Impact of chemical bonding difference of ALD Mo on SiO2 and Al2O3 on the effective work function of the two gate stacks

This study investigates molybdenum deposited by atomic layer deposition (ALD) as a potential gate metallization for flash memory devices. Polycrystalline (110)-oriented, with low-resistivity (∼16 μΩ cm) ALD Mo films were deposited on SiO2 and Al2O3 using hydrogen reduction of Mo-oxychloride precursor. On SiO2, an effective work function (EWF) of 4.75 ± 0.1 eV was obtained for as-deposited samples, and its value increased up to 4.9 ± 0.05 eV upon annealing at 600 °C, whereas on Al2O3, a stable EWF value of 5.05 ± 0.05 eV was observed. The EWF variation is correlated with changes in the composition and chemical bonding at the metal/dielectric interface. The latter were investigated by energy dispersive x-ray spectroscopy and electron energy loss spectroscopy performed using scanning transmission electron microscopy and x-ray photoelectron spectroscopy. This analysis revealed that the presence of Mo oxide at the Al2O3/Mo interface stabilizes the EWF, and the EWF increase on SiO2 is attributed to Si enrichment at the SiO2/Mo interface upon annealing. A theoretical model is suggested to explain the chemical bonding difference on SiO2 and Al2O3, based on the Mo-precursor reactions with the surface groups of the dielectric. This study emphasizes the importance of the precursor/substrate reactions in determining the compositional and, therefore, electrical properties of the metal/dielectric interface, and demonstrates that ALD Mo deposited directly on SiO2 and Al2O3 is a promising candidate for gate metallization of flash devices due to its high EWF.