KR102393686B1 - Polymer and hardmask composition and method of forming patterns - Google Patents

Abstract

상기 화학식 1에서, A 및 B의 정의는 명세서에 기재한 바와 같다.The present invention relates to a polymer including a polymer including a first structural unit represented by the following Chemical Formula 1, a hardmask composition including the polymer, and a pattern forming method using the hardmask composition.
[Formula 1]

In Formula 1, the definitions of A and B are as described in the specification.

Description

Polymer, hard mask 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 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 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, there is provided a polymer including a structural unit represented by the following formula (1).

[Formula 1]

In Formula 1, A is a moiety represented by Formula 2 below, and B is a divalent organic group including at least one quaternary carbon.

[Formula 2]

In Formula 2, X is a substituted or unsubstituted C1 to C3 alkylene group, a substituted or unsubstituted C1 to C3 alkenylene group, NR ^d , O, S or a combination thereof,

R ^a is 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 C10 alkyl group, a 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 C3 to C30 cycloalkenyl group, substituted Or an unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heterocyclic group, or a combination thereof,

R ^b and R ^c are each independently hydrogen, halogen, amine group, cyano group, carboxyl group, substituted or unsubstituted C2 to C30 oxoalkyl group, substituted or unsubstituted C1 to C30 alkoxycarbonyl group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C1 to C30 alkenyl group, substituted or unsubstituted C1 to C30 alkynyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, A substituted or unsubstituted C3 to 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; ,

R ^d is hydrogen, halogen, carboxyl group, substituted or unsubstituted C2 to C30 oxoalkyl group, substituted or unsubstituted C1 to C30 alkoxycarbonyl group, substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C1 to C30 alkenyl group, substituted or unsubstituted C1 to C30 alkynyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted Or an unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heterocyclic group, or a combination thereof,

l is an integer from 0 to 2,

* is the point of connection with other moieties in the polymer of formula (1).

The moiety represented by Chemical Formula 2 may be any one selected from the following Chemical Formulas 2-1 to 2-6.

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

[Formula 2-4] [Formula 2-5] [Formula 2-6]

In Formulas 2-1 to 2-6,

R ^a is 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 C10 alkyl group, a 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 C3 to C30 cycloalkenyl group, substituted Or an unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heterocyclic group, or a combination thereof,

R ^b and R ^c are each independently hydrogen, halogen, amine group, cyano group, carboxyl group, substituted or unsubstituted C2 to C30 oxoalkyl group, substituted or unsubstituted C1 to C30 alkoxycarbonyl group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C1 to C30 alkenyl group, substituted or unsubstituted C1 to C30 alkynyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, A substituted or unsubstituted C3 to 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; ,

R ^d is hydrogen, halogen, carboxyl group, substituted or unsubstituted C2 to C30 oxoalkyl group, substituted or unsubstituted C1 to C30 alkoxycarbonyl group, substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C1 to C30 alkenyl group, substituted or unsubstituted C1 to C30 alkynyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted Or an unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heterocyclic group, or a combination thereof,

R ¹ and R ² are each independently hydrogen, halogen, hydroxyl group, amine group, cyano group, carboxyl group, substituted or unsubstituted C2 to C30 oxoalkyl group, substituted or unsubstituted C1 to C30 alkoxycarbonyl group, substituted or unsubstituted A substituted C1 to C20 alkylamine 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 alkyl group Nyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted A cyclic C3 to C30 heterocyclic group or a combination thereof,

l is an integer from 0 to 2.

l may be 1 or 2.

R ^a is hydrogen, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, oxoethyl group, oxopropyl group, oxobutyl group, It may be a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, an ethoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, a propoxymethyl group, a propoxyethyl group, a propoxypropyl group, or a combination thereof.

R ^b and R ^c are each independently hydrogen, F, Br, Cl, I, a cyano group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted iso-propyl group, substituted or unsubstituted n-butyl group, substituted or unsubstituted iso-butyl group, substituted or unsubstituted sec-butyl group, substituted or unsubstituted tert-butyl group, substituted or unsubstituted It may be an oxoethyl group, a substituted or unsubstituted oxopropyl group, a substituted or unsubstituted oxobutyl group, or a combination thereof.

The moiety represented by Chemical Formula 2 may be any one selected from the following group 1.

[Group 1]

B may include at least one substituted or unsubstituted C6 to C30 aromatic ring.

B may be represented by the following Chemical Formula 3 or Chemical Formula 4.

[Formula 3] [Formula 4]

In Formulas 3 and 4,

Ar ¹ to Ar ⁴ are each independently a substituted or unsubstituted C6 to C30 aryl group,

Ar ¹ and Ar ² each independently exist or combine with each other to form a ring,

Ar ³ and Ar ⁴ are each independently present or combine with each other to form a ring,

L is a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C10 heteroalkylene group, or a combination thereof,

* is the point of connection with other moieties in the polymer of formula (1).

B may be selected from the following group 2.

[Group 2]

In Group 2, L is a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C10 heteroalkylene group, or a combination thereof,

R ³ to R ⁶ are each independently a hydroxyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a halogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or Unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof;

a to d are each independently an integer of 0 to 4,

m and n are each independently an integer of 1 to 3,

* is the point of connection with other moieties in the polymer of formula (1).

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

The second structural unit may be represented by the following Chemical Formula 5.

