Journal of Thermal Analysis and Calorimetry
Volume/Issue:
Volume 105: Issue 1
Crystal structures and thermal properties of some rare earth alkoxides with tertiary alcohols
Possible precursors for atomic layer deposition of rare earth oxides
Authors:
Timo Hatanpää Laboratory of Inorganic Chemistry, University of Helsinki, P. O. Box 55, 00014, Helsinki, Finland

Search for other papers by Timo Hatanpää in
Current site
Google Scholar
PubMed Close
,
Kaupo Kukli Laboratory of Inorganic Chemistry, University of Helsinki, P. O. Box 55, 00014, Helsinki, Finland

Search for other papers by Kaupo Kukli in
Current site
Google Scholar
PubMed Close
,
Mikko Ritala Laboratory of Inorganic Chemistry, University of Helsinki, P. O. Box 55, 00014, Helsinki, Finland

Search for other papers by Mikko Ritala in
Current site
Google Scholar
PubMed Close
, and
Markku Leskelä Laboratory of Inorganic Chemistry, University of Helsinki, P. O. Box 55, 00014, Helsinki, Finland

Search for other papers by Markku Leskelä in
Current site
Google Scholar
PubMed Close
Pages:
61–71
Online Publication Date:
16 Apr 2011
Publication Date:
01 Jul 2011
Article Category:
Research Article
DOI:
https://doi.org/10.1007/s10973-011-1546-1
Keywords:
Rare earth metals; Alkoxides; TG; ALD precursors
Restricted access

Abstract

Rare earth (RE) alkoxides of Y, La, Pr, and Gd were synthesized using three tertiary alcohols namely 2,3-dimethyl-2-butanol, 2,2-dimethyl-3-ethyl-3-pentanol, and 3-isopropyl-2,4-dimethyl-pentan-3-ol. 1H and 13C NMR, elemental analysis (CHN) and MS were used to characterize the complexes. New crystal structures of dimeric [Y(OCEt2tBu)3]2, [La(OCEt2tBu)3]2, [Gd(OCiPr3)3]2, and [La(OCiPr3)3]2 were solved. Thermal properties of these compounds were studied with TG/SDTA and vacuum sublimation experiments. With all the cations Y, La, Pr, and Gd, the compounds with smallest ligand iPrMe2CO− seem to be the most volatile. The compounds with larger alkoxo ligands have lower volatility but their thermal stability is better. Atomic layer deposition experiments showed that RE oxide thin films could be grown from these alkoxides using water as the oxygen precursor.

  • 1. Leskelä, M, Ritala, M. Rare-earth oxide thin films as gate oxides in MOSFET transistors. J Solid State Chem. 2003;171:170 .

  • 2. Leskelä, M, Kukli, K, Ritala, M. Rare-earth oxide thin films for gate dielectrics in microelectronics. J Alloys Comp. 2006;418:27 .

  • 3. Leskelä, M, Ritala, M. Atomic layer deposition chemistry: recent developments and future challenges. Angew Chem Int Ed. 2003;42:5548 .

  • 4. Päiväsaari, J, Niinistö, J, Myllymäki, P, Dezelah IV, C, Winter, CH, Putkonen, M, Nieminen, M, Niinistö, L. Atomic layer deposition of rare earth oxides Fanciulli, M, Scarel, G, eds. Topics in applied physics. 106 Berlin, Heidelberg: Springer-Verlag; 2007 15–32.

    • Search Google Scholar
    • Export Citation

  • 5. Aspinall, HC. Requirements of precursors for MOCVD and ALD of rare earth oxides Fanciulli, M, Scarel, G, eds. Topics in applied physics. 106 Berlin, Heidelberg: Springer-Verlag; 2007 33–72.

    • Search Google Scholar
    • Export Citation

  • 6. Niinistö, J, Petrova, N, Putkonen, M, Niinistö, L, Arstila, K, Sajavaara, T. Gadolinium oxide thin films by atomic layer deposition. J Cryst Growth. 2005;285:191 .

    • Crossref
    • Search Google Scholar
    • Export Citation

  • 7. Nieminen, M, Putkonen, M, Niinistö, L. Formation and stability of lanthanum oxide thin films deposited from beta-diketonate precursor. Appl Surf Sci. 2001;174:155 .

    • Crossref
    • Search Google Scholar
    • Export Citation

  • 8. Potter, RJ, Chalker, PR, Manning, TD, Aspinall, HC, Loo, YF, Jones, AC, Smith, LM, Critchlow, GW, Schumacher, M. Deposition of HfO2, Gd2O3and PrOx by liquid injection ALD techniques. Chem Vap Deposition. 2005;11:159 .

    • Crossref
    • Search Google Scholar
    • Export Citation

  • 9. Lim, BS, Rahtu, A, Gordon, RG. Atomic layer depostion of transition metals. Nat Mater. 2003;2:729 .

