KR20140083421A - Novel acryl monomer, polymer and resist composition comprising the same - Google Patents

Abstract

The present invention provides an acryl monomer of Chemical formula 1 which is useful as a monomer for forming a resist additive that may exhibit high hydrophobicity before development and therefore, separate water and resist during the formation of a pattern, and prevent the drainage of composing elements in a resist such as a low molecular material and a hydrophilic additive, etc., to water, while being transformed into hydrophilic after development and decreasing pattern defects after development; a polymer for adding in a resist including a repeating unit derived from the acryl monomer; and a resist composition including the polymer. In Chemical formula 1, each of the substituents are defined as in the specification.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel acrylic monomer, a polymer and a resist composition containing the acrylic monomer,

The present invention relates to a novel acrylic monomer useful as a monomer for forming a resist additive, a polymer for a resist additive containing the repeating unit derived therefrom, and a resist composition containing the same.

In recent years, miniaturization of photoresist patterns has been demanded due to high integration and high speed of a large scale integrated circuit (LSI). G-line (436 nm) or i-line (365 nm) such as mercury is mainly used as an exposure light source used for forming a resist pattern.

However, as the improvement in the resolution derived from the exposure wavelength approaches the essential limit, a method of shortening the exposure wavelength by means of forming a finer photoresist pattern has been proposed. As a specific example thereof, a short wavelength KrF excimer laser (248 nm) and an ArF excimer laser are used instead of the i-line (365 nm).

The ArF immersion lithography method using an ArF excimer laser as a light source is characterized in that water is impregnated between a projection lens and a wafer substrate. This method uses a refractive index of water at 193 nm to form a pattern even if a lens of NA 1.0 or more is used, and is usually called a liquid immersion exposure method. However, since the resist film directly contacts with pure water, the amine compound added to the resist film as an acid or a quencher by the photoacid generator tends to be dissolved in water, and the shape change And pattern defects due to swelling, various defects such as bubble defects and watermark defects, and the like. In addition, a small amount of water droplets remaining after the scan may penetrate into the resist film and cause defects. Furthermore, in the case of a resist not using a top coat, since a faster scan speed is required at the time of exposure, the resist has to have extreme hydrophobic characteristics before development. In order to reduce the occurrence of pattern defects, 50 ° Or less.

For this reason, a method of forming a protective film or an upper layer film between the resist film and water for the purpose of blocking the resist film and a medium such as water has been proposed. Such a resist protective film can be formed on a resist film without causing intermixing with the resist film while having a sufficient light transmittance of a corresponding wavelength so as not to interfere with exposure, and is dissolved in a medium such as water at the time of liquid immersion exposure A stable film can be formed and maintained, and at the time of development, a property capable of being easily dissolved in an alkaline solution such as a developing solution is required.

As another method, an additive is used mainly for the resist to exhibit high hydrophobicity before the development in the manufacture of the resist, but to exhibit hydrophilicity after the development by generating an alcohol group by the deaeration reaction. However, the conventional resist additive has a low alcohol generation rate, making it difficult to make the static contact angle of the resist surface sufficiently hydrophilic after development.

Patent Document 1: Korea Patent No. 0959841 (Registered on May 18, 2010) Patent Document 2: Korean Patent Laid-Open Publication No. 2011-0084848 (published on July 26, 2011)

It is an object of the present invention to provide a resist composition which exhibits high hydrophobicity before development in the resist pattern formation, separates water and resist, prevents a low molecular substance and a hydrophilic additive which are constituent materials in the resist from escaping into water, And to provide a novel acrylic monomer useful as a resist additive capable of forming a fine resist pattern having excellent sensitivity and resolution by suppressing pattern defects.

Another object of the present invention is to provide a polymer for a resist additive comprising a repeating unit derived from the acrylic monomer.

Still another object of the present invention is to provide a resist composition containing the polymer and a method of forming a resist pattern using the resist composition.

According to one embodiment of the present invention, there is provided an acrylic monomer having a structure represented by the following Formula 1:

[Chemical Formula 1]

In Formula 1,

R is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

X is a branched or cyclic hydrocarbon group having 3 to 30 carbon atoms containing a functional group of the following formula (2) and at least one functional group of the following formula (3)

(2)

(3)

In the above Formulas 2 and 3,

Y is a base liable group containing a fluorine atom, and

Z is a base-sensitive group not containing a fluorine atom.

Preferably, the base-sensitive group containing the fluorine atom is selected from the group consisting of a trifluoroacetyl group, a pentafluoroethylcarbonyl group and a heptafluoropropylcarbonyl group, and the base-sensitive group not containing the fluorine atom is selected from a trichloroacetyl group , A phenylcarbonyl group, a methoxycarbonyl group and a t-butylcarbonyl group.

Preferably, the acrylic monomer of Formula 1 may be a compound having the structure of Formula 1a or 1b.

[Formula 1a]

[Chemical Formula 1b]

According to another embodiment of the present invention, there is provided a polymer for a resist additive comprising a repeating unit derived from the above acrylic monomer.

The polymer may further comprise a repeating unit represented by the following formula (5): < EMI ID =

[Chemical Formula 5]

In Formula 5,

R ¹ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and

R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a heteroalkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, A heteroaryl group, and combinations thereof.

Preferably, the polymer may have the structure of Formula 6:

[Chemical Formula 6]

In Formula 6,

R is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

X is a branched or cyclic hydrocarbon group having 3 to 30 carbon atoms containing a functional group of the following formula (2) and at least one functional group of the following formula (3)

(2)

(3)

(In the above formulas 2 and 3, Y is a base-sensitive group containing a fluorine atom and Z is a base-sensitive group not containing a fluorine atom)

R ¹¹ and R ¹² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a heteroalkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, A heteroaryl group having 5 to 30 carbon atoms, and a combination thereof; and

1, m and n each represent a number representing the molar ratio of the repeating units in the main chain, and 1 + m + n = 1 and 0 <1 / (l + m + n) ) &Lt; / = 0.99, 0 &lt; n / (l + m + n)

,

및

로 이루어진 군에서 선택되는 산 민감성 기이고, 이때 Ra, Rb 및 Rc는 각각 독립적으로 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 30의 시클로알킬기, (탄소수 1 내지 10의 알킬)시클로알킬기, 히드록시알킬기, 탄소수 1 내지 20의 알콕시기, (탄소수 1 내지 10의 알콕시)알킬기, 아세틸기, 아세틸알킬기, 카르복실기, (탄소수 1 내지 10의 알킬)카르복실기, (탄소수 3 내지 18의 시클로알킬)카르복실기, 탄소수 3 내지 30의 헤테로시클로알킬기 및 이들의 조합으로 이루어진 군에서 선택되거나, 또는 서로 인접한 기들끼리 연결되어 탄소수 3 내지 30의 포화되거나 또는 불포화된, 탄화수소 고리 또는 헤테로사이클 고리를 형성할 수 있으며, Rd는 탄소수 1 내지 10의 알킬기이고, p는 0 내지 3의 정수이고, q는 0 내지 10의 정수이며, 그리고Preferably, the R &lt; ²¹ &gt;

,

And

Wherein Ra, Rb and Rc are independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a (cycloalkyl group having 1 to 10 carbon atoms) cycloalkyl group, a hydroxyalkyl group , An alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an acetyl group, an acetylalkyl group, a carboxyl group, a (carboxyalkyl group) Or a combination thereof, or adjacent groups may be connected to form a saturated or unsaturated, saturated or unsaturated, hydrocarbon ring or heterocyclic ring having 3 to 30 carbon atoms, and Rd is a hydrocarbon group having from 1 to 30 carbon atoms P is an integer of 0 to 3, q is an integer of 0 to 10, and

또는

이며, 이때 Re 및 Rf는 각각 독립적으로 탄소수 1 내지 10의 알킬기이거나 서로 연결되어 포화 탄화수소 고리를 형성할 수 있으며, r 및 s는 각각 독립적으로 0 내지 5의 정수이다)일 수 있다.R ²² is

or

And Re and Rf are each independently an alkyl group having 1 to 10 carbon atoms or may be connected to each other to form a saturated hydrocarbon ring, and r and s are each independently an integer of 0 to 5).

