KR20100047046A - I-line chemically amplified positive photoreist and pattern forming method using the same - Google Patents

Abstract

PURPOSE: An i-line chemically amplified positive photoresist and a pattern formation method using thereof are provided to reduce the stationary wave phenomenon generating at the side wall of a resist pattern. CONSTITUTION: An i-line chemically amplified positive photoresist contains a resin, a photoacid generator selected from the group consisting of a compound marked as chemical formula 4, and a compound marked as chemical formula 5, and a quencher. The resin contains a first resin with the average molecular weight of 9,000~11,000, and a second resin with the protective rate of 1~20%.

Description

I-line chemically amplified positive photoreist and pattern forming method using the same

The present invention relates to a photoresist composition of submicron lithography using i-rays and a pattern forming method using the same, and more particularly, to a poly (hydroxystyrene) structural unit and an anthracene polyacrylate structural unit. The present invention relates to an i-ray chemically amplified positive photoresist composition for submicron lithography using i-rays by mixing a resin and a photoacid generator sensitive to i-rays, and a pattern forming method using the same.

In the microfabrication field represented by the manufacture of integrated circuits, the processing size in lithography is on the trend to miniaturization. Recently, there is a need for a technique capable of stably performing micromachining having a width of 0.5 μm or less. Therefore, also in the resist used for this purpose, it is necessary to be able to form a pattern having a line width of 0.5 mu m or less with good accuracy. Therefore, lithography techniques using shorter radiation have been studied. Examples of the radiation include ultraviolet rays represented by i-rays (365 nm), ultraviolet rays represented by KrF excimer lasers (248 nm), X-rays represented by synchrotron radiation, charged particle beams represented by electron beams, and the like. Can be mentioned.

In recent years, various resists for use in response to these radiations have been proposed. Of particular interest among these resists are resists capable of causing a reaction to change their solubility in a developer by the catalysis of an acid generated by irradiation of radiation. This kind of resist is commonly referred to as "chemically amplified resist". Among these, as a method of improving the submicron pattern using ultraviolet rays represented by i-rays (365 nm) so far, a novolak resin for g-ray resists or a Benzonphenone sensitizer (Photo Active Compounds): The improvement of the pattern was approached by adjusting the physical properties of PAC.

However, in the case of pattern formation by photolithography in the case of substrate specificity, the variation of the finished pattern of the resist pattern is easy to occur due to the variation of the depth of focus, the depth of focus is small, and the standing wave phenomenon and the residue on the sidewall of the resist pattern according to the characteristics of the substrate. The problem remained. In addition, it turns out that there is a limit to the implementation of high resolution micropatterns and high sensitivity resists.

Therefore, there is a need for developing a new i-ray positive photoresist composition to solve this problem.

An object of the present invention is a resist suitable for an ultraviolet 365 nm (i-ray) light source, so that a microstructure pattern of 0.4 μm or less can be realized and poly (hydroxystyrene) -based structural units and acrylate-based structures have a small variation according to a substrate. It is to improve the problem of storage stability of the composition by mixing the resin containing the unit and the photo-acid generator sensitive to i-rays. The present invention also provides an i-ray chemically amplified positive photoresist composition for submicron lithography that exhibits high sensitivity and high resolution performance by solving the standing wave phenomenon of the sidewall of the resist pattern and the scum due to the development defect according to the characteristics of the substrate. will be.

In order to achieve the above object, the present invention is a photoacid generation comprising one kind selected from the group consisting of (A) resin, (B) a compound represented by the following formula (4), a compound represented by the formula (5), and mixtures thereof And (C) a quencher, wherein the resin (A) comprises (a-1) a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2) in a molar ratio 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) the structural units represented by the following formula (2) and the structural units represented by the following formula (3) are alternately arranged on a line in a molar ratio of 9.9: 0.1 to 8: 2, with a protective ratio of 1 to 20%, and a weight average It provides an i-ray chemically amplified positive photoresist composition comprising a second resin having a molecular weight of 9,000 to 11,000.

