KR20230019720A - Hardmask composition, and method of forming patterns - Google Patents

Abstract

Provided are (i) a polymer containing a structural unit represented by the following chemical formula 1-1, a structural unit represented by the following chemical formula 1-2, or a combination thereof, (ii) a compound represented by the following chemical formula 2, or (iii) a combination of the polymer (i) and the compound (ii), and a hardmask composition including a solvent, and a pattern forming method using the hardmask composition. X, Y, A^1, A^2, L^1 to L^6, T^1 to T^3, E^1 and E^2, and m and n of the checmial formulas 1-1, 1-2, and 2 are each as described in the specification. The present invention provides a hardmask composition that can be effectively applied to a hardmask layer.

Description

Hard mask composition and pattern forming method {HARDMASK COMPOSITION, AND METHOD OF FORMING PATTERNS}

A hard mask composition and a pattern forming method using the hard mask composition.

In recent years, the semiconductor industry has been developing from hundreds of nanometer-sized patterns to ultra-fine technologies having several to several tens of nanometer-sized patterns. Effective lithographic techniques are essential to realize these ultra-fine technologies.

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

Recently, as the size of a pattern to be formed decreases, it is difficult to form a fine pattern having a good profile only with the above-described typical lithographic techniques. Accordingly, a fine pattern may be formed by forming an auxiliary layer called 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 pattern forming method using the hard mask composition.

A hard mask composition according to an embodiment includes (i) a polymer including a structural unit represented by Chemical Formula 1-1, a structural unit represented by Chemical Formula 1-2, or a combination thereof, (ii) a structural unit represented by Chemical Formula 2 below. A compound represented by, or (iii) a combination of a polymer of (i) above and a compound of (ii) above, and a solvent:

[Formula 1-1] [Formula 1-2]

In Formulas 1-1 and 1-2,

X and Y are each independently a substituted or unsubstituted C4 to C30 aliphatic hydrocarbon ring, a substituted or unsubstituted C6 to C30 aromatic hydrocarbon ring, a substituted or unsubstituted C4 to C30 heterocycle, or a combination thereof. include,

[Formula 2]

In Formula 2 above,

A ¹ and A ² are each independently represented by Formula 3-1 or Formula 3-2 below;

L ¹ to L ⁶ are each independently a single bond, a substituted or unsubstituted C1 to C6 alkylene group, or a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof;

T ¹ to T ³ are each independently a hydroxyl group, a thiol group, a thionyl group, a cyano group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, a substituted or unsubstituted C1 to C30 alkoxy group, or these is a combination of

E ¹ and E ² are each independently a substituted or unsubstituted C4 to C20 aliphatic hydrocarbon ring, a substituted or unsubstituted C6 to C30 aromatic hydrocarbon ring, or a combination thereof;

m and n are each independently an integer from 0 to 5:

[Formula 3-1] [Formula 3-2]

In Chemical Formulas 3-1 and 3-2,

X and Y are as defined in Chemical Formulas 1-1 and 1-2, respectively.

X and Y in Formulas 1-1, 1-2, 3-1 and 3-2 each independently include a substituted or unsubstituted C6 to C30 aromatic hydrocarbon ring.

The substituted or unsubstituted C6 to C30 aromatic hydrocarbon ring includes one substituted or unsubstituted benzene ring, or two or more substituted or unsubstituted benzene rings connected by a single bond or a linking group, or a substituted or unsubstituted ring. It may contain an aromatic hydrocarbon ring in which two or more cyclic benzene rings are condensed.

X in Formulas 1-1, 1-2, 3-1, and 3-2 each independently includes a C10 to C24 aromatic hydrocarbon ring in which two or more substituted or unsubstituted benzene rings are condensed.

X in Formulas 1-1, 1-2, 3-1, and 3-2 each independently includes a C10 to C20 aromatic hydrocarbon ring in which two or more substituted or unsubstituted benzene rings are condensed.

X in Formulas 1-1, 1-2, 3-1, and 3-2 each independently includes an aromatic hydrocarbon ring derived from naphthalene, perylene, or coronene.

Y in Chemical Formulas 1-1 and 1-2 each independently includes an aromatic hydrocarbon ring in which two or more substituted or unsubstituted benzene rings are connected by a single bond or a linking group.

The linking group is -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (Where 1≤p≤10), -(CF ₂ ) _q - (Where, 1≤q≤10), -CR'R"- (Where, R' and R" are each independently hydrogen, a C1 to C10 aliphatic hydrocarbon group, a C6 to C20 aromatic hydrocarbon group, or a C6 to C20 alicyclic hydrocarbon group), -C(CF ₃ )(C ₆ H ₅ )-, -C(CF ₃ ) ₂ -, -C(=O)NH-, a fluorenylene group, or a combination thereof includes

Y in Formulas 1-1 and 1-2 is each independently two substituted or unsubstituted benzene rings that represent a single bond, -O-, -S-, -C(=O)-, or fluorenylene contains aromatic hydrocarbon rings linked by groups.

Y in Chemical Formulas 3-1 and 3-2 each independently includes a substituted or unsubstituted benzene ring or an aromatic hydrocarbon ring in which two or more substituted or unsubstituted benzene rings are condensed.

L ¹ to L ⁶ in Formula 2 are all single bonds.

T ¹ to T ³ in Formula 2 are each independently a hydroxyl group, a thiol group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C10 alkoxy group, or a combination thereof.

All of T ¹ to T ³ in Formula 2 are hydroxyl groups.

E ¹ and E ² in Formula 2 each independently include a substituted or unsubstituted benzene ring or an aromatic hydrocarbon ring in which two or more substituted or unsubstituted benzene rings are condensed.

