Photoluminescence studies of red-emitting NaEu(WO4)2 as a near-UV or blue convertible phosphor

Sodium europium double tungstate [NaEu(WO₄)₂] phosphor was prepared by the solid-state reaction method. Its crystal structure, photoluminescence properties and thermal quenching characteristics were investigated aiming at the potential application in the field of white light-emitting diodes (LEDs). The influences of Sm doping on the photoluminescence properties of this phosphor were also studied. It is found that this phosphor can be effectively excited by 394 or 464 nm light, which nicely match the output wavelengths of near-ultraviolet (UV) or blue LED chips. Under 394 or 464 nm light excitation, this phosphor exhibits stronger emission intensity than the Y₂O₂S:Eu³⁺ or Eu²⁺-activated sulfide phosphor. The introduction of Sm³⁺ ions can broaden the excitation peaks at 394 and 464 nm of the NaEu(WO₄)₂ phosphor and significantly enhance its relative luminance under 400 and 460 nm LEDs excitation. Furthermore, the relative luminance of NaEu(WO₄)₂ phosphor shows a superior thermal stability compared with the commercially used sulfide or oxysulfide phosphor, and make it a promising red phosphor for solid-state lighting devices based on near-UV or blue LED chips.     

Enhancement of red spectral emission intensity of Y3Al5O12:Ce phosphor via Pr co-doping and Tb substitution for the application to white LEDs

We have enhanced color-rendering property of a blue light emitting diode (LED) pumped white LED with yellow emitting Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce) phosphor using addition of Pr and Tb as a co-activator and host lattice element, respectively. Pr³⁺ addition to YAG:Ce phosphor resulted in sharp emission peak at about 610 nm through ¹D₂→³H₄ transition. And when Tb³⁺ substituted Y³⁺ sites, Ce³⁺ emission band shifted to a longer wavelength due to larger crystal field splitting. Y₃Al₅O₁₂:Ce³⁺, Pr³⁺ and (Y_1−xTb_x)₃Al₅O₁₂:Ce³⁺ phosphors were coated on blue LEDs to fabricate white LEDs, respectively, and their color-rendering indices (CRIs, R_a) were measured. As a consequence of the addition of Pr³⁺ or Tb³⁺, CRI of the white LEDs improved to be R_a=83 and 80, respectively. Especially, blue LED pumped (Y_0.2Tb_0.8)₃Al₅O₁₂:Ce³⁺ white LED showed both strong luminescence and high color-rendering property.     

Eu red long afterglow in Y2O2S:Ti, Eu phosphor through afterglow energy transfer

Eu,Ti co-doped Y₂O₂S:0.03Ti,0.03Eu phosphors and single Eu or Ti doped Y₂O₂S phosphors were prepared and their luminescent properties were investigated in detail by photoluminescence (PL) spectra, long afterglow spectra and thermoluminescence spectra measurements. The results showed that Y₂O₂S:Ti,Eu phosphors possess orange-red afterglow color with afterglow time above 5 h. The reddish afterglow color, which corresponds to a set of linear Eu³⁺ emissions at low-energy range (540-630 nm), was demonstrated to come from the energy transfer process from yellow Ti afterglow emissions, the proposed energy transfer mechanism may well explain the Eu³⁺ afterglow emission.     

Photoluminescence and gamma-ray irradiation of SrAl2O4:Euand Y2O3:Eu phosphors

Y₂O₃:Eu³⁺ phosphor is a very attractive material for use as a red phosphor in many fields. SrAl₂O₄:Eu²⁺ belongs to long lasting phosphor (LLP) and it is a useful bluish-green luminescence material, which can also be a promising candidate as a simple and easy-to-use radiation detection element for visual display of two dimensional radiation distributions. In the present study, both these two kinds of phosphors were synthesized using high temperature solid state reactions. In our work, the influence of gamma-ray irradiation on the properties of these two kinds of phosphors was studied by comparing photoluminescence, brightness and the decay curve of unirradiated and gamma-ray-irradiated samples. Conclusions from the present work can be briefly summarized as follows. In irradiated samples, the brightness is decreased without sensible change in the wavelength distribution of the luminescence spectrum and in the decay kinetic upon gamma exposure. Moreover, the emission due to Eu³⁺→Eu²⁺ conversion in Y₂O₃:Eu³⁺ phosphors was not observed in our sample after irradiation to high exposure. Also the brightness of SrAl₂O₄:Eu²⁺ phosphor turned out to decrease after the exposition to ionizing radiation while the luminescence wavelength distribution remained unchanged. The reason for the effect of gamma-ray irradiation on the properties of phosphors is also discussed in the paper.     

