Spectroscopic properties of Ce doped silica annealed at different temperatures

Ce³⁺-doped silica was synthesized by sol-gel technique. The absorption band at 252 nm of Ce³⁺-doped silica is close to the main absorption band of Ce(NO₃)₃ solution. Three different luminescence bands were observed in the samples annealed at temperatures from 100 to 1200 °C, and the intensity of these luminescence bands changed with the alteration of the heat-treating temperatures. In addition to two well-known main luminescence bands of 4f-5d transition of Ce³⁺ with the wavelength at 357 and 450 nm, a rarely reported luminescent band with the wavelength at 344 nm was also observed, which was attributed to some kind of oxygen-related defects of silica.     

Intense red upconversion fluorescence emission in NIR-excited erbium-ytterbium doped laponite-derived phosphor

In this report the optical properties and energy-transfer frequency upconversion luminescence of Er³⁺/Yb³⁺-codoped laponite-derived powders under 975 nm infrared excitation is investigated. The 75%(laponite):25%(PbF₂) samples doped with erbium and ytterbium ions, generated high intensity red emission around 660 nm and lower intensity green emission around 525, and 545 nm. The observed emission signals were examined as a function of the excitation power and annealing temperature. The results indicate that energy-transfer, and excited-state absorption are the major upconversion excitation mechanism for the erbium excited-state red emitting level. The precursor glass samples were also heat treated at annealing temperatures of 300 °C, 400 °C, 500 °C, and 600 °C, for a 2 h period. The dependence of the visible upconversion luminescence emission upon the annealing temperature indicated the existence of an optimum temperature which leads to the generation of the most intense and spectrally pure red emission signal.     

Synthesis process and the luminescence properties of rare earth doped NaLa(WO4)2 nanoparticles

Rare earth doped NaLa(WO₄)₂ nanoparticles have been prepared by a simply hydrothermal synthesis procedure. The X-ray diffraction (XRD) pattern shows that the Eu³⁺-doped NaLa(WO₄)₂ nanoparticles with an average size of 10-30 nm can be obtained via hydrothermal treatment for different time at 180 °C. The luminescence intensity of Eu³⁺-doped NaLa(WO₄)₂ nanoparticles depended on the size of the nanoparticles. The bright upconversion luminescence of the 2 mol% Er³⁺ and 20 mol% Yb³⁺ codoped NaLa(WO₄)₂ nanoparticles under 980 nm excitation could also be observed. The Yb³⁺-Er³⁺ codoped NaLa(WO₄)₂ nanoparticles prepared by the hydrothermal treatment at 180 °C and then heated at 600 °C shows a 20 times stronger upconversion luminescence than those prepared by hydrothermal treatment at 180 °C or by hydrothermal treatment at 180 °C and then heated at 400 °C.     

Investigation on upconversion photoluminescence of Bi3TiNbO9:Er:Yb thin films

Bi₃TiNbO₉:Er³⁺:Yb³⁺ (BTNEY) thin films were fabricated on fused silica by pulsed laser deposition. It was demonstrated that different laser fluence and substrate temperature during growth of BTNEY upconversion photoluminescence (UC-PL) samples control the film’s grain size and hence influences the UC-PL properties. The average grain size of BTNEY thin films deposited on fused silica substrates with laser fluence 4, 5, 6, and 7 J/cm² are 30.8, 35.9, 40.6, and 43.4 nm, respectively. The 525 nm emission intensities increase with the deposition laser fluence and the emission intensities of BTNEY thin film deposited under 700 and 600 °C are almost 24 and 4 times, respectively, as strong as those of samples under 500 °C. The grain size of BTNEY thin film increases with the increasing temperature. UC-PL of BTNEY films is enhanced by increasing grain size of the films.     

