Upconversion properties of Er^3＋/Yb^3＋ co-doped TeO2-Nb2O5-Li2O glasses

The Er^3＋/Yb^3＋ co-doped TeO2-Nb2O5-Li2O glass is prepared by conventional melting method, and its upconversion spectra are measured. The intense green upconversion luminescence upon excitation with a 976 nm laser diode is observed with the naked eyes. The dependence of luminescence intensity on the ratio of Yb^3＋/Er^3＋ is discussed in detail, and the relationship between the ratio of green luminescence intensity to red luminescence intensity and the ratio of Yb^3＋/Er^3＋ is also studied, The luminescence intensity increases with the ratio of Yb^3＋/Er^3＋ increasing. The ratio of Yb^3＋/Er^3＋ plays a more important role than the concentration of Er^3＋ in determining the upconversion luminescence intensity. The ratio of green luminescence intensity to red luminescence intensity reaches a maximum when ratio of Yb^3＋/Er^3＋ is 3. Thus the glass could be one of the potential candidates for LD pumping solid-state lasers.     

Yb^3＋/Er^3＋掺杂氟氧化物微晶玻璃的制备与发光性能

采用高温熔融法制备了Yb3＋/Er3＋掺杂的氟氧化物发光微晶玻璃,确定了最佳熔化温度（1 100℃）和退火温度（440℃,480℃）。测定得到基质玻璃的透过率为85%,掺入稀土后,透过率有所下降,并出现了稀土离子的特征吸收峰。980 nm半导体激光器（LD）激发下样品的上转换发射光谱存在4个明显的发射峰,分别为410,532,546和656 nm,对应于2H9/2→4I15/2,2H11/2→4I15/2,4S3/2→4I15/2和4F9/2→4I15/2跃迁。研究了不同Yb3＋/Er3＋（摩尔分数）和Er3＋浓度对上转换发光强度的影响,当Yb3＋∶Er3＋=4∶1、Er3＋摩尔分数为1.5%时,上转换发光强度达到最高。根据发光强度与泵浦功率之间的关系,确定了上转换发射均为双光子过程。讨论了Yb3＋,Er3＋离子间的能量传递,建立了上转换发光机制。     

Research on upconversion codoped oxyfluoride luminescence in new Er^3＋/Yb^3＋ borosilicate glass ceramics

The upconversion luminescence of Er^3＋/Yb^3＋ ions is researched in a novel transparent oxyfluoride borosil- icate glass and glass ceramics under 980-nm excitation. Fluoride nanocrystals Ba2YF7 are successfully precipitated in glass matrix, which is affirmed by the X-ray diffraction results. Compared with the parent glasses, significant enhancement of upconversion luminescence is observed in the Er^3＋/Yb^3＋ codoped transparent glass-ceramics, which may be due to the variation of coordination environment around Er^3＋ and Yb^3＋ ions after crystallization. The possible upconversion mechanism is also discussed.     

Blue Upconversion Luminescence in Tm^3＋／Yb^3＋-Codoped Lead Chloride Tellurite Glass

The upconversion properties of Tm^3 /Yb3 -codoped lead chloride tellurite glass under 980hm excitation were investigated. The intense blue (476nm) emission and weak red (649 nm) emission corresponding to the ^1G4→4 ^3H6 and ^1G4→^3H4 transitions of Tm^3 ions, respectively, were simultaneously observed at room temperature. The dependence of upconversion intensities on excitation power and the possible upconversion mechanisms are evaluated. The intense blue upconversion luminescence of Tm^3 /Yb^3 -codoped lead chloride tellurite glass can be used as potential host material for the development of blue upconversion optical devices.     

Upconversion Luminescence Dynamics in Er^3＋/Yb^3＋ Codoped Nanocrystalline Yttria

The upconversion luminescence and dynamics in Er^3＋ /Yb^3＋ codoped nanocrystalline yttria （7-65 nm） are studied under 980-nm pulsed laser excitation, It is found that the red emission of ^4F9/2-^4I15/2 and the green emission of ^2H11/2/^4S3/2 in nanoparticles with lower concentration of Yb^3＋ result from a two-photon excitation, In nanocrystals with higher Yb^3＋ concentration, the red emissions from a two-photon excitation, while the green emissions from a three-photon excitation, The luminescence dynamics indicates that as the particle size decreases, both the rise and the decay time constants become shorter, As the size decreases to several nanometres, the rise process nearly disappears, suggesting that the upconversion luminescence originates mainly from self-excitation of Er^3＋, instead of the energy transfer of Yb^3＋→ Er^3＋.     

