KR20000020467A - Monomer for new photoresist, copolymer thereof, and photoresist compound using copolymer - Google Patents

Abstract

PURPOSE: A monomer for new photoresist, copolymer thereof, and photoresist compound is provided to has an excellent etching resistance, an excellent heat resistance, and an excellent adhesiveness by using a lithography process using an optical source of a far ultraviolet rays when manufacturing a micro circuit of a high integrated semiconductor device. CONSTITUTION: A photoresist compound is selected from groups including a mono-2- ethyl-2-hydroxymethylbutyl bicycle£2.2.1|hapt-5-en-2,3-dicarboxylerate, a mono-2- dimethyl-3-hydroxypropyl bicycle£2.2.1|hapt-5-en-2,3-dicarboxylerate, a mono-3- hydroxypropyl bicycle£2.2.1|hapt-5-en-2,3-dicarboxylerate, a mono-3-hydroxyethyl bicycle£2.2.1|hapt-5-en-2,3-dicarboxylerate, a mono-2-ethyl-2-hydroxymethylbutyl bicycle£2.2.1|oct-5-en-2,3-dicarboxylerate, a mono-2-dimethyl-3-hydroxypropyl bicycle£2.2.1|oct-5-en-2,3-dicarboxylerate, a mono-3-hydroxypropyl bicycle£2.2.1|oct-5- en-2,3-dicarboxylerate, a mono-3-hydroxyethyl bicycle£2.2.1|oct-5-en-2,3- dicarboxylerate, a mono-2-ethyl-2-hydroxymethylbutyl tetracyclo£4.4.0.1.1|dodect-7-en- 2,3-dicarboxylerate, a mono-2-dimethyl-3-hydroxypropyl tetracyclo£4.4.0.11|dodect-7-en- 2,3-dicarboxylerate, a mono-3-hydroxypropyl tetracyclo£4.4.0.1.1|dodect-7-en-2,3- dicarboxylerate, and a mono-3-hydroxyethyl tetracyclo£4.4.0.1.1|dodect-7-en-2,3- dicarboxylerate.

Description

Novel photoresist monomers, copolymers thereof and photoresist compositions using the same

The present invention relates to a novel photoresist monomer, a polymer thereof, and a photoresist composition using the polymer, and more particularly, to a photoresist that can be used in a lithography process using a light source in the far ultraviolet region when fabricating a microcircuit of a highly integrated semiconductor device. For monomers, polymers thereof, and photoresist compositions.

To achieve high sensitivity in the microfabrication process of semiconductor fabrication, lithography using chemically amplified deep ultra violet (DUV) light sources such as KrF (249 nm), ArF (193 nm) or EUV light sources has recently been achieved. Suitable photoresist is attracting attention, and its composition is prepared by mixing a photoacid generator and a photoresist polymer having a structure that reacts sensitively to an acid.

The mechanism of action of the photoresist is that the photoacid generator receiving the 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 after the developer treatment, the mask image remains as a positive image on the substrate. In such a lithography process, the resolution may depend on the wavelength of the light source, thereby forming a fine pattern as the wavelength of the light source decreases. Therefore, in recent years, an ultraviolet light source has been adopted as a lithographic light source, and thus a photoresist suitable for such a light source has been demanded.

However, photoresist requires excellent etching resistance, heat resistance and adhesion. In addition, it should be developable in aqueous 2.38% tetramethylammonium hydroxide (TMAH) solution. However, it is very difficult to synthesize polymers satisfying all these properties, in particular, photoresist for far ultraviolet rays. For example, a polymer having a main chain of polyacrylate is easy to synthesize, but there are problems in securing etching resistance and developing process. In order to secure etching resistance, a method of adding an aliphatic cyclic unit to the main chain may be considered, but it is very difficult to configure all of the main chains with aliphatic cyclic units.

In an attempt to solve the above problems, a polymer having a structure represented by the following Chemical Formula 1, in which the main chain is substituted with noborane, acrylate, and maleic anhydride, was developed in Bell Labs.

