In situ infrared spectroscopy of hafnium oxide growth on hydrogen-terminated silicon surfaces by atomic layer deposition

Abstract

The interface formation between HfO2 and H-terminated Si(111) and Si(100) is studied by in situ infrared absorption spectroscopy during atomic layer deposition using alternating tetrakis-ethylmethylamino hafnium (TEMAH) and deuterium oxide (D2O) pulses. The HfO2 growth is initiated by the reaction of TEMAH with Si–H rather than D2O, and there is no evidence for SiO2 formation at moderate growth temperatures (∼100°C). Although Rutherford backscattering shows a linear increase of Hf coverage, direct observations of Si–H, Si–O–Hf, and HfO2 phonons indicate that five cycles are needed to reach the steady state interface composition of ∼50% reacted sites. The formation of interfacial SiO2 (∼0.7nm) is observed after postdeposition annealing at 700°C in ultrapure nitrogen.