KR100251463B1 - Positive photoresist polymer and chemical amplified positive photoresist composition containing the same - Google Patents

Abstract

PURPOSE: A polymer for preparing positive photoresist and a chemically amplified positive photoresist composition containing the polymer are provided, to improve the adhesion to a substrate, the resolution, the heat resistance, the etching resistance and the storage stability after exposure. CONSTITUTION: The polymer has the polystyrene conversion mean molecular weight of 2,000-1,000,000, and its repeating unit is represented by the formula 1, wherein R1, R5 and R8 are independent each another and are H or an alkyl group of C1-C10; R2, R3, R9 and R10 are independent each another and are H, -OH, an alkoxy group or an acetoxy group; R4 and R11 are independent each another and are H, a cyclic, straight or branched alkyl group of C1-C15, an alkoxyalkyl group, an alkoxymethylene group, tetrahydropyranyl group or tetrahydrofuranyl group; R6 and R7 are independent each another and are H, -OH, a cyclic, straight or branched alkyl group of C1-C15, a carboxyl group, an alkoxyalkyloxycarbonyl group, an alkoxymethoxycarbonyl group, tetrahydropranyloxycarbon group or tetrahydrofuranyloxycarbonyl group; and l, m, n and o represent the repeating number, 0≤ 0/(m+n+o)≤0.7, 0.1≤m/(l+n+o)≤0.7, 0≤n/(l+m+o)≤0.7, and 0≤o/(l+m+n)≤0.7. The composition comprises the polymer; an acid generator; and a solvent.

Description

Polymer for preparing positive photoresist and composition of chemically amplified positive photoresist containing same

The present invention relates to a polymer for producing positive photoresist and a chemical amplified positive photoresist compositanon containing the same.

More specifically, the repeating unit relates to a polymer represented by the following general formula (I) and a chemically amplified photoresist composition composed of the polymer, an acid generator and a solvent.

[Formula 1]

(I)

Wherein R ₁ , R ₅ , and R ₈ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, each independently, and R ₂ , R ₃ , R ₉ , and R ₁₀ represent a hydrogen atom, a hydroxyl group, or an alkoxy group , Or an acetoxy group, each independently. R ₄ and R ₁₁ represent a hydrogen atom, a cyclic, straight or branched chain alkyl group having 1 to 15 carbon atoms, an alkoxyalkyl group, an alkoxymethylene group, a tetrahydropyran (hereinafter referred to as THP) group, or tetrahydrofuran ( Tetrahydrofuran: hereinafter referred to as THF). R ₆ and R ₇ are hydrogen atom, hydroxyl group, cyclic, straight or branched chain alkyl group having 1 to 10 carbon atoms, carboxylic acid, alkoxyalkyloxycarbonyl group, alkoxymethoxycarbonyl group, tetrahydropyranyloxycarbonyl group, or It represents a tetrahydrofuranyloxycarbonyl group and is independent of each other. l, m, n and o are the numbers representing the repeating units, respectively, 0≤l / m + n + o≤0.7, 0.1≤m / l + n + o≤0.7, 0≤n / ℓ + m + o≤0.7 And 0 ≦ o / l + m + n ≦ 0.7.

Recently, due to the high integration of semiconductor devices, ultra-fine patterns of 0.2 micron or less are required in the manufacture of ultra-LSI, etc. As a result, the exposure wavelength is further shortened in the g-line or I-line region used in the past. Research on lithography using ultraviolet light, KrF excimer lasers, ArF excimer lasers, X-rays and electron beams is drawing attention.

In the case of phenol resins, which are matrix polymers of resists conventionally used for g-rays, i-rays, and KrF excimer lasers, ArF excimer lasers have high absorption of light and are not suitable for use as matrix resins. In order to compensate for this, many studies have been conducted on the use of polyacrylate derivatives having a relatively low light absorption in the ArF excimer laser as the matrix resin. However, the polyacrylate has a big disadvantage that the absorption of light in the ArF excimer laser region is small but the etching resistance is poor. Recently, a method of increasing the etching resistance by introducing an alicyclic derivative to polyacrylate has been researched to compensate for such disadvantages. However, due to the hydrophobicity of the early cyclic derivatives to improve the etching resistance has a disadvantage of low affinity with the developer.

