Luminescent properties of Eu-activated Sr3B2SiO8: A red-emitting phosphor for white light-emitting diodes

Single-phased Sr₃B₂SiO₈:Eu³⁺ phosphor was prepared by a solid-state method at 1020 °C. The luminescence spectra showed that Sr₃B₂SiO₈:Eu³⁺ phosphor can be effectively excited by near ultraviolet light (393 nm) and blue light (464 nm). When excited at 393 or 464 nm Sr₃B₂SiO₈:Eu³⁺ exhibited the main emission peaks at 611 and 620 nm, which resulted from the supersensitive ⁵D₀→⁷F₂ transition of Eu³⁺. The luminescence intensity of Sr₃B₂SiO₈:Eu³⁺ at 611 and 620 nm reached the maximum when the doping content of Eu³⁺ was 4.5 mol%. Its chromaticity coordinates (0.646, 0.354) were very close to the NTSC standard values (0.67, 0.33). Thus, Sr₃B₂SiO₈:Eu³⁺ is considered to be an efficient red-emitting phosphor for long-UV InGaN-based light-emitting diodes.     

Luminescent properties of Eu3+ and Sm3+ activated M2SiO4 (M=Ba,Sr and Ca) red-emitting phosphors for WLEDs

Eu³⁺ and Sm³⁺ activated M₂SiO₄ (M=Ba, Sr and Ca) red-emitting phosphors were synthesized by a solid state reaction. The results of XRD and SEM measurements show that the samples are single phase and have irregular shape. The excitation and emission spectra indicate that these phosphors were effectively excited by ultraviolet (395 nm) and blue (466 nm) light and exhibited red performance. The charge compensator R⁺ (R⁺=Li⁺, Na⁺ and K⁺) injecting into the host efficiently enhanced the luminescence intensity of the M₂SiO₄: Eu³⁺ and M₂SiO₄: Sm³⁺ phosphors. The emission intensity of M₂SiO₄: Eu³⁺ and Sm³⁺ doping Li⁺ were higher than that of Na⁺ or K⁺.     

Preparation and optical properties of Ce activated (Ca1 − x,Srx)Al2Si2O8 phosphors

(Ca_1 − x, Sr_x)Al₂Si₂O₈:0.06Ce³⁺, M⁺ (M⁺ = Li⁺, Na⁺, K⁺) phosphors have been prepared by conventional solid-state reaction method. The structural and optical properties of the phosphors were characterized by X-ray diffraction (XRD) technique and spectrophotometer, respectively. A regular variation was found among the XRD patterns of (Ca_1 − x, Sr_x)Al₂Si₂O₈:0.06Ce³⁺ phosphors based on the changing of Sr content. With the increase of Sr content, the maximum of emission band presented slight blue shifts (~ 15 nm). The luminescence intensity of CaAl₂Si₂O₈:0.06Ce³⁺ and SrAl₂Si₂O₈:0.06Ce³⁺ were significantly enhanced when K⁺ and Li⁺ were incorporated, respectively.     

Improved luminescent properties of red-emitting Ca0.54Sr0.16Eu0.08Gd0.12(MoO4)0.2(WO4)0.8 phosphor for LED application by charge compensation

The red-emitting Ca_0.54Sr_0.16Eu_0.08Gd_0.12(MoO₄)_0.2(WO₄)_0.8 phosphor is improved in the emission charateristics by charge compensation, of which chromaticity coordinates (CIE) are x=0.66 and y=0.33. Three approaches to charge compensation are investigated, namely (a) 3Ca²⁺/Sr²⁺→2Eu³⁺/Gd³⁺+vacancy, (b) 2Ca²⁺/Sr²⁺→Eu³⁺/Gd³⁺+M⁺(M⁺ is a monovalent cation like Li⁺, Na⁺ and K⁺ employed as a charge compensator) and (c) Ca²⁺/Sr²⁺→Eu³⁺/Gd³⁺+N⁻ (N⁻ is a monovalent anion like F⁻, Cl⁻, Br⁻ and I⁻ employed as charge compensation ions). Through photoluminescent spectra analyzing the radiative and non-radiative relaxation mechanisms of luminescent system are obtained. Under 20 mA forward-bias current, one red-emitting LED is made by combining 390-405 nm-emitting LED chip and the phosphor. The red-emitting phosphor has broad prospects in LED application field.     

