KR101992951B1 - Copolymer, semiconductor device comprising copolymer, composition comprising copolyemr, and preparation method of copolymer - Google Patents

Abstract

<화학식 2>

Ar은 치환 또는 비치환된 C₆-C₂₀ 아릴렌기, 또는 치환 또는 비치환된 C₂-C₂₀ 헤테로아릴렌기이며, R_a 내지 R_b는 서로 독립적으로 수소원자, 치환 또는 비치환된 C₁-C₁₈ 알킬기, 치환 또는 비치환된 C₂-C₁₈ 알케닐기, 치환 또는 비치환된 C₁-C₁₈ 알콕시기, 치환 또는 비치환된 C₆-C₁₈ 아릴기, 치환 또는 비치환된 C₃-C₁₀ 사이클로알킬기, 치환 또는 비치환된 C₃-C₁₈ 알킬아크릴기, 치환 또는 비치환된 C₄-C₁₈ 알킬메타크릴기, 치환 또는 비치환된 C₁-C₁₈ 아미노알킬기, 및 치환 또는 비치환된 C₁-C₁₈ 알킬비닐기, 치환 또는 비치환된 C₆-C₁₈ 아릴알킬기, 및 치환 또는 비치환된 C₆-C₁₈ 알킬아릴기로 구성되는 군에서 선택된 어느 하나이며, m은 1 내지 20의 정수이며, n은 1 내지 200이며, 화학식 1로 표시되는 반복단위와 화학식 2로 표시되는 반복단위의 몰비는 1:99 내지 99:1이다.There is provided a copolymer comprising an arylene ether-based repeating unit represented by the following formula (1) and a siloxane-based repeating unit represented by the following formula (2), a semiconductor device comprising the same,
&Lt; Formula 1 >

(2)

Ar is a substituted or unsubstituted C ₆ -C ₂₀ arylene group or a substituted or unsubstituted C ₂ -C ₂₀ heteroarylene group, and R _a to R _b are each independently a hydrogen atom, a substituted or unsubstituted C ₁ -C ₂₀ arylene group, -C ₁₈ alkyl group, a substituted or unsubstituted C ₂ -C ₁₈ alkenyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkoxy group, a substituted or unsubstituted C ₆ -C ₁₈ aryl group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkyl group, a substituted or unsubstituted C ₃ -C ₁₈ alkyl acrylate group, a substituted or unsubstituted C ₄ -C ₁₈ alkyl methacrylate group, a substituted or unsubstituted C ₁ -C ₁₈ aminoalkyl group, and A substituted or unsubstituted C ₁ -C ₁₈ alkylvinyl group, a substituted or unsubstituted C ₆ -C ₁₈ arylalkyl group, and a substituted or unsubstituted C ₆ -C ₁₈ alkylaryl group, m is an integer of 1 to 20, n is 1 to 200, and the molar ratio of the repeating unit represented by the formula (1) to the repeating unit represented by the formula 1:99 to 99: 1.

Description

TECHNICAL FIELD [0001] The present invention relates to a copolymer, a semiconductor device including the same, a composition including the copolymer, and a method of preparing the copolymer.

Copolymer, a semiconductor device comprising the same, a composition containing the same, and a process for producing the copolymer.

Due to the trend toward miniaturization and high integration of semiconductor devices, defects such as short and crosstalk have been increased by increasing the density of circuit elements and interconnection parts on a semiconductor element substrate.

In order to suppress such defects, insulation of semiconductor devices is required, and an insulation material having a dielectric constant (Low-k) of 3.0 or less is required.

The gapfil process using a dry process such as CVD (Chemical Vapor Deposition) or ALD (Atomic Layer Deposition), etc., has a problem in that the bending of the semiconductor device due to film stress and the step Defects such as seam, voids and cracks of the gap fill region due to the deterioration of the coverage increase, and the device characteristics may be deteriorated. In addition, the drying method is expensive.

On the other hand, a polysilsesquioxane insulating film having a dielectric constant of about 2.5 to 3.1 which can be produced by a spin coating method by a wet method is proposed. The polysilsesquioxane insulating film improves the insulation characteristics, but leaks current occurs or the hardness of the film is low.

The polysilazane insulating film may not provide a sufficiently low dielectric constant, or may be decomposed while noxious gas is generated due to instability in the atmosphere, and the device characteristics may be deteriorated due to generation of noxious gas during the process.

Therefore, there is a demand for a material which can easily form an insulating film by a wet process such as spin coating, has a low dielectric constant, and can suppress formation of pores.

One aspect is to provide a copolymer that can provide low dielectric constant (low-k) and good gap fill properties.

Another aspect is to provide a semiconductor device comprising the copolymer.

Another aspect is to provide a composition comprising the copolymer.

Another aspect is to provide a method for producing the copolymer.

According to one aspect,

There is provided a copolymer comprising an arylene ether-based repeating unit represented by the following formula (1) and a siloxane-based repeating unit represented by the following formula (2)

&Lt; Formula 1 >

(2)

Ar is a substituted or unsubstituted C ₆ -C ₂₀ arylene group or a substituted or unsubstituted C ₂ -C ₂₀ heteroarylene group,

R _a to R _b each independently represent a hydrogen atom, a substituted or unsubstituted C ₁ -C ₁₈ alkyl group, a substituted or unsubstituted C ₂ -C ₁₈ alkenyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkoxy group, A substituted or unsubstituted C ₆ -C ₁₈ aryl group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkyl group, a substituted or unsubstituted C ₃ -C ₁₈ alkyl acryl group, a substituted or unsubstituted C ₄ -C ₁₈ alkyl methacrylate group, a substituted or unsubstituted C ₁ -C ₁₈ aminoalkyl group, and a substituted or unsubstituted C ₁ -C ₁₈ alkyl vinyl group, a substituted or unsubstituted C ₆ -C ₁₈ arylalkyl group, and a substituted or unsubstituted hwandoen C ₆ -C ₁₈ and at least one selected from the group consisting of alkyl groups aryl,

m is an integer of 1 to 20, n is 1 to 200,

The molar ratio of the repeating unit represented by the formula (1) to the repeating unit represented by the formula (2) is 1:99 to 99: 1.

According to another aspect,

A copolymer according to the above; And

A composition comprising an organic solvent is provided.

According to another aspect,

There is provided a semiconductor device comprising an insulating film containing a cured product of the above-mentioned copolymer.

According to another aspect,

Preparing a mixture by mixing an arylene ether oligomer represented by the following formula (11) and a siloxane oligomer represented by the following formula (12); And

And reacting the mixture to prepare a copolymer.

&Lt; Formula 11 >

&Lt; Formula 12 >

Ar is a substituted or unsubstituted C ₆ -C ₂₀ arylene group or a substituted or unsubstituted C ₂ -C ₂₀ heteroarylene group,

R _a to R _b each independently represent a hydrogen atom, a substituted or unsubstituted C ₁ -C ₁₈ alkyl group, a substituted or unsubstituted C ₂ -C ₁₈ alkenyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkoxy group, A substituted or unsubstituted C ₆ -C ₁₈ aryl group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkyl group, a substituted or unsubstituted C ₃ -C ₁₈ alkyl acryl group, a substituted or unsubstituted C ₄ -C ₁₈ alkyl methacrylate group, a substituted or unsubstituted C ₁ -C ₁₈ aminoalkyl group, and a substituted or unsubstituted C ₁ -C ₁₈ alkyl vinyl group, a substituted or unsubstituted C ₆ -C ₁₈ arylalkyl group, and a substituted or unsubstituted hwandoen C ₆ -C ₁₈ and at least one selected from the group consisting of alkyl groups aryl,

Rh and Rg are each independently hydrogen, a hydroxyl group, a halogen group or a substituted or unsubstituted C ₁ -C ₁₈ alkoxy group,

m is an integer of 1 to 20, and n is 1 to 200;

According to one aspect of the present invention, a copolymer having an arylene ether-based repeating unit and a siloxane-based repeating unit at a predetermined ratio can be used to easily produce a low dielectric insulating film having improved gap fill characteristics, And stability can be improved.

1 is a scanning electron microscope (SEM) image of the surface of a coating film obtained by coating the composition prepared in Example 5 on a fine pattern.
2 is a scanning electron microscope (SEM) image of the surface of a coating film obtained by coating the composition prepared in Example 6 on a fine pattern.
3 is a scanning electron microscope (SEM) image of the surface of a coating film obtained by coating the composition prepared in Example 7 on a fine pattern.
4 is a scanning electron microscope (SEM) image of the surface of a coating film obtained by coating the composition prepared in Comparative Example 3 on a fine pattern.

Hereinafter, a copolymer according to exemplary embodiments, a semiconductor device including the same, a composition including the same, and a method for producing a copolymer will be described in more detail.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

In the present specification, "substituted" as used herein means substituted with a hydroxy group or an alkyl group having 1 to 6 carbon atoms, unless otherwise defined.

