Self-assembly of charged microclusters of CdSe/ZnS core/shell nanodots and nanorods into hierarchically ordered colloidal arrays

A thermodynamically driven self-organization of microclusters of semiconductor nanocrystals with a narrow size distribution into periodic two-dimensional (2D) arrays is an attractive low-cost technique for the fabrication of 2D photonic crystals. We have found that CdSe/ZnS core/shell quantum dots or quantum rods, transferred in aqueous phase after capping with the bifunctional surface-active agent DL-cysteine, form on a poly-L-lysine coated surface homogeneously sized micro-particles, droplet-like spheroid clusters and hexagon-like colloidal crystals self-organized into millimetre-sized 2D?hexagonal assemblies. The presence of an organic molecular layer around the micro-particles prevents immediate contact between them, forming an interstitial space which may be varied in thickness by changing the origin of the molecular layer capping nanocrystals. Due to the high refractive index of CdSe and the low refractive index of the interstitial spaces, these structures are expected to have deep gaps in their photonic band, forming hierarchically ordered 2D arrays of potentially photonic materials.     

Excitation wavelength dependence of fluorescence intermittency in CdSe/ZnS core/shell quantum dots

Core/shell CdSe/ZnS quantum dot fluorescence-blinking statistics depend strongly on excitation wavelength. Excitation on the band gap (575 nm) results in inverse-power law "on" time distributions. However, distributions resulting from excitation above the band gap (525 nm) require a truncated power law and are 100 times less likely to display 10-s fluorescence. "Off" time statistics are insensitive to the excitation wavelength. The results may be explained by nonemissive trap states accessed with the higher-photon excitation energies.     

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.     

CdSe/CdS/SiO2 core/shell/shell nanoparticles

Quantum dots (QD) of a CdSe-ZnS core-shell structure are coated with silica spheres to improve their stability in biological buffers and biocompatibility in fluorescence imaging. We found that it was critical to transfer quantum dots from organic phase to aqueous phase before the silica shell growth process. As a result, high quality CdSe-ZnS-SiO2 core-shell-shell nanoparticles were prepared in high yields and their size and distribution are characterized with transmission electron microscopy and dynamic light scattering, which yielded uniform sizes and narrow polydispersity. Single particle fluorescence spectroscopy on the silica-protected quantum dots showed they were stronger emitters with consistent fluorescence intensity and "on-off" behaviors than bare CdSe-ZnS nanocrystals.     

Langmuir-Blodgett films of gold/silica core/shell nanorods

We report the preparation of Langmuir- and Langmuir-Blodgett films of mesoporous silica coated gold nanorods. The silica coating on the gold nanorods was found to prevent the aggregation of the plasmonic particles trapped at the air/water interface. Due to the small aspect ratio of the gold core and the presence of the silica shell, the orientational alignment of the nanorods in the Langmuir-Blodgett film is hindered. After particle deposition, no plasmon coupling was observed, which enables the design of the resulting film's optical property at the particle level. By using mesoporous silica as the shell material, the accessibility of the metal core's surface is preserved. Organic dye (Rhodamine 6G) was found to be able to penetrate into the mesoporous shell of the gold nanorods, resulting in a red shift of the longitudinal plasmon mode.     

Surface-enhanced Raman scattering inside Au@Ag core/shell nanorods

The design and synthesis of plasmonic nanoparticles with Raman-active molecules embedded inside them are of significant interest for sensing and imaging applications.However,direct synthesis of such nanostructures with controllable shape,size,and plasmonic properties remains extremely challenging.Here we report on the preparation of uniform Au@Ag core/shell nanorods with controllable Ag shells of 1 to 25 nm in thickness.1,4-Aminothiophenol (4-ATP) molecules,used as the Raman reporters,were located between the Au core and the Ag shell.Successful embedding of reporter molecules inside the core/shell nanoparticles was confirmed by the absence of selective oxidation of the amino groups,as measured by Raman spectroscopy.The dependence of Raman intensity on the location of the reporter molecules in the inside and outside of the nanorods was studied.The molecules in the interior showed strong and uniform Raman intensity,at least an order of magnitude higher than that of the molecules on the nanoparticle surface.In contrast to the usual surface-functionalized Raman tags,aggregation and clustering of nanoparticles with embedded molecules decreased the surface-enhanced Raman scattering (SERS) signal.The findings from this study provide the basis for a novel detection technique of low analyte concentration utilizing the high SERS response of molecules inside the core/shell metal nanostructures.As an example,we show robust SERS detection of thiram fungicide as low as 10-9 M in solutions.     

