KR19990021118A - Novel Photoresist Copolymer and Photoresist Composition Comprising the Same - Google Patents

Abstract

The present invention relates to a copolymer for preparing a chemically amplified photoresist and a positive photoresist composition containing the same, wherein the repeating unit is a copolymer represented by the following formula (1) and a composition of the photoresist comprising the copolymer and an acid generator. When the resin is synthesized and the photoresist is manufactured and tested, it is excellent in high sensitivity, high resolution, heat resistance, and stability after exposure to radiation such as an ultraviolet ray KrF excimer laser, and an excellent resist pattern is obtained regardless of the substrate type. Could.

[Formula 1]

In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ are each independently a hydrogen atom or a methyl group, and R ₅ , R ₆ , R ₇ , R ₈ are each independently a hydrogen atom, an alkali group, an alkoxy group, An alkoxycarbonyl group or a halogen group is represented, h and g are the integers of 0-8, respectively. w, x, y, and z are numbers representing repeating units, respectively, and satisfy a relationship of 0.3 w 0.9, 0.01 x 0.3, 0.1, y 0.6, and 0.01 z 0.5, and w + x + y + z = 1. And Am is —NR ₉ R ₁₀ , cyclic divalent amines, cyclic divalent amines containing oxygen or sulfur, wherein R ₉ and R ₁₀ are each independently a hydrogen atom, an alkyl group, an aryl group, or a phenyl group.

Description

Photoresist composition comprising a novel photoresist copolymer and a tooth

The present invention relates to a copolymer for preparing a chemically amplified photoresist and a positive photoresist composition containing the same, in particular, a repeating unit of the copolymer represented by the following formula (1) and a photoresist composed of this copolymer and an acid generator It relates to the composition, and more specifically, even after baking after elapsed time, an excellent pattern can be formed, and it has high sensitivity, high resolution, and high heat resistance, and has ultraviolet rays, far ultraviolet rays, excimer lasers, X-rays, electron beams, and the like. It relates to a copolymer for producing a chemically amplified photoresist sensitive to radiation and a positive photoresist composition containing the same.

Recently, due to the high integration of semiconductor devices, ultra-fine patterns in the sub-quarter-micron area are required for the manufacture of ultra-LSI, etc. As a result, the exposure wavelength is shortened in the g-line or i-line region used in the related art. Attention has been drawn to lithography using ultraviolet, KrF excimer lasers, X-rays and electron beams.

Conventionally, photoresists used for g-rays or I-rays are resists using novolak-quinonediazide compounds, and polyhydroxystyrene derivatives having relatively low absorption due to high absorption of light at far ultraviolet rays or KrF excimer laser wavelengths. Chemically amplified photoresist using as a base resin has attracted much attention.

The chemical component of the chemically amplified photoresist is composed of a compound (hereinafter referred to as an acid generator) that generates an acid by radiation, a basic resin whose physical and chemical properties are changed by an acid, a small amount of additives, and a solvent that dissolves them. have.

As such a chemically amplified photoresist, for example, US Pat. No. 4,491,628 is known in which t-butoxycarbooxy group is introduced into polyhydroxystyrene and used as a base resin.

However, the conventional chemically amplified photoresist as described above does not have good resolution and heat resistance, and in particular, a desired pattern may not be obtained when baking after lagging after exposure.

The present invention is to solve the problems of the prior art as described above, an object of the present invention is to introduce an amide group into polyhydroxy styrene as a new functional group, wherein the poly hydroxy styrene is reduced by 5 to 10% with hydrogen gas It is to provide a novel photoresist copolymer capable of minimizing the absorption of polyhydroxy styrene in the far ultraviolet region (248 nm) by using the prepared.

Another object of the present invention is to provide a photoresist composition prepared by preparing a photoresist including the base resin, which is excellent in high sensitivity, high resolution, heat resistance, and stability after exposure, and can obtain an excellent resist pattern regardless of the type of substrate. have.

The novel photoresist copolymer according to the present invention for achieving the above object is characterized in that the polystyrene reduced average molecular weight represented by the copolymer of formula (I) is 1000 ~ 1,000,000.

