Sol–gel synthesis and luminescence of unexpected microrod crystalline Ca5La5(SiO4)3(PO4)3O2:Dy phosphors employing different silicate sources

Ca₅La₅(SiO₄)₃(PO₄)₃O₂ doped with Dy³⁺ were synthesized by sol–gel technology with hybrid precursor employed four different silicate sources, 3-aminopropyl-trimethoxysilane (APMS), 3-aminopropyl-triethoxysilane (APES), 3-aminopropyl-methyl-diethoxysilane (APMES) and tetraethoxysilane (TEOS), respectively. The SEM diagraphs show that there exist some novel unexpected morphological structures of microrod owing to the crosslinking reagents than TEOS as silicate source for their amphipathy template effect. X-ray pictures confirm that Ca₅La₅(SiO₄)₃(PO₄)₃O₂:Dy³⁺ compound is formed by a pure apatitic phase. The Dy³⁺ ions could emit white light in Ca₅La₅(SiO₄)₃(PO₄)₃O₂ compound, and the ratio of Y/B is 1.1, when the Dy³⁺ doped concentration is 1.0 mol%.     

紫外光激发Ce3+掺YVO4蓝光发射性能研究

利用提拉法生长了YVO₄和掺2.0at% CeO₂(或Ce₂(CO₃)₃)的YVO₄: Ce³⁺晶体。样品的XRD测试表明Ce³⁺代替Y³⁺进入晶格, Ce³⁺的加入并没有影响YVO₄的晶格结构。XPS测试显示YVO₄: Ce³⁺晶体中Ce离子3d分裂为882.0、885.8、902.9、908.0和915.9 eV等5个峰, 峰位表明样品中铈离子是以Ce³⁺和Ce⁴⁺两种价态形式存在。YVO₄和YVO₄: Ce³⁺激发谱都呈现出260~360 nm宽带激发, 此激发带源于基质中VO₄^3-离子团的配体O到V的电荷迁移吸收。使用325 nm的紫外线激发时, 两种样品均可发出以440 nm 为中心的宽带蓝光,其中YVO₄发射峰应归属于VO₄^3-离子团中³T₂→¹A₁和³T₁→¹A₁跃迁; 而YVO₄: Ce³⁺的蓝光发射则来源于Ce³⁺的5d→4f 的跃迁。分析可知YVO₄: Ce³⁺中VO₄^3-的π轨道和Ce³⁺的电子波函数能有效地重叠, 使得VO₄^3-和Ce³⁺可通过交换作用有效地向Ce³⁺传递能量, 可大幅提高Ce³⁺的蓝光发射强度。实验结果显示YVO₄: Ce³⁺可作为UV-LED管芯激发的白光发光二极管用高亮度蓝色发光材料。     

YVO4∶Eu3+,Bi3+红色荧光粉的水热合成及其荧光性能

以Y₂O₃、Eu₂O₃、Bi(NO₃)₃·H₂O、浓HNO₃、偏钒酸铵、氨水、无水乙醇和一缩二乙二醇为原料,采用聚乙烯吡咯烷酮(PVP)辅助水热法合成YVO₄: Eu³⁺, Bi³⁺纳米颗粒。使用X射线衍射(XRD)、扫描电镜(SEM)、红外光谱(IR)和荧光光谱(FL)等手段对产品进行了表征和分析。结果表明：合成的样品为YVO₄: Eu³⁺, Bi³⁺纳米颗粒,均具有四方晶相结构,其微结构随反应溶液的的pH值变化。YVO₄: Eu³⁺, Bi³⁺纳米颗粒在619 nm处有较强的红光发射(电偶极跃迁⁵D₀→⁷F₂),在594 nm有较弱的橙光发射(磁偶极跃迁⁵D₀→⁷F₁)。随着Eu/Bi比值的增大材料的荧光先增强后减弱,在Eu/Bi比值为5时样品的红光发射最强。溶液的pH值影响YVO₄: Eu³⁺, Bi³⁺纳米晶的发光强度,其中pH值为10时的样品其红光发射最强。并探讨了YVO₄: Eu³⁺, Bi³⁺纳米晶的发光机理。     

