Internal-strain mediated coupling between polar Bi and magnetic Mn ions in the defect-free quadruple-perovskite BiMn3_3Mn4_4O12_{12}

By means of neutron powder diffraction, we investigated the effect of the polar Bi$^{3+}$ ion on the magnetic ordering of the Mn$^{3+}$ ions in BiMn$_3$Mn$_4$O$_{12}$, the counterpart with \textit{quadruple} perovskite structure of the \textit{simple} perovskite BiMnO$_3$. The data are consistent with a \textit{noncentrosymmetric} spacegroup $Im$ which contrasts the \textit{centrosymmetric} one $I2/m$ previously reported for the isovalent and isomorphic compound LaMn$_3$Mn$_4$O$_{12}$, which gives evidence of a Bi$^{3+}$-induced polarization of the lattice. At low temperature, the two Mn$^{3+}$ sublattices of the $A'$ and $B$ sites order antiferromagnetically (AFM) in an independent manner at 25 and 55 K, similarly to the case of LaMn$_3$Mn$_4$O$_{12}$. However, both magnetic structures of BiMn$_3$Mn$_4$O$_{12}$ radically differ from those of LaMn$_3$Mn$_4$O$_{12}$. In BiMn$_3$Mn$_4$O$_{12}$ the moments $\textbf{M}_{A'}$ of the $A'$ sites form an anti-body AFM structure, whilst the moments \textbf{M}$_{B}$ of the $B$ sites result from a large and \textit{uniform} modulation $\pm \textbf{M}_{B,b}$ along the b-axis of the moments \textbf{M}$_{B,ac}$ in the $ac$-plane. The modulation is strikingly correlated with the displacements of the Mn$^{3+}$ ions induced by the Bi$^{3+}$ ions. Our analysis unveils a strong magnetoelastic coupling between the internal strain created by the Bi$^{3+}$ ions and the moment of the Mn$^{3+}$ ions in the $B$ sites. This is ascribed to the high symmetry of the oxygen sites and to the absence of oxygen defects, two characteristics of quadruple perovskites not found in simple ones, which prevent the release of the Bi$^{3+}$-induced strain through distortions or disorder. This demonstrates the possibility of a large magnetoelectric coupling in proper ferroelectrics and suggests a novel concept of internal strain engineering for multiferroics design.Comment: 9 pages, 7 figures, 5 table

Magnetoelastic coupling in RETiO3 (RE = La, Nd, Sm, Gd, Y)

A detailed analysis of the crystal structure in RETiO3 with RE = La, Nd, Sm, Gd, and Y reveals an intrinsic coupling between orbital degrees of freedom and the lattice which cannot be fully attributed to the structural deformation arising from bond-length mismatch. The TiO6 octahedra in this series are all irregular with the shape of the distortion depending on the RE ionic radius. These octahedron distortions vary more strongly with temperature than the tilt and rotation angles. Around the Ti magnetic ordering all compounds exhibit strong anomalies in the thermal-expansion coefficients, these anomalies exhibit opposite signs for the antiferromagnetic and ferromagnetic compounds. Furthermore the strongest effects are observed in the materials close to the magnetic cross-over from antiferromagnetic to ferromagnetic order

Crystal and magnetic structure of La_{1-x}Sr_{1+x}MnO_{4} : role of the orbital degree of freedom

The crystal and magnetic structure of La_{1-x}Sr_{1+x}MnO_4 (0<x<0.7) has been studied by diffraction techniques and high resolution capacitance dilatometry. There is no evidence for a structural phase transition like those found in isostructural cuprates or nickelates, but there are significant structural changes induced by the variation of temperature and doping which we attribute to a rearrangement of the orbital occupation.Comment: 8 pages, 6 figures, submitted to PR

Influence of low energy argon plasma treatment on the moisture barrier performance of hot wire-CVD grown SiNx multilayers

