Luminescence investigation of Eu activated molybdates red phosphors and their applications in near-UV light-emitting diodes

The red phosphors, Na₅La_1−xSm_x(MoO₄)₄ and Na₅Eu_1−xSm_x(MoO₄)₄, were prepared by solid-state reaction technique at high temperature. Their structure and photo-luminescent properties were investigated. The excitation bands around 400 nm of these phosphors are broadened by Sm³⁺-Eu³⁺ co-doping. And the possible energy transfer process from Sm³⁺ to Eu³⁺ in these compounds is also discussed briefly. The phosphor Na₅Eu_0.90Sm_0.10(MoO₄)₄ exhibits efficient red-emitting with broadened absorption around 400 nm and appropriate CIE chromaticity coordinates (x = 0.66, y = 0.34), bright red light can be observed from the red LED based Na₅Eu_0.90Sm_0.10(MoO₄)₄.     

Novel red phosphors Na2CaSiO4:Eu for light-emitting diodes

Novel red phosphors Na₂CaSiO₄:xEu³⁺ were synthesized using high temperature solid-state reaction and their luminescence characteristics were investigated for the first time. The excitation spectra indicate that the Na₂CaSiO₄:xEu³⁺ phosphors can be effectively excited by ultraviolet (393 nm) light. The emission spectra of Na₂CaSiO₄:xEu³⁺ phosphors invariably exhibit four peaks assigned to the ⁵D₀-⁷F_J (J = 1, 2, 3 and 4) transitions of Eu³⁺ under 393 nm excitation. The Commission Internationale de l’Eclairage (CIE) chromaticity coordinates and quantum efficiency (QE) are (0.66, 0.34) and 58.9%, respectively. The good color saturation and high quantum efficiency indicate that Na₂CaSiO₄:Eu³⁺ phosphors are potential candidate for light-emitting diodes.     

Powder synthesis and white light-emitting properties of Eu3+ co-doped K2CaP2O7:Dy3+ phosphors with energy transfer between Dy3+ and Eu3+

A series of white-emitting K₂CaP₂O₇:Dy³⁺ and K₂CaP₂O₇:Dy³⁺, Eu³⁺ phosphors were synthesized via a solid-state method, and Eu³⁺ was co-doped in K₂CaP₂O₇:Dy³⁺ to improve its white light performance. The influences of preparation temperature and Dy³⁺/Eu³⁺ concentration on the crystal structure and photoluminescence characteristics were investigated. XRD results indicate that K₂CaP₂O₇:Dy³⁺ samples prepared above 700 °C matches the standard K₂CaP₂O₇ phase. Under excitation of 349 nm, K₂CaP₂O₇:Dy³⁺ phosphor exhibited characteristic emission peaks at 487 nm (blue) and 579 nm (yellow), and white emission was realized through combining these blue and yellow emissions. After co-doping Eu³⁺ ions, the co-luminescence of Dy³⁺/Eu³⁺ with energy transfer between Dy³⁺and Eu³⁺ were demonstrated. The chromaticity of white light was controlled by changing the ratio of Dy³⁺/Eu³⁺ concentrations, which lead to a warm white light. Therefore, the results indicate that K₂CaP₂O₇:Dy³⁺, Eu³⁺ powders have a potential application in w-LEDs as single-component white-emitting phosphor.     

Luminescent properties of Sr2Al2SiO7:Ce3+,Eu2+ phosphors for near UV-excited white light-emitting diodes

The Sr₂Al₂SiO₇:Eu²⁺, Ce³⁺ phosphors were synthesized by a high temperature solid-state reaction. Effective energy transfer occurs in Ce³⁺ and Eu²⁺ co-doped Sr₂Al₂SiO₇ due to large spectral overlap between the emission of Ce³⁺ and excitation of Eu²⁺ ions. Co-doping of Ce³⁺ enhances the emission intensity of Eu²⁺ greatly by transferring its excitation energy to Eu²⁺ ions. The critical distance has been estimated to be about 1.83 nm by spectral overlap method. Furthermore, the developed phosphors can generate lights from blue to green region under the excitation of UV radiation by appropriately tuning the activator content. The Sr₂Al₂SiO₇:Eu²⁺,Ce³⁺ phosphors are promising phosphors for warm-white-light-emitting diode because of its effective excitation in the near ultraviolet range.     

