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。     

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。     

离子液体辅助微波法水相合成Cu-In-Zn-S/ZnS量子点及其在白光LED中的应用

Cu-In-Zn-S(CIZS)量子点具有毒性低、发射谱覆盖范围广、Stokes位移大等特点, 在照明领域具有广阔的应用前景。通过离子液体辅助微波法水相合成CIZS量子点, 系统研究了反应时间、配体添加量和前驱体溶液pH对样品的物相组成、显微形貌以及荧光性能的影响。结果表明, 与未添加离子液体制备的样品相比, 离子液体的引入提高了反应速率, 可有效地将反应时间由180 min缩短至30 min; 随着反应时间的延长, 量子点的粒径增大, 其发射峰位由609.2 nm红移至634.6 nm。随着n_{GSH(谷胱甘肽)}/n_(CuInZn)的增大, 量子点的粒径逐渐增大, 导致其发射峰位由622.6 nm红移至631.6 nm, 同时量子点的发光强度逐渐增强; 当该比值为15时, 量子点的荧光强度最高。此外, 随着pH的增大, 去质子化的-SH和-NH₂与量子点的作用逐渐增强, 有效地钝化了量子点的表面态, 使其荧光强度逐渐上升, 当pH为8.5时, 样品的荧光性能最佳, 同时量子点的平均水合粒径由99 nm增大至241 nm; 量子点溶液的Zeta电位为-27.7~-41.1 mV, 说明量子点溶液具有优异的稳定性。通过ZnS表面修饰可有效提高量子点的荧光强度。将CIZS/ZnS量子点与蓝光芯片结合, 获得了显色指数为85.6、发光效率为34.8 lm/W的白光LED器件, 为水相制备的多元量子点在白光LED中的应用提供了参考。     

水相制备CdSe量子点及其ZnS核壳结构量子点

因具有较宽的可调控发光范围,CdSe量子点及其ZnS核壳结构量子点受到了研究者们的普遍关注。采用水相回流法合成了CdSe量子点及其ZnS核壳结构量子点,并结合透射电镜(TEM)、X射线衍射(XRD)、紫外-可见光吸收光谱(UV-Vis)和荧光光谱(PL)对样品进行表征。TEM结果表明,合成的量子点粒径分布较宽且结晶度较高;从XRD分析结果可以看出,CdSe量子点为闪锌矿结构,沿着晶面向外生长ZnS壳层后,谱峰向高角度偏移;从UV-Vis和PL分析结果可以看出,CdSe量子点于500 nm处出现吸收肩峰,于644 nm处出现半高宽较宽的缺陷发光峰;随着反应时间的延长,于577 nm处出现本征发光峰。包覆了ZnS壳层后,量子点不仅发光强度明显增大,而且稳定性显著提高。该合成方法节能环保、生产效率高,具有较大的应用空间。     

油酸中ZnS∶Mn量子点的制备及火腿肠中苏丹Ⅰ测定研究

以氯化锰、氯化锌、硫化钠为原料,在油酸-无水乙醇混合溶剂中,180℃条件下,反应8h,成功制备了ZnS∶Mn量子点。320nm激发条件下,ZnS∶Mn量子点的荧光发射峰位于420nm。且苏丹Ⅰ在350~540nm范围内有较好的吸收,利用苏丹Ⅰ对ZnS∶Mn量子点荧光强度的猝灭建立荧光探针体系,当苏丹Ⅰ浓度在5.0×10-8~7.0×10-7 mol/L内,线性方程为ΔF=389.29-25.12c,相关系数(R)为0.9915(n=5),检测限为1.46×10-8 mol/L。且成功用于实际样品中苏丹Ⅰ的检测,加标回收率在92.8%~99.2%之间。     

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.     

微波法一步制备新型荧光碳量子点及光学性能研究

首次以中药材贝母为碳源,采用微波法一步合成新型荧光碳量子点。通过原料用量、微波功率和反应时间优化,获得了制备荧光碳量子点的最佳实验条件。同时通过透射电镜和X射线光电子能谱仪对荧光碳量子点进行了形貌及结构表征,通过荧光光谱和紫外-可见吸收光谱对荧光碳量子点进行了光学性能研究。结果表明:原料用量2g,微波功率800W,反应时间8min为合成荧光碳量子点最佳反应条件,制备得到的荧光碳量子点平均粒径5nm,最大激发波长310nm,最大荧光发射波长位于400nm处,最大紫外吸收波长280nm。     

CdSe量子点的制备及荧光性能改善

主要讨论了CdSe量子点的制备及荧光性能的改善.采用水相合成方法制备了CdSe量子点,并用X射线粉末衍射仪对所合成的量子点进行表征,用荧光分光光度计研究了量子点的荧光性质.结果表明,采用样品处理温度的调节和ZnS壳层的包覆能在一定程度上改善CdSe量子点的荧光性能.     

