Identification of non-thermal and thermal processes in femtosecond laser-ablated aluminum

Non-thermal and thermal processes due to femtosecond laser ablation of aluminum (Al) at low, moderate, and high-fluence regimes are identified by Atomic Force Microscope (AFM) surface topography investigations. For this purpose, surface modifications of Al by employing 25 fs Ti: sapphire laser pulses at the central wavelength of 800 nm have been performed to explore different nano- and microscale features such as hillocks, bumps, pores, and craters. The mechanism for the formation of these diverse kinds of structures is discussed in the scenario of three ablation regimes. Ultrafast electronic and non-thermal processes are dominant in the lower fluence regime, whereas slow thermal processes are dominant at the higher fluence regime. Therefore, by starting from the ablation threshold three different fluence regimes have been chosen: a lower fluence regime (0.06–0.5 J cm^?2 single-shot irradiation under ultrahigh vacuum condition and 0.25–2.5 J cm^?2 single-shot irradiation in ambient condition), a moderate-fluence regime (0.25–1.5 J cm^?2 multiple-shot irradiation), and a high-fluence regime 2.5–3.5 J cm^?2 multiple-shot irradiation. For the lower fluence (gentle ablation) regime, around the ablation threshold, the unique appearance of individual, localized Nano hillocks typically a few nanometers in height and less than 100 nm in diameter are identified. These Nano hillock-like features can be regarded as a nonthermal, electronically induced phase transition process due to localized energy deposition as a result of Coulomb explosion or field ion emission by surface optical rectification. At a moderate-fluence regime, slightly higher than ablation threshold multiple-pulse irradiation produces bump-formation and is attributed to ultrafast melting (plasma formation). The high-fluence regime results in greater rates of material removal with highly disturbed and chaotic surface of Al with an appearance of larger protrusions at laser fluence well above the ablation threshold. These nonsymmetrical shapes due to inhomogeneous nucleation, cluster formation, and resolidification of a metallic surface after melting are attributable to slow thermal processes (ps time scale).     

fs Laser surface nano-structuring of high refractory ceramics to enhance solar radiation absorbance

The surface and structural modification of titanium (Ti) has been explored after the interaction of ultrashort laser pulses with the surface target. The targets were exposed by femtosecond Ti: Sapphire laser pulses in liquid (ethanol) and dry (air) environment. In order to explore the effect of pulse energy, the targets were exposed to 1,000 succeeding pulses for various pulse energies ranging from 200 to 500 μJ for pulse duration of 25 fs. SEM analyses were performed for central as well as the peripheral ablated areas of the target. It was found that in the case of ethanol (both for central and peripheral ablated areas) there is a grain growth along with nanoscale pores and dots when the target was irradiated for 200 μJ. For intermediate energies (300–400 μJ), grains of 1–2 μm with distinct boundaries are formed in the central ablated area. Whereas in the peripheral ablated area, laser-induced periodic surface structures (LIPSS) and globules are grown. For the highest pulse energy (500 μJ), distinct grains are observed for both regions. However, in the peripheral area the grains are of bigger size with cracks along the boundaries. In case of ablation in air, in the center of ablated areas, island-like structures with multiple ablative layer or LIPSS and nanoscale spheres are observed both for lower and intermediate pulse energies. For the highest pulse energy only nanoscale LIPSS could be observed. For ablation in air at the peripheral areas, well-defined, laser-induced periodic surface structures are observed for all pulse energies. Raman spectroscopy reveals that the liquid (ethanol) environment forms the carbonyl compounds with the metal and induces C–C stretching vibration, whereas in case of air, hydroxo complexes are formed. It has been found that surface treatment of Ti with ultrashort (25 fs) laser radiation in ethanol environment allows the growth of particular surface structures in the form of grains and simultaneously induces changes in its chemical composition.     

