微波辅助合成ZnS∶Ce纳米晶

以乙酸锌为锌源、硫酸高铈为铈源、硫代乙酰胺为硫源、淀粉为分散剂,微波辅助合成了ZnS∶Ce纳米晶。通过X射线衍射仪、红外光谱仪、荧光分光光度计和激光粒度分析仪对其物相结构、原子键价结构、光学性能和颗粒粒径大小进行了表征分析。研究了不同Ce离子掺杂量对产品结构和光学性能的影响。结果表明:所制备的ZnS∶Ce纳米晶体具有闪锌矿立方相结构,其晶粒大小分布范围为3.5~4.5nm;颗粒大小范围为100~600nm,D50=290nm。激发波长为230nm时,其荧光发射峰在408nm处;掺杂Ce离子浓度增加,ZnS∶Ce纳米晶材料的荧光强度降低,其原因是发生了浓度淬灭现象。     

Mn~(2+)掺杂水溶性ZnS量子点的制备及其光致发光性能

采用共沉淀法,在3-巯基丙酸(MPA)为表面修饰剂下,成功制备出Mn2+掺杂水溶性ZnS量子点。利用X射线衍射仪、透射电子显微镜、紫外-可见吸收光谱仪和荧光分光光度计等表征方法研究了Mn2+掺杂剂及掺杂量对ZnS量子点的晶体结构、形貌和发光性能等的影响。结果表明,所得产物为ZnS立方型闪锌矿结构,样品呈不规则球形,粒径主要集中在9.7nm左右;在320nm激发下,Mn2+掺杂ZnS量子点出现两个发射波峰,分别位于587和637nm处,其中587nm处的发射波峰为ZnS表面态缺陷发光,而637nm处的发射波峰则属于Mn2+∶4T1-6A1能级特征发光。同时,利用红外吸收光谱对Mn2+掺杂水溶性ZnS量子点的形成机理进行了初步探讨。     

Mn∶ZnS胶体纳米晶的结构及光谱性质研究

利用一种绿色的合成工艺,采用巯基乙酸作为配体,在水溶液中成功合成了水溶性的Mn∶ZnS纳米晶,并研究了掺杂浓度对Mn∶ZnS纳米晶的结构及光谱性质的影响。XRD结果表明,合成的Mn∶ZnS纳米晶呈立方闪锌矿结构,通过谢乐公式估算的样品的平均晶粒尺寸约为2.1nm;随着掺杂浓度的增加,产物的晶胞参数逐渐减小,表明Mn离子已经掺入到ZnS纳米晶中,该发现与EDX结果相吻合。FT-IR光谱发现,配体巯基乙酸成功包覆在纳米晶的表面。Raman图谱进一步证实,Mn∶ZnS纳米晶为立方闪锌矿结构。UV-Vis吸收谱表明,不同掺杂浓度Mn∶ZnS纳米晶的吸收峰均随粒径的减小向短波长方向移动,通过吸收峰计算的纳米晶平均粒径为2.3nm。     

ZnS∶Mn转光粉的制备及性能研究

通过溶剂热法制备了不同锰离子掺杂量的硫化锌粉体转光剂,并利用SEM、XRD和荧光分光光度计对其形貌、组分、结构及发光性能进行了研究。结果显示,锰离子的掺入影响了硫化锌粉体的粒径,出现晶粒细化的现象。以紫外光作为激发光源,当锰的初始浓度不高于20%时,样品的发光峰通过高斯分峰可分为2个,分别位于465～475nm和570～585nm处;当锰的初始浓度高于20%时,硫化锌的发光峰消失,只出现锰的发光峰(580nm左右),即得到了预期的红色发光。     

α-ZnS:Mn纳米荧光粉热分解法制备及其发光性能

以Zn(NO3)2·6H2O(硝酸锌)、Mn(NO3)2·3H2O(硝酸锰)和Ddtc·3H2O(二乙基二硫代氨基甲酸钠)为原料,制得含硫金属有机配合物。将含硫金属有机配合物在不同反应溶液中,于200℃进行热解,制备了ZnS∶Mn纳米荧光粉。结果表明,样品为六方晶系的高温相α-ZnS∶Mn。在二甘醇加5mL油酸反应溶液中制得的ZnS∶Mn纳米材料紫外吸收峰最高,粒径更小。在323nm光激发下,看到了Mn2+的橘黄色发射峰(585nm)和ZnS的蓝色发射峰(450nm),随着Mn2+离子掺杂量增加,585nm发光强度先增加后减小,掺杂量为4%时达到最大值,而450nm发光强度变化与此相反。     

