Synthesis and characterization of water soluble choline labeled cadmium selenide/zinc selenide/zinc sulfide luminescent quantum dots

Water soluble choline-labeled CdSe/ZnSe/ZnS quantum dot (QD) bioconjugates were synthesized by attaching a thiolated choline analogue to the core-shell QD surface. Characterization was conducted by absorption and luminescence spectroscopy and scanning electron microscopy. QDs with diameters of 5–6 nm resulted and exhibited a luminescence maximum at 663 nm in aqueous solution.     

TiO2/CdS/CdSe quantum dots co-sensitized solar cell with the staggered-gap (type-II) heterojunctions for the enhanced photovoltaic performance

The effect of co-sensitization and ZnS passivation on the photovoltaic performance of CdS quantum dot sensitized solar cells (QDSSCs) were investigated. The deposition of CdS, CdSe quantum dots (QD) and ZnS passivation on TiO₂ photoanode was carried out by successive ionic layer adsorption and reaction (SILAR) method. CdS/CdSe co-sensitization developed two staggered type-II heterojunctions at TiO₂/CdS and CdS/CdSe interfaces and resulted a cascade energy band structure. This suitable band alignment facilitated the double charge transfer mechanism at each heterojunction and transported the electrons easily into the photoanode. The narrow bandgap sensitizers CdS and CdSe significantly improved the potential utilization of solar spectrum with more charge carrier generation. ZnS passivation on QD surface suppressed electrode/electrolyte interfacial charge recombination and facilitated more electron injection from QDs into TiO₂ photoanode. The EDAX elemental mapping results inferred that CdS, CdSe and ZnS have efficiently covered the TiO₂ surface. TiO₂/CdS and CdS/CdSe interfaces and the amorphous nature of ZnS could be verified with HRTEM images. Hence, the co-sensitization and surface passivation played a significant role to enhance the PCE of CdS QDSSC from 1.9% to 4.05%.     

PS/PMMA-CdSe/ZnS Quantum Dots Hybrid Nanofibers for VOCs Sensors

Hybrid nanofibers containing CdSe/ZnS quantum dots have been produced by electrospinning of hybrid latexes to characterize the electro-optical behavior of this novel luminescent sensing material. The latexes are synthesized by seeded semi-batch emulsion polymerization yielding cross-linked core-shell PS/QDs/PMMA particles with efficiently encapsulated quantum dots guaranteeing a good optical stability. Addition of polyvinyl alcohol (PVA) or polyethylene oxide (PEO) to the latexes is necessary to produce polymeric dispersions suitable for electrospinning manufacture of the nanometric fibers. The optimized polymeric dispersions are successfully electrospun obtaining fluorescent nanofibers in both cases. The hybrid nanofibers are sensitive to selected solvents (acetone, methanol and THF) and present positive response making them good candidates for the production of VOC sensors.     

A sandwich-type assay based on quantum dot/aptamer bioconjugates for analysis of E. Coli O157:H7 in microtiter plate format

An optical assay based on CdSe/ZnS quantum dots (QD)/NH₂-Apt bioconjugates for the pathogen detection was presented. QDs with carboxyl functional groups and 72-mer aptamer (against E. coli outer membrane proteins) were used as probes and sensing element. E. coli O157:H7 was selected as a model pathogen and 96-well plate assay in the sandwich hybridization format was constructed. Poly-L-lysine-coated 96-well plate surfaces were used as support material where thiol functionalized aptamers were immobilized by 4-(N-Maleimidomethyl)cyclohexane-1-carboxylic acid 3-sulfo-N-hydroxysuccinimide (sulfo-SMCC). After incubation with the bacteria, CdSe/ZnS QDs/aptamer bioconjugates were added. The fluorescence signals were followed before and after addition of bioconjugates. Probe concentrations, incubation time with E. coli O157:H7 were also optimized. The bioassay could detect the pathogen down to 10² CFU/mL with high selectivity. The detection system was successfully employed in samples, in the presence of interfering compounds.     

