微反应器中利用非配位有机溶剂法可控合成CdSe量子点

采用微反应器技术, 在低毒性的非配位有机溶剂十八烯(ODE)/配体十八烯酸(OA)反应体系中对CdSe量子点进行了尺寸可控合成. 详细探讨了制备条件对生成的CdSe量子点的粒子数及粒子尺寸的影响. 结果表明, 反应温度对生成的粒子数不产生显著影响, 但相对较高的温度有利于具有较强荧光性的CdSe量子点生成. 在固定其他反应条件下, 过量的Se有利于生成大量的小粒子, 当n(Cd):n(Se)=1:5时, 产率可接近100%. 反应物中配体的量直接影响到单体的浓度, 通过控制配体OA浓度和反应时间, 成功地制备了一系列显示从蓝色到红色荧光, 粒径在2.2~4.3nm的CdSe量子点.     

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.     

CdSe与CdSe/ZnS量子点合成及稀土掺杂

在LSS(liquid-solid-solution)多相体系中制得了CdSe、CdSe/ZnS量子点和Eu掺杂的量子点。利用TEM、XRD、PL、EDS对产物进行了表征。TEM结果显示所得的量子点形貌规则、尺寸均匀。XRD结果显示CdSe/ZnS量子点呈六方晶系。PL结果对比表明,合适厚度壳层ZnS包覆后的CdSe量子点发光效率明显提高,发光峰的半高宽有大幅度提高,并分析了所得的结果。掺杂稀土元素Eu后,CdSe(Eu)量子点在红光区域产生了新的发光峰;而CdSe(Eu)/ZnS量子点在红光区域内没有出现发光峰,并阐明了这种现象的原因。     

制成多尺寸量子点太阳能电池

近日,美国圣母大学（University of Notre Dame）～研究小组制备出世界上首例具有多种尺寸量子点的太阳能电池,在TiO2纳米薄膜表面以及纳米管上组装CdSe量子点,吸收光线以后,CdSe向TiO2放射电子,再在传导电极上收集,进而产生光电流。他们研究了2．3～3．7nm四种不同粒径的量子点,发现在505～580nm波段上具有不同的吸收峰。研究人员Prashant V．Kamat介绍说,TiO2纳米管上固定CdSe量子点能够形成规整的组装结构,不仅可以使电子有效地传输至电极表面,还能提高电池效率。长度为800nm的纳米管内外表面均可组装量子点,其传输电子的效率较薄膜高。研究发现,小的量子点能以更快的速度将光子转换为电子,而大的量子点     

Ⅱ-Ⅵ族量子点掺杂玻璃的光学性质及研究进展

由于量子限域效应,尺寸可调的Ⅱ-Ⅵ族量子点掺杂玻璃在光学滤波片、非线性光学器件上的应用已经被广泛研究。玻璃中量子点的光学性质主要由量子点的尺寸、表面状态和周围基质环境决定,通过提高Se/Cd比可以有效地对量子点的表面缺陷进行钝化,实现CdSe量子点的本征发光;进一步调整热处理制度可以促进Zn离子扩散进入CdSe量子点表面,形成CdSe/Cd_(1-x)Zn_xSe核壳结构,使得缺陷发光几乎完全猝灭,从而提高量子点的荧光量子效率;在玻璃中原位合成的CdS/ZnS核壳结构量子点的荧光量子效率可达到53%。随着基础研究中玻璃中Ⅱ-Ⅵ族量子点荧光效率的不断提高,发光二极管(LED)等小型发光器件的制造成为可能。为了满足实际需要,建立核壳结构中量子点表面钝化机理模型,进一步优化量子点荧光效率是下一步需要解决的问题。     

在多相体系中制备核壳型CdSe/ZnS量子点

在多相体系中制得了CdSe/ZnS半导体量子点,采用X射线粉末衍射(XRD)、电子透射显微镜(TEM)等测试手段对产物进行了表征,结果表明CaSe/CdS量子点尺寸均一、形貌规则,具有立方晶体结构.初步研究了此体系的反应机理,并通过紫外-可见吸收光谱和荧光光谱对产物的光学性质进行了分析,结果表明在CASe量子点外面包覆一定厚度的ZnS壳层后,其激子发射强度和量子效率显著提高.     

