(Bi0.5Na0.5)TiO3:Sm3+无铅压电陶瓷的红光发射特性

采用传统的固相反应烧结方法制备了稀土Sm³⁺掺杂的(Bi_0.5Na_0.5)TiO₃无铅压电陶瓷。系统分析了掺杂浓度、烧结温度和离子补偿对发光特性的影响。稀土Sm³⁺离子的加入实现了(Bi_0.5Na_0.5)TiO₃陶瓷的红绿光发射, 其激发光波段位于400~500 nm范围内, 与已经成熟的蓝光LED芯片的发射光谱充分匹配。当烧结温度为1100℃, Sm³⁺离子的掺杂浓度为0.015 mol时, 陶瓷样品呈现最强的发光强度。同时, 通过Li⁺、Na⁺、K⁺离子进行电荷补偿, 有效提高了陶瓷样品的发光性能, 发光强度随离子半径增大而增强。可见, Sm³⁺掺杂的(Bi_0.5Na_0.5)TiO₃材料在光电集成器件中具有很好的应用前景。     

Er3+掺杂量对TiO2:Er粉体上转换发光性能的影响

通过溶胶-凝胶法制备了Er³⁺离子掺杂的TiO₂纳米粉体。通过X射线衍射、荧光检测对制备的纳米晶微结构、发光性能进行了表征。结果表明：纳米晶微结构及粒径随掺杂量呈规律性变化，掺杂稀土离子可抑制其相变。在980nm红外激光泵浦下，其发射峰分别位于527nm、548nm、660nm处，通过改变Er³⁺掺杂量，获得绿红强度比最高为29.3,最低为0.7,实现了单一掺杂改变发光颜色的调控。借助交叉弛豫与浓度猝灭理论，解释了其发光性能的规律性变化，并分析了其上转换机制。     

(Lu0.5In0.5)2O3:Tm3+,Yb3+超细粉末的合成和上转换发光

先用液相沉淀技术合成Lu/In/Tm/Yb四元体系水合碱式碳酸盐类沉淀前驱体,然后将其在1100℃煅烧制备出一系列类球状平均粒度约为110 nm的[(Lu_0.5In_0.5)_0.999-xTm_0.001Yb_x]₂O₃ (x=0~0.05)氧化物固溶体。在980 nm泵浦激光激励下这种氧化物粉体在可见光区发射出强烈的蓝青光(450~510 nm,源于Tm³⁺离子4f¹²电子组态内¹D₂→³H₆,³F₄电子跃迁)和较弱的红光(650~670 nm,源于Tm³⁺离子的¹G₄→³F₄电子跃迁),二者的上转换过程均为双光子吸收。随着Yb³⁺离子浓度的提高1931CIE色坐标上的发射光颜色逐渐由绿光(0.31, 0.54)移向蓝光(0.01, 0.19)。Yb³⁺离子共掺提高了Tm³⁺离子的上转换发光强度,其最佳含量为2.5%。发射474 nm蓝光和654 nm红光的粉体,其荧光寿命分别约为0.84和0.97 ms。     

0.6%Pr,x%La:CaF2的发光性能研究和Judd-Ofelt分析(英文)

氟化钙(CaF₂)是一种良好的激光材料基质,具有较宽的透过范围(0.125～10μm)、良好的导热性(9.71W/(m·K))和低非线性效应系数。在Pr:CaF₂晶体中,[Pr³⁺-Pr³⁺]团簇导致Pr³⁺离子在较低浓度下出现荧光猝灭现象。在CaF₂中共掺入La³⁺离子有可能打破[Pr³⁺-Pr³⁺]团簇。本研究通过温度梯度法(Temperature Gradient Technique, TGT),成功地生长了一系列共掺入不同浓度La³⁺离子的Pr:CaF₂晶体。在室温下采用X射线粉末衍射、吸收光谱、荧光光谱和荧光衰减寿命对Pr,La:CaF₂晶体进行表征。Pr:CaF₂晶体共掺入La³⁺离子后仍具有立方晶体结构。³P₀→^3<...     

