Core-multishell Quantum Dots Research Articles

Importance of Surface Functionalization and Purification for Narrow FWHM and Bright Green-Emitting InP Core–Multishell Quantum Dots via a Two-Step Growth Process

Importance of Surface Functionalization and Purification for Narrow FWHM and Bright Green-Emitting InP Core–Multishell Quantum Dots via a Two-Step Growth Process

Effect of Polymer Capping on Photonic Multi-Core–Shell Quantum Dots CdSe/CdS/ZnS: Impact of Sunlight and Antibacterial Activity

The highly luminescent CdSe/CdS/ZnS core–multi-shell quantum dots (QDs) were prepared without a protective atmosphere through the precursor injection method (phosphine free) in paraffin liquid and oleic acid. Polymers (PEG, PVA, PVP, and PAA) were coated to CdSe/CdS/ZnS core–multi-shell quantum dots to increase stability. However, core–multi-shell structured QDs reveal enhanced emission in the range 355–410 nm by suppressing the defect sensitive cores and nonradioactive recombination in PL spectra. The cubic zinc blended quantum dots with crystallite size in the range 22–44 nm, as confirmed by XRD, were obtained. The resultant absorption spectra of all the samples showed that the samples were absorbent in the UV region over the 302–380 nm range. In the FT-IR spectrum 712, 731, and 400–700 cm–1 band values were assigned to CdSe, CdS, and ZnS band stretching, respectively. Images of CdSe, CdSe/CdS, and CdSe/CdS/ZnS quantum dots obtained from the SEM were spherical whereas QDs capped with different polymers (PEG, PVA, PVP, and PAA) showed nanofibers that were linear and homogeneous size ranged between 12 and 38 nm. These as prepared QDs were placed under visible light for 48 h. After absorbing UV light, the range of UV–vis intensity was enhanced until 389–464 nm and emission intensity enhanced until 492–509 nm, which was confirmed by UV and PL spectra. CdSe/CdS/ZnS QDs with organic ligands revealed antibacterial activity over a broad range against Klebsiella Pneumoniae and Pseudomonas aeruginosa.

Intrinsic blinking characteristics of single colloidal CdSe-CdS/ZnS core-multishell quantum dots

Fluorescence blinking of single colloidal semiconductor quantum dots (QDs) has been extensively studied, and several sophisticated models have been proposed. In this work, we derive Heisenberg equations of motion to carefully study principal transition processes, i.e., photoexcitation, energy relaxation, impact ionization and Auger recombination, radiative and nonradiative recombinations, and tunneling between core states and surface states, of the electron-hole pair in single CdSe-CdS/ZnS core-multishell QDs and show that the on-state probability density distribution of the QD fluorescence obeys the random telegraph signal theory because of the random radiative recombination of the photoexcited electron-hole pair in the QD core, while the off-state probability density distribution obeys the inverse power law distribution due to the series of random walks of the photoexcited electron in the two-dimensional surface-state network after the electron tunnels from the QD core to the QD surface. These two different blinking characteristics of the single QD are resolved experimentally by properly adjusting the optical excitation power and the bin time.

Optical Properties of Quantum Dots with a Core–Multishell Structure

In the last decade, colloidal semiconductor nanocrystals (quantum dots) have been not only studied fundamentally but also applied in photovoltaics, optoelectronics, and biomedicine. Beginning with simple approaches to the deposition of protective shells, e.g., ZnS on CdSe cores, searches for ways to increase the quantum yield of photoluminescence of quantum dots have resulted now in the development of new types of quantum dots characterized not only by record high extinction coefficients but also by high photoluminescence quantum yields. In this work, the optical properties of core–multishell quantum dots have been analyzed. These quantum dots have been specially designed to reach the maximum possible localization of excited charge carriers inside luminescent cores, which makes it possible to reach a photoluminescence quantum yield close to 100%. Core–multishell quantum dot samples with a shell thickness of 3–7 monolayers have been fabricated. Changes in the characteristics of optical transitions in such quantum dots with an increase in the number of layers of the shell have been studied. The effect of the thickness of the shell on the optical properties of prepared quantum dots has been analyzed. In particular, analysis of photoluminescence lifetimes of such quantum dots has revealed a possible alternative mechanism of radiation of core–multishell quantum dots based on the slow charge carrier transfer from the excited outer layer of the CdS shell to the CdSe core.

