In-situ study of Ag nanoparticle hydrosol optical spectra evolution during laser ablation/fragmentation

The results of in-situ monitoring of a laser fragmentation process of a largely polydisperse and morphologically heterogeneous citrate-reduced Ag hydrosol containing a fraction of Ag nanowires are presented. The laser fragmentation was performed using several wavelengths of the incident laser pulses (1064, 532 and 355 nm). Surface plasmon extinction spectra monitoring the nanoparticle fragmentation process were acquired pulse by pulse and related to transmission electron microscopy (TEM) images and statistical TEM image analysis of Ag nanoparticles collected in selected stages of the fragmentation. It was found that, due to different interactions of the laser pulses of various wavelengths with a specific fraction of the Ag nanoparticles in the hydrosol, the course of the fragmentation process depends on the wavelength, leading to different size distributions of the nanoparticles in the resulting hydrosol. The laser pulses of 532 nm wavelength are the most effective for the fragmentation process of the citrate-reduced Ag hydrosol, yielding the narrowest size distribution and the smallest mean radius of the Ag nanoparticles. PACS 81.07.-b; 73.21.-b; 81.16.-c     

The morphology of mass selected ruthenium nanoparticles from a magnetron-sputter gas-aggregation source

We have investigated the morphology of mass selected ruthenium nanoparticles produced with a magnetron-sputter gas-aggregation source. The nanoparticles are mass selected using a quadrupole mass filter, resulting in narrow size distributions and average diameters between 2 and 15 nm. The particles are imaged in situ by scanning electron microscopy and scanning tunneling microscopy (STM) as well as ex-situ using transmission electron microscopy (TEM). For each distribution of mass selected nanoparticles, the height determined by STM and the width determined by TEM are seen to be similar throughout the mass range investigated. The particles are found to have a well-defined morphology for diameters below approximately 6 nm. Larger nanoparticles are less well-defined having rough surfaces, unlike the equilibrium morphology determined from the Wulff construction. The morphology of the particles is, in general, believed to be determined by the conditions inside the gas-aggregation source and the morphology is retained as the particles are soft-landed on the substrate.     

Synthesis and characterization of boron carbide nanoparticles

Boron carbide nanoparticles were made via a reaction of boron, obtained from thermal decomposition of magnesium diboride, with multiwall carbon nanotubes at 1150 °C for 3 h in vacuum. The size of the nanoparticles is smaller than 100 nm. The bamboo structure of the multiwall carbon nanotubes is the key to the successful synthesis of such nanoparticles. Good crystallinity was demonstrated by scanning electron microscope images and X-ray diffraction patterns. The single-crystal nature of each nanoparticle was evidenced by a high-resolution lattice image obtained using a transmission electron microscope. PACS 61.10.Nz; 61.16.Bg; 81.05.Je; 81.07.Bc; 81.07.Wx     

Deriving the mean primary-particle diameter and related quantities from the size distribution and the gravimetric mass of spark generated nanoparticles

Spark generated carbon and iridium nanoparticles were characterised by their electrical-mobility diameter D and by the mass of particulate matter collected in parallel on filter. The particles exhibited slightly skewed lognormal size distributions with mean mobility diameters between 18 and 74 nm. The masses calculated from the measured distributions under the assumption that the particles were spherical (diameter D) and of bulk mass density turned out to be much higher than the gravimetric mass, by factors between 8 and as high as 340. This very pronounced difference initiated a search for an improved relation between particle size and mass. Data analysis suggested that the mass increases linearly with increasing D. Hence the measured distributions were evaluated under the assumption that the spark generated matter was composed of spherical primary nanoparticles of mean diameter d, aggregated in the form of chains of joint length βD, with β>1. Using reasonable values of β between 2 and 4, the mean diameter of carbon primary particles turned out to be 10±1.8 nm, in excellent agreement with size data recently obtained by transmission electron microscopy (TEM). The primary iridium particles were found to be distinctly smaller, with diameters between 3.5±0.6 nm and 5.4±0.9 nm. The comparatively small uncertainty is due to the fact that the primary-particle diameter is proportional to the square root of β. The calculated volume specific surface areas range between 500 and 1700 m²/cm³. These numbers are close to the ‘active’ surface areas previously measured by the BET method. The good agreement with TEM and BET data suggests that the novel approach of nanoparticle characterisation is meaningful. Accordingly, the number concentrations of all individual primary particles rather than the concentrations measured by the mobility analyser should be␣considered the correct dose metric in studies on animal exposure to spark generated nanoparticles. The␣evaluated data imply that the numbers quoted in the literature must be enlarged by factors ranging between about 10 and a maximum as high as 80. An erratum to this article can be found at     

