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.     

Er~(3+)/Yb~(3+)共掺四种玻璃中上转换发光效率的比较及研究

计算了在Er3+/Yb3+共掺的硅酸盐、锗酸盐、磷酸盐和氟化物这四种玻璃基质中施主离子归一化荧光线形函数与受主离子归一化吸收线形函数的重叠积分,交叉弛豫几率.通过求解能级跃迁速率方程,得出4S3/2能级的相对布居数.定义了上转换发光效率可以用自发辐射跃迁几率A61和4S3/2能级的相对布居数之积来表征.分析了由于氟化物中4S3/2能级的无辐射跃迁几率较小而自发辐射跃迁几率较大,因此4S3/2能级有较大的相对布居数,在四种Er3+/Yb3+共掺的玻璃中,氟化物具有较好的上转换发光效率.     

掺铒氧氟碲酸盐玻璃的上转换发光研究

研究了掺铒氧氟碲酸盐玻璃的吸收光谱和上转换发光光谱，分析了Er^3 离子在氧氟碲酸盐玻璃中的上转换发光机理．结果表明：通过975nm的激光二极管(LD)激发，在室温下同时观察到强烈的绿光(524和545nm)和红光(655nm)，分别是由于Er^3 离子^2H11／2→I15／2，^4S3／2→I15／2，和^4F9/2→I15／2跃迁．随PbF2含量增加，绿光的发光强度增加趋势较小，而红光的发光强度增加趋势大于绿光．上转换发光机理主要涉及能量转移和激发态吸收，强烈的绿光和红光激发都是由于双光子吸收过程．     

OH-对掺Er3+/Yb3+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Forster-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.     

PbO对Tm3+/Ho3+/Yb3+共掺碲酸盐玻璃三基色上转换发光的影响

用高温熔融法制备了Tm3+/Ho3+/Yb3+共掺碲酸盐玻璃,在TeO2-ZnO-La2O3玻璃组分的基础上,引入声子能量较低的PbO,研究了PbO对基质样品拉曼光谱以及Tm3+/Ho3+/Yb3+共掺样品上转换发光光谱的影响.结果表明,随着PbO含量的增加,样品的最大声子能量下降比较明显,同时样品的声子态密度也有减小趋势;在975nm波长激光二极管(LD)激励下,随着PbO含量的增加,Tm3+/Ho3+/Yb3+共掺样品上转换蓝光(480nm)、绿光(546nm)和红光(662nm)的发光强度都有明显增强,且PbO的引入对上转换蓝光发光强度的影响要大于其对绿光和红光的影响.     

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+/Ho3+共掺GeS2-In2S3-CsI玻璃上转换发光和能量传递研究

用熔融急冷法制备了系列Er3+/Ho3+共掺80GeS2-10in2S3-10CsI硫卤玻璃,测试了样品的状态稳定性、拉曼光谱、吸收光谱以及上转换光谱.在该样品中出现了强烈的绿光(526、549nm)和红光(660nm),分别对应于2H11/2-4I15/2(Er3+)、4S3/2→4I15/2(Er3+)十5S2(5...     

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.     

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.     

OH- 对 Tm3+/Yb3+ 共掺碲酸盐玻璃上转换发光的影响

研究了Tm3 /Yb3 共掺碲酸盐玻璃的Raman光谱、红外光谱和上转换发光光谱,分析了OH-对Tm3 上转换发光的影响。结果表明,氧氯碲酸盐玻璃的声子能量高于氧氟碲酸盐玻璃的声子能量,但是Tm3 /Yb3 共掺氧氟碲酸盐玻璃的上转换发光强度高于Tm3 /Yb3 共掺氧氯碲酸盐玻璃。分析认为这主要是由于OH-的影响,在氧氟碲酸盐玻璃中OH-的浓度较低,导致Tm3 的荧光寿命高,从而提高Tm3 的上转换发光。在一定程度上,OH-对Tm3 上转换发光的影响大于声子能量对Tm3 上转换发光的影响。研究结果有助于进一步提高Tm3 的发光效率。     

Yb3+/Er3+共掺杂BaY2F8纳米颗粒的水热合成与上转换发光

采用水热方法合成了Yb3+/Er3+共掺杂BaY2F8纳米颗粒,并对其进行了不同温度的热处理,热处理温度为200℃-800℃。研究了热处理温度对纳米粒子的晶相、粒径和上转换发光强度的影响。结果发现随着热处理温度的升高,纳米粒子的粒径和上转换发光强度明显增加。讨论了BaY2F8:Yb3+,Er3+纳米粒子的上转换发光机理。     

