Intersite Coulomb Interactions in Charge-Ordered Systems.

Using ab initio approaches for extended Hubbard interactions coupled to phonons, we reveal that the intersite Coulomb interaction plays important roles in determining various distinctive phases of the paradigmatic charge-ordered materials of Ba_{1-x}K_{x}AO_{3} (A=Bi and Sb). We demonstrated that all their salient doping dependent experiment features such as breathing instabilities, anomalous phonon dispersions, and transition between charge-density wave and superconducting states can be accounted for very well if self-consistently obtained nearest neighbor Hubbard interactions are included, thus establishing a minimal criterion for reliable descriptions of spontaneous charge orders in solids.

Engineering Topological Surface States of Cr-Doped Bi2Se3 Films by Spin Reorientation and Electric Field.

The tailoring of topological surface states in topological insulators is essential for device applications and for exploring new topological phase. Here, we propose a practical way to induce the quantum anomalous Hall phase and unusual metal-insulator transitions in Cr-doped Bi2Se3 films based on the model Hamiltonian and first-principles calculations. Using the combination of in-plane and plane-normal components of the spin along with external electric fields, we demonstrate that the topological state and band structures of topological insulating films exhibit rich features such as the shift of Dirac cones and the opening of nontrivial band gaps. We also show that the in-plane magnetization leads to significant suppression of inter-TSS scattering in Cr-doped Bi2Se3. Our work provides new strategies to obtain the desired electronic structures for the device, complementary to the efforts of an extensive material search.

Spin rectification by orbital polarization in Bi-bilayer nanoribbons.

We investigate the edge states of quantum spin-Hall phase Bi(111) bilayer nano-ribbons (BNRs) and their spin-rectifying effect using first-principles calculations and a non-equilibrium transport method. As low-dimensional materials, BNRs have tunable electronic properties, which are not only dependent on the edge shape, chemical passivation, or external electric fields but also governed by geometrical deformation. Depending on the passivation types, the interaction of the helical edge states in BNRs exhibits various patterns, enabling the valley engineering of the Dirac cones. In addition, the spin texture of the Dirac state is significantly tuned by edge passivation, external electric fields and geometric deformations. We demonstrate that curved BNRs can be used as the spin valves to rectify the electric currents via the edge states. Our results provide a practical way of utilizing two-dimensional topological insulator Bi bilayers for spintronic devices.

Atomic layer-by-layer thermoelectric conversion in topological insulator bismuth/antimony tellurides.

Material design for direct heat-to-electricity conversion with substantial efficiency essentially requires cooperative control of electrical and thermal transport. Bismuth telluride (Bi2Te3) and antimony telluride (Sb2Te3), displaying the highest thermoelectric power at room temperature, are also known as topological insulators (TIs) whose electronic structures are modified by electronic confinements and strong spin-orbit interaction in a-few-monolayers thickness regime, thus possibly providing another degree of freedom for electron and phonon transport at surfaces. Here, we explore novel thermoelectric conversion in the atomic monolayer steps of a-few-layer topological insulating Bi2Te3 (n-type) and Sb2Te3 (p-type). Specifically, by scanning photoinduced thermoelectric current imaging at the monolayer steps, we show that efficient thermoelectric conversion is accomplished by optothermal motion of hot electrons (Bi2Te3) and holes (Sb2Te3) through 2D subbands and topologically protected surface states in a geometrically deterministic manner. Our discovery suggests that the thermoelectric conversion can be interiorly achieved at the atomic steps of a homogeneous medium by direct exploiting of quantum nature of TIs, thus providing a new design rule for the compact thermoelectric circuitry at the ultimate size limit.

Topological phase transition in the interaction of surface Dirac fermions in heterostructures.

Material with a nontrivial topology in its electronic structure enforces the existence of helical Dirac fermionic surface states. We discover emergent topological phases in the stacked structures of topological insulator and band insulator layers where the surface Dirac fermions interact with each other with a particular helicity ordering. Using first-principles calculations and a model Lagrangian, we explicitly demonstrate that such helicity ordering occurs in real materials of ternary chalcogen compounds and determines their topological-insulating phase. Our results reveal the rich collective nature of interacting surface Dirac fermions and pave the way for utilizing topological phases for technological devices such as nonvolatile memories.

