Search Results (65)

Technological advancements for the miniaturization of electronic components highlight a critical role of thin and durable stencils in advanced surface mount technology. Here, we report a transparent and fine film stencil consisting of a clear polyimide film and a functional diamond-like carbon coating layer for the fine-pitch surface mount technology process. High-quality and burr-free apertures in the thin film result from the thermally stable laser-cut process using a repetitive and low-power irradiation of nanosecond pulse laser, enhancing the printing accuracy of solder paste with fewer solder joint defects. The carbon coating layer with an electrostatic discharge composition facilitates smooth and robust surfaces and sidewalls of the apertures for the high solder paste release and high mechanical durability of the fine film stencil. The low-cost and easy fabrication of the fine film stencil accelerates the potential industrial replacement of the conventional metal stencils at a reduced thickness and further open a new opportunity for the mass production of the fine-pitch surface mount technology process. Full article

This study presents colorless polyimides (PIs) suitable for use as plastic substrates in flexible displays, designed to be compatible with controlled soft adhesion and easy delamination (temporary adhesion) processes. For this purpose, we focused on a PI system derived from norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride (CpODA) and 2,2′-bis(trifluoromethyl)benzidine (TFMB). This system was selected with the aim of exhibiting excellent optical transparency and low linear coefficient of thermal expansion (CTE) properties. However, fabricating this PI film via the conventional two-step process was challenging because of crack formation. In contrast, modified one-pot polymerization at 200 °C using a combined catalyst resulted in a homogeneous solution of PI with an exceptionally high molecular weight, yielding a flexible cast film. The solubility of PI plays a crucial role in its success. This study delves into the mechanism behind the significant catalytic effect on enhancing molecular weight. The CpODA/TFMB PI cast film simultaneously achieved very high optical transparency, an extremely high glass transition temperature (T_g = 411 °C), a significantly low linear coefficient of thermal expansion (CTE = 16.7 ppm/K), and sufficient film toughness, despite the trade-off between low CTE and high film toughness. The CpODA/TFMB system was modified by copolymerization with minor contents of another cycloaliphatic tetracarboxylic dianhydride, 5,5′-(1,4-phenylene)-exo-bis(hexahydro-4,7-methanoisobenzofuran-cis-exo-1,3-dione) (BzDAxx). This approach was effective in improving the film toughness without sacrificing the low CTE and other target properties. The peel strengths (σ_peel) of laminates comprising surface-modified glass substrates and various colorless PI films were measured to evaluate the compatibility with the temporary adhesion process. Most colorless PI films studied were found to be incompatible. Additionally, no correlation between σ_peel and PI structure was observed, making it challenging to identify the structural factors influencing σ_peel control. Surprisingly, a strong correlation was observed between σ_peel and CTE of the PI films, suggesting that the observed solid–solid lamination is closely linked to the unexpectedly high surface mobility of the PI films. The laminate using CpODA(90);BzDAxx(10)/TFMB copolymer exhibited suitable adhesion strength for the temporary adhesion process, while meeting other target properties. The modified one-pot polymerization method significantly contributed to the development of colorless PIs suitable for plastic substrates. Full article

Fluorinated polyimide (FPI), renowned for its exceptional low-dielectric properties, colorless transparency, high-temperature resistance, and flexibility, has emerged as an ideal material for addressing challenges in 5G/6G high-frequency signal transmission and flexible electronic substrates. Nevertheless, the structure–property relationship between molecular architectures and the dielectric characteristics of FPI films remains insufficiently understood, necessitating urgent elucidation of the underlying mechanisms. In this study, a diamine monomer containing bis-amide bonds, 4-amino-N-{4-[(4-aminobenzoyl)amino]phenyl}benzamide (PABA), was synthesized. Subsequently, six FPI films (FPAIs, FPEIs, and FPEsIs) with distinct structural features were prepared through homopolymerization of PABA and five other diamines (containing amide bonds, ether, and ester groups) with fluorinated dianhydride (6FDA). Systematic characterization of thermal, mechanical, optical, and dielectric properties revealed that these films exhibit excellent thermal stability (T_g: 296–388 °C), mechanical strength (σ: 152.5–248.1 MPa, E: 2.1–3.4 GPa), and optical transparency (T_{550 nm}: 82–86%). Notably, they demonstrated a low dielectric constant (D_k as low as 2.8) and dielectric loss (D_f down to 0.002) under both low- and high-frequency electric fields. Furthermore, molecular dynamics simulations and quantum chemical were employed to calculate critical physical parameters and HOMO–LUMO energy levels of the six FPIs. This computational analysis provides deeper insights into the structure–performance correlations governing dielectric behavior and optical transparency in FPIs. The findings establish valuable theoretical guidance for designing advanced PI films with tailored dielectric properties and high transparency. Full article

