Novel Polytype of III-VI Metal Chalcogenides Nano Crystals Realized in Epitaxially Grown InTe.

III-VI metal chalcogenides have garnered considerable research attention as a novel group of layered van der Waals materials because of their exceptional physical properties and potential technological applications. Here, the epitaxial growth and stacking sequences of InTe is reported, an essential and intriguing material from III-VI metal chalcogenides. Aberration-corrected scanning transmission electron microscopy (STEM) is utilized to directly reveal the interlayer stacking modes and atomic structure, leading to a discussion of a new polytype. Furthermore, correlations between the stacking sequences and interlayer distances are substantiated by atomic-resolution STEM analysis, which offers evidence for strong interlayer coupling of the new polytype. It is proposed that layer-by-layer deposition is responsible for the formation of the unconventional stacking order, which is supported by ab initio density functional theory calculations. The results thus establish molecular beam epitaxy as a viable approach for synthesizing novel polytypes. The experimental validation of the InTe polytype here expands the family of materials in the III-VI metal chalcogenides while suggesting the possibility of new stacking sequences for known materials in this system.

Atomic Reconstruction and Oxygen Evolution Reaction of Mn3O4 Nanoparticles.

Understanding the chemical states of individual surface atoms and their arrangements is essential for addressing several current issues such as catalysis, energy stroage/conversion, and environmental protection. Here, we exploit a profile imaging technique to understand the correlation between surface atomic structures and the oxygen evolution reaction (OER) in Mn3O4 nanoparticles. We image surface structures of Mn3O4 nanoparticles and observe surface reconstructions in the (110) and (101) planes. Mn3+ ions at the surface, which are commonly considered as the active sites in OER, disappear from the reconstructed planes, whereas Mn3+ ions are still exposed at the edges of nanoparticles. Our observations suggest that surface reconstructions can deactivate low-index surfaces of Mn oxides in OER. These structural and chemical observations are further validated by density functional theory calculations. This work shows why atomic-scale characterization of surface structures is crucial for a molecular-level understanding of a chemical reaction in oxide nanoparticles.

Role of Sr doping and external strain on relieving bottleneck of oxygen diffusion in La2-xSrxCuO4-δ.

In many complex oxides, the oxygen vacancy formation is a promising route to modify the material properties such as a superconductivity and an oxygen diffusivity. Cation substitutions and external strain have been utilized to control the concentration and diffusion of oxygen vacancies, but the mechanisms behind the controls are not fully understood. Using first-principles calculations, we find how Sr doping and external strain greatly enhances the diffusivity of oxygen vacancies in La2-xSrxCuO4-δ (LSCO) in the atomic level. In hole-doped case (2x > δ), the formation energy of an apical vacancy in the LaO layer is larger than its equatorial counterpart by 0.2 eV that the bottleneck of diffusion process is for oxygen vacancies to escape equatorial sites. Such an energy difference can be reduced and even reversed by either small strain (< 1.5%) or short-range attraction between Sr and oxygen vacancy, and in turn, the oxygen diffusivity is greatly enhanced. For fully compensated hole case (2x ≦ δ), the formation energy of an apical vacancy becomes too high that most oxygen vacancies cannot move but would be trapped at equatorial sites. From our electronic structure analysis, we found that the contrasting change in the formation energy by Sr doping and external strain is originated from the different localization natures of electron carrier from both types of oxygen vacancies.

Transition Metal-Free Half-Metallicity in Two-Dimensional Gallium Nitride with a Quasi-Flat Band.

Two-dimensional half-metallicity without a transition metal is an attractive attribute for spintronics applications. On the basis of first-principles calculation, we revealed that a two-dimensional gallium nitride (2D-GaN), which was recently synthesized between graphene and SiC or wurtzite GaN substrate, exhibits half-metallicity due to its half-filled quasi-flat band. We found that graphene plays a crucial role in stabilizing a local octahedral structure, whose unusually high density of states due to a flat band leads to a spontaneous phase transition to its half-metallic phase from normal metal. It was also found that its half-metallicity is strongly correlated to the in-plane lattice constants and thus subjected to substrate modification. To investigate the magnetic property, we simplified its magnetic structure with a two-dimensional Heisenberg model and performed Monte Carlo simulation. Our simulation estimated its Curie temperature (TC) to be ∼165 K under a weak external magnetic field, suggesting that transition metal-free 2D-GaN exhibiting p orbital-based half-metallicity can be utilized in future spintronics.

