Pulse electrodeposition of copper-manganese alloy in deep eutectic solvent

Abstract

Copper-manganese alloy has been established to improve resistance toward electromigration for interconnects. In this work, we employ a deep eutectic solvent (DES) to formulate a nonaqueous electrolyte for pulse current electrodeposition of Cu-Mn alloyed film. Using impedance spectroscopy to record ionic conductivities of DES-based electrolytes, we determine the optimized bath with a Cu/Mn molar ratio of 1:20. We produce an uniform, smooth, and composition-controllable CuMn alloyed film after exploring various pulsing parameters. Signals from X-ray diffractometer (XRD) suggest successful alloying of Cu and Mn with minor presence of MnO2. Profiles from X-ray photoelectron spectroscopy (XPS) validate the metallic nature of Mn from the as-deposited film. Upon Ar annealing, both XRD and XPS exhibit strong signals of MnO2 formation. In addition, images from transmission electron microscope and qualitative elemental chemical mapping indicate Mn atoms in CuMn alloy either diffuse through the underlying Cu seed layer and segregate at the Cu/SiO2 interface, or migrate toward the external surface forming MnO2. (C) 2018 Elsevier B.V. All rights reserved.