Synthesis of β‐Ketoiminato Copper(II) Complexes and Their Use in Copper Deposition

The template synthesis of ethylenediamine ( 1 ) with 2‐acetylcyclopentanone ( 2 ) and [Cu(OAc) 2 · H 2 O] ( 5 ) produced [Cu(1‐(2‐ c C 5 H 6 (O))C(Me)NCH 2 ) 2 )] ( 6 ) in 82 % yield. Reaction of 5 with bis(benzoylacetone)diethylenetriamine ( 7 , = L H) [1] gave [Cu(μ‐OAc)( L )(H 2 O)] 2 ( 8 ). The solid‐state structures of 6 and 8 were determined confirming that 8 possesses intra‐ and intermolecular hydrogen bonds resulting in a dimer formation. The thermal behavior of 6 – 8 was studied by TG and TG‐MS. Under oxygen CuO was formed, whereas under Ar Cu/Cu 2 O ( 6 ) or Cu ( 8 ) was obtained. Complex 6 was used as CVD precursor for Cu and Cu‐oxide deposition (substrate temp., 400–500 °C, N 2 , 60 mL · min –1 ; O 2 , 60 mL · min –1 ; pressure, 0.87–1.5 mbar). The as‐obtained deposits show separated particles of different appearance at the substrate surface as evidenced by SEM. Non ‐volatile 8 was applied as spin‐coating precursor for Cu and CuO formation [conc. 0.25 mol · L –1 ; volume 0.2 mL; 3000 rpm; depos. time 2 min; heating rate 50 K · min –1 ; holding time 60 min (Ar), 120 min (air) at 800 °C]. The samples on silicon consist of granulated particles (Ar) or are non‐dense with a grainy topography (air). EDX and XPS measurements confirmed the formation of Cu (Ar) or CuO (O 2 ) with up to 13 mol‐% C impurity.