KR20140063984A - Novel acryl monomer, polymer and resist composition comprising the same - Google Patents

Abstract

The present invention provides: an acryl monomer denoted by formula 1 effectively used in forming a fine resist pattern having excellent sensitivity, resolution, and improved line edge roughness; a polymer for resist comprising a repeating unit derived from the acryl monomer; and a resist composition comprising the same. In the above formula, each substituent is as defined in the specification.

Description

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

The present invention relates to novel acrylic monomers, polymers and resist compositions containing them useful for patterning using lithography.

Recently, lithography has been actively promoted by high-volumetric manufacturing (HVM) by ArF immersion photolithography, and development is underway to realize a line width of 50 nm or less. In addition, lithography using extreme UV (EUV) is projected as the most promising candidate technology of the next generation lithography technology.

EUV lithography is a next-generation technology that is mainly studied for pattern formation of 30 nm or less, and it is expected that commercialization in all aspects is possible except for defects occurring in the current energy or mask. In addition, the International Roadmap for Semiconductor Technology (ITRS roadmap) suggests that HVM using this technology will be possible by 2015. However, looking at the resist side of EUV lithography, many challenges still remain to be solved for the successful application of such technologies as KrF or ArF.

Among them, it is important to secure a sufficient amount of photons required for pattern implementation. Unlike KrF or ArF lithography, EUV light is absorbed by all materials, so the path of light travels in vacuum, and the mask is irradiated by reflection using a multilayer film that is not transmissive. As a result, a resist with a high power source and high sensitivity is required in the process. However, when the sensitivity (10-15 mJ / cm ² ) required for a strong EUV energy (92.5 eV) is met, a problem arises in that the pattern must be implemented with a small photon. In particular, in the EUV lithography, since the number of photons is smaller than that of ArF lithography due to the characteristic of using a strong light source of 13.5 nm and as a result, the yield of the acid generated in the photoacid generator is low, degradation of fine pattern formation and increase in line edge roughness Causing many problems in pattern formation.

Accordingly, various methods have been researched and developed in order to solve the problem of pattern implementation with low acid yield according to low photons and to obtain a high acid yield at the same sensitivity. In particular, The development and introduction of a sensitizer for increasing the amount of the sensitizer is essential.

Patent Document 1: Korean Patent Publication No. 2004-0086793 (published on October 12, 2004) Patent Document 2: Korean Patent Laid-Open Publication No. 2012-0094842 (disclosed on Aug. 27, 2012)

It is an object of the present invention to provide novel acrylic monomers useful for forming fine resist patterns having excellent sensitivity and resolution, and improved line edge roughness properties.

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

It is still another object of the present invention to provide a resist composition comprising the polymer.

According to one embodiment of the present invention, there is provided an acrylic monomer having the following formula:

[Chemical Formula 1]

In Formula 1,

R ₁ is a hydrogen atom or a functional group represented by the following formula (2)

R _2a and R _2b are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, and a functional group represented by the following formula Any one of R ₁ , R _2a and R _2b is a functional group represented by the following general formula (2)

(2)

(2)

R ₃ is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 30 carbon atoms, a linear or branched heteroalkylene group having 1 to 20 carbon atoms, and a heterocycloalkylene group having 3 to 30 carbon atoms , ≪ / RTI >

R ₄ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a combination thereof)

R is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group and an alkoxy group having 1 to 10 carbon atoms,

m is an integer of 1 to 3;

Preferably, the acrylic monomer may have a structure represented by the following formula (1a) or (1b):

[Formula 1a]

[Chemical Formula 1b]

In the above general formulas (1a) and (1b)

R _3a and R _3b each independently represent a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 30 carbon atoms, a linear or branched heteroalkylene group having 1 to 20 carbon atoms, and a linear or branched alkylene group having 3 to 30 carbon atoms ≪ / RTI > and < RTI ID = 0.0 >

R _4a and R _4b are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and combinations thereof.

Preferably, in the above general formula (1a) or (1b), R _3a and R _3b are each independently a methylene group or an ethylene group, and R _4a and R _4b are each independently a hydrogen atom or a methyl group.

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

The polymer may further comprise a repeating unit derived from an olefinic compound or a heterocycloalkylene-based compound, and the polymer may further include a repeating unit represented by the following formula (6): < EMI ID =

[Chemical Formula 6]

In Formula 6,

R ₅ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and combinations thereof, and

R ₆ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, A heteroaryl group and a combination thereof, and R ₆ is substituted or unsubstituted with a substituent selected from the group consisting of a carbonyl group, a carboxyl group, an ether group, a nitrile group and a halogen group.

