0000000000019545
AUTHOR
Maris Springis
Defect Luminescence of LiBaF3 Perovskites
Blue and red luminescence of undoped LiBaF3 crystals was studied. A broad, isotropic photoluminescence band centered at 410 nm can be excited by 210 nm — 275 nm light in as grown crystals. After X-irradiation at RT a new narrower, anisotropic luminescence band appears at 425 mn which has an additional excitation band at 290 nm. The X-irradiation also creates the F- type centres and anisotropic centres with an absorption band at 630 nm and a luminescence band at 700 nm. No F- centre luminescence is observed. All the other centres mentioned act as radiative recombination centers as well. It is speculated that the origin of the blue luminescence is due to oxygen defects and that the red lumine…
Up-conversion processes in NaLaF4:Er3+
abstract Structural and spectroscopic investigation of NaLaF 4 :Er 3+ material at different doping concentrations ispresented. X-ray diffraction patterns, up-conversion luminescence spectra and decay curves for 2 H 9/2 ? 4 I 15/2 , 4 S 3/2 ? 4 I 15/2 and 4 F 9/2 ? 4 I 15/2 optical transitions in the material are shown and possibleexcitation routes are discussed. Raman spectrum for the undoped material is presented and the effectivephonon energy of the material is estimated. Based on the obtained results application of rare-earth dopedNaLaF 4 in the field of up-conversion phosphors is evaluated. 2009 Elsevier B.V. All rights reserved. 1. IntroductionFor many years rare-earth (RE) doped materi…
Novel synthesis of up-conversion phosphor based on rare-earth doped NaLaF4
In this work Er3+ doped NaLaF4 material has been synthesized Along with the description of the synthesis route, luminescence spectra and decay kinetics of both traditional and up-conversion luminescence of Er3+ will be presented for different Er3+ doping levels. It will be shown that the main mechanisms involved in the creation of the up-conversion luminescence in NaLaF4:Er3+ under excitation at about 975 nm are excited state absorption and energy transfer. Relative impact of either of the mechanisms in NaLaF4:Er3+ depends on both the concentration of Er3+ and on the excitation wavelength: the increase of either the concentration or the excitation wavelength leads to the prevalence of energ…
Colour centres in LiBaF3 crystals
Abstract The origin of the absorption bands in LiBaF 3 created by X-ray irradiation at RT has been investigated. It is found that three absorption bands at 270, 320 and 430 nm represent different electron transitions within a radiation defect effectively created in LiBaF 3 single crystals. Following the Mollwo–Ivey relation we discuss investigations of optical dichroism, magnetic optical dichroism, as well as the assumptions regarding the accumulation kinetics of these absorption bands, the F centre being the main radiation defect created by X-rays in undoped LiBaF 3 crystals at RT.
The F-type centres in YAG crystals
The comparative study of optical properties of thermochemically reduced undoped YAG (Y3Al5O12) crystals is reported. A particular type of the centres often observed in YAG crystals synthesized as w...
