Effect of shell layers on luminescence of colloidal CdSe/Zn(0.5)Cd(0.5)Se/ZnSe/ZnS core/multishell quantum dots

Colloidal CdSe/Zn(0.5)Cd(0.5)Se/ZnSe/ZnS core/multishell quantum dots (QDs) were synthesized by using the well developed successive ion layer adsorption and reaction (SILAR) technique. The UV-vis and PL spectra, TEM, X-ray diffraction and Raman measurement were performed to investigate the structure and optical properties of prepared QDs during the growth of shell layers, which indicated that the stress in CdSe core became stronger with the increasing shell thickness. Due to the gradual adjustment of the lattice parameters in the radial direction and the radial increase of the respective valence- and conduction-band offsets, the optical measurements show a significant enhancement in the photoluminescence quantum yield (QY) and an expedited radiative decay in QDs overcoated with thicker shell. The temperature-dependent optical spectra were measured, and the relation between the microstructure and the optical properties of these core/multishell quantum dots was discussed.     

CdSe/ZnSe量子点的制备及电化学发光性能

利用ZnSe半导体纳米材料晶体结构与CdSe相似、带隙更宽的特点,采用水热法合成了核-壳型CdSe/ZnSe量子点.结果表明:温度在70～160℃时,ZnSe壳逐渐包裹在CdSe核上,反应时间在0～4 h时,内壳在核上是均匀包裹的,当核壳摩尔比为1:3时,CdSe/ZnSe QDs的电化学发光性能最强,其电化学发光强度...     

Photoluminescence-enhanced biocompatible quantum dots by phospholipid functionalization

A simple two-step strategy using phospholipid (PPL) to functionalize core/shell CdSe/ZnS quantum dots (QDs) has been described. The experimental data show that the use of S-H terminated PPL results not only in the high colloidal stability of core/shell CdSe/ZnS QDs in the aqueous phase, but also in the significant enhancement of photoluminescence. The degree of the enhancement is a function of the PPL-CdSe/ZnS QDs sample concentration. These results might be promising for future biological platform in new devices ranging from photovoltaic cells to biosensors and other devices.     

CdSe/Cd1−x Zn x S core/shell quantum dots with tunable emission: growth and morphology evolution

We demonstrate an organic synthesis to fabricate hydrophobic core/shell CdSe/Cd_1?x Zn _x S quantum dots (QDs) with tunable photoluminescence (PL) between green and red at relatively low temperature using trioctylphosphine S reacted directly with cadmium and zinc acetate. A seeded growth strategy was used for preparing large CdSe cores. Large CdSe cores revealed a rod-like morphology while small one exhibited a spherical shape. Being coated with a Cd_1?x Zn _x S shell on spherical CdSe cores with an average size of 3.9 nm in diameter, core/shell QDs exhibited a cubic morphology (a length of 5 nm). In contrast, the core/shell QDs created using a small core (3.3 nm in diameter) show a spherical morphology. Namely, the anisotropic aggregation behavior of CdS monomers on CdSe cores occurs when the rod-like core is coated with a Cd_1?x Zn _x S shell. CdS interlayer plays an important role for such morphology evolution because all CdSe cores with a pure ZnS shell exhibited a spherical morphology. The PL properties of CdSe/Cd_1?x Zn _x S core/shell QDs depended strongly on the size and morphology of the cores. The QDs revealed a narrow and tunable PL spectrum. It is believed that this facile strategy can be extended to synthesize other core–shell QDs at low temperature.     

Structural characterization of CdSe/ZnS core–shell quantum dots (QDs) using TEM/STEM observation

CdSe/ZnS core–shell structured nano-crystal quantum dots (QDs) are ideal candidates for light-emission applications due to their high quantum efficiency, narrow-band, and particle-size-tunable photoluminescence. In particular, their small size results in the quantum confinement of semiconductor nano-crystals, which widens their energy gaps. In general, structural analyses of QDs using a transmission electron microscope (TEM) are very important due to the significantly small size of QDs. We were able to obtain structural information of CdSe/ZnS core–shell QDs using nano-beam diffraction by controlling the nano-probe of the dark field scanning TEM (DF-STEM) mode and strain analysis with high-resolution TEM (HRTEM)/STEM images. Furthermore, we could clearly distinguish the interface between the CdSe core and the ZnS shell from the strain analysis with the HRTEM/STEM images.     

