0000000001309354
AUTHOR
Martin Nikl
On low-temperature luminescence quenching in Gd3(Ga,Al)5O12:Ce crystals
The work was supported by the ERDF funding in Estonia granted to the Center of Excellence TK141 “Advanced materials and high-technology devices for sustainable energetics, sensorics and nanoelec-tronics“ (project No. 2014-2020.4.01.15-0011). Partial support of the projects from the Ministry of Education, Youth and Sports of the Czech Republic no. LO1409, LM2015088 and CZ.02.1.01/0.0/0.0/16 013/ 0001406 is also gratefully acknowledged.
Electron Spin Resonance study of charge trapping in α-ZnMoO4 single crystal scintillator
The origin and properties of electron and hole traps simultaneously appearing in a-ZnMoO4 scintillator after X-ray irradiation at low temperatures (T < 35 K) were studied by Electron Spin Resonance (ESR). ESR spectrum of the electron type trap shows pronounced superhyperfine structure due to the interaction of electron spin with nuclear magnetic moments of 95,97Mo and 67Zn lattice nuclei. Considering the nearly tetragonal symmetry of the center this allows us to identify the electron trap as an electron self-trapped at the (Mo(1)O4) 2 complex. Nearly 60% reduction of the spin–orbit coupling at the Mo(1) ion is caused by the overlap of the Mo and ligand oxygen orbitals indicating an essentia…
Aluminum and Gallium Substitution in Yttrium and Lutetium Aluminum–Gallium Garnets: Investigation by Single-Crystal NMR and TSL Methods
The work reports the results on 71Ga and 27Al NMR investigation of the gallium and aluminum ions distribution over tetrahedral and octahedral positions in the Y3Al5−x GaxO12:Ce single crystals and Lu3Al5−xGaxO12:Ce single-crystalline epitaxial films. The gallium content x varies between 0 and 5 in crystals and between 0.3 and 2 in films.. We find that in both the Y- and Lu-based solid solutions the larger gallium ions are preferably located at the tetrahedral position while the smaller aluminum ions prefer the octahedral position of the garnet host. Based on NMR data, the dependence of fractional occupation parameters of the tetrahedral site of Ga and Al ions on the Ga content is determined…
Eu2+ Stabilization in YAG Structure: Optical and Electron Paramagnetic Resonance Study
A set of Eu-doped Y3Al5O12 (YAG) phosphors in the powder form was successfully synthesized by multiple-step solid-state reaction under the reducing Ar:5%H2 atmosphere. Their physical properties were investigated by means of X-ray diffraction, time-resolved luminescence spectroscopy, and electron paramagnetic resonance (EPR). Special attention was given to well-grounded confirmation of Eu2+ occurrence in the YAG structure. X-ray diffraction confirmed the presence of a major YAG phase in all samples. The influence of Eu concentration, form of doping (EuS, EuF2, or Eu2O3) and number/form of annealing steps was studied. Corresponding characteristics were measured and evaluated in a broad temper…
EPR study of Ce3+ luminescent centers in the Y2SiO5 single crystalline films
Abstract The work reports results of EPR investigation of the Ce3+ incorporation in the Y2SiO5 and (Y,La)2SiO5 single crystalline films (SCFs), grown by liquid phase epitaxy method. The Ce3+ content determined from EPR spectra varied between 0.49 and 0.65 at. % in Y2SiO5 SCFs and strongly increased up to 1.9 at. % in (Y,La)2SiO5 SCF, suggesting a positive role of the La dopant in the incorporation of the Ce3+ ions into Y2SiO5 host. The EPR study showed the presence of only one type of Ce3+ centers (Ce1) corresponding to the localization of Ce3+ ions in the seven–fold coordinated positions of the Y2SiO5 host. No Ce2 center spectra (six-fold coordinated Ce3+ positions) were detected in films …
Optical, Structural and Paramagnetic Properties of Eu-Doped Ternary Sulfides ALnS2 (A = Na, K, Rb; Ln = La, Gd, Lu, Y)
Eu-doped ternary sulfides of general formula ALnS2 (A = Na, K, Rb; Ln = La, Gd, Lu, Y) are presented as a novel interesting material family which may find usage as X-ray phosphors or solid state white light emitting diode (LED) lighting. Samples were synthesized in the form of transparent crystalline hexagonal platelets by chemical reaction under the flow of hydrogen sulfide. Their physical properties were investigated by means of X-ray diffraction, time-resolved photoluminescence spectroscopy, electron paramagnetic resonance, and X-ray excited fluorescence. Corresponding characteristics, including absorption, radioluminescence, photoluminescence excitation and emission spectra, and decay k…
The study of time-resolved absorption and luminescence in PbWO4 crystals
Abstract The transient absorption and luminescence under pulsed electron beam excitation were studied for undoped and La3+ doped PbWO4 crystals. The absorption band at ∼1.0 eV is suggested to be due to self-trapped electrons and the absorption band at 3.5 eV may be due to self-trapped holes. The formation of luminescence centers via electron–hole recombination is affected by La3+ in doped crystals. The large fraction of electrons and holes undergoes thermostimulated recombination within geminate pairs and the spatial separation of geminate pairs components is important in recombination process. The intrinsic (blue) luminescence arises in this recombination. The mechanism of La3+ influence o…
Thermochromic Fluorescence from B18H20(NC5H5)2: An Inorganic–Organic Composite Luminescent Compound with an Unusual Molecular Geometry
BH(NCH) is a rare example of two conjoined boron hydride subclusters of nido and arachno geometrical character. At room temperature, solutions of BH(NCH) emit a 690 nm fluorescence. In the solid state, this emission is shifted to 620 nm and intensifies due to restriction of the rotation of the pyridine ligands. In addition, there is a thermochromicity to the fluorescence of BH(NCH). Cooling to 8 K engenders a further shift in the emission wavelength to 585 nm and a twofold increase in intensity. Immobilization in a polystyrene thin-film matrix results in an efficient absorption of pumping excitation energy at 414 nm and a 609 nm photostable fluorescence. Such fluorescence from polystyrene t…
Effect of Ga content on luminescence and defects formation processes in Gd3(Ga,Al)5O12:Ce single crystals
The work was supported by the Institutional Research Funding IUT02-26 of the Estonian Ministry of Education and Research and the project 16-15569S of the Czech Science Foundation.
