Skip to main content

MOCVD Growth of Rare Earth Oxides:The Case of the Praseodymium/Oxygen System

  • Chapter
  • First Online:
Rare Earth Oxide Thin Films

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

Abstract

Chemical Vapor Deposition (CVD) uses one or more gaseous species (precursors) to form on a substrate, solid phase materials through an activated process. While today a large variety of precursors is known and rather complex deposition routes are involved, a user-friendly classification of precursor compounds as well as a viable discussion of their physical and chemical characteristics can be useful to MOCVD practitioners.

In this Chapter, an overview of both the exploitation and challenges of MOCVD fabrication of praseodymium oxides will be highlighted from different points of view, including the more suited precursors, the synthesis of thin films and their stability on silicon substrates.

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

  • S. Kimura, F. Arai, M. Ikezawa: Optical study on electronic structure of rare-earth sesquioxides, J. Phys. Soc. Jpn. 69, 3451 (2000)

    Article  CAS  Google Scholar 

  • H. L. Wan, X. P. Zhou, W. Z. Weng, R. Q. Long, Z. S. Chao, W. D. Zhang, M. S. Chem, J. Z. Luo, S. Q. Zhou: Catalytic performance, structure, surface properties and active oxygen species of the fluoride-containing rare earth (alkaline earth)-based catalysts for the oxidative coupling of methane and oxidative dehydrogenation of light alkanes, Catal. Today 51, 161 (1999)

    Article  CAS  Google Scholar 

  • J. Robertson: Band offsets of wide-band-gap oxides and implications for future electronic devices, J. Vac. Sci. Technol. B 18, 1785 (2000)

    Article  CAS  Google Scholar 

  • S. Chevalier, G. Bonnet, J. P. Larpin: Metal-organic chemical vapor deposition of Cr2 3 and Nd2 3 coatings. Oxide growth kinetics and characterization, Appl. Surf. Sci. 167, 125 (2000)

    Article  CAS  Google Scholar 

  • S. Jeon, K. Im, H. Yang, H. Lee, H. Sim, S. Choi, T. Jang, H. Hwang: Excellent electrical characteristics of lanthanide (Pr, Nd, Sm, Gd and Dy) oxide and lanthanide-doped oxide for MOS gate dielectric applications, Proc. IEDM Tech. Dig. p. 471 (2001)

    Google Scholar 

  • H. O. Pierson: Handbook of Chemical Vapor Deposition (Noesy, New York 1992)

    Google Scholar 

  • M. L. Hitchman, J. F. Jensen: Chemical Vapor Deposition: Principles and Applications (Academic Press, London 1993)

    Google Scholar 

  • R. G. Haier, L. Eyring: Handbook on the Physics and Chemistry of the Rare Earths (North-Holland, Amsterdam 1994)

    Google Scholar 

  • Z. C. Kang, L. Eyring: Fluorite structural principles: Disordered α -phase to ordered intermediate phases in praseodymia, J. Alloy and Comp. 275–277, 721 (1998)

    Article  Google Scholar 

  • L. Eyring, N. C. Baenzige: On the structure and related properties of the oxides of praseodymium, J. Appl. Phys. 33, 428 (1962)

    Article  CAS  Google Scholar 

  • N. Horio, M. Hiramatsu, M. Nawata, K. Imaeda, T. Torii: Preparation of zinc oxide metal oxide multilayered thin films for low-voltage varistors, Vacuum 51, 719 (1998)

    Article  CAS  Google Scholar 

  • C. W. Nahm: Electrical properties and stability of praseodymium oxide-based ZnO varistor ceramics doped with Er2 3, J. Eur. Ceram. Soc. 23, 1345 (2003)

    Article  CAS  Google Scholar 

  • D. W. Hwang, J. S. Lee, W. Li, S. H. Oh: Electronic band structure and photocatalytic activity of Ln(2)Ti(2)O(7) (Ln = La, Pr, Nd), J. Phys. Chem. B 107, 4963 (2003)

    Article  CAS  Google Scholar 

  • C. Qiu, H. Chen, Z. Xie, M. Wong, H. S. Kwok: Praseodymium oxide coated anode for organic light-emitting diode, Appl. Phys. Lett. 80, 3485 (2002)

    Article  CAS  Google Scholar 

  • H. J. Osten, J. P. Liu, P. Gaworzewski, E. Bugiel, P. Zaumseil: High k gate dielectric with ultra-low leakage current based on praseodymium oxide, Proc. IEDM Tech. Dig. p. 653 (2000)

