钕离子掺杂和钕铝共掺高硅氧玻璃的光谱性质研究

基于多孔玻璃烧结的方法制备了钕离子掺杂和钕铝共掺高硅氧玻璃，测量了掺钕高硅氧玻璃的吸收光谱、荧光光谱和荧光寿命. 利用Judd-Ofelt理论计算得到了钕离子在高硅氧玻璃中的强度参数，计算并对比了掺钕高硅氧玻璃和钕铝共掺高硅氧玻璃的理论荧光寿命、受激发射截面和发光量子效率.讨论了钕铝共掺高硅氧玻璃中铝离子的掺入对玻璃发光性质的影响. 通过与其他掺钕氧化物玻璃和一些商用硅酸盐玻璃的主要光谱性质的比较，掺钕高硅氧玻璃显示了较好的光谱性质，有可能成为一种应用于高能和高频激光领域的新型激光材料. 关键词： 掺钕高硅氧玻璃 钕铝共掺 光谱性质 Judd-Ofelt理论     

Enhanced optical activation of Er in Er-doped Al2O3 powders by Y codoping in a sol-gel method

Enhanced photoluminescence (PL) mechanism of Er³⁺-doped Al₂O₃ powders by Y³⁺ codoping at wavelength 1.53 μm has been investigated through PL measurements of 0.1 mol% Er³⁺- and 0-20 mol% Y³⁺-codoped Al₂O₃ powders prepared at a sintering temperature of 900 °C in a non-aqueous sol-gel method. PL intensity and lifetime of Er³⁺-Y³⁺-codoped Al₂O₃ powders composed of γ-(Al,Er,Y)₂O₃ and θ-(Al,Er,Y)₂O₃ phases increased with increasing Y³⁺-codoping concentration. The 10-20 mol% Y³⁺ codoping in 0.1 mol% Er³⁺-doped Al₂O₃ powders intensified the PL intensity by about 20 times, with a PL lifetime prolonged from 3.5 to 5.8 ms. A maximal increase of the optical activity of Er³⁺ in 0.1 mol% Er³⁺-Y³⁺-codoped Al₂O₃ powders about one order was achieved by 10-20 mol% Y³⁺ codoping. It is found that the improved PL properties for Er³⁺-Y³⁺-codoped Al₂O₃ powders are mainly attributed to enhanced optical activation of Er³⁺ in the Al₂O₃ by Y³⁺ codoping, and to the slightly increased radiative quantum efficiency of Er³⁺ in the Al₂O₃.     

Luminescence enhancement in (Nd+Ce) doped SiO2 : Al2O3 sol–gel glasses

An enhancement in NIR luminescence from Nd³⁺-doped Ce³⁺ co-doped SiO₂+Al₂O₃ sol–gel glasses has been observed. The lasing transition (⁴F_3/2→⁴I_11/2) at 1072 nm from the dual rare-earth Nd³⁺+Ce³⁺-doped glasses has shown an emission strength of about five times that of the single rare-earth ion Nd³⁺-doped glass. From the measurement of lifetimes of the transition at 1072 nm, the transfer rate (W_tr), critical distance (R₀) and energy transfer efficiency (η) of the neodymium glasses have been calculated.     

Energy transfer and infrared-to-visible upconversion luminescence of Er/Yb-codoped halide modified tellurite glasses

We report on the energy transfer and frequency upconversion spectroscopic properties of Er³⁺-doped and Er³⁺/Yb³⁺-codoped TeO₂-ZnO-Na₂O-PbCl₂ halide modified tellurite glasses upon excitation with 808 and 978 nm laser diode. Three intense emissions centered at around 529, 546 and 657 nm, alongwith a very weak blue emission at 410 nm have clearly been observed for the Er³⁺/Yb³⁺-codoped halide modified tellurite glasses upon excitation at 978 nm and the involved mechanisms are explained. The quadratic dependence of fluorescence on excitation laser power confirms the fact that the two-photon contribute to the infrared to green-red upconversion emissions. And the blue upconversion at 410 nm involved a sequential three-photon absorption process.     