Synthesis and the luminescent properties of europium-activated Ca2SnO4 phosphors

The synthesis and photoluminescent (PL) properties of calcium stannate crystals doped with europium grown by mechanically activated in a high energy vibro-mill have been investigated. The characteristics of Ca₂SnO₄:Eu³⁺ phosphors were found to depend on the amounts of europium ions. The XRD profiles revealed that the system, (Ca_1−xEu_x)₂SnO₄, could form stable solid solutions in the composition range of x = 0–7% after being calcined at 1200 °C. The calcined powders emit bright red luminescence centered at 618 nm due to ⁵D₀ → ⁷F₂ electric dipole transition. Both XRD data and the emission ratio of (⁵D₀ → ⁷F₂)/(⁵D₀ → ⁷F₁) reveal that the site symmetry of Eu³⁺ ions decreases with increasing doping concentration. The maximum PL intensity has been obtained for 7 mol% concentration of Eu³⁺ in Ca₂SnO₄.     

Enhancement of Er I13/2 population in Y2O3 by energy transfer to Ce

We report measurements of the energy transfer between Er³⁺ and Ce³⁺ in Y₂O₃. The transition between the Er^{3+ 4}I_11/2 and ⁴I_13/2 excited states can be stimulated by energy transfer to Ce³⁺, augmenting the population in the ⁴I_13/2 state at the expense of that in the ⁴I_11/2 state. Experiments were performed on Y₂O₃ planar waveguides doped with 0.2 at.% erbium and 0–0.42 at.% cerium by ion implantation. From measurements of Er³⁺ decay rates as a function of cerium concentration we derive an energy transfer rate constant of 1.3×10⁻¹⁸ cm³/s. The efficiency of the energy transfer amounts to 0.47 at 0.42 at.% cerium. The energy transfer rate constant measured in Y₂O₃ is two times smaller for Er³⁺→Ce³⁺ than that for Er³⁺→Eu³⁺ in the same material.     

Yb to Er energy transfer and rate-equations formalism in the eye safe laser material Yb:Er:Ca2Al2SiO7

Rate equations formalism is used to predict the population ratio of the Er^{3+ 4}I_13/2 levels involved in the 1.55 μm laser transition in the Yb:Er:CAS laser materials. An effective Yb → Er energy transfer, favourable to the Er³⁺ 1.55 μm laser emission, is demonstrated in this laser host. Indeed, the Yb → Er transfer and the Er → Yb back transfer rates are calculated to be 6 x 10⁻¹⁶ and 0.45 x 10⁻¹⁶ cm³ s⁻¹, respectively. Attempts of codoping the system with Nd³⁺, Eu³⁺ and Ce³⁺ have been realised in order to increase the population of the Er^{3+ 4}I_13/2 laser emitting level. Best results are obtained with Ce³⁺ ion since in the sample containing 6 x 10²⁰ Ce³⁺/cm³, the Er^{3+ 4}I_11/2 level lifetime is divided by a factor of 3 while the Er^{3+ 4}I_13/2 fluorescence lifetime remains unaffected. On the contrary, codoping with Nd³⁺ or Eu³⁺ ions simultaneously decreases the Er^{3+ 4}I_11/2 and ⁴I_13/2 kinetics parameters. The role of the other parameters such as Yb/Er concentrations ratios is also discussed.     

Influence of additional Eu coactivator on the luminescence properties of Tb3Al5O12:Ce, Eu

The luminescence properties of doubly activated terbium aluminium garnet samples were investigated in the present study. Commercial Tb₃Al₅O₁₂:Ce³⁺ (TAG:Ce) shows the typical Ce³⁺ ion luminescence of the allowed Ce³⁺ d–f transition. Eu³⁺ co-doping, however, reveals interesting results. In TAG:Ce, Eu, both Ce³⁺ and Eu³⁺ luminescence was measured at different Ce and Eu activator concentrations. The Ce³⁺ ion can be used as a sensitizer in the TAG lattice that transfers its energy directly or via the Tb sublattice to the activator Eu³⁺. The energy-level diagram was proposed to explain the luminescence mechanism. Application of TAG:Ce, Eu with improved chromaticity coordinates CIE (Commission Internationale de l’Eclairage) and color rendering index (CRI) in light emitting diodes (LEDs) is demonstrated.     

