Luminescence of CaGa<Subscript>2</Subscript>Se<Subscript>4</Subscript>:Eu crystals

We have studied photoluminescence and thermoluminescence (PL and TL) in CaGa₂Se₄:Eu crystals in the temperature range 77–400 K. We have established that broadband photoluminescence with maximum at 571 nm is due to intracenter transitions 4f⁶ 5d–4f⁷ (⁸S_7/2) of the Eu²⁺ ions. From the temperature dependence of the intensity (log I–10³/T), we determined the activation energy (E _a = 0.04 eV) for thermal quenching of photoluminescence. From the thermoluminescence spectra, we determined the trap depths: 0.31, 0.44, 0.53, 0.59 eV. The lifetime of the excited state 4f6 5d of the Eu²⁺ ions in the CaGa₂Se₄ crystal found from the luminescence decay kinetics is 3.8 μsec. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 1, pp. 112–116, January–February, 2009.     

Amplitude gratings generation by selective defect bleaching in KCl:CO<Subscript>3</Subscript>K<Subscript>2</Subscript> crystals

Volume grating formation by spatially-selective defect bleaching is demonstrated in coloured KCl:CO₃K₂ crystals. The sample is coloured by a train of pulses with a wavelength of λ= 266 nm and bleached with a cw Ar-laser with a wavelength of λ= 514.5 nm. Diffraction efficiency for a 1.6 μm grating period is studied both experimentally and theoretically, using the evolution of colour centre concentration. Hologram recording parameters are obtained and the evolution of the spatial grating profile is discussed. Diffraction efficiencies three times higher than previously published efficiencies are obtained. PACS 42.40.Ht; 42.40.Lx; 42.70.Ln     

Photosensitivity and thermosensitivity of polymers doped with Eu(fod)<Subscript>3</Subscript> molecules

We have studied the photoluminescence (PL) spectra of Eu³⁺ ions and the decay kinetics for the photoluminescence intensity on exposure to temperature and UV radiation in polypropylene and oligo(urethane methacrylate) (OUM) doped with Eu(fod)₃ molecules (fod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octadione) by soaking in a supercritical CO₂ solution. We have established that the decay kinetics for the photoluminescence intensity on exposure to UV radiation depends on the temperature of the sample and the concentration of the dopant in it. Based on studies of the spectral characteristics of doped OUM samples, we suggest that this material can be used as a two-color luminescent temperature sensor. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 1, pp. 104-111, January-February, 2009.     

Structure,thermal properties,conductivity and electrochemical stability of di-urethanesil hybrids doped with LiCF<Subscript>3</Subscript>SO<Subscript>3</Subscript>

Variable chain length di-urethane cross-linked poly(oxyethylene) (POE)/siloxane hybrid networks were prepared by application of a sol-gel strategy. These materials, designated as di-urethanesils (represented as d-Ut(Y′), where Y′ indicates the average molecular weight of the polymer segment), were doped with lithium triflate (LiCF₃SO₃). The two host hybrid matrices used, d-Ut(300) and d-Ut(600), incorporate POE chains with approximately 6 and 13 (OCH₂CH₂) repeat units, respectively. All the samples studied, with compositions ∞ > n ≥ 1 (where n is the molar ratio of (OCH₂CH₂) repeat units per Li⁺), are entirely amorphous. The di-urethanesils are thermally stable up to at least 200 °C. At room temperature the conductivity maxima of the d-Ut(300)- and d-Ut(600)-based di-urethanesil families are located at n = 1 (approximately 2.0 × 10⁻⁶ and 7.4 × 10⁻⁵ Scm⁻¹, respectively). At about 100 °C, both these samples also exhibit the highest conductivity of the two electrolyte systems (approximately 1.6 × 10⁻⁴ and 1.0 × 10⁻³ Scm⁻¹, respectively). The d-Ut(600)-based xerogel with n = 1 displays excellent redox stability.     

