KR20030055876A - Derivatives of 3,4-dihydro-2H-pyran, photosensitive polymers using the same and photoresist compositions using the photosensitive polymers - Google Patents

Abstract

The present invention relates to a 3,4-dihydrodi- 2H -pyran derivative, a photosensitive polymer using the same, and a photoresist composition using the photosensitive polymer, wherein the photosensitive polymer according to the present invention has a vinyl ether type active site. It is characterized by having a, 4-dihydrodi- 2H -pyran ring as a polymer backbone. The photoresist composition according to the present invention includes the photosensitive polymer, a photo acid generator and a solvent, and may further include a base additive. The photosensitive polymer according to the present invention has a strong hydrophilic property and excellent adhesion to the film quality of the resist film, it is possible to use a general developer at the time of development, the photoresist composition according to the present invention is ArF (193nm) and next-generation F2 (157nm) excimer It can be exposed by laser, has excellent resistance to dry etching, and has high resolution.

Description

3,4-dihydro-2H-pyran derivatives, photosensitive polymers using the same, and photoresist compositions using the same photosensitive polymers {Derivatives of 3,4-dihydro-2H-pyran, photosensitive polymers using the same and photoresist compositions using the photosensitive polymers }

The present invention relates to a 3,4-dihydrodi- 2H -pyran derivative, a photosensitive polymer using the same, and a photoresist composition using the photosensitive polymer, and more particularly, to ArF (193 nm) and next generation F2 (157 nm) excimer laser. The present invention relates to a photosensitive polymer which can be exposed to light, has excellent resistance to dry etching, and has high resolution, a composition for chemically amplified photoresist using the same, and a patterning method thereof.

As lithography technology has become increasingly micropatterned, revealing the limitations of pattern formation in currently used exposure sources, new sources of exposure with shorter wavelength ranges have emerged. Accordingly, lithography techniques using ArF (193 nm) or F2 (157 nm) lasers, which are shorter energy sources than KrF (248 nm) excimer lasers currently used in semiconductor processes, have emerged, and new resist materials suitable for them are required.

On the other hand, these materials should have high transmittance in the light source in which the resist film is used, should have good etching resistance to the plasma gas used in the dry etching process, and adhere to the underlying film to prevent phenomena such as pattern collapse. It should be good and satisfies basic characteristics such as developing with a general developing solution.

Therefore, in order to satisfy such material properties, there are many material limitations. The main problems have been pointed out mainly in terms of permeability and dry etching resistance of polymer materials.

To date, various materials have been known as next-generation resist materials, and most of them are polymers such as poly (meth) acrylate, cycloolefin-maleic anhydride (COMA), and polynorbornene. Systems have been mainly studied.

However, these materials also have a problem that they do not satisfactorily satisfy the resist properties required above to date.

Accordingly, the first technical problem to be achieved by the present invention is a monomer which can be exposed to ArF (193 nm) and next-generation F2 (157 nm) excimer laser, has excellent resistance to dry etching, and can produce a photosensitive polymer having high resolution. To provide.

In addition, the second technical problem to be achieved by the present invention is to provide a photosensitive polymer obtained by using the monomer.

In addition, a third technical problem to be achieved by the present invention is to provide a chemically amplified photoresist composition using a photosensitive polymer having the above-described efficacy.

In addition, a fourth technical problem to be achieved by the present invention is to provide a photoresist patterning method using the photoresist composition.

In order to achieve the first technical problem, the monomer according to the present invention is characterized by being a 3,4-dihydropyran derivative having an active site of a vinyl ether type such as the following Chemical Formula 1.

Wherein x = 0, 1 and R is hydrogen, halogen, nitrile, hydroxy or alkyl having 1 to 20 carbon atoms, alkyl carbonyl, alkyl ester, alkoxy group.

Meanwhile, R is t-butyl ester, tetrahydropyranyl ester, 1-ethoxyethyl ester, 2-methyl-2-adamantyl ester, 2-ethyl-2-adamantyl ester, 2-propyl-2 Preference is given to any one selected from the group consisting of -adamantyl ester, 8-methyl-8-tricyclodecanyl ester and 8-ethyl-8-tricyclodecanyl ester.

In order to achieve the second technical problem, the photosensitive polymer according to the present invention is characterized in that the polymer main chain includes a repeating unit represented by the following Chemical Formula 2. The polymer preferably has a mass average molecular weight of 3,000 to 50,000.

