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Chirality-controlled synthesis of carbon nanotubes (CNTs) is one of the ultimate goals in the field of nanotube synthesis. At present, direct synthesis achieving a purity of over 90%, which can be called single-chirality synthesis, has been achieved for only two types of chiralities: (14,4) and (12,6) CNTs. Here, we realized an ultrahigh-purity (∼95.8%) synthesis of (6,5) CNTs with a trimetallic catalyst NiSnFe. Partial formation of Ni 3 Sn crystals was found within the NiSnFe nanoparticles. The activation energy for the selective growth of (6,5) CNTs decreased owing to the formation of Ni 3 Sn crystals, resulting in the high-purity synthesis of (6,5) CNTs. Transmission electron microscopy (TEM) reveals that one-dimensional (1D) crystals of periodic strip lines with 8.8 Å spacing are formed within the as-grown ultrahigh-purity (6,5) CNTs, which are well-matched with the simulated TEM image of closely packed 37 (6,5) CNTs with 2.8 Å intertube distance, indicating the direct formation of chirality-pure (6,5)-CNT bundle structures. The photoluminescence (PL) lifetime increases more than 20 times by the formation of chirality-pure bundle structures of (6,5) CNTs compared to that of isolated (6,5) CNTs. This can be explained by exciton delocalization or intertube excitons within bundle structures of chirality-pure (6,5) CNTs.

Pressurized hydrogen-based superconductors are phonon-mediated superconductors that exhibit high phonon frequencies. In these superconductors, in addition to the density of states (DOS) at the Fermi energy ( E F ), the energy dependence of the DOS around E F becomes important for evaluating their transition temperature ( T c ). Systems with peak structures in the DOS around E F , such as I m 3 ¯ m H 3 S and F m 3 ¯ m LaH 10 , highlight this point. We use the fully ab initio Eliashberg method to investigate this phenomenon in I m 3 ¯ m CaH 6 and F m 3 ¯ m ThH 10 with a dip structure in their DOS around E F . Our calculated T c values (225-235 K for CaH 6 at 200 GPa and 156-158 K for ThH 10 at 170 GPa) are quantitatively consistent with the experimental results. Remarkably, our results from the self-consistent treatment of the electron Green's function contrasts with those cases with a peak structure in the DOS. This finding unifies the understanding of how DOS structures influence the evaluation of T c ., (© 2024. The Author(s).)

We investigate ultrafast dynamics of the anomalous Hall effect (AHE) in the topological antiferromagnet Mn_{3}Sn with sub-100 fs time resolution. Optical pulse excitations largely elevate the electron temperature up to 700 K, and terahertz probe pulses clearly resolve ultrafast suppression of the AHE before demagnetization. The result is well reproduced by microscopic calculation of the intrinsic Berry-curvature mechanism while the extrinsic contribution is clearly excluded. Our work opens a new avenue for the study of nonequilibrium AHE to identify the microscopic origin by drastic control of the electron temperature by light.

Cesium ion (Cs + ) resistance has been reported in bacteria but is poorly understood as reports on Cs + -resistant bacteria have been limited. We previously reported a novel Cs + /H + antiporter CshA implicated in Cs + -resistance in Microbacterium sp. TS-1. The present study used the same screening method to isolate novel Cs + -sensitive mutants and their revertants from TS-1. A comparative mutation site analysis using whole-genome sequencing revealed that MTS1_03028 encodes the Mg 2+ transporter MgtE and is a candidate Cs + resistance-related gene. We performed a bioinformatic analysis of MTS1_03028 and complementation experiments on Cs + resistance in the TS-1 MTS1_03028 mutants Mut5 and Mut7 as well as Escherichia coli expressing MTS1_03028 in the presence of Mg 2+ . We established the role of MgtE in Cs + resistance through a functional analysis of TS-1. Enhancing Mg 2+ transport by expression of MTS_03028 conferred increased Cs + resistance. When this strain was exposed to Cs + concentrations exceeding 200 mM, CshA consistently lowered the intracellular Cs + concentration. To our knowledge, the present study is the first to clarify the mechanism of Cs + resistance in certain bacteria. The study findings offer important insights into the mechanism of bacterial resistance to excess Cs + in the environment, suggesting the potential for bioremediation in high Cs-contaminated areas., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Ishida, Koretsune, Ishiuchi, Teshima and Ito.)

