Karen Paz Bastos

Oxygen reaction-diffusion in metalorganic chemical vapor deposition HfO2 films annealed in O2

Composition, atomic transport, and chemical reaction were investigated following annealing in O2 of ultrathin HfO2 films deposited on Si substrates thermally nitrided in NO. The as-prepared thin film composition was established by Rutherford backscattering spectrometry, nuclear reaction analysis, and x-ray photoelectron spectroscopy as a HfO2 film on an intermediate layer containing silicon oxynitride, hafnium silicate, and possibly hafnium–silicon oxynitride. O penetration, incorporation in the bulk of the HfO2/SiOxNy structure, and oxidation of the substrate forming SiO2 were observed.

Nitrogen bonding, stability, and transport in AlON films on Si

The chemical environment of N in nitrided aluminum oxide films on Si(001) was investigated by angle-resolved x-ray photoelectron spectroscopy. Two different bonding configurations were identified, namely N–Al and N–O–Al, suggesting the formation of the AlN and AlO2N compounds. The near-surface region is N-rich and AlN compounds therein are more abundant than AlO2N, whereas in bulk regions the proportions of these two compounds are comparable. Rapid thermal annealing at 1000 °C for 10 s in vacuum or in low-pressure oxygen atmosphere led to the breakage of N–Al bonds in AlN, releasing N and Al. The mobile N is partly lost by desorption from the surface and partly fixed by reacting with the network to form AlO2N. The released Al atoms, which remain immobile, react with oxygen from the film or from the gas phase. Characterization of the films outermost surfaces by low-energy ion scattering revealed that the migration of Si atoms from the substrate across the films, reaching the surface and being oxidized ther...

Effects of post-deposition annealing in O2 on the electrical characteristics of LaAlO3 films on Si

LaAlO3 films were deposited on p-type Si(100) by sputtering from a LaAlO3 target. C×V characteristics were determined in nonannealed and O2-annealed capacitors having LaAlO3 films as dielectric and RuO2 as top electrode. Thermal annealing in O2 atmosphere reduced flat band voltage to acceptable values for advanced Si-based devices. O16–O18 isotopic substitution was characterized by Rutherford backscattering spectrometry and nuclear resonant reaction profiling. Chemical analysis of the films was accomplished by x-ray photoelectron spectroscopy. The electrical improvements observed after thermal annealing in O2 were attributed to the incorporation of oxygen from the gas phase, possibly healing oxygen vacancies in the films and providing mobile oxygen to the interface.

Integrity of hafnium silicate/silicon dioxide ultrathin films on Si

Rapid thermal annealing at 1000 °C of (HfO2)1−x(SiO2)x pseudobinary alloy films deposited on Si were performed in N2 or O2 atmospheres. The effects on the atomic transport, structure, and composition were investigated using isotopic substitution of oxygen, high-resolution transmission electron microscopy, nuclear reaction analyses, narrow nuclear reaction resonance profiling, and grazing angle x-ray reflection.

Environment of hafnium and silicon in Hf-based dielectric films: An atomistic study by x-ray absorption spectroscopy and x-ray diffraction

The atomic structure of HfSiO and HfSiON was investigated before and after thermal annealing using x-ray diffraction and x-ray absorption spectroscopy. In HfSiO, the Hf atoms are arranged in a monoclinic HfO2 structure with Hf as second nearest neighbors, while Si is in a SiO2 environment. Thermal annealing induces crystallization of HfSiO with subtle changes in Hf–Hf distances. In the case of HfSiON, a stable structure is observed around the Hf atoms, which remains unaffected after annealing. Nitrogen is present in the first coordination shell of the Hf atoms, with Si in a SiON environment.

