Polarization of photo-luminescence of ZnS: Cu monocrystals

Different models of luminescence centres are discussed on the basis of measurements of the composition of ZnS monocrystal photo-luminescence in different polarizations and temperature dependence of the degree of polarization. Those of the models submitted by Birman, which assume the polarization to be due to the different force of the oscillators for transitions withEc andEc, or models assuming luminescence polarization to be due to the orientation of the luminescence centres, agree with the results of experiments, i.e. the temperature independence of the degree of polarization and the conformable spectral composition of both polarizations. It is also shown that measurements made up to now of the degree of polarization must be taken as orientational as a consequence of the depolarizing influence of the diffused rays of luminescence on its value.

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ZnS: Cu

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Anisotropic surface effects in Au and Cu monocrystals

Electroreflectance spectra at normal incidence of (100) and (110) faces of gold and copper monocrystals are given, in the spectral range from 0.22–0.7 μm. The fractional change in reflectance is different with (110) faces when light is polarized parallel to the [001] direction and parallel to the [$\text{1}\text{10}$] direction while no anisotropy is seen on (100) faces. This shows that electroreflectance is a powerful tool to investigate metal surfaces where the optical electrons are sensitive to the distribution of the surface atoms.     

Photoluminescence of Cu:ZnS, Ag:ZnS, and Au:ZnS nanoparticles applied in Bio-LED

In this work, transition elements, including Cu²⁺, Ag⁺, and Au³⁺, were used to dope in zinc sulfide (ZnS) by chemical solution synthesis to prepare Cu:ZnS, Ag:ZnS, and Au:ZnS nanoparticles, respectively. Transition elements doping ZnS nanoparticles form the electronic energy level between the conduction band and valance band, which will result in the green light emission. There is a zinc sulfide emission shift from blue (~3.01 eV) to green light (~2.15 eV). We also found that Au:ZnS nanoparticles will emit a green light (~2.3 eV) and a blue light (~2.92 eV) at the same time because the mechanism of blue light emission was not broken after Au element had been doped. Furthermore, we used sodium chlorophyllin copper salt to simulate chlorophyll in biological light emission devices (Bio-LED). We combined copper chlorophyll with Cu:ZnS, Ag:ZnS, and Au:ZnS nanoparticles by a self-assembly method. Then, we measured its photoluminescence spectroscopy and X-ray photoelectron spectroscopy to study its emission spectrum and bonding mode. We found that Au:ZnS nanoparticles are able to emit green and blue light to excite the red light emission of copper chlorophyll, which is a potential application of Bio-LED.     

Luminescence of nanocrystalline ZnS:Cu

Temperature dependent luminescence and luminescence lifetime measurements are reported for nanocrystalline ZnS:Cu²⁺ particles. Based on the variation of the emission wavelength as a function of particle size (between 3.1 and 7.4 nm) and the low quenching temperature (T_q=135 K), the green emission band is assigned to recombination of an electron in a shallow trap and Cu²⁺. The reduction in lifetime of the green emission (from 20 μs at 4 K to 0.5 μs at 300 K) follows the temperature quenching of the emission. In addition to the green luminescence, a red emission band, previously only reported for bulk ZnS:Cu²⁺, is observed. The red emission is assigned to recombination of a deeply trapped electron and Cu²⁺. The lifetime of the red emission is longer (about 40 μs at 4 K) and the quenching temperature is higher.     

核-壳结构的ZnS:Cu/ZnS纳米粒子的制备及发光性质研究

制备了核-壳结构的ZnS:Cu/ZnS纳米粒子以及普通的没有壳的Cu2 掺杂的ZnS纳米粒子,研究了ZnS无机壳层对ZnS:Cu纳米粒子发光性质的影响.透射电子显微镜、激发光谱和发射光谱的研究表明,后加入的Zn2 离子在已经形成的ZnS核表面生长,形成ZnS壳层;而适当厚度的ZnS壳层可以钝化粒子表面,减少无辐射复合中心的数目,抑制表面态对发光的不利影响,提高ZnS:Cu纳米粒子中Cu2 离子在450 nm左右的发光强度.     

Photodielectric Processes in ZnS : Cu Polycrystalline Layers

The frequency dependences of dielectric parameters of zinc sulfide electroluminescent polycrystalline structures doped with copper are studied in the dark and under light excitation in the visible wavelength range. A positive photodielectric effect most pronounced in the low-frequency range was revealed. The experimental results are explained within framework of formation of a space charge in the bulk of a semiconductor. The analysis of data indicates they can be correlated with luminance characteristics of an electroluminescent layer.     

