Hardmask composition, method of forming pattern using the hardmask composition, and hardmask formed from the hardmask composition

1. A hardmask composition comprising:

a solvent; and at least one of

a derivative mixture including a derivative of a two-dimensional (2D) carbon nanostructure and a derivative of a zero-dimensional (0D) carbon nanostructure, or

a composite including a 2D carbon nanostructure and a 0D carbon nanostructure, wherein

the hardmask composition includes the composite, and

the composite is a structure in which the 2D carbon nanostructure is bound to the 0D carbon nanostructure by a linker, and

the 2D carbon nanostructure is at least one of graphene, graphene quantum dots, reduced graphene oxide, and a heteroatom derivative thereof,

the 2D carbon nanostructure is a GNP,

an intensity ratio of a D mode peak to a G mode peak obtained from Raman spectroscopy analysis of the GNP is greater than 0 and less than or equal to 2,

an intensity ratio of a 2D mode peak to a G mode peak is 0.01 or greater,

the 2D carbon nanostructure is mixed with the 0D carbon nanostructure at a ratio of about 3:1 to about 5:1, and

a size of the 2D carbon nanostructure is in a range of about 1 nm to 10 nm.

2. The hardmask composition of claim 1 , wherein

the linker is at least one of an ester group (—C(═O)O—), an ether group (—O—), a thioether group (—S—), a carbonyl group ((—C)═O)—), an amide group (—C(═O)NH—), and an imide group; or

the linker is an organic group derived from at least one of an ester group (—C(═O)O—), an ether group (—O—), a thioether group (—S—), a carbonyl group ((—C)═O)—), an amide group (—C(═O)NH—), and an imide group.

3. The hardmask composition of claim 1 , wherein

the composite is a product of a reaction between the 0D carbon nanostructure including a first reactive functional group and the 2D carbon nanostructure including a second reactive functional group, and

the first reactive functional group and the second reactive functional group independently each include at least one of a halogen atom, a hydroxyl group, an alkoxy group, a cyano group, an amino group, an azide group, a carboxamidine group, a hydrazino group, a hydrazono group, a carbamoyl group, a thiol group, an ester group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, and a phosphoric acid group or a salt thereof.

4. The hardmask composition of claim 1 , wherein

the 0D carbon nanostructure is at least one of a fullerene, a boron buckyball, a carborane, and a derivative thereof.

5. The hardmask composition of claim 1 , wherein a content of carbon in the 2D carbon nanostructure is in a range of about 75 percent by weight (wt %) to about 95 wt %.

6. The hardmask composition of claim 1 , wherein a number of layers of the GNP is greater than 0 and less than or equal to about 300.

7. The hardmask composition of claim 1 , wherein the 0D carbon nanostructure is a fullerene or a derivative thereof, and a number of carbon atoms in the 0D carbon nanostructure is one of 60, 70, 76, 78, 82, 82, and 84.

8. The hardmask composition of claim 7 , wherein, according to analysis of the fullerene by Raman spectroscopy, a maximum absorption peak is observed at a Raman shift of about 1,455 centimeters −1 (cm −1 ) to about 1,500 cm −1 .

9. The hardmask composition of claim 1 , wherein the 2D carbon nanostructure is a 2D sheet having a size to thickness ratio in a range of about 3 to about 30.

10. The hardmask composition of claim 1 , wherein an sp 2 carbon fraction of the GNP is equal to an sp 3 carbon fraction thereof or equal to a multiple of an sp 3 carbon fraction thereof.

11. The hardmask composition of claim 1 , wherein the hardmask composition includes at least one of a compound represented by Formula 2, a compound represented by Formula 3, and a product of a reaction between graphene to which a hydroxyl group is bound and a fullerene to which a carboxyl group is bound:

wherein, in Formula 2, R indicates a group represented by Formula 2a:

wherein, in Formula 3, n is an integer from 1 to 10.

12. The hardmask composition of claim 1 , wherein the solvent is at least one of water, methanol, isopropanol, ethanol, N,N-dimethylformamide, N-methylpyrrolidone, dichloroethane, dichlorobenzene, dimethylsulfoxide, xylene, aniline, propylene glycol, propylene glycol diacetate, 3-methoxyl,2-propanediol, diethylene glycol, gamma-butyrolactone, acetylacetone, cyclohexanone, propylene glycol monomethyl ether acetate, o-dichlorobenzene, nitromethane, tetrahydrofuran, nitromethane, dimethyl sulfoxide, nitrobenzene, butyl nitrite, methyl cellosolve, ethyl cellosolve, diethylether, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, hexane, methylethylketone, methyl isobutylketone, hydroxymethylcellulose, and heptane.

