Superconductivity is a fascinating quantum phenomenon characterized by zero electrical resistance and the Meissner effect. To date, several distinct families of superconductors (SCs) have been discovered. These include three-dimensional (3D) bulk SCs in both inorganic and organic materials as well as two-dimensional (2D) thin film SCs but only in inorganic materials. Here we predict superconductivity in 2D and 3D organic metal–organic frameworks by using first-principles calculations. We show that the highly conductive and recently synthesized Cu-benzenehexathial (BHT) is a Bardeen–Cooper–Schrieffer SC. Remarkably, the monolayer Cu-BHT has a critical temperature (Tc) of 4.43 K, while Tc of bulk Cu-BHT is 1.58 K. Different from the enhanced Tc in 2D inorganic SCs which is induced by interfacial effects, the Tc enhancement in this 2D organic SC is revealed to be the out-of-plane soft-mode vibrations, analogous to surface mode enhancement originally proposed by Ginzburg. Our findings not only shed new light on better understanding 2D superconductivity but also open a new direction to search for SCs by interface engineering with organic materials.Keywords: enhanced critical temperature; first-principles calculations; metal−organic framework; Superconductivity;

Tunable spin transport in nanodevices is highly desirable to spintronics. Here, we predict existence of quantum spin Hall effects and tunable spin transport in As-graphane, based on first-principle density functional theory and tight binding calculations. Monolayer As-graphane is constituted by using As adsorbing on graphane with honeycomb H vacancies. Owing to the surface strain, monolayer As-graphane nanoribbons will self-bend toward the graphane side. The naturally curved As-graphane nanoribbons then exhibit unique spin transport properties, distinctively different from the flat ones, which is a two-dimensional topological insulator. Under external stress, one can realize tunable spin transport in curved As-graphane nanoribon arrays. Such intriguing mechanical bending induced spin flips can offer promising applications in the future nanospintronics devices.Keywords: first-principles calculations; graphane; Topological insulator; tunable spin transport;

We demonstrate a new class of nanostructured topological materials that exhibit a topological quantum phase arising from nanoscale structural motifs. Based on first-principles calculations, we show that an array of bismuth nanotubes (Bi-NTs), a superlattice of Bi-NTs with periodicity in the order of tube diameter, behaves as a nanostructured two-dimensional (2D) quantum spin Hall (QSH) insulator, as confirmed from the calculated band topology and 1D helical edge states. The underpinning mechanism of the QSH phase in the Bi-NT array is revealed to be inversion of bonding–antibonding levels of molecular orbitals of constituent nanostructural elements in place of atomic-orbital band inversion in conventional QSH insulators. The quantized edge conductance of the QSH phase in a Bi-NT array can be more easily isolated from bulk contributions and their properties can be highly tuned by tube size, representing distinctive advantages of nanostructured topological phases. Our finding opens a new avenue for topological materials by extending topological phases into nanomaterials with molecular-orbital-band inversion.

We investigate nonlinear elastic effect (NLEF) on the growth of heteroepitaxial islands, a topic of both scientific and technological significance for their applications as quantum dots. We show that the NLEF induces a thermodynamic self-limiting growth mechanism that hinders the strain relaxation of coherent island beyond a maximum size, which is in contrast to indefinite strain relaxation with increasing island size in the linear elastic regime. This self-limiting growth effect shows a strong dependence on the island facet angle, which applies also to islands inside pits patterned in a substrate surface with an additional dependence on the pit inclination angle. Consequently, primary islands nucleate and grow first in the pits and then secondary islands nucleate at the rim around the pits after the primary islands reach the self-limited maximum size. Our theory sheds new lights on understanding the heteroepitaxial island growth and explains a number of past and recent experimental observations.

