KR20100047038A - A chemically amplified positive photoresist composition - Google Patents

Abstract

PURPOSE: A chemically amplified positive photoresist composition is provided to improve the stickiness for a substrate, and to reduce a standing wave effect generated on a side of a resist pattern. CONSTITUTION: A chemically amplified positive photoresist composition contains a resin, a photoacid generator, an additive including an anthracene derivative, and a quencher. The resin includes a resin component selected from the group consisting of a first resin containing a first unit marked as chemical formula 1a, and a second unit marked as chemical formula 1b in a mol ratio of 2:8~5:5, a second resin, a third resin, and their mixture.

Description

A chemically amplified positive photoresist composition

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to chemically amplified positive photoresist compositions suitable for photolithography, such as those acting by high energy radiation such as far ultraviolet rays, electron beams, X-rays, or radiant light, such as excimer lasers. It relates to a chemically amplified positive photoresist composition excellent in heat resistance.

In recent years, as the degree of integration of integrated circuits has increased, submicron pattern formation has been required. In particular, photolithography using an excimer laser from fluoride krypton (KrF) or argon fluoride (ArF) has been noted in that it enables the production of 64M DRAM to 1G DRAM. As a resist suitable for a photolithography process using such an excimer laser, a so-called chemically amplified resist using an acid catalyst and a chemical amplification effect is adopted. In the case where a chemically amplified resist is used, in the irradiation part of the radiation, the acid generated from the photoacid generator is diffused by the subsequent heat treatment, and the solubility in the alkaline developer of the irradiation part is changed by the reaction using the diffused acid as a catalyst. A type or negative type pattern is obtained.

In chemically amplified positive type resists, particularly positive type resists for KrF excimer laser photolithography, as a poly (hydroxystyrene) resin, a part of its phenolic hydroxyl group is protected by a group in which a phenolic hydroxyl group is dissociated by the action of an acid. It is often used in combination with a generator. Among the groups dissociated by the action of such an acid, a resin having an adamantane-based polymer unit and a specific high polar polymer unit having a specific structure is effective in improving the adhesion to the substrate. In addition, the use of specific materials that increase the resolution of these chemically amplified positive resists enables the implementation of fine contact holes.

However, even when such a material is used, the lower tailing of the profile may occur due to acid inactivation when the substrate has specificity, that is, when the substrate is basic, so that the profile is limited in forming a pattern. In addition, when the substrate is highly reflective, there is a problem that a standing wave phenomenon may appear on the side of the profile. In the case of the specificity of the substrate as described above, in general, variations in the depth of focus of the resist pattern tend to occur due to variations in the depth of focus, and the depth of focus is small. Therefore, conventionally known resist compositions have limitations in resolution, sensitivity, profile, depth of focus, and the like.

SUMMARY OF THE INVENTION An object of the present invention is to provide a chemically amplified positive photoresist composition which can improve adhesion to a substrate, reduce standing wave phenomena occurring on sidewalls of a resist pattern, and have excellent flatness, sensitivity, and resolution. It is also an object of the present invention to provide a chemically amplified positive photoresist composition capable of exhibiting excellent performance such as film retention ratio, applicability and thermal heat resistance and enabling the implementation of micro-sized contact holes and lines. It is also an object of the present invention to provide a chemically amplified positive photoresist composition that reduces the transmittance of the resist coating to reduce the mask error factor. It is also an object of the present invention to provide a chemically amplified positive photoresist composition which can improve the circularity of contact holes, suppress the absorption of radiation, and achieve a stable anti-halation effect.

In order to achieve the above object, the present invention comprises (A) a resin, (B) photoacid generator, (C) an additive comprising an anthracene derivative represented by the following formula (3) and (D) a quencher, wherein (A) The resin includes (a-1) a structural unit represented by the following Chemical Formula 1a and a structural unit represented by the following Chemical Formula 1b in a molar ratio of 2: 8 to 5: 5, and has a glass transition temperature (Tg) of 150 to 170 ° C. A first resin having a weight average molecular weight of 9,000 to 11,000; And (a-2) a second resin having a structural unit represented by the following Chemical Formula 1b and a structural unit represented by the following Chemical Formula 2a in a molar ratio of 9.9: 0.1 to 8: 2, and having a weight average molecular weight of 8,000 to 11,000, 1 comprising a structural unit represented by 1b and a structural unit represented by Formula 2b in a molar ratio of 9.9: 0.1 to 8: 2, and having a weight average molecular weight of 27,000 to 30,000; It provides a chemically amplified positive photoresist composition comprising a species.