胶体量子点多色LED的设计、制备和表征

量子点LED采用胶体量子点为LED发光层,通过调节量子点的尺寸可以制作出覆盖可见以及近红外光谱的量子点LED(QD-LED),而且量子点LED器件发出的光谱范围很窄(光谱半高宽可达30 nm).为了研究不同发光颜色的QD-LED器件特性,本文采用具有523 nm和608 nm发光波长的CdSe/ZnS核壳型量子点为发光层、poly-TPD为空穴传输层、ZnO为电子传输层,制备了量子点红光和绿光LED并讨论了器件的相关特性.这些结果对量子点LED在飞机驾驶舱以及医疗器械照明方面的应用提供了参考,但要满足商业化的需求其寿命、亮度以及效率还需要进一步的提高.     

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。     

羧基CdSe荧光量子点的制备及其荧光特性研究

以氯化镉、硒粉为前驱体,巯基乙酸(TGA)为稳定剂,制备了羧基CdSe量子点,并研究了其荧光特性与影响因素。结果表明,反应温度、反应时间与反应体系的pH值是影响量子点生长和荧光性能的主要因素。制备羧基CdSe量子点的最优条件为反应温度90℃、pH=11、n(Cd)∶n(Se)=2∶1。制备的羧基CdSe量子点的粒径随反应时间的延长而逐渐增大,量子点荧光稳定性好,荧光强度高,光漂白时间延长。     

MoS2/g-C3N4复合催化剂的制备及CdSe量子点敏化产氢性能研究

太阳能光催化分解水制氢被认为是从根本上解决能源与环境问题较为理想的途径之一。在以尿素为原料制得石墨相氮化碳(g-C_3N_4)的基础之上,采用简单的低温溶液反应法将二硫化钼(MoS_2)与石墨相氮化碳(g-C_3N_4)复合得到复合催化剂MoS_2/g-C_3N_4,并利用透射电子显微镜(TEM)、X射线衍射(XRD)、紫外-可见漫反射(DRS)、傅里叶变换红外光谱(FT-IR)和荧光光谱等对该复合光催化剂的组成、形貌和光物理性能进行了表征;进而以CdSe量子点为光敏剂,三乙醇胺(TEOA)为牺牲剂,构建了不含贵金属的三组分光催化产氢体系,并对体系pH值、CdSe量子点浓度等对产氢性能的影响进行了研究。结果表明:将MoS_2纳米颗粒负载到g-C_3N_4上可使g-C_3N_4的光催化产氢性能得到显著提高。当MoS_2负载量为7%(质量比)时,在最佳的条件下(pH=9.0,CdSe量子点的体积为25mL),最大产氢速率达到了141.74μmol·h-1,6h的产氢总量达到了212.61μmol。最后,结合荧光猝灭实验,推测了该体系的产氢机理。     

CdS量子点的制备和光学性质

以醋酸镉、硫粉为原料制备CdS量子点,研究了硫的加入量对其光学性质的影响,结果表明:合成的CdS量子点粒径均匀,分散性较好,随着硫加入量的增加CdS量子点的粒径增大;反应中过量的硫能有效地填补硫空位,从而抑制表面态发光,同时,ODA的修饰也能有效地钝化表面态,减小表面态的发光强度.     

