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The crystal structures of europium niobate, EuNbO3, have been examined over a wide temperature range between 20 and 500 K using synchrotron X-ray diffraction. We have observed two successive structural phase transitions at 360 and 460 K. Below 350 K, EuNbO3 adopts an orthorhombic perovskite structure (space group Imma), which is characterized by NbO6 octahedral tilting about the pseudocubic two-fold axis. The result differs from previous reports in which EuNbO3 was assigned to a cubic aristotype (space group Pm 3 ¯ m) of perovskite at room temperature. At around 360 K, EuNbO3 undergoes a first-order phase transition to a tetragonal symmetry (space group I4/mcm) with the NbO6 octahedral tilting about the pseudocubic four-fold axis. As the temperature is further increased, the I4/mcm tetragonal phase changes into the Pm 3 ¯ m cubic aristotype at 460 K. The tetragonal-to-cubic transformation is characterized as a continuous phase transition.

We have studied electronic properties of perovskite oxyhydrides ATiO3–xHx (A = Ba, Sr). Epitaxial thin films of ATiO3–xHx with various hydride compositions, up to x = 0.58 for Ba and x = 0.45 for Sr, are prepared by the low-temperature CaH2 reduction of the corresponding oxide films deposited on (LaAlO3)0.3(SrAl0.5Ta0.5O3)0.7 (LSAT) substrates by pulsed laser deposition. Resistivity measurements for A = Sr show a metallic phase over a wide range of H– composition, implying a substantial stabilization of H 1s orbitals that should be distributed over O 2p orbitals. On the other hand, for A = Ba, a semiconducting behavior is seen up to ∼5–8% of H– substitution. Interestingly, a similar contrasting behavior is observed in a Nb-substituted BaTiO3 and SrTiO3, which suggests that a local cation–off centering in lightly doped Ba films creates in-gap states in the band structure (as opposed to the Sr films), hindering the electron transport.

We have prepared the oxyhydride perovskite EuTiO(3-x)H(x) (x ≤ 0.3) by a low temperature CaH2 reduction of pyrochlore Eu2Ti2O7 and perovskite EuTiO3. The reduced EuTiO(3-x)H(x) crystallizes in the ideal cubic perovskite (Pm3̅m), where O/H anions are randomly distributed. As a result of electron doping by the aliovalent anion exchange, the resistivity of EuTiO(3-x)H(x) shows metallic temperature dependence. Moreover, an antiferromagnetic-to-ferromagnetic transition is observed even when a small amount of hydride (x ∼ 0.07) is introduced. The Curie temperature TC of 12 K is higher than those of any other EuTiO3-derived ferromagnets. The ferromagnetism can be explained by the Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction between the Eu(2+) spins mediated by the itinerant Ti 3d electrons. The present study shows that controlling the oxide/hydride ratio is a versatile method to tune magnetic and transport properties.

The hydride reduction of a tetragonal layered perovskite LaSrCoO4 is known to yield orthorhombic LaSrCoO3H0.7 with a complete hydride/oxide order within the ab plane. In this study, epitaxial thin films of LaSrCoO4 with a-axis and c-axis orientations have been deposited on (100) and (001) LaSrAlO4 (LSAO) substrates, respectively, and allowed to react with hydride to convert into oxyhydrides. X-ray diffraction, secondary ion mass spectroscopy and thermal desorption spectroscopy experiments indicate that both films are topochemically reduced and can integrate hydride ions with a chemical composition close to that obtained for the powder. A significant reduction in the a-axis was observed for the a-axis oriented LaSrCoO3H0.7 film, indicating hydride/oxide order, as previously reported. In contrast, the c-axis oriented LaSrCoO3H0.7 film remains tetragonal, suggesting hydride/oxide disorder. These results demonstrate that strain engineering can lead to new materials with designed anion arrangement in mixed anion materials.

Lattice volume expansion or amorphization renders EuTiO3 ferromagnetic, although the stable phase of crystalline EuTiO3 is an antiferromagnet. The lattice volume expansion is induced into the crystalline EuTiO3 thin film by utilizing the lattice mismatch between the thin film and a substrate. The magnetization at low temperatures monotonically increases with an increase in lattice volume for the crystalline EuTiO3 thin film, coincident with the results of calculations based on the hybrid Hartree–Fock density functional approach. The ferromagnetic interaction between Eu2+ ions is enhanced by the amorphization as well; the amorphous EuTiO3 thin film becomes a ferromagnet, and the Curie temperature is higher for amorphous Eu2TiO4 than for its crystalline counterpart. The phenomenon, that is, the volume expansion- and amophization-induced ferromagnetism, is explained in terms of the competition between ferromagnetic and antiferromagnetic interactions among Eu2+ ions.

