TW201809885A - Composition for hard mask comprises a copolymer of at least one repeating unit selected from the group consisting of chemical formula 1-1 and 1-2 and a solvent - Google Patents

Abstract

The invention provides a composition for a hard mask, which comprises a copolymer of at least one repeating unit selected from the group consisting of chemical formula 1-1 and 1-2, and a solvent. In the chemical formula 1-1, Ar1 and Ar2 are each independently a divalent arenediyl having 6 to 30 carbon atoms. R1 is an alkyl with 1 to 6 carbon atoms or an aryl having 6 to 35 carbon atoms; Ar1, Ar2 and R1 can each be independently replaced by an alkyl, a hydroxyl, a methoxyl or a phenyl having 1 to 6 carbon atoms, wherein n is an integer from 1 to 190. In the chemical formula as shown in 1-2, Ar1 and Ar2 are each independently a divalent arenediyl having 6 to 30 carbon atoms. R2 is a hydrogen atom or an alkyl with 1 to 6 carbon atoms. Ar1 and Ar2 can each be independently replaced by an alkyl, a hydroxyl, a methoxy or a phenyl having 1 to 6 carbon atoms, wherein n is an integer from 1 to 190.

Description

Composition for hard mask

The present invention relates to a composition for a hard mask.

In the microelectronics industry and industrial fields such as microstructures (for example, micromechanics, magnetoresist magnetic heads, etc.), there is a continuing need to reduce the size of the structure shape. In addition, in the microelectronics industry, there are requirements for reducing the size of microelectronic devices and providing more circuits for a given chip size.

In order to reduce the size, effective lithography is essential.

For a typical photolithography process, first, a resist is coated on the underlying material, and then a radiation exposure is performed to form a resist layer. Next, the developing solution for the resist layer is developed to form a patterned resist layer, and a substance existing in the opening portion of the patterned resist layer is etched to transfer the pattern to the underlying material. After the transfer is completed, a photoresist is exposed in a patterned manner to form a patterned resist layer. Next, an image is developed by contacting the exposed resist layer with an arbitrary substance (typically, an aqueous alkali developing solution). Next, the substance existing in the opening of the patterned resist layer is etched to transfer the pattern to the underlying material. After the transfer is completed, the remaining resist layer is removed.

In order to minimize the reflectivity between the resist layer and the underlying material, In most of the above-mentioned photolithography processes, anti-refractive coating (ARC) is used to increase the resolution. However, during the process of etching the anti-reflective coating after patterning, the resist layer is also consumed in large quantities, and it may be necessary to add patterning in the subsequent etching step.

In other words, in the case of a part of the lithographic imaging process, the used resist sometimes does not have sufficient resistance to the etching step sufficient to effectively transfer a predetermined pattern to the underlying material. Therefore, for the case where an ultra-thin resist layer using a resist material is required to be extremely thin, the case where the substrate to be etched is thick, the case where a deep etching depth is required, or a specific lower layer material needs to be used. In the case of an etchant, a resist underlayer film is used.

The resist underlayer film functions as an intermediate layer between the resist layer and an underlying material that can be patterned from the patterned resist by transfer. The resist underlayer film needs to be resistant to patterning. The etching process required for the resist layer to receive the pattern and transfer the pattern to the underlying material.

In order to form such an underlayer film, many materials have been tried, but improvements to the underlayer film composition continue to be required.

Conventionally, materials for forming an underlayer film have been difficult to apply to a substrate, and therefore, for example, chemical or physical vapor deposition, a special solvent, or high-temperature firing have been used, but these have been costly. Therefore, in recent years, research is being conducted on an underlayer film composition that can be applied by a spin coating method without performing high-temperature firing.

In addition, research is ongoing on the following underlayer film compositions: The resist layer formed on the upper part can be easily etched selectively as a mask, and particularly when the lower layer is a metal layer, it is necessary to pattern the lower layer with the lower layer film as a mask. The etching process is resistant.

Korean Laid-Open Patent No. 10-2010-0082844 discloses a technology regarding a resist underlayer film forming composition.

Prior art literature Patent literature

Korean Published Patent No. 10-2010-0082844

An object of the present invention is to provide a hard mask composition capable of forming a resist underlayer film (hard mask) excellent in heat resistance and coating uniformity.