Er^3＋/Tm^3＋/Yb^3＋ tridoped oxyfluoride glass ceramics with efficient upconversion white-light emission

A novel Tm^3＋/Yb^3＋ triply-doped glass ceramics containing BaF2 nano-crystals are successfully prepared. Fluoride nanocrystals BaF2 are successfully precipitated in glass matrix, which is affirmed by the X-ray diffraction results. The intense blue （476 nm）, green （543 nm）, and red （656 nm） emissions of the glass ceramics are simultaneously observed at room temperature under 980-am excitation, and the emission luminescence intensity increases significantly compared with the precursor glass, which is attributed to the low phonon energy of fluoride nanocrystals when rare-earth ions are incorporated into the precipitated BaF2 nanocrystals. Under 980-nm excitation at 400 mW, the international commission on illumination （CIE） chromaticity coordinate （X = 0.278, Y = 0.358） of the tridoped oxyfluoride glass ceramics＇ upconversion emissions is close to the standard white-light illumination （X = 0.333, Y= 0.333）. The results indicate that Tm^3＋/Yb^3＋ triply doped glass ceramics can act as suitable materials for potential three-dimensional displays applications.     

Enhancement of up-conversion Yb3＋/Tm3＋/Er3＋ tri-doped tellurite glass luminescence properties in transparent oxyfluoride ceramics

Optically transparent Er3＋/Tm3＋/Yb3＋ tri-doped oxyfluoride tellurite based nano-crystallized glass ceramics with the batching composition of 73TeO2-15ZnO-7ZnF2-3YF3-1.5YbF3-0.3ErF3-0.2TmF3 （mol%） is prepared by a conventional melting quenching and the subsequent heat treatment processes. The sizes of grown nano-crystals in glass matrix appear to be smaller than 100 nm from the scanning electron mi- croscope measurement. Visible up-conversion luminescence of the as melted glass and glass ceramics is investigated. The three-color up-conversion luminescence intensities by 980-nm pumping are increased significantly due to the heat treatment, and the blue intensity increases with a higher magnitude than other wavelengths after heat treatment.     

Tm：YVO4晶体中Tm^3＋的发光研究

测量了Tm:YVO4晶体的吸收光谱,以346nm,363nm(^1D2),475nm(^1G4),698nm(^3F2,^3F3)和801nm(^3H4)光激发时的发射光谱,以及位于454nm(^1D2→^3F4),475nm(^1G4→^3H6),646nm(^1G4→^3F4),806nm(^3H4→^3H6)的荧光谱线的激发光谱,对测量的结果进行了详细分析,解释了离子能级间的跃迁过程,提出了Tm:YVO4晶体基质与Tm^3 之间的能量交换的概念和新的跃迁通道,证实了存在^1D2 ^3H6→^1G4 ^3F4以及^1G4 ^3H6→^3H4 ^3H5的能量传递过程,还可能存在交叉弛豫过程^1G4 ^H6→^3F2 ^3F4. 这些过程使得Tm:YVO4晶体难以实现^1D2能级上转换发光（454nm左右）,但475nm的上转换发光（^1G4→^3H6)较强,^3F4能级是潜在红外激光发射能级。     

Frequency Upconversion Fluorescence Emission of Er^3＋-Doped Oxychloride Germanate Glass

Frequency upconversion fluorescence property of Er^3 -doped oxychloride germanate glass is investigated. Intense green and red emissions centred at 525, 546, and 657nm, corresponding to the transitions ^2H11/2→4I15/2,^4S3/2→^4I15/2, and ^4F9/2→^4I15/2, respectively, were simultaneously observed at room temperature. The quadratic dependence of the 525, 546, and 657nm emissions on excitation power indicates that a two-photon absorption process occurs under 975 nm laser diode (LD) excitation. The Raman spectrum investigation indicates that oxychloride germanate glass has the maximum phonon energy at-805cm^-1. The thermal stability of this oxychloride germanate glass is evaluated by differential scanning calorimetry, and thermal stability factor AT(△T = Tx -Tg) is 187℃. Intense upconversion luminescence and good thermal stability indicate that Er^3 -doped oxychloride germanate glass is a promising upconversion laser material.     

