Understanding the response of wide-bandgap materials such as silicon dioxide (fused silica, α-quartz) to light is crucial for achieving precise control and manipulation in ultrafast laser volume structuring at the nanoscale. Surpassing optical resolution, this scale of achievement necessitates manipulating light energy around bulk inhomogeneities while precisely orchestrating selective thermodynamic pathways for absorption confinement, crystal-amorphous transformation and rapid energy quenching within nanometer lengths. We propose multiphysics calculations to elucidate the intricate interplay between electronic structure alterations and structural/hydrodynamical relaxation mechanisms under extreme nonequilibrium conditions. In particular, ab initio calculations reveal a narrowing of the bandgap by several eV and a loss of cohesion within an ultrashort timescale. This approach enables precise control and manipulation, optimizing processing parameters, and exploring novel aspects of solid relaxation induced by intense photoexcitation.
Unraveling the emergence of spontaneous patterns on laser-irradiated materials has been a long-standing pursuit. Periodic surface structures manifest as a result of multiphysical coupling involving electromagnetics, nonlinear optics, plasmonics, fluid dynamics, and thermochemical reactions. Periodic surface structures result from multiphysical coupling: electromagnetics, nonlinear optics, plasmonics, fluid dynamics, and thermochemical reactions. Multi-shot ultrafast laser pulses generate stable periodic patterns influenced by disturbances and nonlinear saturation. Describing pattern growth requires a model with symmetry breaking, scale invariance, stochasticity, and nonlinear properties. Stochastic Swift-Hohenberg modeling replicates hydrodynamic fluctuations near the convective instability threshold in laser-induced self-organized nanopatterns. We demonstrate that deep convolutional networks can learn pattern complexity, connecting model coefficients to experimental parameters for specific pattern design. The model predicts patterns accurately, even with limited data, identifying laser parameter regions and predicting novel patterns independently.
Brief laser pulses can induce autonomous organization of nanostructures pattern without external guidance. This interaction between a laser light and a material is governed by Maxwell's equations. These equations provide the theoretical framework for understanding how electromagnetic waves propagate and interact with matter. The Finite-Difference Time-Domain (FDTD) method models the laser-material interactions, providing insights into absorption, reflection, and scattering over time, ultimately contributing to self-organization within the material. Despite a theoretical understanding, there is no reliable model to predict the self-organization process responsible for the nanostructures. Our work addresses this issue by aiming to predict the surface changes after multiple laser irradiations using neural networks. Deep learning models have undergone advancements and prove suitable for extracting meaningful insights and simulating physical processes. This combination of laser physics and deep learning offer a promising approach to improve our ability to control nanostructures formation on materials.
Wide-bandgap materials such as silicon dioxide (fused silica, α-quartz) can undergo strong excitation when exposed to high-power ultrashort laser pulses. This leads to a high transient electron density in the conduction band, causing distortion in the bands and resulting in a significant bandgap renormalization. Additionally, there is a spatial redistribution of the excited charges, leading to weakening of silica bonds and subsequent reorganization of the crystal structure, further contributing to the change in the bandgap. Through the use of Density Functional Theory, Time-Dependent Density Functional Theory, and GW approximation, the evolution of the bandgap is studied at different levels of excitation, revealing changes of up to several electronvolts on ultrashort timescales.
Understanding spontaneous pattern emergence on laser-irradiated materials is a long-standing interest. Periodic surface structures arise from multiphysical coupling: electromagnetics, nonlinear optics, plasmonics, fluid dynamics, or thermochemical reactions. Multi-shot irradiation with ultrafast laser pulses generates stable periodic patterns arising from localized perturbations influenced by disturbances and nonlinear saturation. Describing pattern growth requires nonlinear dynamics beyond classic equations. The challenge is developing an efficient model with symmetry breaking, scale invariance, stochasticity, and nonlinear properties to reproduce dissipative structures. Stochastic Swift-Hohenberg modeling replicates hydrodynamic fluctuations near the convective instability threshold, inherent in laser-induced self-organized nanopatterns. We will demonstrate that a deep convolutional networks can learn pattern complexity, connecting model coefficients to experimental parameters for designing specific patterns. The model predicts patterns accurately, even with limited non-time series data. It identifies laser parameter regions and could predict novel patterns independently.
