• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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  • 优先权
    • 专利摘要:
    The present invention relates to a polymer represented by the following formula (1) and a method of forming a micropattern using the same. In the above formula, R represents a primary or secondary alcohol having 1 to 10 carbon atoms, m and n each represent a number from 1 to 3, The ratio of a: b: c represents 10-90: 10-90: 10-90. The photoresist resin of the present invention can be used to form ultrafine patterns of 4G and 16G DRAMs and can be used for ArF, EUV, E-beam or ion-beam.
    公开号:KR19990081720A
    申请号:KR1019980016221
    申请日:1998-04-30
    公开日:1999-11-15
    发明作者:정재창；김형기；노치형；이근수；김명수；정민호；복철규；백기호
    申请人:김영환；현대전자산업 주식회사；
    IPC主号:
    专利说明:

    Polymer and method of forming micropattern using same
    The present invention relates to a polymer and a method of forming a micropattern using the same. More specifically, the present invention is a polymer that can be used to form ultra-fine patterns of 4G, 16G DRAM, and can use ArF, E-beam, EUV or ion-beam, KrF or ArF photoresist for TSI (top surface image). It relates to a polymer that can be used for and a method of forming a fine pattern using the same.
    Generally, in the manufacturing process of a semiconductor element, the photosensitive film pattern is used in order to form the semiconductor element pattern of a predetermined shape. However, in order to obtain a desired photoresist pattern, a photoresist is applied onto a semiconductor substrate, the coated photoresist is exposed, and then a developing process is performed to form a photoresist pattern on the semiconductor substrate.
    In preparing a photoresist pattern formed by using a conventional general silylation process, the photoresist is mainly composed of a diazonaphtoquinone substance, a novolac resin or a photoacid generator, and a polyvinylphenol resin. Consists of Therefore, when exposed and baked by light sources ArF, KrF, and I lines, alcohol groups are formed in the exposed portion. After baking, silylation with a silylation agent such as hexamedylsilazane or tetramethyldisilazane results in N-Si bonding. However, since these N-Si bonds are weak, they react with the ROH of the resin to form RO-Si bonds. The silicon combined with the photoresist resin forms a silicon oxide film by dry develop using O 2 plasma, and the lower end of the portion remains after development to form a pattern.
    However, in the method of forming the above-mentioned silicide photosensitive film pattern, it is impossible to form an ultrafine pattern of 0.10 µm L / S or less when using a KrF excimer laser, and when using an ArF light source, Due to the damage of the lens of the exposure machine, exposure should be performed at a low exposure energy of 10 mJ / cm 2 or less.However, with such a low energy, the photoresist film may not be sufficiently exposed to form a pattern. There is a problem that high integration of semiconductor devices is lowered due to lack of resolution.
    Also, in the manufacturing of 4G DRAM or 16G DRAM using an ultra-fine circuit of 100 nm or less, in the case of the wet phenomenon, as the pattern becomes finer, the thickness of the photoresist may be thinner to form the pattern. However, if the pattern is thin, etching is impossible. Therefore, the essential condition for photoresist is etching resistance. However, it is almost impossible to overcome this etching resistance. In addition, the deformation caused by the energy of the optical system becomes a big problem when forming a pattern such as ArF, EUV. Therefore, there is a demand for the development of a highly sensitive photoresist capable of forming patterns even with a small amount of energy.
    Therefore, as an attempt to solve this problem, a top surface image (TSI) process using a sililation process has been proposed. However, even with such a TSI process, an ultrafine pattern of 0.10 μm L / S or less can be obtained using a conventional KrF excimer laser. Formation appeared to be impossible.
    In addition, the conventional photoresist for TSI using an ArF light source uses a polyvinylphenol-based or novolak-based resin. In this case, there is a problem in that the aromatic absorbs ArF light and thus the light sensitivity is low.