One of m and n in Formula 2 is 0, and the other is 1.

Formula 1-1 is represented by one of the following Formulas 1-a to 1-c:

[Formula 1-a]

[Formula 1-b]

[Formula 1-c]

.

.

Formula 1-2 is represented by Formula 1-d below:

[Formula 1-d]

.

.

The compound represented by Chemical Formula 2 includes a compound represented by the following Chemical Formula [2-a] or the following Chemical Formula [2-b]:

[Formula 2-a]

[Formula 2-b]

.

.

According to another embodiment, forming a hard mask layer by applying a hard mask composition according to one embodiment to a material layer and performing heat treatment, forming a photoresist layer on the hard mask layer, exposing the photoresist layer, and forming a photoresist pattern by developing, exposing a portion of the material layer by selectively removing the hard mask layer using the photoresist pattern, and etching the exposed portion of the material layer. A pattern forming method is provided.

A hardmask layer prepared from the hardmask composition according to one embodiment may secure excellent film density and 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 embodied in many different forms and is not limited to the embodiments set forth herein.

Hereinafter, unless otherwise defined herein, 'substituted' means that a hydrogen atom in a compound is deuterium, a halogen atom (F, Br, Cl, or I), a hydroxyl group, a nitro group, a cyano group, an amino group, an azido group, an amino group A dino 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 group or a salt thereof, C1 to C30 Alkyl group, C2 to C30 Alkenyl group, C2 to C30 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalkenyl group, It means that it is substituted with a substituent selected from a C6 to C15 cycloalkynyl group, a C2 to C30 heterocyclic group, and combinations thereof.

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

Unless otherwise defined herein, "aliphatic hydrocarbon ring" includes both "saturated" and "unsaturated" aliphatic hydrocarbon rings.

Unless otherwise defined herein, "saturated aliphatic hydrocarbon ring" means a cyclic hydrocarbon ring in which all carbon-carbon bonds are single bonds, for example, a cycloalkane ring.

Unless otherwise defined herein, “unsaturated aliphatic hydrocarbon ring” includes an aliphatic hydrocarbon ring in which an intercarbon bond includes one or more unsaturated bonds, such as cycloalkenes and cycloalkynes.

In addition, unless otherwise defined in this specification, “hetero” means containing 1 to 3 heteroatoms selected from N, O, S, Se and P.

As used herein, "aryl group" refers to a group having one or more hydrocarbon aromatic moieties, and broadly refers to a form in which hydrocarbon aromatic moieties are connected by a single bond and a ratio in which hydrocarbon aromatic moieties are directly or indirectly fused. Aromatic fused rings are also included. Aryl groups include monocyclic, polycyclic or fused polycyclic (ie, rings that divide adjacent pairs of carbon atoms) functional groups.

In the present specification, "heterocyclic group" is a concept including a heteroaryl group, and in addition to this, in a ring compound such as an aryl group, a cycloalkyl group, a fused ring thereof, or a combination thereof, instead of carbon (C) It means containing at least one hetero atom selected from N, O, S, P, and Si. When the heterocyclic group is a fused ring, the entire heterocyclic group or each ring may include one or more heteroatoms.

More specifically, the substituted or unsubstituted aryl group and/or the substituted or unsubstituted heterocyclic group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted A substituted 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 quarterphenyl group, a substituted or unsubstituted biphenyl group, A substituted 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 an 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 thiazole Diary, substituted or unsubstituted oxadiazolyl group, substituted or unsubstituted thiadiazolyl group, substituted or unsubstituted pyridinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, substituted Or an 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 quinine A nolinyl 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, Substituted or unsubstituted benzthiazinyl group, substituted or unsubstituted acridinyl group, substituted or unsubstituted phenazinyl group, substituted or unsubstituted phenothiazinyl group, substituted or unsubstituted phenoxazinyl group, substituted or unsubstituted A substituted 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, benzopyridothia A jinyl group, a 9,9-dimethyl-9,10-dihydroacridinyl group, a combination thereof, or a combination thereof may be in the form of a fusion, but Not limited. In one embodiment of the present invention, the heterocyclic group or heteroaryl group may be a pyridyl group, an ildolyl group, a carbazolyl group, or a pyridoindolyl group.

In this specification, unless otherwise specified, "combination" means mixing or copolymerization.

Also, in the present specification, the polymer may include both an oligomer and a polymer.

A lithography technique involves forming a film of a resist material on a substrate, performing selective exposure to a specific light source using a mask that forms a certain pattern on the film, and then forming a pattern on the resist film by developing. include the process Meanwhile, in the semiconductor industry, there is an ever-increasing demand for reducing the size of chips. In order to cope with this trend, the line width of the resist patterned in lithography technology must be reduced to several tens of nanometers in size, and the pattern is transferred to the lower layer material by using an etching process on the lower substrate using the pattern formed in this way. However, since the pattern size of the resist is reduced, the height (aspect ratio) of the resist that can withstand the line width is limited, and accordingly, there are cases where the resist does not have sufficient resistance in an etching step. Accordingly, an organic film called a hardmask layer has been used as a resist underlayer to compensate for a thin resist material, a thick substrate to be etched, or a deep pattern.

Since this hard mask layer serves as a second mask between the resist layer and the substrate on which a pattern is to be formed, it needs excellent adhesive strength and film density characteristics to withstand multiple etching processes required for pattern transfer. In addition, when the solubility of the components in the composition for forming the hard mask layer is poor, storage stability is deteriorated, flowability is poor, and defects are likely to occur in the coating process. Therefore, a composition for forming a hard mask is particularly important in terms of excellent solubility, and should be capable of providing a hard mask layer having excellent etch resistance while maintaining excellent adhesion and film density after curing.

