Intrinsic electronically active defects in transition metal elemental oxides

Densities of interfacial and bulk defects in high-kappa dielectrics are typically about two orders of magnitude larger than those in Si-SiO2 devices. An asymmetry in electron and hole trapping kinetics, first detected in test capacitor devices with nanocrystalline ZrO2 and HfO2 dielectrics, is a significant potential limitation for Si device operation and reliability in complementary metal oxide semiconductor applications. There are two crucial issues: i) are the electron and hole traps intrinsic defects, or are they associated with processed- introduced impurities?, and ii) what are the local atomic bonding arrangements and electronic state energies of these traps? In this study, thin film nanocrystalline high-kappa gate dielectrics, TiO2, ZrO2, and HfO2 (group IVB TM oxides), are investigated spectroscopically to identify the intrinsic electronic structures of valence and conduction band states, as well as those of intrinsic bonding defects. A quantitative/qualitative distinction is made between crystal field and Jahn-Teller (J-T) d-state energy differences in nanocrystralline TM elemental oxides, and noncrystalline TM silicates and Si oxynitrides. It is experimentally shown and theoretically supported that a length scale for nanocrystallite size < 2-3 nm i) eliminates J-T d-state term splittings in band edge pi-bonded d-states, and ii) represents a transition from the observation of discrete band edge defects to band-tail defects. Additionally, pi-state bonding coherence can also be disrupted with similar effects on band edge and defect states in HfO2 films which have been annealed in NH3 at 700 degrees C, and display Hf-N bonds in N atom K-1 edge X-ray absorption spectra.