ESR在ACEL ZnS:Mn,Cu和ZnS:Cu材料研究中的应用

ZnS:Mn,Cu粉末发光材料的ESR谱随Mn2+浓度和制备条件的不同有着明显的变化。根据耦合Mn2+的ESR谱理论分析,计算ESR谱参数及其饱和现象表明,当Mn2+浓度>0.2%,Mn2+开始形成离子团,Mn2+团的形成和Mn2+离子与晶格间耦合随Mn2+浓度的增大而增强是发光浓度猝灭的主要原因,Mn2+浓度约为0.7%具有最高发光亮度。本文还讨论了退火条件对ZnS:Mn,Cu ESR谱的影响以及老化的ZnS:Cu中Cu2+的ESR谱。     

Quenching of photoluminescence in ZnS:Cu single crystals

Experiments on the quenching of photoluminescence in ZnS:Cu single crystals by secondary radiation are reported. Quenching of emission at photon energies of 1.4, 1.7, 2.4 and 2.75 eV by photons at 0.93, 1.6, 2.0, 2.4 eV is found, with a possible fifth peak at 2.7 eV. The effect of each secondary band on each emission band is found to be equivalent. This is explained in terms of a model in which all quenching transitions effectively fill a common ground state for the green/blue emission.     

Luminescence properties of co-doped ZnS:Ni,Mn and ZnS:Cu,Cd nanoparticles

Transition metal doped ZnS:Ni and ZnS:Cu and co-doped ZnS:Ni, Mn and ZnS:Cu, Cd nanoparticles were synthesized through the chemical precipitation method in an air atmosphere. The XRD analysis of co-doped samples shows the formation of cubic phase. The average size of nanoparticles ranges from 3.6 to 5.5 nm. The formation of co-doped nanoparticles was confirmed by XRD and PL analysis. The PL spectra show that the obtained nanoparticles have good crystal quality. An optimum concentration of transition metals was selected in co-doped ZnS nanoparticles.     

Shallow hole traps in ZnS: Cu,Al phosphors

Localized shallow trapping levels for minority carries, i.e., holes, in ZnS: Cu, Al phosphors are studied by the Dishman method, i.e. by measuring the temperature dependence of the ratio of the quantum efficiency for the green luminescence by the host excitation to that by the direct copper acceptor excitation over the temperature range from 4.2 K to room temperature. The ratio shows increases in three temperature ranges of 20–53 K, 58–100 K and 180–260 K. These increases are attributed to the release of holes to the valence band from three kinds of traps. Analyzing results, the depths of these traps are determined as 35, 68 and 306 mev.     

The relation between lattice-parameter and particle size in ZnS:Cu Phosphor

The effect of particle size on life time in electroluminescent phosphor was investigated using fractionated samples. The life time of large-particle size phosphors was longer than that of small-particle size phosphor. It was found that particle size has a close relation with the lattice-parameter magnitude; the lattice parameter was larger in a small-particle size phosphor when the activator and coactivator content were the same. It was concluded that the lattice parameter was an important brightness life-time factor.     

Zum Lumineszenz-Abklingverhalten von ZnS/Cu

The decay characteristics of ZnS/(10^?4) Cu have been investigated by ion pulse excitation. The excitation density could be varied by using ions of different masses. The decay is exponential. The decay times depend on the ion pulse duration and on the penetration depth of the used ions. The green emission shows two different decay times. The intensity of the slower component of the green emission could be altered by excitation with UV-light before decay measurement. In the case of the slower component of the green emission we suppose an interaction between the excited states of the luminescence centres and energetically deep electron traps.     

ACEL ZnS：Cu发光体内的Cu+迁移与发光的老化

众所周知,Cu对ZnS粉末ACEL是不可或缺和不可替代的。因此维持Cu和它的存在形式在ZnS晶粒中的稳定对ACEL的老化致关重要。Cu⁺在ZnS中具有很高的热扩散率,500℃时热扩散系数已达10^-9cm²/s,是各种杂质中热扩散最强的杂质。900℃时几分钟内即可使7~10μm的ZnS晶粒完全激活。Cu_xS具有很强的离子导电特性,在电场作用下表现出很强的Cu⁺迁移特性。由于Cu_xS具有很高的电导率,可视为导体,因此在外电场中ZnS晶粒内的Cu_xS导电线处于等电位状态。与Cu_xS导电线电位不同的所有等位面不能与Cu_xS相交叉而发生扭曲。由于电流的流动方向必须与等位面垂直,所以导致流过ZnS晶粒的大部分电流被汇集到Cu_xS导线上,并且在导电线上的电流密度分布呈两端弱、中间强的状态。因此在电场作用下Cu_xS导电线及其周边可能达到很高温度。如上所述,Cu⁺迁移是必然的,以此可以很好地解释Fischer所观察到的发光线对的老化现象。     

Barriers participating in the excitation of electroluminescence of ZnS:Cu

It is shown that heterojunctions of the type Cu_xS-ZnS:Cu cannot determine the brightness and quantum yield of electroluminescence of particles of powdered luminophors. The main contribution comes from the excitation of electroluminescence in surface barriers at places where dislocations reach the surface of crystals. State University for Means of Communication, Moscow. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2. pp. 89–92, February, 1998.     

