Pr^3＋或Sm^3＋掺杂YAG∶Ce的发光特性及其荧光寿命

研究了Pr3 ,Sm3 掺杂对YAG∶Ce发射光谱及其荧光寿命的影响。观察到当掺杂Pr3 时,在609nm处出现Pr3 的发射峰,而掺杂Sm3 时,在616nm处呈现Sm3 的发射峰。掺杂Pr3 或Sm3 增加红光区的发射峰将有利于提高YAG∶Ce荧光粉的显色性。实验中测定了(Y0.95Sm0.01Ce0.04)3Al5O12、(Y0.95Pr0.01Ce0.04)3Al5O12、(Y0.96Ce0.04)3Al5O12的荧光寿命(τ),观察到在YAG∶Ce中掺入Pr3 或Sm3 使Ce3 的荧光寿命减小。实验结果表明,少量掺杂Pr3 或Sm3 并未引起基质的结构的变化。     

白光LED用Ce3/Sm3共掺玻璃和微晶玻璃的发光特性及能量传递研究

采用高温熔融法制备了一系列Ce3+/Sm3+共掺透明微晶玻璃,并研究了其发光特性.在微晶玻璃中Ce3+呈现出基于4f 5d跃迁的较强的宽带蓝光发射,通过调节Ce3+/Sm3+离子的掺杂浓度,Ce3+/Sm3+离子共掺微晶玻璃发光的色度逐渐发生变化,当CeO2/Sm2O3掺杂的量比为1∶1时,制得的微晶玻璃发光色坐标为(0.315,0.296).通过光谱和荧光衰减曲线,研究了Ce3+离子到Sm3+离子的能量传递,在SAZKNGC0.6S0.6微晶玻璃中,Ce3+离子向Sm3+离子传递能量效率约为20%.结果表明,Ce3+/Sm3+共掺微晶玻璃是白光LED的一种潜在基质材料     

锗酸盐玻璃中Yb3+/Tm3+/Ho3+掺杂浓度对2 μm发光的影响

为了研究锗酸盐玻璃中采用Yb3+/Tm3+/Ho3+三掺杂方式实现2 μm激光的可行性,研究了3种稀土离子的掺杂浓度对近2 μm发光的影响,从而对稀土离子掺杂浓度进行优化选择以确定理想的掺杂浓度.实验结果表明,在TmF3掺杂摩尔分数为1%时,随着Yb3+浓度的提高Ho3+的2 μm荧光强度增强;当TmF3掺杂摩尔分数为3%时,随着Yb3+浓度的提高Ho3+的2 μm荧光强度降低;随着Yb3+浓度的提高,Tm3+的近2 μm荧光发射会得到增强,且当Tm3+浓度较高时其发光更为明显,这相对削弱了Ho3+的2 μm荧光.Ho3+2 μm发光受Tm3+/Ho3+的浓度比值影响很大,即用980 nm光抽运三掺杂样品,无论Tm3+浓度单一提高还是Ho3+浓度单一降低,对于Ho3+的2μm荧光都是不利的.     

Yb3+-Tm3+共掺钨钼酸盐纳米晶体的发光特性

以聚乙二醇为络合剂,采用水热法制备了发光性能优越的Yb3+-Tm3+共掺BaGd2(WO4)0.5(MoO4)0.5纳米晶体。改变稀土掺杂量并生产不同掺杂量的BaGd2(WO4)0.5(MoO4)0.5∶Yb3+/Tm3+。以X射线衍射仪(XRD)、扫描电子显微镜(SEM)及透射电子显微镜(TEM)对样品进行表征。结果表明,BaGd2(WO4)0.5-(MoO4)0.5∶Yb3+/Tm3+纳米晶属四方晶系,粒径在25~40nm之间,使用Hitachif-4500分光光度计分析样品,发现当Yb3+/Tm3+为4∶1、Yb3+离子浓度为6.0%时,BaGd2(WO4)0.5(MoO4)0.5∶Yb3+/Tm3+的发光效率最高。当Tm3+离子发生1G4→3H6跃迁时会产生可见光发射,对应于光谱图中475nm处的蓝光;当Tm3+离子发生1G4→3F4跃迁时产生的可见光发射,对应于光谱图中650nm处的红光。光谱图像及泵浦功率的双对数曲线表明,其中蓝光发射是三光子发射过程,红光发射是双光子发射过程。样品的量子产率接近0.9%。Yb3+-Tm3+共掺BaGd2(WO4)0.5(MoO4)0.5纳米晶体的发光性能优异,具有很高的应用价值。     

