The effect of Eu3+ concentration on the Y2O3 host lattice obtained from citrate precursors

This work presents a thermal decomposition study of the precursor resin prepared from the citrate precursor along with structural features and optical properties materials composed by Y₂O₃ and Eu³⁺ containing Y₂O₃ in 0.5, 3, 5 and 7 mol%. The microcrystallite sizes were estimated from the Scherrer equation. The structural and optical properties revealed that the addition of 5 mol% of Eu³⁺ to the Y₂O₃ matrix gave rise to the highest relative emission intensity which was evidenced by the luminescence intensity. The lifetime of the 0.5 mol% Eu³⁺-doped sample suggested two different symmetry sites for Eu³⁺ ions because two different lifetime values were acquired for this sample, while for phosphors doped with 3 or 5 mol% of Eu³⁺ ions only one similar lifetime was observed. When the concentration of Eu³⁺ is 0.5 and 3 mol%, the luminescence intensity is weak due to the low probability of the O^2? - Eu³⁺ charge transfer transition. On the other hand, when the concentration of the Eu³⁺ ions is 7 mol%, a quenching effect is evidenced.     

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.     

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.     

A novel blue-emitting Ca2B5O9Br:Eu2+ phosphor prepared by a microwave calcination route

A blue-emitting Ca₂B₅O₉Br:Eu²⁺ phosphor for white light-emitting diodes was synthesized via a microwave calcination route. The phosphor powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and fluorescence spectrophotometer, respectively. The obtained results revealed that the Ca₂B₅O₉Br:Eu²⁺ phosphor prepared by the microwave calcination route possessed a rod-like morphology with the single phase orthorhombic structure. Based on the photoluminescence analysis, it was found that Ca₂B₅O₉Br:Eu²⁺ phosphor exhibited a broad excitation band chiefly in the near ultraviolet region (270–420 nm) and a blue broad emission band of main peak at 452 nm under the strongest excitation of 411 nm. Further investigation on concentration-dependent emission spectra indicated that Ca₂B₅O₉Br:0.03Eu²⁺ phosphor exhibited the strongest luminescent intensity, and the concentration quenching for the two Eu-site emission centers was caused by dipole–dipole interactions.     

Formation and spectral probing of transparent oxyfluoride glass-ceramics containing (Eu2+, Eu3+:BaGdF5) nano-crystals

In the present study, we report the formation of transparent glass-ceramics containing BaGdF₅ nanocrystals under optimum ceramization of SiO₂–BaF₂–K₂O–Sb₂O₃–GdF₃–Eu₂O₃ based oxyfluoride glass and the energy transfer mechanisms in Eu²⁺ → Eu³⁺ and Gd³⁺ → Eu³⁺ has been interpreted through luminescence study. The modification of local environment surrounding dopant ion in glass and glass ceramics has been studied using Eu³⁺ ion as spectral probe. The optimum ceramization temperature was determined from the differential scanning calorimetry (DSC) thermogram which revealed that the glass transition temperature (T_g), the crystallization onset temperature (T_x), and crystallization peak temperature (T_p) are 563 °C, 607 °C and 641 °C, respectively. X-ray diffraction pattern of the glass-ceramics sample displayed the presence of cubic BaGdF₅ phase (JCPDS code: 24-0098). Transmission electron microscopy image of the glass-ceramics samples revealed homogeneous distribution of spherical fluoride nanocrystals ranging 5–15 nm in size. The emission transitions from the higher excited sates (⁵D_J, J = 1, 2, and 3) as well as lowered asymmetry ratio of the ⁵D₀ → ⁷F₂ transition (forced electric dipole transition) to that of the ⁵D₀ → ⁷F₁ transition (magnetic dipole) of Eu³⁺ in the glass-ceramics when compared to glass sample demonstrated the incorporation of dopant Eu³⁺ ions into the cubic BaGdF₅ nanocrystals with higher local symmetry with enhanced ionic nature. The presence of absorption bands of Eu²⁺ ions and Gd³⁺ ions present in the glass matrix or fluoride nanocrystals in the excitation spectra of Eu³⁺ by monitoring emission at 614 nm indicated energy transfer from (Eu²⁺ → Eu³⁺) and (Gd³⁺ → Eu³⁺) in both glass and glass-ceramics samples.     

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.     

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.     

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.     

