In this paper we have studied the application of metallated porphyrin self assembled monolayers (SAMs) as Cu diffusion barriers for Ultra-Large Scale Integration (ULSI) CMOS applications. The results for Cu/SiO2/Si and Cu/SAM/SiO2/Si MOS CAP structures are compared through a detailed electrical characterization of threshold voltage shift using bias-temperature studies. Material characterization and surface morphology is studied using UV absorption spectra and AFM. Our results show that metallated porphyrin SAMs can be effectively used as Cu diffusion barriers for ULSI applications. © 2008 IEEE.