A composition for a hard mask, comprising a copolymer and a solvent, the copolymer comprising at least one kind of repeating unit selected from the group consisting of the following Chemical Formula 1-1 and Chemical Formula 1-2,

(Wherein Ar ₁ and Ar ₂ are each independently a divalent aromatic hydrocarbon diaryl group (Arenediyl) having 6 to 30 carbon atoms, and R ₁ is an alkyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 35 carbon atoms (Aryl), each of the aforementioned Ar ₁ , Ar ₂ and R ₁ may be further substituted with an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a methoxy group or a phenyl group, and n is an integer from 1 to 190),

(Wherein Ar ₁ and Ar ₂ are each independently a divalent aromatic hydrocarbon diyl group having 6 to 30 carbon atoms, R ₂ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the aforementioned Ar ₁ and Ar ₂ are each independent Ground may be further substituted with an alkyl, hydroxy, methoxy or phenyl group having 1 to 6 carbon atoms, n being an integer from 1 to 190).

2. The composition for a hard mask according to point 1, in the chemical formula 1-1 or the chemical formula 1-2, the Ar ₁ and the Ar ₂ are each independently selected from the following chemical formula a-1 to the following At least one selected from the group consisting of a group represented by chemical formula a-7, and the above-mentioned R ₁ is at least one selected from the group consisting of a group represented by the following chemical formula b-1 to the following chemical formula b-7,

(In the above chemical formula a-7, Ra is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkenyl or alkynyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 30 carbon atoms)

(In the above chemical formula b-7, Ra is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkenyl or alkynyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 30 carbon atoms).

3. The composition for a hard mask according to point 1, wherein the copolymer further comprises a repeating unit of the following Chemical Formula 2,

(Wherein, Ar ₃ carbon atoms, a divalent arene diyl group having 6 to 35, Ar ₄ carbon atoms, an aryl group having 6 to 35, the above-described Ar ₃ and Ar each independently may be C ₄ atoms 1-6 Alkyl, hydroxy, methoxy or phenyl are further substituted, n is an integer from 1 to 190).

4. The composition for a hard mask according to point 3, wherein in the above Chemical Formula 2, the Ar ₃ is selected from the group consisting of a group represented by the following Chemical Formula a-1 to the following Chemical Formula a-7. At least one, in the above Chemical Formula 2, the Ar ₄ is at least one selected from the group consisting of a group represented by the following Chemical Formula b-1 to the following Chemical Formula b-7,

(In the above chemical formula a-7, Ra is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkenyl or alkynyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 30 carbon atoms),

(In the above chemical formula b-7, Ra is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkenyl or alkynyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 30 carbon atoms).

5. The composition for a hard mask according to point 3, wherein the copolymer is a compound produced by condensing an aromatic hydrocarbon compound having 6 to 35 carbon atoms with a compound of the following chemical formula p-1 Adding at least one compound selected from the group consisting of a compound of the following chemical formula p-2 and a compound of the chemical formula p-3 to the prepolymer produced by the reaction,

(In the formula, Ar ₄ is an aryl group having 6 to 35 carbon atoms, Ar ₂ is a divalent aromatic hydrocarbon diyl group having 6 to 35 carbon atoms, and R ₁ is an alkyl group having 1 to 6 carbon atoms or 6 carbon atoms. Aryl groups from 35 to 35, R ₂ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the above-mentioned aromatic compound, Ar ₂ , Ar ₄ , R _1, and R ₂ are each independently an alkyl group having 1 to 6 carbon atoms Radical, hydroxy, methoxy or phenyl).

6. The composition for a hard mask according to point 1, wherein the content of the repeating unit of the chemical formula 1-1 in the copolymer is 5 to 80 mole%.

7. The composition for a hard mask according to point 1, wherein the content of the repeating unit of the chemical formula 1-2 is 2 to 20 mole% in the copolymer.

8. The composition for a hard mask according to point 1, wherein a content of a copolymer including at least one kind of repeating unit selected from the group consisting of the aforementioned Chemical Formula 1-1 and Chemical Formula 1-2 in the total weight of the composition It is 5 to 15% by weight, and the content of the above-mentioned solvent is 85 to 95% by weight.

