KR20220017241A - Hardmask composition and method of forming patterns - Google Patents

Abstract

The present invention relates to a hard mask composition including a first structural unit represented by chemical formula 1 and a second structural unit represented by chemical formula 2, and a patterning method. In chemical formulae 1 and 2, each definition of A, B, L^1 and L^2 is the same as defined in the specification. The hard mask composition according to the present invention can ensure the etching resistance and film density of a hard mask layer at the same time.

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 is developing 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 hard mask composition.

According to an embodiment, a polymer comprising a first structural unit represented by the following Chemical Formula 1 and a second structural unit represented by the following Chemical Formula 2; And it provides a hard mask composition comprising a solvent.

[Formula 1] [Formula 2]

In Formula 1 and Formula 2,

A is a pyrene moiety substituted with at least one hydroxy group,

B is a moiety represented by the following formula (3),

L ¹ and L ² are each independently a divalent organic group represented by Formula 4 below.

[Formula 3]

In Formula 3,

Ar ¹ and Ar ² are each independently a substituted or unsubstituted C6 to C30 aromatic ring.

[Formula 4]

In Formula 4,

X 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,

n is 0 or 1, m is an integer from 0 to 3,

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

A may be any one selected from the following Chemical Formulas 2-1 to 2-3.

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

[Formula 2-3]

In Formulas 2-1 to 2-3,

R ⁵ is a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, a halogen group, a cyano group, an amino group, a substituted or unsubstituted C1 to C30 alkylamino group, a substituted or unsubstituted a 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, or a combination thereof;

a is an integer from 0 to 3.

Ar ¹ and Ar ² are each independently substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted pyrene, substituted or unsubstituted tetracene, substituted or unsubstituted benzophenanthrene, substituted or unsubstituted benzoanthracene, substituted or unsubstituted chrysene, substituted or unsubstituted triphenylene, or a combination thereof.

At least one of Ar ¹ and Ar ² is at least one hydroxyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, a halogen group, a cyano group, an amino group, a substituted or unsubstituted It may be substituted with a C1 to C30 alkylamino group or a combination thereof.

The moiety represented by Formula 3 may be represented by any one of Formulas 3-1 to 3-3 below.

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

[Formula 3-3]

In Formulas 3-1 to 3-3,

R ⁶ and R ⁷ are each independently a hydroxyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, a halogen group, a cyano group, an amino group, a substituted or unsubstituted C1 to C30 group an alkylamino group or a combination thereof,

b and c are each independently an integer of 0 to 5, but the sum of b and c is an integer of 1 to 10.

R ⁶ and R ⁷ are each independently a hydroxyl group, a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted propoxy group, a substituted or unsubstituted butoxy group, a substituted or unsubstituted pentoxy group period or a combination thereof.

X may be any one of substituted or unsubstituted selected from the following group 1.

[Group 1]

In group 1,

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 (4).

R ¹ to R ⁴ are all hydrogen; R ¹ to R ⁴ may each independently be a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, preferably R ¹ to R ⁴ may all be hydrogen have.

m and n may be the same integer.

Formula 4 may be represented by Formula 4-1 or 4-2 below.

[Formula 4-1]

[Formula 4-2]

In Formulas 4-1 and 4-2,

X 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.

L ¹ and L ² may each independently be any one selected from Group 2 below.

[Group 2]

In group 2 above, * is the point of connection with other moieties in the polymer.

L ¹ and L ² may be the same as each other.

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 etch resistance and the film density of the hard mask layer.

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 defined herein, 'substituted' means that a hydrogen atom in a 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, carbayl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C30 alkyl group, C2 to C30 alkenyl group, C2 to C30 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalkenyl group, C6 to 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.

In the present specification, "heterocycle" is a concept including a heteroaromatic ring, and in addition, N, O instead of carbon (C) in a ring compound such as an aromatic ring, an aliphatic ring, a fused ring thereof, or a combination thereof 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 to Also included are fused rings. Aryl groups include monocyclic, polycyclic or fused polycyclic (ie, rings bearing 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.

As used herein, "arylene group" means that there are two linking groups in the substituted or unsubstituted aryl group as 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 first structural unit comprising an aromatic ring substituted with at least one hydroxyl group; and a second structural unit different from the first structural unit and including a moiety in which a plurality of aromatic rings are connected by a single bond.

