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Etude Ab initio des mécanismes réactionnels dans la phase initiale du dépôt par couches atomiques des oxydes à moyenne et forte permittivité sur silicium

Abstract : This work attempts to bring a new light on the understanding of some critical aspects of the physicochemical processes that control Alumina, Zirconia and Hafnia ALD growth, yet not sufficiently understood. These materials are addressed as potentially best candidates to replace gate dielectric SiO2 in the near future electronic applications. Most accurate ab initio correlated methods, like couple-cluster CCSD(T) and CISD(T), with different basis sets functions, as well as the available experimental data have been used for testing by a systematic study the accuracy and the reliability of DFT B3LYP functional. Our results have claimed this hybrid-DFT method to be chosen in predicting of high accurate static and dynamic properties throughout the family of organometallic-like (AlxCyHzOt) and transition metal-based (Zr/HfxClyOzHt) molecular systems. First systematic study of torsional potential surfaces of TMA has been performed and the related features of the hindered rotors of the methyl groups revealed with high accuracy. Laying on these accurate results we have also proposed least-squared fit methods to determine frequency scaling factors subject to different thermodynamic properties and/or thermal conditions. Many-step reaction mechanisms of ALD gas phase precursors of each of the three oxides with residual water, or regime of low pressure H2OÓALD pulses, have been studied in detail. Strong anharmonic internal movements of molecular species throughout the hydrolysis reactions have been observed and qualitatively discussed in relation with their possible effects on the reactions' kinetics. TMA/H2O reactions have been validated as strongly exothermic, while Hafnium and Zirconium tetrachlorides have founded to react endothermically with single H2O molecule. We have also studied in detail reaction mechanisms of the related on-surface ALD-complexes with water vapors. Our theoretical investigations address to the initial stage of ALD growth, more s pecifically on SiO2/Si(001)-2x1 like surfaces. The proposed many-step mechanisms, similar to those discussed for the gas phase, confirmed again the strong reactivity of H2O molecule with on-surface Aluminum hydroxymethylides, and responds strong endothemically as for the hydroxylation of Zirconium and Hafnium on-surface hydroxychlorides. The last two proved a very similar surface chemistry. Finally the cooperative effects of H2O molecules have been considered in our models of reactions, and have revealed dramatic influences on the reactivity Zirconium- and Hafnium hydroxychlorides surfaces. Our results proved the importance of both cooperative interactions of on-surface complexes and H2O molecules in the case of the Zirconia and HafniaÓALD growth, while for Aluminum oxide, presently considered ideal for ALD growth, these effects seem of secondary importance.
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Submitted on : Thursday, October 26, 2006 - 1:55:07 PM
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  • HAL Id : tel-00110050, version 1


Leonard Jeloaica. Etude Ab initio des mécanismes réactionnels dans la phase initiale du dépôt par couches atomiques des oxydes à moyenne et forte permittivité sur silicium. Micro et nanotechnologies/Microélectronique. Université Paul Sabatier - Toulouse III, 2006. Français. ⟨tel-00110050⟩



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