KR102258045B1 - Compound and hardmask composition and method of forming patterns - Google Patents

Abstract

상기 화학식 1에서, Z, L, A 및 R¹ 내지 R¹²의 정의는 명세서에 기재된 바와 같다.It relates to a compound represented by the following Formula 1, a hardmask composition comprising the compound, a hardmask layer including a cured product of the hardmask composition, and a pattern forming method using the hardmask composition.
[Formula 1]

In Formula 1, the definitions of Z, L, A, and R ¹ to R ¹² are as described in the specification.

Description

Compound, hardmask composition, and pattern formation method TECHNICAL FIELD [COMPOUND AND HARDMASK COMPOSITION AND METHOD OF FORMING PATTERNS}

It relates to a compound, a hardmask composition comprising the compound, and a pattern forming method using the hardmask composition.

Recently, the semiconductor industry is developing from a pattern of several hundred nanometers to an ultra-fine technology having a pattern of several to tens of nanometers. Effective lithographic techniques are essential to realize such ultra-fine technology.

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

In recent years, as the size of the pattern to be formed decreases, it is difficult to form a fine pattern having a good profile using only the above-described typical lithographic technique. 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 compound that can improve the etch resistance of the hardmask layer and can be effectively applied to the hardmask layer.

Another embodiment provides a hardmask composition comprising the compound.

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

According to one embodiment, a compound represented by the following formula (1) is provided.

[Formula 1]

In Formula 1,

Z is O or S,

L is a single bond or a double bond,

A is a substituted or unsubstituted hexagonal ring containing at least one nitrogen,

R ¹ to R ¹² are each independently hydrogen, deuterium, halogen, hydroxy group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C1 to C30 alkenyl group, substituted Or an unsubstituted C1 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 To C30 arylalkyl group, a substituted or unsubstituted C6 to C30 heteroarylalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof, R ¹ to R ¹² Are each independently present or two adjacent ones are connected to each other to form a ring.

A is a substituted or unsubstituted non-aromatic hexagonal ring containing at least one nitrogen, and the substitution is at least one substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or It may be substituted with an unsubstituted C3 to C30 heteroaryl group or a combination thereof.

A is a substituted or unsubstituted non-aromatic hexagonal ring containing at least one nitrogen, and the substitution is at least one substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted Or unsubstituted butyl group, substituted or unsubstituted pentyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted A substituted anthracenyl group, a substituted or unsubstituted fluoranthenyl group, a substituted or unsubstituted acenaphthylenyl group, a substituted or unsubstituted acenaphthyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted Benzophenanthrenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted triphenylenyl group, substituted or unsubstituted chrysenyl group, substituted or unsubstituted tetrasenyl group, substituted or unsubstituted benzofluoran Tenyl group, substituted or unsubstituted perylenyl group, substituted or unsubstituted benzopyrenyl group, substituted or unsubstituted naphthoanthracenyl group, substituted or unsubstituted pentacenyl group, substituted or unsubstituted benzoperyle It may be substituted with a nil group, a substituted or unsubstituted dibenzopyrenyl group, a substituted or unsubstituted coronenyl group, or a combination thereof.

At least one of R ¹ to R ⁴ is a hydroxy group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof, and R ¹ to R ⁴ are each independently present or two adjacent to each other may be connected to form a ring. .

The compound represented by Formula 1 may be represented by any one of Formulas 2 and 3 below.

[Formula 2] [Formula 3]

In Formulas 2 and 3,

Z is O or S,

X ¹ to X ³ are each independently CR ^a , CR ^b R ^c , N or NR ^d ,

At least one of X ¹ to X ^{3 is N or NR d} ,

R ¹ to R ¹² and R ^a to R ^d are each independently hydrogen, deuterium, halogen, hydroxy group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C1 To C30 alkenyl group, substituted or unsubstituted C1 to C30 alkynyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 heterocycloalkyl group, A substituted or unsubstituted C1 to C30 arylalkyl group, a substituted or unsubstituted C6 to C30 heteroarylalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof , R ¹ to R ¹² and R ^a to R ^d are each independently present or two adjacent to each other are connected to form a ring.

At least one of R ^a to R ^d is a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted pentyl group, a substituted or unsubstituted A substituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted fluoranthenyl group, a substituted or Unsubstituted acenaphthylenyl group, substituted or unsubstituted acenaphthenyl group, substituted or unsubstituted phenanthrenyl group, substituted or unsubstituted benzophenanthrenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted Triphenylenyl group, substituted or unsubstituted chrysenyl group, substituted or unsubstituted tetrasenyl group, substituted or unsubstituted benzofluoranthenyl group, substituted or unsubstituted perylenyl group, substituted or unsubstituted benzo Pyrenyl group, substituted or unsubstituted naphthoanthracenyl group, substituted or unsubstituted pentacenyl group, substituted or unsubstituted benzoperylenyl group, substituted or unsubstituted dibenzopyrenyl group, substituted or unsubstituted It may be a coronenyl group or a combination thereof.

At least one of X ¹ to X ^{3 is NR d} ,

R ^d may be a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C4 to C30 heteroarylalkyl group, or a combination thereof.

At least one of X ¹ to X ^{3 is NR d} ,

R ^d is a substituted or unsubstituted phenylalkyl group, a substituted or unsubstituted naphthylalkyl group, a substituted or unsubstituted fluorenylalkyl group, a substituted or unsubstituted anthracenylalkyl group, a substituted or unsubstituted fluoranthenylalkyl group, a substituted Or an unsubstituted acenaphthylalkyl group, a substituted or unsubstituted acenaphthenylalkyl group, a substituted or unsubstituted phenanthrenylalkyl group, a substituted or unsubstituted benzophenanthrenylalkyl group, a substituted or unsubstituted pyrenylalkyl group, Substituted or unsubstituted triphenylenylalkyl group, substituted or unsubstituted chrysenylalkyl group, substituted or unsubstituted tetrasenylalkyl group, substituted or unsubstituted benzofluoranthenylalkyl group, substituted or unsubstituted perylenylalkyl group, substituted Or an unsubstituted benzopyrenylalkyl group, a substituted or unsubstituted naphthoanthracenylalkyl group, a substituted or unsubstituted pentacenylalkyl group, a substituted or unsubstituted benzoperylenylalkyl group, a substituted or unsubstituted dibenzopyrenylalkyl group , A substituted or unsubstituted coronenylalkyl group, or a combination thereof.

