Photoacid generator and photoresist comprising same

1. A mixture of structural isomers of a photoacid generator of formula (I):

wherein

each R a in formula 1 is independently H, F, a C 1-10 nonfluorinated organic group, C 1-10 fluorinated organic group, or a combination comprising at least one of the foregoing, provided at least one R a is F or a C 1-10 fluorinated organic group, the C 1-10 fluorinated and nonfluorinated organic groups each optionally comprising O, S, N, or a combination comprising at least one of the foregoing heteroatoms;

L 1 is a linking group comprising a heteroatom comprising O, S, N, F, or a combination comprising at least one of the foregoing;

G + is an onium salt of the formula (II):

wherein in formula (II),

X is S or I,

each R 0 is independently C 1-30 alkyl group; a polycyclic or monocyclic C 3-30 cycloalkyl group; a polycyclic or monocyclic C 4-30 aryl group; or a combination comprising at least one of the foregoing, provided at least one R 0 is substituted where each R 0 is a C 6 monocyclic aryl group, and wherein when X is I, x is 2, and where X is S, x is 3, and

p is 0 or 1, q is an integer of from 1 to 10.

2. The mixture of structural isomers of a photoacid generator of claim 1 , wherein L 1 is a C 1-30 linking group comprising an ether, ester, amine, amide, ketone, acetal, ketal, sulfide, disulfide, thiocarbonyl, sulfonate, sulfonamide, or a combination comprising at least one of the foregoing groups.

3. The mixture of structural isomers of a photoacid generator of claim 1 , wherein L 1 is linear or branched, and fluorinated or non-fluorinated, and comprises a C 1-10 alkylene, C 1-10 alkyleneoxy, C 1-10 ester, C 1-10 amide, C 1-10 sulfonate, C 1-10 sulfonamide, or a combination comprising at least one of the foregoing.

4. The mixture of structural isomers of a photoacid generator of claim 1 , having the formula (III):

wherein X is N, O, or a single bond, L 2 is linear or branched, and fluorinated or non-fluorinated, and comprises a C 1-10 alkylene, C 1-10 alkyleneoxy, C 1-10 ester, C 1-10 amide, C 1-10 sulfonate, C 1-10 sulfonamide, or a combination comprising at least one of the foregoing, each R b is H, a linear or branched C 1-10 alkyl group, or a combination comprising at least one of the foregoing, each R c is H, F, a C 1-10 fluorinated organic group, or a combination comprising at least one of the foregoing provided at least one R c is not H, a is an integer of 0 to 10, and b is an integer of from 1 to 10 provided that a+b is less than or equal to 10, and G + is as defined in Formula (II).

5. The mixture of structural isomers of a photoacid generator of claim 1 , having the formula (IV):

wherein L 3 is a carbonyl, C 1-10 alkylene, C 1-10 alkyleneoxy, C 1-10 ester, or a combination comprising at least one of the foregoing, each R c is H, F, a C 1-10 fluorinated organic group, or a combination comprising at least one of the foregoing, a and c are each an integer of from 0 to 9, and d is an integer of from 1 to 10, provided a+c+d is less than or equal to 10, and G + is as defined for Formula (II).

6. The mixture of structural isomers of a photoacid generator of claim 1 , having the formula (V):

wherein L 3 is a carbonyl, C 1-10 alkylene, C 1-10 alkyleneoxy, C 1-10 ester, or a combination comprising at least one of the foregoing, a is an integer of from 0 to 9, and e is an integer of from 1 to 10, provided a+e is less than or equal to 10, and G + is as defined for Formula (II).

7. The mixture of structural isomers of a photoacid generator of claim 1 , having the formula:

wherein G + is as defined for Formula (II).

8. The mixture of structural isomers of a photoacid generator of claim 1 , wherein G + is sulfonium salt of the formula X to XV:

wherein R 1 and R 2 are independently H, a linear or branched C 1-10 alkyl group, C 2-10 alkenyl, C 1-10 fluoroalkyl group, C 7-10 aralkyl group, C 6-10 aryl group, or a combination comprising at least one of the foregoing, wherein R 1 and R 2 are separate or are connected via a single or double bond to form a carbocycle or heterocycle,

R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are each independently H, halogen, C 1-10 alkyl, C 1-10 alkoxy, C 6-10 aryl, a thiophenoxy, a thioalkoxy, alkoxycarbonyl, or a combination comprising at least one of the foregoing, wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 each optionally include an acid labile group, a base labile group or a base soluble group,

m is an integer of from 1 to 10, and n is 1 or 2.

9. The mixture of structural isomers of a photoacid generator of claim 1 , wherein G + has the formula:

wherein R is a C 1-10 alkyl, C 1-10 fluoroalkyl, C 3-10 cycloalkyl, C 6-10 aryl, C 7-10 aralkyl, or a combination comprising at least one of the foregoing.

10. A photoresist comprising the mixture of structural isomers of a the photoacid generator of claim 1 and an acid deprotectable copolymer.

11. A coated film comprising: (a) a substrate having one or more layers to be patterned on a surface thereof; and (b) a layer of the photoresist of claim 10 over the one or more layers to be patterned.

12. A photoacid generator having the formula (III):

wherein in formula (III),

X in N,

L 2 is linear or branched, and fluorinated or non-fluorinated, and comprises a C 1-10 alkylene, C 1-10 alkyleneoxy, C 1-10 amide, C 1-10 sulfonate, C 1-10 sulfonamide, or a combination comprising at least one of the foregoing,

each R b is H, a linear or branched C 1-10 alkyl group, or a combination comprising at least one of the foregoing,

each R c is H, F, a C 1-10 fluorinated organic group, or a combination comprising at least one of the foregoing provided at least one R c is not H,

a is an integer of 0 to 10, and

b is an integer of from 1 to 10 provided that a+b is less than or equal to 10, and

G + is an onium salt of the formula (II):

wherein in formula (II),

X′ is S or I,

each R 0 is independently C 1-30 alkyl group; a polycyclic or monocyclic C 3-30 cycloalkyl group; a polycyclic or monocyclic C 4-30 aryl group; or a combination comprising at least one of the foregoing, provided at least one R 0 is substituted where each R 0 is a C 6 monocyclic aryl group, and

wherein when X′ is I, x is 2, and when X′ is S, x is 3.

13. A photoacid generator having the formula (IV):

wherein in formula (IV),

L 3 is a carbonyl, C 1-10 alkylene, C 1-10 alkyleneoxy, C 1-10 ester, or a combination comprising at least one of the foregoing,

each R c is H, F, a C 1-10 fluorinated organic group, or a combination comprising at least one of the foregoing,

a and c are each an integer of from 0 to 9, and

d is an integer of from 1 to 10, provided a+c+d is less than or equal to 10, and

G + is an onium salt of the formula (II):

wherein in formula (II),

X is S or I,

each R 0 is independently C 1-30 alkyl group; a polycyclic or monocyclic C 3-30 cycloalkyl group; a polycyclic or monocyclic C 4-30 aryl group; or a combination comprising at least one of the foregoing, provided at least one R 0 is substituted where each R 0 is a C 6 monocyclic aryl group, and

wherein when X is I, x is 2, and where X is S, x is 3.