KR20000034147A - Monomer, polymer thereof and photoresist composition using the same - Google Patents

Abstract

PURPOSE: A polymer for photoresist is provided which has excellent etching resistance and photosensitivity, and is also excellent in adhesive force between substrate and photoresist pattern that the pattern is not collapsed even in highly dense element and has high resolution, and has low optical absorbance that is able to produce more elaborate pattern and therefore is particularly suitable to photolithographic process using a light source of far ultraviolet region, particularly ArF light source. CONSTITUTION: A monomer for photoresist and the polymer thereof have the following chemical formula 2 and 10 respectively:(chemical formula 2), (chemical formula 10), wherein R<SB POS="POST">1</SB> and R<SB POS="POST">2</SB> are independently hydrogen atom, or substituted or non-substituted linear or branched alkyl, cycloalkyl, alkoxyalkyl or cycloalkoxyalkyl having 1 - 10 carbon atom, R<SB POS="POST">5</SB> is hydroxyethyl or hydroxypropyl, and m is a number selected from 0 - 3.

Description

Novel monomers, polymers thereof and photoresist compositions using the same

The present invention relates to a novel monomer, a polymer thereof, and a photoresist composition using the same, and more particularly, to a photoresist monomer having a property suitable for an optical lithography process employing a light source in an far ultraviolet region, a polymer thereof, and a photo using the same. To a resist composition.

Photoresist compositions used in photolithography processes using extreme wavelength light sources, such as E-beams, KrF, EUV, X-rays, in particular ArF light sources, have low light absorption at 193 nm wavelength, and have excellent etch resistance and adhesion. It has to satisfy various conditions such that it can be developed into 2.38 w% tetramethylammonium hydroxide (TMAH) aqueous solution.

To date, many research directions have been gathered in the search for resin at the same level as the novolak resin with high transparency and etching resistance at 193 nm. Accordingly, attempts have been made to improve the etching resistance by introducing alicyclic units into the main chain, but it is very difficult to construct all of the main chains into aliphatic rings, and when the metal is used as a catalyst, Although it can be configured as an aliphatic ring, in this case, it is difficult to remove the metal component contained in the resin, and this method is also difficult to use because the metal component in the resin has a fatal weak effect on the semiconductor device.

In an attempt to solve the above problems, a polymer resin for photoresist represented by the following formula (1) having a structure in which the main chain is substituted with norboran, acrylate and maleic anhydride Developed at Bell Lab.

<Formula 1>

However, such a photoresist polymer resin is norbornene, an aliphatic cyclic unit, in which maleic hydride (part A) used to polymerize alicyclic olefin group does not absorb light having a wavelength of 193 nm. ) Is the only material that can be polymerized, but has a problem in that it is very well dissolved in a 2.38% TMAH solution even when unexposed, resulting in a top loss phenomenon in which the top of the pattern is rounded when the actual photoresist pattern is formed. Therefore, the ratio of the y part containing t-butyl introduced to inhibit dissolution must be greatly increased. However, as the y part increases, the z part (carboxylate part), which increases the adhesion and sensitivity to the underlying layer, is relatively reduced, resulting in the photoresist falling off the wafer during the actual patterning. The disadvantage is that it becomes impossible to form. In addition, during post exposure delay in which the heat treatment is not performed immediately after exposure, a T-top phenomenon occurs in which the lower part of the pattern becomes smaller than the upper part, which makes it difficult to form the pattern itself. Since Ian hydride reacts with the hydroxy group (-OH) which increases the adhesion, there is a possibility that the shelf life of the photoresist is affected.

Therefore, Bell Labs tried to solve this problem by adding a cholesterol-based dissolution inhibitor as an alternating polymer of two-component cycloolefin and maleic hydride. Since the resin having such a molecular structure is fundamentally inferior in reproducibility and increases in cost, it is difficult to use it as a photoresist resin.

In order to solve the above problems, the present invention provides novel monomers for photoresists and polymers thereof.

Another object of the present invention is to provide a photoresist composition comprising the polymer and a semiconductor device manufactured using the same.

1 shows a photograph of a photoresist fine pattern according to a twelfth embodiment of the present invention,

2 shows a photograph of a photoresist fine pattern according to a fifteenth embodiment of the present invention,

3 shows a photograph of a photoresist fine pattern according to a sixteenth embodiment of the present invention.

