Synthesis and physico-chemical characteristics of nanosized particles produced by laser ablation of a nickel target in water

Ablation of Ni targets in water by laser impact (532 nm, 40 mJ/pulse, 10 Hz and 8 ns duration) focused on massive samples (2 mm diameter) generates colloids with fine nanoparticles. The amount of metal released in the solution (measured by mass loss of the target or ICP) was found to increase first linearly with time, but slower after 8 min of impact. The size distribution of the nanoparticles thus produced was measured (by TEM) to be in the range 3–5.3 nm in diameter, with a tendency for the size to be smaller for larger number of laser shots. Actually, nickel oxide nanoparticles were produced, rather than nickel nanoparticles as it was shown by HRTEM. XPS photoemission measurements evidenced the presence of nickel oxide species on the crater of the nickel sample surface after laser ablation.     

Magnetic anisotropy in Ni–Si nanoparticle films produced by ultrashort pulsed laser deposition

Pulsed laser deposition (uPLD) in vacuum by means of subpicosecond laser pulses is a powerful, versatile technique for the production of films constituted by nanoparticles. On impact with the deposition substrate, the nanodrops ejected from the target assume an oblate ellipsoidal shape, solidifying with the major cross-section parallel to the substrate plane. These features and the difficult coalescence among the deposited nanoparticles are peculiar characteristics specific to the films obtained by uPLD. In the case of magnetic nanoparticle films obtained by means of this technique, a magnetization isotropy in the film plane and a hard magnetization axis orthogonal to the film plane are expected. This simple assumption, generated by the specific shape and orientation of the deposited nanoparticles, was not experimentally verified up to now. The present investigation represents the first experimental validation of magnetic anisotropy, determined by the peculiar morphology and topology of the constituent particles, in the uPLD Ni_xSi_100−x nanoparticle films. The in-plane isotropic magnetization behaviour, as well as the presence of a hard magnetization axis perpendicular to the sample surface were demonstrated for all investigated films. The difficult coalescence among the magnetic nanoparticles, even at high Ni volume fractions, is confirmed by the behaviour of the initial magnetization curve, typical for single-domain nanoparticles systems.     

Peculiar properties of nanogranular Ni<Subscript>x</Subscript>Si<Subscript>100-x</Subscript> magnetic films obtained by ultrashort pulsed laser deposition

The use of ultrashort laser pulses enables the deposition of films composed of mono-component nanoparticles exhibiting similar shape and size. Films made of nickel (Ni) and silicon (Si) nanoparticles have been produced and investigated in view of the expected interesting properties, resulting from the uniform distribution of metallic, magnetic Ni particles among semiconductive, non-magnetic Si particles. The morphology of the deposited nanoparticles and the related magnetic and magneto-transport characteristics of the films have been studied for different Ni contents, evidencing properties deriving from the peculiar deposition technique and in particular the important role of the free volume inclusions and the particles tendency to not coalesce. PACS 75.75.+a; 81.07.-b; 81.16.Mk; 73.50.Jt     

Properties of pulsed laser deposited nanocomposite NiO:Au thin films for gas sensing applications

Nanocomposite thin films formed by gold nanoparticles embedded in a nickel oxide matrix have been synthesized by a new variation of the pulsed laser deposition technique. Two actively synchronized laser sources, a KrF excimer laser at 248 nm and an Nd:YAG laser at 355 nm, were used for the simultaneous ablation of nickel and gold targets in oxygen ambient. The structural, morphological, and electrical properties of the obtained nanocomposite films were investigated in relation to the fluence of the laser irradiating the gold target. The nanocomposite thin films were tested as electrochemical hydrogen sensors. It was found that the addition of the gold nanoparticles increased the sensor sensitivity significantly.     

Pulsed electrodeposition and magnetism of two-dimensional assembly of controlled-size Co particles on Si substrates

We present an extremely simple and inexpensive way to obtain controlled-size and density Co metallic particles on Si(1 1 1) using electrodeposition. When unpatterned substrates are used, the particle density and size can be controlled by adjusting the pulse frequency and the total deposition time. Randomly arranged cobalt particles with diameters of few tens of nanometres are obtained for short deposition times. Continuing the deposition, the particle size and density can be increased until coalescence. Magnetic force microscopy images show magnetically coupled/uncoupled particles depending on the size and distance between them. For small decoupled particles, no in-plane uniaxial anisotropy is found, in agreement with transmission electron microscopy observations which show randomly oriented single crystal particles. As the particle coalescence increases, the in-plane anisotropy evaluated from magnetization loops increases as well. When deposited on focused ion beam patterned substrates, well organized nanoparticles with adjustable magnetic anisotropy are obtained. Ferromagnetic resonance measurements performed on these samples reveal that the magnetic anisotropy originates mainly from the particle shape.     

