Laser-induced synthesis of metal–carbon materials for implementing surface-enhanced Raman scattering

Metal–carbon materials exhibiting surface-enhanced Raman scattering have been synthesized by laser irradiation of colloidal systems consisting of carbon and noble metal nanoparticles. The dependence of the Raman scattering intensity on the material composition and laser irradiation conditions has been investigated. The possibility of recording the Raman spectrum of organic dye rhodamine 6G, deposited in amount of 10^–6 M on the substrate obtained from a colloidal solution is demonstrated.     

Thermal Lens Phenomenon Studied by the Z-Scan Technique: Measurement of the Thermal Conductivity of Highly Absorbing Colloidal Solutions

We discuss the thermal lens phenomenon in high-absorbing colloidal systems, studied by using the Z-scan technique. The characteristics of the experimental setup to avoid undesirable effects are presented, in particular when pulsed laser beam is used. We show that a cumulative effect may appear in the experiment with chopped laser beams and compromise the results obtained with this technique. This artefact is more significative when colloidal suspensions are investigated. These materials have different characteristic times of heat and mass diffusion, which must be carefully considered to choose the appropriate time interval for the laser pulse and the time between pulses. Two experimental cases with a chopped laser beam, with and without a shutter, are discussed. The sample employed is a magnetic colloidal suspension (a ferrofluid). This sample has magnetic nanoparticles electrically charged in an aqueous solution with free ions and counter ions. Besides the thermal lens effect, charge and mass diffusion may take place when the sample is illuminated by the Gaussian beam, which imposes a thermal gradient on it. The results show that, with the experimental setup without a shutter, the sample does not achieve a complete relaxation between two laser pulses. This generates a measurable cumulative effect after the sample is illuminated during a relatively long period of time. A time modulation with longer time interval between chopped pulses allows the complete relaxation of the sample. This procedure is important for the correct analysis of the thermal lens effect. Reliable values of the thermal conductivity of the sample in different temperatures are obtained and discussed.     

Laser-assisted generation of gold nanoparticles and nanostructures in liquid and their plasmonic luminescence

Nanoparticles (NPs) and surface nanostructures (NS) are produced via laser ablation of a bulk gold target in liquid using second harmonics of 10 ps Nd:YAG laser (532 nm) with repetition rate of 50 kHz. The morphology and plasmon photoluminescence (PL) properties of obtained nanoscale objects are described. Transmission electron microscopy and field emission scanning electron microscopy are used for morphology characterization of NPs and NS, respectively. Plasmon PL of both gold NPs and NS is experimentally studied using the third harmonics of the Nd:YAG picosecond laser (355 nm) as a pump. The wavelength of intensity maximum of PL of Au NPs colloidal solution virtually coincides with the position of Au NPs plasmon absorption peak. Real-time excitation of both plasmon PL and Raman scattering of surrounding liquid by picosecond laser pulses in aqueous colloidal solution is also investigated. The efficient cross section of plasmon PL of Au NPs colloid is evaluated using Raman scattering of water as a comparative parameter. The results are in good agreement with values obtained in previous works. Plasmon PL from self-organized NS on the Au surface produced via laser ablation is observed for the first time. Its spectrum is compared to PL spectra of both aqueous colloidal solutions of NPs and of NPs deposited on a Si wafer. The obtained experimental data are discussed with reference to the band structure of bulk Au.     

Effect of Laser Exposure on the Process of Silicon Nanoparticle Fabrication

Silicon nanoparticles are obtained by nanosecond laser ablation of a single-crystal wafer under a deionized water layer. Nanoparticle generation mechanisms are studied depending on the incident energy density of laser radiation (7–12 J/cm²) and scanning speed (10–750 mm/s). At a scanning speed of 150–200 mm/s, a maximum of the extinction coefficient of obtained colloidal solutions of nanoparticles is observed, which can be caused by an increase in their mass yield.     