NaGd(WO4)2:Yb3+/Tm3+反蛋白石光子晶体的制备与上转换发光调制研究

三维光子晶体具有长程有序的结构特点, 在可见和近红外光谱范围内有着广泛的应用。光子晶体的一个重要性质是其对嵌入其中的发光中心自发辐射具有调制作用。本研究利用自组装和模板辅助法制备高质量的三维NaGd(WO₄)₂:Yb³⁺/Tm³⁺反蛋白石光子晶体, 探究了光子带隙对Tm³⁺离子上转换荧光发射与发光动力学的调制作用。通过对比分析发现, 由于反蛋白石光子晶体独特的周期性大孔结构和光子带隙效应, 处于光子带隙内的Tm³⁺离子¹G₄-³H₆的发光强度被抑制约45%, 自发辐射速率(SDR)被抑制约30%, 同时上转换局域热效应得到有效的调制。本实验结果对探索新型高效稀土掺杂上转换发光材料和提高上转换发光效率有指导意义。     

Sm3+/Ce3+/Tb3+共掺CaO-B2O3-SiO2发光玻璃的制备及发光性能研究

采用高温熔融法制备了Sm3+/Ce3+/Tb3+共掺杂的CaO-B2O3-SiO2发光玻璃材料,并用荧光分光光度计和CIE色度坐标对其发光性能进行了研究。发射光谱表明,在374nm激发下,Sm3+/Ce3+/Tb3+共掺杂CaO-B2O3-SiO2发光玻璃的发射光谱中同时观测到了红橙光、蓝光和绿光的发射带,这些发射带的混合实现了白光发射。此外,在Sm2O3和Tb4O7含量不变的情况下,随着CeO2含量的减小,Sm3+/Ce3+/Tb3+共掺杂发光玻璃的发光颜色在白光区逐渐由蓝光区附近过渡到黄光区附近。     

Yb3+-Tm3+共掺BiOBr纳米晶的近红外上转换发光特性研究

采用水热法合成了Yb³⁺-Tm³⁺共掺BiOBr纳米晶, 研究了其上转换发光性能。在980 nm光激发下, 样品中Tm³⁺离子实现了³H₄→³H₆、¹G₄→³F₄和¹G₄→³H₆跃迁, 进而发出强烈的近红外光(801 nm)和较弱的红光(655 nm)与蓝光(485 nm)。探讨了样品的上转换发光机理, 上转换发光强度与激发功率的关系表明在980 nm激发下Tm³⁺的蓝光和红光发射为三光子过程, 而近红外发光为双光子过程。随着Yb³⁺浓度增加, 近红外发光显著增强, 近红外光与蓝光(I_{801 nm}/I_{485 nm})的发光强度比高达71.4。研究结果表明, Yb³⁺-Tm³⁺共掺BiOBr纳米晶在生物荧光标记领域具有潜在的应用前景。     

紫外光激发Ce3+掺YVO4蓝光发射性能研究

利用提拉法生长了YVO₄和掺2.0at% CeO₂(或Ce₂(CO₃)₃)的YVO₄: Ce³⁺晶体。样品的XRD测试表明Ce³⁺代替Y³⁺进入晶格, Ce³⁺的加入并没有影响YVO₄的晶格结构。XPS测试显示YVO₄: Ce³⁺晶体中Ce离子3d分裂为882.0、885.8、902.9、908.0和915.9 eV等5个峰, 峰位表明样品中铈离子是以Ce³⁺和Ce⁴⁺两种价态形式存在。YVO₄和YVO₄: Ce³⁺激发谱都呈现出260~360 nm宽带激发, 此激发带源于基质中VO₄^3-离子团的配体O到V的电荷迁移吸收。使用325 nm的紫外线激发时, 两种样品均可发出以440 nm 为中心的宽带蓝光,其中YVO₄发射峰应归属于VO₄^3-离子团中³T₂→¹A₁和³T₁→¹A₁跃迁; 而YVO₄: Ce³⁺的蓝光发射则来源于Ce³⁺的5d→4f 的跃迁。分析可知YVO₄: Ce³⁺中VO₄^3-的π轨道和Ce³⁺的电子波函数能有效地重叠, 使得VO₄^3-和Ce³⁺可通过交换作用有效地向Ce³⁺传递能量, 可大幅提高Ce³⁺的蓝光发射强度。实验结果显示YVO₄: Ce³⁺可作为UV-LED管芯激发的白光发光二极管用高亮度蓝色发光材料。     

