Nanoparticles produced by laser ablation of solids in liquid environment

A review of results on nanoparticles formation is presented under laser ablation of Ag, Au, and Ti solids targets in liquid environments (H₂O, C₂H₅OH, C₂H₄Cl₂, etc.). X-ray diffractometry (XRD), UV-Vis optical transmission spectrometry, and high-resolution transmission electron microscopy (HRTEM) characterise the nanoparticles. The morphology of nanoparticles is studied as a function of both laser fluence and nature of the liquid. The evidence of an intermediate phase of Au-Ag alloy is presented under exposure of a mixture of individual nanoparticles to laser radiation. Self-influence of the beam of a femtosecond laser is discussed under the ablation of the Ag target in liquids under Ti:sapphire laser. The factors are discussed that determine the distribution function of particle size under laser ablation. The influence of laser parameters as well as the nature on the liquid on the properties of nanoparticles is elucidated. PACS 42.62.-b; 61.46.+w; 78.66.-w     

A novel method of nanocrystal fabrication based on laser ablation in liquid environment

Metal nanoparticles can be prepared by a novel technique that consists of the laser ablation of a solid target immersed in a water solution of a metal salt. Silicon was chosen as the most adequate target to synthesize silver and gold nanoparticles from a water solution of either AgNO₃ or HAuCl₄. The influence of both the silver nitrate concentrations and the irradiation time of the Si target on the optical properties of the Au and Ag nanoparticles have been investigated. The crystalline nature of the metal nanoparticles has been determined by X-ray diffraction (XRD). Average size and particle size distribution have been measured by means of TEM. The absorbance spectra show the characteristic band of the surface resonant plasmon of silver and gold nanoparticles.     

Silicon nanoparticles generated by femtosecond laser ablation in a liquid environment

Silicon nanoparticles were generated by femtosecond laser [387 nm, 180 fs, 1 kHz, pulse energy = 3.5 μJ (fluence = 0.8 J/cm²)] ablation of silicon in deionized water. Nanoparticles with diameters from ~5 up to ~200 nm were observed to be formed in the colloidal solution. Their size distribution follows log-normal function with statistical median diameter of ≈20 nm. Longer ablation time leads to a narrowing of the nanoparticle size distribution due to the interaction of the ablating laser beam with the produced nanoparticles. Raman spectroscopy measurements confirm that the nanoparticles exhibit phonon quantum confinement effects and indicate that under the present conditions of ablation they are partially amorphous.     

Promoting the yield of nanoparticles from laser ablation in liquid

We have systematically studied the relationship between the preparation of Ge nanoparticles and the thickness of the water layer upon the pulsed-laser ablation of a Ge target in water. It was found that the average size of the prepared nanoparticles decreases with the thickness of water, and there is an optimum the thickness of water for the largest yield of the produced nanopartciles, which means the thickness of water can be regarded as an important parameter to control the size and yield of the prepared nanoparticles from laser ablation in liquid. The relevant physical mechanism was discussed.     

Metallic nanosieves formed by ultra-short-pulse laser ablation

The formation of free-standing gold nanosieves by ablation with ultra-short laser pulses is demonstrated. Macroscopic areas are generated fast and efficiently by the application of a parallel production technique. The technique is based on a lens array formed by self-assembling quartz microspheres on a thin metal foil. The evaporated foils have a final thickness of 400 nm, and the hole spacing is set by the diameter of the microspheres (∼7 m) while the pore size is ∼700 nm. The characteristic spacing of the generated hole structure is verified by an optical diffraction technique.     

Structures of BiInSn nanoparticles formed through laser ablation

The eutectic alloy of BiInSn was ablated in water by UV pulsed radiation. Electron microscopy of the ablated material shows spherical particles that fall into three size regimes: those with diameters of ～0.5 μm, crystalline and amorphous particles with dimensions of ～30 nm, and amorphous particles that are approximately 1 nm across. The 30-nm amorphous particles are homogeneous, while there are two types of 30-nm crystalline particles, those that separate into three phases and those that are homogeneous. The existence of different characteristic sizes is explained by two mechanisms: phase explosion and Rayleigh instability of the ejected melt.     

Fabrication of tin monosulfide nanosheet arrays using laser ablation

We demonstrate the non-catalytic, low-temperature (∼200°C) synthesis of two-dimensional (2D) tin monosulfide (SnS) nanosheet arrays vertically aligned on the substrate by means of pulsed laser ablation (PLD) process. The prepared nanosheets were characterized using X-ray diffraction, Raman spectroscopy, field-emission electron microscopy, electron probe micro-analysis, and transmission electron microscopy (HRTEM). The growth mechanism of 2D morphological feature, which is widespread but very slim (∼10 nm), is further investigated in detail from the crystallographic point of view by observing highly-resolved lattice images taken from plane-normal and in-plane directions using focused ion-beam manipulation and high-resolution transmission microscopy.     

