Anisotropic dielectric properties of polyimides consisting of various molar ratios of meta to para diamine with trifluoromethyl group

Abstract

AbstractA series of copolyimides based on pyromellitic dianhydride (PMDA) with various molar fractions of 4,4′‐(hexafluoro‐isopropylidene)dianiline (4,4′‐6F) and 3,3′‐(hexafluoro‐isopropylidene)dianiline (3,3′‐6F) were synthesized by a two‐step method. The five different composition copolyimides in the fozrm of {(PMDA+3,3′−6F)m/ (PMDA+4,4′−6F)n were mainly characterized using a dielectric analyzer (DEA) by single surface sensor (in‐plane direction) and thin film parallel plate sensor (out‐of‐plane direction) measurements. DSC, TMA, and XRD were also used to study the structure property. The increasing of molar ratio of para diamine in the copolyimide system up to 35% affected glass transition temperature, coefficient of thermal expansion, in‐plane dielectric constant and out‐of‐plane dielectric constant of copolyimides, correspondingly. The in‐plane dielectric constant was higher than that of the out‐of plane constant for our polyimide films. Anisotropy δε of the dielectric constants was 0.14 for CPI(100/o)a, 0.19 for CPI(85/15)a, 0.11 for CPI(75/25)a, and 0.05 for CPI(65/35)a. The difference in curing history also exhibited an effect on solvent diffusion behavior in our polymer system. Polymers cured at a slower curing rate had smaller CTE than that cured at a faster curing rate, as confirmed by X‐ray diffraction results. Polymers with smaller CTEs had larger dielectric constants at a slower curing rate, and vice versa. The experimental results suggested that CPI(65/35) a with smaller dielectric anisotropy could solve the crosstalk problem and provide equal electrical insulation in microelectronic devices. Therefore, a smaller and faster IC device could, it is hoped, be achieved, with smaller spacing between adjacent metal lines.