Acid generator compounds and photoresists comprising same

1. A photoresist composition comprising:

(a) a polymer; and

(b) an acid generator comprising:

(i) a thioxanthone moiety; and

(ii) one or more covalently linked acid labile-groups,

wherein the acid generator exhibits a reduction potential of −0.9 to 0 V (vs. Ag/AgCl, cathodic peak potential) in a standard reduction potential assay.

2. The photoresist composition of claim 1 wherein the acid generator comprises an acid-labile group of the following Formula (II):

—(C═O)OR 3   (II)

wherein R3 is a non-hydrogen substituent that provides an acid-labile moiety.

3. The photoresist composition of claim 1 wherein the acid generator comprises an acid-labile group of the following Formula (III):

—O(CXY) n R 3   (III)

wherein X and Y are independently hydrogen or a non-hydrogen substituent; R 3 is a non-hydrogen substituent that provides an acid-labile moiety; and n is a positive integer.

4. The photoresist composition of claim 1 wherein the acid generator is covalently bound to a polymer.

5. A method for providing a photoresist relief image, comprising:

a) applying a coating layer of a photoresist composition of claim 1 on a substrate; and

b) exposing the photoresist composition layer to activating radiation and developing the exposed photoresist composition coating layer.

6. The method of claim 5 wherein the photoresist composition layer is exposed to EUV or e-beam radiation.

7. The photoresist composition of claim 1 wherein the cleavage product of the one or more covalently linked acid labile-groups comprises a carboalicyclic group.

8. The photoresist composition of claim 1 wherein the cleavage product of the one or more covalently acid labile-groups comprises an optionally substituted adamantyl group.

9. The photoresist composition of claim 1 wherein the cleavage product of the one or more covalently linked acid labile-groups comprises an optionally substituted cyclopentyl, cyclohexyl or cycloheptyl group.

10. The photoresist composition of claim 1 wherein the cleavage product of the one or more covalently linked acid labile-groups comprises a heteroalicyclic group.

11. The photoresist composition of claim 1 wherein the cleavage product of the one or more covalently linked acid labile-groups comprises an aromatic group.

12. The photoresist composition of claim 11 wherein the cleavage product of the one or more covalently linked acid labile-groups comprises an optionally substituted phenyl or naphthyl.

13. An acid generator comprising:

(i) a thioxanthone moiety; and

(ii) one or more covalently linked acid labile-groups,

wherein the acid generator exhibits a reduction potential of −0.9 to 0 V (vs. Ag/AgCl, cathodic peak potential) in a standard reduction potential assay.

14. A photoresist composition comprising:

(a) a polymer; and

(b) an acid generator compound that comprises a structure of Formula (I):

wherein: Z is a counter anion;

R is a non-hydrogen substituent;

X is >C=0;

each T and each T′ are the same or different non-hydrogen substituent;

each L and each L′ are the same or different acid-labile group, with T, L, T′, and U nonhydrogen groups may be taken together to form a ring;

m and m′ are each independently 0, 1, 3 or 4; and

n and n′ are each independently 0, 1, 2, 3 or 4,

wherein if R does not comprise an acid-labile group, then at least one of n and n′ is greater than zero whereby the acid generator compound comprises at least one acid-labile group; and

wherein the acid generator compound exhibits a reduction potential of −0.9 to 0 V (vs. Ag/AgCl, cathodic peak potential) in a standard reduction potential assay.

15. The photoresist composition of claim 14 wherein the acid generator comprises a structure of Formula (IA):

wherein: Z is a counter anion;

X is >C=0;

each T, each T′ and each T″ are the same or different non-hydrogen substituent;

each L, each L′ and each L″ are the same or different acid-labile group, with T, L, T′, L′, T″ and L″ non-hydrogen groups may be taken together to form a ring;

m and m′ are each independently 0, 1, 2, 3 or 4; m″ is 0, 1, 2, 3, 4 or 5; n and n′ are each independently 0, 1, 2, 3 or 4; n″ is independently 0, 1, 2, 3, 4 or 5; and at least one of n, n′ and n″ are other than 0.

