SEM and Raman spectroscopy analyses of laser-induced periodic surface structures grown by ethanol-assisted femtosecond laser ablation of chromium

The effect of fluence and pulse duration on the growth of nanostructures on chromium (Cr) surfaces has been investigated upon irradiation of femtosecond (fs) laser pulses in a liquid confined environment of ethanol. In order to explore the effect of fluence, targets were exposed to 1000 pulses at various peak fluences ranging from 4.7 to 11.8?J?cm^–2 for pulse duration of ～25?fs. In order to explore the effect of pulse duration, targets were exposed to fs laser pulses of various pulse durations ranging from 25 to 100?fs, for a constant fluence of 11.8?J?cm^–2. Surface morphology and structural transformations have been analyzed by scanning electron microscopy and Raman spectroscopy, respectively. After laser irradiation, disordered sputtered surface with intense melting and cracking is obtained at the central ablated areas, which are augmented with increasing laser fluence due to enhanced thermal effects. At the peripheral ablated areas, where local fluence is approximately in the range of 1.4–4?mJ?cm^–2, very well-defined laser-induced periodic surface structures (LIPSS) with periodicity ranging from 270 to 370?nm along with dot-like structures are formed. As far as the pulse duration is concerned, a significant effect on the surface modification of Cr has been revealed. In the central ablated areas, for the shortest pulse duration (25?fs), only melting has been observed. However, LIPSS with dot-like structures and droplets have been grown for longer pulse durations. The periodicity of LIPSS increases and density of dot-like structures decreases with increasing pulse duration. The chemical and structural modifications of irradiated Cr have been revealed by Raman spectroscopy. It confirms the formation of new bands of chromium oxides and enol complexes or Cr-carbonyl compounds. The peak intensities of identified bands are dependent upon laser fluence and pulse duration.     

Periodic surface structures on crystalline silicon created by 532 nm picosecond Nd:YAG laser pulses

Creation of laser-induced morphology features, particularly laser-induced periodic surface structures (LIPSS), by a 532 nm picosecond Nd:YAG laser on crystalline silicon is reported. The LIPSS, often termed ripples, were produced at average laser irradiation fluences of 0.7, 1.6, and 7.9 J cm⁻². Two types of ripples were registered: micro-ripples (at micrometer scale) in the form of straight parallel lines extending over the entire irradiated spot, and nano-ripples (at nanometer scale), apparently concentric, registered only at the rim of the spot, with the periodicity dependent on laser fluence. There are indications that the parallel ripples are a consequence of the partial periodicity contained in the diffraction modulated laser beam, and the nano-ripples are very likely frozen capillary waves. The damage threshold fluence was estimated at 0.6 J cm⁻².     

Effect of fluence and ambient environment on the surface and structural modification of femtosecond laser irradiated Ti

Under certain conditions, ultrafast pulsed laser interaction with matter leads to the formation of self-organized conical as well as periodic surface structures(commonly reffered to as, laser induced periodic surface structures, LIPSS). The purpose of the present investigations is to explore the effect of fsec laser fluence and ambient environments(Vacuum O_2) on the formation of LIPSS and conical structures on the Ti surface. The surface morphology was investigated by scanning electron microscope(SEM). The ablation threshold with single and multiple(N = 100) shots and the existence of an incubation effect was demonstrated by SEM investigations for both the vacuum and the O_2 environment. The phase analysis and chemical composition of the exposed targets were performed by x-ray diffraction(XRD) and energy dispersive x-ray spectroscopy(EDS), respectively. SEM investigations reveal the formation of LIPSS(nano micro). FFT d-spacing calculations illustrate the dependence of periodicity on the fluence and ambient environment. The periodicity of nano-scale LIPSS is higher in the case of irradiation under vacuum conditions as compared to O_2. Furthermore, the O2 environment reduces the ablation threshold. XRD data reveal that for the O_2 environment, new phases(oxides of Ti) are formed. EDS analysis exhibits that after irradiation under vacuum conditions, the percentage of impurity element(Al) is reduced. The irradiation in the O_2 environment results in 15% atomic diffusion of oxygen.     

Femtosecond laser-induced damage morphologies of crystalline silicon by sub-threshold pulses

The effect of sub-threshold pulses of circularly polarized Ti:sapphire femtosecond laser system on crystalline (1 0 0) silicon wafer was investigated. Surface damage morphologies were studied by irradiating the test silicon surface with pulses (peak fluence of 0.25 J/cm²) in succession. These pulses were below the single-pulse surface damage threshold. After the few initial pulses, the observed surface damage morphologies were found to be characterized by a minor phase change region and a major surface damage area at the center, corresponding to the well-known laser-induced periodic surface structure (LIPSS). Further increase in the number of pulses resulted in the formation of new surface morphologies with different features such as ablation, modification, and re-deposited materials. These features were reproducible and more distinguishable at higher number of pulses.     

