KR20240125309A - Hardmask composition, hardmask layer and method of forming patterns - Google Patents

Abstract

The present invention relates to a hardmask composition comprising a compound represented by the following chemical formula 1 and a solvent, a hardmask layer manufactured from the hardmask composition, and a method for forming a pattern from the hardmask composition.
[Chemical Formula 1]

The definition of the above chemical formula 1 is as described in the specification.

Description

HARDMASK COMPOSITION, HARDMASK LAYER AND METHOD OF FORMING PATTERNS

The present invention relates to a hardmask composition, a hardmask layer comprising a cured product of the hardmask composition, and a method for forming a pattern using the hardmask composition.

The semiconductor industry has recently developed from patterns of several hundred nanometers in size to ultra-fine technologies with patterns of several to tens of nanometers in size. To realize such ultra-fine technologies, effective lithographic techniques are 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.

Recently, as the size of the pattern to be formed has decreased, it has become difficult to form a fine pattern with a good profile using only the typical lithographic technique described above. Accordingly, a fine pattern can be formed by forming an auxiliary layer, also known as a hardmask layer, between the material layer to be etched and the photoresist layer.

One embodiment provides a hardmask composition that can be effectively applied to a hardmask layer.

Another embodiment provides a hardmask layer comprising a cured product of the hardmask composition.

Another embodiment provides a method of forming a pattern using the hardmask composition.

A hard mask composition according to one embodiment comprises a compound represented by the following chemical formula 1 and a solvent.

[Chemical Formula 1]

In the above chemical formula 1,

X ¹ to X ³ are each independently N or CR ^a , wherein R ^a is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,

A ¹ to A ³ are each independently a substituted or unsubstituted C6 to C30 aromatic ring, a substituted or unsubstituted C2 to C40 heteroaromatic ring, or a combination thereof,

L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a combination thereof,

B ¹ to B ³ are each independently a substituted or unsubstituted C6 to C30 aromatic ring group, a substituted or unsubstituted C2 to C40 heteroaromatic ring, or a combination thereof,

n ¹ to n ³ are each independently an integer from 0 to 5, provided that n 1 to n 3 are not simultaneously 0.

One or both of X ¹ to X ³ in chemical formula 1 are N, or all of X ¹ to X ³ are CR ^a , and R ^a is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C2 to C20 heteroaryl group, or a combination thereof.

A ¹ to A ³ in chemical formula 1 are each independently a substituted or unsubstituted C6 to C30 aromatic ring.

A hard mask composition wherein A ¹ to A ³ of chemical formula 1 are each independently any one of a substituted or unsubstituted moiety selected from the following Group 1 and Group 2.

[Group 1]

[Group 2]

In the above group 2, Z is N, O, or S, and M ¹ and M ² are each independently a substituted or unsubstituted C6 to C30 aromatic ring.

A hard mask composition wherein A ¹ to A ³ of chemical formula 1 are each independently any one of substituted or unsubstituted moieties selected from the following Group 1-1 and the following Group 2-1:

[Group 1-1]

[Group 2-1]

In the above group 2-1, Z is N, O, or S, and M ¹ and M ² are each independently a substituted or unsubstituted C6 to C20 aromatic ring.

A ¹ to A ³ of chemical formula 1 are each independently any one of a substituted or unsubstituted moiety selected from the following Group 1-2 and the following Group 2-2:

[Group 1-2]

[Group 2-2]

L ¹ to L ³ in chemical formula 1 are each independently a single bond, a substituted or an unsubstituted C1 to C10 alkylene group, or a combination thereof, and B ¹ to B ³ are each independently a substituted or unsubstituted C6 to C30 aromatic ring group, a substituted or unsubstituted C2 to C40 heteroaromatic ring, or a combination thereof, and n1 to n3 are each independently one of the integers 0 to 3, provided that n1 to n3 are not simultaneously 0.

In chemical formula 1, L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a combination thereof, B ¹ to B ³ are each independently a substituted or unsubstituted C6 to C30 aromatic ring group, and n1 to n3 are each independently 0 or 1, but n1 to n3 are not both 0.

L ¹ to L ³ of the chemical formula 1 are each independently a single bond, a C1 to C10 alkylene group substituted or unsubstituted with a hydroxy group, or a combination thereof, B ¹ to B ³ are each independently any one of a substituted or unsubstituted moiety selected from the following Group 3, and n1 to n3 are each independently 0 or 1, provided that n1 to n3 are not simultaneously 0:

[Group 3]

The above chemical formula 1 is represented by the following chemical formula 1-1, or the following chemical formula 1-2:

[Chemical Formula 1-1]

[Chemical Formula 1-2]

In the above chemical formulas 1-1 and 1-2,

A ⁴ to A ⁹ are each independently a substituted or unsubstituted C6 to C30 aromatic ring, a substituted or unsubstituted C2 to C40 heteroaromatic ring, or a combination thereof,

L ⁴ to L ⁹ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a combination thereof,

B ⁴ to B ⁹ are each independently a substituted or unsubstituted C6 to C30 aromatic ring group, a substituted or unsubstituted C2 to C40 heteroaromatic ring, or a combination thereof,

n4 to n9 are each independently an integer from 0 to 5, provided that n4 to n6 are not both 0, and n7 to n9 are not both 0.

A ⁵ and A ⁶ of the above chemical formula 1-1 are the same, or A ⁸ and A ⁹ of the above chemical formula 1-2 are the same.

The above chemical formula 1 is represented by the following chemical formula 2 or the following chemical formula 3:

[Chemical formula 2]

[Chemical Formula 3]

In the above chemical formulas 2 and 3,

A ⁴ and A ⁷ are each independently substituted or unsubstituted benzene, naphthalene, anthracene, phenanthrene, pyrene, or a combination thereof,

L ⁴ to L ⁹ are each independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a combination thereof,

B ⁵ to B ⁹ are each independently a substituted or unsubstituted phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrene group, or a combination thereof,

n4 to n9 are each independently 0 or 1, provided that n4 to n6 are not simultaneously 0, and n7 to n9 are not simultaneously 0.

