Fracture and Embedment Behavior of Brittle Submicrometer Spherical Particles Fabricated by Pulsed Laser Melting in Liquid Using a Scanning Electron Microscope Nanoindenter.

Generally, hard ceramic carbide particles, such as B4C and TiC, are angulated, and particle size control below the micrometer scale is difficult owing to their hardness. However, submicrometer particles (SMPs) with spherical shape can be experimentally fabricated, even for hard carbides, via instantaneous pulsed laser heating of raw particles dispersed in a liquid (pulsed laser melting in liquid). The spherical shape of the particles is important for mechanical applications as it can directly transfer the mechanical force without any loss from one side to the other. To evaluate the potential of such particles for mechanical applications, SMPs were compressed on various substrates using a diamond tip in a scanning electron microscope. The mechanical behaviors of SMPs were then examined from the obtained load-displacement curves. Particles were fractured on hard substrates, such as SiC, and fracture strength was estimated to be in the GPa range, which is larger than their corresponding bulk bending strength and is 10-40% of their ideal strength, as calculated using the density-functional theory. Contrarily, particles can be embedded into soft substrates, such as Si and Al, and the local hardness of the substrate can be estimated from the load-displacement curves as a nanoscale Brinell hardness measurement.

Behavior of Thermally Induced Nanobubbles during Instantaneous Particle Heating by Pulsed Laser Melting in Liquid.

Pulsed laser melting in liquid (PLML) is a technique to produce submicrometer spherical particles (SMPs). In this process, raw particles dispersed in liquid are selectively heated, and thermally induced nanobubbles (TINBs) at the particle surface are generated and act as a thermal barrier to enhance the temperature increase during heating. However, monitoring TINBs is difficult since PLML is a low-temperature, nonplasma process. Simple transmittance measurements of monodisperse Au SMP (250 nm) colloidal solutions on a transient time scale were used to monitor the temporal dependence of the TINB thickness and the pressure within the bubble. By applying this technique for ZnO and Sn SMP formation, TINBs in the PLML process are important in promoting the formation of large particles via particle merging during laser heating.

Reduction Mechanism of Transition Metal Oxide Particles in Thermally Induced Nanobubbles during Pulsed Laser Melting in Ethanol.

Pulsed laser melting in liquid (PLML) is a technique to fabricate spherical submicrometer particles (SMPs) wherein nanosecond pulsed laser (several tens to several hundreds of mJ pulse-1 cm-2 ) irradiates raw particles dispersed in liquid. Raw particles are transiently heated above the melting point to form spherical particles, which enables pulsed heating of surrounding liquid to form thermally induced bubbles by liquid vaporization. These transient bubbles play an important role as a thermal barrier to rapidly heat the particle. Reduced SMPs are generated from raw metal-oxide nanoparticles by PLML process in ethanol. This reduction cannot be explained by high-temperature thermal decomposition, but by mediation of molecules decomposed from ethanol. Computational simulations of ethanol decomposition by pulsed heating for 100 ns at the temperature 1000-4000 K revealed that ethylene is generated as the main product. Gibbs free energies of oxide reduction reactions mediated by ethylene greatly decreased compared to those without ethylene mediation. This explanation can be applied to reductive SMP formation from various transition metal oxides by PLML.

Room-Temperature Laser Synthesis in Liquid of Oxide, Metal-Oxide Core-Shells, and Doped Oxide Nanoparticles.

Although oxide nanoparticles are ubiquitous in science and technology, a multitude of compositions, phases, structures, and doping levels exist, each one requiring a variety of conditions for their synthesis and modification. Besides, experimental procedures are frequently dominated by high temperatures or pressures and by chemical contaminants or waste. In recent years, laser synthesis of colloids emerged as a versatile approach to access a library of clean oxide nanoparticles relying on only four main strategies running at room temperature and ambient pressure: laser ablation in liquid, laser fragmentation in liquid, laser melting in liquid and laser defect-engineering in liquid. Here, established laser-based methodologies are reviewed through the presentation of a panorama of oxide nanoparticles which include pure oxidic phases, as well as unconventional structures like defective or doped oxides, non-equilibrium compounds, metal-oxide core-shells and other anisotropic morphologies. So far, these materials showed several useful properties that are discussed with special emphasis on catalytic, biomedical and optical application. Yet, given the endless number of mixed compounds accessible by the laser-assisted methodologies, there is still a lot of room to expand the library of nano-crystals and to refine the control over products as well as to improve the understanding of the whole process of nanoparticle formation. To that end, this review aims to identify the perspectives and unique opportunities of laser-based synthesis and processing of colloids for future studies of oxide nanomaterial-oriented sciences.

