核壳结构CdS：Mn/ZnS纳米晶的制备与光学性能研究

以3-巯基丙酸为稳定剂,采用共沉淀法在水相中合成了CdS∶Mn掺杂纳米晶,然后进一步将ZnS包覆于CdS∶Mn纳米晶表面,制备了CdS∶Mn/ZnS核壳结构纳米晶。利用X射线衍射（XRD）,透射电子显微镜（TEM）和紫外-可见吸收光谱（UV-Vis）对纳米晶的结构、形貌和光学性质进行了表征,发现制备的纳米晶具有优秀的单分散性,确认合成了CdS∶Mn/ZnS核壳结构纳米晶。通过荧光光谱（PL）研究了纳米晶的发光性质和光稳定性,结果表明包覆壳层后纳米晶的发光强度显著提高,最高可达8倍,且Mn2＋离子的发光峰峰位置随着ZnS壳层数的增加而红移。此外,核壳纳米晶的光稳定性大大提高。     

水热法制备ZnS∶Cu纳米晶及其光致发光性能

采用水热法制备了不同掺杂浓度的ZnS∶Cu(0~0.6%(原子分数))纳米晶。结果表明,ZnS∶Cu纳米晶为立方晶系闪锌矿结构,晶粒尺寸在3~4nm之间;相比未掺杂的ZnS纳米晶,掺杂ZnS∶Cu纳米晶在500nm处产生了发射光谱(PL)。这是由于发光中心位于446和468nm两个PL光谱与ZnS自身的缺陷有关,发光中心位于500nm的绿光为浅施主能级(S缺陷)与铜t2能级之间跃迁而产生。并且其发光强度随掺杂浓度显著增强,当浓度为0.4%(原子分数)时达到最大值,进而发生了浓度淬灭现象。     

不同壳层的CdS／ZnS核／壳结构量子点的温度相关荧光性质

报导了CdS／ZnS纳米晶体（NCs）的制备过程和其光学}生质。通过采用连续离子层吸附和反应技术（SILAR）,我们用少量的表面活性剂合成了不同壳层的四个样品,包括CdS核纳米晶以及具有1～3层ZnS壳的CdS／ZnS核／壳结构纳米晶体样品。发现具有一层ZnS壳的CdS／ZnS样品的荧光量子产率大约比未包覆壳层的CdS纳米晶体样品的强11倍。另外,随着壳层的增加（增至两到三层）,荧光量子产率呈现下降的趋势。对样品进行了温度相关的光谱测量,发现CdS／ZnS和CdS一样具有特殊的光学特性。     

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。     

Fe掺杂ZnS半导体纳米晶的微乳液法制备及其性能研究

采用Span 80/Tween 80/cyclohexane/wa-ter微乳液体系合成了ZnS∶Fe纳米晶,分别利用XRD、TEM、荧光光谱对其相结构、形貌及光学性能进行了研究。结果表明合成的ZnS∶Fe纳米晶为球形,平均粒度约3nm。随着Fe离子掺杂浓度的增加,发光峰强度先增大后减小,浓度为1%的时候发光峰强最大。对ZnS∶Fe纳米晶的荧光衰减曲线进行测试并计算得到其荧光寿命为3.07ns。     

复合结构纳米晶CdS：Cu/CdS的制备及光学特性

在非配位溶剂中合成了高质量的CdS纳米晶核,并利用Cu2+离子对其进行掺杂,制备了CdS:Cu纳米晶.通过进一步采用连续离子层吸附反应的方法对CdS:Cu纳米晶进行表面修饰,得到CdS:Cu/CdS复合结构纳米晶.利用X射线衍射(XRD),透射电镜(TEM),紫外可见吸收光谱(UV-Vis)和荧光光谱(PL)对其结构、形貌以及光学性质进行了表征和分析,结果表明:所制备的复合结构CdS:Cu/CdS纳米晶为立方闪锌矿结构;与CdS纳米晶核相比,掺杂Cu2+可以使其表面态发光发生红移;在CdS:Cu纳米晶中,通过改变掺杂Cu2+的浓度,可以实现表面态发光在570和620nm之间的连续调节.与未经包覆的CdS:Cu纳米晶相比,包覆层CdS增强了纳米晶CdS:Cu的稳定性.     