Sub-100-nm laser-induced periodic surface structures upon irradiation of titanium by Ti:sapphire femtosecond laser pulses in air

The formation of laser-induced periodic surface structures (LIPSS) on titanium upon irradiation with linearly polarized femtosecond (fs) laser pulses (τ=30 fs, λ=790 nm) in an air environment is studied experimentally and theoretically. In the experiments, the dependence on the laser fluence and the number of laser pulses per irradiation spot has been analyzed. For a moderate number of laser pulses (N<1000) and at fluences between ～0.09 and ～0.35 J/cm², predominantly low-spatial-frequency-LIPSS with periods between 400 nm and 800 nm are observed perpendicular to the polarization. In a narrow fluence range between 0.05 and 0.09 J/cm², high-spatial-frequency-LIPSS with sub-100-nm spatial periods (～λ/10) can be generated with an orientation parallel to the polarization (N=50). These experimental results are complemented by calculations based on a theoretical LIPSS model and compared to the present literature.     

Sub-wavelength surface structures on silicon irradiated by femtosecond laser pulses at 1300 and 2100 nm wavelengths

We present periodic ripples and arrays of protrusions formed on the surface of silicon after irradiation by low-fluence linearly polarized femtosecond laser pulses. Laser-induced periodic surface structures (LIPSS) are observed for irradiation at center wavelengths of 800, ∼ 1300, and ∼ 2100 nm, with the structure periods somewhat less than the incident wavelengths in air. Additionally, we observe structures with spatial periods substantially less than the incident laser wavelengths. These sub-wavelength periodic structures form only when the photon energy is less than the silicon bandgap energy. We discuss a number of factors which may contribute to the generation of this surface morphology.     

Superhydrophobic surfaces fabricated by microstructuring of stainless steel using a femtosecond laser

Fabrication of superhydrophobic surfaces induced by femtosecond laser is a research hotspot of superhydrophobic surface studies nowadays. We present a simple and easily-controlled method for fabricating stainless steel-based superhydrophobic surfaces. The method consists of microstructuring stainless steel surfaces by irradiating samples with femtosecond laser pulses and silanizing the surfaces. By low laser fluence, we fabricated typical laser-induced periodic surface structures (LIPSS) on the submicron level. The apparent contact angle (CA) on the surface is 150.3°. With laser fluence increasing, we fabricated periodic ripples and periodic cone-shaped spikes on the micron scale, both covered with LIPSS. The stainless steel-based surfaces with micro- and submicron double-scale structure have higher apparent CAs. On the surface of double-scale structure, the maximal apparent CA is 166.3° and at the same time, the sliding angle (SA) is 4.2°.     

Morphology control of laser-induced periodic surface structure on the surface of nickel by femtosecond laser

An interesting transition between low spatial frequency laser-induced periodic surface structure(LIPSS) and high spatial frequency LIPSS(HSFL) on the surface of nickel is revealed by changing the scanning speed and the laser fluence. The experimental results show the proportion of HSFL area in the overall LIPSS(i.e., K) presents a quasi-parabola function trend with the polarization orientation under a femtosecond(fs) laser single-pulse train.Moreover, an obvious fluctuation dependence of K on the pulse delay is observed under a fs laser dual-pulse train.The peak value of the fluctuation is found to be determined by the polarization orientation of the dual-pulse train.     

On the physics of self-organized nanostructure formation upon femtosecond laser ablation

We present new results on femtosecond LIPSS on silicon, fostering the dynamic model of self-organized structure formation. The first set of experiments demonstrates LIPSS formation by irradiation with a femtosecond white light continuum. The ripples are, as usual, perpendicular to the light polarization with a fluence-dependent wavelength between 500 and 700 nm. At higher dose (fluence × number of shots), the LIPSS turn to much coarser structures. The second set of experiments displays the dose dependence of pattern evolution at about threshold fluence. In contrast to the general case of multi-pulse LIPSS, where a strong dependence of the structures on the laser polarization is observed, single-shot exposition of silicon at about the ablation threshold results in a concentric pattern of very regular sub-wavelength ripples following the oval shape of the irradiated spot, without any reference to the laser polarization. When increasing the number of pulses, the usual, typical ripples develop and then coalesce into broader perpendicular structures, interlaced with remnants of the first, finer ripples.     

