Photostimulated luminescence properties of BaFBr:Eu under ion irradiation

The photostimulated luminescence (PSL) properties of the phosphor BaFBr:Eu after ion beam irradiation was analyzed; in particular, the PSL intensity dependent on ion fluence. The PSL intensity increased linearly with the ion fluence up to 10¹² ions/cm², and subsequently decreased gradually. The ion fluence dependence was observed to be similar among samples containing different F centers or different Eu concentrations. The fluence dependence was quantitatively analyzed based on a trapping model, in which competition between the trapping processes to storage centers and radiation defects is assumed; the model explained the experimental data quantitatively. The results indicate that radiation defects influence the PSL properties via the trapping of photostimulated electrons.     

Al3+掺杂BaFBr:Eu2+中F(Br-)心的性质

作为光激励发光的首选材料BaFBr:Eu^2 ，在其中掺杂一定量的Al^3 后，其光激励发光谱向长波方向发生了较大的红移现象，红移的机理是掺杂的Al^3 离子取代了BaFBr:Eu^2）晶格中的Ba^2 离子，且处于F（Br^-）心的次近邻位所致。本文利用喇曼光谱和电子顺磁共振谱对受掺杂Al^3 微扰的F（Br^-)心的结构进行了研究，首次在喇曼光谱的高频移区观测到了由于掺参Al^3 所引起的新结构的产生，通过电子顺磁共振谱表征了在BaFBr:Eu^2＋中Al^3 与F（Br^-）心的相对位置，并且得出F（Br^-)心与OF^-心存在着空间相关性。     

BaFBr，BaFBr：Eu~（2＋）和BaFBr：Ce~（3＋）晶体在X射线辐照和光激励过程中发光和光电导的实时原位测量

在自建的多功能实时原位测量发光特性和光电导的实验装置上，测量了ＢａＦＢｒ，ＢａＦＢｒ：Ｅｕ２＋和ＢａＦＢｒ：Ｃｅ３＋单晶在Ｘ射线辐照和光激励过程中的发光强度和光电导。首次从光电导的角度测量到Ｘ射线辐照时，Ｅｕ２＋并没有被离化，而Ｃｅ３＋被离化，离化电子经导带被Ｆ＋心俘获；明确证实了光激励过程中Ｆ心电子的隧穿效应。     

The Measurements of Photostimulated Luminescence in Alkali Doped BaFBr:Eu2☎ at Liquid Nitrogen Temperature

Considerable increase of the photostimulated luminescence (PSL) intensity and red shift of the excitation spectrum was obtained by alkali doping of BaFBr:Eu^2? crystals [1]. The band of the F_A(Br^?) centers about 0.1 eV shifted to low energy side against the “normal” F(Br^?) centers. The F_A(Br^?) centers are destroyed after heating to 330 K.     

Photostimulated luminescence in BaX 2 :Eu 2+ (X=Br,Cl) X-ray storage phosphors

The photostimulated luminescence (PSL) effect in BaX 2 :Eu 2+ (X=Br, Cl) is comparable to that observed in BaFBr:Eu 2+ which is used in commercial X-ray storage phosphor screens. After X-irradiation the PSL stimulation spectra of BaX 2 :Eu 2+ (X=Br, Cl) single crystals are identical to the F centre absorption spectra, i.e. the F centres are the PSL-active electron trap centres. The nature of the hole centres is still unknown. The PSL response time of about 0.70 v s is within experimental error of 0.02 v s identical to the Eu 2+ radiative lifetime, whereas in BaCl 2 :Eu 2+ the PSL response time is 0.60 v s, and thus longer than the Eu 2+ radiative lifetime of 0.47 v s.     

