Learning Complexity to Guide Light-Induced Self-Organized Nanopatterns.

Ultrafast laser irradiation can induce spontaneous self-organization of surfaces into dissipative structures with nanoscale reliefs. These surface patterns emerge from symmetry-breaking dynamical processes that occur in Rayleigh-Bénard-like instabilities. In this study, we demonstrate that the coexistence and competition between surface patterns of different symmetries in two dimensions can be numerically unraveled using the stochastic generalized Swift-Hohenberg model. We originally propose a deep convolutional network to identify and learn the dominant modes that stabilize for a given bifurcation and quadratic model coefficients. The model is scale-invariant and has been calibrated on microscopy measurements using a physics-guided machine learning strategy. Our approach enables the identification of experimental irradiation conditions for a desired self-organization pattern. It can be generally applied to predict structure formation in situations where the underlying physics can be approximately described by a self-organization process and data is sparse and nontime series. Our Letter paves the way for supervised local manipulation of matter using timely controlled optical fields in laser manufacturing.

Learning PDE to Model Self-Organization of Matter.

A self-organization hydrodynamic process has recently been proposed to partially explain the formation of femtosecond laser-induced nanopatterns on Nickel, which have important applications in optics, microbiology, medicine, etc. Exploring laser pattern space is difficult, however, which simultaneously (i) motivates using machine learning (ML) to search for novel patterns and (ii) hinders it, because of the few data available from costly and time-consuming experiments. In this paper, we use ML to predict novel patterns by integrating partial physical knowledge in the form of the Swift-Hohenberg (SH) partial differential equation (PDE). To do so, we propose a framework to learn with few data, in the absence of initial conditions, by benefiting from background knowledge in the form of a PDE solver. We show that in the case of a self-organization process, a feature mapping exists in which initial conditions can safely be ignored and patterns can be described in terms of PDE parameters alone, which drastically simplifies the problem. In order to apply this framework, we develop a second-order pseudospectral solver of the SH equation which offers a good compromise between accuracy and speed. Our method allows us to predict new nanopatterns in good agreement with experimental data. Moreover, we show that pattern features are related, which imposes constraints on novel pattern design, and suggest an efficient procedure of acquiring experimental data iteratively to improve the generalization of the learned model. It also allows us to identify the limitations of the SH equation as a partial model and suggests an improvement to the physical model itself.

Ultrafast bandgap narrowing and cohesion loss of photoexcited fused silica.

Coupling and spatial localization of energy on ultrafast timescales and particularly on the timescale of the excitation pulse in ultrashort laser irradiated dielectric materials are key elements for enabling processing precision beyond the optical limit. Transforming matter on mesoscopic scales facilitates the definition of nanoscale photonic functions in optical glasses. On these timescales, quantum interactions induced by charge non-equilibrium become the main channel for energy uptake and transfer as well as for the material structural change. We apply a first-principles model to determine dynamic distortions of energy bands following the rapid increase in the free-carrier population in an amorphous dielectric excited by an ultrashort laser pulse. Fused silica glass is reproduced using a system of (SiO4)4- tetrahedra, where density functional theory extended to finite-temperature fractional occupation reproduces ground and photoexcited states. Triggered by electronic charge redistribution, a bandgap narrowing of more than 2 eV is shown to occur in fused silica under geometry relaxation. Calculations reveal that the bandgap decrease results from the rearrangement of atoms altering the bonding strength. Despite an atomic movement impacting strongly the structural stability, the observed change of geometry remains limited to 7% of the interatomic distance and occurs on the femtosecond timescale. This structural relaxation is thus expected to take place quasi-instantly following the photon energy flux. Moreover, under intense laser pulse excitation, fused silica loses its stability when an electron temperature of around 2.8 eV is reached. A further increase in the excitation energy leads to the collapse of both the structure and bandgap.

Boosted Spontaneous Formation of High-Aspect Ratio Nanopeaks on Ultrafast Laser-Irradiated Ni Surface.

The capacity to synthesize and design highly intricated nanoscale objects of different sizes, surfaces, and shapes dramatically conditions the development of multifunctional nanomaterials. Ultrafast laser technology holds great promise as a contactless process able to rationally and rapidly manufacture complex nanostructures bringing innovative surface functions. The most critical challenge in controlling the growth of laser-induced structures below the light diffraction limit is the absence of external order associated to the inherent local interaction due to the self-organizing nature of the phenomenon. Here high aspect-ratio nanopatterns driven by near-field surface coupling and architectured by timely-controlled polarization pulse shaping are reported. Electromagnetic coupled with hydrodynamic simulations reveal why this unique optical manipulation allows peaks generation by inhomogeneous local absorption sustained by nanoscale convection. The obtained high aspect-ratio surface nanotopography is expected to prevent bacterial proliferation, and have great potential for catalysis, vacuum to deep UV photonics and sensing.