  • 10. Lim, BS, Rahtu, A, deRouffignac, P, Gordon, RG. Atomic layer deposition of lanthanum aluminium oxide nano-laminates for electrical applications. Appl Phys Lett. 2004;84:3957 .

    • Crossref
    • Search Google Scholar
    • Export Citation

  • 11. Päiväsaari, J, Dezelah, CL, Back, D, El-Kadri, HM, Heeg, MJ, Putkonen, M, Niinistö, L, Winter, CH. Synthesis, structure, and properties of volatile lanthanide complexes containing amidinate ligands: application for Er2O3 thin film growth byatomic layer deposition. J Mater Chem. 2005;15:4224 .

    • Crossref
    • Search Google Scholar
    • Export Citation

  • 12. Putkonen, M, Niinitö, L. Organometallic precursors for atomic layer deposition in CVD precursors. Top Organomet Chem. 2005;9:125 .

  • 13. Bradley, DC, Mehotra, RC, Gaur, DP. Metal alkoxides. London: Academic Press; 1978.

  • 14. Poncelet, O, Sartain, WJ, Hubert-Pfalzgraf, LG, Folting, K, Caulton, KG. Chemistry of yttrium triisopropoxide revisited—characterization and crystal-structure of Y5(μ5-O)(μ3-OiPr)4(μ2-OiPr)4(OiPr)5. Inorg Chem. 1989;28:263 .

    • Crossref
    • Search Google Scholar
    • Export Citation

  • 15. Bradley, DC, Chudzynska, H, Frigo, DM, Hammond, ME, Hursthouse, MB, Mazid, MA. Pentanuclear oxoalkoxide clusters of scandium, yttrium, indium and ytterbium, x-ray crystal-structures of [M5(μ5-O)(μ3-OPri)4 (μ2-OPri)4(OPri)5] (M=In, Yb). Polyhedron. 1990;9:719 .

    • Crossref
    • Search Google Scholar
    • Export Citation

  • 16. Helgesson, G, Jagner, S, Poncelet, O, Hubert-Pfalzgraf, LG. Synthesis and molecular-structure of Nd5(μ5-O)(μ3-OR)2(μ2-OR)6(OR)5(ROH)2 (R=Pri)—the 1st example of a trigonal bipyramidal metal oxoalkoxide. Polyhedron. 1991;10:1559 .

    • Crossref
    • Search Google Scholar
    • Export Citation

  • 17. Bradley, DC, Chudzynska, H, Hursthouse, MB, Motevalli, M. Volatile tris-tertiary-alkoxides of yttrium and lanthanum—the x-ray crystal-structure of [La3(OBu-tert)9(Bu-tertOH)2]. Polyhedron. 1991;10:1049 .

    • Crossref
    • Search Google Scholar
    • Export Citation

  • 18. Anwander, R. Routes to monomeric lanthanide alkoxides Herrmann, WA, eds. Topics in current chemistry. 173 Berlin: Springer; 1996 149.

    • Search Google Scholar
    • Export Citation

  • 19. Kukli, K, Hatanpää, T, Ritala, M, Leskelä, M. Atomic layer deposition of gadolinium oxide films. Chem Vap Deposition. 2007;13:546 .

  • 20. Buhler, JD. Reaction of lithium alkyls with aldehydes and ketones—general study. J Org Chem. 1973;38:904 .

  • 21. Imamoto, T, Takiyama, N, Nakamura, K, Hatajima, T, Kamiya, Y. Reactions of carbonyl-compounds with Grignard-reagents in the presence of cerium chloride. J Am Chem Soc. 1989;111:4392 .

    • Crossref
    • Search Google Scholar
    • Export Citation

  • 22. Bradley DC , Ghotra JS, Hart FA. Low coordination numbers in lanthanide and actinide compounds. 1. Preparation and characterization of tris[bis(trimethylsilyl)-amido]lanthanides. J Chem Soc Dalton Trans. 1973: 1021.

    • Search Google Scholar
    • Export Citation

  • 23. Kottke, T, Stalke, D. Crystal handling at low-temperatures. J Appl Crystallogr. 1993;26:615 .

  • 24. Sheldrick, GM. SADABS, a software for empirical absorption correction. Gottingen, Germany: University of Gottingen; 2000.

  • 25. Sheldrick, GM. A short history of SHELX. Acta Crystallogr Sect A. 2008;64:112 .

  • 26. SHELXTL Reference Manual, Version 5.1; Bruker AXS, Analytical Instrumentation, Madison, Wisconsin, USA; 2000.

  • 27. Suntola, T. Atomic layer epitaxy. Thin Solid Films. 1992;216:84 .

