WO2017115978A1

WO2017115978A1 - Organic film composition and pattern forming method

Info

Publication number: WO2017115978A1
Application number: PCT/KR2016/010587
Authority: WO
Inventors: 최유정; 임재범; 허유미; 강선혜; 문수현
Original assignee: 삼성에스디아이 주식회사
Priority date: 2015-12-29
Filing date: 2016-09-22
Publication date: 2017-07-06

Abstract

The present invention relates to: an organic film composition containing a polymer, which comprises a structural unit represented by chemical formula 1, an additive represented by chemical formula 2, and a solvent; and a pattern forming method using the organic film composition. Chemical formulas 1 and 2 are the same as those defined in the description.

Description

【Specification】

[Name of invention]

Organic film composition and pattern forming method

Technical Field

An organic film composition and a pattern formation method using the organic film composition.

Background Art

In recent years, highly integrated designs due to miniaturization and complexity of electronic devices have accelerated the development of more advanced materials and related processes, and thus lithography using existing photoresists also requires new patterning materials and techniques. It became.

In the patterning process, in order to transfer the fine pattern of the photoresist to the substrate to a sufficient depth without collapse phenomenon, an organic film called a hard mask layer (hard mask layer) may be formed.

The hard mask layer acts as an intermediate layer to transfer the fine pattern of the photoresist to the material filling through the selective etching process. Therefore, the hard mask layer needs properties such as heat resistance and etching resistance to withstand the multiple etching process. On the other hand, it has recently been proposed that the hard mask layer is formed 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 can also improve gap-fill and planarization properties.

In general, heat resistance and etching resistance require an organic film material capable of satisfying both of these properties in terms of spin-on characteristics and an upper layer relationship.

[Detailed Description of the Invention]

[Technical problem]

One embodiment provides an organic film composition having excellent etching resistance as well as gap-fill characteristics and planarization characteristics.

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

Technical Solution

According to one embodiment, comprising a structural unit represented by the formula A composition comprising a polymer, an additive represented by the following Chemical Formula 1, and a solvent is provided.

[Formula 1]

In Chemical Formula 1,

A ¹ is a substituted or unsubstituted divalent ring group, or a substituted or unsubstituted divalent hetero ring group,

B ¹ is a divalent organic group,

* Is the connection point:

[Formula 2]

In Chemical Formula 2,

k, m and n are each independently 0 or 1, and the sum of k, m and n is 2 or 3 and 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 ^ _t )-, oxygen (0), sulfur (S), or-S (0 ₂ ) Where q and t are each independently an integer of 1 to 5 and! ^ 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 cycle Alkenyl 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 heterocycloalkyl group, substituted Or an unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a substituted or Unsubstituted C2 to C20 alkenyl group, or a combination thereof,

R, R 'and R "each independently represent a hydrogen, a hydroxy group, a substituted or unsubstituted monovalent ring having 3 to 30 carbon atoms, a substituted or unsubstituted monovalent compound having 1 to 30 carbon atoms Linear groups or combinations thereof.

In Formula 1, A ¹ may be a divalent ring group including at least two rings in its structure.

In Formula 1, A ¹ is a divalent ring group derived from any one of the compounds listed in Groups 1 and 2 below, and the divalent ring group may be unsubstituted or substituted with at least one hydrogen atom.

[Group 1]

In group 1 above,

M is a substituted or unsubstituted C1 to C5 alkylene group, 0-, -S-, -S0 _2- , or carbonyl: [Group 2]

In group 2 above,

R ° and R ¹ are each independently hydrogen, hydroxy group, hydroxy group, ethoxy group, halogen atom, halogen containing group, substituted or unsubstituted C 1 to C30 alkyl group, substituted or unsubstituted C 6 to C30 aryl group, or these Is a combination.

In Formula 1, B ¹ may be represented by the following Formula 3. [Formula 3]

/ ^H 2 \ a { ^H 2 \

--^ C- ^ L-rC- in Formula 3,

a and b are each independently an integer of 0 to 2,

L is a divalent group derived from any one of the compounds listed in Group 1 below and is a group unsubstituted or substituted with at least one hydrogen atom in the divalent group, or any of the groups listed in Group 3 below.

[Group 1]

In group 1 above,

'M is a substituted or unsubstituted C1 to C5 alkylene group, — 0-,-S-,-S0 _2- , or carbonyl: [Group 3]

In group 3 above,

X ¹ and X ² are each independently a substituted or unsubstituted C6 to C50 arylene group, a substituted or unsubstituted C1 to C10 alkylene oxide-containing group, or a combination thereof, and γ 'and γ ² are each independently hydrogen , A hydroxy group, a hydroxy group, an hydroxy group, a halogen group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, at least one of Y ¹ and Y ² is a substituted or unsubstituted C6 to C30 aryl group,

Z ⁷ to Z ¹⁰ are each independently a hydroxyl group, a hydroxy group, an ethoxy group, a halogen 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 An ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof,

g, h, i and j are each independently an integer of 0 to 2,

k is an integer of 1 to 3,

"*" Is a connection point.

In Group 3, X ¹ and X ² are each independently substituted or unsubstituted in C6

And a C50 arylene group, wherein the C6 to C50 arylene group may be a divalent group derived from any one of the compounds listed in Group 4 below. [Group 4]

One or ^two of Y ¹ and Y ² in the group 3 is a substituted or unsubstituted C6 to C30 aryl group and the C6 to C30 aryl group may be a monovalent group derived from any one of the compounds listed in Group 4.

The organic film composition may include two or more different polymers. The additive may be represented by the following Chemical Formula 2-1 or 2-2.

In Chemical Formula 2-1,

X ^a is ᅳ CH- or nitrogen (N),

R ^la to are each independently hydrogen, a hydroxy group, or a group represented by any one of the following Formulas A to C.

However, at least one of R ^la to R ^5a , at least one of R ^6a to R ^10a , and at least one of R ^{l la} to R ^15a are each independently represented by any one of Formulas A to C. [Formula A]

*-(C¾) _a -Y °-[Formula B]

[Formula c]

* -CR ^x R ^y R ^z

In Chemical Formulas A to C,

a and b are each independently an integer of 0 to 10,

c and d are each independently an integer of 1 to 10,

Y ⁰ is oxygen, sulfur, or -S (0 ₂ )-,

γ 'and γ ² are each independently hydrogen, 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 arylalkyl Ethylene ether groups, substituted or unsubstituted C1 to C30 haloalkyl groups, substituted or unsubstituted C2 to C20 alkenyl groups, or a combination thereof,

R ^x to R ^z are each independently hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof ,

* Is the connection point.

[Formula 2-2]

R ¹

I

R ² ^

In Chemical Formula 2-2,

X ^a is — CH- or nitrogen (N) R ¹ to R ³ are each independently a group represented by the formula (A), (B) or (C).

In Formula 2-1, wherein at least one of the R ^la to R ^5a, at least one of R ^6a to R ^10a, and R ^{l la} to at least one of R ^15a may group represented by the formula (A) independently of each other.

In the above formula (A) wherein a is 1, and the Y ⁰ is oxygen, and wherein Y ¹ can be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof.

The additive may be represented by the following formula 2-3 or 2-4.