The present inventors solve the above problems to prepare a hard mask composition having excellent solubility, improved crosslinking power during curing, and thus, a hard mask layer produced having high etching resistance, adhesive strength, and film density. made an effort As a result, the present invention was completed by confirming that a composition containing a polymer including a specific structural unit and/or a compound as described below together with a solvent can achieve all of the above objects.

Specifically, the hard mask composition according to one embodiment includes (i) a polymer including a structural unit represented by Chemical Formula 1-1, a structural unit represented by Chemical Formula 1-2, or a combination thereof, (ii) a structural unit represented by Chemical Formula 1-1 below; A compound represented by Formula 2, or (iii) a combination of the polymer of (i) and the compound of (ii) above, and a solvent:

[Formula 1-1] [Formula 1-2]

In Formulas 1-1 and 1-2,

X and Y are each independently a substituted or unsubstituted C4 to C30 aliphatic hydrocarbon ring, a substituted or unsubstituted C6 to C30 aromatic hydrocarbon ring, a substituted or unsubstituted C4 to C30 heterocycle, or a combination thereof. include,

[Formula 2]

In Formula 2 above,

A ¹ and A ² are each independently represented by Formula 3-1 or Formula 3-2 below;

L ¹ to L ⁶ are each independently a single bond, a substituted or unsubstituted C1 to C6 alkylene group, or a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof;

T ¹ to T ³ are each independently a hydroxyl group, a thiol group, a thionyl group, a cyano group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, a substituted or unsubstituted C1 to C30 alkoxy group, or these is a combination of

E ¹ and E ² are each independently a substituted or unsubstituted C4 to C20 aliphatic hydrocarbon ring, a substituted or unsubstituted C6 to C30 aromatic hydrocarbon ring, or a combination thereof;

m and n are each independently an integer from 0 to 5:

[Formula 3-1] [Formula 3-2]

In Chemical Formulas 3-1 and 3-2,

X and Y are as defined in Chemical Formulas 1-1 and 1-2, respectively.

As shown in Chemical Formulas 1-1, 1-2, 3-1, and 3-2, the hard mask composition according to an embodiment includes structural units represented by Chemical Formulas 1-1 and/or 1-2. or, by including the moiety represented by Formula 3-1 and/or 3-2 above, the content of nitrogen (N) together with carbon (C) in the polymer and/or compound including them can be significantly increased. . In addition, it is thought that by including the imide structural unit or moiety as described above, the above polymers and compounds have a more rigid structure, thereby improving the etch resistance of the hard mask layer including the imide structural unit or moiety.

In Chemical Formulas 1-1, 1-2, 3-1, and 3-2, X and Y may each independently include a substituted or unsubstituted C6 to C30 aromatic hydrocarbon ring. For example, the substituted or unsubstituted C6 to C30 aromatic hydrocarbon ring includes one substituted or unsubstituted benzene ring, or two or more substituted or unsubstituted benzene rings linked by a single bond or a linking group, Or it may include one in which two or more benzene rings are condensed.

In one embodiment, X in Formulas 1-1, 1-2, 3-1, and 3-2 each independently includes a C10 to C24 aromatic hydrocarbon ring in which two or more substituted or unsubstituted benzene rings are condensed. can do. When X in Formulas 1-1, 1-2, 3-1 and 3-2 includes a C10 to C24 aromatic hydrocarbon ring in which two or more substituted or unsubstituted benzene rings are condensed, the polymer and/or compound By including a planar structure in the structure, the film density of the hard mask layer produced therefrom can be increased and the etch resistance can be further improved. In one embodiment, X in Formulas 1-1, 1-2, 3-1, and 3-2 each independently includes a C10 to C20 aromatic hydrocarbon ring in which two or more substituted or unsubstituted benzene rings are condensed. can do.

In one embodiment, X in Chemical Formulas 1-1, 1-2, 3-1, and 3-2 may each independently include an aromatic hydrocarbon ring derived from naphthalene, perylene, or coronene.

Y in Chemical Formulas 1-1 and 1-2 may each independently include an aromatic hydrocarbon ring in which two or more substituted or unsubstituted benzene rings are connected by a single bond or a linking group.

The linking group is -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (Where 1≤p≤10), -(CF ₂ ) _q - (Where, 1≤q≤10), -CR'R"- (Where, R' and R" are each independently hydrogen, a C1 to C10 aliphatic hydrocarbon group, a C6 to C20 aromatic hydrocarbon group, or a C6 to C20 alicyclic hydrocarbon group), -C(CF ₃ )(C ₆ H ₅ )-, -C(CF ₃ ) ₂ -, -C(=O)NH-, a fluorenylene group, or a combination thereof can include

In one embodiment, Y in Chemical Formulas 1-1 and 1-2 is each independently two substituted or unsubstituted benzene rings having a single bond, -O-, -S-, -C(=O)- , or an aromatic hydrocarbon ring linked by a fluorenylene group.

When Y in Chemical Formulas 1-1 and 1-2 each independently includes an aromatic hydrocarbon ring in which two or more substituted or unsubstituted benzene rings are connected by a single bond, the polymer containing the same is rigid ) while maintaining the structure, the solubility in the solvent may increase as the main chain of the polymer may have a tilted structure rather than a straight line. In addition, when Y includes two or more substituted or unsubstituted aromatic hydrocarbon rings linked by the above linking group rather than a single bond, the connection between the two or more substituted or unsubstituted benzene rings is not fixed. As it becomes fluid, the solubility of the polymer containing it in the solvent may further increase. In addition, when the linking group is -O-, -S-, -C(=O)-, -CH(OH)-, or -S(=O) ₂ -, they are a functional group capable of hydrogen bonding in the polymer or a solvent. By hydrogen bonding with, it may have an effect of increasing the film density due to the formation of additional crosslinks or increasing the solubility in the solvent. Alternatively, when the linking group includes a group that may have steric hindrance such as a fluorene group, solubility in a solvent may be further increased.

