Photo acid generator, chemically amplified resist composition, and patterning process

Patent metadata

Field	Value
Publication number	US-2016004155-A1
Application number	US-201514728620-A
Country	US
Kind code	A1
Filing date	Jun 2, 2015
Priority date	Jul 4, 2014
Publication date	Jan 7, 2016
Grant date	—

Abstract

A photo acid generator represented (1a),

wherein R 01 and R 02 each independently represent a linear monovalent hydrocarbon group having 1 to 20 carbon atoms or a branched or cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms which may be substituted with or interposed by a heteroatom; R 03 represents a linear divalent hydrocarbon group having 1 to 30 carbon atoms or a branched or cyclic divalent hydrocarbon group having 3 to 30 carbon atoms which may be substituted with a heteroatom, or interposed by a heteroatom; and R 01 and R 02 may be mutually bonded to form a ring together with the sulfur atom in the formula. A photo acid generator can give a pattern excellent in resolution and LER and having a rectangular profile in the photolithography using a high energy beam like ArF excimer laser light, EUV, and electron beam as a light source.

First claim

What is claimed is:

1 . A photo acid generator represented by the following general formula (1a),

wherein R 01 and R 02 each independently represent a linear monovalent hydrocarbon group having 1 to 20 carbon atoms or a branched or cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms which may be substituted with a heteroatom, or interposed by a heteroatom; R 03 represents a linear divalent hydrocarbon group having 1 to 30 carbon atoms or a branched or cyclic divalent hydrocarbon group having 3 to 30 carbon atoms which may be substituted with a heteroatom, or interposed by a heteroatom; and R 01 and R 02 may be mutually bonded to form a ring together with the sulfur atom in the formula.

2 . The photo acid generator according to claim 1 ,
wherein the photo acid generator represented by the general formula (1a) is represented by the following general formula (1b),

wherein R 01 and R 02 have the same meanings as defined above; K represents a single bond or a linear divalent hydrocarbon group having 1 to 20 carbon atoms or a branched or cyclic divalent hydrocarbon group having 3 to 20 carbon atoms which may be substituted with a heteroatom, or interposed by a heteroatom; and “n” is 0 or 1.

3 . A chemically amplified resist composition comprising (A) a base resin, (B) the photo acid generator according to claim 1 , and (C) an organic solvent.

4 . A chemically amplified resist composition comprising (A) a base resin, (B) the photo acid generator according to claim 2 , and (C) an organic solvent.

5 . The chemically amplified resist composition according to claim 3 , wherein the component (A) is a polymer compound having a repeating unit represented by the following general formula (2) and a repeating unit represented by the following general formula (3),

wherein R 1 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; Z represents any of a single bond, a phenylene group, a naphthylene group, and a (main chain) —C(═O)—O—Z′—; Z′ represents a phenylene group, a naphthylene group, or a linear alkylene group having 1 to 10 carbon atoms or a branched or cyclic alkylene group having 3 to 10 carbon atoms which may have any of a hydroxyl group, an ether bond, an ester bond, and a lactone ring; XA represents an acid-labile group; and YL represents a hydrogen atom, or a polar group having one or more structures selected from a hydroxyl group, a cyano group, a carbonyl group, a carboxyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, and a carboxylic anhydride.

6 . The chemically amplified resist composition according to claim 4 , wherein the component (A) is a polymer compound having a repeating unit represented by the following general formula (2) and a repeating unit represented by the following general formula (3),

wherein R 1 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; Z represents any of a single bond, a phenylene group, a naphthylene group, and a (main chain) —C(═O)—O—Z′—; Z′ represents a phenylene group, a naphthylene group, or a linear alkylene group having 1 to 10 carbon atoms or a branched or cyclic alkylene group having 3 to 10 carbon atoms which may have any of a hydroxyl group, an ether bond, an ester bond, and a lactone ring; XA represents an acid-labile group; and YL represents a hydrogen atom, or a polar group having one or more structures selected from a hydroxyl group, a cyano group, a carbonyl group, a carboxyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, and a carboxylic anhydride.

7 . The chemically amplified resist composition according to claim 3 , wherein the component (A) is a polymer compound having a repeating unit represented by the following general formula (4) and a repeating unit represented by the following general formula (5),

wherein R 1 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; XA represents an acid-labile group; and G represents an oxygen atom or a carbonyloxy group, with the proviso that when G is a carbonyloxy group, a carbon atom of the carbonyloxy group is bonded to the benzene ring in the general formula (4).

8 . The chemically amplified resist composition according to claim 4 , wherein the component (A) is a polymer compound having a repeating unit represented by the following general formula (4) and a repeating unit represented by the following general formula (5),

wherein R 1 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; XA represents an acid-labile group; and G represents an oxygen atom or a carbonyloxy group, with the proviso that when G is a carbonyloxy group, a carbon atom of the carbonyloxy group is bonded to the benzene ring in the general formula (4).

9 . The chemically amplified resist composition according to claim 3 , further comprising a photo acid generator besides the component (B).

10 . The chemically amplified resist composition according to claim 4 , further comprising a photo acid generator besides the component (B).

11 . The chemically amplified resist composition according to claim 3 , further comprising a quencher.

12 . The chemically amplified resist composition according to claim 4 , further comprising a quencher.

13 . The chemically amplified resist composition according to claim 3 , further comprising a surfactant insoluble in water and soluble in alkaline developer.

14 . The chemically amplified resist composition according to claim 4 , further comprising a surfactant insoluble in water and soluble in alkaline developer.

15 . A patterning process comprising the steps of:
applying the chemically amplified resist composition according to claim 3 onto a substrate; performing exposure by a high energy beam after heat treatment; and performing development by using a developer.

16 . The patterning process according to claim 15 , wherein in the exposure step, a liquid having a refractive index of 1.0 or more is placed between a resist coat film and a projection lens to perform immersion exposure.

17 . The patterning process according to claim 16 , wherein a top coat is applied on the resist coat film, and the liquid having a refractive index of 1.0 or more is placed between the top coat and the projection lens to perform the immersion exposure.

18 . The patterning process according to claim 15 , wherein the high energy beam for exposure is a KrF excimer laser, an ArF excimer laser, an electron beam, or a soft X-ray having a wavelength range of 3 to 15 nm.

19 . A patterning process comprising the steps of:
applying the chemically amplified resist composition according to claim 3 onto a substrate having a layer containing chromium at an outermost layer; imagewise writing with an electron beam aft

Assignees

• Shinetsu Chemical Co

Inventors

• Ohashi Masaki
• Fukushima Masahiro
• Oikawa Kenichi
• Hasegawa Koji

Classifications

• G03F7/2059

  using a scanning corpuscular radiation beam, e.g. an electron beam · CPC title

• G03F7/32

  Liquid compositions therefor, e.g. developers · CPC title

• G03F7/0045 Primary

  with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors · CPC title

• G03F7/16

  Coating processes; Apparatus therefor (applying coatings to base materials in general B05; applying photosensitive compositions to base for photographic purposes G03C1/74) · CPC title

• G03F7/0392

  the macromolecular compound being present in a chemically amplified positive photoresist composition · CPC title