We show that low field magnetoelectric (ME) properties of helimagnets Ba0.5Sr1.5Zn2(Fe1-xAlx)12O22 can be efficiently tailored by Al-substitution level. As x increases, the critical magnetic field for switching electric polarization is systematically reduced from ~1 T down to ~1 mT, and the ME susceptibility is greatly enhanced to reach a giant value of 2.0 x 10^4 ps/m at an optimum x = 0.08. We find that control of nontrivial orbital moment in the octahedral Fe sites through the Al-substitution is crucial for fine tuning of magnetic anisotropy and obtaining the conspicuously improved ME characteristics.
The key physical property of multiferroic materials is the existence of a coupling between magnetism and polarization, i.e. magnetoelectricity. The origin and manifestations of magnetoelectricity can be very different in the available plethora of multiferroic systems, with multiple possible mechanisms hidden behind the phenomena. In this Review, we describe the fundamental physics that causes magnetoelectricity from a theoretical viewpoint. The present review will focus on the main stream physical mechanisms in both single phase multiferroics and magnetoelectric heterostructures. The most recent tendencies addressing possible new magnetoelectric mechanisms will also be briefly outlined.
Multiferroic BaMnF$_4$ powder were prepared by hydrothermal method. Hysteretic field dependent magnetization curve at 5 K confirms the weak ferromagnetism aroused from the canted antiferromagnetic spins by magnetoelectric coupling. The blocking temperature of 65 K for exchange bias coincides well with the peak at 65 K in the zero-field cooled temperature-dependent magnetization curve, which has been assigned to the onset temperature of two-dimensional antiferromagnetism. An upturn kink of exchange field and coercivity with decreasing temperature was observed from 40 K to 20 K, which is consistent with the two-dimensional to three-dimensional antiferromagnetic transition at Neel temperature (~26 K). In contrast to the conventional mechanism of magnetization pinned by interfacial exchange coupling in multiphases, the exchange bias in BaMnF$_4$ is argued to be a bulk effect in single phase, due to the magnetization pinned by the polarization through magnetoelectric coupling.
The intrinsic noncollinear spin patterns in rare-earth pyrochlore are physically interesting, hosting many emergent properties, e.g. spin ice and monopole-type excitation. Recently, the magnetic monopole excitation of spin ice systems was predicted to be magnetoelectric active, while rare experimental works have directly confirmed this scenario. In this work, we performed systematic experimental investigation on the magnetoelectricity of Dy$_2$Ti$_2$O$_7$ by probing the ferroelectricity, spin dynamics, and dielectric behaviors. Two ferroelectric transitions at $T_{c1}$=25 K and $T_{c2}$=13 K have been observed. Remarkable magnetoelectric coupling is identified below the lower transition temperature, with a significant suppression of the electric polarization upon applied magnetic field. It is surprised that the lower ferroelectric transition temperature just coincides with the Ising-spin paramagnetic transition point, below which the quasi-particle-like monopoles are populated, indicating implicit correlation between electric dipoles and spin moments. The possible magnetoelectric mechanisms have also been discussed although a decent theory remains unavailable up to date. Our results will stimulate more investigations to explore multiferroicity in these spin ice systems and other frustrated magnets.
Trirutile-type LiFe$_2$F$_6$ is a charge-ordered material with Fe$^{2+}$/Fe$^{3+}$ configuration. Here its physical properties, including magnetism, electronic structure, phase transition, and charge ordering, are studied theoretically. On one hand, the charge ordering leads to improper ferroelectricity with a large polarization. On the other hand, its magnetic ground state can be tuned from the antiferromagnetic to ferrimagnetic by moderate compressive strain. Thus, LiFe$_2$F$_6$ can be a rare multiferroic with both large magnetization and polarization. Most importantly, since the charge ordering is the common ingredient for both ferroelectricity and magnetization, the net magnetization may be fully switched by flipping the polarization, rendering intrinsically strong magnetoelectric effect and desirable function.
Type-II multiferroic materials, in which ferroelectric polarization is induced by inversion non-symmetric magnetic order, promise new and highly efficient multifunctional applications based on the mutual control of magnetic and electric properties. Although this phenomenon has to date been limited to low temperatures, here we report a giant pressure-dependence of the multiferroic critical temperature in CuBr$_2$. At 4.5 GPa, $T_mathrm{C}$ is enhanced from 73.5 to 162 K, to our knowledge the highest value yet reported for a non-oxide type-II multiferroic. This growth shows no sign of saturating and the dielectric loss remains small under these high pressures. We establish the structure under pressure and demonstrate a 60% increase in the two-magnon Raman energy scale up to 3.6 GPa. First-principles structural and magnetic energy calculations provide a quantitative explanation in terms of dramatically pressure-enhanced interactions between CuBr$_2$ chains. These large, pressure-tuned magnetic interactions motivate structural control in cuprous halides as a route to applied high-temperature multiferroicity.