KR101761897B1 - Additive for resist and resist composition comprising same - Google Patents

Abstract

상기 식에서 각 치환기는 명세서 중에서 정의된 바와 같다. The present invention relates to a resist additive represented by the following general formula (1) and a resist composition comprising the additive, wherein the additive according to the present invention increases the hydrophobicity of the surface of the resist film when applied to a resist composition, The hydrophobicity of the surface is increased to suppress the wetting by water in immersion lithography. In the developing step, the resist film is deaerated by the developing solution to be hydrophilic so that the resist film surface has a low positive contact angle, thereby forming a fine resist pattern having excellent sensitivity and resolution can do:
[Chemical Formula 1]

Wherein each substituent is as defined in the specification.

Description

ADDITIVE FOR RESIST AND RESIST COMPOSITION COMPRISING SAME [0002]

The present invention can improve the hydrophobicity of the surface of the resist film to suppress leaching due to water during immersion lithography, and in the developing process, the resist film is deaerated by the developing solution to be hydrophilic so that the surface of the resist film has a low positive contact angle Sensitivity and resolution, and a resist composition containing the resist additive.

Recent large scale integrated circuits (l arge scale integrated circuit ( LSI) has been demanded to be miniaturized in accordance with high integration and high speed. As an exposure light source used for forming a resist pattern, g-line (436 nm) or i-line (365 nm) such as mercury is mainly used.

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.

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.

Patent Document 1: Korean Patent Publication No. 2006-0029280 (published April 5, 2006) Patent Document 2: Korean Patent Publication No. 2009-0108935 (published on October 19, 2009) Patent Document 3: Korean Patent Laid-Open Publication No. 2011-0084848 (Published on July 26, 2011)

It is an object of the present invention to improve the hydrophobicity of the surface of a resist film so as to suppress irrigation caused by water during immersion lithography and to degrade and become hydrophilic in a developing process so that the resist film surface has a low positive contact angle, And a resist additive capable of forming a fine resist pattern having a resolution.

Another object of the present invention is to provide a resist composition containing the additive and a method of forming a resist pattern using the composition.

In order to achieve the above object, a resist additive according to an embodiment of the present invention is represented by the following general formula (1)

[Chemical Formula 1]

In Formula 1,

Each of R ', R "and R"' is independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halo group, and a haloalkyl group having 1 to 4 carbon atoms in which one of the hydrogen atoms is substituted with a halogen group,

R ₁ is a group having 1 to 20 carbon atoms in a haloalkyl group, a hydrophobic group selected from an organosilicon group, and the group consisting of a hydrocarbon group having a carbon number of 3 to 20, R ₁ a is an organosilicon group, and o is 0, R ₁ is 1 to 20 carbon atoms A haloalkyl group or a hydrocarbon group of 3 to 20 carbon atoms, o is 1,

R ₂ is an alkanediyl group having 1 to 20 carbon atoms, an alkenediyl group having 2 to 20 carbon atoms, a heteroalkanediyl group having 1 to 20 carbon atoms, a heteroalkenediyl group having 2 to 20 carbon atoms, a cycloalkanediyl group having 3 to 30 carbon atoms , A cycloalkenyl diyl group having 3 to 30 carbon atoms, a heterocycloalkanediyl group having 2 to 30 carbon atoms, and a heterocycloalkenediyl group having 3 to 30 carbon atoms,

,

,

,

및 히드록시-2-에틸기로 이루어진 군에서 선택되는 산 민감성 기이고, 이때 R_a, R_b, R_c 및 R_d는 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 헤테로시클로알킬기로 이루어진 군에서 선택되거나, 또는 서로 인접한 기들끼리 연결되어 탄소수 3 내지 30의 포화 또는 불포화 탄화수소 고리 또는 탄소수 2 내지 30의 헤테로사이클기를 형성할 수 있으며, p는 0 내지 3의 정수이고, q는 0 내지 10의 정수이며, R', R" 및 R"'은 각각 독립적으로 수소원자 또는 탄소수 1 내지 10의 알킬기이고, c는 0 내지 6의 정수이고, f는 0 내지 7의 정수이고, 0≤c+f≤15이고,R ₃ and R ₄ are each independently

,

,

,

Wherein R _a , R _b , R _c and R _d 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, ( (Alkyl having 1 to 10 carbon atoms) cycloalkyl group, hydroxyalkyl group, alkoxy group having 1 to 20 carbon atoms, alkyl group having 1 to 10 carbon atoms, acetyl group, acetylalkyl group, carboxyl group, (Cycloalkyl having 3 to 18 carbon atoms) carboxyl group and a heterocycloalkyl group having 3 to 30 carbon atoms, or adjacent groups may be connected to form a saturated or unsaturated hydrocarbon ring having 3 to 30 carbon atoms or a hetero ring having 2 to 30 carbon atoms P is an integer of 0 to 3, q is an integer of 0 to 10, R ', R "and R''each independently represent a hydrogen atom or a C1- C is an integer of 0 to 6, f is an integer of 0 to 7, 0? C + f? 15,

R ₅ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

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

o is an integer of 0 or 1.

In Formula 1, R ₁ represents a fluoroalkyl group having 1 to 10 carbon atoms, a silyl group, an alkylsilyl group having 1 to 10 carbon atoms, a chain or branched alkyl group having 3 to 10 carbon atoms, a monocyclic cycloalkyl group having 3 to 14 carbon atoms An alkyl group, a bicyclic cycloalkyl group having a carbon number of 8 to 18, a tricyclic cycloalkyl group having a carbon number of 10 to 30, and a cyclocyclic cycloalkyl group having a carbon number of 10 to 30.

In Formula 1, R ₁ is selected from the group consisting of a t-butyl group, a trifluoromethyl group, a trimethylsilyl group, a di (trifluoromethyl) isopropyl group, a pentafluoroethyl group, and a heptafluoropropyl group have.

