量子点材料应用于发光二极管的研究进展

量子点材料因具有独特的光学特性而被广泛应用于发光领域,用其作发光层可制成量子点发光二极管。与有机电致发光二极管相比,量子点发光二极管具有发光光谱窄、色域广、稳定性好、寿命长、制作成本低等优势。本文介绍了量子点发光器件在国内外的热点研究方向及取得的成果,并对其发展前景进行展望。     

Detection of bioconjugated quantum dots passivated with different ligands for bio-applications

Bioconjugation of quantum dots has resulted in a significant increase in resolution of biological fluorescent labeling. This intrinsic property of quantum dots can be utilized for sensitive detection of target analytes with high sensitivity; including pathogenic bacteria and cancer monitoring. The quantum dots and quantum dot doped silica nanoparticles exhibit prominent emission peaks when excited at 400 nm but on conjugation to model rabbit antigoat antibodies exhibit diminished intensity of emission peak at 600 nm. It shows that photoluminescence intensity of conjugated quantum dots and quantum dot doped silica nanoparticles could permit the detection of bioconjugation. Samples of conjugated and unconjugated quantum dots and quantum dot doped silica nanoparticles were subjected to enzyme linked immunosorbent assay for further confirmation of bioconjugation. In the present study ligand exchange, bioconjugation, fluorescence detection of bioconjugated quantum dots and quantum dot doped silica nanoparticles and further confirmation of bioconjugation by enzyme linked immunosorbent assay has been described.     

Labelling of cells with quantum dots

Colloidal quantum dots are semiconductor nanocrystals well dispersed in a solvent. The optical properties of quantum dots, in particular the wavelength of their fluorescence, depend strongly on their size. Because of their reduced tendency to photobleach, colloidal quantum dots are interesting fluorescence probes for all types of labelling studies. In this review we will give an overview on how quantum dots have been used so far in cell biology. In particular we will discuss the biologically relevant properties of quantum dots and focus on four topics: labelling of cellular structures and receptors with quantum dots, incorporation of quantum dots by living cells, tracking the path and the fate of individual cells using quantum dot labels, and quantum dots as contrast agents.     

Multicolor quantum dot encoding for polymeric particle-based optical ion sensors

Multicolor quantum dot-encoded polymeric microspheres are prepared with controllable and uniform doping levels that function as chemical sensors on the basis of bulk optode theory. TOP/TOPO-capped CdSe quantum dots and CdTe quantum dots capped with CdS (lambdaem = 610 and 700 nm, lambdaex = 510 nm) are blended with a THF solution of poly(methyl methacrylate-co-decyl methacrylate), poly(n-butylacrylate), or poly(vinyl chloride) plasticized with bis(2-ethylhexyl) sebacate without a need for ligand exchange. Polymeric microspheres are generated under mild, nonreactive conditions with a particle caster that breaks down a polymer stream containing the quantum dots into fine droplets by the vibration of a piezocrystal. The resulting microspheres exhibit uniform size and fluorescence emission intensities. Fluorescent bar codes are obtained by subsequent doping of two quantum dots with different colors and mass ratios into the microspheres. A linear relationship is found between the readout fluorescence ratio of the two types of nanocrystals and the mixing ratio. Quantum dot-encoded ion sensing optode microspheres are prepared by simultaneous doping of sodium ionophore X, chromoionophore II, a lipophilic tetraphenylborate cation exchanger, and TOPO-capped CdSe/CdS quantum dot as the fluorescent label. A net positive charge of the quantum dots is found to induce an anion-exchange effect on the sensor function, and therefore, an increased concentration of the lipophilic cation exchanger is required to achieve proper ion sensing properties. The modified quantum dot-labeled sodium sensing microspheres show satisfactory sodium response between 10(-4) and 0.1 M at pH 4.8, with excellent selectivity toward common interferences. The amount of the carried positive charges of the CdSe quantum dots is estimated as 2.8 mumol/g of quantum dots used in this study.     

