Highly luminescent blue emitting CdS/ZnS core/shell quantum dots via a single-molecular precursor for shell growth

Highly luminescent blue-emitting CdS/ZnS core/shell quantum dots (QDs) were synthesized in N-oleoylmorpholine by two facile steps: first, the CdS core QDs were prepared via a simple one-pot method involving a direct reaction of Cd precursor cadmium stearate and S precursor S powder in solvent N-oleoylmorpholine; second, ZnS shells were successively overcoated on CdS core through the decomposition of single molecular precursor zinc diethyldithiocarbamate. The thickness of shell was precisely tuned by controlling drip feed speed and amount of shell precursor. The obtained CdS/ZnS core/shell QDs showed the maximum photoluminescent quantum yield of 54.8% and narrow spectra bandwidth, exhibiting high monodispersity, good color purity and long fluorescent lifetimes. The CdS/ZnS core/shell QDs with tunable emission wavelength of 424–470 nm were obtained by controlling the thickness of ZnS shell overgrown on different-sized CdS QDs, which are promising materials for blue light-emitting devices.     

核壳结构CdS/ZnS荧光量子点的制备与荧光性能研究

以氧化镉为镉源、硫单质为硫源、油酸为配体、在十八烯体系中合成单分散的CdS纳米颗粒,研究了配体浓度对纳米微粒的生长动力学、颗粒尺寸分布的影响.采用乙基黄原酸锌作为Zn、S源的反应前体,采用逐滴滴加的方法制备了具有核壳结构的CdS/ZnS量子点,吸收光谱和荧光光谱表明CdS/ZnS纳米粒子比单一的CdS纳米粒子具有更优异的发光特性.透射电子显微镜、X射线粉末衍射、X射线光电子能谱、选区电子衍射证明ZnS在CdS表面进行了有效包覆.所制备核壳结构纳米粒子具有较好的尺寸分布,荧光发射峰半高峰宽为18～20nm,荧光量子产率达40%.     

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.     

Interface/surface optical phonon in onion-like quantum dots

We calculate the interface/surface phonon in onion-like quantum dots by using dielectric continuum approach. The form of the phonon potential of the onion-like quantum dots and the electron-phonon interaction Hamiltonian are obtained. Core/shell quantum dots and quantum dot quantum well are studied in detail. The interface/surface phonon modes and corresponding frequencies as a function of the sizes of the structure are investigated. We observe that the asymptotic behavior is depended on the host medium. The sensitivity of the interface/surface phonon frequencies are decreasing with the increasing of the shell thickness. The contribution of different angular momentum quantum numbers to the electron-phonon interaction are given for the onion-like quantum dots. Numerical calculations are performed on the CdS/ZnS and CdS/ZnS/CdS heterostructure which is embedded in the polyethylene.     

Highly luminescent and quantum-yielding CdSe/ZnS core/shell quantum dots synthesized by a kinetically controlled succession route in 18DMA

Highly luminescent and quantum-yielding (QY) CdSe/ZnS core/shell quantum dots (CS QDs) were synthesised via a new succession route in a non-toxic solvent, N,N-Dimethyl-octadecyl-tertiary-amine(18DMA) at a mild temperature. The CS QDs were also proven to be as efficient in reaching high quantum yields (up to 74%) as their reported high-temperature synthesis with organic phosphine ligands. It was demonstrated that the synthesis temperatures directly determine the size by controlling the rate of the monomer diffusion and adsorption. It was also found that the amount of surfactant oleic acid determined the QY of the QDs, whereas it had little influence on the crystallisation.     

Facile consecutive solvothermal growth of highly fluorescent InP/ZnS core/shell quantum dots using a safer phosphorus source

The work presents a facile, stepwise synthetic approach for the production of highly fluorescent InP/ZnS core/shell quantum dots (QDs) by using a safer phosphorus (P) precursor. First, InP quantum dots (QDs) were solvothermally prepared at 180?°C for 24 h by using a P source of P(N(CH(3))(2))(3). The as-grown InP QDs were consecutively placed in another solvothermal condition for ZnS shell overcoating. In contrast to the almost non-fluorescent InP QDs, due to their highly defective surface states, the ZnS-coated InP QDs were highly fluorescent as a result of effective surface passivation. After the shell growth, the resulting InP/ZnS core/shell QDs were subjected to a size-sorting processing, by which red- to green-emitting QDs with quantum yields (QYs) of 24-60% were produced. Solvothermal shell growth parameters such as the reaction time and Zn/In solution concentration ratio were varied and optimized toward the highest QYs of core/shell QDs.     