The resist polymer may have a structure represented by the following formula (7): < EMI ID =

(7)

In Formula 7,

R _5a , R _5b And R _5c are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a combination thereof,

The R _6a and R _6b And R _6c each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, A heteroaryl group having 3 to 30 carbon atoms, and a combination thereof, and R _6a and R _6b And R _6c are each independently substituted or unsubstituted with a substituent selected from the group consisting of a carbonyl group, a carboxyl group, an ether group, a nitrile group and a halogen group,

W is a repeating unit derived from an olefin compound or a heterocycloalkylene compound,

Y is a functional group of the following formula (8a) or (8b)

[Chemical Formula 8a]

[Formula 8b]

(In the above formulas 8a and 8b,

R ₁₁ is a hydrogen atom,

R ₂₁ and R ₂₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group and an alkoxy group having 1 to 10 carbon atoms,

R _a and R _b are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group and an alkoxy group having 1 to 10 carbon atoms,

m1 and m2 are each independently an integer of 1 to 3) and

(a + b + c + d + e) < 0.5, wherein a, b, c, d and e each represent a repeating unit in the main chain, (A + b + c + d + e) < 0.5, 0? C / (a + b + c + ) &Lt; 0.5 and 0 < e / (a + b + c + d + e) < 0.5.

,

및

로 이루어진 군에서 선택되는 산 민감성 기이고, 이때 R', R" 및 R"'은 각각 독립적으로 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 30의 시클로알킬기, (탄소수 1 내지 10의 알킬)시클로알킬기, 히드록시알킬기, 탄소수 1 내지 20의 알콕시기, (탄소수 1 내지 10의 알콕시)알킬기, 아세틸기, 아세틸알킬기, 카르복실기, (탄소수 1 내지 10의 알킬)카르복실기, (탄소수 3 내지 18의 시클로알킬)카르복실기 및 탄소수 3 내지 30의 헤테로시클로알킬기로 이루어진 군에서 선택되거나, 또는 서로 인접한 기들끼리 연결되어 탄소수 3 내지 30의 포화되거나 또는 불포화된, 탄화수소 고리 또는 헤테로사이클 고리를 형성할 수 있으며, R""는 탄소수 1 내지 10의 알킬기이고, z는 0 내지 3의 정수이고, w는 0 내지 10의 정수이며,Preferably, in Formula 7, R &lt; _5a &gt;

,

And

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

또는

이고, 이때 R' 및 R"은 각각 독립적으로 탄소수 1 내지 10의 알킬기이거나 서로 연결되어 포화 탄화수소 고리를 형성할 수 있으며, x 및 y는 각각 독립적으로 0 내지 5의 정수이며, 그리고 R &lt; _5b &gt;

or

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

W may be a repeating unit derived from a compound selected from the group consisting of an alkylene-based compound, a cyclic olefin-based compound, a styrene-based compound, and a furandione-based compound.

More preferably, W may be a repeating unit derived from a compound selected from the group consisting of a vinyl compound, a styrene compound, a norbornene compound, an indene compound, an acenaphthene compound, and a furandione compound.

More preferably, the resist polymer may be selected from the group consisting of compounds having the structures of the following formulas (7a) to (7d):

In the above formulas (7a) to (7d)

_{R 1, R 6a, R 6b} , and R ₆ c will be each independently selected from the group consisting of a hydrogen atom, an alkoxy group, and combinations of alkyl groups having 1 to 10 carbon atoms, having 1 to 10 carbon atoms, and

(a + b + c + d + e) < 0.5, wherein a, b, c, d and e each represent a repeating unit in the main chain, (A + b + c + d + e) < 0.5, 0? C / (a + b + c + ) &Lt; 0.5 and 0 < e / (a + b + c + d + e) < 0.5.

The resist polymer may have a polystyrene reduced weight average molecular weight of 1,000 to 100,000 g / mol by gel permeation chromatography (GPC).

The resist polymer may have a molecular weight distribution of 1 to 3 which is a ratio (Mw / Mn) of a weight-average molecular weight to a number-average molecular weight.

According to another embodiment of the present invention, there is provided a resist composition comprising the above-mentioned resist polymer.

According to another embodiment of the present invention, there is provided a resist composition for extreme ultraviolet lithography comprising the above-mentioned resist polymer.

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

Preferably, 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 acrylic monomer according to the present invention contains a large amount of a molecular light source, particularly oxygen and nitrogen which exhibits a high absorption rate with respect to an EUV light source, and increases the amount of photons that can activate the photoacid generator when applied to a resist, It is possible to generate a large amount of acid from zero to improve the sensitivity and resolution of the resist. In addition, the acrylic monomer generates an acid and an inert gas due to intramolecular rearrangement during light irradiation, and the generated inactive oxidation substrate increases the solubility in a base developer to form a fine pattern having an improved line edge roughness characteristic have.

Accordingly, the polymer derived from the acrylic monomer and the resist containing the same are also useful for forming a fine resist pattern having excellent sensitivity and resolution, and improved line edge roughness characteristics.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a CD-SEM photograph (observation magnification: 120,000 times) of L / S patterns prepared by using the polymer (I) prepared in Synthesis Example 1 of the polymer at various positions.
2 is a CD-SEM photograph (observed magnification: 120,000 times) of L / S patterns prepared by using Polymer (II) prepared in Synthesis Example 2 of Polymer at various positions.
3 is a CD-SEM photograph (observation magnification: 120,000 times) in which L / S patterns prepared by using the polymer of the comparative example (polymer of formula 20) were observed at various positions.

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, halo or halogen means any one selected from the group consisting of fluorine, chlorine, bromine and iodine.

