Water-based route to colloidal Mn-doped ZnSe and core/shell ZnSe/ZnS quantum dots

Relatively monodisperse and highly luminescent Mn(2+)-doped zinc blende ZnSe nanocrystals were synthesized in aqueous solution at 100 °C using the nucleation-doping strategy. The effects of the experimental conditions and of the ligand on the synthesis of nanocrystals were investigated systematically. It was found that there were significant effects of molar ratio of precursors and heating time on the optical properties of ZnSe:Mn nanocrystals. Using 3-mercaptopropionic acid as capping ligand afforded 3.1 nm wide ZnSe:Mn quantum dots (QDs) with very low surface defect density and which exhibited the Mn(2+)-related orange luminescence. The post-preparative introduction of a ZnS shell at the surface of the Mn(2+)-doped ZnSe QDs improved their photoluminescence properties, resulting in stronger emission. A 2.5-fold increase in photoluminescence quantum yield (from 3.5 to 9%) and of Mn(2+) ion emission lifetime (from 0.62 to 1.39 ms) have been observed after surface passivation. The size and the structure of these QDs were also corroborated by using transmission electron microscopy, energy dispersive spectroscopy, and X-ray powder diffraction.     

核-壳结构CdSe/ZnS量子点的制备、硫醇修饰及其光学性能

采用高温有机相包覆技术制备了CdSe/ZnS核壳结构量子点材料,考察了包覆量对量子点材料的光学性能的影响,研究了含脂肪链和芳香基的双硫醇分子1,4-苯二甲硫醇和1,8-辛二硫醇对于具有核-壳结构的CdSe/ZnS量子点材料的修饰作用,考察了修饰作用对于量子点的量子效率和荧光强度等光学性能的影响.实验结果表明:随着硫化锌包覆量的增加,量子点的量子效率及其荧光发射强度明显提高;硫醇的修饰能显著增强量子点的发光强度,随着硫醇浓度的增加,其发光性能增强,但是达到一定程度后,光学性能基本不随硫醇浓度的变化而变化.根据固体核磁共振等实验结果推测:硫醇分子可能部分替代了量子点体系中的正三辛基氧膦配体,稳定了量子点体系,对量子点起修饰保护作用,从而提高了量子点的光学性能.     

Type-II quantum dots: CdTe/CdSe(core/shell) and CdSe/ZnTe(core/shell) heterostructures

Type-II band engineered quantum dots (CdTe/CdSe(core/shell) and CdSe/ZnTe(core/shell) heterostructures) are described. The optical properties of these type-II quantum dots are studied in parallel with their type-I counterparts. We demonstrate that the spatial distribution of carriers can be controlled within the type-II quantum dots, which makes their properties strongly governed by the band offset of the comprising materials. This allows access to optical transition energies that are not restricted to band gap energies. The type-II quantum dots reported here can emit at lower energies than the band gaps of comprising materials. The type-II emission can be tailored by the shell thickness as well as the core size. The enhanced control over carrier distribution afforded by these type-II materials may prove useful for many applications, such as photovoltaics and photoconduction devices.     

CdSe/ZnS quantum dots based fluorescence quenching method for determination of paeonol

Aqueous polymethylmethacrylate (PMMA)-capped CdSe/ZnS quantum dots were used as fluorescence probes for paeonol determination. Based on the fluorescence quenching of aqueous CdSe/ZnS quantum dots caused by paeonol, a simple, sensitive and rapid method was developed. Under the optimal conditions, with excitation and emission wavelengths at 350 nm and 620 nm, respectively, the calibration plot of F0-F with concentration of paeonol was linear in the range of 25.04-175.2 mg L(-1) with correlation coefficient of 0.9986. The limit of detection was 0.017 mg L(-1). The concentration of paeonol in paeonol ointment was determined by the proposed method and the result agreed with the claimed value. Furthermore, the possible fluorescence quenching mechanism was discussed.     

Solar cells sensitized with type-II ZnSe-CdS core/shell colloidal quantum dots

Type-II quantum dots (QDs) were applied for QDs-sensitized solar cells for the first time and showed prominent absorbed photon to current conversion efficiency.     

