KR102558007B1 - Hardmask composition, method of forming patterning using the hardmask composition, and hardmask formed from the hardmask composition - Google Patents

Abstract

A hard mask composition including a complex represented by Chemical Formula 1 and a solvent, a method for forming a pattern using the same, and a hard mask formed therefrom are presented.
[Formula 1]

In Formula 1, R ₁ to R ₈ , X and M are as described in the detailed description.

Description

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

A hard mask composition, a method for forming a pattern using the same, and a hard mask formed therefrom are presented.

Recently, the semiconductor industry is developing into an ultra-fine technology having a pattern of several to several tens of nanometers in size. An effective lithography method is required to realize such ultra-fine technology. Lithography generally includes a process of forming a material layer on a semiconductor substrate, coating a photoresist layer thereon, exposing and developing the photoresist pattern to form a photoresist pattern, and then etching the material layer using the photoresist pattern as a mask.

As the size of a pattern to be formed is reduced, it is difficult to form a fine pattern having a good profile only by a general lithography method. Accordingly, a layer called a “hard mask” may be formed between the material layer to be etched and the photoresist layer to form a fine pattern. The hard mask acts as an intermediate film that transfers the fine pattern of the photoresist to the material layer through a selective etching process. Therefore, the hard mask layer is required to have chemical resistance, heat resistance, and etch resistance to withstand various etching processes.

As semiconductor devices are highly integrated, the line width of the material layer gradually narrows, while the height of the material layer is maintained or relatively increased, resulting in an increase in the aspect ratio of the material layer. Since the etching process must be performed under these conditions, the heights of the photoresist layer and the hard mask pattern must be increased. However, there is a limit to increasing the height of the photoresist layer and the hard mask pattern. Also, in an etching process to obtain a material layer having a narrow line width, the hard mask pattern may be damaged, and thus electrical characteristics of the device may be deteriorated.

In view of the above problems, a method of using a single layer of a conductive or insulating material such as a polysilicon layer, a tungsten layer, or a nitride layer or a multilayer layer in which a plurality of layers are stacked has been proposed as a hard mask. However, since the single-layer or multi-layer film has a high deposition temperature, it may cause a change in physical properties of the material layer, and thus, development of a new hard mask material is required.

One aspect is to provide a hard mask composition having improved solubility in a solvent and excellent etch resistance.

Another aspect is to provide a method of forming a pattern using the hard mask composition.

Another aspect is to provide a hardmask formed using the hardmask composition described above.

According to one aspect,

A hard mask composition including a complex represented by Chemical Formula 1 and a solvent is provided.

[Formula 1]

In Formula 1, X is C(R ₁₁ ) or N,

R_One to R₈ and R₁₁are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C6-C20 aryloxy group, a substituted or unsubstituted C2-C20 heteroaryl group, a substituted or unsubstituted C2- C20 heteroaryloxy group, substituted or unsubstituted C4-C20 carbocyclic group, substituted or unsubstituted C4-C20 carbocyclic oxy group, substituted or unsubstituted C2-C20 heterocyclic group, halogen atom, cyano group, hydroxyl group, imide group, carbonyl group, epoxy group, epoxy group-containing functional group, -C(=O)R, -C(=O)NH₂,-C(=O)OR,-(CH₂)_nCOOH (n = an integer from 1 to 10) and -N (R₉)(R₁₀) is selected from, or R_One and R₂, R₃ and R₄, R₅ and R₆, R₇and R₈can be linked independently of each other to form a ring,

R is hydrogen, C1-C20 alkyl group, C2-C20 alkenyl group, C2-C20 alkynyl group, C6-C20 aryl group, C2-C20 heteroaryl group, or C2-C20 heteroaryloxy group,

R ₉ and R ₁₀ are each independently hydrogen, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C6-C20 aryl group, a C2-C20 heteroaryl group, or a C2-C20 heteroaryloxy group;

M is selected from elements of groups 2 to 11 and 14 and oxides of those elements.

A first step of forming a film to be etched on a substrate according to another aspect;

a second step of supplying the above-described hard mask composition to an upper portion of the film to be etched to form a hard mask including a reaction product of coating and heat treatment of the hard mask composition;

a third step of forming a photoresist layer on the hard mask;

a fourth step of forming a hard mask pattern including a reaction product of the coating and heat treatment of the hard mask composition using the photoresist layer as an etching mask; and

There is provided a pattern formation method comprising a fifth step of etching the film to be etched using the hard mask pattern as an etching mask.

In another aspect, a hard mask including a product obtained by coating and heat-treating the hard mask composition described above is provided.

The hard mask composition according to one aspect has excellent stability, excellent etching resistance and mechanical strength compared to hard masks using conventional polymers, and can be easily removed after an etching process. If such a hard mask is used, a more elaborate pattern with excellent uniformity can be formed.

1 schematically shows a graphene quantum dot according to an embodiment.
2A to 2E are for explaining a method of forming a pattern using a hard mask composition according to an embodiment.
3A to 3D are for explaining a method of forming a pattern using a hard mask composition according to another embodiment.
4 is a photograph showing a result of electron electron microscope (SEM) analysis of a silicon substrate on which a hard mask manufactured according to Manufacturing Example 1 is stacked.

Hereinafter, a hard mask composition according to an embodiment, a method for forming a pattern using the same, and a hard mask formed using the hard mask composition will be described in detail.

A hardmask composition including a composite represented by Chemical Formula 1 is provided.

[Formula 1]

In Formula 1, X is C(R ₁₁ ) or N,

R_One to R₈ and R₁₁are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C6-C20 aryloxy group, a substituted or unsubstituted C2-C20 heteroaryl group, a substituted or unsubstituted C2- C20 heteroaryloxy group, substituted or unsubstituted C4-C20 carbocyclic group, substituted or unsubstituted C4-C20 carbocyclic oxy group, substituted or unsubstituted C2-C20 heterocyclic group, halogen atom, cyano group, hydroxyl group, imide group, carbonyl group, epoxy group, epoxy group-containing functional group, -C(=O)R, -C(=O)NH₂,-C(=O)OR,-(CH₂)_nCOOH (n = an integer from 1 to 10) and -N (R₉)(R₁₀) is selected from, or R_One and R₂, R₃ and R₄, R₅ and R₆, R₇and R₈can be linked independently of each other to form a ring,

R is hydrogen, C1-C20 alkyl group, C2-C20 alkenyl group, C2-C20 alkynyl group, C6-C20 aryl group, C2-C20 heteroaryl group, or C2-C20 heteroaryloxy group,

R ₉ and R ₁₀ are each independently hydrogen, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C6-C20 aryl group, a C2-C20 heteroaryl group, or a C2-C20 heteroaryloxy group;

M is selected from elements of groups 2 to 11 and 14 or oxides thereof.

As described above, various substituents may be used for R ₁ to R ₈ in Formula 1. R ₁ to R ₈ and/or R ₁₁ are, for example, a substituted aryl group, for example, a tertbutylphenyl group, the complex of Formula 1 has improved solubility characteristics in an organic solvent such as N-methyl-2-pyrrolidone (NMP), and thus a hard mask can be easily manufactured.

In Formula 1, R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , R ₇ and R ₈ may be independently connected to each other to form a substituted or unsubstituted C6 to C20 aromatic ring. The C6 to C20 aromatic ring includes, for example, a phenyl group.

The complex represented by Formula 1 may be a complex represented by Formula 2 below or a complex represented by Formula 3 below.

[Formula 2]

In Formula 2, M is at least one selected from Fe, Ni, Co, Mn, Mg, Rh, Os, Ru, Mo, Cr, Zn, Ti, Zr, Si, Cu,

R_One to R₈are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C6-C20 aryloxy group, a substituted or unsubstituted C2-C20 heteroaryl group, a substituted or unsubstituted C2- C20 heteroaryloxy group, substituted or unsubstituted C4-C20 carbocyclic group, substituted or unsubstituted C4-C20 carbocyclic oxy group, substituted or unsubstituted C2-C20 heterocyclic group, halogen atom, cyano group, hydroxyl group, imide group, carbonyl group, epoxy group, epoxy group-containing functional group, -C(=O)R, -C(=O)NH₂,-C(=O)OR,-(CH₂)_nCOOH (n = an integer from 1 to 10) and -N (R₉)(R₁₀) is selected from, or R_One and R₂, R₃ and R₄, R₅ and R₆, R₇and R₈Are linked independently of each other to form a substituted or unsubstituted C6 to C20 aromatic ring,

R is hydrogen, C1-C20 alkyl group, C2-C20 alkenyl group, C2-C20 alkynyl group, C6-C20 aryl group, C2-C20 heteroaryl group, or C2-C20 heteroaryloxy group,

R ₉ and R ₁₀ are each independently hydrogen, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C6-C20 aryl group, a C2-C20 heteroaryl group, or a C2-C20 heteroaryloxy group;

[Formula 3]

In Formula 3, M is at least one selected from Fe, Ni, Co, Mn, Mg, Rh, Os, Ru, Mo, Cr, Zn, Ti(=O), Zr(=O), Si and Cu,

R_One to R₈are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C6-C20 aryloxy group, a substituted or unsubstituted C2-C20 heteroaryl group, a substituted or unsubstituted C2- C20 heteroaryloxy group, substituted or unsubstituted C4-C20 carbocyclic group, substituted or unsubstituted C4-C20 carbocyclic oxy group, substituted or unsubstituted C2-C20 heterocyclic group, halogen atom, cyano group, hydroxyl group, imide group, carbonyl group, epoxy group, epoxy group-containing functional group, -C(=O)R, -C(=O)NH₂,-C(=O)OR,-(CH₂)_nCOOH (n = an integer from 1 to 10) and -N (R₉)(R₁₀) is selected from,

R ₁₁ is selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C6-C20 aryloxy group, a hydroxyl group, a carboxyl group, -C(=O)R, -C(=O)OR, and -N(R ₉ )(R ₁₀ );

R is hydrogen, C1-C20 alkyl group, C2-C20 alkenyl group, C2-C20 alkynyl group, C6-C20 aryl group, C2-C20 heteroaryl group, or C2-C20 heteroaryloxy group,

R ₉ and R ₁₀ are each independently hydrogen, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C6-C20 aryl group, a C2-C20 heteroaryl group, or a C2-C20 heteroaryloxy group.

In Formula 2, R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , R ₇ and R ₈ may be independently connected to each other to form a substituted C6 to C20 aromatic ring. The substituent of the substituted C6 to C20 aromatic ring is, for example, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, a C2-C20 heteroaryl group, a C2-C20 heteroaryloxy group, a hydroxyl group, a carboxyl group, -C(=O)R, -C(=O)OR, and -N(R ₉ )(R ₁₀ ), A halogen atom, a cyano group, etc. are mentioned. R, R ₉ and R ₁₀ are as defined in formula (2).

Since the composite of Chemical Formula 2 or 3 has excellent chemical resistance and thermal stability, a hard mask with improved etch resistance can be manufactured by using the composite.

The complex represented by Chemical Formula 1 may be, for example, a complex represented by Chemical Formula 4 or 4a, a complex represented by Chemical Formula 5a, or a complex represented by Chemical Formula 5b.

