KR101731036B1 - 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 (1-1) 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 in the exposure process when applied to a resist composition, It is possible to suppress reflow by water and form a fine resist pattern having excellent sensitivity and resolution when applied to a resist composition.
[Formula 1-1]

Wherein each substituent is as defined in the specification.

Description

ADDITIVE FOR RESIST AND RESIST COMPOSITION COMPRISING SAME [0002]

The present invention relates to a resist additive capable of forming a fine resist pattern having excellent sensitivity and resolution and capable of suppressing leaching due to water during immersion lithography by increasing the hydrophobicity of the resist film surface 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.

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.

Korea Patent Publication No. 2011-0084848 (disclosed on July 26, 2011) Korean Patent Publication No. 2008-0000522 (published on Jan. 2, 2008) Korean Published Patent No. 2011-0079649 (Published July 7, 2011)

An object of the present invention is to provide a resist additive capable of increasing the hydrophobicity of the surface of a resist film and suppressing leaching due to water during immersion lithography, and capable of forming a fine resist pattern having excellent sensitivity and 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 includes a copolymer represented by the following formula (1-1)

[Formula 1-1]

In Formula 1-1, R ', R "and R"' each independently represent a haloalkyl group having 1 to 4 carbon atoms in which one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen group and a hydrogen atom is substituted with a halogen group ≪ / RTI >

R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms;

R ₅ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a cycloalkenyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, A heterocyclyl group having 2 to 30 carbon atoms, and combinations thereof;

R ₃₁ represents a fluoroalkyl group having 1 to 10 carbon atoms, a silyl group, an alkylsilyl group having 1 to 10 carbon atoms, a chained and branched alkyl group having 3 to 10 carbon atoms, a bicyclic cycloalkyl group having 8 to 18 carbon atoms, And a cyclic cycloalkyl group having 10 to 30 carbon atoms. When R ₃₁ is any one selected from the group consisting of a silyl group and an alkylsilyl group having 1 to 10 carbon atoms, p is 0 and R ₃₁ represents a fluoroalkyl group having from 1 to 10 carbon atoms, a chain and branched alkyl group having from 3 to 10 carbon atoms, a bicyclic cycloalkyl group having from 8 to 18 carbon atoms, a tricyclic cycloalkyl group having from 10 to 30 carbon atoms, and a cyclocyclic cycloalkyl group having from 10 to 30 carbon atoms Alkyl group, p is 1,

R ₃₂ represents 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

로 이루어진 군에서 선택되는 산 민감성 기이고, 이때 Ra, Rb, Rc 및 Rd는 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, x는 0 내지 3의 정수이고, y는 0 내지 10의 정수이며; R ₃₃ is

,

And

Wherein Ra, Rb, Rc and Rd 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) cycloalkyl group, An alkyl group having 1 to 20 carbon atoms, 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 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 heterocyclic group having 2 to 30 carbon atoms, Y is an integer from 0 to 10;

R ₄ is a hydrophobic group selected from the group consisting of an organic silicon group and a hydrocarbon group having 3 to 20 carbon atoms;

M + n + o = 1 and 0 <1 / (m + n + o) <0.9 and 0.2 <m / (1 + m + n + o) < 0.9, p is 0 or 1, It is an integer.

The R ₃₁ may be 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.

,

및

로 이루어진 군에서 선택되는 산 민감성 기이고, 이때 Ra, Rb, Rc 및 Rd는 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, (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, x는 0 내지 3의 정수이고, y는 0 내지 5의 정수일 수 있다.R ₃₃ is

,

And

Wherein Ra, Rb, Rc and Rd 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 bicyclic cycloalkyl group having 8 to 20 carbon atoms, (1 to 5 carbon atoms) cycloalkyl group, a hydroxyalkyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 10 to 30 carbon atoms, a cycloalkyl group having 10 to 30 carbon atoms, An alkyl group, an acetyl group, an acetylalkyl group, a carboxyl group, a (carboxyl group having 1 to 5 carbon atoms) carboxyl group, (a cycloalkyl group having 3 to 10 carbon atoms) carboxyl groups, or adjacent groups are connected to each other to form a saturated Or an unsaturated hydrocarbon ring or a heterocyclic group having 5 to 18 carbon atoms, x is an integer of 0 to 3, y is an integer of 0 to 5 There.

R ₃₃ represents a group selected from the group consisting of 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-2-ethyl, t- .