The matrix resin having a hydrophilic group while complementing the etching resistance may be a copolymer of maleic anhydride and an olefin. However, these resins did not yield satisfactory results.

An object of the present invention is to prepare a matrix resin having etching resistance and hydrophilicity and a resist using the resin while satisfying a pattern of 0.2 micron or less. In order to satisfy the pattern of 0.2 micron or less, the adhesion between the composition of the resist and the substrate is an important factor. In the case of the conventional matrix resin, carboxylic acid was introduced as a means for improving adhesion. However, when the amount of the carboxylic acid increases to some extent or more, the solubility increases in the basic aqueous solution, which causes the disadvantage of changing the basic concentration of the developer.

The present invention is to improve the disadvantage that the conventional chemically amplified photoresist has a high absorption of light at short wavelengths, such as ArF excimer laser, a satisfactory pattern of less than 0.2 micron, and the etching resistance is poor, to improve the hydroxyl group in the matrix resin Adherence was improved to improve adhesion, and cyclic derivatives were introduced into the main chain and alicyclic derivatives in order to improve the etching resistance. As a result, high resolution, heat resistance, etching resistance and post exposure were obtained. The present invention was completed by finding that the storage stability is excellent and that an excellent pattern can be obtained regardless of the type of substrate.

An object of the present invention is to provide a copolymer in which the repeating unit is represented by the following general formula (I).

[Formula 1]

(I)

Wherein R ₁ , R ₅ , and R ₈ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, each independently, and R ₂ , R ₃ , R ₉ , and R ₁₀ represent a hydrogen atom, a hydroxyl group, or an alkoxy group , Or an acetoxy group, each independently. R ₄ and R ₁₁ represent a hydrogen atom, a cyclic, straight or branched chain alkyl group having 1 to 15 carbon atoms, an alkoxyalkyl group, an alkoxymethylene group, a THP group, or a THF group. R ₆ and R ₇ are hydrogen atom, hydroxyl group, cyclic, straight or branched chain alkyl group having 1 to 10 carbon atoms, carboxylic acid, alkoxyalkyloxycarbonyl group, alkoxymethoxycarbonyl group, tetrahydropyranyloxycarbonyl group, or It represents a tetrahydrofuranyloxycarbonyl group and is independent of each other. l, m, n and o are the numbers representing the repeating units, respectively, 0≤l / m + n + o≤0.7, 0.1≤m / l + n + o≤0.7, 0≤n / ℓ + m + o≤0.7 And 0 ≦ o / l + m + n ≦ 0.7.

Still another object of the present invention is to provide a chemically amplified positive photoresist composition composed of a copolymer represented by the general formula (I), an acid generator and a solvent.

The present invention provides a copolymer for producing a positive photoresist represented by the following general formula (I), and a chemically amplified positive photoresist composition composed of the copolymer, an acid generator, and a solvent.

[Formula 1]

(I)

Wherein R ₁ , R ₅ , and R ₈ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, each independently, and R ₂ , R ₃ , R ₉ , and R ₁₀ represent a hydrogen atom, a hydroxyl group, or an alkoxy group , Or an acetoxy group, each independently. R ₄ and R ₁₁ represent a hydrogen atom, a cyclic, straight or branched chain alkyl group having 1 to 15 carbon atoms, an alkoxyalkyl group, an alkoxymethylene group, a THP group, or a THF group. R ₆ and R ₇ are hydrogen atom, hydroxyl group, cyclic, straight or branched chain alkyl group having 1 to 10 carbon atoms, carboxylic acid, alkoxyalkyloxycarbonyl group, alkoxymethoxycarbonyl group, tetrahydropyranyloxycarbonyl group, or It represents a tetrahydrofuranyloxycarbonyl group and is independent of each other. l, m, n and o are the numbers representing the repeating units, respectively, 0≤l / m + n + o≤0.7, 0.1≤m / l + n + o≤0.7, 0≤n / ℓ + m + o≤0.7 And 0 ≦ o / l + m + n ≦ 0.7.

