KR102325837B1 - Polymer and hardmask composition and method of forming patterns - Google Patents

Abstract

상기 화학식 1에서, X, Y, R¹ 및 R²의 정의는 명세서에 기재한 바와 같다.A polymer comprising a substituted or unsubstituted moiety and a substituted or unsubstituted C6 to C30 aromatic moiety represented by the following Chemical Formula 1, a hardmask composition comprising the polymer, and a pattern forming method using the hardmask composition is about
[Formula 1]

In Formula 1, the definitions of X, Y, R ¹ and R ² are as described in the specification.

Description

Polymer, hardmask composition and pattern forming method

It relates to a polymer, a hardmask composition comprising the polymer, 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 polymer that can be effectively applied to a hardmask layer.

Another embodiment provides a hardmask composition comprising the polymer.

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

According to one embodiment, a polymer comprising a substituted or unsubstituted moiety and a substituted or unsubstituted C6 to C30 aromatic moiety represented by the following Chemical Formula 1 is provided.

[Formula 1]

In Formula 1,

X and Y are each independently a substituted or unsubstituted five-membered ring containing at least one hetero atom,

R ¹ and R ² are each independently hydrogen, deuterium, halogen, hydroxy 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 an unsubstituted C1 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 to C30 arylalkyl group, substituted or unsubstituted C6 to C30 heteroarylalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 heteroaryl group, combinations thereof or other adjacent moieties is a connection point.

In Formula 1, X and Y may each independently be a substituted or unsubstituted penta-membered ring including at least one nitrogen atom.

The substituted or unsubstituted moiety represented by Formula 1 may be represented by Formula 2 below.

[Formula 2]

In Formula 2,

X ¹ to X ³ and Y ¹ to Y ³ are each independently CR ^a , CR ^b R ^c , N, NR ^d , O, S, Se or Te,

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

At least one of Y ¹ to Y ^{3 is N, NR d} , O, S, Se or Te,

R ¹ , R ² and R ^a to R ^d are each independently hydrogen, deuterium, halogen, hydroxy group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to 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, A substituted or unsubstituted C1 to C30 arylalkyl group, a substituted or unsubstituted C6 to C30 heteroarylalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, a combination thereof, or It is a point of connection with other adjacent moieties.

In Formula 2, X ¹ , X ³ , Y ¹ and Y ³ are each independently N, NR ^d , O, S, Se or Te,

X ² and Y ² are each independently CR ^a or CR ^b R ^c ;

R ^a to R ^d are each independently hydrogen, deuterium, halogen, hydroxy group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C30 alkenyl group, substituted Or an unsubstituted C1 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 to C30 arylalkyl group, substituted or unsubstituted C6 to C30 heteroarylalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 heteroaryl group, combinations thereof or other adjacent moieties It can be a connection point.

X ¹ in the general formula (2) is the same as Y ¹ X ³ and Y ³ are the same or, X ¹ is the same as Y ³ X ³ may be the same as Y ^1.

The substituted or unsubstituted moiety represented by Formula 1 may be any substituted or unsubstituted moiety selected from the following group 1.

[Group 1]

In group 1,

R ¹ , R ² , R ^a and R ^d are each independently hydrogen, deuterium, halogen, hydroxy 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, A substituted or unsubstituted C1 to C30 arylalkyl group, a substituted or unsubstituted C6 to C30 heteroarylalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, a combination thereof, or It is a point of connection with other adjacent moieties.

The substituted or unsubstituted C6 to C30 aromatic moiety may be any substituted or unsubstituted group selected from the following group 2.

[Group 2]

The substituted or unsubstituted C6 to C30 aromatic moiety may be a condensed ring.

The polymer may include a first structural unit represented by Formula 3 below.

[Formula 3]

In Formula 3,

X and Y are each independently a substituted or unsubstituted five-membered ring containing at least one hetero atom,

R ¹ and R ² are each independently hydrogen, deuterium, halogen, hydroxy 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 an unsubstituted C1 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 to C30 arylalkyl group, a substituted or unsubstituted C6 to C30 heteroarylalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof;

A is a substituted or unsubstituted C6 to C30 aromatic ring.

X and Y in Formula 3 may each independently be a substituted or unsubstituted penta-membered ring including at least one nitrogen atom.

The first structural unit represented by Formula 3 may be represented by Formula 4 below.

[Formula 4]

In Formula 4,

X ¹ , X ³ , Y ¹ and Y ³ are each independently CR ^a , CR ^b R ^c , N, NR ^d , O, S, Se or Te;

at least one of X ¹ and X ^{3 is N, NR d} , O, S, Se or Te,

At least one of Y ¹ and Y ^{3 is N, NR d} , O, S, Se or Te,

R ¹ , R ² and R ^a to R ^d are each independently hydrogen, deuterium, halogen, hydroxy group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to 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, A substituted or unsubstituted C1 to C30 arylalkyl group, a substituted or unsubstituted C6 to C30 heteroarylalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof; ,

A is a substituted or unsubstituted C6 to C30 aromatic ring.

In Formula 4, X ¹ , X ³ , Y ¹ and Y ³ are each independently N, NR ^d , O, S, Se or Te,

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

X ¹ in the general formula (4) is the same as Y ¹ X ³ and Y ³ are the same or, X ¹ is the same as Y ³ X ³ may be the same as Y ^1.

The first structural unit represented by Chemical Formula 4 may be any one selected from the following Chemical Formulas 4-1 to 4-11.