,

,

,

및 히드록시-2-에틸기로 이루어진 군에서 선택되며, 이때 R_a, R_b, R_c 및 R_d는 각각 독립적으로 탄소수 1 내지 10의 알킬기, 탄소수 3 내지 14의 일환식 시클로알킬기, 탄소수 8 내지 20의 이환식 시클로알킬기, 탄소수 10 내지 30의 삼환식 시클로알킬기, 탄소수 10 내지 30의 사환식 시클로알킬기, (탄소수 1 내지 5의 알킬)시클로알킬기, 히드록시알킬기, 탄소수 1 내지 10의 알콕시기, (탄소수 1 내지 5의 알콕시)알킬기, 아세틸기, 아세틸알킬기, 카르복실기, (탄소수 1 내지 5의 알킬)카르복실기, 및 (탄소수 3 내지 10의 시클로알킬)카르복실기로 이루어진 군에서 선택되거나, 또는 서로 인접한 기들끼리 연결되어 탄소수 6 내지 18의 포화 또는 불포화 탄화수소 고리 또는 탄소수 5 내지 18의 헤테로사이클기를 형성할 수 있으며, p는 0 내지 3의 정수이고, q는 0 내지 5의 정수이며, R', R" 및 R"'은 각각 독립적으로 수소원자 또는 탄소수 1 내지 10의 알킬기이고, c는 0 내지 6의 정수이고, f는 0 내지 7의 정수이고, 0≤c+f≤15이다. In Formula 1, R ₃ and R ₄ are each independently

,

,

,

And a hydroxy-2-ethyl group, wherein R _a , R _b , R _c and R _d each independently represent an alkyl group having 1 to 10 carbon atoms, a monocyclic cycloalkyl group having 3 to 14 carbon atoms, A tricyclic cycloalkyl group having 10 to 30 carbon atoms, a cycloalkyl group having 10 to 30 carbon atoms, a cycloalkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group, an alkoxy group having 1 to 10 carbon atoms, ( (Alkyl group having 1 to 5 carbon atoms), an acetyl group, an acetyl group, an acetyl group, an acetyl group, a carboxyl group, a (carboxyl group having 1 to 5 carbon atoms) carboxyl group, and (a cycloalkyl group having 3 to 10 carbon atoms) A saturated or unsaturated hydrocarbon ring having 6 to 18 carbon atoms or a heterocyclic group having 5 to 18 carbon atoms, p is an integer of 0 to 3, and q is an integer of 0 to 5 And R '' are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, c is an integer of 0 to 6, f is an integer of 0 to 7, 0? C + f &Lt; / RTI &gt;

More preferably, R ₃ and R ₄ each independently represent a t-butyl group, a trimethylsilyl group, a hydroxy-2-ethyl group, a 1-methoxypropyl group, a 1-methoxy- Ethoxy-1-ethyl group, 1-ethoxy-1-ethyl group, t-butoxy-2-ethyl group, May be selected from the group consisting of the following formulas (2a) to (2k):

In the above formulas (2a) to (2k), R ', R "and R"' are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a and e are integers of 0 to 15, b is an integer of 0 to 11 , c is an integer of 0 to 6, d is 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, h is an integer of 0 to 4 , 0? C + d? 17, and 0? C + f? 15.

In Formula 1, R ₃ and R ₄ may each independently be selected from the group consisting of the following Formulas 3a to 3h:

The resist additive may be selected from the group consisting of compounds having the following chemical formulas (4) to (11):

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

M + n = 1, and 0 < l / (l + m + n) < 0.99, m / (l + m + n) > 0 and 0 < n / (l + m + n) < 0.99.

delete

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

The resist additive may have a ratio of a weight average molecular weight to a number average molecular weight of 1 to 3.

A resist composition according to another embodiment of the present invention includes the resist additive, a base polymer for a resist, an acid generator, and a solvent.

The resist additive may be included 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 (14) and (15)

[Chemical Formula 14]

[Chemical Formula 15]

In the above formulas 14 and 15,

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, 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, A thiophenoxy group, 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 (16).

[Chemical Formula 16]

(In the formula (16)

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,

and p is an integer of 0 to 2)

The acid generator may be contained in an amount of 0.3 to 10 parts by weight based on 100 parts by weight of the solid content in the resist composition.

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.

A method of forming a resist pattern according to another embodiment of the present invention includes the steps of forming a resist film by coating the resist composition on a substrate, exposing the resist film to a predetermined pattern after the heat treatment, And developing the resist pattern.

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.

When the resist additive is applied to a resist composition, the hydrophobicity of the surface of the resist film is increased to increase the hydrophobicity of the surface of the resist film during the exposure process of immersion lithography, thereby suppressing re-formation due to immersion lithography. And as a result, the surface of the resist film has a low positive contact angle, whereby a fine resist pattern having excellent sensitivity and resolution can be formed.

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.

Unless otherwise specified herein, &quot; halo &quot; or &quot; halogen atom &quot; means any one selected from the group consisting of fluorine, chlorine, bromine and iodine.

Unless stated otherwise in the specification, the prefix 'hetero' means that from 1 to 3 heteroatoms selected from the group consisting of N, O, S and P substitute carbon atoms. For example, a heteroalkyl group means that one to three carbon atoms of the alkyl group are substituted by a heteroatom.

Unless otherwise specified herein, the term "alkyl group" means an alkyl group having 1 to 30 carbon atoms, which is linear or branched, and the alkyl group includes a primary alkyl group, a secondary alkyl group, and a tertiary alkyl group. Specific examples of the alkyl group include, but are not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a t-butyl group.

Unless otherwise specified, the term "cycloalkyl group" means a cycloalkyl group having 3 to 30 carbon atoms, and includes a monocyclic, bicyclic, tricyclic, and sicyclic group. Further, it includes a polycyclic cycloalkyl group containing an adamantyl group, a norbornyl group, and a norbornyl group.

Unless otherwise specified herein, 'alkanediyl' is a divalent atomic group of alkane minus two hydrogen atoms and may be represented by the general formula -C _n H _2n - Alkenediyl 'is a divalent atomic group obtained by subtracting two hydrogen atoms from an alkene, and may be represented by the general formula -C _n H _n -.