Unless otherwise specified herein, a prefixed hetero means one to three heteroatoms selected from the group consisting of N, O, S and P substituting 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, alkyl means an alkyl group of 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 herein, an alkylene (or alkanediyl) is a divalent atomic group obtained by subtracting two hydrogen atoms from an alkane, and may be represented by the general formula -C _n H _2n -.

Unless otherwise specified herein, a heterocycle is a monocyclic or bicyclic heterocycle in which one or more (e.g., one, two, three or four) carbon atoms are replaced by a heteroatom (e.g., N, O, P or S) Means a cyclic radical having 4 to 20 ring atoms. In addition, the above-mentioned ring includes a saturated ring, a partially unsaturated ring, and an aromatic ring (i.e., a heteroaromatic ring), and the hetero atom in the ring may be oxidized or capped, Or a cyclic aromatic radical that forms a quaternary salt. A substituted heterocycle includes a heterocyclic ring substituted with any of the substituents disclosed herein, including, for example, a carbonyl group.

Unless otherwise stated in the present specification, olefin means a linear or cyclic unsaturated hydrocarbon compound containing a double bond. But are not limited to, for example, alkylene, acrylate, styrene, norbornene, indene, acenaphthene, furandione, and the like.

In the present specification, all the compounds or substituents may be substituted or unsubstituted unless otherwise specified. The term "substituted" as used herein 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 nitryl group, an aldehyde group, , A carboxyl 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, It means that one has been replaced.

In the present specification, the 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 unless otherwise specified.

The conventional resists, particularly, the monomers constituting the resist polymer are mainly composed of carbon and hydrogen. However, it is effective to use oxygen and nitrogen which have better EUV absorption in EUV resists. If the EUV resist can not raise the absorption rate of the EUV light source itself, the photon generation amount decreases, the number of the photoacid generators to function is decreased, and the acid yield is lowered, thereby inhibiting pattern formation.

On the contrary, in the present invention, the content of nitrogen and oxygen in the resist polymer is increased to increase the absorption rate to the EUV light source, thereby increasing the acid yield, and inducing rearrangement of the molecule itself after exposure to generate an acid and an inert gas And as a result, the developing speed for the base developer is increased to facilitate the formation of fine patterns.

That is, the monomer according to one embodiment of the present invention has a structure represented by the following Formula 1:

[Chemical Formula 1]

In Formula 1,

R ₁ is a hydrogen atom or a functional group represented by the following formula (2)

R _2a and R _2b are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, and a functional group represented by the following formula Any one of R ₁ , R _2a and R _2b is a functional group represented by the following general formula (2)

(2)

(2)

R ₃ is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 30 carbon atoms, a linear or branched heteroalkylene group having 1 to 20 carbon atoms, and a heterocycloalkylene group having 3 to 30 carbon atoms , &Lt; / RTI &gt;

R ₄ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a combination thereof)

R is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group, and an alkoxy group having 1 to 10 carbon atoms,

m is an integer of 1 to 3;

Preferably R ₁ in formula (I) is a hydrogen atom or a functional group represented by the above formula 2, R _2a and R _2b are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkyl group, a hydroxy group, a fluoroalkyl group having 1 to 5 carbon atoms, An alkoxy group having 1 to 5 carbon atoms, and a functional group represented by the general formula (2), provided that any one of R ₁ , R _2a and R _2b is a functional group represented by the general formula (2). More preferably, R ₁ is a hydrogen atom or a functional group represented by the general formula (2), R _2a and R _2b each independently represent a hydrogen atom, a methyl group, an ethyl group, a perfluoromethyl group, a hydroxyl group, a methoxy group, Functional group, provided that any one of R ₁ , R _2a and R _2b is a functional group of the above formula (2).

Preferably, R is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a fluoroalkyl group having 1 to 5 carbon atoms, a hydroxyl group, and an alkoxy group having 1 to 5 carbon atoms, more preferably a hydrogen atom, A methyl group, an ethyl group, a perfluoromethyl group, a hydroxy group, a methoxy group and an ethoxy group.

Preferably, R ₃ is a linear or branched alkylene group having 1 to 10 carbon atoms, a monocyclic cycloalkylene group having 3 to 14 carbon atoms, a bicyclic cycloalkylene group having 8 to 18 carbon atoms, a tricyclic A cycloalkylene group having 10 to 30 carbon atoms, a heterocycloalkylene group having a divalent linking group containing a heteroatom, a heterocycloalkylene group having a divalent linking group containing a heteroatom in the ring, and Wherein the divalent linking group containing a hetero atom is selected from the group consisting of -O-, -C (= O) -O-, -C (= O) -, -OC ) -O-, -C (= O) -NH-, -NH- ( wherein H is an alkyl group, O may be substituted with a substituent such as a group), -S-, -S (= O ) 2 -, - S (= O) ₂ -O-, and -AO (oxygen atom) -B- (wherein A and B are each independently a substituted or unsubstituted divalent hydrocarbon group &Quot;).&Quot;

