Silicate layer formation at HfO2/SiO2/Si interface determined by x-ray photoelectron spectroscopy and infrared spectroscopy

A high-k Hf-silicate interfacial layer grown by the solid phase reaction between sputtered metallic Hf films and an underlying SiO2/Si substrate through in situ vacuum annealing and subsequent thermal oxidation has been investigated. By means of the chemical shifts of Si 2p, Hf 4f, and O 1s core-level spectra determined by x-ray photoelectron spectroscopy (XPS), the formation of an interfacial Si-O-Si bond as the dominant reaction during in situ thermal oxidation of the Hf/SiO2/Si gate stack has been confirmed. In situ vacuum anneals without air exposure at 700 °C accelerates the interface reaction and results in the formation of Si-rich Hf-silicate interfacial layer. Analysis by Fourier transform infrared spectroscopy (FTIR) has indicated that vacuum annealed samples containing the silicate interface layer effectively suppresses the growth of the interfacial SiOx layer compared to unannealed samples during postdeposition annealing.