Nd photoluminescence study of Nd-doped Si-rich silica films obtained by reactive magnetron sputtering

Nd³⁺-doped silicon-rich silicon oxide (SRSO) thin films have been fabricated by reactive magnetron sputtering of a pure silica target topped with Nd₂O₃ chips. The concentration of Nd ions in the deposited layers is controlled by the number of Nd₂O₃ chips, whereas the incorporation of silicon excess is monitored by the hydrogen partial pressure, P_H2, introduced in the Ar plasma, owing to the ability of hydrogen to reduce the oxygen released by the sputtering of the silica target. Photoluminescence (PL) experiments were made at room temperature using a nonresonant excitation line from an Ar laser. The influences of Nd³⁺ content and P_H2 have been studied to optimize the Nd³⁺ emission. PL spectra reveal a two order of magnitude enhancement of the Nd³⁺ emission around both 0.9 and 1.1 μm, when Si nanoclusters (Si-nc) are formed in the same Nd³⁺-doped matrix. The dependence of the Nd³⁺ PL with P_H2 and Nd concentration is indicative of the occurrence of an efficient energy transfer from the Si-nc to the rare earth ions. The radiative lifetime is also deduced and commented in the light of Nd³⁺-Si-nc coupling.     

Role of Al2O3 in upconversion and NIR emission in Tm and Er codoped calcium fluoro phosphorous silicate glass system

In this study, the principal role of Al₂O₃ on the features of the photoluminescence spectra of Tm³⁺ ion and upconversion phenomenon in Tm³⁺ and Er³⁺ codoped CaF₂−Al₂O₃−P₂O₅−SiO₂ glass system has been investigated. The concentration of Al₂O₃ is varied from 2 to 10 mol% while that of Er³⁺ and Tm³⁺ is fixed. IR and Raman spectral studies have indicated that there is a gradual increase in the degree of disorder in the glass network with increase in the concentration of Al₂O₃ up to 6.0 mol%. This is attributed to the presence of Al³⁺ ions in octahedral positions in larger proportions. When the glasses are doped with Tm³⁺ ions, the blue and red emissions were observed, whereas in Er³⁺ doped glasses blue, green and red emissions were observed. When the glasses are codoped with Tm³⁺ and Er³⁺ ions and excited at 790 nm, all the three emission lines were observed to be reinforced, especially in the glasses mixed with 6.0 mol% of Al₂O₃. The IR emission band detected at about 1.8 μm due to ³F₄→³H₆ transition of Tm³⁺ ions is also observed to be strengthened due to codoping. The reasons for enhancement in the intensity of various emission bands due to codoping have been identified and discussed with the help of rate equations for various emission transitions.     

Optical and electronic polarizability investigation of Nd-doped soda-lime silicate glasses

This paper reports on different physical and optical properties of Nd³⁺-doped soda-lime silicate glass. The glasses containing Nd³⁺ in (65−x)SiO₂:25Na₂O:10CaO:xNd₂O₃ (where x=0.0-5.0 mol%) have been prepared by the melt-quenching method. In order to understand the role of Nd₂O₃ in these glasses the density, molar volume, refractive index and optical absorption were investigated. The results show that the density and molar volume of the glasses increase with an increase in Nd₂O₃ concentration and consequently generate more non-bridging oxygen (NBOs) into glass matrix. The optical absorption spectra were measured in the wavelength range from 300 to 700 nm and the optical band gaps were determined. It was found that the optical band gap decreases with an increase in Nd₂O₃ concentration. On the basis of the measured values of density and refractive index, the Nd³⁺ ion concentration in glasses, the polarizability of oxide ions and optical basicity were theoretically determined.     

