Ba_2Ca(PO_4)_2:Eu~(2+)蓝色荧光粉的合成及其发光特性

采用高温固相法合成了Ba2Ca(PO4)2:Eu2+蓝色荧光粉,研究了合成温度、合成时间、Ba/Ca比值以及Eu2+掺杂量等对材料的物相及发光特性等的影响.研究结果显示,合成温度为900/1200?C,合成时间为4 h时,可以获得纯相的Ba2Ca(PO4)2;以343 nm紫外线作为激发源时,Ba2Ca(PO4)2:Eu2+呈非对称的宽谱特征,主峰位于454 nm,分析认为,Eu2+在Ba2Ca(PO4)2中占据不同的晶体学格位,形成了不同的发光中心,造成材料呈非对称发射;监测454 nm发射峰,对应的激发光谱覆盖200—450 nm区域,主峰位于343 nm,且在长波紫外段(350—410 nm)有很强的激发带;增大Eu2+掺杂量,Eu2+在Ba2Ca(PO4)2中的发射出现了浓度猝灭现象,且材料的发射峰出现了明显的红移;减小基质中Ba/Ca配比,材料在绿色区域的发射逐渐增强,材料的发光颜色由蓝逐渐变为蓝绿色,分析认为,Eu2+进入Ba2Ca(PO4)2基质体系后,不但取代Ba2+的格位,而且取代Ca2+的格位,形成不同的发光中心,从而影响材料的发光特性.     

K_2ZnSiO_4∶Eu~(3+)红色荧光粉的制备及发光性能

采用高温固相法合成了适合近紫外光、蓝光激发的K2ZnSiO4∶Eu3+红色荧光粉,研究了该荧光粉的发光特性。XRD结果显示,所合成的荧光粉主晶相为K2ZnSiO4。样品的激发光谱由O2-→Eu3+电荷迁移带(200~350nm)和Eu3+离子的特征激发峰(350~500nm)组成,最强峰位于396nm,次强峰位于466nm。在396nm和466nm激发下,样品均呈多峰发射,分别由Eu3+离子的5D0→7FJ(J=0,1,2,3,4)能级跃迁产生,其中619nm处峰值最大。增加Eu3+离子的掺杂浓度,荧光粉的发光逐渐增强。在实验测定的浓度范围内,未出现浓度猝灭现象。不同Eu3+浓度样品的色坐标均位于色品图红光区,非常接近NTSC标准。     

红色荧光粉Na_zCa_(1-x-2y-z)Bi_yMoO_4∶Eu_(x+y)~(3+)发光研究

采用高温固相法制备系列红色荧光粉NazCa1-x-2y-zBiyMoO4∶Eux3++y(y,z=0,x=0.24,0.26,0.30,0.34,0.38;x=0.30,y=0.01,0.02,0.03,0.04,0.05,0.06,0.07,z=0;x=0.30,y=0.04,z=0.38)。用X射线粉末衍射(XRD)法测试了所制样品晶相结构。采用荧光光谱仪对样品的发光性能进行了表征,结果表明:当Eu3+单掺杂量浓度x=0.30时,荧光粉(Ca0.70MoO4∶Eu03.+30)的发光强度最强;当Eu3+-Bi3+共掺杂量浓度y=0.03时,电荷迁移带(CTB)强度达到最强,而对于Eu3+特征发射峰,当共掺杂浓度y<0.03时,位于393 nm处的激发峰强度比464 nm强,共掺浓度y>0.03时,464 nm峰比393 nm峰强,共掺浓度为y=0.04时,393和464 nm处两峰位置强度都达到最强。作为电荷补尝剂的Na2CO3掺入上述荧光粉中后,荧光粉激发和发射强度明显地增强。结果表明,通过调节Bi3+/Eu3+掺杂比例可以改变位于近紫外光393 nm和蓝光区464 nm处激发光相对强度。     

