Homogeneous Decomposition of Aryl- and Alkylimido Precursors for the Chemical Vapor Deposition of Tungsten Nitride: A Combined Density Functional Theory and Experimental Study.

MOCVD growth of tungsten nitride (WN) and tungsten carbonitride (WNC) thin films has been reported from the complexes CI(CHCN)W(NR) (1: R = Ph; 2: R = Pr; 3: R = CH). To evaluate the role of the imido substituent in film growth, gas-phase homogeneous decomposition of precursor molecules was investig...

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Publicado en:Journal of the American Chemical Society Vol. 128; no. 42; pp. 13781 - 13789
Autores principales: Yong Sun Won, Young Seok Kim, Anderson, Timothy J., Reitfort, Laurel L., Ghiviriga, Ion, McElwee-White, Lisa
Formato: Artículo
Publicado: American Chemical Society 10/25/2006
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Acceso en línea:Ver este registro en EBSCOhost
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        atl: Homogeneous Decomposition of Aryl- and Alkylimido Precursors for the Chemical Vapor Deposition of Tungsten Nitride: A Combined Density Functional Theory and Experimental Study.
      aug:
        au:
          Yong Sun Won
          Young Seok Kim
          Anderson, Timothy J.
          Reitfort, Laurel L.
          Ghiviriga, Ion
          McElwee-White, Lisa
        affil:
          Department of Chemical Engineering, University of Florida
          Department of Chemistry, University of Florida
      su:
        Nitrides
        Tungsten
        Transition metal nitrides
        Thin films
        Density functionals
        Chemical decomposition
      sug:
        subj:
          Nitrides
          Tungsten
          Transition metal nitrides
          Thin films
          Density functionals
          Chemical decomposition
      ab: MOCVD growth of tungsten nitride (WN) and tungsten carbonitride (WNC) thin films has been reported from the complexes CI(CHCN)W(NR) (1: R = Ph; 2: R = Pr; 3: R = CH). To evaluate the role of the imido substituent in film growth, gas-phase homogeneous decomposition of precursor molecules was investigated using density functional theory (DFT) calculations. Computational results and NMR kinetics of acetonitrile exchange by 2 in solution verified that dissociation of the acetonitrile ligand should be facile for 1–3 in the temperature range used for film growth (>450 °C). A computational search for transition states for cleavage of W-CI bonds in the presence of H carrier gas was consistent with a σ-bond metathesis pathway. Natural bonding orbital (NBO) analysis and bond energy calculations indicated that 1 has a stronger N-C(imido) bond and a slightly weaker W-N bond than 2 and 3, suggesting a greater role for W-N bond cleavage in depositions from 1. These results are consistent with mass spectrometric fragmentation patterns from 1-3 and low nitrogen content in films deposited from 1 as compared to those from 2 and 3.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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