Even more preferably R ₃ represents a methylene group, an ethylene group _{[- (CH 2) 2 -} ], a trimethylene group _{[- (CH 2) 3 -} ], a tetramethylene group _{[- (CH 2) 4 -} ], pentamethylene group _{[- (CH 2) 5 -} ], -CH (CH 3) -, -CH (CH 2 CH 3) -, -C (CH 3) 2 -, -C (CH 3) (CH 2 CH _{3) -, -C (CH 3} ) (CH 2 CH 2 CH 3) -, -C (CH 2 CH 3) 2 -, -CH (CH 3) CH 2 -, -CH (CH 3) CH (CH _{3) -, -C (CH 3} ) 2 CH 2 -, -CH (CH 2 CH 3) CH 2 -, -CH (CH 3) CH 2 CH 2 -, -CH 2 CH (CH 3) CH 2 - , -CH (CH ₃ ) CH ₂ CH ₂ CH ₂ -, and -CH ₂ CH (CH ₃ ) CH ₂ CH ₂ -.

Preferably, in Formula 2, R ₄ may be selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom, a methyl group, an ethyl group, And ethoxy groups.

Preferably, the compound of formula 1 may be a compound of formula 1a or 1b:

[Formula 1a]

[Chemical Formula 1b]

In the general formulas (1a) and (1b), R _3a and R _3b are each as defined for R ₃ , and R _4a and R _4b are respectively as defined for R ₄ .

Preferably, in the above general formulas (1a) and (1b), R _3a and R _3b are each independently an ethylene group, and R _4a and R _4b are each independently a hydrogen atom or a methyl group.

Compounds of formula (I) having the above structure can be prepared by reacting a compound of formula (3) with a compound of formula (4): &lt; EMI ID =

(3)

[Chemical Formula 4]

In the general formulas (2) and (3), R, R ₃ , R ₄ and m are the same as defined above,

R ₁ 'is a hydrogen atom or a functional group of the following formula (5)

R _2a 'and R _2b ' are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, , Provided that any one of R ₁ , R _2a and R _2b is a functional group of the following formula (5)

[Chemical Formula 5]

In Formula 5, X is a halogen group.

Specifically, the compound of formula (3) and the compound of formula (4) may be reacted in the presence of a basic compound in a solvent to prepare a compound of formula (1).

The compounds of formulas (3) and (4) used in the preparation of the compounds of formula (1) can be prepared according to conventional methods or, if possible, are commercially available.

Specifically, examples of the compound of Formula 3 include 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride, 1,2-naphthoquinone- 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride, and the like can be used.

Examples of the compound of Formula 4 include 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, and the like. have.

The compound of the formula (3) and the compound of the formula (4) are preferably reacted in an amount satisfying the stoichiometric ratio.

As the basic compound, triethylamine or the like can be used.

As the solvent, an organic solvent such as dimethylsulfoxide, dichloromethane, chloroform, dichloroethane, acetonitrile, toluene, benzene, 1,4-dioxane and the like can be used.

The acrylic monomer produced by the above method has a high content of nitrogen and oxygen atoms in the compound, and when used as a monomer for preparing a resist polymer, exhibits a high absorption rate with respect to a light source, resulting in an increased acid yield . In particular, the EUV light source exhibits a higher absorption rate at the nitrogen or oxygen atom than carbon. Because of this, it is possible to generate more acid at a higher absorption rate if nitrogen or oxygen atoms are contained in large amounts. The acrylic monomer according to the present invention contains a large amount of nitrogen and oxygen atoms in the molecule and can exhibit a high absorption rate with respect to the EUV light source, which can increase the amount of photons capable of activating the PAG, The sensitivity and the resolution can be improved.

In addition, the acrylic monomer according to the present invention generates an acid and an inert gas due to intramolecular rearrangement after the concentration process when applied to a resist polymer, and as a result, the developing rate for the base developer can be increased.

The following Reaction Scheme 1 schematically shows a reaction mechanism for generating an acid through rearrangement in the molecule during light irradiation of the acrylic monomer according to the present invention. The following Reaction Scheme 1 is only one example for illustrating the present invention, but the present invention is not limited thereto.

[Reaction Scheme 1]

As shown in Reaction Scheme 1, the acid generated by the re-arrangement plays the role of chemically amplified resist (CAR). That is, an acid is formed as in an acid-labile group in conventional resist polymers, thereby increasing solubility in a base developer.

In addition, as shown in the first process of the above mechanism, nitrogen gas is generated during light irradiation. The gas generated in the resist during the exposure increases the development speed for the base developer without contamination with EUV equipment.

According to another embodiment of the present invention, there is provided a resist polymer comprising a repeating unit derived from the monomer of the above formula (1).

The polymer may further comprise a repeating unit derived from an olefin compound or a heterocycloalkylene compound. Specifically, it may further include a repeating unit derived from a compound selected from the group consisting of an alkylene-based compound, a cyclic olefin-based compound, a styrene-based compound, and a furandione-based compound, and preferably a vinyl-based compound, a styrene- A compound derived from a compound selected from the group consisting of an indene compound, an acenaphthene compound, and a furandione compound.