制备条件对ZnS∶Mn纳米晶晶体结构和发光性质的影响

以乙二胺和水为溶剂,采用溶剂热法制备了Mn离子掺杂的ZnS纳米晶,探讨了反应温度、掺杂离子浓度及锌硫比对ZnS:Mn纳米晶晶体结构和发光性质的影响.采用X射线衍射、荧光光谱等手段进行了表征,结果表明,反应温度高于180℃时才会生成纯硫化锌,而调整锌硫比,会得到不同晶型的硫化锌,Mn离子掺杂浓度则对硫化锌的生成和晶型无明显影响,对发光强度有一定影响.在220℃、锌硫比为1:1、Mn离子掺杂浓度为1%的条件下制备的硫化锌纳米晶具有比较好的发光性质.     

Mn掺杂TiO_2负载竹质活性炭纤维的制备及可见光光催化性能研究

采用溶胶-凝胶法和浸渍法制备Mn掺杂TiO2负载竹质活性炭纤维(Mn/Ti-BACF)光催化复合材料,利用扫面电镜(SEM)、X射线衍射仪(XRD)、傅立叶变换红外光谱(FT-IR)、紫外-可见光分光光度计(UV-Vis)等考察了Mn掺杂量对Mn/Ti-BACF复合材料结构和可见光光催化性能的影响。结果发现,Mn掺杂改善了TiO2在竹质活性炭纤维表面的负载;Mn离子的掺杂并没有改变样品基材的碳网结构,也未出现新的Mn—O的特征吸收峰。随着Mn掺杂浓度的增加,Mn/Ti-BACF样品中TiO2粒径逐渐减小,可见光下的吸光度先增加后减少。当n(Mn)∶n(Ti)=1∶200时,样品在可见光下对亚甲基蓝的降解率达到了97.7%。     

制备条件对ZnS：Mn纳米晶晶体结构和发光性质的影响

以乙二胺和水为溶剂,采用溶剂热法制备了Mn离子掺杂的ZnS纳米晶,探讨了反应温度、掺杂离子浓度及锌硫比对ZnS：Mn纳米晶晶体结构和发光性质的影响。采用X射线衍射、荧光光谱等手段进行了表征,结果表明,反应温度高于180℃时才会生成纯硫化锌,而调整锌硫比,会得到不同晶型的硫化锌,Mn离子掺杂浓度则对硫化锌的生成和晶型无明显影响,对发光强度有一定影响。在220℃、锌硫比为1：1、Mn离子掺杂浓度为1%的条件下制备的硫化锌纳米晶具有比较好的发光性质。     

Mn,Cu掺杂对ZnS∶Mn,Cu电致发光材料亮度的影响

采用水热法制备了ZnS∶Mn,Cu电致发光材料,利用透射电镜对发光材料的结构和形貌进行表征,并且探讨了Cu2+、Mn2+掺杂量和反应温度对ZnS∶Mn,Cu发光材料亮度的影响。结果显示,随着Cu2+、Mn2+掺杂量的增加,发光材料的亮度也随之增加,但对于Cu2+、Mn2+掺杂都存在最佳值,当Cu2+掺杂量0.2%,Mn2+掺杂量4%,温度150℃时,得到的电致发光材料亮度较高,粒径约10nm左右。     

Co2+掺杂水溶性ZnS量子点的制备及其光致发光性能

采用共沉淀法,以3-巯基丙酸为表面修饰剂,成功制备出Co2+掺杂水溶性ZnS量子点。采用X射线衍射仪、透射电子显微镜、原子发射光谱仪、紫外-可见吸收光谱仪和荧光分光光度计等,研究了Co2+掺杂剂及掺杂量对ZnS量子点的晶体结构、形貌和发光性能等的影响。结果表明:所得产物均为ZnS立方型闪锌矿结构,量子点呈不规则球形,粒径主要集中在5.2 nm左右;掺杂样品发红色荧光,发光性能明显增强,属于Co2+形成的杂质能级(4A1—4T1)与缺陷的复合发光。同时,利用红外吸收光谱对Co2+掺杂水溶性ZnS量子点的形成机理进行了初步探讨。     

Photoluminescent properties of ZnS:Mn nanoparticles with in-built surfactant

Mn-doped ZnS nanoparticles, having average diameter 3–5 nm, have been synthesized using chemical precipitation technique without using any external capping agent. Zinc blende crystal structure has been confirmed using the X-ray diffraction studies. The effect of various concentrations of Mn doping on the photoluminescent properties of ZnS nanoparticles has been studied. The time-resolved photoluminescence spectra of the ZnS:Mn quantum dots have been recorded and various parameters like lifetimes, trap depths, and decay constant have been calculated from the decay curves at room temperature. The band gap was calculated using UV–Visible absorption spectra.     

