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.     

Removal of mercury species with dithiocarbamate-anchored polymer/organosmectite composites

Mercury is one of the most toxic heavy metals found in solid and liquid waste disposed by chloro-alkali, paint, paper/pulp, battery, pharmaceutical, oil refinery and mining companies. Any form of mercury introduced to nature through any means is converted into a more toxic form such as methylmercury chloride (as produced by aquatic organisms) which usually accumulates in the tissue of fish and birds.

The primary aim of this study was to investigate performance of dithiocarbamate-anchored polymer/organosmectite composites as sorbents for removal of mercury from aqueous solution. The modified smectite nanocomposites then were reacted with carbondisulfide to incorporate dithiocarbamate functional groups into the nanolayer of the organoclay. These dithiocarbamate-anchored composites were used for the removal of mercury species [Hg(II), CH₃Hg(I) and C₆H₅Hg(I)]. Mercury adsorption was found to be dependent on the solution pH, mercury concentration and the type of mercury species to be adsorbed. The maximum adsorption capacities were equal to 157.3 mg g⁻¹ (782.5 μmol g⁻¹) for Hg(II); 214.6 mg g⁻¹ (993.9 μmol g⁻¹) for CH₃Hg(I); 90.3 mg g⁻¹ (325 μmol g⁻¹) for C₆H₅Hg(I). The competitive adsorption capacities (i.e. adsorption capacities based on solutions containing all three mercuric ions) are 7.7 mg g^−l (38.3 μmol g⁻¹), 9.2 mg g^−l (42.6 μmol g⁻¹) and 12.7 mg g⁻¹ (45.7 μmol g⁻¹) for Hg(II), CH₃Hg(I) and C₆H₅Hg(I), respectively, at 10 ppm initial concentration. The adsorption capacities on molar basis were in order of C₆H₅Hg(I) > CH₃Hg(I) > Hg(II).     

In situ co-precipitation synthesis and photoluminescence of YxGd1−xVO4:Tm microcrystalline phosphors by hybrid precursors

Y_xGd_1−xVO₄:Tm³⁺ (5 mol%) phosphors were prepared by in situ co-precipitation technology with the different content ratio of Y/Gd (x = 0.2, 0.3, 0.4, 0.5, 0.6, 0.8, respectively). During the process, rare earth coordination polymers with o-hydroxylbenzoate were used as precursors, composing with polyethylene glycol (PEG) as dispersing media. After heat-treatment of the resulting multicomponent hybrid precursors at 900 °C, the samples were obtained. SEM indicated the particles present good crystalline state, whose crystalline grain sizes were about 0.2–2 μm. Under the excitation of 257 nm, all the materials show the characteristic emission of Tm³⁺ which is the strong blue emission centered at 475 nm originating from ¹G₄ → ³H₆ of Tm³⁺. Besides this, concentration quenching appears in the system of YVO₄:Tm³⁺ and GdVO₄:Tm³⁺. And when x reaches 0.5, the system of Y_xGd_1−xVO₄:Tm³⁺ shows the strongest blue emission.     

Further study on different dopings into PbWO4 single crystals to increase the scintillation light yield

Since we presented our preliminary result (Nucl. Instr. and Meth. A 486 (2002) 170) at SCINT2001, we have continued our efforts to increase the light yield (LY) of PbWO₄ scintillators by extending different dopings with an aim to find a possibility of using PbWO₄ successfully in Positron Emission Tomography (PET). Overall result obtained for single doping as well as double and tripple co-dopings are summarized, including decay characteristics and radiation hardness. The LY in non-doped PbWO₄ crystals with a size of 10×10×(20–30) mm³ is 25–35 photolectrons/MeV (phe/MeV) corresponding to 3–4% of the LY in BGO, when measured with a bialkali photomultiplier during a gate of 1 μs. The maximum LY increased to 49 phe/MeV for single doping with Mo⁶⁺, 80 phe/MeV for double co-doping of Mo⁶⁺+Sb⁵⁺, and 85 phe/MeV for tripple co-doping of Mo⁶⁺+Cd²⁺+Sb⁵⁺. The radiation hardness is larger than 10⁵ Gy for each of the samples co-doped with Mo⁶⁺+Sb⁵⁺ and Mo⁶⁺+Cd²⁺+Sb⁵⁺, while it is much poorer in PWO:Mo⁶⁺. In each of these co-doped samples, a medium-speed green emission in the microsecond range is created besides the fundamental fast (a few nanoseconds range) blue one, giving a peak at 500 nm in the radioluminescence spectrum similarly as in PWO:Mo⁶⁺.     

