水溶性的高荧光CdTe/CdSeⅡ型核壳量子点的合成与表征

用L-半胱氨酸(L-cysteine)作为稳定剂,以制备的CdTe量子点为核模板,水相合成了具有近红外发光的Ⅱ型核壳CdTe/CdSe半导体量子点。实验考察了合成温度,核模板的尺寸和组分比等因素对合成高质量的CdTe/CdSe量子点的影响。用紫外-可见吸收和荧光光谱研究了合成的量子点的光学性质。在优化的合成条件下,荧光发射光谱在586～753nm范围连续可调,荧光量子产率高达68%;通过X-射线衍射(XRD),X射线光电子能谱(XPS)和透射电镜(TEM)对合成的Ⅱ型核壳CdTe/CdSe量子点进行了结构和形貌表征。     

Large-scale synthesis of nearly monodisperse CdSe/CdS core/shell nanocrystals using air-stable reagents via successive ion layer adsorption and reaction

Successive ion layer adsorption and reaction (SILAR) originally developed for the deposition of thin films on solid substrates from solution baths is introduced as a technique for the growth of high-quality core/shell nanocrystals of compound semiconductors. The growth of the shell was designed to grow one monolayer at a time by alternating injections of air-stable and inexpensive cationic and anionic precursors into the reaction mixture with core nanocrystals. The principles of SILAR were demonstrated by the CdSe/CdS core/shell model system using its shell-thickness-dependent optical spectra as the probes with CdO and elemental S as the precursors. For this reaction system, a relatively high temperature, about 220-240 degrees C, was found to be essential for SILAR to fully occur. The synthesis can be readily performed on a multigram scale. The size distribution of the core/shell nanocrystals was maintained even after five monolayers of CdS shell (equivalent to about 10 times volume increase for a 3.5 nm CdSe nanocrystal) were grown onto the core nanocrystals. The epitaxial growth of the core/shell structures was verified by optical spectroscopy, TEM, XRD, and XPS. The photoluminescence quantum yield (PL QY) of the as-prepared CdSe/CdS core/shell nanocrystals ranged from 20% to 40%, and the PL full-width at half-maximum (fwhm) was maintained between 23 and 26 nm, even for those nanocrystals for which the UV-vis and PL peaks red-shifted by about 50 nm from that of the core nanocrystals. Several types of brightening phenomena were observed, some of which can further boost the PL QY of the core/shell nanocrystals. The CdSe/CdS core/shell nanocrystals were found to be superior in comparison to the highly luminescent CdSe plain core nanocrystals. The SILAR technique reported here can also be used for the growth of complex colloidal semiconductor nanostructures, such as quantum shells and colloidal quantum wells.     

Epitaxial growth and photochemical annealing of graded CdS/ZnS shells on colloidal CdSe nanorods

We report the preparation and structural characterization of core/shell CdSe/CdS/ZnS nanorods. A graded shell of larger band gap is grown around CdSe rods using trioctylphosphine oxide as a surfactant. Interfacial segregation is used to preferentially deposit CdS near the core, providing relaxation of the strain at the core/shell interface. The reported synthesis allows for variation of the shell thickness between one and six monolayers, on core nanorods ranging from aspect ratios of 2:1 to 10:1. After an irreversible photochemical annealing process, the core/shell nanorods have increased quantum efficiencies and are stable in air under visible or UV excitation. In addition to their robust optical properties, these samples provide an opportunity for the study of the evolution of epitaxial strain as the shape of the core varies from nearly spherical to nearly cylindrical.     

Enhancement of the photoluminescence of CdSe quantum dots during long-term UV-irradiation: privilege or fault in life science research?

The present study describes an impressive enhancement of the photoluminescence (PL) intensity of low-temperature synthesized CdSe nanocrystals (75 degrees C) during long-term UV-irradiation. The integrated PL-intensity of CdSe core and CdSe/ZnS core/shell nanocrystals, dispersed in chloroform, enhanced about 3 and 6 times, respectively, during 9 h exposure to UV-light, without any significant changes in the characteristic absorbance spectra and shifting of PL-spectra. After termination of the irradiation a comparatively slow photobleaching was detected with tau(1/2) = 6 h for CdSe core and tau(1/2) = 14 h for CdSe/ZnS core/shell nanocrystals. The most impressive was the effect of UV-irradiation on the photoluminescence of water-soluble CdSe nanocrystals. The integrated PL-intensity enhanced about 10 times during 11 h exposure to UV-light and the improved PL-intensity was preserved during 3 days after termination of the irradiation without any significant photobleaching. The results are discussed in the context of application of CdSe nanocrystals as novel fluorophores in life science experiments.     

