KR100527532B1 - Novel photoresist monomer, polymer thereof and photoresist composition containing it - Google Patents

Abstract

The present invention relates to a compound represented by the following formulas (1) to (3) and a photoresist polymer using the same as the monomer, and the photoresist polymer of the present invention is not only excellent in etching resistance, heat resistance and adhesion, but also in tetramethylammonium hydrate as a developer It can be developed in an aqueous solution of Lockside (TMAH) and can be very useful for the lithography process using a light source in the far ultraviolet region, especially a 157 nm light source, when manufacturing a microcircuit of a highly integrated semiconductor device.

[Formula 1]

[Formula 2]

[Formula 3]

In the above formulas, R ₁ , R ₂ and R ₃ are hydrogen, alkyl having 1 to 5 carbon atoms, alkoxyalkyl, 2,3-dihydropyranyl, 2,3-dihydrofuranyl, hydroxyalkyl.

Description

Novel photoresist monomers, polymers and photoresist composition containing it

FIELD OF THE INVENTION The present invention relates to novel photoresist monomers, polymers thereof and photoresist compositions containing the polymers, and more particularly suitable for use in lithographic processes using light sources in the far ultraviolet region in the manufacture of microcircuits of highly integrated semiconductor devices. The present invention relates to a monomer for photoresist, a polymer thereof, a photoresist composition containing the polymer, and a method for producing the same.

In order to achieve high sensitivity in the microfabrication process of semiconductor manufacturing, photolithography is suitable for lithography using a light source in the deep ultra violet (DUV) region which is chemically amplified such as KrF (248 nm), ArF (193 nm) or EUV. The resist is in the spotlight, and such a photoresist is prepared by combining a photoacid generator and a polymer for photoresist having a structure sensitive to acid.

The mechanism of action of the photoresist is that the photoacid generator that receives ultraviolet light from the light source generates an acid, and the polymer main chain or side chain of the exposed portion is decomposed by the acid, and then dissolved in the developer, while the non-exposed site is dissolved. Since the film retains its original structure even after the developer treatment, the mask image remains as a positive image on the substrate. In such a lithography process, the resolution is dependent on the wavelength of the light source, and as the wavelength of the light source becomes smaller, a fine pattern can be formed. Accordingly, a photoresist suitable for such a light source is required.

In addition, photoresists generally have to have a high transmittance for the light source used, and have excellent etching resistance, heat resistance, and adhesion to various kinds of substrates. In addition, in order to be used as a photoresist for a 157nm light source, it is advantageous to develop in a known developer, for example, an aqueous solution of 2.38wt% tetramethylammonium hydroxide (TMAH) in terms of process cost reduction, but all these properties It is very difficult to produce satisfactory polymers, in particular photoresist for far ultraviolet rays. For example, a polymer having a polyacrylate-based main chain is easy to synthesize, but has problems in securing etching and developing processes, and a photoresist has a low transmittance at 157 nm, and thus a good pattern cannot be obtained.

The photoresist polymer that can be used for 157 nm lithography developed so far has not been developed, and therefore, the development of a new structure of the photoresist polymer for 157 nm lithography is urgently required.

The present inventors have been trying to solve the above-mentioned problems of the prior art, and when copolymerizing the dipropazyl malonic acid ester derivative, dipropazyl acetate ester derivative and dipropazyl carbinol of the present invention, these polymers have a wavelength of 157 nm. The present invention was completed by confirming that the transmittance was excellent at, the etching resistance and adhesion, as well as the difference in solubility in the exposed and non-exposed portions of the developer was significant.

It is an object of the present invention to provide novel photoresist monomers having excellent properties, polymers of such monomers and photoresist compositions containing the polymers.

In order to achieve the above object, in the present invention, a novel photoresist monomer having a high transparency in the far ultraviolet region, especially 157nm wavelength, and excellent in etching resistance and adhesion, and a method for producing the same; Polymers of the monomers and methods for their preparation; A photoresist composition containing the polymer; And it provides a semiconductor device manufactured using the photoresist composition.

Hereinafter, the present invention will be described in detail.