Luminescent quantum dots fluorescence resonance energy transfer-based probes for enzymatic activity and enzyme inhibitors

The paper describes the development and characterization of analytical properties of quantum dot-based probes for enzymatic activity and for screening enzyme inhibitors. The luminescent probes are based on fluorescence resonance energy transfer (FRET) between luminescent quantum dots that serve as donors and rhodamine acceptors that are immobilized to the surface of the quantum dots through peptide linkers. Peptide-coated CdSe/ZnS quantum dots were prepared using a one-step ligand exchange process in which RGDC peptide molecules replace trioctylphosphine oxide (TOPO) molecules as the capping ligands of the quantum dots. The peptide molecules were bound to the surface of the CdSe/ZnS quantum dots through the thiol group of the peptide cysteine residue. The peptide-coated quantum dots were labeled with rhodamine to form the FRET probes. The emission quantum yield of the quantum dot FRET probes was 4-fold lower than the emission quantum yield of TOPO-capped quantum dots. However, the quantum dot FRET probes were sufficiently bright to enable quantitative enzyme and enzyme inhibition assays. The probes were used first to test the enzymatic activity of trypsin in solution based on FRET signal changes of the quantum dot-based enzymatic probes in the presence of proteolytic enzymes. For example, exposure of the quantum dot FRET probes to 500 microg/mL trypsin for 15 min resulted in 60% increase in the photoluminescence of the quantum dots and a corresponding decrease in the emission of the rhodamine molecules. These changes resulted from the release of rhodamine molecules from the surface of the quantum dots due to enzymatic cleavage of the peptide molecules. The quantum dot FRET-based probes were used to monitor the enzymatic activity of trypsin and to screen trypsin inhibitors for their inhibition efficiency.     

Hole transport in organic field-effect transistors with active poly(3-hexylthiophene) layer containing CdSe quantum dots

Hybrid field-effect transistors (FETs) based on poly(3-hexylthiophene) (P3HT) containing CdSe quantum dots (QDs) were fabricated. The effect of the concentration of QDs on charge transport in the hybrid material was studied. The influence of the QDs capping ligand on charge transport parameters was investigated by replacing the conventional trioctylphosphine oxide (TOPO) surfactant with pyridine to provide closer contact between the organic and inorganic components. Electrical parameters of FETs with an active layer made of P3HT:CdSe QDs blend were determined, showing field-effect hole mobilities up to 1.1×10^?4 cm²/Vs. Incorporation of TOPO covered CdSe QDs decreased the charge carrier mobility while the pyridine covered CdSe QDs did not alter this transport parameter significantly.     

Facile patterning of hybrid CdSe nanoparticle films by photoinduced surface defects

The photopatterning of CdSe quantum dots (QDs) films is facilitated by preparing defect-rich QDs on selective sites on the film. A key step is UV irradiation in the presence of a polar solvent such as methanol in situ as a "developer" which readily dissolves trioctylphosphine oxide (TOPO) but not the QDs. This results in a dramatically reduced photopatterning time and irradiation intensity requirement. The optical property changes were examined by UV-vis and fluorescence spectroscopy. Furthermore, the photo-oxidized pattern of the CdSe QD film was readily observed by fluorescence microscopy. The chemical change due to attenuation of the P═O vibration of TOPO (due to its removal) could be detected by FT-IR imaging or FT-IR chemical mapping. Thus, the protocol is a simple yet effective way of patterning PL properties of QD films at much reduced exposure time compared to previously reported methods. It may find utility for a host of cell-based film assays and PL display device applications at various resolutions.     

Uncoated, broad fluorescent, and size-homogeneous CdSe quantum dots for bioanalyses

In the present study, we describe the synthesis of highly luminescent uncoated water-soluble CdSe quantum dots (QDs) possessing the following characteristics: approximately 2 nm in diameter, with very good size distribution (in 95% homodispersed) accompanied by a broad-band photoluminescent spectrum. The synthetic procedure is simple, is conducted at room temperature, in the absence of the most popular coordinating ligands (as TOPO or HDA), and is highly reproducible. The obtained CdSe core QDs possessed a comparatively long fluorescence half-life (approximately 30-90 ns, depending on the emission wavelength) detected by time-resolved spectroscopy. These QDs were further conjugated with antibodies and applied in several biochemical analyses.     