Optical Properties of Core-Multishell Quantum Dots

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Transport and release of colloidal 3-mercaptopropionic acid-coated CdSe-CdS/ZnS core-multishell quantum dots in human umbilical vein endothelial cells.

Colloidal semiconductor quantum dots (QDs) have been extensively researched and developed for biomedical applications, including drug delivery and biosensing assays. Hence, it is pivotal to understand their behavior in terms of intracellular transport and toxicological effects. In this study, we focused on 3-mercaptopropionic acid-coated CdSe-CdS/ZnS core-multishell quantum dots (3MPA-QDs) converted from the as-grown octadecylamine-coated quantum dots (ODA-QDs) and their direct and dynamic interactions with human umbilical vein endothelial cells (HUVECs). Live cell imaging using confocal fluorescence microscopy showed that 3MPA-QDs first attached to and subsequently aggregated on HUVEC plasma membrane ~25 min after QD deposition. The aggregated QDs started being internalized at ~2 h and reached their highest internalization degree at ~24 h. They were released from HUVECs after ~48 h. During the 48 h period, the HUVECs responded normally to external stimulations, grew, proliferated and wound healed without any perceptible apoptosis. Furthermore, 1) 3MPA-QDs were internalized in newly formed LysoTracker-stained early endosomes; 2) adenosine 5′-triphosphate-induced [Ca2+]i modulation caused a transient decrease in the fluorescence of 3MPA-QDs that were attached to the plasma membrane but a transient increase in the internalized 3MPA-QDs; and 3) fluorescence signal modulations of co-stained LysoTracker and QDs induced by the lysosomotropic agent Gly-Phe-β-naphthylamide were spatially co-localized and temporally synchronized. Our findings suggest that 3MPA-QDs converted from ODA-QDs are a potential nontoxic fluorescent probe for future use in clinical applications. Moreover, the photophysical strategy and techniques reported in this work are easily applicable to study of direct interactions between other nanoparticles and live cells; contributing to awareness and implementation of the safe applications of nanoparticles.

Influence of surface states on blinking characteristics of single colloidal CdSe-CdS/ZnS core-multishell quantum dot

We carefully characterized the fluorescence blinking of single colloidal CdSe-CdS/ZnS core-multishell quantum dots (QDs) with different surface modifications, including octadecylamine (ODA) coated QDs dispersed in chloroform, aqueous 3-mercaptopropionic acids (3MPA) coated QDs in HEPES solution treated by Ca2+ ions and ethylene glycol tetraacetic acid (EGTA, Ca2+ chelator), and aqueous 3MPA-QDs treated by glycerol. It was found that the on- and off-state probability density distributions displayed different rules. The off-state probability density distributions of all QDs complied well with the inverse power law, while the on-state probability density distributions bended upwards in log-log scale, and the degree of the upwards-bending correlated strongly with QD surface modification and fluorescence brightness of the single QD. Further autocorrelation analysis revealed that the fluorescence time series of a single QD was more random when the single QD showed a stronger fluorescence. Realistic numerical simulations with input parameters from quantum mechanical calculations showed that the QD exciton was first generated by an excitation photon; It radiatively recombined to give QD’s fluorescence response, i.e., the on-state, which displayed the upwards-bended on-state probability density distribution profile; The electron and/or the hole of the photoexcited exciton in the QD core, after tunneling to the QD surface, randomly walked through the two-dimensional network of the QD surface states, resulting in the off-state probability density distribution profile of the inverse power law. Surface modification modified the QD surface-state network, in turn modifying the on/off probability density distribution profiles.Our findings provide us with a novel highway of applying colloidal QDs to study microscopic physical, and chemical, processes in many fields including in vivo and in vitro imaging, sensing and labelling.

CdSe@ZnS/ZnS quantum dots loaded in polymeric micelles as a pH-triggerable targeting fluorescence imaging probe for detecting cerebral ischemic area