In the present invention, first, the dipropazyl malonic acid ester derivative represented by the following Chemical Formula 1 containing various protecting groups; Dipropazyl acetic acid ester derivative of formula (2); And it provides a photoresist monomer selected from the group consisting of dipropazyl carbinol of formula (3).

[Formula 1]

[Formula 2]

[Formula 3]

Wherein R ₁ , R ₂ and R ₃ are the same or different and each is hydrogen, alkyl having 1 to 5 carbon atoms, alkoxyalkyl, 2,3-dihydropyranyl, 2,3-dihydrofuranyl or hydroxy Alkyl.

Preferred examples of the dipropazyl malonic acid ester derivative of Formula 1 are as follows:

Dietary butyl dipropazalmalonate represented by the following formula (4);

[Formula 4]

Di-1-ethoxyethyl dipropazalmalonate represented by Formula 5 below;

[Formula 5]

Di-2-ethoxypropyl dipropazalmalonate represented by the following formula (6);

[Formula 6]

Further preferred examples of the dipropazyl acetic acid ester derivative of Formula 2 are as follows:

Tertiarybutyl dipropazyl acetate represented by Formula 7;

[Formula 7]

1-ethoxyethyl dipropazyl acetate represented by Formula 8;

[Formula 8]

2-ethoxypropyl dipropazyl acetate represented by the following formula (9);

[Formula 9]

In the present invention, (i) the dipropazyl malonic acid ester derivative of Formula 1; (ii) at least one monomer selected from dipropazyl acetic acid ester derivatives of formula (2); And optionally (iii) a polymer repeating unit consisting of dipropazyl carbinol of formula (3).

The molecular weight of the photoresist polymer of the present invention is 3,000 to 100,000, and includes a polymerization repeating unit represented by the following Chemical Formulas 10 to 21:

Poly (dibutylbutyl dipropazalmalonate) of Formula 10;

[Formula 10]

Poly (di-1-ethoxyethyl dipropazalmalonate) represented by Formula 11;

[Formula 11]

Poly (di-2-ethoxypropyl dipropazalmalonate) represented by Formula 12;

[Formula 12]

Poly (di-butyldipropylacetate) of formula (13);

[Formula 13]

Poly (di-1-ethoxyethyl dipropazyl acetate) represented by Formula 14;

[Formula 14]

Poly (di-2-ethoxypropyl dipropazyl acetate) of Formula 15;

[Formula 15]

Poly (di-butylbutyl dipropazolmalonate / dipropazylcarbinol) of Formula 16;

[Formula 16]

Poly (di-1-ethoxyethyl dipropazylmalonate / dipropazylcarbinol) of Formula 17;

[Formula 17]

Poly (di-2-ethoxypropyl dipropazalmalonate / dipropazylcarbinol) of Formula 18;

[Formula 18]

Poly (di-butylbutyl dipropazyl acetate / dipropazylcarbinol) of Formula 19;

[Formula 19]

Poly (di-1-ethoxyethyl dipropazyl acetate / dipropazylcarbinol) of Formula 20;

[Formula 20]

Poly (di-2-ethoxypropyl dipropazyl acetate / dipropazylcarbinol) of Formula 21;

[Formula 21]

In Formulas 16 to 21, the molar ratio of x: y is 0.01-99: 0.01-99.

Photoresist polymers of the present invention can be prepared by metathesis polymerizing each monomer in the presence of a metathesis catalyst, for example, the following steps:

(a) dissolving the catalyst for metathesis polymerization in an organic solvent to prepare a catalyst solution;

(b) adding the catalyst solution to a polymerization solvent and leaving it at a temperature of 20 to 40 ° C. for 10 to 20 minutes;

(c) at least one monomer selected from (i) the dipropazyl malonic acid ester derivative of Formula 1 and (ii) the dipropazyl acetate ester derivative of Formula 2 in the resulting solution of step (b); And optionally (iii) adding a photoresist monomer that is dipropazyl carbinol of Formula 3; And

(d) polymerizing the resultant solution of step (c) under nitrogen or argon atmosphere.