9. The hard mask composition according to point 1, further comprising at least one of a crosslinking agent and a catalyst.

The hard mask composition of the present invention can form a hard mask (resist underlayer film) excellent in heat resistance and coating uniformity.

An embodiment of the present invention relates to a hard mask composition capable of forming a heat-resistant composition by including a copolymer and a solvent containing at least one type of repeating unit selected from the group consisting of Chemical Formula 1-1 and Chemical Formula 1-2. Resist underlayer film (hard mask) with excellent properties and coating uniformity.

Hereinafter, specific embodiments of the present invention will be described. However, this specific embodiment is merely an example, and the present invention is not limited thereto.

In the present invention, when a compound or resin represented by a chemical formula isomers, the compound or resin represented by a related chemical formula means a representative chemical formula including the isomers.

<Composition for Hard Mask>

Copolymer (A) containing at least one repeating unit selected from the group consisting of Chemical Formula 1-1 and Chemical Formula 1-2

The composition for a hard mask of the present invention includes a copolymer (A) and a solvent (B), and the copolymer (A) includes at least one repeating unit selected from the group consisting of the following Chemical Formula 1-1 and Chemical Formula 1-2,

(Wherein Ar ₁ and Ar ₂ are each independently a divalent aromatic hydrocarbon diyl group having 6 to 30 carbon atoms, and R ₁ is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 35 carbon atoms, as described above. Ar ₁ , Ar ₂ and R ₁ each independently may be further substituted with an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a methoxy group, or a phenyl group, and n is an integer from 1 to 190),

(Wherein, Ar ₁ and Ar ₂ each independently represent a divalent aromatic hydrocarbon having a carbon number of 6 to 30-diyl, R ₂ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, said Ar ₁ and Ar ₂ each independently Ground may be further substituted with an alkyl, hydroxy, methoxy or phenyl group having 1 to 6 carbon atoms, n being an integer from 1 to 190).

In the present invention, the copolymer (A) containing at least one type of repeating unit selected from the group consisting of the aforementioned Chemical Formula 1-1 and Chemical Formula 1-2 can make a hard mask formed from the hard mask composition of the present invention. The cover exhibits excellent heat resistance and coating uniformity.

From such a point of view, preferably, in the above Chemical Formula 1-1 or the aforementioned Chemical Formula 1-2 according to an embodiment of the present invention, each of the Ar ₁ and Ar ₂ may be independently selected from the following Chemical Formulas a-1 to At least one of the group consisting of the group represented by the following chemical formula a-7,

(In the above chemical formula a-7, Ra is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkenyl or alkynyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 30 carbon atoms).

In addition, from the aspect of the above effects, preferably, in the above Chemical Formula 1-1 or the aforementioned Chemical Formula 1-2 according to an embodiment of the present invention, the R ₁ may be selected from the following Chemical Formula b-1 to the following Chemical Formula b At least one of the group consisting of the group represented by -7,

(In the above chemical formula b-7, Ra is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkenyl or alkynyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 30 carbon atoms).

According to need, the copolymer (A) according to an embodiment of the present invention may further include a repeating unit of the following Chemical Formula 2,

(Wherein Ar ₃ is a divalent aromatic hydrocarbon diyl group having 6 to 35 carbon atoms, Ar ₄ is an aryl group having 6 to 35 carbon atoms, and each of the above Ar ₃ and Ar ₄ may be independently 1 to 6 carbon atoms. Alkyl, hydroxy, methoxy or phenyl are further substituted, n is an integer from 1 to 190).

From the standpoint that the formed hard mask exhibits excellent heat resistance and coating uniformity, preferably, in the above Chemical Formula 2, the Ar ₃ may be selected from the following Chemical Formula a-1 to the following Chemical Formula a- At least one of the group consisting of 7, in the above chemical formula 2, the above Ar ₄ may be at least one selected from the group consisting of the following chemical formula b-1 to the following chemical formula b-7,

(In the above chemical formula a-7, Ra is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkenyl or alkynyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 30 carbon atoms),

[Chemical Formula b-4]

(In the above chemical formula b-7, Ra is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkenyl or alkynyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 30 carbon atoms).

