Low temperature deposition of SrS:Cu,F ACTFEL device by electron beam evaporation

Photoluminescence (PL) and electroluminescence (EL) of SrS:Cu,F alternating current thin film electroluminescent (ACTFEL) device prepared by electron beam/thermal multi-source evaporation are presented. The active layer was grown at 380 °C and neither post-deposition annealing nor sulphur co-evaporation was performed. Two bands at 380 and 435 nm were present in the PL spectrum, which are suggested to be due to donor acceptor recombination. EL spectrum consisted of an additional band at 535 nm, which is attributed to Cu⁺ intracenter emission. The device exhibited yellowish white EL emission with chromaticity coordinates x=0.25, y=0.27 and low threshold voltage.     

变色的ZnS：Mn/SrS：Ce/ZnS：Mn薄膜电致发光的研究

利用ZnS:Mn/SrS:Ce/ZnS:Mn多层结构,得到了一种可变颜色的薄膜电致发光器件。研究了这一器件的发射光谱随电压和频率的变化,并讨论了随电压的增加,发射光谱中蓝带和黄带的不同增长的原因,以及在不同电压下,发射光谱中蓝带和黄带随频率变化的不同趋势的原因。观察到随驱动频率的增加,发射光谱出现黄-蓝色位移。     

SrS:Ce3+薄膜蓝色交流电致发光及其特性的研究

本文采用了SnO2/Y2O3/ZnS/SrS:Ce3+/ZnS/Y2O3/Al这种多层结构制备了SrS:Ce3+薄膜器件,并得到了较亮的蓝色交流电致发光。在5KHz正弦交流电压的激发下,该器件的最大亮度为100cd/m2左右。讨论了衬底温度与薄膜结晶完整性的关系,认为衬底温度在300—400℃之间有利于获得良好的结晶状态。本文还对SrS:Ce3+薄膜的光谱特性进行了讨论,比较了CeF3和CeCl3分别掺杂时,SrS薄膜的发光特性发现CeCl3掺杂较CeF3掺杂好。同时还看到,SrS:Ce3+薄膜的ACEL亮度和效率较ZnS:Ce3+薄膜要高,认为可能的原因是SrS基质提供了一种适合Ce3+激发的环境。     

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.     

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.     

用ESR研究ZnS微晶的相变

在ZnS和ZnS:Cu磷光体微晶中,共掺杂痕量的Mn2+,通过对ZnS晶体中的Mn2+离子的电子自旋共振(下面简写为ESR)超精细谱的监测,可以研究ZnS和ZnS:Cu微晶随制备时的煅烧温度升高引起的从立方相(β相)到六角相(α相)的相变。痕量Mn2+是一种灵敏的结构相变顺磁探针。     

Effect of structural distortions on the magnetism of doped spin-Peierls CuGeO3

The chemical selectivity and great sensitivity of the Extended X-ray Absorption Spectroscopy technique allowed the determination, in the paramagnetic phase, of the structural distortions induced by doping in the spin-Peierls CuGeO₃ compound. The distorted environments were analyzed as a function of concentration, magnetic nature of impurity and the substitution site (Ni, Mn and Zn impurities on the Cu site, Si impurity on the Ge site). This has led to estimate the variation of the angles and pair distances, and hence to evaluate the magnetic coupling along the Cu chains in the vicinity of the impurities. The antiferromagnetic interaction between Cu first neighbors in the pure sample is found to be weakened around Ni, almost cancelled in the case of Mn doping, and even to change sign, producing a ferromagnetic coupling for Si doping. More generally, the structural distortions on a local scale are shown to be key parameters for the understanding of the magnetic properties of doped spin-Peierls compounds.     

Formation of heavily doped n-type layers in GaAs by multiple ion implantation

Rare earth doping of CaF₂ produces material which gives strong thermoluminescence signals. In an attempt to separate the influence of impurity and intrinsic defects CaF₂ has been implanted with ions of Ce, Dy, Mn, Ca and F. Comparisons are made with chemically doped samples and the effect of thermal treatments have been made in all cases. The cerium and dysprosium ions influence both the shallow charge trapping levels, which determine the temperature of the glow peaks, and the recombination sites which control the photon spectra.

After implantation the strong TL signals show emission at wavelengths near 360 nm for Ce, 480 nm for Dy and for Mn.

Re-excitation of the trapping levels reveals selective emission for some defects, restructuring of less stable defects and major changes in defect concentrations with thermal treatment. The effects of the impurity and intrinsic defects on the spectra are discussed. One major observation is that addition of cerium to “pure” samples does not enhance the TL sensitivity, whereas Dy and Mn both show new glow peaks. In the case of Dy it is thought that the charge trap and the luminescent site are directly linked within one complex defect.     

