KR20210094960A - Copolymer for organic hardmask and composition for organic hardmask - Google Patents

Abstract

Provided are: a copolymer for an organic hard mask in which following (a), (b), (c) and (d) structural units are each independently arranged at random in a molar ratio of 0.05 to 0.45; and a composition for an organic hard mask comprising the same. The definition of a chemical formula 1 is as described in the specification. The copolymer for the organic hard mask of the present invention has excellent solubility in solvents, high etching selectivity and excellent resistance to multi-etching.

Description

A copolymer for an organic hard mask and a composition for an organic hard mask comprising the same

The present invention relates to a copolymer for an organic hard mask having antireflection film properties useful in a lithographic process, and a composition for an organic hard mask comprising the same.

Recently, as the semiconductor industry increasingly requires a miniaturization process, an effective lithography process is essential to realize such ultra-fine technology. 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 hardmask film quality serves as an interlayer that transfers a micropattern of a photoresist to a lower substrate layer through a selective etching process. Therefore, properties such as chemical resistance, heat resistance, and etching resistance are required for the hard mask layer to withstand multiple etching processes. The existing hardmask film quality used was an amorphous carbon layer (ACL) film made by chemical vapor deposition (CVD). There were many inconveniences to use due to photo align problems.

Recently, a spin-on hardmask method of forming a spin-on coating method instead of the chemical vapor deposition method has been introduced. The spin-on coating method forms an organic hardmask composition using an organic polymer material having solubility in a solvent, and the most important characteristic at this time is to form an organic polymer coating film having etching resistance at the same time.

However, the properties for solubility and etching resistance, which are two properties required for such an organic hardmask layer, have a conflicting relationship with each other, and an organic hardmask composition capable of satisfying both of them was needed. Materials introduced into the semiconductor lithography process while satisfying the properties of these organic hardmask materials have been recently introduced (Patent Publication No. 10-2009-0120827, Patent Publication 10-2008-0107210, Patent WO 2013100365 A1), which is hydroxypi These were hardmask materials using an organic hardmask copolymer having an appropriate high molecular weight synthesized by the conventional phenolic resin manufacturing method using hydroxypyrene.

In addition, a composition (Patent Publication No. 10-2012-0038447) in which a novolak resin using carbazole was prepared and used as a resist underlayer was introduced.

However, as the semiconductor lithography process has recently been further refined, in the case of such an organic hard mask material, it is difficult to sufficiently perform a mask role due to the lack of etching selectivity in the etching process compared to the conventional inorganic hard mask material. has been reached Accordingly, there is an urgent need to introduce an organic hardmask material that is more optimized for the etching process.

Republic of Korea Patent Publication No. 10-2012-0038447

An object of the present invention is to provide a copolymer for an organic hard mask having excellent solubility in solvents, high etching selectivity, and sufficient resistance to multi-etching.

Another object of the present invention is to provide an organic hardmask composition that can minimize the reflectivity between the resist and the back surface layer and thus can be usefully used in performing lithographic techniques.

In order to achieve the above object, the present invention

The following (a), (b), (c) and (d) structural units are each independently randomly arranged in a molar ratio of 0.05 to 0.45, and the structures (a), (b), (c) and (d) Provided is a copolymer for an organic hardmask in which the sum of the unit molar ratios is 1:

In the above formula,

X is a substituted or unsubstituted C6 to C30 heteroarylene group,

Y is a C6 to C30 arylene group substituted with one or more hydroxyl groups or a C5 to C30 heteroarylene group substituted with one or more hydroxyl groups,

R ₁ and R ₂ are each independently an absent, substituted or unsubstituted C6 to C30 aromatic ring group or a substituted or unsubstituted C5 to C30 heteroaromatic ring group,

R ₃ is a substituted or unsubstituted C6 to C30 aromatic ring group or a substituted or unsubstituted C5 to C30 heteroaromatic ring group.

Also, the present invention

It provides an organic hard mask composition comprising the copolymer polymer resin for the organic hard mask and an organic solvent.

The copolymer for an organic hard mask of the present invention has excellent solubility in solvents, high etching selectivity, and excellent resistance to multi-etching.