Luminescence of Ce‐doped borate‐oxyfluoride glass ceramics
In the present work we studied the possibility to obtain oxyfluoride glass ceramics based on a lithium and potassium borate glasses with addition of fluorides. Lithium-borate glasses without lanthanum fluoride are transparent up to 275 nm. In samples with LaF3 doped with Ce-activator, an additional absorption at about 300 nm and intense photoluminescence could be observed. Ce-doped potassium-borate glass with addition of fluorides LaF3, LiF and GdF3 was milky and not transparent, an intense photoluminescence has been observed, X-ray diffraction measurements showed a presence of well-pronounced crystalline phases of LiF as well as of GdBO3. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)
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…
X‐irradiation induced photo‐ and thermostimulated luminescence of CsCdF 3 :Mn crystals
Photo- and thermostimulated luminescence (PSL and TSL respectively) of previously X-irradiated CsCdF3 crystal doped with Mn were investigated. After X-irradiation of CsCdF3 crystal at 8 K PSL bands at about 300 nm and 550 nm appear. Several stimulation bands can be revealed for luminescence at 300 nm and 550 nm. The stimulation band at 340 nm is related to an F-type centre absorption band in accordance with the Mollwo-Ivey relation for halide crystals. Subsequent heating of the crystal after X-irradiation at 8 K shows TSL peaks in the temperature regions 8 K – 90 K and 200 K – 300 K. The spectral composition of the TSL involves both bands at 300 nm and 550 nm. Experiments performed allow us…
Cubic and rhombohedral Ba4Lu3F17:Er3+ in transparent glass ceramics: Crystallization and upconversion luminescence
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Luminescence and electron transport properties of GaN and AlN layers
Abstract The transport properties of free charge carriers, photo- and cathodo-luminescence (CV) in GaN and AlN films obtained by MOCVD technique on sapphire and Si substrates, are investigated. The concentration of free charge carriers in GaN is of order 10 17 – 10 19 cm −3 whereas AlN thin films are insulating. The Hall mobility of electrons are 80– 140 cm 2 / V s ). In undoped GaN films the spectral composition of CL is close to photoluminescence (PL) when excited in the region of band–band transitions. The decay time constant of the 3.44 eV UV emission attributed to the bound exciton is considerably less than 1 ns , whereas the 3.26 eV violet (VI) band shows a slow hyperbolical decay ove…
<title>Annealing of radiation defects in x-irradiated LiBaF<formula><inf><roman>3</roman></inf></formula></title>
Results of the glow rate technique application for analysis of the activation energy of thermostimulated annealing of X-ray created F-type color centers in pure and containing oxygen centers LiBaF3 crystals are presented. It is shown that depending on the impurity composition two alternative mechanisms could be involved in the annealing of color centers. It is proposed that either the anion vacancy governed migration of F-centers resulting in recombination with complementary defects, or the thermal delocalization of radiation created fluorine (Fi) interstitials captured by anti-structure defects followed by recombination with all kinds of complementary F-type centers are responsible for the…
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.
Radiation-induced electronic and ionic charge storage and release in sapphire
Radiation-induced thermally stimulated relaxation (TSR) processes in the reduced α-Al 2 O 3 (sapphire) crystal were investigated at 290-650 K by means of the TS current (TSC), ionic depolarisation current (TSDC) and electron emission (TSEE) techniques. After thermal (ionic) polarisation of sapphire wide (∼75 K) and asymmetric ionic dipolar TSDC peak at T max 590 K (disorientation of the anion vacancy-related dipoles) was detected. This peak correlates with the wide TSEE peak at T max 615 K, the radiation-induced electrical degradation (RIED) yield rise above 550 K (T max 745 K) and the chromium emission line broadening ip ruby. Above 450-500 K the anion vacancy hopping (migration) starts. T…
Up-conversion process in erbium doped lithium fluoride bulk crystal, lithium borate glass and glass ceramics
In our research the up-conversion processes in Er doped bulk LiF crystal, lithium borate oxyfluoride glass and lithium borate oxyfluoride glass ceramics were studied: up- conversion and traditional photoluminescence spectra, the up-converted signal as a function of the laser power are presented. It was found that sharp luminescence bands in the visible part of the spectrum appear when the bulk crystal is subjected to IR irradiation at 980 nm by a laser diode. After the heat treatment of the glass submicron crystallites were detected by SEM technique. The presence of LiF crystalline phase in the oxyfluoride glass ceramics was proved by XRD method. The questions about the synthesis of the oxy…
