KR20200139503A - Compound for hardmask, hardmask composition comprising the same, and method for forming fine patterns of semiconductor device using the hardmask composition - Google Patents

Abstract

The present invention relates to a compound for a hardmask, comprising a polycyclic aromatic compound, to a hardmask composition comprising the compound, and to a method for forming a fine pattern of a semiconductor device using the same. The compound for a hardmask of the present invention has excellent gap-fill performance and excellent heat resistance and etching resistance after curing because it has high solvent solubility applicable to a spin-on coating method.

Description

A compound for a hardmask, a hardmask composition containing the compound, and a method for forming a fine pattern of a semiconductor device using the same TECHNICAL FIELD [COMPOUND FOR HARDMASK, HARDMASK COMPOSITION COMPRISING THE SAME, AND METHOD FOR FORMING FINE PATTERNS OF SEMICONDUCTOR DEVICE USING THE HARDMASK COMPOSITION}

The present invention relates to a hardmask compound, a hardmask composition comprising the compound, and a method for forming a fine pattern of a semiconductor device using the same.

Recently, the semiconductor industry is developing from a pattern of several hundred nanometers to an ultra-fine technology having a pattern of several to tens of nanometers. In order to realize such ultra-fine technology, an effective lithographic technique using photoresist material is essential.

A typical lithographic technique involves forming a material layer on a semiconductor substrate, coating a photoresist layer thereon, exposing and developing to form a photoresist pattern, and then etching the material layer using the photoresist pattern as a mask. do.

On the other hand, as the size of the pattern to be formed gradually decreases, it is not easy to form a fine pattern having a good profile with only the above-described typical lithographic technique.

That is, in order to form a fine pattern, as the refining of the resist pattern proceeds, problems such as a resolution problem or a resist pattern collapse after development are caused.

In order to improve this problem, instead of thinning the resist used as an etching mask, it is called a resist underlayer, a so-called hardmask layer, that can function as a mask during substrate processing between the resist and the semiconductor substrate to be etched. A method of introducing a called layer has been proposed.

The hard mask layer is required to have etching resistance suitable for multiple etching processes so that it can serve as an interlayer that transfers the fine pattern of the photoresist to the layer to be etched through a selective etching process, and a representative example thereof is high etching resistance. It has an amorphous carbon layer is applied.

However, since the amorphous carbon layer is formed by chemical vapor deposition (CVD) using methane gas, ethane gas, and acetylene gas as raw materials, the deposition process is complicated and cumbersome.

Recently, instead of chemical vapor deposition, a spin coating method using a spin on carbon material has been proposed. The spin coating method is advantageous in that it is easy to process and improves gap-fill characteristics and planarization characteristics.

However, in general, a hardmask layer applied by a spin-coating technique tends to have poor etching selectivity compared to a hardmask layer formed by a chemical or physical vapor deposition method.

Accordingly, there is a need to develop a material for a hard mask that can not only be formed by a wet method such as spin coating or screen printing, but can also secure excellent etching resistance and heat resistance after formation.

Korean Patent Publication No. 2017-0116044

An object of the present invention is to provide a hardmask compound comprising a polycyclic aromatic compound having a high carbon content in which at least two or more hydroxy groups are substituted at an asymmetric position with each other.

In addition, in the present invention, by including the hardmask compound, it is intended to provide a hardmask composition having excellent gap-fill performance and excellent heat resistance and etching resistance after curing.

In addition, the present invention is to provide a method for forming a fine pattern of a semiconductor device using the hardmask composition.

In order to achieve the above object, an embodiment of the present invention provides a hardmask compound comprising a polycyclic aromatic compound substituted with at least two hydroxy groups.

The polycyclic aromatic compound may be at least one selected from the group consisting of a compound represented by Formula 1 below and a compound represented by Formula 2 below.

[Formula 1]

In Formula 1,

R ₁ and R ₄ are independent of each other, at least one of which is an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the rest is a hydroxy group (-OH), an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms,

R ₂ , R ₃ , R ₅ and R ₆ are Each independently Hydrogen, an alkyl group having 1 to 10 carbon atoms, or -OR _o , wherein R _o is hydrogen or an alkyl group having 1 to 10 carbon atoms.

[Formula 2]

In Chemical Formula 2,

R ₇ , R _7a , R ₈ and R _8a are independent of each other, of which at least two or more are hydroxy groups (-OH), the remainder is an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the hydroxy group ( -OH) has an asymmetric structure with each other,

R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are Each independently Hydrogen, an alkyl group having 1 to 10 carbon atoms, or -OR _o , wherein R _o is hydrogen or an alkyl group having 1 to 10 carbon atoms,

n and m are each independently an integer of 0 to 3.

Specifically, in the compound represented by Formula 1, R ₁ and R ₄ are independent of each other, at least one of which is an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the rest is a hydroxy group (-OH) or an aromatic having 6 to 20 carbon atoms A hydrocarbon group, and R ₂ , R ₃ , R ₅ and R ₆ are Each independently It is hydrogen or -OR _o , wherein R _o may be hydrogen or an alkyl group having 1 to 10 carbon atoms.

More specifically, in Formula 1, R ₁ and R ₄ are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ₂ and R ₅ are each independently Hydrogen or -OR _o , wherein R _o is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ₃ and R ₆ are each independently It can be hydrogen.

In addition, in the compound represented by Formula 2, R ₇ , R _7a , R ₈ and R _8a are independent of each other, at least two of which are hydroxy groups (-OH), and the rest are aromatic hydrocarbon groups having 6 to 20 carbon atoms. , The hydroxy group (-OH) has an asymmetric structure with each other, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are Each independently Hydrogen or -OR _o , wherein R _o is hydrogen or an alkyl group having 1 to 10 carbon atoms, and n and m may each independently be an integer of 0 to 3.

Specifically, in Formula 2, R ₇ and R ₈ are each independently a hydroxy group (-OH) or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R _7a and R _8a are a hydroxy group (-OH), and R ₉ and R ₁₂ is Each independently Hydrogen, or -OR _o , wherein R _o is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ₁₀ and R ₁₁ are each independently Hydrogen, and n and m may each independently be an integer of 0 to 3.

In addition, in an embodiment of the present invention, it is possible to provide a hardmask composition comprising the compound and a solvent for a hardmask of the present invention.

The hardmask compound may be included in an amount of 1% to 65% by weight based on the total weight of the hardmask composition.

The solvent may be at least one or more selected from the group consisting of ketone solvents, cellosolve solvents, ester solvents, alcohol solvents and aromatic hydrocarbon solvents, and specifically cyclohexanone, propylene glycol monomethyl ether, propylene glycol mono It may be at least one selected from the group consisting of methyl ether acetate, ethyl lactate, methyl hydroxyisobutyrate, 1-methoxy-2-propanol, and anisole.

In addition, in an embodiment of the present invention

Coating the hardmask composition of the present invention on the layer to be etched on the substrate;

Curing the hardmask composition to form a hardmask layer;

Forming a photoresist layer over the hardmask layer;

Exposing and developing the photoresist layer to form a photoresist pattern;

Selectively patterning the hardmask layer using the photoresist pattern as an etching mask; And

It provides a method for forming a pattern of a semiconductor device comprising the step of patterning an etched layer by using the patterned hard mask layer as an etching mask.

In the method of the present invention, the step of coating the hardmask composition may be performed by a spin-on coating method.

In addition, the step of curing the hardmask composition may be performed by heat treatment at 100°C to 500°C.

The method of the present invention may further include forming an anti-reflection layer on the hard mask layer after forming the hard mask layer and before forming the photoresist layer.

According to the present invention, by including a polycyclic aromatic compound in which at least two or more hydroxy groups are substituted at an asymmetric position with each other, it has a high solvent solubility applicable to a spin-on coating method, and is high without additives even at low temperatures. It is possible to provide a hardmask compound capable of securing a crosslink density. In addition, by including this, as well as securing excellent gap-fill performance, it is possible to prepare a hardmask composition having excellent heat resistance and etching resistance after curing. Furthermore, by using this, it is possible to provide a method for finely forming a semiconductor device capable of forming a uniform vertical pattern with a high density.

The following drawings attached to the present specification illustrate preferred embodiments of the present invention, and serve to further understand the technical idea of the present invention together with the content of the above-described invention, so the present invention is limited to the matters described in such drawings. It is limited and should not be interpreted.
1 is an electron microscope (SEM) photograph of a cross section of a hard mask film formed using the hard mask composition for evaluating a gap fill of Example 19-1 in Experimental Example 1. FIG.
FIG. 2 is an electron microscope (SEM) photograph of a cross section of a hard mask film formed by using the hard mask composition for evaluating a gap fill of Comparative Example 3-1 in Experimental Example 1. FIG.
3 is an electron microscope (SEM) photograph of a cross section of a hard mask film formed using the hard mask composition for evaluating a gap fill of Comparative Example 4-1 according to Experimental Example 1. FIG.

Hereinafter, the present invention will be described in more detail.

The terms or words used in this specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

The terms used in the present specification are only used to describe exemplary embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise.

In the present specification, terms such as "comprise", "include" or "have" are intended to designate the presence of implemented features, numbers, steps, components, or a combination thereof, and one or more other features or It is to be understood that the possibility of the presence or addition of numbers, steps, elements, or combinations thereof is not preliminarily excluded.

In this specification, "%" means% by weight unless otherwise indicated.

Prior to describing the present invention, in the description of "carbon number a to b" in the specification, "a" and "b" mean the number of carbon atoms included in a specific functional group. That is, the functional group may include "a" to "b" carbon atoms. For example, the "alkyl group having 1 to 5 carbon atoms" is an alkyl group containing 1 to 5 carbon atoms, that is, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH ₂ (CH ₂ )CH ₃ , -CH(CH ₂ )CH ₂ CH ₃ or -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -.

In conventional semiconductor device manufacturing, in order to implement a spin-on carbon layer for a hard mask film having a high selectivity, a material having a high carbon content was used. However, when the carbon content is increased, the solubility is lowered and the amount of solid content that can be dissolved in the solvent is limited, so it is difficult to form a spin-on carbon layer with a uniform thickness, and a thickness that can secure a sufficient etching selectivity. It was not easy to form.

Accordingly, the inventors of the present invention have conducted research to provide a material for a hardmask having high solubility in organic solvents, excellent gap fill performance, and excellent heat resistance and etching resistance after curing. For compounds with a large number of ), it has been found that these requirements are met.

Therefore, the present inventors have high solvent solubility applicable to a spin-on coating method when at least two or more hydroxy groups contain a polycyclic aromatic compound having a high carbon content substituted at an asymmetric position with each other, It is known that a self-crosslinking reaction is possible, so that a high crosslink density can be secured without additives even at a low temperature, as well as a hard mask composition having excellent heat resistance and etching resistance after curing. And completed the present invention.

