skip to main content


This content will become publicly available on June 15, 2024

Title: Atomic‐Scale Insights into the Interlayer Characteristics and Oxygen Reactivity of Bilayer Borophene
Bilayer (BL) two-dimensional boron (i.e., borophene) emerges very recently and holds promise for fascinating physical properties and a variety of electronic applications. Despite this potential, the fundamental chemical properties of BL borophene which form the critical foundation of practical applications has been unexplored. Here, we present atomic-level chemical studies of BL borophene using ultrahigh vacuum tip-enhanced Raman spectroscopy (UHV-TERS). UHV-TERS identifies the vibrational fingerprint of BL borophene from mixed-dimensional borophene polymorphs with angstrom-scale chemical spatial resolution. The observed Raman mode is 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 under UHV. In addition to revealing fundamental chemical insights into BL borophene, this work establishes UHV-TERS as a powerful tool to probe interlayer bonding and chemical properties of layered materials at the atomic scale.  more » « less
Award ID(s):
2211474
NSF-PAR ID:
10501119
Author(s) / Creator(s):
; ; ; ; ; ;
Publisher / Repository:
Wiley
Date Published:
Journal Name:
Angewandte Chemie International Edition
Volume:
62
Issue:
32
ISSN:
1433-7851
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    The chemical interrogation of individual atomic adsorbates on a surface significantly contributes to understanding the atomic-scale processes behind on-surface reactions. However, it remains highly challenging for current imaging or spectroscopic methods to achieve such a high chemical spatial resolution. Here we show that single oxygen adatoms on a boron monolayer (i.e., borophene) can be identified and mapped via ultrahigh vacuum tip-enhanced Raman spectroscopy (UHV-TERS) with ~4.8 Å spatial resolution and single bond (B–O) sensitivity. With this capability, we realize the atomically defined, chemically homogeneous, and thermally reversible oxidation of borophene via atomic oxygen in UHV. Furthermore, we reveal the propensity of borophene towards molecular oxygen activation at room temperature and phase-dependent chemical properties. In addition to offering atomic-level insights into the oxidation of borophene, this work demonstrates UHV-TERS as a powerful tool to probe the local chemistry of surface adsorbates in the atomic regime with widespread utilities in heterogeneous catalysis, on-surface molecular engineering, and low-dimensional materials.

     
    more » « less
  2. Synthetic two-dimensional polymorphs of boron, or borophene, have attracted attention because of their anisotropic metallicity, correlated-electron phenomena, and diverse superlattice structures. Although borophene heterostructures have been realized, ordered chemical modification of borophene has not yet been reported. Here, we synthesize “borophane” polymorphs by hydrogenating borophene with atomic hydrogen in ultrahigh vacuum. Through atomic-scale imaging, spectroscopy, and first-principles calculations, the most prevalent borophane polymorph is shown to possess a combination of two-center–two-electron boron-hydrogen and three-center–two-electron boron-hydrogen-boron bonds. Borophane polymorphs are metallic with modified local work functions and can be reversibly returned to pristine borophene through thermal desorption of hydrogen. Hydrogenation also provides chemical passivation because borophane reduces oxidation rates by more than two orders of magnitude after ambient exposure.

     
    more » « less
  3. 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.

     
    more » « less
  4. Abstract

    Two-dimensional (2D) materials have recently garnered significant interest due to their novel and emergent properties. A plethora of 2D materials have been discovered and intensively studied, such as graphene, hexagonal boron nitride, transitionmetal dichalcogenides (TMDCs), and other metallic compound MXenes (nitrides, phosphides, and hydroxides), as well as elemental 2D materials (borophene, germanene, phosphorene, silicene, etc.). Considering the widespread interest in conventional van der Waals 2D materials, two-dimensional metallic nanosheets (2DMNS), a recent addition to the 2D materials family, have exhibited diverse potential spanning optics, electronics, magnetics, catalysis, etc. However, the close-packed, non-layered structure and non-directional, isotropic bonding of metallic materials make it difficult to access metals in their 2D forms, unlike 2D van der Waals materials, which have intrinsically layered structure (strong in-plane bonding in addition to the weak interlayer interaction). Until now, conventional top-down and bottom-up synthesis schemes of these 2DMNS have encountered various limitations such as precursor availability, substrate incompatibility, difficulty of control over thickness and stoichiometry, limited thermal budget, etc. To overcome these manufacturing limitations of 2DMNS, here we report a facile, rapid, large-scale, and cost-effective fabrication technique of nanometer-scale copper (Cu) 2DMNS via iterative rolling, folding, and calendering (RFC) that is readily generalizable to other conventional elemental metallic materials. Overall, we successfully show a scalable fabrication technique of 2DMNS.

     
    more » « less
  5. null (Ed.)
    Two-dimensional (2D) materials have recently garnered significant interest due to their novel and emergent properties. A plethora of 2D materials have been discovered and intensively studied, such as graphene, hexagonal boron nitride, transition-metal dichalcogenides TMDCs), and other metallic compound MXenes (nitrides, phosphides, and hydroxides), as well as elemental 2D materials (borophene, germanene, phosphorene, silicene, etc.). Considering the widespread interest in conventional van der Waals 2D materials, two-dimensional metallic nanosheets (2DMNS), a recent addition to the 2D materials family, have exhibited diverse potential spanning optics, electronics, magnetics, catalysis, etc. However, the close-packed, non-layered structure and non-directional, isotropic bonding of metallic materials make it difficult to access metals in their 2D forms, unlike 2D van der Waals materials, which have intrinsically layered structure (strong in-plane bonding in addition to the weak interlayer interaction). Until now, conventional top-down and bottom-up synthesis schemes of these 2DMNS have encountered various limitations such as precursor availability, substrate incompatibility, difficulty of control over thickness and stoichiometry, limited thermal budget, etc. To overcome these manufacturing limitations of 2DMNS, here we report a facile, rapid, large-scale, and cost-effective fabrication technique of nanometer-scale copper (Cu) 2DMNS via iterative rolling, folding, and calendering (RFC) that is readily generalizable to other conventional elemental metallic materials. Overall, we successfully show a scalable fabrication technique of 2DMNS. 
    more » « less