Gallium preference for the occupation of tetrahedral sites in Lu3(Al5-xGax)O12multicomponent garnet scintillators according to solid-state nuclear magnetic resonance and density functional theory calculations
Abstract In this study, the distributions of aluminum and gallium atoms over the tetrahedral and octahedral sites in the garnet structure were investigated in mixed Lu3Al5-xGaxO12 crystals by using 27Al and 71Ga magic angle spinning nuclear magnetic resonance (NMR) and single crystal 71Ga NMR. The experimental study was supported by theoretical calculations based on density functional theory (DFT) in order to predict the trends in terms of the substitutions of Al by Ga in the mixed garnets. Both the experimental and theoretical results indicated the non-uniform distribution of Al and Ga over the tetrahedral and octahedral sites in the garnet structure, with a strong preference for Ga occupy…
Luminescence and scintillation properties of Mg-codoped LuAG:Pr single crystals annealed in air
Abstract The influence of the Mg 2+ codoping and annealing in the air on the scintillation and luminescence characteristics of Pr-doped lutetium-aluminum garnet crystals (LuAG) was studied to find a possible positive effect of Pr 4+ . The overall scintillation efficiency under X-ray excitation of the annealed Pr- doped samples decreased with increasing Mg concentration. This was explained by increased overlap of the Pr 3+ 5d-4f emission with the charge-transfer (CT) absorption band of the Pr 4+ ion stabilized by Mg 2+ . This absorption caused even greater decrease of the light yield, as the light is collected from the whole sample volume in the pulse-height spectrum measurement. Electron ce…
Electron paramagnetic resonance study of theCe3+pair centers inYAlO3:Ce scintillator crystals
Single crystals of $\mathrm{YAl}{\mathrm{O}}_{3}$ doped with Ce have been studied by electron paramagnetic resonance (EPR) at the 9.4 and 34 GHz microwave bands. Besides the single-ion $\mathrm{C}{\mathrm{e}}^{3+}$ spectrum, measurements have revealed many satellite lines which belong to the $\mathrm{C}{\mathrm{e}}^{3+}\text{\ensuremath{-}}\mathrm{C}{\mathrm{e}}^{3+}$ pair centers. Their spectra have been fitted by a general effective spin Hamiltonian describing two interacting particles with the spin $S=1/2$. Corresponding $g$ factors and spin-spin coupling constants have been determined. The spin-spin coupling constants are in the range from 0.1 up to $0.65\phantom{\rule{0.16em}{0ex}}\mat…
EPR hyperfine structure of F‐type centres in pure LiBaF 3 crystal
We studied EPR spectra of pure LiBaF3 sample of high quality. For EPR measurements LiBaF3 sample was X-irradiated at room temperature, however spectra could be observed at low temperatures - at 77 K. All hyperfine structure lines of F-type centre could be well resolved contrary to our earlier studies of Fe doped LiBaF3 crystal. Qualitative analysis with g-tensor parameters derived from magneto-optical measurements showed that the F-type centre observed earlier by MCD-EPR techniques is the same F-type centre we observe with the EPR. We analyse origin of the hyperfine structure of the EPR spectra and their angular dependencies and discuss the structure of F-type centres in the LiBaF3 crystal.…
Electron paramagnetic resonance study of exchange coupled Ce3+ ions in Lu2SiO5 single crystal scintillator
Abstract The Ce 3+ ions incorporation inside lutetium oxyorthosilicate (Lu 2 SiO 5 ) single crystals was studied by electron paramagnetic resonance. Already known Ce1 and Ce2 centers originating from the lattice peculiarity allowing two lutetium sites coordinated by different number of the oxygen ions were detected. Remarkably, for the Ce2 center, the determined g 2 tensor is asymmetric and could not be diagonalized as compared to the Ce1 center, for which the three principal values and corresponding axes orientation have been determined and reported previously. Besides, the much weaker resonance lines found in spectra close to those coming from the Ce1 and Ce2, and following them under cry…
Tunable Eu2+ emission in KxNa1 − xLuS2 phosphors for white LED application
