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.     

Interaction of gold nanoparticles with nanosecond laser pulses: Nanoparticle heating

Theoretical and experimental results on the heating process of gold nanoparticles irradiated by nanosecond laser pulses are presented. The efficiency of particle heating is demonstrated by in-vitro photothermal therapy of human tumor cells. Gold nanoparticles with diameters of 40 and 100 nm are added as colloid in the cell culture and the samples are irradiated by nanosecond pulses at wavelength of 532 nm delivered by Nd:YAG laser system. The results indicate clear cytotoxic effect of application of nanoparticle as more efficient is the case of using particles with diameter of 100 nm. The theoretical analysis of the heating process of nanoparticle interacting with laser radiation is based on the Mie scattering theory, which is used for calculation of the particle absorption coefficient, and two-dimensional heat diffusion model, which describes the particle and the surrounding medium temperature evolution. Using this model the dependence of the achieved maximal temperature in the particles on the applied laser fluence and time evolution of the particle temperature is obtained.     

Silicon nanoparticles generated by femtosecond laser ablation in a liquid environment

Silicon nanoparticles were generated by femtosecond laser [387 nm, 180 fs, 1 kHz, pulse energy = 3.5 μJ (fluence = 0.8 J/cm²)] ablation of silicon in deionized water. Nanoparticles with diameters from ~5 up to ~200 nm were observed to be formed in the colloidal solution. Their size distribution follows log-normal function with statistical median diameter of ≈20 nm. Longer ablation time leads to a narrowing of the nanoparticle size distribution due to the interaction of the ablating laser beam with the produced nanoparticles. Raman spectroscopy measurements confirm that the nanoparticles exhibit phonon quantum confinement effects and indicate that under the present conditions of ablation they are partially amorphous.     

Molecular dynamics simulations of aggregation of copper nanoparticles with different heating rates

Molecular dynamics simulations were employed to investigate the heating rates’ effect on aggregation of two copper nanoparticles. The aggregation can be distinguished into three distinct regimes by the contacting and melting of nanoparticles. The nanoparticles contacting at a lower temperature during the sintering with lower heating rate, meanwhile, some temporary stacking fault exists at the contacting neck. The aggregation properties of the system, i.e. neck diameter, shrinkage ratio, potential energy, mean square displacement (MSD) and relative gyration radius, experience drastic changes due to the free surface annihilation. After the nanoparticles coalesced for a stable period, the shrinkage ratio, MSD, relative gyration radius and neck diameter of the system are dramatically changed during the melting process. It is shown that the shrinkage ratio and MSD have relative larger increasing ratio for a lower heating rate. While the evolution of the relative gyration radius and neck diameter is only sensitive to the temperature.     

Flame Temperature Effect on the Structure of SiC Nanoparticles Grown by Laser Pyrolysis

Small SiC nanoparticles (10 nm diameter) have been grown in a flow reactor by CO₂ laser pyrolysis from a C₂H₂ and SiH₄ mixture. The laser radiation is strongly absorbed by SiH₄ vibration. The energy is transferred to the reactive medium and leads to the dissociation of molecules and the subsequent growth of the nanoparticles. The reaction happens with a flame. The purpose of the experiments reported in this paper is to limit the size of the growing particles to the nanometric scale for which specific properties are expected to appear. Therefore the effects of experimental parameters on the structure and chemical composition of nanoparticles have been investigated. For a given reactive mixture and gas velocity, the flame temperature is governed by the laser power. In this study, the temperature was varied from 875°C to 1100°C. The chemical analysis of the products indicate that their composition is a function of the temperature. For the same C/Si atomic ratio in the gaseous phase, the C/Si ratio in the powder increases from 0.7 at 875°C up to 1.02 at 1100°C, indicating a growth mechanism limited by C₂H₂ dissociation. As expected, X-ray diffraction has shown an improved crystallisation with increasing temperature. Transmission electron microscopy observations have revealed the formation of 10 nm grains for all values of laser power (or flame temperature). These grains appear amorphous at low temperature, whereas they contain an increasing number of nanocrystals (2 nm diameter) when the temperature increases. These results pave the way to a better control of the structure and chemical composition of laser synthesised SiC nanoparticles in the 10 nm range.     