Spin splitting of Rashba states in two-dimensional electron system provides a promising mechanism of spin manipulation for spintronics applications. However, Rashba states realized experimentally to date are often outnumbered by spin-degenerated substrate states at the same energy range, hindering their practical applications. Here, by density functional theory calculation, we show that Au one monolayer film deposition on a layered semiconductor surface β-InSe(0001) can possess “ideal” Rashba states with large spin splitting, which are completely situated inside the large band gap of the substrate. The position of the Rashba bands can be tuned over a wide range with respect to the substrate band edges by experimentally accessible strain. Furthermore, our nonequilibrium Green’s function transport calculation shows that this system may give rise to the long-sought strong current modulation when made into a device of Datta-Das transistor. Similar systems may be identified with other metal ultrathin films and layered semiconductor substrates to realize ideal Rashba states.

We predict theoretical existence of intrinsic two-dimensional organic topological insulator (OTI) states in Cu–dicyanoanthracene (DCA) lattice, a system that has also been grown experimentally on Cu substrate, based on first-principle density functional theory calculations. The pz-orbital Kagome bands having a Dirac point lying exactly at the Fermi level are found in the freestanding Cu–DCA lattice. The tight-binding model analysis, the calculated Chern numbers, and the semi-infinite Dirac edge states within the spin–orbit coupling gaps all confirm its intrinsic topological properties. The intrinsic TI states are found to originate from a proper number of electrons filling of the hybridized bands from Cu atomic and DCA molecular orbitals based on which similar lattices containing noble metal atoms (Au and Cu) and those molecules with two CN groups (DCA and cyanogens) are all predicted to be intrinsic OTIs.

Graphene has intrigued the science community by many unique properties not found in conventional materials. In particular, it is the strongest two-dimensional material ever measured, being able to sustain reversible tensile elastic strain larger than 20%, which yields an interesting possibility to tune the properties of graphene by strain and thus opens a new field called “straintronics”. In this article, the current progress in the strain engineering of graphene is reviewed. We first summarize the strain effects on the electronic structure and Raman spectra of graphene. We then highlight the electron–phonon coupling greatly enhanced by the biaxial strain and the strong pseudomagnetic field induced by the non-uniform strain with specific distribution. Finally, the potential application of strain-engineering in the self-assembly of foreign atoms on the graphene surface is also discussed. Given the short history of graphene straintronics research, the current progress has been notable, and many further advances in this field are expected.

We have performed a systematic density functional study of surface energy of MoS2 films as a function of thickness from one to twelve layers with the consideration of van der Waals (vdW) interactions using the vdW-DF and DFT-D2 methods. Both vdW schemes show that the surface energy will increase with the increase of the number of atomic layers and converge to a constant value at about six layers. Based on the calculated surface energies, we further analyze the surface contact angle of water droplets on the MoS2 film surface using Young's equation as a function of thickness in comparison with experiments, from which the water–MoS2 interfacial energy is derived to be independent of MoS2 thickness. Our calculations indicate that the vdW interactions between the MoS2 layers play an important role in determining surface energy, and results in the thickness dependence of the contact angle of water droplets on the MoS2 film surface. Our results explain well the recent wetting experiment [Nano Lett., 2014, 14(8), 4314], and will be useful for future studies of physical and chemical properties of ultrathin MoS2 films.

•Different bonding strength of Ta-Ta metallic interactions and Ta-C covalent bonds determine the relative surface energies.•Structural C vacancies in the ζ-Ta4C3 −x phase play a key role in lowering the basal plane surface energy.•Quantum size effects may play a considerable role in determining accurate surface energies of Ta-C metallic films.Using first-principles method, surface energies of crystal planes of different tantalum carbide phases have been calculated. Quantum size effects are shown to possibly play a considerable role in determining accurate surface energies of these metallic films, which have been neglected in previous works. The γ-TaC phase has a more stable (0 0 1) surface than the close-packed (1 1 1) surface. In the α-Ta2C phase, (0 0 1) surface with only Ta termination is more stable than that of mixed Ta-C termination because the metallic bonds between Ta atoms are weaker than the Ta-C covalent bonds. The same is true for the ζ-Ta4C3 phase. The introduction of structural vacancies in the ζ-Ta4C3 −x phase creates more direct Ta metallic bonds, making the Ta-terminated surfaces even more stable. This is consistent with the experimental observations of cleavage of the basal planes, lamellae bridging of cracks, and the high fracture toughness of ζ-Ta4C3 −x.

