Synthesis and characterization of zinc oxide nanoparticles by laser ablation of zinc in liquid

We report formation of colloidal suspension of zinc oxide nanoparticles by pulsed laser ablation of a zinc metal target at room temperature in different liquid environment. We have used photoluminescence, atomic force microscopy and X-ray diffraction to characterize the nanoparticles. The sample ablated in deionized water showed the photoluminescence peak at 384 nm (3.23 eV), whereas peaks at 370 nm (3.35 eV) were observed for sample prepared in isopropanol. The use of water and isopropanol as a solvent yielded spherical nanoparticles of 14-20 nm while in acetone we found two types of particles, one spherical nanoparticles with sizes around 100 nm and another platelet-like structure of 1 μm in diameter and 40 nm in width. The absorption peak of samples prepared in deionized water and isopropanol are seen to be substantially blue shifted relative to that of the bulk zinc oxide due to the strong confinement effect. The technique offers an alternative for preparing the nanoparticles of active metal.     

Stability Investigation of Colloidal FePt Nanoparticle Systems by Spectrophotometer Analysis

FePt magnetic nanoparticle systems are an excellent candidate for ultrahigh-density magnetic recording. Monodisperse FePt nanoparticles are synthesized by superhydride reduction of FECl2·4H2O and Pt （acac）2 at 263℃ under N2 atmosphere. Transmission electron microscopy （TEM） images show monosize EePt nanoparticles with diameter of 4 nm and a standard deviation of about 10%. The average distance between monodispesre particles is nearly 3 nm, and oleic acid and oleylamine surround the nanoparticles as surfactants. Stability investigation of nanoparticle colloidal solution is done via speetrophotometery analysis. The results for FePt nanoparticles dispersed in hexane indicate that adding surfactants with concentration of 3 × 10^-3 part by volume for centrifugation stage increases the stability of FePt nanoparticles solution with concentration of 16 mg/mL, about 67%.     

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     

Temperature-induced particle self-assembly

Agglomeration of monodisperse thiol-stabilized gold particles with diameters of 6 nm, suspended in organic solvents, was induced by the cooling of the suspension. A sharp transition between the stable suspension and agglomeration resulted. The temperature of the transition depends on the concentration and the compatibility of the solvent. The morphology of the formed particle structures upon agglomeration implies that the used metal colloid can be described as a van der Waals-gas. The particles undergo phase transitions from a stable fluid phase to a metastable phase, in which nucleation and growth occur, or to an instable phase, in which spinodal decomposition occurs. The results will direct research on routes to nanostructured materials using nanoparticles as building blocks.     

Effect of surrounding gas temperature on the morphological evolution of TiO2 nanoparticles generated by laser ablation in tubular furnace

Titanium oxide nanoparticles are synthesized by laser ablation of Ti target in oxygen atmosphere under well-controlled temperature profiles in a tubular furnace. The size and the shape of generated nanoparticles are varied by changing the temperature of furnace. The mobility-based size distributions of generated air-borne nanoparticles are measured using a scanning mobility particle sizer, and the size distributions of primary particles are analyzed by a scanning electron microscope. When the particles are generated by laser ablation at the room temperature, the particles are agglomerates in gas phase with the average mobility diameter of 117 nm and the mean diameter of primary particles of 11 nm. The primary particle diameter increases from 11 to 24 nm by raising the furnace temperature up to 800 °C. Since the mass of Ti vapor ablated from a target is found to be constant regardless of the furnace temperature, this particle growth may be attributed to the reduction in nuclei number as a result of mild quenching at higher temperatures. As the temperature reaches higher than 1,000 °C, the mobility diameter suddenly drops and the primary particle diameter increases due to sintering, and at 1,200 °C the mobility diameter coincides with the primary particle diameter. Since the laser oven method offers an independent control of vapor concentration and the temperature of surrounding atmosphere, it is an effective tool to study the formation process of nanoparticles from primary particles with a given size.     