<Formula 1a>

<Formula 1b>

<Formula 2a>

<Formula 2b>

<Formula 3>

In Formula 1a and Formula 3, R ₁ is a hydrogen atom or a methyl group, R ₂ is a linear, branched or cyclic alkyl group of 1 to 10 carbon atoms, R ₃ and R ₄ are each independently a hydrogen atom , A halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 3 carbon atoms or an aryl group unsubstituted or substituted with a halogen atom,-(CH ₂ ) n ₁ -OR ₅ or-(CH ₂ ) n ₂ -COO-R ₆ , n ₁ and n ₂ are each independently an integer of 0 to 3, R ₅ and R ₆ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or 1 to C An aryl group having 6 to 10 carbon atoms unsubstituted or substituted with an alkyl group of 3 or a halogen atom, X ₁ to X ₈ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, Or substituted with an alkyl group or halogen atom of 1 to 3 carbon atoms Is an aryl group having 6 to 10 carbon atoms unsubstituted.

The chemically amplified positive photoresist composition according to the present invention can reduce standing wave phenomena occurring on the sidewall of the resist pattern, and can provide a resist composition having excellent flatness, sensitivity, and resolution. In addition, the chemically amplified positive photoresist composition according to the present invention has an effect of exhibiting excellent resist performance such as polyfilm retention rate, applicability and heat resistance by using a resin having a protecting group of pivaloyl group and isopropyl group. In addition, the chemically amplified positive photoresist composition according to the present invention is suitable for photolithography using an excimer laser beam such as KrF, and particularly exhibits excellent circularity in the implementation of fine contact holes and can form accurate and precise resist patterns. have.

In addition, by including the anthracene derivative in the chemically amplified positive photoresist composition of the present invention, it is possible to reduce the mask error factor by reducing the transmittance of the resist film. In addition, the chemically amplified positive photoresist composition of the present invention may exhibit an effect of attenuating radiation that diffuses onto the resist film in a region where it is not desired to reflect and be sensitive on the substrate. For this reason, the light absorption phenomenon of radiation with respect to the area | region where it is not preferable to be sensitive to radiation can be suppressed effectively, and the stable antihalation effect can be achieved.

Hereinafter, the present invention will be described in detail.

I. Chemically Amplified Positive Photoresist Composition

The chemically amplified positive photoresist composition of the present invention contains (A) resin, (B) photoacid generator, (C) additive and (D) quencher.

(A) resin included in the chemically amplified positive photoresist composition of the present invention (a-1) is a molar ratio of the structural unit represented by the formula (1a) and the structural unit represented by the formula (1b) of 2: 8 to 5: 5 A first resin having a glass transition temperature (Tg) of 150 to 170 ° C and a weight average molecular weight of 9,000 to 11,000; And (a-2) a second resin having a structural unit represented by the following Chemical Formula 1b and a structural unit represented by the following Chemical Formula 2a in a molar ratio of 9.9: 0.1 to 8: 2, and having a weight average molecular weight of 8,000 to 11,000, 1 selected from the group consisting of a structural unit represented by 1b and a structural unit represented by the following Chemical Formula 2b in a molar ratio of 9.9: 0.1 to 8: 2 and a weight average molecular weight of 27,000 to 30,000; Includes species.

<Formula 1a>

<Formula 1b>

<Formula 2a>

<Formula 2b>

In Formula 1a, R ₁ is a hydrogen atom or a methyl group, R ₂ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, preferably R ₁ is a methyl group, R ₂ is an ethyl group. .

The first resin (a-1) contained in the resin (A) is insoluble or poorly soluble in aqueous alkali solution, but becomes soluble in aqueous alkali solution after dissociation of a functional group unstable with acid by the action of acid. Resin.

In the first resin (a-1), one structural unit represented by Chemical Formula 1a and two to six structural units represented by Chemical Formula 1b are alternately arranged in a line, and thus, the glass transition temperature is 150 to 170 ° C. do. That is, it can be seen that the first resin (a-1) is uniformly distributed between the structural unit represented by the general formula (1a) and the structural unit represented by the general formula (1b).