As a prototype of organic–inorganic hybrid perovskites, CH3NH3PbI3 is attracting extensive attention because of its applications in high-power-conversion-efficiency solar cells. However, the mixed-halide perovskite CH3NH3PbI3–xClx exhibited superior carrier diffusion properties in recent experiments. Using first-principles calculations and the Berry phase method, we calculated the crystal structures and ferroelectric properties of pure and Cl-doped CH3NH3PbI3. The off-center displacement of Pb within the PbI6 octahedron was found to introduce major intrinsic polarization, rather than the off-center displacement of CH3NH3+ within the inorganic lattice or charge polarization within the organic cation, as expected. With chlorine substitution for iodine, the larger electronegativity difference between the halogen and Pb increases the lattice distortion and, hence, the electric polarization increases by as much as ∼50%, which provides a possible mechanism to further assist carrier separation and diffusion in solar cell devices.

We report on the fabrication of a two-dimensional topological insulator Bi(111) bilayer on Sb nanofilms via a sequential molecular beam epitaxy growth technique. Our angle-resolved photoemission measurements demonstrate the evolution of the electronic band structure of the heterostructure as a function of the film thickness and reveal the existence of a two-dimensional spinful massless electron gas within the top Bi bilayer. Interestingly, our first-principles calculation extrapolating the observed band structure shows that, by tuning down the thickness of the supporting Sb films into the quantum dimension regime, a pair of isolated topological edge states emerges in a partial energy gap at 0.32 eV above the Fermi level as a consequence of quantum confinement effect. Our results and methodology of fabricating nanoscale heterostructures establish the Bi bilayer/Sb heterostructure as a platform of great potential for both ultra-low-energy-cost electronics and surface-based spintronics.Keywords: Bi(111) bilayer; Kane−Mele model; quantum spin Hall effect; quantum well states

We predict a family of 2D carbon (C) allotropes, square graphynes (S-graphynes) that exhibit highly anisotropic Dirac fermions, using first-principle calculations within density functional theory. They have a square unit-cell containing two sizes of square C rings. The equal-energy contour of their 3D band structure shows a crescent shape, and the Dirac crescent has varying Fermi velocities from 0.6 × 105 to 7.2 × 105 m/s along different k directions. Near the Fermi level, the Dirac crescent can be nicely expressed by an extended 2D Dirac model Hamiltonian. Furthermore, tight-binding band fitting reveals that the Dirac crescent originates from the next-nearest-neighbor interactions between C atoms. S-graphynes may be used to build new 2D electronic devices taking advantages of their highly directional charge transport.

Based on first-principles and tight-binding calculations, we report that the topological edge states of zigzag Bi(111) nanoribbon can be significantly tuned by H edge adsorption. The Fermi velocity is increased by 1 order of magnitude, as the Dirac point is moved from the Brillouin zone boundary to the Brillouin zone center, and the real-space distribution of Dirac states are made twice more delocalized. These intriguing changes are explained by an orbital filtering effect of edge H atoms, which pushes certain components of the p orbital of edge Bi atoms out of the band gap regime that reshapes the topological edge states. In addition, the spin texture of the Dirac states is also modified, which is described by introducing an effective Hamiltonian. Our findings not only are of fundamental interest but also have practical implications in potential applications of topological insulators.

