KR102456164B1 - Hardmask composition and method of forming patterns - Google Patents

Abstract

상기 화학식 1에서,
A¹, A², B¹, B², C¹, C², L, n¹, n², m 및 *의 정의는 명세서에 기재한 바와 같다.It relates to a hard mask composition including a polymer including a moiety represented by the following Chemical Formula 1, and a solvent, and a pattern forming method.
[Formula 1]

In Formula 1,
The definitions of A ¹ , A ² , B ¹ , B ² , C ¹ , C ² , L, n ¹ , n ² , m and * are as described in the specification.

Description

Hard mask composition and pattern formation method

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

Recently, the semiconductor industry has developed from a pattern of several hundreds of nanometers to an ultra-fine technology having a pattern of several to tens of nanometers. An effective lithographic technique is 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.

Recently, as the size of a pattern to be formed is reduced, 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 hardmask composition that can be effectively applied to a hardmask layer.

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

According to one embodiment, there is provided a hard mask composition including a polymer including a moiety represented by the following Chemical Formula 1, and a solvent.

[Formula 1]

In Formula 1, A ¹ , A ² , B ¹ , B ² , C ¹ and C ² are each independently a substituted or unsubstituted C6 to C30 aromatic ring,

L is a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof,

n ¹ and n ² are each independently an integer from 0 to 5, m is an integer from 0 to 100, and * is a point of connection with another moiety in the polymer.

A ¹ , A ² , B ¹ , B ² , C ¹ and C ² are each independently substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted pyrene, substituted or unsubstituted fluoranthene, substituted or unsubstituted acenaphthalene, substituted or unsubstituted acenaphthene, substituted or unsubstituted benzophenanthrene, substituted or unsubstituted chrysene, substituted or unsubstituted perylene, substituted or unsubstituted benzopyrene, substituted or unsubstituted tetracene, substituted or unsubstituted benzofluoranthene, substituted or unsubstituted dibenzofluoranthene, substituted or unsubstituted benzofurylene, substituted or unsubstituted coronene, substituted or unsubstituted naphthoanthracene, substituted or unsubstituted triphenylene, substituted or pentacene, or a combination thereof.

A ¹ , A ² , B ¹ , B ² , C ¹ and C ² are each independently unsubstituted; A cyano group, a hydroxyl group, a substituted or unsubstituted C1 to C30 alkoxy group, an amino group, a halogen group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof It may be a C30 aromatic ring.

A ¹ and C ² may be equal to each other, A ² and C ¹ may be equal to each other, and B ¹ and B ² may be equal to each other.

L is a single bond, a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted It may be a naphthylene group, a substituted or unsubstituted anthracenylene group, a substituted or unsubstituted phenanthrenylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted fluorenylene group, or a combination thereof.

The moiety represented by Formula 1 may be represented by any one of Formulas 1-1 to 1-4.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4, A ¹ , A ² , B ¹ , B ² , C ¹ and C ² are each independently a substituted or unsubstituted C6 to C30 aromatic ring,

L is a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof,

* is the point of connection with other moieties in the polymer.

The polymer may include a first structural unit represented by Formula 2 below.

[Formula 2]

In Formula 2, X ¹ is a moiety represented by Formula 1, and Y ¹ is a divalent organic group.

Y ¹ may be represented by Formula 3 below.

[Formula 3]

In Formula 3,

Ar ¹ is a substituted or unsubstituted C6 to C30 arylene group,

R ¹ to R ⁴ are each independently hydrogen, deuterium, a halogen group, a nitro group, an amino group, a hydroxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,

R ¹ and R ² are each independently present or linked to each other to form a ring,

R ³ and R ⁴ are each independently present or linked to each other to form a ring,

p ¹ is 0 or 1, q ¹ is an integer from 0 to 3,

* is the point of connection with other moieties in the polymer of formula (2).

Ar ¹ may be any one of substituted or unsubstituted selected from Group 2 below.

[Group 2]

In group 2,

W is a single bond, oxygen (-O-), sulfur (-S-), -SO ₂ -, substituted or unsubstituted ethenylene, carbonyl (-C(=O)-), CR ^a R ^b , NR ^c or a combination thereof,

R ^a to R ^c are each independently hydrogen, halogen, a carboxyl group, a substituted or unsubstituted C2 to C30 oxoalkyl group, a substituted or unsubstituted C1 to C30 alkoxycarbonyl group, a substituted or unsubstituted C1 to C30 alkoxy group, A substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C30 alkenyl group, a substituted or unsubstituted C1 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to a C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heterocyclic group, or a combination thereof;

p is an integer from 1 to 30,

* is the point of connection with other moieties in the polymer of formula (3).

Formula 3 may be represented by Formula 3-1 or 3-2 below.

[Formula 3-1]

[Formula 3-2]

In Formulas 3-1 and 3-2,

Ar ¹ is a substituted or unsubstituted C6 to C30 arylene group,

R ¹ to R ⁴ are each independently hydrogen, deuterium, a halogen group, a nitro group, an amino group, a hydroxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,

R ¹ and R ² are each independently present or linked to each other to form a ring,

R ³ and R ⁴ are each independently present or linked to each other to form a ring,

* is the point of connection with other moieties in the polymer of formula (2).

The polymer may further include a second structural unit different from the first structural unit.

The second structural unit may be represented by the following formula (4).

[Formula 4]

In Formula 4, X ² is a substituted or unsubstituted C6 to C30 aromatic ring, and Y ² is a divalent organic group.

X ² may be any one of substituted or unsubstituted selected from the following group 3.

[Group 3]

.

.

X ² may include at least one hydroxyl group.

Y ² may be represented by the following Chemical Formula 5.

[Formula 5]

In Formula 5,

Ar ² is a substituted or unsubstituted C6 to C30 arylene group,

R ⁵ to R ⁸ are each independently hydrogen, deuterium, a halogen group, a nitro group, an amino group, a hydroxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,

R ⁵ and R ⁶ are each independently present or linked to each other to form a ring,

R ⁷ and R ⁸ are each independently present or linked to each other to form a ring,

p ² is 0 or 1, q ² is an integer from 0 to 3,

* is the point of connection with other moieties in the polymer of formula (4).

Ar ² may be any one of substituted or unsubstituted selected from Group 4 below.

[Group 4]

In group 4,

W is a single bond, oxygen (-O-), sulfur (-S-), -SO ₂ -, substituted or unsubstituted ethenylene, carbonyl (-C(=O)-), CR ^a R ^b , NR ^c or a combination thereof,

R ^a to R ^c are each independently hydrogen, halogen, a carboxyl group, a substituted or unsubstituted C2 to C30 oxoalkyl group, a substituted or unsubstituted C1 to C30 alkoxycarbonyl group, a substituted or unsubstituted C1 to C30 alkoxy group, A substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C30 alkenyl group, a substituted or unsubstituted C1 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to a C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heterocyclic group, or a combination thereof;

p is an integer from 1 to 30,

* is the point of connection with other moieties in the polymer of formula (5).

Formula 5 may be represented by Formula 5-1 or 5-2 below.

[Formula 5-1]

[Formula 5-2]

In Formulas 5-1 and 5-2,

Ar ² is a substituted or unsubstituted C6 to C30 arylene group,

R ⁵ to R ⁸ are each independently hydrogen, deuterium, a halogen group, a nitro group, an amino group, a hydroxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,

R ⁵ and R ⁶ are each independently present or linked to each other to form a ring,

R ⁷ and R ⁸ are each independently present or linked to each other to form a ring,

* is the point of connection with other moieties in the polymer of formula (4).

