微波辅助均相沉淀法制备（Y1-x-y, Lay）2O3:xEu3+红色荧光粉

用微波辅助均相沉淀法制备了一系列（Y_1-x-y, La_y）₂O₃:xEu3+(x=0.01~0.05, y=0.05~0.25) 红色荧光粉.研究Eu3+、La3+的掺杂浓度和煅烧温度对荧光粉性能的影响.通过差热分析仪、红外光谱仪、XRD、SEM和荧光分光光度计,对前驱体热重曲线和FTIR曲线、样品的晶体结构、表面形貌及颗粒大小和荧光性能进行表征.结果表明:前驱体组成为 (Y, La, Eu) OHCO₃·nH₂O;所制备样品为立方晶系;SEM显示荧光粉为均匀分散的球形颗粒,粒度为200 nm左右;较为适宜的焙烧温度为900 ℃;La3+掺杂含量y=10 %, Eu3+掺杂含量x=3 %时,样品荧光粉发光性能最好,最大发射波长为614 nm,对应的是Eu3+的5D₀→7F₂跃迁;样品的色坐标为 (0.654, 0.346).所制备的（Y_1-x-y, La_y）₂O₃:xEu3+荧光粉具备较好的发光强度与色纯度.      

溶胶-凝胶法制备Sr2SiO4:Tb3+绿色荧光粉及其发光性能

采用溶胶-凝胶法合成了一系列适合紫外-近紫外激发的(1-X)Sr₂SiO₄:XTb3+(X=0,0.01,0.02,0.03,0.04,0.05,0.06)绿色荧光粉,并采用X射线衍射(XRD)、扫描电子显微镜(SEM)和荧光光谱(PL)研究了样品的结构及发光性能.由XRD的检测结果可知,合成样品属于单斜晶系的β-Sr₂SiO₄相.由SEM图可知,所有样品都呈无规则块状结构.当监测波长为546 nm,样品的激发光谱的主峰位于370 nm处,属于Tb3+的4f-4f特征跃迁吸收.当激发波长分别为285 nm和250 nm,所有样品在488 nm,547 nm,586 nm,623 nm处都出现了1个强发射峰,分别对应Tb3+的5D₄→7F₆、5D₄→7F₅、5D₄→7F₄和5D₄→7F₃电子跃迁.最强发射峰位于547 nm处,呈现特征为绿光发射.随Tb3+掺杂量增大,发射强度呈现出先增大后减小的变化趋势,即存在浓度猝灭效应.当Tb3+掺杂量为X=0.03时,样品的发光强度最大.      

微波辅助液相沉淀法合成Ca(MoO4)1-x(WO4)x:Eu3+红色荧光粉

以尿素为沉淀剂，采用微波辅助液相沉淀法合成了类球状双基质Ca(MoO₄)_1-x(WO₄)_x:Eu3+红色荧光粉，通过采用XRD、SEM、荧光光谱(PL)等现代分析技术对荧光粉的结构、形貌及发光性能进行了表征.结果表明，制备的Ca(MoO₄)_1-x(WO₄)_x:Eu3+红色荧光粉晶型完整，纯度高，为白钨矿结构；掺杂WO₄2-离子后，CaMoO₄:Eu3+红色荧光粉的发光性能明显增强，当WO₄2-离子的掺杂量x=0.4时，在395 nm激发下，在616 nm处的主发射峰的发光强度达到最大，掺杂浓度过高时会出现浓度淬灭现象.其较优的煅烧温度为1 000 ℃，煅烧时间为4 h.      

Y2MgTiO6:Mn4+/Nd3+的制备及近红外发光性能

采用传统的高温固相反应制备了一系列Y₂MgTiO₆:Mn4+/Nd3+下转换材料。利用稳态激发发射光谱以及瞬态荧光寿命等进行了分析, 在Mn4+→Nd3+能量传递过程中, 在331 nm激发下Nd3+产生885 nm和1 085 nm的红外发射对应于4F_3/2→4I_11/2与4F_3/2→4I_9/2能级跃迁。研究结果证实, 双掺Mn4+/Nd3+的Y₂MgTiO₆在1 085 nm荧光强度比其单掺Nd3+的Y₂MgTiO₆增强了5倍。还进一步阐释了Mn4+→Nd3+能量传递主要是共振能量传递的偶极-偶极机制。近红外发光的下转换材料Y₂MgTiO₆:Mn4+/Nd3+对晶体硅太阳能电池的荧光转换层具有很好的应用价值。      