Oxidation-enhanced thermoelectric efficiency in a two-dimensional phosphorene oxide.

We performed density functional theory calculations to investigate the thermoelectric properties of phosphorene oxide (PO) expected to form by spontaneous oxidation of phosphorene. Since thermoelectric features by nature arise from the consequences of the electron-phonon interaction, we computed the phonon-mediated electron relaxation time, which was fed into the semiclassical Boltzmann transport equation to be solved for various thermoelectric-related quantities. It was found that PO exhibits superior thermoelectric performance compared with its pristine counterpart, which has been proposed to be a candidate for the use of future thermoelectric applications. We revealed that spontaneous oxidation of phosphorene leads to a significant enhancement in the thermoelectric properties of n-doped phosphorene oxide, which is attributed to the considerable reduction of lattice thermal conductivity albeit a small decrease in electrical conductivity. Our results suggest that controlling oxidation may be utilized to improve thermoelectric performance in nanostructures, and PO can be a promising candidate for low-dimensional thermoelectric devices.

Promoting the Reversible Oxygen Redox Reaction of Li-Excess Layered Cathode Materials with Surface Vanadium Cation Doping.

Li-excess layered cathode (LLC) materials have a high theoretical specific capacity of 250 mAh g-1 induced by transition metal (cationic) and oxygen (anionic) redox activity. Especially, the oxygen redox reaction related to the activation of the Li2MnO3 domain plays the crucial role of providing a high specific capacity. However, it also induces an irreversible oxygen release and accelerates the layered-to-spinel phase transformation and capacity fading. Here, it is shown that surface doping of vanadium (V5+) cations into LLC material suppresses both the irreversible oxygen release and undesirable phase transformation, resulting in the improvement of capacity retention. The V-doped LLC shows a high discharge capacity of 244.3 ± 0.8 mAh g-1 with 92% retention after 100 cycles, whereas LLC delivers 233.6 ± 1.1 mAh g-1 with 74% retention. Furthermore, the average discharge voltage of V-doped LLC drops by only 0.33 V after 100 cycles, while LLC exhibits 0.43 V of average discharge voltage drop. Experimental and theoretical investigations indicate that doped V-doping increase the transition metal-oxygen (TM-O) covalency and affect the oxidation state of peroxo-like (O2) n - species during the delithiation process. The role of V-doping to make the oxygen redox reversible in LLC materials for high-energy density Li-ion batteries is illustrated here.

Enhanced reliability of phase-change memory via modulation of local structure and chemical bonding by incorporating carbon in Ge2Sb2Te5.

In this study, we investigated the effect of phase-change characteristics on the device performance of carbon-incorporated Ge2Sb2Te5 (CGST) to understand the origin of the enhanced reliability and stabilization of the device. Macroscopic and microscopic measurements confirmed that the structural stability significantly increased with the incorporation of as much as 10% carbon. After the completion of bond formation between C and Ge, the excess C (>5 atomic%) engages in bonding with Sb in localized regions because of the difference in formation energy. These bonds of C with Ge and Sb induce non-uniform local charge density of the short-range order. Finally, because the strong bonds between Ge and C shorten the short Ge-Te bonds, the high thermal stability of CGST relative to that of GST can be attributed to intensified Peierls distortion. The formation of strong bonds successfully underpins the local structures and reduces the stochastic effect. Moreover, extension of the C bonding to Sb enhances the structural reliability, resulting in highly stable CGST in the amorphous phase. Finally, the device stability of CGST in the reset state of the amorphous structure during the device switching process was significantly improved.

Effects of paramagnetic fluctuations on the thermochemistry of MnO(100) surfaces in the oxygen evolution reaction.

We investigated the effects of paramagnetic (PM) fluctuations on the thermochemistry of the MnO(100) surface in the oxygen evolution reaction (OER) using the "noncollinear magnetic sampling method plus U" (NCMSM+U). Various physical properties, such as the electronic structure, free energy, and charge occupation, of the MnO(100) surface in the PM state with several OER intermediates, were reckoned and compared to those in the antiferromagnetic (AFM) state. We found that PM fluctuation enhances charge transfer from a surface Mn ion to each of the intermediates and strengthens the chemical bond between them, while not altering the overall features, such as the rate determining step and resting state, in reaction pathways. The enhanced charge transfer can be attributed to the delocalized nature of valence bands observed in the PM surface. In addition, it was observed that chemical-bond enhancement depends on the intermediates, resulting in significant deviations in reaction energy barriers. Our study suggests that PM fluctuations play a significant role in the thermochemistry of chemical reactions occurring on correlated oxide surfaces.

