KR20050075576A - Photoresist polymer and its composition for improvement of iso pattern - Google Patents

Photoresist polymer and its composition for improvement of iso pattern Download PDF

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KR20050075576A
KR20050075576A KR1020040003389A KR20040003389A KR20050075576A KR 20050075576 A KR20050075576 A KR 20050075576A KR 1020040003389 A KR1020040003389 A KR 1020040003389A KR 20040003389 A KR20040003389 A KR 20040003389A KR 20050075576 A KR20050075576 A KR 20050075576A
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photoresist
formula
resin
triflate
group
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KR1020040003389A
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Korean (ko)
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손민석
김일형
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주식회사 하이닉스반도체
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0395—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having a backbone with alicyclic moieties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/02—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
    • C08F232/04—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having one carbon-to-carbon double bond
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)

Abstract

포토레지스트용 조성물에 있어서, t-부틸 메타크릴레이트와 같은 결합력이 강한 ESCAP 타입의 단량체를 중합체에 도입함으로써 반응시 활성화 에너지를 높여주게 되어 ISO 패턴 형성시 프로파일을 개선할 수 있다. In the composition for a photoresist, by introducing an ESCAP-type monomer having a strong binding force, such as t-butyl methacrylate, to the polymer to increase the activation energy during the reaction can improve the profile when forming the ISO pattern.

Description

개선된 ＩＳＯ 패턴을 위한 포토레지스트 중합체 및 이를 이용한 포토레지스트조성물{Photoresist polymer and its composition for improvement of ISO pattern} Photoresist polymer and its composition for improvement of ISO pattern

본 발명은 포토 레지스트용 단량체, 이를 포함하는 그의 중합체 및 그 중합체를 이용한 포토레지스트 조성물에 관한 것이다. 더욱 상세하게는, 고집적 반도체 소자의 미세 회로 제작시, KrF(148nm), ArF(193nm), i-line, E-beam, 이온빔, 혹은 EUV의 광원을 사용한 광리소그래피 공정에 적합한 포토레지스트에 사용되는 단량체, 그 중합체 및 이를 이용한 포토레지스트 조성물에 관한 것이다. The present invention relates to a monomer for photoresist, a polymer thereof, and a photoresist composition using the polymer. More specifically, it is used in photoresists suitable for photolithography processes using KrF (148 nm), ArF (193 nm), i-line, E-beam, ion beam, or EUV light source for the manufacture of microcircuits of highly integrated semiconductor devices. A monomer, a polymer thereof, and a photoresist composition using the same.

100 여개의 단계로 이루어지는 반도체 공정 중에서 가장 기본이 되는 첫번째 layer 공정이 소자분리막(ISO Layer) 공정이다. ISO 패턴의 일반적인 모양이 몇가지 있는데, SNC 가 놓여지는 패턴의 SNC 노드 부분의 씬닝(Thinning) 현상이 항상 문제가 되어진다. The first layer process, which is the most basic semiconductor process of about 100 steps, is an ISO layer process. There are some general shapes of ISO patterns, where the thinning of the SNC node part of the pattern on which the SNC is placed is always a problem.

에너지를 조절하거나 렌즈의 노광 조건 등을 조절하여 씬닝 문제를 보상하기도 하지만 한계가 있고, 가장 근원적인 문제해결 방법은 포토레지스트의 물성을 변화 시켜 노광 에너지나 조명계의 변화에 덜 민감한 물질을 패턴 형성에 사용하는 것이다. Although it compensates for thinning problems by adjusting energy or adjusting the exposure conditions of the lens, there are limitations, and the most basic problem solving method is to change the physical properties of the photoresist so that a material less sensitive to the exposure energy or the change of the illumination system is used for pattern formation. Is to use.

그러나, 패턴이 작아지면서 DOF(Depth of Focus) 와 EL(Energy latitude) 마진이 작아지는 문제가 있어, 노광 조건의 변화를 이용한 해결책에는 한계가 있다. However, there is a problem that the depth of focus (DOF) and the energy latitude (EL) margin become smaller as the pattern becomes smaller, and there is a limit to a solution using a change in exposure conditions.

