核壳型ZnS∶Cu/ZnS量子点的制备及发光性质

本文采用水相合成方法制备了ZnS∶Cu量子点并进行了ZnS壳层修饰,研究了壳层厚度对ZnS∶Cu量子点光学性质的影响,采用TEM、XRD、PL、PLE和UV-Vis等测试方法对其进行了表征。实验结果表明,合成的ZnS∶Cu/ZnS量子点为立方闪锌矿,尺寸分布均匀呈球形,分散性良好,经过壳层修饰平均粒径由2 nm增加到3.2 nm。随着ZnS壳与ZnS核量的比的增加,量子点的PLE激发峰位置和UV-Vis吸收谱线出现红移,也说明了量子点的尺寸增大,证明ZnS在ZnS∶Cu量子点的表面生长,形成了核壳结构的ZnS∶Cu/ZnS量子点。随着壳层增厚,量子点与铜离子发光中心相关的发射峰强度先增大后减小,当壳核比n_s/n_c=2.5时,发光强度达到最大。     

Enhanced visible light emission from Co doped ZnS nanoparticles

ZnS nanoparticles with Co²⁺ doping have been prepared at room temperature through a soft chemical route, namely the chemical co-precipitation method. The nanostructures of the prepared nanoparticles have been analyzed using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), selected-area electron diffraction (SAED), and UV-vis spectrophotometer. The sizes of as prepared nanoparticles are found to be in 1–4 nm range. Room-temperature photoluminescence (PL) spectrum of the undoped sample exhibits emission in the blue region with multiple peaks under UV excitation. On the other hand, in the Co²⁺ doped ZnS samples enhanced visible light emissions with emission intensities of ~35 times larger than that of the undoped sample are observed under the same UV excitation wavelength of 280 nm.     

Yellow-orange light emission from Mn2+-doped ZnS nanoparticles

ZnS nanoparticles with Mn²⁺ doping (1–2.5%) have been prepared through a simple soft chemical route, namely the chemical precipitation method. The nanostructures of the prepared undoped ZnS and Mn²⁺-doped ZnS:Mn nanoparticles have been analyzed using X-ray diffraction (XRD), Scanning electron microscope (SEM), transmission electron microscope (TEM) and UV–vis spectrophotometer. The size of the particles is found to be in 2–3 nm range. Room-temperature photoluminescence (PL) spectrum of the undoped sample only exhibits a blue-light emission peaked at ∼365 nm under UV excitation. However, from the Mn²⁺-doped samples, a yellow-orange emission from the Mn^{2+ 4}T₁–⁶A₁ transition is observed along with the blue emission. The prepared 2.5% Mn²⁺-doped sample shows efficient emission of yellow-orange light with the peak emission at ∼580 nm with the blue emission suppressed.     

Control of the shell structure of ZnO–ZnS core-shell structure

Nanostructured ZnO–ZnS core-shell powders were synthesized through a solution method using a thioacetamide (TAA) solution in deionized water. ZnO powder and TAA solution were employed to supply zinc and sulfur ions to form the ZnO–ZnS core-shell structures. The structure of the ZnS shell was strongly affected by the mole concentration of the TAA, and the structural properties were characterized by X-ray diffraction and high-resolution transmission electron microscopy. The optical properties of the nanostructured powders were also compared with those of pure ZnO powder. The ultraviolet (UV) emission was greatly enhanced compared to when pure ZnO powder was used in the nanostructured powder synthesized using the 0.5 M TAA solution, while the UV emission of that with the 0.05 M TAA solution was reduced. The green emission of the nanostructured powders was reduced compared to when the pure ZnO powder was used. The mechanism of the structural changes in the core-shell structures is proposed here and its effect on the luminescent properties is discussed.     

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.     