At least one of R ¹ to R ⁴ is a hydroxy group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof, and R ¹ to R ⁴ are each independently present or two adjacent to each other may be connected to form a ring. .

The compound represented by Formula 2 may be represented by the following Formula 2-1,

The compound represented by Formula 3 may be represented by the following Formula 3-1.

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

In Formulas 2-1 and 3-1,

Z is O or S,

R ¹ to R ¹⁵ are hydrogen, deuterium, halogen, hydroxy group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C1 to C30 alkenyl group, substituted or unsubstituted C1 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 to C30 aryl An alkyl group, a substituted or unsubstituted C6 to C30 heteroarylalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof,

R ¹ to R ¹⁵ are each independently present or two adjacent to each other are connected to each other to form a ring.

At least one of R ¹³ to R ¹⁵ is a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted pentyl group, a substituted or unsubstituted A substituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted fluoranthenyl group, a substituted or Unsubstituted acenaphthylenyl group, substituted or unsubstituted acenaphthenyl group, substituted or unsubstituted phenanthrenyl group, substituted or unsubstituted benzophenanthrenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted Triphenylenyl group, substituted or unsubstituted chrysenyl group, substituted or unsubstituted tetrasenyl group, substituted or unsubstituted benzofluoranthenyl group, substituted or unsubstituted perylenyl group, substituted or unsubstituted benzo Pyrenyl group, substituted or unsubstituted naphthoanthracenyl group, substituted or unsubstituted pentacenyl group, substituted or unsubstituted benzoperylenyl group, substituted or unsubstituted dibenzopyrenyl group, substituted or unsubstituted It may be a coronenyl group or a combination thereof.

R ¹⁵ is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted fluoro. Lantenyl group, substituted or unsubstituted acenaphthylenyl group, substituted or unsubstituted acenaphthyl group, substituted or unsubstituted phenanthrenyl group, substituted or unsubstituted benzophenanthrenyl group, substituted or unsubstituted pyre A nil group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted tetracenyl group, a substituted or unsubstituted benzofluoranthenyl group, a substituted or unsubstituted perylenyl group, A substituted or unsubstituted benzopyrenyl group, a substituted or unsubstituted naphthoanthracenyl group, a substituted or unsubstituted pentacenyl group, a substituted or unsubstituted benzoperylenyl group, a substituted or unsubstituted dibenzopyrenyl group , A substituted or unsubstituted coronenyl group, or a combination thereof.

R ¹⁴ may be a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C4 to C30 heteroarylalkyl group, or a combination thereof.

R ¹⁴ is a substituted or unsubstituted phenylalkyl group, a substituted or unsubstituted naphthylalkyl group, a substituted or unsubstituted fluorenylalkyl group, a substituted or unsubstituted anthracenylalkyl group, a substituted or unsubstituted fluoranthenylalkyl group, a substituted Or an unsubstituted acenaphthylalkyl group, a substituted or unsubstituted acenaphthenylalkyl group, a substituted or unsubstituted phenanthrenylalkyl group, a substituted or unsubstituted benzophenanthrenylalkyl group, a substituted or unsubstituted pyrenylalkyl group, Substituted or unsubstituted triphenylenylalkyl group, substituted or unsubstituted chrysenylalkyl group, substituted or unsubstituted tetrasenylalkyl group, substituted or unsubstituted benzofluoranthenylalkyl group, substituted or unsubstituted perylenylalkyl group, substituted Or an unsubstituted benzopyrenylalkyl group, a substituted or unsubstituted naphthoanthracenylalkyl group, a substituted or unsubstituted pentacenylalkyl group, a substituted or unsubstituted benzoperylenylalkyl group, a substituted or unsubstituted dibenzopyrenylalkyl group , A substituted or unsubstituted coronenylalkyl group, or a combination thereof.

At least one of R ¹ to R ⁴ may be a hydroxy group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof, and R ¹ to R ⁴ are each independently present or two adjacent to each other are connected to form a ring. I can.

According to another embodiment, there is provided a hardmask composition comprising the above-described compound and a solvent.

According to another embodiment, the steps of forming a hardmask layer by applying the above-described hardmask composition on a material layer and heat treatment, forming a photoresist layer on the hardmask layer, exposing and developing the photoresist layer to Forming a photoresist pattern, selectively removing the hardmask layer using the photoresist pattern, exposing a portion of the material layer, and etching the exposed portion of the material layer Provides a method of formation.

It is possible to secure excellent etch resistance, gap-fill characteristics, and planarization characteristics of the hard mask layer.

1 is a reference diagram illustrating a step difference of a hard mask layer by way of example in order to explain a method of evaluating a planarization characteristic.

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

Hereinafter, unless otherwise defined herein, the term'substituted' means that the hydrogen atom in the compound is deuterium, a halogen atom (F, Br, Cl, or I), a hydroxy group, a nitro group, a cyano group, an amino group, an azido group, amidino Group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or 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, C6 It means substituted with a substituent selected from a 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 salt thereof, sulfonic acid group or salt thereof, phosphoric acid or 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 Two adjacent substituents among a 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, and a C2 to C30 heterocyclic group It can also 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.

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

In the present specification, "aryl group" refers to a group having one or more hydrocarbon aromatic moieties, and broadly, hydrocarbon aromatic moieties are linked by a single bond and non-aromatic in which hydrocarbon aromatic moieties are directly or indirectly fused. It also includes fusion rings. Aryl groups include monocyclic, polycyclic or fused polycyclic (ie, rings that share 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, instead of carbon (C) in a cyclic compound such as an aryl group, a cycloalkyl group, a fused ring thereof, or a combination thereof It means containing at least one hetero atom selected from N, O, S, P and Si. When the heterocyclic group is a fused ring, one or more heteroatoms may be included in the entire heterocyclic group or each ring.

More specifically, a substituted or unsubstituted aryl group and/or a substituted or unsubstituted heterocyclic group, 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 non-substituted 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 unsubstituted pyrrolyl group, substituted or unsubstituted pyrazolyl group, substituted or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted oxazolyl group, 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 qui Nolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted benzoxazineyl group, Substituted or unsubstituted benzthiazinyl group, substituted or unsubstituted acridinyl group, substituted or unsubstituted phenazineyl group, substituted or unsubstituted phenothiazinyl group, substituted or unsubstituted phenoxazineyl group, substituted or unsubstituted Cyclic fluorenyl group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothiophenyl group, substituted or unsubstituted carbazolyl group, pyridoindolyl group, benzopyridooxazineyl group, benzopyridothia Jinyl group, 9,9-dimethyl9,10 dihydroacridinyl, a combination thereof, or a combination thereof may be a fused form, but limited thereto It doesn't work. In one example of the present invention, the heterocyclic group or the heteroaryl group may be a pyridyl group, a carbazolyl group, or a pyridoindolyl group.