基于ZnS纳米材料的生物分子检测

利用三种发光波长的ZnS基纳米材料（ZnS、ZnS：Cu和ZnS：Mn）作为荧光标记物进行人免疫球蛋白（IgG）分子的免疫检测,X射线衍射（XRD）表明,过渡金属离子掺杂会导致ZnS纳米晶的结晶化尺寸减小;荧光光谱显示,ZnS、ZnS：Cu和ZnS：Mn纳米材料的发光波长分别为430nm、560nm和590nm。利用羊抗人IgG作为捕获抗体,分别制备免疫检测金基底和ZnS基荧光探针,分别进行空白实验、加入待测物人IgG实验,表明具有很好的检测选择性。     

水溶性纤维素醚/Eu(Ⅲ)的合成及发光特性

合成了具有发光性能的水溶性纤维素醚/Eu（Ⅲ）的配合物,即羧甲基纤维素（CMC）/Eu（Ⅲ）、甲基纤维素（MC）/Eu（Ⅲ）和羟乙基纤维素（HEC）/Eu（Ⅲ）,讨论了这些配合物的结构,并由FTIR加以证实.这些配合物的发射光谱为Eu（Ⅲ）在615nm处的电偶极跃迁（由5D0→7F2）所产生.CMC的取代度对CMC/Eu（Ⅲ）的荧光光谱和强度都产生影响.Eu（Ⅲ）含量也对配合物的荧光强度产生影响,当Eu（Ⅲ）含量为5%（质量比）时,这些水溶性纤维素醚/Eu（Ⅲ）配合物的荧光强度均达到最大.     

基于大分子配体修饰的Cd~(2+)、Mn~(2+)掺杂功能化ZnS纳米晶的制备与表征

以醋酸锌、氯化镉、醋酸锰和硫化钠为原料,采用末端带双键的聚甲基丙烯酸(PMAA)大分子单体为配体,在水溶液中成功制备出分散均匀并具有良好荧光性的Cd2+和Mn2+掺杂复合的ZnS纳米晶.利用电导率分析、TGA、Uv-vis、荧光光谱(PL)等表征手段考察了复合纳米晶结构和光学性能的关系.结果表明,PMAA中的大量羧基是以配位键的形式和纳米晶表面金属原子相结合.通过改变掺入的Cd2+的含量,能够获得从紫外光到可见光范围的ZnS:Cd2+复合纳米晶材料.     

复合结构纳米晶CdS∶Cu/CdS的制备及光学特性

在非配位溶剂中合成了高质量的CdS纳米晶核,并利用Cu²⁺离子对其进行掺杂,制备了CdS∶Cu纳米晶.通过进一步采用连续离子层吸附反应的方法对CdS∶Cu纳米晶进行表面修饰,得到CdS∶Cu/CdS复合结构纳米晶.利用X射线衍射(XRD),透射电镜(TEM),紫外可见吸收光谱(UV-Vis)和荧光光谱(PL)对其结构、形貌以及光学性质进行了表征和分析,结果表明:所制备的复合结构CdS∶Cu/CdS纳米晶为立方闪锌矿结构;与CdS纳米晶核相比,掺杂Cu²⁺可以使其表面态发光发生红移;在CdS∶Cu纳米晶中,通过改变掺杂Cu²⁺的浓度,可以实现表面态发光在570和620nm之间的连续调节.与未经包覆的CdS∶Cu纳米晶相比,包覆层CdS增强了纳米晶CdS∶Cu的稳定性.     

Synthesis and characterization of ZnS:Mn2+ nano-particles for white-light emitting

The sol-gel method was used to obtain a kind of white-light emitting ZnS:Mn2+ nanoparticles capped by methacrylic acid with an average particle size of approximately 7 nm. The photoluminescence spectra, X-ray diffraction spectra, Fourier transform infrared reflection spectra and ultraviolet absorption spectra were used to measure their optical properties and crystal structures. The ZnS:Mn2+ nanoparticles with 0.58 wt% Mn2+ concentration emitted white light when excited by 380 nm. The PL spectrum exhibits two emission peaks under irradiation: one at 480 nm generated from the ZnS matrix, and one at 590 nm emitted by the doped Mn2+ ions. The nanoparticles will only emit white light with the optimum Mn2+ concentration (0.58 wt%). X-ray diffraction demonstrates the synthesized ZnS:Mn2+ nanoparticles have zinc blend crystal structure, and the infrared patterns of the capped ZnS:Mn2+ nanoparticles and methacrylic acid are comparable, indicating that the methacrylic polymer has capped or modified ZnS:Mn2+ nanoparticles.     