Compound for hard mask

In the present specification, a hardmask compound including a polycyclic aromatic compound in which at least two or more hydroxy groups are substituted is provided.

The polycyclic aromatic compound may be at least one selected from the group consisting of a compound represented by Formula 1 below and a compound represented by Formula 2 below.

[Formula 1]

In Formula 1,

R ₁ and R ₄ are independent of each other, at least one of which is an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the rest is a hydroxy group (-OH), an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms,

R ₂ , R ₃ , R ₅ and R ₆ are Each independently Hydrogen, an alkyl group having 1 to 10 carbon atoms, or -OR _o , wherein R _o is hydrogen or an alkyl group having 1 to 10 carbon atoms.

[Formula 2]

In Chemical Formula 2,

R ₇ , R _7a , R ₈ and R _8a are independent of each other, of which at least two or more are hydroxy groups (-OH), the remainder is an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the hydroxy group ( -OH) has an asymmetric structure with each other,

R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are Each independently Hydrogen, an alkyl group having 1 to 10 carbon atoms, or -OR _o , wherein R _o is hydrogen or an alkyl group having 1 to 10 carbon atoms,

n and m are each independently an integer of 0 to 3.

In the present specification, the compound represented by Formula 1 or the compound represented by Formula 2 provided as a hardmask compound includes a polycyclic aromatic group having a high carbon content substituted with at least two hydroxy groups, wherein the two or more hydroxy groups are By having a specific structure substituted at an asymmetrical position, it has low viscosity properties and high solvent solubility applicable to a spin-on coating method. Therefore, when dissolving it in a solvent and using it as a material for forming an underlayer film for lithography, even when applying a substrate having a step (for example, a space pattern or a hole pattern, etc.) Can be secured.

Moreover, since the compound represented by Formula 1 or the compound represented by Formula 2 has many sites capable of crosslinking, self-crosslinking reaction is possible without additives. Therefore, as the hydroxy group (-OH) group bonded in an asymmetric structure is dehydrated in the low-temperature heat treatment process, a crosslinking reaction occurs due to a condensation reaction, forming a high molecular weight polymer in a short time, thereby forming a rigid and robust hardmask layer. Can be formed. Moreover, since the compound represented by Formula 1 or the compound represented by Formula 2 is a compound having a relatively high carbon concentration, high etching resistance after curing can be secured. Moreover, since the film formed by the rigidity of this structure has high heat resistance, it can be used even under high temperature baking conditions.

As described above, when the compound represented by Formula 1 or the compound represented by Formula 2 is used, properties required for forming the hardmask layer, such as excellent gap-fill properties, as well as mechanical properties, heat resistance, chemical resistance, and etching after curing Resistance can be secured.

In particular, since the compound represented by Formula 1 or the compound represented by Formula 2 of the present invention contains a polycyclic aromatic group in which at least two hydroxy groups are asymmetrically substituted at the structural center of the compound, at least two hydroxy groups are polycyclic A compound represented by the following formula (9) located at both ends of the group, or a compound represented by the following formula (10) containing a polycyclic aromatic group in which two or more carboxyl groups are substituted at an asymmetric position instead of a hydroxy group, or two or more hydroxy groups are symmetrically substituted. Compared to the compound represented by Formula 11 below, which contains polycyclic aromatic groups, the hydroxy group (-OH) group is more easily dehydrated under the low temperature heat treatment process, so that the crosslinking bond is more easily formed and a high-density solid hardmask layer Can be formed.

[Formula 9]

[Formula 10]

[Formula 11]

(1) compound represented by formula 1

Specifically, the compound for a hard mask of the present invention may be a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R ₁ and R ₄ are independent of each other, at least one of which is an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the rest is a hydroxy group (-OH), an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms,

R ₂ , R ₃ , R ₅ and R ₆ are Each independently Hydrogen, an alkyl group having 1 to 10 carbon atoms, or -OR _o , wherein R _o is hydrogen or an alkyl group having 1 to 10 carbon atoms.

More specifically, in consideration of ease of crosslinking and solubility in an organic solvent, in Formula 1, R ₁ and R ₄ are independent of each other, of which at least one is an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the rest is a hydroxy group ( -OH) or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ₂ , R ₃ , R ₅ and R ₆ are Each independently Hydrogen or -OR _o , wherein R _o may be hydrogen or an alkyl group having 1 to 10 carbon atoms, and more specifically, in Formula 1, R ₁ and R ₄ are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms , R ₂ and R ₅ are each independently Hydrogen, or -OR _o , wherein R _o is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ₃ and R ₆ are each independently It can be hydrogen.

The compound represented by Formula 1 may be at least one selected from the group consisting of compounds represented by the following Formulas 1a to 1l as a representative example.

[Formula 1a]

[Formula 1b]

[Formula 1c]

[Formula 1d]

[Formula 1e]

[Formula 1f]

[Formula 1g]

[Formula 1h]

[Formula 1i]

[Formula 1j]

[Formula 1k]

[Formula 1l]

The compound represented by Formula 1 is more preferable as the number of hydroxy groups (-OH) as condensed rings and substituents increases in order to facilitate crosslinking. For example, compounds of Formulas 1c and 1d are more preferable than compounds of Formulas 1a and 1b, and compounds of Formulas 1e and 1f are more preferable than compounds of Formulas 1c and 1d.

That is, in order to increase the etching resistance, it is preferable that the carbon content is high because there are many hexagonal condensed rings. However, when the number of condensed rings increases, there is a disadvantage that it is not easy to apply the spin-on coating method because it is not well soluble in a solvent.

Thus, in the present invention, to improve this problem, By including at least two hydroxy group (-OH) substituents, such as the compound represented by Formula 1, solubility can be secured, strong crosslinking bonds can be formed with each other during a thermal crosslinking reaction, and etching resistance can be secured. In particular, since the compound represented by Formula 1 is not in the form of a polymer having a repeating structure, its size is small, and it is well buried in holes such as a hole pattern, thereby securing excellent gap-fill performance. This characteristic can exert a great effect on a thick spin-on carbon material where securing solubility is one of the keys.

Meanwhile, the compound represented by Formula 1 may be synthesized by applying a known polymerization method.

Specifically, (i) at least one compound of the compound represented by the following formula 3 and the compound represented by formula 4 and (ii) an aromatic compound containing a bromine element are added to a reaction solvent, and a polycondensation reaction is performed under the conditions of a polymerization initiator. Can be manufactured.

[Formula 3]

[Formula 4]

In Chemical Formula 4,

R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are Each independently It is hydrogen, an alkyl group having 1 to 10 carbon atoms, or a hydroxy group (-OH).

At this time, the bromine element-containing aromatic compound is bromobenzene, 1-bromonaphthalene, 2-bromonaphthalene, 9-bromoanthracene, 2-bromophenanthrene (2- bromophenanthrene), 1-bromopyrene and 2-bromopyrene may be at least one selected from the group, specifically bromobenzene, 1-bromonaphthalene, 9-bromoanthracene and 1-bro It may be at least one selected from the group as furren.

At this time, at least one compound of the compound represented by Formula 3 and the compound represented by Formula 4: The bromine element-containing aromatic compound is 1:1.5 to 1:5, specifically 1:1.5 to 1: It can be mixed at a molar ratio of 4 (molar concentration ratio). If the mixing ratio of the reactants is out of the above range, side reactions may be caused and the yield may decrease.

In addition, the reaction solvent is not particularly limited as long as it is an organic solvent capable of easily dissolving the compound represented by Formula 3, the compound represented by Formula 4, and the aromatic compound containing a bromine element, and appropriately selected from known organic solvents. I can. For example, the reaction solvent may be methanol, ethanol, propanol, butanol, tetrahydrofuran (THF), dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dimethyl formamide (DMF), or a mixed solvent thereof. For example, these solvents may be used alone, or two or more may be used in combination.

The amount of the reaction solvent used may be appropriately set depending on the type of reactant and catalyst to be used, further reaction conditions, etc., and is not particularly limited. The total amount of the bromine element-containing compound) may be suitably used within the range of 1 part by weight to 2,000 parts by weight based on 100 parts by weight.

In addition, the polymerization initiator may be at least one alkyllithium compound selected from the group consisting of methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, and pentyl lithium, specifically n -Butyl lithium is mentioned.

The polymerization initiator is determined according to the content of the reactant used in the present invention, and specifically, 100 parts by weight of the reaction raw material (e.g., the total content of at least one compound and a bromine element-containing compound of the compounds represented by Chemical Formulas 3 and 4) Based on 0.01 parts by weight to 0.2 parts by weight may be used.

Further, the reaction temperature of the polycondensation reaction can be appropriately selected according to the boiling point of the reaction solvent, but the reaction temperature is preferably higher in order to obtain the compound represented by Formula 1 of the present invention, and specifically, 60 to 200°C The range of is preferred.

Then, after completion of the polycondensation reaction, a saturated aqueous ammonium chloride solution may be added to terminate the reaction.

Then, the obtained product can be obtained by separating from the reaction solution using a known method.

For example, in order to remove unreacted raw materials or polymerization initiators, ethyl acetate was added as an extraction solvent to dilute the reaction solution, and then put it in a separatory funnel and separated and washed with water until the water layer became neutral.

At this time, the extraction solvent may be appropriately used within the range of 100 parts by weight to 1000 parts by weight based on 100 parts by weight of the reactant.

Subsequently, after the organic layer was collected, it was distilled off to obtain a suspension, and then, the obtained suspension was added dropwise while stirring the precipitation solvent, heptane, to precipitate crystals.

After separating the precipitated crystals by filtration, the solid obtained by filtration is washed and dried in vacuo to obtain the compound represented by Formula 1 above.

(2) compound represented by formula 2

In addition, the compound for a hard mask of the present invention may be a compound represented by the following formula (2).

[Formula 2]

In Chemical Formula 2,

R ₇ , R _7a , R ₈ and R _8a are independent of each other, of which at least two or more are hydroxy groups (-OH), the remainder is an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the hydroxy group ( -OH) has an asymmetric structure with each other,

R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are Each independently Hydrogen, an alkyl group having 1 to 10 carbon atoms, or -OR _o , wherein R _o is hydrogen or an alkyl group having 1 to 10 carbon atoms,

n and m are each independently an integer of 0 to 3.

