G. Guha, E. Cartier, M. A. Gribelyuk, N. Bojarczuk, M. C. Copel et al., Atomic beam deposition of lanthanum- and yttrium-based oxide thin films for gate dielectrics, Applied Physics Letters, vol.77, issue.17, p.17, 2000.
DOI : 10.1063/1.1320464

[. Guo and T. Ma, Tunneling leakage current in oxynitride dependence on oxygen/nitrogen content, IEEE Electron Device Letters ?, vol.19, issue.6, 1998.

~. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~, Trap-assisted tunneling in high gate dielectric stacks, ? Journal of Applied Physics ?, vol.87, issue.12, p.8615, 2000.

[. J. Hubbard, D. Schlom, and ?. , Thermodynamic stability of binary oxides in contact with silicon, ? Journal of Material Research, vol.11, p.11, 1996.

~. Imanaka, T. Masui, and Y. Kato, Preparation of the cubic-type La 2 O 3 phase by thermal decomposition of LaI 3, Journal of Solid State Chemistry ?, vol.178, 2005.

~. Kang and S. W. Rhee, Deposition of La[sub 2]O[sub 3] Films by Direct Liquid Injection Metallorganic Chemical Vapor Deposition, Journal of The Electrochemical Society, vol.149, issue.6, 2002.
DOI : 10.1149/1.1477207

S. [. Kuriyama, K. Ohmi, H. Tsutsui, and . Iwai, Effect of post-metallization annealing on electrical characteristics of La 2 O 3 gate thin films, ? Japanese Journal of Applied Physics ?, vol.44, issue.2, 2005.

~. Lee, C. Lee, and Y. Kim, High-k gate dielectrics for sub-100 nm CMOS technology " -Solid- State and Integrated-Circuit Technology, Proceedings. 6th International Conference, pp.22-25, 2001.

[. Lo and D. Buchanan, Quantum-mechanical modeling of electron tunneling current from the inversion layer of ultra-thin-oxide nMOSFET's, IEEE Electron Device Letters, vol.18, issue.5, p.209, 1997.
DOI : 10.1109/55.568766

~. Matsushita, K. Muraoka, K. Kato, Y. Nakasaki, S. Inumiya et al., Novel fabrication process to realize ultra-thin (EOT=0.7 nm) and ultra-low-leakage SiON gate dielectrics, Microelectronic Engineering, vol.80, pp.424-455, 2005.
DOI : 10.1016/j.mee.2005.04.099

[. Miranda, J. Molina, Y. Kim, and H. Iwai, Degradation of high-k La 2 O 3 gate dielectrics using progressive electrical stress, p.45, 2005.

T. [. Muller, S. Sorsch, F. Moccio, K. Baumann, G. Evans-lutterodt et al., The electronic structure at the atomic scale of ultrathin gate oxides, Nature, vol.399, issue.6738, pp.758-761, 1999.
DOI : 10.1038/21602

~. Ng, N. Zhan, N. Zhan, C. Kok, M. Poon et al., Electrical characterization of the hafnium oxide prepared by direct sputtering of Hf in oxygen with rapide thermal annealing, pp.1289-1293, 2003.

~. Ohmi, C. Kobayashi, I. Kashiwagi, C. Ohshima, H. Ishiwara et al., Characterization of La 2 O 3 and Yb 2 O 3 thin films for high-k gate insulator application, Journal of the Electrochemical Society ?, vol.150, issue.7, 2003.

~. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~, Fine structure in the intrinsic absorption edge of TiO 2, ? Physical Review B, vol.18, p.5606, 1978.

[. Peacock and J. Robertson, Band offsets and Schottky barrier heights of high dielectric constant oxides, Journal of Applied Physics, vol.92, issue.8, p.8, 2002.
DOI : 10.1063/1.1506388

~. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~, Schenk and G. Heiser ? " Modeling and simulation of tunnelling through ultra-thin gate dielectrics, Journal of Applied Physics, vol.81, p.7900, 1997.

