Luminescence of transparent glass ceramics containing Er<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript> zirconate-titanate nanocrystals

Luminescence regularities have been studied in new erbium/ytterbium materials based on glasses and glass ceramics of a magnesium-aluminosilicate system containing nanoscale erbium/ytterbium zirconate titanate crystals with the pyrochlore structure. Lifetimes of Yb³⁺ and Er³⁺ ions in the ² F_5/2 state and in the ⁴I_11/2 and ⁴I_13/2 states, respectively, and the efficiency of Yb³⁺ → Er³⁺ energy transfer have been evaluated. The identified spectral-luminescent characteristics of the studied glasses and glass ceramics co-doped with erbium and ytterbium ions show that these materials are promising media for producing laser generation in the spectral range around 1.5 μm.     

A cobalt-doped transparent glass ceramic saturable absorber Q-switch for a LD pumped Yb<Superscript>3+</Superscript>/Er<Superscript>3+</Superscript> glass microchip laser

We fabricate a transparent glass ceramic contains magnesium-aluminum spinel nanocrystallites doped with Co²⁺ ions. The ground-state and excited-state absorption cross section of this glass ceramic at 1.54 μm are estimated to be (2.8 ± 0.3) × 10⁻¹⁹ cm² and (4.8 ± 0.5) × 10⁻²⁰ cm², respectively. For the first time, the passively Q-swithched operation of LD pumped 1.54 μm microchip Yb³⁺/Er³⁺ glass laser is realized with transparent glass ceramic as saturable absorber. The Q-switched pulses of 3.846 kHz in repetition rate, 6.2 ns in duration and 6.3 μJ in energy are obtained. At last, the dependences of pulse width and repetition rate on pump power are also investigated.     

Er3+及Er3+/Yb3+共掺铋酸盐玻璃光谱性质研究

制备了Er³⁺及Er³⁺/Yb³⁺共掺铋酸盐玻璃，测试了样品的吸收光谱、荧光光谱.应用Judd-Oflet理论计算了Er³⁺在铋酸盐玻璃中的光谱强度参数，分别为Ω₂=(5.47—2.92)×10^-20cm²，Ω₄=(2.16—1.22)×10^-20cm², 关键词： 3+')" href="#">Er³⁺ 铋酸盐玻璃 3+/Yb³⁺共掺')" href="#">Er³⁺/Yb³⁺共掺 光谱性质     

掺铒铋酸盐玻璃的光谱性质研究

研究了掺铒铋酸盐玻璃的吸收和荧光光谱性质,应用Judd-Ofelt理论计算了玻璃的三个强度参量Ω_t=(t=2,4,6),分别为Ω₂=3.71×10^-20cm²,Ω₄=1.86×10^-20cm²,Ω₆=1.28×10^-20cm²,计算了Er³⁺离子的自发跃迁几率、荧光分支比等光谱参量.经荧光谱测试发现掺Er³⁺铋酸盐玻璃的荧光半高宽可达70nm.应用McCumber理论计算1.53μm处的受激发射截面可达9×10^-21cm².对Er³⁺离子在不同基质玻璃中光谱特性的比较发现,Er³⁺在铋酸盐玻璃中具有相对较高的受激发射截面和宽的荧光半高宽.     

Spectroscopic study of double sodium-yttrium fluoride crystals doped with erbium Na<Subscript>0.4</Subscript>Y<Subscript>0.6</Subscript>F<Subscript>2.2</Subscript>:Er<Superscript>3+</Superscript>: I. Intensities of luminescence spectra and kinetics of luminescence

