KR20230036203A - A composition of anti-reflective hardmask - Google Patents

Abstract

The present invention provides an anti-reflective hard mask composition which comprises: (a) a copolymer containing a naphthylcarbazole novolak resin represented by following formula 1 or formula 2 or a copolymer blend containing the same; and (b) an organic solvent. According to the present invention, it is possible to provide a lithographic structure with excellent pattern evaluation results due to high etching selectivity compared to an existing organic hard mask and sufficient resistance to multiple etchings.

Description

Hard mask composition for antireflection {A COMPOSITION OF ANTI-REFLECTIVE HARDMASK}

The present invention relates to a hard mask composition having antireflection film properties useful for a lithographic process, an aromatic polymer containing a naphthylcarbazole novolak resin having strong absorption in the ultraviolet wavelength region, and a hard mask comprising the same It's about the composition.

As miniaturization processes are increasingly required in the semiconductor industry, an effective lithographic process is essential to realize these ultra-fine technologies. In particular, the demand for new materials for the hard mask process, which is very essential in the etching process, is increasing.

In general, the hard mask film serves as an intermediate film that transfers a fine pattern of photoresist to a lower substrate layer through a selective etching process. Therefore, the hard mask layer requires properties such as chemical resistance, heat resistance, and etching resistance to withstand multiple etching processes. The existing hard mask film quality used ACL (amorphous carbon layer) film quality made by chemical vapor deposition (CVD) method, but the disadvantages of this are the high unit cost of equipment investment and the particles generated during the process, and the film quality is opaque. It was very inconvenient to use due to photo alignment problems and the like.

Recently, a spin-on hardmask formed by a spin-on coating method has been introduced instead of such a chemical vapor deposition method. In the spin-on coating method, a hard mask composition is formed using an organic polymer material having solubility in a solvent. At this time, the most important characteristic is that an organic polymer coating film having etching resistance should be formed.

However, since solubility and etching resistance, which are two characteristics required for such an organic hard mask layer, are in a conflicting relationship with each other, a hard mask composition capable of satisfying both of them was required. Materials introduced into the semiconductor lithography process while satisfying the characteristics of these organic hard mask materials have recently been introduced (Patent Publication 10-2009-0120827, Patent Publication 10-2008-0107210, Patent WO 2013100365 A1). They were hard mask materials using a copolymer having an appropriate high molecular weight synthesized by a conventional phenol resin manufacturing method using hydroxypyrene.

However, as the recent semiconductor lithographic process undergoes further miniaturization, in the case of organic hard mask materials, it is difficult to sufficiently perform the mask role due to the lack of etching selectivity in the etching process compared to conventional inorganic hard mask materials. it has reached Therefore, the introduction of an organic hard mask material more optimized for the etching process has become urgently needed.

Patent 1: Korean Patent Publication No. 10-2009-0120827, Patent 2: Korean Patent Publication No. 10-2008-0107210, Patent 3: WO 2013100365 A1

An object of the present invention is to provide a hard mask polymer having excellent polymer solubility, high etching selectivity, and sufficient resistance to multiple etching, and a composition including the same.

It is also an object of the present invention to provide a novel hardmask polymer and a composition comprising the same that can be used to perform lithographic techniques as it is capable of minimizing the reflectivity between the resist and the backing layer.

The hard mask composition according to the present invention,

(a) a copolymer or a blend of these copolymers including a naphthylcarbazole novolac resin represented by Formula 1 below; and

(b) organic solvents;

It is an anti-reflection hard mask composition comprising a.

[Formula 1]

In Formula 1, Ar is a C6-C40 aryl group or heterocyclic group, and the aryl group or heterocyclic group may be substituted with a hydroxyl group, a fluorine group, or a nitrile group. R1 and R2 are the same as or different from each other, and are either a hydrogen atom, a C1-C10 alkyl group, a C2-C10 alkenyl group, a C6-C20 aryl group, or a heterocyclic group. Here, R1 and R2 may form a ring together with the carbon atom to which they are bonded. Here, m/(m+n)=0.1 to 1.0, and n/(m+n)=0 to 0.9.

A hard mask composition according to another embodiment of the present invention,

(a) a copolymer or a blend of these copolymers, which is represented by Formula 2 below and includes a naphthylcarbazole novolak resin; and

(b) organic solvents;

It is an anti-reflection hard mask composition comprising a.