In formulas (4a) to (4k), R ', R' 'and R' '' each independently represent a hydrogen atom, 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, 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 8, 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 R ₃₃ may be selected from the group consisting of the following formulas (5a) to (5h).

R ₄ 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 bicyclic cycloalkyl group having 1 to 18 carbon atoms, a tricyclic cycloalkyl group having 10 to 30 carbon atoms, and a cycloalkyl group having 10 to 30 carbon atoms.

R ₄ may be selected from the group consisting of t-butyl, trifluoromethyl, trimethylsilyl, di (trifluoromethyl) isopropyl, pentafluoroethyl and heptafluoropropyl.

R ₅ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 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 cyclic cycloalkyl group having 10 to 30 carbon atoms, a cycloalkenyl group having 3 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 18 carbon atoms, Can be selected from the group.

,

및

로 이루어진 군에서 선택되는 산 민감성 기이거나, 또는

및

로 이루어진 군에서 선택되는 락톤기일 수 있으며, 이때 상기 Ra, Rb, Rc 및 Rd는 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, Re 및 Rf는 각각 독립적으로 탄소수 1 내지 10의 알킬기이거나 서로 연결되어 탄소수 3 내지 30의 포화 탄화수소 고리를 형성할 수 있으며, x는 0 내지 3의 정수이고, y는 0 내지 10의 정수이며, z1 및 w1은 각각 독립적으로 0 내지 3의 정수이고, z2 및 w2는 각각 독립적으로 0 내지 7의 정수이고 0≤z1+w1≤5이고, 0≤z2+w2≤5일 수 있다.Wherein R &lt; _{5 &}

,

And

Or an acid-sensitive group selected from the group consisting of

And

Ra, Rb, Rc and Rd 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) An alkyl group having 1 to 20 carbon atoms, 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) 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 heterocyclic group having 2 to 30 carbon atoms, and Re and Rf Are independently an alkyl group having 1 to 10 carbon atoms or may be connected to each other to form a saturated hydrocarbon ring having 3 to 30 carbon atoms And z1 and w1 are each independently an integer of 0 to 3, z2 and w2 are each independently an integer of 0 to 7 and 0? Z1 + w1? 5, and 0? z2 + w2? 5.

R ₅ is a group selected from the group consisting of 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-2-ethyl, 1-isobutoxy- .

In the above formulas (6a) to (6m), 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 and d are each independently an integer of 0 to 9, f is an integer of 0 to 7, g, i and k are each independently an integer of 0 to 6, h is an integer of 0 to 4, j Is an integer of 0 to 5, 0? C + d? 17, and 0? C + f? 15.

The resist additive may be selected from the group consisting of compounds having the structures of formulas (7) to (10), (15) and (17).

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

[Chemical Formula 15]

[Chemical Formula 17]

M + n + o = 1, and 0 < l / (l + m + n + (1 + m + n + o) < 0.9 and 0.2 < m / (l + m + &Lt; 0.9.

The repeating unit m may be contained in an amount of 30 to 60 mol% in the copolymer of the resist additive.

The resist additive may have a polystyrene reduced weight average molecular weight of 1,000 to 50,000 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 5.

A resist composition according to another embodiment of the present invention includes a 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 chemical formulas (22) and (23).

[Chemical Formula 22]

(23)

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 having 1 to 10 carbon atoms, a benzyl group, 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, and Z in the anion moiety is preferably selected from the group consisting of a thiophenoxy group, a thioalkoxy group having 1 to 30 carbon atoms, 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 the formula 24 &Lt; / RTI &gt;

&Lt; EMI ID =

In the formula (24), V ₁ and V ₂ are each independently a halogen atom, W ₁ is - (C═O) - or - (SO ₂ ) -, W ₂ is an alkynediyl group having 2 to 10 carbon atoms, W ₃ represents a cycloalkylene group having 3 to 30 carbon atoms, an aryldiiyl group having 6 to 30 carbon atoms, an aralkylene group having 7 to 30 carbon atoms, an arylether group having 6 to 30 carbon atoms, an arylsulfide group having 6 to 30 carbon atoms, A heterocycloalkylene group having 1 to 10 carbon atoms, W ₄ is 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, and combinations thereof, o is an integer of 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.

The resist additive according to the present invention can improve the hydrophobicity of the surface of the resist film when applied to a resist composition, suppressing water-induced leaching during the exposure process of immersion lithography, and can form a fine resist pattern having excellent sensitivity and resolution .