Hereinafter, a compound according to an embodiment will be described.

In the compound according to an embodiment, one or more polycyclic compounds including a heterocycle may be connected.

The compound according to an embodiment may include a rigid planar structure in which a linking site between polycyclic compounds including a heterocycle is conjugated.

The compound according to an embodiment may be represented by the following formula (1).

[Formula 1]

In Formula 1,

Z is O or S,

L is a single bond or a double bond,

A is a substituted or unsubstituted hexagonal ring containing at least one nitrogen,

R ¹ to R ¹² are each independently hydrogen, deuterium, halogen, hydroxy group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C1 to C30 alkenyl group, substituted Or an unsubstituted C1 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 To C30 arylalkyl group, a substituted or unsubstituted C6 to C30 heteroarylalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof,

R ¹ to R ¹² are each independently present or two adjacent ones are connected to each other to form a ring.

For example, A may be a substituted or unsubstituted aromatic hexagonal ring containing at least one nitrogen or a substituted or unsubstituted nonaromatic hexagonal ring containing at least one nitrogen.

For example, A may be a substituted or unsubstituted aromatic hexagonal ring containing one nitrogen or a substituted or unsubstituted non-aromatic hexagonal ring containing one nitrogen.

For example, A may be a substituted or unsubstituted aromatic hexagonal ring containing two nitrogens or a substituted or unsubstituted non-aromatic hexagonal ring containing two nitrogens.

For example, A may be a substituted or unsubstituted aromatic hexagonal ring containing three nitrogens or a substituted or unsubstituted non-aromatic hexagonal ring containing three nitrogens.

Since the compound contains a heterocycle, it may exhibit high etch resistance capable of withstanding an etching gas exposed in a subsequent etching process.

In one embodiment, A is a substituted or unsubstituted non-aromatic hexagonal ring containing at least one nitrogen,

The substitution may be substituted with at least one substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof. Here, the aryl group may be, for example, a non-condensed aryl group and/or a condensed aryl group, and the heteroaryl group may be a non-condensed heteroaryl group and/or a condensed heteroaryl group.

Wherein A is substituted with at least one substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof, the overall ring parameters of the compound The (ring parameter) may be increased, and higher etch resistance may be exhibited with respect to the etching gas exposed in the subsequent etching process.

As an example, A is a substituted or unsubstituted non-aromatic hexagonal ring containing at least one nitrogen, and the substitution is at least one substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl A group, a substituted or unsubstituted butyl group, a substituted or unsubstituted pentyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, Substituted or unsubstituted anthracenyl group, substituted or unsubstituted fluoranthenyl group, substituted or unsubstituted acenaphthylenyl group, substituted or unsubstituted acenaphthenyl group, substituted or unsubstituted phenanthrenyl group, substituted or Unsubstituted benzophenanthrenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted triphenylenyl group, substituted or unsubstituted chrysenyl group, substituted or unsubstituted tetrasenyl group, substituted or unsubstituted Benzofluoranthenyl group, substituted or unsubstituted perylenyl group, substituted or unsubstituted benzopyrenyl group, substituted or unsubstituted naphthoanthracenyl group, substituted or unsubstituted pentacenyl group, substituted or unsubstituted It may be substituted with a benzoperylenyl group, a substituted or unsubstituted dibenzopyrenyl group, a substituted or unsubstituted coronenyl group, or a combination thereof, but is not limited thereto.

For example, when the compound is heat-treated, a polycondensation reaction between a plurality of compounds may occur, thereby crosslinking, and at least one of ^{R 1} to R ^{4 is, preferably R 2} and/or R ³ is polycondensation It becomes a reaction site of the reaction and can be crosslinked.

For example, at least one of ^{R 1} to R ^{4 , preferably R 2} and/or R ³ may be a C3 to C30 alkyl group. When substituted with such a long aliphatic alkyl group, the compound may have more excellent storage stability.

For example, ^{at least one of R 1} to R ⁴ is a hydroxy group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof, and R ¹ to R ⁴ are each independently present or two adjacent to each other are connected to form a ring can do. When substituted by a hydrophilic functional group such as an alkoxy group or a hydroxy group, the compound may have more excellent solubility, and accordingly, the affinity with the lower film may increase, and the film flatness of the hardmask layer prepared therefrom may be further improved.

For example, ^{at least two of R 1} to R ⁴ are a hydroxy group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof, and R ¹ to R ⁴ are each independently present or two adjacent to each other are connected to form a ring can do.

For example, R ² and/or R ³ may be a hydroxy group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof, and R ² and R ³ may each be independently present or linked to each other to form a ring.

For example, R ¹ to R ⁴ may be the same as or different from each other.

For example, R ² and R ³ may be the same as or different from each other.

For example, the compound represented by Formula 1 may be represented by any one of Formulas 2 and 3 below.

[Formula 2] [Formula 3]

In Formulas 2 and 3,

Z and R ¹ to R ¹² are as described above,

X ¹ to X ³ are each independently CR ^a , CR ^b R ^c , N or NR ^d ,

At least one of X ¹ to X ^{3 is N or NR d} ,

R ^a to R ^d are each independently hydrogen, deuterium, halogen, hydroxy group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C1 to C30 alkenyl group, substituted Or an unsubstituted C1 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 To C30 arylalkyl group, a substituted or unsubstituted C6 to C30 heteroarylalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof,

Each of R ^a to R ^d is independently present or two adjacent two are connected to each other to form a ring.

For example, at least two of ^{X 1} to X ³ may be ^{N or NR d.}

By controlling the aromaticity of R ^a to R ^d and the number of aromatic rings in the compound, the corrosion resistance of the compound can be controlled.

For example, ^{at least one of R a} to R ^d may be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof. have.

For example, ^{at least one of R a} to R ^d is a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted pentyl group, Substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted anthracenyl group, substituted or unsubstituted fluoranthenyl group , A substituted or unsubstituted acenaphthyl group, a substituted or unsubstituted acenaphthenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted benzophenanthrenyl group, a substituted or unsubstituted pyrenyl group, a substituted Or unsubstituted triphenylenyl group, substituted or unsubstituted chrysenyl group, substituted or unsubstituted tetrasenyl group, substituted or unsubstituted benzofluoranthenyl group, substituted or unsubstituted perylenyl group, substituted or unsubstituted A substituted benzopyrenyl group, a substituted or unsubstituted naphthoanthracenyl group, a substituted or unsubstituted pentacenyl group, a substituted or unsubstituted benzoperylenyl group, a substituted or unsubstituted dibenzopyrenyl group, a substituted or It may be an unsubstituted coronenyl group or a combination thereof.