Formation of nanostructures by an intense femtosecond pulse laser irradiating Au film on sapphire substrate

We investigate the morphology change of Au film on sapphire substrate by irradiating with a 1 kHz femtosecond pulse laser. Under observation of a scanning electron microscope, a textured nanostructure was formed in the exposed area on Au film due to laser ablation and subsequent stress relaxation. This process was strongly determined by the laser intensity profile and the dynamics of molten liquid. With the increasing of laser pulses number, the Au film was broken down and then a few polarization-dependent nanoripples arranged in the same direction appeared on the sapphire surface, which may result from a spatial modulation of energy due to the interference between the incident light and the excited surface plasmon polaritons. In addition, we used an energy dispersive spectrometer to analyze the chemical composition of nanoripples on the surface and in the ablated crater, respectively. The changes of O and Al elements implied that a complicated chemical transformation participated in the nanoripples formation process. We believe that present results are very useful for the analysis of the interaction between femtosecond laser and solids, especially the film material.     

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.     

Identification of ultra-fast electronic and thermal processes during femtosecond laser ablation of Si

Ultra-fast electronic and thermal processes for the energy deposition mechanism during femtosecond laser ablation of Si have been identified by means of atomic force microscopy and Raman scattering techniques. For this purpose, Si targets were exposed with 800-nm, 25-fs Ti:sapphire laser pulses for different laser fluencies in air and under UHV (ultra high vacuum) conditions. Various nano- and microstructures on the surface of the irradiated samples are revealed by a detailed surface topography analysis. Ultra-fast electronic processes are dominant in the lower-fluence regime. Therefore, by starting from the ablation threshold three different fluence regimes have been chosen: a lower-fluence regime (0.06–0.5 J?cm^?2 single-shot irradiation under UHV condition and 0.25–2.5 J?cm^?2 single-shot irradiation in ambient condition), a moderate-fluence regime (0.25–1.5 J?cm^?2 multiple-shot irradiation), and a higher-fluence regime (2.5–3.5 J?cm^?2 multiple-shot irradiation). Around the ablation threshold fluence, most significant features identified at the Si surface are nanohillock-like structures. The appearance of these nanohillocks is regarded as typical features for fast electronic processes (correlated with existence of hot electrons) and is explained on the basis of Coulomb explosion. The growth of these typical features (nanohillocks) by femtosecond laser irradiation is an element of novelty. At moderate irradiation fluence, a ring-shaped ablation with larger bumps and periodic surface structures is observed and is considered as a footprint of ultra-fast melting. Further increase in the laser fluence, i.e. a higher-fluence regime, resulted in strong enhancement of the thermal process with the appearance of larger islands. The change in surface topography provides an innovative clue to differentiate between ultra-fast electronic processes, i.e. Coulomb explosion (sub-100 fs) at a lower-fluence regime and ultra-fast melting (hundreds of fs) at a moderate-fluence regime, and slow thermal processes (ps time scale) at a higher-fluence regime. These fast electronic and thermal processes are well correlated to structural and crystallographic alterations, inferred from Raman spectroscopy.     

Simulation of rippled structure adjustments based on localized transient electron dynamics control by femtosecond laser pulse trains

This study investigates the effects of pulse energy distributions on subwavelength ripple structures (the ablation shapes and subwavelength ripples) using the plasma model with the consideration of laser particle–wave duality. In the case studies, the laser pulse (800 nm, 50 fs) trains consist of double pulses within a train with the energy ratios of 1:2, 1:1, and 2:1. Localized transient electron densities, material optical properties, and surface plasmon generation are strongly affected by the energy distributions. Hence, the adjustment of the ablation shape and subwavelength ripples can be achieved based on localized transient electron dynamics control during femtosecond laser pulse train processing of dielectrics. The simulation results show that better, more uniform structures, in terms of ablation shapes and subwavelength ripples, can be easily formed at a lower fluence or subpulse energy ratio of 1:1 with a fixed fluence. It is also found that pulse trains at a 1:1 energy ratio are preferred for drilling high-aspect-ratio microholes or microchannels.     