[Formula 4]

In Formula 4, M is at least one selected from Fe, Ni, Co, Mn, Mg, Rh, Os, Ru, Mo, Cr, Zn, Ti(=O), Zr(=O), Si and Cu,

[Formula 4a]

In Formula 4a, M is at least one selected from among Fe, Ni, Co, Mn, Mg, Rh, Os, Ru, Mo, Cr, Zn, Ti(=O), Zr(=O), Si and Cu,

R is a monosubstituted or polysubstituted substituent, and is a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, a C2-C20 heteroaryl group, a C2-C20 heteroaryloxy group, a hydroxyl group, -C(=O)OH, -C(=O)OR ₁ (R ₁ is a C-10 alkyl group, a C2-C10 alkenyl group, or C 6-C20 aryl group), -NH ₂ , -N(R ₂ )(R ₃ ) (R ₂ and R ₃ is independently of each other a C1-C10 alkyl group or a C6-C20 aryl group), -(CH ₂ ) _n COOH (n = an integer of 1 to 10), -CONH ₂ , a cyano group, selected from an epoxy group-containing functional group,

[Formula 5a]

In Formula 5a, M is at least one selected from Fe, Ni, Co, Mn, Mg, Rh, Os, Ru, Mo, Cr, Zn, Ti(=O), Zr(=O), Si and Cu,

R ₁₁ is a substituted C6-C20 aryl group;

[Formula 5b]

In Formula 5b, M is at least one selected from among Fe, Ni, Co, Mn, Mg, Rh, Os, Ru, Mo, Cr, Zn, Ti(=O), Zr(=O), Si, and Cu.

By introducing R into the phenyl group of the compound of Formula 4a, its solubility in solvents can be improved compared to the compound of Formula 4.

The complex represented by Formula 1 is, for example, at least one selected from complexes represented by Formulas 6a, 7a, or 8a.

[Formula 6a] [Formula 7a]

[Formula 8a]

In Formulas 6a, 7a, and 8, R is a monosubstituted or polysubstituted substituent, for example, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, a C2-C20 heteroaryl group, a C2-C20 heteroaryloxy group, a hydroxyl group, -C(=O)OH, -C(=O)OR ₁ (R ₁ is C-10 Alkyl group, C2-C10 alkenyl group or C6-C20 aryl group), -NH ₂ , -N(R ₂ )(R ₃ ) (R ₂ and R ₃ is independently selected from a C1-C10 alkyl group or a C6-C20 aryl group), -(CH ₂ ) _n COOH (n = an integer from 1 to 10), -CONH ₂ , a cyano group, and an epoxy group-containing functional group.

In Formulas 6a, 7a, and 8, the bonding position of R is not particularly fixed, and as described above, it may be a monosubstituted substituent or a substituent with 2 to 4 substituents.

The complex represented by Formula 1 may be, for example, at least one selected from complexes represented by Formulas 6 to 12 below.

[Formula 6] [Formula 7]

[Formula 8] [Formula 9]

[Formula 10] [Formula 11]

[Formula 12]

Since the complex of Chemical Formula 12 has a ditertbutylphenyl group as R ₁₁ , its solubility in organic solvents such as N-methylpyrrolidone can be further improved compared to the complex in which R ₁₁ is hydrogen.

Complexes represented by Chemical Formulas 3 to 12 are synthesized according to preparation methods known in the art or are commercially available.

In the hardmask composition according to one embodiment, the content of the composite represented by Formula 1 is 5 to 50 parts by weight, for example, 10 to 50 parts by weight, for example, 15 to 40 parts by weight, based on 100 parts by weight of the hardmask composition. When the content of the composite is within the above range, the stability of the hardmask composition containing the composite is excellent, and the etching resistance of a hardmask formed from the hardmask composition may be improved.

The hard mask composition according to an embodiment may further include at least one selected from a two-dimensional carbon nanostructure, a zero-dimensional carbon nanostructure, a precursor of a two-dimensional carbon nanostructure, a precursor of a zero-dimensional carbon nanostructure, a derivative of a two-dimensional carbon nanostructure, and a derivative of a zero-dimensional carbon nanostructure. When the hard mask composition further contains at least one selected from two-dimensional carbon nanostructures, zero-dimensional carbon nanostructures, precursors thereof, and derivatives thereof, solubility in solvents is improved and the hard mask can be thinned to a uniform thickness.

At least one selected from the group consisting of a two-dimensional carbon nanostructure, a zero-dimensional carbon nanostructure, a precursor of a two-dimensional carbon nanostructure, a precursor of a zero-dimensional carbon nanostructure, a derivative of a two-dimensional carbon nanostructure, and a derivative of a zero-dimensional carbon nanostructure is a halogen atom, a hydroxyl group, an alkoxy group, a cyano group, an amino group, an azide group, a carboxamidine group, a hydrazino group, and a hydrazono group. It may have at least one functional group selected from the group consisting of a carbamoyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof.

Non-limiting examples of the zero-dimensional carbon nanostructures having the aforementioned functional groups include compounds represented by the following Chemical Formula 26.

[Formula 27]

The complex represented by Formula 1 has different solubility in solvents depending on the type of substituent. In addition, when the composite of Chemical Formula 1 is mixed with at least one selected from the above-described two-dimensional carbon nanostructures, zero-dimensional carbon nanostructures, precursors thereof, and derivatives thereof, the solubility in the solvent can be increased to 20% by weight or less, for example, 1 to 20% by weight, for example 8 to 20% by weight, for example, 10 to 18% by weight by appropriately controlling the mixing ratio. The aforementioned two-dimensional carbon nanostructures and zero-dimensional carbon nanostructures can be divided into connected carbon atoms, the definition of which is described in detail as follows.

The term "two-dimensional carbon nanostructure" refers to a carbon nanostructure in which a plurality of carbon atoms are covalently linked to each other to form polycyclic aromatic molecules arranged on one plane to form a sheet structure of a single atomic layer, or a plurality of plate-shaped carbon nanostructures, which are small film pieces, are interconnected to form a network structure arranged on one plane, and combinations thereof are also possible. The carbon atoms linked by covalent bonds form a 6-membered ring as a basic repeating unit, but it is also possible to further include a 5-membered ring and/or a 7-membered ring. The carbon nanostructure may consist of a plurality of layers in which several sheet structures and/or network structures are stacked on each other, and have an average thickness of about 100 nm or less, for example, about 10 nm or less, specifically 0.01 to 10 nm.

The two-dimensional carbon nanostructure may be graphene nanoparticles (GNPs) having a size of 1 to 50 nm, for example 1 to 30 nm, for example 1 to 10 nm, for example 5 to 8 nm, and 300 layers or less.

The two-dimensional carbon nanostructure has a two-dimensional sheet shape, and has a size/thickness ratio of 3 to 30, for example, 5 to 25. Here, when the two-dimensional carbon nanostructure has a plate-like structure, “size” indicates a diameter on a two-dimensional plane, and when the two-dimensional carbon nanostructure has an elliptical or non-spherical structure, “size” may indicate a major axis diameter.

The two-dimensional carbon nanostructure may include, for example, at least one selected from the group consisting of graphene, graphene nanoparticles, graphene quantum dots (GQDs), reduced graphene oxide, derivatives thereof, and heteroatom derivatives thereof.

The term "precursor of two-dimensional carbon nanostructure" refers to a starting material for producing a two-dimensional carbon nanostructure.

The term “zero-dimensional carbon nanostructure” refers to, for example, fullerene series (C20, C26, C28, C36, C50, C60, C70, ….C2n, n=12, 13, 14,…, 100), boron buckyball series (B80, B90, B92), carborane series (C ₂ B ₁₀ H ₁₂ ) and derivatives using them. The zero-dimensional carbon structure has a particle size of 0.6 to 2 nm.

The zero-dimensional carbon or structure may be, for example, fullerene having a thickness of 1 nm or less, specifically 0.7 to 1 nm, and a density of 1.5 to 1.8 g/cm ³ , for example, about 1.7 g/cm ³ . All fullerenes contain sp ² carbons.

The carbon number of the zero-dimensional carbon nanostructure is 26 or more, eg 60 or more, eg 60, 70, 76, 78, 82 or 84.

The term “heteroatom derivative” refers to a derivative containing a heteroatom such as boron (B) or nitrogen (N), and the term “precursor of zero-dimensional carbon nanostructure” refers to a starting material for preparing a zero-dimensional carbon nanostructure.

In the present specification, the term "derivative of a two-dimensional carbon nanostructure" refers to a two-dimensional carbon nanostructure having a reactive functional group. The term "derivative of zero-dimensional carbon nanostructure" refers to a zero-dimensional carbon nanostructure having a reactive functional group. For example, when the zero-dimensional carbon nanostructure is a fullerene, the derivative of the zero-dimensional carbon nanostructure represents a fullerene having a reactive functional group such as hydroxyl functionalized fullerene. And, when the two-dimensional carbon nanostructure is GQD, the derivative of the two-dimensional carbon nanostructure refers to GQD having a reactive functional group such as carboxyl group-functionalized GQD (COOH-functionalized GQD).

In the hard mask composition according to an embodiment, the mixing weight ratio of the composite represented by Chemical Formula 1 and at least one selected from two-dimensional carbon nanostructures, zero-dimensional carbon nanostructures, precursors thereof, and derivatives thereof is 1:99 to 99:1, for example, 1:9 to 9:1.

According to another embodiment, the mixing weight ratio of the composite represented by Chemical Formula 1 and at least one selected from a two-dimensional carbon nanostructure and a zero-dimensional carbon nanostructure is 1:1 to 1:20, for example 1:1 to 1:10, for example 1:2 to 1:8, for example 1:3 to 1:5.

The two-dimensional carbon nanostructure is, for example, a graphene quantum dot having a size of 1 to 30 nm, for example, 1 to 10 nm, and the graphene quantum dot may have at least one functional group G selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group, an epoxy group, an amine group, and an imide group at an end thereof, as shown in FIG. In this way, when the above-described functional groups are bonded to the terminals of the graphene quantum dots, the etching resistance of the hardmask formed from the hardmask composition is excellent compared to the case where the above-described functional groups are present in the center of the graphene quantum dots in addition to the ends.

The two-dimensional carbon nanostructure is, for example, OH-functionalized graphene quantum dots (COOH-functionalized GQDs), COOH-functionalized graphene quantum dots (COOH-functionalized GQDs) or graphene quantum dot precursors.

Any solvent capable of dissolving or dispersing the composite of Chemical Formula 1, a two-dimensional carbon nanostructure, a zero-dimensional nanostructure, a precursor thereof, or a derivative thereof may be used as the solvent of the hard mask composition. Solvents include, for example, water, methanol, isopropanol, ethanol, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dichloroethane, dichlorobenzene, dimethylsulfoxide, aniline, propylene glycol, propylene glycol diacetate, methoxy propanediol, diethylene glycol, acetylacetone, cyclohexanone, γ-butyrolactone, nitromethane, tetrahydrofuran, nitrobenzene Zen, butyl nitrite, methyl cellosolve, ethyl cellosolve, diethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xyrene, hexane, methyl ethyl ketone, methyl isoketone, hydroxymethyl cellulose, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl It is at least one selected from ter (propyleneglycol monomethyl ether: PGME), cyclohexanone, ethyl lactate, and heptane.

The content of the solvent is not particularly limited, and is, for example, 100 to 100,000 parts by weight based on 100 parts by weight of the total weight of the complex of Formula 1. When the content of the solvent is within the above range, the hard mask composition has an appropriate viscosity and excellent film formability.

One of the two-dimensional carbon nanostructures, “Graphene Quantum Dots (GQD)” refers to a material made in the form of a dot or sheet having a size of 10 nm or less to make graphene, a conductor material, into a semiconductor form. The graphene quantum dots refer to graphene oxide quantum dots and/or reduced graphene oxide quantum dots having a size of eg 1 to 50 nm, eg 1 to 30 nm, eg 1 to 10 nm. When the size of the graphene quantum dots is within the above range, the etching rate of the hard mask can be appropriately controlled, and the dispersibility of the graphene quantum dots in the hard mask composition is excellent.

When the graphene quantum dots are spherical (or dot-shaped), "size" represents the average particle diameter of the graphene quantum dots. When the graphene quantum dots have a plate-like structure, "size" indicates a diameter on a two-dimensional plane, and when the graphene quantum dots have an elliptical or sheet shape, "size" may indicate a major axis diameter or a major axis length.