[Formula 4-1] [Formula 4-2]

[Formula 4-3] [Formula 4-4]

[Formula 4-5] [Formula 4-6]

[Formula 4-7] [Formula 4-8]

[Formula 4-9] [Formula 4-10]

[Formula 4-11]

In Formulas 4-1 to 4-11,

R ¹ , R ² and R ^d are each independently hydrogen, deuterium, halogen, hydroxy group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C30 alkene Nyl 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 a substituted or unsubstituted C1 to C30 arylalkyl group, a substituted or unsubstituted C6 to C30 heteroarylalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof;

A is a substituted or unsubstituted C6 to C30 aromatic ring.

The polymer may include two or more structural units selected from Formulas 4-1 to 4-11.

A in Formula 3 may be any one of substituted or unsubstituted selected from Group 2 below.

[Group 2]

A in Formula 3 may be a condensed ring.

The polymer may further include a second structural unit represented by Formula 3 and different from the first structural unit.

According to another embodiment, there is provided a hardmask composition comprising the polymer and a solvent.

According to another embodiment, applying the 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 secure excellent gap-fill properties, planarization properties, and etch resistance of the hardmask layer.

1 is a reference diagram exemplarily showing a step difference of a hard mask layer in order to explain a method for evaluating a planarization characteristic.

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 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 C15 cycloalkynyl group, 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 salt thereof, sulfonic acid group or salt thereof, 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, 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 group in which hydrocarbon aromatic moieties are directly or indirectly fused. Also included are fusion rings. Aryl groups include monocyclic, polycyclic or fused polycyclic (ie, rings that share adjacent pairs of carbon atoms) functional groups.

In the present specification, "heterocyclic group" is a concept including a heteroaryl group, 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 and/or a substituted or unsubstituted heterocyclic group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted A substituted phenanthryl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted quaterphenyl group, a substituted or unsubstituted A substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group, a substituted Or an unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazole Diyl, substituted or unsubstituted oxadiazolyl group, substituted or unsubstituted thiadiazolyl group, substituted or unsubstituted pyridinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, substituted Or an unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted qui Nolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted benzoxazinyl group, A substituted or unsubstituted benzthiazinyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted A substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, a pyridoindolyl group, a benzopyridooxazinyl group, a benzopyridothia Jinyl group, 9,9-dimethyl 9,10 dihydroacridinyl group, a combination thereof, or a combination thereof may be in a fused form, but is not limited In one embodiment of the present invention, the heterocyclic group or the heteroaryl group may be a pyridyl group, a carbazolyl group or a pyridoindolyl group.

As used herein, "aromatic moiety" refers to a non-condensed aromatic moiety, a condensed aromatic moiety, a moiety in which aromatic moieties are connected by a single bond, and each ring condensed to two non-parallel sides on a benzene ring is fused a moiety in which each ring condensed on two non-parallel sides on a benzene ring is connected by a single bond or a double bond, or a combination thereof.

Unless otherwise specified herein, "combination" means mixing or copolymerization.

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

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

The polymer according to one embodiment comprises a substituted or unsubstituted fused heterocyclic moiety and a substituted or unsubstituted aromatic moiety.

The substituted or unsubstituted fused heterocyclic moiety may include a bent structure, wherein the bent structure is the same or different from each other on two non-parallel sides on one ring. may mean a fused structure. For example, the substituted or unsubstituted fused heterocyclic moiety including the bent structure may include a structure in which rings are fused to two sides that are not parallel to each other on a benzene ring, for example, as described below in Formula 1 can be expressed

Since the polymer contains a substituted or unsubstituted fused heterocyclic moiety including a bent structure, solubility in a solvent can be increased, and carbon content can be increased to form a hard polymer layer. High corrosion resistance can be imparted.

The substituted or unsubstituted aromatic moiety may be a substituted or unsubstituted C6 to C30 aromatic moiety, wherein the aromatic moiety 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).

As an example, the substituted or unsubstituted fused heterocyclic moiety may be represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1,

X and Y are each independently a substituted or unsubstituted five-membered ring containing at least one hetero atom,

R ¹ and R ² are each independently hydrogen, deuterium, halogen, hydroxy 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 an unsubstituted C1 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 to C30 arylalkyl group, substituted or unsubstituted C6 to C30 heteroarylalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 heteroaryl group, combinations thereof or other adjacent moieties is a connection point.

By including the moiety of the vent structure represented by Formula 1 above, the polymer can secure a degree of freedom equivalent to that of a conventional methylene group, thereby increasing solubility in a solvent and reducing the carbon content It can be increased to form a hard polymer layer, so that high etch resistance can be imparted.

For example, each of X and Y may independently be a substituted or unsubstituted penta-membered ring containing at least two or more heteroatoms.

For example, each of X and Y may independently be a substituted or unsubstituted penta-membered ring including two heteroatoms.

For example, at least one of X and Y may be a substituted or unsubstituted pentacyclic ring containing at least one nitrogen atom, and preferably, X and Y are each independently a substituted or unsubstituted ring containing at least one nitrogen atom. It may be an unsubstituted pentacyclic ring.

For example, each of X and Y may independently be a substituted or unsubstituted penta-membered ring containing one nitrogen atom.

For example, X and Y may each independently be a substituted or unsubstituted penta-membered ring including two nitrogen atoms.

Here, the substituted or unsubstituted five-membered ring may be a heteroaromatic five-membered ring or a hetero non-aromatic five-membered ring.

For example, R ¹ and R ² may each independently exist or two adjacent ones may be connected to each other to form a ring, but preferably each independently exist.