The first structural unit may include a condensed aromatic ring substituted with at least one hydroxyl group, for example, pyrene substituted with at least one hydroxyl group. Accordingly, the solubility of the polymer in the solvent can be improved, and the polymer can be prepared as a solution and effectively formed into a polymer layer by a solution process such as spin-on coating. In addition, the formed polymer layer may reduce or prevent thermal damage in a subsequent high-temperature process due to high heat resistance and etch resistance, and may reduce or prevent damage by an etching gas exposed in a subsequent etching process.

As an example, the first structural unit may be represented by the following Chemical Formula 1,

[Formula 1]

In Formula 1,

A is a pyrene moiety substituted with at least one hydroxy group,

L ¹ is a divalent organic group.

For example, A may be a pyrene moiety substituted with one hydroxyl group. The polymer contains a pyrene moiety having one hydroxyl group in the first structural unit, so that the CFx etching gas and/or N ₂ /O ₂ mixed gas is more resistant to the polymer than the polymer including the pyrene moiety having one or more hydroxyl groups. It is possible to form a polymer layer having a higher etch resistance to the etchant.

A may be further substituted or unsubstituted with a substituent other than a hydroxyl group. The type and number of substituents other than the hydroxyl group are not limited.

For example, A may be any one selected from the following Chemical Formulas 2-1 to 2-3.

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

[Formula 2-3]

In Formulas 2-1 to 2-3,

R ⁵ is a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, a halogen group, a cyano group, an amino group, a substituted or unsubstituted C1 to C30 alkylamino group, a substituted or unsubstituted a C1 to C30 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, or a combination thereof;

a is an integer from 0 to 3.

For example, R ⁵ 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 ethenyl group, a substituted or unsubstituted pro It may be a phenyl group, a substituted or unsubstituted butenyl group, a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propargyl group, or a combination thereof.

For example, a may be 0 or 1.

For example, L ¹ may be a divalent organic group represented by Formula 4 below. Accordingly, not only can the polymer have excellent etch resistance, but also the solubility in a solvent can be further increased, 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.

[Formula 4]

In Formula 4,

X 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,

n is 0 or 1, m is an integer from 0 to 3,

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

In X, the substituted or unsubstituted C6 to C30 arylene 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, X may be any one of substituted or unsubstituted selected from the following group 1.

[Group 1]

In group 1,

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 (4).

In Group 1, 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, 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 can be

For example, at least two of R ¹ to R ⁴ may be hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.

Specifically, R ¹ and R ² are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; R ³ and R ⁴ may each independently represent hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof. Here, the substituted or unsubstituted substituted or unsubstituted C1 to C30 alkyl group 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 It may be an unsubstituted pentyl group, a substituted or unsubstituted hexyl group, or a combination thereof, but is not limited thereto. In addition, 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 anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted It may be a pyrenyl group or a combination thereof, but is not limited thereto.

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

For example, at least two of R ¹ to R ⁴ may be a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.

Specifically, R ¹ and R ² are a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; R ³ and R ⁴ may be a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof. Here, the substituted or unsubstituted substituted or unsubstituted C1 to C30 alkyl group 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 It may be an unsubstituted pentyl group, a substituted or unsubstituted hexyl group, or a combination thereof, but is not limited thereto. In addition, 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 anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted It may be a pyrenyl group or a combination thereof, but is not limited thereto.

For example, R ¹ to R ⁴ are all hydrogen; R ¹ to R ⁴ may each independently be a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, but preferably, R ¹ to R ⁴ are all hydrogen can Here, the substituted or unsubstituted substituted or unsubstituted C1 to C30 alkyl group 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 It may be an unsubstituted pentyl group, a substituted or unsubstituted hexyl group, or a combination thereof, but is not limited thereto. In addition, 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 anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted It may be a pyrenyl group or a combination thereof, but is not limited thereto.

Accordingly, the polymer can exhibit high film strength and film density, and when a layer having a pattern with a narrow line width is formed on the layer made of the polymer, the warpage of the pattern can be reduced, and a long via or hole can be formed. When a layer having a pattern including holes is formed, a bowing phenomenon of the pattern may be reduced.

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 to R ⁴ may be the same as each other.

For example, when m 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, n may be 0 or 1, and m may be an integer of 0 to 2.