The copolymer according to an embodiment includes an arylene ether-based repeating unit represented by the following formula (1) and a siloxane-based repeating unit represented by the following formula (2)

&Lt; Formula 1 >

(2)

Ar is a substituted or unsubstituted C ₆ -C ₂₀ arylene group or a substituted or unsubstituted C ₂ -C ₂₀ heteroarylene group, and R _a to R _b are each independently a hydrogen atom, a substituted or unsubstituted C ₁ -C ₂₀ arylene group, -C ₁₈ alkyl group, a substituted or unsubstituted C ₂ -C ₁₈ alkenyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkoxy group, a substituted or unsubstituted C ₆ -C ₁₈ aryl group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkyl group, a substituted or unsubstituted C ₃ -C ₁₈ alkyl acrylate group, a substituted or unsubstituted C ₄ -C ₁₈ alkyl methacrylate group, a substituted or unsubstituted C ₁ -C ₁₈ aminoalkyl group, a substituted Or an unsubstituted C ₁ -C ₁₈ alkyl vinyl group, a substituted or unsubstituted C ₆ -C ₁₈ arylalkyl group, and a substituted or unsubstituted C ₆ -C ₁₈ alkylaryl group, m Is an integer of 1 to 20, n is 1 to 200, and the molar ratio of the repeating unit represented by the formula (1) to the repeating unit represented by the formula (2) is 1: 9 9 to 99: 1. For example, the molar ratio of the repeating unit represented by the formula (1) to the repeating unit represented by the formula (2) may be 1:99 to 99: 1. For example, the molar ratio of the repeating unit represented by the formula (1) to the repeating unit represented by the formula (2) may be 1:99 to 90:10. For example, the molar ratio of the repeating unit represented by the formula (1) to the repeating unit represented by the formula (2) may be from 1:99 to 80:20. For example, the molar ratio of the repeating unit represented by formula (1) to the repeating unit represented by formula (2) may be from 1:99 to 70:30. For example, the molar ratio of the repeating unit represented by the formula (1) to the repeating unit represented by the formula (2) may be 1:99 to 60:30. For example, the molar ratio of the repeating unit represented by the formula (1) to the repeating unit represented by the formula (2) may be 1:99 to 50:50. For example, the molar ratio of the repeating unit represented by formula (1) to the repeating unit represented by formula (2) may be 1:99 to 40:60.

The degree of polymerization of the copolymer may be from 2 to 1000. For example, the degree of polymerization of the copolymer may be from 5 to 900. [ For example, the degree of polymerization of the copolymer may be from 5 to 800. For example, the degree of polymerization of the copolymer may be from 5 to 700. [ For example, the degree of polymerization of the copolymer may be from 5 to 600. [ For example, the degree of polymerization of the copolymer may be from 5 to 500. [ For example, the degree of polymerization of the copolymer may be from 5 to 400. [ It is possible to provide improved physical properties in this range of polymerization degree.

Since the copolymer contains an arylene ether-based repeating unit, the thermal stress is low and the shrinkage is suppressed by heat, so that the gas generation amount (outgassing) can be reduced, the heat resistance can be increased, and the dielectric constant can be lowered. Also, since the copolymer contains a siloxane-based repeating unit, it is possible to provide a coating film having improved solubility in an organic solvent, excellent flowability before curing, and improved density. Accordingly, the copolymer has low dielectric constant, low shrinkage, and improved solubility by simultaneously including the repeating unit of arylene ether and the repeating unit of siloxane, thereby providing low dielectric constant and excellent gap fill property.

For example, the arylene ether-based repeating unit in the copolymer may be represented by the following formula (3), and the siloxane repeating unit may be represented by the following formula (4)

(3)

&Lt; Formula 4 >

In the above formulas, Ar 1 and Ar 2 are independently a substituted or unsubstituted C ₆ -C ₂₀ arylene group, or a substituted or unsubstituted C ₂ -C ₂₀ heteroarylene group, and R _c , R _d , R _e and R _f is independently a hydrogen atom, a substituted or unsubstituted C ₁ -C ₁₈ alkyl group, a substituted or unsubstituted C ₂ -C ₁₈ alkenyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkoxy group, a substituted or unsubstituted Substituted or unsubstituted C ₆ -C ₁₈ aryl groups, substituted or unsubstituted C ₃ -C ₁₀ cycloalkyl groups, substituted or unsubstituted C ₃ -C ₁₈ alkyl acrylate groups, substituted or unsubstituted C ₄ -C ₁₈ alkyl methacryloyl A substituted or unsubstituted C ₁ -C ₁₈ aminoalkyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkylvinyl group, a substituted or unsubstituted C ₆ -C ₁₈ aralkyl group, and a substituted or unsubstituted C _A C ₆ -C ₁₈ alkylaryl group, m 1 is an integer of 1 to 10, n 1 and n 2 are each independently selected from the group consisting of 1 to 1 00, and the molar ratio of the repeating unit represented by the general formula (3) to the repeating unit represented by the general formula (4) is 5:95 to 95: 5. For example, the molar ratio of the repeating unit represented by the formula (3) to the repeating unit represented by the formula (4) may be 5:95 to 95: 5. For example, the molar ratio of the repeating unit represented by the formula (3) to the repeating unit represented by the formula (4) may be 5:95 to 90:10. For example, the molar ratio of the repeating unit represented by the formula (3) to the repeating unit represented by the formula (4) may be 5:95 to 80:20. For example, the molar ratio of the repeating unit represented by the formula (3) to the repeating unit represented by the formula (4) may be 5:95 to 70:30. For example, the molar ratio of the repeating unit represented by the formula (3) to the repeating unit represented by the formula (4) may be 5:95 to 60:40. For example, the molar ratio of the repeating unit represented by the formula (3) to the repeating unit represented by the formula (4) may be 5:95 to 50:50. For example, the molar ratio of the repeating unit represented by the formula (3) to the repeating unit represented by the formula (4) may be 5:95 to 40:60.

If m1 exceeds 10, the solubility of the resulting copolymer in an organic solvent may be lowered, and the reactivity between the arylene ether-based repeating unit and the siloxane-based repeating unit may be lowered, making it difficult to produce the copolymer .

For example, when n1 is 1 in the copolymer, n2 may be 0 to 10. For example, when n1 is 2, n2 may be from 0 to 20. For example, when n1 is 3, n2 may be 0 to 30. For example, when n1 is 7, n2 may be from 0 to 70. [

For example, the copolymer may be represented by the following formula (5)

&Lt; Formula 5 >

Wherein Ar 1 and Ar 2 are independently a substituted or unsubstituted C ₆ -C ₂₀ arylene group or a substituted or unsubstituted C ₂ -C ₂₀ heteroarylene group and R _c , R _d , R _e and R _f Are each independently a hydrogen atom, a substituted or unsubstituted C ₁ -C ₁₈ alkyl group, a substituted or unsubstituted C ₂ -C ₁₈ alkenyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkoxy group, a substituted or unsubstituted C ₆ -C ₁₈ aryl group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkyl group, a substituted or unsubstituted C ₃ -C ₁₈ alkyl acrylate groups, substituted or unsubstituted C ₄ -C ₁₈ alkyl methacrylate groups, A substituted or unsubstituted C ₁ -C ₁₈ aminoalkyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkylalkenyl group, a substituted or unsubstituted C ₆ -C ₁₈ arylalkyl group, and a substituted or unsubstituted C ₆ -C ₁₈ is any one selected from the group consisting of aryl groups alkyl, m1 is independently an integer of 1 to 10 with each other, n1 and n2 are each independently 1 Is an integer of not 100, r and s is the mole fraction, and r + s = 1, r: s = 10: 90 ~ 90: 10 and, t is the degree of polymerization it is 2 to 1000. For example, in formula (5), r: s = 10: 90 to 90: 10. For example, in formula (5), r: s = 10: 90 to 80:20. For example, in formula (5), r: s = 10: 90 to 70: 30. For example, in formula (5), r: s = 10: 90 to 60: 40. For example, in formula (5), r: s = 10: 90 to 50: 50. For example, in formula (5), r: s = 10: 90 to 40: 60. For example, in formula (5), t may be from 5 to 1000. For example, in formula (5), t may be from 5 to 900. [ For example, in formula (5), t may be from 5 to 800. For example, in formula (5), t may be from 5 to 700. For example, in formula (5), t may be from 5 to 600. [ For example, t in formula (5) may be from 5 to 500. For example, in formula (5), t may be from 5 to 400. [ It is possible to provide improved physical properties in this range of polymerization degree. The terminal groups disposed at both ends of the copolymer of Formula 5, which are not explicitly shown in Formula 5, may be, for example, a hydroxyl group, a hydrogen, a halogen group, or a C ₁ -C ₁₈ Alkoxy group. For example, in the copolymer of formula (5), when n1 is 1, n2 may be 0 to 10. For example, when n1 is 2, n2 may be from 0 to 20. For example, when n1 is 3, n2 may be 0 to 30. For example, when n1 is 7, n2 may be from 0 to 70. [

For example, in the copolymer, R _c , R _d , R _e, and R _f independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group, an allyl group, A phenyl group, a naphthyl group, or a naphthol group. For example, for example, at least one of R _c , R _d , R _e and R _f in the copolymer may not be an alkyl group. For example, at least one of R _c , R _d , R _e and R _f is an alkenyl group, an alkoxy group, a cycloalkyl group, an alkyl acrylate group, an alkyl methacrylate group, an aminoalkyl group, an aryl group, . For example, at least one of R _c , R _d , R _e and R _f may be a vinyl group, an allyl group, a cyclohexyl group, a phenyl group, a naphthyl group, or a naphthol group.

For example, Arl and Ar2 in the copolymer may be selected independently of each other from the following divalent residue structure:

In the above structural formulas, R ₁ , R ₂ , and R ₃ independently represent a hydrogen atom, a halogen, a hydroxy group, a substituted or unsubstituted C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkenyl group C ₁ A C ₆ alkoxy group, or a C ₆ -C ₂₀ aryl group.

