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We have prevented lattice collapse and developed an OER catalyst with both high activity and stability by slightly increasing Ir-dissolution and balancing the elemental dissolution in BaIr1−xMnxO3 for reconstructing the rigid catalytic surface.

We undertake a detailed high-resolution diffraction study of a novel plain band insulator, La$_2$MgO$_4$, which may be viewed as a structural surrogate system of the undoped end-member of the high-T$_c$ superconductors, La$_{2-x-y}$A$^{2+}_x$RE$^{3+}_y$CuO$_{4}$ (A = Ba, Sr, RE= Rare Earth). We find that La$_2$MgO$_4$ exhibits the infamous low-temperature orthorhombic (LTO) to low-temperature tetragonal (LTT) phase transition that has been linked to the suppression of superconductivity in a variety of underdoped cuprates, including the well known La$_{2-x}$Ba$_{x}$CuO$_4$ ($x=0.125$). Furthermore, we find that the LTO-to-LTT phase transition in La$_2$MgO$_4$ occurs for an octahedral tilt angle in the 4 $^{\circ}$ to 5 $^{\circ}$ range, similar to that which has previously been identified as a critical tipping point for superconductivity in these systems. We show that this phase transition, occurring in a system lacking spin correlations and competing electronic states such as charge-density waves and superconductivity, can be understood by simply navigating the density-functional theory ground-state energy landscape as a function of the order parameter amplitude. This result calls for a careful re-investigation of the origins of the phase transitions in high-T$_c$ superconductors based on the hole-doped, $n = 1$ Ruddelsden-Popper lanthanum cuprates., 6 pages, 4 figures

Enzyme-linked immunosorbent assays (ELISAs) are tests that uses antibody recognition and enzyme catalytic activity to identify a substance, and they have been widely used as a diagnostic tool in the clinic.

We report the temperature and composition dependence of static magnetic susceptibility and Raman spectroscopic measurements on van der Waals antiferromagnets ${\mathrm{Ni}}_{1\ensuremath{-}x}{\mathrm{Fe}}_{x}{\mathrm{PS}}_{3}$. The end members ${\mathrm{NiPS}}_{3}$ and ${\mathrm{FePS}}_{3}$ feature $XY$- and Ising-like magnetism, respectively, enabling chemical tuning of magnetic anisotropy and spin correlations. ${\mathrm{Ni}}_{1\ensuremath{-}x}{\mathrm{Fe}}_{x}{\mathrm{PS}}_{3}$ shows a turnover from the $XY$ to Ising anisotropy through $x\ensuremath{\approx}0.1$. Although the $XY$ anisotropy is rapidly suppressed on introducing Fe content, two-magnon scattering evidences the slow repression of short-range magnetic correlations deep inside the Fe-rich side. Counterintuitively, the two-magnon signal undergoes less renormalization of its energy with increasing $x$ despite the larger spin number and enhanced classical magnetism. The disparate static and dynamic magnetic behaviors indicate the emergence of an exotic spin state in alloy van der Waals magnets.

Lithium-oxide-halide and lithium-hydroxide-halide antiperovskites were explored for potential electrolytes in all-solid Li-ion batteries. A single-phase sample of the Ruddlesden–Popper (RP) series of compounds, LiBr(Li2OHBr)2 with double antiperovskite Li2OHBr layers and rigid rock-salt type LiBr layers, was obtained. Li+-ion vacancies are introduced in the double antiperovskite Li2OHBr layers but not in the LiBr layers and induce two-dimensional Li-ion conduction with low activation energy by mediating Li-ion hopping. In contrast to the Br-containing RP phase, Cl-containing Li-oxide-halide and Li-hydroxide-halide RP phases cannot be crystallized due to the structural mismatch between the antiperovskite layers and rigid LiCl layers.

