Strain-induced topological phase transition in ferromagnetic Janus monolayer MnSbBiS2Te2.

We investigate a strain-induced topological phase transition in the ferromagnetic Janus monolayer MnSbBiS2Te2 using first-principles calculations. The electronic, magnetic, and topological properties are studied under biaxial strain within the range of -8 to +8%. The ground state of monolayer MnSbBiS2Te2 is metallic with an out-of-plane magnetic easy axis. A band gap is opened when a compressive strain between -4% and -7% is applied. We observe a topological phase transition at a biaxial strain of -5%, where the material becomes a Chern insulator exhibiting a quantum anomalous hall (QAH) effect. We find that biaxial strain and spin-orbit coupling (SOC) are responsible for the topological phase transition in MnSbBiS2Te2. In addition, we find that biaxial strain can alter the direction of the magnetic easy axis of MnSbBiS2Te2. The Curie temperature is calculated using the Heisenberg model and is found to be 24 K. This study could pave the way to the design of topological materials with potential applications in spintronics, quantum computing, and dissipationless electronics.

Switchable electronic and enhanced magnetic properties of CrI3 edges.

Owing to its novel electronic and magnetic properties, two-dimensional CrI3 has great potential in the application of spintronic devices. However, as an inevitable line defect, the properties of the edges of CrI3 remain elusive. Here, via first-principles calculations with spin-orbit coupling, we investigated the thermodynamic stabilities, electronic and magnetic properties of thirteen CrI3 edges with different structures. We showed that zigzag edges are more stable than armchair edges, and a CrI3 nanoribbon can be either metallic or insulating depending on its chemical growth conditions. The edge stability and associated electronic properties can be understood in terms of the octahedron ligand field and electron counting model. In most cases, both the magnetic moment and Curie temperature can be enhanced by edges, which are in startle contrast to the surfaces of three-dimensional ferromagnetic materials, where a magnetic dead layer is often observed.

Spin-Triplet Excitonic Insulator: The Case of Semihydrogenated Graphene.

While various excitonic insulators have been studied in the literature, due to the perceived too-small spin splitting, spin-triplet excitonic insulator is rare. In two-dimensional systems such as a semihydrogenated graphene (known as graphone), however, it is possible, as revealed by first-principles calculations coupled with Bethe-Salpeter equation. The critical temperature, given by an effective Hamiltonian, is 11.5 K. While detecting excitonic insulators is still a daunting challenge, the condensation of triplet excitons will result in spin superfluidity, which can be directly measured by a transport experiment. Nonlocal dielectric screening also leads to an unexpected phenomenon, namely, an indirect-to-direct transition crossover between single-particle band and exciton dispersion in the semihydrogenated graphene, which offers yet another test by experiment.

Critical topological nodal points and nodal lines/rings in Kagome graphene.

Critical topological phases, possessing flat bands, provide a platform to study unique topological properties and transport phenomena under a many-body effect. Here, we propose that critical nodal points and nodal lines or rings can be found in Kagome lattices. After the C3 rotation symmetry of a single-layer Kagome lattice is eliminated, a quadratic nodal point splits into two critical nodal points. When the layered Kagome lattices are stacked into a three-dimensional (3D) structure, critical nodal lines or rings can be generated by tuning the interlayer coupling. Furthermore, we use Kagome graphene as an example to identify that these critical phases could be obtained in real materials. We also discuss flat-band-induced ferromagnetism. It is found that the flat band splits into two spin-polarized bands by hole-doping, and as a result the Dirac-type critical phases evolve into Weyl-type phases.

Photoinduced Vacancy Ordering and Phase Transition in MoTe2.

We show that non-equilibrium dynamics plays a central role in the photoinduced 2H-to-1T' phase transition of MoTe2. The phase transition is initiated by a local ordering of Te vacancies, followed by a 1T' structural change in the original 2H lattice. The local 1T' region serves as a seed to gather more vacancies into ordering and subsequently induces a further growth of the 1T' phase. Remarkably, this process is controlled by photogenerated excited carriers as they enhance vacancy diffusion, increase the speed of vacancy ordering, and are hence vital to the 1T' phase transition. This mechanism can be contrasted to the current model requiring a collective sliding of a whole Te atomic layer, which is thermodynamically highly unlikely. By uncovering the key roles of photoexcitations, our results may have important implications for finely controlling phase transitions in transition metal dichalcogenides.

Half-Excitonic Insulator: A Single-Spin Bose-Einstein Condensate.