The reliability and stability are key issues for the commercial utilization of organic photovoltaic devices based on flexible polymer substrates. To increase the shelf-lifetime of these devices, transparent moisture barriers of silicon nitride (SiNx) films are deposited at low temperature by hot wire CVD (HW-CVD) process. Instead of the conventional route based on organic/inorganic hybrid structures, this work defines a new route consisting in depositing multilayer stacks of SiNx thin films, each single layer being treated by argon plasma. The plasma treatment allows creating smoother surface and surface atom rearrangement. We define a critical thickness of the single layer film and focus our attention on the effect of increasing the number of SiNx single-layers on the barrier properties. A water vapor transmission rate (WVTR) of 2 x 10-4 g/(m2 day) is reported for SiNx multilayer stack and a physical interpretation of the plasma treatment effect is given.Direction des Relations Extérieures, Ecole PolytechniquePICS (French–Portuguese No. 5336) projec

Flexible organic–inorganic hybrid layer encapsulation for organic opto-electronic devices

In this work we produce and study the flexible organic–inorganic hybrid moisture barrier layers for the protection of air sensitive organic opto-electronic devices. The inorganic amorphous silicon nitride layer (SiNx:H) and the organic PMMA [poly (methyl methacrylate)] layer are deposited alternatingly by using hot wire chemical vapor deposition (HW-CVD) and spin-coating techniques, respectively. The effect of organic–inorganic hybrid interfaces is analyzed for increasing number of interfaces. We produce highly transparent (∼80% in the visible region) hybrid structures. The morphological properties are analysed providing a good basis for understanding the variation of the water vapor transmission rate (WVTR) values. A minimum WVTR of 4.5 × 10−5g/m2day is reported at the ambient atmospheric conditions for 7 organic/inorganic interfaces. The hybrid barriers show superb mechanical flexibility which confirms their high potential for flexible applications.The authors would like to thank Dr. J.C. Vanel for help in electrical characterizations used in this study. The first author (S.M) acknowledges the financial support from Direction des Relations Extérieures, Ecole Polytechnique during his thesis

The effect of argon plasma treatment on the permeation barrier properties of silicon nitride layers

In this work we produce and study silicon nitride (SiNx) thin films deposited by Hot Wire Chemical Vapor Depo- sition (HW-CVD) to be used as encapsulation barriers for flexible organic photovoltaic cells fabricated on poly- ethylene terephthalate (PET) substrates in order to increase their shelf lifetime. We report on the results of SiNx double-layers and on the equivalent double-layer stack where an Ar-plasma surface treatment was performed on the first SiNx layer. The Ar-plasma treatment may under certain conditions influences the structure of the interface between the two subsequent layers and thus the barrier properties of the whole system. We focus our attention on the effect of plasma treatment time on the final barrier properties. We assess the encapsulation barrier properties of these layers, using the calcium degradation test where changes in the electrical conductance of encapsulated Ca sensors are monitored with time. The water vapor transmission rate (WVTR) is found to be ~3 × 10−3 g/m2·day for stacked SiNx double-layer with 8 min Ar plasma surface treatment.FCT - CNRS PICS (French–Portuguese no: 5336) projectDirection des Relations Extérieures, Ecole Polytechniqu

Effect of argon ion energy on the performance of silicon nitridemultilayer permeation barriers grown by hot-wire CVD on polymers