According to an embodiment of the present invention, the copolymer (A) containing at least one repeating unit selected from the group consisting of the above-mentioned chemical formulas 1-1 and 1-2 can be obtained by using an aromatic hydrocarbon compound having 6 to 35 carbon atoms and A prepolymer produced by a condensation reaction of a compound of the following chemical formula p-1 is produced by adding at least one compound selected from the group consisting of a compound of the chemical formula p-2 and a compound of the chemical formula p-3,

(In the formula, Ar ₄ is an aryl group having 6 to 35 carbon atoms, Ar ₂ is a divalent aromatic hydrocarbon diyl group having 6 to 35 carbon atoms, and R ₁ is an alkyl group having 1 to 6 carbon atoms or 6 carbon atoms. Aryl groups from 35 to 35, R ₂ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the above-mentioned aromatic compound, Ar ₂ , Ar ₄ , R _1, and R ₂ are each independently an alkyl group having 1 to 6 carbon atoms Radical, hydroxy, methoxy or phenyl).

When the copolymer (A) according to an embodiment of the present invention is produced by the above method, the reactivity can be controlled, and the molecular weight adjustment and physical property control of the copolymer (A) can be easily performed.

In addition, since two reactions (a prepolymer production reaction and an addition reaction of at least one compound selected from the group consisting of a compound of p-2 and a compound of chemical formula p-3) can be performed under the same conditions, it can be easily performed. Manufacturing, and can reduce manufacturing costs.

On the other hand, if the compound of p-1 and the compound of p-2, or the compound of p-1 and the compound of formula p-3 are not sequentially added as described above, but are added simultaneously, the polymer is synthesized simultaneously. Gelation is also carried out, so that Solubility in solvents may decrease.

On the other hand, when the above-mentioned aromatic compound is further substituted with a functional group capable of efficiently supplying electrons, the production of the copolymer (A) becomes easy. For example, as the electron donor, it is preferably further substituted by a hydroxyl group or a methoxy group. Substitution, more preferably may be further substituted by a hydroxyl group.

In one aspect of the present invention, the aromatic hydrocarbon compound having 6 to 35 carbon atoms may be at least one compound selected from the group consisting of the following chemical formula ar-1 to the following chemical formula ar-5,

(In the above chemical formula ar-5, Ra is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkenyl or alkynyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 30 carbon atoms).

The compound of the above-mentioned chemical formula p-1 according to an aspect of the present invention may be, for example, at least one compound selected from the group consisting of the following chemical formulas p-1-1 to p-1-4.

The compound of the above-mentioned chemical formula p-2 according to an aspect of the present invention may be, for example, at least one compound selected from the group consisting of the following chemical formulas p-2-1 to p-2-5.

The compound of the above-mentioned chemical formula p-3 according to an embodiment of the present invention may be, for example, at least one compound selected from the group consisting of the following chemical formulas p-3-1 to p-3-3.

The content of the repeating unit of the chemical formula 1-1 according to an embodiment of the present invention may be 5 to 80 mol% in the copolymer (A). When the above range is satisfied, the formed hard mask can exhibit excellent heat resistance and coating uniformity.

On the other hand, the content of the repeating unit of the chemical formula 1-2 according to an aspect of the present invention may be 2 to 20 mole% in the copolymer (A). When the above range is satisfied, the formed hard mask can exhibit excellent heat resistance and coating uniformity.

An embodiment of the present invention includes a compound selected from the group consisting of Chemical Formula 1-1 and Chemical The copolymer (A) of at least one repeating unit in the group consisting of Formulas 1-2 may have a weight average molecular weight according to the n value described above. Specifically, for example, the weight average molecular weight of the copolymer (A) may be 1,000 to 10,000, and preferably 2,000 to 7,000.

Polydispersity index (PDI, Polydispersity index) of a copolymer (A) containing at least one repeating unit selected from the group consisting of Chemical Formula 1-1 and Chemical Formula 1-2 [weight average molecular weight (Mw) / number average molecular weight (Mn )] Is preferably 1.3 to 6.0, and more preferably 1.5 to 4.0.