Chromium carbide thin films deposited by ultra-short pulse laser deposition

Pulsed laser deposition performed by a laser with a pulse duration of 250 fs has been used to deposit films from a Cr₃C₂ target. Due to the different processes involved in the laser ablation when it is performed by an ultra-short pulse source instead of a conventional short pulse one, it has been possible to obtain in vacuum films containing only one type of carbide, Cr₃C₂, as shown by X-ray photoelectron spectroscopy. On the other hand, Cr₃C₂ is not the only component of the films, since a large amount of amorphous carbon is also present. The films, deposited at room temperature, are amorphous and seem to be formed by the coalescence of a large number of particles with nanometric size. The film composition can be explained in terms of thermal evaporation from particles ejected from the target.     

Nanoparticles size modifications during femtosecond laser ablation of nickel in vacuum

Nanoparticles were synthesized by irradiating a nickel target with femtosecond laser pulses in high vacuum, and subsequently analyzed. The proof-of-principle experiments aim to modify the size characteristics of the produced nanoparticles. For nickel it is found that: (i) ultraviolet laser pulses lead to a remarkable change in the nanoparticles size distribution with respect to visible laser pulses; (ii) irradiation of the femtosecond pulses induced ablation plume with a second, delayed ultraviolet laser pulse can change the size characteristics of the produced nanoparticles.     

Details of crystalline growth in co-deposited electroplated nickel films with hard (nano)particles

Electroplated nickel dispersion films with incorporated hard particles, primarily titanium oxide, were studied. A sufficient dispersion of nanometre-scaled particles in Watts solution was reached by application of ultrasonic energy to the galvanic bath. Crystal morphology, mean grain size and formation of textures were examined by electron backscattering diffraction (EBSD), X-ray diffraction (XRD) and transmission electron microscopy (TEM). The typical columnar structure of pure Ni films was refined by means of ultrasound. Incorporation of micron-sized TiO₂ particles generates additional nucleation surfaces in contrast to SiC particles. Textures of the subsequent columnar nickel crystals change from 〈2 1 1〉 (silent condition) or 〈1 1 0〉 (ultrasonic condition) fibre textures in growth direction to 〈1 0 0〉 and 〈1 1 1〉 textures under the influence of nanoparticle incorporation. Moreover, nanoparticles remarkably decrease the grain size and grain aspect ratio. Their incorporation takes place inside the crystals as well as between grains.     

Magnetic nanoparticles as building blocks for high-performance magnetic materials

We report on the magnetic behaviour of films of Fe nanoparticles deposited from the gas phase with sizes in the range 2–3 nm embedded in Ag and Co matrices and Co nanoparticles of the same size embedded in Ag matrices. Magnetometry measurements, using a VSM, of very low volume fraction (1–2%) assemblies of Fe and Co in Ag show perfect superparamagnetism and enable us to confirm that the size distribution of the particles in the matrix is the same as that of the free particles prior to deposition. The hysteresis loops at 2 K, which is below the blocking temperature, show that the particles have a uniaxial anisotropy that is randomly oriented in three dimensions with the Co nanoparticles having a much higher anisotropy than the Fe particles. The soft magnetic behaviour of pure Fe and Co nanoparticle films with no matrix is well described by a random anisotropy model and is consistent with the formation of a correlated super-spin glass (CSSG) characteristic of amorphous materials. The Co nanoparticle films appear to have a lower random anisotropy than the Fe ones in contrast to the behaviour observed for the isolated particles. Films of Fe nanoparticles embedded in Co matrices, whose saturation magnetization exceeds the Slater–Pauling curve, also show magnetic behaviour consistent with a CSSG. At high volume fractions, the films of Fe nanoparticles embedded in Co matrices behave almost identically to films of pure Co nanoparticles.     