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

For example, ^{at least one of R 1} and R ² may be hydrogen, but preferably R ¹ and R ² may each independently be hydrogen.

For example, the connection point of the substituted or unsubstituted moiety represented by Chemical Formula 1 and another moiety adjacent thereto may be included in X and/or Y.

For example, the substituted or unsubstituted moiety represented by Formula 1 may be represented by Formula 2 below.

[Formula 2]

In Formula 2,

R ¹ and R ² are as described above,

X ¹ to X ³ and Y ¹ to Y ³ are each independently CR ^a , CR ^b R ^c , N, NR ^d , O, S, Se or Te,

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

At least one of Y ¹ to Y ^{3 is N, NR d} , O, S, Se or Te,

R ^a to R ^d are each independently hydrogen, deuterium, halogen, hydroxy group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C30 alkenyl group, substituted Or an unsubstituted C1 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 to C30 arylalkyl group, substituted or unsubstituted C6 to C30 heteroarylalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 heteroaryl group, combinations thereof or other adjacent moieties is a connection point.

In Formula 2, a bond indicated by a solid line and a dotted line at the same time means that the bond may be a single bond or a double bond. For example, ^{the bond between X 1} and X ² , the bond between X ² and X ³ , the bond between Y ¹ and Y ^{2 ,} and the bond between Y ² and Y ³ may each independently be a single bond or a double bond.

For example, ^{the bond between X 1} and X ² may be a single bond and the bond between X ² and X ³ may be a double bond, ^{the bond between X 1} and X ² may be a double bond, and the bond between X ² and X ³ may be may be a single bond, ^{a bond between X 1} and X ² may be a single bond, a bond between X ² and X ³ may be a single bond, ^{a bond between Y 1} and Y ² may be a single bond, and Y ² and Y ³ The bond between may be a double bond, the bond between Y ¹ and Y ² may be a double bond and ^{the bond between Y 2} and Y ³ may be a single bond, or ^{the bond between Y 1} and Y ² may be a single bond and The bond between Y ² and Y ³ may be a single bond.

For example, R ¹ , R ² , and R ^a to R ^d may each independently exist, and two adjacent ones may be fused to each other to form a ring, but preferably, they may each independently exist.

For example, ^{at least one of X 1} and X ³ may be N, NR ^d , O, S, Se or Te, and at least one of ^{Y 1} and Y ^{3 may be N, NR d} , O, S, Se or Te. can

For example, X ¹ , X ³ , Y ¹ and Y ³ may each independently be N, NR ^d , O, S, Se, or Te.

For example, in Formula 2, at least one ^{of X 1} , X ³ , Y ¹ and Y ^{3 may be N or NR d} , and specifically, ^{at least one of X 1} , X ³ , Y ¹ and Y ³ is N or NR ^d and the ^{remainder of X 1} , X ³ , Y ¹ and Y ³ may each independently be O, S, Se or Te.

For example, at least two of ^{X 1} , X ³ , Y ¹ and Y ^{3 may be N or NR d} , and specifically, ^{at least two of X 1} , X ³ , Y ¹ and Y ³ may be N or NR ^d and the ^{rest of X 1} , X ³ , Y ¹ and Y ³ may each independently be O, S, Se, or Te. Preferably, at least one of ^{X 1} and X ^{3 is N or NR d} , ^{at least one of Y 1} and Y ³ is N or NR ^d , and the ^{remainder of X 1} , X ³ , Y ^{1 and Y 3} are each independently may be O, S, Se or Te.

For example, X ^1, at least three of X ^3, Y ¹ and Y ³ may be an N or NR ^d, specifically, X ^1, X ^3, at least three of Y ¹ and Y ³ is N or NR ^d , X ¹ , X ³ , Y ¹ and Y ³ may be O, S, Se or Te.

For example, X ¹ , X ³ , Y ¹ and Y ³ may each independently be N or NR ^d .

For example, X ² and Y ² may each independently be CR ^a or CR ^b R ^c . Here, R ^a may be a point of attachment to another adjacent moiety, and R ^b and/or R ^c may be a point of attachment to another adjacent moiety.

For example, in Formula 2, X ¹ , X ³ , Y ¹ and Y ³ are each independently N, NR ^d , O, S, Se or Te, and X ² and Y ² are each independently CR ^a or CR ^b It may be ^{R c .} Here, R ^a may be a point of attachment to another adjacent moiety, and R ^b and/or R ^c may be a point of attachment to another adjacent moiety.

For example, at least one of ^{X 1} , X ³ , Y ¹ and Y ^{3 is N or NR d} , and the ^{rest of X 1} , X ³ , Y ^{1 and Y 3} are each independently O, S, Se or Te, X ² and Y ² may each independently be CR ^a or CR ^b R ^c .

For example, at least two of ^{X 1} , X ³ , Y ¹ and Y ^{3 are N or NR d} , and the ^{rest of X 1} , X ³ , Y ^{1 and Y 3} are each independently O, S, Se, or Te; , X ² and Y ² may each independently be CR ^a or CR ^b R ^c .

For example, at least one of ^{X 1} and X ^{3 is N or NR d} , ^{at least one of Y 1} and Y ³ is N or NR ^d , and the ^{rest of X 1} , X ³ , Y ^{1 and Y 3} are each independently O, S, Se or Te, and X ² and Y ² may each independently be CR ^a or CR ^b R ^c .

For example, at least three of ^{X 1} , X ³ , Y ¹ and Y ^{3 are N or NR d} , and the ^{remainder of X 1} , X ³ , Y ^{1 and Y 3} is O, S, Se or Te, and X ² and Y ² may be each independently CR ^a or CR ^b R ^c .

