KR20040002194A - Photoresist Composition Containing Basic Material and Process for Forming Photoresist Pattern Using the Same - Google Patents

Abstract

PURPOSE: A method for forming a photoresist pattern using a photoresist compound including a basic material is provided to form a vertical profile pattern and precisely form the line width of a semiconductor circuit according to the design by making the density of acid uniform in the thickness direction of the photoresist. CONSTITUTION: The photoresist compound includes chemical amplification-type photoresist resin, photoacid generator, organic solvent and basic material. The photoresist compound is formed on an etch target layer to form a photoresist layer. An exposure process is performed on the photoresist layer. A development process is performed on the resultant structure to form a desired pattern(11).

Description

Photoresist composition containing basic material and photoresist pattern forming method using same {Photoresist Composition Containing Basic Material and Process for Forming Photoresist Pattern Using the Same}

The present invention relates to a chemically amplified photoresist composition comprising a basic substance, and more specifically, (a) a chemically amplified photoresist resin (resin), (b) a photoacid generator, (c) The present invention relates to a chemically amplified photoresist composition comprising (d) a basic substance in a chemically amplified photoresist composition composed of an organic solvent, and a pattern forming method using the same.

A 150nm L / S microcircuit was formed by the conventional semiconductor microcircuit manufacturing process using a 248nm (KrF) light source.To form a finer pattern of 150nm L / S or less, ArF (193nm), F ₂ (157) Research into microcircuit fabrication processes using low wavelength light sources, such as EUV (Extremely Ultraviolet (13 nm)), that is, light sources in the far ultraviolet region, continues.

In addition, since the photoresist resin used for i-line (365 nm) and KrF (248 nm) conventionally contains an aromatic compound, it is too large for 193 nm and cannot be used. Therefore, developing a photoresist resin having good transmittance that is applicable to the wavelength, that is, low absorbance remains a big problem.

The acrylic or cyclic aliphatic resins that do not contain aromatic compounds, which have been researched to date, are also difficult to form good patterns due to their relatively high absorbance for use as a photosensitive agent of 193 nm or less.

Thus developed was a chemically amplified photoresist suitable for the light source in the far ultraviolet region, which is composed of a photoresist resin, a photoacid generator and an organic solvent.

The reaction mechanism for the light of the chemically amplified photoresist is shown in FIG. 1, wherein (a) when the chemically amplified photoresist receives light, (b) an acid is generated from a photoacid generator, and (c) In a subsequent step, the post-exposure bake (PEB) process, catalysis is used to remove the dissolution inhibitor, which is the mechanism of action of the photoresist, from the resin.

Then, the resin does not dissolve in the developer when it contains a dissolution inhibitor, but when the dissolution inhibitor is desorbed by an acid, the resin becomes a hydrophilic resin and has a property of being well soluble in the developer. That is, the solubility of the photoresist in the developing solution is so high that the higher the concentration of acid present therein, the higher the solubility. In this case, the dissolution inhibitor is a group which is desorbed by an acid, and is an acid labile protecting group.

However, as shown in FIG. 2, (a) the upper portion of the chemically amplified photoresist is exposed to a large amount of light, and the acid concentration is high, which causes the development to accelerate, thereby increasing the amount of melting of the photoresist.

On the other hand, since the amount of light reaching the lower portion of the photoresist is low, the concentration of acid generated is low, and thus the development is late, so that the amount of melting of the photoresist is small. Therefore, (b) the profile of the chemically amplified photoresist has a problem that forms a slanted triangular pattern rather than a vertical shape (see FIG. 3).

Therefore, the inventors pay attention to the fact that if a basic material is included in the photoresist to overcome the above problems, a vertical pattern may be obtained by neutralizing the acid generated in the upper portion of the photoresist, and thus absorbance of the light source. The present invention was completed by finding that a relatively large chemically amplified photoresist resin can obtain a vertical pattern instead of an inclined pattern.

The present invention aims to solve the above problems and to provide a photoresist composition capable of forming a vertical pattern.

In addition, an object of the present invention is to provide a pattern forming method using the photoresist composition.

1 is a view showing a photoreaction mechanism of the chemically amplified resin.

