KR100499869B1 - Novel photoresist crosslinker and photoresist composition using the same - Google Patents

Abstract

The present invention relates to a novel crosslinking monomer for a negative photoresist (Formula 1), a polymer thereof and a photoresist composition using the same, which can be used in the far ultraviolet region. In particular, the crosslinking agent of the present invention is a chemically amplified crosslinking agent composed of a polymer. As a result, the crosslinking density is very large, which is useful for preparing ArF (193 nm) or EUV photoresist requiring light sensitivity.

<Formula 1>

Wherein R1 and R2 each represent a C1-10 main chain or branched chain substituted alkyl, a C1-10 branched or main chain substituted ester, a C1-10 chain or side chain substituted ketone, a C1-10 Side-chain or main-chain substituted carboxylic acids between, side-chain or main-chain substituted acetals having 1 to 10 carbon atoms, side-chain or main-chain substituted alkyl having one or more hydroxyl groups (-OH), one Branched or backbone substituted esters having 1 to 10 carbon atoms containing at least one hydroxyl group (—OH), branched or backbone substituted ketones having 1 to 10 carbon atoms containing at least one hydroxyl group (—OH), one Branched or main chain substituted carboxylic acids having 1 to 10 carbon atoms containing at least one hydroxyl group (—OH) and having 1 to 10 carbon atoms containing at least one hydroxyl group (—OH) Side chain or main chain substituted acetal and the like, and R 3 is hydrogen or methyl, respectively.

Description

Novel photoresist crosslinking agent and photoresist composition using same {NOVEL PHOTORESIST CROSSLINKER AND PHOTORESIST COMPOSITION USING THE SAME}

The present invention relates to a crosslinking agent used in a novel negative photoresist that can be used in the far ultraviolet region, a method for preparing the same, and a negative photoresist composition using the same. More specifically, a photoresist crosslinking agent suitable for a photolithography process using a KrF (148 nm), ArF (193 nm), E-beam, ion beam, or EUV light source, and using the same when fabricating a microcircuit of a highly integrated semiconductor device It relates to a photoresist composition.

In order to achieve high sensitivity in the process of forming microcircuits in semiconductor manufacturing, chemically amplified deep ultra violet (DUV) photoresists have been in the spotlight, and their composition is sensitive to photoacid generators and acids. It is prepared by blending the matrix polymer of the structure.

The action mechanism of the photoresist generates acid when the photoacid generator receives ultraviolet light from the light source, and crosslinking occurs due to the crosslinking reaction between the main chain or the side chain of the matrix polymer by the acid generated in this way, and the light-receiving part is applied to the developer. It will not melt away. In this way, the mask image can be left as a negative image on the substrate. In such a photolithography process, the resolution may form a fine pattern as the wavelength of the light source decreases depending on the wavelength of the light source. However, the smaller the wavelength of the exposure light source to form a fine pattern, that is, when the 193nm or EUV (extremely UV) is used, the lens is deformed by this light source has a disadvantage of shortening the life. In order to overcome this disadvantage, a stronger crosslinking agent is required, and since the crosslinking agent is a chemically amplified type, crosslinking with the photoresist resin should occur even with a small amount of energy. However, crosslinkers of this principle have not been developed.

Melamine, which is a commonly used crosslinking agent, has only three functional groups capable of forming crosslinks with acids. In addition, when the crosslinks are formed, the acid is consumed by the crosslinking, so a large amount of acid must be generated and therefore a large amount of energy is required during exposure.

An object of the present invention is to provide a novel crosslinking monomer for photoresist and a method for producing the same.

The present invention also provides a novel chemically amplified crosslinking agent using the crosslinking monomer and a method for producing the same.

Moreover, it aims at providing the photoresist composition suitable for the photoresist process employing an extreme wavelength light source, and its manufacturing method.

In addition, another object of the present invention is to provide a semiconductor device manufactured using the photoresist composition.

In order to achieve the above object, the present invention provides a novel crosslinking monomer represented by the following formula (1).

