Versatile Landscape of Low-k Polyimide: Theories, Synthesis, Synergistic Properties, and Industrial Integration.

The development of microelectronics and large-scale intelligence nowadays promotes the integration, miniaturization, and multifunctionality of electronic and devices but also leads to the increment of signal transmission delays, crosstalk, and energy consumption. The exploitation of materials with low permittivity (low-k) is crucial for realizing innovations in microelectronics. However, due to the high permittivity of conventional interlayer dielectric material (k ∼ 4.0), it is difficult to meet the demands of current microelectronic technology development (k < 3.0). Organic dielectric materials have attracted much attention because of their relatively low permittivity owing to their low material density and low single bond polarization. Polyimide (PI) exhibits better application potential based on its well permittivity tunability (k = 1.1-3.2), high thermal stability (>500 °C), and mechanical property (modulus of elasticity up to 3.0-4.0 GPa). In this review, based on the synergistic relationship of dielectric parameters of materials, the development of nearly 20 years on low-k PI is thoroughly summarized. Moreover, process strategies for modifying low-k PI at the molecular level, multiphase recombination, and interface engineering are discussed exhaustively. The industrial application, technological challenges, and future development of low-k PI are also analyzed, which will provide meaningful guidance for the design and practical application of multifunctional low-k materials.

Dual-Effect Coupling for Superior Dielectric and Thermal Conductivity of Polyimide Composite Films Featuring "Crystal-Like Phase" Structure.

To match the increasing miniaturization and integration of electronic devices, higher requirements are put on the dielectric and thermal properties of the dielectrics to overcome the problems of delayed signal transmission and heat accumulation. Here, a 3D  porous thermal conductivity network is successfully constructed inside the polyimide (PI) matrix by the combination of ionic liquids (IL) and calcium fluoride (CaF2 ) nanofillers, motivated by the bubble-hole forming orientation force. Benefiting from the 3D thermal network formed by IL as a porogenic template and "crystal-like phase" structures induced by CaF2 - polyamide acid charge transfer, IL-10 vol% CaF2 /PI porous film exhibits a low permittivity of 2.14 and a thermal conductivity of 7.22 W m-1 K-1 . This design strategy breaks the bottleneck that low permittivity and high thermal conductivity in microelectronic systems are difficult to be jointly controlled, and provides a feasible solution for the development of intelligent microelectronics.

Dynamic Covalent Adaptable Polyimide Hybrid Dielectric Films with Superior Recyclability.

Polyimides (PIs) used in advanced electrical and electronic devices can be electrically/mechanically damaged, resulting in a significant waste of resources. Closed-loop chemical recycling may prolong the service life of synthetic polymers. However, the design of dynamic covalent bonds for preparing chemically recyclable crosslinked PIs remains a challenging task. Herein, new crosslinked PI films containing a PI oligomer, chain extender, and crosslinker are reported. They exhibit superior recyclability and excellent self-healable ability owing to the synergistic effect of the chain extender and crosslinker. The produced films can be completely depolymerized in an acidic solution at ambient temperature, leading to efficient monomer recovery. The recovered monomers may be used to remanufacture crosslinked PIs without deteriorating their original performance. In particular, the designed films can serve as corona-resistant films with a recovery rate of approximately 100%. Furthermore, carbon fiber reinforced composites (CFRCs) with PI matrices are suitable for harsh environments and can be recycled multiple times at a non-destructive recycling rate up to 100%. The preparation of high-strength dynamic covalent adaptable PI hybrid films from simple PI oligomers, chain extenders, and crosslinkers may provide a solid basis for sustainable development in the electrical and electronic fields.

Rising of Dynamic Polyimide Materials: A Versatile Dielectric for Electrical and Electronic Applications.

Polyimides (PIs) are widely used in circuit components, electrical insulators, and power systems in modern electronic devices and large electrical appliances. Electrical/mechanical damage of materials are important factors that threaten reliability and service lifetime. Dynamic (self-healable, recyclable and degradable) PIs, a promising class of materials that successfully improve electrical/mechanical properties after damage, are anticipated to solve this issue. The viewpoints and perspectives on the status and future trends of dynamic PI based on a few existing documents are shared. The main damage forms of PI dielectric materials in the application process are first introduced, and initial strategies and schemes to solve these problems are proposed. Fundamentally, the bottleneck issues faced by the development of dynamic PIs are indicated, and the relationship between various damage forms and the universality of the method is evaluated. The potential mechanism of the dynamic PI to deal with electrical damage is highlighted and several feasible prospective schemes to address electrical damage are discussed. This study is concluded by presenting a short outlook and future improvements to systems, challenges, and solutions of dynamic PI in electrical insulation. The summary of theory and practice should encourage policy development favoring energy conservation and environmental protection and promoting sustainability.

