核/壳结构的ZnS:Mn/SiO_2纳米粒子的制备及发光性质研究

采用溶剂热法制备了Mn离子掺杂的ZnS纳米粒子(ZnS∶Mn),然后利用正硅酸乙酯(TEOS)的水解反应对其进行了不同厚度的SiO2无机壳层包覆。采用X射线衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)及荧光发射光谱(PL)对样品的结构及光学性质进行了表征和研究。包覆SiO2壳层后,粒子的粒径明显增大并且在ZnS∶Mn纳米粒子表面可以观察到明显的SiO2壳层。XPS测试印证了ZnS∶Mn/SiO2的核壳结构。随着SiO2壳层的增厚,ZnS∶Mn/SiO2的Mn离子的发光先增强后减弱,这是因为SiO2壳层同时具有表面修饰和降低发光中心浓度这两种相反的作用。当壳层厚度(壳与核的物质的量的比)达到5时,发光效果达到最好,其强度达到未包覆样品的7.5倍。     

核/壳结构ZnS : Mn/CdS纳米粒子的制备及发光

利用溶剂热法制备了Mn离子掺杂的ZnS纳米粒子(ZnS : Mn),利用沉淀法对ZnS ∶ Mn纳米粒子进行了不同厚度的CdS无机壳层包覆。采用X射线衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)及光致发光(PL)光谱等手段对样品进行了表征。TEM显示粒子为球形,直径大约在14~18 nm之间。由XRD结果可以看出CdS壳层的形成过程受到了ZnS ∶ Mn核的影响,导致其结晶较差。XRD和XPS测量证明了ZnS : Mn/CdS的核壳结构。随着CdS壳层的增厚,样品的发光强度呈现一直减弱的现象。     

Gold decorated NaYF<Subscript>4</Subscript>:Yb,Er/NaYF<Subscript>4</Subscript>/silica (core/shell/shell) upconversion nanoparticles for photothermal destruction of BE(2)-C neuroblastoma cells

Gold decorated NaYF₄:Yb,Er/NaYF₄/silica (core/shell/shell) upconversion (UC) nanoparticles (~70–80 nm) were synthesized using tetraethyl orthosilicate and chloroauric acid in a one-step reverse microemulsion method. Gold nanoparticles (~6 nm) were deposited on the surface of silica shell of these core/shell/shell nanoparticles. The total upconversion emission intensity (green, red, and blue) of the core/shell/shell nanoparticles decreased by ~31% after Au was deposited on the surface of silica shell. The upconverted green light was coupled with the surface plasmon of Au leading to rapid heat conversion. These UC/silica/Au nanoparticles were very efficient to destroy BE(2)-C cancer cells and showed strong potential in photothermal therapy.     

Synthesis and characterization of Zn3P2/ZnS core/shell nanowires

Fully-surrounded Zn₃P₂/ZnS core/shell nanowires (NWs) were synthesized for the first time via a two-step method: a catalyst free chemical vapor deposition followed by a low-pressure vulcanization process. Field emission scanning electron microscopy, high-resolution transmission electron microscopy, and high-angle angular dark field scanning transmission electron microscopy were used to characterize the morphologies, crystal structure, and element composition of the core/shell NWs. The band structure analysis demonstrates that the Zn₃P₂/ZnS core-shell NW type-II heterostructures have bright potential in photovoltaic nanodevice applications. The core/shell NW growth method used here can be extended to other material system.     

Luminescence enhancement of Mn doped ZnS nanocrystals passivated with zinc hydroxide

Mn-doped ZnS nanocrystals prepared by solvothermal method have been successfully coated with different thicknesses of Zn(OH)₂ shells through precipitation reaction. The impact of Zn(OH)₂ shells on luminescent properties of the ZnS:Mn nanocrystals was investigated. X-ray diffraction (XRD) measurements showed that the ZnS:Mn nanocrystals have cubic zinc blende structure. The morphology of nanocrystals is spherical shape measured by transmission electron microscopy (TEM). ZnS:Mn/Zn(OH)₂ core/shell nanocrystals exhibited much improved luminescent properties than those of unpassivated ZnS:Mn nanocrystals. The luminescence enhancement was observed with the Zn(OH)₂ shell thickening by photoluminescence (PL) spectra at room temperature and the luminescence lifetime of transition from ⁴T₁ to ⁶A₁ of Mn²⁺ ions was also prolonged. This result was led by the effective, robust passivation of ZnS surface states by the Zn(OH)₂ shells, which consequently suppressed nonradiative recombination transitions.     

