Size-dependent blue luminescent CdS nanocrystals synthesized through a single-source molecular precursor route

In this paper, we report on the synthesis of size-dependent blue luminescent CdS nanocrystals by using a new nonhydrolytic single-source molecular method. The size of the synthesized CdS nanocrystals could be easily controlled by adjusting the ratio of reaction sources under inert atmosphere. The studies on the optical properties reveal an obvious size-dependent photoluminescence characteristic of the synthesized nanocrystals.     

Fast-grown CdS quantum dots: Single-source precursor approach vs microwave route

A cross-disciplinary protocol of characterization by joint techniques enables one to closely compare chemical and physical properties of CdS quantum dots (QDs) grown by single source precursor methodology (SSPM) or by microwave synthetic route (MWSR). The results are discussed in relation with the synthesis protocols. The QD average sizes, reproducible as a function of the temperatures involved in the growth processes, range complementarily in 2.8–4.5 nm and 4.5–5.2 nm for SSPM and MWSR, respectively. Hexagonal and cubic structures after X-ray diffraction on SSPM and MWSR grown CdS QDs, respectively, are tentatively correlated to a better crystalline quality of the latter with respect to the further ones, suggested by (i) a remarkable stability of the MWSR grown QDs after exposure to air during several days and (ii) no evidence of their fragmentation during mass spectrometry (MS) analyses, after a fair agreement between size dispersities obtained by transmission electron microscopy (TEM) and MS, in contrast with the discrepancy found for the SSPM grown QDs. Correlatively, a better optical quality is suggested for the MWSR grown QDs by the resolution of n > 1 excitonic transitions in their absorption spectra. The QD average sizes obtained by TEM and deduced from MS are in overall agreement. This agreement is improved for the MWSR grown QDs, taking into account a prolate shape of the QDs also observed in the TEM images. For both series of samples, the excitonic responses vs the average sizes are consistent with the commonly admitted empirical energy-size correspondence. A low energy PL band is observed in the case of the SSPM grown QDs. Its decrease in intensity with QD size increase suggests a surface origin tentatively attributed to S vacancies. In the case of the MWSR grown QDs, the absence of this PL is tentatively correlated to an absence of S vacancies and therefore to the stable behavior observed when the QDs are exposed to air.     

Improved optical properties of CdS quantum dots by ligand exchange

High-quality CdS nanocrystals with highly efficient and narrow band edge emission have been prepared by means of decomposition of suitable precursors in non-coordinating solvents at high temperature. The role played by capping ligands, solvents and their interactions has been investigated by optical measurements. Capping layer exchange treatments with different amines have been carried out suggesting a possible influence of alkylic chain length in modifying the optical properties of CdS nanocrystals. Enhancement of band edge emission has been demonstrated with octylamine ligand.     

Histidine functionalised biocompatible CdS quantum dots synthesised by sonochemical method

Histidine functionalised CdS quantum dots (QDs) have been synthesised by sonochemical method. Transmission Electron Microscopy (TEM) observation shows that the histidine functionalised CdS QDs are well-defined, nearly spherical particles. The X-ray diffraction pattern indicates formation of cubic phase of CdS/histidine QDs. The absorption spectra confirm quantum confinement of histidine functionalised CdS QDs. The photoluminescence property of CdS/histidine QDs is found better than that of CdS QDs. Histidine functionalised CdS QDs, in which histidine acts as a biocompatibiliser, can find potential applications in the biological fields.     

Transfection of aqueous CdS quantum dots using polyethylenimine

In this study, we have examined the transfection of aqueous CdS quantum dots (QDs) in the cytoplasm of PC12 neuronal cells using polyethylenimine (PEI) as carrier. The CdS QDs were prepared using a unique aqueous synthesis method, at 5?nm in size and capped with 3-mercaptopropyltrimethoxysilane (MPS). They exhibited a quantum yield of 7.5% and a zeta potential of -25?mV. With PEI they formed complexes by electrostatic attraction. At PEI/QD number ratios of>100, the PEI-QD complexes obtained exhibited a saturated size of about 24?nm and a zeta potential of about 15?mV. Confocal microscopy showed that PEI-QD complexes of a PEI/QD number ratio of 200 were successfully internalized and uniformly distributed inside the cells, indicating that the PEI-QD complexes were able to rupture the vesicles to enter the cytoplasm without aggregation. In addition, we showed that the presence of the PEI did not reduce the photoluminescence of the QDs and only mildly reduced the mitochondrial activity of the transfected cells-with no apparent reduction at a PEI/QD ratio of <40 to about 30% reduction at a PEI/QD number ratio of 200.     