The polymer may further comprise a repeating unit of formula (6) derived from an acrylic compound:

[Chemical Formula 6]

In Formula 6,

R ₅ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and combinations thereof, and

R ₆ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, And R ₆ may be substituted with a substituent selected from the group consisting of a carbonyl group, a carboxyl group, an ether group, a nitrile group and a halogen group.

Specifically, the polymer according to the present invention may be a compound having the structure of the following formula (7): &lt; EMI ID =

(7)

In Formula 7, R ₃ is as defined above,

R _5a , R _5b And R _5c are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a combination thereof,

The R _6a and R _6b And R _6c each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, A heteroaryl group having 3 to 30 carbon atoms, and a combination thereof, and may be substituted with a substituent selected from the group consisting of a carbonyl group, a carboxyl group, an ether group, a nitrile group and a halogen group,

W is a repeating unit derived from an olefin compound or a heterocycloalkylene compound,

Y is a functional group of the following formula (8a) or (8b)

[Chemical Formula 8a]

[Formula 8b]

(In the above formulas 8a and 8b,

R ₁₁ is a hydrogen atom,

R ₂₁ and R ₂₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group and an alkoxy group having 1 to 10 carbon atoms,

R _a and R _b are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group, and an alkoxy group having 1 to 10 carbon atoms, And m1 and m2 are each independently an integer of 1 to 3), and

(a + b + c + d + e) < 0.5, wherein a, b, c, d and e each represent a repeating unit in the main chain, (A + b + c + d + e) < 0.5, 0? C / (a + b + c + ) &Lt; 0.5 and 0 < e / (a + b + c + d + e) < 0.5.

Preferably, R &lt; _5a &gt; and R &lt; _5b &gt; And R _5c are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom, a methyl group, an ethyl group, a methoxy group, &Lt; / RTI &gt;

Preferably, R _6a may be an acid labile group. By including the acid-sensitive functional group in this way, the hydrophobic property is changed from hydrophobic to hydrophilic by the acid-assisted deprotection at the exposed site in the exposure, and as a result, it can be easily washed away by the developer during development at the exposed site.

,

및

로 이루어진 군에서 선택되는 산 민감성 기이고, 이때 R', R" 및 R"'는 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 포화되거나 또는 불포화된, 탄화수소 고리 또는 헤테로사이클 고리를 형성할 수 있으며, R""는 탄소수 1 내지 10의 알킬기이고, z는 0 내지 3의 정수이고, w는 0 내지 10의 정수이다. Specifically, R &lt; _{6a &}

,

And

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

More preferably, R _6a 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 &Lt; / RTI &gt;

Wherein R ', R "and R'" each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a hydroxy group, an alkylsilyl group having 1 to 10 carbon atoms, and a cycloalkyl group having 3 to 18 carbon atoms And o and s are integers from 0 to 15, p is an integer from 0 to 11, q and r are each independently an integer from 0 to 9, t is selected from the group consisting of 0 to 7 And u and v are each independently an integer of 0 to 6, 0? Q + r? 17, 0? Q + t? 15,

And even more preferably selected from the group consisting of the following formulas (10a) to (10h).

Preferably, in Formula 7, R _6b may be a lactone group.

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

또는

이며(이때 R' 및 R"는 각각 독립적으로 탄소수 1 내지 10의 알킬기이거나 서로 연결되어 포화 탄화수소 고리를 형성할 수 있으며, x 및 y는 각각 독립적으로 0 내지 5의 정수이다)일 수 있으며, 다 바람직하게는 하기 화학식 11a 또는 11b일 수 있다.Specifically, R &lt; _6b &gt;

or

(Where R 'and R "are each independently an alkyl group having 1 to 10 carbon atoms or may be connected to each other to form a saturated hydrocarbon ring, and x and y are each independently an integer of 0 to 5) And may preferably be represented by the following formula (11a) or (11b).

In Formula 7, W may be a repeating unit derived from a compound selected from the group consisting of an alkylene-based compound, a cyclic olefin-based compound, a styrene-based compound, and a furandione-based compound, more preferably a vinyl- Based compound, a norbornene-based compound, an indene-based compound, an acenaphthene-based compound, and a furandione-based compound.

More preferably, W may be selected from the group consisting of the following formulas (12a) or (12b): &lt; EMI ID =

In the above formula (7), the repeating units a, b, c, d and e represent 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 acid enhancer according to the present invention is characterized in that the repeating units a, b, c, d and e satisfy the relationship 0 a / a + b + c + d + e (A + b + c + d + e) < 0.5, 0? B / (a + b + c + d + e) + d + e) < 0.5 and 0 < e / (a + b + c + d + e) < By including the recurring units in the above proportions, a finer pattern can be realized. In particular, by including 50 mol% or less of the monomer-derived repeating unit e in the formula (1), it is possible to form a uniform pattern throughout the wafer, Can be reduced.

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 polymer according to the present invention include compounds having the structures of the following formulas (7a) to (7d), and the order of each repeating unit in the structural formula can be changed:

In the formula 7a to _{7d, R 1, R 6a,} R 6b, R 6 c, a, b, c, d and e are as previously defined.

