Photoluminescence studies of Si/SiO2 nanoparticles synthesized with different laser irradiation wavelengths of nanosecond pulse duration

Photoluminescence (PL) properties of Si nanoparticles (Si-np) produced by irradiating the Si wafer with nanosecond laser pulses at 532, 683 and 1064 nm are studied. Si-np are found to be deposited in a doughnut shape around the irradiated spot. The irradiation wavelength is found to be the main cause for the particle size variation. Exposure of the freshly prepared Si-np to air for different periods of time leads to increased PL intensity reaching saturation after few days. The PL spectrum shows two well resolved peaks around 435 nm (2.85 eV) and 441 nm (2.81 eV) within an hour of exposure of the freshly prepared samples to air with broadening of the emission spectrum on further exposure to air. Possible mechanism of particle size variation and PL emission are discussed.     

1064-nm laser fragmentation of thin Au and Ag flakes in acetone for highly productive pathway to stable metal nanoparticles

The laser-induced fragmentation of thin Au and Ag flakes in acetone by 1064-nm nanosecond laser (with the fluence typically ∼2 J/cm²) potentially offers a highly productive pathway to stable metal nanoparticles in liquid. Acetone serves as a superior liquid medium that keeps fine metal nanoparticles free from precipitation even in such concentrated nanoparticle solutions exceeding ∼0.1 M. Thin metal flakes have good capability to absorb the 1064-nm laser energy as efficiently as in the visible region. A part of the thus laser-heated molten flakes explosively split into submicroparticles, and some other significant part directly into fine nanoparticles. Both kinds of product particles have minor absorption cross-sections for subsequent laser pulses at 1064 nm, and thus no longer fragment further. One of the two kinds of Ag flakes studied in this work yielded fine Ag nanoparticles at a remarkable high production rate of 1.1 mg/min for the input laser power of only ∼0.65 W.     

On 308 nm photofragmentation of the silver nanoparticles

Silver nanoparticles (Ag NPs) were prepared by different chemical methods possessing different sizes 3 ± 2, 8 ± 2, and 20 ± 5 nm. The influence the size of Ag NPs was demonstrated by the absorption and fluorescence spectra, the maximum absorption of Ag NPs increases as the particle size increases. When Ag NPs irradiated with 308 nm excimer laser; the maximum absorption and the full width at half maximum decreased as the number of pulses increased up to 100,000 pulse; due to the size reduction. The fluorescence spectra of Ag NPs and irradiated Ag NPs with 308 nm excimer laser were recorded after excitation at 441.5 nm He-Cd laser, showing a red shift increasing as the particle size is increased.     

Optical and nonlinear optical characteristics of the Ge and GaAs nanoparticle suspensions prepared by laser ablation

The laser ablation of Ge and GaAs targets placed in water and ethanol was carried out using the fundamental radiation of nanosecond Nd:YLF laser. The results of preparation and the optical and nonlinear optical characterization of the Ge and GaAs nanoparticle suspensions are presented. The considerable shift of the band gap energy of the nanoparticles compared to the bulk semiconductors was observed. The distribution of nanoparticle sizes was estimated in the range of 1.5-10 nm on the basis of the TEM and spectral measurements. The nonlinear refractive indices and nonlinear absorption coefficients of Ge and GaAs nanoparticles were defined by the z-scan technique using second harmonic radiation of picosecond Nd:YAG laser (λ = 532 nm).     

Pump-dependent luminescence in the Ag nanoparticles doped by Erbium

A substantial spectral shift of the UV-laser induced luminescence in the Ag nanoparticles (NP) doped by Er³⁺ ions attached to ITO substrates was observed at T = 4.2 K. We have established high energy spectral shift of principal luminescent maxima (from wavelength equal to about 1.45 up to 1.15 μm) with increasing of the pumping nanosecond nitrogen laser power density up to 1.1 GW/cm² operating at λ = 337 nm. With increasing Erbium content with respect to Ag the spectral shift and spectral line broadening increase. It may be caused by specific features of trapping level occupation kinetics on interfaces NP/ITO substrate. The observed process is fully reversible. The luminescence is observed only during excitation by the 337 nm laser pulses and is absent for laser pulses operating at other wavelengths (like excimer laser at 218 nm and nitrogen laser at 371 nm).     