Synthesis spectrum properties of high-quality CdS quantum dots

High-quality CdS quantum dots with zinc-blende structure were prepared in noncoordinating solvent 1-octadence (ODE), using N-oleoyl-morpholine as an alternative solvent for sulfur powder, oleic acid (OA) as capping ligand. Sulfur powder could be dissolved in N-oleoyl-morpholine at room temperature. The kinetics of nucleation/growth was monitored via the temporal evolution of optical properties of the as-prepared CdS quantum dots. Various synthetic parameters were systematically investigated, such as growth temperature of 190 degrees C-260 degrees C, OA concentrations of 1.5 mL-2 mL, and the feed molar ratios of (0.5-3) Cd/1S. With increasing feed molar ratio of Cd/S, little trap emission could be observed. The feed molar ratio of 3Cd/1S was suggested to be the optimal synthetic window, together with the amount of OA 1.5 mL and the growth temperature of 210 degrees C. The quantum dots with growth periods ranging from 0 to 900 s at 210 degrees C exhibited their first excitonic absorption peak changing from 359 nm to 429 nm and the corresponding average size moved from 2.26 nm to 4.41 nm. The narrowest PL FWHM we obtained was 16 nm. Typical HRTEM images revealed that the as-prepared CdS quantum dots had narrow size distribution and high crystallinity.     

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.     

CdS/CdSSe quantum dots in glass matrix

The compositions containing 55 and 60% of silica have been formulated for preparation of glass filters having sharp cut-off at 475 and 575 nm. To achieve cut-off at these wavelengths, the glasses have been doped with CdS/CdSSe and melted at 1200–1300°C. The glass samples were transparent and pale yellow in colour due to presence of CdS/CdSSe tiny nano crystal (Q-dots). In situ growth of CdS/CdSSe nano crystals imparts the yellow/orange/red colour to these glasses. Optical study shows that as prepared glasses have optical cut-off in the range 350–370 nm. The linear crystal growth of CdS/CdSSe in glasses exhibits red shift in optical cut-off. The optical filter having cut-off at 475 nm can be prepared by doping CdS and cut-off filter of wavelength 575 nm by CdSSe. The TEM results show that the CdS/CdSSe nano crystals (Q-dots) ranging from 2–5 nm are uniformly distributed into the glass matrix.     

Luminescent CdS quantum dots as selective ion probes

Water-soluble luminescent CdS quantum dots (QDs) capped by polyphosphate, L-cysteine, and thioglycerol were synthesized in aqueous solution. The ligands were found to have a profound effect on the luminesence response of CdS QDs to physiologically important metal cations. Polyphosphate-capped CdS QDs were sensitive to nearly all mono- and divalent cations, showing no ion selectivity. Conversely, thioglycerol-capped CdS QDs were sensitive to only copper and iron ions. Similar concentrations of physiologically relevant cations, such as zinc, sodium, potassium, calcium, and magnesium ions did not affect the luminescence of thioglycerol-capped CdS QDs. On the other hand, L-cysteine-capped CdS QDs were sensitive to zinc ions and insensitive to other physiologically important cations, such as copper, calcium, and magnium ions. To demonstrate the detection capability of these new ion probes, L-cysteine and thioglycerol-capped CdS QDs were used to detect zinc and copper ions in physiological buffer samples. The detection limits were 0.8 microM for zinc (II) and 0.1 microM for copper (II) ions. The emission enhancement of the QDs by zinc (II) is attributed to activation of surface states, whereas the effective reduction of copper (II) to copper (I) may explain the emission decrease of the thioglycerol-capped CdS QDs when charged with copper ions. Unlike organic fluorescent dyes, the thioglycerol-capped luminescent CdS QDs discriminate between copper and zinc ions and are therefore suitable for the analysis of copper ions in biological samples in the presence of physiological concentrations of zinc ions. The interference of iron ions with zinc and copper ion detection is attributed to an inner filter effect, which is eliminated by adding fluoride ions to form the colorless complex FeF6(3-). To the best of our knowledge, this is first use of luminescent semiconductor quantum dots as selective ion probes in aqueous samples.     

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.     