<Formula 1>

Where

R1 and R2 are each

Main or branched substituted alkyl of 1 to 10 carbon atoms,

Branched or main chain substituted esters having 1 to 10 carbon atoms,

Main or branched substituted ketones having 1 to 10 carbon atoms,

Branched or main chain substituted carboxylic acids having 1 to 10 carbon atoms,

Branched or main chain substituted acetals having 1 to 10 carbon atoms,

Branched or main chain substituted alkyl having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH),

Branched or main chain substituted esters having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH),

Branched or main chain substituted ketones having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH),

Branched or main chain substituted carboxylic acids having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH), or

Side chain or main chain substituted acetals having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH);

R 3 is hydrogen or methyl, respectively.

Further, in order to achieve another object of the present invention, there is provided a novel photoresist crosslinking agent represented by the following formula (4) or (9).

<Formula 4>

<Formula 9>

In Chemical Formula 4 or 9,

R1 and R2 are each

Main or branched substituted alkyl of 1 to 10 carbon atoms,

Branched or main chain substituted esters having 1 to 10 carbon atoms,

Main or branched substituted ketones having 1 to 10 carbon atoms,

Branched or main chain substituted carboxylic acids having 1 to 10 carbon atoms,

Branched or main chain substituted acetals having 1 to 10 carbon atoms,

Branched or main chain substituted alkyl having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH),

Branched or main chain substituted esters having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH),

Branched or main chain substituted ketones having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH),

Branched or main chain substituted carboxylic acids having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH), or

Side chain or main chain substituted acetals having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH);

R3 and R4 are each hydrogen or methyl.

In addition, in order to achieve another object of the present invention,

(i) a photoresist resin,

(ii) a crosslinking agent of Formula 1 or Formula 4,

(iii) a photoacid generator,

(iv) organic solvent

There is provided a photoresist composition comprising a.

Hereinafter, the present invention will be described in more detail with reference to specific examples.

Preparation of Crosslinking Monomer

The inventors have conducted a number of experiments to find that the compound of formula 1 has suitable properties as a crosslinking monomer of negative photoresist.

<Formula 1>

Where

R1 and R2 are each

Main or branched substituted alkyl of 1 to 10 carbon atoms,

Branched or main chain substituted esters having 1 to 10 carbon atoms,

Main or branched substituted ketones having 1 to 10 carbon atoms,

Branched or main chain substituted carboxylic acids having 1 to 10 carbon atoms,

Branched or main chain substituted acetals having 1 to 10 carbon atoms,

Branched or main chain substituted alkyl having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH),

Branched or main chain substituted esters having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH),

Branched or main chain substituted ketones having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH),

Branched or main chain substituted carboxylic acids having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH), or

Side chain or main chain substituted acetals having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH);

R 3 is hydrogen or methyl, respectively.

The compound of Formula 1 reacts with a photoresist resin having a hydroxyl group (-0H) in the presence of an acid to induce crosslinking between the photoresist resins. In addition, it is a chemically amplified crosslinking agent capable of inducing acid (H +) while being combined with the photoresist resin to induce a chain crosslinking reaction. Therefore, the photoresist resin of the exposed portion can be cured with high density in the post-baking process, so that an excellent negative pattern can be obtained.

Preferred crosslinking monomers according to the present invention include compounds represented by the following formula (2) or (3).

<Formula 2>

<Formula 3>

Referring to the reaction mechanism of the crosslinking agent according to the present invention in more detail as follows.

First, the crosslinking agent according to the present invention and the photoresist resin are mixed and then applied onto a predetermined substrate (first step). Subsequently, when a predetermined region of the substrate is exposed, acid is generated at the exposed portion (second step). Due to the acid generated at the exposure site, at the R1 or R2 position, the crosslinking agent and the photoresist resin according to the present invention are crosslinked, and as a result of the crosslinking, an acid is generated again, thereby performing a chain crosslinking action (third step).

Preparation of Crosslinking Agent

The crosslinking monomer according to the present invention can be used as a crosslinking agent by itself, but the form of the homopolymer or copolymer thereof can also be used as the crosslinking agent.

