Photoresist compositions

1. A radiation sensitive composition comprising:

a) a first photoacid generator (PAG) compound P1, which comprises one or more compounds of the structure (A);

b) a second photoacid generator compound P2 which comprises one or more compounds of the structure (B);

c) a polymer component comprising an alkali soluble resin component whose alkali solubility is suppressed by the presence of acid sensitive moieties and whose alkali solubility is returned by treatment with an acid and, optionally, heat; wherein said polymer comprises one or more polymers comprising the monomer unit (C); and

d) a solvent;

wherein structure (A) has the formula:

wherein R 1 and R 2 are each independently selected from the group consisting of C 1 -C 12 fluoroalkyl groups or together R 1 and R 2 are joined with the N to form a (F 2 C) y N ring where y=4-12; R 3 , R 4 , and R 5 are each independently selected from the group consisting of unsubstituted aryl, alkyl or alpha-ketomethyl groups or such groups substituted with an acid sensitive group, or R 3 and R 4 together with the S atom form a cycloalkylsulfonium ring; R 6 to R 11 and R 6′ to R 11′ are independently selected from the group consisting of branched or linear alkyl, alkoxy, halogen, hydrogen, OCO 2 G, OCH 2 CO 2 G, and OG where G=an acid sensitive group;

wherein structure (B) has the formula:

wherein each R 12 is independently selected from the group consisting of a linear, cyclic, or branched C 1 -C 8 fluoroalkyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthalene group, C 6 -C 12 cyclic or alicyclic hydrocarbon, and a linear, cyclic, or branched C 1 -C 8 alkyl group; and

wherein monomeric unit (C) has the formula:

wherein R 13 is selected from the group consisting of H, C 1 -C 4 lower alkyl, CN, and CH 2 CO 2 R 20 ; R 14 and R 15 are each independently selected from the group consisting of H, linear or branched C 1 -C 4 alkyl, and halogen; R 16 is selected from the group consisting of H and branched or linear C 1 -C 4 alkyl; R 17 is selected from the group consisting of substituted or unsubstituted phenyl, a substituted or unsubstituted linear, branched or cyclic C 1 -C 20 alkyl, optionally containing an ether or ester group, a substituted or unsubstituted phenylalkylene, and a substituted or unsubstituted C 6 -C 20 cyclic alkylene ; R 18 and R 19 are each independently selected from the group consisting of H, linear or branched or cyclic C 1 -C 14 alkyl, and C 7 -C 14 alicyclic; R 20 is selected from the group consisting of a C 1 -C 14 branched, linear or cyclic alkyl, substituted or unsubstituted phenyl, and C 7 -C 14 alicyclic group.

2. The radiation sensitive composition of claim 1 wherein the total amount of photoactive generator content in the composition is from about 0.05 to about 20 wt % of the solids content of the composition and photoactive generator compound P1 comprises from about 25 to about 99 wt % and the second photoactive generator compound P2 comprises from about 1 to about 75 wt % of the total photoactive generator content of the composition.

3. The radiation sensitive composition of claim 1 wherein the total amount of photoactive generator content in the composition is from about 1 to about 15 wt % of the solids content of the composition and photoactive generator compound P1 comprises from about 35 to about 90 wt % and the second photoactive generator compound P2 comprises from about 10 to about 65 wt % of the total photoactive generator content of the composition.

4. The radiation sensitive composition of claim 1 wherein the total amount of photoactive generator content in the composition is from about 0.05 to about 20 wt % of the solids content of the composition and photoactive generator compound P1 comprises from about 60 to about 80 wt % and the second photoactive generator compound P2 comprises from about 20 to about 40 wt % of the total photoactive generator content of the composition.

5. The radiation sensitive composition of claim 1 wherein the polymer component comprises from about 75 to about 95 wt % of the total solids content of the composition.

6. The radiation sensitive composition of claim 1 wherein in structure (A) M is S and R 1 and R 2 are C 1 -C 6 perfluoroalkyl and in structure (B) R 12 is linear, branched or cyclic C 1 -C 7 alkyl.

