基于紫外光辐照条件下制备ZnSe/ZnS核壳结构量子点

对传统的水相合成法进行改进,采用更加安全、简便、经济、环保的紫外光辐照方法在室温下合成了ZnSe/ZnS核壳结构量子点。调节pH值、光照时间、反应物配比等实验条件,优化了制备ZnSe/ZnS量子点核壳结构的最佳生长与修饰条件,使其具有良好色散、时间稳定性和发光特性。紫外线照射可以激发自由电子引发化学反应,研究使用了巯基乙酸(TGA)和谷胱甘肽(GSH)作为稳定剂和分散剂,用来控制ZnSe量子点的生长,得到分散均匀的ZnSe量子点。引入的光敏材料是形成ZnS的S源。利用X射线衍射(XRD)、电子显微镜(EM)、能量色散谱仪(EDX)、光致发光光谱(PL)和紫外可见光谱(UV-Vis)对量子点的晶体结构和光学性质进行了表征。结果表明, GSH修饰的ZnSe量子点相比于TGA修饰的ZnSe量子点呈现出更好的稳定性与较少的表面缺陷。ZnS的壳层生长能有效地弥补这一缺陷,但过厚的壳层会导致本征辐射的猝灭。该实验深入探索此类制备方法,并就各类影响因素和合成条件做出细致补充。实验结果结合理论分析得出ZnSe/ZnS核壳结构量子点的最佳合成条件。     

壳层相关的CdSe核/壳量子点发光的热稳定性

测量了CdSe/ZnS(3 ML)核/壳结构及CdSe/CdS(3 ML)/ZnCdS(1 ML)/ZnS(2 ML)核/多壳层结构量子点在80~460 K范围内的光致发光光谱,研究了壳层结构对CdSe量子点发光热稳定性的影响。详细地分析了CdSe量子点的发光峰位能量、线宽和积分强度与温度之间的关系,发现CdSe量子点的发光热稳定性依赖于壳层结构。CdS/ZnCdS/ZnS多壳层结构包覆CdSe量子点在低温和高温部分的热激活能均大于ZnS壳层包覆的CdSe量子点,具有更好的发光热稳定性。此外,在300-460-300 K加热-冷却循环实验中,CdS/ZnCdS/ZnS多壳层结构包覆CdSe量子点的发光强度永久性损失更少,热抵御能力更强。     

空穴传输材料对CdSe核壳量子点的荧光影响

用稳态光谱和时间分辨光谱技术研究了空穴传输材料对CdSe/ZnSe 与CdSe/ZnS核壳量子点的荧光影响。结果表明,空穴传输材料对量子点有较强的猝灭作用,随空穴传输材料分子浓度的增加,量子点的荧光强度明显地被猝灭,同时量子点的荧光寿命也被减短。两种不同空穴传输分子对CdSe/ZnSe量子点的荧光猝灭明显不同。在与相同空穴传输分子相互作用时,包覆ZnS壳层的CdSe核壳量子点荧光猝灭效率明显低于包覆ZnSe壳层的CdSe核壳量子点。量子点的荧光猝灭过程可以解释为静态猝灭和动态猝灭过程,其中静态猝灭来源于量子点表面与空穴传输材料间相互作用,而动态猝灭则主要来源于量子点到空穴传输材料的空穴转移过程。实验结果表明空穴传输材料的种类以及核壳量子点的壳层结构都对其荧光猝灭效应起关键作用。     

脂溶性CdSe/ZnS量子点脂质体复合物的制备及表征

在油相中成功合成了脂溶性CdSe/ZnS核壳量子点纳米粒,粒径平均为4.5 nm,量子产率达29%,发射波长为540 nm。通过薄膜分散法,以蛋黄卵磷脂、胆固醇为膜材,将脂溶性的CdSe/ZnS核壳量子点包覆于脂质体磷脂双分子层中,由于磷脂分子的两亲性,使得脂溶性的CdSe/ZnS核壳量子点同时又具有亲水性。通过透射电镜对脂质体形态进行了表征,倒置荧光显微镜证实了发光CdSe/ZnS核壳量子点成功包埋于脂质体双分子层中,包裹的发光CdSe/ZnS核壳量子点具有更稳定的发光及抗光漂白性质。     

HgTe/CdS/ZnS多壳层量子点的制备与表征

采用一种简单的方法合成HgTe/CdS/ZnS多壳层量子点。首先,以1-硫代甘油为稳定剂,在水相溶液中制备出HgTe核量子点;然后,采用外延生长法依次在HgTe核量子点表面包覆CdS和ZnS壳层,合成出最终具有稳定近红外发光的HgTe/CdS/ZnS多壳层量子点。该合成方法仅需3个步骤,具有操作简单、成本低廉的优点。实验结果显示,当反应温度为90 ℃、反应溶液pH为11.0、反应加热回流时间为4 min时,HgTe/CdS/ZnS多壳层量子点具有最高荧光量子产率36%。     

