Ca8Mg(SiO4)4Cl2中Ce3+和Eu2+的光谱性质和能量传递

首次合成了Ｃｅ＾３＋和Ｅｕ＾２＋共激活氯硅酸镁钙Ｃａ８Ｍｇ（ＳｉＯ４）４Ｃｌ２：Ｃｅ＾３＋，Ｅｕ＾２＋高效绿色荧光粉，报道了它们的漫反射光谱、激发和发射光，观察到氯硅酸镁钙中Ｃｅ＾３＋ Ｅｕ＾２＋     

Potential tunable white-emitting phosphor LiSr4(BO3)3:Ce3+, Eu2+ for ultraviolet light-emitting diodes

A novel Ce³⁺/Eu²⁺ co-activated LiSr₄(BO₃)₃ phosphor has been synthesized by traditional solid-state reaction. The samples could display varied color emission from blue towards white and ultimately to yellow under the excitation of ultraviolet (UV) light with the appropriate adjustment of the relative proportion of Ce³⁺/Eu²⁺. The resonance-type energy transfer mechanism from Ce³⁺ to Eu²⁺ in LiSr₄(BO₃)₃:Ce³⁺, Eu²⁺ phosphors is dominant by electric dipole–dipole interaction, and the critical distance is calculated to be about 29.14 Å by the spectra overlap method. White light was observed from LiSr₄(BO₃)₃:mCe³⁺, nEu²⁺ phosphors with chromaticity coordinates (0.34, 0.30) upon 350 nm excitation. The LiSr₄(BO₃)₃:Ce³⁺, Eu²⁺ phosphor has potential applications as an UV radiation-converting phosphor for white light-emitting diodes.     

A potential red emitting K4Ca(PO4)2: Eu3+ phosphor for white light emitting diodes

Europium (III) ions doped red phosphors K₄Ca(PO₄)₂ were prepared first time by high temperature solid state reaction method. The prepared phosphors structure was examined by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) analyses. The thermal properties of the synthesized phosphor were investigated by differential scanning calorimetry (DSC) analysis. Photoluminescence (PL) spectra of K₄Ca(PO₄)₂:Eu³⁺ phosphors have shown strong red emission at 618 nm (⁵D₀→⁷F₂) with near UV an excitation wavelength of λ_exc=394 nm (⁷F₀→⁵L₆). In addition, the decay curves and CIE color coordinate measurements are also carried out. Hence, emission and excitation characterization of synthesized phosphors shows that the phosphors may be a promising red component for the application in the white light emitting diodes (WLEDs).     

白光LED用Ca_8Mg(SiO_4)_4Cl_2:Eu~(2+),Dy~(3+)发光粉的发光性能

采用高温固相法合成了白光LED用Ca8Mg(SiO4)4Cl2:Eu和Ca8Mg(SiO4)4Cl2:Eu,Dy绿色发光粉。研究发现:共掺Dy可以明显地提高Ca8Mg(SiO4)4Cl2:Eu发光粉的发光性能,表明Dy3+和Eu2+之间存在着能量传递过程。当Dy3+的最佳掺杂摩尔分数为0.02时,发光粉505nm处绿光发射的强度约提高12%。通过对Dy3+和Eu2+光谱特性的分析,Dy3+和Eu2+之间的能量传递机制可归因于无辐射交叉弛豫。     

Luminescent properties of Mg3Ca3(PO4)4: Eu2+ blue-emitting phosphor for white light emitting diodes

A blue-emitting phosphor, Eu²⁺-activated Mg₃Ca₃(PO₄)₄ phosphor was synthesized by conventional solid-state reaction. X-ray powder diffraction (XRD) analysis confirmed the phase formation. Photoluminescence (PL) results showed that Mg₃Ca₃(PO₄)₄: Eu²⁺ could be efficiently excited by UV–visible light from 250 to 430 nm, which matched well with the emission wavelengths of near-UV and UV LED chips. The effects of the doped-Eu²⁺ concentration in Mg₃Ca₃(PO₄)₄: Eu²⁺ on the PL were also investigated. The result reveals that Mg₃Ca₃(PO₄)₄: Eu²⁺ is a potential blue-emitting phosphor for white LEDs.     

