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。     

A convenient ultrasonic irradiation technique for in situ synthesis of zinc sulfide nanocrystallites at room temperature

Nanocrystalline ZnS has been synthesized using a sonochemical reaction of a mixed solution of Zn(NO₃)₂, Na₂S₂O₃ and (CH₃)₂(OH)CH in Ar under ambient conditions. Detailed investigations with X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) are reported. It was found that phase-pure ZnS nanocrystallites were produced, and the ZnS nanoparticles were about 6.5 nm in size, as indicated by TEM observation. The chemical mechanism for the formation of ZnS nanocrystals is discussed. This convenient method is found to be an efficient way to produce other chalcogenides as well. PACS 81.05.Dz; 81.05.Ys; 81.20.Zx     

Structural and optical characterization of ZnS nanoparticles co-doped with Mn and Te

Nanoparticles of Zinc sulfide co-doped with equal atomic percentages of Mn and Te (5, 10 and 15 at%) were synthesized for the first time by chemical co-precipitation method. Thiophenol was used to passivate the surface of the particles. The as-prepared samples were amorphous in nature and nano-crystallinity was induced after calcining at 300 °C/2 h. The nanoparticles were characterized by EDAX, XRD, TEM, optical absorption and PL studies. EDAX spectra revealed only minor deviations of the dopant concentrations from the target compositions. The nanoparticles showed cubic structure. The particle size estimated from XRD/TEM was in the range 3–5 nm. Optical absorption studies showed a blue-shift of the fundamental absorption edge with respect to that of bulk ZnS. PL spectra showed emission in the red region with composition dependent emission wavelength. ZnS nanoparticles doped with Mn (5 and 10 at%) were also synthesized and characterized for comparison.     

Formation of zinc sulfide nanoparticles in HMTA matrix

A hydrothermal method has been optimized for the synthesis of ZnS nanoparticles. The nanoparticles were stabilized using Hexamethylenetetramine (HMTA) as surfactant in aqueous solution. The self-assembling of the surfactant molecules in the water solution forms a unique architecture that can be adopted as the reaction template for the formation of nanomaterials. The average grain size of the nanoparticles calculated from the XRD pattern was of the order of 2 nm which exhibits cubic zinc-blende structure. TEM results showed that the synthesized nanoparticles were uniformly dispersed in the HMTA matrix without aggregation. The spectroscopic results revealed that the synthesized ZnS nanoparticles exhibits strong quantum confinement effect as the optical band gap energy increased significantly compared to the bulk ZnS material. Formation of HMTA capped ZnS nanoparticles were confirmed by FTIR studies. The PL spectra exhibit a strong green emission peak around 502 nm attributed to some self-activated defect centers related to Zn-vacancies.     

One-pot synthesis and optical properties of monodisperse ZnSe colloidal microspheres

Monodisperse ZnSe colloidal microspheres were fabricated by a green one-pot wet chemical strategy through aggregation of primary nanoparticles without expensive organic additives or reductants involved. The as-prepared products were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectrum, X-ray photoelectron spectroscopy (XPS), UV–vis absorption and room-temperature photoluminescence techniques. The size-dependent optical spectra of as-obtained microspheres were blue-shifted in comparison with that of bulk ZnSe and exhibit near band edge luminescence, indicating the quantum confinement effect. The strong and stable blue emission band from the ZnSe colloidal microspheres indicates their potential applications as building blocks in photonic crystals.     

A facile way for preparing tin nanoparticles from bulk tin via ultrasound dispersion

In this paper, we reported a facile and rapid process to prepare tin nanoparticles from bulk tin via ultrasound dispersion. The morphology and structure of synthesized tin nanoparticles were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectrum (XPS) and thermogravimetric analysis (TGA). The results show that the morphology of tin nanoparticles is spherical and the structure of tin nanoparticles has the same crystal structure as the bulk tin. In addition, the tribological property of tin nanoparticles as additives in oil is evaluated on a four-ball tester and the results show that tin nanoparticles exhibit good performance in wear.     

