Skip to main content

Local Structure, Composition and Electronic Properties of Rare Earth Oxide Thin Films Studied Using Advanced Transmission Electron Microscopy Techniques (TEM-EELS)

  • Chapter
  • First Online:
Rare Earth Oxide Thin Films

Part of the book series: Topics in Applied Physics ((TAP,volume 106))

Abstract

This contribution aims to demonstrate the ability of transmission electron microscopy (TEM) and its associated techniques, high-resolution transmission electron microscopy (HRTEM) and electron energy loss spectroscopy (EELS), to contribute to the understanding of the structural, chemical and electronic properties at the nanometre level of rare earth oxide (REO) thin films in the context of their potential use as alternative gate dielectrics to SiO2. A review of the existing work on binary REO and a preliminary work on atomic layer deposited (ALD) Lu2O3/Si stack as-grown and annealed are proposed.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  • T. Wiktorczyk: Rare earth oxide films: their preparation and characterization, Optica Applicata 31, 5 (2001)

    CAS  Google Scholar 

  • G. D. Wilk, R. M. Wallace, J. M. Anthony: High-k gate dielectrics: current status and materials properties considerations, J. Appl. Phys. 89, 5243 (2001)

    Article  CAS  Google Scholar 

  • K. J. Hubbard, D. G. Schlom: Thermodynamic stability of binary oxides in contact with silicon, J. Mater. Res. 11, 2757 (1996)

    CAS  Google Scholar 

  • S. Ohmi, M. Takeda, H. Ishiwara, H. Iwai: Characterization of Lu2O3 high-k thin films on Si(100) fabricated by e-beam deposition method, in ISTC (2002) pp. 251–261

    Google Scholar 

  • L. Marsella, V. Fiorentini: Structure and stability of rare-earth and transition-metal oxides, Phys. Rev. B 69, 172103 (2004)

    Article  CAS  Google Scholar 

  • S. Stemmer: Thermodynamic considerations in the stability of binary oxides for alternative gate dielectrics in complementary metal-oxide-semiconductors, J. Vac. Sci. Technol. B 22, 791 (2004)

    Article  CAS  Google Scholar 

  • M. Fanciulli, S. Spiga, G. Scarel, G. Tallarida, C. Wiemer, G. Seguini: Structural and electrical properties of HfO2 films grown by atomic layer deposition on Si, Ge, GaAs and GaN, Mat. Res. Soc. 786, 341 (2004)

    CAS  Google Scholar 

  • A. Kingon, J. P. Maria, S. K. Streiffer: Alternative dielectrics to silicon dioxide for memory and logic devices, Nature 406, 1032 (2000)

    Article  CAS  Google Scholar 

  • S. Stemmer, J. P. Maria, A. I. Kingon: Structure stability of La2O3/SiO2 layers on Si(001), Appl. Phys. Lett. 79, 102 (2001)

    Article  CAS  Google Scholar 

  • D. H. Tryioso, R. I. Hegde, J. Grant, P. Fejes, R. Liu, D. Roan, M. Ramon, D. Werho, R. Rai, L. B. La, J. Baker, C. Garza, T. Guenther, B. E. White, Jr., P. J. Tobin: Film properties of ALD Hf- and La-gate dielectrics grown on Si with various pre-deposition treatments, J. Vac. Sci. Technol. B 22, 2121 (2004)

    Article  CAS  Google Scholar 

  • J. A. Gupta, D. Landheer, G. I. Sproule, J. P. McCaffrey, M. J. Graham, K.-C. Yang, Z.-H. Lu, W. N. Lennard: Interfacial layer formation in Gd2O3 films deposited directly on Si (001), Appl. Surf. Sci. 173, 318 (2001)

    Article  CAS  Google Scholar 

  • B. Mereu, A. Dimoulas, G. Vellianitis, G. Apostolopoulos, R. Scholz, M. Alexe: Interface trap density in amorphous La2Hf2O7/SiO2 high-k gate stacks on Si, Appl. Phys. A 80, 253 (2004)

    Article  CAS  Google Scholar 

  • D. A. Muller: Gate dielectric metrology using advanced TEM measurements, AIP-Conference-Proceedings 550, 500 (2001)

    CAS  Google Scholar 

  • A. C. Diebold, B. Foran, C. Kisielowsky, D. A. Muller, S. J. Pennycook, E. Principe, S. Stemmer: Thin dielectric film thickness determination by advanced transmission electron microscopy, Microsc. Microanal. 9, 493 (2003)

