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.     

巯基包覆CdSe和CdSe/CdS核壳纳米晶的水相合成与表征

利用水相合成的方法制备了巯基包覆的具有较高荧光量子产率的CdSe和CdSe／CdS纳米晶．水相合成方法的优点是原料低廉、安全可靠和重复性高，缺点是纳米晶的尺寸分布较宽，发光效率不是很高．采用X-射线粉末衍射、吸收和荧光等光谱手段对纳米晶的平均尺度、粒径分布、晶体结构及发光特性进行了表征。在77K到300K的温度范围内，随着温度降低，CdSe纳米晶的发光峰逐渐蓝移，而CdSe／Cds纳米晶发光峰位基本不随温度变化而变化．此外，在325nm激光辐照下，CdSe／CdS纳米晶的荧光寿命比CdSe纳米晶延长了6倍左右，稳定性大幅度提高．以上结果表明，核壳结构的CdSe／CdS纳米晶具有较高的发光效率和良好的稳定性，具有广阔的应用前景．     

水相中CdSe与核/壳CdSe/CdS量子点的制备与发光特性研究

以巯基乙酸为稳定剂在水相中制备了CdSe与核/壳型CdSe/CdS量子点水溶胶, 用紫外-可见吸收光谱和发射光谱研究了它们的发光特性, 并且用X射线粉末衍射(XRD)、透射电镜(TEM)和X射线光电子能谱(XPS)表征了它们的结构、形貌和化学组成, 结果表明使用该方法制备的量子点分散性良好, 而且用CdS对CdSe进行表面修饰以后的发光强度明显提高, 发射光谱和吸收光谱都有红移现象, 不同粒径颗粒的吸收峰的位置也有所不同.     

Highly luminescent blue emitting CdS/ZnS core/shell quantum dots via a single-molecular precursor for shell growth

Highly luminescent blue-emitting CdS/ZnS core/shell quantum dots (QDs) were synthesized in N-oleoylmorpholine by two facile steps: first, the CdS core QDs were prepared via a simple one-pot method involving a direct reaction of Cd precursor cadmium stearate and S precursor S powder in solvent N-oleoylmorpholine; second, ZnS shells were successively overcoated on CdS core through the decomposition of single molecular precursor zinc diethyldithiocarbamate. The thickness of shell was precisely tuned by controlling drip feed speed and amount of shell precursor. The obtained CdS/ZnS core/shell QDs showed the maximum photoluminescent quantum yield of 54.8% and narrow spectra bandwidth, exhibiting high monodispersity, good color purity and long fluorescent lifetimes. The CdS/ZnS core/shell QDs with tunable emission wavelength of 424–470 nm were obtained by controlling the thickness of ZnS shell overgrown on different-sized CdS QDs, which are promising materials for blue light-emitting devices.     

Extracellular biosynthesis of biocompatible CdSe quantum dots

An extracellular biosynthesis method has been developed to prepare cadmium selenide (CdSe) quantum dots (QDs) with strong fluorescence emission by incubating cheap Cd and Se inorganic salts with Escherichia coli (E.coli) bacteria. Ultraviolet–visible absorption spectra, photoluminescence (PL) spectra, and high‐resolution transmission electron microscopy analysis showed that the biosynthesised CdSe QDs have an average size of 3.1 nm, the excellent optical properties with fluorescence emission around 494 nm, and the good crystallinity. It was found that addition of 80 mg of mercaptosuccinic acid resulted in the formation of CdSe QDs with highest PL intensity. Furthermore, Fourier‐transform infrared spectra of as‐synthesised CdSe QDs confirmed the presence of a surface protein capping layer. The biosynthesised CdSe QDs were incorporated into the yeast cells as illustrated by laser confocal scanning microscopy images, showing a great potential in bio‐imaging and bio‐labelling application.Inspec keywords: microorganisms, molecular biophysics, fluorescence, visible spectra, nanofabrication, nanobiotechnology, proteins, cellular biophysics, nanostructured materials, wide band gap semiconductors, cadmium compounds, semiconductor quantum dots, II‐VI semiconductors, transmission electron microscopy, photoluminescence, optical microscopy, ultraviolet spectra, Fourier transform infrared spectra, biological techniques, semiconductor growthOther keywords: biocompatible CdSe quantum dots, extracellular biosynthesis method, cadmium selenide quantum dots, high‐resolution transmission electron microscopy analysis, biosynthesised CdSe QDs, Fourier‐transform infrared spectra, Escherichia coli, ultraviolet‐visible absorption spectra, PL intensity, fluorescence emission, photoluminescence spectra, optical properties, surface protein capping layer, laser confocal scanning microscopy images, bioimaging, biolabelling application, yeast cells, f mercaptosuccinic acid, CdSe     