Hydrogen and deuterium incorporation and transport in hafnium-based dielectric films on silicon

Hydrogen and deuterium incorporation into nitrided and non-nitrided hafnium silicate films on Si during thermal annealing in H1- and H2-containing atmospheres was investigated. H1 profiling was accessed by means of nuclear resonant reaction profiling, whereas H2 incorporation was quantified by nuclear reaction analysis. The effects of preannealing in different atmospheres and temperatures were determined, as well as the losses of H1 and H2 from these structures during postannealing in vacuum. The results reveal a rather uniform depth distribution of incorporated H1, in striking contrast with previous studies on hydrogen in silicon oxide and oxynitrides and hafnium oxide films on Si. These results are discussed in terms of the defects present in each one of the structures studied here.

Compositional stability of hafnium aluminates thin films deposited on Si by atomic layer deposition

We have used nuclear reaction analyses and Rutherford backscattering spectrometry to investigate quantitatively the compositional stability of hafnium aluminate thin films deposited on Si(001) by atomic layer deposition using HfCl4∕H2O and Al(CH3)3∕H2O precursors. It was found that increasing Al∕Hf deposition cycles ratio leads to increasing oxygen deficiency in the as-deposited films as well as to increasing metal losses (up to ∼15%) from the films after rapid thermal annealing at 1000 °C. Furthermore, isotopic substitution experiments, showed that incorporation of oxygen from the gas phase is eased in the cases where deposition conditions failed to supply enough oxygen to complete oxides stoichiometry.

Thermal stability of plasma-nitrided aluminum oxide films on Si

The effect of post-deposition rapid thermal annealing in vacuum and in dry O2 on the stability of remote plasma-assisted nitrided aluminum oxide films on silicon is investigated. The areal densities of Al, O, N, and Si were determined by nuclear reaction analysis and their concentration versus depth distributions by narrow nuclear reaction resonance profiling, with subnanometric depth resolution. Annealing in both vacuum and O2 atmospheres produced partial loss of N from the near-surface regions of the films and its transport into near-interface regions of the Si substrate. Oxygen from the gas phase was incorporated in the AlON films in exchange for O and N previously existing therein, as well as in the near-interface regions of the Si substrate, leading to oxynitridation of the substrate. Al and Si remained essentially immobile under rapid thermal processing, confirming that the presence of nitrogen improves the thermal stability characteristics of the AlON/Si structures in comparison with non-nitrided A...

Thermal behavior of hafnium-based ultrathin films on silicon

We report here on the thermodynamical stability of ultrathin, hafnium-based dielectric films, namely hafnium oxide (HfO2), silicate (HfSixOy), and aluminum silicate (AlHfxSiyOz), deposited on silicon. These materials are promising candidates to replace the well established silicon oxide and oxynitride as gate dielectric materials in advanced Si-based complementary metal–oxide–semiconductor technology. Since there are mandatory requirements on the gate dielectric material, hafnium oxide is currently being modified, by adding silicon and aluminum into the matrix, increasing its thermal stability, and improving its electrical properties. Diffusion-reaction during thermal processing was investigated using isotopic substitution together with ion beam techniques such as Rutherford backscattering spectrometry, narrow nuclear resonance profiling, and nuclear reaction analysis. The chemical changes in the films were accessed by x-ray photoelectron spectroscopy.

Exchange-diffusion reactions in HfSiON during annealing studied by Rutherford backscattering spectrometry, nuclear reaction analysis and narrow resonant nuclear reaction profiling

HfSiON films deposited on Si (001) by reactive sputtering were submitted to rapid thermal annealing at 1000°C in vacuum, N2 and O2 atmospheres. The stability of the dielectric was evaluated by measuring the atomic transport and exchange of the chemical species, using Rutherford backscattering spectrometry, nuclear reaction analysis and narrow resonant nuclear reaction profiling. Annealing in O2 ambient reduced the N concentration mainly from near-surface regions where oxygen was incorporated in comparable amounts. Vacuum annealing, on the other hand, induced N loss preferentially from the Si/dielectric interface and O loss preferentially from near-surface regions. The results are explained in terms of exchange-diffusion reactions occurring in the HfSiON.