    Article  CAS  Google Scholar 

  • A. Y. Du, C. H. Tung, B. H. Freitag, W. Y. Zhang, S. Lim, E. H. Ang, D. Ng: Ultra-thin SiON and high-k HfO2 gate dielectric metrology using transmission electron microscopy, in Proc. 11th Int. Symp. on the Physical and Failure Analysis if Integrated Circuits, IPFA (2004) p. 135

    Google Scholar 

  • P. E. Batson: Simultaneous STEM imaging and electron energy-loss spectroscopy with atomic-column sensitivity, Lett. Nature 366, 727 (1993)

    Article  CAS  Google Scholar 

  • J. Kwo, M. Hong, A. R. Kortan: Properties of high kappa gate dielectrics Gd2O3 and Y2O3 for Si, J. Appl. Phys. 89, 3920 (2002)

    Article  CAS  Google Scholar 

  • D. H. Tryioso, R. I. Hegde, J. Grant, J. K. Schaeffer, D. Roan, B. E. White, Jr., P. J. Tobin: Evaluation of lanthanum based gate dielectrics deposited by atomic layer deposition, J. Vac. Sci. Technol. B 23, 288 (2005)

    Article  CAS  Google Scholar 

  • R. Lo-Nigro, R. Toro, G. Malandrino, V. Raineri, I. L. Fragalà: Electrical properties of MOCVD praseodymium oxide based MOS structures, in Proc. of the 33rd European Solid State Device Research (ESSDERC) (2003) p. 375

    Google Scholar 

  • H. J. Osten, J. P. Liu, E. Bugiel: Epitaxial growth of praseodymium oxide on silicon, Mat. Sci. Eng. B 87, 297 (2001)

    Article  Google Scholar 

  • H. Sim, C. B. Samantaray, T. Lee, H. Yeom, H. Hwang: Electrical characteristics of high-k gate dielectrics with epitaxial Si3N4 interfacial layer on Si(111), Jap. J. Appl. Phys. 43, 7926 (2004)

    Article  CAS  Google Scholar 

  • X. Wu, D. Landheer, T. Quance, M. J. Graham, G. A. Botton: Structural comparison of gadolinium and lanthanum silicate films on Si(100) by HRTEM, EELS and SAED, Appl. Surf. Sci. 200, 15 (2002)

    Article  CAS  Google Scholar 

  • X. B. Lu, Z. G. Liu, Y. P. Wang, Y. Yang, X. P. Wang, H. W. Zhou, B. Y. Nguyen: Structure and dielectric properties of amorphous LaAlO3 and LaAlOxNy films as alternative gate dielectric materials, J. Appl. Phys. 94, 1229 (2003)

    Article  CAS  Google Scholar 

  • A. Li, Q. Shao, H. Ling, J. B. Cheng, D. Wu, Z. G. Liu, N. B. Ming, C. Wang, H. W. Zhou, B. Y. Nguyen: Characteristics of LaAlO3 gate dielectrics on si grown by metalorganic chemical vapor deposition, Appl. Phys. Lett. 83, 3540 (2003)

    Article  CAS  Google Scholar 

  • H. Ono, T. Katsumata: Interfacial reactions between thin rare-earth-metal oxide films and Si substrates, Appl. Phys. Lett. 78, 1832 (2001)

    Article  CAS  Google Scholar 

  • L. F. Edge, D. G. Schlom, R. T. Brewer, Y. J. Chabal, J. R. Williams, S. A. Chambers, C. Hinkle, G. Lucovsky, Y. Yang, S. Stemmer, M. Copel, B. Holländer, J. Schubert: Suppression of subcutaneous oxidation during the deposition of amorphous lanthanum aluminate on silicon, Appl. Phys. Lett. 84, 4629 (2004)

    Article  CAS  Google Scholar 

  • H. Yamada, T. Shimizu, A. Kurokawa, K. Ichii, E. Suzuki: MOCVD of high-dielectric-constant lanthanum oxide thin films, J. Electrochem. Soc. 150, G429 (2003)

    Article  CAS  Google Scholar 

  • J. P. Maria, D. Wicaksana, A. I. Kingon, et al.: High temperature stability in lanthanum and zirconia-based gate dielectrics, J. Appl. Phys. 90, 3476 (2001)

    Article  CAS  Google Scholar 

  • S. Guha, E. Cartier, M. A. Gribelyuk, N. A. Gribelyuk, N. A. Bojarczuk, M. C. Copel: Atomic beam deposition of lanthanum- and yttrium-based oxide thin films for gate dielectrics, Appl. Phys. Lett. 77, 2710 (2000)