The present invention provides a compound of formula 2 as a monomer for photoresist to achieve the above object.

<Formula 2>

Wherein R ₁ and R ₂ are each hydrogen or substituted or unsubstituted linear or branched alkyl, cycloalkyl, alkoxyalkyl or cycloalkoxyalkyl having 1 to 10 carbon atoms, and m is 0 to 3.

Moreover, the compound of following formula (10) is provided as a polymer for photoresists.

<Formula 10>

Wherein R ₁ and R ₂ are each hydrogen or substituted or unsubstituted straight or branched chain alkyl, cycloalkyl, alkoxyalkyl or cycloalkoxyalkyl having 1 to 10 carbon atoms, R ₅ is hydroxyethyl or hydroxypropyl, m is 0-3. The molar percentage ratios of a, b, c and d are (10 to 100): (10 to 90): (10 to 90): (10 to 90).

In order to achieve another object of the present invention, the present invention provides a photoresist composition comprising the polymer of Formula 3, a photoacid generator, and an organic solvent.

Synthesis of Monomers

The present inventors have conducted a number of studies and experiments to solve the above problems of the prior art, as a result, synthesized a compound of formula 2 as a monomer for a photoresist.

<Formula 2>

Wherein R ₁ and R ₂ are each hydrogen or substituted or unsubstituted linear or branched alkyl, cycloalkyl, alkoxyalkyl or cycloalkoxyalkyl having 1 to 10 carbon atoms, and m is 0 to 3.

The compound of Formula 2 is a bicycloalkene derivative, and the photoresist resin formed of the polymerized structure of the bicyclo alkene derivative has excellent etching resistance. In addition, since the light sensitive two carboxylate substituents are included, the solubility difference between the exposed portion and the non-exposed portion is large, and thus a pattern having excellent resolution can be obtained when using a photoresist resin including the same. In addition, since two photosensitive substituents are included, in order to increase the ratio of additional functional monomers, even if the ratio of the monomer of Formula 2 is lowered to some extent in the polymer, it affects the photosensitivity and the solubility difference between the exposed portion and the non-exposed portion. The impact is mitigated.

Hereinafter, specific examples of a novel monomer and a method of preparing the same according to the present invention will be disclosed, but the present invention is not limited thereto.

Example 1 Synthesis of Bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic Acid

After dissolving 1 mol of cyclohexanediene in 500 ml of THF, the temperature was cooled to -30 ° C. In this case, in addition to THF, toluene, ethyl ether, benzene, dichloromethane or chloroform may be used as the organic solvent.

The temperature is maintained at -30 ° C while gradually adding the maleic hydride in the same molar ratio as the cyclolexidiene to the resultant solution. After reacting for about 10 hours, the temperature is gradually increased to room temperature and allowed to react for 10 hours. After completion of the reaction, the organic solvent was removed by a rotary distillation, and bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic anhydride was obtained by vacuum distillation. (Yield 92%)

Subsequently, 0.5 mole of bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic anhydride synthesized above was slowly stirred in a 10 wt% aqueous NaOH solution to dissolve well. Then, the temperature was raised to 85 ° C. and refluxed for 1.5 hours, and then the temperature was slowly lowered to room temperature. 10% sulfuric acid solution was slowly added dropwise to the reaction solution to adjust the pH to neutral, and the organic layer was separated with ethyl acetate using a separatory funnel. Extraction was performed several times and the combined solution was dried over anhydrous MgSO ₄ and distilled under reduced pressure to obtain a bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic acid represented by the following Chemical Formula 3 as a pure white solid. (Yield 98%)

<Formula 3>

Example 2 Synthesis of Dibutylbutyl Bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate

1 mole of bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic acid synthesized in Example 1 was added to the reactor, dissolved in 500 g of tetrahydrofuran solvent and cooled to -10 ° C. . After adding 2 moles of SOCl ₂ to the mixture slowly for 1 hour, 2 moles of tert-butanol was added and allowed to react for about 2 hours while stirring. After completion of the reaction, the temperature is gradually increased to room temperature and allowed to react for 6 hours. After completion of the reaction, the solvent was removed using a rotary distillation, followed by distillation under reduced pressure to obtain a pure butyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate of formula 4 (yield: 81 %).

