Preparing ZnS nanoparticles on the surface of carboxylic poly(vinyl alcohol) nanofibers

This paper presents a new synthetic route to hybridize ZnS semiconductor nanoparticles and poly(vinyl alcohol) (PVA) based electrospinning nanofibers. At first, zinc ions are introduced onto the surface of carboxylic PVA nanofibers. Then sulfide ions are added to react with zinc ions to form ZnS nanoparticles. The average diameter of the nanofibers is about 300 nm, and the diameter of the ZnS nanoparticles is about 5 nm. The photoluminescence spectrum of ZnS/carboxylic PVA nanocomposites has a 60 nm blue shift compared with that of the corresponding bulk ZnS sample. The carboxylic PVA enhances the quantum effects of the ZnS nanoparticles.     

Investigation on one-pot hydrothermal synthesis,structural and optical properties of ZnS quantum dots

The advantage of hydrothermal synthesis of semiconductor quantum dots (QDs) over the control of particles size, morphology and stability is reported here. In a typical synthesis procedure, the zinc and sulfur precursor molar ratio of 1:3 was used in an aqueous solution at 150 °C. The cubic phase of ZnS with average particles size of 5 nm was confirmed and estimated from the X-ray diffraction (XRD) analysis. The composition and purity of the sample were analyzed from (energy dispersive-ray analysis) EDAX and (X-ray photoelectron spectroscopy analysis) XPS spectra. The absorption spectrum shows the large shift in the absorption band over 90 nm due to the quantum confinement of carriers. The emission spectrum of quantum dots carry more evidence on the presence of shallow trap, deep trap in the band gap of the material responsible for weak emission in the spectral region of 450–500 nm. High resolution transmission electron microscope and scanning electron microscope studies reveal the structural and morphological features of ZnS with slightly distorted spherical morphology. We found that the coordinating ability of solvent strongly influences the reaction process and morphology of the products.     

Luminescence of er doped ZnS quantum dots excited by infrared lasers

ZnS:Er quantum dots were prepared in aqueous medium from readily available precursors. The construction, morphology and luminescence properties of the ZnS:Er quantum dots were evaluated by X-ray diffraction (XRD), transmission electron microscopy (TEM), and photoluminescence spectra. The average particle size was calculated using the Scherrer formula to be 4 nm, which is also observed from high resolution transmission electron microscopy (HRTEM) image. Different laser wavelengths at 976 +/- 2 nm and 1480 nm were utilized as the excitation source. ZnS:Er quantum dots had a fluorescence spectrum in 1550 nm region through the 4I13/2 --> 4I15/2 transition. Furthermore, intensity increased with increasing excitation intensity and dopant concentration. The reason for the photoluminescence spectra broadening is discussed. It is because the energy levels of Er3+ are split by a coulombic interaction between electrons, including spin correction and spin-orbit coupling, and eventually by the Stark effect due to ZnS QDs crystal field and local coordination.     

Low-temperature synthesis of hexamethylenetetramine-stabilised ZnS nanoparticles and its photocatalytic properties

ZnS nanoparticles have been synthesised at low temperature by short reaction (80°C for 2?h) via wet chemical route. The nanoparticles were stabilised using hexamethylenetetramine (HMTA) as surfactant in aqueous solution. The average particle size calculated from X-ray diffraction studies was about 4?nm with cubic zincblende structure. The presence of HMTA in the synthesised ZnS nanoparticles was confirmed by FTIR studies. A significant blue shift was observed in the optical absorption band edge for the ZnS nanoparticles as compared to the bulk, indicating a strong quantum confinement. The room temperature photoluminescence (PL) spectrum showed a broad green emission peak at around 502?nm. The photocatalytic property of HMTA-stabilised ZnS nanoparticles were investigated on the decolourisation of methylene blue aqueous solution under UV light irradiation.     

CdSe(ZnS) nanocomposite luminescent high temperature sensor

High temperature luminescence-based sensing is demonstrated by embedding colloidal CdSe(ZnS) quantum dots into a high temperature SiO(2) dielectric matrix. The nanocomposite was fabricated by a solution process method. As-prepared CdSe(ZnS) quantum dots in the nanocomposite sensor show an absorption band at a wavelength of 600 nm (2.06 eV). Photoluminescence (PL) measurements show a room temperature emission peak at 606 nm (2.04 eV). The temperature-dependent emission spectra study shows for the first time a CdSe(ZnS)-SiO(2) nanocomposite-based high temperature sensor. The temperature-dependent spectral and intensity modes of the nanocomposite thin film photoluminescence were investigated from 295-525 K. The sensor shows a variation of the emission wavelength as a function of temperature with a sensitivity of ～ 0.11 nm °C( - 1). The film morphology and roughness are characterized using AFM.     

