Enhanced performance of low-dielectric siloxane-polyimide copolymers: Synthesis and properties

Abstract

Low-dielectric polyimides (PI) films with outstanding overall performance are attractive for next generation microelectronic applications. Herein, a series of two different FPIs and BPIs derived from 4,4′-diaminodiphenyl ether (ODA) and two different functional dianhydrides, 4,4'-(hexafluoroisopropylidene) biphthalic anhydride (6FDA) and 4,4′-(4,4′-isopropyldiphenoxy) biphthalic anhydride (BPADA), respectively, were synthesized by a conventional two-step methodology that included thermoimidatization. Additionally, employing aminopropyl-terminated polydimethylsiloxane PDMS (molecular weight = 1000) as the source of siloxane-oxygen bonds, a series of polyimide siloxane (SiFPIs and SiBPIs) copolymers were synthesized by varying the siloxane content (ranging from 0 to 5 wt%) within the copolymer structure. The effects of siloxane bond on the thermal, solubility, water resistance, dielectric and mechanical properties of polyimide were investigated systematically. The integration of siloxane significantly enhanced the solubility of these copolymers in polar aprotic solvents (DMAC, DMF, NMP), expanding their applicability in diverse processing environments. Crucially, these copolymers exhibited remarkably low dielectric constants—2.90 for SiFPI at 3% PDMS and 2.92 for SiBPI at 4% PDMS—coupled with low loss values, positioning them as prime candidates for advanced microelectronic applications. All the composite films have high thermal stability near pure PI. The introduction of PMDS into PI can improve the elongation at break and at the same time, the composite films still remained with higher modulus and tensile strength. Extensive hydrophobicity assessments through contact angle and water absorption studies underscored the copolymers’ superior moisture resistance, a critical parameter for their potential deployment in high-performance, environmentally sensitive electronic components.