Structural Characterization of Graphite Analogue BCx Synthesized Under Various Conditions and Its Application to Ti Intercalation.

A graphite-like material boron carbide (BCx) was synthesized under various heat treatment conditions and extensively characterized. First, we synthesized the BCx precursor phase by a single-step reaction using a mixed solution of BBr3 and C6H6. We confirmed that the precursor phase had a graphite-like structure with B-C chemical bonds, but its crystallinity was poor. To improve their crystallinity, we annealed the precursor sample at high temperature using a high-frequency furnace and determined the annealing condition. We also investigated the magnetic properties of BCx. The high-temperature annealing for the precursor phase yields the highest Pauli paramagnetic susceptibility χPauli, indicating the highest density of states at the Fermi level. Accordingly, the high-temperature treatment for the precursor phase is significant to improve its crystallinity and physical properties. In addition, we synthesized a Ti-intercalated material TiBC by using the same procedure as that for making the BCx precursor phase. The crystal structure can be indexed by the AlB2 structure, indicating that Ti atoms are intercalated between the BC layers. The χPauli value of TiBC is obtained to be 1 order of magnitude smaller than that of BCx, suggesting the compensation of hole carriers by electron doping through Ti intercalation into the BCx system.

Antiferromagnetic structure with strongly reduced ordered moment of p-electron in CsO2.

We have performed a powder neutron diffraction study on CsO2, where the unpaired electron withs=1/2in theπ∗orbital of the O2-ion is responsible for the magnetism. The magnetic reflections 0120 and 0121 were observed below the Néel temperature of about 10 K. An antiferromagnetic structure with a propagation vector of (0,12, 0) and magnetic moments parallel to thea-axis is the most plausible. The magnitude of the ordered moment is about 0.2 µB, which is considered to be strongly reduced due to the one-dimensionality of the system. We propose a possibleπ∗orbital order that can explain the obtained magnetic structure, and discuss its relation to the one-dimensionality.

Single Crystals of Mixed-Cation Copper-Based Perovskite with Trimodal Bandgap Behavior.

Two-dimensional (2D) hybrid perovskites with novel functionalities and structural diversity are a perfect platform for emerging optoelectronic devices such as photodetectors, light-emitting diodes, and solar cells. Here, we demonstrate that excess concentration of Cesium bromide (CsBr) is key to the formation of easily exfoliated 2D Cs2 Cu(Cl/Br)4 perovskite crystal. Furthermore, by employing this trick to 2D perovskite MA2 Cu(Cl/Br)4 (MA=methylammonium), we achieve a phase-pure easily exfoliated 2D mixed-cation (MA/Cs)2 Cu(Cl/Br)4 perovskite crystal, which exhibits reduced bandgap (1.53 eV) with ferromagnetic behavior and photovoltaic property. The resultant mixed-cation structured device reveals enhanced efficiency compared to all MA and all Cs counterparts. These findings demonstrate the importance of cation-engineering in developing innovative materials with novel properties.

A new protocol for the preparation of superconducting KBi2.

A superconducting KBi2 sample was successfully prepared using a liquid ammonia (NH3) technique. The temperature dependence of the magnetic susceptibility (M/H) showed a superconducting transition temperature (T c) as high as 3.6 K. In addition, the shielding fraction at 2.0 K was evaluated to be 87%, i.e., a bulk superconductor was realized using the above method. The T c value was the same as that reported for the KBi2 sample prepared using a high-temperature annealing method. An X-ray diffraction pattern measured based on the synchrotron X-ray radiation was analyzed using the Rietveld method, with a lattice constant, a, of 9.5010(1) Šunder the space group of Fd3̄m (face-centered cubic, no. 227). The lattice constant and space group found for the KBi2 sample using a liquid NH3 technique were the same as those reported for KBi2 through a high-temperature annealing method. Thus, the superconducting behavior and crystal structure of the KBi2 sample obtained in this study are almost the same as those for the KBi2 sample reported previously. Strictly speaking, the magnetic behavior of the superconductivity was different from that of a KBi2 sample reported previously, i.e., the KBi2 sample prepared using a liquid NH3 technique was a type-II like superconductor, contrary to that prepared using a high-temperature annealing method, the reason for which is fully discussed. These results indicate that the liquid NH3 technique is effective and simple for the preparation of a superconducting KBi2. In addition, the topological nature of the superconductivity for KBi2 was not confirmed.

Industrial separation of oxygen isotopes by oxygen distillation.