For example, at least one of ^{X 1} to X ³ may be ^{CR a} and CR ^b R ^c.

For example, ^{at least one of R a} to R ^c may be hydrogen or deuterium.

For example, ^{at least one of R b} and R ^c may be hydrogen or deuterium.

For example, ^{at least one of R a} to R ^c may be a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof.

For example, ^{at least one of R b} and R ^c may be a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof.

For example, ^{at least one of R a} to R ^c may be a substituted or unsubstituted C6 to C30 alkylaryl group, a substituted or unsubstituted C3 to C30 heteroalkylaryl group, or a combination thereof.

For example, ^{at least one of R b} and R ^c may be a substituted or unsubstituted C6 to C30 alkylaryl group, a substituted or unsubstituted C3 to C30 heteroalkylaryl group, or a combination thereof.

As an example, the above-described compound is a compound containing a substituted or unsubstituted arylalkylamine and a propargyl group, and an aromatic ring compound having an aldehyde group as a reactant to synthesize an intermediate, and the intermediate is cyclized under a PD catalyst. It may be synthesized, but is not limited thereto. By controlling the aromaticity and the number of aromatic rings of the aromatic ring compound having an aldehyde group of the reactant, the corrosion resistance of the compound may be controlled.

For example, at least one of ^{X 1} to X ^{3 is NR d} ,

R ^d may be a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C4 to C30 heteroarylalkyl group, or a combination thereof.

For example, R ^d is a substituted or unsubstituted phenylalkyl group, a substituted or unsubstituted naphthylalkyl group, a substituted or unsubstituted fluorenylalkyl group, a substituted or unsubstituted anthracenylalkyl group, a substituted or unsubstituted fluoranthenyl Alkyl group, substituted or unsubstituted acenaphthylenylalkyl group, substituted or unsubstituted acenaphthenylalkyl group, substituted or unsubstituted phenanthrenylalkyl group, substituted or unsubstituted benzophenanthrenylalkyl group, substituted or unsubstituted pi Renylalkyl group, substituted or unsubstituted triphenylenylalkyl group, substituted or unsubstituted chrysenylalkyl group, substituted or unsubstituted tetrasenylalkyl group, substituted or unsubstituted benzofluoranthenylalkyl group, substituted or unsubstituted perylenyl Alkyl group, substituted or unsubstituted benzopyrenylalkyl group, substituted or unsubstituted naphthoanthracenylalkyl group, substituted or unsubstituted pentacenylalkyl group, substituted or unsubstituted benzoperylenylalkyl group, substituted or unsubstituted dibenzo It may be a pyrenylalkyl group, a substituted or unsubstituted coroneylalkyl group, or a combination thereof, but is not limited thereto.

For example, R ^d may be a substituted or unsubstituted C7 to C30 arylmethyl group, a substituted or unsubstituted C4 to C30 heteroarylmethyl group, or a combination thereof.

For example, R ^d is a substituted or unsubstituted phenylmethyl group, a substituted or unsubstituted naphthylmethyl group, a substituted or unsubstituted biphenylmethyl group, a substituted or unsubstituted fluorenylmethyl group, a substituted or unsubstituted anthracenylmethyl group , Substituted or unsubstituted fluoranthenylmethyl group, substituted or unsubstituted acenaphthylenylmethyl group, substituted or unsubstituted acenaphthenylmethyl group, substituted or unsubstituted phenanthrenylmethyl group, substituted or unsubstituted benzophenanthre Nylmethyl group, substituted or unsubstituted pyrenylmethyl group, substituted or unsubstituted triphenylenylmethyl group, substituted or unsubstituted chrysenylmethyl group, substituted or unsubstituted tetrasenylmethyl group, substituted or unsubstituted benzofluoranthenylmethyl group , A substituted or unsubstituted perylenylmethyl group, a substituted or unsubstituted benzopyrenylmethyl group, a substituted or unsubstituted naphthoanthracenylmethyl group, a substituted or unsubstituted pentacenylmethyl group, a substituted or unsubstituted benzoperylenyl It may be a methyl group, a substituted or unsubstituted dibenzopyrenylmethyl group, a substituted or unsubstituted coroneylmethyl group, or a combination thereof, but is not limited thereto.

For example, the compound represented by Formula 2 may be represented by Formula 2-1 below.

[Formula 2-1]

For example, the compound represented by Formula 3 may be represented by Formula 3-1 below.

[Chemical Formula 3-1]

In Formulas 2-1 and 3-1,

Z and R ¹ to R ¹² are as described above,

R ¹³ to R ¹⁵ are hydrogen, deuterium, halogen, hydroxy group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C1 to C30 alkenyl group, substituted or unsubstituted C1 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 to C30 aryl An alkyl group, a substituted or unsubstituted C6 to C30 heteroarylalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof,

R ¹³ to R ¹⁵ are each independently present or two adjacent to each other are connected to each other to form a ring.

By controlling the aromaticity and the number of aromatic rings of R ¹ to R ¹⁵ , preferably R ¹³ to R ^{15 in} the compound, the etch resistance of the compound can be controlled.

For example, ^{at least one of R 13} to R ¹⁵ may be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof. have.

For example, ^{at least one of R 13} to R ¹⁵ is a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted pentyl group, Substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted anthracenyl group, substituted or unsubstituted fluoranthenyl group , A substituted or unsubstituted acenaphthyl group, a substituted or unsubstituted acenaphthenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted benzophenanthrenyl group, a substituted or unsubstituted pyrenyl group, a substituted Or unsubstituted triphenylenyl group, substituted or unsubstituted chrysenyl group, substituted or unsubstituted tetrasenyl group, substituted or unsubstituted benzofluoranthenyl group, substituted or unsubstituted perylenyl group, substituted or unsubstituted A substituted benzopyrenyl group, a substituted or unsubstituted naphthoanthracenyl group, a substituted or unsubstituted pentacenyl group, a substituted or unsubstituted benzoperylenyl group, a substituted or unsubstituted dibenzopyrenyl group, a substituted or It may be an unsubstituted coroneyl group or a combination thereof, but is not limited thereto.

