology and luminescence (excitation, emission and CIE coordinate) properties of these phosphors have been studied as a function of Ca concentration. Doping of Ca ions into Sr_2.92Ga₂O₆:Eu³⁺ phosphor gives rise to a significant enhancement in overall fluorescence and the optimum emission is attained for pure Ca_2.92Ga₂O₆:Eu³⁺ phosphor for x = 2.92. The intensity ratio of ⁵D₀ → ⁷F₂ to ⁵D₀ → ⁷F₁ transitions (monochromaticity) of Eu³⁺ for different doping concentration of Ca suggests that asymmetry around the Eu³⁺ ion increases with increase in Ca ion concentration, which is responsible for enhanced emission. The excellent optical features, such as broad excitation band (230–480 nm) and excellent emission in red region (at 614 nm), conclude that calcium gallet phosphor could be a potential candidate for light emitting diodes and display applications.