Dynamic Sustainable Polyimide Film Combining Hardness with Softness via a "Mimosa-Like" Bionic Strategy.

Dielectric polyimides (PIs) are ubiquitous as insulation in electrical power systems and electronic devices. Generally, dynamic polyimide is required to solve irreversible failure processes of electrical or mechanical damage, for example, under high temperature, pressure, and field strength. The challenge lies in the design of the molecular structure of rigid polyimide to achieve dynamic reversibility. Herein, a low-molecular-weight polyimide gene unit is designed to crosslink with polyimide ligase to prepare the smart film. Interestingly, due to the variability of gene unit and ligase combinations, the polyimide films combining hardness with softness are designed into three forms via a "Mimosa-like" bionic strategy to adapt to different application scenarios. Meanwhile, the films have good degradation efficiency, excellent recyclability, and can be self-healable, which makes them reuse. Clearly, the films can be used in the preparation of ultrafast sensors with a response time ≈0.15 s and the application of corona-resistant films with 100% recovery. Furthermore, the construction of polyimide and carbon-fiber-reinforced composites (CFRCs) has been verified to apply to the worse environment. Nicely, the composites have the property of multiple cycles and the non-destructive recycle rate of carbon fiber (CF) is as high as 100%. The design idea of preparing high-strength dynamic polyimide by crosslinking simple polyimide gene unit with ligase could provide a good foundation and a clear case for the sustainable development of electrical and electronic polyimides, from the perspective of Mimosa bionics.

Lack of neural load modulation explains attention and working memory deficits in first-episode schizophrenia.

OBJECTIVE: Although working memory (WM) deficits are well-recognized core features of schizophrenia, the underlying pathophysiological substrates of impairment in early psychosis before medication remain unclear. One possibility is that deficits in selective attention contribute to WM impairment. METHODS: EEG was acquired from 25 first-episode drug-naive schizophrenia patients and 26 matched controls while they performed a WM task. RESULTS: Compared with controls, schizophrenia patients showed a deficit in WM capacity in both behavioral and electrophysiological measures. Notably, the increased parieto-occipital pre-encoding stimulus alpha power in patients with schizophrenia predicted their subsequent reduced N2pc and symptom severity, whereas this relationship was absent in controls. Moreover, lacking load effect in neural activities predicted the serious impairment in behavior for schizophrenia. CONCLUSIONS: This pilot study provides preliminary evidence that the lack of load effect in neural activities may serve as potential underlying mechanisms for the impaired selective attention and WM capacity in schizophrenia. Our results emphasize the importance of pre-encoding stimulus alpha power in first-episode drug-naive schizophrenia. SIGNIFICANCE: These findings provide a neurophysiological correlate for the subjective reports of working memory deficits in schizophrenia and indicate the potential effective targets for clinical intervention.

Low-Permittivity Copolymerized Polyimides with Fluorene Rigid Conjugated Structure.

As the miniaturization of electronic appliances and microprocessors progresses, low-permittivity interlayer materials are becoming increasingly important for their suppression of electronic crosstalk, signal propagation delay and loss, and so forth. Herein, a kind of copolyimide (CPI) film with a "fluorene" rigid conjugated structure was prepared successfully. By introducing 9,9-Bis(3-fluoro-4-aminophenyl) fluorene as the rigid conjugated structure monomer, a series of CPI films with different molecular weights were fabricated by in situ polymerization, which not only achieved the reduction of permittivity but also maintained excellent thermodynamic stability. Moreover, the hydrophobicity of the CPI film was also improved with the increasing conjugated structure fraction. The lowest permittivity reached 2.53 at 106 Hz, while the thermal decomposition temperature (Td5%) was up to 530 °C, and the tensile strength was ≥ 96 MPa. Thus, the CPI films are potential dielectric materials for microelectronic and insulation applications.

Stereoselective Synthesis of Dihydrofuranoindoles via the Friedel-Crafts Alkylation/Annulation Cascade Process.

A stereoselective annulation protocol was developed to construct dihydrofuranoindoles from readily available starting materials. In the presence of a bifunctional squaramide, the Friedel-Crafts alkylation/annulation cascade process occurred smoothly to provide dihydrofuranoindoles in 26-95% isolated yields exclusively as trans-diastereomers (38-99% ee). This catalytic protocol was compatible with a range of structurally distinct hydroxyindoles bearing the hydroxyl group at different positions, providing four kinds of dihydrofuranoindoles. Moreover, gram-scale synthesis and further synthetic manipulation of the product were also demonstrated.