Ca1−xMo1−ySiyO4:Eux: A novel red phosphor for white light emitting diodes

Single phase of Ca_1−xMo_1−ySi_yO₄:Eu_x³⁺ (0.18?x?0.26, 0?y?0.04) was synthesized by solid-state method. The photoluminescence investigation indicated that Ca_1−xMoO₄:Eu_x³⁺ (0.18?x?0.26) could be effectively excited by 393 and 464 nm, and it exhibited an intense red emission at 615 nm. The introduction of Si⁴⁺ ions did not change the position of the peaks but strongly enhanced the emission intensity of Eu³⁺ under 393 and 464 nm excitations and showed very good color purity. The emission intensity of optimal Ca_0.8Mo_0.98Si_0.02O₄:Eu_0.2³⁺ sample (excited by 393 nm) was about 5.5 times higher than that of the phosphor Y₂O₂S:0.05Eu³⁺. So this phosphor could be nicely suitable for the application of the UV LED chips.     

Luminescence studies of a combustion-synthesized blue–green BaAlxOy:Eu,Dy nanoparticles

Blue–green emitting BaAl_xO_y:Eu²⁺,Dy³⁺ phosphor was synthesized by the combustion method. The influence of various parameters on the structural, photoluminescence (PL) and thermoluminescence (TL) properties of the phosphor were investigated by various techniques. Phosphor nanocrystallites with high brightness were obtained without significantly changing the crystalline structure of the host. In the PL studies, broad-band excitation and emission spectra were observed with major peaks at 340 and 505 nm, respectively. The observed afterglow is ascribed to the generation of suitable traps due to the presence of the co-doped Dy³⁺ ions. Though generally broad, the peak structure of the TL glow curves obtained after irradiation with UV light was non-uniform with suggesting the contribution to afterglow from multiple events at the luminescent centers. Further insight on the afterglow behavior of the phosphor was deduced from TL decay results.     

Correlated ESR, PL and TL studies on Sr5(PO4)3Cl:Eu thermoluminescence dosimetry phosphor

Electron spin resonance (ESR), thermoluminescence and photoluminescence studies in Eu²⁺ activated Sr₅(PO₄)₃Cl phosphor are reported in this paper. The Sr₅(PO₄)₃Cl:Eu²⁺ phosphor is twice as sensitive as the conventional CaSO₄:Dy phosphor used in thermoluminescence dosimetry of ionizing radiations. It has a linear response, simple glow curve, emission peaking at 456 nm. The defect centers formed in the Sr₅(PO₄)₃Cl:Eu²⁺phosphor are studied by using the technique of ESR. A dominant TL glow peak at 430 K with a smaller shoulder at 410 K is observed in the phosphor. ESR studies indicate the presence at three centers at room temperature. Step annealing measurements show a connection between one of the centers and the dominant glow peak at 430 K. The 430 K TL peak is well correlated with center I, which is tentatively identified as (PO₄)²⁻ radical.     

Synthesis and luminous characteristics of Ba2MgSi2−xAlxO7: 0.1Eu, 0.1Mn phosphor for WLED

The shift of the emission band to longer wavelength (yellow-orange) of the Ba₂MgSi_2−xAl_xO₇: 0.1Eu²⁺ phosphor under the 350-450 nm excitation range has been achieved by adding the codoping element (Mn²⁺) in the host. The single-host silicate phosphor for WLED, Ba₂MgSi_2−xAl_xO₇: 0.1Eu²⁺, 0.1Mn²⁺ was prepared by high-temperature solid-state reaction. It was found experimentally that, its three-color emission peaks are situated at 623, 501 and 438 nm, respectively, under excitation of 350-450 nm irradiation. The emission peaks at 438 and 501 nm originate from the transition 5d to 4f of Eu²⁺ ions that occupy the two Ba²⁺ sites in the crystal of Ba₂MgSi_2−x Al_xO₇, while the 623 nm emission is attributed to the energy transfer from Eu²⁺ ions to Mn²⁺ ions. The white light can be obtained by mixing the three emission colors of blue (438 nm), green (501 nm) and red (623 nm) in the single host. When the concentrations of the Al³⁺, Eu²⁺ and Mn²⁺ ions were 0.4, 0.1 and 0.1 mol, respectively, the sample presented intense white emission. The addition of Al ion to the host leads to a substantial change of intensity ratio between blue and green emissions. White light could be obtained by combining this phosphor with 405 nm light-emitting diodes. The near-ultraviolet GaN-based Ba₂MgSi_1.7 Al_0.3O₇: 0.1Eu²⁺, 0.1Mn²⁺ LED achieves good color rendering of over 85.     

