Spin-selective electron tunneling from excited FA centers to F+ centers in CaO

From pulsed phosphorescence microwave double resonance experiments it is established that electron tunneling between F_A and F⁺ centers in CaO occurs from F_A centers in the excited ³A₁ state. Only the radiative sub-levels within this ³A₁ state act as precursor states in the electron transfer process. The tunneling rate at 1.2 K is determined to be 1.5±0.2s^-1.     

Investigation of defect centres responsible for TL/OSL in MgAl2O4:Tb

Magnesium aluminate doped with Tb³⁺ (MgAl₂O₄:Tb³⁺) was prepared by combustion synthesis. Three thermoluminsence (TL) peaks at 120, 220 and 340 °C were observed. PL and TL emission spectrum shows that Tb³⁺ acts as the luminescent centre. Optically stimulated luminescence (OSL) was observed when stimulated by 470 nm blue light.Electron spin resonance (ESR) studies were carried out to identify the defect centres responsible for the TL and OSL processes in MgAl₂O₄:Tb³⁺. Two defect centres were identified in irradiated MgAl₂O₄:Tb³⁺ phosphor by ESR measurements which was carried out at room temperature and these were assigned to V and F⁺ centres. V centre (hole centre) is correlated to 120 and 220 °C TL peaks and F⁺ centre (electron centre), which acts as a recombination centre is correlated to 120, 220 and 340 °C.     

Red-shift in the photostimulation of the X-ray storage phosphor RbBr:Ga+

Abstract

By means of magnetic circular dichroism of the optical absorption and photostimulated luminescence (PSL) the X-ray induced formation of F_A and F centres in RbBr:(Ga⁺, Li⁺) was investigated. It turnes out that RbBr:Ga⁺ co-doped with 1% Li⁺ in the melt reveals the largest red-shift of the PSL excitation bands to 790 nm, whereby the F_A to F ratio increases up to about 10% with decreasing X-ray dose. This is more than statistically expected (6%). High X-ray doses destroy F_A centres. However, up to 15% of the simultaneously generated F centres could be converted into the F_A species by appropriate bleaching with 633 nm light into the F centre absorption band.     

Photoluminescence of F2+2 centres in additively coloured magnesium oxide

The principle luminescence bands excited in additively coloured MgO by radiation in the wavelength range 170–400 nm are observed at wavelengths of 520, 475, 441 and 375 nm. Polarised luminescence and uniaxial stress measurements on the 441 nm band, the radiative lifetime of 25 msec at 1.6 K and temperature dependence of luminescence intensities of the 375, 441 and 375 nm bands are consistent with the 441 nm band being due to ³B_1u → ¹A_g transitions of the F²⁺₂ centre.     

Synthesis,characterisation, luminescence and defect centres in solution combustion synthesised CaZrO3:Tb3+ phosphor

Tb³⁺ doped CaZrO₃ has been prepared by an easy solution combustion synthesis method. The combustion derived powder was investigated by X-ray diffraction, Fourier-transform infrared spectrometry and scanning electron microscopy techniques. A room temperature photoluminescence study showed that the phosphors can be efficiently excited by 251 nm light with a weak emission in the blue and orange region and a strong emission in green light region. CaZrO₃:Tb³⁺ exhibits three thermoluminescence (TL) glow peaks at 126 °C, 200 °C and 480 °C. Electron Spin Resonance (ESR) studies were carried out to study the defect centres induced in the phosphor by gamma irradiation and also to identify the centres responsible for the TL peaks. The room temperature ESR spectrum of irradiated phosphor appears to be a superposition of two distinct centres. One of the centres (centre I) with principal g-value 2.0233 is identified as an O^? ion. Centre II with an axial symmetric g-tensor with principal values g_=1.9986 and g_?=2.0023 is assigned to an F⁺ centre (singly ionised oxygen vacancy). An additional defect centre is observed during thermal annealing experiments and this centre (assigned to F⁺ centre) seems to originate from an F centre (oxygen vacancy with two electrons). The F centre and also the F⁺ centre appear to correlate with the observed high temperature TL peak in CaZrO₃:Tb³⁺ phosphor.     