White-light long-lasting phosphorescence from Tb-activated Y2O2S phosphor

The white-light long-lasting phosphors Y₂O₂S:Tb³⁺, Sr²⁺ or/and Zr⁴⁺ were prepared and studied. The white-light afterglow emission after the irradiation with 254 nm UV are composed of the blue light emission and the yellowish-green light emission, originating from the transitions of ⁵D₃→⁷F₅, ⁵D₄→⁷F₅ in Tb³⁺ when the Tb³⁺ concentration is not higher than 0.3 at%. The codoped Sr²⁺ and Zr⁴⁺ ions act as trap-creating ions. The afterglow can last over 21 min in the dark for Y₂O₂S:Tb³⁺0.3%, Sr²⁺4%, Zr⁴⁺4% after irradiation by 254 nm ultraviolet light. Y₂O₂S:Tb³⁺ may be a promising material for the development of white-light long-lasting phosphor since the Tb³⁺ has a high luminescent efficiency and the dominant excitation band of 4f →5d is located at 220-300 nm.     

Photoluminescence of Y2O3:Eu thin film phosphors by sol-gel deposition and rapid thermal annealing

Y₂O₃:Eu³⁺ phosphor films have been developed by using the sol-gel process. Comprehensive characterization methods such as Photoluminescent (PL) spectroscopy, X-ray diffraction (XRD) and Fourier Transform Infrared (FTIR) spectroscopy were used to characterize the Y₂O₃:Eu³⁺ phosphor films. In this experiment, the XRD profiles show that the Y₂O₃:Eu³⁺ phosphor films crystallization temperature and optimum annealing temperature occur at about 650 and 750 °C, respectively. The optimum dopant concentration is 12 mol% Eu³⁺ and the critical transfer distance (R_c) among Eu³⁺ ions is calculated to be about 0.84 nm. Vacuum environment is more efficient than oxygen and nitrogen to eliminate the OH content and hence yields higher luminescent phosphor films. The PL emission intensity of Y₂O₃:Eu³⁺ phosphor films is also dependent on the annealing time. It was found that the H₂O impurities were effectively eliminated after annealing time of 25 s at 750 °C in vacuum environment. From the experiment results, the schematic energy band diagram of Y₂O₃:Eu³⁺ phosphor films is constructed.     

Preparation and optical properties of Ag enwrapped Y2O3:Eu nanoparticles in solution and in powders

Ag enwrapped Y₂O₃:Eu³⁺ nanoparticles were prepared by a wet chemistry method, which was dispersed in liquid (glycol) or dried to powders. Their luminescence properties were studied in comparison to those in the un-enwrapped ones. The results demonstrated that in glycol the ⁵D₀-⁷F₂ transitions for Ag enwrapped Y₂O₃:Eu³⁺ nanoparticles became stronger than that for un-enwrapped ones, while the excitation charge transfer band shifted blue. On the contrary, the ⁵D₀-⁷F₂ transitions in Ag enwrapped Y₂O₃:Eu³⁺ powders became weaker than those in the un-enwrapped ones. It was suggested that in liquid the Ag shells thinly deposited in the surface of Y₂O₃:Eu³⁺ and insulated the Y₂O₃:Eu³⁺ from the liquid, which contained large organic vibration modes. As a result, the surface nonradiative energy transfer from Eu³⁺ to the organic modes decreased, and emission intensity of ⁵D₀-⁷F₂ increased. In the Y₂O₃:Eu³⁺ powders, the Ag shells absorbed the excitation light, leading to the decrease in excitation density and the intensity of ⁵D₀-⁷F₂.     

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).     

Preparation and Luminescence Characteristics of Ca3Y2（BO3）4：Eu^3＋ Phosphor

Ca3Y2 （BO3）4：Eu^3＋ phosphor is synthesized by high temperature solid-state reaction method, and the Iuminescence characteristics are investigated. The emission spectrum exhibits two strong red emissions at 613 and 621 nm corresponding to the electric dipole ^5 Do- ^7F2 transition of Eu^3＋ under 365 nm excitation, the reason is that Eu^3＋ substituting for Y^3＋ occupies the non-centrosymmetric position in the crystal structure of Ca3 Y2 （BO3）4. The excitation spectrum for 613 nm indicates that the phosphor can be effectively excited by ultraviolet （UV） （254 nm, 365nm and 400nm） and blue （470nm） light. The effect of Eu^3＋ concentration on the emission intensity of Ca3 Y2 （BO3）4 ：Eu^3＋ phosphor is measured, the result shows that the emission intensities increase with increasing Eu^3＋ concentration, then decrease. The CIE colour coordinates of Ca3Y2 （BO3）4：Eu^3＋ phosphor is （0.639, 0.357） at 15mol% Eu^3＋.     

