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1.
硒化镉发光量子点的制备及其在有机发光器件中的应用   总被引:4,自引:4,他引:0  
硒化镉量子点具有随粒径尺寸改变,而产生发光波长调变的特性,目前已被广泛研究。本研究是由化学溶胶法合成不同粒径尺寸的核壳型CdSe/ZnS硒化镉量子点,其表面包覆十六烷基胺,避免分子团聚现象。在由硒化镉成核温度的控制,成功地制备一系列具有各种尺寸粒径的核壳型硒化镉量子点(2—6nm)。本研究也合成了含有纳米金粒子于核壳型硒化镉量子点,实验结果发现:硒化镉发光效率明显的提高。在有机发光器件的应用方面,将发光波长为505nm核壳型CdSe/ZnS量子点掺入溶有发光波长为570nm铱化合物的氯仿溶液时,其溶液的光致发光光谱表明,原量子点的发光特性消失,只有铱化合物的发光依然存在,且其发光强度呈现明显增强趋势,我们推测此现象源自于量子点到铱化合物能量转移的机制。我们也以含有核壳型硒化镉量子点的铱化合物与PVK混合材料为发光层,成功的制作发光二极管器件,器件的发光效率因核壳型硒化镉的掺杂,明显提高2倍多。  相似文献   

2.
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   

3.
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   

4.
In comparison with conventional organic dyes, quantum dots (QDs) have unique optical and electronic properties, which provide QDs with a wide scope of prospective application in biology and biomedicine. However, the toxicity of QDs and the fluorescence intensity of labeled bacteria must precede their application in bacterial imaging and tracing in vivo. Here, we show that treatment with CaCl2 significantly improved bacterial labeling efficiency of CdSe/ZnS QDs with the CdSe core size of ~3.1 nm (relative fluorescence unit (RFU) value and ratio of fluorescent E. coli) with rising CdSe/ZnS QDs concentration in a concentration-dependent manner. At 12.5 nmol/L CdSe/ZnS QDs concentration, labeled Escherichia coli (E. coli) DH5α appeared as short rod-shaped and luminescent with normal size, and the survival rate and ultrastructure did not change in comparison to the control. But the ratio of fluorescent bacteria and RFU were very low. However, the survival rate of transformed E. coli was significantly inhibited by high CdSe/ZnS QDs concentrations (≥25 nmol/L). Moreover, internalization of CdSe/ZnS QDs resulted in ultrastructure damage of transformed E. coli in a concentration-dependent manner (≥25 nmol/L). Therefore, CdSe/ZnS QDs may not suitable for tracing of bacteria in vivo. Moreover, our study also revealed that colony-forming capability assay and transmission electron microscopy could be used to comprehensively evaluate the toxicity of QDs on labeled bacteria. Our findings do provide a new direction toward the improvement and modification of QDs for use in imaging and tracing studies in vivo.  相似文献   