TSL, OSL and ESR studies in ZnAl2O4:Tb phosphor

ZnAl₂O₄:Tb phosphor was prepared by combustion synthesis. ZnAl₂O₄:Tb exhibits three thermally stimulated luminescence (TSL) peaks around 150, 275 and 350 °C. ZnAl₂O₄:Tb exhibits optically stimulated luminescence (OSL) when stimulated with 470 nm light.Electron spin resonance (ESR) studies were carried out to identify defect centres responsible for TSL peaks observed in ZnAl₂O₄:Tb. Two defect centres are identified in irradiated ZnAl₂O₄:Tb phosphor and these centres are assigned to V and F⁺ centres. V centre appears to correlate with the 150 °C TSL peak, while F⁺ centre could not be associated with the observed TSL peaks.     

Excitation mechanism of Bi3+ luminescence centres in CaS

A systematic approach to investigate the excitation mechanism of Bi³⁺ luminescence centres in CaS has been made from simultaneous measurements of photoluminescence (PL) and photoconductivity (PC), thermoluminescence (TL) and thermally stimulated conductivity (TSC). Changes in PL and PC have been studied in the temperature range 295–505 K. An attempt has been made to explain the correlation between these phenomena with a simple trapped-carrier-free-carrier recombination model. It is found that the charge transfer process dominates in all these phenomena. Conductivity is primarily due to electron traffic through the conduction band, whereas their subsequent recombination through the excited state (³P₁) accounts for the characteristic emission of Bi³⁺.     

Optical properties of (ZnO)0.5(P2O5)0.5 glasses doped with Gd2O3:Eu nanoparticles and Eu2O3

Binary (ZnO)_0.5(P₂O₅)_0.5 glasses doped with Eu₂O₃ and nanoparticles of Gd₂O₃:Eu were prepared by conventional melt-quench method and their luminescence properties were compared. Undoped (ZnO)_0.5(P₂O₅)_0.5 glass is characterized by a luminescent defect centre (similar to L-centre present in Na₂O-SiO₂ glasses) with emission around 324 nm and having an excited state lifetime of 18 ns. Such defect centres can transfer the energy to Eu³⁺ ions leading to improved Eu³⁺ luminescence from such glasses. Based on the decay curves corresponding to the ⁵D₀ level of Eu³⁺ ions in both Gd₂O₃:Eu nanoparticles incorporated as well as Eu₂O₃ incorporated glasses, a significant clustering of Eu³⁺ ions taking place with the latter sample is confirmed. From the lifetime studies of the excited state of L-centre emission from (ZnO)_0.5(P₂O₅)_0.5 glass doped with Gd₂O₃:Eu nanoparticles, it is established that there exists weak energy transfer from L-centres to Eu³⁺ ions. Poor energy transfer from the defect centres to Eu³⁺ ions in Gd₂O₃:Eu nanoparticles doped (ZnO)_0.5(P₂O₅)_0.5 glass has been attributed to effective shielding of Eu³⁺ ions from the luminescence centre by Gd-O-P type of linkages, leading to an increased distance between luminescent centre and Eu³⁺ ions.     

Recombination luminescence of CaSO4:Tb3+ and CaSO4:Gd3+phosphors

A comparative study of the excitation of luminescence by VUV radiation as well as of thermally and photostimulated luminescence has been carried out for CaSO₄:Tb³⁺ and CaSO₄:Gd³⁺ phosphors, where Na⁺ or F⁻ ions are used for charge compensation. The distinction in hole processes for the phosphors with Na⁺ or F⁻ compensators is determined by the differing thermal stability of the holes localized at/near Tb³⁺Na⁺ and Gd³⁺Na⁺ (up to 100–160 K) or at/near Tb³⁺F⁻ V _Ca and Gd³⁺F⁻ V _Ca centers involving also a cation vacancy (up to 400–550 K). Tunnel luminescence in the pairs of localized electrons and holes nearby Tb³⁺ or Gd³⁺ has been detected. The mechanisms of electron-hole, hole-electron and tunnel recombination luminescence as well as a subsequent released energy transfer to RE³⁺ ions are considered.     

