Fuji Photo Film Company, Limited

National Patent Development Corporation

Shinji Sakaguchi

Kenichiro Sato

Takashi Yoshida

Nobuo Tsuji

Yukio Karino

Shiro Tan

Tadayoshi Kokubo

Yasumasa Kawabe

Kazuya Uenishi

Takushi Miyazako

Osamu Takahashi

Toshiaki Aoai

Shigeru Nakamura

Hisashi Okamura

Ichizo Toya

Shigeharu Urabe

Tadao Sugimoto

Koji Shirakawa

Yukio Shinagawa

Makoto Momota

Shinzi Kataoka

Kunihiko Kodama

Masakazu Morigaki

Kazunobu Katoh

Keisuke Shiba

Masayuki Naya

Koichi Kawamura

Taku Nakamura

Seiiti Kubodera

Kiyoshi Nakazyo

Akio Mitsui

Isao Shimamura

Ashita Murai

Jun Arakawa

Yasuhiro Noguchi

Ikutaro Horie

Motohiko Tsubota

Yoshio Sakakibara

Tsumoru Ishii

Shinichi Imai

Sosuke Hanai

Kazunobu Kato

Junn Yamaguchi

Nagao Kameji

Masatoshi Sugiysma

As shown in FIG. A, a first resist film comprising organic high molecules and a second resist film comprising a photosensitive material are sequentially applied to a substrate by the spin coat method or the spray method for forming a two-layer resist. Then, a mask with which a metallic fine opening pattern is formed on a mask substrate comprising a dielectric, such as glass, is tightly contacted with the two-layer resist. Then, light is projected onto the back of the mask substrate to carry out exposure with near field light which is effused from the opening portions of the mask where no metal is formed. Then, a pattern is formed by processing the second resist layer for development with a developing solution. Thereafter, with the pattern in the second resist layer being used as a mask, the first resist layer is dry-etched with O plasma to form a fine pattern having a high aspect ratio, and with the pattern in the two-layer resist, the substrate is worked by etching, vapor deposition, or the like, before the two-layer resist is peeled off.

Fine pattern forming method

There are provided a positive photoresist composition comprising an alkali-soluble resin and a 1,2-naphthoquinonediazide-5-(and/or-4-) sulfonic ester of a tetrahydroxy compound having a specific structure, said ester component having a pattern area in the high-performance liquid chromatography determined using ultraviolet rays of 254 nm accounting for 50% or more of the entire pattern area and a positive photoresist composition comprising an alkali-soluble resin and 1,2-naphthoquinonediazide-5-(and/or -4-)sulfonic esters of two kinds of specific polyhydroxy compounds. The positive photoresist is suitable for ultrafine working and ensures high sensitivity and high resolution and is improved with respect to film thickness dependency and standing wave.

Positive photoresist composition

A positive photoresist composition for ultrafine working ensuring high sensitivity, high resolution, improved film thickness dependency and improved exposure margin, which comprises an alkali-soluble resin and a 1,2-naphthoquinonediazide-5-(and/or -4-)sulfonic ester of a polyhydroxy compound of formula (I), the tetraester component thereof accounting for 50% or more of the entire pattern area determined by high-performance liquid chromatography using ultraviolet rays of 254 nm: ##STR1## wherein X represents ##STR2## and the substituents other than X are as defined in the specification.

Disclosed is a radiation ray sensitive resin composition comprising a water-insoluble, alkali-soluble resin, a water-insoluble, alkali-soluble low-molecular compound and a radiation ray sensitive component, in which said radiation ray sensitive component contains a mixture composed of (A) a napthoquinonediazide sulfonic acid diester of water-insoluble, alkali-soluble low-molecular compounds having three and/or four phenolic hydroxyl groups and (B) a napthoquinonediazide sulfonic acid ester of a water-insoluble, alkali-soluble low-molecular compound having from 5 to 7 phenolic hydroxyl groups, in an amount of 30% or more of said radiation ray sensitive component. The composition is a positive type photoresist having a high resolution and small film thickness dependence. This has a broad latitude for development and leaves a small resist residue after development. This has high heat resistance and is therefore highly resistant to dry etching.

Radiation ray sensitive resin compostion containing at least two

Provided is a positive photoresist composition comprising (A) an alkali-soluble resin prepared by condensation of aldehydes and a mixture of phenols, which comprises (i) thymol, isothymol or a thymol-isothymol mixture and (ii) one or more of a phenol compound represented by the following formula (I); ##STR1## wherein R.sub.1, R.sub.2 and R.sub.3 are the same or different, and each of them represents a hydrogen atom or a methyl group, and optionally, as a third monomer, (iii) a phenol compound other than m-cresol; (B) 1,2-naphthoquinonediazide-5-(and/or -4-)sulfonic acid esters as photosensitive agent; and (C) a low molecular weight compound having from 12 to 50 carbon atoms in all and from 2 to 8 phenolic hydroxy groups.

Provided is a positive working photoresist composition which comprises an alkali-soluble resin and a 1,2-quinonediazide compound, with the resin being a novolak resin obtained by the condensation reaction of monomers comprising specified phenol compounds with formaldehyde.

Positive working photoresist composition

A positive photoresist composition is disclosed, which comprises an alkali-soluble resin, at least one of 1,2-naphthoquinonediazidesulfonic monoesters of specific polyhydroxy compounds, and at least one of 1,2-naphthoquinonediazidesulfonic ester of specific polyhydroxy compounds. The positive photoresist composition exhibits remarkably improved sensitivity and resolution, and broad development latitude regardless of the film thickness, and further, low film thickness dependence of resist performances.