According to another embodiment, applying the above-described hardmask composition on a material layer and heat-treating to form a hardmask layer, forming a photoresist layer on the hardmask layer, exposing and developing the photoresist layer to photoresist Forming a pattern comprising forming a resist 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 provide a way

It is possible to simultaneously secure the solubility of the polymer, the film density of the hard mask layer, and the etch resistance.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art to which the present invention pertains can easily implement them. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

Hereinafter, unless otherwise specified herein, 'substituted' means that a 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, an amidino group group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid 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 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), a hydroxyl group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group , 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 two adjacent substituents of 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 They can also be fused to form rings. For example, the substituted C6 to C30 aryl group may be fused with another adjacent substituted C6 to C30 aryl group to form a substituted or unsubstituted fluorene ring.

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

As used herein, "aromatic ring" refers to a single ring; a condensed aromatic ring in which two or more aromatic rings are condensed; Two or more aromatic rings include a single bond, a C1 to C5 alkylene group, a non-condensed aromatic ring connected by O or C(=O), or a combination thereof.

As used herein, the term "heterocycle" is a concept including a heteroaromatic ring, and in addition, N, O, It means containing at least one hetero atom selected from S, P and Si. When the heterocycle is a fused ring, the entire heterocycle or each ring may include one or more heteroatoms.

As used herein, the term "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 non-aromatic hydrocarbon aromatic moiety directly or indirectly fused. Also included are fused 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, in addition to carbon (C) in a ring 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, the entire heterocyclic group or each ring may include one or more heteroatoms.

More specifically, a substituted or unsubstituted aryl group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted flu Orenyl group, substituted or unsubstituted naphthacenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted quaterphenyl group, substituted or unsubstituted cri A cenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted indenyl group, a combination thereof, or a combination thereof may be in a fused form, but is not limited thereto. .

More specifically, the substituted or unsubstituted heterocyclic group is a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted oxazolyl group, substituted or unsubstituted thiazolyl group, substituted or unsubstituted oxadiazolyl group, substituted or unsubstituted thiadiazole Diyl, substituted or unsubstituted pyridinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted benzofuranyl group, substituted or unsubstituted A substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinazolyl group Nyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted benzoxazinyl group, substituted or unsubstituted benzthiazinyl group, substituted or unsubstituted acridinyl group, substituted Or an unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted A substituted carbazolyl group, a substituted or unsubstituted pyridoindolyl group, a substituted or unsubstituted benzopyridooxazinyl group, a substituted or unsubstituted benzopyridothiazinyl group, a substituted or unsubstituted 9,9-dimethyl9 ,10 dihydroacridinyl group, a combination thereof, or a combination thereof may be in a fused form, but is not limited thereto. In one embodiment of the present invention, the heterocyclic group or the heteroaryl group may be a pyrrole group, an indolyl group or a carbazolyl group.

As used herein, "arylene group" means that there are two linking groups in the substituted or unsubstituted aryl group defined above, for example, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthalene group, a substituted or Unsubstituted anthracenylene group, substituted or unsubstituted phenanthrylene group, substituted or unsubstituted naphthacenylene group, substituted or unsubstituted pyrenylene group, substituted or unsubstituted biphenylene group, substituted or unsubstituted terphenyl Rene group, substituted or unsubstituted quaterphenylene group, substituted or unsubstituted chrysenylene group, substituted or unsubstituted triphenylenylene group, substituted or unsubstituted perylenylene group, substituted or unsubstituted indenylene group, these A combination of or a combination thereof may be in a condensed form, but is not limited thereto.

In addition, in this specification, the polymer means including an oligomer and a polymer.

Hereinafter, a hard mask composition according to an embodiment will be described.

A hardmask composition according to an embodiment includes a polymer and a solvent.

The polymer may include a moiety in which at least one cyclic ether and at least one aromatic ring are condensed, and the moiety may be in which the cyclic ether and the aromatic ring are condensed alternately. Specifically, the cyclic ether may be a 6-membered ring, and two or more of the atoms constituting the 6-membered ring may be oxygen atoms. Specifically, the moiety may be represented by Chemical Formula 1 to be described later.

Accordingly, the polymer can form a hard film-like polymer layer by including an aromatic ring having a high carbon content, thereby improving corrosion resistance, and at the same time, by including a cyclic ether condensed on the aromatic ring, the solubility of the polymer in a solvent is improved. It can be increased to improve the coatability of the hard mask composition.

Specifically, the polymer may include a moiety represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1, A ¹ , A ² , B ¹ , B ² , C ¹ and C ² are each independently a substituted or unsubstituted C6 to C30 aromatic ring,

L is a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof,

n ¹ and n ² are each independently an integer from 0 to 5, m is an integer from 0 to 100,

* is the point of connection with other moieties in the polymer.

the aromatic ring is a single ring; is a fused ring in which two or more aromatic rings are fused; It may be an unfused ring in which two or more aromatic rings are connected by a single bond, a C1 to C5 alkylene group, O or C(=O).

For example, A ¹ , A ² , B ¹ , B ² , C ¹ and C ² may each independently be benzene or a polycyclic aromatic hydrocarbon, wherein the polycyclic aromatic hydrocarbon is a non-condensed aromatic ring, a condensed aromatic ring, or these may be a combination of

For example, A ¹ , A ² , B ¹ , B ² , C ¹ and C ² are each independently substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted pyrene, substituted or unsubstituted fluoranthene, substituted or unsubstituted acenaphthalene, substituted or unsubstituted acenaphthene, substituted or unsubstituted benzophenanthrene, substituted or unsubstituted chrysene, substituted or unsubstituted perylene, substituted or unsubstituted benzopyrene, substituted or unsubstituted tetracene, substituted or unsubstituted benzofluoranthene, substituted or unsubstituted dibenzofluoranthene, substituted or unsubstituted benzoperylene, It may be a substituted or unsubstituted coronene, a substituted or unsubstituted naphthoanthracene, a substituted or unsubstituted triphenylene, a substituted or pentacene, or a combination thereof.

For example, A ¹ , A ² , B ¹ , B ² , C ¹ and C ² are each independently substituted or unsubstituted benzene; A ¹ , A ² , B ¹ , B ² , C ¹ and C ² are each independently substituted or unsubstituted naphthalene; A ¹ , A ² , C ¹ and C ² may each independently be substituted or unsubstituted naphthalene, and B ¹ and B ² may each independently be substituted or unsubstituted benzene.

For example, A ¹ , A ² , B ¹ , B ² , C ¹ and C ² are each independently unsubstituted; A cyano group, a hydroxyl group, a substituted or unsubstituted C1 to C30 alkoxy group, an amino group, a halogen group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof It may be a C30 aromatic ring.

For example, A ¹ , A ² , B ¹ , B ² , C ¹ and C ² are each independently benzene; naphthalene; Cyano group, hydroxyl group, substituted or unsubstituted methoxy group, substituted or unsubstituted ethoxy group, substituted or unsubstituted propoxy group, amino group, halogen group, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or benzene substituted with an unsubstituted propyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a combination thereof; Cyano group, hydroxyl group, substituted or unsubstituted methoxy group, substituted or unsubstituted ethoxy group, substituted or unsubstituted propoxy group, amino group, halogen group, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or naphthalene substituted with an unsubstituted propyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a combination thereof; or a combination thereof.

For example, A ¹ , A ² , B ¹ , B ² , C ¹ and C ² are each independently benzene, cyanobenzene, hydroxybenzene, phenylbenzene, naphthalene, cyanonaphthalene, hydroxynaphthalene, phenylnaphthalene, or It may be a combination of these.

For example, A ¹ , A ² , B ¹ , B ² , C ¹ and C ² may be the same as or different from each other.

For example, A ¹ and C ¹ may be the same as or different from each other.

For example, A ¹ and C ² may be equal to each other, A ² and C ¹ may be equal to each other, and B ¹ and B ² may be equal to each other.