Preparation and characterization of silicone resin nanocomposite containing CdSe/ZnS quantum dots

We report the preparation of the core/shell cadmium selenide/Zinc sulfide quantum dots (CdSe/ZnS QDs)‐silicone resin nanocomposite through the solution‐mixing method, followed by thermal hydrosilylation. After dispersing QDs into Dow Corning two‐component silicone resins (OE6630A and OE6630B at 1:4 mixing ratio by weight), the resins were cured at 150°C for 1.5 h to produce QD‐silicone resin nanocomposites. The curing behavior of the silicone resins resulting from the thermal hydrosilylation was studied using differential scanning calorimetry (DSC). The properties of the QD‐silicone resin nanocomposites were investigated by ultraviolet–visible (UV–vis), fluorescence, confocal laser scanning microscopy (CLSM), atomic force microscopy (AFM), and thermogravimetric analysis (TGA) measurements. The QDs that contain trioctylamine (TOA) as the original ligand can poison the Pt catalyst in the resins and inhibit the curing process by increasing the exothermic peak temperature, at which a lower heat of hydrosilylation is observed. Incorporating a small amount of CdSe/ZnS QDs (0.1 wt%) can greatly improve the thermal stability of the silicone resins. Moreover, CdSe/ZnS QDs tend to form clusters that are relatively homogeneously distributed in a cured silicone resin, offering good optical properties of 11.2 lm W⁻¹ luminous efficiency and 14.6% photoluminescence conversion efficiency (PCE) in light emitting device (LED) test. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Microwave Synthesis of Nearly Monodisperse Core/Multishell Quantum Dots with Cell Imaging Applications

We report in this article the microwave synthesis of relatively monodisperse, highly crystalline CdSe quantum dots (QDs) overcoated with Cd_0.5Zn_0.5S/ZnS multishells. The as-prepared QDs exhibited narrow photoluminescence bandwidth as the consequence of homogeneous size distribution and uniform crystallinity, which was confirmed by transmission electron microscopy. A high photoluminescence quantum yield up to 80% was measured for the core/multishell nanocrystals. Finally, the resulting CdSe/Cd_0.5Zn_0.5S/ZnS core/multishell QDs have been successfully applied to the labeling and imaging of breast cancer cells (SK-BR3).     

Hybrid light-emitting diodes from anthracene-contained polymer and CdSe/ZnS core/shell quantum dots

In this paper, we added CdSe/ZnS core/shell quantum dots (QDs) into anthracene-contained polymer. The photoluminescent (PL) characteristic of polymer/QD composite film could identify the energy transitions of anthracene-contained polymer and QDs. Furthermore, the electroluminescent (EL) characteristic of hybrid LED also identifies emission peaks of blue polymer and QDs. The maximum luminescence of the device is 970 cd/m² with 9.1 wt.% QD hybrid emitter. The maximum luminous efficiency is 2.08 cd/A for the same device.     

The formation mechanism of Cd–S–Se quantum dots with CdSe/CdS core–shell structure within silicate glass

The formation mechanism of Cd–S–Se quantum dots (QDs) with a CdS/CdSe core–shell structure within a silicate glass system was investigated by monitoring the change in the first excitonic absorption peak of CdSe, CdS, and Cd–S–Se QDs as a function of the heat-treatment (HT) duration. When a silicate glass containing QD formation components for CdSe or CdS single-phased QDs was heat-treated, CdSe QDs grew via Ostwald ripening, whereas CdS QDs hardly formed within the given silicate glass matrix. When the glass, including CdO, ZnSe, and ZnS, was utilized for the synthesis of Cd–S–Se QDs within the glass matrix, Cd–S–Se QDs were successfully formed and exhibited similar growth behavior to CdSe QDs during the initial stage of HT. The structural changes in the QD-embedded glasses during HT were also monitored by Raman spectroscopy and discussed, and a possible formation mechanism of CdSe/CdS core–shell-structured QDs within silicate glasses is suggested.     

