Thermal multiferroics in all-inorganic quasi-two-dimensional halide perovskites.

Multiferroic materials, particularly those possessing simultaneous electric and magnetic orders, offer a platform for design technologies and to study modern physics. Despite the substantial progress and evolution of multiferroics, one priority in the field remains to be the discovery of unexplored materials, especially those offering different mechanisms for controlling electric and magnetic orders1. Here we demonstrate the simultaneous thermal control of electric and magnetic polarizations in quasi-two-dimensional halides (K,Rb)3Mn2Cl7, arising from a polar-antipolar transition, as evidenced using both X-ray and neutron powder diffraction data. Our density functional theory calculations indicate a possible polarization-switching path including a strong coupling between the electric and magnetic orders in our halide materials, suggesting a magnetoelectric coupling and a situation not realized in oxide analogues. We expect our findings to stimulate the exploration of non-oxide multiferroics and magnetoelectrics to open access to alternative mechanisms, beyond conventional electric and magnetic control, for coupling ferroic orders.

Pressure-Induced Superconductivity in Iron-Based Spin-Ladder Compound BaFe2+δ(S1-xSex)3.

The iron-based superconductors had a significant impact on condensed matter physics. They have a common structural motif of a two-dimensional square iron lattice and exhibit fruitful physical properties as a strongly correlated electron system. During the extensive investigations, quasi-one-dimensional iron-based spin-ladder compounds attracted much attention as a platform for studying the interplay between magnetic and orbital ordering. In these compounds, BaFe2S3 and BaFe2Se3 were found to exhibit superconductivity under high pressure, having a different crystal and magnetic structure at low temperature. We report a brief review of the iron-based spin-ladder compound and recent studies for BaFe2+δ(S1-xSex)3. BaFe2(S0.75 Se0.25)3 is in the vicinity of the boundary of two different magnetic phases and it is intriguing to perform high pressure experiments for studying superconductivity, since effects of large magnetic fluctuations on superconductivity are expected. The effect of iron stoichiometry on the interplay between magnetism and superconductivity is also studied by changing the iron concentration in BaFe2+δSe3.

Large Magnon Contributions to Thermal Conductance in Quasi-One-Dimensional Fe-Based Ladder Compounds BaFe_{2}(S_{1-x}Se_{x})_{3}.

We investigate the magnetic phase diagram of a solid solution BaFe_{2}(S_{1-x}Se_{x})_{3}, which is categorized into a new family of Fe-based superconductors hosting a quasi-one-dimensional ladder lattice. We show that the antiferromagnetic order is largely suppressed due to bicritical fluctuations in the vicinity of the magnetic transition at x=0.23 from the stripe-type to block-type ordering. Moreover, we observed large magnon contributions in the thermal conductance in a wide x range. These results indicate the quasi-one-dimensional nature of spin systems and give a solid foundation for modeling the material toward unraveling the microscopic mechanism of superconductivity.

Antiferroic electronic structure in the nonmagnetic superconducting state of the iron-based superconductors.

A major problem in the field of high-transition temperature (Tc) superconductivity is the identification of the electronic instabilities near superconductivity. It is known that the iron-based superconductors exhibit antiferromagnetic order, which competes with the superconductivity. However, in the nonmagnetic state, there are many aspects of the electronic instabilities that remain unclarified, as represented by the orbital instability and several in-plane anisotropic physical properties. We report a new aspect of the electronic state of the optimally doped iron-based superconductors by using high-energy resolution angle-resolved photoemission spectroscopy. We find spectral evidence for the folded electronic structure suggestive of an antiferroic electronic instability, coexisting with the superconductivity in the nonmagnetic state of Ba1-x K x Fe2As2. We further establish a phase diagram showing that the antiferroic electronic structure persists in a large portion of the nonmagnetic phase covering the superconducting dome. These results motivate consideration of a key unknown electronic instability, which is necessary for the achievement of high-Tc superconductivity in the iron-based superconductors.

A compact and versatile dynamic flow cryostat for photon science.

We have developed a helium gas flow cryostat for use on synchrotron tender to hard X-ray beamlines. Very efficient sample cooling is achieved because the sample is placed directly in the cooling helium flow on a removable sample holder. The cryostat is compact and easy to operate; samples can be changed in less than 5 min at any temperature. The cryostat has a temperature range of 2.5-325 K with temperature stability better than 0.1 K. The very wide optical angle and the ability to operate in any orientation mean that the cryostat can easily be adapted for different X-ray techniques. It is already in use on different beamlines at the European Synchrotron Radiation Facility (ESRF), ALBA Synchrotron Light Facility (ALBA), and Diamond Light Source (DLS) for inelastic X-ray scattering, powder diffraction, and X-ray absorption spectroscopy. Results obtained at these beamlines are presented here.