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.

As used herein, the prefix &quot; hetero &quot; means that one to three 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 of 3 to 20 carbon atoms consisting solely of carbon and hydrogen, and includes aliphatic chain-like and branched hydrocarbon groups and alicyclic hydrocarbon groups. 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, a cyclic structure composed of maleic anhydride and norbornene derivatives is introduced into the main chain of the copolymer as an additive to the photoresist composition to improve etching resistance, and a hydrophobic group is introduced into the side chain of the repeating unit, The hydrophobicity of the surface of the membrane is increased to suppress the re-precipitation by water during immersion lithography. In development, the hydrophilic group is converted into a hydrophilic group to exhibit solubility to the developer. Further, by introducing an acid- sensitive group into the repeating unit side chain, solubility in an alkali developing solution is increased A fine pattern can be formed without occurrence of a defect phenomenon, and the present invention has been completed.

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

[Formula 1-1]

Specifically, in formula 1-1, R ', R "and R"' each independently represent a haloalkyl group having 1 to 4 carbon atoms in which one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen group and a hydrogen atom is substituted with a halogen group Can be selected from the group consisting of. More preferably a group selected from the group consisting of a hydrogen atom, a methyl group, a fluoro group and a trifluoromethyl group, and still more preferably a hydrogen atom.

Each of R ₁ and R ₂ may be independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. More preferably, each of R ₁ and R ₂ is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, More preferably a hydrogen atom or a methyl group.

R ₃₁ 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 bicyclic cycloalkyl group having 1 to 18 carbon atoms, a tricyclic cycloalkyl group having 10 to 30 carbon atoms, and a cycloalkyl group having 10 to 30 carbon atoms.

P is an integer of 0 or 1; When R ₃₁ is any one selected from the group consisting of a silyl group and an alkylsilyl group having 1 to 10 carbon atoms, p is 0, R ₃₁ is a fluoroalkyl group having 1 to 10 carbon atoms, a chain or branched alkyl group having 3 to 10 carbon atoms, P is 1 or a group selected from the group consisting of a bicyclic cycloalkyl group having 8 to 18 carbon atoms, a tricyclic cycloalkyl group having 10 to 30 carbon atoms and a cyclocyclic cycloalkyl group having 10 to 30 carbon atoms.

More preferably, R ₃₁ 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.

R ₃₂ represents 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 cycloalkenediyl 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.

More preferably, R ₃₂ 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 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 heterocycloalkenediyl group having 3 to 18 carbon atoms, -OCH ₂ -, -OCH (Cl) -, -CO-, -COO-, -O-, -O-, -O-, -O-, _{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 -, -CH _{(CH 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 -SCH ₂ -, -CH ₂ -S-CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ -S _{-CH 2 CH 2 -, -CH 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 - , and -C ₁₀ H ₁₄ - consisting of It is better to choose from the group.

,

및

로 이루어진 군에서 선택되는 산 민감성 기이고, 이때 Ra, Rb, Rc 및 Rd는 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, x는 0 내지 3의 정수이고, y는 0 내지 10의 정수이다.R ₃₃ is

,

And

Wherein Ra, Rb, Rc and Rd 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) cycloalkyl group, An alkyl group having 1 to 20 carbon atoms, 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 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 heterocyclic group having 2 to 30 carbon atoms, 3, and y is an integer of 0 to 10.

,

및

로 이루어진 군에서 선택되는 산 민감성 기이고, 이때 Ra, Rb, Rc 및 Rd는 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, (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, x는 0 내지 3의 정수이고, y는 0 내지 5의 정수일 수 있다.Preferably, R &lt; ₃₃ &gt;

,

And

Wherein Ra, Rb, Rc and Rd 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 bicyclic cycloalkyl group having 8 to 20 carbon atoms, (1 to 5 carbon atoms) cycloalkyl group, a hydroxyalkyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 10 to 30 carbon atoms, a cycloalkyl group having 10 to 30 carbon atoms, An alkyl group, an acetyl group, an acetylalkyl group, a carboxyl group, a (carboxyl group having 1 to 5 carbon atoms) carboxyl group, (a cycloalkyl group having 3 to 10 carbon atoms) carboxyl groups, or adjacent groups are connected to each other to form a saturated Or an unsaturated hydrocarbon ring or a heterocyclic group having 5 to 18 carbon atoms, x is an integer of 0 to 3, y is an integer of 0 to 5 There.

