Monomer, polymer, resist composition, and patterning process

Patent metadata

Field	Value
Publication number	US-10054853-B2
Application number	US-201715483210-A
Country	US
Kind code	B2
Filing date	Apr 10, 2017
Priority date	Apr 14, 2016
Publication date	Aug 21, 2018
Grant date	Aug 21, 2018

Abstract

A monomer having an onium salt structure represented by formula (1) gives a polymer which is fully compatible with resist components. A resist composition comprising the polymer has advantages including reduced acid diffusion, high sensitivity, high resolution, a good balance of lithography properties, and less defects, and is quite effective for precise micropatterning.

First claim

The invention claimed is:

1. A monomer having the formula (1):

wherein Z is a polymerizable group, L 1 is a carbonyl bond, sulfonyl bond or sulfinyl bond, L 2 is a single bond, ether bond, carbonyl bond, ester bond, amide bond, sulfide bond, sulfinyl bond, sulfonyl bond, sulfonic acid ester bond, sulfinamide bond, sulfonamide bond, carbamate bond or carbonate bond, L 3 is a single bond or a C 1 -C 40 straight, branched or cyclic divalent hydrocarbon group which may contain a heteroatom, A 1 is hydrogen, halogen or a C 1-20 straight, branched or cyclic monovalent hydrocarbon group which may contain a heteroatom, X a and X b are each independently hydrogen, fluorine or trifluoromethyl, with the proviso that at least one of X a and X b is a substituent group other than hydrogen, m is an integer of 1 to 4, and M + is an onium cation.

2. The monomer of claim 1 wherein Z is a group having the formula (2) or (3):

wherein R 1 is hydrogen, methyl, fluorine or trifluoromethyl, R 2 is a C 1 -C 12 straight, branched or cyclic monovalent hydrocarbon group which may contain a heteroatom, where there are present a plurality of R 2 , they may be the same or different and they may bond together to form a ring with carbon atoms on the benzene ring, n is an integer of 0 to 4, and the broken line designates a valence bond to L 3 in formula (1).

3. The monomer of claim 1 wherein L 1 is a sulfonyl bond.

4. The monomer of claim 1 wherein L 2 is a single bond and A 1 is hydrogen, fluorine or trifluoromethyl.

5. A polymer comprising recurring units derived from the monomer of claim 1 .

6. A polymer comprising recurring units having the formula (4) or (5):

wherein R 1 is hydrogen, methyl, fluorine or trifluoromethyl, R 2 is a C 1 -C 12 straight, branched or cyclic monovalent hydrocarbon group which may contain a heteroatom, where there are present a plurality of R 2 , they may be the same or different and they may bond together to form a ring with carbon atoms on the benzene ring, L 1 is a carbonyl bond, sulfonyl bond or sulfinyl bond, L 2 is a single bond, ether bond, carbonyl bond, ester bond, amide bond, sulfide bond, sulfinyl bond, sulfonyl bond, sulfonic acid ester bond, sulfinamide bond, sulfonamide bond, carbamate bond or carbonate bond, L 3 is a single bond or a C 1 -C 40 straight, branched or cyclic divalent hydrocarbon group which may contain a heteroatom, A 1 is hydrogen, halogen or a C 1 -C 20 straight, branched or cyclic monovalent hydrocarbon group which may contain a heteroatom, X a and X b are each independently hydrogen, fluorine or trifluoromethyl, with the proviso that at least one of X a and X b is fluorine or trifluoromethyl, m is an integer of 1 to 4, n is an integer of 0 to 4, and M + is an onium cation.