Synthesis, morphology, and optical properties of colloidal CdTe/CdSe and CdTe/CdS nanoheterostructures based on CdTe tetrapods

We report the synthesis of colloidal CdTe/CdSe and CdTe/CdS nanoheterostructures based on CdTe tetrapods with a CdSe or CdS shell. The shell growth takes place on the lateral faces of the tetrapod legs, whereas the leg length remains essentially unchanged. Both the CdSe and CdS shell growth shifts the luminescence of the nanoheterostructures to the near-IR range, up to 850 nm, with a quantum yield of up to 20%. Analysis of the kinetics of the shift of the excitonic absorption band during nanoheterostructure growth suggests that the growth rate of CdS exceeds that of CdSe. The variation of the luminescence wavelength with shell thickness is compared to numerical modeling results.     

Cathodic stripping synthesis and cytotoxity studies of glutathione-capped CdTe quantum dots

A cathodic stripping of Te precursor in the presence of Cd2+ and biocompatible glutathione (GSH) was reported for facile synthesis of lowly cytotoxic and highly luminescent CdTe quantum dots (QDs) in aqueous solution. The photoluminescence, electrogenerated chemiluminescence (ECL), toxicity, and cyto-osmosis of the QDs were evaluated to reveal their potential bio-applications. The morphology and composition of as-prepared QDs were investigated by HRTEM and powder XRD spectroscopy, which indicated that the QDs consisted of a CdTe core coated with a CdS shell. The obtained CdTe/CdS core/shell QDs possessed good crystallinity, narrow monodispersity and long-term stability. These QDs showed high fluorescence quantum yields of 49% to 63% over a broad spectral range of 540-650 nm. Efficient and stable ECL of QDs was observed on the anodic potential region upon the electrode potential cycled between 1.5 and -2.0 V versus Ag/AgCl. Furthermore, human liver cancer HepG2 cells were chosen as model cells for toxicity assay of QDs. Effects of the concentration, size, and incubation time of CdTe QDs capped with GSH or mercaptoacetic acid (MAA) on the cell metabolic viability and cyto-osmosis were evaluated. GSH-capped CdTe QDs could infiltrate cytomembrane and karyothecas, and were less cytotoxic than MAA-capped ones under the same experimental conditions. The reported CdTe QDs could be good candidates of fluorescent and ECL probes for biosensing and cell imaging.     

Synthesis and size dependent optical studies in CdSe quantum dots via inverse micelle technique

Cadmium selenide quantum dots (CdSe QDs) were successfully synthesized without using trioctylphosphine (TOP). The XRD pattern showed zinc-blend phase of the CdSe QDs. The absorption and PL spectra exhibit a strong blue shift as the QDs size decreases due to the quantum confinement effect. In addition, the quantum efficiency of CdSe QDs with TOP capping is higher than CdSe QDs with oleic acid capping. TEM image shows a spherical shape, compact and dense structure of CdSe QDs. A good agreement between the Tauc's model and experimentally measured absorption spectra of CdSe QDs is achieved. The FTIR peak at ～1712 cm^?1 spectra confirms the influence of oleic acid as a capping agent.     

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.     

Enhanced photovoltaic performance of solar cell based on front-side illuminated CdSe/CdS double-sensitized TiO2 nanotube arrays electrode