The above chemical formula 1 is represented by any one of the following chemical formulas 2-1, 2-2, and 3-1 to 3-6:

[Chemical Formula 2-1]

[Chemical Formula 2-2]

[Chemical Formula 3-1]

[Chemical Formula 3-2]

[Chemical Formula 3-3]

[Chemical Formula 3-4]

[Chemical Formula 3-5]

[Chemical Formula 3-6]

The molecular weight of the above compound is 300 g/mol to 5,000 g/mol.

The above compound is included in an amount of 0.1 wt% to 30 wt% based on the total weight of the hard mask composition.

The solvent is propylene glycol, propylene glycol diacetate, methoxy propanediol, diethylene glycol, diethylene glycol butyl ether, tri(ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone or ethyl 3-ethoxypropionate.

According to another embodiment, a hardmask layer comprising a cured product of the hardmask composition described above is provided.

According to another embodiment, there is provided a method of manufacturing a hard mask, comprising: providing a material layer on a substrate; applying the hard mask composition described above on the material layer; heat-treating the hard mask composition to form a hard mask layer; forming a photoresist layer on the hard mask layer; exposing and developing the photoresist layer to form a photoresist pattern; using the photoresist pattern. A pattern forming method is provided, comprising the steps of selectively removing the hard mask layer and exposing a portion of the material layer, and etching the exposed portion of the material layer.

The step of forming the above hard mask layer includes a step of heat treatment at 100°C to 1,000°C.

A hard mask composition according to one embodiment has excellent solubility in a solvent and can be effectively applied to a hard mask layer.

A hard mask layer formed from a hard mask composition according to one embodiment can secure excellent etch resistance.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

Unless otherwise defined herein, the term "substituted" means a compound in which a hydrogen atom is substituted with a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a vinyl group, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C7 to C30 arylalkyl group, a C9 to C30 allylaryl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 It means substituted with a substituent selected from a cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C3 to C30 heterocycloalkyl group, and combinations thereof.

In addition, two adjacent groups among the substituted halogen atom (F, Br, Cl, or I), a hydroxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a C6 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, or a C2 to C30 heterocyclic group. Substituents may be fused to form rings. For example, the substituted C6 to C30 aryl group may be fused with another adjacent substituted C6 to C30 aryl group to form a substituted or unsubstituted fluorene ring.

As used herein, the term "aryl group" refers to a group having one or more hydrocarbon aromatic moieties, and broadly includes a form in which hydrocarbon aromatic moieties are linked by single bonds and a non-aromatic fused ring in which hydrocarbon aromatic moieties are directly or indirectly fused. The aryl group includes a monocyclic, polycyclic, or fused polycyclic (i.e., a ring that shares adjacent pairs of carbon atoms) functional groups.

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

Unless otherwise defined herein, a "heteroaryl group" means an aryl group containing at least one heteroatom selected from the group consisting of N, O, S, P, and Si. Two or more heteroaryl groups may be directly connected via a sigma bond, or, when the heteroaryl group includes two or more rings, the two or more rings may be fused to each other. When the heteroaryl group is a fused ring, each ring may contain 1 to 3 of the heteroatoms.

More specifically, the substituted or unsubstituted aryl group and/or the substituted or unsubstituted heteroaryl group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted quaterphenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted Thiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted benzoxazinyl group, a substituted or unsubstituted benzthiazinyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazinyl group, Or it may be a form in which an unsubstituted phenoxazinyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, a pyridoindolyl group, a benzopyridoxazinyl group, a benzopyridothiazinyl group, a 9,9-dimethyl-9,10-dihydroacridinyl group, a combination thereof, or a combination thereof is fused, but is not limited thereto.

Unless otherwise specified herein, “combination” means mixing or copolymerization.

Additionally, in this specification, “polymer” may include both an oligomer and a polymer.

Unless otherwise specified herein, “weight average molecular weight” is the value measured by dissolving a powder sample in tetrahydrofuran (THF) using Agilent Technologies’ 1200 series Gel Permeation Chromatography (GPC) (column: Shodex LF-804; standard sample: Shodex polystyrene).

Additionally, unless otherwise defined herein, '*' indicates a structural unit of a compound or a connecting point of a compound moiety.

There is a constant demand for reducing chip sizes in the semiconductor industry. To meet this demand, the line width of the resist patterned in lithography technology must be tens of nanometers. Accordingly, the height that can withstand the line width of the resist pattern is limited, and there are cases where the resists do not have sufficient resistance in the etching step. To compensate for this, an auxiliary layer called a hardmask layer is used between the material layer to be etched and the photoresist layer. This hardmask layer acts as an intermediate film that transfers the fine pattern of the photoresist to the material layer through selective etching, so the hardmask layer must have etch resistance to withstand the etching process required for pattern transfer.

Conventional hard mask layers are formed by chemical or physical deposition methods, but these have problems of low economic feasibility due to large equipment scale and high process costs. Therefore, a technology for forming a hard mask layer using a spin-coating technique has recently been developed. The spin-coating technique is easier to process than conventional methods, and the gap-fill characteristics and planarization characteristics of the hard mask layer manufactured thereby can be better, but the etch resistance required for the hard mask layer tends to be somewhat lowered. Therefore, a hard mask composition to which the spin-coating technique can be applied, and a hard mask layer formed thereby, is required to have etch resistance equivalent to that of a hard mask layer formed by a chemical or physical deposition method.

Accordingly, research is being actively conducted to maximize the carbon content contained in the hardmask composition in order to improve the etch resistance of the hardmask layer. However, as the carbon content of the hardmask composition is maximized, the solubility of the composition in a solvent tends to decrease, and thus, it is required to maximize the carbon content of the compound included in the hardmask composition so as to improve the etch resistance of the hardmask layer formed therefrom, while not decreasing the solubility of the compound in a solvent.

A hard mask composition according to one embodiment can increase the carbon content in the composition by including a compound including a plurality of aromatic rings or heteroaromatic rings. Accordingly, a hard mask layer obtained from the composition can have improved etch resistance. In addition, by allowing the aromatic rings or heteroaromatic rings to be connected by a flexible linking group, the solubility of the compound including a plurality of aromatic rings or heteroaromatic rings in a solvent can be improved.

Specifically, a hard mask composition according to one embodiment includes a compound represented by the following chemical formula 1 and a solvent.