The first resin (a-1) includes a structural unit represented by Chemical Formula 1a and a structural unit represented by Chemical Formula 1b in a molar ratio of 2: 8 to 5: 5. When it is contained in the above-mentioned range, it has a structure which is advantageous in suppressing the characteristic of a resist, ie, a development defect, and improving a standing wave, a profile, a residual film ratio, etc.

On the other hand, a resin similar to the first resin (a-1) used in the prior art is a block copolymer separated by hydrophilic and hydrophobic groups in molecular units and separated according to their characteristics, so that glass transition temperature (Tg) is increased. 130-140 degreeC. In contrast, the first resin (a-1) of the present invention has a homogeneous distribution of hydrophilic and hydrophobic groups from molecular units to polymer units of each other, and thus has a glass transition temperature (Tg) of 150 to 170 ° C. It has a structure that is advantageous in suppressing characteristics, that is, developing defects, and improving standing waves, profiles, residual film ratios, and the like.

The weight average molecular weight of the first resin (a-1) was measured by gel permeation chromatography using polystyrene as a converting substance. When the weight average molecular weight is 9,000 to 11,000, the molecular chain is not entangled and deprotection of the protecting group is achieved. There is an easy advantage.

It is preferable that the dispersion degree of said (a-1) 1st resin is 1.4-1.6. It is preferable that the protection rate of said (a-1) 1st resin is 20 to 40%. When the above-described range is satisfied, an excellent pattern profile can be realized due to the excellent resolution, and there is an advantage that no residue occurs by preventing development defects.

(A-2) second resin included in the resin (A), a structural unit represented by Chemical Formula 1b and a structural unit represented by Chemical Formula 2a, and having a weight average molecular weight of 8,000 to 11,000, represented by Chemical Formula 1b At least one selected from the group consisting of a structural unit represented by Formula 2b and a structural unit represented by Chemical Formula 2b and having a weight average molecular weight of 27,000 to 30,000 and a mixture thereof is a resin that is soluble in an aqueous alkali solution.

The second resin includes a structural unit represented by Chemical Formula 1b and a structural unit represented by Chemical Formula 2a in a molar ratio of 9.9: 0.1 to 8: 2. The third resin includes a structural unit represented by Chemical Formula 1b and a structural unit represented by Chemical Formula 2b in a molar ratio of 9.9: 0.1 to 8: 2. When the above range is satisfied, the profile is excellent and the residual film ratio is increased, thereby improving the etching resistance.

The weight average molecular weights of the second and third resins were measured by gel permeation chromatography using polystyrene as a conversion material, and the weight average molecular weights of the second resins were 8,000 to 11,000, The weight average molecular weight is 27,000 to 30,000. If the above range is satisfied, there is an advantage that the thermal stability becomes high.

It is preferable that the said 2nd resin and 3rd resin have a 1 to 20% protection rate, respectively. If the above range is satisfied, the depth of focus according to the substrate is increased, the etching resistance is increased, and the pattern profile is excellent. In particular, it exhibits excellent circularity in the implementation of fine contact holes and can form accurate and precise resist patterns.

In addition, the (A) resin can be manufactured directly or purchased commercially.

The photoacid generator (B) included in the chemically amplified positive photoresist composition of the present invention is a compound that generates an acid by the action of light or radiation, and the material itself or a resist composition comprising such a material may be exposed to ultraviolet or far ultraviolet rays. It is a substance that generates acid by irradiating high energy radiation such as electron beam, X-ray, or radiated light. The acid generated from the photoacid generator (B) dissociates the functional group unstable to the acid present in the structural unit represented by the formula (1a) in the resin (A).

The photoacid generator (B) is one or two selected from onium salt compounds, organic-halogenated alkyl triazine type compounds, disulfone compounds, compounds having a diazomethanesulfonyl skeleton, and sulfonate compounds. It may include more than one species.

