Ultrafast spectroscopy of CdS/CdSe quantum dots

Results from the nonresonance spectroscopy of CdS/CdSe quantum dots (composites of CdSe–CdS nanoparticles (core–shell)) are presented. The nonlinear optical properties of CdS/CdSe QDs in PMMA are studied with fs pulses at 1053 nm using the transient lens technique. QDs generate rapidly oscillating signals with amplitude rise times of around 200 fs and decay times of around 500 fs, while pure PMMA polymer only generates an oscillating signal whose envelope coincides with its autocorrelation function.     

CdSe/CdS/ZnS 量子点体系中的超快载流子动力学

利用飞秒泵浦探测技术对CdSe/CdS/ZnS量子点体系中的超快载流子动力学过程进行了研究. 通过选择不同波长的泵浦光分别激发样品壳层和核层,研究了载流子在壳层和核层中的超快动力学过程. 实验结果表明,载流子在CdS壳层导带中弛豫过程非常迅速(约130 fs),时间明显短于载流子在CdSe核层导带中的弛豫时间(约400 fs). 实验中也发现在CdS壳层和CdSe核层的分界面存在一定量的缺陷态.     

CdSe/CdS核壳量子点复合材料合成及其在白光发光二极管中的应用

采用有机化学合成法,利用正三辛基膦(TOP)辅助的快速注入生长方法,改进传统的制备工艺,实现了CdSe/CdS厚壳层核壳(8.6 ML)量子点复合材料的合成制备,并对所合成的核、核壳量子点及其复合材料的晶格结构、形貌特点与发光性质进行了XRD、TEM、SEM、UV-Vis、PL表征和红光补偿效果测试。测试结果表明,CdSe核具有立方纤锌矿晶格结构;CdSe/CdS量子点复合材料直径为45~75μm,呈菱形规则形貌,且颗粒分散性良好。采用该方法,可以提高量子产率,产率由4%(CdSe核)升至48%(CdSe/CdS核壳量子点);可以增强激子态发光能力,CdSe/CdS核壳量子点复合材料的荧光强度约为CdSe核的13倍。将该材料与YAG∶Ce~(3+)黄色荧光粉组合应用,获得了高光效(148.29 lm/W)、高显色指数(Ra为90.1,R9为97.0)的白光发光二级管,表明按照上述方法获得的CdSe/CdS核壳量子点复合材料在白光发光二极管中深红光波段具有较好的补偿效果。     

Optical properties of 3D photonic crystals filled with CdSe/CdS quantum dots

We study 3D globular photonic crystals based on synthetic opals filled with semiconductor core/shell quantum dots CdSe/CdS by measuring the photoluminescence spectra. The spectra were obtained using 369, 384, and 408 nm LED light excitation and involving a pulse YAG laser operating at 365 and 266 nm. The study shows that the photoluminescence spectra of opal filled with CdSe/CdS changes sufficiently in comparison with spectra taken for pure opal and a reference colloidal solution of CdSe/Cds quantum dots in toluene. Such opals may be used to fabricate a narrow-band light sources.     

Macroscale alignment of CdSe/CdS nanorods by porous anodic alumina templates

Centimeter‐scale assemblies of highly ordered CdSe/CdS core‐shell nanorods have been successfully fabricated by infiltration of the nanorods into the pores of a transparent porous anodic alumina membrane. The high degree of the nanorod ordering is proved by the demonstration of both highly polarized PL and absorption of the aligned nanorods. The measured PL linear polarization degree is 53%. We have found that both the elongated CdS shell and the nearly spherical CdSe core exhibit a strong dependence of absorption on polarization angle with respect to the nanorod axis. We conclude that both CdS shell and CdSe core absorb more efficiently light with polarization along the axis of the nanorod. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Shell-dependent hole transport in highly luminescent CdSe-core CdS/ZnCdS/ZnS multi-shell nanocrystals

The photoinduced hole transfer dynamics from CdSe quantum dots (QDs), shelled with ZnS or CdS/CdZnS/ZnS layers, to organic hole transporting materials (HTMs) is investigated by absorption, steady-state and time-resolved photoluminescence (PL) spectroscopy. The PL intensity and lifetime of the QDs are dramatically quenched when HTMs are added into the dilute QD solution. The quenching efficiency of the QDs significantly decreases with increasing the shell thickness and increases with decreasing the oxidation potential of the HTMs. These facts are correlated with the photoinduced hole transfer from the QDs to the HTMs. The above results are helpful in understanding the photoexcitation dynamics-related phenomena of organic molecule conjugated nano-object.     

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.     