Specifically, A ¹ , A ² , B ¹ , B ² , C ¹ and C ² are each independently benzene, cyanobenzene, hydroxybenzene, phenylbenzene, or a combination thereof; A ¹ , A ² , B ¹ , B ² , C ¹ and C ² are each independently naphthalene, cyanonaphthalene, hydroxynaphthalene, phenylnaphthalene, or a combination thereof; A ¹ , A ² , C ¹ and C ² are each independently naphthalene, cyanonaphthalene, hydroxynaphthalene, phenylnaphthalene, or a combination thereof, and B ¹ and B ² are each independently benzene, cyanobenzene, hydroxy It may be benzene, phenylbenzene, or a combination thereof, but is not limited thereto.

For example, L may include a single bond, a substituted or unsubstituted C1 to C15 alkylene group, or a substituted or unsubstituted C6 to C25 arylene group. Here, the substituted or unsubstituted C1 to C15 alkylene group is, for example, a substituted or unsubstituted C1 to C10 alkylene group, for example, a substituted or unsubstituted C1 to C7 alkylene group, for example, a substituted or It may be an unsubstituted C1 to C5 alkylene group, for example, a substituted or unsubstituted C1 to C4 alkylene group. Also, here, the substituted or unsubstituted C6 to C25 arylene group may be, for example, a substituted or unsubstituted C6 to C20 arylene group, for example, a substituted or unsubstituted C6 to C16 arylene group.

Specifically, L is a single bond, a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, a substituted or unsubstituted phenylene group, a substituted or It may be an unsubstituted naphthylene group, a substituted or unsubstituted anthracenylene group, a substituted or unsubstituted phenanthrenylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted fluorenylene group, or a combination thereof. However, the present invention is not limited thereto.

For example, n ¹ and n ² may each independently be an integer of 0 to 4, for example, may be an integer of 0 to 3, for example, may be an integer of 0 to 2, for example, 0 or 1 can be

For example, n ¹ and n ² may be the same as each other.

For example, n ¹ and n ² may each be 0.

For example, n ¹ and n ² may each be 1.

For example, m may be an integer from 0 to 100, for example, may be an integer from 0 to 70, for example, may be an integer from 0 to 50, for example, may be an integer from 0 to 30, e.g. For example, it may be an integer from 0 to 20, for example, may be an integer from 0 to 15, for example, may be an integer from 0 to 10, for example, may be an integer from 0 to 5, for example , may be an integer of 0 to 3, for example, may be an integer of 0 to 2, for example, may be 0 or 1.

For example, the moiety represented by Formula 1 may be represented by any one of Formulas 1-1 to 1-4 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4, A ¹ , A ² , B ¹ , B ² , C ¹ , C ² , L and * are the same as described above.

The polymer according to an embodiment may include one or a plurality of substituted or unsubstituted moieties represented by the above-described Chemical Formula 1, and a plurality of substituted or unsubstituted moieties represented by the above-described Chemical Formula 1 are mutually exclusive. may be the same or different from each other.

The polymer may include a moiety represented by Chemical Formula 1 described above as a main chain. Accordingly, due to the interaction and/or stacking action between the polymers by the oxygen atom constituting the ring of the cyclic ether (in the moiety represented by Formula 1 above), the layer made of the polymer is Higher film strength and film density can be exhibited. Accordingly, when a layer having a narrow line width pattern is formed on a layer made of a polymer including the moiety represented by Chemical Formula 1 as a main chain, the warpage of the pattern can be reduced, and a long via can be formed. Alternatively, when a layer having a pattern including holes is formed, bowing of the pattern may be reduced.

For example, the polymer may include a first structural unit represented by Formula 2 below.

[Formula 2]

In Formula 2, X ¹ is a moiety represented by Formula 1, and Y ¹ is a divalent organic group. Specifically, the moiety represented by Chemical Formula 1 is the same as described above.

For example, Y ¹ may include a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof. Accordingly, the polymer can not only have excellent etch resistance, but also can further increase solubility in solvents, so that when a film is formed from the composition containing the polymer, when there is a step in the lower substrate (or film), or When forming a pattern, better gap-fill and planarization properties can be provided.

For example, Y ¹ may include a substituted or unsubstituted C1 to C20 alkylene group, for example, may include a substituted or unsubstituted C1 to C15 alkylene group, for example, a substituted or unsubstituted C1 to C15 alkylene group. a C1 to C10 alkylene group, for example, a substituted or unsubstituted C1 to C7 alkylene group, for example, a substituted or unsubstituted C1 to C5 alkylene group, for example, a substituted or unsubstituted C1 to C4 alkyl It may include a rengi. Specifically, Y ¹ may include a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, or a combination thereof.

For example, Y ¹ may further include the aforementioned substituted or unsubstituted C1 to C20 alkylene group and a substituted or unsubstituted C6 to C30 arylene group, for example, the substituted or unsubstituted C6 to C30 aryl group. The ren group may be a single ring and/or a polycyclic ring, and the polycyclic ring may be a condensed ring and/or a non-condensed ring.

For example, Y ¹ may further include a substituted or unsubstituted C1 to C20 alkylene group and a substituted or unsubstituted arylene group selected from the group 2 below.

[Group 2]

In group 2,

W is a single bond, oxygen (-O-), sulfur (-S-), -SO ₂ -, substituted or unsubstituted ethenylene, carbonyl (-C(=O)-), CR ^a R ^b , NR ^c or a combination thereof,

R ^a to R ^c are each independently hydrogen, halogen, a carboxyl group, a substituted or unsubstituted C2 to C30 oxoalkyl group, a substituted or unsubstituted C1 to C30 alkoxycarbonyl group, a substituted or unsubstituted C1 to C30 alkoxy group, A substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C30 alkenyl group, a substituted or unsubstituted C1 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to a C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heterocyclic group, or a combination thereof;

p is an integer from 1 to 30,

* is the point of connection with other moieties in the polymer of formula (2).

In Group 2, each arylene group may be unsubstituted or substituted with one or more substituents. Here, the substituent is, for example, deuterium, halogen, hydroxy group, amino group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 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, substituted or unsubstituted C1 to C30 arylalkyl group, It may be 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, but is not limited thereto.

For example, Y ¹ may be represented by Formula 3 below.

[Formula 3]

In Formula 3,

Ar ¹ is a substituted or unsubstituted C6 to C30 arylene group,

R ¹ to R ⁴ are each independently hydrogen, deuterium, a halogen group, a nitro group, an amino group, a hydroxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,

R ¹ and R ² are each independently present or linked to each other to form a ring,

R ³ and R ⁴ are each independently present or linked to each other to form a ring,

p ¹ is 0 or 1, q ¹ is an integer from 0 to 3,

* is the point of connection with other moieties in the polymer of formula (2).

For example, Ar ¹ may be any one of substituted or unsubstituted selected from Group 2 above.

For example, at least two of R ¹ to R ⁴ may be hydrogen, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; For example, at least one of R ¹ and R ² is hydrogen, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, and at least one of R ³ and R ⁴ is hydrogen, a substituted or unsubstituted C6 to C30 aryl group. an aryl group or a combination thereof; For example, R ¹ to R ⁴ may each independently be hydrogen, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.

For example, at least two of R ¹ to R ⁴ may be hydrogen; For example, at least one of R ¹ and R ² may be hydrogen, and at least one of R ³ and R ⁴ may be hydrogen. For example, R ¹ to R ⁴ may all be hydrogen.

For example, two of R ¹ to R ⁴ may be hydrogen, and the other two of R ¹ to R ⁴ may be a substituted or unsubstituted C6 to C30 aryl group; For example, one of R ¹ and R ² is hydrogen, the other of R ¹ and R ² is a substituted or unsubstituted C6 to C30 aryl group, one of R ³ and R ⁴ is hydrogen, R ³ and The other one of R ⁴ may be a substituted or unsubstituted C6 to C30 aryl group. Here, the substituted or unsubstituted C6 to C30 aryl group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted It may be a phenanthrenyl group, a substituted or unsubstituted pyrenyl group, or a combination thereof, but is not limited thereto.

