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1.
An asymmetrically coupled double quantum dot (QD) system consisting of adjacent CdSe and CdZnMnSe QD layers in a ZnSe matrix was investigated using polarization-selective magneto-photoluminescence (PL). Two well-resolved PL peaks are observed corresponding, respectively, to the CdSe and the CdZnMnSe QDs. The peaks exhibit significant change in the intensity and energy position when a magnetic field is applied. The enhancement of the degree of σ circular polarization emitted by the non-magnetic CdSe QDs is observed in the double layer system, as compared to that observed in CdSe QDs without the influence of neighboring CdZnMnSe QDs. This behavior was discussed in terms of antiferromagnetic interaction between carrier spins localized in pairs of CdSe and CdZnMnSe QDs that are electronically coupled.  相似文献   

2.
Time Resolved Photoluminescence (TRPL) measurements on the picosecond time scale (temporal resolution of 17 ps) on colloidal CdSe and CdSe/ZnS Quantum Dots (QDs) were performed, to elucidate the role of intrinsic and surface states on the emission process. Transient PL spectra reveal three emission peaks with different lifetimes (60 ps, 460 ps and 9–10 ns, from the bluest to the reddest peak). The energy separations among the states, together with their characteristic decay times, allow us to attribute the two higher energy peaks to ±1U and ±1L bright states of the fine structure picture of spherical CdSe QDs, and the third one to surface states emission, respectively. We show that the contribution of surface emission to the PL results to be different for the two samples studied (67% in the CdSe QDs and 32% in CdSe/ZnS QDs), confirming the decisive role of the ZnS shell in the improvement of the surface passivation.  相似文献   

3.
This article describes the synthesis of highly water-soluble Zn x Hg1−x Se y S1−y quantum dots (QDs) in aqueous solution through a simple photo-assisted reaction between ZnSe QDs and mercury(I) nitrate dihydrate [Hg2(NO3)2·2H2O]. In order to deduce the optimal synthesis conditions, we varied several parameters, including the concentrations of mercaptosuccinic acid (MSA) and Hg2(NO3)2·2H2O, the illumination time, and the reaction temperature. When irradiated at temperatures below 80 °C, the ZnSe QDs reacted with the S2− ions formed rapidly from MSA and the Hg2+ ions formed from Hg2 2+ ions to form Zn x Hg1−x Se y S1−y QDs through a process of photo-etching and surface combination. Under different conditions, we prepared a series of Zn x Hg1−x Se y S1−y QDs that emit fluorescence at the maximum wavelengths ranging from 405 to 760 nm. Inductively coupled plasma-mass spectrometry and transmission electron microscopy/energy dispersive spectrometry revealed that the content of Hg in the Zn x Hg1−x Se y S1−y QDs was greater when the synthesis was conducted at higher temperature. The Zn0.88Hg0.12Se0.44S0.56 QDs exhibit improved photostability than crude ZnSe QDs and possess long lifetimes (τ1 ~ 38 ns and τ2 ~ 158 ns).  相似文献   

4.
Device grade quantum dots (QDs) require QDs ensembles to retain their original superior optical properties as in solution. QDs with thick shells are proven effective in suppressing the inter-dot interaction and preserving the emission properties for QDs solids. However, lattice strain–induced defects may form as the shell grows thicker, resulting in a notable photoluminescence quenching. Herein, a well-type CdxZn1−xS/CdSe/CdyZn1−yS QDs is proposed, where ternary alloys CdZnS are adopted to match the lattice parameter of intermediate CdSe by separately adjusting the x and y parameters. The resultant thick-shell Cd0.5Zn0.5S/CdSe/Cd0.73Zn0.27S QDs reveal nonblinking properties with a high PL QY of 99% in solution and 87% in film. The optimized quantum dot light-emitting diodes (QLEDs) exhibit a luminance of 31547.5 cd m−2 at the external quantum efficiency maximum of 21.2% under a bias of 4.0 V. The shell thickness shows great impact on the degradation of the devices. The T50 lifetime of the QLEDs with 11.2 nm QDs reaches 251 493 h, which is much higher than that of 6.5 and 8.4 nm QDs counterparts. The performances of the well-type thick-shell QLEDs are comparable to state-of-the-art devices, suggesting that this type of QDs is a promising candidate for efficient optoelectronic devices.  相似文献   