The use of ultrafast Cylindrical Vector Vortex beams in laser-matter interaction permits to harness new ablation features from inhomogeneous distributions of polarization and beam energy distribution geometry. As a consequence, the ablation process can yield higher ablation efficiency compared to the conventional Gaussian beams. Cylindrical Vector Vortex beams prevent surface quality degradation during ablative processes. When processing stainless steel and titanium, the average surface roughness obtained by deploying Cylindrical Vector beam is up to 94% lower than the Gaussian case, and the processing efficiency is 80% higher.
Fused silica is an indispensable material in emergent photonic applications due to its unique optical, mechanical, and thermal properties, especially when it is nano-structured by an ultrashort laser pulse. The precision of the laser-induced modifications relies heavily on the control of the electron excitations and transient optical properties during the laser pulse. In this work we explored the evolution of fused silica bandgap at high densities of excited electrons, using Finite-Temperature Fractional Occupation Density Functional Theory (FT-DFT). Using a molecular-level approach, a molecular cluster based on (SiO4)4- tetrahedra was shown to reproduce accurately the physical properties of amorphous silica. The proposed theoretical approach (FT-DFT) correctly describes electronic and spatial structure both at the ground state and photoexcitation-induced thermalized hot states. Under electron-matrix nonequilibrium conditions, a bandgap narrowing by 2 eV and more is shown. This is explained by a pure geometry relaxation driven by the electron redistribution during the strong laser-induced excitation. The reason for the bandgap decrease is atomic rearrangement resulting in weakening of the bonds. Such behaviour of the system under excitation has a significative impact on its stability even if changes in geometry are limited to 7.5% bond elongation before the loss of integrity of the system. According to experimental data this atomic rearrangement can be expected on the femtosecond timescale. Defect formation in fused silica due to bond breaking is finally expected to occur for electronic temperatures above 2.8 eV.
Ultrafast-laser irradiated surface is a typical paragon of a self-organizing system, which emerge and organize complex micropatterns and even nanopatterns. An astounding exhibition of dissipative structures consists of various types of randomly and periodically generated nanostructures that originate from a homogeneous metal surface. The formation of nanopeaks, nanobumps, nanohumps and nanocavities patterns with 20–80 nm transverse size unit and up to 100 nm height are reported under femtosecond laser irradiation with a regulated energy dose. We shed the light on the originality of the nanopeaks, having an exceptional aspect ratio on the nanoscale. They are primarily generated on the crests grown between the convective cells formed on the very first pulses. The production of these distinct nanostructures can enable unique surface functionalizations toward the control of mechanical, biomedical, optical, or chemical surface properties on a nanometric scale.
Ultrashort laser irradiation of metal targets results in a variety of coupled processes, such as energy deposition
on surface, electron-ion heating and diffusion, as well as thermal ablation and plasma expansion, mechanical
rupture below the surface, and melt flow, modifying the initial surface morphology on micro/nanometric scales.
Multidimensional simulations capable to predict the consequences of inhomogeneous absorption on hydrodynamic
processes are performed in order to elucidate the mechanisms of surface micro/nanostructure formation and
material removal during multipulse laser ablation in regimes below, near and above laser ablation threshold. On
one hand, the numerical results suggest new ways of control over the properties of periodic and aperiodic surface
structures. On the other hand, the strategies to reduce the surface roughness and to improve the quality and the effciency of ultrashort laser ablation are discussed.
Ultrafast light coupling with metal surfaces shows strong potential for nanostructuring applications relying on the capacity to localize light energy on the nanoscale. Controlling light confinement requires to understand the transient variation of the optical response during ultrafast irradiation. The fundamental approach we propose based on ab initio calculations allows elucidating the influence of electron-phonon nonequilibrium on optical properties. This results from the investigation of the primary processes responsible for the optical change during laser-solid interaction. Calculations are carried out in the framework of the density functional theory associated to quantum molecular dynamics. Our results shed light on the intricate role of electronic structure modifications and possible optical transitions, driving the laser energy absorption into the material. The revealed key processes based on Fermi smearing on an evolving density of states are of paramount interest for controlling laser energy deposition, surface plasmon excitation and subsequent surface nanostructuring. The calculations predict the possibility of an ultrafast laser-driven plasmonic switch on a typically non-plasmonic material (W), confirmed by pump-probe ellipsometric measurements [1]. The consequence of our results is far reaching as they propose also a route for achieving the highest energy confinement under ultrashort laser irradiation.
