Requirements of Precursors for MOCVDand ALD of Rare Earth Oxides

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


This Chapter gives an account of the coordination chemistry of precursors for MOCVD and ALD of rare earth oxides. It opens with a brief introduction to the coordination chemistry of the rare earth elements, and then describes the strategies that have been employed to design and synthesize rare earth complexes with reasonable volatility. The chemical requirements of precursors for MOCVD and ALD are outlined, and it is shown that these requirements may be mutually exclusive. Important classes of precursors, including amides, alkoxides, diketonates and organometallics, are surveyed.


71.55.-i; 72.80.Sk; 73.20.At; 75.47.Lx; 77.55.+f 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. R. D. Shannon: Revised effective ionic-radii and systematic studies of interatomic distances in halides and chalcogenides, Acta Crystallogr. Sect. A 32, 751 (1976) CrossRefGoogle Scholar
  2. A. C. Jones: Molecular design of improved precursors for the MOCVD of electroceramic oxides, J. Mater. Chem. 12, 2576 (2002) CrossRefGoogle Scholar
  3. D. C. Bradley, J. S. Ghotra, F. A. Hart: Low coordination numbers in lanthanide and actinide compounds. 1. Preparation and characterization of tris[bis(trimethylsilyl)-amido]lanthanides, J. Chem. Soc. – Dalton Trans. p. 1021 (1973) Google Scholar
  4. R. Anwander, O. Runte, J. Eppinger, G. Gerstberger, E. Herdtweck, M. Spiegler: Synthesis and structural characterisation of rare-earth bis(dimethylsilyl)amides and their surface organometallic chemistry on mesoporous MCM-41, J. Chem. Soc. – Dalton Trans. p. 847 (1988) Google Scholar
  5. D. C. Bradley, J. S. Ghotra, F. A. Hart: Tris(di-2-propylamido)yttrium and related neodymium and ytterbium compounds, Inorg. Nucl. Chem. Lett. 12, 735 (1976) CrossRefGoogle Scholar
  6. W. J. Evans, R. Anwander, R. J. Doedens, J. W. Ziller: The use of heterometallic bridging moieties to generate tractable lanthanide complexes of small ligands, Angew. Chem. – Int. Ed. Engl. 33, 1641 (1994) CrossRefGoogle Scholar
  7. H. A. Stecher, A. Sen, A. L. Rheingold: Synthesis, structure, and reactivity of tricoordinate cerium(III) aryloxides – the 1st structurally characterized monomeric Ln(OR)3 complexes, Inorg. Chem. 27, 1130 (1988) CrossRefGoogle Scholar
  8. H. A. Stecher, A. Sen, A. L. Rheingold: Synthesis, structure, and reactivity of cerium(iii) alkoxides. 2. Thermal decomposition of Ce(OCtBu3)3 and the structure of [Ce(OCHtBu2)3]2, Inorg. Chem. 28, 3280 (1989) CrossRefGoogle Scholar
  9. W. A. Herrmann, R. Anwander, M. Kleine, W. Scherer: Complexes of the lanthanides. 1. Solvent-free alkoxide complexes of neodymium and dysprosium – crystal and molecular structure of trans-bis(acetonitrile)tris(tri-tert-butylmethoxy)neodymium, Chem. Ber.-Recl. 125, 1971 (1992) Google Scholar
  10. D. C. Bradley, H. Chudzynska, M. E. Hammond, M. B. Hursthouse, M. Motevalli, W. Ruowen: The preparation and characterization of volatile derivatives of trivalent metals using fluorinated alkoxide ligands – X-ray structures of Sc(OCH(CF3)2)3(NH3)2, 7pr(ocme(cf3)2)3(nh3)20, (OCMe(CF3)2)3(THF)3 and Pr(OCMe2(CF3))3, Polyhedron 11, 375 (1992) CrossRefGoogle Scholar