5.
Temperature-dependent photoluminescence (PL) spectroscopy of CuInS2 core and CuInS2/ZnS core–shell quantum dots (QDs) was studied for understanding the influence of a ZnS shell on the PL mechanism. The PL quantum yield and lifetime of CuInS2 core QDs were significantly enhanced after the QD surface was coated with the ZnS shell. The temperature dependences of the PL energy, linewidth, and intensity for the core and core–shell QDs were studied in the temperature range from 92 to 287 K. The temperature-dependent shifts of 98 meV and 35 meV for the PL energies of the QDs were much larger than those of the excitons in their bulk semiconductors. It was surprisingly found that the core and core–shell QDs exhibited a similar temperature dependence of the PL intensity. The PL in the CuInS2/ZnS core–shell QDs was suggested to originate from recombination of many kinds of defect-related emission centers in the interior of the cores.  相似文献   

6.
Microreactor systems existed as a powerful tool for the continuous synthesis of quantum dots. However, the lack of structure optimization for the discrete units led to empirical determination of the length scale, and the properties of the formed products varied in different cases. In this article, the optimizations for the micromixer volume and capillary diameter were presented based on the synthesis of CdSe nanocrystals (NCs). Spectra investigation revealed that the application of a small convective mixer of 36 μL led to 1/3 increase of CdSe concentration in the crude solution. The enhanced mixing of the precursors in this case was also demonstrated favorable to achieve CdSe NCs with narrow PL width. Fast heating and uniform reaction condition achieved in a narrow channel favored the preparation of high quality CdSe NCs under short residence time. However, the application of wide channel did not necessarily result in CdSe NCs with poor quality. Here, we demonstrated that high-quality CdSe NCs with narrow full width at half maximum (FWHM) as 32 nm and high quantum yield (QY) 34.7% could be prepared using an 844 μm inner diameter capillary. Based on the obtained results, the scaled-up synthesis of CdSe NCs was demonstrated, and a high quantity of 0.8 g dry CdSe NCs powder (3.5 nm, σ ~ 8.2%) was obtained within 1 h.  相似文献   

7.
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.  相似文献   

8.
A series of CdSe and CdSe/CdS quantum dots (QDs) labeled with amino acid-modified β-cyclodextrin (β-CD) was prepared by a simple ultrasonic method. These amino acid-modified β-CD-coated QDs are very soluble and stable in biological buffer. They also have high colloidal stability and strong optical emission properties that are similar to those of untreated tri-n-octylphosphine oxide (TOPO)-coated QDs. The quantum yields (QYs) of these amino acid-modified β-CD-coated CdSe and CdSe/CdS QDs in biological buffer were found to be very high. In particular, the QYs of the positively charged l-His-β-CD-coated CdSe/CdS QDs were as high as 33.5±1.8%. In addition, the fluorescence lifetime of these QDs was also very long in PBS solutions as determined by frequency domain spectroscopy. For example, the lifetime of l-His-β-CD-coated CdSe/CdS QDs was 8.6 ns. The in vitro cytotoxicity of these QDs in ECV-304, SH-SY5Y and HeLa cells was found to be lower. l-His-β-CD-coated CdSe/CdS QDs were the least cytotoxic (IC50 95.6±3.2 mg mL?1 in ECV-304 cells after 48 h). The flow cytometry results show that the positively charged amino acid led to a considerable increase in biocompatibility of QDs. This may be attributed to the presence of an amino acid-modified β-CD outer layer, which enhanced the biocompatibility.  相似文献   