The graphene quantum dots have a size of eg 1 to 10 nm, eg 5 to 8 nm, eg 6 to 8 nm, and have 300 layers or less, eg 100 layers or less, specifically 1 to 20 layers. And the thickness of the graphene quantum dots is 100 nm or less, for example, 0.34 to 100 nm. The thickness of the graphene quantum dots is eg 10 nm or less, eg 0.01 to 10 nm, eg 0.34 nm to 10 nm.

Graphene quantum dots have a two-dimensional sheet shape, and have a size/thickness ratio of 3 to 30, for example, 5 to 25. When the graphene quantum dots have a sheet shape, the size (major axis length) is 1 to 10 nm, and the minor axis length is 0.5 to 5 nm. When the size, number of layers, and thickness of the graphene quantum dots are within the above ranges, the stability of the hardmask composition is excellent.

Graphene quantum dots may contain, for example, 100 to 60000 conjugated atoms, for example 100 to 600 conjugated atoms.

As the two-dimensional carbon nanostructure, carboxyl functionalized graphene quantum dots or hydroxyl group functionalized graphene quantum dots (OH functionalized GQD) may be used.

Carboxyl functionalized GQDs can be obtained by adding chloroacetic acid to bare GQDs or hydroxyl functionalized GQDs (OH functionalized GQDs), respectively. In addition, hydroxyl functionalized GQDs (OH-functionalized GNPs) can be obtained by a general method of introducing a hydroxyl group into GQDs. For example, it can be obtained by pulverizing fullerene to a predetermined size, adding a base and an oxidizing agent thereto, and then going through a pulverizing process. An example of a base is sodium hydroxide, and an example of an oxidizing agent is hydrogen peroxide.

The hard mask according to the embodiment has improved etch resistance compared to the conventional hard mask due to improved density.

A hard mask formed from the hard mask composition according to one embodiment contains the metal (M) of the composite of Chemical Formula 1, so that it is possible to form a hard mask having improved etch resistance and a uniform thickness.

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Scattering does not occur in visible light, and the transmittance in the wavelength region of about 633 nm is 1% or less. When the hard mask having improved transmittance is used as described above, it is easier to check the hard mask pattern and the align mark for patterning the layer to be etched, thereby enabling patterning of the etchant layer having a finer and denser pattern size.

The graphene quantum dots contained in the hard mask have a k of 0.5 or less, for example 0.3, specifically 0.1 or less at a wavelength of about 633 nm. For reference, k of graphite is 1.3 to 1.5, and graphene composed of only sp2 bonding structure has k of 1.1 to 1.3.

k is an extinction coefficient and is measured by a spectroscopic ellipsometer measurement method. When k of the graphene quantum dots is within the above range, it is easy to recognize an align mark using a hard mask formed using graphene quantum dots.

The total thickness of the graphene quantum dots is 100 nm or less, eg 0.34 to 100 nm, eg 0.34 to 10 nm. Graphene quantum dots having such a thickness have a stable structure. Graphene quantum dots according to an embodiment contain some oxygen atoms other than carbon rather than a complete C=C/C-C conjugated structure. In addition, a carboxyl group, a hydroxyl group, an epoxy group, a carbonyl group, and the like may be present at the terminal of the graphene quantum dots.

Graphene quantum dots have excellent solvent dispersibility, so it is easy to prepare a hard mask composition and has excellent stability. And the etching resistance to etching gas is improved.

Peaks appear at about 1340-1350 cm ^-1 , about 1580 cm ^-1 , and about 2700 cm ^-1 in the Raman analysis spectrum. This peak gives information about the thickness, crystallinity and charge doping state of the graphene quantum dots. The peak appearing at about 1580 cm ^-1 is a peak called "G mode", which is caused by a vibration mode corresponding to stretching of carbon-carbon bonds, and the energy of "G-mode" is determined by the density of excess charge doped in graphene quantum dots. And the peak appearing at about 2700 cm ^-1 is a peak called "2D-mode" and is useful when evaluating the thickness of graphene quantum dots. The peak at 1340-1350 cm ^-1 is a peak called "D mode" and appears when there are defects in the SP ² crystal structure, and is mainly observed near the edge of the sample or when the sample has many defects. And the ratio of the D peak intensity to the G peak intensity (D/G intensity ratio) gives information about the degree of disorder of the crystal of graphene quantum dots.

An intensity ratio (I _D /I _G ) of the D-mode peak to the G-mode peak obtained by Raman spectroscopic analysis of graphene quantum dots is 2 or less. For example, it is 0.001 to 2.0.

An intensity ratio (I _2D /I _G ) of a 2D mode peak to a G mode peak obtained by Raman spectroscopy of the graphene quantum dots is 0.01 or more. For example, it is 0.01 to 1, specifically 0.05 to 0.5. When the intensity ratio of the D mode peak to the above-mentioned G mode peak and the intensity ratio of the 2D mode peak to the G mode peak are in the above range, the crystallinity of the graphene quantum dots is high and the bonding energy is high because the defects are small, so that the hard mask formed therefrom has excellent etch resistance.

Graphene quantum dots can be composed of a two-dimensional layered structure having a (002) crystal plane peak as a result of X-ray analysis by performing an X-ray diffraction experiment using CuKα. The (002) crystal plane peak appears in the range of 20 to 27°.

The d-spacing of the graphene quantum dots obtained by X-ray diffraction analysis is 0.3 to 0.7 nm, for example, 0.334 to 0.478 nm. When the above range is satisfied, a hard mask composition having excellent etching resistance can be obtained.

Graphene quantum dots according to an embodiment have a higher content of sp2 carbon than sp3 and contain a large number of oxygens compared to conventional amorphous carbon films. The sp2 carbon bond is an aromatic structure and has higher binding energy than that of the sp3 carbon bond.

The sp3 structure is a three-dimensional bonding structure of a regular tetrahedron of carbon, such as diamond, and the sp2 structure is a two-dimensional bonding structure of graphite, which increases the carbon-to-hydrogen ratio (C/H ratio) to secure resistance to dry etching.

The sp ² carbon fraction of the graphene quantum dots is 1 times greater than the sp 3 carbon fraction, for example, 1.0 to 10, and specifically 1.88 to 3.42.

The sp2 carbon atom bonding structure is 30 atomic % or more, for example, 39.7 to 62.5 atomic % by C1s XPS analysis. Due to this mixing ratio, the carbon-carbon bond energy constituting the graphene quantum dots is large, making it difficult to break the bond. Therefore, when the hard mask composition containing such graphene quantum dots is used, etching resistance is improved during an etching process. In addition, the binding force between the adjacent layer and the hard mask is excellent.

A hard mask obtained using existing amorphous carbon mainly contains sp2-oriented carbon atom bonding structure, so it has excellent etching resistance, but has low transparency, causing problems in alignment and generating a lot of particles during the deposition process. A hard mask using diamond-like carbon having a sp3 carbon atom bonding structure has been developed. However, this hard mask also showed limitations in process application due to low etching resistance.

Graphite has a k value of 1.3 to 1.5, and graphene composed of sp2 structure has a k value of 1.1 to 1.3. Graphene quantum dots according to one embodiment have good transparency, with k less than or equal to 1.0, for example, 0.1 to 0.5 within a specific wavelength. Therefore, when such a hard mask is used, it is easy to recognize an alignment mark when forming a pattern of a layer to be etched, so that a more elaborate and uniform pattern can be formed, and it has excellent etching resistance.

A hard mask obtained using the hard mask composition according to an embodiment is mixed with an organic material and an additive, so that it can be easily removed by a general metal hard mask, and patterning of the hard mask is easy.

The hardmask composition may further include a first material selected from an aromatic ring-containing monomer and a polymer containing a repeating unit including an aromatic ring-containing monomer, a hexagonal boron nitride derivative, a metal chalcogenide-based material, and a precursor thereof. At least one second material selected from the group consisting of, or a mixture thereof.

The first material may be in a non-bonded state with the second material, or the first material may be bonded to the second material through a chemical bond. In this way, the first material and the second material connected through chemical bonds have a complex structure. The first material and the second material having the aforementioned functional group may be connected through a chemical bond between the first material and the second material through a chemical reaction.

The chemical bond may be, for example, a covalent bond. Here, the covalent bond includes at least one of an ester group) (-C(=O)O-), an ether group (-O-), a thioether group (-S-), a carbonyl group (-C)=O)-), and an amide group (-C(=O)NH-).

The first material and the second material are a hydroxyl group, a carboxyl group, an amino group, -Si(R_One)(R₂)(R3)(R_One,R2 and R3 are each independently hydrogen, a hydroxyl group, a C1-C30 alkyl group, a C1-C30 alkoxy group, a C6-C30 aryl group, a C6-C30 aryloxy group, or a halogen atom), a thiol group (-SH), -Cl, -C(=O)Cl, -SCH₃, halogen atom, isocyanate group, glycidyloxy group, aldehyde group, epoxy group, imino group, urethane group, ester group, amide group, imide group, acryl group, methacrylic group, -(CH₂)_nCOOH (n = an integer from 1 to 10), -CONH₂, C1-C30 saturated organic group having a photosensitive functional group and C1-C30 unsaturated organic group having a photosensitive functional group.

The aromatic ring-containing monomer may be, for example, a monomer represented by Chemical Formula 13 below.

[Formula 13]

In Formula 13, R is a mono-substituted or multi-substituted substituent and is hydrogen, a halogen atom, a hydroxyl group, an isocyanate group, a glycidyloxy group, a carboxyl group, an aldehyde group, an amino group, a siloxane group, an epoxy group, an imino group, a urethane group, an ester group, an epoxy group, an amide group, an imide group, an acryl group, a methacryl group, an unsubstituted or substituted C1-C30 saturated organic group and at least one selected from the group consisting of unsubstituted or substituted C1-C30 unsaturated organic groups.

R may be a general photosensitive functional group other than the above groups.

The C1-C30 saturated organic group and the C1-C30 unsaturated organic group may have a photosensitive functional group. Here, the photosensitive functional group may include, for example, an epoxy group, an amide group, an imide group, a urethane group, an aldehyde group, and the like.

Examples of the C1-C30 saturated organic group and C1-C30 unsaturated organic group include a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C2-C30C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C6-C30 aryloxy group, A substituted C2-C30 heteroaryl group, a substituted or unsubstituted C2-C30 heteroaryloxy group, a substituted or unsubstituted C4-C30 carbocyclic group, a substituted or unsubstituted C4-C30 carbocyclic oxy group, a substituted or unsubstituted C2-C30 heterocyclic group, and the like.

In Formula 13, the binding position of R is not limited. And although R is shown as one for convenience, all of them may be substituted at substitutable positions.

The aromatic ring-containing monomer may be, for example, a monomer represented by Chemical Formula 14 below.

[Formula 14]

A-L-A'

In Formula 14, A and A' are identically or differently to each other, a monovalent organic group derived from one selected from monomers represented by Formula 13, and

L represents a single bond as a linker, or a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C2-C30 alkenylene group, a substituted or unsubstituted C2-C30 alkynylene group, a substituted or unsubstituted C7-C30 arylene alkylene group, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C2-C30 heteroarylene group, a substituted or unsubstituted C2-C30 30 Heteroarylenealkylene group, substituted or unsubstituted C1-C30 alkyleneoxy group, substituted or unsubstituted C7-C30 arylenealkyleneoxy group, substituted or unsubstituted C6-C30 aryleneoxy group, substituted or unsubstituted C2-C30 heteroaryleneoxy group, substituted or unsubstituted C2-C30 heteroarylenealkyleneoxy group -C(=O)- and -SO₂It is selected from the group consisting of -.