Investigation of thermoluminescence in Li<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript> phosphors doped with Cu,Ag and Mg

Li2B4O7 (LBO)Cu,Ag,Mg phosphors have been prepared by the sintering technique.The roles of the Ag and Mg dopants in the phosphors have been studied using the methods of thermoluminescence (TL) glow curves and TL 3D spectra. The results indicated that proper concentrations of Ag and Mg can enhance the TL of LBOCu.It was also indicated that the intensity of TL peak at ～130℃ is reduced with the increasing Ag concentration, and enhanced with the increasing Mg concentration.From the TL 3D spectra, three emission bands (λ1 = 421 nm,λ2 = 380 nm, λ3 = 350nm) were observed the intensity of low energy emission band is reduced and that of the high energy is enhanced with the increasing dopant Ag; on the contrary, the intensity of low energy emission band is enhanced and that of the high energy one is reduced with the increasing dopant Mg.     

Fluorescent Carbon Dots Capped with PEG<Subscript>200</Subscript> and Mercaptosuccinic Acid

The synthesis and functionalization of carbon nanoparticles with PEG₂₀₀ and mercaptosuccinic acid, rendering fluorescent carbon dots, is described. Fluorescent carbon dots (maximum excitation and emission at 320 and 430 nm, respectively) with average dimension 267 nm were obtained. The lifetime decay of the functionalized carbon dots is complex and a three component decay time model originated a good fit with the following lifetimes: τ ₁ = 2.71 ns; τ ₂ = 7.36 ns; τ ₃ = 0.38 ns. The fluorescence intensity of the carbon dots is affected by the solvent, pH (apparent pK _a of 7.4 ± 0.2) and iodide (Stern-Volmer constant of 78 ± 2 M⁻¹).     

<Superscript>29</Superscript>Si MAS-NMR study of oxide conductors derived from the apatite-type La<Subscript>9.33</Subscript>Si<Subscript>6</Subscript>O<Subscript>26</Subscript> compound

The preparation of (La_9.33−2x/3Sr _x □_0.67−x/3)Si₆O₂₄O₂ (0 ≤ x ≤ 2) samples with different amounts of cation vacancies is reported. Structure and unit-cell parameters were deduced by Rietveld analysis of XRD patterns. Structural features that enhance oxygen conductivity in Sr-doped apatites are discussed. Up to three components were detected in ²⁹Si MAS-NMR spectra which change with the amount and distribution of cation vacancies. In general, oxygen conductivity increases with the amount of vacancies at La1 (6h) sites, passing through a maximum for x = 0.4. In the case of activation energy, a minimum is detected near x = 1.2, indicating that entropic and enthalpic change in different ways. The presence of cation vacancies should enhance oxygen hopping along c-axis; however, the analysis of the frequency dependence of conductivity suggests that oxygen motions are produced along three axes.     

Magnetic properties of LiNi<Subscript>0.5</Subscript>Mn<Subscript>0.47</Subscript>Al<Subscript>0.03</Subscript>O<Subscript>2</Subscript> as positive electrode for Li-ion batteries

The layered LiNi_0.5Mn_0.47Al_0.03O₂ was synthesized by wet chemical method and characterized by X-ray diffraction and analysis of magnetic measurements. The powders adopted the α-NaFeO₂ structure. This substitution of Al for Mn promotes the formation of Li(Ni_0.47²⁺Ni_0.03³⁺Mn_0.47⁴⁺Al_0.03³⁺)O₂ structures and induces an increase in the average oxidation state of Ni, thereby leading to the shrinkage of the lattice unit cell. The concentration of antisite defects in which Ni²⁺ occupies the (3a) Li lattice sites in the Wyckoff notation has been estimated from the ferromagnetic Ni²⁺(3a)–Mn⁴⁺(3b) pairing observed below 140 K. The substitution of 3% Al for Mn reduces the amount of antisite defects from 7% to 6.4–6.5%. The analysis of the magnetic properties in the paramagnetic phase in the framework of the Curie–Weiss law agrees well with the combination of Ni²⁺ (S = 1), Ni³⁺ (S = 1/2) and Mn⁴⁺ (S = 3/2) spin-only values. Delithiation has been made by the use of K₂S₂O₈. According to this process, known to be softer than the electrochemical one, the nickel ions in the (3b) sites are converted into Ni⁴⁺ in the high spin configuration, while Ni²⁺(3a)–Mn⁴⁺(3b) ferromagnetic pairs remain, as the Li⁺(3b) ions linked to the Ni²⁺(3a) ions in the antisite defects are not removed. The results show that the antisite defect is surrounded by Mn⁴⁺ ions, implying the nonuniform distribution of the cations in agreement with previous NMR and neutron experiments.     

