纳米ZnS基白光发射材料的制备和表征

利用溶胶．凝胶法,通过直接掺杂Mn^2 获得白光发射且操作工艺简单的纳米ZnS：Mn荧光粉,使用XRD、UV、PL及VT-IR等方法研究了ZnS：Mn纳米微粒的粒径、结构及荧光特性。结果表明：ZnS：Mn纳米微粒的平均粒径约为7nm,为闪锌矿晶体结构;所制备样品的荧光发射光谱有强度相当的两个峰,一个是峰值位于480nm的基质发光,另一个是峰值位于590nm的橙色光,样品总体发白光;Mn^2 的掺杂量对ZnS：Mn纳米白光荧光粉发光性能的影响很大;在纳米微粒的形成过程中,聚甲基丙烯酸将该纳米粒子包覆。     

表面修饰的ZnS:Mn量子点的发光性质及其对生物分子的检测

采用水热法制备了ZnS:Mn量子点,探讨了掺杂离子浓度对ZnS:Mn量子点的晶体结构和发光性质的影响。通过荧光光谱对样品进行表征。结果表明:掺杂离子的摩尔分数达到2%时,ZnS:Mn量子点在595 nm附近的发光最强;继续增加掺杂浓度反而出现荧光猝灭的现象。本文还研究了表面修饰对量子点形貌和发光性质的影响。通过透射电子显微镜(TEM)观察样品的形貌,发现经过3-巯基丙酸(MPA)修饰后的样品表面团聚现象得到改善,并且尺寸单一、单分散性较好,平均粒径约为5 nm。经过修饰后的样品减少了表面非辐射性缺陷中心,使掺杂Mn2+所引起的595 nm附近的发射峰强度增大。将MPA修饰后的ZnS:Mn量子点与牛血清白蛋白(BSA)分子进行生物偶联,并利用BCA法对偶联上的蛋白含量进行定量检测,结果显示经过修饰后的量子点偶联蛋白的能力更强。     

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。     

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。     

ZnS:Mn纳米晶的制备及其发光性能研究

以C19H42BrN为表面活性剂,采用水热法合成了ZnS:Mn纳米晶,分别利用XRD、TEM、荧光光谱仪对其物相、形貌及光学性能进行了研究。结果表明:ZnS:Mn纳米晶为闪锌矿ZnS结构,颗粒近似球形,平均粒径为4～8 nm。荧光光谱显示,ZnS:Mn纳米晶的荧光发射峰强度随着Mn2+掺杂浓度和表面活性剂含量的增加而逐渐增强。     

核-壳结构的ZnS∶Cu/ZnS纳米粒子的制备及发光性质研究

制备了核-壳结构的ZnS∶Cu/ZnS纳米粒子以及普通的没有壳的Cu2 掺杂的ZnS纳米粒子,研究了ZnS无机壳层对ZnS∶Cu纳米粒子发光性质的影响。透射电子显微镜、激发光谱和发射光谱的研究表明,后加入的Zn2 离子在已经形成的ZnS核表面生长,形成ZnS壳层;而适当厚度的ZnS壳层可以钝化粒子表面,减少无辐射复合中心的数目,抑制表面态对发光的不利影响,提高ZnS∶Cu纳米粒子中Cu2 离子在450 nm左右的发光强度。     

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。     

LaF3∶Ce3+纳米晶的制备及荧光性质

采用水热法制备了掺杂Ce3+的LaF3的纳米粒子,分别用X射线粉末衍射(XRD)和荧光光谱(PL)对样品的结构和性质进行了表征.XRD的结果表明:LaF3∶Ce3+纳米晶标准卡为JCPDS 73-2192,且颗粒平均尺寸为18.7nm,掺入Ce3+杂质后晶格结构没有变化.荧光光谱结果表明:Ce3+呈现其宽带发射,激发峰在245nm处,发射峰在444nm处,随着Ce3+的摩尔浓度比的增加,样品的荧光强度先增大后减小,且Ce3+的掺杂量为4％(摩尔比)时,纳米粒子的荧光强度最强,但更高的掺杂浓度将导致荧光猝灭.     