[Formula 5]

In Formula 5, C is a substituted or unsubstituted C3 to C30 non-aromatic ring group, a substituted or unsubstituted C6 to C30 aromatic ring group, a substituted or unsubstituted heterocyclic group, a fused ring thereof, or a combination thereof; ,

D is a divalent organic group containing at least one quaternary carbon and is the same as or different from B above.

C may include at least one polycyclic ring.

C is a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted acenaphthylenylene group, a substituted or unsubstituted acenaphthenylene group, a substituted or unsubstituted anthracenylene group, substituted or an unsubstituted phenanthrenylene group, a substituted or unsubstituted tetracenylene group, a substituted or unsubstituted triphenylenylene group, a substituted or unsubstituted chrysenylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted a biphenylene group, a substituted or unsubstituted benzophenanthrenylene group, a substituted or unsubstituted benzofluoranthenylene group, a substituted or unsubstituted pentacenylene group, a substituted or unsubstituted binaphthylene group, a substituted or unsubstituted benzopyrenylene group, substituted or unsubstituted perylenylene group, substituted or unsubstituted fluoranthenylene group, substituted or unsubstituted benzoperylenylene group, substituted or unsubstituted coronenylene group, substituted or unsubstituted It may be a cyclic dibenzofluoranthenylene group or a group represented by Formula 6 below.

[Formula 6]

In Formula 6, Y ¹ and Y ² are each independently a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C6 to C30 aromatic ring group, or a substituted or unsubstituted C6 to C30 heterocycle group or a combination thereof,

Ar ⁵ and Ar ⁶ are each independently a substituted or unsubstituted C6 to C30 aryl group,

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

C may include at least one of a hydroxyl group and a substituted or unsubstituted C1 to C30 alkoxy group.

D may include at least one substituted or unsubstituted C6 to C30 aromatic ring.

D may be represented by the following Chemical Formula 7 or Chemical Formula 8.

[Formula 7] [Formula 8]

In Formulas 7 and 8, Ar ¹ to Ar ⁴ are each independently a substituted or unsubstituted C6 to C30 aryl group,

Ar ¹ and Ar ² each independently exist or combine with each other to form a ring,

Ar ³ and Ar ⁴ are each independently present or combine with each other to form a ring,

L is a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C10 heteroalkylene group, or a combination thereof,

* is the point of connection with other moieties in the polymer of formula (1).

D may be selected from group 3 below.

[Group 3]

In group 3, L is a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C10 heteroalkylene group, or a combination thereof,

R ¹ to R ⁴ are each independently a hydroxyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a halogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or Unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof;

a to d are each independently an integer of 0 to 4,

m and n are each independently an integer of 1 to 3,

* is the point of connection with other moieties in the polymer of formula (1).

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 hardmask layer in order to explain a method for evaluating planarization characteristics.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art 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 C15 cycloalkynyl group, C2 to C30 heterocyclic group, and combinations thereof mean substituted with a substituent.

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.

In addition, unless otherwise defined herein, 'heteroalkyl group' is a concept including an alkyl group including an ether moiety, for example, may include an alkyl group substituted with an alkoxy group, specifically, methoxy Methoxy group, methoxyethoxy group, methoxypropoxy group, methoxybutoxy group, ethoxymethoxy group, ethoxyethoxy group, ethoxypropoxy group, ethoxybutoxy group, propoxymethoxy group, propoxy group It may include a oxy group, a propoxy propoxy group, a propoxy butoxy group, a butoxy methoxy group, a butoxy ethoxy group, a butoxy propoxy group or a butoxy butoxy group.

In addition, unless otherwise defined herein, 'heteroalkylene group' is a concept including an alkylene group including an ether moiety, for example, dimethyl ether, methyl ethyl ether, methyl propyl ether , methylbutylether, diethylether, ethylpropylether, ethylbutylether, dipropylether, propylbutylether or an alkylene group containing a dibutylether moiety.

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 fusion 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 and/or a substituted or unsubstituted heterocyclic group includes a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted A substituted or unsubstituted 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, 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.

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 includes a heterocycle including a cyclic ester group and a quaternary carbon. Here, the quaternary carbon is defined as a central carbon in which all four bonds are carbon.

For example, the polymer may include an aromatic ring condensed on a heterocycle including a cyclic ester group, and may include a moiety represented by Chemical Formula 2 to be specifically described later.

By including an aromatic moiety condensed to the heterocyclic group including the heterocyclic group and the heterocyclic group including the cyclic ester group in the polymer, the solubility of the polymer in solvents can be increased, and the carbon content can be increased Because it can form a hard polymer layer, high etch resistance can be imparted.

For example, the polymer may include a structural unit represented by the following formula (1).

[Formula 1]

In Formula 1, A is a moiety represented by Formula 2 below, and B is a divalent organic group including at least one quaternary carbon.

[Formula 2]

In Formula 2, X is a substituted or unsubstituted C1 to C3 alkylene group, a substituted or unsubstituted C1 to C3 alkenylene group, NR ^d , O, S or a combination thereof,

R ^a is 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 C10 alkyl group, a 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 C3 to C30 cycloalkenyl group, substituted Or an unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heterocyclic group, or a combination thereof,

R ^b and R ^c are each independently hydrogen, halogen, amine group, cyano group, carboxyl group, substituted or unsubstituted C2 to C30 oxoalkyl group, substituted or unsubstituted C1 to C30 alkoxycarbonyl group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C1 to C30 alkenyl group, substituted or unsubstituted C1 to C30 alkynyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, A substituted or unsubstituted C3 to 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; ,

R ^d is hydrogen, halogen, carboxyl group, substituted or unsubstituted C2 to C30 oxoalkyl group, substituted or unsubstituted C1 to C30 alkoxycarbonyl group, substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C1 to C30 alkenyl group, substituted or unsubstituted C1 to C30 alkynyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted Or an unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heterocyclic group, or a combination thereof,

l is an integer from 0 to 2,

* is the point of connection with other moieties in the polymer of formula (1).

