Synthesis and photoluminescence characteristics of doped ZnS nanoparticles

Free-standing powders of doped ZnS nanoparticles have been synthesized by using a chemical co-precipitation of Zn²⁺, Mn²⁺, Cu²⁺ and Cd²⁺ with sulfur ions in aqueous solution. X-ray diffraction analysis shows that the diameter of the particles is ∼2–3 nm. The unique luminescence properties, such as the strength (its intensity is about 12 times that of ZnS nanoparticles) and stability of the visible-light emission, were observed from ZnS nanoparticles co-doped with Cu²⁺ and Mn²⁺. The nanoparticles could be doped with copper and manganese during the synthesis without altering the X-ray diffraction pattern. However, doping shifts the luminescence to 520–540 nm in the case of co-doping with Cu²⁺ and Mn²⁺. Doping also results in a blue shift on the excitation wavelength. In Cd²⁺-doped ZnS nanometer-scale particles, the fluorescence spectra show a red shift in the emission wavelength (ranging from 450 nm to 620 nm). Also a relatively broad emission (ranging from blue to yellow) has been observed. The results strongly suggest that doped ZnS nanocrystals, especially two kinds of transition metal-activated ZnS nanoparticles, form a new class of luminescent materials. Received: 16 October 2000 / Accepted: 17 October 2000 / Published online: 23 May 2001     

Synthesis and fluorescence properties of pure and metal-doped spherical ZnS particles from EDTA-metal complexes

Monodispersed spherical ZnS particles as well as doped with Cu, Mn ions were synthesized from metal-chelate solutions of ethylenediamine tetraacetate (EDTA) and thioacetamide (TAA). The characterizations of the ZnS-based particles were investigated via TEM, SEM, XRD, TG/DTA and PL measurements. The sphere size was controlled from 50 nm to 1 μm by adjusting the nucleation temperatures and molar ratio of Zn-EDTA to TAA. The emission intensity continuously increased with the increase of the particle size. When the ZnS microspheres were annealed at 550-800 °C, there were two specific emission bands with the centers at 454 nm and 510 nm, which were associated with the trapped luminescence arising from the surface states and the stoichiometric vacancies, respectively. When Cu²⁺ was introduced into ZnS microspheres, the dominant emission was red-shifted from 454 to 508 nm, fluorescence intensity also sharply increased. However, for the Mn²⁺-doped ZnS, the emission intensity was significantly enhanced without the shift of emission site.     

Strong green luminescence of Ni2+-doped ZnS nanocrystals

ZnS nanoparticles doped with Ni²⁺ have been obtained by chemical co-precipitation from homogeneous solutions of zinc and nickel salt compounds, with S^2- as precipitating anion, formed by decomposition of thioacetamide (TAA). The average size of particles doped with different mole ratios, estimated from the Debye–Scherrer formula, is about 2–2.5 nm. The nanoparticles could be doped with nickel during synthesis without altering the X-ray diffraction pattern. A Hitachi M-850 fluorescence spectrophotometer reveals the emission spectra of samples. The absorption spectra show that the excitation spectra of Ni-doped ZnS nanocrystallites are almost the same as those of pure ZnS nanocrystallites (λ_ex=308–310 nm). Because a Ni²⁺ luminescent center is formed in ZnS nanocrystallites, the photoluminescence intensity increases with the amount of ZnS nanoparticles doped with Ni²⁺. Stronger and stable green-light emission (520 nm) (its intensity is about two times that of pure ZnS nanoparticles) has been observed from ZnS nanoparticles doped with Ni²⁺. Received: 18 December 2000 / Accepted: 17 March 2001 / Published online: 20 June 2001     

Luminescence and structure of ZnO-ZnS thin films prepared by oxidation of ZnS films in air and water vapor

Effect of water vapor quantity at oxidation of undoped ZnS films on structural and luminescent properties of the obtained films was investigated. The films were deposited onto glass substrates by electron beam evaporation. ZnO-ZnS layers were prepared by thermal oxidization of ZnS films at 600 °C in dry or wet atmospheres. The films were characterized by X-ray diffraction, atomic force microscopy and photoluminescence spectroscopy. As-deposited ZnS films were sphalerite crystal structure. The “dry annealing” led to the ZnS phase transition from sphalerite to wurtzite structure and from ZnS to ZnO for a small fraction of the film. After the “wet annealing” the amount of ZnO phase with wurtzite structure growing along the 〈0 0 0 2〉 direction varied from 25% to 95% in dependence on the water vapor quantity. Photoluminescent spectrum at room temperature exhibits green emission with maximum at 2.4 eV. A strong influence of the water vapor on shape and intensity of the emission was observed. Photoluminescent spectra at 22 K consisted of two bands—high-energy band at 2.1-2.4 eV and low energy band at 1.7-1.8 eV. Location and intensity ratio depended on the preparation conditions.     