    Accordingly, the present inventors have conducted numerous studies and experiments to solve the above-mentioned problems of the prior art, and as a result, during the process accompanying TSI by introducing an alicyclic compound (for example, a bicyclic compound) into the photoresist resin, It is possible to secure heat resistance to withstand the post exposure bake and the silylation process with high temperature, and by using a chemically amplified resist composed of a photoacid generator and a polymer, When used, ArF light does not damage the lens of the exposure machine, and resolution is possible even with a small amount of energy (10 mJ / cm 2 or less), and the photoresist pattern collapse or lack of resolution generated when forming a micro pattern using an ArF (193 nm) light source. The phenomenon can be prevented, and a silicon oxide film is formed on the chemically amplified photosensitive film by a silylation process using O 2 plasma. The present invention has been completed to discover the surprising fact that it can increase the etching resistance and heat resistance, and can form a fine pattern by a dry development process.
    1 is a process for producing a photosensitive film pattern using a polymer according to the present invention.
    2 to 6 is an NMR graph according to an embodiment of the present invention.
    7 is a pattern state diagram of a photoresist according to the present invention.
    ◈ Explanation of symbols for the main parts of the drawings
    1: exposure mask 2: photoresist
    3: etching target layer
    The present invention relates to a polymer represented by the following Chemical Formula 1, wherein the polymer can be used not only for TSI but also as a single photosensitive film.
    In the above formula,
    R represents a primary or secondary alcohol having 1 to 10 carbon atoms,
    m and n each represent a number from 1 to 3,
    The ratio of a: b: c represents 10-100: 10-90: 10-90.
    The present invention also relates to a process for preparing the above formula (1) polymer.
    The present invention also relates to a photoresist containing the polymer of Formula 1, a solvent and a photoacid generator.
    The present invention also relates to a method of forming a fine photoresist pattern using the photoresist.
    Hereinafter, the present invention will be described in detail.
    The polymer of Chemical Formula 1 according to the present invention may be prepared by polymerizing maleic hydride represented by Chemical Formula 2, a compound represented by Chemical Formula 3, and a compound represented by Chemical Formula 4 in the presence of a polymerization initiator.

    In the above formula,
    R represents a primary or secondary alcohol having 1 to 10 carbon atoms,
    m and n each represent a number from 1 to 3.
    The compound of the formula (3) used in the present invention is preferably t-butyl 5-norbornene-2-carboxylate, t-butylbicyclo [2,2,2] oct-5-ene-2-carboxylate .
    Formula 4 compound in the present invention includes a compound wherein R is methyl alcohol, ethyl alcohol, propyl alcohol, propyl alcohol, butyl alcohol or pentyl alcohol. Preferably 2-hydroxyethyl 5-norbornene-2-carboxylate, 3-hydroxypropyl 5-norbornene-2-carboxylate, 2-hydroxyethyl bicyclo [2,2,2] oct -5-ene-2-carboxylate or 3-hydroxypropyl bicyclo [2,2,2] oct-5-ene-2-carboxylate is used.
    According to the present invention, the maleic hydride of Formula 2, the compound of Formula 3, and the compound of Formula 4 are reacted in a molar ratio of 1: 0.2 to 0.8: 0.2 to 0.8 to prepare a polymer of Formula 1.
    The polymer of the present invention can be prepared by a conventional polymerization method in the presence of a polymerization initiator. Polymerization methods include, for example, bulk polymerization and solution polymerization. As the polymerization initiator, benzoyl peroxide, 2,2-azobisisobutyronitrile (AIBN), acetyl peroxide, lauryl peroxide, or t-butyl peroxide may be used. Tetrahydrofuran (THF), cyclohexane, methyl ethyl ketone, benzene, toluene, dioxane or dimethylformamide are used as the polymerization solvent. The polymerization is carried out for 5 to 25 hours at a temperature of 60 to 80 ° C. under nitrogen or argon atmosphere. However, it is not limited to these polymerization conditions.
