Design, Synthesis, and Evaluation of a Novel Amphiphilic Alicyclic Polymer Having γ-Hydroxy Acid Structure

Abstract

An amphiphilic alicyclic polymer having γ-hydroxy acid structure has been developed by reduction of poly(5-methylenebicyclo[2,2,1]-2-heptene)-co-(maleic anhydride). This polymer exhibits moderate transparency at 193 nm and good alkali solubility. A two-component negative resist system, consisting of the polymer and an onium salt, produces sub-micrometer patterns without swelling distortion by using an ArF excimer laser stepper. Infrared spectroscopy shows that the insolubilization reaction is mainly intramolecular esterification of γ-hydroxy acid to γ-lactone. The swelling distortion of sub-micrometer patterns can thus be avoided by drastically decreasing the number of carboxyl groups in the exposed area.

Development of high-performance negative-tone resists for 193-nm lithography

“…And the dissolution rates of alicyclic polymer with γ-hydroxy acid (polymer 1) and δ-hydroxy acid (polymer 2) previously reported 13,15 are also plotted. The rate for polymer 1 decreases rapidly when it is stored at 20°C, but the rate for polymer 2 decreases little by little at 20°C.…”

“…The authors previously reported on ArF negative-tone resists based on acid-catalyzed intramolecular esterification. 13,14 We developed alicyclic polymers with a γ-hydroxy acid structure (Scheme 1). It was found that because the acid-catalyzed intramolecular esterification of γ-hydroxy acid into γ-lactone proceeds in the exposed region, the aqueous-base developer cannot penetrate there.…”

“…C NMR spectra of poly(NLA-AdAH) in THF-d8. (a) before hydrolysis and (b) after hydrolysis 13. C NMR spectra of AdLA monomer in THF-d8.…”

“…more stable than polymer 2 which contains δ-hydroxy acid. One of the reasons for this inversion of the order of stability may be the structure of the hydroxy acid, especially the existence of an adjacent alicyclic structure 13. C NMR spectra of poly(DBHA-AdHA) in THF-d8.…”

Kinetic and computational studies on aminolysis of bicyclic carbonates bearing alicyclic structure giving alicyclic hydroxyurethanes

“…15,16 Clarifying the aminolysis behavior of cyclic carbonates with alicyclic structure will be very informative in synthesis of alicyclic alcohols bearing urethane moieties as the protected alcohol groups. In addition, introduction of alicyclic structure to polymer backbone leads to higher thermal and optical properties, [19][20][21][22][23] therefore will afford poly(hydroxyurethane)s with improved properties. We accordingly describe the aminolysis behavior of cyclic carbonates bound to five-and sixmembered alicyclic structures.…”