For example, at least two of R ¹ to R ⁴ may be a substituted or unsubstituted C6 to C30 aryl group; For example, at least one of R ¹ and R ² may be a substituted or unsubstituted C6 to C30 aryl group, and at least one of R ³ and R ⁴ may be a substituted or unsubstituted C6 to C30 aryl group. For example, R ¹ to R ⁴ may be all substituted or unsubstituted C6 to C30 aryl groups. Here, the substituted or unsubstituted C6 to C30 aryl group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted It may be a phenanthrenyl group, a substituted or unsubstituted pyrenyl group, or a combination thereof.

For example, R ¹ to R ⁴ may be the same as or different from each other, for example, R ¹ and R ² may be the same as or different from each other, and R ³ and R ⁴ may be the same as or different from each other.

For example, R ¹ and R ² may each independently exist or combine with each other to form a ring, and R ³ and R ⁴ may each independently exist or combine with each other to form a ring.

For example, q ¹ may be an integer of 0 to 2, and q ¹ may be 0 or 1.

When q ¹ is an integer of 2 or more, a plurality of R ³ may be the same as or different from each other, and a plurality of R ⁴ may be the same as or different from each other.

For example, both q ¹ and p ¹ may be 0, and both q ¹ and p ¹ may be 1.

For example, Chemical Formula 3 may be represented by Chemical Formula 3-1 or 3-2 below.

[Formula 3-1]

[Formula 3-2]

In Formulas 3-1 and 3-2, Ar ¹ , R ¹ to R ⁴ and * are the same as described above.

For example, in Formula 2, Y ¹ may be any one of substituted or unsubstituted selected from the following group A, but is not limited thereto.

[Group A]

In the definition of group A, 'substituted' means further substituted with another substituent, and 'unsubstituted' means not further substituted with another substituent.

The polymer may include one or a plurality of the above-described first structural units, and the number and arrangement of the above-described first structural units included in the polymer are not limited.

For example, the polymer may further include a second structural unit different from the first structural unit. For example, in the polymer, the first structural units may be continuously connected to each other, and the second structural units may be connected to each other. It may be continuously connected, the first structural unit and the second structural unit may be alternately connected, and the first structural unit and the second structural unit may be randomly connected, but is not limited thereto.

As an example, the second structural unit may be represented by the following formula (4).

[Formula 4]

In Formula 4, X ² is a substituted or unsubstituted C6 to C30 aromatic ring, and Y ² is a divalent organic group.

For example, X ² may be benzene or a polycyclic aromatic hydrocarbon, wherein the polycyclic aromatic hydrocarbon may be a non-condensed aromatic ring, a condensed aromatic ring, or a combination thereof, but preferably a condensed aromatic ring. Accordingly, it is possible to impart higher etch resistance to the etching gas of the layer made of the polymer.

For example, X ² may be any one of substituted or unsubstituted selected from Group 3 below.

[Group 3]

.

.

In the definition of Group 3, 'substituted' means further substituted with another substituent, and 'unsubstituted' means not further substituted with another substituent.

The polymer may include the above-described substituted or unsubstituted C6 to C30 aromatic ring at a position corresponding to X ² in Formula 4, thereby increasing the carbon content of the polymer, so that the CFx mixed gas and N ₂ of the polymer-made layer /O ₂ It is possible to provide higher corrosion resistance to the mixed gas.

For example, X ² may include at least one of a hydroxyl group and a substituted or unsubstituted C1 to C30 alkoxy group. When X ² includes at least one hydroxy group or a hydrophilic functional group such as a substituted or unsubstituted C1 to C30 alkoxy group, the polymer may have improved solubility in a solvent and thus excellent gap-fill properties and planarization properties. Specifically, X ² may include at least one hydroxyl group.

For example, X ² is naphthalene, phenanthrene, anthracene, biphenyl, pyrene, benzophenanthrene, tetracene, hydroxy naphthalene, hydroxy phenanthrene, hydroxy anthracene, hydroxy biphenyl, hydroxy pyrene, hydroxy hydroxybenzophenanthrene, hydroxytetracene, dihydroxynaphthalene, dihydroxyphenanthrene, dihydroxyanthracene, dihydroxybiphenyl, dihydroxypyrene, dihydroxybenzophenanthrene, dihydroxytetracene or a combination thereof.

For example, Y ² may include a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof. Accordingly, the polymer can not only have excellent etch resistance, but also can further increase solubility in solvents, so that when a film is formed from the composition containing the polymer, when there is a step in the lower substrate (or film), or When forming a pattern, better gap-fill and planarization properties can be provided.

For example, Y ² may include a substituted or unsubstituted C1 to C20 alkylene group, for example, a substituted or unsubstituted C1 to C15 alkylene group, for example, a substituted or unsubstituted C1 to C10 alkyl Rene group, for example, a substituted or unsubstituted C1 to C7 alkylene group, for example, a substituted or unsubstituted C1 to C5 alkylene group, for example, a substituted or unsubstituted C1 to C4 alkylene group. have. Specifically, Y ² may include a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, or a combination thereof.

For example, Y ² may include the aforementioned substituted or unsubstituted C1 to C20 alkylene group and a substituted or unsubstituted C6 to C30 arylene group, for example, the substituted or unsubstituted C6 to C30 arylene group. The group may be a single ring and/or a polycyclic ring, and the polycyclic ring may be a condensed ring and/or a non-fused ring.

For example, Y ² may further include a substituted or unsubstituted C1 to C20 alkylene group and a substituted or unsubstituted arylene group selected from the group 4 below.

[Group 4]

In the above group 4, W and p are the same as described above, and * is a connection point with another moiety in the polymer of formula (4).

In Group 4, each arylene group may be unsubstituted or substituted with one or more substituents. Here, the substituent is, for example, deuterium, halogen, hydroxy group, amino group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 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, substituted or unsubstituted C1 to C30 arylalkyl group, It may be 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, but is not limited thereto.

As an example, Y ² may be represented by the following Chemical Formula 5.

[Formula 5]

In Formula 5,

Ar ² is a substituted or unsubstituted C6 to C30 arylene group,

R ⁵ to R ⁸ are each independently hydrogen, deuterium, a halogen group, a nitro group, an amino group, a hydroxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,

R ⁵ and R ⁶ are each independently present or linked to each other to form a ring,

R ⁷ and R ⁸ are each independently present or linked to each other to form a ring,

p ² is 0 or 1, q ² is an integer from 0 to 3,

* is the point of connection with other moieties in the polymer of formula (4).

For example, Ar ² may be any one of substituted or unsubstituted selected from Group 4.

For example, at least two of R ⁵ to R ⁸ may be hydrogen, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; For example, at least one of R ⁵ and R ⁶ is hydrogen, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, and at least one of R ⁷ and R ⁸ is hydrogen, a substituted or unsubstituted C6 to C30 aryl group. an aryl group or a combination thereof; For example, R ⁵ to R ⁸ may each independently be hydrogen, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.

For example, at least two of R ⁵ to R ⁸ may be hydrogen; For example, at least one of R ⁵ and R ⁶ may be hydrogen, and at least one of R ⁷ and R ⁸ may be hydrogen. For example, R ⁵ to R ⁸ may all be hydrogen.

For example, two of R ⁵ to R ⁸ may be hydrogen, and the other two of R ⁵ to R ⁸ may be a substituted or unsubstituted C6 to C30 aryl group; For example, one of R ⁵ and R ⁶ is hydrogen, the other of R ⁵ and R ⁶ is a substituted or unsubstituted C6 to C30 aryl group, one of R ⁷ and R ⁸ is hydrogen, R ⁷ and The other one of R ⁸ may be a substituted or unsubstituted C6 to C30 aryl group. Here, the substituted or unsubstituted C6 to C30 aryl group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted It may be a phenanthrenyl group, a substituted or unsubstituted pyrenyl group, or a combination thereof, but is not limited thereto.