Photoluminescence properties of Sr3(PO4)2: Eu2+, Dy3+ double-emitting blue phosphor for white LEDs

Double-emitting blue phosphor Sr₃(PO₄)₂: Eu²⁺, Dy³⁺ was synthesized by solid state reaction under H₂ atmosphere. XRD exhibited the pure hexagonal phase of the prepared phosphor. The photoluminescence results showed that all samples had intense broad absorption band between 250 and 450 nm, which matched well with the near-UV (350–420 nm) emission band of InGaN-based chips. The emission spectrum of Sr₃(PO₄)₂: Eu²⁺, Dy³⁺ consisted of two broad bands, peaked at 485 nm and 410 nm, which originated from two luminescent centers, related to 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ in six-coordinated Sr(I) and ten-coordinated Sr(II) sites respectively. The intensity ratio of two emission bands could be easily tuned by adjusting Dy³⁺ co-doping content, which resulted in color-tunable luminescence in bluish green region to purplish blue region.     

溶胶-凝胶法制备CaAl_2SiO_6:Eu~(2+)荧光粉及其光学性质的研究

采用溶胶-凝胶法制备了CaAl2SiO6∶Eu2+荧光粉,利用X射线衍射仪、荧光光谱仪、热分析仪对其结构和光学性质进行了研究.结果表明,样品经1 000℃CaAl2SiO6∶Eu2+荧光粉在430 nm附近的发光峰为Eu2+中心的4f65d1(t2g)→4f7(8S7/2)跃迁;随Eu2+离子浓度的增加,样品的发光强度先增加后降低,在Eu2+浓度为0.7 mol%时达到最大;CaAl2SiO6∶Eu2+系列荧光粉的激发峰波长在280~390 nm之内,可以作为一种新型的UV-LED用三基色荧光粉.     

Photoluminescence of CaAlSiN3:Eu2+-based fine red-emitting phosphors synthesized by carbothermal reduction and nitridation method

In this research, we have presented the synthesis and characterization of the various Ca_1−xEu_xAl_0.76Si_1.18N₃ (x = 0.01 ∼ 0.1) red-emitting phosphors, which were successfully prepared by carbothermal reduction and nitridation (CTRN) method without the strict needs of high pressure. Here, raw materials were CaCO₃, AlN, Si₃N₄, Eu₂O₃, and C. In particular, C was considered as efficient and robust reducing agent. The influences of reaction temperature, holding time, C content, and Eu²⁺ concentration were investigated in the crystal phase compositions and photoluminescence properties of the as-prepared phosphors. Importantly, CaAlSiN₃:Eu²⁺-based red phosphors with interesting properties were obtained with reaction temperature at 1600 °C for 4 h by atmospheric N₂–10%H₂ pressure, and the C/O ratio of 1.5:1, respectively. The emission peak positions of as-prepared phosphors were red-shifted from 607 nm to 654 nm with Eu²⁺ concentration from 1 mol% to 10 mol%. Meanwhile the highest luminescence intensity was achieved with 2 mol% of Eu²⁺ concentration, which showed high external quantum efficiency up to 71%. Combining the phosphor blend of green-emitting β-sialon:Eu²⁺, yellow-emitting Ca-α-sialon:Eu²⁺, and red-emitting Ca_0.98Eu_0.02Al_0.76Si_1.18N₃ with a blue LED (light emitting diodes), warm white LED can be generated, yielding the color rendering index (Ra) of 93 at correlated color temperature (CCT) of 3295 K. These results indicate that CaAlSiN₃:Eu²⁺-based red-emitting phosphors prepared by facile CTRN are highly promising candidates for warm white LEDs.     