Specific examples of the (B) photoacid generator include diphenyl iodonium trifluoromethanesulfonate, diphenyl (4-toyl) sulfonium-triisopropylbenzenesulfonate, 4-methoxyphenylphenyl iodonium hexafluoro Antimonate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluorophosphate , Bis (4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium Hexafluoroantimonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium 2,4,6-triisopropylbenzenesulfonate, 4-methoxyphenyldiphenylsulfonium hexafluoroantimonate , 4-methoxyphenyldiphenylsulfonium Fluoromethanesulfonate, p-tolyldiphenylsulfonium trifluoromethanesulfonate, p-tolyldiphenylsulfonium perfluorobutanesulfonate, p-tolyldiphenylsulfonium perfluorooctanesulfonate, 2, 4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyl diphenylsulfonium hexafluorophosphate, 4- Phenylthiophenyldiphenylsulfonium hexafluoroantimonate, 1- (2-naphthoylmethyl) thiolanium hexafluoroantimonate, 1- (2-naphthoylmethyl) thiolanium trifluoromethanesulfo Nate, 4-hydroxy-1-naphthyldimethylsulfonium hexafluoroantimonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) Sulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-jade Cyclohexyl) sulfonium perfluorobutanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium perfluorooctanesulfonate, 2-methyl-4,6-bis (trichloromethyl) -1,3, 5-triazine, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine , 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxy-1-naphthyl) -4,6-bis (trichloromethyl) 1,3,5-triazine, 2- (benzo [d] [1,3] dioxolan-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis ( Trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dimethoxystyryl) -4,6- Bis (trichloromethyl) -1,3,5-t Azine, 2- (2-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-butoxystyryl) -4,6-bis ( Trichloromethyl) -1,3,5-triazine, 2- (4-pentyloxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, diphenyl disulfone, Di-p-tolyl disulfone, bis (phenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazomethane, bis (p-tolisosulfonyl) diazomethane, bis (4-t-butyl Phenylsulfonyl) diazomethane, bis (2,4-xylylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, (benzoyl) (phenylsulfonyl) diazomethane, 1-benzoyl- 1-phenylmethyl p-toluenesulfonate (so-called benzointosylate), 2-benzoyl-2-hydroxy-2-phenylethyl p-toluenesulfonate (so-called α-methylolbenzointosylate), 1,2 , 3-benzenetriyl trimethanesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, 2-nitrobenzyl p-toluenesulfonate, 4-nitrobenzyl p-toluene Phonates, N- (phenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) succinamide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoro Methylsulfonyloxy) -5-norbornene-2,3-dicarboxyimide and N- (trifluoromethylsulfonyloxy) naphthalimide, N- (10-camphorsulfonyloxy) naphthali Mead etc. are mentioned.

It is preferable that the said (B) photo-acid generator converted into solid content is contained in 0.1-12 weight part with respect to 100 weight part of said (A) resin converted into solid content. If the above range is satisfied, development defects do not occur, the resolution is excellent, and the pattern profile is excellent. Outside the above-described range, the pattern shape collapses to hardly form a patterned resist layer.

The (C) additive included in the chemically amplified positive photoresist composition of the present invention includes an anthracene derivative represented by the following formula (3).

<Formula 3>

In Formula 3, R ₃ and R ₄ are each independently substituted or unsubstituted with a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 3 carbon atoms, or a halogen atom Aryl group,-(CH ₂ ) n ₁ -OR ₅ or-(CH ₂ ) n ₂ -COO-R ₆ ,

n ₁ and n ₂ are each independently an integer of 0 to 3, and R ₅ and R ₆ are each independently substituted or unsubstituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 3 carbon atoms or a halogen atom; An aryl group having 1 to 6 carbon atoms,

X ₁ to X ₈ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkyl group having 6 to 10 carbon atoms unsubstituted or substituted with an alkyl group or halogen atom having 1 to 3 carbon atoms. It is an aryl group.

Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and the like. Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl and n-hex A practical group, n-octyl group, n-dodecyl group, etc. are mentioned. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group and the like. Examples of the aryl group having 6 to 10 carbon atoms substituted or unsubstituted with an alkyl group having 1 to 3 carbon atoms or a halogen atom include a phenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, o-chlorophenyl group and m-chloro A phenyl group, p-chlorophenyl group, a naphthyl group, etc. are mentioned.

Anthracene derivative represented by the formula (3) is a compound that absorbs radiation in the wavelength region to be irradiated. By including the anthracene derivative represented by Chemical Formula 3 in the chemically amplified positive photoresist composition of the present invention, the transmittance of the resist film can be reduced. It may also exhibit the effect of attenuating radiation which diffuses onto the resist coating in areas where it is undesirable to be reflected and sensitized on the substrate. As a result, it is possible to effectively suppress the absorption of radiation in the area where it is undesirable to be sensitive to radiation, to reduce the transmittance of the resist film, to reduce the mask error factor, and to stabilize the halation. Prevention effect can be achieved.

