Nanoparticles size modifications during femtosecond laser ablation of nickel in vacuum

Nanoparticles were synthesized by irradiating a nickel target with femtosecond laser pulses in high vacuum, and subsequently analyzed. The proof-of-principle experiments aim to modify the size characteristics of the produced nanoparticles. For nickel it is found that: (i) ultraviolet laser pulses lead to a remarkable change in the nanoparticles size distribution with respect to visible laser pulses; (ii) irradiation of the femtosecond pulses induced ablation plume with a second, delayed ultraviolet laser pulse can change the size characteristics of the produced nanoparticles.     

Influence of ambient gas on formation process of Si nanoparticles by laser ablation

We described the influence of a type of gas and its pressure upon the size distribution of Si nanoparticles fabricated by laser ablation in an ambient gas and the plume dynamics during the synthesis. The plume dynamics was investigated by laser-induced fluorescence and ultraviolet Rayleigh scattering. Based on the results, the importance of the gas flow within the ablation plume in the formation of the nanoparticles is understood.     

Synthesis of nanoclusters by nanosecond laser ablation: Direct simulation Monte Carlo modelling

Collisional processes leading to the formation of nanoparticles in a laser-ablated plume are numerically simulated with the aid of an atomistic-level model based on direct simulation Monte Carlo (DSMC) method. The formation of nanoparticles in nanosecond laser ablation of a mono-atomic target is investigated in the presence of an inert background gas. The DSMC procedure is modified in order to account for numerous plume species and to describe several reactions (i.e., recombination/dissociation, sticking, evaporation) taking place in the plume and affecting the size and spatial distribution of the produced nanoclusters. Calculation results allow us to visualize the nanoparticles and to correlate their space distributions with plume dynamics. In addition, cluster size distributions are investigated at different pressures. The effects of the background gas on cluster formation within the plume are furthermore shown.     

Investigation of different liquid media and ablation times on pulsed laser ablation synthesis of aluminum nanoparticles

Aluminum nanoparticles were synthesized by pulsed laser ablation of Al targets in ethanol, acetone, and ethylene glycol. Transmission Electron Microscope (TEM) and Scanning Electron Microscope (SEM) images, Particle size distribution diagram from Laser Particle Size Analyzer (LPSA), UV-visible absorption spectra, and weight changes of targets were used for the characterization and comparison of products. The experiments demonstrated that ablation efficiency in ethylene glycol is too low, in ethanol is higher, and in acetone is highest. Comparison between ethanol and acetone clarified that acetone medium leads to finer nanoparticles (mean diameter of 30 nm) with narrower size distribution (from 10 to 100 nm). However, thin carbon layer coats some of them, which was not observed in ethanol medium. It was also revealed that higher ablation time resulted in higher ablated mass, but lower ablation rate. Finer nanoparticles, moreover, were synthesized in higher ablation times.     

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利用时空分辨的测量技术,测定了XeCl紫外激光烧蚀金属Cu消融粒子的发射光谱随时间与空间的强度分布。通过在不同的氢气压强下拍摄到的XeCl308nm紫外激光烧蚀金属Cu消融粒子的发光羽照片,发现激光消融粒子发光羽的颜色在不同区域有不同的颜色,不同区域的发光羽颜色随环境气压的改变而变化。随环境气压的增大,发光羽不仅逐渐变小,而且逐渐变淡。对激光消融粒子发光羽的机理进行了探讨,激光消融粒子发光羽的发光动力学模式在不同区域有不同的发光模式,且随环境气压的变化而改变。定性地解释了所观察的实验现象。     

Investigation of plumes produced by material ablation with two time-delayed femtosecond laser pulses

We experimentally investigated and herewith reported the results of laser ablation of copper and gold with two time-delayed femtosecond laser pulses at 800 nm in vacuum. The ablation plume dynamic was monitored by fast plume imaging and time- and space-resolved optical emission spectroscopy. Optical microscopy was used to follow the ablation depth as a function of the delay between the two laser pulses. Nanoparticles deposition on mica substrates was analysed by atomic force microscopy.We estimate roughly the plume's atomization degree - that is the mass fraction of atomized material over the total ablated mass - from the relative intensities of radiation emitted from atoms and nanoparticles. It is shown that the atomization degree depends critically on the time delay between both laser pulses and on the characteristic time of electron-lattice relaxation. The increase of the atomization degree is accompanied by the decrease of the ablation depth. Atomic force microscopy measurements confirm the partial atomization of nanoparticles, as the analyses of particle deposition on mica substrates show a large decrease of the number of nanoparticles for large delay between the two pulses.     