Chemical bath-deposited ZnS thin films: Preparation and characterization

Chemical bath deposition of ZnS thin films from NH₃/SC(NH₂)₂/ZnSO₄ solutions has been studied. The effect of various process parameters on the growth and the film quality are presented. The influence on the growth rate of solution composition and the structural, optical properties of the ZnS thin films deposited by this method have been studied. The XRF analysis confirmed that volume of oxygen of the as-deposited film is very high. The XRD analysis of as-deposited films shows that the films are cubic ZnS structure. The XRD analysis of annealed films shows the annealed films are cubic ZnS and ZnO mixture structure. Those results confirmed that the as-deposited films have amorphous Zn(OH)₂. SEM studies of the ZnS thin films grown on various growth phases show that ZnS film formed in the none-film phase is discontinuous. ZnS film formed in quasi-linear phase shows a compact and a granular structure with the grain size about 100 nm. There are adsorbed particles on films formed in the saturation phase. Transmission measurement shows that an optical transmittance is about 90% when the wavelength over 500 nm. The band gap (E_g) value of the deposited film is about 3.51 eV.     

Boosted UV emission at 349 nm from mesoporous ZnS

Relatively oxygen-free mesoporous cubic ZnS particles were synthesised via a facile solvo-hydrothermal route using a water–acetonitrile combination. Boosted UV emission at 349 nm is observed from the ZnS prepared by the solvo-hydrothermal route. The increased intensity of this UV emission is attributed to activation of whispering gallery modes of almost elliptical microstructures made of porous nanostructures.     

SEM and HRTEM analysis of ZnS nanoflakes produced by?a?simple route

In this work, we report the synthesis of ZnS nanostructures by a simple and eco-friendly method that makes possible producing nanoflakes at room temperature. Scanning electron microscopy and transmission electron microscopy methods (mainly bright-field, high resolution and high angle annular dark-field) were used to identify and study the obtained nanostructures. The structure of these nanoflakes consists of nanosized crystalline particles around 1.5 to 3 nm. Domains with different contrast of nanometer-size diameters are formed in the self-assembled nanoflakes as a result of a noncompact arrangement of nanocrystallites during agglomeration and differences in the presence of the organic passivation agent. Agglomeration can be attributed to the amount of crystallites generated at the beginning of the reaction or to an anisotropic interaction between phosphate ions and the surfaces of ZnS clusters, and consequently a bottom-up synthesis is considered, which opens a simple route for the production of nanomaterials with the inclusion of extra elements by a simple way.     

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.     

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.      

Preparation of Highly Stable and Photoluminescent Cadmium-Free InP/GaP/ZnS Core/Shell Quantum Dots and Application to Quantitative Immunoassay

Indium phosphide (InP) quantum dots (QDs) are ideal substitutes for widely used cadmium-based QDs and have great application prospects in biological fields due to their environmentally benign properties and human safety. However, the synthesis of InP core/shell QDs with biocompatibility, high quantum yield (QY), uniform particle size, and high stability is still a challenging subject. Herein, high quality (QY up to 72%) thick shell InP/GaP/ZnS core/shell QDs (12.8 ± 1.4 nm) are synthesized using multiple injections of shell precursor and extension of shell growth time, with GaP serving as the intermediate layer and 1-octanethiol acting as the new S source. The thick shell InP/GaP/ZnS core/shell QDs still keep high QY and photostability after transfer into water. InP/GaP/ZnS core/shell QDs as fluorescence labels to establish QD-based fluorescence-linked immunosorbent assay (QD-FLISA) for quantitative detection of C-reactive protein (CRP), and a calibration curve is established between fluorescence intensity and CRP concentrations (range: 1–800 ng mL⁻¹, correlation coefficient: R² = 0.9992). The limit of detection is 2.9 ng mL⁻¹, which increases twofold compared to previously reported cadmium-free QD-based immunoassays. Thus, InP/GaP/ZnS core/shell QDs as a great promise fluorescence labeling material, provide a new route for cadmium-free sensitive and specific immunoassays in biomedical fields.     