More preferably, R ²¹ is a t-butyl group, a trimethylsilyl group, a hydroxy-2-ethyl group, a 1-methoxypropyl group, a 1-methoxy- Ethoxy-1-ethyl group, t-butoxy-2-ethyl group, 1-isobutoxy-1- , &Lt; / RTI &gt;

In formulas (7a) to (7j), R ', R "and R'" each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, Alkylsilyl group, a and e are integers of 0 to 15, b is an integer of 0 to 11, c and d are each independently an integer of 0 to 9, and f is an integer of 0 to 7 G and i are each independently an integer of 0 to 6, 0? C + d? 17, 0? C + f? 15, and

The R ²² may have the structure of the following formula (10a) or (10b).

The polymer may preferably have a polystyrene reduced weight average molecular weight of 1,000 to 20,000 g / mol by gel permeation chromatography.

The polymer preferably has a weight-average molecular weight to number-average molecular weight of 1 to 3.

Preferably, the polymer may be selected from the group consisting of compounds having the structures of the following formulas (11a) to (11p): &lt; EMI ID =

M, and n are 1 + m + n = 1 and 0 < l / (m + n) /(l+m+n)?.99.

According to another embodiment of the present invention, there is provided a resist composition comprising the above-mentioned polymer for a resist additive, a base polymer for a resist, an acid generator, and a solvent.

The polymer for a resist additive may be contained in an amount of 0.05 to 5% by weight based on the total weight of the resist composition.

The acid generator may be at least one compound selected from the group consisting of compounds represented by the following general formulas (13) and (14)

[Chemical Formula 13]

[Chemical Formula 14]

In the above formulas 13 and 14,

X ₁ , X ₂ , Y ₁ and Y ₂ are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms, an allyl group, a perfluoroalkyl group, a benzyl group, an aryl group having 6 to 30 carbon atoms, And X ₁ and X ₂ and Y ₁ and Y ₂ may combine with each other to form a saturated or unsaturated hydrocarbon ring having 3 to 30 carbon atoms,

X ₃ , X ₄ , X ₅ , Y ₃ , Y ₄ and Y ₅ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, a halogen group, an alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, A thioalkoxy group having 1 to 30 carbon atoms, an alkoxycarbonylmethoxy group having 1 to 20 carbon atoms, and combinations thereof,

Z of the anionic portion is _{OSO 2 CF 3, OSO 2 C} 4 F 9, OSO 2 C 8 F 17, N (CF 3) 2, N (C 2 F 5) 2, N (C 4 F 9) 2, C _{(CF 3) 3, C (} C 2 F 5) 3, C (C 4 F 9) 3, or Is a functional group represented by the following formula (15).

[Chemical Formula 15]

(In the above formula (15)

V ₁ and V ₂ are each independently a halogen atom,

W ₁ is - (C = O) - or - (SO ₂ ) -,

W ₂ is an alkanediyl group having 1 to 10 carbon atoms,

W ₃ is any one selected from the group consisting of a cycloalkanediyl group having 3 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, and a heterocycloalkylene group having 5 to 30 carbon atoms,

W ₄ represents a hydrogen atom, a halogen group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, , A cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 5 to 30 carbon atoms, Or a combination thereof,

o is an integer from 0 to 1,

and p is an integer of 0 to 2)

The resist composition may further comprise an additive selected from the group consisting of an alkali dissolution inhibitor, an acid diffusion inhibitor, a surfactant, and a mixture thereof.

According to another embodiment of the present invention, there is provided a method of manufacturing a resist pattern, comprising: forming a resist film by applying the resist composition on a substrate; exposing the resist film to a predetermined pattern after heat treatment; The resist pattern forming method comprising the steps of:

The exposure process may be performed using a light source selected from the group consisting of KrF excimer laser, ArF excimer laser, extreme ultraviolet laser, X-ray and electron beam.

Other details of the embodiments of the present invention are included in the following detailed description.

The polymer for resist additive prepared from the novel acrylic monomer according to the present invention exhibits high hydrophobicity before development in the resist pattern formation to separate water and resist and prevent the low molecular substances and the hydrophilic additives, , And after development, it is converted into hydrophilicity to reduce pattern defects after development, and a fine resist pattern having excellent sensitivity and resolution can be formed.

1 shows 13 C-NMR (CDCl ₃ , 400 MHz) of the compound (1a) prepared in Synthesis Example 1 of a monomer.
2 shows 1 H-NMR (CDCl ₃ , 400 MHz) of the compound (1a) prepared in Synthesis Example 1 of the monomer.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

In the present specification, all the compounds or substituents may be substituted or unsubstituted unless otherwise specified. Herein, the term "substituted" means that hydrogen is substituted with at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an amino group, a cyano group, a methyl cyano group, an alkoxy group, a nitrile group, an aldehyde group, An ester group, a carbonyl group, an acetal group, a ketone group, an alkyl group, a perfluoroalkyl group, a cycloalkyl group, a heterocycloalkyl group, an allyl group, a benzyl group, an aryl group, a heteroaryl group, a derivative thereof and a combination thereof Or any of the following:

In the present specification, "a combination thereof" means that two or more substituents are bonded to each other through a single bond or a linking group, or two or more substituents are condensed and connected to each other.

In the present invention, a base labile group including a fluorine atom such as a trifluoroacetyl group that affects hydrophobicity and a monomer containing a base-sensitive functional group that does not affect the hydrophobicity are used By preparing a polarity switchable additive for a resist, a high hydrophobicity is exhibited before development in the formation of a resist pattern, thereby separating the water and the resist and preventing the low molecular substances and the hydrophilic additives, which are constituent substances in the resist, And develops hydrophilicity after development to reduce pattern defects after development. In particular, by generating two or more alcohol groups that occur after the degassing reaction, the hydrophilicity after development is amplified to further reduce the occurrence of defects during development. As a result, it is possible to form a good resist pattern after development.

Thus, according to one embodiment of the present invention, there is provided a novel acrylic monomer of formula (1) useful as a monomer for forming a resist additive:

[Chemical Formula 1]

In Formula 1,

R is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group,

Wherein X is a branched or cyclic hydrocarbon group having 3 to 30 carbon atoms and having at least one functional group represented by the following general formula (2) and at least one functional group represented by the following general formula (3) A bicyclic alkyl group having 3 to 20 carbon atoms, a monocyclic cycloalkyl group having 3 to 14 carbon atoms, a bicyclic cycloalkyl group having 8 to 18 carbon atoms, a tricyclic cycloalkyl group having 10 to 30 carbon atoms, a cyclocyclic cycloalkyl group having 10 to 30 carbon atoms And a combination thereof. More preferably, it is an isopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, An octyl group, a norbornyl group, an adamantyl group, and combinations thereof.

