Er3+/Yb3+共掺氟氧微晶玻璃的光谱性质及Judd-Ofelt理论分析

制备了新的Er3+/Yb3+共掺氟氧硅酸盐微晶玻璃,测试了荧光光谱、吸收光谱。研究了氟氧化物微晶玻璃中Er3+离子的上转换发光特性,采用Judd-Ofelt理论对样品光谱进行了分析,拟合得到了强度参数,Ω2=4.4756,Ω4=1.0059,Ω6=1.2098。计算了样品的辐射寿命、跃迁几率、荧光分支比等光谱参数。结果表明,样品通过热处理形成了氟化物微晶,降低了声子能量,提高了上转换效率。绿光、红光上转换荧光强度比玻璃样品增强约2到3倍。Judd-Ofelt理论分析表明Er3+/Yb3+共掺氟氧微晶玻璃具有较高的上转换效率,是制作微型激光器和三维立体显示的优良材料之一。     

YAG:Ce,Yb近红外下转换荧光粉中的离子簇集

通过457 nm和915 nm连续激光器对固相反应法和溶胶-凝胶法制备的YAG:Ce,Yb荧光粉中的Yb3+近红外发光和可见上转换发光能量转移机制进行了研究。两种激发下,溶胶-凝胶法样品的近红外发光猝灭浓度均在5%左右,发光强度变化曲线趋势相近;固相反应法产物,915 nm直接激发猝灭浓度为5%左右,457 nm间接激发猝灭浓度为10%左右,说明固相反应法掺杂离子分布更不均匀。样品中存在来自Yb3+到杂质离子间能量传递和Yb3+-Yb3+离子对的两种上转换发光;固相反应法产物Yb3+-Yb3+离子对协同发光强于溶胶-凝胶法产物,说明Yb3+离子簇集现象较为明显,可能降低此类材料的实际近红外转换效率。     

Er~(3+),Yb~(3+)掺杂氟氧化物微晶玻璃上转换发光的研究

测量了 Er3+掺杂氟氧化物微晶玻璃、Er3+ ,Yb3+掺杂氟氧化物微晶玻璃退火前后 3种样品的吸收光谱、激发光谱、上转换发光光谱及其强度随泵浦光强的变化 ,对比讨论了其上转换发光特性     

Yb3+对掺铒碲酸盐玻璃红外和上转换发光的影响

研制了Er3+/Yb3+共掺TeO2-ZnO-La2O3玻璃,测试了Er3+离子的吸收谱、荧光谱和上转换发光谱,系统研究了975 nm抽运下Yb3+离子对于Er3+离子1.5 μm波段荧光性能及其上转换发光性能的影响.结果表明,随着碲酸盐玻璃中Yb2Os含量的增加,Yb3+离子对Er3+离子的能量传递增强,Er3+离子1.5 μm波段的荧光强度和上转换发光强度相应增大,但后者相对于前者增加更为迅速.通过对粒子数速率方程的理论模拟,计算结果与实验测量结果较为一致,表明Er3+/Yb3+共掺碲酸盐玻璃是一种优良的潜在上转换激光器增益介质.对上转换发光分析表明,强烈的绿光和红光激发是基于双光子的吸收过程.     

光学碱度与能量传递对Bi/Yb3 共掺杂锗酸盐玻璃近红外发光性质的影响

采用传统高温熔融法制备了Bi/Yb3 共掺杂锗酸盐玻璃,通过测试吸收光谱、近红外光谱和荧光衰减寿命,研究了玻璃样品的近红外发光性质。在980nm 或808 nm 激光激发下,均能同时观察到Yb3 和Bi离子的近红外发光,这一结果表明,Yb3 离子与Bi离子之间存在相互能量传递。随着Yb3 离子浓度的增加,玻璃基质的光学碱度和Yb3 离子到 Bi 离子的能量传递效率均增加,讨论了能量传递效率的提高对Bi离子发光的增强作用与光学碱度增加对Bi离子发光的削弱作用的竞争影响机制,获得了Bi/Yb3 近红外发光的机理。     

Eu3+,Li+共掺杂ZnO薄膜结构与发光性质的研究

为了研究Eu3+,Li+共掺杂的ZnO薄膜结构与发光性质,采用脉冲激光沉积方法在P型单晶Si（111）衬底上制备了Eu3+,Li+共掺杂的ZnO薄膜,其中,Eu3+作为发光中心,而Li+作为低价电荷的补偿离子和发光敏化剂。分别对样品进行了X射线衍射谱测试和光致发光谱分析。得出的数据中X射线衍射谱显示,Eu3+,Li+共掺杂的ZnO薄膜具有c轴择优取向,X射线衍射谱中除ZnO晶向以外没有出现其它结晶峰;Eu3+,Li+共掺杂的ZnO薄膜的光致发光谱与ZnO纯晶体薄膜的发射光谱基本相似,但是掺杂ZnO薄膜的紫外发光峰却出现红移现象,峰值位于382nm处,且发光峰也不尖锐。当以395nm的激发光照射样品时,在光致发光光谱中观察到了稀土Eu3+在594nm,613nm附近的特征发光峰。结果表明,掺杂元素Eu3+,Li+均已进入到ZnO晶格中,形成了以Eu3+为发光中心的ZnO纤锌矿结构。     