<Formula 1>

<Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

In Formula 1, Formula 4 and Formula 5, R ₁ is hydrogen or a methyl group, R ₂ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, R ₃ is fluorine, chlorine, bromine, hydroxy group, a nitro group, an oxo group, an ester group, a carbon number of 1 to 6 alkoxy group, an alkyl group or having 6 to 18 carbon atoms having 1 to 12 carbon atoms of the aryl group, R ₄ is C 6 -C 12 aryl group, a halogen atom or a C 6 -C C1-C12 linear or branched alkyl group unsubstituted or substituted by 12 cyclic alkyl groups; It is a C1-C20 linear or branched alkyl group, a C1-C6 alkoxy group, or a C6-C18 aryl group unsubstituted or substituted by a halogen atom.

The present invention also provides a photoresist film using the chemically amplified positive photoresist composition on a substrate, selectively exposing the photoresist film, and post exposure bake (PEB) of the selectively exposed photoresist film. And developing the post-exposure baked photoresist film.

The chemically amplified positive photoresist composition according to the present invention is a resist suitable for a 365 nm (i-ray) light source, and a pattern having a highly sensitive microstructure of 0.4 μm or less can be realized. The standing wave phenomenon can be reduced. In addition, it is possible to provide a resist composition having excellent flatness, sensitivity, and resolution, and there is no problem in storage stability, and it is possible to form a more precise and accurate resist pattern in implementing a scum-free resist performance caused by substrate characteristics. have.

Hereinafter, the present invention will be described in detail.

I. i-ray chemically amplified positive photoresist composition

The i-ray chemically amplified positive photoresist composition of the present invention comprises (A) resin, (B) photoacid generator and (C) quencher.

The resin (A) contained in the i-ray chemically amplified positive photoresist composition of the present invention comprises (a-1) a structural unit represented by the following Chemical Formula 1 and a structural unit represented by the following Chemical Formula 2: 2: 8 to 5: A first resin having a molar ratio of 5 and 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) the structural units represented by the following formula (2) and the structural units represented by the following formula (3) are alternately arranged on a line in a molar ratio of 9.9: 0.1 to 8: 2, with a protective ratio of 1 to 20%, and a weight average A second resin having a molecular weight of 9,000 to 11,000.

<Formula 1>

<Formula 2>

<Formula 3>

In Chemical Formula 1,

R ₁ is hydrogen 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 and R ₂ is an ethyl group.

When the resin (A) is used in the i-ray photoresist process, there is no residual phenomenon due to the development defect, the refinement wave phenomenon is reduced, and the resolution is excellent.

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

In the first resin (a-1), one structural unit represented by Chemical Formula 1 and two to six structural units represented by Chemical Formula 2 are alternately arranged in a linear shape, and thus the glass transition temperature is 150 to 170 ° C. do. That is, it can be seen that the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) of the first resin (a-1) are uniformly distributed.

Resins similar to the first resin (a-1) used in the prior art are block copolymers separated by hydrophilic and hydrophobic groups in molecular units and separated according to their characteristics, so that the glass transition temperature (Tg) is 130 to 130. 140 ° C. In contrast, the first resin (a-1) of the present invention has a glass transition temperature (Tg) of 150 to 170 ° C. due to the uniform distribution of hydrophilic and hydrophobic groups from the molecular unit to the polymerized unit of each other. Has a structure that is advantageous in suppressing the development defect, that is, improving the standing wave, the profile, the residual film ratio, and the like.

It is preferable that the protection rate of said (a-1) 1st resin is 19.5-40%. If the above-mentioned range is satisfied, the pattern profile is excellent by implementing a high sensitivity and excellent resolution, and there is an advantage in that residues are prevented by preventing development defects.

It is preferable that the dispersion degree of said (a-1) 1st resin is 1.4-1.6.

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.

Said (a-2) 2nd resin contained in said (A) resin is resin which becomes soluble in aqueous alkali solution.

