Untersuchungen über Elektronenhaftstellen in ZnS-Phosphoren

Glow curves of different ZnS phosphors were measured and analysed in the temperature region from 4.2 °K to 500 °K. It was attempted to clarify the origin of the glowpeaks observed above 77.4 °K and to attribute them to structural defects in the ZnS lattice. In glow curves started at 4.2 °K a strong dependence of the trap distribution on the method of preparation of phosphors was observed. In particular a ZnS(Cu) phosphor containing oxygen shows a broad continuum of shallow traps between 4.2 °K and 150 °K. In a ZnS(Cu, Ga) phosphor free of oxygen the trap density of the continuum of shallow traps is very small. Moreover this phosphor shows a sharp glowpeak at about 60 °K. The afterglow at the excitation temperatures of 4.2 °K and 77.4 °K was also studied. It is concluded that the rapid amptying of shallow and, to a lesser extent, of deep traps should be due to a tunneling process leading to luminous recombination of the trapped electrons with the activator levels.     

Zur Temperaturabhängigkeit der Elektrolumineszenz von Zinksulfid-Phosphoren

The temperature dependence of brightness waves and of average emission intensity of ZnS powder phosphors excited by square pulses was studied. In certain temperature ranges brightness waves with two peaks in each half-period of the exciting field are observed. Microscopical investigations of individual luminescent areas of a ZnS-grain showed the second peak in the brightness wave to be present in that half-period which in the model of delayed recombination is called the excitation half-period. It is shown that this emission takes place after the excitation process (duration <2μs) is finished and the resulting field in the inner parts of the crystallites has almost faded. Because of this fact and on the basis of glow and built-up investigations in the excitation half-period a spontaneous recombination of electrons thermally released from traps is proposed. Therefore the brightness waves with two peaks, but also emission in the excitation half-period is observed for temperatures at which — in the time average — many traps are still filled but on the other hand the probability for their emptying is already considerable.     

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.     

Thermally stimulated luminescence and infrared studies of CaS : Bi,Tm phosphors

Calcium sulphide phosphors doped with bismuth and thulium are prepared from Indian minerals. The glow curves are recorded in the temperature range of 96–320 °K. The activation energies are determined by analyzing the glow peaks after thermal cleaning, using different methods. The results show that, in these phosphors, the electron traps responsible for thermoluminescence are present prior to irradiation. The infrared absorption spectra are recorded in the range of 4000-250 cm^-1. It is concluded that the traps are due to host lattice defects which may arise from S^-2 ion vacancies, created during phosphor preparation.     

1keV以下的电子荧光及四极彩色荧光显示器结构探讨

本文分析了开发彩色荧光显示器(VFD)所存在的问题;论述了带螺旋端点阴极、前发光型四极平板VFD的结构;探讨了在新型VFD中使用Y2O2S:Eu、ZnS:Cu,Al和ZnS:Ag为三基色发光材料、在阳极电庄≤1keV时实现彩色显示的原理,并给出了一个有十二种发光颜色的频谱显示器件的实例.     

Thermoluminescent properties of Eu and RE co-doped phosphors CaGa2S4:Eu, RE (RE=Ln, excluding Pm, Eu and Lu)

The thermo-luminescence (TL) of rare earth ions RE³⁺ (RE=Ln, excluding Pm, Eu and Lu) co-doped phosphors CaGa₂S₄:Eu²⁺, RE³⁺ was studied between room temperature and 300 °C, and 3D thermo-luminescence of the phosphors were measured from room temperature to 400 °C. The basic material CaGa₂S₄:Eu²⁺, showed at least two bands in the TL glow curve. Changing the auxiliary activator RE³⁺ (rare earth ion), intensities and the positions of the TL glow curve peaks were affected significantly. For the phosphors with long afterglow, auxiliary activator such as Ce³⁺, Pr³⁺, Gd³⁺, Tb³⁺, Ho³⁺, or Y³⁺ created some new defects in these compounds at lower trap levels and enhanced their TL intensities. The Nd³⁺ or Er³⁺ auxiliary activator only enhanced TL intensities to a low extent, so these two phosphors have short persistent luminescence at room temperature. TL intensities of La³⁺, Sm³⁺, Tm³⁺ or Yb³⁺ co-doped phosphors were suppressed greatly and no afterglow was shown. The relationship between auxiliary activators and corresponding thermo-luminescence curves of phosphors CaGa₂S₄:Eu²⁺, RE³⁺ are discussed in detail. According to our results, suitable activation energy and enough high corresponding trap density are necessary for the phosphor with long afterglow.     

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.     

