Photoexcitation in solids brings about transitions of electrons/holes between different electronic bands. If the solid lacks an inversion symmetry, these electronic transitions support spontaneous photocurrent due to the topological character of the constituting electronic bands; the Berry connection. This photocurrent, termed shift current, is expected to emerge on the time-scale of primary photoexcitation process. We observed ultrafast time evolution of the shift current in a prototypical ferroelectric semiconductor by detecting emitted terahertz electromagnetic waves. By sweeping the excitation photon energy across the band gap, ultrafast electron dynamics as a source of terahertz emission abruptly changes its nature, reflecting a contribution of Berry connection upon interband optical transition. The shift excitation carries a net charge flow, and is followed by a swing-over of the electron cloud on the sub-picosecond time-scale of electron-phonon interaction. Understanding these substantive characters of the shift current will pave the way for its application to ultrafast sensors and solar cells.
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