For example, R ¹³ may be hydrogen or deuterium.

For example, R ¹⁵ may be a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof.

For example, R ¹⁵ is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted A substituted fluoranthenyl group, a substituted or unsubstituted acenaphthylenyl group, a substituted or unsubstituted acenaphthenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted benzophenanthrenyl group, a substituted or unsubstituted Substituted pyrenyl group, substituted or unsubstituted triphenylenyl group, substituted or unsubstituted chrysenyl group, substituted or unsubstituted tetrasenyl group, substituted or unsubstituted benzofluoranthenyl group, substituted or unsubstituted per Relenyl group, substituted or unsubstituted benzopyrenyl group, substituted or unsubstituted naphthoanthracenyl group, substituted or unsubstituted pentacenyl group, substituted or unsubstituted benzoperylenyl group, substituted or unsubstituted dibenzo It may be a pyrenyl group, a substituted or unsubstituted coronenyl group, or a combination thereof, but is not limited thereto.

For example, R ¹⁵ may be a substituted or unsubstituted C6 to C30 alkylaryl group, a substituted or unsubstituted C3 to C30 heteroalkylaryl group, or a combination thereof.

For example, R ¹⁵ is a substituted or unsubstituted alkylphenyl group, a substituted or unsubstituted alkylnaphthyl group, a substituted or unsubstituted alkylbiphenyl group, a substituted or unsubstituted alkylfluorenyl group, a substituted or unsubstituted alkylanthracenyl Group, a substituted or unsubstituted alkylfluoranthenyl group, a substituted or unsubstituted alkylacenaphthylenyl group, a substituted or unsubstituted alkylacenaphthyl group, a substituted or unsubstituted alkylphenanthrenyl group, a substituted or unsubstituted Alkylbenzophenanthrenyl group, substituted or unsubstituted alkylpyrenyl group, substituted or unsubstituted alkyltriphenylenyl group, substituted or unsubstituted alkylchrycenyl group, substituted or unsubstituted alkyltetracenyl group, substituted or unsubstituted A substituted or unsubstituted alkyl benzofluoranthenyl group, a substituted or unsubstituted alkyl perylenyl group, a substituted or unsubstituted alkyl benzopyrenyl group, a substituted or unsubstituted alkylnaphthoanthracenyl group, or a substituted or unsubstituted alkylpentacenyl It may be a group, a substituted or unsubstituted alkylbenzoperylenyl group, a substituted or unsubstituted alkyldibenzopyrenyl group, a substituted or unsubstituted alkylcoroneyl group, or a combination thereof, but is not limited thereto.

For example, R ¹⁴ may be a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C4 to C30 heteroarylalkyl group, or a combination thereof.

For example, R ¹⁴ is a substituted or unsubstituted phenylalkyl group, a substituted or unsubstituted naphthylalkyl group, a substituted or unsubstituted fluorenylalkyl group, a substituted or unsubstituted anthracenylalkyl group, a substituted or unsubstituted fluoranthenyl group. Alkyl group, substituted or unsubstituted acenaphthylenylalkyl group, substituted or unsubstituted acenaphthenylalkyl group, substituted or unsubstituted phenanthrenylalkyl group, substituted or unsubstituted benzophenanthrenylalkyl group, substituted or unsubstituted pi Renylalkyl group, substituted or unsubstituted triphenylenylalkyl group, substituted or unsubstituted chrysenylalkyl group, substituted or unsubstituted tetrasenylalkyl group, substituted or unsubstituted benzofluoranthenylalkyl group, substituted or unsubstituted perylenyl Alkyl group, substituted or unsubstituted benzopyrenylalkyl group, substituted or unsubstituted naphthoanthracenylalkyl group, substituted or unsubstituted pentacenylalkyl group, substituted or unsubstituted benzoperylenylalkyl group, substituted or unsubstituted dibenzo It may be a pyrenylalkyl group, a substituted or unsubstituted coroneylalkyl group, or a combination thereof, but is not limited thereto.

For example, R ¹⁴ may be a substituted or unsubstituted C7 to C30 arylmethyl group, a substituted or unsubstituted C4 to C30 heteroarylmethyl group, or a combination thereof.

For example, R ¹⁴ is a substituted or unsubstituted phenylmethyl group, a substituted or unsubstituted naphthylmethyl group, a substituted or unsubstituted biphenylmethyl group, a substituted or unsubstituted fluorenylmethyl group, a substituted or unsubstituted anthracenylmethyl group , Substituted or unsubstituted fluoranthenylmethyl group, substituted or unsubstituted acenaphthylenylmethyl group, substituted or unsubstituted acenaphthenylmethyl group, substituted or unsubstituted phenanthrenylmethyl group, substituted or unsubstituted benzophenanthre Nylmethyl group, substituted or unsubstituted pyrenylmethyl group, substituted or unsubstituted triphenylenylmethyl group, substituted or unsubstituted chrysenylmethyl group, substituted or unsubstituted tetrasenylmethyl group, substituted or unsubstituted benzofluoranthenylmethyl group , A substituted or unsubstituted perylenylmethyl group, a substituted or unsubstituted benzopyrenylmethyl group, a substituted or unsubstituted naphthoanthracenylmethyl group, a substituted or unsubstituted pentacenylmethyl group, a substituted or unsubstituted benzoperylenyl It may be a methyl group, a substituted or unsubstituted dibenzopyrenylmethyl group, a substituted or unsubstituted coroneylmethyl group, or a combination thereof, but is not limited thereto.

The molecular weight of the above-described compound may be, for example, about 500 to 10,000, about 1,000 to 8,000, about 1,500 to 6,000, or about 2,000 to 4,000, but is not limited thereto.

In the case of using a compound having the above molecular weight, it is possible to form a more uniform thin film without deterioration of the formation of pin-holes and voids or thickness distribution during the baking process, as well as when there is a step difference or a pattern on the lower substrate (or film). In the case of forming, it is possible to provide more excellent gap-fill and planarization properties.

According to another embodiment, there is provided a hardmask composition comprising the above-described compound and a solvent.

The solvent included in the hardmask composition is not particularly limited as long as it has sufficient solubility or dispersibility in the compound, but, for example, propylene glycol, propylene glycol diacetate, methoxypropanediol, 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-dimethyl It may include at least one selected from acetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone, and ethyl 3-ethoxypropionate, but is not limited thereto.

