Synthesis and Luminescence Improvement of CaAlSiN_(3) Phosphors Doped with Eu^(2+) and Mn^(2+) for White LEDs

Eu^(2+) and Mn^(2+) co-activated CaAlSiN_(3) red phosphors were produced using the solid-state reaction tech⁃nique in a N2 environment.Excitation spectra,emission spectra,and diffuse reflection spectra were used to study the luminescence characteristics,energy gap,and thermal stability in detail.CaAlSiN_(3)∶Eu^(2+) exhibits an extended emission band when stimulated with 450 nm blue light,which is caused by the 4f65d to 4f7 transition of Eu^(2+).Similar⁃ly,CaAlSiN_(3)∶Mn^(2+) displays a wide emission band centered at 628 nm,which results from Mn^(2+)’s transition from 4T1(4G) to 6A1(6S).When the ions of Mn^(2+)were combined into CaAlSiN_(3)∶Eu^(2+),the photoluminescence intensity of Eu^(2+ )was greatly boosted because there was energy transfer and co-emission between Mn^(2+) and Eu^(2+).Beyond that,CaAlSiN_(3)∶Eu^(2+),Mn^(2+) emerges with splendid thermostability and high quantum efficiency,the quenching temperature surpasses 300℃,and the internal quantum efficiency is determined to be around 84.9%.The white LED was pack⁃aged with a combination of CaAlSiN_(3)∶Eu^(2+),Mn^(2+),LuAG∶Ce3+ and a blue chip.At a warm white-light corresponding color temperature(3009 K) with CIE coordinates(0.4223,0.3748),the color rendering index Ra has reached 93.2.CaAlSiN_(3)∶Eu^(2+),Mn^(2+) would have great application potential as a red-emitting phosphor for white LEDs.

Synthesis and Luminescence of SrZnO_2∶Eu^(3+), Li^+ Phosphor by Long Wavelength UV Excitation

SrZnO2 ： Eu^3 ＋ , Li^＋ phosphor powder by long wavelength UV excitation was synthesized by conventional solid-state reaction method. XRD and PL were employed to characterize their properties. The resuits show that Eu^3＋ ions preferentially occupy Sr^2＋ asymmetry cationic sites, thus emitting 612 nm red light originated from ^5D0 to ^7F2 transition. The luminescent intensity can be greatly enhanced with incorporation of Li^＋ ions. The excitation efficiency in range of 350 - 400 nm also increases greatly due to incorporating Li ^＋ ions. SrZnO2 ： Eu^3 ＋ , Li^＋ is a promising redemitting phosphor by long wavelength UV excitation.

SrZnO_2∶Eu^(3+),Li^+长波紫外激发红光荧光体的合成及发光性能研究

采用高温固相法合成了一种长波紫外激发的SrZnO2∶Eu3+,Li+发光材料,用X射线衍射谱、荧光光谱对样品进行了表征。结果表明,Eu3+离子在SrZnO2基质中主要占据Sr2+离子不对称性格位,发射来源于5D0→7F2612 nm为主的红光。加入电荷补偿剂Li+离子能显著提高发光强度,350~400 nm内的激发峰也有明显提高,同时观察到来自Eu3+离子高能级5D1→7FJ(J=0~2)的跃迁发射,并对其产生机制进行了初步探讨。实验结果表明,SrZnO2∶Eu3+,Li+是一种有发展前途的长波紫外激发红光荧光体。