A fundamental property of solid materials is their stress state. Stress state of a solid or thin film material has profound effects on its thermodynamic stability and physical and chemical properties. The classical mechanical stress (σM) originates from lattice strain (ɛ), following Hooke’s law: σM=Cɛ, where C is elastic constant matrix. Recently, a new concept of quantum electronic stress (σQE) is introduced to elucidate the extrinsic electronic effects on the stress state of solids and thin films, which follows a quantum analog of classical Hooke’s law: σQE=Ξ(Δn), where Ξ is the deformation potential of electronic states and Δn is the variation of electron density. Here, we present mathematical derivation of both the classical and quantum Hooke’s law from density functional theory. We further discuss the physical origin of quantum electronic stress, arising purely from electronic excitation and perturbation in the absence of lattice strain (ɛ=0), and its relation to the degeneracy pressure of electrons in solid and their interaction with the lattice.

Formation of topological quantum phase on a conventional semiconductor surface is of both scientific and technological interest. Here, we demonstrate epitaxial growth of 2D topological insulator, i.e., quantum spin Hall state, on Si(111) surface with a large energy gap, based on first-principles calculations. We show that the Si(111) surface functionalized with one-third monolayer of halogen atoms [Si(111)-33×33-X (X = Cl, Br, I)] exhibiting a trigonal superstructure provides an ideal template for epitaxial growth of heavy metals, such as Bi, which self-assemble into a hexagonal lattice with high kinetic and thermodynamic stability. Most remarkably, the Bi overlayer is atomically bonded to but electronically decoupled from the underlying Si substrate, exhibiting isolated quantum spin Hall state with an energy gap as large as ∼0.8 eV. This surprising phenomenon originates from an intriguing substrate-orbital-filtering effect, which critically selects the orbital composition around the Fermi level, leading to different topological phases. In particular, the substrate-orbital-filtering effect converts the otherwise topologically trivial freestanding Bi lattice into a nontrivial phase; and the reverse is true for Au lattice. The underlying physical mechanism is generally applicable, opening a new and exciting avenue for exploration of large-gap topological surface/interface states.

Topological insulators (TI) are a class of materials exhibiting unique quantum transport properties with potential applications in spintronics and quantum computing. To date, all of the experimentally confirmed TIs are inorganic materials. Recent theories predicted the possible existence of organic TIs (OTI) in two-dimensional (2D) organometallic frameworks. However, those theoretically proposed structures do not naturally exist and remain to be made in experiments. Here, we identify a recently experimentally made 2D organometallic framework, consisting of π-conjugated nickel-bis-dithiolene with a chemical formula Ni3C12S12, which exhibits nontrivial topological states in both a Dirac band and a flat band, therefore confirming the existence of OTI.

Based on systematic first principles calculations, we investigate Sr surface segregation (SSS) in La1−xSrxCo1−yFeyO3−δ (LSCF) (a typical perovskite ABO3 compound), a bottleneck causing efficiency degradation of solid oxide fuel cells. We identify two basic thermodynamic driving forces for SSS and suggest two possible ways to suppress SSS: applying compressive strain and reducing surface charge. We show that compressive strain can be applied through doping of larger elements and surface coating; surface charge can be reduced through doping of higher-valence elements in the Sr- and B-site or lower-valence elements in the La-site and introducing surface A-site vacancies. The net effect of oxygen vacancy is to enhance SSS because its effect of increasing surface charge overrides its effect of inducing compressive strain, while Co substitution of Fe always enhances SSS because it induces tensile strain as well as increases surface charge. Our results explain the recent experimental observation of SSS suppression in LSCF by a La1−xSrxMnO3−δ (LSM) coating.