High-Density Nanowells Formation in Ultrafast Laser-Irradiated Thin Film Metallic Glass.

We present an effective approach for fabricating nanowell arrays in a one-step laser process with promising applications for the storage and detection of chemical or biological elements. Biocompatible thin films of metallic glasses are manufactured with a selected composition of Zr65Cu35, known to exhibit remarkable mechanical properties and glass forming ability. Dense nanowell arrays spontaneously form in the ultrafast laser irradiation spot with dimensions down to 20 nm. The flared shape observed by transmission electron microscopy is ideal to ensure chemical or biological material immobilization into the nanowells. This also indicates that the localization of the cavitation-induced nanopores can be tuned by the density and size of the initial nanometric interstice from the columnar structure of films deposited by magnetron sputtering. In addition to the topographic functionalization, the laser-irradiated amorphous material exhibits structural changes analyzed by spectroscopic techniques at the nanoscale such as energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy. Results reveal structural changes consisting of nanocrystals of monoclinic zirconia that grow within the amorphous matrix. The mechanism is driven by local oxidation process catalyzed by extreme temperature and pressure conditions estimated by an atomistic simulation of the laser-induced nanowell formation.

Super-efficient drilling of metals with ultrafast non diffractive laser beams.

A highly efficient drilling process is found in non-transparent metallic materials enabled by the use of non-diffractive ultrafast Bessel beams. Applied for deep drilling through a 200 µm-thick steel plate, the Bessel beam demonstrates twofold higher drilling efficiency compared to a Gaussian beam of similar fluence and spot size. Notwithstanding that surface ablation occurs with the same efficiency for both beams, the drilling booster results from a self-replication and reconstruction of the beam along the axis, driven by internal reflections within the crater at quasi-grazing incidence, bypassing potential obstacles. The mechanism is the consequence of an oblique wavevectors geometry with low angular dispersion and generates a propagation length beyond the projection range allowed by the geometry of the channel. With only the main lobe being selected by the channel entrance, side-wall reflection determines the refolding of the lobe on the axis, enhancing and replicating the beam multiple times inside the channel. The process is critically assisted by the reduction of particle shielding enabled by the intrinsic self-healing of the Bessel beam. Thus the drilling process is sustained in a way which is uniquely different from that of the conventional Gaussian beam, the latter being damped within its Rayleigh range. These mechanisms are supported and quantified by Finite Difference Time Domain calculations of the beam propagation. The results show key advantages for the quest towards efficient laser drilling and fabrication processes.

Ultrafast Cylindrical Vector Beams for Improved Energy Feedthrough and Low Roughness Surface Ablation of Metals.

The use of ultrafast cylindrical vector vortex beams in laser-matter interactions permits new ablation features to be harnessed from inhomogeneous distributions of polarization and beam geometry. As a consequence, the ablation process can yield higher ablation efficiency compared with conventional Gaussian beams. These beams prevent surface quality degradation during the ablative processes. When processing stainless steel and titanium, the average surface roughness obtained by deploying the cylindrical vector is up to 94% lower than the Gaussian case, and the processing efficiency is 80% higher.

On the Insignificant Role of the Oxidation Process on Ultrafast High-Spatial-Frequency LIPSS Formation on Tungsten.

The presence of surface oxides on the formation of laser-induced periodic surface structures (LIPSS) is regularly advocated to favor or even trigger the formation of high-spatial-frequency LIPSS (HSFL) during ultrafast laser-induced nano-structuring. This paper reports the effect of the laser texturing environment on the resulting surface oxides and its consequence for HSFLs formation. Nanoripples are produced on tungsten samples using a Ti:sapphire femtosecond laser under atmospheres with varying oxygen contents. Specifically, ambient, 10 mbar pressure of air, nitrogen and argon, and 10-7 mbar vacuum pressure are used. In addition, removal of any native oxide layer is achieved using plasma sputtering prior to laser irradiation. The resulting HSFLs have a sub-100 nm periodicity and sub 20 nm amplitude. The experiments reveal the negligible role of oxygen during the HSFL formation and clarifies the significant role of ambient pressure in the resulting HSFLs period.

Initial Morphology and Feedback Effects on Laser-Induced Periodic Nanostructuring of Thin-Film Metallic Glasses.

