Bistability of single 1,5 cyclooctadiene molecules on Si(001)

The adsorption and current-induced bistability of single 1,5 cyclooctadiene molecules on Si(001) were studied in ultrahigh vacuum by low-temperature scanning tunneling microscopy (STM). After a dosage of ≈0.05 L at room temperature followed by cooling to the measuring temperature of 7 K, we find that the cyclic alkene molecule preferably adsorbs in the bridge structure with both C=C double bonds reacting with two adjacent Si dimers via [2+2] cycloaddition reaction. The time-dependent current measured upon tunneling through the adsorbed molecule at fixed STM tip height displays a switching between two current levels with the same mean residence time in each level. Higher bias and/or reduced tip height—and therefore higher current—increase the switching rate, suggesting that the reversible switching is due to inelastic electron tunneling. The observed bistability is interpreted as a dynamic interconversion between two degenerate conformations of the adsorbed molecule.