Aqueous synthesis of CdSe and CdSe/CdS quantum dots with controllable introduction of Se and S sources

A new and convenient route is developed to synthesize CdSe and core–shell CdSe/CdS quantum dots (QDs) in aqueous solution. CdSe QDs are prepared by introducing H₂Se gas into the aqueous medium containing Cd²⁺ ions. The synthesized CdSe QDs are further capped with CdS to form core–shell CdSe/CdS QDs by reacting with H₂S gas. The gaseous precursors, H₂Se and H₂S, are generated on-line by reducing SeO₃ ^2? with NaBH₄ and the reaction between Na₂S and H₂SO₄, and introduced sequentially into the solution to form CdSe and CdSe/CdS QDs, respectively. The synthesized water-soluble CdSe and CdSe/CdS QDs possess high quantum yield (3 and 20 %) and narrow full-width-at-half-maximum (43 and 38 nm). The synthesis process is easily reproducible with simple apparatus and low-toxic chemicals. The relatively standard deviation of maxima fluorescence intensity is only 2.1 % (n = 7) for CdSe and 3.6 % (n = 7) for CdSe/CdS QDs. This developed route is simple, environmentally friendly and can be readily extended to the large-scale aqueous synthesis of QDs.     

Simple method to fabricate large scale quantum dot architectures

We present a facile method of incorporating CdSe/ZnSe core/shell quantum dots (QDs) into 600 nm diameter pores of a two-dimensional lattice made by interference lithography of spin-coated SU-8 photoresist on Si substrates. The luminescent assembly can be formed in an area as large as 1 cm². Confocal luminescence microscopy shows that the QDs can readily fill via capillary action into hexagonal hole arrays with a depth of about 3 µm and a periodicity of about 1 µm. The fabricated large scale architectures are expected to be useful for optical devices such as light emitting diodes.     

Synthesis and photoluminescence of bright water-soluble CdSe/ZnS quantum dots overcoated by hybrid organic shell

Photoluminescence properties from water soluble CdSe/ZnS QDs encapsulated with hybrid trioctylphosphine-poly(acrylamide-co-acrylic acid)-ethanolamine (TOPO-PSMA-EA) shell have been investigated. It was found that PL efficiency of CdSe/ZnS QDs in water was increased 5–30% after introducing PSMA-EA polymers to encapsulate CdSe/ZnS-TOPO QDs. Higher PSMA concentrations were found to enhance the PL efficiency of QDs up to 1.8 folds, which is ascribed to a better packing and passivation of the TOPO-PSMA-EA shell over the QDs. Time-resolved photoluminescence suggested that the mean lifetime of photoexcited carriers in the water-soluble CdSe/ZnS-TOPO-PSMA-EA QDs elongated 2–17 ns compared with that of uncoated samples, indicating that PL quenching defects were effectively removed for CdSe/ZnS QDs with hybrid TOPO-PSMA-EA shell.     

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.     

Organic light-emitting devices fabricated utilizing core/shell CdSe/ZnS quantum dots embedded in a polyvinylcarbazole

Electrical and the optical properties of organic light-emitting devices (OLEDs) fabricated utilizing core/shell CdSe/ZnS quantum dots (QDs) embedded in a polyvinylcarbazole (PVK) layer were investigated. An abrupt increase of the current density above an applied voltage of 12 V for OLEDs consisting of Al/LiF/4,7-diphenyl-1,10-phenanthroline/bis-(2-methyl-8-quinolinolate)-4-(phenylphenolato) aluminium/[CdSe/ZnS QDs embedded in PVK]/poly(3,4-ethylenedioxythiophene) and poly(styrenesulfonate)/ITO/glass substrate was attributed to the existence of the QDs. Photoluminescence spectra showed that the peaks at 390 and 636 nm corresponding to the PVK layer and the CdSe/ZnS QDs were observed. While the electroluminescence (EL) peak of the OLEDs at low voltage range was related to the PVK layer, the EL peak of the OLEDs above 12 V was dominantly attributed to the CdSe/ZnS QDs. The Commission Internationale de l’Eclairage (CIE) chromaticity coordinates of the OLEDs at high voltages were (0.581, 0.380) indicative of a red color. When the holes existing in the PVK layer above 12 V were tunneled into the CdSe/ZnS QDs, the holes occupied by the CdSe/ZnS QDs combined with the electrons in the PVK layer to emit a red color related to the CdSe/ZnS QDs.     

