Improved optical photoluminescence by charge compensation in the phosphor system CaMoO4:Eu

It has been found that charge compensated CaMoO₄:Eu³⁺ phosphors show greatly enhanced red emission under 393 and 467 nm-excitation, compared with CaMoO₄:Eu³⁺ without charge compensation. Two approaches to charge compensation, (a) 2Ca²⁺ → Eu³⁺ + M⁺, where M⁺ is a monovalent cation like Li⁺, Na⁺ and K⁺ acting as a charge compensator; (b) 3Ca²⁺ → 2Eu³⁺ + vacancy, are investigated. The influence of sintering temperature and Eu³⁺ concentration on the luminescent property of phosphor samples is also discussed.     

Optical properties, fluorescence mechanisms and energy transfer in Tm, Ho and Tm -Ho doped near-infrared laser glasses, sensitized by Yb

The optical properties of the rare elements Tm³⁺, Ho³⁺ and Yb³⁺ were systematically investigated in various glasses. The Tm³⁺ doped aluminozircofluoride glass shows higher quantum efficiency, longer lifetime and stronger fluorescence intensity than Tm³⁺ doped YSGG crystal and other Tm³⁺ doped glasses for the ³H₄ → ³H₆ transition. Similar quantum efficiency, longer lifetime and stronger fluorescence intensity were also found in Ho³⁺ doped aluminozircofluoride glass for the ⁵I₇ → ⁵I₈ transition. The higher quantum efficiencies of Tm³⁺ and Ho³⁺ in aluminozircofluoride glass are due to the longer lifetime and the lower phonon energy. The fluorescence mechanisms and energy transfer in the Yb³⁺ -Tm³⁺ system, Yb³⁺ -Ho³⁺ system and Yb³⁺ - Tm³⁺ -Ho³⁺ system were studied. The very strong fluorescence intensities in the Yb³⁺ -Tm³⁺ system for Tm³⁺ and the Yb³⁺ -Tm³⁺ -Ho³⁺ system for Ho³⁺ which are 1.68 times that of Tm³⁺ doped YSGG crystal and 2.25 times that of Tm³⁺---Ho³⁺ codoped YSGG crystal are attributed to the efficient Yb³⁺ → Tm³⁺, Yb³⁺ → Ho³⁺ and Tm³⁺ → Ho³⁺ energy transfer processes. The fluorescence processes are described by cross relaxations of ²F_5/2 → ³H₅ → ³H₄ → ³H₆ → ²F_7/2 and²F_5/2 → ³H₅ (or ²F_5/2 → ⁵I₆ → ³H₅) → ³H₄ → ⁵I₇ → ⁵I₈ → ³H₆ → ²F_7/2.     

Color centers and charge state recharge in γ-irradiated Yb:YAP

Gamma-ray irradiation induced color centers and charge state recharge of impurity and doped ion in 10 at.% Yb:YAP have been studied. The change in the additional absorption (AA) spectra is mainly related to the charge exchange of the impurity Fe²⁺, Fe³⁺ and Yb³⁺ ions. Two impurity color center bands at 255 and 313 nm were attributed to Fe³⁺ and Fe²⁺ ions, respectively. The broad AA band centered at 385 nm may be associated with the cation vacancies and F-type center. The transition Yb³⁺ → Yb²⁺ takes place in the process of γ-irradiation. Oxygen annealing and γ-ray irradiation lead to an opposite effect on the absorption properties of the Yb:YAP crystal. In the air annealing process, the transition Fe²⁺ → Fe³⁺ and Yb²⁺ → Yb³⁺ take place and the color centers responsible for the 385 nm band was destroyed.     