M2SiO4：Re(M=Mg,Ca,Ba;Re=Ce3+,Tb3+)的发光性能

合成了系列M₂SiO₄:Re(M=Mg,Ca,Ba;Re=Ce³⁺,Tb³⁺)样品,研究了样品在真空紫外区域的激发光谱和发射光谱。从激发谱可以看出:M₂SiO₄:Re(M=Mg,Ca,Ba;Re=Ce³⁺,Tb³⁺)在147,172nm有很强的吸收带。用Mg,Ca完全取代Ba₂SiO₄:Tb³⁺中的Ba,相对应的晶体的晶格参数逐渐增大,晶场的能量逐渐减少,其激发光谱随着碱土离子半径的增加向长波方向移动。在172nm真空紫外光激发下,观察到M₂SiO₄:Re(M=Mg,Ca,Ba;Re=Tb³⁺和M₂SiO₄:Re(M=Mg,Ca,Ba;Re=Ce³⁺,Tb³⁺)特征发射;在真空紫外激发下,随着M₂SiO₄:Re(M=Mg,Ca,Ba;Re=Ce³⁺,Tb³⁺)中Ce³⁺含量的增加,M₂SiO₄:Re的特征发射明显减弱,并分析讨论了相关发光现象的成因。     

M2SiO4:Re(M=Mg,Ca,Ba;Re=Ce3+,Tb3+)的发光性能

合成了系列M2SiO4∶Re(M=Mg,Ca,Ba; Re= Ce3 ,Tb3 )样品,研究了样品在真空紫外区域的激发光谱和发射光谱.从激发谱可以看出:M2SiO4∶Re(M=Mg,Ca,Ba; Re= Ce3 ,Tb3 )在147,172 nm有很强的吸收带.用Mg,Ca完全取代Ba2SiO4∶Tb3 中的Ba ,相对应的晶体的晶格参数逐渐增大,晶场的能量逐渐减少,其激发光谱随着碱土离子半径的增加向长波方向移动.在172 nm真空紫外光激发下,观察到M2SiO4∶Re(M=Mg,Ca,Ba; Re=Tb3 和M2SiO4∶Re(M=Mg,Ca,Ba; Re= Ce3 ,Tb3 )特征发射;在真空紫外激发下,随着M2SiO4∶Re(M=Mg,Ca,Ba; Re= Ce3 ,Tb3 )中Ce3 含量的增加,M2SiO4∶Re的特征发射明显减弱,并分析讨论了相关发光现象的成因.     

Persistent luminescence in Ca8Zn(SiO4)4Cl2:Eu2+

A new persistent, green emission is reported for europium activated Calcium Zinc Chlorosilicate (CZCS). The phosphor was prepared by the solid state reaction and characterized using XRD, PL and TL techniques. The decay was characterized by admixture of two exponential components with decay constants 20.2 and 101 s.     

Luminescence properties and energy transfer in Ba2Y(BO3)2Cl:Ce3+,Tb3+ phosphors

Novel green-emitting Ba₂Y(BO₃)₂Cl:Ce³⁺,Tb³⁺ phosphors were synthesized by a solid-state method. X-ray diffraction and photoluminescence spectra were utilized to characterize the structures and luminescence properties of the as-synthesized phosphors, respectively. Ba₂Y(BO₃)₂Cl:Ce³⁺,Tb³⁺ phosphors exhibit blue and green emission bands under the excitation of near-ultraviolet light. An asymmetric blue emission originates from the Ce³⁺ ion, whereas the green emission originates from the Tb³⁺ ion. A spectral overlap is found between the emission band of the Ce³⁺ ion and the excitation band of the Tb³⁺ ion, which supports the occurrence of the energy transfer from the Ce³⁺ ion to the Tb³⁺ ion. Meanwhile, the energy transfer is thoroughly investigated by their photoluminescence decay behaviors. The energy-transfer efficiency from the Ce³⁺ ion to the Tb³⁺ ion is also calculated, and a possible mechanism is proposed.     

用于白光LED的单一基质白光荧光粉Ca2SiO3Cl2:Eu2+,Mn2+的发光性质

用高温固相法合成了Eu2+,Mn2+共激活的Ca2SiO3Cl2高亮度白色发光材料,并对其发光性质进行了研究.该荧光粉在近紫外光激发下发出强的白色荧光,Eu2+中心形成峰值为419 nm和498 nm的特征宽带,通过Eu2+中心向Mn2+中心的能量传递导致了峰值为578 nm的发射,三个谱带叠加从而在单一基质中得到了白光.激发光谱均分布在250-415 nm的波长范围,红绿蓝三个发射带的激发谱峰值分别位于385 nm,412 nm,370 nm和396 nm处,可以被InGaN管芯产生的紫外辐射有效激发.Ca2SiO3Cl2:Eu2+,Mn2+是一种很有前途的单一基质白光LED荧光粉.     