High-gradient magnetic separation of microparticles on membrane separation unit

A simple design of a magnetic separator based on a membrane made of a laser-perforated ferromagnetic foil has been proposed. The separator is primarily intended for analytical and research purposes. The developed magnetic separator of the proposed design has been tested in the separation of a composite aqueous suspension of magnetite nanoparticles adsorbed on hydroxyapatite microparticles. Separation efficiency has been determined via measuring the magnetic moment by the ferromagnetic resonance method; the suspension particle size has been found by dynamic light scattering before and after the separation process. It has been shown that all the particles with a diameter of more than 500 nm are retained during separation; the magnetization of the fraction decreases twofold after passing through the membrane.     

Manufacturing of nanoscale thickness gold lines by laser curing of a discretely deposited nanoparticle suspension

The present work is focused on a novel method for the manufacturing of electric microconductors for semiconductors and other devices. Three different technologies are combined in this technique: controlled (drop on demand) printing, laser curing, and the employment of nanoparticles of matter, possessing markedly different properties (here, melting point) than their bulk counterparts. A modified on demand ink jet process is utilized to print electrically conducting line patterns from a suspension of gold nanoparticles in toluene. Microdroplets of 60–100 μm diameter are generated and deposited on a moving substrate such that the droplets form continuous lines. Focused laser irradiation is utilized in order to evaporate the solvent, melt the metal nanoparticles in the suspension, and sinter the suspended particles to form continuous, electrically conducting gold microlines on a substrate. The ultrafine particles in the suspension have a diameter size range of 2–5 nm. Due to curvature and surface effects of such small particles, the melting point is markedly lower than that of bulk gold (1063 C). Atomic force microscopy and scanning electron microscopy have been employed to investigate the topology of the cured line. In situ visualization of the curing process has been conducted. Results on the effect of the laser irradiation power on the topology and width of the cured line, which is directly related to the electrical conductivity, are reported.     

Monolayer deposition of L10 FePt nanoparticles via electrospray route

The deposition monolayers of L1₀ FePt nanoparticles via an electrospraying method and the magnetic properties of the deposited film were studied. FePt nanoparticles in a size of around 2.5 nm in diameter, prepared by a liquid process, were used as a precursor. The size of the deposited particles can be controlled up to 35 nm by controlling the sprayed droplet size that is formed by adjusting the precursor concentration and the precursor flow rate. The droplets were heated in a tubular furnace at a temperature of up to 900 °C to remove all organic compounds and to transform the FePt particles from disordered face centered cubic to an ordered FCT phase. Finally, the particles were deposited in the form of a monolayer film on a silicon substrate by electrostatic force and characterized by scanning electron microscopy. The monolayer of particles was obtained by the high charge on particles obtained during the electrospraying process. The magnetic properties of the monolayer were investigated by magneto-optic Kerr effect measurements. Coercivity up to 650 Oe for a film consisting of 35 nm L1₀ FePt nanoparticles was observed after heat treatment at a temperature of 800 °C.     

Atomic force microscopy of cobalt nanoparticles with electro-catalytic properties

A method of controlled potential electrodeposition of the cobalt nanoparticles with sizes from 30 to 400 nm on the surface of highly oriented pyrolytic graphite has been developed. The images of nanoparticles were obtained with an atomic force microscope. A computer program was applied to obtain the size distribution of electrodeposited particles depending on the electrodeposition potential, electrolytic concentration, and deposition time. Using voltammetry it has been established that the cobalt nanoparticles with the diameter of about 50 nm show the maximal catalytic activity during electro-oxidation of ethanol.     

Decoration of carbon nanotube with size-controlled L10-FePt nanoparticles for storage media

In this work, first multi-wall carbon nanotubes (MWCNTs) with outer diameter about 20–30 nm are synthesized by a CVD method; they have been purified and functionalized with a two-step process. The approach consists of thermal oxidation and subsequent chemical oxidation. Then, monosize FePt nanoparticles along carbon nanotubes surface are synthesized by a Polyol process. The synthesized FePt nanoparticles are about 2.5 nm in size and they have superparamagnetic behavior with fcc structure. The CNTs surfaces as a substrate prevent the coalescence of particles during thermal annealing. Annealing at the temperature higher than 600 ^°C for 2 h under a reducing atmosphere (90 % Ar + 10 % H₂) leads to phase transition from fcc to fct-L1₀ structure. So, the magnetic behavior changes from the superparamagnetic to the ferromagnetic. Furthermore, after the phase transition, the FePt nanoparticles have finite size with an average of about 3.5 nm and the coercivity of particles reaches 5.1 kOe.     

