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。     

核壳结构CdS/ZnS荧光量子点的制备与荧光性能研究

以氧化镉为镉源、硫单质为硫源、油酸为配体、在十八烯体系中合成单分散的CdS纳米颗粒,研究了配体浓度对纳米微粒的生长动力学、颗粒尺寸分布的影响.采用乙基黄原酸锌作为Zn、S源的反应前体,采用逐滴滴加的方法制备了具有核壳结构的CdS/ZnS量子点,吸收光谱和荧光光谱表明CdS/ZnS纳米粒子比单一的CdS纳米粒子具有更优异的发光特性.透射电子显微镜、X射线粉末衍射、X射线光电子能谱、选区电子衍射证明ZnS在CdS表面进行了有效包覆.所制备核壳结构纳米粒子具有较好的尺寸分布,荧光发射峰半高峰宽为18～20nm,荧光量子产率达40%.     

Cd^2＋参量对于CdSe／CdS／ZnS量子点荧光特性的影响

测量了CdSe、CdSe／CdS／ZnS量子点的吸收光谱和发射光谱,讨论了两种不同量子点的光谱特性。改变核层内Cd^2＋浓度以及壳层内Cd^2＋／Zn^2＋比例,分别测量多组CdSe／CdS／ZnS量子点发射光谱并计算量子产率,结果表明,Cd^2＋浓度45mmol／L或者Cd^2＋／Zn^2＋比例为1／2时,CdSe／CdS／ZnS量子产率最高,从而确定最佳的Cd^2＋定量参数。     

中空CdS/ZnS纳米核壳材料的制备及其光催化性能探究

采用化学浴法制备聚苯乙烯(PS)/CdS纳米核壳材料,在超声波的作用下采用化学浴法制备PS/CdS/ZnS纳米核壳材料,最后溶液刻蚀除去中心模板,得到中空的CdS/ZnS核壳材料。利用SEM、TEM、EDX、XRD和UV-Vis等测试手段对样品的形貌、成分、粒度、微观结构和吸光度等进行了表征。结果表明:该方法制备的CdS/ZnS纳米材料具有空心双壳层结构,颗粒大小均匀,内壳层厚度为85~100nm,外壳层厚度约为40nm,在可见光下具有良好的稳定催化效能,能够多次回收循环利用。     

核壳结构CdS/ZnS@rGA的制备及光催化性能研究

为研究纳米CdS/ZnS@rGA复合材料在可见光下的光催化性能,采用一步溶剂热法合成了以ZnS为壳的CdS/ZnS核壳纳米粒子,将CdS/ZnS核壳纳米粒子附着在rGO纳米片上,并组装成CdS/ZnS@rGA复合气凝胶,用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)等对样品进行了表征,通过亚甲基蓝(MB)的光催化降解实验表明：CdS/ZnS@rGA复合气凝胶的形成不仅可以提高CdS的光稳定性,还可以增强对MB吸附能力,同时对MB的降解有明显的促进作用。可见光反应90 min, 50 mg的CdS/ZnS@rGA对100 mL 20 mg/L MB的去除率最高达到99%。经过5次循环实验,该材料仍具有较好的可重复利用性。     

巯基包覆CdSe和CdSe/CdS核壳纳米晶的水相合成与表征

利用水相合成的方法制备了巯基包覆的具有较高荧光量子产率的CdSe和CdSe／CdS纳米晶．水相合成方法的优点是原料低廉、安全可靠和重复性高，缺点是纳米晶的尺寸分布较宽，发光效率不是很高．采用X-射线粉末衍射、吸收和荧光等光谱手段对纳米晶的平均尺度、粒径分布、晶体结构及发光特性进行了表征。在77K到300K的温度范围内，随着温度降低，CdSe纳米晶的发光峰逐渐蓝移，而CdSe／Cds纳米晶发光峰位基本不随温度变化而变化．此外，在325nm激光辐照下，CdSe／CdS纳米晶的荧光寿命比CdSe纳米晶延长了6倍左右，稳定性大幅度提高．以上结果表明，核壳结构的CdSe／CdS纳米晶具有较高的发光效率和良好的稳定性，具有广阔的应用前景．     

