稀土掺杂上转换发光玻璃陶瓷的制备及性能

实验制备了一类含有SrF2∶Yb3+,Tm3+及SrF2∶Yb3+,Er3+的透明发光玻璃和玻璃陶瓷,对比研究了热处理工艺对玻璃陶瓷相组成、微观结构和光谱性能的影响规律。研究表明,玻璃陶瓷具有立方SrF2纳米晶相均匀分布于玻璃基体的复相结构,利用HRTEM可观测到SrF2纳米晶相的(111)晶面,其晶粒尺度在10~30nm之间,且该析晶相中富集有Yb3+/Tm3+和Yb3+/Er3+。基于此,玻璃陶瓷在980nm LD激光激发下的上转换发光强度较玻璃样品有较大提高。其上转换发光机制分别主要为Yb3+-Yb3+之间的合作上转换,Yb3+-Tm3+和Tm3+-Tm3+之间的交叉弛豫能量传递过程,以及Yb3+-Er3+之间的能量传递上转换。     

掺Er3+的20PbF2-20GaF3-15InF3-20CdF2-15ZnF2-10SnF2玻璃系统的上转换发光性质研究

制备了掺Er3+的20PbF2-20GaF3-15InF3-20CdF2-1 5ZnF2-10SnF2玻璃系统,研究了Er3+离子含量的变化对玻璃上转换发光性能的影响,探讨了761nm激发下玻璃上转换发光的机理.结果表明,在761nm激发下,可以观察到很强的408nm紫色荧光,并且同时观察到了545nm和523nm的绿色荧光.为掺稀土重金属氟化物玻璃应用于短波长上转换激光器提供了依据.     

铒单掺和铒/镱共掺氟氧玻璃的上转换发光性质研究

研究了室温下掺不同摩尔分数Er3+单掺和Er3+/Yb3+双掺的20GaF3-15InF3-17CdF2-15ZnF2-10SnF2-3P2O5-(20-x-y)PbF2-xErF3-yYbF3(x=0.1~0.4,y=1~4)氟氧玻璃的上转换发光性质。755nm激发下,在Er3+单掺系列玻璃中观察到紫色(410nm)、蓝色(465nm)和绿色(522nm、544nm)上转化发光,随着掺杂Er3+浓度的增大,各荧光强度增幅有变缓的趋势。980nm激发下,由于Yb3+的敏化作用,在Er3+/Yb3+双掺系列玻璃中观察到绿色(548nm、527nm)和红色(661nm)上转换发光,固定Er3+浓度,随着Yb3+浓度的增大,各荧光强度先增大后减小,当Yb3+、Er3+掺杂浓度比为15时发光强度最大。该氟氧玻璃具有比氟化物玻璃更好的抗析晶稳定性,掺稀土离子后在不同波长激发下可观察到明亮的红、绿色上转换荧光,是一种有潜质用于红、绿色上转换发光的材料。     

Er3+离子掺杂透明的LaF3-SiO2纳米玻璃-陶瓷的上转换发光

采用溶胶-凝胶法成功制备了一系列Er3 掺杂的透明纳米LaF3-SiO2玻璃-陶瓷样品,并研究了其上转换发光性质与发光机制.研究得到了Er3 浓度对上转换发光的影响规律,拟合了上转换荧光强度与LD工作电流的关系,发现所得结果与理论值能够很好地一致.在980nm激光二极管激发下,获得了发射波长为520、540、660nm的有效上转换发光.在较低的功率泵浦下,540nm波长的绿光波段发射最强,其发光主要过程是处于4F7/2态的Er3 离子能量大部分被弛豫到4S3/2态,再由此激发态跃迁到基态4I15/2态所致.     

Er~(3+)掺杂透明微晶玻璃光谱性质的研究

通过高温熔融法和热处理制备了含有-γBi2WO6纳米晶的Er3+掺杂透明硼铋酸盐微晶玻璃.根据X射线粉末衍射结果和Scherrer公式计算得到-γBi2WO6晶粒大小约为15 nm.由于部分Er3+离子取代Bi3+进入-γBi2WO6纳米晶相中,使得Er3+离子在1.5μm的有效发射带宽由78 nm增加到85 nm,同时Er3+离子在4I13/2能级的荧光寿命由0.67 ms增加到1.43 ms.此外,与原始玻璃相比,在Er3+掺杂硼铋酸盐微晶玻璃中观察到强烈的绿光上转换发光,其上转换发光机制可以归为双光子过程.     

