Monomer, polymer, resist composition, and patterning process

Patent metadata

Field	Value
Publication number	US-10023674-B2
Application number	US-201715426227-A
Country	US
Kind code	B2
Filing date	Feb 7, 2017
Priority date	Feb 10, 2016
Publication date	Jul 17, 2018
Grant date	Jul 17, 2018

Abstract

A monomer having a substituent group capable of polarity switch under the action of acid is provided. A useful polymer is obtained by polymerizing the monomer. A resist composition comprising the polymer has improved development properties and is processed to form a negative pattern having high resolution and etch resistance which is insoluble in alkaline developer.

First claim

The invention claimed is:

1. A monomer having the formula (1a) or (1b):

wherein R 1 to R 3 are each independently a C 1 -C 6 straight, branched or cyclic monovalent hydrocarbon group, R 1 and R 2 may bond together to form an alicyclic group with the carbon atom to which they are attached, R a is hydrogen, methyl or trifluoromethyl, X a is a C 1 -C 10 alkylene group, X b is a C 1 -C 10 straight, branched or cyclic (k 1 +1)-valent hydrocarbon group in which any constituent —CH 2 — moiety may be replaced by —O— or —C(═O)—, with the proviso that X b is exclusive of a group that forms the O—X b bond in the formula which is dissociable under the action of acid, X c is a single bond, methylene or ethylidene, X d is a single bond, methylene or ethylidene, Z a is an atomic group necessary to form a C 3 -C 10 alicyclic group with the carbon atom to which it is attached, A is a polymerizable functional group, and k 1 is 1 or 2.

2. The monomer of claim 1 wherein A is acryloyl or methacryloyl.

3. A polymer comprising recurring units containing as pendant a group having the formula (2a) and/or a group having the formula (2b):

wherein R 1 to R 3 are each independently a C 1 -C 6 straight, branched or cyclic monovalent hydrocarbon group, R 1 and R 2 may bond together to form an alicyclic group with the carbon atom to which they are attached, R 4 is hydrogen, methyl or trifluoromethyl, X a is a C 1 -C 10 alkylene group, X b is a C 1 -C 10 straight, branched or cyclic (k 1 +1)-valent hydrocarbon group in which any constituent —CH 2 — moiety may be replaced by —O— or —C(═O)—, with the proviso that X b is exclusive of a group that forms the O—X b bond in the formula which is dissociable under the action of acid, X c is a single bond, methylene or ethylidene, X d is a single bond, methylene or ethylidene, Z a is an atomic group necessary to form a C 3 -C 10 alicyclic group with the carbon atom to which it is attached, and k 1 is 1 or 2.

4. The polymer of claim 3 wherein the recurring units have the formulae (2aa) or (2bb):

wherein R 1 to R 3 , R a , X a to X d , Z a and k 1 are as defined above, R 4 is hydrogen or methyl.

5. The polymer of claim 3 , further comprising recurring units of at least one type selected from recurring units having the formulae (3) to (5):

wherein R 4 is hydrogen or methyl,
R 5 and R 6 are each independently a C 1 -C 6 straight, branched or cyclic monovalent hydrocarbon group, R 5 and R 6 may bond together to form an alicyclic group with the carbon atom to which they are attached,
R 7 is a C 1 -C 6 straight, branched or cyclic monovalent hydrocarbon group,
R 8 and R 9 are each independently a C 1 -C 6 straight, branched or cyclic monovalent hydrocarbon group, R 8 and R 9 may bond together to form an alicyclic group with the carbon atom to which they are attached,
X 1 and X 2 are each independently a single bond, methylene or ethylidene,
X 3 is a C 1 -C 20 straight, branched or cyclic divalent hydrocarbon group in which any constituent —CH 2 — moiety may be replaced by —O— or —C(═O)—,
Z b is a C 1 -C 9 straight, branched or cyclic aliphatic hydrocarbon group,
Z c is an atomic group necessary to form a C 2 -C 10 alicyclic group with the carbon atom to which it is attached,
Z d is a C 1 -C 20 straight, branched or cyclic aliphatic hydrocarbon group in which any constituent —CH 2 — moiety may be replaced by —O— or —C(═O)—,
with the proviso that Z b is exclusive of a group that forms the O—Z b bond in formula (3) which is dissociable under the action of acid, when X 1 is a single bond, and Z d is exclusive of a group that forms the O—Z d bond in formula (5) which is dissociable under the action of acid,
the total number of carbon atoms in X 1 , Z b , R 5 and R 6 is 5 to 12, the total number of carbon atoms in X 2 , Z c and R 7 is 5 to 12, k 2 is 0 or 1, k 3 is an integer of 2 to 4.