More preferably, R ₃₃ 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, t-isobutoxy-1-ethyl group and the following formulas (4a) to Can be selected from the group.

In formulas (4a) to (4k), R ', R' 'and R' '' each independently represent a hydrogen atom, 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, 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 8, 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 &lt; ₃₃ &gt; may be selected from the group consisting of the following formulas (5a) to (5h).

R ₄ is a hydrophobic group selected from the group consisting of an organic silicon group and a hydrocarbon group having 3 to 20 carbon atoms. Preferably, R ₄ is a fluoroalkyl group having 1 to 10 carbon atoms, a silyl group, an alkylsilyl group having 1 to 10 carbon atoms, A cyclic cycloalkyl group having 3 to 10 carbon atoms, a cyclic 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, and a cycloalkyl group having 10 to 30 carbon atoms Can be selected from the group consisting of.

More preferably, R ₄ may be 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.

R ₅ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a cycloalkenyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, A heterocyclic group having 2 to 30 carbon atoms, and combinations thereof.

Preferably, R ₅ is a hydrogen atom, an alkyl group having a carbon number of 1 to 10, an alkenyl group having a carbon number of 2 to 10, a monocyclic cycloalkyl group having a carbon number of 3 to 14, a bicyclic cycloalkyl group having a carbon number of 8 to 18, A cycloalkyl group, a cycloalkyl group having 10 to 30 carbon atoms, a cycloalkenyl group having 3 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 18 carbon atoms, &Lt; / RTI &gt;

,

및

로 이루어진 군에서 선택되는 산 민감성 기이거나, 또는

및

로 이루어진 군에서 선택되는 락톤기일 수 있으며, 이때 상기 Ra, Rb, Rc 및 Rd는 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, Re 및 Rf는 각각 독립적으로 탄소수 1 내지 10의 알킬기이거나 서로 연결되어 탄소수 3 내지 30의 포화 탄화수소 고리를 형성할 수 있으며, x는 0 내지 3의 정수이고, y는 0 내지 10의 정수이며, z1 및 w1은 각각 독립적으로 0 내지 3의 정수이고, z2 및 w2는 각각 독립적으로 0 내지 7의 정수이고 0≤z1+w1≤5이고, 0≤z2+w2≤5일 수 있다.More preferably, R &lt; ₅ &gt;

,

And

Or an acid-sensitive group selected from the group consisting of

And

Ra, Rb, Rc and Rd 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) An alkyl group having 1 to 20 carbon atoms, 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) 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 heterocyclic group having 2 to 30 carbon atoms, and Re and Rf Are independently an alkyl group having 1 to 10 carbon atoms or may be connected to each other to form a saturated hydrocarbon ring having 3 to 30 carbon atoms And z1 and w1 are each independently an integer of 0 to 3, z2 and w2 are each independently an integer of 0 to 7 and 0? Z1 + w1? 5, and 0? z2 + w2? 5.

More preferably, R ₅ 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 (6a) to Can be selected from the group consisting of.

In the above formulas (6a) to (6m), 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 and d are each independently an integer of 0 to 9, f is an integer of 0 to 7, g, i and k are each independently an integer of 0 to 6, h is an integer of 0 to 4, j Is an integer of 0 to 5, 0? C + d? 17, and 0? C + f? 15.

When the resist additive according to the present invention having the above structure is applied to a resist composition to form a resist film, the resist film is positioned on the resist film surface due to the difference in specific gravity, thereby improving the hydrophobic property of the resist film surface. As a result, it acts like a separate protective film is formed on the surface of the resist film, and prevents the components of the resist film from escaping into the water during the immersion lithography process. Further, the resist film containing the resist additive is dissolved in the developing solution in both the exposed portion and the non-exposed portion in the developing process.

Specifically, the resist additive according to the present invention contains a hydrophobic group in at least one of the norbornene derivative-derived repeating unit 1 and the acrylic derivative-derived repeating unit n portion, thereby improving the hydrophobic property of the resist film surface upon exposure Thereby suppressing leaching by water in the lithography process. Further, at the time of development, a hydroxyl group is generated after being degassed by a developing solution, for example, trimethylammonium hydroxide (TMAH), and converted from a hydrophobic state to a hydrophilic state, Can be suppressed.