7. The radiation sensitive composition of claim 6 wherein R 1 and R 2 are different C 1 -C 6 perfluoroalkyl groups.

8. The radiation sensitive composition of claim 1 wherein in photoactive generator compound P1 the (R 1 SO 2 NSO 2 R 2 ) − group is selected from the group consisting of

(CF 3 SO 2 NSO 2 CF 3 ) − (CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 SO 2 NSO 2 CF 3 ) −

(CF 3 CF 2 SO 2 NSO 2 NCF 2 CF 3 ) −

(CF 3 CF 2 CF 2 CF 2 SO 2 NSO 2 CF 2 CF 2 CF 2 CF 3 ) − (CF 3 CF 2 SO 2 NSO 2 CF 3 ) −

(CF 3 CF 2 CF 2 SO 2 NSO 2 CF 2 CF 2 CF 2 CF 2 CF 3 ) −

(CF 3 CF 2 CF 2 CF 2 SO 2 NSO 2 CF 3 ) −

(CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 SO 2 NSO 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 3 ) −

(CF 3 (CF 2 ) 7 SO 2 NSO 2 CF 3 ) −

and the substituted or unsubstituted R 3 R 4 R 5 S+ group is selected from the group consisting of:

the diaryl iodonium cation is are selected from the group consisting of:

and in the second photoacid generator compound P2 each R 12 is independently selected from the group consisting of methyl, ethyl, n-butyl, t-butyl, cyclohexyl, perfluorobutyl, phenyl, methoxyphenyl, bromophenyl, 4-methoxynaphthalene, naphthalene and adamantly; and

in the polymer comprising monomeric unit (C), R 13 , R 14 , R 15 , R 16 , R 18 , and R 19 =H and R 17 is selected from the group consisting of C 1 -C 4 linear or branched alkyl and a substituted or unsubstituted C 6 -C 20 cyclic alkylene.

9. The radiation sensitive composition of claim 8 wherein the polymer component comprises an additional monomer unit selected from the group consisting of acrylates, methacrylates, vinyl ethers, vinyl esters, substituted and unsubstituted styrenes.

10. The radiation sensitive composition of claim 1 wherein the polymer component comprises an additional monomeric unit that is hydroxystyrene.

11. The radiation sensitive composition of claim 1 wherein photoactive generator compound P1 is selected from the group consisting of

4-(1-butoxyphenyl)diphenylsulfonium bis-(perfluorobutanesulfonyl)imide,

4-(1-butoxyphenyl)diphenylsulfonium bis-(perfluoroethanesulfonyl)imide,

2,4,6-trimethylphenyldiphenylsulfonium bis-perfluorobutanesulfonyl)imide,

2,4,6-trimethylphenyldiphenylsulfonium bis-(perfluoroethanesulfonyl)imide,

toluenediphenylsulfonium bis-(perfluorobutanesulfonyl)imide,

toluenediphenylsulfonium bis-(perfluoroethanesulfonyl)imide,

toluenediphenylsulfonium-(trifluoromethyl perfluorobutylsulfonyl)imide,

tris-(tert-butylphenyl)sulfonium-(trifluoromethyl perfluorobutylsulfonyl)imide,

tris-(tert-butylphenyl)sulfonium bis-(perfluorobutanesulfonyl)imide,

tris-(tert-butylphenyl)sulfonium-bis-(trifluoromethanesulfonyl)imide

the photoactive generator compound P2 is bis(tert-butylsulfonyl)imide, and

the polymer component is selected from 4-[1-(2-cyclohexylethoxy)-ethoxy]styrene-co-4-[1-(t-butoxy)-ethoxy]styrene-co-4-hydroxy styrene-co-4-t-butylstyrene copolymer, [4-(1-ethoxyethoxy)styrene-co-4-hydroxystyrene, and mixtures thereof.

12. A process for producing a patterned image on a substrate, the process comprising the steps of:

a. coating on a suitable substrate a radiation sensitive composition of claim 1 , thereby forming a coated substrate;

b. prebaking the coated substrate;

c. exposing the prebaked coated substrate to actinic radiation;

d. optionally post-baking the exposed coated substrate;

e. developing the exposed coated substrate with a developer thereby forming an uncured relief image on the coated substrate; and

f. baking the developed coated substrate at an elevated temperature thereby curing the image.

13. A process for producing a patterned image on a substrate, the process comprising the steps of:

a. coating on a suitable substrate a radiation sensitive composition of claim 2 , thereby forming a coated substrate;

b. prebaking the coated substrate;

c. exposing the prebaked coated substrate to actinic radiation;

d. optionally post-baking the exposed coated substrate;

e. developing the exposed coated substrate with a developer thereby forming an uncured relief image on the coated substrate; and

f. baking the developed coated substrate at an elevated temperature thereby curing the image.