The said (a-2) 2nd resin is resin which becomes soluble in aqueous alkali solution. The second resin (a-2) includes a structural unit represented by Chemical Formula 2 and a structural unit represented by Chemical Formula 3 in a molar ratio of 9.9: 0.1 to 8: 2. When the above-mentioned range is satisfied, the above-mentioned range is included, which is advantageous in suppressing the characteristics of the resist, that is, developing defects, and improving standing waves, profiles, and residual film ratios.

The weight average molecular weight of the second resin (a-2) was measured by gel permeation chromatography using polystyrene as a conversion material, and the weight average molecular weight was 9,000 to 11,000. If the above-mentioned range is satisfied, thermal stability is improved and dispersion degree is improved.

The protection rate of the said (a-2) 2nd resin is 1 to 20%. When the above range is satisfied, the refinement wave phenomenon according to the substrate is reduced, and the pattern profile is excellent. In addition, it is possible to implement an excellent pattern profile due to the high sensitivity and excellent resolution, there is an advantage that the phenomenon does not occur by preventing the development defect.

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

The photoacid generator (B) included in the i-ray chemically amplified positive photoresist composition of the present invention is 1 selected from the group consisting of a compound represented by the following formula (4), a compound represented by the following formula (5), and a mixture thereof Includes species.

<Formula 4>

<Formula 5>

In Formula 4, R ₃ is fluorine, chlorine, bromine, hydroxy group, nitro group, oxo group, ester group, alkoxy group having 1 to 6 carbon atoms, alkyl group having 1 to 12 carbon atoms or aryl group having 6 to 18 carbon atoms.

In Formula 5, R ₄ is a linear or branched alkyl group having 1 to 12 carbon atoms unsubstituted or substituted with a aryl group having 6 to 12 carbon atoms, a halogen atom or a cyclic alkyl group having 6 to 12 carbon atoms; It is a C1-C20 linear or branched alkyl group, a C1-C6 alkoxy group, or a C6-C18 aryl group unsubstituted or substituted by a halogen atom.

로 표시되는 화합물로 이루어진 군에서 선택되는 1종이다.Preferably, R ₃ and R ₄ are each independently n-propyl group, n-butyl group, n-octyl group, toluyl group, trifluoromethyl group, 2,4,6-trimethylphenyl group, 2,4,6- Triisopropylphenyl group, 4-dodecylphenyl group, 4-methoxyphenyl group, 2-naphthyl group, benzyl group and

It is 1 type chosen from the group which consists of a compound represented by.

The compounds represented by the above formulas (4) and (5) react particularly with i-rays (365 nm) and react with the resin (A) to achieve particularly good results.

The photoacid generator (B) is a compound that generates an acid by the action of light or radiation, and has a high energy such as ultraviolet light, far ultraviolet rays, electron beams, X-rays, or radiation in the material itself or in a resist composition comprising such a material. It is a substance that generates acid by irradiation with radiation. The acid generated from the photoacid generator (B) acts on the structural unit represented by the formula (1) in the resin (A) to dissociate the adamantyl group, which is a functional group unstable to the acid present in the structural unit represented by the formula (1). .

The photoacid generator (B) is preferably contained in 2.2 to 14.8 parts by weight based on 100 parts by weight of the (A) resin. When included in the above-described range, the development defect does not occur, the resolution is excellent, there is an advantage that the pattern profile is excellent. If it is not included in the above-described range, the pattern shape is collapsed to hardly form a patterned resist layer. Here, the content of the (A) resin and (B) photoacid generator is preferably converted to solid content.

The i-ray chemically amplified positive photoresist composition of the present invention comprises (C) a quencher. The (C) quencher prevents performance degradation caused by deactivation of acid associated with post-exposure release. The (C) quencher may further comprise basic compound (s), in particular basic nitrogen-containing organic compounds such as amines. Specific examples of the basic compound used as the (C) quencher may include a compound represented by the following Chemical Formulas 6a to 6j.