水溶性Cu∶CdTe/CdS核壳量子点的合成、表征及细胞毒性检测

采用水相法合成了Cu掺杂CdTe量子点,并用CdS壳层进行包覆,得到了Cu∶CdTe/CdS核壳结构量子点。采用荧光发射光谱(FL)、紫外可见吸收光谱(UV-Vis)、透射电镜(TEM)以及能谱仪(EDS)等手段对CdTe量子点和Cu∶CdTe/CdS核壳量子点进行了表征。研究了不同Cu掺杂浓度、CdS壳层生长时间以及Cd/硫脲物质的量比对Cu∶CdTe掺杂量子点光学性能的影响,并采用人成骨肉瘤细胞(MG-63细胞)对样品做了细胞毒性分析。研究结果表明:通过掺杂和包壳的步骤,合成的Cu∶CdTe/CdS核壳量子点在CdTe量子点的基础上实现了荧光发射红移,荧光强度提高,以及细胞毒性降低。     

Bi／聚苯乙烯壳-核结构纳米复合物的制备及光学性质研究

利用磺化处理后的聚苯乙烯空心球（S-SPS）作硬模板，采用简单的还原方法，大量制备了具有核,壳结构的Bi／S．SPS纳米复合物。产物采用XRD，SEM，TEM，HRTEM和荧光发射谱（PL）等进行了系统的表征．其中核为空心的有机物S-PS球，壳为无机Bi层，包覆在S-Ps表面上的Bi层厚度为50nm左右,纳米复合物的荧光发射谱相对于聚苯乙烯原料而言，具有明显增强且红移的紫外发射。结果表明半导体Bi粉体在有机物表面的包覆，可以明显增强有机物的荧光发射效率，提出了此核-壳纳米复合物的生长机理。     

核壳结构型ZnS包覆ZnS：Cu的合成及其发光性能研究

利用液相化学方法并添加有机表面活性剂合成了ZnS：Cu／ZnS核壳结构,X射线衍射表明,所合成的ZnS具有闪锌矿结构,随着ZnS包覆量的增加,核壳结构尺寸增大并在紫外-可见光谱图中的吸收峰出现红移,荧光光谱中,该纳米材料在510nm处出现荧光发射峰,主要是由于Cu2＋在t2能级上的复合跃迁。作为表面钝化层,ZnS的包覆有效地降低了晶体中Cu2＋的无辐射复合,并明显改善了znS：Cu的发光强度和发光寿命。     

核壳型TiO2／HAP纳米复合光催化剂的制备与表征

采用非均相沉淀的方法，首次在纳米TiO2的表面诱导沉积一层羟基磷灰石（HAP）。通过X射线衍射（XRD）和傅立叶红外光谱（FT-IR）对制备的样品进行结构和成分分析；用原子力显微镜（AFM）、扫描电子显微镜（SEM）和电子能谱仪（EDS）对样品包覆进行表征；采用甲基橙的光催化降解反应和大肠杆菌吸附率测定对所制光催化剂的光催化活性和吸附特性进行了评价；并与纯的纳米TiO2进行比较分析，文中还初步探讨了TiO2／HAP纳米复合材料的包覆机理．结果表明，TiO2／HAP为核壳结构，且包覆均匀，羟基磷灰石包覆层的厚度为8nm。所制备的样品具有良好的光催化活性和对细菌良好的吸附性能。这种核壳型TiO2／HAP纳米复合材料可用作环境净化和杀菌材料．     

Facile synthesis and luminescence characteristics of high-quality CdS: Eu/ZnS core/shell nanocrystals with biocompatibility