白光LED用LaPO4:Eu3+红色荧光粉的合成与表征

利用水热法制备了性能稳定的红色荧光粉LaPO4:Eu3+,同时研究了不同的Eu3+浓度、煅烧温度对荧光粉发光性能的影响.通过X射线粉末衍射(XRD)和扫描电子显微镜(SEM)来表征荧光粉的晶体结构和颗粒大小及形貌;用激发光谱和发射光谱以及荧光衰减曲线来表征荧光粉的荧光性能.结果表明:未煅烧时前躯体主要是六方晶相LaPO4·0.5H2O,煅烧温度在900℃时,所制备样品为单斜相LaPO4:Eu3+;SEM图像显示5 at.%Eu3+掺杂LaPO4呈椭球形,颗粒长约为500 nm,宽约为300 nm.最大发射波长和激发波长分别为592 nm和393 nm,发射光谱中592 nm和612 nm的发射峰对应的是Eu3+离子的5D0→7F1和5D0→7F2跃迁.其荧光寿命为3.32 ms.     

Yb3+，Er3+掺杂Y2Ti2O7荧光粉的制备与上转换发光机理研究

采用溶胶-凝胶法制备合成了(Y_0.98-xYb_xEr_0.02)₂Ti₂O₇(x=0, 0.02, 0.04...0.10)荧光粉, 分别采用XRD和荧光光谱仪对样品的结构和上转换发光性能进行了表征.研究了Yb3+掺杂浓度对样品上转换发光性能的影响, 并对样品的发光机理进行了研究.结果表明, 所得样品为面心立方结构的烧绿石相.在980nm激发下, 样品展现出很强的上转换荧光发射并且发光颜色可以通过Yb3+掺杂浓度来调节.样品上转换绿光和红光发射均为双光子过程并且交叉弛豫过程在上转换红光发射过程中占据主导作用.      

水热法制备Y2O3:Eu及其发光性能的研究

利用水热法制备立方相Y₂O₃:Eu红色荧光粉.在不同掺杂浓度、不同溶液pH值的系列样品中,均观测到Eu3+离子的特征发射.荧光强度与Eu3+离子掺杂浓度关系研究表明:在不同掺杂浓度中,Eu3+离子掺杂浓度为9 %时其相对发射强度最强.在不同溶液pH值所获得的样品中,以溶液pH等于6制备的样品发光效果最好.此外通过与商用Y₂O₃:Eu红色荧光粉比较,发现其荧光强度相当.因此,与传统高温固相法相比,水热法合成Y₂O₃:Eu红色荧光粉是简单易行方案.      

NaYF4∶Yb3+/Nd3+纳米粒子近红外热增强发光及温感研究

采用共沉淀法制备了一系列六方相NaYF₄∶Yb³⁺/Nd³⁺纳米粒子。在980 nm激光激发下,观测到峰值分别位于752 nm、804 nm和862 nm的近红外第一生物窗口发光,分别对应于Nd³⁺的⁴F_7/2→⁴I_9/2、⁴F_5/2→⁴I_9/2以及⁴F_3/2→⁴I_9/2辐射跃迁。特别是,Nd³⁺的上述近红外发光展现出优异的热增强发光性质,其中752 nm发光峰在温度从室温升至443 K时增强倍数达到83.7倍。采用发光强度比系统研究了303 K～443 K温度范围内Nd³⁺的温度传感性能,研究发现采用752 nm和862 nm的发射峰强度比,最大相对灵敏度达到3.07%K^-1     

掺杂离子对红色荧光粉NaLn_4(SiO_4)_3F∶Eu~(3+)(Ln=La,Gd,Y)发光性能的影响

利用高温固相法合成系列Na Ln4(Si O4)3F∶Eu3+(Ln=La,Gd,Y)红色荧光粉,用X射线粉末衍射仪和荧光分光光度计对荧光粉进行结构和性能表征,研究Eu3+浓度以及基质组成的变化对Na Ln4(Si O4)3F∶Eu3+(Ln=La,Gd,Y)发光性能的影响。在394 nm激发下,荧光粉Na La4-x(Si O4)3F∶x Eu3+中的Eu3+主要体现5D0→7F2(616 nm)和5D0→7F1(590 nm)跃迁发射,而且5D0→7F2和5D0→7F1跃迁发射强度比例随Eu3+浓度的增大而变化,较低浓度时5D0→7F1发射比5D0→7F2强,较高浓度时则刚好相反。在273 nm激发下,荧光粉Na La3.9-yGdy(Si O4)3F∶0.1Eu3+或Na La3.9-zYz(Si O4)3F∶0.1Eu3+中Eu3+的5D0→7F2(616 nm)发射随掺杂离子浓度增加而增强,而5D0→7F1发射强度变化不大。因此可以通过改变Eu3+浓度以及基质组成离子Gd3+或Y3+浓度对5D0→7F2和5D0→7F1发射强度加以调整,进而调整荧光粉的红光色度。     