Wherein x = 0, 1 and R is hydrogen, halogen, nitrile, hydroxy or alkyl having 1 to 20 carbon atoms, alkyl carbonyl, alkyl ester, alkoxy group.

According to an embodiment of the present invention, R is t-butyl ester, tetrahydropyranyl ester, 1-ethoxyethyl ester, 2-methyl-2-adamantyl ester, 2-ethyl-2-adamantyl ester, It is preferably one selected from the group consisting of 2-propyl-2-adamantyl ester, 8-methyl-8-tricyclodecanyl ester and 8-ethyl-8-tricyclodecanyl ester.

In another aspect, the present invention provides a photosensitive polymer comprising a repeating unit, such as the following formula (3), characterized in that the mass average molecular weight is 3,000 to 50,000.

Wherein x = 0, 1, R ₁ is hydrogen, halogen, nitrile, hydroxy or alkyl having 1 to 20 carbon atoms, alkyl carbonyl, alkyl ester, alkoxy group, R ₂ is hydrogen or methyl, R ₃ Is hydrogen or a C1-C20 alkyl, hydroxyalkyl, fluoroalkyl group, and m / (m + n) = 0.1-0.9.

Meanwhile, according to the embodiment of the present invention, R ₁ is t-butyl ester, tetrahydropyranyl ester, 1-ethoxyethyl ester, 2-methyl-2-adamantyl ester, 2-ethyl-2-adama Preference is given to any one selected from the group consisting of a methyl ester, 2-propyl-2-adamantyl ester, 8-methyl-8-tricyclodecanyl ester and 8-ethyl-8-tricyclodecanyl ester.

R ₃ is 2-hydroxyethyl, trifluoroethyl, hexafluoroisopropyl, pentafluoropropyl, t-butyl, tetrahydropyranyl, 1-ethoxyethyl, 2-methyl-2-adamantyl , 2-ethyl-2-adamantyl, 2-propyl-2-adamantyl, 8-methyl-8-tricyclodecanyl and 8-ethyl-8-tricyclodecanyl It is preferable.

In addition, the present invention provides a photosensitive polymer comprising a polymer structure as shown in the following formula 4, characterized in that the mass average molecular weight is 3,000 to 50,000.

Wherein x = 0, 1 and R is hydrogen, halogen, nitrile, hydroxy or alkyl having 1 to 20 carbon atoms, alkyl carbonyl, alkyl ester, alkoxy group.

According to an embodiment of the invention, wherein R is t-butyl ester, tetrahydropyranyl ester, 1-ethoxyethyl ester, 2-methyl-2-adamantyl ester, 2-ethyl-2-adamantyl ester , 2-propyl-2-adamantyl ester, 8-methyl-8-tricyclodecanyl ester, 8-ethyl-8-tricyclodecanyl ester, isobornyl ester, norbornyl Preference is given to any one selected from the group consisting of esters, 2-hydroxyethyl esters, 2-hydroxy hexafluoroisopropyl and 2-hydroxy hexafluoroisobutyl.

According to the present invention, the photosensitive polymer including the polymer structure of Formula 3 or 4 further includes at least one selected from the group consisting of norbornene, acrylate, methacrylate derivative and 4-hydroxystyrene derivative as a comonomer. It may be a three or more copolymer made.

On the other hand, in order to achieve the third technical problem, the chemically amplified photoresist composition according to the present invention is characterized in that it comprises the photosensitive polymer, a photo acid generator and a solvent according to the present invention.

The photoacid generator is preferably selected from the group consisting of triphenylsulfonium triflate, diphenyl iodonium triflate and di-t-butylphenyl iodonium triflate.

The content of the photoacid generator is preferably included in 1 to 15% by weight based on the weight of the photosensitive polymer. If it is less than 1% by weight, the sensitivity is too low, if it exceeds 15% by weight may cause a problem that the transmittance of the resist is lowered.

The photoresist composition according to the present invention may further include a base additive.

The base additive is preferably selected from the group consisting of triethylamine, triisobutylamine, triisooctylamine, diethanolamine and triethanolamine, more preferably tertiary amine.

On the other hand, the content of the base additive is preferably 0.01 to 2% by weight based on the weight of the photosensitive polymer. If it is less than 0.01% by weight, T-topping may occur during resist patterning, and if it exceeds 2% by weight, the sensitivity of the resist may be deteriorated.

