Controllable Fabrication of Hydrophilic Surface Micro/Nanostructures of CFRP by Femtosecond Laser.

Carbon fiber reinforced polymer (CFRP), a highly engineered lightweight material with superior properties, is widely used in industrial fields, such as aerospace, automobile, and railway transportation, as well as medical implants and supercapacitor. This work presents an effective surface treatment method for the controllable fabrication of hydrophilic surface micro/nanostructures of CFRP through femtosecond laser processing. Selective removal of the epoxy resin and leaving the carbon fibers exposed are achieved when CFRP is weakly ablated by a femtosecond laser. The diameters and structures of the carbon fibers can be controlled by adjusting the laser processing parameters. Three-dimensional surface micro/nanostructures are processed when CFRP is strongly ablated by a femtosecond laser. Meanwhile, the transformation of the sp2 orbitals to sp3 orbitals of graphitic carbons of carbon fibers is induced by a femtosecond laser. Moreover, the investigation of surface roughness and wettability of femtosecond laser-processed CFRP indicates increased roughness and excellent hydrophilicity (a contact angle of 28.1°). This work reveals the effect of femtosecond laser processing on the regulation of the physicochemical properties of CFRP, which can be applicable to surface treatment and performance control of other fiber-resin composites. The excellent hydrophilicity will be conducive to the combination of CFRP with other materials or to reducing the friction resistance of CFRP used in medical implants.

Femtosecond UV Laser Ablation Characteristics of Polymers Used as the Matrix of Astronautic Composite Material.

Ultrafast laser processing has recently emerged as a new tool for processing fiber-reinforced polymer (FRP) composites. In the astronautic industry, the modified epoxy resin (named 4211) and the modified cyanate ester resin (known as BS-4) are two of the most widely used polymers for polymer-based composites. To study the removal mechanism and ablation process of different material components during the ultrafast laser processing of FRPs, we isolated the role of the two important polymers from their composites by studying their femtosecond UV laser (260 fs, 343 nm) ablation characteristics for controllable machining and understanding the related mechanisms. Intrinsic properties for the materials' transmission spectrum, the absorption coefficient and the optical bandgap (Eg), were measured, derived, and compared. Key parameters for controllable laser processing, including the ablation threshold (Fth), energy penetration depth (δeff), and absorbed energy density (Eabs) at the ablation threshold, as well as their respective "incubation" effect under multiple pulse excitations, were deduced analytically. The ablation thresholds for the two resins, derived from both the diameter-regression and depth-regression techniques, were compared between resins and between techniques. An optical bandgap of 3.1 eV and 2.8 eV for the 4211 and BS-4 resins, respectively, were obtained. A detectable but insignificant-to-ablation difference in intrinsic properties and ablation characteristics between the two resins was found. A systematic discrepancy, by a factor of 30~50%, between the two techniques for deriving ablation thresholds was shown and discussed. For the 4211 resin ablated by a single UV laser pulse, a Fth of 0.42 J/cm2, a δeff of 219 nm, and an Eabs of 18.4 kJ/cm3 was suggested, and they are 0.45 J/cm2, 183 nm, and 23.2 kJ/cm3, respectively, for the BS-4 resin. The study may shed light on the materials' UV laser processing, further the theoretical modeling of ultrafast laser ablation, and provide a reference for the femtosecond UV laser processing characteristics of FRPs for the future.

High-throughput microchannel fabrication in fused silica by temporally shaped femtosecond laser Bessel-beam-assisted chemical etching.

We proposed combining temporally shaped (double-pulse train) laser pulses with spatially shaped (Bessel beam) laser pulses. By using a temporally shaped femtosecond laser Bessel-beam-assisted chemical etching method, the energy deposition efficiency was improved by adjusting the pulse delay to yield a stronger material modification and, thus, a higher etching depth. The etching depth was enhanced by a factor of 13 using the temporally shaped Bessel beam. The mechanism of etching depth enhancement was elucidated by localized transient-free electrons dynamics-induced structural and morphological changes. Micro-Raman spectroscopy was conducted to verify the structural changes inside the material. This method enables high-throughput, high-aspect-ratio microchannel fabrication in fused silica for potential applications in microfluidics.