2 is a cross-sectional view showing a pattern formation when a conventional resin is used.

3 is a pattern photograph obtained when a conventional resin is used.

4 is a cross-sectional view showing the pattern formation in the case of using the resin of the present invention.

5 is a pattern photograph according to Embodiment 6 of the present invention.

6 is a pattern photograph according to the seventh embodiment of the present invention.

7 is a pattern photograph according to the eighth embodiment of the present invention.

8 is a pattern photograph according to a ninth embodiment of the present invention.

9 is a pattern photograph according to the tenth embodiment of the present invention.

<Brief description of the main parts of the drawing>

1: Chemically Amplified Resin 3: Dissolution Inhibitor

5: photoacid generator 7: mask

9, 11: pattern

In order to achieve the above object, the present invention provides a chemically amplified photoresist composition further comprising a basic material in a chemically amplified photoresist resin, a photoacid generator, and an organic solvent.

Hereinafter, the present invention will be described in detail.

As shown in FIG. 4, the basic material coexists with the acid in the photoresist composition during exposure, and then (b) reacts with the acid in a subsequent PEB process to lower the concentration of the acid so that the upper portion of the photoresist is excessive in the developing process. It acts as a quencher to prevent dissolution, and (c) allows the formation of vertical patterns.

That is, since the basic material reacts with the acid actively at the upper portion of the photoresist in which a large amount of light is exposed to increase the concentration of the acid, while reducing the concentration of the acid, the lower amount of light is exposed at the lower portion of the photoresist. The concentration of acid generated is also low, resulting in less reaction between the basic material and the acid. Then, since the acid concentration in the exposed area becomes uniform in the thickness direction of the photoresist, the amount of the photoresist to be dissolved is also equal, so that after development, a vertical photoresist pattern can be obtained (see FIG. 5).

Pyridine or pyridine derivatives are used as the basic substance, and preferably 2-benzyl pyridine, 1,3-di (4-pyridyl) propane (1,3-di (4-pyridyl) propane), 2,2'-dipyridyl, 4,4'-diphenyl-2,2'-dipyridyl (4,4'-diphenyl-2,2'- dipyridyl) and 4-methyl aminopyridine and the like.

In addition, the basic material is included in a ratio of 10 to 50 mol%, preferably 20 to 30 mol% with respect to the photoacid generator.

The chemically amplified photoresist resin includes (i) a cycloolefin moiety having a protecting group sensitive to acid, (ii) a cycloolefin moiety having a hydroxyalkyl group, and (iii) a cyclo having a carboxy or carboxyalkyl group. It is preferable to include the repeating unit which consists of an olefin moiety and (iv) maleic anhydride.

In addition, the chemically amplified photoresist resin preferably comprises a repeating unit represented by the following formula (1).

[Formula 1]

Where

X and Y are CH ₂ , C ₂ H ₄ , oxygen or sulfur,

l, m and n are each an integer selected from 0 to 5,

R ₁ to R ₁₂ are each (i) hydrogen, (ii) an acid sensitive protecting group, (iii) branched or backbone substituted alkyl, ester, ketone, carboxylic acid or acetal having 1 to 10 carbon atoms, or ( iv) branched or main chain substituted alkyl, ester, ketone, carboxylic acid or acetal having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH);

Wherein at least one of R ₁ to R ₄ is a terminal group is hydroxyalkyl, at least one of R ₅ to R ₈ is a protecting group sensitive to an acid, and at least one of R ₉ to R ₁₂ is a carboxyl terminal group Or carboxyalkyl,

More specifically, at least one of R ₁ to R ₄ is —COOR ₁₃ OH, at least one of R ₅ to R ₈ is —COOR _14, and at least one of R ₉ to R ₁₂ is —COOH, wherein wherein R ₁₃ is an alkylene group of C ₁ ~C _10, R ₁₄ is preferably in the acid sensitive protecting group.

a, b, c and d are the polymerization ratios of the respective comonomers.

At this time, more preferable examples of the chemically amplified photoresist resin are as follows.

