Spectroscopic Imaging of Interfacial Interaction-Mediated Phosphorene Growth Pathways on Noble Metals

Interfacial interaction is a key element in epitaxial growth. While theoretical studies have highlighted its importance for the structure and stability of phosphorene on various substrates, direct experimental verification remains scarce. Here, we systematically investigate the interfacial interactions of diverse phosphorene structures on Au(111), Ag(111), and Cu(111) surfaces and reveal a positive correlation between the structural stability and interfacial interaction strength on the same substrate. Crucially, we observed a distinct difference in growth pathways. On Au(111) and Ag(111), the final structures appear to be kinetically limited under the experimental conditions, whereas on Cu(111), the phase evolution tends toward coverage-dependent ordering, suggestive of thermodynamic influence. This distinction may stem from the dominant intralayer bonding on a weakly interacting substrate versus competition between interfacial and intralayer interactions on a strongly coupling substrate. This work experimentally distinguishes kinetically and thermodynamically dominated growth regimes of phosphorene on noble metal substrates, correlating the transition with interfacial interaction strength.