Scattering behavior of nonabsorbing metallic nanoparticles

The optical property of nanosized metallic particles is unique and size-dependent, which cause color variation. In this work, the relationship between diameter and refractive index of nonabsorbing metallic nanoparticles and their scattering properties is studied by using Mie theory. Obtained results indicate that the optical scattering of metallic nanoparticle depends on their refractive index and diameter. The effect of refractive index on optical scattering depends on the nanoparticle diameter. So that, for very fine nanoparticle (10 nm diameter) the effect of refractive index on scattering is not significant. But the effect of refractive index of large size nanoparticle (700–900 nm diameter) on their optical scattering is higher than fine and medium size nanoparticles. The wavelength with maximum scattering depends on refractive index and nanoparticles diameter. In addition, the colorimetric study indicates that the color of nanoparticle depends on their size and refractive index. So that, the lightness, hue, and colorfulness of nanoparticles is changed by changing size and refractive index.     

Controlling SERS intensity by tuning the size and height of a silver nanoparticle array

It is demonstrated that the surface-enhanced Raman scattering (SERS) intensity of R6G molecules adsorbed on a Ag nanoparticle array can be controlled by tuning the size and height of the nanoparticles. A firm Ag nanoparticle array was fabricated on glass substrate by using nanosphere lithography (NSL) combined with reactive ion etching (RIE). Different sizes of Ag nanoparticles were fabricated with seed polystyrene nanospheres ranging from 430 nm to 820 nm in diameter. By depositing different thicknesses of Ag film and lifting off nanospheres from the surface of the substrate, the height of the Ag nanoparticles can be tuned. It is observed that the SERS enhancement factor will increase when the size of the Ag nanoparticles decreases and the deposition thickness of the Ag film increases. An enhancement factor as high as 2×10⁶ can be achieved when the size of the polystyrene nanospheres is 430 nm in diameter and the height of the Ag nanoparticles is 96 nm. By using a confocal Raman mapping technique, we also demonstrate that the intensity of Raman scattering is enhanced due to the local surface plasmon resonance (LSPR) occurring in the Ag nanoparticle array.     

Particle agglomeration and properties of nanofluids

The present study demonstrates the importance of actual agglomerated particle size in the nanofluid and its effect on the fluid properties. The current work deals with 5 to 100 nm nanoparticles dispersed in fluids that resulted in 200 to 800 nm agglomerates. Particle size distributions for a range of nanofluids are measured by dynamic light scattering (DLS). Wet scanning electron microscopy method is used to visualize agglomerated particles in the dispersed state and to confirm particle size measurements by DLS. Our results show that a combination of base fluid chemistry and nanoparticle type is very important to create stable nanofluids. Several nanofluids resulted in stable state without any stabilizers, but in the long term had agglomerations of 250 % over a 2 month period. The effects of agglomeration on the thermal and rheological properties are presented for several types of nanoparticle and base fluid chemistries. Despite using nanodiamond particles with high thermal conductivity and a very sensitive laser flash thermal conductivity measurement technique, no anomalous increases of thermal conductivity was measured. The thermal conductivity increases of nanofluid with the particle concentration are as those predicted by Maxwell and Bruggeman models. The level of agglomeration of nanoparticles hardly influenced the thermal conductivity of the nanofluid. The viscosity of nanofluids increased strongly as the concentration of particle is increased; it displays shear thinning and is a strong function of the level of agglomeration. The viscosity increase is significantly above of that predicted by the Einstein model even for very small concentration of nanoparticles.     

Desorption of surfactant and sintering of surface-modified PdxNi1 − x nanoparticles

A series of Pd_xNi_1 − x nanoparticles in a diameter of 6-7 nm were prepared by wet chemical reduction. They were then modified with two surfactants, stearic acid (SA) and polyethylene glycol (PEG). Desorption of the surfactant was studied using a temperature programmed desorption technique, and the sintering behavior of surface-modified Pd_xNi_1 − x nanoparticles was examined. Since surface energy of the nanoparticles depends on the alloy composition, it can be correlated with the desorption temperature of surfactant from the nanoparticle surface. Because Ni has a higher surface energy, the surfactant desorption temperature increases as the Ni content increases. With the same stoichiometry, the desorption temperature of SA is always higher than that of PEG. The SA-modified nanoparticles have higher thermal stability and are less sintered than PEG-modified nanoparticles. The sintering and growth behavior of the nanoparticles can be correlated with variation of surface energy due to different surface modification.     