In addition, the organic hardmask composition of the present invention can minimize the reflectivity between the resist and the back surface layer, so it can be usefully used to perform lithographic techniques,

In addition, since the packing density is very high, when forming a thin film, the film density increases and provides very excellent etching resistance,

In addition, the high etch selectivity is high enough to resist multiple etches, so it is possible to provide an excellent lithographic structure,

In addition, it is possible to minimize the reflectivity between the resist and the back surface layer by having a refractive index and absorbance within a useful range as an anti-reflection film in the deep UV region such as ArF (193 nm) and KrF (248 nm) during film formation.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art to which the present invention pertains can easily implement them. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

Unless otherwise defined herein, 'hetero' means containing 1 to 3 heteroatoms selected from N, O, S and P.

Hereinafter, a copolymer for an organic hard mask according to an embodiment of the present invention will be described.

In the present invention, the following (a), (b), (c) and (d) structural units are each independently randomly arranged in a molar ratio of 0.05 to 0.45, and (a), (b), (c) and (d) to a copolymer for an organic hard mask in which the sum of the molar ratios of structural units is 1:

In the above formula,

X is a substituted or unsubstituted C6 to C30 heteroarylene group,

Y is a C6 to C30 arylene group substituted with one or more hydroxyl groups or a C5 to C30 heteroarylene group substituted with one or more hydroxyl groups,

R ₁ and R ₂ are each independently an absent, substituted or unsubstituted C6 to C30 aromatic ring group or a substituted or unsubstituted C5 to C30 heteroaromatic ring group,

R ₃ is a substituted or unsubstituted C6 to C30 aromatic ring group or a substituted or unsubstituted C5 to C30 heteroaromatic ring group.

In the above, "substitution" may be a hydrogen atom substituted with a C1 to C5 alkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, or a hydrocarbon group in which they are combined.

Each of R ₁ and R ₂ may independently be a substituted or unsubstituted aromatic quadrangular ring, a substituted or unsubstituted aromatic pentagonal ring, a substituted or unsubstituted aromatic hexagonal ring, or a fused ring thereof.

R ₃ may be a substituted or unsubstituted aromatic quadrangular ring, a substituted or unsubstituted aromatic pentacyclic ring, a substituted or unsubstituted aromatic hexagonal ring, or a fused ring thereof.

The copolymer for an organic hard mask may be usefully used in a composition for a hard mask, and more preferably, may be usefully used in a composition for an anti-reflection hard mask.

The copolymer for the organic hard mask may be a random copolymer of each constituent monomer.

In addition, the copolymer for an organic hard mask is (a) a structural unit and (b) a structural unit is combined with (c) a structural unit or (d) a structural unit,

The (c) constituent unit and (d) constituent unit may be in a form combined with (a) constituent unit or (b) constituent unit.

In an embodiment of the present invention, it may be preferable that X is selected from the following compounds:

.

.

In one embodiment of the present invention, Y may be preferably selected from the following compounds:

.

.

In an embodiment of the present invention, the structural unit (c) may be preferably selected from the following compounds:

.

.

In one embodiment of the present invention, the structural unit (d) may be preferably selected from the following compounds:

In one embodiment of the present invention, the copolymer is more preferably copolymers 1 to 12 in which the structural units (a), (b), (c) and (d) are configured as follows.

[Copolymer 1]

[Copolymer 2]

[Copolymer 3]

[Copolymer 4]

[Copolymer 5]

[Copolymer 6]

[Copolymer 7]

[Copolymer 8]

[Copolymer 9]

[Copolymer 10]

[Copolymer 11]

[Copolymer 12]

In the copolymers 1 to 12, the molar ratio of the sequentially arranged (a), (b), (c) and (d) structural units may be 0.2 to 0.3, respectively. In particular, the molar ratio of the structural units (a), (b), (c) and (d) may be 0.25, respectively.

The copolymer for an organic hard mask represented by Formula 1 of the present invention may have a weight average molecular weight of 800 to 5,000, more preferably 1,000 to 2,000, and particularly preferably 800 to 1,500.

The weight average molecular weight may be a polystyrene reduced average molecular weight measured using gel permeation chromatography. By having a weight average molecular weight within the above range, the copolymer has excellent polymer solubility, high etching selectivity, and resistance to multi-etching.

Also, the present invention

It relates to an organic hard mask composition comprising the copolymer polymer resin for the organic hard mask and an organic solvent.

Since the description of the copolymer for the organic hard mask is the same as that described above, it will be omitted.