For example, Arl and Ar2 in the copolymer may be selected independently of each other from the following divalent residue structure:

Wherein R ₄ , R ₅ and R ₆ are independently of each other a hydrogen atom, a halogen, a hydroxyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert- Propoxy group, phenyl, naphthyl, or naphthol group.

More specifically, the copolymer may be any one of the copolymers represented by the following formulas (6a) to (6k):

&Lt; Formula 6a &

&Lt; Formula 6b >

&Lt; Formula 6c >

<Formula 6d>

<Formula 6e>

(6f)

<Formula 6g>

<Formula 6h>

<Formula 6i>

<Formula 6j>

<Formula 6k>

In the above formulas, m1 is independently an integer of 1 to 10, n1 and n2 are independently an integer of 1 to 100, r and s are molar ratios, r + s = 1, 90 to 90: 10, and t is a polymerization degree of 2 to 1,000. For example, r: s = 10: 90 to 90: 10 in formulas (6a) to (6k). For example, r: s = 10: 90 to 80:20 in formulas (6a) to (6k). For example, r: s = 10: 90 to 70: 30 in formulas 6a to 6k. For example, r: s = 10: 90 to 60: 40 in formulas (6a) to (6k). For example, r: s = 10: 90 to 50: 50 in formulas (6a) to (6k). For example, r: s = 10: 90 to 40: 60 in formulas (6a) to (6k).

For example, in the above formulas, when n1 is 1, n2 is 0 to 10. For example, in the above formulas, when n1 is 2, n2 is 0 to 20. For example, in the above formulas, when n1 is 3, n2 is 0 to 30. For example, when n1 is 7, n2 may be from 0 to 70. Also, the terminal groups disposed at both ends of the copolymer of the above-mentioned formulas (6a) to (6k), which are not explicitly shown in the above formulas, for example, hydroxyl groups can be alkoxy date of hydrogen, halogen, or C ₁ -C _18.

The weight average molecular weight (Mw) of the copolymer may be 1,000 to 20,000. For example, the copolymer may have a weight average molecular weight of 1,000 to 20,000. For example, the weight average molecular weight of the copolymer may be from 3,000 to 20,000. For example, the weight average molecular weight of the copolymer may be from 3,000 to 18,000. For example, the weight average molecular weight of the copolymer may range from 5,000 to 15,000. For example, the weight average molecular weight of the copolymer may be 8,000 to 13,000. For example, the weight average molecular weight of the copolymer may be from 8,000 to 12,000. An improved gap fill property can be obtained in the above-mentioned weight average molecular weight range. The weight average molecular weight can be measured using gel permeation chromatography (GPC) using polystyrene as a standard. When the weight average molecular weight of the copolymer is less than the above-mentioned range, the strength of the film formed on the substrate may be insufficient, and coating and heat resistance may be deteriorated. On the other hand, when the weight average molecular weight of the copolymer exceeds the above-mentioned range, for example, when a composition containing the polymer is applied onto a stepped pattern, the gap fill may not be sufficiently achieved.

The dielectric constant of the copolymer may be 3.0 or less. For example, the dielectric constant of the copolymer may be less than or equal to 2.5. For example, the dielectric constant of the copolymer may be from 0.1 to 3.0. For example, the dielectric constant of the copolymer can be from 0.5 to 3.0. For example, the dielectric constant of the copolymer may be 1.0 to 3.0. For example, the dielectric constant of the copolymer may be 1.5 to 3.0. For example, the dielectric constant of the copolymer may be 1.8 to 3.0.

The composition according to another embodiment includes the above-mentioned copolymer and an organic solvent.

The organic solvent can easily form a coating without forming a void, and the film is slowly dried to improve flatness. The organic solvents include, for example, C ₁ ~ C ₁₀ aliphatic alcohols, C ₂ ~ C ₁₀ aliphatic ethers, C ₂ ~ C ₁₀ aliphatic ketones, C ₃ ~ C ₁₀ aliphatic esters, C ₄ ~ C ₁₀ aliphatic ketones, C ₄ ~ A C ₁₀ cycloaliphatic ester, and a C ₁ to C ₅ alkyl substituted C ₄ to C ₁₀ aliphatic amide. The kind of the organic solvent may be any one that can be used as an organic solvent in the art. More specifically, the organic solvent may be a high boiling solvent that volatilizes at a temperature somewhat lower than the temperature during coating, drying and curing of the composition. The organic solvent includes, for example, aliphatic hydrocarbon solvents such as hexane and heptane; Aromatic hydrocarbon solvents such as anisole, mesitylene and xylene; Ketone-based solvents such as methyl isobutyl ketone, 1-methyl-2-pyrrolidinone, and cyclohexanone; Ether-based solvents such as propylene glycol propyl ether (PGMEA) and propylene glycol monomethyl ether (PGME); Acetate-based solvents such as ethyl acetate, n-butyl acetate, propylene glycol methyl ether acetate and the like; Alcohol-based solvents such as ethyl alcohol, isopropyl alcohol and butyl alcohol; Amide solvents such as dimethylacetamide and dimethylformamide, and the like.

The organic solvent may be included in the range of 100 to 10,000 parts by weight based on 100 parts by weight of the copolymer. In particular, it may be included in the range of 500 to 10,000 parts by weight based on 100 parts by weight of the copolymer so as to prevent voids and improve the flatness of the film.

The dielectric constant of the composition may be 3.0 or less. For example, the dielectric constant of the composition may be less than or equal to 2.5. For example, the dielectric constant of the composition may be between 0.1 and 3.0. For example, the dielectric constant of the composition may be between 0.5 and 3.0. For example, the dielectric constant of the composition may be 1.0 to 3.0. For example, the dielectric constant of the composition may be 1.5 to 3.0. For example, the dielectric constant of the composition may be between 1.8 and 3.0.

At least 5 parts by weight of the copolymer may be dissolved in 100 parts by weight of the organic solvent. For example, at least 7 parts by weight of the copolymer may be dissolved in 100 parts by weight of the organic solvent in the composition. For example, at least 9 parts by weight of the copolymer may be dissolved in 100 parts by weight of the organic solvent in the composition. For example, at least 10 parts by weight of the copolymer may be dissolved in 100 parts by weight of the organic solvent in the composition. Thus, the copolymer can provide improved solubility in organic solvents.

The shrinkage ratio of the coating film obtained from the composition before and after the heat treatment may be 20% or less. For example, the contraction ratio of the coating film obtained from the composition before and after the heat treatment may be 15% or less. For example, the shrinkage ratio of the coating film obtained from the composition before and after the heat treatment may be 12% or less. For example, the shrinkage ratio of the coating film obtained from the composition before and after the heat treatment may be 11% or less. The coating film after the heat treatment means a cured coating film and means a coating film in which the solvent is completely removed and crosslinked. Accordingly, the coating film obtained from the composition by spin coating or the like is completely removed from the solvent by heat treatment at a temperature higher than the boiling point of the organic solvent, and the shrinkage rate is as low as 20% or less even after crosslinking. For example, the thickness reduction of the coating film may be less than 20%.

The copolymer included in the composition may be cured by self-crosslinking reaction at the time of baking even if there is no additional crosslinking agent, but may further include an additive to further improve the gap-fill property.

The composition may further comprise at least one additive selected from the group consisting of, for example, a crosslinking agent, an acid catalyst (or a crosslinking accelerator), and a surfactant.

The crosslinking agent is not particularly limited and is generally used in the technical field, but may be more specifically a heat crosslinking agent. As the crosslinking agent, for example, the crosslinking agent may be at least one of a phenol-based crosslinking agent, a benzyl alcohol crosslinking agent, an isocyanate and an alkoxymethylmelamine crosslinking agent, a substitution factor system, a polymer system containing an epoxy group, and a compound derived therefrom. The crosslinking agent may be added in a proportion of 0.01 to 5 parts by weight, for example, 0.1 to 0.5 parts by weight, based on 100 parts by weight of the copolymer. If the content of the crosslinking agent is less than the above-mentioned range, crosslinking may not be sufficient, and if it exceeds the above-mentioned range, the safety of the insulating film may be deteriorated.

In addition, the crosslinking ability of the crosslinking agent can be activated by the acid catalyst. The use of an acid catalyst together with a crosslinking agent can provide a further improved effect in terms of crosslinking reaction.

The acid catalyst may be, for example, an acid generator. When a composition comprising an acid generator is applied to a suitable substrate and then a thermal process such as a baking process is performed, the crosslinking reaction can be promoted in the presence of an acid generated from the acid generator. The acid generator may be a conventional thermal acid generator. An onium salt-based acid generator which can be selected from a diazonium salt system, a phosphonium salt system, a sulfonium salt system, an iodonium salt system and a combination thereof as an acid generator, a sulfonyldiazomethane-based acid generator, N-sulfonyloxyimide A sulfonic acid-based acid generator, a glyoxime-based acid generator, a triazine-based acid generator, and the like can be selected from the group consisting of an acid generator, a benzoin sulfonate acid generator, a nitrobenzyl sulfonate acid generator, The acid generator may be contained in an amount of 0.01 to 10 parts by weight in 100 parts by weight of the copolymer.