Cyto-/genotoxic effect of CdSe/ZnS quantum dots in human lung adenocarcinoma cells for potential photodynamic UV therapy applications

Quantum dots (QDs) are luminescent nanoparticles (NPs) with promising potential in numerous medical applications, but there remain persistent human health and safety concerns. Although the cytotoxic effects of QDs have been extensively investigated, their genotoxic effects remain under-explored. This study scrutinized the cyto- and genotoxic effects of QDs with a Cadmium selenide/Zinc sulfide (CdSe/ZnS) core/shell, and suggests comprehensive guidelines for the application of QDs in cancer therapy. QDs were used to treat A549 cells in the presence and absence of ultraviolet A/B (UVA/UVB) irradiation. QD-induced cell death was evaluated by 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT), apoptosis, and lactate dehydrogenase (LDH) assays, as well as by real-time PCR analysis of differential mRNA levels of genes, such as ataxia telangiectasia mutated (ATM), p53, and caspase-9, involved in apoptosis. The genotoxic effect of CdSe/ZnS QDs was measured in human cancer cells, for the first time, by comet and micronucleus assays. Treatment with CdSe/ZnS QDs and UVB irradiation resulted in the most severe extent of cell death, indicating strong induction of phototoxicity by CdSe/ZnS QDs in the presence of UVB. Both apoptotic and necrotic cell death were observed upon QDs and UVB combined treatment. The induction of Olive tail moments and micronuclei formation was also most significant when CdSe/ZnS QDs and UVB irradiation were combined. Our results on the genotoxic effect and mechanistic details of CdSe/ZnS QD-induced cell death suggest that UVB irradiation is the most effective method for increasing the potency of QDs during photodynamic cancer therapy.     

Shell distribution on colloidal CdSe/ZnS quantum dots

Scanning transmission electron microscopy (STEM) coupled with electron energy loss spectroscopy (EELS) was used to determine the chemical distribution of semiconductor shell material around colloidal core-shell CdSe/ZnS quantum dots (QDs). EELS signals from positions around the QD indicate a well-defined shell of ZnS surrounding the CdSe core, but the distribution of the shell material is highly anisotropic. This nonuniformity may reflect the differences in chemical activity of the crystal faces of the core QD and implies a nonoptimal QD surface passivation.     

Highly luminescent and quantum-yielding CdSe/ZnS core/shell quantum dots synthesized by a kinetically controlled succession route in 18DMA

Highly luminescent and quantum-yielding (QY) CdSe/ZnS core/shell quantum dots (CS QDs) were synthesised via a new succession route in a non-toxic solvent, N,N-Dimethyl-octadecyl-tertiary-amine(18DMA) at a mild temperature. The CS QDs were also proven to be as efficient in reaching high quantum yields (up to 74%) as their reported high-temperature synthesis with organic phosphine ligands. It was demonstrated that the synthesis temperatures directly determine the size by controlling the rate of the monomer diffusion and adsorption. It was also found that the amount of surfactant oleic acid determined the QY of the QDs, whereas it had little influence on the crystallisation.     

