Photosensitive copolymer and photoresist composition

1. A copolymer having the formula:

wherein R 1 -R 5 are each independently H, C 1-6 alkyl, or C 4-6 aryl, R 6 is a fluorinated or non-fluorinated C 5-30 acid decomposable group; each Ar is independently a monocyclic, polycyclic, or fused polycyclic C 6-20 aryl group; each occurrence of R 7 is —OR 11 where R 11 is a fluorinated or non-fluorinated C 5-30 acid decomposable acetal group comprising a fluorinated or nonfluorinated C 6-25 aryl group; each occurrence of R 8 is independently —OR 11 or a —C(CF 3 ) 2 OR 11 group where each occurrence of R 11 is independently H or a fluorinated or non-fluorinated C 5-30 acid decomposable group; each occurrence of R 9 is independently F, C 1-10 fluoroalkyl, or a C 1-10 fluoroalkoxy group; R 10 is a cation-bound C 10-40 photoacid generator-containing group of the formula

—(Ar″)—O—R 13

wherein Ar″ is a C 6-20 monocyclic, polycyclic, or fused polycyclic aryl group, and

wherein R 14 is H or C 1-4 alkyl, and R 17 is

wherein R 18 is H or a C 1-10 organic group, X is S or I, and h is 2 when X is S, or h is 1 when X is I, and k is 1 to 4, and Z − is an anion; or R 10 is

wherein R 18 is H or a C 1-10 organic group, X is S or I, and h is 2 when X is S, or h is 1 when X is I, k is 1 to 4, and Z − is an anion; mole fraction a is 0 to 0.80; mole fraction b is greater than 0 and less than or equal to 0.80; mole fraction c is 0.01 to 0.80; mole fraction d is greater than zero and less than or equal to 0.80; and mole fraction e is greater than 0 and less than or equal to 0.50; the sum of the mole fractions a+b+c+d+e is 1; 1 and m are independently integers of 1 to 4; and n is an integer of 1 to 5.

2. The copolymer of claim 1 , wherein mole fraction a is greater than 0 and the fluorinated or non-fluorinated C 5-30 acid decomposable group of R 6 is a tertiary alkyl ester group.

3. The copolymer of claim 1 , wherein the copolymer has the formula:

wherein R 12 is an acid decomposable acetal group comprising a fluorinated or non-fluorinated C 6-25 aryl group; each occurrence of R 8 is independently —OH or —C(CF 3 ) 2 OH; each occurrence of R 9 is independently F, C 1-10 fluoroalkyl, or a C 1-10 fluoroalkoxy group; m is an integer of 1 to 4; n is an integer of 1 to 5; mole fraction b is 0.10 to 0.50; mole fraction c is 0.50 to 0.80; mole fraction d is 0.05 to 0.30; mole fraction e is 0.01 to 0.40; and the sum of the mole fractions b+c+d+e is 1.

4. The copolymer claim 1 , wherein the copolymer is of the formula:

wherein R 1 is H or C 1-4 alkyl; R 12 is an acid decomposable acetal group comprising a fluorinated or non-fluorinated C 6-25 aryl group; R 19 is a fluorinated or non-fluorinated C 4-20 tertiary alkyl, a fluorinated or non-fluorinated C 4-20 tertiary cycloalkyl, or a fluorinated or non-fluorinated tertiary or benzylic C 6-20 aryl alkyl; each occurrence of R 9 is independently F, C 1-10 fluoroalkyl, or a C 1-10 fluoroalkoxy group; R 10 is a cation-bound C 10-40 photoacid generator-containing group of the formula

—(Ar″)—O—R 13

wherein Ar″ is a C 6-20 monocyclic, polycyclic, or fused polycyclic aryl group, and

wherein R 14 is H or C 1-4 alkyl, and R 17 is

wherein R 18 is H or a C 1-10 organic group, X is S or I, and h is 2 when X is S, or h is 1 when X is I, and k is 1 to 4, and Z − is

or R 10 is

wherein R 18 is H or a C 1-10 organic group, X is S or I, and h is 2 when X is S, or h is 1 when X is I, k is 1 to 4, and Z − is

mole fraction a is 0 to 0.80; mole fraction b is greater than 0 and less than or equal to 0.80; mole fraction c is 0.01 to 0.80; mole fraction d is greater than zero and less than or equal to 0.80; and mole fraction e is greater than 0 and less than or equal to 0.50; the sum of the mole fractions a+b+c+d+e is 1; 1 and m are independently integers of 1 to 4, and n is an integer of 1 to 5.

5. The copolymer of claim 1 , wherein R 10 is a cation-bound C 10-40 photoacid generator-containing group of the formula

—(Ar″)—O—R 13

wherein Ar″ is a C 6-20 monocyclic, polycyclic, or fused polycyclic aryl group, and

wherein R 14 is H or C 1-4 alkyl, and R 17 is

wherein R 18 is H or a C 1-10 organic group, X is S or I, and h is 2 when X is S, or h is 1 when X is I, and k is 1 to 4, and Z − is an anion.