A feature of the photoresist composition for achieving another object is to include an acid generator that generates an acid by irradiation with a copolymer represented by the following formula (1) and radiation.

Hereinafter, a novel photoresist copolymer and a photoresist composition comprising the same according to the present invention will be described in detail.

The composition of the positive photoresist of the present invention is a composition prepared by dissolving a base resin, an acid generator, and some additives represented by the following formula (1) used as a matrix resin in a solvent.

[Formula 1]

In Chemical Formula 1, R ₁ , R ₂ , R ₃ , and R ₄ are each independently a hydrogen atom or a methyl group, and R ₅ , R ₆ , R ₇ , and R ₈ are each independently a hydrogen atom, an alkali group, or an alkoxy group. , An alkoxycarbonyl group or a halogen group is represented, and h and g are integers of 0-8, respectively. w, x, y, and z are numbers representing repeating units, respectively, and satisfy a relationship of 0.3 w 0.9, 0.01 x 0.3, 0.1, y 0.6, and 0.01 z 0.5, and w + x + y = 1. And Am is —NR ₉ R ₁₀ , cyclic divalent amines, cyclic divalent amines containing oxygen or sulfur, wherein R ₉ and R ₁₀ are each independently a hydrogen atom, an alkyl group, an aryl group, or a phenyl group.

In addition, the hydroxyl group in Chemical Formula 1 serves to improve adhesion and heat resistance, t-butyl acetate group is converted to carboxylic acid by the action of acid during exposure to enhance the dissolution rate, the amide group is exposed It maintains its affinity with the acid generated during the reaction, preventing basic components in the air from contacting the acid and preventing the acid from diffusing over adjacent distances. That is, this amide group plays a role of stabilizing the acid without being changed by the action of the acid.

In Formula 1, 10 to 50% of the substitution amount of the t-butyl acetate group is appropriate, and 1 to 30% of the substitution amount of the amide group is appropriate. Here, if too much t-butyl acetate group or amide group is substituted, the sensitivity is lowered. If the amount is too small, the difference in dissolution rate between the exposed portion and the non-exposed portion decreases, resulting in a poor pattern. That is, the substitution amount of the t-butyl acetate group and the amide group is most appropriate around 25 to 35% and 5 to 15%, respectively, and the reduction amount of polyhydroxystyrene is suitably 5% to 20%.

When the polyhydroxy styrene is reduced to 20% or more, the amount of unsaturated hydrocarbons is reduced, so that absorption in the far ultraviolet region is reduced. However, in the present invention, 5 to 10% of the polyhydroxy styrene reduces the etching resistance. Polyhydroxysterene reduction is most suitable. The molecular weight of the base resin may be up to 1,000 ~ 1,000,000 polystyrene standard molecular weight, 5,000 ~ 50,000 is most appropriate.

Examples of the acid generator used in the present invention include onium salt-based iodide salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like. Among the salts, triphenylsulfonium triflate, diphenyl (4-methylphenyl) sulfonium triflate, triphenylsulfonium, hexafluoroantimonate, diphenylidonium triflate, diphenyliodium methylbenzenesulfon Nate, bis (cyclohexylsulfonyl) diazomethane, bis (2, 4- dimethylphenylsulfonyl) diazomethane, etc. are especially preferable.

Examples of the halogen compound include 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, phenyl-bis (trichloromethyl) -s-triazine and naphthyl-bis (trichloromethyl) -s -Triazine. In addition to these, there are 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaptoquinone compounds, which are diazoketone compounds, and sulfone compounds, sulfonic acid compounds, and nitrobenzyl compounds. Particularly preferred compounds among these acid generators are onium salt compounds and diazoketone compounds. The acid generator is used 0.1 to 30 parts by weight based on 100 parts by weight of the total solid component, it is particularly preferably used in 0.3 to 10 parts by weight. Said acid generator can be used individually or in mixture of 2 or more types.

In the present invention, if necessary, a compound that is decomposed by an acid and promotes dissolution in a developing solution may be used. As a compound which decomposes | dissolves with an acid and accelerates | dissolutions with respect to a developing solution, the compound in which the aromatic polyhydroxy compound was protected by the t-butoxy carbooxy group is mentioned. The amount of the resist used is 5 to 80 parts by weight, preferably 10 to 50 parts by weight based on 100 parts by weight of the total solid component.

