The femtosecond laser ablation of a gold target in aqueous solutions has been used to produce colloidal Au nanoparticles with controlled surface chemistry. A detailed chemical analysis showed that the nanoparticles formed were partially oxidized by the oxygen present in solution. The hydroxylation of these Au-O compounds, followed by a proton loss to give surface Au-O -, resulted in the negative charging of the nanoparticles. The partial oxidation of the gold nanoparticle surface enhances its chemical reactivity and consequently has a strong impact on its growth. In particular, the oxidized surface reacted efficiently with Cland OHto augment its net surface charge. This limited the coalescence of the particles, due to electrostatic repulsion, and led to a significant reduction of their size. Taking advantage of the repulsion effect, efficient size control was achieved using different salts (7 ( 5 nm for 10 mM KCl, 5.5 ( 4 nm for 10 mM NaCl, 8 ( 5 nm for NaOH, pH 9.4), a considerable improvement comparatively to particles prepared in deionized water, using identical ablation conditions, where particles of 1-250 nm were produced. The partially oxidized gold surface was also suitable for surface modification through both covalent and electrostatic interactions during particle formation. Using solutions of N-propylamine, we showed an efficient control of nanoparticle size (5-8 ( 4-7 nm) by the involvement of these interactions. The results obtained help to develop methodologies for the control of laser-ablation-based nanoparticle growth and the functionalization of nanoparticle surfaces by specific interactions.
Femtosecond laser radiation has been used to ablate a gold target in pure deionized water to produce colloidal gold nanoparticles. We report evidence for two different mechanisms of material ablation in the liquid environment, whose relative contributions determine the size distribution of the produced particles. The first mechanism, associated with thermal-free femtosecond ablation, manifests itself at relatively low laser fluences F<400 J/cm2 and leads to very small (3–10 nm) and almost monodispersed gold colloids. The second one, attributed to the plasma-induced heating and ablation of the target, takes place at high fluences and gives rise to a much larger particle size and broad size distribution. The fabricated nanoparticles exhibit plasmon-related optical absorption peak and are of significance for biosensing applications.
An analytical model for the prediction of the dielectric properties of gold–silver alloys is developed. This multi‐parametric model is a modification of the usual Drude–Lorentz model that takes into account the band structure of the metals. It is fitted by a genetic algorithm to the dielectric function of thin alloy films of different gold–silver ratio obtained by ellipsometry. The model is validated for arbitrary alloy compositions by comparing the experimental extinction spectra of alloy nanoparticles with the spectra predicted by Mie theory.
Femtosecond laser radiation has been used to ablate a gold target in aqueous beta-cyclodextrin (CD) solutions to produce stable gold nanoparticle colloids with extremely small size (2 to 2.4 nm) and size dispersion (1 to 1.5 nm). On the basis of XPS and zeta-potential measurements, we propose a model involving chemical interactions between the gold and the CDs. The model includes both the hydrophobic interaction of the Au0 with the interior cavity of the CD and the hydrogen bonding of O- groups on the partially oxidized gold surface with -OH groups of the CDs.
The thermodynamic pathways involved in laser irradiation of absorbing solids are investigated in silicon for pulse durations of 500 fs and 100 ps. This is achieved by accounting for carrier and atom dynamics within a combined Monte Carlo and molecular-dynamics scheme and simultaneously tracking the time evolution of the irradiated material in-T-P space. Our simulations reveal thermal changes in long-range order and state of aggregation driven, in most cases, by nonequilibrium states of rapidly heated or promptly cooled matter. Under femtosecond irradiation near the ablation threshold, the system is originally pulled to a near-critical state following rapid ͑Շ10 −12 s͒ disordering of the mechanically unstable crystal and isochoric heating of the resulting metallic liquid. The latter is then adiabatically cooled to the liquid-vapor regime where phase explosion of the subcritical, superheated melt is initiated by a direct conversion of translational, mechanical energy into surface energy on a ϳ10 −12-10 −11 s time scale. At higher fluences, matter removal involves, instead, the fragmentation of an initially homogeneous fluid subjected to large strain rates upon rapid, supercritical expansion in vacuum. Under picosecond irradiation, homogeneous and, at later times, heterogeneous melting of the superheated solid are followed by nonisochoric heating of the molten metal. In this case, the subcritical liquid material is subsequently cooled onto the binodal by thermal conduction and explosive boiling does not take place; as a result, ablation is associated with a "trivial" fragmentation process, i.e., the relatively slow expansion and dissociation into liquid droplets of supercritical matter near thermodynamic equilibrium. This implies a liquid-vapor equilibration time of ϳ10 −11-10 −10 s and heating along the binodal under nanosecond irradiation. Solidification of the nonablated, supercooled molten material is eventually observed on a ϳ10 −11-10 −9 s time scale, irrespective of the pulse duration.
The generation of nanobubbles around plasmonic nanostructures is an efficient approach for imaging and therapy, especially in the field of cancer research. We show a novel method using infrared femtosecond laser that generates ≈800 nm bubbles around off-resonance gold nanospheres using 200 mJ/cm(2) 45 fs pulses. We present experimental and theoretical work that demonstrate that the nanobubble formation results from the generation of a nanoscale plasma around the particle due to the enhanced near-field rather than from the heating of the particle. Energy absorbed in the nanoplasma is indeed more than 11 times the energy absorbed in the particle. When compared to the usual approach that uses nanosecond laser to induce the extreme heating of in-resonance nanoparticles to initiate bubble formation, our off-resonance femtosecond technique is shown to bring many advantages, including avoiding the particles fragmentation, working in the optical window of biological material and using the deposited energy more efficiently.
Noble metal nanoparticles due to their unique optical properties arising from their interactions with an incident light have been intensively employed in a broad range of applications. This review comprehensively describes fundamentals behind plasmonics, used to develop applications in the fields of biomedical, energy, and information technologies. Basic concepts (electromagnetic interaction and permittivity of metals) are discussed through Mie theory presented as the main model for interpreting phenomena of optical absorption and scattering. The effects of near‐field enhancement, shape, composition, and surrounding medium of nanoparticles on optical properties are described in detail. The review explores and identifies the potential of plasmonic nanoparticles based on their optical properties (e.g., light absorption, scattering, and field enhancement) for developing different applications (biomedical, energy and information technologies). Due to a significant impact of plasmonic nanoparticles on medicine and healthcare products and technologies, the review initially focuses on biomedical applications extensively benefited from optical features of these nanoparticles. Advantages of the optical properties outstandingly implemented are also briefly discussed in other applications, including energy and information technologies. This review concisely summarizes the explored areas based on plasmonic properties, compares advantages of plasmonic nanoparticles over other types of nanomaterials and highlights challenges.
The mechanisms of laser ablation in silicon are investigated close to the threshold energy for pulse durations of 500 fs and 50 ps. This is achieved using a unique model coupling carrier and atom dynamics within a unified Monte Carlo and molecular-dynamics scheme. Under femtosecond laser irradiation, isochoric heating and rapid adiabatic expansion of the material provide a natural pathway to phase explosion. This is not observed under slower, nonadiabatic cooling with picosecond pulses where fragmentation of the hot metallic fluid is the only relevant ablation mechanism.
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