Effect of ZnO as modifier on up and downconversion properties of Ho/Yb doped tellurite glasses

Optical absorption and photoluminescent properties of Ho³⁺/Yb³⁺ co-doped tellurite and zinc tellurite glasses are investigated. The effect of zinc oxide as a modifier on the luminescence properties of above mentioned samples has been explored. Two intense upconversion emission bands centered at 546 (⁵F₄ + ⁵S₂ → ⁵I₈) and 660 nm (⁵F₅ → ⁵I₈) are observed on excitation with 976 nm diode laser. Zinc oxide acts as a quencher for 976 nm excited upconversion emission. The up and downconversion emission spectra are recorded with 532 nm excitation source also. In this case zinc oxide improves the up and downconversion emissions. A large enhancement in upconversion intensity has been observed when Ho³⁺ ion is co-doped with Yb³⁺ ion. The dependence of upconversion intensities on excitation power and on temperature has also been studied. The power dependence study shows a quadratic dependence of the fluorescence intensity on the excitation power while a decrement in emission intensity of all the transitions at different rates with increase in temperature is observed in temperature dependence study. The possible mechanisms are also discussed in order to understand the upconversion and energy transfer processes.     

Thermal loading induced near-infrared broadband upconversion emission of Sm-doped β-NaYbF4 nano-phosphors

A non-closed hydrothermal synthetic processing is improved to synthesize Sm³⁺ doped β-NaYbF₄ nano-phosphors at 98 °C without any high-temperature and high-pressure treatments as a final step. Novel green, red, and near-infrared broadband (799-873 nm) upconversion emissions of Sm³⁺-doped β-NaYbF₄ nano-phosphors under 980 nm excitation are observed. These UC emissions can be assigned to the Sm³⁺ transitions of ⁴G_J, ⁴F_3/2 and ⁶F_11/2→⁶H_J. The half-width of 873 nm emission band is broadened nearly two-fold through the annealing treatment for nano-phosphors. The upconversion process in Yb³⁺-Sm³⁺ system is discussed based on energy transfer mechanisms.     

Kinetics of luminescence of interface defects and resonant Er ions in nanostructured SnO2:SiO2

Silica glass with SnO₂ nanocrystals and Er³⁺ ions are prepared by the sol-gel route and treatment above 1000 °C. Transmission electron microscopy evidences a homogeneous dispersion of nanoclusters 4-6 nm in size in the amorphous silica matrix. Photoluminescence spectra excited at 3.5 eV, outside erbium transitions, show an inhomogeneous spectral distribution of light emission from interface defects, in the range 1.9-2.4 eV, resonant with transitions of erbium ions. The analysis of kinetics and temperature dependence of luminescence allows to quantify the efficiency of the energy transfer channel between nanoclusters and erbium ions.     

Size-effect on concentration quenching in Yb-doped Y3Al5O12 nano-crystals

Ytterbium-doped nano-crystalline powders of yttrium aluminium garnet Y₃Al₅O₁₂ (Yb³⁺-doped YAG) have been prepared by a modified Pechini method. The morphology of the annealed materials was observed using SEM images. The structure and the average crystalline grain sizes have been determined by X-ray powder diffraction measurements. An increase in elongated spherical crystalline grain sizes from 20 to 50 nm has been observed with annealing temperature increasing from 800 to 1200 °C. The Yb³⁺ concentration dependence of both luminescence spectra and lifetimes has been investigated and compared with those reported for the Yb³⁺-doped YAG bulk single crystals. Decays of Yb^{3+ 2}F_5/2 excited state, much longer in nano-crystalline powders than in bulk single crystals, are discussed in terms of refractive index dependence.     

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.     

Upconversion luminescence and mechanisms in Yb-sensitized Tm-doped oxyhalide tellurite glasses

Effect of Yb₂O₃ content on upconversion luminescence and mechanisms in Yb³⁺-sensitized Tm³⁺-doped oxyhalide tellurite glasses were investigated under 980 nm excitation. Intense blue and relatively weak red upconversion emission centered at 476 and 649 nm corresponding to the transitions ¹G₄→³H₆ and ¹G₄→³H₄ of Tm³⁺, respectively, are simultaneously observed at room temperature. The results show that upconversion blue and red emission intensities of Tm³⁺ first increase, reach its maximum at Yb₂O₃%=3 mol%, and then decrease with increasing Yb₂O₃ content. The effect of Yb₂O₃ content on upconversion intensity is discussed, and possible effect mechanisms are evaluated. The investigated results were conducing to increase upconversion luminescence efficiency of Tm³⁺.     