7. The polymer of claim 6 wherein L 1 is a sulfonyl bond.

8. The polymer of claim 6 wherein L 2 is a single bond and A 1 is hydrogen, fluorine or trifluoromethyl.

9. A resist composition comprising a base resin containing the polymer of claim 5 and an organic solvent.

10. The resist composition of claim 9 wherein the polymer further comprises recurring units of at least one type selected from recurring units having the formulae (6) and (7):

wherein R 1 is as defined above, Z A is a single bond, phenylene group, naphthylene group or (backbone)-C(═O)—O—Z′—, Z′ is a C 1 -C 10 straight, branched or cyclic alkylene group which may contain a hydroxyl radical, ether bond, ester bond or lactone ring, or phenylene group or naphthylene group, X A is an acid labile group, and Y A is hydrogen or a polar group having at least one structure selected from the group consisting of hydroxyl, cyano, carbonyl, carboxyl, ether bond, ester bond, sulfonic acid ester bond, carbonate bond, lactone ring, sultone ring and carboxylic anhydride.

11. A resist composition comprising a base resin, an organic solvent, and a photoacid generator,
wherein the base resin contains a polymer comprising recurring units derived from a monomer having the formula (1):

wherein Z is a polymerizable group, L 1 is a carbonyl bond, sulfonyl bond or sulfinyl bond, L 2 is a single bond, ether bond, carbonyl bond, ester bond, amide bond, sulfide bond, sulfinyl bond, sulfonyl bond, sulfonic acid ester bond, sulfinamide bond, sulfonamide bond, carbamate bond or carbonate bond L; is a single bond or a C 1 -C 40 straight, branched or cyclic divalent hydrocarbon group which may contain a heteroatom, A 1 is hydrogen, halogen or a C 1 -C 20 straight, branched or cyclic monovalent hydrocarbon group which may contain a heteroatom, X a and X b are each independently hydrogen, fluorine or trifluoromethyl, with the proviso that at least one of X a and X b is a substituent group other than hydrogen, m is an integer of 1 to 4, and M + is an onium cation, and
the photoacid generator is a photoacid generator other than the compound having the formula (1):

wherein L 1 , L 2 , L 3 , A 1 , X a , X b , m and M + are as defined above, and Z is a polymerizable group.

12. The resist composition of claim 11 wherein the photoacid generator has the formula (8) or (9):

wherein R 101 , R 102 and R 103 are each independently a C 1 -C 20 straight, branched or cyclic monovalent hydrocarbon group which may contain a heteroatom, any two of R 101 , R 102 and R 103 may bond together to form a ring with the sulfur atom to which they are attached, X − is an anion selected from the formulae (8A) to (8D):

wherein R, R fa , R fb1 , R fb2 , R fc1 , R fc2 and R fc3 are each independently fluorine or a C 1 -C 40 straight, branched or cyclic monovalent hydrocarbon group which may contain a heteroatom, or a pair of R fb1 and R fb2 , or R fc1 and R fc2 may bond together to form a ring with the carbon atom to which they are attached and any intervening atoms, R fd is a C 1 -C 40 straight, branched or cyclic monovalent hydrocarbon group which may contain a heteroatom,

wherein R 104 and R 105 are each independently a C 1 -C 30 straight, branched or cyclic monovalent hydrocarbon group which may contain a heteroatom, R 106 is a C 1 -C 30 straight, branched or cyclic divalent hydrocarbon group which may contain a heteroatom, any two of R 104 , R 105 and R 106 may bond together to form a ring with the sulfur atom to which they are attached, L is a single bond, ether bond or a C 1 -C 20 straight, branched or cyclic divalent hydrocarbon group which may contain a heteroatom, X 1 , X 2 , X 3 and X 4 are each independently hydrogen, fluorine or trifluoromethyl, at least one of X 1 , X 2 , X 3 and X 4 is fluorine or trifluoromethyl.

13. The resist composition of claim 9 , further comprising an amine compound.

Assignees

• Shinetsu Chemical Co

Inventors

• Fujiwara Takayuki

Classifications

• G03F7/168

  Finishing the coated layer, e.g. drying, baking, soaking · CPC title

• C07C311/49

  to nitrogen atoms · CPC title

• C07D307/00

  Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom · CPC title

• C08F20/38

  Esters containing sulfur · CPC title

• C08F20/22

  Esters containing halogen · CPC title