KR102296794B1 - Polymer, organic layer composition, and method of forming patterns - Google Patents

Abstract

A polymer comprising a structural unit represented by Formula 1, an aromatic ring-containing compound, and a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, or a nitrate group in the structure thereof A hard mask composition comprising an additive comprising at least one reel group, and a solvent; And it relates to a pattern forming method using the hard mask composition.
The definition of Chemical Formula 1 is as described in the specification.

Description

Organic film composition and pattern formation method {POLYMER, ORGANIC LAYER COMPOSITION, AND METHOD OF FORMING PATTERNS}

An organic film composition, and a method of forming a pattern using the organic film composition.

Recently, high-integration design according to the miniaturization and complexity of electronic devices is accelerating the development of more advanced materials and related processes. Accordingly, lithography using existing photoresists also requires new patterning materials and techniques. became

In the patterning process, an organic layer called a hardmask layer, which is a hard intermediate layer, may be formed in order to transfer the micropattern of the photoresist to the substrate to a sufficient depth without a collapse phenomenon.

The hard mask layer serves as an interlayer that transfers the micropattern of the photoresist to the material layer through a selective etching process. Therefore, the hardmask layer needs properties such as heat resistance and etch resistance to withstand multiple etching processes.

Meanwhile, it has been recently proposed to form the hard mask layer by a spin-on coating method instead of a chemical vapor deposition method. The spin-on coating method is not only easy to process, but also can improve gap-fill properties and planarization properties.

In general, heat resistance and etch resistance have a trade-off with spin-on characteristics, and an organic film material capable of satisfying all of these properties is required.

One embodiment provides an organic film composition that can be coated in a spin-on method and has excellent etch resistance.

Another embodiment provides a pattern forming method using the organic film composition.

According to one embodiment, as a polymer including a structural unit represented by the following Chemical Formula 1, an aromatic ring-containing compound, a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, or a substituted or unsubstituted acetylene group in the structure , an additive including at least one azide group, or a nitrile group, and an organic film composition including a solvent.

[Formula 1]

In Formula 1,

A is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof,

B is a divalent organic group,

At least one of A and B is substituted with a functional group comprising a moiety represented by the following formula (2):

[Formula 2]

In Formula 2,

Z is hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

* is the connection point.

The functional group including the moiety represented by Chemical Formula 2 may be represented by the following Chemical Formula 2′.

[Formula 2′]

In Formula 2',

W is O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,

Z is hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

a is 0 or 1,

b is an integer from 0 to 10,

* is the connection point.

The additive may be represented by the following formula (3).

[Formula 3]

In Formula 3,

k, m and n are each independently 0 or 1, but the sum of k, m and n is 2 or 3,

When k+m+n=3, X is -CH- or nitrogen (N),

When k+m+n=2, X is a direct bond, -(C _q H _2q )-, -(C _t R ^w _2t )-, oxygen (O), sulfur (S), -NH-, or -S (O ₂ )-, wherein q and t are each independently an integer of 1 to 5, and R ^w is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C7 to C20 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 hetero Cycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C1 to C4 alkyl ether group, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted C1 to C30 halo an alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof,

R, R′ and R″ are each independently a substituted or unsubstituted aromatic ring-containing group, wherein R, R′ or R″ are a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted and at least one acetylene group, azide group, or nitrile group.

The additive may be represented by the following Chemical Formula 4 or 5.

[Formula 4]

[Formula 5]

In Formulas 4 and 5,

X ¹ is -CH- or nitrogen (N),

X ² is a direct bond, -(C _q H _2q )-, -(C _t R ^w _2t )-, oxygen (O), sulfur (S), -NH- or -S(O ₂ )-, where q and t is each independently an integer of 1 to 5, and R ^w is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or Unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C7 to C20 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C1 to C4 alkyl ether group, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted C1 to C30 haloalkyl group, substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof,

R ¹ to R ⁵ are each independently an aromatic ring-containing group including at least one group represented by the following formula (6):

[Formula 6]

In Formula 6,

W is O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,

Y is a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, a nitrile group, or a combination thereof,

a is 0 or 1,

b is an integer from 0 to 10,

* is the connection point.

In Formulas 4 and 5, R ¹ to R ⁵ may be each independently represented by Formula 7 below.

[Formula 7]

In Formula 7,

R ^1a to R ^13a are each independently hydrogen, a hydroxyl group, a substituted or unsubstituted C1 to C10 alkyl group, or a group represented by Formula 6, wherein at least one of ^{R 1a} to R ^{13a is a group represented by Formula 6, and} ,

T ¹ and T ² are each independently O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof,

c and d are each independently an integer from 0 to 5,

* is the connection point.

In Formula 1, A may be a substituted or unsubstituted moiety selected from the following groups 1 and 2.

[Group 1]

[Group 2]

In group 2,

Z ¹ and Z ² are each independently NR ^d , O, S, Te or Se,

Z ³ and Z ⁴ are N,

R ^d and R ^e are each independently hydrogen, a hydroxy group, a methoxy group, an ethoxy group, a halogen atom, a halogen-containing group, a substituted or unsubstituted 1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or their It is a combination.

In Formula 1, A may include at least one substituted or unsubstituted aromatic or heteroaromatic ring.

B may be represented by any one of the following Chemical Formulas Z1 to Z4.

[Formula Z1]

[Formula Z2]

[Formula Z3]

[Formula Z4]

In the above formulas Z1 to Z4,

e and f are each independently 0 or 1,

g is an integer from 1 to 5,

Y ¹ to Y ⁴ are each independently any one of a substituted or unsubstituted moiety selected from the following group 3,

* is the connection point:

[Group 3]

In group 3,

M, M′ and M″ are each independently a substituted or unsubstituted C1 to C10 alkylene group, O, S, SO ₂ , CR ^f R ^g , NR ^h , or carbonyl, wherein R ^f to R ^h are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof;

L ¹ is a substituted or unsubstituted C6 to C50 arylene group, a substituted or unsubstituted C1 to C10 alkylene oxide-containing group, or a combination thereof,

r is an integer from 0 to 10,

s is an integer from 0 to 10,

k is an integer from 0 to 3.

The polymer may further include a structural unit represented by the following Chemical Formula 8.