LiGd(W_yMo_(1-y))_2O_(8-x/2)F_x∶Eu~(3+)红色荧光粉的制备和发光特性

采用高温固相法制备了LiGd(W_yMo_(1-y))_2O_(8-x/2)F_x∶0.4Eu~(3+)(x=0~1,y=0~1)系列白光LED用红色荧光粉。通过扫描电子显微镜、X射线衍射仪、红外光谱仪、荧光光谱仪对荧光粉的形貌、结构、光学性能进行了表征。结果表明,Eu~(3+)、F-和WO_4~(2-)的掺杂没有改变LiGd(MoO_4)_2的四方晶系白钨矿结构;F~-和WO_4~(2-)最佳掺杂量分别为x=0.6,y=0.4。在396 nm激发下,LiGd(W_(0.4)Mo_(0.6))_2O_(7.7)F_(0.6)∶0.4Eu~(3+)的发光强度比未掺杂样品提高了60%,量子效率可达66.23%。当温度升高至100℃时,样品的发射强度降为25℃时的76.6%。在460 nm激发下,样品的最强窄带发射峰位于617 nm处,归属于~5D_0→~7F_2跃迁,色坐标为(0.649 9,0.346 3)。5D0能级的荧光寿命曲线遵循单指数规律衰减,随着F-掺杂浓度的增加,5D0能级的荧光寿命不断增加,归因于低声子能量的F-掺入有效减小了能量的无辐射跃迁概率。所制备的LiGd(W_(0.4)Mo_(0.6))_2O_(7.7)F_(0.6)∶0.4Eu~(3+)荧光粉有望应用于白光LED。     

SrLiAl_3N_4∶Eu~(2+)红色荧光粉的制备与发光特性

使用高温固相法于还原气氛中合成了SrLiAl_3N_4∶Eu~(2+)荧光粉并研究了其晶体结构和发光性质。样品均可以被蓝光或紫外光有效激发发射红光。XRD和SEM图谱显示合成了单相SrLiAl3N4。粉体的激发光谱在200~600nm波长范围内呈现出双峰宽带激发带,在267nm、474nm处分别有一个激发峰。发射光谱仅有一个宽带发射峰,峰值在654nm处,属于Eu~(2+)离子的5d→4f特征跃迁。荧光粉发光强度与Eu~(2+)离子掺杂摩尔分数之间的关系表明:随着Eu~(2+)离子掺杂摩尔分数的增加,粉体发光强度先上升后下降,最佳掺杂摩尔分数为0.4%,继续增大Eu~(2+)离子的掺杂量会发生浓度猝灭现象。所准备的SrLiAl_3N_4∶Eu~(2+)荧光粉具有较好的热稳定性和较高的量子效率。     

红色荧光粉NazCa1-x-2y-zBiyMoO4∶Eu3+x+y发光研究

采用高温固相法制备系列红色荧光粉Naz Ca1-x-2y-zBiyMoO4 ∶ Eu3+x+y (y,z=0,x=0.24,0.26,0.30,0.34,0.38; x=0.30,y=0.01,0.02,0.03,0.04,0.05,0.06,0.07,z=0; x=0.30,y=0.04,z=0.38).用X射线粉末衍射(XRD)法测试了所制样品晶相结构.采用荧光光谱仪对样品的发光性能进行了表征,结果表明:当Eu3+单掺杂量浓度x=0.30时,荧光粉(Ca0.70 MoO4∶Eu3+0.30)的发光强度最强;当Eu3+-Bi3+共掺杂量浓度y=0.03时,电荷迁移带(CTB)强度达到最强,而对于Eu3+特征发射峰,当共掺杂浓度y＜0.03时,位于393 nm处的激发峰强度比464 nm强,共掺浓度y＞0.03时,464 nm峰比393 nm峰强,共掺浓度为y=0.04时,393和464 nm处两峰位置强度都达到最强.作为电荷补尝剂的Na2 CO3掺入上述荧光粉中后,荧光粉激发和发射强度明显地增强.结果表明,通过调节Bi3+ /Eu3+掺杂比例可以改变位于近紫外光393 nm和蓝光区464 nm处激发光相对强度.     

一种新型的白光LED用绿色荧光粉Ca_8MgLu(PO_4)_7∶Tb~(3+)

采用高温固相法合成一种单一纯相绿色荧光粉Ca8Mg Lu(PO4)7∶Tb3+,通过X射线衍射(XRD)、荧光光谱(PLE,PL)和荧光寿命曲线研究了Ca8Mg Lu(PO4)7∶Tb3+的发光性能。Ca8Mg Lu(PO4)7∶Tb3+能被378nm的近紫外光激发,Tb3+发生5D4-7F5跃迁发出绿光,色坐标为(0.324,0.592)。Ca8Mg Lu(PO4)7∶Tb3+的量子效率可达84%,热猝灭性能良好:在150℃和200℃的发光强度积分分别是25℃的90.71%和86.36%。研究结果表明Ca8Mg Lu(PO4)7∶Tb3+是一种理想的适于NUV-LED芯片激发的白光LED用绿色荧光粉。     