A soluble photosensitive polyamide ester precursor (BAFPAE) was synthesized through copolymerization of 2,2-bis [4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP) with 4,4′-(4,4′-isopropylidenediphenoxy)bis(phthalic anhydride) (BPADA). Hydroxyethyl methacrylate (HEMA) was incorporated as a photosensitive functional group, and a transparent photosensitive polyimide film was obtained by thermal curing of the precursor film. The effects of reaction temperature and varying HEMA equivalents on the mechanical properties of the film were systematically investigated. The results indicated that the formation of polyacrylate-polyimide interpenetrating polymer networks (IPNs) was pivotal in preserving the mechanical integrity of the material. The optimized BAF-x-y exhibited a toughness of 12.69 MJ m³, a Young’s modulus of 2.86 GPa, an elongation at break of 21.16%, and a tensile strength of 92.68 MPa. Full article

Flexible, wearable biomedical sensors based on laser-induced graphene (LIG) have garnered significant attention due to a straightforward fabrication process and exceptional electrical and mechanical properties. However, most relevant studies rely on commercial polyimide precursors, which suffer from inadequate biocompatibility and weak adhesion between the precursor material and the LIG layer. To address these challenges, we synthesized cross-linked polyurethanes (PUs) with good biocompatibility and used them as substrates for LIG-based wearable pulse sensors. During fabrication, we employed two methods of LIG transfer to achieve optimal transfer yield. We adjusted the thickness of PU films and tailored their mechanical and physicochemical properties by varying the soft segment content to achieve optimal sensor performance. Our findings demonstrate that the success of LIG transfer is strongly influenced by the structure and composition of the polymeric substrate. Tensile testing revealed that increasing the soft segment content in PU films significantly improved their tensile strength, elongation at break, and flexibility, with PU based on 50 wt.% soft segment content (PU-50) showing the best mechanical properties. LIG exhibited minimal sensitivity to humidity, while PU films maintained high transparency (>80% at 500 nm), and PU-50 was non-toxic, with less than 5% lactate dehydrogenase (LDH) release in endothelial cell cultures, confirming its biocompatibility. Adhesion tests demonstrated that LIG transferred onto PU-50 exhibited significantly stronger adhesion compared to other tested substrates, with only a 30% increase in electrical resistance after the Scotch tape test, ensuring stability for wearable sensors. The optimal substrate, a semicrystalline PU-50, yielded superior transfer efficiency. Among all tested sensors, the LIG/PU-50, featuring a 77 μm thick substrate with good mechanical properties and improved adhesion, exhibited the highest signal-to-noise ratio (SNR). This study showcases a skin-safe LIG/PU-based pulse sensor that has significant potential for applications as a wearable patch in medical and sports monitoring. Full article

A mechanically robust flexible transparent conductor with high thermal and chemical stability was fabricated from welded silver nanowire networks (w-Ag-NWs) sandwiched between multilayer graphene (MLG) and polyimide (PI) films. By modifying the gas flow dynamics and surface chemistry of the Cu surface during graphene growth, a highly crystalline and uniform MLG film was obtained on the Cu foil, which was then directly coated on the Ag-NW networks to serve as a barrier material. It was found that the highly crystalline layers in the MLG film compensate for structural defects, thus forming a perfect barrier film to shield Ag NWs from oxidation and sulfurization. MLG/w-Ag-NW composites were then embedded into the surface of a transparent and colorless PI thin film by spin-coating. This allowed the MLG/w-Ag-NW/PI composite to retain its original structural integrity due to the intrinsic physical and chemical properties of PI, which also served effectively as a binder. In view of its unique sandwich structure and the chemical welding of the Ag NWs, the flexible substrate-cum-electrode had an average sheet resistance of ≈34 Ω/sq and a transmittance of ≈91% in the visible range, and also showed excellent stability against high-temperature annealing and sulfurization. Full article