In addition, in order to achieve the fourth technical problem of the present invention, the photoresist patterning method according to the present invention includes resist film formation, soft-bake, exposure, post-exposure bake (PEB), and development. The process proceeds through the steps. This is divided into each step as follows.

(1) Coating step (resist film formation): A step of coating the photoresist composition according to the present invention on a silicon wafer, which depends on the use of the light source, but is preferably coated with a thickness of about 0.2 to 0.7 μm.

(2) Pre-baking step: The step of pre-baking to remove the solvent remaining in the resist film formed above, the baking temperature varies depending on the type of protection group, usually from 100 to 150 ℃ for about 60 to 90 seconds It is preferable to carry out.

(3) an exposure step; Depending on the deep-UV light source used, it is usually desirable to use an energy of 5-100 mJ / cm ² for ArF or F2 lasers.

(4) Post-exposure baking (PEB) step: After the exposure, baking to cause a deprotection reaction, the baking temperature varies depending on the type of protection group, usually from 100 to 150 ℃ for about 60 to 90 seconds It is preferable to carry out.

(5) Developing step: Developing using a developing solution, which is usually performed for about 30 to 60 seconds with 2.38% by weight of TMAH (0.26N, tetramethyl ammonium hydroxide) solution. desirable.

Hereinafter, the present invention will be described in more detail.

The photosensitive polymer according to the present invention has a 3,4-dihydro-2 H -pyran ring having an active site of vinyl ether type as a polymer main chain, and is prepared to have a uniform molecular weight distribution by cationic polymerization or general radical polymerization. Can be. These polymers have an alicyclic structure in which the main chain has an alicyclic structure, and has a form in which various alicyclic protecting groups are substituted with a protecting group in the polymer chain, thereby having a very advantageous structure for dry etching resistance of the resist film. In addition, the absorbance in the DUV region is relatively low, and thus the permeability of the resist film is excellent, and since the polymer chain has an aliphatic ring, the dry etching resistance is good, and when developing the resist pattern, it can be developed as a general developer. In addition, the polymer chain structure of vinyl ether is more hydrophilic than the cyclopolymers such as polynorbornene or COMA structure, and has excellent adhesion to the film quality of the resist film. It also has advantages.

On the other hand, such photosensitive polymers are used for cationic polymerization using various Lewis acid catalyst systems such as BF ₃ -acrylate, AlR ₃ , ZnCl ₂ , SnCl ₄ , WCl ₆ , TiCl ₄ or HI / I ₂ , HI / ZnI ₂ . It can be easily prepared in the form of homopolymer or copolymer having a constant molecular weight distribution, and also copolymers with monomers having electron-deficiency characteristics such as maleic anhydride, acrylate, methacrylate, etc. are common radical catalysts (initiators). It can be manufactured easily using. The Lewis acid catalyst is preferably about 0.1 to 5.0 mol% of the monomer concentration, the mass average molecular weight of the resulting polymer is about 3,000 to 50,000 and the dispersion range is preferably about 1.1 to 2.0.

In the case of the above-mentioned homopolymer or copolymer or higher copolymer, PAG (photoacid generator), and a small amount of base additive are dissolved in various solvents depending on the solubility in the polymer to form a resist composition. As a solvent used here, PGMEA (propylene glycol methyl ether acetate), cyclohexanone, ethyl lactate, etc. are preferable.

Formula 5 below represents an example of a copolymer that can be easily prepared according to the present invention.

Hereinafter, the present invention will be described in more detail with reference to preferred examples, but the present invention is not limited thereto.

Example 1

Synthesis of Monomer (I)

As shown in Scheme 1 below, 2-methyl-2-adamantyl 5-norbornene obtained from the Diels-Alder reaction of cyclopentadiene with 2-methyl-2-adamantyl acrylate. Esterate (10 g, 0.035 mol) and acrolein (3.92 g, 0.07 mol) are added together with a small amount of diethyl ether in a par reactor and then kept at about 150 ° C. and at a pressure of about 100 atm. The reaction was carried out for 18 hours.