Syntheses and applications of Mn-doped II-VI semiconductor nanocrystals

Luminescent Mn-doped II-VI semiconductor nanocrystals have been intensively investigated over the last ten years. Several semiconductor host materials such as ZnS, CdS, and ZnSe have been used for Mn-doped nanocrystals with different synthetic routes and surface passivation. Beyond studies of their fundamental properties including photoluminescence and size, these luminescent nanocrystals have now been tested for practical applications such as electroluminescent displays and biological labeling agents (biomarkers). Here, we first review ZnS:Mn, CdS:Mn/ZnS core/shell, and ZnSe:Mn nanocrystal systems in terms of their synthetic chemistries and photoluminescent properties. Second, based on ZnS:Mn and CdS:Mn/ZnS core/shell nanocrystals as electroluminescent components, direct current electroluminescent devices having a hybrid organic/inorganic multilayer structure are reviewed. Highly luminescent and photostable CdS:Mn/ZnS nanocrystals can further be used as the luminescent biomarkers and some preliminary results are also discussed here.     

A facile and fast approach for the synthesis of doped nanoparticles using a microfluidic device

The microfluidic approach emerges as a new and promising technology for the synthesis of nanomaterials. A microreactor allows a variety of reaction conditions to be quickly scanned without consuming large amounts of raw material. In this study, we investigated the synthesis of water soluble 1-thioglycerol-capped Mn-doped ZnS nanocrystalline semiconductor nanoparticles (TG-capped ZnS:Mn) via a microfluidic approach. This is the first report for the successful doping of Mn in a ZnS semiconductor at room temperature as well as at 80?°C using a microreactor. Transmission electron microscopy and x-ray diffraction analysis show that the average particle size of Mn-doped ZnS nanoparticles is ～3.0?nm with a zinc-blende structure. Photoluminescence, x-ray photoelectron spectroscopy, atomic absorption spectroscopy and electron paramagnetic resonance studies were carried out to confirm that the Mn(2+) dopants are present in the ZnS nanoparticles.     

Synthesis and luminescence properties of ZnS:Mn/ZnS core/shell nanorod structures

Mn-doped ZnS nanorods synthesized by solvothermal method were successfully coated with ZnS shells of various thicknesses. The powder X-ray diffraction (XRD) measurements showed the ZnS:Mn nanorods were wurtzite structure with preferential orientation along c-axis. Transmission electron microscopy images (TEM) revealed that the ZnS shells formed from small particles, growing along a-axis orientation, which was proved by the XRD measurements. Room temperature photoluminescence (PL) spectra showed that the intensity of Mn emission first increased and then decreased with the thickening of the ZnS shells. The effects of ZnS shells on the luminescence properties of ZnS:Mn nanorods is discussed.     

化学合成法制备ZnS基纳米荧光粉研究

描述了一种生产ZnS:M[M=Mn,Cu,Cu(Al)]纳米荧光粉的化学合成方法.运用本方法通过调节巯基乙酸与甲基丙烯酸的摩尔比,可在1.8～3.0nm范围内控制纳米粒子的尺寸.选择面积的电子衍射和X射线衍射证明ZnS:M纳米荧光粉具有闪锌矿结构.透射电镜图像表明ZnS:M纳米荧光粉具有较好的尺寸分布.ZnS:Mn的PL谱表明纳米尺寸的ZnS:Mn与体材料相比具有较高的发光效率。     

The light emission properties of ZnS:Mn nanoparticles

ZnS and Mn-doped ZnS nanoparticles were synthesized via a simple hydrothermal synthesis method. The former emits super bright blue fluorescence light while the latter exhibits super-bright yellow light under a fluorescence microscope. Accordingly, their photoluminescence peaks are located at 420 nm and 580 nm in the spectra excited with 281 nm and 335 nm wavelengths, respectively. The super-bright ZnS:Mn nanoparticles can be used as a yellow fluorescence powder in making LED and plat display, and can be used as biological fluorescence probe to replace CdSe, CdS quantum dos without any damage to mankind and environment.     

