Decay of electronic excitations in CdS and CdS/ZnS colloidal quantum dots: spectral and kinetic investigations

Using the spectral methods of induced absorption, luminescence, and photostimulated luminescence flash, we have experimentally investigated processes of decay of electronic excitations in CdS colloidal quantum dots and in CdS/ZnS “core-shell” systems synthesized in gelatin by the sol-gel method. It has been shown that the decay of electronic excitations in colloidal quantum dots of this type is predominantly related to a fast localization of nonequilibrium charge carriers on surface defects and their subsequent recombination during times on the order of units and tens of picoseconds. The passage to core-shell systems eliminates, to a large extent, surface defects of the core, some of which are luminescence centers. However, upon using the sol-gel synthesis, a noticeable fraction of luminescence centers are formed in the interior of the CdS quantum dot, which, as well as in the case of CdS/ZnS systems, ensures localization of exciton, blocks its direct annihilation, and maintains recombination radiation.     

Auger process in CdS/ZnS core-shell quantum dots

Auger processes are investigated for CdS/ZnS core-shell quantum dots. Auger recombination (AR) lifetime and electron relaxation inside the core are computed. Using the effective-mass theory and by solving a three-dimension Schrödinger equation we predict the dependence of Auger relaxation on size of core-shell nanocrystals. We considered in this work different AR processes: the excited electron (EE), excited hole (EH), multiexciton AR type. Likewise, Auger multiexciton recombination rates are predicted for biexciton. Our results show that biexciton AR type is more efficient than the other AR process (excited electron (EE) and excited hole (EH)). We also found that electron Auger relaxation P→S is very efficient in core-shell nanostructures.     

Photostability comparison of CdTe and CdSe/CdS/ZnS quantum dots in living cells under single and two-photon excitations

The photostability is an outstanding feature of quantum dots (QDs) used as fluorescence probes in biological staining and cell imaging. To find out the related factors in the QD photostability, the photobleaching of naked CdTe QDs and BSA coated CdSe/CdS/ZnS QDs in human hepatocellular carcinoma (QGY) cells and human nasopharynx carcinoma (KB) cells were studied under single photon excitation (SPE) and two-photon excitation (TPE). In these two cell lines the cellular QDs were irradiated by a 405 nm continuous wave laser for SPE or an 800 nm femto-second (fs) laser for TPE. The QD photobleaching with the irradiation time was found to fit a biexponential decay. The fast decay plays a dominant role in the bleaching course and thus can be used as the parameter to quantitatively evaluate the QD photostability. The TPE decreased the QD photobleaching as compared to SPE. The BSA coated core/shell QDs had improved the photostability up to 4-5 times than the naked QDs due to the shielding effect of the QD shell. Therefore, it is better to use core/shell structured QDs as the fluorescence probe combining with a TPE manner for those long-term monitoring studies.     

Spin-flip limited exciton dephasing in CdSe/ZnS colloidal quantum dots

The dephasing time of the lowest bright exciton in CdSe/ZnS wurtzite quantum dots is measured from 5 to 170 K and compared with density dynamics within the exciton fine structure using a sensitive three-beam four-wave-mixing technique unaffected by spectral diffusion. Pure dephasing via acoustic phonons dominates the initial dynamics, followed by an exponential zero-phonon line dephasing of 109 ps at 5 K, much faster than the ~10 ns exciton radiative lifetime. The zero-phonon line dephasing is explained by phonon-assisted spin flip from the lowest bright state to dark-exciton states. This is confirmed by the temperature dependence of the exciton lifetime and by direct measurements of the bright-dark-exciton relaxation. Our results give an unambiguous evidence of the physical origin of the exciton dephasing in these nanocrystals.     

ZnS:Ag/CdS: a new family of color-tunable quantum dots

ZnS:Ag/CdS quantum dots (QDs) have been synthesized by a reverse micelle process under ambient environment. Excited by 350?nm, the emission peak of ZnS:Ag/CdS QDs changes from 425 to 625?nm with increasing the thickness of CdS shells. Although the quantum yields of QDs decrease with CdS shells thickening, the luminescent brightness remains stable throughout. Compared with the traditional color-tunable CdSe QDs, the synthesis of ZnS:Ag/CdS QDs is less toxic and more economic. Therefore, this synthesis process can be regarded as an efficient way to fabricate a series of luminescent nanostructures for a variety of applications.     

