Effect of chlorine concentration on the spectral characteristics of electroluminescence in ZnS: Cu: Cl phosphor

ZnS: Cu: Cl phosphor prepared under a vacuum firing process is found to give blue electroluminescence with emission peak at 460 nm which remains unaltered with the frequency of the excitation voltage. Addition of excess chlorine in the phosphor gives blue, green and red emission at 460, 520 and 640 nm. The intensity of the blue band decreases and it finally disappears as chlorine concentration is increased. A scheme involving three energy levels attributed to Cu²⁺, Cu⁺ and Cl^- centres in ZnS explains the experimental results completely.     

Effect of charged imperfections on electroluminescence of the ZnS:Cu,Cl phosphor

Electroluminescence is very much dependent on the concentration of imperfections created inside the host crystal. The effect of imperfections in ZnS:Cu,Cl is considered for different temperatures and compared with experimental curves. The resemblance supports our theoretical approach, i.e. the impact ionisation mechanism. The phosphor is most sensitive in the concentration range 10¹⁷ to 10¹⁹ per cm³.     

AC electroluminescence of ZnS: Cu,Cl, Mn thin films in the structure In2O3(Sn)-ZnS: Cu,Cl, Mn-SiOx-Al

AC electroluminescence of ZnS: Cu, Cl, Mn thin films in the structure In₂O₃(Sn) - ZnS: Cu, Cl, Mn-SiO_x Al was studied. Vacuum-evaporated films 0.5 to 2.0 μm thick, excited with sinusoidal voltage of 80–200 V and up to 2 kHz gave the luminance response fulfilling Alfrey-Taylor's relation. Thus the electroluminescence model, suggested by these authors for a ZnS monocrystal, can be applied also for ZnS thin films.     

Improved electroluminescence performance of ZnS:Cu,Cl phosphors by ultrasonic treatment

ZnS:Cu,Cl electroluminescence (EL) phosphors were prepared by high-temperature (1150 °C) solid-state reaction, subsequent ultrasonic treatment (t=0-60 min) and final low-temperature annealing process at 750 °C. The as-synthesized phosphors were characterized by X-ray powder diffraction (XRD), UV-vis absorbance spectra, electron probe microanalyzer (EPMA) and photoluminescence (PL) spectra. EL performance was investigated on an EL lamp fabricated by screen-printing at 100 V and 400 Hz. Ultrasound irradiation leads to intensity reductions and width increases of some XRD diffraction peaks, and results in a slight red-shift of UV-vis absorption edge. It also exhibits strong influences on PL and EL properties of the phosphors. Generally, PL performance monotonically declines with the increase of ultrasonic time, while EL performance benefits from the ultrasonic treatment and is superior to that of the commercial ones. The defects in the microstructure induced by the ultrasonic treatment are the fundamental reason for the change of PL and EL performances.     

Chemically produced ZnS: Cu films: Structure,properties, and mechanism of electroluminescence

ZnS: Cu films are prepared with a chemical nonvacuum technique by joint pyrolysis of zinc and copper dithiocarbamates at a substrate temperature between 260 and 300°C. It is shown that the films have the hexagonal lattice and are polycrystalline, with grains oriented mostly in the 〈0001〉 direction. The luminance-voltage characteristics, charge-voltage characteristics, brightness waveforms, electroluminescence spectrum, and degradation characteristics of the phosphors are investigated. A mechanism of electroluminescence and the degradation type are discussed. It is concluded that the MOCVD technique is promising for fabricating ZnS: Cu electroluminescent films.     

Field dependence of a.c. Electroluminescence in ZnS: Mn,Cu, Cl film panels

Electroluminescent (EL) film panels of ZnS: Mn, Cu, Cl operated by a.c. electric field are studied at room temperature. The emission spectrum consists of a single peak at 590 nm. The EL emittance B varies with frequency f of the applied a.c. electric field as B = B_s ? B_m exp ? f/f_c where B_s, B_m and f_c are constants. This equation indicates that B approaches a saturation value B_s when f?f_c and a linear relation between B and f when f?f_c. At a fixed frequency f, B is found to depend on the applied voltage V as B = A exp [-G/F + V^{$\text{1}\text{2}$})] where A, G and F are constants. This formula is valid at all stages of the operating life of the film panel.     

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.     

Photophysical and photoluminescence properties of co-activated ZnS:Cu,Mn phosphors

ZnS:Cu,Mn phosphors were prepared by conventional solid state reaction with the aid of NaCl-MgCl₂ flux at 900 °C. The samples were characterized by X-ray powder diffraction, UV-vis absorbance spectra and photoluminescence spectra. All samples possess cubic structure. Cu has a much stronger effect on the absorption property of ZnS than Mn. Incorporation of Mn into ZnS host only slightly enhances the light absorption, while addition of Cu remarkably increases the ability of absorption due to ground state Cu⁺ absorption. The emission spectra of the ZnS:Cu,Mn phosphors consist of three bands centered at about 452, 520 and 580 nm, respectively. Introduction of Mn significantly quenches the green luminescence of ZnS:Cu. The excitation energy absorbed by Cu is efficiently transferred to Mn activators non-radiatively and the Mn luminescence can be sensitized by Cu behaving as a sensitizer (energy donor).     

Laser phenomena in DCEL of ZnS:Cu:Nd:Cl thin films

The possibility of the occurrence of laser phenomena in the DCEL of thin films of ZnS:Cu:Nd:Cl, designed for display purposes, has been investigated. Evidence of stimulated emission at ～ 1080 nm has been found in both DCEL and cathodoluminescence emission of the films and has been attributed to a tendency to population inversion involving the ${}^4\text{F}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}$ energy level and a sub-level of the ${}^4\text{I}{}_{\mathrm{<mtext>11</mtext><mtext>2</mtext>}}$ energy level. In addition, the expected directional nature of the stimulated emission has been shown to be present at the higher applied voltages.     