<Formula 6a>

<Formula 6b>

<Formula 6c>

<Formula 6d>

<Formula 6e>

<Formula 6f>

<Formula 6g>

<Formula 6h>

<Formula 6i>

<Formula 6j>

In Formulas 6a to 6j, R ₅ to R ₈ , R ₁₀ to R ₁₂ , R ₁₆ , R ₁₇ , R ₂₄ , R ₂₅ , R ₃₅ , R ₃₆ , and R ₃₉ to R ₄₁ 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 preferably has 1 to 6 carbon atoms, the cycloalkyl group preferably has 5 to 10 carbon atoms, and the aryl group preferably has 6 to 10 carbon atoms.

R ₉ , R ₁₃ to R ₁₅ , R ₁₈ to R ₂₃ , and R ₂₆ to R ₃₄ are each independently 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 preferably has 1 to 6 carbon atoms, the cycloalkyl group preferably has 5 to 10 carbon atoms, the aryl group preferably has 6 to 10 carbon atoms, and the alkoxy group preferably has 1 to 6 carbon atoms.

R ₃₇ And R ₃₈ represents 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 4 carbon atoms. It is preferable that the said alkyl group is C1-C6, and it is preferable that the said cycloalkyl group is C5-C10.

A is alkylene, carbonyl, imino, sulfide or disulfide. It is preferable that the said alkylene is C2-C6.

Specific examples of the compound represented by Formula 6a to 6j are 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, didecylamine, N-methyl Aniline, Peperidine, Diphenylamine, Triethylamine, Trimethylamine, Tripropylamine, Tributylamine, Tripentylamine, Trihexylamine, Triheptylamine, Trioctylamine, Trinonylamine, Tridecylamine, Methyldi Butylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyl Decylamine, 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, bipyridine, 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'-dipicorylamine , Tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide and the like.

It is preferable that the said (C) quencher is contained in 0.01-10 weight part with respect to 100 weight part of said (A) resins. When included in the above-described range, an appropriate amount of acid is diffused during the photoresist process, thereby developing only the exposed portion, thereby improving the pattern profile. In addition, since the sensitivity is excellent, excellent photosensitivity can be realized by preventing the pattern profile from being changed due to development defects. Here, the content of the (A) resin and (C) quencher is preferably converted to solid content.

In addition, the chemically amplified positive photoresist composition of the present invention may further include a small amount of various additives such as sensitizers, dissolution inhibitors, other resins, surfactants, stabilizers, dyes and the like except for the (C) quencher.

The i-ray chemically amplified positive photoresist composition of the present invention may be provided in the form of a resist liquid composition comprising components dissolved in 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. Each of these solvents may be used alone or in combination of two or more.

II. Pattern Formation Method

Using the i-ray chemically amplified positive photoresist composition according to the present invention, a resist pattern can be formed in the following manner.

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. 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. The baked photoresist film is developed with an alkaline developer to form a resist pattern .

The alkaline 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 It can be selected from various aqueous alkali solutions, such as hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide, among which tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (usually , 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 to 3 and Comparative Examples 1 to 4: Preparation of Chemically Amplified Positive Photoresist Compositions

The components shown in Table 1 were mixed at the indicated composition ratios, dissolved in 815 parts by weight of propylene glycol monomethyl ether acetate, and then filtered through a fluorine resin filter having a pore diameter of 0.1 μm to prepare a resist solution.

Suzy Photoacid generator Quencher Type (protection rate) Parts by weight Kinds Parts by weight Kinds Parts by weight Example 1 A-1 (25%) / A-2 (7%) 100 B-1 / B-2 2.22 / 2.22 = 4.44 D-1 / D-2 0.45 / 0.45 = 0.9 Example 2 A-1 (25%) / A-2 (7%) 100 B-1 4.44 D-1 / D-2 0.45 / 0.45 = 0.9 Example 3 A-1 (25%) / A-2 (7%) 100 B-2 4.44 D-1 / D-2 0.45 / 0.45 = 0.9 Comparative Example 1 A-1 (25%) / A-2 (7%) 100 B-3 5.93 D-1 / D-2 0.45 / 0.45 = 0.9 Comparative Example 2 A-1 (25%) / A-2 (7%) 100 B-4 5.93 D-1 / D-2 0.45 / 0.45 = 0.9 Comparative Example 3 A-3 (25%) 100 B-3 / B-4 3.35 / 3.35 = 3.7 D-1 / D-2 0.45 / 0.45 = 0.9 Comparative Example 4 A-3 (25%) 100 B-1 / B-2 2.96 / 2.96 = 5.92 D-1 / D-2 0.45 / 0.45 = 0.9