In this paper, we report a facile method to synthesize high quality CdS: Eu nanocrystals (NCs) and CdS: Eu/ZnS NCs with strong photoluminescence (PL). The influence of various experimental variables including the concentration of Eu3+ ions, the reaction time and the reaction temperature were investigated systematically. In addition, the PL properties of CdS: Eu NCs exhibited pH sensitive. Under the acid condition, pH value of the CdS: Eu NCs solution played an important role in determining PL emission intensity. However, under the alkaline condition, the obtained CdS: Eu NCs exhibited a tunable PL emission wavelength (from 490 nm to 610 nm) when pH value was adjusted from pH 7 to 10. After coating with ZnS shell, the CdS: Eu/ZnS NCs showed enhanced PL intensity compare with one of the CdS: Eu NCs. The CdS: Eu NCs and CdS: Eu/ZnS NCs were characterized by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). In addition, the biocompatibility of these NCs was measured by hemolytic test, which indicated that CdS: Eu/ZnS NCs were more biocompatible than CdS: Eu NCs at the same conditions. It can be expected that CdS: Eu/ZnS NCs are promising biolabeling materials.     

CdSe/Cd(x)Zn1-xS core/shell nanocrystals: core morphology and luminescent property

CdSe cores with rod (an aspect ratio of 1.8, d-5 nm) and spherical (an aspect ratio of 1, d-5 nm) morphologies were fabricated by two kinds of organic approaches through adjusting growth processes. Because of large difference of size and morphology, two kinds of cores revealed different absorption spectra. However, these cores exhibited almost same photoluminescence (PL) spectra with a red-emitting PL peak of around 625 nm. This is ascribed that they have a similar size in diameter. A graded Cd(x)Zn1-xS shell of larger band gap was grown around CdSe rods and spheres using oleic acid as a capping agent. Based on the growth kinetics of CdS and ZnS, interfacial segregation was created to preferentially deposit CdS near the core, providing relaxation of the strain at the core/shell interface. For spherical CdSe cores, the homogeneous deposition of the Cd(x)Zn1-xS shell created spherical core/shell nanocrystals (NCs) with a size of 7.1 nm in diameter. In the case of using CdSe cores with rod morphology, the anisotropic aggregation behaviors of CdS monomers on CdSe rods led to the size (approximately 10 nm in diameter) of spherical CdSe/Cd(x)Zn1-xS core/shell NCs with a small difference to the length of the CdSe rod (approximately 8.9 nm). The resulting spherical core/shell NCs created by the rod and spherical cores exhibited almost same PL peak wavelength (652 and 653 nm for using rod and spherical cores, respectively), high PL efficiency up to 50%, and narrow PL spectra (36 and 28 nm of full with at half maximum of PL spectra for the core/shell NCs with CdSe spheres and rods, respectively). These core/shell NCs provide an opportunity for the study of the evolution of PL properties as the shape of semiconductor NCs.     

Optical properties of water-soluble l-cysteine-capped alloyed CdSeS quantum dot passivated with ZnSeTe and ZnSeTe/ZnS shells

Alloyed quantum dots (QDs) passivated with shell materials have valuable optical characteristics suitable for a wide array of applications. In this work, alloyed ternary CdSeS QDs passivated with ZnSeTe and ZnSeTe/ZnS shells have been synthesized via a hot-injection method and a ligand exchange reaction employing l-cysteine as a thiol ligand has been used to obtain these water-soluble nanocrystals for the first time. The photoluminescence (PL) quantum yield (QY) of alloyed l-cysteine-capped CdSeS was 71.2% but decreased significantly to 5.2% upon passivation with a ZnSeTe shell. The red shift in PL emission of the CdSeS/ZnSeTe QDs was attributed to be strain-induced whilst a lattice-induced process likely created defect states in the core/shell interface hence contributing to the decline in the PL QY. Nonetheless, the fluorescence stability of CdSeS/ZnSeTe QDs in aqueous solution was unperturbed. Further passivation with a ZnS shell (CdSeS/ZnSeTe/ZnS) improved the PL QY to a value of 58.7% and thus indicates that the defect state in the QDs core/shell/shell structure was reduced. PL lifetime exciton measurements indicated that the rates of decay of the QDs influenced their photophysical properties.     