High photoluminescence (PL) quantum yield (QY), photostability CdSe@ZnS/ZnS core/multishell quantum dots (CM-QDs) were first applied for bioimaging. The solubility, stability and biocompatible of the fluorescence imaging probes were constructed by self-assembly of CM-QDs and pH-responsive methoxy poly(ethylene glycol)-poly(β-amino ester/amidoamine)-dodecylamine (mPEG-PAEA-DDA) multiblock copolymers. The resulting CM-QDs-loaded mPEG-PAEA-DDA micelles (CM-QDs-PEG-PAEA-DDA) exhibited lower cell cytotoxicity and higher fluorescence intensity than the core/shell CdSe@ZnS QDs-encapsulated mPEG-PAEA-DDA micelles (CS-QDs-PEG-PAEA-DDA). Moreover, the in vivo fluorescence imaging ability confirmed that the CM-QDs-PEG-PAEA-DDA can be employed as a pH-triggerable targeting imaging probe for detection of a rat bearing cerebral ischemia disease. Therefore, we believed that the CM-QDs-PEG-PAEA-DDA may be the next generation of fluorescence imaging probes for targeted diagnosis acidic pathological areas, using pH as a stimulus.

Quantum dots modulate intracellular Ca2+ level in lung epithelial cells.

While adverse effects of nanoparticles on lung health have previously been proposed, few studies have addressed the direct effects of nanoparticle exposure on the airway epithelium. In this work, we examine the response of the pulmonary airway to nanoparticles by measuring intracellular Ca2+ concentration ([Ca2+]i) in the Calu-3 epithelial layer stimulated by 3-mercaptopropionic-acid (3MPA) coated CdSe-CdS/ZnS core-multishell quantum dots (QDs). Simultaneous transient transepithelial electrical resistance (TEER) decrease and global [Ca2+]i increase in Calu-3 epithelial layer, accompanied by cell displacements, contraction, and expansion, were observed under QD deposition. This suggests that a QD-induced global [Ca2+]i increase in the Calu-3 epithelial layer caused the transient TEER decrease. The [Ca2+]i increase was marked and rapid in the apical region, while [Ca2+]i decreased in the basolateral region of the epithelial layer. TEER transient response and extracellular Ca2+ entry induced by QD deposition were completely inhibited in cells treated with stretched-activated (SA) inhibitor GdCl3 and store-operated calcium entry (SOCE) inhibitor BTP2 and in cells immersed in Ca2+-free medium. The voltage-gated calcium channel (VGCC) inhibitor nifedipine decreased, stabilized, and suppressed the TEER response, but did not affect the [Ca2+]i increase, due to QD deposition. This demonstrates that the Ca2+ influx activated by QDs’ mechanical stretch occurs through activation of both SA and SOCE channels. QD-induced [Ca2+]i increase occurred in the Calu-3 epithelial layer after culturing for 15 days, while significant TEER drop only occurred after 23 days. This work provides a new perspective from which to study direct interactions between airway epithelium and nanoparticles and may help to reveal the pathologies of pulmonary disease.

Reducing Blinking in Small Core-Multishell Quantum Dots by Carefully Balancing Confinement Potential and Induced Lattice Strain: The "Goldilocks" Effect.

Currently, the most common way to reduce blinking in quantum dots (QDs) is accomplished by using very thick and/or perfectly crystalline CdS shells on CdSe cores. Ideally, a nontoxic material such as ZnS is preferred to be the outer material in order to reduce environmental and cytotoxic effects. Blinking suppression with multishell configurations of CdS and ZnS has been reported only for "giant" QDs of 15 nm or more. One of the main reasons for the limited progress is that the role that interfacial trap states play in blinking in these systems is not very well understood. Here, we show a "Goldilocks" effect to reduce blinking in small (∼7 nm) QDs by carefully controlling the thicknesses of the shells in multishell QDs. Furthermore, by correlating the fluorescence lifetime components with the fraction of time that a QD spends in the on-state, both with and without applying a threshold, we found evidence for two types of blinking that separately affect the average fluorescence lifetime of a single QD. A thorough characterization of the time-resolved fluorescence at the ensemble and single-particle level allowed us to propose a detailed physical model involving both short-lived interfacial trap states and long-lived surface trap states that are coupled. This model highlights a strategy of reducing QD blinking in small QDs by balancing the magnitude of the induced lattice strain, which results in the formation of interfacial trap states between the inner shell and the outer shell, and the confinement potential that determines how accessible the interfacial trap states are. The combination of reducing blinking while maintaining a small overall QD size and using a Cd-free outer shell of ZnS will be useful in a wide array of applications, particularly for advanced bioimaging.

Bioelectric and Morphological Response of Liquid-Covered Human Airway Epithelial Calu-3 Cell Monolayer to Periodic Deposition of Colloidal 3-Mercaptopropionic-Acid Coated CdSe-CdS/ZnS Core-Multishell Quantum Dots.