First-principles calculations reveal an unusual electronic state (dubbed as half excitonic insulator) in monolayer 1T-MX_{2} (M=Co, Ni and X=Cl, Br). Its one spin channel has a many-body ground state due to excitonic instability, while the other is characterized by a conventional band insulator gap. This disparity arises from a competition between the band gap and exciton binding energy, which exhibits a spin dependence due to different orbital occupations. Such a state can be identified by optical absorption measurements and angle-resolved photoemission spectroscopy. Our theory not only provides new insights for the study of exciton condensation in magnetic materials but also suggests that strongly correlated materials could be fertile candidates for excitonic insulators.

Correction: Significance of hydrogen bonding networks in the proton-coupled electron transfer reactions of photosystem II from a quantum-mechanics perspective.

Correction for 'Significance of hydrogen bonding networks in the proton-coupled electron transfer reactions of photosystem II from a quantum-mechanics perspective' by Jun Chai et al., Phys. Chem. Chem. Phys., 2019, 21, 8721-8728.

Significance of hydrogen bonding networks in the proton-coupled electron transfer reactions of photosystem II from a quantum-mechanics perspective.

The photosynthetic protein complex, photosystem II (PSII), conducts the light-driven water-splitting reaction with unrivaled efficiency. Proton-coupled electron transfer (PCET) reactions at the redox-active tyrosine residues are thought to play a critical role in the water-splitting chemistry. Addressing the fundamental question as to why the tyrosine residue, YZ, is kinetically competent in comparison to a symmetrically placed tyrosine residue, YD, is important for the elucidation of the mechanism of PCET in the water-splitting reaction of PSII. Here, using all-quantum-mechanical calculations we study PCET at the YZ and YD residues of PSII. We find that when YZ is in its protein matrix under physiological conditions, the HOMO of YZ constitutes the HOMO of the whole system. In contrast, the HOMO of YD is buried under the electronic states localized elsewhere in the protein matrix and PCET at YD requires the transfer of the phenolic proton, which elevates the HOMO of YD to become the HOMO of the whole system. This leads to the oxidation of YD, albeit on a slower timescale. Our study reveals that the key differences between the electronic structure of YZ and YD are primarily determined by the protonation state of the respective hydrogen-bonding partners, D1-His190 and D2-His189, or more generally by the H-bonding network of the protein matrix.

Understanding the origin of bandgap problem in transition and post-transition metal oxides.

Improving electronic structure calculations for practical and technologically important materials has been a never-ending pursue. This is especially true for transition and post-transition metal oxides for which the current first-principles approaches still suffer various drawbacks. Here, we present a hierarchical-hybrid functional approach built on the use of pseudopotentials. The key is to introduce different amounts of exact exchange to core and valence electrons. It allows for treating the delocalization errors of sp and d electrons differently, which have been known to be an important source of error for the band structure. Using wurtzite ZnO as a prototype, we show that the approach is successful in simultaneously reproducing the bandgap and d-band position. Importantly, the same approach, without having to change the hybrid mixing parameters from those of Zn, works reasonably well for other binary 3d transition and post-transition metal oxides across board. Our findings thus point out a new direction of systematically improving the exchange functional in first-principles calculations.

Enhanced Light Emission from the Ridge of Two-Dimensional InSe Flakes.

InSe, a newly rediscovered two-dimensional (2D) semiconductor, possesses superior electrical and optical properties as a direct-band-gap semiconductor with high mobility from bulk to atomically thin layers and is drastically different from transition-metal dichalcogenides, in which the direct band gap only exists at the single-layer limit. However, absorption in InSe is mostly dominated by an out-of-plane dipole contribution, which results in the limited absorption of normally incident light that can only excite the in-plane dipole at resonance. To address this challenge, we have explored a unique geometric ridge state of the 2D flake without compromising the sample quality. We observed the enhanced absorption at the ridge over a broad range of excitation frequencies from photocurrent and photoluminescence (PL) measurements. In addition, we have discovered new PL peaks at low temperatures due to defect states on the ridge, which can be as much as ∼60 times stronger than the intrinsic PL peak of InSe. Interestingly, the PL of the defects is highly tunable through an external electrical field, which can be attributed to the Stark effect of the localized defects. InSe ridges thus provide new avenues for manipulating light-matter interactions and defect engineering that are vitally crucial for novel optoelectronic devices based on 2D semiconductors.

Band Alignment and the Built-in Potential of Solids.

The built-in potential is of central importance to the understanding of many interfacial phenomena because it determines the band alignment at the interface. Despite its importance, its exact sign and magnitude have generally been recognized as ill-defined quantities for more than half a century. Here, we provide a common energy reference of bulk matter which leads to an unambiguous definition of the built-in potential and innate (i.e., bulk) band alignment. Further, we find that the built-in potential is explicitly determined by the bulk properties of the constituent materials when the system is in electronic equilibrium, while the interface plays a role only in the absence of equilibrium. Our quantitative theory enables a unified description of a variety of important properties of interfaces, ranging from work functions to Schottky barriers in electronic devices.