Synthesis and characterization of shaped ZnS nanocrystals in water in oil microemulsions

Shaped zinc sulfide nanocrystals were synthesized in W/O microemulsions by using cyclohexane/Triton X-100/n-pentanol/water system. Under different synthetic conditions appearance of two distinct morphologies of ZnS nanocrystals, either cubes or nanowires, was proven by transmission electron microscopy (TEM). The ZnS cubes have an average size of about 25 nm, while the ZnS nanowires have 25 Å diameter and length ranging from several hundred nanometers up to a few microns. The X-ray diffraction analysis (XRD) revealed formation of ZnS with cubic zinc blende crystal structure. Due to two dimensional confinement the exciton of ZnS nanowires is blue shifted compared to the bulk material. Four well-resolved photoluminescence bands in visible spectral region were observed upon excitation of cubic ZnS particles, while in the case of ZnS nanowires emission band was observed at 421 nm. The origin of photoluminescence bands was discussed in details.     

Synergistic effects of SPR and FRET on the photoluminescence of ZnO nanorod heterostructures

Solution-grown ZnO nanorods (NRs) were successfully conjugated with CdSe/ZnS quantum dots (QDs) and Ag nanoparticles (NPs) to suppress intrinsic defect emission and to enhance band-edge emission at the same time. First, high-density and high-crystallinity ZnO NRs of diameter 80–90 nm and length 1.2–1.5 μm were grown on glass substrates using a low-temperature seed-assisted solution method. The as-synthesized ZnO NRs showed sharp photoluminescence (PL) band-edge emission centered at ～377 nm together with broad defect emission in the range of ～450–800 nm. The ZnO NRs were decorated with CdSe/ZnS QDs and Ag NPs, respectively, by sequential drop-coating. The PL of CdSe/ZnS QD||ZnO NR conjugates showed that ZnO band-edge emission decreased by 73.8% due to fluorescence resonance energy transfer (FRET) and charge separation between ZnO and CdSe/ZnS by type II energy band structure formation. On the other hand, Ag NP||CdSe/ZnS QD||ZnO NR conjugates showed increased band-edge emission (by 25.8%) and suppressed defect emission compared to bare ZnO NRs. A possible energy transfer mechanism to explain the improved PL properties of ZnO NRs was proposed based upon the combined effects of FRET and surface plasmon resonance (SPR).     

Preparation of lanthanide doped CdS, ZnS quantum dots in natural polysaccharide template and their optical properties

Employing a biomimic method using polysaccharide as template, luminescent lanthanide ions doped CdS and ZnS quantum dots (QDs) were prepared. According to the results of TEM and absorbance, nanocrystals with an average size of 6 nm were formed under mild condition without any toxic and expensive agent applied. Differentiating from the un-doped CdS and ZnS QDs prepared in polysaccharide template, the lanthanide doped QDs exhibited obvious dopant emission in their photoluminescence spectrum. It was also found that the dopant PL became more prominent with increasing lanthanide doping concentration, while the highest PL intensity was obtained at a doping level of 1% for both of CdS and ZnS QDs. When different lanthanide ions were introduced into the CdS QDs in polysaccharide template, varied emission wavelength were able to be obtained. This study provides an easy, mild and environmental friendly alternative method to prepare doped quantum dots. In addition, the bioactivity and processabilities endowed by the polysaccharide template may expand the applications potential of this type of optical materials.     

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).     

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.     

层状硫化锌的溶剂热法制备

以乙酸锌Zn(CH3COO)2.2H2O为锌源、硫脲SC(NH2)2为硫源、水与乙二胺的混合溶液为反应溶剂、十二烷基磺酸钠C12H25SO3Na形成的胶束为模板,利用溶剂热法制备了具有层状微观形貌的ZnS粉体材料。利用XRD、SEM、EDS等测试手段进行表征,结果表明,所得ZnS粉体材料结晶良好,层状形貌明显;层状ZnS粉体材料在435nm附近有较宽的发射峰,且发光性能明显优于球状ZnS粉体材料。     

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。     

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.     

Zinc Thiolate Enables Bright Cu‐Deficient Cu‐In‐S/ZnS Quantum Dots

Copper indium sulfide (CIS) colloidal quantum dots (QDs) are a promising candidate for commercially viable QD‐based optical applications, for example as colloidal photocatalysts or in luminescent solar concentrators (LSCs). CIS QDs with good photoluminescence quantum yields (PLQYs) and tunable emission wavelength via size and composition control are previously reported. However, developing an understanding and control over the growth of electronically passivating inorganic shells would enable further improvements of the photophysical properties of CIS QDs. To improve the optical properties of CIS QDs, the focus is on the growth of inorganic shells via the popular metal‐carboxylate/alkane thiol decomposition reaction. 1) The role of Zn‐carboxylate and Zn‐thiolate on the formation of ZnS shells on Cu‐deficient CIS (CDCIS) QDs is studied, 2) this knowledge is leveraged to yield >90% PLQY CDCIS/ZnS core/shell QDs, and 3) a mechanism for ZnS shells grown from zinc‐carboxylate/alkane thiol decomposition is proposed.     