Y in Chemical Formulas 3-1 and 3-2 may each independently include one substituted or unsubstituted benzene ring or an aromatic hydrocarbon ring in which two or more substituted or unsubstituted benzene rings are condensed.

When Y in Formulas 3-1 and 3-2 each independently includes one substituted or unsubstituted benzene ring or an aromatic hydrocarbon ring in which two or more substituted or unsubstituted benzene rings are condensed, the formula The film density of a hardmask prepared from the hardmask composition including the compound represented by 2 may be increased, and etch resistance may be further improved. In addition, when an aromatic hydrocarbon ring in which two or more substituted or unsubstituted benzene rings are condensed is included, the corrosion resistance may be increased by increasing the carbon content in the composition.

In one embodiment, all of L ¹ to L ⁶ in Formula 2 may be single bonds. That is, in Chemical Formula 2, the carbon atoms respectively connected to T ¹ to T ³ may be directly connected to E ¹ and E ² , and A ¹ and A ^{2 ,} respectively. In this case, the compound represented by Chemical Formula 2 is not very flexible in structure and can maintain a generally plate-like shape, thereby increasing the film density of a hard mask prepared from a composition containing the compound and improving the etch resistance. there is. However, the compound represented by Chemical Formula 2 may also have an effect of allowing the compound to dissolve well in a solvent by including tertiary carbons respectively linked to T ¹ to T ³ in its structure.

In one embodiment, T ¹ to T ³ in Formula 2 may each independently be a hydroxyl group, a thiol group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C10 alkoxy group, or a combination thereof. . For example, all of T ¹ to T ³ may be hydroxyl groups.

When T ¹ to T ³ in Formula 2 have the above functional groups, the solubility of the compound is improved by cross-linking with another compound through the functional group or by hydrogen bonding with a functional group capable of hydrogen bonding of another compound or solvent. And, it is possible to improve the film density and further improve the etch resistance of a hard mask prepared from a composition including the same.

In one embodiment, E ¹ and E ² in Formula 2 may each independently include one substituted or unsubstituted benzene ring, or an aromatic hydrocarbon ring in which two or more substituted or unsubstituted benzene rings are condensed. there is. The E ¹ and E ² each include a substituted or unsubstituted benzene ring or an aromatic hydrocarbon ring in which two or more substituted or unsubstituted benzene rings are condensed, thereby increasing the carbon content of the compound and preparing a composition containing the same. It is possible to improve the film density of the hard mask and further improve the etch resistance.

In one embodiment, one of m and n in Chemical Formula 2 may be 0 and the other may be 1, but is not limited thereto. When one of m and n in Formula 2 is 0 and the other is 1, the compound has a linear structure as a whole, and thus the film density of the hard mask prepared from the composition including the compound is improved and the corrosion resistance is improved. can be further improved.

In one embodiment, Chemical Formula 1-1 may be represented by one of the following Chemical Formulas 1-a to 1-c, and Chemical Formula 1-2 may be represented by Chemical Formula 1-d, but is not limited thereto:

[Formula 1-a]

[Formula 1-b]

[Formula 1-c]

[Formula 1-d]

.

.

The polymer including the structural unit represented by Chemical Formulas 1-1 and/or 1-2 may be prepared by reacting a tetracarboxylic dianhydride represented by Chemical Formula 1a with a tetraamine compound represented by Chemical Formula 1b. , but is not limited thereto.

[Formula 1a] [Formula 1b]

In Formula 1a, X ¹ is the same as X in Formulas 1-1 and 1-2, and Y ¹ in Formula 1b is the same as Y in Formulas 1-1 and 1-2.

The compound represented by Formula 2 may be represented by the following Formula [2-a] or [2-b], but is not limited thereto:

[Formula 2-a]

[Formula 2-b]

.

.

The compound represented by Chemical Formula 2 is prepared by first reacting the tetracarboxylic dianhydride represented by Chemical Formula 1a with a diamine compound represented by Chemical Formula 1c to prepare a compound represented by Chemical Formula 3-1 or 3-2. Then, the compound is a moiety defined by E ¹ or E ² in Formula 2, that is, a substituted or unsubstituted C4 to C20 aliphatic hydrocarbon ring, a substituted or unsubstituted C6 to C30 aromatic hydrocarbon ring, or a combination thereof. A functional group capable of performing a Friedel-Craf's Reaction with the compound represented by Formula 3-1 or 3-2 in the moiety containing, for example, “XC(=O)- (where, X may be a halogen atom such as F, Cl, Br, I, for example, Cl)" may be prepared by reacting with a substituted compound, but is not limited thereto.

[Formula 1c]

NH ₂ -Y ¹ -NH ₂

In Formula 1c, Y ¹ is the same as Y in Formula 3-1 or Formula 3-2.

In one embodiment, the moiety represented by E ¹ or E ² in Formula 2 of the compound capable of reacting with the compound represented by Formula 3-1 or 3-2 and Friedel-Crafts is one selected from Group 1 below. It may contain one or more substituted or unsubstituted aromatic hydrocarbon rings:

[Group 1]

In one embodiment, the moiety represented by E ¹ or E ² in Formula 2 may include benzene, naphthalene, anthracene, phenanthrene, naphthacene, pyrene, or a combination thereof, for example, The moiety may include benzene, naphthalene, pyrene, or combinations thereof.