Phosphine-free synthesis of high-quality reverse type-I ZnSe/CdSe core with CdS/Cd(x)Zn(1 - x)S/ZnS multishell nanocrystals and their application for detection of human hepatitis B surface antigen

Highly photoluminescent (PL) reverse type-I ZnSe/CdSe nanocrystals (NCs) and ZnSe/CdSe/CdS/Cd(x)Zn(1 - x)S/ZnS core/multishell NCs were successfully synthesized by a phosphine-free method. By this low-cost, 'green' synthesis route, more than 10 g of high-quality ZnSe/CdSe/CdS/Cd(x)Zn(1 - x)S/ZnS NCs were synthesized in a large scale synthesis. After the overgrowth of a CdS/Cd(x)Zn(1 - x)S/ZnS multishell on ZnSe/CdSe cores, the PL quantum yields (QYs) increased from 28% to 75% along with the stability improvement. An amphiphilic oligomer was used as a surface coating agent to conduct a phase transfer experiment, core/multishell NCs were dissolved in water by such surface modification and the QYs were still kept above 70%. The as-prepared water dispersible ZnSe/CdSe/CdS/Cd(x)Zn(1 - x)S/ZnS core/multishell NCs not only have high fluorescence QYs but also are extremely stable in various physiological conditions. Furthermore, a biosensor system (lateral flow immunoassay system, LFIA) for the detection of human hepatitis B surface antigen (HBsAg) was developed by using this water-soluble core/multishell NCs as a fluorescent label and a nitrocellulose filter membrane for lateral flow. The result showed that such ZnSe/CdSe/CdS/Cd(x)Zn(1 - x)S/ZnS core/multishell NCs were excellent fluorescent labels to detect HBsAg. The sensitivity of HBsAg detection could reach as high as 0.05 ng ml( - 1).     

Effect of shell layers on luminescence of colloidal CdSe/Zn(0.5)Cd(0.5)Se/ZnSe/ZnS core/multishell quantum dots

Colloidal CdSe/Zn(0.5)Cd(0.5)Se/ZnSe/ZnS core/multishell quantum dots (QDs) were synthesized by using the well developed successive ion layer adsorption and reaction (SILAR) technique. The UV-vis and PL spectra, TEM, X-ray diffraction and Raman measurement were performed to investigate the structure and optical properties of prepared QDs during the growth of shell layers, which indicated that the stress in CdSe core became stronger with the increasing shell thickness. Due to the gradual adjustment of the lattice parameters in the radial direction and the radial increase of the respective valence- and conduction-band offsets, the optical measurements show a significant enhancement in the photoluminescence quantum yield (QY) and an expedited radiative decay in QDs overcoated with thicker shell. The temperature-dependent optical spectra were measured, and the relation between the microstructure and the optical properties of these core/multishell quantum dots was discussed.     

Fluorescence properties of alloyed ZnSeS quantum dots overcoated with ZnTe and ZnTe/ZnS shells

Fluorescent alloyed ternary ZnSeS quantum dots (QDs) have been synthesized via the pyrolysis of organometallic precursors. The effects of passivation of ZnTe and ZnTe/ZnS shells on the optical properties of the ternary alloyed ZnSeS core have been studied. A ligand exchange reaction using l-cysteine as a capping ligand was used to obtain water-soluble nanocrystals. The nanocrystals were each characterized by UV/vis absorption and fluorescence spectroscopy, transmission electron microscopy, X-ray diffractometry (XRD) and X-ray photoelectron spectroscopy (XPS). The photoluminescence (PL) quantum yield (QY) of alloyed ZnSeS QDs was 14% and this value increased to 27% when ZnTe was overcoated around the surface but further coating with a ZnS shell decreased the PL QY slightly to 24%. This implies that ZnTe shell suppressed non-radiative recombination exciton states in the alloyed core while further layering with a ZnS shell offered no further improvement in suppressing the defect states. XPS analysis confirmed the presence of the first shell layering but showed a weakened intensity signal of S (2p) and Se (3d) for the ZnSeS/ZnTe/ZnS QDs. Our work demonstrates for the first time that shell passivation of alloyed Zn-based QDs can offer improved optical properties. We hope the optical information presented in this work will be useful in the selection of alloyed Zn-based QDs appropriate for the intended application.     

