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.     

Enhanced oscillator strengths and optical parameters of doped ZnS bulk and nanophosphors

We synthesize and investigate the oscillator-strength (OS), dipole-moment (DM), and integrated cross-section values (ICSVs) of singly (Mn) and doubly (Mn and Co or Ni) doped samples of ZnS bulk and nanophosphors. The oscillator-strength values (OSVs) are found to enhance by three orders of magnitude when Co or Ni dopant is incorporated in ZnS:Mn bulk phosphors, which strongly suggests that a quencher dopant triggered an energy-transfer process in the host ZnS material. Nevertheless, although these quencher dopants were previously considered to kill the luminescence from the host material, we used these dopants in ZnS:Mn to create an additional pathway for the relaxation of the carrier, and to initiate the energy-transfer mechanism. On the other hand, a four orders of magnitude enhancement in the OSVs was observed on incorporating the quencher dopants in ZnS:Mn nanophosphors, which is attributed to the fact that our nanosamples are related to a strong-confinement case while the quencher dopant played a significant role in the variation of OSVs. Moreover, the analysis of OSVs showed that excitonic/defect level emission from ZnS host is due to a weak electric dipole transition (WEDT), while a magnetic dipole transition (MDT) dominates in the case of ZnS:Mn nanophosphors. Based on the present investigations, we clearly obtained an origin of excitonic- and impurity-related emission from the doped ZnS bulk and nanophosphor samples, which were almost vague in the previous studies of other researchers.     

ZnS:Mn摩擦发光特性的研究

本文报道了ZnS:Mn具有良好摩擦发光性能。研究了ZnS:Mn发光中心Mn^2 及其含量以及样品的灼烧温度、灼烧时间等条件对样品发光特性的影响。优化浓度配比和制备条件制备出了较高摩抢擦发光效率的ZnS:Mn摩擦发光材料。摩擦发光机理可能是由于机械能使ZnS:Mn的电子从基态激发到激发态所致,而具有较高的摩擦发光效率可能来源于ZnS:Mn具有较宽的激发能量范围。     

ZnS:Mn2+,Sm3+中Mn2+、Sm3+中心之间能量传递的分时光谱研究

前一阶段我们比较系统地研究了ZnS:Mn2+,Sm3+材料中Mn2+中心和Sm3+中心之间的能量传递。通过测量ZnS:Mn2+、ZnS:Sm3+和ZnS:Mn2+,Sm3+三种材料的发射光谱、激发光谱、选择激发发光光谱,证实了Mn2+中心和Sm3+中心之间存在偶极—偶极相互作用的无辐射能量传递。为了进一步研究Mn2+中心和Sm3+中心之间的相互作用及其物理特点,我们又仔细测量了上述三种不同类型材料的分时光谱,这不仅可以更清楚地了解激发停止后Mn2+中心和Sm3+中心之间的相互作用,而且有效地解决了Mn2+中心发射光谱和Sm3+中心某些特征光谱线交叠引起的测量发光衰减的困难。     

Emission spectra of MgSO4:Dy,MgSO4:Tm and MgSO4:Dy,Mn phosphors

MgSO₄:Dy, MgSO₄:Tm and MgSO₄:Dy,Mn thermoluminescence (TL) phosphors have been prepared and their emission spectra were measured using a linear heater and optical multichannel analyzer. Emission bands at about 480, 580 and 660 nm of MgSO₄ doped with Dy were observed in three dimension (3D) glow curve. Emission bands about 360, 460, and 660 nm were observed in a 3D glow curve of MgSO₄ doped with Tm. The emission spectra of MgSO₄:Dy and MgSO₄:Tm are attributed to the characteristic emission wavelengths from transitions of Dy³⁺ and Tm³⁺ respectively. The results show that the structures of traps in matrix materials determine the activation energy distribution and dopant energy levels of rare earth ions are related with the emission spectrum wavelengths of sulfate phosphors. The intensities of the glow peaks in both bands at about 480 and 580 nm in MgSO₄ doped Dy and Mn were dramatically reduced in comparison with that of MgSO₄ doped Dy except above 300°C. It means that the trapping structures of MgSO₄ :Dy phosphor has greatly been altered by the co-dopant Mn but no change is observed in wavelengths of the emission spectra.     

ZnS:Mn2+,Sm3+粉末材料中Mn2+和Sm3+之间的能量传递

研究了ZnS粉末材料中Mn2+中心和Sm3+中心之间的相互作用.通过测量单独由Mn2+或Sm3+掺杂及Mn2+,Sm3+同时掺杂的ZnS粉末材料的发射光谱、激发光谱、发光衰减以及选择激发发光光谱,证实了Mn2+和Sm3+之间存在偶极子-偶极子相互作用的无辐射能量传递.同时还计算了能量传递几率和传递效率.     