Structure-Mediated Excitation of Air Plasma and Silicon Plasma Expansion in Femtosecond Laser Pulses Ablation.

Femtosecond laser-induced surface structures upon multiple pulses irradiation are strongly correlated with the pulse number, which in turn significantly affects successive laser-material interactions. By recording the dynamics of femtosecond laser ablation of silicon using time-resolved shadowgraphy, here we present direct visualization of the excitation of air plasma induced by the reflected laser during the second pulse irradiation. The interaction of the air plasma and silicon plasma is found to enhance the shockwave expansion induced by silicon ablation in the longitudinal direction, showing anisotropic expansion dynamics in different directions. We further demonstrate the vanishing of air plasma as the pulse number increases because of the generation of a rough surface without light focusing ability. In the scenario, the interaction of air plasma and silicon plasma disappears; the expansion of the silicon plasma and shockwave restores its original characteristic that is dominated by the laser-material coupling. The results show that the excitation of air plasma and the laser-material coupling involved in laser-induced plasma and shockwave expansion are structure mediated and dependent on the pulse number, which is of fundamental importance for deep insight into the nature of laser-material interactions during multiple pulses ablation.

Nanoscale material redistribution induced by spatially modulated femtosecond laser pulses for flexible high-efficiency surface patterning.

In this paper, we investigated the material redistribution phenomenon controlled by spatially modulated femtosecond laser pulses on a silicon surface. The intensity distribution was shaped by using a spatial light modulator. The material was first selectively melted and then redistributed by the laser-induced plasma. Thus, complex surface patterns were formed conformal to the laser intensity distribution. Sub-diffraction-limit size can be achieved due to the nanoscale material redistribution. Only one pulse was needed in the surface patterning process, thus greatly favoring the efficiency improvement. Combined with multibeam interference, a large-scale nanostructure array can be fabricated with high efficiency of 1600 µm2/pulse. This method offers a simple, flexible and efficient alternative approach for nanoscale surface patterning applications.

Controllable high-throughput high-quality femtosecond laser-enhanced chemical etching by temporal pulse shaping based on electron density control.

We developed an efficient fabrication method of high-quality concave microarrays on fused silica substrates based on temporal shaping of femtosecond (fs) laser pulses. This method involves exposures of fs laser pulse trains followed by a wet etching process. Compared with conventional single pulses with the same processing parameters, the temporally shaped fs pulses can enhance the etch rate by a factor of 37 times with better controllability and higher quality. Moreover, we demonstrated the flexibility of the proposed method in tuning the profile of the concave microarray structures by changing the laser pulse delay, laser fluence, and pulse energy distribution ratio. Micro-Raman spectroscopy was conducted to elucidate the stronger modification induced by the fs laser pulse trains in comparison with the single pulses. Our calculations show that the controllability is due to the effective control of localized transient free electron densities by temporally shaping the fs pulses.

Gold-film coating assisted femtosecond laser fabrication of large-area, uniform periodic surface structures.

A simple, repeatable approach is proposed to fabricate large-area, uniform periodic surface structures by a femtosecond laser. 20 nm gold films are coated on semiconductor surfaces on which large-area, uniform structures are fabricated. In the case study of silicon, cross-links and broken structures of laser induced periodic surface structures (LIPSSs) are significantly reduced on Au-coated silicon. The good consistency between the scanning lines facilitates the formation of large-area, uniform LIPSSs. The diffusion of hot electrons in the Au films increases the interfacial carrier densities, which significantly enhances interfacial electron-phonon coupling. High and uniform electron density suppresses the influence of defects on the silicon and further makes the coupling field more uniform and thus reduces the impact of laser energy fluctuations, which homogenizes and stabilizes large-area LIPSSs.

Nanopillar arrays with nanoparticles fabricated by a femtosecond laser pulse train for highly sensitive SERRS.