After the reaction was completed, the solvent was removed using a rotary evaporator, and then the product was separated using column chromatography (hexane: ethyl acetate = 4: 1), and the pure product was obtained by recrystallization using ethanol. (Yield 50%)

Example 2

Synthesis of Monomer (II)

As shown in Scheme 2 below, 2-methyl-2-adamantyl 6-dinonorbornene esterate obtained in the Diels-Alder reaction of dicyclopentadiene with 2-methyl-2-adamantyl acrylate (10 g, 0.028 mol) and acrolein (3.2 g, 0.056 mol) were added to a high pressure reactor together with a small amount of diethyl ether, and then reacted for about 18 hours while maintaining a temperature of about 150 ° C and a pressure of about 100 atmospheres.

After the reaction was completed, the solvent was removed using a rotary evaporator, and then the product was separated using column chromatography (hexane: ethyl acetate = 4: 1), and a pure product was obtained by recrystallization using ethanol. (Yield 45%)

Example 3

A monomer was obtained in the same manner as in Examples 1 and 2, except that 2-ethyl-2-adamantyl acrylate was used instead of 2-methyl-2-adamantyl acrylate. (Yield: 47%)

Example 4

Synthesis of Monomers (III, IV)

8-ethyl-8-tricyclodecanyl 5-norbornene esterate (10.5 g) obtained in the Diels-Alder reaction of dicyclopentadiene or cyclopentadiene with 8-ethyl-8-tricyclodecanyl acrylate , 0.035 mol), or 8-ethyl-8-tricyclodecanyl 5-dinobornene esterate (12.8 g, 0.035 mol) with acrolein (3.92 g, 0.07 mol) and a small amount of diethyl ether, respectively, Put in. The reaction temperature was maintained at about 100 ° C. at about 150 ° C. for about 18 hours to obtain monomers (III) and (IV) of the following formula (6).

After the reaction was completed, the solvent was removed using a rotary evaporator, and then the product was separated using column chromatography (hexane: ethyl acetate = 4: 1), and each product was purified by recrystallization using ethanol. there was. (Yield 60%)

Example 5

Synthesis of Homopolymer

As shown in Scheme 3 below, the monomer (I) (3 g, 8.76 mmol) obtained in Example 1 was dissolved in anhydrous methylene chloride (12 g) in a round bottom flask, and then completely purged with nitrogen gas, followed by Boron trifluoride etherate (0.02 g, 1.0 mol%) was added and polymerized at −30 ° C. for 4 hours.

After the end of the polymerization, a small amount of methanol was added to the reaction and then the reaction was slowly precipitated in excess methanol containing a small amount of aqueous ammonia solution. The resulting precipitate was then filtered using glass fibers and once again the precipitate was dissolved in an appropriate amount of THF. It was reprecipitated in n-hexane and then dried in a vacuum oven at 50 ° C. for 24 hours to obtain a homopolymer. (Yield: 85%, mass average molecular weight (Mw) = 10,500, dispersion degree (Mw / Mn) = 1.8 )

Example 6

A homopolymer was obtained in the same manner as in Example 5 except that the monomers (III) and (IV) obtained in Example 4 were used. (When the monomer (III) was used: yield = 80%, mass average molecular weight (Mw). ) = 11,000, dispersion degree = 1.9; using monomer (IV): yield = 78%, mass average molecular weight (Mw) = 9,700, dispersion degree = 2.1)

Example 7

Synthesis of Copolymer

As shown in Scheme 4 below, the monomer (I) (3.4 g, 10 mmol) obtained in Example 1 and the Diels-Alder additive (V) (1.5 g, 10 mmol) of acrolein and norbornene were obtained in a round bottom flask. After dissolving in methylene chloride (25 g) and then completely purged with nitrogen gas, boron trifluoride etherate (0.07 g, 2.5 mol%) was added and polymerized at a temperature of -30 ° C for about 3 hours.

After the end of the polymerization, a small amount of methanol was added to the reaction, and then the reaction was slowly precipitated in excess methanol with a small amount of aqueous ammonia solution. The resulting precipitate was then filtered using glass fibers, and once again the precipitate was dissolved in an appropriate amount of THF. The precipitate was reprecipitated in n-hexane and dried in a vacuum oven at 50 ° C. for about 24 hours to obtain a copolymer. (Yield: 80%, mass average molecular weight (Mw) = 11,400, dispersion degree (Mw / Mn) = 2.1)

