草酸沉淀法制备纳米晶Y2O3:Eu3+及粉体评价

报道了草酸作为沉淀剂并添加表面活性剂合成了纳米晶Y2O3：Eu^3 的方法,其一次粒径为20-30nm,团聚尺寸D50=0.53μm。粉体细且分布均匀。与微米晶比较,该纳米晶的发射光谱发生明显蓝移,色座标合荧光粉要求。     

Controllable synthesis of glass ceramics containing YF3:Eu3+ nanocrystals: Well-preserved Eu and prolonged lifetime

Monolithic luminescent glass-ceramic (GC) embedded with fluoride-based nanocrystals (NCs) has drawn much attention as it is stable and possesses long fluorescent lifetime, while only small partial of optically active ions could enter the fluoride NCs prepared by conventional crystallization process. In this work, YF₃:Eu³⁺ embedded GCs have been controllably synthesized by Spark Plasma Sintering at a relatively low sintering temperature (960°C) within 10 minutes. The GC samples show typical sharp reddish-orange emissions peaking at λ = 590 nm and 620 nm, which can be ascribed to the ⁵D₀ → ⁷F_j transitions of Eu³⁺ located in the tetrahedral coordination sites of the YF₃ NCs. Significantly, a small R/O ratio (photoluminescence intensity ratio of ⁵D₀ → ⁷F₂/⁵D₀ → ⁷F₁) suggests that majority of Eu³⁺ ions are well preserved in YF₃ NCs, which is confirmed by the EDS and TEM results that highly crystallized YF₃:Eu³⁺ NCs are homogeneously dispersed into the silica glass matrix without interfacial reaction. Hence, the lifetime of GC sample is prolonged to 6.8 ms These results demonstrate that Eu³⁺ could be well protected and resided in YF₃ low phonon crystal by this method to fabricate GC composites with high optical performance.     

Eu^3＋、Dy^3＋对CaTiO3：Pr^3＋红色磷光体发光性能的影响

采用改进高温固相法合成了掺杂Eu3+和Dy3+作为共激活离子的红色长余辉磷光体,详细阐述了Eu3+、Dy3+对CaTiO3:Pr3+红色磷光体发光性能的影响.通过X-射线衍射仪和电子扫描显微镜对所得样品的晶相类型及表面形态进行了表征,结果发现,在一定灼烧温度下,Eu3+或/和Dy3+对晶相的作用是协同的,且Eu3+或/和Dy3+对CaTiO3:Pr3+红色磷光体的粒径也有影响.室温条件下采用荧光/磷光发光光度计对其发光性能进行测定,结果表明,一定量的Eu3+或/和Dy3+能显著改善CaTiO3:Pr3+红色磷光体的发光性能.     

红色荧光粉YAl3(BO3)4:Eu3+的制备及发光性能研究

以稀土氧化物、硝酸铝和硼酸为原料,高温固相反应制备了单相红色荧光粉YAl3(BO3)4:Eu3+,用X射线衍射和发射光谱对荧光粉末的结构和发光性能进行了分析.研究了煅烧温度、Eu3+掺杂量对其发光性能的影响.结果表明,反应物在1 250 ℃下煅烧可制得单相YAl3(BO3)4:Eu3+晶体,在YAl3(BO3)4:Eu3+晶体中,Eu3+取代了YAl3(BO3)4晶体中Y3+,占据了非对称中心格位.在394 nm的紫外光激发下,YAl3(BO3)4:Eu3+荧光粉具有很强的发光性能,与(Y,Gd)BO3:Eu3+荧光粉相比,最强发射线波长由596 nm变为618 nm,由橙红色光变为红色光,色纯度有了很大提高.Eu3+的最佳掺杂量为8%(物质的量分数).     

Unusual concentration induced antithermal quenching of the Eu2+ emission at 490 nm in Sr4Al14O25:Eu2+ for near ultraviolet excited white LEDs

Thermal quenching of phosphor is an important challenge for its practical application in phosphor-converted white light-emitting diodes (pc-WLEDs) and it usually becomes aggravated with the increase of activator concentration. Conversely, this work finds the thermal quenching of Eu²⁺ emission at 490 nm in Sr₄Al₁₄O₂₅:Eu²⁺ does not follow this in the temperature range of 300 to 480 K, and the rate of it is even slowed down as the concentration of Eu²⁺ increases. However, at the same time, the experiment on three heating-cooling cycles of Sr₄Al₁₄O₂₅:Eu²⁺ reveals that the thermal degradation of Eu²⁺ emission becomes improved. Once Eu²⁺ ions are doped into Sr₄Al₁₄O₂₅, they will prefer substituting for the 10- and 7-coordinated strontium sites Sr1 and Sr2, respectively. The emission centers Eu1 and Eu2, therefore, appear. The abnormal phenomenon is perhaps partly due to the enhanced energy transfer from the emission center Eu1 at 407 nm to the one Eu2 at 490 nm. It is also found interesting that the introduction of AlN can enhance the emission of Sr₄Al₁₄O₂₅:Eu²⁺ without leading to the deterioration of thermal degradation. In the end, a prototype of pc-WLED was fabricated with Sr₄Al₁₄O₂₅:Eu²⁺ to demonstrate the application of white lighting. This work is not only beneficial to the understanding of the relationship between concentration and thermal quenching, but also conducive to the design of the heavily doped phosphor for WLEDs with better resistance to thermal quenching.     

