Photoacid generator, copolymer, chemically amplified resist composition, and method of forming pattern using the chemically amplified resist composition

1. A photoacid generator represented as

wherein R 1 is a C 1 -C 5 alkoxy group,

R 2 and R 3 are respectively a linear or branched C 1 -C 20 alkyl group, an aryl group, a linear or branched C 1 -C 20 perfluoroalkyl group, a benzyl group, or a C 6 -C 20 aryl group, and A − is a compound represented as

wherein X 1 is a monocyclic or polycyclic C 3 -C 20 hydrocarbon group, a benzyl group, a C 6 -C 20 aryl group, a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 1 -C 10 hydroxy alkyl group, or a cyano group, at least one hydrogen atom of the monocyclic or polycyclic C 3 -C 20 hydrocarbon group is or is not substituted with an ether group, an ester group, a carbonyl group, an acetal group, a nitrile group, a cyano group, a hydroxy group, a carboxyl group, or an aldehyde group, R is a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a nitrogen atom, a sulfur atom, or an oxygen atom, and m is a positive integer of 0 to 2.

2. The photoacid generator of claim 1 , wherein the photoacid generator is obtained through a synthesis reaction of a compound represented as Chemical formula 3 below and a salt represented as Chemical formula 4 below:

wherein R 1 is a C 1 -C 5 alkoxy group; and

wherein R 2 and R 3 are respectively a linear or branched C 1 -C 20 alkyl group, an aryl group, a linear or branched C 1 -C 20 perfluoroalkyl group, a benzyl group, or a C 6 -C 20 aryl group, and A − is a compound represented as Chemical formula 2.

3. A copolymer for a chemically amplified resist composition in which a photoacid generator represented as Chemical formula 1 below is connected with a main chain of the copolymer:

wherein R 1 is a C 1 -C 5 alkoxy group,

R 2 and R 3 are respectively a linear or branched C 1 -C 20 alkyl group, an aryl group, a linear or branched C 1 -C 20 perfluoroalkyl group, a benzyl group, or a C 6 -C 20 aryl group,

and A − is a compound represented as

wherein X 1 is a monocyclic or polycyclic C 3 -C 20 hydrocarbon group, a benzyl group, a C 6 -C 20 aryl group, a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 1 -C 10 hydroxy alkyl group, or a cyano group, at least one hydrogen atom of the monocyclic or polycyclic C 3 -C 20 hydrocarbon group is or is not substituted with an ether group, an ester group, a carbonyl group, an acetal group, a nitrile group, a cyano group, a hydroxy group, a carboxyl group, or an aldehyde group, R is a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a nitrogen atom, a sulfur atom, or an oxygen atom, and m is a positive integer of 0 to 2.

4. The copolymer of claim 3 , wherein the copolymer includes a repeating unit having the photoacid generator.

5. The copolymer of claim 3 , wherein the copolymer further includes at least one of a repeating unit having an acid labile group, a repeating unit having a lactone ring, and a repeating unit having a hydroxy group.

6. The copolymer of claim 3 , wherein the copolymer for a chemically amplified resist composition is represented as the copolymer:

wherein R 1 is a C 1 -C 5 alkoxy group,

R 2 and R 3 are respectively a linear or branched C 1 -C 20 alkyl group, an aryl group, a linear or branched C 1 -C 20 perfluoroalkyl group, a benzyl group, or a C 6 -C 20 aryl group,

R 4 , R 5 and R 6 are respectively a hydrogen atom, or a C 1 -C 30 alkyl group including or not including an ether group, an ester group, a carbonyl group, an acetal group, an epoxy group, a nitrile group, or an aldehyde group,

R 7 , R 8 and R 9 are respectively a hydrogen atom, a methyl group, or a trifluoromethyl group,

X 2 is olefin, vinyl, styrene, or a derivative thereof,

a, b, c, d, and e respectively satisfy 0.01<a/(a+b+c+d+e)<0.4; 0.01<b/(a+b+c+d+e)<0.3; 0.01<c/(a+b+c+d+e)<0.3; 0.01<d/(a+b+c+d+e)<0.3; 0.01<e/(a+b+c+d+e)<0.15,

and A − is a compound represented as

wherein X 1 is a monocyclic or polycyclic C 3 -C 20 hydrocarbon group, a benzyl group, a C 6 -C 20 aryl group, a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 1 -C 10 hydroxy alkyl group, or a cyano group, at least one hydrogen atom of the monocyclic or polycyclic C 3 -C 20 hydrocarbon group is or is not substituted with an ether group, an ester group, a carbonyl group, an acetal group, a nitrile group, a cyano group, a hydroxy group, a carboxyl group, or an aldehyde group, R is a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a nitrogen atom, a sulfur atom, or an oxygen atom, and m is a positive integer of 0 to 2.