Post-perovskite Transition in Anti-structure.

The discovery of the post-perovskite transition, which is the structural transition from the perovskite to post-perovskite structure in MgSiO3 under pressure, has aroused great interests in geosciences. Despite of previous extensive studies, key factors of the post-perovsktie transition are still under hot debate primarily due to the big difficulty in performing systematic experiments under extreme conditions. Hence, search for new materials showing the post-perovskite transition under ambient pressure has been highly expected. We here report a new-type of materials Cr3AX (A = Ga, Ge; X = C, N), which exhibits the post-perovskite transition as a function of "chemical pressure" at ambient physical pressure. The detailed structural analysis indicates that the tolerance factor, which is the measure of the ionic radius mismatch, plays the key role in the post-perovskite transition. Moreover, we found a tetragonal perovskite structure with loss of inversion symmetry between the cubic perovskite and orthorhombic post-perovskite structures. This finding stimulates a search for a ferroelectric state in MgSiO3.

Magnetic Precursor of the Pressure-Induced Superconductivity in Fe-Ladder Compounds.

The pressure effects on the antiferromagentic orders in iron-based ladder compounds CsFe_{2}Se_{3} and BaFe_{2}S_{3} have been studied using neutron diffraction. With identical crystal structure and similar magnetic structures, the two compounds exhibit highly contrasting magnetic behaviors under moderate external pressures. In CsFe_{2}Se_{3} the ladders are brought much closer to each other by pressure, but the stripe-type magnetic order shows no observable change. In contrast, the stripe order in BaFe_{2}S_{3} undergoes a quantum phase transition where an abrupt increase of Néel temperature by more than 50% occurs at about 1 GPa, accompanied by a jump in the ordered moment. With its spin structure unchanged, BaFe_{2}S_{3} enters an enhanced magnetic phase that bears the characteristics of an orbital selective Mott phase, which is the true neighbor of superconductivity emerging at higher pressures.

Erratum: Pressure-Induced Mott Transition Followed by a 24-K Superconducting Phase in BaFe_{2}S_{3} [Phys. Rev. Lett. 115, 246402 (2015)].

This corrects the article DOI: 10.1103/PhysRevLett.115.246402.

Pressure-Induced Mott Transition Followed by a 24-K Superconducting Phase in BaFe_{2}S_{3}.

We performed high-pressure study for a Mott insulator BaFe_{2}S_{3}, by measuring dc resistivity and ac susceptibility up to 15 GPa. We found that the antiferromagnetic insulating state at the ambient pressure is transformed into a metallic state at the critical pressure, P_{c}=10 GPa, and the superconductivity with the optimum T_{c}=24 K emerges above P_{c}. Furthermore, we found that the metal-insulator transition (Mott transition) boundary terminates at a critical point around 10 GPa and 75 K. The obtained pressure-temperature (P-T) phase diagram is similar to those of the organic and fullerene compounds; namely, BaFe_{2}S_{3} is the first inorganic superconductor in the vicinity of bandwidth control type Mott transition.

Pressure-induced superconductivity in the iron-based ladder material BaFe2S3.

All the iron-based superconductors identified so far share a square lattice composed of Fe atoms as a common feature, despite having different crystal structures. In copper-based materials, the superconducting phase emerges not only in square-lattice structures but also in ladder structures. Yet iron-based superconductors without a square-lattice motif have not been found, despite being actively sought out. Here, we report the discovery of pressure-induced superconductivity in the iron-based spin-ladder material BaFe2S3, a Mott insulator with striped-type magnetic ordering below ∼120 K. On the application of pressure this compound exhibits a metal-insulator transition at about 11 GPa, followed by the appearance of superconductivity below Tc = 14 K, right after the onset of the metallic phase. Our findings indicate that iron-based ladder compounds represent promising material platforms, in particular for studying the fundamentals of iron-based superconductivity.

Superconductivity in anti-post-Perovskite vanadium compounds.