Meanwhile, in step (b), the catalyst solution may be added to the polymerization solvent, and then the promoter may be further added by dissolving the promoter in the organic solvent.

The catalyst or cocatalyst uses a transition metal-halide or organometallic compound as a catalyst for metathesis polymerization, wherein the catalyst is selected from the group consisting of MoCl ₅ , WCl ₆ , Mo (OEt) ₅ and PdCl ₂ , Preferably the catalyst is (n-Bu) ₄ Sn or EtAlCl ₂ .

The polymerization solvent is preferably selected from the group consisting of chlorobenzene, 1,4-dioxane, dimethylformamide, cyclohexane, tetrachloromethane and tetrahydrofuran, and the organic solvent for dissolving the catalyst or the promoter is hexane or tetrahydro. It is preferable that it is furan.

This invention also provides the photoresist composition containing the photoresist polymer of this invention mentioned above, an organic solvent, and a photo-acid generator.

The photoacid generator is diphenyl iodo hexafluorophosphate, diphenyl iodo hexafluoro arsenate, diphenyl iodo hexafluoro antimonate, diphenyl paramethoxyphenyl triflate, diphenyl paratoluenyl triflate, diphenyl Paraisobutylphenyl triflate, diphenylpara-t-butylphenyl triflate, triphenylsulfonium hexafluoro phosphate, triphenylsulfonium hexafluoro arsenate, triphenylsulfonium hexafluoro antimonate, triphenylsulfonium Sulphide-based or onium salt-based compounds selected from the group consisting of triflate and dibutylnaphthylsulfonium triflate are mainly used, and it is preferable to use 0.01 to 10 parts by weight based on 100 parts by weight of the resin. When used in less than 0.01 parts by weight the photosensitive sensitivity of the light becomes weak, when used in more than 10 parts by weight of the photo-acid generator absorbs a lot of light to obtain a pattern having a bad cross section.

In addition, the organic solvent may be selected from the group consisting of propylene glycol methyl ether acetate, propylene glycol methyl ether, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate and cyclohexanone. desirable. The organic solvent is used in an amount of 100 to 1000 parts by weight based on 100 parts by weight of the photoresist polymer, which is intended to obtain a desired film thickness. In the present invention, the film thickness is 0.5 μm when used in 500 parts by weight.

The present invention also provides a method of forming a photoresist pattern consisting of the following steps:

(a) applying the photoresist composition of the present invention on the etched layer to form a photoresist film;

(b) exposing the photoresist film; And

(c) developing the result to obtain a desired pattern.

In the process, i) before and after exposure of step (b); Or ii) pre- or post-exposure each of which may further comprise a baking process, which is carried out at 70 to 200 ° C.

In addition, the exposure process is 1 to 100 mJ / cm using a light source having a wavelength of 157nm, a deep ultra violet (DUV), E-beam, X-ray or ion beam including ArF, KrF and EUV as a light source It is preferably carried out with an exposure energy of ^two .

The present invention also provides a semiconductor device manufactured using the photoresist composition of the present invention.

Hereinafter, the present invention will be described in detail by examples. However, the examples are only to illustrate the invention and the present invention is not limited by the following examples.

I. Preparation of Photoresist Monomer

Example 1 Preparation of Dibutyl Butypromalmalonate

36.5 g of butterybutyl malonate was slowly added to a solution in which 7.8 g of sodium was dissolved in 150 ml of ethanol at 0 ° C. After stirring for an hour, 42 g of propazyl bromide was slowly added thereto, refluxed for 1 hour, and ethanol was removed under reduced pressure. The remaining solution was diluted with distilled water and the organic layer was separated. Recrystallization from hexane afforded 40 g of the pure title compound (Yield: 80%).

Example 2 Preparation of Di-1-ethoxyethyl Dipropazalmalonate

41.35 g of the pure title compound of Chemical Formula 5 was synthesized in the same manner as in Example 1, except that 41.90 g of di-1-ethoxyethyl malonate was used instead of dietary butyl malonate (yield: 75%).

Example 3 Preparation of Di-2-ethoxypropyl Dipropazalmalonate

49.13 g of the pure title compound of Formula 6 was synthesized in the same manner as in Example 1, except that 46.64 g of di-2-ethoxypropyl malonate was used instead of dietary butyl malonate (yield: 82%).