基于PLD法制备ZnO:Eu3+,Li+薄膜的发光性质研究

采用脉冲激光沉积(PLD)技术在Si(111)衬底上生长了Eu3+、Li+共掺杂的ZnO薄膜。分别对样品进行了X射线衍射(XRD)谱测试和光致发光(PL)谱分析,重点研究了退火处理对样品结构和发射光谱的影响。XRD谱测试表明,样品具有很好的C轴择优取向。PL谱研究表明,当用325nm光激发样品时,样品的发射光谱仅由ZnO基质的紫外发射和蓝光发射组成,并没有发现稀土Eu3+的特征发光峰;样品的蓝光发射源于电子从Zn填隙形成的浅施主能级到Zn空位形成的浅受主能级跃迁;和真空中退火的样品相比,O2中制备的样品的蓝光发射减弱,紫外发光增强。用395nm的光激发时,退火前样品分别在594nm和613nm处存在两个明显的Eu3+特征发光峰,退火后的样品仅发现Eu3+位于594nm的特征发光峰,这表明,退火处理不利于稀土离子的特征发射,但O2中退火的样品ZnO基质红绿波段发射光谱明显增强。     

Bi_2O_3对Tm~(3+)/Ho~(3+)/Yb~(3+)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+共掺碲酸盐玻璃样品,在TeO2-ZnO-La2O3玻璃组分的基础上,引入声子能量较低的重金属氧化物Bi2O3,研究了Bi2O3组分对基质样品拉曼光谱和Tm3+/Ho3+/Yb3+共掺样品上转换发光光谱的影响。结果发现,在975 nm波长激光二极管(LD)激励下,制备的碲酸盐玻璃样品中可以观察到强烈的红光(662 nm)、绿光(546 nm)和蓝光(480 nm)三基色上转换发光。随着重金属氧化物Bi2O3组分含量的增加,玻璃基质的最大声子能量降低,Tm3+/Ho3+/Yb3+共掺样品的三基色上转换发光强度均有所提高,且Bi2O3组分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。     

Ho3+掺杂Al2O3粉体、薄膜的结构及其发光性能

采用高能球磨法及脉冲激光沉积法(PLD)分别制备了不同浓度的Ho3+∶Al2O3纳米粉体及薄膜,利用X射线衍射仪(XRD)、分光光度计、荧光光谱仪等分析手段研究了Ho3+离子掺杂对Al2O3结构及发光性能的影响。XRD图谱显示粉体样品为六方α-Al2O3结构,薄膜样品为体立方γ-Al2O3结构。1wt%Ho3+掺杂的Al2O3纳米粉体在454nm、540nm附近出现由Ho3+离子能级跃迁引起的吸收峰。采用579nm的激发光源对样品进行荧光光谱检测,发现两种样品在466～492nm波段均出现F+心所引起的缺陷发光峰,且发光峰的强度随Ho3+浓度的增加而增强。     

Ho3+/Yb3+共掺的SiO2-Al2O3-BaO-BaF2微晶玻璃上转换发光研究

制备了Ho3+/Yb3+共掺的氧氟硅酸盐玻璃, 根据玻璃样品的差热分析进行微晶化处理, 测试了Ho3+/Yb3+共掺微晶玻璃的X射线衍射(XRD)图谱、吸收光谱和上转换发光光谱。结果发现, 在980 nm LD激发下, Ho3+/Yb3+共掺的含BaF2纳米晶的氧氟硅酸盐微晶玻璃可以同时观察到绿光(544 nm)和红光(656, 748 nm)上转换发光, 分别对应于Ho3+ 离子的5F4/5S2→5I8, 5F5→5I8和5F4/5S2→5I7能级跃迁, 与未热处理的玻璃样品相比, 微晶玻璃样品的绿光发光强度增强约347倍。研究结果表明含BaF2纳米晶的氧氟硅酸盐微晶玻璃是一种潜在的上转换基质材料。     

Photoluminescence of erbium-doped aluminum oxide films with embedded silicon nanoparticles

Erbium-doped aluminum oxide films with embedded Si nanoparticles have been obtained by magnetron puttering of a composite (Al + Er₂O₃ + Si) target and subsequent electrochemical anodization at room temperature. The photoluminescence (PL) spectra of these films are measured in the temperature range 4.2–300 K. Efficient PL is observed at a wavelength of 1.54 μm without preliminary annealing of the samples, which indicates the possibility of activating Er³⁺ ions without any high-temperature treatment. The aluminum oxide films with embedded Si nanoparticles were observed to show stronger PL at a wavelength of 1.54 μm than similar films without Si nanoparticles. This effect can be explained by additional pumping of Er-based luminescence centers and energy transfer from the Si nanoparticles.     