A substituted C1-C30 alkylene group, a substituted C2-C30 alkenylene group, a substituted C2-C30 alkynylene group, a substituted C7-C30 arylenealkylene group, a substituted C6-C30 arylene group, a substituted C2-C30 heteroarylene group, a substituted C2-C30 heteroarylene alkylene group, a substituted C1-C30 alkyleneoxy group, a substituted C7-C30 aryl The enealkyleneoxy group, the substituted C6-C30 aryleneoxy group, the substituted C2-C30 heteroaryleneoxy group, the substituted C2-C30 heteroarylenealkyleneoxy group is selected from a halogen atom, a hydroxyl group, an isocyanate group, a glycidyloxy group, a carboxyl group, an aldehyde group, an amino group, a siloxane group, an epoxy group, an imino group, a urethane group, an ester group, an epoxy group, an amide group, an imide group, an acrylic group, and a methacrylic group. may be substituted with one or more substituents.

In addition to the above substituents, it may be substituted with photosensitive functional groups.

The first material is at least one selected from the group consisting of a compound represented by Formula 15 and a compound represented by Formula 16 below.

[Formula 15]

In Formula 15, R is as defined in Formula 13 above.

[Formula 16]

In Formula 16, R is as defined in Formula 13 above, and L is as defined in Formula 14 above.

In Formulas 15 and 16, the binding position of R is not limited. And although R is shown as one for convenience, it may be substituted at all substitutable positions.

The weight average molecular weight of the polymer containing the repeating unit including the aromatic ring-containing monomer is 300 to 30,000. If a polymer having such a weight average molecular weight is used, thin film formation is easy and a transparent hard mask can be formed.

The first material is, for example, a compound represented by Chemical Formula 17 below.

[Formula 17]

In Formula 17, A is a substituted or unsubstituted C6 to C30 arylene group,

L is a single bond or a substituted or unsubstituted C1 to C6 alkylene group, and n is 1 to 5.

The arylene group is one selected from the groups listed in Group 1 below.

[Group 1]

The compound represented by Chemical Formula 17 may be, for example, one selected from compounds represented by Chemical Formulas 17a to 17c.

[Formula 17a]

[Formula 17b]

[Formula 17c]

In Formula 17a, 17b or 17c, L ¹ to L ⁴ are each independently a single bond or a substituted or unsubstituted C1 to C6 alkylene group.

The first material is selected from compounds represented by the following Chemical Formulas 17d to 17f.

[Formula 17d] [Formula 17e]

[Formula 17f]

The first material may be a compound represented by Formula 18 below.

[Formula 18]

The first material may be a copolymer represented by Chemical Formula 19 below.

[Formula 19]

In Formula 19, R ₁ is C1-C4 substituted or unsubstituted alkylene; R ₂ , R ₃ , R ₇ and R ₈ are each independently hydrogen, hydroxy, C1-C10 straight-chain, branched-chain or cyclic alkyl, C ₁ -C ₁₀ alkoxy or C6-C30 aryl; R ₄ , R ₅ and R ₆ are each independently hydrogen, hydroxy, C1-C4 alkyl ether, or phenyldialkylene ether; R ₉ is alkylene, phenyldialkylene, hydroxyphenylalkylene or a mixture thereof; x,y is the ratio of the two repeating units in part A, and is greater than or equal to 0 and less than or equal to 1, and x+y=1; n is an integer from 1 to 200 and m is an integer from 1 to 200.

The second material is a polymer represented by Formula 19a, Formula 19b or Formula 19c.

[Formula 19a]

In Formula 19a, x is 0.2 and y is 0.8.

[Formula 19b]

In Formula 19b, x is 0.2, y is 0.8, n = 90 and m = 10.

[Formula 19c]

In Formula 19c, x is 0.2, y is 0.8, n = 90, m = 10.

The first material may be a copolymer represented by Formula 20 or Formula 21 below.

[Formula 20]

[Formula 21]

In Formula 20-21, m and n are each an integer of 1 to 190, R ₁ is hydrogen (-H), a hydroxyl group (-OH), a C1-10 alkyl group, a C6-10 aryl group, an allyl group, and a halogen atom, and R ₂ is a group represented by the following Formula 22, phenyl, chrysene, pyrene, fluoranthrene, anthrone, benzophenone, thioxanthone, Any one of anthracene and derivatives thereof, R ₃ is a conjugated diene, and R ₄ is an unsaturated dienophile.

[Formula 22]

In Formulas 20 and 21, R ₃ is, for example, 1,3-butadienyl or 1,6-cyclopentadienylmethyl, and R ₄ is, for example, vinyl or cyclopentenylmethyl.

The copolymer may be one selected from polymers represented by Formulas 23 to 26 below.

[Formula 23]

In Formula 23, m+n=21, Mw=10,000, and polydispersity is 2.1.

[Formula 24]

In Formula 24, the weight average molecular weight is about 11,000, the polydispersity is 2.1, and m+n=21.

[Formula 25]

In Formula 25, the weight average molecular weight was about 10000, the polydispersity was 1.9, l+m+n = 21, and n+m:l = 2:1.

[Formula 26]

In Formula 26, Mw is about 10,000, polydispersity is about 2.0, and n is about 20.

In the hard mask composition according to the embodiment, the composite and/or the two-dimensional carbon nanostructure represented by Chemical Formula 1, which is a material for forming the hard mask, has a very low reactivity to CxFy gas, which is an etching gas used to etch material layers such as SiO ₂ and SiN, and can improve etching resistance. In addition, when SF ₆ or XeF ₆ , an etching gas having low reactivity to SiO ₂ and SiNx, is used, ashing is easy due to good etching properties. In addition, the hard mask forming material is a material having a band gap and has transparency, so that the process can be easily performed without the need for an additional align mask.

Hexagonal boron nitride derivatives are hexagonal boron nitride (h-BN) or hexagonal boron carbonitride (h-BxCyNz) (where the sum of x, y, and z is 3) in which B and N are regularly formed in a hexagonal ring form, or some of the B and N atoms are substituted with carbon while maintaining the hexagonal ring form.

A metal chalcogenide-based material is a compound composed of at least one Group 16 (chalcogen) element and one or more positive (electropositive element) elements. ), copper (Cu), gallium (Ga), indium (In), tin (Sn), germanium (Ge), and lead (Pb), and sulfur (S), selenium (Se), and tellurium (Te).

The metal chalcogenide-based material is molybdenum sulfide (MoS2), molybdenum selenide (MoSe ₂ ), molybdenum telluride (MoTe ₂ ), tungsten sulfide (WS ₂ ), tungsten selenide (WSe ₂ ), and tungsten telluride (WTe ₂ ). For example, a chalcogenite-based material is molybdenum sulfide (MoS ₂ ).

The aforementioned hexagonal boron nitride is composed of boron atoms and nitrogen atoms alternately located in a planar hexagonal crystal structure. The interlayer structure of hexagonal boron nitride is a structure in which adjacent boron atoms and nitrogen atoms overlap each other due to the polarity of the two atoms, that is, AB stacking. Here, the hexagonal boron nitride may have a layered structure in which nano-level thin sheets are stacked on top of each other, and the layered structure is separated or peeled to include a single layer or several layers of hexagonal boron nitride sheets.

The hexagonal boron nitride derivative according to one embodiment shows a peak at about 1360 cm ^-1 in a Raman spectroscopic spectrum. These peak positions give information about the number of layers of hexagonal boron nitride. Hexagonal boron nitride was found to have a nanosheet structure of single-layer or multi-layer hexagonal boron nitride through AFM, Raman spectroscopy, and TEM analysis.

Hexagonal boron nitride derivatives can be composed of a two-dimensional layered structure having a (002) crystal plane peak as a result of X-ray diffraction experiments using CuKα and X-ray analysis. The (002) crystal plane peak appears in the range of 20 to 27°.

The hexagonal boron nitride derivative has an interlayer spacing (d-spacing) obtained by X-ray diffraction analysis of 0.3 to 0.7 nm, for example, 0.334 to 0.478 nm. And the average grain diameter of the crystals obtained by X-ray diffraction analysis is 1 nm or more, for example, 23.7 to 43.9 Å. When the above range is satisfied, a hard mask composition having excellent etching resistance can be obtained.

The hexagonal boron nitride derivative is formed by stacking single-layer or multi-layer two-dimensional boron nitride.

Hereinafter, a method of manufacturing a hard mask using the hard mask composition according to an embodiment and a method of forming a pattern using the same will be described.

A hard mask composition according to an embodiment may include a complex represented by Chemical Formula 1 and a solvent. A hardmask composition according to another embodiment may contain at least one selected from the composite represented by Chemical Formula 1, a two-dimensional carbon nanostructure, a zero-dimensional carbon nanostructure, a precursor thereof, and a derivative thereof, and a solvent.

The hard mask composition may include a first material selected from an aromatic ring-containing monomer and a polymer containing a repeating unit including an aromatic ring-containing monomer; at least one second material selected from the group consisting of hexagonal boron nitride derivatives, metal chalcogenide-based materials, and precursors thereof; Alternatively, a mixture thereof may be further added.

After forming a film to be etched on the substrate, the above-described hard mask composition is coated on the film to be etched and dried to form a hard mask.

The thickness of the hard mask prepared according to the above process is 10 nm to 10,000 nm. In addition, such a hard mask includes a product obtained by coating and heat-treating the hard mask composition described above.

The hard mask according to an embodiment may contain i) the composite represented by Chemical Formula 1, or ii) the composite represented by Chemical Formula 1 and at least one selected from a two-dimensional carbon nanostructure, a zero-dimensional carbon nanostructure, and derivatives thereof.

A hard mask according to an embodiment includes at least one first material selected from i) the complex of Chemical Formula 1, ii) an aromatic ring-containing monomer, and a polymer containing a repeating unit including an aromatic ring-containing monomer; at least one second material selected from the group consisting of hexagonal boron nitride derivatives, metal chalcogenide-based materials, and precursors thereof; or mixtures thereof.

The hard mask according to an embodiment includes i) the composite of Chemical Formula 1, ii) at least one selected from two-dimensional carbon nanostructures, zero-dimensional carbon nanostructures, and derivatives thereof, and iii) an aromatic ring-containing monomer and an aromatic ring-containing monomer. At least one first material selected from a polymer containing a repeating unit including a monomer; at least one second material selected from the group consisting of hexagonal boron nitride derivatives, metal chalcogenide-based materials, and precursors thereof; or mixtures thereof.

Heat treatment may be selectively performed during or after coating the hard mask composition on the upper surface of the etchant film. It is also possible to omit this heat treatment. This heat treatment step may vary depending on the material of the film to be etched, and is, for example, 1000°C or less, for example, in the range of 50 to 1000°C, for example, 300 to 1,000°C.

The heat treatment is performed in an inert gas atmosphere and vacuum.

As a heat source for the heat treatment process, induction heating, radiant heat, laser, infrared rays, microwaves, plasma, ultraviolet rays, surface plasmon heating, and the like can be used.

The inert atmosphere may be used by mixing nitrogen gas and/or argon gas.

After the heat treatment step, the solvent is removed, and the c-axis purifying process of graphene may proceed.

Subsequently, a process of baking the product from which the solvent is removed without heat treatment or through heat treatment may be performed at 400° C. or less, for example, 100 to 400° C. After this baking process, a step of heat treatment at 800° C. or less, for example, 400 to 800° C. may be further performed.

A thermal reduction process may be performed in the heat treatment step. According to another embodiment, it is also possible to perform only the heat treatment step without going through the above-described baking process. When the heat treatment and baking temperatures are within the above ranges, a hard mask having excellent etching resistance may be manufactured.

The heating rate in the heat treatment and baking step is 1 to 10 ℃ / min. In this temperature increase rate range, process efficiency is excellent without fear of damaging the deposited film due to rapid temperature change.