稀土红色荧光粉SrZnO_2:Eu^(3+)的发光性能

A series of novel luminescent materials, SrZnO2:M (M=Eu3+, or Eu3+ + Li+) have been synthesized by high-temperature solid-state reaction. The structure and luminescence properties of SrZnO2:Eu3+ phosphor were studied through XRD, photoluminescence and Raman spectroscopy. The excitation spectra show a broad intense band and a number of small peaks corresponding to the inner 4f-shell excitations of Eu3+ (the strongest one is at 395 nm for 7F0-5L6). After SrZnO2:Eu3+ phosphor was co-doped with Li+ ions, its charge transfer band extended to longer wavelengths. This resulted in increase of luminescent quantum efficiency of the sample. SrZnO2:Eu3+,Li+ phosphor can be efficiently excited by longer UV. From the fluorescence spectrum of SrZnO2:Eu3+ phosphor, apart from transition emissions of 5D0 → 7FJ (J=0~4), the transition emissions from 5D1 → 7FJ (J=0~2) have been observed. For the SrZnO2:Eu3+ phosphor, under excitation of UV, the dominant emission is at about 612 nm, due to the 5D0 → 7F2 hypersensitive transition. The incorporation of Li+ ions greatly enhanced the luminescence intensity and made emission peak from 5D0 → 7F2 transition red-shifted.

Luminescent properties of Lu_2MoO_6:Eu^(3+) red phosphor for solid state lighting

The Eu^3＋ activated Lu2MoO6 phosphors were synthesized by high-temperature solid-state reaction method. The X-ray diffraction （XRD）, excitation spectra, emission spectra and decay lifetime of the phosphors were measured to characterize the structure and luminescent properties. The XRD results show that all the prepared phosphors can be assigned to the monoclinic structure. The experimental results indicate efficient absorption of near ultraviolet light from the Mo^6＋O^2- group followed by intensive emission in the visible spectral range. The optimal content of Eu3＋ is 10% （mole fraction）. The critical distance Rc and energy transfer mechanism were also discussed in detail. This red emitting material may be applied as a promising red phosphor for the near ultraviolet excited white light emitting diodes.

Luminescent Properties of Green Phosphor Ca_8Mg(SiO_4)_4Cl_2:Eu^(2+), Dy^(3+) for LED Applications

The new phosphor calcium magnesium chlorosilicate, codoped with Eu^2＋ and Dy^3＋, was synthesized with the help of the high temperature solid state reaction in reducing atmosphere. The excitation and emission spectra were very similar to that of Ca8Mg（SiO4）4Cl2 ：Eu^2＋, and the Dy^3＋ concentration influenced the emission intensity of this phosphor. The intensity of Eu^2＋ and Dy^3＋ codoped CMSC was stronger than that of Eu^2＋ singly doped CMSC. The emission spectrum of the Dy^3＋ ion overlapped the absorption band of the Eu^2＋ ion, indicating that an energy transfer from Dy^3＋ to Eu^2＋ took place in CMSC：Eu^2＋, Dy^3＋ phosphor. The mechanism of the energy transfer from Dy^3＋ tO Eu^2＋, in this phosphor, might be resonant energy transfer.

Luminescent properties of Ca_2SiO_4:Eu^(3+) red phosphor for trichromatic white light emitting diodes

The luminescent properties of Eu^3＋doped Ca2SiO4 red phosphors synthesized by the flux fusion reaction method were investigated. It was found that the excitation spectrum included two regions： the weak excitation band below 325 nm and strong narrow peaks above 325 nm. The main peak of the excitation band was located at 400 nm. The peaks located at 290 nm were assigned to the combination of the charge transfer transition of O-Eu, peaks above 325 nm （325, 385, 400, 470, 511, and 539 nm） were assigned to the f-f transitions of Eu^3＋. The emission spectrum was dominated by the red peak located at 612 nm due to the electric dipole transition of ^5D0-^7F2. In addition, the effects of the Eu^3＋ content and charge compensators of Li^＋, Na^＋, K^＋, and Cl^- ions on the emission intensity were investigated. The experiment results suggested that the strongest emission was obtained when the concentration of the Eu^3＋ ions was 0.3 mol^-1, and Li^＋ ions gave the best improvement to enhance the emission intensity. Ca2SiO4：Eu^3＋, Li^＋ was thus suitable for low-cost trichromatic white light emitting diodes （WLED） based on UV InGaN chip.