The compound may be included in, for example, about 0.1 to 50% by weight, about 0.5 to 40% by weight, about 1 to 30% by weight, or about 2 to 20% by weight based on the total content of the hardmask composition. By including the compound in the above range, the thickness, surface roughness, and level of planarization of the hard mask can be controlled.

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

The surfactant may be, for example, a fluoroalkyl-based compound, an alkylbenzene sulfonate, an alkylpyridinium salt, a polyethylene glycol, or a quaternary ammonium salt, but is not limited thereto.

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

In addition, as the crosslinking agent, a crosslinking agent having high heat resistance may be used. As a 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 the molecule can be used.

The thermal acid generator is 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, benzointosylate, 2-nitrobenzyltosylate, and other organic fonate alkyl esters may be used, but the present invention is not limited thereto.

The additive may be included in an amount of about 0.001 to 60 parts by weight, about 0.5 to 40 parts by weight, or about 1 to 30 parts by weight based on 100 parts by weight of the hardmask composition. By including it in the above range, the solubility can be improved without changing the optical properties of the hardmask composition.

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

Hereinafter, a method of forming a pattern using the above-described hardmask composition will be described.

The method of forming a pattern according to an embodiment includes forming a material layer on a substrate, applying a hardmask composition including the above-described compound and a solvent on the material layer, and 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, selectively removing the hardmask 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 can be formed, for example, by a chemical vapor deposition method.

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

The step of heat-treating the hardmask composition may be performed at, for example, about 100 to 700° C. for about 10 seconds to 1 hour.

For example, it 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, a material 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.

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

The step of etching the exposed portion of the material layer may be performed by dry etching using an etching gas, and the etching gas may be CHF ₃ , CF ₄ , Cl ₂ , BCl _3, and a mixed gas thereof.

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, for example, a semiconductor integrated circuit device.

The above-described implementation examples 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 rights.

Compound synthesis

Synthesis Example 1

[Formula 1b]

In a 100 mL round bottom flask, benzyl-(2-bromo-4,5-dimethoxybenzyl)-amine (1.68 g, 5 mmol), 4-methylbenzaldehyde (0.66 g, 5.5 mmol), 1-ethynyl-2- Phenoxybenzene (1.455g, 7.5mmol), 15mol% copper iodide (CuI, 0.1425g) and toluene (30ml) were added, followed by heating at 100°C for 3 hours to proceed with synthesis.

Thereafter, the mixture was filtered through celite and washed with ethyl acetate to obtain a solid. Thereafter, a solution in which the solid (0.3 mmol) was dissolved in dimethylformamide (DMF) was added 10 mol% palladium (II) acetate, 20 mol% triphenylphosphine and cesium carbonate (5 equivalents) to a two-neck round bottom flask and flushed with nitrogen. It was added dropwise to the (flushing) solution. Thereafter, the reaction was carried out for 2 hours in the mixed solution under nitrogen gas conditions at 100°C. After the reaction was cooled to room temperature, it was quenched with saturated aqueous ammonium chloride solution (saturated NH ₄ Cl (aq)). The aqueous layer was extracted with ethyl acetate, washed with brine, and dried over sodium sulfate. After drying, the mixture was concentrated under reduced pressure to obtain a compound represented by Formula 1b.

[Scheme 1]

Synthesis Example 2

[Formula 2b]

A compound represented by Formula 2b was prepared in the same manner as in Synthesis Example 1, except that 1-naphthalenealdehyde (0.858g, 5.5mmol) was used instead of 4-methylbenzaldehyde (0.66g, 5.5mmol).

Synthesis Example 3

[Formula 3b]

A compound represented by Chemical Formula 3b was prepared in the same manner as in Synthesis Example 1, except that 1-pyrenealdehyde (1.26g, 5.5mmol) was used instead of 4-methylbenzaldehyde (0.66g, 5.5mmol).

Synthesis Example 4

[Formula 4b]

A compound represented by Chemical Formula 4b was prepared in the same manner as in Synthesis Example 1, except that 9-anthraldehyde (1.236g, 6.0mmol) was used instead of 4-methylbenzaldehyde (0.66g, 5.5mmol).

Comparative Synthesis Example 1

1-naphthol (28.83 g, 0.2 mol), benzoperylene (41.4 g, 0.15 mol), paraformaldehyde (12.0 g, 0.34 mol), and propylene glycol monomethyl ether acetate (PGMEA) 162 g were added to the flask. 0.19 g of p-toluene sulfonic acid monohydrate was added, and the mixture was stirred at 90°C to 100°C for 5 to 12 hours to proceed with the synthesis. After the reaction, the mixed solution was gradually cooled to room temperature, added to 40 g of distilled water and 400 g of methanol, stirred vigorously, and allowed to stand. The supernatant was removed, and the precipitate was dissolved in 80 g of PGMEA, and then 320 g of methanol was added, stirred vigorously, and allowed to stand (first purification step). The supernatant was removed again, and the precipitate was dissolved in 80 g of PGMEA (second purification process). The first purification step and the second purification step were repeated three times. After purification, the polymer was dissolved in 80 g of PGMEA, and concentrated under reduced pressure to obtain a polymer represented by the following formula (5). (Mw: 2,500)

[Formula 5]

Comparative Synthesis Example 2

Xanton (30g, 0.153mol) and resorcinol (37.04g, 0.336mol) were added to a 500ml two-necked round bottom flask, sulfuric acid (138.67g, 1.414mol) was added, and a reflux condenser was installed, followed by 12 at 120℃. Synthesis proceeded by stirring for a period of time. After the reaction, the mixed solution was cooled to 0° C. and stirred while adding ice water dropwise to obtain a solid. The solid was filtered and washed, and then dried in a vacuum oven at 80° C. for 8 hours to obtain a monomer (51.2 g).

The monomer (50g, 0.131mol) and oxalic acid (0.59g, 0.007mol) were added to a 500ml 3-neck round bottom flask, and ethyl lactate (136.5g) was added. A cooler was installed in the 500ml 3-neck round bottom flask, and 37% formalin (22.15g, 0.273mol) was slowly added dropwise for 1 hour while raising the temperature from 90°C to 100°C, followed by stirring for 12 hours. After stirring, the reaction solution was cooled to room temperature, and then slowly dropped into a mixed solvent of methanol and water to precipitate a polymer. The precipitate was filtered, washed three times with the methanol and water mixed solvent, and dried in a vacuum oven for 48 hours to obtain a polymer represented by the following formula (6). (46.5g, Mw: 2,700).