Luminescent quantum dots fluorescence resonance energy transfer-based probes for enzymatic activity and enzyme inhibitors

The paper describes the development and characterization of analytical properties of quantum dot-based probes for enzymatic activity and for screening enzyme inhibitors. The luminescent probes are based on fluorescence resonance energy transfer (FRET) between luminescent quantum dots that serve as donors and rhodamine acceptors that are immobilized to the surface of the quantum dots through peptide linkers. Peptide-coated CdSe/ZnS quantum dots were prepared using a one-step ligand exchange process in which RGDC peptide molecules replace trioctylphosphine oxide (TOPO) molecules as the capping ligands of the quantum dots. The peptide molecules were bound to the surface of the CdSe/ZnS quantum dots through the thiol group of the peptide cysteine residue. The peptide-coated quantum dots were labeled with rhodamine to form the FRET probes. The emission quantum yield of the quantum dot FRET probes was 4-fold lower than the emission quantum yield of TOPO-capped quantum dots. However, the quantum dot FRET probes were sufficiently bright to enable quantitative enzyme and enzyme inhibition assays. The probes were used first to test the enzymatic activity of trypsin in solution based on FRET signal changes of the quantum dot-based enzymatic probes in the presence of proteolytic enzymes. For example, exposure of the quantum dot FRET probes to 500 microg/mL trypsin for 15 min resulted in 60% increase in the photoluminescence of the quantum dots and a corresponding decrease in the emission of the rhodamine molecules. These changes resulted from the release of rhodamine molecules from the surface of the quantum dots due to enzymatic cleavage of the peptide molecules. The quantum dot FRET-based probes were used to monitor the enzymatic activity of trypsin and to screen trypsin inhibitors for their inhibition efficiency.     

DNA-based programming of quantum dot valency, self-assembly and luminescence

The electronic and optical properties of colloidal quantum dots, including the wavelengths of light that they can absorb and emit, depend on the size of the quantum dots. These properties have been exploited in a number of applications including optical detection, solar energy harvesting and biological research. Here, we report the self-assembly of quantum dot complexes using cadmium telluride nanocrystals capped with specific sequences of DNA. Quantum dots with between one and five DNA-based binding sites are synthesized and then used as building blocks to create a variety of rationally designed assemblies, including cross-shaped complexes containing three different types of dots. The structure of the complexes is confirmed with transmission electron microscopy, and photophysical studies are used to quantify energy transfer among the constituent components. Through changes in pH, the conformation of the complexes can also be reversibly switched, turning on and off the transfer of energy between the constituent quantum dots.     

Electronic transient processes and optical spectra in quantum dots for quantum computing

Quantum dot systems are studied theoretically from the point of view of realization of quantum bit using the orbital state of electronic motion in a quantum dot. Attention is paid to several effects which can influence significantly the application of quantum dot electronic orbital states in quantum computing, for example, the effect of upconversion of the population and the incomplete depopulation of electronic orbital states, the effect of optical line broadening and presence of continuous background in optical spectra. Attention is also paid to the effect of upconversion of electronic population to the wetting-layer or above-barrier electronic states in quantum dot samples. Interaction of electrons with the longitudinal optical phonons is shown to play a significant role in these effects. Possible impact of these phenomena on the realization of quantum bit based on electronic orbital states in quantum dots is discussed.     

Blinking suppression and intensity recurrences in single CdSe-oligo(phenylene vinylene) nanostructures: experiment and kinetic model

We report time-resolved single molecule fluorescence imaging of individual CdSe quantum dots that are functionalized with oligomeric conjugated organic ligands. The fluorescence intensity trajectories from these composite nanostructures display both a strong degree of blinking suppression and intensity fluctuations with characteristic recurrence times on the order of 10-60?s. In addition, fluorescence decay rate measurements of individual hybrid nanostructures indicate significantly modified non-radiative quantum dot decay rates relative to conventional ZnS-capped CdSe quantum dots. We show that a modified diffusive reaction coordinate model with slow fluctuations in quantum dot electron energies (1S(e), 1P(e)) can reproduce the experimentally observed behaviour.     

Atomic layer deposition of lead sulfide quantum dots on nanowire surfaces

Quantum dots provide unique advantages in the design of novel optoelectronic devices owing to the ability to tune their properties as a function of size. Here we demonstrate a new technique for fabrication of quantum dots during the nucleation stage of atomic layer deposition (ALD) of PbS. Islands with sub-10 nm diameters were observed during the initial ALD cycles by transmission electron microscopy, and in situ observations of the coalescence and sublimation behavior of these islands show the possibility of further modifying the size and density of dots by annealing. The ALD process can be used to cover high-aspect-ratio nanostructures, as demonstrated by the uniform coating of a Si nanowire array with a single layer of PbS quantum dots. Photoluminescence measurements on the quantum dot/nanowire composites show a blue shift when the number of ALD cycles is decreased, suggesting a route to fabricate unique three-dimensional nanostructured devices such as solar cells.     

