TWI483069B - Novel acryl monomer, polymer, resist composition comprising same and method for forming resist pattern - Google Patents

Description

New acrylic monomers, polymers, and resists containing the polymer Agent composition and method of forming a resist pattern

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

Recently, with the high integration and high speed of a large integrated circuit (LSI), it is required to refine the photoresist pattern. As the exposure light source for forming the resist pattern, g-rays (436 nm) such as mercury or i-rays (365 nm) or the like are mainly used.

However, the resolution caused by the increase in the exposure wavelength is actually approaching the limit, and as a method of forming a finer photoresist pattern, a method of shortening the wavelength has been proposed. As a specific example, a short-wavelength KrF excimer laser (248 nm), an ArF excimer laser, or the like is used instead of the i-ray (365 nm).

An ArF immersion lithography method using an ArF excimer laser as a light source, characterized in that a lens and a wafer substrate are used Water immersion is carried out between. This method utilizes the refractive index of water in 193 nm, and can form a pattern even if a lens of NA 1.0 or more is used, and is generally called an immersion lithography method. However, since the resist film is directly in contact with water (pure water), the amine compound as an acid or a quener added to the resist film is formed because the photoacid generator is easily dissolved in water. The resist pattern shape or various defect phenomena such as collapse of the expansion pattern, bubble defects, or watermark defects.

For this reason, a method of forming a protective film or an upper film between a resist film and water has been proposed for the purpose of insulating a resist film from a medium such as water. As such a resist protective film, it is required to have a characteristic that the wavelength has sufficient light transmittance so as not to interfere with exposure, and does not cause intermixing with a resist film to be formed on the resist film, and immersion exposure In the case of dissolving in a medium such as water, it is formed in a stable film, and is easily dissolved in an alkaline solution or the like as a developing solution during development.

Prior technical literature

Patent literature

Patent Document 1: Korean License No. 0931924 (authorized by 2009.12 07)

Patent Document 2: Korean franchise authorization No. 0979418 (authorized by 2010.05.18)

Patent Document 3: Korean Patent Laid-Open No. 2011-0004923 (published 2011.07.26)

An object of the present invention is to provide a novel acrylic monomer useful for forming an additive for resisting, which is capable of improving the hydrophobicity of a surface of a resist film during exposure during microfabrication according to an immersion lithography method. Thereby, it is possible to suppress leaching by water, and convert to hydrophilicity in the developing step, so that the surface of the resist film has a low static contact angle, thereby suppressing occurrence of defects and forming fineness with excellent sensitivity and resolution. Resist pattern.

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

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

In order to achieve the object, an acrylic monomer according to an embodiment of the present invention is represented by the following Chemical Formula 1.

In the chemical formula 1, R ¹ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ² is an alkenyl group selected from an alkyl group having 1 to 20 carbon atoms and 2 to 20 carbon atoms. a heteroalkyl group having 1 to 20 carbon atoms, a heteroalkylene 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, and carbon In the group consisting of a heterocycloalkyl group having 2 to 30 atoms and a heterocycloalkenyl group having 3 to 30 carbon atoms, X contains a dendritic unit represented by the following Chemical Formula 2 and is represented by the following Chemical Formula 3 The end unit indicated, In the chemical formulas 2 and 3, R ³ is an alkyl group selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and a carbon number. In the group consisting of a cycloalkyl group of 3 to 30, a cycloalkenyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a heterocyclic group having 2 to 30 carbon atoms, Y is selected from the group consisting of A hydrophobic group in the group consisting of a halogen alkyl group having 1 to 20 carbon atoms, an organic fluorenyl group and a hydrocarbon group having 3 to 20 carbon atoms, and a is an integer of 0 or 1.

The acrylic monomer of Chemical Formula 1 may contain 1 to 3 by the Chemical Formula 2 The dendritic unit represented.

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

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

The polymer may further contain a repeating unit represented by the following Chemical Formula 10.

In the chemical formula 10, R ⁴ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁵ is selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a carbon number of 1 to 10. a heteroalkyl group, 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 a heteroaryl group having 5 to 30 carbon atoms; Any of the groups.

Preferably, the polymer may have the structure of the following Chemical Formula 11.

In the formula 11, R ¹ , R ² and X are the same as defined above, and R ⁴¹ and R ⁴² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁵¹ and R ⁵² are each independently Selected as a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a heteroalkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, or carbon Any one of a group consisting of an aryl group having 6 to 30 atoms and a heteroaryl group having 5 to 30 carbon atoms, and further, l, m and n are molars respectively representing a repeating unit in the main chain. The number of ratios, l+m+n=1,0<1/(l+m+n) 0.99,0 m/(l+m+n) 0.99,0<n/(l+m+n) 0.99.

Preferably, the R ⁵¹ is selected from the group consisting of , with An acid-sensitive group in the group formed, in which case, Ra, Rb and Rc are each independently selected from an alkyl group having 1 to 2 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, (having 1 carbon atom) An alkyl group to 10, a cycloalkyl group, a hydroxyalkyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an ethyl group, an ethoxy group, a carboxyl group, a group consisting of a carboxyl group (alkyl group having 1 to 10 carbon atoms), a carboxyl group (cycloalkyl group having 3 to 18 carbon atoms) and a heterocycloalkyl group having 3 to 30 carbon atoms, or a group adjacent to each other The group is bonded to form a saturated or unsaturated hydrocarbon ring or heterocyclic ring having 3 to 30 carbon atoms, Rd is an alkyl group having 1 to 10 carbon atoms, p is an integer of 0 to 3, and q is an integer of 0 to 10, and , R ⁵² is or In this case, Re and Rf may each independently be an alkyl group having 1 to 10 carbon atoms, or may be bonded to each other to form a saturated hydrocarbon ring, and r and s are each independently an integer of 0 to 5.

More preferably, said R ⁵¹ is selected from the group consisting of t-butyl, trimethylmethanyl, hydroxy-2-ethyl, 1-methoxypropyl, 1-methoxy-1-methylethyl , 1-ethoxypropyl, 1-ethoxy-1-methylethyl, 1-methoxy-1-ethyl, 1-ethoxy-1-ethyl, tert-butoxy-2 a group consisting of -ethyl, 1-isobutoxy-1-ethyl and the following chemical formulas 12a to 12j,

In the chemical formulas 12a to 12j, R', R" and R"' are each independently selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 1 to 10 carbon atoms. In the group consisting of an alkylcarboxyalkyl group and a cycloalkylcarbinyl group having 3 to 18 carbon atoms, a and e are integers of 0 to 15, b is an integer of 0 to 11, and c and d are independent, respectively. An integer from 0 to 9, f is an integer from 0 to 7, and g and i are each independently an integer from 0 to 6, 0 c+d 17,0 c+f Further, the R ⁵² may have a structure of the following chemical formula 14a or 14b.

Preferably, the polymer has a weight average molecular weight of 1000 in terms of polystyrene permeation by gel permeation chromatography. Up to 20,000 g/mol.

It may be preferred that the ratio of the weight average molecular weight to the number average molecular weight of the polymer is from 1 to 3.

Preferably, the polymer is selected from the group consisting of compounds having the structures of the following chemical formulas 15a to 15p.

In the chemical formulas 15a to 15p, l, m and n are l+m+n=1, 0<1/(l+m+n) 0.99,0<m/(l+m+n) 0.99 and 0<n/(l+m+n) 0.99.

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

The resist additive is polymerized with respect to the total weight of the resist composition The content of the substance may be from 0.05 to 5% by weight.

The acid generator may be one or more selected from the group consisting of compounds represented by the following Chemical Formulas 18 and 19.

In the chemical formulas 18 and 19, X ₁ , X _{2 ,} Y ₁ and Y ₂ are each independently selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, an allyl group, a perfluoroalkyl group, a benzyl group, Any one of the group consisting of an aryl group having 6 to 30 carbon atoms and a combination thereof, wherein X ₁ and X ₂ and Y ₁ and Y ₂ are bonded to each other to form a saturation of 3 to 30 carbon atoms. Or an unsaturated hydrocarbon ring.

