Photoacid generating compound and photoresist composition comprising same, coated article comprising the photoresist and method of making an article

1. A compound having the formula (I):

wherein a is an integer of from 1 to 10, and x is an integer of from 1 to 3,

X 1 comprises a fluoroalcohol or fluorinated anhydride,

Y is a single bond, C 1-20 alkylene group, O, S, NR, ester, carbonate, sulfonate, sulfone, or sulfonamide, wherein R is H or C 1-20 alkyl, and wherein the C 1-20 alkylene group is structurally only carbon, or one or more structural carbon atoms in the C 1-20 alkylene group is replaced by oxygen, carbonyl, ester, or a combination comprising at least one of the foregoing,

Ar is a substituted or unsubstituted, C 5 or greater monocyclic, polycyclic, or fused polycyclic cycloalkyl; or a substituted or unsubstituted, C 5 or greater monocyclic, polycyclic, or fused polycyclic aryl group, wherein the cycloalkyl or aryl is a carbocycle or comprises a heteroatom comprising O, S, N, F, or a combination comprising at least one of the foregoing,

each R 1 is independently a substituted C 5-40 aryl, substituted C 5-40 heteroaryl, C 1-40 alkyl, a C 3-40 cycloalkyl, wherein when x is 1, the two groups R 1 are separate or bonded to each other to form a C 4-40 ring structure, and

Z − is a carboxylate, sulfate, sulfonate, sulfamate or the anion of a sulfonimide, wherein when Y is a single bond, Z − is not sulfonate.

2. The compound of claim 1 , wherein a is an integer of from 1 to 4, x is 1, X 1 is a 1,1,1,3,3,3-hexafluoroisopropanol-containing group, and Y is —O—, —S—, NR—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —OCH 2 —(C═O)O—, —OCH 2 C(═O)—, —SO 2 —, —O—SO 2 —, or a combination comprising at least one of the fore going groups, wherein R is H or C 1-6 alkyl.

3. The compound of claim 1 , wherein Ar is a substituted or unsubstituted phenylene, naphthylene, anthracenylene, phenanthrenylene, quinolinylene, dibenzothiophenylene, thioxanthone, thiooxaanthracenylene, or a combination comprising at least one of the foregoing.

4. The compound of claim 1 , wherein R 1 is independently a substituted C 5-20 aryl or a C 1-20 alkyl, wherein when x is 1, the two groups R 1 are separate or bonded to each other to form a C 4-20 ring structure.

5. The compound of claim 1 , the compound having the formulas (Ia), (Ib), (Ic), (Id), or (Ie):

wherein a is an integer of from 1 to 4;

X 1 is a C 3-10 organic group containing a fluoroalcohol, Y is —O—, —S—, NR—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —OCH 2 —(C═O)O—, —OCH 2 C(═O)—, —SO 2 —, —O—SO 2 —, or a combination comprising at least one of the foregoing groups, and R is H or C 1-6 alkyl,

Ar 2 is a substituted or unsubstituted phenylene, naphthylene, anthracenylene, phenanthrenylene, quinolinylene, dibenzothiophenylene, thioxanthone, thioxanthenylene, or a combination comprising at least one of the foregoing,

each R 2 and R 3 is independently a substituted C 5-20 aryl not identical to Ar, or a C 1-20 alkyl, and L is a substituted or unsubstituted C 2-20 alkylene, and

Z − is a sulfate, sulfonate, or the anion of a sulfonimide.

6. The compound of claim 1 , comprising the formulas (IIIa) to (IIIg):

wherein b is an integer of from 1 to 5, w is 0 or 1, and c, d, and e are each an integer of from 1 to 8;

X 2 is a C 3-10 organic group containing a 1,1,1,3,3,3-hexafluoroisopropanol-containing group,

Y is —O—, —S—, NR—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —OCH 2 —(C═O)O—, —OCH 2 C(═O)—, —SO 2 —, —O—SO 2 —, or a combination comprising at least one of the foregoing groups, and R is H or C 1-6 alkyl,

each R 2 and R 3 is independently a substituted C 5-20 aryl not identical to Ar, or a C 1-20 alkyl, and L is a substituted or unsubstituted C 2-20 alkylene, and

Z − is a carboxylate, sulfate, sulfonate, sulfamate, or the anion of a sulfonimide.