The organic solvent is intended to improve coating properties when coating the composition for an organic hard mask, and it is preferable to use an organic solvent having excellent volatility since it evaporates and disappears after coating is performed. For example, a ketone-type solvent, for example, PGMEA, PMEA, DIBK, etc. may be used, and in addition to these, as a solvent known in the art, any solvent that can be used at or above the process temperature is mixed with one type or two or more types. can be used by

The composition for an organic hard mask may further include a crosslinking agent and an acid catalyst.

As the crosslinking agent, for example, at least one selected from the group consisting of melamine-based, amino-based, glycoluryl-based, and bisepoxy compounds may be used. In another embodiment, a crosslinking agent having at least two crosslinking substituents, for example, methoxymethylated glycouryl, butoxymethylated glycouryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxy A compound such as methylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or butoxymethylated thiourea may be used.

A crosslinking agent having high heat resistance may be used as the crosslinking agent, and for example, a compound containing a crosslinking substituent having an aromatic ring (eg, a benzene ring or a naphthalene ring) in a molecule may be used. The crosslinking agent may have, for example, two or more crosslinking sites.

The acid catalyst is methanesulfonic acid, p-toluene sulfonic acid monohydrate, pyridinium p-toluene sulfonate, 2,4,4,6-tetra It may be at least one selected from the group consisting of bromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and alkyl esters of organic sulfonic acids.

The composition for the organic hard mask includes 1 wt% to 20 wt% of the copolymer for the organic hardmask, 0.1 wt% to 5 wt% of the crosslinking agent, 0.001 wt% to 0.05 wt% of the acid catalyst, and the The remaining amount of the organic solvent may be included.

In addition, unavoidable impurities may be further included.

The organic solvent is preferably contained in an amount of 75 to 98% by weight based on the total weight of the composition.

The hard mask composition may be usefully used in an anti-reflection hard mask composition.

When the polymer resin is included in less than 1 part by weight or in excess of 20 parts by weight in the hard mask composition, it is not preferable because it is difficult to match the exact coating thickness because it becomes less than or exceeds the desired coating thickness.

When the crosslinking agent component is included in an amount of less than 0.1% by weight in the hard mask composition, crosslinking properties may not appear, and when it exceeds 5% by weight, the optical properties of the coating film may be changed due to excessive input.

In addition, when the acid catalyst is included in an amount of less than 0.001% by weight in the hard mask composition, crosslinking properties may not appear well, and when it exceeds 0.05% by weight, it is not preferable because it may affect storage stability due to an increase in acidity due to excessive input. .

Hereinafter, preferred examples and comparative examples of the present invention will be described.

The following examples are intended to illustrate the present invention and should not be construed as limiting the scope of the present invention.

Example 1.

In a round bottom flask, 27.00 g (110.99 mmol) of 9-Phenylcarbazole, 16.00 g (110.99 mmol) of 2-Naphthol, 20 g (110.99 mmol) of fluorenone, and 2-Na After dissolving 17.33 g (110.99 mmol) of ptaldehyde (2-Naphthaldehyde) in 187 g of 1,2-dichloroethane, 5.33 g (55.49 mmol) of methanesulfonic acid was added thereto.

The molecular weight was measured using GPC in the middle of the reaction while the polymerization proceeded while maintaining reflux by increasing the reaction temperature.

After reacting for about 20 hours, the reactant was lowered to 20-30° C., and then 100 ml of dichloromethane and 100 ml of water were added. Then, 5.6 g of triethylamine was added for neutralization.

Then, after extracting the organic layer using a separatory funnel, the extraction process by adding water was repeated twice or more, and the organic layer was concentrated with an evaporator.

40 ml of dichloromethane was added to the obtained compound for dissolution, then dropped into 360 ml of metalol, and the resulting solid was again dissolved in an appropriate amount of PGMEA solvent, and then dropped into an excess of ethanol/water (9:1) cosolvent. caught the sediment.

After drying the resulting solid in a vacuum oven at about 50° C. for about 20 hours, copolymer 1 having a weight average molecular weight (Mw) of 1,100 and including the following monomers was obtained.

[Copolymer 1]

Example 2.

