Effect of Systematic Changes of Ti and Hf Si-oxynitride Alloys by Nitrogen Incorporation as a Bond Constraint on Electrical and Material Properties

We have investigated the effect of Si3N4 content in (Ti(Hf)O2)x(Si3N4)y(SiO2)1-x-y pseudo-ternary alloys by tracking systematic changes of electrical properties, including electrically active defects. Results from Soft x-ray photoelectron spectroscopy (SXPS) studies indicate no detectable hole traps for Ti/Hf Si oxynitrides with Si3N4 content >35%; these alloys have equal concentrations of Ti(Hf)O2 and SiO2, ~30-32%, and additionally are stable for annealing in Ar ambients to temperatures of 1100°C. Derivative near edge x-ray absorption spectroscopy (NEXAS) comparisons for the O K1 edges of TiO2 and optimized Ti Si oxynitride alloys provides a significantly reduced average crystal field d-state splitting from 1.9 to 1.6eV, as well as decreased electron trapping, and is correlated with a four-fold coordination of Ti in the Ti Si oxynitride alloys. The flat band voltage shift with varying frequency from 10 kHz to 1MHz in these alloys is less than 12 mV and the compositional dependence of current-voltage characteristics on Si3N4 composition results in the lowest leakage current at a Si3N4 content of ~40 % with the smallest equivalent oxide thickness (EOT) as well. Based on these studies, Transition Metal (TM) Si oxynitride alloys are anticipated to yield EOT <1 nm for scaled CMOS devises.