Luminescent properties of stabled hexagonal phase Sr1−xBaxAl2O4:Eu (x=0.37-0.70)

Stabled hexagonal phase Sr_1−xBa_xAl₂O₄:Eu²⁺ (x=0.37-0.70) was prepared by solid-state method. Result revealed that the structure behavior of the SrAl₂O₄:Eu²⁺ calcined at 1350 °C in a reducing atmosphere for 5 h strongly depended on the Ba²⁺ concentration. With increasing Ba²⁺ concentration, a characteristic hexagonal phase can be observed. When 37-70% of the strontium is replaced by barium, the structure of the prepared sample is pure hexagonal. Photoluminescence and excitation spectra of the samples with different x and doped with 2% Eu²⁺ were investigated. Changes in the emission spectra were observed in the two different phases. The green emission at 505 nm from Eu²⁺ was found to be quite strong in the hexagonal phase. The intensity and peak position of the green luminescence from Eu²⁺ changed with increasing content of Ba²⁺. The strongest green emission was obtained from Sr_0.61Ba_0.37Al₂O₄:Eu²⁺. The decay characteristics of Sr_1−xBa_xAl₂O₄:Eu²⁺ (x=0.37-0.70) showed that the life times also varied with the value of x. Furthermore, the emission colors and decay times varying with x could be ascribed to the variation of crystal lattice.     

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 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.     

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.     

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).     

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.     

A potential red-emitting phosphor CaSrAl2SiO7:Eu for near-ultraviolet light-emitting diodes

A novel red-emitting phosphor CaSrAl₂SiO₇:Eu³⁺ was firstly synthesized through the high temperature solid state reaction at 1300 °C. The structure, diffuse reflection spectra, photoluminescence spectra, color-coordinate parameters and quantum efficiencies (QE) of phosphors were investigated. The obtained CaSrAl₂SiO₇:Eu³⁺ phosphors have the same structure with that of the Ca₂Al₂SiO₇ and Sr₂Al₂SiO₇ phosphor, which have the melilite structure. Optical properties were studied as a function of Eu³⁺ concentration x, when x>0.14, the intensity of absorption of the f–f transitions of Eu³⁺ at 393 nm is stronger than that of the broad charge transfer transition band (CTB) around 254 nm, and which matches well with the output lights of NUV–LEDs, whereas, the concentration of Eu³⁺x≤0.14, the absorption of 393 nm is weaker than that of CTB. The underlying reason of Eu³⁺ concentration on their luminescent properties was investigated and discussed in detail. As a result, comparing with the commercial red phosphor Y₂O₂S:Eu³⁺, the CaSrAl₂SiO₇:xEu³⁺ (x>0.14) phosphor exhibited excellent color purity and much higher brightness and could be considered as promising red phosphors for NUV–LEDs.     

Novel blue-emitting phosphor Sr2.979Eu0.021Al10−xBxSiO20 (x=0, 0.25, 0.5, 0.75 and 1) for PDP applications

A series of blue-emitting phosphor Sr_3−xEu_xAl₁₀SiO₂₀ (x=0-0.025, insteps of 0.0025) have been synthesized and the emission intensity is found to be maximum for x=0.02. The effect of boron substitution in the Al site in Sr₃Al₁₀SiO₂₀:Eu²⁺ phosphor has been investigated to improve the blue emission of Eu²⁺. A series of boron-substituted compositions have been made Sr_2.979Eu_0.021Al_10−xB_xSiO₂₀ (x=0, 0.25, 0.5, 0.75 and 1) and studied their photoluminescence (PL) property under UV and VUV excitation. The X-ray diffraction patterns of Sr_2.979Eu_0.021Al_10−xB_xSiO₂₀ (x=0, 0.25, 0.5, 0.75 and 1) show single phase formation and all the compositions crystallize in monoclinic structure with space group C2/m. Blue emission (due to Eu²⁺ ion) has been found in all compositions and the emission intensity is found to be maximum for x=0.25 and it is ∼2 times higher than that of x=0 composition (PL intensity 62% vs. commercial BAM). Hence, this phosphor could be possible potential candidate for blue light-emitting phosphor for plasma display panel (PDP) applications.     

Effects of dopant concentrations on phosphorescence properties of Eu/Dy-doped Sr3MgSi2O8

Long afterglow Sr₃MgSi₂O₈: Eu, Dy phosphor with high brightness was prepared by sintering at high temperature and weak reductive atmosphere. The luminescent properties of this photoluminescent pigment were studied systematically by investigating concentration effects. The analytical results indicated that the main emission peaks appear at 482 nm. The excitation and emission spectra of this phosphor show that both of them are broadband. This is ascribed to the 4f⁷→4f⁶5d¹ transition of Eu²⁺ in the pigment matrix, which is in good agreement with the calculated value of 470 nm, and implies that luminescent centers Eu²⁺ occupy the deca-coordinated Sr²⁺ sites with the host of Sr₃MgSi₂O₈.     

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.     

