Ultra-high vacuum scanning tunnelling microscopy investigation of free radical adsorption to the Si(111)-7 × 7 surface

Nathan P. Guisinger, Shaun P. Elder, Nathan L. Yoder, Mark Hersam*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

11 Scopus citations


Room-temperature ultra-high vacuum (UHV) scanning tunnelling microscopy (STM) has been employed to investigate free radical chemistry on the Si(111)-7 × 7 surface with atomic-scale spatial resolution. In particular, due to its single-site binding mechanism and extensive previous study on the Si(100)-2 × 1 surface, the nitroxyl free radical 2,2,6,6-tetramethyl-1- piperidinyloxy (TEMPO) was explored. UHV STM imaging of isolated molecules revealed that TEMPO covalently reacts with adatom dangling bonds with high affinity. By monitoring TEMPO adsorption as a function of surface coverage, TEMPO was also found to preferentially bind to centre adatom sites at the initial stages of adsorption. On the other hand, as the surface coverage increased, TEMPO molecules adsorbed to centre adatoms and corner adatoms approached a ratio of 1:1. At all surface coverage levels, TEMPO showed minimal preference for binding to either the faulted or unfaulted half of the unit cell. Consequently, upon saturation, the TEMPO adlayer exhibited long-range ordering and preserved the underlying 7 × 7 surface reconstruction. This study provides fundamental insight into free radical surface chemistry and suggests a direct pathway for forming nearly perfectly ordered organic adlayers on the Si(111)-7 × 7 surface.

Original languageEnglish (US)
Article number044011
Issue number4
StatePublished - Jan 31 2007

ASJC Scopus subject areas

  • Engineering (miscellaneous)
  • Materials Science(all)
  • Physics and Astronomy (miscellaneous)


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