For example, at least two of R ⁵ to R ⁸ may be a substituted or unsubstituted C6 to C30 aryl group; For example, at least one of R ⁵ and R ⁶ may be a substituted or unsubstituted C6 to C30 aryl group, and at least one of R ⁷ and R ⁸ may be a substituted or unsubstituted C6 to C30 aryl group. For example, all of R ⁵ to R ⁸ may be a substituted or unsubstituted C6 to C30 aryl group. Here, the substituted or unsubstituted C6 to C30 aryl group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted It may be a phenanthrenyl group, a substituted or unsubstituted pyrenyl group, or a combination thereof.

For example, R ⁵ to R ⁸ may be the same as or different from each other, for example, R ⁵ and R ⁶ may be the same as or different from each other, and R ⁷ and R ⁸ may be the same as or different from each other.

For example, R ⁵ and R ⁶ may each independently exist or combine with each other to form a ring, and R ⁷ and R ⁸ may each independently exist or combine with each other to form a ring.

For example, q ² may be an integer of 0 to 2, and q ² may be 0 or 1.

When q ² is an integer of 2 or more, a plurality of R ⁷ may be the same as or different from each other, and a plurality of R ⁸ may be the same as or different from each other.

For example, both q ² and p ² may be 0, and both q ² and p ² may be 1.

For example, Chemical Formula 5 may be represented by Chemical Formula 5-1 or 5-2 below.

[Formula 5-1]

[Formula 5-2]

In Formulas 5-1 and 5-2, Ar ² , R ⁵ to R ⁸ and * are the same as described above.

For example, in Formula 4, Y ² may be any one selected from the following group B, but is not limited thereto.

[Group B]

In the definition of group B, 'substituted' means further substituted with another substituent, and 'unsubstituted' means not further substituted with another substituent.

For example, when the polymer includes the above-described first structural unit and the above-described second structural unit, Y ¹ and Y ² may be the same as or different from each other. Specifically, Ar ¹ and Ar ² are the same as or different from each other, R ¹ and R ⁵ are the same as or different from each other, R ² and R ⁶ are the same as or different from each other, R ³ and R ⁷ are the same or different from each other, R ⁴ and R ⁸ may be the same as or different from each other, p ¹ and p ² may be the same as or different from each other, and q ¹ and q ² may be the same as or different from each other.

For example, Y ¹ and Y ² may be the same as each other, and specifically, Ar ¹ and Ar ² are the same as each other, R ¹ and R ⁵ are the same as each other, R ² and R ⁶ are the same as each other, and R ³ and R ⁷ are the same as each other. equal to each other, R ⁴ and R ⁸ may be equal to each other, p ¹ and p ² may be equal to each other, and q ¹ and q ² may be equal to each other.

For example, the polymer may include one or a plurality of the above-described second structural units, and the number and arrangement of the above-described second structural units included in the polymer are not limited.

The molar ratio of the first structural unit to the second structural unit may be, for example, about 0.5:1 to 1.5:1, about 0.7:1 to 1.3:1, or about 0.8:1 to 1.2:1.

The polymer may further include one or two or more structural units not represented by Chemical Formula 2 and/or Chemical Formula 4.

The polymer may have a weight average molecular weight of about 500 to 200,000. More specifically, the polymer may have a weight average molecular weight of about 700 to 100,000, about 800 to 50,000, or about 900 to 10,000. By having a weight average molecular weight in the above range, it can be optimized by controlling the carbon content of the polymer and solubility in a solvent.

On the other hand, the solvent included in the hard mask composition is not particularly limited as long as it has sufficient solubility or dispersibility for the polymer, for example, propylene glycol, propylene glycol diacetate, methoxy propanediol, diethylene glycol, diethylene glycol butyl Ether, tri(ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N,N-dimethylformamide, N,N- It may include at least one selected from dimethylacetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone, and ethyl 3-ethoxypropionate, but is not limited thereto.

The polymer may be included in an amount of, for example, about 0.1 to 60% by weight, such as about 0.5 to 50% by weight, about 1 to 35% by weight, or about 3 to 30% by weight based on the total content of the hardmask composition. By including the polymer in the above range, it is possible to control the thickness, surface roughness, and degree of planarization of the hard mask.

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 alkylbenzenesulfonate, an alkylpyridinium salt, polyethylene glycol, or a quaternary ammonium salt, but is not limited thereto.

The crosslinking agent may be, for example, a melamine-based, substituted urea-based, or polymer-based agent. Preferably, a crosslinking agent having at least two crosslinking substituents is, for example, methoxymethylated glycouryl, butoxymethylated glycouryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxy A compound 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 the crosslinking agent having high heat resistance, a compound containing a crosslinking substituent having an aromatic ring (eg, a benzene ring, a naphthalene ring) in the molecule can be used.

The thermal acid generator is, for example, an acid compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid and/or 2,4 ,4,6-tetrabromocyclohexadienone, benzointosylate, 2-nitrobenzyltosylate, and other organic sulfonic acid 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 40 parts by weight, about 0.01 to 30 parts by weight, or about 0.1 to 20 parts by weight based on 100 parts by weight of the hardmask composition. By including in the above range, solubility can be improved without changing the optical properties of the hardmask composition.

According to another embodiment, there is provided an organic film prepared using the above-described hard mask composition. The organic film may be in a form cured through a heat treatment process after coating the above-described hard mask composition on a substrate, for example, 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. have.

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

A pattern forming method according to an exemplary 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 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 may be formed, for example, by a chemical vapor deposition method.

The hard mask composition is the same 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 thickness of the hard mask composition is not particularly limited, but may be applied, for example, to a thickness of about 50 Å to 200,000 Å.

The heat treatment of the hard mask composition may be performed, for example, at about 100 to 700° C. for about 10 seconds to 1 hour.

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

For example, before the step of 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 exposing of 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.

The etching of the exposed portion of the material layer may be performed by dry etching using an etching gas, the etching gas being, for example, N ₂ /O ₂ , CHF ₃ , CF ₄ , Cl ₂ , BCl ₃ and a mixed gas thereof may 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, an insulating pattern, and may be applied, for example, as various patterns in a semiconductor integrated circuit device.

The above-described embodiment 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.

synthesis of intermediates

Synthesis Example 1

Benzene-1,2-diol (benzene-1,2-diol, 1.21 g, 11.0 mmol), 2,3-difluorobenzonitrile (2,3-difluorobenzonitrile, 1.53 g, 11.0 mmol), potassium carbonate (K ₂ CO ₃ , 2.5 g, 1.81 mmol) and dimethylformamide (DMF, 50 ml) were added, stirred at 70° C. for 20 hours, and then cooled to room temperature. Then, ethyl acetate (200ml) was added, and the organic layer was extracted from the mixture using a separatory funnel. The extracted organic layer was washed with brine, then washed with water three or more times, magnesium sulfate (MgSO4, 20g) was added, stirred, and then filtered. Thereafter, the mixture was separated by column chromatography with a mixed solvent of methylene chloride/hexane at a volume ratio of 1:1, and concentrated by a vacuum distillation to obtain a compound represented by the following formula (1a).

[Formula 1a]

Synthesis Example 2

2,3-difluorobenzonitrile (1.53g, 11.0mmol) instead of tetrafluorobenzonitrile (tetrafluorobenzonitrile, 0.91g, 5.2mmol) was used in the same manner as in Synthesis Example 1, except that The compound expressed was obtained

[Formula 1b]

Synthesis Example 3

4,4'-methylenedibenzene-1,2-diol (4,4'-methylenedibenzene-1,2-diol, 1.22g 5.2mmol) instead of benzene-1,2-diol (1.21g, 11.0mmol) A compound represented by the following Chemical Formula 1c was obtained in the same manner as in Synthesis Example 1 except that .