白光LED用LiY(MoO_4)_2∶RE~(3+)(RE=Eu,Sm,Pr)荧光粉的制备与性能

采用水热法制备了LiY(MoO4)2∶RE3+(RE=Eu、Sm、Pr)系列荧光粉,通过X射线衍射(XRD),扫描电镜(SEM)对该系列荧光粉的物相、形貌进行了表征。结果表明,稀土离子的掺入没有改变荧光粉的晶相,3种稀土离子的加入使得LiY(MoO4)2粉体形成片层状结构。利用PL(光致发光光谱)对样品的发光性能进行了测试,分析了稀土离子掺杂浓度对发光强度的影响并进行浓度猝灭机理分析,结果表明,Eu3+、Sm3+、Pr3+最佳掺杂浓度分别为7%,4%和1.5%。LiY(MoO4)2∶Eu3+荧光粉能够很好地被395nm的紫外光和465nm的蓝光有效激发而发射红光,而Sm3+和Pr3+掺杂的LiY(MoO4)2分别在406和453nm激发下,发射出650和657nm的红光,LiY(MoO4)2∶RE3+(RE=Eu、Sm、Pr)系列荧光粉有望成为白光LED用红色荧光粉。     

稀土离子掺杂硼酸钙发光材料的合成与光谱性质

以硼砂和氯化钙为原料,主要采用化学共沉淀法成功合成了稀土离子Eu3+、Tb3+掺杂的硼酸钙发光材料。通过X射线衍射、荧光光谱对样品物相和发光性能进行了表征。探究了不同的实验条件(即不同煅烧温度、稀土离子浓度)对其发光性能的影响,样品的激发光谱表明,在800℃时,CaB2O4∶Tb3+的发光能力最强;掺杂稀土Tb3+离子的发光材料在5%时发光性能最强。在221nm紫外光激发下,样品在612nm和543nm处有Eu3+和Tb3+离子明显的特征发射峰,而且掺杂Eu3+离子的发光材料的发光性能随着Eu3+浓度的增加而增强。     

Zn3-xMnxTeO6的晶体结构与吸收光谱和磁性研究

本工作主要研究Mn ²⁺离子掺杂的类刚玉系氧化物Zn₃TeO₆(0<x≤2.0)的晶体结构与光学性质和磁性的变化。Zn_3-xMn_xTeO₆粉末样品通过固相反应合成。Mn掺杂量的相图表明, x<1.0时保持单斜(C2/c)结构, 1.0≤x≤1.6为单斜(C2/c)和三方六面体混合相(R-3), x≥1.8时完全转变为R-3相, 且x=2.0时形成ZnMn₂TeO₆, Te-O和Mn/Zn-O键长增大, 八面体发生更大畸变。X射线粉末衍射结构精修也表明R-3相中Zn/MnO₆为畸变八面体。随着Mn ²⁺掺杂含量的增加, Zn_3-xMn_xTeO₆系列化合物不仅结构发生变化, 其颜色也由浅变深。紫外吸收光谱中随着掺杂浓度的增加, 400~550 nm处的吸收增强, 样品的光学带隙也由3.25 eV (x=0.1)逐渐减小到2.08 eV (x=2.0), 分析表明, 可见区吸收的增强是源于MnO₆八面体中Zn/MnO₆八面体中Mn ²⁺离子的d-d跃迁, 导致样品由浅黄色逐渐变为暗黄色。 磁性测试表明, 固溶体的反铁磁转变温度随着Mn ²⁺掺杂量的提高而逐渐增加, 且掺入的Mn ²⁺离子以高自旋态 存在。     