The radionuclide isotopes ( 134 Cs and 137 Cs) of Cesium (Cs), an alkali metal, are attracting attention as major causes of radioactive contamination. Although Cs + is harmful to the growth of plants and bacteria, alkaliphilic bacterium Microbacterium sp. TS-1, isolated from a jumping spider, showed growth even in the presence of 1.2 M CsCl. The maximum concentration of Cs + that microorganisms can withstand has been reported to be 700 mM till date, suggesting that the strain TS-1 is resistant to a high concentration of Cs ions. Multiple reports of cesium ion-resistant bacteria have been reported, but the detailed mechanism has not yet been elucidated. We obtained Cs ion-sensitive mutants and their revertant mutants from strain TS-1 and identified a Cs ion resistance-related gene, MTS1_00475 , by performing SNP analysis of the whole-genome sequence data. When exposed to more than 200 mM Cs + concentration, the intracellular Cs + concentration was constantly lowered by MTS1_00475, which encodes the novel low-affinity Cs + /H + antiporter. This study is the first to clarify the mechanism of cesium resistance in unexplained cesium-resistant microorganisms. By clarifying the new cesium resistance mechanism, it can be expected to be used as a bioremediation tool for treating radioactive Cs + contaminated water., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Koretsune, Ishida, Kaneda, Ishiuchi, Teshima, Marubashi, Satoh and Ito.)

Anomalous Nernst effect (ANE), converting a heat flow to transverse electric voltage, originates from the Berry phase of electronic wave function near the Fermi energy E F . Thus, the ANE provides a sensitive probe to detect a topological state that produces large Berry curvature. In addition, a magnet that exhibits a large ANE using low-cost and safe elements will be useful to develop a novel energy harvesting technology. Here, we report our observation of a high ANE exceeding 3 microvolts per kelvin above room temperature in the kagome ferromagnet Fe 3 Sn with the Curie temperature of 760 kelvin. Our theoretical analysis clarifies that a “nodal plane” produces a flat hexagonal frame with strongly enhanced Berry curvature, resulting in the large ANE. Our discovery of the large ANE in Fe 3 Sn opens the path for the previously unexplored functionality of flat degenerate electronic states and for developing flexible film thermopile and heat current sensors.

Physics of Weyl electrons has been attracting considerable interests and further accelerated by recent discoveries of giant anomalous Hall effect (AHE) and topological Hall effect (THE) in several magnetic systems including non-coplanar magnets with spin chirality or small-size skyrmions. These AHEs/THEs are often attributed to the intense Berry curvature generated around the Weyl nodes accompanied by band anti-crossings, yet the direct experimental evidence still remains elusive. Here, we demonstrate an essential role of the band anti-crossing for the giant AHE and THE in MnGe thin film by using the terahertz magneto-optical spectroscopy. The low-energy resonance structures around ~ 1.2 meV in the optical Hall conductivity show the enhanced AHE and THE, indicating the emergence of at least two distinct anti-crossings near the Fermi level. The theoretical analysis demonstrates that the competition of these resonances with opposite signs is a cause of the strong temperature and magnetic-field dependences of observed DC Hall conductivity. These results lead to the comprehensive understanding of the interplay among the transport phenomena, optical responses and electronic/spin structures., (© 2021. The Author(s).)

Recently found anomalous Hall, Nernst, magnetooptical Kerr, and spin Hall effects in the antiferromagnets Mn 3 X (X = Sn, Ge) are attracting much attention for spintronics and energy harvesting. Since these materials are antiferromagnets, the origin of these functionalities is expected to be different from that of conventional ferromagnets. Here, we report the observation of ferroic order of magnetic octupole in Mn 3 Sn by X-ray magnetic circular dichroism, which is only predicted theoretically so far. The observed signals are clearly decoupled with the behaviors of uniform magnetization, indicating that the present X-ray magnetic circular dichroism is not arising from the conventional magnetization. We have found that the appearance of this anomalous signal coincides with the time reversal symmetry broken cluster magnetic octupole order. Our study demonstrates that the exotic material functionalities are closely related to the multipole order, which can produce unconventional cross correlation functionalities., (© 2021. The Author(s).)

