溶胶-凝胶法制备La2Ce2O7:Eu3+及其发光性能

采用溶胶-凝胶法（Sol-gel）合成La₂Ce₂O₇:Eu3+系列红色荧光粉,并研究煅烧温度、Eu3+掺杂浓度以及不同种类电荷补偿剂对样品发光性能的影响.通过XRD、SEM、荧光光谱对样品的晶体结构、形貌以及发光性能进行测量和表征.结果表明:实验所得样品主晶相为La₂Ce₂O₇,属于萤石结构. Eu3+及电荷补偿剂的掺杂没有改变其晶体结构.合成的样品在467 nm蓝光激发下发出612 nm的红光.样品的发光强度随煅烧温度以及Eu3+掺杂浓度的提高先增强后减弱,样品的较优的煅烧温度为1 100 ℃,Eu3+较优的掺杂浓度为10 %（摩尔百分比）.掺入电荷补偿剂可以有效增强样品的发光强度,其中掺入Li+后发光增强的效果最显著.      

Yb~(3+),Er~(3+)掺杂Y_2Ti_2O_7荧光粉的制备与上转换发光机理

采用溶胶-凝胶法制备合成了(Y_(0.98-x)Yb_xEr_(0.02))_2Ti_2O_7(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Yb~(3+)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980 nm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Yb~(3+)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.     

Gd3+掺杂增强BaWO4∶Tm3+/Yb3+上转换发光效率及温度传感特性研究

提高发光效率是上转换材料研究中尚需解决的关键问题。通过在BaWO₄∶Tm³⁺/Yb³⁺荧光粉中掺入Gd³⁺,研究其对上转换发光效率和温度传感特性的影响。结果表明,Gd³⁺的掺杂使激活离子Tm³⁺的上转换发光强度显著增强,其中Tm³⁺的蓝光(～485 nm)辐射增强31倍。利用荧光强度比方法研究了基于Tm³⁺的³F_2,3和³H₄两个热耦合能级在313 K～573 K范围内的光学温度传感特性,BaWO₄∶Tm³⁺/Yb³⁺/Gd³⁺测温灵敏度最大值为0.0119 K^-1。可见,BaWO₄∶Tm³⁺/Yb³⁺/Gd³⁺具有高的上转换发光效...     

NaYF4:Yb,Er材料的制备及其上转换发光性能

通过沉淀法制备Yb3+和Er3+共掺的NaYF4上转换发光材料,考察了主要制备工艺条件对材料上转换发光性能的影响,并探讨了其上转换发光的机理。利用x射线衍射(XRD)、透射电镜(TEM)、荧光光谱仪对样品进行了表征。结果表明,Yb3+和Er3+的掺杂浓度分别15%(摩尔分数,下同)、3%,焙烧温度为600℃时可得到发光性能较好的六方相NaYF4:Yb,Er上转换材料,其主要上转换途径是Yb3+和Er3+之间的能量转移,且Er3+的红、绿光发射均为双光子过程。     

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.      

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.      

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.      

NaYF4∶Yb,Er材料的制备及其上转换发光性能

通过沉淀法制备Yb3+和Er3+共掺的NaYF4上转换发光材料,考察了主要制备工艺条件对材料上转换发光性能的影响,并探讨了其上转换发光的机理.利用x射线衍射(XRD)、透射电镜(TEM)、荧光光谱仪对样品进行了表征.结果表明,Yb3+和Er3+的掺杂浓度分别15％(摩尔分数,下同)、3％,焙烧温度为600℃时可得到发光性能较好的六方相NaYF4∶Yb,Er上转换材料,其主要上转换途径是Yb3+和Er3+之间的能量转移,且Er3+的红、绿光发射均为双光子过程.     

溶胶-凝胶法制备Y2Zr2O7∶Tm3+及其发光性能研究

以柠檬酸为络合剂采用溶胶-凝胶法制备了（Y1-xTmx）2Zr2O7（x=0.005,0.01,0.03,0.05）荧光粉.采用X-射线衍射分析仪（XRD）、扫描电子显微镜（SEM）和荧光光谱仪分别检测了Y2Zr2O7∶Tm3+的晶体结构、颗粒形貌以及样品的荧光光谱.XRD图谱表明,所得到的产物Y2Zr2O7∶Tm3+为单一相的萤石结构,而且Tm3+的掺杂并没有改变其晶体结构.荧光光谱的测试表明,在359 nm波长的紫外光激发下,1000℃下烧结的（Y1-xTmx）2Zr2O7（x=0.01）样品的发光性能最好,发射峰对应于Tm3+的1D2→3F4跃迁和1G4→3H6跃迁,并对其发光机理进行了探讨.样品在454 nm处的发光强度随Tm3+离子掺杂浓度的增加先升高后降低,即出现了浓度猝灭的现象,当Tm3+掺杂浓度摩尔百分比为1%时,样品的发光强度达到最大.     

