Influence of Heat Accumulation on Morphology Debris Deposition and Wetting of LIPSS on Steel upon High Repetition Rate Femtosecond Pulses Irradiation.

The fabrication of laser-induced periodic surface structures (LIPSS) over extended areas at high processing speeds requires the use of high repetition rate femtosecond lasers. It is known that industrially relevant materials such as steel experience heat accumulation when irradiated at repetition rates above some hundreds of kHz, and significant debris redeposition can take place. However, there are few studies on how the laser repetition rate influences both the debris deposition and the final LIPSS morphology. In this work, we present a study of fs laser-induced fabrication of low spatial frequency LIPSS (LSFL), with pulse repetition rates ranging from 10 kHz to 2 MHz on commercially available steel. The morphology of the laser-structured areas as well as the redeposited debris was characterized by scanning electron microscopy (SEM) and µ-Raman spectroscopy. To identify repetition rate ranges where heat accumulation is present during the irradiations, we developed a simple heat accumulation model that solves the heat equation in 1 dimension implementing a Forward differencing in Time and Central differencing in Space (FTCS) scheme. Contact angle measurements with water demonstrated the influence of heat accumulation and debris on the functional wetting behavior. The findings are directly relevant for the processing of metals using high repetition rate femtosecond lasers, enabling the identification of optimum conditions in terms of desired morphology, functionality, and throughput.

Single-Step Fabrication of High-Performance Extraordinary Transmission Plasmonic Metasurfaces Employing Ultrafast Lasers.

Plasmonic metasurfaces based on the extraordinary optical transmission (EOT) effect can be designed to efficiently transmit specific spectral bands from the visible to the far-infrared regimes, offering numerous applications in important technological fields such as compact multispectral imaging, biological and chemical sensing, or color displays. However, due to their subwavelength nature, EOT metasurfaces are nowadays fabricated with nano- and micro-lithographic techniques, requiring many processing steps and carrying out in expensive cleanroom environments. In this work, we propose and experimentally demonstrate a novel, single-step process for the rapid fabrication of high-performance mid- and long-wave infrared EOT metasurfaces employing ultrafast direct laser writing. Microhole arrays composing extraordinary transmission metasurfaces were fabricated over an area of 4 mm2 in timescales of units of minutes, employing single pulse ablation of 40 nm thick Au films on dielectric substrates mounted on a high-precision motorized stage. We show how by carefully characterizing the influence of only three key experimental parameters on the processed micro-morphologies (namely, laser pulse energy, scan velocity, and beam shaping slit), we can have on-demand control of the optical characteristics of the extraordinary transmission effect in terms of transmission wavelength, quality factor, and polarization sensitivity of the resonances. To illustrate this concept, a set of EOT metasurfaces having different performances and operating in different spectral regimes has been successfully designed, fabricated, and tested. Comparison between transmittance measurements and numerical simulations has revealed that all the fabricated devices behave as expected, thus demonstrating the high performance, flexibility, and reliability of the proposed fabrication method. We believe that our findings provide the pillars for mass production of EOT metasurfaces with on-demand optical properties and create new research trends toward single-step laser fabrication of metasurfaces with alternative geometries and/or functionalities.

Femtosecond laser induced thermophoretic writing of waveguides in silicate glass.

Here in, the fs-laser induced thermophoretic writing of microstructures in ad-hoc compositionally designed silicate glasses and their application as infrared optical waveguides is reported. The glass modification mechanism mimics the elemental thermal diffusion occurring in basaltic liquids at the Earth's mantle, but in a much shorter time scale (108 times faster) and over a well-defined micrometric volume. The precise addition of BaO, Na2O and K2O to the silicate glass enables the creation of positive refractive index contrast upon fs-laser irradiation. The influence of the focal volume and the induced temperature gradient is thoroughly analyzed, leading to a variety of structures with refractive index contrasts as high as 2.5 × 10-2. Two independent methods, namely near field measurements and electronic polarizability analysis, confirm the magnitude of the refractive index on the modified regions. Additionally, the functionality of the microstructures as waveguides is further optimized by lowering their propagation losses, enabling their implementation in a wide range of photonic devices.

Preferential Growth of ZnO Micro- and Nanostructure Assemblies on Fs-Laser-Induced Periodic Structures.