The recent discoveries of strikingly large zero-field Hall and Nernst effects in antiferromagnets Mn 3 X (X = Sn, Ge) have brought the study of magnetic topological states to the forefront of condensed matter research and technological innovation. These effects are considered fingerprints of Weyl nodes residing near the Fermi energy, promoting Mn 3 X (X = Sn, Ge) as a fascinating platform to explore the elusive magnetic Weyl fermions. In this review, we provide recent updates on the insights drawn from experimental and theoretical studies of Mn 3 X (X = Sn, Ge) by combining previous reports with our new, comprehensive set of transport measurements of high-quality Mn 3 Sn and Mn 3 Ge single crystals. In particular, we report magnetotransport signatures specific to chiral anomalies in Mn 3 Ge and planar Hall effect in Mn 3 Sn, which have not yet been found in earlier studies. The results summarized here indicate the essential role of magnetic Weyl fermions in producing the large transverse responses in the absence of magnetization.

Magnetic Weyl semimetals attract considerable interest not only for their topological quantum phenomena but also as an emerging materials class for realizing quantum anomalous Hall effect in the two-dimensional limit. A shandite compound Co 3 Sn 2 S 2 with layered kagome-lattices is one such material, where vigorous efforts have been devoted to synthesize the two-dimensional crystal. Here, we report a synthesis of Co 3 Sn 2 S 2 thin flakes with a thickness of 250 nm by chemical vapor transport method. We find that this facile bottom-up approach allows the formation of large-sized Co 3 Sn 2 S 2 thin flakes of high-quality, where we identify the largest electron mobility (∼2600 cm 2 V -1 s -1 ) among magnetic topological semimetals, as well as the large anomalous Hall conductivity (∼1400 Ω -1 cm -1 ) and anomalous Hall angle (∼32%) arising from the Berry curvature. Our study provides a viable platform for studying high-quality thin flakes of magnetic Weyl semimetal and stimulate further research on unexplored topological phenomena in the two-dimensional limit.

The Weyl semimetal (WSM), which hosts pairs of Weyl points and accompanying Berry curvature in momentum space near Fermi level, is expected to exhibit novel electromagnetic phenomena. Although the large optical/electronic responses such as nonlinear optical effects and intrinsic anomalous Hall effect (AHE) have recently been demonstrated indeed, the conclusive evidence for their topological origins has remained elusive. Here, we report the gigantic magneto-optical (MO) response arising from the topological electronic structure with intense Berry curvature in magnetic WSM Co 3 Sn 2 S 2 . The low-energy MO spectroscopy and the first-principles calculation reveal that the interband transitions on the nodal rings connected to the Weyl points show the resonance of the optical Hall conductivity and give rise to the giant intrinsic AHE in dc limit. The terahertz Faraday and infrared Kerr rotations are found to be remarkably enhanced by these resonances with topological electronic structures, demonstrating the novel low-energy optical response inherent to the magnetic WSM.

Using the ab initio local force method, we investigate the formation mechanism of the helical spin structure in GdRu_{2}Si_{2} and Gd_{2}PdSi_{3}. We calculate the paramagnetic spin susceptibility and find that the Fermi surface nesting is not the origin of the incommensurate modulation, in contrast to the naive scenario based on the Ruderman-Kittel-Kasuya-Yosida mechanism. We then decompose the exchange interactions between the Gd spins into each orbital component, and show that spin-density-wave type interaction between the Gd-5d orbitals is ferromagnetic, but the interaction between the Gd-4f orbitals is antiferromagnetic. We conclude that the competition of these two interactions, namely, the interorbital frustration, stabilizes the finite-Q structure.

Thermoelectric generation using the anomalous Nernst effect (ANE) has great potential for application in energy harvesting technology because the transverse geometry of the Nernst effect should enable efficient, large-area and flexible coverage of a heat source. For such applications to be viable, substantial improvements will be necessary not only for their performance but also for the associated material costs, safety and stability. In terms of the electronic structure, the anomalous Nernst effect (ANE) originates from the Berry curvature of the conduction electrons near the Fermi energy 1,2 . To design a large Berry curvature, several approaches have been considered using nodal points and lines in momentum space 3-10 . Here we perform a high-throughput computational search and find that 25 percent doping of aluminium and gallium in alpha iron, a naturally abundant and low-cost element, dramatically enhances the ANE by a factor of more than ten, reaching about 4 and 6 microvolts per kelvin at room temperature, respectively, close to the highest value reported so far. The comparison between experiment and theory indicates that the Fermi energy tuning to the nodal web-a flat band structure made of interconnected nodal lines-is the key for the strong enhancement in the transverse thermoelectric coefficient, reaching a value of about 5 amperes per kelvin per metre with a logarithmic temperature dependence. We have also succeeded in fabricating thin films that exhibit a large ANE at zero field, which could be suitable for designing low-cost, flexible microelectronic thermoelectric generators 11-13 .