Combustion synthesis and luminescence properties of NaY1−xEux(WO4)2 phosphors

The red phosphors NaY_1−xEu_x(WO₄)₂ with different concentrations of Eu³⁺ were synthesized via the combustion synthesis method. As a comparison, NaEu(WO₄)₂ was prepared by the solid-state reaction method. The phase composition and optical properties of as-synthesized samples were studied by X-ray powder diffraction and photoluminescence spectra. The results show that the red light emission intensity of the combustion synthesized samples under 394 nm excitation increases with increase in Eu³⁺ concentrations and calcination temperatures. Without Y ions doping, the emission spectra intensity of the NaEu(WO₄)₂ phosphor prepared by the combustion method fired at 900 °C is higher than that prepared by the solid-state reaction at 1100 °C. NaEu(WO₄)₂ phosphor synthesized by the combustion method at 1100 °C exhibits the strongest red emission under 394 nm excitation and appropriate CIE chromaticity coordinates (x=0.64, y=0.33) close to the NTSC standard value. Thus, its excellent luminescence properties make it a promising phosphor for near UV InGaN chip-based red-emitting LED application.     

Effect of Ca and Sr alkaline earth ions on luminescence properties of BaAl12O19:Eu nanophosphor

Nanosized barium aluminate materials was doped by divalent cations (Ca²⁺, Sr²⁺) and Eu²⁺ having nominal compositions Ba_1−xMxAl₁₂O₁₉:Eu (M=Ca and Sr) (x=0.1-0.5), were synthesized by the combustion method. These phosphors were characterized by XRD, scanning electron microscopy-energy-dispersive spectrometry (SEM-EDS) and photoluminescence measurement. The photoluminescence characterization showed the presence of Eu ion in divalent form which gave emission bands peaking at 444 nm for the 320 nm excitation (solid-state lighting excitation), while for 254 nm it gave the same emission wavelength of low intensity (1.5 times) compared to 320 nm excitation. It was also observed that alkaline earth metal (Ca²⁺ and Sr²⁺) dopants increase the intensity of Eu²⁺ ion in BaAl₁₂O₁₉ lattice, thus this phosphor may be useful for solid-state lighting.     

Dosimetric properties of rare earth doped LiCaBO3 thermoluminescence phosphors

Lithium Calcium borate (LiCaBO₃) polycrystalline thermoluminescence (TL) phosphor doped with rare earth (RE³⁺) elements has been synthesized by high temperature solid state diffusion reaction. The reaction has produced a very stable crystalline LiCaBO₃:RE³⁺ phosphors. Among these RE³⁺ doped phosphors thulium doped material showed maximum TL sensitivity with favorable glow curve shape. TL glow curve of gamma irradiated LiCaBO₃:Tm³⁺ samples had shown two major well-separated glow peaks at 230 and 430 °C. The glow peak at 430 °C is almost thrice the intensity of the glow peak at 230 °C. The TL sensitivity of the phosphor to gamma radiation was about eight times that of TLD-100 (LiF). Photoluminescence and TL emission spectra showed the characteristic Tm³⁺ peaks. TL response to gamma radiation dose was linear up to 10³ Gy. Post-irradiation TL fading on storage in room temperature and elevated temperatures was studied in LiCaBO₃:Tm³⁺ phosphor.     

Photoluminescence properties of Eu in Y(PO3)3 under VUV excitation

The photoluminescence properties of Y_1−x(PO₃)₃:xEu³⁺ (0<x≤0.2) are investigated. The excitation spectrum of Y_0.85(PO₃)₃:0.15Eu₃⁺ shows that both the (PO₃)₃³⁻ groups and the CT bands of O²⁻-Y³⁺ can efficiently absorb the excitation energy in the region of 120-250 nm. Under 147 nm excitation, the optimal emissive intensity of Y_1−x(PO₃)₃:xEu³⁺ (0<x≤0.2) is about 36% of the commercial phosphor (Y,Gd)BO₃:Eu³⁺, which hints that the absorbed energy by the host matrix could be efficiently transferred to Eu³⁺. We try to study the concentration quenching mechanism of Y_1−x(PO₃)₃:xEu³⁺ (0<x≤0.2) under 147 and 172 nm excitation.     