Synthesis and photoluminescence properties of a cyan-emitting phosphor Ca3(PO4)2:Eu2+ for white light-emitting diodes

In this paper, a cyan-emitting phosphor Ca₃(PO₄)₂:Eu²⁺ (TCP:Eu²⁺) was synthesized and evaluated as a candidate for white light emitting diodes (WLEDs). This phosphor shows strong and broad absorption in 250–450 nm region, but the emission spectrum is prominent at around 480 nm. The emission intensity of the TCP:Eu²⁺ was found to be 60% and 82% of that of the commercial BaMgAl₁₀O₁₇:Eu²⁺ (BAM) under excitation at 340 nm and 370 nm, respectively. Upon excitation at 370 nm, the absolute internal and external quantum efficiencies of the Ca₃(PO₄)₂:1.5%Eu²⁺ are 60% and 42%, respectively. Moreover, a white LED lamp was fabricated by coating TCP:Eu²⁺ with a blue-emitting BAM and a red-emitting CaAlSiN₃:Eu²⁺ on a near-ultraviolet (375 nm) LED chip, driven by a 350 mA forward bias current, and it produces an intense white light with a color rendering index of 75.     

Synthesis of new green-emitting KBa1−xScSi3O9:Eu2+x phosphors for white LEDs

New green-emitting KBa_1−xScSi₃O₉:Eu²⁺_x phosphors for white LEDs were synthesized by a conventional solid-state reaction method. The obtained KBa_1−xScSi₃O₉:Eu²⁺_x phosphors show the strong broad optical absorption band from UV to blue light region and exhibit broad green emission with a peak at 521 nm under excitation at 405 nm due to the allowed 4f⁶5d¹−4f⁷ transition of Eu²⁺. Optimization of Eu²⁺ concentration resulted in the highest green emission peak intensity was obtained at the composition of KBa_0.94ScSi₃O₉:Eu²⁺_0.06, and the relative emission intensity of this phosphor was 32% of that of a commercial YAG:Ce³⁺ phosphor.     

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.     

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.     

Variation of the photoluminescence and vacuum ultraviolet excitation characteristics of BaZr(BO3)2:Eu3+ by the incorporation of Al3+, La3+, or Y3+ into the lattice

The photoluminescence (PL) and vacuum ultraviolet (VUV) excitation properties are studied for the BaZr(BO₃)₂:Eu³⁺ phosphor with incorporating the Al³⁺, La³⁺, or Y³⁺ ion into the lattice. The excitation spectrum shows an absorption band in the VUV region with the band-edge at 200 nm and a very weak charge transfer band of Eu³⁺ at about 226 nm. The luminescence spectrum shows a strong emission at 615 nm (⁵D₀ → ⁷F₂ transition) and weak emission at 594 nm (⁵D₀ → ⁷F₁ transition) in BaZr(BO₃)₂:Eu³⁺, with a good red color purity. The PL intensity is increased by incorporating Al³⁺ into the BaZr(BO₃)₂ lattice. The PL intensity has also increased by incorporating La³⁺ into the lattice, however, the red color purity has deteriorated because of the increased centrosymmetric nature of the site. With the incorporation of Y³⁺ into the BaZr(BO₃)₂ lattice, the PL characteristics of the Eu³⁺ activator resembles that in the YBO₃ lattices. The intensity of the red PL for the Eu³⁺ activator is the highest with good color purity for BaZr(BO₃)₂:Eu³⁺ incorporated with both Al³⁺ (10%) and La³⁺ (0.5%).     

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.     

Preliminary spectroscopic properties of K4SrSi3O9 doped with Eu3+

K₄SrSi₃O₉ doped with Eu³⁺ has been for the first time obtained by the conventional solid-state reactions. The X-ray powder diffraction confirmed that prepared materials were single phase. The excitation, emission spectra and decay time of the emitting level have been measured. The influence of Eu³⁺ concentration on luminescence properties has been analyzed. The luminescence intensity of this material at 100 °C is equal to 94% of emission intensity recorded at room temperature, and makes the material a good candidate for commercial phosphors.     

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.     