The composition may further include a surfactant to improve dispersibility, film thickness uniformity, and fine gaps fill property. The surfactant is generally used in the art and is not particularly limited. More specifically, the coating composition according to the present invention may further include a surfactant to improve the applicability. Surfactants that can be used include, for example, polyether-modified polydimethylsiloxanes, polyester-modified polydimethylsiloxanes, polyether-modified hydroxy-functional polydimethylsiloxanes, polyether-ester modified hydroxy functional polydimethylsiloxanes, Ester-modified polydimethylsiloxane, polyoxyethylene alkyl ethers, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkylallyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters Based surfactant such as polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and the like. The surfactant may be added alone or in combination of two or more. The surfactant may be included in an amount of 0.1 to 10 parts by weight, for example, 0.5 to 5 parts by weight, based on 100 parts by weight of the copolymer.

The composition can be used for gap fill, double patterning or hard mask.

For example, the composition can be filled with holes having an aspect ratio of 1 or more and a diameter of 70 nm or less, which is expressed by a height / diameter by a general spin coating, and the substrate can be planarized to a predetermined thickness. Further, the film filled in the hole has no air void or gap, and the thickness of the film after coating is constant. Also, the composition is excellent in storage stability at which the development speed and molecular weight of the composition are not changed as the storage time passes.

The substrate on which the composition is coated is not particularly limited and may be, for example, a glass substrate, a plastic substrate, a silicon substrate, or a ceramic substrate other than glass.

The method of coating the composition is not particularly limited as long as it is a wet coating method. For example, a slit coating method using a slit nozzle such as a spin coating method, a roll coating method, a spray coating method, a bar coating method, .

The thickness of the coated film may vary depending on the coating method, the concentration of the solid content in the composition, the viscosity, and the like, and may be, for example, 50 to 600 nm, but is not limited to this range and may be appropriately changed depending on the application.

A semiconductor device according to another embodiment includes an insulating film containing at least one selected from the above-mentioned copolymer and a cured product thereof. The capacity and stability of the semiconductor device can be improved by including the above-mentioned copolymer and / or the insulating film containing the cured product thereof. The kind of the semiconductor element is not particularly limited, and any semiconductor element including a low dielectric insulating film formed by using the above-mentioned copolymer in the art can be used. Semiconductor devices are, for example, transistors, memories, and the like.

The insulating film may be formed by coating a composition including the copolymer and the organic solvent, and then performing a baking process of applying at least one of heat of a certain temperature or more and ultraviolet rays of a certain energy or more and curing . By this process, the organic solvent in the composition coated on the substrate is volatilized and a cross-linking reaction of the copolymer is caused to form an organic / inorganic composite low-k insulating film having excellent heat resistance and high film density. At least a part of the siloxane-based repeating units in the curing process is cured by a crosslinking reaction to form a silica structure, so that an organic complex in which arylene ether and silica are covalently bonded can be formed. It is possible to add ultraviolet ray irradiation hardening after hardening at the time of hardening, or to add thermosetting after ultraviolet ray irradiation hardening. The curing process may be performed at 50 to 800 DEG C for 30 to 300 seconds, and the bake may be divided into a plurality of steps. The temperature and time of each baking step can be appropriately adjusted as needed within the above-mentioned range.

The dielectric constant of the insulating film may be 3.0 or less. For example, the dielectric constant of the insulating film may be 2.5 or less. For example, the dielectric constant of the insulating film may be 0.1 to 3.0. For example, the dielectric constant of the insulating film may be 0.5 to 3.0. For example, the dielectric constant of the insulating film may be 1.0 to 3.0. For example, the dielectric constant of the insulating film may be 1.5 to 3.0. For example, the dielectric constant of the insulating film may be 1.8 to 3.0.

A method for preparing a copolymer according to another embodiment includes: preparing a mixture by mixing an arylene ether oligomer represented by the following formula (11) and a siloxane oligomer represented by the following formula (12); And preparing the copolymer by reacting the mixture.

&Lt; Formula 11 >

&Lt; Formula 12 >

Ar is a substituted or unsubstituted C ₆ -C ₂₀ arylene group or a substituted or unsubstituted C ₂ -C ₂₀ heteroarylene group, and R _a to R _b are each independently a hydrogen atom, a substituted or unsubstituted C ₁ -C ₂₀ arylene group, -C ₁₈ alkyl group, a substituted or unsubstituted C ₂ -C ₁₈ alkenyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkoxy group, a substituted or unsubstituted C ₆ -C ₁₈ aryl group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkyl group, a substituted or unsubstituted C ₃ -C ₁₈ alkyl acrylate group, a substituted or unsubstituted C ₄ -C ₁₈ alkyl methacrylate group, a substituted or unsubstituted C ₁ -C ₁₈ aminoalkyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkyl vinyl group, a substituted or unsubstituted C ₆ -C ₁₈ arylalkyl group, and a substituted or unsubstituted C ₆ one selected from the group consisting of a group -C ₁₈ alkyl aryl, Rh And Rg independently represent hydrogen, a hydroxyl group, a halogen group or a substituted or unsubstituted C ₁ -C ₁₈ alkoxy group, m is an integer of 1 to 20 N is an integer of 1 to 200,

The terminal hydroxyl group of the oligomer represented by the formula (11) and the terminal group of the oligomer represented by the formula (12) are reacted with at least one of hydrogen, hydroxyl group, halogen group and alkoxy group so that the polymerization reaction proceeds to produce a copolymer .

In the copolymer preparation method, for example, the oligomer represented by the above formula: the oligomer represented by the above formula (12) may be mixed at a weight ratio of 1: 9 to 5: 5. For example, the oligomer represented by the formula (11): the oligomer represented by the formula (12) may be mixed at a weight ratio of 1: 9 to 4: 6. For example, the oligomer represented by the formula (11): the oligomer represented by the formula (12) may be mixed at a weight ratio of 2: 8 to 4: 6. For example, the oligomer represented by the formula (11): the oligomer represented by the formula (12) may be mixed at a weight ratio of 3: 7.

The higher the content of the siloxane-based oligomer of Chemical Formula 12 is, the higher the solubility is, and the more excellent the flexibility is, the better the gap fill ability is, and the density of the film is increased to improve the mechanical properties of the coating film. When the content of the oligomer of the general formula (11) is more than 9 or the content of the oligomer of the general formula (12) is less than 1, the solubility may be lowered or the flexibility may be decreased and the capping ability may be lowered. When the content of the oligomer of the general formula (11) is less than 1, or when the content of the oligomer of the general formula (12) exceeds 9, the shrinkage due to heat increases and gas generation (outgassing) increases and the dielectric constant can be increased.

For example, in the method for producing a copolymer, the arylene ether oligomer may include an oligomer represented by the following formula (13), and the siloxane oligomer may include an oligomer represented by the following formula (14)

&Lt; Formula 13 >

&Lt; Formula 14 >

In the above formulas, Ar 1 and Ar 2 are independently a substituted or unsubstituted C ₆ -C ₂₀ arylene group, or a substituted or unsubstituted C ₂ -C ₂₀ heteroarylene group, and R _c , R _d , R _e and R _f is independently a hydrogen atom, a substituted or unsubstituted C ₁ -C ₁₈ alkyl group, a substituted or unsubstituted C ₂ -C ₁₈ alkenyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkoxy group, a substituted or unsubstituted Substituted or unsubstituted C ₆ -C ₁₈ aryl groups, substituted or unsubstituted C ₃ -C ₁₀ cycloalkyl groups, substituted or unsubstituted C ₃ -C ₁₈ alkyl acrylate groups, substituted or unsubstituted C ₄ -C ₁₈ alkyl methacryloyl A substituted or unsubstituted C ₁ -C ₁₈ aminoalkyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkylvinyl group, a substituted or unsubstituted C ₆ -C ₁₈ aralkyl group, and a substituted or unsubstituted C ₆ -C ₁₈ which is selected from the group consisting of alkyl groups one aryl, R _h and R _g are each independently hydrogen, a hydroxyl group, a halogen group Is a substituted or unsubstituted C ₁ -C ₁₈ alkoxy group, m1 is an integer from 1 to 10, n1 and n2 is an integer of 1 to 100, independently of each other.

For example, in the method for preparing a copolymer, the arylene ether oligomer may include an oligomer selected from the following formulas (15a) to (15e):

&Lt; Formula 15a &

<Formula 15b>

<Formula 15c>

<Formula 15d>

<Formula 15e>

In the above formulas, m1 is an integer from 1 to 10, R _1, R _2, and R ₃ are independently a hydrogen atom, a halogen, a hydroxyl group from each other, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert- butyl Group, a methoxy group, an ethoxy group, a propoxy group, a phenyl group, a naphthyl group, or a naphthol group.

For example, in the process for preparing a copolymer, the siloxane-based oligomer may include one or more oligomers selected from the following formulas (16a) to (16c).

<Formula 16a>

<Formula 16b>

<Formula 16c>

In the above formulas, n1 and n2 are each independently an integer of 1 to 100, and R _h and R _g are, independently of each other, hydrogen, a hydroxyl group, a halogen group or a substituted or unsubstituted C ₁ -C ₁₈ alkoxy group.

For example, in the process for preparing a copolymer, the reaction may be carried out at a temperature of from 50 캜 to 200 캜 for 1 hour to 100 hours. For example, in the process for preparing a copolymer, the reaction can be carried out at a temperature of from 50 DEG C to 100 DEG C for from 2 hours to 8 hours.

In the method for preparing a copolymer, the oligomer represented by the formula (12) may be prepared by hydrating two or more monomers containing one compound having at least two halogen atoms among the compounds represented by the following formula (17) Or by dissolving it in an organic solvent such as butanol and then heating it.