Effect of magnesium on the performance characteristics of ZnS:Cu,Mn phosphors

We have studied the effect of magnesium added to the starting mixture as MgS or MgCl₂ on the performance characteristics of synthesized ZnS:Cu,Mn phosphor powders. It has been shown that the incorporation of certain amounts of magnesium into the ZnS:Cu,Mn phosphor leads to an increase in photo- and electroluminescence brightness and is favorable for Mn incorporation into the structure of the phosphor. In particular, additional doping of a dc electroluminescent ZnS:Cu,Mn phosphor with 30 mol % Mg ensured not only a shift of its luminescence spectrum to shorter wavelengths, thereby extending the color range of light sources, but also a twofold increase in its brightness.     

Optical properties of Mn-doped ZnS semiconductor nanoclusters synthesized by a hydrothermal process

Undoped and Mn-doped ZnS nanoclusters have been synthesized by a hydrothermal approach. Various samples of the ZnS:Mn with 0.5, 1, 3, 10 and 20 at.% Mn dopant have been prepared and characterized using X-ray diffraction, energy-dispersive analysis of X-ray, high resolution electron microscopy, UV-vis diffusion reflection, photoluminescence (PL) and photoluminescence excitation (PLE) measurements. All the prepared ZnS nanoclusters possess cubic sphalerite crystal structure with lattice constant a = 5.408 ± 0.011 ?. The PL spectra of Mn-doped ZnS nanoclusters at room temperature exhibit both the 495 nm blue defect-related emission and the 587 nm orange Mn²⁺ emission. Furthermore, the blue emission is dominant at low temperatures; meanwhile the orange emission is dominant at room temperature. The Mn²⁺ ion-related PL can be excited both at energies near the band-edge of ZnS host (the UV region) and at energies corresponding to the Mn²⁺ ion own excited states (the visible region). An energy schema for the Mn-doped ZnS nanoclusters is proposed to interpret the photoluminescence behaviour.     

Multicolor luminescence from transition metal ion (Mn2+ and Cu2+) doped ZnS nanoparticles

Mn and Cu doped ZnS nanoparticles in powder form were prepared by a simple solvothermal route. Particle size and crystal structure of the products were investigated through X-ray diffraction study revealing the formation of cubic ZnS nanoparticles of average diameter 2.5 nm. Particle size was also verified by the high resolution transmission electron microscopic images. Blue emission at approximately 445 nm was observed from the undoped sample, which was attributed to the presence of large surface defects. With increasing doping concentration the defect related emission gradually quenches and subsequently the impurity related emissions appeared. Mn doped samples exhibited orange emission at approximately 580 nm which may be attributed to the transition between (4)T1 and (6)A1 energy levels of the Mn2+ 3d states. Whereas, the Cu doped ZnS nanoparticles exhibited a red shifted strong blue emission at approximately 466 nm which is attributed to the transition of the electrons from the surface states to the 't2' levels of Cu impurities.     

Paramagnetic nature of Mn doped ZnS nano particles in opto electronic device application

Manganese (Mn²⁺) doped ZnS nano sized powder was prepared by co precipitation method with different concentration from 1 to 5 %. The X-ray diffraction pattern indicates that the prepared powders are in cubic structure with the crystallite sizes lie in the range of 10–12 nm. Diffuse reflectance studies enlightens that an increment in the band gap (3.38–3.55 eV) with increasing dopant. The morphology and size of the sample could be intuitively determined by field emission scanning electron microscope and it shows that ZnS and Mn doped ZnS nanoparticles are appeared as spherical shape. The replacement of Zn by Mn is confirmed by energy dispersive analysis. TEM images confirm the spherical shape of the nanoparticles and SAED images exhibit the crystalline nature and confirm the cubic nature of the synthesized samples. The prepared luminescent nanoparticles of Mn doped ZnS have emission peak at around 617 nm. The symmetry and electronic structure of the Mn doped samples are studied with electron paramagnetic resonance.The paramagnetic nature of Mn doped ZnS nano particles are validated by using vibrating sample magnetometer spectra at room temperature. Thermal analysis measurement of the samples shows that the thermal stability of Mn doped ZnS is higher than the undoped ZnS. This corroborates that ZnS:Mn doping is attributed to the removal of water and it enhanced the crystallinity.