Physical-Chemical Evolution upon Thermal Treatments of Al 2 O 3 , HfO 2 and Al/Hf Composite Materials Deposited by ALCVD™

This paper presents a systematic investigation of thermal stability of high-k materials deposited on RCA cleaned wafers by ALCVDTM in an ASM PulsarTM 2000 reactor. Physical-chemical evolution of Al2O3, HfO2 and Al/Hf composite materials (nanolaminate and aluminates) was studied considering two types of thermal treatments: quenched vacuum anneals from 300°C to 900°C and furnace atmospheric processes in N2 or O2 at 850°C and 900°C. Material crystallization and changes in film structure were studied by means of TEM, XRD, XRR, XRF, RBS and TOF-SIMS. Non-contact electrical measurements were used to detect modification in EOT and fixed charge. Al2O3 was found still amorphous at 900°C. Not so for HfO2 that crystallized in monoclinic phase at a temperature between 300–400°C. Crystallization temperature and possible phase separation of Al/Hf composite materials were found to be a function of Al2O3 content and film type. In most of these samples, however, a chemical evolution was detected in addition to the above reported crystallization phenomena. All the achieved results demonstrate that depending on thermal treatment conditions, ALCVDTM high-k stability does not only concern phase transition effects but also a transformation of the “SiO2/high-k” system into “doped-SiO2/silicate” stack.