Free-standing TiO₂ nanotube (NT) arrays have been prepared by a two-step anodization method. These translucent TiO₂ NT arrays can be transferred to the fluorine-doped tin oxide glass substrates to form front-side illuminated TiO₂ NT electrodes. The TiO₂ NT electrodes were double-sensitized by CdSe/CdS quantum dots (QDs) through successive ionic layer adsorption and reaction (SILAR) process. The absorption range of the TiO₂ NT electrode was extended from ~380 to 700 nm after sensitization with CdSe/CdS QDs. The SILAR cycles were investigated to find out the best combination of CdS and CdSe QDs for photovoltaic performance. The power conversion efficiency of 2.42 % was achieved by the CdSe(10)/CdS(8)/TiO₂ NT solar cell. A further improved efficiency of 2.57 % was obtained with two cycles of ZnS overlayer on the CdSe(10)/CdS(8)/TiO₂ NT electrode, which is 45.19 % higher than that of back-side illuminated solar cell. Furthermore, the ZnS(2)/CdSe(10)/CdS(8)/TiO₂ NT solar cell possesses a higher stability than CdSe(10)/CdS(8)/TiO₂ NT solar cell during the same period. The better photovoltaic performance of the ZnS(2)/CdSe(10)/CdS(8)/TiO₂ NT solar cell has demonstrated the promising value to design quantum dots-sensitized solar cells with double-sensitized front-side illuminated TiO₂ NT arrays strategy.     

Synthesis of blue fluorescence CdS quantum dots stabilized by L-cysteine in aqueous phase

In this paper we report a novel synthesis method of blue fluorescence CdS quantum dots stabilized by L-cysteine in aqueous phase. When pH value of the core/shell CdTe/CdS colloid solution changed from 11.6 to 1.5, blue fluorescence CdS QDs was obtained. The fluorescence emission wavelength yielded a hypsochromic shift from 540 nm to 438 nm corresponding to the absorption peak position gave a hypsochromic shift from 518 nm to 352 nm. The CdS QDs were characterized by XPS and TEM. And the photostability of CdS QDs solution irradiated with UV lamp under open air condition at room temperature was very stable.     

CdSe and CdSe/ZnS quantum dots for the detection of C-reactive protein

In this study, a method for the detection of C-reactive protein (CRP) using CdSe and CdSe/ZnS quantum dots (QDs) is proposed. CdSe and CdSe/ZnS core-shell QDs are synthesised by using 2-mercaptosuccinic acid (MSA) as a capping agent. These QDs were then subjected to various characterisation studies, namely X-ray diffraction and transmission electron microscope for size and structure, Fourier transform infrared spectroscopy for the confirmation of functional groups, ultraviolet–visible absorption and fluorescence spectroscopy for optical characteristics and dynamic light scattering for hydrodynamic changes of QDs. Two biochemical mixtures were developed: one by mixing blood serum containing CRP and CdSe-phosphorylethanolamine (PEA) and the other by mixing blood serum with CdSe/ZnS-PEA. When these mixtures are observed for fluorescence due to interaction of QDs with CRP, a correlation between changes in fluorescence for different concentrations of CRP is noted. The result demonstrates that CRP can be detected with the help of QDs without using any antibodies.     

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.     

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.     

Synthesis and properties of water-soluble core-shell-shell silica-CdSe/CdS-silica nanoparticles

This paper describes the synthesis of highly water-soluble and fluorescent core-shell-shell silica-CdSe/CdS-silica nanoparticles (CSS silica-QDs-silica NPs). We used cadmium nitrate and 1,1-dimethyl-2-selenourea precursors to synthesize CdSe quantum dots (QDs) in aqueous solution under simultaneous illumination with a diode-pumped solid state green laser and a Xe-Hg lamp. After passivation of the CdSe QDs with CdS, the CdSe/CdS QDs were then conjugated covalently to (3-mercaptopropyl)trimethoxysilane (MPS); we call these nanoparticles "MPS-QDs". We mixed the MPS-QDs with tetraethoxysilane (TEOS), ethanol, and NH3. By controlling the concentrations of the reagents, the stirring speed, and the reaction time, we synthesized CSS silica-QDs-silica NPs having sizes ranging from 75 to 190 nm. The incubation time for preparing the MPS-QDs and their concentrations are important parameters in determining the morphologies of the CSS silica-QDs-silica NPs. When we mixed 50 nM MPS-QDs, 1.1 mM TEOS, and 78 mM NH3 and reacted them at a stirring speed of 750 rpm, we obtained 85-nm-diameter CSS silica-QDs-silica NPs having a QD shell thickness of about 20 nm. The CSS silica-QDs-silica NPs provide a strong photoluminescence intensity (quantum yield 88%) and exhibit enhanced stability both photochemically and in high-conductivity media (e.g., 1.0 M NaCl).     