Luminescent detectors of ionising radiation
Abstract At present in slow neutron imaging an active layer of an imaging plate IP contains a mixture of storage phosphors, usually BaFBr:Eu 2+ used for imaging of X-rays, and a neutron converter material, usually Gd 2 O 3 , LiF. A novel Li-containing luminescent material perspective for a direct neutron conversion and storage is discussed. Irradiation of LiBaF 3 crystals results in generation of Frenkel defect pairs and creation of F-type centres responsible for three absorption bands in UV-and visible spectral region. Because photo-stimulation in each of these absorption bands leads to bleaching of induced absorption, the F-type colour centres are convenient for storage of radiation dose.…
Annealing of color centers in LiBaF 3
Results of the glow rate technique to analyze the activation energy of thermostimulated annealing of X-ray created F -type color centers in LiBaF 3 crystals are presented, showing pure and containing oxygen centers. It is shown that depending on the impurity composition two alternative mechanisms are involved in the annealing of color centers. It is proposed that either the anion vacancy governed migration of F -centers resulting in recombination with complementary defects, or the thermal delocalization of radiation created fluorine ( F i ) interstitials captured by anti-structure defects followed by recombination with all kinds of complementary F -type centers are responsible for the recom…
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…
Selective excitation of up-conversion luminescence by Yb3+–Er3+ energy transfer in glass and crystalline phase of oxyfluoride glass ceramics
Up-conversion luminescence of oxyfluoride glass and glass ceramics containing LaF3 crystallites doped with Yb 3+ and Er 3+ was investigated at low temperature. Excitation of Yb 3+ in the IR region revealed the fast and the slow components of Er 3+ up-conversion luminescence originating from both glass and crystalline phases. The temporal differences of the both kinds of the luminescence allowed reconstructing the excitation spectra of the up-conversion luminescence related to the glass and crystalline phases in the glass ceramics. 2010 Elsevier B.V. All rights reserved.
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…
Radiation Defects in LiBaF3 Perovskites
We investigated the electron paramagnetic resonance (EPR), recombination afterglow, thermostimulated luminescence (TSL) and absorption of LiBaF3 perovskites crystals X-irradiated at 80 K The self-trapped hole centre VK(F2-) oriented along the [110] axis and electron F type (FA) centres are identified. X-irradiation at temperatures below 200 K results in creation of a long-term temperature-independent afterglow-tunnelling luminescence (TL), with main emission bands at 300, 370 nm and 430 nm. The short wavelength TL bands are associated with the tunnelling recombination of the F type centre with the VK centre. The thermal stability of VK centre is estimated to be about 130 K.
<title>Electronic excitations and defects in fluoroperovskite LiBaF<formula><inf><roman>3</roman></inf></formula></title>
A survey of the present situation with respect to knowledge of lattice defects, electronic excitations, such as excitons and localized excitons, as well as energy storage and transfer phenomena in LiBaF3 crystals is given. Both phenomenological models and experimental interpretations of optical absorption bands, tentatively associated with F-type (electron) centers created by X-ray or electron irradiation, is reviewed. Interpretation of three radiative processes (super-fast core-valence transitions, slow trapped exciton luminescence and luminescence of structure defects) observed in undoped LiBaF3 crystals is analyzed with respect to practical application. Attention is paid to the behavior …
Thermal relaxation of colour centres in LiBaF3crystals
Abstract Processes in LiBaF3 crystals caused by the thermal decay of F-type centres created by X-irradiation at room temperature have been examined. It is shown that the thermal decay of F-type centres results in the formation of two kinds of electron centres peaking at 630 nm and 740 nm differing in thermal stability. Weak TSL intensity, accompanying the decay of F-centres, also observed as well as the low value of the process activation energy suggest that due to the presence of moving anion vacancies a random walk of the F-centres occur. We propose that in course of the random walk of the F-centres both the aggregate F-centres are created and the annihilation with some complementary radi…