[Formula 8]

In the formula (8),

X ⁰ is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof,

L ⁰ is a divalent organic group,

* is the connection point.

In Formula 8, X ⁰ may be a substituted or unsubstituted moiety selected from the following groups 1 and 2.

[Group 1]

[Group 2]

In group 2,

Z ¹ and Z ² are each independently NR ^d , O, S, Te or Se,

Z ³ and Z ⁴ are N,

R ^d and R ^e are each independently hydrogen, a hydroxy group, a methoxy group, an ethoxy group, a halogen atom, a halogen-containing group, a substituted or unsubstituted 1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or their It is a combination.

The polymer may include at least one oxygen atom in its structural unit.

Formula 2 may be represented by Formula 2' below.

[Formula 2′]

In Formula 2',

W is O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,

a is 0 or 1,

* is the connection point.

The additive may be represented by any one of the following Chemical Formulas Y1 to Y4.

[Formula Y1]

[Formula Y2]

[Formula Y3]

[Formula Y4]

In the above formulas Y1 to Y4,

T ³ and T ⁴ are each independently O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof,

R ^x to R ^y are each independently hydrogen, a halogen atom, a halogen-containing group, or a substituted or unsubstituted C1 to C20 alkyl group,

R ³³ to R ⁵⁵ are each independently a group represented by the following formula (6):

[Formula 6]

In Formula 6,

W is O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,

Y is a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, a nitrile group, or a combination thereof,

a is 0 or 1,

b is an integer from 0 to 10,

* is the connection point.

The additive may have a molecular weight of 150 to 50,000.

The polymer may have a weight average molecular weight of 500 to 200,000.

The additive may be included in an amount of 5 wt% to 50 wt% based on the total content of the organic film composition.

According to another embodiment, providing a material layer on a substrate, applying the above-described organic film composition on the material layer, heat-treating the organic film composition to form a hardmask layer, silicon on the hardmask layer forming a thin film containing layer, forming a photoresist layer on the silicon-containing thin film layer; exposing and developing the photoresist layer to form a photoresist pattern; There is provided a method of forming a pattern comprising selectively removing a hardmask layer and exposing a portion of the material layer, and etching the exposed portion of the material layer.

The step of applying the organic film composition may be performed by a spin-on coating method.

The heat treatment may include a first heat treatment performed at 50 to 250° C., and a second heat treatment performed at 200 to 500° C. following the first heat treatment.

The method may further include forming a bottom anti-reflective layer (BARC) before forming the photoresist layer.

Provided is an organic film composition capable of being coated in a spin-on method and having excellent etch resistance by including a predetermined polymer and a predetermined additive. The organic film prepared from the organic film composition is excellent in both film density and film flatness.

1 is a view for explaining a method for evaluating planarization characteristics (step difference characteristics),
FIG. 2 is a view for explaining a method for evaluating a thickness uniformity 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.

Unless otherwise defined herein, 'substituted' means that a hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxyl group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amino group Dino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C2 to C20 heteroaryl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 It means substituted with a substituent selected from a to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, and combinations thereof.

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

Hereinafter, an organic film composition according to an embodiment will be described.

The organic film composition according to an embodiment includes a polymer including a structural unit represented by the following Chemical Formula 1, a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, and a substituted or unsubstituted acetylene group as an aromatic ring-containing compound. , an additive including at least one azide group, or a nitrile group, and an organic film composition including a solvent.

[Formula 1]

In Formula 1,

A is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof,

B is a divalent organic group,

At least one of A and B is substituted with a functional group comprising a moiety represented by the following formula (2):

[Formula 2]

In Formula 2,

Z is hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

* is the connection point.

The organic film composition includes a polymer having a predetermined structure and an additive having a predetermined structure. First, the polymer will be described.

The polymer includes one or more structural units represented by Chemical Formula 1, and includes an aromatic ring group-containing portion represented by A and a linking group portion represented by B in the structural unit.

For example, A may be a substituted or unsubstituted aromatic ring-containing group, for example, may include a substituted or unsubstituted moiety selected from the following group 1, but is not limited thereto.

[Group 1]

As another example, A may be a substituted or unsubstituted heteroaromatic ring-containing group, for example, may include a substituted or unsubstituted moiety selected from the following group 2, but is not limited thereto.

[Group 2]

In group 2,

Z ¹ and Z ² are each independently NR ^d , O, S, Te or Se,

Z ³ and Z ⁴ are N,

R ^d and R ^e are each independently hydrogen, a hydroxy group, a methoxy group, an ethoxy group, a halogen atom, a halogen-containing group, a substituted or unsubstituted 1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or their It is a combination.

As another example, A may be a combination of a substituted or unsubstituted aromatic ring-containing group and a substituted or unsubstituted heteroaromatic ring-containing group. For example, in Formula 1, A represents two or more substituted or It may include an unsubstituted benzene ring, for example, it may include 2 to 6 substituted or unsubstituted benzene rings. Here, the benzene ring may be substituted with at least one hydroxyl group.

B representing the linking group in Formula 1 may be a divalent organic linear group, a divalent organic cyclic group, or a combination thereof. For example, B may be represented by any one of the following Chemical Formulas Z1 to Z4, but is not limited thereto.

[Formula Z1]

[Formula Z2]

[Formula Z3]

[Formula Z4]

In the above formulas Z1 to Z4,

e and f are each independently 0 or 1,

g is an integer from 1 to 5,

Y ¹ to Y ⁴ are each independently any one of a substituted or unsubstituted moiety selected from the following group 3,

* is the connection point:

[Group 3]

In group 3,

M, M′ and M″ are each independently a substituted or unsubstituted C1 to C10 alkylene group, O, S, SO ₂ , CR ^f R ^g , NR ^h , or carbonyl, wherein R ^f to R ^h are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof;

L ¹ is a substituted or unsubstituted C6 to C50 arylene group, a substituted or unsubstituted C1 to C10 alkylene oxide-containing group, or a combination thereof,

r is an integer from 0 to 10,

s is an integer from 3 to 10,

k is an integer from 1 to 3.