Wannier90 is an open-source computer program for calculating maximally-localised Wannier functions (MLWFs) from a set of Bloch states. It is interfaced to many widely used electronic-structure codes thanks to its independence from the basis sets representing these Bloch states. In the past few years the development of Wannier90 has transitioned to a community-driven model; this has resulted in a number of new developments that have been recently released in Wannier90 v3.0. In this article we describe these new functionalities, that include the implementation of new features for wannierisation and disentanglement (symmetry-adapted Wannier functions, selectively-localised Wannier functions, selected columns of the density matrix) and the ability to calculate new properties (shift currents and Berry-curvature dipole, and a new interface to many-body perturbation theory); performance improvements, including parallelisation of the core code; enhancements in functionality (support for spinor-valued Wannier functions, more accurate methods to interpolate quantities in the Brillouin zone); improved usability (improved plotting routines, integration with high-throughput automation frameworks), as well as the implementation of modern software engineering practices (unit testing, continuous integration, and automatic source-code documentation). These new features, capabilities, and code development model aim to further sustain and expand the community uptake and range of applicability, that nowadays spans complex and accurate dielectric, electronic, magnetic, optical, topological and transport properties of materials.

The discovery of superconductivity at 200 kelvin in the hydrogen sulfide system at high pressures 1 demonstrated the potential of hydrogen-rich materials as high-temperature superconductors. Recent theoretical predictions of rare-earth hydrides with hydrogen cages 2,3 and the subsequent synthesis of LaH 10 with a superconducting critical temperature (T c ) of 250 kelvin 4,5 have placed these materials on the verge of achieving the long-standing goal of room-temperature superconductivity. Electrical and X-ray diffraction measurements have revealed a weakly pressure-dependent T c for LaH 10 between 137 and 218 gigapascals in a structure that has a face-centred cubic arrangement of lanthanum atoms 5 . Here we show that quantum atomic fluctuations stabilize a highly symmetrical [Formula: see text] crystal structure over this pressure range. The structure is consistent with experimental findings and has a very large electron-phonon coupling constant of 3.5. Although ab initio classical calculations predict that this [Formula: see text] structure undergoes distortion at pressures below 230 gigapascals 2,3 , yielding a complex energy landscape, the inclusion of quantum effects suggests that it is the true ground-state structure. The agreement between the calculated and experimental T c values further indicates that this phase is responsible for the superconductivity observed at 250 kelvin. The relevance of quantum fluctuations calls into question many of the crystal structure predictions that have been made for hydrides within a classical approach and that currently guide the experimental quest for room-temperature superconductivity 6-8 . Furthermore, we find that quantum effects are crucial for the stabilization of solids with high electron-phonon coupling constants that could otherwise be destabilized by the large electron-phonon interaction 9 , thus reducing the pressures required for their synthesis.

Manipulating topological spin textures is a key for exploring unprecedented emergent electromagnetic phenomena. Whereas switching control of magnetic skyrmions, e.g., the transitions between a skyrmion-lattice phase and conventional magnetic orders, is intensively studied towards development of future memory device concepts, transitions among spin textures with different topological orders remain largely unexplored. Here we develop a series of chiral magnets MnSi 1-x Ge x , serving as a platform for transitions among skyrmion- and hedgehog-lattice states. By neutron scattering, Lorentz transmission electron microscopy and high-field transport measurements, we observe three different topological spin textures with variation of the lattice constant controlled by Si/Ge substitution: two-dimensional skyrmion lattice in x = 0-0.25 and two distinct three-dimensional hedgehog lattices in x = 0.3-0.6 and x = 0.7-1. The emergence of various topological spin states in the chemical-pressure-controlled materials suggests a new route for direct manipulation of the spin-texture topology by facile mechanical methods.

