KR100557620B1 - Novel photoresist monomer, polymer thereof and photoresist composition containing it - Google Patents

Abstract

The present invention relates to a novel photoresist monomer, a polymer thereof, and a photoresist composition using the polymer, wherein at least one kind of novel polycycloalkene compound represented by the following general formula (1) and maleic anhydride as a second monomer And / or a copolymer prepared by polymerizing maleimide and the photoresist composition of the present invention containing the polymer are particularly excellent in etching resistance, heat resistance, and adhesion, so that the light source in the far ultraviolet region may be used in the manufacture of microcircuits of highly integrated semiconductor devices. It can be very useful for the lithography process used.

[Formula 1]

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and n are as defined in the specification.

Description

Novel photoresist monomers, polymers and photoresist composition containing it

The present invention relates to a novel photoresist monomer, a polymer thereof and a photoresist composition using the polymer, and more particularly, suitable for use in a lithography process using a light source in the far ultraviolet region in the manufacture of microcircuits of highly integrated semiconductor devices. The present invention relates to a monomer for photoresist, a polymer thereof, a photoresist composition using the polymer, and a method for producing the same.

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

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

In addition, the photoresist generally has to have excellent etching resistance, heat resistance and adhesion, and can be developed in a known developer, for example, an aqueous solution of 2.38% tetramethylammonium hydroxide (TMAH), to reduce the process cost. , In many respects. However, it is very difficult to produce a polymer that satisfies all these properties, especially photoresist for far ultraviolet rays. For example, polymers having a main chain of polyacrylate are easy to synthesize, but have problems in securing etching resistance and developing processes. 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 order to solve the above problems, a polymer having the following structure in which the main chain is substituted with norbornylene, acrylate, and maleic anhydride has been developed at Bell Labs.

However, this resin has a problem that the maleic anhydride portion (A) used to polymerize aliphatic cyclic olefin groups is very well dissolved in 2.38% TMAH even when unexposed. Therefore, in order to suppress the dissolution of the polymer in the non-exposed part, it is necessary to increase the proportion of the Y-substituted part of t-butyl, but the proportion of the Z part which increases the adhesion to the lower layer is relatively reduced. There was a problem that the photoresist falls during patterning. In order to solve this problem, a cholesterol dissolution inhibitor was added to the resin as a two-component system, but since these dissolution inhibitors must be added in a large amount of 30% by weight of the resin, the reproducibility is low and the manufacturing cost is increased. It was difficult to use as a photoresist resin because of the disadvantages.

In addition, many studies have been reported to increase the etching resistance of photoresist resins (Journal of photopolymer science and Technology Vol. 10, No. 3, 511-520 (1997)), but are essential for the formation of ultrafine patterns of 0.10 μm or less. As a result, the thickness of the photoresist should be 0.3 μm or less, and a photoresist capable of withstanding the etching gas at this thickness has not yet been developed.

Accordingly, the present inventors synthesized polycycloalkene monomers and derivatives thereof while trying to solve the above problems of the prior art, and confirmed that the polymers contained in the main chain were excellent in etching resistance and adhesion at the same time. The present invention was completed.

An object of the present invention is to provide a novel photoresist monomer, a copolymer of the monomer, and a photoresist composition containing the copolymer.

In order to achieve the above object, the present invention provides a novel monomer for photoresist and a method for producing the same; Copolymers of the monomers and methods for their preparation; A photoresist composition containing the copolymer; And to provide a semiconductor device manufactured using the photoresist composition.

Hereinafter, the present invention will be described in detail.

The present invention first provides a polycycloalkene-based compound represented by the formula (1) which can be used as a photoresist monomer, and a preparation method thereof.

Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each is hydrogen, branched or main chain substituted alkyl having 1 to 10 carbon atoms, side or main chain substituted ester having 1 to 10 carbon atoms, 1 carbon And branched or main chain substituted ketones having from 1 to 10, branched or main chain substituted carboxylic acids having from 1 to 10 carbon atoms, side chained or main chain substituted acetals having from 1 to 10 carbon atoms, and at least one hydroxyl group (-OH) Branched or main chain substituted alkyl having 1 to 10 carbon atoms, at least one hydroxyl group having at least one hydroxyl group (—OH), at least one hydroxyl group having at least one hydroxyl group (—OH) Branched or backbone substituted ketones having 1 to 10 carbon atoms, branched or backbone substituted carboxylic acids having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH) or one or more Represents the side chain or the main chain of the substituted acetal of between 1 to 10 carbon atoms which contains a hydroxyl group (-OH),

R ₅ and R ₆ represent hydrogen, branched or main chain substituted alkyl or alkoxy having 1 to 10 carbon atoms,

n is an integer selected from 0-5.

The compound of Formula 1 is 1) a monomer for inhibiting dissolution that has a property of dissolving in a developing solution using an acid generated by a light source, 2) an adhesion increasing monomer for increasing adhesion to a wafer, and 3) light. It can be classified as a light sensitivity increasing monomer which increases the sensitivity to

1) The monomer for inhibiting dissolution is preferably selected from the following Chemical Formulas 12, 13, 15, 16, 30, and 31;

Wherein n is an integer selected from 0 to 5.

2) the adhesion increasing monomer is preferably selected from the formulas (24), (25), (27) and (28);

Wherein n is an integer selected from 0 to 5.

3) The light sensitivity increasing monomer is preferably selected from the following formulas (18), (19), (21), (22), (33), (34), (35), and (36).

Wherein n is an integer selected from 0 to 5.

The compound of Formula 1 may be prepared in two ways, the first of which consists of the following steps:

(a) reacting a compound of formula 2 with a compound of formula 3 with Diels-Alder in an organic solvent, and then removing the organic solvent to obtain a compound of formula 4; And

(b) performing a Diels-Alder reaction of the compound of Formula 4 with the compound of Formula 5 in an organic solvent and then removing the organic solvent to obtain a compound of Formula 1.

Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each is hydrogen, branched or main chain substituted alkyl having 1 to 10 carbon atoms, side or main chain substituted ester having 1 to 10 carbon atoms, 1 carbon And branched or main chain substituted ketones having from 1 to 10, branched or main chain substituted carboxylic acids having from 1 to 10 carbon atoms, side chained or main chain substituted acetals having from 1 to 10 carbon atoms, and at least one hydroxyl group (-OH) Branched or main chain substituted alkyl having 1 to 10 carbon atoms, at least one hydroxyl group having at least one hydroxyl group (—OH), at least one hydroxyl group having at least one hydroxyl group (—OH) Branched or backbone substituted ketones having 1 to 10 carbon atoms, branched or backbone substituted carboxylic acids having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH) or one or more Represents the side chain or the main chain of the substituted acetal of between 1 to 10 carbon atoms which contains a hydroxyl group (-OH),

R ₅ and R ₆ represent hydrogen, branched or main chain substituted alkyl or alkoxy having 1 to 10 carbon atoms,

n is an integer selected from 0-5.

In the above production method, the compound of Formula 4 prepared in step (a) is a compound of Formula 1 when n = 0 can be used as a photoresist monomer, of course.