The crystal structures of europium niobate, EuNbO3, have been examined over a wide temperature range between 20 and 500 K using synchrotron X-ray diffraction. We have observed two successive structural phase transitions at 360 and 460 K. Below 350 K, EuNbO3 adopts an orthorhombic perovskite structure (space group Imma), which is characterized by NbO6 octahedral tilting about the pseudocubic two-fold axis. The result differs from previous reports in which EuNbO3 was assigned to a cubic aristotype (space group Pm 3 ¯ m) of perovskite at room temperature. At around 360 K, EuNbO3 undergoes a first-order phase transition to a tetragonal symmetry (space group I4/mcm) with the NbO6 octahedral tilting about the pseudocubic four-fold axis. As the temperature is further increased, the I4/mcm tetragonal phase changes into the Pm 3 ¯ m cubic aristotype at 460 K. The tetragonal-to-cubic transformation is characterized as a continuous phase transition.

Bulk EuTiO3 is known as a compound in which spin and soft phonon mode is strongly coupled. Recent theoretical study suggests that application of stress or formation of strain leads to a drastic change in magnetic and dielectric properties of EuTiO3 and that so-called multiferroic properties emerge under such a situation. In the present study, effect of strain induced by a substrate, on which EuTiO3 thin film is deposited, on the magnetic properties of the film has been experimentally examined. By using a pulsed laser deposition method, EuTiO3 thin film has been deposited on different kinds of substrate, i.e., LaAlO3, SrTiO3, and DyScO3; the lattice parameter of these compounds is smaller than, just the same as, and larger than that of EuTiO3, respectively. X-ray diffraction analysis confirms that the strain induced in the plane of as-deposited EuTiO3 thin films on different substrates is coincident with the lattice parameter of the substrate compounds. Also, all the as-deposited EuTiO3 thin films manifest elongation of lattice in a direction perpendicular to the film surface. Temperature dependence of magnetization indicates that all the thin films exhibit ferromagnetic behavior at low temperatures. The magnetization at 2 K under a magnetic field of 100 Oe is the highest for EuTiO3 on DyScO3 and the lowest for EuTiO3 on LaAlO3. The experimental result is coincident with the first-principles calculations which predict that ferromagnetic spin configuration becomes more stable as the lattice volume of EuTiO3is increased.

EuTiO3-xHx (x ≤ 0.3) is prepared by low temperature CaH2 reduction of Eu2Ti2O7 and EuTiO3 (475—650 °C, 2 d) and characterized by XRD and magnetic measurements.

Amorphous Eu${}_{2}$TiO${}_{4}$ and EuTiO${}_{3}$ have been studied by a combination of the Faraday effect in the visible region and polarization-dependent x-ray absorption spectroscopy at the Eu ${M}_{4,5}$ and ${L}_{2,3}$ edges to examine the role of Eu 4$f$-5$d$ exchange interactions on the ferromagnetic behavior. The bulk-sensitive x-ray absorption spectra (XAS) for Eu ${L}_{2,3}$ edges show that most of the europium ions are present as the divalent state in the amorphous Eu${}_{2}$TiO${}_{4}$ and EuTiO${}_{3}$. The Eu ${M}_{4,5}$ edge x-ray magnetic circular dichroism (XMCD) signals, measured for the amorphous Eu${}_{2}$TiO${}_{4}$, dramatically increase upon cooling through the Curie temperature (16 K) determined by a superconducting quantum interference device (SQUID) magnetometer. Sum-rule analysis of the XMCD at Eu ${M}_{4,5}$ edges measured at 10 K yields a 4$f$ spin magnetic moment of 6.6${\ensuremath{\mu}}_{\mathrm{B}}$ per Eu${}^{2+}$ ion. These results confirm that the ferromagnetic properties exclusively arise from 4$f$ spins of Eu${}^{2+}$. In addition, for both the amorphous Eu${}_{2}$TiO${}_{4}$ and EuTiO${}_{3}$, the temperature and magnetic-field dependence of Eu ${L}_{2,3}$ edge XMCD signals can be scaled with the corresponding magnetization measured by SQUID, indicating that the 5$d$ magnetic polarization of Eu${}^{2+}$ is involved in the process to cause the ferromagnetic interaction between Eu${}^{2+}$ ions. We further discuss the origin of ferromagnetism in the amorphous system on the basis of the energy diagram of Eu 4$f$ and 5$d$ levels deduced from the Faraday effect in the visible region. From the wavelength dependence of Faraday rotation angles of the amorphous EuO-TiO${}_{2}$ system in comparison with those of the divalent Eu chalcogenides as reported previously, it is found that the magnitude of crystal-field splitting of Eu 5$d$ levels in the former is on the same order as that in the latter, which explains an enhanced ferromagnetic exchange interaction between Eu 4$f$ and 5$d$ states.