Hydrofluoric acid pretreatment effect on the formation of silicon submicrometer particles by pulsed laser melting in liquid and their optical scattering property.

Recently, the optical properties of silicon (Si) submicrometer spherical particles have been investigated to understand the dielectric nano-photonic function. Herein, we fabricated Si submicrometer spherical particles with high scattering efficiency using pulsed laser melting in deionized water or ethanol by irradiating laser at 66 mJ pulse-1 cm-2 via third harmonic of Nd:YAG laser. Hydrofluoric acid pretreatment was effective to remove surface oxide of raw Si particles; the laser fluence to obtain well crystallized spherical particles was lowered to 20 mJ pulse-1 cm-2 and the crystallinity of particles obtained were greatly improved without forming unwanted byproducts. The amount of particles was much more than those obtained by conventional fabrication technique. The particle size can be controlled by changing the laser fluence, and the scattering wavelength of colloidal solution can be controlled from visible to the near infrared range by increasing the laser fluence.

Determining the Composite Structure of Au-Fe-Based Submicrometre Spherical Particles Fabricated by Pulsed-Laser Melting in Liquid.

Submicrometre spherical particles made of Au and Fe can be fabricated by pulsed-laser melting in liquid (PLML) using a mixture of Au and iron oxide nanoparticles as the raw particles dispersed in ethanol, although the detailed formation mechanism has not yet been clarified. Using a 355 nm pulsed laser to avoid extreme temperature difference between two different raw particles during laser irradiation and an Fe2O3 raw nanoparticle colloidal solution as an iron source to promote the aggregation of Au and Fe2O3 nanoparticles, we performed intensive characterization of the products and clarified the formation mechanism of Au-Fe composite submicrometre spherical particles. Because of the above two measures (Fe2O3 raw nanoparticle and 355 nm pulsed laser), the products-whether the particles are phase-separated or homogeneous alloys-basically follow the phase diagram. In Fe-rich range, the phase-separated Au-core/Fe-shell particles were formed, because quenching induces an earlier solidification of the Fe-rich component as a result of cooling from the surrounding ethanol. If the particle size is small, the quenching rate becomes very rapid and particles were less phase-separated. For high Au contents exceeding 70% in weight, crystalline Au-rich alloys were formed without phase separation. Thus, this aggregation control is required to selectively form homogeneous or phase-separated larger submicrometre-sized particles by PLML.

Guided Slow Continuous Suspension Film Flow for Mass Production of Submicrometer Spherical Particles by Pulsed Laser Melting in Liquid.

Pulsed laser melting in liquid (PLML) is a technique to fabricate submicrometer crystalline spherical particles of various materials by laser irradiation of suspended raw particles with random shapes. To fully exploit the unique features of PLML-fabricated particles (crystalline and spherical) in practice, a mass-production PLML technique is required. To this end, the present study develops a new slit nozzle that guides the suspension film flow into a non-droplet continuous stream with a low flow rate. These two incompatible flow properties (continuity and slowness) are difficult to be realized for a liquid jet to free space. The suspension film flow was irradiated with a typical laboratory scale-flash lamp pumping laser at 30 Hz pulse frequency. Only a single flow passage of the slit nozzle with a few laser pulse irradiation transformed 95% of the raw particles into spherical particles. This spheroidizing ratio exceeded those of low-rate drip flow and high-rate cylindrical laminar flow directly jetted into free space through a Pasteur pipette nozzle. Extrapolating the data obtained from a 20-ml suspension, the average production rate was determined as 195 mg h-1. The high spheroidizing ratio and yield through the slit nozzle is attributable to the uniquely slow but continuous liquid film flow. The structure of the slit nozzle also prevents particles from adhering to the slit wall during continuous laser irradiation. Thus, the suspension film flow through the newly developed slit nozzle can potentially scale up the PLML technique to mass production.

Pulse-Width Dependence of the Cooling Effect on Sub-Micrometer ZnO Spherical Particle Formation by Pulsed-Laser Melting in a Liquid.