    Google Scholar 

  • G. Adachi, N. Imanaka: The binary rare earth oxides, Chem. Rev. 98, 1479 (1998)

    Article  CAS  Google Scholar 

  • H. J. Osten, J. P. Liu, H. J. Mussig: Band gap and band discontinuities at crystalline Pr2 3/Si(001) heterojunctions, Appl. Phys. Lett. 80, 297 (2002)

    Article  CAS  Google Scholar 

  • L. R. Morss: Thermochemical properties of yttrium, lanthanum and lanthanide elements and ions, Chem. Rev. 76, 827 (1976)

    Article  CAS  Google Scholar 

  • T. J. Marks: Coordination chemistry ruotes to films for superconducting electronics, Pure Appl. Chem. 67, 313 (1995)

    CAS  Google Scholar 

  • M. Tiitta, L. Niinisto: Volatile metal beta-diketonates: ALE and CVD precursors for electroluminescent device thin films, Chem. Vap. Dep. 3, 167 (1997)

    Article  CAS  Google Scholar 

  • J. A. Belot, D. A. Neumayer, C. J. Reedy, D. B. Studebaker, B. J. Hinds, C. L. Stern, T. J. Marks: Volatility by design. Synthesis and characterization of polyether adducts of bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)barium and their implementation as metal-organic chemical vapor deposition precursors, Chem. Mater. 9, 1638 (1997)

    Article  CAS  Google Scholar 

  • N. L. Edleman, A. C. Wang, J. A. Belot, A. W. Metz, J. R. Babcock, A. M. Kawaoka, J. Ni, M. V. Metz, C. J. Flaschenriem, C. L. Stern, L. M. Liable-Sands, A. L. Rheingold, P. R. Markworth, R. P. H. Chang, M. P. Chudzik, C. R. Kannewurf, T. J. Marks: Synthesis and characterization of volatile, fluorine-free beta-ketoiminate lanthanide MOCVD precursors and their implementation in low-temperature growth of epitaxial CeO2 buffer layers for superconducting electronics, Inorg. Chem. 41, 5005 (2002)

    Article  CAS  Google Scholar 

  • G. Malandrino, F. Castelli, I. L. Fragalà: A novel route to the 2nd generation alkaline-earth metal precursors for metal organic chemical vapor deposition: One step synthesis of M(hfa)2tetraglyme (M= Ba, Sr, Ca, and hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentadione), Inorg. Chim. Acta 224, 203 (1994)

    Article  CAS  Google Scholar 

  • S. B. Turnipseed, R. M. Barkley, R. E. Siever: Synthesis and characterization of alkaline-earth-metal beta-diketonate complexes used as precursors for chemical vapor deposition of thin films superconductors, Inorg. Chem. 30, 1164 (1991)

    Article  CAS  Google Scholar 

  • G. Rossetto, A. Polo, F. Bentollo, M. Porchia, P. Zanella: Studies on molecular barium precursors for MOCVD: Synthesis and characterization of barium 2,2,6,6-Tetramethyl-3,5- heptanedionate – X-ray crystal structure of [BA(THD)2.ET2]2, Polyhedron 11, 979 (1992)

    Article  CAS  Google Scholar 

  • G. Malandrino, C. Benelli, F. Castelli, I. L. Fragalà: Synthesis, characterizations, crystal structure and mass transport properties of lanthanum β-diketonate glyme complexes, volatile precursors for metal-organic chemical vapor deposition applications, Chem. Mater. 10, 3434 (1998)

    Article  CAS  Google Scholar 

  • G. Malandrino, R. L. Nigro, F. Castelli, I. L. Fragalà, C. Benelli: Volatile Ce(III)hexafluoroacetylacetonate glyme adducts as promising precursors for MOCVD deposition of CeO2 thin films, Chem. Vap. Dep. 6, 233 (2000)

    Article  CAS  Google Scholar 

  • K. D. Pollard, H. A. Jenkins, R. J. Puddephat: Chemical vapor deposition of cerium oxide using the precursors [Ce(hfac)3(glyme)], Chem. Mater. 12, 701 (2000)

    Article  CAS  Google Scholar 

  • G. Malandrino, O. Incontro, F. Castelli, I. L. Fragalà, C. Benelli: Synthesis, characterization and mass transport properties of two novel gadolinium(III) hexafluoroacetylacetonate polyether adducts: Promising precursors for MOCVD of GdF3 films, Chem. Mater. 8, 1292 (1996)

    Article  CAS  Google Scholar 

  • G. Malandrino, M. Bettinelli, A. Speghini, I. L. Fragalà: Europium ``second generation'' precursors for metal-organic chemical vapor deposition: Characterization and optical spectroscopy, Eur. J. Inorg. Chem. p. 1039 (2001)