Noise figure and gain temperature dependent of praseodymium-doped fiber amplifier by using rate equations

A theoretical study of the temperature dependent noise effects of praseodymium-doped fiber amplifiers (PEDFAs) has been examined. The Pr³⁺-doped ZBLAN fiber amplifier pumped at 1017 nm and Pr³⁺-doped GeGa-sulfied fiber amplifier pumped at 1028 nm are chosen. The temperature-dependent rate and propagation equation related to four-level system consideration which is based on the population difference among amplification levels has been used. The population difference depends on pump and signal powers, Boltzman factor K_B, cross-sections, noise figure (NF) and Pr³⁺ concentration. The numerical results obtained over the temperature range from −20 °C to + 60 °C are used to present an analytical expression for the signal gain and noise figure effects in PDFAs length and noise figure with input pump power. The amplified spontaneous emission (ASE) has been taken into account.     

Growth and spectroscopic properties of Yb-doped Li6Y(BO3)3 single crystal

The spectroscopic properties of high-quality Czochralski grown 20% Yb³⁺-doped Li₆Y(BO₃)₃ single crystal as new promising laser material are presented. The crystal was seeded-grown in the 〈0 1 0〉 direction and its crystallinity was measured using X-ray rocking curve analysis. Low temperature transmission spectrum exhibits broad bands in a short range of wavelengths and two sharp lines at 972.5 and 978 nm, interpreted as two zero-lines of two nonequivalent Yb³⁺ centers inside the lattice. The fluorescence lifetimes associated to these two intense lines are different: 0.867 and 1.33 ms. An attempt of determination of the Stark sublevels energies of the ⁴F_5/2 and ⁴F_7/2 manifolds of the two Yb³⁺ nonequivalent ions is given. The polarized absorption and emission spectra were also recorded at room temperature and we conclude that the most favorable emission line for laser application could be around 1042 nm in n_g polarization.     

Fluorescence and Judd-Ofelt analysis of Nd ions in oxyfluoride glass ceramics containing CaF2 nanocrystals

Judd-Ofelt analyses of Nd³⁺ ions in the oxyfluoride glasses and glass ceramics containing CaF₂ nanocrystals are performed to evaluate the intensity parameters Ω_2,4,6, spontaneous emission probability, radiative lifetime, quantum efficiency, as well as stimulated emission cross-section. The influences of Nd³⁺-doping level and heating temperature on these parameters for the ⁴F_3/2→⁴I_J (J=9/2, 11/2, and 13/2) transitions are systematically discussed. The decrease of intensity parameter Ω₂ evidences the incorporation of Nd³⁺ ions into CaF₂ nanocrystals after crystallization. With increasing of Nd³⁺-doping level, the measured lifetime and quantum efficiency gradually decrease, while the stimulated emission cross-section keeps almost unchanged. For 1.0 mol% Nd³⁺-doped sample, both the emission intensity and the measured lifetime enhance with increasing of heating temperature up to 650 °C. The results indicate that the investigated glass ceramics are potentially applicable as the 1.06 um laser host.     

Luminescence property of Ce-doped silica decorated with S and Cl anions

Ce³⁺-doped silica was synthesized by sol-gel technique and was further decorated with S²⁻ and Cl⁻ anions through chemical exchange in controlled ambient at elevated temperature. The structure and optical property of samples were examined by X-ray diffraction spectrum, XPS pattern, reflection pattern, and photoluminescence patterns. There is a broad luminescence band at 445 nm under the excitation at 320 nm in the Ce³⁺-doped silica heat-treated in air at 1000 °C. The heat-treatment of the sample in vacuum at 800 °C can increase the intensity of luminescence but have no effect on the wavelength of luminescence. The decoration of S²⁻ and Cl⁻ anions cannot only increase the luminescent intensity but also shift the luminescent wavelength to shorter wavelength.     