-3]

In Chemical Formula 2-3,

X ^b is a direct bond,-(C _q H _2q )-,-(C _t R ^w _2t )-, oxygen (0), sulfur (S), or -S (0 ₂ )-, where q and t are respectively Is an integer of 1 to 5 independently and！ ^ is a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 3 to C 30 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 alke Nil group, or a combination thereof,

R ^lb to R ^10b are each independently hydrogen, a hydroxyl group, or a group represented by any one of the following Formulas A to C. [Formula A]

*-(CH ₂ ) _a -Y ° -Y

[Formula C]

* -CR ^x R ^y R ^z

In Chemical Formulas A to C,

a and b are each independently an integer of 0 to 10,

c and d are each independently an integer of 1 to 10,

Y ⁰ is oxygen, sulfur, or -S (0 ₂ )-,

Y ¹ and Y ² are each independently hydrogen, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 3 to C 30 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 An ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof,

* Is the connection point.

[Formula 2-4]

R'-X _b -R ²

In Chemical Formula 2-4,

X ^b is a direct bond,-(C _q H _2q )-,-(C _t R ^w _2t )-, oxygen (0), sulfur (S), or -S (0 ₂ )-where q and t are 1 And 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

R ¹ and R ² are each independently a group represented by the formula (A), (B) or (C).

In Formula 2-3, at least one of R ^lb to R ^5b and at least one of R ^6b to R ^10b may be each independently a group represented by Formula A.

In Formula A, a may be 0 or 1, Y ⁰ is oxygen, and Y ¹ may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof. There is

In Formula 2-3, X ^b is oxygen, at least one of R ^lb to R ^5b , and at least one of R ^6b to R ^10b may be each independently a group represented by Formula C.

At least one of the R ^x to R ^z in the formula (:) may be a hydroxyl group.

The additive may be represented by any one of the following Chemical Formulas 2A to 2G. [Formula 2A]

0-

[Formula 2B]

R ³ ''

[Formula 2C]

[Formula 2F]

In Chemical Formulas 2A to 2G,

R ³³ to R ⁸⁸ are each independently 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

e, f, g, and h are each independently an integer of 1-10.

The polymer may have a weight average molecular weight of 500 to 200,000, and the additive may have a molecular weight of 150 to 50,000.

In the organic film composition, the polymer and the additive may be included in a weight ratio of 90:10 to 50:50.

According to another embodiment, a step of providing a material layer over a substrate, said material Applying the organic film composition on the layer, heat treating the organic film composition to form a hard mask layer, forming a silicon containing thin film layer on the hard mask layer, and forming a photoresist layer on the silicon containing thin film layer Exposing and developing the photoresist layer to form a photoresist pattern, using the photoresist pattern, the silicon-containing thin film layer and the

Selectively removing the hardmask layer, exposing a portion of the material layer, and etching the exposed portion of the material layer.

Applying the organic film composition may be performed by a spin-on coating method.

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

【Effects of the Invention】

By including a predetermined polymer and a predetermined additive, there is provided an organic film composition capable of simultaneously improving etching resistance and solubility.

[Specific contents to carry out invention]

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

It is not limited.

Unless otherwise defined herein, 'substituted' means that a hydrogen atom in a 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 amino group Dino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, 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

Substituted with a substituent selected from a heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group and a combination thereof. In addition, unless otherwise defined herein, "hetero" means containing 1 to 3 heteroatoms selected from N, 0, S and P.

In addition, in this specification, the "monovalent group derived" from A compound means the monovalent group formed by substitution of one hydrogen in A compound. For example, the monovalent group derived from the benzene group becomes a phenyl group. In addition, a divalent group derived from the A compound is a divalent group in which two hydrogens in the A compound are substituted to form two linking points.

it means. Divalent groups derived from, for example, benzene groups become phenylene groups.

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

The organic film composition according to one embodiment includes a polymer including a structural unit represented by Chemical Formula 1, an additive represented by Chemical Formula 2, and a solvent.

[Formula 1

In Chemical Formula 1,

A ¹ is a substituted or unsubstituted divalent cyclic group, or a substituted or unsubstituted heterocyclic group 2 monovalent unsubstituted,

B ¹ is a divalent organic group,

* Is the connection point.

[Formula 2]

() k jR ') m

X

(") n

In Chemical Formula 2,

k, m and n are each independently 0 or 1, and the sum of k, m and n is 2 or 3, and 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 (0), sulfur (S), or-S (0 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 cycle Alkenyl 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 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 Combination of these,

R, R 'and R "are each independently hydrogen, a hydroxy group, a substituted or unsubstituted monovalent ring group having 3 to 30 carbon atoms, a substituted or unsubstituted monovalent linear group having 1 to 30 carbon atoms, or a combination thereof.

The monovalent ring group having 3 to 30 carbon atoms may be, for example, an alicyclic ring group or an aromatic ring group, but is not limited thereto. The monovalent linear group having 1 to 30 carbon atoms may be a monovalent group except a ring group containing 1 to 30 carbons, and specific member elements and structures are not limited.

The organic film composition may simultaneously secure an etching resistance and a gap-fill property by including a polymer having a predetermined structure and an additive. Accordingly, the organic film formed from the organic film composition is excellent in film density and planarization characteristics.

First, the polymer is further described.

The polymer may include a plurality of structural units represented by Chemical Formula 1, and the plurality of structural units may be the same as or different from each other. For example, in Formula 1, A ¹ is a divalent ring group derived from any one of the compounds listed in Group 1, and the divalent ring group may be unsubstituted or substituted with at least one hydrogen atom, It is not limited to this. [Group i]

In group 1 above,

M is a substituted or unsubstituted C1 to C5 alkylene group, -0-, -S-, -S0 _2- , or carbonyl.

The polymer may have rigid properties by including ring groups derived from the compound of Group 1 in its structural unit.

For example, in Formula 1, A ¹ may be a divalent ring group including at least two rings in its structure.

In another embodiment, in Formula 1, A ¹ is a divalent ring group derived from any one of the compounds listed in Group 1 below, and the divalent ring group may be unsubstituted or substituted with at least one hydrogen atom. It is not limited to this.

In group 2 above,

The polymer includes in the structural unit a ring group derived from the compound of Group 2, that is, a ring group containing a hetero atom such as nitrogen, oxygen, or sulfur, thereby increasing the polarity of the polymer by the hetero atom, thereby improving solubility. Let Can be. In addition, the polymer includes a hydrocarbon ring group in its structural unit, whereby the organic film using the polymer can ensure excellent film density. For example, in Formula 2, A ¹ represents that at least one hydrogen atom is a hydroxyl group, thionyl group, thiol group, cyano group, amino group, C1 to C10 alkyl group, C6 to C30 aryl group, C1 to C30 alkoxy group, or It may be substituted by a combination.

For example, the linking group represented by B ¹ in Formula 1 may be represented by the following Formula 3.

[Formula 3] 4 iii. In Chemical Formula 3,

a and b are each independently an integer of 0 to 2,

[Group 1]

In group 1 above,

M is a substituted or unsubstituted C1 to C5 alkylene group, -0-, -S-, -S0 ₂ - a, or a carbonyl group.

