0000000000019543
AUTHOR
Guna Krieke
Defect formation in photochromic Ca2SnO4: Al3+
Abstract Photoluminescence, photochromism and defect formation were analysed in Ca2SnO4 doped with 0–20% Al3+. Bright cyan luminescence attributed to Sn2+ was detected in all samples. Introduction of Al3+ in Ca2SnO4 led to an enhancement of Sn2+ emission by up to 70% in comparison with an undoped sample. After exposure to UV irradiation, two absorbance bands centered at 520 nm and 710 nm and three paramagnetic defects were observed in Al3+-doped Ca2SnO4 samples. The paramagnetic centers were identified as a hole type and two different Sn3+ centers. Electron paramagnetic resonance (EPR) data suggested that one of the Sn3+ centers is located in a close proximity of Al3+. Analysis of the stabi…
Oxidation State and Local Structure of Chromium Ions in LaOCl
This research is funded by the Latvian Council of Science, project “Novel transparent nanocomposite oxyfluoride materials for optical applications”, project No. LZP-2018/1-0335. Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017- TeamingPhase2 under grant agreement No. 739508, project CAMART2.
Electron paramagnetic resonance and photoluminescence investigation of europium local structure in oxyfluoride glass ceramics containing SrF2 nanocrystals
Different compositions of europium doped aluminosilicate oxyfluoride glass ceramics prepared in air atmosphere have been studied by electron paramagnetic resonance (EPR) and optical spectroscopy methods. X-ray diffraction (XRD) and transmission electron microscopy (TEM) measurements show presence of homogenously distributed SrF2 nanocrystals after the heat treatment of the precursor glass. Efficient Eu3+ incorporation in the high symmetry environment of glass ceramics is observed from the photoluminescence spectra. EPR spectra indicate Eu3+ → Eu2+ reduction upon precipitation of crystalline phases in the glass matrix. For composition abundant with Eu2+ in the glassy state such behaviour is …
Ordering of fluorite-type phases in erbium-doped oxyfluoride glass ceramics
In this study, novel transparent Er3+ doped glass ceramics were prepared from melt-quenched oxyfluoride glasses with general composition of Na2O-NaF-BaF2-YbF3-Al2O3-SiO2. The crystallization of fluorite (BaF2, BaF2-YbF3, NaF-BaF2-YbF3 and Na0.5-xYb0.5+xF2+2x) and distorted fluorite (rhombohedral Ba4Yb3F17 and tetragonal NaF-BaF2-YbF3) phases was analysed in glass ceramics with different BaF2 and YbF3 ratio. The phase composition and microstructure were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Intense red upconversion luminescence (UCL) was detected under near-infrared excitation resulting from three photon upconversion followed by cross-relaxation betw…
Cubic and rhombohedral Ba4Lu3F17:Er3+ in transparent glass ceramics: Crystallization and upconversion luminescence
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Novel method of phosphorescent strontium aluminate coating preparation on aluminum
This work was supported by the ERDF , European-Union Project No. 1.1.1.1/16/A/182 .
Upconversion luminescence in transparent oxyfluoride glass ceramics containing hexagonal NaErF4
The authors wish to express gratitude to K. Smits for TEM measurements. This research is funded by the Latvian Council of Science, project “Novel transparent nanocomposite oxyfluoride materials for optical applications”, project No. LZP-2018/1-0335. GK wishes to expresses gratitude to Arnis Riekstins "MikroTik" donation. Donations are administered by the University of Latvia Foundation. © 2019. This work is licensed under a CC BY-NC-ND 4.0 license.
Eu3+ ion distribution in oxyfluoride glass nanocomposites
The authors are grateful to Dr. Andris Fedotovs for photography of the samples. This research is funded by the Latvian Council of Science, project “Novel transparent nanocomposite oxyfluoride materials for optical applications”, project No. LZP-2018/1-0335.
