Type-II quantum dots: CdTe/CdSe(core/shell) and CdSe/ZnTe(core/shell) heterostructures

Type-II band engineered quantum dots (CdTe/CdSe(core/shell) and CdSe/ZnTe(core/shell) heterostructures) are described. The optical properties of these type-II quantum dots are studied in parallel with their type-I counterparts. We demonstrate that the spatial distribution of carriers can be controlled within the type-II quantum dots, which makes their properties strongly governed by the band offset of the comprising materials. This allows access to optical transition energies that are not restricted to band gap energies. The type-II quantum dots reported here can emit at lower energies than the band gaps of comprising materials. The type-II emission can be tailored by the shell thickness as well as the core size. The enhanced control over carrier distribution afforded by these type-II materials may prove useful for many applications, such as photovoltaics and photoconduction devices.     

Aqueous synthesis of glutathione-capped CdTe/CdS/ZnS and CdTe/CdSe/ZnS core/shell/shell nanocrystal heterostructures

Here we demonstrate the aqueous synthesis of colloidal nanocrystal heterostructures consisting of the CdTe core encapsulated by CdS/ZnS or CdSe/ZnS shells using glutathione (GSH), a tripeptide, as the capping ligand. The inner CdTe/CdS and CdTe/CdSe heterostructures have type-I, quasi-type-II, or type-II band offsets depending on the core size and shell thickness, and the outer CdS/ZnS and CdSe/ZnS structures have type-I band offsets. The emission maxima of the assembled heterostructures were found to be dependent on the CdTe core size, with a wider range of spectral tunability observed for the smaller cores. Because of encapsulation effects, the formation of successive shells resulted in a considerable increase in the photoluminescence quantum yield; however, identifying optimal shell thicknesses was required to achieve the maximum quantum yield. Photoluminescence lifetime measurements revealed that the decrease in the quantum yield of thick-shell nanocrystals was caused by a substantial decrease in the radiative rate constant. By tuning the diameter of the core and the thickness of each shell, a broad range of high quantum yield (up to 45%) nanocrystal heterostructures with emission ranging from visible to NIR wavelengths (500-730 nm) were obtained. This versatile route to engineering the optical properties of nanocrystal heterostructures will provide new opportunities for applications in bioimaging and biolabeling.     

Spectroscopy and femtosecond dynamics of type-II CdTe/CdSe core-shell quantum dots.

Syntheses of CdTe/CdSe type-II quantum dots (QDs) using CdO and CdCl2 as precursors for core and shell, respectively, are reported. Characterization was made via near-IR interband emission, transmission electron microscopy (TEM), energy dispersive spectroscopy (EDX), and X-ray diffraction (XRD). Femtosecond fluorescence upconversion measurements on the relaxation dynamics of the CdTe core (in CdTe/CdSe) emission and CdTe/CdSe interband emission reveal that as the size of the core increases from 5.3, 6.1 to 6.9 nm, the rate of photoinduced electron separation decreases from 1.96, 1.44 to 1.07 x10(12) s(-1). The finite rates of the initial charge separation are tentatively rationalized by the small electron-phonon coupling, causing weak coupling between the initial and charge-separated states.     

Use of surface-modified CdTe quantum dots as fluorescent probes in sensing mercury (II)

Thioglycolic acid (TGA)-capped CdTe quantum dots (QDs) were synthesized in aqueous medium, and their interaction with metal cations was studied with UV-vis absorption, steady-state and time-resolved fluorescence spectra. The results demonstrated that Hg(II), Cu(II) and Ag(I) could effectively quench the QD emission based on different action mechanisms: Cu(II) and Ag(I) quenched CdTe QDs because they bound onto particle surface and facilitated non-radiative electron/hole recombination annihilation of QDs; electron transfer process between the capping ligands and Hg(II) was mainly responsible for the remarkable quenching effect of Hg(II). To prevent the approach of metal cations to QD core, the original TGA-capped CdTe QDs were further coated by denatured bovine serum albumin (dBSA). It was found that the dBSA-coated CdTe QDs could be quenched effectively by Hg(II), but Cu(II) and Ag(I) could hardly quench the QDs even at fairly higher concentration levels because the dBSA shell layer effectively prevented the binding of metal cations onto the QD core. On the basis of this fact, a simple, rapid and specific method for Hg(II) determination was proposed. Under optimal conditions, the quenched fluorescence intensity increased linearly with the concentration of Hg(II) ranging from 0.012 x 10(-6) to 1.5 x 10(-6) mol L(-1). The limit of detection for Hg(II) was 4.0 x 10(-9) mol L(-1). The developed method was successfully applied to the detection of trace Hg(II) in real samples.     

