Electronic Origin of Laser-Induced Ferroelectricity in SrTiO₃

Although ultrafast control of the nonthermally driven ferroelectric transition of paraelectric SrTiO₃ was achieved under laser excitation, the underlying mechanism and dynamics of the photoinduced phase transition remain ambiguous. Here, the determinant formation mechanism of ultrafast ferroelectricity in SrTiO₃ is traced by nonadiabatic dynamics simulations. That is, the selective excitation of multiple phonons, induced by photoexcited electrons through the strong correlation between electronic excitation and lattice distortion, results in the breaking of the crystal central symmetry and the onset of ferroelectricity. The accompanying population transition between 3d and 3d orbitals excites multiple phonon branches, including the two high-energy longitudinal optical modes, so as to drive the titanium ion away from the center of the oxygen octahedron and generate a metastable ferroelectric phase. Our findings reveal a cooperative electronic and ionic driving mechanism for the laser-induced ferroelectricity that provides new schemes for the optical control of ultrafast quantum states.