Upconversion luminescence of Er3 +/Yb3 + and their role in the stabilization of cubic NaLaF4 nanocrystals in transparent oxyfluoride glass ceramics
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Temperature and impurity concentration effects on upconversion luminescence in LaInO3 doped with Er3+
In this paper a novel method for synthesis of LaInO3:Er3+ is reported and upconversion luminescence properties of the synthesized material at different temperatures (9–300 K) are studied. The samples were prepared by co-precipitation and subsequent heat treatment of lanthanum, indium and erbium hydroxides. It is shown that the excitation at 980 nm leads to a strong green upconversion luminescence in the material. At the concentrations above 0.1 mol. % of Er3+ the energy transfer upconversion mechanism of the luminescence becomes evident. Further increase of Er3+ content in the material leads to higher red-to-green upconversion luminescence intensity ratio. The mechanisms responsible for the…
Upconversion luminescence in erbium doped transparent oxyfluoride glass ceramics containing hexagonal NaYF4 nanocrystals
Abstract In this work transparent erbium doped oxyfluoride glass ceramics containing hexagonal NaYF 4 nanocrystals has been prepared by melt-quenching and subsequent heat treatment of the precursor glass. The formation of β-NaYF 4 was confirmed by X-ray diffraction measurements. The overall intensity of the upconversion luminescence of the glass ceramics sample is 2 orders of magnitude higher than that of the precursor glass. The observed enhancement of the efficiency is explained by the incorporation of Er 3+ into low-phonon β-NaYF 4 crystalline phase.
Comprehensive study on different crystal field environments in highly efficient NaLaF4:Er3+ upconversion phosphor
Abstract Complex fluorides, especially rare-earth doped NaREF 4 (RE = Y 3+ , La 3+ or Gd 3+ ), are promising materials for the upconversion luminescence mostly due to low phonon energy of their matrices and multisite nature of the crystalline lattice. Although multisite formation in hexagonal NaREF 4 structures has generally been proved, the actual number of the active sites in different structures varies from two (NaGdF 4 ) to seven (NaYF 4 ). The aim of this work has been to study multisite formation in NaLaF 4 :Er 3+ . For this purpose low-temperature site-selective spectroscopy measurements in hexagonal NaLaF 4 :Er 3+ have been performed. Excitation at different wavelengths correspondin…
EPR and optical spectroscopy of neutron-irradiated Gd3Ga5O12 single crystals
Abstract In this paper, we have performed comparative analysis of EPR, optical absorption (OA) and luminescence spectra for a series of Gd3Ga5O12 (GGG) single crystals irradiated with fast neutrons with fluencies varied from 1016 to 1020n/cm2. In a crystal irradiated with the maximum neutron fluence, the EPR spectra demonstrated the formation of several paramagnetic defects. In particular, EPR spectrum shows a strong resonance at (effective) g ≈ 1.4 with practically isotropic behavior in the crystal rotation around the [1 1 1] direction (magnetic field being perpendicular to [1 1 1]) and several weaker lines in the g ≈ 1.1–2.6 region, which show more pronounced angular dependences. While th…
Spectroscopic studies of Cr3+ ions in natural single crystal of magnesium aluminate spinel MgAl2O4
Abstract The natural spinel crystal MgAl2O4 containing the Cr3+ ions was studied experimentally and theoretically in this paper. The absorption and emission spectra at room and low temperatures were recorded. The experimental spectroscopic results were aided with the crystal field calculations, which returned the energy level schemes of the Cr3+ ions at the Al sites with the local D3d symmetry. Effects of the trigonal crystal field were clearly seen in the calculated results, which were compared with the experimental spectra to yield a good agreement between both data sets.