Reduced charge recombination in a co-sensitized quantum dot solar cell with two different sizes of CdSe quantum dot

An efficient photoelectrode is fabricated by sequentially assembling 2.5 nm and 3.5 nm CdSe quantum dots (QDs) onto a TiO2 film. As revealed by UV-vis absorption spectroscopy, two sizes of CdSe QD can be effectively adsorbed on the TiO2 film. With a broader light absorption range and better coverage of CdSe QDs on the TiO2 film, a power conversion efficiency of 1.26% has been achieved for the TiO2/CdSe QD (2.5 nm)/CdSe QD (3.5 nm) cell under the illumination of one Sun (AM 1.5G, 100 mW cm(-2)). Electrochemical impedance spectroscopy shows that the electron lifetime for the device based on TiO2/CdSe QD (2.5 nm)/CdSe QD (3.5 nm) is longer than that for devices based on TiO2/CdSe QD (2.5 nm) and TiO2/CdSe QD (3.5 nm), indicating that the charge recombination at the interface is reduced by sensitizing with two kinds of CdSe QDs.     

Photoluminescence enhancement of quantum dots on Ag nanoneedles

ABSTRACT: Noble-metal nanostructure allows us to tune optical and electrical properties, which has high utility for real-world application. We studied surface plasmon induced emission of semiconductor quantum dots (QDs) on engineered metallic nanostructures. Highly passive organic ZnS capped CdSe QDs were spin coated on poly-(methyl methacrylate) (PMMA) covered Ag films which brought QDs near to metallic surface. We obtained the enhanced electromagnetic field and reduced fluorescence lifetimes from CdSe/ZnS quantum dots (QDs) due to the strong coupling of emitters wave function with the Ag plasmon resonance. Observed changes include a six-fold increase in the fluorescence intensity and striking reduction in fluorescence lifetimes of CdSe/ZnS QDs on rough Ag nanoneedle compared to the case of smooth surfaces. The advantages of using those nanocomposites are expected for high efficiency light-emitting diodes, platform fabrication of biological and environmental monitoring, and high contrast imaging.     

巯基乙酸稳定的CdSe/ZnS核壳结构量子点的制备与表征

用非均相成核原理,在水溶液中制备CdSe/ZnS核壳结构量子点,并研究合成工艺,包括前驱物的滴加方式和用量、CdSe核的水浴反应时间、CdSe与ZnS的摩尔比等因素对CdSe/ZnS核壳结构量子点荧光性能的影响.用透射电子显微镜和x射线衍射仪测试核壳结构量子点的形貌和结构.用紫外吸收光谱与荧光光谱表征CdSe/ZnS核壳结构量子点的荧光性能.结果表明:ZnS壳层在CdSe核量子点表面外延生长,形成了核壳结构;CdSe/ZnS核壳结构量子点的荧光性能明显高于单一的CdSe量子点;合成的工艺条件会显著影响CdSe/ZnS核壳结构量子点的荧光性能.     

CdS and CdSe Quantum Dot-Embedded Silicate Glasses for LED Color Converter

Silicate glasses with CdS and CdSe quantum dots (QDs) were synthesized for application as an inorganic color converter for a 450-nm blue light-emitting diode (LED). CdO and ZnS (or ZnSe) were added, and heat treatment conditions were changed to control QD formation within the silicate matrix. Absorption spectra and high-resolution transmission electron microscopy confirmed the QD formation. Variations in absorption and photoluminescence (PL) spectra were observed with CdSe QD-embedded glasses when heat treatment conditions varied, whereas glasses with CdS QDs did not show noticeable variation. QD-embedded glasses were then mounted on top of a 450-nm LED chip to make a color-converted LED, and their electroluminescence and PL spectra as well as CIE color coordinates were investigated. The practical potential of QD-embedded glasses as an inorganic color converter has been observed, and their spectral properties were discussed.     

