Observation of spontaneous ferroelectric polarization reversal in multiferroic Mn{sub 1−x}Ni{sub x}WO{sub 4} (x ≈ 0.16)

In this Letter, we report the effect of replacing Mn{sup 2+} ions with Ni{sup 2+} on the ferroelectricity of multiferroic MnWO{sub 4} single crystals. When the amount of substitution was close to 16%, the sign of ferroelectric polarization spontaneously became negative with respect to initial dc poling field at a few degrees below T{sub C}. Neutron diffraction intensities revealed a sudden change in the underlying spiral spin ordering that occurred coincidentally with the observed sign reversal. This unusual behavior in zero magnetic fields suggests that strong competitions between the two different magnetic ions may provide an efficient route to manipulation of existing multiferroics.