<Formula 4>

Example 3 Synthesis of Ditetrahydropyranyl Bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate

1 mole of bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic acid synthesized in Example 1 as a starting material was added to the reactor, and the resultant was dissolved in 500 g of tetrahydrofuran solvent and the temperature was reduced to -10 ° C. Cool. Then, 0.02 mol of p-toluenesulfonic acid was slowly added thereto, stirred for 1 hour, and then 2 mol of 3,4-dihydro-2H-pyran was added dropwise as a reaction material, followed by reaction for about 2 hours. After that, the temperature is gradually increased to room temperature and allowed to react for another 5 hours. After completion of the reaction, the solvent was removed using a rotary distillation, followed by distillation under reduced pressure to obtain a ditetrahydropyranyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate of formula 5 (yield). : 75%).

<Formula 5>

Example 4 Synthesis of Ditetrahydrofuranyl Bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate

Ditetrahydrofuranyl bicyclo of the following Chemical Formula 6 was subjected to the same procedure as in Example 3 except that dihydrofuran was used instead of 3,4-dihydro-2H-pyran as the reactant. 2.2.2] oct-5-ene-2,3-dicarboxylate was obtained (yield: 80%).

<Formula 6>

Example 5

Synthesis of 1,1'-diethoxyethyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate

1.1'-diethoxyethyl bicyclo of Chemical Formula 7 was carried out in the same manner as in Example 3, except that ethyl vinyl ether was used instead of 3,4-dihydro-2H-pyran as the reactant. [2.2.2] Oct-5-ene-2,3-dicarboxylate was obtained (yield: 79%).

<Formula 7>

Example 6

Synthesis of 1,1'-Diethylbutoxyethyl Bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate

Except for using tertiary butyl vinyl ether instead of 3,4-dihydro-2H-pyran as the reaction material in the same manner as in Example 3 in the pure state 1,1 '-diet Shiributoxyethyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate was obtained (yield: 73%).

<Formula 8>

Preparation of Polymer

The present inventors also prepared a polymer comprising the monomer of the formula (2). At this time, it is preferable to use maleic anhydride as the second monomer in order to facilitate the bonding between the monomers of the formula (2).

In addition, it is preferable to increase the adhesion between the substrate and the photoresist pattern by using the compound of formula (9) having a hydroxy group as the third monomer.

<Formula 9>

Wherein R ₅ is hydroxyethyl or hydroxypropyl.

On the other hand, it is more preferable to further include a bicyclo [2.2.2] oct-5-ene dicarboxylic acid as the fourth monomer separately from the first monomer.

Preferred photoresist copolymers according to the present invention include compounds represented by the following general formula (10).

<Formula 10>

Wherein R ₁ and R ₂ are each hydrogen or substituted or unsubstituted straight or branched chain alkyl, cycloalkyl, alkoxyalkyl or cycloalkoxyalkyl having 1 to 10 carbon atoms, and R ₅ is hydroxyethyl or hydroxypropyl and m is 0-3.

The molecular weight of the polymer resin for photoresist thus prepared is preferably 3,000 to 100,000. Moreover, it is preferable that the mole% ratio of a, b, c, and d is (10-100): (10-90): (10-90): (10-90).

The photoresist polymer according to the present invention is synthesized by radical polymerization, bulk polymerization and solution polymerization of each monomer in the presence of a polymerization initiator. Polymerization initiators include 2,2, -azobisisobutyronitrile (AIBN), benzoyl peroxide, acetyl peroxide, lauryl peroxide, t-butyl oxide and the like. The solvent used in the polymerization includes tetrahydrofuran, cyclonucleic acid, toluene, benzene, methylethylketone, dioxane, dimethylformamide and the like. The polymerization is carried out at a temperature of 60 to 75 ° C. under nitrogen or argon atmosphere for 4 to 24 hours. However, the present invention is not limited to these polymerization conditions.