阳离子引入对CsPF6:Mn4+红色荧光粉发光性能的影响

采用共沉淀法在室温条件下合成了CsPF₆:Mn4+荧光粉,研究了Li+、Na+、K+阳离子的引入对CsPF₆:Mn4+荧光粉发光强度的影响。所制备的系列荧光粉样品均为立方结构纯相。在蓝光激发下,呈现最强峰位于634 nm处的一系列窄带红色发射。加入K+和Li+后,发光强度增强,加入Na+后发光强度有所减弱,其中加入K+的CsPF₆:Mn4+荧光粉发光强度最强。CsPF₆:Mn4+, K+荧光粉的发射强度随着温度的上升先增强然后由于非辐射跃迁的增加而降低,在423 K时达到最大值,发射强度相较于未引入阳离子的荧光粉发射强度亦增强。阳离子的引入可以有效提升CsPF₆:Mn4+荧光粉的发光性能。      

Luminescent Properties of SrGa2S4 :Eu and Its Application in Green-LEDs

Phosphor SrGa2S4Eu2 was synthesized with a high temperature solid state reaction.Its absorption spectrum, photoluminescence spectra, and fluorescence lifetime were studied in details.The excitation spectrum extended from UV to visible light region, and matched the emission of GaN chip.(Sr1-xEux)Ga2S4 emits strong green light and the concentration quenching did not occur; while the thermal quenching was evident.The emission peak shifted to long wavelength with increasing Eu2 concentration because of the changing of the crystal field strength.The lifetime of Eu2 ion was in the order of microsecond, which was reasonable for d→f transition.The electroluminescence spectrum of as-fabricated PC-LED at IF=20 mA was measured and most of the blue light of blue-LED chip at 460 nm was absorbed by the phosphor and simultaneously down-converted into an intensive green light at 540 nm.The color coordinate was (0.32, 0.63).SrGa2S4Eu2 was a promising phosphor for GaN-based green LEDs.     

Synthesis and Fluorescence Properties of Europium,Terbium Doped Zn^2＋, Cd^2＋, and Cr^3＋ Complexes

Europium and terbium complexes with strong fluorescence intensity and long fluorescence lifetime were prepared. By replacing half of the europium or terbium ion with M （M = Zn^2＋, Cd^2＋, and Cr^3＋） using the doped method, and then incorporating it with 18-crown-6 ether and terephthalic acid, six heteronuclear samples EuZnLL＇Cl3·3H2O（1）, EuCdLL2＇Cl3·5H2O（2）, EuCrLL＇Cl4· 4H2O（3）, TbZnLL＇Cl3·4H2O（4）, TbCdLL＇2Cl3·4H2O（5）, and TbCrLL＇2Cl4 ·4H2O（6） （L = terephthalic acid, L＇= 18-Crown-6 ether） were obtained. The elemental analysis, molar conductivities, rare earth complexometry, Fourier Transform Infrared Spectroscopy （FT-IR）, ultraviolet （UV）, TGA, fluorescence intensity, and fluorescence lifetime of the samples were measured. The results showed that there were good luminescence properties for heteronuclear complexes （1）, （2）, （4）, and （5）, which were even stronger than those of the homonuclear complexes Eu2LL＇2Cl4·4H2O and Tb2LL＇2Cl4 ·4H2O, but the luminescence properties of EuCrLL＇Cl4·4H2O, TbCrLL＇Cl4·4H2O were very weak. A possible luminescence mechanism was suggested by the organic-inorganic doped mechanism and the law of intramolecular energy transfer.     

