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.     

The Influence of Surface Trapping and Dark States on the Fluorescence Emission Efficiency and Lifetime of CdSe and CdSe/ZnS Quantum Dots

To investigate the influence of surface trapping and dark states on CdSe and CdSe/ZnS quantum dots (QDs), we studied the absorption, fluorescence intensity and lifetime by using one-and two-photon excitation, respectively. Experimental results show that both one- and two-photon fluorescence emission efficiencies of the QDs enhance greatly and the lifetime increase after capping CdSe with ZnS due to the effective surface passivation. The lifetime of one-photon fluorescence of CdSe and CdSe/ZnS QDs increase with increasing emission wavelength in a supralinear way, which is attributed to the energy transfer of dark excitons. On the contrary, the lifetime of two-photon fluorescence of bare and core-shell QDs decrease with increasing emission wavelength, and this indicates that the surface trapping is the dominant decay mechanism in this case.     

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.     

Interactions between CdSe/CdS quantum dots and DNA through spectroscopic and electrochemical methods

The interaction of CdSe/CdS quantum dots (QDs) with Herring sperm-DNA (hs-DNA) has been studied by UV-vis spectroscopy and electrochemical method. Cu(phen)₂^2+/1+ (phen = 1, 10-phenanthroline) was used as an indicator for electroactive dsDNA or ssDNA. The apparent association constant has been deduced (4.94 × 10³ M⁻¹ and 2.39 × 10² M⁻¹) from the absorption spectral changes of the dsDNA-QDs and ssDNA-QDs. The results of dissociation method suggest that Cu(phen)₂^2+/1+ is more easily dissociated from dsDNA or ssDNA modified gold electrode (dsDNA/Au or dsDNA/Au) in presence of QDs. The dissociation rate constant (k) of Cu(phen)₂^2+/1+ on dsDNA/Au is 4.48 times higher than that in absence of QDs, while k is 2.34 times higher than that in absence of QDs on ssDNA/Au in Tris buffer with low ionic strength (pH 7.0, 0.5 mM NaCl). The results illuminate that hs-DNA has high affinity for QDs due to electrostatic force, hydrogen bonds, and van der Waals interactions, and the binding force of QDs with dsDNA is stronger than ssDNA.     

Stable biexcitonic lasing of CuCl quantum dots under two-photon resonant excitation

We have observed ultraviolet lasing of CuCl quantum dots embedded in a NaCl single crystalline matrix. Stable ultraviolet lasing of biexciton (two e–h pairs) luminescence has been achieved below 70 K under the two-photon direct excitation of biexcitons of CuCl quantum dots. Laser action occurs with parallely cleaved surfaces of the NaCl crystalline matrix acting as an optical cavity, which shows a very high efficiency of lasing.     

Two-photon absorption from single InGaN/GaN quantum dots

We present a study of the time-integrated and time-resolved photoluminescence properties of single-InGaN/GaN quantum dots (QDs) using two-photon spectroscopy. Two samples containing QDs produced by different growth techniques are examined. We find that two-photon excitation results in the suppression of the emission from the underlying quantum well to which the QDs are coupled and yet relatively strong QD emission is observed. This effect is explained in terms of the enhancement of two-photon absorption in QDs due to the full confinement of carriers. Furthermore, evidence of the presence of excited states is revealed from the two-photon photoluminescence excitation spectra presented in the study.     

Experimental investigation of energy transfer between CdSe/ZnS quantum dots and different-sized gold nanoparticles

Hybrid nanostructures of quantum dots(QDs) and metallic nanostructure are attractive for future use in a variety of optoelectronic devices. For photodetection applications, it is important that the photoluminescence (PL) of QDs is quenched by the metallic nanostructures. Here, the quenching efficiency of CdSe/ZnS core-shell quantum dots (QDs) with different sized gold nanoparticles (NPs) films through energy transfer is investigated by measuring the PL intensity of the hybrid nanostructures. In our research, the gold NPs films are formed by the post-annealing of the deposited Au films on the quartz substrate. We find that the energy transfer from the QDs to the Au NPs strongly depends on the sizes of the Au NPs. For CdSe/ZnS QDs direct contact with the Au NPs films, the largest energy transfer efficiency are detected when the resonance absorption peak of the Au NPs is nearest to the emission peak of the CdSe/ZnS QDs. However, when there is a PMMA spacer between the QDs layer and the Au NPs films, firstly, we find that the energy transfer efficiency is weakened, and the largest energy transfer efficiency is obtained when the resonant absorption peak of the Au NPs is farthest to the emission peak wavelength of CdSe/ZnS QDs. These results will be useful for the potential design of the high efficiency QDs optoelectronic devices.     