Luminescent properties of ZnS:Mn2+/ZnS core/shell nanocrystals

High-quality ZnS:Mn2+/ZnS core/shell nanocrystals (NCs) with a core crystal diameter of 6.1 nm and 1.15 nm thick shells were synthesized via a high-boiling solvent process. The energy levels of the conduction band and valance band are estimated to be -3.2 eV and -6.8 eV by cyclic voltammetry and ultraviolet-visible (UV-vis) absorption spectra. The ZnS:Mn2+/ZnS NC emission peak is primarily located at 580 nm under 310 nm light excitation, originating from the charge transition from 4T1 to 6A1 within the 3d5 configuration of the Mn2+ ion. Based on ZnS:Mn2+/ZnS NCs as the active layer electroluminescent devices, the emission peak mainly locates at 460 nm with one shoulder emission peaking at 580 nm. The photoluminescence and electroluminescence properties of ZnS:Mn2+/ZnS NCs are investigated in the view of charge carrier injection and energy level alignment.     

Synthesis and luminescence properties of ZnS:Mn/ZnS core/shell nanorod structures

Mn-doped ZnS nanorods synthesized by solvothermal method were successfully coated with ZnS shells of various thicknesses. The powder X-ray diffraction (XRD) measurements showed the ZnS:Mn nanorods were wurtzite structure with preferential orientation along c-axis. Transmission electron microscopy images (TEM) revealed that the ZnS shells formed from small particles, growing along a-axis orientation, which was proved by the XRD measurements. Room temperature photoluminescence (PL) spectra showed that the intensity of Mn emission first increased and then decreased with the thickening of the ZnS shells. The effects of ZnS shells on the luminescence properties of ZnS:Mn nanorods is discussed.     

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.     

High resolution imaging analysis of CdSe/ZnS core–shell quantum dots (QDs) using Cs-corrected HR-TEM/STEM

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, high resolution imaging analyses of QDs using a transmission electron microscope are very difficult due to their significantly small size. Successful imaging depends on the capabilities of TEM equipment and the contrast of the QDs sample relative to the supporting film. In this work, all imaging analyses were performed on a TEM equipped with a probe Cs corrector. The samples for observing QDs were prepared by drying each QDs solution on a lacey carbon Cu (300 mesh) grid previously coated with an ultra-thin graphene monolayer (thickness = 0.3 nm), due to the need to minimize the effect of the supported film.     

High color rendering index white LED based on nano-YAG:Ce3+ phosphor hybrid with CdSe/CdS/ZnS core/shell/shell quantum dots

To improve the poor color rendering index (CRI) of YAG:Ce-based white light-emitting diode (LED) due to the lack of red spectral component, core/shell/shell CdSe/CdS/ZnS quantum dots (QDs) were synthesized and blended into nano-YAG:Ce³⁺ phosphors. Prominent spectral evolution has been achieved by increasing the content of QDs. A white LED combining a blue LED with the blends of nano-YAG phosphors and orange- and red-emission QDs with a weight ratio of 1:1:1 was obtained. This kind of white LED showed excellent white light with luminescent efficiency, color coordinates, CRI and correlated color temperature (CCT) of 82.5?lm/W, (0.3264, 0.3255), 91 and 4580?K, respectively.     

Electrically controlled polarized photoluminescence of CdSe/ZnS nanorods embedded in a liquid crystal template

A novel homogeneous composite material, consisting of luminescent CdSe/ZnS quantum nanorods, embedded in the nematic liquid crystal 5CB, has been prepared. Liquid crystal cells and free-standing stretched polymer films incorporating this composite material were characterized using polarized micro-photoluminescence and electro-optical measurements under an applied electric field. A liquid crystal induced, macroscopic orientation of the nanorods in a thin layer of the material has been demonstrated. A conventional liquid crystal cell, filled with this composite, exhibits 40% modulation of the nanorod's photoluminescence intensity when subjected to an external electric field. These results indicate that quantum nanorods may have practical applications in photonic devices.     

Cytotoxicity of colloidal CdSe and CdSe/ZnS nanoparticles

Cytotoxicity of CdSe and CdSe/ZnS nanoparticles has been investigated for different surface modifications such as coating with mercaptopropionic acid, silanization, and polymer coating. For all cases, quantitative values for the onset of cytotoxic effects in serum-free culture media are given. These values are correlated with microscope images in which the uptake of the particles by the cells has been investigated. Our data suggest that in addition to the release of toxic Cd(2+) ions from the particles also their surface chemistry, in particular their stability toward aggregation, plays an important role for cytotoxic effects. Additional patch clamp experiments investigate effects of the particles on currents through ion channels.     

