Improved photoluminescence of ZnS:Mn nanocrystals by microwave assisted growth of ZnS shell

The photoluminescence (PL) of ZnS:Mn nanocrystals was improved greatly by microwave assisted growth of ZnS shell. Under optimized conditions, the luminescence quantum yield of ZnS:Mn nanocrystals increased from 2.8% to 12.1% after the growth of the ZnS shell. Time-resolved fluorescence spectroscopic and electron paramagnetic resonance measurements indicate that the improvement of the dispersivity of the doped Mn ions is responsible for the PL enhancement. Growth of the ZnS shell not only facilitated the diffusion of Mn ions during microwave irradiation but also prohibited the segregation of Mn ions on the particle surface. As a result, more isolated Mn²⁺ ions were produced after the growth of the ZnS shell, and thus the orange luminescence of ZnS:Mn nanocrystals was enhanced greatly.     

Effects of ZnS:Mn/AlN multilayer structure on luminescent properties of nanostructured thin-film EL device

Effects of ZnS:Mn/AlN multilayer structure on luminescent properties of nanostructured (NS) thin-film electroluminescent (TFEL) device of which emission layer is a multilayer composed with ZnS:Mn layers and 0.7-nm-thick AlN interlayers were studied. The bandgap widening and the increased PL efficiency of Mn²⁺ 3d-3d transitions with a decrease in the ZnS:Mn single-layer thickness down to 5 nm were observed, which is ascribed to quantum confinement effects. Meanwhile, the multilayer with 2-nm-thick ZnS:Mn single-layers shows a drop of PL efficiency, indicating the presence of defective region just on AlN. The tendency of the luminous efficiency of the NS-TFEL device against the ZnS:Mn single-layer thickness is similar to the tendency found in the PL efficiency, indicating the importance of the ZnS:Mn/AlN interface for the device performance.     

基于Mn掺杂ZnS量子点-BSA纳米复合材料检测头孢曲松钠

以3-巯基丙酸(MPA)为稳定剂,采用水相合成法合成了具有优良光学性质的Mn掺杂ZnS量子点。该量子点在室温条件下即可发射较强的磷光信号。将量子点与牛血清蛋白(BSA)偶联后,形成了纳米复合材料。由于BSA对量子点表面缺陷进行了有效修复,量子点发出的磷光明显增强。当加入头孢曲松钠后,头孢曲松钠与BSA的相互作用使量子点的磷光被有效猝灭,该磷光猝灭量(△P)与头孢曲松钠的浓度在一定范围内呈良好的线性关系(R=0.99)。量子点与BSA偶联的最佳条件为:pH=7.4,反应温度37 ℃,反应时间40 min,BSA浓度80 mg·L^-1,量子点浓度40 mg·L^-1。反应形成新的生物纳米复合材料,作为头孢曲松钠的磷光探针,其线性范围为0~30 μmol·L^-1,相关系数R=0.99,检出限为0.14 μmol·L^-1,相对标准偏差为1.63%。     

MOCVD技术制备的ZnS:Mn电致发光薄膜结晶性及Mn2+分布

本文报导了用MOCVD技术制备的ZnS:Mn电致发光薄膜为立方晶相,结晶取向性好,颗粒大。从高倍率的扫描电镜拍摄的照片观察到薄膜的表面平滑。SIMS测量表明Mn2+在ZnS薄膜纵向分布均匀,但在两侧有起伏,可能的原因是在生长的初终阶段流量的突变使化合物的化学计量比偏离而产生位错,引起原子的局部堆积,并且由于初终阶段ZnS:Mn生长的衬底不同使原子堆积层厚度不同。     

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。     

Mn掺杂的ZnS(001)表面的电子态特性

利用第一性原理计算Mn在ZnS(001)表面上几种掺杂位置的形成能、局域分波态密度和磁矩.对Mn在ZnS(001)表面上的三种位置的形成能进行比较,得到两种填隙位置是非常稳定的掺杂位置.分析ZnS(001):Mn各种再构表面的电子态密度和电荷密度分布.结果表明,三种表面模型中,自旋向上的Mn原子的3d态和近邻S原子的3p态都有一定的杂化,并且替代掺杂的Mn和邻近S原子的p-d杂化最明显,形成的共价键最强.而自旋向下的Mn原子的3d态比较局域,受S原子的3p态影响较小.计算了三种掺杂表面的磁矩,并分析计算结果.     

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。     

分散有ZnS:Mn2+纳米超微粒的有机薄膜的制备和光学性质

近年来,半导体超微粒的合成及光物理性质研究已成为活跃的领域.由于量子尺寸效应引起的量子点能级结构的变化及其光学性质已经作了大量研究[1-4].1993年,Bhar-gava首次报导了化学反应合成的ZnS Mn超微粒的光学性质[5],掺杂半导体纳米材料的出现,为纳米科学的研究开辟了新的领域.     

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。     

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.     