Detection of neutral products formed during excimer laser ablation of polyimide by UV and VUV laser photoionization/mass spectrometry

Some of the neutral species which are produced in the laser ablation of polyimide have been characterized using multiphoton ionization/time of flight mass spectrometry. Three different wavelengths (193 nm, 157 nm, and 118 nm) have been used in an attempt to effect soft ionization of the products formed during or after the initial laser ablation of the polymer. Neutral photo-ablation products detected using this scheme range from atomic to high molecular weight species which, depending on the probe wavelength, include pure carbon clusters as well as a broad distribution of heteroatom containing clusters. However, there is virtually no overlap in the mass spectra recorded at each probe wavelength. When probing with 193 nm, marked changes are observed in the mass spectra as a function of the probe flux used. At moderate fluxes, pure carbon clusters (fullerenes) are observed. The identification of a large distribution of species other than pure carbon clusters is in dramatic contrast to the recent observation [W.R. Creasy, J.T. Brenna: Chem. Phys. 126, 453 (1988)] of the positively charged ionic species produced, which are solely carbon clusters. These results suggest that the neutral and ionic products observed after ablation of the polymer are due to both condensation of the atomic and molecular fragments which form during the ablation laser pulse and nascent polymer fragments. Various implications of this result for the unambiguous determination of the true ablation product distribution are discussed.     

Growth mechanism of ZnO nanorods from nanoparticles formed in a laser ablation plume

We have succeeded in synthesizing ZnO nanorods by pulsed-laser ablation at comparatively high gas pressures without using a catalyst. The nanorods had an average size of 300 nm and a length of about 6 m. Stimulated emission was observed from the nanorods at 388 nm by optical pumping. As a catalyst was not used in our method, nanorod growth was not controlled by the vapor-liquid-solid (VLS) mechanism. We found that nanoparticles formed by condensation of ablated particles in the laser ablation plume play an important role in nanorod growth. PACS 61.46.+w; 81.07.Bc; 78.66.Hf; 78.67.Bf; 81.16.Mk     

The effect of liquid environment on size and aggregation of gold nanoparticles prepared by pulsed laser ablation

The effects of liquid environment on nucleation, growth and aggregation of gold nanoparticles were studied. Gold nanoparticles were prepared by pulsed laser ablation in deionised water with various concentrations of ethanol and also in pure ethanol. UV/visible extinction and TEM observations were employed for characterization of optical properties and particle sizes respectively. Preparation in water results in smaller size, shorter wavelength of maximum extinction and stable solution with an average size of 6 nm. Nanoparticles in solution with low concentration ethanol up to 20 vol% are very similar to those prepared in water. In the mixture of deionised water and 40 up to 80 vol% ethanol, wavelength of maximum extinction shows a red shift and mean size of nanoparticles was increased to 8.2 nm. Meanwhile, in this case, nanoparticles cross-linked each other and formed string type structures. In ethanol, TEM experiments show a mean size of 18 nm and strong aggregation of nanoparticles. The data were discussed qualitatively by considering effects of polarity of surrounding molecules on growth mechanism and aggregation. This study provided a technique to control size, cross-linking and aggregation of gold nanoparticles via changing the nature of liquid carrier medium.     

Creation of silicon nanocrystals using the laser ablation in liquid

The method for the formation of silicon nanoparticles by picosecond laser pulses is studied upon the surface irradiation of the single-crystal silicon in various liquids. The ablation products are investigated using the atomic-force microscopy and Raman spectroscopy. The experimental results indicate the crystal-line structure of nanoparticles and the dependence of their size on the ablation medium.     

Effect of substrate position on the morphology of boron products by laser ablation

Single-crystalline boron nanobelts having rectangular cross sections with an -tetragonal structure and polycrystalline -rhombohedral boron films were fabricated using a laser ablation technique in a quartz glass tube chamber. The obtained products strongly depended on substrate position. The major products were boron nanobelts when the substrate was situated at the bottom of the tube with the pressure below 50 Pa in the temperature range from 700 °C to 900 °C. The boron product on a substrate at a side position in the tube always had a film morphology. The crystal structures of the obtained boron films, however, were amorphous under the conditions where nanobelts were observed. The products became well crystallized at pressures of 50 to 100 Pa at 900 °C. PACS 81.07.Bc; 81.15.Fg; 81.16.Mk; 79.20.Ds     

Chemical analysis of products obtained by nanosecond laser ablation

The chemical analysis of a laser jet was performed with a combination of laser back mass transfer and X-ray photoelectron spectroscopy (XPS). It was revealed that, as compared to the source material, films deposited from the jet under laser mass transfer in air show increased oxidizability and changed chemical composition.     

