Synthesis of ZnSe quantum dots and ZnSe-ZnS core/shell nanostructures

Colloidal ZnSe nanocrystals were synthesized in hot mixtures of long-chain alkylamines, fatty acids, and alkylphosphines. It was possible to tune the size of nanocrystals by varying the reaction time. Transmission electron microscope images showed the presence of spherical ZnSe nanocrystals and X-ray diffraction pattern of ZnSe nanocrystals showed the existence of both the crystalline phase, namely, wurtzite and zinc blende. The ZnSe nanocrystals were then passivated with higher band gap ZnS; this lead to a 2.6-fold enhancement in the integrated photoluminescence intensity of ZnSe nanocrystals. We also synthesized the reverse type core/shell ZnS/ZnSe nanocrystals. These exhibited a significant red shift in the absorption edge after coating with a thin ZnSe shell.     

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%.     

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.     

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.     

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.     

Synthesis of highly luminescent CdTe/ZnO core/shell quantum dots in aqueous solution

The synthesis and photoluminescence (PL) properties of aqueous CdTe/ZnO core/shell quantum dots (QDs) have been investigated by using thiolglycolic acid as a capping reagent. The highlighted contribution of the present study was CdTe QDs coated with a ZnO shell by controlling the hydrolysis process of Zn(OAc)₂. The QDs benefitted from overcoming the high lattice mismatch between CdTe and ZnO. The PL peak wavelength of the CdTe/ZnO QDs with high PL quantum yields up to 88% was located in a range between 547 and 596 nm by adjusting the size of CdTe cores and the thickness of ZnO shells. The results of X-ray diffraction analysis and transmission electron microscopy observation indicate that the dot-shaped CdTe/ZnO QDs (566 nm) with an average size of 2.2 nm in diameter belong to the cubic CdTe crystal structure. Due to the passivation of surface defects, it is found that the luminescence decay curves accord with a biexponential decay model of exciton and trap radiation behavior. The average PL lifetimes of CdTe (571 nm) and CdTe/ZnO (596 nm) QDs at room temperature are 27.3 and 35.1 ns, respectively.     

CdSe／CdS核壳量子点拉曼光谱的表面模分析

研究了不同壳层厚度(0～5.5ML)的CdSe/CdS核壳量子点的一次和高次拉曼散射,具体分析了CdSe和CdS的表面模随着壳层厚度的变化情况.结果表明,随着壳层厚度的增加,CdSe表面模(SO1)从198cm-1频移到185cm-1,CdS的表面模(SO2)从275cm-1频移到267cm-1,并且SO1和SO2试验结果与由介电连续模型得到的理论值很接近.此外,根据CdSe表面模的频移,对随着CdS壳层厚度的增加而引起的核层(CdSe)的介电常数随环境的变化做出了修正.     

Aqueous synthesis of Zn-based ternary core/shell quantum dots with excellent stability and biocompatibility against different cell lines

Journal of Materials Science - Ternary quantum dots (QDs) such as zinc indium sulphide (ZIS), copper indium sulphide (CIS) and silver indium sulphide (AIS) have received great attention. Among...     

3-component low temperature solvothermal synthesis of colloidal cadmium sulfide quantum dots

We report the solvothermal synthesis of colloidal cadmium sulfide quantum dots via a three-component system affording various particle diameter ranging from 3.368 nm to 8.411 nm. The band gap, and therefore the optical property, of these nanocrystals can be tuned by varying the reaction time and temperature of the system. The results obtained show strong confinement of particles with diameter smaller than the exciton Bohr radius of CdS. The growth kinetics was found to follow a diffusion-controlled process at the initial stage then shifts to a surface-controlled incorporation of reactants to the crystallite after the particle size becomes comparable to the exciton Bohr radius.     

CdSe/CdS core/shell quantum dots as sensitizer of a photorefractive polymer composite

Abstract

CdSe/CdS core/shell, tri-n-octylphosphine oxide passivated, quantum dots are used to sensitize a photorefractive polymer composite. The composite also consists of poly(N-vinylcarbazole) as the nominally charge transporting matrix and an electro-optic chromophore. The efficacy of sensitization and consequent photorefractive performance is investigated using transmission spectroscopy and ellipsometry, two-beam coupling and degenerate four-wave mixing experiments. The photorefractive nature of the photo-induced grating is confirmed by the observation of asymmetric two-beam coupling. Four-wave mixing reveals record diffraction efficiencies for a nano-particle-sensitized photorefractive polymer at the field levels applied (1.3% at 70 V.μm^?1). A recently developed analytical technique is used to extract space-charge field rise time values from degenerate four-wave mixing transients. In turn, analysis of the dependence of the rise time on applied field is used to determine the zero-field charge dissociation efficiency to be 3.6 × 10^?5 ± 0.5 × 10^?5. It is further shown that the magnitude of this parameter accounts for most of the difference in photorefractive response rate between the present material and a similar C₆₀ sensitized composite.     