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。      

Spectroscopic investigations on Er3+/Yb3+-doped oxyfluoride glass ceramics containing YOF nanocrystals

Spectroscopic properties of Er3+/Yb3+-doped transparent oxyfluoride borosilicate glass ceramics containing YOF nanocrystals were systematically investigated. X-ray diffraction (XRD) confirmed the formation of YOF nanocrystals in the glassy matrix. Based on the Judd-Ofelt theory, the intensity parameters Ωi (i=2, 4, 6), spontaneous emission probability, radiative lifetime, radiative quantum efficiency and the effective emission bandwidth were investigated. The upconversion luminescence intensity of Er3+ ions in the glass ceramics increased significantly with the increasing crystallization temperature. The transition mechanisms of the green and red upconversion luminescence were ascribed to a two-photon process, and the blue upconversion luminescence was a three-photon absorption process.     

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.      

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.      

Upconversion luminescence of Y2O3:Er3+, Yb3+ nanoparticles prepared by a homogeneous precipitation method

Y2O3: Er3 , Yb3 nanoparticles were synthesized by a homogeneous precipitation method without and with different concentrations of EDTA 2Na. Upconversion luminescence spectra of the samples were studied under 980 nm laser excitation. The results of XRD showed that the obtained Y2O3:Er3 ,Yb3 nanoparticles were of a cubic structure. The average crystallite sizes calculated were in the range of 28-40 nm. Green and red upconversion emission were observed, and attributed to 2H11/ 2,4S3/ 2→4I15/ 2 and 4F9/ 2→4I15/2 transitions of the Er3 ion, respectively. The ratio of the intensity of green emission to that of red emission drastically changed with a change in the EDTA 2Na concentration. In the sample synthesized without EDTA, the relative intensity of the green emission was weaker than that of the red emission. The relative intensities of green emission increased with the increased amount of EDTA 2Na used. The possible upconversion luminescence mechanisms were discussed.     

NaYF4: Yb,Er@SiO2的高温相变及上转换

通过固-液热分解法合成平均尺寸为27 nm的六方相NaYF₄: Yb, Er上转换纳米晶。制备了NaYF₄: Yb, Er@SiO₂核壳纳米粒子, 壳层厚度约为8 nm。将NaYF₄: Yb, Er@SiO₂分别在不同高温下焙烧3 h, 发现600 ℃下产物物相未发生变化, 但向非晶态过渡; 700、800 ℃下NaYF₄内核与SiO₂壳层发生化学反应, 产物物相均转变为NaYSiO₄。样品均用980 nm红外激光进行激发, 显示出强烈的可见光上转换发射。以初始NaYF₄: Yb, Er@SiO₂的上转换发光强度为对比样, 随着焙烧温度的升高, 样品的发光强度依次提高。这与理论上低声子能量的氟化物发光强度更高不符, 可能原因是高温处理后样品去除了部分晶格缺陷和有机杂质。      

Energy transfer in Tb~（3＋）,Yb~（3＋） codoped Lu_2O_3 near-infrared downconversion nanophosphors

Tb3+ and Yb3+ codoped Lu2O3 nanophosphors were synthesized by the reverse-strike co-precipitation method. The obtained Lu2O3:Tb3+,Yb3+ nanophosphors were characterized by X-ray diffraction (XRD) and photoluminescence (PL) spectra. The XRD results showed that all the prepared nanophosphors could be readily indexed to pure cubic phase of Lu2O3 and indicated good crystallinity. The Tb3+→Yb3+ energy transfer mechanisms in the UV-blue region in Lu2O3 nanophosphors were investigated. The experimental results showed that the strong visible emission around 543 nm from Tb3+ (5D4→7F5) and near-infrared (NIR) emission around 973 nm from Yb3+ (2F5/2→2F7/2) of Lu2O3:Tb3+,Yb3+ nanophosphors were observed under ultraviolet light excitation, respectively. Tb3+ could be effectively excited up to its 4f75d1 state and relaxed down to the 5D4 level, from which the energy was transferred cooperatively to two neighboring Yb3+. The Yb3+ concentration dependent luminescent properties and lifetimes of both the visible and NIR emissions were also studied. The lifetime of the visible emission decreased with the increase of Yb3+ concentration, verifying the efficient energy transfer from the Tb3+ to the Yb3+. Cooperative energy transfer (CET) from Tb3+ to Yb3+ was discussed as a possible mechanism for the near-infrared emission. When doped concentrations were 1 mol.% Tb3+ and 2 mol.% Yb3+, the intensity of NIR emission was the strongest.