Specifically, in consideration of the ease of crosslinking and solubility in an organic solvent, in Formula 2, R ₇ , R _7a , R ₈ and R _8a are independent of each other, and at least two of them are hydroxy groups (-OH), and the rest Is an aromatic hydrocarbon group having 6 to 20 carbon atoms, the hydroxy group (-OH) has an asymmetric structure, and R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are Each independently Hydrogen, or -OR _o , wherein R _o is hydrogen or an alkyl group having 1 to 10 carbon atoms, and n and m may each independently be an integer of 0 to 3.

More specifically, in Formula 2, R ₇ and R ₈ are each independently a hydroxy group (-OH) or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R _7a and R _8a are a hydroxy group (-OH), and R ₉ and R ₁₂ is Each independently Hydrogen, or -OR _o , wherein R _o is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ₁₀ and R ₁₁ are each independently Hydrogen, and n and m may each independently be an integer of 0 to 3.

The compound represented by Formula 2 may be at least one selected from the group consisting of compounds represented by the following Formulas 2a to 2p.

[Formula 2a]

[Formula 2b]

[Formula 2c]

[Formula 2d]

[Formula 2e]

[Formula 2f]

[Chemical Formula 2g]

[Formula 2h]

[Formula 2i]

[Formula 2j]

[Formula 2k]

[Formula 2l]

[Chemical Formula 2m]

[Formula 2n]

[Formula 2o]

[Formula 2p]

The compound represented by Formula 2 is more preferable as the number of fused rings and substituted hydroxyl (-OH) groups increases. For example, the compound of formula 2c is more preferable than the compound of formula 2a, and the compound of formula 2e is more preferable than the compound of formula 2c.

That is, in order to increase the etching resistance, it is preferable that the carbon content is high because there are many hexagonal condensed rings. However, when the number of condensed rings increases, there is a disadvantage that it is not easy to apply the spin-on coating method because it is not well soluble in a solvent.

Thus, in the present invention, to improve this problem, The solubility can be secured by including at least two hydroxy groups (-OH) as substituents, such as the compound represented by Chemical Formula 2, and strong cross-linking can be formed with each other during thermal cross-linking reaction, and etching resistance can be improved. Can be secured.

Meanwhile, the compound represented by Chemical Formula 2 of the present invention can be synthesized by applying a known polymerization method.

Specifically, (i) a compound represented by the following formula (5) and (ii) an aromatic compound containing a bromine element may be added to a reaction solvent, followed by polycondensation reaction under conditions of a polymerization initiator.

[Formula 5]

In Chemical Formula 5,

R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ are Each independently Hydrogen, an alkyl group having 1 to 10 carbon atoms, or a hydroxy group (-OH),

o and p are each independently an integer of 0 to 3.

In this case, the bromine element-containing aromatic compound is bromobenzene, 1-bromonaphthalene, 2-bromonaphthalene, 9-bromoanthracene, 2-bromophenanthrene, 1-bromopyrene and 2-bromopyrene. It may be at least one selected from the group, and specifically, may be at least one selected from the group consisting of bromobenzene, 1-bromonaphthalene, 9-bromoanthracene, and 1-bromopyrene.

At this time, the compound represented by Formula 5: The aromatic compound containing a bromine element may be mixed in a molar ratio of 1:1.5 to 1:5, specifically 1:1.5 to 1:4 (molar concentration ratio) to obtain an optimum yield. . If the mixing ratio of the reactants is out of the above range, side reactions may be caused and the yield may decrease.

The reaction solvent is not particularly limited as long as it is an organic solvent capable of easily dissolving the compound represented by Chemical Formula 5 and the aromatic compound containing a bromine element, and may be appropriately selected from known organic solvents. For example, methanol, ethanol, propanol, butanol, tetrahydrofuran (THF), dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dimethyl formamide (DMF), or a mixed solvent thereof, etc. are exemplified. , These solvents may be used alone, or two or more may be used in combination.

In addition, the amount of the reaction solvent used may be appropriately set according to the type of reactant and catalyst to be used, further reaction conditions, etc., and is not particularly limited, but reaction raw materials (e.g., a compound represented by Formula 5 and a compound containing a bromine element) Total content) It can be suitably used within the range of 1 to 2,000 parts by weight based on 100 parts by weight.

In addition, the polymerization initiator may be at least one alkyllithium compound selected from the group consisting of methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, and pentyl lithium, specifically n -Butyl lithium is mentioned.

The polymerization initiator is determined according to the content of the reactant used in the present invention, and specifically, it is used in an amount of 0.01 parts by weight to 0.2 parts by weight based on 100 parts by weight of the reaction raw material (the total sum of the compound represented by Chemical Formula 5 and the compound containing a bromine element). do.

Further, the reaction temperature of the polycondensation reaction can be appropriately selected according to the boiling point of the reaction solvent, but the reaction temperature is preferably higher in order to obtain the compound represented by Formula 2 of the present invention, and specifically, 60 to 200°C The range of is preferred.

Then, after completion of the polycondensation reaction, a saturated aqueous ammonium chloride solution may be added to terminate the reaction.

Then, the obtained product can be obtained by separating it into a reaction solution using a known method.

For example, in order to remove unreacted raw materials or polymerization initiators, ethyl acetate was added as an extraction solvent to dilute the reaction solution, and then put it in a separatory funnel and separated and washed with water until the water layer became neutral.

At this time, the extraction solvent may be appropriately used within the range of 100 parts by weight to 1000 parts by weight based on 100 parts by weight of the reactant.

Subsequently, after the organic layer was collected, it was distilled off to obtain a suspension, and then, the obtained suspension was added dropwise while stirring the precipitation solvent, heptane, to precipitate crystals.

The precipitated crystals are separated by filtration, and then the solid obtained by filtration is washed and dried in vacuo to obtain a compound represented by Formula 2 above.

Hard mask composition

In addition, in an embodiment of the present invention, it is possible to provide a hardmask composition comprising the compound and a solvent for a hardmask of the present invention.

(1) Compound for hard mask

In the specification of the present invention, since the description of the compound for a hard mask included in the hard mask composition is duplicated with the above, the description thereof will be omitted.

However, with respect to the content of the hardmask compound, the hardmask compound is 1% to 65% by weight, specifically 2% to 50% by weight, more specifically 2% by weight based on the total weight of the hardmask composition % To 35% by weight may be included.

When the hardmask compound is included in the content range in the hardmask composition, excellent gap-fill properties can be secured, and a hardmask composition having excellent heat resistance and etching resistance can be prepared even after curing.

If the content of the compound for the hard mask is less than 1% by weight, it is difficult to coat with a desired thin film thickness, and thus, there is a disadvantage in that the desired etching resistance cannot be secured. In addition, when the content of the compound for a hard mask exceeds 65% by weight, solubility or dispersibility in a solvent decreases, and thus it is difficult to form a film with a uniform thickness.

(2) solvent

The solvent contained in the hardmask composition of the present invention can be used without particular limitation as long as it dissolves the hardmask compound.

Typical examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate. Ester solvents such as tate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, methanol, ethanol, isopropanol, 1-ethoxy-2-propanol Alcohol solvents such as (PGME), aromatic hydrocarbons such as toluene, xylene, and anisole, etc., but are not particularly limited thereto. These solvents may be used alone, or may be used in combination of two or more.

Among the solvents, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl hydroxyisobutyrate, 1-methoxy-2-propanol, or anisole are particularly preferred for safety improvement. Do.

The hardmask composition of the present invention prepared as described above has excellent solubility as a replacement for a thick ACL (High Defectivity, Low Producibility, High Cost) hard mask for low and high temperature processes, so it is excellent for a vertical pattern profile with a large aspect ratio. The gap fill performance can be secured. In addition, since a high degree of crosslinking can be secured by rapid curing at a low temperature, it is applicable to both low and high temperature heat treatment processes.

Therefore, when the hardmask composition of the present invention is used, a uniform film having excellent etching resistance can be formed on the upper, middle, and lower portions of the film requiring high-density film characteristics, and furthermore, the etching mask during the etching process for pattern formation Since the problem of bowing or collapsing of the pattern can be improved, a vertical fine pattern can be formed.

How to form a pattern

In addition, in an embodiment of the present invention

Coating the hardmask composition of the present invention on the layer to be etched on the substrate;

Curing the hardmask composition to form a hardmask layer;

Forming a photoresist layer over the hardmask layer;

Exposing and developing the photoresist layer to form a photoresist pattern;

Selectively patterning the hardmask layer using the photoresist pattern as an etching mask; And

A method of forming a pattern of a semiconductor device including a step of patterning an etched layer using the patterned hard mask layer as an etching mask may be provided.

In the method of the present invention, the layer to be etched may be formed using an oxynitride film or an oxide film.

In the method of the present invention, the step of coating the hardmask composition may be performed by a spin-on coating method.

In addition, the step of curing the hardmask composition may be performed by heat treatment at 100°C to 500°C.

The hard mask layer may be formed to a thickness of about 500 Å to 2000 Å.

At this time, since the hard mask film of the present invention is formed as a single layer, not only can the process step be simplified, but also can be formed by a spin-on coating method, and thus can be formed using conventional photoresist film formation equipment, and subsequent In the process, removal is easy by a conventional removal process, for example, a removal process using a thinner, an alkali solvent or a fluorine gas.

Meanwhile, the method of the present invention may further include forming an antireflection film, for example, a silicon-containing thin film layer on the hardmask layer after the step of forming the hardmask layer and before the step of forming the photoresist layer.

In addition, the method of the present invention is a step of forming an amorphous carbon layer or a polymer layer having a high carbon content on the top of the layer to be etched before coating the composition for a hard mask of the present invention in order to further secure the etching selectivity of the hard mask film. In addition, a two-layer hard mask film may be used.

In the method of the present invention, the patterning may be performed using one or more gases selected from the group consisting of Cl ₂ , Ar, O ₂ /N ₂ , CF ₄ and C ₂ F ₆ .

When performing the etching process, power can be applied in a wide variety depending on the etching equipment, gas used, or the type of process, but preferably, source RF power of about 300 to 1000W and about 0 to 300W. The bias power of is applied.

Meanwhile, in the above method, the photoresist pattern or the hard mask pattern remaining after the etching process may be removed by a removal process using a general thinner composition, an alkali solvent, or a fluorine gas.

The method for forming a fine pattern of a hardmask composition and a semiconductor device according to the present invention is an ultrafine pattern forming process using a short wavelength such as KrF, VUV, EUV, E-beam, X-ray or ion beam, preferably 193 nm ArF light source. Can be applied to

In addition, the present invention provides a semiconductor device manufactured by a method of manufacturing a semiconductor device including the method of forming a pattern of the semiconductor device.

Hereinafter, the present invention will be described in detail by examples. However, the following examples are only for illustrating the present invention, and the contents of the present invention are not limited by the following examples.

Example

Example 1.