9-Phenylcarbazole 27.00 g (110.99 mmol), 9-Phenanthrol 21.56 g (110.99 mmol), Fluorenone 20 g (110.99 mmol) and 2- After dissolving 17.33 g (110.99 mmol) of naphthaldehyde in 200 g of 1,2-Dichloroethane, 5.33 g (55.49 mmol) of methanesulfonic 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 copolymer including copolymer 2 having a weight average molecular weight of 1,200 and including the following monomers.

[Copolymer 2]

Example 3.

In a round bottom flask, 27.00 g (110.99 mmol) of 9-Phenylcarbazole, 24.22 g (110.99 mmol) of (1-hydroxypyrene) 1-Hydroxypyrene, 20 g (110.99 mmol) of fluorenone, and After dissolving 17.33 g (110.99 mmol) of 2-Naphthaldehyde in 207 g of 1,2-Dichloroethane, 5.33 g (55.49 mmol) of methanesulfonic acid was added thereto. added.

After polymerization in the same manner as in Example 1, the polymer was purified and dried in a vacuum oven to obtain a copolymer containing copolymer 3 having a weight average molecular weight of 1,100 and containing the following monomers.

[Copolymer 3]

Example 4.

In a round bottom flask, 27.00 g (110.99 mmol) of 9-Phenylcarbazole, 4,4'-(9H-fluorene-9,9-diyl)diphenol (4,4′-(9-Fluorenylidene) )diphenol) 38.89g (110.99mmol), Fluorenone 20g (110.99mmol) and 2-Naphthaldehyde 17.33g (110.99mmol) 1,2-dichloroethane (1,2- Dichloroethane) was dissolved in 241 g, and 5.33 g (55.49 mmol) of methanesulfonic 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 copolymer including copolymer 4 having a weight average molecular weight of 1,300 and containing the following monomers.

[Copolymer 4]

Example 5.

In a round bottom flask, 9-(1-Naphthyl)carbazole 32.56g (110.99mmol), 2-Naphthol 16.00g (110.99mmol), Fluorenone (Fluorenone) ) 20g (110.99mmol) and 17.33g (110.99mmol) of 2-naphthaldehyde were dissolved in 200g of 1,2-dichloroethane and then methanesulfonic acid 5.33 g (55.49 mmol) was added.

After polymerization in the same manner as in Example 1, the polymer was purified and dried in a vacuum oven to obtain a copolymer containing copolymer 5 having a weight average molecular weight of 1,200 and containing the following monomers.

[Copolymer 5]

Example 6.

9- (1-Naphthyl) carbazole (9- (1-Naphthyl) carbazole) 32.56 g (110.99 mmol), 9-phenantrol (9-Phenanthrol) 21.56 g (110.99 mmol), fluorenone ( Fluorenone) 20g (110.99mmol) and 2-naphthaldehyde 17.33g (110.99mmol) were dissolved in 213g 1,2-Dichloroethane, and then methanesulfonic acid ) 5.33 g (55.49 mmol) was added.

After polymerization in the same manner as in Example 1, the polymer was purified and dried in a vacuum oven to obtain a copolymer containing copolymer 6 having a weight average molecular weight of 1,100 and containing the following monomers.

[Copolymer 6]

Example 7.

9-(1-Naphthyl)carbazole (9-(1-Naphthyl)carbazole) 32.56g (110.99mmol), (1-hydroxypyrene)1-Hydroxypyrene 24.22g (110.99mmol), Fluoro 20g (110.99mmol) of Fluorenone and 17.33g (110.99mmol) of 2-Naphthaldehyde were dissolved in 220g of 1,2-Dichloroethane and then methanesulfonic acid ( Methanesulfonic acid) 5.33 g (55.49 mmol) was added.

After polymerization in the same manner as in Example 1, the polymer was purified and dried in a vacuum oven to obtain a copolymer including copolymer 7 having a weight average molecular weight of 1,100 and containing the following monomers.

[Copolymer 7]

Example 8.

32.56g (110.99mmol) of 9-(1-naphthyl)carbazole, 4,4'-(9H-fluorene-9,9-diyl)diphenol in a round bottom flask (4,4′-(9-Fluorenylidene)diphenol) 38.89g (110.99mmol), Fluorenone 20g (110.99mmol) and 2-Naphthaldehyde 17.33g (110.99mmol) 1, After dissolving in 241 g of 2-dichloroethane (1,2-Dichloroethane), 5.33 g (55.49 mmol) of methanesulfonic 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 copolymer containing copolymer 8 having a weight average molecular weight of 1,200 and containing the following monomers.