If the above-mentioned polydispersity index [weight average molecular weight (Mw) / number average molecular weight (Mn)] is within the above range, copolymerization including at least one repeating unit selected from the group consisting of the above-mentioned chemical formula 1-1 and chemical formula 1-2 Since the effect by the object (A) becomes more excellent, it is preferable.

The content of the copolymer (A) containing at least one type of repeating unit selected from the group consisting of Chemical Formula 1-1 and Chemical Formula 1-2 according to an embodiment of the present invention is not particularly limited as long as it can achieve the purpose of the present invention. For example, The total weight of the composition may be 5 to 15% by weight, and when the above range is satisfied, the effects of the present invention described above can be effectively exhibited. If the content of the copolymer (A) including at least one repeating unit selected from the group consisting of Chemical Formula 1-1 and Chemical Formula 1-2 in the total weight of the composition is less than 5% by weight, it may be difficult to apply the desired coating If the coating thickness is over 15% by weight, the uniformity of coating in the liquid phase may decrease.

Solvent (B)

As long as the solvent according to an embodiment of the present invention is copolymerized with at least one repeating unit selected from the group consisting of the above-mentioned chemical formula 1-1 and chemical formula 1-2, The organic solvent having sufficient solubility (A) is not particularly limited, and examples thereof include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether, PGME), cyclohexanone, ethyl lactate, γ-butyrolactone (GBL), acetyl acetone, and the like, preferably propylene glycol monomethyl ether acetate.

The content of the solvent (B) according to an embodiment of the present invention is not particularly limited as long as it can achieve the purpose of the present invention. The composition of the present invention may include a group selected from the group consisting of Chemical Formula 1-1 and Chemical Formula 1-2 in addition to The balance of the reaction component and other additives of the copolymer (A) of at least one of the repeating units is included. For example, in the case where only the copolymer (A) containing at least one repeating unit selected from the group consisting of Chemical Formula 1-1 and Chemical Formula 1-2 is used in the composition, the solvent may be 85 in the total weight of the composition To 95% by weight, when the above range is satisfied, the effects of the present invention described above can be effectively expressed.

Crosslinking agent and catalyst

In addition, if necessary, the hard mask composition according to an embodiment of the present invention may further include at least one of a crosslinking agent and a catalyst.

The above-mentioned cross-linking agent can cross-link the repeating unit of the polymer by heating in the reaction using a generated acid to perform a catalyst action, as long as it is capable of performing a catalyst action using the generated acid with a copolymer ( The hydroxyl group-reactive crosslinking agent of A) is not particularly limited. As a representative example of such a cross-linking agent, a group selected from the group consisting of melamine, amino resin, glycoluril compound, and double epoxy compound can be used. Any of the groups.

By further including the above-mentioned crosslinking agent, the curing characteristics of the hard mask composition can be further enhanced.

Specific examples of the cross-linking agent include etherified amino resins such as methylated or butylated melamine (for example, N-methoxymethyl-melamine or N-butoxymethyl) -Melamine), methylated or butylated urea resin (Cymel U-65 resin or UFR 80 resin as specific examples), and a glycoluril derivative represented by the following chemical formula L-1 (as Specific examples include Powderlink 1174), and bis (hydroxymethyl) -p-cresol compound) represented by Chemical Formula L-2. In addition, a double epoxy-based compound represented by the following Chemical Formula L-3 and a melamine-based compound represented by the following Chemical Formula L-4 can also be used as a crosslinking agent.

[Chemical formula L-4]

As the catalyst, an acid catalyst or a basic catalyst can be used.

As the acid catalyst, a heat-activated acid catalyst can be used. As an example of the acid catalyst, an organic acid such as p-toluene sulfonic acid monohydrate can be used, and a TAG (thermal acid generator) having storage stability can be mentioned Department of compounds. Thermal acid generators are acid generator compounds that release an acid during heat treatment. For example, pyridinium p-toluene sulfonate, 2,4,4,6-tetrabromocyclohexadienone, and benzene can be used. Evening tosylate, 2-nitrobenzyltosylate, alkyl ester of organic sulfonic acid, and the like.