Vacuum Ultraviolet Excited Photoluminescence Properties of Y_2O_2S:Eu^(3+),Bi^(3+) Phosphor

As an Hg-free lamp using phosphor, the Bi^3＋ and EH^3＋ co-doped Y2O2S phosphors were prepared and their luminescence properties under vacuum ultraviolet（VUV） excitation were investigated. The VUV photoluminescent intensity of Y2O2S：Eu^3＋ was weak, however, considerably stronger red emission at 626 nm with good color purity was observed in Y2O2S：Eu^3＋,Bi^3＋ systems. Investigation on the photoluminescence reveals that the strong VUV luminescence of Y2O2S：Eu^3＋,Bi^3＋ at 147 nm is mainly because the Bi^3＋ acts as a medium and effectively performs the energy transfer process： Y^3＋-O^2-→Bi^3＋→Eu^3＋, while the intense emission band at 172 nm is attributed to the absorption of the characteristic ^1So-^1P1 transition of Bi^3＋ and the direct energy transfer from Bi^3＋ to Eu^3＋. The Y2O2S：Eu^3＋,Bi^3＋ shows excellent VUV optical properties compared with the commercial （Y,Gd）BO3：Eu^3＋. Thus, the Y2O2S：Eu^3＋,Bi^3＋ can be a potential red VUV-excited candidate applied in Hg-free lamps for backlight of liquid crystal display.

Influence of Molten Salt on Luminescent Intensity and Particle Size of Y_2O_3:Eu^(3+) Phosphor

The Y-Eu oxalate precursor was prepared with a homogeneous precipitation method. And the additives, Na2CO3, S, NaCl or their combination, were introduced into the precursor to prepare Y2O3 ：Eu^3＋ red phosphors at 1000 1300 ℃ for 2 h. The effect of molten salts on particle size and luminescent intensity was studied. The experimental results showed that the complex molten salt （Na：CO3 ＋ S ＋ NaCl） was conductive to enhance the luminescent intensity of Y2O3 ：Eu^3＋. The emission intensity of the phosphor prepared with these additives at 1300 ℃ was about 45% higher than that of the one prepared without molten salt, and about 11% higher than that of the corresponding commercial phosphor. Meanwhile, the particle size of Y2O3 ：Eu^3＋ phosphor was controlled effectively with the molten salt.

Vacuum ultraviolet excited photoluminescence properties of Gd_2O_2CO_3:Eu^(3+) phosphor

The Gd2O2CO3：Eu^3＋ with type-Ⅱ structure phosphor was successfully synthesized via flux method at 400 ℃ and their photoluminescence properties in vacuum ultraviolet （VUV） region were examined. The broad and strong excitation bands in the range of 153-205 nm owing to the CO3^2- host absorption and charge transfer （CT） of Gd^3＋-O2^- were observed for Gd2O2CO3：Eu^3＋. Under 172 nm excitation, Gd2O2CO3：Eu^3＋ exhibited strong red emission with good color purity, indicating Eu^3＋ ions located at low symmetry sites and the chromaticity coordination of luminescence for Gd2O2CO3：Eu^3＋ was （x=0.652, y=0.345）. The photoluminescence quenching concentration of Eu^3＋ excited by 172 nm for Gd2O2CO3：Eu^3＋ was about 5%. Gd2O2CO3：Eu^3＋ would be a potential VUV-excited red phosphor applied in mercury-free fluorescent lamps.

Quenching Study on Iron Impurity in Eu^(2+), Dy^(3+) Doped Strontium Aluminate Phosphor Prepared by Nano-Coating Process

A series of long afterglow phosphors, Eu2+, Dy3+, with different iron content were prepared by nano-coating process. The resulted precursors were characterized by Transmission Electron Microscope (TEM), which suggested that the precursor particles had nanometer size distribution. The optical quenching of iron impurity on the phosphor powders were investigated by X-Ray powder Diffraction (XRD) and photoluminescence methods. The XRD indicates that a pure monoclinic SrAl2O4∶Eu2+, Dy3+ was formed at 1200 ℃ and iron impurity up to 296.36×10-4% had no effect on the SrAl2O4∶Eu2+, Dy3+ phase structure. However, the luminescence intensity were strongly dependent on the trace iron impurity, which might be explained that iron displace the aluminium and form Fe-O bond, which competed energy with Eu2+ and transfer red them to infrared sites.