  • 28. Ylilammi, M, Ranta-aho, T. Optical determination of the film thicknesses in multilayer thin-film structures. Thin Solid Films. 1993;232:56 .

    • Crossref
    • Search Google Scholar
    • Export Citation

  • 29. Shannon, RD. Revised effective ionic-radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr Sect A. 1976;32:751 .

    • Crossref
    • Search Google Scholar
    • Export Citation

  • 30. Boyle, TJ, Ottley, LAM. Advances in structurally characterized lanthanide alkoxide, aryloxide, and silyloxide compounds. Chem Rev. 2008;108:1896 .

  • 31. Stecher, HA, Sen, A, Rheingold, AL. 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. 1989;28:3280 .

    • Crossref
    • Search Google Scholar
    • Export Citation

  • 32. Evans, WJ, Golden, RE, Ziller, JW. A comparative synthetic and structural study of triphenylmethoxide and triphenylsiloxide complexes of the early lanthanides, including X-ray crystal-structures of La2(OCPh3)6 and Ce2(OSiPh3)6. Inorg Chem. 1991;30:4963 .

    • Crossref
    • Search Google Scholar
    • Export Citation

  • 33. Sen, A, Stecher, HA, Rheingold, AL. Synthesis, structure, and reactivity of homoleptic cerium(IV) and cerium(III) alkoxides. Inorg Chem. 1992;31:473 .

    • Crossref
    • Search Google Scholar
    • Export Citation

  • 34. Gromada, J, Morteux, A, Chenal, T, Ziller, JW, Leising, F, Carpentier, J-F. Neodymium alkoxides: synthesis, characterization and their combinations with dialkylmagnesiums as unique systems for polymerization and block copolymerization of ethylene and methyl methacrylate. Chem Eur J. 2002;8:3773 .

    • Crossref
    • Search Google Scholar
    • Export Citation

  • 35. Anwander, R, Munch, FC, Priemeier, T, Scherer, W, Runte, O, Hermann, WA. Volatile donor-functionalized alkoxy derivatives of lutetium and their structural characterization. Inorg Chem. 1997;36:3545 .

    • Crossref
    • Search Google Scholar
    • Export Citation

  • 36. Allen, FH. The Cambridge Structural Database: a quarter of a million crystal structures and rising. Acta Crystallogr B. 2002;58:380–388. .

    • Crossref
    • Search Google Scholar
    • Export Citation

  • 37. Dietrich, HM, Meermann, C, Tornroos, KW, Anwander, R. Sounding out the reactivity of trimethylyttrium. Organometallics. 2006;25:4316 .

  • 38. Aspinall, HC, Bickley, JF, Gaskell, JM, Jones, AC, Labat, G, Chalker, PR, Williams, PA. Precursors for MOCVD and ALD of rare earth oxides-complexes of the early lanthanides with a donor-functionalized alkoxide ligand. Inorg Chem. 2007;46:5852 .

    • Crossref
    • Search Google Scholar
    • Export Citation

  • 39. Kritikos M , Moustiakimov M, Wijk M, Westin G. Synthesis, structure and characterisation of Ln5O(OPri)13 with Ln=Nd, Gd or Er. J Chem Soc Dalton Trans. 2001: 1931.

    • Search Google Scholar
    • Export Citation

  • 40. Daniel, SD, Lehn, J-SM, van der Heide, P, Wang, Y, Hoffman, DM. Synthesis of cyclopentadienyl gadolinium and samarium alkoxide complexes. Inorg Chim Acta. 2006;359:257 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • Collapse
  • Expand
Cover Journal of Thermal Analysis and Calorimetry
Journal of Thermal Analysis and Calorimetry
Print ISSN:
1388-6150
Online ISSN:
1572-8943

To see the editorial board, please visit the website of Springer Nature.

Manuscript Submission: HERE

For subscription options, please visit the website of Springer Nature.

Journal of Thermal Analysis and Calorimetry
Language English
Size A4
Year of
Foundation		 1969
Volumes
per Year		 1
Issues
per Year		 24
Founder Akadémiai Kiadó
Founder's
Address		 H-1117 Budapest, Hungary 1516 Budapest, PO Box 245.
Publisher Akadémiai Kiadó
Springer Nature Switzerland AG
Publisher's
Address		 H-1117 Budapest, Hungary 1516 Budapest, PO Box 245.
CH-6330 Cham, Switzerland Gewerbestrasse 11.
Responsible
Publisher		 Chief Executive Officer, Akadémiai Kiadó
ISSN 1388-6150 (Print)
ISSN 1588-2926 (Online)

Monthly Content Usage

Abstract Views Full Text Views PDF Downloads
Jun 2024 8 0 0
Jul 2024 57 0 0
Aug 2024 44 3 5
Sep 2024 45 1 1
Oct 2024 189 1 1
Nov 2024 54 1 0
Dec 2024 7 0 0