  11. P. B. Hitchcock, M. F. Lappert, R. G. Smith, R. A. Bartlett, P. P. Power: Synthesis and structural characterization of the 1st neutral homoleptic lanthanide metal(III) alkyls - [LnR3] [Ln = La or Sm, R = Ch(SiMe3)2], J. Chem. Soc. – Chem. Commun. p. 1007 (1988) Google Scholar
  12. W. J. Evans, T. J. Deming, J. M. Olofson, J. W. Ziller: Synthetic and structural studies of a series of soluble cerium(IV) alkoxide and alkoxide nitrate complexes, Inorg. Chem. 28, 4027 (1989) CrossRefGoogle Scholar
  13. P. S. Gradeff, F. G. Schreiber, K. C. Brooks, R. E. Sievers: Simplified method for the synthesis of ceric alkoxides from ceric ammonium-nitrate, Inorg. Chem. 24, 1110 (1985) CrossRefGoogle Scholar
  14. M. P. Singh, S. A. Shivashankar: Structural and optical properties of polycrystalline thin films of rare earth oxides grown on fused quartz by low pressure MOCVD, J. Cryst. Growth 276, 148 (2005) CrossRefGoogle Scholar
  15. M. P. Singh, C. S. Thakur, K. Shalini, S. Banerjee, N. Bhat, S. A. Shivashankar: Structural, optical, and electrical characterization of gadolinium oxide films deposited by low-pressure metalorganic chemical vapor deposition, J. Appl. Phys. 96, 5631 (2004) CrossRefGoogle Scholar
  16. K. J. Eisentraut, R. E. Sievers: Volatile rare earth chelates, J. Am. Chem. Soc. 87, 5254 (1965) CrossRefGoogle Scholar
  17. W. J. Evans, D. G. Giarikos, M. A. Johnston, M. A. Greci, J. W. Ziller: Reactivity of the europium hexafluoroacetylacetonate (hfac) complex, Eu(hfac)3(diglyme), and related analogs with potassium: Formation of the fluoride hfac `ate' complexes, LnF(hfac)3K(diglyme)2, J. Chem. Soc. – Dalton Trans. p. 520 (2002) Google Scholar
  18. G. Malandrino, R. Licata, F. Castelli, I. L. Fragalà, C. Benelli: New thermally stable and highly volatile precursors for lanthanum MOCVD – Synthesis and characterization of lanthanum beta-diketonate glyme complexes, Inorg. Chem. 34, 6233 (1995) CrossRefGoogle Scholar
  19. K. D. Pollard, H. A. Jenkins, R. J. Puddephatt: Chemical vapor deposition of cerium oxide using the precursors [Ce(hfac)3(glyme)], Chem. Mat. 12, 701 (2000) CrossRefGoogle Scholar
  20. B. D. Fahlman, A. R. Barron: Substituent effects on the volatility of metal beta-diketonates, Adv. Mater. Opt. Electron. 10, 223 (2000) CrossRefGoogle Scholar
  21. W. S. Rees, O. Just, S. L. Castro, J. S. Matthews: Synthesis and magnetic and structural characterization of the first homoleptic lanthanide beta-ketoiminate, Inorg. Chem. 39, 3736 (2000) CrossRefGoogle Scholar
  22. J. A. Belot, A. C. Wang, R. J. McNeely, L. Liable-Sands, A. L. Rheingold, T. J. Marks: Highly volatile, low-melting, fluorine-free precursors for MOCVD of lanthanide oxide-containing thin films, Chem. Vap. Dep. 5, 65 (1999) CrossRefGoogle Scholar
  23. 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) CrossRefGoogle Scholar
  24. W. A. Herrmann, R. Anwander, M. Denk: Complexes of the Lanthanides. 3. Volatile neodymium and yttrium alkoxides with new bulky chelating ligands, Chem. Ber. – Recl. 125, 2399 (1992) Google Scholar