Superconductivity, which is a quantum state induced by spontaneous gauge symmetry breaking, frequently emerges in low-dimensional materials. Hence, low dimensionality has long been considered as necessary to achieve high superconducting transition temperatures (TC). The recently discovered post-perovskite (ppv) MgSiO3, which constitutes the Earth's lowermost mantle (D" layer), has attracted significant research interest due to its importance in geoscience. The ppv structure has a peculiar two-dimensional character and is expected to be a good platform for superconductivity. However, hereunto, no superconductivity has been observed in isostructural materials, despite extensive investigation. Here, we report the discovery of superconductivity with a maximum TC of 5.6 K in V3PnNx (Pn = P, As) phases with the anti-ppv structure, where the anion and cation positions are reversed with respect to the ppv structure. This discovery stimulates further explorations of new superconducting materials with ppv and anti-ppv structures.

Control of bond-strain-induced electronic phase transitions in iron perovskites.

Unusual electronic phase transitions in the A-site ordered perovskites LnCu3Fe4O12 (Ln: trivalent lanthanide ion) are investigated. All LnCu3Fe4O12 compounds are in identical valence states of Ln(3+)Cu(2+)3Fe(3.75+)4O12 at high temperature. LnCu3Fe4O12 with larger Ln ions (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb) show an intersite charge transfer transition (3Cu(2+) + 4Fe(3.75+) → 3Cu(3+) + 4Fe(3+)) in which the transition temperature decreases from 360 to 240 K with decreasing Ln ion size. In contrast, LnCu3Fe4O12 with smaller Ln ions (Ln = Dy, Ho, Er, Tm Yb, Lu) transform into a charge-disproportionated (8Fe(3.75+) → 5Fe(3+) + 3Fe(5+)) and charge-ordered phase below ∼250-260 K. The former series exhibits metal-to-insulator, antiferromagnetic, and isostructural volume expansion transitions simultaneously with intersite charge transfer. The latter shows metal-to-semiconductor, ferrimagnetic, and structural phase transitions simultaneously with charge disproportionation. Bond valence calculation reveals that the metal-oxygen bond strains in these compounds are classified into two types: overbonding or compression stress (underbonding or tensile stress) in the Ln-O (Fe-O) bond is dominant in the former series, while the opposite stresses or bond strains are found in the latter. Intersite charge transfer transition temperatures are strongly dependent upon the global instability indices that represent the structural instability calculated from the bond valence sum, whereas the charge disproportionation occurs at almost identical temperatures, regardless of the magnitude of structural instability. These findings provide a new aspect of the structure-property relationship in transition metal oxides and enable precise control of electronic states by bond strains.

Resonant x-ray diffraction study of the strongly spin-orbit-coupled mott insulator CaIrO3.

We performed resonant x-ray diffraction experiments at the L absorption edges for the post-perovskite-type compound CaIrO(3) with a (t(2g))^{5} electronic configuration. By observing the magnetic signals, we could clearly see that the magnetic structure was a striped ordering with an antiferromagnetic moment along the c axis and that the wave function of a t(2g) hole is strongly spin-orbit entangled, the J(eff)=1/2 state. The observed spin arrangement is consistent with theoretical work predicting a unique superexchange interaction in the J(eff)=1/2 state and points to the universal importance of the spin-orbit coupling in Ir oxides, independent of the octahedral connectivity and lattice topology. We also propose that nonmagnetic resonant scattering is a powerful tool for unraveling an orbital state even in a metallic iridate.

Mechanism of enhanced optical second-harmonic generation in the conducting pyrochlore-type Pb2Ir2O7-x oxide compound.

The structural, electronic, and optical properties of pyrochlore-type Pb(2)Ir(2)O(6)O(0.55)('), which is a metal without spatial inversion symmetry at room temperature, were investigated. Structural analysis revealed that the structural distortion relevant to the breakdown of the inversion symmetry is dominated by the Pb-O' network but is very small in the Ir-O network. At the same time, gigantic second-harmonic generation signals were observed, which can only occur if the local environment of the Ir 5d electrons features broken inversion symmetry. First-principles electronic structure calculations reveal that the underlying mechanism for this phenomenon is the induction of the noncentrosymmetricity in the Ir 5d bands by the strong hybridization with O' 2p orbitals. Our results stimulate theoretical study of inversion-broken iridates, where exotic quantum states such as a topological insulator and Dirac semimetal are anticipated.

Suppression of intersite charge transfer in charge-disproportionated perovskite YCu3Fe4O12.

