Preparation of water-soluble CdTe/CdS core/shell quantum dots with enhanced photostability

CdTe/CdS core/shell quantum dots (QDs) have been synthesized in an aqueous phase using thioacetamide as a sulfur source. The quantum yield was greatly enhanced by the epitaxial growth of a CdS shell, which was confirmed by X-ray photoelectron spectroscopy (XPS) results. The quantum yield of as-prepared CdTe/CdS core/shell QDs without any post-preparative processing reached 58%. The experimental results illustrate that the QDs with core/shell structure show better photostability than thioglycolic acid (TGA)-capped CdTe QDs. The cyclic voltammograms reveal higher oxidation potentials for CdTe/CdS core/shell QDs than for TGA-capped CdTe QDs, which explains the superior photostability of QDs with a core/shell structure. This enhanced photostability makes these QDs with core/shell structure more suitable for bio-labeling and imaging.     

Photostability comparison of CdTe and CdSe/CdS/ZnS quantum dots in living cells under single and two-photon excitations

The photostability is an outstanding feature of quantum dots (QDs) used as fluorescence probes in biological staining and cell imaging. To find out the related factors in the QD photostability, the photobleaching of naked CdTe QDs and BSA coated CdSe/CdS/ZnS QDs in human hepatocellular carcinoma (QGY) cells and human nasopharynx carcinoma (KB) cells were studied under single photon excitation (SPE) and two-photon excitation (TPE). In these two cell lines the cellular QDs were irradiated by a 405 nm continuous wave laser for SPE or an 800 nm femto-second (fs) laser for TPE. The QD photobleaching with the irradiation time was found to fit a biexponential decay. The fast decay plays a dominant role in the bleaching course and thus can be used as the parameter to quantitatively evaluate the QD photostability. The TPE decreased the QD photobleaching as compared to SPE. The BSA coated core/shell QDs had improved the photostability up to 4-5 times than the naked QDs due to the shielding effect of the QD shell. Therefore, it is better to use core/shell structured QDs as the fluorescence probe combining with a TPE manner for those long-term monitoring studies.     

Resonant Raman scattering of ZnS,ZnO, and ZnS/ZnO core/shell quantum dots

Resonant Raman scattering by optical phonon modes as well as their overtones was investigated in ZnS and ZnO quantum dots grown by the Langmuir–Blodgett technique. The in situ formation of ZnS/ZnO core/shell quantum dots was monitored by Raman spectroscopy during laser illumination.     

IR-active vibrational modes of CdTe and CdSe colloidal quantum dots and CdTe/CdSe core/shell nanoparticles and coupling effects

The frequencies of the vibrational modes of CdTe and CdSe quantum dots and CdTe/CdSe core/shell nanoparticles prepared by the colloid chemistry method are determined using IR transmission and IR reflection spectroscopy. The experimental IR transmission spectrum of CdTe and CdSe nanocrystals exhibits a broad minimum located between the frequencies of the transverse optical (TO) and longitudinal optical (LO) phonons of bulk CdTe and CdSe crystals. The frequencies of the modes for ensembles of CdTe and CdSe quantum dots are considerably shifted toward lower frequencies as compared to those calculated for single quantum dots. This is explained by the dipole-dipole interaction between quantum dots. The frequencies of modes for the structures with core/shell nanoparticles differ little from the calculated frequencies. This suggests a weakening of the interaction in these structures due to the enhancement of dielectric screening.     

Investigation of the radiative lifetime in core–shell CdSe/ZnS and CdSe/ZnSe quantum dots

Using the one band effective mass approximation model we computed the optical properties of the spherical shaped CdSe/ZnS and Cdse/ZnSe core–shell quantum dot (CSQD). For each structure we calculated the charge carrier energies and corresponding wave functions. We investigated the dependence of the carrier energies on various parameters of the CSQD, including its size. Then we calculated the radiative recombination lifetime for the two types of CSQDs nanocrystals. We found that as the size of the dot is increased the optical gap of CSQD is reduced, resulting in a reduction in electron energies and an increase in hole energies. We have shown that the radiative recombination lifetime in the CdSe/ZnS and CdSe/ZnSe CSQDs decreased by increasing the shell thickness around the core of the QD. We also showed that the radiative lifetime in the CdSe/ZnS is less than that in the CdSe/ZnSe CSQDs and is sensitive to the size and nature of shell of the semiconductor's material.     

