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.     

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.     

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.     

Decay of electronic excitations in colloidal thioglycolic acid (TGA)-capped CdS/ZnS quantum dots

Investigations of dynamics of exciton relaxation in colloidal thioglycolic acid (TGA)-capped CdS/ZnS core/shell systems with diameter of 3.6 nm by means of femtosecond transient absorption spectroscopy, thermostimulated luminescence (TSL), and decay of luminescence are presented in this paper. It was found that the intensity of trap-state luminescence increases when one and two ZnS monolayers are formed. Also, the lifetime of trap-state luminescence increases. Two types of trap states with different depths were found, using thermostimulated luminescence technique. Localized states of the first type with depth of 0.085 eV do not change their concentration during sell formation. In contrast, trap state of the second type with depth of 0.125 eV are almost completely removed. It was found that the electron lifetime, investigated femtosecond transient absorption is not changed during formation of ZnS shell. It was concluded that localized states are channels of non-radiative recombination, direct quenching the center of trap-state luminescence. The absence of exciton luminescence is caused by rapid localization of holes at luminescence center.     

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.     

Nanotwinning in CdS quantum dots

High resolution transmission electron microscopy, X-ray diffraction and photoluminescence measurements are carried out in order to study the defects in CdS quantum dots (QDs), synthesized in cubic phase by chemical co-precipitation method. The nanotwinning structures in CdS quantum dots (∼2.7 nm) are reported for the first time. Mostly CdS QDs are characterized by existence of nanotwin structures. The twinning structures are present together with stacking faults in some QDs while others exist with grain boundaries. Raman spectroscopy analysis shows intense and broad peaks corresponding to fundamental optical phonon mode (LO) and the first over tone mode (2LO) of CdS at 302 cm⁻¹ and 605 cm⁻¹ respectively. A noticeable shift is observed in Raman lines indicating the effect of phonon confinement. Fourier transform infrared spectroscopy analysis confirms the presence of Cd–S stretching bands at 661 cm⁻¹ and 706 cm⁻¹. The photoluminescence spectrum shows emission in yellow and red regions of visible spectrum. The presence of stacking faults and other defects are explained on the basis of X-rays diffraction patterns and are correlated with photoluminescence spectrum. These nanotwinning and microstructural defects are responsible for different emissions from CdS QDs.     

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.     

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.     

Multiphonon probe in ZnS quantum dots

Raman spectroscopic studies have been performed for ZnS nanoclusters in this study. Cluster size dependent multiphonon properties are reported in detail. A flurry of zone boundary phonons is demonstrated in the scattering process. A strong deformation potential (DP) dominated Raman spectra are reported for cubic ZnS nanocluster of diameter with ∼2.2 nm in size below the quantum confinement. Transverse optic (TO) mode in the multiphonon process shows only even order overtones for 2.2 nm cluster, suggesting the dominance of a two‐phonon process and its integral multiples. The possibility of surface oxidation in the smallest cluster is ruled out as a plausible explanation for the observed even order TO modes which resemble the higher order modes of ZnO. A wave vector‐independence of electron–phonon interaction in quantum dots leads to strong dependence on DP‐related phenomenon. A large DP value for the second‐order process in ZnS than that with respect to the first‐order process is made responsible for the observed phenomenon. Copyright © 2010 John Wiley & Sons, Ltd.     

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.     

Resonant Raman scattering of ZnS,ZnO, and ZnS/ZnO core/shell quantum dots

Resonant Raman scattering by optical phonon modes as well as their overtones was investigated in ZnS and ZnO quantum dots grown by the Langmuir–Blodgett technique. The in situ formation of ZnS/ZnO core/shell quantum dots was monitored by Raman spectroscopy during laser illumination.     

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.     

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.     

Large-scale control of enhancement and quenching of photoluminescence for ZnSe/ZnS quantum dots and Ag nanoparticles in aqueous solution

We investigated the optical properties of hybrid exciton–plasmon coupling ensembles composed of ZnSe/ZnS quantum dots and Ag nanoparticles in aqueous solution. We modulated their average interval by changing the ratio of quantum dots and Ag nanoparticles. The transition from dramatic PL enhancement to PL quenching state was experimentally observed, according to the continuous decrease of the PL lifetime. The PL enhancement rate exceeded 10, with the Purcell factor of 3.5. Meanwhile, the proportion of fast decay increased from 0.3 to 0.6, corresponding to the proportion of slow decay decreased from 0.7 to 0.4. Our experiment is important for the hybrid exciton–plasmon coupling system to be practicable in optoelectronic application.     

Passively Q-switched green laser operation using CdTe/CdS quantum dots

The direct generation of passively Q-switched lasers at a green wavelength has rarely been investigated in the past. In this Letter, we demonstrate a passively Q-switched praseodymium-doped yttrium lithium fluoride green laser at 522 nm using CdTe/CdS quantum dots as a saturable absorber. A maximum average output power of 33.6 m W is achieved with the shortest pulse width of 840 ns. The corresponding pulse energy and peak power reached 0.18 μJ and 0.21 W, respectively. To the best of our knowledge, this is the first demonstration in regard to a quantum dots saturable absorber operating in the green spectral region.     

Synthesis of CdS quantum dots by mechanochemical reaction

2 + Na₂S → CdS + 2NaCl induced by mechanical milling resulted in the formation of CdS particles with an average diameter of < 8 nm. The average particle size was controlled within the range of 4 to 8 nm by varying the size of the grinding media. The onset energy of optical absorption showed a blue shift with decreasing particle size. Received: 29 August 1997/Accepted: 25 September 1997     

Fabrication of highly luminescent InP/Cd and InP/CdS quantum dots

Highly luminescent InP/Cd and InP/CdS core-shell QDs were fabricated by sequential addition of cadmium acetylacetonate and dodecanethiol to InP core solutions, which showed a red-shift in absorption and emission. ICP measurement revealed the existence of cadmium and TEM images showed the increased size of InP/CdS QDs. PXRD data identified zinc blend structures of InP and InP/CdS QDs, which indexed to the (1 1 1), (2 2 0) and (3 1 1) planes. The slight shift of peaks between InP and InP/CdS QDs can demonstrate the existence of CdS shell structures.     

Surface enhanced Raman scattering by CdS quantum dots

Surface enhanced Raman scattering is studied in nanostructures with CdS quantum dots formed using the Langmuir-Blodgett technology. Features due to quantum dot longitudinal optical phonons are observed in the Raman spectra of both free CdS quantum dots and such dots distributed in an organic matrix. The surface enhanced Raman scattering by nanostructures with CdS quantum dots covered by an Ag cluster film is observed experimentally. Applying Ag clusters onto the nanostructure surfaces results in a sharp (40-fold) increase in the intensity of Raman scattering by optical phonons in the quantum dots. It is shown that the dependence of surface enhanced Raman scattering on the excitation energy is resonant with a maximum at the energy corresponding to the maximum absorption coefficient of Ag clusters.