CdSe包覆层数对水溶性CdTe/CdSe (II型)核壳量子点的光学特性和微观结构的影响

在水相合成的CdTe量子点的体系中通过分批次加入新鲜配制的NaHSe和CdCl2溶液,制备出了CdSe包覆层数不同的CdTe/CdSe核壳量子点,并着重考察了CdSe包覆层数对CdTe/CdSe核壳量子点的光学特性以及微观结构的影响.与CdTe量子点相比,CdSe单层包覆的CdTe/CdSe核壳量子点的吸收峰和荧光发射峰出现明显红移;随着CdSe包覆层数的增多,CdTe/CdSe核壳量子点吸收光谱的覆盖范围向长波方向扩展,荧光发射峰强度逐步下降,荧光寿命大幅延长,体现出Ⅱ型核壳量子点的特征.X射线衍射(XRD)分析表明,随着CdSe包覆层数的增多,CdTe/CdSe核壳量子点的粉末衍射峰由CdTe衍射峰位置逐步向CdSe衍射峰位置靠近.CdTe/CdSe核壳量子点因其延伸到近红外区域的宽吸收特性致使其在太阳电池领域具有重要的应用前景.     

CdTe/CdSe核壳量子点的合成及其在指纹显现中的应用

以CdCl2和Te粉为原料,在水相中合成了CdTe量子点核;通过外延生长在CdTe量子点核上包覆一层CdSe量子点,得到具有良好荧光性能的CdTe/CdSe核壳量子点;采用X射线衍射仪、透射电镜、高分辨透射电镜分析了不同反应条件下合成的CdTe/CdSe核壳量子点的晶体结构和微观结构,并对其进行了荧光光谱等测试和指纹显现分析.结果表明,合成的CdTe和CdTe/CdSe量子点粒径在3～5nm之间,粒径分布窄,水分散性良好;可以通过控制反应时间和Te/Se比等得到在500～700nm显示荧光发射峰的CdTe/CdSe核壳量子点.此外,核壳CdTe/CdSe量子点可以有效地和指纹物质结合,可应用于对铝合金油潜指纹的鉴别.     

水溶性CdSe/CdS量子点的合成及其与牛血清蛋白的共轭作用

用巯基乙酸(TGA)作为稳定剂，合成了水溶性的CdSe和核壳结构的CdSe/CdS半导体量子点。吸收光谱和荧光光谱研究表明，核壳结构的CdSe/CdS半导体量子点比单一的CdSe量子点具有更优异的发光特性。用TEM、电子衍射(ED)和XPS分别表征了CdSe和CdSe/CdS纳米微粒的结构、形貌及分散性。红外光谱和核磁共振谱证实了巯基乙酸分子中的硫原子和氧原子与纳米微粒表面的金属离子发生了配位作用。在pH值为7.4的条件下，将合成的CdSe和CdSe/CdS量子点直接与牛血清白蛋白(BSA)相互作用。实验发现，两种量子点均对BSA的荧光产生较强的静态猝灭作用；而BSA对两种量子点的荧光则具有显著的荧光增敏作用，存在BSA时CdSe/CdS量子点的荧光增强是不存在BSA时体系荧光强度的3倍。     

油胺/油酸稳定的CdSe量子点的绿色合成

以液体石蜡为高温反应溶剂,油酸和油胺为混合稳定剂,利用高温热解法一步合成了高质量的CdSe量子点。通过紫外-可见吸收光谱、荧光发射光谱、红外光谱和X射线衍射等手段对量子点的光学性质和结构进行了表征。结果表明,油胺/油酸混合表面活性剂稳定的量子点吸收光谱峰形更尖锐,荧光发射光谱半峰宽更窄。反应温度和反应时间均对量子点的生长过程和光学性质有明显影响,220℃下反应15 min,荧光量子产率可达26%。得到的CdSe量子点为立方晶型,表面同时包覆了油酸和油胺,具有良好的光稳定性。该方法无需使用三烷基膦,价廉环保,且合成的CdSe量子点性质稳定、性能优越,有利于其在分析检测领域中的应用。     