    Article  CAS  Google Scholar 

  • G. A. Botton, J. A. Gupta, D. Landheer, J. P. McCaffrey, G. I. Sproule, M. J. Graham: Electron energy loss spectroscopy of interfacial layer formation in Gd2O3 films deposited directly on Si (001), J. Appl. Phys. 91, 2921 (2002)

    Article  CAS  Google Scholar 

  • D. A. Muller, T. Sorsch, S. Moccio, F. H. Baumann, K. Evans-Lutterodt, G. Timp: The electronic structure at the atomic scale of ultrathin gate dielectrics, Nature 399, 758 (1999)

    Article  CAS  Google Scholar 

  • R. F. Egerton: Electron Energy Loss in the Electron Microscope, 2 ed. (Plenum, New York 1996)

    Google Scholar 

  • L. Reimer (Ed.): Energy-Filtering Transmission Electron Microscopy (Springer, Berlin, Heidelberg 1996)

    Google Scholar 

  • K. Kimoto, K. Kobayashi, T. Aoyama, Y. Mitsui: Analyses of composition and chemical shift of silicon oxynitride film using energy-filtering transmission electron microscope based spatially resolved electron energy loss spectroscopy, Micron 30, 121 (1999)

    Article  CAS  Google Scholar 

  • U. Golla-Schindler, G. Benner, A. Putnis: Laterally resolved EELS for ELNES mapping of the Fe L23- and O K-edge, Ultramicroscopy 96, 573 (2003)

    Article  CAS  Google Scholar 

  • T. Walther: Electron energy-loss spectroscopic profiling of thin film structures: 0.39nm line resolution and 0.04eV precision measurement of near-edge structure shifts at interfaces, Ultramicroscopy 96, 401 (2003)

    Article  CAS  Google Scholar 

  • R. Lo-Nigro, R. G. Toro, G. Malandrino, V. Raineri, I. Fragala: A simple route to the synthesis of Pr2O3 high-k thin films, Adv. Mater. 15, 1071 (2003)

    Article  CAS  Google Scholar 

  • M. MacKenzie, A. J. Craven, D. W. McComb, D. A. Hamilton, S. McFadzean: Spectrum imaging of high-k dielectric stacks, Inst. Phys. Conf. Ser. 199, 299 (2003)

    Google Scholar 

  • G. Scarel, E. Bonera, C. Wiemer, G. Tallarida, S. Spiga, M. Fanciulli, I. L. Fedushkin, H. Schumann, Y. Lebedinskii, A. Zenkevich: Atomic-layer deposition of Lu2O3, Appl. Phys. Lett. 85, 630 (2004)

    Article  CAS  Google Scholar 

  • P. Batson, K. L. Kavanagh, C. Y. Wong, J. M. Woodall: Local bonding and electronic structure obtained from electron energy loss scattering, Ultramicroscopy 22, 89 (1987)

    Article  CAS  Google Scholar 

  • W. M. Skiff, R. W. Carpenter, S. H. Lin: Analysis of valence shell electronic excitations in silicon and its refractory compounds using electron energy loss microspectroscopy, J. Appl. Phys 64, 6328 (1988)

    Article  CAS  Google Scholar 

  • W. M. Skiff, R. W. Carpenter, S. H. Lin: Si L core edge fine structure in an oxidation series of silicon compounds:a comparison of microelectron energy loss spectra with theory, J. Appl. Phys. 58, 3463 (1985)

    Article  CAS  Google Scholar 

  • C. Colliex, M. Gasgnier, P. Trebbia: Analysis of the electron excitation spectra in heavy rare earth metals, hydrides and oxides, Le journal de Physique 37, 397 (1976)

    CAS  Google Scholar 

  • L. M. Brown, C. Colliex, M. Gasgnier: Fine structure analysis in EELS from rare earth sesquioxide thin films, Journal de Physique, Colloque C2, Supp. au n. 2 45, 433 (1984)

    Google Scholar 

  • S. Schamm, G. Zanchi: Study of the dielectric properties near the band gap by VEELS: gap measurements in bulk materials, Ultamicroscop 96, 559 (2003)

    Article  CAS  Google Scholar 

  • E. Dehan, P. Temple-Boyer, R. Henda, J. J. Pedroviejo, E. Scheid: Optical and structural properties of SiOx and SiNx materials, Thin Solid Films 266, 14 (1995)