The anthracene derivative represented by Formula 3 is preferably a compound represented by the following Formula 3a or 3b.

<Formula 3a>

<Formula 3b>

_{N 1, n 2, R 4} , R 6 and X ₁ to X ₈ are as defined above are as defined in the above formula _{3 n 1, n 2, R} 4, R 6 and X ₁ to X _8. Herein, it is preferable that all of X ₁ to X ₈ are hydrogen atoms.

The anthracene derivative represented by Formula 3 is more preferably anthracene-9-methanol, anthracene-9-carboxyethyl and anthracene-9-carboxy-n-butyl. The anthracene derivative represented by Formula 3 may be used alone or in combination of two or more thereof.

It is preferable that 0.1-4 weight part of said (C) additives converted into solid content are contained with respect to 100 weight part of said (A) resin converted into solid content. If the above range is satisfied, the shape of the pattern is excellent and the standing wave phenomenon does not appear on the sidewalls. In addition, the resolution is excellent, it is possible to implement an excellent pattern profile. Outside the above-mentioned range, the resolution becomes poor and the pattern collapses to hardly form a resist layer.

In addition to the anthracene derivative represented by Formula 3, the (C) additive may further include various additives such as sensitizers, dissolution inhibitors, other resins, surfactants, stabilizers, dyes, and the like.

The chemically amplified positive photoresist composition of the present invention comprises (D) a quencher to prevent performance degradation caused by deactivation of the acid associated with post-exposure release. The (D) quencher is preferably a basic compound (s), in particular a basic nitrogen-containing organic compound such as an amine. Specific examples of the basic compound used as the (D) quencher may include a compound represented by the following Chemical Formulas 4a to 4j.

<Formula 4a>

<Formula 4b>

<Formula 4c>

<Formula 4d>

<Formula 4e>

<Formula 4f>

<Formula 4g>

<Formula 4h>

<Formula 4i>

<Formula 4j>

In Formulas 4a to 4j, R ₈ to R ₁₁ , R ₁₃ to R ₁₅ , R ₁₉ , R ₂₀ , R ₂₆ to R ₂₈ , R ₃₈ , R ₃₉ , and R ₄₂ to R ₄₄ each independently represent a hydrogen atom and an alkyl group. , A cycloalkyl group or an aryl group. The alkyl group, cycloalkyl group or aryl group may be substituted or unsubstituted with a hydroxyl group, an amino group or an alkoxy group having 1 to 6 carbon atoms, respectively. The amino group may be substituted with an alkyl group having 1 to 4 carbon atoms. The alkyl group may be an alkyl group having 1 to 6 carbon atoms, the cycloalkyl group may be a cycloalkyl group having 5 to 10 carbon atoms, and the aryl group may be an aryl group having 6 to 10 carbon atoms.

R ₁₂ , R ₁₆ to R ₁₈ , R ₂₀ to R ₂₅ , and R ₂₉ to R ₃₇ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group. The alkyl group, cycloalkyl group, aryl group or alkoxy group may be substituted or unsubstituted with hydroxyl group, amino group or alkoxy group having 1 to 6 carbon atoms, respectively. The amino group may be substituted with an alkyl group having 1 to 4 carbon atoms. The alkyl group may be an alkyl group having 1 to 6 carbon atoms, the cycloalkyl group may be an alkyl group having 5 to 10 carbon atoms, the aryl group may be an aryl group having 6 to 10 carbon atoms, and the alkoxy group may be an alkoxy group having 1 to 6 carbon atoms Can be.

R ₄₀ and R ₄₁ represent an alkyl group or a cycloalkyl group. The alkyl group or cycloalkyl group may be substituted or unsubstituted with a hydroxyl group, an amino group or an alkoxy group having 1 to 6 carbon atoms, respectively. The amino group may be substituted or unsubstituted with an alkyl group having 1 to C4 carbon atoms. The alkyl group may be an alkyl group having 1 to 6 carbon atoms, and the cycloalkyl group may be a cycloalkyl group having 5 to 10 carbon atoms.