Unless otherwise specified herein, an "aryl group" means a compound including a benzene ring and derivatives thereof, for example, two or more benzene rings, such as toluene or xylene having an alkyl side chain attached to a benzene ring, , Naphthalene or anthracene condensed with two or more benzene rings such as fluorene, xanthene or anthraquinone in which two or more benzene rings are bonded through a cycloalkyl group or a heterocycloalkyl group, and the like. Unless otherwise specified in the specification, the aryl group means an aryl group having 6 to 30 carbon atoms.

Unless otherwise stated, the term "hydrocarbon group" means a monovalent hydrocarbon group having 3 to 20 carbon atoms consisting solely of carbon and hydrogen, and includes an aliphatic chain-like or branched hydrocarbon group and an alicyclic hydrocarbon group. Specific examples include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclohexyl, phenyl, tolyl, A biphenyl group, a naphthyl group, and the like.

Unless otherwise specified herein, 'heterocycle' means that at least one (eg, 1, 2, 3 or 4) carbon atoms are replaced by a heteroatom (eg, N, O, P or S) Means a cyclic radical having 4 to 20 ring atoms. The term "heterocycle" includes saturated, partially unsaturated, and aromatic rings (i.e., heteroaromatic rings), and also heteroatoms in the ring are oxidized or tanned to form, for example, N-oxides or 4 Lt; RTI ID = 0.0 &gt; aromatic &lt; / RTI &gt; A substituted heterocycle includes a heterocyclic ring substituted with any of the substituents disclosed herein, including, for example, a carbonyl group.

Examples of heterocycles are pyridyl, dihydropyridyl, tetrahydropyryl (piperidyl), thiazolyl, tetrahydrothiophenyl, tetrahydrothiophenyl sulfur, pyrimidinyl, furanyl, thienyl, pyrrolyl , Pyrazolyl, imidazolyl, tetrazolyl, benzofuranyl, thianaphthalenyl, indolyl, indolenyl, quinolinyl, isoquinolinyl, benzimidazolyl, piperidinyl, 4-piperidinyl, Pyrrolidinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, octahydroisoquinolinyl, azoxycarbonyl, Thiadiazinyl, 6H-1,2,5-thiadiazinyl, 2H, 6H-1,5,2-dithiazinyl, thienyl, thianthrenyl, pyranyl, isobenzofuranyl, chromenyl, xanthanyl , Phenoxatinyl, 2H-pyrrolyl, isothiazolyl, isoxazolyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, 3H-indolyl, 1H-indazoly, furinyl, 4H-quinolizinyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cyinolinyl, , Carbazolyl,? -Carbolinyl, phenanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, furazanyl, phenoxazinyl, isochromanyl, chromanyl, imida Wherein the ring is selected from the group consisting of pyridazinyl, pyrimidinyl, pyrimidinyl, pyrimidinyl, imidazolinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, piperazinyl, indolinyl, isoindolinyl, quinuclidinyl, morpholinyl, oxazolidinyl, benzotriazolyl, , Benzoxazolinyl, isothiouyl, bis-tetrahydrofuranyl each of which may be substituted or unsubstituted, and the corresponding N-oxides thereof (for example pyridyl N-oxide, quinolinyl N -Oxides) or quaternary salts thereof, and the like.

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 case of forming a resist pattern using conventional ArF immersion lithography, an acid or an amine compound contained in the resist film is dissolved in the water impregnated between the projection lens and the wafer substrate, thereby causing contamination of the projection lens, And various defects such as bubble defect and watermark defect are generated.

On the other hand, in the present invention, in immersion photolithography in which a 193 nm ArF excimer laser is used as a light source and a liquid is inserted between the projection station and the substrate to expose the resist, a norbornene monomer-containing repeating unit containing a hydrophobic group The same effects as those obtained by forming the protective film on the resist film in order to protect the resist material by using the resist additive for the resist can be obtained and the recurring units derived from maleic anhydride can be contained in the main chain of the copolymer of the additive in an optimal amount, So that the occurrence of defects on the surface of the resist film is reduced.

That is, the resist additive according to one embodiment of the present invention is a multi-component copolymer represented by the following formula (1)

[Chemical Formula 1]

In Formula 1,

Each of R ', R "and R"' is independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halo group, and a haloalkyl group having 1 to 4 carbon atoms in which one of the hydrogen atoms is substituted with a halogen group,

R ₁ is a group having 1 to 20 carbon atoms in a haloalkyl group, a hydrophobic group selected from an organosilicon group, and the group consisting of a hydrocarbon group having a carbon number of 3 to 20, R ₁ a is an organosilicon group, and o is 0, R ₁ is 1 to 20 carbon atoms A haloalkyl group or a hydrocarbon group of 3 to 20 carbon atoms, o is 1,

R ₂ is an alkanediyl group having 1 to 20 carbon atoms, an alkenediyl group having 2 to 20 carbon atoms, a heteroalkanediyl group having 1 to 20 carbon atoms, a heteroalkenediyl group having 2 to 20 carbon atoms, a cycloalkanediyl group having 3 to 30 carbon atoms , A cycloalkenyl diyl group having 3 to 30 carbon atoms, a heterocycloalkanediyl group having 2 to 30 carbon atoms, and a heterocycloalkenediyl group having 3 to 30 carbon atoms,

,

,

,

및 히드록시-2-에틸기로 이루어진 군에서 선택되는 산 민감성 기이고, 이때 R_a, R_b, R_c 및 R_d는 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 헤테로시클로알킬기로 이루어진 군에서 선택되거나, 또는 서로 인접한 기들끼리 연결되어 탄소수 3 내지 30의 포화 또는 불포화 탄화수소 고리 또는 탄소수 2 내지 30의 헤테로사이클기를 형성할 수 있으며, p는 0 내지 3의 정수이고, q는 0 내지 10의 정수이며, R', R" 및 R"'은 각각 독립적으로 수소원자 또는 탄소수 1 내지 10의 알킬기이고, c는 0 내지 6의 정수이고, f는 0 내지 7의 정수이고, 0≤c+f≤15이고,R ₃ and R ₄ are each independently

