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.     

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.     

巯基丙酸分子对CdSe核壳量子点和 ZnO纳米粒子薄膜之间电荷转移的影响

通过稳态光谱和时间分辨荧光光谱研究了巯基丙酸(MPA)分子对由量子点到ZnO纳米粒子薄膜的电荷转移过程的影响。研究发现,相对于CdSe纳米粒子薄膜样品,没有MPA分子参与作用的CdSe/ZnO薄膜样品和有MPA分子连接的CdSe/MPA/ZnO薄膜样品中都存在从CdSe量子点到ZnO纳米粒子薄膜的有效电荷分离过程,但是相对于CdSe/ZnO样品, CdSe/MPA/ZnO样品中电荷转移速率明显变小。这表明MPA分子本身它并不能促进CdSe到ZnO电荷分离过程,因此可以认为用金属氧化物薄膜直接吸附量子点吸收材料,将能获得高功率转换效率的量子点敏化太阳能电池。     

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.     

Co-sensitized quantum dot solar cell based on ZnO nanowire

An efficient photoelectrode is fabricated by sequentially assembled CdS and CdSe quantum dots (QDs) onto a ZnO-nanowire film. As revealed by UV-vis absorption spectrum and scanning electron microscopy (SEM), CdS and CdSe QDs can be effectively adsorbed on ZnO-nanowire array. Electrochemical impedance spectroscopy (EIS) measured demonstrates that the electron lifetime for ZnO/CdS/CdSe (13.8 ms) is calculated longer than that of ZnO/CdS device (6.2 ms), which indicates that interface charge recombination rate is reduced by sensitizing CdSe QDs. With broader light absorption range and longer electron lifetime, a power conversion efficiency of 1.42% is achieved for ZnO based CdS/CdSe co-sensitized solar cell under the illumination of one Sun (AM 1.5G, 100 mW cm⁻²).     

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。     

Two-step annealed CdS/CdSe co-sensitizers for quantum dot-sensitized solar cells

CdS/CdSe co-sensitizers on TiO₂ films were annealed using a two-step procedure; high temperature (300 °C) annealing of TiO₂/CdS quantum dots (QDs), followed by low temperature (150 °C) annealing after the deposition of CdSe QDs on the TiO₂/CdS. For comparison, two types of films were prepared; CdS/CdSe-assembled TiO₂ films conventionally annealed at a single temperature (150 or 300 °C) and non-annealed films. The 300 °C-annealed TiO₂/CdS/CdSe showed severe coalescence of CdSe QDs, leading to the blocked pores and hindered ion transport. The QD-sensitized solar cell (QD-SSC) with the 150 °C-annealed TiO₂/CdS/CdSe exhibited better overall energy conversion efficiency than that with the non-annealed TiO₂/CdS/CdSe because the CdSe QDs annealed at a suitable temperature (150 °C) provided better light absorption over long wavelengths without the hindered ion transport. The QD-SSC using the two-step annealed TiO₂/CdS/CdSe increased the cell efficiency further, compared to the QD-SSC with the 150 °C-annealed TiO₂/CdS/CdSe. This is because the 300 °C-annealed, highly crystalline CdS in the two-step annealed TiO₂/CdS/CdSe improved electron transport through CdS, leading to a significantly hindered recombination rate.     

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.     

Magneto-bound polaron in CdSe spherical quantum dots: strong coupling approach

The effect of a magnetic field on the ground-state energy of a donor impurity confined in a polar CdSe spherical quantum dot embedded in a nonpolar matrix is studied theoretically. The interaction between the all charge carriers (electron and ion) and the confined longitudinal optical phonons (LO-phonons) is taken into account by considering the strong coupling method (Landau–Pekar approach). A variational calculation is performed in the framework of the effective mass approximation using a trial wave function deduced from the second-order perturbation and assuming that the quantum dot has a finite depth potential.     

Electronic properties of A<Subscript>2</Subscript>B<Subscript>6</Subscript> quantum dots incorporated into Langmuir–Blodgett films

An experimental and theoretical study is performed for features of the electronic spectrum of CdSe/CdS/ZnS quantum dots incorporated into Langmuir–Blodgett films. Analysis of the investigated samples assesses the state of the first three levels of the electron spectrum for a quantum object. Good qualitative and quantitative agreement is achieved between the experimental results and theoretical estimates. It is shown that the mechanism of the observed field emission current through a quantum dot is described satisfactorily by the Morgulis–Stratton theory under the considered experimental conditions.     

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.     

Dots in rods as polarized single photon sources

We report the evidence of a polarized single photon flux from a colloidal nanoparticle. We analyze, by time and polarization resolved spectroscopy measurements, the polarization behavior of a single CdSe/CdS core/shell dot in rod, achieving a polarization ratio at room temperature of ∼75% and a lifetime of the excited state of ∼11 ns.     