ZnS/CdS/ZnS量子点量子阱的荧光衰减

采用反胶束方法制备了ZnS/CdS/ZnS量子点量子阱，并对其光谱性质进行了研究。结果表明所制得的量子点量子阱尺寸分布均匀，平均粒径为4.5nm，发光峰位于515nm左右，归属于CdS体内的施主－受主对复合。ZnS/CdS/ZnS量子点量子阱中CdS的发光比核－壳结构的ZnS/CdS量子点增强了近四倍，荧光寿命也有所增长。     

Light quenching and dark states in colloidal solutions of semiconductor CdSe/ZnS quantum dots

The photodynamics of optical limiting in colloidal solutions of different-size CdSe/ZnS quantum dots is studied. The behavior of the dependences points to a multistage process that includes the bleaching and optical limiting stages. The limiting photodynamics is compared with luminescence dynamics of quantum dots under conditions of high-power excitation. It is shown that the optical limiting efficiency in such media is determined by the position of exciting radiation with respect to the main exciton absorption band of the quantum dot. The roles played by so-called dark states and light quenching in limiting photodynamics are discussed.     

Mercaptopropionic acid capped CdSe/ZnS quantum dots as fluorescence probe for lead(II)

MPA stabilized CdSe/ZnS NCs was applied as a fluorescent probe for the sensitive detection of Pb²⁺ in water. The microreaction was demonstrated as a facile method for the reproducible synthesis of CdSe/ZnS NCs with a high quantum yield. The good stability of CdSe/ZnS NCs was proved by the significant maintaining of photoluminescent (PL) after the ligand exchange with MPA, and was further demonstrated by the excellent PL property in water solution with various pH values. The cation exchange of Zn with Pb led to the linear quenching of PL with the concentration of Pb²⁺, which provided as an opportunity to apply MPA stabilized CdSe/ZnS NCs as fluorescent probes for Pb²⁺. A facile method by adjustment of QDs concentration was demonstrated as a suitable way to approach different detection limits. The detection limits of 0.03 and 3.3 μM were achieved by setting QDs solutions with the absorbance of the first exciton peak as 0.05 and 0.15, respectively.     

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.     

Investigation of electronic and optical properties of (CdSe/ZnS/CdSe/ZnS) quantum dot–quantum well heteronanocrystal

In this article, we have investigated the photoluminescence intensity of quantum dot–quantum well heteronanocrystal with non-linear potential profile which has been analyzed by the finite element numerical methods and is compared with traditional potential profile of same heteronanocrystal. We have probed the effect of carrier localization in layers of heteronanocrystal on the photoluminescence intensity. Moreover, the effects of variation of radius layers such as CdSe core, shell, and ZnS barriers radius on the photoluminescence intensity are studied. Besides, for the first time, we demonstrated the shift of quantum dot–quantum well operation wavelength by introducing non-linear potential profile in the core of heteronanocrystal that can be drastically affected on biological application. Furthermore, in biological application, by tuning the emission wavelengths of quantum dot into the far-red and near-infrared ranges, the non-invasive in vivo imaging technique was developed. In this wavelength window, tissue absorption, scattering, and auto-fluorescence intensities have minimum quantities. In our article with new structure, the relation between size and operation wavelength don’t follow traditional relation.     

Synthesis and characterization of aqueous MPA-capped CdS–ZnS core–shell quantum dots

The novel CdS–ZnS core–shell nanoparticles are synthesized using simple one-step aqueous chemical approach. 3-mercaptopropionic acid (MPA) was used as the capping molecule. The structural and optical properties of the prepared samples are characterized by X-ray diffraction (XRD), UV–vis absorption spectroscopy, photoluminescence (PL) spectroscopy, energy-dispersive X-ray (EDX) and transition electron microscopy (TEM). The studies show that pH contributed noticeably to the growth and optical properties of nanoparticles. The TEM results indicate that the prepared particles have core–shell structure.     