ZnS…Cu电致发光电压传感器及其温度漂移补偿

利用ZnS…Cu电致发光粉末与环氧树脂胶混合,设计制作了一种梯形电极结构的电压传感单元,实现了电致发光电压传感器输出信号的温度漂移补偿。电致发光电压传感信号通过2根塑料光纤传输到2个硅光电探测器,并选择其开路电压作为传感器的输出信号。在同一外加电压条件下,梯形电极区域内的电场分布是不均匀的,因而不同场点的发光亮度不同。通过测量梯形电极区域内2个不同发光点的发光强度随外加电压的变化,并对两路输出电压传感信号进行数据拟合与计算,可获知被测电压的有效值,并可实现对输出信号温度漂移的补偿。在-40~60℃范围内,采用上述温度漂移补偿方法测量了有效值在0.7~1.5 k V范围内的工频电压,传感器输出信号的非线性误差低于1.6%,验证了该温度漂移补偿方法的有效性。     

Anomalous thermal quenching of luminescence in ZnS:Cu phosphor crystals

We studied the thermal quenching of luminescence (TQL) in the case of photoexcitation (PE, _e=313 and 365 nm) and cathodoexcitation (CE) with a high excitation density (10¹⁸ cm^–3· sec^–1) in ZnS:Cu single crystals with various degrees of copper supersaturation, EL-455 and K-83 copper-activated powders, and ZnSCu epitaxial thin films. Our study of TQL in the blue and green bands showed that two types of quenching anomalies are observed in the specimens used. An anomaly of the first type manifests itself in the fact that, with band-to-band excitation (_e = 313 nm and CE). the green band is quenched earlier than the blue band and small steps are observed on the quenching front. This anomaly is explained with the aid of a dislocation model of the blue center. An anomaly of the second type is observed in specimens not supersaturated with copper and consists of the quenching of luminescence beginning earlier at a high excitation (CE) density than at a low excitation (PE) density and proceeds in the same way in the blue and green bands. The thermal depths of the acceptors level are estimated from TQL for the three fundamental luminescence bands 440, 468, and 525 nm which are equal to 0.38 ±0.05, 0.7–0.8, and 0.9–1 eV, respectively.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 38–43, July, 1979.     

Influence factors and mechanism of emission of ZnS:Cu nanocrystals

Copper-doped Zn S(Zn S:Cu) nanocrystals are synthesized by the sol–gel method.The average size of the Zn S:Cu nanocrystals is 3.1 nm.The x-ray diffraction indicates that increasing the Cu-dopant concentration results in a large shift in the diffraction angle.The effects of the dopant concentration,the reactant ratio,and aging temperature on the optical properties of the Zn S:Cu nanocrystals are also investigated.The fluorescence emission mechanism is analyzed by peak deconvolution using Gaussian functions.We find that the emission of the Zn S:Cu nanocrystal is composed of different luminescence centers at 430,470,490,526,and 560 nm.The origins of these emissions are discussed and demonstrated by controlled experiments.     

Thermoluminescence characteristics of inorganically and organically capped ZnS:Cu nanophosphors

ZnS:Cu nanophosphors were prepared by wet chemical methods and characterized by X-ray diffraction (XRD). The typical morphologies of the nanophosphors were investigated by scanning electron microscopy (SEM). The thermoluminescence (TL) properties of inorganically and organically passivated ZnS:Cu nanophosphors were investigated after γ-irradiation using a ⁶⁰Co source at room temperature. The TL glow curve of capped ZnS:Cu showed variation in TL peak and intensity as the capping agent was changed. Amongst the synthesized samples the TL glow curve of SiO₂ capped ZnS:Cu showed the highest TL intensity. It has been found that TL response of SiO₂ capped ZnS:Cu is linear in the range 10-550 Gy. A discussion of the obtained results is also presented.     

Epitaxial growth defects and interfacial structures of Cu deposited on TiO2

Epitaxial growth defects and the interfacial structure between vapor deposited Cu and TiO₂(110) have been studied by combined high-resolution electron microscopy (HREM) and image simulations. The Cu film was found to grow epitaxially with an orientation given by Cu(111)//TiO₂(110) and Cu110//TiO₂ [001]. With this relationship, there exist two equivalent domain orientations which are rotated with respect to each other by 180°. Localized misfit dislocations have not been detected, but {111} stacking faults and microtwins were observed which may occur as a result of 3-D island coalescence. HREM observations and image simulations have been used to study the interface atomic structure. The dominant interfacial structure has a stoichiometric (110) TiO₂ surface with bridging rows of O atoms and occasionally, an interfacial structure having a reduced (110) TiO₂ surface terminated by both Ti and O atoms has been observed locally.     

ZnS:Cu荧光粉中Cu的价态及其形成发光中心的条件

无激活剂znS天蓝色发光必须在存在氧的情况下反应形成游离锌,然后通过吸附、扩散等物理化学过程形成硫空位和填充锌的晶体缺陷、构成天蓝色发光的发光中心,以(Zn)( )结构表示。铜激活的ZnS:Cu荧光粉,Cu发光中心的形成同样需要存在氧的情况下形成游离锌,游离锌扩散入ZnS晶格形成(Zn)( )结构,它是Cu2S或CuCl进入晶体的“接受体”。无论是Cu2S或CuCl进入晶格,Cu均为Cu+状态。