Synthesis of CaWO<Subscript>4</Subscript> nanocolloidal suspension via pulsed laser ablation and its optical properties

Pulsed laser ablation (PLA) in the liquid phase was successfully employed to synthesize calcium tungstate (CaWO₄) nanocolloidal suspension. The crystalline phase, particle morphology and laser ablation mechanism for the colloidal nanoparticles were investigated using XRD, TEM and SEM. The obtained colloidal suspension consisted of well-dispersed CaWO₄ nanoparticles which showed a spherical shape with sizes ranging from 5 to 30 nm. The laser ablation and the nanoparticle forming process were discussed under consideration of the photo-ablation mechanism, where the nanoparticles were generated by rapid condensation of the plume in high pressured ethanol vapor. The optical properties of the prepared CaWO₄ colloidal nanoparticles were analyzed in detail using XPS, Raman spectroscopy, UV-Vis spectroscopy and PL spectrophotometry. The optical band gap was estimated by Tauc and Menths law. PACS 42.62.-b; 82.70.Dd; 78.55.Hx; 81.07.Wx     

Fabrication of gold nanoparticles in water by laser ablation technique and their characterization

A colloidal solution of gold nanoparticles in deionized nanopure water was produced by laser ablation technique without the use of any chemical/surfactant. Spectral characterization and morphological studies of these nanoparticles were carried out by UV-Vis Spectroscopy and Scanning Electron Microscopy, respectively. A number of variables of the ablating laser pulse have been used to control the size of the fabricated nanoparticles. Excellent correlation between ablating laser pulse parameter and optical and morphological parameters of the gold colloids were obtained. The peak of the extinction spectra shows a monotonic blue shift for laser fluence of 410 J/cm² and above. Below this the extinction peak remains fairly constant in wavelength. Blue shifts of the extinction spectra were also observed with increasing re-ablation time of previously ablated gold colloids. Possible explanations of all these observations are discussed.     

A study of the thermal-induced nonlinearity of Au and Ag colloids prepared by the chemical reaction method

The nonlinear optical properties of metal Au and Ag colloidal solutions prepared by the chemical reaction method were investigated by a single beam Z-scan technique. Under CW 633 nm excitation, the Au and Ag colloidal solutions exhibited a large thermal-induced refractive index n₂. At the same time, the thermo-optic coefficients dn/dT of the Au and Ag colloidal solutions were obtained. The mechanism responsible for the process of nonlinear refraction was discussed in term of laser heating effect.     

A Comparative Study of the Determination of Ferrofluid Particle Size by Means of Rotational Brownian Motion and Translational Brownian Motion

Two methods, the Toroidal Technique and the Forced Rayleigh Scattering (FRS) method, were used in the determination of the size of magnetic particles and their aggregates in magnetic fluids. The toroidal technique was used in the determination of the complex, frequency dependent magnetic susceptibility, x(w)=x'(w) - ix"(w) of magnetic fluids consisting of two colloidal suspensions of cobalt ferrite in hexadecene and a colloidal suspension of magnetite in isopar m with corresponding saturation magnetisation of 45.5 mT, 20 mT and 90 mT, respectively. Plots of the susceptibility components against frequency f over the range 10 Hz to 1 MHz, are shown to have approximate Debye-type profiles with the presence of relaxation components being indicated by the frequency, f _max, of the maximum of the loss-peak in the x"(w) profiles. The FRS method (the interference of two intense laser beams in the thin film of magnetic fluid) was used to create the periodical structure of needle like clusters of magnetic particles. This creation is caused by a thermodiffusion effect known as the Soret effect. The obtained structures are indicative of as a self diffraction effect of the used primary laser beams. The relaxation phenomena arising from the switching off of the laser interference field is discussed in terms of a spectrum of relaxation times. This spectrum is proportional to the hydrodynamic particle size distribution. Corresponding calculations of particle hydrodynamic radius obtained by both mentioned methods indicate the presence of aggregates of magnetic particles.     

Anisotropic laser trapping in nematic colloidal dispersion

The interaction between a colloidal particle and a focused laser beam in a nematic liquid crystal reveals an unusual anisotropic Coulomb-like character. Experiments demonstrate two opposite directions in which the particle is attracted to and repelled from the nematic region deformed by the light-induced director reorientation. In this work we present analytical analysis of such behavior and derive the energy of interaction between colloidal particle and deformed director field. The analytical solution is in good agreement with recent results obtained by computer simulation.     