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.     

白光LED用红色荧光粉MMoO4:Eu3+（M=Ca,Sr,Ba）的制备与表征

采用高温固相法制备了红色荧光粉MMoO4:Eu3+(M=Ca,Sr,Ba),用XRD和荧光分光光度计对其物相及发光性能进行表征和研究。结果表明,在800℃时可得到MMoO4(M=Ca,Sr,Ba)物相结构。分别以395nm的近紫外光和465nm的可见光激发样品,MMoO4:Eu3+(M=Ca,Sr,Ba)荧光粉发红光,对应于Eu3+的4f-4f跃迁,其中以616nm发光最强。荧光粉在395nm和465nm的吸收分别与紫外光和蓝光LED芯片相匹配。     

燃烧法合成铕镝掺杂铝酸锶长余辉发光材料的研究

以尿素和硝酸盐溶液为反应介质 ,在 6 0 0℃下用燃烧法一次制备出了Eu2 ,Dy3 掺杂的铝酸锶 (SrAl2 O4 )磷光体。用SEM、XRD研究了所得磷光材料的形态、粒度和物相组成 ,用荧光分光光度计测定了磷光材料的发光性能。结果表明 ,SrAl2 O4 ∶Eu2 ,Dy3 磷光材料的晶体结构属于单斜晶系结构。制备产物在 5 2 0nm处有很强的发射峰 ,它的激发光谱是激发峰峰值 2 90nm的宽带激发。制备产物的形貌呈疏松多孔状 ,晶粒形状为针状 ,长度有 2 0 0nm左右 ,直径在 80nm以下。并探讨了该材料发光性能的影响因素     

Multiple energy transfer between CaNb2O6:Tb3+, Eu3+ for single-component white light-emitting phosphors

Journal of Materials Science: Materials in Electronics - A series of host-activated Tb3+ and Eu3+-co-doped CaNb2O6 (CNO) phosphors with tunable luminescence were synthesized via high-temperature...     

Synthesis and spectroscopic characterization of the K4BaSi3O9:Eu3+

K₄BaSi₃O₉:Eu³⁺ polycrystals were synthesized by solid state method. X-ray powder diffraction measurements confirmed structure of the samples. The excitation and the emission spectra of orthorhombic K₄BaSi₃O₉ doped with Eu³⁺ were investigated. The excitation spectrum exhibits a broad band with maximum at 220 nm corresponding to the charge transfer (CT) transition between O²⁻ and Eu³⁺ ions and smaller 4f–4f transitions. The emission of investigated phosphor was excited at 395 nm and has quantum efficiency (QE) equal 27%. The emission maximum at 616.5 nm was assigned to the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions. The luminescence decay profiles as well as the thermal quenching were measured and analyzed. K₄BaSi₃O₉:Eu³⁺has high temperature quenching of the emission T_0.5 = 335 °C.     

Polyspectral white light emission from Eu3+, Tb3+, Dy3+, Tm3+ co-doped GdAl3(BO3)4 phosphors obtained by combustion synthesis

Polycrystalline sub-micron-sized GdAl₃(BO₃)₄ phosphors co-doped with Eu³⁺, Tb³⁺, Dy³⁺ and Tm³⁺ have been prepared by combustion synthesis with urea. The phosphors have been characterised by X-ray diffraction, scanning electron microscopy, excitation and emission spectroscopy. The chromaticity co-ordinates and the colour temperatures of the fluorescence of the materials presented have been calculated and analysed with Commission Internationale l’Eclairage (CIE) programs and diagrams. Depending on the excitation wavelength, different colour temperatures of the light emitted can be achieved. Due to its polyspectral nature, the emitted light reveals a high colour rendering index.     

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.     