For example, m and n may be the same integer.

For example, both m and n may be 0, and both m and n may be 1.

For example, Chemical Formula 4 may be represented by the following Chemical Formula 4-1 or 4-2.

[Formula 4-1]

[Formula 4-2]

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

For example, L ¹ and L ² may each independently be any one of substituted or unsubstituted selected from the following group 2, but is not limited thereto.

[Group 2]

In group 2 above, * is the point of connection with other moieties in the polymer.

In the definition of Group 2, '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 aforementioned first structural units, and the number and arrangement of the aforementioned 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 described above, the second structural unit may include a moiety in which a plurality of aromatic rings are connected by a single bond. Since the second structural unit includes a moiety in which a plurality of aromatic rings are connected by a single bond, the carbon content of the polymer can be increased to form a harder polymer layer, so that not only the etch resistance can be improved, but also the film density can form an excellent polymer layer.

As an example, the second structural unit may be represented by the following formula (2).

[Formula 2]

In Formula 2,

B is a moiety represented by the following formula (3),

L ² is a divalent organic group.

[Formula 3]

In Formula 3,

Ar ¹ and Ar ² are each independently a substituted or unsubstituted C6 to C30 aromatic ring. Here, the aromatic ring is a benzene 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, C(=O) or OC(=O).

For example, Ar ¹ and Ar ² may each independently include 1 to 4 aromatic rings.

For example, Ar ¹ and Ar ² may each independently be a substituted or unsubstituted benzene ring, or a ring in which 2 to 4 substituted or unsubstituted aromatic rings are condensed. Accordingly, it is possible to form a polymer layer having an excellent film density while improving the solubility of the polymer in a solvent.

For example, Ar ¹ and Ar ² are each independently substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted pyrene, substituted or unsubstituted tetracene, substituted or unsubstituted benzophenanthrene, substituted or unsubstituted benzoanthracene, substituted or unsubstituted chrysene, substituted or unsubstituted triphenylene, or a combination thereof.

For example, at least one of Ar ¹ and Ar ² may be substituted with at least one hydrophilic group, for example, the hydrophilic group may be a hydroxyl group, a substituted or unsubstituted C1 to C30 alkoxy group, or a substituted or unsubstituted C6 to C30 aryl group. It may be an oxy group, a halogen group, a cyano group, an amino group, a substituted or unsubstituted C1 to C30 alkylamino group, and combinations thereof.

When at least one of Ar ¹ and Ar ² is substituted with at least one hydrophilic group, a polymer layer having a better film density may be formed due to a polar bond between the polymers and/or a polar bond within the polymer.

For example, the hydrophilic group may be a hydroxyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, or a combination thereof, for example, a hydroxyl group, a substituted or unsubstituted methoxy group It may be a group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted propoxy group, a substituted or unsubstituted butoxy group, a substituted or unsubstituted pentoxy group, or a combination thereof.

For example, the hydrophilic group may be a hydroxyl group, a substituted or unsubstituted methoxy group, and specifically, a methoxy group substituted with a hydroxyl group, an unsubstituted methoxy group, a substituted or unsubstituted aryl group, or a combination thereof. Here, the substituted or unsubstituted aryl group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted pyrethane group A nyl group, a substituted or unsubstituted tetracenyl group, a substituted or unsubstituted benzophenanthrenyl group, a substituted or unsubstituted benzoanthracenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted triphenylenyl group, or It may be a combination of these.

For example, the moiety represented by Formula 3 may be represented by any one of Formulas 3-1 to 3-3 below.

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

[Formula 3-3]

In Formulas 3-1 to 3-3,

R ⁶ and R ⁷ are each independently a hydrophilic group, wherein the hydrophilic group is as described above,

b and c are each independently an integer from 0 to 5;

For example, b and c may each independently 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 sum of b and c may be an integer of 1 or more, for example, may be an integer of 1 to 10, for example, may be an integer of 1 to 5, for example, may be an integer of 1 to 3 and may be, for example, 1 or 2.

In one example, b may be 0 and c may be 1; b is 1 and c may be 0; b and c may be 1.

For example, L ² may be a divalent organic group represented by Formula 4, and the divalent organic group represented by Formula 4 is the same as described above. Accordingly, not only can the polymer have excellent etch resistance, but also the solubility in a solvent can be further increased, 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.