본 발명의 목적은 원자외선 영역에서 사용되어 질 수 있으면서도 ISO 패턴 형성시 SNC 노드 지역의 프로파일 개선에 큰 효과가 있는 포토레지스트 단량체와 이를 포함하는 중합체 및 그 중합체를 함유한 포토레지스트 조성물을 제공하는 것이다. SUMMARY OF THE INVENTION An object of the present invention is to provide a photoresist monomer, a polymer comprising the same, and a photoresist composition containing the polymer, which can be used in the far-ultraviolet region and has a great effect on improving the profile of the SNC node region when forming an ISO pattern. .

상기 목적을 달성하기 위하여, 본 발명에서는 포토레지스트용 수지의 단량체로 사용되는 것을 특징으로 하는 하기 화학식 1의 화합물을 제공한다. In order to achieve the above object, the present invention provides a compound of formula 1, characterized in that it is used as a monomer of the photoresist resin.

<화학식 1><Formula 1>

또한, 본 발명은, 상기 화학식 1의 화합물을 포함하는 것을 특징으로 하는 포토레지스트용 수지를 제공한다. In addition, the present invention provides a photoresist resin, characterized in that it comprises a compound of the formula (1).

본 발명에 의한 포토레지스트용 수지는 상기 화학식 1로 이루어진 호모중합체 또는 상기 화학식 1의 화합물을 포함하는 공중합체이다. 공중합체 제조시, 함께 사용될 수 있는 단량체로서는 현재 상품화되어 시판중인 ArF 감광제로 사용되는 어떠한 화합물과도 조합 가능하며, 시판중인 대표적인 ArF 감광제의 단량체로서, 발명에 이용될 수 있는 단량체로는 하기와 같은 화학식 2-4 의 화합물이 바람직하다. Resin for photoresists according to the present invention is a homopolymer consisting of the formula (1) or a copolymer comprising the compound of the formula (1). As a monomer which can be used together in the preparation of the copolymer, it can be combined with any compound which is currently commercialized and used as a commercially available ArF photosensitive agent, and is a monomer of a typical commercially available ArF photosensitive agent. Preference is given to compounds of the formula 2-4.

<화학식 2><Formula 2>

<화학식 3><Formula 3>

<화학식 4><Formula 4>

본 발명에 의한 포토레지스트용 수지는 단량체들을 통상의 연쇄중합반응 (radical reaction)에 의해 제조될 수 있다. 사용되는 유기 용매로는 테트라하이드로퓨란, 톨루엔, 벤젠, 메틸에틸케톤 및 디옥산으로 이루어진 군으로부터 선택되어 질 수 있으며, 중합개시제로는 2, 2-아조비스이소부티로니트릴(AIBN), 벤조일퍼옥사이드, 아세틸퍼옥사이드, 라우릴퍼옥사이드 및 t-부틸옥사이드로 이루어진 군에서 선택하는 것이 바람직하다. The resin for photoresists according to the present invention can be produced by monomers in a conventional radical polymerization reaction. The organic solvent used may be selected from the group consisting of tetrahydrofuran, toluene, benzene, methyl ethyl ketone and dioxane, and as polymerization initiators, 2, 2-azobisisobutyronitrile (AIBN), benzoyl per It is preferable to select from the group consisting of oxides, acetyl peroxides, lauryl peroxides and t-butyl oxides.

본 발명에 따른 중합체의 분자량은 4,000 내지 15,000 정도인 것이 바람직하다. The molecular weight of the polymer according to the invention is preferably about 4,000 to 15,000.

또한, 본 발명은 상기의 포토레지스트용 수지를 포함하는 포토레지스트 조성물을 제공한다. Furthermore, this invention provides the photoresist composition containing said photoresist resin.

본 발명에 의한 포토레지스트 조성물은 통상의 포토레지스트용 중합체를 포함할 수도 있다. 즉, 상기 화학식 1을 포함하는 공중합체 및/또는 상기 화학식 1 로 이루어진 호모중합체에 기존에 통상적으로 사용되던 ArF, KrF 및 i-Line 용 포토레지스트 수지와 함께 혼합하여 사용할 수 있다.The photoresist composition according to the present invention may also contain a conventional photoresist polymer. That is, it can be used in combination with a photoresist resin for ArF, KrF and i-Line conventionally used in the copolymer including the formula (1) and / or the homopolymer consisting of the formula (1).

본 발명에 의한 포토레지스트 조성물은 상기의 포토레지스트용 수지 외에도 가교제, 유기용매 및 광산발생제를 포함한다. The photoresist composition according to the present invention includes a crosslinking agent, an organic solvent and a photoacid generator in addition to the photoresist resin.

