Preparation of a nanosilica‐modified negative‐type acrylate photoresist

A new type of negative photoresist, which incorporated nanosized silica into a photosensitive acrylic resin, was developed. First, free‐radical polymerization was employed to synthesize the acrylic resin, polymethyl methacrylate/methacrylic acid/3‐(trimethoxysilyl) propyl methacrylate], and then a silica precursor, prepared by hydrolysis and condensation of tetraethoxysilane in a sol–gel process, was introduced into the as‐formed resin solution. After the addition of photosensitive monomers and photoinitiators, a negative‐type organic–inorganic photoresist was produced. The morphology of the UV‐cured photoresist, as observed by field emission scanning electron microscopy, indicated that the size of the silica domain in the material could be reduced from 300 to about 50 nm by appropriate dosage of 3‐(trimethoxysilyl) propyl methacrylate. Thermogravimetric analysis, dynamic mechanical analysis, differential scanning calorimetry, and thermal mechanical analysis were used to evaluate the thermal and dimensional stabilities of the cured photoresists. It was found that the thermal decomposition temperature and glass‐transition temperature increased, whereas the thermal expansion coefficients before and after the glass transition decreased, with increasing silica content. The incorporation of 3‐(trimethoxysilyl) propyl methacrylate also enhanced the thermal and dimensional stabilities; however, the level of enhancement was moderate for the thermal decomposition temperature and thermal expansion coefficient and low for the glass‐transition temperature. In addition, a photoresist coated on a copper substrate demonstrated high hardness (5H) and strong adhesion (100%) with a resolution of 30 μm. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008