CuInS2纳米晶的制备和发光性质

以十二硫醇为溶剂,通过选择合适的金属源制备了各种尺寸的CuInS₂量子点。观察到随着粒子的尺寸减小,其吸收和发光光谱明显蓝移,存在明显的量子尺寸效应。通过在CuInS₂纳米晶表面包覆ZnS壳层,发现随着壳层厚度增加,其发光量子效率明显提高,最大达到了48%;继续增加壳层厚度,其发光量子效率反而降低。进一步测量它们的荧光寿命,发现包覆ZnS壳层后的CuInS₂纳米晶的荧光寿命明显增加,证实表面包覆明显减少其表面的无辐射复合中心,提高了其发光效率。进一步制备了CuInS₂/ZnS核壳量子点发光二极管,并对其电致发光性质进行了研究。     

生物大分子杂化处理的CdSe/ZnS核/壳量子点多层膜的超快三阶非线性研究

利用静电自组装技术，以生物大分子材料壳聚糖杂化处理具有稳定结构的CdSe/ZnS核/壳量子点，形成复合多层薄膜. 与薄膜的吸收谱线比较，在375nm飞秒激光激发下测量的量子点的光致发光谱存在Stokes位移. 采用Z扫描技术，利用790nm飞秒激光研究了其三阶非线性吸收和折射特性，发现饱和吸收信号来自CdSe/ZnS量子点，而自聚焦的折射信号则部分来自壳聚糖. 测出多层膜的三阶非线性系数分别是β＝6.5×10^-6cm/W，n₂＝1.5×10^-10cm²/W. 关键词： CdSe/ZnS量子点 非线性性能 光致发光谱     

Micro-LED全彩显示中量子点膜层制备及光转换效率优化

将表面配体改性的CdSe/ZnS量子点(Quantum dots)和光刻胶混合,进而采用光刻工艺在InGaN/GaN蓝光Micro-LED上实现了最小尺寸为3μm的高分辨率、高光效的量子点颜色转换膜层.同时系统研究了不同厚度和混合比例的量子点膜层的吸收/发射光谱及光致发光量子产率(PLQY).为优化光转换效率,量子点膜...     

ZnSe:Cu/CdS核壳量子点的合成及光学性能研究

以CdS为壳层材料对核水溶性ZnSe:Cu量子点进行包覆,得到ZnSe:Cu/CdS核壳结构的量子点。研究了壳层厚度对ZnSe:Cu量子点光学性能的影响,采用TEM、XRD、PL和UV-Vis手段对所得样品进行表征。实验结果表明:量子点为立方闪锌矿结构,分散性好,形状为球形,经壳层修饰后量子点的粒径由2.7 nm增大到4.0 nm。随着包覆CdS壳层数的增加,量子点的发射和紫外吸收谱红移,说明量子点在长大,证明CdS壳层生长在ZnSe:Cu量子点的表面,形成了核壳结构的ZnSe:Cu/CdS量子点。包覆CdS壳层后ZnSe:Cu量子点的发光强度减弱,但稳定性得到了提高。     

CdSe/CdS核壳量子点复合材料合成及其在白光发光二极管中的应用

采用有机化学合成法,利用正三辛基膦(TOP)辅助的快速注入生长方法,改进传统的制备工艺,实现了CdSe/CdS厚壳层核壳(8.6 ML)量子点复合材料的合成制备,并对所合成的核、核壳量子点及其复合材料的晶格结构、形貌特点与发光性质进行了XRD、TEM、SEM、UV-Vis、PL表征和红光补偿效果测试。测试结果表明,CdSe核具有立方纤锌矿晶格结构;CdSe/CdS量子点复合材料直径为45~75μm,呈菱形规则形貌,且颗粒分散性良好。采用该方法,可以提高量子产率,产率由4%(CdSe核)升至48%(CdSe/CdS核壳量子点);可以增强激子态发光能力,CdSe/CdS核壳量子点复合材料的荧光强度约为CdSe核的13倍。将该材料与YAG∶Ce~(3+)黄色荧光粉组合应用,获得了高光效(148.29 lm/W)、高显色指数(Ra为90.1,R9为97.0)的白光发光二级管,表明按照上述方法获得的CdSe/CdS核壳量子点复合材料在白光发光二极管中深红光波段具有较好的补偿效果。     

Wurtzite and zinc-blende CdSe based core/shell semiconductor nanocrystals: Structure, morphology and photoluminescence