One of the authors (S.M.) acknowledges Direction des Relations Extérieures of Ecole Polytechnique for financial support.Permeation barriers for organic electronic devices on polymer flexible substrates were realized by combining stacked silicon nitride (SiNx) single layers (50 nm thick) deposited by hot-wire chemical vapor deposition process at low-temperature (~100°C) with a specific argon plasma treatment between two successive layers. Several plasma parameters (RF power density, pressure, treatment duration) as well as the number of single layers have been explored in order to improve the quality of permeation barriers deposited on polyethylene terephthalate. In this work, maximumion energy was highlighted as the crucial parameter making it possible to minimize water vapor transmission rate (WVTR), as determined by the electrical calcium test method, all the other parameters being kept fixed. Thus fixing the plasma treatment duration at 8 min for a stack of two SiNx single layers, a minimum WVTR of 5 × 10−4 g/(m2 day), measured at room temperature, was found for a maximum ion energy of ~30 eV. This minimum WVTR value was reduced to 7 × 10−5 g/(m2 day) for a stack of five SiNx single layers. The reduction in the permeability is interpreted as due to the rearrangement of atoms at the interfaces when average transferred ion energy to target atoms exceeds threshold displacement energy.The authors are grateful to Dr. R. Cortes (PMC, Ecole Polytechnique) for XRR analysis, to Dr. P. Chapon (HORIBA Jobin Yvon) for GD-OES analysis and Dr. J. Leroy (CEA Saclay) for XPS analysis. This work was partly supported by the PICS (FrenchPortuguese) project No. 5336. One of the authors (S.M.) acknowledges Direction des Relations Extérieures of Ecole Polytechnique for financial support

Crystal and magnetic structure of LaTiO3 : evidence for non-degenerate t2gt_{2g}-orbitals

The crystal and magnetic structure of LaTiO3 ~ has been studied by x-ray and neutron diffraction techniques using nearly stoichiometric samples. We find a strong structural anomaly near the antiferromagnetic ordering, T$_N$=146 K. In addition, the octahedra in LaTiO3 exhibit an intrinsic distortion which implies a splitting of the t2g-levels. Our results indicate that LaTiO3 should be considered as a Jahn-Teller system where the structural distortion and the resulting level splitting are enhanced by the magnetic ordering.Comment: 4 pages 5 figure

Structural and Magnetic Instabilities of La2−x_{2-x}Srx_xCaCu2_2O6_6

A neutron scattering study of nonsuperconducting La$_{2-x}$Sr$_x$CaCu$_2$O$_6$ (x=0 and 0.2), a bilayer copper oxide without CuO chains, has revealed an unexpected tetragonal-to-orthorhombic transition with a doping dependent transition temperature. The predominant structural modification below the transition is an in-plane shift of the apical oxygen. In the doped sample, the orthorhombic superstructure is strongly disordered, and a glassy state involving both magnetic and structural degrees of freedom develops at low temperature. The spin correlations are commensurate.Comment: published versio

Correlations of structural, magnetic, and dielectric properties of undoped and doped CaCu3Ti4O12

The present work reports synthesis, as well as a detailed and careful characterization of structural, magnetic, and dielectric properties of differently tempered undoped and doped CaCu3Ti4O12 (CCTO) ceramics. For this purpose, neutron and x-ray powder diffraction, SQUID measurements, and dielectric spectroscopy have been performed. Mn-, Fe-, and Ni-doped CCTO ceramics were investigated in great detail to document the influence of low-level doping with 3d metals on the antiferromagnetic structure and dielectric properties. In the light of possible magnetoelectric coupling in these doped ceramics, the dielectric measurements were also carried out in external magnetic fields up to 7 T, showing a minor but significant dependence of the dielectric constant on the applied magnetic field. Undoped CCTO is well-known for its colossal dielectric constant in a broad frequency and temperature range. With the present extended characterization of doped as well as undoped CCTO, we want to address the question why doping with only 1% Mn or 0.5% Fe decreases the room-temperature dielectric constant of CCTO by a factor of ~100 with a concomitant reduction of the conductivity, whereas 0.5% Ni doping changes the dielectric properties only slightly. In addition, diffraction experiments and magnetic investigations were undertaken to check for possible correlations of the magnitude of the colossal dielectric constants with structural details or with magnetic properties like the magnetic ordering, the Curie-Weiss temperatures, or the paramagnetic moment. It is revealed, that while the magnetic ordering temperature and the effective moment of all investigated CCTO ceramics are rather similar, there is a dramatic influence of doping and tempering time on the Curie-Weiss constant.Comment: 10 pages, 11 figure