The composition of this invention can use an additive as needed. Such additives include surfactants, azo compounds, antihalation agents, adhesion aids, storage stabilizers, and antifoaming agents. Examples of the surfactant include polyoxylauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether, polyethylene glycol dilaurate and the like. These surfactants are preferably used in an amount of 2 parts by weight or less based on 100 parts by weight of the total solid component. Moreover, in addition to the said component, in the positive photoresist composition of this invention, a light absorber may be used in order to improve a sensitivity and resolution. As such a light absorber, a compound of benzophenones or a compound of naphthoquinones is preferable. The amount used is 0.2-30 weight% with respect to a total solid component, Preferably it is 0.5-10 weight%.

In addition, a basic compound may be used to prevent diffusion of acid generated after exposure. Examples of the basic compound include amine compounds and ammonium compounds. For example, triphenyl amine and tetramethylammonium hydroxide. The addition amount of basic compound is 0.05-5 weight part with respect to a total solid component. If the amount is larger than this, the diffusion of the acid is reduced while the sensitivity is disadvantageous.

The photoresist composition in the present invention is usually used after being dissolved in a suitable solvent. In order to obtain a uniform and flat coating film, a solvent having an appropriate evaporation rate and viscosity should be used. Examples of the solvent having such physical properties include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, Diethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl eketone, cyclohexanone, methyl 2- Hydroxypropionate, ethyl 2-hydroxypropionate- 2-heptanone, N-methyl pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, ethyl pyruvate, n-amyl Acetate, ethyl lactap, gamma-butyrolactone, etc. , In some cases, and use of such single or mixed solvent of two or more thereof. The amount of the solvent is adjusted to be uniformly formed on the wafer using an appropriate amount depending on the physical properties of the solvent, that is, volatility and viscosity.

The composition of the present invention is prepared in the form of a solution, applied on a wafer substrate and dried to form a photoresist coating film. At this time, as a coating method on a board | substrate, a resist solution is manufactured and filtered, and this solution can be apply | coated on a board | substrate by methods, such as rotational coating, a shed | coating, or roll coating.

The resist film coated by this method must be partially irradiated with radiation to form a fine pattern. Although the radiation used at this time is not specifically limited, For example, i-ray which is ultraviolet-ray, KrF excimer laser, ArF excimer laser, X-ray, an electron beam, etc. are mentioned.

The developer used for the last development is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, triethylamine, tetramethyl ammonium hydroxide, tetraethylammonium hydroxide It is used by selecting from an aqueous solution containing a lock seed and the like. Among these, tetramethylammonium hydroxide is preferable. If necessary, surfactants, water-soluble alcohols, and the like may be used as additives.

The present invention is specifically described by the following synthesis examples and examples. However, the present invention is not limited to these synthesis examples and examples.

Synthesis Example 1

20 g of 7% reduced polyhydroxystyrene was dissolved in 160 g of acetone, followed by stirring 8.1 g of t-butylbromoacetate, 0.4 g of N, N-dipropyl bromoacetate, and 3.6 g of potassium aodide 8.9 g of potassium carbonate. Add in order. The reaction was stirred at 60 ° C. for 5 hours and then cooled to room temperature to neutralize with glacial acetic acid. After neutralization, the excess precipitates the resin using distilled water. The precipitated resin was filtered, washed with distilled water, dehydrated and dried, and then dissolved in acetone. The precipitated resin was then precipitated, washed, dehydrated and dried in distilled water. The hydroxyl value of polyhydroxystyrene was 25 mol% with N-N and N-N. 22 g of polyhydroxystyrene having 1 mol% of a dipropyl acetamide group substituted and having a polystyrene standard equivalent molecular weight of 6500 were obtained.

Synthesis Example 2

20 g of 7% reduced polyhydroxystyrene was dissolved in 160 g of acetone, followed by stirring 8.1 g of t-butylbromoacetate, 8.1 g of N, N-dipropyl bromoacetate, and 4.1 g of potassium aodide, 10.2 g of potassium carbonate. Add in order. The reaction was stirred at 60 ° C. for 5 hours and then cooled to room temperature to neutralize with glacial acetic acid. Post-treatment of the reaction product was carried out in the same manner as in Synthesis example 1, where the hydroxyl group of polyhydroxystyrene was substituted with 25 mol% of t-butyl acetate group and 15% of N, N-dipropyl acetamide group, and the polystyrene standard molecular weight 21 g of polyhydroxystyrenes were obtained.