For example, X ¹ , X ³ , Y ¹ and Y ³ may each independently be N or NR ^d , and X ² and Y ² may each independently be CR ^a or CR ^b R ^c .

For example, in Formula 2, X ¹ , X ³ , Y ¹ and Y ³ may be the same or different.

For example, in Formula 2, X ¹ may be equal to Y ¹ and X ³ may be equal to Y ^{3 , X 1} may be equal to Y ³ and X ³ may be equal to Y ^{1 .}

For example, the moiety represented by Chemical Formula 2 may be any one selected from the following Chemical Formulas 2-I to 2-V.

[Formula 2-Ⅰ] [Formula 2-Ⅱ]

[Formula 2-Ⅲ] [Formula 2-IV]

[Formula 2-V]

In Formulas 2-I to 2-V, X ¹ to X ³ , Y ¹ to Y ³ , R ¹ and R ² are the same as described above.

For example, the substituted or unsubstituted moiety represented by Formula 1 may be any one of substituted or unsubstituted selected from the following group 1, but is not limited thereto.

[Group 1]

In group 1,

R ¹ , R ² , R ^a and R ^d 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-mentioned Chemical Formula 1, and a plurality of substituted or unsubstituted moieties represented by the above-mentioned Chemical Formula 1 are mutually exclusive. may be the same or different from each other.

As described above, the polymer further includes a substituted or unsubstituted C6 to C30 aromatic moiety together with the substituted or unsubstituted moiety represented by the aforementioned formula (1), thereby increasing the carbon content of the polymer, thereby making it harder Since a polymer layer can be formed, the etch resistance can be improved.

For example, the substituted or unsubstituted C6 to C30 aromatic moiety may be any one selected from the following group 2, but is not limited thereto.

[Group 2]

In group 2, each aromatic moiety may be unsubstituted or substituted with one or more substituents. wherein the substituent is, for example, deuterium, halogen, hydroxy 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, substituted or It may be an 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, the substituted or unsubstituted C6 to C30 aromatic moiety may be a non-condensed ring and/or a condensed ring, but preferably a condensed ring.

For example, the substituted or unsubstituted C6 to C30 aromatic moiety may be substituted with at least one hydroxyl group.

The polymer according to one embodiment may include one or a plurality of the aforementioned substituted or unsubstituted C6 to C30 aromatic moieties, and a plurality of the aforementioned substituted or unsubstituted C6 to C30 aromatic moieties are between each other. may be the same or different from each other.

As an example, the polymer may include one or more first structural units consisting of a substituted or unsubstituted fused heterocyclic moiety represented by the above-mentioned Formula 1 and the above-mentioned substituted or unsubstituted aromatic moiety, and the first The structural unit may be represented by the following formula (3).

[Formula 3]

In Formula 3,

X, Y, R ¹ , and R ² are as described above,

A is a substituted or unsubstituted C6 to C30 aromatic ring.

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 may be any one of substituted or unsubstituted selected from Group 2, but is not limited thereto.

For example, A may be a non-condensed ring and/or a condensed ring, but preferably a condensed ring.

For example, A may be substituted with at least one hydroxyl group.

For example, the first structural unit represented by Formula 3 may be represented by Formula 4 below.

[Formula 4]

In Formula 4, R ¹ , R ² , X ¹ , X ³ , Y ¹ , Y ³ and A are the same as described above.

In Formula 4, a bond indicated by a solid line and a dotted line at the same time means that the bond may be a single bond or a double bond.

For example, the first structural unit represented by Chemical Formula 4 may be any one selected from the following Chemical Formulas 4-I to 4-V.

[Formula 4-Ⅰ] [Formula 4-Ⅱ]

[Formula 4-Ⅲ] [Formula 4-IV]

[Formula 4-V]

In Formulas 4-I to 4-V, X ¹ , X ³ , Y ¹ , Y ³ , A, R ¹ and R ² are the same as described above.

For example, the first structural unit represented by Chemical Formula 4 may be any one selected from the following Chemical Formulas 4-1 to 4-11.

[Formula 4-1] [Formula 4-2]

[Formula 4-3] [Formula 4-4]

[Formula 4-5] [Formula 4-6]

[Formula 4-7] [Formula 4-8]

[Formula 4-9] [Formula 4-10]

[Formula 4-11]

In Formulas 4-1 to 4-11, R ¹ , R ² , R ^d and A are the same as described above.

For example, the polymer may include two or more different first structural units, for example, two or more structural units selected from Formulas 4-1 to 4-11.

The polymer according to an embodiment 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, but preferably the same first structural unit. It may include a structure in which structural units are continuously connected.

For example, the polymer may further include a second structural unit represented by Formula 3 and different from the first structural unit. The polymer may include one or a plurality of second structural units, and the number and arrangement of the aforementioned first and second structural units included in the polymer are not limited. Preferably, it may include a structure in which the first structural unit and the second structural unit are alternately connected.

For example, the polymer may further include a substituted or unsubstituted fluorene moiety.

For example, the substituted or unsubstituted fluorene moiety may be represented by the following Chemical Formula 5.

[Formula 5]

In Formula 5,

L ¹ and L ² are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a C2 to C30 divalent heterocyclic group, or a combination thereof,

Z and W are each independently a substituted or unsubstituted C6 to C30 aromatic ring, a substituted or unsubstituted C6 to C30 heterocyclic ring, or a combination thereof,

' 는 중합체 내 인접한 다른 모이어티와 연결지점을 의미한다.'