Discrete graphitic carbon compounds serve as tunable models for the properties of extended macromolecular structures such as nanotubes. Here, we report synthesis and characterization of a cylindrical C 304 H 264 molecule composed of 40 benzene (phenine) units mutually bonded at the 1, 3, and 5 positions. The concise nine-step synthesis featuring successive borylations and couplings proceeded with an average yield for each benzene-benzene bond formation of 91%. The molecular structure of the nanometer-sized cylinder with periodic vacancy defects was confirmed spectroscopically and crystallographically. The nanoporous nature of the compound further enabled inclusion of multiple fullerene guests. Computations suggest that fusing many such cylinders could produce carbon nanotubes with electronic properties modulated by the periodic vacancy defects., (Copyright © 2019 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

Magnetic properties of MnSb 2 Te 4 were examined through magnetic susceptibility, specific-heat, and neutron-diffraction measurements. As opposed to isostructural MnBi 2 Te 4 with the antiferromagnetic ground state, MnSb 2 Te 4 develops a spontaneous magnetization below 25 K. From our first-principles calculations on the material in a ferromagnetic state, the state could be interpreted as a type-II Weyl semimetal state with broken time-reversal symmetry. Detailed structural refinements using x-ray-diffraction and neutron-diffraction data reveal the presence of site mixing between Mn and Sb sites, leading to the ferrimagnetic ground state. With theoretical calculations, we found that the presence of site mixing plays an important role for the interlayer Mn-Mn ferromagnetic interactions.

Recently, superconductivity was induced by expanding interlayer distance between Bi square nets in anti-ThCr 2 Si 2 -type Y 2 O 2 Bi through incorporation of excess oxygen with increased nominal amount of oxygen. However, such oxygen incorporation was applicable to only Y 2 O 2 Bi among R 2 O 2 Bi ( R = rare earth metal), probably due to a larger amount of oxygen incorporation for Y 2 O 2 Bi. In this study, the interlayer distance in Er 2 O 2 Bi was increased by cosintering with CaO, which served as an oxidant, indicating that excess oxygen was incorporated in Er 2 O 2 Bi. As a result, superconductivity was induced in Er 2 O 2 Bi at 2.2 K.

When a polarized light beam is incident upon the surface of a magnetic material, the reflected light undergoes a polarization rotation 1 . This magneto-optical Kerr effect (MOKE) has been intensively studied in a variety of ferro- and ferrimagnetic materials because it provides a powerful probe for electronic and magnetic properties 2, 3 as well as for various applications including magneto-optical recording 4 . Recently, there has been a surge of interest in antiferromagnets (AFMs) as prospective spintronic materials for high-density and ultrafast memory devices, owing to their vanishingly small stray field and orders of magnitude faster spin dynamics compared to their ferromagnetic counterparts 5-9 . In fact, the MOKE has proven useful for the study and application of the antiferromagnetic (AF) state. Although limited to insulators, certain types of AFMs are known to exhibit a large MOKE, as they are weak ferromagnets due to canting of the otherwise collinear spin structure 10-14 . Here we report the first observation of a large MOKE signal in an AF metal at room temperature. In particular, we find that despite a vanishingly small magnetization of M ~0.002 µ B /Mn, the non-collinear AF metal Mn 3 Sn 15 exhibits a large zero-field MOKE with a polar Kerr rotation angle of 20 milli-degrees, comparable to ferromagnetic metals. Our first-principles calculations have clarified that ferroic ordering of magnetic octupoles in the non-collinear Néel state 16 may cause a large MOKE even in its fully compensated AF state without spin magnetization. This large MOKE further allows imaging of the magnetic octupole domains and their reversal induced by magnetic field. The observation of a large MOKE in an AF metal should open new avenues for the study of domain dynamics as well as spintronics using AFMs., Competing Interests: Competing Interests The authors declare that they have no competing financial interests.

