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D. Résuméaluminium, . Zirconium, and . De-hafnium, Ces matériaux sont considérés des candidats très prometteurs pour remplacer la silice en tant qu'oxyde de grille dans les futurs composants CMOS. La précision et la fiabilité de la méthode DFT associée à la fonctionnelle B3LYP, ont été testées à l'aide des résultats expérimentaux et des méthodes ab initio les plus précises telles que CCSD(T) et CISD(T), en utilisant différents ensembles de fonctions de bases. Nos résultats montrent que la méthode hybride DFT peut prédire de façon précise les propriétés structurales et vibrationnelles de la famille d'organométalliques (Al x C y H z O t ) et des systèmes moléculaires à base de métaux de transition (Zr/Hf x Cl y O z H t ) Les premières études systématiques des surfaces d'énergie potentielle de TMA ont été présentées et les caractéristiques des rotors constitués des groups méthyles ont été rapportées avec une grande précision. Des mécanismes réactionnels, à plusieurs étapes, entre les molécules précurseurs de chacun des trois oxydes et les molécules d'eau résiduelle dans la phase gazeuse du réacteur ALD, ont été étudies en détail. Les mouvements internes fortement anharmoniques des espèces moléculaires présentes tout au long du processus d'hydrolyse ont été déterminés. Les effets qualitatifs sur les cinétiques des réactions ont été discutés également. La forte exothermicité de la réaction TMA/H 2 O a été démontrée, alors que les réactions avec les tétrachlorures de Zirconium et Hafnium ont montré un caractère plutôt endothermique. Nous avons aussi étudié les mécanismes réactionnels de la vapeur d'eau avec des espèces moléculaires chimisorbées en surface. Les réactions interviennent dans les premiers cycles d'ALD sur un substrat de Si(001)-2x1 légèrement oxydé. Les mécanismes que nous proposons sont qualitativement proches des mécanismes d'hydrolyse discutés dans la phase gazeuse : confirmation de la forte réactivité exothermique avec les hydroxyméthyles d'Aluminium, endothermicité des réactions avec hydroxychlorures de Zirconium et Hafnium. Les composés avec le Zirconium et le Hafnium ont des comportements similaires. Enfin, les effets de coopérativité ces effets sont de moindre importance dans le cas de l'oxyde d'aluminium, qui est considéré actuellement comme le matériau le plus compatible avec la technologie actuelle de croissance par ALD

. Abstract, Zirconia and Hafnia ALD growth, yet not sufficiently understood These materials are addressed as potentially promising candidates to replace gate dielectric SiO 2 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 structural and vibrational properties throughout the family of organometallic-like (Al x C y H z O t ) and transition metalbased (Zr/Hf x Cl y O z H t ) 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. Many-step reaction mechanisms of ALD gas phase precursors of each of the three oxides with residual water, or regime of low pressure H 2 O-ALD 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/H 2 O reactions have been validated as strongly exothermic, while Hafnium and Zirconium tetrachlorides have founded to react endothermically with single H 2 O molecule. We have also studied in detail reaction mechanisms of the related on-surface ALD-complexes with water vapors