' means a point of connection with other adjacent moieties in the polymer.

For example, L ¹ and L ² are each independently a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthalene group, a substituted or unsubstituted anthracenylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted a naphthacenylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted quarterphenylene group, a substituted or unsubstituted chrysenylene group, A substituted or unsubstituted triphenylenylene group, a substituted or unsubstituted perylenylene group, a combination thereof, or a combination thereof may be in a fused form, but is not limited thereto.

For example, L ¹ and L ² may each independently be a substituted or unsubstituted C6 to C10 arylene group, for example, a substituted or unsubstituted phenylene group or a substituted or unsubstituted naphthalene group.

For example, L ¹ and L ² may each independently be substituted with a hydroxyl group.

For example, L ¹ and L ² may be the same or different.

For example, each of Z and W may be independently substituted with a hydroxyl group and/or a substituted or unsubstituted C1 to C30 alkynyl group.

For example, Z and W may be the same or different.

For example, L ¹ , L ² , Z and W may each independently include a condensed ring.

For example, the substituted or unsubstituted fluorene moiety may be any one selected from the following group 3, but is not limited thereto.

[Group 3]

' 는 중합체 내 인접한 다른 모이어티와 연결지점을 의미한다.In group 3 above, '

' means a point of connection with other adjacent moieties in the polymer.

The substituted or unsubstituted fluorene moiety includes a quaternary carbon, and the polymer further includes the substituted or unsubstituted fluorene moiety having a quaternary carbon, whereby the CFx mixed gas of the layer made of the polymer It can give high corrosion resistance to Here, the quaternary carbon is defined as a central carbon in which all four bonds are carbon.

The polymer according to one embodiment may include one or a plurality of the aforementioned substituted or unsubstituted fluorene moieties, and a plurality of the aforementioned substituted or unsubstituted fluorene moieties may be the same as or different from each other. .

For example, the polymer may further include a third structural unit represented by Chemical Formula 6.

[Formula 6]

In Formula 6, R ¹ , R ² , X, Y, L ¹ , L ² , Z and W are the same as described above.

For example, the polymer may include one or a plurality of third structural units, and the number and arrangement of the third structural units included in the polymer are not limited. Preferably, it may include a structure in which the above-described first structural unit and the third structural unit are alternately connected.

For example, the polymer may further include a fourth structural unit represented by Chemical Formula 6 and different from the third structural unit. The polymer may include one or a plurality of fourth structural units, and the number and arrangement of the third and fourth structural units included in the polymer are not limited.

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 1,000 to 100,000, about 1,200 to 50,000, or about 1,500 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.

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

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, methoxypropanediol, diethylene glycol, diethylene glycol butyl ether , tri(ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N,N-dimethylformamide, N,N-dimethyl It may include at least one selected from acetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone, and ethyl 3-ethoxypropionate, but is not limited thereto.

The polymer may be included in, for example, about 0.1 to 50% by weight, such as about 0.5 to 40% by weight, about 1 to 30% by weight, or about 3 to 20% 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, substituted urea-based, or polymer-based agent. 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 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, an organic film prepared using the above-described hard mask composition is provided. 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 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.

The method for forming a pattern according to an embodiment includes forming a material layer on a substrate, applying a hardmask composition including the above-described polymer and a solvent on the material layer, and heat-treating the hardmask composition to form a hardmask layer forming a photoresist layer on the 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 coating thickness of the hard mask composition is not particularly limited, but may be applied, for example, to a thickness of about 50 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.

As an 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, and the etching gas may be, for example, CHF ₃ , CF ₄ , Cl ₂ , BCl _{3 ,} or a mixture thereof.

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

1,2,3,4-benzenetetramine tetrahydrochloride (1,2,3,4-benzenetetramine tetrahydrochloride, 28.4) in a 1L 2-neck round-bottomed flask equipped with a condenser g, 0.10 mol), 1,6-Pyrenedicarboxylic acid (1,6-Pyrenedicarboxylic acid, 29.0 g, 0.10 mol), and polyphosphoric acid (300 g) were added, and then 24 hours to 48 hours at 150 ° C. The polymerization reaction was carried out by stirring for a period of time. The reaction was completed when the weight average molecular weight was 1,000 to 5,000. After the polymerization reaction was completed, the reactant was slowly cooled to room temperature, the reactant was neutralized with 1M sodium hydroxide (NaOH) solution, and the resulting solid was filtered. It was washed with distilled water, ethanol, and diethyl ether in that order, and after drying, a polymer represented by the following Chemical Formula 4a was obtained. (MW: 2,500)

[Formula 4a]

Synthesis Example 2

2,4-diamino-1,3-benzenedithiol dihydrochloride (2,4-diamino-1,3-benzenedithiol dihydrochloride, 24.5 g, 0.10 mol), After adding 3,7-dihydroxynaphthalene-2,6-dicarbaldehyde (3,7-dihydroxynaphthalene-2,6-dicarbaldehyde, 21.6 g, 0.10 mol), and polyphosphoric acid (300 g), Synthesis Example 1 A polymer represented by the following Chemical Formula 4b was obtained through the same synthesis process as described above. (MW: 2,300)

[Formula 4b]

Synthesis Example 3

2,4-diamino-1,3-benzenediol dihydrochloride (21.3 g, 0.10 mol), 9 in a 1L two-necked round bottom flask equipped with a condenser , 10-Phenanthrenedicarboxaldehyde (9,10-Phenanthrenedicarboxaldehyde, 23.4 g, 0.10 mol), and polyphosphoric acid (300 g) were added, followed by the same synthesis process as in Synthesis Example 1, and a polymer represented by the following Chemical Formula 4c got (MW: 2,000)