Novel quantum dots: Water-based CdTeSe/ZnS and YAG hybrid phosphor for white light-emitting diodes

Novel water-based core/shell CdTeSe/ZnS quantum dots (QDs) were synthesized by aqueous method. The CdTeSe/ZnS QDs were investigated by high resolution transmission electron microscopy, energy dispersive spectrometry, UV–vis absorption spectra, and photoluminescence spectrum. The as-prepared QDs capped with ZnS shell were spherical in shape with an excellent quantum yield of 16% and emitted bright yellow light. In addition, the CdTeSe/ZnS QDs can be excited by blue or near-UV region, which is an advantage over wavelength converters for white light-emitting diodes (LEDs). White LEDs based on CdTeSe/ZnS QDs, commercially known as Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce), and hybrid phosphor of CdTeSe/ZnS QDs and YAG:Ce, were fabricated. The luminescent properties of the resultant white LEDs were evaluated. The higher red-component in the emission spectrum from CdTeSe/ZnS QDs increased the color rendering index (CRI) value of the commercial YAG:Ce-based white LEDs, and the hybrid phosphor-based white LED had CIE-1993 color coordinate, color temperature, and CRI values of (0.3125, 0.2806), 7108 K and 83.3, respectively.     

胶体量子点多色LED的设计、制备和表征

量子点LED采用胶体量子点为LED发光层,通过调节量子点的尺寸可以制作出覆盖可见以及近红外光谱的量子点LED(QD-LED),而且量子点LED器件发出的光谱范围很窄(光谱半高宽可达30 nm).为了研究不同发光颜色的QD-LED器件特性,本文采用具有523 nm和608 nm发光波长的CdSe/ZnS核壳型量子点为发光层、poly-TPD为空穴传输层、ZnO为电子传输层,制备了量子点红光和绿光LED并讨论了器件的相关特性.这些结果对量子点LED在飞机驾驶舱以及医疗器械照明方面的应用提供了参考,但要满足商业化的需求其寿命、亮度以及效率还需要进一步的提高.     

Zinc Thiolate Enables Bright Cu‐Deficient Cu‐In‐S/ZnS Quantum Dots

Copper indium sulfide (CIS) colloidal quantum dots (QDs) are a promising candidate for commercially viable QD‐based optical applications, for example as colloidal photocatalysts or in luminescent solar concentrators (LSCs). CIS QDs with good photoluminescence quantum yields (PLQYs) and tunable emission wavelength via size and composition control are previously reported. However, developing an understanding and control over the growth of electronically passivating inorganic shells would enable further improvements of the photophysical properties of CIS QDs. To improve the optical properties of CIS QDs, the focus is on the growth of inorganic shells via the popular metal‐carboxylate/alkane thiol decomposition reaction. 1) The role of Zn‐carboxylate and Zn‐thiolate on the formation of ZnS shells on Cu‐deficient CIS (CDCIS) QDs is studied, 2) this knowledge is leveraged to yield >90% PLQY CDCIS/ZnS core/shell QDs, and 3) a mechanism for ZnS shells grown from zinc‐carboxylate/alkane thiol decomposition is proposed.     

Co2+掺杂水溶性ZnS量子点的制备及其光致发光性能

采用共沉淀法,以3-巯基丙酸为表面修饰剂,成功制备出Co2+掺杂水溶性ZnS量子点。采用X射线衍射仪、透射电子显微镜、原子发射光谱仪、紫外-可见吸收光谱仪和荧光分光光度计等,研究了Co2+掺杂剂及掺杂量对ZnS量子点的晶体结构、形貌和发光性能等的影响。结果表明:所得产物均为ZnS立方型闪锌矿结构,量子点呈不规则球形,粒径主要集中在5.2 nm左右;掺杂样品发红色荧光,发光性能明显增强,属于Co2+形成的杂质能级(4A1—4T1)与缺陷的复合发光。同时,利用红外吸收光谱对Co2+掺杂水溶性ZnS量子点的形成机理进行了初步探讨。     

Synthesis of highly photo-stable CuInS2/ZnS core/shell quantum dots

CuInS₂ quantum dots are considered near-ideal fluorophores based on their bright emission and low toxicity. However, CuInS₂ quantum dots are still bothered by their sensitivity to surface chemistry and chemical environment. Traditionally, the CIS QDs require an additional coating process to be encapsulated inside silica sphere or organic polymer. Up till now, few works have been made concerning improving the intrinsic stability of CIS QDs. In an effort to improve the stability of CuInS₂ quantum dots, we came up with a new method by increasing the ZnS shell thickness. These QDs were characterized by photoluminescence, HRTEM, XRD and XRF analysis. We investigated the influence of ZnS shell thickness on the ambient stability of CIS/ZnS QDs. The results demonstrated that a thicker ZnS shell helped significantly improve both photostability and chemical stability of the QDs. Finally, the thick shell QDs were dispersed into transparent polymer matrix and fabricated into a LED device, which also gave much more stability compared with conventional QDs.     

High color rendering index white LED based on nano-YAG:Ce3+ phosphor hybrid with CdSe/CdS/ZnS core/shell/shell quantum dots

To improve the poor color rendering index (CRI) of YAG:Ce-based white light-emitting diode (LED) due to the lack of red spectral component, core/shell/shell CdSe/CdS/ZnS quantum dots (QDs) were synthesized and blended into nano-YAG:Ce³⁺ phosphors. Prominent spectral evolution has been achieved by increasing the content of QDs. A white LED combining a blue LED with the blends of nano-YAG phosphors and orange- and red-emission QDs with a weight ratio of 1:1:1 was obtained. This kind of white LED showed excellent white light with luminescent efficiency, color coordinates, CRI and correlated color temperature (CCT) of 82.5?lm/W, (0.3264, 0.3255), 91 and 4580?K, respectively.     