A-1: The structural units represented by Formula 1 (R ₁ : methyl group, R ₂ : ethyl group) and the structural units represented by Formula 2 are alternately arranged in a line, and the molar ratio of the structural units is 2.5: 7.5, free Resin having a transition temperature (Tg) of 150 ° C. and a molecular weight of 9,150 (manufacturer: Dupont, trade name: SRC-D90)

A-2: A structural unit represented by the formula (3), arranged alternately on a line, a resin having a molecular weight of 10,000 with a 7% protection rate of the anthracene polyacrylate structural unit

A-3: 25% of the hydroxyl groups in the structural unit represented by the formula (2) are ethoxyethyl

Resin with molecular weight 10,000 protected with protecting group

B-1: Sulfonate type photoacid generator in which R ₃ is a normal propyl group in Chemical Formula 4 (manufacturer: Ciba, trade name: CGI-1397)

B-2: Maleimide type photoacid generator in which R ₄ is trifluoromethyl group in Chemical Formula 5 (manufacturer: Ciba, trade name: CGI-NIT)

B-3: 2- (tert-butylsulfonyl (diazo) methylsulfonyl) -2-methylpropene [2- (tert-butylsulfonyl (diazo) methylsulfonyl) -2-methylpropane]

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

C-1: triisopropanolamine

C-2: 2,6-diisopropylaniline

Test Example: Performance Test of Chemically Amplified Positive Photoresist Solution

When the resist solutions of Examples 1-3 and Comparative Examples 1-4 were applied to a silicon wafer treated with hexamethyldisilazane using a spin coater, the film thickness after drying was 0.42 mu m. The substrate on which the dried resist film was formed was performed for 60 seconds on a hot plate at 100 ° C. The exposure dose of the wafer having the precured resist film was gradually reduced using a stepper type exposure machine ['NSR-I11D' manufactured by Nikon Corp., NA = 0.63, sigma = 0.038], having an exposure wavelength of 365 nm (i-ray). Exposure was carried out while changing to form a fine-sized line pattern. Subsequently, in the hot plate, post-exposure bake 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 for depth of focus and profile in a line pattern of 0.4 mu m using a scanning electron microscope.

The results are shown in Table 2.

Standing wave phenomenon resolution Scum Sensitivity (msec / ㎠) Example 1 ◎ ○ ○ 110 Example 2 ◎ ◎ ○ 100 Example 3 ◎ ◎ ○ 110 Comparative Example 1 × × × - Comparative Example 2 × × × - Comparative Example 3 × × × - Comparative Example 4 △ △ × 106

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

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

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

As shown in Table 2, the i-ray chemically amplified positive photoresist compositions of Examples 1 to 3 formed a pattern having a very low standing wave phenomenon, no scum, and a high resolution pattern on the sidewall of the resist pattern (Fig. 1). To 3).

On the other hand, the i-ray chemically amplified positive photoresist compositions of Comparative Examples 1 to 3 use a photoacid generator that does not respond to the i-ray wavelength (365 nm), so that less acid is generated and dissociation of the protecting group does not occur. It was confirmed that the formation of the pattern did not occur (Figures 4 to 6). In addition, in the i-ray chemically amplified positive photoresist composition of Comparative Example 4, a photoacid generator sensitive to the i-ray wavelength (365 nm) was used, but the dissociation energy of the protecting group was low and the pattern specificity was poor due to the influence of the substrate specificity. Appeared to confirm that a lot of scum (Scum) occurs (Fig. 7).