Example 4. Preparation of tert-butyl dipropazyl acetate

27.78 g of the pure title compound of Formula 7 was synthesized in the same manner as in Example 1, except that 19.60 g of tertiary butyl acetate was used instead of dietary butyl malonate (yield: 85%).

Example 5. Preparation of 1-ethoxyethyl dipropazyl acetate

27.6 g of the pure title compound of Formula 8 was synthesized in the same manner as in Example 1, except that 22.30 g of 1-ethoxyethyl acetate was used instead of dietary butyl malonate (yield: 78%).

Example 6 Preparation of 2-Ethoxypropyl Dipropazyl Acetate

30.23 g of the pure title compound of Formula 9 was synthesized in the same manner as in Example 1, except that 24.67 g of 2-ethoxypropyl acetate was used instead of dietary butyl malonate (yield: 80%).

Example 7 Preparation of Dipropazylcarbinol

Grignard was prepared with 1.22 moles of magnesium and 1.49 moles of propazyl bromide and reacted with 0.5 moles of ethylformate at −5 ° C. for 30 minutes. Saturated ammonium chloride solution was slowly added to the reaction solution, followed by extraction with ethyl ether. Ethyl ether was removed under reduced pressure and fractional distillation to synthesize 68 g of pure dipropazylcarbinol of formula 3 (yield: 52%).

II. Preparation of Photoresist Polymer

Example 8 Preparation of Poly (Diethylbutyl Dipropazalmalonate)

Under a nitrogen atmosphere, 10 ml of 1,4-dioxane and MoCl _{5 5} mM solution were carefully placed in a 100 ml reactor with a catalyst and then left at 30 ° C. for 15 minutes. 73.09 g of Dibutyl butyl dipropazyl malonate of Formula 4 prepared in Example 1 was slowly added to the reactor, and polymerized at 60 ° C. for 24 hours, followed by adding some methanol to stop the reaction. The resulting product was dissolved in chloroform and precipitated in methanol, and then the precipitate was filtered and dried under reduced pressure to give 65.78 g of the title polymer of the formula (10) (yield 90%).

Example 9 Preparation of Poly (di-1-ethoxyethyl dipropazolmalonate)

68.93 g of the title polymer of Formula 11 was synthesized in the same manner as in Example 8, except that 81.09 g of di-1-ethoxyethyl dipropazalmalonate was used instead of dibutyl butyl dipropazyl malonate (yield: 85%).

Example 10 Preparation of Poly (di-2-ethoxypropyl Dipropazalmalonate)

64.32 g of the title polymer of Chemical Formula 12 were synthesized in the same manner as in Example 8, except that 88.10 g of di-2-ethoxypropyl dipropazalmalonate was used instead of dibutyl butyl dipropazyl malonate (yield: 73%).

Example 11 Preparation of Poly (Diethylbutyl Dipropazyl Acetate)

42.29 g of the title polymer of Chemical Formula 13 was synthesized in the same manner as in Example 8, except that 48.06 g of tertiarybutyl dipropazyl acetate was used instead of dibutyl butyl dipropazyl malonate (yield: 88%).

Example 12 Preparation of Poly (di-1-ethoxyethyl Dipropazyl Acetate)

36.96 g of the title polymer of Chemical Formula 14 was synthesized in the same manner as in Example 8, except that 52.06 g of 1-ethoxyethyl dipropazyl acetate was used instead of dietary butyl dipropazyl malonate (yield: 71%) .

Example 13. Preparation of Poly (di-2-ethoxypropyl dipropazyl acetate)

41.38 g of the title polymer of Chemical Formula 15 was synthesized in the same manner as in Example 8, except that 55.57 g of 2-ethoxypropyl dipropazyl acetate was used instead of dibutyl butyl dipropazyl malonate (yield: 75%) .

Example 14 Preparation of Poly (Diethylbutyl Dipropazalmalonate / Dipropazylcarbinol)

42.06 g of the title polymer of Chemical Formula 16 was synthesized in the same manner as in Example 8, except that 36.55 g of dibutyl butyldipropazalmalonate and 13.52 g of dipropazylcarbinol were used (yield: 84%).

