Spectral analysis of RE (RE = Sm, Dy, and Tm): P2O5–Al2O3–Na2O glasses

Phosphate glasses in the compositions of 70P₂O₅–15Al₂O₃–14Na₂O–1RE³⁺ (RE = Sm, Dy, and Tm) (mol%) were prepared by melt-quenching technique and characterized optically. The differential thermal analysis (DTA) profile of the host glass was carried out to confirm its thermal stability. For all the glasses absorption, photoluminescence and decay measurements have also been carried out. These glasses have shown strong emission and absorption bands in visible and near-infrared (NIR) region. From the measured absorption spectra, Judd–Ofelt (J–O) intensity parameters (Ω₂, Ω₄ and Ω₆) have been calculated for all the studied ions. For Sm³⁺ doped glass, four emission bands centered at 562 nm (⁴G_5/2 → ⁶H_5/2), 598 nm (⁴G_5/2 → ⁶H_7/2), 644 nm (⁴G_5/2 → ⁶H_9/2), and 704 nm (⁴G_5/2 → ⁶H_11/2) have been observed with 402 nm (⁶H_5/2 → ⁴F_7/2) excitation wavelength. Of them, 598 nm (⁴G_5/2 → ⁶H_7/2) has shown a bright orange emission. With regard to Dy³⁺ doped glass, a blue emission band centered at 486 nm (⁴F_9/2 → ⁶H_15/2) and a bright yellow emission at 575 nm (⁴F_9/2 → ⁶H_13/2) have been observed, apart from 662 nm (⁴F_9/2 → ⁶H_11/2) emission transition with an excitation at 388 nm (⁶H_15/2 → ⁴I_13/2,⁴F_7/2) wavelength. Emission bands of 650 nm (¹G₄ → ³F₄) and 785 nm (¹G₄ → ³H₅) transitions for the Tm³⁺ doped glass, with an excitation wavelength at 466 nm (³H₆ → ¹G₄), have also been observed. The stimulated emission cross-sections of all the emission bands of RE³⁺ glasses (RE = Sm, Dy, and Tm) have been computed based on their measured full-width at half maximum (FWHM, Δλ) and measured lifetimes (τ_m).     

Preparation of SrAl2O4: Eu, Dy nanometer phosphors by detonation method

SrAl₂O₄: Eu²⁺, Dy³⁺ nanometer phosphors were synthesized by detonation method. The particle morphology and optical properties of detonation soot that was heated at different temperatures (600–1100 °C) had been studied systematically by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Results indicated SrAl₂O₄: Eu²⁺, Dy³⁺ nanometer powders in monoclinic system (a = 8.442, b = 8.822, c = 5.160, β = 93.415) can be synthesized by detonation method, when detonation soot was heated at 600–800 °C. The particle size of SrAl₂O₄: Eu²⁺, Dy³⁺ is 35 ± 15 nm. Compared with the solid-state reaction and sol-gel method, synthesis temperature of the detonation method is lower about 500 and 200 °C respectively. After being excited under UN lights, detonation soot and that heated at 600–1100 °C can emit a green light.     

Effect of Mg and Ti doping on the luminescence of Y2O2S:Eu

The Y₂O₂S:Eu³⁺,Mg²⁺,Ti^IV (x_Eu = 0.028, x_Mg = 0.086, x_Ti = 0.03) materials were prepared with the flux fusion method. According to X-ray powder diffraction, the materials had the hexagonal crystal structure. The emission of Y₂O₂S:Eu³⁺,Mg²⁺,Ti^IV was centered at 627 nm (λ_exc : 250 nm) due to the ⁵D₀ → ⁷F₂ transition of Eu³⁺. The excitation spectra (λ_em : 627 nm) showed broad bands at 240 and 320 nm due to the O²⁻ → Eu³⁺ and S²⁻ → Eu³⁺ charge transfer transitions, respectively. The latter band can also overlap with the Ti → Eu³⁺ energy transfer. In the excitation spectra with synchrotron radiation, in addition to the O²⁻ → Eu³⁺ and S²⁻ → Eu³⁺ charge transfer transitions, excitation over the band gap was observed at 4.8 eV (258 nm). The red persistent luminescence due to the ⁵D₀ → ⁷F₂ emission from Eu³⁺ residing in the regular Y³⁺ site of the host was ca. 10 min with 1 min fluorescent lamp irradiation. In addition, a very broad band was observed at 600 nm probably due to the Ti³⁺ emission.     