We report comparative study of core/shell nanocrystals based on wurtzite and novel zinc-blende CdSe core. Both wurtzite and zinc-blende CdSe are coated with CdS shell or CdS/ZnS multishell under identical synthetic parameters. Crystal structure analysis finds that CdS shell is wurtzite on either wurtzite or zinc-blende CdSe cores. Morphology and photoluminescence studies exhibit that for zinc-blende CdSe based samples, the shell growth is in fine epitaxy and the obtained core/shell nanocrystals show high quantum yield both before and after surface modification process; while wurtzite CdSe based samples have irregular shape indicating inhomogeneous shell growth, and are with lower quantum yield. Furthermore, in the photoluminescence spectra exited with UV radiation, wurtzite CdSe based samples show side peaks of independently nucleated nanocrystals from the shell material; while samples with zinc-blende CdSe cores are potent in restricting these byproducts, which may attribute to the highly effective arrestment of precursor ions onto the zinc-blende CdSe surface. These features manifest that zinc-blende CdSe is more talented than conventional wurtzite CdSe in achieving core/shell nanocrystals with higher qualities.     

ZnCuInS/ZnSe/ZnS量子点发光光谱特性的研究

ZnCuInS/ZnSe/ZnS量子点是一种无毒,无重金属的“绿色”半导体纳米材料。在研究中,制备了三种尺寸的ZnCuInS/ZnSe/ZnS核壳量子点,其直径分别为3.3,2.7,2.3 nm。通过测量不同尺寸的ZnCuInS/ZnSe/ZnS量子点的光致发光光谱,其发射峰值波长随尺寸的减小而蓝移。其吸收峰值波长和发射峰值波长分别是510,611(3.3 nm),483,583(2.7 nm)以及447,545 nm(2.3 nm)。ZnCuInS/ZnSe/ZnS量子点具有显著的尺寸依赖效应。ZnCuInS/ZnSe/ZnS量子点的斯托克斯位移分别为398 meV(3.3 nm),436 meV(2.7 nm)以及498 meV(2.3 nm),这样大的斯托克斯位移证明,ZnCuInS/ZnSe/ZnS量子点的发光机制与缺陷能级有关。同时,对直径为3.3 nm的ZnCuInS/ZnSe/ZnS量子点进行了温度依赖的光致发光光谱的测量,当温度为15～90 ℃时,该量子点发射峰值波长随温度的升高而红移,发光强度随温度的升高而降低,说明ZnCuInS/ZnSe/ZnS量子点是以导带能级与缺陷能级之间跃迁为主的复合发光。     

ZnO/ZnS核-壳量子点的双光子吸收效应

利用飞秒激光Z-扫描与泵浦-探测技术,研究了室温下ZnO/ZnS与ZnO/ZnS/Ag核-壳胶体量子点的双光子吸收效应.研究发现:ZnO基核-壳量子点的本征双光子吸收系数比ZnO体材料增大了3个数量级;测量得到的660 nm处的ZnO/ZnS核-壳量子点双光子吸收截面约为4.3×10^-44 cm⁴·s·photon^-1,比相应的ZnS、ZnSe及 CdS量子点大2个数量级;当ZnO/ZnS核-壳量子点镶嵌了银纳米点时,非线性吸收有所增强.ZnO基复合纳米结构的双光子吸收增强可归因于量子限域与局域场效应.     

单核/双壳结构CdSe/CdS/ZnS纳米晶的合成与发光性质

以巯基乙酸为稳定剂,在水溶液中合成了单核/双壳结构的CdSe/CdS/ZnS纳米晶。在内核CdSe和外壳ZnS之间的内壳CdS作为晶格匹配调节层,能够很好的改善核/壳界面处的性能,而且,最外层ZnS能够最大程度地使激子受限。用TEM和XPS对纳米晶进行了表征,并且用光致发光光谱和吸收光谱对不同核壳结构的纳米晶的发光性能进行了比较,结果表明单核/双壳结构的纳米晶具有更加优异的发光特性。     

Facile synthesis of mercaptosuccinic acid-capped CdTe/CdS/ZnS core/double shell quantum dots with improved cell viability on different cancer cells and normal cells

Water-soluble, mercaptosuccinic acid (MSA)-capped CdTe/CdS/ZnS core/double shell quantum dots (QDs) were prepared by successive growth of CdS and ZnS shells on the as-synthesized CdTe/CdS_thin core/shell quantum dots. The formation of core/double shell structured QDs was investigated by ultraviolet-visible (UV–Vis) absorption and photoluminescence (PL) spectroscopy, PL decay studies, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The core/double shell QDs exhibited good photoluminescence quantum yield (PLQY) which is 70% higher than that of the parent core/shell QDs, and they are stable for months. The average particle size of the core/double shell QDs was ～3 nm as calculated from the transmission electron microscope (TEM) images. The cytotoxicity of the QDs was evaluated on a variety of cancer cells such as HeLa, MCF-7, A549, and normal Vero cells by 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) cell viability assay. The results showed that core/double shell QDs were less toxic to the cells when compared to the parent core/shell QDs. MCF-7 cells showed proliferation on incubation with QDs, and this is attributed to the metalloestrogenic activity of cadmium ions released from QDs. The core/double shell CdTe/CdS/ZnS (CSS) QDs were conjugated with transferrin and successfully employed for the biolabeling and fluorescent imaging of HeLa cells. These core/double shell QDs are highly promising fluorescent probe for cancer cell labeling and imaging applications.     

