Structural instability of transition metals upon ultrafast laser irradiation

Precision in laser material structuring is critically defined by the energy flow during the irradiation process, particularly in ultrafast regimes. Alternative to thermal evolutions, nonequilibrium electronic excitation can exercise a direct influence on the atomic bonding delivering a potentially rapid destructuring process. In this context, the atomic disordering of transition metals (Cr, Ni, and Ti) induced by nonequilibrium electronic excitation typical for ultrafast laser processing is studied with an emphasis on the role of the d-band filling and crystalline structure. The density functional theory is used to obtain, from first principles, structural stability criteria and nonthermal disordering pathways on timescales shorter than picosecond electron-phonon dynamics. We show that the hot electrons distort charge distribution in the cold crystalline arrangement and increase the entropy of the system, thus driving the mechanical expansion. The calculated nonequilibrium free-energy potentials indicate that a solid destabilization is possible when electron temperature reaches a universal value of around 2 eV for all considered metals. Under a uniaxial lattice relaxation expected in the laser ablation of surface layers, the charge redistribution and loss of lattice stability is shown to be oriented along specific crystal directions. Moreover, we show that the interatomic potential destabilization is energetically more favorable for Ni than for Cr and Ti. Lattice dynamics is affected by space-charge redistribution induced by Fermi smearing associated with anisotropic expansion due to electron pressure gradients. This ultrafast destructuring mechanism is shown to be a general feature of partially filled d-band transition metals.