Nanoparticle composites: FePt with wide-band-gap semiconductor

We present a simple way to synthesize FePt and ZnO (wide-band-gap semiconductor) nanoparticle composites. The FePt nanoparticles were fabricated using the method reported by Sun et al. By controlling the heating rate, 3 nm FePt nanoparticles were synthesized. Well-dispersed FePt and ZnO nanoparticle composites were prepared by further adding zinc acetate and oleyl amine into the 3 nm FePt nanoparticle dispersion. By controlling the molar ratio of the FePt and zinc acetate, FePt and ZnO nanoparticle composites with different FePt particle fractions were obtained. The intensity of photo luminescence spectra of the nanoparticle composites increases very much with decreasing FePt particle fraction, whereas the peak position shifts a little. After annealing at 550 °C for half an hour, the nanoparticle composites become magnetically hard or semi-hard with coercivity much dependent on the FePt particle volume fraction. The coercivity of the composites increases with annealing temperature. The composites hold the promise of applications in new generation recording and/or optical devices.     

Time-resolved transmission study of fused silica during laser-induced backside dry etching

Laser-induced backside dry etching (LIBDE) is a promising technique for micro- and nanomachining of transparent materials. Although several experiments have already proved the suitability and effectiveness of the technique, there are several open questions concerning the etching mechanism and the concomitant processes. In this paper time-resolved light transmission investigations of etching process of fused silica are presented. 125 nm thick silver coating was irradiated through the carrying 1 mm thick fused silica plate by single pulses of a nanosecond KrF excimer laser. The applied fluences were 0.38, 0.71 and 1 J/cm². During the etching process the irradiated spots were illuminated by an electronically delayed nitrogen laser pumped dye laser. The delay between the pump and probe pulses was varied in the range of 0 ns and 20 μs. It was found that the transmitted probe beam intensity strongly depends on the applied delays and fluences. Scanning electron microscopy and energy dispersive X-ray spectrometry of the etched surface showed the existence of silver droplets and fragments on the illuminated surfaces and silver atoms built into the treated surface layer influencing the transmission behavior of the studied samples.     

Molecular dynamics simulation of neck growth in laser sintering of different-sized gold nanoparticles under different heating rates

The neck growth in the laser sintering of different-sized gold (100) nanoparticles under different heating rates is investigated using a molecular dynamics method. The numerical simulations are carried out for four pairs of two spherical nanoparticles under three different heating rates. For each pair, one nanoparticle has the same diameter of 4 nm and the other nanoparticle’s diameter is varied, ranging from 4 nm to 20 nm. The results show that the solid state sintering automatically takes place by local potential at room temperature. The stable neck width increases as the size of the other nanoparticle increases. Once the limit stable neck width is reached, it no longer is affected by the nanoparticle size. For the subsequent laser heating to the same final temperature, a lower heating rate results in a larger stable neck width due to the longer sintering process. The neck growth mechanisms and rate under various sintering conditions are discussed.     

ZnO nanoparticles produced by novel reactive physical deposition process

This paper reports the deposition of ZnO nanoparticles with controlled sizes and different particle densities and their structural, composition and optical properties. They were deposited by means of a DC magnetron based vacuum nanoparticle source onto different substrates (GaAs, Si and Ti/SiO₂/Si). We believe that this is the first time that such nanoparticles have been produced using this unique technique. Zinc was used as sputtering target to produce zinc nanoparticles which were oxidized in-line using molecular oxygen. The structural properties and chemistry of the ZnO were studied by transmission electron microscopy. An average particle size of 6(±2) nm was produced with uniform size distribution. The particle density was controlled using a quartz crystal monitor. Surface densities of 2.3 × 10¹¹/cm², 1.1 × 10¹³/cm² and 3.9 × 10¹³/cm² were measured for three different deposition runs. The ZnO particles were found to be single crystalline having hexagonal structure. Photoluminescence measurements of all samples were performed at room temperature using a cw He-Cd laser at 325 nm excitation. The UV emission around 375 nm at room temperature is due to excitonic recombination and the broad emission centered at 520 nm may be attributed to intrinsic point defects such as oxygen interstitials.     

