We present a density functional theory study of the thermodynamic and electronic properties of phosphorene nanoribbons. We consider a variety of terminations and reconstructions of ribbon edges, both with and without hydrogen passivation, and calculate an ab intio phase diagram that identifies energetically preferred edges as a function of temperature and hydrogen partial pressure. These studies are also accompanied by detailed electronic structure calculations from which we find that ribbons with hydrogenated edges are typically direct gap semiconductors with fundamental gaps that are in excess of phosphorene, the gaps varying inversely with ribbon width. In contrast, ribbons with bare or partially passivated edges either have metallic edges or are semiconducting with band gaps that are smaller than those of their hydrogenated counterparts due to the appearance of midgap edge states. Overall, our studies provide a basis for tailoring the electronic properties of phosphorene nanoribbons by controlling the edge termination via processing conditions (temperature and hydrogen partial pressure) as well as by confinement of carriers via control over ribbon width.

We report results of first-principles density functional theory calculations, which introduce a new class of carbon nanostructures formed due to creation of covalent interlayer C-C bonds in twisted bilayer graphene (TBG). This interlayer bonding becomes possible by hydrogenation of the graphene layers according to certain hydrogenation patterns. The resulting relaxed configurations consist of two-dimensional (2D) superlattices of diamond-like nanocrystals embedded within the graphene layers, with the same periodicity as that of the Moiré pattern corresponding to the rotational layer stacking in TBG. The 2D diamond nanodomains resemble the cubic or the hexagonal diamond phase. The detailed structure of these superlattice configurations is determined by parameters that include the twist angle, ranging from 0 to ~15 o , and the number of interlayer C-C bonds formed per unit cell of the superlattice. We demonstrate that formation of such interlayer-bonded finite domains causes the opening of a band gap in the electronic band structure of TBG, which depends on the density and spatial 2 distribution of interlayer C-C bonds. We have predicted band gaps as wide as 1.2 eV and found that the band gap increases monotonically with increasing size of the embedded diamond nanodomain in the unit cell of the superlattice. Such nanostructure formation constitutes a promising approach for opening a precisely tunable band gap in bilayer graphene.

Diamond nanothreads (DNTs) are fully sp-bonded one-dimensional carbon nanostructures, synthesized recently through compression of crystalline benzene. They possess outstanding mechanical strength, suitable for the development of novel nanostructured reinforced materials. In this article, we use density functional theory calculations to investigate the feasibility and physical properties of functionalized DNTs. We show that the stacking and covalent bonding of benzene derivative molecules (toluene, aniline, phenol and fluorobenzene) may lead to stable configurations analogous to benzene-derived DNTs, with functional groups (-CH, -NH, -OH, -F) covalently attached to the surface. The same principle was also applied to pyridine, an aromatic heterocyclic compound, resulting in DNTs containing N heteroatoms within the sp C-C chain. We show that the mechanical properties remain practically unaltered compared to the original material, and that the electronic properties can be tuned upon functionalization. The presence of polar functional groups on DNT surfaces are expected to affect their compatibility with other materials and solvents, enabling the development of novel processes and technological applications using DNTs.

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Using molecular-dynamics simulations of tensile deformation and shear loading tests, we determine the mechanical properties of superlattices of diamond-like nanocrystals embedded in twisted bilayer graphene (TBG) generated by covalent interlayer bonding through patterned hydrogenation. We find that the mechanical properties of these superstructures can be precisely tuned by controlling the fraction of sp3-hybridized C-C bonds in the material, fsp3, through the extent of chemical functionalization. The Young modulus and ultimate tensile strength weaken compared with pristine TBG with increasing fsp3, but they remain superior to those of most conventional materials. The interlayer shear modulus increases monotonically with fsp3.

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We report results based on first-principles density functional theory calculations for the structural and electronic properties of fluorinated carbon nanostructures formed by interlayer covalent C−C bonding in twisted bilayer graphene (TBG). These hybrid sp 2 /sp 3 carbon nanostructures consist of superlattices of diamond-like or fullerene-like nanodomains embedded within the graphene layers of TBG. The symmetry and periodicity of these superstructures are determined by the Moirépattern formed by the twisting of the graphene planes of the bilayer and is responsible for the character of the superstructures, which may range from semimetallic to semiconducting or insulating depending on the tuning of specific parameters, such as the twist angle and the density of interlayer C− C bonds. We demonstrate that fluorine chemisorption generates more stable structures than those formed by hydrogen chemisorption, suggesting that functionalizing TBG by controlled patterned fluorination is a better strategy than hydrogenation for synthesis of nanostructures that are stable over a broader temperature range consistently with what has been observed for single-layer graphene. Significant differences found between fluorinated and hydrogenated configurations in their structural parameters, surface properties, and electronic structures suggest that the choice of functionalizing agent can be used for precise tuning of the properties of the resulting nanostructures.

Based on first-principles density functional theory calculations, we report a novel class of carbon nanostructures consisting of superlattice arrangements of caged fullerene configurations of various sizes embedded within planes of twisted bilayer graphene. Formation of these structures is the outcome of interlayer C-C bonding between pairs of graphene planes chemically modified with certain patterns of chemisorbed hydrogen and rotated with respect to each other by angles around 30°. A specific subclass of these nanostructures preserves the main features of the electronic structure of pristine single-layer graphene. Our study proposes possible functionalization strategies to systematically tailor the electronic properties of bilayer graphene.