A positive type alkaline developable thermally stable and photosensitive polymer based on partially O-methylated poly(2,6-dihydroxy-1,5-naphthylene), an acidolytic de-cross-linker, and a photoacid generator

Abstract

A positive working and chemically amplified photosensitive polymer based on partially (30%) O-methylated poly(2,6-dihydroxy-1,5-naphthylene) [PMPDHN (30)], 1,3,5-tris[(2-vinyloxy)ethoxy]benzene (TVEB) as an acidolytic de-cross-linker, and a photoacid generator (5-propylsulfonyloxyimino-5 H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile (PTMA) has been developed. Poly(2,6-dihydroxy-1,5-naphthylene) (PDHN) with a number-average molecular weight of 33,000 was prepared by oxidative coupling polymerization of 2,6-dihydroxynaphthalene (2,6-DHN) using di-μ-hydroxo-bis-[( N, N, N′, N′-tetramethylethylenediamine)copper(II)] chloride [CuCl(OH)TMEDA] as the catalyst in 2-methoxyethanol at room temperature. PDHN was converted to PMPDHN by treating with iodomethane. The resist showed a sensitivity of 19.4 mJ cm −2 and a contrast of 7.5 when it was exposed to 436 nm light, followed by post-baking at 120 °C for 5 min and developing with 2.38 wt% aqueous tetramethylammonium hydroxide (TMAH) solution at 25 °C. A fine positive image featuring 6 μm line and space patterns was obtained on the film exposed to 20 mJ cm −2 of UV-light at 436 nm by the contact-printed mode. The optically estimated dielectric constants (at 1 MHz) of PMPDHN (30) with and without TVEB and PTMA are 3.03 and 3.01, respectively. The moisture absorption (1.7 wt%) of the resist system based on PMPDHN (30) and TVEB is very low compared to that (4.3%) of the resist system consisting of PDHN and 4,4′-methylenebis[2,6-bis(hydroxymethyl)]phenol (MBHP).