High Efficiency Infrared to Visible Upconversion in Er3＋／yb3＋—Doped Lead Halide Tellurite Glass

Strong upconversion luminescence of Er3 /Yb3 -doped lead halide tellurite glass under 976nm excitation is demonstrated. Three emission bands centred at 525 nm, 545 nm, and 655 nm resulting from the transitionsfrom the excited states 2H11/2, 4S3/2, and 4F9/2 to the ground state 4I15/2, respectively, are observed evenat 60mW pumping power. The power dependent intensity and the upconversion mechanisms responsible forthe luminescence are evaluated and discussed. The obtained results might provide useful information for thedevelopments of upconversion lasers.     

Tm3+/Yb3+共掺氟氧硅铝酸盐玻璃陶瓷蓝色上转换发光研究

按摩尔百分比制备了组分为30SiO₂-(20-x-y)Al₂O₃-40PbF₂-10CdF₂-xTm₂O₃-yYb₂O₃的两组Tm³⁺/Yb³⁺共掺杂氟氧硅铝酸盐上转换蓝色发光玻璃陶瓷材料,测量了其在980nm激 关键词： 玻璃陶瓷 上转换发光 3+/Yb³⁺掺杂')" href="#">Tm³⁺/Yb³⁺掺杂 掺杂浓度     

Tm3+/Yb3+共掺铋碲酸盐玻璃中的高效蓝色上转换荧光

制备了高折射率Tm³⁺/Yb³⁺共掺杂铋碲酸盐玻璃，利用棱镜耦合法测量出玻璃在632.8和1550nm波长处的折射率分别为2.0365和1.9795. 对玻璃的吸收、荧光和红外透过光谱展开了测试与分析，根据Judd-Ofelt理论对吸收光谱进行拟合，求得Tm³⁺的振子强度参数Ω_t(t=2，4，6)分别为3.90×10^-20, 2.03×10^-20和9.03×10^{-2 关键词： 3+}/Yb³⁺共掺')" href="#">Tm³⁺/Yb³⁺共掺 铋碲酸盐玻璃 光谱参数 上转换荧光     

Yb3+敏化的Er3+/Ho3+共掺碲酸盐玻璃的上转换发光研究

用高温熔融法制备了系列Er³⁺/Yb³⁺共掺，Ho³⁺/Yb³⁺共掺，和Er³⁺/Yb³⁺/Ho³⁺三掺碲酸盐玻璃，在975nm激光抽运下三种掺杂玻璃中都出现了较强的绿光和红光上转换.研究了Yb³⁺离子对Er³⁺和Ho³⁺离子上转换发光强度的影响以及Yb³⁺→Er关键词： 3+/Yb³⁺/Ho³⁺共掺')" href="#">Er³⁺/Yb³⁺/Ho³⁺共掺 碲酸盐玻璃 光谱性质 上转换     

Up-conversion photoluminescence characteristics of Yb3+:Er3+:Tm3+ co-doped borosilicate glasses

Yb3+:Er3+:Tm3+ co-doped borosilicate glasses are prepared.Their strong up-conversion photoluminescence spectra in a range from ultra-violet to near-infrared,which are excited by a 978-nm laser diode,are measured,and the mechanisms of energy transfer among Yb3+,Er3+ and Tm3+ ions are discussed.The results show that there is an unexpected wavelength at 900-nm emission from Yb3+ Stark splitting levels to pump Tm3+ ions and there exists an optimum pump power.The concentration of the Tm3+ dopant gives rise to a prominent effect on the intensity of visible and near-infrared emissions for the Yb3+:Er3+:Tm3+ co-doped borosilicate glasses.     

Spectroscopic properties and mechanism of Tm^3＋/Er^3＋/Yb^3＋ co-doped oxyfluorogermanate glass ceramics containing BaF2 nanocrystals

Transparent Tm^3＋/Er^3＋/yb^3＋ co-doped oxyfluorogermanate glass ceramics containing BaF2 nanocrystals are prepared. Under excitation of a 980-nm laser diode （LD）, compared with the glass before heat treatment, the Tm^3＋/Er^3＋/yb^3＋ co-doped oxyfluorogermanate glass ceramics can emit intense blue, green and red up-conversion luminescence and Stark- split peaks; X-ray diffraction （XRD） and transmission electron microscope （TEM） results show that BaF2 nanocrystals with an average diameter of 20 nm are precipitated from the glass matrix. Stark splitting of the up-conversion luminescence peaks in the glass ceramics indicates that Tm^3＋, Er^3＋ and （or） Yb^3＋ ions are incorporated into the BaF2 nanocrystals. The up-conversion luminescence intensities of Tm^3＋, Er^3＋ and the splitting degree of luminescence peaks in the glass ceramics increase significantly with the increase of heat treat temperature and heat treat time extension. In addition, the possible energy transfer process between rare earth ions and the up-conversion luminescence mechanism are also proposed.     

