Superconformal Electrodeposition of Cobalt into Micron-Scale Trench with Alkynol Derivatives.

Copper interconnect technology faces limitations due to the electron's mean free path and electromigration, driving the adoption of cobalt alternatives. This study proposes a novel mechanism to achieve superfilling by tuning the adsorption energy of additive molecules on cobalt surfaces. The adsorption energies of additives are tailored by changing molecular structures with different functional groups. Computational results reveal that carbon-carbon triple bonds critically strengthen adsorption, while ether bonds further enhance binding on distinct cobalt crystallographic planes. Specifically, 1,4-bis(2-hydroxyethoxy)-2-butyne (BEO) containing both triple bonds and ether groups exhibits the highest adsorption energy (-22.62 eV). Replacing ether with hydroxyl groups in 2-butyne-1,4-diol (BOZ) reduces the adsorption energy to -10.39 eV, while eliminating triple bonds in 1,4-butanediol diglycidyl ether (BDE) further decreases it to -8.43 eV. Experimental studies demonstrate that BOZ and BEO preferentially adsorb on the (101) and (110) planes of hexagonal close-packed cobalt (HCP-Co) due to their differential adsorption energies. This selective suppression promotes preferential growth along the densely packed (002) orientation. This leads to a trench-filling process dominated by the most densely packed plane, resulting in better electrical performance. Superfilling is achieved when molecular adsorption energies are in the range of 5-8 eV. The work establishes a functional group design strategy to regulate additive adsorption, enabling crystallographic control for advanced cobalt electrodeposition processes.