Er3+/Yb3+共掺氟硅酸盐玻璃陶瓷的制备及其量子剪裁发光行为

本文报道了一类组成为50SiO2-10Al2O3-20ZnF2-20SrF2-3YbF3-0.05ErF3(mol%)的氟氧化物玻璃陶瓷的制备及其量子剪裁发光行为。XRD和TEM分析结果显示,玻璃陶瓷中均匀分布有尺度10~40nm的SrF2析晶相。光谱研究表明,玻璃陶瓷在Er3+激发峰波长377nm激发下存在Er3+向Yb3+的有效能量传递,可实现包括量子剪裁效应在内的波长变换功能。随着热处理温度的升高,玻璃陶瓷的近红外977nm发光逐渐增强,荧光寿命显著增长。     

银纳米晶掺杂玻璃基片对Er3+/Yb3+共掺碲酸盐薄膜的荧光增强及其数值模拟

采用电场辅助热扩散工艺制备了银纳米晶掺杂玻璃基片,用非水解溶胶—凝胶法在基片上制备了Er3+/Yb3+共掺碲酸盐薄膜,研究结果表明,玻璃基片中的银纳米颗粒对Er3+/Yb3+共掺碲酸盐薄膜具有明显的荧光增强效果.利用菲克第一、第二定律、欧姆定律、泊松方程对电场辅助热扩散过程进行了数值模拟,计算了玻璃内银的浓度分布.结果表明:玻璃内银纳米颗粒的总量越大、近玻璃表面银纳米颗粒的浓度和粒度越大、银耗尽层的厚度越小,荧光增强效果越好.此外,不仅近玻璃表面的银纳米颗粒可以产生荧光增强效应,而且远离表面的银纳米颗粒也有荧光增强效应.     

Ho~(3+)掺杂Ge-Ga-S-CsI玻璃中红外发光性能研究

采用熔融冷却法制备了系列不同Ho3+离子掺杂浓度的Ge-Ga-S-CsI玻璃样品,测试了样品的折射率、吸收光谱以及中红外荧光光谱和Ho3+离子5I6能级荧光寿命.应用Judd-Ofelt理论计算了Ho3+离子在该基质玻璃中强度参数Ωi(i=2,4,6)、能级跃迁振子强度fcal、自发跃迁几率Arad等光谱参数.计算了Ho3+:5I5→5I6(3.86μm)和5I6→5I7(2.81μm)跃迁的多声子驰豫速率.讨论了中红外荧光特性与Ho3+离子掺杂浓度之间的关系.结果表明,在900nm激光泵浦下观察到了2.81和3.86μm两处中红外荧光,分别对应于Ho3+:5I6→5I7和5I5→5I6跃迁,当Ho3+离子掺杂浓度从0.5wt%增加到1.0wt%时,两处中红外荧光强度都随相应增加,计算的Ho3+:5I5→5I6和5I6→5I7跃迁多声子驰豫速率分别为29s-1和34s-1.     

Synthesis and luminescence properties of Yb3+–Er3+ co-doped LaOCl nanobelts via electrospinning combined with chlorination technique

LaOCl:Yb³⁺, Er³⁺ nanobelts were prepared by electrospinning combined with a double-crucible chlorination technique using NH₄Cl as chlorinating agent. X-ray powder diffraction analysis indicated that LaOCl:Yb³⁺, Er³⁺ nanobelts were tetragonal with space group P4/nmm. Scanning electron microscope analysis and histograms revealed that width of LaOCl:Yb³⁺, Er³⁺ nanobelts was 6.12 ± 0.18 μm under the 95% confidence level, and the thickness was 113 nm. Transmission electron microscope observation showed that as-obtained LaOCl:Yb³⁺, Er³⁺ nanobelts were composed of nanoparticles. LaOCl:Yb³⁺, Er³⁺ nanobelts emitted strong green and red up-conversion emission centring at 523, 551 and 667 nm, respectively, attributed to ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_l5/2 transitions of Er³⁺ under the excitation of a 980-nm diode laser (DL) excitation. Moreover, the near-infrared characteristic emission of LaOCl:Yb³⁺, Er³⁺ nanobelts was achieved under the excitation of a 532-nm laser. Commission Internationale de L'Eclairage analysis demonstrated that colour-tuned luminescence can be obtained by changing doping concentration of Yb³⁺ and Er³⁺, which could be applied in the fields of optical telecommunication and optoelectronic devices. The up-conversion luminescent mechanism and the formation mechanism of LaOCl:Yb³⁺, Er³⁺ nanobelts were also proposed.     