In this work, we demonstrate the use of laser-induced periodic surface structures (LIPSS) as templates for the selective growth of ordered micro- and nanostructures of ZnO. Different types of LIPSS were first produced in Si-(100) substrates including ablative low-frequency spatial (LSF) LIPSS, amorphous-crystalline (a-c) LIPSS, and black silicon structures. These laser-structured substrates were subsequently used for depositing ZnO using the vapor-solid (VS) method in order to analyze the formation of organized ZnO structures. We used scanning electron microscopy and micro-Raman spectroscopy to assess the morphological and structural characteristics of the ZnO micro/nano-assemblies obtained and to identify the characteristics of the laser-structured substrates inducing the preferential deposition of ZnO. The formation of aligned assemblies of micro- and nanocrystals of ZnO was successfully achieved on LSF-LIPSS and a-c LIPSS. These results point toward a feasible route for generating well aligned assemblies of semiconductor micro- and nanostructures of good quality by the VS method on substrates, where the effect of lattice mismatch is reduced by laser-induced local disorder and likely by a small increase of surface roughness.

The Role of the Laser-Induced Oxide Layer in the Formation of Laser-Induced Periodic Surface Structures.

Laser-induced periodic surface structures (LIPSS) are often present when processing solid targets with linearly polarized ultrashort laser pulses. The different irradiation parameters to produce them on metals, semiconductors and dielectrics have been studied extensively, identifying suitable regimes to tailor its properties for applications in the fields of optics, medicine, fluidics and tribology, to name a few. One important parameter widely present when exposing the samples to the high intensities provided by these laser pulses in air environment, that generally is not considered, is the formation of a superficial laser-induced oxide layer. In this paper, we fabricate LIPSS on a layer of the oxidation prone hard-coating material chromium nitride in order to investigate the impact of the laser-induced oxide layer on its formation. A variety of complementary surface analytic techniques were employed, revealing morphological, chemical and structural characteristics of well-known high-spatial frequency LIPSS (HSFL) together with a new type of low-spatial frequency LIPSS (LSFL with an anomalous orientation parallel to the laser polarization. Based on this input, we performed finite-difference time-domain calculations considering a layered system resembling the geometry of the HSFL along with the presence of a laser-induced oxide layer. The simulations support a scenario that the new type of LSFL is formed at the interface between the laser-induced oxide layer and the non-altered material underneath. These findings suggest that LSFL structures parallel to the polarization can be easily induced in materials that are prone to oxidation.

Femtosecond x-ray diffraction reveals a liquid-liquid phase transition in phase-change materials.

In phase-change memory devices, a material is cycled between glassy and crystalline states. The highly temperature-dependent kinetics of its crystallization process enables application in memory technology, but the transition has not been resolved on an atomic scale. Using femtosecond x-ray diffraction and ab initio computer simulations, we determined the time-dependent pair-correlation function of phase-change materials throughout the melt-quenching and crystallization process. We found a liquid-liquid phase transition in the phase-change materials Ag4In3Sb67Te26 and Ge15Sb85 at 660 and 610 kelvin, respectively. The transition is predominantly caused by the onset of Peierls distortions, the amplitude of which correlates with an increase of the apparent activation energy of diffusivity. This reveals a relationship between atomic structure and kinetics, enabling a systematic optimization of the memory-switching kinetics.

Biomimetic surface structures in steel fabricated with femtosecond laser pulses: influence of laser rescanning on morphology and wettability.

The replication of complex structures found in nature represents an enormous challenge even for advanced fabrication techniques, such as laser processing. For certain applications, not only the surface topography needs to be mimicked, but often also a specific function of the structure. An alternative approach to laser direct writing of complex structures is the generation of laser-induced periodic surface structures (LIPSS), which is based on directed self-organization of the material and allows fabrication of specific micro- and nanostructures over extended areas. In this work, we exploit this approach to fabricate complex biomimetic structures on the surface of steel 1.7131 formed upon irradiation with high repetition rate femtosecond laser pulses. In particular, the fabricated structures show similarities to the skin of certain reptiles and integument of insects. Different irradiation parameters are investigated to produce the desired structures, including laser repetition rate and laser fluence, paying special attention to the influence of the number of times the same area is rescanned with the laser. The latter parameter is identified to be crucial for controlling the morphology and size of specific structures. As an example for the functionality of the structures, we have chosen the surface wettability and studied its dependence on the laser processing parameters. Contact angle measurements of water drops placed on the surface reveal that a wide range of angles can be accessed by selecting the appropriate irradiation parameters, highlighting also here the prominent role of the number of scans.

Controlling the Wettability of Steel Surfaces Processed with Femtosecond Laser Pulses.

