Intense White Luminescence from Combustion Synthesized Ca<Subscript>12</Subscript>Al<Subscript>14</Subscript>O<Subscript>33</Subscript>: Yb<Superscript>3+</Superscript>/Yb<Superscript>2+</Superscript> Single Phase Phosphor

The Ca₁₂Al₁₄O₃₃: Yb³⁺/Yb²⁺ single phase nano-phosphor has been synthesized through combustion route and its luminescence and lifetime studies have been carried out up to 20 K using 976 and 266 nm excitations. The samples heated in open atmosphere have shown the presence of Yb in Yb³⁺ and Yb²⁺ states. The 976 nm excitation results a cooperative upconversion emission at 486 nm due to the Yb³⁺ state and a broad band in the blue region and has been assigned to arise from the defect centers. The 266 nm excitation on the other hand results a broad emission band even from as-synthesized phosphor without doping of Yb, the width of which increases in presence of Yb due to the emission from Yb²⁺ ions formed in heated samples. The white emission covers almost whole visible region with bandwidth 190 nm. The ions in Yb²⁺ state has been found to increase with the increase in heating temperature up to 1,273 K. A back conversion of Yb²⁺ to Yb³⁺ has been observed for higher temperatures. Effect of boric and phosphoric acids as flux on the emission properties of Yb³⁺ and Yb²⁺ states have been examined and discussed. Quantum yield of emission has also been determined for different samples.     

Enhanced photoluminescence of Ca<Subscript>2</Subscript>Al<Subscript>2</Subscript>SiO<Subscript>7</Subscript>:Eu<Superscript>3+</Superscript> by charge compensation method

The effect of compensator on optical properties of Ca₂Al₂SiO₇:Eu³⁺ is systematically investigated by the X-ray powder diffraction, photo-luminescence (PL) properties and lifetime. It is obviously observed that the PL intensity of Eu³⁺ under 394 nm excitation increases in the order of Ca_1.86Eu_0.14Al₂SiO₇ (CAS), Ca_1.72Na_0.14Eu_0.14Al₂SiO₇ (CASNa) and Ca_1.86Eu_0.14Al_2.14Si_0.86O₇ (CASAl), the intensity of Eu³⁺ are 100%, 134%, 184%, and the lifetime of Eu³⁺ are 0.75 ms, 1.28 ms and 1.39 ms, respectively. A charge compensation model is proposed to explain the changes in the emission intensity and lifetime of Eu³⁺ in Ca₂Al₂SiO₇ with different compensation methods. PACS 78.55.-m; 61.72.Ji; 61.43.Gt; 42.70.-a; 74.62.Dh     

Residues at the tip of the pore loop of NR3B-containing NMDA receptors determine Ca<Superscript>2+</Superscript> permeability and Mg<Superscript>2+</Superscript>block

Background  

Members of the complex N-methyl-D-aspartate receptor (NMDAR) subfamily of ionotropic glutamate receptors (iGluRs) conventionally assemble from NR1 and NR2 subunits, the composition of which determines receptor properties. Hallmark features of conventional NMDARs include the requirement for a coagonist, voltage-dependent block by Mg²⁺, and high permeability for Ca²⁺. Both Mg²⁺ sensitivity and Ca²⁺ permeability are critically dependent on the amino acids at the N and N+1 positions of NR1 and NR2. The recently discovered NR3 subunits feature an unprecedented glycine-arginine combination at those critical sites within the pore. Diheteromers assembled from NR1 and NR3 are not blocked by Mg²⁺ and are not permeable for Ca²⁺.     

Influence of magnetic ordering on electronic structure of Tb<Superscript>3+</Superscript> ion in TbFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> crystal

Optical absorption spectra of trigonal crystal TbFe₃(BO₃)₄ have been studied in the region of ⁷F₆ → ⁵D₄ transition in Tb³⁺ ion depending on temperature (2–220 K) and on magnetic field (0–60 kOe). Splitting of the Tb³⁺ excited states, both under the influence of the external magnetic field and effective exchange field of the Fe-sublattice, have been determined. Landé factors of the excited states have been found. Stepwise splitting of one of the absorption lines has been discovered in the region of the Fe-sublattice magnetic ordering temperature. This is shown to be due to the abrupt change of equilibrium geometry of the local Tb³⁺ ion environment only in the excited state of the Tb³⁺ ion. In general, the magnetic ordering is accompanied by temperature variations of the Tb³⁺ local environment in the excited states. The crystal field splitting components have been identified. In particular, it has been shown that the ground state (in D ₃ symmetry approximation) consists of two close singlet states of A ₁ and A ₂ type, which are split and magnetized by effective exchange field of the Fe-sublattice. Orientations of magnetic moments of the excited electronic states relative to that of the ground state have been experimentally determined in the magnetically ordered state of the crystal. A pronounced shift of one of absorption lines has been observed in the vicinity of the TbFe₃(BO₃)₄ structural phase transition. The temperature interval of coexistence of the phases is about 3 K.     

