Femtosecond Laser-induced Periodic Surface Structures Research Articles

Superhydrophobic/-philic SERS Platform Based on Femtosecond Laser-Induced Periodic Surface Structures and Ag Nanoparticles

Superhydrophobic/-philic SERS Platform Based on Femtosecond Laser-Induced Periodic Surface Structures and Ag Nanoparticles

Energy–dependent femtosecond LIPSS on germanium and application in explosives sensing

Abstract In this study, we fabricated laser-induced periodic surface structures (LIPSS) on a germanium surface through laser ablation in air using axicon and femtosecond (fs) pulses. This novel approach permitted the nanoscale material processing outcome refinement via an fs Bessel beam. Our investigations aimed at systematically understanding the formation of periodic structures under various experimental conditions, such as (i) different pulse energies ranging from 50 µJ to 1000 µJ at a constant scan speed and (ii) constant energy with different scan speeds (0.1–3 mm s−1). By adjusting the fluences and scan speeds, we were able to identify the parametric space and alter the periodicity of the low-spatial frequency LIPSS and high-spatial frequency LIPSS on germanium, which were analyzed using field emission scanning electron microscopy. An optimal LIPSS formation over a large area of germanium was achieved at an input energy of 250 µJ and a scan speed of 0.75 mm s−1. Additionally, we measured the contact angles of the Ge nanostructures (GeNSs) to demonstrate their hydrophobic nature and non-wetting properties, providing insights into the behavior of LIPSS. Subsequently, the GeNSs were coated with a ∼15 nm thick gold (Au) film using a thermal deposition method. Utilizing these, the surface-enhanced Raman spectroscopy (SERS) technique detected diverse analytes, such as tetryl (an explosive) at a concentration of 50 µM and thiram (a pesticide) at 500 nM. The SERS enhancement factors for tetryl and thiram molecules on GeNSs coated with a 15 nm-thick Au layer were determined to be 2.5 × 104 and 4.2 × 105, respectively.

Simulation of femtosecond laser-induced periodic surface structures on fused silica by considering intrapulse and interpulse feedback

The formation of laser-induced periodic surface structures (LIPSSs) on fused silica upon irradiation with plane wave, double pulse, spot processing, and scanning processing (pulse duration tp = 35 fs, center wavelength λ = 800 nm, low repetition rate ≈1 kHz) is studied theoretically with an improved three-dimensional finite-difference time-domain plasma model. The model covers both intrapulse feedback under single shot and interpulse feedback under multi-shots, thus enabling better prediction of transient responses during laser–material interaction and the evolution of the ablated morphology and accumulated defects’ density with more shots. In simulations of a single plane wave, a double pulse can modulate LIPSS periodicity. In simulations of spot processing with Gaussian beam, an increase in the number of shots results in a noticeable ablation pattern where high-spatial-frequency LIPSS surrounds low-spatial-frequency LIPSS at a fluence of 2.8 J/cm2. Moreover, simulations of scanning processing with Gaussian beam showcase the broad applicability of this model, revealing that the orientation of the LIPSS depends on the polarization direction rather than the scanning path. This new model provides a powerful tool to simulate the formation of LIPSS on silica, particularly when temporally modulated laser is involved or predicting the evolution of morphology dependent on the number of shots.

Controlling the morphologies of femtosecond laser-induced periodic surface structure on silicon by combining deep learning with energy deposition model

As an important patterning method, femtosecond laser-induced periodic surface structure (LIPSS) has attracted widespread attention in recent years. Due to the complex physical processes involved in the femtosecond laser scanning process, it is difficult to predict the required LIPSS morphologies, which hinders rapid customization of the large-area LIPSS patterns. In this study, a structural optimization method combining data-driven deep learning with energy deposition model was proposed to control LIPSS morphologies of silicon. After femtosecond laser processing under dynamic irradiation condition, four LIPSS morphological types were well defined based on experimental results. Deep learning model was constructed to extract data features by labeling and encoding sample data. The accuracy of self-correlation validation reached 98.0% and the accuracy of cross-correlation validation reached 91.9%. Our results show that the distribution of LIPSS morphological types exhibits the dependence of energy deposition, which is the joint effect of the effective pulse number and accumulative fluence. Moreover, the period of groove (super-wavelength LIPSS) increases with the increase of energy deposition, while the period of LSFL (low spatial frequency LIPSS) slightly decreases with the increase of energy deposition. Through this structural optimization method, customization and online monitoring of large-area LIPSS patterns in the future industrial applications.

Formation and modulation of multi-pulse femtosecond laser-induced periodic surface structures by electromagnetic and partial differential equation simulations.