Mechanism of long-lasting phosphorescence of Eu 2+ in melilite

UV excitation for several Eu 2+ -doped melilite crystals, Eu 2+ :Ca 2 Al 2 SiO 7 (CASM), Eu 2+ :CaSrAl 2 SiO 7 (CSASM), and Eu 2+ :Sr 2 Al 2 SiO 7 (SASM) produces long-lasting phosphorescence (1-10 2 v s) from Eu 2+ ions besides the intrinsic Eu 2+ luminescence. The distribution of the radiative decay rates is due to the recombination of distant pairs of trapped electrons and holes in the crystals. The intensities of the phosphorescence for these crystals were measured as functions of temperature and time. The most intense phosphorescence was obtained from the Eu 2+ : SASM crystal. The decay curves measured for Eu 2+ :SASM below 400 v K fit t m n ( n h 1). This fact shows that the recombination of the distant pairs occurs through tunneling below 400 v K. The temperature dependence of the intensities integrated in a time domain obeys the Arrhenius's equation with two thermal activation energies including radiative and non-radiative processes. These results suggest that holes and electrons recombine radiatively at Eu 2+ sites in the SASM crystal through thermal hopping and tunneling. On the other hand, Eu 2+ :CASM and Eu 2+ :CSASM show different behavior on the decay curves at low temperatures, satisfying t m n ( n >1). This discrepancy may be removed by several electron and/or hole centers with different trapping energy levels.     

Charge-Transfer Processes in Doped Alkali Halides

Defects formation under UV-irradiation in the impurity-induced absorption bands at 4.2 K has been studied for crystals with and without traps for electrons (CsI:Pb and Eu^2?-doped alkali halides, respectively). In both cases the results have been explained by an electron transfer from the impurity-perturbed halogen ion states, resulting in the appearance of electrons and holes in the crystal. In CsI:Pb, the electrons are trapped by lead ions and the holes are self-trapped. In Eu^2?-doped crystals, the electrons and the holes recombine with the formation of excitons, whose decay results in the creation of Frenkel defects.     

Electric field effect on the mechanisms of recombination in KI doped with divalent ions

In KI crystals doped with divalent ions (Eu²⁺, Sr²⁺, Mn²⁺) a strong influence of the electric field is observed, after irradiation, on the carriers (electrons and holes) recombination kinetics. The phenomena are similar whether the electrons, distributed on traps bound to divalent ions, are excited by IR at 4 K, and recombine with trapped holes (V_k centers) or whether the holes are made thermally mobile at T>77 K. It is suggested that this is due to the recombination mechanism: the kinetics are simultaneously controlled by diffusion and tunneling. The tunneling range is a function of the applied field.     

Photoluminescence and photostimulated luminescence in the X-ray storage phosphor BaBr2 doped with cerium

In orthorhombic BaBr₂ : Ce³⁺ two kinds of luminescence bands at room temperature have been attributed to charge-compensated Ce³⁺ centres. One type was associated with potassium (or some other monovalent cation) on a neighbouring Ba site and another one associated with an unidentified defect. A third kind of emission, observed only as low temperature photoluminescence (PL), is ascribed to isolated Ce³⁺ ions. The charge-compensated Ce³⁺ complexes are active both in PL and photostimulated luminescence (PSL) following X-ray irradiation. The PSL is nearly as efficient as in the case of the commercially used X-ray storage phosphor BaFBr:Eu²⁺. The X-ray induced electrons are trapped in F-type centres whose band position is characteristic for the nearby Ce complex. As shown by the fingerprint character of the PSL itself, the hole partner in the recombination is also associated or identical with the same Ce complex.     

Photo-stimulated emission of X-irradiated BaFBr:Eu

Abstract

The photo-stimulated luminescence (PSL) of Eu²⁺-doped BaFBr is excited in the two F centre absorption bands produced by X-irradiation at room temperature. The PSL intensity decreases with decreasing temperature by about a factor of 10. After bleaching at low temperatures the PSL is nearly zero, it can be regenerated by warming the crystal to room temperature. The results are discussed with a new model of the PSL process.     

BaFCl：Eu2+X射线存储机制的探讨

本文报导了BaF2-xClx和BSFCl:Eu2-(0.1%)两种粉未样品的制备过程;及其系列样品的电子自旋共振的实验结果.认为BaFCl:Eu2-存储X射线的过程是:经X射线辐照后;在其晶体中形成自由电子和空穴,阴离子空位俘获一个电子形成F心,而空穴被束缚在两个氯离子上形成Vk(Cl2-)心,Vk(Cl2-)心经迁移被发光中心Eu2+所束缚.     