9.
The paper presents the original study of photoluminescence (PL) and Raman scattering spectra of core–shell CdSe/ZnS quantum dots (QDs) covered by the amine-derivatized polyethylene glycol (PEG) with luminescence interface states. First commercially available CdSe/ZnS QDs with emission at 640 nm (1.94 eV) covered by PEG polymer have been studied in nonconjugated states. PL spectra of nonconjugated QDs are characterized by a superposition of PL bands related to exciton emission in a CdSe core and to the hot electron–hole recombination via high energy luminescence states. The study of high energy PL bands in QDs at different temperatures has shown that these PL bands are related to luminescence interface states at the CdSe/ZnS or ZnS/polymer interface. Then CdSe/ZnS QDs have been conjugated with biomolecules—the Osteopontin antibodies. It is revealed that the PL spectrum of bioconjugated QDs changed essentially with decreasing hot electron–hole recombination flow via luminescence interface states. It is shown that the QD bioconjugation process to Osteopontin antibodies is complex and includes the covalent and electrostatic interactions between them. The variation of PL spectra due to the bioconjugation is explained on the basis of electrostatic interaction between the QDs and biomolecule dipoles that stimulates re-charging QD interface states. The study of Raman scattering of bioconjugated CdSe/ZnS QDs has confirmed that the antibody molecules have the electric dipoles. It is shown that CdSe/ZnS QDs with luminescence interface states are promising for the study of bioconjugation effects with specific antibodies and can be a powerful technique in biology and medicine.  相似文献   

10.
A silanization process was employed to transfer hydrophobic quantum dots (QDs) prepared via an organic route at high temperature into water phase. The QDs were further coated with a thin organic SiO2 shell to form QDs@SiO2 composite nanoparticles by ligand exchange or remaining initial organic ligands on the surface. In this study, QDs with different ligands, either trioctylphosphine oxide (TOPO) or oleic acid (OA), were employed to investigate the effects of ligands on the reverse micelles in preparing QDs@SiO2 nanoparticles. In the preparing process, hydrophobic QDs were silanized by partially hydrolyzed tetraethyl orthosilicate (TEOS). For TOPO-capped CdSe QDs, surface TOPO ligands were completely replaced by partially hydrolyzed TEOS. As for OA-capped CdSe/Cd x Zn1?x S QDs, surface OA ligands were partially replaced. It was found that the ligand exchange drastically reduced the photoluminescence (PL) efficiency of CdSe QDs. Furthermore, the cytotoxicity studies of QDs@SiO2 have been carried out in detail. The results indicate that CdSe/Cd x Zn1?x S QDs@SiO2 composite nanoparticles exhibit lower cytotoxicity compared with CdSe QDs@SiO2, because the SiO2 shell and remained OA ligand layer can effectively prevent the leakage of toxic Cd2+ ions. Meanwhile, it was found that these CdSe/Cd x Zn1?x S QDs@SiO2 nanocomposites could keep excellent PL properties even for 24 h incubating with Siha cells, which indicating that our prepared composite nanoparticles are potentially applicable for cell imaging in biological systems.  相似文献   

11.
Indium phosphide (InP) quantum dots (QDs) are ideal substitutes for widely used cadmium-based QDs and have great application prospects in biological fields due to their environmentally benign properties and human safety. However, the synthesis of InP core/shell QDs with biocompatibility, high quantum yield (QY), uniform particle size, and high stability is still a challenging subject. Herein, high quality (QY up to 72%) thick shell InP/GaP/ZnS core/shell QDs (12.8 ± 1.4 nm) are synthesized using multiple injections of shell precursor and extension of shell growth time, with GaP serving as the intermediate layer and 1-octanethiol acting as the new S source. The thick shell InP/GaP/ZnS core/shell QDs still keep high QY and photostability after transfer into water. InP/GaP/ZnS core/shell QDs as fluorescence labels to establish QD-based fluorescence-linked immunosorbent assay (QD-FLISA) for quantitative detection of C-reactive protein (CRP), and a calibration curve is established between fluorescence intensity and CRP concentrations (range: 1–800 ng mL−1, correlation coefficient: R2 = 0.9992). The limit of detection is 2.9 ng mL−1, which increases twofold compared to previously reported cadmium-free QD-based immunoassays. Thus, InP/GaP/ZnS core/shell QDs as a great promise fluorescence labeling material, provide a new route for cadmium-free sensitive and specific immunoassays in biomedical fields.  相似文献   