X ₃ , X ₄ , X ₅ , Y ₃ , Y ₄ and Y ₅ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a halogen group, an alkoxy group having 1 to 30 carbon atoms, and carbon. An aryl group having 6 to 30 atoms, a thiophenoxy group, a thioalkoxy group having 1 to 3 carbon atoms, an alkoxycarbonylmethoxy group having 1 to 20 carbon atoms, and a combination thereof In any of the groups, the Z of the anion moiety 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 a functional group represented by the following Chemical Formula 20.

In the chemical formula 20, V ₁ and V ₂ are each independently a halogen atom, W ₁ is -(C=O)- or -(SO ₂ )-, and W ₂ is an alkylene group having 1 to 10 carbon atoms. W _{3 is} selected from the group consisting of a cycloalkyl group having 3 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, and a heterocycloalkenyl group having 5 to 30 carbon atoms, and W ₄ is a hydrogen atom, a halogen group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenalkyl group having 1 to 10 carbon atoms, or the like (alkyl group having 1 to 10 carbon atoms) thio group, cycloalkyl group having 3 to 30 carbon atoms, aryl group having 6 to 30 atoms, (aryl group having 6 to 30 carbon atoms), ( Any one of the group consisting of an aryl)thio group having 6 to 30 carbon atoms, a heterocyclic group having 5 to 30 carbon atoms, and a combination thereof, o is an integer of 0 to 1, and p is 0. An integer of up to 2.

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

According to still another embodiment of the present invention, there is provided a method of forming a resist pattern, the method comprising the steps of: coating a resist composition on a substrate to form a resist film; and heat-treating the anti-resistance a step of exposing in a prescribed pattern after etching the film; and a step of developing the exposed resist pattern.

The exposing step can be carried out using a light source selected from the group consisting of a KrF excimer laser, an ArF excimer laser, an extreme ultraviolet laser, an X-ray, and an electron beam.

Specific matters of other embodiments of the invention are included in the detailed description below.

The polymer for resist additive prepared from the novel acrylic monomer according to the present invention can be inhibited from being soaked in water by increasing the hydrophobicity of the surface of the resist film during the exposure step during microfabrication according to the immersion lithography method. When the developing step is performed after the exposure, it is converted into hydrophilicity, so that the surface of the resist film has a low static contact angle, thereby reducing surface defects, and a fine resist pattern having excellent sensitivity and resolution can be formed.

Fig. 1 is a view showing 1H-NMR (CDCl ₃ , 400 MHz) of Compound 4 prepared in Synthesis Example 1 of a monomer.

Hereinafter, embodiments of the invention will be described in detail. However, the present invention is not limited thereto, and the scope of the present invention should be determined by the scope of the patent application.

Unless otherwise stated in the specification, "halo" or "halogen" is any one selected from the group consisting of fluorine, chlorine, bromine and iodine.

Unless otherwise stated in the specification, the prefix "hetero" means the substitution of a carbon atom with one to three heteroatoms selected from the group consisting of N, O, S and P. For example, a heteroalkyl group is one to three carbon atoms in a carbon atom in which an alkyl group is substituted by a hetero atom.

Unless otherwise stated in the specification, "alkyl" refers to a straight or branched alkyl group having 1 to 30 carbon atoms, 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 a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group, but are not limited thereto.

Unless otherwise stated in the specification, "alkenyl" means a hydrocarbon group having one or more unsaturated regions, ie, a carbon-carbon sp ² double bond, a normal, secondary, tertiary or cyclic carbon atom. For example, an alkenyl group can have 2 to 20 carbon atoms (ie, C ₂ -C ₂₀ alkenyl), 2 to 12 carbon atoms (ie, C ₂ -C ₁₂ alkenyl), or 2 to 6 carbon atoms (ie, , C ₂ -C ₆ alkenyl). Examples of suitable alkenyl groups include a secondary ethyl or vinyl group (-CH=CH ₂ ), an allyl group (-CH ₂ CH=CH ₂ ), a cyclopentenyl group (-C ₅ H ₇ ), and a 5-hexyl group. Alkenyl (-CH ₂ CH ₂ CH ₂ CH ₂ CH=CH ₂ ), but is not limited thereto.

Unless otherwise stated in the specification, "alkanediyl" is a divalent radical derivatized by subtracting two hydrogen atoms from an alkane (alkane), which may be represented by the formula -C _n H _2n - (alkenediyl)" is a divalent radical from which two hydrogen atoms are subtracted from an alkene, and can be represented by the formula -C _n H _n -.

Unless otherwise stated in the specification, "cycloalkyl" means a cycloalkyl group having 3 to 30 carbon atoms, including monocyclic, bicyclic, tricyclic and tetracyclic. Further, a polycyclic cycloalkyl group containing an adamantyl group, a norbornyl group, and a norbornyl group is included.

Unless otherwise stated in the specification, "aryl" means a compound containing a benzene ring and a derivative thereof, and for example, may be two or more of toluene or xylene having an alkyl side chain attached to a benzene ring. a naphthalene or anthracene in which a benzene ring is bonded by a single bond, or a benzene ring having two or more benzene rings, a cycloalkyl group or a heterocycloalkyl group as a medium, or a benzene ring condensed with two or more benzene rings. Wait. Unless otherwise stated in the specification, the aryl group is an aryl group having 6 to 30 carbon atoms.

Unless otherwise stated in the specification, "heterocyclyl" refers to the number of ring atoms in which one or more (eg 1, 2, 3 or 4) carbon atoms are replaced by a hetero atom (eg N, O, P or S). 4 to 20 ring groups. The term "heterocyclyl" contains a saturated ring, a partially unsaturated ring, and an aromatic ring (ie, a heteroaryl ring), and further includes, for example, an N-oxide or a tetra which is formed by oxidizing or quaternizing a hetero atom in the ring. A cyclic aryl group of an ammonium salt. The substituted heterocyclic group includes, for example, a heterocyclic ring including a carbonyl group substituted with any of the substituents disclosed in the present application.

Unless otherwise stated in the specification, "hydrocarbyl group" is a monovalent hydrocarbon group having 3 to 20 carbon atoms consisting only of carbon and hydrogen, and contains an aliphatic chain type or branched type hydrocarbon group and a cyclic hydrocarbon group. As a specific example, including hexyl, heptyl, octyl, decyl, decyl, and ten Monoalkyl, dodecyl, cyclohexyl, phenyl, tolyl, xylyl, 2,4,6-trimethylphenyl, benzyl, benzhydryl, trityl, styryl, non Phenyl and naphthyl and the like.

Unless otherwise stated in the specification, all compounds or substituents may be substituted or unsubstituted. Here, substituted means that hydrogen is selected from a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an amine group, a thio group, a methylthio group, an alkoxy group, a nitrile group, an aldehyde group, an epoxy group, an ether. , ester, ester, carbonyl, acetal, keto, alkyl, perfluoroalkyl, cycloalkyl, heterocycloalkyl, allyl, benzyl, aryl, heteroaryl and their Any of the groups consisting of derivatives and combinations thereof are substituted.

Further, unless otherwise stated in the specification, "a combination thereof" means that two or more substituents are bonded by a single bond or a linking group, or two or more substituents are condensed.

When manufacturing a semiconductor element or the like, a photolithography method is used for microfabrication, in which an Ar excimer laser having a wavelength of 193 nm is mainly used as a light source by a immersion lithography method, and a liquid immersion water such as water is injected between the lens and the wafer substrate. After the resist film is immersed, exposure is performed to form a fine pattern. However, the immersion lithography method has a problem that the water-soluble component in the resist film is easily immersed in water by the water during exposure, and the alkaline component contained in the acid or resist contained in the exposure process is The liquid immersed in water so that the shape of the pattern changes or collapses. Further, a small amount of water droplets remaining after the scanning penetrate into the resist film to cause defects. Further, in the case where a resist of a top coat is not used, a faster scanning speed is required at the time of exposure, so that the resist should have extremely hydrophobic characteristics before development, on the other hand, cut back Pattern defects occur and should have a hydrophilicity of 50° or less after development.

Therefore, in the preparation of the resist, the resist is used to exhibit hydrophilicity by developing a dehydration reaction to form a hydroxyl group in order to develop high hydrophobicity before development, and an additive is used. However, in the conventional resist additive, since the rate of formation of a hydroxyl group is low, it is difficult to make the static contact angle of the resist surface have a hydrophilicity of 50 or less after development.

