Search

Polyimide (PI) films are well recognized for their outstanding chemical resistance, radiation resistance, thermal properties, and mechanical strength, rendering them highly valuable in advanced fields such as aerospace, sophisticated electronic components, and semiconductors. However, improving their optical transparency while maintaining excellent thermal properties remains a significant challenge. This review systematically checks over recent advancements in enhancing the optical and thermal performance of PI films, focusing on various strategies through molecular design. These strategies include optimizing the main chain, side chain, non-coplanar structures, and endcap groups. Rigid and flexible structural characteristics in the proper combination can contribute to the balance thermal stability and optical transparency. Introducing fluorinated substituents and bulky side groups significantly reduces the formation of charge transfer complexes, enhancing both transparency and thermal properties. Non-coplanar structures, such as spiro and cardo configurations, further improve the optical properties while maintaining thermal stability. Future research trends include nanoparticle doping, intrinsic microporous PI polymers, photosensitive polyimides, machine learning-assisted molecular design, and metal coating techniques, which are expected to further enhance the comprehensive optical and thermal performance of PI films and expand their applications in flexible displays, solar cells, and high-performance electronic devices. Overall, systematic molecular design and optimization have significantly improved the optical and thermal performance of PI films, showing broad application prospects. This review aims to provide researchers with valuable references, stimulate more innovative research and applications, and promote the deep integration of PI films into modern technology and industry.

With the advent of the 5 G era, advanced packaging applications such as wafer-level fan-out packaging have emerged thanks to efforts to reduce signal loss and increase signal transmission rates. As one of the key materials employed in telecommunication devices, the interlayer dielectric material directly affects signal transmission and device reliability. Among them, polyimide (PI) has become an important interlayer dielectric material because of its excellent comprehensive properties. However, in order to meet the needs high-frequency and high-speed circuits for 5 G networks, it will be necessary to further reduce the dielectric constant and dielectric loss of PI. PI is widely used as a flexible dielectric material due to its excellent electrical insulation properties (dielectric constant ≈ 3.0–4.0, dielectric loss ≈ 0.02), mechanical properties, and thermal resistance. However, further reduction in the dielectric constant will be needed in order for PI-based materials to better meet the current high integration development needs of the microelectronics industry. This article starts from strategies to prepare low dielectric PI that have been developed in the last decade, based on a more systematic and inductive analysis, and prospects the development potential of low dielectric PI.

Two novel electrochromic aromatic polyimides (named as TPA-BIA-PI and TPA-BIB-PI, respectively) with pendent benzimidazole group were synthesized from 1,2-Diphenyl-N,N′-di-4-aminophenyl-5-amino-benzimidazole and 4-Amino-4′-aminophenyl-4″-1-phenyl-benzimidazolyl-phenyl-aniline with 4,4′-(hexafluoroisopropane) phthalic anhydride (6FDA) via two-step polymerization process, respectively. Then, polyimide films were prepared on ITO-conductive glass by electrostatic spraying, and their electrochromic properties were studied. The results showed that due to the π-π* transitions, the maximum UV–Vis absorption bands of TPA-BIA-PI and TPA-BIB-PI films were located at about 314 nm and 346 nm, respectively. A pair of reversible redox peaks of TPA-BIA-PI and TPA-BIB-PI films that were associated with noticeable color changed from original yellow to dark blue and green were observed in the cyclic voltammetry (CV) test. With increasing voltage, new absorption peaks of TPA-BIA-PI and TPA-BIB-PI films emerged at 755 nm and 762 nm, respectively. The switching/bleaching times of TPA-BIA-PI and TPA-BIB-PI films were 13 s/16 s and 13.9 s/9.5 s, respectively, showing that these polyimides can be used as novel electrochromic materials.