[Formula 2]

In Formula 1, m has a range between 3 and 100.

The hard mask composition based on a copolymer containing a naphthylcarbazole novolak resin according to the present invention has an Ohnishi parameter value predicting etch resistance due to a structure in which the carbon content is very high and oxygen is not included in the polymer is very low, which is a very advantageous structure for etch resistance. Since the packing density is very high in terms of the polymer structure, when a thin film is formed, the film density increases and the etching resistance is very excellent. Therefore, it is possible to provide a lithographic structure having excellent pattern evaluation results due to sufficient resistance to multiple etching due to a high etching selectivity compared to conventional organic hard masks.

The hard mask composition based on the naphthylcarbazole novolac resin according to embodiments of the present invention exhibits a useful range of refractive index and absorbance as an antireflection film in the Deep UV region such as ArF (193 nm) and KrF (248 nm) when forming a film. By having it, it is possible to minimize the reflectivity between the resist and the back layer.

The hard mask composition according to the present invention,

(a) a copolymer or a blend of these copolymers including a naphthylcarbazole novolac resin represented by Formula 1 below; and

(b) organic solvents;

It is an anti-reflection hard mask composition comprising a.

[Formula 1]

In Formula 1, Ar is a C6-C40 aryl group or heterocyclic group, and the aryl group or heterocyclic group may be substituted with a hydroxyl group, a fluorine group, or a nitrile group. R1 and R2 are the same as or different from each other, and are either a hydrogen atom, a C1-C10 alkyl group, a C2-C10 alkenyl group, a C6-C20 aryl group, or a C6-C20 heterocyclic group. Here, R1 and R2 may form a ring together with the carbon atom to which they are bonded. Here, m/(m+n)=0.1 to 1.0, and n/(m+n)=0 to 0.9.

The C6~C20 aryl group and the C6~C20 heterocyclic group may be benzene, naphthalene, anthracene, or pyrene.

A hard mask composition according to another embodiment of the present invention,

(a) a copolymer or a blend of these copolymers, which is represented by Formula 2 below and includes a naphthylcarbazole novolak resin; and

(b) organic solvents;

It is an anti-reflection hard mask composition comprising a.

[Formula 2]

In Formula 1, m is 3 to 100.

The weight average molecular weight (Mw) of each of the entire copolymers of Chemical Formulas 1 and 2 may be 1,000 to 50,000, preferably 2,000 to 30,000.

The polymers having the structures of Chemical Formulas 1 and 2 may have, for example, the following forms of Chemical Formula 2 of Chemical Formula 2-1 and the forms of Chemical Formula 1 of Chemical Formulas 2-2 to 2-24.

[Formula 2-1 to 2-20]

The polymers of Chemical Formulas 2-1 to 2-24 may be used in combination with other polymers to improve dissolution properties, coating properties, or curing properties of the entire hard mask composition, and the other polymers may be cresol novolac resins, or It may be aromatic C6-C20 novolak polymeric polymers having a hydroxyl group.

On the other hand, in order to prepare a hard mask composition, the copolymer containing the (a) naphthylcarbazole novolac resin of each of Chemical Formulas 1 and 2 is 1 based on 100 parts by weight of the organic solvent (b) used in the hard mask composition. It is preferably used in ~30% parts by weight. When the polymer prepared from the naphthylcarbazole novolac resin (a) of Chemical Formulas 1 and 2 is used in an amount of less than 1% by weight or more than 30% by weight, the desired coating thickness is less than or exceeds the desired coating thickness, so that the exact coating thickness is adjusted. difficult.

The organic solvent is not particularly limited as long as it has sufficient solubility for the aromatic ring-containing polymer of Formula 1 or Formula 2, and examples thereof include propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone, and ethyl lactate. etc. can be mentioned.

In addition, the antireflective hard mask composition of the present invention may further include (c) a crosslinking agent component and (d) an acid catalyst.