Femtosecond laser induced submicrometer structures on the ablation crater walls of II-VI semiconductors in water

Femtosecond laser ablations (100 fs, 800 nm, 0.2 mJ/pulse) were performed to produce craters on CdS, ZnS:Cu and ZnSe wafers in water. On the surface of the crater walls, a variety of submicrostructural formations were presented, such as the ripples and network structures for CdS, the subwavelength ripples and columnar structures for ZnS:Cu, even the regular cubic-shaped submicron rods for ZnSe. Based on the field-emission scanning electron microscope (FE-SEM) study of the different characteristic surface morphologies, the possible formation mechanisms were discussed correspondingly. For example, two distinct mechanisms are contributing to the different styles of ripples formed on CdS and ZnS:Cu. The former is the interference effects between the incoming laser beam and scattered surface wave, while the latter is the self-organization structure formation. In addition, the re-crystallization of the water-confined hot plasma would play an important role in the formation of ZnS:Cu column structures and ZnSe rods.     

Preparation and characterization of nontoxic magnetic-luminescent nanoprobe

A novel nontoxic,magnetic,and luminescent nanoprobe is prepared by using complex nanoparticles,which are composed of Fe3O4 nanoparticles and Mn-doped ZnS quantum dots(QDs).The nanocomposite probe can provide visible optical and magnetic resonance images simultaneously.Compared with the previously toxic cadmium and mercury based QDs,the superiority of the Mn-doped ZnS QDs is little virulence.The structure and the properties of the particles are characterized by energy dispersive X-ray analysis spectroscopy,X-ray photoelectron spectroscopy,transmission electron microscopy,photoluminescence spectroscopy,and vibrating sample magnetometer.     

Ion-induced secondary electron emission from ZnS thin films deposited by closed-spaced sublimation

ZnS thin films were deposited on soda lime glass and aluminum substrates by close-spaced sublimation technique. The change in composition, structural and optical properties of the films was investigated as a function of the substrate temperature. The deposited films were stoichiometric and crystalline in nature having cubic structure oriented only along (1 1 1) plane. The energy band gap of the films deposited at the substrate temperature of 150, 250 and 350 °C was 3.52, 3.58 and 3.63 eV respectively. These films were then bombarded with 2-10 keV energy pulsed Ar⁺ beam and their electron yield was determined from impinging ion and emitted electron currents. The electron yield of ZnS films was much high as compared to the metals. The electron yield of ZnS films increased with energy of the incident ion and got saturated at about 8 keV. The most important result of this study was that the electron yield of ZnS films having same composition was different. Monte Carlo simulations performed to interpret these experimental findings showed that the dissimilar electron yields of ZnS films is due to the combined effect of energy band gap, surface barrier potential and density of the films.     

Preparation and characterization of ZnS/CdS bi-layer for CdTe solar cell application

In this work, bilayer ZnS/CdS film was prepared as an improved window layer of CdTe solar cell. TEM was used to observe the cross section of the bilayer structure. The total thickness of ZnS/CdS film was about 60 nm, which could allow more photons to pass through it and contribute to the photocurrent. Optical properties of the bilayers were investigated using UV–vis spectroscopy. Compared with poor transmission of standard CdS film in the short wavelength range of 350–550 nm, the transmission of ZnS/CdS was improved and reached above 50%. The ZnS/CdS was annealed with CdCl₂. X-ray photoelectron spectroscopy (XPS) was used to investigate its chemical properties. A possible diffusion between CdS and ZnS was observed after annealing. The efficiency of standard CdS/CdTe solar cell was 9.53%. The device based on ZnS/CdS window layer had a poor 6% efficiency. With annealing treatment on ZnS/CdS layer, the performance was improved and reached 10.3%. In addition, the homogeneity of solar cell performance was improved using ZnS/CdS window layer. A thin ZnS layer was quite effective to reduce the possible shunt paths and short parts of window layer and consequently contributed to fabrication of a homogeneous CdTe solar cell.     

