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Alfilmsdeposited on sputtered‐TiN/Si substrate by metalorganic chemical vapor deposition(MOCVD) from dimethylethylamine alane (DMEAA) were characterized using x‐ray diffraction(XRD),Auger electron spectroscopy(AES),atomic force microscopy(AFM), and transmission electron microscopy (TEM). The TiN filmsputtered on the Si has a preferred orientation along the growth direction with the 〈111〉 of the film parallel to the Si〈111〉. Sputtering of the TiN film on the Si induced strains at the interface. The TiN/Si interface is flat while the Al/TiN interface is rough. There exist many dislocations at the Al/TiN interface. The Al2O3 phase was formed at the Al/TiN interface during the early stages of Aldeposition. In the Al grains, there exist many tangled dislocations and a few Al2O3 particles. With increasing deposition time, the Alfilm surface roughness increases.