低强度飞秒激光激发下CdTe和CdTe/CdS核壳量子点的荧光上转换研究

利用400 nm和800 nm不同波长的低强度飞秒激光,对CdTe和CdTe/CdS核壳量子点溶胶进行激发,研究其稳态和时间分辨荧光性质.800 nm飞秒激光激发下,CdTe和CdTe/CdS核壳量子点产生上转换发光现象,上转换荧光峰与400 nm激发下的荧光峰相比蓝移最多达15 nm,而且蓝移值与荧光量子产率有关.变功率激发确认激发光功率与上转换荧光强度间满足二次方关系,时间分辨荧光的研究表明荧光动力学曲线服从双e指数衰减.提出表面态辅助的双光子吸收模型是低激发强度上转换发光的主要机理.CdTe和CdT 关键词： CdTe量子点 CdTe/CdS核壳量子点 时间分辨荧光 上转换荧光     

Preparation and characterization of ZnS/CdS bi-layer for CdTe solar cell application

In this work, bilayer ZnS/CdS film was prepared as an improved window layer of CdTe solar cell. TEM was used to observe the cross section of the bilayer structure. The total thickness of ZnS/CdS film was about 60 nm, which could allow more photons to pass through it and contribute to the photocurrent. Optical properties of the bilayers were investigated using UV–vis spectroscopy. Compared with poor transmission of standard CdS film in the short wavelength range of 350–550 nm, the transmission of ZnS/CdS was improved and reached above 50%. The ZnS/CdS was annealed with CdCl₂. X-ray photoelectron spectroscopy (XPS) was used to investigate its chemical properties. A possible diffusion between CdS and ZnS was observed after annealing. The efficiency of standard CdS/CdTe solar cell was 9.53%. The device based on ZnS/CdS window layer had a poor 6% efficiency. With annealing treatment on ZnS/CdS layer, the performance was improved and reached 10.3%. In addition, the homogeneity of solar cell performance was improved using ZnS/CdS window layer. A thin ZnS layer was quite effective to reduce the possible shunt paths and short parts of window layer and consequently contributed to fabrication of a homogeneous CdTe solar cell.     

Decay of electronic excitations in CdS and CdS/ZnS colloidal quantum dots: spectral and kinetic investigations

Using the spectral methods of induced absorption, luminescence, and photostimulated luminescence flash, we have experimentally investigated processes of decay of electronic excitations in CdS colloidal quantum dots and in CdS/ZnS “core-shell” systems synthesized in gelatin by the sol-gel method. It has been shown that the decay of electronic excitations in colloidal quantum dots of this type is predominantly related to a fast localization of nonequilibrium charge carriers on surface defects and their subsequent recombination during times on the order of units and tens of picoseconds. The passage to core-shell systems eliminates, to a large extent, surface defects of the core, some of which are luminescence centers. However, upon using the sol-gel synthesis, a noticeable fraction of luminescence centers are formed in the interior of the CdS quantum dot, which, as well as in the case of CdS/ZnS systems, ensures localization of exciton, blocks its direct annihilation, and maintains recombination radiation.     

Manifestation of CdTe quantum dots and interdiffusion in IR reflection spectra of CdTe/ZnTe structures with quantum dots

The IR reflection spectra of structures that consist of alternating layers of CdTe quantum dots and ZnTe barriers and are grown on ZnTe and CdTe/ZnTe buffer layers on GaAs(001) substrates are studied. The spectra are processed using dispersion analysis, and the parameters of the oscillators are determined. In the spectra, quantum dots manifest themselves in the form of a broad band at a frequency close to the frequency of the Fröhlich mode. It is revealed that the spectra contain features associated with the interdiffusion of the CdTe and ZnTe compounds, i.e., bands attributed to the local mode of Zn atoms in the CdTe compound and two gap modes of Cd atoms in the ZnTe compound.     

Facile synthesis and characterization of glass/cobalt core/shell composite spheres with tunable shell morphologies

Polyhedral cobalt microcrystals assembled on hollow glass spheres are successfully synthesized by a facile and easy-control hydrothermal reduction process, and thus hierarchical glass/cobalt core/shell composite hollow spheres are fabricated with low-density (0.96 g cm⁻³). By properly tuning the process conditions and the component of the reaction solution, a series of composite spheres with gradient in morphologies of the shell layer can be prepared. Based on a series of contrast experiments, the probable formation mechanism of the core/shell hierarchical structures is proposed. The magnetic properties of the products are studied and the results demonstrate that the composite spheres present ferromagnetic properties related to the special shell morphologies. The composite hollow spheres thus obtained may have some promising applications in the fields of low-density magnetic materials, conduction, and catalysis, etc. This work provides an additional strategy to prepared core/shell composite spheres with tailored shell morphology and magnetic properties.     

Imaging and spectroscopy of artificial-atom states in core/shell nanocrystal quantum dots.

