尿素用量对燃烧法合成CaAl2O4：Eu2+,Nd3+长余辉材料发光性能的影响

利用金属硝酸盐和尿素的氧化还原反应,通过燃烧法在600℃的炉温下合成了蓝紫色长余辉发光材料CaAl₂O₄:Eu²⁺,Nd³⁺。在金属硝酸盐溶液浓度不变的条件下,通过改变尿素与硝酸根的量的比,合成了多组长余辉材料样品。当尿素用量较少时,Eu³⁺不能完全被还原为Eu²⁺;随尿素用量增加,样品的Eu³⁺特征发射减弱,余辉初始亮度和持续时间均得到改善;当尿素的用量达到理论用量的5倍时,样品余辉特性最好,继续增加尿素用量,余辉亮度和持续时间反而下降。将燃烧法制备的各组样品用活性炭密封,在1000℃条件下反应2h,使Eu³⁺完全被还原为Eu²⁺,同时除去燃烧法反应不完全的杂质,可以一定程度提高材料的余辉发光性能。     

蓝色长余辉材料CaAl_2O_4∶Eu~(2+),Li~+的发光性质

采用高温固相法制备了CaAl_2O_4∶Eu~(2+),Li~+发光材料,并讨论了掺杂Li+对CaAl_2O_4∶Eu~(2+)发光性质的影响。X射线衍射(XRD)和PL测试分析表明,在CaAl_2O_4∶Eu~(2+)中掺入Li~+后,Eu~(2+)的发光有一定的增强,而余辉时间则延长了4倍左右。通过热释光谱测量,分析了其陷阱能级的数量并估算了陷阱能级深度。结果表明,掺杂Li~+会在发光离子周围产生更多的电子陷阱,使陷阱的密度和深度增加,从而提高荧光粉的余辉性能。     

Effect of temperature on the luminescence processes of SrAl2O4:Eu

The UV excited and persistent luminescence properties as well as thermoluminescence (TL) of Eu²⁺ doped strontium aluminates, SrAl₂O₄:Eu²⁺ were studied at different temperatures. Two luminescence bands peaking at 445 and 520 nm were observed at 20 K but only the latter at 295 K. Both Sr-sites in the lattice are thus occupied by Eu²⁺ but at room temperature efficient energy transfer occurs between the two sites. The UV excited and persistent luminescence spectra were similar at 295 K but the excitation spectra were different. Thus the luminescent centre is the same in both phenomena but excitation processes are different. Two TL peaks were observed between 50 and 250 °C in the glow curve. Multiple traps were, however, observed by preheating and initial rise methods. With longer delay times only the high temperature TL peak was observed. The persistent luminescence is mainly due to slow fading of the low temperature TL peak but the step-wise feeding process from high temperature traps is also probable.     

Nature of intrinsic luminescence in the glasses of CaO–Ga2O3–GeO2 system

The intrinsic luminescence of glasses of the CaO–Ga₂O₃–GeO₂ system has been investigated. High chemical purity and optical quality glasses, both undoped and doped with transition and rare-earth ions with different compositions, were obtained by high-temperature synthesis. The influences of the basic glass composition, impurities (Cr³⁺, Mn²⁺, Eu²⁺, Nd³⁺, Ho³⁺, Er³⁺, and Ce³⁺) and different kinds of excitation, on the intrinsic luminescence of the CaO–Ga₂O₃–GeO₂ glasses were investigated. The nature and possible mechanisms of the intrinsic luminescence in glasses of this system are discussed. The proposed models of intrinsic luminescence are supported by electron spin resonance spectroscopy.     