OH^-对掺Er^3＋/Yb^3＋钡镓锗玻璃发光的影响及除水研究

钡镓锗玻璃是一种优质的红外发光材料,而钡镓锗玻璃中少量OH-的存在严重影响玻璃的结构并劣化了玻璃的发光性能.实验研究了在原料中引入氟化物除水和在引入氟化物的基础上进行反应气氛法除水两种方法对Er3+/Yb3+共掺钡镓锗玻璃上转换发光、1.53μm发光的影响,采用Frster-Dexter半经验简化模型分析了OH-和Er3+之间的能量转移几率.结果表明:在引入氟化物的基础上进行反应气氛法除水可以将玻璃中的OH-浓度降低到原来的1/11;随OH-浓度的降低,上转换荧光比1.53μm发光增强更明显,545nm绿光增强了2.8倍;OH-和Er3+之间的能量转移常数为1.75×10-19cm4/s,该值比磷酸盐玻璃中OH-和Er3+之间的能量转移常数稍大.     

Er~(3+)/Yb~(3+)/Tb~(3+)共掺氟氧锗酸盐玻璃上转化发光性质及机理研究(英文)

在980nm激发下,研究了Er3+、Yb3+和Tb3+单掺或共掺氟氧锗酸盐玻璃的上转换发光性质和机理.室温下,观察到了强的绿色和红色上转换发光,其发光中心位于524、546和658nm处,分别对应于Tb3+离子的5D4→7FJ(J=5和0)和Er3+离子的(2H11/2、4S3/2和4F9/2)→4I15/2跃迁.研究了TbF3、YbF3掺杂浓度以及激光功率对上转换发光强度的影响,讨论了Er3+、Yb3+和Tb3+之间的能量传递和上转换机理.     

稀土掺杂TiO2在1064nm激光激发下的上转换发光

为研究TiO2材料的上转换发光特性,采用溶胶-凝胶与共沉淀法制备了La3+、Yb3+和Er3+稀土离子掺杂的TiO2粉末.利用SEM和XRD表征发光材料的结构,探讨了试样在1064nm激发光源常温激发作用下,稀土氧化物的掺杂比例、煅烧温度对上转换发光特性的影响.实验表明,1064nm激光常温激发TiO2基掺杂稀土La2O3、Yb2O3、Er2O3的最佳比例为39∶ 10∶1,经1300℃煅烧可制备出明亮绿色发光的上转换材料.     

Er~(3+)/Yb~(3+)共掺SrF_2纳米晶的溶剂热合成及发光性能研究

采用溶剂热方法制备得到了Er3+和Yb3+共掺杂的SrF2纳米晶,并对其上转换发光性能进行了研究.X-射线衍射结果表明所制备的产物为纯的SrF2.随着溶剂热温度的升高,该纳米晶衍射峰的强度逐渐增强,且与SrF2的标准衍射峰相比,所有衍射峰均向高角度偏移.TEM的结果表明,溶剂热处理后,SrF2颗粒的分散性得到明显改善,且晶粒大小随着溶剂热温度的升高而增大.在980nm激光泵浦下Er3+和Yb3+共掺杂SrF2纳米晶仅能观察到弱的上转换发光,而在500℃和600℃热处理2h后,其上转换发光强度明显增强.上转换发光强度与泵浦功率的关系表明绿光和红光均为双光子吸收过程.     