Synthesis Example 3

20 g of 7% reduced polyhydroxystyrene was dissolved in 160 g of acetone, followed by stirring 8.1 g of t-butylbromoacetate, 3.7 g of N, N-dipropyl bromoacetate, 4.9 g of potassium aodide, and 12.1 g of potassium carbonate. Add in order. The reaction was stirred at 60 ° C. for 5 hours and then cooled to room temperature to neutralize with glacial acetic acid. Post-treatment of the reaction product was carried out in the same manner as in Synthesis example 2, wherein the hydroxyl group of polyhydroxystyrene was substituted with 25 mol% of t-butyl acetate group and 10% of N, N-dipropyl acetamide group, and the polystyrene standard molecular weight 21g of polyhydroxystyrenes which were this 7000 were obtained.

Synthesis Example 4

Synthesis was carried out in the same manner as in Synthesis Example 2 except that 0.3 g of 4-morpholinyl bromoacetate was used instead of 0.4 g of N, N-dichlorophyll bromoacetate in Synthesis Example 2, resulting in polyhydroxystyrene. The hydroxyl value of was substituted with 25 mol% of t-butyl acetate groups and 1 mol% with 4-morpholinyl acetate, and 21g of polyhydroxystyrenes with a polystyrene standard molecular weight of 6600 were obtained.

Synthesis Example 5

Synthesis was carried out in the same manner as in Synthesis Example 2, except that 1.7 g of 4-morpholinyl bromoacetate was used instead of 0.4 g of N, N-dichlorophyll bromoacetate in Synthesis Example 2, resulting in polyhydroxystyrene. The hydroxyl value of was substituted with 25 mol% of t-butyl acetate groups and 5 mol% with 4-morpholinyl acetate, and 22g of polyhydroxystyrenes with a polystyrene standard molecular weight of 6900 were obtained.

Synthesis Example 6

Synthesis was carried out in the same manner as in Synthesis Example 2, except that 3.5 g of 4-morpholinyl bromoacetate was used instead of 0.4 g of N, N-dichlorophyll bromoacetate in Synthesis Example 2, resulting in polyhydroxystyrene. The hydroxyl value of was substituted with 25 mol% of t-butyl acetate groups and 5 mol% with 4-morpholinyl acetate, and 24g of polyhydroxystyrenes with a polystyrene standard cyclic molecular weight of 7,200 were obtained.

Synthesis Example 7

After dissolving 20 g of 7% reduced polyhydroxystyrene in 160 g of acetone, 8.1 g of t-butylbromoacetate, 3.4 g of potassium aodide, and 8.6 g of potassium carbonate are added sequentially with stirring. The reaction is stirred at 60 ° C. for 5 hours, then cooled to room temperature and neutralized with glacial acetic acid. Post-treatment of the reaction product was carried out in the same manner as in Synthesis example 2, whereby the hydroxyl group of polyhydroxystyrene was substituted with 25 mol% of t-butyl acetate group to obtain 21 g of polyhydroxystyrene having a polystyrene standard molecular weight of 6,400.

Synthesis Example 8

Synthesis was carried out in the same manner as in Synthesis Example 6, except that 20 g of unreduced polyhydroxystyrene (polystyrene standard molecular weight 5,300) was used. The hydroxyl group of the polyhydroxystyrene was 25 mol% and 4-mole of t-butyl acetate group. 5 mol% polylinyl acetate was substituted, and 21 g of polyhydroxystyrene having a polystyrene standard molecular weight of 6,700 was obtained.

An embodiment of obtaining a photoresist composition using a copolymer of the above synthesis example and forming a photoresist pattern using the same is as follows.