Blue, green and 0.8 μm Tm, Ho doped upconversion laser glasses, sensitized by Yb

To obtain efficient upconversion laser glass, the optical properties of Tm³⁺ and Ho³⁺ were investigated in various glasses. Fluoride glass was selected as base glass for upconversion. The efficient upconversion fluorescences corresponding to the ¹G₄→³H₆ and ³H₄→³H₆ transitions of Tm³⁺ and the ⁵S₂→⁵I₈ transition of Ho³⁺ were observed in Yb³⁺-Tm³⁺ and Yb³⁺-Ho³⁺ doped aluminozircofluoride glasses excited at 980 nm. The very stronge blue and green emission light can be observed visually. The upconversion processes observed were two-photon processes for ³F₄→³H₆, ⁵S₂→⁵I₈ transitions and three-photon processes for the ¹G₄→³H₆ transition and can be described by a rate equation model. The energy transfer and energy back-transfer were analyzed in Yb³⁺-Tm³⁺ and Yb³⁺-Ho³⁺ systems. The relationship between emission intensity, pumping intensity and dopant concentrations is described using a rate equation model and shows good agreement with experiments. The dynamics of excited state ( ) is also analyzed with the diffusion-limited model based on Yokota-Tanimoto theory.     

Transient light induced grating study of excitation diffusion in Y3Sc2Ga3O12 laser crystals

Excitation migration over the lower energy levels in Y₃Sc₂Ga₃O₁₂ (YSGG) laser crystals doped with Cr, Er, Tm, and Ho ions was studied using the two-wave mixing light induced grating (LIG) technique. The results of the LIG measurements were compared to the data obtained from the luminescence kinetics and spectra overlap studies of the migration. The comparison of the three different spectroscopic techniques allowed more detailed analysis of the complicated pattern of the energy transfer processes in the crystals than any one method alone. The migration was found to be very efficient, especially in highly doped crystals. The diffusion coefficients determined from direct LIG measurements were much higher than those calculated in dipole-dipole approximation from absorption and emission spectral measurements. This implies stronger than dipole-dipole coupling between interacting ions. In Tm doped crystals a surprisingly strong increase of the migration efficiency between Tm concentrations 8 × 10²⁰ cm⁻³ and 1.5 × 10²¹ cm⁻³ was observed both in LIG diffusion and luminescence kinetics experiments. This too cannot be explained in terms of low multipolar energy transfer. Exchange energy transfer and the percolation model are discussed as possible explanations for the experimental results.     

Energy transfer and radiationless relaxation processes in Nd and Cr doped mixed garnet crystals

Four-wave mixing and flourescence dynamics measurements have been used to investigate the energy transfer processes in (Gd,Ca)₃(Ga,Mg,Zr)₂Ga₃O₁₂ crystals doped with Nd³⁺ or codoped with Cr³⁺ and Nd³⁺ ions. The results show that strong, short range energy transfer takes place between Cr³⁺ and Nd³⁺ ions and this is enhanced by long range energy migration among the Cr³⁺ ions. Energy migration was also found to occur among the Nd³⁺ ions. The energy migration properties are affected by the active ion concentration, the distribution of active ions, ion-ion iteraction rates, and temperature. In addition, the pump band to metastable state radiationless relaxation process in the Cr³⁺ ions was characterized by determining the values of the dephasing time from the properties of the four-wave mixing signal. The effects of anharmonic coupling are needed to explain the variation of the T₂-dephasing time as a function of the crystal field splitting between the ²E and ⁴T₂ levels for a series of Cr³⁺-doped materials.     

