A new series of Sr-based phosphates, Sr9−xMnxEu(PO4)7, were synthesized using the high-temperature solid-state method in air. It was found that these compounds have the same structure as ...strontiowhitlockite, which is a β-Ca3(PO4)2 (or β-TCP) structure. The concentration of Mn2+ ions required to form a pure strontiowhitlockite phase was determined. An unusual partial reduction of Eu3+ to Eu2+ in air was observed and confirmed by photoluminescence (PL) and electron spin resonance (ESR) spectra measurements. The PL spectra recorded under 370 nm excitation showed transitions of both 4f5d–4f Eu2+ and 4f–4f Eu3+. The total integral intensity of the PL spectra, monitored at 395 nm, decreased with increasing Mn2+ concentration due to quenching effect of Eu3+ by the Mn2+ levels. The temperature dependence of Eu2+ photoluminescence in a Sr9−xMnxEu(PO4)7 host was investigated. The conditions for the reduction of Eu3+ to Eu2+ in air were discussed.
In this study, a new series of phosphors, Ca9−xZnxGd0.9(PO4)7:0.1Eu3+ (x = 0.00–1.00, step dx 0.05), was synthesized, consisting of centro- and non-centrosymmetric phases with β-Ca3(PO4)2-type ...structure. Crystal structures with space groups R3c (0.00 ≤ x < 0.35) and R3¯c (x > 0.8) were determined using X-ray powder diffraction and the method of optical second harmonic generation. In the region 0.35 ≤ x ≤ 0.75, phases R3c and R3¯c were present simultaneously. Refinement of the Ca8ZnGd(PO4)7 crystal structure with the Rietveld method showed that 71% of Gd3+ ions are in M3 sites and 29% are in M1 sites. A luminescent spectroscopy study of Ca9−xZnxGd0.9(PO4)7:0.1Eu3+ indicated the energy transfer from the crystalline host to the Gd3+ and Eu3+ luminescent centers. The maximum Eu3+ luminescence intensity corresponds to the composition with x = 1.
A new series of Sr-based phosphates, Srsub.9−xMnxEu(POsub.4)sub.7, were synthesized using the high-temperature solid-state method in air. It was found that these compounds have the same structure as ...strontiowhitlockite, which is a β-Casub.3(POsub.4)sub.2 (or β-TCP) structure. The concentration of Mnsup.2+ ions required to form a pure strontiowhitlockite phase was determined. An unusual partial reduction of Eusup.3+ to Eusup.2+ in air was observed and confirmed by photoluminescence (PL) and electron spin resonance (ESR) spectra measurements. The PL spectra recorded under 370 nm excitation showed transitions of both 4f5d–4f Eusup.2+ and 4f–4f Eusup.3+. The total integral intensity of the PL spectra, monitored at 395 nm, decreased with increasing Mnsup.2+ concentration due to quenching effect of Eusup.3+ by the Mnsup.2+ levels. The temperature dependence of Eusup.2+ photoluminescence in a Srsub.9−xMnxEu(POsub.4)sub.7 host was investigated. The conditions for the reduction of Eusup.3+ to Eusup.2+ in air were discussed.
β-Ca3(PO4)2-type phosphors Ca9−xMnxEu(PO4)7 have been synthesized by high-temperature solid-phase reactions. The crystal structure of Ca8MnEu(PO4)7 was characterized by synchrotron X-ray diffraction. ...The phase transitions, magnetic and photoluminescence (PL) properties were studied. The abnormal reduction Eu3+ → Eu2+ in air was observed in Ca9−xMnxEu(PO4)7 according to PL spectra study and confirmed by X-ray photoelectron spectroscopy (XPS). Eu3+ shows partial reduction and coexistence of Eu2+/3+ states. It reflects in combination of a broad band from the Eu2+ 4f65d1 → 4f7 transition and a series of sharp lines attributed to 5D0 → 7FJ transitions of Eu3+. Eu2+/Eu3+ ions are redistributed among two crystal sites, M1 and M3, while Mn2+ fully occupies octahedral site M5 in Ca8MnEu(PO4)7. The main emission band was attributed to the 5D0 → 7F2 electric dipole transition of Eu3+ at 395 nm excitation. The abnormal quenching of Eu3+ emission was observed in Ca9−xMnxEu(PO4)7 phosphors with doping of the host by Mn2+ ions. The phenomena of abnormal reduction and quenching were discussed in detail.
TmMgB5O10 spontaneous crystals were synthesized via the flux-growth technique from a K2Mo3O10-based solvent. The crystal structure of the compound was solved and refined within the space group P21/n. ...The first principles calculations of the electronic structure reveal that TmMg-pentaborate with an ideal not defected crystal structure is an insulator with an indirect energy band gap of approximately 6.37 eV. Differential scanning calorimetry measurements and powder X-ray diffraction studies of heat-treated solids show that TmMgB5O10 is an incongruent melting compound. A characteristic band of the Tm3+ cation corresponding to the 3H6 → 1D2 transition is observed in the photoluminescence excitation spectra of TmMg-borate. The as-obtained crystals exhibit intense blue emission with the emission peaks centered at 455, 479, 667, and 753 nm. The most intensive band corresponds to the 1D2 → 3F4 transition. TmMgB5O10 solids demonstrate the thermal stability of photoluminescence.
•Phosphors with whitlockite-type structure Sr8M2+Sm1-х(PO4)7:xEu3+, M = Mg2+, Zn2+ were synthesized by three type of routes.•The influence of the synthetic route on the luminescent properties was ...revealed.•Solid-state reaction method leads to better crystallinity, and to improvement of the luminescent proprieties.