Time Resolved Fluorescence and Energy Transfer Analysis of Nd<Superscript>3+</Superscript>–Yb<Superscript>3+</Superscript>–Er<Superscript>3+</Superscript> Triply-Doped Ba–Al-Metaphosphate Glasses for an Eye Safe Emission (1.54 μm)

This paper reports on the preparation and systematic analysis of energy transfer mechanisms in Nd³⁺–Yb³⁺–Er³⁺ co-doped new series of barium-alumino-metaphosphate glasses. The time resolved fluorescence of Nd³⁺ in triply doped Ba–Al-metaphosphate glasses have revealed that, Yb³⁺ ions could function as quite efficient bridge for an energy transfer between Nd³⁺ and Er³⁺ ions. As a result, a fourfold emission enhancement at 1.54 μm of Er³⁺ ions has been achieved through an excitation of ⁴F_5/2 level of Nd³⁺ at 806 nm for the glass having 3 mol% Yb³⁺ with an energy transfer efficiency reaching up to 94%. Decay of donor (Nd³⁺) ion fluorescence has been analyzed based on theoretical models such as direct energy transfer model (Inokuti–Hirayama) and migration assisted energy transfer models (Burshtein’s hopping and Yokota–Tanimoto’s diffusion). The corresponding energy transfer parameters have been evaluated and discussed. Primarily, electrostatic dipole–dipole (s ~ 6) interactions are found to be responsible for the occurrence of energy transfer process in theses glasses.     

Observation of stimulated Raman scattering in Y3Al5O12 single crystals and nanocrystalline ceramics and in these materials activated with laser ions Nd3+ and Yb3+

High-order Raman parametric generation was excited in the visible and near-IR regions on the Stokes and anti-Stokes lines of Y₃Al₅O₁₂ single crystals and nanocrystalline ceramics. All generation components, as well as the χ⁽³⁾-active vibrational modes of these materials, were identified. In connection with the extensive use of the Nd³⁺-and Yb³⁺-doped Y₃Al₅O₁₂ crystals and, in recent years, nanocrystalline Y₃Al₅O₁₂: Nd³⁺ ceramics in laser physics and quantum electronics, the applied aspect of the observed nonlinear properties of these materials is outlined.     

钕玻璃的光谱性质

本文分析了Nd³⁺在玻璃中的stark分裂情况,描写了确定荧光能级的实验方法,并给出了钕在四种硅酸盐玻璃中亚稳态和基态能级Stark分裂的实验结果。同时,对十三种不同成份的玻璃,通过光谱实验确定了Nd^{3+ 4}F_3/2态的辐射和无辐射跃迁速率,受激发射截面σ,辐射量子效率η,荧光分支比β和亚稳态寿命τ等激光常用参数。并对实验结果进行了讨论。 关键词：     

High Quantum Efficiency of Nd3+ Ions in a Phosphate Glass System using the Judd–Ofelt Theory

The optical properties of trivalent neodymium embedded in a P₂O₅–Al₂O₃–Na₂O–K₂O phosphate glass system, synthesized by the fusion method, are studied. Absorption, luminescence, lifetime, and Raman spectroscopy measurements were performed and the Judd–Ofelt theory was applied to determine optical parameters such as the quantum efficiency and the stimulated emission cross section of the Nd³⁺-doped glass system. This structure has high quantum efficiency at low Nd³⁺ concentrations, comparable to the efficiency of a commercial YAG:Nd³⁺ crystal. We discuss the mechanisms responsible for the high quantum efficiency observed in the proposed phosphate glass system.     

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     

Green and red up-conversion emissions of Er-Yb-codoped Al2O3 powders prepared by the nonaqueous sol-gel method