Current imaging scanning tunneling microscopy is used to observe the electronic wave functions in InAs/ZnSe core/shell nanocrystals. Images taken at a bias corresponding to the s conduction band state show that it is localized in the central core region, while images at higher bias probing the p state reveal that it extends to the shell. This is supported by optical and tunneling spectroscopy data demonstrating that the s-p gap closes upon shell growth. Shapes of the current images resemble atomlike envelope wave functions of the quantum dot calculated within a particle in a box model.     

The electronic and optical properties of a triexciton in CdSe/ZnS core/shell quantum dot nanocrystals

In the study, we aim to investigate the electronic and optical properties of single excitons, biexcions and triexcitons in a CdSe/ZnS core/shell quantum dot nanocrystal. The electronic structure has been determined by solving of the Poisson–Schrödinger equations self-consistently. In calculations, the exchange-correlation effects between identical particles have been taken into account in the frame of the local density approximation. We have demonstrated that the optical properties of triexciton systems are remarkably different from the single and biexciton systems. Absorption peaks or transition energies of the triexciton system are well separated from those of single- and bi-exciton systems. We have observed that the core-radius dependent transition energy variations of triexcitons are higher when compared with single- and bi-excitonic systems. The transition energy shifts of double and triple excitons with respect to the single exciton have been calculated as a function of the core radius and we have shown that the energy shifts are inversely proportional with the radius. We have also investigated the radius-dependent changes in binding energies and lifetimes of the structures and the comparative results have been discussed in a detail manner.     

Facile synthesis of near-infrared CuInS<Subscript>2</Subscript>/ZnS quantum dots and glycol-chitosan coating for in vivo imaging

This study describes the synthesis method of water-soluble, low-toxicity, photostable highly luminescent probes based on I–III–VI₂ type semiconductor quantum dots (QDs) and the possibility of tumor targeting in living animals. Cd-free high-quality CuInS₂/ZnS core/shell QDs were synthesized, and their surfaces were reacted with mercaptoundecanoic acid for aqueous phase transfer followed by reaction with glycol-chitosan; lastly, Arg-Gly-Asp (RGD) integrin-binding peptide was covalently attached for in vivo tumor targeting. Dowtherm A, a highly viscous heat-transfer organic fluid, was used to control semiconductor crystal growth at high temperature (>230 °C) during organic synthesis. The structural and optical properties of the resulting CuInS₂/ZnS QDs were investigated. The average diameters of CuInS₂ and CuInS₂/ZnS QDs were 3.0 and 3.7 nm, respectively. Cell toxicity and in vivo tumor targetability in RR1022 cancer cell-xenografted mice were further evaluated using cRGDyk-tagged glycol-chitosan-coated CuInS₂/ZnS QDs. Glycol-chitosan-coated MUA-QDs displayed a Z-average diameter of 203.8 ± 7.67 nm in water by dynamic light scattering.

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Graphical abstract In vivo tumor targeting using cRGDyk-tagged glycol-chitosan-coated MUA-CuInS₂/ZnS QDs nanoparticles

     

Atomistic tight-binding computations of the structural and optical properties of CdTe/CdX (X=S and Se)/ZnS core/shell/shell nanocrystals

A study of CdTe/CdX (X=S and Se)/ZnS core/shell/shell nanocrystals is carried out using atomistic tight-binding theory and the configuration interaction method to provide information for applications in bioimaging, biolabeling, display devices and near-infrared electronic instruments. The calculations yield the dependences of the internal and external passivated shells on the natural behaviours of CdTe/CdX (X=S and Se)/ZnS core/shell/shell nanocrystals. The reduction of the optical band gaps is observed with increasing numbers of monolayers in the external ZnS shell due to quantum confinement. Interestingly, the optical band gaps of CdTe/CdS/ZnS core/shell/shell nanocrystals are greater than those of CdTe/CdSe/ZnS core/shell/shell nanocrystals. In the presence of an external ZnS-coated shell, electron–hole wave function overlaps, oscillation strengths, ground-state exchange energies and Stokes shift are improved, whereas ground-state coulomb energies and fine-structure splitting are reduced. The oscillation strengths, Stokes shift and fine-structure splitting are reduced with the increase in external ZnS shell thickness. The oscillation strengths, Stokes shift and fine-structure splitting of CdTe/CdS/ZnS core/shell/shell nanocrystals are larger than those of CdTe/CdSe/ZnS core/shell/shell nanocrystals. Reduction of the atomistic electron–hole interactions is observed with increasing external ZnS shell size. The strong electron–hole interactions are more probed in CdTe/CdS/ZnS core/shell/shell nanocrystals than in CdTe/CdSe/ZnS core/shell/shell nanocrystals.     