Eu~(3+)掺杂浓度对NaYF_4:Eu~(3+)晶体荧光强度的影响

在乙醇和乙二醇的混合溶剂中,用溶剂热法,150℃,反应12 h,成功合成了NaYF4:Eu3+晶体。室温下,用X射线衍射对材料的组成进行了表征,JCPDS号为16-0334。荧光光谱分析表明,在395 nm(7F0→5L4)紫外光激发下,其发射峰在476 nm、540~578 nm、718 nm分别对应着Eu3+的5DJ(J=0,1,2,3)→7FJ(J=1,2,3,4)能级跃迁。并讨论了离子Y3+:Eu3+不同浓度掺杂比对荧光性质的影响。结果表明,Eu3+的最佳掺杂浓度比为5%,当掺杂浓度为10%时,出现荧光猝灭。     

Photoluminescence analysis of Sm3+ and DY3+ doped PVA films

A couple of Poly vinyl alcohol (PVA) films with Sm³⁺ and Dy³⁺ ions have been prepared by a conventional solution cast technique. For these Sm³⁺ and Dy³⁺ doped PVA films, Fourier transform infrared and also absorption spectral measurements have been carried out. Excitation and emission spectra and decay curves have been recorded to understand emission performance of the polymers namely Sm³⁺: PVA film with λ_exci = 400 nm and Dy³⁺: PVA film with λ_exci = 349 nm. Emission performances of these films have been explained in terms of relevant energy level schemes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

YVO4:Eu3+,Bi3+荧光粉的制备及荧光性能研究

用溶胶凝胶法在较低温度下制备了YVO4:Eu3+,Bi3+荧光粉,采用X射线衍射仪(XRD),扫描电子显微镜(SEM)及荧光分光光度计测试,研究了合成产物的结构、表面形貌,分析了在Eu3+含量一定的情况下掺杂Bi3+的浓度的变化对发光性能的影响.结果表明,溶胶凝胶法合成的YVO4:Eu3+,Bi3荧光粉为单相结构、粒径在1 μm左右、无团聚现象;Bi3+对Eu3+离子有敏化作用,在一定浓度下使荧光粉的发射强度增加.     

InBO3:Eu3+荧光粉的制备及光谱特性

合成了InBO3:Eu3 红色荧光粉 ,测定了其发光光谱 ,讨论了其发光亮度与稀土离子Eu3 浓度的关系     

Eu3+在LiSrPO4中的发光及浓度猝灭机理

采用高温固相法合成了白光发光二极管用LiSrPO4:Eu3+红色荧光粉.测量了LiSrPO4:Eu3+的激发和发射光谱,结果显示材料的发射光谱为一系列尖峰,主峰位于616 nm,具有很强的红光发射;激发光谱中O2-→Eu3+的电荷迁移态CTS (220～310 nm)非常低,Eu3+的f→f (310～500 nm)跃迁吸收很强,主峰位于393 nm,与InGaN(350～410 nm)管芯匹配.比较了LiSrPO4:Eu3+与LiCaPO4:Eu3+、LiBaPO4:Eu3+发射光谱的差异,这三种晶体中Eu3+占据的格位对称性按Ca、Sr、Ba顺序逐渐增加.根据Dexter理论判定Eu3+在LiSrPO4中的浓度猝灭机理为电四极-电四极(q-q)相互作用.加入电荷补偿剂Li+、Na+和Cl 均提高了LiSrPO4:Eu3+材料的发射强度.LiSrPO4: Eu3+是一种适合白光发光二极管激发的红色荧光粉.     