In contrast, in the present invention, in order to maximize the difference between the static contact angle before development and the static contact angle after development, there will be 2 ⁿ (n is an integer of 1 or more) hydrophobic groups at the end. The dendritic compound is used as a monomer to prepare an additive for resisting. Therefore, when the pattern is formed by the immersion lithography method, high hydrophobicity is exhibited before development, and conversely, it is converted into hydrophilicity after development, and pattern defects are reduced, in particular, After the de-radical reaction, two or more hydroxyl groups are formed, so that the hydrophilicity after development is improved, and defects are generated at the time of development, and as a result, a good resist pattern can be formed after development.

Therefore, according to an embodiment of the present invention, a novel acrylic monomer of the following Chemical Formula 1 which is useful as a monomer for forming a resist for etching is provided.

In the chemical formula 1, R ¹ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ² is an alkenyl group selected from an alkyl group having 1 to 20 carbon atoms and 2 to 20 carbon atoms. a heteroalkyl group having 1 to 20 carbon atoms, a heteroalkylene group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a cycloalkenylene group having 3 to 30 carbon atoms, and a carbon atom In the group consisting of a heterocycloalkyl group of 2 to 30 and a heterocycloalkenyl group having 3 to 30 carbon atoms, X contains a dendritic unit represented by the following Chemical Formula 2 and represented by the following Chemical Formula 3 End unit.

In the chemical formulas 2 and 3, R ³ is an alkyl group selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and a carbon number. In the group consisting of a cycloalkyl group of 3 to 30, a cycloalkenyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a heterocyclic group having 2 to 30 carbon atoms, Y is selected from the group consisting of A hydrophobic group in the group consisting of a halogen alkyl group having 1 to 20 carbon atoms, an organic fluorenyl group and a hydrocarbon group having 3 to 20 carbon atoms, and a is an integer of 0 or 1.

In the above Chemical Formula 1, R ¹ is preferably a hydrogen atom or a methyl group, and preferably R ² is an alkylene group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and carbon. a heteroalkyl group having 1 to 10 atoms, a heteroalkylene group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, a cycloalkenyl group having 3 to 18 carbon atoms, and a carbon number More preferably selected from the group consisting of a heterocycloalkyl group of 2 to 18 and a heterocycloalkyl group having 3 to 18 carbon atoms, more preferably selected from the group consisting of methylene, ethyl, propyl, and trimethylene. Tetramethylene, pentamethylene, hexamethylene, heptamethylene, 2,2-dimethylpentamethylene, -OCH ₂ -, -OCH(Cl)-, -CO-, -COCH ₂ -, -COCH ₂ CH ₂ -, -CH ₂ -O-CH ₂ -, -CH ₂ -O-CH ₂ CH ₂ -, -CH ₂ CH ₂ -O-CH ₂ -, -CH ₂ -O- CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ -O-CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -O-CH ₂ -, -C(CH ₃ ) ₂ CH ₂ -, -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 -S-CH 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 - are grouped.

Further, in the chemical formula 2, R ³ is preferably a ring-shaped ring selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, and 3 to 14 carbon atoms. An alkyl group, a bicyclic cycloalkyl group having 8 to 18 carbon atoms, a tricyclic cycloalkyl group having 10 to 30 carbon atoms, a tetracyclic cycloalkyl group having 10 to 30 carbon atoms, and 3 to 3 carbon atoms In the group consisting of a cycloalkenyl group of 18, an aryl group having 6 to 18 carbon atoms, and a heterocyclic group having 2 to 30 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, further It is preferably selected from the group consisting of a hydrogen atom, a methyl group and an ethyl group.

In the chemical formula 3, Y may be a fluoroalkyl group selected from the group consisting of 1 to 8 carbon atoms, a germyl group, an alkyl formyl group having 1 to 10 carbon atoms, a chain type having 3 to 10 carbon atoms, and Branched alkyl group, monocyclic cycloalkyl group having 3 to 14 carbon atoms, bicyclic cycloalkyl group having 8 to 18 carbon atoms, tricyclic cycloalkyl group having 10 to 30 carbon atoms, and carbon atom number 10 More preferably selected from the group consisting of a tetracyclic cycloalkyl group of 30, selected from the group consisting of t-butyl, trifluoromethyl, trimethylmethanealkyl, bis(trifluoromethyl)isopropyl, and five In the group consisting of fluoroethyl and heptafluoropropyl.

The acrylic monomer of Chemical Formula 1 contains a plurality of hydrophobic moieties capable of exhibiting water repellency with double bond bonding by radical polymerization, and the hydrophobic moiety is, as in the following Reaction Scheme 1, in the developing step, permeation and development The fluorine portion of the liquid as a hydrophobic portion is detached and converted into a hydroxyl group, thereby exhibiting hydrophilicity. The following Reaction Formula 1 is only an example of the present invention, and the present invention is not limited thereto.

Reaction formula 1

The acrylic monomer of Chemical Formula 1 has a dendritic structure and contains 2 ⁿ (n is an integer of 1 or more) or more hydrophobic groups capable of being converted into a hydrophilic group (for example, a hydroxyl group) through a developing solution, thereby The hydrophilic property after the development step is further improved.

Specifically, it is preferred that the acrylic monomer of Chemical Formula 1 contains 1 to 3 dendritic units represented by the above Chemical Formula 2. When the dendritic unit in the range is contained, the effect of maximizing the difference in static contact angle can be exhibited. If the number of dendritic units is too large, there is a risk that the acrylic monomer of Chemical Formula 1 cannot participate in polymerization. Not good.

More preferably, the acrylic monomer of Chemical Formula 1 may be one or three compounds represented by the following Chemical Formula 1a or 1b containing a dendritic unit represented by Chemical Formula 2.

The compound of Chemical Formula 1 having such a structural feature can be produced by reacting a compound of the following Chemical Formula 4 with a compound of the following Chemical Formula 5a or 5b.

Chemical formula 5bR(C=O)-X

In the chemical formulas 4 and 5, R ¹ and R ² are the same as defined above, X is a halogen group, preferably a chloro group, a bromo group or an iodine group, and Y' and Y" are selected from a carbon number of 1 In the group consisting of a halogen alkyl group of 20, an organic fluorenyl group, and a hydrocarbon group having 3 to 20 carbon atoms, Z contains a dendritic unit of the following chemical formula 6, and contains a hydroxyl group at the terminal.

In the chemical formula 6, R ³ is the same as defined above, and b is an integer of 0 or 1.

In this case, the compound of Chemical Formula 4 can be produced by a production method comprising the steps of reacting a dioxane compound having a carboxyl group with a compound of the following Chemical Formula 7 having a hydroxyl group at the terminal, and then using an ion. The resin is exchanged for processing.

In the chemical formula 7, R ¹ and R ² are the same as defined above.

Specifically, as the compound of Chemical Formula 7, 2-hydroxyethylmethacrylate or hydroxyadamanthanylmethacrylate or the like can be used.

Further, as the dioxane compound containing the carboxyl group, it can be used. 2,2,5-trimethyl-1,3-dioxane-5-carboxylic acid (2,2,5-trimethyl-1,3-dioxane-5-carboxylic acid) or 2,2-dimethyl -1,3-dioxane-5-carboxylic acid or the like.

Further, the dioxane compound containing the carboxyl group may be commercially available or may be directly prepared for use. As an example, when 2,2,5-trimethyl-1,3-dioxan-5-carboxylic acid is used as the dioxane compound containing the carboxyl group, 2,2-bis(hydroxymethyl group) can be used. Propionic acid (2,2-bis(hydroxymethyl)propionic acid) and 2,2-dimethoxypropane in the presence of p-toluenesulfonic acid monohydrate In the case of a reaction catalyst, after performing a reaction in an organic solvent such as acetone, it is neutralized with a salt solution such as a NH ₃ /EtOH solution to prepare 2,2,5-trimethyl-1,3-dioxane- 5-carboxylic acid used.

The following Reaction Formula 2 is a compound (4a) which is represented by a dioxane compound containing a carboxyl group by using 2,2,5-trimethyl-1,3-dioxan-5-carboxylic acid (8). Or step 4b). The following Reaction Formula 2 is only an example for explaining the present invention, and the present invention is not limited thereto.