In addition, a second method for preparing a compound of Formula 1 consists of the following steps:

(a) reacting the compound of formula 2 with maleic anhydride of formula 6 in an organic solvent and then removing the solvent to obtain a compound of formula 7;

(b) dissolving the compound of Formula 7 in an organic solvent and then reacting an alcohol (R ₇ OH) to obtain a compound of Formula 8; And

(c) Diels-Alder reacting the compound of Formula 8 with the compound of Formula 5 in an organic solvent to obtain a compound of Formula 9 included in the compound of Formula 1.

Where                     

R ₅ , R ₆ and R ₇ represent hydrogen, branched or main chain substituted alkyl or alkoxy having 1 to 10 carbon atoms,

n is an integer selected from 0-5.

In the second preparation method, Diels-Alder reacts the compound of Formula 7 and the compound of Formula 5 obtained in step (a) to obtain a compound of Formula 10, wherein the compound of Formula 10 and alcohol (R ₇ OH) may be reacted to obtain a compound of Formula 9 included in the compound of Formula 1.

In the above,

R ₅ , R ₆ and R ₇ represent hydrogen, branched or main chain substituted alkyl or alkoxy having 1 to 10 carbon atoms,

n is an integer selected from 0-5.

In the two preparation methods, the n value of the formula (1) varies depending on the amount of the compound of the formula (5) added, and the n value is increased by 1 per 1.2 moles of the compound of the formula (5). In the present invention, according to the first method, 1 to 6 moles of the compound of Formula 5 is used per 1 mole of the compound of Formula 4, and in the second method, 1 mole of the compound of Formula 8 or compound of Formula 7 1 to 6 moles of the compound of formula 5 are used.

The organic solvent is also selected from the group consisting of tetrahydrofuran (THF), dimethylformamide, dimethylsulfoxide, dioxane, benzene, toluene and xylene.

In addition, the compounds of Formulas 2 and 5 in the preparation method is preferably methylcyclopentadiene.

Meanwhile, in the second preparation method, the compound of Formula 7 or Formula 10, which is used as an intermediate, may be used as a photoresist monomer by itself. In addition to the compounds selected from among the light sensitivity is increased monomers.

In another aspect, the present invention provides a photoresist copolymer, characterized in that it comprises at least one compound of the formula (1). In this case, the polycycloalkene-based compound (compound of Formula 1) as a monomer may include 1) a monomer for inhibiting dissolution selected from Formulas 12, 13, 15, 16, 30, and 31; 2) an adhesion increasing monomer selected from formulas 24, 25, 27 and 28; And 3) at least one monomer of three groups each classified as a light sensitivity increasing monomer selected from Formulas 18, 19, 21, 22, 33, 34, 35, and 36. However, since the polycycloalkene-based compound is excellent in itself, even if the adhesion increasing monomer is not included, it does not reduce the performance of the photosensitive agent so much.

The copolymer of the present invention also comprises at least one compound selected from the group consisting of maleic anhydride and maleimide as the second monomer, the purpose of using maleic anhydride and maleimide is to This is because conventional radical polymerization is difficult and polymerization is possible only when maleic anhydride and maleimide are used.

Thus, the copolymer of the present invention is a polymer comprising (1) a polymer consisting of at least one polycycloalkene compound and maleic anhydride, (2) a polymer consisting of at least one polycycloalkene compound and maleimide (Formula 38) ), And 3) one or more polycycloalkene-based compounds and polymers of maleic anhydride and maleimide (Formula 39).

Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each is hydrogen, branched or main chain substituted alkyl having 1 to 10 carbon atoms, side or main chain substituted ester having 1 to 10 carbon atoms, 1 carbon And branched or main chain substituted ketones having from 1 to 10, branched or main chain substituted carboxylic acids having from 1 to 10 carbon atoms, side chained or main chain substituted acetals having from 1 to 10 carbon atoms, and at least one hydroxyl group (-OH) Branched or main chain substituted alkyl having 1 to 10 carbon atoms, at least one hydroxyl group having at least one hydroxyl group (—OH), at least one hydroxyl group having at least one hydroxyl group (—OH) Branched or backbone substituted ketones having 1 to 10 carbon atoms, branched or backbone substituted carboxylic acids having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH) or one or more Represents the side chain or the main chain of the substituted acetal of between 1 to 10 carbon atoms which contains a hydroxyl group (-OH),

R ₅ and R ₆ represent hydrogen, branched or main chain substituted alkyl or alkoxy having 1 to 10 carbon atoms, wherein the position of R ₆ is not limited to that shown and may be selected as shown in Formula 1, eg For example, when n = 1, R ₆ may be at position 5 or at position 10.

l, m and n may be the same or different and each is an integer selected from 0 to 5,

a is the molar ratio of the monomer for inhibiting dissolution, b is the molar ratio of the adhesion increasing monomer, and c is the molar ratio of the light sensitivity increasing monomer.

The copolymer of the present invention is preferably a molecular weight of 3,000 to 100,000, and a preferable compound of these copolymers may be exemplified by the following compounds:

Poly (1,1-dimethylethyl 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2-carboxylate / 5 or 6-methylbicyclo [2.2.1] -hept-5- En-2-carboxylic acid / 2-hydroxyethyl 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2-carboxylate / maleic anhydride);

Poly (1,1-dimethylethyl 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2-carboxylate / 5 or 6-methylbicyclo [2.2.1] -hept-5- En-2,3-dicarboxylic acid / 2-hydroxyethyl 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2-carboxylate / maleic anhydride);

Poly (1,1-dimethylethyl 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2-carboxylate / 5 or 6-methylbicyclo [2.2.1] -hept-5- En-2-carboxylic acid / 3-hydroxypropyl 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2-carboxylate / maleic anhydride);

Poly (1,1-dimethylethyl 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2-carboxylate / 5 or 6-methylbicyclo [2.2.1] -hept-5- Ene-2,3-dicarboxylic acid / 3-hydroxypropyl 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2-carboxylate / maleic anhydride);

Poly (1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / 5,7 or 5,8-dimethyltetra Cyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylic acid / 2-hydroxyethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7 -Ene-2-carboxylate / maleic anhydride);

Poly (1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / 5,7 or 5,8-dimethyltetra Cyclo [4.4.0.1.1] -dodec-7-ene-2,3-dicarboxylic acid / 2-hydroxyethyl 5,7 or 5,8-dimethyl tetracyclo [4.4.0.1.1] -dode X-7-ene-2-carboxylate / maleic anhydride);

Poly (1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / 1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2,3-dicarboxylate / 2-hydroxyethyl 5,7 or 5,8-dimethyltetracyclo [4.4. 0.1.1] -dodec-7-ene-2-carboxylate / maleic anhydride);

Poly (1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / 5,7 or 5,8-dimethyltetra Cyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylic acid / 3-hydroxypropyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7 -Ene-2-carboxylate / maleic anhydride);

Poly (1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / methyl 5,7 or 5,8-dimethyl Tetracyclo [4.4.0.1.1] -dodec-7-ene-2,3-dicarboxylate / 3-hydroxypropyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1]- Dodec-7-ene-2-carboxylate / maleic anhydride);

Poly (1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / 5,7 or 5,8-dimethyltetra Cyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylic acid / 2-hydroxyethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7 -Ene-2-carboxylate / N-methyl maleimide); And

Poly (1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / 5,7 or 5,8-dimethyltetra Cyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylic acid / 2-hydroxyethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7 -Ene-2-carboxylate / N-ethyl maleimide).

