Multivalued Memory via Freezing of Super-Hard Magnetic Domains in a Quasi 2D-Magnet.

The design of high-density non-volatile memories is a long-standing dream, limited by conventional storage "0" or "1" bits. An alternative paradigm exists in which regions within candidate materials can be magnetized to intermediate values between the saturation limits. In principle, this paves the way to multivalued bits, vastly increasing storage density. Single-molecule magnets, are good examples offering transitions between intramolecular quantum levels, but require ultra-low temperatures and limited relaxation time between magnetization states. It is showed here that the quasi 2D-Ising compound BaFe2 (PO4 )2 overcomes these limitations. The combination of giant magneto-crystalline anisotropy, strong ferromagnetic exchange, and strong intrinsic pinning creates remarkably narrow magnetic domain walls, collectively freezing under Tf ≈15 K. This results in a transition from a soft to a super-hard magnet (coercive force > 14 T). Any magnetization can then be printed and robustly protected from external fields with an energy barrier >9T at 2 K.

Influence of Polymorphism on the Magnetic Properties of Co5TeO8 Spinel.

This study presents the influence of polymorphism on the magnetic properties of Co5TeO8. This compound with a spinel-like structure [Co2]A[Co3Te]BO8 was synthesized into two polymorphs: one disordered within a cubic Fd3̅m structure, where Co2+ and Te6+ ions are randomly distributed on the octahedral B sites [the disordered polymorph can also be presented as an inverse spinel of the formula Co(Co1.5Te0.5)O4] and the other ordered with a cubic P4332 structure where Co2+ and Te6+ ions are ordered on the B sites. The macroscopic magnetic measurements showed that both polymorphs present a ferrimagnetic ordering, below ∼40 K, and a second transition is also observed at 27 K for the ordered polymorph. Neutron powder diffraction data between room temperature and 1.7 K showed as well the presence of short-range magnetic ordered clusters, which appears for both polymorphs below 200 K. At lower temperature, these short-range orders are transformed into long-range ferrimagnetic orders. Below TC = 40 K, the colinear ferrimagnetic structure of the disordered polymorph is described with the I41/am'd' space group. The ordered polymorph undergoes an incommensurate ferrimagnetic spiral spin ordering below TC1 = 45 K, followed by a second magnetic phase transition at TC2 = 27 K. This last transition is associated with the emergence of an additional ferrimagnetic component and an abrupt change in the magnitude of the magnetic propagation vector k = [0, 0, γ] from γ = 0.086 at T = 30 K to γ ≈ 0.14 in the range between 27 and 1.7 K. The magnetic symmetry of the ordered polymorph is described with the P43(00γ)0 magnetic superspace group. We evidenced that the ordering of Co2+/Te6+ on the B sites changes all of the Co-Co and Co-O distances and thus all JAB, JAA, and JBB exchange interactions, between the A and B sites, which are able to stabilize the incommensurate spin modulation in the ordered polymorph.

Strong Magnetic Anisotropy of Epitaxial PrVO3 Thin Films on SrTiO3 Substrates with Different Orientations.

We have probed the structural and magnetic properties of PrVO3 (PVO) thin films grown on the (001)-, (110)-, and (111)-oriented SrTiO3 (STO) substrates. By changing the substrate orientation, the film out-of-plane orientation can be tuned to [110], [100]/[010], and [011]/[311], with different in-plane crystallographic variants. Accommodation of these variants on the different substrates implies different strain states, which have direct influence on the magnetic properties of PVO films. The magnetic moment of PVO films radically enhances from 0.4 µB/f.u. for STO(001) to 2.3 µB/f.u. for STO(111). While films on the (001)-oriented STO substrate display out-of-plane anisotropy, an in-plane anisotropy is observed for films grown on the (110)- and (111)-oriented STO substrates. In addition, a strong uniaxial magnetic anisotropy is also extracted for a partially relaxed film on the (110)-oriented STO substrate. Such findings can help oxide community for the better understanding of magnetic anisotropy in vanadate thin films, a subject that still suffer from significant lack of scientific investigations.

Cascading transitions toward unconventional charge density wave states in the quasi-two-dimensional monophosphate tungsten bronze P4W16O56.