Copper- or manganese-doped ZnS quantum dots as fluorescent probes for detecting folic acid in aqueous media

3-Mercaptopropionic acid-capped core/shell ZnS:Cu/ZnS and ZnS:Mn/ZnS doped quantum dots (QDs) prepared through hydrothermal methods exhibit high photoluminescence intensity as well as good photostability. These water-dispersible nanoparticles exhibit high fluorescence sensitivity to folic acid due to the high affinity of the carboxylate groups and nitrogen atoms of folic acid towards the Zn surface atoms of the doped dots. Quenching of the fluorescence intensity of the QDs allows the detection of folic acid concentrations as low as 11 μM, thus affording a very sensitive system for the sensing of this biologically active molecule in aqueous solution. The possible quenching mechanism is discussed.     

A comparative study of conventional type II and inverted core–shell nanostructures based on CdSe and ZnS

The objective of this work is to investigate structural, morphological and optical properties of conventional CdSe/ZnS core–shell and inverted ZnS/CdSe core–shell nanostructures for opto-electronic device applications. For this purpose both nanostructures were synthesized using chemical bath deposition technique in thin film form. The structural properties were studied using X-ray diffraction technique with Rietveld refinement and transmission electron microscopy (TEM). The surface morphology of synthesized thin film was illustrated in the form 2D and 3D images using atomic force microscopy (AFM). The optical properties were explained using UV–Vis absorption spectroscopy and photo luminescence (PL) spectroscopy in in situ monitoring process. A comparison of estimated particle size from XRD, high resolution AFM and TEM images was resulted in good agreement as 2.1, 2.4 and 2.1 nm respectively for conventional CdSe/ZnS core–shell and as 2.5, 2.5 and 2.2 nm respectively for inverted ZnS/CdSe core–shell nanostructures.     

Synthesis and photoluminescent properties of silica-coated LaCeF<Subscript>3</Subscript>:Tb nanocrystals

La_0.45Ce_0.45F₃:Tb (10 mol% Tb) nanoparticles was synthesized via sonochemical method and then coated with silica (SiO₂) shells through a microemulsion process, resulting in the formation of core/shell structured LaCeF₃:Tb/SiO₂ nanoparticles. The obtained core/shell LaCeF₃:Tb/SiO₂ nanoparticles are spherical and uniform in size (average size about 60 nm), strongly fluorescent, and long fluorescence lifetime (1.87 ms). This kind of nanoparticles was water-soluble, which could be applied in biological labeling and other fields.     

Synthesis of core–shell nanoparticles with a Pt nanoparticle core and a silica shell

A method to prepare a core–shell structure consisting of a Pt metal core coated with a silica shell (Pt(in)SiO₂) is described herein. A silica shell was grown on poly(vinylpyrrolidone) (PVP)-stabilized Pt nanoparticles 2–3 nm in size through hydrolysis and condensation reactions of tetraethyl orthosilicate (TEOS) in a water/ethanol mixture with ammonia as a catalyst. This process requires precise control of the reaction conditions to avoid the formation of silica particles containing multiple Pt cores and core-free silica. The length of PVP molecules, water content, concentration of ammonia and Pt nanoparticles in solution were found to significantly influence the core–shell structure. By optimizing these parameters, it was possible to prepare core–shell particles each containing a single Pt nanoparticle with a silica layer coating approximately 10 nm thick.     