Self-healing optically transparent polyimides have potential applications in optoelectronic device fabrication. In this study, for the first time, we successfully prepared a novel self-healing polyimide film containing reversible disulfide bonds through chemical imidization by introducing cystamine as a self-healing functional monomer into the molecular structure of conventional polyimides. The incorporation of cystamine enabled the films to maintain high transmittance (>87%) and tensile strength (>99 MPa). Meanwhile, tensile tests showed that the prepared film with a cystamine content of 50% achieved an excellent self-healing efficiency of up to 91.8%. Stress relaxation tests further revealed that disulfide bonds were rapidly cleaved upon thermal stimulation and the network topology was rearranged to complete the self-healing process. These results suggest that the dynamic covalent polymer network made of aliphatic disulfide bonds presents a new strategy for the development of optically transparent polyimides with excellent self-healing properties. Full article

The market demand for black polyimide (BPI) has grown hugely in the field of flexible copper-clad laminates (FCCLs) as a replacement for transparent yellow polyimide. The 3,6-bis(thiophen-2-yl)diketopyrrolopyrroles (TDPP) derivative is recognized for its high molar extinction coefficient. In this research, we have synthesized a diamine monomer named 3,6-bis[5-(4-amino-3-fluorophenyl)thiophen-2-yl]-2,5-bis(2-ethylhexyl)pyrrolo[4,3-c]pyrrole-1,4-dione (DPPTENFPDA), featuring a TDPP unit attached by fluorinated benzene rings. The subsequent reaction of DPPTENFPDA with pyromellitic dianhydride (PMDA) yielded an inherent BPI (DPPTENFPPI). By introducing chromophores derived from TDPP, the light absorption spectrum of DPPTENFPPI was broadened and red-shifted, thereby achieving full absorption within the visible spectrum and producing a highly black color that has a cut-off wavelength (λ_cut) of 717 nm and a CIE-Lab coordinate L* of 0.86. Additionally, DPPTENFPPI exhibited a low coefficient of thermal expansion (CTE) and remarkable thermal and electrical performance. Density functional theory calculations were conducted to explore the electronic nature of DPPTENFPPI. The outcomes revealed that the excellent light absorption of DPPTENFPPI predominantly originates from the transition from HOMO to LUMO + 1 within the chromophore moiety. The FCCL made from DPPTENFPPI films has high solder heat resistance and peel strength. This research contributes valuable insights into the structure and design of high-performance intrinsically black PIs for microelectronics applications. Full article

Optically transparent polyimide (PI) films with good atomic oxygen (AO) resistance have been paid extensive attention as thermal controls, optical substrates for solar cells or other components for low Earth orbit (LEO) space applications. However, for common PI films, it is usually quite difficult to achieve both high optical transparency and AO resistance and maintain the intrinsic thermal stability of the PI films at the same time. In the current work, we aimed to achieve the target by using the copolymerization methodology using the fluorinated dianhydride 9,9-bis(trifluoromethyl)xanthene-2,3,6,7-tetracarboxylic dianhydride (6FCDA), the fluorinated diamine 2,2-bis [4-(4-aminophenoxy)phenyl]hexafluoropropane (BDAF) and the polyhedral oligomeric silsesquioxane (POSS)-containing diamine N-[(heptaisobutyl-POSS)propyl]-3,5-diaminobenzamide (DABA-POSS) as the starting materials. The fluoro-containing monomers were used to endow the PI films with good optical and thermal properties, while the silicon-containing monomer was used to improve the AO resistance of the afforded PI films. Thus, the 6FCDA-based PI copolymers, including 6FCPI-1, 6FCPI-2 and 6FCPI-3, were prepared using a two-step chemical imidization procedure, respectively. For comparison, the analogous PIs, including 6FPI-1, 6FPI-2 and 6FPI-3, were correspondingly developed according to the same procedure except that 6FCDA was replaced by 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA). Two referenced PI homopolymers were prepared from BDAF and 6FDA (PI-ref1) and 6FCDA (PI-ref2), respectively. The experimental results indicated that a good balance among thermal stability, optical transparency, and AO resistance was achieved by the 6FCDA-PI films. For example, the 6FCDA-PI films exhibited good thermal stability with glass transition temperatures (T_g) up to 297.3 °C, good optical transparency with an optical transmittance at a wavelength of 450 nm (T₄₅₀) higher than 62% and good AO resistance with the erosion yield (E_y) as low as 1.7 × 10⁻²⁵ cm³/atom at an AO irradiation fluence of 5.0 × 10²⁰ atoms/cm². The developed 6FCDA-PI films might find various applications in aerospace as solar sails, thermal control blankets, optical components and other functional materials. Full article

