A comparative study of conventional type II and inverted core–shell nanostructures based on CdSe and ZnS

The objective of this work is to investigate structural, morphological and optical properties of conventional CdSe/ZnS core–shell and inverted ZnS/CdSe core–shell nanostructures for opto-electronic device applications. For this purpose both nanostructures were synthesized using chemical bath deposition technique in thin film form. The structural properties were studied using X-ray diffraction technique with Rietveld refinement and transmission electron microscopy (TEM). The surface morphology of synthesized thin film was illustrated in the form 2D and 3D images using atomic force microscopy (AFM). The optical properties were explained using UV–Vis absorption spectroscopy and photo luminescence (PL) spectroscopy in in situ monitoring process. A comparison of estimated particle size from XRD, high resolution AFM and TEM images was resulted in good agreement as 2.1, 2.4 and 2.1 nm respectively for conventional CdSe/ZnS core–shell and as 2.5, 2.5 and 2.2 nm respectively for inverted ZnS/CdSe core–shell nanostructures.     

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.     

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.     

CdSe/ZnS纳晶中相干电声耦合效应的二维电子光谱研究

Coherent exciton-phonon coupling in CdSe/ZnS nanocrystals have been investigated by temperature-dependent two-dimensional electronic spectroscopy (2DES) measurements. Benefiting from the ability of 2DES to dissect assembles in nanocrystal films, we have clearly identified experimental evidences of coherent coupling between exciton and phonon in CdSe/ZnS nanocrystals. In time domain, 2DES signals of excitonic transitions beat at a frequency resonant to a longitudinal optical phonon mode; in energy domain, phonon side bands are distinct at both Stokes and anti-Stokes sides. When temperature increases, phonon-induced exciton dephasing is observed with dramatic broadening of homogeneous linewidth. The results suggest exciton-phonon coupling is essential in elucidating the quantum dynamics of excitonic transitions in semiconductor nanocrystals.     

ZnCuInS/ZnS量子点光致发光温度依赖性研究

ZnCuInS/ZnS量子点是一种无重金属"绿色"半导体纳米材料。制备出了直径为2.9nm的ZnCuInS/ZnS核壳量子点。从ZnCuInS/ZnS量子点的吸收及光致发光光谱中可以看到,量子点的斯托克斯位移为410meV。这样大的斯托克斯位移表明,ZnCuInS/ZnS量子点的复合机制与缺陷能级有关。研究并计算了在辐射及非辐射驰豫过程的(Huang-Rhys)因子及平均声子能量。结果表明在50~373K范围内,能量带隙的变化以及光致发光光谱的增宽是分别由光从能带边缘向缺陷能级跃迁及载流子声子耦合导致的。     

CdSe/ZnSe/ZnS多壳层结构量子点的制备与表征

展示了一种简捷的多壳层量子点合成路线。在含有过量Se源的CdSe体系中直接注入Zn源,"一步法"合成了CdSe/ZnSe量子点;进一步以CdSe/ZnSe为"核",表面外延生长ZnS壳层制备了核/壳/壳结构CdSe/ZnSe/ZnS量子点。相对于以往报道的多壳层结构量子点的制备方法,该方法通过减少壳层的生长步骤有效地简化了实验操作,缩短了实验周期,同时减少对原料的损耗。对量子点进行高温退火处理,能够大幅提高CdSe/ZnSe/ZnS量子点的发光量子产率。透射电镜、XRD以及光谱研究表明:所制备的量子点接近球形,核与壳层纳米晶均为闪锌矿结构,最终获得的CdSe/ZnSe/ZnS量子点的光致发光量子产率达到53％。为了实现量子点的表面生物功能化,通过巯基酸进行了表面配体交换修饰,使量子点表面具有水溶性的羧基功能团,并且能够维持较高的光致发光量子产率。     

Characterization of semiconductor core-shell nanoparticles by resonant Raman scattering and photoluminescence spectroscopy

Colloidal CdSe nanoparticles (NPs), passivated with CdS and ZnS, were characterized by resonant Raman scattering and photoluminescence (PL). The effect of the passivating shell, its volume and formation procedure on optical and vibrational spectra is discussed. Analyzing the Raman peaks due to optical phonons inside the core and those related to the core-shell interface allows some understanding of the relation between the core-shell structure and its PL properties to be achieved. In particular, a compositional intermixing at the core/shell interface of the NPs was deduced from the Raman spectra, which can noticeably affect their PL intensity.     