Example 1

100 parts by weight of a polyhydroxystyrene polymer in which the hydroxyl group of the polyhydroxystyrene obtained in Synthesis Example 2 was substituted with 25 mol% of t-butyl acetate group and 1 mol% of N, N-dipropyl acetamide group, and triphenyl as an acid generator 0.8 parts by weight of sulfonium triflate was dissolved in 350 parts by weight of ethyl lactate, and then filtered through a 0.1 μm membrane filter to obtain a resist liquid. The resist was applied using a spinner and baked at 130 ° C. for 60 seconds to obtain a film having a thickness of 0.7 μm. The film was exposed through a pattern chromium mask using a 248 nm KrF excimer laser stepper, baked at 130 ° C. for 60 seconds, then developed and dried in a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds to form a resist pattern. Formed. The resist pattern thus formed was a line-and-space pattern of 0.35 μm at an exposure dose of 25 mJ / cm 2, and the cross-sectional shape of the pattern was rectangular, but the top portion was rounded. However, it was left for 1 hour after exposure and then baked at 130 ° C. for 60 seconds to deform the pattern and form T-top.

Example 2

Except that the hydroxyl group of the polyhydroxystyrene obtained in Synthesis Example 3 used 100 parts by weight of a polyhydroxystyrene polymer substituted with 25 mol% of t-butyl acetate group and 5 mol% of N, N-dipropyl acetamide group A resist pattern was formed in the same manner as in Example 1. The resist pattern thus formed was a line-and-space pattern of 0.25 탆 at an exposure dose of 25 mJ / cm 2, and the cross-sectional shape of the pattern showed a good rectangular shape.

Example 3

Except that the hydroxyl group of the polyhydroxystyrene obtained in Synthesis Example 4 used 100 parts by weight of a polyhydroxystyrene polymer substituted with 25 mol% of t-butyl acetate group and 10 mol% of N, N-dipropyl acetamide group A resist pattern was formed in the same manner as in Example 1. The resist pattern thus formed was a line-and-space pattern of 0.27 μm at an exposure dose of 35 mJ / cm 2, and the cross-sectional shape of the pattern showed a good rectangular shape.

Example 4

100 parts by weight of the polymer used in Example 1 and 2.5 parts by weight of trifetylsulfonium triflate were dissolved in 350 parts by weight of ethyl lactate. A resist pattern was formed in the same manner as in Example 1 except that 40 mol% of tetramethylammonium hydroxide was added to triphenylsulfonium triflate. The resist pattern thus formed was a line-and-space pattern of 0.25 탆 at an exposure dose of 30 mJ / cm 2, and the cross-sectional shape of the pattern showed a good rectangular shape. In addition, it was left for 1 hour after exposure and then baked at 130 ° C. for 60 seconds, showing a good line-and-space pattern of 0.25 μm without deforming the pattern.

Example 5

100 parts by weight of the polymer used in Example 2 and 2.2 parts by weight of trifetylsulfonium triflate were dissolved in 330 parts by weight of ethyl lactate. A resist pattern was formed in the same manner as in Example 2 except that 20 mol% of tetramethylammonium hydroxide was added to the triphenylsulfonium triflate. The resist pattern thus formed was a line-and-space pattern of 0.20 m at an exposure dose of 30 mJ / cm 2, and the cross-sectional shape of the pattern showed a good rectangular shape.

Example 6

100 parts by weight of a polyhydroxystyrene polymer in which the hydroxyl group of the polyhydroxystyrene obtained in Synthesis Example 5 was substituted with 25 mol% of t-butyl acetate group and 1 mol% of 4-morpholinyl acetate, and triphenylsulfoni as an acid generator 1.0 part by weight of um triflate was dissolved in 350 parts by weight of ethyl lactate, and then filtered through a 0.1 µm membrane filter to obtain a resist liquid. The resist was applied using a spinner and baked at 120 ° C. for 60 seconds to obtain a 0.7 μm thick film. The film was exposed through a pattern chromium mask using a 248 nm KrF excimer laser stepper, baked at 130 ° C. for 60 seconds, then developed and dried in a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds to form a resist pattern. Formed. The resist pattern thus formed was a line-and-space pattern of 0.35 μm at an exposure dose of 25 mJ / cm 2, and the cross-sectional shape of the pattern was rectangular, but the top portion was rounded. However, it was left for 1 hour after exposure and then baked at 130 ° C. for 60 seconds to deform the shape of the pattern, indicating T-top formation.