~. Wallace and G. Wilk, High-?? Dielectric Materials for Microelectronics, Solid State and Material Sciences -28, p.231, 2003.
DOI : 10.1080/714037708

[. Wallace and G. Wilk, High-k gate dielectric materials, MRS Bulletin, vol.27, 2002.

[. Wallace and G. Wilk, Exploring the limit of gate dielectric scaling, ?Semiconductor international, p.153, 2001.

[. Wallace and G. Wilk, Identifying the most promising high-k gate dielectrics, ? Semiconductor International ?, vol.227, 2001.

O. Weber, M. Cassé, L. Thevenod, F. Ducroquet, B. Ernst et al., Experimental determination of mobility scattering mechanism in metal gate MOSFETs " - ESSDERC Technology Digest, p.379, 2005.

[. Wilk, R. Wallace, and J. Anthony, High-?? gate dielectrics: Current status and materials properties considerations, Journal of Applied Physics, vol.89, issue.10, 2001.
DOI : 10.1063/1.1361065

~. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~, Lucovsky ? " integration of ultra-thin (1.6 ? 2 nm) RPECVD oxynitride gate dielectrics into dual poly-si gate submicron CMOSFETs " ? Technical Digest of International Electron Devices Meeting, pp.245-253, 1999.

[. Yu and I. Boyd, X-ray diffraction and electrical characterization of photo-CVD zirconium oxide layers, Applied Surface Science, vol.208, issue.209, pp.208-209, 2003.
DOI : 10.1016/S0169-4332(02)01406-X

~. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~, Interfacial stability between zirconium oxide thin films and silicon, ? Microelectronic Engineering ?, vol.66, p.427, 2003.

[. Wilk, R. Wallace, and J. Anthony, High-?? gate dielectrics: Current status and materials properties considerations, Journal of Applied Physics, vol.89, issue.10, 2001.
DOI : 10.1063/1.1361065

~. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~, Low temperature photo-oxidation of silicon using a xenon excimer lamp, Applied Physics Letters ?, vol.71, p.2964, 1997.

~. Damlencourt, F. Bedu, O. Renault, F. Martin, M. Séméria et al., Billon ? " surface treatment for the atomic layer deposition of HfO 2 on silicon, Applied Physics Letters ?, vol.861, 2005.

~. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~, Status and prospects for VUV Ellipsometry (Applied to high K and low K materials)-Characterization and Metrology for ULSI Technology, p.723, 2003.

~. Foster, F. Lopez-gejo, A. Shluger, and R. Nieminen, Vacancy and interstitial defects in hafnia, Physical Review B, vol.65, issue.17, p.174117, 2002.
DOI : 10.1103/PhysRevB.65.174117

[. Fujii, N. Miyata, S. Migita, T. Horikawa, and A. Toriumi, Nano-meter scale crystallization of thin HfO 2 films studied by HF-chemical etching -Applied Physics Letters, p.212907, 2005.

~. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~, Caractérisation et modélisation de l'oxyde d'hafnium comme alternative à la silice pour les futures technologies CMOS submicroniques, 2004.

[. Garros, C. Leroux, and J. Autran, An Efficient Model for Accurate Capacitance-Voltage Characterization of High-k Gate Dielectrics Using a Mercury Probe, Electrochemical and Solid State Letter -5 (3), pp.4-6, 2002.
DOI : 10.1149/1.1450382

M. L. Green, E. Gusev, R. Degraeve, and E. L. Garfunkel, Ultrathin (<4 nm) SiO 2 and Si-O-N gate dielectric layers for silicon microelectronics: understanding the processing, structure, and physical and electrical limits, ? Journal of Applied Physics ?, vol.90, issue.5, 2001.

. [. Grove, Physic and technology of semiconductor devices, 1967.

[. J. Guittet, J. Crocombette, and M. , Gautier-Soyer ? " Bonding and XPS chemical shifts in ZrSiO 4

~. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~, Handbook of X-ray photoelectron spectroscopy ? Perkin-Elmer Corporation, Physical Electronics division, 1979.