Single crystals of the m = 8 member of the low-dimensional monophosphate tungsten bronzes (PO2)4(WO3)2m family were grown by chemical vapour transport technique and the high crystalline quality obtained allowed a reinvestigation of the physical and structural properties. Resistivity measurements revealed three anomalies at T C1 = 258 K, T C2 = 245 K and T C3 = 140 K, never observed until now. Parallel X-ray diffraction investigations showed a specific signature associated with three structural transitions, i.e. the appearance of different sets of satellite reflections below T C1, T C2 and T C3. Several harmonics of intense satellite reflections were observed, reflecting the non-sinusoidal nature of the structural modulations and a strong electron-phonon coupling in the material. These transitions could be associated with the formation of three successive unconventional charge density wave states.

Metamagnetic Transitions versus Magnetocrystalline Anisotropy in Two Cobalt Arsenates with 1D Co2+ Chains.

We have investigated two original hydrated cobalt arsenates based on Co2+ octahedral edge-sharing chains. Their different magnetocrystalline anisotropies induce different types of metamagnetic transitions: spin-flop versus spin-flip. In both compounds, a strong local anisotropy (Ising spins) is favored by the spin-orbit coupling present in the CoO6 octahedra, while ferromagnetic (FM) exchanges predominate in the chains. Co2(As2O7)·2H2O (1) orders antiferromagnetically below TN = 6.7 K. The magnetic structure is a noncollinear antiferromagnetic spin arrangement along the zigzag chains with DFT calculations implying frustrated chains and weakened anisotropy. A metamagnetic transition suggests a spin-flop process above µ0H = 3.2 T. In contrast, in BaCo2As2O8·2H2O (2) linear chains are arranged in disconnected layers, with only interchain ferromagnetic exchanges, therefore increasing its magnetocrystalline anisotropy. The magnetic structure is collinear with a magnetic easy axis that allows a spin-flop to a sharp spin-flip transition below TN = 15.1 K and above µ0H = 6.2 T.

Textured Manganite Films Anywhere.

New paradigms are required in microelectronics when the transistor is in its downscaling limit and integration of materials presenting functional properties not available in classical silicon is one of the promising alternatives. Here, we demonstrate the possibility to grow La0.67Sr0.33MnO3 (LSMO) functional materials on amorphous substrates with properties close to films grown on single-crystalline substrates using a two-dimensional seed layer. X-ray diffraction and electron backscatter diffraction mapping demonstrate that the Ca2Nb3O10- nanosheet (NS) layer induces epitaxial stabilization of LSMO films with a strong out-of-plane (001) texture, whereas the growth of LSMO films on uncoated glass substrates exhibits a nontextured polycrystalline phase. The magnetic properties of LSMO films deposited on NS are similar to those of the LSMO grown on SrTiO3 single-crystal substrates in the same conditions (which is used as a reference in this work). Moreover, transport measurements take advantages of the texture and polycrystalline properties to induce low-field magnetoresistance at low temperature and also a high value of 40% magnetoresistance from 10 to 300 K, making it interesting for sensor applications. Therefore, the NS seed layer offers new perspectives for the integration of functional materials grown at moderate temperatures on any substrate, which will be the key for the development of oxitronics.

Deciphering local complex order by HAADF in a disordered mixed polyanion iron oxide: Sr4Fe2[Fe0.5(SO4)0.25(CO3)0.25]O7.25.

A layered iron compound involving two divalent polyanions (carbonate and sulfate anions) was synthesized by solid state chemistry in a closed ampule in the form of a ceramic. The Sr4Fe2[Fe0.5(SO4)0.25(CO3)0.25]O7.25 compound derives from the third term of the Ruddlesden and Popper family, Sr4Fe3O10. A multiscale approach through transmission electron microscopy (TEM) and powder neutron diffraction (PND) studies shows that SO4 and CO3 groups substitute for the iron polyhedron of the central layer of the perovskite blocks and the absence of long range ordering between sulfate and carbonates and FeO5 groups. Nevertheless, waves disturbing the expected periodicity of the atomic layer are evidenced in HAADF images. An accurate analysis of these images provides a view of the local cationic order correlated with SO4 and CO3 for FeO5 substitution.

Stairlike Aurivillius Phases in the Pseudobinary Bi5Nb3O15-ABi2Nb2O9 (A = Ba and Sr) System: A Comprehensive Analysis Using Superspace Group Formalism.