[Formula 1c]

Synthesis Example 4

3,3',4,4'-biphenyltetraol (3,3',4,4'-biphenyltetrol, 1.14g 5.2mmol) was used instead of benzene-1,2-diol (1.21g, 11.0mmol) A compound represented by the following Chemical Formula 1d was obtained in the same manner as in Synthesis Example 1, except that.

[Formula 1d]

Synthesis Example 5

Benzene-1,2-diol (1.21 g, 11.0 mmol) instead of 4,4'-(9H-fluorene-9,9-diyl)bis(benzene-1,2-diol) (4,4' -(9H-fluorene-9,9-diyl)bis(benzene-1,2-diol), 1.99 g, 5.2 mmol) was prepared in the same manner as in Synthesis Example 1 to prepare a compound represented by the following formula 1e got it

[Formula 1e]

Synthesis Example 6

In the same manner as in Synthesis Example 2, except that 2,3-dihydroxynaphthalene (2,3-dihydroxynaphthalene, 1.67 g, 10.4 mmol) was used instead of benzene-1,2-diol (1.21 g, 11.0 mmol). A compound represented by the following Chemical Formula 1f was obtained.

[Formula 1f]

Synthesis of polymers

Synthesis Example 7: Synthesis of Polymer 1

In a 500 ml flask equipped with a stirrer and a cooling tube, the compound represented by Formula 1a obtained in Synthesis Example 1 (2.1 g, 0.01 mol), 1-naphthol (1.4 g, 0.01 mol), 1,4-bis (methoxymethyl) Benzene (3.3 g, 0.02 mol) and para-toluenesulfonic acid (4.2 g, 0.05 mol) were added, propylene glycol monomethyl ether acetate (PGMEA, 100 g) was added and mixed, followed by stirring at 100° C. for 20 hours. Then, the mixture was cooled and sodium bicarbonate aqueous solution (Sodium bicarbonate, 1N) was added until the pH of the mixture was 5 to 6. Thereafter, ethyl acetate (1,000 ml) was added to the mixture, stirred, and the organic layer was extracted using a separatory funnel. Water (500 ml) was added to the extracted organic layer, and the process of washing the remaining acid and sodium salt by shaking was repeated three or more times, and then the organic layer was finally extracted using a separatory funnel. After the extracted organic layer was concentrated with an evaporator, tetrahydrofuran (1 L) was added to obtain a solution. The solution was slowly added dropwise to a beaker containing hexane (5 L) being stirred to obtain a precipitate, and then the precipitate was filtered to obtain Polymer 1.

As a result of analyzing the polymer obtained using gel permeation chromatography (GPC), the weight average molecular weight (Mw) was 1,500, and the polydispersity (PD) was 1.15.

Synthesis Example 8: Synthesis of Polymer 2

In the same manner as in Synthesis Example 7, except that the compound represented by Formula 1b obtained in Synthesis Example 2 (3.2 g, 0.01 mol) was used instead of the compound represented by Formula 1a (2.1 g, 0.01 mol) obtained in Synthesis Example 1 Polymer 2 was obtained.

As a result of analyzing the obtained polymer using gel permeation chromatography, the weight average molecular weight (Mw) was 2,000, and the polydispersity was 1.20.

Synthesis Example 9: Synthesis of Polymer 3

In the same manner as in Synthesis Example 7, except that the compound represented by Formula 1c obtained in Synthesis Example 3 (4.3 g, 0.01 mol) was used instead of the compound represented by Formula 1a obtained in Synthesis Example 1 (2.1 g, 0.01 mol) Polymer 3 was obtained.

As a result of analyzing the obtained polymer using gel permeation chromatography, the weight average molecular weight (Mw) was 1,750, and the polydispersity was 1.22.

Synthesis Example 10: Synthesis of Polymer 4

In the same manner as in Synthesis Example 7, except that the compound represented by Formula 1d obtained in Synthesis Example 4 (2.0 g, 0.01 mol) was used instead of the compound represented by Formula 1a (2.1 g, 0.01 mol) obtained in Synthesis Example 1 Polymer 4 was obtained.

As a result of analyzing the obtained polymer using gel permeation chromatography, the weight average molecular weight (Mw) was 2,120, and the polydispersity was 1.16.

Synthesis Example 11: Synthesis of Polymer 5

In the same manner as in Synthesis Example 7, except that the compound represented by Formula 1e obtained in Synthesis Example 5 (5.8 g, 0.01 mol) was used instead of the compound represented by Formula 1a (2.1 g, 0.01 mol) obtained in Synthesis Example 1 Polymer 5 was obtained.

As a result of analyzing the obtained polymer using gel permeation chromatography, the weight average molecular weight (Mw) was 1,510, and the polydispersity was 1.23.

Synthesis Example 12: Synthesis of Polymer 6

In the same manner as in Synthesis Example 7, except that the compound represented by Formula 1f obtained in Synthesis Example 6 (4.2 g, 0.01 mol) was used instead of the compound represented by Formula 1a (2.1 g, 0.01 mol) obtained in Synthesis Example 1 Polymer 6 was obtained.

As a result of analyzing the obtained polymer using gel permeation chromatography, the weight average molecular weight (Mw) was 1,490, and the polydispersity was 1.15.

Synthesis Example 13: Synthesis of Polymer 7

Dibenzo[b,e][1,4]dioxin (dibenzo[b,e][1,4]dioxin, 1.8g, 0.01 instead of the compound represented by Formula 1a (2.1g, 0.01mol) obtained in Synthesis Example 1 mol) was used, and polymer 7 was obtained in the same manner as in Synthesis Example 7.

As a result of analyzing the obtained polymer using gel permeation chromatography, the weight average molecular weight (Mw) was 2,040, and the polydispersity was 1.16.

Synthesis Example 14: Synthesis of Polymer 8

Dinaphtho [2,3-b: 2 ', 3'-e] [1,4] dioxin (dinaphtho [2,3-b) instead of the compound represented by Formula 1a (2.1 g, 0.01 mol) obtained in Synthesis Example 1 :2',3'-e][1,4]dioxin, 2.8g, 0.01mol) was obtained in the same manner as in Synthesis Example 7 to obtain Polymer 8.

As a result of analyzing the obtained polymer using gel permeation chromatography, the weight average molecular weight (Mw) was 1,980, and the polydispersity was 1.20.

Synthesis Example 15: Synthesis of Polymer 9

2-phenyl-dibenzo [1,4] dioxin (2-phenyl-dibenzo [1,4] dioxin, 2.6 g, 0.01 mol) instead of the compound represented by Formula 1a obtained in Synthesis Example 1 (2.1 g, 0.01 mol) Polymer 9 was obtained in the same manner as in Synthesis Example 7 except that

As a result of analyzing the obtained polymer using gel permeation chromatography, the weight average molecular weight (Mw) was 1,710, and the polydispersity was 1.16.

Synthesis Example 16: Synthesis of Polymer 10

Using the compound represented by Formula 1a obtained in Synthesis Example 1 (4.2 g, 0.02 mol) instead of the compound represented by Formula 1a (2.1 g, 0.01 mol) obtained in Synthesis Example 1, 1-naphthol (1.4 g, 0.01 mol) ) was not used, and polymer 10 was obtained in the same manner as in Synthesis Example 7.

As a result of analyzing the obtained polymer using gel permeation chromatography, the weight average molecular weight (Mw) was 1,350, and the polydispersity was 1.22.

Synthesis Example 17: Synthesis of Polymer 11

Polymer 11 was obtained in the same manner as in Synthesis Example 16, except that pyrenecarboxaldehyde (4.6 g, 0.02 mol) was used instead of 1,4-bis(methoxymethyl)benzene (3.3 g, 0.02 mol).

As a result of analyzing the obtained polymer using gel permeation chromatography, the weight average molecular weight (Mw) was 1,780, and the polydispersity was 1.12.