Sub-micrometer spherical particles can be synthesized by irradiating particles in a liquid with a pulsed laser (pulse width: 10 ns). In this method, all of the laser energy is supposed to be spent on particle heating because nanosecond heating is far faster than particle cooling. To study the cooling effect, sub-micrometer spherical particles are fabricated by using a pulsed laser with longer pulse widths (50 and 70 ns). From the increase in the laser-fluence threshold for sub-micrometer spherical particle formation with increasing pulse width, it is concluded that the particles dissipate heat to the surrounding liquid, even during several tens of nanoseconds of heating. A particle heating-cooling model considering the cooling effect is developed to estimate the particle temperature during laser irradiation. This model suggests that the liquid surrounding the particles evaporates, and the generated vapor films suppress heat dissipation from the particles, resulting in efficient heating and melting of the particles in the liquid. In the case of small particle sizes and large pulse widths, the particles dissipate heat to the liquid without forming such vapor films.

Synthesis of various 3D porous gold-based alloy nanostructures with branched shapes.

This paper presents a facile and flexible synthesis platform for various 3D porous gold-iron nanostructures based on selective laser heating of colloidal nanoparticles and selective acid treatment. The presented approach allows to create porous gold-based nanostructures with different morphologies. In addition, for the first time, our studies indicate that various nanoarchitectures (brain-like, flower-like, cage-like, or raspberry-like structures) can be obtained by varying the experimental conditions such as size of Au and Fe3O4 nanoparticles, solvent, laser fluence, and irradiation time. We believe that these porous structures will find immediate applications in catalysis and separations, where high surface area and magnetic properties are often simultaneously required.

Preparation and investigation of the formation mechanism of submicron-sized spherical particles of gold using laser ablation and laser irradiation in liquids.

Results of very recent studies have shown that laser irradiation (LI) of colloidal nanoparticles (NPs) using a non-focused laser beam at moderate fluence transforms the NPs to submicron-sized spherical particles (SMPs). For this study, we applied this technique to prepare gold SMPs from source gold NPs prepared by laser ablation of a gold plate in an aqueous solution. Results show that SMPs were obtained from NPs in pure water, but a considerably large amount of the source NPs were sedimented without LI. On the other hand, SMPs were not obtained from NPs stabilized by 1 mM citrate. These findings indicate that the agglomeration of the source NPs prior to the laser-induced melting is important to obtain SMPs, although the sedimentation of the source NPs caused by considerable agglomeration should be reduced to obtain SMPs efficiently. A proper condition of the agglomeration tendency of the source NPs to prepare SMPs reducing the sedimentation of the source NPs was obtainable by simply adjusting the citrate solution concentration. Moreover, investigation of the temporal dynamics of the formation process of SMPs suggested that the agglomeration of the source NPs not only is controlled by citrate but also is induced by LI. LI brings about the decomposition and removal of citrate molecules on the surface of the source NPs, and cause the agglomeration of the source NPs dynamically; then it brings about the fusion of the agglomerated NPs.

Liquid-phase laser process for simple and area-specific calcium phosphate coating.

Simple, mild, and area-specific calcium phosphate (CaP) coating techniques are useful for the production and surface modification of biomaterials. In this study, an area-specific CaP coating technique for polymer substrates was successfully developed using a liquid-phase laser process. In the proposed method, Nd-YAG laser light (355 nm, 30 Hz, and 1-3 W) irradiated an ethylene-vinyl alcohol copolymer (EVOH) substrate immersed in a supersaturated CaP solution for various periods of time (up to 30 min). The CaP-forming ability increased with an increase in the laser power and irradiation period. At the optimal laser power (3 W), a continuous CaP layer formed within 30 min on the laser-irradiated surface of the EVOH substrate. The formation of CaP was attributed to laser absorption by the EVOH substrate, which promoted the surface modification of EVOH and an increase in the temperature of the solution near the surface of the substrate. The resulting CaP coating showed better cell adhesion property than the naked EVOH substrate. The proposed CaP coating technique is simple (quick and single step) and area specific. Furthermore, the present process is carried out under mild conditions, that is, at normal pressures and temperatures in a safe aqueous medium. These are significant advantages of the proposed CaP coating technique.

Synthesis of Au-based porous magnetic spheres by selective laser heating in liquid.

We report the synthesis of Au-based submicrometer-sized spherical particles with uniform morphology/size and integrated porosity-magnetic property in a single particles. The particles are synthesized by a two-step process: (a) selective pulsed laser heating of colloidal nanoparticles to form particles with Au-rich core and Fe-rich shell and (b) acid treatment which leads to formation of porous architecture on particle surface. The simple, fast, inexpensive technique that is proposed demonstrates very promising perspectives for synthesis of composite particles.

Tetragonal zirconia spheres fabricated by carbon-assisted selective laser heating in a liquid medium.

