We elucidate non-isotropic interactions present during laser ablation of ridged surface features under linearly-polarized light and their effect on nanoparticle synthesis via the laser ablation in liquid method. A relationship between the relative polarization/ridge orientation and ablation processes was established by measuring cavitation bubble kinetics, examining the morphology of the ablated surface, and evaluating nanoparticle size distribution. Anisotropic behavior was observed, and this is attributed to selective heating of linear surface structures as confirmed with rigorous coupled-wave analysis. When the incident electric field is aligned parallel to the linear ridges on the target surface, the resulting nanoparticle distributions are much more monodisperse. This phenomenon has a strong influence in the polydispersity and batch-to-batch reproducibility in laser ablation in liquid.
The influence of cavitation bubble dynamics is investigated during nanoparticle synthesis by ps laser ablation of Au targets in distilled and deionized water. The height of the liquid column and the ambient pressure is found to strongly influence both the maximum bubble radius and the collapse time, and thus the nanoparticle size distribution. The bubble radius is fit to the Rayleigh–Plesset equation and the results are compared to earlier studies with ns lasers. These results are interpreted in the light of recent computational work and the strong body of experimental evidence that shows the fundamental role the central cavitation bubble plays in determining the size distribution of nanoparticles in laser ablation in liquids.
The emergence of multidrug-resistant bacteria is a global clinical concern leading some to speculate about our return to a "pre-antibiotics" era of medicine. In addition to efforts to identify novel small-molecule antimicrobial drugs, there has been great interest in the use of metal nanoparticles as coatings for medical devices, wound dressings, and consumer packaging, due to their antimicrobial properties. The wide variety of methods available for nanoparticle synthesis results in a broad spectrum of chemical and physical properties which can affect antibacterial efficacy. This manuscript describes the pulsed laser-ablation in liquids (PLAL) method to create nanoparticles. This approach allows for the fine tuning of nanoparticle size, composition, and stability using post-irradiation methods as well as the addition of surfactants or volume excluders. By controlling particle size and composition, a large range of physical and chemical properties of metal nanoparticles can be explored which may contribute to their antimicrobial efficacy thereby opening new avenues for antibacterial development.
For this paper, single-pulse ablationmechanisms of ultrafast laser pulses (25 ps) were studied for thin gold films (65 nm) on an array of substrates with varying physical properties. Using time-domain thermoreflectance, the interfacial properties of the thin-film systems are measured: in particular, the thermal boundary conductance. We find that an often used, and widely accepted relation describing threshold fluences of homogeneous bulk targets breaks down at the nanoscale. Rather than relying solely on the properties of the ablated Au film, the ablation threshold of these Au/substrate systems is found to be dependent on the measured thermal boundary conductance; we additionally find no discernible trend between the damage threshold and properties of the underlying substrate. These results are discussed in terms of diffusive thermal transport and the interfacial bond strength.
The rise of antibiotic-resistant bacteria is a rapidly growing global health concern. According to the Center for Disease Control, approximately 2 million illnesses and 23,000 deaths per year occur in the USA due to antibiotic resistance. In recent years, there has been a surge in the use of metal nanoparticles as coatings for orthopedic implants, wound dressings, and food packaging, due to their antimicrobial properties. In this report, we demonstrate that the antibacterial efficacy of silver nanoparticles (AgNPs) is enhanced with exposure to light from the visible spectrum. We find that the increased toxicity is due to augmented silver ion release and bacterial uptake. Interestingly, silver ion toxicity does not appear to depend on the formation of reactive oxygen species. Our findings provide a novel paradigm for using light to regulate the toxicity of AgNPs which may have a significant impact in the development of new antimicrobial therapeutics.
In this work, the effect of laser fluence on Au nanoparticles synthesized via laser ablation in liquids is studied for 1064 nm irradiation with 25 ps pulses. Particle size and polydispersity is found to display a negative trend with fluences up to ∼14 J cm(-2). Erratic size tendencies are observed at low fluences, i.e. slightly above the ablation threshold. This overall behavior is reconciled with recent computational studies and to fluctuations in ablation due to surface morphology. The effectiveness of the commonly used surfactant sodium dodecyl sulfate (SDS) is shown to diminish at higher fluence due to pyrolysis. In addition, shadowgraph imaging of the cavitation bubble is shown as a useful technique for determining the ablation threshold. Our findings are in good agreement with threshold values determined by traditional methods and are comparable to computational values, when differences in pulse duration are taken into account.
Titanium dioxide is one of the most important materials today in terms of green technology. In this work, we synthesis ultra-small titanium dioxide nanoparticles (NPs) via a two step process involving infrared laser ablation of a bulk titanium target in DDI water and subsequent irradiation of the colloidal solution with visible light. The as-prepared NPs contain defect states related to oxygen vacancies which lead to visible light sensitization as observed by photodegradation of methylene blue. Irradiation of the colloidal TiO2 solution, with a 532 nm picosecond laser, lead to fragmentation and ultimate formation of ultrasmall (<3 nm) anatase particles. Shadowgraph was utilized to capture shockwave and cavitation bubble propagation during both the ablation and fragmentation processes. High-frequency ripples within the primary shockwave are identified as coming from laser induced stress-wave reflections within the metal target. A blueshift of the bandgap, for the ultra-small NPs, is explained by quantum confinement effects and rationalized using the Brus model. (C) 2015 Elsevier B.V. All rights reserved.