Example 8

Synthesis of Copolymer

In a round bottom flask, monomer (I) (3.4 g, 10 mmol) prepared in Example 1 and a Diels-Alder additive (0.83 g, 5 mmol) of acrolein and 5-norbornene-2-ol were added to methylene chloride (12 g). It was dissolved in, completely purged with nitrogen gas, and then WCl ₆ (1.0 mol%) catalyst solution was added, followed by polymerization at room temperature for about 4 hours. After the end of the polymerization, a small amount of methanol was added to the reaction and then the reaction was slowly precipitated in excess water / methanol (2: 8). The resulting precipitate was then filtered using glass fibers, and once again the precipitate was dissolved in an appropriate amount of THF. The precipitate was reprecipitated in n-hexane and then dried in a vacuum oven at 50 ° C. for about 24 hours to obtain a copolymer of the following Chemical Formula 7. (Yield; 70%, mass average molecular weight (Mw) = 10,600, dispersion degree (Mw) / Mn) = 2.2)

Example 9

Synthesis of Copolymer

Diels-Alder Additive (2.5 g, 10 mmol) of Acrolein and 2-t-Butyl-5-norbornene Esterate in a Round Bottom Flask and Acrolein and 2-hexafluoroisopropyl-5-norbornene Esterate The Diels-Alder Additives (1.7 g, 5 mmol) were dissolved in methylene chloride (12 g), completely purged with nitrogen gas, and then SnCl ₄ (1.0 mol%) catalyst solution was added thereto, followed by room temperature. The polymerization was carried out for about 4 hours. After the end of the polymerization, a small amount of methanol was added to the reaction and then the reaction was slowly precipitated in excess methanol. The resulting precipitate was filtered using glass fibers and then once again the precipitate was dissolved in an appropriate amount of THF. The precipitate was reprecipitated in n-hexane and dried in a vacuum oven at 50 ° C. for about 24 hours to obtain a copolymer of the following Formula 8. (Yield: 80%, mass average molecular weight (Mw) = 10,200, dispersion degree (Mw / Mn) = 1.8)

Example 10

Synthesis of Copolymer

As shown in Scheme 5 below, the monomer (I) obtained in Example 1 (3.4 g, 10 mmol) and 2-hydroxyethyl acrylate (0.4 g, 3 mmol) were added together with t-butyl peroxide (20 mol%) to PGMEA. It was dissolved in (6 g) and placed in an ampoule flask. Oxygen gas remaining in the solution was removed using liquid nitrogen, completely purged with nitrogen gas, and then polymerized at about 130 ° C. for about 3 hours.

After the end of the polymerization, the reaction was slowly precipitated in excess methanol, then the resulting precipitate was filtered using glass fibers and once again the precipitate was dissolved in an appropriate amount of THF. The precipitate was reprecipitated in n-hexane and dried in a vacuum oven at 50 ° C. for about 24 hours to obtain a copolymer. (Yield: 70%, mass average molecular weight (Mw) = 8,700, dispersion degree (Mw / Mn) = 2.2)

Example 11

Synthesis of Copolymer

Diels-Alder Additive (V) (1.5 g, 10 mmol) and 2-methyl-2-adamantyl methacrylate (2.4 g, 10 mmol) of acrolein and norbornene in t-butyl peroxide (20 mol%) And dissolved in PGMEA (6g) and placed in an ampoule flask. Oxygen gas remaining in the solution was removed using liquid nitrogen, completely purged with nitrogen gas, and then polymerized at about 130 ° C. for about 8 hours. After the end of the polymerization, the reaction was slowly precipitated in excess methanol, then the resulting precipitate was filtered using glass fibers and once again the precipitate was dissolved in an appropriate amount of THF. This was reprecipitated in n-hexane and dried in a vacuum oven at 50 ° C. for 24 hours to obtain a copolymer of the following Formula 9. (Yield: 60%, Mass Average Molecular Weight (Mw) = 6,700, Dispersion (Mw) / Mn) = 2.1)

Example 12

Synthesis of Copolymer

As shown in Scheme 6, monomer (II) (4.1 g, 10 mmol) and maleic anhydride (1 g, 10 mmol) obtained in Example 2 were added to a round bottom flask with AIBN (azobisisobutyronitrile) (0.05 g, 1.5 mol%). It was dissolved together in THF (10 g), and then completely purged with nitrogen gas, and then polymerized at about 65 ° C. for 20 hours. After the polymerization was completed, the reactant was slowly dropped into excess methanol to precipitate, the resulting precipitate was filtered, and then dissolved in THF and reprecipitated in excess n-hexane. The resulting precipitate was filtered and dried in a vacuum oven at 50 ° C. for 24 hours to obtain a copolymer. (Yield: 80%, mass average molecular weight (Mw) = 11,600, dispersion degree (Mw / Mn) = 1.9)