Optical properties of core/multishell CdSe/Zn(S,Se) nanocrystals

CdSe nanocrystals are now known as highly efficient fluorescent light sources. Their efficiency is however strongly dependent on the quality of the passivation layers. We show here that using a ZnSe/ZnS bi-layer shell leads to a larger photoluminescence yield than both ZnSe and ZnS simple shells. The intermediate ZnSe layer acts as a lattice parameter adaptation layer to improve on the core/shell interface quality, while the ZnS outer shell maximizes the exciton confinement.     

CdSe/ZnSe量子点在油水两相体系下的聚合物包覆相转移及其光谱表征

采用油水两相溶液体系,借助于双亲聚合物包覆实现了CdSe/ZnSe核壳结构量子点自油相到水相的相转移。油水两相中的聚合物包覆与已经报道的均相溶液中聚合物包覆量子点的方法不同,包覆过程在油水两相界面处完成,有效地减少了聚合物缠绕引起的量子点团聚,实现了聚合物对量子点的无团聚单分散包覆。透射电镜和激光粒度分析仪对聚合物包覆量子点的表征结果表明获得的水溶性量子点具有良好的分散性,均一的水力尺寸。吸收和发射光谱表明聚合物包覆过程对量子点的发射峰位和峰型没有引起明显的改变,维持了较高的量子产率。通过荧光微区成像技术成功实现了对人IgG蛋白的特异性检测,证实这种方法获得的聚合物包覆量子点具有较好的与生物分子偶联的功能化基团,适合于生物学标记应用。     

2018年2期电子期刊

光诱导功能退化是胶体量子点在应用中面临的主要挑战之一,本文针对这一问题研究了使用磁控溅射沉积SiO₂薄膜形成钝化层来提高CdSe/ZnS量子点发光稳定性的方法。首先,通过三正辛基膦辅助连续离子层吸附反应方法合成了615 nm发光的红色CdSe/ZnS量子点。然后将量子点旋涂在SiO₂/Si基片上,再通过磁控溅射方法在量子点上沉积了厚度为20 nm的SiO₂薄膜作为钝化层。使用连续波激光光源分别在空气气氛和真空条件下照射样品,研究了经过不同照射时间后钝化和未钝化量子点的稳态光致发光光谱。结果表明,随着照射时间的延长,没有SiO₂钝化的量子点的PL强度显著降低、PL峰值发生蓝移、FWHM不断增大。对比研究发现,由于SiO₂薄膜能够阻挡空气中的水和氧,减缓了量子点表面的光诱导氧化现象,因此显著提高了CdSe/ZnS量子点的稳定性。     

Re-charging the luminescence states in CdSe/ZnS quantum dots at the conjugation to Osteopontin antibodies

The paper presents the original study of photoluminescence (PL) and Raman scattering spectra of core–shell CdSe/ZnS quantum dots (QDs) covered by the amine-derivatized polyethylene glycol (PEG) with luminescence interface states. First commercially available CdSe/ZnS QDs with emission at 640 nm (1.94 eV) covered by PEG polymer have been studied in nonconjugated states. PL spectra of nonconjugated QDs are characterized by a superposition of PL bands related to exciton emission in a CdSe core and to the hot electron–hole recombination via high energy luminescence states. The study of high energy PL bands in QDs at different temperatures has shown that these PL bands are related to luminescence interface states at the CdSe/ZnS or ZnS/polymer interface. Then CdSe/ZnS QDs have been conjugated with biomolecules—the Osteopontin antibodies. It is revealed that the PL spectrum of bioconjugated QDs changed essentially with decreasing hot electron–hole recombination flow via luminescence interface states. It is shown that the QD bioconjugation process to Osteopontin antibodies is complex and includes the covalent and electrostatic interactions between them. The variation of PL spectra due to the bioconjugation is explained on the basis of electrostatic interaction between the QDs and biomolecule dipoles that stimulates re-charging QD interface states. The study of Raman scattering of bioconjugated CdSe/ZnS QDs has confirmed that the antibody molecules have the electric dipoles. It is shown that CdSe/ZnS QDs with luminescence interface states are promising for the study of bioconjugation effects with specific antibodies and can be a powerful technique in biology and medicine.