CdSe/CdS/SiO2 core/shell/shell nanoparticles

Quantum dots (QD) of a CdSe-ZnS core-shell structure are coated with silica spheres to improve their stability in biological buffers and biocompatibility in fluorescence imaging. We found that it was critical to transfer quantum dots from organic phase to aqueous phase before the silica shell growth process. As a result, high quality CdSe-ZnS-SiO2 core-shell-shell nanoparticles were prepared in high yields and their size and distribution are characterized with transmission electron microscopy and dynamic light scattering, which yielded uniform sizes and narrow polydispersity. Single particle fluorescence spectroscopy on the silica-protected quantum dots showed they were stronger emitters with consistent fluorescence intensity and "on-off" behaviors than bare CdSe-ZnS nanocrystals.     

In vivo Quantum‐Dot Toxicity Assessment

Quantum dots have potential in biomedical applications, but concerns persist about their safety. Most toxicology data is derived from in vitro studies and may not reflect in vivo responses. Here, an initial systematic animal toxicity study of CdSe–ZnS core–shell quantum dots in healthy Sprague–Dawley rats is presented. Biodistribution, animal survival, animal mass, hematology, clinical biochemistry, and organ histology are characterized at different concentrations (2.5–15.0 nmol) over short‐term (<7 days) and long‐term (>80 days) periods. The results show that the quantum dot formulations do not cause appreciable toxicity even after their breakdown in vivo over time. To generalize the toxicity of quantum dots in vivo, further investigations are still required. Some of these investigations include the evaluation of quantum dot composition (e.g., PbS versus CdS), surface chemistry (e.g., functionalization with amines versus carboxylic acids), size (e.g., 2 versus 6 nm), and shape (e.g., spheres versus rods), as well as the effect of contaminants and their byproducts on biodistribution behavior and toxicity. Combining the results from all of these studies will eventually lead to a conclusion regarding the issue of quantum dot toxicity.     

High-Sensitivity Fluorescence Lifetime Thermal Sensing Based on CdTe Quantum Dots

The potential use of CdTe quantum dots as luminescence nano-probes for lifetime fluorescence nano-thermometry is demonstrated. The maximum thermal sensitivity achievable is strongly dependent on the quantum dot size. For the smallest sizes (close to 1 nm) the lifetime thermal sensitivity overcomes those of conventional nano-probes used in fluorescence lifetime thermometry.     

A Ge/Si heterostructure nanowire-based double quantum dot with integrated charge sensor

One proposal for a solid-state-based quantum bit (qubit) is to control coupled electron spins on adjacent semiconductor quantum dots. Most experiments have focused on quantum dots made from III-V semiconductors; however, the coherence of electron spins in these materials is limited by hyperfine interactions with nuclear spins. Ge/Si core/shell nanowires seem ideally suited to overcome this limitation, because the most abundant nuclei in Ge and Si have spin zero and the nanowires can be chemically synthesized defect-free with tunable properties. Here, we present a double quantum dot based on Ge/Si nanowires in which we can completely control the coupling between the dots and to the leads. We also demonstrate that charge on the double dot can be detected by coupling it capacitively to an adjacent nanowire quantum dot. The double quantum dot and integrated charge sensor serve as an essential building block to form a solid-state qubit free of nuclear spin.     

Thermal conductivity of Si-Ge quantum dot superlattices

Quantum dot superlattices (QDSLs) have been proposed for thermoelectric applications as a means of increasing thermal conductivity, σ, and reducing the lattice thermal conductivity, κ(l), to increase the dimensionless thermoelectric figure of merit, ZT. To fully exploit the thermoelectric potential of Si-Ge quantum dot superlattices (QDSLs), we performed a thorough study of the structural interplay of QDSLs with κ(l) using Green-Kubo theory and molecular dynamics. It was found that the resulting κ(l) has less dependence on the arrangement of the dots than to dot size and spacing. In fact, regardless of arrangement or concentration, QDSLs show a minimum κ(l) at a dot diameter of 1.4-1.6 nm and can reach values as low as 0.8-1.0 W mK?1, increasing ZT by orders of magnitude over bulk Si and Ge. The drastic reduction of thermal conductivity in such a crystalline system is shown to be the result of both the stress caused by the dots as well as the quality of the Si-Ge interface.     