Meanwhile, in Formula 1, at least one of A and B is substituted with an acetylene-containing group represented by Formula 2 above. For example, the aromatic ring-containing group or heteroaromatic ring-containing group represented by A is substituted by an acetylene-containing group, the linking group represented by B is substituted by an acetylene-containing group, or both the A and B portions contain acetylene may be substituted by a group. At this time, the number of substitutions is not specifically limited.

For example, the functional group including the moiety represented by Chemical Formula 2 may be a group represented by the following Chemical Formula 2', but is not limited thereto.

[Formula 2′]

In Formula 2',

W is O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,

Z is hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

a is 0 or 1,

b is an integer from 0 to 10,

* is the connection point.

For example, the functional group including the moiety represented by Chemical Formula 2 may be a group represented by the following Chemical Formula 2″, but is not limited thereto.

[Formula 2″]

In the above formula 2″,

W is O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,

a is 0 or 1,

* is the connection point.

For example, the polymer may include at least one oxygen atom in its structure.

The polymer can secure corrosion resistance by including the aromatic ring-containing group or heteroaromatic ring-containing group represented by A in its structural unit, and can secure flexibility by including the organic group represented by B have. In addition, by introducing at least one acetylene into A or B, when the polymer is cured, the acetylene forms a ring structure, thereby further improving the etch resistance of the polymer. Accordingly, the organic film formed using the polymer has excellent film density. In addition, the organic film formed by using the polymer can also secure thickness uniformity (uniformity).

The polymer may further include, for example, a structural unit represented by the following Chemical Formula 8.

[Formula 8]

In the formula (8),

X ⁰ is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof,

L ⁰ is a divalent organic group,

* is the connection point.

In Formula 8, X may be a substituted or unsubstituted moiety selected from Groups 1 and 2, and L ⁰ is a linking group as described in B of Formula 1 above. However, the structural unit represented by Formula 8 does not necessarily include an acetylene functional group, unlike the structural unit represented by Formula 1 above.

Hereinafter, additives included in the organic film composition will be described.

The additive includes at least one substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, or a nitrile group as the aromatic ring-containing compound as described above.

For example, the additive may be represented by Formula 3 below.

[Formula 3]

In Formula 3,

k, m and n are each independently 0 or 1, but the sum of k, m and n is 2 or 3,

When k+m+n=3, X is -CH- or nitrogen (N),

When k+m+n=2, X is a direct bond, -(C _q H _2q )-, -(C _t R ^w _2t )-, oxygen (O), sulfur (S), -NH-, or -S (O ₂ )-, wherein q and t are each independently an integer of 1 to 5, and R ^w is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C7 to C20 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 hetero Cycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C1 to C4 alkyl ether group, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted C1 to C30 halo an alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof,

R, R′ and R″ are each independently a substituted or unsubstituted aromatic ring-containing group, wherein R, R′ or R″ are a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted and at least one acetylene group, azide group, or nitrile group. For example, R, R′ or R″ is, for example, one or two substituted or unsubstituted amine groups, substituted or unsubstituted vinyl groups, substituted or unsubstituted acetylene groups, azide groups, or nitrile groups substituted it may have been

The additive represented by Formula 3 has a structure in which two or three aromatic ring-containing groups are connected to the core represented by X. When the additive represented by Formula 3 has three substituents, the core is carbon or nitrogen, and when the additive has two substituents, the core is a direct bond, carbon, oxygen, sulfur, or -S(O ₂ )-.

For example, when the additive has a structure in which three aromatic ring-containing groups are connected to the core, it may be represented by the following Chemical Formula 4, and when the additive has a structure in which two aromatic ring-containing groups are connected to the core, it is represented by the following Chemical Formula 3 can be

[Formula 4]

[Formula 5]

In Formulas 4 and 5,

X ¹ is -CH- or nitrogen (N),

X ² is a direct bond, -(C _q H _2q )-, -(C _t R ^w _2t )-, oxygen (O), sulfur (S), -NH- or -S(O ₂ )-, where q and t is each independently an integer of 1 to 5, and R ^w is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or Unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C7 to C20 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C1 to C4 alkyl ether group, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted C1 to C30 haloalkyl group, substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof,

R ¹ to R ⁵ are each independently an aromatic ring-containing group including at least one group represented by the following formula (6) in its structure:

[Formula 6]

In Formula 6,

W is O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,

Y is a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, a nitrile group, or a combination thereof,

a is 0 or 1,

b is an integer from 0 to 10,

* is the connection point.

For example, in Formulas 4 and 5, R ¹ to R ⁵ may each independently be represented by Formula 7 below, but is not limited thereto.

[Formula 7]

In Formula 7,

R ^1a to R ^13a are each independently hydrogen, a hydroxyl group, a substituted or unsubstituted C1 to C10 alkyl group, or a group represented by Formula 6, wherein at least one of ^{R 1a} to R ^{13a is a group represented by Formula 6, and} ,

T ¹ and T ² are each independently O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof,

c and d are each independently an integer from 0 to 5,

* is the connection point.

For example, the additive may be represented by any one of the following Chemical Formulas Y1 to Y4, but is not limited thereto.

[Formula Y1]

[Formula Y2]

[Formula Y3]

[Formula Y4]

In the above formulas Y1 to Y4,

T ³ and T ⁴ are each independently O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof,

R ^x to R ^y are each independently hydrogen, a halogen atom, a halogen-containing group, or a substituted or unsubstituted C1 to C20 alkyl group,

R ³³ to R ⁵⁵ are each independently a group represented by Formula 6 above.

For example, the additive may include at least one oxygen atom or nitrogen atom in its structure, for example, 1 to 3 oxygen atoms, or 1 nitrogen atom, but is not limited thereto.

The additive may act, for example, as a crosslinking agent.

As such, the organic film composition includes a polymer into which acetylene is introduced, and an aromatic ring-containing compound, including a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, or a nitrile group. an additive comprising at least one group.

As such, when the polymer and the additive are used simultaneously, the carbon content is relatively increased as the acetylene functional group introduced into the polymer reacts with an amine, acetylene, azide, etc. introduced into the additive during curing to form a ring. Accordingly, the etch resistance may be improved and the etch selectivity may also be improved. Accordingly, the organic film formed by using the organic film composition has excellent film density and pattern formability.