Intraband spectroscopy and band offsets of colloidal II-VI core/shell structures

The interband and intraband spectra of colloidal II-VI CdS and CdSe quantum dot cores and CdSZnSe, CdSCdSe, CdSeCdS, and CdSeZnSe core/shell systems are reported. Infrared absorption peaks between 0.5 and 0.2 eV are observed. The slope of the intraband energy versus the first interband absorption feature is characteristic of the relative band alignments of the materials constituting the core and the shell and it is analyzed within an effective mass model. The analysis provides a new estimate of the band gap of zinc blende CdSe as well as the band offsets in zinc blende and wurtzite CdSe, CdS, and ZnSe.     

Synthesis of core/shell nanoparticles of Au/CdSe via Au-Cd bialloy precursor

We present a novel method for the preparation of ultrasmall Au/CdSe core/shell particles. Au-Cd bialloy particles of 4.7 nm diameter were prepared as the precursor. The Cd component in the precursor reacted with the Se source at a temperature of 205 degrees C and was heated to 250 degrees C, leading to formation of a Au/CdSe core/shell structure. The sizes of Au/CdSe nanoparticles have a narrow distribution with an average size of 6.0 nm and Au core of 2.2 nm diameter. The X-ray diffraction pattern and the images of the high-resolution electron transmission microscopy show that the Au cores and the CdSe shells of Au/CdSe core/shell nanoparticles are both well crystallized, and the CdSe shells are in a cubic phase. The absorption spectrum of the Au/CdSe nanoparticles combines the absorption behaviors of the Au cores and the CdSe shells.     

Core/shell quantum dots with high relaxivity and photoluminescence for multimodality imaging

A series of core/shell CdSe/Zn1-xMnxS nanoparticles were synthesized for use in dual-mode optical and magnetic resonance (MR) imaging techniques. Mn2+ content was in the range of 0.6-6.2% and varies with the thickness of the shell or amount of Mn2+ introduced to the reaction. These materials showed high quantum yield (QY), reaching 60% in organic solvent. Water-soluble nanoparticles were obtained by capping the core/shell particles with amphiphilic polymer, and the QY values in water reached 21%. These materials also demonstrated high relaxivity with r1 values in the range of 11-18 mM-1 s-1 (at room temperature, 7 T). Both optical and MR imaging were performed on nanoparticles in aqueous solution and applied to cells in culture. The results showed that the QY and manganese concentration in the particles was sufficient to produce contrast for both modalities at relatively low concentrations of nanoparticles.     

Type-II core/shell CdS/ZnSe nanocrystals: synthesis, electronic structures, and spectroscopic properties

We report a two-step synthesis of highly luminescent CdS/ZnSe core/shell nanocrystals (emission quantum yields up to 50%) that can produce efficient spatial separation of electrons and holes between the core and the shell (type-II localization regime). Our synthesis involves fabrication of cubic-singony CdS core particles that are subsequently overcoated with a layer of ZnSe in the presence of surfactant-ligands in a noncoordinating solvent. Studies of different growth regime of the ZnSe shell indicate that one approach to obtaining high emission efficiencies is through alloying the CdS/ZnSe interface with CdSe, which leads to the formation of an intermediate ZnCdSe layer with a graded composition. We perform theoretical modeling of these core/shell nanocrystals using effective mass approximation and applying first-order perturbation theory for treating both direct electron-hole coupling and the core/shell interface-polarization effects. Using this model we determine the range of geometrical parameters of the core/shell structures that result in a type-II localization regime. We further applied this model to evaluate the degree of electron-hole spatial separation (quantified in terms of the electron-hole overlap integral) based on measured emission wavelengths. We also discuss the potential applicability of these nanocrystals in lasing technologies and specifically the possibility of single-exciton optical gain in type-II nanostructures.     