The 1 mol% Er³⁺- and 0-20 mol% Yb³⁺-codoped Al₂O₃ powders have been prepared by the nonaqueous sol-gel process using aluminum isopropoxide as precursor, acetylacetone as chelating agent, nitric acid as catalyzer, and hydrated erbium and ytterbium nitrate as dopant under isopropanol environment. The two crystalline types of doped Al₂O₃, γ and θ, and a stoichiometric compound, (Yb,Er)₃Al₅O₁₂, were obtained for all the Er³⁺-Yb³⁺-codoped Al₂O₃ powders at the sintering temperature of 1000 °C. The maximal intensity of both the green and red up-conversion emissions centered at about 523, 545, and 660 nm was observed for the 1 mol% Er³⁺- and 10 mol% Yb³⁺-codoped Al₂O₃ powders. The intensity ratio of the red to green up-conversion emission (I_red/I_green) increased with increasing the Yb³⁺ doping concentration for the Er³⁺-Yb³⁺-codoped Al₂O₃ powders. Furthermore, the intensity ratio of the green up-conversion emission at about 523 to 545 nm (I₅₂₃/I₅₄₅) was proportional to the Yb³⁺ doping concentration and pump electric current, which was associated with the elevated temperature of powders.     

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.     

掺铒高硅氧玻璃光谱性质的研究

应用Judd-Oflet理论计算了新型掺铒高硅氧玻璃中铒离子的强度参量Ω_t(t=2,4,6)，Ω₂=8.15×10^-20，Ω₄=1.43×10^-20，Ω₆=1.22×10^-20，相比于其他氧化物玻璃，表现出较大的Ω_2,6值，反映了铒离子周围的近邻结构不对称性和Er-O键的离子键成分较高.利用McCumber理论计算得到了能级^{关键词： 掺铒高硅氧玻璃 Judd-Ofelt理论 量子效率}     

Mid-Infrared Emission Characteristic and Energy Transfer of Ho<Superscript>3+</Superscript>-Doped Tellurite Glass Sensitized by Tm<Superscript>3+</Superscript>

We report on 2.0-μm emission characteristic and energy transfer of Ho³⁺-doped tellurite glass sensitized by Tm³⁺ upon excitation of a conventional 808 nm laser diode. The Judd-Ofelt strength parameters, spontaneous radiative transition probabilities and radiative lifetime of Ho³⁺ have been calculated from the absorption spectra by using the Judd-Ofelt theory. Significant enhancement of 2.0-μm emission of Ho³⁺ has been observed with increasing Tm³⁺ doping up to 0.7 mol%. The energy transfer coefficient of the forward Tm³⁺→Ho³⁺ is approximately 17 times larger than that of the backward Tm³⁺←Ho³⁺ energy transfer. Our result indicates that the maximum gain of 2.0-μm emission, assigned to the transition of ⁵I₇→⁵I₈ of Ho³⁺, might be achieved from the tellurite glass at the concentration of 0.5 mol% of Tm₂O₃ and 0.15 mol% of Ho₂O₃. The high gain coefficient and quantum efficiency (1.16) along with the large value of the product of the stimulated emission cross-section and the measured radiative lifetime (4.12×10⁻²⁷ m²s) of the Ho³⁺/Tm³⁺-codoped tellurite glasses might find potential applications in efficient 2.0-μm laser.     

Infrared-to-visible up-conversion emissions and thermometric applications of Er 3+-doped Al 2 O 3

Er³⁺-doped Al₂O₃ has been prepared by a sol–gel method, using aluminium isopropoxide [Al(OC₃H₇)₃]-derived Al₂O₃ sols with addition of erbium nitrate [Er(NO₃)₃·5H₂O]. The phase structure of θ-(Al,Er)₂O₃ phase was obtained for the 0.1 mol. % Er³⁺-doped Al₂O₃ at the sintering temperature of 1273 K. The green and red up-conversion emissions centered at about 523, 545 and 660 nm, corresponding respectively to the ² H _11/2, ⁴ S _3/2→⁴ I _15/2 and ⁴ F _9/2→⁴ I _15/2 transitions of Er³⁺, were detected by a 978-nm semiconductor laser diode excitation. The temperature dependence of green up-conversion emissions was studied over a wide temperature range of 295–725 K, and reasonable agreement between the calculated temperatures obtained by the fluorescence intensity ratio theory and the measured temperature was obtained, which proved that Er³⁺-doped Al₂O₃ has a good potential for the development of high-temperature sensors. It has some advantages compared to glasses due to its higher thermal and mechanical resistance and allows measurements in a large temperature range. PACS 78.55.Hx; 81.40.Tv     