18 O-labeled water (Water-18 O) is a widely used starting material of 18 F-labeled diagnostic agents in positron emission tomography (PET). Conventionally, Water-18 O has been separated from other stable oxygen isotope species (16 O, 17 O) by water distillation or nitric oxide distillation. However, conventional methods are costly and may have safety issues. In 2004, we developed the first unit of our novel oxygen isotope separation process by cryogenic oxygen distillation to overcome these issues. To meet the needs of the market, we built a second unit in 2013 and a third in 2016. We are now operating three commercially viable separation units with a total capacity of 600 kg of Water-18 O per year.

Chemical analysis of superconducting phase in K-doped picene.

Potassium-doped picene (K3.0picene) with a superconducting transition temperature (T C) as high as 14 K at ambient pressure has been prepared using an annealing technique. The shielding fraction of this sample was 5.4% at 0 GPa. The T C showed a positive pressure-dependence and reached 19 K at 1.13 GPa. The shielding fraction also reached 18.5%. To investigate the chemical composition and the state of the picene skeleton in the superconducting sample, we used energy-dispersive x-ray (EDX) spectroscopy, MALDI-time-of-flight (MALDI-TOF) mass spectroscopy and x-ray diffraction (XRD). Both EDX and MALDI-TOF indicated no contamination with materials other than K-doped picene or K-doped picene fragments, and supported the preservation of the picene skeleton. However, it was also found that a magnetic K-doped picene sample consisted mainly of picene fragments or K-doped picene fragments. Thus, removal of the component contributing the magnetic quality to a superconducting sample should enhance the volume fraction.

Emergence of superconductivity in (NH3)yMxMoSe2 (M: Li, Na and K).

We report syntheses of new superconducting metal-doped MoSe2 materials (MxMoSe2). The superconducting MxMoSe2 samples were prepared using a liquid NH3 technique, and can be represented as '(NH3)yMxMoSe2'. The Tcs of these materials were approximately 5.0 K, independent of x and the specific metal atom. X-ray diffraction patterns of (NH3)yNaxMoSe2 were recorded using polycrystalline powders. An increase in lattice constant c showed that the Na atom was intercalated between MoSe2 layers. The x-independence of c was observed in (NH3)yNaxMoSe2, indicating the formation of a stoichiometric compound in the entire x range, which is consistent with the x-independence of Tc. A metallic edge of the Fermi level was observed in the photoemission spectrum at 30 K, demonstrating its metallic character in the normal state. Doping of MoSe2 with Li and K also yielded superconductivity. Thus, MoSe2 is a promising material for designing new superconductors, as are other transition metal dichalcogenides.

Recent progress on carbon-based superconductors.

This article reviews new superconducting phases of carbon-based materials. During the past decade, new carbon-based superconductors have been extensively developed through the use of intercalation chemistry, electrostatic carrier doping, and surface-proving techniques. The superconducting transition temperature T c of these materials has been rapidly elevated, and the variety of superconductors has been increased. This review fully introduces graphite, graphene, and hydrocarbon superconductors and future perspectives of high-T c superconductors based on these materials, including present problems. Carbon-based superconductors show various types of interesting behavior, such as a positive pressure dependence of T c. At present, experimental information on superconductors is still insufficient, and theoretical treatment is also incomplete. In particular, experimental results are still lacking for graphene and hydrocarbon superconductors. Therefore, it is very important to review experimental results in detail and introduce theoretical approaches, for the sake of advances in condensed matter physics. Furthermore, the recent experimental results on hydrocarbon superconductors obtained by our group are also included in this article. Consequently, this review article may provide a hint to designing new carbon-based superconductors exhibiting higher T c and interesting physical features.

A new way to synthesize superconducting metal-intercalated C60 and FeSe.

Doping with the optimum concentration of carriers (electrons or holes) can modify the physical properties of materials. Therefore, improved ways to achieve carrier doping have been pursued extensively for more than 50 years. Metal-intercalation is one of the most important techniques for electron doping of organic / inorganic solids, and has produced superconductors from insulators and metallic solids. The most successful examples are metal-intercalated graphite and C60 superconductors. Metal intercalation has been performed using solid-reaction and liquid solvent techniques. However, precise control of the quantity of intercalants in the target solids can be difficult to achieve using these methods, as that quantity depends largely on the initial conditions. Here we report an electrochemical method for metal-intercalation, and demonstrate the preparation of superconductors using organic and inorganic materials (C60 and FeSe). The metal atoms are effectively intercalated into the spaces in C60 and FeSe solids by supplying an electric current between electrodes in a solvent that includes electrolytes. The recorded superconducting transition temperatures, Tc's, were the same as those of metal-intercalated C60 and FeSe prepared using solid-reaction or liquid solvent techniques. This technique may open a new avenue in the search for organic / inorganic superconductors.