Surface nanostructuring by femtosecond laser is an efficient way to manipulate surface topography, creating advanced functionalities of irradiated materials. Thin-film metallic glasses obtained by physical vapor deposition exhibit microstructures free from grain boundaries, crystallites and dislocations but also characterized by a nanometric surface roughness. These singular properties make them more resilient to other metals to form laser-induced nanopatterns. Here we investigate the morphological response of Zr65Cu35 alloys under ultrafast irradiation with multipulse feedback. We experimentally demonstrate that the initial columnar microstructure affects the surface topography evolution and conditions the required energy dose to reach desired structures in the nanoscale domain. Double pulses femtosecond laser irradiation is also shown to be an efficient strategy to force materials to form uniform nanostructures even when their thermomechanical properties have a poor predisposition to generate them.

Self-Organization Regimes Induced by Ultrafast Laser on Surfaces in the Tens of Nanometer Scales.

A laser-irradiated surface is the paradigm of a self-organizing system, as coherent, aligned, chaotic, and complex patterns emerge at the microscale and even the nanoscale. A spectacular manifestation of dissipative structures consists of different types of randomly and periodically distributed nanostructures that arise from a homogeneous metal surface. The noninstantaneous response of the material reorganizes local surface topography down to tens of nanometers scale modifying long-range surface morphology on the impact scale. Under ultrafast laser irradiation with a regulated energy dose, the formation of nanopeaks, nanobumps, nanohumps and nanocavities patterns with 20-80 nm transverse size unit and up to 100 nm height are reported. We show that the use of crossed-polarized double laser pulse adds an extra dimension to the nanostructuring process as laser energy dose and multi-pulse feedback tune the energy gradient distribution, crossing critical values for surface self-organization regimes. The tiny dimensions of complex patterns are defined by the competition between the evolution of transient liquid structures generated in a cavitation process and the rapid resolidification of the surface region. Strongly influencing the light coupling, we reveal that initial surface roughness and type of roughness both play a crucial role in controlling the transient emergence of nanostructures during laser irradiation.

Non-Diffractive Bessel Beams for Ultrafast Laser Scanning Platform and Proof-Of-Concept Side-Wall Polishing of Additively Manufactured Parts.

We report the potential use of non-diffractive Bessel beam for ultrafast laser processing in additive manufacturing environments, its integration into a fast scanning platform, and proof-of-concept side-wall polishing of stainless steel-based additively fabricated parts. We demonstrate two key advantages of the zeroth-order Bessel beam: the significantly long non-diffractive length for large tolerance of sample positioning and the unique self-reconstruction property for un-disrupted beam access, despite the obstruction of metallic powders in the additive manufacturing environment. The integration of Bessel beam scanning platform is constructed by finely adapting the Bessel beam into a Galvano scanner. The beam sustained its good profile within the scan field of 35 × 35 mm2. As a proof of concept, the platform showcases its advanced capacity by largely reducing the side-wall surface roughness of an additively as-fabricated workpiece from Ra 10 µm down to 1 µm. Therefore, the demonstrated Bessel-Scanner configuration possesses great potential for integrating in a hybrid additive manufacturing apparatus.

Multiscale electronic and thermomechanical dynamics in ultrafast nanoscale laser structuring of bulk fused silica.

We describe the evolution of ultrafast-laser-excited bulk fused silica over the entire relaxation range in one-dimensional geometries fixed by non-diffractive beams. Irradiation drives local embedded modifications of the refractive index in the form of index increase in densified glass or in the form of nanoscale voids. A dual spectroscopic and imaging investigation procedure is proposed, coupling electronic excitation and thermodynamic relaxation. Specific sub-ps and ns plasma decay times are respectively correlated to these index-related electronic and thermomechanical transformations. For the void formation stages, based on time-resolved spectral imaging, we first observe a dense transient plasma phase that departs from the case of a rarefied gas, and we indicate achievable temperatures in the excited matter in the 4,000-5,500 K range, extending for tens of ns. High-resolution speckle-free microscopy is then used to image optical signatures associated to structural transformations until the evolution stops. Multiscale imaging indicates characteristic timescales for plasma decay, heat diffusion, and void cavitation, pointing out key mechanisms of material transformation on the nanoscale in a range of processing conditions. If glass densification is driven by sub-ps electronic decay, for nanoscale structuring we advocate the passage through a long-living dense ionized phase that decomposes on tens of ns, triggering cavitation.

Sub-100 nm 2D nanopatterning on a large scale by ultrafast laser energy regulation.