[Chemical Formula 1]

In the above chemical formula 1,

X ¹ to X ³ are each independently N or CR ^a , wherein R ^a is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,

A ¹ to A ³ are each independently a substituted or unsubstituted C6 to C30 aromatic ring, a substituted or unsubstituted C2 to C40 heteroaromatic ring, or a combination thereof,

L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a combination thereof,

B ¹ to B ³ are each independently a substituted or unsubstituted C6 to C30 aromatic ring group, a substituted or unsubstituted C2 to C40 heteroaromatic ring, or a combination thereof,

n ¹ to n ³ are each independently an integer from 0 to 5, provided that n 1 to n 3 are not simultaneously 0.

As described above, the compound included in the hard mask composition according to one embodiment includes a core and A ¹ to A ³ groups directly connected thereto, thereby increasing the carbon content contained in the compound and the composition including the same. Accordingly, the etch resistance of the hard mask layer obtained from the composition can be increased. In addition, by including at least one linking group such as L ¹ to L ³ , flexibility is imparted to the compound, thereby enabling it to be effectively dissolved in a solvent.

In particular, a hard mask composition according to one embodiment may have significantly better solubility in a solvent than a composition including a polymer including a structural unit derived from chemical formula 1 by including a compound represented by chemical formula 1, and thus may be effectively applied to a solution process such as spin-coating.

One or both of X ¹ to X ³ in the above chemical formula 1 may be N and the remainder may be CR ^a , or all of X ¹ to X ³ may be CR ^a . The R ^a may be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C2 to C20 heteroaryl group, or a combination thereof.

For example, R ^a can be hydrogen, an unsubstituted C1 to C5 alkyl group, an unsubstituted C2 to C6 alkenyl group, an unsubstituted C2 to C6 alkynyl group, an unsubstituted C6 to C10 aryl group, or an unsubstituted C2 to C10 heteroaryl group. For example, R ^a is hydrogen, an unsubstituted C1 to C5 alkyl group, or an unsubstituted C6 to C10 aryl group, for example, R ^a is hydrogen.

A ¹ to A ³ of the above chemical formula 1 may be the same as each other, may be all different from each other, and two of A ¹ to A ³ may be the same. Each of the above A ¹ to A ³ may independently be a substituted or unsubstituted C6 to C30 aromatic ring. For example ^, each of the above chemical formula 1 may independently be ^a substituted or unsubstituted moiety selected from the following Group 1:

[Group 1]

For example, A ¹ to A ³ may each independently be substituted or unsubstituted with any one of the moieties selected from the following Group 1-1:

[Group 1-1]

For example, A ¹ to A ³ may each independently be substituted or unsubstituted with any one of the moieties selected from the following Groups 1-2:

[Group 1-2]

Each of A ¹ to A ³ above may independently be a substituted or unsubstituted C2 to C40 heteroaromatic ring. For example, each of A ¹ to A ³ above may independently be a substituted or unsubstituted moiety selected from the following Group 2:

[Group 2]

For example, A ¹ to A ³ may each independently be substituted or unsubstituted with any one of the moieties selected from the following Group 2-1:

[Group 2-1]

In the above Group 2 and Group 2-1, Z is N, O, or S, and M ¹ and M ² are each independently a substituted or unsubstituted C6 to C30 aromatic ring. For example, Z can be N, and M ¹ and M ² are each independently a substituted or unsubstituted C6 to C20 aromatic ring, for example, but not limited to, benzene or naphthalene.

For example, A ¹ to A ³ may each independently be substituted or unsubstituted with any one of the moieties selected from the following Group 2-2, but are not limited thereto:

[Group 2-2]

In the chemical formula 1 above, since A ¹ to A ³ are directly connected to a core composed of an aromatic ring or a heteroaromatic ring, a hard mask layer formed by a composition including such a compound can secure excellent solubility and etch resistance.

In the above chemical formula 1, L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a combination thereof. Accordingly, the compound can secure a high degree of rotational freedom, and a hard mask composition including the same can be effectively applied to a solution process such as spin coating.

The above L ¹ to L ³ can be, for example, a single bond, or a substituted C1 to C10 alkylene group, for example, a substituted C1 to C5 alkylene group. The substitution of the alkylene group can be, for example, a hydroxyl group, an amine group, a thiol group, a methoxy group, or an ethoxy group, for example, a hydroxyl group, but is not limited thereto.

For example, when at least one of L ¹ to L ³ is an alkylene group substituted with a hydroxy group, the solubility in a solvent can be increased.

B ¹ to B ³ of the above chemical formula 1 are each independently a substituted or unsubstituted C6 to C30 aromatic ring group, a substituted or unsubstituted C2 to C40 heteroaromatic ring, or a combination thereof. For example, they may be a substituted or unsubstituted C6 to C30 aromatic ring group, and for example, B ¹ to B ³ of the chemical formula 1 may each independently be a substituted or unsubstituted moiety selected from the following Group 3:

[Group 3]

In addition, B ¹ to B ³ of the above chemical formula 1 may each independently be a substituted or unsubstituted phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, or a pyrene group, for example, a substituted or unsubstituted phenyl group or a naphthalene group.

In the chemical formula 1, n1 to n3 are one of the integers from 0 to 5, for example, one of the integers from 0 to 3, for example, one of the integers from 0 to 2, for example, 0 or 1, but n1 to n3 are not 0 at the same time. As one example, two of n1 to n3 are 1 and the rest are 0, and as another example, n1 to n3 are 1 at the same time, but are not limited thereto.

The above chemical formula 1 can be represented by the following chemical formula 1-1 or the following chemical formula 1-2.

[Chemical Formula 1-1]

[Chemical Formula 1-2]

In the above chemical formulas 1-1 and 1-2, A ⁴ to A ⁹ are each independently a substituted or unsubstituted C6 to C30 aromatic ring, a substituted or unsubstituted C2 to C40 heteroaromatic ring, or a combination thereof.

L ⁴ to L ⁹ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a combination thereof,

B ⁴ to B ⁹ are each independently a substituted or unsubstituted C6 to C30 aromatic ring group, a substituted or unsubstituted C2 to C40 heteroaromatic ring, or a combination thereof,

n4 to n9 are each independently an integer from 0 to 5, provided that n4 to n6 are not both 0, and n7 to n9 are not both 0.