Example 13

Synthesis of Terpolymer

In a round bottom flask, monomer (I) (3.4 g, 10 mmol), maleic anhydride (1 g, 10 mmol) and norbornene (0.94 g, 10 mmol) obtained in Example 1 were mixed with AIBN (0.05 g, 1 mol%) in THF. Dissolved in (6 g). After complete purging with nitrogen gas, the polymerization was carried out at about 65 ° C. for 20 hours. After the polymerization was completed, the reactant was slowly dropped in excess methanol to precipitate, and the resulting precipitate was filtered and then dissolved in THF and reprecipitated in excess n-hexane. The resulting precipitate was filtered and dried in a vacuum oven at 50 ° C. for 24 hours to obtain a terpolymer of formula 10 (yield: 70%, mass average molecular weight (Mw) = 11,200, dispersion degree (Mw / Mn)). = 2.0)

Example 14

Photoresist Compositions and Patterning Processes

The homopolymer (1 g) obtained in Example 5 was dissolved in propylene glycol methyl ether acetate (PGMEA) (7 g) together with triphenylsulfonium triflate (0.01 g), and then triisobutylamine (2 mg) was added thereto completely. Melted. The resist solution was coated on a raw silicon wafer treated with HMDS (hexamethyldisilazane) to a thickness of about 0.3 μm, and then pre-baked at 130 ° C. for about 90 seconds, followed by ArF stepper (0.6NA, (0.75) was used for exposure. Subsequently, a post-exposure bake (PEB) was performed at 130 ° C. for about 60 seconds, and then developed in a 2.38 wt% TMAH (tetramethyl ammonium hydroxide) solution for about 60 seconds to obtain a clean shape at about 15 mJ / cm ² . 180 nm line and space patterns were found.

Example 15

Photoresist Compositions and Patterning Processes

The copolymer (1 g) obtained in Examples 6, 7, 8, 9 and 10 was dissolved in PGMEA (7 g) together with triphenylsulfonium triflate (0.01 g), and then triisooctylamine (2 mg) was added thereto. Completely dissolved. The resist solution was coated on an HMDS-treated raw silicon wafer with a thickness of about 0.3 μm, prebaked at 130 ° C. for about 90 seconds, and then exposed using ArF stepper (0.6NA, σ 0.75). Subsequently, PEB was performed at 130 ° C. for about 60 seconds, and then developed in 2.38 wt% TMAH solution for about 60 seconds. As a result, a clear 180 nm L / S pattern was confirmed at about 11-18 mJ / cm ² .

Example 16

Photoresist Compositions and Patterning Processes

The alternating copolymer (1 g) obtained in Example 11 was dissolved in PGMEA (7 g) together with triphenylsulfonium triflate (0.01 g), and then triisobutylamine (2 mg) was added thereto to completely dissolve it. The resist solution was coated on a HMDS-treated raw silicon wafer to a thickness of about 0.3 μm, prebaked at 130 ° C. for about 90 seconds, and then exposed using an ArF stepper (0.6NA, σ 0.75). Subsequently, PEB was performed at 130 ° C. for about 60 seconds, and then developed in 2.38 wt% TMAH solution for about 60 seconds. As a result, a clear 180 nm L / S pattern was observed at about 13 mJ / cm ² .

The photosensitive polymer according to the present invention has a strong hydrophilic property and is excellent in adhesion to the film quality of a resist film, and a general developer can be used during development. It can be exposed with an excimer laser, has excellent resistance to dry etching, and has high resolution.

Claims (18)