For example, X is a substituted or unsubstituted methylene group. It may be a substituted or unsubstituted ethylene group, a substituted or unsubstituted ethenylene group, NR ^a , O, S, or a combination thereof. Here, the substitution is a hydroxy group, halogen, cyano group, carboxy group, substituted or unsubstituted C2 to C30 oxoalkyl group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted It may be a cyclic C1 to C30 heteroalkyl group or a combination thereof, and more specifically, a hydroxy group, F, Br, Cl, I, a cyano group, a carboxy group, a substituted or unsubstituted oxoethyl group, a substituted or unsubstituted oxopropyl group group, substituted or unsubstituted oxobutyl group, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or unsubstituted propyl group, substituted or unsubstituted butyl group, substituted or unsubstituted methoxy group, substituted Or it may be an unsubstituted ethoxy group, a substituted or unsubstituted propoxy group, a substituted or unsubstituted butoxy group, or a combination thereof.

For example, l may be 1 or 2. That is, when the polymer contains at least one OR ^a , the polymer may have excellent solubility in a solvent, and when a film is formed from the composition containing the polymer, a step or a pattern exists in the lower substrate (or film) In the case of forming , better gap-fill and planarization properties may be provided.

When l is 2, a plurality of R ^a may be the same as or different from each other.

For example, R ^a is hydrogen, 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 linear alkyl group, a substituted or unsubstituted C3 to C30 It may be a branched alkyl group or a group represented by the following Chemical Formula 2-a.

[Formula 2-a]

In Formula 2-a, X' and Y' are each independently a substituted or unsubstituted C1 to C15 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof,

Z' is hydrogen, a C1 to C15 alkyl group, a C6 to C30 aryl group, or a combination thereof;

m' and n' are each independently an integer from 0 to 5, m'+n' is an integer satisfying the range of 2=m'+n'=8,

* is the connection point with the oxygen atom (O) of OR ^a in Formula 2.

For example, X', Y' and Z' are each independently a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, a substituted or unsubstituted It may be a cyclic pentylene group, a substituted or unsubstituted hexylene group, or a combination thereof, and more specifically, X', Y' and Z' are each independently a substituted or unsubstituted methylene group, a substituted or unsubstituted It may be an ethylene group, a substituted or unsubstituted n-propylene group, a substituted or unsubstituted n-butylene group, a substituted or unsubstituted n-pentylene group, or a substituted or unsubstituted n-hexylene group, but is not limited thereto. does not

In Formula 2-a, X' and Y' may be the same as or different from each other, and m' and n' may be the same as or different from each other.

For example, m' and n' are each independently an integer of 0 to 3, for example, may be an integer of 0 to 2, for example, m' may be 1, and n' may be 1.

For example, at least one of m' and n' may be 0.

For example, R ^a is hydrogen, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, oxoethyl group, oxopropyl group, oxo It may be a butyl group, a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, an ethoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, a propoxymethyl group, a propoxyethyl group, or a propoxypropyl group.

For example, R ^b and R ^c are each independently hydrogen, F, Br, Cl, I, a cyano group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or an unsubstituted iso-propyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted iso-butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted tert-butyl group, a substituted Or it may be an unsubstituted oxoethyl group, a substituted or unsubstituted oxopropyl group, a substituted or unsubstituted oxobutyl group, or a combination thereof.

The R ^b and R ^c may be the same as or different from each other.

For example, the moiety represented by Chemical Formula 2 may be any one selected from the following Chemical Formulas 2-1 to 2-6.

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

[Formula 2-4] [Formula 2-5] [Formula 2-6]

In Formulas 2-1 to 2-6,

R ¹ and R ² are each independently hydrogen, halogen, hydroxyl group, amine group, cyano group, carboxyl group, substituted or unsubstituted C2 to C30 oxoalkyl group, substituted or unsubstituted C1 to C30 alkoxycarbonyl group, substituted or unsubstituted A substituted C1 to C20 alkylamine 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 alkyl group Nyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted A cyclic C3 to C30 heterocyclic group or a combination thereof, and R ^a , R ^b , R ^c , R ^d and 1 are the same as described above.

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

For example, R ¹ and R ² are each independently hydrogen, a hydroxyl group, F, Br, Cl, I, a cyano group, a carboxy group, a substituted or unsubstituted oxoethyl group, a substituted or unsubstituted oxopropyl group, a substituted or unsubstituted A substituted or unsubstituted methyl group, 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 methoxy group, a substituted or unsubstituted ethoxy group It may be a group, a substituted or unsubstituted propoxy group, a substituted or unsubstituted butoxy group, or a combination thereof.

