热处理气氛对铈离子掺杂SiO2发光性能的影响

采用溶胶-凝胶技术制备了Ce3 离子掺杂的SiO2粉体,并在H2、Ar和空气三种气氛中分别进行1000℃保温2h的热处理.采用红外光谱仪、紫外-可见吸收光谱仪以及荧光光谱仪对热处理前后成分以及光学性能进行测试,研究不同气氛中的热处理对SiO2粉体中的Ce3 离子光学性能的影响.结果表明,在H2和Ar气氛中热处理,相对于空气气氛而言,样品的发光强度有明显的增强.其中H2气氛中处理的样品发光强度约为空气气氛中处理样品发光强度的12倍.同时热处理气氛的改变也可以通过影响Ce3 离子配位场使其发光波长产生漂移,氢气中处理的样品发光峰位于435 nm,氩气中处理的样品发光峰位于455 nm,而空气中处理的样品发光峰位于445 nm.     

柠檬酸螯合法制备BaHfO3:Ce3+纳米材料及其发光特性

通过柠檬酸螯合法合成BaHfO3:Ce3+纳米粉体.采用TG-DTA、XRD、SEM等手段对粉体进行了表征,用荧光光度仪分析样品的激发光谱和发射光谱.结果表明:在CA:EG=1:3的条件下得到干凝胶前驱体,经1050 ℃煅烧2 h,合成出结晶度高、近似球形、粒径尺寸约为40 nm的BaHfO3:Ce3+纳米粉体.Ce3+掺杂浓度为0.9 mol%的BaHfO3:Ce3+样品激发光谱和发射光谱的相对强度最大.激发光谱有两个较宽的谱带,发光峰值分别在393和445 nm波长处最大.样品在393和445 nm的发射光谱都是由两个发光带组成,在530和590 nm波长处存在最大峰值,对应掺杂Ce3+的5d→2F5/2和5d→2F7/2发光跃迁.然而这两条发射光谱有明显不同,这是因为Ce3+离子的4f基态由两个能量差约为2000 cm-1的能级组成.     

溶胶-凝胶工艺制备SrTiO3:Pr,Ce红色荧光粉及其发光性能研究

通过溶胶-凝胶法结合热处理工艺合成了SrToO3:Pr3 红色荧光粉,研究了共掺Ce离子及其浓度变化对荧光粉发光强度的影响规律.采用X-射线衍射分析(XRD),傅里叶变换红外光谱(FT-IR)和荧光光谱仪(PL)等测试手段对前驱体及热处理样品的相形成过程、物相组成及样品的发光性能进行了测试与表征.荧光光谱测试发现,热处理样品在615nm处存在一个强的红色发光峰,可归属于Pr3 的1D2→3H4跃迁;而激发谱则由一个主峰位于348 nm处的宽带激发带和一系列强度较弱的窄峰构成,分别归属于Pr3 的4f-5d带间跃迁和4f-4f(3H4-4PJ,J=0,1,2和3H4-1D2)跃迁过程.对掺杂不同浓度Ce离子制备的共掺SrTiO3:Pr3 ,Ce荧光体发光性能的研究结果表明,随着掺杂Ce浓度的增加,荧光体发光强度依次下降,对该现象的相关作用机制进行了讨论.     

稀土对ZAlSi12Cu2Mg1陶瓷层性能的影响

通过在Na2SiO2电解液体系中同时添加0．2g／L的Ce^3＋和不同含量的La^3＋以调整电解液组成，研究了Na2SiO3电解液中添加稀土离子对ZAlSi12Cu2Mg1合金微弧氧化陶瓷层相结构和力学性能的影响。结果表明，电解液中添加Ce^3＋和La^3＋，可以显著提高陶瓷层质量，其中添加0．2g／L的Ce^3＋和0．3g／L的La^3＋，所得陶瓷层主要由α—Al2O3、γ-Al2O3、Al2SiO3和非晶相组成，陶瓷层厚为157μm，硬度（HV）为947，经6000r磨损后，ZAlSi12Cu2Mg1合金基体的磨损量为102．2mg，而陶瓷层S1磨损量为19．7mg，仅为铝合金基体的19％。     