Na_0.4Y_0.6F_2.2:Er³⁺ (NYF:Er) crystals with an erbium concentration as high as 100 at. % (Na_0.4Er_0.6F_2.2) were grown by the Bridgman-Stockbarger method. The optical spectra were investigated at low (6 K) and room temperatures. It is shown that the absorption spectrum of NYF:Er crystals contains wide bands (790–801 and 965–980 nm) corresponding to the emission range of laser diodes. The peak absorption cross section σ_a for the band peaked at λ=970.4 nm is 0.15×10^?20 cm². On the basis of the analysis of the absorption and luminescence spectra at low (6 and 12 K) temperatures, the structure of the Stark splitting of erbium levels was determined as a structure of quasi-centers for which Stark components are inhomogeneously broadened. The oscillator strengths of the transitions from the ground state of erbium to excited multiplets were calculated from the absorption spectra measured at T=300 K, and the intensity parameters Ω_t were determined by the Judd-Ofelt method: Ω₂=1.65×10^?20 cm², Ω₄=0.56× 10^?20 cm², and Ω₆=1.01×10^?20 cm². These values of the intensity parameters were used to calculate the probabilities of radiative transitions and the branching ratios. The rates of multiphonon nonradiative transitions in NYF: Er were estimated. The luminescence decay kinetics for radiative levels of erbium ions upon their selective excitation by nanosecond laser pulses was studied. The intracenter lifetimes of radiative levels of erbium ions were determined from the luminescence kinetics upon selective ion excitation by low-intensity light in a sample with a low erbium concentration (0.5%). It is demonstrated that, with an increase in temperature from 6 to 300 K, luminescence from the ⁴ G _11/2, ² G(H)_9/2, and ⁴ F _9/2 levels is quenched as a result of multiphonon nonradiative transitions. Luminescence from the ⁴ I _9/2 level is quenched only insignificantly with increasing temperature, and no quenching of luminescence from the ⁴ I _11/2 and ⁴ I _13/2 levels is observed. The spectra of steady-state luminescence of NYF:Er(0.5–15%) crystals were investigated upon broadband excitation by UV and UV-visible lamp light and selective time-resolved laser excitation. It is shown that low-lying levels of erbium ions separated by an energy gap smaller than 2500 cm^?1 are populated via cascade mechanisms. On the basis of the results obtained, it is concluded that NYF:Er ³⁺ crystals are promising candidates for active media of tunable diode-pumped lasers.     

Spectroscopic study of erbium-activated crystals of double calcium yttrium fluoride Ca<Subscript>0.89</Subscript>Y<Subscript>0.11</Subscript>F<Subscript>2.11</Subscript>:Er<Superscript>3+</Superscript>: I. Intensity of spectra and luminescence kinetics

Ca_0.89Y_0.11F_2.11:Er³⁺ (CYF:Er) crystals with an erbium content of 1–15 at % have been grown. The optical spectra and luminescence kinetics of CYF:Er crystals have been investigated at low (～5 K) and room temperatures. Based on an analysis of the absorption spectra at low temperature, the structure of Stark splitting of erbium levels in CYF:Er crystals is determined. Room-temperature absorption spectra are used to calculate the spectra of absorption cross sections and oscillator strengths of transitions from the erbium ground state to excited multiplets. It is shown that the absorption spectrum of CYF:Er crystals contains broad bands in the ranges of 790–815 and 965–980 nm, which correspond to the range of emission of laser diodes. For the band peaking near 967 nm, the peak absorption cross section is σ _abs ^max = 2.7 × 10^?21 cm². The intensity parameters are determined by the Judd-Ofelt method to be Ω₂ = 1.39 × 10^?20, Ω₄ = 1.34 × 10^?20, and Ω₆ = 2.24 × 10^?20 cm². The radiative transition probabilities, radiative lifetimes, and branching ratios are calculated with these values. The luminescence decay kinetics from excited erbium levels upon selective excitation is investigated and the experimental lifetimes of the 4F _9/2, ⁴ S _3/2, and ⁴ G _11/2 radiative erbium levels are determined. The dependences of multiphonon relaxation rates on the energy gap in CYF:Er crystals are obtained. The rates of nonradiative multiphonon relaxation from radiative erbium levels are determined.     