Eu3+激活K2CaP2O7荧光粉的制备和发光性质

采用高温固相法制备了系列不同浓度Eu³⁺离子掺杂的K₂CaP₂O₇红色荧光粉。通过X射线衍射、扫描电子显微镜、荧光光谱和荧光寿命曲线等手段对荧光粉的物相结构、形貌以及发光性质进行了研究。结果表明所制备的荧光粉均属于单斜结构,Eu³⁺离子掺杂没有引起晶体结构明显变化,荧光粉形貌不规则,颗粒为微米量级且部分发生团聚。在393 nm紫外光激发下,荧光粉显示出红光发射,最强发射峰位于613 nm。Eu³⁺离子掺杂浓度对发光强度有显著影响,最佳掺杂摩尔分数为0.08,由此计算能量传递临界距离为1.61 nm。荧光寿命受掺杂浓度影响较小,当Eu³⁺掺杂摩尔分数为0.005~0.10时,荧光寿命在2.45~2.58 ms范围内。变温发射光谱显示,测试温度为150℃时,荧光粉的发光强度为室温的73%。研究表明,Eu³⁺离子掺杂的K₂CaP₂O₇是性能较好的红色荧光粉。     

实验优化设计Sr_2MgSi_2O_7:Eu~(2+),Dy~(3+)的合成及长余辉特性

为了得到最长有效余辉时间的Sr_2MgSi_2O_7:Eu~(2+),Dy~(3+)荧光粉,应用二次通用旋转组合设计对实验进行全程优化,建立了稀土离子掺杂浓度Eu~(2+),Dy~(3+)和有效余辉时间的二元二次回归方程模型,应用遗传算法计算得到有效余辉时间的理论最大值.采用高温固相法合成了最优掺杂浓度Sr_2MgSi_2O_7:0.5mol%Eu~(2+),1.0mol%Dy~(3+)的荧光粉,在370nm激发下观察到了465nm的特征发射,这归因于Eu~(2+)的4f65d1—4f7跃迁.测量了最优荧光粉的热释发光特性,计算得到了陷阱深度为0.688eV,讨论了长余辉发光的特性.     

Simultaneous excitation of Ce and Eu ions in Tb3Al5O12

Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce) and Tb₃Al₅O₁₂:Ce³⁺ (TAG:Ce) both show the typical Ce³⁺ ion luminescence of the allowed Ce³⁺ d–f transition. Eu³⁺ codoping, however, reveals different results for both matrices: in YAG:Ce,Eu, only the luminescence of the Ce³⁺ ion occurs by excitation within the Ce³⁺ absorption bands. Here, the Eu³⁺ luminescence cannot be sensitized by the Ce³⁺ ion. But in TAG:Ce,Eu, both Ce³⁺ and Eu³⁺ luminescence are measured at several excitation wavelengths: an excitation within the Tb-sublattice results in both Ce³⁺ and Eu³⁺ luminescence, which is not surprising as an energy transfer from Tb³⁺ to Ce³⁺ and Eu³⁺ is well known in literature. In addition, an excitation in the lowest 5d level of Ce³⁺ delivers Eu³⁺ luminescence at room temperature. This means that the Ce³⁺ ion can be used as a sensitizer in the TAG lattice that transfers its energy via the Tb sublattice to the activator Eu³⁺.     

Na_2CaSiO_4:Sm~(3+),Eu~(3+)荧光粉的发光特性和能量传递

利用高温固相法合成Na_2CaSiO_4:Sm~(3+),Eu~(3+)系列荧光粉末,研究了Sm~(3+)和Eu~(3+)掺杂对Na_2CaSiO_4晶体结构的影响、材料发光特性以及存在的能量传递现象.X射线衍射结果表明Sm~(3+)和Eu~(3+)单掺及共掺样品均为单相的Na_2CaSiO_4结构,晶体结构没有改变.Na_2CaSiO_4:Sm~(3+)荧光样品在404 nm激发波长下呈现峰峰值为602 nm的橙红色荧光,来源于~4G_(5/2)→~6H_(7/2)跃迁.Na_2CaSiO_4:Eu~(3+)荧光样品在395 nm激发波长下发射出峰峰值为613 nm的红色荧光.对光谱和荧光寿命的测试和分析结果表明Sm~(3+)与Eu~(3+)之间存在能量传递,通过理论计算得到Sm~(3+)和Eu~(3+)之间的能量传递临界距离为1.36 nm,相互作用形式为电四极-电四极相互作用.随着Eu~(3+)掺杂浓度的增加,能量传递效率也逐渐提高至20.6%.     