In the above-described first structural unit and the above-described second structural unit, L ¹ and L ² may be the same as or different from each other.

Specifically, X of the first structural unit and X of the second structural unit are the same as or different from each other, R ¹ of the first structural unit and R ¹ of the second structural unit are the same as or different from each other, and the first R ² of the structural unit and R ² of the second structural unit are the same as or different from each other, R ³ of the first structural unit and R ³ of the second structural unit are the same as or different from each other, and R of the first structural unit ⁴ and R ⁴ of the second structural unit are the same as or different from each other, m of the first structural unit and m of the second structural unit are the same as or different from each other, and n of the first structural unit and the second structural unit n may be equal to or different from each other.

For example, in the above-described first structural unit and the above-described second structural unit, L ¹ and L ² may be the same as each other, Specifically, X of the first structural unit and X of the second structural unit are the same as each other, R ¹ of the first structural unit and R ¹ of the second structural unit are the same as each other, and R of the first structural unit ² and R ² of the second structural unit are the same as each other, R ³ of the first structural unit and R ³ of the second structural unit are the same as each other, R 4 of the first structural unit and R ⁴ of the second structural unit R ⁴ may be the same as each other, m of the first structural unit may be the same as m of the second structural unit, and n of the first structural unit may be the same as n of the second structural unit.

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

For example, the polymer may include more of the first structural unit than the second structural unit, and for example, a molar ratio of the first structural unit to the second structural unit included in the polymer is about 1:1. to 10:1, about 2:1 to 8:1, or about 3:1 to 6:1, but is not limited thereto.

The polymer may further include one or more structural units not represented by Formula 1 and/or Formula 2 above.

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 800 to 100,000, about 1,000 to 50,000, or about 1,200 to 10,000. By having a weight average molecular weight in the above range, it can be optimized by controlling the carbon content and solubility of the polymer 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, 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 2 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 planarization degree 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, a substituted urea-based, or these polymers. Preferably, crosslinking agents having at least two crosslinking substituents are, 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 a crosslinking agent with 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 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 and/or 2,4 ,4,6-tetrabromocyclohexadienone, benzointosylate, 2-nitrobenzyltosylate, and other organic sulfonic acid alkyl esters may be used, but 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 hard mask 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 for forming a pattern using the above-described hard mask composition will be described.

The method for forming a pattern 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 polymers

Synthesis Example 1

2-hydroxypyrene (7.34g, 33.6mmol), 1,1'-biphenyl-4-ol (1.43g, 8.40mmol), paraformaldehyde (1.27g, 42.3mmol) in a 100ml 2-neck round-bottom flask , p-toluenesulfonic acid (0.041 g), and 1,6-dioxane (40.17 g) were added, followed by stirring under reflux. Thereafter, the polymerization reaction was performed by stirring at 70° C. for 1 to 20 hours, and the reaction was completed when the weight average molecular weight was 2,000 to 3,500. After completion of the polymerization reaction, it was slowly cooled to room temperature, and the reactant was put into 40 g of distilled water and 400 g of methanol, stirred vigorously, and then left still. The supernatant was removed and the precipitate was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA), 320 g of methanol was added thereto, stirred vigorously, and allowed to stand (first step). The supernatant was removed again and the precipitate was dissolved in 80 g of PGMEA (second step). Performing the second process once after the first process is referred to as a one-time purification process, and the purification process was performed three times in total. After three purification steps, the polymer was dissolved in 40 g of cyclohexanone, concentrated under reduced pressure to remove residual methanol and distilled water, and polymer 1 having a structural unit represented by the following Chemical Formula 1a and a structural unit represented by the following Chemical Formula 1b was obtained. . (MW: 2,600 g/mol)

[Formula 1a] [Formula 1b]

Synthesis Example 2

Synthesis Example 1 except that 1,1'-biphenyl-4,4'-diol (1.56 g, 8.40 mmol) was used instead of 1,1'-biphenyl-4-ol (1.43 g, 8.40 mmol) In the same manner as described above, a polymer 2 having a structural unit represented by the following Chemical Formula 1a and a structural unit represented by the following Chemical Formula 1c was obtained. (MW: 2,600 g/mol)

[Formula 1a] [Formula 1c]