Preparation of a ZnS shell on CdSe quantum dots using a single-molecular ZnS precursor

A simple synthetic route to the preparation of a thin ZnS shell on CdSe quantum dot cores from the air-stable, single-molecular precursor zinc diethyldithiocarbamate, Zn(S(2)CNEt(2))(2), in the three-component solvent system octadec-1-ene/oleylamine/tri-n-octylphosphine (ODE/OLA/TOP) is presented. The one-pot synthesis proceeds through heating of the solution of CdSe cores and the amount of crystalline Zn(S(2)CNEt(2))(2) corresponding to a shell thickness of two monolayers of ZnS to 110-120 °C for 1-2 h. The role of the surfactants OLA and TOP and the significance of the temperature and the amount of Zn(S(2)CNEt(2))(2) have been investigated with optical absorption and luminescence spectroscopy. We show that the presence of both OLA and TOP is crucial for the low-temperature growth and that the amount of precursor corresponding to two monolayers of ZnS results in the highest quality of core/shell CdSe/ZnS quantum dots.     

Synthesis of highly photo-stable CuInS2/ZnS core/shell quantum dots

CuInS₂ quantum dots are considered near-ideal fluorophores based on their bright emission and low toxicity. However, CuInS₂ quantum dots are still bothered by their sensitivity to surface chemistry and chemical environment. Traditionally, the CIS QDs require an additional coating process to be encapsulated inside silica sphere or organic polymer. Up till now, few works have been made concerning improving the intrinsic stability of CIS QDs. In an effort to improve the stability of CuInS₂ quantum dots, we came up with a new method by increasing the ZnS shell thickness. These QDs were characterized by photoluminescence, HRTEM, XRD and XRF analysis. We investigated the influence of ZnS shell thickness on the ambient stability of CIS/ZnS QDs. The results demonstrated that a thicker ZnS shell helped significantly improve both photostability and chemical stability of the QDs. Finally, the thick shell QDs were dispersed into transparent polymer matrix and fabricated into a LED device, which also gave much more stability compared with conventional QDs.     

核壳结构CdS/ZnS荧光量子点的制备与荧光性能研究

以氧化镉为镉源、硫单质为硫源、油酸为配体、在十八烯体系中合成单分散的CdS纳米颗粒,研究了配体浓度对纳米微粒的生长动力学、颗粒尺寸分布的影响.采用乙基黄原酸锌作为Zn、S源的反应前体,采用逐滴滴加的方法制备了具有核壳结构的CdS/ZnS量子点,吸收光谱和荧光光谱表明CdS/ZnS纳米粒子比单一的CdS纳米粒子具有更优异的发光特性.透射电子显微镜、X射线粉末衍射、X射线光电子能谱、选区电子衍射证明ZnS在CdS表面进行了有效包覆.所制备核壳结构纳米粒子具有较好的尺寸分布,荧光发射峰半高峰宽为18～20nm,荧光量子产率达40%.     

A highly luminescent ZnS/CdSe/ZnS nanocrystals-tetrapeptide biolabeling agent

Stable colloidal ZnS/CdSe/ZnS nanocrystals capped with hexadecylamine were transferred into water by encapsulation in a protective shell of an amphiphilic polymer. The properties of the products have been investigated by dynamic lighting scattering, absorption, and photoluminescence spectroscopy. These nanocrystals, when conjugated with tuftsin in aqueous suspension, formed an effective labeling reagent for macrophages or lymphocytes. The labeling of cells was demonstrated by confocal microscopy. Hybrid bio-inorganic nanoconjugates are potentially powerful fluorescent tracking tools in biological systems.     

Two-fold emission from the S-shell of PbSe/CdSe core/shell quantum dots

The optical properties of PbSe/CdSe core/shell quantum dots with core sizes smaller than 4 nm in the 5-300 K range are reported. The photoluminescence spectra show two peaks, which become increasingly separated in energy as the core diameter is reduced below 4 nm. It is shown that these peaks are due to intrinsic exciton transitions in each quantum dot, rather than emission from different quantum dot sub-ensembles. Most likely, the energy separation between the peaks is due to inter-valley coupling between the L-points of PbSe. The temperature dependence of the relative intensities of the peaks implies that the two emitting states are not in thermal equilibrium and that dark exciton states must play an important role.     

Continuous white luminescence of ZnS:Pb2+ and core/shell ZnS:Pb2+/ZnS nanocrystals

High-quality water-soluble ZnS:Pb2+ nanocrystals were synthesized via a simple chemical codepositing method. The as-synthesized ZnS:Pb2+ nanocrystals show high monodispersity and crystallinity with a narrow size distribution (3.2 +/- 0.4 nm). ZnS:Pb2+/ZnS core/shell structures were also obtained by coating a ZnS shell displaying significantly enhanced photoluminescence (PL) intensity and photostability. For the ZnS:Pb2+/ZnS samples the position of emission spectrum shows a red-shift of approximately 10 nm, which produces a fairly pure white emission with Commission Internationale de l'Eclairage (CIE) coordinates of (0.31, 0.33). These phenomena are explained by a model of multiple Pb2+ luminescent centers.