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).     

Valency and solubility limit of Cu ions in cubic and hexagonal phases of ZnS:Cu:Mn:Dy(Cl) phosphors

Polycrystalline ZnS:Cu:Mn:Dy (Cl) phosphors with varying concentration of Cu and fixed concentrations of Mn and Dy have been prepared, XRD studies showed that the cubic — hexagonal phase transformation in the phosphors is a sensitive function of Cu concentration so that cubic phase dominates at higher Cu concentrations. It has also been found that Cu enters into the cubic ZnS phase as Cu⁺ while in hexagonal ZnS phase as Cu²⁺ and their solubility limits are around 0.1 wt.% and 0.25 wt.% respectively. Attempt has been made to confirm the existence of Cu⁺ in cubic phase and Cu²⁺ in hexagonal phase from EL emission spectra of the phosphors.     

SrS:Ce/ZnS:Mn-A di-band phosphor for near-UV and blue LED-converted white-light emitting diodes

The SrS:Ce/ZnS:Mn phosphor blends with various combination viz 75:25, 50:50 and 25:75 were assign to generate the white-light emission using near-UV and blue-light emitting diodes (LED) as an excitation source. The SrS:Ce exhibits strong absorption at 427 nm and the corresponding intense emission occurs at 480 and 540 nm due to electron transition from 5d(²D)−4f(²F_5/2, _7/2) of Ce³⁺ ion as a result of spin-orbit coupling. The ZnS:Mn excited under same wavelength shows broad emission band with λ_max=582 nm originates due to 3d (⁴G−⁶S) level of Mn²⁺. Photoluminescence studies of phosphor blend excited using near-UV to blue light confirms the emitted radiation varies from cool to warm white light in the range 430-600 nm, applicable to LED lightings. The CIE chromaticity coordinate values measured using SrS:Ce/ZnS:Mn phosphor blend-coated 430 nm LED pumped phosphors in the ratio 75:25, 50:50 and 25:75 are found to be (0.235, 0.125), (0.280, 0.190) and (0.285, 0.250), respectively.     

Candoluminescence and radical-excited luminescence

The literature on the emission of solids heated in flames or excited by gases containing free radicals or excited molecules is reviewed. Many different emission processes can occur, including selective thermal radiation, candoluminescence, surface chemiluminescence, adsorboluminescence, and chemisorptive luminescence. These effects occur in a wide variety of materials, including BN, various oxides (MgO, ZnO, Y₂O₃, etc.), many impurity-activated phosphors (CaO:Bi, ZnS: Cu, Zn₂SiO₄:Mn, etc.), and organic compounds. Emission may be excited by a number of radicals, including H, O, OH, N, CO and CH. In a flame, the catalytic activity of the solid surface for radical recombination or de-excitation influences both the excitation of luminescence and the temperature of the solid (and hence the incandescence). An outstanding example of high-temperature candoluminescence is the Welsbach mantle (ThO₂ : Ce).     

Brighter glow in ZnS nanocrystals with polarized light

No known reports exist on luminescence enhancement under polarized light excitation. In this study, ZnS nanocrystals have been observed to produce brighter luminescence when excited by polarized light. ZnS:Mn bulk and nanocrystals have shown fivefold to tenfold increase in photoluminescence (PL) intensity when excited with linearly polarized light at 305 nm and 340 nm. Luminescence enhancement to a lesser degree was observed with linearly polarized light excitation for ZnS:Cu, Al and ZnS:Ag, Al nanocrystals. The observations suggest emission intensity dependence on the degree of anisotropy, which could be correlated mainly with the symmetry of the luminescence center and also to a lesser extent with nanoparticle shape asymmetry.     

玻璃中的ZnS:Mn2+超微粒发光的量子尺寸效应

自从Bhargava等^[1]报道了化学反应合成的ZnS:Mn²⁺纳米微粒的光学性质,掺杂半导体纳米微粒发光性质的研究受到了极大的重视。掺杂纳米微粒有可能成为新的一类发光材料.本文报导用熔融法制备的ZnS:Mn²⁺玻璃在光学性质上的量子尺寸效应。     

A simple procedure for electroluminescent phosphor assessment

A simple assessment procedure is described which facilitates optimal selection of an electroluminescent phosphor based on the measurement of two optically deduced energies—absorption and emission. These two energies are used as input for an appraisal analysis based on a classical configuration-coordinate diagram model of the phosphor. A phosphor performance figure-of-merit is proposed as a consequence of the formulation of this assessment procedure. This procedure is then used to rationalize the relative performance of five electroluminescent phosphors (ZnS:Mn, BaAl₂S₄:Eu, SrS:Ce, SrGa₂S₄:Ce, CaGa₂S₄:Ce). Additionally, two cathodoluminescent phosphors (ZnS:Ag and ZnS:Cu) are appraised using this methodology, suggesting that this procedure may be of some utility in the evaluation of other types of phosphors.     