    The polymer of Formula 1 prepared as described above is useful for forming a fine pattern of a semiconductor device. The photoresist of the present invention may be prepared by mixing the polymer of Formula 1 with a solvent and a photoacid generator in a conventional manner. Photoacid generators are sulfur-based or onium-based salts, for example diphenyliodolic acid hexafluoro phosphate, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluoroantionate, diphenyl parameth Methoxyphenyl triflate, diphenyl paratoluenyl triflate, diphenyl paraisobutylphenyl triflate, diphenyl para-t-butylphenyl triflate, triphenylsulfonium hexafluoro phosphate, triphenylsulfonium hexafluoro arse One or more selected from among nate, triphenylsulfonium hexafluor antimonate dibutylnaphthyl sulfonium triflate, and triphenylsulfonium triflate. The photoacid generator is used in an amount of 1 to 20% by weight of the polymer used. This is because the sensitivity is insufficient at 1% or less, and the etching resistance is insufficient at 20% or more. The solvent may be methyl-3-methoxypropionate or a conventional organic solvent such as ethyl-3-ethoxypropionate, methyl-3-methoxypropionate, propylene glycol methyl ether acetate. . The solvent is used in an amount of 100 to 700% by weight of the polymer used. According to the quantity of the said solvent, the photosensitive film of about 0.3-3 micrometers thickness can be formed.
    The present invention also includes a method of forming a fine pattern using the photoresist. Specifically, as shown in FIG. 1, the photoresist 2 is applied on the etching target layer 3 on the substrate 10 to be primarily cured, and the exposure mask 1 is applied to the cured photoresist 2. After exposure to form the exposure area 12, and after the secondary curing, the silylation agent is sprayed on the exposed portion to form a silylation film 14, the silicon oxide film (in a dry developing process using O 2 plasma ( 16) and the etched layer 3 is etched using the silicon oxide film 16 as an etch mask to form an etched layer pattern.
    Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
    1 is a cross-sectional view illustrating a method of forming a siliculation photosensitive film pattern for a TSI of a semiconductor device according to the present invention.
    First, the etching target layer 3 is formed on the substrate 10, and the photoresist 2 is applied on the etching target layer 3 and cured (first curing step). The photoresist is cured after baking for 30 to 300 seconds at a temperature of 110 to 150 ℃ after coating. The photoresist 2 may form an ultrafine pattern of 100 nm or less due to no flow of the photoresist at a high temperature (ie, 150 to 190 ° C.) of a subsequent silylation process. The cured photoresist 2 is exposed to exposure energy of 1 to 50 mJ / cm 2 using ArF, EUV, E-beam, Ion-beam or the like as a light source using an exposure mask 1. After baking for 30 to 300 seconds at a temperature of 110 to 150 ℃, as shown in the reaction schemes 1 and 2, the exposure site is changed to t-butyl group to carboxylic acid by the diffusion of acid, and isobutene is a by-product. The hexamethyldisilazane, which is a silylating agent, facilitates penetration into the photoresist in the subsequent silylation process while being discharged from the photoresist in gaseous state.
    (Scheme 1)
    (Scheme 2)
    Examples of the silylating agent include hexamethyldisilazane, tetramethyldisilazane, dimethylaminodimethylsilane, dimethylaminoethylsilane, dimethylsilyldimethylamine, trimethylsilyldimethylamine, trimethylsilyldiethylamine, dimethylaminopentamethylsilane, and the like. Can be used. The silylation process is carried out at a temperature of 100 to 170 ° C. for about 30 to 300 seconds.
    The key of the photoresist for TSI according to the present invention is that the silylation reaction is promoted by the carboxylic acid generated by the acid. The reaction principle is shown in FIG. Hexamethyldisilazane, a silylating agent, is one of the most basic of amines due to the strong electron donating ability of silicon atoms attached to nitrogen atoms. Therefore, the reaction with the carboxylic acid generated in the photoresist (2) in the sililation process to form an amine salt (amine salt) as shown in part A of FIG. This amine salt reacts very easily with the hydroxy functional groups of the polymer to form a stable Si-O structure such as B in FIG. On the other hand, since there is no generation of carboxylic acid in the non-exposed part, the reaction as shown in FIG. 3 does not occur, and the photoresist is hardened so that hexamethyldisilazane, a silylating agent, is not easily penetrated into the photoresist. The silicon combined with the polymer in the photoresist forms a silicon oxide film by a dry development process using an O 2 plasma, and the lower end of the portion remains as it is after development to form a pattern.