Intensity parameters for Er<Superscript>3+</Superscript> ions in calcium-niobium-gallium garnet crystals

Based on the analysis of the absorption spectra of Er-doped calcium-niobium-gallium garnet (Er:CNGG) crystals according to the Judd-Ofelt theory, the intensity parameters for these crystals are determined to be Θ₂ = 3.43 × 10^?20 cm² Θ₄ = 1.20 × 10^?20 cm², and Θ₆ = 0.58 × 10^?20 cm². The parameters found are compared with the intensity parameters for other laser oxide crystals. Using these intensity parameters, the probabilities of radiative transitions between the energy levels of Er³⁺ ions in CNGG crystals and the luminescence branching ratios β_JJ’ are calculated. From the measured lifetime of the ⁴ I _11/2 level of Er³⁺ ions (τ = 626 μs) and the probability of the radiative transition from this level (A = 192 s^?1), it is found that about 88% of the excitation energy in the Er:CNGG crystals is nonradiatively transferred from the ⁴ I _11/2 to the ⁴ I _13/2 level. It is suggested that an increase in the oscillator strength and in the line strength of the ⁴ I _15/2 → ² H _11/2 transition of Er³⁺ in CNGG crystals, as well as an increase in the intensity parameter Θ₂ with respect to the corresponding parameters for other garnet crystals are caused by the existence in CNGG crystals of Er³⁺ centers with the environment symmetry lower than D ₂.     

Photoluminescence of Er<Superscript>3+</Superscript> ions in layers of quasi-ordered silicon nanocrystals in a silicon dioxide matrix

The spectra and kinetics of photoluminescence from multilayered structures of quasi-ordered silicon nanocrystals in a silica matrix were studied for undoped samples and samples doped with erbium. It was shown that the optical excitation energy of silicon nanocrystals could be effectively transferred to Er³⁺ ions, which was followed by luminescence at a wavelength of 1.5 µm. The effectiveness of energy transfer increased as the size of silicon nanocrystals decreased and the energy of exciting light quanta increased. The excitation of erbium luminescence in the structures was explained based on dipole-dipole interaction (the Förster mechanism) between excitons in silicon nanocrystals and Er³⁺ ions in silica surrounding them.     

Improvement of thermal and spectroscopic behavior of Er<Superscript>3+</Superscript>/Ce<Superscript>3+</Superscript> co-doped tellurite glass for lasing materials

Tellurite glasses (TeO₂–ZnO–Nb₂O₅) mono-doped Er³⁺ and co-doped Er³⁺/Ce³⁺ have been prepared using the melt-quenching technique. To evaluate the effect of Ce³⁺ on the structural, thermal stability of glass hosts and fluorescence properties of Er³⁺, X-ray diffraction patterns, Ftir spectra, differential scanning calorimeter curves, absorption spectra, fluorescence emission spectra, fluorescence lifetimes, up-conversion emission spectra of glass samples were measured and investigated. Using Judd–Ofelt theory, we calculated intensity parameters (Ω₂, Ω₄ and Ω₆), spontaneous emission probabilities, the radiative lifetime, luminescence branching factors and the quantum yield of luminescence for ⁴I_13/2 → ⁴I_15/2 transition. The co-doping with Ce³⁺ was effective on the suppression of up-conversion emission of Er³⁺ owing to the phonon-assisted energy transfer: Er³⁺:⁴I_11/2 + Ce³⁺:²F_5/2 → Er³⁺:⁴I_13/2 + Ce³⁺:²F_7/2 which contributed the effective enhancement of 1.53 µm fluorescence emission. The change in optical properties with the addition of Ce³⁺ ions have been discussed and compared with other glasses. Using the Mc Cumber method for the ⁴I_13/2 → ⁴I_15/2 transition, absorption cross-section, calculated emission cross-section, and gain cross-section values support that TZNEr1Ce1 glass is a potential material for developing broad-band and high-gain erbium-doped fiber amplifiers applied for 1.53 µm.     