Quantum states characterized by nontrivial topology produce interesting electrodynamics and versatile electronic functionalities. One source for such remarkable phenomena is emergent electromagnetic field, which is the outcome of interplay between topological spin structures with scalar spin chirality and conduction electrons. However, it has scarcely been exploited for emergent function related to heat-electricity conversion. Here we report an unusually enhanced thermopower by application of magnetic field in MnGe hosting topological spin textures. By considering all conceivable origins through quantitative investigations of electronic structures and properties, a possible origin of large magneto-thermopower is assigned to the strong energy dependence of charge-transport lifetime caused by unconventional carrier scattering via the dynamics of emergent magnetic field. Furthermore, high-magnetic-field measurements corroborate the presence of residual magnetic fluctuations even in the nominally ferromagnetic region, leading to a subsisting behavior of field-enhanced thermopower. The present finding may pave a way for thermoelectric function of topological magnets.

Weyl fermions have been observed as three-dimensional, gapless topological excitations in weakly correlated, inversion-symmetry-breaking semimetals. However, their realization in spontaneously time-reversal-symmetry-breaking phases of strongly correlated materials has so far remained hypothetical. Here, we report experimental evidence for magnetic Weyl fermions in Mn 3 Sn, a non-collinear antiferromagnet that exhibits a large anomalous Hall effect, even at room temperature. Detailed comparison between angle-resolved photoemission spectroscopy (ARPES) measurements and density functional theory (DFT) calculations reveals significant bandwidth renormalization and damping effects due to the strong correlation among Mn 3d electrons. Magnetotransport measurements provide strong evidence for the chiral anomaly of Weyl fermions-namely, the emergence of positive magnetoconductance only in the presence of parallel electric and magnetic fields. Since weak magnetic fields (approximately 10 mT) are adequate to control the distribution of Weyl points and the large fictitious fields (equivalent to approximately a few hundred T) produced by them in momentum space, our discovery lays the foundation for a new field of science and technology involving the magnetic Weyl excitations of strongly correlated electron systems such as Mn 3 Sn.

Cylinder-shaped graphitic networks in carbon nanotubes have attracted interest from scientists in various disciplines. The chemical synthesis of segments thereof is considered as a challenging and appealing subject in chemistry, and deepens our understanding of curved and conjugated arrays of hexagons. We herein report the synthesis of cylinder-shaped molecules containing non-hexagon bridges in their conjugated systems. Multiple pentagon units were embedded in the cylinder-shaped discrete molecules, and the stereoisomerism originating from their helical carbon arrangements was studied. Structural analysis by NMR, UV/Vis absorption spectroscopy, and single-crystal X-ray diffraction provided fundamental experimental information on the curved systems with conjugation across the pentagons. This study provides the first experimental guide for further explorations of anomalous non-hexagon arrays of graphitic carbon materials with cylindrical shapes., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Recent progress in the fully nonempirical calculation of the superconducting transition temperature (T c ) is reviewed. Especially, this study focuses on three representative light-element high-T c superconductors, i.e., elemental Li, sulfur hydrides, and alkali-doped fullerides. Here, it is discussed how crucial it is to develop the beyond Migdal-Eliashberg (ME) methods. For Li, a scheme of superconducting density functional theory for the plasmon mechanism is formulated and it is found that T c is dramatically enhanced by considering the frequency dependence of the screened Coulomb interaction. For sulfur hydrides, it is essential to go beyond not only the static approximation for the screened Coulomb interaction, but also the constant density-of-states approximation for electrons, the harmonic approximation for phonons, and the Migdal approximation for the electron-phonon vertex, all of which have been employed in the standard ME calculation. It is also shown that the feedback effect in the self-consistent calculation of the self-energy and the zero point motion considerably affect the calculation of T c . For alkali-doped fullerides, the interplay between electron-phonon coupling and electron correlations becomes more nontrivial. It has been demonstrated that the combination of density functional theory and dynamical mean field theory with the ab initio downfolding scheme for electron-phonon coupled systems works successfully. This study not only reproduces the experimental phase diagram but also obtains a unified view of the high-T c superconductivity and the Mott-Hubbard transition in the fullerides. The results for these high-T c superconductors will provide a firm ground for future materials design of new superconductors., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Molecular solids with cooperative electronic properties based purely on π electrons from carbon atoms offer a fertile ground in the search for exotic states of matter, including unconventional superconductivity and quantum magnetism. The field was ignited by reports of high-temperature superconductivity in materials obtained by the reaction of alkali metals with polyaromatic hydrocarbons, such as phenanthrene and picene, but the composition and structure of any compound in this family remained unknown. Here we isolate the binary caesium salts of phenanthrene, Cs(C 14 H 10 ) and Cs 2 (C 14 H 10 ), to show that they are multiorbital strongly correlated Mott insulators. Whereas Cs 2 (C 14 H 10 ) is diamagnetic because of orbital polarization, Cs(C 14 H 10 ) is a Heisenberg antiferromagnet with a gapped spin-liquid state that emerges from the coupled highly frustrated Δ-chain magnetic topology of the alternating-exchange spiral tubes of S = ½ (C 14 H 10 ) •- radical anions. The absence of long-range magnetic order down to 1.8 K (T/J ≈ 0.02; J is the dominant exchange constant) renders the compound an excellent candidate for a spin-½ quantum-spin liquid (QSL) that arises purely from carbon π electrons.