On the energy transfer from Tb to Eu in LiTb1−xEuxP4O12

The undoped stoichiometric materials LiTbP₄O₁₂ and LiEuP₄O₁₂ show effective green Tb³⁺ and red Eu³⁺ luminescence, respectively. Both systems are fully mixable, which offers the possibility of examining the energy transfer from Tb³⁺ to Eu³⁺ in the complete system of LiTb_1−xEu_xP₄O₁₂. As the distance of the rare earth ions is large enough to exclude exchange interaction in these materials, only multipolar interaction is to be expected. Dealing only with forbidden f–f transitions it is possible to produce both Tb³⁺ and Eu³⁺ luminescence at the same time having a suitable Eu³⁺ concentration.     

Sm3+掺杂对CaMoO4:Eu3+红色荧光粉结构和发光性质的影响

采用共沉淀法制备了CaMoO4:Eu3,Sm3+纳米荧光粉材料.系统研究了Sm3+离子的引入对CaMoO4:Eu3+材料的结构和发光性质的影响.结果表明:纳米材料的尺寸随着Sm3+离子掺杂浓度的增加而变小.Sm3+的引入,可实现Sm3+和Eu3+之间的能量传递,使Eu3+在近紫外405 nm处的激发增强,进而使Eu3+...     

Local microstructural analysis for Y_2O_3/Eu~(3+)/Mg~(2+) nanorods by Raman and photoluminescence spectra under high pressure

In this paper, we investigate the Raman and photoluminescence spectra of Y_2O_3/Eu~(3+) and Y_2O_3/Eu~(3+)/Mg~(2+) nanorods under high pressures using 514-nm and 532-nm laser light excitation. We observe transitions from the initial cubic phase to amorphous at pressures higher than 24 GPa for both Y_2O_3/Eu~(3+) and Y_2O_3/Eu~(3+)/Mg~(2+) nanorods. In addition, Y_2O_3/Eu~(3+) and Y_2O_3/Eu~(3+)/Mg~(2+) nanorods exhibit different distorted states after the pressure has been raised to 8 GPa. The analyses of intensity ratios, I_(0-2)/I_(0-1) from ~5D_(0–)~7F2_to~5D_(0–)~7F_1and I_(0-2)A/B of ~5D_(0–)7F_2 transitions indicate that Y_2O_3/Eu~(3+)/Mg~(2+) nanorods exhibit stronger local micro-surrounding characteristics for Eu~(3+) ions in a pressuremodulated crystal field. The doped Mg2+ion results in reducing the crystal ionicity in the distorted lattice state under high pressures. The use of doped ions as an ion modifier can be applied to the study of small local microstructural changes through Eu~(3+) luminescence.     

铈铕共掺高钆氧化物玻璃的发光性能及能量传递效应

在还原气氛下, 采用高温熔融法制备了Eu²⁺/Ce³⁺共掺的高钆氧化物玻璃. 荧光性能测试显示, Ce³⁺能够有效地敏化Eu²⁺的发光, 使Eu²⁺的发光强度增强了2.3倍; 测试对比了Ce³⁺ 发光的荧光寿命随Eu²⁺的掺入前后的变化情况, 计算得出Ce³⁺→Eu²⁺ 的能量传递效率可达61.5%, 并进一步探讨了其能量传递机理. 研究表明: 在高钆氧化物玻璃中, 采用Eu²⁺ 和Ce³⁺ 共掺的方法可有效地增强Eu²⁺ 的发光性能和闪烁性能. 关键词： 发光玻璃 能量传递 荧光寿命     

Sm3+掺杂的SnNb2O6粉体的光谱特性

采用熔盐法制备了Sm³⁺掺杂的SnNb₂O₆粉体, 利用X射线粉末衍射、扫描电子显微镜对其物相和形貌进行了表征, 用激发、发射光谱和荧光寿命对样品的发光性能进行了研究.结果表明:所得样品为单斜晶系的SnNb₂O₆, 在407 nm的激发下, 有较强的橙红色发射, 最强峰位于599 nm, 属于Sm³⁺的⁴G_5/2→⁶H_7/2跃迁.     