[Formula 6]

Formation of organic film

Examples 1 to 4, Comparative Examples 1 and 2

Synthesis Examples 1 to 4, Comparative Synthesis Example 1 And 1,5 g of each compound obtained in Comparative Synthesis Example 2 were weighed, uniformly dissolved in 10 g of a mixed solution of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone in a volume ratio of 7:3, and filtered to obtain a hard mask composition. Was prepared. The hardmask composition was spin-coated on a silicon wafer and then heat treated at about 400° C. for 2 minutes (soft bake) to form an organic film.

Evaluation 1. Corrosion resistance

The thickness of the organic films according to Examples 1 to 4 and Comparative Examples 1 and 2 was measured. Subsequently, the organic layer _{was dry-etched for 120 seconds and 60 seconds using a CFx gas or an N 2} /O ₂ mixed gas, respectively, and the thickness of the organic layer was measured again.

From the difference in thickness of the organic layer before and after dry etching and the etching time, the bulk etch rate (BER) was calculated according to Equation 1 below.

[Calculation 1]

Etching rate (Å/s) = (initial organic layer thickness-organic layer thickness after etching)/etching time

The results are shown in Table 1.

Bulk etch rate (Å/s) CF _x etch rate (Å/s) N ₂ /O ₂ etch rate (Å/s) Example 1 25 26 Example 2 24 25 Example 3 22 23 Example 4 23 25 Comparative Example 1 29 27 Comparative Example 2 33 30

Referring to Table 1, it can be seen that the organic layers according to Examples 1 to 4 have sufficient etch resistance to the etching gas compared to the organic layers according to Comparative Examples 1 and 2.

Evaluation 2. Gap-fill characteristics and flattening characteristics

1 is a reference diagram illustrating a step difference of a hard mask layer by way of example in order to explain a method of evaluating a planarization characteristic.

The hard mask-compositions according to Examples 1 to 4 and Comparative Examples 1 to 2 were applied on a silicon pattern wafer (width (w) 20 nm, depth (d) 200 nm, line & space type pattern) (1), and 120 at 400° C. Bake for a second to form a thin film 2 having a thickness of 2,000 Å.

The gap-fill characteristics were determined by the presence or absence of voids by observing the cross section of the pattern with an FE-SEM facility (Hitachi, S-4800).

For the planarization characteristics (step difference measurement), the thickness of the thickest part (H ₀ ) and the film thickness of the thinnest part (H ₁ ) in FIG. 1 were measured by FE-SEM, and the step (|H ₀ -H ₁ |) Was calculated. The smaller the step (|H ₀ -H ₁ |) is, the better the flattening property.

The results are shown in Table 2.

Gap - Fill characteristics (with or without void) Planarization characteristics (step difference, nm) Example 1 no void 44 Example 2 no void 48 Example 3 no void 54 Example 4 no void 50 Comparative Example 1 Void Yes 77 Comparative Example 2 no void 65

Referring to Table 2, it can be seen that the thin film formed from the hardmask composition according to Examples 1 to 4 can simultaneously secure planarization characteristics and the gap-fill characteristics compared to the thin film formed from the hardmask composition according to Comparative Examples 1 to 2. have.

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 by those skilled in the art using the basic concept of the present invention defined in the following claims are also present. It is within the scope of the invention's rights.

Claims (17)

A hardmask composition comprising a compound represented by the following Formula 1, and a solvent:
[Formula 1]

In Formula 1,
Z is O or S,
L is a single bond or a double bond,
A is a substituted or unsubstituted hexagonal ring containing at least one nitrogen,
R ¹ to R ¹² are each independently hydrogen, deuterium, halogen, hydroxy group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C1 to C30 alkenyl group, substituted Or an unsubstituted C1 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 To C30 arylalkyl group, a substituted or unsubstituted C6 to C30 heteroarylalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof,
R ¹ to R ¹² are each independently present or two adjacent ones are connected to each other to form a ring.
In claim 1,
A is a substituted or unsubstituted non-aromatic hexagonal ring containing at least one nitrogen,
The substitution is substituted with at least one substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof. Composition.
In claim 1,
A is a substituted or unsubstituted non-aromatic hexagonal ring containing at least one nitrogen,
The substitution is at least one substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted pentyl group, a substituted or unsubstituted phenyl group , A substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted fluoranthenyl group, a substituted or unsubstituted Acenaphthylenyl group, substituted or unsubstituted acenaphthenyl group, substituted or unsubstituted phenanthrenyl group, substituted or unsubstituted benzophenanthrenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted triphenyl Renyl group, substituted or unsubstituted chrysenyl group, substituted or unsubstituted tetracenyl group, substituted or unsubstituted benzofluoranthenyl group, substituted or unsubstituted perylenyl group, substituted or unsubstituted benzopyrenyl group , A substituted or unsubstituted naphthoanthracenyl group, a substituted or unsubstituted pentacenyl group, a substituted or unsubstituted benzoperylenyl group, a substituted or unsubstituted dibenzopyrenyl group, a substituted or unsubstituted coronenyl group Or that will be substituted with a combination thereof, a hardmask composition.
In claim 1,
At least one of R ¹ to R ⁴ is a hydroxy group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof,
R ¹ to R ⁴ are each independently present or two adjacent to each other are connected to form a ring, the hardmask composition.
In claim 1,
The compound represented by Formula 1 is represented by any one of the following Formulas 2 and 3, a hardmask composition:
[Formula 2] [Formula 3]