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.     

Optical spectra and excited state relaxation dynamics of Sm<Superscript>3+</Superscript> in Gd<Subscript>2</Subscript>SiO<Subscript>5</Subscript> single crystal

Single crystals of gadolinium orthosilicate Gd₂SiO₅ containing 0.5 at% and 5 at% of Sm³⁺ were grown by the Czochralski method. Optical absorption spectra, luminescence spectra and luminescence decay curves were recorded for these systems at 10 K and at room temperature. Comparison of optical spectra recorded in polarized light revealed that the anisotropy of this optically biaxial host affects the intensity distribution within absorption and emission bands related to transitions between multiplets rather than the overall band intensity. It has been found that among four bands of luminescence related to the ⁴G_5/2→⁶H_J (J=5/2–11/2) transitions of Sm³⁺ in the visible and near infrared region the ⁴G_5/2 →⁶H_7/2 one has the highest intensity with a peak emission cross section of 3.54×10⁻²¹ cm² at 601 nm for light polarized parallel to the crystallographic axis c of the crystal. The luminescence decay curve recorded for Gd₂SiO₅:0.5 at% Sm³⁺ follows a single exponential time dependence with a lifetime 1.74 ms, in good agreement with the ⁴G_5/2 radiative lifetime τ _rad=1.78 ms calculated in the framework of Judd-Ofelt theory. Considerably faster and non-exponential luminescence decay recorded for Gd₂SiO₅:5 at% Sm³⁺ sample was fitted to that predicted by the Inokuti-Hirayama theory yielding the microparameter of Sm³⁺–Sm³⁺ energy transfer C _da=1.264×10⁻⁵² cm⁶×s⁻¹.     

Tunable bluish green to yellowish green Ca<Subscript>2(1-x)</Subscript>Sr<Subscript>2x</Subscript>Al<Subscript>2</Subscript>SiO<Subscript>7</Subscript>:Eu<Superscript>2+</Superscript> phosphors for potential LED application

A series of solid solutions with a general formula of Ca_2(1-x)Sr_2xAl₂SiO₇:Eu²⁺ were synthesized by a high temperature solid state reaction. The structure, diffuse reflection spectra, photoluminescence spectra, color-coordinate parameters and lifetimes of phosphors were investigated. XRD results show that Ca₂Al₂SiO₇ is totally miscible with Sr₂Al₂SiO₇. These solid solution phosphors show a broad excitation band of 350–450 nm that matches well with the output lights of near-UV LEDs and tunable emission from bluish green to yellowish green. These optical properties originate from the 4f⁷–4f⁶5d transition of Eu²⁺ ions. The crystal field strength was considered to be tailed by controlling the host composition, which leads to the shift of absorption band and emission band, and the varying of color coordinates. PACS  78.55.-m; 42.70.-a; 61.05.C-     

On the Luminescence of Ce<Superscript>3+</Superscript>, Eu<Superscript>3+</Superscript>, and Tb<Superscript>3+</Superscript> in Novel Borate LiSr<Subscript>4</Subscript>(BO<Subscript>3</Subscript>)<Subscript>3</Subscript>

This paper reports on the photoluminescence (PL) and time-resolved properties of Ce³⁺, Eu³⁺, and Tb³⁺ in novel LiSr₄(BO₃)₃ powder phosphors. Ce³⁺ shows an emission band peaking at 420 nm under 350-nm UV excitation. Energy transfer from Ce³⁺ to Mn²⁺ takes place in the co-doped samples. Eu³⁺ shows red emission under near UV excitation. LiSr₄(BO₃)₃:Eu³⁺ phosphor could be a suitable candidate for phosphor-converted solid state lighting. The luminescence lifetime is 2.13 ms for Eu³⁺ in LiSr₄(BO₃)₃:0.001Eu³⁺. As Eu³⁺ concentration increasing, the decay curves deviate from exponential behavior. Tb³⁺ shows the strongest ⁵D₄→⁷ F₅ emission line at 540 nm. Decay curves of ⁵D₄→⁷ F₅ and ⁵D₃→⁷ F₅ emission with different Tb³⁺ concentrations were also measured. Cross-relaxation process is discussed based on the decay curves.     