Topological insulators and graphene present two unique classes of materials, which are characterized by spin-polarized (helical) and nonpolarized Dirac cone band structures, respectively. The importance of many-body interactions that renormalize the linear bands near Dirac point in graphene has been well recognized and attracted much recent attention. However, renormalization of the helical Dirac point has not been observed in topological insulators. Here, we report the experimental observation of the renormalized quasiparticle spectrum with a skewed Dirac cone in a single Bi bilayer grown on Bi2Te3 substrate from angle-resolved photoemission spectroscopy. First-principles band calculations indicate that the quasiparticle spectra are likely associated with the hybridization between the extrinsic substrate-induced Dirac states of Bi bilayer and the intrinsic surface Dirac states of Bi2Te3 film at close energy proximity. Without such hybridization, only single-particle Dirac spectra are observed in a single Bi bilayer grown on Bi2Se3, where the extrinsic Dirac states Bi bilayer and the intrinsic Dirac states of Bi2Se3 are well separated in energy. The possible origins of many-body interactions are discussed. Our findings provide a means to manipulate topological surface states.

The Hofstadter butterfly spectrum for Landau levels in a two-dimensional periodic lattice is a rare example exhibiting fractal properties in a truly quantum system. However, the observation of this physical phenomenon in a conventional material will require a magnetic field strength several orders of magnitude larger than what can be produced in a modern laboratory. It turns out that for a specific range of rotational angles twisted bilayer graphene serves as a special system with a fractal energy spectrum under laboratory accessible magnetic field strengths. This unique feature arises from an intriguing electronic structure induced by the interlayer coupling. Using a recursive tight-binding method, we systematically map out the spectra of these Landau levels as a function of the rotational angle. Our results give a complete description of LLs in twisted bilayer graphene for both commensurate and incommensurate rotational angles and provide quantitative predictions of magnetic field strengths for observing the fractal spectra in these graphene systems.

Using first-principles calculations, we have carried out a systematic comparative study of the microscopic atomic defect configurations in cubic and tetragonal yttria-stabilized zirconia (YSZ) and their correlation with the macroscopic lattice parameters and relative phase stability, as a function of Y concentration. We found that Y atoms sit at the second-nearest-neighbor cation sites to oxygen vacancies and repel each other; oxygen vacancies form pairs and these pairs repel each other. Using the optimized defect configurations as inputs, we correctly identify the experimentally observed tetragonal to cubic transition point and predict the changes of lattice parameters with the increasing Y concentration, in excellent agreement with experiment. Our studies reveal an interesting correlation between the microscopic atomic defect configuration and macroscopic lattice properties.Highlights► Correlation between the microscopic atomic defect configuration and macroscopic lattice properties is revealed. ► Y atoms sit at the second-nearest-neighbor cation sites to oxygen vacancies and repel each other. ► Oxygen vacancies form pairs and these pairs repel each other.

Quantum cellular automata (QCA) is an innovative approach that incorporates quantum entities in classical computation processes. Binary information is encoded in different charge states of the QCA cells and transmitted by the inter-cell Coulomb interaction. Despite the promise of QCA, however, it remains a challenge to identify suitable building blocks for the construction of QCA. Graphene has recently attracted considerable attention owing to its remarkable electronic properties. The planar structure makes it feasible to pattern the whole device architecture in one sheet, compatible with the existing electronics technology. Here, we demonstrate theoretically a new QCA architecture built upon nanopatterned graphene quantum dots (GQDs). Using the tight-binding model, we determine the phenomenological cell parameters and cell–cell response functions of the GQD-QCA to characterize its performance. Furthermore, a GQD-QCA architecture is designed to demonstrate the functionalities of a fundamental majority gate. Our results show great potential in manufacturing high-density ultrafast QCA devices from a single nanopatterned graphene sheet.