Fast Luminescence Studies of NaLaF4: Pr3+ Glass Ceramics
Cathodoluminescence (CL) emission and photoluminescence (PL) emission and excitation spectra of $16\mathbf{Na}2\mathbf{O}-9\mathbf{NaF}-5\mathbf{LaF}_{3}-7\mathbf{Al}_{2}\mathbf{O}_{3}-63\mathbf{SiO}_{2}$ (mol%) activated with 3% $\mathbf{PrF}_{3}$ , hereinafter referred to as $\mathbf{NaLaF}_{4}:\mathbf{Pr}_{9}^{3+}$ have been investigated. In particular, CL spectra were measured with time resolution after excitation with a 120 keV electron beam. The characteristic Pr3+ ion emission with fast decay times $\tau_{1}=1.77$ ns and $\tau_{2}=52.97$ ns at peak intensity at 406 nm were observed, which correspond well to the emission bands of the $\mathbf{Pr}^{3+}$ ion in other luminescent materia…
How activator ion concentration affects spectroscopic properties on Ba4Y3F17: Er3+, Yb3+, a new perspective up-conversion material
Abstract Ba4Y3F17 with Er3+ and Yb3+, a promising material for up-conversion luminescence, was synthesized. Excellent isomorphic capacity was detected. Low-temperature measurements show that erbium ions are incorporated in multiple lattice positions, which is inconsistent with the current model of Ba4Y3F17 crystal lattice structure. Activator ion concentration has a different impact on 4S3/2 and 4F9/2, states (for the green and red luminescence, respectively) depopulation. Energy transfer from Er3+ 4S3/2 state to Yb3+ is observed even at low temperature (15 K) while Er-Er cross-relaxation is observed from 120 K and above. Yb3+ concentration has a great impact to red-to-green up-conversion l…
The role of structural disorder on luminescence of Eu-doped Na0.5Bi0.5TiO3
A detailed analysis of photoluminescence of Eu-doped Na0.5Bi0.5TiO3 (NBT) is performed using it as a tool for describing the local structure of NBT. The obtained results reveal the low symmetry of the Eu3+ local environment in NBT, as indicated by the observed maximal number of sublevels of the 5D0→7F1 and the 5D0→7F2 luminescence transitions, clearly observed at low temperatures. Approximation of the luminescence spectra by Gaussian peaks provides valuable information about the shift of the involved levels upon change of the excitation wavelength. Variation in the strength of the crystal field in Eu-doped NBT is evaluated. Temperature dependence of the luminescence above room temperature i…
Luminescence properties of Eu, RE3+ (RE = Dy, Sm, Tb) co-doped oxyfluoride glasses and glass–ceramics
Abstract Eu, RE3+ (RE = Dy, Sm, Tb) co-doped SiO2–CaF2–Al2O3–CaO oxyfluoride glasses have been prepared by the melt quenching method. By heating the precursor glasses at 670 °C for 1 h, glass–ceramics containing CaF2 nanocrystallites were obtained. DTA and XRD measurements were performed. Excitation spectra of the prepared samples as well as photoluminescence spectra at the excitation of 355 nm and 450 nm were measured, CIE colour coordinates and colour rendering indexes were found. In the glass–ceramics the presence of Eu2+ ions was observed by a broad emission band in the 400–500 nm spectral range. The most promising doping combinations for white light luminophores within our research are…
Phase transitions and upconversion luminescence in oxyfluoride glass ceramics containing Ba4Gd3F17 nanocrystals
This is the peer reviewed version of the following article: G. Krieke, A. Sarakovskis, R. Ignatans, J. Gabrusenoks "Phase transitions and upconversion luminescence in oxyfluoride glass ceramics containing Ba4Gd3F17 nanocrystals", Journal of the European Ceramic Society, 2017, 37 (4), which has been published in final form at https://www.sciencedirect.com/science/article/abs/pii/S0955221916306768 This article may be used for non-commercial purposes in accordance with Elsevier Terms and Conditions for Sharing and Self-Archiving.
UV and X-ray excited red persistent luminescence in Mn2+ doped MgGeO3 material synthesized in air and reducing atmosphere
Abstract Materials with long persistent luminescence (PersL) have caused widespread interest among scientists and industry for decades. Currently, there is widely available information on the long persistent luminescence materials with emission in the blue and green spectral range, while the number of publications on the afterglow in the red and near-infrared spectral range is considerably lower. In the course of this work MgGeO3 material doped with 0.1 mol% Mn2+ was produced using solid-state reaction synthesis in ambient and reducing atmospheres. The material exhibits a broad luminescence band with a peak around 680 nm, excited by either X-rays or UV. After cessation of irradiation, the a…
Low-temperature studies of Cr 3+ ions in natural and neutron-irradiated g-Al spinel
This study was supported by a grant from Latvian Council of Science (agreement No. LZP-2018/1-0214).