14. A process for producing a patterned image on a substrate, the process comprising the steps of:

a. coating on a suitable substrate a radiation sensitive composition of claim 3 , thereby forming a coated substrate;

b. prebaking the coated substrate;

c. exposing the prebaked coated substrate to actinic radiation;

d. optionally post-baking the exposed coated substrate;

e. developing the exposed coated substrate with a developer thereby forming an uncured relief image on the coated substrate; and

f. baking the developed coated substrate at an elevated temperature thereby curing the image.

15. A process for producing a patterned image on a substrate, the process comprising the steps of:

a. coating on a suitable substrate a radiation sensitive composition of claim 4 , thereby forming a coated substrate;

b. prebaking the coated substrate;

c. exposing the prebaked coated substrate to actinic radiation;

d. optionally post-baking the exposed coated substrate;

e. developing the exposed coated substrate with a developer thereby forming an uncured relief image on the coated substrate; and

f. baking the developed coated substrate at an elevated temperature thereby curing the image.

16. A process for producing a patterned image on a substrate, the process comprising the steps of:

a. coating on a suitable substrate a radiation sensitive composition of claim 5 , thereby forming a coated substrate;

b. prebaking the coated substrate;

c. exposing the prebaked coated substrate to actinic radiation;

d. optionally post-baking the exposed coated substrate;

e. developing the exposed coated substrate with a developer thereby forming an uncured relief image on the coated substrate; and

f. baking the developed coated substrate at an elevated temperature thereby curing the image.

17. A process for producing a patterned image on a substrate, the process comprising the steps of:

a. coating on a suitable substrate a radiation sensitive composition of claim 6 , thereby forming a coated substrate;

b. prebaking the coated substrate;

c. exposing the prebaked coated substrate to actinic radiation;

d. optionally post-baking the exposed coated substrate;

e. developing the exposed coated substrate with a developer thereby forming an uncured relief image on the coated substrate; and

f. baking the developed coated substrate at an elevated temperature thereby curing the image.

18. A process for producing a patterned image on a substrate, the process comprising the steps of:

a. coating on a suitable substrate a radiation sensitive composition of claim 7 , thereby forming a coated substrate;

b. prebaking the coated substrate;

c. exposing the prebaked coated substrate to actinic radiation;

d. optionally post-baking the exposed coated substrate;

e. developing the exposed coated substrate with a developer thereby forming an uncured relief image on the coated substrate; and

f. baking the developed coated substrate at an elevated temperature thereby curing the image.

19. A process for producing a patterned image on a substrate, the process comprising the steps of:

a. coating on a suitable substrate a radiation sensitive composition of claim 8 , thereby forming a coated substrate;

b. prebaking the coated substrate;

c. exposing the prebaked coated substrate to actinic radiation;

d. optionally post-baking the exposed coated substrate;

e. developing the exposed coated substrate with a developer thereby forming an uncured relief image on the coated substrate; and

f. baking the developed coated substrate at an elevated temperature thereby curing the image.

20. A process for producing a patterned image on a substrate, the process comprising the steps of:

a. coating on a suitable substrate a radiation sensitive composition of claim 9 , thereby forming a coated substrate;

b. prebaking the coated substrate;

c. exposing the prebaked coated substrate to actinic radiation;

d. optionally post-baking the exposed coated substrate;

e. developing the exposed coated substrate with a developer thereby forming an uncured relief image on the coated substrate; and

f. baking the developed coated substrate at an elevated temperature thereby curing the image.

21. A process for producing a patterned image on a substrate, the process comprising the steps of:

a. coating on a suitable substrate a radiation sensitive composition of claim 10 , thereby forming a coated substrate;

b. prebaking the coated substrate;

c. exposing the prebaked coated substrate to actinic radiation;

d. optionally post-baking the exposed coated substrate;

e. developing the exposed coated substrate with a developer thereby forming an uncured relief image on the coated substrate; and

f. baking the developed coated substrate at an elevated temperature thereby curing the image.

22. A process for producing a patterned image on a substrate, the process comprising the steps of:

a. coating on a suitable substrate a radiation sensitive composition of claim 11 , thereby forming a coated substrate;

b. prebaking the coated substrate;

c. exposing the prebaked coated substrate to actinic radiation;

d. optionally post-baking the exposed coated substrate;

e. developing the exposed coated substrate with a developer thereby forming an uncured relief image on the coated substrate; and

f. baking the developed coated substrate at an elevated temperature thereby curing the image.