单核/双壳结构CdSe/CdS/ZnS纳米晶的合成与发光性质

以巯基乙酸为稳定剂,在水溶液中合成了单核/双壳结构的CdSe/CdS/ZnS纳米晶。在内核CdSe和外壳ZnS之间的内壳CdS作为晶格匹配调节层,能够很好的改善核/壳界面处的性能,而且,最外层ZnS能够最大程度地使激子受限。用TEM和XPS对纳米晶进行了表征,并且用光致发光光谱和吸收光谱对不同核壳结构的纳米晶的发光性能进行了比较,结果表明单核/双壳结构的纳米晶具有更加优异的发光特性。     

Raman spectroscopy of ZnS nanostructures

We report Raman scattering results of wurtzite ZnS nanowires, nanocombs, and nanobelts. The Raman spectrum obtained from ZnS nanowires exhibits first‐order phonon modes at 272, 284, and 350 cm⁻¹, corresponding to A₁/E₁ transverse optical, E₂ transverse optical, and A₁/E₁ longitudinal optical phonons, respectively. Several multiphonon modes are also observed. The longitudinal optical phonon mode varies in wavenumber for nanocombs and nanobelts, indicating that the residual strain varies during the morphological change from ZnS nanowires to nanocombs and ultimately to nanobelts. Interestingly, a surface optical (SO) phonon mode varies in wavenumber depending on the shape and surface roughness of the ZnS nanostructures. The surface modulation wavelengths of the ZnS nanowires, nanocombs, and nanobelts are estimated using the SO phonon dispersion relations and the observed SO phonon wavenumbers. Copyright © 2012 John Wiley & Sons, Ltd.     

CdSe &; ZnS core/shell nanoparticles generated by laser ablation of microparticles

Laser Ablation of Microparticles (LAM) is a process of nanoparticle formation in which microparticles in a flowing aerosol are continuously ablated by high-power laser pulses. For the first time, we have produced CdSe/ZnS core/shell nanoparticles using a double ablation apparatus, designed to undergo a two-step LAM process. This process can be inverted to produce ZnS/CdSe core/shell nanoparticles. The present work focuses on the range around ∼15 nm radius heterostructures and uses high-resolution transmission electron microscopy (HRTEM) to image core and shells. For smaller particles, core shell structures have been detected with energy dispersive spectroscopy (EDS) 5 nm spot size beam and fast Fourier transform (FFT) spectra. Differences in the ablation behavior were measured between the two IIB–VIA type semiconductors.     

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.     

Interlevel transitions in core–shell nanodots with dielectric environment

The interlevels absorption in spherical CdSe/ZnS and ZnS/CdSe core–shell nanodots is theoretically investigated taking into account the dielectric environment effect. By considering the joint action of the quantum confinement and polarization charges, the influence of the nanosystem geometry upon the energy spectrum and oscillator strength associated to interlevel transitions is studied. We found that: (1) the low dielectric constant environments significantly blueshift the energy levels; (2) the transition matrix elements and oscillator strengths considerably vary with the core–shell radius ratio; (3) the peak position of the interlevels optical absorption is greatly affected by changing of the shell thickness, but for some geometries the absorption spectrum also becomes sensitive to the environment dielectric properties. The possibility of tuning the resonant energies by using the combined effect of the spatial confinement and dielectric mismatch between the dot and the surrounding medium can be useful in the optoelectronic devices applications.     

球形ZnS/CdSe/ZnS核壳壳量子点的三阶极化率参量相关特征

在有效质量近似下,利用量子力学的密度矩阵理论,采用无限深势阱模型导出了三层球型量子点的三阶非线性光学极化率(自聚焦)的解析表达式.通过数值计算,分析了ZnS/CdSe/ZnS球型核壳结构量子点的三阶极化率(自聚焦)与量子点尺寸和入射光频率之间的关系.结果显示,量子点尺寸增大时,自聚焦效应三阶极化率(自聚焦)的峰值高度增大,峰值位置红移.本文的讨论为实验研究和实际应用提供了理论依据,对于光电器件的研究和改进有参考价值.     