Effects of laser intensity and ambient conditions on the laser-induced plume

Laser ablation presents a promising technique for material processing. The quality of products is strongly influenced by the properties of the laser-induced plume. In compressible flow, the ambient conditions can be transmitted upstream. Therefore, the laser ablation process is strongly affected by the ambient conditions. In this paper, the effects of laser intensity, back pressure and temperature on the laser-induced plume were studied using a numerical model, which calculates the density, pressure and temperature of the laser-induced plume at different laser intensity and ambient conditions. The results are in agreement with experimental results available in the literature and can be used for the optimization of the pulsed laser deposition process.     

电场中不同能量密度激光烧蚀制备纳米硅晶粒分布特性

在室温和10 Pa氩气环境中,引入平行于靶面方向的直流电场,通过改变脉冲激光能量密度烧蚀单晶硅靶,在与羽辉轴线呈不同角度的衬底上沉积纳米硅晶薄膜。利用扫描电子显微镜和拉曼散射谱对沉积样品进行分析,结果表明:随着激光能量密度的增加,位于相同角度衬底上的晶粒尺寸和面密度逐渐变大;在同一激光能量密度下,零度角处衬底上的晶粒尺寸和面密度最大,且靠近接地极板处的值比与之对称角度处略大。通过朗缪尔探针对不同能量密度下烧蚀羽辉中硅离子密度变化的诊断、结合成核区内晶粒成核生长动力学过程,对晶粒分布特性进行了分析。     

脉冲激光诱导Cu靶产生发光羽的特性分析

通过在不同的环境气压下拍摄脉冲激光烧蚀金属Cu诱导产生的发光羽,获取了不同区域具有不同颜色特征的发光羽照片.结果发现:发光羽的颜色随环境气压的改变而变化.采用空间分辨光谱技术,测定了激光诱导金属Cu靶产生发光羽辐射强度的空间分布,以及不同烧蚀环境气压对发光羽辐射强度的影响.研究了脉冲激光烧蚀Cu表面诱导发光的动力学过程,建立了可能的发光羽分区模型,对发光羽的不同区域发光粒子的激发机理进行了探讨,并用之定性地解释了所观察的实验现象.结果分析表明:脉冲激光诱导Cu产生的发光羽可以分为三个区域,不同区域的发光机理不同,Cu原子和Cu离子的激发机理不完全相同.     

Preparation of long-afterglow colloidal solution of Sr2MgSi2O7: Eu, Dy by laser ablation in liquid

We have successfully prepared a novel nanoparticle solution of Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺ with afterglow properties by means of laser ablation in liquid. This process also produced by-products of different kinds, depending on the liquid used. The amount of by-product and the size of the nanoparticles were controlled by the energy density of laser ablation. The amount of by-product was reduced by a decrease in the energy density, which also decreased the particle size of the nanoparticles. The PL spectrum of the nanoparticles was the same as that of the target materials used for laser ablation. The afterglow properties deteriorated with a decrease in particle size. We concluded that an increase in specific surface area caused by a decrease in particle size resulted in the decrease of luminescent intensity.     

Preparation of silver nanoparticles by laser ablation in polyvinylpyrrolidone solutions

We performed laser ablation of a silver plate in polyvinylpyrrolidone (PVP) aqueous solutions to prepare silver nanoparticles. Secondary laser irradiation onto the prepared colloidal solutions was also carried out. It was revealed that the formation efficiency was increased by addition of PVP as well as the stability of nanoparticles. The result of shadowgraph measurements suggested that the increased ablation efficiency by PVP is attributable to increased secondary etching efficiency by the solvent-confined plasma toward the silver plate. On the other hand, the size decrease of the nanoparticles by addition of PVP was more remarkable during the secondary irradiation process than in the laser ablation (nanoparticle preparation) process. This result indicates that emitted materials interact less sufficiently with PVP molecules in the laser ablation process than in the secondary laser irradiation process.     