&Lt; Formula 17 >

Wherein R _11, R _12, R ₁₃ and R ₁₄ each independently represent a hydrogen atom, a hydroxy group, a halogen atom, a substituted or unsubstituted C ₁ -C ₁₈ alkyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkenyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkoxy group, a substituted or unsubstituted C ₆ -C ₁₈ aryl group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkyl group, a substituted or unsubstituted C ₃ - C ₁₈ alkyl acrylate group, a substituted or unsubstituted C ₄ -C ₁₈ alkyl methacrylate group, a substituted or unsubstituted C ₁ -C ₁₈ aminoalkyl group, and a substituted or unsubstituted C ₁ -C ₁₈ alkyl vinyl group , A substituted or unsubstituted C ₆ -C ₁₈ aralkyl group, and a substituted or unsubstituted C ₆ -C ₁₈ alkaryl group.

The oligomer represented by the formula (11) is obtained by carrying out an intermolecular condensation reaction between the hydroxyl groups and at least one kind of monomer in an aromatic compound having at least two hydroxy groups in a molecule under a base catalyst.

An aromatic compound having two or more hydroxy groups in a molecule includes, for example, 1,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-di Naphthalenes such as hydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene 1,2,3-trihydroxynaphthalene and the like, 1,3-dihydroxybenzene, 1,4-di Hydroxybenzene, 2,3,5-trimethyl-1,4-dihydroxybenzene, 5-phenyl-1,3-dihydroxybenzene, 1,2,3-trihydroxybenzene, 1,3,6 Dihydroxy anthracene, 1,5-dihydroxy anthraquinone, 2,6-dihydroxy anthracene, 1,6-dihydroxy anthracene, (9,9-bis (4-hydroxyphenyl) fluorene) and BNF (9,9-Bis (6-hydroxy-2-naphthyl) fluorine).

The organic solvent used in the copolymer preparation method is not particularly limited, and examples thereof include C ₁ -C ₁₀ aliphatic alcohols, C ₂ -C ₁₀ aliphatic ethers, C ₂ -C ₁₀ aliphatic ketones, C ₃ -C ₁₀ aliphatic esters, A C ₄ to C ₁₀ alicyclic ketone, a C ₄ to C ₁₀ alicyclic ester, and a C ₁ to C ₅ alkyl substituted C ₄ to C ₁₀ aliphatic amide. The organic solvent includes, for example, aliphatic hydrocarbon solvents such as hexane and heptane; Aromatic hydrocarbon solvents such as anisole, mesitylene and xylene; Ketone-based solvents such as methyl isobutyl ketone, 1-methyl-2-pyrrolidinone, cyclohexanone, methyl ethyl ketone and acetone; Ether-based solvents such as tetrahydrofuran, isopropyl ether and propylene glycol propyl ether; Acetate-based solvents such as ethyl acetate, n-butyl acetate, propylene glycol methyl ether acetate and the like; Alcohol-based solvents such as ethyl alcohol, isopropyl alcohol and butyl alcohol; Amide solvents such as dimethylacetamide and dimethylformamide; Silicon-based solvent; Or a mixture thereof.

In the method for preparing a copolymer, the catalyst may be further added in the step of preparing a copolymer by reacting the mixture prepared by mixing the arylene ether oligomer represented by the formula (11) and the siloxane oligomer represented by the formula (12). By further including a catalyst, the reaction rate can be improved. The catalyst may be an acid catalyst or a base catalyst.

The siloxane-based oligomer represented by the general formula (12) used in the preparation of the mixture in the copolymer production process can be pretreated. In the pretreatment, an ether-based solvent is added to the siloxane-based oligomer represented by the general formula (12), and the solvent is removed by vaporization, whereby the alcoholic solvent remaining in the siloxane-based oligomer can be removed. The siloxane-based oligomer represented by Formula 12 in which the alcohol-based solvent is removed may be mixed with the arylene ether oligomer represented by Formula 11 to prepare a mixture. The mixture may further comprise a non-alcoholic solvent. Non-alcoholic solvents can be used for ether-based solvents such as propylene glycol methyl ether (PGME) and propylene glycol methyl ether acetate (PGMEA).

As typical examples of the acid catalyst, hydrochloric acid, nitric acid, sulfuric acid, acetic acid, methanesulfonic acid, camphorsulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, oxalic acid, formic acid or a mixture thereof may be used, Any one that can be used as an acid catalyst in the art can be used. Examples of the base catalyst include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; phosphorous compounds such as triphenylphosphine; amines such as triethylamine; But it is not limited to them and any base catalyst can be used in the art.

The content of the acid or base catalyst used in the polymerization reaction for preparing the copolymer may be 0.001 to 5 parts by weight based on 100 parts by weight of the total weight of the oligomers represented by the general formulas (11) and (12). For example, the content of the acid or base catalyst may be 0.01 to 1 part by weight based on 100 parts by weight of the total weight of the oligomer represented by the general formulas (11) and (12). If the amount of the acid or base catalyst is less than 0.001 part by weight, the polymerization rate may decrease and the reaction time may be long and the yield may be decreased. If the amount is more than 5 parts by weight, excessive polymerization may occur, An excessively increased copolymer can be produced.

In the present specification, a substituent is derived by replacing one or more hydrogen ions with other atomic ions or functional groups in an unsubstituted mother group. Unless otherwise stated, when a functional group is considered "substituted ", it is meant that the functional group is an alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, an alkynyl group having 2 to 40 carbon atoms, An alkyl group, a cycloalkenyl group having 3 to 40 carbon atoms, an aryl group having 7 to 40 carbon atoms, or a hydroxyl group. When a functional group is described as "optionally substituted ", it is meant that the functional group may be substituted with the substituent described above.

In the present specification, a and b of "carbon number a to b" mean the carbon number of a specific functional group. That is, the functional group may include a carbon atom from a to b. For example, "alkyl group of 1 to 4 carbon atoms" is an alkyl group having from 1 to 4 carbon atoms, _{i.e., CH 3 -, CH 3 CH} 2 -, CH 3 CH 2 CH 2 -, (CH 3) 2 CH-, CH ₃ CH ₂ CH ₂ CH ₂ -, CH ₃ CH ₂ CH (CH ₃ ) - and (CH ₃ ) ₃ C-.

Nomenclature for a particular radical may include mono-radical or di-radical depending on the context. For example, if a substituent requires two points of attachment to the remaining molecule, the substituent should be understood as a diradical. For example, a particular substituent group requiring two connecting points comprises a di-radical, such as _{-CH 2-, -CH 2 CH 2-,} -CH 2 CH (CH 3) CH 2-,. Other radical nomenclature such as "akylene" clearly indicates that the radical is a di-radical.

As used herein, the term "alkyl group" or "alkylene group" refers to a branched or unbranched aliphatic hydrocarbon group. In one embodiment, the alkyl group may be substituted or unsubstituted. The alkyl group includes alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, But are not necessarily limited thereto, and each of them may be optionally substituted or unsubstituted. In one embodiment, the alkyl group may have from 1 to 6 carbon atoms. For example, the alkyl group having 1 to 6 carbon atoms may be methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, pentyl, 3-pentyl, hexyl and the like.

As used herein, the term "alkenyl group" refers to a hydrocarbon group containing from 2 to 20 carbon atoms including at least one carbon-carbon double bond and includes an ethenyl group, a 1-propenyl group, Butenyl, 2-butenyl, cyclopropenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, and the like. In one embodiment, the alkenyl group may be substituted or unsubstituted. In one embodiment, the alkenyl group may have from 2 to 40 carbon atoms.

As used herein, the term "alkynyl group" refers to a hydrocarbon group containing from 2 to 20 carbon atoms including at least one carbon-carbon triple bond and includes an ethynyl group, a 1-propynyl group, a 1-butynyl group, But are not limited to these. In one embodiment, the alkynyl group may be substituted or unsubstituted. In one embodiment, the alkynyl group may have from 2 to 40 carbon atoms.

As used herein, the term "cycloalkyl group" means a fully saturated carbocycle ring or ring system. Means, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.

As used herein, the term "aromatic" refers to a ring or ring system having a conjugated pi electron system and includes a carbon ring aromatic (e.g., phenyl) and a heterocyclic aromatic (e.g., pyridine) . The term includes monocyclic rings or fused polycyclic rings (i.e., rings that share adjacent pairs of atoms) if the whole ring system is aromatic.

As used herein, the term "aryl group" refers to an aromatic ring in which the ring backbone contains only carbon, a ring system (i.e., two or more fused rings sharing two adjacent carbon atoms) Wherein the ring is a single bond, -O-, -S-, -C (= O) -, -S (= O) _2- , -Si (Ra) (Rb) - (Ra and Rb are, C10 alkyl group), an alkylene group having 1 to 10 carbon atoms which is substituted or unsubstituted with halogen, or -C (= O) -NH-. If the aryl group is a ring system, then each ring in the system is aromatic. For example, the aryl group includes, but is not limited to, a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a naphthacenyl group, and the like. The aryl group may be substituted or unsubstituted.

The term "arylene group" as used herein is an aryl group requiring two or more connecting points. The tetravalent arylene group is an aryl group requiring four connecting points, and the divalent arylene group is an aryl group requiring two connecting points. For example, -C ₆ H ₅ -OC ₆ H ₅ -.

