Transitions from a Kondo-like diamagnetic insulator into a modulated ferromagnetic metal in FeGa3-yGey.

One initial and essential question of magnetism is whether the magnetic properties of a material are governed by localized moments or itinerant electrons. Here, we expose the case for the weakly ferromagnetic system FeGa3-y Ge y , wherein these two opposite models are reconciled, such that the magnetic susceptibility is quantitatively explained by taking into account the effects of spin-spin correlation. With the electron doping introduced by Ge substitution, the diamagnetic insulating parent compound FeGa3 becomes a paramagnetic metal as early as at y=0.01, and turns into a weakly ferromagnetic metal around the quantum critical point y=0.15. Within the ferromagnetic regime of FeGa3-y Ge y , the magnetic properties are of a weakly itinerant ferromagnetic nature, located in the intermediate regime between the localized and the itinerant dominance. Our analysis implies a potential universality for all itinerant-electron ferromagnets.

Linear Trimer Formation with Antiferromagnetic Ordering in 1T-CrSe2 Originating from Peierls-like Instabilities and Interlayer Se-Se Interactions.

Anomalous successive structural transitions in layered 1T-CrSe2 with an unusual Cr4+ valency were investigated by synchrotron X-ray diffraction. 1T-CrSe2 exhibits dramatic structural changes in in-plane Cr-Cr and interlayer Se-Se distances, which originate from two interactions: (i) in-plane Cr-Cr interactions derived from Peierls-like trimerization instabilities on the orbitally assisted one-dimensional chains and (ii) interlayer Se-Se interactions through p-p hybridization. As a result, 1T-CrSe2 has the unexpected ground state of an antiferromagnetic metal with multiple Cr linear trimers with three-center-two-electron σ bonds. Interestingly, partial substitution of Se for S atoms in 1T-CrSe2 changes the ground state from an antiferromagnetic metal to an insulator without long-range magnetic ordering, which is due to the weakening of interlayer interactions between anions. The unique low-temperature structures and electronic states of this system are determined by the competition and cooperation of in-plane Cr-Cr and interlayer Se-Se interactions.

Highly Spin-Frustrated Magnetism in the Topochemically Prepared Triangular Lattice Cluster Magnets Na3 A2 (MoO4 )2 Mo3 O8 (A=In, Sc).

The physical properties of novel cluster-based triangular lattice antiferromagnets Na3 A2 (MoO4 )2 Mo3 O8 (A=In, Sc), synthesized through a topochemical Na-intercalation to nonmagnetic Na2 A2 (MoO4 )2 Mo3 O8 , are reported. The S=1/2 [Mo3 ]11+ clusters form a regular triangular lattice, which gives the magnetic system a strong geometrical spin frustration effect. Despite the strong antiferromagnetic couplings among [Mo3 ]11+ clusters, they show no long-range magnetic orderings down to 0.5 K with the finite residual magnetic entropy. The ground states of Na3 A2 (MoO4 )2 Mo3 O8 have been characterized as a quantum spin liquid, owing to the strong spin frustration of cluster spins on the triangular lattice.

Magnetic-Nonmagnetic Phase Transition with Interlayer Charge Disproportionation of Nb3 Trimers in the Cluster Compound Nb3Cl8.

We grew large single crystals of the cluster magnet Nb3Cl8 with a magnetic triangular lattice and investigated its magnetic properties and crystal structure. In Nb3Cl8, the [Nb3]8+ cluster has a single unpaired spin, making it an S = 1/2 triangular lattice anti-ferromagnet. At low temperatures, Nb3Cl8 exhibits a magnetic-nonmagnetic phase transition driven by a charge disproportionation, in which the paramagnetic [Nb3]8+ clusters transform into alternating layers of nonmagnetic [Nb3]7+ and [Nb3]9+ clusters. The observed exotic phenomenon with the strong correlation between the magnetism and structure are based on the nature of the cluster magnetism.

Competition between the Direct Exchange Interaction and Superexchange Interaction in Layered Compounds LiCrSe2, LiCrTe2, and NaCrTe2 with a Triangular Lattice.

Physical properties of new S = 3/2 triangular-lattice compounds LiCrSe2, LiCrTe2, and NaCrTe2 have been investigated by X-ray diffraction and magnetic measurements. These compounds crystallize in the ordered NiAs-type structure, where alkali metal ions and Cr atoms stack alternately. Despite their isomorphic structures, magnetic properties of these three compounds are different; NaCrTe2 has an A-type spin structure with ferromagnetic layers, LiCrTe2 is likely to exhibit a helical spin structure, and LiCrSe2 shows a first-order-like phase transition from the paramagnetic trigonal phase to the antiferromagnetic monoclinic phase. In these compounds and the other chromium chalcogenides with a triangular lattice, we found a general relationship between the Curie-Weiss temperature and magnetic structures. This relation indicates that the competition between the antiferromagnetic direct d-d exchange interaction and the ferromagnetic superexchange interaction plays an important role in determining the ground state of chromium chalcogenides.