Enzyme-linked immunosorbent assays (ELISAs) are tests that uses antibody recognition and enzyme catalytic activity to identify a substance, and they have been widely used as a diagnostic tool in the clinic. However, performing an ELISA requires various liquid handling steps and long binding times. To solve this problem, we developed a magnetic microfluidic ELISA system (MMF-ELISA). Integration with nickel magnetic nanoparticles can streamline the ELISA process in a fully automated manner for

Charge orders (COs) and entangled topology denote the fundamentals of correlated electron systems at low temperatures, and their profound revelation at atomic scale awaits experimental advances. Here, we report such a spatially resolved investigation using cryogenic atomic-scale electron microscopy and spectroscopy at 100 K, with the CO insulator of $\mathrm{Hg}{\mathrm{Mn}}_{7}{\mathrm{O}}_{12}$ below 240 K as an exemplification. By the cryogenic technique, we can resolve the charge and lattice characteristics of the insulating CO phase at atomic resolution and identify the order parameters (OPs) at play as charge-density-modulated (\ensuremath{\sim}31.4 \AA{}, modulation length) and antiphase (\ensuremath{\sim}10.5 \AA{}) OPs. Both OPs are largely unaddressed forms of COs in correlated oxides and display the emergent topology of intertwining mesoscopic stripes of 10--40 nm in width and \ensuremath{\ge}500 nm in length, distinctly different from the atomically narrow CO stripes conventional to correlated systems and depicting the unique electronic contour of the phase. This preliminary demonstration of the cryogenic unveiling of the OPs and topological landscape paves the way to disentangling the multifarious COs and hidden topology in condensed matters and, meanwhile, calls for further developments in the atomic-scale cryogenic spectral probing at an enhanced speed.

We have successfully grown single crystals of $\mathrm{Pb}{\mathrm{Mn}}_{2}{\mathrm{Ni}}_{6}{\mathrm{Te}}_{3}{\mathrm{O}}_{18}$ and present a comprehensive study of their magnetic, thermodynamic, and Raman spectroscopic properties. $\mathrm{Pb}{\mathrm{Mn}}_{2}{\mathrm{Ni}}_{6}{\mathrm{Te}}_{3}{\mathrm{O}}_{18}$ consists of a planar network of pairwise rotated $\mathrm{Ni}{\mathrm{O}}_{6}$ dimers coupled by corners. Similarities to ${\mathrm{Ni}}_{3}\mathrm{Te}{\mathrm{O}}_{6}$ exist, which forms honeycomb layers. The magnetic susceptibility \ensuremath{\chi} and heat capacity ${C}_{p}$ data reveal an antiferromagnetic phase transition around 84 K, which is evidently hysteretic on warming and cooling between 94 and 40 K with a loop width of about 1.83\ifmmode\pm\else\textpm\fi{} 0.41 K; thus the transition appears to be of first order. \ensuremath{\chi} is anisotropic, with larger values for in-plane fields over the entire measured temperature range. Raman spectroscopy has been employed to investigate the lattice and magnetic excitations of the $\mathrm{Pb}{\mathrm{Mn}}_{2}{\mathrm{Ni}}_{6}{\mathrm{Te}}_{3}{\mathrm{O}}_{18}$ from 5 to 300 K. Besides an anharmonic phonon behavior, i.e., a decay into acoustic phonons, we find a coupling to the spin system at ${T}_{N}=84\phantom{\rule{0.16em}{0ex}}\mathrm{K}$, as well as weak anomalies at ${T}^{*}\ensuremath{\approx}200\phantom{\rule{0.16em}{0ex}}\mathrm{K}$. This second characteristic temperature gives evidence for an instability of the coupled spin/lattice system, as here the phonon linewidths and intensities evidence similar behavior as at ${T}_{N}=84\phantom{\rule{0.16em}{0ex}}\mathrm{K}$. Furthermore, magnetic Raman scattering at $240\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{\ensuremath{-}1}$ is used to estimate an exchange coupling of $J=--86\phantom{\rule{0.16em}{0ex}}\mathrm{K}$ in general agreement with the Curie-Weiss temperature.