Temperature-dependent photoluminescence of water-soluble quantum dots for a bioprobe

The photoluminescence of water-soluble CdSe/ZnS core/shell quantum dots is found to be temperature-dependent: as temperature arising from 280 K to 351 K, the photoluminescence declines with emission peak shifting towards the red at a rate of ∼0.11 nm K⁻¹. And the studies show that the photoluminescence of water-soluble CdSe/ZnS quantum dots with core capped by a thinner ZnS shell is more sensitive to temperature than that of ones with core capped by a thicker one. That is, with 50% decrement of the quantum yield the temperature of the former need to arise from 280 K to 295 K, while the latter requires much higher temperature (315.6 K), which means that the integrality of shell coverage is a very important factor on temperature-sensitivity to for the photoluminescence of water-soluble CdSe/ZnS quantum dots. Moreover, it is found that the water-soluble CdSe quantum dots with different core sizes, whose cores are capped by thicker ZnS shells, possess almost the same sensitivity to the temperature. All of the studies about photoluminescence temperature-dependence of water-soluble CdSe/ZnS core/shell quantum dots show an indispensable proof for their applications in life science.     

Synthesis CdSe(x)S(1-x) core/shell type quantum dots via one injection method

The photoluminescence quantum yield (PL-QY) of ternary colloidal CdSe(x)S(1-x) quantum dots (QDs), which were prepared by a one-injection method, enhances with increasing S content. The possible enhancement mechanism was explored by structural analysis via X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). Both found that the enhancement of PL-QY of ternary CdSe(x)S(1-x) QDs strongly correlated with self-formed core/shell conformation in the non-coordination solution.     

Single-source precursor route for overcoating CdS and ZnS shells around CdSe core nanocrystals

We reported a facile route for overcoating CdS and ZnS shells around colloidal CdSe core nanocrystals. To synthesize such double shelled core/shell nanocrystals, first, CdSe core nanocrystals were prepared in a much “greener” and cheap route, which did not involve the use of hazardous and expensive trioctylphosphine. Then, a low-cost and labor-saving route was adopted for the CdS and ZnS shell growth with the use of thermal decomposition of commercial available air stable single-source precursors cadmium diethyldithio-carbamate and zinc diethyldithiocarbamate in a non-coordinating solvent at intermediate temperatures. Powder X-ray diffraction patterns and transmission electron microscopy images confirm the epitaxial growth of the shell in the core/shell nanocrystals. The photoluminescence quantum yield of the resulting CdSe/CdS/ZnS core/shell nanocrystals can be as high as 90% in organic media and up to 60% after phase transfer into aqueous media. By varying the size of CdSe cores, the emission wavelength of the obtained core/shell nanostructures can span from 554 to 636 nm.     

Fluorescence blinking statistics from CdSe core and core/shell nanorods

We report fluorescence blinking statistics measured from single CdSe nanorods (NRs) of seven different sizes with aspect ratios ranging from 3 to 11. This study also included core/shell CdSe/ZnSe NRs and core NRs with two different surface ligands producing different degrees of surface passivation. We compare the findings for NRs to our measurements of blinking statistics from spherical CdSe core and CdSe/ZnS core/shell nanocrystals (NCs). We find that, for both NRs and spherical NCs, the off-time probability distributions are well described by a power law, while the on-time probability distributions are best described by a truncated power law, P(tau(on)) approximately tau(on)(-alpha)e((-tau)(on)/(tau)(c)). The measured crossover time, tau(c), is indistinguishable within experimental uncertainty for core and core/shell NRs, as well as for core NRs with different ligands, for the same core size, indicating that surface passivation does not affect the blinking statistics significantly. We find that, at fixed excitation intensity, 1/tau(c) increases approximately linearly with increasing NR aspect ratio; for a given sample, 1/tau(c) increases very gradually with increasing excitation intensity. Examining 1/tau(c)versus the single-particle photon absorption rate for all samples indicates that the change in NR absorption cross section with sample size can account for some but not all of the differences in crossover time. This suggests that the degree of quantum confinement may be partially responsible for the aspect ratio dependence of the crossover time.     