    Hereinafter, although this invention is demonstrated concretely based on a manufacture example and an Example, it is not understood that the technical scope of this invention is limited to these.
    Example 1: Sum of poly (maleic anhydride / t-butyl 5-norbornene-2-carboxylate / 2-hydroxyethyl 5-norbornene-2-carboxylate) polymer (Formula 5)
    200 g of tetrahydrofuran (THF) solvent was mixed with 1 mol of maleic anhydride, 0.5 mol of t-butyl 5-norbornene-2-carboxylate and 0.5 mol of 2-hydroxyethyl 5-norbornene-2-carboxylate. After melting, 5.7 g of 2,2'-azobisisobutyronitrile (AIBN) was added thereto, followed by reaction for 10 hours at a temperature of 67 ° C. under a nitrogen atmosphere. After completion of the polymer reaction, the precipitate was caught in ethyl ether and dried to obtain the title poly (maleic anhydride / t-butyl 5-norbornene-2-carboxylate / 2-hydroxyethyl 5-norbornene-2-carbohydrate). 170 g of a carboxylate) polymer was obtained and its NMR data is shown in FIG. (Yield 60%).
    Example 2 Synthesis of Poly (maleic anhydride / t-butyl 5-norbornene-2-carboxylate / 3-hydroxypropyl 5-norbornene-2-carboxylate) polymer (Formula 6)
    200 g of tetrahydrofuran (THF) solvent is mixed with 1 mol of maleic anhydride, 0.5 mol of t-butyl 5-norbornene-2-carboxylate and 0.5 mol of 3-hydroxypropyl 5-norbornene-2-carboxylate. After melting, 6 g of 2,2'-azobisisobutyronitrile (AIBN) was added thereto, followed by reaction at a temperature of 67 ° C. for 10 hours under a nitrogen atmosphere. After completion of the polymer reaction, the precipitate was caught in an ethyl ether solvent and dried to obtain the title poly (maleic anhydride / t-butyl 5-norbornene-2-carboxylate / 3-hydroxypropyl 5-norbornene-2- 167 g of carboxylate) polymer was obtained and its NMR data is shown in FIG. (Yield 57%).
    Example 3: Poly (maleic anhydride / t-butyl bicyclo [2,2,2] oct-5-ene-2-carboxylate / 2-hydroxyethyl 5-norbornene-2-carboxyl Rate) Synthesis of Polymer (Formula 7)
    1 mol maleic anhydride, 0.5 mol t-butyl bicyclo [2,2,2] oct-5-ene2-carboxylate and 0.5 mol 2-hydroxyethyl 5-norbornene-2-carboxylate The solution was dissolved in 200 g of tetrahydrofuran (THF) solvent, 6 g of 2,2'-azobisisobutyronitrile (AIBN) was added thereto, and the mixture was reacted at a temperature of 67 ° C. for 10 hours under a nitrogen atmosphere. After completion of the polymer reaction, the precipitate was caught in hexane solvent and dried to obtain the title poly (maleic anhydride / t-butyl bicyclo [2,2,2] oct-5-ene-2-carboxylate / 2-hydride). 146 g of oxyethyl 5-norbornene-2-carboxylate) polymer was obtained and its NMR data is shown in FIG. (Yield 50%).
    Example 4 Poly (maleic anhydride / t-butyl bicyclo [2,2,2] oct-5-ene-2-carboxylate / 3-hydroxypropyl 5-norbornene-2-carboxyl Synthesis of Polymer)
    1 mole maleic anhydride, 0.5 mole t-butyl bicyclo [2,2,2] oct-5-ene2-carboxylate and 0.5 mole 3-hydroxypropyl 5-norbornene-2-carboxylate The solution was dissolved in 200 g of tetrahydrofuran (THF) solvent, 6 g of 2,2'-azobisisobutyronitrile (AIBN) was added thereto, and the mixture was reacted at a temperature of 67 ° C. for 10 hours under a nitrogen atmosphere. After completion of the polymer reaction, the precipitate was caught in an ethyl ether solvent and dried to obtain the title poly (maleic anhydride / t-butyl bicyclo [2,2,2] oct-5-ene-2-carboxylate / 3- 150 g of hydroxypropyl 5-norbornene-2-carboxylate) polymer was obtained and its NMR data is shown in FIG. 5 (Yield: 50%).