Preparation, structure analysis and photoluminescence properties of MgGa2O4:Mn

In this work the photoluminescence and excitation spectra at room temperature of the spinel-type MgGa₂O₄ with 0.5% and 10.0% of Mn²⁺ have been studied. The polycrystalline samples were synthesized by standard solid-state reaction methods at high temperature. The photoluminescence spectra exhibit green and red emissions for both samples, attributed to ⁴T₁(⁴G) → ⁶A₁(⁶S) transition of Mn²⁺ ion in tetrahedral and octahedral sites of oxygen, respectively. The excitation spectra exhibit features unambiguously assigned to d–d transitions of Mn²⁺ in those kinds of sites. From the excitation spectra and Tanabe–Sugano matrices the crystal field Dq and Racah B parameters were obtained.     

Magnetic susceptibility, spin transition, and electrical conductivity of LaCo1 + xO3 and NdCo1 + xO3

The magnetic susceptibility of Nd₂O₃, NdCo_{1 + x} O₃, and LaCo_{1 + x} O₃ (x = 0, 0.05, 0.1, 0.15) has been measured at temperatures from 80 to 950 K, and the electrical conductivity of the neodymium and lanthanum cobaltites (enriched in cobalt relative to neodymium or lanthanum) with the general formulas Nd(La)Co_{1 + x} O_{3 + 1.5x} , or Nd_{1/(1 + x)}(La)_{1/(1 + x)}CoO_{(3 + 1.5x)/(1 + x)}, has been measured between 300 and 1050 K. The effective magnetic moments of paramagnetic ions have been determined in the temperature ranges of CurieWeiss behavior and have been used to evaluate the fractions of low-, intermediate-, and high-spin Co³⁺ ions. Raising the temperature from 320 to 660 K (non-Curie—Weiss behavior) increases the fraction of high-spin Co³⁺ ions in LaCo_{1 + x} O_{3 + 1.5x} (La_{1/(1 + x)}CoO_{(3 + 1.5x)/(1 + x)} from 27–43 to 56–61%. Moreover, in this temperature range the conductivity of the lanthanum cobaltites rises most steeply. In the range 660–950 K, no spin transition occurs in LaCo_{1 + x} O_{3 + 1.5x} , the slope of the conductivity versus temperature curves gradually decreases, and the conductivity gradually saturates. The conductivity of NdCo_{1 + x} O_{3 + 1.5x} (Nd_{1/(1 + x)}CoO_{(3 + 1.5x)/(1 + x)}) varies considerably in the range 550–950 K, and the spin transition in these cobaltites takes place between 260 and 760 K. Above 760 K, the NdCo_{1 + x} O_{3 + 1.5x} cobaltites with x = 0.05 and 0.10 contain, respectively, 72 and 83% high-spin Co³⁺ ions and 28 and 17% high-spin Co⁴⁺ ions, whereas neodymium cobaltite with x = 0.15 contains 83% high-spin and 17% intermediate-spin Co³⁺ ions. Original Russian Text ? S.V. Shevchenko, L.A. Bashkirov, G.S. Petrov, S.S. Dorofeichik, N.N. Lubinskii, 2008, published in Neorganicheskie Materialy, 2008, Vol. 44, No. 1, pp. 88–94.     

Influence of ZnO additions to 0.8(Mg0.95Co0.05)TiO3–0.2Ca0.6La0.8/3TiO3 ceramics on sintering behavior and microwave dielectric properties

The effects of ZnO addition on the microstructures and microwave dielectric properties of 0.8(Mg_0.95Co_0.05)TiO3–0.2Ca_0.6La_0.8/3TiO₃ ceramics were investigated. ZnO was selected as liquid phase sintering aids to lower the sintering temperature of 0.8(Mg_0.95Co_0.05)TiO3–0.2Ca_0.6La_0.8/3TiO₃ ceramics. With ZnO additives, the densification temperature of 0.8(Mg_0.95Co_0.05)TiO₃–0.2Ca_0.6La_0.8/3TiO₃ can be effectively reduced from 1450 to 1200–1325 °C. The crystalline phase exhibited no phase difference at low addition levels (0.25–2 wt.%). It is found that low-level doping of ZnO (0.25–2 wt.%) can significantly improve the density and dielectric properties of 0.8(Mg_0.95Co_0.05)TiO₃–0.2Ca_0.6La_0.8/3TiO₃ ceramics. The quality factors Q × f were strongly dependent upon the amount of additives. Q × f values of 36 000 and 13 000 GHz could be obtained at 1200–1325 °C with 1 and 2 wt.% ZnO additives, respectively. During all additives ranges, the relative dielectric constants were significantly different and ranged from 23.1 to 27.96. The temperature coefficient varies from 14.1–24.3 ppm/°C.     