Pressure-dependent photoluminescence of CdSe/ZnS quantum dots: Critical point of different pressure regimes

High pressure condition can alter and control the electronic structure of semiconductor quantum dots, and therefore provides novel insight for designing optoelectronic devices. Here we report the pressure-dependent photoluminescence (PL) of CdSe/ZnS core/shell quantum dots (QD) in different pressure regimes. The center of the PL spectrum has blue-shift when hydrostatic pressure increases, due to the increasing bulk modulus. However, the shifting rate becomes lower in the higher pressure regime, i.e. above the critical pressure point, mainly due to the interaction between QDs. Accordingly, the lifetimes of PL drop in the low pressure regime, due to the increased pressure-induced trapping states, then increase above the critical pressure point, indicating the interaction between dots likewise. The observed critical pressures for both cases are consistent with each other, and strongly depend on the QD concentration, which forcefully support the aforementioned interaction model.     

Large two-photon absorbance of chitosan–ZnS quantum dots nanocomposite film

ZnS semiconductor nanoparticles with average size of 3.4 nm were prepared in situ in chitosan film. TEM, UV–vis spectra and PL spectra show the ZnS nanoparticles in chitosan template were monodispersed and well passivated. The two-photon absorption coefficient (β) of the chitosan–ZnS quantum dots (QDs) nanocomposite film was obtained to be 2.29×10² cm/Gw from a standard Z-scan setup with femtosecond laser pusles at 790 nm wavelength. Results show the novel biomacromolecule/QDs nanocomposite film has large third-order optical nonlinear absorption, the mechanism responsible for which was discussed.     

Two-photon excitation of confined biexcitons in CuCl quantum dots

We have studied direct creation processes of confined biexcitons in CuCl quantum dots by polarization-dependent resonant two-photon excitation spectroscopy. The two-photon absorption band for the lowest state of the biexciton (total angular momentum J=0) which appears on the lower energy side of confined exciton band was identified from the analysis of the polarization dependence of the photoluminescence excitation spectrum of the biexciton. Furthermore, the two-photon excitation process for the excited state of the biexciton (J=2) was also found with polarization dependence different from the J=0 biexciton state.     

A new strategy to assemble CdSe/ZnS quantum dots with multi-walled carbon nanotubes for potential application in imaging and photosensitization

With objective to enhance luminescence intensities of carbon nanotubes (CNTs), we hereby report the attachment of CdSe/ZnS quantum dots (QDs) on to the surface of shortened Multi Walled Carbon Nanotubes (sMWCNTs). The resultant QDs-sMWCNTs nanohybrid complex have been characterized by Fourier transform infrared (FT-IR) spectroscopy, optical microscopy (OM), ultraviolet (UV) light, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX) diffraction spectroscopy and thermogravimetric analysis (TGA). Based on IR peaks characteristics of organic functional groups, optical brightness of sMWCNTs under polarized and UV light, the roughness of the sMWCNTs surface as observed in SEM images and black spots observed on the surface of sMWCNTs in TEM images, it is reasonable to conclude that CdSe/ZnS quantum dots (QDs) were attached on to the surface of sMWCNTs. Additionally, signals of Zn, S, Cd and Se along with carbon on the surface of sMWCNTs in EDX data and onset of thermal degradation of QDs-sMWCNTs nanohybrid complex at much lower temperature than that of sMWCNTs under TGA analysis further confirms the formation of QDs-sMWCNTs nanohybrid complex.     

Size-dependent optical properties and carriers dynamics in CdSe/ZnS quantum dots

Size-dependence of optical properties and energy relaxation in CdSe/ZnS quantum dots （QDs） were investigated by two-colour femtosecond （fs） pump-probe （400/800 nm） and picosecond time-resolved photoluminescence （ps TRPL） experiments. Pump-probe measurement results show that there are two components for the excited carriers relaxation, the fast one with a time constant of several ps arises from the Auger-type recombination, which shows almost particle sizeindependence. The slow relaxation component with a time constant of several decades of ns can be clearly determined with ps TRPL spectroscopy in which the slow relaxation process shows strong particle size-dependence. The decay time constants increase from 21 to 34 ns with the decrease of particle size from 3.2 to 2.1 nm. The room-temperature decay lifetime is due to the thermal mixing of bright and dark excitons, and the size-dependence of slow relaxation process can be explained very well in terms of simple three-level model.     