First, the copolymer in which the repeating unit is represented by the general formula (I) is prepared by preparing monomers represented by the following general formula (II), structural formula (III), general formula (IV), and general formula (V) in the presence of a polymerization catalyst. can do.

Ⅱ Ⅲ Ⅳ Ⅴ

Wherein R ₁ , R ₅ , and R ₈ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, each independently, and R ₂ , R ₃ , R ₉ , and R _{10 each} represent a hydrogen atom, a carbon atom at 1 Up to 15 cyclic, straight or branched alkyl groups, alkoxyalkyl groups, alkoxymethylene groups, THP groups, or THF groups are shown. R ₆ and R ₆ are hydrogen, hydroxyl, cyclic, straight or branched alkoxycarbonyl group having 1 to 10 carbon atoms, cyclic, straight or branched chain alkyl group having 1 to 10 carbon atoms, carboxylic acid, An alkoxyalkyloxycarbonyl group, an alkoxymethoxycarbonyl group, a tetrahydropyranyloxycarbonyl group, or a tetrahydrofuranyloxycarbonyl group is shown and is independent of each other.

The copolymer of the present invention may be used as a matrix resin by copolymerizing the monomer represented by the general formula (II) or the monomer represented by the general formula (IV) with maleic anhydride represented by the structural formula (III). Can be. In addition, the monomers represented by the general formula (II), the structural formula (III), and the general formula (IV) can be used as a matrix resin by terpolymerization, and copolymerizes the general formula (II) and the general formula (V). It can also be used as a matrix resin. The monomer represented by general formula (IV) is used, adjusting the usage-amount appropriately according to the density | concentration of a developing solution.

Such copolymers or terpolymers may be block copolymers, random copolymers or graft copolymers. As for the polymerization method of the polymer represented by the said general formula (I), radical polymerization is preferable. The polymerization reaction can be carried out by bulk polymerization, solution polymerization, suspension polymerization, block-suspension polymerization, emulsion polymerization, etc., and polymerization solvents include benzene, toluene, xylene, halogenated benzene, diethyl ether, THF, and esters. At least one selected from among lactones, ketones and amides. As a radical polymerization initiator, it is used as a general radical polymerization initiator such as azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide, azobisisocapronitrile, azobisisovaleronitrile, and t-butylhydroperoxide. If there is no special limitation.

The polymerization temperature of the polymers represented by the general formula (I) is appropriately selected and used depending on the type of catalyst. For example, when a polymerization catalyst is azobisisobutyronitrile, 60-90 degreeC is suitable. The molecular weight of the polymer can be appropriately adjusted using the amount of the polymerization initiator and the reaction time. The residual amount of monomer remaining in the reaction mixture after the end of the polymerization should be 10% by weight or less with respect to the polymer, preferably 3% by weight or less. When unreacted monomer is 3 weight% or more, it is preferable to remove a monomer by distillation under reduced pressure or a solvent.

The polystyrene reduced average molecular weight of the polymer represented by the general formula (I) is 1,000 to 1,000,000, and 3,000 to 50,000 is preferable in consideration of sensitivity, developability, coatability, heat resistance, and the like as a photoresist. If the average molecular weight in terms of polystyrene is less than 3,000, the coating property is inferior, and if it is larger than 70,000, there is a disadvantage in that the sensitivity, resolution, developability, etc. are poor. Moreover, 1-5 are preferable, and, as for molecular weight distribution map, 1.0-1.8 are especially preferable.

Acid generators used in the present invention include onium salt-based iodide salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like, among these salts, triphenylsulfonium triflate and diphenyl (4). -Methylphenyl) sulfonium triplate, diphenyl (4-t-butylphenyl) sulfonium triplate, diphenyl (4-methoxyphenyl) sulfonium triplate, diphenyl (naphthyl) sulfonium tree Plate, dialkyl (naphthyl) sulfonium triplate, triphenylsulfonium hexafluoroantimonate, diphenyl iodinium triplate, diphenyl idiumiumbenzenebenzenesulfonate, bis (cyclohexylsolo) Nil) diazomethane and bis (2,4-dimethylphenylsulfonyl) diazomethane have good effects.

