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.