Early stage of the material removal during ArF laser ablation of graphite

Material removal during ArF excimer laser ablation of graphite at atmospheric pressure was investigated by two independent methods; 1) by observation of the propagating properties of the shock wave generated by the carbonaceous ejecta and 2) by in situ measurement of the size distribution of carbon nanoparticles condensing in the ablation plume. This latter was carried out by a scanning mobility particle sizer system based on a differential mobility analyser. The performed measurements indicate that the material removal during ArF laser ablation consists of two steps at fluences above the threshold fluence. First, a thin layer of carbon (of the order of 1 nm) is removed by a quick desorption process, leading to shockwave formation. This process takes place in a ns time scale, and desorption rate estimations reveal that this can not be explained by thermal surface evaporation. Since to our knowledge there is no thermal process that could account for the estimated desorption rate, it is argued that this is a fast photochemical (i.e. non-thermal) process. The size distribution of the condensed nanoparticles related to this step shows a rising edge at diameters below 10 nm. At fluences above the ablation threshold, the majority of the material is ejected in the second phase, resulting in condensation of carbon nanoparticles, peaking at 50 nm diameters in the size spectrum. Both shockwave formation and material removal are also detected well below the ablation threshold fluence, which is attributed to the photochemical process. PACS 61.46.+w; 81.16.Mk     

Dynamical study of femtosecond-laser-ablated liquid-aluminum nanoparticles using spatiotemporally resolved x-ray-absorption fine-structure spectroscopy

We study the temperature evolution of aluminum nanoparticles generated by femtosecond laser ablation with spatiotemporally resolved x-ray-absorption fine-structure spectroscopy. We successfully identify the nanoparticles based on the L-edge absorption fine structure of the ablation plume in combination with the dependence of the edge structure on the irradiation intensity and the expansion velocity of the plume. In particular, we show that the lattice temperature of the nanoparticles is estimated from the L-edge slope, and that its spatial dependence reflects the cooling of the nanoparticles during plume expansion. The results reveal that the emitted nanoparticles travel in a vacuum as a condensed liquid phase with a lattice temperature of about 2500 to 4200 K in the early stage of plume expansion.     

Ar环境下脉冲激光烧蚀粒子阻尼系数的空间分布

在10 Pa的Ar环境气体中,采用脉冲激光烧蚀技术,分别在半径为2.0,2.5,3.0,3.5和4.0 cm的半圆环不同角度处的衬底上制备了一系列含有纳米晶粒的Si晶薄膜。使用扫描电子显微镜、X射线衍射仪和拉曼光谱仪对其表面形貌和微观结构进行分析表征。结果表明,纳米Si晶粒的平均尺寸和烧蚀粒子的阻尼系数均相对于羽辉轴向呈对称分布,并随着与羽辉轴向夹角的增大而减小;同时,随着衬底半径的增加,晶粒平均尺寸和阻尼系数均逐渐减小。     

Small size TiO2 nanoparticles prepared by laser ablation in water

Titanium dioxide nanoparticles in distilled H₂O solvent were prepared by laser ablation. The experiments were performed irradiating a Ti target with a second harmonic (532 nm) output of a Nd:YAG laser varying the operative fluence between 1 and 10 J cm⁻² and for an ablation time ranging from 10 to 30 min. Electron microscopy measurements have evidenced the predominant presence of nanoparticles with diameter smaller than 10 nm together with agglomerations of 100-200 nm whose content increases with the laser fluence. At low laser fluence the particles’ size distribution shows that more than 85% of the nanoparticles have a size smaller than 5 nm while at mid and high fluences the presence of 5-7 nm nanoparticles is predominant. XPS analysis has revealed the presence of different titanium suboxide phases with the prevalence of Ti-O bonds from TiO₂ species. The optical bandgap values, determined by UV-vis absorption measurements, are compatible with the anatase phase.     

Temporal evolution of laser-ablated Co ions probed by time-of-flight mass spectrometry

A pulsed-field time-of-flight mass spectrometric (TOFMS) technique was used to investigate the expansion dynamics of the ionic species ejected from the visible (λ=532 nm) laser ablation of cobalt target at low laser fluence less than 1 J/cm². The temporal evolution of Co⁺ ions was studied by varying the delay time of the ion repelling pulse with respect to the laser irradiation, which provides significant information on the ablated plume characterization. The obtained TOF mass spectra were well fitted by shifted Maxwell–Boltzmann distributions on a stream velocity, commonly used to describe the measured velocity distributions. The TOF distribution of Co⁺ ions showed a bimodal distribution with fast and slow velocities. These velocities show a decreasing tendency with delay time, which is attributed to the gas collisions between the plume ejecta and to the related gas dynamics. The present results suggest that the in situ measurements of the most probable velocity of ablated ions along the normal to the solid target can be accomplished by the simple technique of a laser ablation/TOFMS.     