二价铕激活的ZnS磷光体的发光

本文详细描述了ZnS:Eu2+磷光体的合成及光致发光性能。首次报导了这种发光材料的特殊长余辉特性。作者测量了热释发光光谱、不同温度下的发射特性的变化及荧光的激发、发射衰减时间,提出两类缔合Eu中心的模型。用不同的缔合Eu中心较好地解释了它的光谱特性及长余辉现象,认为光谱的两个发射带来自不同的缔合Eu中心,即550nm发射带对与ZnS导带电子陷阱相缔合的Eu中心有关,650nm带来自与电子陷阱和空穴陷阱缔合的Eu中心。发射的余辉主要与导带中某种电源电子陷阱存在有关。此外,本文还对与应用有关的阴极射线发光性能进行了报导。     

Optical properties of electroluminescent ZnS doped with Cu+, Mn2+ and Gd3+ ions

ZnS:Gd, ZnS: Cu, Gd and ZnS: Mn, Gd phosphors have been prepared by firing the samples in argon atmosphere. Spectral distributions in these phosphors are discussed with appropriate mechanism. ZnS:Cu, Gd and ZnS:Mn, Gd are found to be examples of multiple band phosphors. Enhancement and quenching of the emission band intensities of all these phosphors have been studied inpel emission. It is observed that Gd³⁺ ions play an important role in transferring their excitation energy to other centres. The voltage and frequency variation ofel brightness are in agreement with collision excitation mechanism in Schottky barrier at the metal semiconductor interface. Studies in phosphorescence and thermoluminescence of these phosphors have also been carried out. It is observed that trap-depth changes slowly with temperature and dopant concentration. The values of trapping parameters have been evaluated. The irregular variation of the life-time of electrons in the traps. with temperature shows the existence of retrapping in these phosphors.     

Thermoactivated spectroscopy of heterovalent impurity traps in CdWO4

Abstract

Recombination luminescence emission spectra, TSL and trap spectra estimated by fractional glow technique (FGT), in nominally pure and Li-, Bi- and Ho-doped CdWO₄, crystals are reported. According to the investigations by FGT heterovalent impurities Li, Bi and Ho causes localized electronic states which act as traps for charge carriers. It is shown that TSL results in emission of known blue-green luminescence band by emptying of the Li⁺-related traps in CdWO₄-Li and yellow luminescence band by emptying of the Bi³⁺-related traps in CdWO₄-Bi. It is proposed that blue-green and yellow luminescence occur by recombination correspondingly of free holes and free electrons at different intrinsic tungstate group related luminescence centers.     

Untersuchungen zur elektronenangeregten Exoelektronenemission an Metallen

The exoelectron-emission from electron irradiated metal specimens was measured in a heatable Geiger-Müller-counter. For a silver specimen the term data (activation energy, frequency factor) of the traps were determined from the shape of the glow curve, using the methods applied on thermoluminescence glow curves. The comparison of the glow curve with theoretical emission curves of monoenergetic traps showed that the glow curve consisted of several emission curves, which had not been resolved in the measurement. For the activation energies of the traps responsible for the emission in the temperature range from 20 to 180 °C we got values of about 1 eV. The computed frequency factors are rather uncertain; they cover the range between 10⁹ and 10¹⁴ sec^?1.     

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.     

热释光谱研究长余辉发光材料的陷阱能级

介绍了热释光剂量计和热释光的基本原理。通过测量长余辉发光材料的热释光谱,并采用一阶动力学近似,可以量化分析长余辉发光材料中的陷阱能级的深度、电荷密度等参数,并可以讨论陷阱能级与长余辉性能的关系,深入理解长余辉过程。     

Luminescence studies of a combustion-synthesized blue–green BaAlxOy:Eu,Dy nanoparticles

Blue–green emitting BaAl_xO_y:Eu²⁺,Dy³⁺ phosphor was synthesized by the combustion method. The influence of various parameters on the structural, photoluminescence (PL) and thermoluminescence (TL) properties of the phosphor were investigated by various techniques. Phosphor nanocrystallites with high brightness were obtained without significantly changing the crystalline structure of the host. In the PL studies, broad-band excitation and emission spectra were observed with major peaks at 340 and 505 nm, respectively. The observed afterglow is ascribed to the generation of suitable traps due to the presence of the co-doped Dy³⁺ ions. Though generally broad, the peak structure of the TL glow curves obtained after irradiation with UV light was non-uniform with suggesting the contribution to afterglow from multiple events at the luminescent centers. Further insight on the afterglow behavior of the phosphor was deduced from TL decay results.     

Blue-emitting LaAlO3:Tm3+, In3+ phosphors for field emission displays

Tm³⁺ and In³⁺ co-doped LaAlO₃ phosphors were prepared by a Pechini sol–gel method and characterized by X-ray diffraction, scanning electron microscope, and cathodoluminescence spectrum. The phosphor is composed of slightly aggregated particles with approximately spherical shape and a narrow size range of 1.0–1.5 μm. Under voltage electron beam excitation, the phosphor shows the characteristic emissions of Tm³⁺. All the color purity, radiant efficiency, luminous efficiency, and stability of the optimum LaAlO₃:0.01Tm³⁺, 0.04In³⁺ phosphor are superior to these of commercial ZnS:Ag,Cl phosphor. These tests suggest that it could be a potential candidate as a blue phosphor for field emission displays.     