(2)

(3)

In the above Formulas 2 and 3,

Y is a base-sensitive group containing a fluorine atom that affects hydrophobicity, and specifically may be a perfluoroalkylcarbonyl group such as a trifluoroacetyl group, a pentafluoroethylcarbonyl group, or a heptafluoropropylcarbonyl group, Is an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. Of these, a trifluoroacetyl group is preferred.

Z is a base-sensitive group containing no fluorine atom so as to affect only the polarity conversion before and after the development without affecting the hydrophobicity, specifically, a trichloroacetyl group, a phenylcarbonyl group, a methoxycarbonyl group or a t-butylcarbonyl group , Wherein the alkyl group is an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, and the aryl group may have 6 to 30 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, An aryl group, preferably an aryl group having 6 to 18 carbon atoms, and the alkoxy group is an alkoxy group having 1 to 10 carbon atoms, preferably an alkoxy group having 1 to 6 carbon atoms. Among these, a trichloroacetyl group or a phenylcarbonyl group is preferable.

The acrylic monomer of formula (1) according to the present invention contains one fluorine atom-containing base sensitive group in the molecule, while the base fluorine atom-free base group has at least one, preferably at least one, functional group X The number of hydrogen atoms that can be substituted with respect to the hydrogen atom, and more preferably from 1 to 10 carbon atoms. The fluorine atom-containing base-sensitive group exhibits high hydrophobicity before development in the resist pattern formation, separating water and resist, and preventing low-molecular substances and hydrophilic additives, which are constituent materials in the resist, from escaping into water. Further, the base-sensitive group containing the fluorine atom is converted into hydrophilic after development to reduce pattern defects after development. On the other hand, base-sensitive groups containing no fluorine atoms do not affect the hydrophobicity, but are converted into hydrophilic groups after the deaeration reaction by the developer. As described above, the acrylic monomer according to the present invention contains at least two fluorine-containing base-sensitive groups in the molecule, thereby exhibiting increased hydrophobicity before development and having two or more base-sensitive groups capable of generating an alcohol group The post-development hydrophilic property can be amplified. As a result, it is possible to form a fine resist pattern having excellent sensitivity and resolution.

Preferably, the acrylic monomer may be a compound having the structure of the following formula (1a) or (1b):

[Formula 1a]

[Chemical Formula 1b]

The acrylic monomer of the formula (1) having the above structure is prepared by sequentially reacting a compound of the following formula (4) with a starting compound providing a fluorine atom-containing base-sensitive group and a base-sensitive group containing no fluorine atom .

[Chemical Formula 4]

Wherein R is the same as defined above,

Xa is a branched alkyl group having 3 to 20 carbon atoms, a branched or cyclic hydrocarbon group having 3 to 30 carbon atoms, preferably containing 2 or more hydroxyl groups, a monocyclic alkyl group having 3 to 14 carbon atoms having 3 to 14 carbon atoms A bicyclic cycloalkyl group having from 8 to 18 carbon atoms, a tricyclic cycloalkyl group having from 10 to 30 carbon atoms, a cycloalkyl group having from 10 to 30 carbon atoms, and combinations thereof, more preferably two or more hydroxyl groups A cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a norbornyl group, an adamantyl group, and combinations thereof.

Specifically, the acrylic monomer of Formula 1 may be prepared by reacting the compound of Formula 4 with a starting compound capable of providing a fluorine atom-containing base-sensitive group in the presence of a basic compound and a base compound capable of providing a base- The order of the reaction is not particularly limited, and the reaction with each of the starting compounds may be repeated according to the number of base-sensitive groups contained in the general formula (1).

As the compound of formula (4), 2-methyl-acrylic acid-3,5-dihydroxy-adamantan-1-yl ester (2-methyl- 3-hydroxy-2-hydroxymethyl-2-methyl-propionyl ester or 2- (adamantan-1-yloxymethyl) - Adamantan-1-yloxymethyl-2-methyl-propane-1,3-diol) and the like can be used.

As the starting compound capable of providing the fluorine atom-containing base-sensitive group, an acid anhydride containing a fluorine atom-containing base-sensitive group can be used, wherein the fluorine atom-containing base-sensitive group is as defined above. Specifically, as the starting compound capable of providing the fluorine atom-containing base-sensitive group, trifluoroacetic anhydride, pentafluoropropionic anhydride, or heptafluorobutyric anhydride may be used. These may be used alone or in combination of two or more.

As the starting compound capable of providing a base-sensitive group containing no fluorine atom, an acid anhydride, a chloride, or a carboxylate containing a base-sensitive group not containing a fluorine atom can be used. In this case, The non-reactive base groups are as defined above. Specific examples thereof include trichloroacetic anhydride, benzoyl chloride, methyl chloroformate, t-butyl bicarbonate or di-t-butyl bicarbonate. t-butyl bicarbonate, etc. These may be used singly or in combination of two or more kinds.

As the basic compound, pyridine, dimethylaminopyridine (DMAP), triethylamine, diethylisopropylamine, or the like may be used. One of them may be used alone Or two or more of them may be used in combination.

The solvent may be selected from the group consisting of esters, ethers, lactones, ketones, amides, alcohols, and combinations thereof. Preferred examples of the solvent include dichloromethane, chloroform, dichloroethane, acetonitrile, Any one selected from the group consisting of dimethylformamide, tetrahydrofuran, dimethylformamide, dimethysulfoxide, acetone, and mixtures thereof may be used together.

The amount of use of the reactants may be determined stoichiometrically.

The following reaction scheme (1) schematically shows a reaction mechanism for generating an alcohol group in a developer treatment of an acrylic monomer according to the present invention. The following Reaction Scheme 1 is only one example for illustrating the present invention, but the present invention is not limited thereto.

[Reaction Scheme 1]

As shown in Reaction Scheme 1, a polymer containing a repeating unit derived from a monomer having the above structure is applied to a resist composition, and when the pattern is formed, the trifluoroacetyl group and the trichloroacetyl group are degassed by the developing solution, . At this time, since the polarity is changed from hydrophobic to hydrophilic, it is possible to improve the accessibility of the developer and the rinse used in the process, and as a result, the defect shown in the pattern profile can be reduced . Particularly, in the acrylic monomer, since all of the base-sensitive groups can be deaerated by the developer irrespective of the presence or absence of fluorine atoms, the amount of alcohol produced thereafter becomes twice or more than that of the monomer of the conventional polarity- And as a result, the degree of change from hydrophobic to hydrophilic groups is turned on and is useful as a polarity switchable enhancer.

In addition, the monomer according to the present invention may contain at least one base sensitive group that affects hydrophobicity, such as trifluoroacetyl, and at least one base labile group that does not affect hydrophobicity, such as trichloroacetyl group , The polarity difference before and after the development is two times or more, but the fluorine atom-containing base-sensitive group that affects the post-development polarity is one and can satisfy the property of relatively low polarity. As a result, the hydrophobicity of the surface of the resist becomes excessively strong, and there is no possibility of occurrence of defects.

According to another embodiment of the present invention, there is provided a polymer for a resist additive (hereinafter, referred to as a 'resist additive') comprising a repeating unit derived from the acrylic monomer of the above formula (1).

The resist additive may further include a repeating unit represented by the following formula (5)

[Chemical Formula 5]

In Formula 5,

R ¹ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and

R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a heteroalkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, A heteroaryl group, and combinations thereof.