Guidelines for efficient direct ablation of dielectrics with single femtosecond pulses

We provide guidelines to femtosecond laser users to select ad hoc laser parameters, namely the fluence and pulse duration, in the context of the development of ablation processes at the surface of dielectrics using single femtosecond pulses. Our results and discussion are based on a comprehensive experimental and theoretical analysis of the energy deposition process at the surface of fused silica samples and of their postmortem ablation characteristics, in the range of intensities from 10¹³ to 10¹⁵ W/cm². We show experimentally and numerically that self-induced plasma transient properties at the pulse timescale dramatically determine the efficiency of energy deposition and affect the resulting ablation morphology. In practice, we determine that the precise measurement of two characteristic fluence values, namely the laser-induced ablation threshold F _th,LIAT and the fluence F _opt for maximum ablation efficiency, are only required to qualify the outcomes of laser ablation at the surface of a dielectric in an extended range of applied fluence.     

Interaction of ultra-short laser pulses with CIGS and CZTSe thin films

The thin-film solar cell technologies based on complex quaternary chalcopyrite and kesterite materials are becoming more attractive due to their potential for low production costs and optimal spectral performance. As in all thin-film technologies, high efficiency of small cells might be maintained with the transition to larger areas when small segments are interconnected in series to reduce photocurrent and related ohmic losses in thin films. Interconnect formation is based on the three scribing steps, and the use of a laser is here crucial for performance of the device. We present our simulation and experimental results on the ablation process investigations in complex CuIn_1?x Ga _x Se₂ (CIGS) and Cu₂ZnSn(S,Se)₄ (CZTSe) cell’s films using ultra-short pulsed infrared (~1 μm) lasers which can be applied to the damage-free front-side scribing processes. Two types of processes were investigated—direct laser ablation of ZnO:Al/CIGS films with a variable pulse duration of a femtosecond laser and the laser-induced material removal with a picosecond laser in the ZnO:Al/CZTSe structure. It has been found that the pulse energy and the number of laser pulses have a significantly stronger effect on the ablation quality in ZnO:Al/CIGS thin films rather than the laser pulse duration. For the thin-film scribing applications, it is very important to carefully select the processing parameters and use of ultra-short femtosecond pulses does not have a significant advantage compared to picosecond laser pulses. Investigations with the ZnO:Al/CZTSe thin films showed that process of the absorber layer removal was triggered by a micro-explosive effect induced by high pressure of sublimated material due to a rapid temperature increase at the molybdenum-CZTSe interface.     

Melting and resolidification of gold film irradiated by laser pulses less than 100 fs

The rapid melting and resolidification of gold films irradiated by laser pulses less than 100 fs are investigated using the dual-hyperbolic two-step model. The solid–liquid interfacial velocity in the ultrafast phase change process is obtained by coupling a hyperbolic interfacial energy balance equation and nucleation dynamics. The results are compared with the experimental data for the 28-fs laser. The effects of laser pulse widths and fluences on melting process are investigated. A phase chart of the variations of pulse widths and fluences is established. The relationship between the melting threshold and ablation threshold is also presented.     

Optodynamic energy conversion efficiency during laser ablation on metal surfaces measured by shadow photography

In this investigation, we used high-speed shadow photography to observe fast optodynamic phenomena such as shock waves and the ablation of flat metal surfaces. These phenomena were induced in air by a Q-switched Nd:YAG laser (λ = 1,064 nm) with a pulse duration of 4 ns and an excitation pulse energy between 10 and 55 mJ. For a good spatial resolution of the shadowgraphs, we used short illumination pulses (30 ps) from a frequency-doubled Nd:YAG laser (λ = 532 nm). Using the shadowgraphs of the shock wave expansion into a half-space, we measured the optodynamic energy conversion efficiency, defined as the ratio between the mechanical energy of the shock wave and the excitation pulse energy. This efficiency increases with an increasing excitation pulse energy. We also present the characteristic shadowgraphs of the ablation of a black-painted metal surface, where the macroscopic material particles are clearly visible. They follow the shock wave and eventually overtake it. As a result, the shape of the shock wave, which normally expands concentrically into the half-space, has an altered form. The presented results reveal the phenomenon of the laser ablation of coated metal surfaces.     