The (c) crosslinking agent component used in the hard mask composition of the present invention is preferably capable of crosslinking the repeating units of the polymer by heating in the reaction catalyzed by the generated acid, and the (d) acid catalyst is thermally activated. It is preferably an acid catalyst that becomes

The cross-linking agent component (c) used in the hard mask composition of the present invention is not particularly limited as long as it can react with the aromatic ring-containing polymer in a manner that can be catalytically functionalized by the resulting acid. Examples of the crosslinking agent include melamine-based, substituted urea-based, and polymer-based materials thereof. Preferably, it is a crosslinking agent having at least two crosslinking substituents, methoxymethylated glycoluril, butoxymethylglycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, Compounds such as methoxymethylation urea, butoxymethylation urea, and methoxymethylation thiourea.

In addition, a crosslinking agent having high heat resistance can be used as the crosslinking agent, and a compound containing a crosslinking substituent having an aromatic ring in the molecule can be preferably used. These compounds may exemplify compounds of the form such as the following structural formula.

As the (d) acid catalyst used in the hard mask composition of the present invention, an organic acid such as p-toluenesulfonic acid monohydrate may be used, and a TAG (Thermal Acid Generator) that promotes storage stability A compound of the system can also be used as a catalyst. TAG is an acid generator compound designed to release acid upon heat treatment, for example, pyridinium P-toluene sulfonate, 2,4,4,6-tetrabromocyclohexadienone, Preference is given to using compounds such as benzoin tosylate, 2-nitrobenzyl tosylate and alkyl esters of organic sulfonic acids.

When the final hardmask composition further comprises (c) a crosslinking agent component and (d) an acid catalyst, the hardmask composition of the present invention is (a) in the form of a naphthylcarbazole novolac resin having strong absorption characteristics in the ultraviolet region. 1 to 30% by weight of a copolymer or a blend of these copolymers, more preferably 3 to 15% by weight, (c) 0.1 to 5% by weight of a crosslinking agent component, more preferably 0.1 to 3% by weight, ( d) 0.001 to 0.05% by weight of an acid catalyst, more preferably 0.001 to 0.03% by weight, and (b) a total of 100% by weight using an organic solvent as the remaining component, preferably 75 to 98% by weight of an organic solvent % is preferred.

Here, when the amount of the naphthylcarbazole novolak resin copolymer is less than 1% by weight or more than 30% by weight, the desired coating thickness is less than or exceeds the desired coating thickness, making it difficult to accurately match the coating thickness.

In addition, when the crosslinking agent component is less than 0.1% by weight, crosslinking properties may not be exhibited, and when it exceeds 5% by weight, optical properties of the coating film may be changed due to excessive input.

In addition, when the acid catalyst is less than 0.001% by weight, crosslinking properties may not be well displayed, and when it exceeds 0.05% by weight, storage stability may be affected due to an increase in acidity due to excessive input.

Hereinafter, the present invention will be described in more detail through examples, but the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Example-1)

After dissolving 14.7 g (50 mmol) of naphthylcarbazole and 1.8 g (60 mmol) of formaldehyde in 50 g of gamma butyrolactone in a 250 mL round flask, 0.6 g of p-toluenesulfonic acid monohydrate was added, followed by polymerization at 80 degrees for 20 hours. did

After polymerization, the reactants are precipitated in an excess of methanol/water (8:2) co-solvent and then neutralized with triethylamine. The resulting precipitate was washed with an excess of methanol for about 1 hour, filtered, and dried in a vacuum oven at 60 degrees for 24 hours to obtain a polymer of Chemical Formula 2-1.

The polymer obtained a high molecular weight average molecular weight (Mw) of 3,600 and a polydispersity (Mw/Mn) of 1.87.

Example-2)

14.7 g (50 mmol) of naphthylcarbazole, 7.2 g (50 mmol) of 1-naphthol, and 3.6 g of formaldehyde were synthesized in the same manner as in Example-1 to synthesize a polymer of Chemical Formula 2-3. After polymer purification, a weight average molecular weight (Mw) of 4,100 and polydispersity (Mw/Mn) of 1.69 were obtained.

Example-3)

14.7 g (50 mmol) of naphthylcarbazole, 10.9 g (50 mmol) of 1-pyrenol, and 3.6 g of formaldehyde were synthesized in the same manner as in Example-1 to synthesize a polymer of Chemical Formula 2-5. After polymer purification, a weight average molecular weight (Mw) of 4,300 and polydispersity (Mw/Mn) of 1.79 were obtained.