Ultra-low Energy Phase Change Memory with Improved Thermal Stability by Tailoring the Local Structure through Ag Doping.

Although Sb2Te3, as a candidate material for next-generation memory devices, has attractive properties such as higher operation speed and lower power consumption than Ge2Sb2Te5, its poor stability prevents its application to commercial memory devices. Transition metal dopants provide enhancements in its phase change characteristics, improving both thermal stability and operation energy. However, the enhancement mechanism remains to be sufficiently investigated, and standard properties need to be achieved. Herein, the phase change properties of Sb2Te3 are confirmed to be enhanced by the incorporation of a heavy transition metal element such as Ag. The crystallization temperature increases by nearly 40%, and the operation energy is reduced by approximately 60%. These enhancements are associated with the changes in the local Sb2Te3 structure caused by Ag incorporation. As the incorporated Ag atoms substitute Sb in the Sb-Te octahedron, this turns into a Ag-Te defective tetrahedron with a strong Ag-Te bond that induces distortion in the crystal lattice. The formation of this bond is attributed to the electron configuration of Ag and its fully filled d orbital. Thus, Ag-doped Sb2Te3 is a promising candidate for practical phase change memory devices with high stability and high operation speed.

Symmetry Dictated Grain Boundary State in a Two-Dimensional Topological Insulator.

Grain boundaries (GBs) are ubiquitous in solids and have been of central importance in understanding the nature of polycrystals. In addition to their classical roles, topological insulators (TIs) offer a chance to realize GBs hosting distinct topological states that can be controlled by their crystal symmetries. However, such roles of crystalline symmetry in two-dimensional (2D) TIs have not been definitively measured yet. Here, we present the first direct evidence of a symmetry-enforced metallic state along a GB in 1T'-MoTe2, a prototypical 2D TI. Using scanning tunneling microscopy, we show a metallic state along a GB with nonsymmorphic lattice symmetry and its absence along another boundary with symmorphic symmetry. Our atomistic simulations demonstrate in-gap Weyl semimetallic states for the former, whereas they demonstrate gapped states for the latter, explaining our observation well. The observed metallic state, tightly linked to its crystal symmetry, can be used to create a stable conducting nanowire inside TIs.

Two-dimensional Dirac fermions on oxidized black phosphorus.

We explore the oxidation of a single layer of black phosphorus using ab initio density functional theory calculations. We search for the equilibrium structures of phosphorene oxides, POx with various oxygen concentrations x (0 ≤ x ≤ 1). By evaluating the formation energies with diverse configurations and their vibrational properties for each of various x values, we identify a series of stable oxidized structures with x and confirm that the oxidation occurs naturally. We also find that oxidation makes some modes from the P-O bonds and P-P bonds IR-active implying that the infrared spectra can be used to determine the degree of oxidation of phosphorene. Our electronic structure calculations reveal that the fully oxidized phosphorene (PO) has a direct band gap of 0.83 eV similar to the pristine phosphorene. Intriguingly, the PO possesses two nonsymmorphic symmetries with the inversion symmetry broken, guaranteeing symmetry-protected band structures including the band degeneracy and four-fold degenerate Dirac points. Our results provide an important guide in the search for the rare example of a Dirac semimetal with a higher level of degeneracy, giving significant insight into the relations between the symmetry of the lattice and band topology of electrons.

Phase-change like process through bond switching in distorted and resonantly bonded crystal.

Although some methods to improve phase-change memory efficiency have been proposed, an effective experimental approach to induce a phase-change like process without external heat energy has not yet been reported. Herein we have shown that GeTe is a prototype phase-change material, which can exhibit a non-thermal phase-change-like process under uniaxial stress. Due to its structural characteristics like directional structural instability and resonance bonding under 1% uniaxial stress, we observed that bond switching in the GeTe film between short and long bonds is possible. Due to this phase change, GeTe displays the same phase-change as crystal layer rotation. Crystal layer rotation has not been observed in the conventional phase change process using intermediate states, but it is related to the structural characteristics required for maintaining local coordination. Moreover, since the resonance bonding characteristics are effectively turned off upon applying uniaxial stress, the high-frequency dielectric constant can be significantly decreased. Our results also show that the most significant process in the non-thermal phase transition of phase-change materials is the modulation of the lattice relaxation process after the initial perturbation, rather than the method inducing the perturbation itself. Finally, these consequences suggest that a new type of phase-change memory is possible through changes in the optical properties under stress.