<Formula 1>

However, this resin has a problem that the maleic anhydride moiety (A) used to polymerize aliphatic cyclic olefin groups is very well soluble in 2.38% TMAH even when unexposed. Therefore, in order to suppress the dissolution of the polymer in the non-exposed part, the proportion of the Y-substituted part of t-butyl should be increased, but the proportion of the Z part which increases the adhesion with the lower layer is relatively reduced. Therefore, there is a problem that PR falls from the substrate during patterning.

To improve this, a cholesterol dissolution inhibitor was added as a two component system. However, since the dissolution inhibitor has to use a very large amount of 30% of the resin by weight ratio, it is difficult to use as a PR resin due to problems such as poor reproducibility and rising manufacturing cost.

In order to solve this problem of the prior art, the present invention provides a novel monomer having excellent etching resistance, heat resistance, and adhesion, and having a significant difference in solubility in the exposed and non-exposed areas of the developer.

Moreover, it aims at providing the photoresist polymer containing the said monomer, and its manufacturing method.

Moreover, the photoresist composition and its manufacturing method are provided using the said novel photoresist polymer.

In order to achieve the above object, the present invention provides a compound of formula (2).

<Formula 2>

Wherein R 1 and R 2 are each hydrogen, methyl or ethyl,

a and b are each 0 to 3,

l is 0 to 2,

m and n are 1-2, respectively.

In addition, to achieve another object of the present invention provides a copolymer comprising a monomer of the formula (3).

In order to achieve another object of the present invention, there is provided a novel photoresist composition comprising the copolymer, a conventional organic solvent, and a conventional photoacid generator.

Synthesis of Monomers

As a monomer suitable for a lithographic process using an far-infrared light source, the inventors have synthesized the compound of formula (2).

<Formula 2>

Wherein R 1 and R 2 are each hydrogen, methyl or ethyl, m and n are each 1 to 2, l is 0 to 2 and a and b are each 0 to 3.

For example, if R1 = R2 = CH2CH3, a = b = 1, l = 0 and m = n = 1,

The compound of Formula 2 is mono-2-ethyl-2-hydroxymethylbutyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate (ie, 5-norbornene-2-carbox). Acid-3- (2,2-diethyl) hydroxypropylcarboxylate,

If R1 = R2 = methyl, a = b = 1, l = 0, m = n = 1,

The compound of Formula 2 is mono-2-dimethyl-3-hydroxypropyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate (ie, 5-norbornene-2-carbox). Acid-3- (2,2-dimethyl) hydroxypropylcarboxylate,

If R1 = R2 = hydrogen, a = b = 1, l = 0 and m = n = 1,

The compound of Formula 2 is mono-3-hydroxypropyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate (ie, 5-norbornene-2-carboxylic acid-3- Hydroxypropylcarboxylate),

If R1 = R2 = hydrogen, a = 0, b = 1 (or a = 1, b = 0), l = 0 and m = n = 1,

The compound of Formula 2 is mono-3-hydroxyethyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate (ie, 5-norbornene-2-carboxylic acid-3- Hydroxyethylcarboxylate),

If R1 = R2 = ethyl, a = b = 1, l = 0 and m = n = 2,

The compound of Formula 2 is mono-2-ethyl-2-hydroxymethylbutyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate,

If R1 = R2 = methyl, a = b = 1, l = 0 and m = n = 1,

Compound 2 is mono-2-dimethyl-3-hydroxypropyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate,

If R1 = R2 = hydrogen, a = b = 1, l = 0 and m = n = 1,

The compound of Formula 2 is mono-3-hydroxypropyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate,

If R1 = R2 = hydrogen, a = 0 and b = 1 (or a = 1 and b = 0), l = 0 and m = n = 1,

The compound of Formula 2 is mono-3-hydroxyethyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate,

If R1 = R2 = ethyl, a = b = 1, l = 1 and m = n = 1,

Compound 2 is mono-2-ethyl-2-hydroxymethylbutyl tetracyclo [4.4.0.1.1] dodex-7-ene-2,3-dicarboxylate,

If R1 = R2 = methyl, a = b = 1, l = 1 and m = n = 1,

The compound of Formula 2 is mono-2-dimethyl-3-hydroxypropyl tetracyclo [4.4.0.1.1] dodex-7-ene-2,3-dicarboxylate,