Energy transfer from the host to Er<Superscript>3+</Superscript> dopants in semiconductor SnO<Subscript>2</Subscript> nanocrystals segregated in sol–gel silica glasses

Undoped and Er³⁺-doped glass–ceramics of composition (100−x)SiO₂–xSnO₂, with x = 5 or 10 and with 0.4 or 0.8 mol% of Er³⁺ ions, were synthesised by thermal treatment of precursor sol–gel glasses. Structural studies were developed by X-Ray Diffraction. Wide band gap SnO₂ semiconductor quantum-dots embedded in the insulator SiO₂ glass are obtained. The mean radius of the SnO₂ nanocrystals, ranging from 2 to 3.2 nm, is comparable to the exciton Bohr radius. The luminescence properties have been analysed as a function of sample composition and thermal treatment. The results show that Er³⁺ ions are partially partitioned into the nanocrystalline phase. An efficient UV excitation of the Er³⁺ ions by energy transfer from the SnO₂ nanocrystal host is observed. The Er³⁺ ions located in the SnO₂ nanocrystals are selectively excited by this energy transfer mechanism. On the other hand, emission from the Er³⁺ ions remaining in the silica glassy phase is obtained by direct excitation of these ions.     

Photo-induced densification in Er<Superscript>3+</Superscript>/Al doped silica preform plates using 193-nm laser light

The growth rate of Bragg gratings written using 193-nm light from an ArF excimer laser is shown to be non-linear with the pulse energy density for Er³⁺ co-doped Al silica. This yields a refractive-index increase up to a few 10⁻³. We then use phase-shift interferometry to measure the sample surface topography following exposure. Subsequently, we formulate an inhomogeneous stress model to analyse the observed change of volume within the core material. Below pulse energies of 550 mJ/cm², the results show that refractive-index changes are primarily due to a densification process. At higher pulse energies material re-expansion occurs.     

Spectroscopic properties of Er<Superscript>3+</Superscript> ions in LiNbO<Subscript>3</Subscript> crystals codoped with HfO<Subscript>2</Subscript>

The results of the spectroscopic analysis of transition strengths for Er³⁺ ions in a series of Hf:Er:LiNbO₃ crystals with variable Hf content and fixed Er content are reported. Unpolarized UV-VIS-NIR absorption spectra, upconversion fluorescence spectra excited at 800 nm, and microsecond time-resolved spectra excited at 400 nm and 800 nm by 800 nm femtosecond laser were measured at room temperature. The HfO₂ incorporation has influence on Er³⁺ radiative lifetimes, and fluorescence branching ratios. For Hf(4 mol %):Er(1 mol %):LiNbO₃, Ω₂=2.63×10^-20 cm², Ω₄=2.86×10^-20 cm², and Ω₆=0.72×10^-20 cm². Ω₂<Ω₄ is contrary to the Er³⁺ general trend of Ω₂>Ω₄>Ω₆ when the Hf content is below its threshold concentration. In addition, the sum of Ω increases with the Hf content when the HfO₂ content below 6 mol % is unfamiliar. The upconversion mechanism is discussed in this work. PACS 71.20.Eh; 77.84.Dy; 42.62.Fi; 42.65.Ky     

Green,blue, red,near-infrared up-conversion luminescence of Yb<Superscript>3+</Superscript>/Er<Superscript>3+</Superscript>/Tm<Superscript>3+</Superscript> co-doped YVO<Subscript>4</Subscript> nanoparticles

YVO₄:Yb³⁺,Er³⁺; YVO₄:Yb³⁺,Tm³⁺; and YVO₄:Yb³⁺,Er³⁺,Tm³⁺ were all synthesized via sol-gel method with a subsequent thermal treatment. Specifically, YVO₄:Yb³⁺,Er³⁺,Tm³⁺ phosphors were prepared with different annealing temperatures to study the influence of temperature. The transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray diffractometer (XRD), and photoluminescent (PL) spectrofluorometer were used to investigate the morphology, crystal structure, and up-conversion luminescent properties of all samples. In summary, all samples were granular-like nanoparticles and well crystallized with the same tetragonal phase as YVO₄. Under the irradiation at 980 nm, YVO₄:Yb³⁺,Er³⁺ phosphors can generate green emission at 525 and 553 nm and red emission at 657 nm, while YVO₄:Yb³⁺,Tm³⁺ phosphors can generate blue emission at 476 nm, red emission at 648 nm, and near-infrared emission at 800 nm. Notably, YVO₄:Yb³⁺,Er³⁺,Tm³⁺ samples can exhibit green emission, blue emission, red emission, and near-infrared emission at the same time, which might endow the as-prepared samples with potential applications in many fields, such as luminous paint, infrared detection, and biological label.     