Optical absorption and emission properties of Gd in silica host

We present a study of the optical properties of Gd-doped sol-gel silica glasses densified at different temperatures (from 450 up to 1050 °C) by means of optical absorption (OA) and radio luminescence (RL). The effect of a post-densification rapid thermal treatment (RTT) at approximately 1800 °C is also considered. Room temperature OA and RL measurements have revealed a slight low-energy shift of Gd³⁺ absorption/emission lines by densification temperature increasing accompanied by a parallel increase of Gd³⁺ RL intensities, especially strong after RTT. These effects are interpreted on the basis of structural modifications of the silica matrix and of the removal of non-radiative channels competing with Gd³⁺ emission. Moreover, RL spectra of fully densified samples display high-energy shoulders on the ⁶P_7/2-⁸S Gd³⁺ emission possibly related to crystal field splitting of the ⁶P_7/2 state. This interpretation is supported by the temperature dependence of RL spectra, investigated in the 10-320 K temperature interval: an increase of the intensity of high-energy components vs. temperature has been observed, which can be interpreted as due to thermally assisted excitation of electrons belonging to the lower ⁶P_7/2 state to higher crystal field states and their subsequent radiative recombination.     

Optical properties of annealed Mn-doped ZnS nanoparticles

Cysteine stabilized ZnS and Mn²⁺-doped ZnS nanoparticles were synthesized by a wet chemical route. Using the ZnS:Mn²⁺ nanoparticles as seeds, silica-coated ZnS (ZnS@Si) and ZnS:Mn²⁺ (ZnS:Mn²⁺@Si) nanocomposites were formed in water by hydrolysis and condensation of tetramethoxyorthosilicate (TMOS). The influence of annealing in air, formier gas, and argon at 200-1000 °C on the chemical stability of ZnS@Si and ZnS:Mn²⁺@Si nanoparticles with and without silica shell was examined. Silica-coated nanoparticles showed an improved thermal stability over uncoated particles, which underwent a thermal combustion at 400 °C. The emission of the ZnS@Si and ZnS:Mn²⁺@Si passed through a minimum in photoluminescence intensity when annealed at 600 °C. Upon annealing at higher temperatures, ZnS@Si conserved the typical emission centered at 450 nm (blue). ZnS:Mn²⁺@Si yielded different high intensity emissions when heated to 800 °C depending on the gas employed. Emissions due to the Mn²⁺ at 530 nm (green; Zn₂SiO₄:Mn²⁺), 580 nm (orange; ZnS:Mn²⁺@Si), and 630 nm (red; ZnS:Mn²⁺@Si) were obtained. Therefore, with a single starting product a set of different colors was produced by adjusting the atmosphere wherein the powder is heated.     

Solvent effect in monoclinic to hexagonal phase transformation in LaPO4:RE (RE=Dy, Sm) nanoparticles: Photoluminescence study

Nanosized phosphor materials, LaPO₄:RE (RE=Dy³⁺, Sm³⁺) have been synthesized using water, dimethyl sulfoxide (DMSO), ethylene glycol (EG) and mixed solvents at a relatively low temperature of 150 °C. X-ray diffraction (XRD) study reveals that as-prepared nanoparticles prepared in DMSO and EG are well crystalline and correspond to monoclinic phase. In the mixed water-DMSO or water-EG solvents, XRD patterns are in good agreement with hexagonal phase, but transformed to monoclinic phase at higher temperature of 900 °C. TEM images show well-dispersed and rice-shaped nanoparticles of diameter 5-10 nm, length of 13-37 nm for Dy³⁺-doped LaPO₄ and diameter of 25-35 nm, length of 73-82 nm for Sm³⁺-doped LaPO₄. Dy³⁺-doped LaPO₄ shows two prominent emission peaks at 480 and 572 nm corresponding to ⁴F_9/2→⁶H_15/2 (magnetic dipole) and ⁴F_9/2→⁶H_13/2 (electric dipole) transitions, respectively. Similarly, for Sm³⁺-doped LaPO₄, three prominent emission peaks at 561, 597 and 641 nm were observed corresponding to ⁴G_5/2→⁶H_5/2, ⁴G_5/2→⁶H_7/2 (magnetic dipole) and ⁴G_5/2→⁶H_9/2 (electric dipole) transitions, respectively. The luminescence intensity of the sample prepared in EG is more than that of DMSO or mixed solvents. Enhancement of luminescence is also observed after heat-treatment at 900 °C due to removal of quencher such as water, organic moiety and surface defects/dangling bonds. The samples are re-dispersible in polar solvent and can be incorporated in polymer film.     