The wettability of a material surface is an essential property that can define the range of applications it can be used for. In the particular case of steel, industrial applications are countless but sometimes limited because of the lack of control over its surface properties. Although different strategies have been proposed to tune the wetting behavior of metal surfaces, most of them require the use of processes such as coatings with different materials or plasma/chemical etching. In this work, we present two different laser-based direct-write strategies that allow tuning the wetting properties of 1.7131 steel over a wide range of contact angles using a high repetition rate femtosecond laser. The strategy consists in the writing of parallel and crossed lines with variable spacing. A detailed morphological analysis confirmed the formation of microstructures superimposed with nanofeatures, forming a hierarchical surface topography that influences the wetting properties of the material surface. Contact angle measurements with water confirm that this behavior is mostly dependent on the line-to-line spacing and the polarization-dependent orientation of the structures. Moreover, we demonstrate that the structures can be easily replicated in a polymer using a laser-fabricated steel master, which enables low-cost mass production. These findings provide a practical route for developing user-defined wetting control for new applications of steel and other materials functionalized by rapid laser structuring.

Author Correction: Coherent scatter-controlled phase-change grating structures in silicon using femtosecond laser pulses.

A correction to this article has been published and is linked from the HTML and PDF versions of this paper. The error has not been fixed in the paper.

Coherent scatter-controlled phase-change grating structures in silicon using femtosecond laser pulses.

Periodic structures of alternating amorphous-crystalline fringes have been fabricated in silicon using repetitive femtosecond laser exposure (800 nm wavelength and 120 fs duration). The method is based on the interference of the incident laser light with far- and near-field scattered light, leading to local melting at the interference maxima, as demonstrated by femtosecond microscopy. Exploiting this strategy, lines of highly regular amorphous fringes can be written. The fringes have been characterized in detail using optical microscopy combined modelling, which enables a determination of the three-dimensional shape of individual fringes. 2D micro-Raman spectroscopy reveals that the space between amorphous fringes remains crystalline. We demonstrate that the fringe period can be tuned over a range of 410 nm - 13 µm by changing the angle of incidence and inverting the beam scan direction. Fine control over the lateral dimensions, thickness, surface depression and optical contrast of the fringes is obtained via adjustment of pulse number, fluence and spot size. Large-area, highly homogeneous gratings composed of amorphous fringes with micrometer width and millimeter length can readily be fabricated. The here presented fabrication technique is expected to have applications in the fields of optics, nanoelectronics, and mechatronics and should be applicable to other materials.

Three-Dimensional Self-Organization in Nanocomposite Layered Systems by Ultrafast Laser Pulses.

Controlling plasmonic systems with nanometer resolution in transparent films and their colors over large nonplanar areas is a key issue for spreading their use in various industrial fields. Using light to direct self-organization mechanisms provides high-speed and flexible processes to meet this challenge. Here, we describe a route for the laser-induced self-organization of metallic nanostructures in 3D. Going beyond the production of planar nanopatterns, we demonstrate that ultrafast laser-induced excitation combined with nonlinear feedback mechanisms in a nanocomposite thin film can lead to 3D self-organized nanostructured films. The process, which can be extended to complex layered composite systems, produces highly uniform large-area nanopatterns. We show that 3D self-organization originates from the simultaneous excitation of independent optical modes at different depths in the film and is activated by the plasmon-induced charge separation and thermally induced NP growth mechanisms. This laser color marking technique enables multiplexed optical image encoding and the generated nanostructured Ag NPs:TiO2 films offer great promise for applications in solar energy harvesting, photocatalysis, or photochromic devices.

Femtosecond laser-controlled self-assembly of amorphous-crystalline nanogratings in silicon.

Self-assembly (SA) of molecular units to form regular, periodic extended structures is a powerful bottom-up technique for nanopatterning, inspired by nature. SA can be triggered in all classes of solid materials, for instance, by femtosecond laser pulses leading to the formation of laser-induced periodic surface structures (LIPSS) with a period slightly shorter than the laser wavelength. This approach, though, typically involves considerable material ablation, which leads to an unwanted increase of the surface roughness. We present a new strategy to fabricate high-precision nanograting structures in silicon, consisting of alternating amorphous and crystalline lines, with almost no material removal. The strategy can be applied to static irradiation experiments and can be extended into one and two dimensions by scanning the laser beam over the sample surface. We demonstrate that lines and areas with parallel nanofringe patterns can be written by an adequate choice of spot size, repetition rate and scan velocity, keeping a constant effective pulse number (N eff) per area for a given laser wavelength. A deviation from this pulse number leads either to inhomogeneous or ablative structures. Furthermore, we demonstrate that this approach can be used with different laser systems having widely different wavelengths (1030 nm, 800 nm, 400 nm), pulse durations (370 fs, 100 fs) and repetition rates (500 kHz, 100 Hz, single pulse) and that the grating period can also be tuned by changing the angle of laser beam incidence. The grating structures can be erased by irradiation with a single nanosecond laser pulse, triggering recrystallization of the amorphous stripes. Given the large differences in electrical conductivity between the two phases, our structures could find new applications in nanoelectronics.

