Luminescence enhancement of Mn doped ZnS nanocrystals passivated with zinc hydroxide

Mn-doped ZnS nanocrystals prepared by solvothermal method have been successfully coated with different thicknesses of Zn(OH)₂ shells through precipitation reaction. The impact of Zn(OH)₂ shells on luminescent properties of the ZnS:Mn nanocrystals was investigated. X-ray diffraction (XRD) measurements showed that the ZnS:Mn nanocrystals have cubic zinc blende structure. The morphology of nanocrystals is spherical shape measured by transmission electron microscopy (TEM). ZnS:Mn/Zn(OH)₂ core/shell nanocrystals exhibited much improved luminescent properties than those of unpassivated ZnS:Mn nanocrystals. The luminescence enhancement was observed with the Zn(OH)₂ shell thickening by photoluminescence (PL) spectra at room temperature and the luminescence lifetime of transition from ⁴T₁ to ⁶A₁ of Mn²⁺ ions was also prolonged. This result was led by the effective, robust passivation of ZnS surface states by the Zn(OH)₂ shells, which consequently suppressed nonradiative recombination transitions.     

壳聚糖中ZnS:Mn纳米微晶的制备及其发光特性

利用壳聚糖通过离子络合的方法制备了ZnS:Mn纳米微晶。壳聚糖含有一些极性基团,既是分散纳米微晶的有机介质,起到孤立微粒、控制粒度的作用,又具有表面修饰作用。通过改变反应物的浓度,得到微晶的尺寸在4.0～7.0nm(计算值).用激发和发射光谱观察了量子尺寸效应造成的光学性质的变化。用FTIR光谱分析了微晶和壳聚糖间的络合作用。     

Fast two-step microwave-activated synthesis of Mn doped ZnS nanocrystals: Comparison of the luminescence and doping process with thermochemical approach

In this work we report a fast two-step microwave activated synthesis of the ZnS:Mn nanocrystals. Zn(NO₃)₂ and Na₂S₂O₃ were used as the precursors and Mn(NO₃)₂ was employed as the source of the impurity. The aqueous synthesis was based on the heat sensitivity of Na₂S₂O₃, which releases some S species on heating. Consequently, the reaction was well activated under microwave irradiation resulting in formation of ZnS:Mn nanocrystals. Thioglycerol (TG) was also used as the capping agent and the catalyst of the reaction. The synthesis process was done in two steps, i.e. 1 min irradiation without TG and then injection of TG and continuation of irradiation. ZnS:Mn nanocrystals were quickly formed in the solution and luminescence was emerged in a few minutes. Optical transmission spectroscopy and X-ray diffraction analysis demonstrated formation of ZnS:Mn nanocrystals with a cubic crystalline structure and 3.0 nm average size. Photoluminescence measurements also showed some spectra with a Mn related peak located at 585 nm. The mentioned peak corresponds to ⁴T₁→⁶A₁ transition in Mn impurities and revealed the effective incorporation of Mn ions inside the nanocrystals. Evolution of the PL was also investigated and showed an increase in longer irradiation times. A qualitative model is also used to justify the necessity of using a two-step method as well as the PL emergence and increase in longer irradiation times. The model is based on separation between the nucleation and growth steps and significant role of TG in these stages. Finally, we present a comparison between the results of microwave activated method and two-step thermochemical approach. Although the synthesis time in microwave activated method was considerably short (less than 5 min), the luminescence properties were quite comparable with long time thermochemical approach. The doping process was also investigated for different Mn/Zn concentrations in two approaches. The results demonstrated that the doping occurred more effectively in the microwave activated synthesis.     

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。     

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。     

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.     

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.     

ZnS:Mn纳米荧光粉的制备

介绍一种制备ZnS:Mn纳米荧光粉的化学合成方法。本合成通过调节甲基丙烯酸与巯基乙酸的摩尔比，可在1.8-3nm范围内对纳米粒径进行很好的控制。生成的聚甲基丙烯酸包敷了ZnS:Mn纳米微粒，从而防止了纳米微粒团聚，同时增强了纳米微粒的抗氧化性，大大提高了纳米荧光粉的发光效率和发光稳定性。通过透射电镜（TEM）、X射线粉末衍射（XRD）和光致发光谱（PL）对所制得的纳米粉末进行了表征。     

核/壳结构ZnS : Mn/CdS纳米粒子的制备及发光

利用溶剂热法制备了Mn离子掺杂的ZnS纳米粒子(ZnS : Mn),利用沉淀法对ZnS ∶ Mn纳米粒子进行了不同厚度的CdS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)及光致发光(PL)光谱等手段对样品进行了表征。TEM显示粒子为球形,直径大约在14~18 nm之间。由XRD结果可以看出CdS壳层的形成过程受到了ZnS ∶ Mn核的影响,导致其结晶较差。XRD和XPS测量证明了ZnS : Mn/CdS的核壳结构。随着CdS壳层的增厚,样品的发光强度呈现一直减弱的现象。     

Temperature dependence of photoluminescence and magnetic properties in Yb-doped ZnS nanocrystals

Zinc sul?de semiconductor nanocrystals doped with Yb³⁺ ions have been prepared through a chemical precipitation method using PVP (polyvinylpyrrolidone) as a capping agent. The structure of the nanoparticles has been analyzed by X-ray diffraction (XRD). The average size of the nanoparticles is found to be 3.7±0.4 nm. Photoluminescence spectra were recorded for doped ZnS nanoparticles as a function of temperature between 9 and 300 K. The results suggest that two emission bands have been observed at different temperatures. The width of 1.269 eV peak increases as temperature is raised. A shift of lower energy emission band has been observed with the change of temperature. Moreover, the magnetic measurement showed that the sample exhibits paramagnetic behavior.     