[Group 3]

In group 3 above,

X ¹ and X ² are each independently a substituted or unsubstituted C6 to C50 arylene group, a substituted or unsubstituted C 1 to C10 alkylene oxide containing group, or a combination thereof,

Y ¹ and Y ² are each independently hydrogen, hydroxy group, methoxy group, hydroxy group, halogen group, substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, and at least one of Y ¹ and Y ² is substituted or It is an unsubstituted C6 to C30 aryl group,

Z ⁷ to Z ¹⁰ are each independently a hydroxy group, a hydroxy group, a special group, a halogen 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

g, h, i and j are each independently an integer of 0 to 2,

k is an integer of 1 to 3,

"*" Is a connection point.

The polymer can increase the flexibility of the polymer by including such linking groups in its structural units. This flexible structure not only improves the solubility by increasing the free volume of the polymer, By lowering the glass transition temperature (T _g ) it is possible to increase the reflow during the baking process, resulting in improved gap-fill performance and planarization.

For example, in Group 3, X ¹ and X ² are each independently a substituted or unsubstituted C6 to C50 arylene group, and the C6 to C50 arylene group is derived from any one of the compounds listed in Group 4 below. It may be a period of time.

[Group 4]

For example, when one or ^two of Y ¹ and Y ² in the group 3 is a substituted or unsubstituted C6 to C30 aryl group, the C6 to C30 aryl group is derived from any one of the compounds listed in Group 4 It may be a period of time.

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

The organic film composition may include two or more polymers including a structural unit represented by Chemical Formula 1. As such, when the two or more different polymers are blended and used, the intended physical properties may be better realized.

Hereinafter, additives included in the organic film composition according to the embodiment will be described. As described above, the organic film composition includes an additive represented by Chemical Formula 2. The additive may include a plurality of parts represented by Chemical Formula 1, and the plurality of parts may have the same structure or different structures. The additive represented by Chemical Formula 2 has a structure in which substituents of two or three benzene rings are connected to the core represented by X in Chemical Formula 2. If the additive is represented by the formula 2 having three substituents of the core is carbon or nitrogen, if having a two substituents wherein the core is a direct bond, carbon, oxygen, sulfur, or -S (0 ₂₎ - a.

For example, when the additive has a structure in which three substituents are connected to the core, the additive may be represented by the following Chemical Formula 2-1 or 2-2.

2-1]

In Chemical Formula 2-1,

X ^a is -CH- or nitrogen (N),

R ^la to R ^15a are each independently hydrogen, a hydroxy group, or a group represented by any one of the following Formulas A to C.

However, at least one of R ^la to R ^5a , at least one of R ^6a to R ^10a , and at least one of R ^{l la} to R ^15a are each independently represented by any one of Formulas A to C.

[Formula A]

*-(CH ₂ ) _a -Y ° -Y ¹

[Formula B]

[Formula C]

* -CR ^x R ^y R ^:

In Chemical Formulas A to C a and b are each independently an integer of 0 to 10,

c and d are each independently an integer of 1 to 10,

Y ⁰ is oxygen, sulfur, or -S (0 ₂ )-,

Y ¹ and Y ² are each independently hydrogen, 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

R ^x to ^ are each independently hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof ,

* Is the connection point.

[Formula 2-2]

R ¹

I

R ² R ³

In Chemical Formula 2-2,

X ^a is -CH- or nitrogen (N),

R ¹ to R ³ are each independently a group represented by the formula (A), (B) or (C).

For example, in Formula 2-1, at least one of R ^la to R ^5a , at least one of R ^6a to R ^10a , and at least one of R ^{l la} to R ^15a are each independently a group represented by Formula A. Can be. As a more specific example, in Formula A, _a is 1 and γ ⁰ is oxygen, and Y ¹ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof Can be. On the other hand, when the additive has a structure in which two substituents are connected to the core may be represented by the following formula 2-3 or 2-4.

2-3]

^ "In Formula 2-3

X ^b is a direct bond,-(C _q H _2q )-,-(C _t R ^w _2t )-, oxygen (0), sulfur (S), or -S (0 ₂ )-, where q and t are respectively Is an integer of 1 to 5 independently and！ ^ 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,

Rib to Riob are each independently hydrogen, a hydroxyl group, or a group represented by any one of the following formulas (A) to (C).

[Formula A]

*-(CH) _a -Y ⁰ -Y '

[Formula B]

[Formula c]

* -CR ^x R ^y R ^z

In Chemical Formulas A to C,

a and b are each independently an integer of 0 to 10,

c and d are each independently an integer of 1 to 10,

Y ⁰ is oxygen, sulfur, or -S (0 ₂ )-,

R ^x to ^ are each independently hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,

* Is the connection point.

[Formula 2-4]

R'-X _b -R ²

In Chemical Formula 2-4,

_X ^b is a direct bond,-(CqH _2q )-,-(C _t R ^w _2t )-, oxygen (0), sulfur (S), or -S (0 ₂ )-where 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, 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 CI to C30 haloalkyl group, substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof,

For example, in Formula 2-3, at least one of R ^lb to R ^5b , and at least one of R ^6b to R ^10b may be each independently a group represented by Formula A. As a more specific example, when at least one of the R ^lb to R ^5b , and at least one of the R ^6b to R ^10b are each independently represented by Formula A, the a is 0 or 1, and the Y ⁰ is oxygen And Y ¹ may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof.

Also, for example, in Formula 2-3, X ^b is oxygen, at least one of R ^lb to R ^5b , and at least one of R ^6b to R ^10b are each

It may be a group represented by the formula (C) independently. As a more specific example, in Formula C, at least one of R ^x to R ^z may be a hydroxy group, and at least one of R ^x to R ^z may be a substituted or unsubstituted C1 to C20 alkyl group, but is not limited thereto. no.

For example, the additive may be represented by any one of the following Chemical Formulas 2A to 2G, but is not limited thereto.

[Formula 2A]

ᄋ —

[Formula 2B]

[Formula 2C]

OH [Formula 2F]

In Chemical Formulas 2A to 2G,

R ³³ to R ⁸⁸ are each independently 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 C 1 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, a substituted or unsubstituted C1 to C30 haloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof,

e, f, g, and h are each independently an integer of 1-10.

Formula _2E may be represented by, for example, Formula 2E ′, Formula 2F may be, for example, represented by Formula 2P, and Formula 2G may be, for example, represented by Formula 2G ′, but this is only illustrative. It doesn't happen. [Formula 2Ε ']

For example, the additive may be a crosslinking agent. The organic film composition may include an additive having such a structure to increase the crosslinking site of the polymer including the fluorene structure, thereby increasing the viscosity of the organic film composition. It is possible to improve the initial flatness of the organic film produced by reducing.

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 a layered-dissolving property or dispersibility to the polymer, for example, propylene glycol, propylene glycol diacetate, mesopropanediol, diethylene glycol, Diethylene glycol butyl ether, tri (ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclonucleanone, ethyl lactate, gamma-butyrolactone, Ν, Ν-dimethylformamide, And at least one selected from Ν, Ν-dimethylacetamide, methylpyridone, methylpyrrolidinone, acetylacetone and ethyl 3-ethoxypropionate.

The polymer may be included in 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 it is possible to control the thickness, surface roughness and degree of planarization of the organic film.

The additive may be included in an amount of about 0.1 to 50% by weight relative to the total content of the organic film composition. By including the additive in the above range, the initial planarization degree of the organic film manufactured may be improved.