Example-4)

14.7 g (50 mmol) of naphthylcarbazole, 17.5 g (50 mmol) of 9,9-bishydroxyphenylfluorene, and 3.6 g of formaldehyde were synthesized in the same manner as in Example-1 to synthesize a polymer of Chemical Formula 2-6. After polymer purification, a weight average molecular weight (Mw) of 4,400 and polydispersity (Mw/Mn) of 1.83 were obtained.

Example-5)

14.7 g (50 mmol) of naphthylcarbazole, 5.9 g (50 mmol) of indole, and 3.6 g of formaldehyde were synthesized in the same manner as in Example-1 to synthesize a polymer of Chemical Formula 2-8. After polymer purification, a weight average molecular weight (Mw) of 5,500 and polydispersity (Mw/Mn) of 1.84 were obtained.

Example-6)

14.7g (50mmol) of naphthylcarbazole, 9.7g (50mmol) of phenylindole, and 3.6g of formaldehyde were synthesized in the same manner as in Example-1 to synthesize a polymer of Chemical Formula 2-9. After polymer purification, a weight average molecular weight (Mw) of 5,100 and polydispersity (Mw/Mn) of 1.85 were obtained.

Example-7)

20.5 g (70 mmol) of naphthylcarbazole, 6.1 g (30 mmol) of pyrene, and 3.6 g of formaldehyde were synthesized in the same manner as in Example-1 to synthesize a polymer of Chemical Formula 2-10. After polymer purification, a weight average molecular weight (Mw) of 4,500 and polydispersity (Mw/Mn) of 1.87 were obtained.

Example-8)

14.7 g (50 mmol) of naphthylcarbazole, 7.2 g (50 mmol) of 1-naphthol, and 1.8 g of formaldehyde and 6.4 g of phenylaldehyde were synthesized in the same manner as in Example-1 to synthesize a polymer of Chemical Formula 2-12. After polymer purification, a weight average molecular weight (Mw) of 3,800 and polydispersity (Mw/Mn) of 1.86 were obtained.

Example-9)

14.7 g (50 mmol) of naphthylcarbazole, 10.9 g (50 mmol) of 1-pyrenol, and 1.8 g of formaldehyde and 6.4 g of phenylaldehyde were synthesized in the same manner as in Example-1 to synthesize a polymer of Chemical Formula 2-13. After polymer purification, a weight average molecular weight (Mw) of 4,300 and polydispersity (Mw/Mn) of 1.89 were obtained.

Example-10)

14.7g (50mmol) of naphthylcarbazole, 17.5g (50mmol) of 9,9-bishydroxyphenylfluorene, and 1.8g of formaldehyde and 6.4g of phenylaldehyde were prepared in the same manner as in Example-1 to obtain the chemical formula 2-14. A polymer was synthesized. After polymer purification, a weight average molecular weight (Mw) of 4,800 and polydispersity (Mw/Mn) of 1.87 were obtained.

Example-11)

14.7 g (50 mmol) of naphthylcarbazole, 5.9 g (50 mmol) of indole, and 1.8 g of formaldehyde and 6.4 g of phenylaldehyde were synthesized in the same manner as in Example-1 to synthesize a polymer of Chemical Formula 2-15. After polymer purification, a weight average molecular weight (Mw) of 5,800 and polydispersity (Mw/Mn) of 1.87 were obtained.

Example-12)

14.7 g (50 mmol) of naphthylcarbazole, 5.9 g (50 mmol) of indole, and 1.8 g of formaldehyde and 9 g of fluorenone were synthesized in the same manner as in Example-1 to synthesize a polymer of Chemical Formula 2-19. After polymer purification, a weight average molecular weight (Mw) of 5,500 and polydispersity (Mw/Mn) of 1.88 were obtained.

Example-13)

14.7 g (50 mmol) of naphthylcarbazole, 7.2 g (50 mmol) of 1-naphthol, and 1.8 g of formaldehyde and 9 g of fluorenone were synthesized in the same manner as in Example-1 to synthesize a polymer of Chemical Formula 2-20. After polymer purification, a weight average molecular weight (Mw) of 5,300 and polydispersity (Mw/Mn) of 1.78 were obtained.

Example-14)

14.7g (50mmol) of naphthylcarbazole, 7.2g (50mmol) of 1-naphthol, and 1.8g of formaldehyde and 9.4g of naphthylaldehyde were synthesized in the same manner as in Example-1 to synthesize a polymer of Chemical Formula 2-21. After polymer purification, a weight average molecular weight (Mw) of 3,300 and polydispersity (Mw/Mn) of 1.88 were obtained.