Spectroscopy and upconversion processes in YAlO3:Ho crystals

Emission from the high lying excited states, energy transfer, and upconversion processes are investigated in YAlO₃:Ho³⁺. Selectively excited emission spectra in the range from 300 to 800 nm starting from the ³D₃, ³G₅, ⁵F₃, ⁵S₂ and ⁵F₅ multiplets were measured at 15 K. This, together with the detailed absorption and excitation measurements at 15 K allowed determination of the Stark energy levels of Ho³⁺ ions in YAlO₃ up to UV energies. The ⁵S₂ fluorescence decays were recorded as a function of temperature and Ho³⁺ concentration in order to investigate the process of quenching of fluorescence due to cross relaxation among two ions. Conversion of red and infrared laser radiation to green ⁵S₂ and blue ⁵F₃ emission is reported. Under pulsed resonant excitation of the ⁵F₅ or ⁵I₅ levels the upconversion was found to be due to energy transfer process between two excited ions. The photon avalanche effect was observed under cw excitation around 585 nm.     

Spectroscopic evidence of inhomogeneous distribution of Nd in YVO4, YPO4 and YAsO4 crystals

Nd³⁺ : YVO₄ is one of the most interesting laser hosts for micro and diode-pumped solid state lasers. We have studied magnetic and optical properties of Nd³⁺ in three zircon type crystals YMO₄ (M=V, As, P). In particular, Nd³⁺ ions exhibit in the three hosts a multisite character observed in the absorption and emission spectra. However, the emission and its dynamics are strongly dependant on the reabsorption mechanisms. In Nd : YVO₄, single crystals containing 7 ± 1 × 10¹⁸ Nd³⁺ ions/cm³, the lifetime is 95 ± 2 μs in good agreement with the calculated radiative lifetime. Electron Paramagnetic Resonance (EPR) measurements are performed to identify the nature of the different substitution sites for Nd³⁺ ions. Nd³⁺ ions are found to be inhomogeneously distributed in tetragonal D_2d symmetry sites, in isolated ions, “shallow clusters” and pairs. Proportions of the different local environments depend on the total neodymium concentration. For instance, 15% of the Nd³⁺ ions are gathered in Nd³⁺–Nd³⁺ pairs for 7.2 ± 0.2 × 10¹⁹ Nd³⁺ ions/cm³.     

Temperature dependencies of excited states lifetimes and relaxation rates of 3–5 phonon (4–6 μm) transitions in the YAG, LuAG and YLF crystals doped with trivalent holmium, thulium, and erbium

The temperature dependencies of the nanosecond multiphonon relaxation (MR) rates of the ³F₃ state of Tm³⁺ in the YLF crystal and of the ⁵F₅ state of Ho³⁺ ion in the YAG and LuAG crystals and of the microsecond MR rates of the ⁴F_9/2 (²H_9/2) state of Er³⁺ ions in YLF were measured in the wide temperature range using direct laser excitation and selective fluorescence kinetics decay registration. For YLF the observed relations are explained by 4-phonon process in the frame of a single-frequency model with hω_eff=450±30 cm⁻¹ for the ³F₃ state of Tm³⁺ and by 5-phonon process with hω_eff=445 cm⁻¹ for the ⁴F_9/2 (²H_9/2) state of Er³⁺. For YAG and LuAG crystals these dependencies are explained by the 3-phonon process with hω_eff=630 cm⁻¹. The decrease of the relaxation rate with the temperature in the range from 13 to 80 K was observed for the ⁴F_9/2 (²H_9/2) state of Er³⁺ in the YLF crystal. It is explained by the redistribution of excited electronic states population of erbium ions over the higher lying Stark levels with different MR probabilities. A good fit of experimental temperature dependence (including the dropping part of the experimental curve) was obtained for single-frequency model (hω_eff=450 cm⁻¹) with W₀₁=8.0×10⁴ s⁻¹ and W₀₂=4.7×10⁴ s⁻¹ accounting Boltzmann distribution of population over two excited Stark levels of the excited state of erbium ions. Employment of this model improves the fit between the experiment and the theory for the ⁵F₅ state of Ho³⁺ ion in YAG as well. Strong influence of the parameters of the non-linear theory of MR, i.e. the reduced matrix elements U^(k) of electronic transitions and the phonon factor of crystal matrix η on the spontaneous MR rates was observed experimentally. The smaller these parameters the slower the spontaneous MR W₀. This fact can be used for searching new active crystal laser media for the mid-IR generation.