Photoluminescence and ratiometric thermo-response of Eu^(2+)and Eu^(3+)in BaAl_(2)B_(2)O_(7):Eu^(2+),Eu^(3+)phosphor materials

A novel Eu^(2+)-Eu^(3+)co-activated ratiometric thermo-sensitive phosphor was developed and synthesized by solid-state reaction.The valence state of Eu,photoluminescence and thermo-sensitive performance of the phosphor prepared either in ambient air or carbothermally were investigated and discussed.The phosphor shows high sensitivity(Sa=0.0173 K^(-1),S_(r)=0.461%/K)and superior signal discriminability(Δν∼10380 cm^(−1)).The thermo-sensitive performance is subject to the dual effects of different thermo-responses by Eu^(2+)versus Eu^(3+)combined with energy transfer from Eu^(2+)to Eu^(3+),so that the sensitivity of the phosphor in the temperature range presents a non-monotonic trend.The development of the BaAl_(2)B_(2)O_(7):Eu^(2+),Eu^(3+)phosphor is not only expected to be relevant for application in the field of temperature sensing,but also of reference significance for improving the sensitivity by means of energy transfer between co-activator ions over a wider temperature range of Eu^(2+)-Eu^(3+)co-activated ratiometric thermo-sensitive phosphors.

Photoluminescence Characteristics of Gd_2Mo_3O_9:Eu Phosphor Particles by Solid State Reaction Method

Eu^3＋-doped Gd2Mo3O9 was prepared by solid-state reaction method using Na2CO3 as flux and characterized by powder X-ray diffractometry. According to X-ray diffraction, this material belonged to a tetragonal system with space group I41/α. The effects of flux content and sintering temperature on the luminescent properties were investigated with the emission and excitation spectra. The results showed that flux content and sintering temperature had effects on the luminescent properties, the optimized flux content and the best temperature was 3 % and 800 ℃ respectively. The excitation and emission spectra also showed that this phosphor could be effectively excited by C-T band （280 nm）, ultraviolet light 395 nm and blue light 465 nm. The wavelengths at 395 and 465 nm were nicely fitting in with the widely applied output wavelengths of ultraviolet or blue LED chips. Integrated emission intensity of Gd2Mo3O9 ： Eu was twice higher than that of Y2O2S ： Eu^3 ＋ under 395 nm excitation. The Eu^3＋ doped Gd2Mo309 phosphor may be a better candidate in solid-state lighting applications.

Luminescence properties and optical sensing behaviors of Sr_(2)GdSbO_(6):Eu^(3+) phosphors

Novel orange-red Sr_(2)GdSbO_(6):xEu^(3+)(x=0,0.05,0.1,0.2,0.3,0.4,0.5 and 0.6) phospho rs were successfully prepared by the traditional high-temperature solid-state method.The results of Rietveld refinement,energy dispersive spectroscopy(EDS) spectrum and elemental mapping demonstrate that Eu^(3+) successfully replaces the Gd^(3+) sites and distributes uniformly in the particles of phosphors.The luminescence properties of Sr_(2)GdSbO_(6):Eu_(3+)phosphors were investigated in detail.The emission spectra of the strongest emission peak is the ^(5)D_(0)→^(7)F_(1)(593 nm) transition,which can emit orange-red light under393 nm excitation.When the doping concentration of Eu3+ions is x=0.2,the luminescence intensity of the phosphors reaches the highest.The detailed mechanism of concentration quenching is attributed to dipole-dipole interaction.The thermal stability values of Sr_(2)GdSbO_(6):0.2Eu^(3+) phosphors are 87%,82% and114% under 393,467 and 527 nm excitations,respectively.The causes of the abnormal thermal quenching under 527 nm excitation were analyzed.Based on the abnormal thermal quenching under527 nm excitation,the optical thermometry properties of Sr_(2)GdSbO_(6):0.2Eu^(3+)phosphors were investigated by fluorescence intensity ratio(FIR) technique,and appreciable relative sensitivity was obtained.The results suggest that Sr_(2)GdSbO_(6):0.2Eu^(3+)phosphors can be potentially applied to w-LEDs and optical thermometers.