Soft X-ray angle-resolved photoemission with micro-positioning techniques for metallic V2O3.

Soft X-ray angle-resolved photoemission has been performed for metallic V2O3. By combining a microfocus beam (40 µm × 65 µm) and micro-positioning techniques with a long-working-distance microscope, it has been possible to observe band dispersions from tiny cleavage surfaces with a typical size of several tens of µm. The photoemission spectra show a clear position dependence, reflecting the morphology of the cleaved sample surface. By selecting high-quality flat regions on the sample surface, it has been possible to perform band mapping using both photon-energy and polar-angle dependences, opening the door to three-dimensional angle-resolved photoemission spectroscopy for typical three-dimensional correlated materials where large cleavage planes are rarely obtained.

Strong Coupling Superconductivity in the Vicinity of the Structural Quantum Critical Point in (Ca(x)Sr(1-x))3Rh4Sn13.

The family of the superconducting quasiskutterudites (Ca(x)Sr(1-x))(3)Rh(4)Sn(13) features a structural quantum critical point at x(c)=0.9, around which a dome-shaped variation of the superconducting transition temperature T(c) is found. Using specific heat, we probe the normal and the superconducting states of the entire series straddling the quantum critical point. Our analysis indicates a significant lowering of the effective Debye temperature on approaching x(c), which we interpret as a result of phonon softening accompanying the structural instability. Furthermore, a remarkably large enhancement of 2Δ/k(B)T(c) and ΔC/γT(c) beyond the Bardeen-Cooper-Schrieffer values is found in the vicinity of the structural quantum critical point. The phase diagram of (Ca(x)Sr(1-x))(3)Rh(4)Sn(13) thus provides a model system to study the interplay between structural quantum criticality and strong electron-phonon coupling superconductivity.

An oxyhydride of BaTiO3 exhibiting hydride exchange and electronic conductivity.

In oxides, the substitution of non-oxide anions (F(-),S(2-),N(3-) and so on) for oxide introduces many properties, but the least commonly encountered substitution is where the hydride anion (H(-)) replaces oxygen to form an oxyhydride. Only a handful of oxyhydrides have been reported, mainly with electropositive main group elements or as layered cobalt oxides with unusually low oxidation states. Here, we present an oxyhydride of the perhaps most well-known perovskite, BaTiO(3), as an O(2-)/H(-) solid solution with hydride concentrations up to 20% of the anion sites. BaTiO(3-x)H(x) is electronically conducting, and stable in air and water at ambient conditions. Furthermore, the hydride species is exchangeable with hydrogen gas at 400 °C. Such an exchange implies diffusion of hydride, and interesting diffusion mechanisms specific to hydrogen may be at play. Moreover, such a labile anion in an oxide framework should be useful in further expanding the mixed-anion chemistry of the solid state.

(Sr(1-x)Ba(x))FeO2 (0.4 ≤ x ≤ 1): a new oxygen-deficient perovskite structure.

Topochemical reduction of (layered) perovskite iron oxides with metal hydrides has so far yielded stoichiometric compositions with ordered oxygen defects with iron solely in FeO(4) square planar coordination. Using this method, we have successfully obtained a new oxygen-deficient perovskite, (Sr(1-x)Ba(x))FeO(2) (0.4 ≤ x ≤ 1.0), revealing that square planar coordination can coexist with other 3-6-fold coordination geometries. This BaFeO(2) structure is analogous to the LaNiO(2.5) structure in that one-dimensional octahedral chains are linked by planar units, but differs in that one of the octahedral chains contains a significant amount of oxygen vacancies and that all the iron ions are exclusively divalent in the high-spin state. Mössbauer spectroscopy demonstrates, despite the presence of partial oxygen occupations and structural disorders, that the planar-coordinate Fe(2+) ions are bonded highly covalently, which accounts for the formation of the unique structure. At the same time, a rigid 3D Fe-O-Fe framework contributes to structural stabilization. Powder neutron diffraction measurements revealed a G-type magnetic order with a drastic decrease of the Néel temperature compared to that of SrFeO(2), presumably due to the effect of oxygen disorder/defects. We also performed La substitution at the Ba site and found that the oxygen vacancies act as a flexible sink to accommodate heterovalent doping without changing the Fe oxidation and spin state, demonstrating the robustness of this new structure against cation substitution.

Pressure- and composition-induced structural quantum phase transition in the cubic superconductor (Sr, Ca)3Ir4Sn13.