[Formula 4c]

Synthesis Example 4

1,2,3,4-benzenetetramine tetrahydrochloride (1,2,3,4-benzenetetramine tetrahydrochloride, 28.4 g, 0.10 mol), benzoperylene-1, After adding 2-dicarboxylic acid (Benzo[ ghi ]perylene-1,2-dicarboxylic acid, 36.4g, 0.10mol), and polyphosphoric acid (300g), the same synthesis process as in Synthesis Example 1 was followed and expressed by the following Chemical Formula 4d A polymer was obtained. (MW: 2,700)

[Formula 4d]

Synthesis Example 5

2,4-diamino-1,3-benzenediol dihydrochloride (2,4-diamino-1,3-benzenediol dihydrochloride, 10.7 g, 0.05 mol), 2 in a 1L 2-neck round bottom flask equipped with a condenser ,4-diamino-1,3-benzenedithiol dihydrochloride (2,4-diamino-1,3-benzenedithiol dihydrochloride, 12.3g, 0.05mol), 1,6-pyrenedicarboxylic acid (1,6 -Pyrenedicarboxylic acid, 29.2 g, 0.10 mol), and polyphosphoric acid (300 g) were added, and then a polymer represented by the following Chemical Formula 4e was obtained through the same synthesis process as in Synthesis Example 1. (MW: 2,400)

[Formula 4e]

Synthesis Example 6

1,2,3,4-benzenetetramine tetrahydrochloride (1,2,3,4-benzenetetramine tetrahydrochloride, 28.4 g, 0.10 mol), 3-hydroxynaphthalene- 2,6-Dicarbaldehyde (3-hydroxynaphthalene-2,6-dicarbaldehyde, 10.0 g, 0.05 mol), 1,6-Pyrenedicarboxylic acid (1,6-Pyrenedicarboxylic acid, 14.6 g, 0.05 mol), and poly After phosphoric acid (300 g) was added, a polymer represented by the following Chemical Formula 4f was obtained through the same synthesis process as in Synthesis Example 1. (MW: 3,300)

[Formula 4f]

Synthesis Example 7

2,4-diamino-1,3-benzenediol dihydrochloride (2,4-diamino-1,3-benzenediol dihydrochloride, 10.7 g, 0.05 mol), 4 ,4'-(9H-fluorene-9-ylidene)bisbenzoic acid (4,4'-(9H-fluorene-9-ylidene)bisbenzoic acid, 20.3 g, 0.05 mol), 1,6-pyrene diene Carboxylic acid (1,6-Pyrenedicarboxylic acid, 14.6 g, 0.05 mol), diethyl sulfate (15.4 g, 0.10 mol), and propylene glycol methyl ether acetate (PGMEA, 134 g) were added. Then, through the same synthesis process as in Synthesis Example 1, a polymer represented by the following Chemical Formula 4g was obtained. (MW: 2,700)

[Formula 4g]

Synthesis Example 8

2,4-diamino-1,3-benzenediol dihydrochloride (2,4-diamino-1,3-benzenediol dihydrochloride, 10.7 g, 0.05 mol), 6 ,6'-(9H-fluorene-9-ylidene)bis-2-naphthalenecarboxylic acid (6,6'-(9H-fluorene-9-ylidene)bis-2-naphthalenecarboxylic acid, 25.4 g, 0.05 mol), After adding 2,6-Naphthalenedicarboxylic acid (2,6-Naphthalenedicarboxylic acid, 9.2 g, 0.05 mol), diethyl sulfate (15.4 g, 0.10 mol), and 134 g of PGMEA, the same synthesis as in Synthesis Example 1 Through the process, a polymer represented by the following Chemical Formula 4h was obtained. (MW: 2,500)

[Formula 4h]

Synthesis Example 9

2,4-diamino-1,3-benzenedithiol dihydrochloride (2,4-diamino-1,3-benzenedithiol dihydrochloride, 24.6 g, 0.10 mol), 6,6'-(3,6-dihydroxy-9H-fluorene-9,9-diyl)di-2-naphthoic acid (6,6'-(3,6-dihydroxy-9H-fluorene-) 9,9-diyl)di-2-naphthoic acid, 26.9 g, 0.05 mol), 1,6-Pyrenedicarboxylic acid (1,6-Pyrenedicarboxylic acid, 14.6 g, 0.05 mol), diethyl sulfate (15.4 g, 0.10) mol), and after 134 g of PGMEA was added, a polymer represented by the following Chemical Formula 4i was obtained through the same synthesis process as in Synthesis Example 1. (MW: 3,100)

[Formula 4i]

Comparative Synthesis Example 1

4,4'-(9H-fluoren-9-ylidene)bisphenol (35.0g, 0.10mol), 1,4-bis(methoxymethyl)benzene (16.6g) in a 500mL two-necked round-bottom flask equipped with a condenser , 0.10 mol), diethyl sulfate (15.4 g, 0.10 mol), and 134 g of propylene glycol methyl ether acetate (PGMEA) were added, and the mixture was stirred at 110° C. for 24 to 48 hours to carry out the synthesis. After the reaction, the mixed solution was cooled to room temperature, diluted with 400 g of ethyl acetate, and washed 10 times with 400 g of distilled water. The organic layer was concentrated under reduced pressure, diluted with 200 g of THF, and added dropwise to 1 kg of hexane to obtain a precipitate. The precipitate was filtered and dried to obtain a polymer represented by the following formula (A). (Mw: 1,700)