Preferably, the additive for regent may be a copolymer represented by the following formula (6)

[Chemical Formula 6]

In Formula 6, R and X are as defined above,

The R ¹¹ And R ¹² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom, a methyl group, and an ethyl group,

R ²¹ and R ²² are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a heteroalkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, An aryl group, a heteroaryl group having 5 to 30 carbon atoms, and a combination thereof,

1, m and n each represent a number representing the molar ratio of the repeating units in the main chain, and 1 + m + n = 1 and 0 <1 / (l + m + n) ) &Lt; / = 0.99, 0 &lt; n / (l + m + n)

Preferably, in Formula 6, R ²¹ may be an acid labile group. By including the acid-sensitive functional group in this way, the hydrophobic property is changed from hydrophobic to hydrophilic by the acid-assisted deprotection at the exposed site in the exposure, and as a result, it can be easily washed away by the developer during development at the exposed site.

,

및

로 이루어진 군에서 선택되는 산 민감성 기이고, 이때 R', R" 및 R"'은 각각 독립적으로 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 30의 시클로알킬기, (탄소수 1 내지 10의 알킬)시클로알킬기, 히드록시알킬기, 탄소수 1 내지 20의 알콕시기, (탄소수 1 내지 10의 알콕시)알킬기, 아세틸기, 아세틸알킬기, 카르복실기, (탄소수 1 내지 10의 알킬)카르복실기, (탄소수 3 내지 18의 시클로알킬)카르복실기 및 탄소수 3 내지 30의 헤테로시클로알킬기 및 이들의 조합으로 이루어진 군에서 선택되거나, 또는 서로 인접한 기들끼리 연결되어 탄소수 3 내지 30의 포화되거나 또는 불포화된, 탄화수소 고리 또는 헤테로사이클 고리를 형성할 수 있으며, R""는 탄소수 1 내지 10의 알킬기이고, z는 0 내지 3의 정수이고, w는 0 내지 10의 정수이다. Specifically, R &lt; ²¹ &gt;

,

And

Wherein R ', R "and R"' are each independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a (cycloalkyl group having 1 to 10 carbon atoms) (Alkyl group having 1 to 10 carbon atoms), a hydroxyalkyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an acetyl group, an acetylalkyl group, a carboxyl group, A carboxyl group, a heterocycloalkyl group having 3 to 30 carbon atoms, and a combination thereof, or adjacent groups may be connected to form a saturated or unsaturated hydrocarbon ring or heterocyclic ring having 3 to 30 carbon atoms , R "&quot; is an alkyl group having 1 to 10 carbon atoms, z is an integer of 0 to 3, and w is an integer of 0 to 10.

More preferably, R ²¹ is a t-butyl group, a trimethylsilyl group, a hydroxy-2-ethyl group, a 1-methoxypropyl group, a 1-methoxy- Ethoxy-1-ethyl group, t-butoxy-2-ethyl group, 1-isobutoxy-1-ethyl group and the following formulas (7a) to It is selected from the group consisting of.

Wherein R ', R "and R'" each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a hydroxy group, an alkylsilyl group having 1 to 10 carbon atoms, a cycloalkylsilyl group having 3 to 18 carbon atoms And o and s are integers of 0 to 15, p is an integer of 0 to 11, q and r are each independently an integer of 0 to 9, t is 0 to 1, And u and v are each independently an integer of 0 to 6, 0? Q + r? 17, and 0? Q + t? 15.

More preferably, R &lt; ²¹ &gt; may be selected from the group consisting of the following formulas (8a) to (8h).

Specifically, it is preferable that the acrylic derivative-derived repeating unit m in the formula (6) has a structure represented by the following formulas (9a) to (9d).

In the above formula (6), R ²² may preferably be a lactone group.

By including such a lactone group, the adhesion on the wafer can be improved.

또는

이며(이때 R' 및 R"은 각각 독립적으로 탄소수 1 내지 10의 알킬기이거나 서로 연결되어 포화 탄화수소 고리를 형성할 수 있으며, x 및 y는 각각 독립적으로 0 내지 5의 정수이다)일 수 있으며, 보다 바람직하게는 하기 화학식 10a 또는 10b일 수 있다.Specifically, R &lt; ²² &gt;

or

(Wherein R 'and R "are each independently an alkyl group having 1 to 10 carbon atoms or may be connected to each other to form a saturated hydrocarbon ring, and x and y are each independently an integer of 0 to 5) Preferably 10a or 10b.

Generally, a static contact angle (SAC) should be formed at 90 ° or more in order to increase the scan speed in exposure to a resist film. However, a high SCA at the time of post-exposure development requires a blob defect , The blot defects can be reduced by making the surface of the resist film have a low SCA in the post-exposure development. On the contrary, the resist additive according to the present invention has a hydrophobic base-sensitive group having a structure in which an electron withdrawing group is substituted at an alpha carbon position, such as a trifluoroacetyl group, thereby increasing the hydrophobicity of the resist film, .

Specifically, in the polymer of Formula 6, the monomer-derived repeating unit 1 of Formula 1 contains a hydrophobic base-sensitive group, thereby improving the hydrophobic property of the surface of the resist film during exposure and leaching by water during the lithography process In the post-exposure development, the hydrophobic group is deaerated by a basic developer such as trimethylammonium hydroxide (TMAH) to be converted into an alcohol group, so that the hydrophilic property is changed to hydrophilic property. Thus, it is possible to improve the accessibility of the developer and the rinse, and as a result, it is possible to reduce defects that appear in the pattern profile.

In addition, since the repeating unit 1 further includes a base-sensitive group which does not affect the hydrophobicity in addition to the hydrophobic base-sensitive group, the number of functional groups that can be deaerated by the developer is two, It is twice as large as that of the additive, so the degree of change from hydrophobic to hydrophilic is large.

The repeating unit 1 also includes a base-sensitive group which does not affect the hydrophobic base-sensitive group and the hydrophobic group, and thus the hydrophobic properties of the resist surface are appropriately controlled, thereby preventing the occurrence of defects due to excessively high hydrophobicity of the resist surface have.

In the polymer of formula (6), the repeating unit (m) derived from an acrylic derivative includes an acid labile group, which is converted from a hydrophobic property to a hydrophilic property by a deprotection reaction by an acid at an exposure site upon exposure, As a result, it is easily washed away by the developing solution at the exposed portion.

In the polymer of formula (6), the acrylic derivative-derived repeating unit (n) contains a lactone group, so that the adhesive force on the wafer can be reinforced.

In the polymer of Formula 6, the repeating units 1, m and n represent the content of each repeating unit in the main chain and mean the substitution rate at which the polymer is dissolved in the developing solution. The polymer according to the present invention is characterized in that the repeating units l, m and n satisfy 0 < l / (m + n) n)? 0.99 and 0 < n / (l + m + n)? 0.99. By including the above recurring units in the above ratio, hydrophobic properties exhibiting little affinity with water can be exhibited during liquid immersion lithography. In particular, by containing the monomer-derived recurring unit 1 of formula (1) in an amount of 70 mol% or less, It is possible to reduce defects and form a uniform pattern throughout the wafer.

The resist additive according to the present invention having the above structure may be a block copolymer, a random copolymer or a graft copolymer.

Specific examples of the resist additive according to the present invention include compounds having the structures of the following formulas (11a) to (11p), and the order of each repeating unit in the structural formula may be changed:

M, and n are 1 + m + n = 1 and 0 < l / (m + n) /(l+m+n)?.99.