Red emission in B- and Li-doped SrAl2O4:Eu phosphor under UV excitation

Samples of SrAl₂O₄:Eu³⁺ doped with B³⁺ and SrAl₂O₄:Eu³⁺ co-doped with B³⁺ and Li⁺ have been prepared by the solid-reaction method. The influence of B³⁺ and Li⁺ contents on luminescence property has been investigated. It is found that the substitution of B³⁺ for Al³⁺ greatly improves red emission intensity at 591, 615 and 701 nm. The dopant Li⁺ as charge compensator in SrAl₂O₄:Eu³⁺, B³⁺ can further enhance luminescence intensity. The strongest red emission is obtained in the Sr(Al_1.9, B_0.1)O₄:Eu_0.02³⁺, Li⁺_0.02 sample. The developed phosphors can be efficiently excited by ultraviolet (UV) light from 350 to 480 nm, which indicates that B³⁺ and Li⁺ co-doped SrAl₂O₄:Eu³⁺ is a good candidate phosphor applied in solid-state lighting in conjunction with white UV light-emitting diodes (LEDs).     

White light-emitting Mg0.1Sr1.9SiO4:Eu phosphors

Divalent europium-activated strontium orthosilicate Sr₂SiO₄:Eu²⁺ and Mg_0.1Sr_1.9SiO₄:Eu²⁺ phosphors were synthesized through the solid-state reaction technique. Their luminescent properties under ultraviolet excitation were investigated. The X-ray diffraction (XRD) results show that these phosphors are of α′-Sr₂SiO₄ phase with a trace of β-Sr₂SiO₄. Doping of Eu²⁺ ion into the crystal lattice results in the lattice constant being expended, while Mg²⁺ makes the lattice constant shrinking. A solid solution with the same crystal structure is formed when Eu²⁺ or Mg²⁺ substitutes part of Sr²⁺ ions and occupies the same lattice sites. The Sr₂SiO₄:Eu²⁺ phosphors show two emission spectra peaked at 535 and 473 nm originated from the 5d-4f transition of Eu²⁺ ion doped in two different Sr²⁺ sites in the host lattice. By substitution of 0.1 mol of Sr²⁺ with Mg²⁺, these two emission bands are tuned to be in the blue and yellow region (459 and 564 nm for Mg_0.1Sr_1.88SiO₄:Eu_0.02), respectively. The tuning effect is discussed. With a combination of the blue and yellow emission bands the phosphors show white color, indicating that these phosphors may become promising phosphor candidates for white light-emitting diodes (LEDs).     

Spherical Zn2SiO4:Eu@SiO2 phosphor particles in core-shell structure: Synthesis and characterization

Spherical SiO₂ particles have been coated with Zn₂SiO₄:Eu³⁺ phosphor layers by a Pechini sol-gel process. The microstructure and luminescent properties of the obtained Zn₂SiO₄:Eu³⁺@SiO₂ particles were well characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), photoluminescence (PL) spectra, and lifetime. The results demonstrate that the Zn₂SiO₄:Eu³⁺@SiO₂ particles, which have regular and uniform spherical morphology, emitted an intensive red light emission at 613 nm under excitation at 395 nm. Besides, the effects of the Eu³⁺ concentration, annealing temperature and charge compensators of Li⁺ ions on the PL emission intensities were investigated in detail.     

Luminescence investigation of red phosphors Ca0.54Sr0.34−1.5xEu0.08Smx(MoO4)y (WO4)1−y for UV-white LED device

Ca_0.54Sr_0.34−1.5xEu_0.08Sm_x(MoO₄)_y (WO₄)_1−y red phosphors were prepared by solid-state reaction using Na⁺ as a charge compensator for light-emitting diodes (LED). The effects of Na⁺ concentration, synthesis temperature, reaction time and Eu³⁺ concentration were studied for the properties of luminescence and crystal structure of red phosphors. The results show that the optimum reaction condition is 6%, 900 °C, 2 h and 8%. The photoluminescence spectra show that red phosphors are effectively excited at 616 nm by 292, 395 and 465 nm. The wavelengths of 465 nm nicely match the widely applied emission wavelengths of blue LED chips.     