Synthesis Example 3

In the same manner as in Synthesis Example 1, except that 1,1'-biphenyl-2-ol (1.43 g, 8.40 mmol) was used instead of 1,1'-biphenyl-4-ol (1.43 g, 8.40 mmol) , to obtain a polymer 3 having a structural unit represented by the following formula (1a) and a structural unit represented by the following formula (1d). (MW: 2,600 g/mol)

[Formula 1a] [Formula 1d]

Synthesis Example 4

Synthesis Example 1 except that 1,1'-biphenyl-2,2'-diol (1.56 g, 8.40 mmol) was used instead of 1,1'-biphenyl-4-ol (1.43 g, 8.40 mmol) In the same manner as described above, a polymer 4 having a structural unit represented by the following Chemical Formula 1a and a structural unit represented by the following Chemical Formula 1e was obtained. (MW: 2,600 g/mol)

[Formula 1a] [Formula 1e]

Synthesis Example 5

The same method as in Synthesis Example 1 except that 4-methoxy-1,1'-biphenyl (1.55 g, 8.40 mmol) was used instead of 1,1'-biphenyl-4-ol (1.43 g, 8.40 mmol) Thus, a polymer 5 having a structural unit represented by the following Chemical Formula 1a and a structural unit represented by the following Chemical Formula 1f was obtained. (MW: 2,300 g/mol)

[Formula 1a] [Formula 1f]

Synthesis Example 6

Synthetic except that 3'-methoxy-1,1'-biphenyl-3-ol (1.69 g, 8.40 mmol) was used instead of 1,1'-biphenyl-4-ol (1.43 g, 8.40 mmol) In the same manner as in Example 1, a polymer 6 having a structural unit represented by the following Chemical Formula 1a and a structural unit represented by the following Chemical Formula 1g was obtained. (MW: 2,500 g/mol)

[Formula 1a] [Formula 1g]

Synthesis Example 7

The one using 2-(naphthalen-1-yl)phenol (2-(naphthalen-1-yl)phenol, 1.85g, 8.40mmol) instead of 1,1'-biphenyl-4-ol (1.43g, 8.40mmol) In the same manner as in Synthesis Example 1 except for, a polymer 7 having a structural unit represented by the following Chemical Formula 1a and a structural unit represented by the following Chemical Formula 1h was obtained. (MW: 2,500 g/mol)

[Formula 1a] [Formula 1h]

Synthesis Example 8

1,1'-biphenyl-2-ol (1.43 g, 8.40 mmol) was used instead of 1,1'-biphenyl-4-ol (1.43 g, 8.40 mmol), and paraformaldehyde (1.27 g, 42.3 mmol) was used. ) in the same manner as in Synthesis Example 1 except that 1,4-bis(methoxymethyl)benzene (1,4-bis(methoxymethyl)benzene, 7.03 g, 42.3 mmol) was used instead of A polymer 8 having a structural unit and a structural unit represented by the following formula 1j was obtained. (MW: 2,800 g/mol)

[Formula 1i] [Formula 1j]

Synthesis Example 9

[1,1'-binaphthalene]-2,2'-diol ([1,1'-binaphthalene]-2,2' instead of 1,1'-biphenyl-4-ol (1.43 g, 8.40 mmol) -diol, 2.41 g, 8.40 mmol) was used, and in the same manner as in Synthesis Example 1, a polymer 9 having a structural unit represented by the following Chemical Formula 1a and a structural unit represented by the following Chemical Formula 1k was obtained. (MW: 2,900 g/mol)

[Formula 1a] [Formula 1k]

Synthesis Example 10

4'-(benzyloxy)-[1,1'-biphenyl]-4-ol (4'-(benzyloxy)-[1] instead of 1,1'-biphenyl-4-ol (1.43 g, 8.40 mmol) , 1'-biphenyl]-4-ol, 2.32 g, 8.40 mmol) was used in the same manner as in Synthesis Example 1, having a structural unit represented by the following Chemical Formula 1a and a structural unit represented by the following Chemical Formula 1l Polymer 10 was obtained. (MW: 2,500 g/mol)

[Formula 1a] [Formula 1l]