空气中退火对钨酸铅纳米晶的影响

以钨酸钠和醋酸铅为原料,加表面活性剂聚乙二醇200,合成钨酸铅纳米晶。合成的样品呈淡黄色,这是由于样品中存在铅空缺和氧空缺导致的。对样品进行X射线和红外分析及透射电子显微镜分析,结果表明:样品结晶良好,粒径在10～20nm之间。将样品在不同温度下退火2h,研究空气中退火对性能的影响。结果表明:在600℃和700℃退火2h后,样品X射线和红外图谱中出现非特征峰;随着退火温度的升高,样品颗粒度变大。样品的光致发光谱中出现蓝色、绿色和红色发光带,随着退火温度的升高,强度增加。在700℃退火2h后,样品颜色变为白色,绿色发光带消失。     

BaHfO3:Ce闪烁陶瓷的制备及发光性能

通过掺杂摩尔分数为0.3%的稀土Ce3+,制备了BaHfO3:Ce闪烁陶瓷,用XRD,TG-DSC,SEM及TEM表征了BaHfO3:Ce物相及形貌,研究了不同烧结工艺下BaHfO3:Ce的致密化及显微组织.结果表明:前驱体的晶化转变存在三个阶段,在900℃煅烧2 h合成出BaHfO3:Ce纳米粒子,形貌为近球状,粒径尺寸约为15 nm.经真空烧结与常压烧结的样品致密化和显微组织存在明显差异:前者在1750℃真空烧结保温1.5 h,样品基本致密化,晶粒尺寸在40-50 μm范围内;而后者晶粒尺寸分布离散性较大.真空烧结后的闪烁陶瓷和同组分粉体样品在530 nm波长的激发光谱中分别存在380-420 nm紫色和420-450 nm蓝色的发光谱带,在391,398和445 nm波长处均出现较强峰值,对应着Ce3+4f→5d能级跃迁的吸收,这表明该闪烁陶瓷的发光强度高于同组分粉体样品.     

Y2SiO5:Ce3+/PMMA稀土发光复合材料的制备及其荧光性能的研究

采用原位聚合法,将蓝色荧光粉(Y2SiO5:Ce3+)和聚甲基丙烯酸甲酯(PMMA)复合,制备出透明且具有蓝色荧光性能的Y2SiO5:Ce3+/PMMA稀土发光复合材料.利用X射线衍射仪(XRD)和傅里叶红外吸收光谱仪(FT-IR)对样品进行结构分析;用扫描电镜(SEM)对样品进行微观形貌观察;用荧光光谱测试仪和紫外-近红外分光光度计对样品的荧光性能和透射光谱进行分析.结果表明:具有X2型单斜晶体结构的Y2SiO5:Ce3+蓝色荧光粉在PMMA中分布均匀,其粒度为0.7～2.0μm.在波长为365 nm紫外光激发下,Y2SiO5:Ce3+/PMMA复合材料能够发射出蓝色荧光,且0.1mol％ Y2SiO5:Ce3+含量的PMMA基复合材料的蓝色荧光透光率高达75％.这表明所制备的Y2SiO5:Ce3+/PMMA复合材料具有良好的蓝色荧光性能,可用于透明固体发光器件的研制.     

Ce~（3＋）,Tb~（3＋）激活的Ln（BO_3,PO_4）绿色荧光粉的合成与真空紫外光谱特性

针对目前PDP用商品绿粉余辉时间较长,以及合成稀土硼酸盐与稀土磷酸盐工序长、能耗高等缺点,本研究以自制的磷酸硼（BPO4）和稀土氧化物为原料,采用一步烧成法合成了结晶良好的Ce3＋、Tb3＋激活的Ln（BO3,PO4）（Ln=La,Y,Gd）绿色荧光粉,并对其在147 nm激发下的光谱性质进行了研究。结果表明：Ln（BO3,PO4）：Ce3＋、Tb3＋（Ln=Y,La,Gd）激发光谱是由来自BO33-和PO43-基质敏化带的120~175 nm和来自Tb3＋离子的4f→5d跃迁的多宽带的175~300 nm组成;改变基质稀土离子,发射光谱中的荧光分支比和色坐标也随之改变,其中以Gd（BO3,PO4）：Ce3＋、Tb3＋荧光粉的荧光分支比为最高;拟合Gd（BO3,PO4）：Ce3＋、Tb3＋荧光粉的衰减曲线后,得出其荧光寿命为2.92 ms,10%的余辉为6.7 ms,优于Zn2SiO4∶Mn2＋商品粉,能够满足PDP器件的要求。     