Photorefractive performance of a CdSe/ZnS core/shell nanoparticle-sensitized polymer

We report the photorefractive performance of a polymer composite sensitized by CdSe/ZnS core/shell nanoparticles, and also comprising poly(N-vinylcarbazole) and an electro-optic chromophore. The nanoparticles are characterized by absorption and photoluminescence spectroscopy, elemental analysis, transmission electron microscopy, and powder x-ray diffraction. The electro-optic response of the composite is measured independently of the photorefractive effect by transmission ellipsometry. An asymmetric two-beam coupling gain of 30.6+/-0.4 cm(-1) is obtained, confirming photorefractivity. Degenerate four-wave mixing is used to assess photorefractive performance and, at a poling field of 70 V microm(-1), yields a diffraction efficiency of 4.21%+/-0.03%, a holographic contrast of 3.05 x 10(-4)+/-1 x 10(-6), a space-charge rise time of 25+/-2 s, and a sensitivity of 4.7 x 10(-5)+/-4 x 10(-6) cm3 J(-1). These results constitute a significant improvement on the performance of previous nanoparticle-sensitized photorefractive polymer composites.     

Intermittent electron transfer activity from single CdSe/ZnS quantum dots

Electron transfer activity from excited single CdSe/ZnS core/shell quantum dots (QDs) to adsorbed Fluorescein 27 was studied by single QD fluorescence spectroscopy. In comparison with QDs, the QD-acceptor complexes showed a shorter average and broader distribution of QD emission lifetimes due to electron transfer to adsorbates. Large fluctuation of lifetimes in single QD/dye complexes was observed, indicating intermittent electron transfer activity from QDs.     

Controlling charge separation and recombination rates in CdSe/ZnS type I core-shell quantum dots by shell thicknesses

Type I core/shell quantum dots (QDs) have been shown to improve the stability and conversion efficiency of QD-sensitized solar cells compared to core only QDs. To understand how the shell thickness affects the solar cell performance, its effects on interfacial charge separation and recombination kinetics are investigated. These kinetics are measured in CdSe/ZnS type I core/shell QDs adsorbed with anthroquinone molecules (as electron acceptor) by time-resolved transient absorption spectroscopy. We show that the charge separation and recombination rates decrease exponentially with the shell thickness (d), k(d) = k(0)e(-βd), with exponential decay factors β of 0.35 ± 0.03 per ? and 0.91 ± 0.14 per ?, respectively. Model calculations show that these trends can be attributed to the exponential decrease of the 1S electron and hole densities at the QD surface with the shell thickness. The much steeper decrease in charge recombination rate results from a larger hole effective mass (than electron) in the ZnS shell. This finding suggests possible ways of optimizing the charge separation yield and lifetime by controlling the thickness and nature of the shell materials.     

Optical properties of CdSe and CdSe/ZnS quantum dots dispersed in solvents of different polarity

Original organic capping TOPO/TOP groups of CdSe and CdSe/ZnS quantum dots (QDs), from mother solution were replaced with 2_mercaptoethanol, which was chosen as model compound, in order to achieve water solubility. Obtained water dispersions of CdSe and CdSe/ZnS QDs were characterized by UV/VIS absorption and luminescence techniques. Luminescence measurements revealed that bare cores are very sensitive to surface capping, transfer into water diminished emission intensity. Core/shell, CdSe/ZnS, QDs are much more resistant to changes of the capping and solvent, and significant part of emission intensity was preserved in water. The article is published in the original.     

Biosilicated CdSe/ZnS quantum dots as photoluminescent transducers for acetylcholinesterase-based biosensors

CdSe/ZnS core/shell quantum dots (QDs) are functionalized with mercaptoundecanoic acid (MUA) and subsequently covered with poly-L-lysine (PLL) as the template for the formation of the silica outer shell. This nanocomposite is used as a transduction and stabilization system for optical biosensor development. The covalent immobilization of the enzyme acetylcholinesterase from Drosophila melanogaster (AChE) during the formation of the biomimetically synthesized silica is used here as a model, relatively unstable enzyme, as a proof of principle. The enzyme is successfully immobilized onto the QDs and then stabilized by the PLL capping and the subsequent formation of the outer nanoporous silica thin shell, giving rise to the QD/AChE/PLL/silica biosensor. It is shown that the poly-L-lysine templated silica outer shell does not modify the optical properties of the quantum dots, while it protects the enzyme from unfolding and denaturation. The small pores of the silica shell allow for the free diffusion of the analyte to the active center of the enzyme, while it does not allow for the proteases to reach the enzyme. The response of the QD/AChE/PLL/silica nano-biosensor to its substrate, acetylcholine chloride, is evaluated by monitoring the changes in the QDs' photoluminescence which are related to the changes in pH. These pH changes of the surrounding environment of the QDs are induced by the enzymatic reaction, and are associated with the analyte concentration in the solution. The biodetection system proposed is shown to be stable with a storage lifetime of more than 2 months. The data presented provides the grounds for the application of this nanostructured biosensor for the detection of AChE inhibitors.     