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.     

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.     

InAs/InP/ZnSe core/shell/shell quantum dots as near-infrared emitters: Bright, narrow-band, non-cadmium containing, and biocompatible

High quality InAs/InP/ZnSe core/shell/shell quantum dots have been grown by a one-pot approach. This engineered quantum dots with unique near-infrared (NIR) fluorescence, possessing outstanding optical properties, and the biocompatibility desired for in vivo applications. The resulting quantum dots have significantly lower intrinsic toxicity compared to NIR emissive dots containing elements such as cadmium, mercury, or lead. Also, these newly developed ultrasmall non-Cd containing and NIR-emitting quantum dots showed significantly improved circulation half-life and minimal reticuloendothelial system (RES) uptake.      

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.     

Photoluminescent, transparent and flexible di-ureasil hybrids containing CdSe/ZnS quantum dots

We describe, in this paper, the sol-gel synthesis of di-ureasil based nanocomposites prepared in situ in the presence of organically capped CdSe quantum dots (QDs) or CdSe QDs which have been coated with a ZnS shell. For the latter a new chemical route to coat the CdSe QDs with ZnS shells was investigated and is now reported. The QDs became well dispersed in the final nanocomposites, whose microstructural homogeneity was evaluated by atomic force microscopy (AFM) and transmission electron microscopy (TEM) analyses. In order to understand the optical behaviour of di-ureasil containing QDs, a detailed photoluminescent study was undertaken for a selected particle size distribution of ZnS coated CdSe QDs (d～4.5?nm). Emission quantum yields up to 0.11 were measured in the final nanocomposites that present a huge (between 3 and 6 orders of magnitude) increase in the lifetime of the QDs (relative to that of isolated ones), as a result of energy transfer occurring between the intimately mixed di-ureasil host and the QDs.     

Optimization of process parameter for synthesis of silicon quantum dots using low pressure chemical vapour deposition

Si quantum dots-based structures are studied recently for performance enhancement in electronic devices. This paper presents an attempt to get high density quantum dots (QDs) by low pressure chemical vapour deposition (LPCVD) on SiO ₂ substrate. Surface treatment, annealing and rapid thermal processing (RTP) are performed to study their effect on size and density of QDs. The samples are also studied using Fourier transformation infrared spectroscopy (FTIR), atomic force microscopy (AFM), scanning electron microscopy (SEM) and photoluminescence study (PL). The influence of Si–OH bonds formed due to surface treatment on the density of QDs is discussed. Present study also discusses the influence of surface treatment and annealing on QD formation.     

'Giant' CdSe/CdS core/shell nanocrystal quantum dots as efficient electroluminescent materials: strong influence of shell thickness on light-emitting diode performance

We use a simple device architecture based on a poly(3,4-ethylendioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)-coated indium tin oxide anode and a LiF/Al cathode to assess the effects of shell thickness on the properties of light-emitting diodes (LEDs) comprising CdSe/CdS core/shell nanocrystal quantum dots (NQDs) as the emitting layer. Specifically, we are interested in determining whether LEDs based on thick-shell nanocrystals, so-called "giant" NQDs, afford enhanced performance compared to their counterparts incorporating thin-shell systems. We observe significant improvements in device performance as a function of increasing shell thickness. While the turn-on voltage remains approximately constant for all shell thicknesses (from 4 to 16 CdS monolayers), external quantum efficiency and maximum luminance are found to be about one order of magnitude higher for thicker shell nanocrystals (≥13 CdS monolayers) compared to thinner shell structures (<9 CdS monolayers). The thickest-shell nanocrystals (16 monolayers of CdS) afforded an external quantum efficiency and luminance of 0.17% and 2000 Cd/m(2), respectively, with a remarkably low turn-on voltage of ~3.0 V.