상기 광산발생제로는 디페닐요도염 헥사플루오르포스페이트, 디페닐요도염 헥사플루오르 아르세네이트, 디페닐요도염 헥사플루오르 안티모네이트, 디페닐파라메톡시페닐 트리플레이트, 디페닐파라톨루에닐 트리플레이트, 디페닐파라이소부틸페닐 트리플레이트, 디페닐파라-t-부틸페닐 트리플레이트, 트리페닐설포늄 헥사플루오르 포스페이트, 트리페닐설포늄 헥사플루오르 아르세네이트, 트리페닐설포늄 헥사플루오르 안티모네이트, 트리페닐설포늄 트리플레이트 및 디부틸나프틸설포늄 트리플레이트 중에서 선택되는 황화염계 또는 오니움염계 화합물이 주로 사용되며, 상기 중합체에 대하여 0.1 내지 10 중량비율로 함유되는 것이 바람직하다. The photoacid generator is diphenyl iodo hexafluorophosphate, diphenyl iodo hexafluoro arsenate, diphenyl iodo hexafluoro antimonate, diphenyl paramethoxy phenyl 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 an amount of 0.1 to 10 weight ratio based on the polymer.

상기 유기용매로는 메틸 3-메톡시프로피오네이트, 에틸 3-에톡시프로피오네이트, 프로필렌글리콜 메틸에테르아세테이트, 사이클로헥사논 및 2-헵타논으로 이루어진 군으로부터 선택되며, 상기 중합체에 대해 200 내지 800 중량비율로 사용되는 것이 바람직하다. The organic solvent is selected from the group consisting of methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propylene glycol methyl ether acetate, cyclohexanone and 2-heptanone, and is 200 to about the polymer. It is preferably used at 800 weight ratio.

상기의 화학식 1의 화합물은 폴리머의 에칭 내성을 높이기 위하여 백본에 메틸기를 첨가하였으며, CO2기 다음에 다른 탄소의 연결이 선형으로 되어있지 않다. 따라서, 결합력이 강한 ESCAP 타입의 이러한 단량체를 포토레지스트 폴리머에 도입하게 되면 여러가지 노광조건의 변화에 대한 민감도를 낮출 수 있으며, 이러한 ESCAP 타입은 활성화 에너지가 높아서 빛의 양이 많이짐에 따른 프로파일이 얇아지는 thinning 의 효과를 최소화 할 수 있는 것이다.The compound of Chemical Formula 1 added a methyl group to the backbone in order to increase the etching resistance of the polymer, and the connection of other carbons after the CO 2 group is not linear. Therefore, the introduction of these monomers of the ESCAP type having a high binding strength into the photoresist polymer can reduce the sensitivity to the change of various exposure conditions.The ESCAP type has a high activation energy and a thin profile due to the large amount of light Loss can minimize the effects of thinning.

또한, 본 발명에서는 하기와 같은 단계로 이루어지는 포토레지스트 패턴 형성방법을 제공한다 :In addition, the present invention provides a photoresist pattern forming method consisting of the following steps:

(a) 본 발명의 포토레지스트 조성물을 피식각층 상부에 도포하여 포토레지스트 막을 형성하는 단계;(a) applying the photoresist composition of the present invention on the etched layer to form a photoresist film;

(b) 상기 포토레지스트 막을 노광하는 단계; 및(b) exposing the photoresist film; And

(c) 상기 결과물을 현상하여 원하는 패턴을 얻는 단계.(c) developing the result to obtain a desired pattern.

상기 과정에서, (b)단계의 i) 노광전 및 노광후; 또는 ii) 노광전 또는 노광후에 각각 베이크 공정을 실시하는 단계를 더 포함할 수 있으며, 이러한 베이크 공정은 70 내지 200℃에서 수행된다.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.

또한, 상기 노광공정은 광원으로서 ArF, KrF 및 i-Line 를 포함하는 원자외선 (DUV; Deep Ultra Violet), E-빔, X-선 또는 이온 빔을 이용하고, 1 내지 100 mJ/cm2의 노광에너지로 수행되는 것이 바람직하다.In addition, the exposure process uses a deep ultraviolet (DUV; Deep Ultra Violet), E-beam, X-ray or ion beam including ArF, KrF and i-Line as a light source, 1 to 100 mJ / cm 2 It is preferably carried out with exposure energy.