Solar cells sensitized with type-II ZnSe-CdS core/shell colloidal quantum dots

Type-II quantum dots (QDs) were applied for QDs-sensitized solar cells for the first time and showed prominent absorbed photon to current conversion efficiency.     

L-Cysteine-coated CdSe/CdS core-shell quantum dots as selective fluorescence probe for copper(II) determination

Quantum dots (QDs) or semiconductor nanocrystals have been receiving great interest in the last few years. In this paper, L-cysteine-coated CdSe/CdS core-shell QDs (λ_em = 585 nm) have been prepared, which have excellent water-solubility. The full width at half maximum (FWHM) of the photoluminescence of these nanocrystals is very narrow (about 30 nm), and the quantum yield (QY) is 15% relative to Rhodamine 6G in ethanol (QY = 95%). With excess free L-cysteine in the solution, the fluorescence intensity of L-cysteine-coated CdSe/CdS QDs showed improved stability. It was found that the fluorescence of L-cysteine-capped CdSe/CdS QDs could be quenched only by copper (II) ions and was insensitive to other physiologically important cations, such as Ca²⁺, Mg²⁺, Zn²⁺, Al³⁺, Fe³⁺, Mn²⁺ and Ni²⁺ etc. Based on this finding, the quantitative analysis of Cu²⁺ with L-cysteine-capped CdSe/CdS QDs has been established. The linear range was from 1.0 × 10^− 8 to 2.0 × 10^− 7 mol L^− 1 and the limit of detection (LOD) was 3.0 × 10^− 9 mol L^− 1 (S/N = 3). The proposed method has first been applied to the determination of Cu²⁺ in vegetable samples with recoveries of 99.6–105.8%.     

Synthesis CdSe(x)S(1-x) core/shell type quantum dots via one injection method

The photoluminescence quantum yield (PL-QY) of ternary colloidal CdSe(x)S(1-x) quantum dots (QDs), which were prepared by a one-injection method, enhances with increasing S content. The possible enhancement mechanism was explored by structural analysis via X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). Both found that the enhancement of PL-QY of ternary CdSe(x)S(1-x) QDs strongly correlated with self-formed core/shell conformation in the non-coordination solution.     

Electrochemical properties of CdSe and CdTe quantum dots

Semiconductor nanocrystal quantum dots (QDs), owing to their unique opto-electronic properties determined by quantum confinement effects, have been the subject of extensive investigations in different areas of science and technology in the past two decades. The electrochemical behaviour of QDs, particularly for CdSe and CdTe nanocrystals, has also been explored, although to a lesser extent compared to the optical properties. Voltammetric measurements can be used to probe the redox levels available for the nanocrystals, which is an invaluable piece of information if these systems are involved in electron transfer processes. Electrochemical data can also foster the interpretation of the spectroscopic properties of QDs, and give insightful information on their chemical composition, dimension, and surface properties. Hence, electrochemical methods constitute in principle an effective tool to probe the quality of QD samples in terms of purity, size dispersion, and surface defects. The scope of this critical review is to discuss the results of electrochemical studies carried out on CdSe and CdTe core and core-shell semiconductor nanocrystals of spherical shape. Examples of emerging or potential applications that exploit electroactive quantum dot-based systems will also be illustrated.     

Oscillating fluorescence in an unstable colloidal dispersion of CdSe/ZnS core/shell quantum dots

Fluorescence oscillation is observed in an ensemble of colloidal CdSe/ZnS core/shell quantum dots (QDs) dispersed in nonpolar solvent under continuous irradiation. The QDs dispersed in toluene gradually aggregate and change their fluorescence intensity, even in the dark. During the aggregation, the QD/toluene suspension is unstable, that is, overdispersed. The fluorescence oscillation is found only in this unstable state before the system reaches steady state. In addition, the aggregation rate is promoted by irradiation and strongly correlates with the oscillation amplitude. Our experimental results indicate that the dispersion instability plays an important role in both linear and nonlinear dynamics of the fluorescence. It is inferred from the experimental results and previous studies that the complex time evolution of fluorescence in the QD/toluene dispersion is possibly due to adsorption and desorption of surface ligand molecules over the course of QD aggregation.     