Electron-impact ionization and dissociation of C<Subscript>2</Subscript>D<Superscript>+</Superscript>

Absolute cross sections for electron-impact single ionization, dissociative excitation and dissociative ionization of the ethynyl radical ion (C₂D⁺)^+) have been measured for electron energies ranging from the corresponding reaction thresholds to 2.5 keV. The animated crossed electron-ion beam experiment is used and results have been obtained for the production of C₂D²⁺, C²⁺, C₂⁺_2^+ , CD⁺, C⁺ and D⁺. The maximum of the cross section for single ionization is found to be (2.01 ± 0.02) × 10^-17 cm², at the incident electron energy of 105 eV. Absolute total cross sections for the various singly charged fragments production are observed to decrease by a factor of almost three, from the largest cross-section measured for C⁺, over C₂⁺_2^+ and CD⁺ down to that of D⁺. The maxima of the cross sections are obtained to be (14.5 ± 0.5) × 10^-17 cm² for C₂⁺_2^+, (12.1 ± 0.1) × 10^-17 cm² for CD⁺, (27.7 ± 0.2) × 10^-17 cm² for C⁺ and (11.1 ± 0.8) × 10^-17 cm² for D⁺. The smallest cross section is measured to be (1.50 ± 0.04) × 10^-18 cm² for the production of the doubly charged ion C²⁺. Individual contributions for dissociative excitation and dissociative ionization are determined for each singly-charged product. The cross sections are presented in closed analytic forms convenient for implementation in plasma simulation codes. Kinetic energy release distributions of dissociation fragments are seen to extend from 0 to 6 eV for the heaviest fragment C₂⁺_2^+, up to 11.0 eV for CD⁺, 14.2 eV for C⁺ and 11.2 eV for D⁺ products.     

Luminescence in Dy<Superscript>3+</Superscript> and Eu<Superscript>3+</Superscript> Activated K<Subscript>3</Subscript>Al<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>

The Dy³⁺ and Eu³⁺ activated K₃Al₂ (PO₄)₃ phosphors were prepared by a combustion synthesis. From a powder X-ray diffraction (XRD) analysis the formation of K₃Al₂ (PO₄)₃ was confirmed. In the photoluminescence emission spectra, the K₃Al₂(PO₄)₃:Dy³⁺ phosphor emits two distinctive colors: blue and yellow whereas K₃Al₂(PO₄)₃:Eu³⁺ emits red color. Thus the combination of colors gives BYR (blue–yellow–red) emissions can produce white light. These phosphors exhibit a strong absorption between 340 and 400 nm which suggest that present phosphor is a promising candidate for producing white light-emitting diodes (LED).     

Synthesis and luminescence properties of the red phosphor CaZrO<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> for white light-emitting diode application

Eu³⁺-doped CaZrO₃ phosphor with perovskite-type structure was synthesized by the high temperature solid-state method. The samples were characterized by X-ray diffraction, scanning electron microscopy, fluorescence spectrophotometer and UV-vis spectrophotometer, respectively. XRD analysis showed that the formation of CaZrO₃ was at the calcinations temperature of 1400°C. The average diameter of CaZrO₃ with 4 mol% doped-Eu³⁺ was 2μm. The PL spectra demonstrated that CaZrO₃:Eu³⁺ phosphor could be excited effectively in the near ultraviolet light region (397 nm) and emitted strong red-emission lines at 616 nm corresponding to the forced electric dipole ⁵ D ₀ → ⁷ F ₂ transitions of Eu³⁺. Meanwhile, the light-emitting diode was fabricated with the Ca_0.96ZrO³:Eu_0.04³⁺ phosphor, which can efficiently absorb ∼ 400 nm irradiation and emit red light. Therefore Ca_0.96ZrO₃:Eu_0.04³⁺ may have applications for a near ultraviolet InGaN chip-based white light-emitting diode.     