The $B$-site ordered double perovskites ${\mathrm{Sr}}_{2}\mathrm{Cu}({\mathrm{Te}}_{1\ensuremath{-}x}{\mathrm{W}}_{x}){\mathrm{O}}_{6}$ provide an excellent arena for investigating exotic phases expected for the ${J}_{1}\text{\ensuremath{-}}{J}_{2}$ square-lattice Heisenberg antiferromagnet. Here, combining magnetic susceptibility and specific-heat measurements with electron spin resonance (ESR) and muon spin rotation/relaxation $(\ensuremath{\mu}\mathrm{SR})$ techniques, we explore a spin-liquid-like state in the vicinity of the N\'eel critical end point $(x=0.05--0.1)$. The specific heat and the ESR and muon relaxation rates give evidence for an energy hierarchy of low-energy excitations, reminiscent of randomness-induced singlet states. In addition, the weak transverse $\ensuremath{\mu}\mathrm{SR}$ data show a fraction of frozen magnetic moments in the random-singlet background. The origin of a random-singlet-like state near the phase boundary is discussed in terms of concomitant exchange randomness and local strain generated by the ${\mathrm{W}}^{6+}\text{\ensuremath{-}}\mathrm{for}\text{\ensuremath{-}}{\mathrm{Te}}^{6+}$ substitution.

The phase diagrams of LaMnO3 perovskites have been intensely studied due to the colossal magnetoresistance (CMR) exhibited by compositions around the 38th doping level. However, phase segregation between ferromagnetic (FM) metallic and antiferromagnetic (AFM) insulating states, which itself is believed to be responsible for the colossal change in resistance under applied magnetic field, has prevented an atomistic-level understanding of the orbital ordered (OO) state at this doping level. Here, through the detailed crystallographic analysis of the phase diagram of a prototype system (AMn3A′Mn4BO12), we show that the superposition of two distinct lattice modes gives rise to a striping of OO Jahn-Teller active Mn3+ and charge disordered (CD) Mn3.5+ layers in a 1:3 ratio. This superposition only gives a cancellation of the Jahn-Teller-like displacements at the critical doping level. This striping of CD Mn3.5+ with Mn3+ provides a natural mechanism though which long range OO can melt, giving way to a conducting state., Nature Communications, 12 (1), ISSN:2041-1723

A breathing pyrochlore system is predicted to host a variety of quantum spin liquids. However, perturbations beyond nearest-neighbor Heisenberg interaction are an obstacle to identifying such exotic states. Here, we utilize a bond-alternating disorder to tune a magnetic ground state in the Cr-based breathing pyrochlore. By combining thermodynamic and magnetic resonance techniques, we provide experimental signatures of a spin-liquid-like state in LiGa1-xInxCr4O8 (x=0.2), namely, a nearly T2-dependent magnetic specific heat and a persistent spin dynamics by muon spin relaxation (μSR). Moreover, 7Li NMR, ZF-μSR, and ESR unveil the dichotomic nature of both temporal and thermal spin fluctuations: slowly fluctuating tetramer singlets at high temperatures and a fast fluctuating spin-liquid-like state at low temperatures. Our results suggest that a bond disorder in the breathing pyrochlore offers a new route to achieve an unexplored state of matter.