To prepare PIs (polyimides) with desirable thermal and mechanical properties is highly demanded due to their widespread applications in flexible optoelectronic devices and printed circuit boards. Here, the PI films of BPDA/4,4′-ODA, BPDA/3,4′-ODA, PMDA/4,4′-ODA, PMDA/3,4′-ODA systems were prepared, and it was found that the PIs with 3,4′-ODA always exhibit a high modulus compared with the PIs with 4,4′-ODA. To disclose the mechanism of high-modulus PI films with 3,4′-ODA, amorphous PI models and uniaxial drawing PI models were established and calculated based on MD simulation. The PI structural deformations at different length scales, i.e., molecular chain cluster scale and repeat unit scale, under the same stress were detailed and analyzed, including the variation of chain conformation, bond length, bond angle, internal rotation energy, and torsion angle. The results indicate that PIs with 3,4-ODA have higher internal rotation energy and smaller deformation with the same stress, consistent with the high modulus.

Polyimide films are currently of great interest for the development of flexible electronics and sensors. In order to ensure a proper integration with other materials and PI itself, some sort of surface modification is required. In this work, microwave oxygen plasma, reactive ion etching oxygen plasma, combination of KOH and HCl solutions, and polyethylenimine solution were used as surface treatments of PI films. Treatments were compared to find the best method to promote the adhesion between two polyimide films. The first selection of the treatment conditions for each method was based on changes in the contact angle with deionized water. Afterward, further qualitative (scratch test) and a quantitative adhesion assessment (peel test) were performed. Both scratch test and peel strength indicated that oxygen plasma treatment using reactive ion etching equipment is the most promising approach for promoting the adhesion between polyimide films.

Polyimides (PIs) represent a benchmark for high-performance polymers on the basis of a remarkable collection of valuable traits and accessible production pathways and therefore have incited serious attention from the ever-demanding medical field. Their characteristics make them suitable for service in hostile environments and purification or sterilization by robust methods, as requested by most biomedical applications. Even if PIs are generally regarded as “biocompatible”, proper analysis and understanding of their biocompatibility and safe use in biological systems deeply needed. This mini-review is designed to encompass some of the most robust available research on the biocompatibility of various commercial or noncommercial PIs and to comprehend their potential in the biomedical area. Therefore, it considers (i) the newest concepts in the field, (ii) the chemical, (iii) physical, or (iv) manufacturing elements of PIs that could affect the subsequent biocompatibility, and, last but not least, (v) in vitro and in vivo biocompatibility assessment and (vi) reachable clinical trials involving defined polyimide structures. The main conclusion is that various PIs have the capacity to accommodate in vivo conditions in which they are able to function for a long time and can be judiciously certified as biocompatible.

The surface morphology of polyamic acid films evolving under heating towards polyimide films is investigated with transmission electron microscopy. Micro-domains observed at the surface of the films are treated statistically and shown to form optimized statistical ensemble(s). The statistical size distribution of the micro-domains is described with the model of reversible aggregation. The distribution parameters, namely the aggregation energy and the mean diameter of micro-domains, are shown to depend on the chemical structure of the polymer and the heating temperature.

This paper presents a continuous single-step route that permits preparation of a thermostable polymer/metal nanocomposite film and to combine different functional properties in a unique material. More precisely, palladium nanoparticles are in situ generated in a polyimide matrix thanks to a designed curing cycle which is applied to a polyamic acid/metal precursor solution cast on a glass plate. A metal-rich surface layer which is strongly bonded to the bulk film is formed in addition to homogeneously dispersed metal nanoparticles. This specific morphology leads to obtaining an optically reflective film. The metal nanoparticles act as gas diffusion barriers for helium, oxygen, and carbon dioxide; they induce a tortuosity effect which allows dividing the gas permeation coefficients by a factor near to 2 with respect to the neat polyimide matrix. Moreover, the ability of the in situ synthesized palladium nanoparticles to entrap hydrogen is evidenced. The nanocomposite film properties can be modulated as a function of the location of the film metal-rich surface with respect to the hydrogen feed. The synthesized nanocomposite could represent a major interest for a wide variety of applications, from specific coatings for aerospace or automotive industry, to catalysis applications or sensors.