Driven by functionality and purity demand for applications of inorganic nanoparticle colloids in optics, biology, and energy, their surface chemistry has become a topic of intensive research interest. Consequently, ligand-free colloids are ideal reference materials for evaluating the effects of surface adsorbates from the initial state for application-oriented nanointegration purposes. After two decades of development, laser synthesis and processing of colloids (LSPC) has emerged as a convenient and scalable technique for the synthesis of ligand-free nanomaterials in sealed environments. In addition to the high-purity surface of LSPC-generated nanoparticles, other strengths of LSPC include its high throughput, convenience for preparing alloys or series of doped nanomaterials, and its continuous operation mode, suitable for downstream processing. Unscreened surface charge of LSPC-synthesized colloids is the key to achieving colloidal stability and high affinity to biomolecules as well as support materials,...

Laser Synthesis and Processing of Colloids: Fundamentals and Applications

Laser ablation of solid targets in the liquid medium can be realized to fabricate nanostructures with various compositions (metals, alloys, oxides, carbides, hydroxides, etc.) and morphologies (nanoparticles, nanocubes, nanorods, nanocomposites, etc.). At the same time, the post laser irradiation of suspended nanomaterials can be applied to further modify their size, shape, and composition. Such fabrication and modification of nanomaterials in liquid based on laser irradiation has become a rapidly growing field. Compared to other, typically chemical, methods, laser ablation/irradiation in liquid (LAL) is a simple and “green” technique that normally operates in water or organic liquids under ambient conditions. Recently, the LAL has been elaborately developed to prepare a series of nanomaterials with special morphologies, microstructures and phases, and to achieve one-step formation of various functionalized nanostructures in the pursuit of novel properties and applications in optics, display, detection, and biological fields. The formation mechanisms and synthetic strategies based on LAL are systematically analyzed and the reported nanostructures derived from the unique characteristics of LAL are highlighted along with a review of their applications and future challenges.

Nanomaterials via Laser Ablation/Irradiation in Liquid: A Review

State of the art in gold nanoparticle synthesis

Laser ablation synthesis in liquid solution (LASiS) is a “green” technique that gives access to the preparation of a library of nanomaterials. Bare noble metal spherical particles, multiphase core–shell oxides, metal–semiconductor heterostructures, layered organometallic compounds and other complex nanostructures can be obtained with the same experimental set up, just by varying a few synthetic parameters. How to govern such versatility is one of the current challenges of LASiS and requires a thorough understanding of the physical and chemical processes involved in the synthesis. In this perspective, the fundamental mechanisms of laser ablation in liquids are summarized, organized according to their temporal sequence and correlated with relevant examples taken from the library of nanomaterials disclosed by LASiS, in order to show how synthesis parameters influence the composition and the structure of products. The resulting framework suggests that, to date, much attention has been devoted to the physical aspects of laser–matter interaction and to the characterization of the final products of the synthesis. Conversely, the clarification of chemical processes active during LASiS deserves more research efforts and requires the synergy among multiple investigation techniques.

What controls the composition and the structure of nanomaterials generated by laser ablation in liquid solution

It is well-known that nanoparticles could cause toxic effects in cells. Alloy nanoparticles with yet unknown health risk may be released from cardiovascular implants made of Nickel–Titanium or Cobalt–Chromium due to abrasion or production failure. We show the bio-response of human primary endothelial and smooth muscle cells exposed to different concentrations of metal and alloy nanoparticles. Nanoparticles having primary particle sizes in the range of 5–250 nm were generated using laser ablation in three different solutions avoiding artificial chemical additives, and giving access to formulations containing nanoparticles only stabilized by biological ligands. Endothelial cells are found to be more sensitive to nanoparticle exposure than smooth muscle cells. Cobalt and Nickel nanoparticles caused the highest cytotoxicity. In contrast, Titanium, Nickel–Iron, and Nickel–Titanium nanoparticles had almost no influence on cells below a nanoparticle concentration of 10 μM. Nanoparticles in cysteine dissolved almost completely, whereas less ions are released when nanoparticles were stabilized in water or citrate solution. Nanoparticles stabilized by cysteine caused less inhibitory effects on cells suggesting cysteine to form metal complexes with bioactive ions in media.

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Cytotoxicity and ion release of alloy nanoparticles.

An analytical model for the prediction of the dielectric properties of gold– silver alloys is developed. This multi-parametric model is a modifi cation of the usual Drude–Lorentz model that takes into account the band structure of the metals. It is fi tted by a genetic algorithm to the dielectric function of thin alloy fi lms 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.

An Analytic Model for the Dielectric Function of Au, Ag, and their Alloys

A femtosecond laser-based method to control the size characteristics of gold colloidal nanoparticles is reported. The method uses the supercontinuum generation produced through a strong nonlinear-optical interaction of the femtosecond radiation with a liquid to fragment relatively large colloids and reduce their agglomeration. The fragmented species then recoalesce to form smaller, less dispersed, and much more stable nanoparticles in the solution. The size of the nanoparticles after the treatment is independent of the initial characteristics of colloids, but depends strongly on laser parameters and on the presence of chemically active species in the solution.

Fragmentation of colloidal nanoparticles by femtosecond laser-induced supercontinuum generation

Inorganic nanoparticles offer novel promising properties for biological sensing and imaging, as well as in therapeutics. However, these applications are often complicated by the possible toxicity of conventional nanomaterials, arising as a result of inadequate purification procedures of nanoparticles obtained via synthetic pathways using toxic or non-biocompatible substances. We review novel femtosecond laser-assisted methods, which enable the preparation of metal nanomaterials in clean, biologically friendly aqueous environment (“green” synthesis) and thus completely solve the toxicity problem. The proposed methods, including laser ablation and fragmentation, make possible the production of stable metal colloids of extremely small size (∼2 nm) with a low coefficient of variation (15–25%). Those nanoparticles exhibit unique surface chemistry and can be used for bio-imaging, cancer treatment and nanoparticle-enhanced Raman spectroscopy.

Ultrafast laser based “green” synthesis of non-toxic nanoparticles in aqueous solutions

A femtosecond laser-assisted method has been developed to produce stable, size-tunable (3 to ∼80 nm) and low dispersed gold nanoparticles. The method implies the formation of initial nanosized seed...

Synthesis of Size-Tunable Polymer-Protected Gold Nanoparticles by Femtosecond Laser-Based Ablation and Seed Growth

A two-step laser-assisted method for the synthesis of small and low-dispersed colloidal gold nanoparticles in deionized water is reported. As the first step, laser ablation from a gold target is used to fabricate relatively large (few tens of nanometers) and size-dispersed colloids. As the second step, self-modification of the femtosecond laser pulse into a white-light supercontinuum is used to perform the secondary ablation of colloids. We show that the latter treatment leads to a drastic reduction of both the mean nanoparticles size and size dispersion as well as to the enhancement of the solution stability. Being prepared in pure deionized water, the colloidal nanoparticles are stable and free of any impurities, making them unique for surface enhanced Raman scattering (SERS) and bio-imaging in vivo applications.

Sébastien Besner

Papers

An Analytic Model for the Dielectric Function of Au, Ag, and their Alloys

Fragmentation of colloidal nanoparticles by femtosecond laser-induced supercontinuum generation

Ultrafast laser based “green” synthesis of non-toxic nanoparticles in aqueous solutions

Synthesis of Size-Tunable Polymer-Protected Gold Nanoparticles by Femtosecond Laser-Based Ablation and Seed Growth

Two-step femtosecond laser ablation-based method for the synthesis of stable and ultra-pure gold nanoparticles in water