In order to demonstrate the formation of laser-induced periodic surface structures (LIPSS), simulations were performed to investigate the effect of multiple femtosecond laser pulses with different laser energy densities on a Ti6Al4V surface. In this work, a set of partial differential equations calculating the electron and lattice temperature variations, followed by coupling with an electric field, is used to analyze the evolution of the periodic surface structure induced by the interaction of the femtosecond laser with the material. As the number of pulses increases, the surface structure of the material changes from none to produce LIPSS structure and from low spatial frequency LIPSS (LSFL) structure to high spatial frequency LIPSS (HSFL) structure. In order to compare the results, single-point laser scanning ablation experiments were carried out at femtosecond laser energy. The experimental results are consistent with the simulation results.

Formation of laser-induced periodic surface structures on Zr-based bulk metallic glasses with different chemical composition

Bulk metallic glasses (BMG) are amorphous metal alloys known for their unique physical and mechanical properties. In the present study, the formation of femtosecond (fs) laser-induced periodic surface structures (LIPSS) on the Zr-based BMGs Zr46Cu46Al8, Zr61Cu25Al12Ti2, Zr52.5Cu17.9Al10Ni14.6Ti5 (Vit105) and Zr57Cu15.4Al10Ni12.6Nb5 (Vit106) was investigated as a function of their different chemical composition. For this purpose, LIPSS were generated on the sample surfaces in an air environment by fs-laser irradiation (λ = 1025 nm, τ = 300 fs, frep = 100 kHz). The surface topography was characterized by scanning electron microscopy and atomic force microscopy. Moreover, the impact of LIPSS formation on the structure and chemical surface composition was analyzed before and after fs-laser irradiation by X-ray diffraction and X-ray photoelectron spectroscopy as well as by transmission electron microscopy in combination with energy dispersive X-ray spectroscopy. Despite the different chemical composition of the investigated BMGs, the fs-laser irradiation resulted in almost similar properties of the generated LIPSS patterns. In the case of Zr61Cu25Al12Ti2, Vit105 and Vit106, the surface analysis revealed the preservation of the amorphous state of the materials during fs-laser irradiation. The study demonstrated the presence of a native oxide layer on all pristine BMGs. In addition, fs-laser irradiation results in the formation of laser-induced oxide layers of larger thickness consisting of an amorphous ZrAlCu-oxide. The precise laser-structuring of BMG surfaces on the nanoscale provides a versatile alternative to thermoplastic forming of BMG surfaces and is of particular interest for the engineering of functional material surfaces.

Femtosecond Laser-Induced Periodic Surface Structures in Titanium-Doped Diamond-like Nanocomposite Films: Effects of the Beam Polarization Rotation.

We study the properties of laser-induced periodic surface structures (LIPSS) formed on titanium-doped diamond-like nanocomposite (DLN) a-C:H:Si:O films during ablation processing with linearly-polarized beams of a visible femtosecond laser (wavelength 515 nm, pulse duration 320 fs, pulse repetition rates 100 kHz-2 MHz, scanning beam velocity 0.05-1 m/s). The studies are focused on (i) laser ablation characteristics of Ti-DLN films at different pulse frequencies and constant fluence close to the ablation threshold, (ii) effects of the polarization angle rotation on the properties of low spatial frequency LIPSS (LSFL), and (iii) nanofriction properties of the 'rotating' LIPSS using atomic force microscopy (AFM) in a lateral force mode. It is found that (i) all LSFL are oriented perpendicular to the beam polarization direction, so being rotated with the beam polarization, and (ii) LSFL periods are gradually changed from 360 ± 5 nm for ripples parallel to the beam scanning direction to 420 ± 10 nm for ripples formed perpendicular to the beam scanning. The obtained results are discussed in the frame of the surface plasmon polaritons model of the LIPSS formation. Also, the findings of the nanoscale friction behavior, dependent on the LIPSS orientation relative to the AFM tip scanning direction, are presented and discussed.

Heat accumulation effects in femtosecond laser-induced subwavelength periodic surface structures on silicon

High-repetition rate femtosecond lasers are shown to drive heat accumulation processes that are attractive for femtosecond laser-induced subwavelength periodic surface structures on silicon. Femtosecond laser micromachining is no longer a nonthermal process, as long as the repetition rate reaches up to 100 kHz due to heat accumulation. Moreover, a higher repetition rate generates much better defined ripple structures on the silicon surface, based on the fact that accumulated heat raises lattice temperature to the melting point of silicon (1687 K), with more intense surface plasmons excited simultaneously. Comparison of the surface morphology on repetition rate and on the overlapping rate confirms that repetition rate and pulse overlapping rate are two competing factors that are responsible for the period of ripple structures. Ripple period drifts longer because of a higher repetition rate due to increasing electron density; however, the period of laser structured surface is significantly reduced with the pulse overlapping rate. The Maxwell–Garnett effect is confirmed to account for the ripple period-decreasing trend with the pulse overlapping rate.