16. The photoresist composition of claim 14 wherein the acid generator comprises a structure of Formula (IC):

wherein: Z is a counter anion;

each T, each T′ and each T″ are the same or different non-hydrogen substituent;

each L, each L′ and each L″ are the same or different acid-labile group, with T, L, T′, L′, T″ and L″ non-hydrogen groups may be taken together to form a ring;

m and m′ are each independently 0, 1, 2, 3 or 4; m″ is 0, 1, 2, 3, 4 or 5; n and n′ are each independently 0, 1, 2, 3 or 4; n″ is independently 0, 1, 2, 3, 4 or 5; and at least one of n, n′ and n″ are other than 0.

17. The photoresist composition of claim 14 wherein the acid generator comprises an acid-labile group of the following Formula (II):

—(C═O)OR 3   (II)

wherein R 3 is a non-hydrogen substituent that provides an acid-labile moiety.

18. The photoresist composition of claim 14 wherein the acid generator comprises an acid-labile group of the following Formula (III):

—O(CXY) n R 3   (III)

wherein X and Y are independently hydrogen or a non-hydrogen substituent; R 3 is a non-hydrogen substituent that provides an acid-labile moiety; and n is a positive integer.

19. The photoresist composition of claim 14 wherein the acid generator compound is covalently bound to a polymer.

20. The photoresist composition of claim 14 wherein the cleavage product of the one or more acid labile-groups comprises a carboalicyclic group.

21. The photoresist composition of claim 20 wherein the cleavage product of the one or more acid labile-groups comprises an optionally substituted adamantyl group.

22. The photoresist composition of claim 20 wherein the cleavage product of the one or more acid labile-groups comprises an optionally substituted cyclopentyl, cyclohexyl or cycloheptyl group.

23. The photoresist composition of claim 14 wherein the cleavage product of the one or more acid labile-groups comprises a heteroalicyclic group.

24. The photoresist composition of claim 14 wherein the cleavage product of the one or more acid labile-groups comprises an aromatic group.

25. The photoresist composition of claim 24 wherein the cleavage product of the one or more acid labile-groups comprises an optionally substituted phenyl or naphthyl.

26. The photoresist composition of claim 14 wherein the acid generator comprises a cation component selected from the following:

10-(5-((2-1(ethylcyclopentyloxy)-2-oxoethoxy)carbonyl)-2-methoxyphenyl)-9-oxo-4,4a,9,10-tetrahydrothioxanthylium;

10-(5-((2-1(ethylcyclopentyloxy)-2-oxoethoxy)carbonyl)-2-methoxyphenyl)-9-oxo-2-(trifluoromethyl)-4,4a,9,10-tetrahydrothioxanthylium;

10-(4-tert-butylphenyl)-2-(2-1(ethylcyclopentyloxy)-2-oxoethoxy)-1,3-dimethyl-9-oxo-9,10-dihydrothioxanthylium; and

10-(4-tert-butylphenyl)2-(2-1(ethylcyclopentyloxy)-2-oxoethoxy)carbonyl)-9-oxo-9,10-dihydrothioxanylium.

27. The photoresist composition of claim 14 wherein the acid generator comprises a cation component selected from the following:

28. The photoresist of claim 14 wherein R comprises an acid-labile group.

29. A photoresist composition comprising:

(a) a polymer; and

(b) an acid generator compound that comprises a structure of Formula (I):

wherein: Z is a counter anion;

R is a non-hydrogen substituent;

X is >C=0;

each T and each T′ are the same or different non-hydrogen substituent;

each L and each L′ are the same or different acid-labile group, with T, L, T′, and L′ nonhydrogen groups may be taken together to form a ring;

m and m′ are each independently 0, 1, 2, 3 or 4; and

n and n′ are each independently 0, 1, 2, 3 or 4,

wherein if R does not comprise an acid-labile group, then at least one of n and n′ is greater than zero whereby the acid generator compound comprises at least one acid-labile group; and

wherein the cleavage product of the one or more covalently linked acid labile-groups comprises a heteroalicyclic group.