Example 15 Preparation of Poly (di-1-ethoxyethyl dipropazolmalonate / dipropazylcarbinol)

32.44 g of the title polymer of Formula 17 was synthesized in the same manner as in Example 8, except that 40.55 g of di-1-ethoxyethyl dipropazalmalonate and 13.52 g of dipropazylcarbinol were used (yield: 80% ).

Example 16 Preparation of Poly (di-2-ethoxypropyl dipropazolmalonate / dipropazylcarbinol)

33.48 g of the title polymer of Chemical Formula 18 was synthesized in the same manner as in Example 8, except that 44.05 g of di-2-ethoxypropyl dipropazalmalonate and 13.52 g of dipropazylcarbinol were used (yield: 76% ).

Example 17 Preparation of Poly (Diethylbutyl Dipropazyl Acetate / Dipropazylcarbinol)

20.9 g of the title polymer of Chemical Formula 19 was synthesized in the same manner as in Example 8, except that 24.03 g of dibutyl butyl dipropazyl acetate and 13.52 g of dipropazylcarbinol were used (yield: 87%).

Example 18 Preparation of Poly (Di-1-ethoxyethyl Dipropazyl Acetate / Dipropazylcarbinol)

18.74 g of the title polymer of Formula 20 was synthesized in the same manner as in Example 8, except that 26.03 g of 1-ethoxyethyl dipropazyl acetate and 13.52 g of dipropazylcarbinol were used (yield: 72%).

Example 19 Preparation of Poly (Di-2-ethoxypropyl Dipropazyl Acetate / Dipropazylcarbinol)

18.06 g of the title polymer of Chemical Formula 21 was synthesized in the same manner as in Example 8, except that 27.78 g of 2-ethoxypropyl dipropazyl acetate and 13.52 g of dipropazylcarbinol were used (yield: 43.73%).

III. Preparation and Pattern Formation of Photoresist Composition

Example 20.

10 g of the polymer of Example 8 and 0.2 g of triphenylsulfonium triflate as a photoacid generator were dissolved in 50 g of propylene glycol methyl ether acetate solvent, and filtered through a 0.1 µm filter to obtain a photoresist composition.

The composition was spin applied onto a silicon wafer and then heated at 100 ° C. for 90 seconds. After heating, it was exposed with an ArF laser exposure equipment and heated again at 120 ° C. for 90 seconds. After the completion of heating, the solution was developed with a 2.38wt% TMAH aqueous solution, and a 0.20 μm L / S pattern was obtained using an ArF exposure machine (see FIG. 1).

Example 21.

A 0.20 μm L / S pattern was obtained in the same manner as in Example 20 except that the polymer of Example 9 was used instead of the polymer of Example 8.

Example 22.

A 0.20 μm L / S pattern was obtained in the same manner as in Example 20 except for using the polymer of Example 10 instead of the polymer of Example 8.

Example 23.

A 0.20 μm L / S pattern was obtained in the same manner as in Example 20 except that the polymer of Example 11 was used instead of the polymer of Example 8.

Example 24.

A 0.20 μm L / S pattern was obtained in the same manner as in Example 20 except for using the polymer of Example 12 instead of the polymer of Example 8.

Example 25.

A 0.20 μm L / S pattern was obtained in the same manner as in Example 20 except that the polymer of Example 13 was used instead of the polymer of Example 8.

Example 26.

A 0.20 μm L / S pattern was obtained in the same manner as in Example 20 except for using the polymer of Example 14 instead of the polymer of Example 8.

Example 27.

A 0.20 μm L / S pattern was obtained in the same manner as in Example 20 except that the polymer of Example 15 was used instead of the polymer of Example 8.

Example 28.

A 0.20 μm L / S pattern was obtained in the same manner as in Example 20 except for using the polymer of Example 16 instead of the polymer of Example 8.

Example 29.

A 0.20 μm L / S pattern was obtained in the same manner as in Example 20 except for using the polymer of Example 17 instead of the polymer of Example 8.