The polymer including the structural unit represented by Chemical Formulas 1-1 and/or 1-2 may have a weight average molecular weight of about 1,000 to 100,000 g/mol. For example, the polymer is about 1,000 to 50,000 g / mol, such as about 1,000 to 20,000 g / mol, about 1,000 to 10,000 g / mol, about 1,000 to 5,000 g / mol, about 1,000 to 4,000 g / mol , It may have a weight average molecular weight of about 1,500 to 35,000 g / mol, about 2,000 to 3,000 g / mol, but is not limited thereto. By having a weight average molecular weight within the above range, solubility in a solvent may be optimized, while film density and etching resistance of a hard mask prepared therefrom may be increased.

The compound represented by Formula 2 may have a molecular weight of about 1,000 to 100,000 g/mol. For example, the compound may be present at about 1,000 to 50,000 g/mol, such as about 1,000 to 20,000 g/mol, about 1,000 to 10,000 g/mol, about 1,000 to 5,000 g/mol, about 1,000 to 4,000 g/mol. , It may have a molecular weight of about 1,500 to 35,000 g / mol, about 2,000 to 3,000 g / mol, but is not limited thereto. By having a molecular weight within the above range, solubility in a solvent may be optimized, while film density and etch resistance of a hard mask prepared therefrom may be increased.

The solvent included in the hard mask composition is not particularly limited as long as it has sufficient solubility and/or dispersibility for the above-described polymer and/or compound, but examples include propylene glycol, propylene glycol diacetate, methoxypropanediol, and 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-dimethylform It may include at least one selected from amide, N,N-dimethylacetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone, ethyl 3-ethoxypropionate, and the like, but is not limited thereto.

The polymer and/or compound may be present in an amount of about 0.1 to 50% by weight, such as about 0.2 to 45% by weight, such as about 0.5 to 40% by weight, based on the total weight of the hardmask composition. About 1 to 35% by weight, for example, about 1.5 to 30% by weight, for example, about 2 to 25% by weight may be included, but is not limited thereto. By including the polymer and/or compound within the above range, the thickness, surface roughness, and degree of planarization of the hard mask can be easily controlled.

The hard mask composition may further include additives such as a surfactant, a crosslinking agent, a thermal acid generator, and a plasticizer.

As the surfactant, for example, fluoroalkyl-based compounds, alkylbenzenesulfonic acid salts, alkylpyridinium salts, polyethylene glycol, quaternary ammonium salts, etc. may be used, but are not limited thereto.

The crosslinking agent may include, for example, melamine-based, substituted urea-based, or these polymer-based. Preferably, a crosslinking agent having at least two cross-linking substituents, for example methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxy Compounds such as methylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or butoxymethylated thiourea can be used.

In addition, as the crosslinking agent, a crosslinking agent having high heat resistance may be used. As the crosslinking agent having high heat resistance, a compound containing a crosslinking substituent having an aromatic ring (for example, a benzene ring or a naphthalene ring) in a molecule may be used.

The thermal acid generator is, for example, an acidic compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid, or/and 2,4 ,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters may be used, but are not limited thereto.

The additive may be included in an amount of about 0 to about 20 parts by weight based on 100 parts by weight of the hard mask composition. When included within the above range, the solubility of the hard mask composition may be improved without changing the optical properties.

According to another embodiment, an organic layer prepared using the hard mask composition described above is provided. The organic film may be formed by coating the above-described hard mask composition on a substrate and then cured through a heat treatment process, and may include, for example, an organic thin film used in electronic devices such as a hard mask layer, a planarization film, a sacrificial film, and a filler. there is.

Hereinafter, a method of forming a pattern using the hard mask composition described above will be described.

A pattern formation method according to an embodiment includes forming a material layer on a substrate, applying a hardmask composition including the above-described polymer and a solvent on the material layer, and heat-treating the hardmask composition to form a hardmask layer. forming a photoresist layer on the hard mask layer, exposing and developing the photoresist layer to form a photoresist pattern, selectively removing the hard mask layer using the photoresist pattern, 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 finally 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 by, for example, a chemical vapor deposition method.

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

The heat treatment of the hardmask composition may be performed at, for example, about 100 to 1,000° C. for about 10 seconds to 1 hour.

For example, the heat treatment of the hardmask composition may include a plurality of heat treatment steps, for example, a first heat treatment step and a second heat treatment step.

By performing at least one step of heat treatment of the hardmask composition at a high temperature of 200° C. or higher, high etching resistance capable of withstanding etching gas and chemical liquid exposed in a subsequent process including an etching process may be exhibited.

For example, forming the hard mask layer may include a UV/Vis curing step and/or a near IR curing step.

For example, the forming of the hard mask layer includes at least one of the first heat treatment step, the second heat treatment step, a UV/Vis curing step, and a near IR curing step, or two or more steps are continuously performed. can include

For example, 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, for example, materials such as SiCN, SiOC, SiON, SiOCN, SiC, SiO, and/or SiN.

For example, before forming the photoresist layer, a bottom anti-reflective coating (BARC) may be further formed on the silicon-containing thin film layer or on the hard mask layer.

Exposing the photoresist layer may be performed using, for example, ArF, KrF, or EUV. In addition, a heat treatment process may be performed at about 100 to 700° C. after exposure.

Etching the exposed portion of the material layer may be performed by dry etching using an etching gas, such as N ₂ /O ₂ , CHF ₃ , CF ₄ , Cl ₂ , BCl ₃ and a mixture thereof. gas can be used.

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

The above-described implementation 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 rights.

