Progress in Polyhedral Oligomeric Silsesquioxane (POSS) Photoresists: A Comprehensive Review across Lithographic Systems.

This paper offers a comprehensive overview of the polyhedral oligomeric silsesquioxane (POSS) and POSS-based composites within the realm of photoresist resin. The study involves a systematic exploration and discussion of the contributions made by POSS across various lithographic systems, with specific emphasis on critical parameters such as film formation, sensitivity, resolution, solubility, and edge roughness. These lithographic systems encompass X-ray lithography (XRL), deep ultraviolet nanoimprint lithography (DUV-NIL), extreme ultraviolet lithography (EUV), and guided self-assembled lithography (DSA). The principal objective of this paper is to furnish valuable insights into the development and utilization of POSS-based photoresist materials in diverse lithographic contexts.

The Recent Advances of Polymer-POSS Nanocomposites With Low Dielectric Constant.

This study provides a comprehensive overview of the preparation methods for polyhedral oligomeric silsesquioxane (POSS) monomers and polymer/POSS nanocomposites. It focuses on the latest advancements in using POSS to design polymer nanocomposites with reduced dielectric constants. The study emphasizes exploring the potential of POSS, either alone or in combination with other materials, to decrease the dielectric constant and dielectric loss of various polymers, including polyimides, bismaleimide resins, poly(aryl ether)s, polybenzoxazines, benzocyclobutene resins, polyolefins, cyanate ester resins, and epoxy resins. In addition, the research investigates the impact of incorporating POSS on improving the thermal properties, mechanical properties, surface properties, and other aspects of these polymers. The entire study is divided into two parts, discussing systematically the role of POSS in reducing dielectric constants during the preparation of POSS composites using both physical blending and chemical synthesis methods. The goal of this research is to provide valuable strategies for designing a new generation of low dielectric constant materials suitable for large-scale integrated circuits in the semiconductor materials domain.

Facile UV-Induced Surface Covalent Modification to Fabricate Durable Superhydrophobic Fabric for Efficient Oil-Water Separation.

In this work, a durable superhydrophobic fabric was fabricated by using a facile UV-induced surface covalent modification strategy. 2-isocyanatoethylmethacrylate (IEM) containing isocyanate groups can react with the pre-treated hydroxylated fabric, producing IEM molecules covalently grafted onto the fabric's surface, and the double bonds of IEM and dodecafluoroheptyl methacrylate (DFMA) underwent a photo-initiated coupling reaction under UV light radiation, resulting in the DFMA molecules further grafting onto the fabric's surface. The Fourier transform infrared, X-ray photoelectron spectroscopy and scanning electron microscopy results revealed that both IEM and DFMA were covalently grafted onto the fabric's surface. The formed rough structure and grafted low-surface-energy substance contributed to the excellent superhydrophobicity (water contact angle of ~162°) of the resultant modified fabric. Notably, such a superhydrophobic fabric can be used for efficient oil-water separation, for example a high separation efficiency of over 98%. More importantly, the modified fabric exhibited excellent durable superhydrophobicity in harsh conditions such as immersion in organic solvents for 72 h, an acidic or alkali solution (pH = 1-12) for 48 h, undergoing laundry washing for 3 h, exposure to extreme temperatures (from -196° to 120°), as well as damage such as 100 cycles of tape-peeling and a 100-cycle abrasion test; the water contact angle only slightly decreased from ~162° to 155°. This was attributed to the IEM and DFMA molecules grated onto the fabric through stable covalent interactions, which could be accomplished using the facile strategy, where the alcoholysis of isocyanate and the grafting of DFMA via click coupling chemistry were integrated into one-step. Therefore, this work provides a facile one-step surface modification strategy for preparing durable superhydrophobic fabric, which is promising for efficient oil-water separation.

The Synergistic Effects of Aminosilane Coupling Agent on the Adhesion Performance of Silane Primer for Silicone Resin Thermal Protection Coating.