A Tunneling Model for Afterglow Suppression in CsI:Tl,Sm Scintillation Materials

Combined radioluminescence, afterglow and thermoluminescence experiments on single-crystal samples of co-doped CsI:Tl,Sm suggest that samarium electron traps scavenge electrons from thallium traps and that electrons subsequently released by samarium recombine non-radiatively with trapped holes, thus suppressing afterglow. Experiments on single crystals support the inference that electrons tunnel freely between samarium ions and are trapped preferentially as substitutional Sm⁺ near V_KA(Tl⁺) centers where non-radiative recombination is the rate-limiting step. Afterglow in microcolumnar films of CsI:Tl,Sm is enhanced by inhomogeneities which impede tunneling between samarium ions, but is partly suppressed by annealing.     

Mechanoluminescence and thermoluminescence of BaFCl:Sm 2+ and BaFBr:Sm 2+ crystals

The alkaline-earth fluorohalide crystals MFX, where M=Ca, Sr, Ba, Pb and X=Cl, Br, I, form an important class of materials crystallizing in the PbFCl-type tetragonal structure which is also called the matlockite structure. These compounds have long been of interest because of the various defect species which can be detected by spin resonance and associated techniques. The crystals were prepared by slow cooling of the melt of a stoichiometric mixture of BaF ₂ and the corresponding chloride or bromide under 0.2 bar of ultrapure argon (5N5), often slightly fluorinated. We have studied the mechanoluminescence (ML) of BaFBr:Sm ²⁺ and BaFCl:Sm ²⁺ crystals. It is seen that after the impact of a moving piston, initially the ML intensity increases with time, attains a maximum value and then it decreases with time up to a particular minimum value, and then it increases again, attaining a peak value and finally disappears. The first peak lies in the deformation region and the second peak lies in the post-deformation region. The ML intensity of the BaFCl:Sm ²⁺ crystal is much higher than the ML intensity of the BaFBr:Sm ²⁺ crystal. For different impact velocities, the ML intensity increases with velocity; and the total ML intensity attains a saturation value for higher impact velocities. The total ML intensity increases with the increase in the applied load. It is suggested that the moving dislocation produced during deformation of crystals captures holes from hole-trapped centers (like H centers), and the subsequent radiative recombination of the dislocation holes with electron gives rise to ML. Thermoluminescence (TL) of BaFBr:Sm ²⁺ and BaFCl:Sm ²⁺ crystals was studied after exposure to ultraviolet rays with the help of a TLD reader. The peak of TL for the BaFBr:Sm ²⁺ crystal is found at ～247°C and for BaFCl:Sm ²⁺ crystals at 283°C. The TL intensity initially increases with increase in the UV radiation and then it attains saturation for higher values of UV exposure. The absorption spectrum was recorded with the help of a UV–visible spectrophotometer (Shimadzu). The band found at 275 nm was attributed to H centers.     

The structure of trapped hole centres in Al-doped TiO2

In rutile single crystals the ESR signals of holes are observed, trapped near [Al]^- and [Al-Al]^- centers upon u.v. excitation with the 405 nm Hg-line. The different centers can be thermally populated and quenched during warm-up of the crystals. Their charge state seems connected with charge transfer processes at other (e.g. Fe³⁺ impurities causing the photochromic behaviour of rutile.     

Eigenst?rstellen in elektronenbestrahltem Zinkoxid

The ESR of zinc oxide single crystals irradiated with 6 × 10¹⁸ electrons/cm² consists of five spectra resulting from interstitial oxygen ions and from holes trapped at zinc vacancies. Irradiation with visible light during the ESR measurements allows to determine the energy levels of the centres. Further the influence of the paramagnetic defects on the electric conductivity is discussed.     

Development of X-ray storage phosphor glass-ceramics

Europium- and bromine-doped fluorozirconate glass-ceramics show a significant photostimulated luminescence (PSL) effect after X-irradiation at room temperature. The PSL is assigned to the 5 d -4 f emission of Eu 2+ ions incorporated in barium bromide crystallites which are formed in the glass matrix upon suitable thermal annealing. The BaBr 2 crystallites grows in both the hexagonal and orthorhombic phases. The PSL efficiency of the glass-ceramic containing predominantly the hexagonal phase is only about 0.0025% of the well-known crystalline storage phosphor BaFBr:Eu used as a standard, whereas the glass-ceramic containing the orthorhombic phase has a relative efficiency of a few percent. Using the same formulation for the fluorozirconate glass-ceramic, but replacing Na by Rb and Li, results in the formation of RbBa 2 Br 5 microcrystallites after suitable annealing. The relative PSL efficiency increases to about 10%. The structural changes in these two fluorozirconate glass-ceramics were monitored by X-ray diffraction, photoluminescence, and electron paramagnetic resonance.     