Upconversion fluorescence modulation of CaTiO3:Yb3+/ Er3+ nanocubes via Zn2+ introduction

rials, CaTiO3:Yb3+/Er3+/Zn2+ nanocubes with uniform size were prepared by solvothermal method in this paper. They were respectively characterized by X-ray diffractometer (XRD), scanning electron microscope (SEM), photoluminescence (PL) spectroscopy and their fluorescence lifetimes. The results show that the average size of the nanocubes is about 550 nm×650 nm×850 nm with good upconversion luminescence (UCL) properties. Under 980 nm laser excitation, the effects of the ratio between activator Er3+ and sensitizer Yb3+ and Zn2+ doping on the upconversion fluorescence properties were investigated, and the optimal ion ratio was obtained. The results of steady-state spectra show that the strongest fluorescence intensity of CaTiO3:Yb3+/Er3+ was obtained with the addition of 10 mol% Zn2+ at a Yb3+/Er3+ molar doping ratio of 3:0.3, which was attributed to the crystal field asymmetry generated by the introduction of Zn2+ ions. The energy transfer and upconversion mechanism between Yb3+ and Er3+ ions in CaTiO3 nanocubes were investigated by analyzing the upconversion fluorescence kinetics.     

Investigation of up-conversion luminescence of Er3+ and Er3+/Yb3+ ions doped in PLZT for active electro-optical applications

The up-conversion luminescence of Er3+ and Er3+/Yb3+ ions doped in lanthanum-modified lead zirconate titanate (PLZT) under 980 nm excitation at room temperature has been investigated. The green upconversion luminescence at 540 and 566 nm was observed in Er3+:PLZT; the greater the concentration of Er3+ ions, the stronger the intensity. In Er3+-Yb3+:PLZT, other than the green up-conversion luminescence at 540 and 566 nm, a relatively weak red up-conversion luminescence at 668 nm was also observed. Both green and red up-conversion luminescence intensities presented an approximately quadratic dependence on excitation power, which indicated that two excitation photons are involved in the up-conversion process of Er3+:PLZT and Er3+-Yb3+:PLZT. The characteristics of PLZT ceramic material were also studied by Raman spectroscopy. This work shows a promising future for developing multifunctional up-conversion electrooptical devices using Er3+ and Er3+/Yb3+ ions doped PLZT.     

Ho3+/Yb3+/Ce3+三掺钽酸锂上转换绿光的研究

在三掺Ce3+的Ho3+/Yb3+/LiTaO3多晶粉中,发现增强上转换绿光并同时抑制上转换红光的新途径,能有效提高上转换发光的单色性.XRD衍射谱结果表明制备粉体仍为三方晶系.980 nm LD激发下,上转换绿光发光强度随Ce3+掺杂浓度增加而增强,并在Ce3+掺杂摩尔分数达15％时,上转换绿光发光效率达到最大,并同时抑制了上转换红光.Ce3+将2F7/2能级上的能量传递给H03+的516能级来增加上转换绿光.并在高掺Ce3+时,新的交叉弛豫过程使Ce3将2 F7/2能级上的能量传递给H03+的5F4/5S2能级,增强了上转换绿光并同时抑制了上转换红光.     

Light Emission in Nd Doped Si-Rich HfO 2 Films Prepared by Magnetron Sputtering

Hafnium oxide films doped with Si and Nd atoms were produced by radio-frequency magnetron sputtering of a HfO2 target topped with calibrated Si and Nd2O3 pellets in pure argon plasma followed by an annealing in nitrogen atmosphere during tA = 15 min at different temperatures (TA = 800–1100°C). The evolution of structural, chemical and luminescent properties of the films with TA was studied by means of the scanning electronic microscopy (SEM), x-ray diffraction (XRD), Raman scattering, energy dispersive x-ray spectroscopy and photoluminescence (PL) methods. The SEM method revealed that the surface of as-deposited film consists of the grains with the mean size of 20–60 nm. Annealing treatment stimulated the growing of the grains (up to 100 nm in lateral size) and film densification. The presence of Si-rich phase was detected by Raman scattering spectra in as-deposited films and those annealed at low TA. The TA increase results in the phase separation process. For the films annealed at TA > 950°C, the tetragonal HfO2 and SiO2 phases were clearly detected by the XRD method. PL spectra of the films were found to be complex. They demonstrated several PL bands in the visible (400–750 nm) and infrared (800–1430 nm) spectral ranges. Besides PL components caused by the recombination of carriers via host defects, the PL signal from Nd3+ ions due to the transition in the 4f inner electronic shell was observed. The highest Nd3+ related PL signal was observed for the films annealed at TA = 950°C. Peculiarities of PL excitation and the mechanism of the phase separation are analysed and discussed.     