The copolymer of the present invention may be prepared by radical polymerization of monomers with a conventional radical polymerization initiator, and the process consists of the following steps:

(a) dissolving at least one kind of the compound of formula 1 and at least one monomer selected from maleic anhydride and maleimide as the second monomer in an organic solvent;

(b) adding a polymerization initiator to the resultant solution of step (a); And

(c) reacting the resultant solution of step (b) under a nitrogen or argon atmosphere.

The radical polymerization of the manufacturing process is performed by solution polymerization, and may also be performed by bulk polymerization.
The organic solvent which is a polymerization solvent in this solution polymerization is a single solvent selected from the group consisting of cyclohexanone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, dioxane, methyl ethyl ketone, benzene, toluene and xylene Or a mixed solvent can be used; The polymerization initiator is benzoyl peroxide, 2,2'-azobisisobutyronitrile (AIBN), acetyl peroxide, lauryl peroxide, t-butyl peracetate, t-butyl hydroperoxide and di-t-butylper It may be selected from the group consisting of oxides.

The present invention also provides a photoresist composition comprising the copolymer, organic solvent and photoacid generator of the present invention.

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 Sulfur-based or onium salt-based compounds selected from triflate and dibutylnaphthylsulfonium triflate are mainly used, and are preferably contained in a proportion of 0.1 to 10% by weight based on the copolymer.

In addition, the organic solvent is selected from the group consisting of methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propylene glycol methyl ether acetate and cyclohexanone, and the ratio of 200 to 1000% by weight based on the copolymer It is preferably used as.

The photoresist composition is prepared by dissolving the copolymer of the present invention in an amount of 10 to 30% by weight with respect to an organic solvent, incorporating a photoacid generator in an amount of 0.1 to 10% by weight with respect to the copolymer and filtering with an ultrafine filter. do.

The photoresist composition of the present invention prepared as described above is particularly excellent in etching resistance, heat resistance and adhesion.

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

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

(b) exposing the photoresist film; And

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

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

In addition, the exposure process is performed using an exposure energy of 1 to 100 mJ / cm ² using a deep ultra violet (DUV; E-beam, X-ray or ion beam including ArF, KrF and EUV as a light source It is desirable to be.

Specifically, for example, the photoresist pattern forming method; After spin-coating the photoresist composition of the present invention on a silicon wafer to produce a thin film, and soft-baking for 1 to 5 minutes in an oven or hot plate at 80 to 150 ℃, exposure using an ultraviolet exposure apparatus or an excimer laser exposure apparatus After that, baking was performed after exposure at 100 to 200 ° C. The wafer thus exposed is immersed in a 2.38% TMAH aqueous solution for 30 seconds to 1 minute 30 seconds to obtain an ultrafine positive resist image.

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

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

I. Preparation of Monomer

In Examples below, Examples 1-6 illustrate a method of preparing the compound of Formula 1 by the first method and Examples 7-12 illustrate a method of preparing the compound of Formula 1 by the second method. .

Example 1

(Step 1)

To 500 g of tetrahydrofuran solvent, 1.2 mol of t-butyl acrylate of Formula 11 and 1.0 mol of methylcyclopentadiene were placed in a 2 L flask, followed by stirring at 70 ° C. for 24 hours. After completion of the reaction, the solvent and excess t-butyl acrylate were removed using a rotary distiller, followed by vacuum distillation to obtain pure 2,2-dimethylethyl 5 or 6-methylbicyclo [2.2.1] hept-5-ene-2 of Chemical Formula 12. -Carboxylate was prepared (yield 85%).

Formula 12

(Step 2)

In 500 g of tetrahydrofuran solvent, 1 mol of the compound of formula 12 prepared in the above (Step 1) and 1-6 mol of methylcyclopentadiene were added to a high pressure reactor. Reaction was carried out at 10 to 30 atm for 10 hours at a temperature of 130 to 150 ℃ to obtain a compound of formula (13). At this time, the value of n varies depending on the amount of methylcyclopentadiene added. As a main product, a molecule having an increase of 1 value per 1.2 moles of methylcyclopentadiene was produced. After completion of the reaction to distillation under vacuum to obtain the target compound of formula (13).

Formula 13

Example 2

(Step 1)

1.2 g of t-butyl methacrylate and 1.0 mole of methylcyclopentadiene of Formula 14 were added to 500 g of tetrahydrofuran solvent and stirred at 70 ° C. for 24 hours. After completion of the reaction, the solvent and excess t-butyl methacrylate were removed by rotary distillation, followed by vacuum distillation to obtain pure 2,2-dimethylethyl 2,5 or 2,6-dimethylbicyclo [2.2.1] hept- 5-ene-2-carboxylate was prepared (yield 55%).

Formula 15

(Step 2)

In 500 g of tetrahydrofuran solvent, 1 mole of the compound of Formula 15 and 1 to 6 moles of methylcyclopentadiene prepared in (Step 1) were added to a high pressure reactor. The reaction was carried out at 10 to 30 atmospheres for 10 hours at a temperature of 130 to 150 ℃ to obtain a compound of formula (16). At this time, the value of n varies depending on the amount of methylcyclopentadiene added. As a main product, a molecule having an increase of 1 value per 1.2 moles of methylcyclopentadiene was produced. After completion of the reaction to distillation under vacuum to obtain the target compound of formula (16).

Formula 16

Example 3

(Step 1)

To 500 g of tetrahydrofuran solvent, 1.2 mol of acrylic acid of Formula 17 and 1.0 mol of methylcyclopentadiene were placed in a 2 L flask, followed by stirring at 70 ° C. for 24 hours. After completion of the reaction, the solvent and excess acrylic acid was removed by rotary distillation, followed by vacuum distillation to prepare pure 5 or 6-methylbicyclo [2.2.1] hept-5-ene-2-carboxylic acid of Chemical Formula 18 (yield 82 %).

Formula 18                     

(Step 2)

In 500 g of tetrahydrofuran solvent, 1 mole of the pure compound of Formula 18 and 1 to 6 mole of methylcyclopentadiene prepared in (Step 1) were added to a high pressure reactor. Reaction was carried out for 10 hours at 10 to 30 atm at a temperature of 130 to 150 ℃ to obtain a compound of formula (19). At this time, the value of n varies depending on the amount of methylcyclopentadiene added. As a main product, a molecule having an increase of 1 value per 1.2 moles of methylcyclopentadiene was produced. After completion of the reaction, distillation under vacuum to obtain the target compound of formula (19).

Formula 19

Example 4

(Step 1)

To 500 g of tetrahydrofuran solvent, 1.2 mol of methacrylic acid of formula 20 and 1.0 mol of methylcyclopentadiene were placed in a 2 L flask, followed by stirring at 70 ° C. for 24 hours. After completion of the reaction, the solvent and excess methacrylic acid was removed by rotary distillation, followed by vacuum distillation to obtain pure 2,5 or 2,6-dimethylbicyclo [2.2.1] hept-5-ene-2-carboxylic acid represented by Chemical Formula 21. Was prepared (yield 52%).