Synthesis of Crosslinked Copolymer

The copolymer of the following formula (4) is one of the preferred crosslinked copolymers according to the present invention.

<Formula 4>

Where

R1 and R2 are each

Main or branched substituted alkyl of 1 to 10 carbon atoms,

Branched or main chain substituted esters having 1 to 10 carbon atoms,

Main or branched substituted ketones having 1 to 10 carbon atoms,

Branched or main chain substituted carboxylic acids having 1 to 10 carbon atoms,

Branched or main chain substituted acetals having 1 to 10 carbon atoms,

Branched or main chain substituted alkyl having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH),

Branched or main chain substituted esters having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH),

Branched or main chain substituted ketones having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH),

Branched or main chain substituted carboxylic acids having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH), or

Side chain or main chain substituted acetals having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH);

R3 and R4 are each hydrogen or methyl.

In addition, a: b is a polymerization ratio of each monomer which participates in copolymerization, and it is preferable that they are 10-100 mol%: 0-30 mol%, respectively.

Hereinafter, an embodiment of a method for producing a crosslinked copolymer according to the present invention is disclosed.

Example 1

30 g of acrolein of Formula 5, 8 g of acrylic acid of Formula 6, 0.8 g of AIBN, and 58 g of tetrahydrofuran were added to a 200 ml flask, followed by 6 hours of reaction at a temperature of 65 ° C. under nitrogen or argon. After the polymer reaction was completed, the polymer was precipitated in an ethyl ether solvent to obtain a polymer (yield 60%).

20 g of the obtained polymer and 200 g of methanol are added to a 500 ml round flask and mixed well. 0.8 g of trifluoromethane sulfonic acid was added thereto, and the mixture was refluxed at 80 ° C. for 7 hours. After refluxing, the mixture was concentrated on a rotary evaporator and precipitated in distilled water to obtain a methoxy substituted polymer.

20 g of this polymer is charged with 250 g of tetrahydrofuran, 250 g of distilled water, and 30 g of potassium hydroxide in a 1000 ml round flask and refluxed at 100 DEG C for 7 hours. After reflux, place in a separatory funnel and separate the distilled water layer and the tetrahydrofuran layer. The separated tetrahydrofuran layer and the water layer were concentrated with a rotary evaporator, and then acetic acid was dropped to pH 4. The precipitate was taken from distilled water and dried under vacuum to obtain a polymer of the following Chemical Formula 7.

<Formula 5>

<Formula 6>

<Formula 7>

Example 2

Except for using ethanol instead of methanol in Example 1 in the same manner as in Example 1 to obtain a polymer of the formula (8).

<Formula 8>

Synthesis of Crosslinked Homopolymer

In addition, the crosslinking agent according to the present invention may have a homopolymer form of the crosslinking monomer represented by the formula (1). The compound of formula 9 discloses a preferred homopolymer according to the invention.

<Formula 9>

Where

R1 and R2 are each

Main or branched substituted alkyl of 1 to 10 carbon atoms,

Branched or main chain substituted esters having 1 to 10 carbon atoms,

Main or branched substituted ketones having 1 to 10 carbon atoms,

Branched or main chain substituted carboxylic acids having 1 to 10 carbon atoms,

Branched or main chain substituted acetals having 1 to 10 carbon atoms,

Branched or main chain substituted alkyl having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH),

Branched or main chain substituted esters having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH),

Branched or main chain substituted ketones having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH),

Branched or main chain substituted carboxylic acids having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH), or

Side chain or main chain substituted acetals having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH);

R3 is hydrogen or methyl and a represents the number of monomers involved in homopolymerization.

A method for synthesizing a preferred crosslinked homopolymer according to the present invention is as follows.