Nanoparticles (NPs) of the organic semiconductor rubrene were formed utilizing the laser ablation in liquids (LAL) method. Thin-films deposited by Matrix Assisted Pulsed Laser Evaporation (MAPLE) served as the ablation targets. We note in the case of amorphous films targets, the absorbed energy is below the threshold value needed for ablation; though polycrystalline films irradiated under the same LAL conditions result in ejecta. It is suggested this stems from an increase in the effective absorption through light trapping within crystalline domains. An observed red-shift in the absorption edge is attributed to the polar aqueous environment and to the crystalline phase.
We have carried out a systematic investigation of laser ablation plume interactions in resonant infrared matrix-assisted pulsed laser evaporation. The laser source utilized in this study was a mid-infrared OPO capable of dual sequential ns pulses with adjustable delay ranging from 1 to 100 μs. This unique capability enabled us both to probe the ablation plume with a second laser pulse, and to effectively double the laser fluence. The primary ablation target used for this study consisted of poly(methyl methacrylate) dissolved in a binary mixture of methanol and toluene. Both the critical thermodynamic and optical properties of the binary mixture were determined and used to interpret our results. We found that deposition rates associated with single pulse irradiation tracks with the optical absorption coefficient in the spectral range from 2,700 to 3,800 nm. In the case of dual sequential pulses, discrepancies in this trend have been linked to the rate of change in the optical absorption coefficient with temperature. The influence of fluence on deposition rate was found to follow a sigmoidal dependence. Surface roughness was observed to have a diametrically opposed trend with pulse delay depending on whether the OH or CH vibrational mode was excited. In the case of CH excitation, we suggest that the rougher films are due to the absorbance of the second pulse by droplets within the plume containing residual solvent which leads to the formation of molecular balloons and hence irregularly shaped features on the substrate.
The study of shock propagation in air and liquid can play an important role in understanding light-matter interactions during laser processing experiments. In this work, we perform plume shadowgraphy experiments on liquid and solid targets of acetone and toluene and calculate the velocity and pressure at the leading edge of the shock front. Our results are compared to recent work in which early blast wave dynamics are studied and the applicability of the classical Taylor–Sedov model is assessed for our data. We observe an enhanced vertical expansion in the shockwave that is attributable to absorption and heating above the surface.
Nanoparticles have been produced by laser ablation of thin gold films on soda lime glass slides that are immersed in distilled and deionized water. The size of the nanoparticles, as determined by fitting the UV–vis absorption spectrum, shows that the average particle radius depends on the thin film thickness in the range of 50–200 nm. A heuristic model is developed to explain these results as being strongly dependent on the average temperature that is reached in the thin films, and the subsequent heating of the surrounding medium. The strong thermal mismatch at the film-substrate boundary appears to play a strong role as well.
We have reported in our previous work that doping low concentrations (up to 10% by weight) of gold nanoparticles (GNP) in a polar nematic 4'-hexyl-4-biphenylcarbonitrile (HBPCN) increases the dielectric anisotropy, while the switching voltage and times, and the nematic-isotropic liquid (IL) transition point of the mixtures are not affected by doped nanoparticles. In the current work we extend our study of the behaviour of HBPCN doped with higher than 10% GNP. We show that at certain gold concentrations -35% and 45% - the nematic-IL phase transition point increases by 15 degrees C in comparison with the pure nematic value. At the same concentrations the dielectric anisotropy increases from its value for the pure nematic by about 2.2 times for 35% and twice for 45%. Also, the threshold voltage increases by 0.2 V for 35% and decreases by 0.15 V for 45%. However, the switching-off times decrease for both concentrations: 7 ms for 35% and 12 ms for 45%. We propose that the described effects of doped GNP on the properties of the nematic are due to the formation of different kinds of aggregations between two components of the mixtures.
MAPLE has long been demonstrated as a successful tool for the deposition of relatively large polymerics and biomaterials. Less work has been done with small-mass organic compounds. In this work, MAPLE has been demonstrated as a viable materials processing technique for 4,5-dihydroxycyclopentenetrione, a diprotic hydroxylic acid, more commonly known as croconic acid ((C=O)3(COH)2). Croconic acid readily dissociates in solution, and, as prepared in the solvent matrices used in this study, was deposited in large part as the solvated croconate conjugate base. Various substrates were utilized and the deposited films were characterized by infrared spectroscopy, atomic and piezo-force microscopy, scanning electron microscopy, and second harmonic generation measurements. This material has potential application in nonlinear optics and green computing as memory elements.