[Formula 1a]

Where

X and Y are each CH ₂ or CH ₂ CH ₂ ,

R ₁₅ , R ₁₇ and R ₁₈ are each hydrogen or substituted or unsubstituted C ₁ -C ₁₀ alkyl,

R ₁₆ is C ₁ -C ₁₀ hydroxyalkyl,

R ^* is an acid sensitive protecting group.

l, m and n are each an integer selected from 0 to 2,

a: b: c: d is respectively 5 to 90 mol%: 5 to 90 mol%: 0 to 90 mol%: 0 to 90 mol%.

The acid-sensitive protecting group is a group that can be detached by an acid, and refers to a dissolution inhibiting agent that determines whether or not the photoresist resin is dissolved in an alkaline developer. That is, when an acid sensitive protecting group is attached, the photoresist resin is suppressed from being dissolved by the alkaline developer, and when the acid sensitive protecting group is released by the acid generated by exposure, the photoresist resin can be dissolved in the developing solution. do. Such acid-sensitive protecting groups can be any one which can play such a role, for example US 5,212,043 (May 18, 1993), WO 97/33198 (September 12, 1997), WO 96/37526 (Nov. 28, 1996), EP 0 794 458 (October 10, 1997) EP 0 789 278 (August 13, 1997), US 5,750,680 (May 12, 1998), US 6,051,678 (April 18, 2000) , GB 2,345,286 A (July 5, 2000), US 6,132,926 (October 17, 2000), US 6,143,463 (Nov. 7, 2000) and US 6,150,069 (11/21/2000) and the like, for example t − Butyl, tetrahydropyran-2-yl, 2-methyl tetrahydropyran-2-yl, tetrahydrofuran-2-yl, 2-methyl tetrahydrofuran-2-yl, 1-methoxypropyl, 1-methoxy -1-methylethyl, 1-ethoxypropyl, 1-ethoxy-1-methylethyl, 1-methoxyethyl, 1-ethoxyethyl, t -butoxyethyl, 1-isobutoxyethyl or 2-acetylment -1-yl and the like can be used.

A poly (t-butyl bicyclo [2.2.1] hept in a form in which the cycloolefin-based comonomers are additionally polymerized with the chemically amplified photoresist resin having the structure described above so as to remain in the main chain without breaking the ring structure. -5-ene-2-carboxylate / 2-hydroxyethyl bicyclo [2.2.1] hept-5-ene-2-carboxylate / bicyclo [2.2.1] hept-5-ene-2- Carboxylic acid / maleic anhydride) or poly (t-butyl bicyclo [2.2.1] hept-5-ene-2-carboxylate / 2-hydroxyethyl bicyclo [2.2 to improve substrate adhesion; .2] oct-5-ene-2-carboxylate / bicyclo [2.2.1] hept-5-ene-2-carboxylic acid / maleic anhydride) and the like.

Further, the photoacid generator may be used as long as it is a compound capable of generating an acid by light, US 5,212,043 (May 18, 1993), WO 97/33198 (September 12, 1997), WO 96/37526 ( Nov. 28, 1996, EP 0 794 458 (October 10, 1997) EP 0 789 278 (August 13, 1997), US 5,750,680 (May 12, 1998), US 6,051,678 (April 18, 2000), GB 2,345,286 A (July 5, 2000), US 6,132,926 (October 17, 2000), US 6,143,463 (Nov. 7, 2000), and US 6,150,069 (November 21, 2000), and the like, and are mainly sulfur sulfide systems Or onium salt compounds.

Specific examples of the compound that can be used as the photoacid generator include phthalimidotrifluoromethanesulfonate, dinitrobenzyltosylate, n-decyldisulfone, naphthylimidotrifluoromethanesulfonate, diphenyl iodo salt hexafluorophosphate , Diphenyl iodo hexafluoro arsenate, diphenyl iodo hexafluoro antimonate, diphenyl paramethoxyphenyl triflate, diphenyl paratoluenyl triflate, diphenyl paraisobutyl phenyl triflate, triphenyl One or more of sulfonium hexafluoro arsenate, triphenylsulfonium hexafluoro antimonate, triphenylsulfonium triflate or dibutylnaphthylsulfonium triflate, and the like may be used. Preference is given to using at a ratio of 0.1 to 10% by weight.