7. The compound of claim 1 , wherein Z − has the formula (II):

A-(L)-(C(R 4 ) 2 ) m —(C(R 5 ) 2 ) n —SO 3 −   (II)

wherein

A is a substituted or unsubstituted, monocyclic, polycyclic, or fused polycyclic C 3 or greater cycloaliphatic group optionally comprising O, S, N, F, or a combination comprising at least one of the foregoing, or a C 3 or greater aliphatic or cycloaliphatic group containing a polymerizable double or triple bond,

R 4 is H, a single bond, or a substituted or unsubstituted C 1-30 alkyl group, wherein when R 4 is a single bond, R 4 is covalently bonded to a carbon atom of A,

each R 5 is independently H, F, or C 1-4 fluoroalkyl, wherein at least one R 5 is not hydrogen,

L is a linking group comprising an —O—, —S—, —C(═O)—, carbonate, carboxylate, sulfonate, sulfate, or a sulfonamide group, and

q is an integer of 0 to 10, m is an integer of greater than or equal to 0, and n is an integer of greater than or equal to 1.

8. A photoresist composition, comprising the compound of claim 1 and a polymer having acid labile protecting groups.

9. A coated substrate, comprising: (a) a substrate having one or more layers to be patterned on a surface thereof; and (b) a layer of a photoresist composition of claim 8 over the one or more layers to be patterned.

10. The photoresist composition of claim 8 , wherein a is an integer of from 1 to 4, x is 1, X 1 is a 1,1,1,3,3,3-hexafluoroisopropanol-containing group, and Y is —O—, —S—, NR—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —OCH 2 —(C═O)O—, —OCH 2 C(═O)—, —SO 2 —, —O—SO 2 —, or a combination comprising at least one of the foregoing groups, wherein R is H or C 1-6 alkyl.

11. The photoresist composition of claim 8 , wherein the compound has one of formulas (Ia), (Ib), (Ic), (Id), or (Ie):

wherein a is an integer of from 1 to 4;

X 1 is a C 3-10 organic group containing a fluoroalcohol, Y is —O—, —S—, NR—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —OCH 2 —(C═O)O—, —OCH 2 C(═O)—, —SO 2 —, —O—SO 2 —, or a combination comprising at least one of the foregoing groups, and R is H or C 1-6 alkyl,

Ar 2 is a substituted or unsubstituted phenylene, naphthylene, anthracenylene, phenanthrenylene, quinolinylene, dibenzothiophenylene, thioxanthone, thioxanthenylene, or a combination comprising at least one of the foregoing,

each R 2 and R 3 is independently a substituted C 5-20 aryl not identical to Ar, or a C 1-20 alkyl, and L is a substituted or unsubstituted C 2-20 alkylene, and

Z − is a sulfate, sulfonate, or the anion of a sulfonimide.

12. The photoresist composition of claim 8 , wherein the compound has one of formulas (IIIa) to (IIIg):

wherein b is an integer of from 1 to 5, w is 0 or 1, and c, d, and e are each an integer of from 1 to 8;

X 2 is a C 3-10 organic group containing a 1,1,1,3,3,3-hexafluoroisopropanol-containing group,

Y is —O—, —S—, NR—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —OCH 2 —(C═O)O—, —OCH 2 C(═O)—, —SO 2 —, —O—SO 2 —, or a combination comprising at least one of the foregoing groups, and R is H or C 1-6 alkyl,

each R 2 and R 3 is independently a substituted C 5-20 aryl not identical to Ar, or a C 1-20 alkyl, and L is a substituted or unsubstituted C 2-20 alkylene, and

Z − is a carboxylate, sulfate, sulfonate, sulfamate, or the anion of a sulfonimide.

13. The photoresist composition of claim 8 , wherein Z − has the formula (II):

A-(L)-(C(R 4 ) 2 ) m —(C(R 5 ) 2 ) n —SO 3 −   (II)

wherein

A is a substituted or unsubstituted, monocyclic, polycyclic, or fused polycyclic C 3 or greater cycloaliphatic group optionally comprising O, S, N, F, or a combination comprising at least one of the foregoing, or a C 3 or greater aliphatic or cycloaliphatic group containing a polymerizable double or triple bond,

R 4 is H, a single bond, or a substituted or unsubstituted C 1-30 alkyl group, wherein when R 4 is a single bond, R 4 is covalently bonded to a carbon atom of A,

each R 5 is independently H, F, or C 1-4 fluoroalkyl, wherein at least one R 5 is not hydrogen,

L is a linking group comprising an —O—, —S—, —C(═O)—, carbonate, carboxylate, sulfonate, sulfate, or a sulfonamide group, and

q is an integer of 0 to 10, m is an integer of greater than or equal to 0, and n is an integer of greater than or equal to 1.