碳量子点的一步合成及其发光性质的研究

本文采用油浴加热柠檬酸一步法合成碳量子点,用HRTEM透射电镜和FTIR红外光谱对其形貌和结构进行表征。研究该碳量子点的荧光性质,初步探讨了其发光的可能机理。实验结果表明,该方法合成的碳量子点粒径大小为3~5 nm,在360 nm处有一个很强的紫外吸收峰,最大激发波长和发射波长分别为365 nm和460 nm,其光学稳定性良好,在pH5.0~7.0范围内,碳量子点的荧光强度随pH的变化比较敏感。     

微波-淀粉辅助合成ZnS纳米晶及其光学性能研究

以乙酸锌为锌源,硫代乙酰胺(TAA)为硫源,淀粉为分散剂,微波辅助合成了硫化锌(ZnS)纳米晶。研究了不同微波温度对ZnS结构和晶粒大小的影响,并对形成机理进行了探讨。通过X射线衍射仪(XRD)、透射电子显微镜(TEM)、电子扫描显微镜(SEM)、傅里叶红外光谱(FT-IR)、紫外-可见吸收光谱(UV-Vis)和荧光分光光度计(FL)对物相、形貌、化学键合性质和光学性能等方面,进行了表征分析。结果表明:制得的样品为纯闪锌矿立方相ZnS,晶格常数为0.5196nm;晶粒大小随着温度增加而增大;粒径分布较窄,粒径100~160nm;禁带宽度处为3.85eV,与体相材料的禁带宽度E_g=3.68eV相比,发生了蓝移,可能是量子限域效应和材料形貌所致;所测样品有1个主发射峰和肩峰,处于蓝绿光谱段,归因于表面缺陷和近带边发射。     

Synthesis and photoluminescence of ZnS quantum dots

Single-phase zinc sulphide (ZnS) quantum dots were synthesized by a chemical method. The influence of the pH value of the Zn(CH3COO)2 solution on the size and photoluminescence properties of the ZnS quantum dots was evaluated. X-ray power diffraction, transmission electron microscopy, and ultraviolet-visible spectroscopy were used to characterize the structure, size, surface states, and photoluminescence properties of ZnS quantum dots. The results showed that the crystal structure of ZnS quantum dots was a cubic zinc blende structure, and their average diameter was about 3.0 nm. ZnS quantum dots with good distribution and high purity were obtained. A strong broad band centered at about 320 nm was observed in the excitation spectrum of ZnS quantum dots. Their emission spectrum peaking at about 408 nm, was due mostly to the trap-state emission. The relative integrated emission intensity of ZnS quantum dots decreased as the pH value of the Zn(CH3COO)2 solution increased, which could be ascribed to the increase in average diameter of the ZnS quantum dots as the pH value of Zn(CH3COO)2 solution increased.     

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.     

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.     

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.     

Studies on optical absorption and photoluminescence of thioglycerol-stabilized ZnS nanoparticles

ZnS quantum dots of size 3 nm are prepared at 303 K using ZnSO₄ and Na₂S₂O₃ precursors with thioglycerol as stabilizing agent. Cd²⁺ doped ZnS were prepared by varying doping concentration from 1 to 8 wt.%. ZnS quantum dots were mixed with CdS quantum dots of size 4 nm in the 3:1, 2:1, 1:1, 1:2, 1:3 and 1:4 M ratio. The nanoparticles were characterized by UV–vis, photoluminescence (PL), XRD and high-resolution TEM measurements. The XRD pattern, high-resolution TEM image and SAED pattern reveal that the nanoparticles are in well-crystallized cubic phase. The band gap of ZnS has increased from the bulk value 3.7 to 4.11 eV showing quantum size effect. Excitonic transition is observed at 274 nm in UV absorption and PL emission at 411 nm. Doping with Cd²⁺ red-shifts both UV and PL spectral bands and enhances the PL band of ZnS nanoparticles. Mixing CdS and ZnS quantum dots in different molar ratios shows red-shift of the band edge in the CdS/ZnS hybrid system. In the 1:1 hybrid system of CdS/ZnS nanoparticles, PL band is red-shifted and the intensity is almost doubled with respect to that of CdS nanoparticles.     