For example, in the organic film composition, the additive including the structural unit represented by Chemical Formula 1, and the additive represented by Chemical Formula 2 may be included in a weight ratio of about 90:10 to 50:50, for example about 70 It may be included in a weight ratio of: 30 to 50:50. By controlling the polymer and additive content in the above range it is possible to form a film having excellent mechanical properties and flatness while ensuring the coating property of the organic film composition. The organic film composition may further include a surfactant, a thermal acid generator, or a plasticizer.

The surfactant may be, for example, an alkylbenzenesulfonic acid salt, an alkylpyridinium salt,

Polyethylene glycol, crab quaternary ammonium salt, etc. may be used, but is not limited thereto.

The thermal acid generator is, for example, Ρ- leulusulfonic acid, trifluoromethanesulfonic acid, pyridinium Ρ- leulusulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid,

Acidic compounds such as hydroxybenzoic acid and naphthalene carboxylic acid, and / or 2,4,4,6-tetrabromocyclonuxadienone, benzointosylate, 2-nitrobenzyltosylate, and other alkyl sulfonate esters It may be used, but is not limited thereto. According to another embodiment, an organic film prepared by using the organic film composition described above is provided. The organic layer may be in the form of the above-described organic layer composition, for example, coated on a substrate and cured through a heat treatment process, and may include, for example, an organic thin film used in an electronic device such as a hard mask layer, a planarization layer, a regenerative layer, a layer release agent, and the like. Could have.

Hereinafter, the method of forming a pattern using the organic film composition mentioned above is demonstrated.

According to one or more exemplary embodiments, a method of forming a pattern includes: providing a material layer on a substrate, applying an organic film composition including the polymer and a solvent on the material layer, and heat treating the organic film composition to form a hard mask layer. Forming a photoresist layer on the hard mask layer; forming a photoresist layer on the silicon mask layer; exposing and developing the photoresist layer to form a photoresist pattern; Selectively the silicon-containing thin film layer and the hard mask layer using

Removing 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, silicon nitride, or the like. The material layer can be formed, for example, by chemical vapor deposition.

The organic film composition is as described above, it 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, and for example, may be applied to a thickness of about 50 to 10,000 A. The heat treatment of the organic layer composition may be performed, for example, at about 100 to 500 ^° C. for about 10 seconds to 1 hour.

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

In addition, a bottom anti-reflective coating (BARC) may be further formed on the silicon-containing thin film layer before the forming of the photoresist layer.

Exposing the photoresist layer may be performed using, for example, ArF, KrF or EUV. It is also possible to perform a heat treatment process at about 100 to 500 ^° C after exposure. Etching the exposed portion of the material layer may be performed by dry etching using an etching gas, which may use, for example, CHF ₃ , CF ₄ , Cl ₂ , BC1 _3, and a combination thereof.

The etched material layer may be formed in a plurality of patterns, and the plurality of patterns may be a metal pattern, a semiconductor pattern, an insulating pattern, or the like, and may be applied in various patterns in a semiconductor integrated circuit device.

[Form for implementation of invention]

Through the following examples will be described in more detail the embodiment of the present invention. However, the following examples are merely for illustrative purposes and do not limit the scope of the present invention. Polymer synthesis

Synthesis Example la

LH-inodole (1 1.7 g, 0.1 mol), 6-hydroxyphenanthrene-1 -carbaldehyde (22.2 g, 0.1 mol), p-Toluenesulfonic acid monohydrate (pTSA, 9.5 g, 0.05 mol), and 1,4- Dioxane (60 g) was added and then stirred at 100 ^° C. Samples were taken from the polymerization reaction product at intervals of 1 hour, and the reaction was completed when the weight average molecular weight of the sample was 3,100. When the reaction was completed, 100 g of distilled water was added to extract pTSA, which was used as a catalyst. After stirring and standing, the supernatant was removed, and the precipitate formed by adding methanol was filtered and the remaining monomers were removed using methane. A polymer (Mw: 3,500) containing the resulting structural unit was obtained.

Chemical formula

Synthesis Example 2a

1,2,3,4-tetrahydroquinoline (13.3 g, 0.1 mol), 9-Fluorenone (18 g _; 0.1 mol), p-Toluenesulfonic acid monohydrate (9.5 g, 0.05 mol), and 1,4-dioxane (94 g) were added, followed by stirring at 100 ^° C. Samples were taken from the polymerization reaction at 1 hour intervals and reaction was completed when the weight average molecular weight of the sample was 3,300. When the reaction was completed, 100 g of distilled water was added to extract pTSA, which was used as a catalyst. After stirring and standing, the supernatant was removed, and the precipitate formed by adding methanol was filtered and the remaining monomers were removed using methanol.

A polymer (Mw: 3,700) containing a structural unit was obtained.

Formula 2a]

Synthesis Example 3a

100 ^{° C} after addition of Thianaphthene (13.4 g, 0.1 mol), 9-Fluorenone (18 g, 0.1 mol), p-Toluenesulfonic acid monohydrate (9.5 g, 0.05 mol), and l, ⁴ -dioxane (92 g) Stirred at C ᅳ Samples were taken from the polymerization reaction product at intervals of 1 hour, and the reaction was completed when the weight average molecular weight of the sample was 2,900. When the reaction was completed, 100 g of distilled water was added to extract pTSA, which was used as a catalyst, and after stirring and standing, the supernatant was removed, and the precipitate formed by adding methane was filtered and the remaining monomers were removed using methanol to be represented by Chemical Formula 3a. felled

A polymer (Mw: 3,200) containing a structural unit was obtained. .

Synthesis Example 4a

In a flask, 9 (10H) -Acridanone (19.5 g, 0.1 mol), Benzophenone (18.2g, 0.1 mol), p-Toluenesulfonic acid monohydrate (9.5 g, 0.05 mol), and 1,4-dioxane (98 g) After addition it was stirred at 100 ^° C. Samples were taken from the polymerization reaction at 1 hour intervals and reaction was completed when the weight average molecular weight of the sample was 2,300. When the reaction was completed, 100 g of distilled water was added to extract pTSA, which was used as a catalyst. After stirring and standing, the supernatant was removed, and the precipitate formed by adding methanol was filtered and the remaining monomers were removed using methanol.

A polymer containing structural units (Mw: 2,800) was obtained.

Formula 4a]

Synthesis Example 5a

After adding 9H-carbazole (16.7 g, 0.15 mol), Anthrone (17.5 g, 0.09 mol), p-Toluenesulfonic acid monohydrate (9.5 g, 0.05 mol), and 1,4-dioxane (152 g) to the flask, 105 Stir at ^° C. Samples were taken from the polymerization reaction product at 1 hour intervals, and the preparation was completed when the weight average molecular weight of the sample was 3,500. When the reaction was completed, 100 g of distilled water was added to extract pTSA, which was used as a catalyst. After stirring and standing, the supernatant was removed, and the precipitate formed by adding methane was filtered and the remaining monomers were removed using methanol. Expressed

A polymer (Mw: 3,800) containing a structural unit was obtained.

Formula 5a]

Synthesis Example 6a

LH-inodole (5.8 g, 0.05 mol), 6,6 '-(9H-fluorene-9,9-diyl) dinaphthalen-2- ol (22.5 g, 0.05 mol), perylene-3 -carbaldehyde (28 g) , 0.1 mol), p-Toluenesulfonic acid monohydrate (pTSA, 9.5 g, 0.05 mol), and 1,4-dioxane (60 g)

Stir at 100 ^° C. Samples were taken from the polymerization reaction product at intervals of 1 hour, and the The reaction was completed when the weight average molecular weight of the sample was 2,200. When the reaction was completed, 100 g of distilled water was added to extract pTSA, which was used as a catalyst. After stirring and standing, the supernatant was removed, and the precipitate formed by adding methanol was filtered and the remaining monomers were removed using methane. A polymer (Mw: 2,600) containing the resulting structural unit was obtained.