Luminescence of Yb, Yb co-doped silica glass for white light source

Yb²⁺, Yb³⁺ co-doped silica glasses were prepared by solid state reaction under vacuum condition for the first time. The luminescence properties of Yb²⁺-doped silica glass were investigated. There are four strong absorption bands in the Ultraviolet (UV) light region due to the 4f¹⁴-4f¹³5d¹ transition of the Yb²⁺ ions. The main emission wavelength of the Yb²⁺-doped silica glass was around 530 nm by the excited wavelength of 398 nm. The full width at half maximum (FWHM) of the excitation and emission bands were 137 nm, 165 nm respectively. The results suggest the Yb²⁺-doped silica glasses may be the potential medium for white light sources based on near UV LED chip.     

Preparation and upconversion property of TeO2:Er/Yb nanoparticles

Different crystal structure of TeO₂ nanoparticles were used as the host materials to prepare the Er³⁺/Yb³⁺ ions co-doped upconversion luminescent materials. The TeO₂ nanoparticles mainly kept the original morphology and phase after having been co-doped the Er³⁺/Yb³⁺ ions. All the as-prepared TeO₂:Er³⁺/Yb³⁺ nanoparticles showed the green emissions (525 nm, 545 nm) and red emission (667 nm) under 980 nm excitation. The green emissions at 525 nm, 545 nm and red emission at 667 nm were attributed to the ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of the Er³⁺ ions, respectively. For the α-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles, three-photon process involved in the green (²H_11/2 → ⁴I_15/2) emission, while two-photon process involved in the green (⁴S_3/2→⁴I_15/2) and red (⁴F_9/2 → ⁴I_15/2) emissions. For the β-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles, two-photon process involved in the green (²H_11/2 → ⁴I_15/2), green (⁴S_3/2 → ⁴I_15/2) and red (⁴F_9/2 → ⁴I_15/2) emissions. It suggested that the crystal structure of TeO₂ nanoparticles had an effect on transition processes of the Er³⁺/Yb³⁺ ions. The emission intensities of the α-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles and β-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles were much stronger than those of the (α + β)-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles.     

无容器制备Er3+/Yb3+共掺La2O3-TiO2-ZrO2玻璃及其上转换发光研究

利用无容器技术制备了(La_0.94-xEr_0.06Yb_x)(Ti_0.95Zr_0.05)_2.25O₆(x=0~0.24, 间隔0.04)球状透明玻璃, 其稀土离子掺杂浓度最大值达到30%。通过DTA分析发现, 玻璃具有很好的热稳定性, x=0时玻璃化转变温度T_g和析晶起始温度T_o分别为818℃和906℃, ΔT(ΔT= T_o-T_g)为88℃, 玻璃形成能力较低。随着Yb³⁺浓度提高, T_g、T_o和ΔT逐渐下降, 说明Yb³⁺降低了玻璃的热稳定性和形成能力。利用紫外可见分光光度计测定了样品的吸收/透过光谱, 玻璃在975 nm具有很强的吸收峰, 表明Yb³⁺可以有效提高玻璃对入射光的吸收强度; 在可见光范围内除特征吸收外具有近70%的透过率, 说明玻璃具有良好的透可见光性能, 有望获得高强上转换发光输出。上转换荧光光谱研究表明: 在980 nm激光泵浦下, 获得了中心位于535、554和672 nm处的绿、红发光带, x=0.16的发光最强, 672 nm处的红光强度是x=0的近130倍。上转换发光强度与泵浦功率关系的分析表明: 535、554 nm处的绿光和672 nm处的红光发光均是双光子发光过程。     

Significant reduction of upconversion emission in CaTiO3: Yb, Er inverse opals

Inverse opal photonic crystals of Yb³⁺, Er³⁺ co-doped CaTiO₃ (CaTiO₃: Yb, Er) were prepared using self-assembled polystyrene templates combined with the infiltration of sol-gel precursor. The influence of the photonic band gap on upconversion emission of Er³⁺ has been investigated in the CaTiO₃: Yb, Er inverse opals. Significant reduction of the upconversion emission was detected if the photonic band-gap overlaps with the Er³⁺ ions emission band.