Novel two-dimensional boron oxynitride predicted using the USPEX evolutionary algorithm.

Oxidation is a unique process that significantly changes the structure and properties of a material. Doping of h-BN by oxygen is a hot topic in material science leading to the possibility of synthesis of novel 2D structures with customized electronic properties. It is still unclear how the atomic structure changes in the presence of external atoms during the oxidation of h-BN. We predict novel two-dimensional (2D) arrangements of boron oxynitride using the evolutionary algorithm of crystal structure prediction USPEX. All considered structures demonstrate semiconducting properties with a reduced bandgap compared with h-BN. Both molecular dynamics and phonon calculations show the dynamical stability of the new 2D B5N3O2 phase, and our calculations demonstrate that it can form a bulk layered structure with an interlayer distance larger than that of pure h-BN. The optical characterization shows a redshift of the absorption spectrum compared with pure h-BN. Incorporation of oxygen into the structure of 2D BN during synthesis or oxidation can dramatically change the covalent network of h-BN while preserving its two-dimensionality and flatness, following the presence of local dipole moments which could improve the piezoelectric properties.

Fluorinated graphene nanoparticles with 1-3 nm electrically active graphene quantum dots.

A new approach to creating a new and locally nanostructured graphene-based material is reported. We studied the electric and structural properties of partially fluorinated graphene (FG) films obtained from an FG-suspension and nanostructured by high-energy Xe ions. Local shock heating in ion tracks is suggested to be the main force driving the changes. It was found that ion irradiation leads to the formation of locally thermally expanded FG and its cracking into nanoparticles with small (∼1.5-3 nm) graphene quantum dots (GQD), embedded in them. The bandgap of GQD was estimated as 1 -1.5 eV. A further developed approach was applied to correct the functional properties of printed FG-based crossbar memristors. Dielectric FG films with small quantum dots may offer prospects in graphene-based electronics due to their stability and promising properties.

Diamane-like Films Based on Twisted G/BN Bilayers: DFT Modelling of Atomic Structures and Electronic Properties.

Diamanes are unique 2D carbon materials that can be obtained by the adsorption of light atoms or molecular groups onto the surfaces of bilayer graphene. Modification of the parent bilayers, such as through twisting of the layers and the substitution of one of the layers with BN, leads to drastic changes in the structure and properties of diamane-like materials. Here, we present the results of the DFT modelling of new stable diamane-like films based on twisted Moiré G/BN bilayers. The set of angles at which this structure becomes commensurate was found. We used two commensurate structures with twisted angles of θ = 10.9° and θ = 25.3° with the smallest period as the base for the formation of the diamane-like material. Previous theoretical investigations did not take into account the incommensurability of graphene and boron nitride monolayers when considering diamane-like films. The double-sided hydrogenation or fluorination of Moiré G/BN bilayers and the following interlayer covalent bonding led to the opening of a gap up to 3.1 eV, which was lower than the corresponding values of h-BN and c-BN. The considered G/BN diamane-like films offer great potential in the future for a variety of engineering applications.

Moiré Diamones: New Diamond-like Films of Semifunctionalized Twisted Graphene Layers.

We proposed novel carbon nanostructures based on a twisted few-layered graphene with one side passivated by hydrogen or fluorine: Moiré diamones on graphene. The presence of a dangling bond at the bottom layer of diamones leads to the appearance of spin density localization, which can be tuned by the variation of the twist angle with the following formation of Moiré diamones. The spin-polarized nature of electronic density distribution was obtained and discussed in detail on the basis of ab initio calculations. Such a feature makes Moiré diamones a promising key element in the field of controllable spintronic devices.

Ultra-Low Thermal Conductivity of Moiré Diamanes.

Ultra-thin diamond membranes, diamanes, are one of the most intriguing quasi-2D films, combining unique mechanical, electronic and optical properties. At present, diamanes have been obtained from bi- or few-layer graphene in AA- and AB-stacking by full hydrogenation or fluorination. Here, we study the thermal conductivity of diamanes obtained from bi-layer graphene with twist angle θ between layers forming a Moiré pattern. The combination of DFT calculations and machine learning interatomic potentials makes it possible to perform calculations of the lattice thermal conductivity of such diamanes with twist angles θ of 13.2∘, 21.8∘ and 27.8∘ using the solution of the phonon Boltzmann transport equation. Obtained results show that Moiré diamanes exhibit a wide variety of thermal properties depending on the twist angle, namely a sharp decrease in thermal conductivity from high for "untwisted" diamanes to ultra-low values when the twist angle tends to 30∘, especially for hydrogenated Moiré diamanes. This effect is associated with high anharmonicity and scattering of phonons related to a strong symmetry breaking of the atomic structure of Moiré diamanes compared with untwisted ones.

Semiconductor nanochannels in metallic carbon nanotubes by thermomechanical chirality alteration.

Carbon nanotubes have a helical structure wherein the chirality determines whether they are metallic or semiconducting. Using in situ transmission electron microscopy, we applied heating and mechanical strain to alter the local chirality and thereby control the electronic properties of individual single-wall carbon nanotubes. A transition trend toward a larger chiral angle region was observed and explained in terms of orientation-dependent dislocation formation energy. A controlled metal-to-semiconductor transition was realized to create nanotube transistors with a semiconducting nanotube channel covalently bonded between a metallic nanotube source and drain. Additionally, quantum transport at room temperature was demonstrated for the fabricated nanotube transistors with a channel length as short as 2.8 nanometers.