Reaction formula 2

The reaction formula 2 will be described. First, a carboxyl group-containing dioxane compound (8) is subjected to an esterification reaction with the compound (7a) of the above chemical formula 7 having a hydroxyl group at the terminal.

The reaction of the dioxane compound containing the carboxyl group with the compound of Chemical Formula 7 may be carried out in the presence of, for example, a dimethylaminopyridine (DMAP, dimethylaminopyridine) base such as N,N'-dicyclohexylcarbodiimide (DCC, In the case of a dehydrating agent of N,N'-dicyclohexylcarbodimide, it is carried out in a solvent such as dichloromethane.

In addition, it can also be prepared by reacting a carboxylic acid with carbonyldiimidazole. The azole is reacted with the compound 7a of the above Chemical Formula 7 having a hydroxyl group at the terminal to prepare the compound of the Chemical Formula 9a.

After the compound 9a precipitated by the reaction of the dioxane compound containing the carboxyl group with the compound of the chemical formula 7 is isolated, the compound 4a of the chemical formula 4 is prepared by treatment with an ion exchange resin in an alcohol solvent such as methanol.

As the ion exchange resin, a cation exchange resin or a commercially available one (DOWEX 50W, S-Sepharose, SP-Sepharose, S-Sephadex, SP-Sephadex, SP-Toyopearl 550C, SP-Toyopearl) can be used. 550M, SP-Toyopearl 650C, SP-Toyopearl 650M, trinitrotoluene SCR-B, trinitrotoluene SCR-04, etc.).

In this case, the compound 4b of Chemical Formula 4 having an increased degree of branching may be further prepared by reacting the compound 4a obtained after the ion exchange resin treatment with a dioxane compound containing a carboxyl group, And subsequent ion exchange resin treatment.

Thus, in order to prepare the compound of Chemical Formula 1 having a desired degree of branching, a step of reacting the compound 4a obtained by the ion exchange resin treatment with a dioxane compound containing a carboxyl group, and repeating the subsequent steps may be carried out. Ion exchange resin treatment.

The compound 1a or 4b of the chemical formula 1 is prepared by reacting the compound 4a or 4b prepared by the above method with the compound 5a of the chemical formula 5a or 5b, as shown in the following Reaction Scheme 3.

Reaction formula 3

In this case, as the compound of the chemical formula 5a, trifluoroacetic acid or pentafluoropropionic anhydride or the like can be used, and as the compound of the chemical formula 5b, hydrazine chloride, bromofluorenyl group, iodonium group or the like can be used.

Further, it is preferred that the reaction be carried out in a solvent such as dichloromethane in the presence of a base such as dimethylaminopyridine or pyridine.

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

The resist additive contains a dendritic side chain derived from the acrylic monomer of Chemical Formula 1 and having 2 ⁿ or more hydrophobic groups at the terminal, so that high hydrophobicity is exhibited before development, and after development, The hydrophobic group is converted into a hydroxyl group so that high hydrophilicity can be exhibited. As a result, in the resist which does not use the quick-drying nail polish, the exposure process can be performed at a rapid scanning speed, and after the development, the hydrophilic property of 50° or less is exhibited, and the pattern can be reduced.

The resist additive may further contain a repeating unit represented by the following Chemical Formula 10.

In the chemical formula 10, R ⁴ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁵ is selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a carbon number of 1 to 10. a heteroalkyl group, 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 a heteroaryl group having 5 to 30 carbon atoms; Any of the groups.

It is preferable that the resist additive is a copolymer represented by the following Chemical Formula 11.

Chemical formula 11

In the above formula 11, R ¹ , R ² and X are the same as described above, and R ⁴¹ and R ⁴² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁵¹ and R ⁵² are each independently Selected as a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, or a carbon atom Any of a group consisting of an aryl group of 6 to 30 and a heteroaryl group having 5 to 30 carbon atoms, and l, m and n are the numbers of the molar ratios respectively indicating the repeating unit in the main chain, l+m+n=1,0<1/(l+m+n) 0.99,0 m/(l+m+n) 0.99,0<n/(l+m+n) 0.99.

Preferably, in the chemical formula 11, R ⁵¹ is selected from , with An acid-sensitive group in the group formed, in which case, Ra, Rb, and Rc are each independently selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, (having 1 carbon atom) An alkyl group to 10, a hydroxyalkyl group, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an ethyl group, an ethane group, a carboxyl group a group consisting of a (carboxyl group having 1 to 10 carbon atoms) carboxyl group, a (cycloalkyl group having 3 to 18 carbon atoms) carboxyl group, and a heterocycloalkyl group having 3 to 30 carbon atoms, or may be each other The ortho group is bonded to form a saturated or unsaturated hydrocarbon ring or heterocyclic ring having 3 to 30 carbon atoms, Rd is an alkyl group having 1 to 10 carbon atoms, p is an integer of 0 to 3, and q is an integer of 0 to 10. R ⁵² is a lactone group, preferably or In this case, Re and Rf may each independently be an alkyl group having 1 to 10 carbon atoms or may be bonded to each other to form a saturated hydrocarbon ring, and r and s are each independently an integer of 0 to 5.

More preferably, in the Chemical Formula 11, R ⁵¹ is selected from the group consisting of t- butyl, trimethylsilyl silicon alkyl, hydroxy-2-ethyl, 1-methoxypropyl, 1-methoxy-1 -methylethyl, 1-ethoxypropyl, 1-ethoxy-1-methylethyl, 1-methoxy-1-ethyl, 1-ethoxy-1-ethyl, uncle a group consisting of butoxy-2-ethyl, 1-isobutoxy-1-ethyl and the following chemical formulas 12a to 12j,

In the chemical formulas 12a to 12j, R', R" and R"' are each independently selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 1 to 10 carbon atoms. In the group consisting of an alkylcarboxyalkyl group and a cycloalkylcarbinyl group having 3 to 18 carbon atoms, a and e are integers of 0 to 15, b is an integer of 0 to 11, and c and d are independent, respectively. An integer from 0 to 9, f is an integer from 0 to 7, and g and i are each independently an integer from 0 to 6, 0 c+d 17,0 c+f Further preferably, it may be selected from the group consisting of the following Chemical Formulas 13a to 13h.

Further, more preferably, in the chemical formula 11, R ⁵² may be the following chemical formula 14a or 14b.

Usually, in order to increase the scanning speed at the time of exposure of the resist film, it is necessary to form a static contact angle (SCA, static contact angle) of 90 or more, but the high SCA becomes a blob defect at the time of development after exposure. The main reason, so the surface of the resist film has a lower SCA when developed after exposure. It can reduce the occurrence of spot defects. For this reason, the additive for resist according to the present invention introduces a hydrophobic group having a structure in which an α-carbon group is substituted with an electron withdrawing group, such as a trihaloethyl group, in the side chain portion, so that the resist film is improved. It is hydrophobic so as to prevent dissolution of the resist component during immersion exposure.

Specifically, in the copolymer of Chemical Formula 10, the monomer-derived repeating unit 1 of Chemical Formula 1 contains a hydrophobic group, so that the lithographic step can be suppressed by increasing the hydrophobicity of the surface of the resist film upon exposure. When it is leached by water, the hydrophobic group at the exposed portion during development after exposure is depolarized by an alkaline developing solution such as trimethylammonium hydroxide (TMAH, trimethylammonium hydroxide) to be converted into an alcohol group, thereby being converted into The hydrophilic property, as a result, has a lower SCA, thereby being able to reduce the occurrence of spot defects.

Further, the repeating unit m derived from the acrylic acid derivative contains an acid labile group, so that the exposed portion is converted from hydrophobic to hydrophilic due to the deprotection reaction of the acid upon exposure, and as a result, the exposed portion at the time of development It is easy to be rinsed by the developer.

Further, the repeating unit n derived from the acrylic acid derivative contains a lactone group, so that the adhesion force on the wafer can be enhanced.

In the copolymer of Chemical Formula 10, the repeating units 1, m and n represent the content of each repeating unit in the main chain, and indicate the substitution ratio at which the copolymer is dissolved by the developing solution. The copolymer according to the present invention contains 0<1/(l+m+n) under the condition that the repeating units l, m and n satisfy l+m+n=1. 0.99, 0 < m / (l + m + n) 0.99 and 0<n/(l+m+n) 0.99. The repeating unit is included in the ratio so as to exhibit a hydrophobic property lower than that of water upon immersion exposure, in particular, a monomer-derived repeating unit 1 containing 70 mol% or less of the formula 1, thereby The CA value at the time of development can be reduced, and the effect of reducing defects can be obtained.