Self-trapped holes and recombination luminescence in LiBaF3 crystals
Abstract We investigated electron paramagnetic resonance (EPR) angular dependencies, recombination afterglow and thermostimulated luminescence of undoped LiBaF3 crystals, X-irradiated at low temperatures. EPR parameters of the F2− molecule oriented along the [1 1 0] direction have been obtained. Based on the value of the g-shift Δg=g⊥−gII=0.02, characteristic for the VK-centres in similar perovskites, we propose that we indeed observed the VK-centres, not the H-centres. X-irradiation below 170 K results in creation of a long-time temperature-independent afterglow due to the tunnelling recombination between close electron and hole centres. The F-type electron centres and the VK as well as pr…
<title>Localized excitons in fluoroperovskite LiBaF<formula><inf><roman>3</roman></inf></formula> crystals</title>
Two radiating processes in LiBaF3 crystals, fast valence-core transitions (5.4 - 6.5 eV) and slow, so called self-trapped exciton luminescence (about 4.3 eV), are important for practical application. Here we present a study of 4.3 eV luminescence under X-ray excitation and photoexcitation as well as under photostimulation after X-irradiation of undoped and Ag-doped LiBaF3 crystals at various temperatures. It is shown that 4.3 eV luminescence appears under X-ray excitation at least from 85 K to 400 K in both undoped and doped crystals. In all samples studied the excitation spectra of 4.3 eV luminescence contain both the main exciton like band at the edge of fundamental absorption at about 10…
<title>Formation of deep acceptor centers in AlGaN alloys</title>
AlGaN alloy thin film materials are of high interest for light emitting diodes (LED of the ultraviolet (UV) spectral region. Origin of the deep intrinsic and impurity Si states in the AlxGa1-xN (0 < x < 0.35) epilayer structures grown by metalorganic chemical vapor deposition (MOCVD) technique have been considered. Effects of the lattice mismatch and Si-doping in the heterostructures of epilayers with different alloy composition are investigated using time resolved photoluminescence (PL) of donor – deep acceptor (DA) pairs. It is shown that the undoped AlGaN alloys, grown on a GaN buffer layer, due to the lattice mismatch contain the increased concentration of cation vacancy (Vcation) defec…
Photoluminescence of neodymium and erbium doped NaLaF4 material
Abstract In the course of this research several NaLaF 4 samples doped with different Er 3+ and Nd 3+ concentrations have been synthesized. For these samples photoluminescence spectra, kinetics and excitation spectra have been measured. It has been found that when samples containing Nd 3+ and Er 3+ impurities are excited in specific Nd 3+ bands not only Nd 3+ but also Er 3+ luminescence bands appear. The studies of the decay kinetics show that there is an energy transfer from Nd 3+ to Er 3+ , moreover “green” and “red” Er 3+ luminescence bands appear as result of two different energy transfer mechanisms. In addition, photoluminescence processes in Nd 3+ ions are investigated. Based on the ob…
Annealing of Radiation Defects in X-Irradiated LiBaF3
AbstractResults of application of the glow rate technique GRT for analysis of the activation energy of thermostimulated annealing of X-ray created F-type color centers in LiBaF3 crystals, pure and containing hetero-valence oxygen centers are presented. It is shown that depending on impurity composition in crystal two alternative mechanisms are involved in annealing of color centers. It is proposed that either the anion vacancy governed migration of F- centers resulting in recombination with complementary defects, or the thermal delocalization of radiation created fluorine (Fi) interstitials captured by anti-structure defects followed by recombination with all kinds of complementary F- type …
Photo- and thermostimulated processes in α-Al2O3
Abstract We reported on the recombination processes determined by the release of electrons from defects connected with the dosimetric 430 K thermostimulated luminescence (TSL) peak as well as with the 260 K TSL peak. These TSL peaks appear in thermochemically reduced α-Al 2 O 3 crystals containing hydrogen and emission of these TSL peaks corresponds to luminescence of the F-center. The X-ray exposure or UV excitation in the absorption band of F-centers at 6.0 eV of reduced α-Al 2 O 3 crystals doped with acceptor impurities results in the appearance of a broad anisotropic complex absorption band in the spectral region 2.5–3.5 eV and in the appearance of a predominant TSL peak at 430 K. Above…