[1] E. Bévillon, J.P. Colombier, V. Recoules, H. Zhang, C. Li, R. Stoian, “Ultrafast switching of surface plasmonic conditions in nonplasmonic metals”, Physical Review B 93 (16), 165416 (2016).
Generation of periodic arrangements of matter on materials irradiated by laser fields of uniform and isotropic energy distribution is a key issue in controlling laser structuring processes below the diffractive limit. Using three-dimensional finite-difference time-domain methods, we evaluate energy deposition patterns below a material's rough surface [1] and in bulk dielectric materials containing randomly distributed nano-inhomogeneities [2]. We show that both surface and volume patterns can be attributed to spatially ordered electromagnetic solutions of linear and nonlinear Maxwell equations. In particular, simulations revealed that anisotropic energy deposition results from the coherent superposition of the incident and the inhomogeneity-scattered light waves. Transient electronic response is also analyzed by kinetic equations of free electron excitation/relaxation processes for dielectrics and by ab initio calculations for metals. They show that for nonplasmonic metals, ultrafast carrier excitation can drastically affect electronic structures, driving a transient surface plasmonic state with high consequences for optical resonances generation [3]. Comparing condition formations of 2D laser-induced periodic surface structures (LIPSS) and 3D self-organized nanogratings, we will discuss the role of collective scattering of nanoroughness and the feedback-driven growth of the nanostructures.
[1] H. Zhang, J.P. Colombier, C. Li, N. Faure, G. Cheng, and R. Stoian, Physical Review B 92, 174109 (2015).
[2] A. Rudenko, J.P. Colombier, and T.E. Itina, Physical Review B 93 (7), 075427 (2016).
[3] E. Bévillon, J.P. Colombier, V. Recoules, H. Zhang, C. Li and R. Stoian, Physical Review B 93 (16), 165416 (2016).
Ultrafast laser pulses can be used to achieve structuring of surfaces at the micro-nano scale. Under certain irradiation conditions, Laser Induced Periodic Surface Structures (LIPSS) are formed. The LIPSS dimensions range from 100 nm to 2-3 micrometers. The characterization is generally conducted after the laser irradiation by systems such as SEM and/or AFM with a resolution beyond the diffraction limit. In this paper, we use a super resolution microscopy technique based on structured illumination for in-situ observation of the irradiated surface. The LIPSS formation on steel and Si is observed IN-SITU and discussed for a multipulse sequence.
We investigate femtosecond laser irradiation of dielectric materials containing randomly-arranged nanoparticles. For this, numerical modeling is performed based on three different methods: Mie theory, static solution of linear Maxwell's equations and a solution of nonlinear Maxwell's equations together with kinetic equations for free electron excitation/relaxation processes. First two approaches are used to define the static intensity distribution and to analyze the electromagnetic interaction between the nanoparticles. The third method allows us to investigate the complex dynamics of the laser-matter interaction. Multiphoton absorption is shown to be responsible for electron plasma generation in the regions of strong intensity enhancements in the vicinity of nanoparticles. The irradiation of the dielectric material leads to the elongation of nanoplasmas by the near-field enhancement perpendicular to the laser polarization and to their strong interaction resulting in periodic arrangement. Numerical results shed light on such effects as femtosecond laser-induced nanograting formation
We measured the dielectric constant of optically excited silicon and tungsten using a dual-angle femtosecond reflectivity pump-probe technique. The energy deposition in the formation of laser-induced periodic surface structures (LIPSS) is then investigated by simulating the laser pulse interaction with an initially random distributed rough surface using 3D-Finite Difference Time Domain (FDTD) method, with the measured dielectric constant as a material input. We found in the FDTD simulation periodic energy deposition patterns both perpendicular and parallel to the laser polarization. The origin of them are discussed for originally plasmonic and non-plasmonic material.
