Acid generators and photoresists comprising same

1. A photoacid generator comprising a group of the following Formulae I or II:

wherein in each of Formulae I and II:

the waved line represents a covalent linkage connecting the depicted moiety to the larger acid generator material;

R 2 , R 3 , R 4 and R 5 are each independently hydrogen or a non-hydrogen substituent, with at least one of R 2 and R 3 being a non-hydrogen substituent;

R 2 and R 3 optionally may be taken together to form a ring;

R 4 and R 5 optionally may be taken together to form a ring; and

R 4 and/or R 5 optionally may be taken together with the covalent linkage to form a ring; and

n is 0 or 1.

2. The photoacid generator of claim 1 wherein the photoacid generator is an onium compound.

3. The photoacid generator of claim 1 wherein the photoacid generator comprises a cation component that comprises a group of Formula I.

4. The photoacid generator of claim 1 wherein the photoacid generator comprises a group of the following formula (IV):

wherein:

x is 1,2 or 3;

a is a positive integer of from 1 to 12;

R 2 and R 3 are each independently hydrogen, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alicyclic; optionally substituted heteroalicyclic; optionally substituted carbocyclic aryl; or optionally substituted heteroaromatic; R 2 and R 3 may be taken together to form an aromatic or non-aromatic cyclic group, with at least one of R 2 and R 3 being a non-hydrogen substituent;

Y is a covalent bond or a linker group;

P is optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alicyclic, optionally substituted heteroalicyclic, optionally substituted carbocyclic aryl, optionally substituted heteroaromatic;

each R 1 is independently optionally substituted alkyl, optionally substituted heteroalkyl; optionally substituted alicyclic; optionally substituted heteroalicyclic; optionally substituted carbocyclic aryl; or optionally substituted heteroaromatic aryl,

when x is 1, two R 1 groups and the adjacent sulfur atom optionally may be taken together to form a ring; and

Z is a counter anion.

5. The photoacid generator of claim 1 wherein the acid generator comprises a group of Formula I.

6. A photoacid generator of claim 1 wherein the photoacid generator is a component of a resin.

7. A photoresist composition comprising 1) a resin and 2) one or more photoacid generators of claim 1 .

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

a) applying a coating layer of a photoresist composition of claim 7 on a substrate; and

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

9. The method of claim 8 wherein the activating radiation is EUV or electron-beam radiation.

10. The photoacid generator of claim 1 wherein the acid generator comprises a group of Formula II.

11. The photoacid generator of claim 1 wherein the acid generator comprises a group of Formula II.

12. A photoresist composition comprising 1) a resin and 2) one or more photoacid generators of claim 5 .

13. A photoresist composition comprising 1) a resin and 2) one or more photoacid generators of claim 10 .

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

a) applying a coating layer of a photoresist composition of claim 12 on a substrate; and

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

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

a) applying a coating layer of a photoresist composition of claim 13 on a substrate; and

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

16. A photoresist composition comprising a resin and a photoacid generator of the following Formula III:

wherein R 2 and R 3 are each independently hydrogen or non-hydrogen substituent, and R 2 and R 3 may be optionally taken together to form a ring such as optionally substituted C 3-30 alicyclic which optionally may have 1, 2, or 3 N, O or S ring members; and

the waved line represents a covalent linkage to the photoacid generator.

17. The photoresist composition of claim 16 wherein at least one, or both, of R 2 and R 3 is a non-hydrogen substituent.

18. A photoresist composition comprising a resin and a photoacid generator of the following Formula V:

wherein in Formula V:

a is an integer from 1 to 12;

x is an integer from 1 to 3,

Y is a linker;

Ar is an optionally substituted C 5 or greater monocyclic, polycyclic, or fused polycyclic cycloalkyl; or an optionally substituted C 5 or greater monocyclic, polycyclic, or fused polycyclic aryl group, wherein the cycloalkyl or aryl is a carbocycle (e.g. phenyl, naphthyl, anthracenyl) or comprises a heteroatom comprising O, S, N, F, or a combination comprising at least one of the foregoing,

each R 1 is independently optionally substituted carbocyclic aryl; optionally substituted heteroaryl; optionally substituted alkyl, a C 3-40 cycloalkyl, wherein when x is 1, two groups R 1 may be optionally taken together to form a ring structure,

R 2 and R 3 independently are hydrogen or a non-hydrogen substituent such as optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alicyclic, optionally substituted heteroalicyclic, optionally substituted carbocyclic aryl or optionally substituted heteroaromatic;

Z − is a non-nucleophilic anion such as carboxylate, sulfate, sulfonate, sulfamate, or the anion of a sulfonamide.

19. A photoresist composition comprising a resin and a photoacid generator of the following Formula VI and VII:

wherein:

a is an integer from 1 to 12;

x is an integer from 1 to 3,

Y is a linker;

Ar is an optionally substituted C 5 or greater monocyclic, polycyclic, or fused polycyclic cycloalkyl; or an optionally substituted C 5 or greater monocyclic, polycyclic, or fused polycyclic aryl group, wherein the cycloalkyl or aryl is a carbocycle (e.g. phenyl, naphthyl, anthracenyl) or comprises a heteroatom comprising O, S, N, F, or a combination comprising at least one of the foregoing,

each R 1 is independently optionally substituted carbocyclic aryl; optionally substituted heteroaryl; optionally substituted alkyl, a C 3-40 cycloalkyl, wherein when x is 1, two groups R 1 may be optionally taken together to form a ring structure,

each R 2 and R 3 independently are hydrogen or a non-hydrogen substituent such as optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alicyclic, optionally substituted heteroalicyclic, optionally substituted carbocyclic aryl or optionally substituted heteroaromatic;

R 4 and/or R 5 can optionally covalently attach to Y to form a ring.

20. The photoresist composition of claim 19 comprising a photoacid generator of Formula VI.

21. The photoresist composition of claim 19 comprising a photoacid generator of Formula VII.