Intermediate intensity levels during the emission intermittency of single CdSe/ZnS quantum dots

We report on an intermediate intensity level in the emission intermittency of single CdSe/ZnS core shell quantum dots, which has been overlooked in previous experiments most likely due to its low quantum efficiency. The intermediate intensity level is observed in CdSe/ZnS quantum dots of large diameter (about 5 nm diameter) and appears to be independent of the general dark state power law dynamics. The dim emission periods are found to be exponentially distributed and thus correspond to similar findings in CdSe/CdS quantum dots, where their existence has been interpreted in terms of the emission of a positively charged trion.     

Enhancement of photoluminescence of the CdSe/CdS quantum dots on quartz substrates in the presence of silver nanoparticles

Multilayer systems consisting of layers of hybrid quantum dots are fabricated. The quantum dots with the CdSe/CdS core/shell structure are chemically synthesized and deposited on the surface of quartz glass that contains ion-synthesized silver nanoparticles in the near-surface region. Silver nanoparticles exhibit optical absorption owing to the localized surface plasmon resonance. Variations in the photoluminescence intensity of the layer related to an increase in the distance from the quartz surface with metal nanoparticles are studied. An increase in the photoluminescence intensity is observed under excitation in the spectral region of the plasmon absorption of silver nanoparticles. An optimal distance between the layers is determined to maximize the enhancement of the photoluminescence of quantum dots in the presence of the near field of metal nanoparticles.     

A novel two-phase thermal approach for synthesizing CdSe/CdS core/shell nanostructure

CdSe/CdS core/shell nanocrystals have been synthesized through a low cost and simple two-phase thermal route. The optical spectroscopy and structural characterization evidenced the core/shell structure of the CdSe/CdS nanoparticles. The X-ray diffraction patterns of CdSe and CdSe/CdS nanoparticles exhibited peak positions corresponding to those of their bulk cubic crystal structures. The X-ray photoelectron spectroscopy data confirmed the elemental composition of the CdSe/CdS nanoparticles. The absorption spectra of core/shell nanoparticles showed red shift with respect to the core CdSe nanoparticles. The photoluminescence study indicates that the intensity of the emission maximum is considerably increased in the core/shell structure as compared with the parent material, and the capping of CdS nanoparticles with CdSe material exhibit a near band-edge emission, indicating a successful passivation by removing surface defects. The high-resolution transmission microscope images of the bare and core/shell nanoparticles ascertained the monodispersed and well-defined spherical particles. The average particle sizes for CdSe and CdSe/CdS nanoparticles are 2.5 and 5 nm, respectively, thus confirming, the larger diameter of CdSe/CdS core/shell nanostructure than the core CdSe nanoparticles.     

水溶胶CdSe/CdS核/壳结构纳米晶制备及光学性质的研究

以巯基乙酸为稳定剂在水溶液中合成了水溶胶CdSe/CdS核/壳结构的量子点,利用X射线粉末衍射(XRD)和X射线光电子能谱(XPS)对量子点结构进行了表征;并对化学组成和尺寸分布进行了研究。通过紫外-可见吸收光谱、激发光谱与发射光谱研究了它们的发光特性。     

Effect of the Semiconductor Quantum Dot Shell Structure on Fluorescence Quenching by Acridine Ligand

The main line of research in cancer treatment is the development of methods for early diagnosis and targeted drug delivery to cancer cells. Fluorescent semiconductor core/shell nanocrystals of quantum dots (e.g., CdSe/ZnS) conjugated with an anticancer drug, e.g., an acridine derivative, allow real-time tracking and control of the process of the drug delivery to tumors. However, linking of acridine derivatives to a quantum dot can be accompanied by quantum dot fluorescence quenching caused by electron transfer from the quantum dot to the organic molecule. In this work, it has been shown that the structure of the shell of the quantum dot plays the decisive role in the process of photoinduced charge transfer from the quantum dot to the acridine ligand, which is responsible for fluorescence quenching. It has been shown that multicomponent ZnS/CdS/ZnS shells of CdSe cores of quantum dots, which have a relatively small thickness, make it possible to significantly suppress a decrease in the quantum yield of fluorescence of quantum dots as compared to both the classical ZnS thin shell and superthick shells of the same composition. Thus, core/multicomponent shell CdSe/ZnS/CdS/ZnS quantum dots can be used as optimal fluorescent probes for the development of systems for diagnosis and treatment of cancer with the use of anticancer compounds based on acridine derivatives.     

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.     