Emergence of double-dome superconductivity in ammoniated metal-doped FeSe.

The pressure dependence of the superconducting transition temperature (Tc) and unit cell metrics of tetragonal (NH3)yCs0.4FeSe were investigated in high pressures up to 41 GPa. The Tc decreases with increasing pressure up to 13 GPa, which can be clearly correlated with the pressure dependence of c (or FeSe layer spacing). The Tc vs. c plot is compared with those of various (NH3)yMxFeSe (M: metal atoms) materials exhibiting different Tc and c, showing that the Tc is universally related to c. This behaviour means that a decrease in two-dimensionality lowers the Tc. No superconductivity was observed down to 4.3 K in (NH3)yCs0.4FeSe at 11 and 13 GPa. Surprisingly, superconductivity re-appeared rapidly above 13 GPa, with the Tc reaching 49 K at 21 GPa. The appearance of a new superconducting phase is not accompanied by a structural transition, as evidenced by pressure-dependent XRD. Furthermore, Tc slowly decreased with increasing pressure above 21 GPa, and at 41 GPa superconductivity disappeared entirely at temperatures above 4.9 K. The observation of a double-dome superconducting phase may provide a hint for pursuing the superconducting coupling-mechanism of ammoniated/non-ammoniated metal-doped FeSe.

qEMF3, a novel QTL for the early-morning flowering trait from wild rice, Oryza officinalis, to mitigate heat stress damage at flowering in rice, O. sativa.

A decline in rice (Oryza sativa L.) production caused by heat stress is one of the biggest concerns resulting from future climate change. Rice spikelets are most susceptible to heat stress at flowering. The early-morning flowering (EMF) trait mitigates heat-induced spikelet sterility at the flowering stage by escaping heat stress during the daytime. We attempted to develop near-isogenic lines (NILs) for EMF in the indica-type genetic background by exploiting the EMF locus from wild rice, O. officinalis (CC genome). A stable quantitative trait locus (QTL) for flower opening time (FOT) was detected on chromosome 3. A QTL was designated as qEMF3 and it shifted FOT by 1.5-2.0 h earlier for cv. Nanjing 11 in temperate Japan and cv. IR64 in the Philippine tropics. NILs for EMF mitigated heat-induced spikelet sterility under elevated temperature conditions completing flower opening before reaching 35°C, a general threshold value leading to spikelet sterility. Quantification of FOT of cultivars popular in the tropics and subtropics did not reveal the EMF trait in any of the cultivars tested, suggesting that qEMF3 has the potential to advance FOT of currently popular cultivars to escape heat stress at flowering under future hotter climates. This is the first report to examine rice with the EMF trait through marker-assisted breeding using wild rice as a genetic resource.

Dynamically fluctuating electric dipole moments in fullerene-based magnets.

We report here the direct evidence of the existence of a permanent electric dipole moment in both crystal phases of a fullerene-based magnet--the ferromagnetic α-phase and the antiferromagnetic α'-phase of tetra-kis-(dimethylamino)-ethylene-C60 (TDAE-C60)--as determined by dielectric measurements. We propose that the permanent electric dipole originates from the pairing of a TDAE molecule with surrounding C60 molecules. The two polymorphs exhibit clear differences in their dielectric responses at room temperature and during the freezing process with dynamically fluctuating electric dipole moments, although no difference in their room-temperature structures has been previously observed. This result implies that two polymorphs have different local environment around the molecules. In particular, the ferromagnetism of the α-phase is founded on the homogeneous molecule displacement and orientational ordering. The formation of the different phases with respect to the different rotational states in the Jahn-Teller distorted C60s is also discussed.

Antiferromagnetic resonance in the Mott insulator fcc-Cs3C60.

The magnetic ground state of the fcc phase of the Mott insulator Cs3C60 was studied using a low-temperature electron spin resonance technique, and antiferromagnetic resonance (AFMR) below 1.57 K was directly observed at ambient pressure. The AFMR modes for the fcc phase of Cs3C60 were investigated using a conventional two-sublattice model with uniaxial anisotropy, and the spin-flop field was determined to be 4.7 kOe at 1.57 K. The static magnetic exchange interactions and anisotropy field for fcc-Cs3C60 were also estimated.

