Oxide Uniformity and Oxygen Scavenging Correlate with Rapid Formation of Atomically Flat Si(111)–H Surfaces

The formation of atomically flat Si(111)–H surfaces was critical for molecular electronics, nanoscale device fabrication, and surface chemistry studies. We systematically investigated how initial oxide composition and dissolved oxygen affected terrace-formation kinetics during ammonium fluoride (NH4F) etching. N-type Si(111) was cleaned with either oxygen plasma or piranha solution to generate, respectively, a more uniform versus a chemically heterogeneous oxide, and then etched in NH4F containing 0–5% (w/v) ammonium sulfite (AS) as an oxygen scavenger. AFM acquired every 2 min over 20 min revealed that plasma-pretreated surfaces reached atomically flat terraces earlier and more reproducibly than piranha-pretreated surfaces. Increasing AS concentration suppressed oxygen-induced etch pits and promoted the earlier appearance of large, well-ordered terraces, whereas prolonged etching led to roughening. XPS and ATR-FTIR corroborated differences in the starting oxides and confirmed post-etch H-termination. Collectively, the results indicated that oxide uniformity together with oxygen scavenging correlated with faster attainment and greater persistence of low-roughness terraces, providing a practical framework for reproducibly preparing hydrogen-terminated Si(111)–H surfaces.