Crystal structure, phase transitions, and magnetic properties of iridium perovskites Sr2MIrO6 (M = Ni, Zn).

Double perovskites containing Ir(6+)/Ir(5+) with formula Sr2MIrO6 (M = Ni, Zn) have been synthesized under high oxygen pressure conditions. Their crystal structures have been studied by X-ray and neutron powder diffraction at room temperature (RT) and 2 K. At RT, these oxides crystallize in the monoclinic space group P2(1)/n with unit-cell parameters a ≈ √2a0, b ≈ √2a0, and c ≈ 2a0, and ß ≈ 90°. The thermal evolution of the structure of the Ni-containing compound shows the presence of two phase transition in the 373-673 K interval following the sequence P2(1)/n → I4/m → Fm3m. These materials have also been characterized by magnetic measurements, suggesting the onset of antiferromagnetic interactions at T(N) = 58 and 46 K, for M = Ni, Zn, respectively. X-ray absorption spectroscopy sheds light on the oxidation states of M and Ir ions within these double perovskites.

Influence of the Bi3+ electron lone pair in the evolution of the crystal and magnetic structure of La(1-x)Bi(x)Mn2O5 oxides.

La(1-x)Bi(x)Mn2O5 (x = 0, 0.2, 0.4, 0.6, 0.8 and 1) oxides are members of the RMn2O5 family. The entire series has been prepared in polycrystalline form by a citrate technique. The evolution of their magnetic and crystallographic structures has been investigated by neutron powder diffraction (NPD) and magnetization measurements. All the samples crystallize in an orthorhombic structure with space group Pbam containing infinite chains of Mn(4+)O6 octahedra sharing edges, linked together by Mn(3+)O5 pyramids and (La/Bi)O8 units. These units become strongly distorted as the amount of Bi increases, due to the electron lone pair of Bi(3+). All the members of the series are magnetically ordered below TN = 25-40 K and they present different magnetic structures. For the samples with low Bi content (x = 0.2 and 0.4) the magnetic structure is characterized by the propagation vector k = (0,0,1/2). The magnetic moments of the Mn(4+) ions placed at octahedral sites are ordered according to the basis vectors (Gx, Ay, 0) whereas the Mn(3+) moments, located at pyramidal sites, are ordered according to the basis vectors (0, 0, Cz). When the content of Bi increases, two different propagation vectors are needed to explain the magnetic structure: k1 = (0,0,1/2) and k2 = (1/2,0,1/2). For x = 0.6 and 0.8, k2 is predominant over k1 and for this propagation vector (k2) the magnetic arrangement is defined by the basis vectors (Gx, Ay,0) and (Fx, Cy, 0) for Mn(4+) and Mn(3+) ions, respectively.

Ferromagnetic Cu-O-Cu coupling in CaCu3Sn4O12 probed by neutron diffraction.

The A-site ordered perovskite oxide with the formula CaCu(3)Sn(4)O(12) has been synthesized in polycrystalline form under moderate pressure conditions (3.5 GPa) in combination with high temperature (1000 °C). This oxide crystallizes in the cubic space group [Formula: see text] (no. 204) with the unit-cell parameter a = 7.64535(6) Å at 300 K. The SnO(6) network is extremely tilted, giving rise to a square planar coordination for Cu(2+) cations. The non-magnetic character of Sn(4+) offers an excellent opportunity to probe the magnetism of Cu(2+) at the A sublattice in CaCu(3)Sn(4)O(12). Magnetic susceptibility shows that this compound is ferromagnetic below T(C) = 10 K, which is an unusual magnetic behaviour in cuprates. This peculiar aspect has been examined by neutron powder diffraction. The refinement of the magnetic structure at 4 K indeed indicates a parallel coupling between Cu(2+) spins with a magnetic moment of 0.5 µ(B)/Cu atom.

On the magnetic structure of PrMn2O5: a neutron diffraction study.