Mechano-chemical synthesis and optical properties of ZnS nanoparticles

In the present work, we report the synthesis and optical properties of ZnS nanoparticles produced by the mechano-chemical route. We used zinc acetate and sodium sulphide as source materials in a high energy planetary ball mill at rotation speed of 300 rpm and vial rotation speed of 600 rpm with ball to powder (BPR or charge ratio CR) 5:1 for 30 and 90 min. The milled powders were washed with methanol to remove impurity and dried at 300 °C for 1 h. The prepared nanoparticles have been characterized using X-ray diffraction (XRD), Field emission scanning electron microscope (FESEM), UV–vis–NIR spectrophotometer and Fluorescence spectroscopy. The crystallite size of the synthesized ZnS nanoparticles is found to be in the range 7–8 nm which was calculated using Debye–Scherer's formula. The value of optical band gap has been found to be in the range 3.80–4.15 eV. Room temperature photoluminescence (PL) spectrum of ZnS samples exhibit a blue emission peaked at 466 nm under UV excitation.     

退火对ZnS/PS复合体系光致发光特性的影响

用脉冲激光沉积(PLD)技术以多孔硅(PS)为衬底生长了ZnS薄膜,分别测量了ZnS、PS以及ZnS/PS复合体系在室温下的光致发光(PL)光谱。结果发现,ZnS/PS复合体系的PL光谱中PS的发光峰位相对于新制备的PS有所蓝移。把该ZnS/PS样品分成三块,在真空400℃分别退火10,20,30 min,研究不同退火时间对ZnS/PS复合体系光致发光特性的影响。发现退火后样品的PL光谱中都出现了一个新的绿色发光带,归结为ZnS的缺陷中心发光。随着退火时间的延长,PS的发光强度逐渐降低且峰位红移。把ZnS的蓝、绿光与PS的红光相叠加,整个ZnS/PS复合体系在可见光区450~700 nm形成一个较宽的光致发光谱带,呈现较强的白光发射。     

Influence of Cu ion implantation on the microstructure and cathodoluminescence of ZnS nanostructures

The microstructure and optical properties of as-synthesized and Cu ion implanted ZnS nanostructures with branched edges are studied by using high-resolution transmission electron microscope (TEM) and spatially-resolved cathodoluminescence measurement. Obvious crystalline deterioration has been observed in Cu-doped ZnS nanostructures due to the invasion of Cu ions into ZnS lattice. It was found that the optical emissions of ZnS nanostructures can be selectively modified through the control of Cu ion dose and subsequent heat treatment. An increase of Cu dopant content will lead to an apparent red-shift of the intrinsic band-gap emission in the UV range and the broadening of defect-related emission in visible range. The influences of Cu ion implantation on the microstructure and related optical properties were discussed.     

Synthesis and photoluminescence,field emission properties of stalactite-like ZnS-ZnO composite nanostructures

Wurtzite stalactite-like quasi-one-dimensional ZnS nanoarrays with ZnO protuberances were synthesized through a thermal evaporation route. The structure and morphology of the samples are studied and the growth mechanism is discussed. X-ray diffraction (XRD) results show both the ZnS stem and the ZnO protuberances have wurtzite structure and show preferred [001] oriented growth. The photoluminescence and field emission properties have also been investigated. Room temperature photoluminescence result shows it has a strong green light emission, which has potential application for green light emitter. Experimental results also show that the stalactite arrays have a good field emission property, with turn-on field of 11.4 V/μm, and threshold field of 16 V/μm. The ZnO protuberances on the ZnS stem might enhance the field emission notably. PACS 81.05.Dz; 81.07.Bc; 81.16.-c; 78.60.Hk; 85.45.Db     

聚氧化乙烯介质中的掺杂硫化锌纳米晶的制备及光学性质

简述了聚氧化乙烯介质中的铽、铕、铥、钆、钇、镓、锰掺杂的硫化锌纳米晶的制备方法以及紫外吸收光谱、激发光谱和光激发发射光谱.制成的硫化锌纳米晶直径为3.0～3.5nm.     

