Synthesis of Calcium(II) Amidinate Precursors for Atomic Layer Deposition through a Redox Reaction between Calcium and Amidines

We have prepared two new Ca(II) amidinates, which comprise a new class of ALD precursors. The syntheses proceed by a direct reaction between Ca metal and the amidine ligands in the presence of ammonia. Bis(N,N′‐diisopropylformamidinato)calcium(II) (1) and bis(N,N′‐diisopropylacetamidinato)calcium(II) (2) adopt dimeric structures in solution and in the solid state. X‐ray crystallography revealed asymmetry in one of the bridging ligands to afford the structure [(η(2)‐L)Ca(μ‐η(2):η(2)‐L)(μ‐η(2):η(1)‐L)Ca(η(2)‐L)]. These amidinate complexes showed unprecedentedly high volatility as compared to the widely employed and commercially available Ca(II) precursor, [Ca(3)(tmhd)(6)]. In CaS ALD with 1 and H(2)S, the ALD window was approximately two times wider and lower in temperature by about 150 °C than previously reported with [Ca(3)(tmhd)(6)] and H(2)S. Complexes 1 and 2, with their excellent volatility and thermal stability (up to at least 350 °C), are the first homoleptic Ca(II) amidinates suitable for use as ALD precursors.