Ⅱ-Ⅵ族化合物薄膜电致发光

电致发光薄膜是平板显示器的重要材料之一,我们从研究ZnS:Mn,Cu直流电致发光薄膜的大面积稳定发光开始,首次将稀土离子引进直流电致发光薄膜,实现了各色的直流电致发光,并研究其激发机理、过热电子的能量分布、稀土离子的碰撞截面和稀土离子发光中心在晶格中的位置等。在国内首先研制成功ZnS:Mn交流电致发光薄膜计算机终端显示器,并扩大面积到640×480像素(对角线10英寸)。为了实现彩色化显示,研制出稀土离子掺杂的各色交流电致发光薄膜。研究不同稀土离子在薄膜中的浓度猝灭,以便提高薄膜的发光亮度。在致力于实现彩色的过程中,首要的任务是提高蓝色电致发光薄膜的亮度和探索新的蓝色电致发光薄膜材料:从ZnS:TmF₃到CaS:TmF₃,发光亮度有了很大的提高;使SrS:Ce薄膜蓝色电致发光的亮度超过1000cd/m²;同时探索纳米Si和非晶Si/SiO₂超晶格结构的蓝色电致发光。成功地实现了ZnS:Mn/SrS:Ce白色电致发光和SrS:HoF₃三基色线谱发射的白色电致发光,发光亮度也超过1000cd/m²。     

退火处理对ZnS: Cu,Mn电致发光材料亮度的影响

ZnS系列电致发光已经在低亮度照明、液晶显示、汽车和航空仪表等领域得到广泛的应用.Mn、Cu是ZnS电致发光材料常用的激活剂,Mn²⁺在晶体中形成橙色发光中心,发光中心波长580nm;Cu⁺在晶体中不但形成发光中心,还形成发光所必需的Cu_xS,因此二者对发光亮度有明显的影响.由于ZnS:Cu,Mn橙色发光材料中的Mn掺杂量较大,影响了发光材料的内在结构,在灼烧过程中Mn化合物的其他成分还可能对发光材料的亮度产生了不利的影响,导致发光材料的亮度远低于蓝绿色材料.采用在退火过程中添加适量的Mn、Cu化合物,通过低温扩散的方式,使Mn²⁺均匀进入到ZnS晶格,获得了亮度较高的ZnS:Cu,MnACEL粉末材料.并对制备工艺中Cu、Mn含量、掺杂Mn化合物的形式、退火温度等对发光亮度的影响进行了讨论.实验中发现,在三种Mn化合物中(碳酸锰、乙酸锰、硫酸锰),以乙酸锰掺杂的材料亮度最高.得到Mn(以乙酸锰为添加物)的添加量为2%、Cu的添加量为0.1%、退火温度为700℃时,所制备的材料亮度最高.低温退火时掺杂Mn的材料亮度比常规材料的亮度高出1倍.     

White-electroluminescent device with horizontally patterned blue/yellow phosphor-layer structure

White-electroluminescent (EL) devices with stripe-patterned and square-patterned phosphor-layer structures are fabricated through a screen printing method: electrode/BaTiO₃ insulator layer/patterned blue ZnS:Cu, Cl and yellow ZnS:Cu, Mn phosphor layer/ITO PET substrate. The luminous intensities of EL devices with stripe-patterned and square-patterned phosphor-layer structures are 33% and 23% higher than a conventional device with the phosphor-layer structure without any patterns using the phosphor blend. It can be explained in terms of the absorption of the emitted blue light of blue phosphor layer by the yellow-emitting phosphor layer. The EL device of our patterned phosphor-layer structure gives the possibility to enhance the luminance.     

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。     

蓝色显示材料及器件的研究

用Ｈ２和ＣＳ２还原法制备Ｃｅ：ＳｒＳ发光材料，分析了两种方法对材料的结构及发光特性的影响，得到了最高亮度为９５０ｃｄ／ｍ＾２（１０００Ｈｚ）的Ｃｅ：ＳｒＳ薄膜电致发光（ＴＦＥＬ）器件；用高温固相法得到Ｃｅ：ＳｒＧａ２Ｓ４荧光粉，用射频溅射沉积的Ｃｅ：ＳｒＧａ２Ｓ４薄膜在６００℃以上、Ｈ２Ｓ气氛下快速热处理可以改善薄膜结晶性能，提高杂质激发峰强度，得到好的光致发光（ＰＬ）发光性能，以陶瓷片作为基片同     

The influence of doping element on structural and luminescent characteristics of ZnS thin films

For the fabrication of green and blue emitting ZnS structures the elements of I, III, and VII groups (Cu, Al, Ga, Cl) are used as dopants. The influence of type of impurity, doping technique, and type of substrate on crystalline structure and surface morphology together with luminescent properties was investigated. The doping of thin films was realized during the growth process and/or post-deposition thermal treatment. ZnS thin films were deposited by physical (EBE) and chemical (MOCVD) methods onto glass or ceramic (BaTiO₃) substrates. Closed spaced evaporation and thermodiffusion methods were used for the post-deposition doping of ZnS films. X-ray diffraction (XRD) techniques, atomic force microscopy (AFM), and measurements of photoluminescent (PL) spectra were used for the investigations. It was shown that the doping by the elements of I (Cu) and III (Al, Ga) groups does not change the crystal structure during the thermal treatment up to 1000 C, whereas simultaneous use of the elements of I (Cu) and VII (Cl) groups leads to decrease of the phase transition temperature to 800 C. The presence of impurities in the growth process leads to a grain size increase. At post-deposition treatment Ga and Cl act as activators of recrystallization process. The transition of ZnS sphalerite lattice to wurtzite one leads to the displacement of the blue emission band position towards the short-wavelength range by 10 nm.     