12.
The electron paramagnetic resonance (EPR) spectra of the trigonal prismatic complexes Tc(abt)3, Tc(bdt)3, Re(abt)3 and Re(bdt)3 (abt, O-aminobenzenethiol; bdt, benzene-1,2-dithiol) in dilute frozen solution are interpreted in terms of an axially symmetric spin Hamiltonian, with g values close to two, principal hyperfine couplings of |A Tc| ~ 5–12 × 10−4 cm−1, nuclear quadrupole couplings of |P Tc| ~ 0.3–0.35 × 10−4 cm−1 and the unusual values 5 × 10−4 cm−1 ~ |A zz Re| < |P Re| ~ |A xx Re| ~ |A yy Re| ~ 25 × 10−4 cm−1. Similar magnitudes of the parameters have been obtained by simulation of the previously published spectra of Re(pda)3, Re(tdt)3 and Re(pdt)3 (pda, O-phenylenediamine; tdt, toluene-3,4-dithiol; pdt, cis-1,2-diphenylethene-1,2-dithiol) by other authors. The unexpectedly large value of P relative to A is a common feature of all the Re tris-dithiolato and related trigonal prismatic complexes studied by EPR and is attributed to the high degree of delocalization of the unpaired electron onto the ligands and the distortion of the electron charge cloud. These factors are less evident in the complexes Tc(abt)3 and Tc(bdt)3. Intermolecular dipolar interactions, narrowed by weak exchange, are responsible for some of the spectral features observed in the solid state and concentrated (≫1 mM) frozen solutions, although there is no evidence for specific solute–solute interactions.  相似文献   

13.
CdSe quantum dots (QDs) prepared using an aqueous sodium selenosulphite and N,N′-dimethylformamide (DMF) in commercial polymethylmethacrylate (PMMA) showed excellent optical properties. Tuning of the absorption and emission wavelengths by varying the selenium concentration with respect to cadmium is studied. As-prepared CdSe quantum dots showed absorption band at 405 nm (3.06 eV) associated with the formation of ‘early-stage’ CdSe nano-particles along with weak absorption at 480–90 nm due to continuous growth of the particles. The blue-green and yellow-green light emissions were observed from as-prepared solutions. Photoluminescence (PL) measurement showed band-edge emissions at around 430 nm for small clusters but a more stable emission at 544 nm for the 1:1 CdSe sample. X-ray diffraction (XRD) pattern of the CdSe/PMMA powder with Cd/Se ratio of 1:1 showed broad pattern for cubic CdSe. Transmission electron microscopy (TEM) showed cube like de-shaped spherical dots in the region of about 5 nm.  相似文献   