For example, the polymer may have a weight average molecular weight of about 500 to 200,000. By having a weight average molecular weight in the above range, it can be optimized by controlling the carbon content and solubility in a solvent of the organic film composition (eg, hard mask composition) including the polymer. Also, for example, the additive may have a molecular weight of about 150 to 50,000.

The solvent included in the organic film composition is not particularly limited as long as it has sufficient solubility or dispersibility for the polymer, for example, propylene glycol, propylene glycol diacetate, methoxy propanediol, diethylene glycol, diethylene glycol butyl ether, Tri(ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetone It may include at least one selected from amide, methylpyrrolidone, methylpyrrolidinone, acetylacetone, and ethyl 3-ethoxypropionate.

The polymer may be included in an amount of about 0.1 to 50% by weight based on the total content of the organic film composition. By including the polymer in the above range, the thickness, surface roughness, and planarization degree of the organic layer can be controlled.

The additive may be included in an amount of about 0.1 to 50% by weight based on the total content of the organic film composition, for example, about 5 to 50% by weight based on the total content of the organic film composition. When the additive is included in the above range, it is possible to improve the initial flatness of the prepared organic film.

The organic film 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, an alkylbenzenesulfonic acid salt, 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 or 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 based on 100 parts by weight of the organic film composition. By including in the above range, solubility can be improved without changing the optical properties of the organic film composition.

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

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

A pattern forming method according to an exemplary embodiment includes providing a material layer on a substrate, applying an organic film composition including the above-described polymer and a solvent on the material layer, and heat-treating the organic film composition to form a hard mask layer forming a silicon-containing thin film layer on the hardmask layer, forming a photoresist layer on the silicon-containing thin film layer, exposing and developing the photoresist layer to form a photoresist pattern, the photoresist pattern selectively removing the silicon-containing thin film layer and the hardmask layer using

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 organic film composition is the same as described above, and may be prepared in a solution form and applied by a spin-on 　 coating method. At this time, the coating thickness of the organic film composition is not particularly limited, but may be applied, for example, to a thickness of about 50 to 10,000 Å.

The heat treatment of the organic film composition may be performed, for example, at about 100 to 500° C. for about 10 seconds to 1 hour.

For example, the heat treatment may include a first heat treatment performed at 50 to 250° C., and a second heat treatment performed at 200 to 500° C. following the first heat treatment.

The silicon-containing thin film layer may be formed of a material such as SiCN, SiOC, SiON, SiOCN, SiC and/or SiN.

Also, 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.

The exposing of the photoresist layer may be performed using, for example, ArF, KrF, or EUV. In addition, after exposure, the heat treatment process may be performed at about 100°C to 500°C.

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 the like, and may be applied as, for example, various patterns in a semiconductor integrated circuit device.

The embodiments of the present invention described above will be described in more detail through the following examples. However, the following examples are for illustrative purposes only and do not limit the scope of the present invention.

polymer synthesis

polymerization example One

Resin polymerization

In a flask, naphthalen-1-ol (14.2 g), paraformaldehyde (6 g), p-toluene sulfonic acid hydrate (1.9 g) and propylene glycol monomethyl ether acetate (PGMEA) (33 g) were added, and then, 80° C. The polymerization reaction was carried out by stirring. During the reaction, the molecular weight was confirmed by GPC and the reaction was completed when the weight average molecular weight was 2,000 to 3,500. After the polymerization reaction was completed, the reactant was slowly cooled to room temperature, 100 g of hexane was added, propylene glycol monomethyl ether acetate was extracted, and then removed using distilled water and methanol to obtain a polymer containing a structural unit represented by the following formula 1a'. (Weight average molecular weight (Mw) = 3,000).

[Formula 1a']

acetylation ( Acetylation _) reaction

In a flask, a polymer (10 g) containing the structural unit of Formula 1a' is dissolved in DMF (40 mL) and stirred in ice water. After 10 minutes of stirring, NaH (1 g) was slowly added dropwise, stirred in ice water for 30 minutes, and then propargyl bromide (80% in tolutene) (5.5 g) was added dropwise. When the reaction is complete, dilute the reaction solution by adding EtOAc (100 mL), and then wash several times with water to remove DMF. When DMF was completely removed, the remaining EtOAc was removed to obtain polymer 1a.

polymerization example 2

Resin polymerization

naphthalen-1-ol (10 g), 1,3-bis(4-(methoxymethyl)phenoxy)benzene (24.3 g), propylene glycol monomethyl ether acetate (PGMEA) (64 g) and diethylsulfate ( 0.3 g) was obtained at 100° C. using the same method as the resin polymerization of Synthesis Example 1 to obtain a polymer including a structural unit represented by Formula 1b′. (Weight average molecular weight (Mw) = 3,500).

[Formula 1b']

acetylation ( Acetylation _) reaction

The same method of Synthesis Example 1 using a polymer (10 g), DMF (50 mL), NaH (0.6 g), and propargyl bromide (80% in tolutene) (2.6 g) containing the structural unit of Formula 1b′ was acetylated to obtain polymer 1b.

polymerization example 3

Resin polymerization

pyrene-1,6-diol (23g), 1,4-bis(methoxymethyl)benzene (25g), propylene glycol monomethyl ether acetate (PGMEA) (48g) and diethylsulfate (0.7g) were added The polymerization reaction was carried out by stirring at 100°C. The reaction was completed when the weight average molecular weight was 2,000 to 3,500. After the polymerization reaction was completed, the reactant was slowly cooled to room temperature, the reactant was added to 20 g of distilled water and 200 g of methanol, stirred vigorously, and then left still. The supernatant was removed and the precipitate was dissolved in 40 g of propylene glycol monomethyl ether acetate (PGMEA), followed by strong stirring using 160 g of methanol and 160 g of water, and then left still (1st). At this time, the obtained supernatant was removed again, and the precipitate was dissolved in 40 g of propylene glycol monomethyl ether acetate (PGMEA) (secondary). The first and second steps were referred to as a one-time purification process, and this purification process was performed three times in total. After the purified polymer was dissolved in 40 g of propylene glycol monomethyl ether acetate (PGMEA), methanol and distilled water remaining in the solution were removed under reduced pressure to obtain a polymer including a structural unit represented by Formula 1c'. (Weight average molecular weight (Mw) = 2,600).