A represents alkylene, carbonyl, imino, sulfide or disulfide. The alkylene may be alkylene having 2 to 6 carbon atoms.

The functional groups represented by any one of R ₈ to R ₄₄ can be straight or branched as long as they can take both straight and branched chain structures.

Specific examples of the compound represented by Formula 4a to Formula 4j include hexylamine, heptylamine, octylamine, nonylamine, decylamine, aniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, 1- or 2-naphthylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane , 4,4'-diamino-3,3'-diethyldiphenylmethane, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, diddecylamine, N- Methylaniline, peperidine, diphenylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyl Dibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonyl , Methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris {2 -(2-methoxyethoxy) ethyl} amine, triisopropanolamine, N, N-dimethylaniline, 2,6-isopropylaniline, imidazole, pyridine, 4-methylpyridine, 4-methylimidazole, b Pyridine, 2,2'-dipyridylamine, di-2-pyridylketone, 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 1,3- Di (4-pyridyl) propane, 1,2-bis (2-pyridyloxy) ethylene, 1,2-bis (4-pyridyl) ethylene, 1,2-bis (2-pyridyloxy) ethane , 4,4-dipyridylsulfide, 4,4-dipyridyldisulfide, 1,2-bis (4-pyridyl) ethylene, 2,2'-dipicorylamine, 3,3'-dipico Rylamine, tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, etc. are mentioned.

It is preferable that the said (D) quencher converted into solid content contains 0.01-10 weight part with respect to 100 weight part of said (A) resin converted into solid content. If the above-mentioned range is satisfied, only a proper amount of acid is diffused and developed on the exposed portion, so that a development defect does not occur, which results in an excellent pattern profile. Outside the above-described range, a problem may occur in that the photosensitivity of the photoresist composition is reduced by lowering the diffusion of acid to cause a change in profile due to lower sensitivity or development defects.

The chemically amplified positive photoresist composition of the present invention may be present in the form of a resist liquid composition by including conventional solvents. The solvent preferably dissolves the components, exhibits a suitable drying rate, and provides a uniform and smooth coating after evaporation of the solvent, and those conventionally used in this field may be used. Examples thereof include glycol ether esters such as ethylcellosolve acetate, methylcellosolve acetate and propylene glycol monomethyl ether acetate; Esters such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate; Ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; Alcohol, such as 3-methoxy- 1-butanol, etc. are mentioned. These solvents may each be used alone or as a mixture of two or more.

II. Pattern Formation Method

Using the chemically amplified positive photoresist composition according to the present invention, a resist pattern can be formed by the following method.

The chemically amplified positive photoresist composition according to the present invention is formed on the etching target layer of the substrate by using a spin coating method. Preferably, the substrate is a silicon wafer or glass. Pre-baking may be performed to form the photoresist film into a solid resist. An electron beam is injected into the photoresist film as an exposure source, and then a post exposure bake is performed on the exposed resist film to diffuse the exposed acid. Heat. The baked photoresist film is developed with an alkaline developer to form a resist pattern .

The alkali developer used in the present invention includes sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, n-propylamine, triethylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide It can be selected from various alkali aqueous solutions, such as a hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide, Among these, tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (typically, Preferred choline).

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.

Examples 1-3 and Comparative Examples 1-4: Preparation of Chemically Amplified Positive Photoresist Compositions

The components shown in Table 1 were mixed at the compositional ratios (in terms of solids) shown, dissolved in 800 parts by weight of propylene glycol monomethyl ether acetate and 142 parts by weight of ethyl lactate, and then a fluorine resin having a pore diameter of 0.1 μm. Filtration through a filter produced a resist solution. The stripping protection rate of the prepared resist solution is 40%, and the stripping protection rate is 2%.

