硒化镉发光量子点的制备及其在有机发光器件中的应用

硒化镉量子点具有随粒径尺寸改变,而产生发光波长调变的特性,目前已被广泛研究。本研究是由化学溶胶法合成不同粒径尺寸的核壳型CdSe／ZnS硒化镉量子点,其表面包覆十六烷基胺,避免分子团聚现象。在由硒化镉成核温度的控制,成功地制备一系列具有各种尺寸粒径的核壳型硒化镉量子点(2—6nm)。本研究也合成了含有纳米金粒子于核壳型硒化镉量子点,实验结果发现：硒化镉发光效率明显的提高。在有机发光器件的应用方面,将发光波长为505nm核壳型CdSe／ZnS量子点掺入溶有发光波长为570nm铱化合物的氯仿溶液时,其溶液的光致发光光谱表明,原量子点的发光特性消失,只有铱化合物的发光依然存在,且其发光强度呈现明显增强趋势,我们推测此现象源自于量子点到铱化合物能量转移的机制。我们也以含有核壳型硒化镉量子点的铱化合物与PVK混合材料为发光层,成功的制作发光二极管器件,器件的发光效率因核壳型硒化镉的掺杂,明显提高2倍多。     

Rapid oxidation of InP nanoparticles in air

InP nanoparticles (NPs) in the size range of 1.5-3 nm were synthesized using colloidal chemistry methods. Exposure of these NPs to air resulted in rapid oxidation, as shown by transmission electron microscopy. Diffraction and spectroscopic measurements confirmed the formation of In₂O₃. Similar behavior was observed for commercial InP NPs, even when capped with a ZnS shell. Photoluminescence studies suggest that the oxidation occurs even while InP NPs are still dispersed in hexane, albeit at a much slower rate.     

Generation of Soft Ferrite Nanoparticles by Pulsed Laser Ablation in Liquids

We generate Mn–ferrite nanoparticles (NPs) by Nd:YAG (1064 nm) laser irradiation in distilled water. We characterize such NPs in terms of the size distribution, shape and chemical composition using transmission electron microscopy (TEM), energy-dispersive X rays (EDS), and Fourier-transform infrared spectroscopy (FTIR). Using a magnetic force microscope (MFM), we show the magnetic properties of the generated nanoparticles.     

Experimental investigation of energy transfer between CdSe/ZnS quantum dots and different-sized gold nanoparticles

Hybrid nanostructures of quantum dots(QDs) and metallic nanostructure are attractive for future use in a variety of optoelectronic devices. For photodetection applications, it is important that the photoluminescence (PL) of QDs is quenched by the metallic nanostructures. Here, the quenching efficiency of CdSe/ZnS core-shell quantum dots (QDs) with different sized gold nanoparticles (NPs) films through energy transfer is investigated by measuring the PL intensity of the hybrid nanostructures. In our research, the gold NPs films are formed by the post-annealing of the deposited Au films on the quartz substrate. We find that the energy transfer from the QDs to the Au NPs strongly depends on the sizes of the Au NPs. For CdSe/ZnS QDs direct contact with the Au NPs films, the largest energy transfer efficiency are detected when the resonance absorption peak of the Au NPs is nearest to the emission peak of the CdSe/ZnS QDs. However, when there is a PMMA spacer between the QDs layer and the Au NPs films, firstly, we find that the energy transfer efficiency is weakened, and the largest energy transfer efficiency is obtained when the resonant absorption peak of the Au NPs is farthest to the emission peak wavelength of CdSe/ZnS QDs. These results will be useful for the potential design of the high efficiency QDs optoelectronic devices.     