An interesting physical phenomenon, electroluminescence, that was originally observed with a hydrocarbon molecule has recently been developed into highly efficient organic light-emitting devices. These modern devices have evolved through the development of multi-element molecular materials for specific roles, and hydrocarbon devices have been left unexplored. In this study, we report an efficient organic light-emitting device composed solely of hydrocarbon materials. The electroluminescence was achieved in the blue region by efficient fluorescence and charge recombination within a simple single-layer architecture of macrocyclic aromatic hydrocarbons. This study may stimulate further studies on hydrocarbons to uncover their full potential as electronic materials., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The electric field effect is a useful means of elucidating intrinsic material properties as well as for designing functional devices. The electric-double-layer transistor (EDLT) enables the control of carrier density in a wide range, which is recently proved to be an effective tool for the investigation of thermoelectric properties. Here, we report the gate-tuning of thermoelectric power in a black phosphorus (BP) single crystal flake with the thickness of 40 nm. Using an EDLT configuration, we successfully control the thermoelectric power (S) and find that the S of ion-gated BP reached +510 μV/K at 210 K in the hole depleted state, which is much higher than the reported bulk single crystal value of +340 μV/K at 300 K. We compared this experimental data with the first-principles-based calculation and found that this enhancement is qualitatively explained by the effective thinning of the conduction channel of the BP flake and nonuniformity of the channel owing to the gate operation in a depletion mode. Our results provide new opportunities for further engineering BP as a thermoelectric material in nanoscale.

We present a physical picture for the emergence of the Dzyaloshinskii-Moriya (DM) interaction based on the idea of the Doppler shift by an intrinsic spin current induced by spin-orbit interaction under broken inversion symmetry. The picture is confirmed by a rigorous effective Hamiltonian theory, which reveals that the DM coefficient is given by the magnitude of the intrinsic spin current. Our approach is directly applicable to first principles calculations and clarifies the relation between the interaction and the electronic band structures. Quantitative agreement with experimental results is obtained for the skyrmion compounds Mn_{1-x}Fe_{x}Ge and Fe_{1-x}Co_{x}Ge.

Coronene, which is the smallest D6h -symmetric polycyclic aromatic hydrocarbon, attracts particular attention as a basic component of electronic materials because it is the smallest fragment of graphene. However, carrier generation by physical methods, such as photo- or electric field-effect, has barely been studied, primarily because of the poor π-conduction pathway in pristine coronene solid. In this work we have developed unprecedented π-stacking columns of cationic coronene molecules by electrochemical hole-doping with polyoxometallate dianions. The face-to-face π-π interactions as well as the partially charged state lead to electrical conductivity at room temperature of up to 3 S cm(-1) , which is more than 10 orders of magnitude higher than that of pristine coronene solid. Additionally, the robust π-π interactions strongly suppress the in-plane rotation of the coronene molecules, which has allowed the first direct observation of the static Jahn-Teller distortion of cationic coronene molecules., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A modern electrophosphorescent organic light-emitting device (OLED) achieves quantitative electro-optical conversion by using multiple layers of molecular materials designed through role allotment for independent and specific functions. A unique, potentially innovative device architecture, i.e. , a single-layer phosphorescent OLED, is currently being developed by designing multirole base materials via a structural combination of multiple functional components in single molecules. The multirole molecules, however, inevitably require multiple processes to synthesize their multiple components and, moreover, to assemble these components synthetically into one molecule. We herein show that the multirole base material for a highly efficient single-layer phosphorescent OLED can be designed and synthesized with a single, very simple aromatic hydrocarbon component of toluene merely through a one-pot macrocyclization. Without requiring the assembly tasks at the synthesis stage, the molecular design allows for a concise one-pot synthesis of, and a quantitative electro-optical conversion in, the single-layer device architecture with a single-component base material.

