Zinc and Cadmium thioamidate complexes: rational design of single-source precursors for the AACVD of ZnS

A series of zinc(II) thioamidate complexes [Zn{SC(iPr)NR}2]n for R = iPr (n =2) (2), tBu (3) (n =1), Ph (4) (n =2) and Cy (5) (n =2) and one cadmium(II) thioamidate complex [Cd{SC(iPr)NtBu}2]3, (6), were designed and synthesised as single-source precursors for AACVD ZnS and CdS. Solid-state structures of all four zinc(II) compounds revealed distorted tetrahedral or trigonal bipyramidal geometries, with varying tendencies for dimeric association, mediated by {Zn‒S} bridging bonds. The thermogravimetric analysis identified the {tBu} derivertive, 3, as the most promising precursor based on its low decomposition onset (118°C) and clean conversion to ZnS. This was attributed to the greater availability of β-hydrogen atoms promoting the pyrolysis mechanism. The corresponding cadmium thioamide 6 was found to crystallise as a trimetallic molecule which lacked the thermal stability to be considered viable for AACVD. Hence, 3 was used to deposit ZnS thin films by AACVD at 200-300°C. Powder X-ray diffraction confirmed phase-pure growth of hexagonal wurtzite ZnS, with approximate crystallite sizes of 15-20 nm. Scanning electron microscopy revealed densely packed spherical nanoclusters. The morphology and crystallinity were most consistent for depositions between 250-300°C. Energy dispersive X-ray spectroscopy indicated slightly sulfur-deficient stoichiometries.