Fabrication and optical properties of NUV-emitting SiO2–SrB4O7:Eu glass–ceramic thin films

SiO₂–SrB₄O₇:Eu²⁺ glass–ceramic thin films were fabricated for possible application in near ultraviolet (NUV) emitting devices. Nano-sized SrB₄O₇:Eu²⁺ powders were prepared by a Pechini-type sol–gel method and a subsequent ball-milling treatment. The powders showed NUV emissions centered at 367 nm, upon irradiation with UV of shorter wavelengths, due to an allowed 4f⁶5d¹ → 4f⁷ electronic transition of Eu²⁺ ions. The glass–ceramic thin films were prepared by dip-coating of tetraethylorthosilicate (TEOS) solutions dispersed with the nano-sized SrB₄O₇:Eu²⁺ powders and a subsequent heat-treatment. It was found that the glass–ceramic thin films had relatively high thermal stability up to 800 °C in terms of the Eu²⁺ emissions. SiO₂ layers surrounding SrB₄O₇:Eu²⁺ appeared to be effective for the surface passivation of the phosphor particles.     

Polarization dependence of the optical response in SnO2 and the effects from heavily F doping

The optical properties of intrinsic SnO₂ (TO) and fluorine doped (FTO) are characterized in terms of the dielectric function ε(ħω) = ε₁(ħω) + iε₂(ħω) by electronic structure calculations. The intrinsic TO shows intriguing absorption characteristics in the 3.0–8.0 eV region: (i) the low energy region of the fundamental band gap (3.2 < ħω < 3.9 eV), the optical transitions Г₃⁺ → Г₁⁺ (valence-band maximum to conduction-band minimum) is symmetry forbidden, and the band-edge absorption is therefore extremely weak. (ii) In the higher energy region (3.9 < ħω < 5.1 eV) the Г₅⁻ → Г₁⁺ transitions (from the second uppermost valence band) is strongly polarized perpendicular to the main c axis. (iii) Transitions with polarization axis parallel to c axis are generated from Г₂⁻ → Г₁⁺ transitions (from the third uppermost valence bands), and dominates at high energies (5.1 < ħω eV). Heavily F doped TO (FTO) with doping concentrations n_F = 4 × 10²⁰ cm^− 3 changes the absorption significantly: (iv) Substitutional F_O generates strong inter-conduction band absorption at 0.8, 2.2, and 3.8 eV which affects also the high frequency dielectric constant ε_∞. (v) Interstitial F_i is inactive as a single dopant, but act as a compensating acceptor in highly n-type FTO. This explains the measured non-linear dependence of the resistivity with respect to F concentration.     

Up-conversion luminescence properties of Y2O2S:Yb,Er nanophosphors

Up-converting yttrium oxysulfide nanomaterials doped with ytterbium and erbium (Y₂O₂S:Yb³⁺,Er³⁺) were prepared with the flux method. The precursor oxide materials were prepared using the combustion synthesis. The morphology of the oxysulfides was characterized with transmission electron microscopy (TEM). The particle size distribution was 10–110 nm, depending on the heating temperature. According to the X-ray powder diffraction (XPD), the crystal structure was found hexagonal and the particle sizes estimated with the Scherrer equation agreeded with the TEM images. Upon the 970 nm infrared (IR) laser excitation, the materials yield moderate green ((²H_11/2, ⁴S_3/2) → ⁴I_15/2 transition) and strong red (⁴F_9/2 → ⁴I_15/2) luminescence. The green luminescence was enhanced with respect to the red one by an increase in both the crystallite size and erbium concentration due to the cross-relaxation (CR) processes. The most intense up-conversion luminescence was achieved with x_Yb and x_Er equal to 0.10 and 0.005, respectively. Above these concentrations, concentration quenching occurred.     

Structural evolution and its influence on luminescence of SiO2–SrF2–ErF3 glass ceramics prepared by sol–gel method

Er³⁺ doped SrF₂–SiO₂ transparent glass ceramics were prepared by sol–gel method and heat treatment. The decomposition of Sr²⁺–CF₃COO⁻ and the formation of SrF₂ nano-crystals were found to proceed synchronously in the xerogel. After crystallization of the xerogel, SrF₂ nano-crystals with 8–10 nm in size distributed homogenously among the glassy matrix, and the microstructure of the glass ceramic was stable under and at the temperature of 800 °C probably due to interfacial interaction between nano-crystals and glassy matrix. When heat-treated at 800 °C, the chemically bonded water in the sample was eliminated, resulting in the appearance of the visible luminescence bands of ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions.     