As the basic catalyst, any one selected from NH ₄ OH or ammonium hydroxide represented by NR ′ ₄ OH (R ′ is an alkyl group) can be used.

In addition, other photosensitive catalysts known in the field of resist technology can be used as long as they have compatibility with other components of the antireflection composition.

When the above-mentioned crosslinking agent is included, the content of the crosslinking agent may be 0.001 to 50 parts by weight, preferably 0.1 to 20 parts by weight, and more preferably 100 parts by weight of the copolymer (A). It may be 1 to 20 parts by weight. In addition, when the catalyst is included, the content of the catalyst may be 0.001 to 50 parts by weight, preferably 0.1 to 20 parts by weight, and more preferably 100 parts by weight of the copolymer (A). It is 1 to 20 parts by weight.

When the content of the cross-linking agent is in the above range, it is possible to obtain appropriate cross-linking characteristics while maintaining the optical characteristics of the formed underlayer film.

In addition, when the content of the catalyst is in the above range, appropriate cross-linking characteristics can be obtained, and the acidity that affects storage stability can be appropriately maintained.

additive

If necessary, the composition for a hard mask of the present invention may further contain additives such as a surfactant. As the surfactant, an alkylbenzenesulfonate, an alkylpyridinium salt, a polyethylene glycol, a quaternary ammonium salt, or the like can be used, but is not limited thereto. At this time, the content of the surfactant may be 1 to 30 parts by weight relative to 100 parts by weight of the copolymer (A). When the content of the surfactant is in the above range, it is possible to obtain appropriate cross-linking characteristics while maintaining the optical characteristics of the formed underlayer film.

In the following, in order to help understand the present invention, preferred embodiments are provided, but these embodiments merely illustrate the present invention, and do not limit the scope of the accompanying patent application. Various embodiments can be carried out within the scope of the present invention and technical ideas Alterations and modifications are obvious to those skilled in the art, and such variations and modifications naturally fall within the scope of the accompanying patent application.

Examples and Comparative Examples

The composition for hard masks of the composition and content (weight%) shown in the following Tables 1 and 2 was manufactured.

A-1: Yu You , (1: 0.7 mole ratio) added to the prepolymer produced by the condensation reaction (acid catalyst: p-toluenesulfonic acid (5 mole% relative to the aromatic alcohol compound)) (Relative to every 1 mole 0.3 mol) (copolymer weight average molecular weight: 3,800)

A-2: Yu You , (1: 0.7 mole ratio) condensation reaction (acid catalyst: p-toluenesulfonic acid (5 mole% relative to aromatic alcohol compound)) added to the prepolymer produced (Relative to every 1 mole 0.3 mol) (copolymer weight average molecular weight: 5,500)

A-3: Yu You (1: 0.7 mole ratio) added to the prepolymer produced by the condensation reaction (acid catalyst: p-toluenesulfonic acid (5 mole% relative to the aromatic alcohol compound)) (Relative to every 1 mole 0.3 mol) (copolymer weight average molecular weight: 6,200)

A-4: Yu You , (1: 0.7 mole ratio) condensation reaction (acid catalyst: p-toluenesulfonic acid (5 mole% relative to aromatic alcohol compound)) added to the prepolymer produced (Relative to every 1 mole 0.3 mol) (copolymer weight average molecular weight: 5,800)

A-5: Yu Yong , (1: 0.7 mole ratio) added to the prepolymer produced by the condensation reaction (acid catalyst: p-toluenesulfonic acid (5 mole% relative to the aromatic alcohol compound)) (Relative to every 1 mole 0.3 mol) (copolymer weight average molecular weight: 7,600)

A-6: Yu Yong (1: 0.7 mole ratio) added to the prepolymer produced by the condensation reaction (acid catalyst: p-toluenesulfonic acid (5 mole% relative to the aromatic alcohol compound)) (Relative to every 1 mole 0.3 mol) (copolymer weight average molecular weight: 7,600)

A-7: Yu Yong , (1: 0.9 mole ratio) added to the prepolymer produced by the condensation reaction (acid catalyst: p-toluenesulfonic acid (5 mole% relative to the aromatic alcohol compound)) (Relative to every 1 mole Copolymer (0.1 mol) (weight average molecular weight: 3,800)