    Article  CAS  Google Scholar 

  • O. Medenbach, D. Dettmar, R. D. Shannon, R. X. Fischer, W. M. Yen: Refractive index and optical dispersion of rare earth oxides using a small-prism technique, J. Opt. A: Pure Appl. Opt 3, 174 (2001)

    Article  CAS  Google Scholar 

  • T. Wiktorczyk: Optical properties of electron beam deposited lutetium oxide thin films, Optica Applicata XXXI (1), 83 (2001)

    Google Scholar 

  • A. V. Prokofiev, A. I. Shelykh, B. T. Melekh: Periodicity in thre band gap variation of Ln2X3 (X = O, S, Se) in the lanthanide series, J. Alloys and Compounds 242, 41 (1996)

    Article  CAS  Google Scholar 

  • H. Nohira, T. Shiraishi, T. Nakamura, K. Takahashi, M. Takeda, S. Ohmi, H. Iwai, T. Hattori: Chemical and electronic structures of Lu2O3 /Si interfacial transition layer, Appl. Surf. Sci. 76, 234 (2003)

    Article  CAS  Google Scholar 

  • G. Seguini, E. Bonera, S. Spiga, G. Scarel, M. Fanciulli: Energy-band diagram of metal/Lu2O3/silicon structures, Appl. Phys. Lett. 85, 5316 (2004)

    Article  CAS  Google Scholar 

  • K. Kimoto, T. Sekiguchi, T. Ayoama: Chemical shift mapping of Si L and K edges using spatially resolved EELS and energy-filtering TEM, J. Electron. Microsc. 46, 369 (1997)

    CAS  Google Scholar 

  • S. Schamm, R. Berjoan, P. Barathieu: Study of the chemical and structural organization of SIPOS films at the nanometer scale by TEM-EELS and XPS, Mat. Sci. Eng. B 107, 58 (2004)

    Article  CAS  Google Scholar 

  • A. Travlos, N. Boukos, G. Apostopoulos, A. Dimoulas, C. Giannakopoulos: EELS study of oxygen supertstructure in epitaxial Y2O3 layers, Mat. Sci. Eng. B 109, 52 (2004)

    Google Scholar 

  • G. Lucovsky, J. G. Hong, C. C. Fulton, Y. Zou, R. J. Nemanich, H. Ade, D. G. Scholm, J. L. Freeouf: Spectroscopic studies of metal high-k dielectrics: transition metal oxides and silicates, and complex rare earth/transition metal oxides, Phys. Stat. Sol. B 241, 2221 (2004)

    Article  CAS  Google Scholar 

  • D. A. Muller, J. Silcox: Delocalization in inelastic scattering, Ultramicroscopy 59, 195 (1995)

    Article  CAS  Google Scholar 

  • S. K. Kang, D. H. Ko, E. H. Kim, M. H. Cho, C. N. Whang: Interfacial reactions in the thin film Y2O3 on chemically oxidized Si(100) substrate systems, Thin Solid Films 353, 8 (1999)

    Article  CAS  Google Scholar 

  • F. Paumier, R. J. Gaboriaud: Interfacial reactions in Y2O3 thin films deposited on Si(100), Thin Solid Film 441, 307 (2003)

    Article  CAS  Google Scholar 

  • P. Ahmet, T. Koida, M. Takakura, K. Nakajima, M.Yoshimoto, H. Koinuma, M. Tanaka, M. Takegushi, T. Chikyow: Diffusion induced amorphization in the crystalline SrTiO3 thin films grown on Si (100) investigated by combinatorial method, Appl. Surf. Sci. 189, 307 (2002)

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Editor information

Marco Fanciulli Giovanna Scarel

Rights and permissions

Reprints and permissions

About this chapter

Cite this chapter

Schamm, S., Scarel, G., Fanciulli, M. Local Structure, Composition and Electronic Properties of Rare Earth Oxide Thin Films Studied Using Advanced Transmission Electron Microscopy Techniques (TEM-EELS). In: Fanciulli, M., Scarel, G. (eds) Rare Earth Oxide Thin Films. Topics in Applied Physics, vol 106. Springer, Berlin, Heidelberg . https://doi.org/10.1007/11499893_11

Download citation

  • DOI: https://doi.org/10.1007/11499893_11

  • Published:

  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-540-35796-4

  • Online ISBN: 978-3-540-35797-1

  • eBook Packages: Physics and AstronomyPhysics and Astronomy (R0)

Publish with us

Policies and ethics