[Formula 1c′]

acetylation ( Acetylation _) reaction

In the same manner as in Synthesis Example 1 using a polymer (10 g), DMF (40 mL), NaH (0.6 g) and propargyl bromide (80% in tolutene) (2.2 g) containing the structural unit of Formula 1c′ Acetylation gave polymer 1c.

polymerization example 4

Resin polymerization

4,4'-(9H-fluorene-9,9-diyl)diphenol (4,4'-(9H-fluorene-9,9-diyl)diphenol) (14 g), 1,4-bis(methyl Synthesis example of toxymethyl)benzene (1,3-bis(methoxymethyl)benzene) (6.6 g), propylene glycol monomethyl ether acetate (PGMEA) (20 g) and diethylsulfate (0.25 g) at 100°C A polymer including a structural unit represented by the formula 1d' was obtained by using the same method as the resin polymerization of 1. (Weight average molecular weight (Mw) = 3,700).

[Formula 1d′]

acetylation ( Acetylation _) reaction

The same method of Synthesis Example 1 using a polymer (9 g), DMF (45 mL), NaH (0.9 g), and propargyl bromide (80% in tolutene) (3.5 g) containing the structural unit of formula 1d' was acetylated to obtain polymer 1d.

polymerization example 5

Resin polymerization

6,6'-(9H-fluorene-9,9-diyl)dinaphthalen-2-ol (18 g), 1,3-bis(methoxymethyl)benzene (1,3-bis(methoxymethyl)benzene) (6.6 g), propylene glycol monomethyl ether acetate (PGMEA) (25 g) and diethylsulfate (0.2 g) at 110 ° C. Using the same method as the resin polymerization of Synthesis Example 1, the structure represented by the formula 1e' A polymer containing units was obtained. (Weight average molecular weight (Mw) = 3,800).

[Formula 1e′]

acetylation ( Acetylation _) reaction

In the same manner as in Synthesis Example 1 using a polymer (10 g), DMF (45 mL), NaH (0.7 g) and propargyl bromide (80% in tolutene) (2.5 g) containing the structural unit of Formula 1e′ Acetylation gave polymer 1e.

polymerization example 6

4,4'-(9H-fluorene-9,9-diyl)dibenzene-1,2-dioll (38 g), 5-hydroxy-1-naphthaldehyde (17 g) Propylene glycol monomethyl ether acetate (PGMEA) (129 g) and diethylsulfate (0.3 g), using the same method as the resin polymerization of Synthesis Example 1 at 100° C., to obtain a polymer including a structural unit represented by Formula 1f′. (Mw: 3,200).

[Formula 1f′]

acetylation ( Acetylation _) reaction

In the same manner as in Synthesis Example 1 using a polymer (10 g), DMF (50 mL), NaH (1.9 g) and propargyl bromide (80% in tolutene) (5.1 g) containing the structural unit of Formula 1f′ Acetylation gave polymer 1f.

polymerization example 7

Resin polymerization

5,5'-(9H-fluorene-9,9-diyl)dibenzene-1,2,3-triol (20 g), 4,4'-oxybis((methoxymethyl)benzene) (26 g), 1H-indol (6 g), propylene glycol monomethyl ether acetate (PGMEA) (123 g) and diethylsulfate

(0.5 g) was subjected to the same synthesis process as in Synthesis Example 1 at 100° C. to obtain a polymer including a structural unit represented by Chemical Formula 1g' (Mw: 3,300).

[Formula 1g′]

acetylation ( Acetylation _) reaction

In the same manner as in Synthesis Example 1 using a polymer (10 g), DMF (50 mL), NaH (1.3 g) and propargyl bromide (80% in tolutene) (3.7 g) containing the structural unit of Formula 1g ′ It was acetylated to obtain 1 g of a polymer.

polymerization example 8

Resin polymerization

naphthalen-1-ol (7.2 g), 1H-indol (5.9 g), 4-hydroxy-1-naphthaldehyde (17 g), propylene glycol monomethyl ether acetate (PGMEA) (129 g) and diethylsulfate (0.3 g) was subjected to the same synthesis process as in Synthesis Example 1 to obtain a polymer including a structural unit represented by Formula 1h' (Mw: 3,700).

[Formula 1h']

acetylation ( Acetylation _) reaction

In the same manner as in Synthesis Example 1 using a polymer (12 g), DMF (55 mL), NaH (1 g) and propargyl bromide (80% in tolutene) (3.4 g) containing the structural unit of Formula 1h' By acetylation, polymer 1h was obtained.

polymerization example 9

Resin polymerization

In a flask, carbazole (16 g), 5-hydroxy-1-naphthaldehyde (17 g), p-Toluenesulfonic acid monohydrate (1.9 g), and 1,4-dioxane (32 g) were added. Then, the mixture was stirred at 100 °C. A sample was taken at intervals of 1 hour from the polymerization product thus obtained, and the reaction was completed when the weight average molecular weight of the sample was 2000 to 3000. When the reaction was completed, 100 g of hexane was added to extract 1,4-dioxane, methanol was added to filter the precipitate formed, and the remaining monomer was removed using methanol to obtain a polymer represented by the following formula 1i' (weight average molecular weight) (Mw) = 2,600).

[Formula 1i']

acetylation ( Acetylation _) reaction

In the same manner as in Synthesis Example 1 using a polymer (10 g), DMF (55 mL), NaH (0.65 g) and propargyl bromide (80% in tolutene) (1.7 g) containing the structural unit of Formula 1i' Acetylation gave polymer 1i.

polymerization example 10

1H-indol-5-ol (13 g), 9-Fluorenone (18 g), p-Toluenesulfonic acid monohydrate (9.5 g), 1,4-dioxane in a flask (91 g) was subjected to the same synthesis process as in Synthesis Example 9 to obtain a polymer including a structural unit represented by Formula 1j' (Mw: 2,900).

[Formula 1j']

acetylation ( Acetylation _) reaction

In the same manner as in Synthesis Example 1 using a polymer (10 g), DMF (50 mL), NaH (0.7 g) and propargyl bromide (80% in tolutene) (1.8 g) containing the structural unit of Formula 1j′ Acetylation gave polymer 1j.

comparison polymerization example One

naphthalen-1-ol (14 g), 1,4-bis(methoxymethyl)benzene (17g), propylene glycol monomethyl ether acetate (PGMEA) (64 g) and diethylsulfate (0.3 g) at 100°C A polymer (Polymer 1k) including a structural unit represented by Formula 1k was obtained by using the same method as the resin polymerization of Synthesis Example 1. (weight average molecular weight (Mw) = 3,000).