LaOBr:Ce,Tb中Ce3+对Tb3+发光的影响

近年来人们对LaOBr:Tb的合成及其发光特性的研究日益增多。LaOBr:Tb不仅是良好的X光增感屏材料,也是较好的阴极射线发光材料。为了进一步提高它的亮度,降低了b的含量(因Tb很贵),寻求LaOBr中Tb3+发光的敏化剂是很重要的。     

Luminescent properties of Li2 (Ca0.99, Eu0.01) SiO4: B3+ particles as a potential bluish green phosphor for ultraviolet light-emitting diodes

In our study, the 1% mol Eu²⁺ doped Li₂CaSiO₄: B³⁺ phosphors were prepared by the combustion method as fluorescent material for ultraviolet, light-emitting diodes (UV-LEDs) used as a light source. The properties of Li₂ (Ca_0.99, Eu_0.01) SiO₄: B³⁺ phosphors with urea concentration, doping boric acid and a series of initiating combustion temperature were investigated. The crystallization and particle sizes of Li₂ (Ca_0.99, Eu_0.01) SiO₄: B³⁺ has been investigated by using powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). Luminescence measurements showed that the phosphors can be efficiently excited by UV to the visible region, and exhibited bluish green light with a peak of 480 nm. The results showed that the boric acid was effective in improving the luminescence intensity of Li₂ (Ca_0.99, Eu_0.01) SiO₄: B³⁺ and the optimum molar ratio of boric acid to calcium nitrate was about 0.06. The optimized phosphors Li₂ (Ca_0.99, Eu_0.01) SiO₄: B _0.06 ³⁺ showed 180% improved emission intensity compared with that of the Li₂ (Ca_0.99, Eu_0.01) SiO₄ phosphors under ultraviolet (λ_ex =287 nm) excitation.      

LaOBr:Ce3+,Tb3+中Ce3+与Tb3+间能量传递

本文利用毫微秒技术在ns秒量级测量了不同浓度组分的LaOBr:Ce3+,Tb3+中Ce3+发射带的衰减常数τCe值和时间分辨光谱,确立了Ce3到Tb3+能量传递过程模型,建立了动力学方程和导出能量传递的计算公式。据此计算出Ce3+到Tb3+的能量传递几率和效率,得出Ce3+,Tb3+的最佳浓度。     

Luminescence and energy transfer of white-light emitting CaAl2SiO6:Ce3+, Tb3+ phosphors

A novel white-light emitting CaAl₂SiO₆: Ce³⁺, Tb³⁺ phosphor has been prepared by a sol–gel method. X-ray diffractometry and spectrofluorometry were used to characterize structural and optical properties of the samples. The results indicate that the crystal structure of the phosphor is a single phase of CaAl₂SiO₆. The excitation band of the phosphor covers a wide region from 240 nm to 380 nm. CaAl₂SiO₆: Ce³⁺, Tb³⁺ phosphors show four emission bands: one at 400 nm for Ce³⁺ and three at 487 nm, 543 nm and 585 nm for Tb³⁺. With appropriate tuning of Tb³⁺ content, white light with different hues can be achieved under UV radiation. The energy transfer mechanism from Ce³⁺ to Tb³⁺ in CaAl₂SiO₆ host was demonstrated to be dipole–dipole interaction.     

Effect of Tb3+ co-doping and particle size on K2Ca2(SO4)3:EU phosphor

K₂Ca₂(SO₄)₃ doped with Eu, and co-doped with Tb were prepared by the solid state diffusion method. The nanoparticles of these phosphors were also prepared by the chemical co-precipitation method. The formation of the compounds was confirmed by XRD. The particle size was calculated by the broadening of the XRD peaks using Scherrer's formula. The particle size was found to be around 20?nm. Thermoluminescence (TL) was studied to see the effect of co-doping and particle size. Tb³⁺ co-doping decreases the intensity in the Eu²⁺ doped phosphor due to the energy transfer and multiple de-excitations through various radiative and non-radiative processes. The K₂Ca₂(SO₄)₃:Eu,Tb phosphor is found to be 0.33 times more sensitive than TLD-700H, but around 15 times more than LiF-TLD 100, and 7 times more than CaSO₄:Dy. The effective atomic number Z_eff is around 15, which is again comparable to CaSO₄:Dy.

