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

Abstract

The template synthesis of ethylenediamine (1) with 2‐acetylcyclopentanone (2) and [Cu(OAc)2·H2O] (5) produced [Cu(1‐(2‐cC5H6(O))C(Me)NCH2)2)] (6) in 82 % yield. Reaction of 5 with bis(benzoylacetone)diethylenetriamine (7, = LH)[1] gave [Cu(μ‐OAc)(L)(H2O)]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/Cu2O (6) or Cu (8) was obtained. Complex 6 was used as CVD precursor for Cu and Cu‐oxide deposition (substrate temp., 400–500 °C, N2, 60 mL·min–1; O2, 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 (O2) with up to 13 mol‐% C impurity.

Synthesis, Characterization, and Electrochemistry of Diferrocenyl β-Diketones, -Diketonates, and Pyrazoles

“…Main-group element and transition metal β-diketonates, including Lewis-base adducts thereof, belong to one of the most investigated metal-organic complexes [ 1 , 2 , 3 , 4 , 5 , 6 , 7 ]. One reason is that they can be prepared by straightforward synthetic methodologies [ 8 , 9 , 10 ], and that many of them are commercially available.…”