Enhanced ferroelectric properties of multilayer SrBi2Ta2O9/SrBi2Nb2O9 thin films for NVRAM applications

Ferroelectric SrBi₂Ta₂O₉/SrBi₂Nb₂O₉ (SBT/SBN) multilayer thin films with various stacking periodicity were deposited on Pt/TiO₂/SiO₂/Si substrate by pulsed laser deposition technique. The X-ray diffraction patterns indicated that the perovskite phase was fully formed with polycrystalline structure in all the films. The Raman spectra showed the frequency of the O–Ta–O stretching mode for multilayer and single layer SrBi₂(Ta_0.5Nb_0.5)₂O₉ (SBNT) samples was 827–829 cm⁻¹, which was in between the stretching mode frequency in SBT (813 cm⁻¹) and SBN (834 cm⁻¹) thin films. The dielectric constant was increased from 300 (SBT) to 373 at 100 kHz in the double layer SBT/SBN sample with thickness of each layer being 200 nm. The remanent polarization (2P_r) for this film was obtained 41.7 μC/cm², which is much higher, compared to pure SBT film (19.2 μC/cm²). The coercive field of this double layer film (67 kV/cm) was found to be lower than SBN film (98 kV/cm).     

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.     

Optimum thickness of carbon stripper foils in tandem accelerator in view of transmission and lifetime

Optimum thickness of charge stripper foils installed at the terminal of a tandem accelerator has been investigated from the view of (1) charge stripping effect, (2) transmission of ions through accelerator, (3) lifetime of foils for the irradiation of ions. For this purpose, measurements have been done for (a) transmission of H, Li, O, Br and Au ions, passing through 12 UD Pelletron tandem accelerator for carbon stripper foils of 1.8–19.5 μg/cm² thickness, at terminal voltages of 5 and 10 MV, and (b) lifetime of 2–15 μg/cm² thick Tanashi foils developed by Sugai by irradiating Au ions at the terminal voltage of 10 MV. The results obtained are as follows: (a) From the view of above items (1) and (2), the optimum thickness of foils is 10 μg/cm² for ions of Z=1, several μg/cm² for Z=8, and less than a few μg/cm² for heavier ions. (b) From the view of item (3), the lifetime of Tanashi foils by means of new arc-discharge method is demonstrated to be much longer than that of commercial foils for foils thicker than about 5 μg/cm² thick. This superiority rapidly decreases with decreasing foil thickness, and at around 2 μg/cm², the lifetime of Tanashi foils is at the most 2.4 times longer than that of commercial foils.     

Spectroscopic evidence of inhomogeneous distribution of Nd in YVO4, YPO4 and YAsO4 crystals

Nd³⁺ : YVO₄ is one of the most interesting laser hosts for micro and diode-pumped solid state lasers. We have studied magnetic and optical properties of Nd³⁺ in three zircon type crystals YMO₄ (M=V, As, P). In particular, Nd³⁺ ions exhibit in the three hosts a multisite character observed in the absorption and emission spectra. However, the emission and its dynamics are strongly dependant on the reabsorption mechanisms. In Nd : YVO₄, single crystals containing 7 ± 1 × 10¹⁸ Nd³⁺ ions/cm³, the lifetime is 95 ± 2 μs in good agreement with the calculated radiative lifetime. Electron Paramagnetic Resonance (EPR) measurements are performed to identify the nature of the different substitution sites for Nd³⁺ ions. Nd³⁺ ions are found to be inhomogeneously distributed in tetragonal D_2d symmetry sites, in isolated ions, “shallow clusters” and pairs. Proportions of the different local environments depend on the total neodymium concentration. For instance, 15% of the Nd³⁺ ions are gathered in Nd³⁺–Nd³⁺ pairs for 7.2 ± 0.2 × 10¹⁹ Nd³⁺ ions/cm³.     

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.     

Recovery of surfactant SDS and Cd2+ from permeate in MEUF using a continuous foam fractionator

The purpose of this study was to investigate the use of foam fractionation to recover valuable surfactant (SDS) and metal ion (Cd²⁺) in the permeate of micellar-enhanced ultrafiltration (MEUF). The effects of operating factors, such as time, air flow rate, feed flow rate, liquid height, foam height, feed surfactant concentration, ethanol concentration and temperature on separation characteristics were studied in the continuous operation. When the concentrations of surfactant (SDS) and metal ion (Cd²⁺) in the feed solution were 500 mg/L and 10 mg/L, an enrichment ratio of 3.1 was achieved for SDS along with 52% removal fraction, as well as 99.35% Cd²⁺ was removed, after optimization of different process parameters. As the optimized results, the air and liquid flow rates were 100 L/h and 5 L/h, liquid and foam heights were 45 cm and 66 cm, respectively, sparger pore size was 10 μm. The Cd²⁺ concentration in the effluent was lower than 0.1 mg/L which could meet the integrated wastewater discharge standard (the first grade of national discharge standards in China).     