Effect of a buffer layer between the shell and ligand on the optical properties of an exciton and biexciton in type-II quantum dot nanocrystals

In this study, we have investigated the effect of the buffer layers on the electronic and optical properties of an exciton (X) and a biexciton (XX) in a type-II CdTe/CdSe quantum dot nanocrystal. In an experimental study, it has been reported that when a CdTe/CdSe quantum dot nanocrystal is coated by a ZnTe material as a buffer layer, the photoluminescence quantum yield is growing from 4 to 20%. We have confirmed theoretically this improvement and extended the calculations to an XX structure. In the calculations, two different semiconductor materials, CdS and ZnTe, have been considered for the buffer layer. We have theoretically shown that the buffer layer causes an increase in the radiative oscillator strength of both X and XX. When the ZnTe is used as the buffer layer, the oscillator strength becomes stronger when compared to CdSe buffer material because of higher conduction band offset between CdSe and ZnTe.     

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.     

Purcell effect in triangular plasmonic nanopatch antennas with three-layer colloidal quantum dots

A model describing a plasmonic nanopatch antenna based on triangular silver nanoprisms and multilayer cadmium chalcogenide quantum dots is introduced. Electromagnetic-field distributions in nanopatch antennas with different orientations of the quantum-dot dipoles are calculated for the first time with the finite element method for numerical electrodynamics simulations. The energy flux through the surface of an emitting quantum dot is calculated for the configurations with the dot in free space, on an aluminum substrate, and in a nanopatch antenna. It is shown that the radiative part of the Purcell factor is as large as 1.7 × 10₂ The calculated photoluminescence lifetimes of a CdSe/CdS/ZnS colloidal quantum dot in a nanopatch antenna based on a silver nanoprism agree well with the experimental results.     

CdSe quantum dot formation induced by amorphous Se

The mechanism allowing the transition from a two-dimensional strained layer of CdSe on ZnSe to self-assembled islands induced by the use of amorphous selenium is still not fully understood. For a better understanding, atomic force microscopy and transmission electron microscopy studies were performed on CdSe films with a thickness close to that for quantum dot formation. Below this thickness, the sample surface results in undulations along the [1 1 0] crystal direction, while few quantum dots are situated in the wave valleys. Plan view transmission electron microscopy studies reveal a strong anisotropy of the islands and show that the Se desorption conditions are crucial.     

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。     

Accurate analysis of electron transfer from quantum dots to metal oxides in quantum dot sensitized solar cells

Electron transfer rate from quantum dot (QD) to metal oxide (MO) in quantum dot sensitized solar cells (QDSSCs) has an important role in the efficiency. In this work, we analyse the electron transfer rate from CdSe, CdS and CdTe QDs to TiO₂, ZnO and SnO₂ MOs by extending the related equations with considering various effects, based on the Marcus theory. In this regard, the effects of QD diameter, QD–MO spacing, the crystalline defects, temperature, and the reorganizational energy, on the electron transfer rate are investigated. The results show that, the maximum electron transfer rate is achieved for CdTe QD with the mentioned three MOs. Moreover, in order to direct the designer to reach the appropriate QDs–MOs combinations for obtaining the maximum electron transfer rate, the average electron transfer rate for various combinations is calculated. For the verification of simulation method, a part of work has been compared with the previous experimental and theoretical results, which indicates the correctness of our simulation algorithm.     

Stark shift and dissociation process of an ionized donor bound exciton in spherical quantum dots

The effect of an electric field on the ground state energy of an exciton bound to an ionized donor (D⁺, X) was studied in CdSe spherical quantum dots where quantum confinement is described by an infinitly deep potential. Calculations have been performed in the framework of the effective mass approximation using a variational method by choosing an appropriate sixty-terms wave function taking into account different interparticles correlations and symetry distorsion induced by the electric field. It appears that the Stark shift is significant even for low fields and depends strongly of spherical dot sizes. The competition between the confinement effect and the Stark effect is discussed as function of the spherical dot size and the applied electric field strength. The (D⁺, X) Stark shift is estimated and its behavior is discussed as a function of the dot radius and electric field strength. The electron and hole average distances have also been calculated and the role of the ionized donor in the excitonic dissociation is established.     

In situ growth of CdSe/CdS quantum dots inside and outside of MWCNTs

The CdSe/CdS quantum dots were grown in situ inside and outside of the multiwalled carbon nanotubes in an innocuous solvent and at a lower temperature. The CdSe/CdS-CNTs nanoheterostructures were characterized by TEM, HRTEM, EDS, XPS and PL. The CdSe/CdS nanocrystals with diameters about 5 nm exhibit an improved PL emission.