[. Holliger, F. Laugier, and J. C. Dupuy, SIMS depth profiling of ultrashallow P, Ge and As implants in Si using MCs2+ ions, Surface and Interface Analysis, vol.23, issue.1, pp.472-476, 2002.
DOI : 10.1002/sia.1341

~. Takeuchi, H. Daewon, and T. King, Observation of bulk HfO2 defects by spectroscopic ellipsometry, Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, vol.22, issue.4, p.1337, 2004.
DOI : 10.1116/1.1705593

R. [. Teren, J. Thomas, P. He, and . Ehrart, Comparison of precursors for pulsed metal???organic chemical vapor deposition of HfO2 high-K dielectric thin films, Thin Solid Films, vol.478, issue.1-2, pp.206-217, 2005.
DOI : 10.1016/j.tsf.2004.11.055

~. Williams, A. Jones, N. Tobin, P. Chalker, S. Taylor et al., Growth of Hafnium dioxide thin films by liquid-injection MOCVD using Alkylamide and Hydroxylamide precursors " ? Chemical Vapor Deposition -9, pp.309-314, 2003.

[. Wilk, R. Wallace, and J. Anthony, High-?? gate dielectrics: Current status and materials properties considerations, Journal of Applied Physics, vol.89, issue.10, 2001.
DOI : 10.1063/1.1361065

H. Wong, B. Sen, V. Filip, and M. Poon, Material properties on interfacial silicate layer and its influence on the electrical characteristics of MOS devices using hafnia as the gate dielectric -Thin Solid Films, p.192, 2006.

~. Yamamoto, S. Hayashi, M. Asai, S. Horii, and H. Miya, Grown by Physical and Chemical Vapor Deposition, Japanese Journal of Applied Physics, vol.42, issue.Part 1, No. 4B, pp.1835-1839, 2003.
DOI : 10.1143/JJAP.42.1835

~. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~, Vanderbilt ? " First-principles study of structural, vibrational, and lattice dielectric properties of hafnium oxide, ?Physical Review B ?, vol.65, p.233106, 2002.

. Pour-compléter-cette-Étude, sur des échantillons de l'ordre de 3 nm déposés à 430°C, sous un flux de 1700 et 3000 sccm d'oxygène. Nous avons vu, dans le chapitre II paragraphe III-B, que la méthode d'ellipsométrie spectroscopique permet d'accéder à des informations sur la structure et la composition du HfO 2 . Les parties réelles et imaginaires de la fonction diélectrique ? sont tracées en fonction de l'énergie des photons pour les deux échantillons (figure III 13) Pour simuler les spectres, un modèle à deux Tauc-Lorentz a été utilisé, Cette méthode permet d'obtenir les paramètres optiques relatifs au matériau

[. Aarik, A. Aidla, H. Mändar, T. Uustare, K. Kukli et al., Phase transformations in hafnium dioxide thin films grown by atomic layer deposition at high temperatures, Applied Surface Science, vol.173, issue.1-2, pp.15-21, 2001.
DOI : 10.1016/S0169-4332(00)00859-X

[. Aarik, A. Aidla, A. Kiisler, T. Uustare, V. Sammelselg et al., Influence of substrate temperature on atomic layer growth and properties of HfO 2 thin films " -Thin Solid Films, p.110, 1999.

[. Afanas-'ev, A. Stesmans, F. Chen, X. Shi, and S. Campbell, Internal photoemission of electrons and holes from (100)Si into HfO 2, ? Applied Physics Letters ?, vol.81, issue.6, p.1053, 2002.

~. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~, Croissance et propriétés de films minces de HfO 2 déposés par Atomic Layer Deposition pour des applications microélectroniques, Université Montpellier II ? Sciences et Techniques du Languedoc, 2003.