Structural and optical properties of monodispersed ZnS/CdS/ZnO and ZnO/ZnS/CdS nanoparticles

Excellent luminescence properties of ZnS/CdS/ZnO and ZnO/ZnS/CdS nanocrystallites synthesized through a simple chemical method at room temperature are reported. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), UV–visible absorption and photoluminescence techniques were used to characterize the undoped ZnS, CdS and ZnO and the novel ZnS/CdS/ZnO and ZnO/ZnS/CdS nanoparticles. The optical properties of ZnS/CdS/ZnO and ZnO/ZnS/CdS nanoparticles reflect a combinational effect of the photoluminescent properties of ZnS, CdS and ZnO.     

Study of optical and thermal properties in nickel doped ZnS nanoparticles using surfactants

The presence of surfactants polyethylene glycol (PEG), polyvinyl pyrrolidone (PVP), sodium hexameta polyphosphate (SHMP) and tri-octyl phosphine oxide (TOPO) on the surface of Ni²⁺ doped ZnS (ZnS:Ni²⁺) nanoparticles resulted variation in their optical properties. The optical properties of each surfactant-capped ZnS:Ni²⁺ nanoparticles were investigated using UV–visible (UV–Vis) absorption and photoluminescence (PL) techniques. The absorption spectra and fluorescent emission spectra showed a significant blue shift compared to that of the bulk zinc sulfide. The effect of the optical properties in colloidal form (wet) and dry samples were investigated. Enhanced PL emission was observed for the dry samples at 80 °C. Thermal properties of the ZnS:Ni²⁺ was also studied using thermo gravimetric-differential thermal analysis (TG-DTA), Fourier transform infra-red spectrometer (FT-IR) and X-ray diffraction (XRD). The results are presented and discussed.     

Glass transition temperature and thermal stability of ZnS/PMMA nanocomposites

In this article, ZnS nanoparticles were prepared by wet chemical precipitation method using zinc sulphate (ZnSO₄), sodium sulphide (Na₂S) and thio-glycerol. These nanoparticles were characterized through X-ray diffraction (XRD) and transmission electron microscope (TEM) measurements. The solution-based processing was used to prepare Poly methyl methacrylate (PMMA) nanocomposites with different weight percents (0, 2, 4, 6 and 8) of ZnS nanoparticles. The obtained ZnS/PMMA nanocomposites were characterized through XRD, scanning electron microscope and TEM measurements. The dynamic mechanical analyzer was used to obtain the storage modulus and glass transition temperature (T _g) of the nanocomposites. The apparent activation energy of the glass transition region was also determined using the Vogel–Fulcher–Tammann equation. The results indicated that the thermal stability of ZnS/PMMA nanocomposites was higher than PMMA and 6 wt. % of ZnS nanoparticles in PMMA matrix showed the maximum activation energy, which indicated that this nanocomposite had higher thermal stability than other composites.     

Photoluminescence characteristics of ZnS nanocrystallites doped with Ti3+and Ti4+

Direct synthesis of ZnS nanocrystallites doped with Ti³⁺ or Ti⁴⁺ by precipitation has led to novel photoluminescence properties. Detailed X-ray diffraction (XRD), fluorescence spectrophotometry, UV–vis spectrophotometry and X-ray photoelectron spectroscopy (XPS) analysis reveal the crystal lattice structure, average size, emission spectra, absorption spectra and composition. The average crystallite size doped with different mole ratios, estimated from the Debye–Scherrer formula, is about 2.6±0.2 nm. The nanoparticles can be doped with Ti³⁺ and Ti⁴⁺ during the synthesis without the X-ray diffraction pattern being altered. The strong and stable visible-light emission has been observed from ZnS nanocrystallites doped with Ti³⁺ (its maximum fluorescence intensity is about twice that of undoped ZnS nanoparticles). However, the fluorescence intensity of the ZnS nanocrystallites doped with Ti⁴⁺ is almost the same as that of the undoped ZnS nanoparticles. The emission peak of the undoped sample is at 440–450 nm. The emission spectrum of the doped sample consists of two emission peaks, one at 420–430 nm and the other at 510 nm. Received: 27 April 2001 / Accepted: 16 August 2001 / Published online: 17 October 2001     

