Cobalt(III) Diazabutadiene Precursors for Metal Deposition: Nanoparticle and Thin Film Growth

We report the synthesis and characterization
of a family of cobalt­(III) metal precursors, based around cyclopentadienyl
and diazabutadiene ligands. The molecular structure of the complexes
cyclopentadienyl-Cobalt­(III)­(N,N′-dicyclohexyl-diazabutadiene)
(2c) and cyclopentadienyl-Cobalt­(III)­(N,N′-dimesityl-diazabutadiene) (2d) are described,
as determined by single crystal X-ray diffraction analysis. Thermogravimetric
analysis of the complexes highlighted the isopropyl derivative CpCo­(iPr2-dab) (2a) as
a possible cobalt metal chemical vapor deposition (CVD) precursor.
Atmospheric pressure CVD (AP-CVD) was employed using precursor 2a to synthesize thin films of metallic cobalt on silicon
substrates under an atmosphere of hydrogen (H2). Analysis
of the thin films deposited at substrate temperatures of 250 °C,
275 °C, 300 °C, 325 °C, and 350 °C, respectively,
by scanning electron microscopy (SEM) and atomic force microscopy
(AFM) reveal temperature dependent growth features: films grown at
325 and 350 °C are continuous and pinhole free, whereas those
films grown at substrate temperatures of 250 °C, 275 °C,
and 300 °C consist of crystalline nanoparticles. Powder X-ray
diffraction (PXRD) and X-ray photoelectron spectroscopy (XPS) all
show the films to be high purity metallic cobalt. Raman spectroscopy
has also been used to prove the absence of cobalt silicides at the
substrate/thin film interface.