柠檬酸稳定的水溶性CdSe和CdSe/CdS量子点的荧光特性

用柠檬酸(citrate)作为稳定剂合成了尺寸分布集中、荧光性质良好的水溶性CdSe量子点。通过调节合成温度可以调控CdSe量子点的尺寸及相应的最大荧光发射波长。当温度由20 ℃增加到95 ℃时,合成的CdSe量子点的平均尺寸由2.0 nm增加到3.2 nm,相应的荧光发射峰由500 nm红移到570 nm,展现出明显的量子尺寸效应。进一步制备了CdSe/CdS核壳量子点,其荧光量子产率比CdSe增加了5～10倍。系统地研究了S/Se物质的量的比对CdSe/CdS量子点荧光特性的影响,通过XPS证实了CdSe/CdS量子点中CdS壳层的存在。利用红外光谱和核磁共振波谱表征了柠檬酸分子中的羧基和羟基氧原子与CdSe量子点表面的Cd离子的配位作用,进而揭示了柠檬酸分子对水溶性CdSe量子点溶液的稳定作用。     

核-壳结构CdSe/ZnS量子点的制备、硫醇修饰及其光学性能

采用高温有机相包覆技术制备了CdSe/ZnS核壳结构量子点材料,考察了包覆量对量子点材料的光学性能的影响,研究了含脂肪链和芳香基的双硫醇分子1,4-苯二甲硫醇和1,8-辛二硫醇对于具有核-壳结构的CdSe/ZnS量子点材料的修饰作用,考察了修饰作用对于量子点的量子效率和荧光强度等光学性能的影响.实验结果表明:随着硫化锌包覆量的增加,量子点的量子效率及其荧光发射强度明显提高;硫醇的修饰能显著增强量子点的发光强度,随着硫醇浓度的增加,其发光性能增强,但是达到一定程度后,光学性能基本不随硫醇浓度的变化而变化.根据固体核磁共振等实验结果推测:硫醇分子可能部分替代了量子点体系中的正三辛基氧膦配体,稳定了量子点体系,对量子点起修饰保护作用,从而提高了量子点的光学性能.     

硫脲修饰ZnSe:Cu量子点的水相合成及荧光特性

以3-巯基丙酸为稳定剂在水相中合成了Cu掺杂的ZnSe量子点(QDs), 并利用硫脲(CH₄N₂S)对其进行表面修饰, 制备出核壳结构的ZnSe:Cu/ZnS 量子点. 制得的量子点呈闪锌矿结构, 尺寸约为5 nm, 有较好的分散性, 其荧光发射峰在460 nm左右. 经CH₄N₂S修饰后, 量子点表面形成了宽禁带的ZnS包覆层, 将电子和空穴限域在了ZnSe:Cu 核内, 减少了表面发生非辐射复合的载流子, 显著提高了量子点的荧光强度. 与Na₂S、硫代乙酰胺(TAA)等常用硫源相比, 以CH₄N₂S为硫源制得的ZnSe:Cu/ZnS 量子点壳层厚度可控, 表面钝化效果更好, 显示出更佳的荧光效率和稳定性. ZnSe:Cu/ZnS 量子点经过紫外线照射后消除了表面的悬空键, 进一步提高了其量子产率, 最终获到了具有较好荧光性质的ZnSe:Cu/ZnS量子点.     

利用离子型Cd源制备ZnSe/CdSe核-壳结构纳米晶

在有机相体系中利用ZnSe前驱体纳米晶制备过程中的富Se环境,以引入Cd2+的方式在相对温和的环境下通过控制Cd2+离子的加入量及调节反应时间,成功制备了ZnSe/CdSe核-壳复合结构纳米晶.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(FL)对其结构形貌以及光学性质进行表征和分析的结果表明,CdSe以外延生长的方式包覆在ZnSe纳米晶表面从而形成具有良好结晶性的核-壳复合结构,其荧光发射始终保持良好单色性,同时实现了在500～620nm可见光范围内的连续可调.     