A fully oxygenated hexagonal 12-layer perovskite $\mathrm{BaFe}{\mathrm{O}}_{3}$ with nominal $\mathrm{F}{\mathrm{e}}^{4+}$ was obtained by high-pressure synthesis. The structure consists of face-sharing $\mathrm{F}{\mathrm{e}}_{3}{\mathrm{O}}_{9}$ octahedral trimers and corner-sharing octahedra. A remarkable series of electronic transitions that relieve the electronic instability of $\mathrm{F}{\mathrm{e}}^{4+}$ are discovered on cooling; $2\mathrm{F}{\mathrm{e}}^{4+}\ensuremath{\rightarrow}\mathrm{F}{\mathrm{e}}^{3+}+\mathrm{F}{\mathrm{e}}^{5+}$ charge disproportionation and ordering over two sites accompanied by a structural distortion at 500 K; charge disproportionation of the remaining $\mathrm{F}{\mathrm{e}}^{4+}$ with magnetic order at 280 K; and an unprecedented charge interchange where $\mathrm{F}{\mathrm{e}}^{3+}$ and $\mathrm{F}{\mathrm{e}}^{5+}$ states are exchanged between two sites with spin orientation change at 50 K. These properties demonstrate the presence of multiple competing ground states in this complex, highly condensed network of corner- and face-sharing octahedra.

Recently, Ag–Bi–I system has attracted significant attention as an emergent material for absorbers in solar cells. We have investigated the single-phase compositions, analyzed the detailed crystal structures, measured optical and electronic properties, and determined the structure–property relations of Ag2−3xBixI2. Single-phase samples with CdCl2-type rhombohedral structures were obtained with Ag-rich compositions (x = 0.45–0.48), while defect-spinel-type cubic structures were stabilized with Bi-rich compositions (x = 0.52–0.57). Both the rhombohedral and cubic structures consisted of the cubic close-packed I-ion sublattices, and the small difference in the Ag/Bi composition resulted in distinct crystal structures. Both the CdCl2-type rhombohedral and defect-spinel-type cubic compounds exhibited semiconducting behavior with proper band gap energies, which indicates that both materials are potentially useful as absorbers in solar cells. The rhombohedral structure compounds have shallower valence band energies, larger indirect band gap energies, and higher electrical conductivity with lower activation energy than the cubic structure compounds. The distinct properties result from the difference in the defect structures, additional Ag occupation in the rhombohedral phase and deficiencies of the octahedral site in the cubic phase.

The oxygen evolution reaction (OER) plays a key role in the electrode reactions of emerging energy conversion technologies such as water splitting and rechargeable metal–air batteries. Herein, we report that stronger electron–electron correlation leads to higher OER activity by a systematic electrochemical study of Ca1−xSrxRuO3. Specifically, we find that when the conducting material is sufficiently near the metal–insulator boundary (Ca0.9Sr0.1RuO3 in this study), it leads to a remarkable activity enhancement by a factor of 17. Our finding suggests that electron correlation not only enhances the initial OER activity but also stabilizes the structure of the catalyst. Therefore, the coexistence of metallic conductivity and strong electron correlation is beneficial for developing highly active OER catalysts. Furthermore, the excellent OER activity at x ∼ 0.1 is accompanied by superior bifunctionality toward the OER and the oxygen reduction reaction (ORR). Our study also revealed that conducting materials close to the metal–insulator boundary are promising oxygen reaction catalysts for energy conversion technologies.

BaFexNi1–xO3 with end members of BaNiO3 (x = 0) and BaFeO3 (x = 1), which, respectively, adopt the 2H and 6H hexagonal perovskite structures, were synthesized, and their crystal structures were investigated. A new single phase, Ba4Fe3NiO12 (x = 0.75), that adopts the 12R perovskite structure with the space group R3m (a = 5.66564(7) A and c = 27.8416(3) A), was found to be stabilized. Mossbauer spectroscopy results and structure analysis using synchrotron and neutron powder diffraction data revealed that nominal Fe3+ occupies the corner-sharing octahedral site while the unusually high valence Fe4+ and Ni4+ occupy the face-sharing octahedral sites in the trimers, giving a charge formula of Ba4Fe3+Fe4+2Ni4+O11.5. The magnetic properties of the compound are also discussed.