,

,

,

Wherein R _a , R _b , R _c and R _d 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, ( (Alkyl having 1 to 10 carbon atoms) cycloalkyl group, hydroxyalkyl group, alkoxy group having 1 to 20 carbon atoms, alkyl group having 1 to 10 carbon atoms, acetyl group, acetylalkyl group, carboxyl group, (Cycloalkyl having 3 to 18 carbon atoms) carboxyl group and a heterocycloalkyl group having 3 to 30 carbon atoms, or adjacent groups may be connected to form a saturated or unsaturated hydrocarbon ring having 3 to 30 carbon atoms or a hetero ring having 2 to 30 carbon atoms P is an integer of 0 to 3, q is an integer of 0 to 10, R ', R "and R''each independently represent a hydrogen atom or a C1- C is an integer of 0 to 6, f is an integer of 0 to 7, 0? C + f? 15,

R ₅ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

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

o is an integer of 0 or 1.

In Formula 1, R ', R "and R"' each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoro group, or a fluoro group having 1 to 4 carbon atoms in which one of the hydrogen atoms is substituted with fluoro An alkyl group, and more preferably a group selected from the group consisting of a hydrogen atom, a methyl group, a fluoro group and a trifluoromethyl group, more preferably a hydrogen atom.

In Formula 1, R ₁ represents a fluoroalkyl group having 1 to 10 carbon atoms, a silyl group, an alkylsilyl group having 1 to 10 carbon atoms, a chain or branched alkyl group having 3 to 10 carbon atoms, a monocyclic cycloalkyl group having 3 to 14 carbon atoms An alkyl group, a bicyclic cycloalkyl group having a carbon number of 8 to 18, a tricyclic cycloalkyl group having a carbon number of 10 to 30, and a cyclocyclic cycloalkyl group having a carbon number of 10 to 30, more preferably a group selected from the group consisting of a t- (Trifluoromethyl) isopropyl, pentafluoroethyl, and heptafluoropropyl groups. The term &quot; alkyl group &quot;

Wherein R ₂ is an alkanediyl group having 1 to 10 carbon atoms, an alkenediyl group having 2 to 10 carbon atoms, a heteroalkanediyl group having 1 to 10 carbon atoms, a heteroalkenediyl group having 2 to 10 carbon atoms, a heteroaryl group having 3 to 18 carbon atoms, , A cycloalkanediyl group having 3 to 18 carbon atoms, a cycloalkenediyl group having 3 to 18 carbon atoms, a heterocycloalkanediyl group having 2 to 18 carbon atoms, and a heterocycloalkanediyl group having 3 to 18 carbon atoms, and more preferably, methylene, ethylidene, propylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, 2,2-dimethyl _{pentamethylene, -OCH 2 -, -OCH (Cl} ) -, -CO-, -COCH 2 -, -COCH ₂ CH ₂ -, -CH ₂ -O-CH ₂ -, -CH ₂ -O-CH ₂ CH ₂ -, -CH ₂ CH ₂ -O-CH ₂ -, -CH ₂ -O-CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ -O-CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -O-CH ₂ -, -C (CH ₃ ) ₂ CH ₂ - _{3) CH 2 -, -CH (} CH 2 CH 3) -, -CH (OCH 3) -, -C (CF 3) (OCH 3) -, -CH 2 -S-CH 2 -, -CH 2 - S-CH ₂ CH ₂ -, -CH ₂ CH ₂ -S-CH ₂ -, -CH ₂ -S-CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ -S-CH ₂ CH ₂ - _{2 CH 2 CH 2 -S-CH} 2 -, -CH (CH 2) CH-, -C (CH 2 CH 2) -, -CH 2 CO-, -CH 2 CH 2 CO-, -CH (CH 3 _{) CH 2 CO-, -CH (OH} ) -, -C (OH) (CH 3) -, -CH (F) -, -CH (Br) -, -CH (Br) CH (Br) -, - _{CH = CH-, -CH 2 CH =} CH-, -CH = CHCH 2 -, -CH = CHCO-, -C 7 H 9 - may be selected from the group consisting of - and -C ₁₀ H _14.

,

,

,

및 히드록시-2-에틸기로 이루어진 군에서 선택되며, 이때 R_a, R_b, R_c 및 R_d는 각 독립적으로 탄소수 1 내지 10의 알킬기, 탄소수 3 내지 14의 일환식 시클로알킬기, 탄소수 8 내지 20의 이환식 시클로알킬기, 탄소수 10 내지 30의 삼환식 시클로알킬기, 탄소수 10 내지 30의 사환식 시클로알킬기, (탄소수 1 내지 5의 알킬)시클로알킬기, 히드록시알킬기, 탄소수 1 내지 10의 알콕시기, (탄소수 1 내지 5의 알콕시)알킬기, 아세틸기, 아세틸알킬기, 카르복실기, (탄소수 1 내지 5의 알킬)카르복실기, 및 (탄소수 3 내지 10의 시클로알킬)카르복실기로 이루어진 군에서 선택되거나, 또는 서로 인접한 기들끼리 연결되어 탄소수 6 내지 18의 포화 또는 불포화 탄화수소 고리 또는 탄소수 5 내지 18의 헤테로사이클기를 형성할 수 있으며, p는 0 내지 3의 정수이고, q는 0 내지 5의 정수이며, R', R" 및 R"'은 각각 독립적으로 수소원자 또는 탄소수 1 내지 10의 알킬기이고, c는 0 내지 6의 정수이고, f는 0 내지 7의 정수이고, 0≤c+f≤15인 것이 바람직하다.In Formula 1, R ₃ and R ₄ are each independently

,

,

,

And a hydroxy-2-ethyl group, wherein R _a , R _b , R _c and R _d are independently selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a monocyclic cycloalkyl group having 3 to 14 carbon atoms, A tricyclic cycloalkyl group having 10 to 30 carbon atoms, a cycloalkyl group having 10 to 30 carbon atoms, a cycloalkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group, an alkoxy group having 1 to 10 carbon atoms, ( (Alkyl group having 1 to 5 carbon atoms), an acetyl group, an acetyl group, an acetyl group, an acetyl group, a carboxyl group, a (carboxyl group having 1 to 5 carbon atoms) carboxyl group, and (a cycloalkyl group having 3 to 10 carbon atoms) A saturated or unsaturated hydrocarbon ring having 6 to 18 carbon atoms or a heterocyclic group having 5 to 18 carbon atoms, p is an integer of 0 to 3, and q is an integer of 0 to 5 And R '' are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, c is an integer of 0 to 6, f is an integer of 0 to 7, 0? C + f Lt; 15.