Lung epithelial cells are extensively exposed to nanoparticles present in the modern urban environment. Nanoparticles, including colloidal quantum dots (QDs), are also considered to be potentially useful carriers for the delivery of drugs into the body. It is therefore important to understand the ways of distribution and the effects of the various types of nanoparticles in the lung epithelium. We use a model system of liquid-covered human airway epithelial Calu-3 cell cultures to study the immediate and long-term effects of repeated deposition of colloidal 3-mercaptopropionic-acid coated CdSe-CdS/ZnS core-multishell QDs on the lung epithelial cell surface. By live confocal microscope imaging and by QD fluorescence measurements we show that the QD permeation through the mature epithelial monolayers is very limited. At the time of QD deposition, the transepithelial electrical resistance (TEER) of the epithelial monolayers transiently decreased, with the decrement being proportional to the QD dose. Repeated QD deposition, once every six days for two months, lead to accumulation of only small amounts of the QDs in the cell monolayer. However, it did not induce any noticeable changes in the long-term TEER and the molecular morphology of the cells. The colloidal 3-mercaptopropionic-acid coated CdSe-CdS/ZnS core-multishell QDs could therefore be potentially used for the delivery of drugs intended for the surface of the lung epithelia during limited treatment periods.

Application of CdSe/ZnS/CdS/ZnS Core–multishell Quantum Dots to Modern OLED Technology

Semiconductor quantum dots (QDs) obtained by means of colloidal synthesis are widely used in fabrication of organic light-emitting devices (OLEDs). We have fabricated QD–OLEDs with an active light-emitting layer formed by novel CdSe/ZnS/CdS/ZnS core–multishell QDs that have luminescence quantum yield of more than 90%. We have compared the performance of QD–OLEDs with different thickness of the active layer and demonstrated that the best performance is achieved at 45-55nm, probably due to field redistribution inside the device. Optimization of the thicknesses of transport layers of QD–OLED is likely to further improve the performance of such devices.

Prepare core–multishell CdSe/ZnS nanocrystals with pure color and controlled emission by tri-n-octylphosphine-assisted method

Core–multishell semiconductor nanocrystals have great potential in light emitting devices (LEDs) display, fluorescent biomarkers and luminescent solar concentrators. However, their applications are strongly limited due to the wide full-width at half-maximum (FWHM), inaccurate controllable emission wavelength, and decreased quantum yield as the shell coverage growth. So there still remains a great challenge for improving the photoluminescence properties of core–multishell quantum dots. In this work, tri-n-octylphosphine (TOP) assisted method was used to prepare CdSe/ZnS QDs with narrow FWHM and controlled emission wavelength, the influence of experimental conditions on the photoluminescent properties of the core–multishell QDs were investigated. The experimental results indicated this is an effective method to prepare core–multishell QDs with pure color emission (FWHM value is smaller than 25nm after coating with 3 monolayers of ZnS), accurately controlled emission and high QY (>95%). This is the smallest FWHM for core–multishell QDs. The emission wavelength of the as-prepared core–multishell QDs can be continuously tuned by simply varying the emission of the core nanocrystals. Furthermore, the knowledge gained in this study enabled us to better understand the mechanism of TOP-assisted method and provide a promise way for light emitting diodes-backlit display with high color saturation.

Heat-induced transformation of CdSe-CdS-ZnS core-multishell quantum dots by Zn diffusion into inner layers.

In this work, we investigate the thermal evolution of CdSe-CdS-ZnS core-multishell quantum dots (QDs) in situ using transmission electron microscopy (TEM). Starting at a temperature of approximately 250 °C, Zn diffusion into inner layers takes place together with simultaneous evaporation of particularly Cd and S. As a result of this transformation, CdxZn1-xSe-CdyZn1-yS core-shell QDs are obtained.

Reversible Modification of CdSe–CdS/ZnS Quantum Dot Fluorescence by Surrounding Ca2+ Ions

It has been known for a long time that the fluorescence intensity of colloidal quantum dots (QDs) becomes modified when free ions are added to the QD solution. The consequences of removing free ions from the QD solution, however, have not been closely investigated. In this work we studied fluorescence from 3-mercaptopropionic acid (3-MPA) coated CdSe–CdS/ZnS core–multishell QDs when free Ca2+ ions were added to and subsequently removed from the QD solution. It was found that QD fluorescence intensity was reduced when Ca2+ ions were added to the QD solution, while the wavelength of the QD fluorescence peak remained unchanged. QD fluorescence recovered when the concentration of free Ca2+ ions in the QD solution was reduced by adding Ca2+ chelator (ethylene glycol tetraacetic acid, EGTA). It was further observed that the time of single QD fluorescence at on-state and QD fluorescence lifetimes were also reduced after adding Ca2+ and then recovered when EGTA was added. Theoretical study shows that a free Ca2+ ...