Example 30.

A 0.20 μm L / S pattern was obtained in the same manner as in Example 20 except that the polymer of Example 18 was used instead of the polymer of Example 8.

Example 31.

A 0.20 μm L / S pattern was obtained in the same manner as in Example 20 except that the polymer of Example 19 was used instead of the polymer of Example 8.

The photoresist using the polymer according to the present invention has excellent transmittance at 157 nm, excellent etching resistance, heat resistance, and adhesiveness, and a developer solution of 2.38% TMAH can be used as a developer. In addition, the adhesiveness was excellent, and satisfactory results were obtained in the resist pattern and the depth of focus (see FIG. 1). Therefore, by using the photoresist composition of the present invention it is possible to reliably manufacture a highly integrated semiconductor device.

1 is a pattern photograph formed using the photoresist composition of the present invention.

Claims (24)

Dipropazyl malonic acid ester derivative of Formula 1; Dipropazyl acetic acid ester derivative of formula (2); And dipropazyl carbinol of formula (3). [Formula 1] [Formula 2] [Formula 3] Wherein R ₁ , R ₂ and R ₃ are the same or different and each is hydrogen, alkyl having 1 to 5 carbon atoms, alkoxyalkyl, 2,3-dihydropyranyl, 2,3-dihydrofuranyl or hydroxy Alkyl. According to claim 1, wherein the dipropazyl malonic acid derivative of Formula 1 Dietary butyl dipropazalmalonate represented by the following formula (4); Di-1-ethoxyethyl dipropazalmalonate represented by Formula 5 below; And A photoresist monomer, characterized in that selected from the group consisting of di-2-ethoxypropyl dipropazalmalonate represented by the formula (6). [Formula 4] [Formula 5] [Formula 6] According to claim 1, wherein the dipropazyl acetate ester derivative of Formula 2 Tertiarybutyl dipropazyl acetate represented by Formula 7; 1-ethoxyethyl dipropazyl acetate represented by Formula 8; And A photoresist monomer, characterized in that selected from the group consisting of 2-ethoxypropyl dipropazyl acetate represented by the following formula (9). [Formula 7] [Formula 8] [Formula 9] at least one monomer selected from (i) a dipropazyl malonic acid ester derivative of Formula 1 and (ii) a dipropazyl acetic acid ester derivative of Formula 2; And optionally (iii) at least one monomer selected from the group consisting of dipropazyl carbinol of formula (3) as a polymer repeating unit. [Formula 1] [Formula 2] [Formula 3] Wherein R ₁ , R ₂ and R ₃ are the same or different and each is hydrogen, alkyl having 1 to 5 carbon atoms, alkoxyalkyl, 2,3-dihydropyranyl, 2,3-dihydrofuranyl or hydroxy Alkyl. The method of claim 4, wherein The molecular weight of the polymer is a photoresist polymer, characterized in that 3,000 to 100,000. The method of claim 4, wherein the polymerization repeating unit Poly (dibutylbutyl dipropazalmalonate) of Formula 10; Poly (di-1-ethoxyethyl dipropazalmalonate) represented by Formula 11; Poly (di-2-ethoxypropyl dipropazalmalonate) represented by Formula 12; Poly (di-butyldipropylacetate) of formula (13); Poly (di-1-ethoxyethyl dipropazyl acetate) represented by Formula 14; Poly (di-2-ethoxypropyl dipropazyl acetate) of Formula 15; Poly (di-butylbutyl dipropazolmalonate / dipropazylcarbinol) of Formula 16; Poly (di-1-ethoxyethyl dipropazylmalonate / dipropazylcarbinol) of Formula 17; Poly (di-2-ethoxypropyl dipropazalmalonate / dipropazylcarbinol) of Formula 18; Poly (di-butylbutyl dipropazyl acetate / dipropazylcarbinol) of Formula 19; Poly (di-1-ethoxyethyl dipropazyl acetate / dipropazylcarbinol) of Formula 20; And A photoresist polymer, characterized in that selected from the group consisting of poly (di-2-ethoxypropyl dipropazyl acetate / dipropazylcarbinol) of formula (21). [Formula 10] [Formula 11] [Formula 12] [Formula 13] [Formula 14] [Formula 15] [Formula 16] [Formula 17] [Formula 18] [Formula 