We show that the quasi-skutterudite superconductor Sr(3)Ir(4)Sn(13) undergoes a structural transition from a simple cubic parent structure, the I phase, to a superlattice variant, the I' phase, which has a lattice parameter twice that of the high temperature phase. We argue that the superlattice distortion is associated with a charge density wave transition of the conduction electron system and demonstrate that the superlattice transition temperature T(*) can be suppressed to zero by combining chemical and physical pressure. This enables the first comprehensive investigation of a superlattice quantum phase transition and its interplay with superconductivity in a cubic charge density wave system.

Pressure driven magnetic order in Sr[Formula: see text]Ca[Formula: see text]Co[Formula: see text]P[Formula: see text].

The magnetic phase diagram of Sr[Formula: see text]Ca[Formula: see text]Co[Formula: see text]P[Formula: see text] as a function of hydrostatic pressure and temperature is investigated by means of high pressure muon spin rotation, relaxation and resonance ([Formula: see text]SR). The weak pressure dependence for the [Formula: see text] compounds suggests that the rich phase diagram of Sr[Formula: see text]Ca[Formula: see text]Co[Formula: see text]P[Formula: see text] as a function of x at ambient pressure may not solely be attributed to chemical pressure effects. The [Formula: see text] compound on the other hand reveals a high pressure dependence, where the long range magnetic order is fully suppressed at [Formula: see text] kbar, which seem to be a first order transition. In addition, an intermediate phase consisting of magnetic domains is formed above [Formula: see text] kbar where they co-exist with a magnetically disordered state. These domains are likely to be ferromagnetic islands (FMI) and consist of an high- (FMI-[Formula: see text]) and low-temperature (FMI-[Formula: see text]) region, respectively, separated by a phase boundary at [Formula: see text] K. This kind of co-existence is unusual and is originating from a coupling between lattice and magnetic degrees of freedoms.

Pressure-induced structural, magnetic, and transport transitions in the two-legged ladder Sr3Fe2O5.

The layered compound SrFeO(2) with an FeO(4) square-planar motif exhibits an unprecedented pressure-induced spin state transition (S = 2 to 1), together with an insulator-to-metal (I-M) and an antiferromagnetic-to-ferromagnetic (AFM-FM) transition. In this work, we have studied the pressure effect on the structural, magnetic, and transport properties of the structurally related two-legged spin ladder Sr(3)Fe(2)O(5). When pressure was applied, this material first exhibited a structural transition from Immm to Ammm at P(s) = 30 ± 2 GPa. This transition involves a phase shift of the ladder blocks from (1/2,1/2,1/2) to (0,1/2,1/2), by which a rock-salt type SrO block with a 7-fold coordination around Sr changes into a CsCl-type block with 8-fold coordination, allowing a significant reduction of volume. However, the S = 2 antiferromagnetic state stays the same. Next, a spin state transition from S = 2 to S = 1, along with an AFM-FM transition, was observed at P(c) = 34 ± 2 GPa, similar to that of SrFeO(2). A sign of an I-M transition was also observed at pressure around P(c). These results suggest a generality of the spin state transition in square planar coordinated S = 2 irons of n-legged ladder series Sr(n+1)Fe(n)O(2n+1) (n = 1, 2, 3, ...). It appears that the structural transition independently occurs without respect to other transitions. The necessary conditions for a structural transition of this type and possible candidate materials are discussed.

Fe-site substitution effect on the structural and magnetic properties in SrFeO2.

We investigated the Fe-site substitution effect on the structural and magnetic properties of the infinite layer iron oxide Sr(Fe(1-x)M(x))O(2) (M = Co, Mn) using synchrotron X-ray diffraction, neutron diffraction, and (57)Fe Mössbauer spectroscopy. Both systems have a similar solubility limit of x ≈ 0.3, retaining the ideal infinite layer structure with a space group of P4/mmm. For the Fe-Co system, both in-plane and out-of-plane axes decrease linearly and only slightly with x, reflecting the ionic radius difference between Fe(2+) and Co(2+). For the Fe-Mn system the lattice evolution also follows Vegard's law but is anisotropic: the in-plane axis increases, while the out-of-plane decreases prominently. The magnetic properties are little influenced by Co substitution. On the contrary, Mn substitution drastically destabilizes the G-type magnetic order, featured by a significant reduction and a large distribution of the hyperfine field in the Mössbauer spectra, which suggests the presence of magnetic frustration induced presumably by a ferromagnetic out-of-plane Mn-Fe interaction.

Synthesis and thermal stability of the solid solution AFeO2 (A = Ba, Sr, Ca).

We have studied the A-site substitution effect on the structural, thermal, and magnetic properties of the infinite layer iron oxide AFeO(2) (A = alkali-earth elements) with an FeO(4) square-planar coordination. Together with the previous study showing a total substitution by Ca, Ba substitution is found to be tolerable up to 30%, presenting almost the same substitutional range as that found in ACuO(2) under high pressure. Notably, Ba substitution shows little influence on the magnetic properties, in contrast to expectations from first principles calculations. The temperature at which oxidation to an AFeO(2.5) phase occurs and its transformation rate show a wide variation tunable solely by the out-of-plane distance.