Restructuring of plasmonic nanoparticle aggregates with arbitrary particle size distribution in pulsed laser fields

We have studied processes of interaction of pulsed laser radiation with resonant groups of plasmonic nanoparticles(resonant domains) in large colloidal nanoparticle aggregates having different interparticle gaps and particle size distributions.These processes are responsible for the origin of nonlinear optical effects and photochromic reactions in multiparticle aggregates.To describe photo-induced transformations in resonant domains and alterations in their absorption spectra remaining after the pulse action,we introduce the factor of spectral photomodification.Based on calculation of changes in thermodynamic,mechanical,and optical characteristics of the domains,the histograms of the spectrum photomodification factor have been obtained for various interparticle gaps,an average particle size,and the degree of polydispersity.Variations in spectra have been analyzed depending on the intensity of laser radiation and various combinations of size characteristics of domains.The obtained results can be used to predict manifestation of photochromic effects in composite materials containing different plasmonic nanoparticle aggregates in pulsed laser fields.     

Relation between the photoreaction of p-nitrobenzoic acid onto silver-coated filters and the surface roughness, as detected by SERS and AFM

The SERS of p-nitrobenzoic acid has been first obtained in Ag hydrosol and compared with those deriving from filtration of colloidal silver. The roughness of the Ag-coated filters has been examined by AFM measurements and related to the SERS enhancement. The addition of chloride anions to the colloidal suspension strongly increases the surface roughness of the solid metal substrates and activates the photoreaction of the adsorbate by irradiation with green laser light.     

Self‐organized colloidal crystals for photonics and laser applications

We present an overview of recent developments in the fabrication and uses of colloidal crystals (CCs) for photonics and laser applications. Microparticles with a diameter in the range from 10 nm to 10 μm often have an intrinsic capability to spontaneously organize themselves from a colloidal suspension into 3D lattice structures. Such highly ordered 3D architectures of microparticles are called colloidal crystals (CCs). The CC structures have received tremendous attention as one of the facile and high‐throughput fabrication techniques of photonic crystals (PCs). We introduce here interesting precedents not only of diverse techniques of high‐quality CC structures, but also of their versatile applications in optical sensors responding to various external stimuli. This review also highlights a new potential use of the CCs as low‐threshold laser devices. We believe that a wide variety of CC architectures will play leading roles in the next generation of optoelectronic devices.     

Optical properties of nanocomposites based on polymers and metal nanoparticles

The optical properties of nanocomposites of metal nanoparticles and polymers of two types have been studied. Gold and silver nanoparticles were obtained by laser ablation of corresponding metal targets in acetone and chloroform. The thus formed colloidal solutions were used to prepare nanocomposites of these nanoparticles in polymer matrices of polymethylmethacrylate (PMMA) and fluorine-containing polymer LF-32. The polymer matrix is found to promote aggregation of the metal nanoparticles under study into elongated chains. In turn, metal nanoparticles affect the polymer matrix. In the case of PMMA, suppression of the vibrational peaks of polymer in the low-frequency region of its Raman spectrum occurs. In the case of LF-32, gold and silver nanoparticles amplify the Raman signal of the polymer matrix. In addition, the Raman spectra of nanocomposites indicate aggregation of disordered carbon around the nanoparticles obtained by laser ablation in organic solvents. The possibilities of studying the ultrafast (about 1 ps) optical response of the nanocomposites obtained in order to use it in photonics elements are discussed.     

Subsurface defect characterization and laser-induced damage performance of fused silica optics polished with colloidal silica and ceria

This paper mainly focuses on the influence of colloidal silica polishing on the damage performance of fused silica optics. In this paper, nanometer sized colloidal silica and micron sized ceria are used to polish fused silica optics. The colloidal silica polished samples and ceria polished samples exhibit that the root-mean-squared(RMS) average surface roughness values are 0.7 nm and 1.0 nm, respectively. The subsurface defects and damage performance of the polished optics are analyzed and discussed. It is revealed that colloidal silica polishing will introduce much fewer absorptive contaminant elements and subsurface damages especially no trailing indentation fracture. The 355-nm laser damage test reveals that each of the fused silica samples polished with colloidal silica has a much higher damage threshold and lower damage density than ceria polished samples. Colloidal silica polishing is potential in manufacturing high power laser optics.     