硬脂酸盐熔融法合成(Y,Lu)AG:Ce荧光粉及荧光性能研究

采用硬脂酸盐熔融新方法合成了[(Y_1-xLu_x)_1-yCe_y]₃Al₅O₁₂固溶体荧光粉(x=0’0.5, y=0.005’0.03), 并通过XRD、SEM、BET和PL-PLE等方法对该荧光粉进行了表征。结果表明, 纯相石榴石在800℃的低温下即可生成, 而不经过YAM和YAP中间相。煅烧所得[(Y_1-xLu_x)_1-yCe_y]₃Al₅O₁₂ 荧光粉具有良好的均一性和分散性, 并在455 nm蓝光激发下于544 nm附近呈现最强黄光发射。粉体的发光强度随煅烧温度升高而增大, 归因于结晶度提高和表面缺陷减少。发现Ce³⁺的荧光猝灭浓度为1.5%, 猝灭机制为Ce-Ce间的交换相互作用和晶格缺陷。发现发射峰位随Ce³⁺含量增加而红移, 而最强激发峰和发射峰随Lu³⁺含量增大而蓝移, 归因于Ce³⁺离子5d激发态能级重心移动和晶体场劈裂的共同作用。     

Ba3Gd(PO4)3:Eu3+荧光粉的合成及发光性质

采用高温固相反应法合成了不同Eu³⁺掺杂浓度的Ba₃Gd(PO₄)₃荧光粉。利用X射线衍射对产生的晶体结构进行了分析, 证实产物为纯相, Eu³⁺的引入没有导致晶体结构的改变。利用Van Uitert模型对⁵D₀能级荧光的浓度猝灭行为进行了研究, 发现浓度猝灭是由于Eu³⁺间交换相互作用所导致。分析了⁵D₀荧光发射的温度依赖, 给出了荧光温度猝灭行为符合横向穿越模型, 并通过非线性拟合获得了激活能。利用Eu³⁺的发射光谱和荧光衰减数据, 计算了⁵D₀→⁷F_J辐射跃迁速率及荧光分支比, 同时得到了光学跃迁强度参数。     

柔性Eu3+掺杂SiO2纳米纤维薄膜的制备及其发光性能

采用溶胶-凝胶法结合静电纺丝技术制备了柔性Eu³⁺掺杂SiO₂纤维薄膜, 采用SEM、XRD、FT-IR、TG和PL等测试方法对材料进行表征。Eu³⁺掺杂SiO₂纤维薄膜在热处理后纤维直径变小, 纤维表面平滑无粘连。通过控制升温速度, 纤维薄膜经热处理后仍具有较高的力学强度, 750℃热处理后其拉伸强度可达4.31 MPa, 经过多次弯曲仍能保持原样。在392.6 nm光源激发下, Eu³⁺掺杂SiO₂纤维薄膜在570~670 nm附近呈现出来自于⁵D₀→⁷F_J的发射峰。当Eu³⁺掺杂浓度为8mol%时, 经过750℃热处理后Eu³⁺掺杂SiO₂纤维薄膜的发光强度达到最大值。     

On the relationship between emission color and Ce concentration in garnet phosphors

It is known that the emission color of Ce³⁺ doped garnets is strongly redshifted at higher Ce³⁺ concentrations. In this report, we study the cause of this redshift in Lu₃Al₅O₁₂:Ce³⁺ (LuAG:Ce) phosphors. These changes in emission color with Ce³⁺ concentration are mainly attributed to a combination of inhomogenous broadening for Ce³⁺ in LuAG and energy transfer from high energy Ce³⁺ ions to low energy Ce³⁺ ions. Evidence for inhomogenous broadening and energy transfer is given through time resolved measurements. Potential reasons for inhomogenous broadening of Ce³⁺ in these phosphors are also discussed.     

Improved optical photoluminescence by charge compensation in the phosphor system CaMoO4:Eu

It has been found that charge compensated CaMoO₄:Eu³⁺ phosphors show greatly enhanced red emission under 393 and 467 nm-excitation, compared with CaMoO₄:Eu³⁺ without charge compensation. Two approaches to charge compensation, (a) 2Ca²⁺ → Eu³⁺ + M⁺, where M⁺ is a monovalent cation like Li⁺, Na⁺ and K⁺ acting as a charge compensator; (b) 3Ca²⁺ → 2Eu³⁺ + vacancy, are investigated. The influence of sintering temperature and Eu³⁺ concentration on the luminescent property of phosphor samples is also discussed.     