구체적으로, 상기 포토레지스트 패턴 형성방법을 예로 들면; 본 발명의 포토레지스트 조성물을 실리콘 웨이퍼에 스핀 도포하여 박막을 제조한 다음, 80 내지 170℃의 오븐 또는 열판에서 1 내지 5분간 소프트 베이크하고, 원자외선 노광장치 또는 엑시머 레이저 노광장치를 이용하여 노광한 후, 100 내지 200℃에서 노광후 베이크한다. 이렇게 노광한 웨이퍼를 2.38TMAH 수용액에서 1분 30초간 침지함으로써 초미세 레지스트 화상을 얻을 수 있게 된다.Specifically, for example, the method of forming the photoresist pattern; The photoresist composition of the present invention was spin-coated onto a silicon wafer to prepare a thin film, and then soft-baked in an oven or hot plate at 80 to 170 ° C. for 1 to 5 minutes, and exposed using an ultraviolet ray exposure apparatus or an excimer laser exposure apparatus. Then, it bakes after exposure at 100-200 degreeC. The wafer thus exposed is immersed in a 2.38 TMAH aqueous solution for 1 minute and 30 seconds to obtain an ultrafine resist image.

또한, 본 발명에서는 상기 본 발명의 포토레지스트 조성물을 이용하여 상기 패턴 형성방법에 의하여 제조된 반도체 소자를 제공한다.In addition, the present invention provides a semiconductor device manufactured by the pattern forming method using the photoresist composition of the present invention.

이하 본 발명을 실시예에 의하여 상세히 설명한다. 단 실시예는 발명을 예시하는 것일 뿐 본 발명이 하기 실시예에 의하여 한정되는 것은 아니다. 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.

실시예 1. 호모중합체의 제조Example 1 Preparation of Homopolymer

상기 화학식 1의 t-부틸 메타크릴레이트 30g, 중합개시제 AIBN 0.6g에 테트라하이드로퓨란 75g을 250cc 플라스크에 넣고 질소 혹은 아르곤 상태에서 65℃의 온도에서 8시간 반응시켰다. 고분자 반응 완료 후 에틸 에테르 용매에서 고분자를 침전시켜 중합체를 얻었다(수율 60%, 중량평균분자량 5,650).To 30 g of t-butyl methacrylate of Formula 1 and 0.6 g of polymerization initiator AIBN, 75 g of tetrahydrofuran was added to a 250 cc flask and reacted at a temperature of 65 ° C. under nitrogen or argon for 8 hours. After completion of the polymer reaction, the polymer was precipitated in an ethyl ether solvent to obtain a polymer (yield 60%, weight average molecular weight 5,650).

실시예 2. 공중합체의 제조Example 2. Preparation of Copolymer

상기 화학식 1 의 단량체 0.1몰과 상기 화학식 2 의 단량체 0.06몰, 상기 화학식 3 의 단량체 0.01몰, 상기 화학식 4 의 단량체 0.03몰, 중합개시제인 AIBN 0.5g에 테트라하이드로퓨란 20g을 250cc 플라스크에 넣고 질소 혹은 아르곤 상태에서 65℃의 온도에서 10시간 반응시켰다. 고분자 반응 완료후 에틸 에테르 용매에서 고분자 침전을 시켜 하기와 같은 공중합체를 얻었다 (수율 65%, 중량평균분자량 6,230). 0.1 g of the monomer of Formula 1 and 0.06 mol of the monomer of Formula 2, 0.01 mol of the monomer of Formula 3, 0.03 mol of the monomer of Formula 4, 20 g of tetrahydrofuran in 0.5 g of AIBN, a polymerization initiator, were placed in a 250 cc flask. It was made to react for 10 hours at the temperature of 65 degreeC in argon state. After completion of the polymer reaction, the polymer was precipitated in an ethyl ether solvent to obtain a copolymer as follows (yield 65%, weight average molecular weight 6,230).

실시예 3-1. 포토레지스트 조성물의 제조 Example 3-1. Preparation of Photoresist Composition

상기 실시예 1에서 제조한 호모중합체 8g, 폴리(바이싸이크로[2.2.1]헵트-5-엔 / 2-하이드록시에틸바이싸이크로[2.2.1]헵트-5-엔 2-카르복실레이트 / 말레익 안하이드라이드) 12g과, 폴리(3, 3 -디메톡시프로펜) 가교제 5g과, 광산발생제로 트리페닐 설포늄 트리플레이트 0.6g을 유기용매인 프로필렌 글리콜 메틸 에테르 아세테이트 200g에 녹여 포토레지스트 조성물을 제조하였다. 8 g of the homopolymer prepared in Example 1, poly (bicyclo [2.2.1] hept-5-ene / 2-hydroxyethylbicyclo [2.2.1] hept-5-ene 2-carboxylate 12 g of maleic anhydride, 5 g of poly (3,3-dimethoxypropene) crosslinking agent, and 0.6 g of triphenyl sulfonium triflate as a photoacid generator were dissolved in 200 g of propylene glycol methyl ether acetate as an organic solvent. The composition was prepared.