Formula 21

(Step 2)

In 500 g of tetrahydrofuran solvent, 1 mole of the compound of formula 21 prepared in step (1) and 1 to 6 moles of methylcyclopentadiene were added to a high pressure reactor. The compound of Chemical Formula 22 was obtained by reacting at a temperature of 130 to 150 ° C. for 10 hours at 10 to 30 atmospheres. At this time, the value of n varies depending on the amount of methylcyclopentadiene added. As a main product, a molecule having an increase of 1 value per 1.2 moles of methylcyclopentadiene was produced. After completion of the reaction by distillation under vacuum to obtain the target compound of formula 22.

Formula 22                     

Example 5

(Step 1)

1.2 g of 2-hydroxyethyl acrylate of Formula 23 and 1.0 mol of methylcyclopentadiene were added to a 500 L tetrahydrofuran solvent in a 2 L flask, followed by stirring at 70 ° C. for 24 hours. After completion of the reaction, the solvent and excess 2-hydroxyethyl acrylate were removed by rotary distillation, followed by vacuum distillation to obtain pure 2-hydroxyethyl 5 or 6-methylbicyclo [2.2.1] hept-5-ene- 2-carboxylate was prepared (yield 80%).

Formula 24                     

(Step 2)

In 500 g of tetrahydrofuran solvent, 1 mole of the compound of formula 24 prepared in step (1) and 1 to 6 moles of methylcyclopentadiene were added to a high pressure reactor. The compound of Chemical Formula 25 was obtained by reacting at a temperature of 130 to 150 ° C. for 10 hours at 10 to 30 atmospheres. At this time, the value of n varies depending on the amount of methylcyclopentadiene added. As a main product, a molecule having an increase of 1 value per 1.2 moles of methylcyclopentadiene was produced. After completion of the reaction to distillation under vacuum to obtain the target compound of formula 25.

Formula 25

Example 6

(Step 1)

1.2 mol of 3-hydroxypropyl acrylate and 1.0 mol of methylcyclopentadiene of Formula 26 were added to 500 g of tetrahydrofuran solvent and stirred at 70 ° C. for 24 hours. After completion of the reaction, the solvent and excess 3-hydroxypropyl acrylate were removed by rotary distillation, followed by vacuum distillation to obtain pure 3-hydroxypropyl 5 or 6-methylbicyclo [2.2.1] hept-5-ene- 2-carboxylate was prepared (yield 83%).

Formula 27

(Step 2)

In 500 g of tetrahydrofuran solvent, 1 mol of the pure compound of Formula 27 prepared in the above (Step 1) and 1-6 mol of methylcyclopentadiene were added to a high pressure reactor. The reaction was performed at 10 to 30 atmospheres for 10 hours at a temperature of 130 to 150 ° C. to obtain a compound of formula 28. At this time, the value of n varies depending on the amount of methylcyclopentadiene added. As a main product, a molecule having an increase of 1 value per 1.2 moles of methylcyclopentadiene was produced. After completion of the reaction by distillation under vacuum to obtain the target compound of formula 28.

Formula 28

Example 7

(Step 1)

1 mole of methylcyclopentadiene and 1 mole of maleic anhydride of Chemical Formula 6 were added to 500 g of tetrahydrofuran solvent, followed by stirring at 70 ° C. for 24 hours. After completion of the reaction, the solvent was removed by rotary distillation and vacuum distillation to obtain pure 5 or 6-methyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride of formula 29 (yield) 91%).

(Step 2)

0.5 mole of the pure compound of Chemical Formula 29 prepared in (Step 1) was dissolved in 500 ml of tetrahydrofuran and then 0.5 mole of t-butanol was added thereto. After 1 g of hydrochloric acid was added thereto, the mixture was refluxed at a temperature of 70 ° C. for 20 hours and cooled to room temperature to form crystals. The resultant was vacuum dried to form 1,1-dimethylethyl 5 or 6-methyl bicyclo [2.2. 1] hept-5-ene-2,3-dicarboxylate was obtained (yield 73%).

Formula 30

(Step 3)

In 500 g of tetrahydrofuran solvent, 1 mol of the compound of Chemical Formula 30 prepared in the above (Step 2) and 1-6 mol of methylcyclopentadiene were added to a high pressure reactor. The compound of Chemical Formula 31 was obtained by reacting at a temperature of 130 to 150 ° C. for 10 hours at 10 to 30 atmospheres. At this time, the value of n varies depending on the amount of methylcyclopentadiene added. As a main product, a molecule having an increase of 1 value per 1.2 moles of methylcyclopentadiene was produced. After completion of the reaction to distillation under vacuum to obtain the target compound of formula (31). In addition to vacuum distillation, it may also be classified as recrystallization from ethyl ether. However, this case is a mixture when n is 1, 2, 3, 4, 5. This mixture can also be used as a monomer.

Formula 31

The compound of Formula 31 may be prepared by the method of Example 8 below using the compound of Formula 32.

Example 8

300 g of tetrahydrofuran solvent, 1 mol of the compound of Formula 29, and 1-6 mol of methylcyclopentadiene were put in a high pressure reactor. The compound of Chemical Formula 31 was obtained by reacting at a temperature of 130 to 150 ° C. for 10 hours at 10 to 30 atmospheres. At this time, the value of n varies depending on the amount of methylcyclopentadiene added. As a main product, a molecule having an increase of 1 value per 1.2 moles of methylcyclopentadiene was produced. After completion of the reaction by distillation under vacuum to obtain a compound of formula (32). 0.5 mole of the compound of Formula 32 was mixed well with 500 ml of tetrahydrofuran solvent and 0.5 mole of t-butanol was added thereto. 1 g of hydrochloric acid was added thereto, refluxed at a temperature of 70 ° C. for 20 hours, and cooled to room temperature to form crystals. The crystals were dried in vacuo to prepare a target compound of Chemical Formula 31.                     

Example 9

(Step 1)

0.5 mole of the pure compound of Chemical Formula 29 prepared in (Step 1) of Example 7 was dissolved in 500 ml of tetrahydrofuran, and 0.5 mole of methanol was added thereto. After 1 g of hydrochloric acid was added thereto, the mixture was refluxed at a temperature of 70 ° C. for 20 hours, and cooled to room temperature. Crystals were formed by vacuum drying, which was then dried under vacuum to obtain methyl 5 or 6-methyl bicyclo [2.2.1] hept-5. -Ene-2,3-dicarboxylate was obtained (yield 72%).

Formula 33

(Step 2)

In 500 g of tetrahydrofuran solvent, 1 mol of the compound of Chemical Formula 33 prepared in (Step 1) and 1-6 mol of methylcyclopentadiene were added to a high pressure reactor. Reaction was carried out for 10 hours at 10 to 30 atm at a temperature of 130 to 150 ℃ to obtain a compound of formula 34. At this time, the value of n varies depending on the amount of methylcyclopentadiene added. As a main product, a molecule having an increase of 1 value per 1.2 moles of methylcyclopentadiene was produced. After completion of the reaction, the resultant was vacuum distilled to obtain the target compound of Chemical Formula 34. In addition to vacuum distillation, it may also be classified by recrystallization from ethyl ether. However, this case is a mixture when n is 1, 2, 3, 4, 5. This mixture can also be used as a monomer.

Formula 34

The compound of Formula 34 may be prepared by the method of Example 10 below using the compound of Formula 32.