The long-range magnetic ordering of PrMn(2)O(5) has been studied on polycrystalline samples from neutron diffraction and specific heat measurements. The onset of antiferromagnetic ordering is observed at T(N) ≈ 25 K. In the temperature interval 18 K < T < 25 K the magnetic structure is defined by the propagation vector k(1) = (1/2,0,0). Below 18 K, some additional magnetic satellites appear in the NPD patterns, which are indexed with k(2) = (0,0,1/2). Therefore, below 18 K the magnetic structure consists of two independent magnetic domains, defined by the propagation vectors k(1) and k(2). The magnetic structure of the k(1)-domain is given by the basis vectors (C(x),0,0) and (C(x)',0,0) for Mn(4h) and Mn(4f), respectively. In the k(2)-domain, the magnetic structure is defined by the basis vectors (0,0,G(z)) and (F(x)',G(y)',0) for Mn(4h) and Mn(4f), respectively. At T = 1.5 K, for the magnetic phase associated with k(1), the magnetic moments of the Mn atoms at the 4h and 4f sites are 1.82(7) and 1.81(6) µ(B), respectively; for the magnetic phase associated with k(2), the magnetic moments for the Mn(4h) and Mn(4f) atoms are 0.59(5) and 2.62(5) µ(B), respectively.

Magnetic and structural features of the NdNi(1 - x)Mn(x)O3 perovskite series investigated by neutron diffraction.

Selected members of the perovskite series NdNi(1 - x)Mn(x)O(3) (0 ≤ x ≤ 1) have been prepared by a soft chemistry technique, followed by thermal treatments either under high oxygen pressure (x ≤ 0.5) or in air (x > 0.5). The crystal and magnetic structures have been studied by means of neutron diffraction, complemented with magnetic susceptibility measurements. For x = 0.25, 0.75, the crystal structure of the perovskites can be defined in the orthorhombic Pbnm space group, with Ni and Mn distributed at random over the octahedral sites of the structure. In contrast, the x = 0.5 compound crystallizes in a monoclinic P 2(1)/n structure containing two different octahedral positions, occupied by Ni and Mn, respectively. This is a result of the charge disproportionation of Ni(3+) + Mn(3+) to give Ni(2+) + Mn(4+) cations. The Ni(2+)O(6) octahedra are considerably larger than the Mn(4+)O(6) octahedra. This compound can be considered as a double perovskite of composition Nd(2)NiMnO(6). Unlike NdNiO(3) and NdMnO(3), which exhibit an antiferromagnetic ordering at low temperatures, the intermediate samples for x = 0.25, 0.50, 0.75 exhibit a ferromagnetic arrangement of (Ni, Mn) spins, with the moments aligned along the z axis, as probed using neutron diffraction. A maximum T(C) of 200 K is observed for x = 0.5, whereas T(C) = 150 K and 130 K are observed for x = 0.25 and 0.75, respectively. While NdNiO(3) is metallic above 200 K, a semiconducting behavior is determined between 120-300 K for the intermediate compositions.

Magnetic and electronic properties of RNiO3 (R = Pr, Nd, Eu, Ho and Y) perovskites studied by resonant soft x-ray magnetic powder diffraction.

Soft x-ray resonant magnetic powder diffraction of the ([Formula: see text]) reflection at the Ni L(2, 3) edges is used to study the magnetic and electronic properties of a series of RNiO(3) materials (with R = Pr, Nd, Eu, Ho and Y) below the metal-insulator transition. The polarization and energy dependence of the reflection gives further support for a non-collinear magnetic structure and charge disproportionation in the whole RNiO(3) series. Only small changes in the spectra of the magnetic ([Formula: see text]) reflection and in the absorption spectra could be detected. The results are discussed with comparison to charge transfer multiplet calculations. Our results emphasize that the lighter and heavier RNiO(3) compounds are very similar from the point of view of their local electronic and magnetic state despite the strong change of the metal-to-insulator transition temperature.

High-pressure synthesis and neutron diffraction investigation of the crystallographic and magnetic structure of TeNiO3 perovskite.

