Volatile Hexavalent Oxo-amidinate Complexes: Molybdenum and Tungsten Precursors for Atomic Layer Deposition

Aidan R. Mouat, Anil U. Mane, Jeffrey W. Elam, Massimiliano Delferro, Tobin J Marks, Peter C Stair

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

New complexes MoO2(tBuAMD)2 (1) and WO2(tBuAMD)2 (2) (AMD = acetamidinato) are synthesized and fully characterized as precursors for atomic layer deposition (ALD). They contain metal-oxo functionalities not previously utilized in ALD-type growth processes and are fully characterized by 1H and 13C NMR, X-ray diffraction (XRD), Fourier transform infrared, thermogravimetric analysis, single-crystal XRD, and elemental analysis. Guided by quartz-crystal microbalance studies, ALD growth methodologies for both complexes have been developed. Remarkably, these isostructural compounds exhibit dramatic differences in ALD properties. Using 1 and O3, amorphous, ultrathin molybdenum oxynitride (MoON) films are grown on Si(100) wafers. Using 2 and H2O yields amorphous WO3 films on Si(100) wafers that crystallize as WO3 nanowires upon annealing. Although 1/H2O and 2/O3 growth was attempted, effective ALD growth could only be obtained with 1/O3 and 2/H2O, underscoring reactivity differences in these precursors. Film thicknesses, compositions, and optical and electrical parameters are characterized by variable angle spectroscopic ellipsometry, X-ray reflectivity, grazing incidence X-ray diffraction, X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and atomic force microscopy techniques. The hitherto unknown ALD chemistry of group VI metal-oxo compounds lays a foundation for their use in the ALD synthesis of heterogeneous catalysts.

Original languageEnglish
Pages (from-to)1907-1919
Number of pages13
JournalChemistry of Materials
Volume28
Issue number6
DOIs
Publication statusPublished - Mar 22 2016

ASJC Scopus subject areas

  • Materials Chemistry
  • Chemical Engineering(all)
  • Chemistry(all)

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