More specifically, R ¹ and R ² are each independently hydrogen, a hydroxyl group, Br, a cyano group, a carboxy group, an oxoethyl group, an oxopropyl group, an oxobutyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a bromomethyl group, Bromoethyl group, bromopropyl group, methoxymethyl group, methoxyethyl group, methoxypropyl group, ethoxymethyl group, ethoxyethyl group, ethoxypropyl group, propoxymethyl group, propoxypropyl group, methoxy group, ethoxy group, It may be a propoxy group, a butoxy group, or a combination thereof.

For example, the moiety represented by Chemical Formula 2 may be any one selected from the following group 1, but is not limited thereto.

[Group 1]

The polymer according to one embodiment may include one or a plurality of substituted or unsubstituted moieties (A) represented by the above-described Chemical Formula 2, and a plurality of substituted or unsubstituted moieties represented by the above-mentioned Chemical Formula 2 The tees may be the same or different from each other.

As described above, the polymer further includes a divalent organic group (B) containing a quaternary carbon together with a substituted or unsubstituted moiety represented by the above-mentioned formula (2), wherein the polymer contains a quaternary carbon, Since the carbon content of the polymer can be increased, it is possible to impart high etch resistance to the CFx mixed gas and the N ₂ /O ₂ mixed gas of the layer made of the polymer.

B may include at least one substituted or unsubstituted C6 to C30 aromatic ring. Accordingly, the carbon content of the polymer can be increased to form a harder polymer layer, and thus the etch resistance can be further improved.

As an example, B may be represented by the following Chemical Formula 3 or Chemical Formula 4.

[Formula 3] [Formula 4]

In Formulas 3 and 4,

Ar ¹ to Ar ⁴ are each independently a substituted or unsubstituted C6 to C30 aryl group,

Ar ¹ and Ar ² each independently exist or combine with each other to form a ring,

Ar ³ and Ar ⁴ are each independently present or combine with each other to form a ring,

L is a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C10 heteroalkylene group, or a combination thereof,

* is the point of connection with other moieties in the polymer of formula (1).

By including a divalent organic group containing a quaternary carbon represented by Chemical Formula 3 or Chemical Formula 4, the polymer can have excellent corrosion resistance as described above, and can further increase solubility in a solvent, so that the polymer When forming a film with a composition containing

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

For example, Ar ¹ to Ar ⁴ may each independently 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, Ar ¹ and Ar ² may combine with each other to form a ring, and Ar ³ and Ar ⁴ may combine with each other to form a ring, and thus, the polymer may form a hard polymer layer, resulting in higher etch resistance can be given

For example, Ar ¹ to Ar ⁴ are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted anthra group Cenyl group, substituted or unsubstituted fluoranthenyl group, substituted or unsubstituted acenaphthylenyl group, substituted or unsubstituted acenaphthenyl group, substituted or unsubstituted phenanthrenyl group, substituted or unsubstituted benzophenanthrene A nyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted tetracenyl group, a substituted or unsubstituted benzofluoranthenyl group, A substituted or unsubstituted perylenyl group, a substituted or unsubstituted benzopyrenyl group, a substituted or unsubstituted naphthoanthracenyl group, a substituted or unsubstituted pentacenyl group, a substituted or unsubstituted benzofurylenyl group, a substituted Or it may be an unsubstituted dibenzopyrenyl group, a substituted or unsubstituted coronenyl group, or a combination thereof.

As an example, B may be selected from group 2 below.

[Group 2]

In group 2,

R ³ to R ⁶ are each independently a hydroxyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a halogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or Unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof;

a to d are each independently an integer of 0 to 4,

m and n are each independently an integer of 1 to 3,

Ar ¹ To Ar ⁴ , L and * are the same as described above.

For example, a to d may each independently be an integer of 0 to 2, for example, may be 0 or 1, for example, may be 0.

The polymer according to one embodiment may include one or a plurality of divalent organic groups (B) including the aforementioned quaternary carbon, and a plurality of the aforementioned divalent organic groups (B) including the aforementioned quaternary carbons (B) They may be the same or different from each other.

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.

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

The second structural unit may be represented by the following Chemical Formula 5.

[Formula 5]

In Formula 5, C is a substituted or unsubstituted C3 to C30 non-aromatic ring group, a substituted or unsubstituted C6 to C30 aromatic ring group, a substituted or unsubstituted heterocyclic group, a fused ring thereof, or a combination thereof; ,

D is a divalent organic group containing at least one quaternary carbon and is the same as or different from B above.

The polymer includes the above-described cyclic group at a position corresponding to C in Formula 5, so that the carbon content of the polymer can be increased, so that the layer made of the polymer has high corrosion resistance to CFx mixed gas and N ₂ /O ₂ mixed gas can be given

C may include at least one polycyclic ring, and the polycyclic ring may be a condensed ring and/or a non-condensed ring. As described above, when the polymer includes a polycyclic ring, higher corrosion resistance to the etching gas of the layer made of the polymer can be imparted.

For example, C is a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted acenaphthylenylene group, a substituted or unsubstituted acenaphthenylene group, a substituted or unsubstituted anthracenyl group Rene group, substituted or unsubstituted phenanthrenylene group, substituted or unsubstituted tetracenylene group, substituted or unsubstituted triphenylenylene group, substituted or unsubstituted chrysenylene group, substituted or unsubstituted pyrenylene group, substituted Or an unsubstituted biphenylene group, a substituted or unsubstituted benzophenanthrenylene group, a substituted or unsubstituted benzofluoranthenylene group, a substituted or unsubstituted pentacenylene group, a substituted or unsubstituted binaphthylene group, a substituted or an unsubstituted benzopyrenylene group, a substituted or unsubstituted perylenylene group, a substituted or unsubstituted fluoranthenylene group, a substituted or unsubstituted benzoperylenylene group, a substituted or unsubstituted coronenylene group, It may be a substituted or unsubstituted dibenzofluoranthenylene group or a group represented by the following formula (6).