[Formula A]

Comparative Synthesis Example 2

1-hydroxypyrene (21.8 g, 0.10 mol), 1-naphthol (14.5 g, 0.10 mol), paraformaldehyde (6.0 g, 0.2 mol), diethyl sulfate in a 500 mL 2-neck round-bottom flask equipped with a condenser. (15.4 g, 0.10 mol), and PGMEA (115 g) were added, and the mixture was stirred at 110° C. for 24 to 48 hours to proceed with the synthesis. After the reaction, the mixed solution was cooled to room temperature, diluted with 400 g of ethyl acetate, and washed 10 times with 400 g of distilled water. The organic layer was concentrated under reduced pressure, diluted with 200 g of THF, and added dropwise to 1 kg of hexane to obtain a precipitate. The precipitate was filtered and dried to obtain a polymer represented by the following formula (B). (Mw: 1,700)

[Formula B]

Comparative Synthesis Example 3

Indole (11.72 g, 0.10 mol), 9-fluorenone (18.02 g, 0.10 mol), and p-toluenensulfonic acid (1.90) were placed in a 500 mL two-necked round-bottom flask equipped with a condenser. g, 0.01 mol), and 70 g of PGMEA were added, and a polymer represented by the following Chemical Formula C was obtained through the same synthesis process as in Synthesis Example 1. (MW: 1,300)

[Formula C]

Formation of hard mask composition: Examples 1 to 9 and Comparative Examples 1 to 3

Each of the polymers obtained in Synthesis Examples 1 to 9 and Comparative Synthesis Examples 1 to 3 was weighed by 3.0 g, uniformly dissolved in 17 g of cyclohexanone, filtered through a 0.1 μm Teflon filter, and Examples 1 to 9 and Comparative Examples 1 to 3 hard mask compositions were prepared.

Evaluation 1. Gap-Fill Characteristics and Planarization Characteristics

1 is a reference diagram exemplarily showing a step difference of a hard mask layer in order to explain a method for evaluating a planarization characteristic.

The hard mask compositions according to Examples 1 to 9 and Comparative Examples 1 to 3 were applied on a silicon pattern wafer by adjusting the mass ratio of solute to solvent to 3 to 97, respectively, and baked to form an organic film having a thickness of 1,100 Å.

The gap-fill characteristics were determined by observing the pattern cross-section using a scanning electron microscope (SEM) to determine the presence or absence of voids.

_{The planarization characteristics (step difference measurement) are the average value (h 1} ) of the thickness of the thin film measured at three arbitrary points where the pattern is not formed on the substrate in FIG. The average value (h ₂ ) of the thickness was measured by FE-SEM and calculated, and the step (|h ₁ - h ₂ |) was calculated. The smaller the step (|h1-h2|), the better the planarization characteristic.

The results are shown in Table 1.

Gap-Fill Characteristics (with/without Void) Planarization characteristics (step difference, Å) Comparative Example 1 no void 125 Comparative Example 2 no void 139 Comparative Example 3 no void 150 Example 1 no void 105 Example 2 no void 103 Example 3 no void 118 Example 4 no void 114 Example 5 no void 107 Example 6 no void 117 Example 7 no void 119 Example 8 no void 111 Example 9 no void 107

Referring to Table 1, the organic film formed from the hardmask composition according to Examples 1 to 9 has planarization characteristics and gap-fill characteristics equivalent to those of the organic film formed from the hardmask composition according to Comparative Example 1, and Comparative Examples 2 and It can be seen that the organic layer formed from the hardmask composition according to 3 has better planarization properties and gap-fill properties than the organic layer.

Evaluation 2. corrosion resistance

The hard mask compositions according to Examples 1 to 9 and Comparative Examples 1 to 3 were spin-coated on a silicon wafer by adjusting the mass ratio of solute to solvent to 15 to 85, respectively, and then heat-treated at about 400° C. for 2 minutes to have a thickness of 4,000 Å of an organic film was formed.

The thickness of the organic layer was measured, and then the organic layer _{was dry-etched using CHF 3} /CF ₄ 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 by Equation 1 below from the difference in the thickness of the organic layer before and after dry etching and the etching time.

[Formula 1]

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/s) CHF ₃ /CF ₄ etch rate (Å/s) N ₂ /O ₂ etch rate (Å/s) Comparative Example 1 28.3 27.5 Comparative Example 2 31.5 26.0 Comparative Example 3 26.0 24.0 Example 1 24.3 22.4 Example 2 25.6 23.1 Example 3 24.9 21.6 Example 4 24.3 23.4 Example 5 23.2 21.9 Example 6 24.0 21.6 Example 7 23.6 21.5 Example 8 23.4 21.9 Example 10 25.4 22.7

Referring to Table 2, it can be seen that the organic film prepared with the hard mask composition according to Examples 1 to 9 exhibits the same or improved etch resistance as compared to the organic film prepared with the hard mask composition according to Comparative Examples 1 to 3. have.

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 present. It belongs to the scope of the invention.