    Example 5 Poly (maleic anhydride / t-butyl 5-norbornene-2-carboxylate / 2-hydroxyethyl bicyclo [2,2,2] oct-5-ene-2-carboxyl Rate) Synthesis of Polymer (9)
    1 mole of maleic anhydride, 0.5 mole of t-butyl 5-norbornene-2-carboxylate, 0.5 mole of 3-hydroxypropyl bicyclo [2,2,2] oct-5-ene-2-carboxylate After molar was dissolved in 200 g of tetrahydrofuran (THF) solvent, 6 g of 2,2'-azobisisobutyronitrile (AIBN) was added thereto, followed by reaction at a temperature of 67 ° C. for 10 hours under a nitrogen atmosphere. After completion of the polymer reaction, the precipitate was caught in an ethyl ether solvent and dried to obtain the title poly (maleic anhydride / t-butyl 5-norbornene-2-carboxylate / 2-hydroxyethyl bicyclo [2,2, 2] Oct-5-ene-2-carboxylate) 150g of polymer was obtained and its NMR data is shown in FIG. (Yield 51%).
    Example 6 Poly (maleic anhydride / t-butyl 5-norbornene-2-carboxylate / 3-hydroxypropyl bicyclo [2,2,2] oct-5-ene-2-carboxyl Rate) Synthesis of Polymer (Formula 10)
    1 mole of maleic anhydride, 0.5 mole of t-butyl 5-norbornene-2-carboxylate and 0.5 mole of 3-hydroxypropyl bicyclo [2,2,2] oct-5-ene-2-carboxylate After molar mole was dissolved in 200 g of tetrahydrofuran (THF) solvent, 6 g of 2,2'-azobisisobutyronitrile (AIBN) was added thereto, and the reaction was carried out at a temperature of 60 to 70 ° C. under a nitrogen atmosphere for 10 hours. After completion of the polymer reaction, the precipitate was caught in an ethyl ether solvent and dried to obtain the title poly (maleic anhydride / t-butyl 5-norbornene-2-carboxylate / 3-hydroxypropyl bicyclo [2,2, 2] oct-5-ene-2-carboxylate) 168 g of a polymer was obtained (yield: 56%).
    Example 7: Poly (maleic anhydride / t-butyl bicyclo [2,2,2] oct-5-ene-2-carboxylate / 2-hydroxyethyl bicyclo [2,2,2] Synthesis of Oct-5-ene-2-carboxylate) Polymer
    1 mole maleic anhydride, 0.5 mole t-butyl bicyclo [2,2,2] oct-5-ene-2-carboxylate and 2-hydroxyethyl bicyclo [2,2,2] oct- 0.5 mole of 5-ene-2-carboxylate was dissolved in 200 g of tetrahydrofuran (THF) solvent, 6 g of 2,2'-azobisisobutyronitrile (AIBN) was added thereto, and the temperature was 67 ° C. under a nitrogen atmosphere. The reaction is carried out for 10 hours. After completion of the polymer reaction, the precipitate was caught in an ethyl ether solvent and dried to obtain the title poly (maleic anhydride / t-butyl bicyclo [2,2,2] oct-5-ene-2-carboxylate / 2- 156 g of hydroxyethyl bicyclo [2,2,2] oct-5-ene-2-carboxylate) polymer was obtained (yield: 52%).