We report the possibility of extending the so-called stairlike Aurivilius phases in the pseudobinary Bi5Nb3O15-ABi2Nb2O9 (A = Ba and Sr) over a wide range of compositions. These phases are characterized by a discontinuous stacking of [Bi2O2] slabs and perovskite blocks, leading to long-period intergrowths stabilized as a single phase. When analyses from precession electron diffraction tomography and X-ray and neutron powder diffraction are combined, the monoclinic incommensurately modulated structure with q = αa* + γc* previously proposed for the ABi7Nb5O24 composition could be generalized to the Bi5Nb3O15-ABi2Nb2O9 (A = Ba and Sr) compounds. Considering the compositions expressed as (A,Bi)1- xNb xO3-3 x, the stacking sequence associated with compositions ranging from x = 2/5 to 3/8 is governed by the component γ of the modulation vector and can be predicted following a Farey tree hierarchy independently to the A cation. The length of the steps, characteristic of the stairlike nature, is controlled by the α component and depends on the substitution ratio A/Bi and the nature of A (A = Ba and Sr). This study highlights the compositional flexibility of stairlike Aurivillius phases.

Combining Multiscale Approaches for the Structure Determination of an Iron Layered Oxysulfate: Sr4Fe2.5O7.25(SO4)0.5.

The new iron layered oxysulfate Sr4Fe2.5O7.25(SO4)0.5 has been prepared by a solid-state reaction in closed ampules into the form of ceramics and single crystals. Its atomic structure has been solved by means of spectroscopy, diffraction techniques, and high-resolution electron microscopy. Sr4Fe2.5O7.25(SO4)0.5 is a layered structure that derives from the Ruddelsden-Popper (RP) phases with the layer stacking sequence SrO/SrFeO2.5/SrFe0.5(SO4)0.5O1.25/SrFeO2.5. Within the mixed Fe3+/SO42- layer, the sulfur atoms are slightly shifted from the B site of the perovskite and each sulfate group shares two corners with iron pyramids in the basal plan without any order phenomenon. The electronic conductivity is thermally activated, while no ionic conductivity is detected.

Comprehensive Study of Oxygen Storage in YbFe2O4+x (x ≤ 0.5): Unprecedented Coexistence of FeOn Polyhedra in One Single Phase.

The multiferroic LuFe2.5+2O4 was recently proposed as a promising material for oxygen storage due to its easy reversible oxidation into LuFe3+2O4.5. We have investigated the similar scenario in YbFe2O4+x, leading to a slightly greater oxygen storage (OSC) capacity of 1434 µmol O/g. For the first time, the structural model of LnFe2O4.5 was fully understood by high-resolution microscopy images, and synchrotron and neutron diffraction experiments, as well as maximum entropy method. The oxygen uptake promotes a reconstructive shearing of the [YbO2] sub-units controlled by the adaptive Ln/Fe oxygen coordination and the Fe2/3+ redox. After oxidation, the rearrangement of the Fe coordination polyhedra is unique such that all available FeOn units (n = 6, 5, 4 in octahedra, square pyramids, trigonal bipyramids, tetrahedra) were identified in modulated rows growing in plane. This complex pseudo-ordering gives rise to short-range antiferromagnetic correlation within an insulating state.

Preferred Orientation Contribution to the Anisotropic Normal State Resistivity in Superconducting Melt-Cast Processed Bi2Sr2CaCu2O8+δ.

We describe how the contribution of crystallographic texture to the anisotropy of the resistivity of polycrystalline samples can be estimated by averaging over crystallographic orientations through a geometric mean approach. The calculation takes into account the orientation distribution refined from neutron diffraction data and literature values for the single crystal resistivity tensor. The example discussed here is a melt-cast processed Bi2Sr2CaCu2O8+δ (Bi-2212) polycrystalline tube in which the main texture component is a <010> fiber texture with relatively low texture strength. Experimentally-measured resistivities along the longitudinal, radial, and tangential directions of the Bi-2212 tube were compared to calculated values and found to be of the same order of magnitude. Calculations for this example and additional simulations for various texture strengths and single crystal resistivity anisotropies confirm that in the case of highly anisotropic phases such as Bi-2212, even low texture strengths have a significant effect on the anisotropy of the resistivity in polycrystalline samples.

Chemical Strain Engineering of Magnetism in Oxide Thin Films.