Discovery of Amorphous Iron Hydrides via Novel Quiescent Reaction in Aqueous Solution.

Novel amorphous iron hydrides (AIHs) are synthesized for the first time under ambient conditions by employing novel "quiescent reaction", without stirring for mixing solutions, during a conventional aqueous reduction-precipitation process. The kind and morphology of AIHs are dependent on the processing condition, where two types are found, with one form consisting of a tangle of uniform nanowires and the other being granular in nature. Both AIHs undergo transformation to crystalline α-Fe by heat treatment at 600 °C. The nanowire AIH exhibits the hydrogen content of 0.10 wt%, while the granular AIH of 0.22 wt%. Their magnetic and thermal properties are accordingly different, and the non-diffusive hydrogen contributes to stability of AIHs. It is strongly suggested that, by use of quiescent reaction, iron-hydrogen clusters are formed and preserved at an early stage of precipitation reaction, and subsequently aggregated into novel AIHs, preventing α-Fe crystallization. Hence, the AIHs would be categorized as metastable hydrides stabilized with iron-hydrogen clusters. In addition, newly discovered quiescent reaction in aqueous solution, from which unprecedented AIHs are derived, sheds new light on fundamental and essential aqueous reaction.

Investigation of ionic and anomalous magnetic behavior in CrSe2 using 8Li ß-NMR.

We have studied a mosaic of 1T-CrSe2 single crystals using ß-detected nuclear magnetic resonance of 8Li from 4 to 300 K. We identify two broad resonances that show no evidence of quadrupolar splitting, indicating two magnetically distinct environments for the implanted ion. We observe stretched exponential spin lattice relaxation and a corresponding rate (1/T 1) that increases monotonically above 200 K, consistent with the onset of ionic diffusion. A pronounced maximum in 1/T 1 is observed at the low temperature magnetic transition near 20 K. Between these limits, 1/T 1 exhibits a broad minimum with an anomalous absence of strong features in the vicinity of structural and magnetic transitions between 150 and 200 K. Together, the results suggest 8Li+ site occupation within the van der Waals gap between CrSe2 trilayers. Possible origins of the two environments are discussed.

CaFeO2: a new type of layered structure with iron in a distorted square planar coordination.

CaFeO(2), a material exhibiting an unprecedented layered structure containing 3d(6) iron in a high-spin distorted square-planar coordination, is reported. The new phase, obtained through a low-temperature reduction procedure using calcium hydride, has been characterized through powder neutron diffraction, synchrotron X-ray diffraction, Mossbauer spectroscopy, XAS experiments as well as first-principles DFT calculations. The XAS spectra near the Fe-K edge for the whole solid solution (Sr(1-x)Ca(x))FeO(2) supports that iron is in a square-planar coordination for 0

Stability of the infinite layer structure with iron square planar coordination.

The recently discovered SrFeO2 prepared by a soft chemical route from a precursor SrFeO3 has the "infinite layer" (IL) structure with an unprecedented FeO4 square-planar coordination. We show that the IL structure has significant solubility to yield Sr1-xCaxFeO2 (0

Tetramer spin singlet instability in the fluorine-substituted pyrochlore superconducting system Cd2Re2O7-x F x.

We synthesized polycrystalline samples of the fluorine-substituted pyrochlore rhenates Cd2Re2O7-x F x , and investigated their magnetic, transport and structural properties. The transition temperature T s1, where each Re4 tetrahedron in the Re pyrochlore network alternately expands and contracts, decreases with increasing x from 200 K at x = 0 to 100 K at x = 0.5. The strong x dependence of the magnetic and transport properties at the low-temperature phase indicates that the driving force of structural phase transition is fluctuations of the tetramer spin singlet formation in order to release the spin frustration in the pyrochlore lattice. Furthermore, we found unconventional superconducting properties in Cd2Re2O7-x F x . It was found that the superconducting phase transition temperature T c markedly decreases with increasing x, suggesting that the addition of imperfection suppresses a condensation of Cooper-pair. In addition, the estimated upper critical field at zero temperature exceeds the Pauli paramagnetic limit and increases with increasing x in spite of the reduction of T c. Hence, Cd2Re2O7-x F x is suggested to be an exotic superconductor realized in the itinerant electron systems on a spin frustrated lattice.

Structure and magnetic properties of a new ferrimagnet containing a paramagnetic [Cr(CN)5(NO)]3- building block.

A new Prussian-blue type molecular magnet containing a paramagnetic [Cr(CN)5(NO)]3- building block has been synthesized and characterized; the observed magnetic behavior displays the nature of a ferrimagnet.