[Formula 6]

In Formula 6, Y ¹ and Y ² are each independently a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C6 to C30 aromatic ring group, or a substituted or unsubstituted C6 to C30 heterocycle group or a combination thereof,

Ar ⁵ and Ar ⁶ are each independently a substituted or unsubstituted C6 to C30 aryl group,

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

For example, Ar ⁵ and Ar ⁶ are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted anthra group Cenyl group, substituted or unsubstituted fluoranthenyl group, substituted or unsubstituted acenaphthylenyl group, substituted or unsubstituted acenaphthenyl group, substituted or unsubstituted phenanthrenyl group, substituted or unsubstituted benzophenanthrene A nyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted tetracenyl group, a substituted or unsubstituted benzofluoranthenyl group, A substituted or unsubstituted perylenyl group, a substituted or unsubstituted benzopyrenyl group, a substituted or unsubstituted naphthoanthracenyl group, a substituted or unsubstituted pentacenyl group, a substituted or unsubstituted benzofurylenyl group, a substituted Or it may be an unsubstituted dibenzopyrenyl group, a substituted or unsubstituted coronenyl group, or a combination thereof.

For example, Y ¹ and Y ² may be a single bond or a substituted or unsubstituted one selected from the following groups 4 and 5.

[Group 4]

In group 4,

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

R ^e to R ^g 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;

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

[Group 5]

In group 5,

Z ¹ is NR ^h , PR ⁱ , P(=O)R ^j , O or S;

Z ² is N or P,

R ^h to R ^j 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;

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

More specifically, C may be any one of substituted or unsubstituted groups selected from the following groups 6 to 8.

[Group 6]

In Group 6, Y ¹ and Y ² are the same as described above, and * is a connection point with another moiety in the polymer of Formula 3.

[Group 7]

In the above group 7, * is a point of connection with another moiety in the polymer of formula (3).

[Group 8]

In Group 8, Z ¹ and Z ² are the same as described above, and * is a connection point with another moiety in the polymer of formula (3).

C may include at least one of a hydroxyl group and a substituted or unsubstituted C1 to C30 alkoxy group. When C includes at least one hydroxy group or a hydrophilic functional group such as a substituted or unsubstituted C1 to C30 alkoxy group, the polymer may increase solubility in a solvent, thereby having excellent gap-fill properties and planarization properties.

As described above, the polymer further includes a divalent organic group (D) containing a quaternary carbon at a position corresponding to Chemical Formula 5, and by including the quaternary carbon, it is possible to increase the carbon content of the polymer, It can provide corrosion resistance.

D may include at least one substituted or unsubstituted C6 to C30 aromatic ring. Accordingly, the carbon content of the polymer can be increased to form a harder polymer layer, and thus the etch resistance can be further improved.

D may be represented by the following Chemical Formula 7 or Chemical Formula 8.

[Formula 7] [Formula 8]

In Formulas 7 and 8, * is a connection point with another moiety in the polymer of Formula 3, and Ar ¹ to Ar ⁴ and L are the same as described above.

As an example, D may be selected from group 3 below.

[Group 3]

In Group 3, * is a connection point with another moiety in the polymer of Formula 3, and Ar ¹ to Ar ⁴ , L, R ¹ to R ⁴ , a to d, m and n are as described above.

For example, the polymer may include one or a plurality of second structural units, the plurality of second structural units may be the same as or different from each other, and The number and arrangement are not limited, and may include a structure in which second structural units are continuously connected and/or a structure in which the above-described first structural units and second structural units are alternately connected.

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

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

The 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, 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 acid compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid and/or 2,4 ,4,6-tetrabromocyclohexadienone, benzointosylate, 2-nitrobenzyltosylate, and other organic sulfonic acid alkyl esters may be used, but the present invention is not limited thereto.

The additive may be included in an amount of about 0.001 to 40 parts by weight, about 0.01 to 30 parts by weight, or about 0.1 to 20 parts by weight based on 100 parts by weight of the hardmask composition. By including in the above range, solubility can be improved without changing the optical properties of the hard mask composition.

According to another embodiment, there is provided an organic layer 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. there is.

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 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, 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 for example, may be applied 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

7-hydroxy-2H-chromen-2-one (10 g), 9H-fluoren-9-one (9H-fluoren-9-one, 7.56) in a 1L flask g) was added. Then, a solution of p-toluene sulfonic acid monohydrate (7.2 g) and 3-mercaptopropionic acid (3-mercaptopropionic acid, 4.454 g) in propylene glycol monomethyl ether acetate (PGMEA, 300 g) was added to the flask, and 100 The polymerization reaction was carried out by stirring at ℃, and the reaction was completed when the weight average molecular weight was 3,000 to 3,500. After completion of the polymerization reaction, the reactant was dissolved in ethyl acetate (Ethyl acetate, 500ml), washed with water sufficiently to remove the catalyst and metal impurities, and then the solvent was removed under reduced pressure. Thereafter, the pressure was reduced to 150° C. and 2 mmHg to remove moisture and unreacted monomers to obtain a polymer having a structural unit represented by Chemical Formula 1a. (MW: 4,000)