Generation and characterization of NiO nanoparticles by continuous wave fiber laser ablation in liquid

Pulsed laser ablation in liquid (PLAL) has been widely applied for the generation of nanoparticles (NPs). We report on the generation of NiO NPs using a high-power, high-brightness continuous wave (CW) fiber laser source at a wavelength of 1,070 nm. Characterization of such NPs in terms of size distribution, shape, chemical composition, and phase structure was carried out by transmission electron microscopy (TEM), high-resolution TEM equipped with energy-dispersive X-ray (EDX), and X-ray diffraction (XRD). The results revealed the formation of NiO NPs in water with an average size of 12.6 nm. The addition of anionic surfactant sodium dodecyl sulfate (SDS) reduced the size of NiO NPs down to 10.4 nm. The shape of the NPs was also affected by the SDS, showing the change of shapes from spherical domination in water to tetragonal with increased SDS concentrations. Furthermore, the NiO NPs generated in water and SDS solutions were dual phase containing both cubic and rhombohedral structures. It was also found that the NiO NPs were single crystalline in nature irrespective of the size and shape.     

Interaction of ZnS nanoparticles with flavins and glucose oxidase: A fluorimetric investigation

Interactions of luminescence, water soluble ZnS nanoparticles (NPs) with flavins and glucose oxidase have been thoroughly investigated through optical spectroscopy. The photoluminescence of ZnS nanoparticles was quenched severely (～60%) by riboflavin while other flavins such as flavin mononucleotide (FMN) and flavin adenine dinucleotide (FAD) show quenching to different extents under analogous conditions. However, interestingly no effect in luminescence intensity of ZnS NPs was observed with protein bound flavins such as in glucose oxidase. Fluorescence lifetime measurement confirmed the quenching to be static in nature. Scavenging of photo-generated electron of ZnS nanoparticles by the flavin molecules may be attributed to the decrease in luminescence intensity. Quenching of ZnS nanoparticles with flavins follows the linear Stern–Volmer plot. The Stern–Volmer constants decreased in the following order: K_S?V (Riboflavin)> K_S?V (FAD)> K_S?V (FMN). This interaction study could generate useful protocol for the fluorimetric determination of riboflavin (vitamin B₂) content and also riboflavin status in biological systems.     

The structure and photoluminescence properties of TiO<Subscript>2</Subscript>-coated ZnS nanowires

The structure and photoluminescence properties of TiO₂-coated ZnS nanowires were investigated. ZnS nanowires were synthesized by thermal evaporation of ZnS powder and then coated with TiO₂ by using the metal organic chemical vapor deposition (MOCVD) technique. We performed scanning electron microscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy, and photoluminescence (PL) spectroscopy to characterize the as-synthesized and TiO₂-coated ZnS nanowires. TEM and XRD analyses revealed that the ZnS core and the TiO₂ coatings had crystalline zinc blende and crystalline anatase structures, respectively. PL measurement at room temperature showed that the as-synthesized ZnS nanowires had two emissions: a blue emission centered in the range from 430 to 440 nm and a green emission at around 515 nm. The green emission was found to be dominant in the ZnS nanowires coated with TiO₂ by MOCVD at 350°C for one or more hours, while the blue emission was dominant in the as-synthesized ZnS nanowires. Also the mechanisms of the emissions were discussed.     

Influence of surfactant structures in luminescence enhancement dynamics during nucleation and growth of aqueous ZnS nanoparticles and their photoactivation due to illumination with UV/visible light

Nanostructured semiconductor architectures have attractive optical properties mainly including bright photoluminescence (PL) resulting from the radiative recombination of charge carriers on surface states. Various approaches have been employed for the modification of surface states of these nanostructures to design new nanomaterials with enhanced PL primarily in aqueous medium to enable their applications in biological samples. Here, we report the varying efficiencies of three commercial surfactants viz. cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC) and cetylpyridinium chloride (CPyC) on the dynamics of PL emission enhancement during initial growth and Ostwald ripening of ZnS nanoparticles (NPs). The counterion has been estimated to behave differently to govern the PL enhancement. The exceptionally high tendency of CPyC in PL enhancement has been assigned to participation of π-electrons of pyridinium ring. The impact of UV-light in photoactivation of surfactant stabilized ZnS NPs has been utilized in exploring significance of surfactants in improving the surface emitting states in water soluble semiconductor NPs.     