In the above chemical formula 1-1, A ⁴ to A ⁶ may all be different from each other, or may all be the same from each other, for example, two of A ⁴ to A ⁶ may be the same, for example, A ⁵ and A ⁶ may be the same, but are not limited thereto.

In the above chemical formula 1-2, A ⁷ to A ⁹ may all be different from each other, or may all be the same from each other, for example, two of A ⁷ to A ⁹ may be the same, for example, A ⁸ and A ⁹ may be the same, but are not limited thereto.

For example, the chemical formula 1 may be represented by the following chemical formula 2 or the following chemical formula 3, but is not limited thereto.

[Chemical formula 2]

[Chemical Formula 3]

In the above chemical formulas 2 and 3,

A ⁴ and A ⁷ are each independently substituted or unsubstituted benzene, naphthalene, anthracene, phenanthrene, pyrene, or a combination thereof,

L ⁴ to L ⁹ are each independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a combination thereof,

B ⁵ to B ⁹ are each independently a substituted or unsubstituted phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrene group, or a combination thereof,

n4 to n9 are each independently 0 or 1, provided that n4 to n6 are not simultaneously 0, and n7 to n9 are not simultaneously 0.

For example, the chemical formula 1 may be represented by any one of the following chemical formulas 2-1, 2-2, and 3-1 to 3-6, but is not limited thereto.

[Chemical Formula 2-1]

[Chemical Formula 2-2]

[Chemical Formula 3-1]

[Chemical Formula 3-2]

[Chemical Formula 3-3]

[Chemical Formula 3-4]

[Chemical Formula 3-5]

[Chemical Formula 3-6]

The compound may have a molecular weight of 300 g/mol to 5,000 g/mol. For example, it can have a molecular weight of 400 g/mol to 5,000 g/mol, for example, 500 g/mol to 5,000 g/mol, for example, 500 g/mol to 4,500 g/mol, for example, 500 g/mol to 4,000 g/mol, for example, 600 g/mol to 4,500 g/mol, for example, 600 g/mol to 4,000 g/mol, for example, 700 g/mol to 5,000 g/mol, for example, 700 g/mol to 4,500 g/mol, for example, 700 g/mol to 4,000 g/mol, for example, 700 g/mol to 3,500 g/mol, but is not limited thereto. By having a molecular weight within the above range, the carbon content and solubility in a solvent of a hard mask composition including the compound can be controlled and optimized.

The compound may be included in an amount of 0.1 wt% to 30 wt% based on the total weight of the hardmask composition. For example, about 0.2 wt% to 30 wt%, for example, about 0.5 wt% to 30 wt%, for example, about 1 wt% to 30 wt%, for example, about 1 wt% to 25 wt%, for example, about 1 wt% to 20 wt%, but is not limited thereto. By including the compound in the above range, the thickness, surface roughness, and flattening degree of the hardmask can be easily controlled.

The hardmask composition according to one embodiment may include a solvent, and in one embodiment, the solvent may include at least one selected from, but not limited to, propylene glycol, propylene glycol diacetate, methoxy propanediol, diethylene glycol, diethylene glycol butyl ether, tri(ethylene glycol)monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone, or ethyl 3-ethoxypropionate. The solvent is not particularly limited as long as it has sufficient solubility and/or dispersibility for the compound.

The above hard mask composition may additionally contain additives such as a surfactant, a crosslinking agent, a thermal acid generator, and a plasticizer.

The surfactant may include, but is not limited to, fluoroalkyl compounds, alkylbenzene sulfonates, alkyl pyridinium salts, polyethylene glycol, quaternary ammonium salts, etc.

The cross-linking agent may include, for example, a melamine-based, a substituted urea-based, or a polymer-based thereof. Preferably, a cross-linking agent having at least two cross-linking-forming substituents may be used, for example, a compound such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or butoxymethylated thiourea.

In addition, a crosslinking agent having high heat resistance can be used as the crosslinking agent. A compound containing a crosslinking-forming substituent having an aromatic ring (e.g., a benzene ring, a naphthalene ring) in the molecule can be used as the crosslinking agent having high heat resistance.

The above-mentioned thermal acid generator may be, but is not limited to, acidic compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid, and/or 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic alkyl esters of technical acids.

According to another embodiment, a hardmask layer comprising a cured product of the hardmask composition described above is provided.

A method of forming a pattern using the hard mask composition described below is described.

A method for forming a pattern according to one embodiment comprises the steps of providing a material layer on a substrate, applying a hardmask composition comprising the above-described polymer and a solvent on the material layer, heat-treating the hardmask composition to form a hardmask layer, forming a photoresist layer on the hardmask layer, exposing and developing the photoresist layer to form a photoresist pattern, and using the photoresist pattern. A method of forming a substrate, comprising: selectively removing the hard mask layer and exposing a portion of the material layer; and etching the exposed portion of the material layer. The substrate may be, for example, a silicon wafer, a glass substrate, or a polymer substrate.

The material layer is a material to be ultimately patterned, and may be, for example, a metal layer such as aluminum or copper, a semiconductor layer such as silicon, or an insulating layer such as silicon oxide or silicon nitride. The material layer may be formed, for example, by a chemical vapor deposition method.

The hard mask composition is as described above, and can be prepared in a solution form and applied by a spin-on coating method. At this time, the coating thickness of the hard mask composition is not particularly limited, but can be applied to a thickness of, for example, about 50 to 200,000 Å.

The step of heat treating the hard mask composition may be performed, for example, at about 100° C. to 1,000° C. for about 10 seconds to 1 hour. As an example, the step of heat treating the hard mask composition may include a plurality of heat treatment steps, and may include, for example, a first heat treatment step and a second heat treatment step.

In one embodiment, the step of heat treating the hard mask composition can include one heat treatment step performed at, for example, about 100° C. to 1,000° C. for about 10 seconds to 1 hour, and as an example, the heat treatment step can be performed under an air atmosphere, and can be performed under an atmosphere having a nitrogen concentration of 1 wt% or less, or an oxygen concentration of 1 wt% or less.