利用核壳结构实现纳米颗粒的多色上转换发光

将多色荧光标记技术应用于生物信息检测可实现快速、实时、同步大规模检测目标生物分子的目的,利用上转换纳米粒子作为多色荧光探针可有效地避免生物组织自荧光对检测信号的影响。本文制备了具有核-壳结构的稀土氟化物纳米粒子,并通过在核与壳不同位置共掺杂不同浓度的敏化离子和发光离子来改变发光离子各发射峰之间的相对强度。利用不同颜色和强度的发射光谱实现了纳米粒子的多色上转换发光。利用透射电子显微镜成像、X射线衍射分析、发光光谱等测量手段对多色上转换发光纳米粒子进行了形貌、结构和上转换发光性质的表征。实验结果表明,具有核-壳结构的纳米粒子尺寸小于30 nm,呈球形。在980 nm红外光激发下,纳米粒子呈现从红色到蓝紫色的颜色可变的上转换发光。     

壳聚糖/LaF3:Eu3+纳米复合粒子的简易合成及发光特性

在水溶液中采用化学共沉淀法制备了壳聚糖/LaF3∶Eu3+纳米复合粒子.通过透射电子显微镜(TEM),X射线衍射(XRD),傅立叶变换近红外(FT-IR)光谱对样品进行了表征.结果表明:所得纳米复合粒子大小在 20 nm左右,粒径均匀,表面包覆的壳聚糖使其易溶于水,并具备了与生物蛋白偶联的多个基团.测量了该纳米复合粒子的激发光谱与发射光谱,详细说明了各发光峰对应能级的跃迁及其发光机理,分析了不同掺杂浓度对其相对发光强度的影响.结果表明:当 Eu3+离子掺杂摩尔分数为 10%时,样品的相对发光强度达到最大值.最后介绍了壳聚糖/LaF3∶Eu3+纳米复合粒子与荧光蛋白 FITC偶联的方法,以表明其在生物学中潜在的应用价值.     

Characterization and luminescent properties of SiO2:ZnS:Mn and ZnS:Mn nanophosphors synthesized by a sol-gel method

ZnS and SiO₂-ZnS nanophosphors, with or without different concentration of Mn²⁺ activator ions, were synthesized by using a sol-gel method. Dried gels were annealed at 600 °C for 2 h. Structure, morphology and particle sizes of the samples were determined by using X-ray diffraction (XRD), highresolution transmission electron microscopy (HRTEM) and field emission scanning electron microscopy (FESEM). The diffraction peaks associated with the zincblende and the wurtzite structures of ZnS were detected from as prepared ZnS powders and additional diffraction peaks associated with ZnO were detected from the annealed powders. The particle sizes of the ZnS powders were shown to increase from 3 to 50 nm when the powders were annealed at 600 °C. An UV-Vis spectrophotometer and a 325 nm He-Cd laser were used to investigate luminescent properties of the samples in air at room temperature. The bandgap of ZnS nanoparticles estimated from the UV-Vis data was 4.1 eV. Enhanced orange photoluminescence (PL) associated with ⁴T₁→⁶A₁ transitions of Mn²⁺ was observed from as prepared ZnS:Mn²⁺and SiO₂-ZnS:Mn²⁺ powders at 600 nm when the concentration of Mn²⁺ was varied from 2-20 mol%. This emission was suppressed when the powders were annealed at 600 °C resulting in two emission peaks at 450 and 560 nm, which can be ascribed to defects emission in SiO₂ and ZnO respectively. The mechanism of light emission from Mn²⁺, the effect of varying the concentration on the PL intensity, and the effect of annealing are discussed.     

Synthesis and photoluminescence characteristics of doped ZnS nanoparticles

Free-standing powders of doped ZnS nanoparticles have been synthesized by using a chemical co-precipitation of Zn²⁺, Mn²⁺, Cu²⁺ and Cd²⁺ with sulfur ions in aqueous solution. X-ray diffraction analysis shows that the diameter of the particles is ∼2–3 nm. The unique luminescence properties, such as the strength (its intensity is about 12 times that of ZnS nanoparticles) and stability of the visible-light emission, were observed from ZnS nanoparticles co-doped with Cu²⁺ and Mn²⁺. The nanoparticles could be doped with copper and manganese during the synthesis without altering the X-ray diffraction pattern. However, doping shifts the luminescence to 520–540 nm in the case of co-doping with Cu²⁺ and Mn²⁺. Doping also results in a blue shift on the excitation wavelength. In Cd²⁺-doped ZnS nanometer-scale particles, the fluorescence spectra show a red shift in the emission wavelength (ranging from 450 nm to 620 nm). Also a relatively broad emission (ranging from blue to yellow) has been observed. The results strongly suggest that doped ZnS nanocrystals, especially two kinds of transition metal-activated ZnS nanoparticles, form a new class of luminescent materials. Received: 16 October 2000 / Accepted: 17 October 2000 / Published online: 23 May 2001     