场致发光薄膜ZnS:Mn,Er内Mn中心和Er中心的相互作用

首次提出了场致发光中Mn及稀土离子的能量传递问题.研究了同时掺有Mn和Er的ZnS:Mn,Er薄膜在脉冲激发下场致发光的衰减常数与杂质浓度的关系.证实了由Mn到Er的能量传递.估计了传递系数及传递效率.     

(Zn、Cd)S:Cu、Br黄色交流电致发光材料的晶体结构和发光特性

本文首次提出一种制备黄色交流粉末电致发光材料的新方法.在以ZnS为基质的绿色材料的基础上,低温扩散CdS,获得系列黄材料.并测量了晶体结构和发光特性.     

Influence of pH on luminescence from water-soluble colloidal Mn-doped ZnSe quantum dots capped with different mercaptoacids

Water-soluble ZnSe/ZnS core–shell quantum dots with ZnSe core doped by manganese ions show different luminescence response to pH changes in aqueous solutions depending on the type of solubilizing agents (thioglycolic acid, mercaptoundecanoic acid, sodium mercaptopropylsulfonate). In the case of long-chain mercaptoundecanoic acid only excitonic emission is affected by pH changes. Short-chain thioglycolic acid brings about equal excitonic/Mn emission variations with pH, while mercaptopropylsulfonate-stabilized quantum dots are insensitive to pH. The mechanism discussed here is based on the competition between different relaxation channels for excited excitons in ZnSe: excitonic radiative recombination, energy transfer to Mn ion and the photogenerated electron trapping due to the presence of protonated carboxyl group. ZnSe:Mn/ZnS quantum dots stabilized with long-chain mercaptoacids may be used as a new type of fluorescence ratiometric pH-sensor or indicator.     

Strong green luminescence of Ni2+-doped ZnS nanocrystals

ZnS nanoparticles doped with Ni²⁺ have been obtained by chemical co-precipitation from homogeneous solutions of zinc and nickel salt compounds, with S^2- as precipitating anion, formed by decomposition of thioacetamide (TAA). The average size of particles doped with different mole ratios, estimated from the Debye–Scherrer formula, is about 2–2.5 nm. The nanoparticles could be doped with nickel during synthesis without altering the X-ray diffraction pattern. A Hitachi M-850 fluorescence spectrophotometer reveals the emission spectra of samples. The absorption spectra show that the excitation spectra of Ni-doped ZnS nanocrystallites are almost the same as those of pure ZnS nanocrystallites (λ_ex=308–310 nm). Because a Ni²⁺ luminescent center is formed in ZnS nanocrystallites, the photoluminescence intensity increases with the amount of ZnS nanoparticles doped with Ni²⁺. Stronger and stable green-light emission (520 nm) (its intensity is about two times that of pure ZnS nanoparticles) has been observed from ZnS nanoparticles doped with Ni²⁺. Received: 18 December 2000 / Accepted: 17 March 2001 / Published online: 20 June 2001     

Electrical breakdown in ZnS:Mn films grown by rf-magnetron sputtering

We have studied the electrical breakdown field strength E_br of ZnS films doped with Mn(ZnS:Mn), produced by rf magnetron sputtering, as a function of film thickness d in the system Al-ZnS:Mn-Al. Electron-microscope studies have shown that breakdown is initiated under inhomogeneous field conditions imposed both by the roughness of the aluminum electrode and by the polycrystallinity of the ZnS:Mn film. An observed increase in E_br as d is reduced below 0.7 µm, with no polarity effect in breakdown under dc field conditions, is explained in terms of an electron-thermal breakdown model.Institute for Automation and Radio Electronics, Tomsk. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 41–44, March, 1993.     

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。     

Photo and electroluminescence properties in Zns: (Cu,La) and Zns: (Ag,La) phosphors

A method for preparation of ZnS: (Cu, La) and ZnS: (Ag, La) phosphors is described. Photo and electroluminescence of these phosphors have been studied. The voltage and frequency variation of EL brightness have also been reported. The results agree with the collision-excitation mechanism in the Schottky barrier. The emission of blue, green and yellow bands has been interpreted in terms of different electronic transitions. Simultaneous action of both the field and the 3650 Å radiation has been studied. An attempt has also been made to explain the quenching and enhancement.