Synthesis and characterization of aqueous MPA-capped CdS–ZnS core–shell quantum dots

The novel CdS–ZnS core–shell nanoparticles are synthesized using simple one-step aqueous chemical approach. 3-mercaptopropionic acid (MPA) was used as the capping molecule. The structural and optical properties of the prepared samples are characterized by X-ray diffraction (XRD), UV–vis absorption spectroscopy, photoluminescence (PL) spectroscopy, energy-dispersive X-ray (EDX) and transition electron microscopy (TEM). The studies show that pH contributed noticeably to the growth and optical properties of nanoparticles. The TEM results indicate that the prepared particles have core–shell structure.     

Influence of Shell Formation on Morphological Structure,Optical and Emission Intensity on Aqueous Dispersible NaYF4:Ce/Tb Nanoparticles

A highly water-dispersible NaYF₄:Ce/Tb (core), NaYF₄:Ce/Tb@NaYF₄(core/shell) and NaYF₄:Ce/Tb@NaYF₄@SiO₂ (core/shell/SiO₂) nanoparticles (NPs) were synthesized via a general synthesis approach. The growth of an inert NaYF₄ and silica shell (~14 nm) around the core-NPs resulted in an increase of the average size of the nanopaticles as well as broadening of their size distribution. The optical band-gap energy slightly decreases after shell formation due to the increase the crystalline size. To optimize the influence of shell formation a comparative analysis of photoluminescence properties (excitation, emission, and luminescence decay time) of the core, core/shell, and core/shell/SiO₂ NPs were measured. The emission intensity was significantly enhanced after inert shell formation around the surface of the core NPs. The Commission International de l’Eclairage chromaticity coordinates of the emission spectrum of core, core/shell, core/shell/SiO₂ NPs lie closest to the standard green color emission at 545 nm. By quantitative spectroscopic measurements of surface-modified core-NPs, it was suggested that encapsulation with inert and silica layers was found to be effective in retaining both luminescence intensity and dispersibility in aqueous environment. Considering the high aqueous dispersion and enhanced luminescence efficiency of the core-NPs make them an ideal luminescent material for luminescence bioimaging and optical biosensors.     

Facile synthesis of mercaptosuccinic acid-capped CdTe/CdS/ZnS core/double shell quantum dots with improved cell viability on different cancer cells and normal cells

Water-soluble, mercaptosuccinic acid (MSA)-capped CdTe/CdS/ZnS core/double shell quantum dots (QDs) were prepared by successive growth of CdS and ZnS shells on the as-synthesized CdTe/CdS_thin core/shell quantum dots. The formation of core/double shell structured QDs was investigated by ultraviolet-visible (UV–Vis) absorption and photoluminescence (PL) spectroscopy, PL decay studies, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The core/double shell QDs exhibited good photoluminescence quantum yield (PLQY) which is 70% higher than that of the parent core/shell QDs, and they are stable for months. The average particle size of the core/double shell QDs was ～3 nm as calculated from the transmission electron microscope (TEM) images. The cytotoxicity of the QDs was evaluated on a variety of cancer cells such as HeLa, MCF-7, A549, and normal Vero cells by 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) cell viability assay. The results showed that core/double shell QDs were less toxic to the cells when compared to the parent core/shell QDs. MCF-7 cells showed proliferation on incubation with QDs, and this is attributed to the metalloestrogenic activity of cadmium ions released from QDs. The core/double shell CdTe/CdS/ZnS (CSS) QDs were conjugated with transferrin and successfully employed for the biolabeling and fluorescent imaging of HeLa cells. These core/double shell QDs are highly promising fluorescent probe for cancer cell labeling and imaging applications.     

Morphology-engineered strain transformation in Ge/GeO2 core/shell nanoparticles

Growth of nanoparticles embedded in a host matrix can lead to substantial strain. Ge/GeO₂ core/shell nanoparticles embedded in amorphous Al₂O₃ matrix is fabricated by the pulsed laser deposition method and rapid thermal annealing technique, which is confirmed by the experimental HRTEM result and consistent with Zhdanov׳s theoretical prediction. A finite-element calculation is performed to investigate the tuning effect on the strain by the morphology evolution of the Ge/GeO₂ core/shell nanoparticle embedded in Al₂O₃ matrix. The simulated result indicates that the strain at the interface between the core and the shell strongly depends on the morphology of the nanoparticles. Moreover, it can be found that there is a dramatic transformation of the strain on Ge core from tensile to compressive strain during the shrinkage of Ge core and the expansion of GeO₂ shell. The simulated results indicate that the strain can be designed by tuning the morphology of the nanoparticles, which provides an opportunity to engineer the properties of the nano-sized core/shell structures.     