Transition metal oxides having a perovskite structure form a wide and technologically important class of compounds. In these systems, ferroelectric, ferromagnetic, ferroelastic, or even orbital and charge orderings can develop and eventually coexist. These orderings can be tuned by external electric, magnetic, or stress field, and the cross-couplings between them enable important multifunctional properties, such as piezoelectricity, magneto-electricity, or magneto-elasticity. Recently, it has been proposed that additional to typical fields, the chemical potential that controls the concentration of ion vacancies in these systems may reveal an efficient alternative parameter to further tune their properties and achieve new functionalities. In this study, concretizing this proposal, the authors show that the control of the content of oxygen vacancies in perovskite thin films can indeed be used to tune their magnetic properties. Growing PrVO3 thin films epitaxially on an SrTiO3 substrate, the authors reveal a concrete pathway to achieve this effect. The authors demonstrate that monitoring the concentration of oxygen vacancies through the oxygen partial pressure or the growth temperature can produce a substantial macroscopic tensile strain of a few percent. In turn, this strain affects the exchange interactions, producing a nontrivial evolution of Néel temperature in a range of 30 K.

Unusual Relaxor Ferroelectric Behavior in Stairlike Aurivillius Phases.

New ferroelectric layered materials were found in the pseudobinary system Bi5Nb3O15-ABi2Nb2O9 (A= Ba, Sr and Pb). Preliminary observations made by transmission electron microscopy indicate that these compounds exhibit a complex incommensurately modulated structure. A (3 + 1)D structural model is obtained using ab initio phasing by charge flipping based on the analysis of precession electron diffraction tomography data. The (3 + 1)D structure is further validated by a refinement against neutron powder diffraction. These materials possess a layered structure with discontinuous [Bi2O2] slabs and perovskite blocks. While these structural units are characteristics of Aurivillius phases, the existence of periodic crystallographic shear planes offers strong similarities with collapsed or stairlike structures known in high-Tc superconductors and related compounds. Using dielectric spectroscopy, we study the phase transitions of these new layered materials. For A = Ba and Sr, a Vögel-Fulcher-like behavior characteristic of the so-called relaxor ferroelectrics is observed and compared to "canonical" relaxors. For A = Sr, the absence of a Burns temperature separated from the freezing temperature appears as a rather unusual behavior.

Common Building Motifs in Ba2Fe3(PO4)4·2H2O, BaFe3(PO4)3, and Na3Fe3(PO4)4: Labile Fe(2+)/Fe(3+) Ordering and Charge-Dependent Magnetism.

Two new mixed-valence Fe(2/3+) barium phosphates have been synthesized in hydrothermal conditions and characterized: Ba2Fe(2.66+)3(PO4)4·2H2O (compound 1, ratio Fe(3+)/Fe(2+) = 2:1, orthorhombic space group Pbca, a = 6.71240(10) Å, b = 10.6077(2) Å, c = 20.9975(5) Å, R1 = 3.39%) and BaFe(2.33+)3(PO4)3 (compound 2, ratio Fe(3+)/Fe(2+) = 1:2, orthorhombic, space group Imma with a = 10.5236(3) Å, b = 13.4454(4) Å, c = 6.6411(2) Å, R1 = 1.63%). 1 has a two-dimensional crystal structure built of [Fe(2.5+)2Fe(3+)1(PO4)4](4-) layers with charge segregation on two individual Fe crystal sites, in contrast to the single valence on these two sites found in similar layers of Na3Fe(3+)3(PO4)4. The crystal structure of 2 is formed of the same layers but condensed into a 3D [Fe(2+)2Fe(3+)1(PO4)3](2-) framework. The complete Fe(2+) vs Fe(3+) charge ordering on the two available sites differs from what was found in the two previous cases and denotes a remarkable charge adaptability of the common elementary units. Compared to the antiferromagnetic Na3Fe(3+)3(PO4)4 the partial iron reduction into Fe(2+) is responsible for strong ferromagnetic components along the c-easy axis for both 1 and 2. Additionally 1 shows multiple magnetization steps in the perpendicular direction, giving raise to atypical anisotropic magnetism into a complex magnetic phase diagram.

Magnetodielectric Effect in Crystals of the Noncentrosymmetric CaOFeS at Low Temperature.

Single crystals of the stoichiometric iron calcium oxysulfide CaOFeS have been grown by a solid-state reaction. Structural analysis of CaOFeS at room temperature by combining single-crystal X-ray diffraction data and transmission electron microscopy leads to a stoichiometric hexagonal noncentrosymmetric P63mc layered structure isostructural to CaOZnS. It is built from alternating layers made of FeOS3 tetrahedra sharing sulfur apexes and stacked with Ca(2+) planes. All Fe-O bonds are parallel to the stacking axis; this breaks the centrosymmetry, leading to a polar structure. The dielectric measurements reveal the existence of a magnetodielectric effect near 33 K in good agreement with the Neel temperature, as evidenced near 35 K by specific heat measurements reported by a different group.

