On the relationship between emission color and Ce3+ 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.     

Sensitized luminescence and energy transfer in Ce and Eu codoped calcium magnesium chlorosilicate

Ce³⁺ and Eu²⁺ ions codoped calcium magnesium chlorosilicate [Ca₈Mg(SiO₄)₄Cl₂] phosphors have been synthesized and characterized. Intense bluish-green light was observed under ultraviolet and blue light excitations. The diffuse reflection, excitation and emission spectra of Ca₈Mg(SiO₄)₄Cl₂:Ce³⁺,Eu²⁺ were measured at room temperature, and enhancement of Eu²⁺ emission was confirmed. The fluorescence lifetimes of Ce³⁺ were measured, and the mechanism of nonradiative energy transfer from Ce³⁺ to Eu²⁺ is found to be electric dipole–dipole interaction. The probabilities and efficiencies of nonradiative energy transfer were also calculated, and the results indicate that the efficiency can be as high as 86% in this material system.     

Lu2.94Al5O12:0.06Ce3+绿色荧光粉的制备及光致发光

采用高温固相法制备了Lu_2.94Al₅O₁₂:0.06Ce³⁺绿色荧光粉。通过X射线粉末衍射(XRD)、扫描电子显微镜(SEM)和光致发光光谱(PL)对样品的物相、形貌及发光性能进行了表征。结果表明,所合成的Lu_2.94Al₅O₁₂:0.06Ce³⁺绿色荧光粉为立方晶系,表面为类球形。激发光谱中,位于340和450 nm的激发峰分别归属于4f的两个能级到5d能级的跃迁而产生的吸收,340 nm处的激发峰是由于发光是由于²F_5/2到5d的跃迁,而450nm处的激发峰是由于²F_7/2到5d的跃迁。发射光谱中,位于525 nm的发射峰对应Ce³⁺的4f-5d电子跃迁。当Ce₃₊掺杂量为6%,1500℃煅烧5 h时,Lu_2.94Al₅O₁₂:0.06Ce³⁺绿色荧光粉CIE色坐标为(0.3683,0.5959),是一种可以用作白光LED的绿色荧光粉。     

Synthesis and spectral properties of Ce[Ag(CN)2]3

Cerium ion luminescence in crystalline hosts forms the basis of many blue phosphor and scintillator technologies. We report the synthesis of luminescent single crystals of cerium dicyanoargentate. The luminescence properties are characterized using both steady-state and time-resolved spectroscopy. The broad, overlapping dicyanoargentate and Ce³⁺ emissions are decomposed into three Gaussians, revealing the characteristic dicyanoargentate emission at 350 nm while the Ce³⁺ 5d–4f transitions are observed at 359 nm and 391 nm. Excitation measurements show that the 4f–5d Ce³⁺ absorption overlaps the 320 nm emission of the dicyanoargentate ions, leading to a strong coupling between the dicyanoargentate energy donors and Ce³⁺ acceptors. We conclude that the cerium is excited through an energy transfer process from the dicyanoargentate species, resulting in strong room temperature luminescence.     

掺铈多组分硅酸盐玻璃电子辐照着色研究

采用吸收光谱、电子顺磁共振谱和光致发光谱对掺Ce多组分硅酸盐玻璃K509在10 MeV电子辐照下的色心动力学进行了研究。结果表明, 电子辐照引起K509玻璃可见光透过率降低的色心类型为非桥氧空穴色心HC1和HC2。在剂量率一定的情况下, 色心浓度随总剂量的增大呈指数函数增大; 在总剂量一定的情况下, 色心浓度随剂量率增大呈指数函数减小。Ce³⁺荧光强度的变化表明辐照过程中Ce³⁺浓度与辐照总剂量负相关, 与辐照剂量率正相关, 验证了掺Ce玻璃耐辐照机理: Ce³⁺吸收辐照产生的空穴从而抑制空穴色心HC1和HC2的形成, 且不引入额外的可见光波段吸收。通过对Ce³⁺宽带荧光峰进行高斯拟合, 得到了K509中Ce³⁺能级结构图。     

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。     

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。     

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.     