Kohn anomalies in topological insulator thin films: first-principles study.

Kohn anomaly is a non-smooth phonon softening induced by electron-phonon coupling in low-dimensional metals. Some measurements claimed that Kohn anomalies are present in topological materials due to the Dirac fermions in the bulk or in the surface. However, first-principles calculations have not reproduced the Kohn anomalies, especially, on the surface of topological insulators. It is still unclear about the origin of the controversy for the existence of the Kohn anomaly whether it is a numerical shortcoming or misinterpretation in measurement. In this study, we investigate the surface Kohn anomaly in two topological insulators Bi2Se3and SnSe using the state-of-the-art Wannier interpolation schemes. We find that Bi2Se3exhibits the Kohn anomaly but only in the bulk-like phonon modes by structural confinement along thec-axis. Interestingly, SnSe exhibits the surface Kohn anomaly in support of the experimental report on Pb0.7Sn0.3Se. We show that double Dirac cones in SnSe surface states are responsible for the Kohn anomaly, which is even enhanced if the subsurface states are partially occupied.

Lattice dynamical properties of antiferromagnetic oxides calculated using self-consistent extended Hubbard functional method.

We study the lattice dynamics of antiferromagnetic transition-metal oxides by using self-consistent Hubbard functionals. We calculate the ground states of the oxides with the on-site and intersite Hubbard interactions determined self-consistently within the framework of density functional theory. The on-site and intersite Hubbard terms fix the errors associated with the electron self-interaction in the local and semilocal functionals. Inclusion of the intersite Hubbard terms in addition to the on-site Hubbard terms produces accurate phonon dispersion of the transition-metal oxides. Calculated Born effective charges and high-frequency dielectric constants are in good agreement with experiment. Our study provides a computationally inexpensive and accurate set of first-principles calculations for strongly-correlated materials and related phenomena.

Controlling energy gap of bilayer graphene by strain.

Using the first principles calculations, we show that mechanically tunable electronic energy gap is realizable in bilayer graphene if different homogeneous strains are applied to the two layers. It is shown that the size of the energy gap can be simply controlled by adjusting the strength and direction of these strains. We also show that the effect originates from the occurrence of strain-induced pseudoscalar potentials in graphene. When homogeneous strains with different strengths are applied to each layer of bilayer graphene, transverse electric fields across the two layers can be generated without any external electronic sources, thereby opening an energy gap. The results demonstrate a simple mechanical method of realizing pseudoelectromagnetism in graphene and suggest a maneuverable approach to fabrication of electromechanical devices based on bilayer graphene.

Efficient Training of Machine Learning Potentials by a Randomized Atomic-System Generator.

Machine learning potentials provide an efficient and comprehensive tool to simulate large-scale systems inaccessible by conventional first-principles methods still in a similar level of accuracy. One critical issue in constructing machine learning potentials is to build training data sets cost-effectively that can represent the potential energy surface in a wide range of configurations. We develop a scheme named randomized atomic-system generator (RAG) to produce the training sets that widely cover the potential energy surface by combining the random sampling and structural optimization. We apply the scheme to construct the machine learning potentials for simulation of chalcogen-based phase change materials. Constructed machine learning potentials successfully simulate the dynamics of melting and crystallization processes of binary GeTe at a level comparable to first-principles simulations. The visual analysis shows that the RAG-generated training set represents the crystallization process including the amorphous phases. From the velocity autocorrelation function obtained from the molecular dynamics simulations, we calculate the phonon density of states to analyze the vibrational properties during crystallization.

Effect of vacancy disorder in phase-change materials.

Ge-Sb-Te-based phase-change materials (PCMs) exhibit contrasting electrical and optical properties upon change in atomic structures, which contain the octahedral p -orbital bonding and also substantial disordered vacancies. While extensive studies have been carried out, there is little detailed analysis of how the vacancy distribution and bonding nature are inter-correlated to affect the physical properties. We studied the effect of vacancy distribution on the octahedral p -bonding network in PCMs using a simple tight-binding model and ab initio calculations. We showed that the octahedral p -bonding network can be described as a collection of independent linear chains and that the vacancy disorders are rephrased as a distribution of atomic chain pieces. This finding enables to link the vacancy distribution to various aspects of materials properties such as total energy, structural distortions, and charge localization.