Static energy transfer for Mn : Pr system in Phosphate glasses

The process of energy transfer from divalent manganese to trivalent praseodymium ions is studied with the help of Forster–Dexter theory. Some of the important energy transfer parameters such as transfer probability (P_SA), quantum yield of energy transfer (μ), critical radius (R₀) and critical concentration of the acceptor (C_A) are evaluated for the energy transfer pairs Mn²⁺ : Pr³⁺, Pr³⁺ : Pr³⁺ in phosphate glasses. The transfer of energy from Mn²⁺ to Pr³⁺ was confirmed by recording the fluorescence decay curves of Mn²⁺ emission corresponding to various activator concentrations which show a non-exponential behaviour. Large values of transfer probabilities and transfer efficiencies suggest that Mn²⁺ ion can act as a good sensitizer to Pr³⁺ ion in phosphate glass.     

Preparation, characterization, non-isothermal reaction kinetics, thermodynamic properties, and safety performances of high nitrogen compound: hydrazine 3-nitro-1,2,4-triazol-5-one complex

An optimized and validated spectrophotometric method has been developed for the determination of uranyl ion in the presence of other metal ions. The method is based on the chelation of uranyl ion with meloxicam via β-diketone moiety to produce a yellow colored complex, which absorbs maximally at 398 nm. Beer's law is obeyed in the concentration range of 5–60 μg/mL with apparent molar absorptivity and Sandell's sensitivity of 5.02 × 10⁴ L/mol/cm and 0.1 μg/cm²/0.001 absorbance unit, respectively. The method has been successfully applied for the determination of uranyl ion in synthetic mixture and soil samples. Results of analysis were statistically compared with those obtained by Currah's spectrophotometric method showing acceptable recovery and precision.     

Non-linear optothermal properties of metal-free phthalocyanine

The non-linear optical properties of metal-free phthalocyanine (MFPC) thin films were examined using the second harmonic at 532 nm from a pulsed Nd:YAG laser, and the continuous wave He–Ne and Ar⁺ lasers. The He–Ne laser transmission at fixed input intensity was found to increase temporally within a period of 12 h. The third-order non-linear susceptibilities (χ⁽³⁾) by four-wave mixing were measured for films of different thickness. The saturation intensity of MFPC, and its absorption cross-section, at 633 nm from a He–Ne laser, are reported. An optical bistability was recorded using a He–Ne laser. An AND logic gate was also demonstrated in the system. These phenomena in the system are attributed to refractive index modulation by thermal excitations.     

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.     

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).     

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.     

Ion-burst method for positive and negative ion species measurements

A simple method for positive and negative ion species measurements utilizing ion bursts is presented. In this ion-burst method, the ion bursts are excited by a potential applied to a mesh grid immersed in the plasma. Since the velocity of the ion burst is dependent on the excitation voltage and the ion mass, the ion species can be determined from measurement of the ion-burst velocity. In the DC discharge of an Ar/SF₆ gas mixture, the positive ion species are found to be Ar⁺, SF₃⁺ and SF₅⁺, and the negative ion species are found to be F⁻ and SF₆⁻. These results are compared with the spectrum analysis using a quadrupole mass spectrometry system and show qualitative agreement with them.     

On the formation of radiation-induced defects in fluoroaluminate glasses

The spectra of electron paramagnetic resonance (EPR) of fluoroaluminate glass (FAG-36) based on mineral usovite Ba₂CaMgAlF₁₄ were studied. The paramagnetic centers responsible for EPR signals were induced by ion bombardment of the substrates prepared from this glass. The N⁺, O⁺, Ar⁺ and Pb + ions with energy E = 150 keV were used. The integrated dose D was 2 × 10¹⁶ ions/cm². It is shown by means of isochronal anneal experiments and computer simulation of the EPR spectra that they contain four components: broad Gaussian line (GL) with g = 2.016 and σ oscillating in the range 30–40; two anisotropic spectra with g_z = 2.016, g_y = 2.009; g_x = 2.001 (FA₁) and g_z = 2.045; g_y = 2.010; g_x = 1.98 (FA₂) as well as narrow isotropic line of Lorentzian shape with g = 2.0025 and ΔH = 0.6 mT. The comparison of obtained results with literature data for γ-irradiated fluoride glasses and ion-implanted oxide glasses of different compositions permitted to conclude that GL is due to hole defects typical of fluoride glasses and localized on several anions (fluorines and oxygen(s)); anisotropic FA₁- and FA₂-spectra are attributed to molecular 0₂⁻-ions, and narrow isotropic signal is supposedly assigned to big molecular ions (O₂O⁻, 0₄⁻ , CO⁺, CO⁻) located in voids of damaged implantation layer.     

Optical absorption and nonlinear transmission of tetrahedral V (d) in yttrium aluminum garnet

The saturation of the optical absorption in V³⁺ : YAG crystal is investigated. The absorption cross section of tetrahedral V³⁺ at 1.08 μm is estimated to be 8.2±2.5x10^-18 cm². Q-switching and passive mode-locking for a number of solid state lasers with wavelengths at 747 nm, 780 nm, 1.06 μm and 1.34 μm have been obtained with a V³⁺ :YAG saturable absorber.     

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.