Example 3

100 g of acrolein, 66 g of tetrahydrofuran (THF), and 2 g of AIBN as a polymerization initiator were placed in a 500 ml round bottom flask, and the flask was vacuumed and reacted at 65 ° C for 5 hours. After the reaction was completed, the produced white solid (poly acrolein) was filtered and washed several times with ethyl ether (yield 60%). The resultant 60 g of the white solid and 500 g of methanol were put into a 1000 ml round bottom flask, followed by After adding 1 ml of fluoromethyl sulfonic acid as a catalyst, the reaction is performed at room temperature (25 ° C.) for 24 hours. White solids that were not initially dissolved (poly acrolein) are dissolved in methanol as the reaction is completed. After completion of the reaction, methanol was removed by a distillation to make a thick state, and precipitated in distilled water was dried in vacuo to obtain a compound of Formula 10.

<Formula 10>

Example 4

A cross-linked homopolymer of Formula 11 was obtained in the same manner as in Example 3, except that metacrolein was used instead of acrolein.

<Formula 11>

Example 5

Except for using ethanol instead of methanol in the same manner as in Example 1 to obtain a cross-linked homopolymer of the formula (12).

<Formula 12>

Example 6

A cross-linked homopolymer of Formula 13 was obtained in the same manner as in Example 1 except that ethanol was used instead of methanol and metacrolein was used instead of acrolein.

<Formula 13>

Preparation of Photoresist Compositions and Formation of Patterns

Hereinafter, the manufacturing method of the negative photoresist composition using the crosslinking agent which concerns on this invention is demonstrated.

Since the crosslinking agent according to the present invention is a chemically amplified crosslinking agent, the photoresist composition according to the present invention comprises (i) a photoresist resin, (ii) a crosslinking agent according to the present invention, and (iii) an acid generator. (Iv) organic solvents are used to mix these materials.

The photoresist resin refers to a conventional photoresist polymer, and particularly suited to an extreme wavelength (250 nm or less). In addition, instead of the photoresist resin, a mixture of each photoresist monomer constituting the same may be used to directly polymerize the crosslinking agent.

The photoacid generator is a sulfur salt-based or onium salt-based diphenyl iodo hexafluorophosphate, diphenyl iodo hexafluoro arsenate, diphenyl iodo hexafluoro antimonate, diphenyl paramethoxyphenyl triflate, diphenyl Paratoluenyl triflate, diphenylparaisobutylphenyl triflate, diphenylpara-t-butylphenyl triflate, triphenylsulfonium hexafluoro phosphate, triphenylsulfonium hexafluor arsenate, triphenylsulfonium hexa One or two or more of fluorine antimonate, triphenylsulfonium triflate and dibutylnaphthylsulfonium triflate may be used.

As the organic solvent, cyclohexanone, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propylene glycol methyl ether acetate or other conventional organic solvents can be used.

First, the photoresist composition prepared according to the present invention is spin-coated on a silicon wafer to form a thin film, and then soft baked for 1 to 5 minutes in an oven or a hot plate at 70 to 200 ° C., more preferably 80 to 150 ° C., After exposing using an ultraviolet exposure apparatus or an excimer laser exposure apparatus, post-baking is performed at 10-200 degreeC more preferably at 100-200 degreeC. In this case, ArF light, KrF light, E-beam, X-ray, extremely ultra violet (EUV), deep ultra violet (DUV) and the like may be used as the exposure source, and the exposure energy is preferably 0.1 to 100 mJ / cm 2. .

The wafer thus exposed is immersed in an alkali developer, for example, 0.01 to 5 wt% of TMAH aqueous solution, especially 2.38% or 2.5% TMAH aqueous solution, and developed for a predetermined time, preferably for 1 minute and 30 seconds, to obtain an ultrafine pattern. .

Example 7

(i) 20 g of a photoresist resin of formula (14), (ii) 10 g of crosslinking agent of formula (7) obtained in Example 1 of the present invention, and (iii) 0.6 g of triphenyl sulfonium triflate as photoacid generator (iv) A photoresist composition was prepared by dissolving in 200 g of an organic solvent, propylene glycol methyl ether acetate.

<Formula 14>

The said d: e: f is a polymerization ratio of each monomer which comprises a photoresist resin.