Ca2SiO4:Dy3+材料的制备及其发光特性

采用高温固相法制备了Ca₂SiO₄:Dy³⁺发光材料.在365nm紫外光激发下,测得Ca₂SiO₄:Dy³⁺材料的发射光谱为一多峰宽谱,主峰分别位于486nm,575nm和665nm处;监测575nm发射峰,测得材料的激发光谱为一多峰宽谱,主峰分别位于331nm,361nm,371nm,397nm,435nm,461nm和478nm处.研究了Dy³⁺掺杂浓度对Ca₂SiO₄:Dy³⁺材料发射光谱及发光强度的影响,结果显示,随Dy³⁺浓度的增大,黄、蓝发射峰强度比(Y/B)逐渐增大,利用Judd-Ofelt理论解释了其原因;随Dy³⁺浓度的增大,Ca₂SiO₄:Dy³⁺材料发光强度先增大,在Dy³⁺浓度为4 mol%时到达峰值,而后减小,根据Dexter理论其浓度猝灭机理为电偶极-电偶极相互作用.研究了电荷补偿剂Li⁺,Na⁺和K⁺对Ca₂SiO₄:Dy³⁺材料发射光谱的影响,结果显示,不同电荷补偿剂下,随电荷补偿剂掺杂浓度的增大,Ca₂SiO₄:Dy³⁺材料发射光谱强度的演化趋势相同,即Ca₂SiO₄:Dy³⁺材料发射峰强度先增大后减小,但不同电荷补偿剂下,材料发射峰强度最大处对应的补偿剂浓度不同,对应Li⁺,Na⁺和K⁺时,浓度分别为4mol%,4mol%和3mol%. 关键词： 白光LED 2SiO₄:Dy³⁺')" href="#">Ca₂SiO₄:Dy³⁺ 发光特性 电荷补偿     

Energy transfer between activators at different crystallographic sites in Sr3SiO5:Eu

A yellow phosphor, Sr₃SiO₅:Eu²⁺, was synthesized by a high temperature solid-state method. Sr₃SiO₅:Eu²⁺ exhibits a single yellow emission under the blue radiation excitation. However, Sr₃SiO₅:Eu²⁺ shows a two-peak emission under the ultraviolet radiation excitation when Eu²⁺ doping content is less than 0.01 mol. Moreover, the blue emission disappears and the yellow emission reaches the peak value when Eu²⁺ doping content is 0.01 mol. Namely, the energy transfer takes place between the Eu²⁺ activators, which is located at two different crystallographic sites in the Sr₃SiO₅. And the energy transfer mechanism is the dipole-dipole interaction.     

Sr2CeO4:Eu and Sr2CeO4:5 mol% Eu, 3 mol% Dy microphosphors: Wet chemistry synthesis from hybrid precursor and photoluminescence properties

In this article, Sr₂CeO₄:x mol% Eu³⁺ and Sr₂CeO₄:5 mol%Eu³⁺, 3 mol% Dy³⁺ phosphors were synthesized from assembling hybrid precursors by wet chemical method. As-prepared samples present uniform grain-like morphology and the particle size is about 0.2 μm. The luminescence spectra of Sr₂CeO₄:x mol% Eu³⁺ have been measured to examine the influence of the intensity of red emission lines for Eu³⁺ on the concentration of Eu³⁺, showing that the intensity of the red emission increases with an increase of the concentration from 1 to 5 mol%. Additionally, from the emission spectra of Sr₂CeO₄:5 mol%Eu³⁺, 3 mol% Dy³⁺ phosphors, the characteristic lines of Dy³⁺ have also been observed. This result indicates that there also exists an energy transfer process between Sr₂CeO₄ and Dy³⁺.     