Origin of robust out-of-plane ferroelectricity in d1T-MoS2 monolayer.

The d1T-MoS2, distorted-1T group-VIB transition metal dichalcogenides monolayer, is considered as promising atomically thin out-of-plane ferroelectric materials. We study the origin of the ferroelectricity in d1T-MoS2 monolayer using first-principles calculations and the Landau theory of phase transition. In contrast to conventional improper ferroelectrics, we find that the polarization has dependence on both primary and secondary modes. It turns out that the charge imbalance between chalcogen atoms at different symmetry sites is the source for the out-of-plane polarization without any out-of-plane displacement in the primary mode. The secondary mode following the primary mode cancels partially the polarization and secures it against the depolarization field. We show that the polarization of d1T-MoS2 is robust to external electric fields and can be manipulated by the uniaxial strain.

Origin of distorted 1T-phase ReS2: first-principles study.

Group-VIIB transition metal dichalcogenides (TMDCs) are known to be stabilized solely in a distorted 1T phase termed as 1T″ phase, which is compared to many stable or metastable phases in other TMDCs. Using first-principles calculations, we study the structural origin of 1T″ phase group-VIIB TMDCs. We find that quasi 1D Peierls-like instability is responsible for the transition to the 1T″ phase ReS2 monolayer from the 1T' phase, another distorted 1T phase. Two half-filled bands in 1T'-ReS2 make sharp peaks in the Lindhard function that prompt the charge density wave (CDW) phase with large band gap opening. Our calculations show that overlapping of the two bands in a broad energy range leads to robust CDW phase or stable 1T″ phase in group-VIIB TMDCs against compositional variation, which is in stark contrast to typical Peierls instability driven by a single band. Calculated total energy curve near the critical point exhibits the feature of the first-order Landau transition due to local chemical bonding. The structural stability of the 1T″ phase in group-VIIB TMDCs is thus guaranteed by two half-filled bands and local chemical bonding.

Nanostructured topological state in bismuth nanotube arrays: inverting bonding-antibonding levels of molecular orbitals.

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.

Super low work function of alkali-metal-adsorbed transition metal dichalcogenides.

Discovering the materials that have work functions less than 1 eV is essential for efficient thermionic energy converter (TEC). The lowest work function of materials reported so far is in a range of about 1 eV. Here, to design low work function materials, we perform first-principles calculations on selected materials of transition metal dichalcogenide as substrates and alkali metals as adsorbates. The work function of our selected materials has a dip ubiquitously independent of the true binding distances of the adsorbates and exhibits contrasting behavior between empty d-shell elements (K, Rb, and Cs) and the others (Li and Na). We show that the interaction of empty d-orbitals of alkali metals and lone pair electrons of chalcogen is a key to the behavior of the work function. From calculated key parameters that determine the work function, we find that, regardless of the amount of charge transfer, K on WTe2 induces the largest surface dipole moment, which consequently makes the surface work function of as small as 0.8 eV, the smallest reported to date, and that the work function is lowered further to 0.7 eV by lattice strains. We demonstrate that the thermal efficiency of TEC using the low work function material exceeds that of thermoelectric materials with figure of merit of 5-10 in temperature range of 880-1200 K.

Topological phase transition and quantum spin Hall edge states of antimony few layers.

While two-dimensional (2D) topological insulators (TI's) initiated the field of topological materials, only very few materials were discovered to date and the direct access to their quantum spin Hall edge states has been challenging due to material issues. Here, we introduce a new 2D TI material, Sb few layer films. Electronic structures of ultrathin Sb islands grown on Bi2Te2Se are investigated by scanning tunneling microscopy. The maps of local density of states clearly identify robust edge electronic states over the thickness of three bilayers in clear contrast to thinner islands. This indicates that topological edge states emerge through a 2D topological phase transition predicted between three and four bilayer films in recent theory. The non-trivial phase transition and edge states are confirmed for epitaxial films by extensive density-functional-theory calculations. This work provides an important material platform to exploit microscopic aspects of the quantum spin Hall phase and its quantum phase transition.