Comparative Synthesis Example 1

2-hydroxypyrene (9.18g, 42.1mmol), 6-hydroxy-2-naphthaldehyde (6-hydroxy-2-naphthaldehyde, 7.24g, 42.0mmol), p-toluene in a 100ml 2-neck round-bottom flask Sulfonic acid (4.0 g, 23.2 mmol) and 1,6-dioxane (38 g) were added, followed by stirring under reflux. Thereafter, the polymerization reaction was performed by stirring at 110° C. for 1 to 20 hours, and the reaction was completed when the weight average molecular weight was 2,000 to 3,500. After completion of the polymerization reaction, it was slowly cooled to room temperature, and the reactant was put into 40 g of distilled water and 400 g of methanol, stirred vigorously, and then left still. After removing the supernatant and dissolving the precipitate in 80 g of cyclohexanone, 320 g of methanol was added thereto, stirred vigorously, and allowed to stand (first step). The supernatant was removed again and the precipitate was dissolved in 80 g of cyclohexanone (second step). Performing the second process once after the first process is referred to as a one-time purification process, and the purification process was performed three times in total. After three purification steps, the polymer was dissolved in 40 g of cyclohexanone, and concentrated under reduced pressure to remove residual methanol and distilled water to obtain Comparative Polymer 1 having a structural unit represented by the following Chemical Formula A. (MW: 2,700 g/mol)

[Formula A]

Comparative Synthesis Example 2

1,1'-biphenyl-4-ol (7.15g, 42.0mmol), pyrene-1-carbaldehyde (9.67g, 42.0mmol), p-toluene in a 100ml 2-neck round-bottom flask Sulfonic acid (4.0 g, 23.2 mmol), and 1,6-dioxane (39 g) were added, followed by stirring under reflux. Thereafter, the polymerization reaction was performed by stirring at 110° C. for 1 to 20 hours, and the reaction was completed when the weight average molecular weight was 2,000 to 3,500. After completion of the polymerization reaction, it was slowly cooled to room temperature, and the reactant was put into 40 g of distilled water and 400 g of methanol, stirred vigorously, and then left still. After removing the supernatant and dissolving the precipitate in 80 g of cyclohexanone, 320 g of methanol was added thereto, stirred vigorously, and allowed to stand (first step). The supernatant was removed again and the precipitate was dissolved in 80 g of cyclohexanone (second step). Performing the second process once after the first process is referred to as a one-time purification process, and the purification process was performed three times in total. After three purification steps, the polymer was dissolved in 40 g of cyclohexanone, and concentrated under reduced pressure to remove residual methanol and distilled water, thereby obtaining Comparative Polymer 2 having a structural unit represented by the following Chemical Formula B. (MW: 2,300 g/mol)

[Formula B]

Comparative Synthesis Example 3

4,4'-(9-fluorenylidene)diphenol (4,4'-(9-fluorenylidene)diphenol, 8.84g, 21.0mmol), 1,1'-biphenyl- 4,4'-diol (3.03 g, 16.3 mmol), paraformaldehyde (1.27 g, 42.3 mmol), p-toluenesulfonic acid (0.16 g), and PGMEA (27 g) were added, and the mixture was stirred under reflux. Thereafter, the polymerization reaction was performed by stirring at 70° C. for 1 to 20 hours, and the reaction was completed when the weight average molecular weight was 2,000 to 3,500. After completion of the polymerization reaction, it was slowly cooled to room temperature, and the reactant was put into 40 g of distilled water and 400 g of methanol, stirred vigorously, and then left still. After removing the supernatant and dissolving the precipitate in 80 g of PGMEA, 320 g of methanol was added, stirred vigorously, and then left still (first step). The supernatant was removed again and the precipitate was dissolved in 80 g of PGMEA (second step). Performing the second process once after the first process is referred to as a one-time purification process, and the purification process was performed three times in total. After three purification steps, the polymer was dissolved in 40 g of PGMEA, concentrated under reduced pressure to remove residual methanol and distilled water, and Comparative Polymer 3 having a structural unit represented by the following Chemical Formula C and a structural unit represented by the following Chemical Formula 1c was obtained. (MW: 2,500 g/mol)

[Formula C] [Formula 1c]