Solution-based II-VI core/shell nanowire heterostructures

We demonstrate the solution-phase synthesis of CdS/CdSe, CdSe/CdS, and CdSe/ZnTe core/shell nanowires (NWs). On the basis of bulk band offsets, type-I and type-II heterostructures are made, contributing to the further development of low-dimensional heteroassemblies using solution-phase chemistry. Core/shell wires are prepared by slowly introducing shell precursors into a solution of premade core NWs dispersed in a noncoordinating solvent at moderate temperatures (215-250 degrees C). Resulting heterostructures are characterized through low- and high-resolution transmission electron microscopy, selected area electron diffraction, and energy dispersive X-ray analysis. From these experiments, initial shell growth appears to occur through either Stranski-Krastanov or Volmer-Weber island growth. However, beyond a critical shell thickness, nucleation of randomly oriented nanocrystals results in a polycrystalline coat. In cases where overcoating has been achieved, corresponding elemental analyses show spatially varying compositions along the NW radial direction in agreement with expected element ratios. Electronic interactions between the core and shell were subsequently probed through optical studies involving UV-vis extinction spectroscopy, photoluminescence experiments, and transient differential absorption spectroscopy. In particular, transient differential absorption studies reveal unexpected shell-induced changes in core NW Auger kinetics at high carrier densities. Previously seen three-carrier Auger kinetics in CdS (bimolecular in CdSe) NWs were suppressed by the presence of a CdSe (CdS) shell. These observations suggest the ability to influence NW optical/electrical properties by coating them with a surrounding shell, a method which could be important for future NW optical studies as well as for NW-based applications.     

Manipulation of the morphology of semiconductor-based nanostructures from core-shell nanoparticles to nanocables: the case of CdSe/SiO(2)

The morphology of CdSe/SiO(2) was manipulated from core-shell-structured nanoparticles to nanocables by using a chemical vapor deposition (CVD) process. The growth of nanocables, with cores no more than 20 nm in diameter, is initiated by the formation of core-shell nanoparticles with SiO(2) as matrix and CdSe clusters dispersed inside. After the subsequent vaporization of the SiO(2) matrix, the follow-up CdSe vapor crystallizes with the remaining CdSe clusters as nuclei to form CdSe nanowires as the furnace was cooled to 1200 degrees C. During the controlled cooling of the furnace, the SiO vapor re-deposits to sheathe the nanowires. The thickness of the shell and the diameter of core were successfully controlled. The photoluminescence measurements show that the CdSe/SiO(2) nanocables have strong visible-light emission bands located at 590 and 688 nm, which are attributed to the defects induced by SiO(2) sheaths nanowires and the quantum confinement effect of the CdSe, respectively. The UV/Vis absorption spectra of the naked CdSe nanowires further validate the above-mentioned quantum confinement effect. The deterministic growth of these nanocables is very important for the design of the nanodevices based on them.     

Photoassisted synthesis of CdSe and core-shell CdSe/CdS quantum dots

This paper describes the synthesis of core-shell CdSe/CdS quantum dots (QDs) in aqueous solution by a simple photoassisted method. CdSe was prepared from cadmium nitrate and 1,1-dimethylselenourea precursors under illumination for up to 3 h using a pulsed Nd:YAG laser at 532 nm. The effects that the temperature and the laser irradiation process have on the synthesis of CdSe were monitored by a series of experiments using the precursors at a Cd:Se concentration ratio of 4. Upon increasing the temperature (80-140 degrees C), the size of the CdSe QDs increases and the time required for reaching a maximum photoluminescence (PL) is shortened. Although the as-prepared CdSe QDs possess greater quantum yields (up to 0.072%) compared to those obtained by microwave heating (0.016%), they still fluoresce only weakly. After passivation of CdSe (prepared at 80 degrees C) by CdS using thioacetamide as the S source (Se:S concentration ratio of 1) at 80 degrees C for 24 h, the quantum yield of the core-shell CdSe/CdS QDs at 603 nm is 2.4%. Under UV irradiation of CdSe/CdS for 24 h using a 100-W Hg-Xe lamp, the maximum quantum yield of the stable QDs is 60% at 589 nm. A small bandwidth (W1/2 < 35 nm) indicates the narrow size distribution of the as-prepared core-shell CdSe/CdS QDs. This simple photoassisted method also allows the preparation of differently sized (3.7-6.3-nm diameters) core-shell CdSe/CdS QDs that emit in a wide range (from green to red) when excited at 480 nm.     