Laser induced synthesis of nanoparticles in liquids

The review of results on nanoparticles formation is presented under laser ablation of Ag, Au, and Cu-containing solid targets in liquid environments (H₂O, C₂H₅OH, C₂H₄Cl₂, etc.). X-ray diffractometry (XRD), UV-vis optical transmission spectrometry, and high resolution transmission electron microscopy (HRTEM) characterize the nanoparticles. The morphology of nanoparticles is studied as the function of both laser fluence and nature of the liquid. The possibility to control the shape of nanoparticles by ablation of an Au target by an interference pattern of two laser beams is demonstrated. Formation of alloyed Au-Ag and Ag-Cu nanoparticles is reported under laser exposure of a mixture of individual nanoparticles. The effect of internal segregation of brass nanoparticles is discussed due to their small lateral dimensions. The factors are discussed that determine the distribution function of particles size under laser ablation. The influence of laser parameters as well as the nature on the liquid on the properties of nanoparticles is elucidated.     

Determination of anisotropy constants of protein encapsulated iron oxide nanoparticles by electron magnetic resonance

Angle-dependent electron magnetic resonance was performed on 4.9, 8.0, and 19 nm iron oxide nanoparticles encapsulated within protein capsids and suspended in water. Measurements were taken at liquid nitrogen temperature after cooling in a 1 T field to partially align the particles. The angle dependence of the shifts in the resonance field for the iron oxide nanoparticles (synthesized within Listeria-Dps, horse spleen ferritin, and cowpea chlorotic mottle virus) all show evidence of a uniaxial anisotropy. Using a Boltzmann distribution for the particles’ easy-axis direction, we are able to use the resonance field shifts to extract a value for the anisotropy energy, showing that the anisotropy energy density increases with decreasing particle size. This suggests that surface anisotropy plays a significant role in magnetic nanoparticles of this size.     

Structural and morphological characterization of TiO2 nanostructured films grown by nanosecond pulsed laser deposition

TiO₂ has attracted a lot of attention due to its photocatalytic properties and its potential applications in environmental purification and self cleaning coatings, as well as for its high optical transmittance in the visible-IR spectral range, high chemical stability and mechanical resistance. In this paper, we report on the growth of TiO₂ nanocrystalline films on Si (1 0 0) substrates by pulsed laser deposition (PLD). Rutile sintered targets were irradiated by KrF excimer laser (λ = 248 nm, pulse duration ∼30 ns) in a controlled oxygen environment and at constant substrate temperature of 650 °C. The structural and morphological properties of the films have been studied for different deposition parameters, such as oxygen partial pressure (0.05-5 Pa) and laser fluence (2- 4 J/cm²). X-ray diffraction (XRD) shows the formation of both rutile and anatase phases; however, it is observed that the anatase phase is suppressed at the highest laser fluences. X-ray photoelectron spectroscopy (XPS) measurements were performed to determine the stoichiometry of the grown films. The surface morphology of the deposits, studied by scanning electron (SEM) and atomic force (AFM) microscopies, has revealed nanostructured films. The dimensions and density of the nanoparticles observed at the surface depend on the partial pressure of oxygen during growth. The smallest particles of about 40 nm diameter were obtained for the highest pressures of inlet gas.     

Synthesis and magnetic characterization of nickel ferrite nanoparticles prepared by co-precipitation route

Magnetic nanoparticles of nickel ferrite (NiFe₂O₄) have been synthesized by co-precipitation route using stable ferric and nickel salts with sodium hydroxide as the precipitating agent and oleic acid as the surfactant. X-ray diffraction (XRD) and transmission electron microscope (TEM) analyses confirmed the formation of single-phase nickel ferrite nanoparticles in the range 8-28 nm depending upon the annealing temperature of the samples during the synthesis. The size of the particles (d) was observed to be increasing linearly with annealing temperature of the sample while the coercivity with particle size goes through a maximum, peaking at ∼11 nm and then decreases for larger particles. Typical blocking effects were observed below ∼225 K for all the prepared samples. The superparamagnetic blocking temperature (T_B) was found to be increasing with increasing particle size that has been attributed to the increased effective anisotropy energy of the nanoparticles. The saturation moment of all the samples was found much below the bulk value of nickel ferrite that has been attributed to the disordered surface spins or dead/inert layer in these nanoparticles.     