5.
Particular features and quenching mechanisms of exciton luminescence of water-soluble nanocomposites that are formed as a result of the interaction of surface charged semiconductor quantum dots (QDs) CdSe/ZnS (d CdSe = 2.8 nm) and cationic porphyrins (H2TMPyrP4+ and ZnTMPyrP4+) have been studied theoretically and experimentally. It has been found that, in CdSe/ZnS??Porphyrin conjugates, there occurs long-range inductive resonance electronic excitation energy transfer from surface modified (with thioglycolic or mercaptoundecanoic acid) QDs to porphyrins, which is accompanied by quenching of the exciton luminescence of QDs and an increase in the fluorescence intensity of porphyrin. It has been shown that, when mercaptoundecanoic acid is used as a QD shell, the QD luminescence quenching efficiency by porphyrins follows the F?rster-Galanin theory and depends on the overlap integral between the CdSe/ZnS luminescence band and the absorption spectra of free-base porphyrin H2TMPyrP4+ and its metal complex ZnTMPyrP4+. It has been revealed that, as the QDs ? Zn-porphyrin intercenter distance decreases from 39.1 (mercaptoundecanoic acid) to 30.1), a considerable QD luminescence quenching is observed; however, the energy transfer efficiency substantially decreases, from 55% in the former case to 23% in the latter one. Based on the spectral-luminescent data and quantum-chemical calculations, it has been found that the chemical change of H2TMPyrP4+ in the structure of the complex with CdSe/ZnS QDs passivated by thioglycolic or mercaptoundecanoic acid is caused by the formation of a metal complex ZnTMPyrP4+. Based on calculations of the redox-potentials, it has been concluded that the low luminescence quantum yield of CdSe/ZnS QDs passivated by residues of mercaptocarboxylic acids S?(CH2) n COO? and its dependence on the number of CH2 groups are related to the possibility of photoinduced electron transfer from the HOMO of passivating molecules to QDs (QD* ? S?(CH2)nCOO? hole transfer). It has been shown that the quenching of the exciton luminescence of QDs in heterogeneous structures CdSe/ZnS(thioglycolic acid)??ZnTMPyrP4+, which is complementary to the energy transfer, can be caused by the photoinduced electron transfer that involves the participation of the LUMO of the ZnTMPyrP4+ molecule (QD* ? ZnTMPyrP4+).  相似文献   

6.
Quantum dots' sensitized solar cells (QDSSCs) can create the high-performance and low-cost photovoltaic in the future. In this study, we synthesized the film of TiO2/CdS/CdSe/ZnS photoanodes by successive ionic layer adsorption reaction (SILAR) method. The absorption spectra, photoluminescent spectra and electrochemical impedance spectra (EIS) of the film TiO2/CdS/CdSe/ZnS photoanodes show that the structure of energy levels in the conduction band (CB) of photoanode materials CdS, CdSe, and ZnS quantum dots (QDs) can absorb a great number of photons in each region and inject stimulated electrons quickly into the conduction band (CB) of TiO2. Furthermore, we also studied the influence of the SILAR cycles on the dynamic resistance, the lifetime of electrons in QDSSCs through Nyquist and Bode.  相似文献   

7.
The optical properties of a composite material consisting of a thin polymer film, which is activated by semiconductor CdSe/ZnS quantum dots (QDs) and silver nanoparticles, on a transparent dielectric substrate have been investigated. It is revealed that the presence of silver nanoparticles leads to an increase in the QD absorption (by a factor of 4) and in the fluorescence intensity (by a factor of 10), whereas the fluorescence time drops by a factor of about 10. Excitation of the composite medium by a pulsed laser is found to result in narrowing of the fluorescence band and a sublinear dependence of its intensity on the pulse energy. In the absence of silver nanoparticles, the fluorescence spectrum of QDs is independent of the excitation-pulse energy density, and the fluorescence intensity depends linearly on the pulse energy in the entire range of energy densities, up to 75 mJ/cm2.  相似文献   

8.
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   

9.
The aim of this work is to investigate the effect of silica (SiO2) nanoparticles (NPs) on optical and dielectric properties of BBEA nematic liquid crystal (NLC). For optical analysis the photoluminescence (PL) and UV-absorbance experiments have been performed. The doped system is showing enhancement in the intensity of photoluminescence with varying concentration of nanoparticles. A red shift is observed in the emission spectra of NLC doped with silica nanoparticles. The PL emission peak of NLC is observed at 377.3 nm which is shifted to 379.7 nm in the presence of silica nanoparticles. We have also observed the enhancement in the value of UV absorption for silica doped systems in comparison to the pure system. Energy band gap of pure and doped systems has been calculated and it is found that the energy band gap is decreasing with concentration which is a promising result of this study. The dielectric parameters of the pure and doped NLC systems were carried out as a function of frequency and temperature. Different dielectric parameters such as relative permittivity, loss factor and dielectric conductivity have been measured. The pure and silica nanoparticles doped systems has shown decreased value of dielectric permittivity and loss factor at lower frequency region and at higher frequency regions these values became constant. The value of relative permittivity also decreases with concentration. The increased value of a.c. conductivity for doped systems can be utilized in device designing. Moreover, the temperature dependence of the birefringence (Δn) was determined from the transmitted intensity of light for pure and doped systems and the improvement in its value for both composites has been observed. Improved value of birefringence has pronounced applications in optical devices.  相似文献   