Structural and optical characterization of Ni-doped CdS quantum dots

Ni-doped CdS quantum dots have been prepared by chemical precipitation technique. The X-diffraction results indicated that the particle size of Ni-doped CdS nanoparticles is smaller than that of undoped CdS and no secondary phase was observed. The average grain size of the nanoparticles is found to lie in the range of 2.7–4 nm. The compositional analysis results show that Cd, Ni, and S are present in the samples. HRTEM studies reveal that the average particle size of undoped and Ni-doped CdS quantum dots is 2 and 3 nm, respectively. Raman spectra shows that 1LO, 2LO, and 3LO peaks of the Ni-doped CdS samples are slightly red shifted when compared to that of undoped CdS. The absorption edge of Ni-doped CdS nanoparticles is found to shift towards the higher-wavelength (red shift) side when compared to that of undoped CdS and the band gap is observed to lie in the range of 3.79–3.95 eV. This band gap is higher than that of the bulk CdS and is due to quantum confinement effect present in CdS nanoparticles.     

Temperature dependent luminescence of azobenzene capped CdS quantum dots

Cadmium sulfide (CdS) quantum dots (QDs) are prepared at room temperature by "form-fill-seal" method, while the azobenzene is used as surfactant to control the particle size and to prevent agglomeration. The typical size of CdS nanoparticles is estimated as 2 nm by X-ray diffraction. The absorption spectra of CdS QDs are measured at room temperature and a new absorption peak associated with the surface excited state is found. The luminescence property of the CdS QDs is studied at room temperature and low temperature. Two photoluminescence peaks exist in the temperature range of 8-300 K. One peak at 460 nm is attributed to CdS QDs, while the other one at 667 nm comes from the transition of surface excited state and its intensity decreases with temperature increasing.     

Chiral shells and achiral cores in CdS quantum dots

We report and explain circular dichroism in semiconductor quantum dots. CdS nanocrystals capped with penicillamine enantiomers were prepared and found to be both highly luminescent and optically active. No new features in circular dichroism were observed as the nanocrystal grew larger. Density functional calculations reveal that penicillamine strongly distorts surface Cd, transmitting an enantiomeric structure to the surface layers and associated electronic states. The quantum dot core is found to remain undistorted and achiral.     

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.     

Cytotoxicity tests of water soluble ZnS and CdS quantum dots

Cytotoxicity tests of zinc sulfide (ZnS) and cadmium sulfide (CdS) quantum dots (QDs) synthesized via all-aqueous process with various surface conditions were carried out with human endothelial cells (EA hy926) using two independent viability assays, i.e., by cell counting following Trypan blue staining and by measuring Alamar Blue (AB) fluorescence. The ZnS QDs with all four distinct types of surface conditions were nontoxic at both 1 microM and 10 microM concentrations for at least 6 days. On the other hand, the CdS QDs were nontoxic only at 1 microM, and showed significant cytotoxicity at 10 microM after 3 days in the cell counting assay and after 4 days in the AB fluorescence assay. The CdS QDs with (3-mercaptopropyl)trimethoxysilane (MPS)-replacement plus silica capping were less cytotoxic than those with 3-mercaptopropionic acid (MPA) capping and those with MPS-replacement capping. Comparing the results of ZnS and CdS QDs with the same particle size, surface condition and concentration, it is indicated that the cytotoxicity of CdS QDs and the lack of it in ZnS QDs were probably due to the presence and absence of the toxic Cd element, respectively. The nontoxicity of the aqueous ZnS QDs makes them favorable for in vivo imaging applications.     

Synthesis of anisotropic CdS nanostructures via a single-source route

A cadmium tetrahydroisoquinoline dithiocarbamate (DTC) complex has been used as single-source precursor for the synthesis of highly faceted hexadecylamine (HDA) capped CdS nanoparticles. Hexagonal and close to cubic shaped particles with distinct lattice fringes are visible in the high resolution transmission electron microscopy images. Crystalline particles in the shape of a hexagon are clearly visible in the high resolution TEM images. The X-ray diffraction pattern of the particles is indexed to the stable wurtzite phase of CdS. The optical absorption spectrum of the particles is blue shifted from bulk CdS and the photoluminescence (PL) spectrum shows a relatively narrow emission peak.     

Temperature-dependent Raman study of thermal parameters in CdS quantum dots

We report on the strong temperature-dependent thermal expansion, α(D), in CdS quantum dots (QDs) embedded in a glass template. We have performed a systematic study by using the temperature-dependent first-order Raman spectra, in CdS bulk and in dot samples, in order to assess the size dependence of α(D), and where the role of the compressive strain provoked by the glass host matrix on the dot response is discussed. We report the Grüneisen mode parameters and the anharmonic coupling constants for small CdS dots with mean radius R?～?2.0?nm. We found that γ parameters change, with respect to the bulk CdS, in a range between 20 and 50%, while the anharmonicity contribution from two-phonon decay channel becomes the most important process to the temperature-shift properties.