Photoresist composition

Patent metadata

Field	Value
Publication number	US-9507259-B2
Application number	US-201213482595-A
Country	US
Kind code	B2
Filing date	May 29, 2012
Priority date	May 27, 2011
Publication date	Nov 29, 2016
Grant date	Nov 29, 2016

Abstract

A photoresist composition comprises an acid-sensitive polymer, and a cyclic sulfonium compound having the formula:

(R a ) 1 —(Ar)—S + (—CH 2 —) m · − O 3 S—(CR b 2 ) n -(L) p -X

wherein each R a is independently a substituted or unsubstituted C 1-30 alkyl group, C 6-30 aryl group, C 7-30 aralkyl group, or combination comprising at least one of the foregoing, Ar is a monocyclic, polycyclic, or fused polycyclic C 6-30 aryl group, each R b is independently H, F, a linear or branched C 1-10 fluoroalkyl or a linear or branched heteroatom-containing C 1-10 fluoroalkyl, L is a C 1-30 linking group optionally comprising a heteroatom comprising O, S, N, F, or a combination comprising at least one of the foregoing heteroatoms, X is a substituted or unsubstituted, C 5 or greater monocyclic, polycyclic or fused polycyclic cycloaliphatic group, optionally comprising a heteroatom comprising O, S, N, F, or a combination comprising at least one of the foregoing, and 1 is an integer of 0 to 4, m is an integer of 3 to 20, n is an integer of 0 to 4, and p is an integer of 0 to 2.

First claim

The invention claimed is:

1. A composition comprising:
an acid-sensitive polymer, and
a cyclic sulfonium compound having the formula:
(R a ) 1 —(Ar)—S + (—CH 2 —) m · − O 3 S—(CR b 2 ) n —(L) p —X

or the formula:
(R a ) 1 —(Ar)—S + (—CH 2 —) m ·

wherein
R a is isopropyl, t-butyl, cyclopentyl, or cyclohexyl,
Ar is para-phenylene,
each R b is independently F or a linear C 1-4 perfluoroalkyl group,
L is a C 1-30 linking group including an C(═O)—NR— or —O—C(═O)—NR— moiety, wherein R is H or X,
X is a substituted or unsubstituted, C 5 or greater polycyclic or fused polycyclic cycloaliphatic group, optionally comprising a heteroatom comprising O, S, N, F, or a combination comprising at least one of the foregoing,
Z 1 is —O— or —O—C(═O)—,
R 18 to R 21 are independently H, F, C 1-10 alkyl, or C 1-10 fluoroalkyl,
R 22 is norbornyl, cholate, a C 8 caged lactone, or a 1- or 2-adamantyl group optionally comprising an —OH, —OCH 3 , or —OCF 3 group, and
1 is 1, m is 4, n is 2, p is 1, r is 2 to 4, and s is 0 to 4,
provided that when Z 1 is —O—C(═O)— and s is 0, r is 4,
wherein the acid-sensitive polymer comprises:
(i) a structural unit comprising a monocyclic acid-cleavable group protecting a base-soluble group,
(ii) a structural unit comprising a polycyclic acid-cleavable group protecting a base-soluble group,
wherein the structural unit having the monocyclic or polycyclic acid-cleavable protective group is derived from
a monomer having the formula:
H 2 C═C(R c )—C(═O)—O-A 1

wherein R c is H, C 1-6 alkyl, F, or CF 3 and A 1 is a C 4-50 tertiary alkyl-containing group in which a tertiary center of A 1 is connected to an ester oxygen atom of the monomer, or
a monomer having the formula:
H 2 C═C(R d )—C(═O)—O—C(R e ) 2 —O—(CH 2 ) o -A 2

wherein R d is H, C 1-6 alkyl, F, or CF 3 , each R e is independently H or a C 1-4 alkyl group, A 2 is a C 1-30 cycloaliphatic group, and o is an integer of 0-4,
(iii) a structural unit derived from a lactone monomer, and
(iv) a structural unit derived from a polar monomer comprising a hydrogen donor group.

2. The composition of claim 1 , wherein X is substituted or unsubstituted and is a C 19 or less adamantyl group, C 19 or less norbornenyl group, C 7-20 lactone, steroidal group, or C 20 or greater non-steroidal organic group.

3. The composition of claim 1 , wherein X is substituted or unsubstituted and is C 19 or less norbornenyl group, C 7-20 lactone, steroidal group, or C 20 or greater non-steroidal organic group.

4. The composition of claim 1 , wherein:
X is —CH 2 -Ad, -Ad, or a steroidal group, and Ad is a 1- or 2-adamantyl group optionally comprising a substituent group comprising —OH, C 1-20 alkoxy, C 1-20 haloalkoxy, or a combination comprising at least one of the foregoing.

5. The composition of claim 1 , wherein the base soluble group comprises a carboxylic acid group, sulfonic acid group, amide group, sulfonamide group, sulfonimide group, imide group, phenol group, thiol group, azalactone group, hydroxyoxime group, or a combination comprising at least one of the foregoing.