    Example 8: Poly (maleic anhydride / t-butyl bicyclo [2,2,2] oct-5-ene-2-carboxylate / 3-hydroxypropyl bicyclo [2,2,2] Synthesis of Oct-5-ene-2-carboxylate) Polymer
    1 mole maleic anhydride, 0.5 mole t-butyl bicyclo [2,2,2] oct-5-ene2-carboxylate and 3-hydroxypropyl bicyclo [2,2,2] oct-5 -0.5 moles of ene-2-carboxylate was dissolved in 200 g of tetrahydrofuran (THF) solvent, and 6 g of 2,2'-azobisisobutyronitrile (AIBN) was added thereto. React time. After completion of the polymer reaction, the precipitate was caught in an ethyl ether solvent and dried to obtain the title poly (maleic anhydride / t-butyl bicyclo [2,2,2] oct-5-ene-2-carboxylate / 3- 150 g of hydroxypropyl bicyclo [2,2,2] oct-5-ene-2-carboxylate) polymer was obtained (yield: 49%).
    Application Example 1 Preparation and Pattern Formation of Photoresist
    10 g of a poly (maleic anhydride / t-butyl 5-norbornene-2-carboxylate / 2-hydroxyethyl 5-norbornene-2-carboxylate) polymer synthesized in Example 1 was substituted with ethyl 3- After dissolving in 40 g of ethoxypropionate solvent, 0.4 g of triphenylsulfonium triplate was added, filtered through a 0.10 μm filter, coated on the surface of the wafer, and a photoresist pattern was formed in the same manner as in FIG. Is shown in FIG.
    Application Example 2 Preparation and Pattern Formation of Photoresist
    Application using 10 g of a poly (maleic anhydride / t-butyl 5-norbornene-2-carboxylate / 3-hydroxypropyl 5-norbornene-2-carboxylate) polymer synthesized in Example 2 A photoresist pattern was formed in the same manner as in Example 1.
    Application Example 3 Preparation and Pattern Formation of Photoresist
    Poly (maleic anhydride / t-butyl bicyclo [2,2,2] oct-5-ene-2-carboxylate / 2-hydroxyethyl 5-norbornene-2- synthesized in Example 3 A photoresist pattern was formed in the same manner as in Application Example 1 using 10 g of a carboxylate) polymer.
    Application Example 4 Preparation and Pattern Formation of Photoresist
    Poly (maleic anhydride / t-butyl bicyclo [2,2,2] oct-5-ene-2-carboxylate / 3-hydroxypropyl 5-norbornene-2- synthesized in Example 4 A photoresist pattern was formed in the same manner as in Application Example 1 using 10 g of a carboxylate) polymer.
    Application Example 5 Preparation and Pattern Formation of Photoresist
    Poly (maleic hydride / t-butyl 5-norbornene-2-carboxylate / 2-hydroxyethyl bicyclo [2,2,2] oct-5-en-2-car synthesized in Example 5 10 g of a carboxylate polymer was used to form a photoresist pattern in the same manner as in Application Example 1.
    Application Example 6 Preparation and Pattern Formation of Photoresist
    Poly (maleic anhydride / t-butyl 5-norbornene-2-carboxylate / 3-hydroxypropyl bicyclo [2,2,2] oct-5-ene-2- synthesized in Example 6 A photoresist pattern was formed in the same manner as in Application Example 1 using 10 g of a carboxylate) polymer.
    Application Example 7 Preparation and Pattern Formation of Photoresist
    Poly (maleic anhydride / t-butyl bicyclo [2,2,2] oct-5-ene-2-carboxylate / 2-hydroxyethyl bicyclo [2,2, 2] Photoresist pattern was formed in the same manner as in Application Example 1 using 10 g of oct-5-ene-2-carboxylate) copolymer resin.
    Application Example 8 Preparation and Pattern Formation of Photoresist
    Poly (maleic anhydride / t-butyl bicyclo [2,2,2] oct-5-ene-2-carboxylate / 3-hydroxypropyl bicyclo [2,2, 2] Photoresist pattern was formed in the same manner as in Application Example 1 using 10 g of oct-5-ene-2-carboxylate) polymer.