Using molecular dynamics (MD) simulations, we have investigated the kinetics of the graphene edge folding process. The lower limit of the energy barrier is found to be ∼380 meV/Å (or about 800 meV per edge atom) and ∼50 meV/Å (or about 120 meV per edge atom) for folding the edges of intrinsic clean single-layer graphene (SLG) and double-layer graphene (DLG), respectively. However, the edge folding barriers can be substantially reduced by imbalanced chemical adsorption, such as of H atoms, on the two sides of graphene along the edges. Our studies indicate that thermal folding is not feasible at room temperature (RT) for clean SLG and DLG edges and is feasible at high temperature only for DLG edges, whereas chemical folding (with adsorbates) of both SLG and DLG edges can be spontaneous at RT. These findings suggest that the folded edge structures of suspended graphene observed in some experiments are possibly due to the presence of adsorbates at the edges. Open image in new window

We demonstrate theoretically a new mechanism for the energy-selective manipulation of electron beam by nanostructured heterodimensional graphene junctions (HDGJs). Beam splitting, collimation, and beam-guide can all be realized by designing HDGJs of different dimensionality, size and orientation. Importantly, these different functions can be combined together by predesigned patterning of multiple HDGJ units in one graphene sheet, making it feasible for large-scale integration of quantum devices. Based on transport simulations, we further suggest an method to map out the electron beam propagation path through HDGJs by scanning probe microscopy.Keywords: electron beam manipulation; graphene junction; graphene transport; scanning probe microscopy

We predict a new class of 2-D crystalline “bulk” magnets—the graphene nanohole (GNH) superlattices with each GNH acting like a “super” magnetic atom, using first principles calculations. We show that such superlattices can exhibit long-range magnetic order above room temperature, with a collective magnetic behavior governed by inter-NH spin spin interactions in additional to intra-NH spin ordering. Furthermore, magnetic semiconductors can be made by doping magnetic NHs into semiconducting NH superlattices. The possibility of engineering magnetic GNHs for storage media and spintronics applications is discussed.

Based on the underlying graphene lattice symmetry and an itinerant magnetism model on a bipartite lattice, we propose a unified geometric rule for designing graphene-based magnetic nanostructures: spins are parallel (ferromagnetic (FM)) on all zigzag edges which are at angles of 0° and 120° to each other, and antiparallel (antiferromagnetic (AF)) at angles of 60° and 180°. The rule is found to be consistent with all the systems that have been studied so far. Applying the rule, we predict several novel graphene-based magnetic nanostructures: 0-D FM nanodots with the highest possible magnetic moments, 1-D FM nanoribbons, and 2-D magnetic superlattices.

Based on systematic first principles calculations, we investigate Sr surface segregation (SSS) in La1−xSrxCo1−yFeyO3−δ (LSCF) (a typical perovskite ABO3 compound), a bottleneck causing efficiency degradation of solid oxide fuel cells. We identify two basic thermodynamic driving forces for SSS and suggest two possible ways to suppress SSS: applying compressive strain and reducing surface charge. We show that compressive strain can be applied through doping of larger elements and surface coating; surface charge can be reduced through doping of higher-valence elements in the Sr- and B-site or lower-valence elements in the La-site and introducing surface A-site vacancies. The net effect of oxygen vacancy is to enhance SSS because its effect of increasing surface charge overrides its effect of inducing compressive strain, while Co substitution of Fe always enhances SSS because it induces tensile strain as well as increases surface charge. Our results explain the recent experimental observation of SSS suppression in LSCF by a La1−xSrxMnO3−δ (LSM) coating.

We have performed a systematic density functional study of surface energy of MoS2 films as a function of thickness from one to twelve layers with the consideration of van der Waals (vdW) interactions using the vdW-DF and DFT-D2 methods. Both vdW schemes show that the surface energy will increase with the increase of the number of atomic layers and converge to a constant value at about six layers. Based on the calculated surface energies, we further analyze the surface contact angle of water droplets on the MoS2 film surface using Young's equation as a function of thickness in comparison with experiments, from which the water–MoS2 interfacial energy is derived to be independent of MoS2 thickness. Our calculations indicate that the vdW interactions between the MoS2 layers play an important role in determining surface energy, and results in the thickness dependence of the contact angle of water droplets on the MoS2 film surface. Our results explain well the recent wetting experiment [Nano Lett., 2014, 14(8), 4314], and will be useful for future studies of physical and chemical properties of ultrathin MoS2 films.