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Abstract As a neighbor of carbon in the periodic table, boron exhibits versatile structural and electronic configurations, with its allotropes predicted to possess intriguing structures and properties. Since the experimental realization of two‐dimensional (2D) boron sheets (borophene) on Ag(111) substrates in 2015, the experimental study of the realization and characteristics of borophene has drawn increasing interest. In this review, we summarize the synthesis and properties of borophene, which are mainly based on experimental results. First, the synthesis of borophene on different substrates, as well as borophane and bilayer borophene, featuring unique phases and properties, are discussed. Next, the chemistry of borophene, such as oxidation, hydrogenation, and its integration into heterostructures with other materials, is summarized. We also mention a few works focused on the physical properties of borophene, specifically its electronic properties. Lastly, the brief outlook addresses challenges toward practical applications of borophene and possible solutions. 

Fundamental understanding of chemistry and physical properties at the nanoscale enables the rational design of interface-based systems. Surface interactions underlie numerous technologies ranging from catalysis to organic thin films to biological systems. Since surface environments are especially prone to heterogeneity, it becomes crucial to characterize these systems with spatial resolution sufficient to localize individual active sites or defects. Spectroscopy presents as a powerful means to understand these interactions, but typical light-based techniques lack sufficient spatial resolution. This review describes the growing number of applications for the nanoscale spectroscopic technique, tip-enhanced Raman spectroscopy (TERS), with a focus on developments in areas that involve measurements in new environmental conditions, such as liquid, electrochemical, and ultrahigh vacuum. The expansion into unique environments enables the ability to spectroscopically define chemistry at the spatial limit. Through the confinement and enhancement of light at the apex of a plasmonic scanning probe microscopy tip, TERS is able to yield vibrational fingerprint information of molecules and materials with nanoscale resolution, providing insight into highly localized chemical effects. 

Abstract Scanning tunneling microscopy‐based tip‐enhanced Raman spectroscopy (TERS) is a powerful analytical technique for surface characterization, providing both topological and chemical information with sub‐nm spatial resolution, well below the diffraction limit of light. In order to take advantage of plasmonic activity, it is necessary to use silver (Ag) probes due to their plasmonic range in the visible region. However, the Ag probe fabrication process remains challenging and is not yet standardized in practice, leading to inconsistent enhancements even for two similar types of tips prepared consecutively. In this work, we demonstrate an alternative way to reuse and recycle a plasmonic tip for distinct molecular systems inside an ultrahigh vacuum (UHV). We provide evidence of the ability to recycle tips without compromising the TERS experimental results. A long‐term preservation (>2 months) of plasmonically active probes inside UHV is demonstrated.