Luminescence and temperature-sensing properties of Y4GeO8:Bi3+,Eu3+ phosphor

In this paper, Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor with dual emission centers was elaborated via conventional solid-state reaction technology. Thorough research on the structure, morphology, and luminous properties of Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor, the potential applications in optical thermometry were investigated by means of fluorescence intensity ratio and thermochromic techniques. Under 290 and 347 nm excitation, Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor presents broadband emission from ³P₁ → ¹S₀ transition of Bi³⁺ ions and characteristic emission peaks from 4f–4f transition of Eu³⁺ ions. Outstanding temperature-sensing capabilities are acquired from Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor. The maximum relative sensitivity (S_r) can attain 1.51% K⁻¹ (λ_ex = 290 nm). With temperature raising (303–513 K), the emitted color of Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor (λ_ex = 290 nm) shifts from faint yellow to red with a high chromaticity shift (0.180), which can be distinguished by the unaided eye clearly. Our results indicate that Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor has potential applications in optical temperature measurement and high-temperature safety marker.     

掺铽的铝酸锶铕镝磷光体的发光特性及晶相分析

采用高温固相法在弱还原气氛下制备了掺入Tb3 的SrAl2O4:Eu2 ,Dy3 磷光体.研究了Tb3 对SrAl2O4:Eu2 ,Dy3 磷光体的发光性能的影响.结果发现,引入Tb3 以后,对基质SrAl2O4的晶体结构基本上没有影响,也未改变磷光体的发光光谱,却使磷光体的初始亮度显著提高,并使余辉时间延长.其余辉强度随时间的变化由最初的快衰减过程和随后的慢衰减过程组成,符合t-1.1的双曲线规律.并初步探讨了Tb3 的作用机制.     

Amplified spontaneous emission of Eu(DBM)3Phen doped step‐index polymer optical fiber by end‐pumping with a YAG

Eu(DBM)₃Phen doped poly(methyl methacrylate) core step‐index polymer optical fiber (SI POF) has been fabricated and related properties of the doping material were discussed. Amplified spontaneous emission (ASE) at 613 nm of a SI POF with 40 cm length has been observed at ambient temperature by end‐pumping with a YAG at 355 nm. The threshold of the absorbed pump power for the onset of ASE is about 0.01 mJ. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 912–916, 2005     

水热法合成SrAl2O4:Eu2+,Dy3+长余辉材料

研究了SrAl2O4：Eu^2 ，Dy^3 长余辉材料的一种新合成方法。首先利用水热法制备出该发光材料的前驱体，然后将此前驱体粉体在还原气氛下高温烧结，得亮度高，余辉时间长的洲SrAl2O4：Eu^2 ，Dy^3 超细长余辉材料，并对其发光性能进行了研究。并对水热法和复合沉淀法合成的此种材料进行了比较。     

Eu3+,Ce3+共掺硼硅酸锌玻璃的发光性能及能量传递

采用高温液相法制备了50ZnO-30SiO2-20B2O3∶Eu3+,Ce3+玻璃。测试了样品的激发光谱和发射光谱。结果表明:在紫外光激发下,该玻璃可以发出明亮的红色光。其中580 nm,593 nm,617 nm,655 nm和706 nm波长处的发射峰分别对应于Eu3+的5D0→7F0,5D0→7F1,5D0→7F2,5D0→7F3和5D0→7F4跃迁发射,其中5D0→7F2跃迁发射强度最大,同时发现在450 nm处存在Ce3+的5D→2FJ(J=7/2,5/2)特征发射峰。首次发现在该发光玻璃50ZnO-30SiO2-20B2O3∶Eu3+,Ce3+中存在着Ce3+→Eu3+能量传递现象,其中Ce3+起敏化作用。     

Preparation and photoluminescence enhancement of Au nanoparticles embedded LaPO4:Eu3+ inverse opals

In this work, we present a facile preparation approach of Au nanoparticles embedded LaPO₄:Eu³⁺ inverse opal photonic crystals. In the typical preparation process, the transparent LaPO₄:Eu³⁺ sol including HAuCI₄ was infiltrated into the opal templates. After the sintering, the 10‐20 nm Au nanoparticles were formed in the interior of nano‐sized wall of LaPO₄:Eu³⁺ inverse opal and the Au nanoparticles embedded LaPO₄:Eu³⁺ inverse opals were obtained. The luminescence of Au nanoparticles embedded LaPO₄:Eu³⁺ inverse opal was investigated. The emission peaks located at the 593 (⁵D₀→⁷F₁), 618 (⁵D₀→⁷F₂) and 698 nm (⁵D₀→⁷F₄) from Eu³⁺ ions were observed. The 593, 618, and 698 nm emissions of Au nanoparticles embedded LaPO₄:Eu³⁺ inverse opals were enhanced in contrast to these of LaPO₄:Eu³⁺ inverse opal without the Au nanoparticles, which is from the excitation field enhancement caused by the localized surface plasmon resonance of Au nanoparticles.     

