As the current top-down microchip manufacturing processes approach their resolution limits, there is a need for alternative patterning technologies that offer high feature densities and edge fidelity with single-digit nanometer resolution. To address this challenge, bottom-up processes have been considered, but they typically require sophisticated masking and alignment schemes and/or face materials' compatibility issues. In this work, we report a systematic study into the impact of thermodynamic processes on the area selectivity of chemical vapor deposition (CVD) polymerization of functional [2.2]paracyclophanes (PCP). Adhesion mapping of preclosure CVD films by atomic force microscopy (AFM) provided a detailed understanding of the geometric features of the polymer islands that form under different deposition conditions. Our results suggest a correlation between interfacial transport processes, including adsorption, diffusion, and desorption, and thermodynamic control parameters, such as substrate temperature and working pressure. This work culminates in a kinetic model that predictes both area-selective and nonselective CVD parameters for the same polymer/substrate ensemble (PPX-C + Cu). While limited to a focused subset of CVD polymers and substrates, this work provides an improved mechanistic understanding of area-selective CVD polymerization and highlights the potential for thermodynamic control in tuning area selectivity.
Keywords: area-selective deposition; chemical vapor deposition; polymer; surface modification; thin films.