As used herein, the term "heteroaryl group" refers to a single ring, a plurality of fused rings, or a plurality of rings wherein a single bond is replaced by a single bond, -O-, -S-, -C (= O) O) ₂ -, -Si (Ra) (Rb) - (Ra and Rb are independently of each other an alkyl group having 1 to 10 carbon atoms), an alkylene group having 1 to 10 carbon atoms, O) -NH-, and at least one ring atom is not a carbon, i. E., A heteroatom. In the fused ring system, one or more heteroatoms may be present in only one ring. In the fused ring system, one or more heteroatoms may be present in only one ring. For example, heteroatoms include, but are not necessarily limited to, oxygen, sulfur and nitrogen. For example, heteroaryl groups include furanyl, thienyl, imidazolyl, quinazolinyl, quinolinyl, isoquinolinyl, quinolinyl, quinolinyl, But are not limited to, quinoxalinyl, pyridinyl, pyrrolyl, oxazolyl, indolyl, and the like.

The term "heteroarylene group" as used herein is a heteroaryl group requiring two or more connecting points. The tetravalent heteroarylene group is a heteroaryl group requiring four connecting points, and the divalent heteroarylene group is a heteroaryl group requiring two connecting points.

The term "aralkyl group" and "alkylaryl group" used herein mean an aryl group connected as an substituent group via an alkylene group, such as an aralkyl group having 7 to 14 carbon atoms, Phenylpropyl group, naphthylalkyl group, and the like. In one embodiment, the alkylene group is a lower alkylene group (i.e., an alkylene group having from 1 to 4 carbon atoms).

As used herein, a "cycloalkenyl group" is a carbocycle ring or ring system having one or more double bonds, which is an aromatic ring-free ring system. For example, a cyclohexenyl group.

As used herein, a "heterocyclyl group" is a non-aromatic ring or ring system comprising at least one heteroatom in the ring skeleton.

As used herein, "halogen" is a stable element belonging to Group 17 of the Periodic Table of the Elements, for example, fluorine, chlorine, bromine or iodine, in particular fluorine and / or chlorine.

The weight average molecular weight of the copolymer is measured by GPC (Gel Permeation Chromatography) on a polystyrene standard sample.

The present invention will be described in more detail by way of the following examples and comparative examples. However, the examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

(Copolymer weight average molecular weight measurement condition)

In the following examples, the weight average molecular weight (Mw) of oligomers and copolymers was measured by performing gel permeation chromatography (GPC) using a GPC apparatus of WATERS, and the measurement conditions were as follows:

Standard sample: Standard polystyrene (Shodex, model: SL-105)

GPC column: Shodex KF-801, KF-802, KF-8031 (7.8 mm ㅧ 300 mm)

Oven temperature: 40 ° C

Sample concentration: 1%

Sample injection amount: 50 μl

Carrier Solvent: tetrahydrofuran (THF)

Flow rate: 1 ml / min

(Oligomer production)

Synthesis Example 1

55 g (0.5 mol) of 1,3-dihydroxybenzene was added to a reactor filled with nitrogen, 110 g of propylene glycol methyl ether acetate (PGMEA) solvent was added and stirred, and 1,3-dihydroxybenzene was completely dissolved . After heating the reactor to 150 ° C., 4 g (0.1 mole) of sodium hydroxide was added, and the reaction was carried out for 9 hours while removing water generated in the reaction using a Dean-Stark Trap installed in the reactor. After completion of the reaction, distilled water was added in an excess amount to precipitate the reaction product, and then the supernatant was removed. The reaction product was dissolved by adding 165 g of methyl ethyl ketone to the solution in which the supernatant liquid was removed, precipitated again with excess distilled water, and dried under reduced pressure to remove the solvent. As a result, about 30 g of an arylene ether-based solid oligomer represented by the following formula (15a) was obtained. GPC analysis was performed on the obtained oligomer, and as a result, the weight average molecular weight in terms of standard polystyrene was about 1,312

&Lt; Formula 15a &

(R₁=수소)

(R &lt; ₁ &gt; = hydrogen)

Synthesis Example 2

An oligomer was prepared in the same manner as in Synthesis Example 1, except that 55 g (0.5 mol) of 1,3-dihydroxybenzene was changed to 80 g (0.5 mol) of 2,7-dihydroxynaphthalene. About 43 g of an arylene ether-based solid oligomer represented by the following formula (15b) was obtained. As a result of GPC analysis of the obtained oligomer, the weight average molecular weight in terms of standard polystyrene was about 1,853.

<Formula 15b>

(R₁및 R₂=수소)

(R ₁ and R ₂ = hydrogen)

Synthesis Example 3

An oligomer was prepared in the same manner as in Synthesis Example 1 except that 55 g (0.5 mol) of 1,3-dihydroxybenzene was changed to 175 g (0.5 mol) of 9-bis (4-hydroxyphenyl) fluorene . About 40 g of an arylene ether-based solid oligomer represented by the following formula (15e) was obtained. As a result of GPC analysis of the obtained oligomer, the weight average molecular weight converted to standard polystyrene was about 2,002.

<Formula 15e>

(R₁및 R₂=수소)

(R ₁ and R ₂ = hydrogen)

Synthesis Example 4

(0.28 mol) of dichloromethylvinylsilane and 18.06 g (0.14 mol) of dichlorodimethylsilane were charged into a reactor under a nitrogen atmosphere, followed by the addition of 31.13 g (0.42 mol) of tert-butanol as a solvent Followed by stirring at 30 ° C for 60 minutes. Then, the reactor temperature was raised to 65 DEG C over 10 minutes, and the reaction proceeded. Hydrochloric acid (HCl) gas and tert-butylchloride gas generated in the reaction were collected by passing through a silicone oil trap and a water trap. Followed by stirring at 65 DEG C for 4 hours to prepare a siloxane-based oligomer represented by the following formula (16a). The weight average molecular weight (Mw) of the oligomer was about 1,820.

The reaction product containing the copolymer was cooled to 30 ° C over about 20 minutes, and then propylene glycol methyl ether acetate (PGMEA) was added and vacuum distilled to remove the alcohol .

<Formula 16a>

(R_h= 하이드록시기, R_g= 수소, n1=7, n2=15)

(R _h = hydroxyl group, R _g = hydrogen, n 1 = 7, n 2 = 15)

(Copolymer preparation)

Example 1: Polyarylene ether + polysiloxane (3: 7 weight ratio)

The siloxane-based oligomer represented by the formula (16a) prepared in Synthesis Example 4 and the arylene ether oligomer represented by the Formula (15a) prepared in Synthesis Example 1 were fed into the reactor at a weight ratio of 7: 3 and stirred at 20 ° C for 30 minutes Lt; / RTI &gt; Nitric acid as an acid catalyst was added in an amount of 1 part by weight based on 100 parts by weight of the oligomer, the temperature of the reactor was raised to 85 캜 over 30 minutes, and the reaction was carried out for 4 hours to obtain a copolymer represented by the following formula 6a. The weight average molecular weight of the copolymer was about 9,430. The molar ratio of polyarylene ether: polysiloxane in the copolymer was 16:38.

&Lt; Formula 6a &

Example 2: Polyarylene ether + polysiloxane (3: 7 weight ratio)

The siloxane oligomer represented by Formula 16a prepared in Synthesis Example 4 and the oligomer represented by Formula 15b prepared in Synthesis Example 2 were added to the reactor at a weight ratio of 7: 3 and dissolved at 20 ° C for 30 minutes. The acid catalyst monohy- nitric acid was added in an amount of 1 part by weight based on 100 parts by weight of the oligomer, the temperature of the reactor was raised to 85 ° C over 30 minutes, and the reaction was carried out for 4 hours to obtain a copolymer represented by the following formula 6d. The weight average molecular weight of the copolymer was about 10,489.

The molar ratio of polyarylene ether: polysiloxane in the copolymer was 15:38.

<Formula 6d>

Example 3: Polyarylene ether + polysiloxane (3: 7 weight ratio)

The oligomer represented by Formula 16a prepared in Synthesis Example 4 and the oligomer represented by Formula 15e prepared in Synthesis Example 3 were added to the reactor at a weight ratio of 7: 3 and dissolved at 20 占 폚 for 30 minutes. Nitric acid serving as an acid catalyst was added in an amount of 1 part by weight based on 100 parts by weight of the oligomer, the temperature of the reactor was elevated to 85 캜 over 30 minutes, and the reaction was carried out for 4 hours to obtain a copolymer represented by Formula 6e. The weight average molecular weight of the copolymer was about 11,410.

The molar ratio of polyarylene ether: polysiloxane in the copolymer was 16:38.

<Formula 6e>

Example 4: Polyarylene ether + polysiloxane (7: 3 weight ratio)

The oligomer of Formula 16a prepared in Synthesis Example 4 and the oligomer of Formula 15e prepared in Synthesis Example 3 were added to the reactor at a weight ratio of 3: 7 and dissolved at 20 ° C for 30 minutes. Nitric acid as an acid catalyst was added in an amount of 1 part by weight based on 100 parts by weight of the oligomer, the temperature of the reactor was raised to 85 캜 over 30 minutes, and the reaction was carried out for 4 hours to obtain a copolymer represented by the above formula 6e. The weight average molecular weight of the copolymer was about 8,410.

The molar ratio of polyarylene ether: polysiloxane in the copolymer was 38:16.