Gold nanoparticles coated LIPSS on GaAs for trace detection of RDX and Tetryl

Femtosecond laser-induced periodic surface structures (LIPSS) on GaAs were accomplished using ablation in the air by varying the input pulse energy (5–100 μJ). A single laser scan line was drawn at each energy, and sub-wavelength LIPSS were observed within each line. Their morphology was thoroughly analysed, and their formation mechanisms were discussed with appropriate theoretical support (SIPE-Drude model). These GaAs-LIPSS have good quality over large ablation areas, and the periodicity (663±16 nm) was nearly the same for all energies. Further, a set of GaAs-LIPSS was produced within an area of 2 × 2 mm2 utilizing an optimized energy of 5 μJ. Photoluminescence and Raman studies were performed to understand the laser-induced damage on these structures. Subsequently, these samples were coated with a 25 nm Au layer and annealed at 400 °C in ambience. The resulting plasmonic Au nanoparticles decorated GaAs-LIPSS were used as SERS substrates for detecting dye (MB) and explosive (RDX, Tetryl) molecules. Enhancement factors of ∼105 and ∼104 (lowest detected concentrations of 10−9 M and 10−5 M) were recorded for dye and explosive molecules, respectively. We believe that these results will aid in further developing GaAs-LIPSS with smaller feature sizes for improved sensing and optoelectronic applications.

Femtosecond Laser Fabrication of Anisotropic Structures in Phosphorus- and Boron-Doped Amorphous Silicon Films.

Femtosecond laser-modified amorphous silicon (a-Si) films with optical and electrical anisotropy have perspective polarization-sensitive applications in optics, photovoltaics, and sensors. We demonstrate the formation of one-dimensional femtosecond laser-induced periodic surface structures (LIPSS) on the surface of phosphorus- (n-a-Si) and boron-doped (p-a-Si) amorphous silicon films. The LIPSS are orthogonal to the laser polarization, and their period decreases from 1.1 ± 0.1 µm to 0.84 ± 0.07 µm for p-a-Si and from 1.06 ± 0.03 to 0.98 ± 0.01 for n-a-Si when the number of laser pulses per unit area increases from 30 to 120. Raman spectra analysis indicates nonuniform nanocrystallization of the irradiated films, with the nanocrystalline Si phase volume fraction decreasing with depth from ~80 to ~40% for p-a-Si and from ~20 to ~10% for n-a-Si. LIPSS' depolarizing effect, excessive ablation of the film between LIPSS ridges, as well as anisotropic crystalline phase distribution within the film lead to the emergence of conductivity anisotropy of up to 1 order for irradiated films. Current-voltage characteristic nonlinearity observed for modified p-a-Si samples may be associated with the presence of both the crystalline and amorphous phases, resulting in the formation of potential barriers for the in-plane carrier transport and Schottky barriers at the electric contacts.

Controlling LIPSS formation on Ni surface using near-infrared laser beam and its low-order harmonics

Ultrafast laser ablation of metal surfaces is a common physical process used to generate periodic surface structures with tuneable multifunctionality for various applications in science and technology. In this work, the formation of femtosecond laser-induced periodic surface structures (LIPSSs) is investigated with 50 kHz repetition rate laser of 40 fs pulse duration and a central wavelength () along with its second () and third ) harmonic components. The variation in the LIPSS periodicity is demonstrated by changing the wavelength of the ablating laser pulses. LIPSS with periodicity ∼0.85 m at the fundamental ablating pulses, ∼0.42 m periodicity at the second harmonic, and ∼0.35 m periodicity at the third harmonic were observed. The third harmonic radiation was generated in an air-filament with minimal temporal delay with respect to the fundamental driving pulses to structure Nickel surfaces at ambient conditions. The approach demonstrates the potential for generating very fine LIPSS on materials’ surfaces using the efficient high-order harmonics of an infrared fundamental laser beam.