In particular, unlike conventional acid generators, onium salts such as the following general formulas (VI), (IX) and (IX) serve as dissolution inhibitors in the non-exposed part and exhibit dissolution accelerator effects in the exposed part. This onium salt is synthesized using perfluoroalkanesulfonic anhydride [CF ₃ (CF ₂ ) _n SO ₂ —O—SO ₂ (CF ₂ ) _n CF ₃ ].

[Formula 3]

Ⅵ Ⅶ Ⅷ

Herein, R ₁ , R ₂ , and R ₅ represent an alkyl group, an allyl group, a naphthalenyl group, or an aryl group, and are each independently, and R ₃ and R ₄ represent a hydrogen atom, an alkyl group, or an alkoxy group, and are each independently. n is an integer of 0-14.

The acid generator is used in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the total solid component, and particularly preferably 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 which is decomposed by an acid to promote dissolution in a developer may be used. Compounds which are decomposed by an acid to promote dissolution in a developing solution are alicyclic derivatives having a functional group which can be easily changed to a deprotecting group by an acid such as a t-butyl ester group. 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 photoresist composition of this invention can use an additive as needed. Such additives include surfactants, anti-halation agents, adhesion aids, storage stabilizers, and antifoaming agents. Examples of the surfactant include polyoxylauryl ether, polyoxystearyl ether, polyoxyethylene oleyl ether, polyethylene glycol dilaurylate 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. In addition, a basic compound may be used to prevent diffusion of acid generated after exposure. 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, but the sensitivity is lowered.

The photoresist composition of the present invention is used after being dissolved in a solvent having a suitable evaporation rate and viscosity in order to obtain a uniform and flat coating film. Examples of the solvent having such physical properties include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate , Propylene glycol monopropyl ether acetate, methyl ethyl ketone, cyclohexanone, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-heptanone, ethyl lactate, gamma-butyrolactone, and the like. Depending on these, these single or 2 or more types of mixed solvent are used. 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, ie volatility, viscosity, and the like.

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 substrate, a resist solution is prepared and filtered, and then the solution can be applied onto the substrate by a method such as rotary coating, spill 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 rays, KrF excimer laser which is far ultraviolet rays, ArF excimer laser, X-rays, an electron beam which is a charged particle beam, etc. are heated according to the kind of acid generator. It can also be processed.

The developer used for the last development is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, n-propylamine, triethylamine, tetramethylammonium 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.

<Acid generator synthesis>

13 g of t-butyl o-tolyloxy acetate and 13 g of phenyl sulfoxide were dissolved in dichloromethane and 9.5 ml of triflic anhydride was slowly added at -78 ° C. Inject. After reacting at the same temperature for 1 hour, the temperature was gradually raised and neutralized with potasum carbonate (K ₂ CO ₃ ) at -40 ° C. The reaction mixture is placed in a beaker containing excess distilled water and ether to remove the organic layer, and the aqueous layer is extracted with dichloromethane. After separating the organic layer, the solvent is removed by distillation under reduced pressure to obtain an oily product. Recrystallization of this compound with hexane and ethyl acetate yields the pure compound of formula (A) in 23 g (72%) yield.

A B

C D

In the same manner, structural formulas [B], [C], and [D] were synthesized and obtained in yields of 83%, 25%, and 51%, respectively.

<Synthesis of Monomers of Formula (II)>

Synthesis Example 1

15 g of t-butyl deoxycholate and 3.4 ml of methacryloyl chloride are dissolved in a dichloromethane solvent, and 7 ml of triethylamine is slowly added dropwise at 0 ° C. The solution is reacted for 2 hours and then washed with distilled water. The organic layer is separated, dried over anhydrous magnesium sulfate [MgSO ₄ ], and the solvent is removed by distillation under reduced pressure. The reaction product was recrystallized with ethyl acetate and n-hexane to give 11g (yield 65%) of the compound of formula (E).

E F G H I

In the same manner, compounds of formulas (F), (G), (H) and (I) were obtained in yields of 43%, 78%, 69%, and 57%, respectively.