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.     

Preparation and characterization of titania/ZnS core-shell nanotubes

Core-shell nanocomposites of titania nanotubes/ZnS quantum dots have been prepared by using a hydrothermal synthetic method and characterized by using various microscopic and spectroscopic methods. ZnS quantum dots surround the outsides of titania nanotubes having the inner and the outer diameters of 15 and 30 nm, respectively, with a thickness of 2 nm. The nanocomposites suspended in water show a broader absorption spectrum shifted to a longer wavelength by 20 nm and emit substantially stronger ZnS luminescence having significantly slower decay kinetics than bare ZnS nanoparticles in water. The support of TiO2 nanotubes is found to enhance the optical properties of ZnS considerably.     

Mn‐doped ZnS quantum dots‐chlorin e6 shows potential as a treatment for chondrosarcoma: an in vitro study

Chondrosarcoma is the second‐most malignant cancer of the bone and routine treatments such as chemotherapy and radiotherapy have not responded to the treatment of this cancer. Due to the resistance of chondrosarcoma to radiotherapy, the combination of therapeutic methods has been considered in recent years. In this study, a novel combination approach is used that allows photodynamic therapy to be activated by X‐rays. The synthesis of Mn‐doped zinc sulphide (ZnS) quantum dots was carried out and chlorin e6 photosensitiser attached by covalent and non‐covalent methods and their application as an intracellular light source for photodynamic activation was investigated. The toxicity of each nanoparticles was evaluated on chondrosarcoma cancer cells (SW1353) before and after radiation. Also, the effect nanoparticle‐photosensitiser conjugated type was investigated in the therapeutic efficacy. The characterisation test (SEM, TEM, EDS, TGA, XRD and ICP analyses) was shown successful synthesis of Mn‐doped ZnS quantum dots. Chondrosarcoma cancer cell viability was significantly reduced when cells were treated with MPA‐capped Mn‐doped ZnS quantum dots‐chlorin e6 with spermine linker and with covalent attachment (P  ≤ 0.001). These results indicate that X‐ray can activate the quantum dot complexes for cancer treatment, which can be a novel method for treatment of chondrosarcoma.Inspec keywords: semiconductor quantum dots, X‐ray diffraction, transmission electron microscopy, cadmium compounds, cellular biophysics, drugs, manganese, biomedical materials, cancer, quantum dots, nanofabrication, ultraviolet spectra, zinc compounds, fluorescence, scanning electron microscopy, nanoparticles, nanomedicine, bone, photochemistry, photodynamic therapy, tumours, II‐VI semiconductors, laser applications in medicineOther keywords: noncovalent methods, photodynamic activation, chondrosarcoma cancer cells, chondrosarcoma cancer cell viability, quantum dot complexes, cancer treatment, malignant cancer, routine treatments, radiotherapy, therapeutic methods, Mn‐doped zinc sulphide quantum dots, in vitro study, MPA‐capped Mn‐doped ZnS quantum dots‐chlorin e6, nanoparticle‐photosensitiser conjugated type, ZnS, Mn, ZnS:Mn     

Cadmium sulfide photoluminescence in poly(methyl methacrylate)-matrix composites

Poly(methyl methacrylate)-matrix composites containing cadmium, lead, and zinc sulfides and also mixed (cadmium lead and cadmium zinc) sulfides were prepared by reacting metal salts with thioacetamide. The transmission of the composites in the range λ > 500 nm is 92% at absorbing layer thicknesses of ≤5 mm. The photoluminescence (PL) of the composites in the wavelength range 500–820 nm is due to the cadmium sulfide, and that in the wavelength range 300–550 nm arises from the zinc sulfide. It results from radiative recombination at levels of extrinsic structural defects in CdS and ZnS, respectively. The PL excitation spectra contain excitonic absorption bands of cadmium sulfide and zinc sulfide quantum dots. The PL of the cadmium sulfide in the composites is influenced by the presence of lead(II) and zinc(II) ions and the complexation of cations on the surface of the particles.