The polymer according to the present invention may have a polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") of 1,000 to 100,000 g / mol by gel permeation chromatography (GPC). When the weight average molecular weight of the polymer is too small, there is a possibility that the etch resistance is insufficient. When the weight average molecular weight is too large, appropriate film formation may be difficult or alkaline solubility may be deteriorated. Preferably, a weight average molecular weight of 2,000 to 10,000 g / mol is preferable because it can exhibit excellent solubility in a developer.

The polymer 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 polymer according to the present invention having the above structure may be prepared by polymerizing at least one monomer selected from the group consisting of the monomers of the formula (1), the olefin monomers and the acrylic monomers having the structures of the following formulas (13a) to (13c) For example, by polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, bulk suspension polymerization, emulsion polymerization, and the like.

[Chemical Formula 13a]

[Chemical Formula 13b]

[Chemical Formula 13c]

In the above formulas, R _5a to R _5c and R _6a to R _6c are as defined above.

Preferably, the polymer according to the present invention can be polymerized by radical polymerization, wherein the radical polymerization initiator is selected from the group consisting of azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), lauryl peroxide, azobisisobutyronitrile There are no particular limitations as long as it is used as a general radical polymerization initiator such as capro nitrile, 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 polymer according to the present invention contains a repeating unit derived from an acrylic monomer having the high content of oxygen and nitrogen, and thus exhibits a high absorption rate with respect to a light source, particularly an EUV light source. As a result, The amount of photon capable of activating the photoacid can be increased, thereby increasing the amount of acid generated in the photoacid generator.

The resist polymer generates an acid and an inert gas by molecular rearrangement in a repeating unit derived from the acrylic monomer of the above formula (1) upon irradiation with light, and the generated acid and the inert gas form a developing rate for the base developer The increase rate can be increased. Although the above-described reaction mechanism is described for use in EUV resists, the present invention is not limited thereto, but can be applied to all lithography using CAR type such as KrF, ArF, X-ray, and the like.

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

Specifically, the resist composition includes a solvent together with the polymer as a base polymer for a resist.

The polymer is the same as described above, and the 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.

Further, it may further comprise a base polymer which is usually used as a base resin in forming a resist film together with the above-mentioned polymer. Specific examples thereof include polymers obtained by a ring-opening metathesis reaction of a (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 copolymerizing any one of anthracene, indene, hydroxyindene, acenaphthylene, and norbornadiene, a novolak resin, and a mixture thereof.

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.

The resist composition may further comprise an acid generator.

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 this formula,

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 this formula,

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 may be selected from the group consisting of the functional groups represented by the following general formulas (17-1) to (17-36)

In the above formulas (14) and (15), preferable cation moieties include the structures represented by the following formulas (18-1) to (18-16)

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 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. When the content of the acid diffusion inhibitor is less than 0.01 part by weight, the influence of the retardation after exposure 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 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 dose of about 1 to 200 mJ / cm 2, preferably about 10 to 100 mJ / cm 2, the film is irradiated at 60 to 150 ° C for 1 to 5 minutes, preferably at 80 to 130 ° C for 1 to 3 Minute Post Exposure Bake (PEB).

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

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

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

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

[Monomeric Synthetic example  One]

20 g of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride (i) and 20 g of 2-hydroxynaphthoquinone were dissolved in 200 ml of dichloromethane. 8.7 g of 2-hydroxyethyl methacrylate (ii) was added thereto, and the mixture was stirred at room temperature for dissolution. As a result, 5.9 g of triethylamine was slowly added dropwise to the resulting solution, and the reaction was allowed to proceed. The progression and termination of the reaction were confirmed by thin layer chromatography, and the reaction was terminated after stirring for 5 hours. The organic layer was separated from the resulting reaction solution, and the separated organic layer was washed with NaOH aqueous solution three times to remove impurities, followed by extraction with distilled water several times. As a result, the solvent was removed from the collected organic layer to give the target compound (iii) (yield: 75%).

[Monomeric Synthetic example  2]

20 g of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride (v) (20 g) and 2-heptanone were added to 200 ml of dichloromethane And 8.7 g of (2-hydroxyethyl methacrylate) (ii) were added and dissolved at room temperature by stirring. As a result, 5.9 g of triethylamine was slowly added dropwise to the resulting solution, and the reaction was allowed to proceed. The progression and termination of the reaction were confirmed by thin layer chromatography, and the reaction was terminated after stirring for 5 hours. The organic layer was separated from the resulting reaction solution, and the separated organic layer was washed with NaOH aqueous solution three times to remove impurities, followed by extraction with distilled water several times. The solvent was removed from the resulting organic layer to give the desired compound (v) (yield: 77%).

[Polymer Synthetic example  One]

1.50 g of norbornene for polymerization and 0.70 g of dimethyl azobis isobutylate as a polymerization initiator were poured and dissolved in a flask together with 11.02 g of 1,4-dioxane. Nitrogen gas was used to displace the inside of the flask with nitrogen, and the temperature inside the flask was raised to 50 캜. When the inside temperature of the flask reached 50 캜, 4.00 g of the monomer (iii) prepared in Synthesis Example 1 of the monomer, 2.31 g of gamma-butyrolactone methacrylate, 2.30 g of hydroxyadamantane methacrylate A mixture of 1.50 g of hydroxyl adamantane methacrylate and 11.02 g of 1-methyl adamantane methacrylate and 1,4-dioxane was dripped for 2 hours using a feeding pump, The inside temperature of the flask was raised to 75 캜. After completion of the dropwise addition, the reaction was carried out at the same temperature for 3 hours. The resulting reaction solution was cooled to room temperature, precipitated with excess n-hexane / isopropyl alcohol, and the resulting precipitate was separated by filtration. The separated precipitate was washed with the same solvent as in the filtration and dried under reduced pressure to obtain 9.50 g of polymer (I).