Er3+/Yb3+共掺碲钨酸盐玻璃的光谱性质和热稳定性的研究

制备了Er³⁺和Yb³⁺共掺的碲钨酸盐玻璃样品65TeO₂-25 WO₃-10R_mO_n(R_mO_n=PbO,BaO),(65+x)TeO₂-(25-x)WO ₃-10La₂O₃ (x=0,5,10), (60+x)TeO₂-(30 -x)WO₃-10Bi₂O₃ (x=0,5,10).测试了玻璃样品的吸收光谱、荧光光谱、能级寿命及热稳定性能.结果表明除含Bi ₂O₃的碲钨酸盐玻璃外，其余玻璃样品均没出现析晶开始温度(T_x)，说明碲钨酸盐 是一种适合于光纤拉制的玻璃基质材料.应用Judd-Ofelt理论计算了强度参数Ω_t(t=2, 4,6)，研究表明Ω₂在碲钨酸盐玻璃中主要受到Er-O键的共价性的影响，而Er^{3 +} 离子周围配位场的非对称性影响可以忽略.测得了Er³⁺在15 μm发射谱的荧光 半高宽 (FWHM=71—77nm)和Er³⁺的⁴I_13/2能级寿命 (τ^m=3—34 ms).应用McCumber理论计算了Er³⁺在15 μm处的受激发射截面(σ^peak=068—103×10^-20 cm²).比较了Er³⁺在不同玻璃基质里 的15 μm荧光带宽和发射截面，研究结果表明碲钨酸盐玻璃是一种制备宽带光纤放大器的理想基质材料.     

Tm3+/Yb3+共掺氧卤碲酸盐玻璃上转换发光研究

研究了Tm³⁺/Yb³⁺共掺氧卤碲酸盐玻璃的上转换发光光谱，分析了Tm₂O₃含量对Tm³⁺/Yb³⁺共掺氧卤碲酸盐玻璃上转换发光的影响机理.结果表明：在Tm³⁺/Yb³⁺共掺氧卤碲酸盐玻璃的上转换发光中，Tm³⁺存在较强的浓度猝灭效应.随Tm₂O₃含量增加，Tm³⁺的上转换蓝光和红光强度先增加，后降低，在0.1mol% Tm₂O₃达到最大.该结果有助于进一步提高Tm³⁺的上转换发光效率.     

卤化铅调整Tm3+/Yb3+共掺碲酸盐玻璃上转换发光研究

研究了卤化铅调整Tm³⁺/Yb³⁺共掺碲酸盐玻璃的热稳定性能、Raman 光谱和上转 换发光光谱，分析了Tm³⁺/Yb³⁺共掺氧卤碲酸盐玻璃的上转换发光 机理.结果发 现：混合卤化铅调整Tm³⁺/Yb³⁺共掺碲酸盐玻璃具有好的热稳定性 能、低的声 子能量、强的上转换蓝光.这表明混合卤化铅调整Tm³⁺/Yb³⁺共掺碲 酸盐玻璃是一种上转换蓝光激光器的潜在基质材料. 关键词： 氧卤碲酸盐玻璃 上转换光谱 发光机理 上转换蓝光激光器     

Tm3+/Yb3+共掺碲酸盐玻璃的近红外发光及能量传递机理

采用高温熔融法制备了组分为TeO₂-ZnO-Na₂O的Tm³⁺离子单掺和Tm³⁺/Yb³⁺共掺碲酸盐玻璃,应用Judd-Ofelt理论计算分析了玻璃样品的强度参量Ω_t(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τ_rad等光谱参量,测量得到了不同Yb³⁺离子掺杂浓度下玻璃样品的Tm³⁺离子上转换发光谱.结果显示,在980 nm泵浦光激励下玻璃样品发射出强烈的近红外上转换荧光.对Tm³⁺离子上转换发光分析表明,强烈的Tm³⁺离子近红外上转换发光主要来自于Yb³⁺/Yb³⁺离子间的共振能量传递以及基于单声子和双声子辅助的Yb³⁺/Tm³⁺离子间的非共振能量传递过程,并进一步计算得到了声子贡献比和能量传递系数.最后,计算分析了Tm³⁺:³F₄→³H₆能级间跃迁的1.8 μm波段吸收截面、受激发射截面和增益系数.研究表明,Yb³⁺/Tm³⁺共掺TeO₂-ZnO-Na₂O玻璃可以作为近红外波段固体激光器的潜在增益基质.