Electroreduction of Perchlorinated Silanes for Si Electrodeposition

Abstract

The electrochemical reactivity and suitability of hexachlorodisilane and tetrakis(trichlorosilyl)silane as Si ec-LLS electrodeposition precursors in several electrolyte solutions have been investigated. Voltammetric data indicated that perchlorinated silanes exhibit mechanistically similar electrochemical responses as SiCl4, regardless of the Si–Si bond content in the precursor. The voltammetric responses were a strong function of the concentration of the precursor, indicating the participation of electrogenerated intermediates during the reduction and concomitant Si electrodeposition. Variation of the anion in the supporting electrolyte was found to be a critical factor for the thermal and chemical stability of the precursor bath. A combination of chronoamperometry and electron microscopy data were used to study the deposition efficiency specifically for hexachlorodisilane. The faradaic efficiency was low, regardless of overpotential or the composition of the electrolyte. Cumulatively, these data show that while larger chlorosilanes can be used for conventional Si electrodeposition over a wider range of conditions, their chemical instability and propensity for low faradaic efficiency limit their utility as reagents relative to SiCl4 for Si electrodeposition by ec-LLS.