Formula 6a]

Synthesis Example 7a

In a 500 mL two-neck flask, 20.0 g (0.125 mol) of 1,8-dihydroxynaphthalene, 20.8 g (0.125 mol) of 1,4-bis (methoxymethyl) benzene (hereinafter referred to as BMMB), 0.58 g (3.75 mmol) of diethylsulfate, and PGMEA After the addition of 62.0 g, the reaction was carried out by stirring at 100 ^° C. for 2 to 15 hours. The reaction was completed when the weight average molecular weight was 2,000 to 3,500. After completion of the polymerization reaction, the reaction mass was slowly cooled to room temperature, and the reaction mass was stirred dropwise with 40 g of distilled water and 400 g of methanol dropwise. The supernatant was removed and the precipitate was dissolved in 80 g of PGMEA, followed by vigorous stirring and standing with 320 g of methanol and 320 g of water. The supernatant obtained at this time was removed again and the precipitate was dissolved in 80 g of PGMEA. When the process after cooling said the purification process once, a total of three purification processes were performed. After dissolving the purified polymer in 80 g of PGMEA, to remove the solvent remaining in the solution under reduced pressure to obtain a polymer (Mw: 3,700) comprising a structural unit represented by the formula (7a).

[Formula 7a]

Synthesis Example 8a

20.0 g (0.1 14 mol), 1,3,6-trihydroxynaphthalene, 4,4'-oxybis ((methoxymethyl) benzene) (hereinafter referred to as OBMMB) 29.3 g (0.1 14 mol), 0.53 g diethylsulfate in a 500 mL two-neck flask (3.41 mmol) and 75 g of PGMEA were added thereto, and then a polymer (Mw: 3,500) including a structural unit represented by Chemical Formula 8a was obtained through the same synthesis procedure as in Synthesis Example 7a.

Synthesis Example 9a

20.0 g (0.103 mol) of 9-phenanthrol, 26.6 g (0.103 mol) of OBMMB, 0.48 g (3.09 mmol) of diethylsulfate, and 71 g of PGMEA were added to a 500 mL two-neck flask, followed by the same synthesis procedure as in Synthesis Example 7a. A polymer (Mw: 3,800) comprising a structural unit represented by Chemical Formula 9a was obtained.

Formula 9a]

Synthesis Example 10a

30.0 g (0.078 mol) of 4,4 '-(9H-fluorene-9,9-diyl) dibenzene-l, 3-diol in 500 mL two-necked polar flask, 13.0 g (0.078 mol) of BMMB, 0.36 g (2.35) diethylsulfate mmol), and 65 g of PGMEA were added thereto, and then a polymer (Mw: 3,500) including a structural unit represented by Chemical Formula 10a was obtained through the same synthesis procedure as in Synthesis Example 7a.

[Formula 10a]

Synthesis Example 11a

40.0 g (0.083 mol) of 4,4 '-(9H-fluorene-9,9-diyl) dinaphthalene-l, 3-diol, 21.4 g (0.083 mol) of OBMMB, 0.38 g (2.49 mmol) diethylsulfate in a 500 mL two-neck flask ), And

After adding 93 g of PGMEA, a polymer (Mw: 3,200) including a structural unit represented by Chemical Formula 11a was obtained through the same synthesis procedure as in Synthesis Example 7a.

[Formula 1 1a]

Synthesis Example 12a

12.4 g (0.057 mol) 1-hydroxypyrene, 10 g (0.057 mol) 1,4,8-trihydroxynaphthalene, 29.3 g (0.1 14 mol) OBMMB, 0.53 g (3.41 mmol) diethylsulfate, and PGMEA 78 After adding g, a polymer (Mw: 2,800) containing a structural unit represented by Chemical Formula 12a was obtained through the same synthesis procedure as in Synthesis Example 7a.

Formula

4,4 '-(9H-fluorene-9,9-diyl) dibenzene-l, 3-diol 15.0 g (0.039 mol), 1,5-dihydroxynaphthalene 6.28 g (0.039 mol), BMMB 13.0 g (0.078 mol) ), 0.36 g (2.35 mmol) of diethylsulfate, and 52 g of PGMEA were added thereto, and the same as in Synthesis Example 7a.

Comprising a structural unit represented by the formula 13a through a synthetic process

A polymer (Mw: 3,500) was obtained. 13a]

Synthesis Example 14a

In a 500 mL two-neck flask, 20.0 g (0.125 mol) of 1,8-dihydroxynaphthalene, 10.4 g (0.063 mol) of BMMB, 16.1 g (0.063 mol) of OBMMB, 0.58 g (3.75 mmol) of diethylsulfate, and

After adding 71.0 g of PGMEA, a polymer (Mw: 3,600) including a structural unit represented by Chemical Formula 14a was obtained through the same synthesis procedure as in Synthesis Example 7a.

Formula Ma]

Synthesis Example 15a

In a flask, 24.3 g (0.125 mol) of phenanthren-3-ol, 20.8 g (0.125 mol) of 1,4-bis (methoxymethyl) benzerie (hereinafter referred to as BMMB), 0.58 g (3.75 mmol) of diethylsulfate, and 62.0 g of PGMEA After the addition, the 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 completion of the polymerization reaction, the reaction mixture was slowly cooled to room temperature, and then the reaction product was stirred dropwise with 40 g of distilled water and 400 g of methane. The supernatant was removed and the precipitate was dissolved in 80 g of PGMEA, followed by vigorous stirring and standing with 320 g of methanol and 320 g of water. The supernatant obtained at this time was removed again and the precipitate was dissolved in 80 g of PGMEA. When the post-penetration process was referred to as one purification process, a total of three purification processes were performed. After dissolving the purified polymer in 80 g of PGMEA, and removing the solvent remaining in the solution under reduced pressure to obtain a polymer (Mw: 3,700) comprising a structural unit represented by the formula (15a). 15a]

Synthesis Example 16a

30.6 g (0.1 14 mol) perylen-2-ol, 4,4 '-oxybis ((methoxymethyl) benzene)

(Hereinafter referred to as OBMMB) 29.3 g (0.1 14 mol), diethylsulfate 0.53 g (3.41 mmol), and 75 g of PGMEA were added, and the structural unit represented by the formula (16a) was subjected to the same synthesis procedure as in Synthesis Example 15a. A polymer (Mw: 3,500) was obtained.

Formula 16a]

Synthesis Example 17a

45.5 g (0.103 mol) of 4,4 '-(9H-fluorene-9,9-diyl) diphenol, 22.3 g (0.103 mol) of 2,6-bis (methoxymethyl) naphthalene, 0.48 g (3.09 mmol) of diethylsulfate, After PGMEA 7 lg was added, a polymer (Mw: 3,800) including a structural unit represented by Chemical Formula 17a was obtained through the same synthesis procedure as in Synthesis Example 15a.