Microwave Assisted Sintering and Photoluminescence Properties of BaaSi6OleNe：Eu^2＋ Green Phosphors

Eu^2＋-doped Ba3Si6012N2 green phosphors were prepared by microwave assisted sintering method at 1275℃ for 4 h, while the counterparts using conventional solid-state reaction method were synthesized at temperature higher than 1300℃ and for to 10 h. Microwave assisted sintering could reduce the activation energy and enhance the diffu- sion rate, thus greatly improved the sintering. Moreover, the influence of Si3N4 content on phase formation, morphol- ogy, absorption, and quantum efficiency, and photoluminescence properties of phosphors were studied. As a result, the Ba3Si6OI2N2：Eu^2＋ samples sintered by microwave assisted sintering method have a higher phase purity and photo- luminescence intensity under ultraviolet excitation as compared with samples sintered in the conventional tube furnace The proposed method is a potential preparation method for the oxynitride phosphors with strong photoluminescence and high phase purity.

Simultaneous enhancement of red luminescence and thermal stability of a novel red phosphor:A Li^(+)-Eu^(3+)co-occupied site strategy in BaAl_(2)Ge_(2)O_(8)lattices

The rapid development of phosphor-converted white light emitting diodes(pc-WLEDs)requires new red phosphors with efficient and thermally stable luminescence for high-quality warm-white lighting.However,it is still a challenge to discover red phosphors with facile synthesis,high internal quantum efficiency(IQE),excellent thermal stability and high color purity.Herein,a novel red-emitting Eu^(3+)activated barium dialuminum digermanate(BaAl_(2)Ge_(3)O_(8),EAGO)phosphor showing strong red emission at 610 nm was prepared.The IQE is improved from 32.91%to 78.84%by employing a charge compensation strategy.The lithium-ion co-dop ed BAGO:Eu^(3+)phosphor exhibits a nearly twofold increase in integral photoluminescence(PL)intensity and the high color purity reaches 94.17%.Impressively,the PL intensity of the BAGO:Eu^(3+),Li^(+)phosphor drops by only 2.6%at 150℃of that at room temperature.Finally,the pc-WLED using the red BAGO:Eu^(3+),Li^(+)phosphor exhibits white light with the chromaticity coordinate of(0.3515,0.3495),a high color-rendering index of 92 and a low correlated color temperature of 4746 K.All these results manifest that BAGO:Eu^(3+),Li^(+)phosphor is a suitable red phosphor for nearultraviolet(NUV)chip-based pc-WLEDs.

Synthesis and optical properties of highly efficient Na_(3)KMg_(7)(PO_(4))_(6):Eu^(2+)blue phosphor for full-spectrum white-light-emitting diodes:The role of Li_(2)CO_(3)flux

Full-spectrum phosphor-converted white-light-emitting diodes(pc-WLED)are emerging as a mainstream technology in semiconductor lighting.Nevertheless,high-performance blue phosphor which can be excited efficiently by a 400 nm NUV diode chip is still lacking.Herein,we present a blue-emitting Na_(3)KMg_(7)(PO_(4))6:Eu^(2+)phosphor synthesized by the solid-reaction method.Particularly,we find that the using of Li_(2)CO_(3)as flux can significantly improve the crystal quality and thus the emission efficiency of the phosphor.Meanwhile,the excitation peak of the phosphor shifts from 365 to 400 nm,which is pivotal for efficient NUV(400 nm)diode chip excitation.The practical Eu^(2+)concentration is also enhanced by using Li_(2)CO_(3)as flux,and the absorption efficiency is greatly increased.This phosphor exhibits superior PL thermal stability,namely retains 94%integrated photoluminescence intensity at 150℃of that at 25℃.As a result,the optimized phosphor shows an emission band peaked at 437 nm with a bandwidth of 40 nm and a high external photoluminescence quantum yield of 51.7%.Finally,a pc-WLED was fabricated by using NKMPO:Eu^(2+)blue,Sr_(2)SiO_(4):Eu^(2+)green,CaAlSiN_(3):Eu^(2+)red phosphors,and a 400 nm NUV diode chip.It shows a high color rendering index of R_(a)=96.4 and a correlated color temperature of 4358 K.These results prove that NKMPO:Eu^(2+)is a promising blue phosphor for full-spectrum WLED based on NUV diode chips.