<Formula 6e>

Comparative Example 1: Polysiloxane alone

0.28 mol of trimethoxyvinylsilane and 0.14 mol of dimethyldimethoxysilane were added to the reactor under a nitrogen atmosphere, and the mixture was stirred at 20 캜 for 10 minutes to prepare a mixture. Then, a solution prepared by dissolving 0.05 mol of nitric acid in 0.42 mol of ultrapure water (18 MOhm) was slowly added to the mixture over 20 minutes. After the addition of the ultrapure water was completed, the temperature in the reactor was raised to 30 DEG C over about 10 minutes, and then the reaction product was hydrated by stirring for 1 hour. After hydration, the temperature in the reactor was raised to 85 캜 over about 30 minutes, and then the mixture was stirred for 3 hours to prepare a polysiloxane copolymer. The weight average molecular weight (Mw) of the copolymer was about 4,430.

The reaction product containing the copolymer was cooled to 30 ° C over about 20 minutes, and then propylene glycol methyl ether acetate (PGMEA) was added and vacuum distilled to remove the alcohol .

(Preparation of composition)

Example 5

10 g of the copolymer of formula (6a) prepared in Example 1 and 100 g of propylene glycol methyl ether acetate were mixed to prepare a composition for a microgap fill of the present invention (solid content: 10% by weight).

Example 6

10 g of the copolymer of formula (6d) prepared in Example 2 and 100 g of propylene glycol methyl ether acetate were mixed to prepare a composition for a microgap fill of the present invention (solid content: 10% by weight).

Example 7

10 g of the copolymer of Formula 6e prepared in Example 3 and 100 g of propylene glycol methyl ether acetate were mixed to prepare a composition for a microgap fill of the present invention (solid content 10% by weight).

Example 8

10 g of a copolymer of the formula 6e prepared in Comparative Example 1 and 100 g of propylene glycol methyl ether acetate were mixed to prepare a composition for a microgap fill of the present invention (solid content 10% by weight).

Comparative Example 2

10 g of the polyarylene ether-based copolymer of formula (15e) prepared in Synthesis Example 3 and 100 g of propylene glycol methyl ether acetate were mixed to prepare a composition for a microgap fill of the present invention (solid content: 10% by weight).

Comparative Example 3

10 g of the polysiloxane-based copolymer prepared in Comparative Example 1 and 100 g of propylene glycol methyl ether acetate were mixed to prepare a microgap fill composition (solid content 10% by weight) of the present invention.

Evaluation Example 1: Evaluation of solubility

The propylene glycol methyl ether (PGME) and propylene glycol methyl ether acetate (PGMEA) solvents were used as solvents for the copolymers prepared in Examples 1 to 4, Synthesis Example 3 and Comparative Example 1 to confirm their solubility in the organic solvents. 10 parts by weight of the copolymer prepared in Examples 1 to 4, Synthesis Example 3 and Comparative Examples 1 and 2 were added to 90 parts by weight of a solvent at 20 캜, respectively, and stirred for 60 minutes to prepare a 10% by weight solution. The results of the test were visually determined to be soluble or insoluble, and the results are shown in Table 1 below.

The dissolution is a state in which there is no precipitate even after lapse of 10 minutes from the stop of the stirring, and the precipitate is precipitated on the bottom after lapse of 10 minutes after stopping the stirring.

Organic solvent Composition Dissolution PGME Synthesis Example 3 Insoluble Example 1 Dissolution Example 2 Dissolution Example 3 Dissolution Example 4 Insoluble Comparative Example 2 Dissolution PGMEA Synthesis Example 3 Insoluble Example 1 Dissolution Example 2 Dissolution Example 3 Dissolution Example 4 Insoluble Comparative Example 2 Dissolution

As shown in Table 1, the solubility of the homopolymer of Synthesis Example 3, which is an arylene ether polymer, and the copolymer of Comparative Example 1, which has a high content of arylene ether polymer in the entire copolymer, decreased.

Evaluation Example 2: Optical property evaluation

The low-k film-forming composition for gap fill obtained in Examples 5 to 8 and Comparative Examples 2 to 3 was applied to a 12-inch wafer (KLA-TENCOR) using a track instrument (TEL-ACT-8, TEL) SFX100) and then baked at 80 DEG C, 250 DEG C, and 400 DEG C for 60 seconds for 3 seconds to form a cured coating film.

The thickness of each of the formed coating layers was measured using a thickness, refractive index and extinction coefficient meter (M2000D, Woollam), and then the uniformity was calculated. The results are shown in Table 2 below. Uniformity can be calculated using the following equation (1). The refractive index and extinction coefficient were also measured using the same machine.

&Quot; (1) &quot;

Uniformity (%) = [(thickness maximum value - thickness minimum value) / (2 x average thickness)] x 100

Average thickness
(A) Refractive index (n) @ 633 nm Absorption coefficient (k)
@ 633 nm Uniformity
(%) Example 5 3707 1.36 0 0.73 Example 6 3653 1.35 0 0.77 Example 7 3712 1.36 0 0.31 Comparative Example 3 4167 1.43 0 0.37

Referring to Table 2, the coating films obtained by using the compositions for forming low-k dielectric films for microgap filling of Examples 5 to 7 were excellent in coating property and uniformity. The coating layer means that a coating layer is formed on the surface of the coating film without any pattern or unevenness.

In particular, the coating film obtained from the composition of Example 7 showed excellent uniformity similar to that of the polysiloxane-based coating film of Comparative Example 3.

Evaluation Example 3: Evaluation of shrinkage ratio

In the evaluation example 2, the thickness of the coating film before the baking process after the formation of the coating film was measured, the thickness of the coating film after the 3-step baking process was measured, and the contraction ratio was calculated. The shrinkage ratio can be calculated using the following equation (2).

&Quot; (1) &quot;

Shrinkage ratio (%) = [(thickness of coating film before baker-thickness of coating film after three-step baker) / thickness of coating film before baker] × 100

Baker thickness before coating [Å] After the 3-step bake process, the coating thickness [Å] Shrinkage [%] Example 5 4148 3707 10.6% Example 6 3989 3653 8.4% Example 7 3910 3712 5.0% Comparative Example 3 5416 4167 23.0%

Referring to Table 3, the coating film formed using the composition for forming a microgap fill for microgap filling of Examples 5 to 7 had a shrinkage rate lower than that of the polysiloxane-based coating film of Comparative Example 3.

Evaluation Example 4: Measurement of Dielectric Constant

The dielectric constant of the cured coating film formed in Evaluation Example 2 was measured, and the results are shown in Table 4 below.

The dielectric constant was measured using a metal-insulator semiconductor (MIS) method.

In the MIS method, a silicon wafer having a silver paste having a thickness of about 120 nm as the upper electrode and a lower resistance value (0.0001? Cm) as the lower electrode is used, and a cured coating film is disposed between the upper electrode and the lower electrode Capacitance-voltage profile was measured under the condition of 1MHz using a wafer prober (4200CSC, CASCADE) on the fabricated capacitors, and electrostatic capacitance was obtained from the CV graph. The electrode thickness and the electrode area Can be applied to Equation (3) to calculate the dielectric constant value of the thin film.

&Quot; (3) &quot;

C = (ε ₁ ε ₀ A) / d

Where C is the capacitance,? ₁ is the relative dielectric constant,? ₀ is the vacuum dielectric constant, A is the area of the electrode, and d is the thickness of the film.

Dielectric constant [k] Example 5 2.37 Example 6 2.24 Example 7 2.11 Comparative Example 3 3.89

As shown in Table 4, the dielectric constant of the coating film made of the copolymer obtained from the composition for gapfill of Examples 5 to 7 was 2.40 or less, and the dielectric constant of the coating film made of the copolymer obtained from the composition of Comparative Example 3 was 3 .

Evaluation Example 5: Evaluation of gap fill characteristics

The depth was measured on an 8-inch silicon wafer, the 180-nm pattern was formed on a 3.2-micro contact hole, and a 12-inch wafer was measured using a track instrument (TEL-ACT-8, TEL) The dielectric film forming composition and the polysiloxane-based composition of Comparative Example 3 were each applied by spin coating and then baked at 80 DEG C and 250 DEG C for about 60 seconds and at 400 DEG C for 5 minutes, respectively, to form a coating film. The gap-fill characteristics of the coating film formed using FE-SEM (Jeol Co., 15kv, 20k magnification) were measured, and the results are shown in Figs. As shown in Figs. 1 to 4, the insulating films of Figs. 1 to 3 formed from the compositions of Examples 5 to 7 were excellent in the gap fill property.

On the other hand, the insulating film of FIG. 4 formed in the composition of Comparative Example 3 was voided due to the formation of pores in the middle.