14.
Herein a novel approach is reported to achieve tunable and high photoluminescence (PL) quantum yield (QY) from the self‐grown spherical TiO2 quantum dots (QDs) on fluorine doped TiO2 (F‐TiO2) flowers, mesoporous in nature, synthesized by a simple solvothermal process. The strong PL emission from F‐TiO2 QDs centered at ≈485 nm is associated with shallow and deep traps, and a record high PL QY of ≈5.76% is measured at room temperature. Size distribution and doping of F‐TiO2 nanocrystals (NCs) are successfully tuned by simply varying the HF concentration during synthesis. During the post‐growth rapid thermal annealing (RTA) under vacuum, the arbitrary shaped F‐TiO2 NCs transform into spherical QDs with smaller sizes and it shows dramatic enhancement (≈163 times) in the PL intensity. Electron spin resonance (ESR) and X‐ray photoelectron spectroscopy (XPS) confirm the high density of oxygen vacancy defects on the surface of TiO2 NCs. Confocal fluorescence microscopy imaging shows bright whitish emission from the F‐TiO2 QDs. Low temperature and time resolved PL studies reveal that the ultrafast radiative recombination in the TiO2 QDs results in highly efficient PL emission. A highly stable, biologically inert, and highly fluorescent TiO2 QDs/flowers without any capping agent demonstrated here is significant for emerging applications in bioimaging, energy, and environmental cleaning.  相似文献   

15.
The change in the intensity of the photoluminescence (PL) spectra of nematic liquid crystal (NLC) composites as a function of the concentration of CdSe/ZnS semiconductor quantum dots (QDs) and TiO2 and ZrO2 nanoparticles ~5 nm in diameter has been investigated. It is shown that the PL-quenching intensity in composites with CdSe/ZnS QDs exceeds that in composites with TiO2 and ZrO2 nanoparticles. The lowfrequency spectra of these composites with a concentration of 0.1 wt %, recorded in the range of 102–103 Hz, and the content of mobile ions in them have been investigated. It is found that the dielectric loss in the composite with CdSe/ZnS QDs is much higher and the content of mobile ions is larger by a factor of 3 than in the composites with TiO2 and ZrO2 nanoparticles. It is shown that an increase in the CdSe/ZnS QD concentration in NLC composites leads to an increase in the dielectric loss and a decrease in the PL intensity. Possible mechanisms of the interaction between NLC molecules and CdSe/ZnS QDs are discussed.  相似文献   

16.
This article presents the evolution of the photo-luminescence (PL) of silicon quantum dots (QDs) with an average diameter of 5–6 nm dispersed in alcohol under different conditions. Two samples were considered after alcohol dispersion: freshly synthesized (kept in air for 2 days) QDs which do not exhibit luminescence and air-aged (kept in air for 2 years) QDs exhibiting red-IR luminescence. Experiments performed with addition of a small volume of water, followed by heating for different times showed that the oxidation occurs gradually until transforming totally the initial material in SiO2. The oxidation process does not enable the appearance of PL from the Si core for dispersed non-aged powders, while it results in a blue shift of the PL maximum intensity for the aged ones. The results obtained after UV illumination clearly indicate an effect of the UV irradiation on the luminescence of QDs dispersed in aqueous environment, and the treatments with acidic water lead to the conclusion of a possible enhancement of the PL by hydrogen passivation of the non-radiative defects. This result should be taken into account for post-production treatments and applications, more particularly, considering a controlled and safe use of luminescent Si QDs.  相似文献   

17.
Characterization of samples of cadmium selenide quantum dots (CdSe) QDs dissolved in toluene colloidal solutions at a concentration of 1.4 mg/ml was carried out through UV–Vis absorption and photoluminescence (PL) spectroscopy. The size-dependent absorption and red-shifted PL emission peak wavelengths could be tuned between 510–576 and 545–606 nm respectively. Optical absorption spectral measurements yielded CdSe QDs having diameters about ~ 2.44–3.69 nm with energy gaps 2.32–2.08 eV which are higher than the bulk CdSe (1.74 eV) reminiscent of quantum confinement. This is found to be in good agreement with the semi-empirical pseudopotential model. In addition, the first excitonic absorption transition 1S(e)1S3/2(h) oscillator strength and the corresponding fluorescence radiative decay time of CdSe QDs are assessed using relevant Einstein relations for absorption and emission in a two-level system. The elaborated calculations would anticipate that the transition oscillator scale with the CdSe QD radius as ~ R2.54. Correspondingly, the calculated radiative decay times decrease from 56.4 to 23.2 ns which scale with CdSe QDs radius as ~ R?2.155 in fairly good agreement with experimental values reported in the literature.  相似文献   