The resist additive according to the present invention may have a polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") of from 1,000 to 20,000 g / mol by gel permeation chromatography (GPC). When the weight average molecular weight of the polymer is too small, it may cause intermixing or elution into pure water in the case of liquid immersion light. If it is too large, proper film formation may be difficult or alkaline solubility may be deteriorated. Preferably, the weight average molecular weight of 2,000 to 10,000 g / mol is preferable because it can exhibit excellent solubility in a developing solution without concern for elution into pure water.

The resist additive preferably has a molecular weight distribution (Mw / Mn) of a weight-average molecular weight to a number-average molecular weight of 1 to 5, more preferably 1 to 3. If the molecular weight distribution of the weight is more than 3, the line edge roughness may not be good. Therefore, when used as a photoresist composition, the resist additive, which is a range of the weight average molecular weight and the molecular weight distribution, can exhibit appropriate physical properties in terms of developability, coatability and heat resistance.

The resist additive according to the present invention having the above structure may be prepared by a conventional polymerization method such as bulk polymerization, solution polymerization, suspension polymerization or polymerization using an acrylic monomer having the formula (1) and optionally an acrylic monomer having a structure represented by the following formula , Bulk suspension polymerization, emulsion polymerization, and the like.

[Chemical Formula 12]

In Formula 12, R ¹ and R ² are as defined above.

Preferably, the resist additive according to the present invention may be polymerized by radical polymerization, and examples of the radical polymerization initiator include azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), lauryl peroxide, azo There is no particular limitation as long as it is used as a general radical polymerization initiator such as bisisocapronitrile, azobisisobalonitrile, and t-butylhydroperoxide.

As the polymerization solvent, at least one selected from benzene, toluene, xylene, halogenated benzene, diethyl ether, tetrahydrofuran, esters, ethers, lactones, ketones, amides and alcohols is used.

The polymerization temperature in the polymerization reaction is appropriately selected depending on the kind of the catalyst. The molecular weight distribution of the polymer to be produced can be appropriately controlled by changing the amount of the polymerization initiator used and the reaction time. After the polymerization is completed, the unreacted monomers and by-products remaining in the reaction mixture are preferably removed by a precipitation method using a solvent.

According to another embodiment of the present invention, there is provided a resist composition comprising the resist additive.

Specifically, the resist composition includes a resist base polymer, an acid generator, and a solvent together with a resist additive.

The resist additive is the same as that described above, and may be contained in an amount of 0.01 to 5% by weight, preferably 0.05 to 1% by weight based on the total weight of the resist composition. If the content of the resist additive is less than 0.05 wt%, the effect of the use of the additive is insignificant, and if it exceeds 5 wt%, the CA value exceeds the appropriate CA value to cause water mark defects.

The base polymer for resist can be used without particular limitation as long as it is used as a base resin at the time of forming a resist film. Specific examples thereof include polymers obtained by ring-opening metathesis reaction of (meth) acrylic acid ester polymer, (? -Trifluoromethyl) acrylic acid ester-maleic anhydride copolymer, cycloolefin-maleic anhydride copolymer, polynorbornene and cycloolefin (Meth) acrylic acid ester derivatives, styrene, vinylnaphthalene, vinyl anthracene, vinyl pyrene, hydroxyvinyl naphthalene, hydroxyvinyl (meth) acrylate, and the like; a polymer compound obtained by hydrogenating a polymer obtained by ring-opening metathesis reaction of a cycloolefin; A polymer compound obtained by copolymerizing any one of anthracene, indene, hydroxyindene, acenaphthylene, and norbornadiene, a novolak resin, and a mixture thereof.

The base polymer may be contained in an amount of 3 to 20% by weight based on the total weight of the resist composition. If the content of the polymer is less than 3% by weight, the viscosity of the composition becomes too low to form a film having a desired thickness, and there is a problem that the pattern loss is increased by a relatively large amount of the photoacid generator. If the weight% is exceeded, the thickness of the film becomes too thick, the transmittance of the radiation becomes poor, and it is difficult to obtain a vertical pattern.

The acid generator is a photoacid generator (hereinafter referred to as "PAG") which is an onium salt based iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, pyridinium salt , And imides may be used. Preferably, at least one of the sulfonium salts represented by the following formulas (13) and (14) can be used, more preferably triphenylsulfonium nonaplate can be used:

[Chemical Formula 13]

[Chemical Formula 14]

In the above formulas 13 and 14,

X ₁ , X ₂ , Y ₁ and Y ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an allyl group, a perfluoroalkyl group having 1 to 10 carbon atoms, a benzyl group, an aryl group having 6 to 30 carbon atoms, And X ₁ and X ₂ and Y ₁ and Y ₂ may combine with each other to form a saturated or unsaturated hydrocarbon ring having 3 to 30 carbon atoms,

X ₃ , X ₄ , X ₅ , Y ₃ , Y ₄ and Y ₅ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a halogen group, an alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, Thiophenoxy, thioalkoxy having 1 to 30 carbon atoms, alkoxycarbonylmethoxy having 1 to 20 carbon atoms, and combinations thereof.

Z of the anionic portion is _{OSO 2 CF 3, OSO 2 C} 4 F 9, OSO 2 C 8 F 17, N (CF 3) 2, N (C 2 F 5) 2, N (C 4 F 9) 2, C _{(CF 3) 3, C (} C 2 F 5) 3, C (C 4 F 9) 3, or Is a functional group represented by the following formula (15)

[Chemical Formula 15]

In Formula 15,

V ₁ and V ₂ are each independently a halogen atom,

W ₁ is - (C = O) - or - (SO ₂ ) -,

W ₂ is an alkanediyl group having 1 to 10 carbon atoms,

W ₃ represents a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an arylthio group having 6 to 30 carbon atoms, A heterocyclic group, and a heterocyclic group,

W ₄ represents a hydrogen atom, a halogen group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, Or a combination thereof,

o is an integer from 0 to 1,

p is an integer of 0 to 2;

By including the cyclic alkyl group in the anion in the acid generator, the diffusion length of the acid in the resist film can be appropriately kept short, and high permeability can be exhibited. As a result, a high-resolution resist can be obtained.

Preferably, the anion moiety Z of formula (15) may be selected from the group consisting of the functional groups represented by the following general formulas (16a) to (16l) and (17a) to (17x)

In the above formulas (13) and (14), preferred cation moieties include the following structures represented by the following formulas (18a) to (18p):

The acid generators may be used alone or in admixture of two or more. The acid generator may be included in an amount of 0.3 to 15 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the polymer solid content. When the content of the acid generator is more than 15 parts by weight, the perpendicularity of the pattern is remarkably decreased. When the content of the acid generator is less than 0.3 parts by weight, the flexibility of the pattern may be lowered.

In order to obtain a uniform and flat resist coating film, it is preferable to use the polymer and the acid generator in a solvent having an appropriate evaporation rate and viscosity and use it. Examples of the solvent usable in the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Esters such as acetate and propylene glycol monopropyl ether acetate; Ketones such as methyl isopropyl ketone, cyclohexanone, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-heptanone, ethyl lactate and gamma-butyrolactone. They may be used singly or in combination of two or more.

The amount of the solvent to be used can be appropriately controlled depending on the physical properties of the solvent, such as volatility, viscosity, etc., so that a uniform resist film can be formed.

In addition, the resist composition according to the present invention may further contain additives in accordance with the purpose of improving the coatability and the like.