中频反应磁控溅射制备Al2O3:CeCl3薄膜及其光致发光特性

应用中频反应磁控溅射技术制备了Al2O3:CeCl3的非晶薄膜.Ce3+含量和薄膜的化学成分通过X射线散射能谱(EDS)测量.薄膜试样的晶体结构用x射线衍射分析.俄歇电子谱用于对薄膜材料的化学组分进行定性分析.薄膜的光致发光峰是在370 nm到405 nm范围内,它们来自于Ce3+离子的5d1激发态向基态4f1的两个劈裂能级的跃迁.发光强度强烈地依赖于薄膜中的掺杂浓度和沉积时的基片温度.薄膜发光来自于氯化铈分子中的发光中心,而不是其他的掺杂Ce3+离子.随铈含量增加,光致发光峰向低能方向移动,可能与薄膜中存在氯元素有关.     

Fe^3＋／Ce^3＋掺杂纳米TiO2的制备及光催化性能研究

采用溶胶-凝胶法制备了不同粒径的纯纳米TiO2和掺杂Fe^3＋和Ce^3＋的纳米TiO2。样品的X射线衍射（XRD）和透射电镜（TEM）表征说明：在相同的制备条件下，掺杂可以减小粒子粒径，掺Fe^3＋和Ce^3＋可以抑制晶相转变。光催化降解NO2的结果表明，在相同的制备方法和掺杂量的条件下合成的光催化剂对亚硝酸盐的降解率由高到低的顺序为：掺铁TiO2〉掺铈TiO2〉TiO2。     

Luminescence properties of sol–gel derived Sr2(Ce1−xSnx)O4 blue phosphors

Monophasic Sr₂(Ce_1?xSn_x)O₄ phosphors (x = 0–0.07) were prepared via the sol–gel process. A broad excitation band ascribed to the Ce⁴⁺–O^2? transition was observed in the range of 200–450 nm. With doping Sn⁴⁺ ions into the host, the intensity of the low-energy peak enhanced remarkably due to a decrease in crystal field. The intensity ratio of the low-energy peak to the high-energy peak increased with the amount of Sn⁴⁺ ions doped. Moreover, the red shift of the excitation peaks was observed due to an increase in the bond length of Ce–O. Upon excitation at around 346 nm, the intensity of the blue emission peak peaking at 483 nm was enhanced with doping Sn⁴⁺ ions. The doping of tin ions was found to significantly improve the luminescence characteristics of the prepared phosphors when they were excited under UV light.     

High yield luminescence of a novel europium complex by excimer excitation and f–f absorption of Eu

A new organic ligand, 2-allyl-1,3-diphenyl-1,3-propanedione (ADP), and the corresponding quaternary Eu³⁺ complex, bi (ADP) (dibenzoyl methane) (1,10-phenanthroline) europium(III) [Eu(ADP)₂(DBM)(Phen)] have been synthesized. Excellent red luminescence from the Eu³⁺ complex was observed excited at 419 nm, and the broad visible excitation band is attributed to excimer absorption. The luminescence quantum yield excited at 419 nm (34 ± 3%) was higher than that at 380 nm (30 ± 3%). This is the first time to find strong and high yield excimer excitation absorption for a europium complex at room temperature, therefore, the excimer absorption band located in visible region (400–500 nm). Moreover, very high yields of direct f–f excitation absorption of Eu³⁺ ions at 466 nm (104 ± 10%) and 536 nm (96 ± 10%) were firstly observed, and the excitation spectrum for the europium complex in solid state is extended in wide region from 220 nm to 580 nm.     

