Evidence for centrosymmetry breaking and multiferroic properties in the A-site ordered quadruple perovskite YMn$_3$Mn$_4$O$_{12}$

Abstract

By means of single-crystal X-ray diffraction we have revealed the breaking of centrosymmetry when lowering the temperature under T$_s$ = 200 K concomitantly with the setting of a commensurate superstructure in the small A-site quadruple perovskite YMn$_3$Mn$_4$O$_{12}$. This results is in agreement with all data already reported for this compounds and solve the previous inconsistency about the Yttrium position. The superstructure is characterized by the appearing of satellite reflections in the single crystal pattern, consistent with an I-centered pseudo-orthorhombic commensurate supercell with $a \approx \sqrt{a_F} = 10.4352(7)$ \AA, $b \approx 2b_F = 14.6049(9)$ \AA, $c \approx \sqrt{c_F} = 10.6961(7)$ \AA and $\beta = 90.110(3)^\circ$, where F stands for the "fundamental" high-temperature cell ($a_F \approx c_F \approx 7.45$ \AA, $b_F \approx 7.34$ \AA, and $\beta \approx 90^\circ$). The space-group was unequivocally found to be Ia, which is non polar, thus allowing for a non-zero polarization in the material. We then have investigated in detail the pyrocurrent, transport, dielectric and the DC and AC magnetic properties of polycrystalline sample of YMn$_3$Mn$_4$O$_{12}$ over a wide temperature range. These measurements clearly highlight several critical temperatures in the material and correlation between the different orders: i) the centrosymmetry is broken at high temperature (T$_S$ = 200K), ii) then the long-range magnetic order of B-sites occurs at T$_{N,B}$ = 108 K and at this same temperature the compound enters in an insulating dielectric state. iii) Finally, a remnant polarization is stabilized concomitantly with a magnetic anomaly at T* = 70 K. We propose that YMn$_3$Mn$_4$O$_{12}$ is a peculiar magnetic ferroelectric in which the polar state is driven by short-range magnetic order.