铜掺杂ZnSe量子点荧光探针测定镉(Ⅱ)

基于镉(Ⅱ)与ZnSe/Cu量子点之间的荧光猝灭作用,提出了用ZnSe/Cu量子点作为荧光探针测定镉的方法。通过微波辅助加热,在水溶液中合成了巯基丙酸修饰的ZnSe/Cu量子点。用荧光光谱、紫外光谱研究了ZnSe/Cu量子点与镉(Ⅱ)的相互作用。在pH为7.4的三羟甲基氨基甲烷-盐酸缓冲溶液和1.5×10-4 mol·L-1 ZnSe/Cu量子点溶液中测定镉(Ⅱ)。镉(Ⅱ)的质量浓度在0.025~0.40mg·L-1范围与ZnSe/Cu量子点荧光猝灭强度呈线性关系,方法的检出限(3s/k)为0.021 6mg·L-1。方法应用于水样的测定,回收率为98.0%,102%。对0.15mg·L-1镉(Ⅱ)标准溶液测定11次,测定值的相对标准偏差为6.7%。     

CdSe/CdS量子点荧光探针用于司帕沙星的测定

在规定的条件下和pH 11的碱性溶液中,通过镉（Ⅱ）、巯基乙酸（TGA）与硒化氢钾乙醇溶液之间的反应制得TGA修饰的CdSe量子点（QD′s）,再将此量子点和硫化钠溶液反应制得TGA修饰的CdSe/CdS量子点。基于喹诺酮类抗生素司帕沙星与CdSe/CdS量子点的荧光猝灭作用,用CdSe/CdS量子点作为荧光探针测定了...     

pH-sensitive Photoluminescence of CdSe/ZnSe/ZnS Quantum Dots in Human Ovarian Cancer Cells

The photoluminescence of mercaptoacetic acid (MAA)-capped CdSe/ZnSe/ZnS semiconductor nanocrystal quantum dots (QDs) in SKOV-3 human ovarian cancer cells is pH-dependent, suggesting applications in which QDs serve as intracellular pH sensors. In both fixed and living cells the fluorescence intensity of intracellular MAA-capped QDs (MAA QDs) increases monotonically with increasing pH. The electrophoretic mobility of MAA QDs also increases with pH, indicating an association between surface charging and fluorescence emission. MAA dissociates from the ZnS outer shell at low pH, resulting in aggregation and loss of solubility, and this may also contribute to the MAA QD fluorescence changes observed in the intracellular environment.     

Synthesis of InAs/CdSe/ZnSe core/shell1/shell2 structures with bright and stable near-infrared fluorescence

A complex InAs/CdSe/ZnSe core/shell1/shell2 (CSS) structure is synthesized, where the intermediate CdSe buffer layer decreases strain between the InAs core and the ZnSe outer shell. This structure leads to significantly improved fluorescence quantum yield as compared to previously prepared core/shell structures and enables growth of much thicker shells. The shell growth is done using a layer-by-layer method in which the shell cation and anion precursors are added sequentially allowing for excellent control, and a good size distribution is maintained throughout the entire growth process. The CSS structure is characterized using transmission electron microscopy, as well as by X-ray diffraction and X-ray photoelectron spectroscopy which provide evidence for shell growth. The quantum yield for CSS with small InAs cores reaches over 70%-exceptional photoluminescence intensity for III-V semiconductor nanocrystals. In larger InAs cores there is a systematic decrease in the quantum yield, with a yield of approximately 40% for intermediate size cores down to a few percent in large cores. The CSS structures also exhibit very good photostability, vastly improved over those of organically coated cores, and transformation into water environment via ligand exchange is performed without significant decrease of the quantum yield. These new InAs/CdSe/ZnSe CSS nanocrystals are therefore promising near-IR chromophores for biological fluorescence tagging and optoelectronic devices.     