Magnetoelectric effect driven by magnetic domain modification in LuFe2O4.

The magnetocapacitance effect was investigated using impedance spectroscopy on single crystals of LuFe(2)O(4). The intrinsic impedance response could be separated from the interfacial response and showed a clear hysteresis loop below T(Ferri)∼240 K under the magnetic field. The neutron diffraction experiment under the magnetic field proves the origin of the dielectric property related to the motion of the nanosized ferromagnetic domain boundary. These results imply that the modification of the microscopic domain structure is responsible for the magnetoelectric effect in LuFe(2)O(4).

Strong intramolecular electron-phonon coupling in the negatively charged aromatic superconductor picene.

Superconductivity was recently discovered in solid potassium-intercalated picene (K(3)22ph), in which the picene molecule becomes trianionic (22ph(3-)). In this Letter, we conduct a theory-based study of the superconductivity of 22ph(3-) within the framework of BCS theory. We estimate the density of states N(ε(F)) on the Fermi level to be 2.2 states per (eV molecule spin) by using the theoretical intramolecular electron-phonon coupling l(x) and the experimental superconducting transition temperature T(c) of 18 K. The theoretical value is consistent with the 1.2 states per (eV molecule spin) determined experimentally for K(3)22ph with T(c)=18 K, indicating the validity of our theoretical treatment and the electron-phonon mechanism for superconductivity. The predicted l(x), 0.206 eV, for 22ph(3-) is larger than any value reported for organic superconductors, so picene may have the largest l(x) among the superconductors reported so far.

Metal-intercalated aromatic hydrocarbons: a new class of carbon-based superconductors.

New carbon-based superconductors are synthesized by intercalating metal atoms into the solid-phase hydrocarbons picene and coronene. The highest reported superconducting transition temperature, T(c), of a hydrocarbon superconductor is 18 K for K(3)picene. The physics and chemistry of the hydrocarbon superconductors are extensively described for A(x)picene (A: alkali and alkali earth-metal atoms) for x = 0-5. The theoretical picture of their electronic structure is also reviewed. Future prospects for hydrocarbon superconductors are discussed from the viewpoint of combining electronics with condensed-matter physics: modification of the physical properties of hydrocarbon solids is explored by building them into a field-effect transistor. The features of other carbon-based superconductors are compared to clarify the nature of hydrocarbon superconductors.

Superconductivity in alkali-metal-doped picene.

Efforts to identify and develop new superconducting materials continue apace, motivated by both fundamental science and the prospects for application. For example, several new superconducting material systems have been developed in the recent past, including calcium-intercalated graphite compounds, boron-doped diamond and-most prominently-iron arsenides such as LaO(1-x)F(x)FeAs (ref. 3). In the case of organic superconductors, however, no new material system with a high superconducting transition temperature (T(c)) has been discovered in the past decade. Here we report that intercalating an alkali metal into picene, a wide-bandgap semiconducting solid hydrocarbon, produces metallic behaviour and superconductivity. Solid potassium-intercalated picene (K(x)picene) shows T(c) values of 7 K and 18 K, depending on the metal content. The drop of magnetization in K(x)picene solids at the transition temperature is sharp (<2 K), similar to the behaviour of Ca-intercalated graphite. The T(c) of 18 K is comparable to that of K-intercalated C(60) (ref. 4). This discovery of superconductivity in K(x)picene shows that organic hydrocarbons are promising candidates for improved T(c) values.

Antiferromagnetic ordering driven by the molecular orbital order of C(60) in alpha'-tetra-kis-(Dimethylamino)-ethylene-C(60).

We have studied the ground state of a fullerene-based magnet, the alpha;{'}-phase tetra-kis-(dimethylamino)-ethylene-C60 (alpha'-TDAE-C(60)), by electron spin resonance and magnetic torque measurements. Below T(N) = 7 K, nonparamagnetic field dependent resonances with a finite excitation gap (1.7 GHz) are observed along the a axis. Strong enhancement in their intensity as temperature is decreased is inconsistent with excitation from a singlet state, which had been proposed for the alpha'-phase ground state. Below T(N), nonquadratic field dependence of the magnetic torque signal is also observed in contrast to quadratic field dependence in the paramagnetic phase. The angle-dependent torque signals below T(N) indicate the existence of an anisotropy of the bulk magnetization. From both experiments, we propose an antiferromagnetic ground state driven by the cooperative orientational ordering of C(60) in the alpha'-TDAE-C(60).