La_(1-x)YO_3∶xPr~(3+)荧光粉的溶液燃烧法合成及发光特性

为了研究紫外光作用下La1-xYO3∶xPr3+荧光粉的光致发光特性和发光机理,以尿素为辅助燃烧原料,采用溶液燃烧合成法,制备了不同掺杂浓度的La1-xYO3∶xPr3+荧光粉样品.通过X-射线衍射、扫描电子显微镜和光谱学手段,对La1-xYO3∶xPr3+荧光粉的晶相结构、形貌和发光性质进行了表征和研究.结果表明,所制备的LaYO3∶Pr3+样品具有立方晶形结构,在波长为295nm紫外光源的激发下,荧光粉发射出很强的绿色荧光.随着Pr3+离子掺杂浓度的增加,荧光粉的绿色发光强度也随之增强.当掺杂浓度增至1.0mol%时,其绿色发光强度达到最大.之后,随着Pr3+离子掺杂浓度的进一步增加,荧光粉的绿色发光强度开始逐渐减弱,出现浓度猝灭效应.     

白光LED用新型Ce,Pr掺杂的YAG单晶荧光材料的光谱性能研究

为了改善白光LED用荧光材料效率低、均匀性差、光衰大、寿命短及物化性能差等不足,本文采用单晶荧光材料取代荧光粉来制备白光LED,并对白光LED用新型YAG单晶荧光材料的制备和光谱性能进行了研究.采用提拉法生长了白光LED用Ce∶YAG及Pr,Ce∶YAG晶体,并通过吸收光谱,激发、发射光谱对晶体材料的光谱特性进行表征.研究表明,Ce∶YAG单晶荧光材料可以被发射波长460 nm左右的蓝光芯片有效激发,产生一个范围为480~650 nm宽峰发射.通过Pr3+,Ce3+离子共掺杂可以有效补偿Ce3+离子单掺杂YAG荧光材料发光中的红色发光成分.     

水热法合成纳米晶NaYF_4∶Er~(3+),Tm~(3+),Yb~(3+)的上转换发光特性

以EDTA为络合剂,用水热法合成了Er3+,Tm3+和Yb3+共掺杂的NaYF4纳米晶。XRD和TEM的结果表明:粒径约为30 nm,属于六方晶系。在980 nm半导体激光器激发下,研究了不同Er3+离子掺杂浓度对Tm3+和Er3+离子上转换发光性能的影响,光强与泵浦功率的双对数曲线表明,474,525,539,650 nm的发射均属于双光子过程,408 nm的发射属于三光子过程。讨论了样品的协作敏化和声子辅助共振能量传递的上转换发光机制。     

补偿离子掺杂与烧成温度对SrTiO_3∶0.002Pr~(3+)材料的红色发光特性的影响

采用高温固相反应法合成SrTiO3∶Pr3+系发光材料,利用荧光光谱、XRD等分析手段,研究了工艺参数,如不同价态K、Ca和A l离子掺杂,以及1 050~1 300℃不同烧成温度对SrTiO3∶Pr3+体系发光性能的影响,以获得具有较好综合发光性能的SrTiO3∶Pr3+系发光材料。选择不同价态补偿离子掺杂是为了研究电荷补偿作用机制对该类材料发光性能的作用。结果表明:随着烧成温度的升高,磷光体发光强度先增加后减弱,在1 150℃烧成的材料其发光强度最大。无补偿掺杂与K、Ca或A l离子掺杂的所有样品均发出源于Pr3+的1D2→3H4跃迁的610 nm红色光。在不同价态补偿离子掺杂样品中,以掺A l的SrTiO3∶Pr3+体系发光强度最好;其发光强度比无补偿离子掺杂SrTiO3∶Pr3+材料的发光强度提高10倍左右。另一方面,与A l离子具有类似的引入阴离子电荷缺陷的K离子掺杂材料的发光强度则基本没有变化,其发光强度与没有电荷补偿作用的无掺杂及Ca离子掺杂SrTiO3∶Pr3+材料相似。上述实验结果可从电荷缺陷及微观固溶结构两方面的联合作用机制进行解释。在引入电荷缺陷的掺杂体系中,只有在发光离子PrS+r最近邻的Ti格位引入的电荷缺陷才能有效地起电荷补偿作用,达到增强发光强度的作用。研究结果给出了合理的制备工艺条件,并且提供了一种可有效提高发光强度的补偿离子掺杂的选择依据。     