More preferably, R ₃ and R ₄ each independently represent a t-butyl group, a trimethylsilyl group, a hydroxy-2-ethyl group, a 1-methoxypropyl group, a 1-methoxy- Ethoxy-1-ethyl group, 1-ethoxy-1-ethyl group, t-butoxy-2-ethyl group, Is an acid sensitive group selected from the group consisting of the following formulas (2a) to (2k):

In the above formulas (2a) to (2k), R ', R "and R'" are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a and e are integers of 0 to 15, b is an integer of 0 to 11 , c is an integer of 0 to 6, d is 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, h is an integer of 0 to 4 , 0? C + d? 17, and 0? C + f? 15.

More preferably, R ₃ and R ₄ are each independently selected from the group consisting of the following formulas (3a) to (3h):

In the general formula (1), R ₅ is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms, more preferably hydrogen or a methyl group.

Generally, a static contact angle (SAC) of 90 ° or more must be formed in order to increase a scan speed in exposure to a resist film. However, a high SCA in a post-exposure developing process requires a blob defect It is possible to reduce the blot defect by making the surface of the resist film have a low SCA. On the contrary, the copolymer according to the present invention contains a recurring unit derived from maleic anhydride in the main chain in an optimal amount, and thus, it is possible to produce a copolymer which is dehydrated by a developer (for example, 2.38 wt% trimethylammonium hydroxide (TMAH) The additive of the present invention is a copolymer in which the electron withdrawing group is substituted at the alpha carbon position such as trihaloacetyl in the side chain portion of the copolymer. The hydrophobicity of the resist film can be increased and the elution of the resist film component during immersion exposure can be prevented.

More specifically, in the copolymer of the resist additive according to the present invention, the norbornene derivative-derived repeating unit 1 contains a hydrophobic group, thereby improving the hydrophobic property of the surface of the resist film during exposure, leaching can be suppressed. At the time of development, the hydrophobic group at the exposed site is dehydrogenated by the developer as shown in the following reaction formula 1 to become a hydroxy group, and the characteristics are changed to be hydrophilic. As a result, the resist film surface has a low SCA It is possible to reduce the blob bonding. In addition, the acid labile group attached to the terminal, for example, the t-butyl group, is converted from hydrophobic to hydrophilic by the acid-assisted deprotection reaction at the exposed site, and as a result, do. The following Reaction Scheme 1 is only one example of the present invention, but the present invention is not limited thereto.

[Reaction Scheme 1]

In the copolymer according to the present invention, the maleic anhydride-derived repeating unit m is ring-opened by a developing solution to form a carboxyl group at a non-exposure site and has a hydrophilic property to the surface . The modified surface has the same properties as the developing solution, thereby facilitating the development process, thereby reducing defects that may appear when the surface has a hydrophobic character. The following Reaction Scheme 2 is only one example of the present invention, but the present invention is not limited thereto.

[Reaction Scheme 2]

Further, in the copolymer according to the present invention, the acrylic derivative-derived repeating unit n contains an acid-sensitive functional group, so that the acid-sensitive functional group is deprotected at the time of exposure to change from hydrophobic to hydrophilic. As a result, It is easily washed away.

The repeating units 1, m and n of the copolymer represent the content of each repeating unit in the main chain and mean the substitution rate at which the copolymer is dissolved in the developer. The copolymer according to the present invention is characterized in that the molar ratios l, m and n of the repeating units satisfy 0 <1 / (l + m + n) <0.9, m / (l + m + n) > 0 and 0 < n / (l + m + n) < 0.9. By including the above-mentioned repeating units in the above ratio, hydrophobic properties exhibiting less affinity with water at immersion exposure can be exhibited.

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 represented by the following formulas (4) to (11), and the order of each repeating unit in the structural formula may be changed:

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

M + n = 1, and 0 < l / (l + m + n) < 0.99, m / (l + m + n) > 0 and 0 < n / (l + m + n) < 0.99.

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 copolymer 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 3, more preferably 1 to 2. 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 can be produced by subjecting a norbornene derivative having the structure of Formula 12, a maleic anhydride monomer, and an acrylic monomer having a structure represented by Formula 13 below to an ordinary polymerization method, For example, by polymerization methods such as polymerization, solution polymerization, suspension polymerization, bulk suspension polymerization, emulsion polymerization, and the like.

[Chemical Formula 12]

[Chemical Formula 13]

In the general formulas (12) and (13), R ', R ", R"', R ₁ to R ₅ and o are as defined above.

Preferably, the copolymer according to the present invention can be polymerized by radical polymerization, and examples of the radical polymerization initiator include azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), lauryl peroxide, azobis There is no particular limitation as long as it is used as a general radical polymerization initiator such as isocapronitrile, azobisisobalonitrile, and t-butyl hydroperoxide.

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.

The resist additive according to the present invention obtained by controlling the kind and content of the monomers according to the above-described production method has appropriate hydrophobic properties and is suitable for a resist composition which is transparent to exposure light, And it is also possible to reduce the formation of various defects that may occur in the exposure process.

Thus, 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 included in an amount of 0.05 to 5% 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. If the additive exceeds 5 wt%, it may cause a water-meter defect.