与掺杂浓度相关的ZnS∶Mn纳米粒子的发光性质

采用溶胶法制备了Mn掺杂的ZnS纳米粒子,探讨了掺杂离子浓度对ZnS∶Mn纳米粒子的晶体结构和发光性质的影响。通过X射线衍射（XRD）对样品的结构进行了表征,结果表明：所制备的ZnS∶Mn纳米粒子为立方闪锌矿结构,其在Mn离子的掺杂浓度达到6%时不发生分相,但随着掺杂浓度的增加,纳米粒子的平均粒径会减小。光致发光光谱和荧光光谱的结果表明：通过改变掺杂离子的浓度可实现对ZnS∶Mn纳米粒子590 nm附近荧光发射波长的调节。此外,研究了温度对纳米粒子形貌和发光性质的影响。高分辨透射电子显微镜（HRTEM）观察发现,经过50℃陈化1 h后的ZnS∶Mn样品的平均粒径增大约为20 nm,且加热陈化有利于ZnS∶Mn纳米粒子中Mn2＋在590 nm处产生荧光。     

Role of space charge in the development of the electroluminescence of ZnS(Cu,Mn) film capacitors

It is shown that the conditions required for the development of electroluminescence are provided during one half-period in ZnS(Cu, Mn) film electroluminescent capacitors, while the brightness wave develops during the next half-period.Translated from Izvestiya VUZ. Fizika, No. 12, pp. 90–95, December, 1969.     

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.     

Infrared quenching of electroluminescence in ZnS: Mn thin-film electroluminescent structures

Electroluminescence from thin-film electroluminescent devices is found to be quenched after IR irradiation of the devices in the interval between exciting voltage pulses. The IR irradiation decreases the emission intensity in the spectral range 530–540 nm, while increasing it between 640 and 690 nm. These effects are explained by IR-induced charge exchange between the deep centers due to V _S ²⁺ and V _S ⁺ sulfur vacancies, an increase in the concentration of the latter vacancies, and the redistribution of the channels of impact excitation of Mn²⁺ and V _S ⁺ centers in favor of V _S ⁺ centers. The cross section and rate of impact excitation of V _S ⁺ centers, the photoexcitation cross section for V _S ²⁺ centers, the IR radiation absorption coefficient, the internal quantum efficiency of electroluminescence, and the probability of radiative relaxation of Mn²⁺ centers, as well as the electron multiplication factor in the phosphor layer, are evaluated.     

On the mechanism of the double-comet-shaped electroluminescence in ZnS:Cu crystals

Brightness waves of electroluminescent comets in ZnS:Cu single crystals have been investigated to decide whether the recombination occurs spontaneously or delayed by one half-period. Brightness waves during rising and decay, in addition to modifications of brightness waves due to disturbances of the stationary excitation by voltage pulses, exhibit delayed emission and a reservoir of excited centres exists in the stationary case. These results together with the time dependent blue-to-green ratio of the emission may be explained best on the basis of a bipolar field-emission model as proposed by Fischer.     

微波吸收法研究Mn,Cu掺杂对ZnS:Mn,Cu光生载流子复合过程的影响

采用微波吸收法，测量了ZnS:Mn,Cu粉末材料受到超短脉冲激光激发后，其光生电子和浅束缚态电子的衰减过程.发现Mn,Cu的浓度对导带电子的寿命有明显的影响，提高掺杂浓度会使光生电子的寿命大大缩短，还研究了掺杂浓度对光致发光强度的影响. 关键词： 发光材料 硫化锌 光电子 微波吸收技术     

147Pm激发的ZnS：Cu,Cl发光粉的研究

以高纯ZnS粉末为基质,采用高温转相、扩散,以及表面涂敷工艺,制得了¹⁴⁷Pm激发的ZnS:Cu,Cl发光粉。分析了ZnS:Cu,Cl的晶体结构,测量了ZnS:Cu,Cl的激发光谱、发射光谱、发光亮度。其晶体结构主要是六方纤锌矿型结构,激发光谱峰值波长为341nm,发射光谱峰值波长为513nm,初始发光亮度达到312mcd/m₂。由激发光谱的峰值波长341nm推算得到六方ZnS晶体的禁带宽度为3.64eV。分析了¹⁴⁷Pm激发的ZnS:Cu,Cl发光粉的发光寿命,其发光寿命达到5年以上。还探讨了该放射性发光粉的发光机理。¹⁴⁷Pm激发的ZnS:Cu,Cl的稳定发光,实际上是激发过程与复合过程的准平衡。ZnS:Cu,Cl的绿色发光来源于深施主-深受主对的复合发射。实验结果的分析表明,ZnS:Cu,Cl中深施主-深受主之间的能级间隔约为2.42eV。     

On the relationship between the optical characteristics of electroluminescence and the structure properties of ZnS:Cu

Conclusions Heat treatment of ZnSCu powder electroluminescent phosphors at a constant activator concentration affects the phase transition -ZnS -ZnS, which takes place through an intermediate phase. The amount of the intermediate phase depends on both the annealing temperature and time as well as on the rate of cooling.The electroluminescence spectrum of ZnSCu at a constant activator concentration depends on the annealing temperature and time and the rate of cooling and is correlated with the structure of the phosphor and the activation energy for the diffusion of copper in ZnS.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii Fizika, No. 6, pp. 22–25, June, 1971.