Untersuchung des „Auroral Afterglow“ und seiner Präparationsstadien

The intensity decay of negative bands of N ₂ ⁺ and of first positive bands of N₂ in the auroral afterglow has been measured. An explanation, seeming possible for the decay curves of the first ones is proposed. By this the intensity decay in the beginning of the afterglow at high ionic densities is determined by the recombination of N ₂ ⁺ with electrons. Later, the ambipolar diffusion of the charge carriers to the wall causes the time dependance. A value of the ambipolar diffusion coefficient in nitrogen, derived from the measurements is given by the relationD _a ·p ≈ 124cm² sec^?1 Torr. The temperature of the charge carriers is estimated to be 313? K. The intensity decay of the pos. group in the afterglow seems mainly to be due to the diffusion of metastable particles to the wall.     

Zn元素替代对MgGa2O4∶Cr3+的结构和发光性能的影响

采用高温固相法按化学式Zn_xMg_(1-x)Ga₂O₄∶Cr3+(x=0,0.2,0.6,0.8,1.0)配比原料制备了一系列红色长余辉发光材料。X射线衍射(XRD)分析表明样品物相均为面心立方结构。光致发光特性表明样品的红光发射峰均由以Cr3+为发光中心的电子2E—4A₂跃迁所致,Cr3+的激发带与基质发射带之间有大面积重叠,两者间存在有效的能量传递。余辉衰减曲线与热释光谱分析表明,不同Zn掺入量的样品余辉衰减快慢不同,是由于其中存在的陷阱能级深度不同,且陷阱能级越深,其余辉时间越长。     

Photoluminescence of Eu single doped and Eu/Dy codoped Sr2Al2SiO7 phosphors with long persistence

This paper reports the preparation of long persistent Sr₂Al₂SiO₇:Eu²⁺ and Sr₂Al₂SiO₇:Eu²⁺, Dy³⁺ phosphors and the comparison of their photoluminescent properties. The silicate phosphors prepared by solid-state reaction routine showed a broad blue emission peaking at 484 nm when activated by UV illumination. Such a bluish-green emission can be attributed to the intrinsic 4f-5d transitions of Eu²⁺. After the UV source was switched off, long persistent phosphorescence could be observed by naked eyes for both samples in darkness. Afterglow measurements revealed that Eu/Dy codoped phosphor possesses better afterglow properties than the Eu single doped one, since the maximum lifetime (τ_max=99 s) of the photons calculated from the decay profile is much larger than that of the Eu single doped phosphor (τ_max=82 s). TSL results suggested that the difference in afterglow properties was caused by the difference in the electron traps within the crystal lattice. For Eu/Dy codoped phosphor, the doping of Dy ions produced electron traps with trap depth of 0.52 eV, which is suitable and therefore leads to good persistence. However, in the case of Eu single doped phosphor, the trap depth is 0.88 eV, which is really too deep an energy barrier to overcome, and therefore a poor persistence was observed in the experiment.     

Effects of non-stoichiometry and substitution on photoluminescence and afterglow luminescence of Sr4Al14O25:Eu, Dy phosphor

The effects of nonstoichiometry and cationic substitution on photoluminescence and afterglow characteristics of strontium aluminate phosphor (Sr₄Al₁₄O₂₅:Eu²⁺, Dy³⁺) were investigated. Photoluminescence intensity of both the strontium-deficit and -rich phosphors was enhanced, but no definite correlation was observed between the afterglow intensity and non-stoichiometry. The photoluminescence emission maxima were either blue or green shifted in case of non-stoichiometric phosphors, whereas the afterglow emission maxima were not affected by the non-stoichiometry. Substitution of strontium by calcium resulted in white afterglow emission at higher calcium concentration. The emission centers in case of photoluminescence and afterglow emission appear to be different. Addition of silver significantly enhanced the afterglow intensity due to increased trap density.     

Dosimetric properties of rare earth doped LiCaBO3 thermoluminescence phosphors

Lithium Calcium borate (LiCaBO₃) polycrystalline thermoluminescence (TL) phosphor doped with rare earth (RE³⁺) elements has been synthesized by high temperature solid state diffusion reaction. The reaction has produced a very stable crystalline LiCaBO₃:RE³⁺ phosphors. Among these RE³⁺ doped phosphors thulium doped material showed maximum TL sensitivity with favorable glow curve shape. TL glow curve of gamma irradiated LiCaBO₃:Tm³⁺ samples had shown two major well-separated glow peaks at 230 and 430 °C. The glow peak at 430 °C is almost thrice the intensity of the glow peak at 230 °C. The TL sensitivity of the phosphor to gamma radiation was about eight times that of TLD-100 (LiF). Photoluminescence and TL emission spectra showed the characteristic Tm³⁺ peaks. TL response to gamma radiation dose was linear up to 10³ Gy. Post-irradiation TL fading on storage in room temperature and elevated temperatures was studied in LiCaBO₃:Tm³⁺ phosphor.