Further, the resist additive according to the present invention contains a norbornene derivative-derived repeating unit 1 and an acrylic derivative-derived repeating unit o, respectively, and contains an acid-sensitive functional group, whereby the hydrophobic property is changed from a hydrophobic property to a hydrophilic property by an acid- As a result, it is possible to exhibit an increased solubility in an alkali developing solution at the time of development.

Further, the maleic anhydride-derived repeating unit m in the resist additive according to the present invention is ring-opened by a developing solution at a non-exposed portion to form a carboxyl group and double the hydrophilic property to the surface. As a result, it enables lithography with fewer defects.

The repeating units 1, m and n constituting the copolymer of the resist additive according to the present invention are the numbers representing the content of each repeating unit in the main chain, and mean the substitution rate at which the copolymer is dissolved in the developing solution. The resist additive according to the present invention is characterized in that the repeating units l, m, n and o satisfy 0 <1 / (l + m + n + o) <0.9, 0.2 m / (l + m + n + o) < 0.9, 0? n / (l + m + n + o)? 0.9 and 0? o / By including the repeating units in the ratio, the affinity with water at the time of liquid immersion lithography can exhibit hydrophobicity with low hydrophilicity. In particular, by including the maleic anhydride-derived repeating unit m in an amount exceeding 20 mol% The hydrophilic property is sufficiently increased and can be easily dissolved in the developer. More preferably, the copolymer contains 30 to 60 mol% of the maleic anhydride-derived repeating unit m.

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

The resist additive may be selected from the group consisting of compounds having the structures of formulas (7) to (10), (15) and (17).

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

[Chemical Formula 15]

[Chemical Formula 17]

M + n + o = 1, and 0 < l / (l + m + n + (1 + m + n + o) < 0.9 and 0.2 < m / (l + m + &Lt; 0.9.

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 50,000 g / mol by gel permeation chromatography (GPC). When the weight average molecular weight of the resist additive is too small, it may cause intermixing or elution into pure water in the case of liquid immersion exposure. If it is too large, proper film formation may be difficult or alkaline solubility may be deteriorated. Preferably, a weight average molecular weight of 2,000 to 20,000 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 of 1 to 5, more preferably 1 to 3, which is a ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight. If the molecular weight distribution of the weight is more than 5, the line edge roughness may not be good. Therefore, when a copolymer that satisfies the weight average molecular weight and the molecular weight distribution range is used as an additive for a photoresist composition, proper physical properties can be exhibited in terms of developability, coating ability, and heat resistance.

The resist additive according to the present invention having the above structure can be produced by reacting at least one acrylic monomer among a norbornene derivative, a maleic anhydride monomer, and optionally an acrylic monomer having the structure of Chemical Formulas 20 and 21, By polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, bulk suspension polymerization, emulsion polymerization, and the like.

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

In the above formulas 19 to 21, R ', R ", R'", Ra, Rb, Rc and R ₁ to R ₅ 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.

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. When the content of the resist additive is less than 0.05 wt%, the effect of the use of the additive is insignificant. When the content of the resist additive exceeds 5 wt%, the resolution and roughness of the resist decrease.

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. Preferably, at least one of the sulfonium salts represented by the following formulas (22) and (23) can be used, more preferably triphenylsulfonium nonaplate can be used:

[Chemical Formula 22]

(23)

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 having 1 to 10 carbon atoms, a benzyl group, 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 a combination thereof, and is preferably selected from the group consisting of thiophenoxy,

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) is _{3, C (C 4 F 9} ) 3 or a group represented by the formula 24:

&Lt; EMI ID =

In Formula 24, V ₁ and V ₂ are each independently a halogen atom,

W ₁ is - (C = O) - or - (SO ₂ ) -,

W ₂ is an alkynediyl group having 2 to 10 carbon atoms,

W ₃ represents a cycloalkylene group having 3 to 30 carbon atoms, an aryldiiyl group having 6 to 30 carbon atoms, an aralkylene group having 7 to 30 carbon atoms, an arylether group having 6 to 30 carbon atoms, an arylsulfide group having 6 to 30 carbon atoms, Lt; / RTI &gt; to 30, and &lt; RTI ID = 0.0 &gt;

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;

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, Formula 24 may be selected from the group consisting of the functional groups represented by the following Formulas 24a to 24l, and 25a to 25x.