Stimulated Emission and Lasing from CdSe/CdS/ZnS Core‐Multi‐Shell Quantum Dots by Simultaneous Three‐Photon Absorption

Three-photon pumped stimulated emission and coherent random lasing from colloidal CdSe/CdS/ZnS core-multishell quantum dots are achieved for the first time. These results can offer new possibilities in biology and photonics, as well as at their intersection of biophotonics.

Synthesis of highly luminescent and biocompatible CdTe/CdS/ZnS quantum dots using microwave irradiation: a comparative study of different ligands

We compared the effects of several ligands frequently used in aqueous synthesis, including L-cysteine, L-cysteine hydrochloride, N-acetyl-L-cysteine (NAC), glutathione and 3-mercaptopropionic acid, for microwave synthesis of CdTe quantum dots (QDs) in a sealed vessel with varied temperatures and times, and then developed a rapid microwave-assisted protocol for preparing highly luminescent, photostable and biocompatible CdTe/CdS/ZnS core-multishell QDs. The effects of molecular structures of these ligands on QD synthesis under high temperatures were explored. Among these ligands, NAC was found to be the optimal ligand in terms of the optical properties of resultant QDs and reaction conditions. The emission wavelength of NAC-capped CdTe QDs could reach 700 nm in 5 min by controlling the reaction temperature, and the resultant CdTe/CdS/ZnS core-multishell QDs could achieve the highest quantum yields up to 74% with robust photostability. In addition, the effects of temperature, growth time and shell-precursor ratio on shell growth were examined. Finally, cell culturing indicated the low cytotoxicity of CdTe/CdS/ZnS core-multishell QDs as compared to CdTe and CdTe/CdS QDs, suggesting their high potential for applications in biomedical imaging and diagnostics.

Facile synthesis of transparent and fluorescent epoxy–CdSe–CdS–ZnS core–multi shell polymer nanocomposites

A facile and environmentally benign approach for the synthesis of highly transparent and fluorescent CdSe–CdS–ZnS core–multi-shell polymer nanocomposites is presented. The CdSe–CdS–ZnS core–multi-shell quantum dots (QDs) were prepared via a continual precursor injection and phosphine free method in paraffin liquid and oleic acid without a protective atmosphere. The as-prepared core–multi-shell QDs were dispersed directly in an epoxy polymer matrix via a melt mixing technique. The QDs showed better dispersibility and good optical properties in the epoxy matrix. The transmission electron microscopy (TEM) images showed that the as-synthesized QDs are small, spherical and are well dispersed inside the polymer matrix without any change in morphology. It was found that the nanocomposite filled with yellow-emitting QDs had more transparency compared to the neat epoxy. The luminescence of the neat polymer shifted from the blue region to the yellow region in the nanocomposite. The fluorescent lifetime analysis of the as-prepared core–multi shell and the polymer nanocomposite showed a decrease compared to the core while the tensile measurements showed an increase in the tensile properties of the nanocomposite in comparison with the neat polymer.

Efficient two-photon absorption of CdSe-CdS/ZnS core-multishell quantum dots under the excitation of near-infrared femtosecond pulsed laser

We report that two-photon absorption (TPA) properties of semiconductor CdSe-core CdS/ZnS-multishell quantum dots (QDs) in toluene under excitation of femtosecond laser at 800 nm. The results show efficient TPA process and large TPA cross section of three types of size QDs, which is 1900, 5710, and 16060 GM (1 GM = 10−50 cm4 s photon−1), respectively. TPA cross section dramatically increases with increased core size, showing a strong size-dependence effect. Furthermore, two-photon excitation (TPE) fluorescence intensity not only depends on TPA capacity, but also relies on improved quantum yield resulting from passivation of QD surface by different coated monolayers (MLs). These facts in combination with the narrow fluorescence bandwidth make these QDs as promising probes for multicolor two-photon microscopy.