~. Cho, N. Nguyen, C. Richter, J. Ehrstein, B. Lee et al., dielectric HfO2 thin films and the high-temperature annealing effects on their optical properties, Applied Physics Letters, vol.80, issue.7, p.1249, 2002.
DOI : 10.1063/1.1448384

~. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~, Elaboration par PE-MOCVD à injection de couches minces d'oxydes d'Yttrium pour les applications en microélectronique avancée, Thèse, 2004.

~. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~, Caractérisation et modélisation de l'oxyde d'hafnium comme alternative à la silice pour les futures technologies CMOS submicroniques, 2004.

~. Kato, T. Nango, T. Miyagawa, T. Katagiri, K. S. Seol et al., Plasma-enhanced chemical vapor deposition and characterization of high-permittivity hafnium and zirconium silicate films, Journal of Applied Physics, vol.92, issue.2, p.1106, 2002.
DOI : 10.1063/1.1487911

~. J. Lee, T. Jeon, D. Kwong, R. Clark, and ?. , rapid thermal chemical vapor deposition process for advanced gate dielectrics, Journal of Applied Physics -92, 2002.
DOI : 10.1063/1.1500420

~. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~-musgrave, Y. Widjaja, J. Han, E. Garfunkel, and ?. , Atomistic simulations of surface chemical reactions for growing high-k gate stack, p.2030, 2003.

[. Song, Z. Zhang, C. Huffman, S. Bae, J. Ssim et al., Integration issues of high-k and metal gate into conventional CMOS technology " ? Thin Solid Films, p.170, 2006.

~. Takeuchi, H. Daewon, and T. J. King, Observation of bulk HfO2 defects by spectroscopic ellipsometry, Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, vol.22, issue.4, p.1337, 2004.
DOI : 10.1116/1.1705593

~. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~, Vanderbilt ? First-principles study of structural, vibrational, and lattice dielectric properties of hafnium oxide, p.233106, 2002.

R. Du-chapitre, I. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~, and . ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~, Optical characterization of HfO 2 thin films grown by atomic layer deposition, ? Thin Solid Films ?, vol.466, pp.41-47, 2004.

[. Aarik, A. Aidla, H. Mandar, V. Sammelselg, T. Uustare et al., Texture development in nanocrystalline hafnium dioxide thin films grown by atomic layer deposition, Journal of Crystal Growth, vol.220, issue.1-2, pp.105-113, 2000.
DOI : 10.1016/S0022-0248(00)00831-9

[. M. De-almeida and I. J. Baumvol, Reaction???diffusion in high-k dielectrics on Si, Surface Science Reports, vol.49, issue.1-3, pp.1-114, 2003.
DOI : 10.1016/S0167-5729(02)00113-9

M. A. Arrio, P. Sainctavit, C. Cartier-dit-moulin, T. Mallah, M. Verdaguer et al., Edges, Journal of the American Chemical Society, vol.118, issue.27, pp.6422-6427, 1996.
DOI : 10.1021/ja9542698

URL : https://hal.archives-ouvertes.fr/hal-00083109

[. Cho, N. Nguyen, C. Richter, J. Ehrstein, B. Lee et al., dielectric HfO2 thin films and the high-temperature annealing effects on their optical properties, Applied Physics Letters, vol.80, issue.7, p.1249, 2002.
DOI : 10.1063/1.1448384

~. , ~. D. Seiler, A. Diebold, T. Shaffner, R. Mcdonald et al., Status and Prospects for VUV Ellipsometry (applied to high K and low K materials " -Characterization and metrology for ULSI Technology, E.M Secula ? American Institut of Physics Melville NY ?, vol.683, p.723, 2003.

~. Ferrieu, K. Dabertrand, S. Lhostis, V. Ivanova, G. Rolland et al., Observation of HfO2 thin films by deep UV spectroscopic ellipsometry, Journal of Non-Crystalline Solids, vol.353, issue.5-7, 2006.
DOI : 10.1016/j.jnoncrysol.2006.10.032

URL : https://hal.archives-ouvertes.fr/hal-00463075

~. Kosacki, V. Petrovsky, and H. Anderson, Band gap energy in nanocrystalline ZrO2:16%Y thin films, Applied Physics Letters, vol.74, issue.3, p.341, 1999.
DOI : 10.1063/1.123065

J. Droopad, A. Curless, J. Demkov, K. Finder, and ?. Eisenbeiser, Materials and physical properties of novel high-k and medium-k gate dielectrics, Material Research Society Proceedings ? 670, pp.1-1, 2002.