Suzy Photoacid generator additive Quencher Type (protection rate) Parts by weight Kinds Parts by weight Kinds Parts by weight Kinds Parts by weight Example 1 A-1 (40%) / A-2 (2%) 100 B-1 / B-2 4.83 / 2.07 = 6.9 C-1 1.03 D-1 / D-2 0.06 / 0.06 = 0.12 Example 2 A-1 (40%) / A-3 (2%) 100 B-1 / B-2 4.83 / 2.07 = 6.9 C-1 1.03 D-1 / D-2 0.06 / 0.06 = 0.12 Example 3 A-1 (40%) / A-2 (2%) / A-3 (2%) 100 B-1 / B-2 4.83 / 2.07 = 6.9 C-1 1.03 D-1 / D-2 0.06 / 0.06 = 0.12 Comparative Example 1 A-1 (40%) 100 B-1 / B-2 4.83 / 2.07 = 6.9 - - D-1 / D-2 0.06 / 0.06 = 0.12 Comparative Example 2 A-1 (40%) / A-2 (2%) 100 B-1 / B-2 4.83 / 2.07 = 6.9 C-1 4.14 D-1 / D-2 0.06 / 0.06 = 0.12 Comparative Example 3 A-1 (40%) / A-3 (2%) 100 B-1 / B-2 4.83 / 2.07 = 6.9 - - D-1 / D-2 0.06 / 0.06 = 0.12 Comparative Example 4 A-1 (40%) / A-3 (2%) 100 B-1 / B-2 4.83 / 2.07 = 6.9 C-1 4.14 D-1 / D-2 0.06 / 0.06 = 0.12 Comparative Example 5 A-1 (40%) / A-2 (2%) / A-3 (2%) 100 B-1 / B-2 4.83 / 2.07 = 6.9 C-1 4.14 D-1 / D-2 0.06 / 0.06 = 0.12

A-1: The structural units represented by the general formula (1a) (R ₁ : methyl group, R ₂ : ethyl group) and the structural units represented by the general formula (1a) are alternately arranged in a line, the molar ratio of the structural unit is 4: 6, the glass transition Resin whose temperature (Tg) is 150 degreeC and molecular weight is 9,150 (manufacturer: Dupont, brand name: SRC-D90)

A-2: The structural unit represented by the formula (1b) and the structural unit represented by the formula (2a) are alternately arranged on a line, and the resin having a protection rate of pivaroyl group of 2% and a weight average molecular weight of 9,000

A-3: The structural unit represented by the formula (1b) and the structural unit represented by the formula (2b) are arranged alternately on the line, the resin having an isopropyl group protection of 2% and a weight average molecular weight of 28,000.

B-1: 2- (tert-butylsulfonyl (diazo) methylsulfonyl) -2-methylpropene [2- (tert-butylsulfonyl (diazo) methylsulfonyl) -2-methylpropane]

B-2: triphenylsulfonium 2,4,6-triisopropylbenzenesulfonate

C-1: a compound represented by Formula 3 (R ₃ : CH ₂ OH, R ₄ : CH ₂ OH, X ₁ to X ₈ : hydrogen)

D-1: triisopropanolamine

D-2: 2,6-diisopropylaniline

Test Example: Performance Test of Chemically Amplified Positive Photoresist Solution

The film thicknesses of the resist solutions of Examples 1-3 and Comparative Examples 1-5 were applied to a silicon wafer treated with an organic antireflective film using a spin coater and dried, followed by a film thickness of 0.300 µm. The substrate on which the dried resist film was formed was performed for 60 seconds on a hot plate at 110 ° C. While slowly changing the exposure dose of the wafer having the bent resist film using a scanning exposure apparatus ['NSR-S203B' manufactured by Nikon Corp., NA = 0.68, sigma == 0.75] having an exposure wavelength of 248 nm (KrF), Exposure was performed to form contact holes and line patterns. Subsequently, post exposure bake at the hot plate was performed at 110 ° C. for 60 seconds. In addition, paddle development was performed for 60 seconds using an aqueous 2.38% tetramethylammonium hydroxide solution. The pattern after development was measured using a scanning electron microscope to determine the depth of focus and the profile and the mask error factor in 0.15 탆 contact holes and line patterns. The results are shown in Table 2.