Size-dependent electronic and optical properties of an exciton in CdSe/CdS/CdSe/CdS multilayer spherical quantum dot

The electronic and optical properties of a single exciton in a CdSe/CdS/CdSe/CdS quantum dot is studied by using effective mass approximation with parabolic confinement. The Coloumbic interaction between electron and hole is included by Hartree potential. A self-consistent technique is used to calculate the energy eigenvalue and wavefunction of exciton. Based on this approximation we investigate the effect of core size, shell thickness, well width on exciton binding energy, absorption spectra, and oscillator strength. The results provide the tuning possibility of electronic and optical properties of multilayer quantum dot with layer thickness.     

Wurtzite and zinc-blende CdSe based core/shell semiconductor nanocrystals: Structure, morphology and photoluminescence

We report comparative study of core/shell nanocrystals based on wurtzite and novel zinc-blende CdSe core. Both wurtzite and zinc-blende CdSe are coated with CdS shell or CdS/ZnS multishell under identical synthetic parameters. Crystal structure analysis finds that CdS shell is wurtzite on either wurtzite or zinc-blende CdSe cores. Morphology and photoluminescence studies exhibit that for zinc-blende CdSe based samples, the shell growth is in fine epitaxy and the obtained core/shell nanocrystals show high quantum yield both before and after surface modification process; while wurtzite CdSe based samples have irregular shape indicating inhomogeneous shell growth, and are with lower quantum yield. Furthermore, in the photoluminescence spectra exited with UV radiation, wurtzite CdSe based samples show side peaks of independently nucleated nanocrystals from the shell material; while samples with zinc-blende CdSe cores are potent in restricting these byproducts, which may attribute to the highly effective arrestment of precursor ions onto the zinc-blende CdSe surface. These features manifest that zinc-blende CdSe is more talented than conventional wurtzite CdSe in achieving core/shell nanocrystals with higher qualities.     

Shell thickness dependence of exciton trapping in colloidal core/shell nanorods

We quantitatively investigated, by time-resolved photoluminescence (PL) spectroscopy, the shell thickness dependence of exciton trapping and its effects on the PL quantum yield (QY) in colloidal CdSe/CdS/ZnS core/shell quantum rods. The defects passivation, due to a thin shell (0.6 monolayer), leads to a 2 times reduction of the trapping from both emitting and high-energy excited states, thus explaining the observed 4.3 times increase of the PL QY. Moreover, the QY decrease in the thick shell (1.3 monolayers) sample is fully explained in terms of increased trapping from the emitting states, which is ascribed to new defects caused by the strain relaxation at the core-shell interface.     

CdSe/CdS核/壳型纳米晶的光谱特性

以巯基乙酸为稳定剂制备了CdSe/CdS核／壳型纳米晶。用光吸收谱（Abs)、光致发光谱（PL）及光致发光激发谱（PLE）研究了CdS壳层对CdSe纳米晶电子结构，从而对其吸收和发光性能的影响。根据PL和PLE的结果以及带边激子精细结构的计算结果，我们用尺寸很小的纳米晶中所形成的基激缔合物解释了PL光谱与吸收边之间较大的Stokes位移。     

Electroluminescence of CdSe/CdS quantum dots and the transfer of the exciton excitation energy in an organic light-emitting diode

A light emitting diode has been developed on the basis of multilayer nanostructures in which CdSe/CdS semiconductor colloidal quantum dots serve as emitters. Their absorption, photo-, and electroluminescence spectra have been obtained. The strong influence of the size effect and the density of particles in the layer on the spectral and electrophysical characteristics of the diode has been demonstrated. It has been shown that the rates of the transfer of the exciton excitation energy from organic molecules to quantum dots increase strongly even at a small increase in the radius of the core (CdSe) of a particle and depend strongly on the thickness of the shell (CdS) of the particle. The optimal arrangement of the layer of quantum dots with respect to the p-n junction has been estimated from the experimental data. The results demonstrate that the spectral characteristics and rates of the electron processes in light-emitting devices based on quantum dots incorporated into an organic matrix can be efficiently controlled.     

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.     

Near-unity quantum yields of biexciton emission from CdSe/CdS nanocrystals measured using single-particle spectroscopy

Biexciton photoluminescence (PL) quantum yields (Q(2X)) of individual CdSe/CdS core-shell nanocrystal quantum dots with various shell thicknesses are derived from independent PL saturation and two-photon correlation measurements. We observe a near-unity Q(2X) for some nanocrystals with an ultrathick 19-monolayer shell. High Q(2X)'s are, however, not universal and vary widely among nominally identical nanocrystals indicating a significant dependence of Q(2X) upon subtle structural differences. Interestingly, our measurements indicate that high Q(2X)'s are not required to achieve complete suppression of PL intensity fluctuations in individual nanocrystals.