Synthesis, structural and optical characterization of nanocrystalline ZnS:Cu embedded in silica matrix

The synthesis of Cu doped ZnS nanoparticles inside the pore of an inorganic silica gel matrix is presented. The synthesized nanoparticles were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX). X-ray diffraction pattern reveals the crystalline wurtzite phase of ZnS. The existence of silica gel in modeling morphologies of the nanoparticles was characterized using Fourier transform infrared (FTIR) spectrometer. Thickness of the silica shell was also calculated. UV- absorption spectrum shows the appearance of an absorption peak at 273 nm which confirms the blue shift as compared to that of bulk ZnS. The photoluminescence (PL) emission spectrum of the sample showed a broad band in the range 465-510 nm due to the transition from the conduction band edge of ZnS nanocrystals to the acceptor like t₂ state of Cu.     

Preparation and characterizations of SiO2-coated nanoparticles of Mn0.4Zn0.6Fe2O4

Core/shell nanoparticles consisting of a magnetic core of zinc-substituted manganese ferrite (Mn_0.4Zn_0.6Fe₂O₄) and a shell of silica (SiO₂) are prepared by a sol-gel method using tetraethyl orthosilicate (TEOS) as a precursor material for silica and salts of iron, manganese and zinc as the precursor of the ferrite. Three weight percentages of the shell materials of SiO₂ are used to prepare the coated nanoparticles. The X-ray diffractograms (XRD) of the coated and uncoated magnetic nanoparticles confirmed that the magnetic nanoparticles are in their mixed spinel phase in an amorphous matrix of silica. Particles sizes of the samples annealed at different temperatures are estimated from the width of the (3 1 1) line of the XRD pattern using the Debye-Sherrer equation. The information regarding the crystallographic structure together with the particles sizes extracted from the high-resolution transmission electron microscopy (HRTEM) of a few selected samples are in agreement with those obtained from the XRD. HRTEM observations revealed that particles are coated with silica. The calculated thickness is in agreement with that obtained from the HRTEM pictures. Hysteresis loops observed in the temperature range 300 down to 5 K and Mössbauer spectra at room temperature indicate superparamagnetic relaxation of the nanoparticles.     

CdSe &; ZnS core/shell nanoparticles generated by laser ablation of microparticles

Laser Ablation of Microparticles (LAM) is a process of nanoparticle formation in which microparticles in a flowing aerosol are continuously ablated by high-power laser pulses. For the first time, we have produced CdSe/ZnS core/shell nanoparticles using a double ablation apparatus, designed to undergo a two-step LAM process. This process can be inverted to produce ZnS/CdSe core/shell nanoparticles. The present work focuses on the range around ∼15 nm radius heterostructures and uses high-resolution transmission electron microscopy (HRTEM) to image core and shells. For smaller particles, core shell structures have been detected with energy dispersive spectroscopy (EDS) 5 nm spot size beam and fast Fourier transform (FFT) spectra. Differences in the ablation behavior were measured between the two IIB–VIA type semiconductors.     

Influence of Surface Coating on Structural and Photoluminescent Properties of CaMoO4:Pr Nanoparticles