Formation process of Si nanoparticles in rare gas observed by a decomposition method

We have investigated the formation process of silicon nanoparticles after laser ablation of silicon targets in argon gas. The nanoparticles exhibit bright photoluminescence in the visible wavelength range and can be applied to opto-electronic devices. In order to observe silicon nanoparticles, we have developed a decomposition method. The nanoparticles were probed by detecting light emission resulting from decomposition using a second laser. This method enables us to observe nanoparticles that cannot be observed directly by the methods applied so far. We have observed that the nanoparticles grow in time periods of 1.0-1.8 ms following ablation in Ar gas at 5 Torr when Si targets are ablated at 5 J/cm² with a pulse width of 7 ns. The nanoparticles begin to grow above ablation spots slightly apart from the targets just after thermalization of the plume. We also found that the growth is delayed at higher fluxes of ablation laser light.     

Pulsed laser ablation of borocarbide targets probed by time-of-flight mass spectrometry

Excimer laser ablation of superconductive borocarbide material (YNi₂B₂C) in typical conditions for the deposition of superconductive thin films has been investigated using time-of-flight mass spectrometry. The mass spectra show the presence of all the target elemental ionized atoms as well as diatomics. The ablation yield of the metal ions is a strongly increasing function of the laser fluence, while the contrary is true for non-metal ions. The dependence of non-metal light mass diatomic ions on laser fluence indicates the presence of aggregation processes as the laser fluence is increased. Moreover, evidence of aggregation processes involving metallic ions at high laser fluence is also obtained by the mass spectra. An interesting aspect of our results is the observation of an ion spatial distribution characterized by the presence of the lighter species at the plume edges, while the heavier ones are concentrated at the plume center.     

Picosecond and femtosecond pulsed laser ablation and deposition of quasicrystals

A Nd:glass laser with pulse duration of 250 fs and 1.3 ps has been used to evaporate a Al₆₅Cu₂₃Fe₁₂ quasicrystalline target. The gaseous phase obtained from the ablation process has been characterised by several techniques such as emission spectroscopy, quadrupole mass spectrometry and ICCD imaging, used to study the plume composition, energy and morphology. The results show that the ablation processes in the short-pulse regimes are very different to the nanosecond one. In particular the plume angular distribution shows a characteristic high cosine exponent and the composition is completely stoichiometric and independent from the laser fluence. Furthermore the mass spectra indicate the presence of clusters, both neutral and ionised and the emission from the target suggest a rapid thermalisation leading to the melting of the surface. To clarify the ablation process some films have been deposited, on oriented silicon, at different experimental conditions and analysed by scanning electron microscopy, atomic force microscopy, energy dispersive X-ray analysis and X-ray diffraction. The analyses show the presence of nanostructured films retaining the target stoichiometry but consisting of different crystalline and non crystalline phases. In particular the nanostructure supports the hypothesis of the melting of the target during the ablation and a mechanism of material ejection is proposed for both picosecond and femtosecond regimes.     

Features of plasma plume evolution and material removal efficiency during femtosecond laser ablation of nickel in high vacuum

We present an experimental characterization describing the characteristics features of the plasma plume dynamics and material removal efficiency during ultrashort, visible (527 nm, ≈300 fs) laser ablation of nickel in high vacuum. The spatio-temporal structure and expansion dynamics of the laser ablation plasma plume are investigated by using both time-gated fast imaging and optical emission spectroscopy. The spatio-temporal evolution of the ablation plume exhibits a layered structure which changes with the laser pulse fluence F. At low laser fluences (F<0.5 J/cm²) the plume consists of two main populations: fast Ni atoms and slower Ni nanoparticles, with average velocities of ≈10⁴ m/s for the atomic state and ≈10² m/s for the condensed state. At larger fluences (F>0.5 J/cm²), a third component of much faster atoms is observed to precede the main atomic plume component. These atoms can be ascribed to the recombination of faster ions with electrons in the early stages of the plume evolution. A particularly interesting feature of our analysis is that the study of the ablation efficiency as a function of the laser fluence indicates the existence of an optimal fluence range (a maximum) for nanoparticles generation, and an increase of atomization at larger fluences. PACS 52.50.-b; 52.38.Mf; 79.20.Ds; 81.07.-b