One-step and rapid synthesis of composition-tunable and water-soluble ZnCdS quantum dots

ZnCdS quantum dots have been successfully prepared at room temperature in aqueous solution with sodium hexametaphosphate as stabilizer and thioacetamide as the source of S. The photoluminescence (PL) spectra and UV-Vis absorption spectra of the ZnCdS quantum dots were determined on the basis of the initial Cd/Zn mole ratio (Cd/Zn = 8/0, 7/1, 6/2, 5/3, 4/4, 3/5, 2/6, 1/7 and 0/8) and the concentration of thioacetamide. The emission peaks first showed a red shift and then a blue shift with the increasing initial Zn concentration, which provided the evidence of formation of CdS/ZnCdS core/shell and ZnCdS alloyed quantum dots. The ZnCdS quantum dots were compared with CdS (ZnS) quantum dots doped with Zn2+ (Cd2+). The samples have also been characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectra (XPS).     

Synthesis and optoelectrochemical properties of ZnS:Mn nanocrystals

Mn2+ ions doped ZnS semiconductor nanocrystals (ZnS:Mn NCs) were synthesized using colloidal chemical method at 70 degrees C without any capping agents. The as-prepared undoped ZnS and ZnS:Mn NCs were characterized by UV-Vis absorption spectra, fluorescent emission spectra, X-ray powder diffraction (XRD), inductively coupled plasma analysis (ICP), X-ray photoelectron spectroscopy (XPS), Dynamic light scattering (DLS), cyclic voltammogram and electronic transmission microscopy (TEM). The dependence of photoluminescence of ZnS:Mn NCs on dopant concentration was studied. The results show that Mn2+ ions mainly stay at ZnS nanocystal surface, and Mn2+-surface defect state complex was formed, as a result of which, surface defect emission of ZnS nanocrystals was substituted with Mn2+-related PL emission. The strongest fluorescent emission intensity was obtain at 1.85 at% Mn2+ doped ZnS:Mn NCs. The Mn2+ doped ZnS:Mn NCs are of 5 nm in diameter. The emission peak at 575 nm is attributed to d-d (4T1 --> 6A1) transition of Mn2+ ions. The existence of Mn2+-related photoluminescence could be well correlated with cyclic voltammogram of Mn2+-doped NCs, where pair of oxidation and reduction peaks were clearly observed due to the doped Mn2+ ions. The adsorbed Mn2+ ions on ZnS NCs produced neither Mn2+ emission nor redox peaks. For heavily doped ZnS:Mn NCs (4.87 at%), redox peaks gap in cyclic voltammogram became larger and new oxidation peak appeared. Correspondingly, when the Mn2+ doping concentration reached 4.87 at%, the Mn2+-related emission totally disappears due to the Mn-Mn interactions. This work implys that electrochemical technique is possibly an useful tool to probe the local structure of doped Mn2+ ions.     

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.     

Hydrothermal synthesis and luminescent properties of microtubes constructed by fluffy Zns:Mn2+ with nanostructures

Tubular micrometer-sized ZnS:Mn2+ constructed by fluffy nanostructures were fabricated in the mixed solutions of water and ethanol in a fixed volume ratio with the aid of ethylenediamine. In the X-ray diffraction pattern, the products obtained in the presence and absence of ethylenediamine show the wurtzite and sphalerite phases, respectively. Field-emission scanning electron microscopic images reveal the evolution process from nanowires to fluffy ZnS:Mn2+ to microtubes with the reaction times of 2, 4, and 8 hours at 100 degrees C, and the basal nanowires are below 10 nm in diameter. Photoluminescence and photoluminescence excitation spectra were investigated. The results suggest that the wurtzite phase, instead of the sphalerite phase ZnS:Mn2+ is luminescence-active for the 4T1 -6A1 transition of the Mn2+ in the ZnS host. The excitation spectra monitored at orange emission bands exhibit sharp peaks at 320, 326 and 327 nm with increasing reaction times of 2, 4, and 8 hours, respectively, indicating the energy transfer from ZnS host to Mn2+ ions, and the blue-shifts compared with the band gap absorption of the bulk counterpart (344 nm) are also observed due to the quantum confinement effects. The formation mechanism of the wurtzite one-dimensional nanostructures at such a low temperature is proposed based on a molecular template mechanism involving the bidentate coordinating ligand, ethylenediamine, and the possible formation mechanism of novel tubular structure are also discussed.     