Co-Precipitation Synthesis and Spectral Characteristics of Long Afterglow Phosphor Y2O2 S： Sm^3＋, Mg^2＋ , Ti^4＋

Y2O2S：Sm^3＋, Mg^2＋, Ti^4＋ phosphor was synthesized by co-precipitation method. The crystalline structure of all synthesized phosphors was investigated by XRD. The result showed that all synthesized phosphors had a hexagonal crystal structure, which was the same as Y2O2S. The emission spectrum and excitation spectrum were measured, and the effect of Sm^3 ＋ molar ratio on the spectra was discussed. The emission spectra of the phosphors showed three emission peaks due to typical transitions of Sm^3 ＋ （4G5/2→6HJ ,J = 5/2, 7/2, 9/2）, and the emission peaks at 606 nm was stronger than others. With the increase of Sm^3 ＋ molar ratio, the emission intensity was strengthened. The excitation peaks were ascribed to the representative energy transition 4f→4f of Ti^4＋ phosphor prepared by co-precipitation method was Sm^3＋ ions. The results indicated that the Y2O2S ： Sm^3＋ , Mg^2＋ , an efficient long afterglow phosphor.     

作为白光LED用铕掺杂氟化镧红色荧光粉的制备与光谱性能研究

采用水热法制备具有单一相六方晶系的LaF₃:Eu3+纳米荧光粉.通过X射线粉末衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、光致发光光谱(PL)和荧光衰减曲线对LaF₃:Eu3+纳米荧光粉进行表征.LaF₃:Eu3+荧光粉的激发光谱主要由250 nm处的宽带(O2-→Eu3+的电荷转移跃迁)和一些尖峰(Eu3+ f-f跃迁)构成,其中位于近紫外区396 nm处有一较强的激发峰.通过发射光谱探测Eu3+在LaF₃晶体中的局部晶场环境.在298 K下激发光谱和发射光谱可知,在六方晶系的LaF₃纳米晶体中的Eu3+晶格位置从D_4h降至到C_2v,这是由于晶格变化所造成的.在396 nm激发下,观测到较优掺杂浓度为10%的LaF₃:Eu3+荧光粉在591 nm(5D₀→7F₁跃迁)处有强烈的红色发射峰.其发光性能表明,LaF₃:Eu3+红色荧光粉在近紫外发光二极管领域具有潜在的应用价值.      

Facile sol-gel combustion synthesis and photoluminescence enhancement of CaZrO3：Sm3＋ nanophosphors via Gd3＋ doping

CaZrO3:Sm and CaZrO3:Sm,Gd nanophosphors were synthesized by a facile and efficient sol-gel combustion method. Their structure and optical properties were studied. The photoluminesce (PL) results showed that the phosphor could be efficiently excited by irradiation at wavelengths in the visible light region (350-430nm). The CaZrO3:Sm nanophosphor exhibited strong yellow-green, orange and red emissions with peak wavelength centered at 565nm (4G5/2→6H5/2), 601nm (4G5/2→6H7/2) and 645nm (4G5/2→6H9/2), respectively. The incorporation of Gd3+ ions could greatly improve the luminescence intensity. The highest emission intensity was observed with 2mol.% Gd3+ doped CaZrO3:3mol.% Sm powder. The material had potential application in the development of materials for LED’s and other optical devices in the visible region.     

Luminescence of samarium doped hydroxyapatite containing strontium: Effects of doping concentration

A series of samarium (Sm) doped hydroxyapatites containing strontium (Sr) with controllable and adjustable luminescence were designed and prepared via chemical hydrolysis co-precipitation method. The effects of doping concentration of Sm on the structure, composition, photoluminescence (PL), energy transfer, substitute site, fluoresce lifetime and luminescence color of samples were investigated. It is shown that the introduction of Sr ions induces the structure and composition change for Sm doped samples. The typical transitions of Sm³⁺ at 564, 601, 648 and 707 nm due to ⁴G_5/2→⁶H_J/2 (J = 5, 7, 9 and 11) transition under the excitation of 404 nm were detected. The PL intensity is affected by the Sr/Ca ratio and Sm concentration, and the optimal concentration of Sm is 0.8 mol% when Sr/Ca ratio equals 7/3. The non-radiative transitions and energy transfer of Sm ions are the main reason for the quenching, and the interactions among ions are ascribed to dipole–dipole type by theoretical calculation. Besides, the ratio of PL intensity between 601 and 648 nm (r_O/R = I_{601 nm}/I_{648 nm}) indicates the symmetry and substitution process of Sm ions to Ca/Sr ions. The fluorescence lifetime (τ) decreases with the concentration of Sm increasing, which is the result of the decrease of distance and the enhanced interaction between Sm ions. The CIE chromaticity coordinates and luminescence color of samples are in the orange-red region and have close relation with the concentration of Sm. Furthermore, the cytotoxicity evaluation and confocal laser scanning microscopy (CLSM) observation of samples via cells indicate the good biocompatibility and safe use of this kind of bio-based luminescent materials for their potential efficient fluorescence labeling and detection.