Example

Synthesis Example: Synthesis of Polymers and Compounds

Synthesis Example 1: Synthesis of Polymer 1

1,8-naphthalene dianhydride (5g, 25.23mmol) and benzene-1,2,4,5-tetraamine (2.73g, 25.23mmol, 1eq) and acetic acid (300mL) were added to a 500mL flask equipped with a stirrer and a condenser. Then, polymerization was performed by stirring at 120° C. for 24 to 48 hours. The reaction was completed when the weight average molecular weight was between 1,000 g/mol and 5,000 g/mol. After completion of the polymerization reaction, the reactant was slowly cooled to room temperature, the reactant was neutralized with 1M NaOH solution, and the resulting solid was filtered. The solid was washed sequentially with distilled water, ethanol, and diethyl ether, and then dried to obtain Polymer 1 having a weight average molecular weight of about 2,500 g/mol. This reaction is shown in Scheme 1 below:

(Scheme 1)

→

.

→

.

Synthesis Example 2: Synthesis of Polymer 2

Perylenetetracarboxylic dianhydride, 3,3'-Diaminobenzidine, and acetic acid were added to a 500mL flask equipped with a stirrer and a condenser, and then a polymer having a weight average molecular weight of about 2,600 g/mol was obtained through the same synthesis process as in Synthesis Example 1. This reaction is represented by Scheme 2 below.

(Scheme 2)

. →

.

Synthesis Example 3: Synthesis of Polymer 3

Perylenetetracarboxylic dianhydride, 4,4'-oxybis (benzene-1,2-diamine) and acetic acid were added to a 500mL flask equipped with a stirrer and a condenser, and then the same synthesis process as in Synthesis Example 1 was performed to obtain a weight average molecular weight of about 2,800g/ mol of polymer 3 was obtained. This reaction is shown in Scheme 3 below:

(Scheme 3)

n. →

n.

Synthesis Example 4: Synthesis of Polymer 4

After adding 1,8-naphthalene dianhydride, 9,9-Bis (3,4-diaminophenyl) fluorene and acetic acid to a 500mL flask equipped with a stirrer and a condenser, the weight average molecular weight was about 2,100 through the same synthesis process as in Synthesis Example 1 g/mol of polymer 4 was obtained. This reaction is shown in Scheme 4 below:

(Scheme 4)

. →

.

Synthesis Example 5: Synthesis of Compound 1

After adding 1,8-naphthalene dianhydride (8.4g, 31.32mmol), o-phenylenediamine (6.77g, 62.60mmol) and acetic acid (400mL) to a 500mL flask equipped with a stirrer and a condenser, 24 hours to 48 hours at 120 ° C. Stir for an hour. After completion of the reaction, the reactant was slowly cooled, and the reactant was neutralized with 1M NaOH solution, and the resulting solid was filtered. This solid was washed with distilled water, ethanol, and diethyl ether in that order, and then dried to obtain a compound represented by Chemical Formula 2-5-1 shown in Scheme 5 below.

A solution was prepared by adding the compound of Formula 2-5-1, pyrene-1-carbonyl chloride, and 1,2-dichloroethane to the flask. After slowly adding aluminum chloride to the solution, the mixture was reacted by stirring at 60° C. for 8 hours. When the reaction was completed, methanol was added and a precipitate formed was filtered and dried.

After adding the compound obtained above, 20.26 g of 1-dodecanethiol, 6.74 g of potassium hydroxide, and DMF to the flask, the reaction was stirred at 60° C. for 8 hours. The reaction mixture was cooled and neutralized to about pH 6 to 7 with 5% hydrochloric acid solution, and the precipitate formed was filtered and dried.

A solution was prepared by adding the compound obtained above and 37.4 g of tetrahydrofuran to the flask. A 10 g aqueous solution of sodium borohydride was slowly added to the solution, followed by stirring at room temperature for 24 hours to react. When the reaction is complete, neutralized to about pH 7 with a 5% hydrochloric acid solution, extracted with ethyl acetate and dried to obtain Compound 1 represented by Formula 2-a below.

(Scheme 5)

(Formula 2-5-1)

(Formula 2-a)

Synthesis Example 6: Synthesis of Compound 2

Perylenetetracarboxylic dianhydride, naphthalene-2,3-diamine and acetic acid were added to a 500mL flask equipped with a stirrer and a condenser, and then the compound represented by Chemical Formula 2-6-1 in Scheme 6 was obtained through the same synthesis process as in Synthesis Example 5. got it

A solution was prepared by adding the compound of Formula 2-6-1, terephthaloyl chloride, and 1,2-dichloroethane to the flask. Subsequently, through the same synthesis process as in Synthesis Example 5, Compound 2 represented by Formula 2-b was obtained.

(Scheme 2)

(Formula 2-6-1)

(Formula 2-b)

Comparative Synthesis Example 1: Synthesis of Compound A

To a 500 mL flask was added perylene and methoxy naphthoyl chloride and 1,2-dichloroethane. Aluminum chloride was slowly added to the solution and stirred at room temperature for 1 hour. When the reaction was completed, methanol was added and the precipitate formed was filtered and dried.

In a flask, the compound obtained above, 36.21 g of 1-dodecanethiol, 12.55 g of potassium hydroxide, and DMF After adding 315 g, the reaction was stirred at 120° C. for 8 hours. The reaction mixture was cooled and neutralized to about pH 6 to 7 with 5% hydrochloric acid solution, and the precipitate formed was filtered and dried.

