Metal-insulator transition in Nd(1-x)Eu(x)NiO(3) compounds

Polycrystalline Nd(1-x)Eu(x)NiO(3) (0≤x≤0.5) compounds were synthesized in order to investigate the character of the metal-insulator (MI) phase transition in this series. Samples were prepared through the sol-gel route and subjected to heat treatments at ∼1000 °C under oxygen pressures as high as 80 bar. X-ray diffraction (XRD) and neutron powder diffraction (NPD), electrical resistivity ρ(T), and magnetization M(T) measurements were performed on these compounds. The NPD and XRD results indicated that the samples crystallize in an orthorhombic distorted perovskite structure, space group Pbnm. The analysis of the structural parameters revealed a sudden and small expansion of ∼0.2% of the unit cell volume when electronic localization occurs. This expansion was attributed to a small increase of ∼0.003 Å of the average Ni-O distance and a simultaneous decrease of ∼-0.5° of the Ni-O-Ni superexchange angle. The ρ(T) measurements revealed a MI transition occurring at temperatures ranging from T(MI)∼193 to 336 K for samples with x = 0 and 0.50, respectively. These measurements also show a large thermal hysteresis in NdNiO(3) during heating and cooling processes, suggesting a first-order character of the phase transition at T(MI). The width of this thermal hysteresis was found to decrease appreciably for the sample Nd(0.7)Eu(0.3)NiO(3). The results indicate that cation disorder associated with increasing substitution of Nd by Eu is responsible for changing the first-order character of the transition in NdNiO(3).