Crystal structure of BaCa2MgSi2O8 and the photoluminescent properties activated by Eu

Rietveld refinements of X-ray powder diffraction data have confirmed the crystal structure of BaCa₂MgSi₂O₈ prepared by a standard solid-state method. The final reliable factors were R_wp=10.91%, R_p=8.10%, R_I=2.71%, and R_F=1.14%. BaCa₂MgSi₂O₈ crystallizes in the trigonal space group P3¯m1 (no. 164) with a=5.430(3) Å and c=6.807(2) Å. The oxide has a layered structure constructed from the unit layers built up by corner-sharing MgO₆ octahedra and SiO₄ tetrahedra. Ba and Ca atoms occupy the distinct crystallographic sites; Ba atom is sited in the interlayer space and Ca atom is embedded in the layer framework. This structure was not disrupted by doping of Eu²⁺ ions.The Eu²⁺-doped BaCa₂MgSi₂O₈ exhibited an intense blue emission based on 5d-4f electron transitions of Eu²⁺ ions under 254 nm excitation. This emission has a sufficient chromaticity as a blue phosphor. An additional analysis of the emission spectra using an empirical formula indicates that Eu²⁺ is distributed into both Ba and Ca sites.     

Synthesis and crystal structures and luminescent properties of divalent europium-doped Ba2ZnSi2O7 and BaZn2Si2O7

The monoclinic Ba₂ZnSi₂O₇:Eu²⁺ blue-green-emitting phosphor and the orthorhombic BaZn₂Si₂O₇:Eu²⁺ green-emitting phosphor were prepared by combustion-assisted synthesis method as the fluorescent materials for ultraviolet-light-emitting diodes (UV-LEDs) performed as a light source. The crystallinity and luminescence were investigated using X-ray diffraction (XRD) and photoluminescence (PL) spectroscopy. Pure monoclinic Ba₂ZnSi₂O₇ and orthorhombic BaZn₂Si₂O₇ crystallize completely at 1100 °C. The doped Eu²⁺ ions did not cause any significant change in the host structure. The emission spectra presented an emission position red shift of up to 16 nm from Ba₂ZnSi₂O₇:Eu²⁺ to BaZn₂Si₂O₇:Eu²⁺. The excitation spectra of Ba₂ZnSi₂O₇:Eu²⁺ and BaZn₂Si₂O₇:Eu²⁺ were broad-banding, extending from 260 to 465 nm, which match the emission of UV-LEDs.     

Crystal structure and photoluminescence properties of Eu-activated Ba2LiB5O10 phosphors

A novel orange-yellow-emitting Ba₂LiB₅O₁₀:Eu²⁺ phosphor has been synthesized by traditional high temperature solid state reaction. A monoclinic crystal structure of Barium lithiumborates Ba₂LiB₅O₁₀ was verified by the investigation of X-ray diffraction (XRD). The compound crystallizes in the space group of P121/m1(11) (Z = 2) with the unit cell parameters a = 4.414(1) Å, b = 14.576(2) Å, c = 6.697(2) Å and β = 104.26(2)°. Barium and lithium atoms are located in distorted octahedral and tetrahedral oxygen coordinations, respectively. Upon around 365 nm excitation, the Eu²⁺-activated Ba₂LiB₅O₁₀ phosphors exhibit a single broad emission band with the maximum at about 587 nm, due to the 4f⁶5d → 4f⁷(8S_7/2) transition of Eu²⁺. This work investigates the relationship between luminescence properties and structural characterization of the Ba₂LiB₅O₁₀: Eu²⁺. This newly developed phosphor shows high potential as a phosphor conversion for white LED applications.     

Photoluminescence properties of Sr1-xSi2O2N2: Eux as green to yellow-emitting phosphor for blue pumped white LEDs

This study evaluated potential applications of green to yellow-emitting phosphors (Sr_1−xSi₂O₂N₂: Eu²⁺_x) in blue pumped white light emitting diodes. Sr_1-xSi₂O₂N₂: Eu²⁺_x was synthesized at different Eu²⁺ doping concentrations at 1450 °C for 5 h under a reducing nitrogen atmosphere containing 5% H₂ using a conventional solid reaction method. The X-ray diffraction patterns of the prepared phosphor (Sr_1-xSi₂O₂N₂: Eu²⁺_x) were indexed to the SrSi₂O₂N₂ phase and an unknown intermediate phase. The photoluminescence properties of these phosphors (Sr_1−xSi₂O₂N₂: Eu²⁺_x) showed that the samples were excited from the UV to visible region due to the strong crystal field splitting of the Eu²⁺ ion. The emission spectra under excitation of 450 nm showed a bright color at 545-561 nm. The emission intensity increased gradually with increasing Eu²⁺ doping concentration ratio from 0.05 to 0.15. However, the emission intensity decreased suddenly when the Eu²⁺ concentration ratio was >0.2. As the doping concentration of Eu²⁺ was increased, there was a red shift in the continuous emission peak. These results suggest that Sr_1-xSi₂O₂N₂: Eu₂⁺_x phosphor can be used in blue-pumped white light emitting diodes.     