Influence of calcination temperature on luminescent properties of Sr3Al2O6:Eu, Dy phosphors prepared by sol–gel-combustion processing

The detailed preparation process of Eu²⁺ and Dy³⁺ ion co-doped Sr₃Al₂O₆ phosphor powders with red long afterglow by sol–gel-combustion method in the reducing atmosphere is reported. X-ray diffraction, scanning electron microscopy and photoluminescence spectroscopy are used to investigate the effects of synthesis temperature on the crystal characteristics, morphology and luminescent properties of the as-synthesized Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphors. The results reveal that Sr₃Al₂O₆ crystallizes completely when the combustion ash is sintered at 1200 °C. The excitation and the emission spectra indicate that the excitation broad-band lies chiefly in visible range and the phosphor powders emit strong light at 618 nm under the excitation of 472 nm. The light intensity and the light-lasting time of Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphors are increased when increasing the calcination temperatures from 1050 to 1200 °C. The afterglow of Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphors sintered at 1200 °C lasts for over 600 s when the excited source is cut off. The red emission mechanism is discussed according to the effect of nephelauxetic and crystal field on the 4f⁶5d¹ → 4f⁷ transition of the Eu²⁺ ions.     

VUV–UV spectroscopic properties of RE (RE = Ce, Eu and Tb)-doped KMLn(PO4)2 (M = Ca, Sr; Ln = Y, La, Lu)

The VUV excited luminescent properties of Ce³⁺, Eu³⁺ and Tb³⁺ in the matrices of KMLn(PO₄)₂ (M²⁺ = Ca, Sr; Ln³⁺ = Y, La, Lu) were investigated. The bands at about 155 nm in the VUV–UV excitation spectra are attributed to the host lattice absorption, which indicates that the optical band gap of KMLn(PO₄)₂ is about 8.0 eV. Ce³⁺-doped samples show typical Ce³⁺ emission in the range of 300–450 nm, and the energy transfer from host lattice to Ce³⁺ is efficient. For Eu³⁺-doped samples, the O²⁻–Eu³⁺ CTBs are observed to be at about 228 nm except KSrLu(PO₄)₂:Eu³⁺ (247 nm). As for Tb³⁺-doped samples, typical 4f → 5d absorption bands in the region of 175–250 nm were observed.     

Enhancement of fatigue endurance and retention characteristic in Bi3.25Eu0.75Ti3O12 thin films

The effects of moderate annealing temperature (600–800 °C) on the microstructure, fatigue endurance, retention characteristic, and remnant polarization (2P_r) of Bi_3.25Eu_0.75Ti₃O₁₂ (BET) thin films prepared by metal-organic decomposition (MOD) were studied in detail. 2P_r (66 µC/cm² under 300 kV/cm), fatigue endurance (3% loss of 2P_r after 1.2 × 10¹⁰ switching cycles), and retention characteristic (no significant polarization loss after 1.8 × 10⁵s) for BET thin film annealed at 700 °C are better than those for thin films annealed at other temperature. The mechanisms concerning the dependence of microstructure and ferroelectric properties on the annealing temperature were discussed.     

UV–VUV spectroscopy of rare earth doped persistent luminescence materials

The electronic and defect energy level structure of polycrystalline SrAl₂O₄:Eu²⁺,R³⁺ persistent luminescence materials were studied with thermoluminescence and UV–VUV synchrotron radiation emission and excitation spectroscopy. Theoretical calculations using the density functional theory (DFT) were carried out simultaneously with the experimental work. The experimental band gap energy (E_g) value of 6.6 eV agrees very well with the DFT value of 6.4 eV. The 4f⁷ → 4f⁶5d¹ excitation bands of Eu²⁺ were found rather similar irrespective of the R³⁺ co-dopant. The trap level energy distribution depended strongly on the R³⁺ co-dopant except for the shallowest trap energy above the room temperature remaining the same, however. The different processes in the mechanism of persistent luminescence from SrAl₂O₄:Eu²⁺,R³⁺ was constructed and discussed.     

The polar cluster like behavior in Ti substituted BaZrO3 ceramics

In this paper we report the evolution of the polar cluster like behavior with the incorporation of Ti⁴⁺ ion in BaZrO₃ Ceramics. Dielectric behavior of BaZr_xTi_(1−x)O₃ (x = 1.00, 0.95, 0.90, 0.85) ceramics is studied in the temperature range from 300 to 30 K. Polar cluster like behavior becomes more prominent with the increase in content of Ti⁴⁺ ion. The dielectric relaxation is analyzed by Vogel–Fulcher relation and Arrhenius law. Frequency dependence of dielectric constant and low loss tangent of these materials can be useful for the potential applications at low temperature.     