In the above formulas (22) and (23), preferred cation moieties include those represented by the following formulas (26a) to (26p):

The acid generators may be used alone or in admixture of two or more. The acid generator may be contained in an amount of 0.3 to 15 parts by weight, preferably 0.3 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, still more preferably 2 to 10 parts by weight, per 100 parts by weight of the polymer solid content By weight. 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 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 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.

The resist composition according to the present invention having the above composition can be dissolved in a developing solution in both the exposed part and the non-exposed part in the development process after the ArF light source irradiation, exhibits improved line width roughness, Both of the L / S patterns show excellent resolution. 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 composition sensitive to radiation such as deep ultraviolet rays such as KrF excimer laser, ArF excimer laser or F2 excimer laser, X-rays such as synchrotron radiation, .

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

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

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 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. 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 an additive such as a surfactant 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- hydroxypropanoic acid tert- yl) - (3-hydroxy) propionic acid tert-butyl ester: BHP), 105.75 g of trifluoroacetic anhydride and 4.67 g of dimethylpyridine-4-yl- 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 resulting 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, 1H), 0.82 (d, 1H), 1.25 (m, 1H), 1.42 (m, 1H), 1.58 (s 1H), 1.7 (m, 1H), 1.9 (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 Synthesis Example 1 )

30 g of the polymerization monomer BHP-5 prepared in Synthesis Example 1 of the monomer and 1.65 g of dimethyl azobisisobutyrate as a polymerization initiator were mixed with 58.2 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 inside temperature of the flask was raised to 75 캜, a solution prepared by dissolving 8.8 g of maleic anhydride in 58.2 g of 1,4-dioxane was slowly added dropwise to the flask using a syringe pump for 2 hours. The reaction was continued at the same temperature for 5 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 methanol, and the precipitate was filtered. Upon filtration, the filtrate was washed with the same solvent and dried under reduced pressure to obtain 20 g of polymer (IV) having the following structural formula. The polystyrene reduced weight average molecular weight (Mw) of this polymer was 3260 g / mol, and the ratio of the weight average molecular weight to the number average molecular weight was Mw / Mn = 1.38.

(Polymer Synthetic example  3)

30 g of the polymerization monomer BHP-5 prepared in Synthesis Example 1 of the monomer and 2.48 g of dimethyl azobisisobutylate as a polymerization initiator were added to a flask together with 80 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 inside temperature of the flask was raised to 75 캜, a solution prepared by dissolving 8.8 g of maleic anhydride and 14.01 g of? -Butyrolactyl methacrylate in 80 g of 1,4-dioxane was treated with a syringe pump for 2 hours And slowly dropped into the flask. The reaction was continued at the same temperature for 5 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 methanol, and the precipitate was filtered. Upon filtration, the filtrate was washed with the same solvent and dried under reduced pressure to obtain 42 g of polymer (VI) having the following structural formula. The polystyrene reduced weight average molecular weight (Mw) of this polymer was 4,300 g / mol, and the ratio of the weight average molecular weight to the number average molecular weight was Mw / Mn = 1.45.

(Polymer Synthetic example  5)

3-Bicyclo [2,2,1] hept-5-en-2-yl-3-hydroxy-propionic acid tert- yl-3-hydroxy-propionic acid tert-butylester: BHP) and 1.93 g of dimethyl azobisisobutyrate as a polymerization initiator were added to a flask together with 35.79 g of 1,4-dioxane. 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 inside temperature of the flask was raised to 75 캜, a solution prepared by dissolving 9.24 g of methyladamantane methacrylate and 6.55 g of? -Butyrolactyl methacrylate in 35.79 g of 1,4-dioxane was charged into a syringe pump Was slowly added dropwise to the flask for 2 hours. The reaction was continued at the same temperature for 5 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 methanol, and the precipitate was filtered. Upon filtration, the filtrate was washed with the same solvent and dried under reduced pressure to obtain 19 g of a polymer (VIII) having the following structural formula. The polystyrene reduced weight average molecular weight (Mw) of this polymer was 6,231 g / mol, and the ratio of the weight average molecular weight to the number average molecular weight was Mw / Mn = 1.92.

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

( Example  And Comparative Example )

1.0 g of each of the polymers synthesized in Polymer Synthesis Examples 1, 3 and 5 as an additive to the resist composition was added to a resist base polymer (Mw: 8,500 g / mol, Mw / Mn: 1.75, (X: y: z: w) of 1: 1: 1: 1) and 0.31 g of the photoacid generator represented by the following Formula 28 were mixed with 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 resist compositions (Examples 1 and 3 and Comparative Example 1).