近紫外宽带激发LED用红色荧光粉(Gd_(1-x)Eu_x)6(Te_(1-y)Mo_y)O_(12)的制备与性能

利用高温固相法制备了一种新型红色荧光粉(Gd_(1-x)Eu_x)_6(Te_(1-y)Mo_y)O_(12),研究了Eu~(3+)单掺和Eu~(3+),Mo~(6+)共掺Gd_6TeO_(12)荧光粉的结构、形貌和荧光性能.实验结果表明,所合成的粉体为纯相.在393 nm近紫外光激发下,(Gd_(1-x)Eu_x)_6(Te_(1-y)Mo_y)O_(12)荧光粉发出特征红光,位于632 nm处的发射主峰属于Eu~(3+)的~5D_0→~7F_2跃迁.当Eu~(3+)掺杂浓度超过20%(物质的量分数)时发光出现浓度淬灭,经证实这是由电偶极-电偶极相互作用造成的.随着工作温度升高,荧光粉发光强度减小,计算得到Eu~(3+)热淬灭过程中的激活能为0.1796 eV.当(Gd_(0.8)Eu_(0.2))_6TeO_(12)中共掺Mo~(6+_(取代Te~(6+)),该荧光粉发射光谱的峰位、强度变化不大,但是Mo~(6+)-O~(2-)电荷迁移态显著增大了近紫外波段的激发带宽度,可以有效提高激发效率.具有近紫外宽带激发特征的(Gd_(0.8)Eu_(0.2))_6(Te_(0.6)Mo_(0.4))O_(12)是一种潜在的白光LED用荧光粉材料.     

新型红色荧光粉Na2Ca4(PO4)2SiO4:Eu3+,Bi3+的制备及发光特性

用高温固相法合成了用于白光LED的Na2Ca4(1-x-y)(PO4)2SiO4:xEu3+,yBi3+红色荧光粉.研究了助熔剂H3BO3、二次煅烧时间和稀土掺杂量等制备条件对样品发光性质的影响.结果表明,在1 200℃、助熔剂H3BO3加入量为样品质量的3.8%时可得到更有利于发光的α-NCPS基质,而且掺入Eu3+、Bi3+之后,基质的晶格结构没有发生明显变化;适宜的二次煅烧时间为1.5 h.Bi3+的共掺杂可以通过能量传递大幅提高Eu3+的发光强度,当Eu3+、Bi3+的摩尔分数分别为x=0.04和y=0.01时,粉体具有最强的红光发射.表明这种荧光粉是一种可很好用于近紫外芯片的白光LED的红色荧光粉.     

新型红色荧光粉Na2Ca4(PO4)2SiO4:Eu3+,Bi3+的制备及发光特性

用高温固相法合成了用于白光LED的Na2Ca4(1-x-y)(PO4)2SiO4:xEu3+,yBi3+红色荧光粉.研究了助熔剂H3BO3、二次煅烧时间和稀土掺杂量等制备条件对样品发光性质的影响.结果表明,在1 200℃、助熔剂H3BO3加入量为样品质量的3.8%时可得到更有利于发光的α-NCPS基质,而且掺入Eu3+...     

Eu^2＋：Sr9Ca（PO4）6Cl2中的新型色心及其光激励发光

本文报道了Ｅｕ＾２＋：Ｓｒ９Ｃａ（ＰＯ４）６Ｃｌ２的新型色心。它的吸收带主峰分别位于７０８，７８５，８４５及９９０ｎｍ。用对应于Ｆ心吸收带和这些吸收带波长的光束分别激励样品时得到相同的光激励发光。通过对比研究表明，这些吸收带是由Ｆ心的缔合中心，即由ＦＡ心产生的。由于这些色心的吸收带偏离Ｅｕ＾２＋的发射波长（４５０ｎｍ）更远，故更适应于Ｅｕ＾２＋：Ｓｒ９Ｃａ（ＰＯ４）６Ｃｌ２光波励发光的研究和开发。     

水热法制备的NaEu(MoO4)2-x(WO4)x固溶体微晶及其发光特性

采用水热法制备了NaEu(MoO4)2-x(WO4)x固溶体微晶; 通过X射线衍射(XRD)、扫描电镜(SEM)和荧光分析(FA)对所制备的微晶进行了表征。XRD结果表明NaEu(MoO4)2-x(WO4)x微晶呈现典型的四方晶相白钨矿结构。SEM分析表明微晶呈米粒状。荧光分析显示, NaEu(MoO4)2-x(WO4)x微晶在370～386 nm之间呈现MO2-4 配离子(M=Mo,W)的特征发射峰, 发射波长随x的增大而减小; 同时, Eu3+在592 nm(5D0→7F1)和614 nm(5D0→7F2)的特征发射峰均明显显现, 强度随x的增大而逐渐增大。     

Size-dependent microstructure and europium site preference influence fluorescent properties of Eu-doped Ca10(PO4)6(OH)2 nanocrystal