6. The composition of claim 1 , wherein A 1 is a C 1-30 linking group including an —C(═O)—NR— or —O—C(═O)—NR— moiety, where R is X.

7. The composition of claim 1 , wherein L is —CH 2 —CH 2 —O—C(═O)— or —O—CF 2 —CF 2 —.

8. The composition of claim 1 , wherein A 1 is t-butyl, 1-ethylcyclopentyl, 1-methylcyclopentyl, 1-ethyl cyclohexyl, 1-methyl cyclohexyl, 2-ethyl-2-adamantyl, 2-methyl-2-adamantanyl, 1-adamantylisopropyl, 2-isopropyl-1-admantanyl, or a combination comprising at least one of the foregoing.

9. The composition of claim 1 , wherein the acid-sensitive polymer comprises the residue of a monomer having the formula

wherein R o is H, C 1-6 alkyl, or CF 3 .

10. The composition of claim 1 , further comprising a quencher comprising an amine, an amide, a carbamate, or a combination comprising at least one of the foregoing, a solvent, and optionally an additive comprising an embedded surface active additive, a surfactant, or a combination comprising at least one of the foregoing.

11. A patternable film comprising:
an acid-sensitive polymer, and
a cyclic sulfonium compound having the formula:
(R a ) 1 —(Ar)—S + (—CH 2 —) m · − O 3 S—(CR b 2 ) n —(L) p -X

or the formula:
(R a ) 1 —(Ar)—S + (—CH 2 —) m ·

wherein
R a is a isopropyl, t-butyl, cyclopentyl, or cyclohexyl,
Ar is para-phenylene,
each R b is independently F or a linear C 1-4 perfluoroalkyl group,
L is a C 1-30 linking group including an —C(═O)—NR— or —O—C(═O)—NR— moiety, wherein R is H or X,
X is a substituted or unsubstituted, C 5 or greater polycyclic or fused polycyclic cycloaliphatic group, optionally comprising a heteroatom comprising O, S, N, F, or a combination comprising at least one of the foregoing, and
Z 1 is —O— or —O—C(═O)—,
R 18 to R 21 are independently H, F, C 1-10 alkyl, or C 1-10 fluoroalkyl,
R 22 is norbornyl, cholate, a C 8 caged lactone, or a 1- or 2-adamantyl group optionally comprising an —OH, —OCH 3 , or —OCF 3 group,
1 is 1, m is 4, n is 2, p is 1, r is 2 to 4, and s is 0 to 4,
provided that when Z 1 is —O—C(═O)— and s is 0, r is 4,
wherein the acid-sensitive polymer comprises
(i) a structural unit comprising a monocyclic acid-cleavable group protecting a base-soluble group,
(ii) a structural unit comprising a polycyclic acid-cleavable group protecting a base-soluble group,
wherein the structural unit having the monocyclic or polycyclic acid-cleavable protective group is derived from
a monomer having the formula:
H 2 C═C(R c )—C(═O)—O-A 1

wherein R c is H, C 1-6 alkyl, F, or CF 3 and A 1 is a C 4-50 tertiary alkyl-containing group in which a tertiary center of A 1 is connected to an ester oxygen atom of the monomer, or
a monomer having the formula:
H 2 C═C(R d )—C(═O)—O—C(R e ) 2 —O—(CH 2 ) o -A 2

wherein R d is H, C 1-6 alkyl, F, or CF 3 , each R e is independently H or a C 1-4 alkyl group, A 2 is a C 1-30 cycloaliphatic group, and o is an integer of 0-4,
(iii) a structural unit derived from a lactone monomer, and
(iv) a structural unit derived from a polar monomer comprising a hydrogen donor group.

12. The patternable film of claim 11 , wherein the acid-sensitive polymer comprises the residue of a monomer having the formula

wherein R o is H, C 1-6 alkyl, or CF 3 .

13. A formulation comprising:
an acid-sensitive polymer,
a solvent, and
a cyclic sulfonium compound having the formula:
(R a ) 1 —(Ar)—S + (—CH 2 —) m · − O 3 S—(CR b 2 ) n —(L) p -X

or the formula:
(R a ) 1 —(Ar)—S + (—CH 2 —) m ·

wherein
R a is isopropyl, t-butyl, cyclopentyl, or cyclohexyl,
Ar is para-phenylene,

Assignees

• Li Mingqi
• Aqad Emad
• Liu Cong
• Chen Ching-Lung
• Yamada Shintaro
• Xu Cheng-Bai
• Mattia Joseph
• Rohm & Haas Elect Mat

Inventors

• Li Mingqi
• Aqad Emad
• Liu Cong
• Chen Ching-Lung
• Yamada Shintaro
• Xu Cheng-Bai
• Mattia Joseph

Classifications

• G03F7/0045 Primary

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

• G03F7/004 Primary

  Photosensitive materials (G03F7/12, G03F7/14 take precedence) · CPC title

• G03F7/0397

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