Ultrafast Bessel beams are ideal sources for high aspect ratio submicron structuring applications because of their nondiffracting nature and higher stability in nonlinear propagation. We report here on the interaction of ultrafast Bessel beams at various laser energies and pulse durations with transparent materials (fused silica) and define their impact on photoinscription regimes, i.e., formation of positive and negative refractive index structures. The laser pulse duration was observed to be key in deciding the type of the structures via excitation efficiency. To understand the relevant mechanisms for forming these different structures, the free carrier behavior as a function of laser pulse duration and energy was studied by capturing instantaneous excitation profiles using time-resolved microscopy. Time-resolved imaging and simulation studies reveal that low carrier densities are generated for ultrashort pulses, leading to soft positive index alterations via presumably nonthermally induced structural transitions involving defects. On the other hand, the high free carrier density generation in the case of longer pulse durations leads to hydrodynamic expansion, resulting in high aspect ratio submicron-size wide voids. Delayed ionization, carrier defocusing, and lower nonlinear effects are responsible for the confinement of energy, resulting in efficient energy deposition on-axis.
Nonlinear propagation of intense ultrafast laser pulses inside transparent materials has a strong influence on the fabrication quality and accuracy for 3D laser-material processing. Due to their ability to maintain near-constant fluence profiles over an appreciable distance along the propagation direction in linear and nonlinear media, ultrafast Bessel beams are ideal sources for high aspect ratio sub-micron structuring applications. We report here on the interaction of transparent materials, especially fused silica, with ultrafast non-diffractive beams of moderate cone angle at various laser energies and pulse durations and define their impact on photoinscription regimes, i.e. formation of isotropic and non-isotropic (positive and negative) refractive index structures. The laser pulse duration was observed to be key in deciding the type of the structures via excitation efficiency. To understand the significant mechanisms for forming these different structures, the free carrier behavior as a function of laser pulse duration and energy was studied by capturing instantaneous excitation profiles using time-resolved microscopy. Time-resolved imaging and simulation studies reveal that low carrier densities are generated for ultrashort pulses leading to soft positive index alterations via presumably non-thermally induced structural transitions via defects. On the other hand, the high free carrier density generation in the case of longer pulse durations leads to a hydrodynamic expansion resulting in high aspect ratio sub-micron size wide voids. Delayed ionization, carrier defocusing and lower nonlinear effects are responsible for the confinement of energy, resulting in efficient energy deposition on-axis.
Due to a large material removal rate and a minimal collateral damage, subpicosecond laser pulse offers many advantages for material processing. Post-experimental examination of ultrashort laser material ablation shows that the heated surface of the bulk does not exhibit thermal damage. A lot of complicated physical processes follow intense laser irradiation and have often been modeled in over-simplified way to explain experimental results. Because a more complete understanding of the damage mechanisms would be very interesting and would open new applications in the scientific research community and industry. A detailed model of the ultrashort response to reproduce ablation process is presented, describing dynamical electronic properties such as temperature, pressure and energy. To simulate the interaction between the laser and the metallic target, these theoretical models are inserted inside a 1D Lagrangian hydrodynamic code. It is still a very challenging task to disentangle the cumulative/competitive effects of all physical processes if included at once in numerical simulations. Adding the different processes into numerical simulations on a one by one basis allow to assess their contributions to the quantity of ejected matter on a large range of laser intensity. Experimental results related to the influence of multi-pulses or tailored pulses for ablation efficiency with ultrafast pulses(pulse duration up to 5 ps) has been obtained. A significant improvement of the micro structuring quality in metals is demonstrated, and the theoretical approach presented allow to manage the optimal temporal shape of pulses. An efficient process control can be reached and the industrial applications will be evidenced.
In the range of intensity 1013-1014 W/cm2, material processing with ultrashort laser pulses is characterized by the absence of a plasma shielding effect and a small heat affected zone. The understanding of sub-picosecond laser pulse effects involves detailed study of laser-solid interaction processes. The dependence on fluence and pulse duration of the ablation rate can be studied experimentally. To analyse the laser-metal ablation mechanisms, we have inserted an electron-ion decoupling into a hydrodynamic code. The hydrodynamic simulations reveal many details of the processes yielding ablation.
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