Example 7

Example 6 except that the hydroxyl group of the polyhydroxystyrene obtained in Synthesis Example 6 used 100 parts by weight of a polyhydroxystyrene polymer substituted with 25 mol% of t-butyl acetate group and 5 mol% of 4-morpholinyl acetate. A resist pattern was formed in the same manner as in. The resist pattern thus formed was a line-and-space pattern of 0.20 m at an exposure dose of 25 mJ / cm 2, and the cross-sectional shape of the pattern showed a good rectangular shape.

Example 8

Example 6 except that the hydroxyl group of the polyhydroxystyrene obtained in Synthesis Example 7 used 100 parts by weight of a polyhydroxystyrene polymer substituted with 25 mol% of t-butyl acetate group and 10 mol% of 4-morpholinyl acetate. A resist pattern was formed in the same manner as in. The resist pattern thus formed was a line-and-space pattern of 0.20 m at an exposure dose of 30 mJ / cm 2, and the cross-sectional shape of the pattern showed a good rectangular shape.

Example 9

100 parts by weight of the polymer used in Example 6 and 3.0 parts by weight of trifetylsulfonium triflate were dissolved in 330 parts by weight of ethyl lactate. A resist pattern was formed in the same manner as in Example 6 except that 50 mol% of tetramethylammonium hydroxide was added to the triphenylsulfonium triflate. The formed resist pattern was a line-and-space pattern of 0.30 mu m at an exposure dose of 30 mJ / cm 2, and the cross-sectional shape of the pattern showed a good rectangular shape. In addition, leaving for 1 hour after exposure and baking at 130 ° C. for 60 seconds showed a good line-and-space pattern of 0.25 μm without deforming the shape of the pattern.

Example 10

100 parts by weight of the polymer used in Example 7 and 2.5 parts by weight of trifetylsulfonium triflate were dissolved in 330 parts by weight of ethyl lactate. A resist pattern was formed in the same manner as in Example 6 except that 30 mol% of tetramethylammonium hydroxide was added to the triphenylsulfonium triflate. The formed resist pattern was a line-and-space pattern of 0.17 mu m at an exposure dose of 35mj / cm < 2 >, and the cross-sectional shape of the pattern showed a good rectangular shape.

Looking at the results of the comparative review of the present inventors with respect to the above embodiments are as follows.

Comparative Example 1

100 parts by weight of the polyhydroxystyrene polymer in which the hydroxyl group of the polyhydroxystyrene obtained in Synthesis Example 8 was substituted with 25 mol% of t-butyl acetate group, and 0.8 parts by weight of triphenylsulfonium triflate were dissolved in 350 parts by weight of ethyl lactate. Evaluation was performed in the same manner as in Example 1 after the test. The resist pattern thus formed was a line-and-space pattern of 0.45 탆, and the cross-sectional shape of the pattern was poor as a T-top form.

Comparative Example 2

100 parts by weight of a polyhydroxystyrene polymer in which the hydroxyl group of the polyhydroxystyrene obtained in Synthesis Example 9 was substituted with 25 mol% of t-butyl acetate group and 5 mol% of 4-morpholinyl acetate, triphenylsulfonium triflate 2.5 parts by weight was dissolved in 350 parts by weight of ethyl lactate. A resist pattern was formed in the same manner as in Example 6 except that 30 mol% of tetramethylammonium hydroxide was added to the triphenylsulfonium triflate. The resist pattern thus formed exhibited a pattern of 0.18 μm at an exposure dose of 57 mj / cm 2.

As described above, the novel photoresist copolymer and the photoresist composition including the same according to the present invention are synthesized with a copolymer represented by the repeating unit represented by the formula (1), and then prepared and tested by a photoresist. Resist patterns with excellent sensitivity, high resolution, heat resistance and stability after exposure to radiation such as an ultraviolet KrF excimer laser and excellent substrates were obtained regardless of the type of substrate.