溶剂热制备花状ZnO纳米晶及光性能表征

利用溶剂热法,以乙酸锌（Zn（CH3COO）2·2H2O）和氢氧化钠（NaOH）为源,在乙二醇和水的混合溶剂中制备出了花状氧化锌纳米晶体,用X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）和选区电子衍射（SAED）测试分析,发现样品为六方纤锌矿结构的ZnO单晶,花状晶体的大小约为600nm,单个花瓣的长、宽分别约为300nm、100nm。对比实验发现,产物形貌对NaOH浓度的依赖性很大。紫外可见吸收光谱（UV—vis spectra）显示,产物除了本征吸收外,在长波方向（600nm处）也有一宽化的、较强的吸收峰。室温荧光光谱（PL spectra）显示,产物在400—480nm有一明显的发光带,且在405nm和472nm处有两个较强的发光峰。     

Effect of biocompatible glutathione capping on core–shell ZnS quantum dots

Glutathione capped quantum dots are a potential candidate for different applications like ligand exchange in living cells, cell imaging and detection of glucose levels. Keeping these in mind, glutathione capped ZnS quantum dots were synthesized by using the thiol group of the capping agent by chemical precipitation method. Morphological characterizations were done by XRD and TEM. X-ray diffraction (XRD) measurements showed that the nanocrystals have Zinc Blende structure. Grain size and particle size shows a little variation with glutathione capping. Optical characterizations were done by UV–visible absorption, FTIR and energy resolved photoluminescence. UV–visible studies shows that the band gap also shows a small variation with glutathione capping. FTIR studies confirm glutathione capping on the surface of ZnS quantum dots. Room temperature energy resolved photoluminescence spectrum of samples exhibited a defect-related blue emission band. However, the PL properties seem to start tunability at higher concentration of glutathione which is a very good sign for extending this research further.     

水溶性ZnS量子点的共沉淀法制备、 表征及其光学性能

以硫化钠和乙酸锌为反应物,3-巯基丙酸为表面包覆剂,利用共沉淀法制备了水溶性ZnS量子点。并采用X射线衍射仪、透射电子显微镜和荧光分光光度计等对样品的结构、形貌、粒径和光学性能进行了表征。结果表明:所得样品为ZnS立方型闪锌矿结构,量子点的形状呈不规则球形,粒径主要集中在4.8nm左右;样品在585～590nm之间出现了黄色荧光发射波峰。同时,利用红外光谱对ZnS量子点的合成机理进行了初步分析。     

运用微通道技术制备氧化锌材料

以醋酸锌(Zn(CH3COO)2.2H2O)和氨水(NH3.H2O)为反应物,对比运用微通道和搅拌釜为反应器时所得产物氧化锌形貌的差别。运用同轴环管微通道作为反应器经过水热过程合成一种直径在0.5~1μm,长度在20~30μm左右新型的棒状氧化锌材料。结果表明,以搅拌釜为反应器得到的产物为不均匀的纳米颗粒,经过水热过程后转变成为直径在1μm左右的均匀星状结构。以在线高速照相机来观察液体在微通道中的流动状态,发现其为均匀的层流流动,讨论运用微通道合成氧化锌的成核和生长机理。     

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。     

Synthesis and characterization of water-soluble <Emphasis Type="SmallCaps">l</Emphasis>-cysteine-modified ZnS nanocrystals doped with silver

The water-soluble Ag⁺-doped ZnS nanocrystals surface capped with cysteine (expressed as ZnS:Ag/Cys) were synthesized in aqueous solution by using l-cysteine as surface modifier. The crystal structure, size, shape, component, and spectral properties of ZnS:Ag/Cys nanocrystals were characterized by X-ray power diffraction, transmission electron microscope, energy dispersive X-ray analysis, inductively coupled plasma atomic emission spectrometry, infrared spectrum, UV–Vis absorption spectrum, and photoluminescence spectrum. The results show that the spherical ZnS:Ag/Cys nanocrystals with an average diameter of 2.6 nm have good fluorescent characteristics, their fluorescence intensity is enhanced greatly after doped with Ag⁺. And the sulfur atoms in cysteine molecules are coordinated with metal ions on the surface of the nanocrystals, the cysteine modified on the surface of ZnS:Ag/Cys nanocrystals renders the nanocrystals water soluble and biocompatible. The ZnS:Ag/Cys nanocrystals have potential applications in molecular assembly and biological fluorescence analysis.