As a bridge between the coating and the substrate, the primer has a direct impact on the adhesion performance of silicone resin thermal protection coating. In this paper, the synergistic effects of an aminosilane coupling agent on the adhesion performance of silane primer were investigated. The results show that silane primer containing N-aminoethyl-3-aminopropylmethyl-dimethoxysilane (HD-103) formed a continuous and uniform film on the surface of the substrate. Two amino groups of HD-103 were conducive to moderate and uniform hydrolysis of the silane primer system, and the introduction of dimethoxy groups was more conducive to the improvement of interfacial layer density and the formation of the planar surface structure, thus enhancing the bond strength at the interface. When the content was 13 wt%, it exhibited excellent synergistic effects on adhesive properties, and the adhesive strength reached 1.53 MPa. The possible morphology and composition of the silane primer layer were investigated by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). A thermogravimetric infrared spectrometer (TGA-IR) was used to analyze the thermal decomposition of the silane primer layer. The results showed that the alkoxy groups in the silane primer were first hydrolyzed to form Si-OH, and then the dehydration and condensation reactions between Si-OH and the substrate formed a firm network structure.

One-Step Covalent Surface Modification to Achieve Oil-Water Separation Performance of a Non-Fluorinated Durable Superhydrophobic Fabric.

In this work, a durable superhydrophobic fabric was fabricated by a facile covalent surface modification strategy, in which the anchoring of 10-undecenoyl chloride (UC) onto the fabric through the esterification reaction and covalent grafting of n-dodecyl-thiol (DT) via thiol-ene click chemistry were integrated into one step. Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) measurement results demonstrated that UC and DT were covalently grafted onto the fabric surface. The formed gully-like rough structure by the grafted UC and DT on the fabric surface together with the inherent microfiber structure, combined with the grafted low-surface-energy materials of UC and DT, gave the resultant modified DT-UC@fabric superhydrophobic performance. The superhydrophobic DT-UC@fabric was used for separation of oil-water mixtures; it exhibited high separation efficiency of more than 98%. In addition, it presented excellent durability against mechanical damage; even after 100 cyclic tape-peeling and abrasion tests, the DT-UC@fabric could preserve superhydrophobic performance, which was ascribed to the formed covalent interactions between the fabric surface and the grafted UC and DT. Therefore, this work provided a facile, efficient strategy for fabricating superhydrophobic composites with excellent durability, which exhibited a promising prospect in the application of self-cleaning and oil-water separation.

Stable electrically conductive, highly flame-retardant foam composites generated from reduced graphene oxide and silicone resin coatings.

To acheive flexible polyurethane (PU) foam composites with stable electrical conductivity and high flame retardancy involved first coating of graphene oxide (GO) onto PU foam surfaces and then chemically reducing the GO with hydrazine to form reduced GO (RGO). The RGO-coated PU foam is then dipped into a solution containing silicone resin (SiR) and silica nano-particles and cured. The resulting composites (PU-RGO-SiR) show superior flame retardancy, thermal stability and mechanical stability relative to the PU starting materials or PU coated with either RGO or SiR alone. The electrical conductivity of the PU-RGO-SiR composites (as high as 118 S m-1 at room temperature) could almost be retained but with small loss of 9.5% of the original value after 150 cyclic compression. When the samples were subjected to a temperature range from -50 to 400 °C, the electrical conductivity could remain constant at -50 °C, 25 °C, 100 °C, 200 °C, and even at 300 °C and 400 °C; the electrical-conductivity exhibited mild vibration but the vibration range was not beyond 5.6%. Flame retardancy tests show that the limiting oxygen index (LOI) increases from 14.7% for the pure foam to 31.5% for PU-RGO-SiR, and the PU-RGO-SiR composites exhibit a 65% reduction in the peak heat release rate (pHRR) and a 30% reduction in total smoke release (TSR). Thus, stable electrically conductive and highly flame-retardant foam composites have potential applications even in a variety of harsh conditions like high temperature, flame, organic solvents, and external compression.

Efficient Flame Detection and Early Warning Sensors on Combustible Materials Using Hierarchical Graphene Oxide/Silicone Coatings.

Design and development of smart sensors for rapid flame detection in postcombustion and early fire warning in precombustion situations are critically needed to improve the fire safety of combustible materials in many applications. Herein, we describe the fabrication of hierarchical coatings created by assembling a multilayered graphene oxide (GO)/silicone structure onto different combustible substrate materials. The resulting coatings exhibit distinct temperature-responsive electrical resistance change as efficient early warning sensors for detecting abnormal high environmental temperature, thus enabling fire prevention below the ignition temperature of combustible materials. After encountering a flame attack, we demonstrate extremely rapid flame detection response in 2-3 s and excellent flame self-extinguishing retardancy for the multilayered GO/silicone structure that can be synergistically transformed to a multiscale graphene/nanosilica protection layer. The hierarchical coatings developed are promising for fire prevention and protection applications in various critical fire risk and related perilous circumstances.