6. The copolymer of claim 1 , wherein R 10 is

wherein R 18 is H or a C 1-10 organic group, X is S or I, and h is 2 when X is S, or h is 1 when X is I, k is 1 to 4, and Z − is an anion.

7. A photoresist composition, comprising:

a copolymer having the formula:

wherein R 1 -R 5 are each independently H, C 1-6 alkyl, or C 4-6 aryl; R 6 is a fluorinated or non-fluorinated C 5-30 acid decomposable group; each Ar is independently a monocyclic, polycyclic, or fused polycyclic C 6-20 aryl group; R 7 is —OR 11 where R 11 is a fluorinated or non-fluorinated C 5-30 acid decomposable acetal group comprising a fluorinated or nonfluorinated C 6-25 aryl group; each occurrence of R 8 is independently —OR 11 or a —C(CF 3 ) 2 OR 11 group where each occurrence of R 11 is independently H or a fluorinated or non-fluorinated C 5-30 acid decomposable group; each occurrence of R 9 is independently F, C 1-10 fluoroalkyl, or a C 1-10 fluoroalkoxy group; R 10 is a cation-bound C 10-40 photoacid generator-containing group of the formula

R 10 =—(Ar″)—O—R 13

wherein Ar″ is a C 6-20 monocyclic, polycyclic, or fused polycyclic aryl group, and

wherein R 14 is H or C 1-4 alkyl, and R 17 is

wherein R 18 is H or a C 1-10 organic group, X is S or I, and h is 2 when X is S, or h is 1 when X is I, and k is 1 to 4, and Z − is an anion; or R 10 is

wherein R 18 is H or a C 1-10 organic group, X is S or I, and h is 2 when X is S, or h is 1 when X is I, k is 1 to 4, and Z − is an anion; mole fraction a is 0 to 0.80, mole fraction b is greater than 0 and less than or equal to 0.80, mole fraction c is 0.01 to 0.80, mole fraction d is greater than zero and less than or equal to 0.80; and mole fraction e is greater than 0 and less than or equal to 0.50, the sum of the mole fractions a+b+c+d+e is 1, l and m are independently integers of 1 to 4, and n is an integer of 1 to 5;

a photo-destroyable base;

a solvent; and

optionally, a non-polymer bound photoacid generator.

8. The photoresist composition of claim 7 , wherein the photo-destroyable base comprises a cation comprising:

and

an anion comprising:

or

RCO 2 —

wherein each R in the cation or anion is independently H, a C 1-20 alkyl, a C 1-20 alkoxy, a C 6-20 aryl, or a C 6-20 alkyl aryl.

9. A method of forming an electronic device, comprising:

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

(b) patternwise exposing the photoresist composition layer to activating radiation; and

(c) developing the exposed photoresist composition layer to provide a resist relief image.

10. The method of claim 9 , wherein mole fraction a is greater than 0 and the fluorinated or non-fluorinated C 5-30 acid decomposable group of R 6 is a tertiary alkyl ester group.

11. The method of claim 9 , wherein the copolymer has the formula:

wherein R 12 is an acid decomposable acetal group comprising a fluorinated or non-fluorinated C 6-25 aryl group; each occurrence of R 8 is —OH or —C(CF 3 ) 2 OH; each occurrence of R 9 is independently F, C 1-10 fluoroalkyl, or a C 1-10 fluoroalkoxy group; m is an integer of 1 to 4; n is an integer of 1 to 5; mole fraction b is 0.10 to 0.50; mole fraction c is 0.50 to 0.80; mole fraction d is 0.05 to 0.30 mole fraction e is 0.01 to 0.40 and the sum of the mole fractions b+c+d+e is 1.

12. The method of claim 9 , wherein R 10 is a cation-bound C 10-40 photoacid generator-containing group of the formula

—(Ar″)—O—R 13

wherein Ar″ is a C 6-20 monocyclic, polycyclic, or fused polycyclic aryl group, and

wherein R 14 is H or C 1-4 alkyl, and R 17 is

wherein R 18 is H or a C 1-10 organic group, X is S or I, and h is 2 when X is S, or h is 1 when X is I, and k is 1 to 4, and Z − is an anion.

13. The method of claim 9 , wherein R 10 is

wherein R 18 is H or a C 1-10 organic group, X is S or I, and h is 2 when X is S, or h is 1 when X is I, k is 1 to 4, and Z − is an anion.

14. The method of claim 9 , wherein the activating radiation is selected from e-beam and extreme ultraviolet.

15. The photoresist composition of claim 7 , wherein mole fraction a is greater than 0 and the fluorinated or non-fluorinated C 5-30 acid decomposable group of R 6 is a tertiary alkyl ester group.

