CdSe quantum dots decorated by mercaptosuccinic acid as fluorescence probe for Cu

Water-soluble CdSe quantum dots (QDs) were synthesized using mercaptosuccinic acid (MSA) as a stabilizer. The growth process and characterization of CdSe quantum dots were determined by transmission electron microscopy (TEM), X-ray diffraction (XRD), photoluminescence (PL) spectroscopy, Ultraviolet-visible (UV-vis) spectroscopy, and Fourier transform infrared (FT-IR) spectroscopy. Results demonstrated the MSA-capped CdSe QDs were highly crystalline and possessed good optical properties. Further, the resulting products could be used as fluorescent probes to detect Cu²⁺ ions in physiological buffer solution. The response was linearly proportional to the concentration of Cu²⁺ ion in the range 2×10⁻⁸- 3.5×10⁻⁷ mol L⁻¹ with a detection limit of 3.4 nmol L⁻¹.     

Non-injection and one-pot approach to CdSe: Eu<Superscript>3+</Superscript> hybrid nanocrystals with tunable photoluminescence from green to red

Europium ion-doped CdSe hybrid nanocrystals (CdSe:Eu³⁺ NCs) as a class of new luminescent materials have drawn increasing attention in recent years owing to their remarkable optical properties. In this paper, we report a facile method to prepare CdSe:Eu³⁺ NCs using oleic acid (OA) as the capping agent. With this non-injection and one-pot synthesized approach, the formation and surface passivation of CdSe:Eu³⁺ NCs are performed simultaneously and result in intrinsic luminescence. The as-prepared CdSe:Eu³⁺ NCs are characterized by transmission electron microscopy, X-ray diffraction, and energy-dispersive X-ray spectroscopy (EDX). Their optical properties are also studied by UV–vis and photoluminescence spectra. Moreover, the effects of feed ratios and reaction temperatures on the optical properties are further investigated. The results show that the luminescent spectra of CdSe:Eu³⁺ NCs are tunable from green (490 nm) to red (630 nm) and gradually redshift with the increase of the nanoparticle size from 2.5 to 4.4 nm. Upon decoration with 2-thenoyltrifluoroacetone (TTA), the luminescence of europium ion drastically increases and efficient energy transfer from CdSe host to the europium ion is proposed. In addition, an MTT and apoptosis assay show CdSe:Eu³⁺ NCs have low cellular toxicity and could be used as fluorescence imaging for human epithelial type 2 (Hep-2) cells. These properties make CdSe:Eu³⁺ NCs a potential candidate for biological labeling, immunoassays, and optical sensing.

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Graphical abstract Stable and luminescent CdSe:Eu³⁺ hybrid nanocrystals were synthesized, and the luminescence is tunable from green to red by the variation of reaction temperatures and feed ratios. Moreover, CdSe:Eu³⁺ NCs show low cellular toxicity and could be used as fluorescence probes for Hep-2 cells.

     

Fixed-distance coupling and encapsulation of heterogeneous quantum dots using phonon-assisted photo-curing

We propose a novel method of coupling heterogeneous quantum dots at fixed distances and capsulating the coupled quantum dots by utilizing nanometric local curing of a photo-curable polymer caused by multistep electronic transitions based on a phonon-assisted optical near-field process between quantum dots. Because the coupling and the capsulating processes are triggered only when heterogeneous quantum dots floating in a solution closely approach each other to induce optical near-field interactions between them, the distances between the coupled quantum dots are physically guaranteed to be equal to the scale of the optical near fields. To experimentally verify our idea, we fabricated coupled quantum dots, consisting of CdSe and ZnO quantum dots and a UV-curable polymer. We also measured the photoluminescence properties due to the quantum-dot coupling and showed that the individual photoluminescences from the CdSe and ZnO quantum dots exhibited a trade-off relationship.     