Aqueous synthesis of glutathione-capped CdTe/CdS/ZnS and CdTe/CdSe/ZnS core/shell/shell nanocrystal heterostructures

Here we demonstrate the aqueous synthesis of colloidal nanocrystal heterostructures consisting of the CdTe core encapsulated by CdS/ZnS or CdSe/ZnS shells using glutathione (GSH), a tripeptide, as the capping ligand. The inner CdTe/CdS and CdTe/CdSe heterostructures have type-I, quasi-type-II, or type-II band offsets depending on the core size and shell thickness, and the outer CdS/ZnS and CdSe/ZnS structures have type-I band offsets. The emission maxima of the assembled heterostructures were found to be dependent on the CdTe core size, with a wider range of spectral tunability observed for the smaller cores. Because of encapsulation effects, the formation of successive shells resulted in a considerable increase in the photoluminescence quantum yield; however, identifying optimal shell thicknesses was required to achieve the maximum quantum yield. Photoluminescence lifetime measurements revealed that the decrease in the quantum yield of thick-shell nanocrystals was caused by a substantial decrease in the radiative rate constant. By tuning the diameter of the core and the thickness of each shell, a broad range of high quantum yield (up to 45%) nanocrystal heterostructures with emission ranging from visible to NIR wavelengths (500-730 nm) were obtained. This versatile route to engineering the optical properties of nanocrystal heterostructures will provide new opportunities for applications in bioimaging and biolabeling.     

Low power operated highly luminescent ferroelectric liquid crystal doped with CdSe/ZnSe core/shell quantum dots

We report the enhancement in the molecular ordering of ferroelectric liquid crystal (FLC) doped with CdSe/ZnSe graded core/shell (CZ) quantum dots (QDs) by using optical methods. Significant decrease in operating voltage and enhancement in optical brightness are assigned to the large primary order parameter (θ) and hence anchoring of FLC molecules by CZ QDs. The enhancement in photoluminescence is conjectured to be due to an increase in molecular alignment yielding higher absorption which is confirmed by excitation spectra. These observations would definitely offer a promising tool to get superior core/shell QD incorporated FLC-based display devices.     

Transparent conducting films of CdSe(ZnS) core(shell) quantum dot xerogels

A method of fabricating sol-gel quantum dot (QD) films is demonstrated, and their optical, structural and electrical properties are evaluated. The CdSe(ZnS) xerogel films remain quantum confined, yet are highly conductive (10(-3) S cm(-1)). This approach provides a pathway for the exploitation of QD gels in optoelectronic applications.     

Ionic impurities in nematic liquid crystal doped with quantum dots CdSe/ZnS

We investigated the dielectric losses and the ionic currents in the nematic liquid crystal (NLC) doped with semiconductor quantum dots (QDs) of CdSe/ZnS core – shell type and covered with trioctylphosphine oxide (TOPO) molecules. The dielectric loss tangent of the NLC composites increased with increasing the QDs concentration from 0.1 to 0.3 wt%. The density of mobile ions in the composites increased linearly and the average values of ions mobility in the composites decreased with increasing the QDs concentration. The fast ions with the mobility of about 10^–10 m²/V·s and the slow ions with the mobility of about 10^–11 m²/V·s were detected in the NLC composites. The growth of the content of slow ions took place with increasing the QDs concentrations. Increasing the dielectric loss tangent was observed with increasing the duration of sonication time of the NLC composites to prepare homogeneous suspensions. The fragmentation of the CdS/ZnS shell as a result of the sonication may lead to the appearance of the slow ions in the NLC composites.     

Emission-tunable microwave synthesis of highly luminescent water soluble CdSe/ZnS quantum dots

Water soluble CdSe/ZnS nanoparticles with emission maxima from 511 nm to 596 nm and quantum efficiencies ranging from 11% to 28% are synthesized in a facile two-step method in ambient atmospheric conditions using a commercially available microwave reactor.     

Characterization of the adsorption of oligonucleotides on mercaptopropionic acid-coated CdSe/ZnS quantum dots using fluorescence resonance energy transfer

Semiconductor quantum dots (QDs) coated with thioalkyl acid ligands are often used as probes and reporters for nucleic acid sensing, or protein sensing using aptamers, and are also potential vectors for gene delivery. In such applications, the interactions that potentially lead to the adsorption of oligonucleotides onto the surface of colloidal QDs are an important consideration. To explore such interactions, fluorescence resonance energy transfer (FRET) between QDs and oligonucleotides labeled with a fluorescent dye was used to identify and characterize a set of conditions that favor strong adsorption on 3-mercaptopropionic acid (MPA)-coated CdSe/ZnS QDs. Adsorption curves and competitive binding experiments were used to determine that the order of affinity for nucleobase adsorption was dC>dA≥dG?dT. The length of the oligonucleotide sequence was also important, with an 80-mer sequence adsorbing more strongly than its 20-mer analog. Adsorption decreased with increasing pH and corresponded to the ionization of the carboxylic acid groups of the MPA ligands. Increased ionic strength partially offsets ligand ionization and increased the extent of adsorption. The interaction between QDs and oligonucleotides was labile, with increases in adsorption at lower concentrations of oligonucleotide and with an increasing number of oligonucleotides per QD. The results were consistent with a hydrogen-bonding model for adsorption, where neutral thioalkyl acid ligands interact favorably with nucleobases and ionized ligands resist adsorption.     