  25. R. Anwander, F. C. Munck, T. Priermeier, W. Scherer, O. Runte, W. A. Herrmann: Volatile donor-functionalized alkoxy derivatives of lutetium and their structural characterization, Inorg. Chem. 36, 3545 (1997) CrossRefGoogle Scholar
  26. H. C. Aspinall, J. Gaskell, P. A. Williams, A. C. Jones, P. R. Chalker, P. A. Marshall, J. F. Bickley, L. M. Smith, G. W. Critchlow: Growth of praseodymium oxide thin films by liquid injection MOCVD using a novel praseodymium alkoxide precursor, Chem. Vap. Dep. 9, 235 (2003) CrossRefGoogle Scholar
  27. O. Poncelet, L. G. Hubertpfalzgraf, J. C. Daran, R. Astier: Alkoxides with polydentate alcohols – synthesis and structure of [Y(OC2H4OMe)3]10, a hydrocarbon soluble cyclic decamer, J. Chem. Soc. – Chem. Commun. p. 1846 (1989) Google Scholar
  28. Y. F. Loo, R. O` Kane, A. C. Jones, H. C. Aspinall, R. J. Potter, P. R. Chalker, J. F. Bickley, S. Taylor, L. M. Smith: Deposition of HfO2 and ZrO2 films by liquid injection MOCVD using new monomeric alkoxide precursors, J. Mater. Chem. 15, 1896 (2005) CrossRefGoogle Scholar
  29. Y. K. Gunko, F. T. Edelmann: Organolanthanides in materials science, Comments Inorg. Chem. 19, 153 (1997) Google Scholar
  30. J. M. Birmingham, G. Wilkinson: The cyclopentadienides of scandium, yttrium and some rare earth elements, J. Am. Chem. Soc. 78, 42 (1956) CrossRefGoogle Scholar
  31. W. A. Herrmann, R. Anwander, F. C. Munck, W. Scherer: Complexes of the lanthanides. 4. Alkyl-substituted and donor- substituted cyclopentadienyl complexes of neodymium, Chem. Ber.-Recl. 126, 331 (1993) Google Scholar
  32. T. Nakamura, T. Nishimura, R. Tai, K. Tachibana: Reaction mechanism of a lanthanum precursor in liquid source metalorganic chemical vapor deposition, Mater. Sci. Eng. B – Solid State Mater. Adv. Technol. 118, 253 (2005) Google Scholar
  33. H. A. Luten, W. S. Rees, V. L. Goedken: Preparation and structural characterization of, and chemical vapor deposition studies with, certain yttrium tris(beta-diketonate) compounds, Chem. Vap. Dep. 2, 149 (1996) CrossRefGoogle Scholar
  34. 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. Mat. 8, 1292 (1996) CrossRefGoogle Scholar
  35. G. Malandrino, G. G. Condorelli, R. Lo Nigro: MOCVD of LaAlO3 films from a molten precursor mixture: Characterization of liquid and gas and deposited phases, Chem. Vap. Dep. 10, 171 (2004) CrossRefGoogle Scholar
  36. R. G. Gordon, S. Barry, R. N. R. Broomhall-Dillard, D. J. Teff: Synthesis and solution decomposition kinetics of flash- vaporizable liquid barium beta-diketonates, Adv. Mater. Opt. Electron. 10, 201 (2000) CrossRefGoogle Scholar
  37. S. Horii, K. Yamamoto, M. Asai, H. Miya, M. Niwa: Metalorganic chemical vapor deposition of HfO2 films through the alternating supply of tetrakis(1-methoxy-2-methyl-2-propoxy)-hafnium and remote-plasma oxygen, Jpn. J. Appl. Phys. Part 1 - Regul. Pap. Short Notes Rev. Pap. 42, 5176 (2003) Google Scholar
  38. P. A. Williams, A. C. Jones, N. L. Tobin, P. R. Chalker, S. Taylor, P. A. Marshall, J. E. Bickley, L. M. Smith, H. O. Davies, G. W. Critchlow: Growth of hafnium dioxide thin films by liquid-injection MOCVD using alkylamide and hydroxylamide precursors, Chem. Vap. Dep. 9, 309 (2003) CrossRefGoogle Scholar