We theoretically show that an interlayer bias voltage in the AB-stacked bilayer graphene nanoribbons with armchair edges induces an electric polarization along the ribbon. Both tight-binding and ab initio calculations consistently indicate that when the bias voltage is weak, the polarization shows opposite signs depending on the ribbon width modulo three. This nontrivial dependence is explained using a two-band effective model. A strong limit of the bias voltage in the tight-binding model shows either one-third or zero polarization, which agrees with the topological argument.

Motivated by the recent experiment on the size and helicity control of skyrmions in Mn(1-x)Fe(x)Ge, we study how the Dzyaloshinskii-Moriya (DM) interaction changes its size and sign in metallic helimagnets. By means of first-principles calculations, we successfully reproduce the non-trivial sign change of the DM interaction observed in the experiment. While the DM interaction sensitively depends on the carrier density or the detail of the electronic structure such as the size of the exchange splitting, its behavior can be systematically understood in terms of the distribution of anticrossing points in the band structure. By following this guiding principle, we can even induce gigantic anisotropy in the DM interaction by applying a strain to the system. These results pave the new way for skyrmion crystal engineering in metallic helimagnets.

Organic crystals are likely to have a large degree of structural relaxation near their surfaces because of the weak inter-molecular interactions. The design of organic field-effect transistors requires a detailed knowledge of the surface relaxation as the carriers usually transfer within the first few molecular layers at the semiconductor surfaces, and their transport properties reflect the structural changes through the transfer integral. Here, we report the direct observation of the surface relaxation of an organic semiconductor, a tetracene single crystal, by means of X-ray crystal truncation rod scattering measurements. A significant degree of surface relaxation is observed, taking place only in the first monolayer at the semiconductor surface. First principles calculations show that the resultant transfer integrals are completely different between the bulk and surface of the semiconductor.

We study boron-doped carbon nanotubes by first-principles methods based on the density functional theory. To discuss the possibility of superconductivity, we calculate the electronic band structure and the density of states (DOS) of boron-doped (10,0) nanotubes by changing the boron density. It is found that the Fermi level density of states D (∊ F ) increases upon lowering the boron density. This can be understood in terms of the rigid band picture where the one-dimensional van Hove singularity lies at the edge of the valence band in the DOS of the pristine nanotube. The effect of three-dimensionality is also considered by performing the calculations for bundled (10,0) nanotubes and boron-doped double-walled carbon nanotubes (10,0)@(19,0). From the calculation of the bundled nanotubes, it is found that interwall dispersion is sufficiently large to broaden the peaks of the van Hove singularity in the DOS. Thus, to achieve the high D (∊ F ) using the bundle of nanotubes with single chirality, we should take into account the distance from each nanotube. In the case of double-walled carbon nanotubes, we find that the holes introduced to the inner tube by boron doping spread also on the outer tube, while the band structure of each tube remains almost unchanged.

Superconductivity in carbon nanotubes (CNTs) is attracting considerable attention. However, its correlation with carrier doping has not been reported. We report on the Meissner effect found in thin films consisting of assembled boron (B)-doped single-walled CNTs (B-SWNTs). We find that only B-SWNT films consisting of low boron concentration leads to evident Meissner effect with Tc=12 K and also that a highly homogeneous ensemble of the B-SWNTs is crucial. The first-principles electronic-structure study of the B-SWNTs strongly supports these results.

The two-dimensional t-J model on a triangular lattice is studied using high-temperature expansions. By studying the entropy and spin susceptibility, we find that the sign of the hopping integral t is very crucial. In the case of t>0, the peak of the spin susceptibility moves to the high-temperature region with hole doping, which indicates the appearance of the resonating-valence-bond state. In contrast, for t<0, the peak of the spin susceptibility disappears with hole doping and the entropy at low temperatures behaves as S=gammaT with large coefficient gamma, representing a large effective mass. This behavior is understood from the competition between Nagaoka's ferromagnetism and singlet formation.