[Copolymer 8]

Example 9.

In a round bottom flask, 22.45 g (110.99 mmol) of Pyrene, 16.00 g (110.99 mmol) of 2-Naphthol, 20 g (110.99 mmol) of Fluorenone and 2-naphtaldehyde (2-Naphthol) Naphthaldehyde) 17.33 g (110.99 mmol) was dissolved in 177 g of 1,2-dichloroethane, and 5.33 g (55.49 mmol) of methanesulfonic 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 copolymer including copolymer 9 having a weight average molecular weight of 1,100 and containing the following monomers.

[Copolymer 9]

Example 10.

In a round bottom flask, 22.45 g (110.99 mmol) of Pyrene, 21.56 g (110.99 mmol) of 9-Phenanthrol, 20 g (110.99 mmol) of Fluorenone and 2-naphthaldehyde (2 -Naphthaldehyde) 17.33 g (110.99 mmol) was dissolved in 190 g of 1,2-dichloroethane, and 5.33 g (55.49 mmol) of methanesulfonic 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 copolymer containing copolymer 10 having a weight average molecular weight of 1,100 and containing the following monomers.

[Copolymer 10]

Example 11.

In a round-bottom flask, 22.45 g (110.99 mmol) of Pyrene, 24.22 g (110.99 mmol) of (1-hydroxypyrene) 1-Hydroxypyrene, 20 g (110.99 mmol) of Fluorenone and 2-naphthaldehyde 17.33g (110.99mmol) of (2-Naphthaldehyde) was dissolved in 196g of 1,2-dichloroethane, and 5.33g (55.49mmol) of methanesulfonic 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 copolymer containing copolymer 11 having a weight average molecular weight of 1,200 and containing the following monomers.

[Copolymer 11]

Example 12.

In a round bottom flask, 22.45 g (110.99 mmol) of pyrene, 38.89 g of 4,4'-(9H-fluorene-9,9-diyl)diphenol (4,4′-(9-Fluorenylidene)diphenol) (110.99mmol), 20g (110.99mmol) of Fluorenone and 17.33g (110.99mmol) of 2-Naphthaldehyde were dissolved in 230g of 1,2-Dichloroethane. Then, 5.33 g (55.49 mmol) of methanesulfonic 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 copolymer containing copolymer 12 having a weight average molecular weight of 1,300 and containing the following monomers.

[Copolymer 12]

Comparative Example 1.

In a round bottom flask, 13.50 g (55.49 mmol) of 9-Phenylcarbazole, 8.00 g (55.49 mmol) of 2-Naphthol, and 20 g (110.99 mmol) of fluorenone were 1,2 - After dissolving in 97 g of dichloroethane (1,2-Dichloroethane), 5.33 g (55.49 mmol) of methanesulfonic acid was added thereto.

The molecular weight was measured using GPC in the middle of the reaction while the polymerization proceeded while maintaining reflux by increasing the reaction temperature.

After reacting for about 20 hours, the reactant was lowered to 20-30° C., and then 100 ml of dichloromethane and 100 ml of water were added. Then, 5.6 g of triethylamine was added for neutralization.

Then, after extracting the organic layer using a separatory funnel, the process of extraction by adding water was repeated twice or more, and the organic layer was concentrated with an evaporator.

40 ml of dichloromethane was added to the obtained compound for dissolution, then dropped into 360 ml of metalol, and the resulting solid was again dissolved in an appropriate amount of PGMEA solvent, and then dropped into an excess of ethanol/water (9:1) cosolvent. caught the sediment.

After drying the resulting solid in a vacuum oven at about 50° C. for about 20 hours, a copolymer A having a weight average molecular weight (Mw) of 1,100 and containing the following monomers was obtained.

[Copolymer A]

Comparative Example 2.

In a round bottom flask, 13.50 g (55.49 mmol) of 9-Phenylcarbazole, 8.00 g (55.49 mmol) of 2-Naphthol, and 17.33 g (110.99) of 2-Naphthaldehyde mmol) was dissolved in 91 g of 1,2-dichloroethane, and 5.33 g (55.49 mmol) of methanesulfonic acid was added thereto.

After polymerization in the same manner as in Comparative Example 1, the polymer was purified and dried in a vacuum oven to obtain a copolymer B having a weight average molecular weight of 1,100 and including the following monomers.