Dependence of ablation threshold and LIPSS formation on copper thin films by accumulative UV picosecond laser shots

The ablation threshold and Laser-induced periodic surface structure (LIPSS) formation on copper thin film were investigated using a picosecond laser (Nd:YAG laser: 266 nm, 42 ps, 10 Hz). We show that the ablation threshold varies with respect to the number of laser shots (N) on two different substrates. The single-shot ablation threshold was estimated to be close to 170 ± 20 mJ/cm². The incubation coefficient was estimated to be 0.68 ± 0.03 for copper thin films on silicon and glass substrates. In addition, morphology changes of the ablated regions, in the same spot area, were studied as a function of fluence and number of laser shots. An intermediate structure occurred with a mix of low spatial frequency LIPSS (LSFL), high spatial frequency LIPSS (HSFL) and regular spikes at a fluence F < 250 mJ/cm² and 1,000 < N ≤ 10.000 shots. LSFL was observed with a spatial period close to the irradiation wavelength and an orientation perpendicular to the laser polarization, and HSFL with a spatial period of ～120 nm and a parallel orientation. Lastly, the global relationship between the laser parameters (i.e. fluence and number of shots) and LIPSS formation was established in the form of a 2D map.     

Femtosecond laser-induced periodic surface structures on steel and titanium alloy for tribological applications

Laser-induced periodic surface structures (LIPSS, ripples) were generated on stainless steel (100Cr6) and titanium alloy (Ti6Al4V) surfaces upon irradiation with multiple femtosecond laser pulses (pulse duration 30 fs, central wavelength 790 nm). The experimental conditions (laser fluence, spatial spot overlap) were optimized in a sample-scanning geometry for the processing of large surface areas (5 × 5 mm²) covered homogeneously by the nanostructures. The irradiated surface regions were subjected to white light interference microscopy and scanning electron microscopy revealing spatial periods around 600 nm. The tribological performance of the nanostructured surface was characterized by reciprocal sliding against a ball of hardened steel in paraffin oil and in commercial engine oil as lubricants, followed by subsequent inspection of the wear tracks. For specific conditions, on the titanium alloy a significant reduction of the friction coefficient by a factor of more than two was observed on the laser-irradiated (LIPSS-covered) surface when compared to the non-irradiated one, indicating the potential benefit of laser surface structuring for tribological applications.     

飞秒激光诱导钛表面形成高空间频率周期条纹结构

利用波长为800 nm的飞秒激光,在空气和去离子水中诱导钛表面形成不同的周期条纹结构。在空气中,激光能量密度为0.265 J/cm2时,钛表面主要形成周期为500~560 nm低空间频率条纹结构;激光能量密度为0.102 J/cm2时,主要形成的是周期为220~340 nm高空间频率条纹结构。两种条纹均垂直于入射激光偏振方向,且条纹周期随着脉冲重叠数的增大而增大。在水中,除形成垂直激光偏振方向、周期为215~250 nm的高空间频率条纹结构,还形成了平行于激光偏振方向且周期约为入射激光波长八分之一的高空间频率条纹结构。利用表面等离子体理论、二次谐波及Sipe理论对各种周期条纹结构的形成机理进行分析,发现周期条纹结构的形成与钛表面氧化层有密切的关系。     

Rippled area formed by surface plasmon polaritons upon femtosecond laser double-pulse irradiation of silicon: the role of carrier generation and relaxation processes

The formation of laser-induced periodic surface structures (LIPSS, ripples) upon irradiation of silicon with multiple irradiation sequences consisting of femtosecond laser pulse pairs (pulse duration 150 fs, central wavelength 800 nm) is studied numerically using a rate equation system along with a two-temperature model accounting for one- and two-photon absorption and subsequent carrier diffusion and Auger recombination processes. The temporal delay between the individual equal-energy fs-laser pulses was varied between 0 and ～4 ps for quantification of the transient carrier densities in the conduction band of the laser-excited silicon. The results of the numerical analysis reveal the importance of carrier generation and relaxation processes in fs-LIPSS formation on silicon and quantitatively explain the two time constants of the delay-dependent decrease of the low spatial frequency LIPSS (LSFL) area observed experimentally. The role of carrier generation, diffusion and recombination is quantified individually.     

飞秒激光烧蚀硅材料表面形成周期波纹形貌研究

基于Sipe-Drude模型和表面等离子体激元(SPP)的干涉理论分别对单脉冲飞秒激光诱导硅表面形成低频率周期性波纹进行分析研究.探究了波长800 nm、脉宽150 fs的单个飞秒激光烧蚀硅造成不同激发水平下波纹形貌的变化,考虑到材料的光学性质变化(由Drude模型得到的介电常数变化),引入包含双温方程的电子数密度模型.计算结果表明,Sipe-Drude和SPP理论都适用于分析和解释高激发态下周期性波纹,但Sipe-Drude理论更适合分析更为广泛的周期性波纹结构.同时,波纹延伸方向总是垂直于入射激光偏振方向,其空间周期略小于激光波长,并受到入射激光通量的影响.在激光通量为0.38 J/cm~2时,波纹周期达到最小值.另外,还得到了不同入射角度的波纹周期变化情况,并在不同偏振态下随入射角度增大时波纹周期呈现相反的变化趋势.该研究对于理解飞秒激光造成硅表面形成周期结构及其在加工硅材料领域具有重要参考意义.     