Role of surface ligands in optical properties of colloidal CdSe/CdS quantum dots

In order to study the role of surface ligands in determining optical properties of colloidal quantum dots (QDs), we have selectively fabricated and studied CdSe/CdS core-shell QDs with strongly confined electron and hole states attached with commonly used surface ligands. Optical properties, viz. absorption and fluorescence of these QDs, are characterized from which salient changes have been observed for different ligand substitutions which, through theoretical analysis, can be associated with electronic structure properties of the QD-ligand composite systems, in particular localization of wave functions of electrons and holes in the QDs and the band matching of the HOMO-LUMO gap of the ligands. The findings can be utilized to facilitate the understanding and optimization of properties of QD biomarkers with functionalizing surface ligands for targeting cellular objects.     

Exciton spin relaxation in colloidal CdSe quantum dots at room temperature

Size dependence of spin dynamics in colloidal CdSe quantum dots (QDs) are investigated with circularly polarized pump-probe transmission spectroscopy at room temperature. The excitation energy is tuned to resonance with the lowest exciton (1S(h)1S(e)) energy of the CdSe QDs. The exciton spin dynamics of CdSe QD with the diameter of 5.2 nm shows monoexponential decay with a typical time constant of about 1-3 ps depending on the excitation energy. For the cases of CdSe QDs with smaller size (with the diameter of 4.0 and 2.4 nm), the exciton spin relaxation shows biexponential decay, a fast component with time constant of several ps and a slow one with time constant of hundreds of ps to nanosecond time scale. The fast spin relaxation arises from the bright-dark transition, i.e., J = ±1 ? -/+2 transition. This process is dominated by the hole spin flips, while the electron spin conserves. The slow spin relaxation is attributed to the intralevel exciton transitions (J = ±1 ? -/+1 transition), which is relevant to the electron spin flip. Our results indicate that the exciton spin relaxation pathways in CdSe QD are controllable by monitoring the particle size, and polarized pump-probe spectroscopy is proved to be a sensitive method to probe the exciton transition among the fine structures.     

Use of CdSe/ZnS core-shell quantum dots as energy transfer donors in sensing glucose

In the present work, CdSe/ZnS core-shell quantum dots were synthesized and conjugated with enzymes, glucose oxidase (GOD) and horseradish peroxidase (HRP). The complex of enzyme-conjugated QDs was used as QD-FRET-based probes to sense glucose. The QDs were used as an electron donor, whereas GOD and HRP were used as acceptors for the oxidation/reduction reactions involved in oxidizing glucose to gluconic acid. Electron transfer between the redox enzymes and the electrochemical reduction of H₂O₂ (or O₂) occurred rapidly, resulting in an increase of the turnover rate of the electron exchange between the substrates (e.g. glucose, H₂O₂ and O₂) and the enzymes (GOD, HRP), as well as between the QDs and the enzymes. The transfer of non-radiative energy from the QDs to the enzymes resulted in the fluorescence quenching of the QDs, corresponding to the increase in the concentration of glucose. The linear detection ranges of glucose concentrations were 0–5.0 g/l (R = 0.992) for the volume ratios of 10/5/5, 0.2–5.0 g/l (R = 0.985) for the volume ratios of 10/5/3 and 1.0–5.0 g/l (R = 0.982) for the volume ratios of 10/5/0. Temperature (29–37 °C), pH (6–10) and some ions (NH₄⁺, NO₃⁻, Na⁺, Cl⁻) had no interference effect on the glucose measurement.     

Observation of correlated emission intensity and polarization fluctuations in single CdSe/ZnS quantum dots

Time-resolved single-nanoparticle spectroscopy has been carried out to examine the luminescence characteristics of individual CdSe/ZnS core/shell quantum dots. In particular, the possible correlations between emission intensity, lifetime, spectrum, and polarization fluctuations have been investigated. The emission polarization was found to be correlated with the luminescence intensity in a nonlinear way. The low-emissive states were found to correlate with red-shifted spectrum, increased nonradiative decay, and low degree of emission polarization. The observations are consistent with the model that charged quantum dots can be emissive.