Three dimensional accurate morphology measurements of polystyrene standard particles on silicon substrate by electron tomography

Polystyrene latex (PSL) nanoparticle (NP) sample is one of the most widely used standard materials. It is used for calibration of particle counters and particle size measurement tools. It has been reported that the measured NP sizes by various methods, such as Differential Mobility Analysis, dynamic light scattering (DLS), optical microscopy (OM), scanning electron microscopy (SEM) and atomic force microscopy (AFM), differ from each other. Deformation of PSL NPs on mica substrate has been reported in AFM measurements: the lateral width of PSL NPs is smaller than their vertical height. To provide a reliable calibration standard, the deformation must be measured by a method that can reliably visualize the entire three dimensional (3D) shape of the PSL NPs. Here we present a method for detailed measurement of PSL NP 3D shape by means of electron tomography in a transmission electron microscope. The observed shape of the PSL NPs with 100 nm and 50 nm diameter were not spherical, but squished in direction perpendicular to the support substrate by about 7.4% and 12.1%, respectively. The high difference in surface energy of the PSL NPs and that of substrate together with their low Young modulus appear to explain the squishing of the NPs without presence of water film.     

Layered nanocomposite of zinc sulfide covered reduced graphene oxide and their implications for electrocatalytic applications

Herein, we have synthesized zinc sulfide nanospheres (ZnS NPs) encapsulated on reduced graphene oxide (RGO) hybrid by an ultrasonic bath (50 kHz/60 W). The physical and structural properties of ZnS NPs@RGO hybrid were analyzed by TEM, XRD, EIS and EDS. As-prepared ZnS NPs@RGO hybrid was applied towards the electrochemical determination of caffeic acid (CA) in various food samples. The ZnS NPs@RGO hybrid modified electrode (GCE) exhibited an excellent electrocatalytic performance towards caffeic acid detection and determination, when compared to other modified electrodes. Therefore, the electrochemical sensing performance of the fabricated and nanocomposite modified electrode was significantly improved owing to the synergistic effect of ZnS NPs and RGO catalyst. Furthermore, the hybrid materials provide highly active electro-sites as well as rapid electron transport pathways. The proposed electrochemical caffeic acid sensor produces a wide linear range of 0.015–671.7 µM with a nanomolar level detection limit (3.29 nM). In addition, the real sample analysis of the proposed sensor has applied to the determination of caffeic acid in various food samples.     

Photoluminescent properties of ZnS nanoparticles prepared by electro-explosion of Zn wires

We study the photoluminescent properties of ZnS nanoparticles without the influence of dopants or magnetic impurities. The ZnS nanoparticles reported in this case were synthesized by a novel method of electro-explosion of wire (EEW). The nanoparticles were prepared employing electro-explosion of pure zinc wires in a cell filled with sulfide ions to produce a free-standing compound ZnS semiconductor. To investigate the structural and optical properties, these nanoparticles were characterized by X-ray powder diffraction (XRD), atomic force microscopy (AFM), UV–visible and photoluminescence (PL) spectroscopy. Consistent with the enhancement of the PL intensity of the 443 nm peak due to deep blue emission of ZnS particles, the XRD of the nanoparticles reveals a hexagonal phase of ZnS nanocrystallites prepared by our novel synthesis technique.      

Aqueous phase Ag nanoparticles with controlled shapes fabricated by a modified nanosphere lithography and their optical properties

We have developed a modified nanosphere lithography (NSL) process to fabricate surface-confined Ag nanoparticles (NPs) with controlled shapes. NPs with different shapes, such as triangular, quadrilateral, pentagon or trapezoidal with rounded tips or edges, can be fabricated by this process. These Ag NPs can be dislodged into water forming NPs in an aqueous environment. The developed process results in better NP shape retaining than those obtained using the routine NSL process. The UV-vis absorption of the surface-confined Ag NPs show distinct blue shift and reduced intensity after surface modification. The NPs produced by the modified NSL and dislodged in water have significantly less density of debris as observed by transmission electron microscopy and UV-vis absorption spectrum.     