In one embodiment, the step of heat treating the hard mask composition comprises a first heat treatment step performed at, for example, about 100° C. to 1,000° C., for example, about 100° C. to 800° C., for example, about 100° C. to 500° C., for example, about 150° C. to 400° C., for about 30 seconds to 1 hour, for example, about 30 seconds to 30 minutes, for example, about 30 seconds to 10 minutes, for example, about 30 seconds to 5 minutes. Also, the second heat treatment step may be continuously included, for example, at about 100° C. to 1,000° C., for example, about 300° C. to 1,000° C., for example, about 500° C. to 1,000° C., for example, about 500° C. to 600° C., for about 30 seconds to 1 hour, for example, about 30 seconds to 30 minutes, for example, about 30 seconds to 10 minutes, for example, about 30 seconds to 5 minutes. As an example, the first and second heat treatment steps may be performed under an air atmosphere, and may be performed under an atmosphere having a nitrogen concentration of 1 wt% or less, or an oxygen concentration of 1 wt% or less.

By performing at least one step of the heat treatment step of the above hard mask composition at a high temperature of 200° C. or higher, high etch resistance capable of withstanding etching gases and chemical liquids exposed in subsequent processes including an etching process can be exhibited.

In one embodiment, the step of forming the hardmask layer may include a UV/Vis curing step and/or a near IR curing step.

In one embodiment, the step of forming the hardmask layer may include at least one of the first heat treatment step, the second heat treatment step, the UV/Vis curing step, and the near IR curing step, or may include two or more steps sequentially.

In one embodiment, the method may further include forming a silicon-containing thin film layer on the hard mask layer. The silicon-containing thin film layer may be formed of a material such as SiCN, SiOC, SiON, SiOCN, SiC, SiO and/or SiN.

In one embodiment, a bottom anti-reflective coating (BARC) may be further formed on top of the silicon-containing thin film layer or on top of the hard mask layer prior to the step of forming the photoresist layer.

In one embodiment, the step of exposing the photoresist layer can be performed using, for example, ArF, KrF, or EUV. Additionally, a heat treatment process can be performed at about 100° C. to 700° C. after exposure.

In one embodiment, the step of etching the exposed portion of the material layer can be performed by dry etching using an etching gas, and the etching gas can be, for example, N ₂ /O ₂ , CHF ₃ , CF ₄ , Cl ₂ , BCl ₃ and a mixed gas thereof.

The above etched material layer can be formed into a plurality of patterns, and the plurality of patterns can be various, such as a metal pattern, a semiconductor pattern, an insulating pattern, etc., and can be applied as various patterns in a semiconductor integrated circuit device, for example.

The embodiments of the present invention described above will be described in more detail through the following examples. However, the following examples are for illustrative purposes only and do not limit the scope of the present invention.

Synthesis of compounds

Intermediate synthesis example 1

1-Acetylpyrene (19.54 g, 0.080 mol) and m-xylene (19.65 g) are added to a 500 ml flask and stirred for 10 minutes. Dodecylbenzenesulfonic acid (2.61 g, 8.00 mmol) is added and stirred at 140°C for 18 hours. At 100°C, 30 g of toluene is added, cooled to 50°C, 200 g of methanol is added and stirred at room temperature for 1 hour. After filtering the precipitate, 20 g of toluene is added to the precipitate, stirred for 1 hour, filtered to collect the precipitate, and dried to obtain a compound represented by the following chemical formula 2-1a.

[Chemical Formula 2-1a]

Intermediate synthesis example 2

In a 500 ml flask, add 1-Acetylpyrene (15.00 g, 0.061 mol), 1-Pyrenecarboxaldehyde (7.07 g, 0.031 mol), and DMSO (95 g) and stir for 10 minutes. Then, add 2.15 g of 40% KOH aqueous solution and stir at 80°C for 12 hours. Cool the reaction mass to 60°C, add ammonium acetate (11.83 g, 0.15 mol), and stir at 120°C for 24 hours. After cooling to room temperature, add 190 g of methanol and stir for 1 hour. After filtering the sediment, 20 g of toluene and 20 g of methanol are added to the sediment, stirred for 1 hour, and the sediment is filtered to recover and dried to obtain a compound represented by the following chemical formula 3-1a.

[Chemical Formula 3-1a]

Intermediate synthesis example 3

A compound represented by the following chemical formula 3-2a is obtained using the same method as in Intermediate Synthesis Example 2, except that 6.33 g of 9-anthracenecarboxaldehyde is used instead of 7.07 g of 1-pyrenecarboxaldehyde.

[Chemical Formula 3-2a]

Intermediate synthesis example 4

A compound represented by the following chemical formula 3-3a is obtained using the same method as in Intermediate Synthesis Example 2, except that 4.79 g of 1-naphthaldehyde is used instead of 7.07 g of 1-pyrenecarboxaldehyde.

[Chemical Formula 3-3a]

Intermediate synthesis example 5

A compound represented by the following chemical formula 3-4a is obtained using the same method as in Intermediate Synthesis Example 2, except that 5.72 g of 6-methoxy-2-naphthaldehyde is used instead of 7.07 g of 1-pyrenecarboxaldehyde.

[Chemical Formula 3-4a]

Intermediate synthesis example 6

A compound represented by the following chemical formula 3-5a is obtained using the same method as in Intermediate Synthesis Example 2, except that 4.18 g of p-anisaldehyde is used instead of 7.07 g of 1-pyrenecarboxyaldehyde.

