Stability and electronic properties of gallenene.

Two-dimensional metals offer intriguing possibilities to explore the metallic and other related properties in systems with reduced dimensionality. Here, following recent experimental reports of synthesis of two-dimensional metallic gallium (gallenene) on insulating substrates, we conduct a computational search of gallenene structures using the Particle Swarm Optimization algorithm, and identify stable low energy structures. Our calculations of the critical temperature for conventional superconductivity yield values of ∼7 K for gallenene. We also emulate the presence of the substrate by introducing the external confining potential and test its effect on the structures with unstable phonons.

Probing borophene oxidation at the atomic scale.

Two-dimensional boron (i.e. borophene) holds promise for a variety of emerging nanoelectronic and quantum technologies. Since borophene is synthesized under ultrahigh vacuum (UHV) conditions, it is critical that the chemical stability and structural integrity of borophene in oxidizing environments are understood for practical borophene-based applications. In this work, we assess the mechanism of borophene oxidation upon controlled exposure to air and molecular oxygen in UHV via scanning tunneling microscopy andspectroscopy, x-ray photoelectron spectroscopy, and density functional theory calculations. While borophene catastrophically degrades almost instantaneously upon exposure to air, borophene undergoes considerably more controlled oxidation when exposed to molecular oxygen in UHV. In particular, UHV molecular oxygen dosing results in single-atom covalent modification of the borophene basal plane in addition to disordered borophene edge oxidation that shows altered electronic characteristics. By comparing these experimental observations with density functional theory calculations, further atomistic insight is gained including pathways for molecular oxygen dissociation, surface diffusion, and chemisorption to borophene. Overall, this study provides an atomic-scale perspective of borophene oxidation that will inform ongoing efforts to passivate and utilize borophene in ambient conditions.

Borophene synthesis beyond the single-atomic-layer limit.

Synthetic two-dimensional (2D) materials have no bulk counterparts and typically exist as single atomic layers due to substrate-stabilized growth. Multilayer formation, although broadly sought for structure and property tuning, has not yet been achieved in the case of synthetic 2D boron: that is, borophene1,2. Here, we experimentally demonstrate the synthesis of an atomically well-defined borophene polymorph beyond the single-atomic-layer (SL) limit. The structure of this bilayer (BL) borophene is consistent with two covalently bonded α-phase layers (termed BL-α borophene) as evidenced from bond-resolved scanning tunnelling microscopy, non-contact atomic force microscopy and density functional theory calculations. While the electronic density of states near the Fermi level of BL-α borophene is similar to SL borophene polymorphs, field-emission resonance spectroscopy reveals distinct interfacial charge transfer doping and a heightened local work function exceeding 5 eV. The extension of borophene polymorphs beyond the SL limit significantly expands the phase space for boron-based nanomaterials.

Step-Edge Epitaxy for Borophene Growth on Insulators.

Borophene─a monatomic layer of boron atoms─stands out among two-dimensional (2D) materials, with its versatile properties tantalizing for physics exploration and next-generation devices. Yet its phases are all synthesized on and stay bound to metal substrates, hampering both characterization and use. Borophene growth on an inert insulator would allow postsynthesis exfoliation, but the weak adhesion to such a substrate results in a high 2D nucleation barrier, preventing clean borophene growth. This challenge can be circumvented in a strategy devised and demonstrated here with ab initio calculations. Naturally present 1D-defects, the step-edges on an h-BN substrate surface, enable boron epitaxial assembly, reduce the nucleation dimensionality, and lower the barrier by an order of magnitude (to 1.1 eV or less), yielding a v1/9 phase. Weak borophene adhesion to the insulator makes it readily accessible for comprehensive property tests or transfer into the device setting.

Nano-Thermodynamics of Chemically Induced Graphene-Diamond Transformation.

Nearly 2D diamond, or diamane, is coveted as an ultrathin sp3 -carbon film with unique mechanics and electro-optics. The very thinness (≈h) makes it possible for the surface chemistry, for example, adsorbed atoms, to shift the bulk phase thermodynamics in favor of diamond, from multilayer graphene. Thermodynamic theory coupled with atomistic first principles computations predicts not only the reduction of required pressure (p/p∞  > 1 - h0 /h) but also the nucleation barriers, definitive for the kinetic feasibility of diamane formation. Moreover, the optimal adsorbent chair-pattern on a bilayer graphene results in a cubic diamond lattice, while for thicker precursors the adsorbent boat-structure tends to produce hexagonal diamond (lonsdaleite), if graphene is in AA' stacking to start with. As adsorbents, H and F are conducive to diamond formation, while Cl appears sterically hindered.