The polystyrene reduced weight average molecular weight (Mw) of the obtained polymer was 7350 g / mol, and the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight was 2.24.

[Polymer Synthetic example  2]

In Synthesis Example 1 of the polymer, 3-bicyclo [2,2,1] hept-5-en-2-yl-t-butoxycarbonyloxy-propionic acid t-butyl ester Except that 2.5 g of 3-bicyclo [2.2.1] hept-5-en-2-yl-tertbutoxycarbonyloxy-propionic acid tert-butyl ester was used as a polymerization initiator II) &lt; / RTI &gt;

The polystyrene reduced weight average molecular weight (Mw) of the obtained polymer was 7640 g / mol and the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight was 2.18.

[Polymer Synthetic example  3]

Except that 3.2 g of norbornane carbolactone methacrylate was used as a polymerization monomer instead of gamma-butyrolactone methacrylate in Synthesis Example 1 of the polymer, the same procedure as in Synthesis Example 1 of the polymer To obtain 9.56 g of polymer (III).

The polystyrene reduced weight average molecular weight (Mw) of the obtained polymer was 7890 g / mol, and the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight was 2.35.

[Polymer Synthetic example  4]

Except that 2.8 g of the monomer (v) prepared in Synthesis Example 2 of the above-mentioned monomer was used in place of the monomer (iii) prepared in Synthesis Example 1 of the above monomer as the polymerization monomer in Synthesis Example 1 of the polymer. Was carried out in the same manner as in Synthesis Example 1 to obtain 9.56 g of Polymer (IV).

The polystyrene reduced weight average molecular weight (Mw) of the obtained polymer was 7250 g / mol, and the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight was 2.05.

[ Test Example : pattern Formability  evaluation]

In order to form a resist film of the polymer according to the present invention and to evaluate the properties of the resulting resist film, a resist composition comprising each of the polymers prepared in Synthesis Example 1 or 4 of the polymer was prepared, and the L / S pattern .

Specifically, 1.0 g each of the polymer (I or II) prepared in Synthesis Example 1 or 2 of the polymer, 0.31 g of the photoacid generator of the following formula (19) and 0.07 g of triisopropanol amine as an inhibitor were dissolved in 80 g of propylene glycol Dissolved in propyleneglycol monoethyl ether acetate (PGMEA), and filtered through a polypropylene filter having a size of 0.2 mu m to prepare a resist.

[Chemical Formula 19]

An antireflection film (BARC) having a film thickness of 90 nm was formed on a silicon substrate. The resist 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 .

Next, exposure was performed at 100 ° C. for 60 seconds using EUV immersion exposure equipment, and then PEB was performed at 130 ° C., and developed with a 2.38% by weight TMAH developer for 60 seconds to form a 50 nm L / S (line and space) pattern.

The pattern of the L / S pattern formed in the above was observed with a CD-SEM (critical dimension scanning electron microscope). For comparison of pattern formability, a polymer having a structure of Formula 20 (Mw: 11850 g / mol, Mw / Mn: 1.97, molar ratio of each repeating unit (p: q: r: s) of 30:35:30:30 ), A resist pattern was formed in the same manner as described above, and evaluated:

[Chemical Formula 20]

The results are shown in Figs.

1 is a CD-SEM photograph of a polymer obtained by using the polymer (I) prepared in Synthesis Example 1, and FIG. 2 is a photograph of the polymer (II) prepared in Synthesis Example 2 of the polymer FIG. 3 is a CD-SEM photograph of a L / S pattern prepared by using a polymer of the comparative example (polymer of formula (20)).

As shown in FIGS. 1 to 3, when a pattern is formed using the polymer (I or II) containing a repeating unit derived from the monomer according to the present invention, the polymer exhibits excellent pattern formation as compared with the polymer used as a comparative example can confirm.