Toward highly efficient CdS/CdSe quantum dots-sensitized solar cells incorporating ordered photoanodes on transparent conductive substrates

A series of ordered photoanodic architectures (including ordered TiO(2) nanotube arrays (TNT), ZnO nanorods, ZnO/TiO(2) core/shell nanostructures) for CdS/CdSe sensitized solar cells (QDSCs), were fabricated directly on transparent conductive oxide glasses by a facile sol-gel assisted template process. The morphologies, optical and electrical properties of TNTs and CdS/CdSe co-sensitized TNTs have been demonstrated. The effect of CdSe deposition time on the cell performance was clarified, and the growth mechanism of the CdSe quantum dots on the surface of the TNTs has been proposed as well. Furthermore, the evolution of open-circuit photovoltage (V(oc)) towards CdSe deposition time has been investigated by electrochemical impedance spectroscopy (EIS). A promising light-to-electricity conversion efficiency of up to 4.61% has been achieved with 3 μm long TNT arrays, which is the best record for sandwich-type ordered TNT-based QDSCs.     

Enhanced ultraviolet emission from ZnS-coated ZnO nanowires fabricated by self-assembling method

A simple chemical route for ZnS-coated ZnO nanowires with preferential (002) orientation is reported. Sodium sulfide and zinc nitrate were employed to supply S and Zn atoms at 60 degrees C to form ZnS-coated ZnO nanowires structures. Electron diffraction measurement shows that the ZnO/ZnS core-shell nanostructure is single crystalline. Interesting features are found in the photoluminescence (PL) spectra of ZnS-coated ZnO nanostructures. After coating, the UV emission of nanorods is dramatically enhanced at the expense of the green emission. The core/shell structure with higher band gap shell material and reduced surface states should be responsible for this PL enhancement.     

Effects of surface passivation on the exciton dynamics of CdSe nanocrystals as observed by ultrafast fluorescence upconversion spectroscopy

The exciton dynamics of CdSe nanocrystals are intimately linked to the surface morphology. Photo-oxidation of the selenium surfaces of the nanocrystal leads to an increase in radiative decay efficiency from both the band edge and deep trap emission states. The addition of the primary amine hexadecylamine curtails nonradiative excitonic decay attributed to the dangling surface selenium orbitals by passivation of those trap sites by the methylene protons on the amine, leading to enhanced band edge emission and the absence of deep trap emission. Furthermore, CdSeZnSe core/shell nanocrystals are not immune from contributions from surface states because of the alignment of the band structures of the core and shell materials.     

Rational synthetic strategy: From ZnO nanorods to ZnS nanotubes

We demonstrate here that ZnS nanotubes can be successfully synthesized via a facile conversion process from ZnO nanorods precursors. During the conversion process, ZnO nanorods are first prepared as sacrificial templates and then converted into tubular ZnO/ZnS core/shell naonocomposites through a hydrothermal sulfidation treatment by using thioacetamide (TAA) as sulfur source. ZnS nanotubes are finally obtained through the removal of ZnO cores of tubular ZnO/ZnS core/shell naonocomposites by KOH treatment. The photoluminescence (PL) characterization of the as-prepared products shows much enhanced PL emission of tubular ZnO/ZnS core/shell nanocomposites compared with their component counterparts. The probable mechanism of conversion process is also proposed based on the experimental results.     

Controllable Conversion of CdNCN Nanoparticles into Various Chalcogenide Nanostructures for Photo-driven Applications

Semiconductor nanocrystals of tunable shell/core configurations have great potential in photo-driven applications such as photoluminescence and photocatalysis, but few strategies realize a controllable synthesis with respect to both the size of the core and the shell with high crystallinity. Here, a new synthetic method based on cadmium cyanamide (CdNCN) nanoparticle anion exchange reactions was developed to access solid or hollow CdSe nanocrystals with tunable size and CdNCN@CdS heterostructures with modulated shell/core thickness. The gradual shift and narrow width of photoluminescence features demonstrate the high crystallinity and monodispersity of the resulting CdSe nanocrystals. In the CdNCN@CdS heterostructures, synergistic effects of the photocarrier separation is observed between the CdS shell and CdNCN core, which leads to great improvement in photocatalysis with optimized shell/core ratio.