Formation of microtower structures on nanosecond laser ablation of liquid metals

We report the formation of microtower structures, observed on multishot nanosecond laser irradiation of liquid metals (Ga, In, Sn–Pb alloy, Wood’s metal). Ablation in a reactive ambient gas (air, nitrogen, sulfur hexafluoride, nitrogen trifluoride) is shown to lead to a tower-like structure growing on the irradiated surface at a rate of 3–20 μm per pulse depending on laser fluence and the types of metal and ambient gas. The interplay between different processes in the heat-affected zone of the irradiated samples is analyzed, including ablation, thermal expansion, temperature variations of viscosity, surface tension, thermal stresses, capillary effects, and surface chemistry. A clear picture of microtower origin has been established, and qualitative modeling can explain the formation mechanism.     

纳秒激光烧蚀下液态金属表面微结构的形成(英文)

首次发现了在不同保护气体及多脉冲UV-IR激光的照射下,液态金属的微型突起和微结构的形成。测量表明,针对不同的金属和保护气,这种结构的单脉冲生成速率可达(5～20)μm/pulse,形成了长度为1～2 mm,直径约为焦点两倍的单个微型突起。最后,介绍了控制微结构形状的可能性,并讨论了它们的应用潜力。     

纳秒激光烧蚀下液态金属表面微结构的形成

首次发现了在不同保护气体及多脉冲uV—IR激光的照射下,液态金属的微型突起和微结构的形成。测量表明,针对不同的金属和保护气,这种结构的单脉冲生成速率可达（5—20）μm／pulse,形成了长度为1～2mm,直径约为焦点两倍的单个微型突起。最后,介绍了控制微结构形状的可能性,并讨论了它们的应用潜力。     

Rotational spectra of S- and S-containing isotopologues of laser ablation generated tin monosulfide

Using a newly constructed source, tin monosulfide is produced by the reaction between carbonyl sulfide and the products resulting from the ablation of tin metal by the pulsed output of a frequency-doubled Nd:YAG laser (λ = 532 nm). Entrained in argon carrier gas, SnS is introduced into the cavity of a Balle-Flygare Fourier transform microwave spectrometer that has a frequency range encompassing the two lowest rotational transitions (J = 1 − 0 and 2 − 1) for this molecule. Except for ¹¹⁵Sn³⁴S, spectra are obtained in natural abundance for all ³⁴S-containing isotopologues with naturally occurring tin isotopes. Additionally, spectra were obtained for the rare isotopologues, ¹¹⁵Sn³²S and ¹²⁰Sn³³S. Resolution of the hyperfine structure in the latter species allows a more precise determination of its ³³S nuclear quadrupole coupling constant. Spectra for all species containing ³⁴S are analyzed in terms of mass-independent Dunham parameters and are combined with all available isotopologues to determine Born-Oppenheimer breakdown terms for both tin and sulfur.     

Generation of Ag nanospikes via laser ablation in liquid environment and their activity in SERS of organic molecules

The formation of dense arrays of nanospikes occurs under laser ablation of bulk silver immersed in liquids such as water or ethanol. The average height of spikes is 50 nm and their density on the target amounts to 10¹⁰ cm^-2. This effect is observed with sufficiently short laser pulses. In particular, either a 350 ps or a 90 ps Nd:YAG lasers are used operating in their fundamental harmonics. These nanospikes are characterized by UV–visible reflection spectrometry and atomic force microscopy. The oscillations of electrons within Ag nanospikes results in a permanent coloration of the surface and a modification of the optical reflection spectra of the metal. Nanospikes show a peak of plasmon resonance around 380 nm, which shifts to the visible range upon oxidation in air. The initial spectrum may be restored by reduction of the oxidized Ag surface through processing in an ammonia aqueous solution. Scanning the laser beam along the metal surface allows its nanostructuring over extended areas (∼1 cm²). The nanostructured Ag surface shows enhanced Raman scattering of acridine molecules at a concentration of 10^-5 M/l, whereas initial Ag target do not show any signal within the accuracy of measurements. PACS 68.65.k; 64.70.Dv; 79.20.Ds; 42.62.Cf     

Mass spectrometric analysis of clusters formed in laser ablation of a sample

Experimental data are used as a basis for discussion of the principal methods of cluster formation in the laser ablation of targets: condensation during expansion of the cloud of evaporated material, clustering at the surface accompanying redeposition of material back on the target, and emission of entire nanoblocks from the target. Methods of distinguishing between these processes are discussed. Zh. Tekh. Fiz. 69, 81–84 (September 1999)