The Role of the Eu<Superscript>3+</Superscript> Concentration on the SrMoO<Subscript>4</Subscript>:Eu Phosphor Properties: Synthesis,Characterization and Photophysical Studies

SrMoO₄ doped with rare earth are still scarce nowadays and have attracted great attention due to their applications as scintillating materials in electro-optical like solid-state lasers and optical fibers, for instance. In this work Sr_1−xEu_xMoO₄ powders, where x = 0.01; 0.03 and 0.05, were synthesized by Complex Polymerization (CP) Method. The structural and optical properties of the SrMoO₄:Eu³⁺ were analyzed by powder X-ray diffraction patterns, Fourier Transform Infra-Red (FTIR), Raman Spectroscopy, and through Photoluminescent Measurements (PL). Only a crystalline scheelite-type phase was obtained when the powders were heat-treated at 800 °C for 2 h, 2θ = 27.8° (100% peak). The excitation spectra of the SrMoO₄:Eu³⁺ (λ_Em. = 614 nm) presented the characteristic band of the Eu^3 + 5L₆ transition at 394 nm and a broad band at around 288 nm ascribed to the charge-transfer from the O (2p) state to the Mo (4d) one in the SrMoO₄ matrix. The emission spectra of the SrMoO₄:Eu³⁺ powders (λ_Exc. = 394 and 288 nm) show the group of sharp emission bands among 523–554 nm and 578–699 nm, assigned to the ⁵D₁→⁷F_{0,1and 2} and ⁵D₀→⁷F_{0,1,2,3 and 4}, respectively. The band related to the ⁵D₀→⁷F₀ transition indicates the presence of Eu³⁺ site without inversion center. This hypothesis is strengthened by the fact that the band referent to the ⁵D₀→⁷F₂ transition is the most intense in the emission spectra.     

Spectroscopic properties of Er<Superscript>3+</Superscript> ions in LiNbO<Subscript>3</Subscript> crystals codoped with HfO<Subscript>2</Subscript>

The results of the spectroscopic analysis of transition strengths for Er³⁺ ions in a series of Hf:Er:LiNbO₃ crystals with variable Hf content and fixed Er content are reported. Unpolarized UV-VIS-NIR absorption spectra, upconversion fluorescence spectra excited at 800 nm, and microsecond time-resolved spectra excited at 400 nm and 800 nm by 800 nm femtosecond laser were measured at room temperature. The HfO₂ incorporation has influence on Er³⁺ radiative lifetimes, and fluorescence branching ratios. For Hf(4 mol %):Er(1 mol %):LiNbO₃, Ω₂=2.63×10^-20 cm², Ω₄=2.86×10^-20 cm², and Ω₆=0.72×10^-20 cm². Ω₂<Ω₄ is contrary to the Er³⁺ general trend of Ω₂>Ω₄>Ω₆ when the Hf content is below its threshold concentration. In addition, the sum of Ω increases with the Hf content when the HfO₂ content below 6 mol % is unfamiliar. The upconversion mechanism is discussed in this work. PACS 71.20.Eh; 77.84.Dy; 42.62.Fi; 42.65.Ky     

High contrast <Emphasis Type="Italic">D</Emphasis><Subscript>1</Subscript> line electromagnetically induced transparency in nanometric-thin rubidium vapor cell

The electromagnetically induced transparency (EIT) on the atomic D ₁ line of rubidium is studied using a nanometric-thin cell with atomic vapor column length in the range of L=400–800 nm. It is shown that the reduction of the cell thickness by four orders as compared with an ordinary cm-size cell still allows to form an EIT resonance for L=λ=794 nm with the contrast of up to 40%. Further reduction of thickness to L=λ/2 leads to significant reduction of EIT contrast, verifying that the key parameter for EIT in wavelength-scale-thickness cells is not the value of L itself but L/λ ratio. Remarkable distinctions of EIT formation in nanometric-thin and ordinary cells are demonstrated. Well-resolved splitting of the EIT resonance in a magnetic field for L=λ can be used for magnetometry with nanometric spatial resolution. The presented theoretical model well describes the observed results.     