电子俘获材料SrS:Eu,Sm,Er的光谱特性和光存储特性

提出一种Er3+改进的电子俘获光存储材料SrS∶Eu0.002,Sm0.002,Erx,其中,0≤x≤0.006。通过水热反应,研究了不同退火温度对荧光粉晶相形成的影响,以及不同含量的Er3+对荧光粉的发光性质以及光存储特性的影响。结果表明,Er3+的引入导致荧光增强及光存储特性提高。当Er3+的摩尔分数x=0.003时,荧光强度、光激励发光强度及光存储量出现最大值,分别为不含Er3+时的1.9倍、2倍和3.5倍。同时,Er3+的掺入不改变样品的晶体结构和衰减特性。     

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。     

Interactions between Surface Impurities and the Electron–Hole System of a Semiconductor Crystal

The effects of creation and annihilation of impurities on the surface of a highly doped semiconductor under changes in the surface concentration n of dopant atoms constituting impurities are predicted theoretically. The effects are determined by electrostatic interactions of charged surface impurity species with charge carriers and semiconductor ions. The effects are observed in a certain range of n, provided the surface impurities exhibit donor (acceptor) properties, and the semiconductor is doped with an acceptor (donor) impurity.     

Mn-N共掺p型ZnO的第一性原理计算

基于密度泛函理论的第一性原理平面波超软赝势法对ZnO(Mn,N)体系的晶格结构、形成能、态密度以及电荷密度进行了计算和理论研究.研究结果表明,Mn和N共掺杂ZnO体系具有更低的杂质形成能和更高的化学稳定性,更加适合p型掺杂.Mn和N以1:2的比例掺杂时,体系的形成能降低,体系更稳定;同时,体系中形成双受主能级缺陷,使得杂质固溶度增大,体系中载流子数增多,p型化特征更明显.此外,研究发现相比于N单掺杂ZnO体系,Mn和N原子共掺杂ZnO体系有更多的杂质态密度穿越费米能级,在导带与价带之间形成更宽的受主N 2p的杂质态,同时空穴有效质量变小.与Mn-N共掺杂体系相比,Mn-2N共掺杂体系的受主杂质在费米能级附近的态密度更加弥散,非局域化特征明显.因此,Mn-N共掺杂有望成为p型掺杂的更有效的手段.     

ZnS∶Cu-罗丹明B的荧光共振能量转移性质

为了解决现有的基于量子点荧光共振能量转移体系的生物毒性问题,选用无毒的ZnS∶Cu量子点与罗丹明B构建新型荧光共振能量转移体系。通过共沉淀法成功制备了形貌均一的ZnS∶Cu纳米晶量子点。在此基础上,测试了不同掺杂浓度的ZnS∶Cu量子点及罗丹明B的荧光光谱。然后,通过对ZnS∶Cu量子点的表面修饰构建了以ZnS∶Cu量子点为供体、罗丹明B为受体的荧光共振能量转移体系。实验结果表明:ZnS∶2%Cu量子点的发光光谱与罗丹明B的吸收光谱在481 nm处有较大重合,说明构建荧光共振能量转移的最佳铜掺杂摩尔分数为2%。通过计算发现以ZnS∶2%Cu量子点为供体、罗丹明B为受体的荧光共振能量转移体系的能量转移效率为25.8%。进一步实验结果表明,罗丹明B浓度也能够影响能量转移。     

Mutual passivation of donors and isovalent nitrogen in GaAs

We study the mutual passivation of shallow donor and isovalent N in GaAs. We find that all the donor impurities, SiGa, GeGa, SAs, and SeAs, bind to N in GaAs:N, which has a large N-induced band-gap reduction relative to GaAs. For a group-IV impurity such as Si, the formation of the nearest-neighbor SiGa-NAs defect complex creates a deep donor level below the conduction band minimum (CBM). The coupling between this defect level with the CBM pushes the CBM upwards, thus restoring the GaAs band gap; the lowering of the defect level relative to the isolated SiGa shallow donor level is responsible for the increased electrical resistivity. Therefore, Si and N mutually passivate each other's electrical and optical activities in GaAs. For a group-VI shallow donor such as S, the binding between SAs and NAsdoes not form a direct bond; therefore, no mutual passivation exists in the GaAs:(S+N) system.