A novel blue-emitting long-lasting proyphosphate phosphor Sr2P2O7:Eu,Y

By introducing the Y³⁺ into Sr₂P₂O₇:Eu²⁺, we successfully prepared a kind of new phosphor with blue long-lasting phosphorescence by the high-temperature solid-state reaction method. In this paper, the properties of Sr₂P₂O₇:Eu²⁺,Y³⁺ were investigated utilizing XRD, photoluminescence, luminescence decay, long-lasting phosphorescence and thermoluminescence (TL) spectra. The phosphor emitted blue light that was related to the 4f⁶5d¹-⁸S_7/2 transition of Eu²⁺. The bright blue phosphorescence could be observed by naked eyes even 8 h after the excitation source was removed. Two TL peaks at 317 and 378 K related to two types of defects appeared in the TL spectrum. By analyzing the TL curve the depths of traps were calculated to be 0.61 and 0.66 eV. Also, the mechanism of LLP was discussed in this report.     

Effect of Sr substitution on photoluminescent properties of BaAl2O4:Eu, Dy

Phosphor material BaAl₂O₄:Eu²⁺, Dy³⁺ with varying compositions of Sr substitution were prepared by the solid-state synthesis method. The phosphor compositions were characterized for their phase and crystallinity by XRD, SEM and TEM. Photoluminescence (PL) properties were investigated measuring PL and decay time for varying Ba/Sr compositions. The PL results show the blue shift in the luminescence properties in Sr substituted BaAl₂O₄:Eu²⁺, Dy³⁺ compared to parent BaAl₂O₄:Eu²⁺, Dy³⁺. It is probably due to the influence of 5d electron states of Eu²⁺ in the crystal field because of atomic size variation causing crystal defects. Dy³⁺ ion doping in the phosphor generates deep traps, which results in long afterglow phosphorescence.     

A potential red phosphor LiGd(MoO4)2:Eu for light-emitting diode application

Eu³⁺-doped LiGd(MoO₄)₂ red phosphor was synthesized by solid-state reaction, and its photoluminescent properties were measured. The effect of Eu³⁺ doping concentration on PL intensity was investigated, and the optimum concentration of Eu³⁺ doped in LiGd(MoO₄)₂ was found to be 30 mol%. Compared with Y₂O₂S:0.05Eu³⁺, Na_0.5Gd_0.5MoO₄:Eu³⁺ and KGd(MoO₄)₂:Eu³⁺, the LiGd(MoO₄)₂:Eu³⁺ phosphor showed a stronger excitation band around 395 nm and a higher intensity red emission of Eu³⁺ under 395 nm light excitation. For the first time, intensive red light-emitting diodes (LEDs) were fabricated by combining phosphor and a 395 nm InGaN chip, confirming that the LiGd(MoO₄)₂:Eu³⁺ phosphor is a good candidate for LED applications.     

Structural, luminescent and thermal properties of blue SrAl2O4:Eu, Dy phosphor filled low-density polyethylene composites

The performance of nanophase luminophors is usually compromised by environmentally induced degradation. In this study, composites of low density polyethylene (LDPE) with various concentrations of the blue-emitting europium and dysprosium co-doped strontium aluminate (SrAl₂O₄:Eu²⁺,Dy³⁺) phosphor were investigated. The blue long-lasting phosphorescence of the composites was observed in the dark after removal of the excitation light. X-ray diffraction analysis revealed the presence of the SrAl₂O₄ phase in the composites. PL spectra of the composites have two sets of peaks, major broad bands peaking at about 4855 Å and minor ones at wavelengths between 4115 and 4175 Å, attributed to the 4f-5d transition of Eu²⁺. DSC and TGA results show that the introduction of the phosphor in LDPE matrix caused a slight reduction in the crystallinity of LDPE but a significant increase in the stability of the composites.     

Synthesis and luminescence investigation of RE (Eu, Tb and Ce)-doped lithium silicate (Li2SiO3)

Synthesis and photoluminescence (PL) investigations of lithium metasilicate doped with Eu³⁺, Tb³⁺ and Ce³⁺ were carried out. PL spectra of Eu-doped sample showed peaks corresponding to the ⁵D₀→⁷F_j (j=1, 2, 3 and 4) transitions under ultraviolet excitation. Strong red emission coming from the hypersensitive ⁵D₀→⁷F₂ transition of Eu³⁺ ion suggested the presence of the dopant ion in structurally disordered environment. Tb³⁺-doped silicate sample showed blue-green emission corresponding to the ⁵D₄→⁷F_j (j=6, 5 and 4) transitions. Ce-doped sample under excitation from UV, showed a broad emission band in the region 350-370 nm with shoulders around 410 nm. The fluorescence lifetimes of Eu³⁺ and Tb³⁺ ions were found out to be 790 and 600 μs, respectively. For Ce³⁺, the lifetime was of the order of 45 ns. PL spectra of the europium- and terbium-doped samples were compared with commercial red (Y₂O₃:Eu³⁺) and green (LaPO₄:Tb³⁺) phosphors, respectively. It was found that the emission from the doped silicate sample was 37% of the commercial phosphor in case of the Tb-doped sample and 8% of the commercial phosphor in case of the Eu-doped sample.     