A series of new Sr-based phosphors Sr8M2+Sm1-х(PO4)7:xEu3+, M = Mg2+, Zn2+ with β-Ca3(PO4)2-type structure was synthesized and studied. The Sr8MgEu(PO4)7 was obtained by three types of synthetic routs: high temperature solid-state, hydrothermal and sol-gel methods. The influence of synthesis routes and annealing conditions on luminescent properties was studied and analyzed taking into account the data on average crystallite size and grain size determination. It was shown that the synthesis method has a defining role on the phosphor’s properties. The solid-state route gives the best powders crystallinity and the highest intensity of emission. The samples were characterized by strong emission in visible region at 615 nm originating from 5D0 → 7F2 transition of Eu3+ and 600 nm originating from the 5G5/2 → 4H7/2 transition of Sm3+. Also, it was revealed that Zn-substituted samples exhibit higher intensity than Mg-containing ones due to larger particle size and lower scattering of light and higher light absorption. Photoluminescence decay curves were measured and the dependence of decay times on activator concentrations was revealed. The CIE chromaticity coordinates were close to red standard. The prototypes of LED devices were characterized by strong emission with warm correlated color temperature. The investigated compounds can be used as a potential commercial phosphor for solid-state lighting application.
A series of novel phosphates with the general formulas Ca9Gd0.9−xTm0.1Smx(PO4)7 and Ca9Gd0.9−yTmySm0.1(PO4)7 were synthesized by solid-state method. As-obtained phosphates were characterized by ...powder X-ray diffraction and second harmonic generation analyses, dielectric measurements, luminescence spectroscopy. All samples were single phase and characterized by the whitlockite-type structure with space group R3c. An influence of admixture concentration of REE3+ ions in the initial host on dielectric properties was studied in details. Synthesized phosphates are characterized by intensive luminescence. The emission in the orange region of the visible spectrum is observed for Ca9Gd0.9Sm0.1(PO4)7 with a maximum intensity band at 602 nm. The line in blue region at 455 nm, which corresponds to 1D2 → 3F4 Tm3+ transition, is registered for Ca9Gd0.9Tm0.1(PO4)7. Emission in the white region of CIE coordinates was registered for Tm-Sm co-doped compounds.
UV-induced photoluminescence of organosilica films with ethylene and benzene bridging groups in their matrix and terminal methyl groups on the pore wall surface was studied to reveal optically active ...defects and understand their origin and nature. The careful selection of the film's precursors and conditions of deposition and curing and analysis of chemical and structural properties led to the conclusion that luminescence sources are not associated with the presence of oxygen-deficient centers, as in the case of pure SiO
. It is shown that the sources of luminescence are the carbon-containing components that are part of the low-k-matrix, as well as the carbon residues formed upon removal of the template and UV-induced destruction of organosilica samples. A good correlation between the energy of the photoluminescence peaks and the chemical composition is observed. This correlation is confirmed by the results obtained by the Density Functional theory. The photoluminescence intensity increases with porosity and internal surface area. The spectra become more complicated after annealing at 400 °C, although Fourier transform infrared spectroscopy does not show these changes. The appearance of additional bands is associated with the compaction of the low-k matrix and the segregation of template residues on the surface of the pore wall.
Ca8CdEu(PO4)7 polycrystalline material with a β-Ca3(PO4)2-type (β-TCP) structure was obtained using a solid state technique. The structure was refined by Rietveld method using powder synchrotron ...X-ray diffraction data. The analysis of applying approaches confirmed that the Ca8CdEu(PO4)7 structure is similar to R3¯с structures of Ca8MEu(PO4)7 (M = Mg, Zn). The photoluminescence properties were studied under UV excitation and compared with previously investigated Ca8MEu(PO4)7 (M = Mg, Zn, Ca). The substitution of Ca2+ by M2+ influences on the efficiency of energy transfer between the host and the luminescent ion. The influence of second coordination-sphere interactions on the luminescent properties of Ca8MEu(PO4)7 was revealed. Based on the difference on the PL spectra of Eu3+ in Ca8MEu(PO4)7 with R3с or R3¯с structures the site-selective method for determination of space group in β-TCP-type compounds was proposed. It is thus shown that the Eu3+ was used as an optical probe to determine the site symmetry of studied hosts.
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•Ca8CdEu(PO4)7 red phosphor with a β-TCP structure was synthesized by a solid state technique.•The structure and luminescent properties were systematically studied.•The site-selective method for determination of space group in β-TCP-type compounds was proposed.•The properties of Ca8CdEu(PO4)7 were compare with Ca8MEu(PO4)7 similar compounds.
The luminescent Z-scan technique with time resolution is applied to the study of the luminescence properties of CH3NH3PbBr3 single crystals representative of the family of hybrid organic–inorganic ...lead perovskites successfully applied recently in photovoltaics and currently investigated as potential nanosecond scintillators. The third harmonic of Ti-sapphire laser (λ = 266 nm) with a pulse duration of 26 fs and 1 kHz frequency was applied for the luminescence excitation creating the charge carriers with the estimated density from 1017 to 1021 cm−3 in the temperature range from 13 to 300 K. Temperature and excitation density dependence of the luminescence yield and kinetics is interpreted with the consideration of the temperature-dependent binding of electrons and holes into excitons, a saturation of defects responsible for the non-radiative relaxation channel competing with exciton creation; absorption saturation resulting in the increased penetration depth of the excitation radiation and hence the increased contribution of the re-absorption.
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