Zn2+掺杂诱导Eu3+激活BiOCl层状半导体的反常发光性能研究

采用固相法在500℃下成功制备Zn²⁺掺杂BiOCl:Eu³⁺层状半导体, 并研究了Zn²⁺ (0~20mol%)掺杂对Eu³⁺激活BiOCl层状半导体发光性能的影响。利用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜(SEM)、傅里叶变换红外光谱(FT-IR)、激发-发射光谱、荧光寿命衰减曲线对样品的结构和性能进行表征。研究发现, 随Zn²⁺掺杂浓度增大, BiOCl晶体结构不变, Eu³⁺荧光寿命延长, 但发光强度却出现先减后增的反常现象。综合分析表明这可能与BiOCl特殊的层状结构有关。通过XRD和XPS的表征可以推断: 当Zn²⁺掺杂浓度≤10mol%, Zn²⁺在BiOCl中掺杂方式以晶胞层间隙掺杂为主; 当Zn²⁺掺杂浓度>10mol%后, 掺杂方式逐渐向取代掺杂转变。两种掺杂机制对Eu³⁺荧光寿命的改变以及形成缺陷对基质能量传递效率的影响可能是形成上述反常现象的主要原因。研究结果有助于认识稀土掺杂层状半导体的发光性能及影响规律, 并对Eu³⁺掺杂BiOCl这类新型发光材料的开发设计具有指导意义。     

Ce掺杂SrMgF4超结构多晶体的吸收/光致发光光谱

稀土(RE)离子掺杂的钙钛矿型氟化物是可调谐光学材料的候选材料。本工作通过沉淀法合成了SrMgF₄: xCe (x = 0, 0.007, 0.013和0.035)粉末。X射线衍射(XRD)分析表明所获得的荧光粉具有单斜超结构, 价态分析证实存在Ce³⁺/Ce⁴⁺混合价, 在紫外光区通过不同波长的激发光观察到两个荧光带B和C。当Ce³⁺多面体的对称性从高对称变为低对称时, 源于单斜超结构的晶体场导致能级发生强烈的改变。     

易分散球形YAG:Ce3+荧光粉的制备和性能

将微波均相沉淀与喷雾干燥相结合,并添加助熔剂辅助煅烧制备出单相YAG:Ce³⁺荧光粉体,研究了微波均相沉淀与喷雾干燥的共同作用对煅烧条件和YAG:Ce³⁺荧光粉颗粒形貌、分散性和荧光性能的影响。结果表明,这种单相YAG:Ce³⁺荧光粉体具有良好分散性,平均粒径为2μm;将微波均相沉淀与喷雾干燥相结合能制备出分散性好的球形YAG前驱体颗粒;添加NaF助熔剂使煅烧温度降低至1150℃,并得到纯YAG晶相;随着NaF添加量的增加荧光粉结晶度提高、发光强度增强、发射光谱蓝移;NaF添加量（质量分数）为6%时荧光粉的荧光强度最高,且与单一助熔剂比较,H₃BO₃ NaF混合助熔剂能更好的改善YAC:Ce³⁺的荧光性能。     

Cerium doped soda-lime-silicate glasses: effects of silver ion-exchange on optical properties