[Formula 1k]

additive synthesis

Synthesis example One

In a 500ml round flask, stir bar, 4,4'-(4,4'-(propane-2,2-diyl)bis(4,1-phenylene))bis(oxy)dianiline (10 g), water (60 ml ), crushed ice (15 g) and stirred in ice water for 10 minutes, conc. HCl (20 ml) is slowly added dropwise. Here, NaNO2 dissolved in water (15 ml) is added dropwise for about 10 minutes using a dropping funnel. After stirring for 20 minutes, KI dissolved in water (15 ml) is slowly added dropwise using a dropping funnel. After stirring for 1 hour and 30 minutes, check TLC and when the reaction is complete, the filtered solid is dissolved in EA and washed with _{NaHSO 3 and water.} The solvent of the organic layer was removed to obtain 8 g of an additive represented by the following Chemical Formula 2a.

[Formula 2a]

Synthesis example 2

4,4'-(biphenyl-4,4'-diylbis(oxy))dianiline (9 g), NaN0 ₂ (4 g), NaN ₃ (4.7 g), conc. Using the same method as in Synthesis Example 1 using HCl (15 ml), an additive represented by the following Chemical Formula 2b was obtained.

[Formula 2b]

Synthesis example 3

4,4'-(biphenyl-4,4'-diylbis(oxy))dianiline (9 g), NaN0 ₂ (4 g), NaN ₃ (4.7 g), conc. An additive represented by the following Chemical Formula 2c was obtained by using the same method as in Synthesis Example 1 using HCl (15 ml).

[Formula 2c]

Synthesis example 4

4,4'-(4,4'-(propane-2,2-diyl)bis(4,1-phenylene))bis(oxy)dianiline (10 g), NaN02 (4 g), KI (12.1 g) , conc. A solid intermediate (7.7 g) was obtained in the same manner as in Synthesis Example 1 using HCl (20 ml). The obtained intermediate (5.7 g) was dissolved in tetrahydrofuran (40 mL), and then i pro-MgBr 2.9M (9 mL) was slowly added dropwise at -40°C. After 30 minutes, dried DMF (10 mL) was slowly added dropwise, followed by stirring at room temperature for 2 hours. 100 mL of ethyl acetate was added dropwise to the resulting reaction solution, and then washed several times with water. EtOAc was removed to obtain Chemical Formula 2d'.

[Formula 2d′]

The obtained compound 2d' (4.3 g) was dissolved in tetrahydrofuran (50 mL) and stirred in ice water. Lithium aluminum hydride (0.75 g) was slowly added dropwise to the prepared solution and stirred in ice water for 2 hours. When the reaction is complete, a 10% aqueous solution of NaOH (0.75 g), H 2 O (1.5 g), and 10% NaOH (2.3 g) are slowly added dropwise in order. After sufficiently stirring at room temperature, the resulting filtrate was filtered under reduced pressure to remove THF, dissolved in EtOAc (100 mL), and washed several times with water. After the remaining organic solvent was completely removed, an intermediate 2d was obtained. The obtained 2d was dissolved in DMF (20 mL), stirred in ice water for 10 minutes, and then NaH (60%) (1 g) was slowly added dropwise. After stirring in ice water for 30 minutes, propargyl bromide (80% in tolutene) (4 mL) is added dropwise. When the reaction is complete, dilute the reaction solution by adding EtOAc (100 mL), and then wash several times with water to remove DMF. When DMF was completely removed, the remaining EtOAc was removed to obtain an additive (4.5 g) represented by Formula 2d.

[Formula 2d]

Synthesis example 5

4,4'-(1,3-phenylenebis(oxy))dianiline (210 g), NaN0 ₂ (5.7 g), NaCN (4.7 g), conc. An additive represented by the following Chemical Formula 2e was obtained using the same method as in Synthesis Example 1 using HCl (15 ml).

[Formula 2e]

Synthesis example 6

Prepare an additive represented by the following Chemical Formula 2f (manufactured by TCI, product name: 2,2-bis[4-(4-aminophenoxy)-phenyl]propanen).

[Formula 2f]

Preparation of hard mask composition

Example 1 to 14; comparative example 1 to 2

The polymer and additives were dissolved in a propylene glycol monomethyl ether acetate (PGMEA) solvent and filtered to prepare a hard mask composition.

Compositions of polymers and additives are shown in Table 1 below.

polymer additive Example 1 polymer 1a Formula 2a Example 2 polymer 1b Formula 2a Example 3 polymer 1c Formula 2a Example 4 polymer 1d Formula 2b Example 5 polymer 1e Formula 2b Example 6 polymer 1f Formula 2a Example 7 1 g of polymer Formula 2a Example 8 polymer 1h Formula 2c Example 9 Polymer 1i Formula 2a Example 10 polymer 1j Formula 2e Example 11 polymer 1d Formula 2f Example 12 polymer 1f Formula 2b Example 13 1 g of polymer Formula 2c Example 14 Polymer 1i Formula 2d Comparative Example 1 polymer 1k - Comparative Example 2 polymer 1a - Comparative Example 3 polymer 1b -

Evaluation 1: Flattening Characteristics

After spin-on coating the composition described in Table 1 on a patterned silicon wafer (trench width 10 μm, trench depth 100 nm) to form a thin film through a bake process, the cross-section was observed using V-SEM equipment.

The content of solids in the hard mask composition was adjusted so that the thickness of the composition on the bare wafer was 2000 Å after primary heat treatment at 180° C. for 120 seconds and then secondary heat treatment at 400° C. for 120 seconds. The hardmask composition was spin-on coated, and then the thin film was subjected to a primary heat treatment at 180° C. for 120 seconds, followed by a second heat treatment at 400° C. for 120 seconds.

The planarization characteristic is observed by measuring the difference (ie, step difference) in the film thickness of the resist underlayer film in the portion with the hole and the portion without the hole. 1 is an enlarged cross-sectional view illustrating an arbitrary pattern on a silicon wafer coated with a coating solution. The thickness indicated by the arrow in FIG. 1 corresponds to the step.