锶含量对稀土Eu掺杂锶钙羟基磷灰石发光性能及取代位置的影响

采用化学共沉淀法制备了一系列Sr含量不同的铕掺杂锶钙羟基磷灰石粉体(Ca_10-x-Sr_x-HAp: Eu), 通过X射线衍射(XRD)、荧光光谱以及发光能量传递等研究了锶含量对稀土掺杂锶钙羟基磷灰石结构、荧光性能和取代位置的影响。XRD分析表明, 掺杂Eu对锶钙羟基磷灰石样品的结构无明显影响, 而Sr含量增加会使得样品的结晶程度和晶面间距增大。光谱分析表明, 在394 nm波长激发下, Ca_10-x-Sr_x-HAp: Eu样品在596 nm和618 nm处的荧光强度随着Sr含量的增加先升高再降低, 最强峰值出现在Ca₃-Sr₇-HAp: Eu样品中。同时, 样品的荧光寿命随着Sr含量增加也出现相同的变化。此外, 随着基体中Sr含量的增加, 样品的电偶极跃迁与磁偶极跃迁强度比值(I_R/I_O)先增加后减小, 而Eu荧光衰减过程中不同格点之间的能量传递参数(f)则先减小后增大, 两者的转折点都出现在Ca₃-Sr₇-HAp: Eu样品中。实验表明: Eu在基质晶格中的取代位置受Sr在基质中含量和位置的影响, 通过Sr/Ca比例的调节则可以使得Eu在基质中取代不同位点的比例变化进而获得可调节的荧光性能。     

Preparation of Eu: YVO4 red and Ce, Tb: LaPO4 green phosphors by hydrolyzed colloid reaction (HCR) technique

Eu³⁺: YVO₄ red and Ce³⁺, Tb³⁺: LaPO₄ green phosphors were prepared by newly discovered hydrolized colloid reaction (HCR) technique at low temperature (< 100 °C) and atmospheric pressure utilizing subsequent calcining and reductive treatments, respectively. The incorporation of activators (Eu³⁺ and Ce³⁺, Tb³⁺) in these very porous powders was checked by X-ray diffraction (XRD), scanning electron microscopy (SEM) and luminescence investigations.     

Mg共掺杂Gd3(Al,Ga)5O12:Ce晶体快发光的作用机理

Gd₃(Al,Ga)₅O₁₂:Ce (GAGG:Ce)闪烁体综合性能优异, 应用前景广阔。为加快GAGG的发光衰减速度, 本研究通过提拉法生长了Mg共掺的Gd₃(Al,Ga)₅O₁₂:Ce单晶。测试结果显示, 随着Mg²⁺掺杂浓度增加, 晶体的闪烁衰减速度加快, 光输出降低。传统解释认为, Mg²⁺通过电荷补偿作用将部分Ce³⁺转换成Ce⁴⁺, 后者的发光速度更快。本研究尝试从缺陷的形成与抑制的角度来讨论Mg改善GAGG:Ce晶体闪烁性能的作用机理。由于Ce的离子半径比Gd大, Ce离子掺入将导致发光中心Ce_Gd附近的晶格发生畸变。畸变结果为近邻的八面体格位空间变大, 反位缺陷将更容易在这些变大的八面体格位形成。最终每个发光中心Ce_Gd被四个反位缺陷Gd_Al包裹, 后者捕获载流子, 延缓从基体到发光中心的能量传递, 导致发光速度变慢。由于Mg的离子半径介于Gd和Al之间, Mg_Al将更容易在上述畸变的八面体格位形成, 这会抑制反位缺陷Gd_Al在发光中心Ce_Gd附近形成(或富集), 最终降低(甚至消除)反位缺陷对发光中心的不良影响。XEL测试结果显示, 随着Mg掺杂量增大, 与反位缺陷相关的发射峰强度变弱, 这可以证明Mg对反位缺陷有抑制作用。     

Eu2+和Dy3+掺杂浓度对Sr2MgSi2O7材料的荧光和长余辉性能的影响

采用高温固相法制备得到Sr₂MgSi₂O₇: Eu²⁺和Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺发光粉, 并详细研究了Eu²⁺和Dy³⁺的掺杂浓度对Sr₂MgSi₂O₇材料的荧光和长余辉性能的影响。所有样品都在470 nm附近呈现较宽的发光峰, 这可归因于Eu²⁺离子的4f⁶5d→4f⁷电子能级跃迁。当Eu²⁺掺杂浓度超过淬灭浓度, 其浓度淬灭效应导致发光粉的荧光强度下降和余辉时间减短。同时, 发射峰的峰位随Eu²⁺浓度的增加而发生红移, 这主要由于晶体场分裂能和斯托克斯位移变化造成的, 而电子云扩大效应变化所产生的影响相对较弱。Dy³⁺离子会抑制荧光, 但有助于延长余辉时间。当其掺杂浓度超过10mol%时, Eu²⁺\Dy³⁺离子通过隧道复合机制发生浓度淬灭, 从而使材料的长余辉寿命减少。     