长余辉发光材料CaAl2O4∶Eu2+,Gd3+ 的制备和发光性能研究

采用高温固相法制备了CaAl₂O₄∶Eu²⁺,Gd³⁺ 长余辉发光材料。利用X射线衍射(XRD)和荧光光谱测试等手段对所制备的样品进行结构表征和发光性能的分析,探究Eu²⁺摩尔分数为3.5%,硼酸质量分数为0.5%,Gd³⁺摩尔分数分别为2%,3%,4%,5%时样品的发光性能。研究结果表明:实验成功地合成了CaAl₂O₄∶Eu²⁺,Gd³⁺粉晶,并且Eu²⁺和Gd³⁺的引入并未引起CaAl₂O₄晶体结构的改变。样品的激发光谱和发射光谱均为宽带谱,且发射光谱的最大峰值位于444 nm左右,属于Eu²⁺的4f⁶5d→4f⁷跃迁,所发光为蓝光。蓝色荧光粉CaAl₂O₄∶3.5%Eu²⁺,3%Gd³⁺的发光强度最好。     

MSO4:Eu2+(M =Mg,Ca, Sr,Ba)的等电子陷阱与热释光特性

在硫酸盐掺入稀土元素的研究中, 得到了几种掺入Eu²⁺的碱土金属硫酸盐磷光体MSO₄:Eu²⁺ (M =Mg, Ca, Sr, Ba), 这组磷光体具有与掺入三价稀土离子(Tm³⁺, Dy³⁺, Eu³⁺)的碱土金属硫酸盐截然不同的热释光特性, 热释光三维发光谱中只呈现一个热释光峰, 对γ和βup辐射的热释光剂量响应为线性-亚线性响应. 结果清楚地显现出Eu²⁺对碱土金属阳离子的等价取代而形成的等电子陷阱对这些磷光体的热释光特性起了关键性的作用, Eu²⁺等电子陷阱与基质中的本征缺陷SO₄^2-形成的缺陷复合体作为热释光多阶段过程的基本作用单元, 基本上产生一次作用热释光事件. SrSO₄:Eu²⁺是一种典型的等电子陷阱发光的磷光体, 它具有相当高的热释光和光释光发光效率.     

纳米纤维状Sr3Al2O5Cl2:Eu2+,Tm3+的白色长余辉性能

采用高温固相法在800℃下制备出系列白色长余辉荧光粉Sr₃Al₂O₅Cl₂：Eu²⁺,Tm³⁺,并研究了它们的结构、形貌及发光性能。样品Sr_2.91Al₂O₅Cl₂：0.04Eu²⁺,0.05 Tm³⁺具有单一晶相和纳米纤维结构。该样品在紫外光激发下表现出两个很强的宽带发射（分别位于~448 nm和~590 nm）。它的余辉寿命大约是20 min。利用此种荧光粉所制作出的白光LED器件表现出很强的白光发射。     

