Porous Polymer Films with Tunable Pore Size and Morphology by Vapor Deposition

[Image: see text] The fabrication of porous polymer thin films with precise thickness and morphological control through conventional solvent-based techniques is challenging. Herein, we present a fabrication method for porous polymer thin films based on chemical vapor deposition that provides control over pore size, pore morphology, and film thickness. The porous films are prepared by co-depositing crystallizable porogen molecules with cross-linked poly(glycidyl methacrylate) (pGMA) thin films, which are synthesized by initiated chemical vapor deposition (iCVD). As the porogen is deposited, it crystallizes and phase-separates from the polymer film; simultaneous polymerization of pGMA limits crystal growth, controlling the size of crystals. Using naphthalene as porogen resulted in thin films with pore sizes from 5.9 to 24.2 μm and porosities ranging from 59.4 to 78.4%. Using octamethylcyclotetrasiloxane as porogen, which is miscible with the GMA monomer, drastically reduced the pore dimensions, ranging from 14.4 to 65.3 nm with porosities from 8.0 to 33.2%. The film morphology was highly dependent on the relative kinetics of porogen crystallization, phase separation, and heterogeneous polymerization. The kinetics of these competing processes are discussed qualitatively based on nucleation theory and Cahn–Hilliard theory. Fourier-transform infrared spectroscopy confirmed the retention of the reactive epoxide functionality of glycidyl methacrylate, which can enable further chemical derivatization as required for application in optoelectronics, sensing, separations, and biomedical devices.