Growth process of TiC clusters from Ti nanoparticles with evaporated carbon layer

Titanium carbide formation by the solid–solid reaction on the surface of Ti nanoparticles was studied in situ using a high-resolution transmission electron microscope with a heating stage. The cross-sectional image of the Ti surface was clearly observed. Vacuum-deposited carbon covered the whole the surface of Ti nanoparticles in spite of the partly evaporation on the nanoparticle surface. The diffusion of the carbon atoms inside the Ti nanoparticles depended on the size of the nanoparticles. When the Ti nanoparticle diameter was less than 30 nm, carbon atoms diffused into the Ti nanoparticle and formed TiC. The superstructure of the Ti nanoparticles was observed, which revealed the growth process of TiC to be the diffusion of carbon atoms. For Ti nanoparticles with diameter larger than 30 nm it was observed that diffusion of Ti atoms into the carbon layer was dominant, which resulted in formation of TiC in the carbon layer at the surface of Ti nanoparticles.     

Optimal sample preparation for nanoparticle metrology (statistical size measurements) using atomic force microscopy

Optimal deposition procedures are determined for nanoparticle size characterization by atomic force microscopy (AFM). Accurate nanoparticle size distribution analysis with AFM requires non-agglomerated nanoparticles on a flat substrate. The deposition of polystyrene (100 nm), silica (300 and 100 nm), gold (100 nm), and CdSe quantum dot (2–5 nm) nanoparticles by spin coating was optimized for size distribution measurements by AFM. Factors influencing deposition include spin speed, concentration, solvent, and pH. A comparison using spin coating, static evaporation, and a new fluid cell deposition method for depositing nanoparticles is also made. The fluid cell allows for a more uniform and higher density deposition of nanoparticles on a substrate at laminar flow rates, making nanoparticle size analysis via AFM more efficient and also offers the potential for nanoparticle analysis in liquid environments.     

Naturally grown Ag nanoparticles on quartz substrates as SERS substrate excited by a 488 nm diode laser system for SERDS

A silver nanoparticle ensemble was prepared under ultrahigh vacuum (UHV) conditions by Volmer–Weber growth on a quartz substrate for surface-enhanced Raman scattering (SERS) investigations of pyrene molecules. To tune the surface plasmon resonance frequency in the vicinity of the excitation wavelength of 488 nm of the diode laser, the morphology of the silver nanoparticles was optimized. The substrates were mounted in a flow-through cell as part of the optical Raman set-up. A microsystem diode laser generates two slightly different emission wavelengths (λ=487.61 nm and λ=487.91 nm) with a spectral width <10 pm and an optical power of 20 mW, i.e. SERS experiments are possible but also shifted excitation Raman difference spectroscopy (SERDS) can be carried out. For trace analysis of pyrene in water we demonstrate SERS/SERDS experiments which lead to a limit of detection of 2 nmol/l for pyrene. These results suggest that with silver nanoparticle ensembles excited at their plasmon resonance at 488 nm combined SERS/SERDS measurements can be effectively performed for in-situ trace analysis of pollutant chemicals in water.     

Sintering kinetic measurement of nickel nanoparticle agglomerates by electrical mobility classification

The gas-phase sintering kinetics of nickel nanoparticle agglomerates was investigated by a two step electrical mobility classification. The first electrostatic classifier sorted the agglomerated mono-area nickel nanoparticles generated by pulsed laser ablation, and then the subsequent heating process created the sintered nickel nanostructures. The second electrostatic classifier combined with the condensation nucleus counter scanned the shrinkage of the agglomerated mono-area nickel nanoparticles due to the sintering process. The change in the mono-area particle mobility size measured by the electrical mobility classification technique was compared with the results of the existing coalescence model to extract the kinetic parameters for the sintering of nickel particles. The optimum activation energy found in this study was ∼63 kJ/mol, which falls between the diffusion of nickel atoms (∼49 kJ/mol) and the migration and coalescence of nickel particles (∼78 kJ/mol).     