CaMoO₄:Pr(core), CaMoO₄:Pr@CaMoO₄ (core/shell) and CaMoO₄:Pr@CaMoO₄@SiO₂ (core/shell/shell) nanoparticles were synthesized using polyol method. X-ray diffraction (XRD), thermogravimatric analysis (TGA), UV–vis absorption, optical band gap energy analysis, Fourier transform infrared (FTIR), FT-Raman and photoluminescence (PL) spectroscopy were employed to investigate the structural and optical properties of the synthesized core and core/shell nanoparticles. The results of the XRD indicate that the obtained core, core/shell and core/shell/shell nanoparticles crystallized well at ~150 °C in ethylene glycol (EG) under urea hydrolysis. The growth of the CaMoO₄ and SiO₂ shell (~12 nm) around the CaMoO₄:Pr core nanoparticles resulted in an increase of the average size of the nanopaticles as well as in a broadening of their size distribution. These nanoparticles can be well-dispersed in distilled water to form clear colloidal solutions. The photoluminescence spectra of core, core/shell and core/shell/shell nanoparticles show the characteristic charge transfer emission band of MoO₄ ^2? (533 nm) and Pr³⁺ 4f²?→?4f², with multiple strong ³H₄?→?³P₂, ¹D₂?→?³H₄ and ³P₀?→?³?F₂ transitions located at ~490, 605 and 652 nm, respectively. The emission intensity of the CaMoO₄:Pr@CaMoO₄ core/shell and CaMoO₄:Pr@CaMoO₄@SiO₂ core/shell/shell nanoparticles increased ~4.5 and 1.7 times,respectively, with respect to those of CaMoO₄:Pr core nanoparticles. This indicates that a significant amount of nonradiative centers existing on the surface of CaMoO₄:Pr@CaMoO₄ core/shell nanoparticles can be eliminated by the shielding effect of CaMoO₄ shells.     

Distinguishing the core from the shell in MnO(x)/MnO(y) and FeO(x)/MnO(x) core/shell nanoparticles through quantitative electron energy loss spectroscopy (EELS) analysis

The structural and chemical characterization of inverted bi-magnetic MnO_x(antiferromagnetic)/MnO_y(ferrimagnetic) and FeO_x(soft-ferrimagnetic)/MnO_x(hard-ferrimagnetic) core/shell nanoparticles has been carried out by means of scanning transmission electron microscopy with electron energy loss spectroscopy analysis, (S)TEM-EELS. Quantitative EELS was applied to assess the local composition of the nanoparticles by evaluating the local Mn oxidation state based on the Mn L₃/L₂ peak intensity ratio and the Mn L₃ peak onset. The analysis allows to unambiguously distinguish the core from the shell and to determine the nature of the involved manganese oxides in both cases. The results evidence that the structure of the nanoparticles is, in fact, more complex than the one designed by the synthesis parameters.     

Mn2+ as a radial pressure gauge in colloidal core/shell nanocrystals

The fluorescence of Mn2+ doped in the shell of CdS/ZnS core/shell nanocrystals at radially controlled position is used as a local probe of pressure in the nanocrystal shell. The redshift of the fluorescence with increasing shell thickness indicates a pressure of more than 4 GPa for 7.5 monolayers of ZnS. The radial dependence and magnitude of the pressure derived from the Mn2+ fluorescence shift are in good agreement with the spherically symmetric elastic continuum model and the 7% misfit between the core and the epitaxial shell.     

Synthesis of high quality and monodisperse CdS:Mn/ZnS and CdS:Mn/CdS core–shell nanoparticles

CdS:Mn²⁺/ZnS and CdS:Mn²⁺/CdS core–shell nanoparticles were synthesized in aqueous medium via chemical precipitation method in an ambient atmosphere. Polyvinylpyrrolidone (PVP) was used as a capping agent. The effect of the shell (ZnS and CdS) thickness on CdS:Mn²⁺ nanoparticles was investigated. Inorganically passivated core/shell nanocrystals having a core (CdS:Mn²⁺) diameter of 4 nm and a ZnS-shell thickness of ∼0.5 nm exhibited improved PL intensity. Optimum concentration of doping ions (Mn²⁺) was selected through optical study. For all the core–shell samples two emission peaks were observed, the first one is band edge emission in the lower wavelength side due to energy transfer to the Mn²⁺ ions in the crystal lattice; the second emission is characteristic peak of Mn²⁺ ions (⁴T₁ → ⁶A₁). The XRD, TEM and PL results showed that the synthesized core–shell particles were of high quality and monodisperse.