Improving color rendering index of Mn-doped ZnO nanorods on silicon-based substrate

Porous silicon pillar array(PSPA) samples which are ideal substantial materials with dominant electronic and luminescence properties were prepared by surface etching method. ZnO nanorods with or without Mn doping grown uniformly and aligned onto PSPA regardless of lattice matching show various photoluminescence(PL)properties. The doped Mn ions in ZnO nanorods were directly observed by X-ray photoelectron spectroscopy(XPS),and ZnO structures were detected by X-ray diffraction(XRD). As the doping concentration increases,XRD peaks of ZnO nanorods shift to low angle. The influences of doping Mn ions on luminescence properties of ZnO nanorods were investigated. Except for the ultraviolet(UV) PL band, the broad PL band is observed at visible region. The band could be divided into three separate bands(orange, green and red) by Lorentzian deconvolution. The intensity of orange PL band firstly increases then decreases, and then gets the maximum at the doping Mn-to-Zn molar ratio of 2.0:100.0 which is the most effective doping concentration. The green PL band is attributed to zinc vacancy of ZnO, the orange PL band to Mn ions recombination of itself, and the red PL band to oxygen vacancy of ZnO, respectively. As the Mn-doped ZnO nanorods could emit yellow green luminescence excited by UV radiation, and doped Mn ions could improve the color rendering index of the luminescence, the nanorods could be used as promising white-light emitters in the future.     

Luminescence based on energy transfer in xerogels doped with Ln2−xTbx(WO4)3

This paper presents preparation, optical absorption and photoluminescence properties of luminescent materials consisting of Ln_2−xTb_x(WO₄)₃ [where Ln = Gd(III) or La(III)] incorporated into silica xerogel. Photoluminescence behaviour of the salt in the rigid matrix was studied by the luminescence spectroscopy. The excitation spectra of the system Ln_2−xTb_x(WO₄)₃ show an intense broad band with a maximum placed at about 240 nm. This band is attributed to ligand–metal charge transfer (LMCT) inside the tungstate group. On the other hand, Tb³⁺ ion exhibits its characteristic emission in the material. Owing to energy transfer from the excited tungstate groups to the Tb³⁺ ions the emission intensity is improved. The energy transfer from WO₄²⁻ group to Tb(III) ion is particularly effective for such dopants as Gd_0.4Tb_1.6(WO₄)₃ or La_0.8Tb_1.2(WO₄)₃ incorporated into SiO₂ xerogel. Concentration of the emission quenchers such as water molecules and OH groups was reduced by thermal treatment. The high emission intensity and easy preparation of these systems make them potential candidates for application as luminescent materials.     

UV and VUV optical excitations in wide band gap materials doped with rare earth ions: 4f–5d transitions

From the point of view of luminescence applications, large band gap materials such as fluoride compounds are suitable matrices into which a small concentration of foreign ions called activators can be incorporated. To improve the knowledge of the optical properties of the overall system, the investigation of the different interactions of UV and VUV electromagnetic radiations with the condensed matter was undertaken. The excitation of the luminescence induced in rare earth ion activators doped in LiYF₄, LaF₃ and YF₃ was recorded in a wide continuous spectral region from 5 to 15 eV using synchrotron radiation as a photon source. The main interest of this work was focused on the localization in energy of the different photon absorption mechanisms occurring in these fluoride compounds doped with rare earth ions.     

Spectroscopic properties of Yb and Er ions in heavy metal glasses

Selected heavy metal glasses containing Yb³⁺ and Er³⁺ ions have been studied. Near-infrared luminescence spectra at 1.53 μm and up-conversion spectra of Er³⁺ ions were registered under excitation of Yb³⁺ ions by 975 nm diode laser line. The luminescence bands correspond to ⁴I_13/2-⁴I_15/2 (NIR), ⁴S_3/2-⁴I_15/2 (green) and ⁴F_9/2-⁴I_15/2 (red) transitions of Er³⁺, respectively. The optical transitions of rare earth ions have been examined as a function of glass host. The unusual large spectral linewidth nearly close to 110 nm for ⁴I_13/2-⁴I_15/2 transition of Er³⁺ ions in Yb-Er co-doped lead borate glass was obtained, whereas long-lived NIR luminescence at 1.53 μm was detected in lead germanate glass. The NIR luminescence and up-conversion phenomena strongly depend on stretching vibrations of glass host, which was confirmed by FT-IR spectroscopy.     