Al3+/Yb3+/P5+掺杂对石英玻璃紫外透过和紫外激发荧光的影响

采用溶胶-凝胶法结合高温真空烧结工艺制备了不同浓度的Al³⁺/Yb³⁺/P⁵⁺掺杂石英玻璃。研究了P⁵⁺和Al³⁺的引入对Yb³⁺掺杂石英玻璃紫外透过和紫外激发荧光光谱, 以及Yb4d电子结合能的影响, 并初步探索了其机理。研究结果表明, Al³⁺/Yb³⁺/P⁵⁺掺杂石英玻璃在190~300 nm波段的吸收主要来源于O^2-→Yb³⁺的电荷迁移吸收, 其谱带位置和Yb4d电子结合能随Yb³⁺的第二配位元素(Al、Si、P)电负性增大向高能方向移动。真空烧结条件下, 引入Al³⁺会引发石英玻璃中Yb³⁺还原为Yb²⁺, 其典型的吸收峰位于330 nm处; 然而, 在Al³⁺/Yb³⁺共掺的基础上再引入P⁵⁺, 且P⁵⁺/Al³⁺摩尔比大于1时, 可以有效抑制Yb²⁺的形成。紫外光激发引起的近红外发光(976 nm)是电子从电荷迁移态弛豫到Yb³⁺激发态向基态跃迁的结果, 可见发光(525 nm)归因于Yb²⁺的5d→4f跃迁。本文研究结果对通过优化工艺和调整组分制备出高性能的Yb³⁺掺杂光纤具有一定的指导意义。     

Growth and spectroscopy of Dy doped in ZnWO4 crystal

Single-crystal ZnWO₄:Dy³⁺ was grown by Czochralski technique. The XRD, absorption spectra as well as fluorescence spectrum are investigated and the Judd–Ofelt intensity parameters Ω₂, Ω₄, Ω₆ are obtained to be 7.76 × 10⁻²⁰ cm², 0.57 × 10⁻²⁰ cm², 0.31 × 10⁻²⁰ cm², respectively. Calculated radiative transition rate, branching ratios and radiative lifetime for different transition levels of ZnWO₄:Dy³⁺ crystals are presented. Fluorescence lifetime of ⁴F_9/2 level is 158 μs and quantum efficiency is 66%.The most intense fluorescence line at 575 nm correlative with transition ⁴F_9/2 → ⁶H_13/2 is potentially for application of yellow lasers.     

Optically active Er–Yb codoped Y2O3 films produced by pulsed laser deposition

Optically active Er³⁺:Yb³⁺ codoped Y₂O₃ films have been produced on c-cut sapphire substrates by pulsed laser deposition from ceramic Er:Yb:Y₂O₃ targets having different rare-earth concentrations. Stoichiometic films with very high rare-earth concentrations (up to 5.5 × 10²¹ at cm^− 3) have been achieved by using a low oxygen pressure (1 Pa) during deposition whereas higher pressures lead to films having excess of oxygen. The crystalline structure of such stoichiometric films was found to worsen the thicker the films are. Their luminescence at 1.53 μm and up-conversion effects have been studied by pumping the Yb³⁺ at 0.974 μm. The highest lifetime value (up to 4.6 ms) is achieved in films having Er concentrations of ≈ 3.5 × 10²⁰ at cm^− 3 and total rare-earth concentration ≈ 1.8 × 10²¹ at cm^− 3. All the stoichiometric films irrespective of their rare-earth concentration or crystalline quality have shown no significant up-conversion.     

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.     

Frequency upconversion of Tm and Yb codoped YLiF4 synthesized by hydrothermal method

In this paper, YLiF₄ codoped with Tm³⁺ and Yb³⁺ ions was synthesized by hydrothermal method. Yb³⁺ concentration is fixed at 1.5%, and Tm³⁺ concentration is changed from 0.1 to 0.4%. Intense upconversion luminescence is observed when the samples are excited by 980 nm. The dependence of upconversion luminescence on Tm³⁺ concentrations is presented. The results show that upconversion luminescence increases with the Tm⁺ concentration and gets its peak at 0.3 mol%. Under the excitation of 980 nm, the blue emission of 479 nm and the red emission of 647 nm are both duo to two photons process, and the UV emission of 361 nm is attributed to the three photons process. We also analyse the upconversion mechanism and process.     