~. Park, . Park, C. Cho, and ?. Hwang, Interfacial reaction between chemical vapor deposited HfO 2 thin films and HF-cleaned Si substrate during film growth and post-annealing, ? Applied Physics Letters ?, vol.80, p.13, 2002.

P. [. Price, T. Hung, and B. Rhoad, Spectroscopic ellipsometry characterization of HfxSiyOz films using the Cody???Lorentz parameterized model, Applied Physics Letters, vol.85, issue.10, p.1701, 2004.
DOI : 10.1063/1.1784889

~. Takeuchi, H. Daewon, and T. King, Observation of bulk HfO2 defects by spectroscopic ellipsometry, Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, vol.22, issue.4, p.1337, 2004.
DOI : 10.1116/1.1705593

~. W. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~-wiemer, S. Ferrari, M. Fanciulli, G. Pavia, L. Lutterotti et al., Combining grazing incidence X-ray diffraction and X-ray reflectivity for the evaluation of the structure evolution of HfO 2 thin films with annealing " ? Thin Solid Films, pp.134-137, 2004.

[. Wilk, R. Wallace, and J. Anthony, Hafnium and zirconium silicates for advanced gate dielectrics, Journal of Applied Physics, vol.87, issue.1, 2000.
DOI : 10.1063/1.371888

~. Xie, Y. Zhao, and M. White, Interfacial oxide determination and chemical/electrical structures of HfO 2 /SiO x /Si gate dielectrics " ? Solid-state Electronics -48, pp.2071-2077, 2004.

~. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~, Vanderbilt ? First-principles study of structural, vibrational, and lattice dielectric properties of hafnium oxide, p.233106, 2002.

. Tracy, Limits of optical and X-ray metrology applied to thin gate dielectrics, pp.166-171, 2005.

R. Du-chapitre, V. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~, and . ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~, Texture development in nanocrystalline hafnium dioxide thin films grown by ALD, Journal of Crystal Growth ?, vol.220, pp.105-113, 2000.

~. Chen, W. J. Yoo, and D. S. Chan, Investigation of Wet Etching Properties and Annealing Effects of Hf-Based High-k Materials, Journal of The Electrochemical Society, vol.153, issue.5, pp.483-491, 2006.
DOI : 10.1149/1.2184929

~. Fujii, N. Miyata, S. Migita, T. Horikawa, and A. Toriumi, Nanometer-scale crystallization of thin HfO2 films studied by HF-chemical etching, Applied Physics Letters, vol.86, issue.21, p.212907, 2005.
DOI : 10.1063/1.1939073

I. Références-de-l-'annexe, N. Cho, C. Nguyen, J. Richter, B. Ehrstein et al., Spectroscopic ellipsometry of high-k dielectric HfO 2 films and high temperature annealing effects on their optical properties, Applied Physics Letters, vol.80, p.7, 2002.

S. Gonchond-de, Film Substrat Film Substrat Figure A.III 2: Exemple de spectre de réflectivité des rayons X

I. Références-de-l-'annexe, A. Rochat, F. Chabli, M. Bertin, C. Olivier et al., Attenuated total reflection spectroscopy for infrared analysis of thin layers on a semiconductor substrate, Journal of Applied Physics ?, vol.91, issue.8, 2002.

. Si, solide) + O 2 (gaz ) SiO 2 (solide

. La-vitesse-d-'attaque-du, SiO 2 dans cette solution a été mesurée à 7 nm/min (à 23 °C) Par cette technique

S. Le-nettoyage, Standard Clean 1) s'effectue par immersion du substrat de silicium dans un bain de pH 9