Ultrafast on-demand exciton formation in a single-molecule junction by tailored terahertz pulses.

The ultrafast manipulation of molecular states by charge transfer is essential for characterizing and controlling molecular dynamics. In this study, we demonstrated exciton formation in a single molecule through ultrafast electron tunneling processes between a molecule and a metal tip of a scanning tunneling microscope (STM) using a phase-controlled terahertz (THz) pulse. The pronounced luminescence of the well-defined molecular system under the distinct carrier-envelope phase of the THz pulse revealed that sequential state-selective electron-tunneling processes to the frontier molecular orbitals promoted ultrafast exciton formation in the molecule at the STM junction. Furthermore, ultrafast control of exciton formation was achieved using phase- and delay-controlled THz pulse pairs, providing a route for the regulation of molecular dynamics and the emergence of new molecular functions.