Example 10

0.5 mole of the compound of Chemical Formula 32 prepared in Example 8 was mixed well with 500 ml of tetrahydrofuran solvent, and 0.5 mole of methanol was added thereto. 1 g of hydrochloric acid was added thereto, and the mixture was refluxed at a temperature of 70 ° C. for 20 hours and then cooled to room temperature to form crystals. The crystals were dried in vacuo to prepare a target compound of Chemical Formula 34.

Example 11

(Step 1)

0.5 mole of the pure compound of Chemical Formula 29 prepared in (Step 1) of Example 7 was dissolved in 500 ml of an aqueous NaOH solution, refluxed at 80 ° C. for 1.5 hours, and then the temperature was slowly lowered. After neutralizing with diluted hydrochloric acid, the organic layer was separated and extracted with ethyl acetate using a separatory funnel. This was dried in vacuo to give 5 or 6-methyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid of formula 35 (yield 80%).

Formula 35

(Step 2)

In 500 g of tetrahydrofuran solvent, 1 mol of the compound of Chemical Formula 35 prepared in the above (Step 1) and 1-6 mol of methylcyclopentadiene were added to a high pressure reactor. Reaction was carried out for 10 hours at 10 to 30 atm at a temperature of 130 to 150 ℃ to obtain a compound of formula 36. At this time, the value of n varies depending on the amount of methylcyclopentadiene added. As a main product, a molecule having an increase of 1 value per 1.2 moles of methylcyclopentadiene was produced. After completion of the reaction to distillation under vacuum to obtain the target compound of formula 36. In addition to vacuum distillation, it may also be classified by recrystallization from ethyl ether. However, this case is a mixture when n is 1, 2, 3, 4, 5. This mixture can also be used as a monomer.

Formula 36                     

The compound of Formula 36 may be prepared by the method of Example 12 below using the compound of Formula 32.

Example 12

0.5 mole of the compound of Chemical Formula 32 prepared in Example 8 was dissolved in 500 ml of an aqueous NaOH solution, refluxed at 80 ° C. for 1.5 hours, and then the temperature was slowly decreased. After neutralizing with diluted hydrochloric acid, the organic layer was separated and extracted with ethyl acetate using a separatory funnel. This was dried in vacuo to give the target compound of formula 36.

II. Preparation of Polymer

Example 13

0.8 mole of the monomer of Formula 12 prepared in (Step 1) of Example 1, 0.05 mole of the monomer of Formula 18 prepared in (Step 1) of Example 3, of formula 24 prepared in (Step 1) of Example 5 0.15 mol of monomer and 1.0 mol of maleic anhydride were dissolved in tetrahydrofuran, and 2 weight% of AIBN, a polymerization initiator, was added to the total weight of the monomer, followed by nitrogen or argon at a temperature of about 60 to 70 ° C. under a vacuum atmosphere. The reaction was carried out for 4 to 24 hours.

The polymer thus produced was precipitated in ethyl ether or hexane and dried to obtain poly (1,1-dimethylethyl 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2- Carboxylate / 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2-carboxylic acid / 2-hydroxyethyl 5 or 6-methylbicyclo [2.2.1] -hept-5 -En-2-carboxylate / maleic anhydride).

Example 14

Except for using the compound of Formula 35 prepared in (Step 1) of Example 11 instead of the monomer of Formula 18 in the same manner as in Example 13 above poly (1,1-dimethylethyl 5 or 6-Methylbicyclo [2.2.1] -hept-5-ene-2-carboxylate / 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2,3-dicarboxylic acid / 2-hydroxyethyl 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2-carboxylate / maleic anhydride).

Example 15

Except for using the compound of formula 27 prepared in (step 1) of Example 6 instead of the monomer of formula 24 in the same manner as in Example 13 poly (1,1-dimethylethyl 5 or 6-Methylbicyclo [2.2.1] -hept-5-ene-2-carboxylate / 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2-carboxylic acid / 3- Hydroxypropyl 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2-carboxylate / maleic anhydride).

Example 16

Poly (1,1-dimethylethyl 5 or 6-methylbicyclo [2.2.1]-of formula 43, in the same manner as in Example 15, except that the compound of formula 35 was used instead of the monomer of formula 18 Hept-5-ene-2-carboxylate / 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2,3-dicarboxylic acid / 3-hydroxypropyl 5 or 6-methyl Bicyclo [2.2.1] -hept-5-ene-2-carboxylate / maleic anhydride) was prepared.

Example 17

0.8 moles of 1,1-dimethylethyl 5,7 or 5,8-dimethyl tetracyclo [4.4.0.1.1] dodec-7-ene-2-carboxylate monomer of formula 44, 5,7 of formula 45 Or 0.05 moles of 5,8-dimethyl tetracyclo [4.4.0.1.1] dodec-7-ene-2-carboxylic acid monomer, 2-hydroxyethyl 5,7 or 5,8-dimethyl tetracyclo of formula 46 [5.4.0.1.1] 0.15 mol of dodec-7-ene-2-carboxylate monomer and 1.0 mol of maleic anhydride were dissolved in tetrahydrofuran and the total weight of the monomer in which AIBN was added as a polymerization initiator After the addition of 2% by weight, the mixture was reacted for 4 to 24 hours at a temperature of about 60 to 70 ° C. under a nitrogen or argon vacuum atmosphere.

The polymer thus produced was precipitated in ethyl ether or hexane and dried to obtain poly (1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec- 7-ene-2-carboxylate / 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylic acid / 2-hydroxyethyl 5,7 Or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / maleic anhydride).

Example 18

Except for using 0.05 mole of 5,7 or 5,8-dimethyl tetracyclo [4.4.0.1.1] dodec-7-ene-2,3-dicarboxylic acid monomer of the formula And poly (1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-en-2- of Chemical Formula 49 in the same manner as in Example 17; Carboxylate / 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2,3-dicarboxylic acid / 2-hydroxyethyl 5,7 or 5, 8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / maleic anhydride) was prepared.

Example 19

1,1-dimethylethyl 5,7 or 5,8-dimethyl tetracyclo [4.4.0.1.1] dodec-7-ene-2,3-dicarboxylate monomer of the formula Except for using moles, the same procedure as in Example 17 was carried out using poly (1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec- 7-ene-2-carboxylate / 1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.0.1.1] -dodec-7-ene-2,3-dicar Carboxylate / 2-hydroxyethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / maleic anhydride).

Example 20

Using 0.05 mol of 3-hydroxypropyl 5,7 or 5,8-dimethyl tetracyclo [4.4.0.1.1] dodec-7-ene-2-carboxylate monomer of the formula Except for the poly (1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene- of formula 53 in the same manner as in Example 17 except that 2-carboxylate / 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylic acid / 3-hydroxypropyl 5,7 or 5,8 -Dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / maleic anhydride) was prepared.

Example 21

Use of 0.05 mol of methyl 5,7 or 5,8-dimethyl tetracyclo [4.4.0.1.1] dodec-7-ene-2,3-dicarboxylate monomer of formula 54 in place of the compound of formula 45 Except for poly (1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2 of formula 55, in the same manner as in Example 20 except for -Carboxylate / methyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2,3-dicarboxylate / 3-hydroxypropyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / maleic anhydride) was prepared.