In this study, Eu³⁺-doped nanocrystalline Ca₁₀(PO₄)₆(OH)₂ (Ca_10−xEu_x(PO₄)₆(OH)₂) with different particle sizes have been prepared by the thermal decomposition of precursors. Size-dependent microstructure could be observed in nanocrystalline Ca_10−xEu_x(PO₄)₆(OH)₂. The lattices of Ca_10−xEu_x(PO₄)₆(OH)₂ nanocrystals were more distorted in comparison with the bulk, and the smaller the particle size, the more distorted the lattices. Room temperature photoluminescence showed europium site preference was also size-dependent, with the majority of Eu³⁺ ions occupying Ca(II) sites in the bulk, but more and more Eu³⁺ ions occupying Ca(I) sites in Ca_10−xEu_x(PO₄)₆(OH)₂ with decreasing particle size. Fluorescent properties of Ca_10−xEu_x(PO₄)₆(OH)₂ were considered to be influenced by both microstructure and site preference of Eu³⁺ ions. An abnormal strong intensity of ⁵D₀-⁷F₀ transition was observed in bulk and larger Ca_10−xEu_x(PO₄)₆(OH)₂ nanocrystals, but the relative intensities of ⁵D₀-⁷F₀ transition to ⁵D₀-⁷F_1,2,3,4 transition of Eu³⁺ became weaker as the particle sizes decreased. As the particle sizes became smaller, the ratios of the red emission transition (⁵D₀-⁷F₂) to the orange emission transition (⁵D₀-⁷F₁) (R/O values) first increased by comparing the bulk sample with 96 nm sample, and then decreased by comparing 96 nm sample to 57 nm sample. The quenching concentrations of Ca_10−xEu_x(PO₄)₆(OH)₂ samples increased with decreasing particle size. Possible mechanisms responsible for these phenomena were proposed. Since nanosized Ca_10−xEu_x(PO₄)₆(OH)₂ showed higher fluorescent intensities, higher R/O values and higher quenching concentrations, this material is considered to be a promising phosphor.     

Improved luminescent properties of red-emitting Ca0.54Sr0.16Eu0.08Gd0.12(MoO4)0.2(WO4)0.8 phosphor for LED application by charge compensation

The red-emitting Ca_0.54Sr_0.16Eu_0.08Gd_0.12(MoO₄)_0.2(WO₄)_0.8 phosphor is improved in the emission charateristics by charge compensation, of which chromaticity coordinates (CIE) are x=0.66 and y=0.33. Three approaches to charge compensation are investigated, namely (a) 3Ca²⁺/Sr²⁺→2Eu³⁺/Gd³⁺+vacancy, (b) 2Ca²⁺/Sr²⁺→Eu³⁺/Gd³⁺+M⁺(M⁺ is a monovalent cation like Li⁺, Na⁺ and K⁺ employed as a charge compensator) and (c) Ca²⁺/Sr²⁺→Eu³⁺/Gd³⁺+N⁻ (N⁻ is a monovalent anion like F⁻, Cl⁻, Br⁻ and I⁻ employed as charge compensation ions). Through photoluminescent spectra analyzing the radiative and non-radiative relaxation mechanisms of luminescent system are obtained. Under 20 mA forward-bias current, one red-emitting LED is made by combining 390-405 nm-emitting LED chip and the phosphor. The red-emitting phosphor has broad prospects in LED application field.     

Growth and laser properties of Nd:Ca4YO(BO3)3 crystal

Nd:Ca₄YO(BO₃)₃ (Nd:YCOB) crystal was grown by the Czochralski method, and its structure was measured by using a four circle X-ray diffractometer. The transparent spectrum from 200 to 2600 nm was measured at room temperature. The fluorescence spectrum near 1.06 μm showed that the main emission wavelength of Nd:YCOB crystal was centered at 1060.8 nm. Laser output at 1.06 μm has been demonstrated when it was pumped by a Ti:sapphire laser at the wavelength of 794 nm, the highest output power was 68 mW under pumping power of 311 mW, the pumping threshold was 163 mW and slope efficiency was 46.9%. The self-frequency doubled green light has been observed when it was pumped by a Ti:sapphire or a laser diode (LD). A 14.5 mm Nd:YCOB crystal sample cut at (θ, φ)=(90°, 33°) was used for type I second-frequency generation (SHG) of the 1.06 μm laser pulse. The SHG conversion efficiency was 22%.     