17a]

Synthesis Example 18a

Into the flask, 16.9 g (0.078 mol) of 7H-benzo [c] carbazole, 13.4 g (0.078 mol) of 6-hydroxy-2-naphthaldehyde, 0.36 g (2.35 mmol) of diethylsulfate, and 65 g of PGMEA were added. Through the same synthesis process as the structural unit represented by the formula (18a) A polymer (Mw: 3,500) was obtained.

18a]

Synthesis Example 19a

15.0 g (0.083 mol) of 9,10-dihydroacridine, 16.1 g (0.083 mol) of anthracen-9 (10H) -one, 0.38 g (2.49 mmol) of diethylsulfate, and 93 g of PGMEA were added to the flask. Through the same synthesis process, a polymer (Mw: 3,200) including a structural unit represented by Chemical Formula 19a was obtained.

Synthesis Example 20a

1.1 g (0.057 mol) of acridin-9 (10H) -one 1, 12.7 g (0.057 mol) of 6-hydroxyanthracene-2-carbaldehyde, 0.53 g (3.41 mmol) of diethylsulfate, and 78 g of PGMEA were added to the flask. Through the same synthesis procedure as in Example 15a, a polymer (Mw: 2,800) including a structural unit represented by Chemical Formula 20a was obtained.

Equation 20a]

Triphenylamine (5 g, 20.38 mmol) After dissolving in dimethylformamide (DMF) (30 g), N-Bromosuccimmide (11.97 g, 67.23 mmol) is added dropwise, followed by stirring at room temperature for 12 hours. Extracted with dichloromethane (DCM), the solvent was removed, and the product was separated using column chromatography to obtain the following compound S1.

[Compound S1]

In a flask, the compound SI (0.5 g, 1.04 mmol) was added.

It was dissolved in tetrahydrofuran (THF) (5 mL) and then slowly added dropwise n-BuLi 1.6M in hexane (2.3 mL, 3.64 mmol) at -78 ^° C. next

Bromomethyl methyl ether (Bromomethyl methyl ether) (0.65 g, 5.2 mmol) was added dropwise and the mixture was slowly heated and stirred for 1 hour and 30 minutes. Using NH ₄ C1 solution

Quench, extract with EtOAc, remove solvent, remove product

Separation was performed using column chromatography to obtain a compound represented by the following formula lb.

Synthesis Example 2b

3,3 ', 5,5'-Tetrakis (methoxymethyl)-[l, l' -Biphenyl] -4,4'-diol (3g, 8.27mmol) was dissolved in DMF (30g) ， NaH 60% in mineral oil (0.83 g, 20.75 mmol) was added dropwise at 0 ^° C., and Mel (2.93 g, 20.64 mmol) was further added dropwise. After stirring for 12 hours at room temperature, NH ₄ C1 solution was added, extracted with EtOAc, and the solvent was removed. Product Column chromatography was isolated to obtain a compound represented by the following formula (2b).

2b]

Synthesis Example 3b

After dissolving in l, l'-Oxybis [4-methoxy-benzene] (3g, 13.02mmol) ¾-DCM (50mL), A1C1 ₃ (8g, 60mmol) was added dropwise at 0 ^° C. Thereafter, acetyl chloride (4.71 g, 60 mmol) was further added dropwise and stirred at room temperature for 12 hours. HC1 solution was added and extracted with DCM to remove solvent. Product

Purified by column chromatography to obtain the following compound S2.

[Compound S2]

The compound S2 (3g, 7.52mmol) was dissolved in anhydrous THF (50g), and then lithium aluminum hydride (1.138g, 30 mmol) was added dropwise at 0 ^° C and for 2 hours at room temperature. Stirred. 6N NaOH was added and extracted with EtOAc, and the solvent was removed. The product was purified by column chromatography to obtain a compound represented by the following formula (3b).

Formula 3b]

Preparation of Hard Mask Composition

Examples 1-20 Solid content of the composition shown in Table 1 is propylene glycol monomethyl ether

A hard mask composition was prepared by dissolving in propylene glycol monomethyl ether acetate (PGMEA) solvent and filtering.

TABLE 1

Resin 1: Additive 1: Resin 1 of additive 2 1 Additive 2

% By weight Example 1 Formula la Formula lb Formula 2c 70: 29.9: 0.1 Example 2 Formula 2a Formula 3b Formula 3c 70: 29.9: 0.1 Example 3 Formula 2b Formula lc 70: 29.9: 0.1

Formula 3a

Example 4 Formula 3b-70:30 Example 5 Formula lb ᅳ 70:30 Example 6 Formula 4a Formula 2b-70:30 Example 7 Formula 3b Formula 2c 70: 29.9: 0.1 Example 8 Formula lb Formula 3c 70: 29.9: 0.1 Example 9 Formula 5a Formula 2b Formula 3c 70: 29.9: 0.1 Example 10 Formula 3b Formula 3c 70: 29.9: 0.1 Example 11 Formula lb Formula lc 70: 29.9: 0.1 Example 12 Formula 6a Formula 2b Formula lc 70: 29.9: 0.1 Example 13 Formula 3b Formula lc 70: 29.9: 0.1 Example 14 Formula 8a Formula lb Formula lc 70: 29.9: 0.1 Example 15 Formula 9a Formula lb Formula lc 70: 29.9: 0.1 Example 16 Formula 10a Formula lb Formula lc 70: 29.9: 0.1 Example 17 Formula 11a Formula 2b Formula 2c 70: 29.9: 0.1 Example 18 Formula 12a Formula 2b Formula 2c 70: 29.9: 0.1 Example 19 Formula 13a Formula 3b Formula 3c 70: 29.9: 0.1 Example 20 Formula 14a Formula 3b Formula 4c 70: 29.9: 0.1 Comparative Example 1 Formula 2a--100

Comparative Example 2 Formula 4a--100 Comparative Example 3 Chemical Formulas 5a--100

Comparative Example 4 Formula 6a--100

Comparative Example 5 Chemical Formulas 8a--100

Comparative Example 6 Formulas 10a--100

Comparative Example 7 Chemical Formulas 12a--100

Comparative Example 8 Chemical Formulas 14a--100 Chemical Formulas lc, 2c, and 3c of Additive 2 in Table 1 above are represented as follows. Formula lc]

In addition, propylene glycol monomethyl ether acetate (PGMEA) and ethyl lactate (EL) were dissolved in a mixed solvent mixed with 7: 3 (volume ratio) by solid content of the composition shown in Table 2 below. After filtration to prepare a hard mask composition.

TABLE 2

Resin 1: Resin 2: Resin 1 Additive 1 Resin 2 Additive 1

% By weight Example 21 Formula 15a Formula 18a Formula lb 45:45: 10 Example 22 Formula 16a Formula 19a Formula 2b 45:45:10 Example 23 Formula 17a Formula 20a Formula 3b 45:45: 10 Comparative Example 9 Formula 15a--100 Evaluation 1: Evaluation of gap-fill and planarization characteristics

Hardmask compositions according to Examples 1,3,7,9,10,14,16, 18, 21, 22 and 23, and Comparative Examples 2, 3, 5, 7 and 9 (patterned content: after applying a weight of about 6 ^_0/0) and subjected to 2 minutes in a baking process 350 ^° C, using a V-SEM equipments gap-fill characteristics were observed.