TeNiO(3) has been prepared under moderate pressure conditions (3.5 GPa), starting from a reactive TeO(2) and Ni(OH)(2) mixture contained in a sealed platinum capsule under the reaction conditions (850 °C for 2 h). The sample has been studied by neutron powder diffraction (NPD) data and magnetization measurements. TeNiO(3) crystallizes in an orthorhombically-distorted perovskite structure (space group Pnma) with the unit cell parameters a = 5.9588(1) Å, b = 7.5028(1) Å and c = 5.2143(1) Å. The NiO(6) octahedral network is extremely tilted, shaping a trigonal-pyramidal environment for the Te, where it is effectively coordinated to three oxygen atoms at Te-O distances of 1.92 Å. Below T(N) ≈ 130 K, it experiences an antiferromagnetic ordering, as demonstrated by susceptibility and NPD measurements. Above the Néel temperature, a paramagnetic moment of 3.24(1) µ(B)/f.u. and θ(Weiss) = -199(1) K are obtained from the reciprocal susceptibility. Below T(N), the magnetic reflections observed in the neutron patterns can be indexed with a propagation vector k = 0. The magnetic structure corresponds to the magnetic mode G(y)F(z). The magnetic moments are oriented along the y-direction, with a canting along the z-axis. This ferromagnetic component explains the weak ferromagnetism observed in the magnetization isotherms; the infrequent shape of the magnetization cycles suggests a metamagnetic transition below 0.2 T. At T = 2.5 K, the ordered magnetic moment for the Ni(2+) ions is 1.88(5) µ(B) for the G(y) mode and 0.9(2) µ(B) for the F(x) mode.

Study of the valence state and electronic structure in Sr(2)FeMO(6) (M = W, Mo, Re and Sb) double perovskites.

The knowledge of the oxidation state of the transition metal cations in Sr(2)FeMO(6) (M = W, Mo, Re and Sb) double perovskites is of paramount importance to understand their appealing magnetoresistive or magnetic properties. We present a systematic investigation of the valences of Fe, W, Mo, Re and Sb cations in these perovskites using three different and complementary techniques of analysis. We have used a diffraction method, neutron powder diffraction (NPD), coupled with the bond-valence model; and two spectroscopy methods, X-ray photoemission spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). These two techniques are also complementary since XPS analyses the surface of the samples whereas XAS probes the bulk material. The analysis of the Fe K-edge spectra of the four samples shows a clear shift of the Fe K-edge as the valence of iron increases in the sequence M = W, Mo, Re and Sb. In addition, XANES pre-edge structures unveil a progressive reduction in the occupancy level of the Fe-3d band as the oxidation state of iron increases along the sequence M = W, Mo, Re and Sb. Finally, XANES computations have determined the electronic structures of Sr(2)FeWO(6), Sr(2)FeMoO(6), Sr(2)FeReO(6) and Sr(2)FeSbO(6).

Slow dynamics in hard condensed matter: a case study of the phase separating system NdNiO(3).

We report the time dependent response of electrical resistivity in the non-magnetic perovskite oxide NdNiO(3) in its phase separated state and provide a physical explanation of the observations. We also model the system and make an accurate Monte Carlo simulation of the observed behavior. While cooling, a phase separation takes place in the system below its metal-insulator transition temperature and in this state the material exhibits various dynamical phenomena such as relaxation of resistivity, dependence of resistivity on cooling rate and rejuvenation of the material after ageing. These phenomena signal that the phase separated state of NdNiO(3) is not in thermodynamic equilibrium, and we conjecture that it consists of supercooled paramagnetic metallic and antiferromagnetic insulating phases. The supercooled phases are metastable and they switch over to the insulating equilibrium state stochastically, and this can account for the slow dynamics observed in our system. We also verify the predictive power of our model by simulating the result of a new experiment and confirming it by actual measurements.

High-pressure synthesis of the double perovskite Sr(2)FeMoO(6): increment of the cationic ordering and enhanced magnetic properties.