The thickness of the hard mask is, for example, 10 nm to 10,000 nm.

In the present specification, when the hard mask composition contains graphene quantum dots, which are two-dimensional carbon nanostructures, the graphene quantum dots may be prepared according to a method described later. According to the first manufacturing method, a graphite intercalation compound (GIC) is obtained by intercalating intercalation into graphite, and graphene quantum dots can be obtained therefrom.

For example, sodium potassium tartrate is used as the intercalation material. When potassium sodium tartrate is used as the intercalation material, it is inserted into graphite without an additional surfactant or solvent in a solvothermal reaction to obtain a graphite intercalation compound, and through a process of selecting the particle size of the resultant, desired graphene quantum dots can be obtained. Potassium sodium tartrate can simultaneously serve as an intercalator and solvent.

The solvothermal reaction may proceed, for example, in an autoclave. The solvothermal reaction is carried out at, for example, 25 to 400°C, specifically about 250°C.

As the graphite used as a starting material, natural graphite, kish graphite, synthetic graphite, expandable graphite or expanded graphite, or a mixture thereof may be used. According to the second manufacturing method, graphite may be obtained by acid treatment. For example, an acid and an oxidizing agent are added to graphite, reacted by heating, and cooled to room temperature (25° C.) to obtain a graphene quantum dot precursor-containing mixture. A desired graphene quantum dot can be obtained by adding an oxidizing agent to the precursor-containing mixture to oxidize it, and then working it up.

Examples of the acid include sulfuric acid, nitric acid, acetic acid, phosphoric acid, hydrofluoric acid, perchloric acid, trifluoroacetic acid, hydrochloric acid, m-chlorobenzoic acid, and mixtures thereof. And as the oxidizing agent, for example, potassium permanganate, potassium perchlorate, ammonium persulfate, and mixtures thereof may be used. Examples of the acid and oxidizing agent are as described above. The content of the oxidizing agent is, for example, 0.00001 to 30 parts by weight based on 100 parts by weight of graphite.

The above-described reaction of adding an acid and an oxidizing agent to the graphite and heating the graphite may be performed, for example, using microwaves. Microwaves have a power of 50 to 1500 W and a frequency of 2.45 to 60 GHz. The time for applying the microwave varies depending on the frequency of the microwave, but for example, the microwave is applied for 10 to 30 minutes.

The work-up process includes adjusting the reaction product that has undergone the oxidation process to room temperature, adding deionized water thereto to dilute the reaction mixture, and adding a base thereto to carry out a neutralization reaction. In addition, in the work-up process, desired graphene quantum dots can be obtained through a particle selection process from the result of the neutralization reaction.

Hereinafter, a method for preparing functional group-bonded graphene quantum dots will be described. Hydroxy-bonded graphene quantum dots have a wide range of applications because of their excellent solubility in solvents.

A method of manufacturing a hydroxyl-bonded graphene quantum dot according to an embodiment is as follows.

Graphene quantum dots having a single crystal can be obtained by performing a hydrothermal fusion reaction of a polycyclic aromatic hydrocarbon under an aqueous alkaline solution condition. The hydrothermal melting reaction under the aqueous alkali solution condition is carried out in the range of 90 to 200 ° C. In this hydrothermal melting reaction, when an alkaline species such as OH ⁻ is present, hydrogen removal, condensation or graphitization, and edge functionalization occur. Examples of the polycyclic aromatic hydrocarbon include pyrene and 1-nitropyrene.

During the hydrothermal melting reaction described above, an amine-based material such as NH ₃ and NH ₂ NH ₂ may be added. The addition of these materials gives water-soluble OH- and amine-functionalized graphene quantum dots.

Before carrying out the hydrothermal melting reaction described above, a nitration reaction of polycyclic aromatic hydrocarbons is performed. This nitration reaction can be carried out using hot nitric acid (hot HNO3).

A method of forming a pattern using a hard mask composition according to an embodiment will be described with reference to FIGS. 2A to 2E .

Referring to FIG. 2A , a film to be etched 11 is formed on the substrate 10 . A hard mask 12 is formed by supplying the hard mask composition according to an embodiment to the upper portion of the film to be etched 11 .

The process of supplying the hard mask composition is carried out according to one selected from spin coating, air spray, electrospray, dip coating, spray coating, doctor blade method, and bar coating. Since the hard mask can be manufactured according to the above-described method, the manufacturing cost of the hard mask is reduced, the manufacturing process itself is simplified, and the manufacturing process time is reduced compared to the case of using a method such as chemical vapor deposition.

According to one embodiment, the step of supplying the hard mask composition may be applied by a spin-on coating method. At this time, the coating thickness of the hard mask composition is not limited, but may be, for example, 10 to 10,000 nm thick, specifically 10 to 1,000 nm thick.

The substrate is not particularly limited, and for example, Si substrate, glass substrate, GaN substrate, silica substrate, nickel (Ni), cobalt (Co), iron (Fe), platinum (Pt), palladium (Pd), gold (Au), aluminum (Al), chromium (Cr), copper (Cu), manganese (Mn), molybdenum (Mo), rhodium (Rh), iridium (Ir), tantalum (Ta), titanium (Ti) ), a substrate containing at least one selected from tungsten (W), uranium (U), vanadium (V), and zirconium (Zr), and at least one selected from polymer substrates may be used.

A photoresist layer 13 is formed on the hard mask 12 .

As shown in FIG. 2B, a photoresist pattern 13a is formed by exposing and developing the photoresist layer 13 in a conventional manner.

Exposing the photoresist layer may be performed using, for example, ArF, KrF, or EUV. After exposure, a heat treatment process may be performed at about 200 to 500°C.

During the development, a developing solution such as an aqueous solution of tetramethyl ammonium hydroxide (TMAH) may be used.

Thereafter, the hard mask 12 is etched using the photoresist pattern 13a as an etching mask to form a hard mask pattern 12a on the upper portion of the film to be etched 11 (FIG. 2C).

The hard mask pattern has a thickness of 10 nm to 10,000 nm. When having this thickness range, not only film uniformity is excellent, but also it is possible to accurately realize a small pattern size and has excellent etch resistance.

Etching may be performed by, for example, a dry etching method using an etching gas. As the etching gas, for example, at least one selected from CF ₄ , CHF ₃ , Cl ₂ and BCl ₃ is used.

According to one embodiment, a mixed gas of C ₄ F ₈ and CHF ₃ is used as an etching gas, and the mixing ratio thereof is 1:10 to 10:1 by volume.

The film to be etched may be formed in a plurality of patterns. The plurality of patterns may be various, such as a metal pattern, a semiconductor pattern, an insulator pattern, and the like. For example, it can be applied in various patterns in semiconductor integrated circuit devices.

The film to be etched contains a material to be finally patterned, and may be, for example, a metal layer such as aluminum or copper, a semiconductor layer such as silicon, or an insulating layer such as silicon oxide or silicon nitride. The film to be etched may be formed according to various methods such as sputtering, electron beam deposition, chemical vapor deposition, and physical vapor deposition. The film to be etched may be formed by, for example, chemical vapor deposition.

As shown in FIGS. 2D and 2E , the film to be etched 11 is etched using the hard mask pattern 12a as an etching mask to form a film to be etched pattern 11a having a desired fine pattern.

When the hard mask composition according to one embodiment is used, a solution process is possible, so a separate coating facility is not required, and ashing-off is easy in an oxygen atmosphere and mechanical properties are excellent.

A hard mask according to an embodiment may be used as a stopper by being inserted between an etching mask or other layers to manufacture a semiconductor device.

Hereinafter, a method of forming a pattern using a hard mask composition according to another embodiment will be described with reference to FIGS. 3A to 3D.

Referring to FIG. 3A , a film to be etched 21 is formed on the substrate 20 . As the substrate 20, a silicon substrate is used.

The film to be etched 21 may be formed of, for example, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a silicon silicide (SiC) film, or a derivative film thereof. Thereafter, a hard mask composition is supplied to the upper portion of the film to be etched 21 to form a hard mask 22 .

An antireflection layer 30 is formed on the hard mask 22 . Here, the anti-reflection layer 30 may be formed of an inorganic anti-reflection layer, an organic anti-reflection layer, or a combination thereof. In FIGS. 3A to 3C , a case in which the antireflection film 30 is composed of an inorganic antireflection film 32 and an organic antireflection film 34 is exemplified.

The inorganic antireflection film 32 is, for example, a SiON film. As the organic antireflection film 34, a photoresist and a commercially available polymer film having a suitable refractive index and high absorption coefficient for the exposure wavelength can be used.

The thickness of the antireflection film is, for example, 100 to 500 nm.

A photoresist layer 23 is formed on the antireflection layer 30 .

A photoresist pattern 23a is formed by exposing and developing the photoresist layer 23 in a conventional manner. Thereafter, the antireflection film 30 and the hard mask 22 are sequentially etched using the photoresist pattern 23a as an etching mask to form a hard mask pattern 22a on the etched film 21 . The anti-reflection film pattern 30a is composed of an inorganic anti-reflection film pattern 32a and an organic anti-reflection film pattern 34a.

3B shows that the photoresist pattern 23a and the antireflection film pattern 30a remain on the hard mask pattern 22a after the formation, but in some cases, part or all of the photoresist pattern 23a and the antireflection film pattern 30a may be removed during an etching process for forming the hard mask pattern.

3C shows a state in which only the photoresist pattern 23a is removed.

The film to be etched is etched using the hard mask pattern 22a as an etching mask to form a desired film pattern 21a (FIG. 3D).

As described above, after forming the film to be etched pattern 21a, the hard mask pattern 22a is removed. The hard mask pattern according to the embodiment can be easily removed through a conventional removal process and has almost no residue after removal.

As non-limiting examples of the hard mask pattern removal process, O ₂ ashing and wet strip processes may be used. Wet stripping can be performed using, for example, alcohol, acetone, a mixture of nitric and sulfuric acids, and the like.

The graphene quantum dots of the hard mask formed according to the above process can secure sufficient resistance to dry etching because the content of the sp2 carbon structure is higher than the content of the sp3 carbon structure. In addition, such a hard mask has excellent transparency, so it is easy to check alignment marks for patterning.

A pattern formed using the hard mask composition according to an embodiment may be used in manufacturing and designing an integrated circuit device according to a semiconductor device manufacturing process. For example, it can be used when forming patterned material layer structures such as metal wires, holes for contacts or vias, insulating sections (eg, Damascne Trench (DT) or shallow trench isolation (STI), trenches for capacitor structures, etc.).

Hereinafter, “alkyl” in the present specification refers to a fully saturated branched or unbranched (or straight-chain or linear) hydrocarbon.

Non-limiting examples of “alkyl” include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, n-heptyl, and the like.

One or more hydrogen atoms in “alkyl” is a halogen atom, a C1-C20 alkyl group substituted with a halogen atom (e.g. CCF₃, CHCF₂, CH₂F, CCl₃ etc.), C1-C20 alkoxy, C2-C20 alkoxyalkyl, hydroxy group, nitro group, cyano group, amino group, C1-C20 alkylamino group, amidino group, hydrazine group, hydrazone group, carboxyl group or its salt, sulfonyl group, sulfamoyl group, sulfonic acid group or its salt, phosphoric acid or its salt, C1-C20 alkyl group, C2- It may be substituted with a C20 alkenyl group, a C2-C20 alkynyl group, a C1-C20 heteroalkyl group, a C6-C20 aryl group, a C6-C20 arylalkyl group, a C6-C20 heteroaryl group, a C7-C20 heteroarylalkyl group, a C6-C20 heteroaryloxy group, or a C7-C20 heteroaryloxyalkyl group.

The term “halogen atom” includes fluorine, bromine, chlorine, iodine, and the like.