실시예 3-2. 포토레지스트 조성물의 제조 Example 3-2. Preparation of Photoresist Composition

상기 실시예 2 에서 제조한 공중합체 20g, 가교제로서 폴리(3,3-디메톡시프로펜) 5g, 광산발생제로서 트리페닐설포늄 트리플레이트 0.6g 을 유기용매인 프로필렌글리콜 메틸에테르 아세테이트 200g 에 녹여 포토레지스트 조성물을 제조하였다.20 g of the copolymer prepared in Example 2, 5 g of poly (3,3-dimethoxypropene) as a crosslinking agent, and 0.6 g of triphenylsulfonium triflate as a photoacid generator were dissolved in 200 g of propylene glycol methyl ether acetate as an organic solvent. A photoresist composition was prepared.

실시예 4. 포토레지스트 패턴의 형성Example 4 Formation of Photoresist Pattern

상기의 방법으로 제조된 포토레지스트 조성물을 실리콘 웨이퍼에 도포하여 150℃에서 90초 동안 베이크 한 후 ArF 노광장비로 노광하고 이어 140℃에서 90초 동안 다시 베이크 한 후 2.38wtTMAH 현상액에서 현상하여 0.13㎛ L/S의 초미세패턴을 얻었다. The photoresist composition prepared by the above method was applied to a silicon wafer, baked at 150 ° C. for 90 seconds, exposed with an ArF exposure apparatus, and then baked again at 140 ° C. for 90 seconds, and then developed in a 2.38 wt TMAH developer to develop 0.13 μm L. An ultrafine pattern of / S was obtained.

본 발명에 의하면, 결합력이 강한 ESCAP 타입의 단량체를 중합체에 도입함으로써 반응시 활성화 에너지를 높여주게 되어 ISO 패턴 형성시 프로파일을 개선할 수 있다. 즉, 본 발명에 따라 첨가된 ESCAP 타입의 단량체를 포함하는 포토레지스트 조성물은 그렇지 않은 조성물에 비해 활성화 에너지가 높아 빛 에너지 량의 변화에 덜 민감하게 된다. 따라서 ISO 패턴을 형성할 때, 상대적으로 빛이 많이 들어오는 SNC Node 지역의 씨닝 현상을 개선할 수 있다. According to the present invention, by introducing an ESCAP-type monomer having a strong binding force into the polymer, the activation energy is increased during the reaction, thereby improving the profile when forming the ISO pattern. That is, the photoresist composition comprising the ESCAP-type monomer added according to the present invention has a higher activation energy than the composition that is not so that it is less sensitive to changes in the amount of light energy. Therefore, when forming the ISO pattern, it is possible to improve the thinning of the SNC Node region, which receives a lot of light.

또한, 조명계 등의 일관성의 변화에 의해 Eop(마진 체크를 통한 정해진 적정 양의 에너지)에서 벗어난 에너지가 전달되더라도 패턴의 프로파일에는 영향을 미치지 않도록 하는 효과가 있다. 즉, 공정 마진 측면에서 적용할 수 있는 에너지 폭이 커지므로 좀 더 쉽게 공정을 진행할 수 있고, 해상력에 있어서도 개선된 특성을 타나내게 된다. In addition, even if energy deviated from Eop (a predetermined amount of energy through a margin check) is transmitted by a change in the consistency of the illumination system, the profile of the pattern is not affected. That is, since the energy width that can be applied in terms of process margins increases, the process can be more easily performed, and improved characteristics can be exhibited in resolving power.