(Preparation of the compound of formula 1a)

In a nitrogen atmosphere, 20 g of bromobenzene was weighed into a 500 ml three-neck flask equipped with a thermometer and a reflux tube, and 200 ml of tetrahydrofuran was added, followed by uniform stirring. The flask was cooled with dry ice, and 30 ml of a 2.5 mol/L n-butyllithium-hexane solution was added dropwise over 20 minutes, and then aged for 5 hours. After completion of the aging, the refrigerant was changed to an ice bath, and 50 g of a 20 wt% 1,4-cyclohexanedione solution was added dropwise at -20°C over 20 minutes. After aging at room temperature for 5 hours, the reaction was stopped with 100 ml of saturated aqueous ammonium chloride solution. After diluting with 400 ml of ethyl acetate, it was transferred to a separatory funnel and separated and washed with water until the water layer became neutral. The organic layer was recovered, the solvent was distilled off, and a suspension was obtained. To the obtained suspension, 300 g of heptane was added dropwise while stirring to precipitate crystals. The crystals were collected by filtration with a funnel, washed three times with 300 ml of a washing solution (ethyl acetate:hexane = 1:2 volume ratio), and dried in vacuo at 60° C. to obtain a compound represented by Chemical Formula 1a (yield: 93%).

-1H-NMR (400 MHz, (CD3)2SO, Bruker) δ(ppm) = 7.54 (d, 4H), 7.38 (t, 6H), 3.65 (s, 2H), 2.02 (t, 4H), 1.77 ( t, 4H)

-Weight average molecular weight (Mw, GPC (Gel Permeation Chromatography, Waters): 268.4

-MS (MALDI-TOF, Voyager): m/z = 268.1 (100%)

(Example 1-1: Preparation of a hard mask composition for evaluating a gap fill)

Organic solvent (propylene glycol monomethyl ether acetate, PGMEA): cyclohexanone = 5:5 volume ratio) After dissolving 10 g of the compound represented by Formula 1a in 90 g, it was filtered through a 0.45 µm syringe filter, and a hard mask composition for gapfill evaluation Was prepared.

(Example 1-2: Preparation of hard mask composition for evaluation of etching (ething))

After dissolving 30 g of the compound represented by Formula 1a in 70 g of an organic solvent (PGMEA: cyclohexanone = 5:5 by volume), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for etching evaluation.

Example 2.

(Preparation of a compound of Formula 1i)

(Step 1)

In a nitrogen atmosphere, 30.00 g of 2,5-dihydroxy-1,4-benzoquinone, 34.6 g of methyl iodide, and 10.6 g of sodium hydride were added to N,N- in a 500 ml 3-neck flask equipped with a thermometer and a reflux tube. After adding to 200 g of dimethylformamide, the mixture was stirred at 40° C. for 12 hours. The reaction product was aged at room temperature for 1 hour, neutralized with a 5% hydrogen chloride solution to pH 7, and the precipitate formed was filtered and dried under vacuum to obtain a compound represented by the following formula (6).

[Formula 6]

(Step 2)

In a nitrogen atmosphere, 20 g of bromobenzene was weighed into a 500 ml 3-neck flask equipped with a thermometer and a reflux tube, 200 ml of tetrahydrofuran was added, and the mixture was stirred uniformly. The flask was cooled with dry ice, and 30 ml of a 2.5 mol/L n-butyllithium-hexane solution was added dropwise over 20 minutes, and then aged for 5 hours. After completion of the aging, the refrigerant was changed to an ice bath, and 50 g of the compound represented by Formula 6 prepared in (Step 1) was dissolved in tetrahydrofuran at -20° C. to prepare a reaction solution of 20% by weight, followed by 20 minutes. It was dripped. After aging at room temperature for 5 hours, the reaction was stopped with 100 ml of saturated aqueous ammonium chloride solution. After dilution with 400 ml of ethyl acetate, it was transferred to a separatory funnel and separated and washed with water until the water layer became neutral. The organic layer was recovered, the solvent was distilled off, and a suspension was obtained. To the obtained suspension, 300 g of heptane was added dropwise while stirring to precipitate crystals. The crystals were collected by filtration through a funnel, washed three times with 300 ml of a washing solution (ethyl acetate:hexane = 1:2 volume ratio), and dried under vacuum at 60° C. to obtain a compound represented by Formula 1i (yield: 96%). .

-1H-NMR (400 MHz, (CD3)2SO): δ(ppm) = 7.54 (d, 4H), 7.38 (t, 6H), 3.65 (s, 2H), 3.30 (s, 6H), 3.25 (t , 2H), 2.13 (d, 2H), 1.88 (d, 2H)

-Weight average molecular weight (Mw): 328.4

-MS (MALDI-TOF): m/z = 328.2 (100%)

Example 3.

(Preparation of the compound of formula 1b)

In a nitrogen atmosphere, in a 250 ml three-neck flask equipped with a thermometer and a reflux tube, 15.3 g of a compound represented by Formula 1i prepared in Example 2, 16.1 g of 1-dodecancyol, and 5.5 g of potassium hydroxide were N,N- After adding to 89 g of dimethylformamide, the mixture was dissolved at room temperature, and the oil bath was heated to 140° C. and reacted with stirring for 12 hours. The reaction mixture was slowly cooled, neutralized to pH 7 with 5% hydrogen chloride solution, and the precipitate formed was filtered and dried in vacuo to obtain a compound represented by Formula 1b (yield: 91%).

-1H-NMR (400 MHz, (CD3)2SO): δ(ppm) = 7.54 (d, 4H), 7.38 (t, 6H), 3.65 (s, 2H), 3.63 (t, 2H), 3.58 (s , 2H), 2.15 (d, 2H), 1.90 (d, 2H)

-Weight average molecular weight (Mw): 300.3

-MS (MALDI-TOF): m/z = 300.1 (100%)

(Example 3-1: Preparation of a hard mask composition for evaluating a gap fill)

After dissolving 10 g of the compound represented by Formula 1b in 90 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for evaluating a gap fill.

(Example 3-2: Preparation of hard mask composition for etching evaluation)

After dissolving 30 g of the compound represented by Formula 1b in 70 g of an organic solvent (PGMEA: cyclohexanone = 5:5 by volume), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for etching evaluation.

Example 4.

(Preparation of a compound of formula 2i)

(Step 1)

In a nitrogen atmosphere, 2,6-dihydroxy-anthraquinone 20.00 g, methyl iodide 23.1 g, sodium hydride 7.1 g were added to N,N-dimethylformamide in a 500 ml 3-neck flask equipped with a thermometer and reflux tube. After adding to 150g, the mixture was stirred at 40° C. for 12 hours. The reaction product was aged at room temperature for 1 hour, and then the precipitate formed by neutralizing with a 5% hydrogen chloride solution to pH 7 was filtered and dried in vacuo to obtain a compound represented by the following formula (7) (yield: 86%).

[Formula 7]

(Step 2)

In a nitrogen atmosphere, 13 g of bromobenzene was weighed into a 500 ml 3-neck flask equipped with a thermometer and a reflux tube, 130 ml of tetrahydrofuran was added, and the mixture was stirred uniformly. The flask was cooled with dry ice, and 20 ml of a 2.5 mol/L n-butyllithium-hexane solution was added dropwise over 20 minutes, and then aged for 5 hours. After completion of aging, 33.0 g of the compound represented by Formula 7 prepared in (Step 1) was dissolved in tetrahydrofuran to prepare a reaction solution of 20% by weight, and then the reaction solution was changed to an ice bath at -20°C. It was dripped over a minute. After aging at room temperature for 5 hours, the reaction was stopped with 70 ml of saturated aqueous ammonium chloride solution. After diluting with 250 ml of ethyl acetate, it was transferred to a separatory funnel and separated and washed with water until the water layer became neutral. The organic layer was recovered, the solvent was distilled off, and a suspension was obtained. To the obtained suspension, 200 g of heptane was added dropwise while stirring to precipitate crystals. The crystals were collected by filtration with a funnel, washed three times with 200 ml of a washing solution (ethyl acetate:hexane = 1:2 volume ratio), and dried in vacuo at 60° C. to obtain a compound represented by Formula 2i (yield: 88%).

-1H-NMR (400 MHz, (CD3)2SO): δ(ppm) = 7.38 (t, 6H), 7.36 (d, 4H), 7.20 (d, 2H), 6.82 (s, 2H), 6.70 (d , 2H), 3.83 (s, 6H), 3.65 (s, 2H)

-Weight average molecular weight (Mw): 424.5

-MS (MALDI-TOF): m/z = 424.2 (100%)

Example 5.

(Preparation of a compound of formula 2a)

In a nitrogen atmosphere, 10.0g of a compound represented by Formula 2i prepared in Example 4, 10.7g of 1-dodecancyol, and 3.7g of potassium hydroxide were added to a 250 ml 3-neck flask equipped with a thermometer and a reflux tube. After adding to 60 g of dimethylformamide, dissolving at room temperature, heating the oil bath to 140°C, and reacting with stirring for 12 hours. The reaction mixture was slowly cooled, neutralized to pH 7 with a 5% hydrogen chloride solution, and the precipitate formed was filtered and dried in vacuo to obtain a compound represented by the following formula 2a (yield: 87%).

-1H-NMR (400 MHz, (CD3)2SO): δ(ppm) = 7.38 (t, 6H), 7.36 (d, 4H), 7.14 (d, 2H), 6.78 (d, 2H), 6.66 (d , 2H), 5.35 (s, 2H), 3.65 (s, 2H)

-Weight average molecular weight (Mw): 396.4

-MS (MALDI-TOF): m/z = 396.1 (100%)

(Example 5-1: Preparation of a hard mask composition for evaluating a gap fill)

After dissolving 10 g of the compound represented by Formula 2a in 90 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hard mask composition for evaluating a gap fill.

(Example 5-2: Preparation of hard mask composition for etching evaluation)

After dissolving 30 g of the compound represented by Formula 2a in 70 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for etching evaluation.

Example 6.

(Preparation of the compound of formula 2j)

(Step 1)

In a nitrogen atmosphere, 2,8-dihydroxy-5,12-naphthacenequinone 20.00 g, methyl iodide 23.1 g, sodium hydride 7.1 g were added to a 500 ml 3-neck flask equipped with a thermometer and a reflux tube. ,N-dimethylformamide was added to 150g and then stirred at 40°C for 12 hours. The reaction product was aged for 1 hour at room temperature, and then the precipitate formed by neutralizing with a 5% hydrogen chloride solution to pH 7 was filtered and dried in vacuo to obtain a compound represented by the following formula (8) (yield: 79%).