Cerium oxide nanoparticles protect primary mouse bone marrow stromal cells from apoptosis induced by oxidative stress

The sintering of a silver (Ag) nanoparticle film by laser beam irradiation was studied using a CW DPSS laser. The laser sintering of the Ag nanoparticle thin film gave a transparent conductive film with a thickness of ca. 10 nm, whereas a thin film sintered by conventional heat treatment using an electronic furnace was an insulator because of the formation of isolated silver grains during the slow heating process. The laser sintering of the Ag nanoparticle thin film gave a unique conductive network structure due to the rapid heating and quenching process caused by laser beam scanning. The influences of the laser sintering conditions such as laser scan speed on the conductivity and the transparency were studied. With the increase of scan speed from 0.50 to 5.00 mm/s, the surface resistivity remarkably decreased from 4.45 × 10⁸ to 6.30 Ω/sq. The addition of copper (Cu) nanoparticles to silver thin film was also studied to improve the homogeneity of the film and the conductivity due to the interaction between the oxidized surface of Cu nanoparticle and a glass substrate. By adding 5 wt% Cu nanoparticles to the Ag thin film, the surface resistivity improved to 2.40 Ω/sq.     

Experimental study of nanoparticles penetration through commercial filter media

In this study, nanoparticle penetration was measured with a wide range of filter media using silver nanoparticles from 3 nm to 20 nm at three different face velocities in order to define nanoparticle filtration characteristics of commercial fibrous filter media. The silver particles were generated by heating a pure silver powder source via an electric furnace with a temperature of 870°C, which was found to be the optimal temperature for generating an adequate amount of silver nanoparticles for the size range specified above. After size classification using a nano-DMA, the particle counts were measured by an Ultrafine Condensation Particle Counter (UCPC) both upstream and downstream of the test filter to determine the nanoparticle penetration for each specific particle size. Particle sampling time continued long enough to detect more than 10⁵ counts at the upstream and 10 counts at the downstream sampling point so that 99.99% efficiency can be detected with the high efficiency filter. The results show a very high uniformity with small error bars for all filter media tested in this study. The particle penetration decreases continuously down to 3 nm as expected from the classical filtration theory, and together with a companion modeling paper by␣Wang et al. in this same issue, we found no significant evidence of nanoparticle thermal rebound down to 3 nm.     

Nanoparticle Tracking Analysis: Enhanced Detection of Transparent Materials

This study proposes a novel and simple in-house design of a nanoparticle tracking analysis (NTA) device for the online characterization of nanoparticles in an aqueous solution. The particle size distribution of two sets of model nanoparticles, for example, transparent (SiO₂) and opaque (TiO₂) materials with respect to water as a dispersion medium could be successfully analyzed. Experiments are conducted using two different laser wavelengths of 632.8 (red) and 510 nm (green) and a range of concentrations. The accuracy of the green laser is larger compared to the red laser for all particle concentrations used. The measured average diameter using the presented in-house NTA setup is in the acceptable range compared to the electron microscopy data. The average diameter of the transparent (SiO₂) and opaque (TiO₂) samples is calculated as 36.29 and 27.26 nm using NTA, 36.44 and 27.8 nm analyzing field emission scanning electron microscopy images, and 23.97 and 19.7 nm analyzing transmission electron microscopy images. In the new viewing sample holder, nanoparticles undergo mere Brownian motion with no bulk drift velocity. The effect of solid concentration and wavelength of the laser light on the performance of the NTA sensor is investigated, and the optimal concentration range for model particles is reported.     