CdSe/ZnS量子点在倏逝波光纤pH传感中的应用

将新型量子点荧光传感技术与光纤倏逝波传感技术相结合,发展了一种基于量子点荧光效应并结合倏逝波传导进行溶液酸碱度检测的新型传感技术,具有灵敏度高、检测速度快、便于微环境检测、可实现远程探测、实时监测和原位分析等特点。详细介绍了用于倏逝波传感的锥柱组合型光纤荧光探头的制备方法,量子点在光纤探头表面的修饰流程,光谱与强度两种光纤pH传感平台的建立,并分别从响应范围、线性度、重复性和稳定性等方面对CdSe/ZnS量子点应用于光纤pH传感进行了评价。结果表明,在pH值为2~12的范围内,CdSe/ZnS量子点的荧光光谱信号的峰位在强酸和强碱的情况下都会产生红移,且红移量随pH值的变化呈线性关系,其量子点荧光强度信号随pH值的减小呈线性降低关系,通过在强酸和强碱下交替测试的实验表明其具有较好的重复性,利用荧光强度传感平台进行实时监测的实验表明其具有较好的稳定性。因此,将CdSe/ZnS量子点用于倏逝波光纤pH传感具有可行性,在生物化学、环境监测、医学临床、食品安全等领域的pH值测量方面有着广泛的应用前景。     

Single-Photon Emitter at 80 K Based on a Dielectric Nanoantenna with a CdSe/ZnSe Quantum Dot

The emission characteristics of a source of single photons based on an epitaxial heterostructure with CdSe/ZnSe quantum dots and a cylindrical waveguide with a varying cross section formed in a resist layer by electron-beam lithography are investigated. It is shown that a flux of single photons at a wavelength of 530 nm with an average rate of about 1 MHz and the value g(²)(0) = 0.15 ± 0.03 of the second-order correlation function at zero delay can be generated under optical pumping at 80 K.     

Porphyrin decorated CdSe quantum dots for direct fluorescent sensing of metal ions

In this study, we report on a novel hybrid structure for the direct sensing of metal ions based on the use of CdSe quantum dots functionalized with tetrapyridyl-substituted porphyrin, a cation-selective carrier. It is shown that the porphyrin ion carrier coordinates to Cd atoms of the CdSe quantum dots through the Lewis basic pyridyl groups. The porphyrin-quantum dot ligation allows for the direct communication between the porphyrin and the underlying CdSe quantum structure. The quantum yield of CdSe is maintained despite the robust capping generated when the unmetallated porphyrins coordinate onto the quantum dots. Upon coordination with zinc ions, this porphyrin capping is shown to strongly contribute to the increase in the fluorescence efficiency of CdSe, via an activating interaction with the quantum dots surface. The results provide the grounds for the development of highly sensitive and selective nano-optode sensing systems.     

Hole mobility and trapping in PVK films doped with CdSe/CdS and CdSe quantum dots

Experimental study of the hole mobility in polyvinylcarbazole (PVK) films doped with two kinds of nanocrystals, on bare core CdSe and core-shell CdSe/CdS quantum dots, with concentrations ranging from 3 · 10¹⁰ to 3 · 10¹⁵ cm⁻³, is presented. The quantum dots investigated were made using colloidal chemistry. The hole mobility was measured using the time-of-flight technique as a function of the applied electrical field in the range 10⁵–10⁶ V/cm and for temperatures from 20°C to 50°C. The transient curves, being featureless on a linear plot, show on a double logarithmic scale a sharp inflection point indicating a dispersive carrier drift process. The recovered values of the mobility are in the range 3 · 10⁻⁸–10⁻⁶ cm²·V⁻¹·s⁻¹ and their field and temperature dependences can be analyzed formally within the framework of the Gaussian disorder model proposed by B?ssler. The energetic disorder is, within the experimental accuracy, independent of the concentration and type of quantum dots for the CdSe quantum dots at all concentrations and for the CdS/CdSe quantum dots up to 10¹⁴ cm⁻³. The spatial disorder factors are very large (from 5.3 to 8.7) and do not depend in a systematic way upon the type and concentration of quantum dots (QDs). The experiments show that the apparent mobility does not change considerably with concentration, but it was found that the samples with CdSe/CdS quantum dots at concentrations from 10¹⁵ to 3 · 10¹⁵ cm⁻³ show a decreased photocurrent response. The dependence of the time-integrated transients (corresponding to the full charge value) upon the quantum-dot concentration has been determined. Differences in total photogenerated charge for pure and doped polymer films imply that the quantum dots of that type are the hole traps with capture times much more smaller than the transit time and with emission times a few orders longer than the transit time. CdSe quantum dots without a shell do not seem to exhibit the same properties as core shells and do not produce considerable changes in the charge transfer, even at a density of 10¹⁵ cm⁻³.     