激光脉冲对内层等离子体辐射源的影响

本文的基本思想是设计双层金铝薄膜靶以检测激光脉冲宽度与等离子体消融深度的关系,找出有效的等离子体加热方法以产生更强更亮的等离子体辐射源.由于有预脉冲激光的存在,表层金薄膜首先被消融,由主脉冲携带的大能量就能较易穿过表层金等离子体将能量聚焦在内层铝靶上,由此产生内层高温等离子体.又由于外层低温等离子体存在,其将有效的阻碍内高温等离子体因膨胀而引起的能量损失.对无预脉冲而言,直接入射激光能量都沉积在靶表层形成表层高温等离子体.但是激光直接入射而产生的等离子体辐射总强度只比由预脉冲情况下产生的金等离子体辐射强度增加15%.而预脉冲能量只占激光总能量的2%.实验结果显示Al光谱线主要来自类氢,类氦离子跃迁.Au等离子体光谱线主要来自它的N带,O带和P带谱.我们也观察到一个明显的软X射线短波发射极限.所有结果显示由于预脉冲的存在将对靶各层等离子体辐射产生极大的影响     

Mutual influence of Auger and non-radiative recombination processes under silicon femtosecond laser irradiation

The results of theoretical study of the contribution of recombination processes in additional heating of the surface of monocrystalline silicon during multipulse femtosecond laser processing are presented to discussion. The numerical evaluations are made in regimes of the laser radiation below the ablation threshold, when the microgeometry of the surface is formed due to the processes of self-organization. The influence of Auger recombination processes on the photoexcitation of the semiconductor during the pulse and relaxation after the pulse is studied in detail. It is shown that the additional heating of the surface due to non-radiative recombination is extremely small at pulse repetition rate 10 Hz–1 MHz. Mutual influence of recombination processes of both types is shown.     

Biocompatible film deposition by using Nd:YAG pulsed laser

A Nd:YAG laser operating at the fundamental wavelength (1064 nm) and at the second harmonic (532 nm), with 9 ns pulse duration, 100–900 mJ pulse energy, and 30 Hz repetition rate mode, was employed to ablate in vacuum (10^?6 mbar) biomaterial targets and to deposit thin films on substrate backings. Titanium target was ablated at the fundamental frequency and deposited on near-Si substrates. The ablation yield increases with the laser fluence and at 40 J/cm ² the ablation yield for titanium is 1.2×10¹⁶ atoms/pulse. Thin film of titanium was deposited on silicon substrates placed at different distance and angles with respect to the target and analysed with different surface techniques (optical microscopy, scanning electron spectrosopy (SEM), and surface profile).

Hydroxyapatite (HA) target was ablated to the second harmonic and thin films were deposited on Ti and Si substrates. The ablation yield at a laser fluence of 10 J/cm ² is about 5×10¹⁴ HA molecules/pulse. Thin film of HA, deposited on silicon substrates placed at different distance and angles with respect to the target, was analysed with different surface techniques (optical microscopy, SEM, and Raman spectroscopy).

Metallic films show high uniformity and absence of grains, whereas the bio-ceramic film shows a large grain size distribution. Both films found special application in the field of biomaterial coverage.     

Laser-induced fabrication of randomly distributed nanostructures in fused silica surfaces

The nanostructuring of dielectrics is a big challenge for laser patterning methods. In this study a novel laser structuring method for the fabrication of randomly distributed nanostructures, called laser-induced front side etching using in situ pre-structured metal layers (IPSM-LIFE), is presented. The pulsed laser irradiation of a thin metal film deposited onto a dielectric substrate with fluences below the ablation threshold results in the formation of randomly distributed metal structures by self-assembly processes. Further pulsed laser irradiation of these metal structures with higher or equal laser fluences causes the formation of complex patterns at the surface of the dielectric due to localized ablation and melting processes of the dielectric surface induced by the absorption of the laser energy by the metal structures and the local energy transfer into the dielectric surface. The pattern formation observed in the film and the dielectrics substrate after irradiation of 10 nm chromium layers on fused silica, with laser pulses (Δt _p =25 ns, λ=248 nm), was studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Different features with a lateral size down to a few tens of nanometers, like concentric ring patterns, donut-like structures, and bar patterns were observed at the dielectric.     

