Dual‐Tone Patterned Mesoporous Silicate Films Templated From Chemically Amplified Block Copolymers

Directly patterned mesoporous silicate films are prepared using positive‐ and negative‐tone strategies by performing phase selective silica condensation within lithographically exposed poly(styrene‐b‐tert‐butyl acrylate) (PS‐b‐PtbA) templates containing photoacid generators. The use of supercritical fluid as a process medium enables rapid diffusion of the silicate precursor within the prepatterned block copolymer template film without disrupting its morphology. Template exposure through the mask triggers area selective generation of acid, which in turn both deprotects the poly(tert‐butyl acrylate) block to yield a poly(acrylic acid) block and provides a catalyst for silica precursor condensation yielding pattern formation at the device level. Because the acid generated in the UV exposed field preferentially segregates into hydrophilic poly(acrylic acid) domains of the phase segregated, deprotected block copolymer, precursor condensation is simultaneously controlled at nanoscopic length scales via templating by the underlying block copolymer morphology. The ability of PS‐b‐PtbA to undergo chemical transformation in two stages, deprotection followed by crosslinking, enables precise replications of the photomask in positive and negative tones. Detemplating via calcination yields patterned mesoporous silicate films without etching. Template formulations are optimized using infrared spectroscopic studies and the silicate films are characterized using electron microscopy and scanning force microscopy.