Synthesis and luminescence properties of red-emitting phosphors NaY0.87Eu0.13(WO4)1.2(MoO4)0.8

A series of NaY_1−yEu_y(WO₄)_2−x(MoO₄)_x (x=0−2 and y=0.06−0.15) phosphors have been prepared by a combustion route. X-ray powder diffraction, photoluminescence excitation and emission spectra were used to characterize the resulting samples. The excitation spectra of these phosphors show the strongest absorption at about 396 nm, which matches well with the commercially available n-UV-emitting GaN-based LED chip. Their emission spectra show an intense red emission at 616 nm due to the ⁵D₀→⁷F₂ electric dipole transition of Eu³⁺. As the Mo content increases, the intensity of the ⁵D₀→⁷F₂ emission of Eu³⁺ activated at wavelength of 396 nm increases and reaches a maximum when the relative ratio of Mo/W is 2:3. The intense red-emission of the tungstomolybdate phosphors at near-UV excitation suggests that the material is a potential candidate for white light emitting diode (WLEDs).     

Luminescence properties of a new Mn-activated red long-afterglow phosphor

A new phosphor, CaZnGe₂O₆:Mn²⁺, which emits red long-lasting phosphorescence centered at 648 nm upon UV light excitation, is prepared by the conventional high-temperature solid-state method and its luminescent properties are systematically investigated in this paper. XRD, photoluminescence, thermoluminescence spectra and afterglow decay curve are used to characterize the synthesized phosphor. This phosphor is well crystallized by calcination at 1150 °C for 3 h and possesses excellent performance. The color coordinate values of this phosphor are x=0.64, y=0.26 under 250 nm UV light excitation. Under 250-nm UV light irradiation, this phosphor shows obvious long-lasting phosphorescence that can be seen with the naked eye in the dark clearly after the irradiation source has been removed for more than 3 h. The possible mechanism of this red-light-emitting long-afterglow phosphor is also investigated based on the experiment results.     

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.     

Green Eu-doped Ba3Si6O12N2 phosphor for white light-emitting diodes: Synthesis, characterization and theoretical simulation

The Eu²⁺-doped Ba₃Si₆O₁₂N₂ green phosphor (Eu_xBa_3−xSi₆O₁₂N₂) was synthesized by a conventional solid state reaction method. It could be efficiently excited by UV-blue light (250-470 nm) and shows a single intense broadband emission (480-580 nm). The phosphor has a concentration quenching effect at x=0.20 and a systematic red-shift in emission wavelength with increasing Eu²⁺ concentration. High quantum efficiency and suitable excitation range make it match well with the emission of near-UV LEDs or blue LEDs. First-principles calculations indicate that Ba₃Si₆O₁₂N₂:Eu²⁺ phosphor exhibits a direct band gap, and low band energy dispersion, leading to a high luminescence intensity. The origin of the experimental absorption peaks is clearly identified based on the analysis of the density of states (DOS) and absorption spectra. The photoluminescence properties are related to the transition between 4f levels of Eu and 5d levels of both Eu and Ba atoms. The 5d energy level of Ba plays an important role in the photoluminescence of Ba₃Si₆O₁₂N₂:Eu²⁺ phosphor. The high quantum efficiency and long-wavelength excitation are mainly attributed to the existence of Ba atoms. Our results give a new explanation of photoluminescence properties and could direct future designation of novel phosphors for white light LED.     

Synthesis and luminescent properties of a new red-emitting phosphor for solid-state lighting: Eu0.1GdxLa1.9−xTeO6 (0.02?x?0.1)

The photoluminescence (PL) emission and excitation behavior of red-emitting Eu_0.1Gd_xLa_1.9−xTeO₆ (0.02?x?0.1) powder phosphors is reported. Three dominant bands centered at 395, 466 and 534 nm characterized the excitation spectrum. Under the excitation of 395 nm UV light, the emission spectrum exhibits an intense peak centered at 616 nm corresponding to the ⁵D₀→⁷F₂ transition of Eu³⁺. Because the f→f transitions are located in the wavelength range of blue or near-UV range, optimized phosphor, Eu_0.10Gd_0.08La_1.82TeO₆, is a promising material for solid-state lighting based on GaN LEDs applications.     

