We present a systematic density functional theory study of the electronic properties, optical spectra, and relative thermodynamic stability of semiconducting graphene nanoribbons. We consider ribbons with different edge nature including bare and hydrogen-terminated ribbons, several crystallographic orientations, and widths up to 3 nm. Our results can be extrapolated to wider ribbons providing a qualitative way of determining the electronic properties of ribbons with widths of practical significance. We predict that in order to produce materials with band gaps similar to Ge or InN, the width of the ribbons must be between 2 and 3 nm. If larger bang gap ribbons are needed (like Si, InP, or GaAs), their width must be reduced to 1-2 nm. According to the extrapolated inverse power law obtained in this work, armchair carbon nanoribbons of widths larger than 8 nm will present a maximum band gap of 0.3 eV, while for ribbons with a width of 80 nm the maximum possible band gap is 0.05 eV. For chiral nanoribbons the band gap oscillations rapidly vanish as a function of the chiral angle indicating that a careful design of their crystallographic nature is an essential ingredient for controlling their electronic properties. Optical excitations show important differences between ribbons with and without hydrogen termination and are found to be sensitive to the carbon nanoribbon width. This should provide a practical way of revealing information on their size and the nature of their edges.

We present a novel comprehensive first-principles theoretical study of the electronic properties and relative stabilities of edge-oxidized zigzag graphene nanoribbons. The oxidation schemes considered include hydroxyl, carboxyl, ether, and ketone groups. Using screened exchange density functional theory, we show that these oxidized ribbons are more stable than hydrogen-terminated nanoribbons except for the case of the etheric groups. The stable oxidized configurations maintain a spin-polarized ground state with antiferromagnetic ordering localized at the edges, similar to the fully hydrogenated counterparts. More important, edge oxidation is found to lower the onset electric field required to induce half-metallic behavior and extend the overall field range at which the systems remain half-metallic. Once the half-metallic state is reached, further increase of the external electric field intensity produces a rapid decrease in the spin magnetization up to a point where the magnetization is quenched completely. Finally, we find that oxygen containing edge groups have a minor effect on the energy difference between the antiferromagnetic ground state and the above-lying ferromagnetic state.

The interlayer sliding energy landscape of hexagonal boron nitride (h-BN) is investigated via a van der Waals corrected density functional theory approach. It is found that the main role of the van der Waals forces is to "anchor" the layers at a fixed distance, whereas the electrostatic forces dictate the optimal stacking mode and the interlayer sliding energy. A nearly free-sliding path is identified, along which bandgap modulations of ∼ 0.6 eV are obtained. We propose a simple geometrical model that quantifies the registry matching between the layers and captures the essence of the corrugated h-BN interlayer energy landscape. The simplicity of this phenomenological model opens the way to the modeling of complex layered structures, such as carbon and boron nitride nanotubes.The interlayer potential landscape in layered materials is essential for understanding their mechanical and electromechanical behavior. For example, nanoelectromechanical systems (NEMS) based on low dimensional structures of such materials often rely on mechanical deformations such as twisting [1][2][3] and bending [4][5][6]. These processes involve relative sliding of the layers, which exhibits a corrugated energy landscape even in atomically flat systems, such as graphite and hexagonal boron nitride (h-BN). This corrugation arises from the non-uniform charge density distribution around the atomic positions within each layer [7][8][9]. It is well accepted that the most important factors that govern corrugation in such system are electrostatic and dispersion interactions. However, a clear picture of how the complex interplay between these factors determines the corrugated energy landscape and its manifestation in unique material properties has not emerged yet.Previous efforts towards the understanding of these phenomena have utilized density functional theory (DFT) with (semi-)local approximations [9][10][11][12]. However, these methods do not provide an appropriate description of dispersive interactions. Several approaches within DFT have been developed to overcome this problem, demonstrating successful treatment of dispersion effects in graphite [13][14][15] and h-BN [13,14,16]. However, to the best of our knowledge, such studies have not addressed the question of corrugation.In this letter, we present a theoretical study of the intricate interplay between dispersion and electrostatic interactions in layered materials. As an illustrative example we choose the case of h-BN, where both types of interactions are expected to have a considerable influence on the landscape of the interlayer potential. Using a first-principles van der Waals (vdW) corrected DFT approach, we show that dispersion interactions play the role of fixing the interlayer distance, while the electrostatic forces determine the optimal stacking mode and the interlayer sliding corrugation. In addition, we predict the existence of a nearly free-sliding path along which considerable bandgap modulations are obtained. Finally, we propose a simple geometrical model that quantifies ...

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Structural superlubricity is a fascinating tribological phenomenon, in which the lateral interactions between two incommensurate contacting surfaces are effectively cancelled resulting in ultralow sliding friction. Here we report the experimental realization of robust superlubricity in microscale monocrystalline heterojunctions, which constitutes an important step towards the macroscopic scale-up of superlubricity. The results for interfaces between graphite and hexagonal boron nitride clearly demonstrate that structural superlubricity persists even when the aligned contact sustains external loads under ambient conditions. The observed frictional anisotropy in the heterojunctions is found to be orders of magnitude smaller than that measured for their homogeneous counterparts. Atomistic simulations reveal that the underlying frictional mechanisms in the two cases originate from completely different dynamical regimes. Our results are expected to be of a general nature and should be applicable to other van der Waals heterostructures.

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We present a comparative assessment of the accuracy of two different approaches for evaluating dispersion interactions: interatomic pairwise corrections and semiempirical meta-generalized-gradient-approximation (meta-GGA)-based functionals. This is achieved by employing conventional (semi)local and (screened-)hybrid functionals, as well as semiempirical hybrid and nonhybrid meta-GGA functionals of the M06 family, with and without interatomic pairwise Tkatchenko-Scheffler corrections. All of those are tested against the benchmark S22 set of weakly bound systems, a representative larger molecular complex (dimer of NiPc molecules), and a representative dispersively bound solid (hexagonal boron nitride). For the S22 database, we also compare our results with those obtained from the pairwise correction of Grimme (DFT-D3) and nonlocal Langreth-Lundqvist functionals (vdW-DF1 and vdW-DF2). We find that the semiempirical kinetic-energy-density dependence introduced in the M06 functionals mimics some of the nonlocal correlation needed to describe dispersion. However, long-range contributions are still missing. Pair-wise interatomic corrections, applied to conventional semilocal or hybrid functionals, or to M06 functionals, provide for a satisfactory level of accuracy irrespectively of the underlying functional. Specifically, screened-hybrid functionals such as the Heyd-Scuseria-Ernzerhof (HSE) approach reduce self-interaction errors in systems possessing both localized and delocalized orbitals and can be applied to both finite and extended systems. Therefore, they serve as a useful underlying functional for dispersion corrections.

Despite their partial ionic nature, many layered diatomic crystals avoid internal electric polarization by forming a centrosymmetric lattice at their optimal van-der-Waals stacking. Here, we report a stable ferroelectric order emerging at the interface between two naturally-grown flakes of hexagonal-boron-nitride, which are stacked together in a metastable non-centrosymmetric parallel orientation. We observe alternating domains of inverted normal polarization, caused by a lateral shift of one lattice site between the domains. Reversible polarization switching coupled to lateral sliding is achieved by scanning a biased tip above the surface. Our calculations trace the origin of the phenomenon to a subtle interplay between charge redistribution and ionic displacement, and provide intuitive insights to explore the interfacial polarization and its unique “slidetronics” switching mechanism.