Functional Performance of Silicon with Periodic Surface Structures Induced by Femtosecond Pulsed Laser

A micro/nano surface structure can produce specific properties, such as super hydrophilicity, low reflectance property, etc. A femtosecond laser-induced periodic surface structure is an important manufacturing process for the micro/nano structure. This research investigated the effects of scanning intervals and laser power on the surface morphology, wetting properties, and reflectance properties of LIPSS based on a silicon wafer. The results showed that the laser power had a significant effect on the surface morphology and wettability of silicon. With the increase of laser power, the surface roughness, etching depth and surface hydrophilicity increased. However, the laser power had little effect on the surface reflectance. The scanning interval had a great influence on the wettability and reflectance property of silicon. With the decrease of the scanning interval, the surface hydrophobicity and reflectance of silicon first decrease and then remain basically stable from 10 μm.

Electromagnetic origin of femtosecond laser-induced periodic surface structures on GaP crystals.

The formations of different types of laser-induced periodic surface structures (LIPSS) on the surface of GaP crystals with different laser fluence are researched in experiments. The transition from the high spatial frequency LIPSS (HSFL) to the low spatial frequency LIPSS (LSFL) occurred as the number of the irradiated laser pulse increased. The finite difference time domain method combined with the holographic ablation model is used to simulate the LIPSS formation under the irradiation of multiple pulses. Different types of ripples are predicted by the electromagnetic approach. Results demonstrate that the electromagnetic origins of HSFL and LSFL are due to the interference of incident field and the scattering field under the multi-pulse irradiation.

Effects of supra-wavelength periodic structures on the formation of 1D/2D periodic nanostructures by femtosecond lasers

Femtosecond laser-induced periodic surface structure (fs-LIPSS) is a high-throughput parallel laser patterning method to fabricate various surface structures of sub-micrometer scale; the morphology and regularity of the structured surface determine its function. In this paper, single and double femtosecond laser beams are used to fabricate nanostructures on a silicon substrate. In the experiments, it is found that the appearance of supra-wavelength structures with periods longer than the laser wavelength not only deteriorate the regularity of the sub-wavelength periodic ripples but also hinder the fabrication of the deep sub-wavelength ripples when a single femtosecond laser is used. In addition, when double time-delayed femtosecond laser beams are used, 2D nanostructures, such as hexagonally arranged nano-hole array, cannot be fabricated once the supra-wavelength structures appear. The formation mechanism of the supra-wavelength periodic structures, which cannot be explained by the interference between the incident laser and surface plasmon polaritons, may be attributed to the hydrothermal wave on the molten surface layer. These findings provide insights to understand the mechanisms of 1D and 2D nanostructures produced by single and dual femtosecond laser beams, which is critical for fabricating functional surfaces.

Femtosecond LIPSS on indium-tin-oxide thin films at IR wavelengths.

We investigated laser-induced periodic surface structures (LIPSS) generated on indium-tin-oxide thin films with femtosecond laser pulses in the infrared region. Using pulses between 1.6 and 2.4 µm central wavelengths, we observed robust LIPSS morphologies with a periodicity close to λ/10. Supporting finite-difference time-domain calculations suggests that the surface forms are rooted in the field localization in the surface pits leading to a periodically increased absorption of the laser pulse energy that creates the observed periodic structures.

Controlled periodicities of ladder-like structures via femtosecond laser of wavelength from 400 nm to 2200 nm

A special type of femtosecond laser-induced periodic surface structures (LIPSS) combined of low spatial frequency LIPSS (LSFL) and high spatial frequency LIPSS (HSFL) are fabricated simultaneously on a stainless-steel surface. These LSFL and embedded HSFL are oriented orthogonal to each other and appear like a ladder-like structure. The periodicity of these structures is systematically controlled by varying the wavelength covering a broad range from 400 nm to 2200 nm. This work demonstrates that the LSFL periodicities can be varied from λ/1.7 to λ/4.7 with the increase in wavelength. We demonstrated the control of HSFL periodicities is possible anywhere from 44 nm to 95 nm (λ/8 to λ/30). Our results show that the LSFL periodicities vary linearly with wavelengths up to 1500 nm. However, at higher wavelengths, the LSFL periodicities cannot increase beyond a maximum limit, suggesting some possible constraints in forming surface plasmon mode frequencies. Similar behavior is observed in the formation of HSFL periodicities with wavelength variation, suggesting that the embedded HSFL periodicities depend on the primary LSFL formations. These new experimental insights will help to understand several existing theories or develop new theoretical models that describe the formation of the LIPSS. We demonstrated the fabrication of controlled ladder-like structures with LSFL spatial periodicity from 240 nm to 780 nm on stainless steel surfaces. The desired periodic structures can be printed on any large area, with a plethora of applications in science and industry.

