Heating and cooling in current-carrying molecular junctions is a crucial issue in molecular electronics. The microscopic mechanism involves complex factors such as energy inputs, molecular properties, electrode materials, and molecule-electrode coupling. To gain an in-depth understanding, it is a desired experiment to assess vibrational population that represents the energy distribution stored within the molecule. Here, we demonstrate the direct observation of vibrational heating in a single C60 molecule by means of tip-enhanced Raman spectroscopy (TERS). The heating of respective vibrational modes is monitored by anti-Stokes Raman scattering in the TERS spectra. The precise control of the gap distance in the single-molecule junction allows us to reveal a qualitatively different heating mechanism in distinct electron transport regimes, namely, the tunneling and single-molecule point contact (SMPC) regimes. Strong Joule heating via inelastic electron-vibration scattering occurs in the SMPC regime, whereas optical heating is predominant in the tunneling regime. The strong Joule heating at the SMPC also leads to a pronounced red shift of the Raman peak position and line width broadening. Furthermore, by examining the SMPC with several types of contact surfaces, we show that the heating efficiency is related to the current density at the SMPC and the vibrational dissipation channels into the electrode.
Keywords: inelastic electron−vibration coupling; molecular point contact; single-molecule Joule heating; single-molecule junction; tip-enhanced Raman spectroscopy.