Photolumiscent Properties of Nanorods and Nanoplates Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript>

Nanorods and nanoplates of Y₂O₃:Eu³⁺ powders were synthesized through the thermal decomposition of the Y(OH)₃ precursors using a microwave-hydrothermal method in a very short reaction time. These powders were analyzed by X-ray diffraction, field emission scanning electron microscopy, Fourrier transform Raman, as well as photoluminescence measurements. Based on these results, these materials presented nanoplates and nanorods morphologies. The broad emission band between 300 and 440 nm ascribed to the photoluminescence of Y₂O₃ matrix shifts as the procedure used in the microwave-hydrothermal assisted method changes in the Y₂O₃:Eu³⁺ samples. The presence of Eu³⁺ and the hydrothermal treatment time are responsible for the band shifts in Y₂O₃:Eu³⁺ powders, since in the pure Y₂O₃ matrix this behavior was not observed. Y₂O₃:Eu³⁺ powders also show the characteristic Eu³⁺ emission lines at 580, 591, 610, 651 and 695 nm, when excited at 393 nm. The most intense band at 610 nm is responsible for the Eu³⁺ red emission in these materials, and the Eu³⁺ lifetime for this transition presented a slight increase as the time used in the microwave-hydrothermal assisted method increases.     

Growth defect W<Superscript>3+</Superscript>-W<Superscript>2+</Superscript> of CdWO<Subscript>4</Subscript> crystals

CdWO₄ crystals grown by the Czochralski method at the low-temperature gradient were investigated with electron spin resonance (ESR) spectroscopy. ESR spectra did not contain the spectra of impurity ions typical for the CdWO₄ structure, i.e., Fe³⁺, Mn²⁺, and Cr³⁺. At the same time, in the studied crystals a complex ESR spectrum having the hyperfine structure due to two nonequivalent tungsten atoms was observed (W¹⁸³;I=1/2; natural abundance, 14.28%). Angular dependence analysis and simulation of ESR spectra have shown that this novel spectrum is described by a spin-Hamiltonian with the following parameters:D=839 G,E=80 G,g _xx=2.01,g _yy=1.97,g _zz=1.987 and electron spinS=7/2. There is one magnetically nonequivalent position of the center in the crystal structure and the direction ofD _zz andg _zz corresponds to the direction of W_n-W_n+2 (or Cd_n-Cd_n+2) in the crystal structure. Because of the fact that it is in principle impossible to achieve the electron stateS=7/2 for the d-shell of one transition metal ion and taking into account the fact that such electron state is realized for two nonequivalent tungsten atoms, we suppose the defect structure to be the chain W²⁺-M⁺-W³⁺. In the structure of this defect the ion M⁺ is diamagnetic, the ions W²⁺ and W³⁺ have electron spinS=2 andS=3/2, respectively. The necessary condition for such defect to exist is to place this chain of ions in cadmium positions for the charge compensation. the reason for such defects to form is supposed to be the incorporation of M⁺ ions into the CdWO₄ lattice. The presence of W²⁺ and W³⁺ in Cd positions in the defect structure provides the charge compensation and the lowering of the lattice stress.     

Sensitizer-dependent up-conversion of Ho<Superscript>3+</Superscript> in nanocrystalline Y<Subscript>2</Subscript>O<Subscript>3</Subscript>

Ho³⁺–Yb³⁺ co-doped Y₂O₃ nanocrystals were synthesized by firing hydroxy carbonate precursors. Yb³⁺-concentration-dependent up-conversion properties of Ho³⁺ in Y₂O₃ nanocrystals have been investigated. The relative intensity of up-converted red emission increases more quickly than that of the green and the near-infrared ones with the enhancement of the concentration of Yb³⁺. It is believed that the energy process ⁵ S ₂ (⁵F₄) (Ho) + ⁵ I ₇ (Ho) →⁵ I ₆ (Ho)+⁵ F ₅ (Ho) plays an important role in the population of the ⁵ F ₅ level of Ho³⁺. The result indicates that the intensity ratio of the green emission to the red one can be tuned by changing the sensitizer concentration. PACS 78.55.-m     

Functional distribution of Ca<Superscript>2+</Superscript>-coupled P2 purinergic receptors among adrenergic and noradrenergic bovine adrenal chromaffin cells

Background  

Adrenal chromaffin cells mediate acute responses to stress through the release of epinephrine. Chromaffin cell function is regulated by several receptors, present both in adrenergic (AD) and noradrenergic (NA) cells. Extracellular ATP exerts excitatory and inhibitory actions on chromaffin cells via ionotropic (P2X) and metabotropic (P2Y) receptors. We have taken advantage of the actions of the purinergic agonists ATP and UTP on cytosolic free Ca²⁺ concentration ([Ca²⁺]_i) to determine whether P2X and P2Y receptors might be asymmetrically distributed among AD and NA chromaffin cells.     