Synthesis Example 2

After dissolving 10 g of monomer [I] in a THF / H ₂ O solvent, a catalytic amount of toluenesulfonic acid was added, followed by stirring at room temperature for 8 hours. After stirring, excess ethyl acetate is added and washed with distilled water. The organic layer was separated, dried over magnesium sulfate, and the solvent was removed by distillation under reduced pressure to obtain a pure monomer of the following structural formula (J) in a yield of 8.3 g.

J

<Synthesis of Monomers of Formula (IV)>

Synthesis Example 3

154 ml of t-butanol with 67 g of cis-5-norbornene-endo-2,3-dicarboxylic anhydride and 50 g of dimethylaminopyridine It was dissolved in and stirred at 80 ° C. for 15 hours. The reaction mixture was neutralized with an excess of 5% aqueous HCl solution, extracted with ethyl acetate, dried over anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure to obtain 91 g of a monomer of the following structural formula (K) (yield 93%).

(K)

Synthesis of Polymer

Synthesis Example (1)

10g / 2g / 0.5g of the monomer of the structural formula (E) / maleic anhydride / the monomer of the structural formula (K) was dissolved in 50 ml of toluene, and the inside of the reactor was replaced with nitrogen gas, and then 0.01 mol / L of AIBN was added. Stir at 70 ° C. for 15 hours. The reaction mixture was cooled to room temperature and then added dropwise into an excess of methanol / distilled water (4/1) mixed solvent to obtain a white precipitate. The precipitate was filtered, washed with a mixed solvent and dried in vacuo to give 6 g of resin (1). The polystyrene standard molecular weight of this resin was 23,000.

Synthesis Example (2)

10 g / 2 g / 0.3 g of the monomer of the formula (F) / maleic anhydride / the monomer of the formula (K) was dissolved in toluene and polymerized in the same manner as in the polymer synthesis example (1) to obtain 7.26 g of the resin (2). Got it. The polystyrene standard molecular weight of this resin was 34,000.

Synthesis Example (3)

10 g / 2.3 g / 1 g of the monomer of the structural formula (G) / maleic anhydride / the monomer of the structural formula (K) was dissolved in toluene and polymerized in the same manner as in the polymer synthesis example (1) to 5.6 g of the resin (3). Got it. The polystyrene standard molecular weight of this resin was 22,000.

Synthesis Example (4)

10 g / 2.1 g / 1.5 g of the monomer of the structural formula (H) / maleic anhydride / the monomer of the structural formula (K) was dissolved in toluene and polymerized in the same manner as in the polymer synthesis example (1) to 6.4 g of the resin (4). Got. The polystyrene standard molecular weight of this resin was 31,000.

Synthesis Example (5)

10 g / 2 g / 1.4 g of the monomer of the formula (I) / maleic anhydride / the monomer of the formula (K) was dissolved in toluene and polymerized in the same manner as in the polymer synthesis example (1) to obtain 7.5 g of the resin (5). Got it. The polystyrene standard molecular weight of this resin was 19,000.

Synthesis Example (6)

10 g / 10.5 g of the monomers of the above structural formulas (E) / (I) were dissolved in 120 ml of toluene, and the inside of the reactor was replaced with nitrogen gas, followed by addition of 0.05 mol / L of AIBN, followed by stirring at 90 ° C. for 3 hours. The reaction mixture is cooled to room temperature and then added dropwise into an excess of methanol / distilled water (4/1) mixed solvent to obtain a white precipitate. The precipitate was filtered, washed with a mixed solvent, and dried in vacuo to obtain 14 g of Resin (6). The polystyrene standard molecular weight of this resin was 33,000.

Synthesis Example (7)

10 g / 10.2 g of the monomers of the above structural formulas (F) / (I) were dissolved in toluene, respectively, to give 8.2 g of resin (7) in the same manner as in Synthesis Example (6). The polystyrene standard molecular weight of this resin was 25,000.

Synthesis Example (8)

The monomer of the structural formulas (E) / (J) was dissolved in 10 g / 8.9 g of toluene, respectively, and was carried out in the same manner as in Synthesis Example (6) to obtain 8.7 g of resin (7). The polystyrene standard molecular weight of this resin was 37,000.