Nanofabrication of tailored surface structures in dielectrics using temporally shaped femtosecond-laser pulses.

We have investigated the use of tightly focused, temporally shaped femtosecond (fs)-laser pulses for producing nanostructures in two dielectric materials (sapphire and phosphate glass) with different characteristics in their response to pulsed laser radiation. For this purpose, laser pulses shaped by third-order dispersion (TOD) were used to generate temporally asymmetric excitation pulses, leading to the single-step production of subwavelength ablative and subablative surface structures. When compared to previous works on the interaction of tightly focused TOD-shaped pulses with fused silica, we show here that this approach leads to very different nanostructure morphologies, namely, clean nanopits without debris surrounding the crater in sapphire and well-outlined nanobumps and nanovolcanoes in phosphate glass. Although in sapphire the debris-free processing is associated with the much lower viscosity of the melt compared to fused silica, nanobump formation in phosphate glass is caused by material network expansion (swelling) upon resolidification below the ablation threshold. The formation of nanovolcanoes is a consequence of the combined effect of material network expansion and ablation occurring in the periphery and central part of the irradiated region, respectively. It is shown that the induced morphologies can be efficiently controlled by modulating the TOD coefficient of the temporally shaped pulses.

Micro- and submicrostructuring thin polymer films with two and three-beam single pulse laser interference lithography.

In this work we report the application of two and three-beam single pulse laser interference lithography to thin polymer films of poly(trimethylene terephthalate) (PTT). By irradiating the sample surface with temporary and spatially overlapped single pulses from two or three coherent beams and changing the angles of incidence, we have accomplished the fabrication of large-area polymer micro and submicrogratings as well as submicrometric cavities arranged in a hexagonal lattice. The characterization of the structures in real space by atomic force microscopy (AFM) and scanning electron microscopy (SEM) has allowed us to determine the formation mechanism of the microgratings to be based on different ablation regimes depending on the local fluence. Moreover, complementary characterization of the submicrometric cavities in reciprocal space by grazing incidence small-angle X-ray scattering (GISAXS) confirms the existence of large areas where two-dimensional order is present. The experiments presented in this work demonstrate the suitability of single pulse laser interference lithography for micro and submicrostructuring polymer films, opening up new possibilities for patterning and paving the way for potential applications where polymer structures are involved.

Near-field nanoimprinting using colloidal monolayers.

We experimentally and theoretically explore near-field nanopatterning obtained by irradiation of hexagonal monolayers of micron-sized polystyrene spheres on photosensitive Ge(2)Sb(5)Te(5) (GST) films. The imprinted patterns are strongly sensitive to the illumination conditions, as well as the size of the spheres and the orientation of the monolayer, which we change to demonstrate control over the resulting structures. We show that the presence of multiple scattering effects cannot be neglected to describe the resulting pattern. The experimental patterns imprinted are shown to be robust to small displacements and structural defects of the monolayer. Our method enables the design and experimental verification of patterns with multiple focii per particle and complex shapes, which can be directly implemented for large scale fabrication on different substrates.

Nanostructuring thin polymer films with optical near fields.

In the present work, we report on the application of optical near fields to nanostructuring of poly(trimethylene terephthalate) (PTT) thin films. By exposure to a single ultraviolet nanosecond laser pulse, the spatial intensity modulation of the near-field distribution created by a silica microsphere is imprinted into the films. Setting different angles of incidence of the laser, elliptical or circular periodic ring patterns can be produced with periods as small as half the laser wavelength used. These highly complex patterns show optical and topographical contrast and can be characterized by optical microscopy (OM) and atomic force microscopy (AFM). We demonstrate the key role of the laser wavelength and coherence length in achieving smooth, extended patterns in PTT by using excimer laser (193 nm) and Nd:YAG laser (266 nm) pulses. Reference experiments performed in Ge2Sb2Te5 (GST) demonstrate that nanopatterning in PTT is triggered by ablation as opposed to GST, in which nanopatterning originates from laser-induced phase change, accompanied by a small topographical contrast. The experiments presented in this work demonstrate the suitability of optical near fields for structuring polymer films, opening up new possibilities for nanopatterning and paving the way for potential applications where optical near fields and polymer nanostructures are involved.

Femtosecond-resolved ablation dynamics of Si in the near field of a small dielectric particle.

