阅读说明：本技术 聚合物、有机膜组成物及图案形成方法 (Polymer, organic film composition and pattern forming method ) 是由 郑铉日 金瑆焕 金昇炫 朴裕信 朴惟廷 辛乘旭 林栽范 于 2018-09-17 设计创作，主要内容包括：本公开是有关于一种聚合物、包含所述聚合物的有机膜组成物以及使用所述有机膜组成物形成图案的方法,其中所述聚合物包括由化学式1表示的结构单元、以及由化学式2或3表示的结构单元。化学式1至3的定义与在说明书中的描述相同。[化学式1]<Image he="198" wi="321" file="RE-DDA0002570566850000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>[化学式2]<Image he="191" wi="285" file="RE-DDA0002570566850000012.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>[化学式3]<Image he="239" wi="291" file="RE-DDA0002570566850000013.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present disclosure relates to a polymer, an organic film composition comprising the polymer, and a method of forming a pattern using the organic film composition, wherein the polymer includes a structural unit represented by chemical formula 1, anda structural unit represented by chemical formula 2 or 3. The definitions of chemical formulas 1 to 3 are the same as described in the specification. [ chemical formula 1] [ chemical formula 2] [ chemical formula 3])

1. A polymer comprising

A structural unit represented by chemical formula 1, and

a structural unit represented by chemical formula 2 or chemical formula 3:

[ chemical formula 1]

[ chemical formula 2]

[ chemical formula 3]

Wherein, in chemical formulas 1 to 3,

a is a moiety represented by the formula X,

b is a substituted or unsubstituted C6 to C30 aromatic ring group,

Ar¹and Ar²Independently a substituted or unsubstituted benzene ring or a condensed ring thereof,

m is an integer ranging from 0 to 5, and

is a connection point:

[ chemical formula X ]

Wherein, in the chemical formula X,

Ar³substituted or unsubstituted tetragonal rings, substituted or unsubstituted pentagonal rings, substituted or unsubstituted hexagonal rings or condensed rings thereof,

R^ais hydrogen, hydroxy, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heteroaryl, or combinations thereof,

Z^aindependently is hydroxy, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heteroaryl, or combinations thereof, and

n is 0 or 1.

2. The polymer of claim 1, wherein in chemical formula 1, B is one of a substituted or unsubstituted moiety of group 1:

[ group 1]

3. The polymer of claim 1, wherein in chemical formula 1, a is one of the moieties of group 2:

[ group 2]

Wherein, in group 2,

R¹and R²Independently hydrogen, hydroxy, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heteroaryl, or combinations thereof:

provided that in group 2, each moiety's hydrogen is independently replaced or not replaced by: hydroxyl, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heteroaryl, or combinations thereof.

4. The polymer according to claim 1, wherein in chemical formula 2, Ar¹And Ar²Independently a substituted or unsubstituted benzene moiety, a substituted or unsubstituted naphthalene moiety, a substituted or unsubstituted anthracene moiety, a substituted or unsubstituted phenanthrene moiety, a substituted or unsubstituted naphthacene moietyA moiety, a substituted or unsubstituted biphenylene moiety, a substituted or unsubstituted pyrene moiety, a substituted or unsubstituted perylene moiety, a substituted or unsubstituted benzoperylene moiety, or a substituted or unsubstituted coronene moiety.

5. The polymer of claim 1, wherein the weight average molecular weight of the polymer is in the range of 1,000 to 200,000.

6. An organic layer composition comprising:

a polymer comprising a structural unit represented by chemical formula 1 and a structural unit represented by chemical formula 2 or chemical formula 3, and

solvent:

[ chemical formula 1]

[ chemical formula 2]

[ chemical formula 3]

Wherein, in chemical formulas 1 to 3,

a is a moiety represented by the formula X,

b is a substituted or unsubstituted C6 to C30 aromatic ring group,

Ar¹and Ar²Independently a substituted or unsubstituted benzene ring or a condensed ring thereof,

m is an integer ranging from 0 to 5, and

is a connection point, and is a connection point,

[ chemical formula X ]

Wherein, in the chemical formula X,

Ar³substituted or unsubstituted tetragonal rings, substituted or unsubstituted pentagonal rings, substituted or unsubstituted hexagonal rings or condensed rings thereof,

R^ais hydrogen, hydroxy, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heteroaryl, or combinations thereof,

Z^aindependently is hydroxy, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heteroaryl, or combinations thereof, and

n is 0 or 1.