[Copolymer B]

Preparation of a composition for an anti-reflective organic hard mask comprising the copolymer of Examples 1 to 12 and Comparative Examples 1 to 2

Each of the copolymers prepared in Examples 1 to 12 and Comparative Examples 1 to 2 was weighed 0.9 g each, and 0.1 g of a glycoluryl compound crosslinking agent (Powderlink 1174) and a urethane curing catalyst, pyridinium P-toluene sulfonate (Pyridinium) 1 mg of P-toluene sulfonate) was dissolved in 9 g of propylene glycol monomethyl ether acetate (PGMEA), filtered, and antireflection organic hard mask containing the copolymers of Examples 1 to 12 and Comparative Examples 1 to 2, respectively A composition was prepared.

Sample solutions prepared by the copolymers of Examples 1 to 12 and Comparative Examples 1 to 2 were spin-coated on a silicon wafer, respectively, and a temperature of 240° C. was applied for 60 seconds, and a film having a thickness of 3000 Å was obtained. Eggplant was formed with a composition film for an antireflection organic hard mask comprising the copolymer of Examples 1 to 12 and Comparative Examples 1 to 2.

Test Example 1: Evaluation of the etch resistance of the copolymers of Examples 1 to 12 and Comparative Examples 1 to 2

After spin-on coating the composition for an organic hard mask comprising the copolymer of Examples 1 to 12 and Comparative Examples 1 to 2 on a silicon wafer, heat treatment at 400° C. for 90 seconds on a hot plate to a thickness of 3,000 Å A thin film was formed.

Then, the thin film _{was dry-etched for 60 seconds and 100 seconds using N 2} /O ₂ mixed gas and CF _x gas, respectively, and then the thickness of the thin film was measured again. The bulk etch rate (BER) was calculated by Equation 1 below from the thickness and etching time of the thin film before and after dry etching, and is shown in Table 1 below.

[Equation 1]

(Initial thin film thickness - thin film thickness after etching) / Etching time (Å/s)

Etch rate (CF _x , Å/s) Etch rate (N ₂ /O ₂ , Å/s) Example 1 17.41 49.33 Example 2 17.61 49.62 Example 3 18.21 50.12 Example 4 16.59 48.47 Example 5 16.85 48.41 Example 6 17.69 49.11 Example 7 18.04 49.85 Example 8 16.57 48.15 Example 9 17.32 49.30 Example 10 16.11 48.88 Example 11 17.26 49.03 Example 12 16.91 48.50 Comparative Example 1 19.21 51.98 Comparative Example 2 20.81 52.68

Test Example 2: Evaluation of optical properties of copolymers of Examples 1 to 12 and Comparative Examples 1 to 2

After spin-on coating the composition for an organic hard mask comprising the copolymer of Examples 1 to 12 and Comparative Examples 1 to 2 on a silicon wafer, heat treatment at 400° C. for 90 seconds on a hot plate to a thickness of 3,000 Å A thin film was formed.

At this time, refractive index n and extinction coefficient k for the formed 　 films were respectively obtained. The device used is an Ellipsometer (J. A. Woollam) and the measurement results are shown in Table 2.

sample type Optical Characteristics (193nm) Optical Characteristics (248nm) refractive index (n) extinction coefficient (k) refractive index (n) extinction coefficient (k) Example 1 1.53 0.70 1.71 0.53 Example 2 1.52 0.69 1.70 0.52 Example 3 1.53 0.70 1.72 0.52 Example 4 1.51 0.68 1.71 0.51 Example 5 1.50 0.71 1.73 0.53 Example 6 1.50 0.69 1.71 0.54 Example 7 1.52 0.70 1.70 0.51 Example 8 1.54 0.69 1.71 0.52 Example 9 1.51 0.69 1.72 0.52 Example 10 1.51 0.68 1.71 0.53 Example 11 1.52 0.69 1.73 0.52 Example 12 1.53 0.70 1.72 0.51 Comparative Example 1 1.51 0.69 1.71 0.54 Comparative Example 2 1.50 0.70 1.73 0.51

As confirmed in Table 2, as a result of the evaluation, the composition for an organic hard mask comprising the copolymer of Examples 1 to 12 and Comparative Examples 1 to 2 was obtained at ArF (193 nm) and KrF (248 nm) wavelengths. It was confirmed that it had a refractive index and absorbance usable as an anti-reflection film. Generally, the refractive index range of the material used for the semiconductor anti-reflection film is about 1.4 to 1.8, and the important thing is the extinction coefficient. Accordingly, the composition for an organic hard mask according to the present embodiments may be used as an anti-reflection film.