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. Full article

With the increasing demand for innovative electronic products, LED transparent screens are gradually entering the public eye. Polyimide (PI) materials combine high temperature resistance and high transparency, which can be used to prepare flexible copper-clad laminate substrates. The physical and chemical properties of PI materials differ from copper, such as their thermal expansion coefficients (CTEs), surface energy, etc. These differences affect the formation and stability of the interface between copper and PI films, resulting in a short life for LED transparent screens. To enhance PI-copper interfacial adhesion, aminopropyl-terminated polydimethylsiloxane (PDMS) can be used to increase the adhesive ability. Two diamine monomers with a trifluoromethyl structure and a sulfone group structure were selected in this research. Bisphenol type A diether dianhydride is a dianhydride monomer. All three of the above monomers have non−coplanar structures and flexible structural units. The adhesion and optical properties can be improved between the interface of the synthesized PI films and copper foil. PI films containing PDMS 0, 1, 3, and 5 wt% were analyzed using UV spectroscopy. The transmittance of the PI-1/3%, PI-1/5%, PI-2/3%, and PI-2/5% films were all more than 80% at 450 nm. Meanwhile, the T_d 5% and T_{d 10%} heat loss and Tg temperatures decreased gradually with the increase in PDMS. The peel adhesion of PI-copper foil was measured using a 180° peel assay. The effect of PDMS addition on peel adhesion was analyzed. PIs-3% films had the greatest peeling intensities of 0.98 N/mm and 0.85 N/mm. Full article

Thickness measurement of thin films is essential for quality control in the manufacturing process of the semiconductor and display industries. Real-time monitoring of film thickness during production is an urgent technical problem to be solved. In this study, a method for large-area thickness measurement of transparent films based on a multichannel spectral interference sensor is proposed. The sensor simultaneously acquires multichannel spectral interference signals through a combination of fan-out fiber optic bundles, detection probes, and an imaging spectrometer. The spectral data are calibrated and transformed into the wavenumber dimension, and then the power spectral density estimation method is used to demodulate the data frequency to swiftly derive the film thickness. The thickness measurement capacity of the proposed system is successfully validated on two standard film samples with a relative deviation of less than 0.38% and a relative standard deviation of less than 0.044%. The total spectral acquisition and calculation time for a single multichannel measurement was approximately 7.5 ms. The experimental results on polyimide films show that the measurement efficiency of the system is at least 4 times higher than that of the traditional system, indicating the potential of the multichannel spectral interference sensor for online monitoring in film production. Full article

In order to prepare polyimide (PI) films with a low dielectric constant and excellent comprehensive performance, a two-step method was employed in this study to integrate β-cyclodextrin into a semi-aromatic fluorine-containing polyimide ternary system. By introducing trifluoromethyl groups to reduce the dielectric constant, the dielectric constant was further reduced to 2.55 at 10 MHz. Simultaneously, the film exhibited noteworthy thermal stability (a glass transition temperature exceeding 300 °C) and a high coefficient of thermal expansion. The material also demonstrated outstanding mechanical properties, boasting a strength of 122 MPa and a modulus of 2.2 GPa, along with high optical transparency (transmittance reaching up to 89% at 450 nm). Moreover, the inherent high transparency of colorless polyimide (CPI) combined with good stretchability contributed to the attainment of a low dielectric constant. This strategic approach not only opens up new opportunities for novel electroactive polymers but also holds potential applications in flexible displays, circuit printing, and chip packaging. Full article