In Formulas 2 and 3,
Z is O or S,
X ¹ to X ³ are each independently CR ^a , CR ^b R ^c , N or NR ^d ,
At least one of X ¹ to X ^{3 is N or NR d} ,
R ¹ to R ¹² and R ^a to R ^d are each independently hydrogen, deuterium, halogen, hydroxy group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C1 To C30 alkenyl group, substituted or unsubstituted C1 to C30 alkynyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 heterocycloalkyl group, A substituted or unsubstituted C1 to C30 arylalkyl group, a substituted or unsubstituted C6 to C30 heteroarylalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof ,
R ¹ to R ¹² and R ^a to R ^d are each independently present or two adjacent ones are connected to each other to form a ring.
In clause 5,
At least one of R ^a to R ^d is a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted pentyl group, a substituted or unsubstituted A substituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted fluoranthenyl group, a substituted or Unsubstituted acenaphthylenyl group, substituted or unsubstituted acenaphthenyl group, substituted or unsubstituted phenanthrenyl group, substituted or unsubstituted benzophenanthrenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted Triphenylenyl group, substituted or unsubstituted chrysenyl group, substituted or unsubstituted tetrasenyl group, substituted or unsubstituted benzofluoranthenyl group, substituted or unsubstituted perylenyl group, substituted or unsubstituted benzo Pyrenyl group, substituted or unsubstituted naphthoanthracenyl group, substituted or unsubstituted pentacenyl group, substituted or unsubstituted benzoperylenyl group, substituted or unsubstituted dibenzopyrenyl group, substituted or unsubstituted Coronenyl group or a combination thereof, a hardmask composition.
In clause 5,
At least one of X ¹ to X ^{3 is NR d} ,
R ^d is a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C4 to C30 heteroarylalkyl group, or a combination thereof, a hardmask composition.
In clause 5,
At least one of X ¹ to X ^{3 is NR d} ,
R ^d is a substituted or unsubstituted phenylalkyl group, a substituted or unsubstituted naphthylalkyl group, a substituted or unsubstituted fluorenylalkyl group, a substituted or unsubstituted anthracenylalkyl group, a substituted or unsubstituted fluoranthenylalkyl group, a substituted Or an unsubstituted acenaphthylalkyl group, a substituted or unsubstituted acenaphthenylalkyl group, a substituted or unsubstituted phenanthrenylalkyl group, a substituted or unsubstituted benzophenanthrenylalkyl group, a substituted or unsubstituted pyrenylalkyl group, Substituted or unsubstituted triphenylenylalkyl group, substituted or unsubstituted chrysenylalkyl group, substituted or unsubstituted tetrasenylalkyl group, substituted or unsubstituted benzofluoranthenylalkyl group, substituted or unsubstituted perylenylalkyl group, substituted Or an unsubstituted benzopyrenylalkyl group, a substituted or unsubstituted naphthoanthracenylalkyl group, a substituted or unsubstituted pentacenylalkyl group, a substituted or unsubstituted benzoperylenylalkyl group, a substituted or unsubstituted dibenzopyrenylalkyl group , A substituted or unsubstituted coronenylalkyl group or a combination thereof, a hardmask composition.
In clause 5,
At least one of R ¹ to R ⁴ is a hydroxy group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof,
R ¹ to R ⁴ are each independently present or two adjacent to each other are connected to each other to form a ring, hardmask composition.
In clause 5,
The compound represented by Formula 2 is a compound represented by Formula 2-1,
The compound represented by Formula 3 is a compound represented by the following Formula 3-1, a hardmask composition:
[Chemical Formula 2-1] [Chemical Formula 3-1]

In Formulas 2-1 and 3-1,
Z is O or S,
R ¹ to R ¹⁵ are hydrogen, deuterium, halogen, hydroxy group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C1 to C30 alkenyl group, substituted or unsubstituted C1 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 to C30 aryl An alkyl group, a substituted or unsubstituted C6 to C30 heteroarylalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof,
R ¹ to R ¹⁵ are each independently present or two adjacent to each other are connected to each other to form a ring.
In claim 10,
At least one of R ¹³ to R ¹⁵ is a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted pentyl group, a substituted or unsubstituted A substituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted fluoranthenyl group, a substituted or Unsubstituted acenaphthylenyl group, substituted or unsubstituted acenaphthenyl group, substituted or unsubstituted phenanthrenyl group, substituted or unsubstituted benzophenanthrenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted Triphenylenyl group, substituted or unsubstituted chrysenyl group, substituted or unsubstituted tetrasenyl group, substituted or unsubstituted benzofluoranthenyl group, substituted or unsubstituted perylenyl group, substituted or unsubstituted benzo Pyrenyl group, substituted or unsubstituted naphthoanthracenyl group, substituted or unsubstituted pentacenyl group, substituted or unsubstituted benzoperylenyl group, substituted or unsubstituted dibenzopyrenyl group, substituted or unsubstituted Coronenyl group or a combination thereof, a hardmask composition.
In claim 10,
R ¹⁵ is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted fluorine. Lantenyl group, substituted or unsubstituted acenaphthylenyl group, substituted or unsubstituted acenaphthyl group, substituted or unsubstituted phenanthrenyl group, substituted or unsubstituted benzophenanthrenyl group, substituted or unsubstituted pyre A nil group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted tetracenyl group, a substituted or unsubstituted benzofluoranthenyl group, a substituted or unsubstituted perylenyl group, A substituted or unsubstituted benzopyrenyl group, a substituted or unsubstituted naphthoanthracenyl group, a substituted or unsubstituted pentacenyl group, a substituted or unsubstituted benzoperylenyl group, a substituted or unsubstituted dibenzopyrenyl group , A hardmask composition that is a substituted or unsubstituted coronenyl group or a combination thereof.
In claim 10,
R ¹⁴ is a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C4 to C30 heteroarylalkyl group, or a combination thereof, a hardmask composition.
In claim 10,
R ¹⁴ is a substituted or unsubstituted phenylalkyl group, a substituted or unsubstituted naphthylalkyl group, a substituted or unsubstituted fluorenylalkyl group, a substituted or unsubstituted anthracenylalkyl group, a substituted or unsubstituted fluoranthenylalkyl group, a substituted Or an unsubstituted acenaphthylalkyl group, a substituted or unsubstituted acenaphthenylalkyl group, a substituted or unsubstituted phenanthrenylalkyl group, a substituted or unsubstituted benzophenanthrenylalkyl group, a substituted or unsubstituted pyrenylalkyl group, Substituted or unsubstituted triphenylenylalkyl group, substituted or unsubstituted chrysenylalkyl group, substituted or unsubstituted tetrasenylalkyl group, substituted or unsubstituted benzofluoranthenylalkyl group, substituted or unsubstituted perylenylalkyl group, substituted Or an unsubstituted benzopyrenylalkyl group, a substituted or unsubstituted naphthoanthracenylalkyl group, a substituted or unsubstituted pentacenylalkyl group, a substituted or unsubstituted benzoperylenylalkyl group, a substituted or unsubstituted dibenzopyrenylalkyl group , A substituted or unsubstituted coronenylalkyl group or a combination thereof, a hardmask composition.
In claim 10,
At least one of R ¹ to R ⁴ is a hydroxy group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof,
R ¹ to R ⁴ are each independently present or two adjacent to each other are connected to form a ring, the hardmask composition.
delete Applying the hardmask composition according to any one of claims 1 to 15 on the material layer and performing heat treatment to form a hardmask layer,
Forming a photoresist layer on the hardmask layer,
Exposing and developing the photoresist layer to form a photoresist pattern,
Selectively removing the hardmask 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.

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