Nanosize induced effects in luminescent ZnS:Mn2+ quantum dots

Nanocrystals (NCs) of II–VI semiconductors of few nanometers average size, called quantum dots (QDs), are now intensely investigated as radiation detectors. Besides the expected quantum confinement and influence of surface states, our electron paramagnetic resonance investigations of cZnS QDs doped with Mn²⁺ ions, correlated with structural data, underline that other properties should be also taken into consideration in developing the II–VI semiconductor QDs as radiation detectors. Thus, the preferential localization of Mn²⁺ in the core of the cubic ZnS QDs at substitutional Zn²⁺ cation sites next to a stacking lattice defect is expected to lead, besides changes in the impurity energy levels, to specific aggregation properties. An outer shell of different composition can also influence the structural properties of the QDs core with effects on the optical properties as well.     

Low toxic and highly luminescent CdSe/Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Zn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>S quantum dots with thin organic SiO<Subscript>2</Subscript> coating for application in cell imaging

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 Zn_1?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 Zn_1?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 Zn_1?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.     

Electronic tongue — An array of non-specific chemical sensors — For analysis of radioactive solutions

A variety of novel sensing materials on the basis of phosphine oxides for solvent polymeric sensors have been developed and studied. It was found that phosphine oxide sensors exhibit good sensitivity to rare earth metal cations, such as La³⁺, Pr³⁺, Nd³⁺, Eu³⁺ and also to Y³⁺. Polymeric sensors can be comprised into electronic tongue sensor arrays that may allow detection of several rare-earth metal ions simultaneously in mixed solutions. Such sensor arrays are highly promising for environmental and industrial sensing, e.g., for analysis of spent nuclear fuel.     

Spin-orbit coupling and crystal-field splitting in the electronic and optical properties of nitride quantum dots with a wurtzite crystal structure

We present an sp ³ tight-binding model for the calculation of the electronic and optical properties of wurtzite semiconductor quantum dots (QDs). The tight-binding model takes into account strain, piezoelectricity, spin-orbit coupling and crystal-field splitting. Excitonic absorption spectra are calculated using the configuration interaction scheme. We study the electronic and optical properties of InN/GaN QDs and their dependence on structural properties, crystal-field splitting, and spin-orbit coupling.     

Fabrication of rare-earth/quantum-dot nanocomposites for color-tunable sensing applications

We developed a new fluorescent nanocomposite by using a layer-by-layer approach to link NaYF₄:Ce,Tb rare-earth (RE) nanocrystals and CdSe/ZnSe semiconductor quantum dots (QDs) with opposite charges. Under ultraviolet light excitation, the nanocomposites exhibited both the green Tb emission centered at 550 nm, and the red QD emission at 650 nm. Sensing applications showed that the red QD emission was quenched by trace amount of Cu²⁺ (or Ag⁺) ions due to the ion displacement mechanism, while the green RE emission kept constant. Thus, the nanocomposites with the decreased QD/RE emission intensity ratio and changed fluorescence output color provided a visible “indicator” to detect metal ions quantificationally. In comparison with single emission materials, the dual emission nanocomposites can be a more reliable probe for various sensing applications.     