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 , Imide and the like can be used, and preferably at least one of the sulfonium salts represented by the following formulas (14) and (15) can be used, more preferably triphenylsulfonium nonaplate can be used:

[Chemical Formula 14]

[Chemical Formula 15]

In the above formulas 14 and 15,

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 (16)

[Chemical Formula 16]

In Formula 16,

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 (16) may be selected from the group consisting of the functional groups represented by the following formulas (17a) to (17l) and (18a to 18x)

In the above formulas (14) and (15), preferred examples of the cation moiety include the following formulas (19a) to (19p)

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 basic compound may be contained in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 1 part by weight based on 100 parts by weight of the polymer solid content. If the content of the basic compound is less than 0.01 part by weight, the influence of the latent period after exposure may increase, which may affect the shape of the pattern. If the content is more than 5 parts by weight, the resolution and sensitivity may decrease.

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 amount 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.

[ Manufacturing example : Synthesis of monomers and polymers]

(Monomeric Synthetic example  One)

(2,2,2-trifluoro-acetoxy) -propionic acid tert-butyl ester (3-bicyclo [2.2.1] hept- Synthesis of monomers (hereinafter referred to as &quot; BHP-5 &quot;) hept-5-en-2-yl-3- (2,2,2- trifluoro-acetoxy)

3-Bicyclo [2,2,1] hept-5-en-2-yl-3-hydroxy-propionic acid tert- yl-3-hydroxy-propionic acid tert-butyl ester BHP) 100 g of (II), 105.75 g of trifluoroacetic anhydride (III) and 100 g of dimethyl-pyridine-4 -yl-amine) was dissolved in 1 L of methylene chloride, 46.71 g of triethylamine was slowly added dropwise at 0 ° C, and the mixture was stirred at room temperature for 3 hours. The resultant reaction product was dissolved in 500 ml of methylene chloride, washed with acid and distilled water, and only the organic layer was separated. The solvent in the separated organic layer was removed and 130 g of intermediate product BHP-5 (compound (I)) was obtained.

1 H-NMR (ppm) 0.6 (d, 1 H), 0.82 (d, 1 H), 1.25 (m, 1H), 2.08 (m, 12H), 2.15-2.6 (m, 3H), 2.88 (m, 2H), 4.7 (s, 1 H), 6.22 (s, 1 H)

(Polymer Synthetic example  One)

15 g of the polymerization monomer BHP-5 prepared in Synthesis Example 1 of the monomer and 1.24 g of dimethy azobisobutylate as a polymerization initiator were added to a flask together with 12 g of 1,4-dioxane And then mixed. Nitrogen gas was used to displace the inside of the flask with nitrogen, and then the temperature inside the flask was raised to 75 占 폚. When the temperature inside the flask was raised to 75 캜, 2 g of maleic anhydride and 2-methyl-acrylic acid 2-isoprophy-adamantan- 2-yl ester) in 12 g of 1,4-dioxane was slowly added dropwise to the flask for 2 hours using a syringe pump. The reaction was continued at the same temperature for 3 hours to complete the polymerization, and the temperature of the resultant reaction solution was cooled to room temperature. The reaction solution cooled to room temperature was precipitated with excess hexane (n-hexane) and the precipitate was filtered. The resulting filtrate was dried under reduced pressure to obtain 12 g of a polymer (IV) having the following structural formula. The polystyrene reduced weight average molecular weight (Mw) of this polymer was 6577 g / mol, and the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight was 1.6.

(Polymer Synthetic example  2)

15 g of the polymerization monomer BHP-5 prepared in Synthesis Example 1 of the monomer and 1.24 g of dimethyl azobisisobutylate as a polymerization initiator were added to a flask together with 12 g of 1,4-dioxane, followed by mixing. Nitrogen gas was used to displace the inside of the flask with nitrogen, and then the temperature inside the flask was raised to 75 占 폚. When the temperature inside the flask was raised to 75 ° C, 2 g of maleic anhydride and 1 g of 1-ethyl-1- (1-methylene-allyloxy) -cyclohexane Dioxane in 12 g of 1,4-dioxane was slowly added dropwise to the flask for 2 hours using a syringe pump. The reaction was continued at the same temperature for 3 hours to complete the polymerization, and the temperature of the resultant reaction solution was cooled to room temperature. The reaction solution cooled to room temperature was precipitated with an excess amount of hexane, and the precipitate was filtered. The resulting filtrate was dried under reduced pressure to obtain 13 g of a polymer (V) having the following structural formula. The weight average molecular weight (Mw) of the polymer in terms of polystyrene was 4500 g / mol, and the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight was 1.5.

(Polymer Synthetic example  3)

15 g of the polymerizable monomer prepared in Synthesis Example 1 of the monomer and 1.24 g of dimethyl azobisisobutylate as a polymerization initiator were added to a flask together with 12 g of 1,4-dioxane, followed by mixing. Nitrogen gas was used to displace the inside of the flask with nitrogen, and then the temperature inside the flask was raised to 75 占 폚. When the temperature inside the flask was raised to 75 ° C, 2 g of maleic anhydride and 1 g of 1-methyl-1- (1-methylene-allyloxy) -cyclopentane Was dissolved in 12 g of 1,4-dioxane, and the resulting solution was slowly added dropwise to the flask for 2 hours using a syringe pump. The reaction was continued at the same temperature for 3 hours to complete the polymerization, and the temperature of the resultant reaction solution was cooled to room temperature. The reaction solution cooled to room temperature was precipitated with an excess amount of hexane, and the precipitate was filtered. The resulting filtrate was dried under reduced pressure to obtain 11 g of a polymer (VI) having the following structural formula. The polystyrene reduced weight average molecular weight (Mw) of the polymer was 5000 g / mol, and the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight was 1.6.