In the above, the present invention has been described in detail only with respect to the described embodiments, but it is obvious to those skilled in the art that various changes and modifications are possible within the scope of the technical spirit of the present invention, and it is natural that such variations and modifications belong to the appended claims.

Claims (15)

The following (a), (b), (c) and (d) structural units are each independently randomly arranged in a molar ratio of 0.05 to 0.45, and the structures (a), (b), (c) and (d) A copolymer for an organic hard mask in which the sum of the unit molar ratios is 1:

In the above formula,
X is a substituted or unsubstituted C6 to C30 heteroarylene group,
Y is a C6 to C30 arylene group substituted with one or more hydroxyl groups or a C5 to C30 heteroarylene group substituted with one or more hydroxyl groups,
R ₁ and R ₂ are each independently an absent, substituted or unsubstituted C6 to C30 aromatic ring group or a substituted or unsubstituted C5 to C30 heteroaromatic ring group,
R ₃ is a substituted or unsubstituted C6 to C30 aromatic ring group or a substituted or unsubstituted C5 to C30 heteroaromatic ring group. According to claim 1,
wherein R ₁ and R ₂ are each independently a substituted or unsubstituted aromatic quadrangular ring, a substituted or unsubstituted aromatic pentacyclic ring, a substituted or unsubstituted aromatic hexagonal ring, or a fused ring thereof. for copolymers. According to claim 1,
wherein R ₃ is a substituted or unsubstituted aromatic quadrangular ring, a substituted or unsubstituted aromatic pentagonal ring, a substituted or unsubstituted aromatic hexagonal ring, or a fused ring thereof. According to claim 1,
Wherein X is a copolymer for an organic hard mask, characterized in that selected from the following compounds:

According to claim 1,
Wherein Y is a copolymer for an organic hard mask, characterized in that selected from the following compounds:

. According to claim 1,
The (c) structural unit is a copolymer for an organic hard mask, characterized in that selected from the following compounds:

. According to claim 1,
The (d) structural unit is a copolymer for an organic hard mask, characterized in that selected from the following compounds:

According to claim 1,
The copolymer is a copolymer for a hard mask, characterized in that the (a), (b), (c) and (d) structural units are copolymers 1 to 12 configured as follows:
[Copolymer 1]

[Copolymer 2]

[Copolymer 3]

[Copolymer 4]

[Copolymer 5]

[Copolymer 6]

[Copolymer 7]

[Copolymer 8]

[Copolymer 9]

[Copolymer 10]

[Copolymer 11]

[Copolymer 12]

According to claim 1,
In the copolymers 1 to 12, the (a), (b), (c) and (d) structural units have a molar ratio of 0.2 to 0.3, respectively. According to claim 1,
The copolymer for an organic hard mask has a weight average molecular weight of 800 to 5,000. An organic hardmask composition comprising the copolymer polymer resin for an organic hardmask of any one of claims 1 to 10 and an organic solvent. 12. The method of claim 11,
The organic hardmask composition further comprises a crosslinking agent and an acid catalyst. 13. The method of claim 12,
The organic hard mask composition is based on the total weight of the composition,
(a) 1 to 20% by weight of a polymer resin;
(b) 0.1-5% by weight of a crosslinking agent component;
(c) 0.001 to 0.05% by weight of an acid catalyst; and
(d) an organic hard mask composition comprising a residual amount of an organic solvent. 13. The method of claim 12,
The crosslinking agent is a composition for an organic hard mask, characterized in that at least one selected from the group consisting of a melamine resin, an amino resin, a glycoluryl compound and a bisepoxy compound. 13. The method of claim 12,
The acid catalyst is methanesulfonic acid (Methanesulfonic acid), p-toluene sulfonic acid monohydrate (p-toluenesulfonic acid monohydrate), pyridinium p-toluene sulfonate (Pyridinium p-toluene sulfonate), 2,4,4,6-tetrabro A composition for an organic hard mask, characterized in that at least one selected from the group consisting of mocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and an alkyl ester of organic sulfonic acid.