If R1 = R2 = hydrogen, a = b = 1, l = 1 and m = n = 1,

The compound of Formula 2 is mono-3-hydroxypropyl tetracyclo [4.4.0.1.1] dodex-7-ene-2,3-dicarboxylate,

If R1 = R2 = hydrogen, a = 0 and b = 1 (or a = 1 and b = 0), l = 1 and m = n = 1,

The compound of Formula 2 is mono-3-hydroxyethyl tetracyclo [4.4.0.1.1] dodex-7-ene-2,3-dicarboxylate,

If R1 = R2 = ethyl, a = b = 1, l = 0 and m = n = 2,

Compound 2 is mono-2-ethyl-2-hydroxymethylbutyl tetracyclo [4.4.0.1.1] dodex-7-ene-2,3-dicarboxylate,

If R1 = R2 = methyl, a = b = 1, l = 1 and m = n = 1,

The compound of Formula 2 is mono-2-dimethyl-3-hydroxypropyl tetracyclo [4.4.0.1.1] dodex-7-ene-2,3-dicarboxylate,

If R1 = R2 = hydrogen and a = b = 1, l = 0 and m = n = 1,

The compound of Formula 2 is mono-3-hydroxypropyl tetracyclo [4.4.0.1.1] dodex-7-ene-2,3-dicarboxylate,

If R1 = R2 = hydrogen, a = 0 and b = 1 (or a = 1 and b = 0), l = 0 and m = n = 1,

The compound of Formula 2 is mono-3-hydroxyethyl tetracyclo [4.4.0.1.1] dodex-7-ene-2,3-dicarboxylate.

The compound of Formula 2 is prepared by reacting a compound of Formula 3 with a compound of Formula 4 under an acid catalyst or a base catalyst.

<Formula 3>

Wherein R 1 and R 2 are each H or alkyl,

m and n are each 0-3.

<Formula 4>

Examples of the compound of formula 3 include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-diethyl-1,3-propanedi Ol, 2,2-dimethyl-1,3-propanediol, diethylene glycol, and the like. Examples of the compound represented by Chemical Formula 4 include 5-norbornene-2,3-dicarboxylic anhydride and the like. There is this. Moreover, tetrahydrofuran, dimethylformamide, dioxane, benzene, toluene etc. can be used as an organic solvent.

Example 1

Synthesis of 5-norbornene-2-carboxylic acid-3-hydroxyethylcarboxylate

0.1 mol of ethylene glycol is added to 100 ml of tetrahydrofuran and cooled to -20 ° C. After cooling, 0.1 mol of NaH was added and stirred for 20-30 minutes. After stirring, 0.1 mol of 5-norbornene-2,3-dicarboxylic anhydride was slowly added, followed by reaction at room temperature for 24 hours. After the reaction, the tetrahydrofuran was distilled off, and the remaining solution was mixed with 500 ml of 0.2N HCl solution, and then crystallized in a refrigerator for several days. The resulting material was filtered, washed with 100 ml of cold water, and dried to obtain the compound of Formula 5 Was obtained as a pure colorless solid (86%, 19.4 g).

<Formula 5>

In this case, NaH is used as the reaction catalyst, but other basic catalysts such as KH, CaH 2, Na 2 CO 3, K 2 CO 3, LDA (lithium diisopropylamide), and the like may also be used. In addition, acid catalysts such as sulfuric acid, acetic acid and nitric acid may be used instead of the basic catalyst. In addition, although hydrochloric acid (HCl) is used as a neutralizing agent, general acids such as nitric acid and sulfuric acid acetic acid can also be used. When an acid catalyst is used, a base is used as a neutralizing agent.

On the other hand, the crystallization takes considerable time (more than a week). Thus, to improve this, the solution neutralized by hydrochloric acid solution treatment is extracted with 500 ml of ethyl acetate. Subsequently, the extracted ethyl acetate layer was dehydrated with MgSO 4 or Na 2 SO 4, and the resulting solution was filtered and the filtrate was vacuum distilled to obtain a white solid in a crude state, which was purified by recrystallization from acetone / petroleum ether. It is also possible to obtain a compound of the formula (5) in the state (78%, 17.6 g).