    As described above, the ArF photoresist according to the present invention can ensure heat resistance to withstand the post-exposure bake process and the silication process with high temperature during the process accompanying TSI, and when the ArF light source is used, The silicon oxide film is formed by a silication process using O 2 plasma on a chemically amplified photoresist that can prevent the lens damage of the lens and can be resolved with a small amount of energy of 10 mJ / cm 2 , thereby increasing the etching resistance and heat resistance. The micro pattern may be formed by a dry development process. Therefore, the use of the photoresist of the polymer according to the present invention enables high integration of semiconductor devices.
    权利要求:
    Claims (26)
    [1" claim-type="Currently amended] A polymer represented by the following formula (1).
    Formula 1

    In the above formula,
    R represents a primary or secondary alcohol having 1 to 10 carbon atoms,
    m and n each represent a number from 1 to 3,
    The ratio of a: b: c represents 10-90: 10-90: 10-90.
    [2" claim-type="Currently amended] The polymer of claim 1 wherein the polymer is poly (maleic anhydride / t-butyl 5-norbornene-2-carboxylate / 2-hydroxyethyl 5-norbornene-2-carboxylate).
    [3" claim-type="Currently amended] The polymer of claim 1 wherein the polymer is poly (maleic anhydride / t-butyl 5-norbornene-2-carboxylate / 3-hydroxypropyl 5-norbornene-2-carboxylate).
    [4" claim-type="Currently amended] The method of claim 1, wherein the polymer is poly (maleic anhydride / t-butyl bicyclo [2,2,2] oct-5-ene-2-carboxylate / 2-hydroxyethyl 5-norbornene -2-carboxylate).
    [5" claim-type="Currently amended] The method of claim 1, wherein the polymer is poly (maleic anhydride / t-butyl bicyclo [2,2,2] oct-5-ene-2-carboxylate / 3-hydroxypropyl 5-norbornene -2-carboxylate).
    [6" claim-type="Currently amended] The method of claim 1, wherein the polymer is poly (maleic anide / t-butyl 5-norbornene-2-carboxylate / 2-hydroxyethyl bicyclo [2,2,2] oct-5-ene- 2-carboxylate).
    [7" claim-type="Currently amended] The method of claim 1 wherein the polymer is poly (maleic anhydride / t-butyl 5-norbornene-2-carboxylate / 3-hydroxypropyl bicyclo [2,2,2] oct-5-ene -2-carboxylate).
    [8" claim-type="Currently amended] The method of claim 1, wherein the polymer is poly (maleic anhydride / t-butyl bicyclo [2,2,2] oct-5-ene-2-carboxylate / 2-hydroxyethyl bicyclo [2]. , 2,2] oct-5-ene-2-carboxylate).
    [9" claim-type="Currently amended] The method of claim 1, wherein the polymer is poly (maleic anhydride / t-butyl bicyclo [2,2,2] oct-5-ene-2-carboxylate / 3-hydroxypropyl bicyclo [2]. , 2,2] oct-5-ene-2-carboxylate).
    [10" claim-type="Currently amended] A method for preparing a polymer represented by the following Chemical Formula 1, characterized by reacting a maleic anhydride represented by the following Chemical Formula 2, a compound represented by the following Chemical Formula 3, and a compound represented by the following Chemical Formula 4 in the presence of a polymerization initiator.
    Formula 2

    Formula 3

    Formula 4

    Formula 1

    In the above formula,
    R represents a primary or secondary alcohol having 1 to 10 carbon atoms,
    m and n each represent a number from 1 to 3,
    The ratio of a: b: c represents 10-90: 10-90: 10-90.
    [11" claim-type="Currently amended] The method of claim 10, wherein the polymerization initiator is any one of benzoyl peroxide, 2,2-azobisisobutyronitrile (AIBN), acetyl peroxide, lauryl peroxide or t-butyl peroxide Polymer preparation method.
    [12" claim-type="Currently amended] The method of claim 10, wherein the solvent of the polymerization step is any one of tetrahydrofuran (THF), cyclohexane, methyl ethyl ketone, benzene, toluene, dioxane or dimethylformamide.