阴离子取代合成Sr3LaAxV3-xO12:Eu3+(A=Mo,W)白光荧光粉

通过高温固相法合成Sr₃LaA_xV_3-xO₁₂:Eu³⁺（A=Mo,W）荧光粉,利用MoO₄^2-和WO₄^2-取代基质中部分VO₄^3-,改变基质组成和结构,进而影响基质和激活剂Eu³⁺离子的发光性能。采用X射线衍射（XRD）、扫描电子显微镜（SEM）和荧光分光光度计对所合成样品的物相、形貌、荧光性能及荧光寿命进行表征。研究表明,MoO₄^2-和WO₄^2-的部分掺杂对基质发光位置和强度均有影响,能明显减弱VO₄^3-的发光,但对Eu³⁺离子发光影响不大,添加电荷补偿剂F^-可以加强VO₄^3-对Eu³⁺离子的能量传递。通过调整基质VO₄^3-发光和Eu³⁺离子发光,可以得到单一基质的白光荧光粉。初步探讨了阴离子掺杂对Eu³⁺离子红光发射增强的机理。     

Y3+和Gd3+对LaBO3:Eu3+发光粉结构和发光性能的影响

采用溶胶凝胶-燃烧法合成了系列不同掺杂浓度Y³⁺和Gd³⁺的LaBO₃∶Eu³⁺发光粉,对其结构、形貌和发光性能进行了表征。XRD研究结果表明：发光粉的结构与基质掺杂离子的种类和掺杂浓度有关系。荧光光谱结果表明：适量比例Y³⁺和Gd³⁺离子掺杂将提高LaBO₃∶Eu³⁺发光粉的发光强度。Y³⁺和Gd³⁺离子最佳掺杂摩尔分数分别为1.5%和12.5%。⁵D₀→⁷F₂与⁵D₀→⁷F₁跃迁发射的相对强度比值说明：掺杂改变LaBO₃∶Eu³⁺中Eu³⁺局域环境的对称性。发光性能改变主要受晶体结构、掺杂离子电负性影响。Gd³⁺离子掺杂更有利于发光粉结构稳定性和发光性能的改善。     

红色荧光粉La2Mo2O9:Eu3+,W6+的制备及发光性能

采用高温固相法合成出La₂Mo₂O₉:Eu³⁺,W⁶⁺系列红色荧光粉,其结构为立方晶系的β- La₂Mo₂O₉。在395 nm光激发下,样品La_1.40Mo₂O₉:0.60Eu³⁺发射出很强的红光,最强发射峰位于616 nm处。适量地掺杂W⁶⁺离子可以提高样品的激发和发射强度,在395 nm光激发下,La_1.40Mo_1.84O₉:0.60Eu³⁺,0.16W⁶⁺荧光粉的Eu³⁺的⁵D₀→⁷F₂跃迁发射强度最大,是样品La_1.40Mo₂O₉:0.60Eu³⁺的1.23倍。最后,将La_1.40Eu_0.60Mo_1.84O₉:0.16W⁶⁺荧光粉与~395 nm发射的InGaN芯片一起制作成红光发光二极管(LED),该LED发射出很强的红光。     

钙钛矿锰氧化物(La_(1-x)Eu_x)_(4/3)Sr_(5/3)Mn_2O_7(x=0,0.15)的磁性和电性研究

通过传统固相反应法制备了钙钛矿锰氧化物(La1-xEux)4/3Sr5/3Mn2O7(x=0,0.15)多晶样品,并且对其磁性和电性进行了研究.磁性测量表明:随着温度的降低,样品经历了一个复杂的转变过程,在温度为T*时经历二维短程铁磁有序转变,在温度为TC时进入三维长程铁磁态.随着Eu的掺杂,T*和TC减小,并且样品(La0.85Eu0.15)4/3Sr5/3Mn2O7在低温区表现出自旋玻璃行为.电性质测量表明:在母体La4/3Sr5/3Mn2O7中La位掺杂Eu后电阻率明显变大,金属绝缘转变温度TMI降低,磁电阻峰值增大.这些影响归因于较小的Eu3+离子替代La3+离子导致平均离子半径减小,晶格发生畸变.此外,较小的Eu3+离子优先占据层间岩盐层的R-site,使La3+,Sr3+,Eu3+离子在(La0.85Eu0.15)4/3Sr5/3Mn2O7中的分布更加有序,所以x=0.15的样品的ρ-T曲线只有一个峰.