Enhancement of persistent luminescence in Ca2SnO4: Sm3+
Abstract Reddish-orange persistent luminescent Ca2SnO4: 0.1% Sm3+ co-doped with 0–10% Gd3+ was prepared using solid state synthesis. The phase formation and morphology was analyzed using X-ray diffraction and scanning electron microscopy. Incorporation of Sm3+ and Gd3+ in Ca2SnO4 lattice was investigated using site-selective spectroscopy and electron paramagnetic resonance. In all samples reddish-orange persistent luminescence and photochromic effect was observed after excitation with UV as well as X-rays. The thermostimulated luminescence curves indicated that the introduction of Gd3+ increases the number of shallow traps of charges which enhance the intensity of persistent luminescence. I…
Multisite formation in gadolinium doped SrF2 nanoparticles
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The role of disorder on Er3+ luminescence in Na1/2Bi1/2TiO3
Abstract Photoluminescence in Er-doped NBT is studied at different temperatures. Remarkable reduction of the luminescence intensity in the green spectral range is found in the poled state comparing with the depoled state. Luminescence spectra at low temperatures reveal continuous wavelength shift of some maxima belonging to the 4 S 3/2 → 4 I 15/2 transition depending on the excitation wavelength, which is explained by large variety of different environments around Er 3+ related to the random distribution of Na + and Bi 3+ in A-sublattice of the ABO 3 perovskite structure. Poling extends the wavelength range where shift of luminescence maxima is observed in the direction of longer excitati…
Shortwave Ultraviolet Persistent Luminescence of Sr2MgSi2O7: Pr3+
Currently, extensive research activities are devoted to developing persistent phosphors which extend beyond the visible range. In some emerging applications, long-lasting emission of high-energy photons is required; however, suitable materials for the shortwave ultraviolet (UV–C) band are extremely limited. This study reports a novel Sr2MgSi2O7 phosphor doped with Pr3+ ions, which exhibits UV–C persistent luminescence with maximum intensity at 243 nm. The solubility of Pr3+ in the matrix is analysed by X-ray diffraction (XRD) and optimal activator concentration is determined. Optical and structural properties are characterised by photoluminescence (PL), thermally stimulated lumi…
Crystallization and upconversion luminescence of distorted fluorite nanocrystals in Ba2+ containing oxyfluoride glass ceramics
Abstract In this study novel Er 3+ -doped transparent glass ceramics were prepared from melt-quenched glasses with general composition of Na 2 O-NaF-BaF 2 -YF 3 -Al 2 O 3 -SiO 2 . The phase composition of the annealed glass ceramics strongly depends on the BaF 2 content in glass matrix. Crystallization of β-NaYF 4 , cubic fluorite type, tetragonal nanocrystals and rhombohedral Ba 4 Y 3 F 17 was observed. An introduction of BaF 2 in the glass matrix suppresses the crystallization of β-NaYF 4 , promotes the formation of Ba 2+ containing fluoride phases and reduces the cross-relaxation between Er 3+ ions in fluoride crystals. Small rate of the nonradiative processes and low local symmetry of r…
Rare earth doped glass–ceramics containing NaLaF4 nanocrystals
Abstract Oxyfluoride glasses 16Na 2 O–9NaF–5LaF 3 –7Al 2 O 3 –63SiO 2 (mol%) activated with 3% terbium, dysprosium, praseodymium and neodymium fluorides have been prepared and studied by differential thermal analysis, cathodoluminescence, X-ray induced luminescence, X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy. We found out that the presence of crystalline phase enhances the X-ray induced luminescence intensity. X-ray induced luminescence is the most intense for the sample activated with terbium and treated at 700 °C, whereas the praseodymium and neodymium activated samples have the fastest decay times.
Upconversion luminescence of a transparent glass ceramics with hexagonal Na(Gd,Lu)F4 nanocrystals
Novel Er3+ doped transparent glass ceramics containing hexagonal Na(Gd,Lu)F4 nanocrystals were prepared from oxyfluoride glasses. The distribution of rare earth ions in the crystalline and glassy phase has been analyzed by X-ray diffraction and erbium luminescence decay kinetics measurement. A strong deviation of rare earth ion content in fluoride nanocrystals in comparison to the base glass has been observed. Preferential incorporation of Gd3+ over Lu3+ ions in the fluoride lattice leads to the stabilization of hexagonal Na(Gd,Lu)F4 structure and prevents the formation of cubic fluorite type solid solutions. A considerable enhancement of upconversion luminescence correlates with the format…