Reversible topochemical exsolution of iron in BaFe(2+)2(PO4)2.

BaFe(2+) 2 (PO4 )2 was recently prepared and identified as the first 2D-Ising ferromagnetic oxide with an original reentrant structural transition driven by high-spin Fe(2+) ions arranged in honeycomb layers. Both long-term air exposure and moderate temperature (T>375 °C) leads to topochemical oxidation into iron-depleted compounds with mixed Fe(2+) /Fe(3+) valence. This process is unique, as the exsolution is effective even from single crystal with preservation of the initial crystallinity, and the structure of the deficient BaFe2-x (PO4 )2 (x

Two-orbital three-electron stabilizing interaction for direct Co2+ - As3+ bonds involving square-planar CoO4 in BaCoAs2O5.

The quest for new oxides with cations containing active lone-pair electrons (E) covers a broad field of targeted specificities owing to asymmetric electronic distribution and their particular band structure. Herein, we show that the novel compound BaCoAs2 O5, with lone-pair As(3+) ions, is built from rare square-planar Co(2+) O4 involved in direct bonding between As(3+) E and Co(2+) dz2 orbitals (Co-As=2.51 Å). By means of DFT and Hückel calculations, we show that this σ-type overlapping is stabilized by a two-orbital three-electron interaction allowed by the high-spin character of the Co(2+) ions. The negligible experimental spin-orbit coupling is expected from the resulting molecular orbital scheme in O3 AsE-CoO4 clusters.

Across the structural re-entrant transition in BaFe2(PO4)2: influence of the two-dimensional ferromagnetism.

BaFe2(PO4)2 was recently prepared by hydrothermal synthesis and identified as the first two-dimensional (2D) Ising ferromagnetic oxide, in which honeycomb layers made up of edge-sharing FeO6 octahedra containing high-spin Fe(2+) ions (S = 2) are isolated by PO4 groups and Ba(2+) cations. BaFe2(PO4)2 has a trigonal R-3 structure at room temperature but adopts a triclinic P-1 structure below 140 K due to the Jahn-Teller (JT) instability arising from the (t2g)(4)(eg)(2) configuration. The triclinic crystal structure was refined to find significantly distorted Fe(2+)O6 octahedra in the honeycomb layers while the distortion amplitude QJT was estimated to 0.019 Å. The JT stabilization energy is estimated to be ∼7 meV per formula unit by DFT calculations. Below ∼70 K, very close to the ferromagnetic transition temperature Tc = 65.5 K, the structure of BaFe2(PO4)2 returns to a trigonal R-3 structure in the presence of significant ferromagnetic domains. This rare re-entrant structural transition is accompanied by a discontinuous change in the quadrupolar splitting of Fe(2+), as determined by Mössbauer spectroscopy. EPR measurements show the presence of magnetic domains well above Tc , as expected for a ferromagnetic 2D Ising system, and support that the magnetism of BaFe2(PO4)2 is uniaxial (g⊥ = 0).

Puzzling polymorphism of layered Ba(CoPO4)2.

In this paper, we present the phase diagram and magnetic properties of the layered Co(2+)-based compounds of formula Ba(CoPO4)2 for which the rhombohedral γ form is well-known for its quasi-2D XY topology that is responsible for magnetization steps. The structural resolution of the new, room temperature-stable monoclinic α form shows similitude with the hydrated homologue Ba(CoPO4)2·H2O and consists of the stacking between [CoPO4](-) sheets with chain subunits. We show by means of high temperature powder XRD and thermal analyses that the α form transforms into several polymorphs also exhibiting layered architectures upon heating. Three reversible transitions at 773, 893, and 993 K were observed from DTA which allowed us to define several forms as follows: α → α' → α″ → ß. The crystallographic relationships between the several polymorphs and hydrate analogue are discussed. The α' and α″ cell parameters involve a direct relationship with the α form, whereas the trigonal ß phase was fully solved and found isomorphic with the compounds CaZn2P2O8 and BaAl2Si2O8. The magnetic study of the α form shows an antiferromagnetic ordering at T(N) = 17 K, with spins canting below T(N). Then, the analysis of the magnetic interactions paths occurring within the layers evidence superexchange paths and additional supersuperexchange paths between the chains. This scheme leads to a hexagonal frustrated topology responsible for the canted spin structure in a 2D-topology of anisotropic Co(2+) magnetic ions.