树形分子包覆的ZnS量子点对潜指纹的荧光标记成像研究

在Zn2+离子与聚酰胺-胺(PAMAM)树形分子配位的基础上,制备了稳定的PAMAM树形分子包覆的ZnS量子点(quantum dots,QDs),并用紫外-可见吸收光谱(UV-Vis)和荧光发射光谱进行了表征。结果表明,Zn2+离子能与PAMAM树形分子发生配位络合作用,且饱和配位时间为6h;在波长365nm紫外光的激发下,PAMAM树形分子包覆的ZnS量子点发射出明亮的蓝色荧光,荧光发射峰约位于450nm。最后,将得到的PAMAM树形分子包覆的ZnS量子点纳米复合材料应用于锡纸上潜指纹的荧光标记成像研究,发现指纹可以被清晰识别,呈现明亮的蓝色荧光指纹。     

Synthesis and stabilization of ZnS nanoparticles embedded in silica nanospheres

The silica-coated ZnS nanocomposites have been synthesized by a seeded-growth procedure in iso-propanol. The results of XRD, HRTEM and UV absorption show that the ZnS nanoparticles can be incorporated in the silica nanospheres without changing the particle size, and the composites are of multi-core structure. UV absorption and emission spectra have been performed to check the character of the composites, which show that the silica shell not only increases the PL intensity, but also greatly improves the anti-oxidation ability and thermal stability. PACS 81.05.Dz; 81.16.Be; 81.65.Rv; 78.55.Et; 78.66.Hf     

Enhanced blue emission from ZnS–ZnO composites confined in SBA-15

A new optical material, the ZnO nanoparticles that are modified with ZnS and confined in SBA-15, has been prepared through the controllable sulfuration at relatively low temperature (40 °C) from the ZnO/SBA-15 composites. The precursor composites can be prepared through a novel path in which the zinc is well dispersed by directly grinding zinc nitrate into the as-synthesized SBA-15 occluded with template followed by calcination, and it is possible to control the conversion of ZnO to ZnS by adjusting the reaction time. The resulting samples are characterized by XRD, nitrogen adsorption–desorption and photoluminescence (PL) spectroscopy. ZnO–ZnS composites, mainly confined in the mesopore of SBA-15, exhibit dramatically enhanced blue emission at the expense of the UV emission.     

双功能配体在ZnSTb乙醇溶胶合成中的应用

以双功能团配体SCN^-链接ZnS和稀土离子Tb³⁺,制备了ZnSTb乙醇溶胶,以紫外吸收和光致发射光谱研究了其光学性质.该溶胶经紫外激发得到了Tb³⁺的四个特征发射,分别对应于Tb³⁺的⁵D₄→⁷F_J(J=6,5,4,3)跃迁;Tb³⁺的特征发射可能来自ZnS到Tb³⁺的能量传递,即ZnS纳米微粒吸收能量,并将其通过SCN^-桥传递给稀土离子Tb³⁺,从而导致Tb³⁺的特征发射.文中还讨论了对双功能团桥联配体的一般要求.     

Highly luminescent undoped and Mn-doped ZnS nanoparticles by liquid phase pulsed laser ablation

In this paper we report the synthesis of highly luminescent ZnS and Mn-doped ZnS nanoparticles with uniform particle size distribution by liquid phase pulsed laser ablation. The formation of nanosized ZnS crystallites was confirmed by high-resolution transmission electron microscopy (HRTEM) images. The optical properties of these nanoparticles were studied by room temperature photoluminescence (PL) spectra. The PL emission from the ZnS nanoparticles shows a sharp peak in the UV region (334 nm) corresponding to the band edge and a broad peak in the visible region which can be attributed to the sulphur vacancies, cation vacancies and surface states in the nanocrystals. The yellow emission from the Mn-doped ZnS nanoparticles can be attributed to the radiative transition between ⁴T₁ and ⁶A₁ levels within the 3d⁵ orbital of Mn²⁺.     