Electronic structure of thallous centres and Tl+ - Vk recombination in KCl crystal

Parameters of impurity Tl ion required for the calculation of different thallous centres in alkali halides are obtained for the semiempirical method of the intermediate neglect of differential overlap (INDO). The electronic structure of Tl⁺, Tl²⁺ centres in KCl is calculated. The potential energy curves for the recombination of nearest Tl⁺, V_$\text{k}$ centres against the breathing vibrational mode of the V_$\text{k}$ centre are calculated. This recombination (hole trapping) is found to be nonradiative tunneling with small activation energy rather than radiative one. A number of experimental data is also discussed in the light of the present calculations.     

EPR spectra of colour centres in x-irradiated BaCl2:K+ and BaCl2:Ag+

X-irradiation at 80°K leads to the formation of V_K centres and, in addition, perturbed F centres in the case of BaCl₂:K⁺. The V_K centres spectra exhibit a superhyperfine structure. A warming to 130°K of crystals X-irradiated at 80°K causes the V_K centres to be perturbed, and besides leads to the formation of (AgCl₄)^2? complexes in BaCl₂:Ag⁺.     

A rapid combustion process for the preparation of MgSrAl10O17:Eu phosphor and related luminescence and defect investigations

Blue-emitting europium-ion-doped MgSrAl₁₀O₁₇ phosphor, prepared using the combustion method, is described. An efficient phosphor can be prepared by this method in a muffle furnace maintained at 500 °C in a very short time of few minutes. The phosphor is characterized by powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy and BET surface area measurements. Photoluminescence (PL) spectra revealed that europium ions were present in divalent oxidation state. The thermoluminescence (TL) glow curve shows two peaks at around 178 and at 354 °C. The defect centres formed in the phosphor are studied using electron spin resonance (ESR). The ESR spectrum indicates the presence of Fe³⁺ ions in the non-irradiated system. Irradiated MgSrAl₁₀O₁₇:Eu exhibits lines due to radiation-sensitive Fe³⁺ ion and a defect centre. The centre is characterized by an isotropic g-value of 2.0012 and is assigned to a F⁺ centre. The radiation-sensitive Fe³⁺ ion appears to correlate with the main TL peak at 178 °C. During irradiation an electron is released from Fe²⁺ and is trapped at an anion vacancy to form F⁺ centre. During heating, an electron is liberated from the defect centre and recombines with Fe³⁺ emitting light.     

Synthesis, characterization, optical absorption, luminescence and defect centres in Er3+ and Yb3+ co-doped MgAl2O4 phosphors

The Er³⁺–Yb³⁺ co-doped MgAl₂O₄ phosphor powders have been prepared by the combustion method. The phosphor powders are well characterized by X-ray diffraction (XRD) and energy dispersive (EDX) techniques. The absorption spectrum of Er³⁺/Er³⁺–Yb³⁺ doped/co-doped phosphor powder has been recorded in the UV–Vis–NIR region of the electro-magnetic spectrum. The evidence for indirect pumping under 980 nm excitation of Er³⁺ from Yb³⁺ was observed in the MgAl₂O₄ matrix material. Electron spin resonance (ESR) studies were carried out to identify the defect centres responsible for the thermally stimulated luminescence (TSL) process in MgAl₂O₄:Er³⁺ phosphor. Three defect centres were identified in irradiated phosphor by ESR measurements which were carried out at room temperature and these were assigned to an O^? ion and F⁺ centres. O^? ion (hole centre) appears to correlate with the low temperature TSL peak at 210 °C and one of the F⁺ centres (electron centre) is related to the high temperature peak at 460 °C.     