[Formula 1a]

Synthesis Example 2

7-(methoxymethoxy)-2H-chromen-2-one, 10 g instead of 7-hydroxy-2H-chromen-2-one (10 g) ) was used, and a polymer having a structural unit represented by Formula 1b was prepared in the same manner as in Synthesis Example 1. (Mw: 4,000)

[Formula 1b]

Synthesis Example 3

In a 1L flask, 7-hydroxy-2H-chromen-2-one (7-hydroxy-2H-chromen-2-one, 10g), 4,4'-(9H-fluorene-9,9-diyl) Diphenol (4,4'-(9H-fluorene-9,9-diyl)diphenol, 14.7 g) and 9H-fluoren-9-one (9H-fluoren-9-one, 15.12 g) were added. Thereafter, a solution of p-toluene sulfonic acid monohydrate (0.9 g) and 3-mercaptopropionic acid (3-mercaptopropionic acid, 10 g) in propylene glycol monomethyl ether acetate (PGMEA, 400 g) was added to the flask, and 100° C. The polymerization reaction was carried out by stirring in a , and the reaction was completed when the weight average molecular weight was 3,000 to 3,500. After completion of the polymerization reaction, the reactant was dissolved in ethyl acetate (Ethyl acetate, 500ml), washed with water sufficiently to remove the catalyst and metal impurities, and then the solvent was removed under reduced pressure. Thereafter, the pressure was reduced to 150° C. and 2 mmHg to remove moisture and unreacted monomers to have a structural unit represented by Formula 1a and a structural unit represented by Formula 1c, and a structural unit represented by Formula 1a and Formula 1c. A polymer having a molar ratio of structural units of 1:1 was obtained. (MW: 4,000)

[Formula 1a] [Formula 1c]

Synthesis Example 4

6,6'-(9H-) instead of 4,4'-(9H-fluorene-9,9-diyl)diphenol (4,4'-(9H-fluorene-9,9-diyl)diphenol, 10g) Synthesis Example 3 except that fluorene-9,9-diyl)dinaphthalen-1-ol (6,6'-(9H-fluorene-9,9-diyl)dinaphthalen-1-ol, 10 g) was used A polymer having a structural unit represented by Formula 1a and a structural unit represented by Formula 1d was prepared in the same manner as described above. The molar ratio between the structural unit represented by Formula 1a and the structural unit represented by Formula 1d included in the polymer is 1:1. (Mw: 4,000)

[Formula 1a] [Formula 1d]

Synthesis Example 5

4,4'-(9H-fluorene-9,9-diyl)diphenol (4,4'-(9H-fluorene-9,9-diyl)diphenol, 10g) instead of 1-naphthol (1-naphthol, 10g) was used, and a polymer having a structural unit represented by Formula 1a and a structural unit represented by Formula 1e was prepared in the same manner as in Synthesis Example 3. The molar ratio between the structural unit represented by Formula 1a and the structural unit represented by Formula 1e included in the polymer is 1:1. (Mw: 4,000)

[Formula 1a] [Formula 1e]

Synthesis Example 6

7-tert-butoxy-2H-chromen-2-one (7-tert-butoxy-2H-chromen-2-one, 10 g) instead of 7-hydroxy-2H-chromen-2-one (10 g) A polymer having a structural unit represented by Formula 1f was prepared in the same manner as in Synthesis Example 1, except that it was used. (Mw: 4,000)

[Formula 1f]

Comparative Synthesis Example 1

Put 7-hydroxy-2H-chromen-2-one (7-hydroxy-2H-chromen-2-one, 10g), formalin aqueous solution (37wt%, 1.26g) and oxalic acid (5g) in a flask, 100 ℃ The synthesis was carried out by stirring for 24 hours. After the reaction, the mixed solution was dissolved in methyl isobutyl ketone (500 ml), washed with water sufficiently to remove the catalyst and metal impurities, and then the solvent was removed under reduced pressure. Thereafter, the pressure was reduced to 150° C. and 2 mmHg to remove moisture and unreacted monomers to obtain a polymer having a structural unit represented by Chemical Formula A. (MW: 4,000)

[Formula A]

Comparative Synthesis Example 2

In a flask, 7-hydroxy-2H-chromen-2-one (7-hydroxy-2H-chromen-2-one, 10g), 1-naphthol (6.05g), aqueous formalin solution (37wt%, 2.38g) and oxalic acid (1 g) was added, and the mixture was stirred at 100° C. for 24 hours to proceed with the synthesis. After the reaction, the mixed solution was dissolved in methyl isobutyl ketone (500 ml), washed with water sufficiently to remove the catalyst and metal impurities, and then the solvent was removed under reduced pressure. Thereafter, the pressure was reduced to 150° C. and 2 mmHg to remove moisture and unreacted monomers to obtain a polymer having a structural unit represented by Formula A and a structural unit represented by Formula B. The molar ratio of the structural unit represented by Formula A and the structural unit represented by Formula B included in the polymer is 1:1. (MW: 4,000)

[Formula A] [Formula B]