In this case, when the amount of the photoacid generator is used in an amount of 0.1 wt% or less, the sensitivity of the photoresist to light is weak. When the photoacid generator is used at 10 wt% or more, the photoacid generator absorbs a lot of ultraviolet rays and generates a large amount of acid, so that a bad cross section is obtained. You get

The organic solvent can be any one commonly used, US 5,212,043 (May 18, 1993), WO 97/33198 (September 12, 1997), WO 96/37526 (Nov. 28, 1996), EP 0 794 458 (September 10, 1997) EP 0 789 278 (August 13, 1997), US 5,750,680 (May 12, 1998), US 6,051,678 (April 18, 2000), GB 2,345,286 A (2000. 7. 5), US 6,132,926 (October 17, 2000), US 6,143,463 (11/7/2000) and US 6,150,069 (11/21/2000) and the like, preferably diethylene glycol diethyl ether diethyl ether), methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propylene glycol methyl ether acetate, cyclohexanone or 2-heptanone, and the like can be used alone or in combination. It is used at a ratio of 100 to 2000% by weight relative to the resin, to obtain a photoresist film of a desired thickness.

In addition, the present invention provides a method of forming a photoresist pattern consisting of the following steps:

(a) forming a photoresist film by applying the photoresist composition of the present invention including the basic material on the etched layer;

(b) exposing the photoresist film; And

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

In the above process, the method may further include performing a baking process before and / or after exposure in step (b), and the baking process is performed at 70 to 200 ° C.

In addition, the exposure process is preferably performed with an exposure energy of 1 to 100 mJ / cm ² using ArF, KrF, VUV, EUV, E-beam, X-rays or ion beam as a light source.

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 Chemically Amplified Photoresist Compositions.

Example 1. Preparation of Photoresist Composition

Poly (t-butyl bicyclo [2.2.1] hept-5-ene-2-carboxylate / 2-hydroxyethyl bicyclo [2.2.1] hept-5-ene-2-carboxylate / bicyclo [2.2.1] hept-5-ene-2-carboxylic acid / maleic hydride) Photoresist: 10 g of photoresist polymer and 0.2 g of phthalimidotrifluoromethanesulfonate dissolved in 80 g of propylene glycol methyl ether acetate An additional 0.02 g of 2-benzyl pyridine was added to the composition to prepare a photoresist composition of the present invention.

Example 2. Preparation of Photoresist Composition

The photoresist composition of the present invention was prepared in the same manner as in Example 1, except that 0.04 g of 1,3-di (4-pyridyl) propane was used instead of 2-benzyl pyridine of Example 1.

Example 3. Preparation of Photoresist Composition

The photoresist composition of the present invention was prepared in the same manner as in Example 1, except that 0.03 g of 2,2′-dipyridyl was used instead of 2-benzyl pyridine of Example 1.

Example 4. Preparation of Photoresist Composition

The photoresist composition of the present invention was prepared in the same manner as in Example 1, except that 0.06 g of 4,4'-diphenyl-2,2'-dipyridyl was used instead of 2-benzyl pyridine of Example 1. Prepared.

Example 5. Preparation of Photoresist Composition

The photoresist composition of the present invention was prepared in the same manner as in Example 1, except that 0.02 g of 4-methyl aminopyridine was used instead of 2-benzyl pyridine of Example 1.

II. Pattern formation method using a chemically amplified photoresist composition.

Example 6 Pattern Formation Using Photoresist Composition of the Present Invention

The composition of Example 1 was applied to a silicon wafer and baked at 140 ° C. for 90 seconds, then exposed with an ArF exposure equipment, and then baked again at 140 ° C. for 90 seconds, and developed in a 2.38 wt% TMAH developer to develop a vertical 0.1 μm L. An ultrafine pattern of / S was obtained (see FIG. 5).

Example 7 Pattern Formation Using Photoresist Composition of the Present Invention

The composition of Example 2 was applied to a silicon wafer and baked at 140 ° C. for 90 seconds, then exposed with an ArF exposure equipment, and then baked again at 140 ° C. for 90 seconds, and developed in a 2.38 wt% TMAH developer to develop a vertical 0.1 μm L. An ultrafine pattern of / S was obtained (see FIG. 6).

