In Situ STM Investigation of Gold Reconstruction and of Silicon Electrodeposition on Au(111) in the Room Temperature Ionic Liquid 1-Butyl-1-methylpyrrolidinium Bis(trifluoromethylsulfonyl)imide

The electrodeposition of silicon on Au(111) was investigated by cyclic voltammety (CV) and by in situ scanning tunneling microscopy (STM) in the room temperature ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide with a SiCl(4) concentration of 0.1 mol/L. A main reduction process begins in the cyclic voltammogram at about -1800 mV versus ferrocene/ferrocinium, which is correlated to the electrodeposition of elemental semiconducting silicon. It has been found that at an electrode potential more negative than the open circuit potential (OCP), the Au(111) surface is subject to a restructuring/reconstruction both in the case of the pure ionic liquid and in the presence of SiCl(4). The first STM-probed silicon islands with 150-450 pm in height appear at about -1700 mV versus ferrocene/ferrocinium. Their lateral and vertical growth leads to the formation of a rough layer with silicon islands of up to 1 nm in height. At about -1800 mV the islands merge and form silicon agglomerates. In situ I/U tunneling spectroscopy reveals a band gap of 1.1 +/- 0.2 eV for layers of about 5 nm in height, a value that has to be expected for semiconducting silicon.