Thermally stable blue-emitting NaSrPO4:Eu phosphor for near UV white LEDs

A novel blue light emitting NaSr_1 − xPO₄:Eu²⁺_x (x = 0.001 to 0.02) phosphors were prepared by solid-state reaction method to investigate its optical properties and thermal stability for its application in white light-emitting diodes (w-LEDs). The excitation and emission spectra of the prepared phosphor reveal a broad emission peak centered at 460 nm which arises due to 4f-5d transitions of Eu²⁺ upon the near ultra-violet (n-UV) excitation wavelength at 380 nm. The effect of Eu²⁺ doping concentration and sintering temperature on the emission intensity of NaSrPO₄:Eu²⁺ was investigated along with its chromaticity coordinates. The temperature dependent luminescence properties of the prepared phosphor show better results than that of the commercial YAG:Ce³⁺phosphor. Besides, their XRD, FT-IR, SEM, TG, and DTA profiles have also been analyzed to explore its structural details.     

Luminescence enhancement of Eu-doped calcium magnesium silicate blue phosphor for UV-LED application

(Ca_1−x,Eu_x)MgSi_2yO_6+δ blue phosphor was prepared by spray pyrolysis and the photoluminescence properties were optimized by controlling concentration of Si element and the activator content. At y=1.0, the concentration quenching in the luminescent intensity appeared when the Eu²⁺ content (x) was 0.01 (1 at%). Such quenching concentration was changed with the concentration of silicon (y), which was increased with an increase in the quantity of excess Si (y>1.0). The highest luminescent intensity was achieved when the Eu²⁺ content (x) and the Si concentration (y) were 0.04 and 1.3, respectively. According to X-ray diffraction (XRD) analysis, the tetragonal SiO₂ phase was formed as a minor phase when the y value was larger than 1.3. The formation of SiO₂ phase, however, did not reduce but increased the luminescent intensity when the Eu²⁺ content was optimized again. As a result, the luminescent intensity of the phosphor particles optimized in the content of both Si and Eu²⁺ was about 150% improved compared with that of the CaMgSi₂O₆:Eu sample (x=0.01, y=1.0).     

Eu and Ce emission in sulphate based phosphors

Polycrystalline KMgSO₄Cl:Eu and Na₅(PO₄)SO₄:Ce phosphors prepared by a wet chemical method have been studied for its photoluminescence (PL) and thermoluminescence (TL) characteristics. The TL glow curve of the compound has a prominent peak at 200 °C and may be useful for TL study. TL sensitivity of the KMgSO₄Cl:Eu phosphor is found to be 1.7 times less than that of TLD—CaSO₄:Dy. The presence of bands at around 420, 435 and 445 nm in the PL emission spectra of the phosphor suggests the presence of Eu²⁺ in the host compound. Moreover a TL glow curve of the Na₅(PO₄)SO₄:Ce gives a better understanding of the TL mechanism (peaks at 271 and 310 °C) involved in the concerned phosphor. The PL emission spectra are observed at 382 nm for the various concentrations. In this paper we report PL and TL characteristics of KMgSO₄Cl:Eu halosulphate and Na₅(PO₄)SO₄:Ce phosphate sulphate phosphors first time.     

Luminescence and chromaticity of alkaline earth aluminate MxSr1−xAl2O4:Eu (M: Ca,Ba)

In order to prepare fluorescent material for UV-LED used as illumination light source, two series of Eu²⁺ doped (1 mol%) alkaline earth aluminate phosphors Ca_xSr_1−xAl₂O₄ and Ba_xSr_1−xAl₂O₄ were prepared. The crystal structure, relative quantum efficiency(Qr), peak wavelength(λ_p), color tuning and chromaticity were investigated by XRD patterns and photoluminescence (PL) on samples prepared by solid solution system (s series) and powder mixing system (m series) respectively. For the s series, the synthesized Ca_xSr_1−xAl₂O₄:Eu²⁺ powders show that the structure transforms from monoclinic to hexagonal at x?0.5, and λ_p increases from 442.3 to 529.7 nm with decreasing x. For the Ba_xSr_1−xAl₂O₄:Eu²⁺ system, the structure transforms from monoclinic to hexagonal at x?0.3, and λ_p decreases from 520.5 to 502.2 nm continuously from x=0 to 1. The shift in λ_p could be explained by the crystal field effect, which is affected by different coulomb attractive forces due to the various fraction of alkaline earth cation in the host lattice. Different phosphor properties prepared by either solid solution or powder mixing methods were characterized by chromaticity measurements for both reflective and transmissive modes.     