Example 8. Pattern Formation Using Photoresist Composition of the Present Invention

The composition of Example 3 was applied to a silicon wafer and baked at 140 ° C. for 90 seconds, then exposed with ArF exposure equipment, and then baked again at 140 ° C. for 90 seconds, and developed in a 2.38 wt% TMAH developer to develop a vertical 0.1 μm L. An ultrafine pattern of / S was obtained (see FIG. 7).

Example 9. Pattern Formation Using Photoresist Composition of the Present Invention

The composition of Example 4 was applied to a silicon wafer and baked at 140 ° C. for 90 seconds, then exposed with an ArF exposure equipment, and then baked again at 140 ° C. for 90 seconds, and developed in a 2.38 wt% TMAH developer to develop a vertical 0.1 μm L. An ultrafine pattern of / S was obtained (see FIG. 8).

Example 10 Pattern Formation Using Photoresist Composition of the Present Invention

The composition of Example 5 was applied to a silicon wafer and baked at 140 ° C. for 90 seconds, then exposed with an ArF exposure equipment, and then baked again at 140 ° C. for 90 seconds, and developed in a 2.38 wt% TMAH developer to develop a vertical 0.1 μm L. An ultrafine pattern of / S was obtained (see FIG. 9).

Comparative Example 1. Preparation of conventional photoresist composition

Poly (t-butyl bicyclo [2.2.1] hept-5-ene-2-carboxylate / 2-hydroxyethyl bicyclo [2.2.1] hept-5-ene-2-carboxylate / bicyclo [2.2.1] Hept-5-ene-2-carboxylic acid / maleic hydride) 10 g of a photoresist polymer and 0.2 g of phthalimidotrifluoromethanesulfonate are dissolved in 80 g of propylene glycol methyl ether acetate. The composition was prepared.

Comparative Example 2. Pattern Formation Using Conventional Photoresist Composition

The composition of Comparative Example 1 was applied to a silicon wafer and baked at 140 ° C. for 90 seconds, then exposed with an ArF exposure apparatus, and then baked again at 140 ° C. for 90 seconds, and developed in a 2.38 wt% TMAH developer to form an inclined pattern. Was obtained (see FIG. 3).

As described above, the photoresist composition containing the basic material is uniform in the concentration of the acid in the photoresist thickness direction, thereby obtaining not only a vertical profile pattern but also incidentally measuring the line width by SEM. The reproducibility is improved, the work efficiency is increased, and the line width of the semiconductor circuit can be manufactured exactly as designed, so that the characteristics of the semiconductor can be improved.

Claims (22)