Example 2

Synthesis of 5-norbornene-2-carboxylic acid-3-hydroxypropylcarboxylate.

As a starting material, a compound of the following Chemical Formula 6 was obtained as a colorless solid by the same method as Example 1 except for using 1,3-propanediol instead of ethylene glycol ( 88%, 21.1 g).

<Formula 6>

Example 3

Synthesis of 5-norbornene-2-carboxylic acid-3-hydroxybutylcarboxylate.

As a starting material, a compound of the following Chemical Formula 7 was obtained as a colorless solid in the same manner as in Example 1 except for using 1,4-butanediol instead of ethylene glycol ( 89%, 22.6 g).

<Formula 7>

Example 4

Synthesis of 5-norbornene-2-carboxylic acid-3-hydroxypentylcarboxylate

In the same manner as in Example 1, except that 1,5-pentanediol was used instead of ethylene glycol as a starting material, a compound of formula 8 was obtained as a colorless solid ( 85%, 22.8 g).

<Formula 8>

Example 5

Synthesis of 5-norbornene-2-carboxylic acid-3- (2,2-diethyl) hydroxypropylcarboxylate

The same method as Example 1 except for using 2,2-diethyl-1,3-propanediol (2,2-diethyl-1,3-propandiol) instead of ethylene glycol as a starting material The compound of formula 9 was obtained as a colorless solid (91%, 26.9 g).

<Formula 9>

Example 6

Synthesis of 5-norbornene-2-carboxylic acid-3- (2,2-dimethyl) hydroxypropylcarboxylate

The same method as Example 1 except for using 2,2-dimethyl-1,3-propanediol (2,2-dimethyl-1,3-propandiol) instead of ethylene glycol as starting material The compound of formula 10 was obtained as a colorless solid (90%, 24.1 g).

<Formula 10>

Synthesis of Copolymer

On the other hand, the inventors of the present invention synthesized a copolymer in which the compound is included in the main chain in view of the fact that the monomer of the formula (2) has an excellent adhesion to the substrate and at the same time have an aliphatic olefin structure with excellent etching resistance.

On the other hand, in order to facilitate the polymerization between the monomers of Formula 3, it is preferable to add maleic hydride as the second monomer.

In addition, in order to improve the sensitivity, it is preferable to further add an aliphatic cyclic olefin compound substituted with carboxylic acid as the third monomer.

Based on this point, the present inventors synthesized the copolymer of following formula (11).

<Formula 11>

Wherein R 1 and R 2 are each hydrogen, methyl or ethyl and R 3 is hydrogen or straight or branched chain substituted or unsubstituted alkyl having 1 to 10 carbon atoms.

A and b are each 0 to 3, l is 0 to 2, and m and n are 1 to 2, respectively. The polymerization ratio of each monomer is x: y: z = 100: 5-95: 5-95 (mol%) when the molar ratio (%) of maleic hydride is 100.

The novel photoresist polymer of Formula 11 preferably has a molecular weight of 3,000 to 100,000.

The copolymer of Formula 11 is a compound of Formula 2 as a first monomer, a maleic anhydride of Formula 12 as a second monomer and a compound of Formula 13 as a third monomer in a conventional organic solvent, The resultant solution is prepared by adding a conventional radical polymerization initiator to radical polymerization.

<Formula 12>

<Formula 13>

Wherein R 3 is hydrogen, straight or branched substituted alkyl or unsubstituted alkyl having 1 to 10 carbon atoms, m and n are each 1 to 2 and l is 0 to 2.

The above polymerization reaction is performed by bulk polymerization or solution polymerization, and a single solvent such as cyclohexanone, methyl ethyl ketone, benzene, toluene, dioxane, dimethelformamide, or a mixed solvent thereof may be used as the polymerization organic solvent. have. As the polymerization initiator, benzoyl peroxide, 2,2'-azobisisobutyronitrile (AIBN), acetyl peroxide, lauryl peroxide, t-butyl peracetate and the like can be used.