As the additive, any additive which is usually applied to a resist composition can be used without any particular limitation, and specific examples thereof include an alkali dissolution inhibitor, an acid diffusion inhibitor, and a surfactant, and one kind or two or more kinds thereof .

The above-mentioned alkali dissolution inhibitor can be applied as long as it is an alkali dissolution inhibitor generally applied to a resist composition. Specific examples thereof include phenol and carboxylic acid derivatives.

The acid diffusion inhibitor acts to control the diffusion phenomenon when the acid generated from the acid generator diffuses into the resist film by light irradiation and to suppress the chemical reaction in the unexposed area. By using such an acid diffusion inhibitor, it is possible to improve the storage stability of the radiation-sensitive resin composition and to further improve the resolution of the resist, and to improve the resolution of the resist pattern by changing the line width of the resist pattern The change can be suppressed.

Examples of such an acid diffusion inhibitor include basic compounds such as ammonia, methylamine, isopropylamine, n-hexylamine, cyclopentylamine, methylenediamine, ethylenediamine, dimethylamine, diisopropylamine, N, N ', N', N ', N'-tetramethylmethylenediamine, N, N'-dimethylethylenediamine, N, N-dimethylethylenediamine, trimethylamine, N, N, N ', N'-tetramethyltetraethylenepentamine, dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine, tetramethylammonium hydroxide Aniline, aniline, aniline, N, N-dimethyltoluidine triphenylamine, phenylenediamine, pyrrole, oxazole, isoxazole, thiazole, isothiazole, imidazole, pyrazole, pyrroline, pyrrolidine, imidazoline Derivatives, imidazolidine derivatives, pyridine derivatives, pyridazine derivatives Amines such as pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives and morpholine; (2-hydroxypyridine, 2-hydroxypyridine, aminocresol, 2,4-quinolinone, and the like) Diol, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine; Amide derivatives such as formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide and benzamide; And imide derivatives such as phthalimide, succinimide and maleimide.

The acid diffusion inhibitor may be contained in an amount of 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight, based on 100 parts by weight of the polymer solid content. If the content of the acid diffusion inhibitor is less than 0.01 part by weight, the influence of the post exposure latency is increased, which may affect the shape of the pattern. If the content is more than 5 parts by weight, the resolution and sensitivity may be lowered.

Specific examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene, and polyethylene glycol dilaurate. However, the surfactant is not limited thereto. It is not.

By using the resist composition according to the present invention having the above composition, it exhibits improved line width roughness upon formation of a resist pattern, and exhibits excellent resolution in both C / H pattern and L / S pattern. In addition, it has a good process window, so that a good pattern profile can be obtained regardless of the type of substrate, and an improved contrast is exhibited. Accordingly, the resist composition can be used as a positive chemical amplification photoresist that is sensitive to radiation such as deep ultraviolet rays such as KrF excimer laser, ArF excimer laser or F ₂ excimer laser, X-rays such as synchrotron radiation, And is useful as a composition.

According to another embodiment of the present invention, there is provided a pattern forming method using the resist composition.

Specifically, the pattern forming method includes a step of forming a resist film by applying the resist composition onto a substrate, a step of exposing the resist film to a predetermined pattern after the heat treatment, and a step of developing the exposed resist pattern do.

As the substrate, a wafer substrate can be used, and as a coating method on the substrate, rotational coating, flow coating, or roll coating can be used.

Specifically, it is applied on a substrate such as a silicon wafer so that the film thickness becomes 0.3 to 2.0 mu m, and this is pre-baked at 60 to 150 DEG C for 1 to 10 minutes, preferably at 80 to 130 DEG C for 1 to 5 minutes.

Subsequently, the resist film is partially irradiated with radiation to form a fine pattern. The radiation usable here is not particularly limited, but an ultraviolet ray, an ultraviolet ray, a KrF excimer laser, an ArF excimer laser, an F2 excimer laser, an X-ray and an electron beam as a charged particle ray can be used. And can be appropriately selected depending on the kind.

Specifically, after irradiating radiation at an exposure dose of about 1 to 200 mJ / cm 2, preferably about 10 to 100 mJ / cm 2, the film is irradiated at 60 to 150 ° C for 1 to 5 minutes, preferably at 80 to 130 ° C for 1 to 3 Minute Post Exposure Bake (PEB).

The resist pattern exposed after the exposure process is developed by a conventional method such as a dip method, a puddle method or a spray method for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, A desired pattern is formed. Examples of the developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium methanesulfonate, ammonia, ethylamine, n-propylamine, triethylamine, tetramethylammoniumhydroxide or tetraethylammoniumhydroxide And the like can be used, and it is preferable to use tetramethylammonium hydroxide.

Optionally, the developer may further comprise additives such as surfactants or water-soluble alcohols.

As described above, a fine resist pattern having excellent sensitivity and resolution can be formed by the pattern forming method using the resist composition according to the present invention.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

[Production Example: Synthesis of monomers and polymers]

Synthesis Example 1 of Monomer

Step 1

30 g of 2-methyl-acrylic acid-3,5-dihydroxy-adamantan-1-yl ester (1) and 2 g of trichloro 36.71 g of trichloroacetic anhydride was placed in 150 g of acetone and stirred at room temperature. After confirming that the reactants were completely dissolved, 9.39 g of pyridine was slowly added dropwise to the resultant solution. After dropwise addition, 0.8 g of 4-dimethylaminopyridine (DMAP) was added and the mixture was stirred at room temperature for 2 hours Lt; / RTI &gt; After confirming that the reaction was completed, the resulting reaction product was washed with 150 g of methylene chloride and 1.7% aqueous hydrochloric acid, and then washed twice with distilled water. After separating the organic layer from the resultant reaction product, the solvent was removed and compound (2) was obtained through column chromatography.

Step 2

24.96 g of trifluoroacetic anhydride and 47 g of the compound (2) prepared above were placed in 150 g of acetone and stirred at room temperature. After confirming that the reactants were completely dissolved in acetone, 9.39 g of pyridine was slowly added dropwise to the resultant solution. After the addition of pyridine was completed, 0.8 g of 4-dimethylaminopyridine was added and the mixture was stirred at room temperature for 2 hours. After confirming that the reaction was completed, the resulting reaction product was washed with 150 g of methylene chloride and 1.7% aqueous hydrochloric acid solution, and then washed twice with distilled water. After separation of the organic layer from the resulting reaction product, the solvent was removed and compound (1a) was obtained via column chromatography.

The obtained compound was confirmed by &lt; 13 &gt; C and 1H NMR. The results are shown in Figs. 1 and 2, respectively.

Synthesis Example 2 of Monomer

Except that 16.7 g of benzoyl chloride was used in place of 36.71 g of trichloroacetic acid anhydride in the preparation of the compound (1a) in the step 1 in Synthesis Example 1 of the monomer described above. Was carried out in the same manner as above to obtain the compound (3), and 42 g of the obtained compound (3) was used in place of 47 g of the compound (2) 1b).