Influence of rare-earth oxides on structure and crystallization properties of Bi2O3–B2O3 glass

Bi₂O₃·B₂O₃ glasses doped with rare-earth oxides (RE₂O₃) (RE³⁺ = La³⁺, Pr³⁺, Sm³⁺, Gd³⁺, Er³⁺ and Yb³⁺) were prepared by the melting–quenching method. The relationships between composition and properties were demonstrated by IR, DSC, XRD and SEM analysis. The results show that the network structure resembles that of undoped Bi₂O₃·B₂O₃ glass, composing of [BO₃], [BO₄] and [BiO₆] units. RE₂O₃ stabilizes the glass structure as a modifier. Transition temperature (T_g) increases linearly with cationic field strength (CFS) of RE³⁺. La₂O₃, Pr₂O₃, Sm₂O₃ and Gd₂O₃ are benefit to promote the formation of BiBO₃ crystal. When Er₂O₃ and Yb₂O₃ are introduced, respectively, the main crystal phase changes to Bi₆B₁₀O₂₄. Transparent surface crystallized samples are obtained by reheating at 460–540 °C for 5 h. In this case, needle like BiBO₃ crystal or rare-earth-doped BiBO₃ crystal (Pr_xBi_1−xBO₃ and Gd_xBi_1−xBO₃) are observed, which is promising for non-linear optical application.     

Yb3+,Tb3+共掺杂Sr2B2O5荧光粉的制备及其下转换发光性能的研究

采用高温固相法合成了Tb³⁺, Yb³⁺共掺杂的Sr₂B₂O₅荧光粉。通过X射线衍射(XRD)和荧光光谱(PL)对样品的物相结构和发光性质进行了表征。XRD结果表明, 合成样品为单斜结构的Sr₂B₂O₅相。分别使用543 nm和980 nm的监测波长, 得到的激发光谱均在354 nm、374 nm处有较强的激发峰, 其中374 nm处最强, 说明Sr₂B₂O₅荧光材料在近紫外光区对太阳光有很强的吸收; 在374 nm( Tb³⁺:⁷F₆→⁵D₃) 紫外光激发下, 观察到Tb³⁺: ⁵D₄→⁷F_J ( J = 6, 5, 4, 3) 可见光区发射光, 并检测到Yb³⁺: ²F_5/2→²F_7/2的近红外发射光。通过研究激发光谱和发射光谱与Yb³⁺掺杂浓度的关系, 发现在单斜晶体Sr₂B₂O₅中, Yb³⁺具有很高的猝灭浓度。     

Partition, luminescence and energy transfer of Er/Yb ions in oxyfluoride glass ceramic containing CaF2 nano-crystals

A complete spectroscopic investigation of energy transfer processes in oxyfluoride glass ceramics containing CaF₂ nano-crystals doped with various amounts of Er³⁺ and Yb³⁺ was reported. An enhancement of the 1.53 μm emission and infrared to visible up-conversion fluorescence was confirmed experimentally due to efficient non-radiative energy transfer from Yb³⁺ to Er³⁺ ions concentrated in CaF₂ nano-crystals. The efficiency of Yb³⁺ to Er³⁺ energy transfer in excess of 85% was obtained for 0.5 mol% Er³⁺/2.0 mol% Yb³⁺ co-doped glass ceramic. Using rate equation formulism, the coefficient of Yb³⁺ to Er³⁺ energy transfer was determined to be about 3.5 times higher than that of Er³⁺ to Yb³⁺ energy back transfer, which is sufficient to provide high ⁴I_11/2 population of Er³⁺ to improve the fluorescence of the co-doped glass ceramics.     