Example 7

Poly (maleic anhydride / mono-2-ethyl-2-hydroxymethylbutyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate / t-butyl bicyclo [2.2.1 ] Hept-5-ene-2-carboxylate) polymer synthesis.

1.0 mole of maleic anhydride, 0.2 moles of mono-2-ethyl-2-hydroxymethylbutyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate, and t 0.8 moles of -butyl bicyclo [2.2.1] hept-5-ene-2-carboxylate are dissolved in tetrahydrofuran. Then, 0.5 to 10 g of the polymerization initiator AIBN (azobisiso butyronitrile) was added to the resulting solution, and then reacted at a temperature of about 60 to 70 ° C. under nitrogen or argon for 4 to 24 hours.

The polymer thus produced is precipitated in ethyl ether or hexane, and then dried to obtain poly (maleic hydride / mono-2-ethyl-2-hydroxymethylbutyl bicyclo [2.2.1]. Hept-5-ene-2,3-dicarboxylate / t-butyl bicyclo [2.2.1] hept-5-ene-2-carboxylate) polymer was obtained. (Yield 39%)

Example 8

Mono-2-ethyl-2-hydroxymethylbutyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate instead of 0.2 mole of mono-2-ethyl-2-hydroxymethylbutyl bi Poly (maleic anhydride / mono-2-ethyl-2 in the same manner as in Example 7 except for using 0.2 mole of cyclo [2.2.2] oct-5-ene-2,3-dicarboxylate Hydroxymethylbutyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate / t-butyl bicyclo [2.2.1] hept-5-ene-2-carboxylate) Obtained (yield 36%).

Example 9

0.8 moles of t-butyl bicyclo [2.2.2] oct-5-endo-2-carboxylate is used instead of 0.8 moles of t-butyl bicyclo [2.2.1] hept-5-ene-2-carboxylate Poly (maleic anhydride / mono-2-ethyl-2-hydroxymethylbutyl bicyclo [2.2.1] hept-5-ene-2,3-dicar in the same manner as in Example 7 except that A carboxylate / t-butyl bicyclo [2.2.2] oct-5-endo-2-carboxylate) polymer was obtained. (Yield 38%)

Example 10

0.8 moles of t-butyl bicyclo [2.2.2] oct-5-endo-2-carboxylate is used instead of 0.8 moles of t-butyl bicyclo [2.2.1] hept-5-ene-2-carboxylate Poly (maleic anhydride / mono-2-ethyl-2-hydroxymethylbutyl bicyclo [2.2.2] oct-5-ene-2,3-dicar in the same manner as in Example 8 except that Voxylate / t-butyl bicyclo [2.2.2] oct-5-endo-2-carboxylate) was obtained (yield 37%).

Synthesis of Photoresist Composition

By mixing the novel photoresist copolymer according to the present invention with a conventional organic solvent and a conventional photoacid generator, a novel photoresist composition suitable for a lithography process using an far ultraviolet light source, in particular an ArF light source, can be prepared.

At this time, the amount of copolymer used may vary depending on the type of organic solvent and photoacid generator, lithography conditions, and the like. In general, the organic solvent is preferably used at 200 to 1000 wt% of the copolymer, and the photoacid generator is preferably used at a ratio of 0.05 to 10 wt% of the copolymer.

After dissolving the novel copolymer according to the present invention in an organic solvent, adding a photoacid generator such as onium salt or eutectic acid to 0.05 to 10% by weight of the novel photoresist copolymer, the resulting solution is ultrafine. Filtration with a filter produces a photoresist solution.

At this time, the photoacid generator is a sulfide salt or onium salt, diphenyl iodo hexafluorophosphate, diphenyl iodo hexafluoro arsenate, diphenyl iodo hexafluoro antimonate, diphenyl paramethoxy phenyl triflate, Diphenylparatoluenyl triflate, diphenylparaisobutylphenyl triflate, diphenylpara-t-butylphenyl triflate, triphenylsulfonium hexafluoro phosphate, triphenylsulfonium hexafluoro arsenate, triphenylsul One or two or more of phonium hexafluor antimonate, triphenylsulfonium triflate, dibutylnaphthylsulfonium triflate may be used.