A method to study polydispersity of humic acid from fluorescence quenching by Cu<Superscript>2+</Superscript> ions

The spectral dependence of Stern–Volmer constants (K_SV^lK_{SV}^{\lambda} ) for fluorescence quenching by Cu²⁺ ions in a standard sample of humic acid (HA) (IHSS) with monochromatic excitation (λ_ex = 337.1 nm) conditions has been studied in the spectral range 400–600 nm. This is interpreted within a concept implying that HA macromolecules possess the property of polydispersity, which means that fluorophore-containing sites are different in terms of chemical nature and spatial accessibility. Modeling data show that the minimum number of spectral components required for the simulated spectral dependence of K_SV^lK_{SV}^{\lambda} to agree as closely as possible with that observed experimentally is three.     

Sensitizing of Sm<Superscript>3+</Superscript> fluorescence by silver dopant in the TiO<Subscript>2</Subscript> films

Composite material based on a TiO₂ matrix doped with Sm³⁺ ions and co-doped with silver was investigated. Samarium ions together with nano- and micro-aggregates of silver were incorporated into the titanium alkoxide during the sol-gel process. Samarium ions were excited either directly (λ _exc = 488 nm) or through the TiO₂ host (λ _exc = 355 nm). It was revealed that samarium fluorescence (λ _exc = 488 nm) in gelled TiO₂ films is enhanced by up to 20 times in the vicinity of silver inclusions. Sensitizing and plasmonic mechanisms of enhancement in Sm³⁺ fluorescence are discussed.     

Impedance spectroscopy study of Pb<Subscript>2</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript> compound

The lead pyrophosphate, Pb₂P₂O₇, compound was prepared by conventional solid-state reaction and identified by X-ray powder diffractometer. Pb₂P₂O₇ has a triclinic structure whose electrical properties were studied using impedance spectroscopy technique. Both impedance and modulus analysis exhibit the grain and grain boundary contribution to the electrical response of the sample. The temperature dependence of the bulk and grain boundary conductivity were found to obey the Arrhenius law with activation energies E _g = 0.66 eV and E _gb = 0.67 eV, respectively. The scaling behavior of the imaginary part of the complex impedance suggests that the relaxation describes the same mechanism at various temperatures.     

Baric changes in refractive indices of K<Subscript>2</Subscript>ZnCl<Subscript>4</Subscript> crystals

The influence of uniaxial pressure applied along the principal crystallophysical directions on the dispersion and temperature dependences of the refractive indices n _i of K₂ZnCl₄ crystals has been investigated. The n _i values are found to be fairly sensitive to uniaxial pressure, whereas an uniaxial stress does not change the behavior of the dispersion and temperature dependences of n _i . The baric changes in n _i have been studied. The electronic polarizability α _i , refractions R, and parameters of UV oscillators (λ_0i , B _1i ) of mechanically deformed K₂ZnCl₄ crystals have been calculated. The contributions of UV and IR oscillators to n _i (λ) have been estimated for different temperatures, spectral regions, and stresses. A significant baric shift of the points of the paraelectric phase-incommensurate phase-commensurate phase transitions to different temperature ranges, depending on the direction of pressure application, is found; this shift is due to the effect of uniaxial stress on the K₂ZnCl₄ crystal structure.     

Effects of dopant on the electrochemical properties of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> anode materials

The effects of dopant on the electrochemical properties of spinel-type Li_3.97M_0.1Ti_4.94O₁₂ (M = Mn, Ni, Co) and Li_(4-x/3)Cr_xTi_(5-2x/3)O₁₂(x = 0.1, 0.3, 0.6, 0.9, 1.5) were systematically investigated. Charge-discharge cycling were performed at a constant current density of 0.5 mA/cm² between the cut-off voltages of 3.0 and 1.0 V, the experimental results showed that Cr³⁺ dopant improved the reversible capacity and cycling stability over the pristine Li₄Ti₅O₁₂. The substitution of the Mn³⁺ and Ni³⁺ slightly decreased the capacity of the Li₄Ti₅O₁₂. Dopants such as Co³⁺ to some extent worsened the electrochemical performance of the Li₄Ti₅O₁₂.     

