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

MAGNETIC BEHAVIOUR AND PHASE TRANSITION IN [ThCu3] (Mn4)O12

Le composé [ThCu3] (Mn4)o12 appartient à la série des oxydes [AC3] (B4)O12 de structure pérovskite dans lesquels les sites [A] icosaédriques sont occupés par les cations Th4+, les sites [C] plans-carrés par les cations Cu2+ et les sites (B) octaédriques par les cations Mn3+ et Mn4+ en proportions égales. Diverses mesures indiquent un comportement ferrimagnétique avec une température d'ordre TN = 430 K, une aimantation spontanée à 4,2 K de 9 µB/unité de formule et une transition à Tt = 180 K. La structure ferrimagnétique, déduite des expériences de diffraction neutronique est en accord avec les valeurs des interactions magnétiques tirées des mesures d'aimantation et de susceptibilité. La transition Tt a été étudiée par des mesures d'aimantation et de diffraction des rayons X. Elle est caractérisée par une variation thermique anormale du paramètre de maille et du moment magnétique, sans changement de la symétrie cristallographique et magnétique.The compound [ThCu3] (Mn4)O12 belongs to the series of [AC3] (B4) O12 perovskite-like oxides in which the icosahedral sites [A] are occupied by the Th4+ cations, the square planar sites [C] by the Cu2+ cations, and the octahedral sites (B) by the Mn3+ and Mn4+ cations in equal proportion. Previous measurements indicated a ferrimagnetic behavior with an ordering temperature TN= 430 K, a spontaneous magnetization of 9µB/formula unit at 4.2 K and a magnetic transition at Tt = 180 K. The ferrimagnetic structure, as determined from powder neutron diffraction data, is consistent with the values of magnetic interactions that can be estimated from magnetization and susceptibility measurements. The low temperature transition has been studied by magnetization measurements and X-Rays techniques. It seems to be of second order with anomalies in the cubic cell parameter and of the magnetic moments. No changes in cristallographic symmetry and magnetic structure are observed