Comparing study of subpicosecond and nanosecond wet etching of fused silica

The effectiveness of the laser induced backside wet etching (LIBWE) of fused silica produced by subpicosecond (600 fs) and nanosecond (30 ns) KrF excimer laser pulses (248 nm) was studied. Fused silica plates were the transparent targets, and naphthalene-methyl-methacrylate (c = 0.85, 1.71 M) and pyrene-acetone (c = 0.4 M) solutions were used as liquid absorbents. We did not observe etching using 600 fs laser pulses, in contrast with the experiments at 30 ns, where etched holes were found. The threshold fluences of the LIBWE at nanosecond pulses were found to be in the range of 360-450 mJ cm⁻² depending on the liquid absorbers and their concentrations. On the basis of the earlier results the LIBWE procedure can be explain by the thermal heating of the quartz target and the high-pressure bubble formation in the liquid. According to the theories, these bubbles hit and damage the fused silica surface. The pressure on the irradiated quartz can be derived from the snapshots of the originating and expanding bubbles recorded by fast photographic setup. We found that the bubble pressure at 460 mJ cm⁻² fluence value was independent of the pulse duration (600 fs and 30 ns) using pyrene-acetone solution, while using naphthalene-methyl-methacrylate solutions this pressure was 4, 5 times higher at 30 ns pulses than it was at 600 fs pulses. According to the earlier studies, this result refers to that the pressure should be sufficiently high to remove a thin layer from the quartz surface using pyrene-acetone solution. These facts show that the thermal and chemical phenomena in addition to the mechanical effects also play important role in the LIBWE procedure.     

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.     

Magnetic properties and morphology of Ni nanoparticles synthesized in gas phase

We report on the size, structure and magnetic properties of Ni nanoparticles fabricated with a free-jet sputtering nanoparticle source. It is found how the pressure of the inert gas and the diameter of the source nozzle can control the particle size and coercivity in a wide range. Measurements of the specific magnetic moment of Ni nanoparticles are reported. A particular growing regime is found at high pressures over 1.8 mbar observing a further aggregation process that leads to nanoparticle agglomerates with diameters larger than 100 nm with a low dispersion in size.     

Enhanced photoluminescence of ZnO-SiO2 nanocomposite particles and the analyses of structure and composition

Stable blue-green photoluminescent ZnO-SiO₂ nanocomposite particles exhibiting quantum efficiency as high as 34.8% under excitation at 360 nm were prepared using a spray-drying process from a feed solution that contained both luminescent ZnO nanoparticles synthesized by a sol-gel method and commercially-available SiO₂ nanoparticles. The effects of silica nanoparticle size and SiO₂-to-ZnO concentration ratio on the PL properties of the composite particles were investigated. The internal structure and chemical composition were investigated in detail using elemental mapping, which revealed that ZnO nanoparticles were well-dispersed within silica nanoparticle matrix. At a LiOH concentration of 0.23 M, the predicted ZnO crystallite diameter before and after spray drying was approximately constant at 3.3 and 3.6 nm, respectively. This result indicates that ZnO particle growth was inhibited and therefore the PL property of ZnO nanoparticles was stably preserved in the composite.     

Direct observation of phase transitions by time-resolved pyro/reflectometry of KrF laser-irradiated metal oxides and metals

New experimental results are obtained by coupling both time-resolved reflectivity and rapid infrared pyrometry under a hemispherical reactor. The heating source KrF laser beam (28 ns, 248 nm) is homogenized and as for probing, a CW He-Ne laser beam (10 mW, 633 nm) is used.Using both methods infrared pyrometry with an IR detector cooled with liquid nitrogen and sensitive in the spectral range 1-12 μm, and time-resolved reflectivity with a rapid photodiode, we were able to study complex thermodynamic transitions with nanosecond time resolution. Three different materials are studied by varying the KrF fluence (energy/surface) from 100 to 2000 mJ/cm²: thin films melting (Au/Ni), the threshold of plasma formation (Ti), and complex liquid phase segregation under semi-conductor state (ZnO). The formation of a liquid Zn film induced by temperature gradient is well evidenced by our signals. Also melting of thin films irradiated by low laser fluences (less than 500 mJ/cm²) translates the typical thermodynamic behavior. Finally, wide fluence dynamic (400-2000 mJ/cm²) is analyzed in the case of Ti surface, and results show two distinguished regimes: first one bellow 1000 mJ/cm² corresponding to the early stage plasma initiation, and second one over 1000 mJ/cm² to the dynamics of plasma expansion.     