Enhanced photoluminescence features of Eu3+-modified di-ureasil-zirconium oxocluster organic–inorganic hybrids

In this work, a series of transparent di-ureasil hybrids containing different amounts of methacrylic acid modified zirconium tetrapropoxide (ZrMcOH) nanoclusters (5–85 mol%) and incorporating EuCl₃ and [Eu(tta)₃(H₂O)₂] (tta = thenoyltrifluoroacetonate) complex were prepared. These hybrids are multi-wavelength emitters due to the convolution of the host intrinsic emission (electron–hole recombinations occurring in siliceous and urea cross-linkages) Eu³⁺ intra-4f⁶ transitions. The ZrMcOH incorporation deviates the maximum excitation wavelength of the hybrid host intrinsic emission from the UV (365 nm) to the blue (420 nm) and enhances the absolute emission quantum yield from 6.0 ± 0.6% to 9.0 ± 0.9%, and contributes to an increase in the ⁵D₀ lifetime values, quantum efficiency due to a decrease in the non-radiative transition probability and OH groups coordinated to the Eu³⁺ ions.     

A novel red phosphor Na2Ca4Mg2Si4O15:Eu3+ for plasma display panels

A novel red emitting phosphor, Eu³⁺-doped Na₂Ca₄Mg₂Si₄O₁₅, was prepared by the solid-state reaction. X-ray powder diffraction (XRD) analysis confirmed the formation of Na₂Ca₄Mg₂Si₄O₁₅:Eu³⁺. Field-emission scanning electron-microscopy (FE-SEM) observation indicated a narrow size-distribution of about 300 nm for the particles with spherical shape. Upon excitation with vacuum ultraviolet (VUV) and near UV light, the phosphor showed strong red-emission lines at around 611 and 617 nm, respectively, corresponding to the forced electric dipole ⁵D₀ → ⁷F₂ transition of Eu³⁺, and the highest PL intensity at 617 nm was found at a content of about 8 mol% Eu³⁺. The optical properties study suggests that it is a potential candidate for plasma display panels (PDPs) application.     

Luminescence properties of Na3SrB5O10:Dy3+ plate-like microstructures for solid state lighting applications

A series of novel plate-like microstructure Na₃SrB₅O₁₀ doped with various Dy³⁺ ions concentration have been synthesized for the first time by solid-state reaction (SSR) method. X-ray diffraction (XRD) results demonstrated that the prepared Na₃SrB₅O₁₀:Dy³⁺ phosphors are single-phase pentaborates with triclinic structure. The plate-like morphology of the phosphor is examined by Field emission scanning electron microscopy (FE-SEM). The existence of both BO₃ and BO₄ groups in Na₃SrB₅O₁₀:Dy³⁺ phosphors are identified by Fourier transform infrared (FT-IR) spectroscopy. Upon excitation at 385 nm, the PL spectra mainly comprising of two broad bands: one is a blue light emission (∼486 nm) and another is a yellow light emission (∼581 nm), originating from the transitions of ⁴F_9/2 → ⁶H_15/2 and ⁴F_9/2 → ⁶H_13/2 in 4f⁹ configuration of Dy³⁺ ions, respectively and the optimized dopant concentration is determined to be 3 at.%. Interestingly, the yellow-to-blue (Y/B) emission integrated intensity ratio is close to unity (0.99) for 3 at.% Dy³⁺ ions, suggesting that the phosphors are favor for white illumination. Moreover, the calculated Commission International de l’Eclairage (CIE) chromaticity coordinates of Na₃SrB₅O₁₀:Dy³⁺ phosphors shows the values lie in white light region and the estimated CCT values are located in cool/day white light region.     

Photoluminescence properties of Eu2+-activated Ca2Y2Si2O9 phosphor

Eu²⁺-activated Ca₂Y₂Si₂O₉ phosphors with different Eu²⁺ concentrations have been prepared by a solid-state reaction method at high temperature and their photoluminescence (PL) properties were investigated. Photoluminescence results show that Eu²⁺-doped Ca₂Y₂Si₂O₉ can be efficiently excited by UV–visible light from 300 to 425 nm. Ca₂Y₂Si₂O₉: Eu²⁺ exhibits broad band emission in the wavelength range of 425–700 nm, due to the 4f⁶5d¹ → 4f⁷5d⁰ transition of the Eu²⁺ ions located at two different sites ((Ca/Y)1 and (Ca/Y)2) in Ca₂Y₂Si₂O₉. The effect of the Eu²⁺ concentration in Ca₂Y₂Si₂O₉ on the PL properties was investigated in detail. The results showed that the relative PL intensity reaches a maximum at 1 mol% of Eu²⁺, and a red-shift of the emission bands from these two different sites was observed with increasing Eu²⁺ concentration. Also there exists energy transfer between these two Eu²⁺ sites. The potential applications of Ca₂Y₂Si₂O₉: Eu²⁺ have been pointed out.