7. A chemically amplified resist composition including a copolymer and a solvent, in which a photoacid generator represented as Chemical formula 1 below is connected with a main chain of the copolymer:

wherein R 1 is a C 1 -C 5 alkoxy group, R 2 and R 3 are respectively a linear or branched C 1 -C 20 alkyl group, an aryl group, a linear or branched C 1 -C 20 perfluoroalkyl group, a benzyl group, or a C 6 -C 20 aryl group, and A − is a compound represented as

wherein X 1 is a monocyclic or polycyclic C 3 -C 20 hydrocarbon group, a benzyl group, a C 6 -C 20 aryl group, a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 1 -C 10 hydroxy alkyl group, or a cyano group, at least one hydrogen atom of the monocyclic or polycyclic C 3 -C 20 hydrocarbon group is or is not substituted with an ether group, an ester group, a carbonyl group, an acetal group, a nitrile group, a cyano group, a hydroxy group, a carboxyl group, or an aldehyde group, R is a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a nitrogen atom, a sulfur atom, or an oxygen atom, and m is a positive integer of 0 to 2.

8. The chemically amplified resist composition of claim 7 , wherein the copolymer is synthesized by polymerization of monomers including the photoacid generator, and about 0.5 to 15 parts by weight of the photoacid generator with respect to about 100 parts by weight of a total solid of the chemically amplified resist composition is used upon the polymerization.

9. The chemically amplified resist composition of claim 7 , wherein an amount of the copolymer is about 3 wt. % to 20 wt. % with respect to a total amount of the chemically amplified resist composition.

10. A method of forming a pattern using a chemically amplified resist composition including a copolymer and a solvent, the method comprising:

coating a substrate with the chemically amplified resist composition including the copolymer and the solvent, a main chain of the copolymer being connected with a photoacid generator represented as Chemical formula 1 below, and drying the coated composition to form a resist layer;

selectively exposing the resist layer; and

developing the exposed resist layer:

wherein R 1 is a C 1 -C 5 alkoxy group, R 2 and R 3 are respectively a linear or branched C 1 -C 20 alkyl group, an aryl group, a linear or branched C 1 -C 20 perfluoroalkyl group, a benzyl group, or a C 6 -C 20 aryl group, and A − is a compound represented as

wherein X 1 is a monocyclic or polycyclic C 3 -C 20 hydrocarbon group, a benzyl group, a C 6 -C 20 aryl group, a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 1 -C 10 hydroxy alkyl group, or a cyano group, at least one hydrogen atom of the monocyclic or polycyclic C 3 -C 20 hydrocarbon group is or is not substituted with an ether group, an ester group, a carbonyl group, an acetal group, a nitrile group, a cyano group, a hydroxy group, a carboxyl group, or an aldehyde group, R is a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a nitrogen atom, a sulfur atom, or an oxygen atom, and m is a positive integer of 0 to 2.

11. The method of claim 10 , wherein a light source for the exposing is any light source selected from a KrF excimer laser, an ArF excimer laser, an Extreme Ultra Violet (EUV) light, an X-ray, and an electron-beam (e-beam).

12. The method of claim 10 , wherein a light wavelength of the light source for the exposing is about 180 nm to 250 nm.

13. The copolymer of claim 12 , wherein the copolymer has a weight average molecular weight (Mw) of about 500 to 100,000.

14. The copolymer of claim 3 , wherein the copolymer for a chemically amplified resist is represented as any copolymer of Chemical formulas below, which are

wherein a, b, c, d, and e respectively satisfy 0.01.<a/(a+b+c+d+e)<0.4; 0.01<b/(a+b+c+d+e)<0.3; 0.01<c/(a+b+c+d+e)<0.3; 0.01<d/(a+b+c+d+e)<0.3; 0.01<e/(a+b+c+d+e)<0.15.