The optical properties and energy transition process in nanocomposite of polyvinyl-pyrrolidone polymer and Mn-doped ZnS

This study has been carried out on the optical properties of polyvinyl-pyrrolidone (PVP), the energy transition process in nanocomposite of PVP capped ZnS:Mn nanocrystalline and the influence of the PVP concentration on the optical properties of the PVP capped ZnS:Mn nanocrystalline thin films synthesized by the wet chemical method. The microstructures of the samples were investigated by X-ray diffraction, the atomic absorption spectroscopy, and transmission electron microscopy. The results showed that the prepared samples belonged to the sphalerite structure with the average particle size of about 2–3 nm. The optical properties of samples are studied by measuring absorption, photoluminescence (PL) spectra and time-resolved PL spectra in the wavelength range from 200 to 700 nm at 300 K. From data of the absorption spectra, the absorption edge of PVP polymer was found about of 230 nm. The absorption edge of PVP capped ZnS:Mn nanoparticles shifted from 322 to 305 nm when the PVP concentration increases. The luminescence spectra of PVP showed a blue emission with peak maximum at 394 nm. The luminescence spectra of ZnS:Mn–PVP exhibits a blue emission with peak maximum at 437 nm and an orange–yellow emission of ion Mn²⁺ with peak maximum at 600 nm. While the PVP coating did not affect the microstructure of ZnS:Mn nanomaterial, the PL spectra of the PVP capped ZnS:Mn samples were found to be affected strongly by the PVP concentration.     

Synthesis and photoluminescent and nonlinear optical properties of manganese doped ZnS nanoparticles

In this work we synthesized ZnS:Mn²⁺ nanoparticles by chemical method using PVP (polyvinylpyrrolidone) as a capping agent in aqueous solution. The structure and optical properties of the resultant product were characterized using UV-vis optical spectroscopy, X-ray diffraction (XRD), photoluminescence (PL) and z-scan techniques. UV-vis spectra for all samples showed an excitonic peak at around 292 nm, indicating that concentration of Mn²⁺ ions does not alter the band gap of nanoparticles. XRD patterns showed that the ZnS:Mn²⁺ nanoparticles have zinc blende structure with the average crystalline sizes of about 2 nm. The room temperature photoluminescence (PL) spectrum of ZnS:Mn²⁺ exhibited an orange-red emission at 594 nm due to the ⁴T₁-⁶A₁ transition in Mn²⁺. The PL intensity increased with increase in the Mn²⁺ ion concentration. The second-order nonlinear optical properties of nanoparticles were studied using a continuous-wave (CW) He-Ne laser by z-scan technique. The nonlinear refractive indices of nanoparticles were in the order of 10⁻⁸ cm²/W with negative sign and the nonlinear absorption indices of these nanoparticles were obtained to be about 10⁻³ cm/W with positive sign.     

Surface modification and fluorescent properties of Mn2+-doped and undoped ZnS nanoparticles

Abstract

ZnS nanoparticles and Mn²⁺-doped ZnS nanoparticles were prepared by a reverse micelle reaction system. In addition, ZnS and Mn²⁺-doped ZnS nanoparticles were modified with poly(vinyl alcohol) (PVA) and 1-dodecanethiol (C₁₂H₂₅SH). The average particle size of the ZnS sample is determined around 2.3 nm by using the well-known Scherrer equation, which is in accordance with the results obtained from UV–vis and TEM analysis. Fluorescence intensity of the Mn²⁺-doped ZnS nanoparticles increases with increasing Mn²⁺ content compared with undoped ZnS nanoparticles, and coating PVA can also make fluorescence intensity increase. Different Zn²⁺/S^2- or C₁₂H₂₅SH/Zn²⁺ can affect intensity of PL emission peak and its position, which is discussed in this paper.     