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

Specific examples of the anti-corrosion additive according to the present invention include compounds having the following chemical formulas 15a to 15p, and in the structural formula, the order of each repeating unit can be changed.

In the chemical formulas 15a to 15p, l, m and n are l+m+n=1, 0<1/(l+m+n) 0.99,0<m/(l+m+n) 0.99,0<n/(l+m+n) 0.99.

The additive for resist according to the present invention may have a weight average molecular weight (hereinafter referred to as "Mw") in terms of polystyrene by gel permeation chromatography (GPC, gel permeation chromatography) of 1,000 to 20,000 g/mol. When the weight average molecular weight of the copolymer is too small, it may cause dissolution in pure water during mixing or immersion exposure. Large, it may be difficult to form a suitable film or reduce alkali solubility. It is preferred that the weight average molecular weight is from 2,000 to 10,000 g/mol, does not elute in pure water, and exhibits excellent solubility to the developer.

Further, it is preferred that the ratio of the weight average molecular weight to the number average molecular weight of the resist for the resist Mw/Mn has a molecular weight distribution of from 1 to 5, more preferably from 1 to 3. Further, if the molecular weight distribution of the polymer exceeds 3, the line edge roughness may be poor. Therefore, when the resist additive belonging to the weight average molecular weight and the molecular weight distribution range is used as a photoresist composition, the corresponding physical properties can be exhibited in terms of developability, coatability, and heat resistance.

The additive for resist according to the present invention having the structure as described above, an acrylic derivative having the structure of the following Chemical Formula 16 and an acrylic monomer having a structure of the following Chemical Formula 17 can be selected by a usual polymerization method such as a bulk. Polymerization, solution polymerization, suspension polymerization, bulk suspension polymerization, emulsion polymerization and other polymerization methods are prepared by polymerization.

Chemical formula 17

In the chemical formulas 16 and 17, R ¹ , R ² , R ⁴ , R ⁵ and X are the same as defined above.

Preferably, the additive for resist according to the present invention is polymerized by radical polymerization. In this case, as the radical polymerization initiator, for example, azobisisobutyronitrile (AIBN) or benzamidine peroxide (BPO) is used. Conventional radical polymerization initiators such as laurel, azobisisohexylamine nitrile, azobisisovaleronitrile and t-butyl hydroperoxide are not particularly limited.

Further, as the polymerization solvent, one or more selected from the group consisting of benzene, toluene, xylene, halogenated benzene, diethyl ether, tetrahydrofuran, esters, ethers, lactones, ketones, guanamines, and alcohols are used.

The polymerization temperature at the time of the polymerization reaction is appropriately selected depending on the type of the catalyst. Further, the molecular weight distribution of the produced polymer can be appropriately adjusted by changing the amount of the polymerization initiator used and the reaction time. Unreacted monomers and by-products remaining in the reaction mixture after completion of the polymerization are preferably removed by solvent precipitation.

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

Specifically, the resist composition contains a resist for resist and a base polymer for a resist, an acid generator, and a solvent.

The resist additive is the same as described above with respect to the resist group The total weight of the product may be from 0.01 to 5% by weight, preferably from 0.05 to 1% by weight. When the content of the resist additive is less than 0.05% by weight, the effect by using an additive is small, and if it exceeds 5% by weight, the CA value is exceeded, and watermark defects may occur, which is not preferable.

When the base polymer for a resist is used as a matrix resin in forming a resist film, it can be used without particular limitation. As a specific example, a (meth) acrylate polymer, (α-trifluoromethyl) acrylate-maleic anhydride copolymer, a cycloolefin-maleic anhydride copolymer, a polynorbornene, a permeation ring may be used. a polymer compound obtained by a ring-opening metathesis reaction of an olefin, a polymer compound obtained by adding hydrogen to a polymer obtained by a ring-opening metathesis reaction of a cyclic olefin, and a hydroxystyrene and a (meth) acrylate a polymer copolymerized with any of a derivative, styrene, vinyl naphthalene, vinyl anthracene, vinyl anthracene, hydroxyvinylnaphthalene, hydroxyvinyl anthracene, anthracene, hydroxyanthracene, decene, norbornadiene A group consisting of a compound, a novolac resin, and a mixture thereof.

The base polymer may be contained in an amount of from 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 is too low, so that it is difficult to form a film of a desired thickness, and pattern loss is severe due to a relatively large amount of photoacid generator. At 20% by weight, the film thickness is too thick to reduce the radiation penetration force, and it is difficult to obtain a longitudinal pattern.

The acid generator is a photoacid generator (hereinafter referred to as "PAG"), and iodonium salts, sulfonium salts, sulfonium salts, diazonium salts, Pyridinium salts or quinone imines, etc. One or more of the sulfonium salts represented by the following Chemical Formulas 18 and 19 are preferably used, and more preferably, a triphenylsulfur trifluoromethanesulfonate or a potassium perfluorobutanesulfonate is used.

In the chemical formulas 18 and 19, X ₁ , X ₂ , Y ₁ and Y ₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an allyl group, and a total of 1 to 10 carbon atoms. Any one of the group consisting of a fluoroalkyl group, a benzyl group, an aryl group having 6 to 30 carbon atoms, and a combination thereof, wherein X ₁ and X ₂ and Y ₁ and Y ₂ may be bonded to each other to form a carbon. a saturated or unsaturated hydrocarbon ring having 3 to 30 atoms, and X ₃ , X ₄ , X ₅ , Y ₃ , Y ₄ and Y ₅ are each independently selected from a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, and a halogen group. An alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a thiophenoxy group, a thioalkoxy group having 1 to 30 carbon atoms, and a carbon number Any one of the group consisting of 1 to 20 alkoxycarbonylmethoxy and combinations thereof, and the Z of the anion moiety 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} ) A functional group represented by the following Chemical Formula 20.

In the chemical formula 20, V ₁ and V ₂ are each independently a halogen atom, W ₁ is -(C=O)- or -(SO ₂ )-, and W ₂ is an alkylene group having 1 to 10 carbon atoms. W ₃ is selected from 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, and a carbon atom. Any one of the group consisting of an arylthio group having 6 to 30 and a heterocyclic group having 5 to 30 carbon atoms, and W ₄ is an alkane selected from a hydrogen atom, a halogen group, and having 1 to 10 carbon atoms. a group, an alkoxy group having 1 to 10 carbon atoms, a halogen alkyl 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 the like Any one of the groups consisting of combinations, o is an integer from 0 to 1, and p is an integer from 0 to 2.

The anion in the acid generator contains a cyclic alkyl group, thereby being able to The local retention of the acid in the resist film is short, and high permeability is exhibited. As a result, a high-resolution resist can be obtained.

It is preferred that the anion portion Z of the chemical formula 20 may be selected from the group consisting of functional groups represented by the following Chemical Formulas 21a to 21l and 22a to 22x.

Further, in the chemical formulas 18 and 19, preferred examples of the cationic moiety include the structures represented by the following chemical formulas 23a to 23p.

The acid generators as described above may be used singly or in combination of two or more. Further, the acid generator is used in an amount of 100 parts by weight relative to the solid content of the polymer. The content may be from 0.3 to 15 parts by weight, preferably from 0.5 to 10 parts by weight, more preferably from 2 to 10 parts by weight. When the content of the acid generator exceeds 15 parts by weight, the perpendicularity of the pattern is remarkably lowered, and when it is less than 0.3 parts by weight, the bendability of the pattern may be lowered.

In order to obtain a uniform smooth resist coating film, it is preferred to use the polymer and the acid generator in a solvent having a suitable volatilization speed and viscosity. Examples of the solvent which can be used in the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, methyl cellulose cellosolve, ethyl cellulose cellosolve, and propylene glycol monomethyl. Esters such as ethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl isopropyl ketone, cyclohexanone, ethyl methyl 2-hydroxypropionate, B A ketone such as ethyl 2-hydroxypropionate, 2-heptanone, ethyl lactate or γ-butyrolactone may be used alone or in combination of two or more.