Spectral manifestations of hybrid association of CdS colloidal quantum dots with methylene blue molecules

We have studied the spectral properties of mixtures formed by CdS colloidal quantum dots with an average diameter of 2.5 nm and methylene blue molecules and that are dispersed into gelatin. We have revealed that, in the presence of CdS quantum dots, the luminescence intensity of methylene blue increases. We suggest a model of this effect, which is based on electronic excitation energy transfer from luminescence centers of CdS quantum dots to methylene blue molecules.     

Temperature-dependent photoluminescence of dimethylzinc-treated ZnSe/ZnS quantum dots

Temperature-dependent photoluminescence (PL) measurements were carried out ZnSe/ZnS quantum dots (QDs) grown with post-growth interruption under a dimethylzinc (DMZn) flow. The PL spectra showed sigmoidal peak shifts and V-shaped full width at half maximum (FWHM) variations with increasing temperature, which strongly suggest that the QD structure of ZnSe/ZnS is quite similar to that of other material systems grown in the Stranski–Krastanov mode. Apparent differences are revealed as a consequence of DMZn treatment: (i) the PL spectra of ZnSe/ZnS QDs showed peaks at higher energies and persisted up to 300 K, and(ii) the minimum points of the V-shaped FWHM appear at a higher temperature compared to H₂-purged ZnSe/ZnS QDs. Experimental results demonstrate the enhancement of localization energy.     

Radiative quantum efficiency of CdSe/ZnS quantum dots suspended in different solvents

The radiative quantum efficiencies η of the CdSe/ZnS core-shell nanoparticles embedded into polymethyl methacrylate (PMMA) and suspended in three different solvents: chloroform (CHCl₃), toluene (C₆H₅CH₃) and tetrahydrofuran (C₄H₈O) were measured using thermal lens (TL) technique. The mode-mismatched pump-probe TL measurements were accomplished in function of the CdSe/ZnS quantum-dot concentration (12-60 mg/ml) at λ_e = 594 nm (pump) and λ_p = 632.8 nm (probe). The values obtained for η were higher for CdSe/ZnS nanoparticles suspended in tetrahydrofuran and chloroform, as compared to the values for toluene. Thermal diffusivity (D) and the absolute nonradiative quantum efficiency (φ) were determined.     

Electron–phonon interaction in CdS/ZnS quantum dot

Electron–phonon effects on the two first electronic states in both CdS and GaAs quantum dots are investigated. Both confined longitudinal optical (LO) and surface optical (SO) phonons are considered. We use the intermediate-type variational approach. We find that, shifts caused by phonon contribution on electronic energies are more significant for CdS quantum dot. We find, also, that, contrary to GaAs based quantum dots, we shouldn’t neglect the SO phonon contribution for CdS based ones, especially for small dots.     

Nonlinear absorption and refraction of light in a colloidal solution of CdSe/ZnS quantum dots upon two-photon resonant excitation

This paper reports on the results of an investigation into the nonlinear transmission of individual ultrashort pulses of a train generated by a mode-locked laser through a colloidal solution of CdSe/ZnS quantum dots in toluene upon two-photon resonant excitation of the fundamental optical transition. The specific features of the nonlinear transmission are explained in terms of the two-photon absorption and self-defocusing processes. Analysis of the experimental results makes it possible to separate the self-defocusing processes that are governed by the inertialess change in the refractive index due to the interaction of high-power optical pulses with bound electrons and those determined by the nonlinear change in the refractive index under the action of two-photon-excited carriers in a quantum dot.     

Pairing of spin excitations in lateral quantum dots

We demonstrate the existence of correlated electronic states as paired spin excitations of lateral quantum dots in the integer quantum Hall regime. Starting from the spin-singlet filling-factor nu=2 droplet, by increasing the magnetic field we force the electrons to flip spins and increase the spin polarization. We identify the second spin-flip process as one accompanied by correlated, spin depolarized phases, interpreted as pairs of spin excitons. The correlated states are identified experimentally in few-electron lateral quantum dots using high source-drain voltage spectroscopy.