Transition Metal Elemental Oxides Research Articles

Intrinsic Electronically Active Defects in Transition Metal Elemental Oxides

Densities of interfacial and bulk defects in high-κ 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-κ 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 π-bonded d-states, and ii) represents a transition from the observation of discrete band edge defects to band-tail defects. Additionally, π-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 °C, and display Hf–N bonds in N atom K1 edge X-ray absorption spectra.

Spectroscopic studies of O-vacancy defects in transition metal oxides

Dielectrics comprised of nano-crystalline 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 of nano-crystalline films. Engineering solutions in which grain boundary defects are suppressed include: (i) ultra-thin, <2 nm, HfO2 fims, (ii) chemically phase separated high HfO2 content silicate films, and (iii) non-crystalline Zr/Hf Si oxynitride films.

Intrinsic bonding defects in transition metal elemental oxides

Gate dielectrics comprised of nanocrystalline HfO 2 in gate stacks with thin SiO 2/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 HfO 2 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, HfO 2 dielectric layers, in which grain boundary formation is suppressed by effectively eliminating inter-primitive unit cell π-bonding interactions, ii) chemically phase separated high HfO 2 silicates in which inter-primitive unit cell p-bonding interactions are suppressed by the two nanocrystalline grain size limitations resulting from SiO 2 inclusions, and iii) non-crystalline Zr/Hf Si oxynitrides without grain boundary defects.