Comparative Synthesis Example 3

In a flask, 7-hydroxy-2H-chromen-2-one (7-hydroxy-2H-chromen-2-one, 10g), 1,5-dihydroxynaphthalene (6.7g), aqueous formalin solution (37wt%, 2.5 g) and oxalic acid (2 g) were added, and the mixture was stirred at 100° C. for 24 hours to proceed with the synthesis. After the reaction, the mixed solution was dissolved in methyl isobutyl ketone (500 ml), washed with water sufficiently to remove the catalyst and metal impurities, and then the solvent was removed under reduced pressure. Thereafter, the pressure was reduced to 150° C. and 2 mmHg to remove moisture and unreacted monomers, and a polymer having a structural unit represented by Formula A and a structural unit represented by Formula C was obtained. The molar ratio of the structural unit represented by Formula A and the structural unit represented by Formula C included in the polymer is 1:1. (MW: 4,000)

[Formula A] [Formula C]

Formation of hard mask composition: Examples 1 to 6 and Comparative Examples 1 to 3

Each of the polymers obtained in Synthesis Examples 1 to 6 and Comparative Synthesis Examples 1 to 3 was weighed by 3.0 g, uniformly dissolved in 17 g of PGMEA, filtered through a 0.1 μm Teflon filter, and Examples 1 to 6 and Comparative Examples 1 to A hard mask composition of 3 was prepared.

Evaluation 1. Gap-Fill Characteristics and Planarization Characteristics

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

The hard mask compositions according to Examples 1 to 6 and Comparative Examples 1 to 3 were coated 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 characteristic (step difference measurement) is the average value (h ₁ ) of the thickness of the thin film measured at three arbitrary points where no pattern is formed on the substrate in FIG. 1 and the thickness of the thin film measured at three arbitrary points where the pattern is formed on the substrate The average value (h ₂ ) of the thickness was measured by 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.

polymer Gap-Fill Characteristics
(With or without Void) flattening properties
(step difference, Å) Comparative Example 1 Comparative Synthesis Example 1 no void 170 Comparative Example 2 Comparative Synthesis Example 2 no void 175 Comparative Example 3 Comparative Synthesis Example 3 no void 150 Example 1 Synthesis Example 1 no void 105 Example 2 Synthesis Example 2 no void 114 Example 3 Synthesis Example 3 no void 107 Example 4 Synthesis Example 4 no void 117 Example 5 Synthesis Example 5 no void 119 Example 6 Synthesis Example 6 no void 121

Referring to Table 1, it can be seen that the organic film formed from the hardmask compositions according to Examples 1 to 6 has superior planarization properties than the organic films formed from the hardmask compositions according to Comparative Examples 1 to 3.

Evaluation 2. Corrosion resistance

The hard mask compositions according to Examples 1 to 6 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 mixed 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 2.

composition polymer Bulk etch rate(Å/s) CHF ₃ /CF ₄ etch rate (Å/s) N ₂ /O ₂ etch rate (Å/s) Comparative Example 1 Comparative Synthesis Example 1 28.3 27.5 Comparative Example 2 Comparative Synthesis Example 2 31.5 26.0 Comparative Example 3 Comparative Synthesis Example 3 26.0 24.0 Example 1 Synthesis Example 1 24.3 22.4 Example 2 Synthesis Example 2 24.3 23.4 Example 3 Synthesis Example 3 23.2 21.9 Example 4 Synthesis Example 4 24.0 21.6 Example 5 Synthesis Example 5 23.6 21.5 Example 6 Synthesis Example 6 23.4 21.9

Referring to Table 2, it can be seen that the organic film prepared with the hard mask composition according to Examples 1 to 6 exhibits improved etch resistance compared to the organic film prepared with the hard mask composition according to Comparative Examples 1 to 3.

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

Claims (19)

A polymer comprising a first structural unit represented by the following formula (1), and
menstruum
A hard mask composition comprising:
[Formula 1]

In Formula 1,
A is a moiety represented by any one of Formulas 2-1 to 2-6,
B is a group represented by the following formula (3) or (4):
[Formula 2-1] [Formula 2-2] [Formula 2-3]

[Formula 2-4] [Formula 2-5] [Formula 2-6]

In Formulas 2-1 to 2-6,
R ^a is 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 C10 alkyl group, a 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 C3 to C30 cycloalkenyl group, substituted Or an unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heterocyclic group, or a combination thereof,
R ^b and R ^c are each independently hydrogen, halogen, amine group, cyano group, carboxyl group, substituted or unsubstituted C2 to C30 oxoalkyl group, substituted or unsubstituted C1 to C30 alkoxycarbonyl group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C1 to C30 alkenyl group, substituted or unsubstituted C1 to C30 alkynyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, A substituted or unsubstituted C3 to 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; ,
R ^d is hydrogen, halogen, carboxyl group, substituted or unsubstituted C2 to C30 oxoalkyl group, substituted or unsubstituted C1 to C30 alkoxycarbonyl group, substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C1 to C30 alkenyl group, substituted or unsubstituted C1 to C30 alkynyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted Or an unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heterocyclic group, or a combination thereof,
R ¹ and R ² are each independently hydrogen, halogen, hydroxyl group, amine group, cyano group, carboxyl group, substituted or unsubstituted C2 to C30 oxoalkyl group, substituted or unsubstituted C1 to C30 alkoxycarbonyl group, substituted or unsubstituted A substituted C1 to C20 alkylamine 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 alkyl group Nyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted A cyclic C3 to C30 heterocyclic group or a combination thereof,
l is an integer from 0 to 2:
[Formula 3] [Formula 4]