Nanosecond and femtosecond UV laser ablation of polymers: Influence of molecular weight

We examine the nanosecond and femtosecond UV laser ablation of poly(methyl methacrylate) (PMMA) as a function of molecular weight (M_w). For laser ablation with nanosecond laser pulses, at the excimer wavelengths 248 nm and 193 nm, we show that high temperatures develop; yet the dynamics of material ejection differs depending on polymer M_w. The results on the nanosecond ablation of polymers are accounted within the framework of bulk photothermal model and the results of molecular dynamics simulations. Turning next to the 248 nm ablation with 500 fs laser pulses, the ablation threshold and etching rates are also found to be dependent on polymer M_w. In addition, ablation results in morphological changes of the remaining substrate. Plausible mechanisms are advanced.     

Hierarchical nanoparticle morphology for platinum supported on SrTiO3 (0 0 1): A combined microscopy and X-ray scattering study

The morphology of metal nanoparticles supported on oxide substrates plays an important role in heterogeneous catalysis and in the nucleation of thin films. For platinum evaporated onto SrTiO₃ (0 0 1) and vacuum annealed we find an unexpected growth formation of Pt nanoparticles that aggregate into clusters without coalescence. This hierarchical nanoparticle morphology with an enhanced surface-to-volume ratio for Pt is analyzed by grazing incidence small-angle X-ray scattering (GISAXS), X-ray fluorescence (XRF), atomic force microscopy (AFM) and high-resolution scanning electron microscopy (SEM). The nanoparticle constituents of the clusters measure 2-4 nm in size and are nearly contiguously spaced where the average edge-to-edge spacing is less than 1 nm. These particles make up the clusters, which are 10-50 nm in diameter and are spaced on the order of 100 nm apart.     

Heat dissipation mechanism of magnetite nanoparticles in magnetic fluid hyperthermia

The relative contributions of Néel and Brownian relaxations on magnetic heat dissipation were studied by investigating the physical, magnetic and heating characteristics of magnetite nanoparticle suspensions with average diameters of 12.5 and 15.7 nm. Heating characteristics depended on the dispersion states of particles. The specific absorption rates (SAR) dropped by 27% for the 12.5 nm particles to 16.8×10⁻⁹ W g⁻¹ Oe⁻² Hz⁻¹ and by 67% for the 15.7 nm particles to 9.69×10⁻⁹ W g⁻¹ Oe⁻² Hz⁻¹, when the particle rotation was suppressed by dispersing magnetite nanoparticles in hydro-gel.     

The potential of UV femtosecond laser ablation for varnish removal in the restoration of painted works of art

Despite significant advances, laser ablation with nanosecond pulses presents limitations in dealing with the restoration of classes of painted works of art, such as paintings with a very thin layer of varnish. Femtosecond laser processing promises the means for overcoming such limitations. To this end, femtosecond ablation of two typical varnishes, dammar and mastic, is examined. For these varnishes, processing by Ti:Sapphire irradiation (800 nm) turns out to be ineffective. In contrast, irradiation with 248 nm ∼500 fs laser pulses results in a higher etching resolution (etching rates of ∼1 μm/pulse or less). For irradiation with few laser pulses at moderate laser fluences, etched morphology is far smoother than in the processing with nanosecond laser pulses. Furthermore, chemical modifications are considerably reduced (by nearly an order of magnitude), and exhibit a number of additional novel differences. Both etching rates and extent of chemical modifications are largely independent of varnish absorptivity. In all, femtosecond UV laser irradiation is indicated to hold a high potential, offering new perspectives for the restoration of painted works of art. Finally, a tentative model is advanced accounting in a consistent way for the observations.