    Google Scholar 

  • R. Lo Nigro, G. Malandrino, I. L. Fragalà: MOCVD of cerium dioxide (100) oriented films on random Hastelloy C 276, Chem. Mater. 13, 4402 (2001)

    Article  CAS  Google Scholar 

  • R. Lo Nigro, R. Toro, G. Malandrino, I. L. Fragalà: Heteroepitaxial growth of nanostructured cerium dioxide thin films by MOCVD on a (001) TiO2 substrate, Chem. Mater. 15, 1434 (2003)

    Article  CAS  Google Scholar 

  • G. Malandrino, I. L. Fragalà, P. Scardi: Heteroepitaxy of LaAlO3 (100) on SrTiO3 (100): situ growth of LaAlO3 thin films by metal-organic chemical vapor deposition from a liquid single-source, Chem. Mater. 10, 3765 (1998)

    Article  CAS  Google Scholar 

  • J. M. Zhang, F. DiMeo Jr, B. W. Wessels, D. L. Schultz, T. J. Marks, J. L. Schindler, C. R. Kanerwurf: A new route to high-Tc superconducting Bi–Sr–Ca–Cu–O thin films: improved deposition efficiency and film morphology using ammonia–argon mixtures as the carrier gas, J. Appl. Phys. 71, 2769 (1992)

    Article  CAS  Google Scholar 

  • S. B. Turnipseed, R. M. Barkley, R. E. Sievers: Synthesis and characterization of alkaline-earth-metal beta-diketonate complexes used as precursors for chemical vapor deposition of thin film superconductors, Inorg. Chem. 30, 1164 (1991)

    Article  CAS  Google Scholar 

  • S. Liang, C. S. Chern, Z. Q. Shi, P. Lu: Control of CeO2 growth by metalorganic chemical vapor deposition with a special source evaporator, J. Cryst. Growth 151, 359 (1995)

    Article  CAS  Google Scholar 

  • H. A. Luten, W. S. Rees Jr., V. L. Goedkend: Preparation and structural characterization, and chemical vapor deposition studies with, certain yttrium tris(beta-diketonate) compounds, Chem. Vap. Dep. 2, 149 (1996)

    Article  CAS  Google Scholar 

  • K. J. Eisentraut, R. E. Siever: Volatile rare earth chelates, J. Am. Chem. Soc. 87, 5254 (1965)

    Article  CAS  Google Scholar 

  • R. Lo Nigro, R. G. Toro, G. Malandrino, I. L. Fragalà: Study of the thermal properties of Pr(III) precursors and their implementation in the MOCVD growth of praseodymium oxide films, J. Electrochem. Soc. 151, F206 (2004)

    Article  CAS  Google Scholar 

  • R. Lo Nigro, R. G. Toro, G. Malandrino, V. Raineri, I. L. Fragalà: A simple route to the synthesis of Pr2 3 high-k films, Adv. Mater. 15, 1071 (2003)

    Article  CAS  Google Scholar 

  • R. Lo Nigro, R. G. Toro, G. Malandrino, G. G. Condorelli, V. Raineri, I. L. Fragalà: Praseodymium silicate as a high k dielectric candidate: An insight on the Pr2 3 film/Si substrate interface fabricated through an MOCVD process, Adv. Funct. Mater. 15, 838 (2005)

    Article  CAS  Google Scholar 

  • D. K. Fork, D. B. Fenner, T. H. Geballe: Growth of epitaxial PrO2 thin films on hydrogen terminated Si (111) by pulsed lased deposition, J. Appl. Phys. 68, 4316 (1990)

    Article  CAS  Google Scholar 

  • H. Ogasawara, A. Kotani, R. Potze, G. A. Sawatzky, B. T. Thole: Praseodymium 3D-core and 4D-core photoemission spectra of Pr2 3, Phys. Rew. B 44, 5465 (1991)

    Article  CAS  Google Scholar 

  • J. X. Wu, Z. M. Wang, F. Q. Li, M. S. Ma: Photoemission study of the oxidation and the post-annealing behaviors of a Pr-covered Si(100) surface, Appl. Surf. Sci. 225, 229 (2004)

    Article  CAS  Google Scholar 

  • S. Lütkehoff, M. Neumann, A. 'Slebarski: 3and 4 X-ray-photoelectron spectra of Pr under gradual oxidation, Phys. Rev. B 52, 13808 (1995)