Colorless and transparent polyimide (CPI) films with good atomic oxygen (AO) resistance and high thermal endurance are highly required in low earth orbit (LEO) space exploration. Conventional CPI films based on fluoro-containing 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) have been widely used in space applications. However, the AO erosion yields and glass transition temperatures (T_g) of the 6FDA-based CPI films have to be modified in order to meet the severe serving environments. In the current work, novel CPI films based on a multi-ring fluoro-containing 9,9-bis(trifluoromethyl)xanthene-2,3,6,7-tetracarboxylicdianhydride (6FCDA) monomer were developed. In order to enhance the AO resistance of the derived CPI film, a phosphorus-containing aromatic diamine, 2,5-bis[(4-aminophenoxy)phenyl]diphenylphosphine oxide (BADPO) was used to polymerize with the dianhydride to create the organo-soluble resin. Then, two phosphorus-containing CPI films (PPI), including PPI-1 (6FDA-BADPO) and PPI-2 (6FCDA-BADPO) were prepared by thermally curing of the PPI solutions at elevated temperatures. The PPI films maintained good optical transparency with transmittance values over 80% at a wavelength of 450 nm. PPI-2 exhibited a T_g value of 311.0 °C by differential scanning calorimetry (DSC) measurement, which was 46.7 °C higher than that of the PPI-1 counterpart (T_g = 264.3 °C). In addition, the PPI-2 film showed a coefficient of linear thermal expansion (CTE) value of 41.7 × 10⁻⁶/K in the range of 50~250 °C, which was apparently lower than that of the PPI-1 sample (CTE = 49.2 × 10⁻⁶/K). Lastly, both of the two PPI films exhibited good AO resistance with the erosion yields (E_y) of 6.99 × 10⁻²⁵ cm³/atom for PPI-1 and 7.23 × 10⁻²⁵ cm³/atom for PPI-2 at an exposure flux of 5.0 × 10²⁰ atoms/cm². The E_y values of the current PPI films were obviously lower than that of the standard polyimide (PI) film based on pyromellitic dianhydride (PMDA) and 4,4′-oxydianiline (ODA) (E_y = 3.0 × 10⁻²⁴ cm³/atom). Full article

Neat polyimide films are known to be dense and rigid. They are therefore not suitable for use in membranes, sensors and sustainable energy storage applications. In this study, a novel technique has been used to simultaneously improve the porosity, rigidity, damping ability and impact resistance of polyimide membranes. It is demonstrated that dispersion of a small amount of polyaniline copolymer-modified clay of about 0.25–0.5 wt.% into the polyimide matrix resulted in an enhanced storage modulus while maintaining high damping ability and glass transition temperature, T_g. Novel polyimide/substituted polyaniline-copolymer-clay nanocomposite membranes containing poly(N-ethyl-aniline-co-aniline-2-sulfonic-acid)-modified-clay (SPNEAC) was successfully prepared and incorporated into the polyimide matrix to form modified clay/polyimide nanocomposites. UV-Vis analysis of the nanocomposite films shows that the optical transparency of the SPNEAC-PI nanocomposite membranes decreased with increasing SPNEAC concentration due to the high UV-Vis absorption of SPNEAC. Transmittance of about 3% was observed in the nanocomposite membrane containing 5 wt.% modified clay at 500 nm wavelength, which is significantly lower than that for the neat PI membrane of about 36%. The dispersion of SPNEAC containing a high concentration of clay (≥40 wt.% clay), in polyimide matrix, resulted in the attainment of a higher degree of imidization than was possible for the organoclay/polyimide nanocomposite. This behavior is believed to be due to the synergistic interaction between PI and SPNEAC. A correlation of the morphology and elastic modulus of the SPNEAC2/PI nanocomposites shows that at low loading of SPNEAC 2 ≤ 0.5 wt.%, the cross-sectional morphology of the composite is an open, spiky, weblike structure with a storage modulus of about 1 GPa, but it progressively evolves into densely packed microspheroids with storage moduli of ≥2 GPa at 10 wt.% SPNEAC2. The impact energy of SPNEAC/PI composites, calculated from the α-transition peak area, increased with increasing SPNEAC loading and were about 4 times that of neat PI at 10 wt.% SPNEAC. Full article