The photoresist composition thus prepared was applied onto a silicon wafer, soft baked at 110 ° C. for 90 seconds, and then exposed with an ArF exposure apparatus, followed by post-baking at 110 ° C. for 90 seconds, followed by development with a 2.38 wt% TMAH developer. An ultrafine negative pattern of 0.13 µm L / S was obtained.

In this case, the irradiated exposure energy was 15 mJ / cm 2, and the curing sensitivity of the photoresist composition was very excellent even at such a low intensity exposure energy because of the excellent crosslinking ability of the crosslinking agent (formula 7) used.

Example 8

A photoresist composition was manufactured in the same manner as in Example 3, except that the compound of Formula 15 was used as a photoresist resin instead of the compound of Formula 14, to form a photoresist pattern. As a result, an ultrafine negative pattern of 0.18 µm L / S was obtained.

<Formula 15>

The said d: e: f is a polymerization ratio of each monomer which comprises a photoresist resin.

Example 9

A photoresist composition was manufactured in the same manner as in Example 7, except that the compound of Formula 16 was used as a photoresist resin instead of the compound of Formula 14, and then a photoresist pattern was formed using the compound. As a result, an ultrafine negative pattern of 0.20 µm L / S was obtained.

<Formula 16>

The said d: e: f is a polymerization ratio of each monomer which comprises a photoresist resin.

Example 10

Except for using the compound of Formula 17 as a photoresist resin instead of the compound of Formula 14 to prepare a photoresist composition in the same manner as in Example 7, and then used to form a photoresist pattern. As a result, an ultrafine negative pattern of 0.20 µm L / S was obtained.

<Formula 17>

The said d: e: f is a polymerization ratio of each monomer which comprises a photoresist resin.

Example 11

A photoresist composition was prepared in the same manner as in Example 7, except that the compound of Formula 18 was used as a photoresist resin instead of the compound of Formula 14, and then a photoresist pattern was formed using the compound. As a result, an ultrafine negative pattern of 0.20 µm L / S was obtained.

<Formula 18>

The said d: e: f is a polymerization ratio of each monomer which comprises a photoresist resin.

When the photoresist composition is prepared using the novel crosslinking agent according to the present invention, the density of crosslinking is so great that the difference in the degree of curing of the photoresist resin between the exposed portion and the non-exposed portion becomes remarkable, and thus the photo having a better profile A resist pattern can be obtained. In addition, since the crosslinking agent according to the present invention is a chemically amplified type, it is possible to achieve a sufficient effect by using only a small amount of photoacid generator, thereby solving the problem caused by the inclusion of a large amount of photoacid generator, and excellent light sensitivity, so low exposure Sufficient exposure effect can be achieved by irradiating an energy. Therefore, it is suitable for photolithography employing ultra fine patterns, especially light sources in extreme wavelength regions such as ArF (193 nm) light sources.

Claims (23)