Example 1

1.5 parts by weight of the acid generator [A] synthesized in Synthesis Example 1 based on 100 parts by weight of the resin (1) of the monomer (E) / maleic anhydride / (K) obtained in Synthesis Example (1). It was dissolved in 400 parts by weight of cypionate. The resulting solution was filtered through a 0.1 μm membrane filter to obtain a coating solution of a positive resist.

The coating liquid thus obtained was applied to a silicon wafer using a spinner and dried at 110 ° C. for 90 seconds to obtain a film having a thickness of 0.6 μm. The film was exposed through a pattern chrome mask using a 193 nm ArF excimer laser stepper and then heat treated at 110 ° C. for 90 seconds, followed by development, washing and drying for 60 seconds with a 2.38 wt% tetramethylammonium hydroxide aqueous solution. Formed.

The resist pattern thus formed was a line-and-space pattern of 0.15 mu m. The cross-sectional shape of this resist pattern was almost square, and the exposure amount was 8 mJ / cm ^2, but some acid diffusion phenomenon appeared.

Example 2

To 1.5 parts by weight of the resin (1) of the monomer (E) / maleic anhydride / (K) of the polymer synthesis example (1), 1.5 parts by weight of the acid generator [A] synthesized in the acid generator synthesis example 1 It was dissolved in 400 parts by weight of ethoxypropionate. A resist pattern was formed in the same manner as in Example 1 except that ammonium hydroxide was added to the coating liquid of the resist with respect to the acid generator.

The resist pattern thus formed was a line-and-space pattern of 0.14 mu m. The adhesion state of this resist pattern was favorable, and the cross-sectional shape was a favorable square state which is not influenced by standing waves. The exposure amount was 10 mJ / cm 2.

Example 3

A resist pattern was formed in the same manner as in Example 1 except that 2.0 parts by weight of the acid generator [B] was used instead of 1.5 parts by weight of the acid generator [A] used in Example 1.

The resist pattern thus formed was a line-and-space pattern of 0.15 mu m. The cross-sectional shape of this resist pattern was in a good rectangular shape unaffected by standing waves, and the exposure amount was 14 mJ / cm 2.

Example 4

A resist pattern was formed in the same manner as in Example 1 except that 2.0 parts by weight of the acid generator [C] was used instead of 1.5 parts by weight of the acid generator [A] used in Example 1.

The resist pattern thus formed was a line-and-space pattern of 0.16 mu m. The cross-sectional shape of this resist pattern was in a good rectangular shape unaffected by standing waves, and the exposure amount was 16 mJ / cm ² .

Example 5

A resist pattern was formed in the same manner as in Example 1 except that 2.2 parts by weight of the acid generator [D] was used instead of 1.5 parts by weight of the acid generator [A] used in Example 1.

The resist pattern thus formed was a line-and-space pattern of 0.165 mu m. The cross-sectional shape of this resist pattern was in a good rectangular shape unaffected by standing waves, and the exposure amount was 18 mJ / cm ² .

Example 6

1.5 parts by weight of the acid generator [A] obtained in Synthesis Example 1 based on 100 parts by weight of the resin (2) of the monomer F / maleic anhydride / K obtained in Synthesis Example (2), 400 parts by weight of ethyl 3-ethoxypropionate Dissolved in parts. A resist pattern was formed in the same manner as in Example 1 except that methyl ammonium hydroxide was added to the coating solution of the resist with respect to the acid generator.

The resist pattern thus formed was a line-and-space pattern of 0.17 mu m. The adhesion state of this resist pattern was favorable, and the cross-sectional shape was almost square. The exposure amount was 15 mJ / cm ² .

Example 7

1.5 parts by weight of the acid generator [A] obtained in Synthesis Example 1 based on 100 parts by weight of the resin (2) of the monomer G / maleic anhydride / K obtained in Synthesis Example (3), 400 parts by weight of ethyl 3-ethoxypropionate Dissolved in parts. A resist pattern was formed in the same manner as in Example 1 except that methyl ammonium hydroxide was added to the coating solution of the resist with respect to the acid generator.

The resist pattern thus formed was a line-and-space pattern of 0.17 mu m. The adhesion state of this resist pattern was favorable, and the cross-sectional shape was almost square. The exposure amount was 14 mJ / cm ² .

