Structural and Dynamic Properties of Gallium Alkoxides.

ABSTRACT: A comparison of chlorido-gallium functionalized alkoxides as precursors for aerosol-assisted chemical vapor deposition (AACVD) was carried out. Variable-temperature (VT)-NMR studies were used to probe the fluxional behavior of these alkoxides in solution, and hence their utility as precursors. The synthesis involved the initial isolation of the dimer [GaCl(NMe₂)₂]₂ via a salt metathesis route from GaCl₃ and 2 equiv of LiNMe₂. This dimer was then reacted with 4 equiv of HOCH₂CH₂CH₂NEt₂, resulting in the formation of Ga[?-(OCH₂CH₂CH₂NEt₂)₂GaCl₂]₃ (1). Mass spectrometry and VT-NMR confirmed the oligomeric structure of 1. Tuning of the ligand properties, namely, the chain length and substituents on N, resulted in formation of the monomers [GaCl(OR)₂] (R = CH₂CH₂NEt₂, (2); CH₂CH₂CH₂NMe₂, (3)). VT-NMR studies, supported by density functional theory calculations, confirmed that the ligands in both 2 and 3 possess a hemilabile coordination to the gallium center, owing to either a shorter carbon backbone (2) or less steric hindrance (3). Both 2 and 3 were selected for use as precursors for AACVD: deposition at 450 °C gave thin films of amorphous Ga₂O₃, which were subsequently annealed at 1000 °C to afford crystalline Ga₂O₃ material. The films were fully characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, UV-visible spectroscopy, and energy dispersive X-ray analysis.

SUBMITTER: Mears KL 

PROVIDER: S-EPMC7007204 | biostudies-literature | 2019 Aug

REPOSITORIES: biostudies-literature