Analysis of the charge transfer mechanisms responsible for the current-voltage characteristics of Ca<Subscript>4</Subscript>Ga<Subscript>2</Subscript>S<Subscript>7</Subscript>: Eu<Superscript>3+</Superscript> single crystals

The current-voltage characteristics of Ca₄Ga₂S₇: Eu³⁺ single crystals are measured for the first time, and the processes affecting these characteristics are analyzed theoretically. It is demonstrated that Ca₄Ga₂S₇: Eu³⁺ single crystals are high-resistance semiconductors with a resistivity of ～10⁹ Ω cm and a relative permittivity of 10.55. The electrical properties of the studied materials are governed by traps with activation energies of 0.13 and 0.19 eV and a density ranging from 9.5×10¹⁴ to 2.7×10¹⁵ cm^?3. The one-carrier injection is observed in weak electric fields. In electric fields with a strength of more than 4×10³ V/cm, traps undergo thermal field ionization according to the Pool-Frenkel mechanism. At low temperatures and strong fields (160 K and 5×10⁴ V/cm), the electric current is most likely due to hopping conduction by charge carriers over local levels in the band gap in the vicinity of the Fermi level.     

Spectroscopic Properties and Energy Transfer Analysis of Tm<Superscript>3+</Superscript>-Doped BaF<Subscript>2</Subscript>-Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>-GeO<Subscript>2</Subscript>-La<Subscript>2</Subscript>O<Subscript>3</Subscript> Glass

This paper reports on the spectroscopic properties and energy transfer analysis of Tm³⁺-doped BaF₂-Ga₂O₃-GeO₂-La₂O₃ glasses with different Tm₂O₃ doping concentrations (0.2, 0.5, 2.0, 2.5, 3.0, 3.5, 3.5, 4.0 wt%). Mid-IR fluorescence intensities in the range of 1,300 nm−2,200 nm have been measured when excited under an 808 nm LD for all the samples with the same pump power. Energy level structure and Judd-Ofelt parameters have been calculated based on the absorption spectra of Tm³⁺, cross-relaxation rates and multi-phonon relaxation rates have been estimated with different Tm₂O₃ doping concentrations. The maximum fluorescence intensity at around 1.8 μm has been obtained in Tm₂O₃-3 wt% sample and the maximum value of calculated stimulated emission cross-section of Tm³⁺ in this sample is about 0.48 × 10⁻²⁰ cm² at 1,793 nm, and there is not any crystallization peak in the DSC curve of this sample, which indicate the potential utility of Tm³⁺-doped BaF₂-Ga₂O₃-GeO₂- La₂O₃ glass for 2.0-μm optical fiber laser.     

Spectral properties of neodymium in POCl<Subscript>3</Subscript>-BCl<Subscript>3</Subscript>-Nd<Superscript>3+</Superscript>

We measured the absorption and luminescence spectra of Nd³⁺ ions in an inorganic solvent POCl₃-BCl₃. The spectra were analyzed in terms of the Judd-Ofelt theory. We calculated the Judd-Ofelt parameters, oscillator strengths, spontaneous emission probabilities, luminescence quantum yield, and the stimulated emission cross section for the laser transition ⁴ F _3/2 → ⁴ I _11/2 of the neodymium ion in a POCl₃-BCl₃-Nd³⁺ solution.     

Color Change Upconversion Mechanism of Y<Subscript>6</Subscript>O<Subscript>5</Subscript>F<Subscript>8</Subscript>: Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript> Microtubes by Using Time-Resolve Spectra

The mechanism of the upconversion processes in Y₆O₅F₈: 2%Er³⁺/X%Yb³⁺ (X = 3, 10, 20) microtubes has been explored. The luminescent properties of the as prepared sample is investigated by utilizing up- /downconversion, decay and time resolve spectra. The results indicate that the red and green emission are clearly competitive depending on the Yb³⁺ concentration. High Yb³⁺ concentration induces the enhancement of the energy-back-transfer (EBT), process, which leads to the quenching of green emission and enhances the red emission. So it is possible to utilize the temporal evolutions of emission bands to deeply understand the color change UC mechanisms.     

Low-Frequency Optically Detected EPR of Sm<Superscript>3+</Superscript> in Cs<Subscript>2</Subscript>NaYF<Subscript>6</Subscript> Single Crystal

The Sm³⁺ ion in the Cs₂NaYF₆ single crystal was studied by optically detected electron paramagnetic resonance spectroscopy. Magnetic resonance signals were recorded by Faraday rotation at the frequency of 0.6–0.85 GHz and magnetic fields of about 0.14 T. The hyperfine parameters of ¹⁴⁷Sm³⁺ and ¹⁴⁹Sm³⁺ isotopes were determined.