Submicrometer-sized tetragonal zirconia spheres are synthesized by carbon-assisted selective pulsed laser heating in a liquid medium at room temperature. Sphere formation and phase transformation from the monoclinic to the tetragonal phase are only observed by laser irradiation of a colloidal solution containing raw zirconia mechanically milled with nanocarbon. This result indicates that nanocarbon, having close contact with zirconia particles, plays a very important role in forming submicrometer-sized tetragonal zirconia spheres.

General bottom-up construction of spherical particles by pulsed laser irradiation of colloidal nanoparticles: a case study on CuO.

The development of a general method to fabricate spherical semiconductor and metal particles advances their promising electrical, optical, magnetic, plasmonic, thermoelectric, and optoelectric applications. Herein, by using CuO as an example, we systematically demonstrate a general bottom-up laser processing technique for the synthesis of submicrometer semiconductor and metal colloidal spheres, in which the unique selective pulsed heating assures the formation of spherical particles. Importantly, we can easily control the size and phase of resultant colloidal spheres by simply tuning the input laser fluence. The heating-melting-fusion mechanism is proposed to be responsible for the size evolution of the spherical particles. We have systematically investigated the influence of experimental parameters, including laser fluence, laser wavelength, laser irradiation time, dispersing liquid, and starting material concentration on the formation of colloidal spheres. We believe that this facile laser irradiation approach represents a major step not only for the fabrication of colloidal spheres but also in the practical application of laser processing for micro- and nanomaterial synthesis.

Untraditional approach to complex hierarchical periodic arrays with trinary stepwise architectures of micro-, submicro-, and nanosized structures based on binary colloidal crystals and their fine structure enhanced properties.

A unique approach for fabricating complex hierarchical periodic arrays with trinary stepwise architectures of micro- and submicro- as well as nanosized structures by combining a novel double-layered binary colloidal crystal with pulsed laser deposition techniques is developed. The present strategy is universal and nanostructures with different materials can be easily prepared in the complex hierarchical periodic arrays. This approach offers the advantage of low costs compared to conventional lithographic techniques. These as-prepared unique structures cannot be directly fabricated by conventional lithography. These special hierarchically structured arrays demonstrate fine structure-enhanced performances, including superhydrophilicity without UV irradiation and surface enhanced Raman scattering (SERS), which is highly valuable for designing micro/nanodevices, such as biosensors or microfluidic devices.

Single-crystalline rutile TiO2 hollow spheres: room-temperature synthesis, tailored visible-light-extinction, and effective scattering layer for quantum dot-sensitized solar cells.

A general synthesis of inorganic single-crystalline hollow spheres has been achieved through a mechanism analogous to the Kirkendall effect, based on a simple one-step laser process performed at room temperature. Taking TiO(2) as an example, we describe the laser process by investigating the influence of experimental parameters, for example, laser wavelength, laser fluence/irradiation time, liquid medium, and concentration of starting materials, on the formation of hollow spheres. It was found that the size-tailored TiO(2) hollow spheres demonstrate tunable light scattering over a wide visible-light range. Inspired by the effect of light scattering, we introduced the TiO(2) hollow sphere's scattering layer in quantum dot-sensitized solar cells and achieved a current notable 10% improvement of solar-to-electric conversion efficiency, indicating that TiO(2) hollow spheres are potential candidates in optical and optoelectronic devices.

Controlling exchange bias in Fe3O4/FeO composite particles prepared by pulsed laser irradiation.

Spherical iron oxide nanocomposite particles composed of magnetite and wustite have been successfully synthesized using a novel method of pulsed laser irradiation in ethyl acetate. Both the size and the composition of nanocomposite particles are controlled by laser irradiation condition. Through tuning the laser fluence, the Fe3O4/FeO phase ratio can be precisely controlled, and the magnetic properties of final products can also be regulated. This work presents a successful example of the fabrication of ferro (ferri) (FM)/antiferromagnetic (AFM) systems with high chemical stability. The results show this novel simple method as widely extendable to various FM/AFM nanocomposite systems.

Preparation of silver spheres by selective laser heating in silver-containing precursor solution.

Dispersed uniform submicron-sized silver spheres were prepared by selective laser heating in the silver-containing precursor solution, which was produced by dissolving the irregular Ag2O in aliphatic amine. By optimizing the process conditions, silver spheres in the range of 578 ± 109 nm were obtained. The smooth surface morphology and solid structure were studied by SEM and TEM. The silver content was characterized by XRD and EDS. Finally, the mechanism of the silver spheres formation was also discussed in detail.