[Formula 8]

(Step 2)

In a nitrogen atmosphere, 13 g of bromobenzene was weighed into a 500 ml 3-neck flask equipped with a thermometer and a reflux tube, 130 ml of tetrahydrofuran was added, and the mixture was stirred uniformly. The flask was cooled with dry ice, and 20 ml of a 2.5 mol/L n-butyllithium-hexane solution was added dropwise over 20 minutes, and then aged for 5 hours. After completion of aging, 33.0 g of the compound represented by Formula 8 prepared in (Step 1) was dissolved in tetrahydrofuran to prepare a 20% by weight reaction solution, and then the reaction solution was changed to an ice bath at -20°C. It was dripped over 20 minutes. After aging at room temperature for 5 hours, the reaction was stopped with 70 ml of saturated aqueous ammonium chloride solution. After diluting with 250 ml of ethyl acetate, it was transferred to a separatory funnel and separated and washed with water until the water layer became neutral. The organic layer was recovered, the solvent was distilled off, and a suspension was obtained. To the obtained suspension, 200 g of heptane was added dropwise while stirring to precipitate crystals. The crystals were collected by filtration with a funnel, washed three times with 200 ml of a washing solution (ethyl acetate:hexane = 1:2 volume ratio), and dried in vacuo at 60° C. to obtain a compound represented by Chemical Formula 2j (yield: 78%).

-1H-NMR (400 MHz, (CD3)2SO): δ(ppm) = 7.91 (d, 1H), 7.38 (t, 6H), 7.37 (s, 2H), 7.36 (d, 4H), 7.33 (s , 1H), 7.20 (d, 1H), 7.18 (d, 1H), 6.82 (d, 1H), 6.70 (d, 1H), 3.83 (s, 6H), 3.65 (s, 2H)

-Weight average molecular weight (Mw): 474.5

-MS (MALDI-TOF): m/z = 474.2 (100%)

Example 7.

(Preparation of the compound of formula 2b)

In a nitrogen atmosphere, in a 250 ml three-neck flask equipped with a thermometer and a reflux tube, 10.0 g of a compound represented by Formula 2j prepared in Example 6, 10.7 g of 1-dodecancyol, and 3.7 g of potassium hydroxide were added to N,N- It was added to 60 g of dimethylformamide, dissolved at room temperature, heated to 140°C, and reacted with stirring for 12 hours. The reaction mixture was slowly cooled, neutralized to pH 7 with 5% hydrogen chloride solution, and the precipitate formed was filtered and dried in vacuo to obtain a compound represented by Formula 2b (yield: 85%).

-1H-NMR (400 MHz, (CD3)2SO): δ(ppm) = 7.93 (d, 1H), 7.38 (t, 7H), 7.36 (d, 5H), 7.26 (s, 1H), 7.14 (d , 1H), 7.11 (d, 1H), 6.78 (s, 1H), 6.66 (d, 1H), 5.35 (s, 2H), 3.65 (s, 2H)

-Weight average molecular weight (Mw): 446.5

-MS (MALDI-TOF): m/z = 446.2 (100%)

(Example 7-1: Preparation of a hard mask composition for evaluating a gap fill)

After dissolving 10 g of the compound represented by Formula 2b in 90 g of an organic solvent (PGMEA: cyclohexanone = 5:5 by volume), it was filtered through a 0.45 μm syringe filter to prepare a hard mask composition for evaluating a gap fill.

(Example 7-2: Preparation of a hard mask composition for etching evaluation).

After dissolving 30 g of the compound represented by Chemical Formula 2b in 70 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for etching evaluation.

Example 8.

(Preparation of a compound of formula 1c)

A compound represented by Formula 1c (yield: 92%) was obtained in the same manner as in Example 1, except that 1-bromonaphthalene was used instead of bromobenzene.

-1H-NMR (400 MHz, (CD3)2SO): δ(ppm) = 8.18 (d, 2H), 8.05 (d, 2H), 7.92 (d, 2H), 7.54 (t, 2H), 7.52 (t , 2H), 7.42 (t, 2H), 7.00 (d, 2H), 3.65 (s, 2H), 2.04 (t, 4H), 1.79 (t, 4H)

-Weight average molecular weight (Mw): 368.5

-MS (MALDI-TOF): m/z = 368.2 (100%)

(Example 8-1: Preparation of a hard mask composition for evaluating a gap fill)

After dissolving 10 g of the compound represented by Formula 1c in 90 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hard mask composition for evaluating a gap fill.

(Example 8-2: Preparation of hard mask composition for etching evaluation)

After dissolving 30 g of the compound represented by Chemical Formula 1c in 70 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for etching evaluation.

Example 9.

(Preparation of a compound of Formula 1d)

In a nitrogen atmosphere, 20 g of 1-bromonaphthalene was weighed into a 500 ml 3-neck flask equipped with a thermometer and a reflux tube, and 200 ml of tetrahydrofuran was added, followed by uniform stirring. The flask was cooled with dry ice, and 30 ml of a 2.5 mol/L n-butyllithium-hexane solution was added dropwise over 20 minutes, and then aged for 5 hours. After completion of aging, the refrigerant was changed to an ice bath and 50.0 g of the compound represented by Formula 6 prepared in (Step 1) of Example 2 was dissolved in tetrahydrofuran at -20 degrees to prepare a reaction solution of 20% by weight. , It was dripped over 20 minutes. After aging at room temperature for 5 hours, the reaction was stopped with 100 ml of saturated aqueous ammonium chloride solution. After dilution with 400 ml of ethyl acetate, it was transferred to a separatory funnel and separated and washed with water until the water layer became neutral. The organic layer was recovered, the solvent was distilled off, and a suspension was obtained. To the obtained suspension, 300 g of heptane was added dropwise while stirring to precipitate crystals. The crystals were collected by filtration with a funnel, washed three times with 300 ml of a washing solution (ethyl acetate:hexane = 1:2 volume ratio), and dried under vacuum at 60° C. to obtain a compound represented by Formula 1d (yield: 87%). .

-1H-NMR (400 MHz, (CD3)2SO): δ(ppm) = 8.18 (d, 2H), 8.05 (d, 2H), 7.92 (d, 2H), 7.54 (t, 2H), 7.52 (t , 2H), 7.42 (t, 2H), 7.00 (d, 2H), 3.65 (s, 2H), 3.63 (t, 2H), 3.58 (s, 2H), 2.17 (d, 2H), 1.79 (d, 2H)

-Weight average molecular weight (Mw): 400.5

-MS (MALDI-TOF): m/z = 400.2 (100%)

(Example 9-1: Preparation of a hard mask composition for evaluating a gap fill)

After dissolving 10 g of the compound represented by Formula 1d in 90 g of an organic solvent (PGMEA: cyclohexanone = 5:5 by volume), it was filtered through a 0.45 μm syringe filter to prepare a hard mask composition for evaluating a gap fill.

(Example 9-2: Preparation of hard mask composition for etching evaluation)

After dissolving 30 g of the compound represented by Formula 1d in 70 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for etching evaluation.

Example 10.

(Preparation of a compound of formula 2c)

In a nitrogen atmosphere, 13 g of 1-bromonaphthalene was weighed into a 500 ml 3-neck flask equipped with a thermometer and a reflux tube, 130 ml of tetrahydrofuran was added, and the mixture was stirred uniformly. The flask was cooled with dry ice, and 20 ml of a 2.5 mol/L n-butyllithium-hexane solution was added dropwise over 20 minutes, and then aged for 5 hours. After completion of the aging, 33.0 g of the compound represented by Formula 7 prepared in (Step 1) of Example 4 was dissolved in tetrahydrofuran to prepare a reaction solution of 20% by weight, and then the refrigerant was changed to an ice bath at -20°C. The reaction solution was added dropwise over 20 minutes. After aging at room temperature for 5 hours, the reaction was stopped with 70 ml of saturated aqueous ammonium chloride solution. After diluting with 250 ml of ethyl acetate, it was transferred to a separatory funnel and separated and washed with water until the water layer became neutral. The organic layer was recovered, the solvent was distilled off, and a suspension was obtained. To the obtained suspension, 200 g of heptane was added dropwise while stirring to precipitate crystals. The crystals were collected by filtration with a funnel, washed three times with 200 ml of a washing solution (ethyl acetate:hexane = 1:2 volume ratio), and dried under vacuum at 60° C. to obtain a compound represented by Formula 2c (yield: 83%).

-1H-NMR (400 MHz, (CD3)2SO): δ(ppm) = 8.18 (d, 2H), 8.05 (d, 2H), 7.92 (d, 2H), 7.54 (t, 2H), 7.52 (t , 2H), 7.42 (t, 2H), 7.14 (d, 2H), 7.00 (d, 2H), 6.78 (s, 2H), 6.66 (d, 2H), 5.35 (s, 2H), 3.65 (s, 2H)

-Weight average molecular weight (Mw): 496.6

-MS (MALDI-TOF): m/z = 496.2 (100%)

(Example 10-1: Preparation of a hard mask composition for evaluating a gap fill)

After dissolving 10 g of the compound represented by Formula 2c in 90 g of an organic solvent (PGMEA: cyclohexanone = 5:5 by volume), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for evaluating a gap fill.

(Example 10-2: Preparation of hard mask composition for etching evaluation)

After dissolving 30 g of the compound represented by Formula 2c in 70 g of an organic solvent (PGMEA: cyclohexanone = 5:5 by volume), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for etching evaluation.

Example 11.

(Preparation of a compound of formula 2d)

In a nitrogen atmosphere, v 13 g was weighed into a 500 ml three-necked flask equipped with a thermometer and a reflux tube, and 130 ml of tetrahydrofuran was added, followed by uniform stirring. The flask was cooled with dry ice, and 20 ml of a 2.5 mol/L n-butyllithium-hexane solution was added dropwise over 20 minutes, and then aged for 5 hours. After completion of the aging, 33.0 g of the compound represented by Formula 8 prepared in Example 6 (Step 1) was dissolved in tetrahydrofuran to prepare a 20% by weight reaction solution, and then the refrigerant was changed to an ice bath at -20°C. The reaction solution was added dropwise over 20 minutes. After aging at room temperature for 5 hours, the reaction was stopped with 70 ml of saturated aqueous ammonium chloride solution. After diluting with 250 ml of ethyl acetate, it was transferred to a separatory funnel and separated and washed with water until the water layer became neutral. The organic layer was recovered, the solvent was distilled off, and a suspension was obtained. To the obtained suspension, 200 g of heptane was added dropwise while stirring to precipitate crystals. The crystals were collected by filtration with a funnel, washed three times with 200 ml of a washing solution (ethyl acetate:hexane = 1:2 volume ratio), and dried in vacuo at 60° C. to obtain a compound represented by Formula 2d (yield: 82%).