3,4-dihydro- 2H -pyran derivative having an active site of a vinyl ether type such as the following formula (1). (One) Wherein x = 0, 1 and R is hydrogen, halogen, nitrile, hydroxy or alkyl having 1 to 20 carbon atoms, alkyl carbonyl, alkyl ester, alkoxy group. The compound of claim 1, wherein R is t-butyl ester, tetrahydropyranyl ester, 1-ethoxyethyl ester, 2-methyl-2-adamantyl ester, 2-ethyl-2-adamantyl ester, 2 3,4-di, characterized in that any one selected from the group consisting of -propyl-2-adamantyl ester, 8-methyl-8-tricyclodecanyl ester and 8-ethyl-8-tricyclodecanyl ester Hydro- 2H -pyran derivatives. The photosensitive polymer characterized by the polymer main chain containing a repeating unit as shown in the following formula (2). (2) The compound of claim 3, wherein R is t-butyl ester, tetrahydropyranyl ester, 1-ethoxyethyl ester, 2-methyl-2-adamantyl ester, 2-ethyl-2-adamantyl ester, 2 A photosensitive polymer, characterized in that any one selected from the group consisting of -propyl-2-adamantyl ester, 8-methyl-8-tricyclodecanyl ester and 8-ethyl-8-tricyclodecanyl ester. The photosensitive polymer according to claim 3, comprising a repeating unit as in the following formula (3). (3) Wherein x = 0, 1, R ₁ is hydrogen, halogen, nitrile, hydroxy or alkyl having 1 to 20 carbon atoms, alkyl carbonyl, alkyl ester, alkoxy group, R ₂ is hydrogen or methyl, R ₃ Is hydrogen or a C1-C20 alkyl, hydroxyalkyl, fluoroalkyl group, and m / (m + n) = 0.1-0.9. The compound of claim 5, wherein R ₁ is t-butyl ester, tetrahydropyranyl ester, 1-ethoxyethyl ester, 2-methyl-2-adamantyl ester, 2-ethyl-2-adamantyl ester, A photosensitive polymer, characterized in that any one selected from the group consisting of 2-propyl-2-adamantyl ester, 8-methyl-8-tricyclodecanyl ester and 8-ethyl-8-tricyclodecanyl ester. The compound of claim 5, wherein R ₃ is 2-hydroxyethyl, trifluoroethyl, hexafluoroisopropyl, pentafluoropropyl, t-butyl, tetrahydropyranyl, 1-ethoxy ethyl, 2-methyl Consisting of 2-adamantyl, 2-ethyl-2-adamantyl, 2-propyl-2-adamantyl, 8-methyl-8-tricyclodecanyl and 8-ethyl-8-tricyclodecanyl Photosensitive polymer, characterized in that any one selected from the group. The photosensitive polymer according to claim 3, comprising a repeating unit as in the following formula (4). (4) Wherein x = 0, 1 and R is hydrogen, halogen, nitrile, hydroxy or alkyl having 1 to 20 carbon atoms, alkyl carbonyl, alkyl ester, alkoxy group. The compound of claim 8, wherein R is t-butyl ester, tetrahydropyranyl ester, 1-ethoxyethyl ester, 2-methyl-2-adamantyl ester, 2-ethyl-2-adamantyl ester, 2 -Propyl-2-adamantyl ester, 8-methyl-8-tricyclodecanyl ester, 8-ethyl-8-tricyclodecanyl ester, isobornyl ester, norbornyl ester, A photosensitive polymer, characterized in that any one selected from the group consisting of 2-hydroxyethyl ester, 2-hydroxy hexafluoroisopropyl and 2-hydroxy hexafluoroisobutyl. The photosensitive polymer as described in any one of Claims 3-9 whose weight average molecular weights (Mw) are 3,000-50,000. 10. The three or more member according to any one of claims 5 to 9, further comprising at least one selected from the group consisting of norbornene, acrylate, methacrylate derivatives and 4-hydroxystyrene derivatives as comonomers. A photosensitive polymer, characterized in that the copolymer. 10. A photoresist composition comprising the photosensitive polymer according to any one of claims 3 to 9, a photo acid generator and a solvent. 13. The photoresist composition of claim 12, wherein the photoacid generator is selected from the group consisting of triphenylsulfonium triflate, diphenyl iodonium triflate and di-t-butylphenyl iodonium triflate. The photoresist composition of claim 12, wherein the content of the photoacid generator is 1 to 15 wt% based on the weight of the photosensitive polymer. 13. The photoresist composition of claim 12, further comprising a base additive. 16. The photoresist composition of claim 15, wherein said base additive is selected from the group consisting of triethylamine, triisobutylamine, triisooctylamine, diethanolamine and triethanolamine. The photoresist composition of claim 15, wherein the base additive is present in an amount of about 0.01 wt% to about 2 wt% based on the weight of the photosensitive polymer. (a) coating the resist composition of claim 12 on a silicon wafer; (b) pre-baking to remove solvent remaining in the resist film formed above; (c) exposing to an exposure source; (d) after said exposure, post exposure baking to cause a deprotection reaction; And (e) developing using a developing solution.