Comparative Synthesis Example 4

2-hydroxypyrene (6.99 g, 32.0 mmol), 6,6'-(9H-fluorene-9,9-diyl)bis(naphthalen-2-ol) (6, 6'-(9H-fluorene-9,9-diyl)bis(naphthalen-2-ol), 14.4g, 32.0mmol), 1,4-bis(methoxymethyl)benzene (8.59g, 51.7mmol), p -Toluenesulfonic acid (0.24 g), and PGMEA (70 g) were added, and the mixture was stirred under reflux. Thereafter, the polymerization reaction was performed by stirring at 70° C. for 1 to 20 hours, and the reaction was completed when the weight average molecular weight was 2,000 to 3,500. After completion of the polymerization reaction, it was slowly cooled to room temperature, and the reactant was put into 40 g of distilled water and 400 g of methanol, stirred vigorously, and then left still. After removing the supernatant and dissolving the precipitate in 80 g of PGMEA, 320 g of methanol was added, stirred vigorously, and then left still (first step). The supernatant was removed again and the precipitate was dissolved in 80 g of PGMEA (second step). Performing the second process once after the first process is referred to as a one-time purification process, and the purification process was performed three times in total. After three purification processes, the polymer was dissolved in 40 g of cyclohexanone, and concentrated under reduced pressure to remove residual methanol and distilled water, and Comparative Polymer 4 having a structural unit represented by the following Chemical Formula 1i and a structural unit represented by the following Chemical Formula D was obtained. got it (MW: 3,000 g/mol)

[Formula 1i]

[Formula D]

Evaluation 1. Evaluation of corrosion resistance

Polymers 1 to 10 and Comparative Polymers 1 to 4 obtained in Synthesis Examples 1 to 10 and Comparative Synthesis Examples 1 to 4 were added to PGMEA or PGMEA/cyclohexanone in a 1:1 volume ratio, respectively, and uniformly dissolved to obtain a solid content of about 15 To 20 wt% of the hard mask compositions of Examples 1-1 to 10-1 and Comparative Examples 1-1 to 4-1 were prepared.

After spin-coating the hard mask compositions according to Examples 1-1 to 10-1 and Comparative Examples 1-1 to 4-1 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 5,000 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 1 below.

[Formula 1]

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

The results are shown in Table 1.

Bulk etch rate(Å/s) CFx N ₂ /O ₂ Example 1-1 (Polymer 1) 27.3 21.9 Example 2-1 (Polymer 2) 26.8 22.2 Example 3-1 (Polymer 3) 27.9 21.4 Example 4-1 (Polymer 4) 28.1 22.2 Example 5-1 (Polymer 5) 26.8 23.0 Example 6-1 (Polymer 6) 27.0 23.3 Example 7-1 (Polymer 7) 27.8 21.4 Example 8-1 (Polymer 8) 27.4 21.6 Example 9-1 (Polymer 9) 27.0 22.5 Example 10-1 (Polymer 10) 27.8 21.4 Comparative Example 1-1 (Comparative Polymer 1) 28.3 25.0 Comparative Example 2-1 (Comparative Polymer 2) 28.7 24.8 Comparative Example 3-1 (Comparative Polymer 3) 29.5 26.3 Comparative Example 4-1 (Comparative Polymer 4) 30.6 27.1

Referring to Table 1, the organic film prepared with the hard mask composition according to Examples 1-1 to 10-1 has sufficient corrosion resistance to etching gas, so that the hard mask composition according to Comparative Examples 1-1 to 4-1 is used. It can be seen that the etching resistance to the etching gas is improved compared to the prepared organic layer.

Evaluation 2. Membrane Density

Synthesis Examples 1 to 10 in a mixed solvent of PGMEA/cyclohexanone in a 1:1 volume ratio And Polymers 1 to 10 and Comparative Polymers 1 to 4 obtained in Comparative Synthesis Examples 1 to 4 were respectively added and uniformly dissolved in Examples 1-2 to 10-2 and Comparative Examples 1-2 to 4- having a solid content of about 5 wt% A hard mask composition of 2 was prepared.

After spin-coating the hard mask compositions according to Examples 1-2 to 10-2 and Comparative Examples 1-2 to 4-2 on a silicon wafer, respectively, heat treatment at about 400° C. for about 2 minutes on a hot plate Thus, an organic film having a thickness of about 700 Å to 900 Å was formed.

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

The results are shown in Table 2.