Improved performance of nanocrystal quantum dots-based LEDs by modifying hole transport layer

Reported herein are the effects of the fabrication variables and surface capping of nanocrystal quantum dots (NQDs) on the characteristics of NQDs-based light-emitting diodes (LEDs). The molecular weight of the hole transport layer (HTL) material and the annealing conditions of the NQDs layer were chosen as fabrication process variables. Their effects on the layer characteristics and device efficiency were characterized. The maximum brightness varied over 50% according to the molecular weight of the HTL material. The optimized annealing temperature was shown to improve the maximum brightness by 20%. The surface-capping molecules of the NQDs were changed from conventional trioctyl phosphine/trioctyl phosphine oxide (TOPO/TOP) to pyridine and were incorporated into LEDs, and its effects on the device characteristics were discussed.     

Surface modification of CdSe quantum dots for biosensing applications: Role of ligands

For an optimum performance of colloidal nanocrystal devices for a variety of applications such as photonic devices, solar cells and biological labelling, the determining factors are the nanocrystal surface and size. In this work, these two factors have been tuned via wet chemistry to tailor the material properties: The absorption and emission spectra have been tailored by choice of the nanocrystal size; nanocrystal shape by surface modification and photoluminescence (PL) efficiency determined by surface traps, has been tuned via appropriate selection of the nanocrystal capping ligands. Here, we have shown that through ligand-exchange process, the surface of the CdSe quantum dots (QDs) can be modified by replacing the longer-chain ligands of conventional trioctyl phosphine oxide (TOPO) or oleic acid (OA) with shorter-chain ligand of butyl amine. This imparts colloidal stability and water solubility to CdSe QDs for its potential applications in biosensors and biological imaging. It is conjectured that crystallite sizes, oxidation potential of CdSe QDs and stereochemical compatibility of ligands (TOPO, oleic acid and butyl amine) greatly influences the photophysics and photochemistry of CdSe QDs.     

有缺陷和无缺陷量子点内应变分布的比较与分析

阐述了量子点内能级结构与应变的关系,用ANSYS7．1计算了有缺陷和无缺陷两种情况下：InAs／GaAs量子点的应变分布,通过对计算结果的比较,讨论了两种情况下不同的应变分布对量子点电子结构影响的不同结果,指出有缺陷时量子点各能级的改变量都与无缺陷时不同,无缺陷时应变的作用只是使能级平行移动;有缺陷时,缺陷将使量子点内能级结构复杂化,有缺陷时发光波长和发光光谱都比无缺陷时复杂。     

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.     

Arginine-glycine-aspartic acid-conjugated dendrimer-modified quantum dots for targeting and imaging melanoma

Angiogenesis is essential for the development of malignant tumors and provides important targets for tumor diagnosis and therapy. Quantum dots have been broadly investigated for their potential application in cancer molecular imaging. In present work, CdSe quantum dots were synthesized, polyamidoamine dendrimers were used to modify surface of quantum dots and improve their solubility in water solution. Then, dendrimer-modified CdSe quantum dots were conjugated with arginine-glycine-aspartic acid (RGD) peptides. These prepared nanoprobes were injected into nude mice loaded with melanoma (A375) tumor xenografts via tail vessels, IVIS imaging system was used to image the targeting and bio-distribution of as-prepared nanoprobes. The dendrimer-modified quantum dots exhibit water-soluble, high quantum yield, and good biocompatibility. RGD-conjugated quantum dots can specifically target human umbilical vein endothelial cells (HUVEC) and A375 melanoma cells, as well as nude mice loaded with A735 melanoma cells. High-performance RGD-conjugated dendrimers modified quantum dot-based nanoprobes have great potential in application such as tumor diagnosis and therapy.