Directional Forces by Momentumless Excitation and Order-to-Order Transition in Peierls-Distorted Solids: The Case of GeTe.

Time-dependent density-functional theory molecular dynamics reveals an unexpected effect of optical excitation in the experimentally observed rhombohedral-to-cubic transition of GeTe. The excitation induces coherent forces along [001], which may be attributed to the unique energy landscape of Peierls-distorted solids. The forces drive the A_{1g} optical phonon mode in which Ge and Te move out of phase. Upon damping of the A_{1g} mode, phase transition takes place, which involves no atomic diffusion, defect formation, or the nucleation and growth of the cubic phase.

Flatbands and Emergent Ferromagnetic Ordering in Fe_{3}Sn_{2} Kagome Lattices.

A flatband representing a highly degenerate and dispersionless manifold state of electrons may offer unique opportunities for the emergence of exotic quantum phases. To date, definitive experimental demonstrations of flatbands remain to be accomplished in realistic materials. Here, we present the first experimental observation of a striking flatband near the Fermi level in the layered Fe_{3}Sn_{2} crystal consisting of two Fe kagome lattices separated by a Sn spacing layer. The band flatness is attributed to the local destructive interferences of Bloch wave functions within the kagome lattices, as confirmed through theoretical calculations and modelings. We also establish high-temperature ferromagnetic ordering in the system and interpret the observed collective phenomenon as a consequence of the synergetic effect of electron correlation and the peculiar lattice geometry. Specifically, local spin moments formed by intramolecular exchange interaction are ferromagnetically coupled through a unique network of the hexagonal units in the kagome lattice. Our findings have important implications to exploit emergent flat-band physics in special lattice geometries.

Remote epitaxy of copper on sapphire through monolayer graphene buffer.

In this work, we show that remote heteroepitaxy can be achieved when Cu thin film is grown on single crystal, monolayer graphene buffered sapphire(0001) substrate via a thermal evaporation process. X-ray diffraction and electron backscatter diffraction data show that the epitaxy process forms a prevailing Cu crystal domain, which is remotely registered in-plane to the sapphire crystal lattice below the monolayer graphene, with the (111) out-of-plane orientation. As a poor metal with zero density of states at its Fermi level, monolayer graphene cannot totally screen out the stronger charge transfer/metallic interactions between Cu and substrate atoms. The primary Cu domain thus has good crystal quality as manifested by a narrow crystal misorientation distribution. On the other hand, we show that graphene interface imperfections, such as bilayers/multilayers, wrinkles and interface contaminations, can effectively weaken the atomic interactions between Cu and sapphire. This results in a second Cu domain, which directly grows on and follows the graphene hexagonal lattice symmetry and orientation. Because of the weak van der Waals interaction between Cu and graphene, this domain has inferior crystal quality. The results are further confirmed using graphene buffered spinel(111) substrate, which indicates that this remote epitaxial behavior is not unique to the Cu/sapphire system.

Non-phase-separated 2D B-C-N alloys via molecule-like carbon doping in 2D BN: atomic structures and optoelectronic properties.

Two-dimensional (2D) B-C-N alloys have recently attracted much attention but unfortunately, Chemical Vapor Deposition (CVD) B-C-N alloys typically phase separate. In spite of that, our analysis of the B-C-N alloy fabricated by electron-beam irradiation suggests that non-phase-separated B-C-N may in fact exist with a carbon concentration up to 14 at%. While this analysis points to a new way to overcome the phase-separation in 2D B-C-N, by first-principles calculations, we show that these B-C-N alloys are made of motifs with even numbers of carbon atoms, in particular, dimers or six-fold rings (in a molecule-like form), embedded in a 2D BN network. Moreover, by tuning the carbon concentration, the band gap of the B-C-N alloys can be reduced by 35% from that of BN. Due to a strong overlap of the wavefunctions at the conduction band and valance band edges, the non-phase-separated B-C-N alloys maintain the strong optical absorption of BN.

Prediction of Ideal Topological Semimetals with Triply Degenerate Points in the NaCu_{3}Te_{2} Family.