高场电致发光过程的动力学分析

本文通过对交流(ZnS:Mn,Cu)和直流(ZnS:Mo,Cu(Cu))两种不同结构的粉末发光材料的发光光谱,时间分辨发光光谱,电流波形,发光亮度波形,发光衰减以及发光强度与掺杂浓度的关系等方面的研究,对Mn和Cu这两种不同类型的发光中心的高场电致发光过程进行了分析,并用一个统一的模型对两种不同类塑的发光中心建立了发光动力学方程,由此解得Mn中心和Cu中心的发光强度随时间的变化规律表达式,它们分别包括了Mn中心和Cu中心发光亮度波形的所有情形。我们从动力学分析出发,找到了影响Cu中心和Mn中心发光强度的主要因素,并从理论上预言了提高发光强度的可能途径。     

Diffusional relaxation in ZnS after thermal doping at 800°C

Photoluminescence spectra of powdered ZnS thermally doped with MnS are studied. Correlations are demonstrated between variations in the luminescence characteristics of ZnS:Mn, on one hand, and some features of radiation center formation and the diffusion of Mn in ZnS after processing, on the other. It is found that after manganese doping at a temperature (T = 800°C) lower than the phase transition temperature of ZnS, relaxation processes owing to diffusion of Mn in ZnS take place in the material over times as long as 6.10³ h. It is shown that 6.10³ h after doping the α-MnS phase is essentially completely dissolved in the volume of the ZnS. Diffusion of Mn in powdered ZnS is found to occur via several channels, rapid diffusion along interior boundaries and slow diffusion via interstitial space, which indicates the existence of different activation energies for diffusion of Mn depending on its localization within the ZnS lattice.     

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).     

玻璃基质中ZnS纳米晶Mn2+的EPR谱

用融熔法制备分散有ZnS:Mn²⁺纳米晶的纳硼硅(Na₂O-B₂O₃-SiO₂)玻璃在不同温度、时间对样品进行退火处理,得到不同尺寸的纳米晶.研究了玻璃基质中ZnS:Mn²⁺纳米晶的EPR谱、微波功率饱和EPR谱及发射光谱,发现Mn²⁺有二种组态,即替位组态和间隙位组态.分析结果表明替位组态Mn²⁺及周围立方晶场的畸变程度直接影响光学发光特性.     

核/壳结构的ZnS:Mn/SiO_2纳米粒子的制备及发光性质研究

采用溶剂热法制备了Mn离子掺杂的ZnS纳米粒子(ZnS∶Mn),然后利用正硅酸乙酯(TEOS)的水解反应对其进行了不同厚度的SiO2无机壳层包覆。采用X射线衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)及荧光发射光谱(PL)对样品的结构及光学性质进行了表征和研究。包覆SiO2壳层后,粒子的粒径明显增大并且在ZnS∶Mn纳米粒子表面可以观察到明显的SiO2壳层。XPS测试印证了ZnS∶Mn/SiO2的核壳结构。随着SiO2壳层的增厚,ZnS∶Mn/SiO2的Mn离子的发光先增强后减弱,这是因为SiO2壳层同时具有表面修饰和降低发光中心浓度这两种相反的作用。当壳层厚度(壳与核的物质的量的比)达到5时,发光效果达到最好,其强度达到未包覆样品的7.5倍。     

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。     

Synthesis of robust water-soluble ZnS:Mn/SiO2 core/shell nanoparticles

Water-soluble Mn doped ZnS (ZnS:Mn) nanocrystals synthesized by using 3-mercaptopropionic acid (MPA) as stabilizer were homogeneously coated with a dense silica shell through a multi-step procedure. First, 3-mercaptopropyl triethoxy silane (MPS) was used to replace MPA on the particle surface to form a vitreophilic layer for further silica deposition under optimal experimental conditions. Then a two-step silica deposition was performed to form the final water-soluble ZnS:Mn/SiO₂ core/shell nanoparticles. The as-prepared core/shell nanoparticles show little change in fluorescence intensity in a wide range of pH value.     

Laser-induced down-conversion parameters of singly and doubly doped ZnS phosphors

Singly and doubly doped ZnS phosphors have been synthesized using flux method. Laser-induced photoluminescence has been observed in ZnS-doped phosphors when these were excited by the pulsed UV N₂ laser radiation. Due to down-conversion phenomenon, fast phosphorescence emission in the visible region is recorded in milliseconds time domain for ZnS:Mn while in the case of ZnS:Mn:killer (Fe, Co and Ni) the lifetime reduces to microseconds time domain. Experimentally observed luminescent emission parameters of excited states such as, lifetimes, trap-depth values and decay constants have been reported here at room temperature. The high efficiency and fast recombination times observed in doped ZnS phosphors make these materials very attractive for optoelectronic applications.     

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。     

Temperature dependence of the dielectric strength of zinc sulfide films

The temperature dependence of the dielectric strength E_pn of ZnS:Mn films produced by high-frequency magnetron sputtering was investigated in the range T=20–200°C. It is shown that processes associated with removal of adsorbed water from the ZnS:Mn films are responsible for the maximum on the E_pn=f(T) curve. Data on the temperature dependence of the capacitance and loss-angle are given for thin-film systems based on ZnS:Mn. Tomsk State Academy of Control Systems and Radioelectronics. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 6, pp. 91–94, June, 1966.