-1H-NMR (400 MHz, (CD3)2SO): δ(ppm) = 8.18 (d, 2H), 8.05 (d, 2H), 7.93 (d, 1H), 7.92 (d, 2H), 7.54 (t , 2H), 7.52 (t, 2H), 7.42 (t, 2H), 7.38 (s, 1H), 7.36 (s, 1H), 7.26 (s, 1H), 7.14 (d, 1H), 7.11 (d, 1H), 7.00 (s, 2H), 6.78 (d, 1H), 6.66 (d, 1H), 5.35 (s, 2H), 3.65 (s, 2H)

-Weight average molecular weight (Mw): 546.6

-MS (MALDI-TOF): m/z = 546.2 (100%)

(Example 11-1: Preparation of a hard mask composition for evaluating a gap fill)

After dissolving 10 g of the compound represented by Formula 2d in 90 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hard mask composition for evaluating a gap fill.

(Example 11-2: Preparation of hard mask composition for etching evaluation)

After dissolving 30 g of the compound represented by Chemical Formula 2d in 70 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for etching evaluation.

Example 12.

(Preparation of a compound of Formula 1e)

A compound represented by Chemical Formula 1e (yield: 82%) was obtained in the same manner as in Example 1, except that 9-bromoanthracene was used instead of bromobenzene.

-1H-NMR (400 MHz, (CD3)2SO): δ(ppm) = 8.15 (s, 2H), 7.96 (d, 4H), 7.89 (d, 4H), 7.38 (d, 4H), 7.37 (t , 4H), 3.65 (s, 2H), 2.04 (t, 4H), 1.79 (t, 4H)

-Weight average molecular weight (Mw): 468.6

-MS (MALDI-TOF): m/z = 468.2 (100%)

(Example 12-1: Preparation of a hard mask composition for evaluating a gap fill)

After dissolving 10 g of the compound represented by Formula 1e in 90 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for evaluating a gap fill.

(Example 12-2: Preparation of hard mask composition for etching evaluation)

After dissolving 30 g of the compound represented by Formula 1e in 70 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for etching evaluation.

Example 13.

(Preparation of the compound of formula 1f)

A compound represented by Formula 1f (yield: 72%) was obtained in the same manner as in Example 9, except that 9-bromoanthracene was used instead of 1-bromonaphthalene.

-1H-NMR (400 MHz, (CD3)2SO): δ(ppm) = 8.15 (s, 2H), 7.96 (d, 4H), 7.89 (d, 4H), 7.38 (t, 4H), 7.37 (t , 4H), 3.65 (s, 2H), 3.63 (m, 2H), 3.58 (d, 2H), 2.17 (d, 2H), 1.92 (d, 2H)

-Weight average molecular weight (Mw): 500.6

-MS (MALDI-TOF): m/z = 500.2 (100%)

(Example 13-1: Preparation of a hard mask composition for evaluating a gap fill)

After dissolving 10 g of the compound represented by Formula 1f in 90 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hard mask composition for evaluating a gap fill.

(Example 13-2: Preparation of hard mask composition for etching evaluation)

After dissolving 30 g of the compound represented by Formula 1f in 70 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for etching evaluation.

Example 14.

(Preparation of a compound of formula 2e)

A compound represented by Formula 2e (yield: 70%) was obtained in the same manner as in Example 10, except that 9-bromoanthracene was used instead of 1-bromonaphthalene.

-1H-NMR (400 MHz, (CD3)2SO): δ(ppm) = 8.15 (s, 2H), 7.96 (d, 4H), 7.89 (d, 4H), 7.38 (t, 4H), 7.37 (t , 4H), 7.14 (d, 2H), 6.78 (s, 2H), 6.66 (d, 2H), 5.35 (s, 2H), 3.65 (s, 2H)

-Weight average molecular weight (Mw): 596.7

-MS (MALDI-TOF): m/z = 596.2 (100%)

(Example 14-1: Preparation of a hard mask composition for evaluating a gap fill)

After dissolving 10 g of the compound represented by Formula 2e in 90 g of an organic solvent (PGMEA: cyclohexanone = 5:5 by volume), it was filtered through a 0.45 μm syringe filter to prepare a hard mask composition for evaluating a gap fill.

(Example 14-2: Preparation of hard mask composition for etching evaluation)

After dissolving 30 g of the compound represented by Formula 2e in 70 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for etching evaluation.

Example 15.

(Preparation of Formula 2f Compound)

A compound represented by Formula 2f (yield: 66%) was obtained in the same manner as in Example 11, except that 9-bromoanthracene was used instead of 1-bromonaphthalene.

-1H-NMR (400 MHz, (CD3)2SO): δ(ppm) = 8.15 (s, 2H), 7.96 (d, 4H), 7.93 (d, 1H), 7.89 (d, 4H), 7.38 (t , 5H), 7.37 (t, 4H), 7.36 (s, 1H), 7.26 (s, 1H), 7.14 (d, 1H), 7.11 (d, 1H), 6.78 (s, 1H), 6.66 (d, 1H), 5.35 (s, 2H), 3.65 (s, 2H)

-Weight average molecular weight (Mw): 646.7

-MS (MALDI-TOF): m/z = 646.2 (100%)

(Example 15-1: Preparation of a hard mask composition for evaluating a gap fill)

After dissolving 10 g of the compound represented by Formula 2f in 90 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hard mask composition for evaluating a gap fill.

(Example 15-2: Preparation of hard mask composition for etching evaluation)

After dissolving 30 g of the compound represented by Chemical Formula 2f in 70 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for etching evaluation.

Example 16.

(Preparation of a compound of formula 1g)

A compound represented by Formula 1e (yield: 78%) was obtained in the same manner as in Example 1, except that 1-bromopyrene was used instead of bromobenzene.

-1H-NMR (400 MHz, (CD3)2SO): δ(ppm) = 8.00 (d, 4H), 7.93 (s, 4H), 7.82 (t, 2H), 7.81 (d, 8H), 3.65 (s , 2H), 2.02 (t, 4H), 1.77 (t, 4H)

-Weight average molecular weight (Mw): 516.6

-MS (MALDI-TOF): m/z = 516.2 (100%)

(Example 16-1: Preparation of a hard mask composition for evaluating a gap fill)

After dissolving 10 g of the compound represented by Formula 1e in 90 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for evaluating a gap fill.

(Example 16-2: Preparation of hard mask composition for etching evaluation)

After dissolving 30 g of the compound represented by Formula 1e in 70 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for etching evaluation.

Example 17.

(Preparation of a compound of formula 1h)

A compound represented by Chemical Formula 1h (yield: 80%) was obtained in the same manner as in Example 9, except that 1-bromopyrene was used instead of 1-bromonaphthalene.

-1H-NMR (400 MHz, (CD3)2SO): δ(ppm) = 8.00 (d, 4H), 7.93 (s, 4H), 7.82 (t, 2H), 7.71 (t, 8H), 3.65 (s , 2H), 3.63 (d, 2H), 3.58 (d, 2H), 2.15 (s, 2H), 1.90 (s, 2H)

-Weight average molecular weight (Mw): 548.6

-MS (MALDI-TOF): m/z = 548.2 (100%)

(Example 17-1: Preparation of a hard mask composition for evaluating a gap fill)

After dissolving 10 g of the compound represented by Formula 1h in 90 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hard mask composition for evaluating a gap fill.

(Example 17-2: Preparation of hard mask composition for etching evaluation)

After dissolving 30 g of the compound represented by Formula 1h in 70 g of an organic solvent (PGMEA: cyclohexanone = 5:5 by volume), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for etching evaluation.

Example 18.

(Preparation of compound of formula 2g)

A compound represented by Chemical Formula 2g (yield: 79%) was obtained in the same manner as in Example 10, except that 1-bromopyrene was used instead of 1-bromonaphthalene.

-1H-NMR (400 MHz, (CD3)2SO): δ(ppm) = 8.00 (d, 4H), 7.93 (s, 4H), 7.82 (t, 2H), 7.71 (t, 8H), 7.14 (d , 2H), 6.78 (s, 2H), 6.66 (d, 2H), 5.35 (s, 2H), 3.65 (s, 2H)

-Weight average molecular weight (Mw): 644.7

-MS (MALDI-TOF): m/z = 644.2 (100%)

(Example 18-1: Preparation of a hard mask composition for evaluating a gap fill)

After dissolving 10 g of the compound represented by Chemical Formula 2g in 90 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for evaluating a gap fill.

(Example 18-2: Preparation of hard mask composition for etching evaluation)

After dissolving 30 g of the compound represented by Formula 2g in 70 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for etching evaluation.

Example 19.

(Formula 2h compound preparation)

A compound represented by Formula 2h (yield: 77%) was obtained in the same manner as in Example 11, except that 1-bromopyrene was used instead of 1-bromonaphthalene.

-1H-NMR (400 MHz, (CD3)2SO): δ(ppm) = 8.00 (d, 4H), 7.93 (d, 5H), 7.82 (t, 2H), 7.71 (t, 8H), 7.38 (s , 1H), 7.36 (s, 1H), 7.26 (s, 1H), 7.14 (d, 1H), 7.11 (d, 1H), 6.66 (d, 1H), 5.35 (s, 2H), 3.65 (s, 2H)

-Weight average molecular weight (Mw): 694.8

-MS (MALDI-TOF): m/z = 694.2 (100%)

(Example 19-1: Preparation of a hard mask composition for evaluating a gap fill)

After dissolving 10 g of the compound represented by Formula 2h in 90 g of an organic solvent (PGMEA: cyclohexanone = 5:5 by volume), it was filtered through a 0.45 μm syringe filter to prepare a hard mask composition for evaluating a gap fill.

(Example 19-2: Preparation of hard mask composition for etching evaluation)

After dissolving 30 g of the compound represented by Formula 2h in 70 g of an organic solvent (PGMEA: cyclohexanone = 5:5 by volume), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for etching evaluation.

Comparative Example 1.

(Preparation of compound of formula 9)

Under a nitrogen atmosphere, a solution of anthraquinone (18.2 g) in 150 mL anhydrous tetrahydrofuran (THF) was added dropwise to 200 mL of a solution of 1M phenylmagnesium bromide in THF at 0°C. After completion of the dropwise addition, the reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was poured into 100 mL saturated ammonium chloride solution. The mixture was extracted twice with diethyl ether. The combined ether solution was dried over MgSO ₄ , and the solvent was removed under reduced pressure to obtain Intermediate 1.