18.
The sizes of semiconductor nanocrystals of CdSe/CdS quantum dots (QDs) synthesized by the colloidal method were estimated using small-angle X-ray scattering. The distribution of QD nanocrystals in organic solvents of different polarities and in polymer gels and matrices is studied. Structural invariants of scattering QD particles (heterogeneities of the electron density)—namely, inertia radii and sizes, forms, and dispersive composition of particles—are determined. The contribution of scattering by QDs in solutions and gels is calculated. The effective sizes of particles and their aggregates are determined, and the parameters of the distribution over the QD sizes in organic solvents and polymer matrices are estimated. The typical distance between particles in samples is determined. The position of the maximum at the beginning of the small-angle scattering curves corresponds to the distance d m = 2π/h 0 between the planes (here, h 0 is the position of the maximum on the scale h). It is 74–76.9 ? for solutions, 60 ? for gels, and 99 ? for polymer matrices with concentrations of up to 0.15% and 77 ? for those with the concentrations exceeding 0.15%, which is close to the estimation of the sizes of separate CdSe QDs that was obtained from the distribution histograms (60–80 ?). This result shows that CdSe/CdS QDs introduced in the polymer matrices disperse to form either separate particles or small aggregates and located at a distance on the order of 80 ? from each other.  相似文献   

19.
A fluorescent hybrid cadmium sulphide quantum dots (QDs) dendrimer nanocomposite (DAB-CdS) synthesised in water and stable in aqueous solution is described. The dendrimer, DAB-G5 dendrimer (polypropylenimine tetrahexacontaamine) generation 5, a diaminobutene core with 64 amine terminal primary groups. The maximum of the excitation and emission spectra, Stokes’ shift and the emission full width of half maximum of this nanocomposite are, respectively: 351, 535, 204 and 212 nm. The fluorescence time decay was complex and a four component decay time model originated a good fit (χ = 1.20) with the following lifetimes: τ 1 = 657 ps; τ 2 = 10.0 ns; τ 3 = 59.42 ns; and τ 4 = 265 ns. The fluorescence intensity of the nanocomposite is markedly quenched by the presence of nitromethane with a dynamic Stern-Volmer constant of 25 M−1. The quenching profiles show that about 81% of the CdS QDs are located in the external layer of the dendrimer accessible to the quencher. PARAFAC analysis of the excitation emission matrices (EEM) acquired as function of the nitromethane concentration showed a trilinear data structure with only one linearly independent component describing the quenching which allows robust estimation of the excitation and emission spectra and of the quenching profiles. This water soluble and fluorescent nanocomposite shows a set of favourable properties to its use in sensor applications.  相似文献   

20.
Room-temperature time-resolved luminescence measurements on single CdSe/ZnS quantum dots (QDs) are presented. Fluorescence emission spectra were recorded over periods of up to 30 minutes with a time resolution as small as 6 ms. For QDs in ambient air, a clear 30–40 nm blue shift in the emission wavelength is observed, before the luminescence stops after about 2–3 minutes because of photobleaching. In a nitrogen atmosphere, the blue shift is absent while photobleaching occurs after much longer times (i.e., 10–15 minutes). These observations are explained by photoinduced oxidation. The CdSe surface is oxidized during illumination in the presence of oxygen. This effectively results in shrinkage of the CdSe core diameter by almost 1 nm and consequently in a blue shift. The faster fading of the luminescence in air suggests that photoinduced oxidation results in the formation of non-radiative recombination centers at the CdSe/CdSeOx interface. In a nitrogen atmosphere, photoinduced oxidation is prevented by the absence of oxygen. Additionally, a higher initial light output for CdSe/ZnS QDs in air is observed. This can be explained by a fast reduction of the lifetime of the long-lived defect states of CdSe QDs by oxygen.  相似文献   

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