Temperature-dependent photoluminescence of water-soluble quantum dots for a bioprobe

The photoluminescence of water-soluble CdSe/ZnS core/shell quantum dots is found to be temperature-dependent: as temperature arising from 280 K to 351 K, the photoluminescence declines with emission peak shifting towards the red at a rate of ∼0.11 nm K⁻¹. And the studies show that the photoluminescence of water-soluble CdSe/ZnS quantum dots with core capped by a thinner ZnS shell is more sensitive to temperature than that of ones with core capped by a thicker one. That is, with 50% decrement of the quantum yield the temperature of the former need to arise from 280 K to 295 K, while the latter requires much higher temperature (315.6 K), which means that the integrality of shell coverage is a very important factor on temperature-sensitivity to for the photoluminescence of water-soluble CdSe/ZnS quantum dots. Moreover, it is found that the water-soluble CdSe quantum dots with different core sizes, whose cores are capped by thicker ZnS shells, possess almost the same sensitivity to the temperature. All of the studies about photoluminescence temperature-dependence of water-soluble CdSe/ZnS core/shell quantum dots show an indispensable proof for their applications in life science.     

水溶性的高荧光CdTe/CdSeⅡ型核壳量子点的合成与表征

用L-半胱氨酸(L-cysteine)作为稳定剂,以制备的CdTe量子点为核模板,水相合成了具有近红外发光的Ⅱ型核壳CdTe/CdSe半导体量子点。实验考察了合成温度,核模板的尺寸和组分比等因素对合成高质量的CdTe/CdSe量子点的影响。用紫外-可见吸收和荧光光谱研究了合成的量子点的光学性质。在优化的合成条件下,荧光发射光谱在586～753nm范围连续可调,荧光量子产率高达68%;通过X-射线衍射(XRD),X射线光电子能谱(XPS)和透射电镜(TEM)对合成的Ⅱ型核壳CdTe/CdSe量子点进行了结构和形貌表征。     

An effective oxidation route to blue emission CdSe quantum dots

Nearly monodisperse CdSe quantum dots with blue emission are obtained through an oxidation approach, in which CdSe particles can be etched into smaller ones. During the oxidation process, CdSe with yellow emission (546 nm) can be rapidly oxidized to blue emission (466 nm) due to its incompletely crystallized structure. Further oxidation results in the slow blue-shift of the photoluminescence peak to 433nm. The quantum fluorescence efficiency of CdSe with blue emission is about 10%, and surface-trap emission becomes evident when the PL peak of CdSe reaches the blue-violet region, since the surface atom ratio increases. This oxidation route offers a simple and mild way to get extremely small CdSe quantum dots.     

水溶性CdSe量子点的合成及其作为荧光探针对大肠杆菌的快速检测

采用水相法以谷胱甘肽为稳定剂合成高稳定性的CdSe量子点,利用化学偶联剂的作用使得量子点表面基团与菌体之间的成功结合,对偶联的条件进行了优化.基于荧光分析法建立了一种快速简便的大肠杆菌检测定量分析方法.研究结果表明:合成的量子点具有稳定、荧光性能良好等突出优点.通过偶联剂量子点能与大肠杆菌结合,其荧光强度与大肠杆菌浓度...     

Selective turn-on fluorescence detection of cyanide in water using hydrophobic CdSe quantum dots

The ability of 2,2'-bipyridine-bound copper(ii) ions to quench the photoluminescence of hydrophobic CdSe quantum dots is used to create a novel, selective turn-on fluorescence cyanide sensor.     

Molecularly imprinted polymeric film on semiconductor nanoparticles analyte detection by quantum dot photoluminescence

Incorporation of semiconductor nanoparticles into molecularly imprinted polymer provides a sensor material which can be easily shaped and with better selectivity because the bound template would quench the photoluminescence (PL) emission of quantum dots significantly. In this work, artificial receptors of various templates were synthesized with functional monomers such as methacrylic acid (MAA), semiconductor like CdSe/ZnS core-shell derivatized with 4-vinylpyridine and ethylene glycol dimethacrylic acid as the cross-linker. The quenching of photoluminescence emissions is presumably due to the fluorescence resonance energy transfer between quantum dots and template molecules. The photoluminescence emission is unaffected upon incubation of analyte with the blank control polymer.