Effect of local environment and Sm-codoping on the luminescence properties in the Eu-doped potassium tungstate phosphor for white LEDS

The luminescence properties of Eu³⁺- and Sm³⁺-doped potassium tungstate phosphors were investigated. The K_4−3(x+y) (WO₄)₂:Eu_x³⁺,Sm_y³⁺ phosphor was produced by solid-state reactions, followed by re-firing with a flux. The phosphor showed a strong absorption in the near-UV to green region due to 4f-4f electron transitions of the Eu³⁺ and Sm³⁺ ions, generating a red emission. The excitation spectrum could be adjusted by Sm³⁺-codoping. A small amount of Sm³⁺, acting as a sensitizer, increased the energy absorption peak at 405 nm. The crystal structure and local environment around the Eu³⁺ ions were determined using the Rietveld method. The crystal structure of this phosphor was determined to be monoclinic with a space group of C2/c. The small Eu-0 distance in the crystal led to high energy-level splitting at the ⁵D₀→⁷F₂ transition of the Eu³⁺ ions, resulting in more emission peaks.     

Luminescent properties of HTP AgGd1−xW2O8:Eux and AgGd1−x(W1−yMoy)2O8:Eux phosphor for white LED

Intense red phosphors, AgGd_1−xEu_x(W_1−yMo_y)₂O₈ (x=0.0-1.0, y=0.0-1.0), have been synthesized through traditional solid-state reaction and characterized by X-ray diffraction (XRD) and photoluminescence (PL). XRD results reveal that AgGd_1−xEu_xW₂O₈ synthesized at 1000 °C has a tetragonal crystal structure, which is named as high temperature phase (HTP) AgGdW₂O₈. All phosphors compositions with Eu³⁺ show red and green emission on excitation either in the charge-transfer or Eu³⁺ levels. Analysis of the emission spectra with different Eu³⁺ concentrations reveal that the optimum dopant concentration for Eu³⁺ is x=0.6 in the HTP AgGd_1−xEu_xW₂O₈ (x=0.0-1.0). Studies on the AgGd_0.4Eu_0.6(W_1−yMo_y)₂O₈ (y=0.0-1.0) and AgGd_1−xEu_x(W_0.7Mo_0.3)₂O₈ (x=0.0-1.0) show that the emission intensity is maximum for compositions with y=0.3 and x=0.5, respectively, and a decrease in emission intensity is observed for higher y or x values. The Mo⁶⁺ and Eu³⁺ co-doped AgGd(WO₄)₂ phosphors show higher emission intensity in comparison with the singly Eu³⁺-doped AgGd(WO₄)₂ in UV region. The intense emission of the tungstate/molybdate phosphors under 394 and 465 nm excitations, respectively, suggests that these materials are promising candidates as red-emitting phosphors for near-UV/blue GaN-based white LED for white light generation.     

Low-voltage cathodoluminescence property of Li-doped Gd2−xYxO3:Eu

Cathodoluminescent (CL) spectra of Li-doped Gd_2−xY_xO₃:Eu³⁺ solid-solution (0.0?x?0.8) were investigated at low voltages (300 V-1 kV). The CL intensity is maximum for the composition of x=0.2 and gradually reduces with increasing the amount of substituted Y content. In particular, small (∼100 nm) particles of Li-doped Gd_1.8Y_0.2O₃:Eu³⁺ are obtained by firing the citrate precursors at only 650°C for 18 h. Relative red-emission intensity at 300 V of this phosphor is close to 180% in comparison with that of commercial red phosphor Y₂O₃:Eu³⁺. An increase of firing temperature to 900°C results in 400-600 nm sized spherical particles. At low voltages (300-800 V), the CL emission of 100 nm sized particles is much stronger than that of 400-600 nm sized ones. In contrast, the larger particles exhibit the higher CL emission intensity at high voltages (1-10 kV). Taking into consideration small spherical morphology and effective CL emission, Li-doped Gd_1.8Y_0.2O₃:Eu³⁺ appears to be an efficient phosphor material for low voltage field emission display.