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。     

ZnS型荧光粉的粒度、形貌和荧光发射谱的研究

本文主要对两种 Zn S型荧光粉 Zn S∶ Cu+和 Zn S∶ Mn2 +进行了研究。我们烧制了两种样品之后 ,对其进行了超声分散和包膜。经过超声分散和包膜处理后的样品的粒度分布分别为高斯型粒度分布 ,两者的中心粒度分别为 1 0微米和 2 0微米。两种样品的 SEM实验结果表明 ,经分散和包膜之后的颗粒形貌基本为圆形 ,颗粒的分散度很好 ,我们还分别测量了两者经过处理后的样品的荧光发射谱。 Zn S∶ Cu+ 的绿色发射峰值为 1 8860 cm- 1,Zn S∶ Mn2 + 的橙色发射峰值为 1 71 0 0 cm- 1。     

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.     

Studies on the spin Hamiltonian parameters for Mn2+ in the ZnS nanocrystals and bulks

The spin Hamiltonian parameters (zero-field splitting D, g factors and hyperfine structure constants) are theoretically studied for Mn²⁺ in the ZnS nanocrystals and bulks from the perturbation formulae of these quantities for trigonal and cubic tetrahedral 3d⁵ clusters, respectively. The trigonal Mn²⁺ centre in the ZnS nanocrystals is attributed to the impurity–ligand bond angle related to the C₃ axis about 0.39° larger than that (≈109.47°) of an ideal tetrahedron. Almost the same g factors and hyperfine structure constants for the nanocrystals and bulks can be ascribed to similar crystal-field environments (i.e. comparable cubic field parameters Dq), nearly the same covalency (i.e. the equal covalency factors N) and the Mn²⁺ 3d–3s orbital admixture (i.e. the identical core polarisation constants κ) in both systems. The ligand orbital and spin–orbit coupling contributions are found to be important and should be included in the electron paramagnetic resonance analysis in view of significant covalency.     

Raman scattering study of molecules adsorbed on ZnS nanocrystals

The adsorption of 4‐mercaptopyridine (4‐Mpy) molecules on ZnS nanocrystals was investigated by means of Raman spectroscopy. We compared the Raman signals of 4‐Mpy molecules adsorbed on ZnS nanocrystals and Ag substrate. The differences in the adsorption of 4‐Mpy molecules on the semiconductor and the metal substrate were noted. The results demonstrated that adsorbed species on the semiconductor ZnS nanocrystals can be detected by Raman spectroscopy. Copyright © 2006 John Wiley & Sons, Ltd.     

Facile synthesis and magnetic properties of manganese doped ZnS nanorods

The synthesis of both Mn(II) doped and undoped ZnS nanorods were carried out using a simple soft-chemical route using mercaptoethanol as capping agent. Their morphological, structural and magnetic properties are presented. The crystal structures of the as obtained products were investigated through X-ray diffraction study reveals the formation of hexagonal wurtzite structure. The growth of the nanorods is achieved by careful control over the precursor addition, temperature and time duration. The nanorods are single crystalline and the diameter of the rods was found to vary in the range of 20-50 nm. Vibrating sample magnetometer measurements at room temperature show paramagnetic behavior for the doped nanorods.     

核-壳结构的ZnS:Mn纳米粒子的荧光增强

采用反胶束方法制备了ZnS :Mn纳米粒子并对其进行了ZnS壳层修饰 ,采用发射光谱和激发光谱对其光学性质进行了研究。与未包覆的ZnS:Mn纳米粒子相比 ,核 壳结构的ZnS :Mn纳米粒子来自于Mn2 离子的 5 80nm的发光增强了数倍 ,归因于ZnS壳增加了Mn2 离子到纳米颗粒表面的距离 ,减弱了Mn2 离子向表面猝灭中心的传递。样品制备后 ,核 壳结构的ZnS :Mn纳米粒子在 5 80nm的发光随时间略有增强 ,激发光谱的位置未发生明显变化 ,而未包覆的ZnS:Mn纳米粒子在 5 80nm的发光显著增强 ,同时自激活发光减弱 ,激发光谱明显发生红移 ,说明未包覆的ZnS :Mn纳米粒子的尺寸随时间增大 ,而核 壳结构的ZnS :Mn纳米粒子尺寸基本不变。     

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.     

Synthesis and optical properties of Cr doped ZnS nanoparticles capped by 2-mercaptoethanol

Nanoparticles of Zn_1−xCr_xS (x=0.00, 0.005, 0.01, 0.02 and 0.03) were prepared by a chemical co-precipitation reaction from homogenous solutions of zinc and chromium salts. These nanoparticles were sterically stabilized using 2-mercaptoethanol. Here a study of the effect of Cr doping on structural, morphological and optical properties of nanoparticles was undertaken. Elemental analysis, morphological, structural and optical properties have been investigated by energy dispersive analysis of X-rays (EDAX), scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM) and UV-visible spectroscopy .EDAX measurements confirmed the presence of Cr in the ZnS lattice. XRD showed that ZnS:Cr nanoparticles crystallized in zincblende structure with preferential orientation along (1 1 1) plane. The average sizes of the nanoparticles lay in the range of 3-6 nm and lattice parameters were in the range of 5.2-5.4 Å. Lattice contraction was observed with an increase of Cr concentration. The particle size and lattice parameters obtained from TEM and SAED images were in agreement with the XRD results. The absorption edge shifted to lower wavelengths with an increase in Cr concentration as per UV-Vis spectroscopy. The band gap energy values were in the range of 3.85-4.05 eV. This blueshift is attributed to the quantum confinement effect.