Luminescence and OSL study of the inorganic compounds Tl-doped (NH4)2BeF4 and (NH4)2SiF6

The search of materials with efficient optically stimulated luminescence (OSL) properties and a high hydrogen content for fast neutron dosimetry has led to the development of Tl⁺-doped ammonium salts (NH₄)₂SiF₆ and (NH₄)₂BeF₄. Preliminary OSL studies have shown that the OSL in (NH₄)₂SiF₆:Tl⁺ and (NH₄)₂BeF₄:Tl⁺is efficient. In order to optimise the OSL emission and its detection, the identification of the luminescent centres in the OSL process is necessary. This study focuses on the identification of the luminescent centres associated with Tl⁺ based on optical studies in the vacuum UV (VUV) at different temperatures.     

Physico-chemical characterization of electrochemical deposit of Ca10(PO4)6(OH)2 on copper surfaces

Surface modification of biomaterials to improve biocompatibility without changing their bulk properties is desired for many clinical applications and has become an emerging technology in biomaterial research and industry. In the present study, a sample electrochemical method of coating the solid surfaces of copper, with a film of apatite, was developed. Thin layer of calcium phosphate crystals formed on the surfaces of copper, was carried out by electrochemical methods, and characterized by XRD, infrared spectroscopy and chemical analysis.     

High-pressure Raman spectroscopic studies on orthophosphates Ba3(PO4)2 and Sr3(PO4)2

By using diamond anvil cell (DAC), high-pressure Raman spectroscopic studies of orthophosphates Ba₃(PO₄)₂ and Sr₃(PO₄)₂ were carried out up to 30.7 and 30.1 GPa, respectively. No pressure-induced phase transition was found in the studies. A methanol:ethanol:water (16:3:1) mixture was used as pressure medium in DAC, which is expected to exhibit nearly hydrostatic behavior up to about 14.4 GPa at room temperature. The behaviors of the phosphate modes in Ba₃(PO₄)₂ and Sr₃(PO₄)₂ below 14.4 GPa were quantitatively analyzed. The Raman shift of all modes increased linearly and continuously with pressure in Ba₃(PO₄)₂ and Sr₃(PO₄)₂. The pressure coefficients of the phosphate modes in Ba₃(PO₄)₂ range from 2.8179 to 3.4186 cm⁻¹ GPa⁻¹ for ν₃, 2.9609 cm⁻¹ GPa⁻¹ for ν₁, from 0.9855 to 1.8085 cm⁻¹ GPa⁻¹ for ν₄, and 1.4330 cm⁻¹ GPa⁻¹ for ν₂, and the pressure coefficients of the phosphate modes in Sr₃(PO₄)₂ range from 3.4247 to 4.3765 cm⁻¹ GPa⁻¹ for ν₃, 3.7808 cm⁻¹ GPa⁻¹ for ν₁, from 1.1005 to 1.9244 cm⁻¹ GPa⁻¹ for ν₄, and 1.5647 cm⁻¹ GPa⁻¹ for ν₂.     

Photoluminescence and thermoluminescence characterization of Eu- and Dy -activated Ca3(PO4)2 phosphor

Rare-earth-doped polycrystalline Ca₃(PO₄)₂:Eu, Ca₃(PO₄)₂:Dy and Ca₃(PO₄)₂:Eu,Dy phosphors prepared by a modified solid-state synthesis has been studied for its X-ray diffraction, thermoluminescence (TL) and photoluminescence (PL) characteristics. The PL emission spectra of the phosphor suggest the presence of Eu³⁺ ion in Ca₃(PO₄)₂:Eu and Dy³⁺ ion in Ca₃(PO₄)₂:Dy lattice sites. The TL glow curve of the Ca₃(PO₄)₂:Eu compounds has a simple structure with a prominent peak at 228 °C, while Ca₃(PO₄)₂:Dy peaking at 146 and 230 °C. TL sensitivity of phosphors are compared with CaSO₄: Dy and found 1.52 and 1.20 times less in Ca₃(PO₄)₂:Eu and Ca₃(PO₄)₂:Dy phosphors, respectively. The Ca₃(PO₄)₂:Eu,Dy phosphors shows switching behavior under two different excitation wavelengths and enhancement in PL intensity of Dy³⁺ ions were reported. The paper discusses the photoluminescence and thermoluminescence behavior of Eu³⁺ and Dy³⁺ ion in Ca₃(PO₄)₂ hosts, it may be applicable to solid-state lighting as well as thermoluminescence dosimetry applications.     

Recombination luminescence mechanisms in Ba3(PO4)2

The effect of hole self-trapping in Ba₃(PO₄)₂ at low temperatures has been studied. The TSL peak at 135 K is due to hole delocalization and diffusion by thermally activated hopping between perfect lattice sites, resulting in a composite uv band, corresponding to the tunneling recombination of holes with localized electrons.