The term “heteroalkyl” refers to an alkyl group containing heteroatoms.

“Alkenyl” refers to a branched or unbranched hydrocarbon having at least one carbon-carbon double bond. Non-limiting examples of the alkenyl group include vinyl, allyl, butenyl, isopropenyl, isobutenyl, and the like, and one or more hydrogen atoms of the alkenyl group may be substituted with the same substituents as those of the aforementioned alkyl group.

"Alkynyl" refers to a branched or unbranched hydrocarbon having at least one carbon-carbon triple bond. Non-limiting examples of the “alkynyl” include ethynyl, butynyl, isobutynyl, propynyl, and the like.

“Aryl” also includes groups in which an aromatic ring is fused to one or more carbon rings. Non-limiting examples of “aryl” include phenyl, naphthyl, tetrahydronaphthyl, and the like.

In addition, one or more hydrogen atoms of the “aryl” group may be substituted with substituents similar to those of the above-mentioned alkyl group.

“Heteroaryl” refers to a monocyclic or bicyclic organic compound containing at least one heteroatom selected from N, O, P or S, and the remaining ring atoms being carbon. The heteroaryl group may include, for example, 1-5 heteroatoms and 5-10 ring members. The S or N may be oxidized and have various oxidation states.

Examples of heteroaryl include thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl group, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thia Diazolyl, 1,3,4-thiadiazolyl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, 1,2,4-triazol-3-yl, 1,2,4-triazole- 5-yl, 1,2,3-triazol-4-yl, 1,2,3-triazol-5-yl, tetrazolyl, pyridyl-2-yl, pyridyl-3-yl, pyrazin-2-yl, pyrazin-4-yl, pyrazin-5-yl, pyrimidin-2-yl, pyrimidin-4-yl, or pyrimidin-5-yl.

The term "heteroaryl" includes heteroaromatic rings fused to one or more aryl, cycloaliphatic, or heterocycles.

As used in formulas, “carbocyclic” groups refer to saturated or partially unsaturated, non-aromatic monocyclic, bicyclic or tricyclic hydrocarbon groups.

Examples of monocyclic hydrocarbons include cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl and the like. Examples of bicyclic hydrocarbons include bornyl, decahydronaphthyl, bicyclo[2.1.1]hexyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.1]heptenyl, or bicyclo[2.2.2]octyl. And examples of tricyclic hydrocarbons include adamantly and the like.

A “heterocycle” is a ring group containing at least one heteroatom and may contain 5 to 20, for example 5 to 1-carbon atoms. Here, the heteroatom is one selected from among sulfur, nitrogen, oxygen and boron.

"Cyclic heteroalkylene group" refers to a divalent cyclic hydrocarbon containing at least one heteroatom.

Alkoxy, aryloxy and heteroaryloxy refer herein to alkyl, aryl and heteroaryl bonded to an oxygen atom, respectively. And an alkylene group, a heteroalkylene group, an arylene group, and a heteroarylene group are used in the same sense as the aforementioned alkyl group, heteroalkyl group, aryl group, and heteroaryl group, except that they are divalent groups.

Hereinafter, specific examples are presented. However, the embodiments described below are merely intended to specifically illustrate or describe, and are not meant to be limited thereto.

Hereinafter, specific examples are presented. However, the embodiments described below are only intended to specifically illustrate or describe, and are not meant to be limited thereto.

manufacturing example One

2 g of citric acid (Aldrich) was dissolved in 300 ml of 3 mM NaOH aqueous solution, and then reacted in an autoclave at 160 ^° C for 4 hours. The product was cooled to room temperature (25° C.), ethanol was added, and centrifugation was performed to separate the product and the unreacted product. The separated product was dissolved in 300 ml of deionized water and then filtered through a microporous membrane having a pore size of 0.22 μm to remove insoluble carbon products. The resulting product obtained through filtration was subjected to dialysis for 2 days to obtain graphene quantum dots having an OH group bonded thereto. The graphene quantum dots to which OH groups were bonded had a sheet type with a major axis length of about 5 nm.

manufacturing example 2

20 mg of graphite (Alfa Aesar) was dissolved in concentrated sulfuric acid (100 ml), and then sonication was performed for 1 hour. After adding 1 g of KMnO ₄ to the resulting product, the temperature of the reaction mixture was adjusted to be below about 25°C.

The resulting product was refluxed for 10 minutes by applying microwave (power: 600W) at normal pressure. The reaction mixture was cooled to adjust the temperature of the reaction mixture to about 25° C., then 700 ml of deionized water was added to the reaction mixture to dilute the reaction mixture, and the pH of the reaction mixture was adjusted to about 7 by adding sodium hydroxide while the reaction mixture was placed in an ice bath.

The reaction product was filtered using a porous membrane having a pore diameter of about 200 nm to separate and remove graphene having a large size. The obtained filtrate was subjected to dialysis to remove the residue, centrifugation to separate and remove medium-sized graphene, and drying to obtain sheet-type graphene quantum dots having a major axis length of about 10 nm.

manufacturing example 3

2 g of pyrene and 160 ml of nitric acid were added and refluxed at 80 DEG C for about 12 hours to obtain a reaction mixture containing 1,3,6-trinitropyrene. After cooling the reaction mixture to room temperature, it was diluted by adding 1 l of deionized water and water thereto, and then filtered through a microporous membrane having a pore size of 0.22 μm.

1.0 g of 1,3,6-trinitropyrene obtained through filtration was dispersed in 0.6 l of 0.2 M NaOH aqueous solution, and ultrasonic waves (500 W, 40 kHz) were applied thereto for 2 hours. The resulting suspension was reacted at 200° C. for 10 hours in an autoclave. After cooling the resulting product to room temperature, the resulting product was filtered through a microporous membrane having a pore size of 0.22 μm to remove insoluble carbon products. 10 ml of hydrochloric acid and 1 L of deionized water were added to the solution that passed through the microporous membrane, stirred, and filtered through a microporous membrane having a pore size of 0.22 μm to remove sodium ions and chlorine ions. The slurry remaining on the microporous membrane was dried to obtain sheet-type graphene quantum dots having a major axis length of about 7 nm to which OH groups were bonded. The graphene quantum dots prepared according to Preparation Examples 1 and 3 have a structure in which oxygen-containing functional groups are formed at the ends, and the graphene quantum dots prepared according to Preparation Example 2 have edges and planes of graphene using microwaves during the preparation process. It has a structure in which oxygen-containing functional groups are formed.

manufacturing example 4

Chloroacetic acid was added to the OH group-bonded graphene quantum dots obtained in Preparation Example 3, and heat treatment was performed at 80° C. for 60 minutes. After heat treatment, a coupling reaction was performed to obtain COOH-functionalized GNP. The major axis length of the COOH-functionalized GQDs was about 7 nm.

Example One: hard mask preparation of the composition

A hardmask composition was prepared by mixing the composite represented by Formula 6 (Aldrich) and the OH-functionalized GQD obtained in Preparation Example 3 at a weight ratio of 1:4 and adding N-methyl-2-pyrrolidone thereto. The content of the complex of Formula 6 and the OH-functionalized GQDs in the hardmask composition was 10% by weight based on the total weight of the composition.

[Formula 6]

Example 2-3: hard mask preparation of the composition

A hardmask composition was prepared in the same manner as in Example 1, except that the mixing weight ratio of the composite represented by Formula 6 and the OH-functionalized GQD (size: about 7 nm) obtained according to Preparation Example 3 was changed to 1:3 and 1:5, respectively.

Example 4-6: hard mask preparation of the composition

A hardmask composition was prepared in the same manner as in Example 1, except that the composite represented by Chemical Formula 7, the composite represented by Chemical Formula 8, and the composite represented by Chemical Formula 9 were respectively used instead of the composite represented by Chemical Formula 6.

Example 7: hard mask preparation of the composition

A hardmask composition was prepared in the same manner as in Example 1, except that the composite represented by Chemical Formula 10 was used instead of the composite represented by Chemical Formula 6.

Example 8: hard mask preparation of the composition

A hardmask composition was prepared by mixing a composite represented by Formula 6 (Aldrich), OH-functionalized GQD obtained according to Preparation Example 3, and fullerene represented by Formula 27 at a weight ratio of 1:4:1 and adding N-methyl-2-pyrrolidone thereto. The total content of the complex of Formula 6, OH-functionalized GQDs, and fullerenes in the hardmask composition was 10% by weight based on the total weight of the composition.

[Formula 6] [Formula 27]

Example 9: hard mask preparation of the composition

In preparing the hard mask composition, a hard mask composition was prepared in the same manner as in Example 1, except that the weight ratio of the composite represented by Formula 6 (Aldrich), the OH-functionalized GQD obtained in Preparation Example 3, and the fullerene was changed to 1:4:2.

production example 1: Manufacturing of a silicon substrate on which a silicon oxide pattern is formed

The hard mask composition obtained in Example 1 was spin-coated on a silicon substrate having a silicon oxide film formed thereon. Subsequently, baking was performed at 400° C. for 2 minutes to form a hard mask having a thickness of about 72 nm including a product obtained by treating the hard mask composition.

1700 Å of ArF photoresist (PR) was coated on the hard mask, and pre-bake was performed at 110° C. for 60 seconds. Exposure was performed using an exposure equipment manufactured by ASML (XT: 1400, NA 0.93), followed by post-bake at 110° C. for 60 seconds. Subsequently, photoresist patterns were formed by developing with a 2.38 wt % aqueous solution of tetramethyl ammonium hydroxide (TMAH).

Dry etching was performed with a CF ₄ /CHF ₃ mixed gas using the photoresist pattern as a mask. Etching conditions are chamber pressure 20mT, RF power 1800W, C ₄ F ₈ /CHF ₃ (4/10 volume ratio), and the time is 120 seconds.

After performing the dry etching, O ₂ ashing and wet strip processes were performed on the hard mask and the organic material to obtain a silicon substrate having a silicon oxide pattern, which is a desired final pattern.

production example 2-9: Manufacturing of silicon substrate on which silicon oxide patterns are formed

It was carried out according to the same method as Preparation Example 1, except that the hardmask compositions prepared according to Examples 2 to 9 were used instead of the hardmask compositions obtained according to Example 1, respectively.

comparative example One

A hard mask composition was prepared by dissolving the monomer represented by Formula 18 in a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA), methylpyrrolidone, and gamma -butyrolactone (40:20:40 (v/v/v)) and then filtering.

[Formula 18]

A hard mask composition obtained according to the above process was obtained. After coating the silicon oxide on a silicon substrate formed by a spin-on coating method, heat treatment was performed at 400° C. for 120 seconds to form a hard mask including spin-on-carbon (SOC).

1700 Å of ArF photoresist (PR) was coated on the hard mask, and pre-bake was performed at 110° C. for 60 seconds. Each exposure was performed using an exposure equipment manufactured by ASML (XT: 1400, NA 0.93), and then post-bake was performed at 110° C. for 60 seconds. Subsequently, photoresist patterns were formed by developing with a 2.38 wt % aqueous solution of tetramethyl ammonium hydroxide (TMAH).

Dry etching was performed with a CF ₄ /CHF ₃ mixed gas using the photoresist pattern as a mask. Etching conditions are chamber pressure 20mT, RF power 1800W, C ₄ F ₈ /CHF ₃ (4/10 volume ratio), and the time is 120 seconds.

After performing dry etching, O ₂ ashing and wet strip processes were performed on the hard mask and the organic material to obtain a silicon substrate having a silicon oxide pattern, which is a desired final pattern.

reference example One

0.5 g of the OH-functionalized quantum dots obtained in Preparation Example 3 was dispersed in 1 L of water to obtain a hard mask composition. The hard mask composition was applied on a silicon substrate on which silicon oxide was formed according to a spin-on coating method, and then heat treatment was performed at 400° C. for 2 minutes. Subsequently, baking was performed at 400 ° C. for 1 hour, followed by vacuum heat treatment at 600 ° C. for 1 hour to form a hard mask containing OH-functionalized graphene quantum dots having a thickness of about 200 nm.