Example 8

1.5 parts by weight of the acid generator [A] obtained in Synthesis Example 1 based on 100 parts by weight of the resin (4) of the monomer H / maleic anhydride / K obtained in Synthesis Example (4), 400 parts by weight of ethyl 3-ethoxypropionate Dissolved in parts. A resist pattern was formed in the same manner as in Example 1 except that methyl ammonium hydroxide was added to the coating solution of the resist with respect to the acid generator.

The resist pattern thus formed was a line-and-space pattern of 0.17 mu m. The adhesion state of this resist pattern was favorable, and the cross-sectional shape was a favorable square state which was not influenced by standing waves. The exposure amount was 16 mJ / cm ² .

Example 9

1.5 parts by weight of the acid generator [A] obtained in Synthesis Example 1 based on 100 parts by weight of the resin (5) of the monomer I / maleic anhydride / K obtained in Synthesis Example (5), 400 parts by weight of ethyl 3-ethoxypropionate Dissolved in parts. A resist pattern was formed in the same manner as in Example 1 except that methyl ammonium hydroxide was added to the coating solution of the resist with respect to the acid generator.

The resist pattern thus formed was a line-and-space pattern of 0.16 mu m. The adhesion state of this resist pattern was favorable, and the cross-sectional shape was a favorable square state which was not influenced by standing waves. The exposure amount was 10 mJ / cm ² .

Example 10

1.5 parts by weight of the acid generator [A] obtained in Synthesis Example 1 was dissolved in 400 parts by weight of ethyl 3-ethoxypropionate based on 100 parts by weight of the resin (6) obtained in Polymer Synthesis Example (6). A resist pattern was formed in the same manner as in Example 1 except that methyl ammonium hydroxide was added to the coating solution of the resist with respect to the acid generator.

The resist pattern thus formed was a 0.20 mu m line-and-space pattern. This resist had a poor coating condition and had a slightly non-uniform cross section. The exposure amount was 16 mJ / cm ² .

Example 11

1.5 parts by weight of the acid generator [A] obtained in Synthesis Example 1 was dissolved in 400 parts by weight of ethyl 3-ethoxypropionate based on 100 parts by weight of the resin (7) obtained in Polymer Synthesis Example (7). A resist pattern was formed in the same manner as in Example 1 except that methyl ammonium hydroxide was added to the coating solution of the resist with respect to the acid generator.

The resist pattern thus formed was a line-and-space pattern of 0.17 mu m. The adhesion state of this resist pattern was favorable. The cross-sectional shape was good as almost a square. The exposure amount was 14 mJ / cm ² .

Example 12

1.5 parts by weight of the acid generator [A] obtained in Synthesis Example 1 was dissolved in 400 parts by weight of ethyl 3-ethoxypropionate based on 100 parts by weight of the resin (8) obtained in Polymer Synthesis Example (8). A resist pattern was formed in the same manner as in Example 1 except that methyl ammonium hydroxide was added to the coating solution of the resist with respect to the acid generator.

The resist pattern thus formed was a line-and-space pattern of 0.17 mu m. The adhesion state of this resist pattern was favorable, and the cross-sectional shape was almost square. The exposure amount was 16 mJ / cm ² .

The matrix resin prepared in the present invention improves adhesion to the substrate by introducing a hydroxy group and a carboxylic acid group, and improves the etching resistance by introducing a cyclic group (CYCLIC GROUP) and a pendant cyclic group in the main chain. I was.

The photoresist using the matrix resin of the present invention was excellent in high resolution, heat resistance, etching resistance, storage stability after exposure, and an excellent resist pattern was obtained regardless of the type of substrate.