7. The organic layer composition of claim 6, wherein in chemical formula 1, B is one of a substituted or unsubstituted moiety of group 1:

[ group 1]

8. The organic layer composition of claim 6, wherein in chemical formula 1, A is one of the moieties of group 2:

[ group 2]

Wherein, in group 2,

R¹and R²Independently hydrogen, hydroxy, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heteroaryl, or combinations thereof:

provided that in group 2, each moiety's hydrogen is independently replaced or not replaced by: hydroxyl, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heteroaryl, or combinations thereof.

9. The organic layer composition of claim 6, wherein in chemical formula 2, Ar¹And Ar²Independently a substituted or unsubstituted benzene moiety, a substituted or unsubstituted naphthalene moiety, a substituted or unsubstituted anthracene moiety, a substituted or unsubstituted phenanthrene moiety, a substituted or unsubstitutedSubstituted naphthacene moieties, substituted or unsubstitutedA moiety, a substituted or unsubstituted biphenylene moiety, a substituted or unsubstituted pyrene moiety, a substituted or unsubstituted perylene moiety, a substituted or unsubstituted benzoperylene moiety, or a substituted or unsubstituted coronene moiety.

10. The organic layer composition of claim 6, wherein the weight average molecular weight of the polymer ranges from 1,000 to 200,000.

11. The organic layer composition of claim 6, wherein the amount of the polymer is 0.1 to 30 wt% based on the total amount of the organic layer composition.

12. A method of forming a pattern comprising

A material layer is formed on a substrate,

applying the organic layer composition of any one of claims 6 to 11 on the material layer,

heat-treating the organic layer composition to form a hard mask layer,

forming a thin layer comprising silicon on the hard mask layer,

forming a photoresist layer on the thin silicon-containing layer,

exposing and developing the photoresist layer to form a photoresist pattern,

selectively removing the thin layer comprising silicon and the hard mask layer using the photoresist pattern to expose portions of the material layer, an

The exposed portion of the material layer is etched.

13. The method of forming a pattern according to claim 12, wherein the organic layer composition is coated using a spin coating method.

14. The method of forming a pattern according to claim 12, wherein the method of forming a pattern further comprises forming a bottom anti-reflective coating (BARC) layer before forming the photoresist layer.

Technical Field

The present disclosure relates to a novel polymer, an organic layer composition comprising the polymer, and a method of forming a pattern using the organic layer composition.

Background

Recently, the semiconductor industry has developed to an ultra-fine technology having a pattern with a size of several nanometers to several tens of nanometers. Such ultra-fine technology essentially requires efficient lithography (lithographic technologies).

Typical lithographic techniques include: providing a material layer on a semiconductor substrate; coating a photoresist layer thereon; exposing and developing the photoresist layer to provide a photoresist pattern; and etching the material layer using the photoresist pattern as a mask.

Currently, it is difficult to provide a fine pattern having an excellent profile only by the above-described typical lithography technique according to miniaturization of a pattern to be formed. Accordingly, a layer called a hard mask layer may be formed between the material layer and the photoresist layer to provide a fine pattern.

The hard mask layer functions as an intermediate layer to transfer a fine pattern of photoresist to the material layer through a selective etching process. Accordingly, the hard mask layer needs to have characteristics such as heat resistance and etching resistance in order to withstand multiple etching processes.

On the other hand, a spin-on coating (spin-on coating) method has been recently proposed to form the hard mask layer instead of a Chemical Vapor Deposition (CVD) method. The spin coating method can be easily performed and can also improve gap filling characteristics and planarization characteristics.

The hardmask composition applied to the spin coating method may generally include a resin having a maximized carbon content to increase etching selectivity. In this case, since the resin is not dissolved in a solvent mainly used for semiconductors due to reduced solubility, the hardmask composition may be difficult to coat in a spin coating method. To solve this problem, another solvent having better solubility has been conventionally proposed, but the solvent may not smell well or deteriorate coating uniformity. Further, when the carbon content is reduced to increase the solubility, there is a problem of lowering the etching resistance. Therefore, there is a need for an organic layer composition material that improves storage stability, enhances solubility so as to use a solvent mainly used for a semiconductor process, and maximizes carbon content.