Novel nanoparticle matter: ZrN-nanoparticles

This work presents the results of the first preparation (to the best of current knowledge) and investigation of ZrN nanoparticles. The particles were produced by laser ablation/evaporation and adiabatic expansion from zirconium nitride powder targets. The particle size could be varied by applying different seeding gas flows. The size distributions were fairly narrow with mean diameters from 2R=5.5 nm to 2R=6.5 nm. Compositional analysis by secondary ion mass spectrometry (SIMS) and transmission electron microscopy (TEM) revealed, that almost stoichiometric crystalline particles were formed. The in-situ optical transmission spectroscopy measurements yielded a single plasmon resonance in the visible spectrum. PACS 81.07.-b; 78.67.-n     

Matrix assisted growth of nanoparticles and nanoporous films

Since the inception of matrix assisted pulsed laser evaporation (MAPLE), a large body of research has focused on the structure and property preservation of soft materials. Departing from this precedent, a variation of MAPLE to grow complex inorganic nanoparticles and nanoporous thin films from acetate precursors is presented. While some aspects of MAPLE are retained, a weakly absorbing matrix solvent is used to promote absorption by the precursors, leading to photothermal decomposition. The diffusion of ions within the laser interaction volume results in the formation of nanoparticles, which are then ejected by subsequent pulses. The acetate precursors were processed into colloidal suspensions in deionized water and frozen to form solid targets, followed by irradiation with a pulsed excimer laser at fluences ranging from 0.25 to 0.75 J/cm². Nanoparticles and nanoporous films of unary, binary, and ternary metallic and oxide systems were deposited at room temperature onto substrates of Si and electron-transparent grids. Size distributions varied between different material systems with negligible pressure and energy effects, with distribution extrema ranging from 2 to 100 nm in diameter. Characterization of the nanoparticles was performed by high resolution scanning and transmission electron microscopy, and energy dispersive x-ray spectroscopy.     

Effect of insitu annealing on physical properties of Si nanoparticles synthesized by pulsed laser ablation

Silicon nanocrystalline particles with a uniform size were successfully synthesized by a sequential system of pulsed-laser ablation, insitu annealing and a size classification using a differential mobility analyzer (DMA). Transmission electron microscopy (TEM) observations revealed that the insitu annealing was quite effective in improving morphological uniformity of the particles; most of the nanoparticles annealed above a temperature of 900 °C showed a spherical shape. The silicon nanoparticles classified after the annealing showed a very narrow size-distribution with a geometrical standard deviation of approximately 1.1. Raman scattering measurement and high-resolution TEM observation showed that the annealing was also effective in improving a crystallinity of the particles. The silicon nanoparticles showed photoluminescence (PL) in near-IR and visible region at room temperature, which depended on the insitu annealing condition; the full-width at half-maximum (FWHM) of the PL spectrum decreased with the increase in annealing temperature and reached as narrow as 190 meV corresponding to the sharp size distribution of the emitting particles. PACS 81.40.Pq; 81.07.Bc     

Surfactant assisted surface studies of zinc sulfide nanoparticles

We report a simple soft chemical method for the synthesis of ZnS nanoparticles using varying concentration of cationic surfactant CTAB and examine its surface properties. Powder X-ray diffraction, UV-vis spectroscopy, photoluminescence spectroscopy, selective area electron diffraction, and transmission electron microscopy are used to characterize the as prepared ZnS nanoparticles. XRD and TEM measurements show the size of polydispersed ZnS nanoparticles is in the range of 2-5 nm with cubic phase structure. The photoluminescence spectrum of ZnS nanoparticles exhibits four fluorescence emission peaks centered at 387 nm, 412 nm, 489 nm and 528 nm showing the application potential for the optical devices. In Raman spectra of ZnS nanoparticles, the modes around 320, 615 and 700 cm⁻¹ are observed.     