Photoluminescence quenching of CdTe/CdS core-shell quantum dots in aqueous solution by ZnO nanocrystals

Photoluminescence (PL) properties of 3-mercaptopropionic acid (MPA) coated CdTe/CdS core-shell quantum dots (QDs) in aqueous solution in the presence of ZnO colloidal nanocrystals were studied by steady-state and time-resolved PL spectroscopy. The PL quenching of CdTe/CdS core-shell QDs with addition of purified ZnO nanocrystals resulted in a decrease in PL lifetime and a small red shift of the PL band. It was found that CdTe(1.5 nm)/CdS type II core-shell QDs exhibited higher efficiency of PL quenching than the CdTe(3.0 nm)/CdS type I core-shell QDs, indicating an electron transfer process from CdTe/CdS core-shell QDs to ZnO nanocrystals. The experimental results indicated that the efficient electron transfer process from CdTe/CdS core-shell QDs to ZnO nanocrystals could be controlled by changing the CdTe core size on the basis of the quantum confinement effect.     

CdTe/CdS核壳结构量子点超快载流子动力学

在水相合成CdTe以及CdTe/CdS核壳结构量子点基础上, 利用基于抽运-探测技术的瞬态差分透射技术研究了CdTe量子点以及不同CdS壳层厚度的CdTe/CdS量子点的最低激子能态的超快激发与弛豫动力学. 研究表明:相比于CdTe,CdTe/CdS量子点的电子空穴由于空间分离,其所需的激发时间要长于电子空穴空间重叠态所需要的激发时间.随着壳层厚度的增加, 量子点表面的钝化有效地减少了表面态相关弛豫机理,并延长相对应的弛豫时间.     

Disappearance of quantum chaos in coupled chaotic quantum dots

Statistical properties of the single electron levels confined in the semiconductor (InAs/GaAs, Si/SiO₂) double quantum dots (DQDs) are considered. We demonstrate that in the electronically coupled chaotic quantum dots the chaos with its level repulsion disappears and the nearest neighbor level statistics becomes Poissonian. This result is discussed in the light of the recently predicted “huge conductance peak” by R.S. Whitney et al. [Phys. Rev. Lett. 102 (2009) 186802] in the mirror symmetric DQDs.     

Temperature-dependent photoluminescence of vertically stacked self-assembled CdSe quantum dots in ZnSe

We studied the optical properties of multiple layers of self-assembled CdSe quantum dots (QDs) embedded in ZnSe, grown by molecular beam epitaxy. The ZnSe barrier thicknesses separating the QD layers ranged from 30 to 60 monolayers (ML). For stacks with thinnest ZnSe barriers photoluminescence (PL) measurements reveal blue shifts as large as 180 meV relative to PL observed for single QD layers. The amount of blue shift decreases with increasing barrier thickness, and for the 60 ML spacer the PL energy returns to that emitted by a single layer of QDs. Temperature dependence of the integrated intensity of the emission spectra reveals that the activation energy for PL quenching is largest for barrier thicknesses of 30 and 45 ML. We tentatively attribute these effects to a decrease in the size of the vertically stacked QDs when the thickness of the barrier layers is small.     

Hole mobility and trapping in PVK films doped with CdSe/CdS and CdSe quantum dots

Experimental study of the hole mobility in polyvinylcarbazole (PVK) films doped with two kinds of nanocrystals, on bare core CdSe and core-shell CdSe/CdS quantum dots, with concentrations ranging from 3 · 10¹⁰ to 3 · 10¹⁵ cm⁻³, is presented. The quantum dots investigated were made using colloidal chemistry. The hole mobility was measured using the time-of-flight technique as a function of the applied electrical field in the range 10⁵–10⁶ V/cm and for temperatures from 20°C to 50°C. The transient curves, being featureless on a linear plot, show on a double logarithmic scale a sharp inflection point indicating a dispersive carrier drift process. The recovered values of the mobility are in the range 3 · 10⁻⁸–10⁻⁶ cm²·V⁻¹·s⁻¹ and their field and temperature dependences can be analyzed formally within the framework of the Gaussian disorder model proposed by B?ssler. The energetic disorder is, within the experimental accuracy, independent of the concentration and type of quantum dots for the CdSe quantum dots at all concentrations and for the CdS/CdSe quantum dots up to 10¹⁴ cm⁻³. The spatial disorder factors are very large (from 5.3 to 8.7) and do not depend in a systematic way upon the type and concentration of quantum dots (QDs). The experiments show that the apparent mobility does not change considerably with concentration, but it was found that the samples with CdSe/CdS quantum dots at concentrations from 10¹⁵ to 3 · 10¹⁵ cm⁻³ show a decreased photocurrent response. The dependence of the time-integrated transients (corresponding to the full charge value) upon the quantum-dot concentration has been determined. Differences in total photogenerated charge for pure and doped polymer films imply that the quantum dots of that type are the hole traps with capture times much more smaller than the transit time and with emission times a few orders longer than the transit time. CdSe quantum dots without a shell do not seem to exhibit the same properties as core shells and do not produce considerable changes in the charge transfer, even at a density of 10¹⁵ cm⁻³.     

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.