The planarization characteristic is excellent as the difference (step difference) in the film thickness between the patterned portion and the non-patterned portion is not large. The results are as shown in Table 2.

Step (nm) Example 1 26 nm Example 2 13 nm Example 3 25 nm Example 4 18 nm Example 5 27 nm Example 6 28 nm Example 7 16 nm Comparative Example 1 33 nm Comparative Example 2 39 nm

Referring to Table 2, it can be seen that the thin films formed from the hard mask compositions according to Examples 2 to 7 have a superior degree of planarization compared to the thin films formed from the hard mask compositions according to Comparative Examples 1 and 2.

Evaluation 2: Thickness Uniformity

After spin-on coating the hard mask compositions according to Examples 7 to 14 and Comparative Examples 1 and 3 on a silicon wafer on a 12-inch silicon wafer, and then first heat-treating the thin film at 180° C. for 120 seconds. Secondary heat treatment was performed at 400° C. for 120 seconds. The solid content was adjusted so that the thickness of the thin film after the secondary heat treatment was completed was 2,000 Å.

The uniformity was calculated by Equation 2 below after selecting 19 points as shown in FIG. 2, measuring the thin film thickness at these 19 points, respectively. The thickness of the thin film was measured using K-MAC equipment. The results are as shown in Table 3.

[Formula 2]

Uniformity (%) = (highest thickness of thin film at 19 points - lowest thickness of thin film at 19 points) /(average thickness of thin film at 19 points) X 100

Uniformity (%) Example 7 < 2% Example 8 < 2% Example 9 < 2% Example 10 < 2% Example 11 < 2% Example 12 < 2% Example 13 < 2% Example 14 < 2% Comparative Example 1 7% Comparative Example 3 6%

Referring to Table 3, it can be seen that the thin films formed from the hard mask compositions according to Examples 7 to 14 have superior thickness uniformity compared to the thin films formed from the hard mask compositions according to Comparative Examples 1 and 3.

Rating 3: coatability

On a silicon wafer, the hard mask compositions according to Examples 1 to 8 and Comparative Examples 2 and 3 were spin-on coated with the hard mask composition, followed by primary heat treatment at 180° C. for 120 seconds, followed by secondary heat treatment at 400° C. for 120 seconds. A thin film was formed by heat treatment. The solid content was adjusted so that the thickness of the thin film after the secondary heat treatment was completed was 2,000 Å.

The surface of the prepared thin film was observed with an electron microscope. The results are shown in Table 4 below.

coatability Example 1 Good Example 2 Good Example 3 Good Example 4 Good Example 5 Good Example 6 Good Example 7 Good Example 8 Good Comparative Example 2 error Comparative Example 3 error

As shown in Table 4, the thin films formed from the hard mask compositions according to Examples 1 to 8 were excellent in coating properties compared to the thin films formed from the hard mask compositions according to Comparative Examples 2 and 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 belongs to the scope of the invention.

Claims (20)

A polymer comprising a structural unit represented by the following formula (1), an aromatic ring-containing compound, a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, or an additive comprising at least one nitrile group, and
menstruum
containing
Hard mask composition:
[Formula 1]

In Formula 1,
A is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof,
B is a divalent organic group,
At least one of A and B is substituted with a functional group comprising a moiety represented by the following formula (2):
[Formula 2]

In Formula 2,
Z is hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,
* is the connection point,
In the above 'substituted or unsubstituted', substitution means that a hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C2 to C20 heteroaryl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalke It means substituted with a substituent selected from a nyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, and combinations thereof. In claim 1,
The functional group including the moiety represented by the formula (2) is a hard mask composition represented by the following formula (2'):
[Formula 2′]

In Formula 2',
W is O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,
Z is hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,
a is 0 or 1,
b is an integer from 0 to 10,
* is the connection point,
In the above 'substituted or unsubstituted', substitution means that a hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C2 to C20 heteroaryl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalke It means substituted with a substituent selected from a nyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, and combinations thereof. In claim 1,
The additive is a hard mask composition represented by the following Chemical Formula 3:
[Formula 3]

In Formula 3,
k, m and n are each independently 0 or 1, but the sum of k, m and n is 2 or 3,
When k+m+n=3, X is -CH- or nitrogen (N),
When k+m+n=2, X is a direct bond, -(C _q H _2q )-, -(C _t R ^w _2t )-, oxygen (O), sulfur (S), -NH-, or -S (O ₂ )-, wherein q and t are each independently an integer of 1 to 5, and R ^w is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C7 to C20 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 hetero Cycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C1 to C4 alkyl ether group, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted C1 to C30 halo an alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof,
R, R′ and R″ are each independently a substituted or unsubstituted aromatic ring-containing group, wherein R, R′ or R″ are a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted at least one acetylene group, azide group, or nitrile group,
In the above 'substituted or unsubstituted', substitution means that a hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C2 to C20 heteroaryl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalke It means substituted with a substituent selected from a nyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, and combinations thereof. In claim 3,
The additive is a hard mask composition represented by the following Chemical Formula 4 or 5:
[Formula 4]

[Formula 5]

In Formulas 4 and 5,
X ¹ is -CH- or nitrogen (N),
X ² is a direct bond, -(C _q H _2q )-, -(C _t R ^w _2t )-, oxygen (O), sulfur (S), -NH- or -S(O ₂ )-, where q and t is each independently an integer of 1 to 5, and R ^w is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or Unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C7 to C20 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C1 to C4 alkyl ether group, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted C1 to C30 haloalkyl group, substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof,
R ¹ to R ⁵ are each independently an aromatic ring-containing group including at least one group represented by the following formula (6):
[Formula 6]

In Formula 6,
W is O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,
Y is a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, a nitrile group, or a combination thereof,
a is 0 or 1,
b is an integer from 0 to 10,
* is the connection point,
In the above 'substituted or unsubstituted', substitution means that a hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C2 to C20 heteroaryl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalke It means substituted with a substituent selected from a nyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, and combinations thereof. In claim 4,
In Formulas 4 and 5, R ¹ to R ⁵ are each independently a hard mask composition represented by Formula 7:
[Formula 7]