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.     

Synthesis and characterization of ZnS nanoparticles in water/AOT/n-heptane microemulsions

ZnS nanoparticles were synthetized using water-containing AOT reversed micelles as nanoreactors and characterized by UV-Vis spectrophotometry, HRTEM (high-resolution transmission electron microscopy), SAED (selected-area electron diffraction), and digital image processing. The experimental data evidence a slow growing process of fractal-like ZnS nanoparticles’ coupled with a change of their photophysical properties. Both these processes are well described by power laws. The nanoparticles size is mainly controlled by the micellar size. After evaporation of the organic solvent, it has been found that the deposit is constituted by smaller and more stable ZnS nanoparticles bathed in a surfactant matrix. Received: 20 April 1999 / Accepted: 23 April 1999 / Published online: 8 September 1999     

Combinatorial study of nanoparticle dispersion in surface-grafted macromolecular gradients

Surface-tethered assemblies of polymers with gradually varying molecular weight (MW) and/or grafting density are utilized to control the dispersion of nanosized particles. Using several case studies we show that these gradient polymer specimens represent ideal systems for combinatorial exploration of the parameters that control the distribution of the particles in surface-grafted layers. We demonstrate that the particle distribution is governed by the interplay between the particle size and the grafting density and molecular weight of the polymer brush.     

Effects of ZnS:Mn/AlN multilayer structure on luminescent properties of nanostructured thin-film EL device

Effects of ZnS:Mn/AlN multilayer structure on luminescent properties of nanostructured (NS) thin-film electroluminescent (TFEL) device of which emission layer is a multilayer composed with ZnS:Mn layers and 0.7-nm-thick AlN interlayers were studied. The bandgap widening and the increased PL efficiency of Mn²⁺ 3d-3d transitions with a decrease in the ZnS:Mn single-layer thickness down to 5 nm were observed, which is ascribed to quantum confinement effects. Meanwhile, the multilayer with 2-nm-thick ZnS:Mn single-layers shows a drop of PL efficiency, indicating the presence of defective region just on AlN. The tendency of the luminous efficiency of the NS-TFEL device against the ZnS:Mn single-layer thickness is similar to the tendency found in the PL efficiency, indicating the importance of the ZnS:Mn/AlN interface for the device performance.     

Preparation of luminescent ZnS:Cu nanoparticles for the functionalization of transparent acrylate polymers

Highly luminescent ZnS:Cu nanoparticles were synthesized in a coprecipitation route using aqueous salt solutions and thiopropionic acid as stabilizer. The method yields a stable, transparent particle dispersion in water and allows for a good control over particle size in the range of 3-10 nm as determined by dynamic light scattering, small angle X-ray scattering and transmission electron microscopy. Strong luminescence of the nanoparticles was observed under UV-excitation and emission colors could be adjusted in the range of blue to green by varying the Cu-doping concentration. The phase transfer of the ZnS:Cu nanoparticles into non-polar solvents using octylamine was used for a hydrophobic surface functionalization. The hydrophobic particles were used for the fabrication of transparent bulk nanocomposites via in situ-polymerization of dispersions in laurylacrylate. A high transparency of the composite materials, and the luminescence of the ZnS:Cu nanoparticles is retained during the phase transfer and the polymerization process allowing for the integration of a new luminescent functionality into the polymer material.     

Third-order elastic constants of ZnS and ZnSe

The complete set of non-vanishing third-order elastic constants of the semiconductors ZnS and ZnSe is obtained theoretically. The strain energy density is estimated using finite strain elasticity theory by considering the interactions up to two nearest neighbours of each atom in the unit cell of these compounds. This energy density is compared with the strain dependent lattice energy density from the continuum model approximation. The second-order parameter of the potential function φ is obtained from the measured principal axis C_ij. The third-order potential parameter is estimated by assuming a Lennard-Jones type of interatomic potential. The interlattice displacements as well as the second-order elastic constants are evaluated along with the six third-order elastic constants of ZnS and ZnSe. Using these second- and third-order elastic constants of ZnS, the pressure derivatives of second-order elastic constants are evaluated. The second- and third-order elastic constants of ZnSe are compared with the available experimental values. The third-order elastic constants show anisotropy in different directions.