The double perovskite Sr(2)FeMoO(6) has been prepared in polycrystalline form by high-pressure methods, starting from a precursor developed via a citrate technique, containing an elevated degree of anti-site disordering. The application of high external pressure (2 GPa) to Sr(2)FeMoO(6) promotes the long distance Fe/Mo cationic order, due to the smaller lattice volume of the ordered sample. Both the disordered perovskite obtained at ambient pressure and the sample synthesized under high-pressure methods have been characterized by means of x-ray diffraction, neutron powder diffraction and magnetic measurements. The magnetic properties of the two oxides have been compared; the specimen prepared under high pressure not only presents an improved cationic ordering, but also displays a superior saturation magnetization and a sharpener ferromagnetic transition at a significantly high temperature of 430 K.

Evidence of kinetically arrested supercooled phases in the perovskite oxide NdNiO(3).

We report the time and temperature dependent response of thermopower in the non-magnetic perovskite oxide NdNiO(3). We find that on cooling below the metal-insulator transition temperature the system evolves into a phase separated state which consists of supercooled metallic and insulating phases. This phase separated state exhibits out of equilibrium features, such as cooling rate dependence and time dependence. The existence of these dynamical features is attributed to the transformation of supercooled metallic phases to the insulating state. On cooling, a small fraction of the supercooled phases get kinetically arrested in a glassy state and these supercooled phases remain in that state down to low temperature. In the heating cycle the arrested states de-arrest above 150 K and this results in the reappearance of time dependent features.

On the evolution of the DyNiO3 perovskite across the metal-insulator transition though neutron diffraction and Mössbauer spectroscopy studies.

The structural changes of polycrystalline DyNiO3 perovskite across the metal-insulator transition (TMI = 564 K) have been studied by high resolution neutron diffraction techniques together with Mössbauer spectroscopy, in a sample doped with 1.5 at.% 57Fe. In the insulating (semi-conducting) regime, below T(MI), the perovskite is monoclinic, space group (SG) P21/n, and the crystal structure contains two chemically different Ni1 and Ni2 cations, as a result of the charge disproportionation of Ni3+ cations. The beta parameter, characterizing the low-temperature monoclinic distortion, is smaller than 90.04 degrees for T < TMI, indicating a strongly pseudo-orthorhombic symmetry, although the internal monoclinic symmetry, implying the splitting and shifts of oxygen positions around the two Ni sites is perfectly detected by neutrons. Above TMI, DyNiO3 becomes orthorhombic, SG Pbnm. Upon heating across TMI, there is an abrupt convergence of the two sets (Ni1 and Ni2) of three Ni-O bond lengths, in the monoclinic-insulating phase, to three unique Ni-O distances in the orthorhombic-metallic phase upon entering the metallic region. The 57Fe Mössbauer spectra of an iron-doped (1.5 at.%) DyNiO3 sample recorded in the insulating, paramagnetic temperature range (TN < T < TMI) are discussed by supposing that the Fe3+ probe cations replace nickel in the two octahedral Ni1 and Ni2 sites. Electric field gradient calculations have shown that the 57Fe hyperfine parameters of Fe1 and Fe2 subspectra reflect a specificity of local structure corresponding to large (Ni1O6) and small (Ni2O6) octahedra. At T > TMI, the 57Fe spectrum gives clear evidence for the formation of an unique state for iron probe atoms and could, therefore, imply that the charge disproportionation in the (NiO6) subarray completely vanishes at the insulator-->metal transition.

Evolution of the crystal structure of RVO3 (R = La, Ce, Pr, Nd, Tb, Ho, Er, Tm, Yb, Lu, Y) perovskites from neutron powder diffraction data.