A novel and facile strategy for highly flame retardant polymer foam composite materials: Transforming silicone resin coating into silica self-extinguishing layer.

In this study, a novel strategy was developed to fabricate highly flame retardant polymer foam composite materials coated by synthesized silicone resin (SiR) polymer via a facile dip-coating processing. Applying the SiR polymer coating, the mechanical property and thermal stability of SiR-coated polymer foam (PSiR) composites are greatly enhanced without significantly altering their structure and morphology. The minimum oxygen concentration to support the combustion of foam materials is greatly increased, i.e. from LOI 14.6% for pure foam to LOI 26-29% for the PSiR composites studied. Especially, adjusting pendant group to SiOSi group ratio (R/Si ratio) of SiRs produces highly flame retardant PSiR composites with low smoke toxicity. Cone calorimetry results demonstrate that 44-68% reduction in the peak heat release rate for the PSiR composites containing different R/Si ratios over pure foam is achieved by the presence of appropriate SiR coating. Digital and SEM images of post-burn chars indicate that the SiR polymer coating can be transformed into silica self-extinguishing porous layer as effective inorganic barrier effect, thus preserving the polymer foam structure from fire. Our results show that the SiR dip-coating technique is a promising strategy for producing flame retardant polymer foam composite materials with improved mechanical properties.

Facile Surface Modification of Hydroxylated Silicon Nanostructures Using Heterocyclic Silanes.

Heterocyclic silanes containing Si-N or Si-S bonds in the ring undergo a ring opening reaction with -OH groups at the surface of porous Si nanostructures to generate -SH or -NH functional surfaces, grafted via O-Si bonds. The reaction is substantially faster (0.5-2 h at 25 °C) and more efficient than hydrolytic condensation of trialkoxysilanes on similar hydroxy-terminated surfaces, and the reaction retains the open pore structure and photoluminescence of the quantum-confined silicon nanostructures. The chemistry is sufficiently mild to allow trapping of the test protein lysozyme, which retains its enzymatic activity upon release from the modified porous nanostructure.

2,3,4,5-Tetraphenylsilole-based conjugated polymers: synthesis, optical properties, and as sensors for explosive compounds.

A series of linear 2,5-tetraphenylsilole-vinylene-type polymers were successfully synthesized for the first time. The tetraphenylsilole moieties were linked at their 2,5-positions through a vinylene bridge with p-dialkoxybenzenes to obtain polymer PSVB and with 3,6-carbazole to obtain polymer PSVC. For comparison, 2,5-tetraphenylsilole-ethyne-type polymer PSEB was also synthesized, in which the vinylene bridge of PSVB was replaced with an ethyne bridge. Very interestingly, the bridging group (vinylene or ethyne) had a significant effect on the photophysical properties of the corresponding polymers. The fluorescence peak of PSEB at 504 nm in solution originated from the emission of its silole moieties, whereas PSVB and PSVC emitted yellow light and no blueish-green emission from the silole moieties was observed, thus demonstrating that the emissions of PSVB and PSVC were due to their polymer backbones. More importantly, the 2,5-tetraphenylsilole-ethyne polymer exhibited a pronounced aggregation-enhanced emission (AEE) effect but the 2,5-tetraphenylsilole-vinylene polymer was AEE-inactive. Moreover, both AEE-active 2,5-tetraphenylsilole-ethyne polymer and AEE-inactive 2,5-tetraphenylsilole-vinylene polymers were successfully applied as fluorescent chemosensors for the detection of explosive compounds.

Novel ladder π-conjugated materials--sila-pentathienoacenes: synthesis, structure, and electronic properties.

A novel series of ladder π-conjugated materials--sila-pentathienoacenes (Si-PTA) are synthesized and characterized. Crystal structures of the compounds show that the length of alkyl chains substituting on the thiophene ring has a significant influence on molecular packing. A densely packed structure with an interfacial distance of about 3.66 Å between the adjacent molecules is observed for the compound with shorter alkyl chains. However, a large interfacial distance (7.99 Å) is obtained for another compound because of the insertion of long alkyl chains between two planes. The investigation of the optical and electrochemical properties shows that the silylene bridge incorporated into the pentathienoacene framework exerts a clear effect on the electronic properties by the σ*-π* conjugation. Although only a slight enhancement is observed for the HOMO levels, with respect to that of pentathienoacene, the LUMO levels are significantly lowered. The observed electronic properties are consistent with the theoretical calculations.