Abstract
A series of UV-curable hybrid composite blends containing a carboxylic acid functionalized polyimidewith varying amounts of high molecular weight (~1 K) PEG-grafted ladder-structured polysilsesquioxanes copolymerized with methacryl groups were fabricated and their structural, thermal, mechanical, and surface properties characterized. At a composite weight ratio of polyimide above 50 wt.%, a stark shift from amorphous to crystalline polyethylene glycol (PEG) phases were observed, accompanied by a drastic increase in both surface moduli and brittleness index. Moreover, fabricated composites were shown to have a wide range water contact angle, 9.8°–73.8°, attesting to the tunable surface properties of these amphiphilic hybrid polymer composites. The enhanced mechanical properties, combined with the utility of tunable surface hydrophilicity allows for the possible use of these hybrid polymer composites to be utilized as photosensitive polyimide negative photoresists for a myriad of semiconductor patterning processes.
Highlights
High performance polymers such as polyimides have been widely been researched for a myriad of applications requiring high thermal stability, low dielectric constant, high free fractional volume, low coefficient of thermal expansion, and high optical transparency [1,2,3]
Number average molecular weight (Mn ) and molecular weight distributions (Mw /Mn ) of the polymers were measured by JASCO PU-2080 plus gel permeation chromatography (GPC) system equipped with refractive index detector (RI-2031 plus), UV detector (λ = 254 nm, UV-2075 plus), and Viscotek SLS apparatus using THF as the mobile phase at 40 ◦ C with a flow rate of 1 mL/min
Unlike ladder structured polysilsesquioxanes grafted with a polyethylene glycol (PEG) molecular weight of
Summary
High performance polymers such as polyimides have been widely been researched for a myriad of applications requiring high thermal stability, low dielectric constant, high free fractional volume, low coefficient of thermal expansion, and high optical transparency [1,2,3]. While exhibiting excellent properties by itself, in certain applications such as those in various semiconductor processes of fabricating patterned surfaces requiring photosensitive resist layers, polyimides and their organically modified variants have been reported to have some limitations in thermal, thermomechanical, and electrical properties [11] Strategies to enhance such properties have often resorted to the hybridization method with inorganic or organic–inorganic hybrid materials [12,13]. In both studies a high degree of interface heterogeneity between polyimide and silica limited the extent to which the hybridization strategy aimed to target the enhancement factor of selective gas permeation Another widely reported method includes the use of aminosilane precursors to co-polymerize and imidize with anhydrides, leaving an alkoxysilane terminus to which sol-gel based hydrolysis–condensation networking of Si–O–Si bonds was possible. Copolymerization of methacryl groups allowed for UV-curing and an examination of their surface mechanical properties as a function of PEG crystalline phases controlled through a high ladder-like polysilsesquioxane composite fraction
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