6. The polymer of claim 3 , further comprising recurring units of at least one type selected from recurring units having the formulae (A) to (D):

wherein R 4 is hydrogen or methyl, Z A is a C 1 -C 20 fluoroalcohol-containing group, exclusive of a structure undergoing a polarity switch under the action of acid, Z B is a C 1 -C 20 phenolic hydroxyl-containing group, Z C is a C 1 -C 20 carboxyl-containing group, Z D is a substituent group having a lactone structure, sultone structure, carbonate structure, cyclic ether structure, acid anhydride structure, alcoholic hydroxyl, alkoxycarbonyl, sulfonamide or carbamoyl moiety, X 4 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, naphthylene, —O—R 01 —, or —C(═O)—Z X —R 01 —, Z X is —O— or —NH—, and R 01 is a C 1 -C 6 straight, branched or cyclic alkylene, C 2 -C 6 straight, branched or cyclic alkenylene, phenylene or naphthylene group, which may contain a carbonyl, ester, ether or hydroxyl moiety.

7. The polymer of claim 3 , further comprising recurring units of at least one type selected from recurring units having the formulae (f1) to (f5):

wherein R 11 is each independently hydrogen or methyl, R 12 is a single bond, phenylene, —O—R 25 —, or —C(═O)—Z 22 —R 25 —, Z 22 is —O— or —NH—, R 25 is a C 1 -C 6 straight, branched or cyclic alkylene group, C 2 -C 6 straight, branched or cyclic alkenylene group or phenylene group, which may contain a carbonyl (—CO—), ester (—COO—), ether (—O—) or hydroxyl moiety, L is a single bond or —Z 33 —C(═O)—O—, Z 33 is a C 1 -C 20 straight, branched or cyclic divalent hydrocarbon group which may contain a heteroatom, Z 11 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—R 26 —, or —C(═O)—Z 44 —R 25 —, Z 44 is oxygen or NH, R 26 is a C 1 -C 6 straight, branched or cyclic alkylene group, C 2 -C 6 straight, branched or cyclic alkenylene group or phenylene group, which may contain a carbonyl, ester, ether or hydroxyl moiety, M − is a non-nucleophilic counter ion, R 13 to R 24 are each independently a C 1 -C 20 straight, branched or cyclic monovalent hydrocarbon group which may contain a heteroatom, R 13 and R 14 may bond together to form a ring with the sulfur atom to which they are attached, any two or more of R 15 , R 16 and R 17 or any two or more of R 18 , R 19 and R 20 may bond together to form a ring with the sulfur atom to which they are attached.

8. The polymer of claim 3 , further comprising recurring units of at least one type selected from recurring units having the formulae (X-1) to (X-4):

wherein R 1A is hydrogen, methyl or trifluoromethyl, R 2A to R 4A are each independently hydrogen or a C 1 -C 15 straight, branched or cyclic monovalent hydrocarbon group in which any constituent —CH 2 — moiety may be replaced by —O— or —C(═O)—, X 1A is a C 1 -C 15 straight, branched or cyclic divalent hydrocarbon group in which any constituent —CH 2 — moiety may be replaced by —O— or —C(═O)—, X 2A is

Assignees

• Shinetsu Chemical Co

Inventors

• Sagehashi Masayoshi
• Fukushima Masahiro
• Hasegawa Koji
• Adachi Teppei
• Katayama Kazuhiro
• Hatakeyama Jun

Classifications

• G03F7/0397

  the macromolecular compound having an alicyclic moiety in a side chain · CPC title

• G03F7/0388

  with ethylenic or acetylenic bands in the side chains of the photopolymer · CPC title

• C07C2603/14

  Benz[f]indenes; Hydrogenated benz[f]indenes · CPC title

• G03F7/0046

  with perfluoro compounds, e.g. for dry lithography (G03F7/0048 takes precedence) · CPC title

• G03F7/2004

  characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light · CPC title