Thermal Stability and Orthogonal Functionalization of Organophosphonate Self-Assembled Monolayers as Potential Liners for Cu Interconnect

In this study, we investigated the thermal stabilities of butylphosphonic acid (BPA) and aminopropyltriethoxysilane (APTES) self-assembled monolayers (SAM) on a Si substrate. The thermal desorption and the thermal cleavage of the BPA and APTES SAM film on the Si substrate were studied by X-ray photoelectron spectroscopy (XPS) upon thermal treatment from 50 to 550 degrees C. XPS analyses show that the onset of the thermal desorption of the APTES monolayer occurs at 250 degrees C and the APTES SAM completely decomposed at 400 degrees C. Conversely, BPA SAM on Si shows that the onset of thermal desorption occurs at 350 degrees C, and the BPA SAM completely desorbed at approximately 500 degrees C. Our study revealed that the organophosphonate SAM is a more stable SAM in modifying the dielectric sidewalls of a Cu interconnect when compared to organosilane SAM. To overcome the spontaneous reaction of the organophosphonate film on the metal substrate, a simple orthogonal functionalization method using thiolate SAM as a sacrificial layer was also demonstrated in this study.