Electronic structure and optical property of semiconductor nanocrystallites

Semiconductor nanostructures show many special physical properties associated with quantum confinement effects, and have many applications in the opto-electronic and microelectronic fields. However, it is difficult to calculate their electronic states by the ordinary plane wave or linear combination of atomic orbital methods. In this paper, we review some of our works in this field, including semiconductor clusters, self-assembled quantum dots, and diluted magnetic semiconductor quantum dots. In semiconductor clusters we introduce energy bands and effective-mass Hamiltonian of wurtzite structure semiconductors, electronic structures and optical properties of spherical clusters, ellipsoidal clusters, and nanowires. In self-assembled quantum dots we introduce electronic structures and transport properties of quantum rings and quantum dots, and resonant tunneling of 3-dimensional quantum dots. In diluted magnetic semiconductor quantum dots we introduce magnetic-optical properties, and magnetic field tuning of the effective g factor in a diluted magnetic semiconductor quantum dot.     

Calixarene capped quantum dots as luminescent probes for Hg ions

Luminescent and stable CdSe/ZnS core/shell quantum dots (QDs) capped with sulfur calixarene are prepared for the selective determination of mercury ions in acetonitrile with high sensitivity.     

Optical properties of water-soluble l-cysteine-capped alloyed CdSeS quantum dot passivated with ZnSeTe and ZnSeTe/ZnS shells

Alloyed quantum dots (QDs) passivated with shell materials have valuable optical characteristics suitable for a wide array of applications. In this work, alloyed ternary CdSeS QDs passivated with ZnSeTe and ZnSeTe/ZnS shells have been synthesized via a hot-injection method and a ligand exchange reaction employing l-cysteine as a thiol ligand has been used to obtain these water-soluble nanocrystals for the first time. The photoluminescence (PL) quantum yield (QY) of alloyed l-cysteine-capped CdSeS was 71.2% but decreased significantly to 5.2% upon passivation with a ZnSeTe shell. The red shift in PL emission of the CdSeS/ZnSeTe QDs was attributed to be strain-induced whilst a lattice-induced process likely created defect states in the core/shell interface hence contributing to the decline in the PL QY. Nonetheless, the fluorescence stability of CdSeS/ZnSeTe QDs in aqueous solution was unperturbed. Further passivation with a ZnS shell (CdSeS/ZnSeTe/ZnS) improved the PL QY to a value of 58.7% and thus indicates that the defect state in the QDs core/shell/shell structure was reduced. PL lifetime exciton measurements indicated that the rates of decay of the QDs influenced their photophysical properties.     

Structural characterization of CdSe/ZnS core–shell quantum dots (QDs) using TEM/STEM observation

CdSe/ZnS core–shell structured nano-crystal quantum dots (QDs) are ideal candidates for light-emission applications due to their high quantum efficiency, narrow-band, and particle-size-tunable photoluminescence. In particular, their small size results in the quantum confinement of semiconductor nano-crystals, which widens their energy gaps. In general, structural analyses of QDs using a transmission electron microscope (TEM) are very important due to the significantly small size of QDs. We were able to obtain structural information of CdSe/ZnS core–shell QDs using nano-beam diffraction by controlling the nano-probe of the dark field scanning TEM (DF-STEM) mode and strain analysis with high-resolution TEM (HRTEM)/STEM images. Furthermore, we could clearly distinguish the interface between the CdSe core and the ZnS shell from the strain analysis with the HRTEM/STEM images.     

Photoluminescence-enhanced biocompatible quantum dots by phospholipid functionalization

A simple two-step strategy using phospholipid (PPL) to functionalize core/shell CdSe/ZnS quantum dots (QDs) has been described. The experimental data show that the use of S-H terminated PPL results not only in the high colloidal stability of core/shell CdSe/ZnS QDs in the aqueous phase, but also in the significant enhancement of photoluminescence. The degree of the enhancement is a function of the PPL-CdSe/ZnS QDs sample concentration. These results might be promising for future biological platform in new devices ranging from photovoltaic cells to biosensors and other devices.     

Shell distribution on colloidal CdSe/ZnS quantum dots

Scanning transmission electron microscopy (STEM) coupled with electron energy loss spectroscopy (EELS) was used to determine the chemical distribution of semiconductor shell material around colloidal core-shell CdSe/ZnS quantum dots (QDs). EELS signals from positions around the QD indicate a well-defined shell of ZnS surrounding the CdSe core, but the distribution of the shell material is highly anisotropic. This nonuniformity may reflect the differences in chemical activity of the crystal faces of the core QD and implies a nonoptimal QD surface passivation.     

CdSe量子点的制备及荧光性能改善

主要讨论了CdSe量子点的制备及荧光性能的改善.采用水相合成方法制备了CdSe量子点,并用X射线粉末衍射仪对所合成的量子点进行表征,用荧光分光光度计研究了量子点的荧光性质.结果表明,采用样品处理温度的调节和ZnS壳层的包覆能在一定程度上改善CdSe量子点的荧光性能.