Set of Eu2+-doped KxNa1 − xLuS2 phosphors (x = 0–1) in the form of transparent crystalline hexagonal platelets was successfully synthesized by chemical reaction under the flow of hydrogen sulfide. Their physical properties were investigated by means of X-ray diffraction, X-ray fluorescence, time-resolved luminescence spectroscopy and electron paramagnetic resonance. Special attention was given to photoluminescence emission spectra under the 395 nm and 455 nm excitation aiming to obtain white emission with tunable color temperature. EPR method was employed to understand the Eu2+ incorporation and distribution in the KxNa1 − xLuS2 hosts. CIE xy-coordinates were calculated to compare effects o…
Charge trapping processes and energy transfer studied in lead molybdate by EPR and TSL
Abstract Charge trapping and energy transfer processes are investigated in PbMoO4 single crystals by electron paramagnetic resonance (EPR) and wavelength-resolved thermally stimulated luminescence (TSL) in a correlated manner. New signals produced by two differently perturbed Mo5+ centers (Mo2 and Mo3) were observed in EPR spectra measured in the crystals after 420 nm light irradiation. Two sets of spin-Hamiltonian parameters, g tensor and the 95,97Mo, 207Pb (super) hyperfine tensors, have been determined and analyzed in terms of crystal field and LCAO-MO theories. A significant overlap of the Mo 5d1 and 6s6p ligand Pb orbitals was deduced for the Mo3 whereas the Mo2 center seemed to be not…
Magnetooptical studies of defects and recombination luminescence in LiBaF3
Abstract Optically detected EPR investigations have been performed on the recombination luminescence (RL-EPR) of LiBaF3 crystal, X-irradiated at T=4.2 K . RL-EPR lines of VK- centres were found, as well as further lines of a defect with S= 1 2 and an axial g-tensor with its main axis along a [1 0 0] direction of the crystal. Measurements of the magnetic circular dichroism of the absorption (MCDA) have been performed on LiBaF3 crystals X-irradiated at two temperatures ( 4.2 K and RT). After irradiation at T=4.2 K , the main MCDA bands peak at 453 and 500 nm , but after irradiation at T=300 K , the main bands peak at 444 and 390 nm , there is a change of the sign between the peaks in both cas…
LPE growth and study of the Ce3+ incorporation in LuAlO3:Ce single crystalline film scintillators
This work reports the results of the optical and electron paramagnetic resonance (EPR) investigation of the Ce3+ incorporation in single crystalline film (SCF) scintillators of Ce-doped LuAlO3 perovskite, grown by the liquid phase epitaxy method onto YAlO3 substrates using a PbO–B2O3 flux. The absorption, luminescence and EPR spectra showed the presence of the main Ce3+ center type (CeLu) corresponding to the location of Ce3+ ions in the twelve-fold coordinated cuboctahedral positions of the LuAlO3 host. Also the dimer CeLu–CeLu centers were found in the EPR spectra of the LuAP:Ce SCFs. No EPR spectrum of the Ce3+ ions located in the octahedral positions of Al3+ cations has been detected in…
Effect of Mg 2+ ions co-doping on luminescence and defects formation processes in Gd 3 (Ga,Al) 5 O 12 :Ce single crystals
The work was supported by the Institutional Research Funding IUT02-26 of the Estonian Ministry of Education and Research and the project 16-15569S of the Czech Science Foundation.
Thermostimulated recombination processes in LiBaF3 crystals
Abstract The creation of radiation defects in LiBaF 3 crystals at 10 K and the processes of their thermostimulated recombination are investigated. The methods of optical absorption, thermal bleaching of color centers, thermostimulated luminescence and fractional glow technique are used. The radiation defects anneal in a multi-stage process accompanied with thermo-luminescence at 20, 46, 105, 130, 170, 210 and 270 K . Differences in the optical absorption spectra measured before and after the TSL peaks are obtained and recombination parameters are determined. The TSL peak at 20 K arises from the delocalization of H-centers. The presence of two TSL peaks related to V K -centers at 105 and 130…
CCDC 1514165: Experimental Crystal Structure Determination
Related Article: Michael G. S. Londesborough, Jiří Dolanský, Luis Cerdán, Kamil Lang, Tomáš Jelínek, Josep M. Oliva, Drahomír Hnyk, Daniel Roca-Sanjuán, Antonio Francés-Monerris, Jiří Martinčík, Martin Nikl, John D. Kennedy|2017|Adv. Opt. Mater.|5|1600694|doi:10.1002/adom.201600694