Synthesis Example 18: Synthesis of Polymer 12

Polymer 12 was obtained in the same manner as in Synthesis Example 16, except that paraformaldehyde (0.6 g, 0.02 mol) was used instead of 1,4-bis(methoxymethyl)benzene (3.3 g, 0.02 mol).

As a result of analyzing the obtained polymer using gel permeation chromatography, the weight average molecular weight (Mw) was 1,220, and the polydispersity was 1.10.

Synthesis Example 19: Synthesis of Polymer 13

Polymer 13 was obtained in the same manner as in Synthesis Example 7, except that hydroxypyrene (2.2 g, 0.01 mol) was used instead of 1-naphthol (1.4 g, 0.01 mol).

As a result of analyzing the obtained polymer using gel permeation chromatography, the weight average molecular weight (Mw) was 1,510, and the polydispersity was 1.17.

Comparative Synthesis Example 1: Synthesis of Comparative Polymer 1

Comparative Polymer 1 was obtained in the same manner as in Synthesis Example 7, except that biphenyl (1.5 g, 0.01 mol) was used instead of the compound (2.1 g, 0.01 mol) represented by Formula 1a obtained in Synthesis Example 1.

As a result of analyzing the obtained polymer using gel permeation chromatography, the weight average molecular weight (Mw) was 1,810, and the polydispersity was 1.24.

Comparative Synthesis Example 2: Synthesis of Comparative Polymer 2

Comparative Polymer 2 was obtained in the same manner as in Synthesis Example 18, except that pyrene (2.0 g, 0.01 mol) was used instead of the compound (2.1 g, 0.01 mol) represented by Formula 1a obtained in Synthesis Example 1.

As a result of analyzing the obtained polymer using gel permeation chromatography, the weight average molecular weight (Mw) was 1,550, and the polydispersity was 1.28.

Evaluation 1. Solubility evaluation

5 g of each of Polymers 1 to 13 and Comparative Polymers 1 and 2 obtained in Synthesis Examples 7 to 19 and Comparative Synthesis Examples 1 to 2 were added to 45 g of PGMEA and uniformly dissolved to prepare a 15 wt% solution, followed by filtration with a 0.1 μm Teflon filter did. The mass of the obtained solid content was measured by drying the filtered mixed solution in an oven at 160° C. for 2 hours. From this, the amount of reduction in solid content was calculated by the following formula (1).

[Formula 1]

Decrease in solid content (%) = {(Initial mass of the polymer added-mass of solids obtained by drying the mixed solution at 160° C. for 2 hours after filtration)/Initial mass of the polymer added} x 100

The results are shown in Table 1.

Solubility Synthesis Example 7 (Polymer 1) ◎ Synthesis Example 8 (Polymer 2) ◎ Synthesis Example 9 (Polymer 3) ◎ Synthesis Example 10 (Polymer 4) ○ Synthesis Example 11 (Polymer 5) ◎ Synthesis Example 12 (Polymer 6) ○ Synthesis Example 13 (Polymer 7) ◎ Synthesis Example 14 (Polymer 8) ○ Synthesis Example 15 (Polymer 9) ◎ Synthesis Example 16 (Polymer 10) ◎ Synthesis Example 17 (Polymer 11) ○ Synthesis Example 18 (Polymer 12) ◎ Synthesis Example 19 (Polymer 13) ◎ Comparative Synthesis Example 1 (Comparative Polymer 1) X Comparative Synthesis Example 2 (Comparative Polymer 2) X

◎ : solid content Less than 2% reduction

○: Solid content reduction 2% or more to 3% or less

X: more than 3% reduction in solid content

Referring to Table 1, it can be seen that the polymers according to Synthesis Examples 7 to 19 have improved solubility compared to the polymers according to Comparative Synthesis Examples 1 to 2.

Evaluation 2. Evaluation of corrosion resistance

Add 1 g each of Polymers 1 to 13 and Comparative Polymers 1 to 2 obtained in Synthesis Examples 7 to 19 and Comparative Synthesis Examples 1 to 2 and 1 g each to 10 g of PGMEA or PGMEA/cyclohexanone mixed solvent at a volume ratio of 5:5, and uniformly dissolve 10 wt. % of the hard mask compositions of Examples 1-1 to 13-1 and Comparative Examples 1-1 to 2-1 were prepared.

After spin-coating the hard mask compositions according to Examples 1-1 to 13-1 and Comparative Examples 1-1 to 2-1 on a silicon wafer, respectively, heat treatment was performed at about 400° C. for 2 minutes on a hot plate. After forming an organic film with a thickness of about 3,500 Å, the thickness of the organic film was measured with a thin film thickness meter (K-MAC). Then, the organic layer was dry-etched using CFx gas and N ₂ /O ₂ gas for 100 seconds and 60 seconds, respectively, and then the thickness of the organic layer was measured again.

The bulk etch rate (BER) was calculated from the difference in the thickness of the organic layer before and after dry etching and the etching time by Equation 2 below.

[Formula 2]

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

The results are shown in Table 2.

Bulk etch rate (Å/sec) N ₂ /O ₂ CFx Example 1-1 (Polymer 1) 24.2 28.9 Example 2-1 (Polymer 2) 24.1 28.8 Example 3-1 (Polymer 3) 24.2 29.0 Example 4-1 (Polymer 4) 23.1 26.7 Example 5-1 (Polymer 5) 25.1 26.8 Example 6-1 (Polymer 6) 23.0 26.3 Example 7-1 (Polymer 7) 24.2 28.8 Example 8-1 (Polymer 8) 24.2 28.5 Example 9-1 (Polymer 9) 22.8 26.8 Example 10-1 (Polymer 10) 23.3 28.3 Example 11-1 (Polymer 11) 22.6 27.0 Example 12-1 (Polymer 12) 24.8 29.0 Example 13-1 (Polymer 13) 24.3 27.6 Comparative Example 1-1 (Comparative Polymer 1) 26.0 29.8 Comparative Example 2-1 (Comparative Polymer 2) 25.2 29.3

Referring to Table 2, the organic film prepared with the hard mask composition according to Examples 1-1 to 13-1 has sufficient corrosion resistance to the etching gas, so that the hard mask composition according to Comparative Examples 1-1 to 2-1 is used. It can be seen that the etching resistance to the etching gas is improved compared to the prepared organic layer.

Evaluation 3. Membrane Density

Synthesis Examples 7 to 19 in 10 g of PGMEA or a mixed solvent of PGMEA/cyclohexanone in a volume ratio of 5:5 and 1 g each of Polymers 1 to 13 and Comparative Polymers 1 to 2 obtained in Comparative Synthesis Examples 1 and 2, respectively, and uniformly dissolved in 4 wt% of Examples 1-2 to 13-2 and Comparative Examples 1-2 to 2-2 A hard mask composition was prepared.

After spin-coating the hard mask compositions according to Examples 1-2 to 13-2 and Comparative Examples 1-2 to 2-2 on a silicon wafer, respectively, heat treatment at about 400° C. for about 2 minutes on a hot plate Thus, an organic film with a thickness of about 800 Å was formed.

The film density of the formed organic film was measured with an X-ray reflectometer.

The results are shown in Table 3.

Film density (g/cm ³ ) Example 1-2 (Polymer 1) 1.43 Example 2-2 (Polymer 2) 1.42 Example 3-2 (Polymer 3) 1.43 Example 4-2 (Polymer 4) 1.43 Example 5-2 (Polymer 5) 1.45 Example 6-2 (Polymer 6) 1.40 Example 7-2 (Polymer 7) 1.47 Example 8-2 (Polymer 8) 1.42 Example 9-2 (Polymer 9) 1.55 Example 10-2 (Polymer 10) 1.42 Example 11-2 (Polymer 11) 1.43 Example 12-2 (Polymer 12) 1.50 Example 13-2 (Polymer 13) 1.43 Comparative Example 1-2 (Comparative Polymer 1) 1.32 Comparative Example 2-2 (Comparative Polymer 2) 1.39

Referring to Table 3, the organic film formed from the hard mask composition according to Examples 1-2 to 13-2 showed improved film density compared to the organic film formed from the hard mask composition according to Comparative Examples 1-2 to 2-2. can confirm.