Manganese-doped ZnSe quantum dots as a probe for time-resolved fluorescence detection of 5-fluorouracil

Quantum dots (QDs) are generally used for the conventional fluorescence detection. However, it is difficult for the QDs to be applied in time-resolved fluorometry due to their short-lived emission. In this paper, high-quality Mn-doped ZnSe QDs with long-lived emission were prepared using a green and rapid microwave-assisted synthetic approach in aqueous solution. Fluorescence lifetime of the Mn-doped ZnSe QDs was extended as long as 400 μs, which was 10,000 times higher than that of conventional QDs such as CdS, CdSe, and CdTe. The QDs exhibited an excellent photostability over 35 h under continuous irradiation at 260 nm. Capped with mercaptopropionic acid (MPA), the Mn-doped ZnSe QDs were used for the time-resolved fluorescence detection of 5-fluorouracil (5-FU) with the detection limit of 128 nM. The relative standard deviation for seven independent measurements of 1.5 μM 5-FU was 3.8%, and the recovery ranged from 93% to 106%. The results revealed that the Mn-doped ZnSe QDs could be a good candidate as a luminescence probe for highly sensitive time-resolved fluorometry.     

Traps and performance of MEH-PPV/CdSe(ZnS) nanocomposite-based organic light-emitting diodes

We report the fabrication and investigations of organic light-emitting diodes (OLEDs) using a composite made by mixing poly[2-methoxy-5(2'-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) with CdSe/ZnS core/shell quantum dots (QDs). The electroluminescence efficiency of the studied devices was found to be improved as compared to devices using MEH-PPV. Moreover, the current density decreased with increasing QD concentration. We checked the effects of QDs on the electrical transport by determining the trap states, making use of the charge-based deep level transient spectroscopy (Q-DLTS) technique. The most striking result obtained is the decrease in trap density when adding QDs to the MEH-PPV polymer film. These results suggest that QDs would heal defects in nanocomposite-based devices and that CdSe/ZnS QDs prevent the trap center formation.     

Phosphine-free synthesis of high-quality reverse type-I ZnSe/CdSe core with CdS/Cd(x)Zn(1 - x)S/ZnS multishell nanocrystals and their application for detection of human hepatitis B surface antigen

Highly photoluminescent (PL) reverse type-I ZnSe/CdSe nanocrystals (NCs) and ZnSe/CdSe/CdS/Cd(x)Zn(1 - x)S/ZnS core/multishell NCs were successfully synthesized by a phosphine-free method. By this low-cost, 'green' synthesis route, more than 10 g of high-quality ZnSe/CdSe/CdS/Cd(x)Zn(1 - x)S/ZnS NCs were synthesized in a large scale synthesis. After the overgrowth of a CdS/Cd(x)Zn(1 - x)S/ZnS multishell on ZnSe/CdSe cores, the PL quantum yields (QYs) increased from 28% to 75% along with the stability improvement. An amphiphilic oligomer was used as a surface coating agent to conduct a phase transfer experiment, core/multishell NCs were dissolved in water by such surface modification and the QYs were still kept above 70%. The as-prepared water dispersible ZnSe/CdSe/CdS/Cd(x)Zn(1 - x)S/ZnS core/multishell NCs not only have high fluorescence QYs but also are extremely stable in various physiological conditions. Furthermore, a biosensor system (lateral flow immunoassay system, LFIA) for the detection of human hepatitis B surface antigen (HBsAg) was developed by using this water-soluble core/multishell NCs as a fluorescent label and a nitrocellulose filter membrane for lateral flow. The result showed that such ZnSe/CdSe/CdS/Cd(x)Zn(1 - x)S/ZnS core/multishell NCs were excellent fluorescent labels to detect HBsAg. The sensitivity of HBsAg detection could reach as high as 0.05 ng ml( - 1).     

核壳型量子点-纳米金颗粒组装体高效检测神经性毒剂模拟剂

实验设计制备了一种由12层硫化锌包覆硒化镉的核壳型量子点(CdSe/12ZnS QDs)和纳米金颗粒(Au NPs)自组装形成的CdSe/12ZnS QDs/Au NPs复合结构, 并将其应用于神经性毒剂模拟剂氰基磷酸二乙酯(Diethyl Cyanophosphonate, DCNP)的高效检测。QDs由于与Au NPs存在荧光共振能量转移作用(Fluorescence Resonance Energy Transfer, FRET)而发生荧光猝灭, 乙酰胆碱酯酶(AChE)水解氯化硫代乙酰胆碱(ATC)生成的硫胆碱能够将量子点取代而使量子点荧光恢复。当QDs与Au NPs的摩尔浓度比为20 : 1时, QDs荧光猝灭效果最佳, AChE浓度为1.0×10 ^-3 U/L时, QDs荧光恢复效果最好。DCNP的存在会抑制AChE的活性, 减少硫胆碱的生成并降低QDs的荧光恢复效率, 通过对QDs荧光恢复效率测定能够检测DCNP。在最优条件下对DCNP的检测结果表明, 量子点的荧光恢复效率与DCNP浓度的对数在5.0×10 ^-9~5.0×10 ^-4mol/L的范围内存在良好的线性关系, 检出限达5.0×10 ^-9mol/L。     