All-optical probe of coherent spin waves

A novel, all-optical method to excite and detect spin waves in magnetic materials is presented. By exploiting the temperature dependence of the magnetic anisotropy, an ultrashort laser pulse is efficiently converted in a picosecond "anisotropy field" pulse that triggers a coherent precession of the magnetization. Recording the temporal evolution of the precessing spins by a time-delayed probe-pulse provides a quantitative method to study locally the magnetic anisotropy, as well as switching and damping phenomena in micromagnetic structures. Applications to nickel and permalloy ( Ni80Fe20) films are discussed, particularly showing the possibility to explore standing spin waves in thin films.     

Magnetic/non-magnetic nanoparticles films with peculiar properties produced by ultrashort pulsed laser deposition

Films of magnetic nanoparticles uniformly mixed with non-magnetic nanoparticles have been produced by ultrashort pulsed laser deposition. These films present innovative characteristics with respect to their counterparts produced by standard techniques, as for example nanosecond laser ablation or sputtering, due to the peculiar shape and preferential distribution of their constituent nanoparticles. In the present investigation, the difficult coalescence among the deposited nanoparticles, specific characteristic of the ultrashort pulsed laser deposition, is particularly stressed for what concerns its effect on the collective magnetic behaviour. In particular, we observed that, even for a significant fraction of magnetic particles, the films exhibit an unusual high remanent magnetization, together with relatively low values of saturation and coercive fields, showing a strong squareness of the hysteresis loops. In perspective, these nanogranular films appear very promising for potential application as permanent magnets and in magnetic recording.     

Evolution of surface morphology of NiO thin films under swift heavy ion irradiation

NiO nanoparticle thin films grown on Si substrates were irradiated by 107 MeV Ag⁸⁺ ions. The films were characterized by glancing angle X-ray diffraction and atomic force microscopy. Ag ion irradiation was found to influence the shape and size of the nanoparticles. The pristine NiO film consisted of uniform size (∼100 nm along major axis and ∼55 nm along minor axis) elliptical particles, which changed to also of uniform size (∼63 nm) circular shape particles on irradiation at a fluence of 3 × 10¹³ ions cm⁻². Comparison of XRD line width analysis and AFM data revealed that the particles in the pristine films are single crystalline, which turn to polycrystalline on irradiation with 107 MeV Ag ions.     

Formation of TiN-Ir particle films using pulsed-laser deposition and their electrolytic properties in producing hypochlorous acid

Using sintered TiN and TiN-Ir (Ir contents: 5.9-14.2 at.%) targets, pulsed-laser deposition (PLD) was carried out to produce thin films composed of nanoparticles and particulates in the presence of nitrogen gas. The size (2-100 nm) of the produced crystalline TiN nanoparticles increased as nitrogen pressure was increased in the range from 1.33 to 1.33 × 10² Pa. At a pressure of 1.33 × 10³ Pa, amorphous TiN nanoparticles combined in the form of chains. Large Ir particulates with diameters of up to 2 μm were particularly prominent in TiN-Ir films. Size distributions of the Ir particulates were dependent on ablation laser wavelength; that is, the diameter decreased at laser wavelength shortened. The TiN-Ir films with different Ir contents and morphologies on Ti substrates were evaluated as electrolysis electrodes for water disinfection. The highest current efficiency was 0.45%, which is comparable to that of conventional Ti-Pt electrodes, for a chloride-ion concentration of 9 mg dm⁻³.     

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.     

Effects of particle size and laser wavelength on heating of silver nanoparticles under laser irradiation in liquid

Laser energy absorption results in significant heating of metallic nanoparticles and controlling the heating of nanoparticles is one of the essential stages of selective cell targeting. It is necessary to note that the laser action should be done by laser pulses with a wavelength that is strongly absorbed by the particles and it is important to select wavelengths that are not absorbed by the medium. Laser pulse duration must be chosen sufficiently short to minimize heat flow emitted from absorbing particles. Numerical calculations based on Mie theory were used to obtain the effect of laser wavelength and particle size on absorption factor for colloidal silver nanoparticles with radii between 5 and 50 nm. Calculations for acquiring temperatures under irradiations of pulsed KrF laser and pulsed Nd:YAG laser were performed. We showed that for low wavelengths of the laser, smaller nanoparticles have larger absorption efficiency compared to larger nanoparticles and in high wavelengths, temperature of all particles increased in the same way.