Synthesis Example 1 of Polymer

(2,2,2-trichloro-acetoxy) -3- (2,2,2-trifluoro-acetoxy) -adamantan-1-yl ester (2- 10 g of 2-methyl-acrylic acid-5- (2,2,2-trichloro-acetoxy) -3- (2,2,2-trifluoro-acetoxy) -adamantan- 1 g of 2-methyl-acrylic acid 1-methyl-cyclohexyl ester and 2 g of 2-methyl-acrylic acid 2-oxo-tetrahydro-furan- -furan-3-yl ester was dissolved in 255 g of 1,4-dioxane was added to 1 g of dimethyl azobis butyronitrile (DMAB) as an initiator The mixture was placed in a jacket reactor and stirred. At this time, the temperature of the circulator was set at 75 ° C, the temperature of the reactor was gradually increased, and the mixture was stirred at 75 ° C for 8 hours. After completion of the reaction was confirmed, the resulting reaction solution was added dropwise to 2.4 L of n-hexane and 1 L of methanol to precipitate the precipitate, and the precipitate was filtered and dried in vacuo to obtain polymer (I). The polystyrene reduced weight average molecular weight of this polymer was 14000 g / mol, and the molar ratio (1: m: n) of each repeating unit was 1: 1: 1.

Synthesis Example 2 of Polymer

Synthesis of the polymer was carried out in the same manner as in Synthesis Example 1 except that 1- (2-isopropyl-adamantan-2-yl) -3-methyl- 2-yl) -3-methyl-but-3-en-2-one and 2-methyl-acryloylic acid 2-oxo-tetrahydro-furan- Methyl-acrylic acid 5-oxo-4-oxa-tricyclo [4.2.1.03,7] non-2-yl ester instead of 2-methyl-acrylic acid 2-oxo-tetrahydro- furan- (2-methyl-acrylic acid 5-oxo-4-oxa-tricyclo [4.2.1.03,7] non-2-yl ester) To give polymer (II). The weight average molecular weight of the polymer in terms of polystyrene was 13,000 g / mol, and the molar ratio (1: m: n) of each repeating unit was 1: 1: 1.

Synthesis Example 3 of Polymer

Benzoic acid 3- (2-methyl-acryloyloxy) -5- (2,2,2, -trifluoro-acetoxy) -adamantan- 1- yl ester (Benzoic acid 3- acryloyloxy-5- (2,2,2-trifluoro-acetoxy) -adamantan-1-yl ester), 10 g of 2-methyl- acrylic acid 1-isopropyl-cyclohexyl ester, cyclohexyl ester) and 17 g of 2-methyl-acrylic acid 2-methyl-acrylic acid 2-oxo-tetrahydro-furan-3- (1,4-dioxane) was added to a jacket reactor together with 1.2 g of dimethyl azobis butyronitrile (DMAB) as an initiator and stirred. At this time, the temperature of the circulator was set at 75 ° C, the temperature of the reactor was gradually increased, and the mixture was stirred at 75 ° C for 7 hours. After confirming that the reaction was completed, the resulting reaction solution was added dropwise to 2.5 L of n-hexane and 1 L of methanol and precipitated. The precipitate was filtered and vacuum dried to obtain polymer (III). The polystyrene reduced weight average molecular weight of this polymer was 9500 g / mol, and the molar ratio (1: m: n) of each repeating unit was 1: 1: 1.

Polymer Synthesis Example 4

Synthesis of the polymer was carried out in the same manner as in Synthesis Example 3 except that 1- (2-isopropyl-adamantan-2-yl) -3-methyl- 2-yl) -3-methyl-but-3-en-2-one and 2-methyl-acryloylic acid 2-oxo-tetrahydro-furan- Methyl-acrylic acid 5-oxo-4-oxa-tricyclo [4.2.1.03,7] non-2-yl ester instead of 2-methyl- 1.03,7] non-2-yl ester) was used as the polymer (IV). The weight average molecular weight of the polymer in terms of polystyrene was 10,000 g / mol, and the molar ratio (l: m: n) of each repeating unit was 1: 1: 1.

[Test Example 1: Evaluation of hydrophobicity of additives]

1.0 g of the polymer (I or III) synthesized in Polymer Synthesis Examples 1 and 3 was dissolved in 20 g of 4-methyl pentanol, and the solution was filtered with a 0.2-micrometer polypropylene filter to remove the resist . The resist prepared above was spin-coated on a silicon substrate, and then baked at 100 DEG C for 60 seconds to form a resist film having a thickness of 50 nm.

The formed resist film was measured for surface static contact angle before and after development using a surface static contact angle meter. Specifically, the silicon substrate on which the resist film is formed is held horizontally, and 50 占 퐇 of pure water is dropped thereon to form water droplets. Thereafter, the silicon substrate is gradually tilted to measure the angle of inclination of the silicon substrate , And the silicon substrate on which the resist film was formed was developed with 2.38 wt% TMAH developer for 60 seconds, and then the static contact angle after development was measured in the same manner as above.

Further, for the purpose of comparison, the static contact angle before and after the development was measured by the same method as above using the compounds of the following formulas (19) and (20) used as conventional resist additives.

[Chemical Formula 19]

In the above formula, the molar ratio l: m: n of each repeating unit is 1: 1: 1.

[Chemical Formula 20]

In the above formula, the molar ratio l: m: n of each repeating unit is 1: 1: 1.

The results are shown in Table 1 below.

Additive polymer The compound of formula 19 The compound of formula 20 Synthesis Example 1 of Polymer Synthesis Example 3 of Polymer Before development
Electrostatic contact angle (°) 92 97 92 91 After development
Electrostatic contact angle (°) 56 42 42 43 Contact angle difference (°) 36 55 50 48

Referring to Table 1 above, the compound of Formula 20 containing two base-sensitive groups and the compound prepared in Synthesis Examples 1 and 2 of Polymer showed a large polarity change compared to the compound of Formula 19 containing only one base-sensitive group. However, the compound of Formula 20, which contains two base-sensitive groups including a fluorine atom, such as a trifluoroacetyl group as a base-sensitive group, is a compound in which the trifluoroacetyl group is a base-sensitive functional group and increases hydrophobicity due to the content of fluorine atoms , The hydrophobicity of the surface of the resist before development is too strong, and accordingly, defects are easily generated, which may adversely affect the pattern profile. On the contrary, the compounds (I and III) prepared in Synthesis Examples 1 and 2 of the polymer according to the present invention contain a base-sensitive functional group that affects hydrophobicity and a base-sensitive functional group that does not affect hydrophobicity , The surface of the resist shows a hydrophobicity at the level of the conventional polarity changeable additive, that is, the compound of the above formula (19), while the polarity difference before and after the development is nearly doubled because of the presence of two base-sensitive groups.

[Test Example 2: Formation of resist film and measurement of properties of the prepared resist film]

(Examples 1 to 4)

5 g of a resist polymer (Mw: 8,500 g / mol, Mw / Mn: 1.75, molar ratio of each repeating unit (x: y: z: w) of 1: 1: 1: 1) 0.5 g of each of the additive polymers synthesized in Synthesis Examples 1 to 4, 0.31 g of the photoacid generator represented by the following Chemical Formula 22 and 0.07 g of triisopropanol amine as an inhibitor were dissolved in 80 g of propyleneglycol monoethyl ether acetate, PGMEA), and then filtered through a polypropylene filter having a size of 0.2 mu m to prepare a composition for forming a photoresist film.

[Chemical Formula 21]

[Chemical Formula 22]

An antireflection film (BARC) having a film thickness of 90 nm was formed on a silicon substrate. The composition for forming a photoresist film was coated on the substrate having the antireflection film formed thereon and baked at 110 DEG C for 60 seconds, A photoresist film having a thickness of 120 nm was formed.