Example 7 Poly (Diethylbutyl Bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate / 2-hydroxyethyl 5-norbornene-2-carboxylate / bicyclo [ 2.2.2] Synthesis of Oct-5-ene-2,3-dicarboxylic acid / maleic hydride) polymer

0.85 mol of dibutyl butyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate, 0.1 mol of 2-hydroxyethyl 5-norbornene-2-carboxylate, bicyclo [2.2. 2] After putting 0.05 mol of oct-5-ene-2,3-dicarboxylic acid and 1 mol of maleic hydride in a tetrahydrofuran solvent, 5.5 g of AIBN was added to a polymerization reagent and stirred. The polymerization temperature was fixed at 67 ° C. and polymerization was carried out under nitrogen atmosphere for 10 hours. After completion of the polymerization reaction, the polymer was precipitated in an ethyl ether solvent and dried in vacuo to obtain a copolymer of formula 11 in pure state. (Yield 32%)

<Formula 11>

Example 8

Poly (ditetrahydropyranyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate / 2-hydroxyethyl 5-norbornene-2-carboxylate / bicyclo [2.2. 2] Synthesis of Oct-5-ene-2,3-dicarboxylic acid / maleic anhydride) polymer

Ditetrahydropyranyl bicyclo [2.2.2] oct-5-ene-2,3-dicar instead of dietarybutyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate Except that the addition of the carboxylate was carried out in the same procedure as in Example 7 to obtain a compound of formula 12 (yield 30.5%).

<Formula 12>

Example 9 poly (ditetrahydrofuranyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate / 2-hydroxyethyl 5-norbornene-2-carboxylate / ratio Synthesis of cyclo [2.2.2] oct-5-ene-2,3-dicarboxylic acid / maleic anhydride) polymer

Ditetrahydrofuranyl bicyclo [2.2.2] oct-5-ene-2,3-dicar instead of dietarybutyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate Except that the addition of the carboxylate was carried out in the same procedure as in Example 7 to obtain a compound of formula 13 (yield 30.5%).

<Formula 13>

Example 10 poly (1,1'-diethoxyethyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate / 2-hydroxyethyl 5-norbornene-2-carboxyl Synthesis of Rate / Bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic acid / maleic anhydride) polymer

1,1'-diethoxyethyl bicyclo [2.2.2] oct-5-ene-2,3 instead of dietarybutyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate A compound of the following Chemical Formula 14 was obtained in the same manner as in Example 7, except that dicarboxylate was added (yield 31.5%).

<Formula 14>

Example 11 Poly (1,1'-Diethylbutoxyethyl 5-norbornene-2,3-dicarboxylate / 2-hydroxyethyl 5-norbornene-2-carboxylate / bicyclo [2.2 .2] Synthesis of Oct-5-ene-2,3-dicarboxylic acid / maleic hydride) polymer

Add 1,1'-ethoxyethyl 5-norbornene-2,3-dicarboxylate instead of dietary butyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate Except for the same procedure as in Example 7, to obtain a compound of Formula 15 (yield 32%).

<Formula 15>

Synthesis of Photoresist Composition and Micropattern Formation Using Same

The photoresist polymer of Formula 10 prepared as described above is useful for forming a fine pattern of a semiconductor device. The present inventors prepared a photoresist composition by mixing the polymer of Formula 10 with a conventional organic solvent and a photoacid generator.

Phtoacid generators are sulfur-based or onium-based salts, for example triphenylsulfonium triflate or dibutylnaphthylsulfonium triflate. The photoacid generator is used in an amount of 0.05 to 10% by weight of the used photoresist resin. When it is used at 0.05 wt% or less, the photosensitive sensitivity of the photoresist becomes weak, and when it is used at 10 wt% or more, the photoacid generator absorbs a lot of ultraviolet rays, thereby obtaining a pattern having a bad cross section.

As the organic solvent, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, cyclohexanone, propylene glycol methyl ether acetate and the like can be used. The solvent is used in an amount of 200 to 1000% by weight of the used photoresist resin to obtain a photoresist of a desired thickness.

Meanwhile, a fine pattern was formed on a semiconductor substrate using the photoresist composition according to the present invention.

First, the photoresist composition according to the present invention is spin coated on a silicon wafer and then baked. Subsequently, after exposure with an exposure apparatus using ArF light, it is post-baked for about 1 to 2 minutes. In this case, the soft bake and post bake process may be performed at 70 to 200 ° C. As the exposure source, KrF, E-beam, EUV (extremely ultraviolet), ion beam, etc. may be used in addition to ArF.

Thereafter, it was developed in a 2.38w% TMAH aqueous solution to obtain a fine pattern. The obtained micropattern showed excellent adhesion and sensitivity which did not collapse even at high density of 0.15 탆 or less. EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated concretely based on an Example, it is not understood that the technical scope of this invention is limited to these.