    [13" claim-type="Currently amended] The method of claim 10, wherein the polymerization process is performed for 5 to 25 hours at a temperature of 60 to 80 ° C. under a nitrogen or argon atmosphere.
    [14" claim-type="Currently amended] A photoresist comprising the polymer of formula (I) as defined in any one of claims 1 to 9, a solvent and a photoacid generator.
    [15" claim-type="Currently amended] 15. The photoresist according to claim 14, wherein the photoacid generator is sulfide salt or onium salt salt.
    [16" claim-type="Currently amended] The method of claim 14, wherein the photoacid generator is diphenyl iodo hexafluoro phosphate, diphenyl iodo salt hexafluoro arsenate, diphenyl iodo salt hexafluor antiionate, diphenyl paramethoxyphenyl triflate, diphenyl paratoluenyl Triflate, Diphenyl Paraisobutylphenyl Triflate, Diphenyl Para-t-Butylphenyl Triflate, Triphenylsulfonium Hexafluor Phosphate, Triphenylsulfonium Hexafluor Arsenate, Triphenylsulfonium Hexafluor Antimonate A photoresist, characterized in that one or more selected from dibutylnaphthyl sulfonium triflate, triphenylsulfonium triflate.
    [17" claim-type="Currently amended] 15. The photoresist of claim 14 wherein the solvent is ethyl-3-ethoxypropionate, methyl-3-methoxypropionate, propylene glycol methyl ether acetate.
    [18" claim-type="Currently amended] 15. The photoresist according to claim 14, wherein the photoacid generator contains 1 to 20% by weight of the polymer used.
    [19" claim-type="Currently amended] 15. The photoresist of claim 14 wherein said solvent contains in an amount of 100 to 700 weight percent of the polymer used.
    [20" claim-type="Currently amended] A photoresist, characterized in that the fine pattern is formed by the reaction of Scheme 2.
    (Scheme 2)

    [21" claim-type="Currently amended] A method of forming a fine pattern, characterized in that to form a pattern by a silylation process using the photoresist defined in claim 14.
    [22" claim-type="Currently amended] 22. The method of forming a micropattern according to claim 21, wherein the first and second curing of the photoresist are performed at a temperature of 110 to 150 캜 for about 30 to 300 seconds.
    [23" claim-type="Currently amended] 22. The method of forming a micropattern according to claim 21, wherein the exposure in the silylation process is performed at an exposure energy of 1 to 50 mJ / cm 2 using ArF, EUV, E-beam, or Ion-beam.
    [24" claim-type="Currently amended] The method of claim 21, wherein the silylating agent of the silylation is hexamethyldisilazane, tetramethyldisilazane, dimethylaminodimethylsilene, dimethylaminoethylsilene, dimethylsilyldimethylamine, trimethylsilyldimethylamine, trimethylsilyldiethylamine Or dimethylaminopentamethylsilane.
    [25" claim-type="Currently amended] 22. The method of claim 21, wherein the silylation process is performed at a temperature of 100 to 170 ° C for about 30 to 300 seconds.
    [26" claim-type="Currently amended] A semiconductor device formed using the photoresist of claim 14.
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    同族专利:
    公开号 | 公开日
    DE19919794A1|1999-12-09|
    US6316162B1|2001-11-13|
    GB9909916D0|1999-06-30|
    JPH11349639A|1999-12-21|
    KR100376983B1|2003-08-02|
    JP3895886B2|2007-03-22|
    CN1221856C|2005-10-05|
    GB2336845B|2002-09-04|
    GB2336845A|1999-11-03|
    CN1235171A|1999-11-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1998-04-30|Application filed by 김영환, 현대전자산업 주식회사
    1998-04-30|Priority to KR1019980016221A
    1999-11-15|Publication of KR19990081720A
    2003-08-02|Application granted
    2003-08-02|Publication of KR100376983B1
    优先权:
    申请号 | 申请日 | 专利标题
    KR1019980016221A|KR100376983B1|1998-04-30|1998-04-30|Photoresist polymer and method for forming micropattern by using the same|
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