16. The photoresist composition of claim 7 , wherein the copolymer has the formula:

wherein R 12 is an acid decomposable acetal group comprising a fluorinated or non-fluorinated C 6-25 aryl group; each occurrence of R 8 is independently —OH or —C(CF 3 ) 2 OH; each occurrence of R 9 is independently F, C 1-10 fluoroalkyl, or a C 1-10 fluoroalkoxy group; m is an integer of 1 to 4; n is an integer of 1 to 5; mole fraction b is 0.10 to 0.50; mole fraction c is 0.50 to 0.80; mole fraction d is 0.05 to 0.30; mole fraction e is 0.01 to 0.40; and the sum of the mole fractions b+c+d+e is 1.

17. The photoresist composition of claim 7 , wherein the copolymer is of the formula:

wherein R 1 is H or C 1-4 alkyl, R 12 is an acid decomposable acetal group comprising a fluorinated or non-fluorinated C 6-25 aryl group, R 19 is a fluorinated or non-fluorinated C 4-20 tertiary alkyl, a fluorinated or non-fluorinated C 4-20 tertiary cycloalkyl, or a fluorinated or non-fluorinated tertiary or benzylic C 6-20 aryl alkyl, each occurrence of R 9 is independently F, C 1-10 fluoroalkyl, or a C 1-10 fluoroalkoxy group; R 10 is a cation-bound C 10-40 photoacid generator-containing group of the formula

—(Ar″)—O—R 13

wherein Ar″ is a C 6-20 monocyclic, polycyclic, or fused polycyclic aryl group, and

wherein R 14 is H or C 1-4 alkyl, and R 17 is

wherein R 18 is H or a C 1-10 organic group, X is S or I, and h is 2 when X is S, or h is 1 when X is I, and k is 1 to 4, and Z − is

or R 10 is

wherein R 18 is H or a C 1-10 organic group, X is S or I, and h is 2 when X is S, or h is 1 when X is I, k is 1 to 4, and Z − is

mole fraction a is 0 to 0.80; mole fraction b is reater than 0 and less than or equal to 0.80; mole fraction c is 0.01 to 0.80; mole fraction d is greater than zero and less than or equal to 0.80; and mole fraction e is greater than 0 and less than or equal to 0.50; the sum of the mole fractions a+b+c+d+e is 1; 1 and m are independently integers of 1 to 4, and n is an integer of 1 to 5.

18. The photoresist composition of claim 7 , wherein R 10 is a cation-bound C 10-40 photoacid generator-containing group of the formula

—(Ar″)—O—R 13

wherein Ar″ is a C 6-20 monocyclic, polycyclic, or fused polycyclic aryl group, and

wherein R 14 is H or C 1-4 alkyl, and R 17 is

wherein R 18 is H or a C 1-10 organic group, X is S or I, and h is 2 when X is S, or h is 1 when X is I, and k is 1 to 4, and Z − is an anion.

19. The photoresist composition of claim 7 , wherein R 10 is

wherein R 18 is H or a C 1-10 organic group, X is S or I, and h is 2 when X is S, or h is 1 when X is I, k is 1 to 4, and Z − is an anion.

20. A coated substrate, comprising:

a photoresist layer comprising a photoresist composition comprising a copolymer having the formula:

wherein R 1 -R 5 are each independently H, C 1-6 alkyl, or C 4-6 aryl; R 6 is a fluorinated or non-fluorinated C 5-30 acid decomposable group; each Ar is independently a monocyclic, polycyclic, or fused polycyclic C 6-20 aryl group; each occurrence of R 7 is —OR 11 where R 11 is a fluorinated or non-fluorinated C 5-30 acid decomposable acetal group comprising a fluorinated or nonfluorinated C 6-25 aryl group; each occurrence of R 8 is independently —OR 11 or a —C(CF 3 ) 2 OR 11 group where each occurrence of R 11 is independently H or a fluorinated or non-fluorinated C 5-30 acid decomposable group; each occurrence of R 9 is independently F, C 1-10 fluoroalkyl, or a C 1-10 fluoroalkoxy group; R 10 is a cation-bound C 10-40 photoacid generator-containing group of the formula

R 10 =—(Ar″)—O—R 13

wherein Ar″ is a C 6-20 monocyclic, polycyclic, or fused polycyclic aryl group, and

wherein R 14 is H or C 1-4 alkyl, and R 17 is

wherein R 18 is H or a C 1-10 organic group, X is S or I, and h is 2 when X is S, or h is 1 when X is I, and k is 1 to 4, and Z − is an anion; or R 10 is

wherein R 18 is H or a C 1-10 organic group, X is S or I, and h is 2 when X is S, or h is 1 when X is I, k is 1 to 4, and Z − is an anion; mole fraction a is 0 to 0.80, mole fraction b is greater than 0 and less than or equal to 0.80, mole fraction c is 0.01 to 0.80, mole fraction d is greater than zero and less than or equal to 0.80, and mole fraction e is greater than 0 and less than or equal to 0.50, the sum of the mole fractions a+b+c+d+e is 1, l and m are independently integers of 1 to 4, and n is an integer of 1 to 5;

a photo-destroyable base; and

optionally, a non-polymer bound photoacid generator;

wherein the photoresist layer is in contact with a surface of a substrate.