ZBLAN玻璃中Nd~(3+),Tm~(3+),Yb~(3+)的上转换发光特性

采用高温固相法制备了Nd,Tm和Yb掺杂的ZBLAN玻璃上转换材料.Tm3+,Yb3+的摩尔浓度分别固定为0.01%,0.3%,Nd3+摩尔浓度变化范围为0.1%～2%.在室温下,测试了样品在300～1 000nm间的吸收光谱.在798 nm近红外光激发下,测试了样品的上转换光谱.实验发现,样品在798 nm红外光激发下发出了较强的多波段(红,蓝和绿)的可见光.由上转换可见光各波段的发射谱线,给出了能级跃迁机制.蓝光主要来源于Tm3+的激发态1G4到基态3H6的跃迁,绿光来源于Nd3+的2H7/2到基态4I9/2的跃迁,红光来源于Nd3+的2H11/2到基态4i9/2的跃迁.研究发现,在Nd3+,Tm3+,Yb3+:ZBLAN玻璃样品中存在激发态吸收,能最转移和交叉弛豫等上转换过程.其发光机理是Nd3+,TM3+和Yb3+离子之间的能量转移.根据Nd3+摩尔浓度不同其上转换发光强度不同,分析了掺入稀土的浓度对上转换发光效率的影响.当Nd3+浓度为1.5%(摩尔分数)时上转换发光最强,大于1.5%后发光开始减弱.     

Lu_2O_3:Yb~(3+),Tm~(3+)纳米晶的结构和上转换发光性能研究

采用共沉淀法制备了Yb3+和Tm3+共掺杂的Lu2O3纳米晶,用X射线衍射(XRD)、场发射扫描电子显示镜(SEM)和上转换光谱对样品进行了表征。研究了Tm3+浓度和煅烧温度对粉末的结构和上转换发光性能的影响。结果表明,制备出的纳米晶具有纯的Lu2O3相,结晶性较好。在980 nm半导体激光器激发下,样品发射出蓝光、红光和近红外光,并且当Tm3+掺杂摩尔分数超过0.2%时,出现了浓度猝灭效应。随着煅烧温度的增加,纳米晶的尺寸增大,上转换发光强度增强。发射强度与激发功率的关系表明,蓝光490 nm和红光653 nm的发光是三光子过程,近红外811 nm的发光是双光子过程。     

Photoluminescence investigations of Li2SiO3:Ln (Ln=Er3+, Eu3+, Dy3+, Sm3+) phosphors

In this study, we report a comprehensive structural and photoluminescence (PL) study on lithium metasilicate (Li₂SiO₃) phosphor ceramics doped with four rare earth (RE) ions. X-ray diffraction (XRD) patterns show a dominant phase, characteristic of the orthorhombic structure Li₂SiO₃ compound and the presence of dopants has no effect on the basic crystal structure of the material. The first excited state Er³⁺ luminescence at 1.54 μm arises from a sharp atomic-like radiative transition between the ⁴I_13/2 state and the ⁴I_15/2 state (ground level) under a 532 nm line of an Ar ion laser excitation. Sm doped samples showed Sm³⁺ emission characteristics corresponding to the some ⁴G_5/2→⁶H_j (j=5/2,9/2,11/2) transitions indicating a strong crystal-field effect. PL spectra of Eu doped material exhibited peaks corresponding to the ⁵D₀→⁷F_j (j=0,1,2,3 and 4) transitions under 405 nm excitation. The dominant red color emission at 612 nm from the hypersensitive (⁵D₀→⁷F₂) transition of Eu³⁺ indicates the inversion antisymmetry crystal field around Eu³⁺ ion, which is favorable to improve the red color purity. Dy doped samples showed the Dy³⁺ emission characteristic due to the ⁴F_9/2→⁶H_13/2 transition. Their relative intensity ratios also suggested the presence of a symmetric environment around the metal ion. We suggest that lithium metasilicate has enough potential candidates to be a phosphor material.     

Synthesis,crystal structure,and luminescence properties of CaY2Ge3O10:Ln3+, Ln = Eu,Tb

The crystal structure and luminescence properties of CaY₂Ge₃O₁₀:Ln³⁺ (Ln = Eu, Tb) germanates synthesized via a conventional solid-state reaction and an ethylenediaminetetraacetic acid complexing process are studied. The CaY_{2 ? x} Ln _x Ge₃O₁₀ (Ln = Eu, Tb; x = 0–1.0, 2.0; Δx = 0.1) solid solutions have a monoclinic structure (space group P2₁/c, Z = 4), in which dopant ions occupy three nonequivalent noncentrosymmetric sites with different Ca²⁺/Ln³⁺ ratios. The effect of the synthesis methods, dopant concentrations, and excitation wavelengths on the luminescence properties of the compounds obtained is determined.     