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

Formation of Photoresist Pattern

After spin-coating a photoresist composition prepared according to the present invention on a silicon wafer to form a thin film, soft bake for 1 to 5 minutes in an oven or hot plate at 70 to 200 ° C., more preferably 80 to 150 ° C., and After exposing using an 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, EUV, DUV and the like may be used as the exposure source, and the exposure energy is preferably 0.1 to 30 mJ / cm 2.

The wafer thus exposed is immersed in a 2.38% TMAH aqueous solution for 1 minute 30 seconds to develop an ultrafine positive resist image.

Example 11

Poly (maleic anhydride / mono-2-ethyl-2-hydroxymethylbutyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate / t-butyl bicyclo [2.2.1 ] 10g of hept-5-ene-2-carboxylate is dissolved in 40g of 3-methoxymethyl propionate solvent, and then triphenyl sulfonium triflate, a photoacid generator. Alternatively, 0.01 to 1 g of dibutyl naphthyl sulfonium triflate was added and stirred, and then filtered through a 0.10 μm filter to obtain a photoresist composition. The photoresist composition thus prepared was applied over the predetermined etching target layer on the semiconductor device, and then exposed using a 193 nm ArF light source. And post-baking the photoresist. The semiconductor device was developed by immersion in an aqueous 2.38% tetramethylammonium hydroxide (TMAH) solution. When the photoresist thickness was about 0.3 mu m, an L / S pattern of 0.13 mu m was obtained.

Example 12

Poly (maleic anhydride / mono-2-ethyl-2-hydroxymethylbutyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate / t-butyl bicyclo [2.2.1 ] Poly (maleic anhydride / mono-2-ethyl-2-hydroxymethylbutyl bicyclo [2.2.2] oct-5-ene-2, instead of 10 g of hept-5-ene-2-carboxylate), A photoresist pattern was obtained in the same manner as in Example 3 except for using 10 g of 3-dicarboxylate / t-butyl bicyclo [2.2.1] hept-5-ene-2-carboxylate) . The obtained pattern was 0.13 mu m when the photoresist thickness was about 0.3 mu m.

The novel photoresist polymers described above not only have excellent etching resistance, heat resistance, and adhesion, but also have a significant difference in solubility between exposed and non-exposed areas with respect to a developing solution, thereby enabling the formation of high-resolution photoresist patterns. In addition, satisfactory results can be obtained even at the depth of focus. Therefore, high integration of the semiconductor is possible by using the photosensitive polymer according to the present invention.

The above detailed description and examples of the present invention have been disclosed for purposes of illustration, and the technical scope of the present invention should not be construed as being limited thereto.

Claims (33)

