Positive-Working Alkaline-Developable Photosensitive Polyimide Precursor Based on Poly(amic acid) and Dissolution Inhibitor.

Abstract

A poly(amic acid) (PAA) was prepared by ring-opening polyaddition of 4,4'-hexafluoroisopropyridenebis(phthalic anhydride) and 1,3-bis(4-aminophenoxy)benzene. The PAA film was very soluble to a tetramethylammonium hydroxide (TMAH) aqueous solution, whereas the dissolution inhibitor, 2,3,4-tris(1-oxo-2-diazonaphthoquinone-5-sulfonyloxy)-benzophenone (D5SB) effectively suppresses the solubility. This film could lead to polyimide exhibiting good thermal stability. An UV-vis.spectrum of the PAA film indicated excellent tranceparency to i-line (365 nm) and the PAA containing 20 wt% of D5SB showed a sensitivity of 100 mJicm2 and contrast of 7. 1, after exposed to i-line followed by developing with a 0.1 % TMAH aq. at room temperture. When this pattern printed film was heated at 200 °C for 24 hour to derive polyimide film, the pattern was maintained without any flow through the imidization.

The Photopolymer Science and Technology Award

“…Thermally stable and photosensitive polymers, especially photosensitive polyimides (PSPIs) (18)(19)(20)(21)(22) and polybenzoxazoles (PSPBOs) (27)(28)(29)(30)(31)(32), are widely used as protection and insulation layers of very-large-scale integrationcircuit multichip modules for computers. Even though PSPIs and PSPBOs have greatly enhanced the progress of microelectronics so far, more technological innovations involving simpler processes and more valuable properties such as transparency, low dielectric constant, higher sensitivity, low temperature cyclization, etc.…”

A Positive-Type Alkaline-Developable Photosensitive Polyimide Based on the Poly(amic acid) from 2,2′,6,6′-Biphenyltetracarboxylic Dianhydride and 1,3-Bis(4-aminophenoxy)benzene, and a Diazonaphthoquinone

“…The dissolution rate of PAAs in 2.38 wt % aqueous tetramethylammonium hydroxide (TMAHaq) solution is, however, too high to get a sufficient contrast in dissolution rates between unexposed and exposed areas when combined with DNQ derivatives. In a previous paper, 8 we reported the preparation of PSPIs consisting of highly hydrophobic PAAs and DNQ derivatives. PAA-BB is very high hydrophobic: a high dissolution contrast between unexposed and exposed areas could, therefore, be obtained by using DNQ-1, a highly hydrophobic DNQ derivative (Scheme 3).…”

Alkaline-developable Positive-type Photosensitive Polyimide based on Fluorinated Poly(amic acid) and Fluorinated Diazonaphthoquinone

“…Based on these considerations, we reported two positive-type and alkaline developable PSPIs [17,18], in which the PAA obtained from 4,4'-hexafluoroisopropyridene-bis(phthalic anhydride) (6FDA) and 1,3-bis(4-aminophenoxy)benzene, or dianhydrides, pyromellitic dianhydrides and biphenyltetracarboxylic dianhydrides, with 2,2'-bis(trifluoromethyl)benzidine, and 2,3,4-tris(1-oxo-2-diazonaphthoquinone-4-yl-sulfonyloxy) benzophenone (D4SB) were used as a matrix and a dissolution inhibitor, respectively. Quite recently, we reported a new fluorinated diazonaphthoquinone (FDNQ) prepared by the reaction of 1,2-naphthoquinone-2-diazido-5-sulfonyl chloride with 4,4'-(hexafluoroisopropylidene) diphenol as a photoactive compound (PAC).…”