The Effect of Plasma Treatment on Adsorbed Iodine as a Catalyst in Chemical Vapor Deposition of Copper and Application to Filling of Deep Trenches with High Aspect Ratios

Abstract

Plasma treatment was introduced in order to control the catalytic properties of iodine in catalyst-enhanced chemical vapor deposition (CECVD) of copper (Cu). The iodine adatoms are deactivated (i.e., lose their catalytic effect) by forming Cu–I bonds through reaction with Cu atoms by the bombardment of ions during the plasma treatment. The surface concentration of effective iodine adatoms that can act as catalysts decreases exponentially with an increasing of ion exposure which is the product of ion flux and plasma treatment time. The deactivated iodine can be reactivated by annealing above 200 °C. The enhancement factor, defined as the ratio of the enhanced deposition rate of Cu film by the adsorbed iodine to the deposition rate without the catalytic effect of iodine, is proportional to the surface concentration of effective iodine adatoms. The distribution of the surface concentration of effective iodine adatoms inside the trench can be controlled by the plasma treatment. CECVD coupled with plasma treatment enables void-free filling of deep trenches with an aspect ratio of 14.