Novel shooting method with simple control strategy for fiber lasers

A novel shooting method with excellent simple control strategy is developed for solving the failure to convergence of the traditional shooting methods themselves in fiber lasers model. Compared with the published literature, the novel shooting method provides a clear physical understanding method for getting the threshold pump power and the exact results with given random functions in Yb³⁺-doped fiber lasers and Er³⁺-doped fiber lasers. Then, the results in Er³⁺-doped fiber lasers and Yb³⁺-doped fiber lasers demonstrate that the solutions using the novel shooting method has high accuracy of 10⁻⁸ W with several iteration steps, which have extended the applicable range of the end-pumped power even lower than 1 mW pump power. Furthermore, compared with 1480 nm pump for the threshold and slope efficiencies of the Er³⁺-doped fiber lasers, 978 nm fiber lasers can extend wider scope of application and be pump source in the coming future. Finally, the lower threshold and higher slope efficiency at 975 nm than those of 910 nm pump in Yb³⁺-doped fiber lasers, 975 nm pump laser provides for broad band excellent cladding pump source.     

激光二极管抽运下铥/镱共掺碲镓酸盐玻璃光谱特性研究

研究了808 nm和977 nm激光二极管抽运下铥/镱共掺TeO₂-Ga₂O₃-R₂O(R=Li，Na，K)玻璃光谱特性.利用Judd-Ofelt 理论计算了Tm³⁺离子在碲镓酸盐玻璃中自发辐射跃迁概率、荧光分支比和辐射寿命等光谱参数.在977 nm激光二极管抽运下，观测到Tm³⁺/Yb³⁺共掺碲镓酸盐玻璃很强的476 nm上转换蓝光(¹G₄→³H₆)和较弱的650 nm上转换红光(¹G₄→³H₄和³F_2，3→³H₆).分析表明476 nm蓝光发射为三光子吸收过程，650 nm红光发射为双光子和三光子混合吸收过程；而在808 nm激光二极管抽运下，玻璃上转换蓝色荧光为双光子吸收过程.实验发现，随着碱金属离子半径的增大，977 nm激光二极管抽运下蓝光上转换发光强度增强，而用808 nm激光二极管抽运蓝光上转换发光无明显的变化. 关键词： 碲镓酸盐玻璃 铥镱共掺 Judd-Ofelt 理论 上转换     

Thermal effect on multiphonon-assisted anti-Stokes excited upconversion fluorescence emission in Yb3+-sensitized Er3+-doped optical fiber

The temperature effect upon infrared-to-visible frequency upconversion fluorescence emission in Yb³⁺-sensitized Er³⁺-doped germanosilicate optical fibers excited with cw radiation at 1.064 μm is investigated. The experimental results revealed an eightfold enhancement in the visible upconversion emission intensity as the fiber temperature was increased from 17 °C to 180 °C. The fluorescence emission enhancement is attributed to the temperature-dependent multiphonon-assisted anti-Stokes excitation process of the ytterbium sensitizer. A theoretical approach that takes into account a sensitizer absorption cross-section, which depends on the phonon occupation number, has proven to agree very well with the experimental data Received: 6 April 1999 / Revised version: 27 August 1999 / Published online: 27 January 2000