BiFeO3 ceramics were investigated by means of infrared reflectivity and time domain THz transmission spectroscopy at temperatures 20 -950 K and the magnetodielectric effect was studied at 10 -300 K with the magnetic field up to 9 T. Below 175 K, the sum of polar phonon contributions into the permittivity corresponds to the value of measured permittivity below 1 MHz. At higher temperatures, a giant low-frequency permittivity was observed, obviously due to the enhanced conductivity and possible Maxwell-Wagner contribution. Above 200 K the observed magnetodielectric effect is caused essentially through the combination of magnetoresistance and the Maxwell-Wagner effect, as recently predicted by Catalan (Appl. Phys. Lett. 88, 102902 (2006)). Since the magnetodielectric effect does not occur due to a coupling of polarization and magnetization as expected in magnetoferroelectrics, we call it improper magnetodielectric effect. Below 175 K the magnetodielectric effect is by several orders of magnitude lower due to the decreased conductivity. Several phonons exhibit gradual softening with increasing temperature, which explains the previously observed highfrequency permittivity increase on heating. The observed non-complete phonon softening seems to be the consequence of the first-order nature of the ferroelectric transition.
X-ray diffraction, dynamical mechanical analysis and infrared reflectivity
studies revealed an antiferrodistortive phase transition in EuTiO3 ceramics.
Near 300K the perovskite structure changes from cubic Pm-3m to tetragonal
I4/mcm due to antiphase tilting of oxygen octahedra along the c axis (a0a0c- in
Glazer notation). The phase transition is analogous to SrTiO3. However, some
ceramics as well as single crystals of EuTiO3 show different infrared
reflectivity spectra bringing evidence of a different crystal structure. In
such samples electron diffraction revealed an incommensurate tetragonal
structure with modulation wavevector q ~ 0.38 a*. Extra phonons in samples with
modulated structure are activated in the IR spectra due to folding of the
Brillouin zone. We propose that defects like Eu3+ and oxygen vacancies strongly
influence the temperature of the phase transition to antiferrodistortive phase
as well as the tendency to incommensurate modulation in EuTiO3.Comment: PRB, in pres
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