Intermediate 1 (8g), pyrene-1-ol (13g) and p-TSA monohydrate (0.3g) were added to 100 mL 1,2-dichloroethane, and the mixture was stirred at 70° C. for 4 hours. The reaction mixture was cooled to room temperature and insoluble matter was removed by filtration. The filtrate was washed once with 100 mL of 0.5% ammonium bicarbonate aqueous solution and then twice with deionized water (100 mL each). 1,2-dichloroethane was removed under reduced pressure to obtain a compound represented by the following formula (9).

[Formula 9]

(Comparative Example 1-1: Preparation of a hard mask composition for evaluating a gap fill)

After dissolving 10 g of the compound represented by Formula 9 in 90 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for evaluating a gap fill.

(Comparative Example 1-2: Preparation of hard mask composition for etching evaluation)

After dissolving 30 g of the compound represented by Chemical Formula 9 in 70 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hard mask composition for etching evaluation.

Comparative Example 2.

(Preparation of compound of formula 10)

Into a flask, 4.7 g of pyromellitic dianhydride, 10.0 g of 1-methoxypyrene, and 287 g of 1,2-dichloroethane were put together and stirred. After slowly adding 17.22 g of aluminum chloride to the solution, it was heated and stirred at 60° C. for 12 hours. After completion of the reaction, the reactant was added dropwise to methanol, and the formed precipitate was filtered and dried to obtain an intermediate 2

10.00 g of the intermediate 2, 14.82 g of 1-dodecancyol, 4.93 g of potassium hydroxide, and 69.43 g of N, N-dimethylformamide were added to the flask, followed by stirring at 110° C. for 8 hours. The reaction mixture was cooled, neutralized with a 5% hydrogen chloride solution to a pH of 6-7, and the formed precipitate was filtered and dried to obtain a compound of Formula 10 below.

[Formula 10]

(Comparative Example 2-1: Preparation of a hard mask composition for evaluating a gap fill)

After dissolving 10 g of the compound represented by Formula 10 in 90 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hard mask composition for evaluating a gap fill.

(Comparative Example 2-1: Preparation of hard mask composition for etching evaluation)

After dissolving 30 g of the compound represented by Chemical Formula 10 in 70 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for etching evaluation.

Comparative Example 3.

(Preparation of compound of formula 11)

A 200 mL container was prepared equipped with a stirrer, a cooling tube and a burette. To this container, 30 g of 4,4'-binol, 15 g of 4-biphenylaldehyde, and 100 mL of butyl acetate were added, and 3.9 g of p-toluenesulfonic acid was added to prepare a reaction solution. The reaction solution was stirred at 90° C. for 3 hours to react. Then, the reaction solution was concentrated, 50 g of heptane was added to precipitate a reaction product, cooled to room temperature, and filtered to separate. After drying the solid obtained by filtration, it was separated and purified by column chromatography to obtain a compound represented by the following formula (11). (Figure 2)

[Formula 11]

(Comparative Example 3-1: Preparation of a hard mask composition for evaluating a gap fill)

After dissolving 10 g of the compound represented by Formula 11 in 90 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hard mask composition for evaluating a gap fill.

(Comparative Example 3-2: Preparation of hard mask composition for etching evaluation)

After dissolving 30 g of the compound represented by Chemical Formula 11 in 70 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for etching evaluation.

Comparative Example 4.

(Preparation of compound of formula 12)

37.16 g of 9,9-bis(4-hydroxyphenyl)fluorene and 2.84 g of paraformaldehyde were added to a three-necked flask equipped with a thermometer, a condenser and a mechanical stirrer under nitrogen. Subsequently, 0.153 g of p-toluenesulfonic acid monohydrate was dissolved in 58 g of propylene glycol monomethyl ether acetate (PGMEA), and this solution was added into a three-necked flask, followed by polymerization while stirring at 95° C. for 6 hours. Thereafter, the polymerization reaction solution was put into a large amount of hexane, and the precipitated polymer was filtered to obtain an intermediate 4. Next, 20 g of the intermediate 4 obtained above, 80 g of N,N-dimethylacetamide and 16.68 g of potassium carbonate were placed in a three-necked flask equipped with a thermometer, a condenser and a mechanical stirrer under nitrogen. Subsequently, it heated to 80 degreeC, and after adding 14.36 g of propargyl bromide, reaction was performed, stirring for 6 hours. Thereafter, 40 g of methyl isobutyl ketone and 80 g of water were added to the reaction solution to perform liquid separation, and then the organic phase was introduced into a large amount of methanol, and the formed precipitate was filtered and dried to obtain a compound represented by the following formula (12). (Fig. 3)

[Formula 12]

(Comparative Example 4-1: Preparation of a hard mask composition for evaluating a gap fill)

After dissolving 10 g of the compound represented by Formula 12 in 90 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hard mask composition for evaluating a gap fill.

(Comparative Example 4-2: Preparation of hard mask composition for etching evaluation)

After dissolving 30 g of the compound represented by Chemical Formula 11 in 70 g of an organic solvent (PGMEA: cyclohexanone = 5:5 volume ratio), it was filtered through a 0.45 μm syringe filter to prepare a hardmask composition for etching evaluation.

Experimental example

Experimental Example 1. Evaluation of Gap Fill Characteristics

Examples 1-1, 3-1, 5-1, and 7-1 on the wafer on which the line and space pattern was formed with a line width of 30 nm and a pattern height of 220 nm. The hardmask composition prepared for evaluating the gap-fill in Example 19-1 and the hardmask composition prepared for evaluating the gap-fill in Comparative Examples 1-1 to 4-1 were each coated with a thickness of 250 nm using a spin coater.

Subsequently, baking was performed at 240° C. for 1 minute and double baking at 400° C. for 2 minutes in a chamber using a hot plate to form a hard mask film. The cross-section of the formed hardmask film was observed using an FE-SEM (manufactured by Hitachi: S-4300) equipment, and the results are shown in Table 1 below.

At this time, if the step ratio of the hard mask film formed on the high pattern thickness (line part) and the low part (space part) is 3 nm or less, it is marked as very good, and if the step ratio is 3 nm to 10 nm or less, it is good, and the step ratio is 10 nm to 15 nm. If it is less than or equal to 15 nm, it is marked as defective. In addition, the occurrence of voids was also indicated.

Step ratio Void formation Example 1-1 Good - Example 3-1 Good - Example 5-1 Good - Example 7-1 Very good - Example 8-1 Good - Example 9-1 Good - Example 10-1 Good - Example 11-1 Very good - Example 12-1 Good - Example 13-1 Good - Example 14-1 Very good - Example 15-1 Very good - Example 16-1 Very good - Example 17-1 Very good - Example 18-1 Very good - Example 19-1 Very good - Comparative Example 1-1 Bad - Comparative Example 2-1 Bad - Comparative Example 3-1 Very bad - Comparative Example 4-1 Very good Void formation

Looking at Table 1, in the case of the hard mask composition for evaluating the gap-fill prepared in Example 1-1, Example 3-1, Example 5-1, and Example 7-1 to Example 19-1, the gap-fill characteristics were It is excellent, and it can be seen that the step ratio is low and voids do not occur even when the gap fill process is performed on a fine pattern having a small line width. At this time, when the cross section of the hardmask film formed using the hardmask composition for evaluating the gap-fill of Example 19-1 was checked using an electron microscope (SEM), it can be seen that the gap-fill property is very excellent (see FIG. 1). That is, in the case of the hardmask composition for evaluating the gap-fill prepared in Examples 1-1, 3-1, 5-1, and 7-1 to 19-1, the thermal crosslinking functional group has an asymmetric structure. Since the eggplant contains a compound for a hard mask, it can be seen that the degree of crosslinking increases when crosslinking by heat and crosslinking at low temperatures is easy, increasing the density of the underlayer film and reducing the shrinkage caused by heat, so that the step ratio is high.

On the other hand, in the case of the hardmask composition for evaluating the gap-fill prepared in Comparative Examples 1-1 to 4-1, the gap-fill properties were in Example 1-1, Example 3-1, Example 5-1, and Example 7-1. It can be seen that compared to the hardmask composition for evaluating the gap fill prepared in Example 19-1.

For example, as shown in FIG. 2, when looking at the cross section of the hard mask film formed using the hard mask composition for evaluating the gap fill of Comparative Example 3-1, the gap fill characteristics were very poor, and as shown in FIG. 3, Comparative Example 4-1 Looking at the cross section of the hardmask film formed using the hardmask composition for evaluating the gap fill, it can be seen that voids occur.

Experimental Example 2. Etching resistance evaluation (1)

A 3.6 µm-thick amorphous carbon layer was deposited on a 200 mm-thick silicon wafer by chemical vapor deposition (CVD), and then an etching process was performed for 350 seconds using a CF ₄ plasma gas. The thickness of the thin film removed after the etching was completed was measured and shown in Table 2 as a reference example.

Next, the hardmask compositions prepared for etching evaluation in Examples 1-2, 5-2, 7-2 to 19-2 and Comparative Examples 2-2 to 4 on a silicon wafer having a thickness of 200 mm After spin-coating each hardmask composition (4g) prepared for etching evaluation in -2, bake for 1 minute at 240℃ in a high temperature hot plate chamber, and double bake at 400℃ for 2 minutes to make a 3.6 µm-thick hard mask A film was formed.

For each of the hardmask films, dry etching was performed for 60 seconds using a CF ₄ plasma gas, and then the etched thin film thickness (Å) per second (sec) was measured and shown in Table 2 below. In addition, the ratio (%) of the thickness remaining after etching to the initial thickness was measured and described in Table 2 below.

Etched thin film thickness (Å/s) Thickness after etching (%) Reference example 17.0 100 Example 1-2 20.3 84 Example 5-2 20.7 82 Example 7-2 20.3 84 Example 8-2 19.4 88 Example 9-2 20.9 81 Example 10-2 19.9 85 Example 11-2 19.6 87 Example 12-2 18.8 90 Example 13-2 20.1 85 Example 14-2 19.4 88 Example 15-2 19.2 88 Example 16-2 18.6 91 Example 17-2 19.7 86 Example 18-2 19.2 89 Example 19-2 19.0 89 Comparative Example 2-2 23.6 72 Comparative Example 3-2 22.1 77 Comparative Example 4-2 22.9 74

Looking at Table 2, in the case of the amorphous carbon layer of the reference example, it can be seen that the etched thickness per second (sec) for the CF ₄ plasma gas is 17.0 Å/s.

On the other hand, with respect to the second embodiment 1-2, Example 5-2, Example 7-2 film hard mask is formed by etching using the hard mask composition of the evaluation to Example 19-2 CF ₄ plasma gas of the invention ( The etched thickness per sec) increased from 18.6 Å/s to 20.9 Å/s, compared to the reference example, but improved compared to the hard mask film formed from the hard mask composition of Comparative Examples 2-2 to 4-2. Can be seen.