    Article  Google Scholar 

  • G. F. Cerefolini, C. Galati, S. Lorenti, L. Renna, O. Viscuso, C. Bongiorno, V. Raineri, C. Spinella, G. G. Condorelli, I. L. Fragalà, A. Terrasi: The early oxynitridation stages of hydrogen-terminated (100) silicon after exposure to N2:N2O. III. Initial conditions, Appl. Phys. A 77, 403 (2003)

    Article  Google Scholar 

  • D. Schmeisser, H. J. Mussig: The Pr2 3/Si(001) interface studied by synchrotron radiation photo-electron spectroscopy, Solid State Electron. 47, 1607 (2003)

    Article  CAS  Google Scholar 

  • J. F. Malder, W. F. Stickel, P. E. Sobol, K. D. Bomben: Handbook of X-ray Photoelectron Spectroscopy (Perkin-Elmer, Eden Proucie 1992)

    Google Scholar 

  • D. D. Sarma, C. N. R. Rao: XPES studies of oxides of 2nd-row and 3nd-row transition-metals including rare earths, J. Electron. Spectrosc. Relat. Phenom. 20, 25 (1980)

    Article  CAS  Google Scholar 

  • T. Gouguosi, D. Niu, R. W. Ashcraft, G. N. Parson: Carbonate formation during post-deposition ambient exposure of high-dielectrics, Appl. Phys. Lett. 83, 3543 (2003)

    Article  Google Scholar 

  • J. J. Chambers, G. N. Parson: Physical and electrical characterization of ultrathin yttrium silicate insulators on silicon, J. Appl. Phys. 90, 918 (2001)

    Article  CAS  Google Scholar 

  • S. Jeon, H. Hwang: Electrical and physical characteristics of PrTix y for metal-oxide-semiconductor gate dielectric applications, Appl. Phys. Lett. 81, 4856 (2002)

    Article  CAS  Google Scholar 

  • A. Fissel, J. Dabrowski, H. J. Osten: Photoemission and initio theoretical study of interface and film formation during epitaxial growth and annealing of praseodymium oxide on Si(001), J. Appl. Phys. 91, 8986 (2002)

    Article  CAS  Google Scholar 

  • R. Lo Nigro, V. Raineri, C. Bongiorno, R. Toro, G. Malandrino, I. L. Fragalà: Dieletric properties of Pr2 3 high-k films grown by metalorganic chemical vapor deposition on silicon, Appl. Phys. Lett. 83, 129 (2003)

    Article  CAS  Google Scholar 

  • R. Lo Nigro, R. Toro, G. Malandrino, P. Fiorenza, V. Raineri, I. L. Fragalà: Effects of deposition temperature on the microstructural and electrical properties of praseodymium oxide based films, Mater. Sci. Eng. B 118, 117 (2005)

    Article  Google Scholar 

  • R. Lo Nigro, R. Toro, G. Malandrino, V. Raineri, I. L. Fragalà: Electrical properties of MOCVD praseodymium oxide based MOS structures, Proc. ESSDERC p. 375 (2003)

    Google Scholar 

  • D. Chadwick, J. McAleese, K. Senliw, B. C. H. Steele: On the application of XPS to ceria films grown by MOCVD using a fluorinated precursors, Appl. Surf. Sci. 99, 417 (1996)

    Article  CAS  Google Scholar 

  • Y. J. Cho, M. Noma, Y. Hamakawa: Filtered full-color thin-film electroluminescent device with ZnS:TbOF/ZnS:PrOF phosphor layers, Sensors Mater. 9, 25 (1997)

    CAS  Google Scholar 

  • S. Kuck, I. Sokolska: Room temperature emission from the Pr3+1S0-level in PrF3, Appl. Phys. A: Mater. Sci. Process. 77, 469 (2003)

    Article  Google Scholar 

  • G. Malandrino, R. Lo Nigro, P. Rossi, P. Dapporto, I. L. Fragalà: A volatile Pb(II) β-diketonate diglyme complex as a promising precursor of MOCVD of lead oxide films, Inorg. Chim. Acta 357, 3927 (2004)

    Article  CAS  Google Scholar 

  • M. E. Fragala, G. Compagnini, G. Malandrino, C. Spinella, O. Puglisi: Silver nanoparticles dispersed in polyimide thin film matrix, Eur. Phys J. D 9, 631 (1999)

    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

Nigro, R.L., Malandrino, G., Toro, R.G., Fragalà, I.L. MOCVD Growth of Rare Earth Oxides:The Case of the Praseodymium/Oxygen System. 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_3

Download citation

Publish with us

Policies and ethics