Claims (20)

A substituted or unsubstituted moiety represented by the following formula (1) and
Polymers comprising substituted or unsubstituted C6 to C30 aromatic moieties:
[Formula 1]

In Formula 1,
X and Y are each independently a substituted or unsubstituted five-membered ring containing at least one hetero atom,
R ¹ and R ² are each independently hydrogen, deuterium, halogen, hydroxy group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or an unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C6 to C30 heteroarylalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 heteroaryl group, combinations thereof or other adjacent moieties is a connection point. In claim 1,
X and Y of Formula 1 are each independently a substituted or unsubstituted pentacyclic ring containing at least one nitrogen atom. In claim 1,
A substituted or unsubstituted moiety represented by Formula 1 is a polymer represented by Formula 2 below:
[Formula 2]

In Formula 2,
X ¹ to X ³ and Y ¹ to Y ³ are each independently CR ^a , CR ^b R ^c , N, NR ^d , O, S, Se or Te,
At least one of X ¹ to X ^{3 is N, NR d} , O, S, Se or Te,
At least one of Y ¹ to Y ^{3 is N, NR d} , O, S, Se or Te,
R ¹ , R ² and R ^a to R ^d are each independently hydrogen, deuterium, halogen, hydroxy group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 heterocycloalkyl group, A substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C6 to C30 heteroarylalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, a combination thereof, or It is a point of connection with other adjacent moieties. In claim 3,
In Formula 2, X ¹ , X ³ , Y ¹ and Y ³ are each independently N, NR ^d , O, S, Se or Te,
X ² and Y ² are each independently CR ^a or CR ^b R ^c ;
R ^a to R ^d are each independently hydrogen, deuterium, halogen, hydroxy group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or an unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C6 to C30 heteroarylalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 heteroaryl group, combinations thereof or other adjacent moieties A polymer that is a point of connection. In claim 3,
In Formula 2, X ¹ is the same as ^{Y 1 and X 3} is the same as ^{Y 3,}
X ¹ is the same as ^{Y 3 and X 3} is the same as ^{Y 1 polymer.} In claim 1,
The substituted or unsubstituted moiety represented by Formula 1 is a substituted or unsubstituted polymer selected from the following group 1:
[Group 1]

In group 1,
R ¹ , R ² , R ^a and R ^d are each independently hydrogen, deuterium, halogen, hydroxy group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 heterocycloalkyl group, A substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C6 to C30 heteroarylalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, a combination thereof, or It is a point of connection with other adjacent moieties. In claim 1,
The substituted or unsubstituted C6 to C30 aromatic moiety is a substituted or unsubstituted polymer selected from Group 2 below.
[Group 2]

In claim 1,
The substituted or unsubstituted C6 to C30 aromatic moiety is a condensed ring polymer. In claim 1,
The polymer is a polymer comprising a first structural unit represented by the following Chemical Formula 3:
[Formula 3]

In Formula 3,
X and Y are each independently a substituted or unsubstituted five-membered ring containing at least one hetero atom,
R ¹ and R ² are each independently hydrogen, deuterium, halogen, hydroxy group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or an unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C6 to C30 heteroarylalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof;
A is a substituted or unsubstituted C6 to C30 aromatic ring. In claim 9,
X and Y of Formula 3 are each independently a substituted or unsubstituted penta-membered ring including at least one nitrogen atom. In claim 9,
The first structural unit represented by the formula (3) is a polymer represented by the following formula (4):
[Formula 4]

In Formula 4,
X ¹ , X ³ , Y ¹ and Y ³ are each independently CR ^a , CR ^b R ^c , N, NR ^d , O, S, Se or Te;
at least one of X ¹ and X ^{3 is N, NR d} , O, S, Se or Te,
At least one of Y ¹ and Y ^{3 is N, NR d} , O, S, Se or Te,
R ¹ , R ² and R ^a to R ^d are each independently hydrogen, deuterium, halogen, hydroxy group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 heterocycloalkyl group, A substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C6 to C30 heteroarylalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof; ,
A is a substituted or unsubstituted C6 to C30 aromatic ring. In claim 11,
In Formula 4, X ¹ , X ³ , Y ¹ and Y ³ are each independently N, NR ^d , O, S, Se or Te,
R ^a to R ^d are each independently hydrogen, deuterium, halogen, hydroxy group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or an unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C6 to C30 heteroarylalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof. In claim 11,
In Formula 4, X ¹ is the same as ^{Y 1 and X 3} is the same as ^{Y 3,}
X ¹ is the same as ^{Y 3 and X 3} is the same as ^{Y 1 polymer.} In claim 11,
The first structural unit represented by Chemical Formula 4 is a polymer selected from the following Chemical Formulas 4-1 to 4-11:
[Formula 4-1] [Formula 4-2]

[Formula 4-3] [Formula 4-4]

[Formula 4-5] [Formula 4-6]

[Formula 4-7] [Formula 4-8]

[Formula 4-9] [Formula 4-10]

[Formula 4-11]

In Formulas 4-1 to 4-11,
R ¹ , R ² and R ^d are each independently hydrogen, deuterium, halogen, hydroxy group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkene Nyl group, substituted or unsubstituted C2 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 a cyclic C7 to C30 arylalkyl group, a substituted or unsubstituted C6 to C30 heteroarylalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof;
A is a substituted or unsubstituted C6 to C30 aromatic ring. 15. In claim 14,
The polymer is a polymer comprising two or more structural units selected from Formulas 4-1 to 4-11. In claim 9,
A of Formula 3 is a substituted or unsubstituted polymer selected from Group 2 below.
[Group 2]

In claim 9,
A of Formula 3 is a condensed ring polymer. In claim 9,
The polymer is represented by Formula 3 and further comprises a second structural unit different from the first structural unit. 19. A polymer according to any one of claims 1 to 18, and
menstruum
A hard mask composition comprising a. Forming a hardmask layer by applying the hardmask composition according to claim 19 on the material layer and heat-treating it;
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.

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