Spectroscopic properties, energy transfer and structural analysis of Sr2CeO4:M+ and Sr2CeO4:Eu3+, M+ (M+ = Li+, Na+, K+)

The room-temperature luminescent emission characteristics of Sr₂CeO₄:M⁺ and Sr₂CeO₄:Eu³⁺,M⁺ (M⁺ = Li⁺, Na⁺, K⁺) have been investigated under UV excitation. By introducing appropriate alkali metal cations dopants (Li⁺, Na⁺, K⁺) into the crystalline lattice, not only emission color of the blue-white-emitting Sr₂CeO₄ doped with low Eu³⁺ content can be tuned to green, but also the red emission intensity of Sr₂CeO₄ doped with high Eu³⁺ concentration is strengthened significantly. The relevant mechanisms have been elucidated in detail.     

Sol-gel growth of Gd2MoO6:Eu nanocrystalline layers on SiO2 spheres (SiO2@Gd2MoO6:Eu) and their luminescent properties

SiO₂@Gd₂MoO₆:Eu³⁺ core-shell phosphors were prepared by the sol-gel process. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectra (EDS), transmission electron microscopy (TEM), photoluminescence (PL) spectra as well as kinetic decays were used to characterize the resulting SiO₂@Gd₂MoO₆:Eu³⁺ core-shell phosphors. The XRD results demonstrate that the Gd₂MoO₆:Eu³⁺ layers on the SiO₂ spheres begin to crystallize after annealing at 600 °C and the crystallinity increases with raising the annealing temperature. The obtained core-shell phosphors have a near perfect spherical shape with narrow size distribution (average size ca. 600 nm), are not agglomerated, and have a smooth surface. The thickness of the Gd₂MoO₆:Eu³⁺ shells on the SiO₂ cores could be easily tailored by varying the number of deposition cycles (50 nm for four deposition cycles). The Eu³⁺ shows a strong PL luminescence (dominated by ⁵D₀-⁷F₂ red emission at 613 nm) under the excitation of 307 nm UV light. The PL intensity of Eu³⁺ increases with increasing the annealing temperature and the number of coating cycles.     

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.     

Enhanced luminescence of GdTaO4:Eu thin-film phosphors by K doping

The effect of K⁺ ions on GdTaO₄:Eu³⁺ thin-film phosphors was investigated in order to improve their luminescent properties. The GdTaO₄:Eu_0.1, K_x thin films were synthesized by sol-gel process, and characterized through measuring their microstructure and luminescence. The results indicated that photoluminescence (PL) intensity of GdTaO₄:Eu³⁺ film was improved remarkably by K doping. There were two maxima in the curve of PL intensity against K⁺ dopant concentration, where one was improved up to 2.1 times at x = 0.001 and the other was enhanced up to 2.7 times at x = 0.05. The first maximum was regarded as the alteration of the local environment surrounding the Eu³⁺ activator by incorporation of K⁺ ions, and the second maximum was due to the flux effect. Additionally, the luminescence increased with the increase of firing temperature from 800 °C to 1200 °C.     

Charge compensation on the luminescence properties of ZnWO4:Tb phosphors via hydrothermal synthesis

A phosphor Tb³⁺-doped ZnWO₄ (ZWO:Tb) phosphors were prepared by a hydrothermal method. X-ray powder diffraction (XRD) analysis revealed that the as-obtained sample is pure ZnWO₄ phase. The excitation and emission spectra indicated that the phosphor could be well excited by ultraviolet light (272 nm) and emit blue light at about 491 nm and green light at about 545 nm. Significant energy transfer from WO₄²⁻ groups to Tb³⁺ ions has been observed. Two approaches to charge compensation are investigated: (a) 2Zn²⁺ = Tb³⁺ + M⁺, where M⁺ is a monovalent cation like Li⁺, Na⁺ and K⁺ acting as a charge compensator; (b) 3Zn²⁺ = 2Tb³⁺ + vacancy. Compared with two charge compensation patterns in the ZnWO₄:Tb³⁺, it has been found that ZnWO₄:Tb³⁺ phosphors used Li⁺ as charge compensation show greatly enhanced bluish-green emission under 272 nm excitation.     

