The influence of semiconductors surface properties becomes increasingly significant as devices are scaled down to micro- and nanoscale dimensions. Consequently, surface engineering has become a critical step for optimizing device performance. Wet chemical etching of Si(111) in 40% NH4F solution is a well-established method for producing atomically flat, hydrogen terminated surfaces that can be readily functionalized with organic monolayers through a well-established Si surface chemistry. These modified surfaces have found applications in wide range of devices including electrochemical sensors, transistors and photovoltaic cells. Si etching in NH4F proceeds through two concurrent pathways: electrochemical and chemical etching. Electrochemical etching is initiated by charge carriers, particularly holes, which promotes isotropic oxidation of Si, leading to surface roughening. In contrast, chemical etching removes Si atoms from surface defects, steps and kinks while preserving atoms on thermodynamically stable Si(111) terraces, resulting in surface flattening. Since holes are the majority carriers in p-type Si(111), controlling the balance between these two competing pathways is essential for achieving atomically flat surfaces. In this study, open-circuit potential (OCP) measurements were employed to monitor the etching dynamics of p-Si(111) in real time. The OCP response was used to identify the condition that balance chemical and electrochemical etching, thereby enabling reproducible formation of atomically flat Si(111) surfaces. The resulting surface morphology was verified using atomic force microscopy (AFM)