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In this study, we successfully synthesized a novel A-site columnar-ordered perovskite CaZnV2O6. This compound features a square-planar-coordinated Zn2+ disorder, which is the same characteristic as the centrosymmetric paraelectric CaMnTi2O6. Unlike CaMnTi2O6, which shows a centrosymmetric paraelectric-noncentrosymmetric ferroelectric transition, CaZnV2O6 retains Pauli-paramagnetic metallicity arising from itinerant V4+ d1 electrons and centrosymmetry down to 5 K. Based on analogous compounds, we expect CaZnV2O6 to provide a new playground for the electronic and magnetic states of V4+.
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Bi0.5Pb0.5FeO3 with 1:1 mixture of Bi and Pb having charge degrees of freedom at the A-site of perovskite oxide ABO3 is obtained for the first time by high-pressure synthesis. Comprehensive synchrotron X-ray powder diffraction, optical second harmonic generation, Mössbauer spectroscopy, and hard X-ray photoemission spectroscopy measurements revealed that Bi0.5Pb0.5FeO3 is a canted antiferromagnetic insulator crystalizing in a nonpolar tetragonal I4/mcm structure with â2a × â2a × 2a unit cell and has unusually Pb charge disproportionated Bi3+0.5Pb2+0.25Pb4+0.25Fe3+O3 charge distribution. The valence of transition metal M in Bi0.5Pb0.5MO3 changes from 3.5+ to 3+ and finally to 2+ from Mn to Fe and to Ni, from left to right in the periodic table as the 3d-level becomes deeper. The valences of Bi and Pb increase to compensate for the decrease in the M's valence, and Pb changes from 6s2 (2+) to 6s0 (4+) before Bi changes.
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Spontaneous polarization (Ps) of novel order-disorder type lead-free ferroelectric CaMnTi2O6 was successfully enhanced by partial V4+ substitution for Ti4+. A synchrotron X-ray diffraction study revealed that the polar displacement of octahedrally coordinated (Ti, V) in CaMn(Ti1-xVx)2O6 (0 ≤ x ≤ 0.4) increases with V4+ substitution having Jahn-Teller activity owing to the d1 electronic configuration. Our magnetic study suggested the presence of antisite disorder between Ca2+ and square planar coordinated Mn2+ associated with Mn-V intermetallic charge transfer for x ≥ 0.4, resulting in decreases in spontaneous polarization and the ferroelectric-paraelectric transition temperature. This is the first report on the enhanced polarization owing to the Jahn-Teller distortion of V4+ without stereochemical Pb2+ or Bi3+.
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Negative thermal expansion (NTE) induced by simultaneous mechanisms, that is, charge transfer and polar-nonpolar transitions, was observed for the first time in BiNi1-xFexO3 (0.25 ≤ x ≤ 0.5). The low-temperature phase was found to have a polar structure (space group of R3c) with a Bi3+0.5(1+x)Bi5+0.5(1-x)Ni2+1-xFe3+xO3 charge distribution and short-range ordering of Bi3+ and Bi5+. The volume reduction upon heating that was induced by charge transfer between Bi5+ and Ni2+ decreased with increasing x because of the reduction in the amount of Ni2+. Simultaneous polar-nonpolar transition also contributed to NTE, and a composition-independent enhanced volume reduction of â¼2% was observed.
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BiCoO3 is a PbTiO3 type of perovskite oxide with a giant tetragonal distortion (c/a = 1.27) that shows a pressure-induced transition from tetragonal to orthorhombic phases accompanied by a large volume shrinkage at 3 GPa. In this study, we carried out electron doping of BiCoO3 by substituting Ti4+ for Co3+ in order to destabilize the tetragonal phase and observe a giant negative thermal expansion (NTE) at ambient pressure. BiCo1-xTixO3 (x = 0, 0.1, 0.2, and 0.25) was successfully obtained by using high-pressure synthesis. However, the c/a ratio of the tetragonal phase was almost constant against x (≤0.2), and NTE was not observed at any x, suggesting that the tetragonal distortion coupled with high-spin Co3+ is robust against electron doping. In x = 0.25, a metastable orthorhombic phase was obtained by the high-pressure synthetic process, while it partially transformed into a tetragonal phase after annealing at 600 K. The stability of the giant tetragonal phase is strongly connected with the spin state of Co3+.