In this work we analyze the ablation dynamics of crystalline Si in the intense near field generated by a small dielectric particle located at the material surface when being irradiated with an infrared femtosecond laser pulse (800 nm, 120 fs). The presence of the particle (7.9 µm diameter) leads to a strong local enhancement (ca. 40 times) of the incoming intensity of the pulse. The transient optical response of the material has been analyzed by means of fs-resolved optical microscopy in reflection configuration over a time span from 0.1 ps to about 1 ns. Characteristic phenomena like electron plasma formation, ultrafast melting and ablation, along with their characteristic time scales are observed in the region surrounding the particle. The use of a time resolved imaging technique allows us recording simultaneously the material response at ordinary and large peak power densities enabling a direct comparison between both scenarios. The time resolved images of near field exposed regions are consistent with a remarkable temporal shift of the ablation onset which occurs in the sub-picosend regime, from about 500 to 800 fs after excitation.

Quantitative imaging of the optical near field.

When exposing small particles on a substrate to a light plane wave, the scattered optical near field is spatially modulated and highly complex. We show, for the particular case of dielectric microspheres, that it is possible to image these optical near-field distributions in a quantitative way. By placing a single microsphere on a thin film of the photosensitive phase change material Ge(2)Sb(5)Te(5) and exposing it to a single short laser pulse, the spatial intensity modulation of the near field is imprinted into the film as a pattern of different material phases. The resulting patterns are investigated by using optical as well as high-resolution scanning electron microscopy. Quantitative information on the local optical near field at each location is obtained by calibrating the material response to pulsed laser irradiation. We discuss the influence of polarization and angle of incidence of the laser beam as well as particle size on the field distribution. The experimental results are in good quantitative agreement with a model based on a rigorous solution of Maxwell's equations. Our results have potential application to near-field optical lithography and experimental determination of near fields in complex nanostructures.

Effect of air-flow on the evaluation of refractive surgery ablation patterns.

An Allegretto Eye-Q laser platform (Wavelight GmbH, Erlangen, Germany) was used to study the effect of air-flow speed on the ablation of artificial polymer corneas used for testing refractive surgery patterns. Flat samples of two materials (PMMA and Filofocon A) were ablated at four different air flow conditions. The shape and profile of the ablated surfaces were measured with a precise non-contact optical surface profilometer. Significant asymmetries in the measured profiles were found when the ablation was performed with the clinical air aspiration system, and also without air flow. Increasing air-flow produced deeper ablations, improved symmetry, and increased the repeatability of the ablation pattern. Shielding of the laser pulse by the plume of smoke during the ablation of plastic samples reduced the central ablation depth by more than 40% with no-air flow, 30% with clinical air aspiration, and 5% with 1.15 m/s air flow. A simple model based on non-inertial dragging of the particles by air flow predicts no central shielding with 2.3 m/s air flow, and accurately predicts (within 2 µm) the decrease of central ablation depth by shielding. The shielding effects for PMMA and Filofocon A were similar despite the differences in the ablation properties of the materials and the different full-shielding transmission coefficient, which is related to the number of particles ejected and their associated optical behavior. Air flow is a key factor in the evaluation of ablation patterns in refractive surgery using plastic models, as significant shielding effects are found with typical air-flow levels used under clinical conditions. Shielding effects can be avoided by tuning the air flow to the laser repetition rate.

Suitability of Filofocon A and PMMA for experimental models in excimer laser ablation refractive surgery.

Experimental corneal models in plastic (in PMMA, and more recently in Filofocon A, a contact lens material) have been proposed recently to overcome some of the limitations of the theoretical approaches aiming at improving the predictability of corneal reshaping by laser ablation. These models have also been proposed for accurate assessment of corneal laser ablation patterns. In this study Filofocon A and PMMA optical and ablation properties were studied using an experimental excimer laser set-up. The effective absorption coefficient and the ablation thresholds of these materials were obtained as a function of the number of pulses. Both materials follow a Beer-Lambert law in the range of fluences used in refractive surgery, and the number of incubation pulses is less than 4 (PMMA) and 2 (Filofocon A) above 140 mJ/cm2. We found that above 40 pulses for Filofocon A and 70 pulses for PMMA, ablation threshold and effective absorption coefficients can be considered constant (F th = 90 mJ/cm2 and alpha eff = 36000 cm(-1), for Filofocon A, and F th = 67 mJ/cm2 and alpha eff = 52000 cm(-1) for PMMA, respectively). The absence of ablation artifacts (central islands), a lower number of incubation pulses, a lower pulse-number dependence of the ablation threshold, and a good correspondence between alpha eff and the absorption coefficient alpha estimated from spectroscopic measurements make Filofocon A a more appropriate material than PMMA for experimental models in refractive surgery and for calibration of clinical lasers.