14. The compound of claim 1 , wherein X 1 is a 1,1,1,3,3,3-hexafluoroisopropanol-containing group.

15. A method of making a relief image, comprising

coating a substrate with a photoresist layer comprising

a polymer having acid deprotectable groups, and

a compound having the formula (I):

wherein a is an integer of from 1 to 10, and x is an integer of from 1 to 3,

X 1 comprises a fluoroalcohol or fluorinated anhydride,

Y is a single bond, C 1-20 alkylene group, O, S, NR, ester, carbonate, sulfonate, sulfone, or sulfonamide, wherein R is H or C 1-10 alkyl, and wherein the C 1-20 alkylene group is structurally only carbon, or one or more structural carbon atoms in the C 1-20 alkylene group is replaced by oxygen, carbonyl, ester, or a combination comprising at least one of the foregoing,

Ar is a substituted or unsubstituted, C 5 or greater monocyclic, polycyclic, or fused polycyclic cycloalkyl; or a substituted or unsubstituted, C 5 or greater monocyclic, polycyclic, or fused polycyclic aryl group, wherein the cycloalkyl or aryl is a carbocycle or comprises a heteroatom comprising O, S, N, F, or a combination comprising at least one of the foregoing,

each R 1 is independently a substituted C 5-40 aryl, substituted C 5-40 heteroaryl, C 1-40 alkyl, a C 3-40 cycloalkyl, wherein when x is 1, the two groups R 1 are separate or bonded to each other to form a C 4-40 ring structure, and

Z − is a carboxylate, sulfate, sulfonate, sulfamate, or the anion of a sulfonimide, wherein when Y is a single bond, Z − is not sulfonate;

patternwise exposing the photoresist composition layer to actinic radiation; and

developing the pattern by treatment with an aqueous alkaline developer to form a positive tone relief image, or with an organic solvent developer to form a negative tone relief image.

16. The method of making a relief image of claim 15 , wherein X 1 is a 1,1,1,3,3,3-hexafluoroisopropanol-containing group.

17. The method of claim 15 , wherein a is an integer of from 1 to 4, x is 1, X 1 is a 1,1,1,3,3,3-hexafluoroisopropanol-containing group, and Y is —O—, —S—, NR—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —OCH 2 —(C═O)O—, —OCH 2 C(═O)—, —SO 2 —, —O—SO 2 —, or a combination comprising at least one of the foregoing groups, wherein R is H or C 1-6 alkyl.

18. The method of claim 15 , wherein the compound has one of formulas (Ia), (Ib), (Ic), (Id), or (Ie):

wherein a is an integer of from 1 to 4;

X 1 is a C 3-10 organic group containing a fluoroalcohol, Y is —O—, —S—, NR—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —OCH 2 —(C═O)O—, —OCH 2 C(═O)—, —SO 2 —, —O—SO 2 —, or a combination comprising at least one of the foregoing groups, and R is H or C 1-6 alkyl,

Ar 2 is a substituted or unsubstituted phenylene, naphthylene, anthracenylene, phenanthrenylene, quinolinylene, dibenzothiophenylene, thioxanthone, thioxanthenylene, or a combination comprising at least one of the foregoing,

each R 2 and R 3 is independently a substituted C 5-20 aryl not identical to Ar, or a C 1-20 alkyl, and L is a substituted or unsubstituted C 2-20 alkylene, and

Z − is a sulfate, sulfonate, or the anion of a sulfonimide.

19. The method of claim 15 , wherein the compound has one of formulas (IIIa) to (IIIg):

wherein b is an integer of from 1 to 5, w is 0 or 1, and c, d, and e are each an integer of from 1 to 8;

X 2 is a C 3-10 organic group containing a 1,1,1,3,3,3-hexafluoroisopropanol-containing group,

Y is —O—, —S—, NR—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —OCH 2 —(C═O)O—, —OCH 2 C(═O)—, —SO 2 —, —O—SO 2 —, or a combination comprising at least one of the foregoing groups, and R is H or C 1-6 alkyl,

each R 2 and R 3 is independently a substituted C 5-20 aryl not identical to Ar, or a C 1-20 alkyl, and L is a substituted or unsubstituted C 2-20 alkylene, and

Z − is a carboxylate, sulfate, sulfonate, sulfamate, or the anion of a sulfonimide.

20. The method of claim 15 , wherein Z − has the formula (II):

A-(L)-(C(R 4 ) 2 ) m —(C(R 5 ) 2 ) n —SO 3 −   (II)

wherein

A is a substituted or unsubstituted, monocyclic, polycyclic, or fused polycyclic C 3 or greater cycloaliphatic group optionally comprising O, S, N, F, or a combination comprising at least one of the foregoing, or a C 3 or greater aliphatic or cycloaliphatic group containing a polymerizable double or triple bond,

R 4 is H, a single bond, or a substituted or unsubstituted C 1-30 alkyl group, wherein when R 4 is a single bond, R 4 is covalently bonded to a carbon atom of A,

each R 5 is independently H, F, or C 1-4 fluoroalkyl, wherein at least one R 5 is not hydrogen,

L is a linking group comprising an —O—, —S—, —C(═O)—, carbonate, carboxylate, sulfonate, sulfate, or a sulfonamide group, and

q is an integer of 0 to 10, m is an integer of greater than or equal to 0, and n is an integer of greater than or equal to 1.