Next, in order to reproduce the liquid immersion exposure, a pure water rinse was performed on the film after the exposure for 5 minutes. That is, exposure was performed with an ArF scanner 306C (NA = 0.78, 6% halftone mask) manufactured by Nikon Corporation, rinsing was performed for 5 minutes while pure water was added, PEB was performed after exposure at 110 캜 for 60 seconds, A short-time development was carried out.

As a result of observing the formed pattern, it was confirmed that a fine pattern having good pattern forming property without surface bonding was formed.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, Of the right.

Claims (17)

An acrylic monomer having a structure represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
R is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
X is a branched or cyclic hydrocarbon group having 3 to 30 carbon atoms containing a functional group of the following formula (2) and at least one functional group of the following formula (3)
(2)

(3)

In the above Formulas 2 and 3,
Y is a base liable group containing a fluorine atom, and
Z is a base-sensitive group not containing a fluorine atom. The method according to claim 1,
The fluorine atom-containing base-sensitive group is selected from the group consisting of a trifluoroacetyl group, a pentafluoroethylcarbonyl group and a heptafluoropropylcarbonyl group,
Wherein the fluorine atom-free base-sensitive group is selected from the group consisting of a trichloroacetyl group, a phenylcarbonyl group, a methoxycarbonyl group, and a t-butylcarbonyl group. The method according to claim 1,
The acrylic monomer of the formula (1) is a compound having the structure of the following formula (1a) or (1b).
[Formula 1a]

[Chemical Formula 1b]

A polymer for a resist additive comprising a repeating unit derived from the acrylic monomer according to claim 1. 5. The method of claim 4,
Wherein the polymer further comprises a repeating unit represented by the following formula (5): &lt; EMI ID =
[Chemical Formula 5]

In this formula,
R ¹ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and
R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a heteroalkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, A heteroaryl group, and combinations thereof. 5. The method of claim 4,
Wherein the polymer has a structure represented by the following formula (6): < EMI ID =
[Chemical Formula 6]

In Formula 6,
R is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
X is a branched or cyclic hydrocarbon group having 3 to 30 carbon atoms containing a functional group of the following formula (2) and at least one functional group of the following formula (3)
(2)

(3)

(In the above formulas 2 and 3, Y is a base-sensitive group containing a fluorine atom, and Z is a base-sensitive group not containing a fluorine atom)
R ¹¹ and R ¹² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a heteroalkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, A heteroaryl group having 5 to 30 carbon atoms, and a combination thereof; and
1, m and n each represent a number representing the molar ratio of the repeating units in the main chain, and 1 + m + n = 1 and 0 <1 / (l + m + n) ) &Lt; / = 0.99, 0 &lt; n / (l + m + n) The method according to claim 6,
The R &lt; ^{21 &}

,

And

Wherein Ra, Rb and Rc are independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a (cycloalkyl group having 1 to 10 carbon atoms) cycloalkyl group, a hydroxyalkyl group , An alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an acetyl group, an acetylalkyl group, a carboxyl group, a (carboxyalkyl group) having 1 to 10 carbon atoms, a carboxy group having 3 to 18 carbon atoms, To 30, or adjacent groups may be connected to form a saturated or unsaturated, saturated or unsaturated hydrocarbon ring or heterocyclic ring having 3 to 30 carbon atoms, and Rd is a group selected from the group consisting of 1 to 10 carbon atoms Alkyl group, p is an integer of 0 to 3, q is an integer of 0 to 10, and
R ²² is

or

, Wherein Re and Rf are each independently an alkyl group having 1 to 10 carbon atoms or may be connected to each other to form a saturated hydrocarbon ring, and r and s are each independently an integer of 0 to 5. The method according to claim 6,
The R ²¹ is preferably a t-butyl group, a trimethylsilyl group, a hydroxy-2-ethyl group, a 1-methoxypropyl group, a 1-methoxy- Is selected from the group consisting of methylethyl, 1-methoxy-1-ethyl, 1-ethoxy-1-ethyl, t-butoxy- And,

In formulas (7a) to (7j), R ', R "and R'" each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, Alkylsilyl group, a and e are integers of 0 to 15, b is an integer of 0 to 11, c and d are each independently an integer of 0 to 9, f is an integer of 0 to 7 G and i are each independently an integer of 0 to 6, 0? C + d? 17, 0? C + f? 15, and
And R &lt; ²² &gt; has the structure of the following formula (10a) or (10b).

5. The method of claim 4,
Wherein the polymer has a polystyrene reduced weight average molecular weight of 1,000 to 20,000 g / mol by gel permeation chromatography. 5. The method of claim 4,
Wherein the polymer has a ratio of a weight average molecular weight to a number average molecular weight of 1 to 3. 5. The method of claim 4,
Wherein the polymer is selected from the group consisting of compounds having a structure of the following formulas (11a) to (11p):

M, and n are 1 + m + n = 1 and 0 < l / (m + n) /(l+m+n)?.99. 12. A resist composition comprising the polymer for a resist additive according to any one of claims 4 to 11, a base polymer for a resist, an acid generator, and a solvent. 13. The method of claim 12,
Wherein the polymer for a resist additive is contained in an amount of 0.05 to 5% by weight based on the total weight of the resist composition. 13. The method of claim 12,
Wherein the acid generator is at least one compound selected from the group consisting of compounds represented by the following formulas (13) and (14).
[Chemical Formula 13]

[Chemical Formula 14]

In the above formulas 13 and 14,
X ₁ , X ₂ , Y ₁ and Y ₂ are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms, an allyl group, a perfluoroalkyl group, a benzyl group, an aryl group having 6 to 30 carbon atoms, And X ₁ and X ₂ and Y ₁ and Y ₂ may combine with each other to form a saturated or unsaturated hydrocarbon ring having 3 to 30 carbon atoms,
X ₃ , X ₄ , X ₅ , Y ₃ , Y ₄ and Y ₅ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, a halogen group, an alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, A thioalkoxy group having 1 to 30 carbon atoms, an alkoxycarbonylmethoxy group having 1 to 20 carbon atoms, and combinations thereof,
Z of the anionic portion is _{OSO 2 CF 3, OSO 2 C} 4 F 9, OSO 2 C 8 F 17, N (CF 3) 2, N (C 2 F 5) 2, N (C 4 F 9) 2, C _{(CF 3) 3, C (} C 2 F 5) 3, C (C 4 F 9) 3, or Is a functional group represented by the following formula (15).
[Chemical Formula 15]

(In the above formula (15)
V ₁ and V ₂ are each independently a halogen atom,
W ₁ is - (C = O) - or - (SO ₂ ) -,
W ₂ is an alkanediyl group having 1 to 10 carbon atoms,
W ₃ is any one selected from the group consisting of a cycloalkanediyl group having 3 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, and a heterocycloalkylene group having 5 to 30 carbon atoms,
W ₄ represents a hydrogen atom, a halogen group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, , A cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 5 to 30 carbon atoms, Or a combination thereof,
o is an integer from 0 to 1, and
and p is an integer of 0 to 2) 13. The method of claim 12,
Wherein the resist composition further comprises an additive selected from the group consisting of an alkali dissolution inhibitor, an acid diffusion inhibitor, a surfactant, and a mixture thereof. Applying a resist composition according to claim 12 onto a substrate to form a resist film,
Exposing the resist film to a predetermined pattern after the heat treatment, and
Developing the exposed resist pattern
And forming a resist pattern on the resist pattern. 17. The method of claim 16,
Wherein the exposure step is carried out using a light source selected from the group consisting of KrF excimer laser, ArF excimer laser, extreme ultraviolet laser, X-ray and electron beam.

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