Photoresist composition

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,

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.

14. The formulation of claim 13 , 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 .