Erbium excitation in a SiO<Subscript>2</Subscript>: Si-nc matrix under pulsed pumping

The photoluminescence of Er³⁺ ions in a SiO₂ matrix containing silicon nanocrystals 3.5 nm in diameter is studied under resonant and nonresonant pulsed pumping with pulses 5 ns in duration. The effective erbium excitation cross section under pulsed pumping, σ_eff = 8.7 × 10^?17 cm₂, is close to that for nanocrystals. Comparison of the erbium photoluminescence intensity obtained for a SiO₂ matrix with and without nanocrystals made it possible to determine the absolute concentration of optically active nanocrystals capable of exciting erbium ions, the concentration of optically active erbium, and the average number of erbium ions excited by one nanocrystal. The study revealed that excitation transfer from one erbium ion to another is a relatively slow process, which accounts for the low efficiency of erbium ion excitation under pulsed pumping in a SiO₂ matrix containing silicon nanocrystals.     

一种新型掺铒碲酸盐玻璃的光谱性质研究

研究了一种新型掺Er³⁺碲酸盐玻璃的光谱性质；应用Judd-Ofelt理论计算了碲 酸盐玻璃中Er³⁺离子的强度参数Ω(Ω₂=479×10^-20 cm²,Ω₄= 152×10^-20cm²,Ω₆=066×10^-20cm2)，计算了离子的自发跃迁概 率，荧光分支比；应用McCumber理论计算了Er³⁺的受激发射截面(σ_{e=1040×1 0^-21cm²)，Er³⁺离子⁴I13/ 2→⁴I15/2发射谱的 荧光半高宽(FWHM=655nm)及各能级的荧光寿命(⁴I13/2 能级为τrad =399ms)；比较了不同基质玻璃以及不同类型碲酸盐玻璃中Er³⁺离子的光谱 特性， 结果表明该掺铒碲酸盐玻璃具有更好的光谱性能，更适合于掺Er³⁺光纤放大 器实现宽带和高增益放大. 关键词： 碲酸盐玻璃 光谱性质 Judd-Ofelt理论}     

Energy transfer and upconversion in erbium–ytterbium-doped fluoride phosphate glasses

The energy-transfer rate coefficient from ytterbium to erbium (K) and upconversion rate coefficient for erbium (C) are determined by analysis of erbium fluorescence decay under different pumping conditions. A simple rate-equation model was used to describe the fluorescence dynamics. Numerical analysis of the model delivered K and C as fit parameters to the experimental curves. Values of K ranging from 0.75–1.42×10^-16 cm³/s and C from 0.8–1.7×10^-18 cm³/s were found. The results obtained are of the same magnitude as results for phosphate glasses reported in the literature. Further analysis showed that high erbium concentrations (2×10²⁰ cm^-3) need a much higher pump intensity to reach threshold due to increased losses caused by upconversion. Received: 14 January 2002 / Published online: 7 February 2002     

Spectroscopic properties of Er<Superscript>3+</Superscript> in Sc:LiNbO<Subscript>3</Subscript> crystal

The results of Er³⁺ ion spectroscopic analysis in Sc:LiNbO₃ crystals were reported. The line strengths from the ground state to the excited state were evaluated from the measured unpolarized absorption spectrum and analyzed by using standard Judd–Ofelt theory. For Sc(3 mol. %):Er (1 mol. %):LiNbO₃ crystal, the obtained intensity parameters are: Ω₂=3.72×10^-20 cm², Ω₄=1.07×10^-20 cm², and Ω₆=0.98×10^-20 cm². The fluorescence spectra and microsecond time-resolved spectra were investigated in the visible region. The excited state absorption transition strengths at 800 nm excitation were evaluated based on Judd–Ofelt theory. The results obtained here were compared to results from other research on Er:LiNbO₃ crystals. PACS 71.20.Eh; 77.84.Dy; 42.70.Hj; 42.62.Fi; 42.65.Ky     