A compound of formula <Formula 2> Wherein R 1 and R 2 are each hydrogen, methyl or ethyl, a and b are each 0 to 3, l is 0 to 2, m and n are 1-2, respectively. The compound of claim 1, wherein the compound is Mono-2-ethyl-2-hydroxymethylbutyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate (i.e. 5-norbornene-2-carboxylic acid-3- ( 2,2-diethyl) hydroxypropylcarboxylate, Mono-2-dimethyl-3-hydroxypropyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate (ie, 5-norbornene-2-carboxylic acid-3- ( 2,2-dimethyl) hydroxypropylcarboxylate, Mono-3-hydroxypropyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate, Mono-3-hydroxyethyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate (ie, 5-norbornene-2-carboxylic acid-3-hydroxyethylcarboxylate ), Mono-2-ethyl-2-hydroxymethylbutyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate, Mono-2-dimethyl-3-hydroxypropyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate, Mono-3-hydroxypropyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate, Mono-3-hydroxyethyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate, Mono-2-ethyl-2-hydroxymethylbutyl tetracyclo [4.4.0.1.1] dodex-7-ene-2,3-dicarboxylate, Mono-2-dimethyl-3-hydroxypropyl tetracyclo [4.4.0.1.1] dodex-7-ene-2,3-dicarboxylate, Mono-3-hydroxypropyl tetracyclo [4.4.0.1.1] dodex-7-ene-2,3-dicarboxylate, Mono-3-hydroxyethyl tetracyclo [4.4.0.1.1] dodex-7-ene-2,3-dicarboxylate, Mono-2-ethyl-2-hydroxymethylbutyl tetracyclo [4.4.0.1.1] dodex-7-ene-2,3-dicarboxylate, Mono-2-dimethyl-3-hydroxypropyl tetracyclo [4.4.0.1.1] dodex-7-ene-2,3-dicarboxylate, Mono-3-hydroxypropyl tetracyclo [4.4.0.1.1] dodex-7-ene-2,3-dicarboxylate, and Mono-3-hydroxyethyl tetracyclo [4.4.0.1.1] dodex-7-ene-2,3-dicarboxylate. (a) dissolving a compound of formula 3 as a starting material in a conventional organic solvent, (b) adding and reacting the compound of formula 4 to the resultant solution of step (a) in the presence of an acid catalyst or a base catalyst; (c) removing the organic solvent from the resultant solution of step (b); (d) neutralizing by adding a neutralizing agent to the resultant solution of step (c); (e) crystallizing the resultant solution of step (d). <Formula 2> Wherein R 1 and R 2 are each hydrogen, methyl or ethyl, a and b are each 0 to 3, l is 0 to 2, m and n are 1-2, respectively. <Formula 3> Wherein R 1 and R 2 are each H or alkyl, m and n are each 0-3. <Formula 4> According to claim 3, wherein the compound of formula 3 is ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-diethyl-1,3- And propanediol and 2,2-dimethyl-1,3-propanediol. The method of claim 3, wherein the compound of Formula 3 is used in the same mole number or in excess of the compound of Formula 4. According to claim 3, wherein the base catalyst of step (b) is selected from the group consisting of NaH, KH, CaH2, Na2CO3, K2CO3 and LDA (lithium diisopropylamide), the acid catalyst is selected from the group consisting of sulfuric acid, nitric acid and acetic acid How to feature. The method of claim 3, wherein the crystallization of step (e) is performed by leaving the solution containing the neutralizing agent in the refrigerator for at least one week. The method of claim 3, wherein the crystallization of step (e) (f) extracting the resulting solution with the neutralizing agent added with ethyl acetate, (g) dehydrating the extracted ethyl acetate layer, and filtering the resulting solution; (h) vacuum distilling the filtrate obtained in step (g) to obtain a white solid, (i) recrystallizing the white solid obtained from step (h). The method of claim 8, wherein the dehydration step (g) is performed using MgSO 4 or Na 2 SO 4. Copolymer comprising a compound of formula (2). <Formula 2> Wherein R 1 and R 2 are each hydrogen, methyl or ethyl: a and b are each 0 to 3 l is 0 to 2; m and n are 1-2, respectively. The copolymer according to claim 10, further comprising maleic hydride as the second monomer. The copolymer according to claim 10 or 11, further comprising a compound of formula (13) as a third monomer. <Formula 13> Wherein R 3 is hydrogen, straight or branched chain substituted or unsubstituted alkyl having 1 to 10 carbon atoms. The copolymer according to claim 12, wherein the copolymer is a compound represented by the following Chemical Formula 11. <Formula 11> Wherein R 1 and R 2 are each hydrogen, methyl or ethyl, R3 is hydrogen, straight or branched substituted alkyl or unsubstituted alkyl having 1 to 10 carbon atoms, a and b are each 0 to 3, l is 0 to 2, m and n are 1-2, respectively. The method of claim 13, wherein the copolymer is x: y: z = 100: 5-95: 5-95 (mol%) when the molar ratio (%) of maleic hydride is set to 100 coalescence. The copolymer of claim 10, wherein the copolymer has a molecular weight of 3,000 to 100,000. The method of claim 10, wherein the copolymer Poly (maleic anhydride / mono-2-ethyl-2-hydroxymethylbutyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate / t-butyl bicyclo [2.2.1 ] Hept-5-ene-2-carboxylate); Poly (maleic anhydride / mono-2-ethyl-2-hydroxymethylbutyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate / t-butyl bicyclo [2.2.1 ] Hept-5-ene-2-carboxylate); Poly (maleic anhydride / mono-2-ethyl-2-hydroxymethylbutyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate / t-butyl bicyclo [2.2. 