Journal of Vacuum Science & Technology B, Vol.19, No.4, 1201-1211, 2001
Characterization of Cu surface cleaning by hydrogen plasma
When a Cu surface is exposed to a clean room ambient, a surface layer containing Cu2O, CUO, Cu(OH)(2), and CuCO3 is formed. Thermal treatment in a vacuum combined with hydrogen plasma can remove this layer. Water and carbon dioxide desorb during the thermal treatment and the hydrogen plasma reduces the remaining Cu oxide. Ellipsometric, x-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectroscopy analyses indicate that the mechanism of interaction of the H-2 plasma with this layer depends on temperature. When the temperature is below 150 degreesC, H-2 plasma cannot completely reduce Cu oxide. Hydrogen diffuses through the oxide and hydrogenation of the Cu laver is observed. The hydrogenated Cu surface has a higher resistance than a nontreated Cu layer. The hydrogen plasma efficiently cleans the Cu surface when the substrate temperature is higher than 150 degreesC. In this case, hydrogen atoms have enough activation energy to reduce Cu oxide and adsorbed water forms as a byproduct of Cu oxide reduction. When the wafer temperature is higher than 350 degreesC, the interaction of the Cu film with hydrogen and residual oxygen is observed.