A "non-dynamical" way of describing room-temperature paramagnetic manganese oxide.

We present a new approach based on static density functional theory (DFT) to describe paramagnetic manganese oxides, representative paramagnetic Mott insulators. We appended spin noncollinearity and a canonical ensemble to the magnetic sampling method (MSM), which is one of the supercell approaches based on the disordered local moment model. The combination of the noncollinear MSM (NCMSM) with DFT+U represents a highly favorable computational method called NCMSM+U to accurately determine the paramagnetic properties of MnO with moderate numerical cost. The effects of electron correlations and spin noncollinearity on the properties of MnO were also investigated. We found that the spin noncollinearity plays an important role in determining the detailed electronic profile and precise energetics of paramagnetic MnO. Our results illustrate that the NCMSM+U approach may be used for insulating materials as an alternative to the ab initio framework of dynamic mean field theory based on DFT in the simulation of the room-temperature paramagnetic properties.

Closing the Surface Bandgap in Thin Bi2Se3/Graphene Heterostructures.

Topological insulator (TI), a band insulator with topologically protected edge states, is one of the most interesting materials in the field of condensed matter. Bismuth selenide (Bi2Se3) is the most spotlighted three-dimensional TI material; it has a Dirac cone at each top and bottom surface and a relatively wide bandgap. For application, suppression of the bulk effect is crucial, but in ultrathin TI materials, with thicknesses less than 3 QL, the finite size effect works on the linear dispersion of the surface states, so that the surface band has a finite bandgap because of the hybridization between the top and bottom surface states and Rashba splitting, resulting from the structure inversion asymmetry. Here, we studied the gapless top surface Dirac state of strained 3 QL Bi2Se3/graphene heterostructures. A strain caused by the graphene layer reduces the bandgap of surface states, and the band bending resulting from the charge transfer at the Bi2Se3-graphene interface induces localization of surface states to each top and bottom layer to suppress the overlap of the two surface states. In addition, we verified the independent transport channel of the top surface Dirac state in Bi2Se3/graphene heterostructures by measuring the magneto-conductance. Our findings suggest that the strain and the proximity effect in TI/non-TI heterostructures may be feasible ways to engineer the topological surface states beyond the physical and topological thickness limit.

Low Lattice Thermal Conductivity of a Two-Dimensional Phosphorene Oxide.

A fundamental understanding of the phonon transport mechanism is important for optimizing the efficiency of thermoelectric devices. In this study, we investigate the thermal transport properties of the oxidized form of phosphorene called phosphorene oxide (PO) by solving phonon Boltzmann transport equation based on first-principles density functional theory. We reveal that PO exhibits a much lower thermal conductivity (2.42-7.08 W/mK at 300 K) than its pristine counterpart as well as other two-dimensional materials. To comprehend the physical origin of such low thermal conductivity, we scrutinize the contribution of each phonon branch to the thermal conductivity by evaluating various mode-dependent quantities including Grüneisen parameters, anharmonic three-phonon scattering rate, and phase space of three-phonon scattering processes. Our results show that its flexible puckered structure of PO leads to smaller sound velocities; its broken-mirror symmetry allows more ZA phonon scattering; and the relatively-free vibration of dangling oxygen atoms in PO gives rise to additional scattering resulting in further reduction in the phonon lifetime. These results can be verified by the fact that PO has larger phase space for three-phonon processes than phosphorene. Furthermore we show that the thermal conductivity of PO can be optimized by controlling its size or its phonon mean free path, indicating that PO can be a promising candidate for low-dimensional thermoelectric devices.

Latent Order in High-Angle Grain Boundary of GaN.

We report the existence of latent order during core relaxation in the high-angle grain boundaries (GBs) of GaN films using atomic-resolution scanning transmission electron microscopy and ab initio density functional theory calculations. Core structures in the high-angle GBs are characterized by two pairs of Ga-N bonds located next to each other. The core type correlates strongly with the bond angle differences. We identify an order of core relaxation hidden in the high-angle GBs by further classifying the 5/7 atom cores into a stable 5/7 core (5/7(S)) and a metastable 5/7 core (5/7(M)). This core-type classification indicates that metastable cores can exist at real high-angle GBs under certain circumstances. Interestingly, 5/7(M) exhibits distinct defect states compared to 5/7(S), despite their similar atomic configurations. We investigate the reconstruction of defect states observed in 5/7(M) by analyzing the real-space wave functions. An inversion occurred between two localized states during the transition from 5/7(S) to 5/7(M). We suggest an inversion mechanism to explain the formation of new defect states in 5/7(M).

