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Crystal structure and composition are inter-dependent and decoupling their effects on surface reactivity is challenging. Using low-energy electron microscopy to spatially and temporally resolve the oxide film growth during the oxidation of NiAl(100), we differentiate such coupled effects by monitoring oxide growth while simultaneously fine-tuning the surface structure and composition during oxidation. We demonstrate that the oxidation of chemically ordered surfaces results in compact oxide island growth whereas non-compact oxide growth during the surface phase transition. By incorporating the surface phase transition induced chemical disordering into kinetic Monte Carlo simulations, we show that the non-compact oxide growth is induced by the composition effect on the surface diffusion of oxygen, which can be described by the concept of “ant in the labyrinth”.

In this invited paper, we demonstrate how physical analysis techniques that are commonly used in integrated circuits failure analysis can be applied to detect the failure defects associated with ultrathin gate dielectric wear-out and breakdown in [email protected] materials and investigate the associated failure mechanism(s) based on the defect chemistry. The key contributions of this work are perhaps focused on two areas: (1) how to correlate the failure mechanisms in [email protected]/metal gate technology during wear-out and breakdown to device processing and materials and (2) how the understanding of these new failure mechanisms can be used in proposing ''design for reliability'' (DFR) initiatives for complex and expensive future CMOS nanoelectronic technology nodes of 22nm and 15nm. Hf-based [email protected] materials in conjunction with various gate electrode technologies will be used as main examples while other potential [email protected] gate materials such as cerium oxide (CeO"2) will also be demonstrated to further illustrate the concept of DFR.