The planarization characteristics were measured by measuring the thickness of the hard mask layer formed from the SEM cross-sectional image and measuring the height of the hard mask layer formed in the cell and the height of the hard mask layer formed in the Peri, respectively. (Step) was calculated to determine the flattening characteristics from the step value. The smaller the step value, the better the planarization characteristic.

The results are shown in Table 3 below.

TABLE 3

Gap Fill Characteristics (with or without voids) Planarization Characteristics (step difference, nm)

Example 1 No void 28

Example 3 void none 30

Example 7 void none 29

Example 9 void none 35

Example 10 void none 37

Example 14 void none 26

Example 16 void none 33

Example 18 void none 29

Example 21 void none 35

Example 22 void none 32

Example 23 void none 28

Comparative Example 2 void 65 Comparative Example 3 void 77

Comparative Example 5 void 84

Comparative Example 7 void 76

Comparative Example 9 void 79 Referring to Table 3, the thin film formed from the hard mask composition according to Comparative Examples 2, 3, 5, and 7 has a large level difference, so that the planarization property is not good, and voids are also observed in the pattern, thereby causing gaps. Peel performance is not good.

On the contrary, according to Examples 1,3,7,9, 10, 14, 16, 18 and 21,22 and 23

The thin film formed from the hard mask composition has a small level difference compared to the thin film formed from the hard mask composition according to Comparative Examples 2, 3, 5, 7, and 9, and has excellent flattening degree, and no void is observed so that gap-fill performance is also achieved. It can be confirmed that it is good. Evaluation 2: corrosion resistance evaluation

Hardmask compositions according to Examples 1, 2, 3, 5, 8, 11, 14, 16, 18, 21, 22 and 23 and Comparative Examples 1, 3, 4, 5, 7 and 9 on the silicon wafer (polymer content : spin about 14 weight ^_0/0) is formed on a silicon wafer pattern-coated on the coating method. Subsequently, after the heat treatment at 400 ^° C. for 120 seconds to form a thin film, the thickness of the formed thin film was measured using a ST-5000 thin film thickness meter of K-MAC.

Subsequently, the thin film was subjected to dry etching for 60 seconds using Ν ₂ / θ ₂ mixed gas (50mT / 300W / 10O ₂ / 50Ν ₂ ), and the thickness of the thin film was measured again. The bulk etch rate (BER) was calculated by the following equation 1 from the thin film thickness and the etching time before and after dry etching.

On the other hand, the hard mask composition according to Examples 1, 2, 3, 5, 8, 11, 14, 16, 18, 21, 22 and 23 and Comparative Examples 1, 3, 4, 5, 7 and 9 on the silicon wafer ( Polymer content: about 14 weight ⁰ /.) Was coated on the patterned silicon wafer by spin-on coating method. Subsequently, after the heat treatment at 400 ^° C. for 120 seconds to form a thin film, the thickness of the formed thin film was measured using a ST-5000 thin film thickness meter of K-MAC.

Then, CFx gas (100 in the thin film: a 1.1176 million / 42 _4/60 (15 ^ 1 ᄋ ₂₎

After performing dry etching for 60 seconds each, the thickness of the thin film was measured again. From the thin film thickness and the etching time before and after the dry etching, the etching rate (bulk etch rate, BER) was calculated by the following formula 1.

[Calculation 1]

Bulk etch rate (BER) = (Initial thin film thickness-thin film thickness after etching) / etching

Time (A / sec)

The results are shown in Table 4.

TABLE 4

Referring to Table 4, the thin films formed from the hard mask compositions according to Examples 1, 2, 3, 5, 8, 1 1, 14, 16, 18, 21, 22, and 23 are Comparative Examples 1, 3, 4, 5 , According to 7, and 9 As compared to a thin film formed from the composition can be seen that a low etch rate for the N _{_2/0 2} heunhap gas and CFx gas.

From this the hardmask compositions according to Examples 1,2,3,5,8,11,14,16,18,21,22 and 23 are hardmasks according to Comparative Examples 1,3,4,5,7 and 9 It can be seen that the bulk etch properties are improved compared to the composition. Evaluation 3: Pattern Formation Characteristics

A 3000 A thick silicon oxide (SiO _x ) layer was formed on the silicon wafer by chemical vapor deposition (CVD). Then after applying the hard mask composition in accordance with an embodiment 1,4,6,9, 12, 13, 14, 15 and 16, and Comparative Examples 1, 2 and 5 on the silicon oxide film by the spin coating method, 350 ^° Heat treatment was performed for 2 minutes to form a hard mask layer.

Subsequently, a silicon nitride (SiN _x ) layer was formed on the hard mask layer by chemical vapor deposition. Subsequently, the photoresist for KrF was spin-coated and heat-treated at 11 CTC for 60 seconds, and then exposed using an ASML (XT: 1400, NA 0.93) exposure equipment and developed with tetramethylammonium hydroxide (2.38 wt% TMAH aqueous solution).

Then using the photoresist patterned by the above process as a mask

The silicon nitride (SiN _x ) layer was dry etched using a CHF ₃ / CF ₄ mixed gas plasma. Then using a silicon nitride (SiN _x ) layer patterned by the above process as a mask

N _{_2/0 2} heunhap the using gas plasma Examples 1,4,6,9, made from 12, 13, 14, 15 and 16, and Comparative Examples 1, 2 and 5, the hard mask composition of the hard mask layer Was dry etched. The cross section of the hard mask pattern was observed using an electron scanning microscope (SEM). The results are shown in Table 5.

TABLE 5

Hardmask pattern

Example 1 Vertical Shape

Example 4 Vertical Shape

Example 6 Vertical Shape

Example 9 Vertical Shape

Example 12 Vertical Shape Example 13 ^' Vertical Shape

Example 14 Vertical Shape

Example 15 Vertical Shape

Example 16 Vertical Shape

Comparative Example 1 Tapered Shape

Comparative Example 2 Pattern Falling

Comparative Example 5 Pattern Collapse Referring to Table 5, the hardmask layers formed from the hardmask compositions according to Examples 1,4,6,9, 12, 13, 14, 15 and 16 were all patterned in a vertical shape, whereas the comparison Examples of the hard mask layer formed from the hard mask compositions according to Examples 1 and 2 may be patterned into a tapered shape in which the cross-section becomes narrower toward the upper end of the patterning pattern without being vertically patterned, or the pattern of the collapsed shape is poor in adhesion to the lower layer. It can be seen that it forms. Although the 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 of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of the invention.

Claims

【Patent Claims】【Claim 1】 An organic membrane composition containing a polymer containing a structural unit represented by the following Chemical Formula 1, an additive represented by the following Chemical Formula 2, and a solvent:

[Formula 1]

In Formula 1,

A ¹ is a substituted or unsubstituted divalent cyclic group, or a substituted or unsubstituted divalent heterocyclic group,

B ¹ is a divalent organic group,

* is a connection point:

[Formula 2]

(R)k. _vR ')m

X

(")n

In Formula 2,

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

_When k ⁺ _m ₊ n ₌ ₂ , -, where q and t are each independently an integer of 1 to 5, and ^ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C3 to C30 cycloalke. Nyl group, substituted or unsubstituted CI 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 an unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or any of these. is a combination, and R, R' and R" are each independently hydrogen, a hydroxyl group, a substituted or unsubstituted monovalent ring group having 3 to 30 carbon atoms, a substituted or unsubstituted monovalent linear group having 1 to 30 carbon atoms, or a combination thereof. am.