A novel method for synthesis of colloidal silver nanoparticles by arc discharge in liquid

This paper presents a novel, inexpensive and one-step approach for synthesis of silver nanoparticles (Ag NPs) using arc discharge between titanium electrodes in AgNO₃ solution. The resulting nanoparticles were characterized using UV–Vis spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Silver nanoparticles of 18 nm diameter were formed during reduction of AgNO₃ in plasma discharge zone. Optical absorption spectroscopy of as prepared samples at 15 A arc current in AgNO₃ solution shows a surface plasmon resonance around 410 nm. It was found that sodium citrate acts as a stabilizer and surface capping agent of the colloidal nanoparticles. SEM images exhibit the increase of reduced nanoparticles in 6 min arc duration compared with 1 min arc duration. TEM image of the sample prepared at 6 min arc duration shows narrow size distribution with 18 nm mean particle size. Antibacterial activities of silver nanoparticles were investigated at the presence of Escherichia coli (E-coli) bacteria.     

Small angle X-ray scattering studies on structures of alkylthiol stabilized-silver nanoparticles in solution

Silver nanoparticles (SNPs), which were stabilized with various alkylthiols, were studied in detail with synchrotron small angle X-ray scattering, UV-Vis spectroscopy and transmission electron microscopy (TEM). UV spectra of SNPs capped with various alkylthiols showed the characteristic surface plasmon bands at ∼ 450 nm. However, the spectral shapes of SNPs with relatively short butanethiols became weaker and asymmetrically broader in the longer wavelength region. Their nanostructures were deliberately characterized by small angle X-ray scattering analysis based on a hard sphere model and TEM results. PACS 61.05.cf; 61.46.Df; 81.07.Pr     

Characterization of Ag and Au nanoparticles created by nanosecond pulsed laser ablation in double distilled water

Pulsed laser ablation of Ag and Au targets, immersed in double-distilled water is used to synthesize metallic nanoparticles (NPs). The targets are irradiated for 20 min by laser pulses at different wavelengths—the fundamental and the second harmonic (SHG) (λ = 1064 and 532 nm, respectively) of a Nd:YAG laser system. The ablation process is performed at a repetition rate of 10 Hz and with pulse duration of 15 ns. Two boundary values of the laser fluence for each wavelength under the experimental conditions chosen were used—it varied from several J/cm² to tens of J/cm². Only as-prepared samples were measured not later than two hours after fabrication. The NPs shape and size distribution were evaluated from transmission electron microscopy (TEM) images. The suspensions obtained were investigated by optical transmission spectroscopy in the near UV and in the visible region in order to get information about these parameters. Spherical shape of the NPs at the low laser fluence and appearance of aggregation and building of nanowires at the SHG and high laser fluence was seen. Dependence of the mean particle size at the SHG on the laser fluence was established. Comments on the results obtained have been also presented.     

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 chromium silicide with laser pulses

Thin chromium films, 60 nm thick, were deposited onto single-crystal silicon wafers. The samples were irradiated with 30 ns single pulses from a Nd: glass laser at fluences ranging from 0.4 to 2.25 J/cm². Rutherford backscattering spectrometry, transmission electron microscopy and electron diffraction measurements evidence the formation of CrSi₂ layers at the Cr/Si interface. The silicide thickness depends on the laser fluence.     

Optical properties of metal nanoparticles synthesized in a polymer by ion implantation: A review

Polymer composite layers irradiated by 30-keV Ag⁺ ions with doses from 3.1×10¹⁵ to 7.5×10¹⁶ cm^?2 and an ion current of 4 µA/cm² are investigated. The composites were examined using Rutherford backscattering (RBS), transmission electron microscopy (TEM), and optical spectroscopy. As follows from electron microscopy and electron microdiffraction data, ion implantation is a promising tool for synthesizing silver nanoparticles in the surface region. The optical density spectra taken of these composites demonstrate that the silver nanoparticles exhibit unusually weak plasma resonance. The formation of silver nanoparticles in layers carbonized by ion implantation is considered. Based on the Mie theory, optical extinction spectra for silver particles in the polymer and carbon matrices are simulated and optical spectra for complex silver core-carbon sheath nanoparticles are calculated. The physics behind the experimental optical spectra of the composite is discussed.     

Synthesis and antibacterial activity of silver nanoparticles with different sizes

Silver nanoparticles with different sizes (7, 29, and 89 nm mean values) were synthesized using gallic acid in an aqueous chemical reduction method. The nanoparticles were characterized using transmission electron microscopy (TEM), dynamic light scattering (DLS), X-ray diffraction (XRD), and ultraviolet–visible (UV–Vis) absorption spectroscopy; the antibacterial activity was assessed using the standard microdilution method, determining the minimum inhibitory concentration (MIC) according to the National Committee for Clinical Laboratory Standards. From the microscopies studies (TEM) we observed that silver nanoparticles have spherical (7 and 29 nm) and pseudospherical shape (89 nm) with a narrow size distribution. The sizes of the silver nanoparticles were controlled by varying some experimental conditions. It was found that the antibacterial activity of the nanoparticles varies when their size diminishes.     