20GaF3-15InF3-20CdF2-15ZnF2-18PbF2-10SnF2-2TmF3玻璃光谱性质研究

制备了掺Tm^3 离子GICZPS玻璃：20GaF3-15InF3-20CdF2-15ZnF2-18PbF2-10SnF2-2TmF3，用Judd-Ofelt理论计算了玻璃的光学参数，研究了玻璃的发光性质，并探讨了其发光机理．结果表明，在641nm激发下，可以观察到485nm(^1G4→^3H6)和528nm(^1G2→^3H5)两个上转换荧光发射峰。     

975 nm脉冲激励下铋酸盐玻璃中铒离子荧光的动态响应

用高温熔融退火法制备了组分为Bi_2O_3-B_2O_3-SiO_2掺铒铋酸盐玻璃,测试分析了铋酸盐玻璃中铒离子的光谱特性,着重研究了975nm脉冲泵浦光激励下1.5 μm波段荧光的动态响应.研究表明,对应脉冲泵浦光上下边沿,铒离子荧光存在着一个上升和下降响应过程,响应速率取决于4I13/2能级Er~(3+)离子荧光寿命.随着B_2O_3组分含量的提高,玻璃中OH基引起的能量传递导致Er~(3+)离子荧光寿命相应减小,荧光响应随之相应加快.     

Li~+共掺杂对掺Er~(3+):TiO_2上转换发光的增强作用·

采用非水性溶胶-凝胶法制备了0.1%Er~(3+)(摩尔分数,下同)、0%～2%Li~+共掺杂TiO_2粉末,在980nm半导体激光器(LD)激发下获得了中心波长526nm、550nm的绿色和663nm的红色上转换发光.Li~+共掺杂对掺Er~(3+):TiO_2的相结构未产生影响,但极大增强了上转换发光强度.随Li~+共掺杂摩尔分数的逐渐增大,绿色和红色上转换发光强度先增大后减小,当Li~+摩尔分数为1%时,上转换发光强度达到最大,绿色和红色上转换发光强度分别比掺Er~(3+):TiO_2提高了约330倍、30倍和60倍.Er~(3+)Li~+共掺杂TiO_2粉末的绿色和红色上转换发光均为双光子吸收过程.Li~+共掺杂不改变Er~(3+)的上转换发光机制,但破坏了Er~(3+)的局部晶体场对称性,影响了Er~(3+)内部4f能级的跃迁几率,导致上转换发光强度增强.     

热处理制度对Pr3+-Yb3+掺杂氟氧微晶玻璃光谱特性的影响

氟氧化物微晶玻璃具有良好的机械性能、化学稳定性和优异的发光性能,是作为量子剪裁的理想介质材料。本文选择55SiO2-5Na2O-20Al2O3-20CaF2作为稀土掺杂的基础玻璃,通过对玻璃进行不同的热处理从而获得了不同的Pr3+-Yb3+共掺微晶玻璃。通过吸收光谱、发射光谱和荧光衰减曲线的比较,发现升高热处理温度或延长保温时间会导致近红外区域的发射峰增强,Pr3+的荧光寿命降低,且计算表明,Pr3+-Yb3+之间的能量传递效率增加了。     

White Light Emission Characteristics of Tb~(3+)/Sm~(3+) Co-Doped Glass Ceramics Containing YPO_4 Nanocrystals

The Tb~(3+)/Sm~(3+) single-doped and co-doped glasses and glass ceramics containing YPO_4 nanocrystals have been synthesized by melt quenching method. The structural and luminescent properties of these glass specimens were investigated. Under 375 nm wavelength excitation, the emission spectra combined with blue, green and red bands were observed, which achieved the white light emission. Moreover, the energy transfer between Tb~(3+) and Sm~(3+)ions was validated by decay lifetime measurement and energy level diagram.The color coordinates(x = 0.333, y = 0.333), correlated color temperature(5595 K) and the color rendering index(Ra = 80.5) indicated that the glass ceramics were considered to be good lighting source. Hence,the YPO_(4-) based Tb~(3+)/Sm~(3+) co-doped glass ceramics can act as potential matrix materials for white lightemitting diodes under ultraviolet excitation.     

Enhanced emissions of Eu(3+) by energy transfer from ZnO quantum dots embedded in SiO(2) glass

SiO(2):Eu(3+) based bulk composites containing ZnO quantum dots were synthesized by an in situ sol-gel process. The quantum dots homogeneously distributed among the SiO(2) glass matrix exhibited a broad ultraviolet emission band centered at 385?nm. The ZnO ultraviolet luminescence intensity decreased monotonically with increasing Eu(3+) doping concentration, while the Eu(3+) visible emission was intensified significantly by the precipitation of ZnO quantum dots, ascribed to the energy transfer from ZnO to Eu(3+). The Eu(3+) luminescence at 612?nm for the sample with 20?mol% ZnO was about ten times stronger than that for the sample without ZnO. The influence of ZnO or Eu(3+) concentration on the energy transfer process is discussed.     