BRCAA1 antibody- and Her2 antibody-conjugated amphiphilic polymer engineered CdSe/ZnS quantum dots for targeted imaging of gastric cancer

Successful development of safe and highly effective nanoprobes for targeted imaging of in vivo early gastric cancer is a great challenge. Herein, we choose the CdSe/ZnS (core-shell) quantum dots (QDs) as prototypical materials, synthesized one kind of a new amphiphilic polymer including dentate-like alkyl chains and multiple carboxyl groups, and then used the prepared amphiphilic polymer to modify QDs. The resultant amphiphilic polymer engineered QDs (PQDs) were conjugated with BRCAA1 and Her2 monoclonal antibody, and prepared BRCAA1 antibody- and Her2 antibody-conjugated QDs were used for in vitro MGC803 cell labeling and in vivo targeted imaging of gastric cancer cells. Results showed that the PQDs exhibited good water solubility, strong photoluminescence (PL) intensity, and good biocompatibility. BRCAA1 antibody- and Her2 antibody-conjugated QD nanoprobes successfully realized targeted imaging of in vivo gastric cancer MGC803 cells. In conclusion, BRCAA1 antibody- and Her2 antibody-conjugated PQDs have great potential in applications such as single cell labeling and in vivo tracking, and targeted imaging and therapeutic effects'' evaluation of in vivo early gastric cancer cells in the near future.     

Preparation and Characterization of Silica-Coated Magnetic–Fluorescent Bifunctional Microspheres

Bifunctional magnetic–fluorescent composite nanoparticles (MPQDs) with Fe₃O₄ MPs and Mn:ZnS/ZnS core–shell quantum dots (QDs) encapsulated in silica spheres were synthesized through reverse microemulsion method and characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, vibration sample magnetometer, and photoluminescence (PL) spectra. Our strategy could offer the following features: (1) the formation of Mn:ZnS/ZnS core/shell QDs resulted in enhancement of the PL intensity with respect to that of bare Mn:ZnS nanocrystals due to the effective elimination of the surface defects; (2) the magnetic nanoparticles were coated with silica, in order to reduce any detrimental effects on the QD PL by the magnetic cores; and (3) both Fe₃O₄ MPs and Mn:ZnS/ZnS core–shell QDs were encapsulated in silica spheres, and the obtained MPQDs became water soluble. The experimental conditions for the silica coating on the surface of Fe₃O₄ nanoparticles, such as the ratio of water to surfactant (R), the amount of ammonia, and the amount of tetraethoxysilane, on the photoluminescence properties of MPQDs were studied. It was found that the silica coating on the surface of Fe₃O₄ could effectively suppress the interaction between the Fe₃O₄ and the QDs under the most optimal parameters, and the emission intensity of MPQDs showed a maximum. The bifunctional MPQDs prepared under the most optimal parameters have a typical diameter of 35 nm and a saturation magnetization of 4.35 emu/g at room temperature and exhibit strong photoluminescence intensity.     

Compositional Dependence of CdSe Quantum Dot Formation on Silicate Host Glass Composition

Silicate glasses were synthesized with additional CdO and ZnSe of varying content. When CdO was added up to 3 mol% with the amount of ZnSe fixed at 1 mol%, absorption due to Se₂^? color centers significantly decreased and the color of glasses was bleached without any evidence of CdSe quantum dots (QDs). However, characteristic absorption due to CdSe QDs appeared without additional heat treatment when the ZnSe content exceeded 1.5 mol%, whereas the CdO content was fixed at 1 mol%. Raman spectra and transmission electron microscopy verified the formation of CdSe QDs. The role of CdO and ZnSe in CdSe QD formation has been discussed in relation to their structural contribution within silicate glasses.     

Effect of phase transition on SiO2-coated CsPbBr3/Cs4PbBr6 quantum dots: Air-stability and quantum efficiency improvement

To develop white light-emitting diodes (WLEDs) with wide color gamut for displays, compared with nitride-based phosphors and traditional core-shell quantum dots (QDs) such as CdSe, InP, CuInS₂, all-inorganic perovskite QDs CsPbX₃ (X = Cl, Br, I) were more promising luminescent materials due to tunable wavelength, narrow emission spectrum and high quantum efficiency. However, when QDs were made into solid form (powders or films), poor air-stability and drastic decrease of quantum efficiency would be observed in CsPbBr₃. These drawbacks would restrict their practical applications. To resolve these issues, in this paper, we proposed a new concept that zero-dimensional perovskite QDs powders Cs₄PbBr₆ with outstanding quantum efficiency and long lifetime up to three months could be successfully prepared via silica-coated method and crystal phase transition in low-temperature synthesis. This phenomenon of phase transition would be discussed in detail and the quantum efficiency could be improved from 31.41% to 45.87%. Moreover, green LEDs with high color purity of 92% and luminous efficiency of 88.59 lm/W could also be achieved by using this material. Therefore, our proposed perovskite QDs powders Cs₄PbBr₆ had extreme potential for displays applications.     