Claims (11)

포토레지스트용 수지의 단량체로 사용되는 것을 특징으로 하는 하기 화학식 1의 화합물.The compound of formula 1, characterized in that used as a monomer of the resin for photoresist. <화학식 1><Formula 1> 제 1 항 기재의 화합물을 포함하는 것을 특징으로 하는 포토레지스트용 수지.Resin for photoresists containing the compound of Claim 1. 제 2항에 있어서, The method of claim 2, 상기 수지는 호모중합체 또는 공중합체인 것을 특징으로 하는 포토레지스트용 수지.The resin is a photoresist, characterized in that the homopolymer or copolymer. 제 3항에 있어서, The method of claim 3, wherein 상기 공중합체는 하기 화학식 2 내지 4의 화합물 및 이들의 혼합물로 이루어진 군에서 선택되어진 하나 이상의 단량체를 포함하는 것을 특징으로 하는 포토레지스트용 수지. The copolymer is a resin for a photoresist, characterized in that it comprises at least one monomer selected from the group consisting of a compound of the formula 2 to 4 and mixtures thereof. <화학식 2><Formula 2> <화학식 3><Formula 3> <화학식 4><Formula 4> 제 2항 내지 제 4항 중 어느 하나에 의한 포토레지스트용 수지를 포함하는 것을 특징으로 하는 포토레지스트 조성물.A photoresist composition comprising the resin for photoresist according to any one of claims 2 to 4. 제 5항에 있어서, The method of claim 5, 상기 포토레지스트용 수지는 통상의 포토레지스트용 중합체를 포함하는 것을 특징으로 하는 포토레지스트용 조성물. The photoresist resin is a photoresist composition, characterized in that it comprises a conventional photoresist polymer. 제 5항에 있어서, The method of claim 5, 디페닐요도염 헥사플루오르포스페이트, 디페닐요도염 헥사플루오르 아르세네이트, 디페닐요도염 헥사플루오르 안티모네이트, 디페닐파라메톡시페닐 트리플레이트, 디페닐파라톨루에닐 트리플레이트, 디페닐파라이소부틸페닐 트리플레이트, 디페닐파라-t-부틸페닐 트리플레이트, 트리페닐설포늄 헥사플루오르 포스페이트, 트리페닐설포늄 헥사플루오르 아르세네이트, 트리페닐설포늄 헥사플루오르 안티모네이트, 트리페닐설포늄 트리플레이트 및 디부틸나프틸설포늄 트리플레이트로 이루어진 군으로부터 선택된 적어도 하나의 광산발생제를 더 포함하는 것을 특징으로 하는 포토레지스트 조성물.Diphenyluredo hexafluorophosphate, diphenylureate hexafluoro arsenate, diphenyluredo salt hexafluoro antimonate, diphenylparamethoxyphenyl triflate, diphenylparatoluenyl triflate, diphenylparaisobutylphenyl tri Plates, diphenylpara-t-butylphenyl triflate, triphenylsulfonium hexafluoro phosphate, triphenylsulfonium hexafluoro arsenate, triphenylsulfonium hexafluoro antimonate, triphenylsulfonium triflate and dibutyl A photoresist composition further comprising at least one photoacid generator selected from the group consisting of naphthylsulfonium triflate. 제 5항에 있어서, The method of claim 5, 시클로헥사논, 메틸 3-메톡시프로피오네이트, 에틸 3-에톡시프로피오네이트 및 프로필렌글리콜 메틸에테르 아세테이트로 이루어진 군으로부터 선택된 적어도 하나의 유기용매를 더 포함하는 것을 특징으로 하는 포토레지스트 조성물.A photoresist composition further comprising at least one organic solvent selected from the group consisting of cyclohexanone, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and propylene glycol methylether acetate. (a) 제5항 기재의 조성물을 소정의 피식각층 상부에 도포하는 단계와,(a) applying the composition of claim 5 on top of a predetermined layer of etching; (b) 노광장치를 이용하여 상기 기판을 노광하는 단계와,(b) exposing the substrate using an exposure apparatus; (c) 상기 결과물을 현상하는 단계를 포함하는 것을 특징으로 하는 포토레지스트 패턴 형성방법.and (c) developing the resultant photoresist pattern. 제 9 항에 있어서,The method of claim 9, 상기 노광장치는 ArF, KrF, i-Line 으로 이루어진 군으로부터 선택된 노광원을 사용하는 것을 특징으로 하는 방법.And said exposure apparatus uses an exposure source selected from the group consisting of ArF, KrF and i-Line. 제 9항 기재의 방법에 의해 제조된 반도체 소자.The semiconductor device manufactured by the method of Claim 9.
KR1020040003389A 2004-01-16 2004-01-16 Photoresist polymer and its composition for improvement of iso pattern KR20050075576A (en)

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