A photoresist composition comprising (a) a chemically amplified photoresist resin, (b) a photoacid generator, (c) an organic solvent, and (d) a basic substance. The method of claim 1, The basic material is a photoresist composition, characterized in that the pyridine or pyridine derivatives. The method of claim 2, The basic substance is 2-benzyl pyridine, 1,3-di (4-pyridyl) propane, 2,2'-dipyridyl ( 2,2'-dipyridyl), 4,4'-diphenyl-2,2'-dipyridyl (4,4'-diphenyl-2,2'-dipyridyl) and 4-methyl aminopyridine Photoresist composition, characterized in that selected from the group consisting of. The method of claim 1, The basic material is a photoresist composition, characterized in that contained in a ratio of 10 to 50 mol% with respect to the photoacid generator. The method of claim 4, wherein The basic material is a photoresist composition, characterized in that contained in a ratio of 20 to 30 mol% with respect to the photoacid generator. The method of claim 1, The chemically amplified photoresist resin (i) a cycloolefin moiety having an acid sensitive protecting group, (ii) a cycloolefin moiety having a hydroxyalkyl group, (iii) a cycloolefin moiety having a carboxy or carboxyalkyl group, (iv) a photoresist composition comprising a repeating unit consisting of maleic anhydride. The method of claim 6, The chemically amplified photoresist resin photoresist composition comprising a repeating unit represented by the formula (1). [Formula 1] Where X and Y are CH ₂ , C ₂ H ₄ , oxygen or sulfur, l, m and n are each an integer selected from 0 to 5, R ₁ to R ₁₂ are each (i) hydrogen, (ii) an acid sensitive protecting group, (iii) branched or backbone substituted alkyl, ester, ketone, carboxylic acid or acetal having 1 to 10 carbon atoms, or ( iv) branched or main chain substituted alkyl, ester, ketone, carboxylic acid or acetal having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH); At this time, at least one or more of R ₁ to R ₄ terminal group is hydroxyalkyl, At least one of R ₅ to R ₈ is a protecting group in which the terminal group is acid sensitive, At least one of R ₉ to R ₁₂ has a terminal group of carboxy or carboxyalkyl, a, b, c and d are the polymerization ratios of the respective comonomers. The method of claim 7, wherein At least one of R ₁ to R ₄ is —COOR ₁₃ OH, At least one of R ₅ to R ₈ is —COOR ₁₄ , At least one of R ₉ to R ₁₂ is —COOH, In this case, R ₁₃ is C ₁ -C ₁₀ alkylene, R ₁₄ is an acid sensitive protecting group. The method of claim 7, wherein The chemically amplified photoresist resin is a photoresist composition, characterized in that represented by the formula (1a). [Formula 1a] Where X and Y are each CH ₂ or CH ₂ CH ₂ , R ₁₅ , R ₁₇ and R ₁₈ are each hydrogen or substituted or unsubstituted C ₁ -C ₁₀ alkyl, R ₁₆ is C ₁ -C ₁₀ hydroxyalkyl, R ^* is an acid sensitive protecting group, l, m and n are each an integer selected from 0 to 2, a: b: c: d is respectively 5 to 90 mol%: 5 to 90 mol%: 0 to 90 mol%: 0 to 90 mol%. The method of claim 6, The acid sensitive protecting groups are t -butyl, tetrahydropyran-2-yl, 2-methyl tetrahydropyran-2-yl, tetrahydrofuran-2-yl, 2-methyl tetrahydrofuran-2-yl, 1- Methoxypropyl, 1-methoxy-1-methylethyl, 1-ethoxypropyl, 1-ethoxy-1-methylethyl, 1-methoxyethyl, 1-ethoxyethyl, t -butoxyethyl, 1- Photoresist composition, characterized in that selected from the group consisting of isobutoxyethyl and 2-acetylment-1-yl. The method of claim 9, The chemically amplified photoresist resin is poly (t-butyl bicyclo [2.2.1] hept-5-ene-2-carboxylate / 2-hydroxyethyl bicyclo [2.2.1] hept-5-ene- 2-carboxylate / bicyclo [2.2.1] hept-5-ene-2-carboxylic acid / maleic hydride) or poly (t-butyl bicyclo [2.2.1] hept-5-ene-2 -Carboxylate / 2-hydroxyethyl bicyclo [2.2.2] oct-5-ene-2-carboxylate /bicyclo[2.2.1]hept-5-ene-2-carboxylic acid / maleicane Hydride) photoresist composition. The method of claim 1, The photoresist composition is a photoresist composition, characterized in that the sulfur salt-based or onium salt-based compound. The method of claim 1, 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 1, The photoresist composition is a photoresist composition, characterized in that used in 0.1 to 10% by weight relative to the photoresist resin. The method of claim 1, The organic solvent is composed of diethylene glycol diethylether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propylene glycol methyl ether acetate, cyclohexanone and 2-heptanone. A photoresist composition comprising one or more selected from the group. The method of claim 1, The organic solvent is a photoresist composition, characterized in that used in 100 to 2000% by weight relative to the photoresist resin. (a) applying the photoresist composition of claim 1 over the etched layer to form a photoresist film; (b) exposing the photoresist film; And (c) developing the resultant to obtain a desired pattern. The method of claim 17, And (b) performing a baking step before (i) before and after exposure or (ii) before or after exposure, respectively, in step (b). The method of claim 18, The baking process is a photoresist pattern forming method, characterized in that performed at 70 to 200 ℃. The method of claim 17, Wherein the exposure process is performed using ArF (193 nm), KrF (248 nm), VUV (157 nm), EUV (13 nm), E-beam, X-ray or ion beam. The method of claim 17, The exposure process is a photoresist pattern forming method, characterized in that performed with an exposure energy of 1 to 100 mJ / cm ² . A semiconductor device manufactured by the method of claim 17.