Crosslinked Carbon Dots as Ultra‐Bright Fluorescence Probes

Carbon dots (surface‐passivated small carbon nanoparticles) are crosslinked to result in fluorescence probes containing one or multiple dots. For the single‐dot probes, the crosslinking further stabilizes the dot structure, while for those packed with multiple dots, the individual probe imaging results demonstrate that the fluorescence properties are additive, with more dots for higher emission intensities in a proportional fashion, thus enabling the preparation of ultra‐bright fluorescence probes.     

异质外延自组织量子点弹性应变场分布的研究

通过有限元法,在ANSYS环境下,利用二维模型对自组织应变外延异质结透镜形量子点的应力应变分布情况进行了系统分析。分析过程分别考虑了孤立量子点系统、单层多量子点系统以及量子点超晶格系统3种情况,结果表明单层和超晶格多量子点系统衬底之间存在的长程相互作用力对量子点及其周围的应力应变分布有显著影响。在计算应变对多量子点系统的电子结构的影响时,必须将多量子点系统整体考虑。     

Temperature Effects on the Self-trapping Energy of a Polaron in a GaAs Parabolic Quantum Dot

The temperature and the size dependences of the self-trapping energy of a polaron in a GaAs parabolic quantum dot are investigated by the second order Rayleigh-Schrodinger perturbation method using the framework of the effective mass approximation. The numerical results show that the self-trapping energies of polaron in GaAs parabolic quantum dots shrink with the enhancement of temperature and the size of the quantum dot. The results also indicate that the temperature effect becomes obvious in small quantum dots     

异质外延自组织锥形量子点长程相互作用对弹性应变场分布的影响

利用有限元法,在ANSYS 环境下,利用二维模型对自组织应变外延异质结锥形量子点的应力应变分布情况进行了系统分析.分析过程分别考虑了孤立锥形量子点系统、单层多量子点系统以及量子点超晶格系统三种情况,结果表明,单层和超晶格多量子点系统衬底之间存在的长程相互作用力对量子点及其周围的应力应变分布有显著影响.在计算应变对多量子点系统的电子结构的影响时,必须将多量子点之间的相互作用对应变的贡献考虑进去.     

量子点/碳复合材料在碱金属离子电池的应用进展EI北大核心

碱金属离子电池作为可充电电池,是目前重要的储能设备之一。它凭借能量密度大、工作电压高、无“记忆效应”、自放电小、绿色无污染等优点在近些年来受到人们的广泛关注。电极材料是影响碱金属离子电池电化学性能的重要因素之一,因此,寻求比容量高、结构稳定的电极材料是推动碱金属离子电池发展的关键。量子点/碳复合材料(QDs/C)集合量子点与碳材料的优势,是碱金属离子电池优异的候选电极材料。本文首先对量子点进行简要介绍,然后分别综述单质量子点/碳复合材料、化合物量子点/碳复合材料及异质结构量子点/碳复合材料在碱金属离子电池中的应用进展。最后,分析量子点/碳复合材料作为碱金属离子电池电极材料的优势与不足,针对目前存在的问题提出了未来发展的方向:(1)探索新型方法,解决量子点及其复合材料的团聚问题;(2)研究SEI膜的结构性能等,解决首次库仑效率偏低的问题;(3)明确反应机理,获取更优异的电化学性能。     

Transient reflection: a versatile technique for ultrafast spectroscopy of a single quantum dot in complex environments

Increasingly complex structures such as optical antennas or cavities are coupled to self-assembled quantum dots to harvest their quantum-optical properties. In many cases, these structures pose a problem for common methods of ultrafast spectroscopy used to write and read out the state of the quantum dot. We present a pure far-field method that only requires optical access to the quantum dot and does not impose further restrictions on sample design. We demonstrate Rabi oscillations and perturbed free induction decay of single GaAs quantum dots that have a dipole moment as small as 18 D. Our method will greatly facilitate ultrafast spectroscopy of complex quantum-optical circuits.