Microwave dielectric and elastic properties of glass-added Ba6−3xR8+2xTi18O54 (x = 2/3)

Microwave dielectric properties of Ba_6−3xSm_8+2xTi₁₈O₅₄ (x = 2/3) [BST] ceramics with the addition of 0–3 wt.% of various glasses have been studied. It has been found that the addition of 0.5 wt.% of the glasses decreases the sintering temperature by about 150 °C. In general, addition of 0.5 wt.% of Zn, Mg and Pb-based glasses deteriorate the quality factor, whereas aluminum and barium borosilicates do not decrease it considerably. The quality factor and dielectric constant decrease with increasing amount of glass. The temperature coefficient of resonant frequency shifts towards positive or negative depending on the composition of the glass. A glass–ceramic composite with a dielectric constant 64, Q × f nearly 8500 GHz and near to zero τ_f could be obtained at a sintering temperature of 1175 °C when 3–4 wt.% Al₂O₃–B₂O₃–SiO₂ glass was added to BST ceramic. The Young's modulus decreases with increasing amount of glass, irrespective of the composition of glass.     

Electrochemical characteristics of Ba0.5Sr0.5Co0.8Fe0.2O3−δ–Sm0.2Ce0.8O1.9 composite materials for low-temperature solid oxide fuel cell cathodes

In this paper, Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ–xSm_0.2Ce_0.8O_1.9 (BSCF–xSDC, x = 0–60 wt.%) composite cathodes were prepared by soft chemical methods, and then examined for potential applications in lower temperature solid oxide fuel cells. Both DC polarization and AC impedance spectroscopy measurements indicated that the addition of SDC electrolyte into BSCF remarkably improved the electrochemical properties. The optimum composition was found to be BSCF–30SDC, which exhibited 5.5 times higher polarization current density and 15.1% polarization resistance, compared with the pure-phase BSCF cathode at 550 °C.     

Effects of Ho2O3 addition on defects of BaTiO3

Effects of Ho₂O₃ addition on defects of BaTiO₃ ceramic have been studied in terms of electrical conductivity at 1200 °C as a function of oxygen partial pressure (P_O2°) and oxygen vacancy concentration. The substitution of Ho³⁺ for the Ti site in Ba(Ti_1−xHo_x)O_3−0.5x resulted in a significant shift of conductivity minimum toward lower oxygen pressures and showed an acceptor-doped behavior. The solubility limit of Ho on Ti sites was confirmed less than 3.0 mol% by measuring the electrical conductivity and the lattice constant. Oxygen vacancy concentrations were calculated from the positions of P_O2° in the conductivity minima and were in good agreement with theoretically estimated values within the solubility limit. The Curie point moved to lower temperatures with increasing the oxygen vacancy concentration and Ho contents.     

Nature of intrinsic and impure luminescence of MAlP2O7 crystals

The results of the photoluminescence (PL) investigation of pure and chromium-doped MAlP₂O₇ (M = Na, K, Cs) compounds are presented. The spectra of the intrinsic luminescence of MAlP₂O₇ crystals consist of a separated UV band at a peak position near 330 nm and a complex wide band which covers the region of visible light up to 750 nm at excitation by VUV synchrotron radiation. The “red” band in 600–1000 nm diapason appears in the PL spectra of crystals doped with chromium ions. The effect of the temperature on the structure, the peak positions and intensities of the luminescence bands was studied. An assumption about the nature of the intrinsic PL was made. The “red” luminescence was considered as a result of the ⁴Т₂ → ⁴А₂ radiation transitions in the impurity Cr³⁺ ions located in the intermediate crystal field.     

Yellow-emitting phosphor of Sr3B2O6:Eu for application to white light-emitting diodes

This work focuses on the development of Eu²⁺-doped strontium (Sr)-borate as a yellow-emitting phosphor and its application to the fabrication of white light-emitting diodes (LEDs). Synthesis of Eu²⁺-doped Sr-borate phosphors was finely tuned for obtaining the efficient yellow luminescence through varying host composition, Eu concentration, and firing temperature. The 1300 °C-fired Eu²⁺-doped Sr₃B₂O₆, which was found to be the most efficient candidate to date, was used for white LED fabrication. Their optical properties were evaluated, resulting in warm white lights with CIE chromaticity coordinates of (0.340–0.372, 0.287–0.314) and color rendering indices of 75–77 under the forward currents of 5–40 mA.