Preparation and characterization of overcoated II-VI quantum dots

A convenient route for the synthesis of high-quality overcoated II-VI quantum dots (QDs) is reported in this paper. Simple salts, such as Cd(Ac)2 and Zn(Ac)2 were used to replace organometallics, whose disadvantage is obvious. Size-tunable core/shell structured QDs (CdSe/ZnS, CdSe/CdS, etc.) were synthesized. They were of narrow size distribution and had good monodispersivity and photoluminescence (PL) properties. The spectrum was symmetrical and sharp-pointed (with the full width at half-maximum (fwhm) of about 20-30 nm). The quantum yield (QY) was improved to 60-80% from 20-30% for bare QDs and remained stable at least for 6 months. The primary overcoated QDs were modified with biomacromolecules by a direct mechanical rubbing strategy, which is very simple and fast. The results obtained by UV-vis, PL, atomic force microscopy (AFM), and fluorescence microscopy imaging showed that the modified QDs were of good fluorescent and monodisperse characteristics. They are likely to be used further for biological labels.     

Optimization of CdSe layer on modified ZnO hierarchical spheres by spin-SILAR for efficient CdS/CdSe co-sensitized solar cells

In this study, after CdS quantum dots sensitized ZnO hierarchical spheres (ZnO HS), we used a simple process to deposit CdSe QDs on ZnO by spin-coating-based SILAR, and applied to photoanodes of quantum dots-sensitized solar cells. Before CdS and CdSe QDs deposition, the ZnO HS photoanodes were modified by Zn(CH₃COO)₂·2H₂O methanol solution to further enhance the open-circuit voltage and power conversion efficiency (PCE). The program of modifying photoanodes and the number of CdSe spin-SILAR cycles are evaluated on the optical and electrochemical properties of the cells. As a result, a high energy conversion efficiency of 2.49 % was obtained by using modified ZnO HS/CdS photoanode under AM 1.5 illumination of 100 mW cm^?2. And further decorated by the CdSe QDs, the ZnO HS/CdS/CdSe cell achieved a PCE of 5.36 % due to the modification of ZnO HS nanostructure, the enhanced absorption in the visible region, the lower recombination reaction and higher electron lifetime.     

The influence of capping thioalkyl acid on the growth and photoluminescence efficiency of CdTe and CdSe quantum dots

The influence of thioalkyl acid ligand was evaluated during aqueous synthesis at 100?°C and under hydrothermal conditions (150?°C) of CdTe and CdSe quantum dots (QDs). Experiments performed with 3-mercaptopropionic acid (MPA), 6-mercaptohexanoic acid (MHA) and 11-mercaptoundecanoic acid (MUA) demonstrated that the use of MHA and MUA allowed for the preparation of very small nanoparticles (0.6-2.5?nm) in carrying out the reaction under atmospheric pressure or in an autoclave and that the photophysical properties of QDs were dependent on the ligand and on the synthesis conditions. The influence of various experimental conditions, including the Te-to-Cd ratio, temperature, and precursor concentration, on the growth rate of CdTe or CdSe QDs has been systematically investigated. The fluorescence intensities of CdTe QDs capped with MPA, MHA, or MUA versus pH were also found to be related to the surface coverage of the nanoparticles.     

Proton-resistant quantum dots: Stability in gastrointestinal fluids and implications for oral delivery of nanoparticle agents

Semiconductor quantum dots (QDs) have shown great promise as fluorescent probes for molecular, cellular and in vivo imaging. However, the fluorescence of traditional polymer-encapsulated QDs is often quenched by proton-induced etching in acidic environments. This is a major problem for applications of QDs in the gastrointestinal tract because the gastric (stomach) environment is strongly acidic (pH 1–2). Here we report the use of proton-resistant surface coatings to stabilize QD fluorescence under acidic conditions. Using both hyperbranched polyethylenimine (PEI) and its polyethylene glycol derivative (PEG-grafted PEI), we show that the fluorescence of core shell CdSe /CdS/ ZnS QDs is effectively protected from quenching in simulated gastric fluids. In comparison, amphiphilic lipid or polymer coatings provide no protection under similarly acidic conditions. The proton-resistant QDs are found to cause moderate membrane damage to cultured epithelial cells, but PEGylation (PEG grafting) can be used to reduce cellular toxicity and to improve nanoparticle stability.      

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.