13. The hardmask composition of claim 1 further comprising:

one of a first material, a second material, and a mixture of the first material and the second material, wherein

the first material includes one of a monomer containing an aromatic ring and a polymer including a repeating unit containing the monomer, and

the second material includes one of hexagonal boron nitride, a chalcogenide-based material, and a precursor thereof.

14. A method of forming a pattern, the method comprising:

forming an etching layer on a substrate;

forming a hardmask on the etching layer, the forming the hardmask including providing the hardmask composition of claim 1 on the etching layer, wherein the hardmask includes the composite of the 2D carbon nanostructure and the 0D carbon nanostructure;

forming a photoresist layer on the hardmask;

forming a hardmask pattern, the forming the hardmask pattern including etching the composite using the photoresist layer as an etching mask; and

etching the etching layer using the hardmask pattern as an etching mask.

15. The method of claim 14 , further comprising:

performing a heat treatment on the hardmask composition during or after the providing of the hardmask composition on the etching layer.

16. The method of claim 14 , wherein a thickness of the hardmask is in a range of about 10 nm to about 10,000 nm.

17. The method of claim 14 , wherein the forming the hardmask includes using at least one of spin coating, air spraying, electrospraying, dip coating, spray coating, doctor blade coating, and bar coating during the providing the hardmask composition.

18. The method of claim 14 , wherein the forming the hardmask includes mixing the derivative of the 2D carbon nanostructure, the derivative of the 0D carbon nanostructure, and the solvent.

19. The method of claim 18 , wherein

the derivative of the 2D carbon nanostructure is at least one of a COOH-functionalized GNP and a GNP precursor, and

the derivative of the 0D carbon nanostructure is an OH-functionalized fullerene.

20. The method of claim 14 , wherein the forming the hardmask includes

mixing the solvent and the composite including the 2D carbon nanostructure and the 0D carbon nanostructure, or

mixing the solvent, the derivative of the 2D carbon nanostructure, and the derivative of the 0D carbon nanostructure.

21. The method of claim 14 , wherein

the forming the hardmask pattern includes forming a laminate structure, and

the laminate structure includes the 2D carbon nanostructure and the 0D carbon nanostructure.

22. A hardmask comprising:

a composite including a 2D carbon nanostructure and a 0D carbon nanostructure, wherein

the composite is a structure in which the 2D carbon nanostructure is bound to the 0D carbon nanostructure by a linker,

the 2D carbon nanostructure is at least one of graphene, graphene quantum dots, reduced graphene oxide, and a heteroatom derivative thereof,

the 2D carbon nanostructure is a GNP,

an intensity ratio of a D mode peak to a G mode peak obtained from Raman spectroscopy analysis of the GNP is greater than 0 and less than or equal to 2,

an intensity ratio of a 2D mode peak to a G mode peak is 0.01 or greater,

the 2D carbon nanostructure is mixed with the 0D carbon nanostructure at a ratio of about 3:1 to about 5:1,

a size of the 2D carbon nanostructure is in a range of about 1 nm to 10 nm.

23. A hardmask composition comprising:

at least one of a two-dimensional (2D) carbon nanostructure and a derivative of the 2D carbon nanostructure; and

at least one of a zero-dimensional (0D) carbon nanostructure and a derivative of the 0D carbon nanostructure, wherein

the 2D carbon nanostructure is a GNP,

an intensity ratio of a D mode peak to a G mode peak obtained from Raman spectroscopy analysis of the GNP is greater than 0 and less than or equal to 2,

an intensity ratio of a 2D mode peak to a G mode peak is 0.01 or greater, and

the at least one of a two-dimensional (2D) carbon nanostructure and a derivative of the 2D carbon nanostructure is mixed with the at least one of a zero-dimensional (0D) carbon nanostructure and a derivative of the 0D carbon nanostructure at a ratio of about 3:1 to about 5:1, and

a size of the 2D carbon nanostructure is in a range of about 1 nm to 10 nm.

24. The hardmask composition of claim 23 , wherein

the hardmask composition include the 0D carbon nanostructure, and the 0D carbon nanostructure is at least one of a fullerene, a boron buckyball, a carborane, and a derivative thereof.

25. The hardmask composition of claim 23 , wherein

the hardmask composition include the 2D carbon nanostructure.

26. The hardmask composition of claim 23 , wherein

the at least one of the 2D carbon nanostructure and the derivative of the 2D carbon nanostructure is the 2D carbon nanostructure,

the at least one of the 0D carbon nanostructure and the derivative of the 0D carbon nanostructure is the 0D carbon nanostructure, and

the 2D carbon nanostructure and the 0D carbon nanostructure are connected to each other by a linker functional group.