Characterization and Lithographic Application of Calix[4]resorcinarene Derivatives

Abstract

Calix[4]resorcinarenes were prepared by the condensation of resorcinol and aldehydes (acetaldehyde, benzaldehyde, and 4-isopropylbenzaldehyde), and two isomers, C 4v (ccc) and C 2v (ctt), were separated by fractional crystallization. The products were characterized by NMR and FTIR, and their dissolution rate in aqueous base was measured. The eight hydroxyl groups of the calix[4]resorcinarenes were protected with acid labile t-butoxycarbonyl and t-butoxycarbonylmethyl. The protected calixarenes were thoroughly characterized by differential scanning calorimetry, FTIR, and variable-temperature 1H and 13C NMR. Their interaction with 4-isopropylphenol through hydrogen bonding was investigated by 13C NMR and correlated with their inhibition effect of dissolution of poly(4-hydroxystyrene-co-t-butyl acrylate) in an aqueous base, as studied by quartz crystal microbalance. Finally, the protected calixarenes were employed as a dissolution inhibitor of polyhydroxystyrene-based deep UV and electron beam chemical amplification resists to improve their contrast and performance.

Combinatorial Optimization of a Molecular Glass Photoresist System for Electron Beam Lithography

“…In the field of EBL particularly the groups of Shirota6, 16 and Ober8, 9, 17 employ various molecular glass resists. Moreover, using calix[4]resorcinarene derivatives Ueda et al18 could generate structures in the range of 40 nm, Yamada et al19 used a positive‐tone molecular glass resist material based on 1,3,5‐tris( p ‐( p ‐hydroxyphenyl)phenyl)benzene to produce half‐pitch 36 nm line space patterns utilizing a 100 kV electron beam tool, and Robinson et al20 created 20 nm lines with fullerene resists.…”

Phenolic antioxidants based on calixarene: Synthesis, structural characterization, and antioxidative properties in natural rubber

“…Resorcinol 13.21 g (0.12 mol) and 40% acetaldehyde aqueous solution 13.21 g (0.12 mol) were first dissolved in aqueous ethanol solution containing 60 mL of ethanol and 52 mL of distilled water. Subsequently, 30 mL of concentrated hydrochloric acid was slowly dropped in 30 min at room temperature and stirred at 70 °C for 2 h under N 2 . The obtained white solid product was recrystallized in 160 mL of 50 vol % aqueous ethanol solution, and the yield was 54%.…”

Bond contribution model for the prediction of glass transition temperature in polyphenol molecular glass resists

“…Some of the families that we have divided molecular resists into are polyphenols, arylbenzenes, calixarenes, steroids and cholates, spirocompounds, and dendrimers. 24,25 Steroids and cholates are usually derived from natural products and contain a four ring carbon skeleton fashion. Polyphenols are generally synthesized by acid catalyzed condensation of phenols with ketones, aldehydes, and tertiary alcohols and usually have a triaryl carbon on which two of the aryl groups are phenols.…”