Preparation and photoluminescent properties of doped nanoparticles of ZnS by solid-state reaction

Nanometer-sized Eu³⁺-doped ZnS and Mn²⁺-doped ZnS particles were prepared by solid-state method at low temperature. The structures and properties of those materials were characterized by X-ray diffraction (XRD) and photoluminescent spectroscopy techniques. The XRD patterns reveal that the doped ZnS nanoparticles belong to zinc-blende structure. The concentration of doping ions has little effect on the sizes of the doped ZnS nanoparticles, which mainly depends on the temperature of preparation. The emission peaks from the ⁵D₀→⁷F_J (J=1, 2, and 4) electronic energy transitions of Eu³⁺ were observed in the emission spectra of the ZnS:Eu³⁺ nanoparticles. The intensity ratio of the two peaks from the ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transitions indicates that more Eu³⁺ ions occupy the sites with no inversion symmetry. For the ZnS:Mn²⁺ nanoparticles, an orange emission from the ⁴T₁→⁶A₁ transition of Mn²⁺ is present, indicating that the doping ions occupy the positions of the ZnS lattices. Meanwhile, UV-induced luminescence enhancement was observed for the ZnS:Mn²⁺ nanoparticles, the possible reason of which is discussed primarily.     

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     

Synthesis of high quality and monodisperse CdS:Mn/ZnS and CdS:Mn/CdS core–shell nanoparticles

CdS:Mn²⁺/ZnS and CdS:Mn²⁺/CdS core–shell nanoparticles were synthesized in aqueous medium via chemical precipitation method in an ambient atmosphere. Polyvinylpyrrolidone (PVP) was used as a capping agent. The effect of the shell (ZnS and CdS) thickness on CdS:Mn²⁺ nanoparticles was investigated. Inorganically passivated core/shell nanocrystals having a core (CdS:Mn²⁺) diameter of 4 nm and a ZnS-shell thickness of ∼0.5 nm exhibited improved PL intensity. Optimum concentration of doping ions (Mn²⁺) was selected through optical study. For all the core–shell samples two emission peaks were observed, the first one is band edge emission in the lower wavelength side due to energy transfer to the Mn²⁺ ions in the crystal lattice; the second emission is characteristic peak of Mn²⁺ ions (⁴T₁ → ⁶A₁). The XRD, TEM and PL results showed that the synthesized core–shell particles were of high quality and monodisperse.     

Synthesis and photoluminescence of water-soluble Mn-doped ZnS quantum dots

The water-soluble Mn²⁺-doped ZnS quantum dots (Mn:ZnS d-dots) were synthesized by using thioglycolic acid (TGA) as stabilizer in aqueous solutions in air, and characterized by X-ray powder diffraction (XRD), UV-vis absorption spectra and photoluminescence (PL) emission spectroscopy. The sizes of Mn:ZnS d-dots were determined to be about 2 nm using XRD measurements and the UV-vis absorption spectra. It was found that the Mn²⁺⁴T₁ → ⁶A₁ emission intensity of Mn:ZnS d-dots significantly increased with the increase of Mn²⁺ concentration, and showed a maximum when Mn²⁺ doping content was 1.5%. If Mn²⁺ concentration continued to increase, namely more than 1.5%, the Mn²⁺⁴T₁ → ⁶A₁ emission intensity would decrease. In addition, the effects of TGA/(Zn + Mn) molar ratio on PL were investigated. It was found that the peak intensity ratio of Mn²⁺⁴T₁ → ⁶A₁ emission to defect-states emission showed a maximum when the TGA/(Zn + Mn) molar ratio was equal to 1.8.     

Synthesis, characterization and optical properties of water-soluble ZnS:Mn nanoparticles

ZnS nanoparticles with Mn²⁺ doping (0.5-20%) have been prepared through a simple chemical method, namely the chemical precipitation method. The structure of the nanoparticles has been analyzed using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM) and UV-vis spectrometer. The size of the particles is found to be 3-5 nm range. Photoluminescence spectra were recorded for undoped ZnS nanoparticles using an excitation wavelength of 320 nm, exhibiting an emission peak centered at around 445 nm. However, from the Mn²⁺-doped samples, a yellow-orange emission from the Mn²⁺⁴T₁-⁶A₁ transition is observed along with the blue emission. The prepared Mn²⁺-doped sample shows efficient emission of yellow-orange light with the peak emission 580 nm with the blue emission suppressed. The maximum PL intensity is observed only at the excitation energy of 3.88 eV (320 nm). Increase in stabilizing time up to 48 h in de-ionized water yields the enhancement of emission intensity of doped (4% Mn²⁺) ZnS. The correlation made through the concentration of Mn²⁺ versus PL intensity resulted in opposite trend (mirror image) of blue and yellow emissions.