RVO3 perovskites have been prepared in the widest range of R (3+) ionic size, from LaVO3 to LuVO3. Pure polycrystalline samples have been obtained by a citrate technique leading to reactive RVO4 precursors, followed by thermal treatments in a reducing H2/N2 (15/85%) flow to stabilize V(3+) cations. These oxides have been studied at room temperature by high-resolution neutron powder diffraction to follow the evolution of the crystal structures along the series. The distortion of the orthorhombic perovskite (space group Pbnm), characterized by the tilting angle of the VO6 octahedra, progressively increases from La to Lu due to simple steric factors. Additionally, all of the perovskites show a subtle distortion of the VO6 octahedra which significantly increases from La to Tb, and then slightly decreases for the last terms of the series. The stability of the crystal structure is also discussed in light of bond-valence arguments.

High-pressure synthesis and study of the crystal and magnetic structure of the distorted SeNiO3 and SeMnO3 perovskites.

We describe the preparation of SeMO(3) (M = Ni, Mn) under high pressure conditions (3.5 GPa), starting from reactive H(2)SeO(3) and MO mixtures, contained in sealed gold capsules under the reaction conditions 850 degrees C for 1 h. The polycrystalline samples have been studied by neutron powder diffraction (NPD) data and magnetization measurements. SeMO(3) (M = Ni, Mn) are orthorhombically distorted perovskites (space group Pnma). Below T(N) approximately 104 K (M = Ni) and T(N) approximately 53.5 K (M = Mn) these oxides experience an antiferromagnetic ordering, as demonstrated by susceptibility and NPD measurements. The magnetic reflections observed in the neutron patterns can be indexed with a propagation vector k = 0. Both compounds present the same magnetic structure, which is given by the basis vector (0, 0, A(z)). It can be described as antiferromagnetic (010) layers of magnetic moments lying along the c direction, which are antiferromagnetically coupled along the b direction. For the Ni(2+) ions, the ordered magnetic moment at T = 2.3 K is 2.11(3) micro(B), whereas for Mn(2+) at T = 2.6 K, |m| = 4.64(2) micro(B), consistent with the electronic configurations te (Ni(2+)) and te (Mn(2+)).

Finding universal correlations between cationic disorder and low field magnetoresistance in FeMo double perovskite series.

We search for general patterns that explain the low field magnetoresistance at low temperatures in the system A(2-x)A'xFeMoO6. The observed linear dependence of the low field magnetoresistance with the saturation magnetization for the series is related to the antisite disorder at the Fe and Mo sites. This is explained in terms of a spin dependent crossing of intragranular barriers originated from the presence of antiferromagnetic SrFeO3 patches that naturally develop when antisite disorder occurs in the double perovskite. The presence of a moderate level of antisite disorder is at the very root of low field magnetoresistance although effects such as disorder distribution, connectivity, or morphology add their contribution.

Evolution of the Jahn-Teller distortion of MnO6 octahedra in RMnO3 perovskites (R = Pr, Nd, Dy, Tb, Ho, Er, Y): a neutron diffraction study.

Stoichiometric RMnO3 perovskites have been prepared in the widest range of R3+ ionic sizes, from PrMnO3 to ErMnO3. Soft-chemistry procedures have been employed; inert-atmosphere annealings were required to synthesize the materials with more basic R cations (R = Pr, Nd), in order to minimize the unwanted presence of Mn4+. On the contrary, annealings in O2 flow were necessary to stabilize the perovskite phases for the last terms of the series, HoMnO3, ErMnO3, and YMnO3, thus avoiding or minimizing the formation of competitive hexagonal phases with the same stoichiometry. The samples have been investigated at room temperature by high-resolution neutron powder diffraction to follow the evolution of the crystal structures along the series. The results are compared with reported data for LaMnO3. The distortion of the orthorhombic perovskite (space group Pbnm), characterized by the tilting angle of the MnO6 octahedra, progressively increases from Pr to Er due to simple steric factors. Additionally, all of the perovskites show a distortion of the MnO6 octahedra due to the orbital ordering characteristic of the Jahn-Teller effect of Mn3+ cations. The degree of orbital ordering slightly increases from La to Tb and then remains almost unchanged for the last terms of the series. The stability of the crystal structure is also discussed in light of bond-valence arguments.