Example-15)

14.7g (50mmol) of naphthylcarbazole, 5.9g (50mmol) of indole, and 1.8g of formaldehyde and 9.4g of naphthylaldehyde were synthesized in the same manner as in Example-1 to synthesize a polymer of Chemical Formula 2-24. After polymer purification, a weight average molecular weight (Mw) of 3,500 and polydispersity (Mw/Mn) of 1.87 were obtained.

Comparative Example) Synthesis of Phenolic Polymer

35 g (100 mmol) of 9,9-bishydroxyphenylfluorene and 11.7 g (110 mmol) of benzaldehyde were dissolved in 109 g of PGMEA, and then 1 g of concentrated sulfuric acid was added thereto.

After polymerization in the same manner as in Example-1, the polymer was purified and dried in a vacuum oven to obtain a polymer having a weight average molecular weight (Mw) of 3,600.

Preparation of hard mask composition

1 g of the polymer and 300 ppm of the surfactant prepared in Examples 1 to 15 and Comparative Examples were completely dissolved in 7 g of propylene glycol monomethyl ether acetate (PGMEA) and 2 g of cyclohexanone, and then filtered using a 0.1 um Melbrain filter. Thus, samples of Examples 1 to 13 and Comparative Examples were prepared.

Each of the sample solutions prepared in Examples 1 to 15 and Comparative Example was spin-coated on a silicon wafer and baked at 240° C. for 60 seconds to form a film having a thickness of 3000 Å.

At this time, the refractive index n and extinction coefficient k of the formed films were respectively obtained. The equipment used was an ellipsometer (J. A. Woollam), and the measurement results are shown in Table 1.

As a result of the evaluation, it was confirmed that there was a refractive index and absorbance usable as an antireflection film at ArF (193 nm) and KrF (248 nm) wavelengths. In general, the refractive index range of materials used as semiconductor anti-reflection films is about 1.4 to 1.8, and the important thing is the absorption coefficient, and the higher the absorbance, the better. It can be seen that the hard mask composition according to the embodiments can be used as an antireflection film.

sample type Optical properties (193nm) Optical properties (248nm) Refractive index (n) Extinction coefficient (k) Refractive index (n) Extinction coefficient (k) Example 1 1.54 0.44 1.70 0.53 Example 2 1.53 0.45 1.71 0.54 Example 3 1.52 0.55 1.73 0.56 Example 4 1.55 0.53 1.73 0.57 Example 5 1.54 0.56 1.70 0.53 Example 6 1.53 0.55 1.71 0.54 Example 7 1.52 0.58 1.73 0.56 Example 8 1.55 0.59 1.73 0.57 Example 9 1.56 0.54 1.74 0.58 Example 10 1.54 0.51 1.72 0.53 Example 11 1.55 0.53 1.73 0.57 Example 12 1.56 0.52 1.74 0.58 Example 13 1.54 0.50 1.72 0.53 Example 14 1.59 0.42 1.73 0.56 Example 15 1.54 0.43 1.71 0.52 Comparative Example 1.48 0.58 1.95 0.35

Lithographic Evaluation of Antireflective Hardmask Compositions

Each of the sample solutions prepared in Examples 2, 3, and 4 and Comparative Example was spin-coated on an aluminum-coated silicon wafer and baked at 240° C. for 60 seconds to form a coating film having a thickness of 3000 Å.

Coat photoresist for KrF on each of the formed coating films, bake at 110 ° C for 60 seconds, and expose using ASML (XT: 1400, NA 0.93) exposure equipment, respectively, and then TMAH (tetramethyl ammonium hydroxide) as a 2.38 wt% aqueous solution. Each was developed for 60 seconds. Then, as a result of examining each 90 nm line and space pattern using V-SEM, the results shown in Table 2 were obtained. The EL (expose latitude) margin according to the change in the exposure amount and the DoF (depth of focus) margin according to the change in the distance from the light source were considered and recorded in Table 2.