Engineering InAs(x)P(1-x)/InP/ZnSe III-V alloyed core/shell quantum dots for the near-infrared

Quantum dots with a core/shell/shell structure consisting of an alloyed core of InAs(x)P(1-x), an intermediate shell of InP, and an outer shell of ZnSe were developed. The InAs(x)P(1-x) alloyed core has a graded internal composition with increasing arsenic content from the center to the edge of the dots. This compositional gradient results from two apparent effects: (1) the faster reaction kinetics of the phosphorus precursor compared to the arsenic precursor, and (2) a post-growth arsenic-phosphorus exchange reaction that increases the arsenic content. The cores have a zinc blend structure for all compositions and show tunable emission in the near-infrared (NIR) region. A first shell of InP leads to a red-shift and an increase in quantum yield. The final shell of ZnSe serves to stabilize the dots for applications in aqueous environments, including NIR biomedical fluorescence imaging. These NIR-emitting core/shell/shell InAs(x)P(1-x)/InP/ZnSe were successfully used in a sentinel lymph node mapping experiment.     

Characterization of CdTe/CdSe quantum dots-transferrin fluorescent probes for cellular labeling

In this paper, we prepared three types of transferrin-quantum dots conjugates (QDs-Tf) using three different methods (electrostatic interaction, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) coupling, denatured transferrin (dTf) coating). Fluorescence emission spectra, surface characteristics, zeta potentials of quantum dots (QDs) and QDs-Tf fluorescent probes were characterized by spectrophotometer, capillary electrophoresis, and dynamic light scattering. Fluorescent imaging of HeLa cells was also performed by QDs and QDs-Tf fluorescent probes. It was found that the fluorescence imaging performances of QDs-Tf probes prepared by electrostatic interaction and EDC coupling were better compared with the one prepared by dTf coating. Then a real-time single cell detection system was established to quantitatively evaluate cell labeling effects of QDs-Tf fluorescent probes. It was found that for cell labeling efficiency, the proportion of cells labeled by quantum dot probes to a group of cells, QDs-Tf probe prepared by EDC coupling showed the highest labeling efficiency (85.55 ± 3.88%), followed by electrostatic interaction (78.86 ± 9.57%), and dTf coating showed the lowest (40.09 ± 10.2%). This efficiency order was confirmed by flow cytometry results. This study demonstrated the relationship between conjugation methods and the resultant QDs-Tf probes and provided a foundation for choosing appropriate QDs-Tf probes in cell labeling.     

Photoassisted synthesis of CdSe and core-shell CdSe/CdS quantum dots

This paper describes the synthesis of core-shell CdSe/CdS quantum dots (QDs) in aqueous solution by a simple photoassisted method. CdSe was prepared from cadmium nitrate and 1,1-dimethylselenourea precursors under illumination for up to 3 h using a pulsed Nd:YAG laser at 532 nm. The effects that the temperature and the laser irradiation process have on the synthesis of CdSe were monitored by a series of experiments using the precursors at a Cd:Se concentration ratio of 4. Upon increasing the temperature (80-140 degrees C), the size of the CdSe QDs increases and the time required for reaching a maximum photoluminescence (PL) is shortened. Although the as-prepared CdSe QDs possess greater quantum yields (up to 0.072%) compared to those obtained by microwave heating (0.016%), they still fluoresce only weakly. After passivation of CdSe (prepared at 80 degrees C) by CdS using thioacetamide as the S source (Se:S concentration ratio of 1) at 80 degrees C for 24 h, the quantum yield of the core-shell CdSe/CdS QDs at 603 nm is 2.4%. Under UV irradiation of CdSe/CdS for 24 h using a 100-W Hg-Xe lamp, the maximum quantum yield of the stable QDs is 60% at 589 nm. A small bandwidth (W1/2 < 35 nm) indicates the narrow size distribution of the as-prepared core-shell CdSe/CdS QDs. This simple photoassisted method also allows the preparation of differently sized (3.7-6.3-nm diameters) core-shell CdSe/CdS QDs that emit in a wide range (from green to red) when excited at 480 nm.     

