A stable rhombohedral phase in ferroelectric Hf(Zr)₁₊O₂ capacitor with ultralow coercive field

Hafnium oxide-based ferroelectric materials are promising candidates for next-generation nanoscale devices because of their ability to integrate into silicon electronics. However, the intrinsic high coercive field of the fluorite-structure oxide ferroelectric devices leads to incompatible operating voltage and limited endurance performance. We discovered a complementary metal-oxide semiconductor (CMOS)-compatible rhombohedral ferroelectric Hf(Zr)₁₊O₂ material rich in hafnium-zirconium [Hf(Zr)]. X-ray diffraction combined with scanning transmission electron microscopy reveals that the excess Hf(Zr) atoms intercalate within the hollow sites. We found that the intercalated atoms expand the lattice and increase the in-plane and out-of-plane stresses, which stabilize both the rhombohedral phase (r-phase) and its ferroelectric properties. Our ferroelectric devices, which are based on the r-phase Hf(Zr)₁₊O₂, exhibit an ultralow coercive field (~0.65 megavolts per centimeter). Moreover, we achieved a high endurance of more than 10¹² cycles at saturation polarization. This material discovery may help to realize low-cost and long-life memory chips.