Hydrothermal preparation of one-dimensional assemblies of PbS nanoparticles

The preparation of one-dimensional assemblies of PbS nanoparticles is described. By treating the suspension of PbCl₂ powders in aqueous thioacetamide solution at 120 °C for 18 h, PbS nanoparticles were synthesized in regular chain-like patterns. The particles were less than 100 nm in sizes, and were organized into micron-length assemblies. The starting agents have much influence on the morphology of the products. The possible growth mechanism is also discussed.     

Nanoparticles of: Synthesis and superparamagnetic properties

By using oil in water micelles, cobalt ferrite particles having an average diameter around 3 nm were synthetised. These nanoparticles are characterized by the presence of cation vacancies and no Fe(II) is observed, as it has been described in literature previously. Chemical interfacial treatment allows to coat the particles with citrate derivatives. The magnetic properties of uncoated and coated particles strongly diluted in a polymer substrate are compared by magnetization measurements and ⁵⁷Fe M?ssbauer spectroscopy. The anisotropy constant is shown to be independent of coating, whereas the magnetization is found to be larger in the uncoated particles. Received 3 February 1998     

Birefringence and scattering of light in colloidal solutions of magnetite in kerosene

The birefringence and dynamic and static scattering of light in colloidal solutions of magnetite nanoparticles in kerosene with different concentrations of the solid phase have been investigated. It is shown that these solutions contain both individual colloidal particles about 12 nm in diameter and their aggregates up to 100?600 nm in diameter. The largest aggregates are formed in solutions with the lowest concentration (on the order of 0.001 vol % or lower). The presence of relatively large aggregates makes it possible to observe specific features of optical anisotropy relaxation in these solutions, which are related to the non-Rayleigh character of light scattering from magnetite-particle aggregates.     

Synthesis of immunomagnetic nanoparticles and their application in the separation and purification of CD34 hematopoietic stem cells

The silica-coated superparamagnetic nanoparticles with the uniform diameter of about 60 nm were synthesized by reverse microemulsions method. And the magnetic nanoparticles were modified with N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (AEAPS). The immunomagnetic nanoparticles were then successfully prepared by covalently immobilizing anti-CD34⁺ monoclonal antibodies to the surface of amino silane modified magnetic particles. The cell separation results showed that the synthesized immunomagnetic nanoparticles could rapidly and conveniently separate the CD34⁺ cells with high efficiency and specificity than normal ones. The surface morphology of separated target cells was examined by scanning electron microscope (SEM). Atomic force microscope (AFM) also characterized the magnetic materials on the surface of the separated target cells for the first time, which further confirmed that the target cells were separated by the immunomagnetic nanoparticles. The viability of the separated cells was studied by culturing method and Beckman Vi-cell viability analyst. Therefore, our experiments provided a new, direct, rapid mode to separate target cells.     

Surface effects in maghemite nanoparticles

A consistent model is presented for the variation of saturation magnetization with particle size in maghemite nanoparticles, based on the existence of a magnetically disordered layer with a constant thickness of 1 nm. For particles smaller than 3 nm, layer thickness increases rapidly, and M_S is already zero for 2.5 nm particle size. Magnetization measurements have been performed on maghemite–polymer nanocomposites with low size dispersion and a regular distribution of particles in the matrix. A representative number of samples have been studied with a diameter size in the range from 1.5 to 15 nm and ±10% of size dispersion.     

