The interfacial layer between the Al₂O₃ layer and the Si₃N₄ layer formed after postdeposition annealing (PDA) of TaN/Al₂O₃/Si₃N₄/SiO₂/Si (TANOS) stacks was investigated using transmission electron microscopy (TEM), scanning transmission electron microscopy, and electron energy loss spectroscopy (EELS). From the result of the TEM analysis, it was found that the 2-nm-thick interface layer between Al₂O₃ and Si₃N₄ layers was amorphous. The high-loss EELS analysis showed that the phases of the interfacial layer weakly bound together instead of the substoichiometric silicon oxide and amorphous Al₂O₃ near the bottom interface of the crystalline Al₂O₃. The low-loss EELS analysis showed that aluminum existed in metallic state at the interface. Therefore, we speculated that SiO(x)N(y) could be formed by oxidation of Si₃N₄ during PDA and that metallic aluminum could be formed by the decomposition of weakly bound amorphous Al₂O₃ during electron irradiation. These complicated reactions near the interface could induce oxygen deficiency in the Al₂O₃ layer and finally degrade the retention properties of TANOS stacks.