Positive photoresist composition containing alkali soluble resins and

A positive photoresist composition is described, which comprises an alkali-soluble resin and 1,2-naphthoquinone-diazido-5-(and/or -4-)sulfonate of a polyhydroxy compound represented by the following formula (I): ##STR1## wherein R.sub.1 to R.sub.11 are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxyl group, an acyl group or a cycloalkyl group, provided that at least one of R.sub.1 to R.sub.11 is a cycloalkyl group; A represents -CH(R.sub.12)-, in which R.sub.12 represents a hydrogen atom or an alkyl group; and m represents 2 or 3.

There is provided a positive working photosensitive composition suitable for photosensitive lithographic printing plate or photoresist for fine processing, which comprises a quinonediazide ester compound having the structure characterized by containing in the same molecule both quinonediazide structure and N-sulfonylamide [--C(.dbd.O)--NHSO.sub.2 --] or sulfonamide [--NHSO.sub.2 --] structure which are positioned independently of each other.

Positive working photosensitive compositions

The present invention provides a positive-working photoresist composition comprising an alkali-soluble resin and a 1,2-naphthoquinonediazide-5-(and/or -4-)sulfonic ester of a specific water-insoluble alkali-soluble low molecular compound, wherein the high-performance liquid chromatography of the ester with an ultraviolet ray at 254 nm shows that the patterns corresponding to the diester components and complete ester component of the ester each fall within the specific range and a positive-working photoresist composition comprising a water-insoluble alkali-soluble resin, a water-insoluble alkali-soluble low molecular compound, and an ionization-sensitive radioactive compound which comprises a mixture of a naphthoquinone-diazidesulfonic diester of a water-insoluble alkali-soluble low molecular compound having three phenolic hydroxyl groups as an ionization-sensitive radioactive compound (A) and a naphthoquinonediazidesulfonic diester of a water-insoluble alkali-soluble low molecular compound having four phenolic hydroxyl groups as an ionization-sensitive radioactive compound (B) in an amount of 30% or more by weight based on the total amount of the ionization-sensitive radioactive compound.

Positive-working photoresist composition

A photoresist composition is disclosed containing an alkali-soluble resin and a photosensitive substance obtained by reaction of a polyhydroxy compound and (a) a 1,2-naphthoquinonediazido-5-(and/or -4-)sulfonyl chloride(s), said photosensitive substance being a mixture of photosensitive compounds (1) to (3): (1) a photosensitive compound having at least one hydroxyl group per molecule and having a number ratio of 1,2-naphthoquinonediazido-5-(and/or -4-)sulfonyl chloride sulfonate groups to hydroxyl groups within the range of from 3 to 20, contained in the photosensitive substance in an amount of 50 wt % or more; (2) a photosensitive compound where all the hydroxyl groups in the polyhydroxy compound have been 1,2-naphthoquinonediazidosulfonyl-esterified, contained in the photosensitive substance in an amount of 30 wt % to 0 wt %; and (3) a photosensitive compound having three or more hydroxyl groups which have not been 1,2-naphthoquinonediazidosulfonyl-esterified per molecule, contained in the photosensitive substance in an amount of 20 wt % to 0 wt %. The composition is suitable to exposure with g-ray, i-ray and excimer laser to provide a sharp resist image. The photoresist composition also has high sensitivity, high resolving power, precise reproducibility to provide resist images having good sectional shapes, broad development latitude, high heat resistance and good storage stability.

A positive-type photoresist composition is described as including:

Positive-type photoresist composition

A positive type photoresist composition which comprises an alkali soluble novolak resin and at least one light-sensitive material represented by the following general formulae (I) to (IV) to provide a resist pattern with high resolution, high reproduction fidelity, desirable sectional shape, wide latitude of development, high heat resistance and high storage stability: ##STR1## (wherein X represents --CO--, or --SO.sub.2 --; p represents an integer from 2 to 4; R's may be the same or different, each being --H, --OH, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted acyloxy group, ##STR2## provided that R always contains at least one of ##STR3## ; R.sub.1 represents ##STR4## a substituted or unsubstituted di- to tetra-valent alkyl group, or a substituted or unsubstituted di- to tetra-valent aromatic group; and l, m and n Represent O or an integer of from 1 to 3, provided that at least one of them is not zero).

A positive-working photoresist composition is disclosed, which comprises (1) a light-sensitive material obtained by reacting a polyhydroxy compound containing at least one group represented by the following general formula (I) per molecule with at least one of 1,2-naphthoquinonediazido-5-sulfonyl chloride and 1,2-naphthoquinonediazido-4-sulfonyl chloride, and (2) an alkali-soluble novolak resin: ##STR1## wherein R.sub.1 and R.sub.2 each represents a hydrogen atom or a C.sub.1 -C.sub.4 straight or branched alkyl or alkoxy group, provided that R.sub.1 and R.sub.2 do not represent hydrogen atoms at the same time; and X represents a divalent organic group.

A light-sensitive resin composition comprising a light-sensitive substance represented by the formula (A) shown below and an alkali-soluble resin: ##STR1## wherein R.sub.1 to R.sub.8 are independently hydrogen, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group, an amino group, a monoalkylamino group, a dialkylamino group, an acylamino group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, a carboxyl group, a cyano group, a nitro group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, -OD, or ##STR2## (wherein R is hydrogen, or an alkyl group, and D is a 1,2-naphthoquinonediazido-5-sulfonyl group or a 1,2-naphthoquinonediazido-4-sulfonyl group);

Growing community of inventors

Minami-ashigara, Japan

Shinji Sakaguchi