Ultrafast solid–liquid–vapor phase change of a gold film induced by pico- to femtosecond lasers

Melting, vaporization and resolidification processes of thin gold film irradiated by a femtosecond pulse laser are studied numerically. The nonequilibrium heat transfer in electrons and lattice is described using a two-temperature model. The solid–liquid interfacial velocity, as well as elevated melting temperature and depressed solidification temperature, is obtained by considering the interfacial energy balance and nucleation dynamics. An iterative procedure based on energy balance and gas kinetics law to track the location of liquid–vapor interface is utilized to obtain the material removal by vaporization. The effect of surface heat loss by thermal radiation was discussed. The influences of laser fluence and duration on the evaporation process are studied. Results show that higher laser fluence and shorter laser pulse width lead to higher interfacial temperature, deeper melting and ablation depths.     

飞秒激光在空气和水中对硅片烧蚀加工的实验研究

采用1 kHz,800 nm,50 fs—24 ps的钛宝石激光脉冲对单晶硅样品在空气和水溶液环境中的烧蚀加工特性进行了研究.实验观察到了超短脉冲激光在空气氛围中烧蚀形成的双层环状结构,分析揭示了加工区域中心和边缘的烧蚀物理机制分别为热熔化和库仑爆炸,并测量了双层环状结构半径随入射激光能量、脉冲数及持续时间等的变化关系,结果表明获取较大深-宽比的加工效果需选择小能量脉冲激光的多次作用.在水溶液环境中,实验发现飞秒激光在样品表面诱导产生了亚微米量级的多孔状结构,而皮秒激光则更容易实现对硅表面的非热性去除.这是由于激光诱导的光机械应力和空泡效应随脉冲宽度变大而增强所致,在实验上确立了区分这两种不同加工状态的临界脉冲宽度. 关键词： 飞秒激光 硅片 激光加工     

Single-pulse drilling study on Au,Al and Ti alloy by using a picosecond laser

Picosecond laser single pulse ablation of Au, Al and Ti alloy (Ti6Al4V) was experimentally investigated with a laser pulse width of 10 ps at a wavelength of 1064 nm for potential industrial micromachining applications. The diameters, depths and morphologies of the drilled craters were studied. Two novel phenomena were found: as hole diameters decreased with fluence, a change of slope of the trend line indicated a change in ablation mechanism for Al and Ti alloy, metallic materials with short electron-phonon coupling times (<10 ps), while Au showed no such transition: an isolated island structure was also observed on Au due to significant melt expulsion. A one-dimensional two-temperature model has been used to discriminate different ablation phenomena. It is shown that metallic materials with different electron–phonon coupling constant have different ablation characteristics in the ps regime. This study could be very helpful for metallic material micromachining with high repetition rate ps lasers pulses which indicates that high throughput may be achieved as well as good machining quality.     

Large area laser surface micro/nanopatterning by contact microsphere lens arrays

Laser surface micro/nanopatterning by particle lens arrays is a well-known technique. Enhanced optical fields can be achieved on a substrate when a laser beam passes through a self-assembled monolayer of silica microspheres placed on the substrate. This enhanced optical field is responsible for ablative material removal from the substrate resulting in a patterned surface. Because of the laser ablation, the microspheres are often ejected from the substrate during laser irradiation. This is a major issue impeding this technique to be used for large area texturing. We explored the possibility to retain the spheres on the substrate surface during laser irradiation. A picosecond laser system (wavelength of 515 nm, pulse duration 6.7 ps, repetition rate 400 kHz) was employed to write patterns through the lens array on a silicon substrate. In this experimental study, the pulse energy was found to be a key factor to realize surface patterning and retain the spheres during the process. When the laser pulse energy is set within the process window, the microspheres stay on the substrate during and after laser irradiation. Periodic patterns of nanoholes can be textured on the substrate surface. The spacing between the nanoholes is determined by the diameter of the microspheres. The depth of the nanoholes varies, depending on the number of laser pulses applied and pulse energy. Large area texturing can be made using overlapping pulses obtained through laser beam scanning.