Red luminescence of ZnS: Fe crystals

In order to elucidate the nature of the red emission band at 660 nm in ZnS: Fe crystals, the equilibrium luminescence, the thermoluminescence and the photoinduced EPR signals were measured, using UV, or the simultaneous UV + IR excitations. In addition, the polarization properties and the light-pressure shift of the red luminescence were studied. On the basis of the obtained results and of the data reported in the literature and concerning the red and IR emissions in ZnS: Fe a donor-acceptor model is proposed, in which the transition Cl^2?→Fe³⁺ would give rise to the 660 nm band.     

Investigation of structural,optical and electrical properties of ZnS thin films prepared by nebulized spray pyrolysis for solar cell applications

Zinc sulfide (ZnS) thin films have been deposited on microscopic glass and fluorine doped tin oxide substrates by nebulized spray pyrolysis technique with different substrate temperature and molar concentration. The structural, morphological, optical and electrical properties of the prepared ZnS thin films have been studied using X-ray diffraction (XRD), field emission scanning electronic microscopy (FESEM), UV–Vis spectrophotometer and Hall effect measurement. XRD patterns confirm that the prepared films are hexagonal wurtzite structure, with (100) as preferred orientation. The structural parameters such as crystallite size, dislocation density and microstrain have been calculated from XRD study. Hydrophilic and hydrophobic nature is revealed by contact angle measurements. FESEM image of the ZnS thin films show smooth and uniform spherical grains are uniformly arranged on the films surface. Optical transmittance spectrum illustrate that the ZnS films were high transparent in the visible region and gets absorbed in the UV region. The optical band gap value of the ZnS thin films decreased with the increasing substrate temperature. The average transmittance is found to be 82% and direct band gap value is 3.56 eV at 400 °C for set D. The Activation energy of the prepared ZnS films was determined from the graph between ln (ρ) versus temperature (K^?1) using a four-probe method.     

功能性ZnS纳米荧光探针的合成及其光谱性质研究

报道了功能性ZnS纳米荧光探针的合成与表征 ,同时研究了纳米粒子的荧光衰变寿命 ,考察了该纳米荧光探针的吸收光谱和荧光发射光谱特性。与此同时 ,研究了不同蛋白质和核酸对该纳米荧光探针的吸收光谱和荧光发射光谱的影响 ,实验表明 ,蛋白质的加入使得该纳米荧光探针的吸收和发射光谱强度均增强 ,而核酸的加入则使其吸收和发射光谱强度均减弱。据此 ,可望将该纳米荧光探针应用于生物大分子的分析测定     

核壳结构CdS/ZnS纳米微粒的制备与光学特性

用微乳液法制备CdS纳米微粒 ,以ZnS对其进行表面修饰 ,得到具有核壳结构的CdS/ZnS纳米微粒 .采用X射线衍射 (XRD)、透射电镜 (TEM )表征其结构、粒度和形貌 ,紫外 可见吸收光谱 (UV)、光致发光光谱(PL)表征其光学特性 .制得的CdS近似呈球形 ,直径为 3.3nm ;以XRD和UV证实了CdS/ZnS核壳结构的实现 .研究了不同ZnS壳层厚度对CdS纳米微粒光学性能的影响 ,UV谱表明随着壳层厚度的增加纳米微粒的吸收带边有轻微的红移 ,同时短波吸收增强 ;PL谱表明壳层ZnS的包覆可减少CdS纳米微粒的表面缺陷 ,带边直接复合发光的几率增大 ,具有合适的壳层厚度时发光效率大大提高 .     

Determination of depths and frequency factors of traps by UV amplitude modulated excitation

A study is made of the photoluminescence of ZnS-type phosphors submitted to a UV excitation modulated at various frequencies. The resulting emission shows a modulation rate and a phase shift which are functions of the occupancy of the various groups of traps, and therefore depend on temperature. Starting from the phase shift, the activation energy as well as the frequency factor of various trapping levels in ZnS/Cu and CdS, ZnS/Mn, Au samples have been computed. These results are compared with those deduced from ordinary or fractional glow curves. The advantage of the present modulated excitation method is to yield simultaneously both the activation energy and the frequency factor.