[Chemical Formula 3-5a]

Final synthesis example 1

In a 500 ml flask, add the compound represented by the chemical formula 2-1a (8.15 g, 0.012 mol) obtained in the above intermediate synthesis example 1, 2-Naphthoyl chloride (4.58 g, 0.024 mol), and 196 g of 1,2-dichloroethane, and stir for 30 minutes under nitrogen conditions. After stirring at 0°C for 10 minutes, slowly add AlCl ₃ (3.2 g, 0.024 mol) and stir for 4 hours at 10°C under nitrogen conditions. Then, add 4-Methoxybenzoyl chloride (2.05 g, 0.012 mol) and AlCl ₃ (1.6 g, 0.012 mol), and stir at room temperature for 10 hours. After slowly adding 200 g of methanol, stirring for 1 hour and filtering the precipitate, add 150 g of methanol and 150 g of distilled water to the precipitate and stir for 1 hour. Filter the precipitate to collect it and dry to obtain a solid. To the obtained solid compound, add 70 g of N-methylpyrrolidone (NMP), 1-dodecanethiol (6.68 g, 0.033 mol), and KOH (2.47 g, 0.044 mol) and stir at 85°C for 6 hours. Add 350 g of hexane at room temperature and stir for 30 minutes, collect the precipitate, add 100 g of ethyl acetate, and slowly add 10% HCl aqueous solution until the aqueous layer becomes neutral to slightly acidic. After removing the aqueous layer, distilled water (100 g) is added, and the organic layer extraction is repeated three times, and the organic layer extract is depressurized. After that, 20 g of tetrahydrofuran is added to dissolve the obtained solid compound, and slowly added dropwise to 300 g of hexane, the obtained precipitate is filtered, recovered, and dried to obtain a solid. To the obtained solid compound, 57 g of tetrahydrofuran and 24 g of methanol are added and stirred. At 0°C, NaBH ₄ (5.67 g, 0.15 mol) is slowly added, stirred for 5 hours, and then stirred at room temperature for 4 hours. Add 150 g of ethyl acetate, and slowly add 10% HCl aqueous solution until the aqueous layer becomes slightly acidic. After removing the aqueous layer, distilled water is added to repeat the organic layer extraction three times, and the organic layer extract is depressurized to obtain a solid. Add 20 g of tetrahydrofuran to the obtained solid compound to dissolve the solid, and slowly add dropwise to 300 g of hexane to obtain a precipitate. Filter the obtained precipitate to recover it, and dry it to obtain a compound represented by the following chemical formula 2-1.

[Chemical Formula 2-1]

Final synthesis example 2

Instead of using 2-Naphthoyl chloride (4.58 g, 0.024 mol) and 4-Methoxybenzoyl chloride (2.05 g, 0.012 mol) in that order, use 4-Methoxybenzoyl chloride (4.09 g, 0.024 mol) and 2-Naphthoyl chloride (2.29 g, 0.012 mol) in that order, respectively, using the same method as in Final Synthesis Example 1, to obtain a compound represented by Chemical Formula 2-2 below.

[Chemical Formula 2-2]

Final synthesis example 3

A compound represented by the following chemical formula 3-1 is obtained using the same method as the final synthesis example 1, except that the compound represented by the chemical formula 3-1a obtained in the intermediate synthesis example 2 (8.16 g, 0.012 mol) is used instead of the compound represented by the chemical formula 2-1a obtained in the intermediate synthesis example 1 (8.15 g, 0.012 mol).

[Chemical Formula 3-1]

Final synthesis example 4

Except that the compound represented by chemical formula 3-2a obtained in Intermediate Synthesis Example 3 (7.87 g, 0.012 mol) is used instead of the compound represented by chemical formula 2-1a obtained in Intermediate Synthesis Example 1 (8.15 g, 0.012 mol), a mixture of a compound represented by chemical formula 3-2 below and a compound represented by chemical formula 3-3 below is obtained using the same method as in Final Synthesis Example 1.

[Chemical Formula 3-2]

[Chemical Formula 3-3]

Final Synthesis Example 5

A compound represented by chemical formula 3-3a obtained in Intermediate Synthesis Example 4 (7.27 g, 0.012 mol) is used instead of the compound represented by chemical formula 2-1a obtained in Intermediate Synthesis Example 1 (8.15 g, 0.012 mol), 2-Naphthoyl chloride 2.29 g (0.012 mol) is used instead of 4.58 g (0.024 mol) of 2-Naphthoyl chloride, and AlCl ₃ 1.60 g (0.012 mol) is used instead of AlCl ₃ (3.2 g, 0.024 mol) at 0°C, thereby obtaining a compound represented by compound 3-4 below using the same method as in Final Synthesis Example 1.

[Chemical Formula 3-4]

Final synthesis example 6

In a 500 ml flask, add the compound represented by the chemical formula 3-4a (7.63 g, 0.012 mol) obtained in the above intermediate synthesis example 5, 2-Naphthoyl chloride (4.58 g, 0.024 mol), and 196 g of 1,2-dichloroethane, and stir for 30 minutes under nitrogen conditions. After stirring at 0°C for 10 minutes, slowly add AlCl ₃ (3.2 g, 0.024 mol) and stir for 4 hours under nitrogen conditions at 10°C, and then stir for 10 hours at room temperature. Thereafter, using the same method as in the final synthesis example 1, a compound represented by the following chemical formula 3-5 is obtained.

[Chemical Formula 3-5]

Final Synthesis Example 7

A compound represented by the following chemical formula 3-6 is obtained using the same method as the final synthetic example 6, except that the compound represented by the chemical formula 3-5a obtained in the intermediate synthetic example 6 (7.02 g, 0.012 mol) is used instead of the compound represented by the chemical formula 3-4a obtained in the intermediate synthetic example 5 (7.63 g, 0.012 mol).

[Chemical Formula 3-6]

Comparative Synthesis Example 1

Except that perylene (3.03 g, 0.012 mol) is used instead of the compound (8.15 g, 0.012 mol) represented by chemical formula 2-1a obtained in Intermediate Synthesis Example 1, and 2.29 g (0.012 mol) of 2-Naphthoyl chloride is used instead of 4.58 g (0.024 mol), a compound represented by chemical formula 4-1 below is obtained using the same method as in Final Synthesis Example 1.

[Chemical Formula 4-1]

Comparative Synthesis Example 2

A compound represented by the following chemical formula 4-2 is obtained using the same method as the final synthetic example 1, except that benzoperylene (3.32 g, 0.012 mol) is used instead of the compound (8.15 g, 0.012 mol) represented by the chemical formula 2-1a obtained in intermediate synthetic example 1, and 2.29 g (0.012 mol) of 2-naphthoyl chloride is used instead of 4.58 g (0.024 mol).

[Chemical Formula 4-2]

Preparation of hard mask composition

Example 1

3 g of the compound represented by the chemical formula 2-1 obtained in Final Synthesis Example 1 was dissolved in 10 g of propylene glycol monomethyl ether acetate (PGMEA), and then filtered through a 0.1 μm Teflon filter to prepare a hard mask composition.