Surface plasmon enhanced energy transfer in metal-semiconductor hybrid nanostructures

We report a type of hybrid nanostructures composed of ZnO nanoparticles, CdSe/ZnS core/shell quantum dots (QDs), and Ag nanoprisms. With ultraviolet light illumination, the energy absorbed by ZnO nanoparticles was transferred to the CdSe/ZnS core/shell QDs inducing a photoluminescence (PL) emission. To enhance the PL emission, Ag nanoprisms were doped in the ZnO nanoparticles and the QDs. Enhanced energy transfer from the ZnO nanoparticles to the QDs via the surface plasmon effect of the Ag nanoprisms was also demonstrated. The PL emission dependence was investigated as a function of the doped Ag nanoprism concentration and a 7.4 times PL enhancement was obtained at an Ag nanoprism concentration of 5 × 10(-8) M.     

Reversible Electrochemical Control over Photoexcited Luminescence of Core/Shell CdSe/ZnS Quantum Dot Film

Semiconductor quantum dots (QDs) are widely used in light-emitting diodes and solar cells. Electrochemical modulation is a good way to understand the electrical and optical properties of QDs. In this work, the effects of electrochemical control on photoluminescence (PL) spectra in core/shell CdSe/ZnS QD films are studied. The results show different spectral responses for surface emission and core emission when a negative electrochemical potential is applied: the core emission is redshifted while the surface emission is blueshifted. The former is attributed to the electrostatic expansion of the excitonic wave function, due to the asymmetric distribution of adsorbed cations on the surface of the dots. The latter is attributed to the occupation of lower surface states by the injected electrons, i.e., the photoexcited electrons are more likely to be trapped onto higher surface states, leading to a blueshift of the surface emission. Both the spectral shift and the accompanying PL-quenching processes are reversible by resetting the potential.     

The Role of Intrinsic and Surface States on the Emission Properties of Colloidal CdSe and CdSe/ZnS Quantum Dots

Time Resolved Photoluminescence (TRPL) measurements on the picosecond time scale (temporal resolution of 17 ps) on colloidal CdSe and CdSe/ZnS Quantum Dots (QDs) were performed. Transient PL spectra reveal three emission peaks with different lifetimes (60 ps, 460 ps and 9–10 ns, from the bluest to the reddest peak). By considering the characteristic decay times and by comparing the energetic separations among the states with those theoretically expected, we attribute the two higher energy peaks to ± 1 ^U and ± 1 ^L bright states of the fine structure picture of spherical CdSe QDs, and the third one to surface states emission. We show that the contribution of surface emission to the PL results to be different for the two samples studied (67% in the CdSe QDs and 32% in CdSe/ZnS QDs), confirming the decisive role of the ZnS shell in the improvement of the surface passivation.     

A highly efficient ZnS/CdS@TiO2 photoelectrode for photogenerated cathodic protection of metals

Shell-core nanostructured ZnS/CdS quantum dots (QDs) were assembled uniformly on the surface of TiO₂ nanotube arrays by sequence chemical bath deposition (CBD) of CdS and ZnS in alcohol solution system. The morphology and chemical composition of the obtained composite thin films were characterized by scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray spectroscopy. The effect of solvent and immersion cycles for the photoanode preparation on the photoelectrochemical activity and photogenerated cathodic protection property was investigated. It is found that the nanostructured CdS QDs (20 cycles) coated on TiO₂ nanotube arrays show a remarkably enhanced photoelectrochemical activity. The coating of ZnS QD shells (5 cycles) is able to improve the stability of the CdS@TiO₂ photoanode under white-light irradiation. After the irradiation light is turned off, the photogenerated cathodic protection of 403 stainless steel (403SS) can be remained for several hours.