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.     

Effect of radiation trapping on the emission properties of Er: I13/2 → I15/2 transition in oxide glasses

The effect of radiation trapping on the emission properties of Er³⁺-doped tellurite and phosphate glasses has been investigated as the function of sample thickness and doping concentration. It was found that radiation trapping exists generally in two glass matrices, even at low doping concentration (0.1 mol% Er₂O₃). The larger effect of radiation trapping in tellurite glasses compared with phosphate glasses is due to its larger emission cross-section at 1.5 μm band and the spectral overlap between the emission and absorption spectra of Er³⁺: ⁴I_13/2 ↔ ⁴I_15/2transition. Due to radiation trapping, the measured lifetime of the Er³⁺: ⁴I_13/2 level in tellurite glasses increases by about 11–37% with increasing the sample thickness at the different erbium doping concentration, while 6–17% for phosphate glasses. And the full-width at half maximum of fluorescence (FWHM) of Er³⁺: ⁴I_13/2 → ⁴I_15/2 transition in tellurite glasses increased by about 15–64% with increasing the sample thickness, while 11–55% for phosphate glasses. It caused a high overestimation on the figure of merits (FOM) for amplifier bandwidth (σ_e × FWHM).     

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.     

Optical properties of Er-doped SiO2-GeO2-Al2O3 planar waveguide fabricated by sol–gel processes

In this paper, we report silica based planar waveguides doped with Er³⁺, and co-doped with GeO₂ and Al₂O₃. These sol–gel derived planar waveguides were fabricated on SOS (silica on silicon) using multiple spin-coating and rapid thermal processing (RTP). Investigation has been made on their characteristics in terms of their application in optical amplification and lasing, including photoluminescence (PL), fluorescence lifetime, refractive index, propagation loss, surface roughness, Fourier transform infrared (FTIR) spectrum and X-ray diffraction (XRD) analysis. The propagation loss of a 20-layer planar waveguide was measured to be about 1.6 dB/cm for TE₀ and 2.2 dB/cm for TM₀ mode. A strong emission transition (⁴I_13/2→⁴I_15/2) at 1.536 μm with a lifetime of 3.6 ms has been obtained for an optimized molar composition of 90SiO₂: 10GeO₂: 20AlO_1.5: 1ErO_1.5.     

Infrared absorption and Zeeman effect in Nd doped YVO4

Low temperature infrared transmission studies of Nd³⁺ doped YVO₄ were performed, under a magnetic field B c, in the 1800–8000 cm⁻¹ range of the ⁴I_9/2→⁴I_11/2, ⁴I_13/2, and ⁴I_15/2 Nd³⁺ crystal-field transitions. Good agreement is obtained between the experimental and calculated g-factors. Frequencies of the satellites in the ⁴I_9/2→⁴F_3/2 transitions of the Nd³⁺ isolated ion confirm the presence of ferromagnetic interactions between pairs of coupled Nd³⁺ ions that lift the Kramers doublet degeneracies of their ground state and excited multiplets.     

Controllable formation of Er–Yb codoped Al2O3 films by the non-aqueous sol–gel method

1 mol%Er³⁺–10 mol%Yb³⁺ codoped Al₂O₃ thin films have been prepared on thermally oxidized SiO₂/Si(110) substrates by a dip-coating process in the non-aqueous sol–gel method from the hydrolysis of aluminum isopropoxide [Al(OC₃H₇)₃] under isopropanol environment. Addition of N,N-dimethylformamide (DMF) as a drying control chemical additive (DCCA) into the sol suppresses formation of the cracks in the Er³⁺–Yb³⁺ codoped Al₂O₃ thin films when the rare-earth ion is doped with a high doping concentration. Homogeneous, smooth and crack-free Er³⁺–Yb³⁺ codoped Al₂O₃ thin films form at the conditions by a molar ratio of 1:1 for DMF:Al(OC₃H₇)₃. A strong photoluminescence spectrum with a broadband extending from 1.400 to 1.700 µm centered at 1.533 µm is obtained for the Er³⁺–Yb³⁺ codoped Al₂O₃ thin films, which is unrelated to the addition of DMF. Controllable formation of the Er³⁺–Yb³⁺ codoped Al₂O₃ thin films may be explained by the fact that the DMF assisted the deprotonation process of Al–OH at the surfaces of gel particles, resulting in enhancement of the degree of polymerization of sols and improvement of the mechanical properties of gel thin films.     