1 is a photograph taken of a profile formed of a resist composition of Example 1 using a scanning electron microscope.

FIG. 2 is a photograph of a pattern formed of the resist composition of Example 2 and taken of a profile using a scanning electron microscope. FIG.

3 is a photograph taken of a profile formed of a resist composition of Example 3 using a scanning electron microscope.

4 is a photograph of a pattern formed of a resist composition of Comparative Example 1 and taken of a profile using a scanning electron microscope.

FIG. 5 is a photograph of a pattern formed of the resist composition of Comparative Example 2 and taken of a profile using a scanning electron microscope. FIG.

6 is a photograph in which a pattern is formed of the resist composition of Comparative Example 3 and the profile is taken using a scanning electron microscope.

7 is a photograph in which a pattern is formed of the resist composition of Comparative Example 4 and a profile is taken using a scanning electron microscope.

Claims (8)

(A) a resin, (B) a compound represented by the following formula (4), a compound represented by the formula (5) and a mixture thereof, and a photoacid generator comprising (1) selected from the group consisting of The above (A) resin (a-1) A structural unit represented by the following formula (1) and a structural unit represented by the following formula (2) 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) The structural units represented by the following formula (2) and the structural units represented by the following formula (3) are alternately arranged on a line in a molar ratio of 9.9: 0.1 to 8: 2, the protective ratio is 1 to 20%, and the weight average molecular weight I-ray chemically amplified positive photoresist composition comprising a second resin of 9,000 to 11,000: <Formula 1>

<Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

In Formula 1, Formula 4 and Formula 5, R ₁ is hydrogen or a methyl group, R ₂ is a straight, branched or cyclic alkyl group having 1 to 10 carbon atoms, R ₃ is fluorine, chlorine, bromine, hydroxy group, nitro group, oxo group, ester group, alkoxy group having 1 to 6 carbon atoms, alkyl group having 1 to 12 carbon atoms or aryl group having 6 to 18 carbon atoms, R ₄ is a straight or branched chain alkyl group having 1 to 12 carbon atoms which is unsubstituted or substituted with a aryl group having 6 to 12 carbon atoms, a halogen atom or a cyclic alkyl group having 6 to 12 carbon atoms; It is a C1-C20 linear or branched alkyl group, a C1-C6 alkoxy group, or a C6-C18 aryl group unsubstituted or substituted by a halogen atom. The method according to claim 1, Based on 100 parts by weight of the (A) resin, 2.2 to 14.8 parts by weight of the photoacid generator (B); I-ray chemically amplified positive photoresist composition comprising (C) 0.01 to 10 parts by weight of the quencher. The method according to claim 1, In Chemical Formula 1, R ₁ is a methyl group and R ₂ is an ethyl group i-ray chemically amplified positive photoresist composition. The method according to claim 1, I-ray chemically amplified positive photoresist composition, characterized in that (a-1) the first resin has a dispersion degree of 1.4 to 1.6. The method according to claim 1, I-ray chemically amplified positive photoresist composition, characterized in that (a-1) the first resin has a protection rate of 19.5% to 40%. The method according to claim 1, In Formulas 4 and 5, R ₃ and R ₄ are each independently n-propyl group, n-butyl group, n-octyl group, toluyl group, trifluoromethyl group, 2,4,6-trimethylphenyl group, 2 , 4,6-triisopropylphenyl group, 4-dodecylphenyl group, 4-methoxyphenyl group, 2-naphthyl group, benzyl group and

I-ray chemically amplified positive photoresist composition, characterized in that one kind selected from the group consisting of compounds represented by. The method according to claim 1, The (C) quencher is an i-ray chemically amplified positive photoresist composition, characterized in that it comprises an organic compound. Forming a photoresist film on the substrate using the i-ray chemically amplified positive photoresist composition of the substrate according to claim 1; Selectively exposing the photoresist film; Post exposure bake (PEB) the selectively exposed photoresist film; And And developing the post-exposure baked photoresist film.

Images