Interaction of Rare Earth Ions in Sr2MgSi2O7：Eu^2＋,Dy^3＋ Material

To discuss the function of Eu and Dy and their interaction in Sr2 Mg Si2O7：Eu^2＋,Dy^3＋ long afterglow material,the Eu and Dy single doped and their co-doped Sr2 Mg Si2O7：Eu^2＋,Dy^3＋ were prepared.The samples were characterized by X-ray diffraction（XRD）,decay curves,photoluminescence（PL）,and thermoluminescence（TL）.The results indicate that Sr2 Mg Si2O7：Eu has afterglow properties,and the doping of Eu ion in Sr2 Mg Si2O7：Eu^2＋,Dy^3＋ can lower the depth of traps.Eu ion can not only serve as luminescence center,but also produce traps in the matrix,meanwhile,it also exerts certain influences on the traps produced by Dy in Sr2 Mg Si2O7：Eu^2＋,Dy^3＋.The Dy ion can not act as luminescence center but relates to the change of the traps in the Sr2 Mg Si2O7 matrix.

Enhanced luminescence efficiency and thermal stability via introduction of non-rare earth Bi^(3+)in Gd_5Si_(2)BO_(13):Eu^(3+)

A series of Gd_5Si_(2)BO_(13):Eu^(3+)and non-rare earth Bi^(3+)ions doped Gd_5Si_(2)BO_(13):Eu^(3+)phosphors was successfully synthesized via high-temperature solid-state method,and the as-obtained phosphors were studied on their phase structures,luminescence characteristics,thermal stability and luminescence lifetime.Transient fluorescence spectroscopy data show that the addition of Bi^(3+)can obviously enhance the emission intensity of Eu^(3+)in the near-ultraviolet band owing to energy transfer from Bi^(3+)to Eu^(3+).Besides,the addition of Bi^(3+)can improve the thermal stability of a single-doped phosphor Gd_5Si_(2)BO_(13):0.35Eu^(3+)from 70.33%to 87.45%at 150℃and the quantum yield from 58.80%to 78.61%at room temperature.Finally,Gd_5Si_(2)BO_(13):Eu^(3+),Bi^(3+)was used to encapsulate white light-emitting diodes(WLEDs)with green((Ba,Sr)_(2)SiO_(4):Eu^(2+))and blue(BaMgAI_(10)O_(17):Eu^(2+))commercial phosphors.The color rendering index of WLEDs was calculated to be larger than 90,and the color temperature was estimated to be 4300-4500 K,which demonstrate that Gd_5Si_(2)BO_(13):Eu^(3+),Bi^(3+)can be regarded as a red phosphor with great potential application.This paper can provide a new insight into design of high-efficiency phosphors by introducing non-rare earth Bi^(3+)ions via energy transfer from Bi^(3+)to Eu^(3+).

Preparation and characterization of flower-like SrAl_2O_4:Eu^(2+),Dy^(3+) phosphors by sol-gel process

A flower-like Eu^2＋ and Dy^3＋ co-doped SrAl2O4 long-lasting phosphorescent （LLP） phosphor was synthesized via the inorganic- salt-based sol-gel method. The crystal structure, morphology and optical properties of the composite were characterized. X-ray diffraction diffusion （XRD） data and DSC-TG curves of the phosphor revealed that the SrAl2O4 crystallites have been formed after the precursor was calcined at 900 ℃ and to be single-phase SrA1204 at 1100 ℃. The SEM photographs indicated that the sample exhibited a universal flower-like morphology with crystallite size of about l-2μm. After being irradiated with ultraviolet （UV） light, the flower-like phosphor emitted long-lasting green phosphorescence with an excitation peak at 365 nm and emission peak at 500 nm which was ascribed to the characteristic 5d-4f transition of Eu^2＋. Both the PL spectra and the luminance decay curve revealed that this phosphor exhibited efficient luminescence and long lasting properties.