Inelastic Electron Tunneling Spectroscopy

Inelastic electron tunneling spectroscopy (IETS) is an experimental tool for studying the vibrations of molecular adsorbates on metal oxides. It yields vibrational spectra of the adsorbates with high resolution (< 0.5 meV) and high sensitivity (< 1013 molecules are required to provide a spectrum). An additional advantage is the fact that optically forbidden transitions may be observed as well. Within IETS, an oxide layer with molecules adsorbed on it is put between two metal plates. A bias voltage is applied between the two contacts. An energy diagram of the metal-oxide-metal device under bias is shown in the top figure. The metal contacts are characterized by a constant density of states, filled up to the Fermi energy. The metals are assumed to be equal. The adsorbates are situated on the oxide material. They are represented by a single bridge electronic level, which is the upper dashed line. If the insulator is thin enough, there is a finite probability that the incident electron tunnels through the barrier. Since the energy of the electron is not changed by this process, it is an elastic process. This is shown in the right figure.

Some of the tunneling electrons can lose energy by exciting vibrations of the oxide or the adsorbate. These inelastic processes lead to a second tunneling path, which gives an additional current contribution to the tunneling current. Since the incident electron should have enough energy to excite this vibration, there is a minimum energy that is the onset of this (inelastic) process. This is shown in the middle figure, where the lower dashed line is a vibronic state. This minimum energy for the electron corresponds with a minimum bias voltage, which is the onset for the additional contribution. The inelastic contribution to the current is small compared to the elastic tunneling current (~0.1%) and is more clearly seen as a peak in the second derivative of the current to the bias voltage, as can be seen in the bottom figure.

There is however also an important correction to the elastic component of the tunneling current at the onset. This is a second order effect in electron-vibration coupling, where a vibration is emitted and reabsorbed or vice versa. This is shown in the upper figure on the right. Depending on the energetic parameters of the system, this correction may be negative and it may outweigh the positive contribution of the inelastic current, resulting in a dip in the IETS spectrum. This is experimentally verified in both regular IETS and in STM-IETS and is also predicted theoretically. Not only peaks and dips may be observed, but depending on the energetic parameters also derivative-like features may be observed, both experimentally and theoretically.

Read more about Inelastic Electron Tunneling Spectroscopy:  STM-IETS

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