核壳结构CdS/ZnS纳米微粒的制备与光学特性

用微乳液法制备CdS纳米微粒 ,以ZnS对其进行表面修饰 ,得到具有核壳结构的CdS/ZnS纳米微粒 .采用X射线衍射 (XRD)、透射电镜 (TEM )表征其结构、粒度和形貌 ,紫外 可见吸收光谱 (UV)、光致发光光谱(PL)表征其光学特性 .制得的CdS近似呈球形 ,直径为 3.3nm ;以XRD和UV证实了CdS/ZnS核壳结构的实现 .研究了不同ZnS壳层厚度对CdS纳米微粒光学性能的影响 ,UV谱表明随着壳层厚度的增加纳米微粒的吸收带边有轻微的红移 ,同时短波吸收增强 ;PL谱表明壳层ZnS的包覆可减少CdS纳米微粒的表面缺陷 ,带边直接复合发光的几率增大 ,具有合适的壳层厚度时发光效率大大提高 .     

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.      

Optical measurements of ZnS nanoparticles aqueous solution

We synthesized zinc sulfide (ZnS) nanopowders with size ranging from 2 to 100 nm by a simple, low-cost, and mass production chemical method. The nanoparticles (NPs) were characterized by X-ray powder diffraction (XRD), atomic force microscopy (AFM), transmission electron microscopy (TEM), and UV-vis absorption spectroscopy. Our study concerns also the change in the refractive index of deionized water in presence of ZnS nanospheres. We present experimental results on effective index variation of water dispersed ZnS NPs at different wavelengths in visible spectrum.     

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.     

Synthesis and characterization of mesoporous ZnS with narrow size distribution of small pores

Pure, nanocrystalline cubic ZnS forming a stable mesoporous structure was synthesized at room temperature by a non-toxic surfactant-assisted liquid–liquid reaction, in the 9.5–10.5 pH range of values. The appearance of an X-ray diffraction (XRD) peak in the region of very small angles (∼ 2°) reveals the presence of a porous material with a narrow pore size distribution, but with an irregular arrangement of the pores, a so-called worm hole or sponge-like material. The analysis of the wide angle XRD diffractograms shows the building blocks to be ZnS nanocrystals with cubic structure and average diameter of 2 nm. Transmission electron microscopy (TEM) investigations confirm the XRD results; ZnS crystallites of 2.5 nm with cubic (blende) structure are the building blocks of the pore walls with pore sizes from 1.9 to 2.5 nm, and a broader size distribution for samples with smaller pores. Textural measurements (N₂ adsorption–desorption isotherms) confirm the presence of mesoporous ZnS with a narrow range of small pore sizes. The relatively lower surface area of around 100 m²/g is attributed to some remaining organic molecules, which are filling the smallest pores. Their presence, confirmed by IR spectroscopy, seems to be responsible for the high stability of the resulting mesoporous ZnS as well. PACS  61.46.Df; 68.37.Lp; 78.67.-n; 81.05.Ea; 81.07.Bc     

Influence of pH on the preparation of dispersed Ag–TiO<Subscript>2</Subscript> nanocomposite

