Intrinsic bonding defects in transition metal elemental oxides

Gate dielectrics comprised of nanocrystalline HfO2 in gate stacks with thin SiO2/SiON interfacial transition regions display significant asymmetries with respect to trapping of Si substrate injected holes and electrons. Based on spectroscopic studies, and guided by ab initio theory, electron and hole traps in HfO2 and other transition metal elemental oxides are assigned to O-atom divacancies, clustered at internal grain boundaries. Three engineering solutions for defect reduction are identified: i) deposition of ultra-thin, < 2 nm, HfO2 dielectric layers, in which grain boundary formation is suppressed by effectively eliminating inter-primitive unit cell π-bonding interactions, ii) chemically phase separated high HfO2 silicates in which inter-primitive unit cell p-bonding interactions are suppressed by the two nanocrystalline grain size limitations resulting from SiO2 inclusions, and iii) non-crystalline Zr/Hf Si oxynitrides without grain boundary defects.