Synthesis of Mn-doped ZnS architectures in ternary solution and their optical properties

Mn-doped ZnS sea urchin-like architectures were fabricated by a one-pot solvothermal route in a ternary solution made of ethylenediamine, ethanolamine and distilled water. The as-prepared products were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and photoluminescence spectra (PL). It was demonstrated that the as-prepared sea urchin-like architectures with diameter of 0.5-1.5 μm were composed of nanorods, possessing a wurtzite structures. The preferred growth orientation of nanorods was found to be the [0 0 2] direction. The PL spectra of the Mn-doped ZnS sea urchin-like architectures show a strong orange emission at 587 nm, indicating the successful doping of Mn²⁺ ions into ZnS host. Ethanolamine played the role of oriented-assembly agent in the formation of sea urchin-like architectures. A possible growth mechanism was proposed to explain the formation of sea urchin-like architectures.     

Synthesis of ZnS nanorods by annealing precursor ZnS nanoparticles in NaCl flux

ZnS nanorods were fabricated by annealing precursor ZnS nanoparticles, which were prepared by one-step, solid-state reaction of ZnCl₂ and Na₂S through grinding by hand at ambient temperature, in NaCl flux. The as-prepared ZnS nanorods have diameters of 40-80 nm, and lengths up to several micrometers. The structural features and chemical composition of the nanorods were investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), high-resolution transmission electron microscopy (HRTEM), and Raman spectra.     

Surface modification of the nanoparticles by an atmospheric room-temperature plasma fluidized bed

Using hexamethyldisiloxane (HMDSO) monomer, the magnetic nanoparticles (NPs) of nickel oxide (NiO) were modified by using an atmospheric room-temperature plasma fluidized bed (ARPFB). The plasma gas temperature of the ARPFB was not higher than 325 K, which was favorable for organic polymerization. The plasma optical emission spectrum (OES) of the gas mixture consisting of argon (Ar) and HMDSO was recorded by a UV-visible monochromator. The as-treated NPs were characterized by means of scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The results show that the assembling NPs were isolated greatly after modified by the organosilicon polymer. Moreover, this treatment process changed the wettability of the NPs from super-hydrophilicity to super-hydrophobicity, and the contact angle (CA) of water on the modified NPs surface exceeded 150°. Therefore, the ARPFB is a prospective technology for the NPs surface modification according to the different requirements.     

Formation of hexagonal shaped wurtzite zinc sulphide nano rods

Zinc sulfide nanorods with good photoluminescence have been successfully fabricated using a simple sol-gel process via ultrasonication, with mercaptoethanol as capping agent. The formation of ZnS nucleation, followed by subsequent growth, is significant in obtaining highly oriented ZnS nanorods. Temperature, time, and capping agent also proved to be significant factors in the growth of ZnS nanorods and greatly affect their photo luminescent properties. X-ray diffraction (XRD) analysis, low and high-resolution transmission electron microscopy (TEM & HRTEM), selected-area electron diffraction (SAED) pattern, and scanning electron microscopy (SEM) indicated that the ZnS nanorods were single crystal in nature and that they had grown up preferentially along the [0001] direction. This simple method of nucleation, followed by their successive growth, resulted in the development of an effective and low-cost fabrication process for high-quality ZnS nanorods with good photo luminescent properties that can be applied to luminescent sensors and optoelectronic devices.     

ZnO–ZnS heterostructures with enhanced optical and photocatalytic properties

ZnO–ZnS heterostructures were fabricated via using ZnO rods as template in different Na₂S aqueous solutions. These heterostructures are 5–6 μm in length and formed by coating ZnO rod with a layer of porous ZnS shell comprising primary crystals about 10 nm in diameter. Subsequently, intact ZnS polycrystalline tubes were obtained by removing the ZnO cores with 25% (wt) ammonia. The as-prepared products were characterized by scanning electronic microscopy (SEM), transmission electronic microscopy (TEM), X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDX), Fourier transform infrared (FT-IR), and electrochemical impedance spectroscopy (EIS). It was found that the electron transfer between ZnS shell and ZnO core strongly affect the photoluminescence and photocatalytic performances of these heterostructures. The rapid transfer of photo-induced electrons from the ZnS shell to the ZnO core leads to enhanced ultraviolet emission. However, if this correlation was destroyed, then the corresponding heterostructure exhibits improved photocatalytic efficiency due to the reduced volume recombination of the charge carries and the multiple reflection effect. Finally, a model based on band-gap alignment was proposed to elucidate the underlying mechanism of the enhanced UV emission and photocatalytic activity of these unique heterostructures.     