Example 2

3 g of the compound represented by the chemical formula 2-2 obtained in Final Synthesis Example 2 was dissolved in 10 g of propylene glycol monomethyl ether acetate (PGMEA), and then filtered through a 0.1 μm Teflon filter to prepare a hard mask composition.

Example 3

A hard mask composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 3-1 obtained in Final Synthesis Example 3 was used instead of the compound represented by Chemical Formula 2-1 obtained in Final Synthesis Example 1.

Example 4

A hard mask composition was prepared in the same manner as in Example 1, except that a mixture of a compound represented by Chemical Formula 3-2 and a compound represented by Chemical Formula 3-3 obtained in Final Synthesis Example 4 was used instead of the compound represented by Chemical Formula 2-1 obtained in Final Synthesis Example 1.

Example 5

A hard mask composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 3-4 obtained in Synthesis Example 5 was used instead of the compound represented by Chemical Formula 2-1 obtained in Final Synthesis Example 1.

Example 6

A hard mask composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 3-5 obtained in Final Synthesis Example 6 was used instead of the compound represented by Chemical Formula 2-1 obtained in Final Synthesis Example 1.

Example 7

A hard mask composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 3-6 obtained in Final Synthesis Example 7 was used instead of the compound represented by Chemical Formula 2-1 obtained in Final Synthesis Example 1.

Comparative Example 1

A hard mask composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 4-1 obtained in Comparative Synthesis Example 1 was used instead of the compound obtained in Final Synthesis Example 1.

Comparative Example 2

A hard mask composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 4-2 obtained in Comparative Synthesis Example 2 was used instead of the compound obtained in Final Synthesis Example 1.

Evaluation 1: Evaluation of etching resistance

Each composition according to Examples and Comparative Examples was spin-coated on a silicon wafer, and baked at 200°C for 60 seconds to form a hardmask layer having a thickness of 1,500 Å. An ArF photoresist was coated on each formed hardmask layer, baked at 110°C for 60 seconds, and then exposed using an exposure device from ASML (XT:1450G, NA 0.93) and developed with TMAH (2.38 wt% aqueous solution) to obtain a 60 nm line-and-space pattern. The photoresist pattern was further cured at 110°C for 60 seconds, and dry etching was performed on the photoresist pattern and the hardmask layer for 20 seconds using a CHF ₃ /CF ₄ mixed gas, and the cross-section was observed using FE-SEM to measure the etching rate and evaluate the etching resistance against halogen plasma. The evaluation criteria for etching resistance are as follows, and the evaluation results are shown in Table 1 below.

<Evaluation criteria for etching resistance>

◎: Etching speed less than 10Å/sec

○: Etching speed 10Å/sec or more but less than 11Å/sec

△: Etching speed 11Å/sec or more but less than 12Å/sec

X: Etching speed 12Å/sec or higher

division Etching in my body Example 1 ◎ Example 2 ◎ Example 3 ◎ Example 4 ◎ Example 5 ○ Example 6 ◎ Example 7 ○ Comparative Example 1 △ Comparative Example 2 ○

Referring to Table 1 above, it was confirmed that the etching rates of the hardmask layers formed from the hardmask compositions according to Examples 1 to 4 and Example 6 were less than 10Å/sec, which was lower than the etching rate of the hardmask layer formed from the hardmask composition according to Comparative Example 1, which was 10Å/sec or more and less than 11Å/sec. That is, it can be confirmed that the etch resistance of the hardmask layers formed from the hardmask compositions according to Examples 1 to 4 and Example 6 is superior to that of Comparative Example 1. In addition, it can be confirmed that the etch resistance of the hardmask layers formed from the hardmask compositions according to Examples 5 and 7 and the hardmask layer formed from the hardmask composition according to Comparative Example 2 are at the same level.

Evaluation 2: Solubility Evaluation

The compositions of the examples and comparative examples were stirred at 50°C for 1 hour, and then 1) the state of dissolution of the compound at 50°C was checked, cooled to room temperature, 2) the state of dissolution of the compound at 25°C was checked, stirred at room temperature for 6 hours, and 3) the state of dissolution of the compound was rechecked when left at 25°C, thereby measuring the solubility. The criteria for evaluating solubility are as follows, and the evaluation results are shown in Table 2 below.

<Solubility Evaluation Criteria>

◎: When left at room temperature, no undissolved compounds are visible to the naked eye.

○: At room temperature, no undissolved compound is visible to the naked eye, but when left at room temperature, a small amount of undissolved compound is visible to the naked eye.

△: Compounds that are not dissolved in a heated state are not visible to the naked eye, but compounds that are not dissolved in a room temperature state are visible to the naked eye.

X: A small amount of undissolved compound is visually observed under heating.

division Solubility Example 1 ○ Example 2 ◎ Example 3 ○ Example 4 ◎ Example 5 ◎ Example 6 ◎ Example 7 ◎ Comparative Example 1 △ Comparative Example 2 X

Referring to Table 2 above, the hardmask compositions according to Examples 1 to 7 did not completely dissolve the compounds in the solvent or only a very small amount was dissolved when left at room temperature. In contrast, it was confirmed that the hardmask compositions according to Comparative Examples 1 and 2 did not dissolve the compounds at room temperature. Therefore, it can be confirmed that the hardmask compositions according to Examples 1 to 7 have improved solubility compared to the hardmask composition according to the Comparative Example.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the invention is not limited thereto, and various modifications and improvements made by those skilled in the art using the basic concept of the invention defined in the claims described below also fall within the scope of the present invention.