沉淀法制备ZnS∶Cr纳米晶及其光学性能研究

以十二烷基苯磺酸钠和六偏磷酸钠作为分散剂,采用沉淀法制备了ZnS及不同掺杂浓度的ZnS∶Cr纳米晶。利用XRD和TEM对纳米晶物相和形貌进行了分析。结果表明,ZnS和ZnS∶Cr纳米晶均为立方闪锌矿结构,利用谢乐公式估算ZnS和ZnS∶Cr纳米晶平均粒径分别为2.1和2.2nm。TEM观察到纳米晶近似为球形,平均粒度为3nm左右,具有较好的单分散性且分布均匀。荧光光谱(PL)表明,纳米晶在420、440和495nm处有发射谱带,前两者被认为是S空位深陷阱发光,后者被认为是表面态或中心辐射复合发光。     

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.     

Luminescence properties of nano-crystalline Ba3MgSi2O8:Eu2+, Mn2+ phosphors

Ba3MgSi2O8:Eu2+, Mn2+ phosphors were synthesized by the sol-gel method and high temperature solid-state reaction method, respectively. XRD (X-ray diffraction), FT-IR (Fourier transform infrared spectroscopy), PL (photoluminescence spectra), and PLE (photoluminescence excitation spectra) were measured to characterize the samples. Emission and excitation spectra of our Ba3MgSi2O8:Eu2+, Mn2+ phosphors monitored at 441, 515, and 614 nm are depicted in the paper. The emission intensities of 441 and 515 nm emission bands increase with increasing Eu2+ concentration, while the peak intensity of the 614 nm band increases with increasing Mn2+ concentration. We conclude that the 515 nm emission band is attributed to the 4f(6)5d transition of Eu2+ ions substituted by Ba2+ sites in Ba2SiO4. The 441 nm emission band originates from Eu2+ ions, while the 614 nm emission band originates from Mn2+ ions of Ba3MgSi2O8:Eu2+, Mn2+. Nano-crystalline Ba3MgSi2O8:Eu2+, Mn2+ phosphors prepared by the sol-gel method show higher color rendering and better color temperature in comparison with the samples prepared by high temperature solid-state reaction method.     

CdSe胶质量子点的电致发光特性研究

采用胶体化学法合成硒化镉(CdSe)胶质量子点, 在此基础上制成了以CdSe胶质量子点为有源层, 结构为ITO/ZnS/CdSe/ZnS/Al的电致发光(EL)器件. 透射电镜测量表明量子点的尺寸为4.3 nm, 扫描电子显微镜测量ZnS薄膜和Al薄膜结果显示表面均较为平整, 由器件结构的X射线衍射分析观察到了CdSe(111)、ZnS(111)等晶面的衍射, 表明器件中包含了CdSe量子点和ZnS绝缘层材料. 光致发光谱表征胶质量子点的室温发光峰位于614 nm, 电致发光测量得到器件在室温下的发光波长位于450 ~ 850 nm, 峰值在800 nm附近. 本文对电致发光机制及其与光致发光谱的区别进行了讨论.     

低温水热法制备ZnS:Co+Cr纳米晶及其光学性能研究

采用低温水热法制备出3-巯基丙酸(MPA)修饰的ZnS:Co+Cr纳米晶. 利用X射线衍射仪、粒度分析仪、透射电镜、紫外-可见分光光度计、荧光分光光度计和XPS能谱仪等对ZnS:Co+Cr纳米晶的结构、形貌、粒径分布和发光性能进行了表征. 结果表明: 合成的ZnS:Co+Cr纳米晶有较好的单分散性, 平均粒径为9.3 nm, 均为立方闪锌矿结构; ZnS:Co+Cr纳米晶的吸收边位于320 nm处, 并在728 nm处出现Co²⁺的特征吸收峰; 当Cr²⁺浓度为0.75at%, 水热反应温度为160℃时, ZnS:Co+Cr纳米晶PL峰最强; XPS能谱表明Cr²⁺部分被氧化成Cr³⁺。