稀土掺杂复式钨酸盐纳米晶体的制备及发光性能

应用水热合成技术制备了稀土掺杂复式钨酸盐NaRe（WO4）2（Re=La,Y,Gd）纳米晶体,水热合成温度随Re^3＋种类的不同而呈现较大的差异.稀土离子在NaRe（WO4）2纳米晶体中处于非反演对称中心位置.在980nm红外光激发下,Yb^3＋和Er^3＋共掺的NaRe（WO4）2纳米晶体可产生明显的绿色上转换发光,发光机理为双光子过程.     

高分子网络凝胶法制备YAG:Er~(3+)纳米晶粉体及其光谱性质

采用高分子网络凝胶法,在较低温度下制备了YAG:Er~(3+)纳米晶粉体.分别用热重-差热分析(TG-DSC)、X射线衍射(XRD)、扫描电子显微镜(SEM)以及激发和发射光谱对样品进行了表征.结果表明:石榴石晶相的形成温度为880℃,与YAG纳米晶粉体相比,用Er~(3+)代替Y~(3+)后,YAG:Er~(3+)纳米晶粉体还是以石榴石晶相为主,未发生明显变化;YAG:Er3~(3+)纳米晶粉体有丰富的吸收谱线,并且在260nm激发光激发下YAG:Er~(3+)纳米晶粉体可以发射出377nm紫光,可以作为紫光光源的考虑对象.     

掺Er~(3+)重金属氧氟锗酸盐玻璃光谱性质研究

研究了重金属氧氟锗酸盐玻璃中Er3+离子的吸收光谱、有效吸收和发射线宽、荧光光谱、荧光半高宽、荧光寿命、带宽特性和增益性能.应用Judd-Ofelt理论计算了Er3+离子的强度参数Ωt(t=2,4,6),应用McCumber计算了能级4I13/2→4I15/2跃迁的吸收和受激发射截面.结果显示,随PbF2含量增加,Er3+离子的强度参数Ω6,吸收线宽、发射线宽、荧光半高宽、荧光寿命、带宽特性和增益性能都增加.表明掺Er3+重金属氧氟锗酸盐玻璃可作为宽带光纤放大器潜在的基质材料.     

Site-selective spectroscopy in Sm(3+)-doped sol-gel-derived nano-glass-ceramics containing SnO(2) quantum dots

Nano-glass-ceramics of composition 95SiO(2)-5SnO(2) doped with 0.4 Sm(3+) (mol%) were synthesized by the thermal treatment of precursor sol-gel glasses. Structural and luminescence measurements were carried out. The precipitated SnO(2) nanocrystals in the glass matrix constitute a wide bandgap quantum-dot system with size comparable to the bulk exciton Bohr radius. A site-selective excitation, by energy transfer from the semiconductor host, reveals that a fraction of the Sm(3+) ions are incorporated in the SnO(2) nanocrystals, whereas the rest remains in the silica glassy phase. An evolution in the Sm(3+) emission spectra has been observed when the SnO(2) nanocrystals are excited with different UV wavelengths, which has been ascribed to selective excitation of nanocrystal sets with predetermined size.     

Size-induced crystal field parameter change and tunable infrared luminescence in Ni(2+)-doped high-gallium nanocrystals embedded glass ceramics

Transparent Ni(2+)-doped Li(2)O-Ga(2)O(3)-SiO(2) glass ceramics (GCs) were prepared and characterized. By controlling the size of the nanocrystals, the infrared luminescence is tunable. It could be ascribed to alteration of the crystal field strength Dq of octahedral Ni(2+), which is due to the changes of the lattice parameters. The change in optical signals at telecommunication bands when the seed beam passes through the bulk sample with or without 980?nm excitation was also demonstrated for the first time. The coefficient of the change in optical signals at 1.3?μm is calculated as 0.26?cm(-1). The changes in optical signal have shown similar wavelength dependence on the luminescence property.