High-efficiency-and-quality nanostructuring of molybdenum surfaces by orthogonally polarized blue femtosecond lasers

Femtosecond laser-induced periodic surface structures featured by a mask-free and one-step procedure provide a new fascinating prospect for the high precision manufacture applicable to diverse materials, but still face challenges in both the fabrication efficiency and the structure quality. Here, a homogenous large-area nanolithography is implemented on molybdenum surface, through using cylindrical focusing of double temporally delayed blue femtosecond lasers with orthogonal polarizations. The achieved grating structures present some unique features including the ablated narrow groove width of 100 nm, the small period of 245 nm, the smooth ridge profiles, and especially the uniform distribution in a mm-scaled range without bending, spitting and interruption. The calculated structure orientation angle shows an unprecedentedly minimum dispersion value of 5°, indicting a significant improvement on the structure uniformity compared with the observations of the single-beam femtosecond laser irradiation. The simulation results reveal that the transient spatiotemporal correlations between the localized electromagnetic field distributions from the double orthogonally polarized laser pulses constitutes a positive feedback mechanism to regularize the growth of the surface structures. A macro-sized surface pattern of such uniform structures displays good monochromatic colors and excellent broadband antireflection performances. This efficient laser nanolithography facilitates the applications in the fields of nanooptics.

Multi-Angular Colorimetric Responses of Uni- and Omni-Directional Femtosecond Laser-Induced Periodic Surface Structures on Metals.

We investigated the colorimetric behaviors of metal surfaces with unidirectional low-spatial-frequency laser-induced periodic surface structures (UD-LSFLs) and omnidirectional LSFLs (OD-LSFLs) fabricated using femtosecond laser pulse irradiation. With the CIE standard illuminant D65, incident at −45°, we show that UD-LSFLs on metals transform polished metals to gonio-apparent materials with a unique behavior of colorimetric responses, depending on both the detection and rotation angles, whereas OD-LSFLs have nearly uniform gonio-apparent colors at each detection angle, regardless of their rotation. These colorimetric behaviors can be observed not only at the angles of diffraction but also near the angle of reflection, and we find that the power redistribution due to Rayleigh anomalies also plays an important role in the colorimetric responses of UD- and OD-LSFLs, in addition to diffraction.

Extremely regular periodic surface structures in a large area efficiently induced on silicon by temporally shaped femtosecond laser

Femtosecond laser-induced periodic surface structures (LIPSS) have several applications in surface structuring and functionalization. Three major challenges exist in the fabrication of regular and uniform LIPSS: enhancing the periodic energy deposition, reducing the residual heat, and avoiding the deposited debris. Herein, we fabricate an extremely regular low-spatial-frequency LIPSS (LSFL) on a silicon surface by a temporally shaped femtosecond laser. Based on a 4 f configuration zero-dispersion pulse shaping system, a Fourier transform limit (FTL) pulse is shaped into a pulse train with varying intervals in the range of 0.25–16.2 ps using periodic π -phase step modulation. Under the irradiation of the shaped pulse with an interval of 16.2 ps, extremely regular LSFLs are efficiently fabricated on silicon. The scan velocity for fabricating regular LSFL is 2.3 times faster, while the LSFL depth is 2 times deeper, and the diffraction efficiency is 3 times higher than those of LSFL using the FTL pulse. The formation mechanisms of regular LSFL have been studied experimentally and theoretically. The results show that the temporally shaped pulse enhances the excitation of surface plasmon polaritons and the periodic energy deposition while reducing the residual thermal effects and avoiding the deposition of the ejected debris, eventually resulting in regular and deeper LSFL on the silicon surface.

Numerical FDTD-based simulations and Raman experiments of femtosecond LIPSS.

The article describes the results of finite-difference time-domain (FDTD) mathematical modeling of electric field strength distribution near the gold laser-induced periodic surface structures (LIPSS). Both theoretical and experimental results have been described for two fabricated morphologies: round «hill-like» and grating structures. The structures were fabricated by using a femtosecond Yb-fiber laser with a wavelength of λ=1032 nm, pulse duration τ=280 fs, and repetition rate υ=25 kHz. Morphological properties of the surfaces have been investigated by means of scanning electron microscopy (SEM). The plasmonic activity was analyzed by means of the surface-enhanced Raman spectroscopy (SERS) technique. FDTD-calculated electric field values were converted into the electromagnetic field enhancement coefficient and the theoretical SERS intensity. The prospects of the theoretical approach for LIPSS to evaluate optimal field amplification and light scattering parameters has been shown. The presented approach could be applied as a basis for performing the methods of controlled synthesis for LIPPS.