Luminescence properties of Y2O3:Bi3+, Ln3+ (Ln=Sm,Eu, Dy,Er, Ho) and the sensitization of Ln3+ by Bi3+

The spectroscopic characterization of yttria, singly and doubly doped with Ln³⁺ (Ln=Sm, Eu, Dy, Er, Ho) and Bi³⁺ ions, is performed through excitation spectra, emission spectra and decay time measurements. The obtained spectroscopic data clearly indicate that energy transfer takes place from Bi³⁺ to Ln³⁺ ions. The energy transfer efficiency of Bi³⁺→Ln³⁺ and quantum efficiency of Ln³⁺ were calculated. Upon excitation of 370 nm (Bi³⁺ excitation band), the quantum efficiency of Ln³⁺ varies from ～4% to ～44%. The energy transfer efficiency increases continuously with increasing Ln³⁺ concentrations, whereas the variation of the quantum efficiency of Ln³⁺ is complicated. The quantum efficiency of Ln³⁺ is discussed in terms of electron transfer and cross relaxation.     

LnAlO3中Ce3+,Tb3+,Dy3+的发光及Ce-Tb,Ce-Dy的敏化发光(Ln=La,Gd,Y)

本文采用BaF2作为助熔剂和抑制剂经固相反应合成了一系列以LnAlO3(Ln=La,Gd,Y)为基质的磷光体,系统地研究了LnAlO3中Ce3+,Tb3+,Dy3+的发光及Ce-Tb,Ce-Dy的敏化发光,发现随Ln的不同,LnAlO3作为基质对激活剂的发光性质的影响也不同,本文得到一些规律性结果,并作了讨论。     

多体系多波长计算光度法同时测定镧铈镨钕钐铕钆

本文以DBC-偶氮氯膦为显色剂,并且在显色体系中加入不同量的EDTA-Na2P2O7作为竞争配位剂,使得七组分轻稀土组分间吸收光谱灵敏度的差别逐渐加大,从而增加了轻稀土混合物体系组分间吸收光谱的线性独立性.利用数值稳定性较强的约束优化算法--可变容差法处理光谱数据,对不同浓度比例的七组分轻稀土混合物体系(La3+,Ce3+,Pr3+,Nd3+,S m3+,Eu3+,Gd3+)的测定,取得了较满意的结果.     

Photoacoustic Spectra of Sm3+, Eu3+, Dy3+ Complexes

The complexes crystals of Sm(Ac)3.4H₂O, Eu(Ac)3.4H₂O and a new complex Dy2(Ac)(NO3)4.12H₂O were synthesized and their PA spectra were determined firstly. All their PA spectra absorptions are interpreted. The fluorescence properties of Sm³⁺, Eu³⁺, Dy³⁺ and the relaxation process models were studied by their PA spectra.     

5d-4f luminescence of Nd3+, Gd3+, Er3+, Tm3+, and Ho3+ ions in crystals of alkaline earth fluorides

The vacuum ultraviolet emission spectra of alkaline-earth fluoride (CaF₂, SrF₂, BaF₂) crystals with rare earth impurity ions (Nd, Gd, Er, Tm, Ho) have been investigated. The main luminescence bands are described well by the transitions from the lowest excited 5d state to different 4f levels of rare earth ions.     

Lithium ion conductivity of the B-site substitution in Li3xLa0.67−xRE y III Ti1−2yPyO3 system (REIII=Sc3+, Y3+, Nd3+, Sm3+, Eu3+, Yb3+)

The B-site substituted perovskite solid solution systems Li_3xLa_0.67−xRE_yTi_1−2yP_yO₃ (RE=Sc, Y, Nd, Sm, Eu, Yb) have been investigated. Perovskite solid solutions formed in the range of x=0.10, y<0.10 for RE=Sc³⁺, Y³⁺, Yb³⁺, x=0.10, y≤0.05 for RE=Nd³⁺, Sm³⁺, Eu³⁺. Li_0.3La_0.57Nd_0.05Ti_0.9P_0.05O₃ has the highest bulk conductivity of 4.31×10⁻⁴ S·cm⁻¹ and the highest total conductivity of 2.52×10⁻⁴ S·cm⁻¹ at room temperature in all prepared compositions. The compositions have low activation energies of about 24–30 kJ/mol in the temperature ranges of 298–523 K. SEM studies showed that the sample made by solid-state reaction has a sphere-like morphology and a rough particle with particle size of about 50 μm. The research results also indicated that the reaction temperature decreases and the electrochemical stabilities of the titanate-based perovskite-type solid solutions are improved by using RE³⁺ and P⁵⁺ replaced Ti⁴⁺ on B-site in the Li_3xLa_0.67−xTiO₃ parent.