2] oct-5-endo-2-carboxylate); And Poly (maleic anhydride / mono-2-ethyl-2-hydroxymethylbutyl bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylate / t-butyl bicyclo [2.2. 2] oct-5-endo-2-carboxylate). (a) dissolving a compound of Formula 2 and maleic anhydride in a conventional organic solvent, (b) adding a polymerization initiator to the resultant solution. <Formula 2> Wherein R 1 and R 2 are each hydrogen, methyl or ethyl, a and b are each 0 to 3, l is 0 to 2, m and n are 1-2, respectively. 18. The method of claim 17, further comprising adding a compound of formula 13 as a third monomer. <Formula 13> Wherein R 3 is hydrogen, straight or branched chain substituted or unsubstituted alkyl having 1 to 10 carbon atoms. The method of claim 17, wherein the organic solvent is tetrahydrofuran, dimethyl formamide, dimethyl sulfoxide, dioxane, methyl ethyl ketone, benzene, toluene And xylene. 20. The method of claim 19, wherein the polymerization initiator is selected from the group consisting of 2,2-azobisisobutyronitrile (AIBN), acetyl peroxide, lauryl peroxide and t-butyl for oxide. Method of Preparation of Copolymer. In a photoresist composition comprising a photoresist resin, a conventional organic solvent and a conventional photoacid generator, The photoresist resin is a photoresist composition, characterized in that the copolymer comprising a compound of the formula (2). <Formula 2> Wherein R 1 and R 2 are each hydrogen, methyl or ethyl, a and b are each 0 to 3, l is 0 to 2, m and n are 1-2, respectively. The photoresist composition of claim 21, wherein the resin is a compound of Formula 11 below. <Formula 11> Wherein R 1 and R 2 are each hydrogen, methyl or ethyl, R3 is hydrogen, straight or branched substituted alkyl or unsubstituted alkyl having 1 to 10 carbon atoms, a and b are each 0 to 3, l is 0 to 2, m and n are 1-2, respectively. The photoresist composition of claim 21, wherein the photoacid generator is a sulfide salt or an onium salt salt. 24. The method of claim 23, wherein the photoacid generator is diphenyl iodo hexafluorophosphate, diphenyl iodo hexafluoro arsenate, diphenyl iodo hexafluoro antimonate, diphenyl paramethoxy phenyl triflate, diphenyl paratoluene Neyl Triflate, Diphenylparaisobutylphenyl Triflate, Diphenylpara-t-butylphenyl Triflate, Triphenylsulfonium Hexafluor Phosphate, Triphenylsulfonium Hexafluor Arsenate, Triphenylsulfonium Hexafluor Antimo A photoresist composition comprising one or two or more selected from the group consisting of nates, triphenylsulfonium triflate and dibutylnaphthylsulfonium triflate. The photoresist composition of claim 21, wherein the photoacid generator is used at a ratio of 0.05 to 10% by weight based on the resin. The photoresist composition of claim 21, wherein the organic solvent is selected from the group consisting of cyclohexanone, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate and propylene glycol methyl ether acetate. 22. The photoresist composition of claim 21, wherein the organic solvent is used in an amount of 200 to 1000 wt% with respect to the resin. (a) forming a photoresist film by applying a photoresist composition including a copolymer including a compound represented by Chemical Formula 2, a photoacid generator, and an organic solvent to a substrate; (b) exposing the photoresist film; And (c) developing the photoresist film. <Formula 2> Wherein R 1 and R 2 are each hydrogen, methyl or ethyl, a and b are each 0 to 3, l is 0 to 2, m and n are 1-2, respectively. 29. The method of claim 28, further comprising the step of performing a baking process before or after step (b). 29. The method of claim 28, wherein the baking process is performed at 70-200 ° C. 31. The method of claim 30, wherein step (b) is performed using an ArF, KrF, DUV, EUV, E-beam or X-ray light source. 32. The method of claim 31, wherein step (b) is performed by irradiating exposure energy of 0.1-10 mJ / cm 2. A semiconductor device manufactured by the method of claim 28.