Encapsulating bis(β-ketoiminato) polyethers. Volatile, fluorine-free barium precursors for metal - Organic chemical vapor deposition

Daniel B. Studebaker, Deborah A. Neumayer, Bruce J. Hinds, Charlotte L. Stern, Tobin J Marks

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The synthesis, characterization, and incorporation in volatile metal - organic chemical vapor deposition (MOCVD) precursors of a new class of linked β-ketoiminate-polyether-β-ketoiminate ligands is presented. These ligands are designed to encapsulate alkaline-earth cations having low charges and large ionic radii. Barium complexes having the general formula Ba[(RCOCHC(R')N)2(R'')] (R = tert-butyl or CF3; R' = tert-butyl, methyl, or CF3; R'' = -(CH2CH2O)4CH2CH2- or -(CH2CH2O)5CH2CH2)-) were prepared and characterized by 1H and 13C NMR spectroscopy, elemental analysis, and mass spectrometry. Single-crystal X-ray diffraction analysis of 2,2,5,25,28,28-hexamethyl-9,12,15,18,21-pentaoxa-4,25,diene-6,24-diimino-3,27 -pentacosadionatobarium(II) reveals a monomeric, nine-coordinate, tricapped trigonal prismatic coordination geometry. Single-crystal X-ray structural analysis of 1,1,1,24,24,24-hexafluoro-4,21-ditrifluoromethyl-8,11,14,17-tetraoxa-3,21-die ne-5,20-diimino-2,23-tetracosadionatobarium(II)·2DMSO reveals a monomeric, ten-coordinate, distorted tetracapped trigonal prismatic coordination geometry. Volatility data are presented for these barium complexes, demonstrating viability as MOCVD precursors. In addition, it is demonstrated that thin epitaxial films of BaTiO3 can be grown on (001) MgO by low-pressure MOCVD techniques using one of these barium complexes and Ti(dipivaloylmethanate)2(isopropoxide)2 as precursors.

Original languageEnglish
Pages (from-to)3148-3157
Number of pages10
JournalInorganic Chemistry
Issue number15
Publication statusPublished - Jul 24 2000


ASJC Scopus subject areas

  • Inorganic Chemistry

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