Smart Design of Fermi Level Pinning in HfO₂‐Based Ferroelectric Memories

Abstract How and why the reliability of ferroelectric HfO₂‐ and HZO (Hf_0.5Zr_0.5O₂)‐based memory devices strongly depends on the choice of electrode materials is currently under intense discussion. Interface conditions such as band alignment, defect formation, and doping are recognized as decisive and interrelated parameters, but a unified picture of the physical mechanisms is still missing. Here, two opposite scenarios of band alignment are found in TiN/HZO/TiN and IrO₂/HZO/IrO₂ using hard X‐ray photoelectron spectroscopy, revealing on the one hand the conditions for a stable device performance, and the origin of their degradation on the other. As a key difference, TiN electrodes scavenge oxygen from the HZO, while IrO₂ electrodes supply it. Considering the electronic doping limit of HfO₂, a key condition for the stability of ferroelectric devices can be identified: The alignment of the charge neutrality levelwith respect to the metallic Fermi level, which is pinned by the doping limit. Stable device performance can only be achieved for oxygen‐deficient HfO₂‐based interfaces, where the Fermi level of the metal electrode is close to the conduction band of the ferroelectric insulator. This empirical model explains the fatigue behavior of HfO₂‐based capacitors using either oxygen‐scavenging TiN or oxygen‐supplying IrO₂ electrodes.