19] [Formula 20] [Formula 21] Wherein x: y is 0.01-99 mol%: 0.01-99 mol%. (a) dissolving the catalyst for metathesis polymerization in an organic solvent to prepare a catalyst solution; (b) adding the catalyst solution to a polymerization solvent and leaving it at a temperature of 20 to 40 ° C. for 10 to 20 minutes; (c) at least one monomer selected from (i) a dipropazyl malonic acid ester derivative of Formula 1 and (ii) a dipropazyl acetate ester derivative of Formula 2 in the resulting solution of step (b); And optionally (iii) adding at least one monomer selected from the group consisting of dipropazyl carbinol of Formula 3; And (d) polymerizing the resultant solution of step (c) under an atmosphere of nitrogen or argon. [Formula 1] [Formula 2] [Formula 3] Wherein R ₁ , R ₂ and R ₃ are the same or different and each is hydrogen, alkyl having 1 to 5 carbon atoms, alkoxyalkyl, 2,3-dihydropyranyl, 2,3-dihydrofuranyl or hydroxy Alkyl. The method of claim 7, wherein The catalyst solution in step (a) is a method for producing a photoresist polymer, characterized in that the prepared by further adding a promoter. The method according to claim 7 or 8, The catalyst or cocatalyst is a method of producing a photoresist polymer, characterized in that the transition metal-halide or organometallic compound. The method of claim 9, The catalyst is selected from the group consisting of MoCl ₅ , WCl ₆ , Mo (OEt) ₅ and PdCl ₂ ; The cocatalyst is (n-Bu) ₄ Sn or EtAlCl _{2 The} method of producing a photoresist polymer, characterized in that. The method of claim 7, wherein The polymerization solvent is selected from the group consisting of chlorobenzene, 1,4-dioxane, dimethylformamide, cyclohexane, tetrachloromethane and tetrahydrofuran. The method according to claim 7 or 8, The organic solvent for dissolving the catalyst or cocatalyst is selected from the group consisting of hexane, tetrahydrofuran and cyclohexane. A photoresist composition comprising a photoresist polymer, an organic solvent and a photoacid generator according to claim 4. delete The method of claim 13, The photoacid generator is diphenyl iodo hexafluorophosphate, diphenyl iodo hexafluoro arsenate, diphenyl iodo hexafluoro antimonate, diphenyl paramethoxyphenyl triflate, diphenyl paratoluenyl triflate, diphenyl Paraisobutylphenyl triflate, diphenylpara-t-butylphenyl triflate, triphenylsulfonium hexafluoro phosphate, triphenylsulfonium hexafluoro arsenate, triphenylsulfonium hexafluoro antimonate, triphenylsulfonium A photoresist composition comprising one or more selected from the group consisting of triflate and dibutylnaphthylsulfonium triflate. The method of claim 13, The photoresist composition is characterized in that used in 0.01 to 10 parts by weight based on 100 parts by weight of the polymer. The method of claim 13, The organic solvent is selected from the group consisting of propylene glycol methyl ether acetate, propylene glycol methyl ether, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate and cyclohexanone. Resist composition. The method of claim 13, The organic solvent is a photoresist composition, characterized in that used in 100 to 1000 parts by weight based on 100 parts by weight of the polymer. (a) applying the photoresist composition of claim 13 over the etched layer to form a photoresist film; (b) baking the photoresist film; (c) exposing the baked photoresist film; (d) baking the exposed photoresist film; And (e) developing the resultant to obtain a desired pattern. delete delete The method of claim 19, The exposure process uses deep ultraviolet (DUV; Deep Ultra Violet), E-beam, X-ray, F ₂ or ion beam including KrF (248 nm), ArF (153 nm), VUV (157 nm) and EUV as the light source. A method of forming a photoresist pattern, characterized in that carried out. delete A semiconductor device manufactured using the method of manufacturing a semiconductor device comprising the method of claim 19.