However, very low sensitivity was observed in the case of nanoparticles. The decrease in the sensitivity is attributed to the particle size effect i.e., the volume-to-surface ratio. Study of photoluminescence (PL) of the material is also carried out.     

Ca2SiO4:Dy3+材料的制备及其发光特性

采用高温固相法制备了Ca2SiO4:Dy3 发光材料,在365 nm紫外光激发下,测得Ca2SiO4:Dy3 材料的发射光谱为一多峰宽谱,主峰分别位于486 nm,575 nm和665 nm处;监测575 nm发射峰,测得材料的激发光谱为一多峰宽谱,主峰分别位于331 nm,361 nm,371 nm,397 nm,435 nm,461 nm和478 nm处,研究了Dy3 掺杂浓度对Ca2SiO4:Dy3 材料发射光谱及发光强度的影响,结果显示,随Dy3 浓度的增大,黄、蓝发射峰强度比(Y/B)逐渐增大,利用Judd-Ofelt理论解释了其原因;随Dy3 浓度的增大,Ca2SiO4:Dy3材料发光强度先增大,在Dy3浓度为4 mol%时到达峰值,而后减小,根据Dexter理论其浓度猝灭机理为电偶极-电偶极相互作用,研究了电荷补偿剂Li ,Na 和K 对Ca2SiO4:Dy3 材料发射光谱的影响,结果显示,不同电荷补偿剂下,随电衙补偿剂掺杂浓度的增大,Ca2SiO4:Dy3 材料发射光谱强度的演化趋势相同,即Ca2SiO4:Dy3材料发射峰强度先增大后减小,但不同电荷补偿剂下,材料发射峰强度最大处对应的补偿剂浓度不同,对应Li ,Na 和K 时,浓度分别为4 mol%,4 mol%和3 mol%.     

White light emission from blue and near ultraviolet light-emitting diodes precoated with a Sr3SiO5:Ce3+,Li+ phosphor

White-light-emitting diodes (WLEDs) were fabricated by combining a yellow Sr3SiO5:Ce3+, Li+ phosphor with a blue light-emitting diode (LED) (460 nm chip) or a near ultraviolet (n-UV) LED (405 nm chip), respectively. Color temperature (Tc) of Sr3SiO5:Ce3+, Li+-based WLEDs could be tuned from 6500 to 100,000 K (blue LED pumping) and from 4900 to 50,000 K (n-UV LED pumping) without mixing with other phosphors. The blue LED-pumped WLED showed excellent white light (luminous efficiency=31.7 lm/W, Tc=6857 K) at 20 mA. This WLED showed a stable color coordinates property against an increase of the forward current. An n-UV LED-pumped WLED also showed bright white light (25.0 lm/W, 5784 K) at 20 mA.     

Ba3Tb(BO3)3:Ce3+:一种白光LED用绿色荧光粉

采用高温固相法合成了Ba3Tb(BO3)3和Ba3Tb(BO3)3:Ce3+两种绿色荧光粉,并研究了材料的发光性质.Ba3Tb(BO3)2材料呈多峰发射,发射峰位于439,493,547,589和629 nm,分别对应Tb3+的5D3→7F4和5D4→7F1=6,5,4,3跃迁发射,主峰为547 nm;监测547 nm发射峰,所得激发光谱由4f75d1宽带吸收(200-330 nm)和4f4f电子吸收(330-400 nm)组成,主峰为380 nm.以Ce3+激活Ba3Tb(BO3)3,所得Ba3Tb(BO3)3:Ce3+与Ba3Tb(BO3),材料的发射光谱分布相同,但发射强度明显增强,说明Ce3+对Tb3+产生了很好的敏化作用;监测547 nm最强发射峰,所得激发光谱为宽带,主峰位于360 nm.改变H3BO3量,Ba3Tb(BO3)3:Ce3+材料的发射强度随之变化,当H3BO3过量15 wt%时,发射强度最大.上述研究结果表明Ba3Tb(BO3)3:Ce3+是一种很好的适于UV-LED管芯激发的白光LED用绿色荧光粉.