New red phosphor for near-ultraviolet light-emitting diodes with high color-purity

New red phosphors, Na₅Eu(MoO₄)₄ doped with boron oxide were prepared by the solid-state reaction. Their structure and photo-luminescent properties were investigated. With the introduction of boron oxide, the red emission intensity of the phosphors under 395 nm excitation is strengthened, with high color-purity (x = 0.673, y = 0.327). The single red light-emitting diode was obtained by combining InGaN chip with the red phosphor, bright red light can be observed by naked eyes from the red light-emitting diodes under a forward bias of 20 mA.     

Luminescent properties of Eu doped α-Gd2(MoO4)3 phosphor for white light emitting diodes

A novel red emitting phosphor α-Gd₂(MoO₄)₃:Eu³⁺ was developed for white light emitting diodes (LEDs). The phosphor was prepared by solid-state reaction. The effects of the flux content and the activator concentration on the crystal structure, morphology and luminescent properties were investigated by using XRD, SEM, and fluorescent spectra. These results showed that this phosphor can be effectively excited by ultraviolet (UV) (395 nm) and blue (465 nm) light, matching the output wavelengths of ultraviolet or blue LED chips. The α-Gd₂ (MoO₄)₃ phosphor may be a better candidate for solid state lighting application.     

Luminescent properties of Al2O3:Tb3+ powders embedded in polyethylene terephthalate films

The luminescent properties of Al₂O₃:Tb³⁺ powders embedded in polyethylene terephthalate (PET) films have been studied. Luminescent Al₂O₃:Tb³⁺ polycrystalline powders were synthesized by a simple evaporation method. The powder embedded films were obtained by the spray pyrolysis technique. The photoluminescence and cathodoluminescence emission spectra from these samples show, in both cases, luminescence peaks associated with transitions within the electronic energy levels of Tb³⁺ ions. The dominant peak is at 544 nm corresponding to the ⁵D₄ to ⁷F₅ transition. In the case of the powder embedded films, the CIE coordinates depend on the excitation wavelength because there is a blue emission contribution from the PET host. UV–Vis% transmission measurements on these films show that they are transparent (∼80% and 95% T).     

Preparation and characterization of boron oxide-based red-emitting phosphors using Eu,Al and Ca additives

New red-emitting phosphors have been produced and studied by investigating the effects of various additives such as europium (Eu), aluminum (Al), and calcium (Ca) on the photoluminescence performance of boron oxide-based phosphors. When both Eu and Ca ions were added, Ca₃B₂O₆:Eu phosphors could be synthesized via a straightforward process using a liquid precursor. The photoluminescent spectra of Ca₃B₂O₆:Eu phosphors exhibited a red emission at 611 nm under 254 nm excitation, and the internal quantum efficiency reached 41.5% when the concentration of Eu ion was fixed at an optimal condition of 0.13 M.     

Molten salt synthesis and photoluminescence properties of novel red emitting phosphors Ba5(VO4)3Cl:Eu3+,K+

A series of Ba₅(VO₄)₃Cl:Eu³⁺,K⁺ phosphors have been synthesized by the molten salt synthesis method. The crystalline structure, morphology, photoluminescence properties and lifetimes were characterized using X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM) and photoluminescence spectroscopy, respectively. XRD indicates that the Ba₅(VO₄)₃Cl:Eu³⁺,K⁺ phosphors are synthesized successfully via molten salt method. SEM image demonstrates that the obtained phosphors have hexagonal polyhedron morphology. The photoluminescence spectra reveal that the as-prepared phosphors exhibit a bright red emission under the excitation of blue or near ultraviolet light. The concentration quenching was also investigated, and the dipole–dipole interaction is responsible for the concentration quenching of fluorescence emission of Eu³⁺ ions in Ba₅(VO₄)₃Cl phosphor. The present work suggests that the Ba₅(VO₄)₃Cl:Eu³⁺,K⁺ phosphors would be a potential candidate for light emitting devices.