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…
Degradation features of BaF2 scintillators under radiation and magnetic fields
Degradation features of BaF2 scintillators have been examined in combined γ- and n-radiation and strong magnetic fields. Created radiation defects have been investigated by optical magnetooptical, and ODMR techniques. It is shown that the magnetic field has no selective action on defects of different structure. The magnetic field slightly diminishes the efficiency of creation of impurity color centers. The decrease of the creation rate at a magnetic field of B = 1 T does not exceed 10%. The nature of these radiation defects in BaF2 scintillators obtained by different technologies is discussed. Degradations-Eigenschaften von BaF2-Szintillatoren wurden in kombinierter γ- und Neutronen-Strahlu…
Thermally and optically stimulated radiative processes in LiBaF3 crystals
Abstract In LiBaF3 crystals both valence–core transitions (5.4– 6.5 eV ) and so-called self-trapped exciton luminescence (about 4.3 eV ) are important for practical application. Here, we present a study of 4.3 eV luminescence under photo- and thermostimulation after X-irradiation of undoped LiBaF3 crystals at various temperatures. Optically stimulated luminescence as a result of electron recombination with both self-trapped holes and holes localized at some defects, were observed after X-irradiation below 130 K and that of electron recombination with defect-localized holes was observed after X-irradiation above 130 K . The spectra of thermo-stimulated luminescence (TSL) contain a broad band…
Multicolor Up-Conversion Luminescence in Rare-Earth Doped NaLaF4
In this work we tried to achieve multicolor up-conversion luminescence in low phonon energy material NaLaF4 doped with different Er3+ Tm3+ and Yb3+ concentrations. Up-conversion luminescence was measured and main luminescence bands from Er3+ and Tm3+ in red, green and blue spectral regions were observed. The relative intensities of the luminescence bands could be changed by changing the doping levels of rare-earth ions. Changes in the up-conversion luminescence color could be achieved by applying different infrared pump power density. The color coordinates of the multicolor up-conversion luminescence depending on doping level as well as on the pump power density were presented in CIE (x, y)…
<title>Photostimulated recombination processes in x-irradiated CsCdF<formula><inf><roman>3</roman></inf></formula>:Mn crystals</title>
Fluoride crystals with the perovskite structure doped with rare-earth ions and other activators are interesting materials for laser hosts, scintillators, and detectors of ionizing radiation. Therefore, an actual task is to clarify the structure of the radiation-induced defects and recombination processes in these crystals. Compared to other fluoroperovskites, considerably less information is available concerning to the radiation-induced processes in the CsCdF3 crystals. We present a study of photostimulated luminescence (PSL) in the previously x-irradiated CsCdF3 crystal doped with Mn (0.05%). After the x-irradiation of the crystal, optical stimulation at 320 nm leads to the appearance of 3…
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…
Nature of the blue luminescence bands in PbWO4
Abstract The photoluminescence spectrum of PbWO 4 is composed of blue and green bands, previously attributed to the regular WO 4 group and to the defect-related WO 3 group, respectively. Untill now only green emission was observed in the thermostimulated luminescence (TSL) above 77 K. Investigation of the TSL spectra starting from 20 K indicates that the blue band, being definitely present at least in the 28 K TSL peak, is also due to recombination emission at defect sites.
Excited state absorption and energy-transfer mechanisms of up-conversion luminescence in Er3+-doped oxyfluoride glass ceramics at different temperatures
Abstract Oxyfluoride silicate glass SiO2–Al2O3–Na2CO3–NaF–LaF3–ErF3 was synthesized. The glass transition and crystallization temperatures were determined by differential thermal analysis. Glass ceramics containing LaF3:Er3+ crystallites of size ∼20 nm were formed in the glass matrix after the heat treatment of the precursor glass in the vicinity of the crystallization temperature. Up-conversion luminescence, excitation spectra as well as time-resolved up-conversion luminescence of the glass and glass ceramics were studied at different temperatures. The up-conversion transients showed that at room temperature the dominant mechanism of the up-conversion luminescence in the glass ceramics is …