The solvent can be appropriately adjusted in accordance with the physical properties of the solvent, that is, the volatility, the viscosity, etc., so that a uniform resist film can be formed.

Further, for the purpose of improving coatability and the like, the resist composition according to the present invention may further contain an additive.

The additive is not particularly limited as long as it is generally applicable to the resist composition, and specific examples thereof include an alkaline dissolution inhibitor, an acid diffusion inhibitor, a surfactant, and the like. A single type, or a mixture of two or more types.

The alkaline dissolution inhibitor can be used as long as it is an alkaline dissolution inhibitor which can be suitably used for a resist composition, and specific examples thereof include a phenol or a carboxylic acid derivative.

The acid diffusion inhibitor functions to suppress diffusion and development of an acid generated from the acid generator when diffused by the light irradiation to the resist film, thereby suppressing a chemical reaction in the unexposed portion. By using such an acid diffusion inhibitor, the storage stability of the radiation-sensitive linear resin composition can be improved, and the resolution as a resist can be further improved, and the time (PED) from the exposure to the development processing can be suppressed. The line width of the resist pattern changes.

As the acid diffusion inhibitor, a basic compound can be used, and specific examples thereof include ammonia, methylamine, isopropylamine, n-hexylamine, cyclopentylamine, methylenediamine, ethylenediamine, and dimethylamine. Diisopropylamine, diethylenediamine, N,N-dimethyldiamine, N,N-dimethylethylenediamine, trimethylamine, triethylamine, N,N,N',N'-tetra Methyldiamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyltetraethylamine,diethylamine,methylethyl Propylamine, benzylamine, phenethylamine, benzyldimethylamine, tetramethylammonium hydroxide, aniline, N,N-dimethylanilintriphenylamine, phenylenediamine, pyrrole, oxazole, isoxazole , thiazole, isothiazole, imidazole, pyrazole, pyrroline, pyrrolidine, imidazoline derivative, imidazolidine derivative, pyridine derivative, pyridazine derivative, pyrimidine derivative, pyrazine derivative, pyrazoline derivative , pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, amines such as morpholine, amino acids, hydrazine carboxylic acids, amino acid derivatives (eg niacin, alanine, arginine, Aspartic acid, etc.), 3-pyridinesulfonic acid, p-toluenesulfonic acid Nitrogen compounds such as pyridinium salt, 2-hydroxypyridine, amino-m-cresol, 2,4-quinolinediol, 2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine, Indoleamine, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, decylamine propionate, a decylamine derivative such as benzamide or phthalimide, A quinone imine derivative such as amber imine or maleimide.

The acid diffusion inhibitor may be included in an amount of from 0.01 to 20 parts by weight, preferably from 0.1 to 15 parts by weight, based on 100 parts by weight of the polymer solid content. If the content of the acid diffusion inhibitor is less than 0.01 parts by weight, the influence on the delay time after exposure may be large, which may affect the shape of the image, and if it exceeds 5 parts by weight, the resolution and sensitivity may be lowered.

The surfactant is used for improving coatability, developability, and the like, and specific examples thereof include polyoxyethylene lauryl ether, octadecyl polyoxyethylene ether, polyoxyethylene, and polyethylene glycol dilaurate. Etc., but not limited to this.

When a resist pattern is formed by using the resist composition of the present invention having the composition as described above, an improved line width roughness is exhibited, and both the C/H pattern and the L/S pattern are excellent. Resolution. In addition, since it has a good process window, an excellent pattern profile can be obtained regardless of the type of substrate, and an improved contrast is exhibited. Therefore, the resist composition is induced by X-rays such as KrF excimer laser, ArF excimer laser or F ₂ excimer laser such as far ultraviolet rays, synchrotron radiation, and charged particles such as EUV. It is useful for chemically amplified positive photoresist compositions.

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

Specifically, the method of forming the pattern includes the steps of: coating a resist composition on a substrate to form a resist film; and thermally exposing the resist film to perform exposure in a predetermined pattern; And developing the exposed resist pattern The steps of the case.

A wafer substrate can be used for the substrate, and a method of coating the substrate can be performed by a method such as spin coating, flow coating, or roll coating.

Specifically, a film thickness of 0.3 to 2.0 μm is coated on the substrate of the tantalum wafer, which is prebaked at 60 to 150 ° C for 1 to 10 minutes, preferably at 80 to 130 ° C for 1 to 5 minutes.

Next, in order to form a fine pattern, a part of the resist film is irradiated with radiation. In this case, the radiation that can be used is not particularly limited, but an ultraviolet ray I-ray, a far ultraviolet ray KrF excimer laser, an ArF excimer laser, an F2 excimer laser, an X-ray, a charged particle beam can be used. The electron beam or the like can be appropriately selected and used depending on the type of the acid generator.

Specifically, the radiation is irradiated so that the exposure amount is about 1 to 200 mJ/cm ² , preferably about 10 to 100 mJ/cm ² , and then post-exposure baking (PEB) at 60 to 150 ° C for 1 to 5 minutes, preferably Bake at 80 to 130 ° C for 1 to 3 minutes after exposure.

The resist pattern exposed after the exposure step is subjected to a dipping method, a puddle method, a spray method, or the like, and is immersed in a developing solution for 0.1 to 3 minutes for development, preferably 0.5 to 2. Minutes to form the desired pattern on the substrate. In this case, as the developer which can be used, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium methane citrate, ammonia, ethylamine, n-propylamine, triethylamine, tetramethyl hydroxide can be used. An aqueous solution of ammonium or tetraethylammonium hydroxide or the like is preferably tetramethylammonium hydroxide.

Further, the developer may optionally further contain an additive such as a surfactant or a water-soluble alcohol.

By the method of forming a pattern by using the resist composition according to the present invention as described above, it is possible to form a fine resist pattern having excellent sensitivity and resolution.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail so as to be easily implemented by those skilled in the art to which the present invention pertains. However, the invention can be implemented in a variety of different ways, but is not limited to the embodiments described herein.

Preparation: Synthesis of monomers and polymers

Monomer synthesis example 1

30.0 g of 2,2-bis(hydroxymethyl)propionic acid and 41.4 mL of 2,2-dimethoxypropane and 2.13 g of p-toluenesulfonic acid monohydrate (p -toluenesulfonic acid monohydrato) into 300mL of acetone and stirred at room temperature for 2 hours to prepare a mixture. After neutralizing the mixture solution obtained by adding NH ₃ /EtOH solution, the solvent was removed by a rotary concentrator. The thus obtained reactant was washed with methylene chloride and distilled water to obtain Compound 1.

16 g of 2-hydroxyethylmethacrylate and 23.5 g of the prepared compound 1 and 4.2 g of dimethylaminopyridine (DMAP, dimethylaminopyridine) and 27.9 g of N,N'-di The mixture prepared by mixing cyclohexylcarbodiimide (DCC, N, N'-dicyclohexylcarbodimide) in 300 mL of dichloromethane was stirred at normal temperature for 24 hours. After the resulting reactant was filtered to remove the precipitate, the compound 2 was obtained by column chromatography.

15 g of the prepared Compound 2 and 8 g of an ion exchange resin (50W-X2, manufactured by Dowex Co., Ltd.) were placed in methanol, and stirred at a temperature of 40 ° C for 12 hours. After the completion of the reaction, the ion exchange resin was removed by a Celite filter, and then the solvent was removed by a rotary concentrator to obtain Compound 3.

15 g of the prepared Compound 3 and 85 g of anhydrous trifluoroacetic acid and 5 g of dimethylaminopyridine and 40 mL of pyridine were placed in 200 mL of dichloromethane, and stirred at normal temperature for 12 hours. After completion of the reaction, the unreacted material was removed by using distilled water, and the compound 4 was obtained by column chromatography.

The compound 4 was subjected to nuclear magnetic resonance spectrum analysis, and the results are shown in Fig. 1.