Encapsulation of highly confined CdSe quantum dots for defect free luminescence and improved stability

This is the first report on the generation of trap states and their effective elimination in highly confined CdSe quantum dots in order to obtain enhanced and stable optical properties prepared by aqueous route. Surface plays an important role in optical properties of quantum dots (QDs) and surface modification of quantum dots can improve optical properties. In present work luminescent CdSe QDs were prepared using 2-Mercaptoethanol (2-ME) as stabilizing agent and encapsulated by polymer. Different concentrations of 2-ME were used to tune the emission spectra with respect to their reduced size. Addition of 2-ME to CdSe QDs enhances the trap emission and quenching band edge emission due to (i) increased surface to volume ratio and; (ii) presence of high concentration of sulfide ions as confirmed from EDX analysis as sulfide ions possesses the hole scavenging characteristics. Polymer encapsulation of QDs was carried out to make them stable and to improve their optical properties. Even though there are previous reports addressing the improved optical properties by polymer encapsulation and silica encapsulation but experimentally it has not been reported yet experimentally. In this work we have synthesized and characterized water soluble polymer encapsulated QDs and proved the facts experimentally. Photoluminescence spectroscopy clearly reveals the role of polymer encapsulation in boosting the optical properties of CdSe QDs. FTIR spectra validate the presence of biocompatible functional groups on CdSe4/PEG (Polymer encapsulated QDs).     

Laser-Patterned Carbon-Supported Graphitic Carbon Nitride Quantum Dots for Flexible Nanozyme-Based Fluoride Sensor

Graphitic carbon nitride quantum dots (g-CNQDs)-based colorimetric sensors are typically solution-based and hence incompatible with wearable electronics. Today's competitive technology demands safe and reliable, high-performance sensors suitable for integration with sophisticated electronics—all at a low cost. Herein, a flexible and reusable solid-state fluoride ion sensor manufactured by combining the intriguing surface properties of laser-patterned carbon (LP-C) with the sensitivity of g-CNQDs is reported. LP-C is obtained by direct IR-laser writing onto polyimide films, and g-CNQDs are synthesized via a solvent-free and zero-waste green process. The hybrid of LP-C and g-CNQDs (g-CNQDs/LP-C), mimics the natural enzyme horseradish peroxidase and oxidizes the chromogenic substrate 3,3’,5,5’-tetramethylbenzidine in the presence of H₂O₂ in acidic media. The highly selective and user-friendly nanozyme sensors feature a lower limit of detection of 0.568 ± 0.006  × 10⁻⁶ m (23.8 ± 1.5 µg L⁻¹) with linearity in the range of 0.5 × 10⁻⁶ to 100  × 10⁻⁶ m . A sensing mechanism based on the electronic transitions of g-CNQDs and LP-C, the two variants of nitrogen-containing carbon used in this work, is established. Finally, the device is tested for fluoride ion sensing in natural water samples collected from the Uhl river in Mandi, India.     

Strong Photoluminescence Enhancement from Colloidal Quantum Dot Near Silver Nano-Island Films

We present the fabrication and optical investigation of highly random self-assembled, nano-scale films, probing their influence on the luminescence properties of near surface CdSe/ZnS colloidal quantum dots. When compared to quantum dots distributed on unstructured quartz substrates, the average luminescence intensity is found to be enhanced by a factor of 160×. The silver nanoparticles are prepared using slow thermal evaporation on quartz substrates and post-deposition annealing to produce a randomly-arranged layer of smooth nano-islands. Clear polarization dependent hot spots are observed. Such hot spots deliver a maximal enhancement of the emission intensity of 240× and have a spatial density of (0.050±0.002) μm^− 2. The results show that silver nano-island films strongly enhance the optical efficiency of near quantum dots emitters.     