Example 22

Except for using 1.0 mol of N-methyl maleimide of formula 56 instead of 1.0 mol of maleic anhydride, poly (1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec- 7-ene-2-carboxylic acid / 2-hydroxyethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / N-methyl Maleimide) was prepared.

Example 23

Except for using 1.0 mol of N-ethyl maleimide of formula 58 instead of 1.0 mol of maleic anhydride, poly (1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec- 7-ene-2-carboxylic acid / 2-hydroxyethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / N-ethyl Maleimide) was prepared.

III. Preparation and Pattern Formation of Photoresist Composition

Example 24

10 g of the polymer obtained in Example 13 was dissolved in 60 g of propylene glycol methyl ether acetate solvent, 0.12 g of triphenyl sulfonium triflate or dibutyl naphthyl sulfonium triflate as a photoacid generator was stirred, and then 0.10 μm. Filtration with a filter produced the photoresist composition of the present invention.

After spin coating the composition on a silicon wafer to prepare a thin film, softbaking for 1 to 5 minutes in an oven or hot plate at 80 to 150 ℃, dimming using an ultraviolet exposure apparatus or an excimer laser exposure apparatus, 100 Baking after light control at 200 ℃. The wafer thus exposed was immersed in a 2.38% TMAH aqueous solution for 30 seconds to 1 minute 30 seconds to obtain an ultrafine positive resist image.

Example 25

A photoresist composition was prepared in the same manner as in Example 24, except that the polymer prepared in Example 14 was used to form a photoresist pattern.

Example 26

A photoresist composition was prepared in the same manner as in Example 24, except that the polymer prepared in Example 15 was used to form a photoresist pattern.

Example 27

A photoresist composition was prepared in the same manner as in Example 24, except that the polymer prepared in Example 16 was used to form a photoresist pattern.

Example 28

A photoresist composition was prepared in the same manner as in Example 24, except that the polymer prepared in Example 17 was used to form a photoresist pattern.

Example 29

A photoresist composition was prepared in the same manner as in Example 24, except that the polymer prepared in Example 18 was used to form a photoresist pattern.

Example 30

A photoresist composition was prepared in the same manner as in Example 24, except that the polymer prepared in Example 19 was used to form a photoresist pattern.

Example 31

A photoresist composition was prepared in the same manner as in Example 24, except that the polymer prepared in Example 20 was used to form a photoresist pattern.

Example 32

A photoresist composition was prepared in the same manner as in Example 24, except that the polymer prepared in Example 21 was used to form a photoresist pattern.

Example 33

A photoresist composition was prepared in the same manner as in Example 24, except that the polymer prepared in Example 22 was used to form a photoresist pattern.

Example 34

A photoresist composition was prepared in the same manner as in Example 24, except that the polymer prepared in Example 23 was used to form a photoresist pattern.

According to the present invention, a photoresist composition which is particularly excellent in etching resistance, heat resistance and adhesion can be obtained, from which a semiconductor device having excellent reliability can be manufactured.

Claims (37)

Polycycloalkene-based compound of formula 1, characterized in that used as a photoresist monomer. Formula 1

Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each is hydrogen, branched or main chain substituted alkyl having 1 to 10 carbon atoms, side or main chain substituted ester having 1 to 10 carbon atoms, 1 carbon And branched or main chain substituted ketones having from 1 to 10, branched or main chain substituted carboxylic acids having from 1 to 10 carbon atoms, side chained or main chain substituted acetals having from 1 to 10 carbon atoms, and at least one hydroxyl group (-OH) Branched or main chain substituted alkyl having 1 to 10 carbon atoms, at least one hydroxyl group having at least one hydroxyl group (—OH), at least one hydroxyl group having at least one hydroxyl group (—OH) Branched or backbone substituted ketones having 1 to 10 carbon atoms, branched or backbone substituted carboxylic acids having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH) or one or more Represents the side chain or the main chain of the substituted acetal of between 1 to 10 carbon atoms which contains a hydroxyl group (-OH), R ₅ and R ₆ represent hydrogen, branched or main chain substituted alkyl or alkoxy having 1 to 10 carbon atoms, n is an integer selected from 0-5. The method of claim 1, The monomers include 1) a monomer for inhibiting dissolution that has a property of dissolving in a developing solution using an acid generated by a light source, 2) an adhesion increasing monomer for increasing adhesion to a wafer, and 3) a sensitivity to light. Polycycloalkene-based compound, characterized in that it is classified as an increased light sensitivity increasing monomer. The method of claim 2, The monomer for inhibiting dissolution is a polycycloalkene-based compound, characterized in that selected from the following formula 12, 13, 15, 16, 30 and 31. Formula 12

Formula 13

Formula 15

Formula 16

Formula 30

Formula 31

Wherein n is an integer selected from 0 to 5. The method of claim 2, Adhesion increasing monomer is a polycycloalkene-based compound, characterized in that selected from the formula 24, 25, 27 and 28. Formula 24

Formula 25

Formula 27

Formula 28

Wherein n is an integer selected from 0 to 5. The method of claim 2, The light sensitivity increasing monomer is a polycycloalkene-based compound, characterized in that selected from the formula 18, 19, 21, 22, 33, 34, 35 and 36. Formula 18

Formula 19

Formula 21

Formula 22

Formula 33

Formula 34

Formula 35

Formula 36

Wherein n is an integer selected from 0 to 5. (a) reacting a compound of formula 2 with a compound of formula 3 with Diels-Alder in an organic solvent, and then removing the organic solvent to obtain a compound of formula 4; And (b) performing a Diels-Alder reaction of the compound of Formula 4 with the compound of Formula 5 in an organic solvent and then removing the organic solvent to obtain a compound of Formula 1. Formula 1

Formula 2

Formula 3

Formula 4

Formula 5

Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each is hydrogen, branched or main chain substituted alkyl having 1 to 10 carbon atoms, side or main chain substituted ester having 1 to 10 carbon atoms, 1 carbon And branched or main chain substituted ketones having from 1 to 10, branched or main chain substituted carboxylic acids having from 1 to 10 carbon atoms, side chained or main chain substituted acetals having from 1 to 10 carbon atoms, and at least one hydroxyl group (-OH) Branched or main chain substituted alkyl having 1 to 10 carbon atoms, at least one hydroxyl group having at least one hydroxyl group (—OH), at least one hydroxyl group having at least one hydroxyl group (—OH) Branched or backbone substituted ketones having 1 to 10 carbon atoms, branched or backbone substituted carboxylic acids having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH) or one or more Represents the side chain or the main chain of the substituted acetal of between 1 to 10 carbon atoms which contains a hydroxyl group (-OH), R ₅ and R ₆ represent hydrogen, branched or main chain substituted alkyl or alkoxy having 1 to 10 carbon atoms, n is an integer selected from 0-5. The method of claim 6, The compound of Formula 2 and Formula 5 is a method for producing a compound of Formula 1, characterized in that methylcyclopentadiene. The method of claim 6, The compound of Formula 5 is a method for producing a compound of Formula 1, characterized in that 1 to 6 moles are used per 1 mole of the compound of Formula 4. The method of claim 6, The organic solvent is selected from the group consisting of tetrahydrofuran (THF), dimethylformamide, dimethyl sulfoxide, dioxane, benzene, toluene and xylene. (a) reacting the compound of formula 2 with maleic anhydride of formula 6 in an organic solvent and then removing the solvent to obtain a compound of formula 7; (b) dissolving the compound of Formula 7 in an organic solvent and then reacting an alcohol (R ₇ OH) to obtain a compound of Formula 8; And (c) a method of preparing the compound of formula 1, comprising the step of obtaining a compound of formula 9 included in the compound of formula 1 by Diels-Alder reacting the compound of formula 8 with the compound of formula 5 in an organic solvent . Formula 1