Polymer Synthesis Example 1

10 g of 2-methyl-acrylic acid (3-[3-(2,2,2-trifluoro-ethoxime) 2-(2-(2,2,2-trifluoro-ethoxymethyl)-propenyloxy])(2-methyl-acrylic acid 3-[3-(2,2,2-trifluoro-) Acetoxy)-2-(2,2,2-trifluoro-acetoxymethyl)-propionyloxy]) compound, 1 g of 2-methyl-acrylic acid 1-methyl-cyclohexyl ester And 15 g of 2-methyl-acrylic acid 2-oxo-tetrahydro-furan-3-yl ester with 255 g of 1,4- A solution obtained by dissolving dioxane (1,4-dioxane) was placed in a jacket reactor together with 1 g of DMA azobisbutyronitrile (DMAB, dimethyl azobis butyronitrile) as an initiator. Stir. After the circulator temperature was set to 75 ° C, the temperature of the reactor was gradually increased, followed by stirring at 75 ° C for 8 hours. After the completion of the reaction, the resulting reaction solution was added dropwise to a mixture of 2.4 L of n-hexane and 1 L of methanol, 2.5 L of n-hexane and 0.125 L of methanol, and the precipitate was precipitated as a result. The product was dried under vacuum to obtain a polymer (I) represented by the following chemical formula. The polystyrene-equivalent weight average molecular weight Mw of the polymer was 16,000 g/mol, and the molar ratio of each repeating unit was 1:m:n=30:40:30.

Polymer Synthesis Example 2

The polymer, except 1-(2-isopropyl-adamantan-2-yl)-3-methyl-but-3-en-2-one (1-(2-isopropyl-adamantan-2-) Yl)-3-methyl-but-3-en-2-one) Substituting 2-methyl-acrylic acid 1-methyl-cyclohexyl ester in Synthesis Example 1 And, 2-methyl-acrylic acid 5-oxo-4-oxa-tricyclo[2-methyl-acrylic acid 5-(2-oxo-4-oxa-tricyclo[ 4.2.1.03,7]non-2-yl ester) 2-methyl-acrylic acid 2-oxo-tetrahydro-furan-3- In the same manner as in Synthesis Example 1 of the above polymer, a polymer (II) represented by the following chemical formula was obtained. The polystyrene-equivalent weight average molecular weight Mw of the polymer was 11,000 g/mol, and the molar ratio of each repeating unit was 1:m:n=35:35:30.

Polymer Synthesis Example 3

10 g of 2-[2-methyl-3-(2,2,2-trifluoro-ethenyloxy)-2-(2,2,2-trifluoro-ethenyloxy) 2-methacrylate 2-methyl-acrylic acid 2-[2-methyl-3-(2,2,2-trifluoro-acetoxy)-2-(2,2,2- Trifluoro-acetoxym Ethyl)-propionyloxy]-ethyl ester) compound, 2 g of 2-methyl-acrylic acid 1-isopropyl-cyclohexyl ester and 17 g of 2-methacrylic acid 2 -2-methyl-acrylic acid 2-oxo-tetrahydro-furan-3-yl ester with 270 g of 1,4-dioxane The solution prepared by dissolving was placed in a jacket reactor together with 1.2 g of DMA azobisbutyronitrile (DMAB, dimethyl azobis butyronitrile) and stirred. The circulator temperature was set to 75 ° C, and the temperature of the reactor was gradually increased, followed by stirring at 75 ° C for 7 hours. After the completion of the reaction, the resulting reaction solution was dropped into 2.5 L of n-hexane and 1 L of methanol to precipitate, and then the precipitate was filtered and vacuum dried to obtain a polymerization represented by the following chemical formula. (III). The polymer had a polystyrene-equivalent weight average molecular weight of 9000 g/mol, and the molar ratio of each repeating unit was 1:m:n=25:45:30.

Polymer Synthesis Example 4

In addition to 1-(2-isopropyl-adamantan-2-yl)-3-methyl-but-3-en-2-one (1-(2-isopropyl-adamantan-2-yl)-3- Methyl-but-3-en-2-one) substitution 2-methyl-acrylic acid 1-isopropyl-cyclohexyl ester of Example 3, and 5-oxo-4-oxo 2-methacrylate Trimethyl [4.2.1.03,7]non-2-yl ester (2-methyl-acrylic acid 5-oxo-4-oxa-tricyclo[4.2.1.03,7]non-2-yl ester) The same procedure as in Synthesis Example 1 of the above polymer was carried out except for 2-methyl-acrylic acid 2-oxo-tetrahydro-furan-3-yl ester. In the method, a polymer (IV) represented by the following chemical formula is obtained. The polymer had a polystyrene-equivalent weight average molecular weight of 11,000 g/mol, and the molar ratio of each repeating unit was 1:m:n=25:45:30.

Test Example 1: Evaluation of hydrophobicity of additives

1.0 g of the polymer synthesized in Synthesis Example 1 of the polymer was separately dissolved in 25 g of 4-methyl pentanol, and then filtered through a 0.2 μm-sized polypropylene filter. A resist is prepared. After the prepared resist was spin-coated on a tantalum substrate, it was baked at 100 ° C for 60 seconds to form a resist film having a film thickness of 50 nm.

With respect to the formed resist film, the static contact angle of the surface before and after development was measured using a surface static contact angle measuring instrument. Specifically, the level remains formed The ruthenium substrate of the resist film was dropped with 50 μl of pure water to form a water drop, and then the ruthenium substrate was gradually tilted, and the ruthenium substrate roll angle at which the water drop started to roll was measured, and the ruthenium on which the resist film was formed was formed. The substrate was subjected to development by using a 2.38 wt% TMAH developing solution for 60 seconds, and the static contact angle after development was measured in the same manner as above.

Further, for comparison, the surface static contact angle before and after development was measured by the same method as described above using the compound of the following Chemical Formula 24 which was conventionally used as a resist additive.

In the chemical formula 24, the molar ratio l:m:n of each repeating unit is 50:30:20.

As a result, the static contact angle before development of the resist film containing the polymer (I) synthesized in Synthesis Example 1 of the polymer was 97°, and the surface static contact angle after development was 42°, on the other hand, The surface static contact angle of the resist film of the resist additive of Chemical Formula 23 before development was 92°, and the static contact angle after development was 56°.

From this result, it is understood that when the polymer (I) prepared in Synthesis Example 1 of the polymer is used as a resist additive, the difference between the static contact angle before development of the resist film and the static contact angle after development can be made larger. As a result, there is no fear of elution in water at the time of exposure, and the static contact angle at the time of development after exposure is 50 or less, and the hydrophilicity is further increased, so that the occurrence of defects can be reduced.

Test Example 2: Formation of a resist film and measurement of characteristics of the prepared resist film

The base polymer for resist represented by the following Chemical Formula 25 (Mw: 8,500 g/mol, Mw/Mn: 1.75, and the molar ratio of each repeating unit is x:y:z:w=1:1:1: 1) 5 g, 1.0 g of the polymer (I) synthesized in Synthesis Example 1 of the polymer, 0.31 g of a photoacid generator represented by the following Chemical Formula 26, and triisopropanol amine as an inhibitor (triisopropanol amine) 0.07 g was dissolved in 80 g of propylene glycol monoethyl ether acetate (PGMEA, propylene glycol monoacetate acetate), and then filtered using a 0.2 μm-sized polypropylene filter to prepare a resist.

An antireflection film (BARC) having a film thickness of 90 nm was formed on the ruthenium substrate, and the resist prepared above was coated on the substrate on which the antireflection film was formed, and then baked at 110 ° C for 60 seconds to form a film. A resist film having a thickness of 120 nm.

Next, in order to simulate immersion exposure, the exposed film was washed with pure water for 5 minutes. That is, using an ArF scanner 306C manufactured by Nikon (NA = 0.78, 6% halftone The mask was subjected to exposure and then washed with pure water for 5 minutes, and subjected to post-exposure baking (PEB) at 110 ° C for 60 seconds, followed by immersion for 60 seconds with 2.38 wt% of TMAH developer for development.

The ruthenium substrate on which the resist film prepared above was formed was cut to evaluate the sensitivity. At this time, the sensitivity was taken as a sensitivity (mJ/cm ² ) with a 1:1 resolution exposure amount of 65 nm L/S.

For comparison, the sensitivity was measured after the resist film was formed in the same manner as described above except that the additive was not used.

As a result of the measurement, the resist film using the resist additive according to the present invention has almost the same sensitivity as the resist film formed without adding an additive, and exhibits a sensitivity of 10 to 20 mJ/cm ² .

Further, in the case of the resist film to be compared, the acid generated during the pure water washing step was dissolved in water, so that a shape change such as a T-top shape pattern was observed, but the additive containing the present invention was contained. No shape change was observed in the resist film.