Through the detailed studies utilizing x-ray and neutron powder diffraction and magnetometry measurements, we report the magnetic phase transitions in the B-site disorder perovskite oxide PrFe0.5Cr0.5O3. The Fe3+/Cr3+ sublattice was observed to form a long-range magnetic order with the GxFz configuration below TN = 270 K from neutron powder diffraction. It then undergoes the second-order phase transition to FxGz spin configuration below 210 K and the transition ends at ~170 K. On the other hand, long range magnetic ordering with FxCy configuration at Pr3+ sublattice can be identified at base temperature. The magnetic phase diagram is derived with spontaneous spin ordering and reorientation at A- and B-sublattices.

A Sr analogue of Ca0.5Bi0.5FeO3, Sr0.5Bi0.5FeO3, containing unusually high valence Fe3.5+ ions was synthesized by using a high-pressure technique. It relieves the electronic instability due to the unusually high valence of Fe3.5+ by a single charge disproportionation (CD) transition (Fe3.5+ -> 0.75Fe(3+) + 0.25Fe(5+)) rather than the successive CD and intermetallic charge transfer (CT) transitions seen in Ca0.5Bi0.5FeO3. Conduction-band narrowing due to the significant bend in the Fe-O-Fe bond in the rhombohedral R (3) over barc crystal structure stabilized the charge-disproportionated state at low temperatures. Most importantly, Bi3+ ions in Sr0.5Bi0.5FeO3 do not act as countercations accepting oxygen holes as they do in Ca0.5Bi0.5FeO3, resulting in the absence of the intermetallic CT transition. The large cavity of the A-site Sr ions prevents the charge-transferred Bi5+ from being stabilized. In the charge-disproportionated state the nearest-neighbor Fe3+ spins align antiferromagnetically and one-fourth of the Fe3+ spins are randomly replaced by Fe5+ spins coupled ferromagnetically with the neighboring Fe3+ spins.

We have studied Fe1-xCoxSi (0 ≤ x ≤ 1) crystals using the electrical resistivity (ρ), Seebeck coefficient (S), and thermal conductivity (κ) measurements, to examine the influence of Co substitution on the electrical and thermal transport properties of FeSi. Notably, a metal-insulator transition occurs at x = 0.3 for the Fe1-xCoxSi series, as the closure of band-gap of FeSi occurs upon Co substitution. Besides, the substituent (Co) induced a significant variation in the Seebeck coefficient, including two sign crossovers. These observations are ascribed to the asymmetric electronic band structure of the Fe1-xCoxSi compounds. The analysis of thermal conductivity demonstrated that Co substitution has a strong effect on the low-temperature phonon thermal transport of FeSi via boundary scattering and point-defect scattering. Most intriguingly, the substituted end compound CoSi has the largest room temperature thermoelectric figure of merit of about 0.06 which is four orders of magnitude larger than that of undoped FeSi.

dc and ac magnetic susceptibility, magnetization, specific heat, and Raman scattering measurements are combined to probe low-lying spin excitations in $\ensuremath{\alpha}$-${\mathrm{Ru}}_{1\ensuremath{-}x}{\mathrm{Ir}}_{x}{\mathrm{Cl}}_{3}$ ($x\ensuremath{\approx}0.2$), which realizes a disordered spin liquid. At intermediate energies ($\ensuremath{\hbar}\ensuremath{\omega}g3\text{ }\text{ }\mathrm{meV}$), Raman spectroscopy evidences linearly $\ensuremath{\omega}$-dependent Majorana-like excitations, obeying Fermi statistics. This points to robustness of a Kitaev paramagnetic state under spin vacancies. At low energies below 3 meV, we observe power-law dependences and quantum-critical-like scalings of the thermodynamic quantities, implying the presence of a weakly divergent low-energy density of states. This scaling phenomenology is interpreted in terms of the random hoppings of Majorana fermions. Our results demonstrate an emergent hierarchy of spin excitations in a diluted Kitaev honeycomb system subject to spin vacancies and bond randomness.