核-壳结构CdSe/ZnS量子点的制备、硫醇修饰及其光学性能

采用高温有机相包覆技术制备了CdSe/ZnS核壳结构量子点材料,考察了包覆量对量子点材料的光学性能的影响,研究了含脂肪链和芳香基的双硫醇分子1,4-苯二甲硫醇和1,8-辛二硫醇对于具有核-壳结构的CdSe/ZnS量子点材料的修饰作用,考察了修饰作用对于量子点的量子效率和荧光强度等光学性能的影响.实验结果表明:随着硫化锌包覆量的增加,量子点的量子效率及其荧光发射强度明显提高;硫醇的修饰能显著增强量子点的发光强度,随着硫醇浓度的增加,其发光性能增强,但是达到一定程度后,光学性能基本不随硫醇浓度的变化而变化.根据固体核磁共振等实验结果推测:硫醇分子可能部分替代了量子点体系中的正三辛基氧膦配体,稳定了量子点体系,对量子点起修饰保护作用,从而提高了量子点的光学性能.     

Aqueous synthesis of CdSe and CdSe/CdS quantum dots with controllable introduction of Se and S sources

A new and convenient route is developed to synthesize CdSe and core-shell CdSe/CdS quantum dots(QDs) in aqueous solution.The gaseous precursors,H2Se and H2S,generated on-line by reducing SeO 3 2à with NaBH 4 and the reaction between Na 2 S and diluted H2SO 4,are used to form high-quality CdSe and CdSe/CdS QDs,respectively.The synthesized water-soluble CdSe and CdSe/CdS QDs possess high quantum yield(3% and 20%) and narrow full-width-at-half-maximum(43 nm and 38 nm).The synthesis process is easily reproducible with simple apparatus and low-toxic chemicals,and can be readily extended to the large-scale aqueous synthesis of QDs.     

Aqueous synthesis and characterization of TGA-capped CdSe quantum dots at freezing temperature

CdSe quantum dots (QDs) have traditionally been synthesized in organic phase and then transferred to aqueous solution by functionalizing their surface with silica, polymers, short-chain thiol ligands, or phospholipid micelles. However, a drastic increase in the hydrodynamic size and biotoxicity of QDs may hinder their biomedical applications. In this paper, the TGA-capped CdSe QDs are directly synthesized in aqueous phase at freezing temperature, and they prove to possess high QY (up to 14%).     

Functionalized manganese-doped zinc sulfide core/shell quantum dots as selective fluorescent chemodosimeters for silver ion

Zinc sulfide quantum dots doped with Mn(II) ions and coated with a shell of zinc sulfide were prepared, and their surface was modified with iminodiacetic acid to form a QDs-conjugate (QDs-IDA). Such modification effectively improves the water-solubility and luminescence quantum yield of the quantum dots. The optical properties and structural features were characterized by photometry, ¹H NMR and fluorescence spectroscopy. The results displayed that QDs-IDA selectively respond to Ag (I) ion in phosphate buffer solution (pH 7.3) in quenching the fluorescence of QDs-IDA. A good linear relationship exists in the concentration range from 5.0?×?10^?7 mol·L^?1 to 4.5?×?10^?6 mol·L^?1 and the detection limit is 2.6?×?10^?7 mol·L^?1. The sensing mechanism was assumed to result from complex formation between the iminodiacetic acid of QDs-IDA and silver (I) ion which promoted photo-induced electron transfer.     

Determination of vanadium(V) with CdTe quantum dots as fluorescent probes

CdTe quantum dots (QDs) were modified with thioglycolic acid (TGA) and synthesized in aqueous medium. The optimum fluorescence intensity was found to be at pH 6.24 with a CdTe QDs concentration of 4.96 × 10⁻⁷ mol L⁻¹. The quenched fluorescence intensity of CdTe QDs is linearly proportional to V(V) concentration from 10 to 200 ng mL⁻¹ with correlation coefficient R = 0.9985. The limit of detection for V(V) was 2.07 ng mL⁻¹. The proposed method was successfully applied to the analysis of trace amounts of V(V) in water samples with recovery of 96.5–101.8%, and the results were in good agreement with those of electrothermal atomic absorption spectrometry.     

Low power operated highly luminescent ferroelectric liquid crystal doped with CdSe/ZnSe core/shell quantum dots

We report the enhancement in the molecular ordering of ferroelectric liquid crystal (FLC) doped with CdSe/ZnSe graded core/shell (CZ) quantum dots (QDs) by using optical methods. Significant decrease in operating voltage and enhancement in optical brightness are assigned to the large primary order parameter (θ) and hence anchoring of FLC molecules by CZ QDs. The enhancement in photoluminescence is conjectured to be due to an increase in molecular alignment yielding higher absorption which is confirmed by excitation spectra. These observations would definitely offer a promising tool to get superior core/shell QD incorporated FLC-based display devices.