Structural and morphological characterizations of ZnO films grown on GaAs substrates by MOCVD

The production of boron carbide (B₄C) nanoparticles was investigated in a conventional high temperature furnace reactor. The reaction was carried out by heating a mixture of amorphous carbon and amorphous boron at 1550 °C to efficiently obtain a quantity of B₄C. Scanning electron microscopy studies showed the average size of B₄C particles was 200 nm, ranging from 50 nm to 350 nm. X-ray diffraction transmission electron microscopy and electron diffraction studies indicated that the prepared nanoparticles were crystalline B₄C with a high density twin structure. High resolution transmission electron microscopy and selected area diffraction were also used to further characterize the structure of the prepared B₄C particles, while energy dispersive spectroscopy and electron energy loss spectroscopy were used to determine the stoichiometry of the product. A solid state diffusion reaction mechanism is proposed.     

Structural characterization of shock-affected sapphire

The presence of dislocations has been revealed by numerical processing of high–resolution transmission electron microscopy images from the regions affected by a shock wave propagation. The shock wave was triggered by a single 220 fs duration pulse of 30 nJ at an 800 nm wavelength inside sapphire at approximately 10 μm depth. The shock-amorphised sapphire has a distinct boundary with the crystalline phase, which is not wet etchable even at a dislocation density of ≃8×10¹² cm^-2. PACS 81.07.-b; 96.50.Fm; 62.50.+p; 47.40.Nm; 81.40.-z     

Room-temperature synthesis of Mn3O4 nanorods

Nanocrystalline Mn₃O₄ hausmannite has been easily prepared from manganese(II) acetate tetrahydrated, dissolved in a mixture of N,N’-dimethylformamide (DMF) and water (10%) at room temperature, without post-treatment of heating. Stability of the Mn₃O₄ colloidal dispersion was monitored by UV-visible electronic absorption spectroscopy. X-ray powder diffraction (XRD) pattern demonstrates its good phase purity. Analysis by transmission electron microscopy (TEM) image shows homogeneous nanorods with a narrow size distribution, being the average diameter and length of 6.58 nm and 17.44 nm, respectively. Moreover, the facility of the hausmannite nanorods to adhere to glass wall in this solvent mixture has allowed the formation of thin films which were analyzed by atomic force microscopy (AFM). PACS 81.07.Bc; 81.16.Be; 61.46.+w     

Rapid extra-/intracellular biosynthesis of gold nanoparticles by the fungus <Emphasis Type="Italic">Penicillium</Emphasis> sp.

In this work, the fungus Penicillium was used for rapid extra-/intracellular biosynthesis of gold nanoparticles. AuCl₄ ⁻ ions reacted with the cell filtrate of Penicillium sp. resulting in extracellular biosynthesis of gold nanoparticles within 1 min. Intracellular biosynthesis of gold nanoparticles was obtained by incubating AuCl₄ ⁻ solution with fungal biomass for 8 h. The gold nanoparticles were characterized by means of visual observation, UV–Vis absorption spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDX). The extracellular nanoparticles exhibited maximum absorbance at 545 nm in UV–Vis spectroscopy. The XRD spectrum showed Bragg reflections corresponding to the gold nanocrystals. TEM exhibited the formed spherical gold nanoparticles in the size range from 30 to 50 nm with an average size of 45 nm. SEM and TEM revealed that the intracellular gold nanoparticles were well dispersed on the cell wall and within the cell, and they are mostly spherical in shape with an average diameter of 50 nm. The presence of gold was confirmed by EDX analysis.     

In situ electron beam irradiated rapid growth of bismuth nanoparticles in bismuth-based glass dielectrics at room temperature

In this study, in situ control growth of bismuth nanoparticles (Bi⁰ NPs) was demonstrated in bismuth-based glass dielectrics under an electron beam (EB) irradiation at room temperature. The effects of EB irradiation were investigated in situ using transmission electron microscopy (TEM), selected-area electron diffraction and high-resolution transmission electron microscopy. The EB irradiation for 2–8 min enhanced the construction of bismuth nanoparticles with a rhombohedral structure and diameter of 4–9 nm. The average particle size was found to increase with the irradiation time. Bismuth metal has a melting point of 271 °C and this low melting temperature makes easy the progress of energy induced structural changes during in situ TEM observations. This is a very useful technique in nano-patterning for integrated optics and other applications.