dc and ac magnetic susceptibility, magnetization, specific heat, and Raman scattering measurements are combined to probe low-lying spin excitations in α-Ru_{1-x}Ir_{x}Cl_{3} (x≈0.2), which realizes a disordered spin liquid. At intermediate energies (ℏω3 meV), Raman spectroscopy evidences linearly ω-dependent Majorana-like excitations, obeying Fermi statistics. This points to robustness of a Kitaev paramagnetic state under spin vacancies. At low energies below 3 meV, we observe power-law dependences and quantum-critical-like scalings of the thermodynamic quantities, implying the presence of a weakly divergent low-energy density of states. This scaling phenomenology is interpreted in terms of the random hoppings of Majorana fermions. Our results demonstrate an emergent hierarchy of spin excitations in a diluted Kitaev honeycomb system subject to spin vacancies and bond randomness.

We report on magnetization M(H), dc and ac magnetic susceptibility χ(T), specific heat C_{m}(T) and muon spin relaxation (μSR) measurements of the Kitaev honeycomb iridate Cu_{2}IrO_{3} with quenched disorder. In spite of the chemical disorders, we find no indication of spin glass down to 260 mK from the C_{m}(T) and μSR data. Furthermore, a persistent spin dynamics observed by the zero-field muon spin relaxation evidences an absence of static magnetism. The remarkable observation is a scaling relation of χ[H,T] and M[H,T] in H/T with the scaling exponent α=0.26-0.28, expected from bond randomness. However, C_{m}[H,T]/T disobeys the predicted universal scaling law, pointing towards the presence of additional low-lying excitations on the background of bond-disordered spin liquid. Our results signify a many-faceted impact of quenched disorder in a Kitaev spin system due to its peculiar bond character.

We report high-precision magnetization ([Formula: see text]), magnetic susceptibility ([Formula: see text]), specific heat (C

We report the high pressure synthesis of a layered perovskite Ca2GeO4 which is found to have the Ruddlesden–Popper structure with I41/acd symmetry. Consonant with\ud our recent predictions [Ablitt et al., npj Computational Materials, 2017, 3, 44], the phase displays pronounced uniaxial negative thermal expansion over a large temperature range. Negative thermal expansion that persists over a large temperature range is very unusual in the perovskite structure, and its occurrence in this instance can be understood to arise due to both soft lattice vibrations associated with a phase competition and the unusually compliant nature of this structure, which effectively couples thermal expansion in the layer plane to lattice contractions perpendicular to the layering direction via a “corkscrew” mechanism.

We report on magnetization M(H), dc and ac magnetic susceptibility χ(T), specific heat C_{m}(T) and muon spin relaxation (μSR) measurements of the Kitaev honeycomb iridate Cu_{2}IrO_{3} with quenched disorder. In spite of the chemical disorders, we find no indication of spin glass down to 260 mK from the C_{m}(T) and μSR data. Furthermore, a persistent spin dynamics observed by the zero-field muon spin relaxation evidences an absence of static magnetism. The remarkable observation is a scaling relation of χ[H,T] and M[H,T] in H/T with the scaling exponent α=0.26-0.28, expected from bond randomness. However, C_{m}[H,T]/T disobeys the predicted universal scaling law, pointing towards the presence of additional low-lying excitations on the background of bond-disordered spin liquid. Our results signify a many-faceted impact of quenched disorder in a Kitaev spin system due to its peculiar bond character.