Claims (20)

A copolymer comprising an arylene ether-based repeating unit represented by the following formula (3) and a siloxane-based repeating unit represented by the following formula (4)
(3)

&Lt; Formula 4 >

Ar 1 and Ar 2 are independently a substituted or unsubstituted C ₆ -C ₂₀ arylene group or a substituted or unsubstituted C ₂ -C ₂₀ heteroarylene group,
R _c , R _d , R _e and R _f independently represent a hydrogen atom, a substituted or unsubstituted C ₁ -C ₁₈ alkyl group, a substituted or unsubstituted C ₂ -C ₁₈ alkenyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkoxy group, a substituted or unsubstituted C ₆ -C ₁₈ aryl group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkyl group, a substituted or unsubstituted C ₃ -C ₁₈ alkyl acrylate group, a substituted or unsubstituted a C ₄ -C ₁₈ alkyl methacrylate group, a substituted or unsubstituted C ₁ -C ₁₈ aminoalkyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkyl vinyl group, a substituted or unsubstituted C ₆ -C ₁₈ aryl An alkyl group, and a substituted or unsubstituted C ₆ -C ₁₈ alkylaryl group,
m1 is an integer of 2 to 20, n1 and n2 are independently from each other 2 to 200,
The molar ratio of the repeating unit represented by formula (3) to the repeating unit represented by formula (4) is 1:99 to 99: 1. The copolymer according to claim 1, wherein the arylene ether-based repeating unit is represented by the following general formula (3) and the siloxane-based repeating unit is represented by the following general formula (4)
(3)

&Lt; Formula 4 >

In the above equations,
Ar 1 and Ar 2 are independently a substituted or unsubstituted C ₆ -C ₂₀ arylene group or a substituted or unsubstituted C ₂ -C ₂₀ heteroarylene group,
R _c , R _d , R _e and R _f independently represent a hydrogen atom, a substituted or unsubstituted C ₁ -C ₁₈ alkyl group, a substituted or unsubstituted C ₂ -C ₁₈ alkenyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkoxy group, a substituted or unsubstituted C ₆ -C ₁₈ aryl group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkyl group, a substituted or unsubstituted C ₃ -C ₁₈ alkyl acrylate groups, substituted or unsubstituted hwandoen C ₄ -C ₁₈ alkyl methacrylate group, a substituted or unsubstituted C ₁ -C ₁₈ aminoalkyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkyl vinyl group, a substituted or unsubstituted C ₆ -C ₁₈ unsubstituted An aralkyl group, and a substituted or unsubstituted C ₆ -C ₁₈ alkylaryl group,
m1 is an integer of 2 to 10, n1 and n2 are independently an integer of 2 to 100,
The molar ratio of the repeating unit represented by the formula (3) to the repeating unit represented by the formula (4) is 5:95 to 95: 5. The copolymer according to claim 1, wherein the copolymer is represented by the following formula (5):
&Lt; Formula 5 >

In this formula,
Ar 1 and Ar 2 are independently a substituted or unsubstituted C ₆ -C ₂₀ arylene group or a substituted or unsubstituted C ₂ -C ₂₀ heteroarylene group,
R _c , R _d , R _e and R _f independently represent a hydrogen atom, a substituted or unsubstituted C ₁ -C ₁₈ alkyl group, a substituted or unsubstituted C ₂ -C ₁₈ alkenyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkoxy group, a substituted or unsubstituted C ₆ -C ₁₈ aryl group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkyl group, a substituted or unsubstituted C ₃ -C ₁₈ alkyl acrylate group, a substituted or unsubstituted a C ₄ -C ₁₈ alkyl methacrylate group, a substituted or unsubstituted C ₁ -C ₁₈ aminoalkyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkyl, an alkenyl group, a substituted or unsubstituted C ₆ -C ₁₈ arylalkyl group , And a substituted or unsubstituted C ₆ -C ₁₈ alkylaryl group,
m1 is an integer of 2 to 10, n1 and n2 are independently an integer of 2 to 100, r and s are molar ratios, r + s = 1, r: s = 10:90 to 90:10, t is a degree of polymerization and is 2 to 1000; 4. The organic electroluminescent device according to claim 3, wherein R _c , R _d , R _e and R _f independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group, an allyl group, , A phenyl group, a naphthyl group, or a naphthol group. 4. The copolymer of claim 3 wherein Arl and Ar2 are independently selected from the following divalent residue structure:

In the above structural formulas,
R ₁ , R ₂ and R ₃ independently of one another are a hydrogen atom, a halogen, a hydroxy group, a substituted or unsubstituted C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkenyl group, a C ₁ -C ₆ alkoxy Or a C ₆ -C ₂₀ aryl group. 4. The copolymer of claim 3 wherein Arl and Ar2 are independently selected from the following divalent residue structure:

In the above structural formulas,
R ₄ , R ₅ and R ₆ independently represent a hydrogen atom, a halogen, a hydroxyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert- butyl group, a methoxy group, , Naphthyl, or a naphthol group. The copolymer according to claim 1, wherein the copolymer is any one of the copolymers represented by the following formulas (6a) to (6k):
&Lt; Formula 6a &

&Lt; Formula 6b >

&Lt; Formula 6c >

<Formula 6d>

<Formula 6e>

(6f)

<Formula 6g>

<Formula 6h>

<Formula 6i>

<Formula 6j>

<Formula 6k>

In the above equations,
r and s are independently an integer of 2 to 10, n1 and n2 are independently an integer of 2 to 100, r and s are mole fractions, r + s = 1, r: s = 10, and t is a degree of polymerization of 2 to 1000. The copolymer according to claim 1, having a weight average molecular weight of 1,000 to 20,000. The copolymer according to claim 1, wherein the dielectric constant is 3.0 or less. 10. A copolymer according to any one of claims 1 to 9; And
A composition comprising an organic solvent. The composition according to claim 10, wherein at least 5 parts by weight of the copolymer is dissolved in 100 parts by weight of the organic solvent. The composition according to claim 10, wherein the coating film obtained from the composition has a shrinkage ratio before and after heat treatment of 20% or less. 11. The composition of claim 10, further comprising at least one additive selected from a crosslinking agent, an acid catalyst, and a surfactant. 11. The composition of claim 10, wherein the composition is used for gap fill, double patterning or hard mask. 10. A semiconductor device comprising an insulating film containing at least one selected from a copolymer according to any one of claims 1 to 9 and a cured product thereof. Mixing an arylene ether oligomer represented by the following formula (13) and a siloxane oligomer represented by the following formula (14) to prepare a mixture; And
And reacting the mixture to prepare a copolymer.
&Lt; Formula 13 >

&Lt; Formula 14 >

Ar 1 and Ar 2 are independently a substituted or unsubstituted C ₆ -C ₂₀ arylene group or a substituted or unsubstituted C ₂ -C ₂₀ heteroarylene group,
R _c , R _d , R _e and R _f independently represent a hydrogen atom, a substituted or unsubstituted C ₁ -C ₁₈ alkyl group, a substituted or unsubstituted C ₂ -C ₁₈ alkenyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkoxy group, a substituted or unsubstituted C ₆ -C ₁₈ aryl group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkyl group, a substituted or unsubstituted C ₃ -C ₁₈ alkyl acrylate group, a substituted or unsubstituted a C ₄ -C ₁₈ alkyl methacrylate group, a substituted or unsubstituted C ₁ -C ₁₈ aminoalkyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkyl vinyl group, a substituted or unsubstituted C ₆ -C ₁₈ aryl An alkyl group, and a substituted or unsubstituted C ₆ -C ₁₈ alkylaryl group,
Rh and Rg are each independently hydrogen, a hydroxyl group, a halogen group or a substituted or unsubstituted C ₁ -C ₁₈ alkoxy group,
m1 is an integer of 2 to 20, and n1 and n2 are independently from each other 2 to 200; The method for producing a copolymer according to claim 16, wherein the arylene ether oligomer comprises an oligomer represented by the following formula (13), and the siloxane oligomer comprises an oligomer represented by the following formula (14)
&Lt; Formula 13 >

&Lt; Formula 14 >

In the above equations,
Ar 1 and Ar 2 are independently a substituted or unsubstituted C ₆ -C ₂₀ arylene group or a substituted or unsubstituted C ₂ -C ₂₀ heteroarylene group,
R _c , R _d , R _e and R _f independently represent a hydrogen atom, a substituted or unsubstituted C ₁ -C ₁₈ alkyl group, a substituted or unsubstituted C ₂ -C ₁₈ alkenyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkoxy group, a substituted or unsubstituted C ₆ -C ₁₈ aryl group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkyl group, a substituted or unsubstituted C ₃ -C ₁₈ alkyl acrylate groups, substituted or unsubstituted hwandoen C ₄ -C ₁₈ alkyl methacrylate group, a substituted or unsubstituted C ₁ -C ₁₈ aminoalkyl group, a substituted or unsubstituted C ₁ -C ₁₈ alkyl vinyl group, a substituted or unsubstituted C ₆ -C ₁₈ unsubstituted An aralkyl group, and a substituted or unsubstituted C ₆ -C ₁₈ alkylaryl group,
R _h and R _g are each independently hydrogen, a hydroxyl group, a halogen group or a substituted or unsubstituted C ₁ -C ₁₈ alkoxy group,
m1 is an integer of 2 to 10, and n1 and n2 are independently an integer of 2 to 100. The method for producing a copolymer according to claim 16, wherein the arylene ether oligomer comprises an oligomer selected from the following formulas (15a) to (15e)
&Lt; Formula 15a &

<Formula 15b>

<Formula 15c>

<Formula 15d>

<Formula 15e>

In the above equations,
m1 is an integer of 4 to 10,
R ₁ , R ₂ and R ₃ independently represent a hydrogen atom, a halogen, a hydroxyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert- butyl group, a methoxy group, , Naphthyl, or a naphthol group. The method for producing a copolymer according to claim 16, wherein the siloxane-based oligomer comprises at least one oligomer selected from the following formulas (16a) to (16c):
<Formula 16a>

<Formula 16b>

<Formula 16c>

In the above equations,
n1 and n2 are each independently an integer of 2 to 100,
R _h and R _g are, independently of each other, hydrogen, a hydroxy group, a halogen group or a substituted or unsubstituted C ₁ -C ₁₈ alkoxy group. 17. The process for producing a copolymer according to claim 16, wherein the reaction is carried out at a temperature of 50 to 200 DEG C for 1 to 100 hours.

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