Coupling ultrafast light irradiation to surface nanoreliefs leads to periodic patterns, achieving record processing scales down to tens of nanometers. Driven by near-field interactions, the promising potential of the spontaneous pattern formation relies on the scaling up of one-step manufacturing processes. Here, we report the self-assembly of unconventional arrays of nanocavities of 20 nm diameter with a periodicity down to 60 nm upon ultrafast laser irradiation of a nickel surface. In stark contrast to laser-induced surface ripples, which are stochastic and suffer from a lack of regularity, the 2D patterns present an unprecedented uniformity on extreme scales. The onset of nanocavity arrays ordered in a honeycomb lattice is achieved by overcoming the anisotropic polarization response of the surface by a delayed action of cross-polarized laser pulses. The origin of this self-arrangement is identified as a manifestation of Marangoni convection instability in a nanoscale melt layer, destabilized by the laser-induced rarefaction wave.

Additive and Substractive Surface Structuring by Femtosecond Laser Induced Material Ejection and Redistribution.

A novel additive surface structuring process is devised, which involves localized, intense femtosecond laser irradiation. The irradiation induces a phase explosion of the material being irradiated, and a subsequent ejection of the ablative species that are used as additive building blocks. The ejected species are deposited and accumulated in the vicinity of the ablation site. This redistribution of the material can be repeated and controlled by raster scanning and multiple pulse irradiation. The deposition and accumulation cause the formation of µm-scale three-dimensional structures that surpass the initial surface level. The above-mentioned ablation, deposition, and accumulation all together constitute the proposed additive surface structuring process. In addition, the geometry of the three-dimensional structures can be further modified, if desirable, by a subsequent substractive ablation process. Microstructural analysis reveals a quasi-seamless conjugation between the surface where the structures grow and the structures additively grown by this method, and hence indicates the mechanic robustness of these structures. As a proof of concept, a sub-mm sized re-entrant structure and pillars are fabricated on aluminum substrate by this method. Single units as well as arrayed structures with arbitrary pattern lattice geometry are easily implemented in this additive surface structuring scheme. Engineered surface with desired functionalities can be realized by using this means, i.e., a surface with arrayed pillars being rendered with superhydrophobicity.

Nanopore-mediated ultrashort laser-induced formation and erasure of volume nanogratings in glass.

Ultrashort laser nanostructuring of glasses has attracted increasing interest over the last few decades due to numerous applications in three-dimensional nanofabrication, optical data storage, and development of nanofluidic and polarization-sensitive devices. The knowledge of the influence of laser parameters on the nanostructure formation/erasure is still lacking. In this work, laser-induced modifications and mechanisms of glass decomposition in fused silica are numerically investigated. Cavitation is shown to be the primary mechanism responsible for void formation at the center of the heat-affected zone. Multipulse accumulation processes providing higher local temperatures/pressures lead to the rapid formation of cavitation nanopores, lying in the origin of self-organized nanogratings. Femtosecond laser-interaction threshold conditions required for nanograting formation/erasure are defined in agreement with the available experimental findings. For this, a detailed multi-physical modeling is performed taking into account laser pulse propagation in nonlinear and dispersive media, electronic relaxation/excitation processes, electron-ion heat transfer and thermal diffusion. Based on the calculated temperatures, classical nucleation theory, viscoelastic energy conservation law and the Rayleigh-Plesset model, threshold conditions leading to nanopore formation, stability and growth are investigated as a function of laser energy, pulse duration and repetition rate. The performed numerical study not only contributes to a better fundamental understanding of ultrashort laser-induced modifications on the nanoscale but should also be helpful in defining the optimal laser parameters for nanostructuring or avoiding nanostructure organization and in developing techniques for nanograting rewriting.

In-situ high-resolution visualization of laser-induced periodic nanostructures driven by optical feedback.

Optical feedback is often evoked in laser-induced periodic nanostructures. Visualizing the coupling between surfaces and light requires highly-resolved imaging methods. We propose in-situ structured-illumination-microscopy to observe ultrafast-laser-induced nanostructures during fabrication on metallic glass surfaces. This resolves the pulse-to-pulse development of periodic structures on a single irradiation site and indicates the optical feedback on surface topographies. Firstly, the quasi-constancy of the ripples pattern and the reinforcement of the surface relief with the same spatial positioning indicates a phase-locking mechanism that stabilizes and amplifies the ordered corrugation. Secondly, on sites with uncorrelated initial corrugation, we observe ripple patterns spatially in-phase. These feedback aspects rely on the electromagnetic interplay between the laser pulse and the surface relief, stabilizing the pattern in period and position. They are critically dependent on the space-time coherence of the exciting pulse. This suggests a modulation of energy according to the topography of the surface with a pattern phase imposed by the driving pulse. A scattering and interference model for ripple formation on surfaces supports the experimental observations. This relies on self-phase-stabilized far-field interaction between surface scattered wavelets and the incoming pulse front.