Luminescence Properties of Cobalt-Doped ZnO Films Prepared by Sol–Gel Method

Pure ZnO and Co-doped ZnO films have been deposited on coverslip substrates by sol–gel spin coating. The morphological, structural, and optical properties of the films were investigated. The microstructure of the ZnO films became increasingly fine and the crystalline size decreased with Co doping. Analysis of x-ray diffraction (XRD) and Raman spectra reveals that Co²⁺ ions are substituted for Zn²⁺ ions in the ZnO lattice without changing its wurtzite structure. Co doping induces a decrease of the band-gap energy and fluorescence quenching of the emission bands. The spectra related to transitions within the tetrahedral Co²⁺ ions in the ZnO host crystal were observed in absorption and luminescence spectra. Photoluminescence (PL) spectra under different excitation energies and PL excitation spectra for the visible emissions suggest that the orange–red emission and green emission could be related to interstitial zinc (Zn_i) shallow donors and oxygen vacancy (V _O) deep donors, respectively. The red emission of Co-doped ZnO film could be assigned to the radiative transitions within the tetrahedral Co²⁺ ions in the ZnO host crystal after band-to-band excitation. A consistent explanation for the pure and Co-doped ZnO films is that the red emission under the excitation energy below the band gap is probably associated with extended Zn_i states.     

Yb~(3 )-Ho~(3 )双掺杂ZBLAN玻璃中Ho~(3 )的上转换发光

室温下用ＬＤ（０．９７μｍ）作为激发源，测出不同双掺浓度（Ｙｂ３＋－Ｈｏ３＋）玻璃Ｙｂ３＋敏化Ｈｏ３＋离子的可见上转换发光光谱，给出了单掺和双掺玻璃中的Ｙｂ３＋荧光寿命。双掺玻璃中Ｙｂ３＋荧光寿命明显降低，Ｙｂ３＋对Ｈｏ３＋离子的敏化上转换发光是非常有效的，并讨论了敏化机理。     

Ho3+/Yb3+共掺碲酸盐玻璃的上转换发光及能量传递机理

用高温熔融法制备了Ho3+单掺和Ho3+/Yb3+共掺、组分为TeO2-ZnO-Na2O的碲酸盐玻璃,应用Judd-Ofelt(JO)理论计算分析了玻璃的强度参数Ωt(t=2,4,6)、自发辐射跃迁几率A、荧光分支比β和荧光辐射寿命τrad等各项光谱参数。通过测量上转换光谱,着重研究了Yb3+掺杂对于Ho3+上转换发光性能的影响,分析了Yb3+/Yb3+以及Yb3+/Ho3+间的能量传递过程。结果显示,975nm泵浦下Ho3+的上转换发光主要来自于Yb3+/Yb3+间的共振能量传递以及基于单声子和双声子辅助的Yb3+/Ho3+间的能量传递过程,并计算得到了声子贡献比和能量传递微观参数。同时,计算分析了Ho3+:5 I7→5 I8能级跃迁的吸收截面、受激发射截面和增益系数。研究表明,Yb3+/Ho3+共掺TeO2-ZnO-Na2O玻璃可以作为上转换激光器和2.0μm波段固体激光器的潜在增益基质。     

Yb3+/Er3+共掺ZnF2粉末上转换发光特性研究

为了研究ZnF₂作为基质材料、稀土离子Yb3+和Er3+共掺摩尔分数不同时的发光性能,采用高温固相法,在820℃时制备稀土掺杂ZnF₂样品,并对各个样品进行上转换发射光谱测试。将激发功率与上转换发射功率进行曲线拟合,确定Yb3+和Er3+光子吸收过程。结果表明,在980nm半导体激光器激发下,样品在可见光区域内存在533nm,555nm和655nm 3个上转换发射峰,发射的红光强度大于绿光强度,吸收光子数目依次为1.73,1.75,1.88,确定3个发射峰均对应于双光子吸收。此研究说明稀土离子掺杂ZnF₂材料将在上转换红色荧光粉领域有重要的应用前景。