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 (16)

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

In Formula 1,
R ₁ is a hydrogen atom or a functional group represented by the following formula (2)
R _2a and R _2b are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, and a functional group represented by the following formula Any one of R ₁ , R _2a and R _2b is a functional group represented by the following general formula (2)
(2)

(2)
R ₃ is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 30 carbon atoms, a linear or branched heteroalkylene group having 1 to 20 carbon atoms, and a heterocycloalkylene group having 3 to 30 carbon atoms , &Lt; / RTI &gt;
R ₄ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a combination thereof)
R is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group and an alkoxy group having 1 to 10 carbon atoms,
m is an integer of 1 to 3; The method according to claim 1,
An acrylic monomer having a structure represented by the following formula (1a) or (1b):
[Formula 1a]

[Chemical Formula 1b]

In the above general formulas (1a) and (1b)
R _3a and R _3b each independently represent a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 30 carbon atoms, a linear or branched heteroalkylene group having 1 to 20 carbon atoms, and a linear or branched alkylene group having 3 to 30 carbon atoms &Lt; / RTI &gt; and &lt; RTI ID = 0.0 &gt;
R _4a and R _4b are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and combinations thereof. 3. The method of claim 2,
R _3a and R _3b are each independently a methylene or ethylene group
And R _4a and R _4b are each independently a hydrogen atom or a methyl group. A resist polymer comprising a repeating unit derived from the acrylic monomer according to claim 1. 5. The method of claim 4,
Wherein the polymer further comprises a repeating unit derived from an olefin compound or a heterocycloalkylene compound. 5. The method of claim 4,
Wherein the polymer further comprises a repeating unit represented by the following formula (6): &lt; EMI ID =
[Chemical Formula 6]

In Formula 6,
R ₅ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and combinations thereof, and
R ₆ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, A heteroaryl group and a combination thereof, and R ₆ is substituted or unsubstituted with a substituent selected from the group consisting of a carbonyl group, a carboxyl group, an ether group, a nitrile group and a halogen group. 5. The method of claim 4,
A resist polymer having a structure represented by the following formula (7): < EMI ID =
(7)

In Formula 7,
R _5a , R _5b And R _5c are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a combination thereof,
The R _6a and R _6b And R _6c each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, A heteroaryl group having 3 to 30 carbon atoms, and a combination thereof, and R _6a and R _6b And R _6c are each independently substituted or unsubstituted with a substituent selected from the group consisting of a carbonyl group, a carboxyl group, an ether group, a nitrile group and a halogen group,
W is a repeating unit derived from an olefin compound or a heterocycloalkylene compound,
Y is a functional group of the following formula (8a) or (8b)
[Chemical Formula 8a]

[Formula 8b]

(In the above formulas 8a and 8b,
R ₁₁ is a hydrogen atom,
R ₂₁ and R ₂₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group and an alkoxy group having 1 to 10 carbon atoms,
R _a and R _b are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group and an alkoxy group having 1 to 10 carbon atoms,
m1 and m2 are each independently an integer of 1 to 3) and
(a + b + c + d + e) < 0.5, wherein a, b, c, d and e each represent a repeating unit in the main chain, (A + b + c + d + e) < 0.5, 0? C / (a + b + c + ) &Lt; 0.5 and 0 < e / (a + b + c + d + e) &lt; 0.5. 8. The method of claim 7,
Wherein R &lt; _{5a &}

,

And

, Wherein R ', R "and R"' are each independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a (cycloalkyl group having 1 to 10 carbon atoms) (Alkyl group having 1 to 10 carbon atoms), a hydroxyalkyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an acetyl group, an acetylalkyl group, a carboxyl group, A carboxyl group and a heterocycloalkyl group having 3 to 30 carbon atoms, or groups adjacent to each other may be connected to form a saturated or unsaturated hydrocarbon ring or heterocyclic ring having 3 to 30 carbon atoms, and R " Is an alkyl group having 1 to 10 carbon atoms, z is an integer of 0 to 3, w is an integer of 0 to 10,
R &lt; _5b &gt;

or

, Wherein R 'and R "are each independently an alkyl group of 1 to 10 carbon atoms or may be connected to each other to form a saturated hydrocarbon ring, x and y are each independently an integer of 0 to 5,
W is a repeating unit derived from a compound selected from the group consisting of an alkylene-based compound, a cyclic olefin-based compound, a styrene-based compound, and a furandione-based compound. 8. The method of claim 7,
And W is a repeating unit derived from a compound selected from the group consisting of a vinyl compound, a styrene compound, a norbornene compound, an indene compound, an acenaphthene compound, and a furandione compound. 8. The method of claim 7,
A compound having a structure represented by the following formulas (7a) to (7d):

In the above formulas (7a) to (7d)
_{R 1, R 6a, R 6b} , and R ₆ c will be each independently selected from the group consisting of a hydrogen atom, an alkoxy group, and combinations of alkyl groups having 1 to 10 carbon atoms, having 1 to 10 carbon atoms, and
(a + b + c + d + e) < 0.5, wherein a, b, c, d and e each represent a repeating unit in the main chain, (A + b + c + d + e) < 0.5, 0? C / (a + b + c + ) &Lt; 0.5 and 0 < e / (a + b + c + d + e) < 0.5. 5. The method of claim 4,
Wherein the polymer has a polystyrene reduced weight average molecular weight of 1,000 to 100,000 g / mol by gel permeation chromatography (GPC). 5. The method of claim 4,
Wherein the polymer has a molecular weight distribution of 1 to 3, wherein the ratio of the weight average molecular weight to the number average molecular weight is (Mw / Mn). A resist composition comprising the resist polymer according to claim 4. 5. A resist composition for extreme ultraviolet lithography comprising the resist polymer according to claim 4. Forming a resist film by applying the resist composition according to claim 13 on a substrate,
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. 16. The method of claim 15,
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.

Images