Formula 2

Formula 5

Formula 6

Formula 7

Formula 8

Formula 9

Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each is hydrogen, branched or main chain substituted alkyl having 1 to 10 carbon atoms, side or main chain substituted ester having 1 to 10 carbon atoms, 1 carbon And branched or main chain substituted ketones having from 1 to 10, branched or main chain substituted carboxylic acids having from 1 to 10 carbon atoms, side chained or main chain substituted acetals having from 1 to 10 carbon atoms, and at least one hydroxyl group (-OH) Branched or main chain substituted alkyl having 1 to 10 carbon atoms, at least one hydroxyl group having at least one hydroxyl group (—OH), at least one hydroxyl group having at least one hydroxyl group (—OH) Branched or backbone substituted ketones having 1 to 10 carbon atoms, branched or backbone substituted carboxylic acids having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH) or one or more Carbon atoms which contains a hydroxyl group (-OH) represents the side chain or the main chain substituted acetal from 1 to 10, R ₅ , R ₆ and R ₇ represent hydrogen, branched or main chain substituted alkyl or alkoxy having 1 to 10 carbon atoms, n is an integer selected from 0-5. The method of claim 10, Diels-Alder reacts the compound of Formula 7 and the compound of Formula 5 obtained in step (a) to obtain a compound of Formula 10, and reacts the compound of Formula 10 with alcohol (R ₇ OH) to be included in the compound of Formula 1 Method for producing a compound of formula 1 characterized in that the step of obtaining a compound of formula (9). Formula 10

In the above, R ₅ , R ₆ and R ₇ represent hydrogen, branched or main chain substituted alkyl or alkoxy having 1 to 10 carbon atoms, n is an integer selected from 0-5. The method of claim 10, The compound of Formula 2 and Formula 5 is a method for producing a compound of Formula 1, characterized in that methylcyclopentadiene. The method according to claim 10 or 11, wherein The compound of Formula 5 is a method for producing a compound of Formula 1, characterized in that 1 to 6 moles are used per 1 mole of the compound of Formula 8 or the compound of Formula 7. The method of claim 10, The organic solvent is selected from the group consisting of tetrahydrofuran (THF), dimethylformamide, dimethyl sulfoxide, dioxane, benzene, toluene and xylene. The method according to claim 10 or 11, wherein The compound of formula 7 or formula 10 is a method for producing a compound of formula 1, characterized in that can be used as a photoresist monomer. delete A copolymer for a photoresist, characterized in that it comprises at least one compound of the formula (1). Formula 1

Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each is hydrogen, branched or main chain substituted alkyl having 1 to 10 carbon atoms, side or main chain substituted ester having 1 to 10 carbon atoms, 1 carbon And branched or main chain substituted ketones having from 1 to 10, branched or main chain substituted carboxylic acids having from 1 to 10 carbon atoms, side chained or main chain substituted acetals having from 1 to 10 carbon atoms, and at least one hydroxyl group (-OH) Branched or main chain substituted alkyl having 1 to 10 carbon atoms, at least one hydroxyl group having at least one hydroxyl group (—OH), at least one hydroxyl group having at least one hydroxyl group (—OH) Branched or backbone substituted ketones having 1 to 10 carbon atoms, branched or backbone substituted carboxylic acids having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH) or one or more Represents the side chain or the main chain of the substituted acetal of between 1 to 10 carbon atoms which contains a hydroxyl group (-OH), R ₅ and R ₆ represent hydrogen, branched or main chain substituted alkyl or alkoxy having 1 to 10 carbon atoms, n is an integer selected from 0-5. The method of claim 17, The copolymer is a monomer for inhibiting dissolution selected from Formula 12, 13, 15, 16, 30, and 31; 2) an adhesion increasing monomer selected from formulas 24, 25, 27 and 28; And 3) at least one monomer of 3 groups each classified into an optical sensitivity increasing monomer selected from Formulas 18, 19, 21, 22, 33, 34, 35, and 36. Formula 12

Formula 13

Formula 15

Formula 16

Formula 30

Formula 31

Formula 24

Formula 25

Formula 27

Formula 28

Formula 18

Formula 19

Formula 21

Formula 22

Formula 33

Formula 34

Formula 35

Formula 36

In the above, n is an integer selected from 0 to 5. The method of claim 17, The copolymer is a photoresist copolymer, characterized in that it comprises one or more compounds selected from the group consisting of maleic anhydride and maleimide as the second monomer. The method according to any one of claims 17 to 19, The copolymer is a photoresist copolymer, characterized in that selected from the formula (37) to formula (39). Formula 37