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An epitaxial film of YbFe2O4, a candidate for oxide electronic ferroelectrics, was fabricated on yttrium-stabilized zirconia (YSZ) substrate by magnetron sputtering technique. For the film, second harmonic generation (SHG), and a terahertz radiation signal were observed at room temperature, confirming a polar structure of the film. The azimuth angle dependence of SHG shows four leaves-like profiles and is almost identical to that in a bulk single crystal. Based on tensor analyses of the SHG profiles, we could reveal the polarization structure and the relationship between the film structure of YbFe2O4 and the crystal axes of the YSZ substrate. The observed terahertz pulse showed anisotropic polarization dependence consistent with the SHG measurement, and the intensity of the emitted terahertz pulse reached about 9.2% of that emitted from ZnTe, a typical nonlinear crystal, implying that YbFe2O4 can be applied as a terahertz wave generator in which the direction of the electric field can be easily switched.
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To investigate photoinduced phenomena in various materials and molecules, ultrashort pulsed x-ray and electron sources with high brightness and high repetition rates are required. The x-ray and electron's typical and de Broglie wavelengths are shorter than lattice constants of materials and molecules. Therefore, photoinduced structural dynamics on the femtosecond to picosecond timescales can be directly observed in a diffraction manner by using these pulses. This research created a tabletop ultrashort pulsed electron diffraction setup that used a femtosecond laser and electron pulse compression cavity that was directly synchronized to the microwave master oscillator (â¼3 GHz). A compressed electron pulse with a 1 kHz repetition rate contained 228 000 electrons. The electron pulse duration was estimated to be less than 100 fs at the sample position by using photoinduced immediate lattice changes in an ultrathin silicon film (50 nm). The newly developed time-resolved electron diffraction setup has a pulse duration that is comparable to femtosecond laser pulse widths (35-100 fs). The pulse duration, in particular, fits within the timescale of photoinduced phenomena in quantum materials. Our developed ultrafast time-resolved electron diffraction setup with a sub-100 fs temporal resolution would be a powerful tool in material science with a combination of optical pump-probe, time-resolved photoemission spectroscopic, and pulsed x-ray measurements.
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Correlated electron systems can undergo ultrafast photoinduced phase transitions involving concerted transformations of electronic and lattice structure. Understanding these phenomena requires identifying the key structural modes that couple to the electronic states. We report the ultrafast photoresponse of the molecular crystal Me4P[Pt(dmit)2]2, which exhibits a photoinduced charge transfer similar to transitions between thermally accessible states, and demonstrate how femtosecond electron diffraction can be applied to directly observe the associated molecular motions. Even for such a complex system, the key large-amplitude modes can be identified by eye and involve a dimer expansion and a librational mode. The dynamics are consistent with the time-resolved optical study, revealing how the electronic, molecular, and lattice structures together facilitate ultrafast switching of the state.
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The quasistable state in the photoinduced phase transition for the quasi-one-dimensional quarter-filled organic conductor (EDO-TTF)2PF6 has been examined by ultrafast reflective measurements and time-dependent model calculations incorporating both electron-electron and electron-phonon interactions. The transient optical conductivity spectrum over a wide probe photon-energy range revealed that photoexcitation induced a new type of charge-disproportionate state. Additionally, coherent and incoherent oscillations dependent on probe photon energies were found, as predicted by the calculation.
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A 1:1 adduct of chloranilic acid with 5,5'-dimethyl-2,2'-bipyridine, in which two kinds of molecules are connected by infinite hydrogen bond chains, exhibits a distinct dielectric phase transition when cooled. Below T(c)(=318 K) the hydrogen atoms participating in hydrogen bonding undergo long-range ordering and form an antiferroelectric-like state, taking a single minimum potential in the high-temperature phase (T>T(c)) due to the bifurcate hydrogen bond system. The proton-transfer phenomenon was clearly observed by electron density distribution analysis using a maximum entropy method of synchrotron x-ray diffraction data.
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The research on ferroelectric materials-mostly inorganic compounds or organic polymers-is increasingly motivated by both basic scientific concerns and the potential for practical applications in electronics and optics. Ferroelectricity in organic solids would be important for the development of all-organic electronic and photonic devices. The conventional approach to making organic ferroelectrics is based on the use of polar molecules. Here we report that through supramolecular assembly of nonpolar conjugated molecules, a remarkable ferroelectric response can be obtained in co-crystals of low-molecular-weight organic compounds. Co-crystals of phenazine and chloranilic acid reveal large spontaneous polarization and sizable room-temperature dielectric constants exceeding 100. The present findings provide an approach to making potentially useful organic ferroelectric materials.
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A phase transition in an organic charge-transfer complex, which originates from the neutral-ionic valence instability, can be tuned toward zero kelvin with use of external pressure or chemical modification as a control parameter. The phase diagram and observed dielectric behaviors are typical of quantum paraelectricity, yet this zero-kelvin transition point namely, the quantum critical point, accompanies large quantum fluctuation of the molecular charge, as demonstrated by the molecular vibrational mode spectra. The result indicates that the pi-electron transfer between donor and acceptor molecules is coupled with the zero-point lattice dynamics around the quantum critical point.