Effect of irradiation history on the preparation of laser induced periodic microstructure on polyimide surface

Although UV laser is proved to be an effective tool to prepare microstructure on polymer surface, laser ablation accompanied by the formation of laser induced periodic surface structure (LIPSS) limits its application in many fields. The purpose of this report is to investigate the effect of pre-irradiation in advance, using a low-fluence laser, on the LIPSS formation. The properties of pre-irradiated PI films were characterized by X-ray photoelectron spectroscopy (XPS), surface tension based on the contact angle measurements and UV-vis spectra. It was found that pre-irradiation at low fluence led to the changes in surface property such as chemical components though no LIPSS was formed. As a result, threshold of LIPSS formation on such pre-irradiated PI film decreased and fine LIPSS with deeper amplitude was obtained.     

Ultraviolet laser microstructuring of silicon and the effect of laser pulse duration on the surface morphology

The study of the laser pulse duration effect on the silicon micro-spikes morphology is presented. The microcones were produced by ultraviolet (248 nm) laser irradiation of doped Si wafers in SF₆ environment. The laser pulse duration was adjusted at 450 fs, 5 ps and 15 ns. We have analyzed the statistical nature of the spikes’ morphological characteristics, such as periodicity and apex angle by exploiting image processing techniques, on SEM images of the irradiated samples. The correlation of the quantitative morphological characteristics with the laser parameters (pulse duration, laser fluence and number of pulses) provides new insight on the physical mechanisms, which are involved on the formation of Si microcones.     

Periodic patterning of silicon by direct nanosecond laser interference ablation

The production of periodic structures in silicon wafers by four-beam is presented. Because laser interference ablation is a single-step and cost-effective process, there is a great technological interest in the fabrication of these structures for their use as antireflection surfaces. Three different laser fluences are used to modify the silicon surface (0.8 J cm⁻², 1.3 J cm⁻², 2.0 J cm⁻²) creating bumps in the rim of the irradiated area. Laser induced periodic surface structures (LIPSS), in particular micro and nano-ripples, are also observed. Measurements of the reflectivity show a decrease in the reflectance for the samples processed with a laser fluence of 2.0 J cm⁻², probably caused by the appearance of the nano-ripples in the structured area, while bumps start to deteriorate.     

Laser-induced damage and periodic stripe structures of a CaF_2 single crystal by an ArF excimer laser

The laser-induced damage threshold of a calcium fluoride(CaF2)single crystal was obtained by a 193 nm ArF excimer laser.The damage morphology of the crystal was analyzed.The results showed that the surface of CaF2 single crystal broke along the natural cleavage plane under ArF excimer laser irradiation,some fragments fell off,and Newton’s rings were observed on the curved fragments.Laser-induced periodic stripe structures(LIPSS)appeared on the surface layer beneath the fragments that peeled off.The spacing of LIPSS was measured,and the formation mechanism of LIPSS was analyzed based on the interference model.     

Thermocavitation melt instability and micro-crown formation near the threshold for femtosecond laser spallation of a silicon surface

Thermocavitation instability of a molten layer on a silicon surface was experimentally revealed in the form of a microscale surface crown-like feature produced by multiple infrared or visible femtosecond laser pulses near the spallation threshold fluence. The number of crown spikes varied versus the crown perimeter, monotonically increasing with increasing laser shot number. The instability dynamics was described in terms of the intermediate crown structures (the spike number) using the proposed thermocavitation model based on the Kuramoto-Sivashinsky hydrodynamic equation.     

Dynamics of the formation of laser-induced periodic surface structures on dielectrics and semiconductors upon femtosecond laser pulse irradiation sequences

The formation of laser-induced periodic surface structures (LIPSS) upon irradiation of fused silica and silicon with multiple (N _DPS) irradiation sequences consisting of linearly polarized femtosecond laser pulse pairs (pulse duration ～150 fs, central wavelength ～800 nm) is studied experimentally. Nearly equal-energy double-pulse sequences are generated allowing the temporal pulse delay Δt between the cross-polarized individual fs-laser pulses to be varied from ?40 ps to +40 ps with a resolution of ～0.2 ps. The surface morphologies of the irradiated surface areas are characterized by means of scanning electron and scanning force microscopy. Particularly for dielectrics in the sub-ps delay range striking differences in the orientation and spatial characteristics of the LIPSS can be observed. For fused silica, a significant decrease of the LIPSS spatial periods from ～790 nm towards ～550 nm is demonstrated for delay changes of less than ～2 ps. In contrast, for silicon under similar irradiation conditions, the LIPSS periods remain constant (～760 nm) for delays up to 40 ps. The results prove the impact of laser-induced electrons in the conduction band of the solid and associated transient changes of the optical properties on fs-LIPSS formation.