Low temperature synthesis of iron containing carbon nanoparticles in critical carbon dioxide

We develop a low temperature, organic solvent-free method of producing iron containing carbon (Fe@C) nanoparticles. We show that Fe@C nanoparticles are self-assembled by mixing ferrocene with sub-critical (25.0 °C), near-critical (31.0 °C) and super-critical (41.0 °C) carbon dioxide and irradiating the solutions with UV laser of 266-nm wavelength. The diameter of the iron particles varies from 1 to 100 nm, whereas that of Fe@C particles ranges from 200 nm to 1 μm. Bamboo-shaped structures are also formed by iron particles and carbon layers. There is no appreciable effect of the temperature on the quantity and diameter distributions of the particles produced. The Fe@C nanoparticles show soft ferromagnetic characteristics. Iron particles are crystallised, composed of bcc and fcc lattice structures, and the carbon shells are graphitised after irradiation of electron beams.     

Kinetics of colloidal fractal aggregation by differential dynamic microscopy

We study the kinetics of an aggregation process induced by adding salt to a stable colloidal suspension of 73 nm (diameter) particles. Despite the subdiffraction size of the colloidal particles, the process is monitored via optical microscopy, which is used here to obtain time-resolved scattering information about the colloidal aggregates. The radius of the aggregates is determined as a function of time and their fractal dimension is extracted. Our results are compatible with a diffusion limited aggregation process, as independently confirmed by spectral turbidimetry measurements on the same sample.     

Magnetic properties of self-assembled nanostructure films on the base of amorphous Ni granules

We report on structural and magnetic properties of granular films consisting of 2.5 nm Ni nanoparticles. The films are fabricated by the original laser electrodispersion technique, which allows producing nearly monodisperse and amorphous particles. Atomic force microscopy (AFM) study shows that in 8 nm thickness films the particles are self-assembled in clusters with the lateral size 100-150 nm and the height of about 8 nm. Performed by SQUID, the films magnetization measurements reveal superparamagnetic behaviour, characteristic for an ensemble of non-interacting single domain magnetic particulates. It is found that the magnetic moment of the particulate is equal to that of about 3000 individual Ni nanoparticles and the blocking temperature is close to room temperature. Defined from magnetic measurements, the size of single domain particulates correlates well with the size of the clusters determined from AFM images. We propose that exchange interaction plays an important role in the formation of the particulates by aligning the magnetic moments of the individual Ni nanoparticles inside the clusters. Presence of magnetic clusters with high blocking temperature makes the fabricated films potentially useful for high-density magnetic data storage applications.     

一种新型银溶胶的制备、表征及其SERS活性的研究

报道了用一种化学还原方法制备银溶胶的新方法。用紫外-可见光谱和透射电镜研究银纳米粒子的形成过程,粒子形状及粒径分布。结果表明,在反应初期形成球形和棒状两种形状的银纳米粒子,随着反应的进行,大部分的棒状粒子逐渐变为球形粒子,最终棒状粒子少于银纳米粒子总数的3%。因此,最终得到了一种形状均一的,平均粒径为17nm银纳米粒子。同时也用紫外-可见光谱研究了Cl-的加入对这种银纳米粒子光谱性质的影响,结果表明Cl-加速了银纳米粒子的聚集。这种银溶胶有着较高的SERS活性。     

Surface-modification of indium tin oxide nanoparticles with titanium dioxide by a nonaqueous process and its photocatalytic properties

Indium tin oxide nanoparticles prepared by co-precipitation were re-dispersed in benzyl alcohol and modified successfully with titanium dioxide using titanium tetrachloride as precursor. The morphologies and the re-dispersing processes of both the initial and modified indium tin oxide nanoparticles were investigated, respectively. The photocatalytic properties of the modified nanoparticles were compared with commercial P25 photocatalyst. It was found that (i) the average diameter of the initial indium tin oxide nanoparticles was 10.7 nm and that of the surface-modified nanoparticles was 14.5 nm; (ii) the optimal ultrasonication time was 10.0 min and 8.0 min for the initial and surface-modified ITO nanoparticles, respectively; (iii) the modified particles possessed a higher photocatalytic activity than commercial P25 photocatalyst in the photodegradation of rhodamine B in aqueous medium at pH 5.00; (iv) the pH of the medium markedly influences the photodegradation efficiency.