Electrical characterization of the [N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>][N(C<Subscript>2</Subscript>H<Subscript>5</Subscript>)<Subscript>4</Subscript>]ZnCl<Subscript>4</Subscript> compound

The [N(CH₃)₄][N(C₂H₅)₄]ZnCl₄ compound has been synthesized by a solution-based chemical method. The X-ray diffraction study at room temperature revealed an orthorhombic system with P2₁2₁2 space group. The complex impedance has been investigated in the temperature and frequency ranges 420–520 K and 200 Hz–5 MHz, respectively. The grain interior and grain boundary contribution to the electrical response in the material have been identified. Dielectric data were analyzed using the complex electrical modulus M ^* for the sample at various temperature. The modulus plots can be characterized by full width at half height or in terms of a non-exponential decay function ϕ(t) = exp[(−t/τ) ^β ]. The detailed conductivity study indicated that the electrical conduction in the material is a thermally activated process. The variation of the AC conductivity with frequency at different temperatures obeys the Almond and West universal law.     

Photoluminescence of CuInS<Subscript>2</Subscript> single crystals grown by traveling heater and chemical vapor transport methods

Photoluminescence of CuInS₂ single crystals grown by both the traveling heater method (THM) and chemical vapor transport (CVT) has been investigated at 4.2, 78, and 300 K. Intense emission in the near-band-edge region caused by free and bound excitons has been detected for both types of crystals. Taking into account the energy position of the luminescence line of the ground (n = 1) and first excited (n = 2) states, the binding energy for free A excitons has been estimated to be about 19.7 and 18.5 meV for CuInS₂ grown by CVT and THM, respectively. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 2, pp. 232–236, March–April, 2009.     

Growth and magneto-optical properties of LiTb(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystal

Lithium terbium molybdate (LiTb(MoO₄)₂) single crystal was grown by the Czochralski method. The lattice parameters of the crystal were determined by X-ray diffraction analysis. The absorption coefficient and the Faraday rotation spectrum (B=1.07 T) were investigated at wavelengths of 400–1500 nm at room temperature. Verdet constants of LiTb(MoO₄)₂ crystal at 532-, 633- and 1064-nm wavelengths were measured by the extinction method. The results show that LiTb(MoO₄)₂ crystal has a larger magneto-optical figure of merit than that of terbium gallium garnet at wavelengths of 600–1500 nm.     

Luminescence and selective heat radiation of Yb<Subscript>2</Subscript>O<Subscript>3</Subscript> upon the resonant and thermal laser excitation

Yb₂O₃ polycrystals with a size of up to 10 mm are synthesized using the sintering and melting of the ultrapure Yb₂O₃ powders by the CO₂-laser radiation with the power P _L ≤ 100 W at the wavelength λ = 10.6 μm at the melting point T _m = 2703 K, forming due to surface tension in melt, and crystallization in air. The analysis of the polycrystal microstructure using the methods of optical and electron microscopy and X- ray diffractometry shows that perfect oxide crystallites are formed in the course of crystallization after melting-through. The transformation of the luminescence and selective heat radiation (SHR) spectra of the Yb₂O₃ polycrystals is studied under the resonant excitation at λ ≈ 975 nm using a laser diode and the laser heating at the wavelength λ = 10.6 μm. When the resonant excitation power of the Yb³⁺ ions increases from 0.15 to 4.5 W, the Stokes luminescence of the Yb₂O₃ polycrystals is sequentially transformed into SHR and the thermal radiation of the crystal lattice. The transformation of the emission spectra of the Yb₂O₃ polycrystals with an increase in the laser heating intensity by about four orders of magnitude can be represented as the low-temperature heat radiation, spectral burst of the thermodynamically nonequilibrium SHR of the Yb³⁺ ions, and the high-temperature radiation of the crystal lattice. The temperature dependence of the luminescence spectra and SHR of the Yb₂O₃ polycrystals on the intensity of the laser and laser-thermal excitation and the concentration quenching of the Yb³⁺ luminescence in oxides indicate the key role of the interaction of the f-electron shell of the Yb³⁺ ions with the natural oscillations of the crystal lattice in the processes of the multiphonon excitation and nonradiative (multiphonon) and radiative (vibronic) relaxation.