Topological modification of the electronic structure by Bi-bilayers lying deep inside bulk Bi2Se3.

We observe the modified surface states of an epitaxial thin film of a homologous series of (Bi2)m(Bi2Se3)n, as a topological insulator (TI), by angle-resolved photoemission spectroscopy measurements. A thin film with m : n = 1 : 3 (Bi8Se9) has been grown with Bi2 bilayers embedded every other three quintuple layers (QLs) of Bi2Se3. Despite the reduced dimension of continuous QLs due to the Bi2 heterolayers, we find that the topological surface states stem from the inverted Bi and Se states and the topologically nontrivial structures are mainly based on the prototype of 3D TI Bi2Se3 without affecting the overall topological order.

Quantum Electronic Transport of Topological Surface States in ß-Ag2Se Nanowire.

Single-crystalline ß-Ag2Se nanostructures, a new class of 3D topological insulators (TIs), were synthesized using the chemical vapor transport method. The topological surface states were verified by measuring electronic transport properties including the weak antilocalization effect, Aharonov-Bohm oscillations, and Shubnikov-de Haas oscillations. First-principles band calculations revealed that the band inversion in ß-Ag2Se is caused by strong spin-orbit coupling and Ag-Se bonding hybridization. These investigations provide evidence of nontrivial surface state about ß-Ag2Se TIs that have anisotropic Dirac cones.

A first-principles study on three-dimensional covalently-bonded hexagonal boron nitride nanoribbons.

We studied three-dimensional honeycomb-structure boron nitride (BN) allotrope using first-principles calculations and the tight-binding method. Interconnected by sp(3)-bonding at the vertices, hexagonal BN nanoribbons construct highly-porous, covalently-bonded hexagonal BN nanoribbons (CBBNs). We investigated the structural and mechanical properties of CBBNs with various sizes, compared with those of carbon and other BN allotropes. The mechanical and thermal stabilities are also checked. Our calculations show that, despite the high porosity and low mass density, CBBNs are stable and mechanically hard materials as cubic BN. Moreover, our calculated results suggest that CBBNs can be regarded as a binary alloy of sp(2)- and sp(3)-bonded BNs following the Vegard's rule in average bond lengths and bulk moduli. Calculated band structures show that the band gap of CBBNs has similar variation upon increasing size as BN nanoribbons and is also limited by the second-neighbor interaction between the pz states of sp(2)-bonded atoms in adjacent nanoribbons.

Quantum anomalous Hall and quantum spin-Hall phases in flattened Bi and Sb bilayers.

Discovery of two-dimensional topological insulator such as Bi bilayer initiates challenges in exploring exotic quantum states in low dimensions. We demonstrate a promising way to realize the Kane-Mele-type quantum spin Hall (QSH) phase and the quantum anomalous Hall (QAH) phase in chemically-modified Bi and Sb bilayers using first-principles calculations. We show that single Bi and Sb bilayers exhibit topological phase transitions from the band-inverted QSH phase or the normal insulator phase to Kane-Mele-type QSH phase upon chemical functionalization. We also predict that the QAH effect can be induced in Bi or Sb bilayers upon nitrogen deposition as checked from calculated Berry curvature and the Chern number. We explicitly demonstrate the spin-chiral edge states to appear in nitrogenated Bi-bilayer nanoribbons.

Ultimately short ballistic vertical graphene Josephson junctions.

Much efforts have been made for the realization of hybrid Josephson junctions incorporating various materials for the fundamental studies of exotic physical phenomena as well as the applications to superconducting quantum devices. Nonetheless, the efforts have been hindered by the diffusive nature of the conducting channels and interfaces. To overcome the obstacles, we vertically sandwiched a cleaved graphene monoatomic layer as the normal-conducting spacer between superconducting electrodes. The atomically thin single-crystalline graphene layer serves as an ultimately short conducting channel, with highly transparent interfaces with superconductors. In particular, we show the strong Josephson coupling reaching the theoretical limit, the convex-shaped temperature dependence of the Josephson critical current and the exceptionally skewed phase dependence of the Josephson current; all demonstrate the bona fide short and ballistic Josephson nature. This vertical stacking scheme for extremely thin transparent spacers would open a new pathway for exploring the exotic coherence phenomena occurring on an atomic scale.