Formula 38

Formula 39

Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each is hydrogen, branched or main chain substituted alkyl having 1 to 10 carbon atoms, side or main chain substituted ester having 1 to 10 carbon atoms, 1 carbon And branched or main chain substituted ketones having from 1 to 10, branched or main chain substituted carboxylic acids having from 1 to 10 carbon atoms, side chained or main chain substituted acetals having from 1 to 10 carbon atoms, and at least one hydroxyl group (-OH) Branched or main chain substituted alkyl having 1 to 10 carbon atoms, at least one hydroxyl group having at least one hydroxyl group (—OH), at least one hydroxyl group having at least one hydroxyl group (—OH) Branched or backbone substituted ketones having 1 to 10 carbon atoms, branched or backbone substituted carboxylic acids having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH) or one or more Represents the side chain or the main chain of the substituted acetal of between 1 to 10 carbon atoms which contains a hydroxyl group (-OH), R ₅ and R ₆ represent hydrogen, branched or main chain substituted alkyl or alkoxy having 1 to 10 carbon atoms, wherein the position of R ₆ is not limited to that shown and may be selected as shown in Formula 1, eg For example, when n = 1, R ₆ may be at position 5 or at position 10. l, m and n may be the same or different and each is an integer selected from 0 to 5, a is the molar ratio of the monomer for inhibiting dissolution, b is the molar ratio of the adhesion increasing monomer, and c is the molar ratio of the light sensitivity increasing monomer. The method of claim 17, The copolymer has a molecular weight of 3,000 to 10,000 copolymer for photoresist, characterized in that. The method of claim 17, The copolymer is poly (1,1-dimethylethyl 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2-carboxylate / 5 or 6-methylbicyclo [2.2.1]- Hept-5-ene-2-carboxylic acid / 2-hydroxyethyl 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2-carboxylate / maleic anhydride); Poly (1,1-dimethylethyl 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2-carboxylate / 5 or 6-methylbicyclo [2.2.1] -hept-5- En-2,3-dicarboxylic acid / 2-hydroxyethyl 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2-carboxylate / maleic anhydride); Poly (1,1-dimethylethyl 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2-carboxylate / 5 or 6-methylbicyclo [2.2.1] -hept-5- En-2-carboxylic acid / 3-hydroxypropyl 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2-carboxylate / maleic anhydride); Poly (1,1-dimethylethyl 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2-carboxylate / 5 or 6-methylbicyclo [2.2.1] -hept-5- Ene-2,3-dicarboxylic acid / 3-hydroxypropyl 5 or 6-methylbicyclo [2.2.1] -hept-5-ene-2-carboxylate / maleic anhydride); Poly (1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / 5,7 or 5,8-dimethyltetra Cyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylic acid / 2-hydroxyethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7 -Ene-2-carboxylate / maleic anhydride); Poly (1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / 5,7 or 5,8-dimethyltetra Cyclo [4.4.0.1.1] -dodec-7-ene-2,3-dicarboxylic acid / 2-hydroxyethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dode X-7-ene-2-carboxylate / maleic anhydride); Poly (1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / 1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2,3-dicarboxylate / 2-hydroxyethyl 5,7 or 5,8-dimethyltetracyclo [4.4. 0.1.1] -dodec-7-ene-2-carboxylate / maleic anhydride); Poly (1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / 5,7 or 5,8-dimethyltetra Cyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylic acid / 3-hydroxypropyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7 -Ene-2-carboxylate / maleic anhydride); Poly (1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / methyl 5,7 or 5,8-dimethyl Tetracyclo [4.4.0.1.1] -dodec-7-ene-2,3-dicarboxylate / 3-hydroxypropyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1]- Dodec-7-ene-2-carboxylate / maleic anhydride); Poly (1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / 5,7 or 5,8-dimethyltetra Cyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylic acid / 2-hydroxyethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7 -Ene-2-carboxylate / N-methyl maleimide); And Poly (1,1-dimethylethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylate / 5,7 or 5,8-dimethyltetra Cyclo [4.4.0.1.1] -dodec-7-ene-2-carboxylic acid / 2-hydroxyethyl 5,7 or 5,8-dimethyltetracyclo [4.4.0.1.1] -dodec-7 -Ene-2-carboxylate / N-ethyl maleimide) copolymer for a photoresist, characterized in that. (a) dissolving at least one kind of the compound of Formula 1 and at least one monomer selected from maleic anhydride and maleimide as the second monomer in an organic solvent; (b) adding a polymerization initiator to the resultant solution of step (a); And (c) a method of producing a copolymer for photoresist comprising the step of reacting the resultant solution of step (b) under nitrogen or argon atmosphere. Formula 1

Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each is hydrogen, branched or main chain substituted alkyl having 1 to 10 carbon atoms, side or main chain substituted ester having 1 to 10 carbon atoms, 1 carbon And branched or main chain substituted ketones having from 1 to 10, branched or main chain substituted carboxylic acids having from 1 to 10 carbon atoms, side chained or main chain substituted acetals having from 1 to 10 carbon atoms, and at least one hydroxyl group (-OH) Branched or main chain substituted alkyl having 1 to 10 carbon atoms, at least one hydroxyl group having at least one hydroxyl group (—OH), at least one hydroxyl group having at least one hydroxyl group (—OH) Branched or backbone substituted ketones having from 1 to 10 carbon atoms, branched or backbone substituted carboxylic acids having from 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH) or one or more Side or main chain substituted acetals having 1 to 10 carbon atoms containing a hydroxyl group (-OH) on the phase, R ₅ and R ₆ represent hydrogen, branched or main chain substituted alkyl or alkoxy having 1 to 10 carbon atoms, n is an integer selected from 0-5. The method of claim 23, wherein The organic solvent is selected from the group consisting of cyclohexanone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, dioxane, methyl ethyl ketone, benzene, toluene and xylene . The method of claim 23, wherein The polymerization initiators are benzoyl peroxide, 2,2'-azobisisobutyronitrile (AIBN), acetyl peroxide, lauryl peroxide, t-butyl peracetate, t-butyl hydroperoxide and di-t-butyl Method for producing a photoresist copolymer, characterized in that selected from the group consisting of peroxides. In a photoresist composition comprising a photoresist copolymer, an organic solvent, and a photoacid generator, the photoresist copolymer includes one or two or more kinds of compounds represented by Formula 1 as a first monomer, and a second A photoresist composition comprising as a monomer at least one compound selected from maleic anhydride and maleimide. Formula 1

Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each is hydrogen, branched or main chain substituted alkyl having 1 to 10 carbon atoms, side or main chain substituted ester having 1 to 10 carbon atoms, 1 carbon And branched or main chain substituted ketones having from 1 to 10, branched or main chain substituted carboxylic acids having from 1 to 10 carbon atoms, side chained or main chain substituted acetals having from 1 to 10 carbon atoms, and at least one hydroxyl group (-OH) Branched or main chain substituted alkyl having 1 to 10 carbon atoms, at least one hydroxyl group having at least one hydroxyl group (—OH), at least one hydroxyl group having at least one hydroxyl group (—OH) Branched or backbone substituted ketones having 1 to 10 carbon atoms, branched or backbone substituted carboxylic acids having 1 to 10 carbon atoms containing one or more hydroxyl groups (—OH) or one or more Represents the side chain or the main chain of the substituted acetal of between 1 to 10 carbon atoms which contains a hydroxyl group (-OH), R ₅ and R ₆ represent hydrogen, branched or main chain substituted alkyl or alkoxy having 1 to 10 carbon atoms, n is an integer selected from 0-5. The method of claim 26, The photoresist is a photoresist composition, characterized in that the sulfur salt or onium salt. The method of claim 27, The photoacid generator is diphenyl iodo hexafluorophosphate, diphenyl iodo hexafluoro arsenate, diphenyl iodo hexafluoro antimonate, diphenyl paramethoxyphenyl triflate, diphenyl paratoluenyl triflate, diphenyl Paraisobutylphenyl triflate, diphenylpara-t-butylphenyl triflate, triphenylsulfonium hexafluoro phosphate, triphenylsulfonium hexafluoro arsenate, triphenylsulfonium hexafluoro antimonate, triphenylsulfonium A photoresist composition comprising one or more selected from the group consisting of triflate and dibutylnaphthylsulfonium triflate. The method of claim 26, The photoresist composition is a photoresist composition, characterized in that used in 0.1 to 10% by weight relative to the photoresist copolymer. The method of claim 26, The organic solvent is selected from the group consisting of methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propylene glycol methyl ether acetate and cyclohexanone. The method of claim 26, The organic solvent is a photoresist composition, characterized in that used in 200 to 1000% by weight relative to the photoresist copolymer. (a) applying the photoresist composition of claim 26 over the etched layer to form a photoresist film; (b) exposing the photoresist film; And (c) developing the resultant to obtain a desired pattern. The method of claim 32, I) pre-exposure and post-exposure of step (b); Or ii) performing a baking process before or after exposure, respectively. The method of claim 33, The baking process is a photoresist pattern forming method, characterized in that performed at 70 to 200 ℃. The method of claim 32, The exposure process is a photoresist pattern forming method using a deep ultraviolet (DUV; E-beam, X-ray or ion beam including ArF, KrF and EUV as a light source. The method of claim 32, The exposure process is a photoresist pattern forming method, characterized in that performed with an exposure energy of 1 to 100 mJ / cm ² . A semiconductor device manufactured by the method of claim 32.