Claims (10)

The copolymer for photoresists whose polystyrene reduced average molecular weight represented by the copolymer of following formula (1) is 1000-1,000,000. [Formula 1] In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ are each independently a hydrogen atom or a methyl group, and R ₅ , R ₆ , R ₇ , R ₈ are each independently a hydrogen atom, an alkali group, an alkoxy group, An alkoxycarbonyl group or a halogen group is represented, h and g are the integers of 0-8, respectively. w, x, y, and z are numbers representing repeating units, respectively, and satisfy a relationship of 0.3 w 0.9, 0.01 x 0.3, 0.1, y 0.6, and 0.01 z 0.5, and w + x + y + z = 1. And Am is —NR ₉ R ₁₀ , cyclic divalent amines, cyclic divalent amines containing oxygen or sulfur, wherein R ₉ and R ₁₀ are each independently a hydrogen atom, an alkyl group, an aryl group, or a phenyl group. According to claim 1, wherein the substitution amount of the t-butyl acetate group in the formula (1) is 10 to 50%, the substitution amount of the amide group is 1 to 30%, the reduced amount of polyhydroxy styrene is 5% to 20% Copolymer for photoresist which is used. A chemically amplified positive photoresist composition comprising a copolymer represented by the following formula (1) and an acid generator that generates an acid by irradiation with radiation. [Formula 1] In formula (I), R ₁ , R ₂ , R ₃ , R ₄ are each independently a hydrogen atom or a methyl group, and R ₅ , R ₆ , R ₇ , R ₈ are each independently a hydrogen atom, an alkali group, an alkoxy group, An alkoxycarbonyl group or a halogen group is represented, h and g are the integers of 0-8, respectively. w, x, y, and z are numbers representing repeating units, respectively, and satisfy a relationship of 0.3 w 0.9, 0.01 x 0.3, 0.1, y 0.6, and 0.01 z 0.5, and w + x + y + z = 1. And Am is —NR ₉ R ₁₀ , cyclic divalent amines, cyclic divalent amines containing oxygen or sulfur, wherein R ₉ and R ₁₀ are each independently a hydrogen atom, an alkyl group, an aryl group, or a phenyl group. The method of claim 3, wherein the acid generator is triphenylsulfonium triflate, diphenyl (4-methylphenyl) sulfonium triflate, diphenyl (4-t- butylphenyl) sulfonium triflate, diphenyl ( 4-methoxyphenyl) sulfonium triflate, triphenylsulfonium hexafluoroantimonate, diphenylidonium triflate, diphenyliodium methylbenzenesulfonate, bis (cyclohexylsulfonyl) diazo Methane, bis (2,4-dimethylphenylsulfonyl) diazomethane, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, phenyl-bis (trichloromethyl) -s- A positive photoresist composition characterized by using at least one selected from triazine and naphthyl-bis (trichloromethyl) -s-triazine. The positive photoresist composition of claim 3, wherein the acid generator uses 0.1 to 30 parts by weight based on 100 parts by weight of the total solid component. The total solid component according to claim 3, wherein the compound, which is decomposed by an acid in the photoresist composition to promote dissolution in a developing solution, is a compound protected by a t-butoxycarbooxy group, which is an aromatic polyhydroxy compound, by a total weight of 100 parts by weight. A positive photoresist composition, which is added in an amount of 5 to 80 parts by weight per part. The said photoresist composition is a surfactant, an azo compound, an antihalation agent, an adhesion | attachment adjuvant, a storage stabilizer, and an antifoamer. Surfactants include one or more selected from polyoxy lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonylphenol ether, polyethylene glycol dilaurate A positive photoresist composition comprising the addition of two substances. A positive photoresist composition according to claim 3, wherein a compound of benzophenones or a compound of naphthoquinones is added to the photoresist composition as a light absorber for improving sensitivity and resolution. A positive photoresist composition according to claim 3, wherein triphenyl amine and tetramethylammonium hydroxide are added to the photoresist composition as an amine compound or an ammonium compound which is a basic compound. The ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol ether, diethylene as solvents of the photoresist composition. Glycol dipropyl ether, diethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl ether ketone, cyclohexane Non, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-heptanone, N-methyl pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, ethyl Pyruvate, n-amyl acetate, ethyl lactape, gamma-bu At least one selected from a lactone as a positive photoresist composition which is characterized by using in combination.