A photoresist crosslinking monomer represented by the following formula (1). <Formula 1> Where R1 and R2 are each Main or branched substituted alkyl of 1 to 10 carbon atoms, Branched or main chain substituted esters having 1 to 10 carbon atoms, Main or branched substituted ketones having 1 to 10 carbon atoms, Branched or main chain substituted carboxylic acids having 1 to 10 carbon atoms, Branched or main chain substituted acetals having 1 to 10 carbon atoms, Branched or main chain substituted alkyl having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH), Branched or main chain substituted esters having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH), Branched or main chain substituted ketones having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH), Branched or main chain substituted carboxylic acids having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH), or It is selected from the group consisting of branched or main chain substituted acetals having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH), R 3 is hydrogen or methyl, respectively. The method of claim 1, The cross-linking monomer is a cross-linking monomer, characterized in that the compound of formula (2) or formula (3). <Formula 2> <Formula 3> The photoresist crosslinking agent selected from the group which consists of a crosslinking monomer of Claim 1, its homopolymer, and its copolymer. The method of claim 3, The copolymer (i) a first comonomer comprising the crosslinking monomer according to claim 1, (ii) (meth) acrylic acid as a second comonomer Crosslinking agent comprising a. The method of claim 4, wherein The copolymer is a crosslinking agent, characterized in that the compound of formula (4). <Formula 4> Where R1 and R2 are each Main or branched substituted alkyl of 1 to 10 carbon atoms, Branched or main chain substituted esters having 1 to 10 carbon atoms, Main or branched substituted ketones having 1 to 10 carbon atoms, Branched or main chain substituted carboxylic acids having 1 to 10 carbon atoms, Branched or main chain substituted acetals having 1 to 10 carbon atoms, Branched or main chain substituted alkyl having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH), Branched or main chain substituted esters having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH), Branched or main chain substituted ketones having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH), Branched or main chain substituted carboxylic acids having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH), or It is selected from the group consisting of branched or main chain substituted acetals having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH), R3 and R4 are each hydrogen or methyl. The method of claim 5, The a: b is a polymerization ratio of each comonomer, each crosslinking agent, characterized in that 10 to 100 mol%: 0 to 30 mol%. The method of claim 3, The copolymer is a crosslinking agent, characterized in that selected from the group consisting of the compound of formula (7) or formula (8). <Formula 7> <Formula 8> The method of claim 3, The homopolymer is a crosslinking agent, characterized in that the compound of formula (9). <Formula 9> Where R1 and R2 are each Main or branched substituted alkyl of 1 to 10 carbon atoms, Branched or main chain substituted esters having 1 to 10 carbon atoms, Main or branched substituted ketones having 1 to 10 carbon atoms, Branched or main chain substituted carboxylic acids having 1 to 10 carbon atoms, Branched or main chain substituted acetals having 1 to 10 carbon atoms, Branched or main chain substituted alkyl having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH), Branched or main chain substituted esters having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH), Branched or main chain substituted ketones having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH), Branched or main chain substituted carboxylic acids having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH), or Side chain or main chain substituted acetals having 1 to 10 carbon atoms containing at least one hydroxyl group (-OH); R3 is hydrogen or methyl and a represents the number of monomers involved in homopolymerization. The method of claim 8, The homocopolymer is any one of the compounds of the formulas (10) to (13). <Formula 10> <Formula 11> <Formula 12> <Formula 13> (i) a photoresist resin, (ii) at least one crosslinking agent selected from the group consisting of the crosslinking monomer according to claim 1, these homopolymers, and copolymers thereof; (iii) a photoacid generator, (iv) A photoresist composition comprising an organic solvent. The method of claim 10, The photoresist resin composition, characterized in that it comprises a conventional photoresist polymer. The method of claim 10, The photoresist resin is a photoresist composition, characterized in that selected from the group consisting of compounds of the following formula 14, 15, 16, 17 and 18. <Formula 14> <Formula 15> <Formula 16> <Formula 17> <Formula 18> The said d: e: f is a polymerization ratio of each comonomer which comprises the said photoresist resin. The method of claim 10, 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 Photoresist composition, characterized in that 1 or 2 or more selected from the group consisting of triflate and dibutylnaphthylsulfonium triflate. The method of claim 10, The organic solvent is selected from the group consisting of cyclohexanone, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate and propylene glycol methylether acetate. (a) applying the photoresist composition of claim 10 on top of a predetermined etching layer to form a photoresist film; (b) exposing the photoresist film using an exposure apparatus; and (c) developing the resultant photoresist pattern. The method of claim 15, And the exposure apparatus uses an exposure source selected from the group consisting of ArF light (193 nm), KrF light (248 nm), E-beam, X-ray, EUV and deep ultra violet (DUV). The method of claim 15, Wherein said developing step is performed using an alkaline developer. The method of claim 17, The alkaline developer is characterized in that 0.01 to 5wt% TMAH aqueous solution. The method of claim 17, Wherein said alkaline developer is 2.38 wt% aqueous TMAH solution. The method of claim 15, And before and / or after the step (b). The method of claim 20, The baking process is characterized in that performed for 1 to 5 minutes at 70 to 200 ℃. The method of claim 15, And wherein said photoresist pattern is a negative pattern. A semiconductor device manufactured by the method of claim 15.