Standing wave phenomenon resolution profile MEF Example 1 ◎ ◎ ○ ○ Example 2 ◎ ◎ ◎ ◎ Example 3 ◎ ○ ○ ○ Comparative Example 1 × ○ △ × Comparative Example 2 ◎ × △ × Comparative Example 3 × ○ × ◎ Comparative Example 4 ◎ × △ × Comparative Example 5 ◎ × △ ×

* Standing wave phenomenon: ◎: Very low, ○: Low, △: High, X: Poor

※ Resolution: ◎: Very high, ○: High, △: Low, X: Poor

※ Profile: ◎: Very good, ○: Good, △: Low, X: Poor

※ Mask error factor: ◎: Very low, ○: Low, △: High, X: Very high

As shown in Table 2, the chemically amplified positive photoresist compositions of Examples 1 to 3 have a very low standing wave phenomenon occurring on the sidewall of the resist pattern and a pattern having excellent resolution. On the other hand, Comparative Example 1 was found that the standing wave phenomenon is severe, the profile is badly formed and the mask error factor is also very high. In Comparative Example 2, the standing wave phenomenon was excellent, but the resolution was poor due to the excessive use of the additive. In Comparative Example 3, the mask error factor was excellent, but the standing wave phenomenon was severe, and the profile was poor. In Comparative Example 4 and Comparative Example 5, the resolution was bad due to the excessive use of the additive, and thus the mask error factor was also very high.

Claims (9)

(A) a resin, (B) a photoacid generator, (C) an additive containing an anthracene derivative represented by the following formula (3), and (D) a quencher, The above (A) resin (a-1) A structural unit represented by the following formula (1a) and a structural unit represented by the following formula (1b) in a molar ratio of 2: 8 to 5: 5, the glass transition temperature (Tg) is 150 to 170 ℃ and the weight average molecular weight The first resin having 9,000 to 11,000; And (a-2) A second resin containing a structural unit represented by the following Chemical Formula 1b and a structural unit represented by the following Chemical Formula 2a in a molar ratio of 9.9: 0.1 to 8: 2, and having a weight average molecular weight of 8,000 to 11,000; A third resin having a structural unit represented by the following formula and a structural unit represented by the following Chemical Formula 2b in a molar ratio of 9.9: 0.1 to 8: 2, and having a weight average molecular weight of 27,000 to 30,000, and a mixture thereof A chemically amplified positive photoresist composition comprising: <Formula 1a>

<Formula 1b>

<Formula 2a>

<Formula 2b>

<Formula 3>

In Chemical Formulas 1a and 3, R ₁ is a hydrogen atom or a methyl group, R ₂ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 3 carbon atoms or an aryl group unsubstituted or substituted with a halogen atom,-( CH ₂ ) n ₁ -OR ₅ or-(CH ₂ ) n ₂ -COO-R ₆ , n ₁ and n ₂ are each independently an integer of 0 to 3, R ₅ and R ₆ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 10 carbon atoms unsubstituted or substituted with a halogen atom, X ₁ to X ₈ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkyl group having 6 to 10 carbon atoms unsubstituted or substituted with an alkyl group or halogen atom having 1 to 3 carbon atoms. It is an aryl group. The method according to claim 1, Based on 100 parts by weight of the (A) resin converted into solids, 0.1 to 12 parts by weight of the (B) photoacid generator in terms of solid content; 0.1 to 4 parts by weight of the additive (C) in terms of solids; A chemically amplified positive photoresist composition comprising 0.01 to 10 parts by weight of the (D) quencher, converted into solids. The method according to claim 1, In Chemical Formula 1a, R ₁ is a methyl group, and R ₂ is an ethyl group. The method according to claim 1, A chemically amplified positive photoresist composition, wherein the dispersity of the first resin (a-1) is 1.4 to 1.6. The method according to claim 1, Chemical amplification-type positive photoresist composition, characterized in that the protective ratio of the (a-1) first resin is 20 to 40%. The method according to claim 1, The protective ratio of the second resin is a chemically amplified positive photoresist composition, characterized in that 1% to 20%. The method according to claim 1, The protective ratio of the third resin is a chemically amplified positive photoresist composition, characterized in that 1% to 20%. The method according to claim 1, The anthracene derivative represented by Chemical Formula 3 may be a compound represented by Chemical Formula 3a or a compound represented by Chemical Formula 3b. <Formula 3a>

<Formula 3b>

_{N 1, n 2, R 4} , R 6 and X ₁ to X ₈ are as defined above are as defined in the above formula _{3 n 1, n 2, R} 4, R 6 and X ₁ to X _8. The method according to claim 1, The (B) photoacid generator is selected from the group consisting of an onium salt compound, an organic-halogenated alkyl triazine type compound, a disulfone compound, a compound having a diazomethanesulfonyl skeleton, and a sulfonate compound. A chemically amplified positive photoresist composition comprising a species or two or more species.