Relationship among the Water Adsorption, Polymer Structure, and High-Frequency Dissipation Factor: Precise Analysis of Water Adsorption of Low-Dielectric Constant Polyimide Films

The development of polyimide (PI) films with both a low dielectric constant and low dissipation factor at high frequency is an urgent requirement in a new generation of mobile communication technology. Although some breakthroughs have been made in the study of low-dielectric constant polyimide, the main influencing factors and regulation of the high-frequency dissipation factors are still unclear, which severely limits its development and application, and they deserve further study. In this work, we prepared a series of low-dielectric constant polyimide films and measured their high-frequency dielectric properties at different humidity levels by using a homemade system. The free volume and water adsorption of these polyimide films were precisely evaluated by positron annihilation lifetime spectroscopy and the dynamic vapor sorption method, respectively. Our study shows that the main factor affecting the high-frequency dissipation factor of low-dielectric constant PI films is the water adsorption, and the influence of water adsorption capacity and water binding intensity on the increase of the high-frequency dissipation factor is analyzed in detail. The main factors affecting the water adsorption of these polyimide films are the free volume, molecular polarity index (MPI), and morphology. In the case of a similar structure, imide ring density, and morphology, the free volume of DP-BPDA, MDA-BPDA, TPM-BPDA, and FDA-BPDA gradually increases, resulting in an increase in water adsorption and high-frequency dissipation factors. HMDA-BPDA achieves a low water adsorption of 0.44% due to its appropriate free volume, low MPI, and partial crystallinity, thus achieving good comprehensive performance: low dielectric constant (2.84) and low dissipation factor (0.0029) at 50% RH. Therefore, for polymer materials, designing structures with low polarization, appropriate free volume, and low water adsorption will be an effective strategy to achieve both a low dielectric constant and low dissipation factor.