4.5 Article

Controlling the Thermal Stability and Volatility of Organogold(I) Compounds for Vapor Deposition with Complementary Ligand Design

Journal

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Volume 2019, Issue 46, Pages 4927-4938

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.201901087

Keywords

Atomic layer deposition; Precursor design; Gold; Structure elucidation; Ligand effects

Funding

  1. Natural Sciences and Engineering Research Council (NSERC) of Canada through the Alexander Graham Bell CGS-D scholarship
  2. Carleton University [186853]
  3. NSERC [RGPIN-2016-06276]
  4. Canada Foundation for Innovation (CFI)
  5. Nova Scotia Research and Innovation Trust Fund
  6. Natural Sciences and Engineering Research Council of Canada (NSERC) [RGPIN-2014-06250]

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Atomic layer deposition (ALD) of gold is being studied by multiple research groups, but to date no process using non-energetic co-reactants has been demonstrated. In order to access milder co-reactants, precursors with higher thermal stability are required. We set out to uncover how structure and bonding affect the stability and volatility of a family of twelve organogold(I) compounds using a combination of techniques: X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and density functional theory (DFT). Small, unsubstituted phosphonium ylide ligands bind more strongly to Au(I) than their silyl-substituted analogues, but the utility of both these ligands suffers due to their poor volatility and substantial thermal decomposition. Pentafluorophenyl (C6F5) is introduced as a new, very electronegative ligand for gold vapor deposition precursors, and it was found that the disadvantage to volatility due to pi-stacking and other intermolecular interactions in the solid state was overshadowed by dramatic improvements to kinetic and thermodynamic stability. We introduce a new figure of merit to compare and rank the suitability of these and other complexes as precursors for vapor deposition. Finally, DFT calculations on four compounds that have high figures of merit show a linear correlation between the gold-coordinative ligand bond dissociation energies and the observed decomposition temperatures, highlighting and justifying this design strategy.

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