1700 Å of ArF photoresist (PR) was coated on the hard mask, and pre-bake was performed at 110° C. for 60 seconds. After each exposure was performed using an exposure equipment from ASML (XT: 1400, NA 0.93), post-bake was performed at 110°C for 60 seconds. Subsequently, photoresist patterns were formed by developing with a 2.38 wt % aqueous solution of tetramethyl ammonium hydroxide (TMAH).

Dry etching was performed with a CF ₄ /CHF ₃ mixed gas using the photoresist pattern as a mask. Etching conditions are chamber pressure 20mT, RF power 1800W, C ₄ F ₈ /CHF ₃ (4/10 volume ratio), and the time is 120 seconds.

After performing dry etching, O ₂ ashing and wet strip processes were performed on the hard mask and the organic material to obtain a silicon substrate having a silicon oxide pattern, which is a desired final pattern.

evaluation example 1: Solubility test

A solubility test for NMP was conducted on a mixture of the composite of Chemical Formula 6 used in preparing the hardmask composition of Example 1 at a weight ratio of 1:4 and the graphene quantum dots obtained according to Preparation Example 3.

The solubility test results are shown in Table 1 below. Table 1 shows the solubility of the complex of Formula 6 together for comparison with the solubility of the mixture of the complex of Formula 6 and the graphene quantum dots of Preparation Example 3.

division Solubility (% by weight) Complex of Formula 6 less than 2% by weight A mixture of the composite of Formula 6 and the graphene quantum dots of Preparation Example 3 at a weight ratio of 1:4 10% by weight

Referring to Table 1, the mixture of the composite of Formula 6 mixed at a weight ratio of 4:1 and the graphene quantum dots obtained according to Preparation Example 3 has a very improved solubility in NMP compared to the solubility of the composite of Formula 6 in NMP.

evaluation example 2: X-ray photoelectron spectroscopy ( XPS ) analyze

XPS analysis was performed on the hard masks prepared according to Manufacturing Example 1 and Reference Example 1. XPS analysis was performed using Quantum 2000 (Physical Electronics. Inc.) (acceleration voltage: 0.5 to 15 keV, 300 W, energy resolution: about 1.0 eV, minimum analysis area: 10 micro, sputter rate: 0.1 nm/min).

The content of carbon, nitrogen, oxygen and magnesium was analyzed through the XPS analysis, and the results are shown in Table 2 below.

division C (atomic %) N (atomic %) O (atomic %) Mg (atomic %) Reference Example 1 GQD (powder) 81.19 1.91 16.90 - Manufacturing example 1 hard mask
(MgPc:GQD = 1:4 wt) 81.68 3.71 14.09 0.52

In Table 2, MgPc represents a complex of Formula 6.

Referring to Table 2, it can be seen that the hard mask of Preparation Example 1 has a reduced oxygen content and an increased carbon content compared to the hard mask of Reference Example 1. According to Preparation Example 1 using the hard mask having such a composition, a hard mask having improved stability and etching selectivity could be manufactured.

evaluation example 3: etching resistance

1) Production example 1-9

The etching resistance was evaluated by measuring the difference in thickness of the hard mask before and after dry etching using the hard mask manufactured according to Production Examples 1-9 and Reference Example 1, and calculating the etching rate according to Equation 1 below. The etching resistance evaluation results are shown in Table 3 below.

[Equation 1]

Etch rate = (initial hardmask thickness - hardmask thickness after etching) / etch time (seconds)

division Etch rate (nm/sec) Manufacturing example 1 0.74 Production example 2 0.72 Manufacturing example 3 0.78 Manufacturing example 4 0.77 Production example 5 0.72 Production example 6 0.73 Manufacturing example 7 0.73 Production example 8 0.74 Production example 9 0.75 Reference Example 1 0.85

Referring to Table 3, it was found that according to Production Examples 1-9, the etching rate was lower than that of Reference Example 1 and the etching selectivity increased. From this, it can be seen that the hard mask composition used in Example 1 has improved etching resistance compared to the case of Reference Example 1.

evaluation example 4: scanning electron microscope

The substrate on which the hard mask was manufactured according to Preparation Example 1 was analyzed using a scanning electron microscope (SEM), and the analysis results are shown in FIG. 4 .

Referring to this, it was confirmed that a hard mask containing the composite of Formula 6 (MgPc) and graphene quantum dots (GQDs) was formed in a uniform thin film on the silicon oxide film of the silicon substrate.

Although one embodiment has been described above, it is not limited thereto, and various modifications and implementations are possible within the scope of the claims and the detailed description of the invention and the accompanying drawings, and this also falls within the scope of the invention.

1: graphene quantum dots 2: functional group
10, 20: Substrate 11a, 21a: Etch film pattern
12a, 22a: hard mask pattern 13a: photoresist pattern

Claims (25)

It includes a complex represented by Formula 1 and a solvent,
The hard mask composition further includes at least one selected from a two-dimensional carbon nanostructure, a zero-dimensional carbon nanostructure, a precursor thereof, and a derivative thereof,
The two-dimensional carbon nanostructure is at least one selected from graphene, graphene quantum dots, reduced graphene oxide, derivatives thereof, and heteroatom derivatives thereof,
A hard mask composition wherein the zero-dimensional carbon nanostructure is at least one selected from fullerene, boron buckyball, carborane, and derivatives thereof:
[Formula 1]

In Formula 1, X is C(R ₁₁ ) or N,
R ₁ 내지 R ₈ 및 R ₁₁ 은 서로 독립적으로 수소, 치환 또는 비치환된 C1-C20 알킬기, 치환 또는 비치환된 C1-C20 알콕시기, 치환 또는 비치환된 C2-C20 알케닐기, 치환 또는 비치환된 C2-C20 알키닐기, 치환 또는 비치환된 C6-C20 아릴기, 치환 또는 비치환된 C6-C20 아릴옥시기, 치환 또는 비치환된 C2-C20 헤테로아릴기, 치환 또는 비치환된 C2-C20 헤테로아릴옥시기, 치환 또는 비치환된 C4-C20 탄소고리기, 치환 또는 비치환된 C4-C20 탄소고리옥시기, 치환 또는 비치환된 C2-C20 헤테로고리기, 할로겐 원자, 시아노기, 하이드록시기, 이미드기, 카르보닐기, 에폭시기, 에폭시기 함유 작용기, -C(=O)R, -C(=O)NH ₂ , -C(=O)OR, -(CH ₂ ) _n COOH(n=1 내지 10의 정수임) 및 -N(R ₉ )(R ₁₀ )중에서 선택되고, 또는 R ₁ 및 R ₂ , R ₃ 및 R ₄ , R ₅ 및 R ₆ , R ₇ 및 R ₈ 은 서로 독립적으로 연결되어 고리를 형성할 수 있고,
R is hydrogen, C1-C20 alkyl group, C2-C20 alkenyl group, C2-C20 alkynyl group, C6-C20 aryl group, C2-C20 heteroaryl group, or C2-C20 heteroaryloxy group,
R ₉ and R ₁₀ are each independently hydrogen, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C6-C20 aryl group, a C2-C20 heteroaryl group, or a C2-C20 heteroaryloxy group;
M is an element selected from Groups 2 to 11 and Group 14 or an oxide thereof. According to claim 1,
In Formula 1, R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , R ₇ and R ₈ are independently connected to each other to form an unsubstituted or substituted C6 to C20 aromatic ring A hardmask composition. According to claim 1,
A hard mask composition in which the complex represented by Formula 1 is a complex represented by Formula 2 below or a complex represented by Formula 3 below:
[Formula 2]

In Formula 2, M is at least one element selected from Fe, Ni, Co, Mn, Mg, Rh, Os, Ru, Mo, Cr, Zn, Ti, Zr, Si, and Cu, or an oxide thereof;
R ₁ 내지 R ₈ 은 서로 독립적으로 수소, 치환 또는 비치환된 C1-C20 알킬기, 치환 또는 비치환된 C1-C20 알콕시기, 치환 또는 비치환된 C2-C20 알케닐기, 치환 또는 비치환된 C2-C20 알키닐기, 치환 또는 비치환된 C6-C20 아릴기, 치환 또는 비치환된 C6-C20 아릴옥시기, 치환 또는 비치환된 C2-C20 헤테로아릴기, 치환 또는 비치환된 C2-C20 헤테로아릴옥시기, 치환 또는 비치환된 C4-C20 탄소고리기, 치환 또는 비치환된 C4-C20 탄소고리옥시기, 치환 또는 비치환된 C2-C20 헤테로고리기, 할로겐 원자, 시아노기, 하이드록시기, 이미드기, 카르보닐기, 에폭시기, 에폭시기 함유 작용기, -C(=O)R, -C(=O)NH ₂ ,-C(=O)OR, -(CH ₂ ) _n COOH(n=1 내지 10의 정수임) 및 -N(R ₉ )(R ₁₀ )중에서 선택되고, 또는 R ₁ 및 R ₂ , R ₃ 및 R ₄ , R ₅ 및 R ₆ , R ₇ 및 R ₈ 은 서로 독립적으로 연결되어 치환된 또는 비치환된 C6 내지 C20의 방향족 고리를 형성하며,
R is hydrogen, C1-C20 alkyl group, C2-C20 alkenyl group, C2-C20 alkynyl group, C6-C20 aryl group, C2-C20 heteroaryl group, or C2-C20 heteroaryloxy group,
R ₉ and R ₁₀ are each independently hydrogen, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C6-C20 aryl group, a C2-C20 heteroaryl group, or a C2-C20 heteroaryloxy group;
[Formula 3]

In Formula 3, M is at least one selected from Fe, Ni, Co, Mn, Mg, Rh, Os, Ru, Mo, Cr, Zn, Ti(=O), Zr(=O), Si and Cu,
R ₁ 내지 R ₈ 은 서로 독립적으로 수소, 치환 또는 비치환된 C1-C20 알킬기, 치환 또는 비치환된 C1-C20 알콕시기, 치환 또는 비치환된 C2-C20 알케닐기, 치환 또는 비치환된 C2-C20 알키닐기, 치환 또는 비치환된 C6-C20 아릴기, 치환 또는 비치환된 C6-C20 아릴옥시기, 치환 또는 비치환된 C2-C20 헤테로아릴기, 치환 또는 비치환된 C2-C20 헤테로아릴옥시기, 치환 또는 비치환된 C4-C20 탄소고리기, 치환 또는 비치환된 C4-C20 탄소고리옥시기, 치환 또는 비치환된 C2-C20 헤테로고리기, 할로겐 원자, 시아노기, 하이드록시기, 이미드기, 카르보닐기, 에폭시기, 에폭시기 함유 작용기, -C(=O)R, -C(=O)NH ₂ ,-C(=O)OR, -(CH ₂ ) _n COOH(n=1 내지 10의 정수임) 및 -N(R ₉ )(R ₁₀ )중에서 선택되고,
R ₁₁ is selected from hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C6-C20 aryloxy group, a hydroxy group, a carboxyl group, -C(=O)R, -C(=O)OR, and -N(R ₉ )(R ₁₀ );
R is hydrogen, C1-C20 alkyl group, C2-C20 alkenyl group, C2-C20 alkynyl group, C6-C20 aryl group, C2-C20 heteroaryl group, or C2-C20 heteroaryloxy group,
R ₉ and R ₁₀ are each independently hydrogen, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C6-C20 aryl group, a C2-C20 heteroaryl group, or a C2-C20 heteroaryloxy group. According to claim 1,
A hardmask composition in which the complex represented by Formula 1 is a complex represented by Formula 4, a complex represented by Formula 4a, a complex represented by Formula 5a, or a complex represented by Formula 5b:
[Formula 4]

