Metal-Catalyzed Addition Polymers for 157 nm Resist Applications. Synthesis and Polymerization of Partially Fluorinated, Ester-Functionalized Tricyclo[4.2.1.0^2,5]non-7-enes

Abstract

Fluorinated tricyclo[4.2.1.02,5]non-7-ene-3-carboxylic acid esters are shown to undergo metal-catalyzed addition polymerization. The resulting homopolymers are transparent at 157 nm and demonstrate the utility of these monomers in development of photoresists for 157 nm lithography. Fluorinated tricyclononene (TCN) structures with ester substituents exhibit up to 3 orders of magnitude more transparency at 157 nm than conventional ester-functionalized norbornene structures as determined by gas-phase vacuum-ultraviolet spectroscopy and variable angle spectroscopic ellipsometry. Unlike their fluorinated norbornene counterparts, the fluorinated, ester-functionalized TCN monomers successfully undergo transition-metal-catalyzed addition polymerization to produce polymers with high glass transition temperatures and the etch resistance required for photolithographic resist materials applications. The potential use of fluorinated TCN structures for 157 nm photoresists is demonstrated through the synthesis and characterization of TCN monomers and polymers.

Metal catalysts for the vinyl/addition polymerization of norbornene

“…Hence, the polymerization of substituted derivatives proceeds slower than in the case of the unsubstituted norbornene monomer [77,78]. Examples for the polymerization of substituted norbornenes are given in [77][78][79][80][81][82][83][84][85].…”

Quadricyclane—thermal cycloaddition to polyfluorinated carbonyl compounds

“…Compared with reported reactions of 1 with acrylates, which proceed only at elevated temperature and involve exclusively the C=C bond of acrylate [17,18], bis(trifluoromethyl)ketene (4) reacts with 1 selectively producing oxetane 5 (Eq. 2).…”

Cyclopentadienyl Nickel and Palladium Complexes/Activator System for the Vinyl‐Type Copolymerization of Norbornene with Norbornene Carboxylic Acid Esters: Control of Polymer Solubility and Glass Transition Temperature

“…[1][2][3] However, poor solubility of the polymer in common organic solvents and poor adhesion to common substrate materials are serious disadvantages for the processing of these polymer materials, for example into transparency films and deep ultraviolet photoresist materials. [4] Even though some catalysts have been known to give soluble poly(norbornene)s under certain conditions, mechanical brittleness makes the film formation difficult.…”