Eu2+/Tb3+掺杂的Sr2Si5N8基荧光粉的制备与发光性能

采用碳热还原氮化法合成了Eu²⁺/Tb³⁺掺杂的Sr₂Si₅N₈基荧光粉, 并重点研究了Tb³⁺-Eu²⁺共掺时Sr₂Si₅N₈基荧光粉的发光性能。研究结果表明: 由于Tb³⁺的f → d间的跃迁是自旋允许的, Sr₂Si₅N₈:Tb³⁺在330 nm激发光下, 在490、543、585和623 nm四处各有一发射峰, 它们分别来源于Tb³⁺的⁵D₄ → ⁷F_j (j = 6、5、4、3)能级跃迁; 掺入Tb³⁺对Sr_1.96Si₅N₈:0.04Eu²⁺的激发谱和发射谱的形状及峰位无明显影响, 当共掺离子Tb³⁺浓度为x = 0.01时, 样品发射强度比未共掺的Sr_1.96Si₅N₈:0.04Eu²⁺提高了约20%, Tb³⁺主要通过电多极能量传递的方式转向Eu²⁺。     

Ce3+掺杂Li2O-MgO-Al2O3-SiO2玻璃的结构与荧光猝灭现象

采用熔融淬冷法制备了不同浓度Ce³⁺离子掺杂的20Li₂O-5MgO-20Al₂O₃-55SiO₂玻璃闪烁材料。采用X射线衍射(XRD)、高分辨透射电镜(HRTEM)技术、密度检测等方法研究了玻璃的微观结构随Ce³⁺离子掺杂浓度的变化规律, 采用荧光分光技术检测了玻璃的紫外光致激发光谱(PLE)、发射光谱(PE)。研究结果表明: 在不对称的晶体场作用下, Ce³⁺离子5d能级被劈裂为5个组分; 随着玻璃基质内Ce³⁺离子掺杂浓度增大, 玻璃的非晶化程度加深; 5d能级的劈裂宽度随之增大, 由此导致激发带向低能量端展宽、发射光谱明显红移; Ce³⁺离子的荧光发射强度随Ce³⁺离子掺杂浓度先升高、后降低, 浓度猝灭过程成为其荧光发射效率降低的主要原因。     

Sr2Si5N8:Eu2+荧光粉的制备及其发光性能研究

以Sr₂CO₃、Si₃N₄和Eu₂O₃为原料, 以C为主要还原剂, 采用碳热还原氮化工艺合成Sr₂Si₅N₈:Eu²⁺荧光粉, 着重研究了C、Sr₂CO₃添加量及Eu²⁺浓度对产物物相及发光性能的影响。研究结果表明: 当C与Si₃N₄的摩尔比 n_c/=9/5时,合成出Sr₂Si₅N₈:Eu²⁺单相荧光粉, 添加适当过量的Sr₂CO₃可提高合成产物的N含量, 且荧光粉的发光强度与其N含量呈现正相关关系。在450 nm蓝光激发下, 受Eu²⁺的4f⁶5d¹ → 4f⁷跃迁作用, Sr₂Si₅N₈:Eu²⁺荧光粉在550~700 nm波段范围产生非对称宽带发射。随着Eu²⁺掺杂浓度由1.5mol%增加到20mol%, 荧光粉的发光强度先增强后减弱, 达到2mol%时发生浓度淬灭现象; 发射主峰由608 nm逐步红移至641 nm; CIE色坐标从(0.606, 0.393)位移至(0.656, 0.343), 是一种可用于白光LED的优质红色荧光粉。     

The luminescence of doped and undoped BaLn2(MoO4)4 (Ln = La,Gd)

The luminescence of nominally pure BaLn₂(MoO₄)₄ (Ln = La,Gd) is reported. Below 300 K molybdate emission is observed. The following activators were investigated: Eu³⁺, Tb³⁺, Pb²⁺ and Bi³⁺. The two lanthanide ions show their characteristic emission, the two s² configuration ions give an emission in which the host-lattice group as well as the activator is involved. The luminescence properties of these compositions are discussed and compared with those of related materials.