In Formulas 3 and 4,
Ar ¹ to Ar ⁴ are each independently a substituted or unsubstituted C6 to C30 aryl group,
Ar ¹ and Ar ² are each independently present or combine with each other to form a ring,
Ar ³ and Ar ⁴ each independently exist or combine with each other to form a ring,
L is a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C10 heteroalkylene group, or a combination thereof;
* is a point of connection with other moieties in the polymer of formula (1). delete In claim 1,
l is 1 or 2 of the hard mask composition. In claim 1,
R ^a is hydrogen, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, oxoethyl group, oxopropyl group, oxobutyl group, A hard mask composition comprising a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, an ethoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, a propoxymethyl group, a propoxyethyl group, a propoxypropyl group, or a combination thereof. In claim 1,
R ^b and R ^c are each independently hydrogen, F, Br, Cl, I, a cyano group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted iso-propyl group, substituted or unsubstituted n-butyl group, substituted or unsubstituted iso-butyl group, substituted or unsubstituted sec-butyl group, substituted or unsubstituted tert-butyl group, substituted or unsubstituted A hard mask composition comprising a oxoethyl group, a substituted or unsubstituted oxopropyl group, a substituted or unsubstituted oxobutyl group, or a combination thereof. In claim 1,
The moiety represented by any one of Chemical Formulas 2-1 to 2-6 is a hard mask composition selected from the following Group 1.
[Group 1]

delete delete In claim 1,
B is a hard mask composition selected from the following group 2:
[Group 2]

In group 2,
L is a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C10 heteroalkylene group, or a combination thereof,
R ³ to R ⁶ are each independently a hydroxyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a halogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or Unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof;
a to d are each independently an integer of 0 to 4,
m and n are each independently an integer of 1 to 3,
* is the point of connection with other moieties in the polymer of formula (1). In claim 1,
The hard mask composition wherein the polymer further comprises a second structural unit different from the first structural unit. In claim 10,
The second structural unit is a hard mask composition represented by the following Chemical Formula 5:
[Formula 5]

In Formula 5,
C is a substituted or unsubstituted C3 to C30 non-aromatic ring group, a substituted or unsubstituted C6 to C30 aromatic ring group, a substituted or unsubstituted heterocyclic group, a fused ring thereof, or a combination thereof,
D is a divalent organic group containing at least one quaternary carbon and is the same as or different from B above. In claim 11,
C is a hard mask composition comprising at least one polycyclic ring. In claim 11,
C is a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted acenaphthylenylene group, a substituted or unsubstituted acenaphthenylene group, a substituted or unsubstituted anthracenylene group, substituted or an unsubstituted phenanthrenylene group, a substituted or unsubstituted tetracenylene group, a substituted or unsubstituted triphenylenylene group, a substituted or unsubstituted chrysenylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted a biphenylene group, a substituted or unsubstituted benzophenanthrenylene group, a substituted or unsubstituted benzofluoranthenylene group, a substituted or unsubstituted pentacenylene group, a substituted or unsubstituted binaphthylene group, a substituted or unsubstituted benzopyrenylene group, substituted or unsubstituted perylenylene group, substituted or unsubstituted fluoranthenylene group, substituted or unsubstituted benzoperylenylene group, substituted or unsubstituted coronenylene group, substituted or unsubstituted A hard mask composition comprising a cyclic dibenzofluoranthenylene group or a group represented by the following formula (6):
[Formula 6]

In Formula 6,
Y ¹ and Y ² are each independently a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C6 to C30 aromatic ring group, a substituted or unsubstituted C6 to C30 heterocyclic group, or a combination thereof ego,
Ar ⁵ and Ar ⁶ are each independently a substituted or unsubstituted C6 to C30 aryl group,
* is the point of connection with other moieties in the polymer of formula (3). In claim 11,
C is a hydroxy group and a hard mask composition comprising at least one of a substituted or unsubstituted C1 to C30 alkoxy group. In claim 11,
D is a hardmask composition comprising at least one substituted or unsubstituted C6 to C30 aromatic ring. In claim 11,
D is a hard mask composition represented by the following Chemical Formula 7 or Chemical Formula 8:
[Formula 7] [Formula 8]

In Formulas 7 and 8,
Ar ¹ to Ar ⁴ are each independently a substituted or unsubstituted C6 to C30 aryl group,
Ar ¹ and Ar ² each independently exist or combine with each other to form a ring,
Ar ³ and Ar ⁴ are each independently present or combine with each other to form a ring,
L is a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C10 heteroalkylene group, or a combination thereof,
* is the point of connection with other moieties in the polymer of formula (1). 17. In claim 16,
D is a hard mask composition selected from the following group 3:
[Group 3]

In group 3,
L is a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C10 heteroalkylene group, or a combination thereof,
R ¹ to R ⁴ are each independently a hydroxyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a halogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or Unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof;
a to d are each independently an integer of 0 to 4,
m and n are each independently an integer of 1 to 3,
* is the point of connection with other moieties in the polymer of formula (1). delete 18. A method comprising: applying a hardmask composition according to any one of claims 1, 3 to 6, and 9 to 17 on the material layer and heat-treating to form a hardmask layer;
forming a photoresist layer over the hardmask layer;
exposing and developing the photoresist layer to form a photoresist pattern;
selectively removing the hardmask layer using the photoresist pattern and exposing a portion of the material layer; and
etching the exposed portion of the material layer;
A pattern forming method comprising a.

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