  39. H. C. Aspinall, P. A. Williams, J. Gaskell, A. C. Jones, J. L. Roberts, L. M. Smith, P. R. Chalker, G. W. Critchlow: Growth of lanthanum silicate thin films by liquid injection MOCVD using tris[bis(trimethylsilyl)amido]lanthanum, Chem. Vap. Dep. 9, 7 (2003) CrossRefGoogle Scholar
  40. H. C. Aspinall, J. Gaskell, P. A. Williams, A. C. Jones, P. R. Chalker, P. A. Marshall, L. M. Smith, G. W. Critchlow: Growth of praseodymium oxide and praseodymium silicate thin films by liquid injection MOCVD, Chem. Vap. Dep. 10, 83 (2004) CrossRefGoogle Scholar
  41. M. J. Hynes, M. T. Mooney, A. Moloney: The reactions of zinc(II) with 1,3-diketones in aqueous solution – Catalysis by cacodylic acid during complex formation, J. Chem. Soc.-Dalton Trans. p. 313 (1993) Google Scholar
  42. J. Paivasaari, M. Putkonen, L. Niinistö: A comparative study on lanthanide oxide thin films grown by atomic layer deposition, Thin Solid Films 472, 275 (2005) CrossRefGoogle Scholar
  43. J. Paivasaari, M. Putkonen, T. Sajavaara, L. Niinistö: Atomic layer deposition of rare earth oxides: Erbium oxide thin films from beta-diketonate and ozone precursors, J. Alloy. Compd. 374, 124 (2004) CrossRefGoogle Scholar
  44. D. M. Hausmann, E. Kim, J. Becker, R. G. Gordon: Atomic layer deposition of hafnium and zirconium oxides using metal amide precursors, Chem. Mat. 14, 4350 (2002) CrossRefGoogle Scholar
  45. R. R. Fraser, T. S. Mansour, S. Savard: Acidity measurements on pyridines in tetrahydrofuran using lithiated silylamines, J. Org. Chem. 50, 3232 (1985) CrossRefGoogle Scholar
  46. K. Kukli, M. Ritala, T. Pilvi, T. Sajavaara, M. Leskelä, A. C. Jones, H. C. Aspinall, D. C. Gilmer, P. J. Tobin: Evaluation of a praseodymium precursor for atomic layer deposition of oxide dielectric films, Chem. Mat. 16, 5162 (2004) Google Scholar
  47. R. J. Potter, P. R. Chalker, T. D. Manning, H. C. Aspinall, Y. F. Loo, A. C. Jones, L. M. Smith, G. W. Critchlow, M. Schumacher: Deposition of HfO2, Gd2O3 and PrOx by liquid injection ALD techniques, Chem. Vap. Dep. 11, 159 (2005) CrossRefGoogle Scholar
  48. F. G. Bordwell, J. P. Cheng, G. Z. Ji, A. V. Satish, X. M. Zhang: Bond-dissociation energies in DMSO related to the gas-phase, J. Am. Chem. Soc. 113, 9790 (1991) CrossRefGoogle Scholar
  49. J. Niinistö, M. Putkonen, L. Niinistö: Processing of Y2O3 thin films by atomic layer deposition from cyclopentadienyl-type compounds and water as precursors, Chem. Mat. 16, 2953 (2004) CrossRefGoogle Scholar
  50. M. Putkonen, M. Nieminen, J. Niinistö, L. Niinistö: Surface-controlled deposition of Sc2O3 thin films by atomic layer epitaxy using beta-diketonate and organometallic precursors, Chem. Mat. 13, 4701 (2001) CrossRefGoogle Scholar
  51. A. Gervasini, A. Auroux: Thermodynamics of adsorbed molecules for a new acid-base topochemistry of alumina, J. Phys. Chem. 97, 2628 (1993) CrossRefGoogle Scholar

Authors and Affiliations

  1. 1.Department of Chemistry, Donnan and Robert Robinson LaboratoriesUniversity of LiverpoolLiverpoolUnited Kingdom

Personalised recommendations