Optical absorption and refraction index change of a confined exciton in a spherical quantum dot nanostructure

Electronic energies of an exciton confined in a strained Zn_1−x Cd _x Se/ZnSe quantum dot have been computed as a function of dot radius with various Cd content. Calculations have been performed using Bessel function as an orthonormal basis for different confinement potentials of barrier height considering the internal electric field induced by the spontaneous and piezoelectric polarizations. The optical absorption coefficients and the refractive index changes between the ground state (L = 0) and the first excited state (L = 1) are investigated. It is found that the optical properties in the strained ZnCdSe/ZnSe quantum dot are strongly affected by the confinement potentials and the dot radii. The intensity of the total absorption spectra increases for the transition between higher levels. The obtained optical nonlinearity brings out the fact that it should be considered in calculating the optical properties in low dimensional semiconductors especially in quantum dots.     

CdSe量子点的线性和非线性光学特性

主要从实验和理论两个方面,探讨了强受限尺寸区域内不同尺寸对CdSe量子点线性和非线性光学性质的影响.用吸收光谱研究了量子点尺寸与吸收峰之间的关系,用皮秒Z扫描技术研究了共振和非共振情况下(激发光波长分别为532和1064nm),尺寸与三阶非线性极化率之间的关系.基于电子能量状态理论和局域场增强理论对量子点进行分析,得到了CdSe不同尺寸的三阶非线性效应,研究了尺寸对量子点非线性光学性质的影响.结果表明,由激发态粒子数布局改变和纳米颗粒增大引起的非线性共振增强效应相当,二者共同作用使得三阶极化率增强20倍左右,且用532nm的共振频率激发4.3nm CdSe量子点时,χ⁽³⁾具有最大值2.0×10^-11esu. 关键词： CdSe量子点 三阶非线性 Z扫描')" href="#">Z扫描 量子限域效应     

Self-diffraction at a dynamic photonic crystal formed in a colloidal solution of quantum dots

Self-diffraction at a one-dimensional dynamic photonic crystal formed in the colloidal solution of CdSe/ZnS quantum dots has been discovered. This self-diffraction appears simultaneously with self-diffraction at induced transparency channels at the resonant excitation of the main electron–hole (excitonic) transition of quantum dots by two laser beams with a Gaussian intensity distribution over the cross section. It is shown that a nonlinear change in the absorption of colloidal quantum dots results in the formation of a transparency channel and an induced amplitude diffraction grating, and a significant nonlinear change in the refractive index (Δn ≈ 10^?3) in the absorbing medium is responsible for the formation of the dynamic photonic crystal. Self-diffracted laser beams are revealed propagating not only in directions corresponding to self-diffraction at the induced diffraction grating but also in directions satisfying the Laue condition.     

Studying the possibility of deep laser cooling of <Superscript>24</Superscript>Mg atoms in an optical lattice: Two-level quantum model

The possible deep laser cooling of ²⁴Mg atoms in a deep optical lattice in the presence of an additional pumping field resonant to the narrow 3s3s¹S₀ → 3s3p³P₁ (λ = 457 nm) optical transition is studied. Two quantum models of the laser cooling of atoms in the optical trap are compared. One is based on the direct numerical solution to the kinetic quantum equation for an atomic density matrix; it considers both optical pumping and quantum recoil effects during interaction between the atoms and field photons. The second, simplified model is based on decomposing the states of the atoms over the levels of vibration in the optical trap and analyzing the evolution of these states. The comparison allows derivation of optical field parameters (pumping field intensity and detuning) that ensure cooling of the atoms to minimal energies. The conditions for fast laser cooling in an optical trap are found.     

Optical characterization of quantum dots entrained in microstructured optical fibers

We present a study of the basic optical properties of colloidal CdSe/ZnS core/shell quantum dots entrained in a microstructured optical fiber. Quantum dots suspended in heptane were pulled into the holes surrounding the solid core of a microstructured optical fiber of the holey fiber class via capillary action and are found to remain in the fiber. In this experiment, a laser coupled into the fiber photoexcited quantum dots along the length of the fiber. Quantum dot emission was observed to couple into the fiber core and propagate along the fiber. To investigate the use of such a system in fiber-based light generation or amplification, a second laser overlapping the low-energy portion of the quantum dot emission was simultaneously coupled into the fiber. We observed apparent amplification of this light when photoexciting the quantum dots well above their bandedge.