10.
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   

11.
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.  相似文献   

12.
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   

13.
In this work we synthesized ZnS:Mn2+ nanoparticles by chemical method using PVP (polyvinylpyrrolidone) as a capping agent in aqueous solution. The structure and optical properties of the resultant product were characterized using UV-vis optical spectroscopy, X-ray diffraction (XRD), photoluminescence (PL) and z-scan techniques. UV-vis spectra for all samples showed an excitonic peak at around 292 nm, indicating that concentration of Mn2+ ions does not alter the band gap of nanoparticles. XRD patterns showed that the ZnS:Mn2+ nanoparticles have zinc blende structure with the average crystalline sizes of about 2 nm. The room temperature photoluminescence (PL) spectrum of ZnS:Mn2+ exhibited an orange-red emission at 594 nm due to the 4T1-6A1 transition in Mn2+. The PL intensity increased with increase in the Mn2+ ion concentration. The second-order nonlinear optical properties of nanoparticles were studied using a continuous-wave (CW) He-Ne laser by z-scan technique. The nonlinear refractive indices of nanoparticles were in the order of 10−8 cm2/W with negative sign and the nonlinear absorption indices of these nanoparticles were obtained to be about 10−3 cm/W with positive sign.  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.
Metal sulphide quantum dots (QDs) have broad applications. Sulphate-reducing bacteria (SRB) have been recognized as synthesizers of metal sulphides, with the characteristics of a high-production efficiency and easy product harvest. However, SRB are incapable of synthesizing metal sulphide QDs. In the present study, cheap hydroxypropyl starch (HPS) was used to assist SRB in manufacturing the ZnS QDs. The results exhibited that the HPS accelerated the growth of SRB and reduction of SO4 2+ into S2?, while it blocked the precipitation between S2? and Zn2+ to control the nucleation and growth of ZnS, resulting in the formation of ZnS QDs. When the HPS concentration increased from 0.2 to 1.6 g/L, the average crystal size (ACS) of ZnS QDs dropped from 5.95 to 3.34 nm, demonstrating the controlled biosynthesis of ZnS QDs. The ZnS QDs were coated or adhered to by both HPS and proteins, which played an important role in the controlled biosynthesis of ZnS QDs. The remarkable blue shift of the narrow UV absorption peak was due to the quantum confinement effect. The sequential variation in the colour of the photoluminescence spectrum (PL) from red to yellow suggested a tunable PL of the ZnS QDs. The current work demonstrated that SRB can fabricate the formation of ZnS QDs with a controlled size and tunable PL at a high-production rate of approximately 8.7 g/(L × week) through the simple mediation of HPS, with the yield being 7.46 times the highest yield in previously reported studies. The current work is of great importance to the commercialization of the biosynthesis of ZnS QDs.  相似文献   

16.
A facile method for synthesizing color-tunable magnetic and luminescent hybrid bifunctional nanoparticles is presented. A series of CdSe/ZnS core-shell quantum dots (QDs) with different sizes were successfully fabricated and self-assembled to Fe3O4 magnetic nanoparticles (MNP), which were subsequently coated with a polyethyleneimine (PEI) layer to prevent large aggregates. The hydrophobic QDs capped with trioctylphosphine oxide (TOPO) formed a coating surrounding MNP, and were transferred into hydrophilic phase by PEI with high efficiency. The samples were characterized by TEM, FT-IR, XRD, EDS, UV-vis spectrophotometer, fluorescent spectrophotometer and PPMS. Results show that the original properties of the nanoparticles were well-preserved in the hybrid structure. All MNP-QDs hybrid nanoparticles showed paramagnetic behavior and the nanocomposites were still highly luminescent with no shift in the PL peak position.  相似文献   

