Room-temperature large magnetoelectricity in a transition metal doped ferroelectric perovskite

There is increasing interest in novel magnetoelectric (ME) materials that exhibit robust ME coupling at room temperature (RT) for advanced memory, energy, spintronics, and other multifunctional device applications, by making use of the ability to control polarization with a magnetic field and/or magnetization via an electric field. Obtaining ME materials with strong ME coupling, understanding the origin, and manipulating its processing along with composition to realize large ME coefficients at RT constitute an important step in multiferroic research. To address this, we have investigated the multiferroic and ME properties of Ni-doped $\mathrm{Pb}({\mathrm{Zr}}_{0.20}{\mathrm{Ti}}_{0.80}){\mathrm{O}}_{3}$ (PZT). We find that the ferroelectric $({T}_{\mathrm{C}}\ensuremath{\sim}700\phantom{\rule{0.16em}{0ex}}\mathrm{K})$ and weak ferromagnetic (\ensuremath{\sim}602 K) phase transitions of Ni-doped PZT are well above room temperature (RT), leading to a strong ME coupling coefficient (${\ensuremath{\alpha}}_{E,31}$) of $11.7\phantom{\rule{0.16em}{0ex}}\mathrm{mV}\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{--1}\phantom{\rule{0.16em}{0ex}}{\mathrm{Oe}}^{--1}$ (${H}_{\mathrm{ac}}=1\phantom{\rule{0.16em}{0ex}}\mathrm{Oe}$ and $f=1\phantom{\rule{0.16em}{0ex}}\mathrm{kHz}$). While x-ray diffraction suggests a single-phase material, high-resolution transmission electron microscopy reveals regions with and without Ni present; thus magnetoelectric coupling between two phases is possible. First-principles calculations suggest the $(\mathrm{N}{\mathrm{i}}_{\mathrm{Pb}}{)}^{\ifmmode\times\else\texttimes\fi{}}$ defect is likely to be responsible for the experimental observed magnetism and ME coupling in Ni-doped PZT. We further demonstrate that Ni-doped PZT exhibits low loss tangent, low leakage current, large saturation polarization, and weak ferromagnetism. Ultimately, our work demonstrates that Ni-doped PZT is a cost-effective RT multiferroic with strong ME coupling.