This work presents a novel method for fabricating repeatable, uniform, large-area, highly sensitive, surface-enhanced resonance Raman scattering (SERRS) substrates combined with silicon nanopillar arrays and silver nanoparticles. The proposed method consists of two steps: (1) induce periodic ripples in deionized water using a linearly polarized femtosecond laser; and (2) generate dense 80-nm-diameter nanopillar arrays with silver nanoparticles in silver nitrate solution with a 90° rotated polarization, femtosecond double-pulse train. As the pulse delay increases from 0 to 1000 fs, the mean size of the silver nanoparticles reduces, and the average number of nanoparticles increases, which, in turn, increases the enhancement factor of SERRS signals up to 1.1×10(9). Furthermore, melamine (down to 125 ppb) was detected by the fabricated SERRS substrates.

Production rate enhancement of size-tunable silicon nanoparticles by temporally shaping femtosecond laser pulses in ethanol.

This paper proposes an efficient approach for production-rate enhancement and size reduction of silicon nanoparticles produced by femtosecond (fs) double-pulse ablation of silicon in ethanol. Compared with a single pulse, the production rate is ~2.6 times higher and the mean size of the NPs is reduced by ~1/5 with a delay of 2 ps. The abnormal enhancement in the production rate is obtained at pulse delays Δt > 200 fs. The production-rate enhancement is mainly attributed to high photon absorption efficiency. It is caused by an increase in localized transient electron density, which results from the first sub-pulse ionization of ethanol molecules before the second sub-pulse arrives. The phase-change mechanism at a critical point might reduce nanoparticle size.

Femtosecond laser high-efficiency drilling of high-aspect-ratio microholes based on free-electron-density adjustments.

We studied the micromachining of high-aspect-ratio holes in poly(methylmethacrylate) using a visible double-pulse femtosecond laser based on free-electron-density adjustments. Hole depth and aspect ratio increased simultaneously upon decreasing the wavelength in the visible-light zone. When the pulse energy reached a high level, the free-electron density was adjusted by using a double-pulse laser, which induced fewer free electrons, a lower reflectivity plasma plume, and more pulse energy deposition in the solid bottom. Thus, the aspect ratio of the hole was improved considerably. At a moderate pulse energy level, a 1.3-1.4 times enhancement of both the ablation depth and the aspect ratio was observed when the double-pulse delay was set between 100 and 300 fs, probably due to an enhanced photon-electron coupling effect through adjusting the free-electron density. At a lower pulse energy level, this effect also induced the generation of a submicrometer string. In addition, the ablation rate was improved significantly by using visible double pulses.

Doping effects on ablation enhancement in femtosecond laser irradiation of silicon.

We have conducted an experimental investigation on highly efficient femtosecond laser micromachining of silicon through N-type doping. We found that the material removal amount has a close relationship with the doping concentration rather than with the doping types. The amount of material removal was enhanced gradually as doping densities increased. When the doping density reached higher than 10(18) cm(-3), the ablation threshold was considerably reduced, up to 15%-20%. The results of the experiment indicate that the high density of initial free electrons by doping is the fundamental reason for efficiency improvement, and bandgap shrinkage also plays an important role. The electrons are excited more easily from the valance band to the conduction band and acquire higher initial kinetic energy, which then promotes the material ablation process.

Generation and elimination of polarization-dependent ablation of cubic crystals by femtosecond laser radiation.

We experimentally showed that the π/2-period oscillation of an ablation area with laser polarization direction can be observed in GaAs, ZnSe, MgO and LiF with cubic crystal by a femtosecond laser (800 nm, 100 fs) and that the modulation in the ablation area can be controlled by the laser fluence. While the polarization dependence is sustained in a wide range of laser fluences for a narrow band-gap crystal, it is strongly suppressed with a slight augmentation of laser fluence in a wide band-gap material. The polarization-dependent ablation is explained by the crystal's orientation-dependent reduced-electron mass and the resultant contrasting nonlinear absorptions with slightly different reduced electron mass. The interplay between photoionization and avalanche ionization is discussed to interpret the influence of laser fluence on polarization-dependent ablation. Based on Keldysh's theory, polarization-dependent ablation occurs in a mixed regime between tunneling and multiphoton ionization.