Claims (5)

A polymer for producing a positive photoresist having a repeating unit represented by the following general formula (I) and having a polystyrene reduced average molecular weight of 2,000 to 1,000,000. (I) Wherein R ₁ , R ₅ , and R ₈ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, each independently, and R ₂ , R ₃ , R ₉ , and R ₁₀ represent a hydrogen atom, a hydroxyl group, or an alkoxy group , Or an acetoxy group, each independently. R ₄ and R ₁₁ represent a hydrogen atom, a cyclic, straight or branched chain alkyl group having 1 to 15 carbon atoms, an alkoxyalkyl group, an alkoxymethylene group, a tetrahydropyran (THP) group, or a tetrahydrofuran (THF) group. R ₆ and R ₇ are hydrogen atom, hydroxyl group, cyclic, straight or branched chain alkyl group having 1 to 10 carbon atoms, carboxylic acid, alkoxyalkyloxycarbonyl group, alkoxymethoxycarbonyl group, tetrahydropyranyloxycarbonyl group, or It represents a tetrahydrofuranyloxycarbonyl group and is independent of each other. l, m, n and o are the numbers representing the repeating units, respectively, 0≤l / m + n + o≤0.7, 0.1≤m / l + n + o≤0.7, 0≤n / ℓ + m + o≤0.7 And 0 ≦ o / l + m + n ≦ 0.7. The polymer according to claim 1, wherein the polystyrene standard molecular weight used for at least one monomer selected from the monomer groups represented by the following general formulas (II) to (V) is 2,000 to 1,000,000. [Formula 2] Ⅱ Ⅲ Ⅳ Ⅴ Wherein R ₁ , R ₅ , and R ₈ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, each independently, and R ₂ , R ₃ , R ₉ , and R _{10 each} represent a hydrogen atom, a carbon atom at 1 Up to 15 cyclic, straight or branched alkyl groups, alkoxyalkyl groups, alkoxymethylene groups, THP groups, or THF groups are shown. R ₆ and R ₆ are hydrogen, hydroxyl, cyclic, straight or branched alkoxycarbonyl group having 1 to 10 carbon atoms, cyclic, straight or branched chain alkyl group having 1 to 10 carbon atoms, carboxylic acid, An alkoxyalkyloxycarbonyl group, an alkoxymethoxycarbonyl group, a tetrahydropyranyloxycarbonyl group, or a tetrahydrofuranyloxycarbonyl group is shown and is independent of each other. The composition of the chemically amplified positive photoresist whose repeating unit consists of a polymer represented by following General formula (I), an acid generator, and a solvent. (I) Wherein R ₁ , R ₅ , and R ₈ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, each independently, and R ₂ , R ₃ , R ₉ , and R ₁₀ represent a hydrogen atom, a hydroxyl group, or alkoxy Group or acetoxy group and each independently. R ₄ and R ₁₁ represent a hydrogen atom, a cyclic, straight or branched chain alkyl group having 1 to 15 carbon atoms, an alkoxyalkyl group, an alkoxymethylene group, a tetrahydropyran (THP) group, or a tetrahydrofuran (THF) group. R ₆ and R ₇ are hydrogen atom, hydroxyl group, cyclic, straight or branched chain alkyl group having 1 to 10 carbon atoms, carboxylic acid, alkoxyalkyloxycarbonyl group, alkoxymethoxycarbonyl group, tetrahydropyranyloxycarbonyl group, or It represents a tetrahydrofuranyloxycarbonyl group and is independent of each other. l, m, n and o are the numbers representing the repeating units, respectively, 0≤l / m + n + o≤0.7, 0.1≤m / l + n + o≤0.7, 0≤n / ℓ + m + o≤0.7 And 0 ≦ o / l + m + n ≦ 0.7. The chemically amplified positive photoresist composition according to claim 3, wherein the acid generator is an onium salt compound represented by the following general formulas (VI), (IX) and (IX). Ⅵ Ⅶ Ⅷ Herein, R ₁ , R ₂ , and R ₅ represent an alkyl group, an allyl group, a naphthalenyl group, or an aryl group, and are each independently, and R ₃ and R ₄ represent a hydrogen atom, an alkyl group, or an alkoxy group, and are each independently. n is an integer of 0-14. The chemical method according to claim 4, which is a method of synthesizing using perfluoroalkanesulfonic anhydride [CF ₃ (CF ₂ ) _n SO ₂ —O—SO ₂ (CF ₂ ) _n CF ₃ ] at the time of acid generator synthesis. Amplified Positive Photoresist Composition. Here, it is an integer of n = 0-14.