Extremely high electrical conductance of microporous 3D graphene-like zeolite-templated carbon framework.

We report the remarkably high electrical conductance of microporous 3D graphene-like carbons that were formed using lanthanum (La)-catalyzed synthesis in a Y zeolite (LaY) template investigated using conductive atomic force microscopy (C-AFM) and theoretical calculations. To uncover the relation between local electrical conductance and the microporous structures, we tuned the crystallographic ordering of LaY-templated carbon systems by changing the heating temperature. The structure of the LaY-templated carbon prepared at the higher temperature has graphene-like sp 2 hybridized bonds, which was confirmed using high-resolution transmission electron microscopy and X-ray diffraction measurements. C-AFM current-voltage spectroscopy revealed that the local current flow in the LaY-templated carbon depends on the quantity of C-C bonds within the narrow neck between the closed supercages (i.e. there are three types of carbon: carbon with heat treatment, carbon without heat treatment, and carbon synthesized at low temperature). The difference in electrical conductance on the LaY-templated carbon was also confirmed via theoretical computation using the Boltzmann transport theory and the deformation potential theory based on the density functional theory. These results suggest that the degree of order of the pores in the 3D zeolite-templated carbon structures is directly related to electrical conductance.

Ab initio study of aspirin adsorption on single-walled carbon and carbon nitride nanotubes.

Using density functional theory, we investigate the adsorption properties of acetylsalicylic acid (aspirin) on the outer surfaces of a (10,0) carbon nanotube (CNT) and a (8,0) triazine-based graphitic carbon nitride nanotube (CNNT). The adsorption energies for the CNNT and CNT are 0.67 and 0.51 eV, respectively, and hence, the aspirin molecule binds more strongly to the CNNT. The stronger adsorption energy for the binding to the CNNT is ascribed to the high reactivity of its nitrogen atoms with high electron affinity. The CNNT exhibits local electric dipole moments that cause strong charge redistribution in the adsorbed aspirin molecule. The influence of an external electric field on the adsorption of aspirin on the nanotubes is explored by examining modifications in their electronic band structures, partial densities of states, and charge distributions. An electric field applied along a particular direction is found to induce molecular states of aspirin that lie within the in-gap region of the CNNT. This implies that the CNNT can be potentially utilized for the detection of aspirin.

The determining factor of a preferred orientation of GaN domains grown on m-plane sapphire substrates.

Epitaxial lateral overgrowth in tandem with the first-principles calculation was employed to investigate the determining factor of a preferred orientation of GaN on SiO2-patterned m-plane sapphire substrates. We found that the (1100)-orientation is favored over the (1103)-orientation in the region with a small filling factor of SiO2, while the latter orientation becomes preferred in the region with a large filling factor. This result suggests that the effective concentration determines the preferred orientation of GaN: the (1100)- and (1103)-orientations preferred at their low and high concentrations, respectively. Our computational study revealed that at a low coverage of Ga and N atoms, the local atomic arrangement resembles that on the (1103) surface, although the (1100) surface is more stable at their full coverage. Such a (1103)-like atomic configuration crosses over to the local structure resembling that on the (1100) surface as the coverage increases. Based on results, we determined that high effective concentration of Ga and N sources expedites the growth of the (1103)-orientation while keeping from transition to the (1100)-orientation. At low effective concentration, on the other hand, there is a sufficient time for the added Ga and N sources to rearrange the initial (1103)-like orientation to form the (1100)-orientation.

Is hexagonal boron nitride always good as a substrate for carbon nanotube-based devices?

Hexagonal boron nitride sheets have been noted especially for their enhanced properties as substrates for sp(2) carbon-based nanodevices. To evaluate whether such enhanced properties would be retained under various realistic conditions, we investigate the structural and electronic properties of semiconducting carbon nanotubes on perfect and defective hexagonal boron nitride sheets under an external electric field as well as with a metal impurity, using density functional theory. We verify that the use of a perfect hexagonal boron nitride sheet as a substrate indeed improves the device performances of carbon nanotubes, compared with the use of conventional substrates such as SiO2. We further show that even the hexagonal boron nitride with some defects can show better performance as a substrate. Our calculations, on the other hand, also suggest that some defective boron nitride layers with a monovacancy and a nickel impurity could bring about poor device behavior since the imperfections impair electrical conductivity due to residual scattering under an applied electric field.