(27)

(28)

An antireflection film (BARC) having a film thickness of 90 nm was formed on a silicon substrate. The resist composition prepared above was coated on the substrate having the antireflection film formed thereon and baked at 100 DEG C for 60 seconds to form a resist film having a thickness of 120 nm Film.

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

Specifically, the substrate on which the resist 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 so that the angle of the silicon substrate Angle and receding contact angle were measured. The results are shown in Table 1 below.

Next, in order to reproduce the liquid immersion exposure, a pure water rinse was performed on the exposed resist film 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.

The prepared silicon substrate 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.

Resist composition Additive for Resist Falling angle (°) Receding contact angle (°) Sensitivity (mJ / cm ² ) Example 1 Polymer 1 (IV) 89 78 34 Example 3 Polymer 3 (VI) 82 73 33 Comparative Example 1 Polymer 5 (VIII) 75 65 Not patternable

Referring to Table 1, the resist films formed using the resist compositions of Examples 1 and 3 including a copolymer as a resist additive according to the present invention were prepared in the same manner as in Comparative Example 1 (Comparative Example 1) in which Polymer 5 (VIII) A higher angle of inclination and a receding contact angle than those of the resist film formed using the resist composition of the present invention. From these results, it can be seen that the resist film made from the resist compositions of Examples 1 and 3 has sufficient hydrophobicity, and therefore, it is unnecessary to form a protective film for the resist film during liquid immersion lithography. Also, the resist film formed using the resist compositions of Examples 1 and 3 exhibited excellent sensitivity characteristics improved upon liquid immersion exposure, whereas the resist composition of Comparative Example 1 did not form a pattern and thus the sensitivity measurement was impossible.

While the invention has been shown and described with reference to certain preferred embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. And falls within the scope of the invention.

Claims (21)

A resist additive represented by the following formula (1-1);
[Formula 1-1]

In Formula 1-1,
R ', R''andR''' are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen 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 and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms;
R ₅ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a cycloalkenyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, A heterocyclyl group having 2 to 30 carbon atoms, and combinations thereof;
R ₃₁ represents a fluoroalkyl group having 1 to 10 carbon atoms, a silyl group, an alkylsilyl group having 1 to 10 carbon atoms, a chained and branched alkyl group having 3 to 10 carbon atoms, a bicyclic cycloalkyl group having 8 to 18 carbon atoms, And a cyclic cycloalkyl group having 10 to 30 carbon atoms, which is a hydrophobic group selected from the group consisting of a hydrogen atom,
When R ₃₁ is any one selected from a silyl group and an alkylsilyl group having 1 to 10 carbon atoms, p is 0,
R ₃₁ is selected from the group consisting of a fluoroalkyl group having 1 to 10 carbon atoms, a chain and branched alkyl group having 3 to 10 carbon atoms, a bicyclic cycloalkyl group having 8 to 18 carbon atoms, a tricyclic cycloalkyl group having 10 to 30 carbon atoms, Cycloalkyl group, p is 1,
R ₃₂ represents 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 ₃₃ is

,

And

Wherein Ra, Rb, Rc and Rd 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) cycloalkyl group, An alkyl group having 1 to 20 carbon atoms, 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 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 heterocyclic group having 2 to 30 carbon atoms, Y is an integer from 0 to 10;
R ₄ is a hydrophobic group selected from the group consisting of an organic silicon group and a hydrocarbon group having 3 to 20 carbon atoms;
M + n + o = 1 and 0 <1 / (m + n + o) <0.9 and 0.2 <m / (1 + m + n + o) < 0.9, 0 &
p is an integer of 0 or 1; The method according to claim 1,
Wherein R ₃₁ 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 ₃₃ is

,

And

Wherein Ra, Rb, Rc and Rd 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 bicyclic cycloalkyl group having 8 to 20 carbon atoms, (1 to 5 carbon atoms) cycloalkyl group, a hydroxyalkyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 10 to 30 carbon atoms, a cycloalkyl group having 10 to 30 carbon atoms, An alkyl group, an acetyl group, an acetylalkyl group, a carboxyl group, a (carboxyl group having 1 to 5 carbon atoms) carboxyl group, (a cycloalkyl group having 3 to 10 carbon atoms) carboxyl groups, or adjacent groups are connected to each other to form a saturated Or an unsaturated hydrocarbon ring or a heterocyclic group having 5 to 18 carbon atoms, x is an integer of 0 to 3, and y is an integer of 0 to 5 Additives for resist. The method according to claim 1,
R ₃₃ represents a group selected from the group consisting of 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-2-ethyl, t- By weight of a resist additive.