Effects of silver ion-exchange on optical absorption (OA) and photoluminescence (PL) spectra of a cerium doped soda-lime-silicate glass at room temperature are investigated. The optical spectra are described in terms of the characteristic transitions 4f↔5d originated in Ce³⁺ ions placed mainly in two different sites of the glass network. As Ag⁺ ions are introduced into the cerium doped glass, they are reduced to elementary silver (Ag⁰) which are favoured by the reaction Ce³⁺+Ag⁺→Ce⁴⁺+Ag⁰. Then, the number of Ce³⁺ ions decrease inversely with depth from the surface contrarily to Ce⁴⁺ ions does, and elementary silver diffuses and aggregates to form nanoparticles. As a consequence of these changes, the OA spectra of exchanged samples increase substantially in the UV range and the luminescence decreases significantly. The high sensitivity of PL together with deconvolution analysis of spectra, however, allows us to detect changes in the excitation and emission spectra from the earlier stages of ion-exchange. This indicates that during the ion-exchange we deal with fast processes (much shorter than 1 min). In fact, transmission electron microscopy observations of samples from the glass exchanged for a short time as 1 min at 325°C show the presence of a scanty number of silver nanoparticles, which confirms this point. Furthermore, with increasing the length of time of ion-exchange, PL spectra exhibit a progressive red shift indicative in part of a covalence increment in the oxygen–cerium coordinated bonding. We observe no luminescence from Ag⁺ ions and other silver molecular species in contrast with other preliminary PL studies on silver ion-exchange in soda-lime-silicate glasses free of cerium. The effect is discussed on the basis of a supplementary increase in the number of Ce⁴⁺ ions mainly due to the reaction Ce³⁺+Ag⁺→Ce⁴⁺+Ag⁰, which prevents efficiently the luminescence of the silver centers.     

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.     

实验优化设计中频反应溅射Al2O3:Ce薄膜发光性质研究

为了得到最优发光的薄膜材料成分参数,采用均匀设计和二次通用旋转组合设计相结合的方法建立发光强度与薄膜中氧含量和Ce³⁺ 离子掺杂浓度的回归方程,并用遗传算法求其取最大值时的解。用中频反应磁控溅射技术制备了相应成分的Al₂O₃:Ce非晶薄膜。在320nm光激发下,获得了较理想的发射光谱,对薄膜发光机理分析表明:薄膜的光致发光来自于Ce³⁺ 离子的5d1激发态向基态4f1的两个劈裂能级的跃迁。发光强度强烈的依赖于薄膜的掺杂浓度和氧元素含量。XPS检测表明,Al₂O₃:Ce薄膜中存在Ce³⁺ 。Ce³⁺ 含量和薄膜的化学成分是通过X射线散射能谱(EDS)测量的。薄膜试样的晶体结构应用X射线衍射分析。     

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.     

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。     

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.     

Low-temperature synthesis of nanocrystalline ZnGa2O4:Tb phosphors via the Pechini method

The synthesis of trivalent terbium doped ZnGa₂O₄ nanosized new phosphors by the Pechini method was reported. Well-crystallized ZnGa₂O₄:Tb³⁺ phosphors were obtained at low-temperature about 550 °C. The phosphors formed porous agglomerates which consist of spherical nanocrystallites with a uniform size at about 30 nm. The photoluminescence of the phosphors included both the luminescence of ZnGa₂O₄ host and characteristic emission of Tb³⁺, and the excitation spectra showed an energy transfer from the host lattice to the activator. The Tb³⁺ emission from the phosphors prepared by the Pechini process was more intensive than that of phosphors by solid-state reaction process.     

Cathodoluminescence of rare-earth-doped zinc aluminate films

Eu-, Tb-, and Tm-doped zinc aluminate (ZnAl₂O₄) thin film phosphors were prepared by the spray pyrolysis technique at an ambient pressure. The effects of preparation conditions on the cathodoluminescence properties of the films were studied. Films containing Tb³⁺ and Tm³⁺ ions exhibited green and blue cathodoluminescence, respectively. For films doped with europium, both red emission lines from Eu³⁺ and a broad blue–green emission band from Eu²⁺ were observed. The CIE (Commission Internationale de L'Eclairage) chromatic coordinates, dominant wavelength, and color purity were determined for each phosphor. The luminance and efficiency of these phosphors at a current density of 57 μA/cm² are found to be linearly dependent on the excitation voltage.     

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。