A novel iron perovskite YCu3Fe4O12 was synthesized under high pressure and high temperature of 15 GPa and 1273 K. Synchrotron X-ray and electron diffraction measurements have demonstrated that this compound crystallizes in the cubic AA'3B4O12-type perovskite structure (space group Im3, No. 204) with a lattice constant of a = 7.30764(10) Šat room temperature. YCu3Fe4O12 exhibits a charge disproportionation of 8Fe(3.75+) → 3Fe(5+) + 5Fe(3+), a ferrimagnetic ordering, and a metal-semiconductor-like transition simultaneously at 250 K, unlike the known isoelectronic compound LaCu3Fe4O12 that currently shows an intersite charge transfer of 3Cu(2+) + 4Fe(3.75+) → 3Cu(3+) + 4Fe(3+), an antiferromagnetic ordering, and a metal-insulator transition at 393 K. This finding suggests that intersite charge transfer is not the only way of relieving the instability of the Fe(3.75+) state in the A(3+)Cu(2+)3Fe(3.75+)4O12 perovskites. Crystal structure analysis reveals that bond strain, rather than the charge account of the A-site alone, which is enhanced by large A(3+) ions, play an important role in determining which of intersite charge transfer or charge disproportionation is practical.

B-site deficiencies in A-site-ordered perovskite LaCu3Pt(3.75)O12.

An A-site-ordered perovskite LaCu3Pt(3.75)O12 was synthesized by replacing Ca(2+) with La(3+) in a cubic quadruple AA'3B4O12-type perovskite CaCu3Pt4O12 under high-pressure and high-temperature of 15 GPa and 1100 °C. In LaCu3Pt(3.75)O12, 1/16 of B-site cations are vacant to achieve charge balance. The B-site deficiencies were evidenced by crystal structure refinement using synchrotron X-ray powder diffraction, hard X-ray photoemission spectroscopy, and soft X-ray absorption spectroscopy, leading to the ionic model La(3+)Cu(2+)3Pt(4+)(3.75)O(2-)12. Magnetic susceptibility data for this compound indicated a spin-glass-like behavior below T(g) = 3.7 K, which is attributed to disturbance of the antiferromagnetic superexchange interaction by the B-site deficiencies.

Pd(2+)-incorporated perovskite CaPd3B4O12 (B = Ti, V).

Novel A-site ordered perovskites CaPd(3)Ti(4)O(12) and CaPd(3)V(4)O(12) were synthesized under high-pressure and high-temperature of 15 GPa and 1000 °C. These compounds are the first example in which a crystallographic site in a perovskite-type structure is occupied by Pd(2+) ions with a 4d(8) low spin configuration. The ionic models for these compounds were determined to be Ca(2+)Pd(2+)(3)Ti(4+)(4)O(12) and Ca(2+)Pd(2+)(3)V(4+)(4)O(12) by structural refinement using synchrotron X-ray powder diffraction, hard X-ray photoemission, and soft X-ray absorption spectroscopy. Magnetic susceptibility, electrical resistivity, and specific heat measurements demonstrated diamagnetic insulating behavior for CaPd(3)Ti(4)O(12) in contrast to the Pauli-paramagnetic metallic nature of CaPd(3)V(4)O(12).

Superconducting phase at 7.7 K in the HgxReO3 compound with a hexagonal bronze structure.

We have successfully synthesized a new rhenium-based hexagonal bronze material, HgxReO3, which exhibits superconductivity with the transition temperature Tc=7.7 K at ambient pressure and 11.1 K at 4 GPa. This compound is a superconductor with the highest Tc among hexagonal bronzes. Moreover, it presents the novel crystallographic feature that (Hg2)2+ polycations, in contrast to monatomic cations in known hexagonal bronzes, are incorporated into open channels. There is evidence that conducting electrons tightly couple with Hg-related phonons. Our results inspire detailed studies on the role of the rattling phonon in the occurrence of superconductivity in the hexagonal bronzes.

CaCu3Pt4O12: the first perovskite with the B site fully occupied by Pt(4+).

A novel A-site ordered perovskite CaCu(3)Pt(4)O(12) was synthesized under high pressure and high temperature of 12 GPa and 1250 degrees C. CaCu(3)Pt(4)O(12) is the first perovskite in which the B site is fully occupied by Pt(4+). The crystal structure refinement based on the synchrotron powder X-ray diffraction data shows that CaCu(3)Pt(4)O(12) crystallizes in the space group Im3 (cubic) with a lattice constant of a = 7.48946(10) A. The magnetic susceptibility data show the antiferromagnetic transition at T(N) = 40 K, which is attributed to the magnetic ordering of Cu(2+) spins with S = 1/2.