Low-dielectric polyimide (PI) nanofoams were prepared by introducing nanopores into the PI matrix containing fluorine groups. The nanopores were formed by thermolysis of the thermally labile content, namely, polyethylene glycol (PEG) oligomers, in air. The prepared PI nanofoams were characterized by Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and broadband dielectric spectroscopy. Results indicated that the PI nanofoams showed nanosized closed pores, excellent thermal stability, and a low dielectric constant of 2.12. The dielectric constant of the as-prepared nanofoams was stable within −150 °C to 150 °C. The thermal decomposition process of PEG in the PI matrix was designed and optimized to control the decomposition rate of PEG and the diffusion rate of the decomposition products of PEG. The dielectric constant of the nanofoams significantly decreased from 2.45 to 2.12 as the heating rate decreased from 5 °C min−1 to 1 °C min−1. The as-prepared PI nanofoams exhibited excellent properties and thus could be used in the microelectronics industry as a dielectric layer, multi-chip modules, or integrated circuit chips.