Example 12

10 g of the polymer of Example 7 and 0.12 g of triphenylsulfonium triflate were dissolved in 60 g of ethyl 3-ethoxypropionate, and then filtered through a 0.10 μm filter to prepare a photoresist solution. The solution is spin coated onto a silicon wafer, and then bayed at 110 ° C. for 90 seconds. After baking, the resultant is exposed to ArF laser exposure equipment and then baked again at 110 ° C. for 90 seconds. Subsequently, the resultant was developed in an aqueous 2.38w% tetramethylammonium hydroxide solution for 40 seconds to obtain 0.13 μm L / S pattern as shown in FIG. 1.

Example 13

A 0.14 µm L / S pattern was obtained in the same manner as in Example 12 except that the polymer of Example 8 was used.

Example 14

A 0.14 µm L / S pattern was obtained in the same manner as in Example 12 except that the polymer of Example 9 was used.

Example 15

A 0.14 μm L / S pattern as shown in FIG. 2 was obtained in the same manner as in Example 12 except that the polymer of Example 10 was used.

Example 16

A 0.14 μm L / S pattern as shown in FIG. 3 was obtained in the same manner as in Example 12 except for using the polymer of Example 11.

The photoresist polymer according to the present invention is excellent in etch resistance because the backbone is composed of a bicycloalkene monomer, and includes a first monomer having two carboxylate groups, and thus has excellent photosensitivity and a hydroxy group. Including the third monomer having a good adhesion between the substrate and the photoresist pattern has a high resolution without falling down pattern even in a high-density device, and because the light absorption rate is low in the extreme wavelength can be formed finer fine pattern, especially ArF light source It is suitable for the photolithography process to be used.

Claims (30)