(Polymer Synthetic example  4)

15 g of the polymerizable monomer prepared in Synthesis Example 1 of the monomer and 1.24 g of dimethyl azobisisobutylate as a polymerization initiator were added to a flask together with 12 g of 1,4-dioxane, followed by mixing. Nitrogen gas was used to displace the inside of the flask with nitrogen, and then the temperature inside the flask was raised to 75 占 폚. When the temperature inside the flask was raised to 75 ° C, 2 g of maleic anhydride and 6 g of acrylic acid 2-methyl-adamantan-2-yl ester were added to 1,4- Dioxane (12 g) was slowly added dropwise to the flask for 2 hours using a syringe pump. The reaction was continued at the same temperature for 3 hours to complete the polymerization, and the temperature of the resultant reaction solution was cooled to room temperature. The reaction solution cooled to room temperature was precipitated with an excess amount of hexane, and the precipitate was filtered. The resulting filtrate was dried under reduced pressure to obtain 12 g of a polymer (VII) having the following structural formula. The polystyrene reduced weight average molecular weight (Mw) of the polymer was 6,200 g / mol, and the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight was 1.63.

(Polymer Synthetic example  5)

15 g of the polymerizable monomer prepared in Synthesis Example 1 of the monomer and 1.24 g of dimethyl azobisisobutylate as a polymerization initiator were added to a flask together with 12 g of 1,4-dioxane, followed by mixing. Nitrogen gas was used to displace the inside of the flask with nitrogen, and then the temperature inside the flask was raised to 75 占 폚. When the temperature inside the flask was raised to 75 ° C, 2 g of maleic anhydride and 2 g of acrylic acid 2-ethyl-adamantan-2-ylester 1-methylene-allyloxy-cyclopentane -yl ester) in 12 g of 1,4-dioxane was slowly added dropwise to the flask for 2 hours using a syringe pump. The reaction was continued at the same temperature for 3 hours to complete the polymerization, and the temperature of the resultant reaction solution was cooled to room temperature. The reaction solution cooled to room temperature was precipitated with an excess amount of hexane, and the precipitate was filtered. The resulting filtrate was dried under reduced pressure to obtain 13 g of a polymer (VI) having the following structural formula. The polystyrene reduced weight average molecular weight (Mw) of this polymer was 5930 g / mol, and the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight was 1.55.

[ Test Example  1: Evaluation of hydrophobicity of additive]

1.0 g of the polymer synthesized in Polymer Synthesis Examples 1 to 5 was dissolved in 25 g of 4-methyl pentanol, and the solution was filtered through a 0.2-micrometer polypropylene filter to prepare a resist protective film composition. (Mw: 7,900 g / mol, Mw / Mn: 1.73, molar ratio of each repeating unit: x: y: z = 1: : 1) was used as Comparative Example 1.

Each of the resist protective film compositions prepared above was spin-coated on a silicon substrate and baked at 100 DEG C for 60 seconds to form a 50-nm-thick resist protective film.

The falling angle and the receding contact angle were measured with respect to the formed resist protective film.

Specifically, the silicon substrate on which the resist protective film was formed was held horizontally, and 50 占 퐇 of pure water was dropped thereon to form water droplets. Thereafter, the silicon substrate was gradually inclined, and the angle of the silicon substrate (Tilting angle) and receding contact angle were measured. The results are shown in Table 1 below.

Types of Polymers as Resist Additives Pre-development
Falling angle (°) Retraction contact angle before development (°) (&Amp;thetas;) after development Retraction contact angle after development (°) Synthesis Example 1 Polymer (IV) 93.7 78.6 74.2 42. Synthesis Example 2 Polymer (V) 95.1 79.9 75.8 44.2 Synthesis Example 3 Polymer (VI) 94.5 79.5 72.6 43.7 Synthesis Example 4 Polymer (VII) 92.6 78.1 71.4 41.3 Synthesis Example 5 Polymer (VIII) 93.5 79.1 72.7 42.6 Comparative Example 1 Polymer (IX) 88.5 67.8 84.2 64.2

Referring to Table 1 above, it can be seen that the resist protective film comprising the polymer prepared in Polymer Synthesis Examples 1 to 5 has high water repellency and is difficult to dissolve in water, has high alkali solubility and can be easily peeled off with an alkaline developer at the time of development Able to know. In addition, it can be seen that the polymers produced in Polymer Synthesis Examples 1 to 5 have little adverse effects on the angle of tortuosity and the receding contact angle.

[ Experimental Example : Resist film  Formed and manufactured Of the resist film  Characteristic measurement]

( Example  1 to 5)

5 g of a resist polymer (Mw: 8,500 g / mol, Mw / Mn: 1.75, the molar ratio of each repeating unit: x: y: z: w = 1: 1: 1: 1) 1.0 g of each of the polymers synthesized in Examples 1 to 5, 0.31 g of the photoacid generator represented by the following Formula 21 and 0.07 g of triisopropanol amine as an inhibitor were dissolved in 80 g of propyleneglycol monoethyl ether acetate, PGMEA), followed by filtration through a polypropylene filter having a size of 0.2 mu m to prepare a composition for forming a photoresist film.

[Chemical Formula 20]

[Chemical Formula 21]

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.

( Comparative Example  2)

A resist film was formed in the same manner as in Example 1 except that the resist additive was not used.

The silicon substrate on which the resist film formed in Examples 1 to 5 and Comparative Example 2 was formed was cut to evaluate the sensitivity. At this time, the sensitivity was defined as the exposure amount for resolving 65 nm L / S to 1: 1. The measurement results are shown in Table 2 below.

Types of Polymers as Resist Additives Sensitivity (mJ / cm ² ) 65 nm pattern shape Example 1 Polymer (IV) 35.7 No refining wave phenomenon Example 2 Polymer (V) 43.5 No refining wave phenomenon Example 3 Polymer (VI) 52.4 No refining wave phenomenon Example 4 Polymer (VII) 52.7 No refining wave phenomenon Example 5 Polymer (VIII) 48.5 No refining wave phenomenon Comparative Example 2 - 49.2 Roughness severe

Referring to Table 2, when a resist film is formed of a resist composition containing no resist additive as in Comparative Example 2, and pure water rinsing is carried out after exposure, since a generated acid is dissolved in water, a T-top pattern is formed But no change in shape was observed in the case of Examples 1 to 5 including the polymer prepared in Synthesis Examples 1 to 5 as a resist additive.

