In modern Cu interconnections in microelectronics, weak adhesion between the chemical-mechanical polished copper surface and the dielectric capping material can lead to rapid electromigration of Cu and early failure of the wiring. A self-aligned chemical vapor deposition (CVD) Mn capping process is introduced to strengthen the interface between Cu and dielectric insulators without increasing the resistivity of Cu. In this CVD process, a vapor mixture of Mn precursor and molecular hydrogen deposits Mn selectively on copper and not at all on the adjacent, previously deactivated surfaces of insulators. Deactivation of the insulator surfaces is accomplished by exposure to vapors containing reactive alkylsilyl groups. The presence of Mn at the Cu/insulator interface greatly increases the strength of the bonding between Cu and the insulator. The debonding energy increases approximately linearly with the amount of Mn at the interface, up to values so large that the interface could not be broken apart. This Mn-enhanced binding strength of Cu to insulators is observed for all insulators tested, including plasma-enhanced chemical vapor deposited Si3N4, SiCNOH, SiO2, and low-k SiCOH, as well as thermal SiO2 and atomic-layer-deposited SiO2. This selective CVD Mn capping process should increase the lifetime of advanced copper interconnections. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3364799] All rights reserved.