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.
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.
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.
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