Efficient quasi-stationary charge transfer from quantum dots to acceptors physically-adsorbed in the ligand monolayer

Alkanoate-coated CdSe/CdS core/shell quantum dots(QDs)with near-unity photoluminescence(PL)quantum yield and monoexponential PL decay dynamics are applied for studying quasi-stationary charge transfer from photo-excited QDs to quinone derivatives physically-adsorbed within the ligand monolayer of a QD.Though PL quenching efficiency due to electron transfer can be up to>80%,transient PL and transient absorption spectra reveal that the charge transfer rate ranges from single-digit nanoseconds to sub-nanoseconds,which is~3 orders of magnitude slower than that of static charge transfer and?2 orders of magnitude faster than that of collisional charge transfer.The physically-adsorbed acceptors can slowly(500-1,000 min dependent on the size of the quinone derivatives)desorb from the ligand monolayer after removal of the free acceptors.Contrary to collisional charge transfer,the efficiency of quasi-stationary charge transfer increases as the ligand length increases by providing additional adsorption compartments in the elongated hydrocarbon chain region.Because ligand monolayer commonly exists for a typical colloidal nanocrystal,the quasi-stationary charge transfer uncovered here would likely play an important role when colloidal nanocrystals are involved in photocatalysis,photovoltaic devices,and other applications related to photo-excitation.     

Calixarene capped quantum dots as luminescent probes for Hg ions

Luminescent and stable CdSe/ZnS core/shell quantum dots (QDs) capped with sulfur calixarene are prepared for the selective determination of mercury ions in acetonitrile with high sensitivity.     

Silica-shelled single quantum dot micelles as imaging probes with dual or multimodality

The present study describes a stabilization of single quantum dot (QD) micelles by a "hydrophobic" silica precursor and an extension of a silica layer to form a silica shell around the micelle using "amphiphilic" and "hydrophilic" silica precursors. The obtained product consists of approximately 92% single nanocrystals (CdSe, CdSe/ZnS, or CdSe/ZnSe/ZnS QDs) into the silica micelles, coated with a silica shell. The thickness of the silica shell varies, starting from 3-4 nm. Increasing the shell thickness increases the photoluminescence characteristics of QDs in an aqueous solution. The silica-shelled single CdSe/ZnS QD micelles possess a comparatively high quantum yield in an aqueous solution, a controlled small size, sharp photoluminescence spectra (fwhm approximately 30 nm), an absence of aggregation, and a high transparency. The surface of the nanoparticles is amino-functionalized and ready for conjugation. A comparatively good biocompatibility is demonstrated. The nanoparticles show ability for intracellular delivery and are noncytotoxic during long-term incubation with viable cells in the absence of light exposure, which makes them appropriate for cell tracing and drug delivery. The presence of the hydrophobic layer between the QD and silica-shell ensures an incorporation of other hydrophobic molecules with interesting properties (e.g., hydrophobic paramagnetic substances, hydrophobic photosensitizers, membrane stabilizers, lipid-soluble antioxidants or prooxidants, other hydrophobic organic dyes, etc.) in the close proximity of the nanocrystal. Thus, it is possible to combine the characteristics of hybrid materials with the priority of small size. The silica-shelled single QD micelles are considered as a basis for fabrication of novel hybrid nanomaterials for industrial and life science applications, for example, nanobioprobes with dual modality for simultaneous application in different imaging techniques (e.g., fluorescent imaging and functional magnetic resonance imaging).