Disclosure of Invention

[ problem ] to

Drawings

Fig. 1 is a flow chart illustrating a method of forming a pattern according to an embodiment.

Embodiments provide a novel polymer having improved etch resistance and layer density while ensuring solubility and storage stability.

Another embodiment provides an organic layer composition comprising the polymer.

Yet another embodiment provides a method of forming a pattern using the organic layer composition.

[ solution ]

According to an embodiment, there is provided a polymer including a structural unit represented by chemical formula 1, and a structural unit represented by chemical formula 2 or chemical formula 3.

[ chemical formula 1]

[ chemical formula 2]

[ chemical formula 3]

In the chemical formulae 1 to 3,

a is a moiety represented by the formula X,

b is a substituted or unsubstituted C6 to C30 aromatic ring group,

Ar¹and Ar²Independently a substituted or unsubstituted benzene ring or a condensed ring thereof,

m is an integer ranging from 0 to 5, and

is a connection point, and is a connection point,

[ chemical formula X ]

Wherein, in the chemical formula X,

Ar³is a substituted or unsubstituted tetracyclic ringSubstituted or unsubstituted pentagonal rings, substituted or unsubstituted hexagonal rings or condensed rings thereof,

R^ais hydrogen, hydroxy, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heteroaryl, or combinations thereof,

Z^aindependently is hydroxy, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heteroaryl, or combinations thereof, and

n is an integer ranging from 0 to 2.

In chemical formula 1, B may be one of substituted or unsubstituted moieties of group 1.

[ group 1]

In chemical formulas 1 to 3, a may be one of the moieties of group 2.

[ group 2]

In the group 2, the first group is a group,

R¹and R²Independently hydrogen, hydroxy, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroAlkyl, substituted or unsubstituted C2 to C30 heteroaryl, or combinations thereof:

provided that in group 2, each portion of hydrogen may be independently replaced or not replaced by: hydroxyl, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heteroaryl, or combinations thereof.

In chemical formula 2 or chemical formula 3, Ar¹And Ar²May be independently substituted or unsubstituted benzene (benzzene) moiety, substituted or unsubstituted naphthalene (naphthalene) moiety, substituted or unsubstituted anthracene (anthracene) moiety, substituted or unsubstituted phenanthrene (phenanthrene) moiety, substituted or unsubstituted tetracene (tetracene) moiety, substituted or unsubstituted benzene (tetracene) moietyA (chrysene) moiety, a substituted or unsubstituted triphenylene moiety, a substituted or unsubstituted pyrene moiety, a substituted or unsubstituted perylene moiety, a substituted or unsubstituted benzoperylene moiety, or a substituted or unsubstituted coronene moiety.

The weight average molecular weight of the polymer may range from 1,000 to 200,000.

According to another embodiment, an organic layer composition comprising the polymer and a solvent is provided.

The polymer may be included in an amount of 0.1 to 30 wt% based on the total amount of the organic layer composition.

According to another embodiment, a method of forming a pattern includes: the method includes forming a material layer on a substrate, coating an organic layer composition including a polymer and a solvent on the material layer, heat-treating the organic layer composition to form a hard mask layer, forming a thin silicon-containing layer on the hard mask layer, forming a photoresist layer on the thin silicon-containing layer, exposing and developing the photoresist layer to form a photoresist pattern, selectively removing the thin silicon-containing layer and the hard mask layer using the photoresist pattern to expose a portion of the material layer, and etching the exposed portion of the material layer.

The organic layer composition may be coated by a spin coating method.

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

[ advantageous effects ]

A polymer according to an embodiment may include a combination of: heterocyclic groups including indole (indole) structures, ring groups having a tertiary carbon bond, and ring groups having a quaternary carbon bond. Therefore, when the polymer is used as an organic layer material, an organic layer having etching resistance and layer density and ensuring solubility and storage stability can be provided.