We have investigated the nature of the short-range magnetic phase region of ${\mathrm{Sr}}_{2\ensuremath{-}x}{\mathrm{La}}_{x}{\mathrm{IrO}}_{4}$ ($0\ensuremath{\le}x\ensuremath{\le}0.14$). This so-called spin-orbit Mott insulator's predicted transition to superconductivity with electron doping has remained elusive. Instead, short-range magnetism prevails over an extensive doping range up to the La solubility limit. We find evidence for quantum critical-like fluctuations of the short-range magnetic phase, in both a scaling relation of the ac susceptibility $\ensuremath{\chi}{T}^{\ensuremath{\alpha}}$ and the magnetization $M{T}^{\ensuremath{\alpha}\ensuremath{-}1}$ with $\ensuremath{\alpha}=0.4--0.5$, as well as in the time-field scaling ($t/{H}^{\ensuremath{\gamma}}$) of the $\ensuremath{\mu}\mathrm{SR}$ asymmetry function. Our combined study of ac susceptibility and $\ensuremath{\mu}\mathrm{SR}$, on the one hand, uncovers a two-stage weak symmetry breaking to spin freezing or proximate spin glass and to a subsequent spin glass within the short-range magnetic phase. On the other hand, we demonstrate that magnetic correlations become more static above $x=0.06$ in spite of an apparent dilution of magnetic moments, indicative of enhanced inhomogeneities in a higher La-doping regime.

BaFe

It is of great interest to design and make materials in which ferroelectric polarisation is coupled to other order parameters such as lattice, magnetic and electronic instabilities. Such materials will be invaluable in next-generation data storage devices. Recently, remarkable progress has been made in understanding improper ferroelectric coupling mechanisms that arise from lattice and magnetic instabilities. However, although theoretically predicted, a compact lattice coupling between electronic and ferroelectric (polar) instabilities has yet to be realised. Here we report detailed crystallographic studies of a novel perovskite Hg$^{\textbf{A}}$Mn$^{\textbf{A'}}_{3}$Mn$^{\textbf{B}}_{4}$O$_{12}$ that is found to exhibit a polar ground state on account of such couplings that arise from charge and orbital ordering on both the A' and B-sites, which are themselves driven by a highly unusual Mn$^{A'}$-Mn$^B$ inter-site charge transfer. The inherent coupling of polar, charge, orbital and hence magnetic degrees of freedom, make this a system of great fundamental interest, and demonstrating ferroelectric switching in this and a host of recently reported hybrid improper ferroelectrics remains a substantial challenge., 9 pages, 7 figures

We investigated moderate-temperature oxygen diffusion mechanisms in Sr2ScGaO5 with Brownmillerite structure type. From oxygen isotope 18O−16O exchange experiments we determined that oxygen mobility sets in above 550 °C. Temperature-dependent neutron and X-ray (synchrotron) diffraction experiments allowed us to correlate the oxygen mobility with a subtle phase transition of the orthorhombic room-temperature structure with I2mb space group toward Imma, going along with a disorder of the (GaO4)∞-tetrahedral chains. From lattice dynamical simulations we could clearly evidence that dynamic switching of the (GaO4)∞-tetrahedral chains from its R to L configuration sets in at 600 °C, thus correlating oxygen diffusion with the dynamic disorder. Oxygen ion diffusion pathways are thus constrained along the onedimensional oxygen vacancy channels, which is a different diffusion mechanism compared to that of the isostructural CaFeO2.5, where diffusion of the apical oxygen atoms into the vacant lattice sites are equally involved in the diffusion pathway. The proposed ordered room-temperature structure in I2mb is strongly supported by 17O, 45Sc, and 71Ga NMR measurements, which indicate the presence of crystallographically unique sites and the absence of local disordering effects below the phase transition. The electric field gradient tensor components measured at the nuclear sites are found to be in excellent agreement with calculated values using the WIEN2k program. The oxygen site assignment has been independently confirmed by 17O{45Sc} transfer of adiabatic populations double-resonance experiments.

A modified traveling solvent floating zone (TSFZ) technique was used to successfully grow a large size and high quality single crystal of multiferroic material YBaCuFeO 5 . This modified TSFZ growth uses a stoichiometric feed rod and pure copper oxide as the initial flux without prior knowledge of the complex phase diagram involving four elements, and the optimal flux for the growth of incongruently melt crystal is self-adjusted after a prolonged stable pulling. The wetting of the feed rod edge that often perturbs the molten zone stability was avoided by adding 2 wt% B 2 O 3 . The optimal flux concentration for the YBaCuFeO 5 growth can be extracted to be near YBaCuFeO 5 :CuO=13:87 in molar ratio. The crystal quality was confirmed by the satisfactory refinement of crystal structure of space group P 4 mm and the two consecutive anisotropic antiferromagnetic phase transitions near 455 K and 170 K.