Preparation and luminescence properties of Y2(WO4)3: Eu3+

A red-emitting Y₂(WO₄)₃: Eu³⁺ phosphor (orthorhombic high temperature phase, anhydride) is prepared by two different methods: the firing of mixtures of constituent oxides and that of precipitates from aqueous solutions. After optimizing preparation conditions, the cathodoluminescence brightness reaches 56% that of Y₂O₂S: Eu³⁺, a commercial red phosphor for color TV. Formation of a high temperature phase below the reported transition temperature is noted in the fired precipitates. This phase occurrence is shown to depend on the treatment of the precipitates to be fired. Reflection difference measurement of Eu-doped and undoped samples assigns an excitation band of about 245 nm to the Eu-O charge transfer band. Different by-products in the two preparation methods are identified by measuring emission spectra under selective excitation. Reversible hydration-dehydration of the phosphor is demonstrated by successively measuring photoluminescence first in vacuum and then in air at various temperatures. No deterioration of luminescence efficiency is observed after repeating this reversible structural change.     

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.     

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.     

Effects of Na2CO3 flux addition on the structure and photoluminescence properties for Eu-doped YVO4 phosphor

The luminescence properties of (Y_0.9Eu_0.1)VO₄ phosphor with Na₂CO₃ flux prepared using the solid-state reaction were investigated. The XRD patterns show that all of the peaks are attributed to the YVO₄ phase. The best crystallinity was obtained with 2 wt% Na₂CO₃ flux addition. The surface morphology of (Y_0.9Eu_0.1)VO₄ phosphor changed from fluffy to a bar shape structure after Na₂CO₃ flux addition due to the tetragonal crystal system of YVO₄. The calcined powders emit bright red luminescence centered at 618 nm due to the ⁵D₀→⁷F₂ electric dipole transition under an excitation wavelength of 318 nm; its intensity was increased about 15% with 2 wt% Na₂CO₃ flux addition. Red shift behavior was observed for the charge transfer state (CTS) absorption, which was due to the grain size of (Y_0.9Eu_0.1)VO₄ phosphor increasing with increasing flux content. For 2 wt% Na₂CO₃ flux addition, the red emission of the (Y_0.9Eu_0.1)VO₄ phosphor had CIE chromaticity coordinates of (0.66, 0.34), which are very close to the NTSC system standard red chromaticity coordinates of (0.67, 0.33).     

Emission analysis of Eu:MgLaLiSi2O7 powder phosphor

Newly synthesized reference MgLaLiSi₂O₇ and red luminescent Eu³⁺:MgLaLiSi₂O₇ powder phosphors have been successfully developed by a solid-state reaction method to analyze their emission and structural properties from the measurement of their XRD, SEM, FTIR and PL spectra. Emission spectra of Eu³⁺ powder phosphors have shown strong red emissions at 613 nm (⁵D₀→⁷F₂). These phosphors have also shown bright red emissions under a UV source. Based on the red emission performance, the Eu³⁺ concentration has been optimized to be at 0.3 mol%.     

First applicability of ZnGa2O4 : Ge, Li, Mn phosphor for a plasma display panel

The green emission intensity of ZnGa₂O₄:Ge⁴⁺, Li⁺, Mn²⁺ excited by the vacuum ultraviolet line of 147 nm reaches 70% of commercial green Zn₂SiO₄:Mn²⁺. The vacuum ultraviolet excitation spectra consist of four peaks. In a plasma display test bed filled with Ar and Ne plasma discharged by a radio-frequency generator of 13.6 MHz, ZnGa₂O₄:Ge⁴⁺, Li⁺, Mn²⁺ and commercial Zn₂SiO₄:Mn²⁺ phosphor screens show a linear increase in luminance with increasing self bias voltages. Increasing gas pressures cause the luminance to increase. Also, on increasing the self bias voltages and the gas pressures, the current densities of ZnGa₂O₄:Ge⁴⁺, Li⁺, Mn²⁺ phosphor screens are increased; this is the same behavior as that of the commercial phosphor.