Two- and three-photon upconversion of LaOBr:Er

In this work, the LaOBr:Er³⁺ (0.1%) powders were prepared by solid state reaction. The structural properties of LaOBr:Er³⁺ were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and Raman spectroscopy. The results show that LaOBr:Er³⁺ has low phonon energy, which indicate that LaOBr:Er³⁺ may have high luminescent efficiency. Under excitation into ⁴I_11/2 level of Er³⁺ ions by 980 nm laser, the two- and three-photon upconverted luminescence of LaOBr:Er³⁺ were recorded. The most intense emissions were come from the ²H_11/2, ⁴S_3/2 → ⁴I_15/2 transitions. The upconversion mechanisms were studied in detail through laser power dependence, and results show that excited state absorption is responsible for the upconversion. The upconversion properties indicate that LaOBr:Er³⁺ may be used in upconversion phosphors.     

Optical properties of rare earth ion (Nd, Er and Tb)-doped alumina films prepared by the sol–gel method

Rare earth ion (Nd³⁺, Er³⁺ and Tb³⁺)-doped alumina films were prepared by the sol–gel method using aqueous alumina sol. The effects of dopant concentration and treatment temperature on the optical properties, absorption and emission were examined for the doped films. Alumina films prepared by this method gave a high dopant concentration (0–15 mol% per alumina). Significant concentration quenching did not occur in this concentration range. The emissions from ⁵D₃ and ⁵D₄ of Tb³⁺-doped film reflected sensitively a matrix environment around Tb³⁺ ions. Er³⁺- and Nd³⁺-doped alumina films resonantly excited by cw Ti–sapphire laser (800 nm) showed upconversion emission at room temperature. The former gave 548 nm (⁴S_3/2→⁴I_15/2) and 640 nm (⁴F_9/2→⁴I_11/2) signals, and the latter 640 nm (⁴G_7/2→⁴I_11/2), which were dependent on alumina.     

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.     

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.     

Effect of Y codoping on luminescence decays of the I level in Er-doped AlO powders prepared by a sol-gel method

The luminescence lifetime of the 0.01 mol.%–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 has been investigated to explore the enhanced mechanism of photoluminescence properties of the Er³⁺-doped Al₂O₃ by Y³⁺ codoping. For the 0.1 mol.% Er³⁺–Y³⁺-codoped Al₂O₃ powders, the measured lifetime of Er³⁺ gradually increases with increasing Y³⁺ concentration. Consequently, codoping with 20 mol.% Y³⁺ leads to an increase in the measured lifetime from 3.5 to 5.8 ms. By comparing the measured lifetime for different Er³⁺ concentrations in the Al₂O₃ powders, the radiative lifetime of both the Er³⁺-doped and the Er³⁺–Y³⁺-codoped Al₂O₃ powders is estimated to be about 7.5 ms. Infrared absorption spectra indicate that Y³⁺ codoping does not change the –OH content in the Er³⁺–Y³⁺-codoped Al₂O₃ powders. The prolonged luminescence lifetime of the ⁴I_13/2 level of Er³⁺ in Er³⁺-doped Al₂O₃ powders by Y³⁺ codoping is ascribed to the decrease in the energy transfer rate between the Er³⁺ ions and the Er³⁺ and –OH, respectively, due to the suppressed interaction between Er³⁺ ions.     

实验优化设计中频反应溅射Al2O3:Ce薄膜发光性质研究

为了得到最优发光的薄膜材料成分参数,采用均匀设计和二次通用旋转组合设计相结合的方法建立发光强度与薄膜中氧含量和Ce³⁺ 离子掺杂浓度的回归方程,并用遗传算法求其取最大值时的解。用中频反应磁控溅射技术制备了相应成分的Al₂O₃:Ce非晶薄膜。在320nm光激发下,获得了较理想的发射光谱,对薄膜发光机理分析表明:薄膜的光致发光来自于Ce³⁺ 离子的5d1激发态向基态4f1的两个劈裂能级的跃迁。发光强度强烈的依赖于薄膜的掺杂浓度和氧元素含量。XPS检测表明,Al₂O₃:Ce薄膜中存在Ce³⁺ 。Ce³⁺ 含量和薄膜的化学成分是通过X射线散射能谱(EDS)测量的。薄膜试样的晶体结构应用X射线衍射分析。     

Optimization of spectroscopic properties of Yb-doped refractory sesquioxides: cubic Y2O3, Lu2O3 and monoclinic Gd2O3

Absorption and emission spectra are given for Yb³⁺-doped Y₂O₃, Lu₂O₃ and Gd₂O₃ at room temperature. Y₂O₃ and Lu₂O₃ as close cubic matrices, show Yb³⁺ similar spectra different of Yb³⁺ in Gd₂O₃ monoclinic structure. Here, we use a new method to study and optimize the main spectroscopic properties with only one concentration gradient sample. Finally, assignments of Yb³⁺ Stark levels and Raman vibrations in Y₂O₃, Lu₂O₃ and Gd₂O₃ single crystal are given.     