Triply degenerate points (TDPs) in band structure of a crystal can generate novel TDP fermions without high-energy counterparts. Although identifying ideal TDP semimetals, which host clean TDP fermions around the Fermi level (E_{F}) without coexisting with other quasiparticles, is critical to explore the intrinsic properties of this new fermion, it is still a big challenge and has not been achieved up to now. Here, we disclose an effective approach to search for ideal TDP semimetals via selective band crossing between antibonding s and bonding p orbitals along a line in the momentum space with C_{3v} symmetry. Applying this approach, we have successfully identified the NaCu_{3}Te_{2} family of compounds to be ideal TDP semimetals, where two, and only two, pairs of TDPs are located around the E_{F}. Moreover, we demonstrate a fundamental mechanism to modulate energy splitting between a pair of TDPs, and we illustrate the intrinsic features of TDP Fermi arcs in these ideal TDP semimetals.

Semi-Dirac semimetal in silicene oxide.

A semi-Dirac semimetal is a material that exhibits linear band dispersion in one direction and quadratic band dispersion in the orthogonal direction and, therefore, hosts massless and massive fermions at the same point in the momentum space. While a number of interesting physical properties have been predicted in semi-Dirac semimetals, it has been rare to realize such materials in condensed matter. Based on the fact that some honeycomb materials are easily oxidized or chemically absorb other atoms, here, we theoretically propose an approach of modifying their band structures by covalent addition of group-VI elements and strain engineering. We predict a silicene oxide with the chemical formula of Si2O to be a candidate semi-Dirac semimetal. Our approach is backed by the analysis and understanding of the effect of p-orbital frustration on the band structure of graphene-like materials.

Giant lattice expansion by quantum stress and universal atomic forces in semiconductors under instant ultrafast laser excitation.

Femtosecond lasers (fs) can cause a disparity between electronic and lattice temperatures in the very short period after irradiation. In this relatively cool lattice regime, the material properties can differ drastically from those under thermal equilibrium. In particular, first-principles calculations reveal two general mechanical effects on semiconductors. Firstly, the excitation can induce a negative pressure on the lattice, causing a >10% expansion, even for superhard diamond. Secondly, it induces inhomogeneous local forces on the atoms, for both perfect and distorted lattices. In the case of phase-change-memory for Ge2Sb2Te5 and GeTe alloys, such random forces cause a simultaneous phase transition from crystalline to amorphous, which enables faster data writing. These excitation effects are further supported by the time-dependent density functional theory. This work could be an important step in advancing fs laser techniques for the atomic-level control of structures, rather than relying on traditional melting or ablation approaches which often apply to much larger and non-atomic scales.

Stacking Fault Enriching the Electronic and Transport Properties of Few-Layer Phosphorenes and Black Phosphorus.

Interface engineering is critical for enriching the electronic and transport properties of two-dimensional materials. Here, we identify a new stacking, named Aδ, in few-layer phosphorenes (FLPs) and black phosphorus (BP) based on first-principles calculation. With its low formation energy, the Aδ stacking could exist in FLPs and BP as a stacking fault. The presence of the Aδ stacking fault induces a direct to indirect transition of the band gap in FLPs. It also affects the carrier mobilities by significantly increasing the carrier effective masses. More importantly, the Aδ stacking enables the fabrication of a whole spectrum of lateral junctions with all the type-I, II, and III alignments simply through the manipulation of the van der Waals stacking without resorting to any chemical modification. This is achieved by the widely tunable electron affinity and ionization potential of FLPs and BP with the Aδ stacking.

Kinetics stabilized doping: computational optimization of carbon-doped anatase TiO2 for visible-light driven water splitting.

Using density functional theory calculation we investigate the carbon doping of anatase TiO2, a technique widely studied for visible-light driven water splitting. By a detailed analysis of the thermodynamics of C defects in TiO2, we show that any significant concentration of C dopants in the TiO2 lattice must be a result of non-equilibrium doping, which emphasizes the importance of kinetics stabilized C defects. Based on the band gaps calculated using hybrid density functionals, we exclude the possibility of C occupying Ti lattice sites or interstitial sites to enhance visible-light absorption of TiO2, as extensively discussed in the literature. Also, the recently proposed defect with a CO species occupying two O sites yields a too small band gap for water splitting. Two defects that can effectively reduce the band gap for the water splitting application are identified to be: (1) the CO-VO complex, i.e., a C substituting for O (CO) paired with an O vacancy (VO) and (2) the (C2)2O complex with a C dimer (C2) occupying two neighboring O vacancies. Compared with the CO-VO complex, (C2)2O exhibits strong binding (greater than 2.5 eV) between the two C atoms, which could significantly enhance its kinetic stability to survive from high temperature annealing. With a reduced band gap of about 1.4 eV, carbon dimers could be ideal for kinetic doping of anatase TiO2 to enhance its visible-light activity in photocatalytic reactions. Molecular doping using C2H2 or C2H4 as C precursors has been proposed to introduce the carbon dimers into TiO2.