Spectroscopic properties of Nd<Superscript>3+</Superscript>:CaNb<Subscript>2</Subscript>O<Subscript>6</Subscript> crystal

The absorption spectra, fluorescence spectrum and fluorescence decay curve of Nd³⁺ ions in CaNb₂O₆ crystal were measured at room temperature. The peak absorption cross section was calculated to be 6.202×10⁻²⁰ cm² with a broad FWHM of 7 nm at 808 nm for E//a light polarization. The spectroscopic parameters of Nd³⁺ ions in CaNb₂O₆ crystal have been investigated based on Judd-Ofelt theory. The parameters of the line strengths Ω _t are Ω ₂=5.321×10⁻²⁰ cm²,Ω ₄=1.734×10⁻²⁰ cm²,Ω ₆=2.889×10⁻²⁰ cm². The radiative lifetime, the fluorescence lifetime and the quantum efficiency are 167 μs, 152 μs and 91%, respectively. The fluorescence branch ratios are calculated to be β ₁=36.03%,β ₂=52.29%,β ₃=11.15%,β ₄=0.533%. The emission cross section at 1062 nm is 9.87×10⁻²⁰ cm².     

荧光俘获效应对掺饵氧化物玻璃光谱性质的影响

测试了不同掺杂浓度和样品厚度下掺铒磷酸盐和碲酸盐玻璃的吸收光谱、荧光光谱和荧光寿 命，计算了Er³⁺离子在1.53 μm处的吸收截面(σ_a)、发射截面(σ _e)、自发辐射跃迁概率(A_rad)、辐射跃迁寿命(τ_rad) 、以及辐射跃迁量子效率(η)等光谱参数.讨论了荧光俘获效应对掺铒磷酸盐和碲酸盐玻璃 光谱性质及光谱参数的影响.结果表明即使在铒离子低掺杂浓度(0.1 mol% Er₂O ₃)下，荧光俘获效应也普遍存在于掺铒玻璃材料中，使得荧光寿命(τ_{f)和荧光半高宽(FWHM)随样品的厚度和铒离子掺杂浓度增加而增大，导致碲酸盐和磷酸 盐玻璃中τf分别增加11%—37％和6%—17%，FWHM分别增加15%—64%和11%—55% ，使得掺铒玻璃材料的放大品性参数(σe×FWHM) 也相应被估高.由于铒离子在 碲酸盐玻璃中在1.53 μm处吸收和发射截面重叠面积较大，加之铒离子在前者基质中的发射 截面高于后者，使得掺铒碲酸盐玻璃中的荧光俘获效应高于磷酸盐玻璃. 关键词： 荧光俘获 铒离子 碲酸盐玻璃 磷酸盐玻璃}     

混合形成体对掺铒碲酸盐玻璃的热力学稳定性和发光性能的影响

研究了混合形成体效应对掺铒碲酸盐玻璃热力学稳定性、1.53 μm发光特性和上转换发光强度的影响.通过拉曼光谱测试,分析了WO₃,Nb₂O₅,GeO₂等氧化物对Er³⁺离子配位场结构,以及对发光谱的非均匀展宽机理的作用.结果表明,通过掺杂适当声子能量的网络形成体氧化物,不但可获得热力学稳定性较好的玻璃,还可有效降低Er³⁺离子⁴I_11/2能级的寿命,在抑制Er³⁺离子在可见光波段的上转换发光的同时不致劣化其在1.53 μm的发光特性.本文制得的碲酸盐玻璃具有较大的受激发射截面((9.64—10.96)×10^-21cm²)和荧光半高宽(FWHM)(50—67 nm),热力学稳定性良好,是一种理想的掺Er³⁺宽带有源光纤用基质玻璃. 关键词： 掺铒碲酸盐玻璃 混合形成体 1.53 μm发光 声子能量