Film density (g/cm ³ ) Example 1-2 (Polymer 1) 1.47 Example 2-2 (Polymer 2) 1.44 Example 3-2 (Polymer 3) 1.48 Example 4-2 (Polymer 4) 1.45 Example 5-2 (Polymer 5) 1.42 Example 6-2 (Polymer 6) 1.43 Example 7-2 (Polymer 7) 1.45 Example 8-2 (Polymer 8) 1.43 Example 9-2 (Polymer 9) 1.45 Example 10-2 (Polymer 10) 1.45 Comparative Example 1-2 (Comparative Polymer 1) 1.33 Comparative Example 2-2 (Comparative Polymer 2) 1.32 Comparative Example 3-2 (Comparative Polymer 3) 1.29 Comparative Example 4-2 (Comparative Polymer 4) 1.26

Referring to Table 2, the organic film formed from the hard mask composition according to Examples 1-2 to 10-2 showed improved film density compared to the organic film formed from the hard mask composition according to Comparative Examples 1-2 to 4-2. 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 belongs to the scope of the right of the invention.

Claims (13)

a polymer including a first structural unit represented by the following Chemical Formula 1 and a second structural unit represented by the following Chemical Formula 2; and a hardmask composition comprising a solvent:
[Formula 1] [Formula 2]

In Formula 1 and Formula 2,
A is a pyrene moiety substituted with at least one hydroxy group,
B is a moiety represented by the following formula (3),
L ¹ and L ² are each independently a divalent organic group represented by the following Chemical Formula 4:
[Formula 3]

In Formula 3,
Ar ¹ and Ar ² are each independently a substituted or unsubstituted C6 to C30 aromatic ring:
[Formula 4]

In Formula 4,
X 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,
n is 0 or 1, m is an integer from 0 to 3,
* is the point of connection with other moieties in the polymer.
In claim 1,
A is any one selected from the following formulas 2-1 to 2-3 hard mask composition:
[Formula 2-1] [Formula 2-2]

[Formula 2-3]

In Formulas 2-1 to 2-3,
R ⁵ is a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, a halogen group, a cyano group, an amino group, a substituted or unsubstituted C1 to C30 alkylamino group, a substituted or unsubstituted a 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, or a combination thereof;
a is an integer from 0 to 3.
In claim 1,
Ar ¹ and Ar ² are each independently substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted pyrene, substituted or unsubstituted tetracene, substituted or unsubstituted benzophenanthrene, substituted or unsubstituted benzoanthracene, substituted or unsubstituted chrysene, substituted or unsubstituted triphenylene, or a combination thereof.
In claim 1,
At least one of Ar ¹ and Ar ² is at least one hydroxyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, a halogen group, a cyano group, an amino group, a substituted or unsubstituted A hard mask composition substituted with a C1 to C30 alkylamino group, or a combination thereof.
In claim 1,
The moiety represented by Formula 3 is a hard mask composition represented by any one of Formulas 3-1 to 3-3:
[Formula 3-1] [Formula 3-2]

[Formula 3-3]

In Formulas 3-1 to 3-3,
R ⁶ and R ⁷ are each independently a hydroxyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, a halogen group, a cyano group, an amino group, a substituted or unsubstituted C1 to C30 group an alkylamino group or a combination thereof,
b and c are each independently an integer of 0 to 5, but the sum of b and c is an integer of 1 to 10.
In claim 1,
R ⁶ and R ⁷ are each independently a hydroxyl group, a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted propoxy group, a substituted or unsubstituted butoxy group, a substituted or unsubstituted pentoxy group A hard mask composition that is a period or a combination thereof.
In claim 1,
X is a substituted or unsubstituted hard mask composition selected from the following group 1:
[Group 1]

In group 1,
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 (4).
In claim 1,
R ¹ to R ⁴ are all hydrogen,
R ¹ to R ⁴ are each independently a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.
In claim 1,
m and n are integers equal to each other.
In claim 1,
Chemical formula 4 is a hard mask composition represented by the following Chemical Formula 4-1 or 4-2:
[Formula 4-1]

[Formula 4-2]

In Formulas 4-1 and 4-2,
X 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.
In claim 1,
L ¹ and L ² are each independently any one selected from the following group 2: a hard mask composition:
[Group 2]

In group 2 above, * is the point of connection with other moieties in the polymer.
In claim 1,
L ¹ and L ² are the same hard mask composition.
A step of applying the hardmask composition according to any one of claims 1 to 12 on the material layer and heat-treating it 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.