The effect of alkaline earth metallic ions on the photoluminescence properties of sol-gel silica glass

Mg²⁺-, Ca²⁺-, Sr²⁺- and Ba²⁺-doped silica glasses have been prepared using sol-gel processing by employing Si(OC₂H₅)₄, MgCl₂6H₂O, CaCl₂2H₂O, SrCl₂6H₂O and BaCl₂2H₂O as precursors, with HCl as a catalyst. The UV–visibleabsorption spectra of the doped samples are almost the same as those of the undoped sample. The absorption bands of alkaline earth metallic ions have not been observed in the doped samples. Strong visible light has been observed from sol- gel silica glasses doped with alkaline earth metallic ions. The relative fluorescence intensity of the Sr²⁺-doped (the impurity mole ratio of Sr²⁺ was 0.268%) and the Ba²⁺-doped (the impurity mole ratio of Ba²⁺ was 0.448%) samples was about 4 times that of the undoped sample. The relative fluorescence intensity of the Mg²⁺-doped (the impurity mole ratio of Mg²⁺ was 0.069%) sample was about 2.5 times that of the pure glass sample. The relative fluorescence intensity of the Ca²⁺- doped (the impurity mole ratio of Ca²⁺ was 0.179%) sample was about 3 times that of the pure glass sample. Alkaline earth metallic ions affect the formation and conversion of luminescent defects in sol-gel silica glass. Thus, the relative fluorescence intensity of the doped samples increases more than that of the undoped sample. Received: 17 April 2001 / Accepted: 6 June 2001 / Published online: 30 August 2001     

Comparative investigation on spectroscopic properties of Er between Ce-doped and B2O3-added bismuth glasses

The comparative investigation on the spectroscopic properties of Er³⁺ in low phonon energy Bi₂O₃-GeO₂-Ga₂O₃-Na₂O glasses codoped with Ce³⁺ ion and added with B₂O₃ component, respectively, is presented. With increasing Ce₂O₃ content from 0 to 0.8 mol% or B₂O₃ content from 0 to 15 mol%, the lifetime of Er³⁺:⁴I_11/2 level decreases dramatically from 607 to 283 μs or to 197 μs, and the upconversion fluorescence is quenched in both glass samples. The nonradiative energy transfer from Er³⁺:⁴I_11/2→Ce³⁺:²F_5/2 or the enhanced multiphonon relaxation process together with the energy transfer between Er³⁺ and OH⁻ groups are, respectively, responsible for the results. Meanwhile, the lifetime of ⁴I_13/2 level remains almost unchanged in Er³⁺/Ce³⁺-codoped glasses whereas it decreases rapidly in B₂O₃-added cases. As a result, Er³⁺/Ce³⁺ codoping improves the 1.5 μm fluorescence emission intensity, however, B₂O₃ addition has a negative effect on it. The research results indicate that the Er³⁺/Ce³⁺-codoped bismuth glasses will be preferable for obtaining efficient 980 nm pumped EDFA.     

Laser-diode-pumped Yb:YAG laser as a new pump source and its application to an Er3+, Yb3+-codoped high-output-power fiber amplifier

We propose a laser-diode-pumped Yb:YAG laser as a novel practical fiber amplifier pump source, and describe its first successful application of high-output-power operation (850 mW=+29.3 dB m) of an Er³⁺,Yb³⁺-codoped fiber amplifier at 1.55 μm. We have developed both bulk and microchip Yb:YAG lasers and obtained 3.3 W and 2.7 W, respectively, in the cw mode at room temperature. Laser-diode-pumped Yb:YAG lasers are shown to have a potential applicability to such fiber amplifiers as Pr³⁺-doped amplifiers and Tm³⁺-doped amplifiers, as well as Er³⁺,Yb³⁺-codoped fiber amplifiers. Received: 12 August 1999 / Revised version: 3 September 1999 / Published online: 20 October 1999