A-8: Yu You , (1: 0.9 mole ratio) added to the prepolymer produced by the condensation reaction (acid catalyst: p-toluenesulfonic acid (5 mole% relative to the aromatic alcohol compound)) (Relative to every 1 mole Copolymer (0.1 mol) (weight average molecular weight: 5,500)

A-9: Yu Yong , (1: 0.9 mole ratio) added to the prepolymer produced by the condensation reaction (acid catalyst: p-toluenesulfonic acid (5 mole% relative to the aromatic alcohol compound)) (Relative to every 1 Copolymer (0.1 mol) (weight average molecular weight: 6,200)

A-10: Yu Yong , (1: 0.9 mole ratio) added to the prepolymer produced by the condensation reaction (acid catalyst: p-toluenesulfonic acid (5 mole% relative to the aromatic alcohol compound)) (Relative to every 1 mole Copolymer (0.1 mol) (weight average molecular weight: 5,800)

A-11: Yu You (1: 0.9 mole ratio) added to the prepolymer produced by the condensation reaction (acid catalyst: p-toluenesulfonic acid (5 mole% relative to the aromatic alcohol compound)) (Relative to every 1 mole Copolymer (0.1 mol) (weight average molecular weight: 7,600)

A-12: Simultaneous investment , , (1: 0.9: 0.1 mole ratio), except that a condensation reaction was performed, a copolymer produced in the same manner as in Example 1 (weight average molecular weight: 8,600)

A'-1: by , Copolymer (weight average molecular weight: 2,900) produced by condensation reaction (acid catalyst: p-toluenesulfonic acid (5 mol% relative to aromatic alcohol compound)) of (1: 1 mole ratio)

A'-2: With , Copolymer (weight average molecular weight: 4,700) produced by condensation reaction (acid catalyst: p-toluenesulfonic acid (5 mol% relative to aromatic alcohol compound)) of (1: 1 mole ratio)

A'-3: With Copolymer (weight average molecular weight: 5,500) produced by condensation reaction (acid catalyst: p-toluenesulfonic acid (5 mol% relative to aromatic alcohol compound)) of (1: 1 mole ratio)

A'-4: With , Copolymer (weight average molecular weight: 2,900) produced by condensation reaction (acid catalyst: p-toluenesulfonic acid (5 mol% relative to aromatic alcohol compound)) of (1: 1 mole ratio)

A'-5: With , Copolymer (weight average molecular weight: 4,700) produced by condensation reaction (acid catalyst: p-toluenesulfonic acid (5 mol% relative to aromatic alcohol compound)) of (1: 1 mole ratio)

A'-6: With Copolymer (weight average molecular weight: 5,500) produced by condensation reaction (acid catalyst: p-toluenesulfonic acid (5 mol% relative to aromatic alcohol compound)) of (1: 1 mole ratio)

B-1: Propylene glycol monomethyl ether acetate

C-1: N-methoxymethyl-melamine resin

D-1: pyridinium p-toluenesulfonate

E-1: Triethylene glycol

Experimental example

1. Heat resistance evaluation

The composition was vacuum-dried to remove the solvent, and a part of the sample was taken, and the mass loss rate was measured while increasing the temperature to 800 ° C. by using thermogravimetric analysis (TGA) under nitrogen.

Mass loss rate = {(initial mass-mass at 800 ° C) / initial mass} × 100%

<Heat resistance judgment>

◎: Quality loss rate is less than 10%

○: The mass loss rate is 10% or more and less than 15%

△: The mass loss rate is 15% or more and less than 25%

×: Mass loss rate is 25% or more

2. Coating uniformity

After the composition was dried, it was spin-coated so as to have a thickness of 5 μm, and dried with a hot air dryer at 100 ° C. for 3 minutes, and then the surface was confirmed with the naked eye.

<Coating Uniformity Determination>

○: Unevenness of coating surface was not observed with naked eyes

△: Local unevenness was confirmed with naked eyes

×: Unevenness was observed on the entire surface with naked eyes

With reference to Table 3, it was confirmed that both the heat resistance and the coating uniformity of the examples were excellent, but the coating uniformity of the comparative example was excellent, but the effect on the heat resistance was significantly reduced.