Cr+ centres in mixed polytype ZnS single crystal

The glow peaks of mixed polytype ZnS: Cu, Cr, Cl crystals were identified as produced by three Cr⁺ centres observed by electron paramagnetic resonance (EPR): one cubic (C) and two axial (H₁ and H₂). The characteristics of these centres were partly found by the methods of interrupted thermoluminescence, infrared stimulation, “thermo-EPR” (variation of the EPR signal with heating of a previously excited crystal) and also by decay of glow areas and of the three Cr⁺EPR signals after excitation at different temperatures. Moreover, these measurements showed the important part played by the non-thermal emptying of the Cr⁺ traps. This emptying occurs through photoexcitation of the trapped electrons by the reabsorbed luminescence light or through recombination of these electrons with free holes. Both of these processes diminish the efficiency of phosphorescence when the crystal is cooled; so it was necessary to take them into account when analysing the experimental results. The percentage of H₁ and H₂ found by EPR and luminescence is in agreement with the percentage of the hexagonalicity as found from the birefringence measurements. The crystal field calculation gives account of three centres in such a mixed polytype crystal.     

(F2+)A centers in lithium-doped KCl

Optical properties of the lithium (F₂⁺)_A center are reported and compared to those of the sodium (F₂⁺)_A and the intrinsic F₂⁺ centers.     

LiF:F+2-centre laser for intracavity spectroscopy

We describe a broad-band uncooled LiF:F⁺₂ colour centre laser (880–970 nm), pumped by a pulsed Xe-ion laser, for intracavity spectroscopy. Spectra of molecular absorption and gain, and of time-resolved absorption by atomic metastables demonstrate the versatility of the system.     

Photoionization processes in F aggregate centres of LiF crystal

Extensive studies have been carried out on the optical conversion of F and F-aggregate colour centres produced in lithium fluoride single crystal on gamma irradiation. Using 308 nm XeCl laser it has been shown that significantly large population build-up of F ₃ ⁺ centre and reduction in the population of undesirable F₂ centres can be achieved in gamma irradiated crystal at room temperature due to multistep photoionization processes. These and other investigations have provided a scheme for possible laser action based on F ₃ ⁺ colour centres in LiF crystal at room temperature.     

Luminescence studies on ZnO-P2O5 glasses doped with Gd2O3:Eu nanoparticles and Eu2O3

Zinc phosphate glasses doped with Gd₂O₃:Eu nanoparticles and Eu₂O₃ were prepared by conventional melt-quench method and characterized for their luminescence properties. Binary ZnO-P₂O₅ glass is characterized by an intrinsic defect centre emission around 324 nm. Strong energy transfer from these defect centres to Eu³⁺ ions has been observed when Eu₂O₃ is incorporated in ZnO-P₂O₅ glasses. Lack of energy transfer from these defect centres to Eu³⁺ in Gd₂O₃:Eu nanoparticles doped ZnO-P₂O₅ glass has been attributed to effective shielding of Eu³⁺ ions from the luminescence centre by Gd-O-P type of linkages, leading to an increased distance between the luminescent centre and Eu³⁺ ions. Both doped and undoped glasses have the same glass transition temperature, suggesting that the phosphate network is not significantly affected by the Gd₂O₃:Eu nanoparticles or Eu₂O₃ incorporation.     

Blue long-lasting phosphorescence of Ti-doped BaZrO3 perovskites

Long-lasting phosphorescence was observed from Ti-doped BaZrO₃ perovskite synthesized by a solid-state reaction. The phosphorescence color is blue and the phosphorescence can still be seen with the naked eye in the dark for 30 min or more after stopping UV irradiation. By the measurements of electron spin resonance (ESR) spectra, it was confirmed that F⁺ center and Zr³⁺ exist in non-luminescent undoped BaZrO₃ and their concentrations decreased with the additive amount of TiO₂. It is expected that the luminescence center is F_A center composed of Ti³⁺ and F⁺ center.     

Self-consistent analysis of absorption and emission data forF A centres in alkali halides

Summary A theory which explains self-consistently the emission and the polarization rotation of transmitted light has been developed forF _A centres in crystals with cubic symmetry. Azimuthal dependences ofF _A luminescence in alkali halides are very informative for determining the electron-phonon interaction as well as the parameters related to the structural and optical quality for coulour centre lasers crystals. The theoretical results are applied to the interpretation of the luminescence properties ofF _A (Li) centres in KCl, RbCl and KF.