Spontaneous periodic ordering on the surface and in the bulk of dielectrics irradiated by ultrafast laser: a shared electromagnetic origin.

Periodic self-organization of matter beyond the diffraction limit is a puzzling phenomenon, typical both for surface and bulk ultrashort laser processing. Here we compare the mechanisms of periodic nanostructure formation on the surface and in the bulk of fused silica. We show that volume nanogratings and surface nanoripples having subwavelength periodicity and oriented perpendicular to the laser polarization share the same electromagnetic origin. The nanostructure orientation is defined by the near-field local enhancement in the vicinity of the inhomogeneous scattering centers. The periodicity is attributed to the coherent superposition of the waves scattered at inhomogeneities. Numerical calculations also support the multipulse accumulation nature of nanogratings formation on the surface and inside fused silica. Laser surface processing by multiple laser pulses promotes the transition from the high spatial frequency perpendicularly oriented nanoripples to the low spatial frequency ripples, parallel or perpendicular to the laser polarization. The latter structures also share the electromagnetic origin, but are related to the incident field interference with the scattered far-field of rough non-metallic or transiently metallic surfaces. The characteristic ripple appearances are predicted by combined electromagnetic and thermo-mechanical approaches and supported by SEM images of the final surface morphology and by time-resolved pump-probe diffraction measurements.

Scattering effects and high-spatial-frequency nanostructures on ultrafast laser irradiated surfaces of zirconium metallic alloys with nano-scaled topographies.

The origin of high-spatial-frequency laser-induced periodic surface structures (HSFL) driven by incident ultrafast laser fields, with their ability to achieve structure resolutions below λ/2, is often obscured by the overlap with regular ripples patterns at quasi-wavelength periodicities. We experimentally demonstrate here employing defined surface topographies that these structures are intrinsically related to surface roughness in the nano-scale domain. Using Zr-based bulk metallic glass (Zr-BMG) and its crystalline alloy (Zr-CA) counterpart formed by thermal annealing from its glassy precursor, we prepared surfaces showing either smooth appearances on thermoplastic BMG or high-density nano-protuberances from randomly distributed embedded nano-crystallites with average sizes below 200 nm on the recrystallized alloy. Upon ultrashort pulse irradiation employing linearly polarized 50 fs, 800 nm laser pulses, the surfaces show a range of nanoscale organized features. The change of topology was then followed under multiple pulse irradiation at fluences around and below the single pulse threshold. While the former material (Zr-BMG) shows a specific high quality arrangement of standard ripples around the laser wavelength, the latter (Zr-CA) demonstrates strong predisposition to form high spatial frequency rippled structures (HSFL). We discuss electromagnetic scenarios assisting their formation based on near-field interaction between particles and field-enhancement leading to structure linear growth. Finite-difference-time-domain simulations outline individual and collective effects of nanoparticles on electromagnetic energy modulation and the feedback processes in the formation of HSFL structures with correlation to regular ripples (LSFL).

Growth Twinning and Generation of High-Frequency Surface Nanostructures in Ultrafast Laser-Induced Transient Melting and Resolidification.

The structural changes generated in surface regions of single crystal Ni targets by femtosecond laser irradiation are investigated experimentally and computationally for laser fluences that, in the multipulse irradiation regime, produce sub-100 nm high spatial frequency surface structures. Detailed experimental characterization of the irradiated targets combining electron back scattered diffraction analysis with high-resolution transmission electron microscopy reveals the presence of multiple nanoscale twinned domains in the irradiated surface regions of single crystal targets with (111) surface orientation. Atomistic- and continuum-level simulations performed for experimental irradiation conditions reproduce the generation of twinned domains and establish the conditions leading to the formation of growth twin boundaries in the course of the fast transient melting and epitaxial regrowth of the surface regions of the irradiated targets. The observation of growth twins in the irradiated Ni(111) targets provides strong evidence of the role of surface melting and resolidification in the formation of high spatial frequency surface structures. This also suggests that the formation of twinned domains can be used as a sensitive measure of the levels of liquid undercooling achieved in short pulse laser processing of metals.