A solution was prepared by adding the compound obtained above and 100 mL of tetrahydrofuran to the flask. A 10 g aqueous solution of sodium borohydride was slowly added to the solution, followed by stirring at room temperature for 24 hours to react. Upon completion of the reaction, the mixture was neutralized to about pH 7 with a 5% hydrochloric acid solution, extracted with ethyl acetate and dried to obtain a compound represented by Formula A below.

The molecular weight of the compound was 1,800 g/mol, and the polydispersity (PD) obtained using gel permeation chromatography (GPC) was 1.21.

[Formula A]

Comparative Synthesis Example 2: Synthesis of Polymer B

After putting 50g (0.23mol) of 1-hydroxypyrene in a 500mL flask, add 1-naphthaldehyde (35.9g, 0.23mol), dissolve 200g of PGMEA, and then add p-toluenesulfonic acid (11g, 0.23mol). 0.005 mol) was added, and polymerization was performed by stirring at 90 to 120° C. for about 12 hours. The polymerization reaction was completed until the weight average molecular weight was 2,000 g/mol to 3,000 g/mol, thereby obtaining Polymer B including a structural unit represented by Formula B below.

As a result of measuring the weight average molecular weight (Mw) and polydispersity (PD) of polymer B obtained using gel permeation chromatography (GPC), the weight average molecular weight (Mw) was 3,450 g/mol and , Polydispersity (PD) was 1.80.

[Formula B]

Examples and Comparative Examples

1. Preparation of hard mask composition and evaluation of solubility

1.2 g of each of the polymers and compounds obtained in Synthesis Examples 1 to 6 and Comparative Synthesis Examples 1 and 2 were weighed and uniformly dissolved in 10 g of a mixed solution of PGMEA and cyclohexanone in a 7:3 volume ratio, followed by 0.1 μm Teflon. After filtering through a filter, hardmask compositions according to Examples 1 to 6 and Comparative Examples 1 and 2 were prepared.

On the other hand, before preparing the hard mask composition, each of the polymers and compounds was dissolved in the mixed solution of PGMEA and cyclohexanone, filtered through the Teflon filter, and solubility was evaluated through a loss-on-drying method. Specifically, the solid content in the solution that passed through the Teflon filter was measured, and the weight of each polymer and compound obtained therefrom was compared with the weight before dissolving them in the mixed solution, respectively. When the weight % was exceeded, it was marked with 'x', when it was in the range of 1 to 2 weight %, '○', and when it was less than 1 weight %, it was marked with '◎'. The results are shown in Table 1 below.

2. Preparation and evaluation of organic film

After spin-coating the hard mask composition according to Examples 1 to 6 and Comparative Examples 1 and 2 on a silicon wafer, respectively, heat treatment at 400° C. for 2 minutes on a hot plate to form an organic film with a thickness of about 4,000 Å. formed.

The thickness of the formed organic film was measured using a thin film thickness meter manufactured by K-MAC, and the organic film was dry etched using a CHF ₃ /CF ₄ mixed gas for 100 seconds, respectively, and then the thickness of the organic film was measured again. A bulk etch rate (BER) was calculated from the difference in thickness of the organic film before and after dry etching and the etching time by Equation 1 below.

[Calculation 1]

Etch rate (Å/s) = (initial organic film thickness - organic film thickness after etching) / etching time

In addition, the etching test is performed in the same manner as in the above method, but the thickness of the organic film is measured again after dry etching using a N ₂ /O ₂ mixed gas instead of the CHF ₃ /CF ₄ mixed gas for 60 seconds. The etch rate was calculated according to.

Etch rate calculation results according to the etching test are shown in Table 1 below.

In addition, after spin-coating the hard mask composition according to Examples 1 to 6 and Comparative Examples 1 and 2 on a silicon wafer, respectively, heat treatment at about 400 ° C. for 2 minutes on a hot plate to obtain a thickness of about 1,000 An organic film of Å was formed.

The film density of the formed organic film was measured using PAN alytical's X-ray diffraction equipment, and the results are shown in Table 1 below.

polymer
or compound solubility Membrane Density (g/cm ³ ) Bulk etch rate
(Å/s) CH _x
mixed gas N ₂ /O ₂
mixed gas Example 1 Synthesis Example 1 ○ 1.43 23.8 23.0 Example 2 Synthesis Example 2 ○ 1.42 23.4 21.7 Example 3 Synthesis Example 3 ○ 1.45 24.8 22.6 Example 4 Synthesis Example 4 ◎ 1.43 24.0 22.5 Example 5 Synthesis Example 5 ◎ 1.41 23.7 21.3 Example 6 Synthesis Example 6 ○ 1.38 23.7 21.0 Comparative Example 1 Comparative Synthesis Example 1 ◎ 1.30 28.5 23.7 Comparative Example 2 Comparative Synthesis Example 2 ◎ 1.29 26.2 24

Referring to Table 1, after all of the polymers and compounds according to Synthesis Examples 1 to 6 were dissolved in a mixed solution, the weight of the solid content in the solution passing through the Teflon filter was less than 1% by weight relative to the weight before dissolving the polymer and compound ( It can be seen that the polymer of Synthesis Example 4 and the compound of Synthesis Example 5) has sufficient solubility in the range of 1% to 2% by weight (polymer of Synthesis Example 1 to Synthesis Example 3 and compound of Synthesis Example 6). .

In addition, it can be confirmed that the organic films prepared from the hard mask compositions according to Examples 1 to 6 exhibit sufficient etching resistance to etching gas compared to the organic films prepared from the hard mask compositions according to Comparative Examples 1 and 2. there is.

Furthermore, it can be seen that the organic film formed from the hardmask composition according to Examples 1 to 6 has improved film density compared to the organic film formed from the hardmask composition according to Comparative Example 1 and Comparative Example 2.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concept of the present invention defined in the following claims are also present. It falls within the scope of the right of invention.