In this paper, data concerning the effect of pH on the morphology of Ag–TiO₂ nanocomposite during photodeposition of Ag on TiO₂ nanoparticles is reported. TiO₂ nanoparticles prepared by sol–gel method were coated with Ag by photodeposition from an aqueous solution of AgNO₃ at various pH levels ranging from 1 to 10 in a titania sol, under UV light. The as-prepared nanocomposite particles were characterized by UV–vis absorption spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), and N₂ adsorption/desorption method at liquid nitrogen temperature (−196 °C) from Brunauer–Emmett–Teller (BET) measurements. It is shown that at a Ag loading of 1.25 wt.% on TiO₂, a high-surface area nanocomposite morphology corresponding to an average of one Ag nanoparticle per titania nanoparticle was achieved. The diameter of the titania crystallites/particles were in the range of 10–20 nm while the size of Ag particles attached to the larger titania particles were 3 ± 1 nm as deduced from crystallite size by XRD and particle size by TEM. Ag recovery by photo harvesting from the solution was nearly 100%. TEM micrographs revealed that Ag-coated TiO₂ nanoparticles showed a sharp increase in the degree of agglomeration for nanocomposites prepared at basic pH values, with a corresponding sharp decrease in BET surface area especially at pH > 9. The BET surface area of the Ag–TiO₂ nanoparticles was nearly constant at around a value of 140 m² g⁻¹ at all pH from 1–8 with an anomalous maximum of 164 m² g⁻¹ when prepared from a sol at pH of 4, and a sharp decrease to 78 m² g⁻¹ at pH of 10.     

Preparation and characterization of polyindole–ZnO composite polymer electrolyte with LiClO<Subscript>4</Subscript>

This paper describes the preparation and conductivity studies of polyindole–ZnO composite polymer electrolyte (CPE) with LiClO₄. Polyindole–ZnO-based polymer nanocomposites were prepared by chemical method and characterized by XRD, infrared (IR), scanning electron microscope (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The IR spectrum confirms the intermolecular interaction between polyindole and ZnO. The significant spectral changes of polyindole and ZnO nancomposites reveal the strong interaction between polyindole and ZnO nanoparticles. The structural morphologies of the ZnO, polyindole, and polyindole–ZnO are obtained from SEM. The TEM image of polyindole nanocomposite shows that ZnO is embedded in polyindole matrix. An enhanced conductivity of 4.405 × 10⁻⁷ S cm⁻¹ at 50 °C for the CPE was determined from impedance studies.     

Synthesis and characterization of Cu doped ZnS nanoparticles using TOPO and SHMP as capping agents

Undoped and Cu²⁺ doped (0.2-0.8%) ZnS nanoparticles have been synthesized through chemical precipitation method. Tri-n-octylphosphine oxide (TOPO) and sodium hexametaphosphate (SHMP) were used as capping agents. The synthesized nanoparticles have been analyzed using X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier transform infrared spectrometer (FT-IR), UV-vis spectrometer, photoluminescence (PL) and thermo gravimetric-differential scanning calorimetry (TG-DTA) analysis. The size of the particles is found to be 4-6 nm range. Photoluminescence spectra were recorded for ZnS:Cu²⁺ under the excitation wavelength of 320 nm. The prepared Cu²⁺-doped sample shows efficient PL emission in 470-525 nm region. The capped ZnS:Cu emission intensity is enhanced than the uncapped particles. The doping ions were identified by electron spin resonance (ESR) spectrometer. The phase changes were observed in different temperatures.     

The synthesis of highly oriented GaN nanowire arrays

Highly oriented GaN nanowire arrays have been achieved by the catalytic reaction of gallium with ammonium. The resulting materials were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM) and selected-area electron diffraction (SAED). SEM images show that the resulting materials are nanowire arrays with a uniform length of about 10 μm. XRD, EDS, TEM and SAED indicate that the nanowire arrays are single-crystal hexagonal GaN with a wurtzite structure. They have diameters of 10 to 20 nm. Received: 2 October 2002 / Accepted: 7 October 2002 / Published online: 17 December 2002 RID="*" ID="*"Corresponding author. E-mail: wwwangjc@sina.com