Spectroscopy of Er and Er–Yb-doped phosphate glasses

Optical absorption and emission properties of Er and Er–Yb-doped phosphate glasses are investigated both at low and room temperature in the near infrared spectral region between 800 and 2000 nm, and the results are thoroughly discussed in connection with the expected transitions originating from the crystal-field split ⁴I_15/2 and ⁴I_13/2 levels of the Er³⁺ ion. Accurate measurements of the ⁴I_13/2 fluorescence lifetimes and the determination of the stimulated emission cross section for the Er transition at 1.5 μm are also reported. Excited state absorption (ESA) from the metastable ⁴I_13/2 level towards the higher energy levels is measured in the 450–1200 nm spectral region. The ESA absorption peaks are in good agreement with the positions of the higher states of the 4f¹¹ Er³⁺ manifold.     

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.     

Preparation and optical properties of sol–gel derived Er-doped Al2O3–Ta2O5 films

Thin films of the system xAl₂O₃–(100 − x)Ta₂O₅–1Er₂O₃ were prepared by a sol–gel method and a dip-coating technique. The influences of the composition and the crystallization of the films on Er³⁺ optical properties were investigated. Results of X-ray diffraction indicated that the crystallization temperature of Ta₂O₅ increased from 800 to 1000 °C with increased values of x. In crystallized films, the intensities of the visible fluorescence and upconversion fluorescence tend to decrease with an increase in x values, due to the high phonon energy of Al₂O₃; the strongest fluorescence is observed in a crystallized film for x = 4 heat treated at 1000 °C. In amorphous films obtained by heat treatment at relatively low temperatures the Er³⁺ fluorescence could not be observed because strong fluorescence from organic residues remaining in the films thoroughly covered the Er³⁺ fluorescence. On the other hand, the Er³⁺ upconversion fluorescence in the amorphous films was observed to be stronger than that in the crystallized films. The strongest upconversion fluorescence is observed in an amorphous film for x = 75 heat treated at 800 °C.     

Synthesis and spectral properties of Ce[Ag(CN)2]3

Cerium ion luminescence in crystalline hosts forms the basis of many blue phosphor and scintillator technologies. We report the synthesis of luminescent single crystals of cerium dicyanoargentate. The luminescence properties are characterized using both steady-state and time-resolved spectroscopy. The broad, overlapping dicyanoargentate and Ce³⁺ emissions are decomposed into three Gaussians, revealing the characteristic dicyanoargentate emission at 350 nm while the Ce³⁺ 5d–4f transitions are observed at 359 nm and 391 nm. Excitation measurements show that the 4f–5d Ce³⁺ absorption overlaps the 320 nm emission of the dicyanoargentate ions, leading to a strong coupling between the dicyanoargentate energy donors and Ce³⁺ acceptors. We conclude that the cerium is excited through an energy transfer process from the dicyanoargentate species, resulting in strong room temperature luminescence.     

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.     

Cr-Tm ion pairs in Gd3Ga5O12 garnet

A study is presented about Cr³⁺→Tm³⁺ energy transfers in Gd₃Ga₅O₁₂ garnet at 10 K. By time-resolved spectroscopy and analysis of decay kinetics we determine the nature of the interaction and we show the existence of chromium-thulium pairs in which the chromium emission wavelength is shifted from 693.6 to 694 nm.     

YVO4∶Eu3+,Bi3+红色荧光粉的水热合成及其荧光性能

以Y₂O₃、Eu₂O₃、Bi(NO₃)₃·H₂O、浓HNO₃、偏钒酸铵、氨水、无水乙醇和一缩二乙二醇为原料,采用聚乙烯吡咯烷酮(PVP)辅助水热法合成YVO₄: Eu³⁺, Bi³⁺纳米颗粒。使用X射线衍射(XRD)、扫描电镜(SEM)、红外光谱(IR)和荧光光谱(FL)等手段对产品进行了表征和分析。结果表明：合成的样品为YVO₄: Eu³⁺, Bi³⁺纳米颗粒,均具有四方晶相结构,其微结构随反应溶液的的pH值变化。YVO₄: Eu³⁺, Bi³⁺纳米颗粒在619 nm处有较强的红光发射(电偶极跃迁⁵D₀→⁷F₂),在594 nm有较弱的橙光发射(磁偶极跃迁⁵D₀→⁷F₁)。随着Eu/Bi比值的增大材料的荧光先增强后减弱,在Eu/Bi比值为5时样品的红光发射最强。溶液的pH值影响YVO₄: Eu³⁺, Bi³⁺纳米晶的发光强度,其中pH值为10时的样品其红光发射最强。并探讨了YVO₄: Eu³⁺, Bi³⁺纳米晶的发光机理。