Effect of inorganic shells on luminescence properties of ZnS:Ag nanoparticles

The hydrothermally synthesized Ag-doped ZnS (ZnS:Ag) nanoparticles have been coated with inorganic shells by a chemical precipitation method. The ZnS:Ag/ZnS, ZnS:Ag/CdS, and ZnS:Ag/ZnO core–shell nanoparticles with different thickness of ZnS, CdS, and ZnO shells have been prepared. The effects of shells on the luminescence properties of ZnS:Ag cores have been investigated through the photoluminescence (PL) spectra and luminescence stabilities of products. In the core–shell nanoparticles involved here, the ZnO shell can most significantly enhance the luminescence of ZnS:Ag cores. The 450 nm emission intensity of ZnS:Ag/ZnO nanoparticles is up to 125 % of that of ZnS:Ag nanoparticles. However, the ZnO shell can hardly influence the luminescence stability under ultraviolet irradiation. The ZnS shell can only increase the luminescence of ZnS:Ag cores to some extent, but it can improve the luminescence stability under ultraviolet irradiation. Although the CdS shell can improve the luminescence stability to some extent, it quenches the luminescence of ZnS:Ag nanoparticles dramatically.     

Highly luminescent blue emitting CdS/ZnS core/shell quantum dots via a single-molecular precursor for shell growth

Highly luminescent blue-emitting CdS/ZnS core/shell quantum dots (QDs) were synthesized in N-oleoylmorpholine by two facile steps: first, the CdS core QDs were prepared via a simple one-pot method involving a direct reaction of Cd precursor cadmium stearate and S precursor S powder in solvent N-oleoylmorpholine; second, ZnS shells were successively overcoated on CdS core through the decomposition of single molecular precursor zinc diethyldithiocarbamate. The thickness of shell was precisely tuned by controlling drip feed speed and amount of shell precursor. The obtained CdS/ZnS core/shell QDs showed the maximum photoluminescent quantum yield of 54.8% and narrow spectra bandwidth, exhibiting high monodispersity, good color purity and long fluorescent lifetimes. The CdS/ZnS core/shell QDs with tunable emission wavelength of 424–470 nm were obtained by controlling the thickness of ZnS shell overgrown on different-sized CdS QDs, which are promising materials for blue light-emitting devices.     

Luminescent properties of ZnS:Mn2+/ZnS core/shell nanocrystals

High-quality ZnS:Mn2+/ZnS core/shell nanocrystals (NCs) with a core crystal diameter of 6.1 nm and 1.15 nm thick shells were synthesized via a high-boiling solvent process. The energy levels of the conduction band and valance band are estimated to be -3.2 eV and -6.8 eV by cyclic voltammetry and ultraviolet-visible (UV-vis) absorption spectra. The ZnS:Mn2+/ZnS NC emission peak is primarily located at 580 nm under 310 nm light excitation, originating from the charge transition from 4T1 to 6A1 within the 3d5 configuration of the Mn2+ ion. Based on ZnS:Mn2+/ZnS NCs as the active layer electroluminescent devices, the emission peak mainly locates at 460 nm with one shoulder emission peaking at 580 nm. The photoluminescence and electroluminescence properties of ZnS:Mn2+/ZnS NCs are investigated in the view of charge carrier injection and energy level alignment.