Eigenstörstellen in elektronenbestrahltem Zinkoxid

The ESR of zinc oxide single crystals irradiated with 6 × 10¹⁸ electrons/cm² consists of five spectra resulting from interstitial oxygen ions and from holes trapped at zinc vacancies. Irradiation with visible light during the ESR measurements allows to determine the energy levels of the centres. Further the influence of the paramagnetic defects on the electric conductivity is discussed.     

Stimulation von ZnS-Phosphoren mit langwelligem Infrarot

Stimulation experiments with ZnS phosphors, using IR wavelengths from 2 to 15μ, were performed at the temperature of liquid helium. For this purpose a cryostat was constructed which allowed to keep the samples and the screening device at the temperature of liquid helium. Moreover glow curves after different decay times at 6 °K were taken. After excitation of ZnS phosphors a strong release of carriers from relatively deep traps is taking place although the phosphor is kept at the temperature of liquid helium. This emptying of traps is accompanied by a luminous recombination of the released electrons with the activator levels producing an intense afterglow which can be observed over a long time. This phenomenon cannot be explained by thermal release of trapped electrons into the conduction band, followed by recombination with the activator levels because of the depth of the emptied traps. The rate of thermal carrier release was calculated to be about 10^?29 sec^?1 for 0,05 eV deep traps, but the observed rate was of the order of 10^?4 sec^?1. An emptying of traps by IR-stimulation can be excluded because the phosphor was surrounded by a concentric screening device kept at 4.2 °K. The effect can be explained by luminous tunneling of trapped electrons to the activator levels. An estimate of the tunneling rate gives a value agreeing with the experimental results. If such a “tunnel afterglow” does exist a spectral shift to longer wavelengths compared to the usual fluorescence and phosphorescence is to be expected. This could be actually observed. Additional experiments included IR-stimulated emission after various decay times, glow curves taken after such stimulation, and studies of the influence of temperature. The results rule out the possibility that the carriers were released from the traps by IR light. Apparently, IR radiation affects the potential barrier between the traps and the activators so that the rate of recombination by tunneling increases.     

掺杂型BaFBr:Eu2+的热释发光性质的研究

BaFBr:Eu^2 是利用色心存储电子－空穴对并用可见光激励读出存储信息（产生Eu^2 的4f^65d→4f^7的跃迁）的优良的光激励发光材料。通过热释发光技术研究了BaFBr:Eu^2 的热激活行为，对其低温段和高温段的热释发光峰分别进行了归属，通过对BaFBr:Eu^2 以及掺杂Na^ 或Al^3 的BaFBr:Eu^2 的热释发光（TL）谱和光激励发光（PSL）谱的表征，指出在BaFBr:Eu^2 中掺杂Na^ 或Al^3 影响了F（Br^-）色心，使其陷阱深度变涛，并从理论上加以计算，得出的热致激发能量的变化与光致激光能量的变化能很好地吻合。     

Evidence for the spin-dependent scattering of conduction electrons on Mn2+ ions in Hg1−xMnxTe and Cd1−xMnxSe mixed crystals

Changes in the resistivity of Hg_1?xMn_xTe and Cd_1?xMn_xSe mixed crystals associated with paramagnetic resonance of the Mn²⁺ ions have been observed at liquid helium temperature in a strong magnetic field. The effect was recorded by monitoring the submillimeter radiation induced photoconductivity in a swept magnetic field. An increase in the resistivity associated with EPR of the Mn²⁺ ions is interpreted in terms of the spin- dependent scattering of electrons on magnetic impurities, the spins of which are selectively depolarised by means of paramagnetic resonance. Some additional effects influencing the experiments are also discussed.