As a result of the pattern evaluation, good results were confirmed in terms of profile or margin, and it was found that the EL margin and DoF margin required in the lithographic pattern evaluation were satisfied.

sample type pattern characteristics EL margin (ΔmJ/energy mJ) DoF margin (μm) pattern shape Example 2 0.3 0.3 cubic Example 3 0.4 0.3 cubic Example 4 0.4 0.4 cubic Comparative Manufacturing Example 0.2 0.2 undercut

Etching Characteristics Evaluation of Antireflective Hard Mask Compositions

In Examples 3, 4, 5 and Comparative Example, the patterned specimens were subjected to dry etching of the lower SiON anti-reflection film (BARC) with a CHF ₃ /CF ₄ mixed gas using PR as a mask, followed by O ₂ /N ₂ mixing Dry etching of the hard mask was performed again using the SiON antireflection film as a mask with gas. Thereafter, the silicon nitride (SiN) film is dry etched using the hard mask as a mask with the CHF ₃ /CF ₄ mixture gas, and then O ₂ ashing and wet strip process for the remaining hard mask and organic materials proceeded.

Immediately after hard mask etching and silicon nitride etching, cross-sections of each specimen were examined with V-SEM, and the results are listed in Table 3. As a result of the etch evaluation, the pattern shapes after hard mask etching and silicon nitride etching did not show bowing in each case and were all good, so that the etching process of the silicon nitride film was well performed due to sufficient resistance to the etching process. confirmed that

Sample Pattern shape (after hard mask etch) Pattern shape (after SiN etching) Example 3 vertical shape vertical shape Example 4 vertical shape vertical shape Example 5 vertical shape vertical shape Comparative Example slightly bowing Boeing shape

Claims (11)

(a) a copolymer or a blend of these copolymers including a naphthylcarbazole novolac resin represented by Formula 1 below; and
(b) organic solvents;
Characterized in that comprising a, anti-reflection hard mask composition.
[Formula 1]

In Formula 1, Ar is a C6-C40 aryl group or heterocyclic group, and the aryl group or heterocyclic group may be substituted with a hydroxyl group, a fluorine group, or a nitrile group. R1 and R2 are the same as or different from each other, and are either a hydrogen atom, a C1-C10 alkyl group, a C2-C10 alkenyl group, a C6-C20 aryl group, or a C6-C20 heterocyclic group. Here, R1 and R2 may form a ring together with the carbon atom to which they are bonded. Here, m/(m+n)=0.1 to 1.0, and n/(m+n)=0 to 0.9. (a) a copolymer or a blend of these copolymers, which is represented by Formula 2 below and includes a naphthylcarbazole novolak resin; and
(b) organic solvents;
Characterized in that it comprises, an anti-reflection hard mask composition
[Formula 2]

In Formula 1, m has a range of 3 to 100. According to claim 1,
An antireflective hard mask composition, characterized in that R1 and R2 are hydrogen atoms. According to claim 1,
An antireflective hard mask composition, characterized in that R1 is a hydrogen atom and R2 is benzene. According to claim 1,
An antireflective hard mask composition, characterized in that R1 is a hydrogen atom and R2 is naphthalene. According to claim 1,
An antireflective hard mask composition, characterized in that R1 and R2 are bonded to each other to have a fullerene structure. According to claim 1 or 2,
The hard mask composition further comprises a crosslinking agent and an acid catalyst component, the anti-reflection hard mask composition. According to claim 7,
The hard mask composition,
(a) 1 to 30% by weight of a copolymer containing the naphthylcarbazole novolac resin of Formula 1 or Formula 2 or a blend of these copolymers;
(b) 0.1 to 5% by weight of a crosslinking agent component;
(c) 0.001 to 0.05% by weight of an acid catalyst; and
(d) An anti-reflection hard mask composition, characterized in that it consists of a total of 100% by weight using an organic solvent as the remaining components. According to claim 7,
The crosslinking agent is methoxymethylated glycoluril, butoxymethylglycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated urea, Anti-reflection hard mask composition, characterized in that at least one selected from the group consisting of oxymethylated thiourea compounds. According to claim 7,
The acid catalyst is p-toluenesulfonic acid monohydrate, pyridinium p-toluene sulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzo An antireflection hard mask composition, characterized in that at least one selected from the group consisting of phosphorus tosylate, 2-nitrobenzyl tosylate and organic sulfonic acid alkyl esters. The copolymer comprising the naphthylcarbazole novolak resin included in the antireflective hard mask composition of claim 1 is characterized in that any one of the following Chemical Formulas 2-2 to 2-24.