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.     

Synthesis and Eu concentration-dependent photoluminescence of Gd2−xEuxO3 nanowires

The nanowire growth behavior and photoluminescence characteristics of red-emitting oxide phosphor Gd_2−xEu_xO₃ have been investigated in the function of activator (Eu³⁺) concentrations (x=0.08, 0.12, 0.16, 0.20, and 0.24). Nanowires of Gd_2−xEu_xO₃ phosphor were prepared by the dehydration of corresponding hydroxides Gd_1−x/2Eu_x/2(OH)₃ obtained by the hydrothermal reaction. Highly uniform nanowires of 20-30 nm in diameter can grow up to several tens of micrometers in length. A number of defects on the surface of Gd_1.92Eu_0.08O₃ nanowires, which are induced during structural transformation from hexagonal hydroxide to cubic oxide, strongly decrease the luminescence efficiency in comparison with that of the bulk phosphor. In contrast, the photoemission intensity of nanowires is significantly improved with increasing Eu³⁺ content (x) of Gd_2−xEu_xO₃ solid solution. The highest relative emission intensity of nanowires is observed when the x value is close to x=0.20. This content is much higher than the optimal concentration of Eu³⁺ (x=0.08-0.10) for the bulk Gd₂O₃:Eu powder.     

Luminescent properties of KGd1−x(WO4)2:Eux and KGd1−x(WO4)2−y(MoO4)y:Eux phosphors in UV-VUV regions

KGd_1−x(WO₄)_2−y(MoO₄)_y:Eu³⁺_x(0.1?x?0.75, y=0 and 0.2) phosphors are synthesized through traditional solid-state reaction and their luminescent properties in ultraviolet (UV) and vacuum ultraviolet (VUV) regions are investigated. Under 147 nm excitation, these phosphors show characteristic red emission with good color purity. In order to improve their emission intensity, the MoO₄²⁻ (20 wt%) is introduced into the anion of KGd_1−x(WO₄):Eu³⁺_x. The Mo⁶⁺ and Eu³⁺ co-doped KGd(WO₄)₂ phosphors show higher emission intensity in comparison with the singly Eu³⁺-doped KGd(WO₄)₂ in VUV region. The chromaticity coordination of KGd_0.45(WO₄):Eu³⁺_0.55 is (x=0.669, y=0.331), while that of KGd_0.45(WO₄)_1.8(MoO₄)_0.2:Eu³⁺_0.55 is (x=0.666, y=0.334) in VUV region.     

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.     

Intense green/yellow emission in Ca8Zn(SiO4)4Cl2:Eu, Mn through energy transfer for blue-LED lighting

Eu²⁺ and Mn²⁺ co-doped Ca₈Zn(SiO₄)₄Cl₂ phosphors have been synthesized by a high temperature solid state reaction. Energy transfer from Eu²⁺ to Mn²⁺ is observed. The emission spectra of the phosphors show a green band at 505 nm of Eu²⁺ and a yellow band at 550 nm of Mn²⁺. The excitation spectra corresponding to 4f⁷-4f⁶5d transition of Eu²⁺ cover the spectral range of 370-470 nm, well matching UV and/or blue LEDs. The shortening of fluorescent lifetimes of Eu²⁺ followed by simultaneous increase of fluorescent intensity of Mn²⁺ with increasing Mn²⁺ concentrations is studied based on energy transfer. Upon blue light excitation the present phosphor can emit intense green/yellow in comparison with other chlorosilicate phosphors such as Eu²⁺ and Mn²⁺ co-doped Ca₈Mg(SiO₄)₄Cl₂ and Ca₃SiO₄Cl₂, demonstrating a potential application in phosphor converted white LEDs.     

Photoluminescence of Eu single doped and Eu/Dy codoped Sr2Al2SiO7 phosphors with long persistence

This paper reports the preparation of long persistent Sr₂Al₂SiO₇:Eu²⁺ and Sr₂Al₂SiO₇:Eu²⁺, Dy³⁺ phosphors and the comparison of their photoluminescent properties. The silicate phosphors prepared by solid-state reaction routine showed a broad blue emission peaking at 484 nm when activated by UV illumination. Such a bluish-green emission can be attributed to the intrinsic 4f-5d transitions of Eu²⁺. After the UV source was switched off, long persistent phosphorescence could be observed by naked eyes for both samples in darkness. Afterglow measurements revealed that Eu/Dy codoped phosphor possesses better afterglow properties than the Eu single doped one, since the maximum lifetime (τ_max=99 s) of the photons calculated from the decay profile is much larger than that of the Eu single doped phosphor (τ_max=82 s). TSL results suggested that the difference in afterglow properties was caused by the difference in the electron traps within the crystal lattice. For Eu/Dy codoped phosphor, the doping of Dy ions produced electron traps with trap depth of 0.52 eV, which is suitable and therefore leads to good persistence. However, in the case of Eu single doped phosphor, the trap depth is 0.88 eV, which is really too deep an energy barrier to overcome, and therefore a poor persistence was observed in the experiment.