A Sr analogue of Ca

Using magnetization, dielectric constant, and neutron diffraction measurements on a high quality single crystal of YBaCuFeO

Cation ordering in the 1322 perovskite CaCu3Fe2Nb2O12 has been investigated by synchrotron X-ray diffraction structure analysis, high-resolution electron microscopy, and magnetic measurements. All of the samples have full 1:3 ordering of Ca and Cu cations at the perovskite A-sites, but the Fe and Nb cations at the B sites show different degrees of ordering depending on the synthesis conditions. A slow-cooled sample has almost complete rock-salt-type 1:1 cation ordering at the B sites, but a rapidly cooled sample has no long-range B-cation arrangement. The ordered compound shows a large saturated magnetization (5.7 μB/formula unit (fu)) below 170 K due to the ferrimagnetism of the A′-site Cu2+ and B-site Fe3+ spins, whereas the B-site disordered form has a small magnetization (

We report high-precision magnetization ([Formula: see text]), magnetic susceptibility ([Formula: see text]), specific heat (C p (T, H)) and 'zero-field' electrical resistivity, [Formula: see text], data taken on Gd2Te3 single crystal over wide ranges of temperature and magnetic field (H), with either [Formula: see text]-axis or [Formula: see text]-plane. [Formula: see text] and [Formula: see text] unambiguously establish that the b-axis is the easy direction of magnetization whereas any direction in the ac-plane is a hard direction. The [Formula: see text]-type anomaly in 'zero-field' specific heat, C p (T, H = 0), and an abrupt drop in [Formula: see text] (characteristic of the paramagnetic (PM) - antiferromagnetic (AFM) phase transition) are observed at the Neel temperature, [Formula: see text] K. [Formula: see text] and C p (T,H) clearly demonstrate that [Formula: see text] shifts to lower temperatures with increasing H irrespective of whether H points in the easy or hard direction. When [Formula: see text], the [Formula: see text] isotherms at temperatures in the range 2.5 K [Formula: see text] [Formula: see text] K reveal the existence of a field-induced spin-flop (SF) transition at fields 4.0 T [Formula: see text] [Formula: see text] [Formula: see text] 4.5 T. The first principles electronic band structure and density of states calculations, based on the density functional theory, correctly predict an AFM ground state (stabilized primarily by the 4f Gd3+ - 5p Te2-- 4f Gd3+ superexchange interactions) and the observed semi-metallic behavior for the Gd2Te3 compound. Moreover, these calculations yield the values [Formula: see text] [Formula: see text] for the ordered magnetic moment per Gd atom at T = 0, [Formula: see text] mJ mol-1 K-2 for the Sommerfeld coefficient for the electronic specific heat contribution and [Formula: see text] K for the Curie-Weiss temperature, respectively. These theoretical estimates conform well with the corresponding experimental values [Formula: see text] [Formula: see text], [Formula: see text] mJ mol-1 K-2 and [Formula: see text] K.

We report on the crystal growth and magnetic property studies of layered Na2Ni2TeO6 and Na2Cu2TeO6. The former has a honeycomb layer composed of NiO6 octahedra and the latter is composed of paired CuO4 plaquettes connected through TeO6 octahedra. The 3D antiferromagnetic (AF) phase transition is defined with the peak of dχ/dT at ~27 K for Na2Ni2TeO6 and confirmed with specific heat measurement. A comparison is made between the magnetic behavior of Na2Ni2TeO6 and BaNi2V2O8, with a similar Ni honeycomb network of different centers. Na2Cu2TeO6 has been confirmed to have a spin gap of Δ/kB ~ 262 K due to spin dimerization of Cu2+S = 1/2 within each paired CuO4 plaquette.