Preparation and luminescent properties of BaCa2Si3O9:Eu

A blue emitting phosphor of the triclinic BaCa₂Si₃O₉:Eu²⁺ was prepared by the combustion-assisted synthesis method and an efficient blue emission ranging from the ultraviolet to visible was observed. The luminescence and crystallinity were investigated using luminescence spectrometry and X-ray diffractometry (XRD), respectively. The emission spectrum shows a single intensive band centered at 445 nm, which corresponds to the 4f⁶5d¹→4f⁷ transition of Eu²⁺. The excitation spectrum is a broad extending from 260 to 450 nm, which matches the emission of ultraviolet light-emitting diodes (UV-LEDs). The critical quenching concentration of Eu²⁺ in BaCa₂Si₃O₉:Eu²⁺ phosphor is about 0.05 mol. The corresponding concentration quenching mechanism is verified to be a dipole-dipole interaction. The CIE of the optimized sample Ba_0.95Ca₂Si₃O₉:Eu_0.05²⁺ was (x, y)=(0.164, 0.111). The result indicates that BaCa₂Si₃O₉:Eu²⁺ can be potentially useful as a UV radiation-converting phosphor for white light-emitting diodes (LEDs).     

Enhanced photoluminescence properties of Zn2SiO4:Mn co-activated with Y/Li under VUV excitation

A series of green phosphors Zn_1.92−2xY_xLi_xSiO₄:0.08Mn²⁺ (0≤x≤0.03) were prepared by solid-state synthesis method. Phase and lattice parameters of the synthesized phosphors were characterized by powder X-ray diffractometer (XRD) and the co-doped effects of Y³⁺/Li⁺ upon emission intensity and decay time were investigated under 147 nm excitation. The results indicate that the co-doping of Y³⁺/Li⁺ has favorable influence on the photoluminescence properties of Zn₂SiO₄:Mn²⁺, and the optimal photoluminescence intensity of Zn_1.90Y_0.01Li_0.01SiO₄:0.08Mn²⁺ is 103% of that of commercial phosphor when the doping concentration of Y³⁺/Li⁺ is 0.01 mol. Additionally, the decay time of phosphor is much shortened and the decay time of Zn_1.90Y_0.01Li_0.01SiO₄:0.08Mn²⁺ is 3.39 ms, shorter by 1.83 ms than that of commercial product after Y³⁺/Li⁺ co-doping.     

Synthesis of Y2Si2O7:Eu nanocrystal and its optical properties

Nanocrystalline Y₂Si₂O₇:Eu phosphor with an average size about 60 nm is easily prepared using silica aerogel as raw material under ultrasonic irradiation and annealing temperature at 300-600 °C and this nanocrystalline decomposes into Y₂O₃:Eu and silica by heat treatment at 700-900 °C. The excitation broad band centered at 283 and 254 nm results from Eu³⁺ substituting for Y³⁺ in Y₂Si₂O₇ and Y₂O₃/SiO₂, respectively. Compared with Y₂O₃:Eu/SiO₂ crystalline, the PL excitation and emission peaks of Y₂Si₂O₇:Eu nanocrystalline red-shift and lead to the enhance of its luminescence intensity due to the different chemical surroundings of Eu³⁺ in above nanocrystallines. The decrease of PL intensity may be ascribed to quenching effect resulting from more defects in Y₂O₃:Eu/SiO₂ crystalline.     

Blue-emitting long-lasting phosphor, Sr3Al10SiO20:Eu,Ho

A novel blue-emitting long-lasting phosphor Sr₃Al₁₀SiO₂₀:Eu²⁺,Ho³⁺ is prepared by the conventional high-temperature solid-state technique and their luminescent properties are investigated. XRD, photoluminescence (PL) and thermoluminescence (TL) are used to characterize the synthesized phosphors. These phosphors are well crystallized by calcinations at 1500-1600 °C for 3 h. The phosphor emits blue light and shows long-lasting phosphorescence after it is excited with 254/365 nm ultraviolet light. TL curves reveal the introduction of Ho³⁺ ions into the Sr₃Al₁₀SiO₂₀:Eu²⁺ host produces a highly dense trap level at appropriate depth, which is the origin of the long-lasting phosphorescence in this kind of material. The long-lasting phosphorescence lasts for nearly 6 h in the light perception of the dark-adapted human eye (0.32 mcd/m²). All the results indicate that this phosphor has promising potential practical applications.