Laser beam filamentation in fractal aggregates

We investigate filamentation of a cw laser beam in soft matter such as colloidal suspensions and fractal gels. The process, driven by electrostriction, is strongly affected by material properties, which are taken into account via the static structure factor, and have impact on the statistics of the light filaments.     

Mechanism of pulse laser interaction with colloidal nanoparticles

The laser is a very powerful and very useful instrument in modern nanoscience and nanotechnology. The knowledge of the interaction mechanism of the laser beam with nanoparticles is needed to control the laser processing of different nano‐objects. It was shown that the particle heating–melting–evaporation model can be successfully applied for many phenomena arising when colloidal nanoparticle interact with pulsed laser beams. The general approach of this model is discussed in detail. The two main components of the model, light absorption by particles, and the thermodynamics of phase transitions in particulate material are considered. Special attention is devoted to the correct estimation of the possible heat losses. The way in which the phase diagrams, where the different phase conditions of particle material are presented in laser fluence−particle diameter coordinates, were produced is demonstrated. It is shown how this model can be applied for understanding the mechanism of such complicated processes as particle‐size reduction and submicrometer spherical particle growth, as well as other processes that occur when colloidal particles are irradiated by a pulsed laser.     

激光散射法测试超细颗粒粒度分布的研究

本文系统研究了样品制备条件对激光散射法测试超细颗粒粒度的影响,例如:分散介质的选择、分散剂的类型和浓度、分散颗粒的浓度、超声分散的时间和强度等。并与其他TEM结果进行了对比。研究表明:只有将各种条件最优化,获得高度分散和稳定的悬浮体系或胶体体系,才能最终精确地得到颗粒的粒度分布结果。     

Pulse laser deposition of cluster nanostructures from colloidal single-component systems

We study the formation and deposition of clusters of nanoparticles from colloidal systems onto a support surface as a result of local pulse laser impact. The processes of abnormal diffusion influencing the formation of relief due to changes in the diffusion coefficient near surface irregularities are analyzed. Numerical simulation is performed for the mechanism of deposition of particles from the colloidal system as a result of local laser impact.     

Pd2+ reduction and gasochromic properties of colloidal tungsten oxide nanoparticles synthesized by pulsed laser ablation

Tungsten oxide nanoparticles were fabricated by a pulsed laser ablation method in deionized water using the first harmonic of a Nd:YAG laser (λ=1064 nm) at three different laser pulse energies (E1 =160, E2 =370 and E3 =500 mJ/pulse), respectively. The aim is to investigate the effect of laser pulse energy on the size distribution and gasochromic property of colloidal nanoparticles. The products were characterized by dynamic light scattering (DLS), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and UV-Vis spectroscopy. The results indicated that WO₃ nanoparticles were formed. After ablation, a 0.2 g/l PdCl₂ solution was added to activate the solution against hydrogen gas. In this process Pd²⁺ ions were reduced to deposit fine metallic Pd particles on the surface of tungsten oxide nanoparticles. The gasochromic response was measured by H₂ and O₂ gases bubbling into the produced colloidal Pd–WO₃. The results indicate that the number of unreduced ions (Pd²⁺) decreases with increasing laser pulse energy; therefore, for colloidal nanoparticles synthesized at the highest laser pulse energy approximately all Pd²⁺ ions have been reduced. Hence, the gasochromic response for this sample is nearly reversible in all cycles, whereas those due to other samples are not reversible in the first cycle.     

The photoacoustic effect from particles and bubbles

Irradiation of colloidal suspensions with the output of a high power, pulsed laser can give rise to chemical reactions and phase transitions that are linked to the production of ultrasound. Transient grating experiments, which record both photoacoustic and photothermal processes, show the effects of the concentration of heat at the sites of colloidal particles, chemical reactions leading to the formation of stable gaseous species, and the production of steam bubbles. The efficiency of sound by these processes is, in general, determined by the rapidity of the density change that follows the absorption of the laser radiation.