Electrostatic assembly of CdTe quantum dots with different charged ligands into TiO2 porous film for solar cells

We have demonstrated an approach for the electrostatic assembly of CdTe quantum dots (QDs) with different charged ligands as sensitizers, achieving high coverage and good dispersion in TiO₂ porous films. The CdTe QD-sensitized TiO₂ porous films were subjected to thermal annealing in a high vacuum chamber to remove the ligand linker, resulting in the formation of direct heterojunctions between the bare CdTe QDs and TiO₂ for a favorable charge transfer. The as-received CdTe QD-sensitized TiO₂ porous films were employed as photoanodes for quantum dot-sensitized solar cells (QSSCs), and the photocurrent density reached as high as 4.69 mA/cm² under a standard illumination condition of simulated AM 1.5G (100 mW/cm²).     

Dependence of the interband transition and the activation energy on the ZnTe spacer thickness in CdTe/ZnTe double quantum dots

Photoluminescence (PL) measurements were carried out to investigate the interband transition and the activation energy in CdTe/ZnTe double quantum dots (QDs). While the excitonic peaks corresponding to the interband transition from the ground electronic subband to the ground heavy-hole (E₁-HH₁) in the CdTe/ZnTe double QDs shifted to higher energy with decreasing ZnTe spacer thickness from 30 to 10 nm due to transformation from CdTe QDs to Cd_xZn_1−xTe QDs, the peaks of the (E₁-HH₁) transitions shifted to lower energy with decreasing spacer thickness from 10 to 3 nm due to the tunneling effects of the electrons between CdTe double QDs. The decrease in the activation energy with decreasing ZnTe spacer thickness might originate from an increase in the number of defects in the ZnTe spacer. The present results can help improve the understanding of the interband transition and the activation energy in CdTe/ZnTe double QDs.     

Control of the binding energy by tuning the single dopant position,magnetic field strength and shell thickness in ZnS/CdSe core/shell quantum dot

Recently, the new tunable optoelectronic devices associated to the inclusion of the single dopant are in continuous emergence. Combined to other effects such as magnetic field, geometrical confinement and dielectric discontinuity, it can constitute an approach to adjusting new transitions. In this paper, we present a theoretical investigation of magnetic field, donor position and quantum confinement effects on the ground state binding energy of single dopant confined in ZnS/CdSe core/shell quantum dot. Within the framework of the effective mass approximation, the Schrödinger equation was numerically been solved by using the Ritz variational method under the finite potential barrier. The results show that the binding energy is very affected by the core/shell sizes and by the external magnetic field. It has been shown that the single dopant energy transitions can be controlled by tuning the dopant position and/or the field strength.     

核壳结构磁性复合纳米材料的可控合成与性能

具有核/壳结构的磁性复合纳米材料是十分重要的功能材料,其综合物性受材料微结构的影响,而这很大程度上又取决于复合体系的可控合成.本文综述了近二十年来有关核/壳磁性复合纳米材料的制备、表征及性能研究方面的进展,讨论的体系主要有：铁氧体基永磁/软磁（反铁磁）复合纳米材料、非磁性体包覆磁性核而成的复合纳米材料、用磁性颗粒催化合成的碳基复合纳米材料、基于交换偏置效应而设计的复合纳米材料、核-壳同轴结构的一维复合纳米材料和核/壳/壳三元结构的磁性复合纳米材料等.构建复合体系的组分包括M型永磁铁氧体、3d过渡金属（及其合金、氧化物、碳化物）、多铁化合物、非磁性体（比如绝缘体、半导体、有机分子）和碳材料等,着重分析了复合纳米材料的热稳定性、光致发光性能、光电催化能力、电化学特性、微波吸收性能、磁电阻效应、永磁体性能、高频软磁特性、交换偏置效应及其相关现象.最后,对核/壳结构磁性复合纳米材料的未来发展趋势进行了展望,并在基础研究和改性应用方面提出了一些建议.     

The influence of cysteamine and counterion concentrations on the properties of CdSe/ZnS quantum dots

The influence of the cysteamine surfactant concentration on the stability of CdSe/ZnS nanoparticles (NPs) solubilized by this compound at the phase interface between two immiscible liquids is considered. The steady-state and time-resolved fluorescence spectroscopy data show that the fluorescence quantum yield of cysteamine-coated NPs and their stability to aggregation in a potassium phosphate buffer are determined by the balance between the concentrations of surfactant in the aqueous phase and hydrophobic NPs in the nonpolar phase (chloroform, toluene, etc.). It is found that the brightest and most stable hydrophilic NPs can be obtained by completely coating them by cysteamine molecules without a surfactant deficit or excess in the reaction at the phase interface.