Formation of ZnS nanorods by simple evaporation technique

Semiconductor nanocrystals and nanorods whose properties are largely determined by the quantum confinement effect are currently being intensively studied by materials scientists, physicists and chemists. Zinc sulphide (ZnS), a II–VI group semiconductor material possessing a direct band gap of 3.66 eV, has recently been extensively investigated due to its multifaceted applications. We report the synthesis of ZnS nanorods by a simple physical vapor deposition method and an in-detail surface analysis for device applications. Our interest in this material mainly lies behind its use as an n-window layer for our investigations on different window layers for CdTe- and CIS (Copper Indium diselenide) based solar cells and for photocatalytic production of hydrogen from water using the photocatalysts CdS/ZnS. ZnS films are deposited onto well-cleaned glass substrates at a vacuum of 5×10^-5 Torr and various parameters are determined. The distance between the substrate and the source was maintained at 0.15 cm. The deposition time was about 20 min at a constant rate of evaporation and the substrates were maintained at room temperature. Structural analysis reveals the cubic nature of the crystallites, which is confirmed from atomic force microscopy (AFM) analysis. The AFM analysis reveals the formation of nanorods due to coalescence, which is substantiated from sectional analysis. A further analysis reveals the preferential growth of the nanorods and the coalescence limited by the energy in the (002) face. The composition was analyzed using an energy-dispersive X-ray method (EDX) and the film was found to possess excess sulfur. The band gap of the vacuum-deposited ZnS film was found to be 3.6 eV. PACS 61.16.Ch; 79.60.Jv; 61.46.+w; 61.50.Ah     

The Influence of Surface-Modification Technology on the Spectral Characteristics of Hydrophilic CdSe/ZnS Nanoparticles upon Interaction with Polyelectrolytes

The spectral and kinetic characteristics of CdSe/ZnS nanoparticles (NPs) surface-modified with cysteamine by two different methods are considered upon interaction with polyelectrolytes. With the use of steady-state and time-resolved fluorescence spectroscopies, it is shown that the fluorescence intensity and stability of NPs in the presence of polyelectrolytes depend on the surface-modification method. It is found that hydrophilic NPs obtained at the interface between two immiscible liquids (chloroform–water) are more resistant to aggregation.     

Two‐Photon Imaging of a Cellular Line Using Organic Fluorescent Nanoparticles Synthesized by Laser Ablation

A comparative study of the optical properties of organic fluorescent nanoparticles fabricated by laser ablation (NPs‐LA), reprecipitation (NPs‐RP), and microemulsion (NPs‐ME) methods is presented. These nanoparticles contain a fluorene‐based p‐conjugated molecule (BT2). Distinctive electronic transitions are observed in samples due to the specific way in which the molecule BT2 is assembled in each type of nanoparticles; for instance, transitions involved in absorption and emission spectra of NPs‐LA result in blueshifting with respect to the molecular solution of BT2, whereas redshifting is observed in NPs‐RP and NPs‐ME. Further, the results show that under infrared excitation, the aqueous suspensions of NPs‐LA exhibit the highest fluorescence induced by two‐photon absorption (≈790 GM at 740 nm), as well as the best photostability, compared with aqueous suspensions of NPs‐RP and NPs‐ME. The nanoparticles synthetized by the three aforementioned methods are employed as exogenous agents for the visualization of human cervical cancer cell line (HeLa) using confocal and two‐photon microscopy. Under similar experimental conditions, it is found that microscopy images of the best quality are obtained with NPs‐LA. These results show that laser ablation is a suitable technique for the fabrication of organic fluorescent nanoparticles used as contrast agents for in vitro fluorescence microscopy.