In Formula 7,
R ^1a to R ^13a are each independently hydrogen, a hydroxyl group, a substituted or unsubstituted C1 to C10 alkyl group, or a group represented by Formula 6, wherein at least one of ^{R 1a} to R ^{13a is a group represented by Formula 6, and} ,
T ¹ and T ² are each independently O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof,
c and d are each independently an integer from 0 to 5,
* is the connection point,
In the above 'substituted or unsubstituted', substitution means that a hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C2 to C20 heteroaryl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalke It means substituted with a substituent selected from a nyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, and combinations thereof. In claim 1,
In Formula 1, A is a substituted or unsubstituted moiety selected from the following groups 1 and 2, a hard mask composition:
[Group 1]

[Group 2]

In group 2,
Z ¹ and Z ² are each independently NR ^d , O, S, Te or Se,
Z ³ and Z ⁴ are N,
R ^d and R ^e are each independently hydrogen, a hydroxy group, a methoxy group, an ethoxy group, a halogen atom, a halogen-containing group, a substituted or unsubstituted 1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or their is a combination,
In the above 'substituted or unsubstituted', substitution means that a hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C2 to C20 heteroaryl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalke It means substituted with a substituent selected from a nyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, and combinations thereof. In claim 1,
In Formula 1, A is to include at least one substituted or unsubstituted aromatic, heteroaromatic ring,
In the above 'substituted or unsubstituted', substitution means that a hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C2 to C20 heteroaryl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalke A hard mask composition, which means substituted with a substituent selected from a nyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, and combinations thereof. In claim 1,
The B is a hard mask composition represented by any one of the following Chemical Formulas Z1 to Z4:
[Formula Z1]

[Formula Z2]

[Formula Z3]

[Formula Z4]

In the above formulas Z1 to Z4,
e and f are each independently 0 or 1,
g is an integer from 1 to 5,
Y ¹ to Y ⁴ are each independently any one of a substituted or unsubstituted moiety selected from the following group 3,
* is the connection point:
[Group 3]

In group 3,
M, M′ and M″ are each independently a substituted or unsubstituted C1 to C10 alkylene group, O, S, SO ₂ , CR ^f R ^g , NR ^h , or carbonyl, wherein R ^f to R ^h are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof;
L ¹ is a substituted or unsubstituted C6 to C50 arylene group, a substituted or unsubstituted C1 to C10 alkylene oxide-containing group, or a combination thereof,
r is an integer from 0 to 10,
s is an integer from 0 to 10,
k is an integer from 0 to 3,
In the above 'substituted or unsubstituted', substitution means that a hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C2 to C20 heteroaryl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalke It means substituted with a substituent selected from a nyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, and combinations thereof. In claim 1,
The polymer is a hard mask composition further comprising a structural unit represented by the following Chemical Formula 8:
[Formula 8]

In the formula (8),
X ⁰ is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof,
L ⁰ is a divalent organic group,
* is the connection point,
In the above 'substituted or unsubstituted', substitution means that a hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C2 to C20 heteroaryl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalke It means substituted with a substituent selected from a nyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, and combinations thereof. In claim 9,
In Formula 8, X ⁰ is a substituted or unsubstituted moiety selected from the following groups 1 and 2 of the hard mask composition:
[Group 1]

[Group 2]

In group 2,
Z ¹ and Z ² are each independently NR ^d , O, S, Te or Se,
Z ³ and Z ⁴ are N,
R ^d and R ^e are each independently hydrogen, a hydroxy group, a methoxy group, an ethoxy group, a halogen atom, a halogen-containing group, a substituted or unsubstituted 1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or their is a combination,
In the above 'substituted or unsubstituted', substitution means that a hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C2 to C20 heteroaryl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalke It means substituted with a substituent selected from a nyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, and combinations thereof. In claim 1,
The polymer is a hardmask composition comprising at least one oxygen atom in its structural unit. In claim 1,
The formula 2 is a hard mask composition represented by the following formula 2':
[Formula 2′]

In Formula 2',
W is O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,
a is 0 or 1,
* is the connection point,
In the above 'substituted or unsubstituted', substitution means that a hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C2 to C20 heteroaryl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalke It means substituted with a substituent selected from a nyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, and combinations thereof. In claim 1,
The additive is a hard mask composition represented by any one of the following formulas Y1 to Y4:
[Formula Y1]

[Formula Y2]

[Formula Y3]

[Formula Y4]

In the above formulas Y1 to Y4,
T ³ and T ⁴ are each independently O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof,
R ^x to R ^y are each independently hydrogen, a halogen atom, a halogen-containing group, or a substituted or unsubstituted C1 to C20 alkyl group,
R ³³ to R ⁵⁵ are each independently a group represented by the following formula (6):
[Formula 6]

In Formula 6,
W is O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,
Y is a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, a nitrile group, or a combination thereof,
a is 0 or 1,
b is an integer from 0 to 10,
* is the connection point,
In the above 'substituted or unsubstituted', substitution means that a hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C2 to C20 heteroaryl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalke It means substituted with a substituent selected from a nyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, and combinations thereof. In claim 1,
The additive is a hard mask composition having a molecular weight of 150 to 50,000. In claim 1,
The polymer is a hard mask composition having a weight average molecular weight of 500 to 200,000. In claim 1,
The hard mask composition comprising the additive in an amount of 5 wt% to 50 wt% based on the total content of the hardmask composition. providing a layer of material over the substrate;
applying a hardmask composition according to any one of claims 1 to 16 over the material layer;
forming a hard mask layer by heat-treating the hard mask composition;
forming a silicon-containing thin film layer on the hard mask layer;
forming a photoresist layer on the silicon-containing thin film layer;
exposing and developing the photoresist layer to form a photoresist pattern;
selectively removing the silicon-containing thin film layer and 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. In claim 17,
The step of applying the hard mask composition is a pattern forming method performed by a spin-on coating method. In claim 17,
The heat treatment is a pattern forming method comprising a first heat treatment performed at 50 to 250 °C, and a second heat treatment that is followed by the first heat treatment and proceeds at 200 to 500 °C. In claim 17,
and forming a bottom anti-reflective layer (BARC) prior to forming the photoresist layer.

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