17.
Achieving bright, reliable, robust, and stable probes for in vivo imaging is becoming extremely urgent for the cancer imaging research community. To date very few works have reported on elucidating in the varied and chemically complex biological milieu. The authors report detailed investigations of the synthesis of near‐infrared, water dispersive, strongly luminescent, and highly stable PbS/CdS/ZnS core/shell/shell quantum dots (QDs). These QDs are extremely stable, they could keep their initial morphology, dispersion status, and photoluminescence (PL) in phosphate buffered saline buffer for as long as 14 months. The QDs also show excellent photostability and could keep ≈80% of their initial PL intensity after 1 h continuous, strong UV illumination. More interestingly, they show negligible toxicity to cultured cells even at high QDs concentration. Given these outstanding properties, the QDs are explored for in vivo, tumor imaging in mice. With one order of magnitude lower QD concentration (0.04 mg mL–1), significantly weaker laser intensity (0.04 W cm–2 vs ≈1 W cm–2), and considerably shorter signal integration time (≤1 ms vs hundreds of ms) as compared to the best reported rare earth doped nanoparticles, the QDs show high emission intensity even at injection depth of ≈2.5 mm.  相似文献   

18.
《Composite Interfaces》2013,20(7):425-432
Abstract

ZnS nanoparticles and Mn2+-doped ZnS nanoparticles were prepared by a reverse micelle reaction system. In addition, ZnS and Mn2+-doped ZnS nanoparticles were modified with poly(vinyl alcohol) (PVA) and 1-dodecanethiol (C12H25SH). The average particle size of the ZnS sample is determined around 2.3 nm by using the well-known Scherrer equation, which is in accordance with the results obtained from UV–vis and TEM analysis. Fluorescence intensity of the Mn2+-doped ZnS nanoparticles increases with increasing Mn2+ content compared with undoped ZnS nanoparticles, and coating PVA can also make fluorescence intensity increase. Different Zn2+/S2- or C12H25SH/Zn2+ can affect intensity of PL emission peak and its position, which is discussed in this paper.  相似文献   

19.
CdS:Mn2+/ZnS and CdS:Mn2+/CdS core–shell nanoparticles were synthesized in aqueous medium via chemical precipitation method in an ambient atmosphere. Polyvinylpyrrolidone (PVP) was used as a capping agent. The effect of the shell (ZnS and CdS) thickness on CdS:Mn2+ nanoparticles was investigated. Inorganically passivated core/shell nanocrystals having a core (CdS:Mn2+) diameter of 4 nm and a ZnS-shell thickness of ∼0.5 nm exhibited improved PL intensity. Optimum concentration of doping ions (Mn2+) was selected through optical study. For all the core–shell samples two emission peaks were observed, the first one is band edge emission in the lower wavelength side due to energy transfer to the Mn2+ ions in the crystal lattice; the second emission is characteristic peak of Mn2+ ions (4T1 → 6A1). The XRD, TEM and PL results showed that the synthesized core–shell particles were of high quality and monodisperse.  相似文献   

20.
光诱导功能退化是胶体量子点在应用中面临的主要挑战之一,本文针对这一问题研究了使用磁控溅射沉积SiO2薄膜形成钝化层来提高CdSe/ZnS量子点发光稳定性的方法。首先,通过三正辛基膦辅助连续离子层吸附反应方法合成了615 nm发光的红色CdSe/ZnS量子点。然后将量子点旋涂在SiO2/Si基片上,再通过磁控溅射方法在量子点上沉积了厚度为20 nm的SiO2薄膜作为钝化层。使用连续波激光光源分别在空气气氛和真空条件下照射样品,研究了经过不同照射时间后钝化和未钝化量子点的稳态光致发光光谱。结果表明,随着照射时间的延长,没有SiO2钝化的量子点的PL强度显著降低、PL峰值发生蓝移、FWHM不断增大。对比研究发现,由于SiO2薄膜能够阻挡空气中的水和氧,减缓了量子点表面的光诱导氧化现象,因此显著提高了CdSe/ZnS量子点的稳定性。  相似文献   

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