Enhanced luminescence properties of Eu3+ in La2MoO6 by nonsensitization of Bi3+

It was unusual for Bi³⁺ ions to enhance the emission intensity of phosphors via nonsensitization. Here, La₂MoO₆:Eu³⁺, Bi³⁺ phosphors were successfully synthesized by a high temperature solid-state reaction method in air atmosphere. As the increase of doping concentration of Bi³⁺, the emission spectra of La₂MoO₆:Eu³⁺, Bi³⁺ phosphors had obvious shifts, splits and the enhancement of intensities, which indicated that the characteristics of the phosphors were modified. To analyze these phenomena, the crystal structure refinements, spectral characteristic analyze and Judd-Ofelt theoretical calculation were mainly performed. Bi³⁺ ions played the role of the nonsensitizer and affected the distortion of the crystal, the sites of Eu³⁺ ions, the field splitting energy and the internal quantum yield. Moreover the nephelauxetic effects of Bi³⁺ ions and the ET process caused synergistically the life times of La₂MoO₆:Eu³⁺, Bi³⁺ phosphors to increase and then gradually decrease. The CIE coordinates of phosphors changed within a small range. This study might be instrumental in promoting the further application of Bi³⁺ ions in rare earth luminescent materials.     

Fe~(3+)、Eu~(3+)共掺纳米TiO_2光催化降解N-(2-苯并咪唑基)-氨基甲酸甲酯

采用溶胶-凝胶-微波法制备Fe3+、Eu3+共掺杂纳米TiO2(Fe/Eu-TiO2),并通过紫外-可见吸收光谱(UV-Vis)、荧光光谱(FS)、X射线衍射(XRD)、扫描电镜(SEM)、比表面积测定(BET)等手段对其进行表征。结果表明:在500℃氮气保护下退火制得的Fe/Eu-TiO2为锐钛矿相纳米颗粒,平均粒径为20—50 nm;对可见光的响应范围为370—770 nm。光催化降解N-(2-苯并咪唑基)-氨基甲酸甲酯(多菌灵)的实验表明,Fe3+、Eu3+共掺杂对TiO2光催化表现出协同增效作用,在可见光下能产生更多的羟基自由基,对多菌灵降解速率常数kapp为0.046 66 min-1,大于分别单掺Fe3+和Eu3+的TiO2纳米粒子。     

纳米Y_2O_2S:Eu~(3+)红色荧光粉的间接法制备及发光性质

用间接法制备纳米级红色荧光粉Y2O2S:Eu3+(物质的量之比为Eu3+/Y3+=0.02)。XRD测试表明,制得纳米级的Y2O2S:Eu3+为单一纯相。透射电子显微镜(TEM)扫描结果显示纳米材料的平均颗粒尺寸为30 nm,与Debye-Scherre公式计算的结果基本一致。荧光光谱中,激发光谱分为3个区域,200-280 nm的区域为Y2O2S基质的激子激发带,峰值为262 nm;280-380 nm的区域属于Eu3+→O2-(S2-)的电荷迁移带,峰值为319 nm;而位于399 nm和472 nm的线状光谱则属于Eu3+的4 f组态内部电子之间的跃迁。     

Enhancing emission intensity and thermal stability by charge compensation in Sr2Mg3P4O15:Eu3+

Charge compensation was the effective methods to enhance the luminescence properties of phosphors. In this paper, novel single‐phased orange light emitting Sr₂Mg₃P₄O₁₅:Eu³⁺ phosphors were prepared by solid state method. The phase purity and luminous characteristics were examined in detail. Meanwhile, three kinds of charge compensation methods (co‐doping the alkali metal R⁺ (R⁺ = Li, Na, and K), substituting Si⁴⁺ for P⁵⁺ and self‐compensation) were employed to solve the charge imbalance problem between Sr²⁺ and Eu³⁺. The results showed that emission intensity of Eu³⁺ was improved by 1.43 (Li⁺), 1.58 (Na⁺), 1.53 (K⁺), 1.61 (Si⁴⁺), and 1.30 (self) times than that of Sr_1.6Mg₃P₄O₁₅:0.40Eu³⁺, respectively, and there was no change in the emitting color simultaneously. Furthermore, as the temperature reached at 423 K, the emission intensity increased from 41.67% of Sr_1.6Mg₃P₄O₁₅:0.40Eu³⁺ to 55.69% (Li⁺), 61.62% (Na⁺), 58.98% (K⁺), 71.15% (Si⁴⁺), and 80.59% (self) of that at room temperature. The reasons of those phenomena were the reduction in ion vacancies caused by charge imbalance through the charge compensation process. The specific mechanisms were elaborated in detail. Overall, this research validated that the charge compensation strategies could be severed as the key method to improve the luminescence properties, especially the thermal stability of phosphor.