In Formula 4, M is at least one selected from among Fe, Ni, Co, Mn, Mg, Rh, Os, Ru, Mo, Cr, Zn, Ti(=O), Zr(=O), Si and Cu,
[Formula 4a]

In Formula 4a, M is at least one selected from Fe, Ni, Co, Mn, Mg, Rh, Os, Ru, Mo, Cr, Zn, Ti(=O), Zr(=O), Si and Cu,
R is a monosubstituted or polysubstituted substituent, and is a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, a C2-C20 heteroaryl group, a C2-C20 heteroaryloxy group, a hydroxyl group, -C(=O)OH, -C(=O)OR ₁ (R ₁ is a C-10 alkyl group, a C2-C10 alkenyl group, or C 6-C20 aryl group), -NH ₂ , -N(R ₂ )(R ₃ ) (R ₂ and R ₃ is independently of each other a C1-C10 alkyl group or a C6-C20 aryl group), -(CH ₂ ) _n COOH (n = an integer of 1 to 10), -CONH ₂ , a cyano group, selected from an epoxy group-containing functional group,
[Formula 5a]

In Formula 5a, M is at least one selected from among Fe, Ni, Co, Mn, Mg, Rh, Os, Ru, Mo, Cr, Zn, Ti(=O), Zr(=O), Si and Cu,
R ₁₁ is a substituted C6-C20 aryl group;
[Formula 5b]

In Formula 5b, M is at least one selected from Fe, Ni, Co, Mn, Mg, Rh, Os, Ru, Mo, Cr, Zn, Ti(=O), Zr(=O), Si, and Cu. According to claim 1,
A hardmask composition in which the complex represented by Formula 1 is at least one selected from the complexes represented by Formula 6a, Formula 7a, and Formula 8a:
[Formula 6a] [Formula 7a]

[Formula 8a

In Formulas 6a, 7a, and 8, R is a monosubstituted or polysubstituted substituent, for example, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, a C2-C20 heteroaryl group, a C2-C20 heteroaryloxy group, a hydroxyl group, -C(=O)OH, -C(=O)OR ₁ (R ₁ is C-1 0 alkyl group, C2-C10 alkenyl group or C6-C20 aryl group), -NH ₂ , -N(R ₂ )(R ₃ ) (R ₂ and R ₃ is independently of each other a C1-C10 alkyl group or a C6-C20 aryl group), -(CH ₂ ) _n COOH (n = an integer from 1 to 10), -CONH ₂ , a cyano group, and an epoxy group-containing functional group. According to claim 1,
A hard mask composition in which the composite represented by Chemical Formula 1 is at least one selected from among the composites represented by Chemical Formulas 6 to 12:
[Formula 6] [Formula 7]

[Formula 8] [Formula 9]

[Formula 10] [Formula 11]

[Formula 12]
According to claim 1,
The content of the composite is 5 to 50 parts by weight based on 100 parts by weight of the hard mask composition. delete delete According to claim 1,
The two-dimensional carbon nanostructure has a size of 1 to 50 nm, and a hard mask composition of 300 layers or less. According to claim 1,
A hard mask composition in which a mixing weight ratio of the composite represented by Formula 1 and at least one selected from a two-dimensional carbon nanostructure and a zero-dimensional carbon nanostructure is 1:99 to 99:1. According to claim 1,
The two-dimensional carbon nanostructure is a graphene quantum dot having a size of 1 to 10 nm,
A hard mask composition having at least one functional group selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group, an epoxy group, an amine group, and an imide group at an end of the graphene quantum dots. According to claim 1,
The hardmask composition of claim 1, wherein the two-dimensional carbon nanostructure is OH-functionalized graphene quantum dots (OH-functionalized GQD) or COOH-functionalized graphene quantum dots (COOH-functionalized GQD). According to claim 1,
The solvent is water, methanol, isopropanol, ethanol, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dichloroethane, dichlorobenzene, dimethylsulfoxide, aniline, propylene glycol, propylene glycol diacetate, methoxy propanediol, diethylene glycol, acetylacetone, cyclohexanone, γ-butyrolactone, nitromethane, tetrahydrofuran, nitrobenzene, Butyl nitrite, methyl cellosolve, ethyl cellosolve, diethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, methyl ethyl ketone, methyl isoketone, hydroxymethyl cellulose, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether ( A hard mask composition comprising at least one selected from propyleneglycol monomethyl ether (PGME), cyclohexanone, ethyl lactate, and heptane. According to claim 1,
The hard mask composition may include a first material selected from an aromatic ring-containing monomer and a polymer containing a repeating unit including an aromatic ring-containing monomer;
at least one second material selected from the group consisting of hexagonal boron nitride, chalcogenide-based materials, and precursors thereof; or
A hard mask composition further comprising a mixture of the first material and the second material. According to claim 15,
A hard mask composition in which the aromatic ring-containing monomer and the polymer containing repeating units including the aromatic ring-containing monomer are at least one selected from a monomer represented by Chemical Formula 13 and a monomer represented by Chemical Formula 14:
[Formula 13]

In Formula 13, R is a mono-substituted or multi-substituted substituent and is hydrogen, a halogen atom, a hydroxyl group, an isocyanate group, a glycidyloxy group, a carboxyl group, an aldehyde group, an amino group, a siloxane group, an epoxy group, an imino group, a urethane group, an ester group, an epoxy group, an amide group, an imide group, an acrylic group, a methacrylic group, an unsubstituted or substituted C1-C30 saturated organic group And at least one selected from the group consisting of unsubstituted or substituted C1-C30 unsaturated organic groups,
[Formula 14]
AL-A'
In Formula 14, A and A' are identically or differently to each other, a monovalent organic group derived from one selected from monomers represented by Formula 13, and
L은 링커(linker)로서 단일결합을 나타내거나 치환 또는 비치환된 C1-C30 알킬렌기, 치환 또는 비치환된 C2-C30 알케닐렌기, 치환 또는 비치환된 C2-C30 알키닐렌기, 치환 또는 비치환된 C7-C30 아릴렌알킬렌기, 치환 또는 비치환된 C6-C30 아릴렌기, 치환 또는 비치환된 C2-C30 헤테로아릴렌기, 치환 또는 비치환된 C2-C30 헤테로아릴렌알킬렌기, 치환 또는 비치환된 C1-C30 알킬렌옥시기, 치환 또는 비치환된 C7-C30 아릴렌알킬렌옥시기, 치환 또는 비치환된 C6-C30 아릴렌옥시기, 치환 또는 비치환된 C2-C30 헤테로아릴렌옥시기, 치환 또는 비치환된 C2-C30 헤테로아릴렌알킬렌옥시기 -C(=O)- 및 -SO ₂ -로 이루어진 군으로부터 선택된다.
A substituted C1-C30 alkylene group, a substituted C2-C30 alkenylene group, a substituted C2-C30 alkynylene group, a substituted C7-C30 arylenealkylene group, a substituted C6-C30 arylene group, a substituted C2-C30 heteroarylene group, a substituted C2-C30 heteroarylenealkylene group, a substituted C1-C30 alkyleneoxy group, a substituted C7-C30 aryl The enealkyleneoxy group, the substituted C6-C30 aryleneoxy group, the substituted C2-C30 heteroaryleneoxy group, the substituted C2-C30 heteroarylenealkyleneoxy group is selected from a halogen atom, a hydroxyl group, an isocyanate group, a glycidyloxy group, a carboxyl group, an aldehyde group, an amino group, a siloxane group, an epoxy group, an imino group, a urethane group, an ester group, an epoxy group, an amide group, an imide group, an acryl group, and a methacryl group. may be substituted with one or more substituents. According to claim 15,
A hard mask composition in which the aromatic ring-containing monomer is at least one selected from compounds represented by Chemical Formulas 17a to 17c:
[Formula 17a]

[Formula 17b]

[Formula 17c]

In Formula 17a, 17b or 17c, L ¹ to L ⁴ are each independently a single bond or a substituted or unsubstituted C1 to C6 alkylene group. According to claim 15,
A hard mask composition in which the aromatic ring-containing monomer is at least one selected from compounds represented by Chemical Formulas 17d to 17f:
[Formula 17d] [Formula 17e]

[Formula 17f]
A first step of forming a film to be etched on a substrate;
a second step of supplying the hard mask composition of claim 1 to an upper portion of the film to be etched to form a hard mask including a reaction product of the coating and heat treatment of the hard mask composition;
a third step of forming a photoresist layer on the hard mask;
a fourth step of forming a hard mask pattern including a reaction product of the coating and heat treatment of the hard mask composition using the photoresist layer as an etching mask; and
and a fifth step of etching the film to be etched using the hard mask pattern as an etching mask. According to claim 19,
A method of forming a pattern in which heat treatment is performed during or after coating the hard mask composition on an upper portion of the film to be etched. According to claim 20,
The method of forming a pattern in which the heat treatment is carried out at a temperature of 1000 ° C or less. According to claim 19,
The hard mask composition supplied in the second step
It is prepared by mixing the complex represented by Formula 1 and a solvent; or
A method for forming a pattern prepared by mixing the composite represented by Formula 1 with at least one selected from two-dimensional carbon nanostructures, zero-dimensional carbon nanostructures, and precursors thereof, and a solvent. According to claim 19,
The method of forming a pattern having a thickness of the hard mask of 10 nm to 10,000 nm. A hard mask comprising a product obtained by coating and heat-treating the hard mask composition of claim 1. The method of claim 24,
The hard mask i) includes a complex represented by Formula 1, or
ii) A hard mask comprising a composite represented by Formula 1 below and at least one selected from a two-dimensional carbon nanostructure, a zero-dimensional carbon nanostructure, and derivatives thereof:
[Formula 1]

In Formula 1, X is C(R ₁₁ ) or N,
R ₁ 내지 R ₈ 및 R ₁₁ 은 서로 독립적으로 수소, 치환 또는 비치환된 C1-C20 알킬기, 치환 또는 비치환된 C1-C20 알콕시기, 치환 또는 비치환된 C2-C20 알케닐기, 치환 또는 비치환된 C2-C20 알키닐기, 치환 또는 비치환된 C6-C20 아릴기, 치환 또는 비치환된 C6-C20 아릴옥시기, 치환 또는 비치환된 C2-C20 헤테로아릴기, 치환 또는 비치환된 C2-C20 헤테로아릴옥시기, 치환 또는 비치환된 C4-C20 탄소고리기, 치환 또는 비치환된 C4-C20 탄소고리옥시기, 치환 또는 비치환된 C2-C20 헤테로고리기, 할로겐 원자, 시아노기, 하이드록시기, 이미드기, 카르보닐기, 에폭시기, 에폭시기 함유 작용기, -C(=O)R, -C(=O)NH ₂ ,-C(=O)OR, -(CH ₂ ) _n COOH(n=1 내지 10의 정수임) 및 -N(R ₉ )(R ₁₀ )중에서 선택되고, 또는 R ₁ 및 R ₂ , R ₃ 및 R ₄ , R ₅ 및 R ₆ , R ₇ 및 R ₈ 은 서로 독립적으로 연결되어 고리를 형성할 수 있고,
R is hydrogen, C1-C20 alkyl group, C2-C20 alkenyl group, C2-C20 alkynyl group, C6-C20 aryl group, C2-C20 heteroaryl group, or C2-C20 heteroaryloxy group,
R ₉ and R ₁₀ are each independently hydrogen, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C6-C20 aryl group, a C2-C20 heteroaryl group, or a C2-C20 heteroaryloxy group;
M is selected from elements of groups 2 to 11 and 14 or oxides thereof.