Low temperature nanoparticle sintering with continuous wave and pulse lasers

New manufacturing methods are being sought for electronics production. Printable electronics is a promising method for producing low cost and large-scale electronics. In printable electronics nanoparticle inks printed on the surface of substrate contain additives, such as dispersing agent and carrier fluids that provide good printing properties by changing the viscosity and separating the nanoparticles of the ink. In the sintering process ink particles are heated to a certain, ink-specific temperature. During the sintering process the carrier fluid and dispersing agents are evaporated from the ink. Additional heating after evaporation causes the nanoparticles to start to agglomerate. A small particle size allows the use of a considerably lower sintering temperature than with bulk silver, for example 220 °C. The sintering process is usually utilized with a convection oven, with a long sintering time, and the thermal load on the surrounding material can become too great as components and patterns are formed from layers of different type inks. Hence, alternative sintering methods are sought. This paper describes tests done with two different types of laser; pulsed and continuous wave lasers. Laser sintering enables short sintering times and selective sintering, making it possible for printed structures to contain fragile active components produced with other technologies.     

Preparation of luminescent Si nanoparticles by tailoring the size,crystallinity and surface composition

The preparation of sizeable quantities of luminescent Si nanoparticles (Si-np) with controlled morphology is a challenging task. Here, we describe two strategies aiming at size reduction of the Si-np produced in a laser-assisted silane pyrolysis reactor without detrimental effects on the process yield and on the nanoparticle structural and compositional properties. The first method is based on the addition of a sensitizer gas to dilute silane and consequently reduce the nucleation centres density without decreasing the reaction temperature. The second consists in the introduction of a collector at a variable distance from the irradiated region to freeze the particle growth and decrease the inter-particle sintering probability. We report on the characterization of the produced Si-np, and we show that by combining the two methods, we are able to prepare 4 nm crystalline core size nanoparticles with a productivity of 1 g per hour. We also describe the enhancement effect of the wet-chemical oxidation processes on the luminescence emission intensity of the Si-np.     

Nanostructures of gold coated iron core-shell nanoparticles and the nanobands assembled under magnetic field

Pure metal iron nanoparticles are unstable in the air. By a coating iron on nanoparticle surface with a stable noble metal, these air-stable nanoparticles are protected from the oxidation and retain most of the favorable magnetic properties, which possess the potential application in high density memory device by forming self-assembling nanoarrays. Gold-coated iron core-shell structure nanoparticles (Fe/Au) synthesized using reverse micelles were characterized by transmission electron microscopy (TEM). The average nanoparticle size of the core-shell structure is about 8 nm, with about 6 nm diameter core and 1∼2 nm shell. Since the gold shell is not epitaxial growth related to the iron core, the morié pattern can be seen from the overlapping of iron core and gold shell. However, the gold shell lattice can be seen by changing the defocus of TEM. An energy dispersive X-ray spectrum (EDS) also shows the nanoparticles are air-stable. The magnetic measurement of the nanoparticles also proved successful synthesis of gold coated iron core-shell structure. The nanoparticles were then assembled under 0.5 T magnetic field and formed parallel nanobands with about 10 μm long. Assembling two dimensional ordered nanoarrays are still under going. Received 29 November 2000     

Size-tuneable synthesis of nickel nanoparticles

A facile method is described for synthesising nickel nanoparticles via the thermal decomposition of an organometallic precursor in the presence of excess n-trioctylphosphine as a capping ligand. For the first time, alkylamines with different chain lengths were employed as size-limiting agents in this synthesis. A direct correlation is demonstrated between the size of the alkylamine ligands used and the mean diameter of the nickel nanoparticles obtained. The use of bulky oleylamine as a size-limiting agent over a reaction period of 30 min led to the growth of nickel nanoparticles with a mean diameter of 2.8 ± 0.9 nm. The employment of less bulky N,N-dimethylhexadecylamine groups led to the growth of nickel nanoparticles with a mean diameter of 4.4 ± 0.9 nm. By increasing the reaction time from 30 to 240 min, while employing oleylamine as the size-limiting agent, the mean diameter of the nickel nanoparticles was increased from 2.8 ± 0.9 to 5.1 ± 0.7 nm. Decreasing the amount of capping ligand present in the reaction system allowed further growth of the nickel nanoparticles to 17.8 ± 1.3 nm. The size, structure and morphology of the nanoparticles synthesised were characterised by transmission electron microscopy and powder X-ray diffraction; while magnetic measurements indicated that the particles were superparamagnetic in nature.