Yb to Er energy transfer and rate-equations formalism in the eye safe laser material Yb:Er:Ca2Al2SiO7

Rate equations formalism is used to predict the population ratio of the Er^{3+ 4}I_13/2 levels involved in the 1.55 μm laser transition in the Yb:Er:CAS laser materials. An effective Yb → Er energy transfer, favourable to the Er³⁺ 1.55 μm laser emission, is demonstrated in this laser host. Indeed, the Yb → Er transfer and the Er → Yb back transfer rates are calculated to be 6 x 10⁻¹⁶ and 0.45 x 10⁻¹⁶ cm³ s⁻¹, respectively. Attempts of codoping the system with Nd³⁺, Eu³⁺ and Ce³⁺ have been realised in order to increase the population of the Er^{3+ 4}I_13/2 laser emitting level. Best results are obtained with Ce³⁺ ion since in the sample containing 6 x 10²⁰ Ce³⁺/cm³, the Er^{3+ 4}I_11/2 level lifetime is divided by a factor of 3 while the Er^{3+ 4}I_13/2 fluorescence lifetime remains unaffected. On the contrary, codoping with Nd³⁺ or Eu³⁺ ions simultaneously decreases the Er^{3+ 4}I_11/2 and ⁴I_13/2 kinetics parameters. The role of the other parameters such as Yb/Er concentrations ratios is also discussed.     

Valency states of Yb, Eu, Dy and Ti ions in Li2B4O7 glasses

Absorption and emission spectra of Eu and Dy, Yb and Ti ions in Li₂B₄O₇ glasses grown in oxygen and hydrogen gas atmospheres were measured for valency states and lattice-sites analysis. For the Li₂B₄O₇ glass doped with Eu²⁺, Eu³⁺ and Dy³⁺ ions which were grown in oxidizing and reducing atmospheres, absorption and emission bands due to these ions were investigated before and after γ-irradiation. For the Yb³⁺-doped Li₂B₄O₇ glass, a weak, broad band was observed near the sharp 976.3 nm absorption band. The origin of this band is discussed in comparison with other glasses. Moreover, irradiation experiments using γ-rays were also performed in order to investigate the possibility of valency change of Yb ions. It was found that Ti⁴⁺ ions, which are produced under oxidizing atmosphere, change to Ti³⁺ ions after γ-irradiation with a dose of 10⁵ Gy. An additional absorption band observed at about 500 nm is due to the Ti³⁺ ions accompanied by charge-compensating vacancy and does not give any emission.     

Crystal growth and spectral properties of pure and Co-doped Mg3B2O6 crystal

Novel pure and cobalt-doped magnesium borate crystals (Mg₃B₂O₆) have been grown successfully by the Czochralski technique for the first time. Crystal growth, X-ray powder diffraction (XRD) analysis, absorption spectrum, fluorescence spectrum as well as fluorescence decay curve of Co²⁺:Mg₃B₂O₆ (MBO) were described. From the absorption peaks for the octahedral Co²⁺ ions, the crystal-field parameter Dq and the Racah parameter B were estimated to be 943.3 cm⁻¹ and 821.6 cm⁻¹, respectively. The fluorescence lifetime of the transition ⁴T₁(⁴P) → ⁴T₂ centered at 717 nm was measured to be 9.68 ms.     

Analysis of VUV and optical spectra of Cs2NaYF6 crystals doped with Tm

This study presents a detailed interpretation and analysis of the reported interconfigurational spectra of Tm³⁺ in Cs₂NaYF₆ [V.N. Makhov, N.M. Khaidukov, D. Lo, J.C. Krupa, M. Kirm, E. Negodin, Opt. Mater. 27 (2005) 1131]. Since only spin-forbidden d–f emission bands are observed for Tm³⁺ in this host, it is unsuitable for use as a scintillator because the emission lifetime is too long. The d–f emission spectrum is well-explained by calculation and most of the intensity is located in one band: 4f¹¹5d¹ (high-spin) → 4f^{12 3}H₆. Measurements from the bands in the d–f excitation spectrum do not provide the accurate separation energy of the high and low-spin states. Strict O_h point group selection rules are operative for the optical spectra. The electronic states of the 4f¹¹5d¹ configuration (briefly, d-electron states, hereafter) are calculated to span from 58,318 cm⁻¹ to 86,900 cm⁻¹. At least five structured bands are observed in the excitation spectrum and their intensities are fairly well simulated by calculation. The 4f¹² → 4f¹³ (np₆)⁻¹ charge transfer band is assigned between 140 and 120 nm (83,000–71,000 cm⁻¹) and excitation into this band leads to f–f emission, bypassing the d-electron states.     