极化子效应对核壳量子点中光学克尔效应的影响

在有效质量近似下利用量子力学的密度矩阵理论,采用无限深势阱模型解三维薛定谔方程得到电子的本征能量和波函数.从理论上计算了考虑极化子效应后,在导带子带间跃迁时ZnS/CdSe柱型核壳结构量子点光学克尔效应的三阶极化率.通过数值计算,分析了电子-LO声子和电子-IO声子相互作用对ZnS/CdSe柱型核壳结构量子点光学克尔效应的三阶极化率的影响.结果表明：极化子效应对光学克尔效应的三阶极化率 有很大影响,并且影响的大小与量子点的尺寸大小有关.       

极化子效应对ZnS/CdSe核壳量子点光吸收系数的影响

在有效质量近似下,利用量子力学密度矩阵理论,从理论上研究了考虑极化子效应后核壳量子点中线性、三阶非线性以及总的光吸收系数在不同条件下随入射光能量变化的关系。通过数值计算,分析了电子-LO声子和电子-IO声子相互作用对ZnS/CdSe柱型核壳结构量子点光吸收系数的影响。结果表明,极化子效应对光吸收系数有很大影响,不同声子模式对光吸收系数影响大小不同。考虑电子-LO声子后,光吸收系数被大大提高。另外,入射光强和弛豫时间对系统的吸收系数也有很大影响。     

Evolution of Luminescence with Shell's Thickness in Colloidal CdSe/CdS Core/Shell Quantum Dots

We synthesize colloidal CdSe/CdS core/shell quantum dots with different shell thicknesses, and there are five samples including CdSe core dots, and CdSe/CdS core/shell dots with 1-4 CdS layers. X-ray diffraction and Raman measurements indicate that the stress in CdSe core becomes stronger with the increasing shell thickness, and the optical measurements show that when the shell becomes thicker, the photoluminescence quantum yield is enhanced, and the radiative decay is also expedited. The temperature-dependent optical spectra are measured. The relation between the microstructure and the optical properties is discussed.     

Determination of Thermal History by Photoluminescence of Core‐Shelled Quantum Dots Going Through Heating Events

A kind of novel thermal history nanosensors are theoretically designed and experimentally demonstrated to permanently record thermal events. The photoluminescence (PL) spectrum of core‐shelled quantum dots (QDs) CdSe/ZnS irreversibly shifts with heating histories (temperature and duration) of thermal events. The induced PL shift of the QDs CdSe/ZnS is employed to permanently record thermal histories. We further model a kind of thermal history nanosensor based on the thermal‐induced phenomena of core‐shelled QDs to permanently record thermal histories at microscale and demonstrate to reconstruct temperature and duration of heating events simultaneously from PL spectra of the QDs. The physical mechanism of the sensors is discussed.     

CdSe/ZnS Fluorescent Nanoparticles as Nanoprobes of Local pH in Diagnostics of Oncology

We discuss the fluorescence spectra from a set of points in histological sections of colon tissue with different levels of pathology that were stained with hydrophilic semiconductor CdSe/ZnS nanoparticles that were modified by a unique method at the phase interface. The shifts in the fluorescence spectra that were recorded for stained cells at different pathologies are described using the electrochromism of the nanoparticles. Aqueous solutions of the CdSe/ZnS nanoparticles with different pH values are used as systems that model the acidity of a biological medium. It has been shown that the shifts of the fluorescence bands of the CdSe/ZnS nanoparticles are caused by a change in the local electrical field that is induced by solvated ions near their surface at different pH values of the solutions. The application of the CdSe/ZnS nanoparticles as nanoprobes for the local pH in biological tissue is discussed in the context of this 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.     

Size controlled synthesis of semiconductor nanocrystals in a continuous-flow mode microcapillary reactor

A microcapillary reactor with 320 μm inner diameter was utilized for CdSe nanoparticle synthesis. The influence of the reaction temperature and flow rate of precursors on the size and size distribution of prepared CdSe nanoparticles was systematically studied. The as-prepared nanoparticles exhibit sharp excitonic absorption and photoluminescence peak (FWHM 30 nm) with a quantum-yield around 10–40%. The microcapillary reactor was also used for CdSe/ZnS core-shell nanoparticle synthesis in continuous-flow mode. The quantum yield of the core-shell nanoparticles was found to be considerably influenced by the reactor temperature and have a close correlation with the thickness of ZnS shell under growth. An optimized quantum yield up to 70% was obtained for the CdSe/ZnS core-shell nanoparticles.