The preferred embodiments of the present invention have been described in detail above, but the scope of the present invention is not limited thereto, and various modifications and improvements will be made by those skilled in the art using the basic concepts of the invention described in the claims. Forms are all within the scope of protection of the present invention.

Claims (17)

An acrylic monomer having the structure of the following Chemical Formula 1, In the chemical formula 1, R ¹ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ² is an alkylene group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and carbon. a heteroalkyl group having 1 to 20 atoms, a heteroalkylene 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, and a carbon number In the group consisting of a heterocycloalkyl group of 2 to 30 and a heterocycloalkenyl group having 3 to 30 carbon atoms, X contains a dendritic unit represented by the following Chemical Formula 2 and represented by the following Chemical Formula 3 End base unit, In the chemical formula 2 and the chemical formula 3, R ³ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a group consisting of 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, and a heterocyclic group having 2 to 30 carbon atoms, Y A hydrophobic group selected from the group consisting of a halogen alkyl group having 1 to 20 carbon atoms and an organic fluorenyl group, a is an integer of 0 or 1. The acrylic monomer according to claim 1, wherein the acrylic monomer of the chemical formula 1 contains 1 to 3 dendritic units represented by the chemical formula 2. The acrylic monomer according to claim 1, wherein the acrylic monomer of the chemical formula 1 is a compound having the following chemical formula 1a or chemical formula 1b: A polymer for resist additive containing a repeating agent derived from an acrylic monomer as described in claim 1 unit. The polymer for resist additive according to claim 4, wherein the polymer further contains a repeating unit represented by the following Chemical Formula 10: In the chemical formula 10, R ⁴ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁵ is a hetero atom selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a carbon number of 1 to 10. a group consisting of an alkyl group, 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 a heteroaryl group having 5 to 30 carbon atoms Any of the groups. The polymer for resist additive according to claim 4, wherein the polymer has the structure of the following Chemical Formula 11: In the chemical formula 11, R ¹ , R ² and X are the same as R ¹ , R ² and X as defined in the acrylic monomer according to claim 1 of the patent application, and R ⁴¹ and R ⁴² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁵¹ and R ⁵² are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a heteroalkyl group having 1 to 10 carbon atoms, and a carbon number. Any one of the group consisting of a cycloalkyl group of 3 to 30, a heterocycloalkyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a heteroaryl group having 5 to 30 carbon atoms, And l, m and n are respectively used to represent the number of molar ratios of the repeating unit in the main chain, l+m+n=1, 0<l/(l+m+n) 0.99,0 m/(l+m+n) 0.99,0<n/(l+m+n) 0.99. The polymer for resist additive according to claim 6, wherein the R ⁵¹ is selected from the group consisting of with An acid-sensitive group in the group formed, in which case, Ra, Rb, and Rc are each independently selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, (having 1 carbon atom) An alkyl group to 10, a hydroxyalkyl group, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an ethyl group, an ethane group, a carboxyl group a group consisting of a (carboxyl group having 1 to 10 carbon atoms) carboxyl group, a (cycloalkyl group having 3 to 18 carbon atoms) carboxyl group, and a heterocycloalkyl group having 3 to 30 carbon atoms, or adjacent to each other The group linkage may form a saturated or unsaturated hydrocarbon ring or heterocyclic ring having 3 to 30 carbon atoms, Rd is an alkyl group having 1 to 10 carbon atoms, p is an integer of 0 to 3, and q is an integer of 0 to 10. And R ⁵² is or In this case, Re and Rf are each independently an alkyl group having 1 to 10 carbon atoms, or may be bonded to each other to form a saturated hydrocarbon ring, and r and s are each independently an integer of 0 to 5. The polymer for resist additive according to claim 6, wherein the R ⁵¹ is selected from the group consisting of t-butyl, trimethylmethanyl, hydroxy-2-ethyl, 1-methoxy Propyl, 1-methoxy-1-methylethyl, 1-ethoxypropyl, 1-ethoxy-1-methylethyl, 1-methoxy-1-ethyl, 1- Ethoxy-1-ethyl, tert-butoxy-2-ethyl, 1-isobutoxy-1-ethyl and a group consisting of the following Chemical Formula 12a to Chemical Formula 12j, In the chemical formula 12a to the chemical formula 12j, R', R" and R"' are each independently selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 1 to 10 carbon atoms. In the group consisting of an alkylcarboxyalkyl group of 10 and a cycloalkylcarbinyl group having 3 to 18 carbon atoms, a and e are integers of 0 to 15, b is an integer of 0 to 11, and c and d are respectively Independently an integer from 0 to 9, f is an integer from 0 to 7, and g and i are each independently an integer from 0 to 6, 0 c+d 17,0 c+f 15, and the R ⁵² has the structure of the following chemical formula 14a or chemical formula 14b: The polymer for resist additive according to claim 4, wherein the polymer has a weight average molecular weight of 1,000 to 20,000 g/mol in terms of polystyrene by gel permeation chromatography. The polymer for resist additive according to claim 4, wherein the ratio of the weight average molecular weight to the number average molecular weight of the polymer is from 1 to 3. The polymer for resist additive according to claim 4, wherein the polymer is selected from the group consisting of compounds having the structures of the following Chemical Formula 15a to Chemical Formula 15p: In the chemical formula 15a to the chemical formula 15p, l, m and n are l+m+n=1, 0<l/(l+m+n) 0.99, 0 < m / (l + m + n) 0.99 and 0<n/(l+m+n) 0.99. A resist composition containing a polymer for a resist additive according to any one of claims 4 to 11, a base polymer for a resist, and an acid generator. Agents and solvents. The resist composition according to claim 12, wherein the content of the polymer for the resist additive is 0.05 to 5% by weight based on the total weight of the resist composition. The resist composition according to claim 12, wherein the acid generator is one or more compounds selected from the group consisting of compounds represented by the following Chemical Formula 18 and Chemical Formula 19: In the chemical formula 18 and the chemical formula 19, X ₁ , X ₂ , Y ₁ and Y ₂ are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an allyl group, a perfluoroalkyl group, Any one of the group consisting of a benzyl group, an aryl group having 6 to 30 carbon atoms, and a combination thereof, wherein X ₁ and X ₂ and Y ₁ and Y ₂ may be bonded to each other to form a carbon number of 3 to 30. a saturated or unsaturated hydrocarbon ring, X ₃ , X ₄ , X ₅ , Y ₃ , Y ₄ and Y ₅ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a halogen group, and a carbon number of 1. Alkoxy group to 30, aryl group having 6 to 30 carbon atoms, thiophenoxy group, thioalkoxy group having 1 to 30 carbon atoms, alkoxycarbonylmethoxy group having 1 to 20 carbon atoms And any one of the group consisting of the combination thereof, the Z of the anion 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 a functional group represented by the following Chemical Formula 20: In the chemical formula 20, V ₁ and V ₂ are each independently a halogen atom, W ₁ is -(C=O)- or -(SO ₂ )-, and W ₂ is an alkylene group having 1 to 10 carbon atoms. W ₃ is any one selected from the group consisting of a stretched cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a heterocyclic alkyl group having 5 to 30 carbon atoms, ₄ is selected from the group consisting of a hydrogen atom, a halogen group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogen atom having 1 to 10 carbon atoms. a group, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aryl group having 6 to 30 carbon atoms Any one of the group consisting of (aryl group having 6 to 30 carbon atoms), heterocyclic group having 5 to 30 carbon atoms, and a combination thereof, o is an integer of 0 to 1, and p is An integer from 0 to 2. The resist composition of claim 12, wherein the resist composition further contains an additive selected from the group consisting of alkaline dissolution inhibitors, acid diffusion inhibitors, surfactants, and the like The mixture consists of a mixture of groups. A method of forming a resist pattern, comprising the steps of: coating a resist composition as described in claim 12 on a substrate to form a resist film; and heat-treating the resist film a step of exposing in a prescribed pattern; and a step of developing the exposed resist pattern. The method of forming a resist pattern according to claim 16, wherein the exposing step utilizes a laser selected from the group consisting of a KrF excimer laser, an ArF excimer laser, an extreme ultraviolet laser, an X-ray, and an electron beam. Light sources in the group formed are implemented.