Claims (9)

A composition for a hard mask, comprising a copolymer and a solvent, the copolymer comprising at least one repeating unit selected from the group consisting of the following Chemical Formula 1-1 and Chemical Formula 1-2, In Chemical Formula 1-1, Ar ₁ and Ar ₂ are each independently a divalent aromatic hydrocarbon diyl group (Arenediyl) having 6 to 30 carbon atoms, and R ₁ is an alkyl group having 1 to 6 carbon atoms or 6 to 6 carbon atoms. Aryl (Aryl), Ar ₁ , Ar ₂ and R ₁ each independently may be further substituted with an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a methoxy group or a phenyl group, and n is an integer from 1 to 190, In Chemical Formula 1-2, Ar ₁ and Ar ₂ are each independently a divalent aromatic hydrocarbon diyl group having 6 to 30 carbon atoms, R ₂ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Ar ₁ and Ar ₂ Each of them may be further substituted with an alkyl group, a hydroxyl group, a methoxy group, or a phenyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 190. The composition for a hard mask according to claim 1, wherein in Chemical Formula 1-1 or Chemical Formula 1-2, Ar ₁ and Ar ₂ are each independently selected from the following Chemical Formula a-1 to Chemical Formula a-7 At least one of the group consisting of the represented group, and R ₁ is at least one selected from the group consisting of the group represented by the following chemical formula b-1 to the following chemical formula b-7, In Chemical Formula a-7, Ra is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkenyl or alkynyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 30 carbon atoms, In Chemical Formula b-7, Ra is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkenyl or alkynyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 30 carbon atoms. The composition for a hard mask according to claim 1, wherein the copolymer further comprises a repeating unit of the following chemical formula 2, In Chemical Formula 2, Ar ₃ is a divalent aromatic hydrocarbon diyl group having 6 to 35 carbon atoms, Ar ₄ is an aryl group having 6 to 35 carbon atoms, and each of Ar ₃ and Ar ₄ may be independently 1 carbon atom. Alkyl, hydroxy, methoxy or phenyl are further substituted to 6 and n is an integer from 1 to 190. The composition for a hard mask according to claim 3, wherein in Chemical Formula 2, Ar ₃ is at least one selected from the group consisting of the following Chemical Formula a-1 to the following Chemical Formula a-7, in Chemical Formula 2, Ar ₄ is at least one selected from the group consisting of the following chemical formula b-1 to the following chemical formula b-7, In Chemical Formula a-7, Ra is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkenyl or alkynyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 30 carbon atoms, In Chemical Formula b-7, Ra is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkenyl or alkynyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 30 carbon atoms. The composition for a hard mask according to claim 3, wherein the copolymer is a compound produced by a condensation reaction of an aromatic hydrocarbon compound having 6 to 35 carbon atoms and a compound of the following chemical formula p-1 At least one compound selected from the group consisting of a compound of the following chemical formula p-2 and a compound of the chemical formula p-3 is added to the produced prepolymer, In the formula, Ar ₄ is an aryl group having 6 to 35 carbon atoms, Ar ₂ is a divalent aromatic hydrocarbon diyl group having 6 to 35 carbon atoms, and R ₁ is an alkyl group having 1 to 6 carbon atoms or 6 to 6 carbon atoms. An aryl group of 35, R ₂ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the aromatic compound, Ar ₂ , Ar ₄ , R ₁ and R ₂ are each independently an alkyl group having 1 to 6 carbon atoms, Hydroxyl, methoxy or phenyl is further substituted. The composition for a hard mask according to claim 1, wherein the content of the repeating unit of the chemical formula 1-1 is 5 to 80 mol% in the copolymer. The composition for a hard mask according to claim 1, wherein the content of the repeating unit of the chemical formula 1-2 is 2 to 20 mole% in the copolymer. The hard mask composition according to claim 1, wherein the total weight of the composition includes at least one kind selected from the group consisting of the chemical formula 1-1 and the chemical formula 1-2. The content of the copolymer of the multiple units is 5 to 15% by weight, and the content of the solvent is 85 to 95% by weight. The hard mask composition according to claim 1, further comprising at least one of a crosslinking agent and a catalyst.