Claims (18)

(i) a structural unit represented by Formula 1-1 below, a structural unit represented by Formula 1-2 below, or a polymer comprising a combination thereof, (ii) a compound represented by Formula 2 below, or (iii) the above A combination of the polymer of (i) and the compound of (ii) above, and
Hardmask composition comprising a solvent:
[Formula 1-1] [Formula 1-2]

In Formulas 1-1 and 1-2,
X and Y are each independently a substituted or unsubstituted C4 to C30 aliphatic hydrocarbon ring, a substituted or unsubstituted C6 to C30 aromatic hydrocarbon ring, a substituted or unsubstituted C4 to C30 heterocycle, or a combination thereof. include,
[Formula 2]

In Formula 2 above,
A ¹ and A ² are each independently represented by Formula 3-1 or Formula 3-2 below;
L ¹ to L ⁶ are each independently a single bond, a substituted or unsubstituted C1 to C6 alkylene group, or a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof;
T ¹ to T ³ are each independently a hydroxyl group, a thiol group, a thionyl group, a cyano group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, a substituted or unsubstituted C1 to C30 alkoxy group, or these is a combination of
E ¹ and E ² are each independently a substituted or unsubstituted C4 to C20 aliphatic hydrocarbon ring, a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, or a combination thereof;
m and n are each independently an integer from 0 to 5;
[Formula 3-1] [Formula 3-2]

In Chemical Formulas 3-1 and 3-2,
X and Y are as defined in Chemical Formulas 1-1 and 1-2, respectively. The hardmask composition of claim 1, wherein X and Y of Chemical Formulas 1-1, 1-2, 3-1, and 3-2 each independently include a substituted or unsubstituted C6 to C30 aromatic hydrocarbon ring. In claim 2, wherein the substituted or unsubstituted C6 to C30 aromatic hydrocarbon ring includes one substituted or unsubstituted benzene ring, or a ring in which two or more substituted or unsubstituted benzene rings are connected by a single bond or a linking group. , or a ring in which two or more substituted or unsubstituted benzene rings are condensed. In claim 1, X in Formulas 1-1, 1-2, 3-1, and 3-2 is each independently a C10 to C24 aromatic hydrocarbon ring in which two or more substituted or unsubstituted benzene rings are condensed. A hard mask composition comprising: In claim 1, X in Formulas 1-1, 1-2, 3-1, and 3-2 is each independently a C10 to C20 aromatic hydrocarbon ring in which two or more substituted or unsubstituted benzene rings are condensed. A hard mask composition comprising: The hardmask of claim 1, wherein X in Chemical Formulas 1-1, 1-2, 3-1, and 3-2 each independently includes an aromatic hydrocarbon ring derived from naphthalene, perylene, or coronene. composition. The hardmask composition of claim 1, wherein Y in Chemical Formulas 1-1 and 1-2 each independently includes an aromatic hydrocarbon ring in which two or more substituted or unsubstituted benzene rings are connected by a single bond or a linking group. In claim 7, the linking group is -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, - (CH ₂ ) _p - (Where 1≤p≤10), -(CF ₂ ) _q - (Where, 1≤q≤10), -CR'R"- (Where, R' and R" are each independently hydrogen, a C1 to C10 aliphatic hydrocarbon group, a C6 to C20 aromatic hydrocarbon group, or a C6 to C20 alicyclic hydrocarbon group), -C(CF ₃ )(C ₆ H ₅ )-, -C(CF ₃ ) ₂ -, -C(=O)NH-, a fluorenylene group, or a combination thereof A hard mask composition comprising a. In claim 1, Y in Formulas 1-1 and 1-2, each independently, two substituted or unsubstituted benzene rings are single bonds, -O-, -S-, -C (= O)- , or an aromatic hydrocarbon ring linked by a fluorenylene group. In claim 1, Y in Chemical Formulas 3-1 and 3-2 each independently includes one substituted or unsubstituted benzene ring, or an aromatic hydrocarbon ring in which two or more substituted or unsubstituted benzene rings are condensed. A hard mask composition to do. The hardmask composition of claim 1 , wherein all of L ¹ to L ⁶ in Formula 2 are single bonds. The hardmask composition of claim 1, wherein T ¹ to T ³ in Chemical Formula 2 are all hydroxyl groups. In claim 1, in Formula 2, E ¹ and E ² are each independently a substituted or unsubstituted benzene ring, or an aromatic hydrocarbon ring in which two or more substituted or unsubstituted benzene rings are condensed. A hard mask composition to do. The hardmask composition of claim 1, wherein one of m and n in Chemical Formula 2 is 0 and the other is 1. The hardmask composition of claim 1, wherein Chemical Formula 1-1 is represented by one of the following Chemical Formulas 1-a to 1-c:
[Formula 1-a]

[Formula 1-b]

[Formula 1-c]

. The hardmask composition of claim 1, wherein Chemical Formula 1-2 is represented by the following Chemical Formula 1-d:
[Formula 1-d]

. The hardmask composition of claim 1, wherein the compound represented by Chemical Formula 2 includes a compound represented by the following Chemical Formula [2-a] or the following Chemical Formula [2-b]:
[Formula 2-a]

[Formula 2-b]

. Forming a hard mask layer by applying a hard mask composition according to any one of claims 1 to 17 on a material layer and heat-treating;
forming a photoresist layer over the hard mask layer;
Exposing and developing the photoresist layer to form a photoresist pattern;
selectively removing the hard mask layer using the photoresist pattern and exposing a portion of the material layer; and
Etching the exposed portion of the material layer
Pattern forming method comprising a.