In particular, the hardmask films formed using the hardmask compositions for etching evaluation of Examples 1-2, 5-2, and 7-2 to 19-2 had a thickness ratio of 81 In% or more, it can be seen that it is higher than the hard mask film formed from the hard mask composition of Comparative Examples 2-2 to 4-2. Therefore, the hard mask films formed using the hard mask compositions for etching evaluation of Examples 1-2, 5-2, and 7-2 to 19-2 have higher etch resistance against CF ₄ plasma gas. Therefore, it is possible to form a hardmask film having a relatively low thickness, and thus it can be seen that the occurrence rate of pattern warpage during etching can be reduced.

Experimental Example 3. Etching resistance evaluation (2)

After depositing a 3.6 µm-thick amorphous carbon layer on a 200 mm-thick silicon wafer by using a chemical vapor deposition method (CVD), then, for 60 seconds each using O ₂ /N ₂ plasma mixed gas. During the etching process was performed. Then, the thickness of the thin film according to the etching time was measured and shown as a reference example in Table 3 below.

Then, compared with the hardmask composition prepared for etching evaluation in Examples 1-2, 3-2, 5-2, 7-2 to 19-2 on a silicon wafer of 200 mm thickness After spin-coating each of the hardmask compositions (4g) prepared for etching evaluation in Examples 1-2 to 4-2, bake for 1 minute at 240°C in a high temperature hot plate chamber, and double bake at 400°C for 2 minutes. A 3.6 µm-thick hardmask film was formed.

Using O ₂ /N ₂ plasma mixed gas for the hard mask film, 140 seconds (etch rate 10%), 360 seconds (etch rate 25%), 720 seconds (etch rate 50%), 1000 seconds (etch rate) 70%) for dry etching, and then the average thin film thickness (Å) etched per second (sec) was measured and shown in Table 3 below. In addition, the thickness ratio (%) remaining after the average etching relative to the initial thickness was measured and shown in Table 3 below.

In addition, the etching rate (bulk etch rate, BER) is calculated by introducing the etched thin film thickness (Å) for each etching time (eg, 140 seconds, 360 seconds, 720 seconds, and 1000 seconds) to the following (Equation 1). And, their standard deviation (Standard derivation, hereinafter referred to as'Stdev') is shown in Table 3 below.

(Equation 1) Etching rate (BER) = (initial thin film thickness-thin film thickness after etching) / etching time

Etched average
Thin film thickness (Å/s) Average etch thickness
ratio (%) O ₂ /N ₂ etch rate
(Stdev) Reference example 13.9 100 - Example 1-2 19.3 72 0.19 Example 3-2 18.7 74 0.17 Example 5-2 22.5 62 0.17 Example 7-2 21.7 64 0.17 Example 8-2 18.1 77 0.18 Example 9-2 23.4 60 0.16 Example 10-2 20.3 69 0.16 Example 11-2 19.1 73 0.16 Example 12-2 17.2 81 0.19 Example 13-2 20.2 69 0.17 Example 14-2 18.1 77 0.17 Example 15-2 17.3 80 0.17 Example 16-2 18.6 75 0.18 Example 17-2 19.0 73 0.16 Example 18-2 18.3 76 0.16 Example 19-2 17.3 80 0.16 Comparative Example 1-2 24.1 58 0.29 Comparative Example 2-2 28.2 49 0.33 Comparative Example 3-2 26.8 52 0.26 Comparative Example 4-2 27.5 51 0.35

Referring to Table 3, in the case of the amorphous carbon layer as a reference example, it can be seen that the etching thickness per second (sec) for the O ₂ /N ₂ plasma mixed gas is 13.9 Å/s.

On the other hand, O ₂ /N _{2 of a} hardmask film formed using the hardmask composition for etching evaluation of Examples 1-2, 3-2, 5-2, and 7-2 to 19-2 The etching thickness per second (sec) for the plasma mixed gas was 23.4 Å/s or less, which was increased compared to the reference example, but the hardmask film formed using the hardmask composition for etching evaluation of Comparative Examples 1-2 to 4-2 It can be seen that it is improved compared to.

In addition, the hardmask film formed using the hardmask composition for etching evaluation of Examples 1-2, 3-2, 5-2, 7-2 to 19-2 was compared to the initial thickness after etching. It can be seen that the remaining thickness ratio is 60% or more, and has higher etch resistance compared to the hard mask film formed from the hard mask compositions of Comparative Examples 1-2 to 4-2.

In particular, the hardmask film formed using the hardmask composition for etching evaluation of Examples 1-2, 3-2, 5-2, 7-2 to 19-2 was O ₂ /N ₂ The surface deviation value for the etching rate of the plasma mixed gas is significantly lower than that of the hard mask composition of Comparative Examples 1-2 to 4-2, thus securing a more uniform etching rate for the O ₂ /N ₂ plasma mixed gas You can see that you can.

From these results, when using the compound for a hardmask of the present invention containing a polycyclic aromatic compound in which at least two or more hydroxy groups are substituted at an asymmetrical position, the density of the hardmask film increases and the resistance to O ₂ /N ₂ plasma mixed gas is increased. It can be seen that it is possible to form a hardmask film having a high etching rate and a uniform etching rate. Accordingly, it can be predicted that a hardmask film having a lower thickness can be formed, and accordingly, the occurrence rate of pattern warpage during etching can be reduced.

Claims (16)

A hardmask compound comprising a polycyclic aromatic compound in which at least two or more hydroxy groups are substituted in an asymmetric position with each other.
The method according to claim 1,
The polycyclic aromatic compound is at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2):
[Formula 1]

In Formula 1,
R ₁ and R ₄ are independent of each other, at least one of which is an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the rest is a hydroxy group (-OH), an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms,
R ₂ , R ₃ , R ₅ and R ₆ are Each independently Hydrogen, an alkyl group having 1 to 10 carbon atoms, or -OR _o , wherein R _o is hydrogen or an alkyl group having 1 to 10 carbon atoms.

[Formula 2]

In Chemical Formula 2,
R ₇ , R _7a , R ₈ and R _8a are independent of each other, of which at least two or more are hydroxy groups (-OH), the remainder is an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the hydroxy group ( -OH) has an asymmetric structure with each other,
R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are Each independently Hydrogen, an alkyl group having 1 to 10 carbon atoms, or -OR _o , wherein R _o is hydrogen or an alkyl group having 1 to 10 carbon atoms,
n and m are each independently an integer of 0 to 3.
The method according to claim 1,
In Formula 1, R ₁ and R ₄ are independent of each other, at least one of which is an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the rest is a hydroxy group (-OH) or an aromatic hydrocarbon group having 6 to 20 carbon atoms,
R ₂ , R ₃ , R ₅ and R ₆ are Each independently Hydrogen or -OR _o , wherein R _o is hydrogen or an alkyl group having 1 to 10 carbon atoms.
The method according to claim 1,
In Formula 1, R ₁ and R ₄ are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms,
R ₂ and R ₅ are each independently Hydrogen, or -OR _o , wherein R _o is hydrogen or an alkyl group having 1 to 10 carbon atoms,
R ₃ and R ₆ are each independently A compound for a hard mask that is hydrogen.
The method according to claim 1,
The compound represented by Formula 1 is at least one compound selected from the group consisting of compounds represented by the following Formulas 1a to 1l.
[Formula 1a]

[Formula 1b]

[Formula 1c]

[Formula 1d]

[Formula 1e]

[Formula 1f]

[Formula 1g]

[Formula 1h]

[Formula 1i]

[Formula 1j]

[Formula 1k]

[Formula 1l]

The method according to claim 1,
In Formula 2, R ₇ , R _7a , R ₈ and R _8a are independent of each other, at least two of which are hydroxy groups (-OH), the rest are aromatic hydrocarbon groups having 6 to 20 carbon atoms, and the hydroxy group (-OH ) Have an asymmetric structure with each other,
R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are Each independently Hydrogen, or -OR _o , wherein R _o is hydrogen or an alkyl group having 1 to 10 carbon atoms,
n and m are each independently an integer of 0 to 3, wherein the hardmask compound.
The method according to claim 1,
In Chemical Formula 2,
R ₇ and R ₈ are each independently a hydroxy group (-OH) or an aromatic hydrocarbon group having 6 to 20 carbon atoms,
R _7a and R _8a are hydroxy groups (-OH),
R ₉ and R ₁₂ are Each independently Hydrogen, or -OR _o , wherein R _o is hydrogen or an alkyl group having 1 to 10 carbon atoms,
R ₁₀ and R ₁₁ are each independently Hydrogen,
n and m are each independently an integer of 0 to 3, wherein the hardmask compound.
The method according to claim 1,
The compound represented by Formula 2 is at least one compound selected from the group consisting of compounds represented by the following Formulas 2a to 2p.
[Formula 2a]

[Formula 2b]

[Formula 2c]

[Formula 2d]

[Formula 2e]

[Formula 2f]

[Chemical Formula 2g]

[Formula 2h]

[Formula 2i]

[Formula 2j]

[Formula 2k]

[Formula 2l]

[Chemical Formula 2m]

[Formula 2n]

[Formula 2o]

[Formula 2p]

A hard mask composition comprising the compound for a hard mask of claim 1 and a solvent.
The method of claim 9,
The hardmask composition is contained in an amount of 1% to 65% by weight based on the total weight of the hardmask composition.
The method of claim 9,
The hardmask composition is at least one selected from the group consisting of a ketone-based solvent, a cellosolve-based solvent, an ester-based solvent, an alcohol-based solvent, and an aromatic hydrocarbon solvent.
The method of claim 9,
The solvent is at least one selected from the group consisting of cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl hydroxyisobutyrate, 1-methoxy-2-propanol, and anisole. Hardmask composition.
Coating the hardmask composition of claim 9 on the top of the layer to be etched on the substrate;
Curing the hardmask composition to form a hardmask layer;
Forming a photoresist layer over the hardmask layer;
Exposing and developing the photoresist layer to form a photoresist pattern;
Selectively patterning the hardmask layer using the photoresist pattern as an etching mask; And
Patterning a layer to be etched by using the patterned hard mask layer as an etching mask.
The method of claim 13,
The step of coating the hardmask composition is a method of forming a pattern of a semiconductor device to be performed by a spin-on coating method.
The method of claim 13,
Curing the hardmask composition is a method of forming a pattern of a semiconductor device to be performed by heat treatment at 100 ℃ to 500 ℃.
The method of claim 13,
The method of forming a pattern of a semiconductor device further comprising forming an antireflection layer on the hardmask layer after the forming of the hardmask layer and before the forming of the photoresist layer.

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