Claims (19)

A hard mask composition comprising a compound represented by the following chemical formula 1 and a solvent:
[Chemical Formula 1]

In the above chemical formula 1,
X ¹ to X ³ are each independently N or CR ^a , wherein R ^a is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,
A ¹ to A ³ are each independently a substituted or unsubstituted C6 to C30 aromatic ring, a substituted or unsubstituted C2 to C40 heteroaromatic ring, or a combination thereof,
L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a combination thereof,
B ¹ to B ³ are each independently a substituted or unsubstituted C6 to C30 aromatic ring group, a substituted or unsubstituted C2 to C40 heteroaromatic ring, or a combination thereof,
n1 to n3 are each independently an integer from 0 to 5, but n1 to n3 cannot be 0 at the same time.
In the first paragraph, a hard mask composition wherein one or both of X ¹ to X ³ of the chemical formula 1 are N, or X ¹ to X ³ are all CR ^a , and R ^a is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C2 to C20 heteroaryl group, or a combination thereof.
A hard mask composition in claim 1, wherein A ¹ to A ³ of the chemical formula 1 are each independently a substituted or unsubstituted C6 to C30 aromatic ring.
In the first paragraph, A ¹ to A ³ of the chemical formula 1 are each independently any one of the substituted or unsubstituted moieties selected from the following Group 1 and Group 2: Hard mask composition:
[Group 1]

[Group 2]

In the above group 2,
Z is N, O, or S,
M ¹ and M ² are each independently a substituted or unsubstituted C6 to C30 aromatic ring.
In the first paragraph, A ¹ to A ³ of the chemical formula 1 are each independently one of a substituted or unsubstituted moiety selected from the following Group 1-1 and the following Group 2-1: Hard mask composition:
[Group 1-1]

[Group 2-1]

In the above group 2-1,
Z is N, O, or S,
M ¹ and M ² are each independently a substituted or unsubstituted C6 to C20 aromatic ring.
In the first paragraph, A ¹ to A ³ of the chemical formula 1 are each independently one of a substituted or unsubstituted moiety selected from the following Group 1-2 and the following Group 2-2: A hard mask composition:
[Group 1-2]

[Group 2-2]

In the first paragraph, L ¹ to L ³ of the chemical formula 1 are each independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a combination thereof,
A hard mask composition wherein B ¹ to B ³ are each independently a substituted or unsubstituted C6 to C30 aromatic ring group, a substituted or unsubstituted C2 to C40 heteroaromatic ring, or a combination thereof, and n1 to n3 are each independently one of the integers from 0 to 3, provided that n1 to n3 are not both 0.
In the first paragraph, L ¹ to L ³ of the chemical formula 1 are each independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a combination thereof,
B ¹ to B ³ are each independently a substituted or unsubstituted C6 to C30 aromatic ring group,
A hard mask composition wherein n1 to n3 are each independently 0 or 1, but n1 to n3 are not simultaneously 0.
In the first paragraph, L ¹ to L ³ of the chemical formula 1 are each independently a single bond, a C1 to C10 alkylene group with or without a substituted hydroxy group, or a combination thereof,
B ¹ to B ³ are each independently any one of a substituted or unsubstituted moiety selected from the following group 3,
A hard mask composition wherein n1 to n3 are each independently 0 or 1, but n1 to n3 are not 0 at the same time:
[Group 3]

In the first paragraph, the chemical formula 1 is a hard mask composition represented by the following chemical formula 1-1 or the following chemical formula 1-2:
[Chemical Formula 1-1]

[Chemical Formula 1-2]

In the above chemical formulas 1-1 and 1-2,
A ⁴ to A ⁹ are each independently a substituted or unsubstituted C6 to C30 aromatic ring, a substituted or unsubstituted C2 to C40 heteroaromatic ring, or a combination thereof,
L ⁴ to L ⁹ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, or a combination thereof,
B ⁴ to B ⁹ are each independently a substituted or unsubstituted C6 to C30 aromatic ring group, a substituted or unsubstituted C2 to C40 heteroaromatic ring, or a combination thereof,
n4 to n9 are each independently an integer from 0 to 5, provided that n4 to n6 are not both 0, and n7 to n9 are not both 0.
In clause 10, a hard mask composition wherein A ⁵ and A ⁶ of the chemical formula 1-1 are the same, or A ⁸ and A ⁹ of the chemical formula 1-2 are the same.
In the first paragraph, the chemical formula 1 is a hard mask composition represented by the following chemical formula 2 or the following chemical formula 3:
[Chemical formula 2]

[Chemical Formula 3]

In the above chemical formulas 2 and 3,
A ⁴ and A ⁷ are each independently substituted or unsubstituted benzene, naphthalene, anthracene, phenanthrene, pyrene, or a combination thereof,
L ⁴ to L ⁹ are each independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a combination thereof,
B ⁵ to B ⁹ are each independently a substituted or unsubstituted phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrene group, or a combination thereof,
n4 to n9 are each independently 0 or 1, provided that n4 to n6 are not simultaneously 0, and n7 to n9 are not simultaneously 0.
In the first paragraph, the chemical formula 1 is a hard mask composition represented by any one of the following chemical formulas 2-1, 2-2, and 3-1 to 3-6:
[Chemical Formula 2-1]

[Chemical Formula 2-2]

[Chemical Formula 3-1]

[Chemical Formula 3-2]

[Chemical Formula 3-3]

[Chemical Formula 3-4]

[Chemical Formula 3-5]

[Chemical Formula 3-6]

A hard mask composition in claim 1, wherein the molecular weight of the compound is 300 g/mol to 5,000 g/mol.
In the first paragraph, a hard mask composition in which the compound is included in an amount of 0.1 wt% to 30 wt% based on the total weight of the hard mask composition.
A hard mask composition in claim 1, wherein the solvent is propylene glycol, propylene glycol diacetate, methoxy propanediol, diethylene glycol, diethylene glycol butyl ether, tri(ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone or ethyl 3-ethoxypropionate.
A hard mask layer comprising a cured product of a hard mask composition according to any one of claims 1 to 16.
A step of providing a material layer on a substrate;
A step of applying a hard mask composition according to any one of claims 1 to 16 on the above material layer,
A step of forming a hard mask layer by heat treating the above hard mask composition,
A step of forming a photoresist layer on the above hard mask layer,
A step of forming a photoresist pattern by exposing and developing the above photoresist layer,
A step of selectively removing the hard mask layer using the photoresist pattern and exposing a portion of the material layer, and
A step of etching the exposed portion of the above material layer,
A pattern forming method including:
A pattern forming method in claim 18, wherein the step of forming the hard mask layer includes a step of heat treating at 100°C to 1,000°C.