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)

A resist additive represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
Each of R ', R "and R"' is independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halo group, and a haloalkyl group having 1 to 4 carbon atoms in which one of the hydrogen atoms is substituted with a halogen group,
R ₁ is a group having 1 to 20 carbon atoms in a haloalkyl group, a hydrophobic group selected from an organosilicon group, and the group consisting of a hydrocarbon group having a carbon number of 3 to 20, R ₁ a is an organosilicon group, and o is 0, R ₁ is 1 to 20 carbon atoms A haloalkyl group or a hydrocarbon group of 3 to 20 carbon atoms, o is 1,
R ₂ is an alkanediyl group having 1 to 20 carbon atoms, an alkenediyl group having 2 to 20 carbon atoms, a heteroalkanediyl group having 1 to 20 carbon atoms, a heteroalkenediyl group having 2 to 20 carbon atoms, a cycloalkanediyl group having 3 to 30 carbon atoms , A cycloalkenyl diyl group having 3 to 30 carbon atoms, a heterocycloalkanediyl group having 2 to 30 carbon atoms, and a heterocycloalkenediyl group having 3 to 30 carbon atoms,
R ₃ and R ₄ are each independently

,

,

,

Wherein R _a , R _b , R _c and R _d 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, ( (Alkyl having 1 to 10 carbon atoms) cycloalkyl group, hydroxyalkyl group, alkoxy group having 1 to 20 carbon atoms, alkyl group having 1 to 10 carbon atoms, acetyl group, acetylalkyl group, carboxyl group, (Cycloalkyl having 3 to 18 carbon atoms) carboxyl group and a heterocycloalkyl group having 3 to 30 carbon atoms, or adjacent groups are connected to each other to form a saturated or unsaturated hydrocarbon ring having 3 to 30 carbon atoms or a hetero ring having 2 to 30 carbon atoms P is an integer of 0 to 3, q is an integer of 0 to 10, R ', R "and R''each independently represent a hydrogen atom or a C1- C is an integer of 0 to 6, f is an integer of 0 to 7, 0? C + f? 15,
R ₅ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
1, m, and n each represent a molar ratio of repeating units in the main chain, and 1 + m + n = 1 and 0 <1 / ) &Gt; 0 and 0 &lt; n / (l + m + n) < 0.99, and
o is an integer of 0 or 1. The method according to claim 1,
Wherein R ₁ represents a fluoroalkyl group having 1 to 10 carbon atoms, a silyl group, an alkylsilyl group having 1 to 10 carbon atoms, a chain or branched alkyl group having 3 to 10 carbon atoms, a monocyclic cycloalkyl group having 3 to 14 carbon atoms, A tricyclic cycloalkyl group having 10 to 30 carbon atoms, and a cycloalkyl group having 10 to 30 carbon atoms. The method according to claim 1,
Wherein R ₁ is selected from the group consisting of a t-butyl group, a trifluoromethyl group, a trimethylsilyl group, a di (trifluoromethyl) isopropyl group, a pentafluoroethyl group and a heptafluoropropyl group. The method according to claim 1,
R ₃ and R ₄ are each independently

,

,

,

And a hydroxy-2-ethyl group, wherein R _a , R _b , R _c and R _d each independently represent an alkyl group having 1 to 10 carbon atoms, a monocyclic cycloalkyl group having 3 to 14 carbon atoms, A tricyclic cycloalkyl group having 10 to 30 carbon atoms, a cycloalkyl group having 10 to 30 carbon atoms, a cycloalkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group, an alkoxy group having 1 to 10 carbon atoms, ( (Alkyl group having 1 to 5 carbon atoms), an acetyl group, an acetyl group, an acetyl group, an acetyl group, a carboxyl group, a (carboxyl group having 1 to 5 carbon atoms) carboxyl group, and (a cycloalkyl group having 3 to 10 carbon atoms) A saturated or unsaturated hydrocarbon ring having 6 to 18 carbon atoms or a heterocyclic group having 5 to 18 carbon atoms, p is an integer of 0 to 3, and q is an integer of 0 to 5 And R '' are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, c is an integer of 0 to 6, f is an integer of 0 to 7, 0? C + f Lt; / = 15. The method according to claim 1,
R ₃ and R ₄ are each independently 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, 2k. &Lt; / RTI &gt;

In the above formulas (2a) to (2k), R ', R "and R"' are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a and e are integers of 0 to 15, b is an integer of 0 to 11 , c is an integer of 0 to 6, d is 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, h is an integer of 0 to 4 , 0? C + d? 17, and 0? C + f? 15. The method according to claim 1,
Wherein R ₃ and R ₄ are each independently selected from the group consisting of the following formulas (3a) to (3h):

The method according to claim 1,
Wherein the resist additive is selected from the group consisting of compounds having the following chemical formulas (4) to (11):
[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

M + n = 1, and 0 < l / (l + m + n) < 0.99, m / (l + m + n) > 0 and 0 < n / (l + m + n) < 0.99. delete The method according to claim 1,
Wherein the resist additive has a polystyrene reduced weight average molecular weight of 1,000 to 20,000 g / mol by gel permeation chromatography. The method according to claim 1,
Wherein the resist additive has a weight-average molecular weight to number-average molecular weight of 1 to 3. A resist composition comprising the resist additive according to any one of claims 1 to 7, and a resist base polymer, an acid generator, and a solvent. 12. The method of claim 11,
Wherein the resist additive is contained in an amount of 0.05 to 5% by weight based on the total weight of the resist composition. 12. The method of claim 11,
Wherein the acid generator is at least one compound selected from the group consisting of compounds represented by the following general formulas (14) and (15).
[Chemical Formula 14]

[Chemical Formula 15]

In the above formulas 14 and 15,
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, 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, A thiophenoxy group, 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 (16).
[Chemical Formula 16]

(In the formula (16)
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,
and p is an integer of 0 to 2) 12. The method of claim 11,
Wherein the acid generator is contained in an amount of 0.3 to 10 parts by weight based on 100 parts by weight of the solid content in the resist composition. 12. The method of claim 11,
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. 12. A method of forming a resist pattern, comprising the steps of: applying a resist composition according to claim 11 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.