In-situ atomic-level observation of reversible first-order transition in Hf0.5 Zr0.5 O₂ ferroelectric film

In this work, we revealed the dynamic process of atomic structure transitions of ferroelectric (FE) Hf
0.5
Zr
^0.5
O
²
(HZO) film across Curie temperature ${\mathrm{T}}_{\mathrm{c}}$ in spherical aberration corrected transmission electron microscope (Cs-TEM) with in-situ controlled heating and cooling. We have the following new observations: (1) A first-order transition between polar orthorhombic (o−) and nonpolar tetragonal (t−) phases occurs as heating up to ${\mathrm{T}}_{\mathrm{c}}$, while the reverse process is triggered by cooling with obvious thermal hysteresis $(\Delta \mathrm{T}\approx 298^{o}\mathrm{C})$; (2) Monoclinic (m−) phase contributes to the stability of o-structure by introducing local compressive stress; (3) The cooling t-to-o transition is identified as martensitic-like transformation, therefore increasing the phase change driving force would be helpful to FE enhancement. This work provides solid evidences on structure transitions near ${\mathrm{T}}_{\mathrm{c}}$ of HZO film at atomic-scale, laying foundation for understanding the physical nature of ferroelectricity in hafnium oxide materials.