In formulas (4a) to (4k), R ', R''andR''' each independently represent a hydrogen atom, 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, 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 8, 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,
And R &lt; ₃₃ &gt; is selected from the group consisting of the following formulas (5a) to (5h).

The method according to claim 1,
R ₄ 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 ₄ is selected from the group consisting of t-butyl, trifluoromethyl, trimethylsilyl, di (trifluoromethyl) isopropyl, pentafluoroethyl and heptafluoropropyl. The method according to claim 1,
R ₅ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 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 cyclic cycloalkyl group having 10 to 30 carbon atoms, a cycloalkenyl group having 3 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 18 carbon atoms, Lt; / RTI &gt; additive for resist. The method according to claim 1,
Wherein R &lt; _{5 &}

,

And

Or an acid-sensitive group selected from the group consisting of

And

Ra, Rb, Rc and Rd 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) An alkyl group having 1 to 20 carbon atoms, 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) 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 heterocyclic group having 2 to 30 carbon atoms, and Re and Rf Are independently an alkyl group having 1 to 10 carbon atoms or may be connected to each other to form a saturated hydrocarbon ring having 3 to 30 carbon atoms And z1 and w1 are each independently an integer of 0 to 3, z2 and w2 are each independently an integer of 0 to 7 and 0? Z1 + w1? 5, and 0? z2 + w2? 5. The method according to claim 1,
R ₅ is a group selected from the group consisting of 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-2-ethyl, 1-isobutoxy- Resist additive:

In the above formulas (6a) to (6m), 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 and d are each independently an integer of 0 to 9, f is an integer of 0 to 7, g, i and k are each independently an integer of 0 to 6, h is an integer of 0 to 4, j Is an integer of 0 to 5, 0? C + d? 17, and 0? C + f? 15. The method according to claim 1,
Wherein the additive for resists is selected from the group consisting of compounds having the structures of formulas (7) to (10), (15) and (17).
(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

[Chemical Formula 15]

[Chemical Formula 17]

M + n + o = 1, and 0 < l / (l + m + n + (1 + m + n + o) < 0.9 and 0.2 < m / (l + m + &Lt; 0.9. The method according to claim 1,
Wherein the repeating unit m is contained in an amount of 30 to 60 mol% in the copolymer of the resist additive. The method according to claim 1,
Wherein the resist additive has a polystyrene reduced weight average molecular weight of 1,000 to 50,000 g / mol by gel permeation chromatography. The method according to claim 1,
Wherein the resist additive has a ratio of a weight average molecular weight to a number average molecular weight of from 1 to 5. A resist composition comprising the resist additive according to any one of claims 1 to 14, a base polymer for a resist, an acid generator and a solvent. 16. The method of claim 15,
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. 16. The method of claim 15,
Wherein the acid generator is at least one compound selected from the group consisting of compounds represented by the following chemical formulas (22) and (23).
[Chemical Formula 22]

(23)

In the above formulas (22) and (23)
X ₁ , X ₂ , Y ₁ and Y ₂ each independently represent hydrogen, 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 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 a combination thereof, and is preferably selected from the group consisting of thiophenoxy,
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) is _{3, C (C 4 F 9} ) 3 or a group represented by the formula 24:
&Lt; EMI ID =

In the formula (24)
V ₁ and V ₂ are each independently a halogen atom,
W ₁ is - (C = O) - or - (SO ₂ ) -,
W ₂ is an alkynediyl group having 2 to 10 carbon atoms,
W ₃ represents a cycloalkylene group having 3 to 30 carbon atoms, an aryldiiyl group having 6 to 30 carbon atoms, an aralkylene group having 7 to 30 carbon atoms, an arylether group having 6 to 30 carbon atoms, an arylsulfide group having 6 to 30 carbon atoms, Lt; / RTI &gt; to 30, and &lt; RTI ID = 0.0 &gt;
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; 16. The method of claim 15,
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. 16. The method of claim 15,
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 15 on 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. 21. The method of claim 20,
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.