Preparation and characterization of Eu^3＋-doped CaCO3 phosphor by microwave synthesis

A Eu³⁺-doped CaCO₃ phosphor with red emission was prepared by microwave synthesis. The scanning electron microscopy (SEM) image and laser particle size analysis show that the CaCO₃:Eu³⁺ particles are needle-like in the length range of 5.0–10.0 μm. The results of X-ray diffraction (XRD) analysis, Fourier transform infrared spectroscopy (FT-IR), and Raman spectroscopy indicate that pure aragonite CaCO₃:Eu³⁺ is prepared using microwave irradiation and the Eu³⁺ ion as a luminescence center inhabits the site of Ca²⁺. The photoluminescence excitation (PLE) spectrum shows that the strong broad band at around 270 nm and weak sharp lines in 300–550 nm are assigned to the charge transfer band of Eu³⁺-O²⁻ and intra-configurational 4f-4f transitions of Eu³⁺, respectively. The photoluminescence (PL) spectrum implies that the red luminescence can be attributed to the transitions from the ⁵D₀ excited level to the ⁷F _J (J = 0, 1, 2, 3, 4) levels of Eu³⁺ ions with the mainly electric dipole transition ⁵D₀ → ⁷F₂ (614 and 620 nm), and the Eu³⁺ ions prefer to occupy the low symmetric site in the crystal lattice.     

Influence of the Nd3+ ions content on the FTIR and the visible up-conversion luminescence properties of nano-structure BaTiO3, prepared by sol–gel technique

The nano-structure BaTiO₃ (BT) powder doped with different concentrations of Nd³⁺ ions were annealed at 750 °C for 1 h to form nano-structure tetragonal phase of BT powder. The structure properties studied using XRD and FTIR methods. Sensitized up-conversion luminescence observed under excitation of 808 nm diode laser, suggesting that the Nd³⁺ ions-doped BT might be an ideal up-conversion material for infrared excitation. The influence of increasing the concentration of the Nd³⁺ ions on the luminescence intensity investigated using laser diode. The up-conversion mechanisms in the doped system will be discussed by analyzing the energy level structures of the Nd³⁺ ions.     

白光LED用新型Eu或Gd共掺杂的Ce:YAG单晶荧光材料的光谱性能研究

开展了白光LED用新型YAG单晶荧光材料的制备和光谱性能研究,采用提拉法生长Eu,Ce:YAG及Gd,Ce:YAG晶体,并通过吸收光谱,激发、发射光谱及电光性能等对晶体材料的光谱特性进行表征。结果表明,Eu或Gd共掺杂的Ce:YAG单晶荧光材料均可以被波长460nm左右的蓝光芯片有效激发,产生一个范围为480～650nm的宽峰发射。Eu3+或Gd3+共掺杂会对Ce3+离子的发光产生影响:Eu3+离子的掺杂,会对Ce3+离子的发光产生淬灭效应;而Gd3+离子取代基质Y3+离子可以使Ce3+离子的发射峰发生红移。     

溶剂热法合成YAG:Ce荧光粉体的研究

采用溶剂热法,以乙二胺为溶剂,碳酸氢铵沉淀法制备的沉淀产物为前驱体,在低温下合成了YAG:Ce荧光粉体.研究了反应时间对合成产物的组成、分散性以及荧光性能的影响,结果表明:在200 ℃低温保温5 h条件下,可得到颗粒尺寸为260～280 nm的球形YAG:Ce颗粒,颗粒尺寸均匀,且分散性好;荧光性能表征显示,其发射光谱为一宽带,峰值在530 nm附近,对应于Ce~(3+)的最低5d能级到4f能级跃迁所发出的光,可与高效蓝光LED匹配制备双基色白光LED,用于新型节能光源.