Atomic‐Scale Insights into the Interlayer Characteristics and Oxygen Reactivity of Bilayer Borophene

Abstract Bilayer (BL) two‐dimensional boron (i.e., borophene) has recently been synthesized and computationally predicted to have promising physical properties for a variety of electronic and energy technologies. However, the fundamental chemical properties of BL borophene that form the foundation of practical applications remain unexplored. Here, we present atomic‐level chemical characterization of BL borophene using ultrahigh vacuum tip‐enhanced Raman spectroscopy (UHV‐TERS). UHV‐TERS identifies the vibrational fingerprint of BL borophene with angstrom‐scale spatial resolution. The observed Raman spectra are directly correlated with the vibrations of interlayer boron–boron bonds, validating the three‐dimensional lattice geometry of BL borophene. By virtue of the single‐bond sensitivity of UHV‐TERS to oxygen adatoms, we demonstrate the enhanced chemical stability of BL borophene compared to its monolayer counterpart by exposure to controlled oxidizing atmospheres in UHV. In addition to providing fundamental chemical insight into BL borophene, this work establishes UHV‐TERS as a powerful tool to probe interlayer bonding and surface reactivity of low‐dimensional materials at the atomic scale.