Blue phosphorene (BlueP) has attracted considerable attention, and Cu(111) has been widely explored as a potential growth substrate. However, although several experiments have interpreted phosphorus-derived phases on Cu(111) as BlueP or BlueP-related structures, the chemical identity and atomic registry of the early-stage stripe phases remain unresolved. Here, by combining first-principles calculations with systematic structural searches, we identify a ${\mathrm{Cu}}_3{\mathrm{P}}_2$ ribbonlike surface alloy as the lowest-energy candidate for these stripe phases within the explored configuration space, rather than a direct pure BlueP overlayer. The simulated scanning tunneling microscopy contrast of this model is consistent with the observed stripe features, while its registry with Cu(111) accounts for the reported orientation locking. We further show that ${\mathrm{Cu}}_3{\mathrm{P}}_2$ ribbons can be periodically stitched into longer-period Cu–P superstructures that are energetically favored among the structures considered. In contrast, direct BlueP formation on bare Cu(111) is less favorable than several low-energy Cu–P surface-alloy structures. These results clarify the atomic structure and orientation-locking mechanism of phosphorus-induced stripe phases on Cu(111) and provide an atomic-scale basis for understanding the subsequent coverage-dependent evolution of the P/Cu(111) system.

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• Nucleation on surfaces
• Interfaces
• Surface growth
• Ab initio molecular dynamics
• First-principles calculations