【Claim 2】

In paragraph 1,

In Formula 1, A ¹ is a divalent cyclic group containing at least two rings in its structure.

[Claim 3]

In paragraph 1,

In the above formula, A ¹ is a divalent cyclic group derived from any one of the compounds listed in Groups 1 and 2 below, wherein the divalent cyclic group has at least one hydrogen atom substituted or unsubstituted. An organic film composition:

[Group 1]

In group 1 above,

M is a substituted or unsubstituted C1 to C5 alkylene group, — 0-, -S-, -S0 ₂ -, or carbonyl:

[Group 2]

In group 2 above,

R ⁰ and R ¹ are each independently hydrogen, a hydroxy group, a methoxy group, an eroxy group, a halogen atom, a halogen-containing group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or any of these It's a combination.

【Claim 4】

In paragraph 1,

In Formula 1, B ¹ is an organic film composition represented by the following Formula 3: [Formula 3]

In Formula 3 above,

a and b are each independently integers from 0 to 2,

L is a divalent group derived from any one of the compounds listed in Group 1 below, in which at least one hydrogen atom is substituted or unsubstituted, or one of the groups listed in Group 3 below.

[Group 1]

In group 1 above,

M is a substituted or unsubstituted C1 to C5 alkylene group, -0-, -S-, -S0 ₂ -, or carbonyl: [Group 3]

In group 3 above,

X ¹ ^and

Y ¹ and Y ² are each independently hydrogen, a hydroxy group, a meroxy group, an ethoxy group, a halogen group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, but at least one of Y ¹ and Y ² is substituted or It is an unsubstituted C6 to C30 aryl group,

Z ⁷ to Z ¹⁰ are each independently a hydroxy group, a meroxy group, an eroxy group, a halogen group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, or a substituted or unsubstituted C1 to C30 group. C20 alkylamine group, substituted or unsubstituted C7 to C20 arylalkyl group, substituted or unsubstituted C1 to C20

g, h, i and j are each independently integers from 0 to 2,

is an integer from 1 to 3,

is the connection point.

【Claim 5】

In paragraph 4:

In Group 3, X ¹ ^and Composition: [Group 4]

[Claim 6]

In paragraph 4,

In Group 3, when one or two of Y ¹ and Y ² are substituted or unsubstituted C6 to C30 aryl groups, the C6 to C30 aryl group is a monovalent group derived from any one of the compounds listed in Group 4 below. Composition:

[Group 4]

【Claim 7】

In paragraph 1:

An organic membrane composition containing two or more different polymers.

【Claim 8】

In paragraph 1: The additive is an organic membrane composition represented by the following formula 2-1 or 2-2:

In Formula 2-1,

X ^a is -CH- or nitrogen (N),

Rla to RlSa are each independently hydrogen, a hydroxy group, or a group represented by any one of the following formulas _{ , to C.

However, at least one of R ^la to R ^5a , at least one of R ^6a to R ^10a , and at least one of R ^{l la} to R ^15a are each independently a group represented by any one of the following formulas A to C.

[Formula A]

*-(CH ₂ ) _a -Y ⁰ -Y'

[Formula B]

[Formula C]

*-C R ^x R ^y R ^z

In the above formulas A to C,

a and b are each independently integers from 0 to 10,

c and d are each independently integers from 1 to 10,

Y ⁰ is oxygen, sulfur, or -S(0 ₂ )-,

Y ¹ and Y ² are each independently hydrogen, 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, or 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 aryl An alkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof,

^R

* is a connection point.

[Formula 2-2]

In Formula 2-2,

X ^a is -CH- or nitrogen (N),

R ¹ to R ³ are each independently a group represented by Formula A, Formula B, or Formula C.

【Claim 9】

In paragraph 18,

In Formula 2-1, at least one of R ^la to R ^5a , at least one of R ^6a to R ^10a , and at least one of R ^lla to R ^15a are each independently a group represented by Formula A. Organic film composition.

【Claim 10】

In paragraph 8,

In Formula A, a is 1, Y ⁰ is oxygen, and Y ¹ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof. An organic layer composition.

【Claim 11】

In paragraph 1, The additive is an organic membrane composition represented by the following formula 2-3 or 2-4: -3]

In Formula 2-3,

^and _{_} _{_} _{_} ^_ _{_} _{_} Independently, it is 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, or a substituted or unsubstituted C3 to C30 cycloalkenyl group. 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 hetero Aryl 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 ^lb to R ^10b are each independently hydrogen, a hydroxy group, or a group represented by any one of the following formulas A to C.

[Formula A]

*-(CH ₂ ) _a -Y°-Y ^I

[Formula B]

[Formula C]

*-C R ^x R ^y R ^z In the above formulas A to C,

a and b are each independently integers from 0 to 10,

c and d are each independently integers from 1 to 10,

Y ⁰ is oxygen, sulfur, or -s(o ₂ )-,

γ ^ΐ and γ ² are each independently hydrogen, 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, or a substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C7 to C20 arylalkyl group, substituted or unsubstituted C1 to C20

^R ^_ ,

* is a connection point.

[Formula ^2-4 ]

R'-Xb-R ²

In Formula 2-4,

^and _{_} _{_} _{_} ^_ _{_} _{_} is an integer from 5 to 5, and 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, or 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 An ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof, R ¹ and R ² are each independently a group represented by Formula A, Formula B, or Formula C.

[Claim 12]

In paragraph 11:

In Formula 2-3, at least one of R ^lb to R ^5b and at least one of R ^6b to R ^10b are each independently a group represented by Formula A. The organic layer composition.

【Claim 13】

In paragraph 11,

In the formula A, a is 0 or 1, Y ⁰ is oxygen, and Y ¹ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof. Membrane composition.

【Claim 14】

In paragraph 11:

In Formula 2-3, X ^b is oxygen, and at least one of R ^lb to R ^5b and at least one of R ^6b to R ^10b are each independently a group represented by Formula C.

【Claim 15】

In paragraph 11:

In the formula C, at least one of R ^x to R ^z is a hydroxy group.

【Claim 16】

In paragraph 1, .

The additive is an organic membrane composition represented by any one of the following formulas 2A to 2G: [Formula 2A]

[Formula 2B]

[Formula 2C]

[Formula 2E]

In Formulas 2A to 2G,

R ³³ to R ⁸⁸ are each independently 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, or 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 An ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof, e, f, g and h are each independently integers from 1 to 10.

【Claim 17】

In paragraph 1:

The polymer has a weight average molecular weight of 500 to 200,000,

The additive is an organic membrane composition having a molecular weight of 150 to 50,000.

【Claim 18】

In paragraph 11,

An organic membrane composition comprising the polymer and additives in a weight ratio of 90:10 to 50:50.

【Claim 19】

providing a layer of material over a substrate,

Applying the organic film composition according to any one of claims 1 to 18 on the material layer,

forming a hard mask layer by heat-treating the organic film 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. Steps to form a photoresist pattern

selectively removing the silicon-containing thin film layer and the hard mask 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:

【Claim 20】

In paragraph 19,

A pattern forming method wherein the step of applying the organic layer composition is performed by a spin-on coating method.

【Claim 21】

In paragraph 19:

Before forming the commercial photoresist layer, a floor anti-reflection layer (BARC) is applied. Pattern forming method further comprising the step of forming