A novel compound represented by the following formula (2). <Formula 2> Wherein R ₁ and R ₂ are each hydrogen or substituted or unsubstituted linear or branched alkyl, cycloalkyl, alkoxyalkyl or cycloalkoxyalkyl having 1 to 10 carbon atoms, and m is 0 to 3. The method of claim 1, The compound is bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic acid, tert-butyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate, Ditetrahydropyranyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate, ditetrahydrofuranyl bicyclo [2.2.2] oct-5-ene-2,3-dica Carboxylate, 1,1'-diethoxyethyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate and 1,1'-dibutaryethyl methoxycyclo [2.2.2] ] Oct-5-ene-2,3-dicarboxylate. (a) preparing bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic acid as starting material, (b) reacting the starting material in an organic solvent with a reactant selected from the group consisting of tert-butanol, 3,4-dihydro-2H-pyran, dihydrofuran, ethyl vinyl ether and tertiary butyl vinyl ether Method for producing a novel compound according to claim 1, characterized in that it comprises a step. The method of claim 3, wherein Step (a) is (i) reacting cyclohexanediene and maleic anhydride in an organic solvent to obtain bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic anhydride, (ii) hydrolyzing the bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic anhydride to give bicyclo [2.2.2] oct-5-ene-2,3-dicar Producing an acid. The method of claim 4, wherein Wherein in the step (i) the maleic anhydride is used in the same molar number or slightly in excess of the cyclohexanediene. The method of claim 3, wherein In step (b), the reactant is characterized in that it is used twice or slightly in excess of the number of moles of the starting material. The method of claim 3, wherein The step (b) is characterized in that it is carried out under acidic catalyst or under basic conditions. The method of claim 3, wherein The organic solvent is selected from the group consisting of toluene, tetrahydrofuran, ethyl ether, benzene, dichloromethane and chloroform. A photoresist polymer comprising a monomer of the formula (2). <Formula 2> Wherein R ₁ and R ₂ are each hydrogen or substituted or unsubstituted linear or branched alkyl, cycloalkyl, alkoxyalkyl or cycloalkoxyalkyl having 1 to 10 carbon atoms, and m is 0 to 3. The method of claim 9, Wherein said polymer comprises maleic hydride as a second monomer. The method of claim 9 or 11, The polymer is a polymer, characterized in that it further comprises a compound of formula (9) as a third monomer. <Formula 9> Wherein R ₅ is hydroxyethyl or hydroxypropyl. The method according to any one of claims 9 to 11, Said polymer comprising bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic acid. The method of claim 9, The polymer is a polymer, characterized in that the compound of formula (10). <Formula 10> Wherein R ₁ and R ₂ are each hydrogen or substituted or unsubstituted straight or branched chain alkyl, cycloalkyl, alkoxyalkyl or cycloalkoxyalkyl having 1 to 10 carbon atoms, and R ₅ is hydroxyethyl or hydroxypropyl and m is 0-3. The method of claim 13, The polymer has a molecular weight of 3,000 to 1000,000. The method of claim 13, The ratio of a, b, c and d is 10 to 100: 10 to 90: 10 to 90: 10 to 90 based on the mole%. The method of claim 13, The polymer is poly (dibutylbutyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate / 2-hydroxyethyl 5-norbornene-2-carboxylate / bicyclo [2.2 .2] oct-5-ene-2,3-dicarboxylic acid / maleic hydride), Poly (ditetrahydropyranyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate / 2-hydroxyethyl 5-norbornene-2-carboxylate / bicyclo [2.2. 2] oct-5-ene-2,3-dicarboxylic acid / maleic hydride), Poly (ditetrahydrofuranyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate / 2-hydroxyethyl 5-norbornene-2-carboxylate / bicyclo [2.2. 2] oct-5-ene-2,3-dicarboxylic acid / maleic hydride), Poly (1,1'-diethoxyethyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate / 2-hydroxyethyl 5-norbornene-2-carboxylate / bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic acid / maleic anhydride) and Poly (1,1'-dibutyoxyethyl 5-norbornene-2,3-dicarboxylate / 2-hydroxyethyl 5-norbornene-2-carboxylate / bicyclo [2.2.2] oct -5-ene-2,3-dicarboxylic acid / maleic hydride). (a) dissolving the monomer of Formula 2 and maleic anhydride in an organic solvent, (b) a method of producing a copolymer for photoresist according to claim 9, comprising the step of polymerizing by adding a polymerization initiator to the resulting solution. The method of claim 17, Wherein said polymerization initiator is selected from the group consisting of 2,2, -azobisisobutyronitrile (AIBN), benzoyl peroxide, acetyl peroxide, lauryl peroxide and t-butyl oxide. The method of claim 17, The organic solvent is selected from the group consisting of tetrahydrofuran, toluene, benzene, methylethylketone and dioxane. A photoresist composition comprising a photoresist polymer comprising a monomer of the formula (2), a photoacid generator, and an organic solvent. <Formula 2> Wherein R ₁ and R ₂ are each hydrogen or substituted or unsubstituted linear or branched alkyl, cycloalkyl, alkoxyalkyl or cycloalkoxyalkyl having 1 to 10 carbon atoms, and m is 0 to 3. The method of claim 20, The photoresist polymer is a photoresist composition, characterized in that the compound of formula (10). <Formula 10> Wherein R ₁ and R ₂ are each hydrogen or substituted or unsubstituted straight or branched chain alkyl, cycloalkyl, alkoxyalkyl or cycloalkoxyalkyl having 1 to 10 carbon atoms, and R ₅ is hydroxyethyl or hydroxypropyl and m is 0-3. The method of claim 20, Said photoacid generator is triphenylsulfonium triflate or dibutyl naphthylsulfonium triflate. The method of claim 20, The content of the photoacid generator is a photoresist composition, characterized in that 0.05 to 10% by weight of the polymer. The method of claim 20, The organic solvent is a photoresist composition, characterized in that selected from the group consisting of ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, cyclohexanone and propylene glycol methyl ether acetate. The method of claim 20, The content of the organic solvent is a photoresist composition, characterized in that 200 to 1000% by weight of the polymer. (a) coating the photoresist composition of claim 20 on a wafer, (b) exposing the wafer; (c) developing the resultant with a developer to obtain a predetermined pattern. The method of claim 26, A method of forming a photoresist pattern further comprising the step of performing a baking process before or after the exposure in step (b), respectively. The method of claim 27, The baking process is a photoresist pattern forming method, characterized in that performed at 70 ~ 200 ℃. The method of claim 26, The exposure process is a photoresist pattern forming method characterized in that it is performed using ArF, KrF, E-beam, X-ray, EUV, DUV or ion beam. A semiconductor device manufactured by the method of claim 26.