Although 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 as defined in the following claims are also presented. It is within the scope of the invention.

Claims (18)

A hard mask composition comprising a polymer comprising a moiety represented by the following Chemical Formula 1, and a solvent:
[Formula 1]

In Formula 1,
A ¹ , A ² , B ¹ , B ² , C ¹ and C ² are each independently a substituted or unsubstituted C6 to C30 aromatic ring,
L is a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof,
n ¹ and n ² are each independently an integer of 0 to 5,
m is an integer from 0 to 100,
* is the point of connection with other moieties in the polymer. In claim 1,
Wherein A ¹ , A ² , B ¹ , B ² , C ¹ and C ² are each independently substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted biphenyl, substituted or unsubstituted anthracene , substituted or unsubstituted pyrene, substituted or unsubstituted fluoranthene, substituted or unsubstituted acenaphthalene, substituted or unsubstituted acenaphthene, substituted or unsubstituted benzophenanthrene, substituted or unsubstituted chrysene, substituted or unsubstituted perylene, substituted or unsubstituted benzopyrene, substituted or unsubstituted tetracene, substituted or unsubstituted benzofluoranthene, substituted or unsubstituted dibenzofluoranthene, substituted or unsubstituted benzoperylene, substituted or unsubstituted coronene, substituted or unsubstituted naphthoanthracene, substituted or unsubstituted triphenylene, substituted or pentacene, or a combination thereof. In claim 1,
A ¹ , A ² , B ¹ , B ² , C ¹ and C ² are each independently unsubstituted; A cyano group, a hydroxyl group, a substituted or unsubstituted C1 to C30 alkoxy group, an amino group, a halogen group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof A hardmask composition comprising a C30 aromatic ring. In claim 1,
A ¹ and C ² are the same as each other,
A ² and C ¹ are the same as each other,
B ¹ and B ² are the same hard mask composition. In claim 1,
L is a single bond, a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted A hard mask composition comprising a naphthylene group, a substituted or unsubstituted anthracenylene group, a substituted or unsubstituted phenanthrenylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted fluorenylene group, or a combination thereof. In claim 1,
The moiety represented by Formula 1 is a hard mask composition represented by any one of Formulas 1-1 to 1-4:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,
A ¹ , A ² , B ¹ , B ² , C ¹ and C ² are each independently a substituted or unsubstituted C6 to C30 aromatic ring,
L is a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof,
* is the point of connection with other moieties in the polymer. In claim 1,
The polymer is a hard mask composition comprising a first structural unit represented by the following Chemical Formula 2:
[Formula 2]

In Formula 2,
X ¹ is a moiety represented by Formula 1,
Y ¹ is a divalent organic group. In claim 7,
Y ¹ is a hard mask composition represented by the following Chemical Formula 3:
[Formula 3]

In Formula 3,
Ar ¹ is a substituted or unsubstituted C6 to C30 arylene group,
R ¹ to R ⁴ are each independently hydrogen, deuterium, a halogen group, a nitro group, an amino group, a hydroxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,
R ¹ and R ² are each independently present or linked to each other to form a ring,
R ³ and R ⁴ are each independently present or linked to each other to form a ring,
p ¹ is 0 or 1,
q ¹ is an integer from 0 to 3,
* is the point of connection with other moieties in the polymer of formula (2). In claim 8,
Ar ¹ is a substituted or unsubstituted hard mask composition selected from the following group 2:
[Group 2]

In group 2,
W is a single bond, oxygen (-O-), sulfur (-S-), -SO ₂ -, substituted or unsubstituted ethenylene, carbonyl (-C(=O)-), CR ^a R ^b , NR ^c or a combination thereof,
R ^a to R ^c are each independently hydrogen, halogen, a carboxyl group, a substituted or unsubstituted C2 to C30 oxoalkyl group, a substituted or unsubstituted C1 to C30 alkoxycarbonyl group, a substituted or unsubstituted C1 to C30 alkoxy group, A substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C30 alkenyl group, a substituted or unsubstituted C1 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to a C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heterocyclic group, or a combination thereof;
p is an integer from 1 to 30,
* is the point of connection with other moieties in the polymer of formula (3). In claim 8,
Chemical formula 3 is a hard mask composition represented by the following Chemical Formula 3-1 or 3-2:
[Formula 3-1]

[Formula 3-2]

In Formulas 3-1 and 3-2,
Ar ¹ is a substituted or unsubstituted C6 to C30 arylene group,
R ¹ to R ⁴ are each independently hydrogen, deuterium, a halogen group, a nitro group, an amino group, a hydroxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,
R ¹ and R ² are each independently present or linked to each other to form a ring,
R ³ and R ⁴ are each independently present or linked to each other to form a ring,
* is the point of connection with other moieties in the polymer of formula (2). In claim 7,
The polymer is a hard mask composition further comprising a second structural unit different from the first structural unit. In claim 11,
The second structural unit is a hard mask composition represented by the following Chemical Formula 4:
[Formula 4]

In Formula 4,
X ² is a substituted or unsubstituted C6 to C30 aromatic ring,
Y ² is a divalent organic group. In claim 12,
X ² is a substituted or unsubstituted hard mask composition selected from the following group 3:
[Group 3]

. In claim 12,
X ² is a hard mask composition comprising at least one hydroxyl group. In claim 12,
Y ² is a hard mask composition represented by the following Chemical Formula 5.
[Formula 5]

In Formula 5,
Ar ² is a substituted or unsubstituted C6 to C30 arylene group,
R ⁵ to R ⁸ are each independently hydrogen, deuterium, a halogen group, a nitro group, an amino group, a hydroxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,
R ⁵ and R ⁶ are each independently present or linked to each other to form a ring,
R ⁷ and R ⁸ are each independently present or linked to each other to form a ring,
p ² is 0 or 1,
q ² is an integer from 0 to 3,
* is the point of connection with other moieties in the polymer of formula (4). In claim 15,
Ar ² is a substituted or unsubstituted hard mask composition selected from the following group 4:
[Group 4]

In group 4,
W is a single bond, oxygen (-O-), sulfur (-S-), -SO ₂ -, substituted or unsubstituted ethenylene, carbonyl (-C(=O)-), CR ^a R ^b , NR ^c or a combination thereof,
R ^a to R ^c are each independently hydrogen, halogen, a carboxyl group, a substituted or unsubstituted C2 to C30 oxoalkyl group, a substituted or unsubstituted C1 to C30 alkoxycarbonyl group, a substituted or unsubstituted C1 to C30 alkoxy group, A substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C30 alkenyl group, a substituted or unsubstituted C1 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to a C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heterocyclic group, or a combination thereof;
p is an integer from 1 to 30,
* is the point of connection with other moieties in the polymer of formula (5). In claim 15,
Chemical formula 5 is a hard mask composition represented by the following Chemical Formula 5-1 or 5-2:
[Formula 5-1]

[Formula 5-2]

In Formulas 5-1 and 5-2,
Ar ² is a substituted or unsubstituted C6 to C30 arylene group,
R ⁵ to R ⁸ are each independently hydrogen, deuterium, a halogen group, a nitro group, an amino group, a hydroxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,
R ⁵ and R ⁶ are each independently present or linked to each other to form a ring,
R ⁷ and R ⁸ are each independently present or linked to each other to form a ring,
* is the point of connection with other moieties in the polymer of formula (4). 18. A method comprising: applying the hardmask composition according to any one of claims 1 to 17 on the material layer and heat-treating to form a hardmask layer;
forming a photoresist layer over the hardmask layer;
exposing and developing the photoresist layer to form a photoresist pattern;
selectively 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;
A pattern forming method comprising a.