Assessment of electrical and optical properties of heavily Fe-implanted semi-insulating InP

We report total compensation of InP layers n-doped to levels as high as n=2×10¹⁸ cm⁻³ by high temperature (>200°C) MeV Fe implantation and annealing. The electronic density and the active Fe (in the form of the Fe²⁺/Fe³⁺ deep acceptor states) profiles are obtained from the comparison between the current–voltage (I–V) characteristics and the outcome of a numerical simulation. These results are confirmed by photo-induced current transient spectroscopy (PICTS) experiments, which show a correlation between the Fe activation and the background doping concentration. A deeper insight into the properties of the Fe²⁺/Fe³⁺ centers is gained by Fourier transform infrared (FTIR) photoluminescence measurements, showing intense and sharp emission peaks at 3.5 μm, associated with Fe intracenter transitions. The corresponding lifetimes have been studied by time resolved integrated photoluminescence measurements.     

Synthesis and the luminescent properties of europium-activated Ca2SnO4 phosphors

The synthesis and photoluminescent (PL) properties of calcium stannate crystals doped with europium grown by mechanically activated in a high energy vibro-mill have been investigated. The characteristics of Ca₂SnO₄:Eu³⁺ phosphors were found to depend on the amounts of europium ions. The XRD profiles revealed that the system, (Ca_1−xEu_x)₂SnO₄, could form stable solid solutions in the composition range of x = 0–7% after being calcined at 1200 °C. The calcined powders emit bright red luminescence centered at 618 nm due to ⁵D₀ → ⁷F₂ electric dipole transition. Both XRD data and the emission ratio of (⁵D₀ → ⁷F₂)/(⁵D₀ → ⁷F₁) reveal that the site symmetry of Eu³⁺ ions decreases with increasing doping concentration. The maximum PL intensity has been obtained for 7 mol% concentration of Eu³⁺ in Ca₂SnO₄.     

Effect of heat treatment on photoluminescence behavior of BaMgAl10O17:Eu phosphors

The blue phosphor of BaMgAl₁₀O₁₇:Eu²⁺ (BAM) powders were prepared by solid-state reaction. The thermal degradation of BAM phosphor significantly reduces the intensity of the blue emission. BAM is reduced by an amount of 50% after heating at around 800 °C for 1 h. Photoluminescence (PL) excitation and emission spectra showed that the blue emission of 450 nm peak decreased with increasing annealing temperature. The ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transition of Eu³⁺ were observed at 590 and 615 nm emission lines over 1100 °C. Electron paramagnetic resonance (EPR) spectrum also detected two signals of Eu²⁺, corresponding to g=3.7156(9) for 88 mT, and g=2.9507(9) for 133 mT. X-ray absorption near edge structure (XANES) spectrum decreased the intensity of Eu²⁺ for 6977 eV with increasing annealing temperature, while high-energy peak of Eu³⁺ for 6984 eV was increased. The combined use of X-ray and neutron data by the Rietveld refinement appears to support that the secondary phase of EuMgAl₁₁O₁₉ magnetoplumbite structure in BAM may be formed by heat treatment.     

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。     

Microstructural changes inside the lamellar structures of alloy ZA27

The microstructural changes inside the lamellar structure of the cast and aged alloy ZA27 were studied using TEM, XRD and SEM techniques. Using TEM, the network of transitional phase η_m^′ was determined to be of an fcc crystal structure inside the lamellae η phase during ageing at 150 °C. The mechanism of the decomposition of the η phase lamellae can be summarized as follows: η → η_m^′ + η′ →  + η. The adjacent co-existence of the ε phase and the T′ phase inside the phase lamellae confirmed that a four phase transformation,  + ε → T′ + η, had occurred during the prolonged ageing.